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11.phosphorus speciation in drinking water treatment residuals

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11.phosphorus speciation in drinking water treatment residuals

  1. 1. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 6 | P a g e www.iiste.org Phosphorus Speciation in Drinking Water Treatment Residuals (WTRs) and Biosolids-Amended Soils Using XANES Spectroscopy Mahdy Ahmed Department of Soil and Water, College of Agriculture, Alexandria University, Alexandria Elshatby,21545, Alexandria University, Alexandria, Egypt Tel: 003-02-5904684 E-mail: amahdy73@yahoo.com Elkhatib Elsayed Department of Soil and Water, College of Agriculture, Alexandria University, Alexandria Elshatby,21545, Alexandria University, Alexandria, Egypt Tel: 003-02-5904684 E-mail: selkhatib1@yahoo.com Fathi Nieven Salinity and Alkalinity Soils Research Laboratory Ministry of Agriculture, Cairo, Egypt Tel: 003-02-5046479 E-mail: nieven74@yahoo.com Zhi-Qing Lin Environmental Sciences Program & Department of Biological Sciences Southern Illinois University, Edwardsville, Illinois 62026, USA E-mail: zhlin@siue.edu Abstract X-ray absorption near-edge structure (XANES) spectroscopy (a non-destructive chemical-speciation technique) is a useful technique available for determining the speciation of P in various environmental samplesTwo incubation studies were conducted to assess the P species formed in an originally neutral and alkaline soil in response to high biosolids and/or WTRs applications using P K-edge X-ray absorption near edge structure (XANES) spectroscopy. The results indicated that combination of P standards yielding the best linear combination fits for biosolids were phytic acid (26.03%) and Cu3(PO4)2 (73.09%) and a little of P-sorbed to Al hydroxide (0.89%). However, The combination of P standards yielding the best linear combination fits for WTRs were P-sorbed to Fe hydroxide (64.19%), phytic acid (30.72%) and P-sorbed to Al hydroxide (5.07%). The P speciation in 10 g kg-1 -treated clay soils were phytic acid (19.08%), Mn3 (PO4)2 (0.79%), Phytic acid(K,Mg salt)(11.22%), Cu3(PO4)2 (7.26%), and hydroxyapatite (57.98%). Addition of WTRs modified the P speciation in biosolids- amended soils, and the changes varied depending on biosolids and WTRs application rates. The P speciation in soils depends on the soil type and application rates of biosolids and WTRs. Keywords: Biosolids, P, XANES, WTRs, Soils 1. Introduction Land application of biosolids on agricultural fields generally serves two main purposes: first, it provides essential nutrients to crops; and second, it serves as a means of waste disposal for wastewater treatments plants. Biosolids supplies phosphorus (P) to the soil (Kingery et al. 1993; Evers 1998), and contributes to increased yields of forage and field crops where P was previously limiting production (Brink et al 2002; Cooperband et al. 2002; Balkcom et al. 2003). However, when land application is aimed primarily at supplying nitrogen (N) to crops and/or reducing the waste volume, P applied with biosolids can far exceed the amount of P required by most crops (Eghball et al. 1999). For example, a typical N:P uptake ratio for corn is 7.5:1 (U.S. EPA 1981), while the N:P ratio for biosolids reported in
  2. 2. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 7 | P a g e www.iiste.org the literature tends to be approximately 2.5:1 (Edwards & Daniel 1992). Initially soils will retain most of the P applied in excess of crop uptake through various transformation processes including immobilization, adsorption, and precipitation. Apart from plant uptake, P can be lost by surface erosion (Pionke et al. 2000; Smith et al. 2001) and/or subsequently by leaching (McDowell et al. 2004). Such losses have resulted in eutrophication of rivers and lakes in the past decades (Daniel et al. 1998; Sharpley et al. 2001). Adsorptions to surfaces of iron (Fe) and aluminum (Al) oxides and clay minerals and precipitation as secondary Fe and Al P minerals are predominant reactions for solution P in acidic soils and as Ca P minerals in alkaline soils. Alum [Al2(SO4)3⋅18H2O] is commonly used at municipal drinking water treatment plants for water purification. It is added at the head of the water treatment process to remove fine particulates and, therefore, reduce water turbidity. Alum serves as a coagulant and forms particulate complexes that are then settled out and removed along with lime sludge, termed as water treatment residues (WTRs). These WTRs commonly contain high levels of aluminum (Al), calcium (Ca), iron (Fe) and other major cations that have potential for reacting with P to form water- insoluble phosphate compounds and reduce the bioavailability of P in agricultural soils (Basta et al. 2000). For example, O’Connor & Elliott (2002) indicated that the addition of WTRs had dramatically reduced soluble P in soil leachates. Staats et al. (2004) further reported that the use of alum as a poultry litter amendment effectively reduced soluble P in the poultry litter. As a result, one may suggest that the co-application of WTRs and biosolids promote agricultural land use of biosolids (Elliot et al. 2002). There is, however, a limited amount of information on potential chemical interaction between P in biosolids and major cations in WTRs, particularly regarding P speciation and temporal dynamics in the mixture of biosolids and WTRs. Furthermore, chemical processes for the co-precipitation and chemical-physical processes for adsorption of P with amorphous Al- and Fe-hydrous oxides or other minerals, which are major components in biosolids and/or WTRS, needs to be elucidated. P speciation in soils amended with biosolids and drinking water treatment residuals(WTRs) is essential in providing information to formulate best management practices(BMPs) to mitigate surface water degradation through eutrophication ( Beauchemin et al. 2003; Shober et al. 2006; Ajiboye & Akinremi 2007). Different P species have very different physiochemical properties, which can determine their relative tendency to precipitate, adsorb, or dissolve in soil solution. Shober et a. (2006) conducted P speciation analysis on biosolids that had been treated with Al2(SO4)3 or FeCl3 compounds that are commonly used in drinking water treatment. Their study showed a reduced solubility of P in biosolids that were treated with the chemicals. Other P-speciation studies using biosolids and animal manures have elucidated consistent results regarding chemical forms of P (Beauchemin et al. 2003; Ajiboye et al. 2007). These previous studies determined that the dominant P species were calcium phosphate species such as hydroxyapatite (calcium phosphate or HAP) and amorphous Al- and Fe- P species (Beauchemin et al. 2003; Shober