Water Safety Plan Guide Treatment Processes – Iron and Manganese Removal Version 1, Ref P8.2 January 2014 Citation: Ministry of Health. 2014. Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal, Version 1, ref p8.2. Wellington: Ministry of Health. Published in January 2014 by the Ministry of Health PO Box 5013, Wellington, New Zealand ISBN: 978-0-478-42750-9 (print) ISBN: 978-0-478-42751-6 (online) Previously published in 2002 as Public Health Risk Management Plan Guide: Treatment Processes – Iron and Manganese Removal, Version 1, ref p8.2. This publication’s title and any reference within the text to ‘public health risk management plan’ were changed in January 2014 to reflect the December 2013 legislation change of the term ‘public health risk management plan’ to ‘water safety plan’. No other changes have been made to this document. This document is available at: www.health.govt.nz This work is licensed under the Creative Commons Attribution 4.0 International licence. In essence, you are free to: share ie, copy and redistribute the material in any medium or format; adapt ie, remix, transform and build upon the material. You must give appropriate credit, provide a link to the licence and indicate if changes were made. Contents Introduction 1 Risk Summary 3 Risk Information Table 4 Contingency Plans 12 Water Safety Plan Performance Assessment 14 Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal iii Introduction Iron and manganese are undesirable in water because of their effect on the appearance and taste of the water, their ability to cause staining, and the health effects of manganese. They can be removed by: oxidising them to form particles in the water, then letting the particles settle, or filtering them out of the water adsorbing them onto ion-exchange resins. Oxidation can be carried out by: aeration – blowing air through the water – spraying the water in the air using dissolved chemical oxidants – chlorine – chlorine dioxide – ozone – potassium permanganate (KMnO4) (see Guide P7.1) (see Guide P7.2) (see Guide P7.3) adsorbing the metals onto greensand.1 This Guide is mainly concerned with removal using potassium permanganate, aeration, greensand and ion-exchange resins. If an event occurs during the removal of these metals (ie, the process doesn’t work properly), the following could happen: if there is incomplete removal of manganese, the manganese may cause sickness if too much oxidant is added, sickness may result from the oxidants themselves if germs get into the water during aeration, these germs may cause sickness if germs grow in the ion-exchange resin, these germs may cause sickness. The use of chemicals during the removal process can present risks to the health of treatment plant staff. These are acknowledged, but are not discussed further as such risks are the subject of health and safety in employment legislation. The success of removal by oxidation depends on: the oxidant used – stronger oxidants, and higher oxidant concentrations give better oxidation (see Guides P7.1, P7.2, P7.3) pH – oxidation is faster at higher pH values (see Guide P8.1) organic matter attached to the metal – this makes oxidation difficult. 1 A naturally-occurring mineral treated with manganese which assists in the oxidation of the metals. Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 1 After oxidation, the process used to remove the insoluble metal compounds will affect how well the metal is removed (see the appropriate Guides in the P5 series for coagulation/flocculation and sedimentation, and in the P6 series for filtration). Greensand filters can oxidise and filter the metals in one step. These filter beds need to be treated with potassium permanganate either continuously or periodically, when the filter stops removing the metals properly. The risk information contained in Guide P6.1 is also helpful for operating greensand filters. For the ion-exchange process to work, the metals must be in a dissolved form. Air and other oxidants must therefore be kept out of the water until after it passes through the ion-exchange unit. 2 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Ref P8.2 Version 1, January 2014 Risk Summary The two events creating the greatest risk involved in the removal of iron and manganese from water are adding too much oxidant to the water (see P8.2.2) and germs getting into the water during aeration (see P8.2.1). The most important preventive measures are: monitor the process to be sure the right dose is used, regardless of how the quality of the incoming water may change (see P8.2.2, P7.1.2.4 (chlorine) and P7.2.2.4 (chlorine dioxide)) regularly maintain the dosing equipment (P8.2.2.3, P7.1.2.1 (chlorine) and P7.2.2.1 (chlorine dioxide)) place netting over aerator grills to stop entry of larger animals (P8.2.3.1). (References in parentheses are to the Risk Information Table.) Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 3 Risk Information Table Reliable information about water quality is essential for the proper management of a water supply. Knowledgeable and skilled staff are also essential for minimising the public health risks associated with water supplies. Please read the staff training (Guide G1) and the monitoring guides (Guide G2). While we haven’t pointed out every detail of how these documents are linked with the present document, the links are many and are important. Abbreviations: DWSNZ – Drinking-Water Standards for New Zealand; MAV – Maximum acceptable value – see DWSNZ:2000 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Removal by oxidation Event: NOT ALL THE MANGANESE REMOVED Possible hazards: Manganese Level of risk: Low P8.2.1.1 Treatment option not right for the water chemistry. P8.2.1.2 pH level is unsatisfactory for the water chemistry. Before designing the treatment plant, use bench-scale and pilotscale tests to select the best treatment for the water chemistry. Before designing the treatment plant, use bench-scale and pilotscale tests to determine the best pH level for the treatment option in use. Manganese. Manganese. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Carry out tests to identify a more appropriate treatment for the water. Monitor the manganese concentration while adjusting the pH to determine the best pH level. P8.2.1.3 A number of oxidants can be used for the precipitation of iron and manganese. In addition to the causes of incomplete oxidation noted in P8.2.1.1 and P8.2.1.2, another possible cause is that the oxidant concentration is too low. For oxidation by chlorine, chlorine dioxide or ozone, refer to the event of oxidant concentration too low in Guides P7.1 (chlorine), P7.2 (chlorine dioxide) or P7.3 (ozone). In all cases, manganese should be added to the list of determinands to monitor, especially when determining the correct dosing set-point (dose rate), and the indicators noted above should also be included. 4 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Ref P8.2 Version 1, January 2014 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Event: NOT ALL THE MANGANESE REMOVED cont’d The possible causes and preventive measures etc., of incomplete oxidation by potassium permanganate (KMnO4), aeration and greensand filtration are covered below. P8.2.1.4 KMnO4/air dose set-point incorrect/ dose calculation incorrect. P8.2.1.5 KMnO4/air supply exhausted. From time to time have a second person check the dose calculations. Regular manual checks on controller calibration. Manganese. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Use a dose controller (eg, reduction-oxidation controller) that will take account of changes in water chemistry, or monitor the manganese concentration often enough so that changes in water chemistry can be matched. Dosing controller incorrectly calibrated. P8.2.1.6 Use bench-scale and pilot-scale tests to determine the best KMnO4 dose or aeration rate. Install an alarm to warn when the KMnO4 supply is running low. Ensure a reserve supply of KMnO4 is kept on site. Keep records of oxidant use to provide a guide to the length of time the chemical supply is likely to last. Manganese. Manganese. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Calibration schedule not signed off. Manganese concentration is more than 50% of the MAV. Maintenance log. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Carry out manual checks on manganese removal and adjust oxidant dose accordingly. Start calculation checks. Recalibrate controller. Increase oxidant dose rate until recalibration can be undertaken. Install alarm system. Urgently order replacement chemicals. Start log of oxidant use. Initiate pump maintenance programme. Schedule a preventive maintenance programme for air pumps. Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 5 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Event: NOT ALL THE MANGANESE REMOVED cont’d P8.2.1.7 KMnO4 supply adequate, but KMnO4 is not being dosed into the water: – Dosing pump failure – Feedlines blocked. Routine maintenance of dosing pumps and feedlines to ensure they are not blocked (see Guide P10). P8.2.1.8 Dose controller malfunction. Do routine controller maintenance. Replace controller with a reliable unit if the present unit is suspect. Manganese. Maintenance log. Manganese. Maintenance log. Maintenance log shows ongoing problems with pump or line blockage. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). 6 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Identify cause of fault and rectify. Determine what steps can be taken to stop it happening again. Identify cause of fault and rectify. Replace controller with a new unit. Maintenance log shows frequent maintenance needed. Ref P8.2 Version 1, January 2014 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Event: NOT ALL THE MANGANESE REMOVED cont’d P8.2.1.9 KMnO4 dosing solution concentration incorrect, or prepared with incorrect chemical. P8.2.1.10 Poor air circulation for droplet, or thinfilm, aerator. P8.2.1.11 Poor nozzle design in spray aerator. From time to time have a second person check calculations used for preparation of KMnO4 dosing solution. Check KMnO4 concentration in each new batch of dosing solution prepared. Manganese. Permanganate concentration in dosing solution. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Supplier’s certification of analysis. Ensure that chemicals are delivered to the correct bin, that bins are labelled, and that an operator is there to supervise chemical delivery. Checks show frequent incorrect calculations. Provide for staff additional training in calculations for solution preparation. Ensure that chemical supplier is aware of the need for the operator to be present when chemicals are delivered. Obtain a new batch of chemical from the supplier, if quality unsatisfactory. Check quality of KMnO4 delivered. Do calculations and tests during design to ensure air circulation will allow enough oxygen to dissolve in the water. Design to ensure droplets are given longest possible time in the air to allow oxygen exchange (nozzle design and trajectory are important). Ref P8.2 Version 1, January 2014 Manganese. Manganese. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Calculations show air circulation too low. Manganese concentration is more than 50% of the MAV. Re-calculate chemical quantities required for the dosing solution, and prepare a new solution. If aerator relies on natural draft, consider installation of blowers to provide forced draft. Modify the aerator to minimise obstructions to air flow. Replace nozzles. Modify spray trajectory. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 7 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Event: NOT ALL THE MANGANESE REMOVED cont’d P8.2.1.12 Poor design of aerator. During design do pilot trials to check that the type of aerator chosen, and its design, will provide adequate oxidation of the metals. Manganese. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Trials/calculations show design is unsatisfactory. Replace or modify the aerator. P8.2.1.13 See P6 Guide series for a discussion of events, causes, preventive measures etc. associated with the use of standard filters, and those using greensand for combined oxidation and Poor removal of filtration. precipitated metal by filtration. P8.2.1.14 Greensand performance inadequate. P8.2.1.15 Power failure. Ensure KMnO4 dose (in the influent, or in off-line regeneration) is adequate to maintain the oxidising capacity of the bed. Manganese. Ensure that concentrations of other chemically reduced determinands in the water (eg, organic matter, nitrite, ammonia and hydrogen sulphide) are not so high that they exhaust the bed’s oxidising capacity. Provide sufficient time for the bed to “ripen” after bringing it back online. Schedule routine filter maintenance. This should check for channelling for example (see also Guide P6.1). Provide stand-by generator to ensure continuity of power. Continuity of power. Manganese concentration is more than 50% of the MAV. No sign of insoluble manganese formation directly after oxidation (metals must be insoluble to be removed). Loss of power. Adjust dose rate. Undertake a more complete check on the water chemistry and reconsider this treatment option if reduced determinand concentrations are high. Modify operational procedure. Start a filter maintenance programme. Refuel generator, if appropriate. Event: OXIDANT DOSE TOO HIGH Possible hazards: Manganese (if KMnO4 used as an oxidant), chlorine, chlorine dioxide or KMnO4. Level of risk: Moderate P8.2.2.1 Possible causes of overdosing with chlorine and chlorine dioxide are discussed in the relevant Guides for the individual oxidants. See Guides P7.1 (chlorine) and P7.2 (chlorine dioxide). Overdosing with ozone will not create a public health risk because of the rapid decay of this oxidant. The causes and preventive measures etc. associated with the use of KMnO4 as an oxidant are noted below. 8 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Ref P8.2 Version 1, January 2014 Causes Preventive measures Checking preventive measures What to check P8.2.2.2 KMnO4 dose rate set incorrectly or incorrect dose calculation. P8.2.2.3 Dosing controller malfunction. P8.2.2.4 Do bench-scale and pilot-scale testing to determine the best KMnO4 dose or aeration rate. From time to time get a second person to checks on the dose calculation. Routine controller maintenance. Dosing controller incorrectly calibrated. Signs that action is needed Manganese concentration more than 50% of its MAV. Pink water. KMnO4 dose. Use a controller (oxidation –reduction potential) that will automatically adjust the dose rate to ensure the right oxidant dose is used, or monitor often enough that the oxidant dose can be adjusted to match changes in water chemistry. Manganese. KMnO4 