EUROPEAN COMMISSION DIRECTORATE-GENERAL JRC JOINT RESEARCH CENTRE Institute for Prospective Technological Studies (IPTS) Sustainable Production and Consumption Unit European IPPC Bureau 26 November 2010 Analysis of the questionnaires received on the performance of central waste water treatment plants for the review of the Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical Sector BREF INTRODUCTION This document has been prepared as a reference for the review of the Common Waste Water and Waste Gas Treatment/Management Systems in the Chemical Sector (CWW) BREF by a subgroup of the CWW technical working group (TWG). The list of the members of the CWW TWG that participated in the work of this subgroup is given in the Annexes (see Section 4.1). This document presents the results of the analysis made by the ad hoc CWW TWG subgroup of the questionnaires received regarding the performance of European central waste water treatment plants (WWTPs). The CWW TWG subgroup held two meetings in Paris (on 11– 12 January 2010 and on 24–25 June 2010) to discuss the data from the questionnaires and this document presents the result of the discussions held together with some background information researched by the European IPPC Bureau. For information, the mandate of the CWW TWG subgroup can be found in Section 4.2. This document notably takes into account many updates on the data initially provided in the questionnaires. It also takes into account information from the 'Comparative analysis of the first series of chemical BREFs' (dated December 2007) as well as the BAT conclusions reached in the first series of chemical BREFs. Furthermore, information contained in the 'Statistical analysis of monitoring data from waste water effluents of the chemical industry' – input of the German delegation to the TWG BREF CWW dated 24 March 2010 has also been taken into account in the elaboration of this document. The document is organised into three sections. Section 1 provides some background information on the questionnaires received. Section 2 analyses the performance data reported for some key parameters. The performances reported are put into perspective by comparing them with the BATAEL conclusions reached in the elaboration of the first series of chemical BREFs. Section 3 discusses the variability of the monitoring results. SR/EIPPCB/BP CWW TWG subgroup November 2010 1 TABLE OF CONTENTS INTRODUCTION ...................................................................................................................................... 1 TABLE OF CONTENTS ........................................................................................................................... 3 1 BACKGROUND ON THE QUESTIONNAIRES RECEIVED ........................................................ 4 1.1 General ........................................................................................................................................... 4 1.2 Representativity of the questionnaires ............................................................................................ 5 1.3 Quality of the questionnaires .......................................................................................................... 6 1.4 Characteristics of the central waste water treatment plants ............................................................ 8 1.4.1 General .................................................................................................................................. 8 1.4.2 Type of discharge and type of receiving waters .................................................................... 8 1.4.3 Main characteristics of the waste water influents treated ...................................................... 9 1.4.4 Main unit processes at the central WWTPs ......................................................................... 11 2 ANALYSES OF KEY PARAMETERS ............................................................................................ 13 2.1 General ......................................................................................................................................... 13 2.2 Sum parameters ............................................................................................................................ 15 2.2.1 COD, TOC, and BOD5 ........................................................................................................ 15 2.2.1.1 COD ....................................................................................................................... 15 2.2.1.2 TOC........................................................................................................................ 22 2.2.1.3 BOD5 ...................................................................................................................... 25 2.2.2 TSS ...................................................................................................................................... 30 2.2.3 AOX .................................................................................................................................... 35 2.3 Metals ........................................................................................................................................... 41 2.3.1 General ................................................................................................................................ 41 2.3.2 Cadmium (Cd) ..................................................................................................................... 46 2.3.3 Chromium total (Total-Cr)................................................................................................... 48 2.3.4 Chromium VI (Cr VI) .......................................................................................................... 50 2.3.5 Copper (Cu) ......................................................................................................................... 52 2.3.6 Mercury (Hg) ....................................................................................................................... 55 2.3.7 Nickel (Ni) ........................................................................................................................... 58 2.3.8 Lead (Pb) ............................................................................................................................. 61 2.3.9 Zinc (Zn) .............................................................................................................................. 63 2.4 Other parameters ........................................................................................................................... 67 2.4.1 Nitrogen compounds ............................................................................................................ 67 2.4.1.1 General ................................................................................................................... 67 2.4.1.2 Total nitrogen (Total-N) ......................................................................................... 67 2.4.1.3 Ammonia (as NH4-N)............................................................................................. 75 2.4.1.4 Nitrite (as NO2-N) .................................................................................................. 79 2.4.1.5 Nitrate (as NO3-N) ................................................................................................. 81 2.4.2 Phosphorus compounds ....................................................................................................... 84 2.4.2.1 General ................................................................................................................... 84 2.4.2.2 Total phosphorus (Total-P) .................................................................................... 85 2.4.2.3 Phosphate (as PO4-P) ............................................................................................. 89 2.4.3 Phenols ................................................................................................................................ 90 2.4.4 Chlorides .............................................................................................................................. 93 2.4.5 Sulphates .............................................................................................................................. 97 2.4.6 Cyanides (free) .................................................................................................................. 100 2.4.7 Toxicity.............................................................................................................................. 103 2.4.7.1 General ................................................................................................................. 103 2.4.7.2 Fish or fish egg toxicity........................................................................................ 104 2.4.7.3 Daphnia toxicity ................................................................................................... 106 2.4.7.4 Algae toxicity ....................................................................................................... 107 2.4.7.5 Bacterial luminescence toxicity ........................................................................... 108 3 DISCUSSION CONCERNING THE VARIABILITY OF MONITORING RESULTS ............ 110 SR/EIPPCB/BP CWW TWG subgroup November 2010 3 1 Background on the questionnaires received 1.1 General A total of 70 questionnaires on the performances of European central waste water treatment plants (WWTPs) have been received by the European IPPC Bureau as of 25 March 2010. Most of them have been submitted using the Word template agreed upon at the kick-off meeting of June 2008. An overview of these questionnaires is given in Table 1.1. Organisation/Member State that submitted questionnaires Austria Belgium CEFIC DE 4 FR 1 IT 1 NL 1 SE 1 UK 10 Number of questionnaires received as of 25/03/2010 1 7 Questionnaire codes 68 49, 50, 51, 52, 53, 54, 55 18 17, 18, 19, 20 (1), 21, 22, 23 (1), 24, 25, 26, 27, 28, 29, 30 (2), 31, 32, 33, 34 Czech Republic France (as Member State) France (direct submission by operators) 3 61, 62, 63 3 35, 60, 64 5 38, 39 (2), 40, 41, 57 Germany 19 Italy Portugal Spain United Kingdom (direct submission by operator) Total received: 5 2 6 01, 02, 03, 041, 042, 05, 06, 07, 08, 09, 10, 11, 12, 13, 14, 15, 16, 36, 56 42 (1), 45, 46, 58, 69 (3) 43, 44 37, 47, 48, 65 (4), 66 (4), 67 (4) 1 59 (2) 70 Taken into account for the analysis in this document: 63 20, 23 and 42 have been removed (1) 30, 39, 55 and 59 have been removed (2) (1) Removed for the analysis because: 23 was the same as 01; 20 was the same as 02; 42 is considered outside of the scope of the CWW BREF. (2) Removed for the analysis because: 30 has no information on the chemical production carried out; 39 does not treat waste waters coming chemical production; 55 has no information on emissions; 59 is the same as 32 and information on 32 is more complete. (3) Submitted on 12/02/2010. (4) Main treatment process is oxidation with H2O2. Table 1.1: Overview of the questionnaires received for the review of the CWW BREF on the performance of central WWTPs 1.2 Confidentiality of questionnaires Only a few questionnaires received by the EIPPCB were initially submitted in confidentiality. After discussions with the submitters, the latter removed the claim for confidentiality on the whole questionnaires. However, some data (few) in some of the questionnaires were claimed as confidential (generally the cost information) and was treated as such by the EIPPCB. Consequently, confidentiality is not considered a major issue for questionnaires in the review of the CWW BREF contrary to other BREFs. 4 November 2010SR/EIPPCB/Analysis questionnaires CWW CEFIC indicated that cost data are considered very sensitive in regard to antitrust issues. It considers that a WWTP, as basic infrastructure facilities, determines the competiveness of production. 1.3 Representativity of the questionnaires The questionnaires have the characteristics listed below: Relatively large number of questionnaires received (i.e. 70, of which 63 were taken for analysis, see Table 1.1). Questionnaires arise from 11 different Member States (AT, BE, CZ, DE, ES, FR, IT, NL, PT, SE, UK). Questionnaires cover direct (88 %) and indirect (12 %) discharges to receiving waters. Questionnaires reflect treatment of waste waters originating from IPPC installations from the organic sector (57 %), the inorganic sector (7 %) and both sectors (36 %). Questionnaires reflect different sizes of WWTPs, from relatively small WWTPs treating less than 10000 m3/yr (i.e. #38, #66, and #05) to large WWTPs treating volumes of waste waters above 20000000 m3/yr (i.e. #10 treating 24455000 m3/yr and #02 treating 120000000 m3/yr). This is shown in Figure 1.1. (WWTPs #02 and #10 are outside of the graph scale and are not shown in the figure). It can be noted that the waste water treatment capacity was not considered suitable for analysis/comparison because there is no common definition/understanding of waste water treatment capacity in the industry. The different sizes of WWTPs are also reflected in the annual influent load of COD reported, ranging from approximately 100 t/y – 24382 t/y (see Figure 1.2). Questionnaire #02 did not report COD in the influent, however it reported 50115 t/y TOC in the influent which is equivalent to about 145000 t/y COD. This means that the questionnaires cover WWTPs treating influent load of COD ranging from approximately 100 t/y – 145000 t/y. Average amount of waste water treated per year Average waste water treated Capacity of treatment 20000 19000 14 18000 17000 16000 22 15000 11 13000 49 12000 45 11000 10000 43 69 03 9000 041 35 8000 7000 46 63 WW treated (1000 m3 /yr) 14000 5000 4000 3000 2000 1000 0 0 38 66 05 65 32 58 52 62 41 60 24 33 29 31 34 51 67 08 40 47 19 53 25 28 56 27 61 26 37 36 09 68 17 01 18 57 12 21 48 07 13 54 50 06 042 15 16 64 44 6000 10 20 30 40 50 60 Central WWTPs Figure 1.1: Average volume of waste water treated per year in the central WWTPs reported CEFIC indicated that for Germany, the questionnaires submitted are representative of rather medium and large central WWTPs treating waste waters coming from medium-size chemical SR/EIPPCB/BP CWW TWG subgroup November 2010 5 production sites. Questionnaires do not represent the situation of indirect discharge very well (only nine questionnaires reflect the situation of central WWTPs that discharge indirectly to receiving waters, i.e. #09, #24, #31, #38, #56, #48, #65, #66, #68). COD loads treated in the Central WWTPs Annual influent COD load (t/y) 30000 25000 20000 15000 49 28 68 22 63 10000 5000 44 06 67 17 35 29 69 18 54 24 19 40 41 62 65 33 042 60 08 61 25 50 64 01 21 041 57 45 0 0 Figure 1.2: 1.4 WWTPs 33 Minimum, average, and maximum influent COD loads treated in the central WWTPs reported Quality of the questionnaires The quality of the questionnaires improved significantly with the work of the TWG subgroup who collected important information that was missing (i.e. not initially reported in the questionnaires submitted), in particular concerning: the type of recipient waters (i.e. Questionnaires numbers #041, #042, #05, #06, #07, #08, #09, #10, #11, #12, #13, #14, #15, #16, #43) the amount of waste water treated per year (i.e. Questionnaires numbers #06, #07, #20, #27, #31, #43, #54) the treatment steps/unit operations and processes (i.e. Questionnaires numbers #05, #06, #08, #24, #25, #28, #29, #40, #41, #63). Also, the TWG subgroup made numerous corrections and clarifications on a number of individual data in the compiled Excel list of questionnaires. This process of correction/clarification was very time consuming and was carried out mainly in the period January to November 2010. The EIPPCB proposed a rating of the individual questionnaires according to the completeness of the information provided. The following specific criteria have been used: A: very complete set of data submitted using the agreed upon template: i.e. #01, #02, #17, #21, #22, #24, #27, #28, #29, #34, #35, #36, #41, #43, #44, #46, #49, #50, #54, #56, #57, #58, #61, #62, #65, #67, #68, #69. 6 November 2010SR/EIPPCB/Analysis questionnaires CWW B: fairly complete set of data submitted using the agreed upon template: i.e. #03, #25, #33, #38, #40, #45, #53, #63, #64. C: set of data may not always be sufficient (background information is limited): #041, #042, #05, #06, #07, #08, #09, #10, #11, #12, #13, #14, #15, #16, #18, #19, #26, #32, #37, #47, #51, #52, #60, #66. D: fairly incomplete set of data: i.e. #48. E: very incomplete set of data: i.e., #31. SR/EIPPCB/BP CWW TWG subgroup November 2010 7 1.5 Characteristics of the central waste water treatment plants 1.5.1 General The WWTPs treat waste waters coming from one or several installations under the scope of the vertical chemical BREFs. 1.5.2 Type of discharge and type of receiving waters Effluents from central WWTPs are discharged to the following receiving waters: Direct releases (54 central WWTPs): ◦ ◦ ◦ ◦ ◦ river (i.e. #01, #02, #03, #041, #042, #05, #06, #07, #08, #10, #11, #12, #13, #14, #15, #16, #17, #18, #19, #21, #22, #26, #32, #35, #36, #41, #45, #49, #50, #51, #52, #53, #54, #56, #57, #60, #61, #62, #63, #67) lake (i.e. #64) canal (i.e. #27, #40) sea (i.e. #29, #33, #34, #37, #43, #44, #47, #48, #69) estuary (i.e. #25, #28). Indirect releases (9 central WWTPs): ◦ ◦ biological WWTP for further treatment (i.e. #09, #24, #38, #46, #58, #65, #66, #68), sometimes together with municipal waste water (i.e. #65) or in a municipal WWTP (i.e. #09, #24, #38, #58, #66, #68) settling lagoon (#31). The repartition of central WWTPs according to the type of discharge (direct/indirect) and the type of receiving waters are shown in Figure 1.3 and Figure 1.4 respectively. Type of discharge Direct releases Indirect releases Indirect releases: 9 installations (14 %) Direct releases: 54 installations (86 %) Figure 1.3: 8 Type of discharge from central WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW Receiving water River Canal Sea River: 40 install. (63 %) Estuary Lake Settling lagoon Municipal WWTP Municipal WWTP: 8 install. (13 %) Canal: 2 install. (3 %) Settling lagoon: 1 install. (2 %) Lake: 1 install. (2 %) Figure 1.4: 1.5.3 Estuary: 2 install. (3 %) Sea: 9 install. (14 %) Repartition of central WWTPs according to the receiving water Main characteristics of the waste water influents treated Central WWTPs have been put in one of the three following groups depending on the origin of the waste waters: Central WWTPs treating waste waters originating from IPPC installations of organic sectors (i.e. LVOC, OFC, POL) (36 WWTPs or 57 %): o Direct discharges: #01, #06, #07, #08, #11, #12, #13, #14, #15, #16, #18, #19, #25, #26, #28, #29, #33, #34, #36, #37, #40, #41, #47, #48, #51, #52, #53, #54, #57, #60, #62, #64; o Indirect discharges: #09, #24, #65, #66; Central WWTPs treating waste waters originating from IPPC installations of inorganic sectors (i.e. LVIC-S, LVIC-AAF, SIC, CAK) (5 WWTPs or 8 %): o Direct discharges: #042, #05, #32, #56; o Indirect discharges: #31; Central WWTPs treating waste waters originating from IPPC installations of both organic and inorganic sectors (22 WWTPs or 35 %): o Direct discharges: #02, #03, #041, #10, #17, #21, #22, #27, #35, #43, #44, #45, #49, #50, #61, #63, #67, #69; o Indirect discharges: #38, #46, #58, #68. The repartition of central WWTPs according to the main characteristics of the waste water influents treated is shown in Figure 1.5. SR/EIPPCB/BP CWW TWG subgroup November 2010 9 Type of discharge and main characteristics of the effluent treated Direct ─ mainly organic: 32 (51 %) Direct ─ both organic and inorganic: 18 (29 %) Direct ─ mainly organic Direct ─ both organic and inorganic Direct ─ mainly inorganic Indirect ─ mainly organic Indirect ─ mainly inorganic: 1 (2 %) Indirect ─ both organic and inorganic: 4 (6 %) Figure 1.5: 10 Direct ─ mainly inorganic: 4 (6 %) Indirect ─ both organic and inorganic Indirect ─ mainly inorganic Indirect ─ mainly organic: 4 (6 %) Repartition of central WWTPs according to the main characteristics of the waste water influents treated November 2010SR/EIPPCB/Analysis questionnaires CWW 1.5.4 Main unit processes at the central WWTPs In order to compare emission levels from the various installations, the techniques used were grouped. Central waste water treatment is always a combination of individual treatment steps. For example, the most commonly used activated sludge process is generally preceeded and followed by a solids removal step. The activated sludge process may be combined with simultaneous nitrification/denitrification and/or phosphorus removal depending on the composition of the waste water. The heterogeneous combinations and, in addition, the different denominations used in the questionnaires for the same technique made it difficult to group installations. Complete-mixed activated sludge was identified as the main final unit process for waste waters with organic substances and direct discharges. In the EIPPCB analysis of the questionnaires, it was assumed that unit processes denominated ''biological treatment'' or similar could be put into the same category unless more specific information was given. The installations using complete-mix activated sludge process were then further categorised according to: flat tanks, tower biology, or membrane bioreactor solids removal techniques central pretreatment steps, e.g. anaerobic step, additional activated sludge process, physico-chemical treatments occurrence of simultaneous nitrogen and/or phosphorus removal. The main unit processes used at the central WWTPs are: Physico-chemical treatments only (14 central WWTPs): ◦ ◦ ◦ ◦ ◦ ◦ ◦ Physico-chemical and biological treatment or only biological treatment (49 central WWTPs): ◦ ◦ ◦ ◦ ◦ 1 ad hoc chemical treatments (i.e. #05) neutralisation (for 54% of the plants) precipitation/flocculation followed by a solids removal step (e.g. sedimentation, filtration, or flotation) (i.e. #042, #27, #31, #32, #56); #27 with stripping as pretreatment oil-water separation and flotation (i.e. #26, #35, #46) oxidation with H2O2 (i.e. #65, #66, #67) decantation + sedimentation + ultrafiltration + stripping (i.e. #38) skimming and sedimentation (i.e. #53). Complete-mixed activated sludge (CMAS) flat tank (i.e. Questionnaires numbers #01, #02, #03, #041, #06, #09, #10, #11, #12, #17, #18, #19, #22, #24, #25, #28, #37, #40, #43, #44, #47, #48, #49, #50, #51, #52, #54, #57, #58, #60, #61, #62, #63, #64, #68) CMAS tower biology (i.e. #07, #13, #14, #15, #16, #21, #45, #57) Complete-mixed activated sludge membrane bioreactor (i.e. #08, #21, #36, #411, #69) Fixed-bed reactor (i.e. #29) Expanded bed process (i.e. #33, #34). Only part of the effluent is treated by a membrane bioreactor SR/EIPPCB/BP CWW TWG subgroup November 2010 11 With respect to solids (TSS) removal step, the following techniques are applied at central WWTPs: sedimentation (i.e. #02, #03, #041, #06, #07, #09, #12, #13, #14, #15, #16, #17, #18, #19, #22, #24, #25, #28, #37, #40, #43, #44, #47, #48, #49, #52, #54, #57, #62, #63, #68) ultrafiltration, including membrane bioreactor (i.e. #08, #21, #36, #412, #69) sand filtration (i.e. #01, #34, #45, #61) reverse osmosis (i.e. #58) has an effect on TSS removal. However it is not designed for this purpose flotation (i.e. #10, #11, #21, #29, #33, #50, #51, #60, #64). Depending on the organic load of the influent, a variety of central pretreatment processes are used, including: additional activated sludge processes (i.e. #01, #041, #08, #09, #10, #14, #33, #41, #61, #63); trickling filter (i.e. #07, #57) anaerobic pretreatment (i.e. #16, #29) oxidation (i.e. #18, #58) fixed-bed reactor (i.e. #24) oil-water separation (i.e. #45) stripping (i.e. #55). Several of the installations apply simultaneous nitrogen and/or phosphorous removal (Note: For some installations nitrogen and/or phosphorus removal were not explicitly mentioned but could be derived from the influent and effluent data): biological nitrogen removal via nitrification/denitrification (i.e. #01, #02, #03, #041, #06, #07, #08, #09, #10, #11, #12, #14, #16, #21, #22, #34, #36, #37, #40, #41, #45, #49, #50, #52, #57, #60, #61, #63, #69) phosphorus removal, either biologically and/or via precipitation (i.e. #01, #02, #03, #041, #06, #07, #10, #12, #14, #16, #57, #63). It can be noted that the complete-mixed activated sludge system is used (in combination with other techniques) in 49 central WWTPs, i.e. more than half of the central WWTPs covered by the questionnaires. 