et al. 2006; Ajiboye et al. 2007). All of the P species are precipitated minerals (or not surface adsorbed) and thus are not subject to a Pmax adsorption value. It was observed by Beauchemin et al. (2003) that HAP was the most dominant species at all pH levels observed, but especially dominant at lower pH values. Because of the thermodynamic stability of HAP, it can be a major sink for P in a non labile state. When compared to manures, HAP is more dominant in biosolids and the water soluble P concentration was higher in extractions of manures than biosolids (Ajiboye et al. 2007). It has been suggested that the lower P lability and higher HAP dominance in biosolids result from the lime stabilization often used for treatment before land application (Ajiboye et al. 2007). X-ray absorption near-edge structure (XANES) spectroscopy (a non-destructive chemical-speciation technique) is a useful technique available for determining the speciation of P in various environmental samples (Khare et al. 2005; Sato et al. 2005; Pickering et al. 1995). Because of the non-destructive nature of this technique, XANES analysis directly identifies the chemical species present without significant chemical modification. Each chemical species has a characteristic emission spectrum. Known standards are analyzed and then a curve fitting technique is applied to determine P species present in unknown samples. The objective of this study was: to assess the P species formed in an originally neutral and alkaline soil in response to high biosolids and/or WTRs applications using P K- edge x-ray absorption near edge structure (XANES) spectroscopy. 2. Materials and Methods 2.1 Sample Collection and Preparation Three Egyptian soil types were selected for this study: Kafr El-Dawar soil (Typic torrifluvent, from
  3. 3. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 8 | P a g e www.iiste.org Elbohera Governorate, Egypt), El-Bostan soil (Typic torripsamment, from Elbohera Governorate, Egypt), and Borg Al-Arab soil (Typic calciorthids, from Alexandria Governorate, Egypt). Soils were collected from a depth of 0-15 cm at each sampling location. Air-dried soil samples were ground and subsequently sieved (< 2 mm). The experimental dried biosolids were obtained from the General Organization Sanitory (GOS) in Alexandria City (Station No 9), Egypt. The WTRs were collected from the drinking water treatment plant in Kafr El-Dawar, Elbohera Governorate, Egypt. Both biosolids and WTRs were air-dried and sieved (< 2 mm) prior to use (Makris & Harris 2005).The general physio- chemical properties of the soils, biosolids, and WTRs are compiled in Table (1). Soil pH and electrical conductivity (EC) were determined using the paste extract method (Richards 1954); WTR and biosolid pH and EC were analyzed using 1:2.5 suspension (Richards 1954); Calcium carbonate content was determined by calcimeter (Nelson 1982); Particle size distribution was measured according to the hydrometer method (Day 1965); The organic matter content (OM) of the samples was determined by dichromate oxidation method (Nelson & Sommers 1982); Cation exchange capacity (CEC) was determined using 1 M NaOAC (Rhoades 1982). In addition, KCl-extractable Al was determined colorimetrically using 8-hydroxy quinoline butyl acetate method (Bloom et al. 1978). The available phosphorus was determined according to Olsen & Sommers (1982). The DTPA extractable heavy metals was determined according to Lindsay & Norvell,(1978). Concentrations of total metals were determined using ICP-MS according to Ure (1995). Field capacity (FC) was determined by the pressure-plate method (Tan 1996). The American soil was collected from an agricultural field in Liberty, Illinois located at 685872E, 44201764N zone 15s. The soil had not been amended with biosolids or animal manures for at least 25 years. Soils were analyzed for general properties according to Page et al. (1982) (Table 2). Biosolids were collected from the Troy Municipal Wastewater Treatment Plant in Troy, Illinois in February, 2005. The plant treats domestic sewage sludge for a community of approximately 10,000 residents with no input from major industry. The water content of the biosolids was 75%. The pH of the biosolids was 11.9±0.2. Biosolids were stored indoors in plastic buckets. Drinking water treatment residuals (WTRs) were collected from the Hartford Drinking Water Treatment Facility in Hartford, Illinois in September, 2005. The facility has been in operation since 1971 serving a community of approximately 1,500 residents. The WTRs were turbulently released from the water treatment process as liquid containing suspended solid particulates at a concentration of a few percent. The WTRs were taken directly from holding tanks, where coagulated particulates and alum and lime treatment are allowed to precipitate from water. Once WTRs were in buckets and tubs they rapidly precipitated so the water could be decanted off. Water was removed at collection and for the weeks following collection until the WTRs reached a moisture content of 100%. The pH of the WTRs was 9.0±0. WTRs were stored indoors in plastic buckets. Moisture content for all experiments was determined by weighing moist samples then oven drying and weighing dry samples. Soils, biosolids, and WTRs were chemically characterized using inductively coupled plasma mass spectroscopy (ICP-MS) to determine concentrations of different elements (Table 2). Samples were oven-dried at 45ºC for 3 days and ground to a fine powder in an agate mortar and pestle. Ground samples were digested using EPA method 3050B for sludges and soils. 2.2 Soils Incubation Experiments In the Egyptian experiment, different application rates of WTRs (0, 1, 2, 3, and 4%, w/w, DW) and biosolids (0, 1, 2 and 3%, w/w) were added to each soil by fixing one rate of biosolids and varying the rate of WTRs. The experimental soil was thoroughly mixed with the biosolids and WTRs and then the treated soil was transferred to a large plastic bin. The soils that were not treated with the biosolids and WTRs were used as the control. Distilled water was added to obtain the desired soil field capacity (FC). The treated soils were then transferred to polypropylene jars, and brought to the field capacity. The soil moisture content in the treated soil was kept constantly at the field capacity level during the incubation period by periodically weighing the jars and adding distilled water to compensate for the water loss through evaporation. The jars were covered with perforated plastic film and incubated at 25 °C for 60 days. The experimental design was a split-split plot design, with four replicates of each treatment (240 jars). After the incubation period, soil samples were air-dried, crushed to pass a 2-mm sieve, and stored till chemical analysis.
