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This paper aims to describe the performance of a soil washing plant (SWP) for remediating a per- and poly-fluoroalkyl substances (PFASs)-contaminated soil with a high clay content (61%). The SWP used both physical and chemical processes; fractionation of the soil particles by size and partitioning of PFASs into the aqueous phase to remove PFASs from the soil. Contaminated water was treated in series with granulated activated carbon (GAC) and ion-exchange resin and reused within the SWP. Approximately 2200 t (dry weight) of PFAS-contaminated soil was treated in 25 batches of 90 t each, with a throughput of approximately 11 t soil/hr. Efficiency of the SWP was measured by observed decreases in total and leachable concentrations of PFASs in the soil. Average removal efficiencies (RE) were up to 97.1% for perfluorocarboxylic acids and 94.9% for perfluorosulfonic acids. REs varied among different PFASs depending on their chemistry (functional head group, carbon chain length) and were independent of the total PFAS concentrations in each soil batch. Mass balance analysis found approximately 90% of the PFAS mass in the soil was transferred to the wash solution and > 99.9% of the PFAS mass in the wash solution was transferred onto the GAC without any breakthrough., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Charles Grimison reports a relationship with Ventia Services that includes: employment., (Crown Copyright © 2022. Published by Elsevier B.V. All rights reserved.)

Disinfection by-products (DBPs) are formed through the disinfection of water containing precursors such as natural organic matter or anthropogenic compounds (e.g., pharmaceuticals and pesticides). Due to the ever increasing use of plastics, elastomers, and other polymers in our daily lives, polymer-based materials (PBMs) are detected more frequently and at higher concentrations in water and wastewater. The present review provides a comprehensive and systematic analysis of the contribution of PBMs - including elastomers, tire waste, polyelectrolytes, and microplastics - as precursors of DBPs in water and wastewater. Literature shows that the presence of PBMs can lead to the leaching of dissolved organic matter (DOM) and subsequent formation of DBPs upon disinfection in aqueous media. The quantity and type of DBPs formed strongly depends on the type of polymer, its concentration, its age, water salinity, and disinfection conditions such as oxidant dosage, pH, temperature, and contact time. DOM leaching from elastomers and tire waste was shown to form N-nitrosodimethylamine up to concerning levels of 930 ng/L and 466,715 ng/L, respectively upon chemical disinfection under laboratory conditions. Polyelectrolytes can also react with chemical disinfectants to form toxic DBPs. Recent findings indicate trihalomethanes formation potential of plastics can be as high as 15,990 µg/L based on the maximum formation potential under extreme conditions. Our analysis highlights an overlooked contribution of DOM leaching from PBMs as DBP precursors during disinfection of water and wastewater. Further studies need to be conducted to ascertain the extent of this contribution in real water and wastewater treatment plants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs ( C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs ( C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship ( R 2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF 2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

The aim of this study was to assess the soil-water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil-water partitioning coefficients (log  K d values) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol ( R 2 = 0.94, p < 0.0001). Across all soils, the K d values of all short-chain PFASs (≤5 -CF2- moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5  log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The K d values of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Two pesticide risk indicators, Pesticide Impact Rating Index (PIRI) and Environmental Potential Risk Indicator for Pesticides (EPRIP), were used to determine the likelihood of off-site transport to surface water of pesticides used in a cherry (Prunus avium cultivars) and an apple (Malus domestica cultivars) orchard. The predictions of off-site transport of some of the pesticides were verified against actual pesticide concentrations in surface water continuously monitored over two years. To our knowledge, only one other study in the published literature has attempted this. Of the chemicals monitored there was good agreement between the predictions and the field measurements from the apple orchard, but less so for the cherry orchard. In both risk indicators the attenuation factor based on the width of the buffer strip over-estimated the effectiveness of the buffer strip. There was good agreement between the EPRIP and PIRI risk assessment except for ethephon which EPRIP rated a higher risk than PIRI and dithianon which EPRIP rated a lower risk than PIRI. A strong correlation was found between the field observations and the EPRIP predicted environmental concentrations for the majority of cases. This study showed that even simple risk indicators (e.g. PIRI and EPRIP) can be good predictors for a first tier risk assessment of pesticide transport to neighbouring water bodies., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

