Environmental Technology, Vol. 22. pp 1253-1262 © Selper Ltd, 2001 REFIXATION OF PHOSPHATES RELEASED DURING BIO-P SLUDGE HANDLING AS STRUVITE OR ALUMINIUM PHOSPHATE N. JARDIN*1 AND H.J. PÖPEL2 1Ruhrverband, 2 Kronprinzenstr. 37, D-45128 Essen, Germany Carl-Ulrich-Str. 39A, D-64297 Darmstadt, Germany (Received 28 February 2001; Accepted 20 March 2001) ABSTRACT Phosphate release and phosphate fixation during sludge treatment of waste activated sludge was investigated with a pilot plant for enhanced biological phosphorus removal, complemented by laboratory investigations of sludge samples from different large enhanced biological phosphorus removal plants. The major part of the eliminated phosphorus in the pilot plant was due to the storage of polyphosphate in the waste activated sludge and was accompanied by an uptake of magnesium and potassium. Stabilising waste activated sludge from the enhanced biological phosphorus removal pilot plant results in a hydrolysis of polyphosphate. As a result of polyphosphate hydrolysis in stabilising systems, phosphate, magnesium and potassium are released, but only potassium remains in solution whereas magnesium and a part of the released phosphate was precipitated as struvite. Another large fraction of the released phosphate was fixed by participation of aluminium. Keywords Enhanced biological phosphorus removal, sludge treatment, polyphosphate, struvite INTRODUCTION Most of the new or expanded wastewater treatment plants are designed for the so-called enhanced biological phosphorus removal process (EBPR; for an overview of the main types of EBPR processes see [1]). In contrast to conventional plants, the phosphorus content of the activated sludge solids from this process reaches values of up to 7 %. Phosphorus can be bound in the activated sludge mainly by three mechanisms. One is as physiological phosphorus, that is, P for metabolism and growth. Second, in plants with EBPR, additional phosphorus can be stored as polyphosphate (poly-P), Men+2PnO3n+1 (n indicates the chain length of poly-P and Me represents a metal cation). Usually, magnesium (Mg) and potassium (K) are associated with poly-P synthesis. Finally, a physicochemical fixation of phosphate mainly by precipitation or adsorption can occur. From a theoretical point of view, most of the phosphorus eliminated in the form of poly-P should be released during the anaerobic treatment of waste activated sludge (WAS) [2]. In contrast, at most large plants in Europe the soluble phosphorus concentration of digested sludge is often very low [3-6] whereas from other plants additional phosphorus loads of up to 100 % are reported [7-9]. In order to pursue the fate of the total phosphorus during wastewater and sludge treatment, an EBPR pilot plant with different sludge treatment systems has been operated over a 2 year period. Some of the results obtained during this study are presented in this paper with special respect to (i) the determination of type and extent of phosphate fixation in WAS, (ii) the estimation of the amount of P-release and the resulting P-feedback during sludge stabilisation, and (iii) the investigation of physico-chemical P-fixation mechanisms in stabilising systems. MATERIALS AND METHODS The pilot plant (PP) consisted of two continuous flow activated sludge systems both operated with settled domestic sewage (Figure 1). Plant 2 has been operated with an anaerobic zone for EBPR, whereas plant 1 served as a control without an anaerobic tank. The WAS of the EBPR plant was withdrawn directly from the activated sludge tank to prevent anaerobic conditions prior to sludge treatment. Thickening of the sludge was carried out with a centrifuge, a flotation unit or by gravity thickening. Thereafter, the thickened sludge was mixed with primary sludge and pumped into the stabilising system that consisted of an anaerobic-mesophilic digester (AMS) and aerobic-thermophilic stabilisation (ATS). The stabilising reactors were operated in parallel at different 1253 retention times (AMS: 15 to 30 days; ATS: 3 to 12 days), temperatures (AMS: 35°C; ATS: 50 to 65°C) and solid concentrations (1 to 5 % total solids (TS). The design parameters and the average operating conditions of the EBPR and conventional pilot plant in the first experimental year are shown in Tables 1 and 2, respectively. Because of the very low phosphorus content of the domestic sewage used for the experiments, the inflow of the pilot plant was supplemented with phosphoric acid, and in some experimental phases, with acetic acid to improve EBPR. For the investigation of physicochemical P-fixation mechanisms sludge samples from different large and pilot