2 Only part of the effluent is treated by a membrane bioreactor 12 November 2010SR/EIPPCB/Analysis questionnaires CWW 2 Analyses of key parameters 2.1 General The following sections discuss the reported performance of central WWTPs over a number of parameters and review the BAT Associated Emission Levels (AELs) conclusions achieved in the first series of chemical BREFs. In order to help the discussion on the performances achieved and to make the link to the techniques used, a number of graphs have been made. The following symbols have been used in these graphs: Symbol Type of discharge Effluent Effluent Effluent Effluent Effluent Effluent Influent Influent Influent Influent Influent Influent Average values Type of waste water (WW) treated Direct discharge from central WWTP treating organic WW Direct discharge from central WWTP treating organic and inorganic WW Direct discharge from central WWTP treating inorganic WW Indirect discharge from central WWTP treating organic WW Indirect discharge from central WWTP treating organic and inorganic WW Indirect discharge from central WWTP treating inorganic WW Direct discharge from central WWTP treating organic WW Direct discharge from central WWTP treating organic and inorganic WW Direct discharge from central WWTP treating inorganic WW Indirect discharge from central WWTP treating organic WW Indirect discharge from central WWTP treating organic and inorganic WW Indirect discharge from central WWTP treating inorganic WW Maximum values 80th percentile 90th percentile Average values determined without removing abnormal discharges Highest monthly averages (i.e. smoothed out) No information ─ probably real maximum (i.e. outliers not removed) Outliers removed Predefined maximum value Real maximum (i.e. outliers not removed) Legend Also, the following abbreviations have been used in the graphs for the techniques reported: Abbreviatio n Adsorp. Abbreviation Definition Strip. Neut. Stripping Mechanical treatment (screen, grit chambers) Balancing of flows and loads Central incineration of WW containing recalcitrant TOC Neutralisation P precip. Phosphorus removal by precipitation Pond./lag. Prec./coag./floc. OWS Sed.1 Lag. Flot. Precipitation/coagulation/flocculation Oil-water separation (Primary) sedimentation Lagoon Flotation Biofilt. Memb. Bior. Anaerob. Nitri./deni. OHP CMAS_FT Complete-mixed activated sludge flat tank CMAS_MBR CMAS_TB Complete-mixed activated sludge tower biology Meca. Bal. Inciner. SR/EIPPCB/BP CWW TWG subgroup November 2010 Definition Adsorption Coag./floc. Coagulation/flocculation Sed.2 Final sedimentation Filtr. Filtration RO Reverse osmosis (RO) Polishing pond/sedimentation lagoon Biofilters Membrane bioreactor Anaerobic treatment Nitrification/denitrification Oxidation with H2O2 Complete-mixed activated sludge membrane bioreactor 13 Concentrations given in the graphs showing both influent and effluent emissions are average values, generally averages of 24-hour daily composite samples. Abatement efficiencies in the graphs have been calculated based on average values (generally averages of 24-hour daily composite samples) on concentration and load data, both coinciding in the majority of cases. For each parameter analysed, concentrations in the effluent of the set of central WWTPs are presented in a table so as to display the minimum (over the set of central WWTPs), the maximum, as well as the 10th, 25th, 50th, 75th and 90th percentiles. Percentiles were estimated taking the total number of data for a given parameter, multiplying it by the respective percentage (i.e. 10 %, 25 %, 50 %, 75 %, and 90 %) and rounding it to an integer. 14 November 2010SR/EIPPCB/Analysis questionnaires CWW 2.2 2.2.1 Sum parameters COD, TOC, and BOD5 Substances which have an unfavourable influence on the oxygen balance are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. 2.2.1.1 COD Background information on COD Chemical oxygen demand (COD) is commonly used to indirectly measure the amount of organic compounds in water by measuring the mass of oxygen needed for their total oxidation to carbon dioxide. The most widespread COD monitoring methods use dichromate as an oxidising agent. COD has to be considered in relation to total suspended solids (TSS) since TSS removal efficiency affects performance achieved with respect to COD (see Section 2.2.2). Care has to be taken when converting COD to TOC or vice versa using ratios; these ratios need to be well established for each case. Theoretical COD/TOC ratios of organic substances range from 0.67 (oxalic acid) to 5.33 (methane). For those central WWTPs which reported both COD and TOC data (only 8 WWTPs out of 63), COD/TOC ratios range from 2.23 to 7.01 for the influent (median 3.15) and from 1.73 to 5.54 for the effluent (median 3.17). One central WWTPs reported ratios outside the theoretical range: #44 with COD/TOC ratio of 7.01 for the influent. For WWTP #042, this could be caused by the high concentrations of inorganic substances. For economic and environmental reason, COD was replaced to some extent by TOC in Germany. To understand the consequences of this, the German national environmental agency (UBA) published a study in 1999 which compared the COD/TOC ratios for different industrial sectors. For the chemical industry, 1053 samples of 38 effluents were analyzed. The average COD/TOC ratio was 2.98, the 10th percentile was 2.39, and the 90th percentile was 4.02. The average did not change much (2.91+/-0.4) when the values <10th percentile and >90th percentile were not taken into account. Since the biological treatment is mainly an oxidative process, the COD/TOC ratio in the effluent is rather expected to be low. On the other hand, inorganic substances that contribute to the COD may be formed in the process or pass it without oxidation (esp. ammonia; maybe TSS), and oxidized material (CO2) is removed from the process. The quoted results show that in the end most effluents are expected to be in the range 2.5 – 3.5 in terms of COD/TOC ratio. Germany considers that COD concentrations are not standalone parameters for evaluating BAT. The abatement efficiency is generally a more pertinent parameter than the concentration in the effluent. Because of the strong dependency of the COD abatement efficiency on the production mix and the pretreatment techniques used, there should additionally be comments on this data, especially if COD concentration is relatively high and/or abatement efficiency is relatively low (see BREF OFC). Overview of central WWTP performance on COD Figure 2.1 presents the COD concentration in the influent and effluent of central biological WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 15 Figure 2.1: COD concentration in the influent and effluent of central biologial WWTPs It can be noted that WWTPs showing either relatively high BOD5 and/or TSS values in the effluent (i.e. #24, #28, #29, #37, #44, #57, #68) or WWTPs treating only waste waters coming from OFC plants (i.e. #06, #41, #19) tend to have higher COD emissions. Figure 2.2 presents the specific waste sludge in central WWTPs using complete-mixed activated sludge (CMAS) systems. 16 November 2010SR/EIPPCB/Analysis questionnaires CWW Specific waste sludge in central WWTPs using complete-mixed activated (CMAS) systems Sludge (t dry solids) per t of COD abated 12 11 19 10 9 8 7 6 61 5 4 60 3 2 1 49 25 44 24 01 50 28 57 54 40 62 17 64 22 69 0 0 Figure 2.2: 18 WWTPs Specific waste sludge in central WWTPs using complete-mixed activated sludge systems Figure 2.3 presents the specific energy consumption of central WWTPs using (CMAS) systems. It can be noted that installations #08, #21, #36, #41 and #69 use membrane bioreactors, which explains higher specific energy consumption. Energy (in KWh) per kg of COD abated Specific energy consumption of central WWTPs using complete-mixed activated sludge (CMAS) systems 36 041 34 32 30 28 26 24 22 69 20 18 16 14 61 12 10 8 41 08 60 6 4 19 2 49 18 28 63 44 01 68 17 57 21 40 25 45 36 0 0 Figure 2.3: WWTPs 21 Specific energy consumption of central WWTPs using complete-mixed activated sludge systems SR/EIPPCB/BP CWW TWG subgroup November 2010 17 Number of plants reporting data 51 out of the 63 WWTPs reported COD concentration values in the effluent (or 81 %) and 42 (or 82 %) of these reported COD values in the influent. 39 WWTPs reported COD loads in the effluent and 33 WWTPs in the influent. Peaks of emissions At 7 WWTPs (i.e. #25 1041 mg/l; #24, 1217 mg/l; #38, 1650 mg/l; #68, 1900 mg/l; #29, 2100 mg/l; #65, 6461 mg/l and #28, 8106 mg/l), average effluent COD is above 1000 mg/l. It can be noted that WWTPs #24, #38 and #65 are indirect dischargers and that WWTPs #38 and #65 are physico-chemical WWTPs. Averaging periods used for reporting emissions Most of the averaging periods reported are yearly averages (often of 24-hour daily composite samples). Techniques reported to minimise/reduce COD discharge The following pretreatment operations (carried out at the installation(s) from which the waste waters originate) have been reported in the questionnaires: stripping distillation adsorption extraction chemical oxidation biological treatment filtration. Treatment operations carried out in the central WWTPs are summarised in Section 1.5.4. BAT-AELs for COD in the existing series of chemical BREFs BAT-AELs for COD in the existing series of chemical BREFs are given in Table 2.1. 18 November 2010SR/EIPPCB/Analysis questionnaires CWW BREF (year adopted) Abatement efficiency (%) Emission levels (mg/l) 76 – 96 ( ) 30 – 250 (2) 1 CWW Load levels For final waste water discharge into surface water without dilution with rainwater and/or uncontaminated cooling water Free oil/hydrocarbons discharged into a receiving water For waste water emissions for the whole LVOC sector. The LVOC BREF also defines BAT-AELs for the illustrative processes (2003) 30 – 125 (3) 30 – 125 (4) LVOC (2002) OFC (2005) >95 (5) Remarks 12 – 250 (6) After treatment in a biological WWTP 19 – 30 g/t prod. 30 g/t prod. 50 – 480 g/t prod. 150 – 200 g/t prod. 3000 – 5000 g/t prod. POL (2006) LDPE GPPS PVC ESBR VSF LVIC-S (2006) LVICAAF No BAT-AELs (2006) SIC (2006) Refineries (2003) 30 – 125 (7) 3– 70 (8) g/t cop (1) Low performance rates for low contaminant concentrations. For a better comparability of strategies with or without central biological WWTP, COD-performance is based on the raw contaminant load, i.e. the load before treatment and recycling/recovery procedures. (2) Averaging period not indicated. (3) Monthly average. (4) Averaging period not indicated. The lower end of this range is determined by values of 30 – 45 mg/l for lower olefin effluents. (5) Combination of pretreatment and biological treatment. (6) Yearly average. (7) Monthly average. One Member State claims that the upper level of the concentration should be 75 and the upper value for the load should be 45 because a standard biotreater reduces the COD content by 90-97 %. As a consequence, 75 is easy to achieve in a well designed and operated biox. cop: crude oil or feedstocks processed. (8) Yearly average. Table 2.1: BAT-AELs for COD in the existing (adopted) series of chemical BREFs Reported achieved performance The COD concentrations in the effluent and the abatement efficiencies of central WWTPs are given in Table 2.2. The abatement efficiency in load versus the concentration in the effluent for COD at central biological WWTPs is given in Figure 2.4. SR/EIPPCB/BP CWW TWG subgroup November 2010 19 Abatement efficiency in load versus concentration in effluent for COD Average abatement efficiency on load (%) 100 95 90 85 80 80 70 60 50 40 30 20 10 0 Figure 2.4: Parameter COD average (mg/l) COD abatement based on concentrations (%) (6) COD abatement based on loads (%) (12) 0 100 400 400 200 300 Effluent average concentration (mg/l) 9000 Abatement efficiency in load versus the concentration in the effluent for COD at central biological WWTPs Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 9 (1) 28 (2) 52 (3) 105 (4) 295 (5) 1217 8106 44 60 82 (7) 89 (8) 95 (9) 98 (10) 99 (11) 44 52 73 (13) 88 92 (15) 95 (16) 98 (17) (1) #13 (DE) yearly average of 2h samples taken daily, abatement efficiency of 98 %. (2) #08 (DE) yearly average, abatement efficiency of 95 %. (3) #11 (DE) average based on 22 measurements. (4) #49 (BE) yearly average of 24-hour composite samples, abatement efficiency of 80 – 95 %. (5) #41 (FR); yearly averages of 24-hour composite samples, abatement efficiency of 89.6 %. (6) 42 values are summarised in this row. (7) #15 (DE), effluent average COD 148 mg/l. (8) #19 (CEFIC), effluent average 161 mg/l. (9) #40 (FR), effluent average 50 mg/l. (10) #52 (BE), effluent average 67 mg/l. (11) #58 (IT), effluent average 16 mg/l. (12) 31 values are summarised in this row. (13) #68 (AT), effluent average COD 1900 mg/l. (15) #33 (CEFIC), effluent average COD 39 mg/l. (16) #08 (DE), effluent average COD 28 mg/l. (17) #01 (DE), effluent average COD 82 mg/l. Table 2.2: 20 COD concentrations in the effluent and abatement efficiencies of central WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW It should be noted that good performers also include plants discharging indirectly to the receiving water (e.g. #58 with 16 mg/l as a yearly average and #093 with 57 mg/l as yearly average). Abatement efficiencies reported are in the range of 44 – 98 % on load. For the 50th percentile of central WWTPs and higher, abatement efficiencies on load are in the range of 88 – 98 %. Efficiencies reported for load and concentrations match in the vast majority of cases. It can be noted that several installations achieve abatement efficiencies higher than 90% with average effluent concentrations below 100 mg/l (see Figure 2.4). Fluctuations of emissions around the average (in concentration) Maximum COD values reported (often 24-hour composite samples) vary around the average by approximately a factor of 2 to 10 or more, but more generally by between 2 and 4. Changes of production or events such as shutdowns at the level of the individual chemical production plants can explain variations in COD emissions. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), COD is considered not quantifiable below 7 mg O2/l. Two international standards for measuring COD exist. ISO 6060 (1989) is applicable to water with a value between 30 mg/l and 700 mg/l. The chloride contents must not exceed 1000 mg/l. If the value exceeds 700 mg/l, the water sample is diluted. For greatest accuracy, it is preferable that the value of the sample is in the range of 300 mg/l to 600 mg/l. ISO 15705 (2002) uses the sealed tube method which is applicable up to a COD value of 1000 mg/l and a chloride concentration not exceeding 1000 mg/l. The method has a detection limit of 6 mg/l for photometric detection at 600 nm, and 15 mg/l for titrimetric detection. In addition, sealed tube tests for a COD range of 5 – 60 mg/l are commercially available. According to industry, sealed tube tests (called ultralow range, e.g. from HACH) being sensitive to chlorides lead to inaccurate results for waste waters with high chloride content. Industry therefore considers more appropriate to use TOC measurements. The TWG subgroup considers that the limit of detection (LOD) of COD is around 50 mg O2/l when high concentrations of sulphite are present. Parameters that affect performance High removal of the total organic loads depends mainly on the removal of the refractory organic fraction of this total load as well as on the optimum operation of the biological part of the treatment system to remove the biodegradable part. Relevant refractory organic loading needs adequate pretreatment. The OFC BREF indicates that refractory organic loading is not relevant if the waste water stream shows a bioeliminability of greater than about 80 – 90 %. In cases with lower bioeliminability, the refractory organic loading is not relevant if it is lower than the range of about 7.5 – 40 kg TOC per batch or per day. Once the refractory organic loading has been taken care of before the biological treatment, a number of parameters have to be kept under control to ensure the highest efficiency of the biological treatment (in terms of abatement/removal of pollutants, energy efficiency, production of sludge, odour nuisance, etc.). These parameters are, for the most part, specific to each type of biological treatment process used (suspended growth or fixed film processes) and to the technology chosen for the treatment process (e.g. trickling filter, sequencing batch reactor, membrane bioreactor). However, as a rule of thumb, smooth operation, especially with limited variations of loads and characteristics of the influent waste water, is generally desirable, especially for activated sludge processes. One should also bear in mind that (seasonal) ambient temperatures as well as the waste water temperature affect the biological treatment. 3 WWTP #09 used to discharge effluents directly to the receiving water SR/EIPPCB/BP CWW TWG subgroup November 2010 21 It should be noted that biological treatment takes time (days to weeks) to recover from upset conditions (sudden variations in the flow and load). In extreme conditions the whole population of bacteria/microorganisms has to be replaced. Fixed biomass could be less sensitive. In petroleum refineries, for example, excessive amounts of spent caustic (used to abate SOX emissions) can quickly overwhelm a waste water treatment system due to the normally high chemical oxygen demand (COD) of the spent caustic. Another issue can be a significant increase in ammonia and sulphide loads that result from upsets in the operation of sour-water strippers. These loads can, in turn, upset a biological treatment system if it is not designed to handle ammonia and sulphide. Restrictions on water usage or high water recycling can explain relatively high concentration of COD (and of pollutants in general) even if high abatement efficiency are achieved. Relation between performance and techniques used, as reported in the questionnaires There are no clear performance trend associated with the use of certain techniques or combinations of techniques. A large panel of techniques allow for achieving COD discharges below the 50th percentile for COD (i.e. 105 mg/l as a yearly average of 24-hour composite samples). Regardless of the type of treatment system selected, one of the keys to effective biological treatment is to develop and maintain an acclimated, healthy biomass, sufficient in quantity to handle maximum flows and the organic loads to be treated. 2.2.1.2 TOC Background information on TOC Total organic carbon (TOC) analysis is used to directly measure the amount of organic compounds in water. The most widespread methods use a combustion chamber to completely oxidise the organic substances to carbon dioxide which is then measured by spectrometry. Inorganic carbon is not included in the TOC. Identifying changes in the normal/expected TOC concentrations can be a good indicator of potential threats to a waste water treatment system. Various online TOC analysers exist. There is a trend to replace COD by TOC for economic and ecological reasons. Overview of central WWTP performance on TOC Figure 2.5 presents the TOC concentration in the influent and effluent of central biological WWTPs. 22 November 2010SR/EIPPCB/Analysis questionnaires CWW TOC concentration in the influent and effluent of central biological WWTPs 500 400 Number of central WWTPs 06 CMAS_TB+Anaerob.+Sed.2 36 CMAS_FT+Sed.2 47 Inciner.+CMAS_FT+Sed.2 17 CMAS_MBR+Filt. 48 CMAS_FT 51 CMAS_FT+Sed.2 OWS+CMAS_FT+Sed.2 44 041 CMAS_FT+Sed.2 50 10 CMAS_FT+Flot. 01 49 16 37 CMAS_FT 02 CMAS_FT+Sed.2+Flot. 54 07 CMAS_FT+Sed.2 11 CMAS_FT+CMAS_TB CMAS_FT+Sed.2 09 CMAS_FT+Sed.2+Flot. CMAS_FT+Sed.2+Flot. CMAS_FT+Sed.2+Pond/lag. 22 CMAS_FT+Filt. 0 08 CMAS_FT+Sed.2 0 34 CMAS_FT+Sed.2 69 CMAS_MBR 100 Exp.-bed+Flot.+Adsorp.+Filt. influent 150-550 200 CMAS_FT+Sed.2 300 CMAS_FT+CMAS_MBR+Filt. TOC (mg/l) 25 24 Overview of average values (mg/l) Maximum 339 90th percentile 133 75th percentile 60 50th percentile 39 25th percentile 18 10th percentile 12 Minimum 4 Figure 2.5: TOC concentration in the influent and effluent of central biological WWTPs Number of plants reporting data Out of the 63 WWTPs, 28 reported TOC concentration values in the effluent (or 44 %) and only about half of these reported TOC values in the influent. Peaks of emissions At one WWTP, the TOC in the effluent is above 200 mg/l (i.e. #25, TOC of 339 mg/l). Averaging periods used for reporting emissions The vast majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce TOC discharge The techniques are the same as those indicated under the COD section (see Section 2.2.1.1). BAT-AELs for TOC in the existing series of chemical BREFs No BAT-AELs for TOC are given in the series of chemical BREFs. Reported achieved performance The TOC concentrations in the effluent and the abatement efficiencies of central WWTPs are given in Table 2.3. The abatement efficiency in load versus the concentration in the effluent for TOC is given in Figure 2.6. SR/EIPPCB/BP CWW TWG subgroup November 2010 23 Abatement efficiency in load versus concentration in effluent for TOC Average abatement efficiency on load (%) 100 95 90 85 80 80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 80 90 100 100 200 300 400 Effluent average concentration (mg/l) Figure 2.6: Parameter TOC average (mg/l) TOC abatement based on concentrations (%) (6) TOC abatement based on loads (%) (7) Abatement efficiency in load versus the concentration in the effluent for TOC Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 3 (1) 6 (2) 13 (3) 35 (4) 59 (5) 158 339 39.2 73.4 84.8 93.4 94.7 96.5 97.0 39.1 78.3 80.3 92.8 94.7 96.9 97.3 (1) #042 (DE) yearly average, abatement efficiency of 80 %. (2) #56 (DE), yearly averages of of 24-hour composite samples. (3) #22 (CEFIC) based on qualified samples taken daily, abatement efficiency of 93.4 %. (4) #49 (BE) yearly average of 24-hour composite samples, abatement efficiency of 80 – 95 %. (5) #17 (CEFIC) averaging period not indicated. (6) 17 figures are summarised in this row. (7) 13 figures are summarised in this row. Table 2.3: TOC concentrations in the effluent and abatement efficiencies of central WWTPs Abatement efficiencies on loads reported are in the range 39.1 – 97.3 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are in the range of 93 – 97 %, similar to COD abatement efficiencies. Fluctuations of emissions around the average (in concentration) Maximum TOC values reported vary around the average by a factor 1.1 to 4.3 or more, but more generally by between 2 and 3. 24 November 2010SR/EIPPCB/Analysis questionnaires CWW Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), TOC is considered not quantifiable below 10 mg/l. The international standards for measuring TOC are EN 1484 (1997) and ISO 8245 (1999). Both standards are guidelines to measure TOC by oxidation via combustion, addition of an appropriate oxidant, UV-radiation, or any other high-energy radiation. The carbon dioxide formed is determined either directly or after reduction while the final determination of carbon dioxide is carried out by a number of different procedures, for example: infrared spectrophotometry, titration, thermal conductivity, conductometry, coulometry, use of carbon dioxide-sensitive sensors and flame ionisation detection. Inorganic carbon is removed by acidification and purging, or is determined separately. EN 1484 gives an application range of 0.3 mg/l to 1000 mg/l while the lower value is only applicable in special cases, for example drinking water, measured with instruments capable of measuring these low levels. Parameters that affect performance See discussion under the COD parameter (see Section 2.2.1.1). Relation between performance and techniques used as reported in the questionnaires See discussion under the COD parameter (see Section 2.2.1.1). 2.2.1.3 BOD5 Background information on BOD5 BOD5 measures the amount of dissolved oxygen required or consumed in five days at a constant temperature for the microbiological decomposition (oxidation) of organic material in water The concentration in the effluent is generally a more pertinent parameter than the abatement efficiency. CEFIC indicated that BOD5 is not a parameter that is used much in Germany to monitor industrial discharges of waste water. COD and TOC are preferred because they are considered more reliable and because they are faster to determine. CEFIC also indicated that BOD5 is not an accurate parameter to describe the efficiency of biological treatment because: The monitoring method used is not very accurate considering reproducibility and methodology dependence (dilution method versus respirometer for example); The analytical result depends on local conditions of the laboratory, such as the used inoculum for the test; BOD measurement does not allow any prediction on the performance within the WWTP. It only provides an indication whether the waste water is easily degradable to a certain rate. Germany said that the BOD5 data it delivered (i.e. 90 percentile values) reflects the variations of the biological WWTPs. For most of the BOD values given in the German questionnaires, BOD5 has been monitored weekly. The ratio BOD5/COD in the raw effluent cannot be used as an operative parameter for the waste water treatment, but gives a rough indication of biodegradability. As a rule of thumb, BOD/COD ratios before treatment of <0.2 indicate relatively undegradable organic substances, ratios between 0.2 and 0.4 indicate moderately to highly degradable organic substances, and ratios of >0.4 indicate highly degradable organic substances (see revised CWW BREF Draft 1, Section 3.2.3.4.3). BOD5/COD ratios in the influents and effluents of CWWs are shown in Table 2.4. The OFC BREF indicates that the Zahn-Wellens test provides more useful information than is possible from the BOD/TOC ratio (see Section 4.3.1.3 of the OFC BREF). SR/EIPPCB/BP CWW TWG subgroup November 2010 25 Parameter BOD5/COD ratios in influent (1) BOD5/COD ratios in effluent (2) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.00 (2) 0.22 0.33 0.45 0.53 0.58 0.81 0.00 (2) 0.03 0.05 0.10 0.18 0.29 0.44 (1) There are 30 values summarised in this row. (2) Installation #65. Possibly a data error because an influent of BOD5 at 2 mg/l and an effluent of BOD5 at 1 mg/l seem to be low figures. (2) 39 values are summarised in this row. Table 2.4 BOD5/COD ratios in the influents and effluents of CWWs. As can be seen from Table 2.4, more than 90 % of the WWTPs surveyed treat waste waters with BOD5/COD ratios >0.2. i.e. waste waters with presumably moderately to highly degradable organic substances. In the effluents, the BOD5/COD ratios are mostly <0.2 indicating waste waters with relatively undegradable substances. Overview of central WWTP performance on BOD5 Figure 2.7 presents the BOD5 concentration in the influent and effluent of central biological WWTPs. 