The application of fixed bed high rate nitrifying trickling filters (NTFs) for the removal of track organic chemicals of concern (CoC) is less well known than their application to nutrient removal in water treatment. Particularly, the effect of exogenous organic carbon substrate (sucrose) loading on the performance of NTFs is not well understood. A laboratory-scale NTF system was operated in recirculation mode, with the objective of removing ammonia and CoC simultaneously. The efficiency of a high rate NTF for removal both of low concentration of ammonia (5 mg NH4-N L(-1)) and different concentrations of CoC in the presence of an exogenous organic carbon substrate (30 mg total organic carbon (TOC) L(-1)) was investigated. In the presence of exogenous organic carbon, the results demonstrated that the high rate NTF was able to successfully remove most of the CoCs investigated, with the removal ranging from 20.2% to 87.54%. High removal efficiencies were observed for acetaminophen (87.54%), bisphenol A (86.60%), trimethoprim (86.24%) and 17α-ethynylestradiol (80.60%). It was followed by the medium removal efficiency for N, N-diethyl-m-toluamide (61.31%) and atrazine (56.90%). In contrast, the removal of caffeine (28.43%) and benzotriazole (20.20%) was poorer in the presence of exogenous organic carbon. The removal efficiency for CoC was also compared with the results obtained in our previous study in the absence of exogenous organic carbon. The results showed that the addition of exogenous organic carbon was able to improve the removal of some of the CoC. Significant TOC percentage removals (45.68%-84.43%) and ammonia removal rate (mean value of 0.44 mg NH4-N L(-1) h(-1)) were also achieved in this study. The findings from this study provide valuable information for optimising the efficiency of high rate NTF for the removal of ammonia, CoC and TOC., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Attenuation of pharmaceuticals due to natural sunlight is expected to be an important removal pathway in wastewater treatment plants using treatment lagoon systems. In this work, the photolysis of two antidepressants, amisulpride and desipramine, has been investigated in both ultrapure water and wastewater under simulated solar irradiation. Results showed that for amisulpride short irradiation times (t1/2 approximately 3h in pure water and 4h in wastewater) were adequate to degrade the parent compound while a longer exposure period was required for desipramine (t1/2 of approximately 36 h in pure water), although its degradation is enhanced almost three times by indirect photolysis in wastewaters. A significant number of transformation products (TPs) were identified for both pharmaceuticals by high-resolution mass spectrometry. In general, TPs formed are not persistent although acute toxicity tests for desipramine and its TPs showed an increase of the mixture toxicity after solar irradiation, suggesting that some TPs may be more toxic than the parent compound. In wastewaters collected from treatment lagoons, only amisulpride and one of its major TPs, TP 357, were detected. This indicates that long solar exposure times may be necessary for an effective elimination of these substances in lagoon systems or that photolysis may not be the main removal pathway for these particular compounds., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Perfluoroalkyl substances (PFASs) have received great attention from the public and scientific community due to their potential adverse impacts on the ecosystem and human health. We investigated the occurrence and distribution of 16 PFASs from 2 classes of PFASs-perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids-in the archived surface sediments of five major rivers (Yellow River, Hai River, Liao River, Zhujiang River, and Dongjiang River) in northern and southern China. The study was also performed during the wet and dry seasons. Perfluorooctanoic acid and perfluorooctane sulfonic acid were the most frequently detected (detection frequency = 100 and 63 %, respectively) in the sediments of the five rivers; the concentrations ranged from 0.08 to 0.99 ng/g dry weight (dw) and were lower than the limit of detection (

The anti-microbial agent triclosan (TCS), and its derivative methyl-triclosan (Me-TCS), are discharged with treated effluents from wastewater treatment plants to receiving environments. We investigated the bioconcentration of TCS and Me-TCS in mussels (Mytilus galloprovincialis) exposed to TCS (100 ng L(-1)) for 30 days in seawater aquaria (19±2°C) with fresh phytoplankton as a food source. Bioconcentration increased with time reaching a steady-state around 24-30 days. The bioconcentration factor (log BCF) for TCS were 2.81 L kg(-1) (dry weight) and 4.13 L kg(-1), when lipid normalised concentrations were used. Mussels were also deployed in cages at four marine locations receiving effluents from WWTPs. The mean (±SD) TCS and Me-TCS concentrations for mussels from these sites were 9.87 (±1.34) and 6.99 (±2.44) μg kg(-1). The study showed that mussels can be a useful tool for monitoring pollution of TCS and Me-TCS in marine and estuarine environments., (Copyright © 2013. Published by Elsevier Ltd.)