  4. 4. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 9 | P a g e www.iiste.org In the American experiment, all samples of soil, biosolid and WTR were ground to a fine powder using a ceramic mortar and pestle. After grinding, each of the three components (biosolids, WTRs, and soil) was weighed appropriately to provide each of the following treatments: WTR rates (0, 20, 40, 80, and 160 g WTRs kg-1 soil). Each WTR treatment level was crossed with biosolid loading rates of (0, 25, and 50g biosolid kg-1 soil). The experimental design used was a completely randomized design repeated for each level of biosolids application. This design was chosen because the purpose of the objective of the experiment was to determine the effects of WTRs. The mixtures were scaled to provide a total of 50g of soil, biosolid, and WTRs combined. Sample mixtures were placed into plastic cups and saturated with distilled water. The samples were placed randomly on a bench at room temperature for a period of 30 days. After ten days of incubation all samples were re-saturated then re-saturated again at 20 days. At 30 days the samples were removed from the plastic cups and laid on drying paper to air dry for 3 days. After air drying was complete, all samples were ground in a ceramic mortar and pestle then placed into plastic bags. 2.3 X-ray absorption near-edge structure (XANES) analysis The XANES analysis was carried out at the Synchrotron Radiation Centre (SRC) at Stoughton, Wisconsin. The biosolids and sample mixtures of biosolids and WTRs were attached in a thin layer over double-sided conducting carbon tape, and the sample target was positioned at a 45-degree angle to the X-ray beam. X-ray absorption spectra (near edge structure) were collected by monitoring the P K- edge fluorescence using the double crystal monochromator (DCM) beam-line of the Canadian Synchrotron Radiation Facility, having a 13-element Ge detector and cryostat for spectrum collection in a series of replicate scans. The source electron energy ranged from 800 to 1000 MeV, with a current ranging from approximately 120 to 250 mA. Additional information regarding the P calibration has been reported in details previously by Lombi et al. (2006) and Ajiboye et al. (2007). The analysis of the XANES spectra was performed using an edge-fitting method using SIXPack software as described by Webb (2005). The normalized edge spectrum of a sample containing unknown P species was fitted to a liner combination of the spectra of standard P compounds by using a least-squares minimization procedure. 2.4 Phosphorus standards for XANES spectroscopy Based on the principle components analysis (PCA) identification (Seiter et al. 2008), the following 14 P standards were selected to fit potential P species present in the biosolids and WTRs samples: AlPO4 crystal, wet, amorphous AlPO4, P-sorbed on amorphous Al2(OH)3 , Ca3(PO4)3, Na3PO4.12H2O, (NH4)MgPO4·xH2O, Phytic acid (corn) (H12IP6), CaH10P6 , Ca6IP6 , Na12IP6 , Phytic acid dodecasodium (C6H17NaO24P6) , K4Mg2H4IP6 , K2H10IP6 , and Hydroxyapatite. SixPACK software (Webb 2005) was used to average replicate spectra from each sample and fit the averaged spectra to those of standards. The software calculated the percentage of each P standard in the sample using a least squares fit. The PCA analysis eliminated insignificant P species leaving only those contributing a major component in the sample. 3. Results and Discussion 3.1 Phosphorus Forms inBbiosolids and WTRs The heterogeneity of the biosolids and WTRs samples provided a challenge for the interpretation of the P-XANES spectra. However, several distinctive features could be identified on the spectra (Figure 1). The combination of P standards yielding the best linear combination fits for biosolids were Ba6 with phytic acid (26.03%) and Cu3 (PO4)2(73.09%) and a little of P-sorbed to Al hydroxide (0.89%).However, The combination of P standards yielding the best linear combination fits for WTRs were P-sorbed to Fe hydroxide (64.19%), phytic acid (30.72%) and P-sorbed to Al hydroxide (5.07%). This is largely in consistent with the results reported by Shober et al (2006) and Daniel (2010). 3.2 Phosphorus Forms in Biosolids-Treated Soils
  5. 5. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 10 | P a g e www.iiste.org The relative proportion of phosphate that best fit biosolids, WTRs, and selected WTRs-Biosolids- treated soils XANES spectra in linear combination fitting are shown in Table (3). The combination of P standards yielding the best linear combination fits for 10 g kg-1 -treated Kafr El- Dawar soils were phytic acid (Na salt)(19.08%), Mn3 (PO4)2(0.79%), KMgH9IP6(11.22%), Cu3(PO4)2(7.26%),phytic acid(3.67%), and Hydroxyapatite(57.98%)(Table 3). Also, the best linear combination fits for 10 g kg-1 -treated El-Bostan soils were amorphous Fe-phosphate (47.02%), KH2PO4(10.93%), Hydroxyapatite(17.21%), P-sorbed to Al hydroxide(16.13%), and Al Fe PO4(8.70%).However, the P-XANES spectra of 10 g kg-1 -treated Borg Al-Arab soils were 31.16%±0.02 Zn3 (PO4)2, 12.63%±0.01Al PO4, 3.10% ± 0.02 Cu3(PO4)2, 13.16%±0.02 Hydroxyapatite, 11.37%±0.02 Fe hydroxide with P-sorbed, 15.58% ± 0.03 CaH10P6, and 12.90%±0.03 H12 IP6(phytic acid). In contrast, the increasing of biosolids application rates to 30 g kg-1 changed the percentage of compounds presented in biosolids-treated soils (Table 3). The P-XANES spectra of 30 g kg-1 -treated Kafr El-Dawar soils were 15.34% ± 0.02 amorphous Al-phosphate, 29.53% ± 0.01 Al PO4, 39.67% ± 0.02 CaH10P6, and15.46%±0.02 H12 IP6 .While, in El-Bostan soils treated with 30 g kg-1 