26 November 2010SR/EIPPCB/Analysis questionnaires CWW BOD5 concentration in the influent and effluent of central WWTPs (detail) Figure 2.7: CMAS_FT CMAS_FT OWS+CMAS_FT+Sed.2 CMAS_MBR+Sed.2 CMAS_TB+Anaerob.+Sed.2 16 41 CMAS_FT+CMAS_TB+Sed.2 50 63 57 14 15 52 CMAS_FT 61 CMAS_FT 45 OWS+CMAS_FT+Flot. 041 CMAS_FT+Sed.2 49 CMAS_FT+Filt.+Pond/lag. OWS+CMAS_TB+Sed.2+Filt. 07 62 43 24 40 64 CMAS_TB+Sed.2 06 19 CMAS_TB+Sed.2 60 CMAS_FT 12 Inciner.+CMAS_FT+Sed.2 CMAS_FT+Sed.2 54 CMAS_FT+Sed.2 22 CMAS_FT+CMAS_TB 01 CMAS_FT+Filt. 13 03 CMAS_FT+Sed.2 0 08 CMAS_MBR 0 CMAS_TB+Sed.2 10 CMAS_FT+Sed.2 20 CMAS_FT+Flot. 30 CMAS_FT+Sed.2+Pond/lag. BOD5 (mg/l) 40 CMAS_FT+Sed.2+Flot. CMAS_FT+Sed.2+Pond/lag. 50 28 Number of central WWTPs BOD5 concentration in the influent and effluent of central biological WWTPs Number of plants reporting data Out of the 63 WWTPs, 42 reported BOD5 concentration values in the effluent (or 67 %) and 34 WWTPs reported BOD5 values in the influent. Peaks of emissions At eight WWTP, average BOD5 in the effluent is above 50 mg/l (i.e. #44, 58 mg/l; #46, 72.9 mg/l; #29, 150 mg/l; #37, 269 mg/l; #68, 270 mg/l; #38, 300 mg/l; #65, 1133 mgl/l; #28, 2931 mg/l, direct discharge to estuary). It can be noted that WWTPs #46, #24, #68, #38, and #65 are indirect dischargers and that WWTPs #46, #38 and #65 are physico-chemical WWTPs. Averaging periods used for reporting emissions The vast majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce BOD5 discharge The techniques used to remove COD (see Section 2.2.1.1) may remove (part of the) BOD too; on the other hand, pretreatment of COD may in certain cases raise BOD (conversion of nondegradable to biodegradable matter e.g. by partial oxydation). The only technique which is a priori dedicated to remove BOD is biological treatment (removal of C). BAT-AELs for BOD5 in the existing series of chemical BREFs The BAT-AELs for BOD5 in the existing (adopted) series of chemical BREFs are given in Table 2.5. SR/EIPPCB/BP CWW TWG subgroup November 2010 27 BREF (year adopted) Abat. efficiency (%) Emission levels (mg/l) CWW 2 – 20 (1) (2003) <20 (2) LVOC <20 (3) (2002) OFC (2005) POL (2006) LDPE GPPS PVC ESBR VSF LVIC-S >99 Load levels Remarks Free oil/hydrocarbons discharged into a receiving water After central biological treatment After central biological treatment. The LVOC BREF also defines BAT-AELs for the illustrative processes After treatment in a biological WWTP 1 – 18 (4) (2006) LVIC-AAF (2006) SIC (2006) Refineries 2 – 20 (5) 0.5 – 11 (6) g/t cop (2003) (1) BOD5: monthly average. (2) In general. Averaging period not indicated. In the case of activated sludge, a typical application is a low-loaded biological stage with a daily COD load of ≤0.25 kg/kg sludge. (3) BOD: daily average. A typical design for this treatment plant is a lowly loaded biological treatment plant, which in the case of an activated sludge plant is a COD load of ≤ 0.25 kg COD/kg sludge (as dry solids) per day. (4) Yearly average. (5) Monthly average. (6) Yearly average. Table 2.5: BAT AELs for BOD5 in the existing (adopted) series of chemical BREFs Reported achieved performance The BOD5 concentrations in the effluent and the abatement efficiencies of central WWTPs are given in Table 2.6. The abatement efficiency in load versus the concentration in the effluent for BOD5 at central biological WWTPs is given in Figure 2.8. 28 November 2010SR/EIPPCB/Analysis questionnaires CWW Abatement efficiency in load versus concentration in effluent for BOD5 Average abatement efficiency on load (%) 100 98 96 94 92 90 90 45 0 Figure 2.8: Parameter BOD5 average (mg/l) BOD5 abatement based on concentrations (%) (6) BOD5 abatement based on loads (%) (7) 10 0 50 50 40 20 30 Effluent average concentration (mg/l) 3000 Abatement efficiency in load versus the concentration in the effluent for BOD 5 at central biological WWTPs Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 1 (1) 1.5 (1 bis) 2.5 (2) 5 (3) 7.5 (4) 26.9 (5) 150 2931 51.1 68.6 94.5 97.6 98.9 99.6 99.9 51.1 65.3 91.0 97.7 98.6 99.5 99.9 (1) #08 (DE) yearly average, abatement efficiency of 99.7 %. (1 bis) #53 (BE) 24-hour composite samples (in proportion to the volume of discharged waste water). (2) #03 (DE) quarter average of 14 samples (one sample/week), abatement efficiency of 99 %. (3) #60 (FR) yearly average of 24-hour composite samples, abatement efficiency of 98.7 %. (4) #52 (BE) yearly average, abatement efficiency of 99.7 %. (5) #63 (CZ) yearly average of 24-hour composite samples, abatement efficiency of 96.3 %.. (6) 34 figures are summarised in this row. (7) 26 figures are summarised in this row. Table 2.6: BOD5 concentrations in the effluent and abatement efficiencies of central WWTPs Abatement efficiencies reported are in the range 51.1 – 99.9 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are generally >97.5 %. Efficiencies reported for load and concentrations match in the vast majority of the cases. Fluctuations of emissions around the average (in concentration) Maximum BOD5 values reported vary around the average by approximately a factor of 2 to 8 or more, but more generally by between 2.5 and 5. SR/EIPPCB/BP CWW TWG subgroup November 2010 29 Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), BOD5 is considered not quantifiable below 3 mg O2/l. Four international standards for measuring BOD exist. EN 1899-1 (1998) and ISO 5815-1 (2003) specify a BOD determination of waters by dilution and seeding with suppression of nitrification by allylthiourea. They are applicable to all waters having biochemical oxygen demands greater than or equal to 3 mg/l of oxygen (the limit of determination) and not exceeding 6000 mg/l of oxygen. EN 1899-2 (1998) and ISO 5815-2 (2003) specify a BOD determination of waters of undiluted samples. They are applicable to BOD values greater than or equal to 0.5 mg/l of oxygen (the limit of determination) and not exceeding 6 mg/l of oxygen. Parameters that affect performance See discussion on biological treatment under the COD parameter (see Section 2.2.1.1). Since BOD<COD, monitoring of BOD is not essential when COD/TOC is low. Relation between performance and techniques used as reported in the questionnaires See discussion under the COD parameter (see Section 2.2.1.1). Germany considers that it can be expected that BOD concentration in the effluent/performance is less dependent on the variation of the production than COD/TOC, and can be controlled by the proper handling of the final treatment alone. 2.2.2 TSS Background information on TSS Materials in suspension are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. There are some reasons to link the analysis of TSS with those of COD/TOC, phosphorus and BOD5. If BOD/COD/TOC removal functions poorly, TSS emissions may be affected. Conversely, high TSS values can correlate with/cause high concentrations of other parameters, namely BOD, COD/TOC, total phosphorus, total nitrogen, and metals. It is possible to have higher TSS values in the effluent than in the influent (e.g. #68, where the excess sludge is removed in a downstream municipal WWTP), which is due to the presence of biomass. Therefore, it does not make sense to calculate abatement efficiencies for the whole central WWTP, which are heterogeneous combinations of different unit processes. The concentration in the effluent is generally a more pertinent parameter than the abatement efficiency. Overview of central WWTP performance on TSS Figure 2.9 presents the TSS concentration in the influent and effluent of central biological WWTPs. Figure 2.10 presents the TSS concentration in the influent and effluent of central physico-chemical WWTPs. 30 November 2010SR/EIPPCB/Analysis questionnaires CWW TSS concentration in the influent and effluent of central biological WWTPs (detail) 51 29 Figure 2.9: Meca.+Flot.+Filt. 0 CMAS_MBR 0 61 21 33 54 19 43 Sed.2+Flot. 50 44 Air_flot. Sed.1+Sed.2 Meca.+Sed.2 Sed.2+Pond/lag. 62 49 60 influent 20-430 Flot. 64 Meca.+OWS+Sed.1+Sed.2 OWS+Air_flot.+Flot. 41 041 Meca. 40 09 Sed.2 07 45 37 Sed.1 03 02 Sed.1+Sed.2 01 08 Filt.+Pond/lag. 34 Sed.1+Filt. 10 Sed.1+Sed.2 20 Sed.2+CMAS_MBR Sed.1 30 Air+flot. 40 Sed.1+Sed.2 50 OWS+Sed.1+Sed.2+Filt. 60 Sed.1+Flot. TSS (mg/l) 70 Meca.+OWS+Sed.1+Sed.2 17 Sed.2 80 Sed.2 48 90 Flot. 100 29 Number of central WWTPs TSS concentration in the influent and effluent of central biological WWTPs It is to be noted that there is only one TSS measurement for WWTP #51. It can be noted that WWTPs showing either relatively high BOD5 and/or COD/TOC values in the effluent (i.e. #18, #24, #25, #57) tend to have higher TSS emissions. SR/EIPPCB/BP CWW TWG subgroup November 2010 31 TSS concentration in the influent and effluent of central physico-chemical WWTPs 500 direct organic 400 dir. org.+inor. direct organic ind. org.+inor. dir. org.+inor. inder. organic ind. org.+inor. 300 0 32 Sed.+Air+flot. 0 67 Meca.+Sed. 042 35 27 53 OWS+Air_flot. 100 Sed.1+Filt. inder. organic Sed.1+Sed.2 200 Meca.+OWS+Sed.1+Flot. 65 38 46 9 Number of central WWTPs Overview of average values (mg/l) Maximum 89 90th percentile 55 75th percentile 28 50th percentile 24 25th percentile 15 10th percentile 9 Minimum 5 TSS concentration in the influent and effluent of central physico-chemical WWTPs (detail) 100 OWS+Air_flot. 46 90 80 50 40 30 20 32 10 0 Figure 2.10: Meca.+Sed. 042 0 Sed.+Air+flot. 67 35 65 53 38 27 Sed.1+Filt. 60 Meca.+OWS+Sed.1+Flot. TSS (mg/l) 70 Sed.1+Sed.2 direct organic TSS (mg/l) dir. org.+inor. 9 Number of central WWTPs TSS concentration in the influent and effluent of central physico-chemical WWTPs Number of plants reporting data Out of the 63 WWTPs, 48 reported TSS values in the effluent (or 76 %) and only about half of these reported TSS values in the influent. Peaks of emissions At two WWTPs, TSS is above 1000 mg/l (i.e. #28 with 1729 mg/l and #68 with 1900 mg/l). It can be noted that WWTP #68 is an indirect discharger. Averaging periods used for reporting emissions Most of the averaging periods reported are yearly averages of 24-hour daily composite samples (e.g. #07 reported an average of 300 random samples, #35 reported a yearly average of monthly averages values). 32 November 2010SR/EIPPCB/Analysis questionnaires CWW Techniques reported to minimise/reduce TSS discharge The following pretreatment operations (carried out at the installation(s) from which the waste waters originate) have been reported in the questionnaires: grit separation of solids coagulation and flocculation sedimentation of solids filtration microfiltration and ultrafiltration nanofiltration (NF). These can also be carried out as part of a central biological treatment plant. Treatment operations carried out in the central WWTPs are summarised in Section 1.5.4. Membrane bioreactors achieve high TSS removal and smaller plant footprint (no need for a secondary clarifier and tertiary filtration system, elevated mixed liquor concentrations are possible), however energy consumption is an important cross-media effect as shown in Figure 2.3. Conventional activated sludge processes can in some cases be retrofitted to accommodate membranes. However, membranes are not applicable to all sites. BAT-AELs for TSS in the existing series of chemical BREFs The BAT-AELs for TSS in the existing (adopted) series of chemical BREFs is given in Table 2.7. BREF (year adopted) CWW (2003) Abatement efficiency (%) Emission levels (mg/l) Load levels Remarks 10 – 20 (1) Monthly average for final waste water discharge into surface water, without dilution with rainwater and/or uncontaminated cooling water 10 – 20 (2) After treatment in a biological WWTP LVOC (2002) OFC (2005) POL (2006) LDPE GPPS PVC ESBR VSF 10 g/t prod. 10 g/t prod. 0.5 – 2.5 kg/t TiO2 (3) 1 – 40 kg/t TiO2 (4) LVIC-S (2006) LVIC-AAF (2006) SIC (2006) Refineries (2003) 2 – 50 (5) 1 – 25 g/t cop (6) (1) Monthly average. (2) Yearly average. (3) Titanium dioxide – chloride route. (4) Titanium dioxide – sulphate route. (5) Monthly average. (6) Yearly average. cop: crude oil or feedstock processed. Table 2.7: BAT AELs for TSS in the existing (adopted) series of chemical BREFs Abatement efficiency and emission levels associated with techniques used to remove TSS as reported in the adopted CWW BREF are given in Table 2.8. SR/EIPPCB/BP CWW TWG subgroup November 2010 33 Abatement efficiency (%) 60 – 90 Emission levels (mg/l) <10 90 – 98 85 – 96 10 – 20 Filtration 50 – 99.99 <10 Microfiltration and ultrafiltration about 100 close to 0 Techniques used Sedimentation Air flotation Table 2.8: Load levels Remarks After final clarifier of central WWTP Activated sludge after final clarifier, input 20–250 mg/l Activated sludge floc Sand filter, dependent on filter aids Energy is an important crossmedia effect. These techniques are used especially when water is to be reused Abatement efficiency and emission levels associated with techniques used to remove TSS as reported in the adopted CWW BREF Reported achieved performance The TSS concentration in the effluent of central WWTPs is given in Table 2.9. Parameter TSS average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 1.1 (1) 9 (2) 15 (3) 28 (4) 80 (5) 150 1900 (1) #08 (DE) yearly average based on 150 measurements, (2) #61 (CZ) yearly average of 24-hour composite samples. (3) #59 (UK) ) yearly average of 24-hour composite samples. (4) #27 (CEFIC) yearly average of weekly samples. (5) #29 (CEFIC) based on spot samples once per week + online turbidity measurement. Table 2.9: TSS concentration in the effluent of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum TSS values reported vary around the average approximately by a factor of 1.5 to 10, but more generally by between approximately 2 and 3. Seasonal variations (e.g. rain period) and the treatment of storm water (sometimes from a nearby city) may cause higher variability in TSS effluent concentration. This has to be taken into account in deriving BAT conclusions. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), TSS is considered not quantifiable below 2 mg/l. Two international standards, EN 872 (2005) and ISO 11923 (1997), describe a method for the determination of suspended solids in raw waters and waste waters by filtration though glass-fibre filters. The lower limit of the determination is in both cases approximately 2 mg/l. Since TSS at the outlet of biological treatment plants consists mainly of organic matter and COD/TOC also cover suspended matter, monitoring of TSS is not essential when COD/TOC is low. Relation between performance and techniques used as reported in the questionnaires 34 November 2010SR/EIPPCB/Analysis questionnaires CWW The performance of the central WWTPs with respect to the removal of solids depends on the techniques used, but also on the characteristics of the waste waters and the operating conditions of the installations (e.g. residence time in the final clarifier in the case of sedimentation). TSS values of mostly below 20 mg/l are achieved by installations using sand filtration (e.g. #34: 5 mg/l, #01: 6 mg/l, #61: 9 mg/l, #32: 15 mg/l, and #45: 22 mg/l). Installations using ultrafiltration as the main solids removal step (often as part of a membrane bioreactor) also tend to show low TSS values in the effluent (i.e. #36: <detection limit, #69: <5 mg/l, #414: 17 mg/l, and #38: 26 mg/l). No information on TSS is available for installation #58 which uses reverse osmosis (RO). Installations using flotation tend to show higher TSS values in the effluent (15 – 100 mg/l), although 3 out of the 8 installations reporting the use of flotation (i.e. #33, #35, #64) achieve TSS values below 20 mg/l, the upper range of the BAT level of the current CWW BREF. The largest spread of TSS effluent values is found when sedimentation as the main solids removal step is used (5 – 1900 mg/l). Nevertheless, 8 out of 30 installations using sedimentation achieve TSS values below 20 mg/l, and 3 installations implementing sedimentation achieve TSS values below or equal to 10 mg/l. 2.2.3 AOX Background information on AOX AOX is a sum parameter which indicates the overall level of organohalogen compounds (chlorine, bromine and iodine) in water samples. It is important as many organohalogen compounds are toxic (especially the fat-soluble chlorinated group – dioxins, furans, and polychlorinated phenolic compounds) and/or persistent. However, as a sum parameter, AOX gives neither information on the chemical structure of organohalogen compounds present nor on their toxicity. The AOX method has the advantage that it is quite a simple measurement if it is compared to the alternative methods of measuring levels of individual compounds which are complex and require costly equipment. High concentrations of organic compounds or inorganic chlorides may interfere with the AOX measurement. AOX is an operational parameter, i.e. the measurement procedure determines the result. AOX cannot be used to monitor very volatile compounds. AOX is routinely monitored in Germany. AOX or EOX is also monitored, albeit less routinely it seems, in Austria, France (EOX), Belgium, the Czech Republic, Italy, the Netherlands (EOX) and Spain. It is worth noting that 31 out of the 70 WWTPs (or 44%) reported AOX or EOX values in the effluent. AOX or EOX has been reported by Austria (i.e. #68), Belgium (i.e. #50, #53, #54), the Czech Republic (i.e. #61, #63), France (i.e. #35, #38, #60), Germany, Spain (i.e #47, #65). AOX values are generally higher than EOX values (possibly by a factor of 10). AOX is the only parameter used in Germany, whereas both AOX and EOX are used in Belgium, France and the Netherlands. Both EOX and AOX parameters are included in the basic environmental quality standards for discharge into surface water in Belgium (Flanders). Furthermore, AOX or EOX is included in the Flemish sectoral discharge conditions for industrial waste water. CEFIC raised the question whether there is sufficient data on AOX/EOX to draw BAT conclusions for the whole EU. Germany pointed out that the data delivered for Germany reflect a broad spectrum of chemical sites (regarding production mix, large and medium size sites). For questionnaires #17 and #36, the Organic Fine Chemicals (OFC) BREF should be referred to where high AOX values are explained. AOX is one of the key pollutants of the European Pollution Release and Transfer Register (E-PRTR). 4 Only a part of the whole effluent is treated by the membranes. In 2009, the average concentration was 10 mg/l compared to 17 mg/l in 2007. SR/EIPPCB/BP CWW TWG subgroup November 2010 35 Specific information regarding AOX abatement presented in the vertical chemical BREFs is discussed in the following paragraphs. It is important to note that this parameter is mainly associated with the production of organic chemicals and silicones. In the CAK, LVIC-AAF and LVIC-S BREFs, there is no information on AOX reported. In SIC processes, AOX emissions are not regarded as a common general environmental issue for the sector as a whole. AOX could be carried by the waste water from plants producing silicones. The techniques reported for AOX abatement are chemical oxidation, nanofiltration/reverse osmosis, adsorption, stripping, incineration, anaerobic biological digestion and aerobic biological digestion. In some LVOC processes, i.e. the production of lower olefins, aromatics, oxygenated compounds, nitrogenated compounds and halogenated compounds, the waste waters contain AOX loads after pretreatment and prior to biological treatment. Waste water streams containing high AOX/EOX loads are preferably pretreated or recovered separately, e.g. by (chemical) oxidation, adsorption, filtration, extraction, (steam) stripping, hydrolysis (to improve biodegradability) or anaerobic pretreatment. The LVOC TWG acknowledged that it was difficult to describe BAT-AELs for AOX that were applicable for all LVOC processes as the waste water characteristics are strongly influenced by the applied processes, operational process variability, water consumption, source control measures and the extent of pretreatment. Nevertheless, based on their expert judgement, a general BAT-AEL for AOX was set. In OFC processes, the main sources for waste water streams with relevant AOX loads are processes/operations involving halogenated solvents and halogenated intermediates, products and by-products. Mass balances for emissions inventories are mentioned as being essential for understanding on-site processes and the development of improvement strategies. Pretreatment includes, e.g. distillation, stripping, activated carbon adsorption, extraction and membrane processes. The pretreatment can also be done by oxidation, e.g. chemical oxidation, high pressure wet oxidation and low pressure wet oxidation, or disposal (incineration). After pretreatment, the effluent is sent to biological treatment. The BAT-AELs set can be seen in Table 2.10. It is important to notice that the OFC BREF with its diverse sectors shows systematic similarities with the CWW BREF. In fact, the discussion on AOX was based on a similar set of reference plants. In POL processes, AOX emissions occur during PVC production. Since AOX also covers solid compounds, the parameter is used to control overall PVC recovery/removal. Further, AOX emissions can occur during viscose fibre and viscose filament yarn production. However, no further information is reported. Overview of central WWTP performance on AOX Figure 2.11 presents the AOX concentration in the influent and effluent of central biological WWTPs. 36 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.11: AOX concentration in the influent and effluent of central biological WWTPs The following points are woth worth mentionning: EOX is reported for WWTP #17. WWTPs #36 and #06 are special cases dealt with in the OFC BREF. At WWTP #57, the use of bleach treatment as pretreatment is the reason for high AOX At WWTP #68 (AT), 2 samples were taken in 2009 and the results showed <0.01 mg/l and 0.012 mg/l for AOX. Number of plants reporting data AOX values (concentrations and/or loads) have been reported by Austria (i.e. #68), Belgium (i.e. #49, #53, and #54), the Czech Republic (i.e. #61, and #63), France (i.e. #35, #38, and #60), Germany (i.e. #01, #02, #03, #041, #042, #06, #07, #09, #10, #11, #12, #13, #14, #15, #16, #36, and #56), Italy (i.e. #69), Spain (i.e. #47, and #65), Industry (i.e. Questionnaires #17, #21, #22, #25, and #57). Out of the 63 WWTPs, 31 reported AOX concentration values in the effluent (or 49 %). Of these values, 30 are of spot-type while one is given as a range-type value (i.e. <0.20 mg/l). Peaks of emissions At four WWTPs (i.e. #57 with 3.6 mg/l, #17 with 9.6 mg/l – EOX, #36 with 17 mg/l, and #65 with 29.3 mg/l), AOX/EOX is above 1 mg/l. These data are not shown on the figure above. It can be noted that for #65, the figure of 29.3 mg/l is based on a single measurement that is not considered very reliable by the operator. The operator considers that this is due to the complexity of the AOX analysis that requires a first stage of absorption, digestion and usually photometric final analysis. According to Spain, depending on the interferences, it is advisable to use absorbent polymer instead of charcoal for the absorption stage (e.g. if there are many chlorides). Additionally, very high COD may give false on AOX. Averaging periods used for reporting emissions Often, the averaging periods reported are yearly averages of 24-hour daily composite samples. SR/EIPPCB/BP CWW TWG subgroup November 2010 37 Techniques reported to minimise/reduce AOX discharge The main techniques to reduce AOX emissions are the segregation and selective pretreatment of waste water streams from processes where AOX is an issue. The following pretreatment operations (carried out at the installation(s) from which the waste waters originate) have been reported in the questionnaires: oxidation (i.e. #07) stripping (i.e. #12, #14, #15, #17, #19, #21, #22, #36, #68) adsorption on activated carbon (i.e. #13, #15, #21) decantation (i.e. #17) oil-water separation (i.e. #27) distillation (i.e. #36, #68). Regarding AOX removal at the central WWTPs, the following techniques were reported: oxidation (i.e. #65 where a wet oxidation process with H2O2 is used to remove several pollutants including AOX); stripping (i.e. #27, #38); adsorption on activated carbon (e.g. #07, #34); reverse osmosis (i.e. #58). BAT-AELs for AOX in the existing series of chemical BREFs The BAT-AELs for AOX in the existing (adopted) series of chemical BREFs is given in Table 2.10. 