We investigated the biodegradation of three selected benzotriazoles (BTs), namely benzotriazole (BT), 5-methyl-benzotriazole (5-TTri) and 5-chloro-benzotriazole (CBT), in aquifer materials. Biodegradation experiments were conducted in microcosms with fresh groundwater and aquifer sediment materials under aerobic and anaerobic (nitrate, sulfate, and Fe (III) reducing) conditions. All three BTs were degraded by microorganisms in aquifer materials under aerobic and anaerobic conditions. Under aerobic conditions, BT and 5-TTri were found to be degraded fastest with their half-lives of 43 days and 31 days, respectively, among the redox conditions used. Under anaerobic conditions, CBT was found to be degraded better with its half-life of 21 days under nitrate reducing conditions than under aerobic conditions with its half-life of 47 days. The two BT derivatives 5-TTri and CBT could be biotransformed into BT via demethylation and dechlorination reactions, respectively., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This study investigated the sorption-desorption behaviour of four pesticides by a by-product from mineral sand mining, commonly referred to as neutralised used acid (NUA). In batch studies the average amount of pesticide removed after 6h was 69% for atrazine, 89% for diuron, 61% for 2,4-D and 83% for chlorpyrifos. The lower sorption of 2,4-D to NUA compared with the other pesticides studied is most likely to be due to the high pH of the solutions (7.8 to 8.8) which would have resulted in 2,4-D being predominantly in an anionic form. The presence of other pesticides only significantly decreased the amount of 2,4-D sorbed from 59% to 34% when present in a mixture. Little (2 to 17%) diuron, chlorpyrifos, atrazine or 2,4-D were found to desorb from the NUA. The presence of nitrate or phosphate had minimal effect on the amount of diuron or atrazine sorbed to the NUA. However, all phosphate and nitrate treatments significantly (P<0.05) decreased the amount of 2,4-D sorbed (<50%) compared with when 2,4-D was present alone (65%). This study has shown that NUA has potential to be used as a sorbent for pesticides., (Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.)

We investigated the occurrence and removal of four benzotriazoles (BTs) (benzotriazole: BT; 5-methyl-benzotriazole: 5-TTri; 5-chloro-benzotriazole: CBT; 5,6-dimethyl-benzotriazole: XTri) and six UV filters (benzophenone-3: BP-3; 3-(4-methylbenzylidene)camphor: 4-MBC; octyl 4-methoxycinnamate: OMC; 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro benzotriazole: UV-326; 2-(2'-Hydroxy-5'-octylphenyl)-benzotriazole: UV-329; octocrylene: OC) in a full scale municipal wastewater treatment in South Australia. BT, 5-TTri and BP-3 were found as the dominant compounds detected in the wastewater samples with average concentrations up to 5706 ± 928 ng/L, 6758 ± 1438 ng/L and 2086 ± 1027 ng/L in influent, and up to 2439 ± 233 ng/L, 610 ± 237 ng/L and 153 ± 121 ng/L in effluent, respectively. In the biosolid, 4-MBC and OC were found with the highest concentrations of 962 ± 135 ng/g and 465 ± 65 ng/g, respectively. Sorption onto sludge played a dominant role in the removal for UV filters, especially for 4-MBC, UV-326 and OC, which accounted for 54%-92% of influent loads, while biological degradation played a significant role for the other compounds., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Biodegradation of the ultraviolet (UV) filter benzophenone-3 (BP-3) was investigated in the laboratory to understand its behavior and fate under oxic and anoxic (nitrate, sulfate, and Fe [III]-reducing) conditions. Biodegradation experiments were conducted in microcosms with 10% of activated sludge and digested sludge under oxic and anoxic conditions, respectively. Benzophenone-3 was well degraded by microorganisms under each redox condition. Under the redox conditions studied, the biodegradation half-life for BP-3 had the following order: oxic (10.7 d) > nitrate-reducing (8.7 d) > Fe (III)-reducing (5.1 d) > sulfate-reducing (4.3 d) ≥ anoxic unamended (4.2 d). The results suggest that anaerobic biodegradation is a more favorable attenuation mechanism for BP-3. Biodegradation of BP-3 produced two products, 4-cresol and 2,4-dihydroxybenzophenone, under oxic and anoxic conditions. Biotransformation of BP-3 to 2,4-dihydroxybenzophenone by way of demethylation of the methoxy substituent (O-demethylation) occurred in cultures under each redox condition. The further biotransformation of 2,4-dihydroxybenzophenone to 4-cresol was inhibited under oxic, nitrate-reducing, and sulfate-reducing conditions., (Copyright © 2011 SETAC.)