dose. Maintenance log. Replacement of a suspect controller with a reliable unit. Regular manual checks on the controller’s calibration. Corrective action KMnO4 dose. Manganese concentration more than 50% of its MAV. Pink water. Maintenance log shows frequent maintenance needed. Maintenance log not signed off. Manganese concentration more than 50% of its MAV. Pink water. Calibration schedule not signed off. KMnO4 dose. KMnO4 concentration in the dosing solution. Manganese concentration more than 50% of its MAV. Pink water. KMnO4 concentration in the dosing solution above the level expected. Carry out manual checks on manganese concentration and adjust the oxidant dose accordingly. Start checks on the dose calculations. Identify cause of fault and rectify. Replace controller with new unit. Recalibrate controller. Decrease dose rate until recalibration. Event: OXIDANT DOSE TOO HIGH cont’d P8.2.2.5 KMnO4 dosing solution concentration too high. Check the concentration of the KMnO4 dosing solution when it is first prepared. Separate chemical storage from dosing solution preparation tanks to reduce the likelihood of chemical spillage into the tanks. Ref P8.2 Version 1, January 2014 Determine the cause of the high KMnO4 concentration and rectify. Provide training in the preparation of oxidant solutions (including calculations). Identify the reasons for any spillage and rectify if possible. Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 9 Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Event: GERMS INTRODUCED DURING AERATION Possible hazards: Germs. Level of risk: Moderate1 P8.2.3.1 Microorganisms introduced into the water during aeration, either in the airstream or through animals entering the aerator. 1 Place netting over aerator grills to stop entry of larger animals (eg, birds, rats, etc). Microbiological water quality. E. coli or coliforms detected in a 100 ml sample taken after the aerator. Provide disinfection following aeration to inactivate germs that get into the water. Disinfection of the water following aeration. The consequences of the event, and therefore the level of risk, will be influenced by how well following disinfection processes works. Causes Preventive measures Checking preventive measures What to check Corrective action Signs that action is needed Removal by ion exchange Event: INCOMPLETE REMOVAL OF MANGANESE Possible hazards: Manganese. Level of risk: Low P8.2.4.1 Check water chemistry before selecting the treatment option to determine the concentrations of ions that will be adsorbed by the resin (commonly iron, manganese, calcium and magnesium). This will allow an estimate of operational time before regeneration will be required, and how much the hardness of the water will interfere with the iron and manganese removal. Monitor changes in treated water chemistry (eg, calcium, manganese) to determine when the resin is exhausted and regeneration is required. Ion-exchange resin exhausted. 10 Manganese. Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Manganese concentration more than 50% of its MAV. Consider a different treatment process. Ref P8.2 Version 1, January 2014 Causes Preventive measures Checking preventive measures What to check P8.2.4.2 Ion-exchange resin is fouled. P8.2.4.3 Check water chemistry before selecting the treatment option to determine whether the water contains organic material which will foul the resin, or whether the water contains insoluble iron or manganese which foul the resin. Manganese. Turbidity. Provide pre-treatment (eg, filters) to remove particulate matter from the water. Check when the exchanger is first installed that it has been properly packed. Signs that action is needed Ensure that air cannot come into contact with the water before it enters the ionexchange unit to avoid oxidation of iron and manganese. Channels in the ionexchange resin bed. Corrective action Manganese concentration more than 50% of its MAV. Turbid water entering the ion-exchange unit. Pretreat the water to remove organic matter. Consider a different treatment process. Locate and seal paths by which air may enter the system before the ionexchange unit. Install appropriate pretreatment, or improve the performance of the treatment already in use. Exchange unit rapidly fouled. Manganese. Manganese concentration more than 50% of its MAV. Repack the exchanger or return to the manufacturer. Microbiological quality. High counts of total bacteria. Regenerate and back-flush. Hardness not being reduced. Clean resin to remove bead fouling. Iron and/or manganese not being removed. Disinfect the water after the ion-exchanger. Odour. Event: BUILD-UP OF GERMS IN THE RESIN BED Possible hazards: Germs. Level of risk: Low1 P8.2.5.1 Organic matter and microorganisms trapped in the resin bed. 1 Regeneration of the resin at the frequency recommended by the manufacturer. This will also back-flush the bed and remove organic material. Regularly clean (de-foul) the resin beads with the recommended cleaning agent if iron or manganese are present in the water. Carry out treatment to remove organic matter from the water before the softener. Calcium. Magnesium. Iron. Manganese. The consequences of the event, and therefore the level of risk, will be influenced by how well subsequent disinfection processes work. Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 11 Contingency Plans If an event happens despite preventive and corrective actions you have taken, you may need to consult with the Medical Officer of Health to assess how serious a problem is. Event – Faecal matter gets into the water through the aerator Indicators: Required actions: Responsibility: 12 Faecal indicator organisms or pathogens are continually detected in the water leaving the plant. Knowledge of an animal having entered the aerator. Widespread sickness in the community linked to the water supply. Follow the actions given in Figure 3.2 of the DWSNZ:2000. Identify the reason for the failure and rectify. Record cause of system failure and steps taken to correct. Modify your water safety plan if necessary. Manager designated responsible for the water supply. Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Ref P8.2 Version 1, January 2014 Event – Very high oxidant concentration Indicators: Required actions: Responsibility: Knowledge of a major spillage or overdose of oxidant into the water. Pink colour of the water (KMnO4 overdose). Inability to obtain pink colour from DPD chlorine indicator despite high chlorine dose rates (NB this indicates chlorine levels well in excess of the MAV – very high chlorine or chlorine dioxide levels bleach the pink colour that normally develops in their presence). Water develops a strongly chlorinous odour. Widespread complaints of taste and odour, or black particles in the water or staining (KMnO4 overdose), or illness in the community. Close down the plant. Provide another source of potable water until water of acceptable quality can again be supplied. Inform the MOH of the situation. Identify the cause of the problem and rectify. Dump the reservoir water, or add chemicals to neutralise the oxidant if more appropriate (neutralisation may be required before any water is dumped anyway). Flush the distribution system, if excessive levels of chlorine are also present in the distribution system, and monitor water quality until chlorine concentrations are again back to normal operating levels. Warn consumers to thoroughly flush their taps before drawing water for use (if they are likely to have been affected). Record cause of system failure and steps taken to correct. Modify your water safety plan if necessary. Manager designated responsible for the water supply. Ref P8.2 Version 1, January 2014 Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal 13 Water Safety Plan Performance Assessment To make sure that your supply’s water safety plan (formerly known as a Public Health Risk Management Plan, PHRMP) is working properly, periodic checks are needed. The overview document outlines what needs to be done. The following table provides the detailed information for checking this particular supply element. What to measure or observe: Chlorine, chlorine dioxide or KMnO4 residuals. Faecal indicators (E. coli). Manganese concentrations greater than 50% of the MAV in the treated water. Follow the protocols set out in DWSNZ:2000. Note that the presence of faecal indicators may be influenced by factors other than the operation of the aerator. How often: What to do with the results: Responsibility: 14 For the monitoring frequencies for FAC and E. coli measurements see DWSNZ:2000 Section 3.3.2. Manganese should be monitored at least once a month if not in transgression of the MAV. Record results to meet legislative requirements or to allow water safety plan performance assessment. The WINZ database is good for this. The collected data need to be periodically reviewed to see whether problems with this supply element are developing. This should be done as frequently as the manager responsible considers necessary to minimise risk to public health arising from this supply element. Should this review show any unusual incidents, indicate that proper procedures are not being carried out, highlight poor laboratory results or indicate that poor water quality is reaching customers, then review the procedures for managing iron and manganese removal. Evaluate the monitoring results, and any actions taken as the result of having to implement a contingency plan, to see if the water safety plan needs modification – eg, preventive measures are up to date; the contingency plan steps are still adequate; and changes to the iron and manganese removal process are recognised in the plan. Manager designated responsible for the water supply. Water Safety Plan Guide: Treatment Processes – Iron and Manganese Removal Ref P8.2 Version 1, January 2014