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Estrogenic compounds may enter the environment when biosolids are applied to land. In the present study, soil samples were collected over 4 mo from a field trial following addition of biosolids. The recombinant yeast estrogen screen bioassay identified estrogenic activity in the soil at all sampling times to concentrations up to 2.3 µg 17β-estradiol equivalency/kg. The present results indicate the potential for estrogenic compounds to persist in soil following biosolids application.

Personal care products (PCPs) and endocrine disrupting compounds (EDCs) are groups of organic contaminants that have been detected in biosolids around the world. There is a shortage of data on these types on compounds in Australian biosolids, making it difficult to gain an understanding of their potential risks in the environment following land application. In this study, 14 biosolids samples were collected from 13 Australian wastewater treatment plants (WWTPs) to determine concentrations of eight compounds that are PCPs and/or EDCs: 4-t-octylphenol (4tOP), 4-nonylphenol (4NP), triclosan (TCS), bisphenol A (BPA), estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2). Concentration data were evaluated to determine if there were any differences between samples that had undergone anaerobic or aerobic treatment. The concentration data were also compared to other Australian and international data. Only 4tOP, 4NP, TCS, and BPA were detected in all samples and E1 was detected in four of the 14 samples. Their concentrations ranged from 0.05 to 3.08 mg/kg, 0.35 to 513 mg/kg, <0.01 to 11.2 mg/kg, <0.01 to 1.47 mg/kg and <45 to 370 μg/kg, respectively. The samples that were obtained from WWTPs that used predominantly anaerobic treatment showed significantly higher concentrations of the compounds than those obtained from WWTPs that used aerobic treatment. Overall, 4NP, TCS and BPA concentrations in Australian biosolids were lower than global averages (by 42%, 12% and 62%, respectively) and 4tOP concentrations were higher (by 25%), however, of these differences only that for BPA was statistically significant. The European Union limit value for NP in biosolids is 50 mg/kg, which 4 of the 14 samples in this study exceeded., (Copyright © 2010 Elsevier B.V. All rights reserved.)

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.

Six sewage sludges from five sewage treatment plants in Australia were incubated for up to 21 months. Carbon losses at the end of the 21-mo incubation varied substantially. The remaining organic matter was isolated by treatment with hydrofluoric acid (HF) and characterized using a range of solid-state (13)C nuclear magnetic resonance (NMR) spectroscopic techniques. By every measure (signal distribution in cross polarization [CP] and Bloch decay [BD] spectra, carbon NMR observability determined by spin counting, and the appearance of proton spin relaxation editing subspectra), the chemical composition of the residual organic matter appeared to be little different from that of the original sludges, even for those sludges that experienced the greatest carbon losses. Importantly, these NMR properties distinguish sewage sludge organic matter from soil organic matter. Thus, it should be possible to follow the decomposition of sewage sludge organic matter applied to soils in the field using solid-state (13)C NMR spectroscopy.

The effect of biosolids amendment on cadmium sorption coefficient (K(d)) was determined for soils in a biosolids field trial. The sorptive properties of biosolids are thought to have a significant controlling effect upon the availability/uptake and mobility of potentially toxic metals. K(d) values for the three biosolids were 10-30 times greater than those for unamended soil. Elevated K(d) values were still apparent 1 and 2 years after biosolids amendment (100 t ha(-1)) for two of the three biosolids. Chemical extractants (sodium hypochlorite and hydrofluoric acid, respectively) were used in an attempt to determine K(d) values of isolated inorganic and organic fractions. For both biosolids amended soils and unamended controls, Cd sorption appeared to be dominated by the inorganic fraction, potentially indicating the overriding importance of this fraction in controlling metal mobility. However, for the biosolids themselves, the sum of inorganic and organic fraction contributions to K(d) accounted for less than half the K(d) of the whole biosolids. This discrepancy was attributed to the loss of highly sorptive water soluble species in both chemical extractions.

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.

Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.