Figure 1. Table 1 Flow diagram of the pilot plant. Design parameters of the pilot plants (mean values during the first experimental year). parameter plant 1 plant 2 volume (m3) influent flow (m3 h-1) aerobic HRT1 (h) anaerobic HRT1 (h) MCRT (d) 10 2.5 4 2.6 16 4 2.5 1.5 2.6 1 EBPR and conventional plants were used. The characteristics of these sludges are summarised in Table 3. To investigate the pH-dependent release of phosphate an acidimetric titration was performed. For this purpose, a 1-l sludge sample was titrated with concentrated HCl. Once a desired pH was achieved, 40 ml of sludge was withdrawn and incubated for 24 h to establish equilibrium. Usually, the acidimetric titration covers a pH range from original pH to a pH of 1. After the incubation period, the pH was measured again and the samples were centrifuged at 30,000g for 10 minutes followed by 0.45-m filtration. In the filtrate PO4-P and the major cations were analysed. Table 2. hydraulic retention time based on influent flow rate 1254 Average operating conditions of the pilot plants (mean values during the first experimental year). parameter plant 1 plant 2 influent effluent effluent BOD5 (mg l-1) COD (mg l-1) Ptot (mg l-1) TKN (mg l-1) 175 340 12.4 66 20 82 10.3 23 14 62 3.3 23 NH4-N (mg l-1) 48 Table 3. 19 21 Characterisation of the sludges used for the investigations of physico-chemical P-fixation mechanisms. sludge name (abbreviation) origin DS EBPR MS Digester sludge from a large EBPR plant with main stream process (PHOREDOX) Stabilised sludge from a large EBPR plant with main stream process (ISAH) Digester sludge from the EBPR pilot plant with main stream process (A/O) Digester sludge from a large EBPR plant with side stream process (PHOSTRIP) Digester sludge from a large plant with simultaneous precipitation (Fe) Primary sludge stab ES EBPR MS DS EBPR MS PP DS EBPR SS DS Sim PS aTS TSa) [g l-1] VS b) [%] pH P Ca Mg K Al Fe [mg g-1] [mg g-1] [mg g-1] [mg g-1] [mg g-1] [mg g-1] 38.6 51.4 7.32 27 51.5 9.8 7.4 17.1 15.2 29.8 59.6 6.82 42.8 40.6 10 13 35 11.6 28.8 58.4 7.29 52.2 45.2 11.2 16.9 23.8 10.5 25.9 55.8 7.46 26.8 57.8 7.7 6.8 26.3 12 49.3 51.5 7.8 27.2 85.4 5.8 2 17 49.7 40.6 75.5 5.46 10 31.6 3.6 5.6 17.2 10.2 = Total solids, b) VS = Volatile solids All sludges were examined further with a sequential dilution test. Because of the successive reduction of total solids concentration in the course of the dilution procedure, the solubility behaviour of precipitated solids can be selectively modified without changing pH. For this test, 50 ml of sludge was filled in a 100-ml volumetric flask. Deionised water (A. dest) was added to make up 100 ml and subsequently, the dilution was vigorously shaken for 2 minutes. From this dilution step another 50 ml were transferred to the next 100-ml flask, and the dilution procedure was repeated as described until a final dilution of 1 to 1024 was reached. After an equilibration period of 24 hours the samples were centrifuged, filtrated and analysed for phosphorus and cations. P-fractionations were used to differentiate between the phosphorus fixation mechanisms. For this purpose a modified method of Psenner et al. [10] and Uhlmann et al. [11] was used. The fractionation consists of sequential extractions of the sludge samples with different extracting chemicals followed by incubation, centrifugation and analysis of the supernatant. In the supernatant PO4-P (after 0.45-m filtration) and Ptot were determined. PO4-P concentration represents the so-called dissolved reactive phosphate (DRP) and the difference between Ptot and PO4-P is called the nonreactive phosphate (NRP). Elementary analyses of P, Ca, Mg, K, Al and Fe in the sludge samples were performed by means of atomic absorption spectrometry (AAS) with a Perkin Elmer 2100. Soluble Ca2+, Mg2+, K+ and Na+ were analysed by ion chromatography with a Dionex ISP 2000. Al3+ was determined by a colorimetric method using chromazurol S. X-ray diffraction analyses were performed using a STOE powder diffraction system. For energy dispersive X-ray spectroscopy a Joel JSM 35 scanning microscope and a Tracor 5500 were used. With this system the element distribution of the samples could be visualised for a total of 8 elements at the same time. All other analyses were performed according to DEV [12]. RESULTS AND DISCUSSION Type and Mechanisms of P-binding in WAS During the 2-year experimental period, the P, Mg, K, Ca, Fe and Al contents of the WAS from the EBPR plant were determined weekly. From a correlation analysis, it was found that magnesium and potassium were significantly correlated on an = 0.01 level with phosphorus. This indicates that polyP