biosolids application rate, the best linear combination fits were 14.84%±0.005 Al PO4, 19.51%±0.03 CaH10P6, and65.64% ± 0.02 H12 IP6(phytic acid). Also, the forms in Borg Al-Arab soils were 32.27%±0.02 amorphous Al-phosphate, 21.39% ± 0.01 Al PO4, 17.61% ± 0.01 Hydroxyapatite, 21.01%±0.02 Ammonium magnesium phosphate, 1.62% ± 0.01 K4Mg2H4IP6 , and 6.07% ± 0.01 Al Fe PO4. Similarly, the P-speciation of USA biosolids used in this study was similar. The combination of P standards yielding the best linear combination fits for USA 50 g kg-1 biosolids-treated soil were 13.50% ± 0.06 K Mg Hg IP6, 47.50% ± 0.02 Fe hydroxide with P-sorbed, and 38.80% ± 0.04 H12IP6(Table 3). Spectrum of the other treatments was discarded from the result because of its strong spectral noise and unreliability. These results coincide with the results of Shober et al (2006) and Daniel (2010),but different results were found in the study of Sato et al.(2005). This may suggest that certain forms of P were present in the biosolids-treated soil that was not adequately represented by the standards used for fitting. A greater variety of P standards may need to be considered in future work. 3.3 Phosphorus Forms in WTRs-Biosolids-Treated Soils Addition of WTRs modified the P speciation in biosolids-amended soils, and the changes varied depending on the specific P speciation and biosolids and WTRs application rates (Figs.2 and 3,Table 3). In 10 g.kg-1 biosolids-amended Kafr El-Dawar soil, addition of 10 g.kg-1 WTRs significantly changed the P speciation and the best linear combination fits were 83.82% ± 0.01 Al hydroxide with P-sorbed and 16.19% ± 0.01 Al Fe PO4 ,so proportion of phosphate sorbed to Al hydroxide increased after WTRs application. However, for El-Bostan soil, the P speciation were 45.36%±0.02 Al PO4, 51.17%±0.01 H12 IP6, and 3.45%±0.02 Al Fe PO4.While, the P speciation in Borg Al-Arab soil were 5.39%±0.01 Al Fe PO4, 45.36%±0.02 Al PO4, 51.17%±0.01 H12 IP6, and 3.45%±0.02 Al Fe PO4. While one may assume that portion of total P in biosolids that was fitted as Al-hydroxide-bound P can actually be the sum of weakly sorbed P and soluble hydrated salts (e.g., K or Na phosphate), as differences in the XANES spectral features of aqueous P standards and PO4 sorbed to Al hydroxides were subtle (Peak et al., 2002), it is also possible that PO4 sorbed to Al hydroxide becomes more and more in-reversible with the progress of P absorption that occurs by penetrating from outer layer to the inner layer of the subject granular. Thus, potentials for loss of P to water resource can be reduced. Increasing application rate of WTRs to 40 g.kg-1 did not change P speciation in Kafr El-Dawar and El-Bostan soils(Table 3), but the proportion of forms was changed. On the contrary, P speciation in Borg Al-Arab soil were changed and the best linear combination fits were 23.62%±0.05 Al PO4, 46.37%±0.02 Hydroxyapatite, 26.81%±0.0 H12 IP6, and 3.18%±0.04 Fe hydroxide with P-sorbed.The Hydroxyapatite form was predominant in Borg Al-Arab soil because it has a high content of calcium carbonate. Mechanisms of appearance of CaP compounds in the soil upon manure application include (i) formation of secondary CaP minerals; (ii) phosphate adsorption to the surface of CaCO3 (Peak et al., 2002); and/or (iii) surface precipitates of phosphate with adsorbed calcium on Fe-oxide surface. In soils amended with high rate of biosolids(30 g.kg-1 ), application of 10 g.kg-1 WTRs significantly changed the P speciation and proportion of forms found.For example, the P speciation in Kafr El-Dawar soil were 14.27%±0.02 Ca3 (PO4)2, 71.49%±0.02 Hydroxyapatite, and 14.23%±0.004 Al Fe PO4.while, the best linear combination fits were 18.86%±0.05 Ca3 (PO4)2, 47.23%±0.04 Hydroxyapatite, 5.35%±0.03 CaH10P6, and 28.55%±0.02 H12 IP6 in El-Bostan soils(Table 3). However, the forms in Borg Al-Arab soil were 24.95%±0.01 Al
  6. 6. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 11 | P a g e www.iiste.org PO4, and75.04%±0.01H12 IP6. Additionally, increasing WTRs application rate up to 40 g.kg-1 significantly increased the proportion of Al hydroxide with P-sorbed(61.13%±0.02) in Kafr El-Dawar soil and the other forms of P were 38.91%±0.02 Cd6IP6.However, the proportion of Al hydroxide with P-sorbed (14.68%±0.02) was lower in El-Bostan soil than that of Kafr El-Dawar soil. Also, the other P forms were 3.40%±0.02 Cu3(PO4)2, 49.16%±0.02 Hydroxyapatite, and 32.74%±0.02 Al Fe PO4.While, the P speciation in Borg Al-Arab soil were completely different at the high rate of WTRs, the best linear combination fits were 38.96%±0.02 Ba6IP6, 46.26%±0.01 Cu3(PO4)2, and 14.79%±0.03 Cd6IP6(Fig.2 and Table 3).In comparison, in the 50 gkg-1 biosolids-treated Troy soil, application of 40 gkg-1 DWTRs have changed the P speciation in soil in comparison with control soil(Fig.3 and Table 3). The best linear combination fits were 76.67%±0.05 Ba6IP6, and 23.33%±0.01 Cu3(PO4)2 .Other studies have different results on P speciation, for examples the study of Beachemin et al.,(2003) revealed that the XANES results indicated that phosphate adsorbed on Fe- or Al-oxide minerals was present in all soils, with a higher proportion in acidic than in slightly alkaline samples. Calcium phosphate also occurred in all soils, regardless of pH. In agreement with chemical fractionation results, XANES data showed that Ca-phosphate was the dominant P forms in one acidic (pH 5.5) and in the two slightly alkaline (pH 7.4-7.6) soil samples. X-ray absorption near edge structure spectroscopy directly identified certain forms of soil P, while chemical fractionation