38 November 2010SR/EIPPCB/Analysis questionnaires CWW BREF (year adopted) CWW (2003) LVOC (2002) OFC (2005) Abatement efficiency (%) none Emission levels (mg/l) Load levels Split view: one Member State insists on naming BAT-AELs for AOX based on the examples given in Annex 7.6.2. They state that in this Member State on some chemical sites with production of chloro-organic chemicals and central waste water treatment plants, AOX emission levels between 0.16 and 1.7 mg/l are achieved. The TWG did not follow this request. The examples presented (see Annex 7.6.2) were interpreted as consisting of different statistical data sets which did not allow naming BAT-AELs. It was even mentioned that one of the lowest AOX emission values reported as examples represented poor performance, whereas the highest emission value came from a site with very good performance. Under these conditions, the TWG saw it to be unsuitable to give BAT-AELs for AOX For waste water emissions for the whole LVOC sector. The LVOC BREF also defines BAT-AELs for the illustrative processes After treatment in a biological WWTP. none <1 (1) 0.1 – 1.7 (2) POL (2006) PVC Remarks 1 - 12 g/t PVCM AOX levels of 0.5 – 8.5 at the inlet of the central WWTPs is the BAT-AEL. The upper range relates to cases where halogenated compounds are processed in numerous processes and the corresponding waste water streams are pretreated and/or where the AOX is very bioeliminable. In the final effluent are achieved for PVC production sites or combined EDC, VCM and PVC production LVIC-S (2006) LVIC-AAF (2006) SIC (2006) Refineries (2003) (1) Most LVOC processes can achieve an AOX value of below 1 mg/l. (2) Yearly average. The upper end of the range results from numerous AOX relevant productions and pretreatment of waste water streams with significant AOX loads. Table 2.10: BAT-AELs for AOX in the existing (adopted) series of chemical BREFs SR/EIPPCB/BP CWW TWG subgroup November 2010 39 Reported achieved performance The AOX concentrations in the effluent and the abatement efficiencies of central WWTPs are given in Table 2.11. Parameter AOX average (mg/l) AOX abatement based on concentrations (%) (6) AOX abatement based on loads (%) (7) Minimum 10th percentile 25th percentile 50th percentile 0.23 (4) 0.28 (4 bis) 75th percentile 90th percentile Maximum 0.03 (1) 0.08 (2) 0.1 (3) 0.6 (5) 0.9 29.3 (8) -10.0 40.0 52.5 76.7 85.7 86.7 88.9 -16.9 -16.9 40.4 59.6 78.7 83.1 89.0 (1) #09 (DE) based on 19 measurements. (2) #56 (DE) averaging period not indicated. (3) #11 (DE) average based on 20 measurements. (4) #16 (DE) yearly average of 24-hour composite samples. (4 bis) #53 (BE) 24 hours composite samples (in proportion to the volume of discharged waste water). (5) #49 (BE) yearly average of 24-hour composite samples. (6) 17 figures are summarised in this row. (7) 13 figures are summarised in this row. (8) #65 (ES) which is a physico-chemical WWTP. A maximum of 17 mg/l is achieved for WWTP #36 (DE). Table 2.11: AOX concentrations in the effluent and abatement efficiencies of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 24 installations. Maximum AOX values reported vary around the average by a factor of 1.3 to 5.4, but more generally by between approximately 2 and 3. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), AOX is considered not quantifiable below 20 µg/l. The most widely accepted monitoring method is EN ISO 9562 (2004) which replaced the European standard EN 1485 (1997). The standard specifies a method for the direct determination of an amount of usually 10 µg/l in water of organically-bound chlorine, bromine and iodine (expressed as chloride) adsorbable on activated carbon. This method is applicable to test samples with concentrations of inorganic chloride ions of less than 1 g/l. Samples with higher concentrations are diluted prior to analysis. No European or International standard for the determination of EOX exists. The standard for the determination of EOX in Germany is DIN 38408/H8 (1984) and NEN 6402 (1991) in Belgium (Flanders). Parameters that affect performance Organohalogen compounds are part of the organic load of waste waters. AOX is therefore a part of COD/TOC, and, if biodegradable, also of BOD5. See therefore the discussion under the COD parameter in Section 2.2.1.1. Relation between performance and techniques used as reported in the questionnaires See the discussion under the COD parameter in Section 2.2.1.1. 40 November 2010SR/EIPPCB/Analysis questionnaires CWW 2.3 2.3.1 Metals General Background information on metals, their abatement and BAT conclusions reached in the chemical BREFs Important characteristics of (heavy) metals which influence waste water treatment are given below: Metals are not degradable and almost all of them are adsorbed to the sludge or passed through the biological WWTP. High levels of metals can inhibit the biological processes in central WWTPs, but certain concentrations are needed for the growth of the organisms. High metal loadings in sewage sludge cause problems for disposal (in the case of agricultural use of sewage sludge) Once discharged to water, metals from sediment can remobilise in the waterbody (river or sea). The waste waters of many chemical processes contain metals, e.g. they are contained in the materials used for chemical processing (feedstock, auxiliaries and catalysts). The corrosion of pipes and equipment is also an important source of metals (especially Cu, Zn, Cr, Ni) in effluents of central WWTPs (in low concentrations, however often representing the main input regarding loads). Specific information regarding metals removal presented in the vertical chemical BREFs is discussed in the following paragraphs. The OFC, SIC, LVOC and LVIC-S BREFs describe several techniques that are used to reduce the content of metals in waste waters. The CAK BREF covers mainly the abatement of mercury from mercury cell plants. Historical mercury contamination of land and waterways from mercury cell plants is reported as a major environmental problem at some sites. Considerable emissions of mercury can also occur with run-off water. Mercury emitted to water from mercury cell facilities mainly arises from: bleed from brine purification and condensates the wash water from the cell cleaning operations rainwater from the electrolysis hall the rinsing water from maintenance areas. In CAK processes, waste water contaminated with mercury is collected from all sources and is generally treated in a waste water treatment plant. The amount of waste water can be reduced by filtration and the washing of the sludges to remove mercury before feeding the condensate back into the brine. The use of process-integrated techniques, e.g. the monitoring of possible leakages and the recovery of mercury, good housekeeping and the use of salt with low impurity content are reported. End-of-pipe measures include precipitation as sulphide and mercury removal from hydrogen gas and caustic soda. In LVIC-AAF processes, metals such as nickel and vanadium (introduced with the feedstock) are suspended as oxides and are also partially present as salts in the soot water circuit. To prevent an accumulation of these compounds in the water circuit, some of the extracted water has to be drained. The waste water is treated by flocculation, applying settlers and/or filters, and being finally discharged after biological treatment. Heavy metal emissions occur during phosphoric acid and AN/CAN production. The use of raw materials (coke, gypsum) with lower heavy metal content is reported as essential. No BAT-AELs were derived for metals in the LVIC-AAF BREF. SR/EIPPCB/BP CWW TWG subgroup November 2010 41 Metals are regarded as major contaminants for LVIC-S processes. The problem arises as metals naturally occur in the main raw materials (e.g. limestone, coke, brine, feedstock and scrap iron). In soda ash production, metals are not retained in the product, but pass through the process to be finally released mainly with suspended solids in the waste waters from distillation. No BATAELs were defined for soda ash production. The main reason was that 90 % of the metals emissions originate from the use of raw materials (limestone and salt brine), and the operators have little influence on changing the currently exploited limestone or brine deposit. However, the emissions of metals in the production of soda ash were thoroughly investigated in the LVICS BREF and detailed data from examples plants were reported. Also, the management of waste waters from the production of soda ash was illustrated in detail. In titanium dioxide and food phosphates production, metals are also passed to the waste waters. BAT-AELs were set only for titanium dioxide production using the sulphate route (see Table 2.12). However, techniques are described in order to reduce the presence of metals in the waste waters, i.e.: the selection of raw materials which contain a lower content of metals, e.g. quality limestone, salt brine, coke, feedstock and scrap iron deposition and dispersion separation of solids and filtration sedimentation using settling ponds. In SIC processes, the use of catalysts creates waste water contaminated with metals. Metals could be carried by the waste water from plants producing pigments, explosives, silicones and nickel salts. Segregation and separation of the waste water containing metals is essential. The techniques used for their removal are sedimentation, air flotation, filtration, precipitation, crystallisation, chemical reduction, nanofiltration/reverse osmosis, adsorption, ion exchange, evaporation, and anaerobic biological digestion. No generic BAT conclusions on the abatement of metals in waste water were derived. The BAT-AELs set for speciality inorganic pigments are shown in Table 2.12. For LVOC processes, metals are also regarded as major water pollutants. The main source is the use of catalysts. The metals (from catalysts) are treated or recovered separately, because they cannot be removed efficiently in biological treatment plants. The techniques used are chemical precipitation (creating a sludge that may allow metal recovery), ion exchange, electrolytic recovery or reverse osmosis. The treated waste water streams are discharged to a combined biological treatment plant for further treatment. The BAT-AELs set for metals in the LVOC BREF can be seen in Table 2.12. In OFC processes, metals are involved in chemical processing, e.g. as feedstock, auxiliaries and catalysts. Mass balances for emissions inventories are considered essential for understanding on-site processes and the development of improvement strategies. The main factor to actively influence the emission level of heavy metals is the segregation and selective pretreatment of waste water streams from processes where heavy metals are used deliberately. If equivalent removal levels can be demonstrated in comparison with the combination of pretreatment and biological waste water treatment, heavy metals can be eliminated from the total effluent using only the biological waste water treatment process, provided that the biological treatment is carried out on-site and the treatment sludge is incinerated. The BAT-AELs set for metals in the OFC BREF are shown in Table 2.12. It is important to notice that the OFC BREF with its diverse sectors shows systematic similarities with the CWW BREF. In fact, the discussion on metals was based on a similar set of reference plants. In the POL BREF, there is little information reported on the presence of metals in waste waters and/or their abatement. BAT-AELs for metals in the existing series of chemical BREFs are given in Table 2.12. 42 November 2010SR/EIPPCB/Analysis questionnaires CWW BREF (year adopted) CAK CWW (2003) LVOC (2002) Hg Cd Cu, Cr, Ni, Pb Zn, Sn OFC (2005) Cu Cr Ni Zn Abateme nt Emission Load efficienc levels Remarks levels y (mg/l) (%) No BAT-AELs for mercury were set; however, it is reported in the document that the best performing mercury cell plants achieve total mercury losses to air and water, with products in the range of 0.2 – 0.5 g/t chlorine capacity as a yearly average Split view: the following long term mean values (yearly of 24-hour mixed samples) in some examples of chemical sites at the discharge point/last waste water treatment stage could be reached (without dilution of the waste water with rain and cooling water): Cd 0.02 – 0.833 μg/l; Hg 0.01 – 0.84 μg/l; Pb 10 – 100 μg/l; Cr 10 – 30 μg/l; Cu 20 – 60 μg/l; Ni 10 – 80 μg/l; Zn 4 – 174 μg/l. TWG members further state that the none none values are influenced by the portion of productions relevant to metals and hence are dependent on the production mix, which can cause higher values in special cases, especially in fine chemicals production. With regard to releases into public sewerage systems, the effect of the WWTP would have to be taken into account in so far as it would be ensured that the metals are not shifted to other media For waste water emissions for the whole LVOC sector. Values refer to 1 0.05 ( ) tributary streams after dedicated 0.2 (1) pretreatment and before final treatment. 1 0.5 ( ) The LVOC BREF also defines BAT1 2() AELs for the illustrative processes 0.007 – 0.1 (2) 0.004 – 0.05 (2) 0.01 – 0.05 (2) <0.1 (2) After treatment in a biological WWTP POL (2006) Zn 10 – 50 g/t of viscose staple fibres LVIC-S (2006) Hg Cd 0.32 – 0.0015 mg/t TiO2 (3) 1 – 2000 mg/t TiO2 (3) LVIC-AAF (2006) SIC (2006) Cd Crtotal Pb Refineries (2003) (4) <=0.1 <0.5 (4) 50 g/t end-prod. (4) 5 – 10 g/t end-prod. (4) 20 – 40 g/t end-prod. (4) <0.1 – 4 (5) (1) As daily averages. (2) Yearly average. The upper end of the range results from the deliberate use of metals or heavy metal compounds in numerous processes and the pretreatment of waste water streams from such use. (3) Titanium dioxide – sulphate route. 4 ( ) Annual average. Production of inorganic pigments. (5) Total metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, V, Zn), monthly average. It should not be understood from this range that the amount of very toxic metals (e.g. As, Cd, Hg, Pb) can reach concentrations of this order of magnitude. Two Member States claimed that the group of metals should be split into two groups according to their toxicity. One Member State claimed that ranges should be given for individual metals. These last two requests came after the agreement in the TWG meeting on total metals. Table 2.12: BAT-AELs for metals in the existing (adopted) series of chemical BREFs SR/EIPPCB/BP CWW TWG subgroup November 2010 43 Plants reporting data One installation (#41) reported total concentrations for metals which were not used in the analysis given the lack of details. Averaging periods used for reporting emissions Sampling frequency varies considerably, from once per day to once per year. Mostly grab samples or composite samples over a short duration (2 – 24 h) were taken. If mentioned, averaging periods are on a yearly basis. Techniques reported that reduce metal discharges The main techniques to reduce emissions of metals are the segregation and selective pretreatment of waste water streams from processes where metals are an issue. During biological treatment of waste water, metals can be removed by biomass as a positive effect either through an active uptake (bioaccumulation) or by passive biosorption. The extent to which metals are removed depends on several factors, for example pH, nature and concentration of biomass and inorganic particles, chemical state of metal ion (oxidation state, complexation). Parameters that affect performance The removal of metals is a positive effect of biological waste water treatment. Increasing the concentration of biomass during treatment and reducing solids in the effluent increases the transfer of metals to the sludge and thus increases their removal. This is especially true for those metals which tend to be bound to particles. Examples are given below for Total-Cr and Cu. Organo-metallic compounds may be more difficult to remove from waste waters (this depends on the compounds and the waste water composition. Under unfavourable conditions, the achievable elimination may be lower and/or the treatment more difficult/expensive). The correlation between TSS in the effluent of central WWTPs and concentration of Total-Cr in the effluent of central WWTPs is shown in Figure 2.12. Correlation between TSS in the effluent of central WWTPs and concentration of total Cr in the effluent of central WWTPs Concentration of total Cr (in microg/l) in the effluent of central WWTPs 320 200 100 50 50 40 30 20 10 0 0 50 100 150 150 2000 TSS concentration (in mg/l) in the effluent of central WWTPs) 44 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.12: Correlation between TSS in the effluent of central WWTPs and concentration of Total-Cr in the effluent of central WWTPs The correlation between TSS in the effluent of central WWTPs and concentration of Cu in the effluent of central WWTPs is shown in Figure 2.13. Correlation between TSS in the effluent of central WWTPs and concentration of Cu in the effluent of central WWTPs Concentration of total Cu (in microg/l) in the effluent of central WWTPs 1050 200 200 150 100 50 0 0 50 100 150 150 1850 TSS concentration (in mg/l) in the effluent of central WWTPs) Figure 2.13: Correlation between TSS in the effluent of central WWTPs and concentration of Cu in the effluent of central WWTPs Relation between performance and techniques used as reported in the questionnaires In many cases, high removal efficiencies are achieved by the central WWTP and special pretreatment is only used for selected tributary streams (see abatement efficiencies in the tables presented in the following sections). Given that removal of metals is a positive effect and that applied techniques are heterogeneous combinations of basic operations, no relationship between performance and specific techniques could be established. The evaluation of questionnaires pointed out that high removal efficiency with relatively low concentrations at the outlet can be achieved by central WWTPs depending on local conditions (see Table 2.15, Table 2.17, Table 2.19, and Table 2.20). Limits of detection (LOD) and quantification (LOQ) Limits of detection and quantification depend on the analytical method, the instruments and the reagents used, but also on the presence of interfering constituents (matrix). Lower limits of application (LLA) and LODs/LOQs are described in European (CEN) and International standards (ISO) but are sometimes outdated. SR/EIPPCB/BP CWW TWG subgroup November 2010 45 Industry considers that the WWTPs exibiting metal concentrations below the limit of detection both in the effluent and influent cannot be considered to make conclusions on BAT. 2.3.2 Cadmium (Cd) Background information on cadmium Although cadmium is not expected at the outlet of central WWTPs, CEFIC indicated that cadmium can be found as a by-product of production e.g. in the effluent of phosphate production (cadmium is found as a trace element in phosphate rock used in chemical production (e.g. phosphoric acid production), when catalysts are used in production. Cadmium emissions at sites which do not use cadmium in their process are expected to be below the limit of quantification (i.e. <2 µg/l). Germany suggested that the CWW should not propose BAT-AELs for cadmium and that this should be left to the relevant vertical BREFs. Overview of central WWTP performance on Cd Figure 2.14 presents the Cd concentration in the influent and effluent of central biological WWTPs and Figure 2.16 presents the Cd concentration in the influent and effluent of central physico-chemical WWTPs. Figure 2.14: 46 Cd concentration in the influent and effluent of central biological WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.15: Cd concentration in the influent and effluent of central physico-chemical WWTPs It is to be noted that WWTP #69 discharges in the Venice lagoon. Number of plants reporting data Out of the 63 WWTPs, 26 reported Cd values in the effluent. Of these values, 10 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <dl. Cd concentrations in the influent were reported in 9 questionnaires of which 6 are reported as <X, <dl, "0", and between X and Y. Therefore, no analysis on abatement efficiencies was performed. Peaks of emissions Peaks occur at plant #58 (IT) where a Cd value of 10 µg/l is reported, at plant #27 (CEFIC, UK) where a Cd value of 5 µg/l is reported. Also, plants #24 (CEFIC, UK) and #43 (PT) report values of <5000 µg/l and <50 µg/l, respectively. Techniques reported to minimise/reduce Cd discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: precipitation and filtration (with other metals) ion exchange (with other metals). Reported achieved performance The Cd concentrations in the effluents of central WWTPs are given in Table 2.13. Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum Cd average (µg/l) (1) 0.1 0.1 0.4 1.0 1.9 10.0 10.0 SR/EIPPCB/BP CWW TWG subgroup November 2010 47 (1) Only spot-type values different from 0 are summarised in this table (10 figures). In addition, 2 plants report <0.5 µg/l, 2 plants <1 µg/l, 2 plants <10 µg/l, 1 plant <50 µg/l, and 1 plant <5000 µg/l. Table 2.13: Cd concentrations in the effluents of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 11 installations. For 3 of these installations, minimum and maximum values were both exactly the same as the average value (i.e. #21, #27, #58). For one installation, a maximum value was given while the average was below the detection limit (i.e. #43). For the remaining 7 installations, maximum Cd values reported vary around the average by approximately a factor of 1.25 to 2.5. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders) as well as in France, Cd is considered not quantifiable below 2 µg/l (however, questionnaires #49 and #53 reported values of 0.4 µg/l and 1.4 µg/l respectively). Analytical methods to measure Cd include ICP-OES with an approximate LOQ of 0.2 µg/l (EN ISO 11885) and ICP-MS with a lower limit of application of approximately 0.1 µg/l (EN ISO 17294-1). 2.3.3 Chromium total (Total-Cr) The corrosion of pipes and equipment is an important source of chromium in the influent of WWTPs. Overview of central WWTP performance on Total-Cr Figure 2.16 presents the Total-Cr concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. 48 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.16: Total-Cr concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs It can be noted that: WWTP #69 discharges in the Venice lagoon. WWTPs #02 and #06 treat waste waters from the production of dyes. Number of plants reporting data Out of the 63 WWTPs, 30 reported Total-Cr values in the effluent. Of these values, 15 are of spot-type while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Total-Cr concentrations in the influent were reported by 12 questionnaires of which 3 are reported as <X, <detection limit, and "0". Peaks of emissions Peaks occur at installation #28 (CEFIC, UK) where a Total-Cr value of 104 µg/l is reported and at installation #58 (IT) where a Total-Cr value of 70 µg/l is reported. Installation #43 (PT) reports a value of <300 µg/l. Techniques reported to minimise/reduce Total-Cr discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: precipitation and filtration (with other metals) ion exchange (with other metals) activated sludge systems. CEFIC indicated that chromium total can be effectively abated by biological treatment; this is shown by #02 and #49. However this depends on the components that chromium is fixed upon SR/EIPPCB/BP CWW TWG subgroup November 2010 49 as in the case of #06 (complexed chromium cannot be effectively abated by biological treatment and therefore all relevant waste water streams are pretreated – see the OFC BREF). Reported achieved performance The Total-Cr concentrations in the effluents of central WWTPs are given in Table 2.14. Parameter Total-Cr average (µg/l) (1) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.08 0.48 2.1 6 30 70 104 (1) Only spot-type values different from 0 are summarised in this table (15 figures). In addition, 3 plants report <5 µg/l, 3 plants <10 µg/l, 1 plant <50 µg/l, and 1 plant <300 µg/l. Table 2.14: Total-Cr concentrations in the effluents of central WWTPs Abatement efficiencies based on concentrations and loads were calculated for 6 and 4 installations, respectively (Table 2.15). Central WWTP Total-Cr abatement based on concentrations (%) Total-Cr abatement based on loads (%) Table 2.15: #06 #49 #58 #02 #22 #67 46 60 – 90 92 >92 97 >99 95 97 91 43 Total-Cr abatement efficiencies of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 16 installations. For two installations, a maximum value was given while the average was below the detection limit (i.e. #02, #05). For the remaining 14 installations, maximum Total-Cr values reported vary around the average by approximately a factor of 2 to 15, but more generally by between approximately 2 and 8. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Cr total is considered not quantifiable below 10 µg/l (however, questionnaires #49, #53 and #54 reported values of 6 µg/l, 0.48 µg/l and 1 µg/l respectively). In France, the LOQ is 5 µg/l for chromium and chromium compounds. Analytical methods to measure Total-Cr include ICP-OES with an approximate LOQ of 2 µg/l (EN ISO 11885) and ICP-MS with a lower limit of application of approximately 1 µg/l (EN ISO 17294 1). 