formation, which usually is accompanied by an uptake of these cations, has taken place. The linear regression between the cations and the phosphorus content of the WAS is sketched in Figure 2. From this graph a molar uptake ratio of 0.335 M Mg M-1 P and 0.258 M K M-1 P can be calculated which agrees well with values reported in the literature (e.g. [13, 14]). No correlation between P and Ca, Fe or Al was found. Consequently, the amount of physicochemically fixed phosphorus in the WAS of the EBPR plant was very low under the operating conditions used in this study. Although these dependencies provided a strong 1255 indication that at least part of the phosphorus is fixed as polyP, it was not possible to calculate the exact amount of poly-P storage. To quantify the amount of poly-P, P-fractionations were used. Figure 3 shows the results of the periodically performed fractionations of the WAS from the EBPR plant. As can be seen from this figure, the major part of total phosphorus is recovered as NaOH-NRP. In WAS from plants with EBPR, this fraction usually consists of organic Figure 2. phosphorus and poly-P, whereas at plants with iron or aluminium precipitation the major part of precipitated phosphorus is also found in this fraction. A differentiation between the different P-species is facilitated if the counterions are considered. Potassium gives especially valuable indications toward P-binding in the NaOH-fraction. Because of the former uptake in the course of poly-P synthes is, potassium is expected to be released simultaneously with Dependence between phosphorus and magnesium/potassium content in WAS. 1256 Figure 3. P-fractionation of WAS (bars indicate standard error). poly-P during the alkaline extraction. Because potassium Figure 4 summarises P-fractionations of both anaerobicusually participates only to a small degree in precipitation or mesophilic and aerobic-thermophilic stabilised sludge. adsorption reactions in wastewater and sludge treatment, it Clearly, the NaOH-NRP fraction that comprises the major can be assumed that high potassium levels in the extracts are part of poly-P was reduced to below 4 % (ATS) and 6 % mainly the result of poly-P hydrolysis. Therefore, we looked (AMS) of total P. Considering that organic phosphorus will for a dependence between potassium and NRP/DRP also be found in this fraction, the poly-P content of the sludge concentrations in the different extracts. For the NaOH-NRP samples tends to be zero. From these fractionations it is fraction, this dependence is also depicted in Figure 3. From obvious that a shift from the NaOH-NRP fraction in WAS this graph it can be seen that NaOH-NRP and potassium are towards the NaOH-, HCl- and to a lesser extent to the very closely correlated. This clearly demonstrates that for the original-DRP fraction has occurred. The former two fractions WAS from the pilot plant, the major part of phosphorus in the mainly consist of physicochemically fixed phosphorus, NaOH-NRP fraction can be assigned to poly-P. Furthermore, whereas the latter fraction represents the soluble phosphate in for the other fractions, a similar correlation between DRP and the stabilising system. potassium was found (data not shown). In all, a poly-P The same result, that is, a complete release of poly-P, content of 50 to 70 % of total P could be calculated assuming was obtained performing potassium balances for the an exchange ratio between phosphorus and potassium of stabilising systems [16], assuming that potassium is released 0.26 M K M-1 P. during poly-P hydrolysis and does not participate in precipitation reactions and remains, therefore, in soluble P-release and P-fixation During Sludge Stabilisation form. Although these experiments provide evidence that Because of the elevated temperatures in anaerobicstabilising WAS from EBPR plants with AMS or ATS causes a mesophilic (T = 35°C) or aerobic-thermophilic (T = 50 to 60°C) rapid hydrolysis of poly-P, only a part of the released stabilisation, it could be expected that complete poly-P phosphate remains in solution. In our experiments the hydrolysis occurs within a fraction of the usual retention time amount of soluble PO4-P depended mainly on the total of these stabilising systems. Using P-release kinetics [15] it can P-concentration in the stabilising system, which primarily be estimated that 90 % of the poly-P is hydrolysed within 1.5 reflects the amount of poly-P in the inflow to AMS or ATS. days at 35°C and within 7 hours at 60°C. Beside this At total P concentrations in the stabilising system of 1,000 theoretical calculation, further evidence for a complete release to 1,500 mg l-1 Ptot, which is common