A new method using gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the determination of four benzotriazoles, i.e. benzotriazole (BT), 5-methylbenzotriazole (5-TTri), 5-chlorobenzotriazole (CBT), 5,6-dimethylbenzotriazole (XTri), and six UV filters, i.e. benzophenone-3 (BP-3), 3-(4-methylbenzylidene)camphor (4-MBC), octyl 4-methoxycinnamate (OMC), 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro benzotriazole (UV-326), 2-(2'-hydroxy-5'-octylphenyl)-benzotriazole (UV-329), and octocrylene (OC) in ground water, effluent and biosolid samples. Solid phase extraction (SPE) and pressurized liquid extraction (PLE) were applied as the preconcentration method for water samples (ground water and effluent) and biosolid samples, respectively. The optimized method allowed us to quantify all target compounds with the method detection limits ranging from 0.29 to 11.02 ng/L, 0.5 to 14.1 ng/L and 0.33 to 8.23 ng/g in tap water, effluent and biosolid samples, respectively. The recoveries of the target analytes in tap water, effluent and biosolid samples were 70-150%, 82-127% and 81-133%, respectively. The developed analytical method was applied in the determination of these target compounds in ground water, effluent and biosolid samples collected from Bolivar sewage treatment plants in South Australia. In effluent samples, the target compounds BT, 5-TTri, CBT, XTri and BP-3 tested were detected with the maximum concentration up to 2.2 μg/L for BT. In biosolid samples, eight out of ten compounds tested were found to be present at the concentrations ranging between 18.7 ng/g (5-TTri) and 250 ng/g (4-MBC)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

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 present study assessed contamination and toxicity of sediments from seven remediated and remnant wetland sites within Sydney Olympic Park, Australia, and four unremediated sites adjacent to its boundary using chemical analysis and a luminescent bacterial biosensor assay (Escherichia coli). Concentrations of metals (Pb, Cr, Cu, Ni, Zn, Cd, and As) and persistent organic chemicals (DDT and its metabolites, dichlorodiphenyldichloroethane and dichlorodiphenyldichloroethylene; polycyclic aromatic hydrocarbons; polychlorinated biphenyls; and polychlorinated dibenzo-p-dioxins and dibenzofurans) in sediments and their pore-water samples were determined. Zinc concentrations were the highest of the metals in the sediments (84-618 mg/kg), and at eight sites, metal concentrations in sediments exceeded the Australian ecological trigger values for Pb, Zn, and Ni. Concentrations of organic contaminants in the sediments exceeded the trigger values at all 11 sites for DDTs, at 6 sites for polycyclic aromatic hydrocarbons, and 5 sites for polychlorinated biphenyls. Sediment samples from the four unremediated sites outside the Sydney Olympic Park had dioxin concentrations greater than 200 pg (toxic equivalency per gram). The same four sites were identified as contaminated in pore-water toxicity tests with the luminescent biosensor, generally consistent with the bioavailable fractions of the contaminants (pore-water and Tenax extraction data), as well as dioxin levels, in the sediments. Preliminary toxicity identification and evaluation tests of the pore water from the four sites outside the park demonstrated that organic contaminants were the main cause of toxicity to E. coli, with no evidence that metals contributed to the toxicity of the pore water.