provided indirect supporting data and gave insight on additional forms of P such as organic pools that were not accounted for by the XANES analysis. Gungr et al.. (2007) studied the P speciation in raw and anaerobically digested dairy manure with an emphasis on the Ca and Mg phosphate phases. Qualitative analysis of P by XANES spectra indicated that the Ca orthophosphate phases, except dicalcium phosphate anhydrous (DCPA) or monetite(CaHPO4), were not abundant in dairy manure. Linear combination fitting (LCF) of the P standard compounds showed that 57 and 43 % of P was associated with DCPA and struvite, respectively, in the raw manure. In anaerobically digested sample, 78.2% of P was present as struvite and 21.8% of P was associated with Hydroxyapatite (Hap).the P speciation shifted toward Mg orthophosphates and least soluble Ca orthophosphates following anaerobic digestion. Similarity between the aqueous orthophosphate, newberyite (MgHPO4.3H2O), and struvite spectra can cause inaccurate P speciation determination when dairy manure is analyzed solely using P XANES spectroscopy; however, XANES can be used in conjunction with XRD to quantify the distribution of inorganic P species in animal manure. Sato et al.,(2005) reported that P XANES spectra of poultry manure showed no evidences of crystalline P minerals but dominance of soluble CaP species and free and weakly bound phosphates(aquoues phosphate and phosphate adsorbed on soil minerals).Phosphate in unamended neighboring forest soil(pH 4.3) was mainly associated with iron compounds such as strengite and Fe-oxides. Soils with a short-term manure history contained both Fe-associated phosphates and soluble CaP species such as dibasic calcium phosphate (DCP) and amorphous calcium phosphate (ACP). Long term manure application resulted in a dominance of CaP forms, however, none of the manure-amended soils showed the presence of crystalline CaP. Seiter et al.(2008) studied the P speciation in alum-amended poultry litter, and the results indicated that traditional sequential fractionation procedures may not account for variability in P speciation in heterogeneous animal manures. XANES analysis showed that P is present in inorganic (P sorbed on Al oxides, calcium phosphates) and organic forms (phytic acid, polyphosphates, and monoesters) in alum- and non-alum- amended poultry litter. 4. Conclusion Revealing the complex nature of phosphate chemistry within environmental samples is an analytical challenge requiring new techniques and analytical approaches. Studies using sequential chemical extractions and nuclear magnetic resonance techniques have provided a wealth of information on bulk scale biosolids phosphorus composition. Speciation provides valuable information about the fate P may take in the soil and water environment. Phosphorous compounds found in biosolids were predominately the PO4 sorbed to Al hydroxide, followed by β-tricalcium phosphate, hydroxyapatite, and phytic acid. The addition of WTRs increased the proportion of PO4 sorbed to Al hydroxide and increased the proportion of aluminum phosphate. Addition of WTRs modified the P speciation in biosolids-amended soils, and the changes varied depending on the specific P speciation and biosolids and WTRs application rates. The P speciation in 4.
  7. 7. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 12 | P a g e www.iiste.org 5.Aknolowdgement The authors are grateful to the Synchrotron Radiation Center (SRC) for the beamtime award (to Zhang and Lin) with the Canadian Synchrotron Radiation Facility (CSRF). SRC is financially supported by the National Science Foundation (DMR-0084402), and CSRF is supported by National Research Council and NSERC (MFA) of Canada References Ajiboye, B., Akinremi,O.O.,Hu,Y. & Flaten,D.N. (2007), “Phosphorus Speciation of Sequential Extracts of Organic Amendments Using Nuclear Magnetic Resonance and X-ray Absorption Near-Edge Structure Spectroscopies”, Journal of Environmental. Quality 36,1563-1576. Balkcom, K. S., Adams,J.F. & Hartzog,D.L(.2003), “Peanut Yield Response to Poultry Litter and Municipal Sludge Application”, Communication in Soil Science and. Plant Analysis 34, 801-814. Basta, N.T., Zupancic,R.J. & Dayton, E.A.(2000), “Evaluating Soil tests to Predict Bermudagrass Growth in Drinking Water Treatment Residuals with Phosphorus Fertilizer”, Journal of Environmental. Quality 29,2007-2012. Beauchemin,S.,Hesterberg,D.Chou,J.,Beauchemin,M.Simard,R.R.,&Sayers,D.E.(2003).”Speciation of Phosphorus in Phosphorus-Enriched Agricultural Soils using X-ray Absorption Near-Edge Structure Spectroscopy and Chemical Fractionation” Journal of Environmental. Quality 32(5),1809-1819. Bloom,P.R., Mr Weave,R.,& Mcbride,M.B.(1978),”The Spectrophotometric and Flurometric Determination of Aluminum with 8-Hydroxyquinoline and Butyl Acetate Extraction”, Soil Science Society. of America Journal 42,712-716. Brink, G. E.,Rowe,D.E.,& Sistani,K.R.(2002) “Broiler Litter Application Effects on Yield and Nutrient Uptake of ‘Alicia’ Bermuda grass”, Agronomy Journal 94, 911-916. Cooperband, L.,Bollero,G. & Coale,F.(2002), “Effect of Poultry Litter and Composts on Soil Nitrogen and Phosphorus Availability and Corn Production. Nut. Cycl. Agroecosys. 62,185-194. Daniel, T. C., N.Sharpley,A., & Lemunyon,J.L.(1998),”Agricultural Phosphorus and Eutrophication: A Symposium Overview”, Journal of Environmental. Quality 27,251-257. Day, P.R.(1965), “Particle Fraction and Particle Size Analysis”, in Black,C.A.,Evans,D.D., Ensminger,L.E., White,J.L.,& Clark,F.E.(eds), Methods of Soil Analysis (Part I). American Society of Agronomy, Madison, Wisconsin, USA. pp: 545—566. Edwards, D. R., & Daniel,T.C.