for large wastewater of the stored poly-P in our experiments was provided by treatment plants, the amount of soluble phosphate accounts P-fractionations and potassium balances. for not more than 20 % of Ptot, whereas at excellent EBPR 1257 Figure 4. P-fractionation of anaerobic-mesophilic and aerobic-thermophilic stabilised sludges (bars indicate standard error). conditions with a total P concentration of up to 4,000 mg l-1, systems, a precipitation of magnesium in the form of the amount of PO4-P increased to 38 % of Ptot. MgNH4PO46 H2O (struvite) seems to be the most likely From the results obtained so far it seems clear that the reaction to occur. In fact, struvite was found in most of the difference between released phosphorus and the soluble sludge samples as was demonstrated by X-ray powder phosphorus concentration observed during stabilisation was diffractometry and energy dispersive X-ray spectroscopy mainly fixed by physicochemical mechanisms. To estimate the (EDXS). This is shown in Figure 5 for a digested sludge amount of physicochemical phosphorus fixation, some of the sample from the EBPR pilot plant. The diffraction pattern (A) possible counterions for precipitation and/or adsorption of the sludge agrees well with the theoretically expected reactions were examined further. In view of their high pattern for struvite and, furthermore, EDXS shows (B) that amounts in stabilised sludge, aluminium, magnesium, and phosphorus and magnesium are closely correlated in the calcium should be the most likely counterions for sample. physicochemical fixation of phosphorus. Furthermore, all sludge samples were examined by a Beside the sludges from the pilot plant, different sequential dilution procedure in which dissolution of stabilised sludge samples from large wastewater treatment precipitated solid phases is achieved through progressive plants with or without EBPR, which are described in detail in dilution of the sludge sample. The results of these tests are Materials and Methods, were also included in the summarised in Figure 6 by correlating the amount of released investigations. They were examined towards possible magnesium with the released phosphate in the course of the interactions of magnesium, aluminium and calcium with sequential dilution. For the EBPR sludges a surprisingly high phosphate. correlation between phosphate and magnesium release was Magnesium is affected by sludge stabilisation in two found. To verify that the observed release behaviour was ways. First, because of the degradation of organic material a mainly due to the dissolution of struvite, digested sludge part of the physiological magnesium is dissolved, and second, from the pilot plant, which was supplemented with magnesium is released in the course of poly-P hydrolysis. In phosphate and magnesium to induce struvite precipitation view of the high ammonium concentrations in stabilising (struvite formation was proved by X-ray diffraction), was also 1258 Figure 5. X-ray diffraction pattern and distribution diagram of phosphorus and magnesium for a digested sludge sample from the EBPR pilot plant (A: X-ray diffraction pattern; B: distribution of P and Mg from EDXS). Figure 6. Phosphate and magnesium release during the sequential dilution test. investigated with the sequential dilution test. A comparison with the EBPR sludges reveals a nearly identical release behaviour which provides further evidence that the released amounts of magnesium and phosphate in the EBPR sludge samples are due to the dissolution of struvite solids. From the sequential dilution test the amount of struvite in the original sample could easily be determined using the total phosphate and magnesium release during the dilution procedure. The amount of P-fixation in the form of struvite was highest in the EBPR sample from the pilot plant (37 % of Ptot) and was usually in the range of 20 to 30 % of Ptot [17]. Greater deviations from the predicted release behaviour were only found in the sludge samples from the plant with simultaneous precipitation, which is obviously due to a dissolution of iron phosphate. Because of the substitution of detergent phosphates with zeolites in Germany (e.g. zeolite A: Na12(AlO2)12(SiO2)12·27 H2O), sludges from wastewater treatment plants usually show relatively high aluminium concentrations (in the sludge samples: 17 to 35 mg Al g-1 TS). Therefore, aluminium was also considered as a possible counterion for phosphate precipitation or adsorption in stabilised sludge. Although in none of the sludges indications for crystalline aluminium solids were found, acidimetric titration of the sludge samples reveals a significant