2.3.4 Chromium VI (Cr VI) Chromium VI is not expected at the outlet of central WWTPs. Also, Germany suggested that the CWW should not propose BAT-AELs for chromium VI which should be removed at the source and that this should be left to the relevant vertical BREFs. Overview of central WWTP performance on Cr VI Figure 2.17 presents the Cr VI concentration in the influent and effluent of central biological WWTPs and of central physico-chemical WWTPs. 50 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.17: Cr VI concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs It can be noted that WWTP #69 discharges in the Venice lagoon. Number of plants reporting data Out of the 63 WWTPs, 12 reported Cr VI values in the effluent. Of these values, 2 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Cr VI concentrations in the influent are SR/EIPPCB/BP CWW TWG subgroup November 2010 51 reported by 4 questionnaires of which 2 are reported as <X, <detection limit, and "0". Therefore, no analysis on abatement efficiencies was performed. Peaks of emissions Installation #58 (IT) reports a Cr VI value of 100 µg/l. Installation #43 (PT) reports a value of <50 µg/l. Techniques reported to minimise/reduce Cr VI discharge Reduction of Cr VI to Cr III, then abatement of Total-Cr as been reported in the questionnaires. Reported achieved performance Given that only two installations reported emission values of a spot-type, Table 2.16 lists all reported values. Central WWTP Cr VI (µg/l) average Cr VI (µg/l) maximum Table 2.16: #44 #05 #52 #61 #46 #62 #69 #06 #51 #43 #58 <dl 0 0 0.01 <0.1 <1 <2.1 <10 <10 <50 100 20 0.20 <22 100 Cr VI concentrations in the effluents of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 4 installations (Table 2.16). Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Cr VI is considered not quantifiable below 10 µg/l. Analytical methods to measure Cr VI include spectrometry with 1,5 Diphenylcarbazide in a concentration range of 50 – 3000 µg/l (ISO 11083) and flow analysis (FIA/CFA) in a concentration range of 2 – 2000 µg/l (EN ISO 23913). 2.3.5 Copper (Cu) The corrosion of pipes and equipment is an important source of copper in waste waters. At some sites, the manufacture or use of copper-based catalysts, the manufacture of organic copper compounds (e.g. dyes) or catalyst residues from large volume organic chemical (LVOC) production are a source of copper in waste waters. Background information on copper For questionnaire 27, copper from catalysts is the main source of copper emissions. Overview of central WWTP performance on Cu Figure 2.18 presents the Cu concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. 52 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.18: Cu concentration in the influent and effluent of central biological WWTPs It can be noted that WWTP #69 discharges in the Venice lagoon. Number of plants reporting data SR/EIPPCB/BP CWW TWG subgroup November 2010 53 Out of the 63 WWTPs, 34 reported Cu values in the effluent. Of these values, 26 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Cu concentrations in the influent were reported by 17 questionnaires of which 2 are reported as <X, <detection limit, and "0". Peaks of emissions Peaks occur at installations #28 (CEFIC, UK) and #27 (CEFIC, UK) where Cu values of 581 µg/l and 202 µg/l, respectively, are reported. It can be noted that WWTP #27 has no biological treatment and WWTP #28 has very high TSS emissions (i.e. 1729 mg/l). Techniques reported to minimise/reduce Cu discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: precipitation and filtration (with other metals) ion exchange (with other metals) activated sludge systems. In many cases, biological treatment can be used effectively to abate copper. Germany pointed out that for questionnaire #06, because complexing agents are present in the waste water, a pre-treatment by precipitation and flocculation is used before the central WWTP to remove metals. Reported achieved performance The Cu concentrations in the effluents and the abatement efficiencies of central WWTPs are given in Table 2.17. Parameter Cu average (µg/l) (1) Cu abatement based on concentrations (%) (2) Cu abatement based on loads (%) (3) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.71 2 8 10 50 100 581 11.1 11.1 52.7 85.7 98.3 > 99.3 100 50 50 64.9 84.6 95.9 96.6 100 (1) Only spot-type values different from 0 are summarised in this row (26 figures). In addition, 1 plant reports <1 µg/l, 1 plant <10 µg/l, 1 plant <20 µg/l, 1 plant <25 µg/l, 1 plant <50 µg/l, and 1 plant <100 µg/l. (2) 13 figures are summarised in this row. (3) 10 figures are summarised in this row. Table 2.17: Cu concentration and abatement efficiencies in the effluent of central WWTPs CEFIC indicated that for questionnaire #02 where copper values of 1095 µg/l are reported (about 500 kg Cu/day) in the influent, high abatement efficiency is achieved (>96 %; 34 µg/l in the effluent). Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 19 installations. Maximum Cu values reported vary around the average by between 1.7 and 15.5, but more generally by between approximately 2 and 6. The ratio between maximum concentrations and average concentrations tends to be higher for installations with lower average concentrations. 54 November 2010SR/EIPPCB/Analysis questionnaires CWW Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Cu is considered not quantifiable below 25 µg/l (however, questionnaires #49, #53 and #54 reported values of 20 µg/l, 17 µg/l and 2 µg/l respectively). In France, the LOQ is 5 µg/l for copper and copper compounds. Analytical methods to measure Cu include ICP-OES with an approximate LOQ of 2 µg/l (EN ISO 11885) and ICP-MS with a lower limit of application of approximately 1 µg/l (EN ISO 17294-1). 2.3.6 Mercury (Hg) The production of chlorine using the mercury process as well as old productions can be important sources of mercury for central WWTPs. Incineration processes are also sources of mercury (from waste gas treatment). Mercury can relatively easily adsorb onto sludge which has to be controlled if sludge is incinerated. Overview of central WWTP performance on Hg Figure 2.19 presents the Hg concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 55 Figure 2.19: Hg concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs It can be noted that: WWTP #69 discharges in the Venice lagoon. For WWTP #22, there is a common pretreatment for mercury from the mercury process and from waste incineration. The questionnaire refers to a year where the process was still in use. WWTPs #46 and #58 are indirect dischargers. Number of plants reporting data Out of the 63 WWTPs, 26 reported Hg values in the effluent. Of these values, 10 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Concentrations of Hg in the influent of the central WWTPs were reported by 11 questionnaires of which 7 are reported as <X, <detection limit, and "0". Peaks of emissions Peaks occur at installations #46 (IT) and #58 (IT) where Hg values of 2 µg/l and 5 µg/l, respectively, are reported. In addition, installations #43 (PT) and #51 (BE) report values of <20 µg/l and <10 µg/l, respectively. Techniques reported to minimise/reduce Hg discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: 56 precipitation and filtration ion exchange precipitation and ion exchange in #12 specific Hg removal in #14 (not further specified) November 2010SR/EIPPCB/Analysis questionnaires CWW activated carbon activated sludge systems combined with sludge incineration/waste gas treatment. Reported achieved performance The Hg concentrations in the effluents of central WWTPs are given in Table 2.18. SR/EIPPCB/BP CWW TWG subgroup November 2010 57 Parameter Hg average (µg/l) (1) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.13 0.13 0.2 0.3 1 2 5 (1) Only spot-type values different from 0 are summarised in this row (10 figures). In addition, two plants report <0.1 µg/l, two plants <0.2 µg/l, one plant <0.32 µg/l, one plant <1 µg/l, one plant <10 µg/l, andone1 plant <20 µg/l. Table 2.18: Hg concentration in the effluent of central WWTPs Abatement efficiencies based on concentrations and loads were calculated for 4 plants, (see Table 2.19). Central WWTP Hg abatement based on concentrations (%) Hg abatement based on loads (%) Table 2.19: #21 #49 #22 #042 77 75 - 90 88 100 89 100 78 #02 100 Hg abatement efficiencies of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 8 installations. Maximum Hg values reported vary around the average by between approximately 1 and 4, but more generally by between approximately 2 and 3. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Hg is considered not quantifiable below 0.25 µg/l. In France, the LOQ is 0.5 µg/l for mercury and mercury compounds. Analytical methods to measure Hg include atomic fluorescence spectrometry (AFS) in a concentration range of 0.01 – 10 µg/l (EN ISO 17852) and cold vapour atomic absorption spectrometric (AAS) in a concentration range of 0.1 – 10 µg/l (EN 1483). 2.3.7 Nickel (Ni) The corrosion of pipes and equipment is an important source of nickel together with the use of nickel-based catalysts. Process gas scrubber/input from heavy fuel oil, catalyst manufacture or catalyst residues from large volume organic chemical (LVOC) production are also source of nickel emissions. Nickel in soluble form is more difficult to remove. Overview of central WWTP performance on Ni Figure 2.20 presents the Ni concentration in the influent and effluent of central biological WWTPs and phycico-chemical WWTPs. 58 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.20: Ni concentration in the influent and effluent of central biological WWTPs and phycico-chemical WWTPs It can be noted that WWTP #69 discharges in the Venice lagoon. SR/EIPPCB/BP CWW TWG subgroup November 2010 59 Number of plants reporting data Out of the 63 WWTPs, 31 reported Ni values in the effluent. Of these values, 20 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Concentrations of Ni in the influent of the central WWTPs were reported by 12 questionnaires of which 2 are reported as <X, <detection limit, and "0". Peaks of emissions A peak occurs at installation #60 (FR) where a Ni value of 280 µg/l is reported. In addition, installation #43 (PT) reports a Ni concentration of <300 µg/l. Techniques reported to minimise/reduce Ni discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: precipitation and filtration (with other metals) ion exchange (with other metals) filtration (#07) activated sludge systems. Reported achieved performance The Ni concentrations in the effluents of central WWTPs are given in Table 2.20. Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum Ni average (µg/l) (1) 2 4 5 20 50 74 280 1 ( ) Only spot-type values different from 0 are summarised in this row (20 figures). In addition, one plant reports <1 µg/l, one plant <5 µg/l, two plants <10 µg/l, and one plant <300 µg/l. Table 2.20: Ni concentrations in the effluents of central WWTPs Abatement efficiencies based on concentrations and loads were calculated for 9 and 7 installations, respectively (see Table 2.21). Central WWTP Ni abatement based on concentrations (%) Ni abatement based on loads (%) Table 2.21: #35 #49 #36 #60 #07 #02 5.6 0 - 60 43 44 55 73 11 55 73 5.6 #25 88 #46 #58 97 98 99 Ni abatement efficiencies of central WWTPs. Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 15 installations. For one installation, a maximum value was given while the average was below the detection limit (#05). Maximum Ni values reported vary around the average by between 1.3 and 6 except one installation with 22.7. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders) as well as in France, Ni is considered not quantifiable below 10 µg/l. Analytical methods to measure Ni include ICP-OES with an approximate LOQ of 2 µg/l (EN 60 November 2010SR/EIPPCB/Analysis questionnaires CWW ISO 11885) and ICP-MS with a lower limit of application of approximately 1 µg/l (EN ISO 17294-1). 2.3.8 Lead (Pb) Overview of central WWTP performance on Pb Figure 2.21 presents the Pb concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 61 Figure 2.21: Pb concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs It can be noted that: WWTP #69 discharges in the Venice lagoon. For WWTP #32, lead-based stabiliser production is the reason for high Pb emissions. Number of plants reporting data Out of the 63 WWTPs, 25 reported Pb values in the effluent. Of these values, 14 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Concentrations of Pb in the influent of the central WWTPs were reported by 11 questionnaires of which 2 are reported as <X, <detection limit, and "0". Peaks of emissions A peak occurs at installation #32 (CEFIC, UK) where a Pb value of 400 µg/l is reported. In addition, installation #43 (PT) reports a Pb concentration of <300 µg/l. It can be noted that WWTP #32 treats waste waters arising from a speciality inorganic chemical plant producing lead based stabilisers for PVC. Techniques reported to minimise/reduce Pb discharge Precipitation with sodium carbonate as a pretreatment and treatment operation as well as activated sludge systems (carried out at the installation(s) from which the waste waters originate or the central WWTP) has been reported in the questionnaires. Reported achieved performance The Pb concentrations in the effluents of central WWTPs are given in Table 2.22. 62 November 2010SR/EIPPCB/Analysis questionnaires CWW Parameter Pb average (µg/l) (1) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.8 0.8 2.8 6 30 400 400 (1) Only spot-type values different from 0 are summarised in this row (11 figures). In addition, one plant reports <1 µg/l, three plants <5 µg/l, one plant <10 µg/l, and one plant <300 µg/l. Table 2.22: Pb concentrations in the effluents of central WWTPs Abatement efficiencies based on concentrations and loads were calculated for 4 and 5 installations, respectively (see Table 2.23). Central WWTP #49 Pb abatement based on 60 – 100 concentrations (%) Pb abatement based on loads (%) Table 2.23: #58 #46 97.0 100.0 98.6 #02 #35 #32 100.0 100 100.0 100.0 Pb abatement efficiencies of central WWTPs. Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 10 installations. Maximum Pb values reported vary around the average by between 1.8 and 10.5 except one installation which reports exactly the same maximum value as the average value. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Pb is considered not quantifiable below 25 µg/l. In France, the LOQ is 5 µg/l for lead and lead compounds. Analytical methods to measure Pb include ICP-OES with an approximate LOQ of 5 µg/l (EN ISO 11885) and ICP-MS with a lower limit of application of approximately 0.1 µg/l (EN ISO 17294-1). 2.3.9 Zinc (Zn) The corrosion of pipes and equipment (tank insulation, building roofs) is an important source of zinc. Raw materials are also a source of zinc that can ultimately be released into water. Overview of central WWTP performance on Zn Figure 2.22 presents the Zn concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 63 Figure 2.22: 64 Zn concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW It can be noted that WWTP #69 discharges in the Venice lagoon. Number of plants reporting data Out of the 63 WWTPs, 33 reported Zn values in the effluent. Of these values, 29 are of spottype while the others are given as range-type values (i.e. <X or <dl) or as "0". The latter could be assumed to be equivalent to <detection limit. Zn concentrations in the influent were reported by 17 questionnaires. Peaks of emissions Peaks occur at installations #24 (CEFIC, UK) and #28 (CEFIC, UK), #57 (FR) where Zn values of 800 µg/l, 1016 µg/l, and 1440 µg/l, respectively, are reported. It can be noted that all these WWTPs exibit high TSS emissions (i.e. 114 mg/l at #24; 1729 mg/l at #28; 122 mg/l at #57). Techniques reported to minimise/reduce Zn discharge The following pretreatment and treatment operations (carried out at the installation(s) from which the waste waters originate or the central WWTP) have been reported in the questionnaires: precipitation and filtration (with other metals) ion exchange (with other metals) activated sludge systems. Reported achieved performance The Zn concentrations in the effluents and the abatement efficiencies of central WWTPs are given in Table 2.24. Parameter Zn average (µg/l) (1) Zn abatement based on concentrations (%)(2) Zn abatement based on loads (%)(3) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 4 14 40 64 161 400 1440 28.9 46.7 56.8 82.8 85.6 99.4 99.7 20.8 20.8 49.2 80.3 85.3 88.6 94.8 (1) Only spot-type values different from 0 are summarised in this row (29 figures). In addition, 1 plant reports <1 µg/l, 1 plant <10 µg/l, and 1 plant <20 µg/l. (2) 15 figures are summarised in this row. (3) 12 figures are summarised in this row. Table 2.24: Zn concentrations in the effluent and abatement efficiencies of central WWTPs Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 22 installations. Maximum Zn values reported vary around the average by between 1.2 and 9.3, but more generally by between approximately 2 and 6. The ratio between maximum concentrations and average concentrations tends to be higher for installations with lower average concentrations. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Zn is considered not quantifiable below 25 µg/l. In France, the LOQ is 10 µg/l for zinc and zinc compounds. Analytical methods to measure Zn include ICP-OES with an approximate LOQ of 1 µg/l (EN ISO 11885) and ICP-MS with a lower limit of application of approximately 1 µg/l (EN ISO 17294-1). The operator of the WWTP #57 indicated a limit of quantification for zinc of 50 µg/l. SR/EIPPCB/BP CWW TWG subgroup November 2010 65 66 November 2010SR/EIPPCB/Analysis questionnaires CWW 2.4 Other parameters 2.4.1 Nitrogen compounds 2.4.1.1 General Background information on nitrogen compounds While nitrogen is essential to living species, excessive concentrations of certain nitrogen species in water can lead to significant environmental problems (eutrophication). However, nitrogen, like phosphorus and carbon, is needed in the biological processes of waste water treatment so that organisms that decompose the organic load can reproduce. When the industrial waste waters do not contain enough nitrogen for optimum growth of the organisms used in treatment, addition of inorganic nitrogen is carried out. A concentration ratio of BOD5 : N : P = 100 : 5 : 1 is often considered optimal for aerobic waste water treatment. For anaerobic treatments steps, the ratio is BOD5 : N : P = 100 : 0.5 : 0.1 (C. Forster, Wastewater Treatment and Technology, 2003). Nitrogen compounds and in particular nitrates are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. CEFIC pointed out that all nitrogen-related parameters (i.e. nitrogen total, ammonia, nitrate and nitrite) are very sensitive to sampling and analytical methods (which is not so much the case for COD). CEFIC indicated that the removal of nitrogen undergoes a larger variety during operation. The nitrification mechanism as autotrophic is based on very sensitive and slowly growing bacteria compared to the heterotrophic COD degradation. Therefore the variability of maximum to average will be much higher compared to e.g. COD or TOC performance. The following parameters should be analysed together: nitrogen total, ammonia, nitrate and nitrite. Expressed as NH4-N, Nitrate-N, etc. Depending on the influent, except for total nitrogen, inorganic nitrogen compounds result partly from the biological treatment process. Therefore, concentration in the effluent is generally a parameter more pertinent than abatement efficiency. 2.4.1.2 Total nitrogen (Total-N) TNb (Total Bound Nitrogen) is a measure of the concentration of ammonia, ammonium salts, nitrites, nitrates and organic nitrogen components (dissolved nitrogen is not detected). It allows a rapid assessment of the total nitrogen compound load in a water sample. TNb can be determined simultaneously with TOC. The method is standardized by DIN 38409-H27 and EN 12260. It applies for freshwater, seawater, drinking water, surface water and wastewater. The method covers the measurement range 0.5 mg/l – 200 mg/l. More highly concentrated samples should be diluted. TKN (Total Kjeldahl Nitrogen) is a measure of the concentration of ammonia/ammonium (NH3/NH4+) and organic-Nitrogen. However, a series of organic compounds is incompletely detected by the Kjeldahl method. In Germany, Total-Inorganic-N as the sum of NH4-N, NO2-N and NO3-N is commonly measured. TNb, is therefore higher than Total-Inorganic-N. A comment was made that total nitrogen should not be expressed as a sum, since it is an analytical parameter on its own (i.e. TNb). It has to be mentioned, that the analytical methods of Total-N as TNb (by thermal SR/EIPPCB/BP CWW TWG subgroup November 2010 67 oxidation) and Total-N by TKN (Kjeldahl hydrolysis and stripping) lead to non-comparable results. Overview of central WWTP performance on Total-N Figure 2.23, Figure 2.24 and Figure 2.25 present the Total-N (mainly as TNb), total inorganic N and TKN concentration in the influent and effluent of central biological WWTPs and physicochemical WWTPs. 10 54 64 19 60 21 09 37 52 (TNb) Nitri./deni. (TNb) Nitri./deni. (TNb) Nitri./deni. 10 43 (TNb+free ammonia) Nitri./deni. 49 (Total Nitrogen, no information on analytical method used) 40 47 (TNb+free ammonia) Nitri./deni. (TKN+NO2+NO3) Nitri./deni. (TNb) Nitri./deni. (TNb+free ammonia) Nitri./deni. 48 (TKN+NO2+NO3) Nitri./deni. 11 (TNb+free ammonia) 20 (TKN+NO2+NO3) (TNb) Nitri./deni.+Adsorp. 30 (TNb+free ammonia) 40 (TKN+NO2+NO3) 50 (TNb) Nitri./deni. Total Nitrogen (mostly as TNb) (mg/l) 60 (Sum of N-NH3, N-NO2, N-NO3 and org-N calculated from the different measured species (i.e not TNb)) 70 (Total-N (oxidative combustion + chemiluminisence)) Total Nitrogen (mostly as TNb) concentration in the influent and effluent of central biological WWTPs 50 51 34 0 0 18 Number of central WWTPs Overview of average values (mg/l) Maximum 59 90th percentile 41 75th percentile 28 50th percentile 18 25th percentile 9 10th percentile 7 Minimum 3 Total Nitrogen (mostly as TNb) concentration in the influent and effluent of central physico-chemical WWTPs Total Nitrogen (mostly as TNb) (mg/l) 20 46 10 53 (TKN+NO2+NO3) Strip. (TNb+free ammonia) 38 (TKN+NO2+NO3) 15 5 0 0 3 Number of central WWTPs Overview of average values (mg/l) Maximum 15 90th percentile 15 75th percentile 14 50th percentile 13 25th percentile 10 10th percentile 7 Minimum 6 Figure 2.23: 68 Total-N (mainly as TNb) concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW 12 13 16 02 06 63 041 09 14 24 Nitri./deni. Inciner.+Nitri./deni. Nitri./deni. Nitri./deni. 03 07 Nitri./deni. 11 Nitri./deni. Nitri./deni. 22 Nitri./deni. 10 Nitri./deni. Nitri./deni. 20 Nitri./deni. 30 Nitri./deni. Total Inorganic N (mg/l) 40 Nitri./deni. (Sum of NH4-N+NO2-N+NO3-N) Nitri./deni. 50 Nitri./deni. Total Inorganic N concentration in the influent and effluent of central biological WWTPs 36 15 01 08 62 0 0 19 Number of central WWTPs Overview of average values (mg/l) Maximum 32 90th percentile 25 75th percentile 19 50th percentile 9 25th percentile 6 10th percentile 4 Minimum 0.9 Total Inorganic N concentration in the influent and effluent of central physico-chemical WWTPs 20 15 Total Inorganic N (mg/l) 05 042 10 5 56 0 0 3 Number of central WWTPs Overview of average values (mg/l) Maximum 14 90th percentile 13 75th percentile 13 50th percentile 11 25th percentile 6 10th percentile 3 Minimum 1.5 Figure 2.24: Total inorganic N concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 69 TKN concentration in the influent and effluent of central biological WWTPs 20 60 5 45 (TKN+NO2+NO3) Nitri./deni. (TKN+NO2+NO3) (<3 mg/l) Nitri./deni. 10 Nitri./deni. TKN (mg/l) 15 58 64 69 0 0 5 Number of central WWTPs Overview of average values (mg/l) Maximum 14 90th percentile 11 75th percentile 7 50th percentile 7 25th percentile 7 10th percentile 4 Minimum 3 TKN concentration in the influent and effluent of central physico-chemical WWTPs 400 65 TKN (mg/l) 300 200 100 35 0 0 2 Number of central WWTPs Overview of average values (mg/l) Maximum 339 90th percentile 307 75th percentile 259 50th percentile 178 25th percentile 98 10th percentile 49 Minimum 17 Figure 2.25: TKN concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs It can be noted that At WWTP #36, a disturbance over some weeks explains the large variations. Germany considers that Questionnaire #14 is a special case because the very high nitrogen content in the influent comes from a special biochemical process that carries out a pretreatment. Number of plants reporting data Out of the 63 WWTPs, 49 reported Total nitrogen values in the effluent (or 78%) and only about half of these reported Total-N values in the influent. 