(1992), “Environmental Impacts of On-Farm Poultry Waste Disposal-A review”, Bioresearch Technology 41,9-33. Eghball, B. & Power,J.F.(1999), “Phosphorus- and Nitrogen-based Manure and Compost Applications: Corn Production and Soil Phosphorus”, Soil Science Society. of America Journal 63, 895-901. Elliott, H.A., O’Connor, G.A., & Brinton, S.(2002),”Waste Management: Phosphorus Leaching from Biosolid-Amended Sandy Soils”, Journal of Environmental. Quality. 31,681-689. Evers, G.(1998),”Comparison of Broiler Poultry and Commercial Fertilizer for Coastal Bermudagrass Production in the Southeastern US”, Journal. Sustainable Agriculture. 12,55-77. Gungr,K.,Jurgensen,A.,& Karthikeyan,K.G.(2007),”Determination of Phosphorus Speciation in Dairy Manure Using XRD and XANES Spectroscopy”, Journal of Environmental. Quality. 36,1856-1863. Huff, D.L.(2010),”Effects of Co-application of Biosolids and Drinking Water Treatment Residuals on Phosphorus Availability in Agricultural Soils”, MSc, Environmental Science Program,Southern Illinois University Edwardsville,Edwardsville,Illinois,USA. Jones, J.B.(2001), Laboratory Guide of Conducting Soil Tests and Plant Analysis. CRC Press. New York, Washington, D.C. Khare, N., Hesterberg,D. & Martin,J.D.(2005), “XANES Investigation of Phosphate Sorption in Single and Binary Systems of Iron and Aluminum Oxide Minerals”, Environmental Science &Technology 39 (7),2152-2160. Kingery, W. L.,Wood,C.W.,Delaney,D.P.,Williams,J.C.,Mullins,J.L.,&
  8. 8. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 13 | P a g e www.iiste.org Vansanten,E. (1993),”Implications of Long-Term Land Application of Poultry Litter in Tall Fescue Pastures” Journal Production Agronomy 6, 390-395. Lindsay, W.L., & Norvell, W.A.(1978),”Development of a DTPA Soil Test for Zinc, Iron, Manganese, and Copper”, Soil Science Society. of America Journal 42, 421-428. Lombi, E., Scheckel,K.G., Armstrong,R.D., Forrester,S., Cutler,J.N.,& Paterson,D. (2006),” Speciation and Distribution of Phosphorus in a Fertilized Soil: A synchrotron-Based Investigation”, Soil Science Society. of America Journal 70, 2038-2048. Makris, K.C., Harris,W.G., O’Connor,G.A., Obreza,T.A.,&Elliott,T.A.(2005), “Physicochemical Properties Related to Long-Term Phosphorus Retention by Drinking-Water Treatment Residuals”, Environmental. Science and .Technology 39,4280-4289. McDowell, R. W., & Sharpley,A.N.(2004),” Variation of Phosphorus Leached from Pennsylvanian Soils Amended with Manures, Composts or Inorganic Fertilizer” Agr. Ecosys.Environ. 102, 17-27. Nelson, D.W., &Sommers,L.E.(1982),” Total carbon, Organic Carbon and Oorganic Matter”, in Page,A.L., Miller,R.L., &Keeney,D.R.(eds), Methods of Soil Analysis. American Society of Agronomy, Madison, Wisconsin, UAS. pp.539-549. Nelson, R.E.(1982),” Carbonate and gypsum” , in Page,A.L., Miller,R.L., &Keeney,D.R.(eds), Methods of Soil Analysis. American Society of Agronomy, Madison, Wisconsin, UAS. pp 181--197 O’Connor, G.A, & Elliott,H.A.(2002),” Co-application of Biosolids and Water Treatment Residuals”, 17th WCSS, 14-21 August 2002, Thailand. Olsen, S.R., &Sommers,L.E.(1982), “Phosphorus” , in Page,A.L., Miller,R.L., &Keeney,D.R.(eds), Methods of Soil Analysis. American Society of Agronomy, Madison, Wisconsin, UAS.pp: 403--427. Peak, D., Sims, J. T., & Sparks, D.L. (2002),” Solid-Waste Speciation of Natural and Alum-Amended Poultry LitterUusing XANES Spectroscopy. Environmental Science & Technology 36,4253-4261. Pickering, I.J., Brown,Jr.G.E., & Tokunaga,T.K.(1995),” Quantitative Speciation of Selenium in Soils Using X-ray Absorption Spectroscopy”,. Environmental Science & Technology 29(9), 2456-2459. Pionke, H. B.,Gburek,W.G., & Sharpley,A.N.(2000),” Critical Source Area Controls on Water Quality in An Agricultural Watershed Located in the Chesapeake Basin. Ecological Engineering 14, 325-335. Rhoades, J.D.(1982),” Cation Exchange Capacity” , in Page,A.L., Miller,R.L., &Keeney,D.R.(eds), Methods of Soil Analysis. American Society of Agronomy, Madison, Wisconsin, UAS pp:149-157. Richards, L.A.(1954),” Diagnosis and Improvement of Saline and Alkaline Soils. USDA. Handbook 60.US Government Printing Office, Washington, DC. SAS Institute. (1994).” SAS/STAT User's Guide”, Version 6.4th edition. SAS Inst., Cary, N.C. Sato,S., Solomon, D. Hyland, C. Ketterings, Q.M., & Lehmann, J.(.2005),” Phosphorus Speciation in Manure and Manure-Amended Soils Using XANES Spectroscopy”, Environmental Science &Technology., 39(19), 7485-7491. Seiter, J.M., Staats-Borda,K.E.,Ginder-Vogel,M., & Sparks,D.(2008),” XANES Spectroscopic Analysis of Phosphorus Speciation in Alum-Amended Poultry Litter”, Journal of Environmental Quality 37, 477-485. Sharpley, A. N.,McDowell,R.W., & Kleinman,P.J.A.(2001),” Phosphorus Loss from Land to Water: Integrating Agricultural and Environmental Management”, Plant Soil 237, 287-307. Shober, A.L., Hesterberg,D.L., Sims,J.T. & Gardner,S.(2006),” Characterization of Phosphorus Species in Biosolids and Manures Using XANES Spectroscopy”, Journal of Environmental Quality. 35,:1983- 1993. Smith, K. A.,Jackson,D.R& Withers,P.J.A.(2001),” Nutrient Losses by Surface Runoff Following the Application of Organic Manures to Arable Land”, Environmental Pollution 112, 53-60. Staats, K.E., Arai,Y., & Sparks,D.L.(2004),”Alum Amendment Effects on Phosphorous Release and Distribution in Poultry Litter-Amended Sandy soils”, Journal of Environmental Quality.33, 1904-1911. Tan, K.H.(1996), Soil Sampling, Preparation, and Analysis. Marcel Dekker, Inc. New York. Basel. Hong Kong.