participation of aluminium in phosphate fixation as is shown in Figure 7. Below pH 3 to pH 3.5, the release behaviour of both aluminium and phosphate is very similar, whereas greater differences for the phosphate release exist at higher pH values which are mainly due to the release of other solid phases (e.g. struvite). For the EBPR sludges from plants with the main stream process, the amount of P fixed by interaction with aluminium, was calculated as 35 to 52 % of Ptot. Although the exact mechanisms of phosphate-aluminium interactions are not clear yet, we believe that phosphate is mainly fixed by surface reactions, such as complexation or adsorption to aluminium solids. Calcium was also considered as one of the possible counterions for phosphate fixation in stabilising systems and was, therefore, further examined. Just as with aluminium, no crystalline calcium phases were found in any of the sludges. Because most of the possible calcium-phosphate precipitates are acid-labile, acidimetric titration was used to determine the amount of possible calcium-phosphate fixation. In Figure 8 the release of calcium is normalised to the total calcium content of the sludge samples. Some interesting information concerning possible interactions between calcium and phosphate could be obtained from this graph. First, although there are quite great differences in the total calcium concentrations in the sludge samples, only minor differences are found in the release behaviour normalised to the total concentration. Furthermore, the behaviour of the different sludges (e.g. primary sludge, EBPR sludge and digested sludge supplemented with phosphate and magnesium) is nearly the same. Second, a correlation between the release of phosphate and calcium was not found in any of the titrations 1259 (data not shown). Therefore, it seems likely that calcium did not participate in phosphate fixation reactions and was mainly Figure 7. bound by other mechanisms in the sludge samples, such as adsorption to hydroxyl surfaces. Al3+ and PO4-P release in the course of acidimetric titration. In cases of high P-concentrations in sludge water, precipitation of phosphate in the centrate or filtrate of the dewatering facility can be necessary. In principle, all common chemicals for phosphate precipitation could be used but in view of the relatively high ammonium concentrations and the high alkalinity of the process water, precipitation with calcium can require large amounts of lime. Using iron, the reduction of Fe3+ to Fe2+ has to be considered. Figure 9 shows the results of PO4 precipitation in sludge water using different chemicals and different initial phosphate concentrations. As can be seen from these figures, aluminium proved to be most effective on a molar base. Usually, more than 80 % of the soluble phosphate was precipitated at a molar dosage of 1 M Al M-1 P, whereas for calcium and iron an 80 % elimination was achieved only when a molar dosage of 2 M Ca M-1 P or 1.5 M Fe M-1 P was reached. CONCLUSIONS Under the conditions of this study 50 to 70 % of total phosphorus in WAS of the EBPR pilot plant was stored as poly-P which could be calculated on the basis of P-fractionations and potassium balances. Poly-P synthesis was always accompanied by an uptake of magnesium and potassium at a molar ratio of 0.34 M Mg M-1 P and 0.26 M K M-1 P, respectively. Poly-P hydrolysis during stabilising WAS was complete within the retention time of the stabilising systems which could be demonstrated by P-fractionations and potassium balances. However, because of physicochemical fixation mechanisms only a part of the released phosphate remains in solution. In the P-fractionation a shift from the NaOH-NRP fraction of the WAS (primarily poly-P) toward the NaOHand HCl-DRP fractions (primarily physicochemical P-fixation) in stabilised sludge was observed. The amount of soluble phosphate in the stabilising system depends mainly on poly-P content in the WAS. From the results obtained in our study, the P-feedback on the average large EBPR plant, characterised by a total P content of not more than 35 mg P g-1 TS in the WAS, was estimated to be below 20 % of the influent P load. In the stabilising system the released phosphate was fixed mainly by two mechanisms: First, because of the simultaneous release of magnesium during poly-P hydrolysis, a part of the released phosphate was precipitated as struvite. Second, another fraction of released phosphate was fixed by interactions with aluminium, probably by surface reactions on aluminium solids. No participation of calcium in phosphate fixation reactions was found. 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