70 November 2010SR/EIPPCB/Analysis questionnaires CWW Peaks of emissions At one WWTP, Total nitrogen in the effluent is above 100 mg/l (i.e. #65, Total-N of 339 mg/l, indirect discharge). Averaging periods used for reporting emissions The majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce nitrogen discharge A combination of several of the following techniques can be carried out: Pretreatment at the installation(s) from which the waste waters originate, e.g.: o o o o o oxidation with UV radiation (i.e. #02: conversion of EDTA) conversion of cyanide (see Section 2.4.6) distillation, stripping (i.e. #02, #15, #50, #61: ammonia; #50: aniline, nitrobenzene) recycling of nitric acid (i.e. #11, #15) sedimentation (i.e. #63; #69: dimethylacetamide). Other techniques which are used to treat COD/TOC loads equally apply to organic N, e.g. wet oxidation with hydrogen peroxide, wet air oxidation, and adsorption. Treatments at the central WWTP: o o biological nitrogen elimination (nitrification/denitrification) reverse osmosis, evaporation, crystallisation (i.e. #05: recovery of nitrate). BAT-AELs for Total-N in the existing series of chemical BREFs The BAT-AELs for Total-N in the existing (adopted) series of chemical BREFs are given in Table 2.25. SR/EIPPCB/BP CWW TWG subgroup November 2010 71 BREF (year adopted) CWW (2003) Abatement efficiency (%) none Emission levels (mg/l) Load levels For final waste water discharge into surface water, without dilution with rainwater and/or uncontaminated cooling water For waste water emissions for the whole LVOC sector. The LVOC BREF also defines BAT-AELs for the illustrative processes After treatment in a biological WWTP 5 – 25 (1) LVOC (2002) 10 – 25 (2) OFC (2005) 2 – 20 (3) Remarks POL (2006) LDPE GPPS PVC ESBR VSF <0.9 kg N-NH3/t prod. (4) LVIC-S (2006) Steam stripping under controlled pH conditions LVIC-AAF (2006) SIC (2006) Refineries (2003) 1.5 – 25 (5) 0.25 – 10 (7) 0.5 – 15 g/t cop (6) 0.1 – 6 g/t cop (8) (1) Total inorganic N: sum of NH4-N, NO2-N and NO3-N. (2) Total nitrogen: the exact figure largely depends on the applied processes and type of biological treatment system (N removal). (3) Yearly average, inorganic N: the upper end of the range results from production of organic compounds containing nitrogen or from, e.g. fermentation processes. (4) Soda ash production. (5) Total nitrogen, monthly average. Industry believe that, where nitrogen is not a pollutant of concern in the receiving waters, denitrification cannot be BAT as the environmental benefit to the receiving water is very low, while the cost both in Euros (capital expenditure) and the CO2 emissions are high. (6) Total nitrogen, yearly average. One Member State claims that the upper level of the range should be 8. They demonstrated (based on actual data) that a figure below 8 can easily be achieved with a stripper or a nitrification/denitrification step. cop: crude oil or feedstock processed. (7) Ammoniacal nitrogen (as N), monthly average. One Member State claims that the upper level should be 5. Those levels can be reached by strippers and biological nitrification/denitrification step. (8) Total nitrogen, yearly average. One Member State claims that the upper level of the range should be 8. They demonstrated (based on actual data) that a figure below 8 can easily be achieved with a stripper or a nitrification/denitrification step. cop: crude oil or feedstock processed. Table 2.25: BAT AEL for nitrogen compounds in adopted BREFs Reported achieved performance The Total-N concentrations in the effluent and abatement efficiencies of central WWTPs are given in Table 2.26. 72 November 2010SR/EIPPCB/Analysis questionnaires CWW Parameter Total-N average (mg/l) Total-N abatement based on concentrations (%)(6) Total-N abatement based on loads (%)(7) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.9 (1) 3 (2) 7 (3) 14 (4) 25 (5) 42 339 11.6 30.2 43.4 72.8 85.0 89.4 93.8 -3.9(8) 11.6 43.9 76 85.6 89.8 93.7 (1) #62 (CZ) yearly average of grab samples. (2) #34 (CEFIC) yearly average of weekly samples, abatement efficiency of 81.3 %. (3) #07 (DE) ) yearly average of 365 mixed samples, abatement efficiency of 91 %. (4) #60 (FR) yearly average of 24-hour composite samples, abatement efficiency of 35 %. (5) #49 (BE) yearly average of 24-hour composite samples, abatement efficiency of 50 – 95 %. (6) 28 figures are summarised in this row. (7) 22 figures are summarised in this row. (8) #60, possibly data error. Table 2.26: Total-N concentrations in the effluent and abatement efficiencies of central WWTPs Abatement efficiencies reported are in the range 11 – 95 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are >70 %. Fluctuations of emissions around the average (in concentration) Maximum Total-N values reported vary around the average by approximately a factor of between 1.5 and 5, but more generally between approximately 2 and 3. Large short-term variations can be explained by the nature of the microorganisms used for nitrification/denitrification. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), Total-N is considered not quantifiable below 2 mg/l. Total-N can be quantified by direct determination or separate determinations of TKN, nitrite, and nitrate and by adding the three values. For the direct determination, the following international standards exist: EN 12260 (2003) specifies a method for quantifying the TNb (total nitrogen bound) by combustion and detection of nitrogen oxides using chemiluminescence. Typical detection limits are around 0.5 mg/l. EN ISO 11905-1 (1998) specifies a method using oxidative digestion of Total-N with peroxodisulphate to nitrate which is then quantified. ISO 29441 (2010) specifies a method for the determination of total nitrogen after in-line UV digestion and flow analysis with spectrometric detection. Mass concentrations range from 2 mg/l to 20 mg/l, but other concentration ranges are possible, e.g. 0.2 mg/l to 2 mg/l. EN 25663 is used to dtermine Kjeldahl nitrogen (mineralisation with selemium). Parameters that affect performance Ammonification The first step in the removal of Total-N during biological treatment is conversion of organic N to ammonia/ammonium. For domestic sewage, where organic N consists of urea and faecal material, this already takes place to a certain extent while travelling through sewer pipes. In case of waste waters from chemical installations, some organic N might be recalcitrant to ammonification. The ratio of ammonia (NH3) versus ammonium (NH4+) is affected by pH and temperature. At conditions typical for most biological waste water treatment plants (pH of 6 to 8.5, temperatures of 10 to 40 ºC), far more ammonium than ammonia is produced. SR/EIPPCB/BP CWW TWG subgroup November 2010 73 Nitrification Nitrification is a two-step process. Bacteria known as Nitrosomonas convert ammonia and ammonium to nitrite. Next, bacteria called Nitrobacter finish the conversion of nitrite to nitrate. The reactions are generally coupled and proceed rapidly to the nitrate form; therefore, nitrite levels at any given time are usually low. These bacteria known as 'nitrifiers' are strict 'aerobes', meaning they must have free dissolved oxygen to perform their work. Nitrification occurs only under aerobic conditions at dissolved oxygen levels of 1.0 mg/l or more. At dissolved oxygen (DO) concentrations of less than 0.5 mg/l, the growth rate is minimal. Nitrification requires a long retention time, a low food to microorganism ratio (F:M), a high mean cell residence time (measured as MCRT or sludge age), and adequate buffering (alkalinity). The nitrification process produces acid. This acid formation lowers the pH of the biological population in the aeration tank and can cause a reduction of the growth rate of nitrifying bacteria. The optimum pH for Nitrosomonas and Nitrobacter is between 7.5 and 8.5; most treatment plants are able to effectively nitrify with a pH of 6.5 to 7.0. Nitrification stops at a pH below 6.0. The nitrification reaction (that is, the conversion of ammonia to nitrate) consumes 7.1 mg/l of alkalinity as CaCO3 for each mg/L of ammonia nitrogen oxidised. An alkalinity of no less than 50 – 100 mg/l is required to ensure adequate buffering. Water temperature also affects the rate of nitrification. Nitrification reaches a maximum rate at temperatures between 30 and 35 ºC. At temperatures of 40 ºC and higher, nitrification rates fall to near zero. At temperatures below 20 ºC, nitrification proceeds at a slower rate, but will continue at temperatures of 10 ºC and less. However, if nitrification is lost, it will not resume until the temperature increases to well over 10 ºC. Some of the most toxic compounds to nitrifiers include cyanide, thiourea, phenol and metals such as silver, mercury, nickel, chromium, copper and zinc. Nitrifying bacteria can also be inhibited by nitrous acid and free ammonia. Denitrification The biological reduction of nitrate (NO3) to nitrogen gas (N2) by facultative heterotrophic bacteria is called denitrification. 'Heterotrophic' bacteria need a carbon source as food to live. 'Facultative' bacteria can get their oxygen by taking dissolved oxygen out of the water or by taking it off of nitrate molecules. Denitrification occurs when oxygen levels are depleted and nitrate becomes the primary oxygen source for microorganisms. The process is performed under anoxic conditions, when the dissolved oxygen concentration is less than 0.5 mg/l, ideally less than 0.2. When bacteria break apart nitrate to gain the oxygen, the nitrate is reduced to nitrous oxide (N2O), and, in turn, nitrogen gas (N2). Since nitrogen gas has low water solubility, it escapes into the atmosphere as gas bubbles. Free nitrogen is the major component of air, thus its release does not cause any environmental concern. Optimum pH values for denitrification are between 7.0 and 8.5. Denitrification is an alkalinity producing process. Approximately 3.0 to 3.6 mg/l of alkalinity (as CaCO3) is produced per mg/l of nitrate, thus partially mitigating the lowering of pH caused by nitrification in the mixed liquor. Since denitrifying bacteria are facultative organisms, they can use either dissolved oxygen or nitrate as an oxygen source for metabolism and oxidation of organic matter. If dissolved oxygen and nitrate are present, bacteria will use the dissolved oxygen first. That is, the bacteria will not lower the nitrate concentration. Denitrification occurs only under anaerobic or anoxic conditions. 74 November 2010SR/EIPPCB/Analysis questionnaires CWW Another important aspect of denitrification is the requirement for carbon; that is, the presence of sufficient organic matter to drive the denitrification reaction. Organic matter may be in the form of raw waste water, or supplemental carbon. Conditions that affect the efficiency of denitrification include nitrate concentration, anoxic conditions, presence of organic matter, pH, temperature, alkalinity and the effects of trace metals. Denitrifying organisms are generally less sensitive to toxic chemicals than nitrifiers, and recover from toxic shock loads quicker than nitrifiers. Temperature affects the growth rate of denitrifying organisms, with greater growth rate at higher temperatures. Denitrification can occur between 5 and 40ºC, and these rates increase with temperature and type of organic source present. The highest growth rate can be found when using methanol or acetic acid. A slightly lower rate using raw waste water will occur, and the lowest growth rates are found when relying on endogenous carbon sources at low water temperatures. Three installations report the addition of external carbon sources to ensure/improve the denitrification process (i.e. #63: methanol, #45 and #69: acetic acid). Relation between performance and techniques used as reported in the questionnaires The performance of biological nitrogen removal (nitrification/denitrification) depends on a number of plant operating conditions as described above. Most of these operating conditions were not asked for in the questionnaires. Therefore, it is difficult to establish relationships with the reported performance levels. 2.4.1.3 Ammonia (as NH4-N) Background information on ammonia Ammonia can be present in the influent of central WWTPs (reported in the range 0.66 – 517 mg/l). Ammonia/ammonium is also formed as a first step in the removal of Total-N in central WWTP using biological treatments (i.e. ammonifaction, where organic N is converted to ammonia/ammonium, see Section 2.4.1.2). Ammonia is on one hand assimilated to bacterial cells (leading thus to net growth) and on the other hand oxidised to nitrite and nitrate. Nitrifying organisms are present in almost all aerobic biological treatment processes, but usually their numbers are limited. (From Chemistry for Environmental Engineering and Science fifth Edition) Free ammonia in concentrations above about 0.2 mg/l can cause fatalities in several species of fish. Overview of central WWTP performance on ammonia Figure 2.26 presents the ammonia concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 75 76 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.26: Ammonia concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Concentration in the effluent can be > concentration in the influent because of ammonification, e.g. WWTP #29, #35, #60. Number of plants reporting data Out of the 63 WWTPs, 34 reported ammonia values in the effluent (or 54 %) and about 60 % of these reported NH4-N values in the influent. Peaks of emissions At one WWTP, NH4-N in the effluent is above 100 mg/l, i.e. #65 with NH4-N of 158 mg/l. It can be noted that the main treatment at WWTP #65 is oxidation with H2O2 and that the effluent from WWTP #65 is further treated in a biological WWTP. Averaging periods used for reporting emissions The majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce ammonia discharge A combination of several of the following techniques can be used: Pretreatment at the installation(s) from which the waste waters originate, e.g.: o stripping (e.g. #21, #61). Treatments at the central WWTP: o biological nitrogen elimination (nitrification/denitrification). BAT-AELs for ammoniacal nitrogen in the existing series of chemical BREFs The BAT-AELs for NH4-N in the existing (adopted) series of chemical BREFs are given in Table 2.27. SR/EIPPCB/BP CWW TWG subgroup November 2010 77 BREF (year adopted) Abatement efficiency (%) Refineries (2003) Emission levels (mg/l) Load levels 1.5 – 25 (1) 0.25 – 10 (3) 0.5 – 15 g/t cop (2) 0.1 – 6 g/t cop (4) Remarks (1) Total nitrogen, monthly average. Industry believe that, where nitrogen is not a pollutant of concern in the receiving waters, denitrification cannot be BAT as the environmental benefit to the receiving water is very low, while the cost both in Euros (capital expenditure) and the CO2 emissions are high. (2) Total nitrogen, yearly average. One Member State claims that the upper level of the range should be 8. They demonstrated (based on actual data) that a figure below 8 can easily be achieved with a stripper or a nitrification/denitrification step. cop: crude oil or feedstock processed. (3) Ammoniacal nitrogen (as N), monthly average. One Member State claims that the upper level should be 5. Those levels can be reached by strippers and a biological nitrification/denitrification step. (4) Total nitrogen, yearly average. One Member State claims that the upper level of the range should be 8. They demonstrated (based on actual data) that a figure below 8 can easily be achieved with a stripper or a nitrification/denitrification step. cop: crude oil or feedstock processed. Table 2.27: BAT-AELs for ammoniacal nitrogen in adopted BREFs Reported achieved performance The NH4-N concentration in the effluent of central WWTPs is given in Table 2.28. Parameter NH4-N average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.1 (1) 0.4 (2) 1 (3) 2.9 (4) 10 (5) 50 158 (1) #42 (DE) yearly average. (2) #62 (CZ) yearly average of grab samples, abatement efficiency of 83.6 %. (3) #01 (DE) yearly average of 24-hour composite samples, abatement efficiency of 98.1 %. (4) #33 (CEFIC) daily average of 24-hour flow proportionate samples analysed daily. (5) #06 (DE) yearly average of 24-hour composite samples. Table 2.28: Ammoniacal nitrogen (NH4-N) in the effluent of central WWTPs (both biological and physico-chemical WWTPs) Abatement efficiencies reported are in the range 24 – 99.6 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are generally >83 %. Fluctuations of emissions around the average (in concentration) Maximum NH4-N values reported vary around the average by approximately a factor of 1.5 to 20, but more generally between approximately 2 and 8. Changes of temperature, seasonal effects, change of production, start-ups and shutdowns and result in higher variability in the emissions of ammonia. However, the gap between min/max and average values tend to be larger than for other parameters like COD. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), ammonia is considered not quantifiable below 0.25 mg/l (0.2 mgN/l). Literature reports that ammonia nitrogen can be determined over a range of 0.02 to 2 mg/l by an automated phenate procedure. Parameters that affect performance Suspended-growth nitrification and denitrification processes are very much dependent on temperature, pH, dissolved oxygen, residence time and sludge age. The dynamic of ammonia removal by bacteria is different than the removal of COD due to the differing nature of the bacteria involved. It is therefore important to know that changes in 78 November 2010SR/EIPPCB/Analysis questionnaires CWW production can occur so as to possibly take the necessary measures to minimise ammonia emissions, if the interactions are known and the measures applicable. Relation between performance and techniques used as reported in the questionnaires The sensitivity of nitrification causes large variations of emissions as this can be seen in Figure 2.26. 2.4.1.4 Nitrite (as NO2-N) Background information on nitrite and its measurement Nitrite nitrogen seldom appears in concentrations greater than 1 mg/l in waste water effluents. Its concentration in surface waters and groundwaters is normally much below 0.1 mg/l. For this reason sensitive methods are needed for its measurement. Nitrite is seldom found in waste waters from the chemical industry. Also, there are analytical problems to measure nitrite because of its fast conversion to nitrate. This is the reason why the monitoring of nitrite is seldom performed in the influent of the central WWTPs (only 9 plants – or 13 % – reported nitrite concentrations in the influent of WWTPs). Nitrite in the influent of central WWTPs is reported to be generally in the range of 0.16 – 0.8 mg/l. Nitrite is generated when nitrification processes are used at central WWTPs. Nitrification is a two-step process that first converts ammonia and ammonium to nitrite and then rapidly to nitrate, so that nitrite levels at any given time are usually low. Overview of central WWTP performance on nitrite Figure 2.27 presents the nitrite concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 79 Figure 2.27: Nitrite concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Number of plants reporting data 21 out of the 63 WWTPs reported nitrite values in the effluent (or 33 %) and about 40 % of these reported nitrite values in the influent. Germany indicated that the nitrite emissions given in questionnaire #36 are the result of an abnormal situation and could not be considered representative data. This is probably also the case for questionnaires #37, #38 and #41. Peaks of emissions At three WWTP, nitrite in the effluent is above 1 mg/l (i.e. #37 with nitrite of 2.4 mg/l, #38 with nitrite of 3.2 mg/l and #41 with nitrite of 3.7 mg/l). Averaging periods used for reporting emissions The majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce nitrite discharge Nitrite is an intermediate compound generated in the nitrification process in the removal of ammonia from waste waters. The biological conversion of ammonium to nitrate proceeds rapidly to the nitrate form; therefore, nitrite levels at any given time are usually low. BAT-AELs for nitrite in the existing series of chemical BREFs No BAT-AELs for nitrite are given in the series of chemical BREFs. Reported achieved performance The NO2-N concentration in the effluent of central WWTPs is given in Table 2.29. 80 November 2010SR/EIPPCB/Analysis questionnaires CWW Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum NO2-N average (mg/l) 0.0096 (1) 0.04 (2) 0.1 (3) 0.4 (4) 0.64 (5) 2.4 3.7 (1) #03 (DE) average of continuous results of measurement over three month (14 samples, one sample/week). Might be below the limit of detection/quantification, could DE confirm the value? (2) #62 (CZ) yearly average of grab samples taken 3 times per week. (3) #36 (DE) working day sample (5 x/week). (4) #01 (DE) yearly average of 24-hour composite samples, abatement efficiency of 60 % on the load. (5) #63 (CZ) yearly average of 24-hour composite samples taken 25 times per year. Table 2.29: Nitrite (as NO2-N) in the effluent of central WWTPs Abatement efficiencies reported are in the range -50 – 91.9 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are >53 %. Concentrations greater than 1 mg/l are generally found when a facility is partially nitrifying. Fluctuations of emissions around the average (in concentration) Maximum nitrite values reported vary around the average by approximately a factor of 1.5 to 20, but more generally by between approximately 3 and 8. According to CEFIC, because the nitrite parameter, like the other nitrogen-related parameters, is very sensitive to sampling and velocity of analytics, the use of yearly averages are sufficient to control this parameter. Nitrate and nitrite undergo fast biodegradation and transformation (nitrification/denitrification). Reliable information is only based on online systems. Therefore, both nitrate and nitrite parameters should be presented as sum. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), nitrite is considered not quantifiable below 0.1 mg/l (0.03 mgN/l). Parameters that affect performance Suspended-growth nitrification and denitrification processes are very much dependent on temperature, pH and dissolved oxygen. Nitrification occurs only under aerobic conditions at dissolved oxygen levels of 1.0 mg/l or more. At dissolved oxygen (DO) concentrations less than 0.5 mg/l, the growth rate is minimal. Relation between performance and techniques used as reported in the questionnaires Central WWTPs are not specifically designed to remove nitrite per se (they are possibly designed to remove Total-N) because nitrite is an 'intermediary' pollutant generated when using nitrification processes and is rapidly converted to nitrate (except when there are disturbances). 2.4.1.5 Nitrate (as NO3-N) Background information on nitrate and its measurement Substances which contribute to eutrophication such as nitrates, are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Microbiological processes in central waste water treatment plants convert ammonia to nitrate. (From Chemistry for Environmental Engineering and Science, fifth Edition) Obtaining reliable nitrate nitrogen analysis is difficult. Several procedures exist. SR/EIPPCB/BP CWW TWG subgroup November 2010 81 Overview of central WWTP performance on nitrate Figure 2.28 presents the nitrate concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. NO3 - N concentration in the influent and effluent of central physico-chemical WWTPs 50 direct organic ind. org.+inor. dir. org.+inor. inder. organic direct organic NO3-N (mg/l) 30 20 38 inder. organic dir. org.+inor. 10 53 35 05 042 Filt. ind. org.+inor. direct organic dir. org.+inor. 40 65 46 0 0 Number of central WWTPs 7 Overview of average values (mg/l) Maximum 14 90th percentile 11 75th percentile 9 50th percentile 6.9 25th percentile 4.9 10th percentile 2.9 Minimum 0.1 82 November 2010SR/EIPPCB/Analysis questionnaires CWW NO3 - N concentration in the influent and effluent of central physico-chemical WWTPs (detail) 10 042 9 05 8 53 NO3-N (mg/l) 7 6 65 35 5 4 3 2 1 46 0 0 6 Number of central WWTPs Figure 2.28: Nitrate concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Number of plants reporting data Out of the 63 WWTPs, 26 reported nitrate values in the effluent (or 41 %) and about half of these reported nitrate values in the influent. Peaks of emissions At one WWTP, nitrite in the effluent is above 30 mg/l (i.e. #61 with nitrate of 97 mg/l). Averaging periods used for reporting emissions Many averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce nitrate discharge Nitrate is converted to nitrogen gas in the denitrification process. BAT-AELs for nitrate in the existing series of chemical BREFs No BAT-AELs for nitrate are given in the series of chemical BREFs. Reported achieved performance The NO3-N concentration in the effluent of central WWTPs is given in Table 2.30. Parameter NO3-N average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.08 (1) 0.47 (2) 1.7 (3) 4.8 (4) 9.2 (5) 17 97 (1) #46 (IT) average of daily values. Might be below the limit of detection/quantification, could IT confirm the value? (2) #60 (FR) yearly average of 24-hour composite samples taken daily, abatement efficiency of 93 %. (3) #45 (IT) average of quarterly analysis (each of 3 hours continuous sample). (4) #35 (FR) yearly average of monthly average values, abatement efficiency of -16.9 %. (5) #042 (DE) yearly average. Table 2.30: Nitrate (as NO3-N) in the effluent of central WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 83 Abatement efficiencies reported are in the range -81 – 97.9 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are >53 %. Fluctuations of emissions around the average (in concentration) Maximum nitrate values reported vary around the average by approximately a factor of 1.5 to 25, but more generally by between approximately 1.5 and 8. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), nitrate is considered not quantifiable below 0.5 mg/l (0.1 mg N/l). Literature reports that ion chromatographic and capillary ion electrophoresis methods is highly useful for analysis with nitrate nitrogen concentrations greater than about 0.2 mg/l and that with the cadmium reduction method, nitrate concentrations as low as 0.01 mg/l can be detected. Parameters that affect performance Suspended-growth nitrification and denitrification processes are very much dependent on temperature, pH and dissolved oxygen. Relation between performance and techniques used as reported in the questionnaires The sensitivity of nitrification causes large variations of emissions as this can be seen in Figure 2.28. 2.4.2 Phosphorus compounds 2.4.2.1 General Background information on phosphorus compounds and their treatment Organophosphorus compounds as well as phosphates are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Phosphorus is present in waste waters in inorganic and organic forms. The inorganic forms are orthophosphates (i.e. HPO42-/H2PO4-) and polyphosphates. Organically bound phosphorus is usually of minor importance. Polyphosphates can be used as a means of controlling corrosion. Phosphorus discharge has to be controlled in the same way as nitrogen discharge in order to avoid eutrophication of surface waters. It is reported that to avoid algal blooms under summer conditions, the critical level of inorganic phosphorus is near 0.005 mg/l. Microorganisms utilise phosphorus for cell synthesis and energy transport. As a result, 10 to 30 percent of the influent phosphorus is removed during traditional biological treatments [Metcalf and Eddy]. Biological phosphorous removal can be enhanced by the presence of an anaerobic tank (nitrate and oxygen are absent) prior to the aeration tank. Under these conditions a group of heterotrophic bacteria, called polyphosphate-accumulating organisms are selectively enriched in the bacterial community within the activated sludge. These bacteria accumulate large quantities of polyphosphate within their cells and the removal of phosphorus is said to be enhanced. Therefore, these bacteria do not only consume phosphorus for cellar components but also accumulate large quantities of polyphosphate within their cells; up to a fraction of 5 – 7% of the biomass. When the industrial waste waters do not contain enough phosphorus for optimum growth of the organisms used in treatment, the addition of inorganic phosphates is carried out (see also Section 2.4.1.1). Many central WWTPs reported on the consumption of phosphoric acid (i.e. #17, #18, #19, #21, #22, #28, #34, #40, #41, #45, #48, #50, #52, #58, #60, #61, #63, #64) and some others unspecifically on nutrients (i.e. #25, #29, #51). Apart from the biological waste water treatment, sludge digestion may also require the addition of nutrients. 84 November 2010SR/EIPPCB/Analysis questionnaires CWW 2.4.2.2 Total phosphorus (Total-P) Overview of central WWTP performance on Total-P Figure 2.29 presents the Total-P concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. 2.0 1.9 1.8 1.7 1.6 1.5 1.4 1.3 1.2 1.1 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 52 44 08 12 02 14 041 10 Adsorp.+Filt.+P_precip. 11 62 34 13 69 21 45 03 60 16 07 54 19 15 63 Filt. 06 61 Filt. 01 Filt. 22 P_precip. 37 Filt. Total P (mg/l) Total P concentration in the influent and effluent of central biological WWTPs (detail) 0 28 Number of central WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 85 Figure 2.29: Total-P concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Phosphorous emissions are very sensitive to the C/N/P ratio. CEFIC indicated that, in many cases, total phosphorus emissions does not only reflect emissions from production only but also dosing to biotreatment. In some periods, the dosing level has to be raised to ensure a solid bacteria growth. Germany indicated that it considers 1.5 mg/l of phosphorus (as yearly average) in the effluent to be a high but reasonable level considering the local situation. Number of plants reporting data Out of the 63 WWTPs, 45 reported Total-P values in the effluent (or 71 %) and 21 WWTPs reported Total-P values in the influent. Peaks of emissions At three WWTP, Total phosphorus in the effluent is above 10 mg/l, i.e. #65, with Total-P of 10.2 mg/l (indirect dicharge), #28 with 18.4 mg/l (indirect discharge and high TSS emissions – 1729 mg/l), and #38 with 23.1 mg/l (indirect discharge and high BOD5 emissions – 300 mg/l). Averaging periods used for reporting emissions The majority of averaging periods reported are yearly averages (e.g. of 24-hour daily composite samples, of weekly samples, of bi-monthly samples, of samples taken four times per year). Techniques reported to minimise/reduce Total-P discharge A combination of several of the following techniques is used to minimise/reduce Total-P discharges: Pretreatment at the installation(s) from which the waste waters originate, e.g.: o 86 precipitation. Treatments at the central WWTP by one of the following techniques: November 2010SR/EIPPCB/Analysis questionnaires CWW o o biological phosphorus removal (P incorporated into the cell biomass) precipitation (e.g. with lime, ferric chloride or alum, e.g. #06, #34, #36), before, during or after the biological treatment. It can be noted that chemical precipitation for phosphorus removal increases the volume of sludge produced (on an average of 26 % – Sedlak 1991 –) and often results in a sludge with poor settling and dewatering characteristics. Also, precipitation with metal salts can depress the pH. If nitrification is required, additional alkalinity will be consumed and the pH will drop further. With biological phosphorus removal, the need for chemical addition is reduced or eliminated. Other benefits of biological phosphorus removal are: reduced sludge production, improved sludge settleability and dewatering characteristics, reduced oxygen requirements, and reduced process alkalinity requirements. BAT-AELs for Total-P in the existing series of chemical BREFs The BAT-AELs for Total-P in the existing (adopted) series of chemical BREFs are given in Table 2.31. Abatement efficiency (%) BREF (year adopted) CWW (2003) none Emission levels (mg/l) Load Levels Remarks 0.5 – 1.5 (1) For final waste water discharge into surface water, without dilution with rainwater and/or uncontaminated cooling water 0.2 – 1.5 (2) After treatment in a biological WWTP LVOC (2002) OFC (2005) POL (2006) LDPE GPPS PVC ESBR VSF LVIC-S (2006) LVIC-AAF (2006) 0.5 – 2 kg/t of raw P (3) SIC (2006) Refineries (2003) (1) Total P: lower range from nutrient feed in biological WWTP, upper range from production processes. (2) Yearly average, Total-P: the upper end of the range results from the production of compounds containing P. (3) Production of phosphorus compounds. Table 2.31: BAT-AELs for phosphorus compounds in adopted BREFs Reported achieved performance The Total-P concentrations in the effluent and the abatement efficiencies of central WWTPs are given in Table 2.32. SR/EIPPCB/BP CWW TWG subgroup November 2010 87 Parameter Total-P average (mg/l) Total-P abatement based on concentrations (%) (6) Total-P abatement based on loads (%) (7) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.03 (1) 0.16 (2) 0.49 (3) 0.7 (4) 2 (5) 4.1 23 24.6 20 – 50 46.7 64.3 87.6 95.3 98.5 46.0 46.0 54.3 78.5 90.0 97.7 97.8 (1) #042 (DE) yearly average. (2) #22 (CEFIC) yearly average of daily qualified samples. (3) #37 (ES) no averaging period indicated (samples taken once per week), abatement efficiency of 25 %. (4) #15 (DE) yearly average. (5) #53 (BE) 24 hours composite samples (in proportion to the volume of discharged waste water). (6) 20 figures are summarised in this row. (7) 13 figures are summarised in this row. Table 2.32: WWTPs Total-P concentrations in the effluent and abatement efficiencies of central Abatement efficiencies reported are in the range 24.6 – 98.5 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are generally >50 %, suggesting that chemical precipitation of phosphorus is carried out in addition to biological phosphorus removal. Fluctuations of emissions around the average (in concentration) Maximum Total-P values reported vary around the average by approximately a factor of 1.2 to 10, but more generally by between approximately 1.5 and 3. Limits of detection (LOD) and quantification (LOQ) Two international standards for the determination of Total-P exist: EN ISO 6878 (2004) specifies methods for the determination of different types of phosphates including Total-P after decomposition. The methods are applicable to all kinds of water. Phosphorus concentrations within the range of 0.005 mg/l to 0.8 mg/l may be determined. A solvent extraction procedure allows smaller phosphorus concentrations to be determined with a detection limit of about 0.0005 mg/l. EN ISO 15681 – parts 1 and 2 (2003) specify flow methods (FIA/CFA) for the determination of Total-P for the mass concentration range from 0.1 mg/l to 10 mg/l. Parameters that affect performance The key to (enhanced) biological phosphorus removal is the exposure of the microorganisms to alternating anaerobic and aerobic conditions [Metcalf & Eddy]. Care has to be taken that phosphorous released during sludge treatment (e.g. during sludge digestion due to cell hydrolysis) does not re-enter into the waste water treatment. The precipitation of phosphates is dependant on, for example, type and concentration of flocculants, pH value, mixing regime, and residence time. Relation between performance and techniques used as reported in the questionnaires The performance of (enhanced) biological phosphorus removal and the precipitation of phosphates depend on a number of plant operating conditions as described above. Most of these operating conditions were not asked for in the questionnaires. Therefore, it is difficult to establish relationships with the reported performance levels. 88 November 2010SR/EIPPCB/Analysis questionnaires CWW 2.4.2.3 Phosphate (as PO4-P) Background information on phosphate and their treatment Substances which contribute to eutrophication such as phosphates, are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Overview of central WWTP performance on phosphate Figure 2.30 presents the phosphate concentration in the influent and effluent of central biological WWTPs. Figure 2.30: Phosphate concentration in the influent and effluent of central biological WWTPs Number of plants reporting data Out of the 63 WWTPs, 11 reported PO4-P values in the effluent (or 17 %) and about 72 % of these reported PO4-P values in the influent. Peaks of emissions At one WWTP, PO4-P in the effluent is above 5 mg/l (i.e. #41 with 12 mg/l). Averaging periods used for reporting emissions Many averaging periods reported are yearly averages. Techniques reported to minimise/reduce PO4-P discharge Treatment at the central WWTP by one of the following technique: biological phosphorus removal (P incorporated into the cell biomass) precipitation (e.g. with ferric chloride or alum) and further removal as chemical precipitates (i.e. TSS). No pretreatments have been reported in the questionnaires. SR/EIPPCB/BP CWW TWG subgroup November 2010 89 BAT-AELs for PO4-P in the existing series of chemical BREFs No BAT-AELs for phosphates are given in the series of chemical BREFs. Reported achieved performance The PO4-P concentration in the effluent of central WWTPs is given in Table 2.33. Parameter PO4-P average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0 (1) 0.03 (2) 0.13 (3) 0.6 (4) 1 (5) 1.49 12 (1) #042 (DE) yearly average. Should be interpreted as below the limit of detection/quantification. (2) #64 (FR) yearly average based on two samples per week. (3) #62 (CZ) yearly average of grab samples. (4) #041 (DE) yearly average. (5) #52 (BE) yearly average. Table 2.33: PO4-P in the effluent of central WWTPs Abatement efficiencies reported are in the range 25 – 99 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are >88 %. Fluctuations of emissions around the average (in concentration) Maximum PO4-P values reported vary around the average by approximately a factor of 1.5 to 15, but more generally by between approximately 1.5 and 6.5. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), phosphate is considered not quantifiable below 0.15 mg/l (0.05 mg P/l). Phosphates can be determined by the two international standards mentioned above for the determination of Total-P: the application ranges for EN ISO 6878 (2004) are 0.005 mg/l to 0.8 mg/l and for EN ISO 15681 – parts 1 and 2 (2003) regarding ortho-phosphate 0.01 – 1.0 mg/l. Other international standards for measuring ortho-phosphate exist, e.g. EN ISO 10304-1 (2007) using ion chromatography. Parameters that affect performance See discussion under Total-P parameter in Section 2.4.2.2. Relation between performance and techniques used as reported in the questionnaires See discussion under Total-P parameter in Section 2.4.2.2. 2.4.3 Phenols Background information on phenols and their treatment Persistent hydrocarbons and persistent and bioaccumulable organic substances (some phenols present such characteristics) are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Phenol can be quite toxic to bacteria in concentrated solution. However, literature reports that phenol can serve as food for aerobic bacteria without serious toxic effects at levels as high as 500 mg/l. CEFIC indicated that it considers that the phenol parameter as sum parameter such as the ''phenol index'' is an old fashion parameter and that emissions of phenols as individual component from industrial installations are generally low. Consequently, CEFIC considers that 90 November 2010SR/EIPPCB/Analysis questionnaires CWW it is not worth spending too much time on the analysis of this parameter, because phenol is readily degradable under normal WWTP conditions. Overview of central WWTP performance on phenols Figure 2.31 presents the phenols concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. Figure 2.31: Phenols concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 91 Some participants expressed concern over the fact that phenols in waste waters can be determined by various methods and that the corresponding results would not be comparable. For Questionnaires #46, #65, and #66 where high phenol emissions are shown, the WWTPs discharge indirectly to the receiving water. Number of plants reporting data Out of the 63 WWTPs, 19 reported phenols values in the effluent (or 30 %) and about half of these reported phenols values in the influent. High phenols concentration in the influent corresponds to central WWTPs treating waste waters from installations where phenolic compounds are used/produced (e.g. #47, #61, #65, #66). Peaks of emissions At nine WWTPs, phenols in the effluent are above 100 µg/l with phenols being above 1000 µg/l at four WWTPs (i.e. #65, #66, #46, #28). Averaging periods used for reporting emissions Many averaging periods reported are yearly averages. Techniques reported to minimise/reduce phenols discharge A combination of several of the following techniques are reported to be used: pretreatment at the installation(s) from which the waste waters originate, e.g.: o o extraction (i.e. #57, #61) adsorption with activated carbon (i.e. #50); treatments at the central WWTP: o o biological treatment using complete-mixed activated sludge (i.e. #28, #47, #50, #57, #60, #61, #64) oxidation with H2O2 (i.e. #65, #66). BAT-AELs for phenols in the existing series of chemical BREFs No BAT-AELs for phenols are given in the series of chemical BREFs. Reported achieved performance The phenols concentration in the effluent of central WWTPs are given in Table 2.34. Parameter Phenols average (µg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0 (1) 0.1 (2) 6 (3) 50 (4) 400 (5) 6700 9100 (1) #41 (FR) yearly average of 24-hour composite samples. Might be below the limit of detection/quantification, could FR confirm the value? (2) #02 (DE) one month composite sample. Might be below the limit of detection/quantification, could DE confirm the value? (3) #45 (IT) average of quarterly analysis (each of 3-hour continuous samples). (4) #61 (CZ) yearly average of 24-hour composite samples. (5) #47 (ES) yearly average of 24-hour composite samples. Table 2.34: Phenols in the effluent of central WWTPs Abatement efficiencies reported are in the range 52 – 99.9 %. For the 50th percentile of central WWTPs and higher, abatement efficiencies are generally >90 %. 92 November 2010SR/EIPPCB/Analysis questionnaires CWW Fluctuations of emissions around the average (in concentration) Maximum phenols values reported vary around the average by approximately a factor of 1 to 16, but more generally by between approximately 2 and 6. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), phenol is considered not quantifiable below 0.2 µg/l. Several international standards for determining phenols exist. The phenol index can be measured by ISO 6439 (1990) which gives procedures for drinking waters, surface waters, brines (saline waters), domestic waters and industrial waters. After a preliminary distillation the test sample are analysed according to specific application by the direct colorimetric method (4aminoantipyrine) and by the chloroform extraction method. Another possibility is to use flow analysis (flow injection analysis – FIA – and continuous flow analysis – CFA) according to EN ISO 14402 (1999). The phenol index is an operationally defined parameter. Therefore the results depend largely on the applied procedure. Specific phenols can be determined by: ISO 81651-1 (1992) and ISO 8165-2 (1999): selected monovalent phenols; EN ISO 17495 (2003): nitrophenols; EN ISO 18857-1 (2006): alkylphenols; ISO 18857-2 (2009): alkylphenols, their ethoxylates and bisphenol A; ISO 24293 (2009) isomers of nonylphenol; EN 12673 (1998): chlorophenols. Results from the different analytical methods are difficult to compare. Regarding the phenol index, the recovery for distinct phenol varies considerably. In addition, different national standards for measuring the phenol index are in use, e.g. DIN 38406-16, NF T 90-204, APAT IRSA 5070 A1/A2. Parameters that affect performance The removal of phenols in activated sludge processes is reported to be sensitive to temperature and higher performance is achieved in cold rather than warm weather. Relation between performance and techniques used as reported in the questionnaires The conventional treatment methods adopted for removal of phenol depend upon the maintenance of the toxic limit of phenol concentration and adequate acclimatisation of the biomass. The trickling filter and the activated sludge process are generally in use for the treatment of phenolic waste water. In the activated sludge process, the requirement of air for aeration increases with phenol concentration. The phenol loading removal is effective only up to a certain level. Some discharged effluent standards being 0.1 mg/l, the conventional methods are not efficient to bring down the phenol concentration to such a low level in the treated effluent. 2.4.4 Chlorides Background information on chlorides and their treatment Chlorides are not included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Chloride occurs in all natural waters in widely varying concentration (very high in sea and ocean, on average 19 g/l). Freshwater organisms can be harmed by excessive chloride concentrations, e.g. EC10(48 h) and EC50(48 h) values of 3.9 and 12 g/l, respectively, are reported for the standardised fish egg test with danio rerio (German Association of Chemists (GDCh) 2005, Lammer et al. 2009 and references within). Chloride in reasonable concentrations is not harmful to humans. At concentration above 250 mg/l it gives a salty taste to water. The literature reports that chloride concentrations of >1000 mg/l have a negative effect on the biological removal of phosphorus in WWTPs. The literature reports that chloride concentrations of >10000 mg/l have negative effects on the biological removal of nitrogen in WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 93 Germany is of the opinion that salt concentration (chloride, sulphate and/or the sum of both) is a useful information concerning treatment conditions and the interpretation of some other parameters (e.g. bioassays). Germany also considers that regarding salts, the abatement efficieny of biological treatment is low and is not a pertinent parameter. Overview of central WWTP performance on chlorides Figure 2.32 presents the chlorides concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. 94 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.32: Chlorides concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Number of plants reporting data Out of the 63 WWTPs, 27 reported chloride values in the effluent (or 43 %). Of these values, 26 are of spot-type while one is given as a range-type value (i.e. <500 mg/l). Chloride values in the influent were reported by 14 installations. Peaks of emissions There are very large variations on the concentrations of chlorides discharged with several values in the range of 1000 – 10000 mg/l and a peak at 20500 mg/l (i.e. #17). Averaging periods used for reporting emissions Many averaging periods reported are yearly averages. Techniques reported to minimise/reduce chlorides discharge Waste waters loaded with chlorides can be treated by nanofiltration or reverse osmosis (i.e. #58). BAT-AELs for chlorides in the existing series of chemical BREFs The BAT-AELs for chlorides in the existing (adopted) series of chemical BREFs are given in Table 2.35. SR/EIPPCB/BP CWW TWG subgroup November 2010 95 Abatement efficiency (%) BREF (year adopted) Emission levels (mg/l) CWW (2003) LVOC (2002) OFC (2005) POL (2006) LDPE GPPS PVC ESBR VSF LVIC-S (2006) LVIC-AAF (2006) SIC (2006) Refineries (2003) (1) Titanium dioxide – chloride route. Table 2.35: Load levels Remarks 38 – 330 kg/t TiO2 (1) BAT-AELs for chlorides in adopted BREFs Reported achieved performance The chlorides concentration in the effluent of central WWTPs is given in Table 2.36. Parameter Chlorides average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 54 64 (1) 472 (2) 1330 (3) 3468 (4) 6230 20500 (1) #62 (CZ) yearly average of grab samples. (2) #54 (BE) yearly average of 24-hour composite samples. (3) #07 (DE) yearly average based on weekly 24-hour mixed samples, abatement efficiency of 4 %. (4) #65 (ES) yearly average of monthly samples, abatement efficiency of 42 %. Table 2.36: Chlorides in the effluent of central WWTPs Abatement efficiencies based on concentrations are in the range of -22 – 92 %. Abatement efficiencies reported are generally low, below 40 %, except for #58 (IT) where an abatement efficiency of 92 % is reported (i.e. reduction from 1075 mg/l to 90 mg/l). It should be noted that reverse osmosis is used at #58. Industry therefore considers that central WWTPs have no impact on chloride abatement. Fluctuations of emissions around the average (in concentration) Maximum values above detection limits in addition to the average value were reported by 17 installations. Maximum chlorides values reported vary around the average by approximately a factor of 1 to 3 (one installation with a factor of 10.8), but more generally by between approximately 1.2 and 2. Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), chloride is considered not quantifiable below 25 mg/l. Several international standards for measuring chloride exist. ISO 9297 (1989) uses titration with silver nitrate and chromate indicator (Mohr's method) and is applicable to concentrations between 5 mg/l and 150 mg/l. Due to many interferences the method is not applicable to heavily polluted waters of low chloride content. EN ISO 10304-1 (2007) uses ion chromatography for the determination of chloride with a lower application limit of 0.1 mg/l. Parameters that affect performance Not relevant since the central WWTP is not generally used to reduce chlorides. Relation between performance and techniques used as reported in the questionnaires 96 November 2010SR/EIPPCB/Analysis questionnaires CWW Chlorides are basically not removed by biological and most physico-chemical treatments in the central WWTPs. On the contrary, chlorides are often added to the waste waters, either during neutralisation/acifdification using hydrochloric acid or during flocculation using aluminium or iron chlorides. CEFIC questioned if exist to abate chlorides and, if so, if BAT conclusions should be derived for this parameter. Chlorides may be a more pertinent parameter to consider in the vertical chemical BREFs. Referring to a recent workshop, CEFIC informed that high salt concentrations may hinder nitrification. Biological treatment plants (carbon removal) work even at very high salt concentrations (<5%). CEFIC considers that chlorides are only considered in regard to the impact on the performance of the WWTP, i.e. sedimentation, velocity of bacterial growth, or the interference on analytics, i.e. AOX measurements and biotests. 