  9. 9. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 14 | P a g e www.iiste.org U.S. Environmental Protection Agency.(1981),”Process Design Manual- Land Treatment of Municipal Wastewater”; EPA 625/1-81-013; Center for Environmental Research Information: Cincinnati,OH, Ure, A. M.(1995),” Methods of Soil Analysis for Heavy Metals in Soils”, in Alloway,B.J.(ed) ,Heavy Metals in Soils,(2nd Edition). Blackie Academic and Professional, London, pp:58-95 Webb, S. M.(2005),” SIXPack: A graphical User Interface for XAS Analysis Using IFEFFIT”. Phys. Scr., T115, 1011–1014. Table 1.Some physical and chemical characteristics of studied soils, WTRs and biosolids in Egypt Characteristics Units Kafr El- Dawar El-Bostan Borg Al- Arab WTRs Biosolids pH 8.13 ± 0.05a) 7.69 ± 0.05 8.08 ± 0.06 7.45 ± 0.06 6.69 ± 0.03 EC dSm-1 2.66 ± 0.11 3.84 ± 0.12 2.92 ± 0.06 1.67 ± 0.04 11.25 ± 0.12 CaCO3 g kg-1 57.90 ± 0.60 2.40 ± 0.30 356.80 ± 2.60 nd c) nd Sand g kg-1 596.4 ± 4.20 868.2 ± 5.10 740.00 ± 3.70 nd nd Silt g kg-1 141.3 ± 1.50 25.10 ± 0.30 101.50 ± 1.90 nd nd Clay g kg-1 262.30 ± 3.70 106.70 ± 2.20 158.50 ± 3.20 nd nd Texture S.C.L L.S S.L nd nd O.M b) g kg-1 8.50 ± 0.15 1.00 ± 0.04 4.60 ± 0.15 57.00 ± 2.00 450.00 ± 1.67 KCl-Al mg kg-1 1.03 ± 0.04 0.13 ± 0.02 0.08 ± 0.02 28.18 ± 1.03 4.22 ± 0.13 Olsen-P mg kg-1 24.75 ± 0.25 2.89 ± 0.14 18.70 ± 0.80 24.00 ± 2.00 48.60 ± 1.62 CEC Cmol(+)kg- 1 39.13 ± 0.98 8.70 ± 0.20 26.00 ± 2.02 34.78 ± 0.34 73.57 ± 0.51 Total Elements: N g kg-1 nd nd nd 4.20 ± 0.13 32.00 ± 1.56 P g kg-1 nd nd nd 1.90 ± 0.15 4.60 ± 0.12 K g kg-1 nd nd nd 2.20 ± 0.21 1.90 ± 0.08 Al g kg-1 nd nd nd 38.01 ± 0.93 3.10 ± 0.23 Ni mg kg-1 25.01 ± 0.02 14.00 ± 0.11 17.02 ± 0.03 9.40 ± 0.07 108.00 ± 1.01 Pb mg kg-1 35.08 ± 0.17 14.00 ± 0.11 62.20 ± 0.35 76.00 ± 0.17 143.00 ± 0.64 Cu mg kg-1 30.22 ± 0.79 43.21 ± 0.22 24.06 ± 0.07 49.00 ± 0.02 128.00 ± 0.44 Cd mg kg-1 3.30 ± 0.18 2.10 ± 0.11 4.50 ± 0.03 3.00 ± 0.02 4.00 ± 0.15 DTPA-Extractable Metals: Ni mg kg-1 8.92 ± 0.04 5.13 ± 0.05 7.17 ± 0.05 2.49 ± 0.07 12.12 ± 0.24 Pb mg kg-1 6.13 ± 0.02 2.18 ± 0.08 5.69 ± 0.12 1.58 ± 0.04 62.13 ± 0.22 Cu mg kg-1 9.09 ± 0.03 3.13 ± 0.05 4.98 ± 0.03 1.20 ± 0.1 11.83 ± 0.15 Cd mg kg-1 0.33 ± 0.02 0.18 ± 0.02 0.26 ± 0.04 0.09 ± 0.02 0.72 ± 0.04 a) Means of three samples ± SD. b) O.M: organic matter; S.C.L: sandy clay loam, L.S: loamy sand, S.L: sandy loam c) nd: not determined Table 2. General properties of the experimental biosolids, WTRs, and soils in Illinois, USA. Values are means ± standard deviation (n = 3) Characteristics Units WTRs Biosolids Soil
  10. 10. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 15 | P a g e www.iiste.org pH 9.00±0.05 11.9±0.2 6.27±0.12 EC dSm -1 1.88±0.05 6.15±0.11 1.05±0.07 Texture nd nd Silty loam O.M g kg -1 67.6±0.5 380.2±3.2 20.3±0.6 Available-N mg kg -1 19.06±1.56 78.09±1.05 23.34±0.59 KCl-Al mg kg -1 125.07±4.5 34.67±0.58 75.23±1.52 Available-P mg kg -1 17.12±0.54 53.99±2.51 26.00±4.00 CEC cmol(+)kg -1 43.12±5.54 76.00±3.5 10.53±0.06 ICP-MS analysis: Aluminum (Al) g kg -1 12.6±0.05 71.9±0.7 71.0±0.47 Sodium (Na) g kg -1 0.5±0.02 1.5±0.02 <0.001 Iron (Fe) g kg -1 121.0±4.0 82.3±2.9 123.2±4.9 Potassium (K) g kg -1 0.5±0.01 30.7±0.8 10.6±0.6 Magnesium (Mg) g kg -1 12.6±0.5 3.6±0.3 1.5±0.02 Silver (Ag) mg kg -1 <0.002 2.00±0.12 <0.002 Arsenic (As) mg kg -1 <0.1 11.51±0.26 3.80±0.19 Boron (B) mg kg -1 12.30±0.58 109.07±5.06 6.55±1.05 Calcium (Ca) mg kg -1 266.07±2.28 309.34±11.28 1.61±0.06 Cadmium (Cd) mg kg -1 0.05±0.00 1.57±0.06 0.37±0.03 Cobalt (Co) mg kg -1 0.44±0.04 3.00±0.02 7.53±0.37 Chromium (Cr) mg kg -1 3.83±0.08 23.72±0.69 12.82±0.59 Copper (Cu) mg kg -1 0.86±0.10 342.07±6.70 11.34±0.60 Manganese (Mn) mg kg -1 7021.85±279.71 3321.74±63.71 7822.82±444.63 Molybdenum (Mo) mg kg -1 0.03±0.04 4.60±0.18 0.45±0.07 Nickel (Ni) mg kg -1 7.75±0.71 30.15±0.59 13.50±0.55 Lead (Pb) mg kg -1 0.05±0.00 29.16±0.32 20.30±0.54 Zinc (Zn) mg kg -1 10.95±0.85 190.86±0.83 64.19±2.15 Table 3.Relative proportion of phosphate that best fit biosolids, WTRs, and selected WTRs-Biosolids- treated soils XANES spectra in linear combination fittinga . Treatments Soil WTRs Biosolids Kafr El-Dawar El-Bostan Borg Al-Arab USA-soil 5.07%±0.05 Al hydroxide with P- sorbed 26.03%±0.01 Ba6IP6 64.19%±0.07 Fe hydroxide with P- sorbed 73.09%±0.03 Cu3(PO4)2 30.72%±0.02 H12IP6 0.89%± 0.02 Al hydroxide with P- sorbed 10 Biosolids(B) 19.08%±0.02 Na12 I P6 47.02%±0.05 amorphous Fe- phosphate 31.16%±0.02 Zn3 (PO4)2 0.79%±0.02 Mn3 (PO4)2 10.93%±0.01 KH2PO4 12.63%±0.01 Al PO4 11.22%±0.04 KMgH9IP6 17.21%±0.01 Hydroxyapatite 3.10%±0.02 Cu3(PO4)2
  11. 11. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 16 | P a g e www.iiste.org 7.26%±0.01 Cu3(PO4)2 16.13%±0.01 Al hydroxide with P-sorbed 13.16%±0.02 Hydroxyapatite 57.98%±0.01 Hydroxyapatite 8.70%±0.04 Al Fe PO4 11.37%±0.02 Fe hydroxide with P-sorbed 3.67%±0.03 H12 IP6 15.58%±0.03 CaH10P6 12.90%±0.03 H12 IP6 10B+10WTRs 83.82%±0.01 Al hydroxide with P-sorbed 45.36%±0.02 Al PO4 79.74%±0.01 Al PO4 16.19%±0.01 Al Fe PO4 51.17%±0.01 H12 IP6 4.12%±0.01 Al hydroxide with P-sorbed 3.45%±0.02 Al Fe PO4 10.74%±0.01 Fe hydroxide with P-sorbed 5.39%±0.01 Al Fe PO4 10B+40WTRs 76.45%±0.01 Al PO4 8.65%±0.02 Al PO4 23.62%±0.05 Al PO4 23.53%±0.01 H12 IP6 58.72%±0.01 H12 IP6 46.37%±0.02 Hydroxyapatite 32.62%±0.02 Al Fe PO4 3.18%±0.04 Fe hydroxide with P-sorbed 26.81%±0.0 H12 IP6 30B 15.34%±0.02 amorphous Al- phosphate 14.84%±0.005 Al PO4 32.27%±0.02 amorphous Al- phosphate 29.53%±0.01 Al PO4 19.51%±0.03 CaH10P6 21.39%±0.01 Al PO4 39.67%±0.02 CaH10P6 65.64%±0.02 H12 IP6 17.61%±0.01 Hydroxyapatite 15.46%±0.02 H12 IP6 21.01%±0.02 Amm.magnesium phosphate 1.62%±0.01 K4Mg2H4IP6 6.07%±0.01 Al Fe PO4 30B+10WTRs 14.27%±0.02 Ca3 (PO4)2 18.86%±0.05 Ca3 (PO4)2 24.95%±0.01 Al PO4 71.49%±0.02 Hydroxyapatite 47.23%±0.04 Hydroxyapatite 75.04%±0.01 H12 IP6 14.23%±0.004 Al Fe PO4 5.35%±0.03 CaH10P6 28.55%±0.02 H12 IP6 30B+40WTRs 61.13%±0.02 3.40%±0.02 38.96%±0.02
  12. 12. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 17 | P a g e www.iiste.org Al hydroxide with P-sorbed Cu3(PO4)2 Ba6IP6 38.91%±0.02 Cd6 IP6 49.16%±0.02 Hydroxyapatite 46.26%±0.01 Cu3(PO4)2 14.68%±0.02 Al hydroxide with P-sorbed 14.79%±0.03 Cd6IP6 32.74%±0.02 Al Fe PO4 50B 13.50%±0.06 K Mg Hg IP6 47.50%± 0.02 Fe hydroxide with P-sorbed 38.80% ±0.04 H12IP6 50B+40WTRs 76.67% ±0.05 Ba6IP6 23.33% ±0.10 Cu3(PO4)2 a Percentage after normalization to sum= 100 ± standard errors for the linear coefficients. Biosolids Energy (eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 5 6 Al hydroxide with P-sorbed Cu3(PO4)2 Data Ba6IP6 Fit
  13. 13. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 18 | P a g e www.iiste.org DWTR Energy (eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 5 Al hydroxide with P-sorbed H12 IP6 Fe hydroxide with P-sorbed Data Fit Figure 1. Phosphorus K-edge XANES spectra for biosolids and WTRs of Egypt.
  14. 14. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 19 | P a g e www.iiste.org 30 Biosolids + 40 DWTR-Borg Al-Arab soil Energy(eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 5 6 Cu3 (PO4)2 Cd6 I P6 Data Ba6 I P6 Fit 30 Biosolids+40 DWTR -Kafr El-Dawar soil Energy(eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 5 6 7 Al hydroxide with P-sorbed Cd6 IP6 Data Fit 30 Biosolids+40 DWTR- El-Bostan soil Energy(eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 5 Al hydroxide with P-sorbed Cu3 (PO4 )2 Hydroxylapatite Data Al/Fe PO4 Fit Figure 2. Phosphorus K-edge XANES spectra for 30 g.kg-1 biosolids-treated Egyptian soils amended with 40 g.kg-1 WTRs.
  15. 15. Journal of Environment and Earth Science www.iiste.org ISSN 2224-3216 (Paper) ISSN 2225-0948 (Online) Vol 1, No.1, 2011 20 | P a g e www.iiste.org 50 Biosolids Energy (eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 1 2 3 4 Ca H10 hexaphosphate H12 Z hexaphosphate Fe hydroxide with P sorbed data fit 50 biosolids + 40 DWTRs Energy (eV) 2140 2160 2180 2200 2220 NormalizedAbsorption 0 2 4 6 8 Cu3(PO4)2 data B6 Inositol hexaphosphate fit Figure 3. Phosphorus K-edge XANES spectra for 50 g.kg-1 bisolids and 50 g.kg-1 bisolids and 40 g.kg-1 WTRs-treated Troy soils.
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