2.4.5 Sulphates Background information on sulphates and their treatment Sulphates are not included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. As for chlorides, sulphates may be a more pertinent parameter to consider in the vertical chemical BREFs, e.g. in the Polymers (POL) and OFC BREFs. The sulphate ion is one of the major anions occurring in natural waters. It is of importance because of its cathartic effect upon humans when it is present in excessive amounts. It is important to control sulphates in the influent of waste water treatment plants because of the potential to create odour (formation of hydrogen sulphide) and corrosion problems in sewers (by oxidation of hydrogen sulphide to sulphuric acid). Freshwater organisms can be harmed by excessive sulphate concentrations. Overview of central WWTP performance on sulphates Figure 2.33 presents the sulphates concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. SR/EIPPCB/BP CWW TWG subgroup November 2010 97 Figure 2.33: Sulphates concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Number of plants reporting data Out of the 63 WWTPs, 23 reported sulphates values in the effluent (or 37 %). Of these values, 22 are of spot-type while one is given as range-type value (i.e. <40 mg/l). Sulphate values in the influent were reported by 8 installations. 98 November 2010SR/EIPPCB/Analysis questionnaires CWW Peaks of emissions There are very large variations on the concentrations of sulphates discharged with several values in the range of 1000 – 5000 mg/l. Averaging periods used for reporting emissions Many averaging periods reported are yearly averages. Techniques reported to minimise/reduce sulphates discharge Waste waters loaded with sulphates can be treated by nanofiltration and reverse osmosis. BAT-AELs for sulphates in the existing series of chemical BREFs The BAT-AELs for sulphates in the existing (adopted) series of chemical BREFs are given in Table 2.37. BREF (year adopted) CWW (2003) LVOC (2002) OFC (2005) Abatement efficiency (%) Emission levels (mg/l) POL (2006) LDPE GPPS PVC ESBR VSF Load levels Remarks 200 – 300 kg/t prod. 100 – 550 kg/t TiO2 (1) LVIC-S (2006) LVIC-AAF (2006) SIC (2006) Refineries (2003) (1) Titanium dioxide – sulphate route. Table 2.37: BAT-AELs for sulphates in adopted BREFs Reported achieved performance The sulphates concentration in the effluent of central WWTPs is given in Table 2.38. Parameter Sulphates average (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0.5 (1) 62 (2) 238 (3) 938 (4) 1481 (5) 1720 5032 (1) #45 (IT) average of quarterly analysis (each of 3-hour continuous samples). Value is quite low compared with typical concentrations of fresh water and could be below the limit of detection/quantification. Could IT confirm the value? (2) #58 (IT) average of 267 samples (with a standard deviation of 27), abatement efficiency of 92 %. (3) #01 (DE) yearly average of 52 weekly samples. (4) #46 (IT) average of daily values. (5) #02 (DE) 2-hour composite sample. Table 2.38: Sulphates in the effluent of central WWTPs Abatement efficiencies based on concentrations are in the range of -14 – 92 %. Abatement efficiencies reported are generally low and below 43 %, except for #58 (IT) where an abatement SR/EIPPCB/BP CWW TWG subgroup November 2010 99 efficiency of 92 % is reported (i.e. reduction from 737 mg/l to 62 mg/l). It should be noted that reverse osmosis is used at #58. Industry therefore considers that central WWTPs have no impact on sulphate abatement. Fluctuations of emissions around the average (in concentration) Maximum sulphates values reported vary around the average by a factor of 1.1 to 2.6 with one exception (i.e. factor of 6.9). Limits of detection (LOD) and quantification (LOQ) In Belgium (Flanders), sulphate is considered not quantifiable below 25 mg/l. Several international standards for measuring sulphate exist. EN ISO 10304-1 (2007) uses ion chromatography for the determination of sulphate with a lower application limit of 0.1 mg/l. ISO 22743 (2006) specifies a continuous flow analysis (CFA) method for the determination of sulphate in various types of water including waste water. The method is applicable to samples with a mass concentration of 30 mg/l to 300 mg/l. Other concentration ranges are applicable, provided they cover exactly one decade of concentration units (e.g. 100 mg/l to 1000 mg/l). Parameters that affect performance Not relevant since the central WWTP is not generally used to reduce sulphates. Relation between performance and techniques used as reported in the questionnaires Sulphates are basically not removed by biological and most physico-chemical treatments in the central WWTPs, with the exemption of the addition of calcium hydroxide or lime which may lead to the precipitation of calcium sulphate. On the contrary, sulphates are often added to the waste waters either during neutralisation/acidification using sulphuric acid or during flocculation using aluminium or iron sulphates. 2.4.6 Cyanides (free) Background information on cyanides and their measurements Cyanides are included in the indicative list of substances to be taken into account for fixing emission limit values in Annex III of the IPPC Directive. Cyanides can be present in water in dissolved or particulate form. They can be found as cyanide ions (CN-), hydrogen cyanide (HCN), complex bound cyanides, organically bound cyanides, e.g. nitriles and cyanohydrins, and other inorganic forms, e.g. cyanogen chloride (chlorocyan, NCCl), cyanogen bromide, trimethylsilyl cyanide ((CH3)3SiCN). Free cyanide is commonly designated as CN-, although it is actually defined as the total of CN-and HCN. Many cyanide-containing compounds are highly toxic, but some are not. For example, organic cyanides and hexacyanoferrates (ferrocyanide and ferricyanide, where the cyanide is already tightly bound to an iron ion) have low toxicities. The most dangerous cyanides are inorganic cyanides such as hydrogen cyanide and salts derived from it, such as potassium cyanide (KCN) and sodium cyanide (NaCN), among others. Also some compounds readily release HCN or the cyanide ion (CN-), such as trimethylsilyl cyanide upon contact with water and cyanoacrylates upon pyrolysis. The primary concern regarding aqueous cyanide is that it could volatilise, especially when the pH is below 8. The cyanide ion (CN-) has a relatively short half-life because it can serve as a source of energy for aerobic bacteria, provided the concentration is kept below its toxic threshold to them. In the USA, a drinking water standard of 0.2 mg/l is included to protect against industries with direct discharges to natural waters. For context, EU drinking water standards are 0.05 mg/l (for total cyanide). Overview of central WWTP performance on cyanides 100 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.34 presents the cyanides concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs. CN (free) concentration in the influent and effluent of central physico-chemical WWTPs 0.5 direct organic dir. org.+inor. ind. org.+inor. 0.4 ind. org.+inor. direct organic inder. organic inder. organic dir. org.+inor. CN (mg/l) direct organic dir. org.+inor. 0.3 0.2 46 0.1 35 0.0 0 2 Number of central WWTPs Overview of average values (mg/l) Maximum 0.087 90th percentile 0.083 75th percentile 0.077 50th percentile 0.068 25th percentile 0.058 10th percentile 0.052 Minimum 0 Figure 2.34: Cyanide concentration in the influent and effluent of central biological WWTPs and physico-chemical WWTPs Number of plants reporting data Out of the 63 WWTPs, 11 reported free cyanide values in the effluent (or 17 %) and only two reported free cyanides values in the influent. SR/EIPPCB/BP CWW TWG subgroup November 2010 101 Peaks of emissions There are very large variations on the concentrations of free cyanides discharged with two values in the range of 0.1 – 0.5 mg/l. Averaging periods used for reporting emissions Some averaging periods reported are yearly averages. Techniques reported to minimise/reduce cyanides discharge At an adequately low level, cyanides are biodegradable in an adaptated WWTP (see OFC BREF). The rate of biodegradation depends on the activity and adaptation of the WWTP. When influent concentrations are high (in the range of 4 to 5 mg/l), there is a risk of toxicity for the bacteria of the biological treatment. The following pretreatment techniques are reported: conversion to glyconitrile with formaldehyde and sodium hydroxide (i.e. #02, #28) oxidation with hydrogen peroxide (i.e. #35) bleach treatment (i.e. #57) complexation with iron and oxidation with ozone (i.e. #61) oxidation with hypochlorite (i.e. #63, #68) oxidation under alkaline conditions (i.e. #69). BAT-AELs for cyanides in the existing series of chemical BREFs No BAT-AELs for free cyanides are given in the series of chemical BREFs. Reported achieved performance The free cyanides concentration in the effluent of central WWTPs is given in Table 2.39. Parameter Free cyanides (mg/l) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 0 (1) 0.0012 (2) 0.007 (3) 0.05 (4) 0.09 (5) 0.15 0.3 (1) #57 (FR) Monthly monitoring of 24-hour composite sample. Below the limit of detection/quantification, could FR confirm the value? (2) #69 (IT) Daily analysis in laboratory (grab samples). Averaging period not indicated. Might be below the limit of detection/quantification, could IT confirm the value? (3) #63 (CZ) Yearly average of 24-hour composite samples taken 12 times per year (total cyanides). Might be below the limit of detection/quantification, could CZ confirm the value? (4) #35 (FR) Yearly average based on monthly samples. (5) #46 (IT) average of daily values. Table 2.39: Cyanides in the effluent of central WWTPs Abatement efficiencies could not be indicated due to the lack of influent data. Fluctuations of emissions around the average (in concentration) Maximum cyanides values reported vary around the average by approximately a factor of 2 to 11, but more generally by between approximately 2 and 3. Limits of detection (LOD) and quantification (LOQ) Cyanides are usually measured as a sum parameter. Depending on the analytical method used, more or less cyanide species are included. Easily liberatable cyanide is usually understood as the sum of all cyanide compounds which release hydrogen cyanide at a pH value of 4, which includes alkaline and alkaline earth cyanides. Prussiates (nitrosylcyano complexes of iron) and cyanides of cobalt and are partially included. Total cyanide usually includes all inorganic forms of cyanides including complex bound cyanides and also cyanohydrins. Nitriles, cyanates (OCN-), thiocyanates (SCN-), and cyanogen chloride are not included. 102 November 2010SR/EIPPCB/Analysis questionnaires CWW In Belgium (Flanders), free cyanides are considered not quantifiable below 0.01 mg CN-/l. Several international standards for measuring cyanides exist: ISO 6703-1 (1984) describes the determination of total cyanide, ISO 6703-2 (1984) the determination of easily liberatable cyanide, and ISO 6703-3 (1984) the determination of cyanogen chloride. ISO 6703-2 consists of three methods with different application ranges: the photometric method with pyridine/barbituric acid: 0.002 to 0.025 mg/l; the titrimetric method using the tyndall effect: >0.005 mg/l; the titrimetric method using an indicator: >0.05 mg/l. EN ISO 14403 (2002) describes a method for the determination of total cyanide and free cyanide by continuous flow analysis. The method is based on digestion with UV radiation in case of total cyanide and spectrophotometric detection. The method is applicable to various types of water in the range of 0.002 – 0.5 mg/l. Parameters that affect performance Not relevant since the central WWTP is not generally used to reduce cyanides. Relation between performance and techniques used as reported in the questionnaires According to the OFC BREF, due to their toxicity, cyanides are removed from rich and lean waste water streams, e.g. by pH adjustment and oxidative destruction with H2O2. Depending on the individual case, it may be also possible to enable safe degradation of cyanides in a biological WWTP. The use of NaOCl for pretreatment is not considered as BAT due to the potential for formation of AOX. Reconditioning of different cyanide loaded streams can enable re-use and substitution of raw materials. Cyanides occurring in waste water streams together with high COD loads can be pretreated oxidatively by techniques such as wet oxidation with O2 under alkaline conditions. In such cases, cyanide levels <1 mg/l are achievable in the treated waste water stream. 2.4.7 Toxicity 2.4.7.1 General Relatively few toxicity data have been submitted in the questionnaires. The data submitted mainly concern German plants with a few data corresponding to French (i.e. Questionnaires #41 and #57) and Italian installations (Questionnaire #69). It can be noted that Germany made a special contribution titled 'Compilation of Biotest Results from Waste Water Effluents of the Chemical Industry' dated December 2008. This contribution is included in this document as Annex Error! Reference source not found.. Background information on toxicity and their measurements During the last few years biological test methods/systems have raised more and more interest. Fish/fish egg tests, daphnia tests, algae tests and luminescent bacteria tests are all common test methods for the toxicity assessment of complex waste water streams. They are often used to obtain additional information that can be gained from sum parameter measurements (COD, BOD, AOX, EOX, etc.). With toxicity tests it is possible to asses the possible hazardous character of waste water in an integrated manner and to asses all synergistic effects which may occur because of the presence of a lot of different single pollutants. Apart from the possibility of using the toxicity tests to estimate potential hazardous effects on the ecosystem/surface water, these tests can help to protect or to optimise biological waste water treatment plants (see MON BREF). Several international standards for the measurement of toxicity in waste waters exist, e.g. EN ISO 6341 (1996) for daphnia magna, EN ISO 8692 (2004) for algae, EN ISO 11348, parts 1–3 (2008) for luminescent bacteria, EN ISO 20079 (2006) for duckweed, EN ISO 15088 (2008) for zebrafish eggs. SR/EIPPCB/BP CWW TWG subgroup November 2010 103 Toxicity tests require expertise that may not be available at all plants/regions yet and toxicity tests are not amenable to be carried out at high frequency. Techniques reported to minimise/reduce toxicity There are no specific techniques to reduce toxicity in waste waters. All treatment steps as summarised in the sections above which lead to the reduction of the concentration of toxic organic and inorganic compounds (e.g. metals, ammonia, cyanides, phenols, and toxic parts of COD/TOC/BOD) are applicable. BAT-AELs for toxicity in the existing series of chemical BREFs The BAT-AELs for toxicity in the existing (adopted) series of chemical BREFs are given in Table 2.40. BREF Emission levels Remarks (year adopted) CWW (2003) LVOC (2002) OFC (2005) LIDF 1 – 2 (1) LIDD 2 – 4 (1) After treatment in a biological WWTP LIDA 1 – 8 (1) LIDL 3 – 16 (1) LIDEU 1.5 (1) POL (2006) LVIC-S (2006) LVIC-AAF (2006) SIC (2006) Refineries (2003) (1) Yearly averages. Lowest ineffective dilution (LID). Refers to toxicity levels. Subscripts refer to fish/fish eggs (F), daphnia (D), algae (A), luminescent bacteria (L), and genotoxicity (EU). Table 2.40: 2.4.7.2 BAT-AELs for LID in adopted BREFs Fish or fish egg toxicity Overview of central WWTP performance for fish or fish egg toxicity Figure 2.35 presents the fish or fish egg dilution factor in the effluent of central WWTPs. 104 November 2010SR/EIPPCB/Analysis questionnaires CWW Figure 2.35: Fish or fish egg dilution factor in the effluent of central WWTPs Number of plants reporting data 19 out of the 63 WWTPs (17 from DE and 2 from CEFIC - n DE) reported fish or fish egg toxicity values in the effluent (or 30 %). Peaks of emissions Peaks occurs at installation #10 (DE) where a LID value of 4 is reported and at installation #11 (DE) where LID value of 6 is reported. Averaging periods used for reporting emissions Averaging periods are generally not indicated. Average values are based on a number of measurements spanning from 5 to 21. Reported achieved performance The toxicity to fish/fish eggs in the effluent of central WWTPs is given in Table 2.41. Toxicity to fish/fish eggs (LIDF) Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum 1 (1) 1 (2) 1 (3) 1 - 2 (4) 3 (5) 4 6 (1) #03 (DE) yearly averages of 4 samples of the supervisory body. (2) #08 (DE) averaging period and number of samples not indicated. (3) #13 (DE) averaging period and number of samples not indicated. (4) #041 (DE) averaging period and number of samples not indicated. (5) #06 (DE) averaging period and number of samples not indicated. Table 2.41: Toxicity to fish/fish eggs in the effluent of central WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 105 2.4.7.3 Daphnia toxicity Overview of central WWTP performance for daphnia toxicity Figure 2.36 presents the daphnia dilution factor in the effluent of central WWTPs. Figure 2.36: Daphnia dilution factor in the effluent of central WWTPs Number of plants reporting data Out of the 63 WWTPs, 17 (15 from DE, 1 From France and 1 from CEFIC) reported daphnia toxicity values in the effluent (or 27 %). Peaks of emissions Peaks occurs at installation #36 (DE) where a LID value of 3 is reported and at installation #11 (DE) where LID value of 5 is reported. Averaging periods used for reporting emissions Averaging periods are generally not indicated (yearly averages are indicated for two sites). Average values are based on a number of measurements spanning from 5 to 20. Reported achieved performance The toxicity to daphnia in the effluent of central WWTPs is given in Table 2.42. Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum Toxicity to daphnia (LIDD) 1 (1) 1 (2) 1 (3) 1 (4) 2 (5) 3 5 (1) #22 (CEFIC) averaging period and number of samples not indicated. (2) #03 (DE) yearly average of 4 samples of the supervisory body. (3) #09 (DE) 90th percentile. (4) #15 (DE) averaging period and number of samples not indicated. (5) #06 (DE) averaging period and number of samples not indicated. Table 2.42: 106 Toxicity to daphnia in the effluent of central WWTPs November 2010SR/EIPPCB/Analysis questionnaires CWW 2.4.7.4 Algae toxicity Overview of central WWTP performance for algae toxicity Figure 2.37 presents the algae dilution factor in the effluent of central WWTPs. Figure 2.37: Algae dilution factor in the effluent of central WWTPs Number of plants reporting data Out of the 63 WWTPs, 17 (16 from DE and 1 from CEFIC) reported algae toxicity values in the effluent (or 27 %). Peaks of emissions Peaks occur at installation #36 (DE) where a LID value of 16 is reported and at installation #06 (DE) where LID value of 24 is reported. Averaging periods used for reporting emissions Averaging periods are generally not indicated (yearly averages are indicated for one site). The number of measurements span from 5 to 22. Reported achieved performance The toxicity to algae in the effluent of central WWTPs is given in Table 2.43. Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum Toxicity to algae (LIDA) 1 (1) 1 (2) 1 (3) 1 (4) 2 – 3 (5) 4 24 (1) #03 (DE) yearly average of 4 samples of the supervisory body. (2) #08 (DE) averaging period and number of samples not indicated. (3) #12 (DE) averaging period and number of samples not indicated. (4) #22 (CEFIC) averaging period and number of samples not indicated. (5) #16 (DE) averaging period and number of samples not indicated. Table 2.43: Toxicity to algae in the effluent of central WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 107 2.4.7.5 Bacterial luminescence toxicity Overview of central WWTP performance for bacterial luminescence toxicity Figure 2.38 presents the bacterial luminescence dilution factor in the effluent of central WWTPs. Figure 2.38: Bacterial luminescence dilution factor in the effluent of central WWTPs Number of plants reporting data Out of the 63 WWTPs, 19 (16 from DE, 1 from FR, 1 from IT and 1 from CEFIC) reported bacterial luminescence toxicity values in the effluent (or 30 %). Installation #41 (FR) reported toxicity values in Equitox/m3 stemming from the commercial Microtox® test. Conversion to LID values is not straightforward. Peaks of emissions Peaks occurs at installation #11 (DE) and #14 (DE) where a LID value of 4 is reported, at installation #01 (DE) where a LID value of 5 is reported, at installation #15 (DE) where a LID value of 7 is reported, and at installation #06 (DE) where LID value of 12 is reported. Averaging periods used for reporting emissions Averaging periods are generally not indicated (yearly averages are indicated for two sites). Average values are based on a number of measurements spanning from 5 to 20. Reported achieved performance The toxicity to luminescent bacteria in the effluent of central WWTPs is given in Table 2.44. 108 November 2010SR/EIPPCB/Analysis questionnaires CWW Parameter Minimum 10th percentile 25th percentile 50th percentile 75th percentile 90th percentile Maximum Toxicity to luminescent bacteria (LIDL) 1 (1) 1 (2) 1 (3) 2 (4) 4 (5) 7 12 (1) #03 (FR) yearly average of 4 samples of the supervisory body. (2) #08 (DE) averaging period and number of samples not indicated. (3) #22 (CEFIC) averaging period and number of samples not indicated. (4) #12 (DE) averaging period and number of samples not indicated. (5) #11 (DE) average based on 22 measurements. Table 2.44: Toxicity to luminescent bacteria in the effluent of central WWTPs SR/EIPPCB/BP CWW TWG subgroup November 2010 109 3 Discussion concerning the variability of monitoring results The information in this section is mainly drawn from the 'Statistical analysis of monitoring data from waste water effluents of the chemical industry' – Input of the German delegation to the TWG BREF CWW document dated 24 March 2010 submitted by Heino Falcke. In technical terms, the spread or variability is mainly influenced by temporary changes of the raw loads, compensatory measures (e.g. staple tanks) and the elimination rates (and maybe the formation of substances) at the waste water treatment plant. Parameters are expected to show a low spread when many productions at the site contribute to it (e.g. waste water flow and TOC at large sites; comparison of the spread of TOC and AOX). The variance associated with the sampling and chemical analysis may influence the results especially at values near the detection limit. In some cases, a high spread of the data may reflect the fact that there is little reason in controlling the variation (e.g. when there is a further treatment in a municipal treatment plant or when values are far below the emission limit values set in the permit). The document concludes that as a fairly reproducible measure for the spread of data, Germany prefers the 90th percentile respective the ratio of 90th percentile and average value. Depending on the parameter, most of the data sets show a ratio of <2. Higher ratio values may be found when average values are low or when significant trends 2007 – 2009 give an additional spread. 110 November 2010SR/EIPPCB/Analysis questionnaires CWW 4 ANNEXES 4.1 Members of the CWW TWG subgroup for the analysis of questionnaires Belgium: An Derden (VITO) Czech Republic: Jana Brabencová (CENIA, Czech Environmental Information Agency) France: Pierre Chrisment (DRIRE Lorraine) Rodolphe Gaucher (INERIS) Pascale Vizy (Ministry for Ecology, Energy, Sustainable Development and the Sea) Italy: Nicoletta Trotta (Ministry of Environment) Germany: Heino Falcke (Landesamt fuer Natur, Umwelt und Verbraucherschutz Nordrhein-Westfalen) Dieter Kaltenmeier (Regierungspräsidium Freiburg) Portugal: Inês Brás (Environment Portuguese Agency) Célia Maria Peres (Environment Portuguese Agency) Industry: Stefan Dommes (CEFIC) Peter Hartl (CEFIC) Nicolas Lesage (CEFIC) Nathalie Swinnen (CEFIC) Gerhard Zimmer (CEFIC) European Commission: Achim Boenke (DG ENTR) Thomas Brinkman (DG JRC/IPTS/European IPPC Bureau) Serge Roudier (DG JRC/IPTS/European IPPC Bureau) SR/EIPPCB/BP CWW TWG subgroup November 2010 111 4.2 Mandate of the CWW TWG subgroup and working methods The TWG subgroup agreed to the following mandate for its work: better understand/explain how data have been collected and presented (e.g. are the maximum values real or have outlier values been removed?); evaluate the questionnaires received, explain reasons for the environmental performance displayed, help identify inconsistencies/errors and help correct them; eliminate/remove double counts; identify needs for further information (e.g. data requested but not provided in the questionnaires, information not requested in questionnaires but deemed necessary such as the illustration of the variability of some parameters over a certain period of time); determine parameters important in the determination of BAT; help determine the best way to present the information from the questionnaires in the BREF. No final decisions affecting the BREF, BAT or BAT-AELs will be made by the subgroup. The TWG subgroup will make recommendations for the whole TWG to consider. One issue that is not within the mandate of the CWW TWG subgroup includes the proposals for BAT conclusions and associated emission and consumption levels which will be made by the EIPPCB taking into account discussions within the CWW TWG subgroup. 112 November 2010SR/EIPPCB/Analysis questionnaires CWW SR/EIPPCB/BP CWW TWG subgroup November 2010 113 5 REFERENCES Chemistry for Environmental Engineering and Science, fifth Edition 114 November 2010SR/EIPPCB/Analysis questionnaires CWW