We report a survey on the occurrence of estrogens (estrone, E1; 17beta-estradiol, E2; 17alpha-ethynylestradiol, EE2) and xenoestrogens (bisphenol-A, BPA; 4-t-octylphenol, 4-t-OP; 4-nonylphenols, 4-NP; and nonylphenol mono- and di-ethoxylates, NPE1 and NPE2) in effluents from five wastewater treatment plants and their receiving waters in South East Queensland. The total xenoestrogen concentrations in effluent ranged between 2446 ng/L and 6579 ng/L, with 4-NP and NPE1-2 having much higher concentration levels than BPA and 4-t-OP. The estrogen levels in effluent varied from 9.12 to 32.22 ng/L for E1, from 1.37 ng/L to 6.35 ng/L for E2 and from 0.11 ng/L to 1.20 ng/L for EE2. No significant differences (p<0.05) in the concentrations of the selected estrogenic compounds were found for the effluents from the five sewage treatment plants. The estrogens and xenoestrogens were also found in the receiving waters at relatively lower concentration levels due to dilution of effluents in the rivers. Based on the chemical analysis data and relative potency of the compound from in vitro and in vivo bioassays from the literature, the calculated in vitro EEQ values (estrogen equivalents) in the receiving river waters downstream of the effluent discharge points ranged from 1.32 to 11.79 ng/L, while the in vivo EEQ values (vitellogenin response in rainbow trout) ranged from 2.48 to 21.18 ng/L. The three estrogens accounted for the majority of the EEQ in the water samples. This study indicates that the rivers of South East Queensland are at potential risk.

Organic and inorganic contamination was assessed for sediments from wetlands and water bodies within the Sydney Olympic Park (SOP, remediated sites) and its surroundings (unremediated sites) and urban reference sites in the Sydney Basin. Among the seven elements analysed (As, Cd, Cr, Cu, Pb, Ni and Zn), Zn concentrations were the highest, followed by Pb, Cu and Cr in the sediments of SOP. Significantly higher concentrations (p < 0.05) of DDTs were found in sediments of the Homebush Bay and Parramatta River sites compared with the urban reference sites, mainly due to past manufacturing of DDT in the Homebush Bay area. However, no significant differences (p > 0.05) in concentrations were found for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) as well as DDTs between sediments from SOP and the urban reference sites. Source indicators suggest that PAHs in the sediments originated from combustion processes. Two distinct groups of dioxin profiles were observed within SOP and its surroundings. Levels of dioxins were more than 100 pg WHO-TEQ/g dry weight of sediment at five sites adjacent to the SOP boundaries. Based on the findings of the chemical profiles of the contaminants, the remediated sites in SOP can be regarded as similar to the urban reference sites within the Sydney Basin, while the adjacent unremediated sites have higher concentrations, especially of dioxins, that could still affect organisms in the aquatic environment.

Occurrence of eight selected pharmaceutically active compounds (PhACs; caffeine, carbamazepine, triclosan, gemfibrozil, diclofenac, ibuprofen, ketoprofen and naproxen) were investigated in effluents from fifteen sewage treatment plants (STPs) across South Australia. In addition, a detailed investigation into the removal of these compounds was also carried out in four STPs with different technologies (Plant A: conventional activated sludge; plant B: two oxidation ditches; plant C: three bioreactors; and plant D: ten lagoons in series). The concentrations of these compounds in the effluents from the fifteen STPs showed substantial variations among the STPs, with their median concentrations ranging from 26 ng/L for caffeine to 710 ng/L for carbamazepine. Risk assessment based on the "worst case scenario" of the monitoring data from the present study suggested potential toxic risks to aquatic organisms posed by carbamazepine, triclosan and diclofenac associated with such effluent discharge. With the exception of carbamazepine and gemfibrozil, significant concentration decreases between influent and effluent were observed in the four STPs studied in more detail. Biodegradation was found to be the main mechanism for removing concentrations from the liquid waste stream for the PhACs within the four STPs, while adsorption onto sludge appeared to be a minor process for all target PhACs except for triclosan. Some compounds (e.g. gemfibrozil) exhibited variable removal efficiencies within the four STPs. Plant D (10 lagoons in series) was least efficient in the removal of the target PhACs; significant biodegradation of these compounds only occurred from the sixth or seventh lagoon.

Biodegradation and adsorption of selected endocrine-disrupting chemicals (EDCs), namely oestrogens (E2 and EE2) and phenolic compounds (BPA, 4-t-OP and 4-n-NP), in aquifer materials was investigated in the laboratory in order to understand the behaviour and fate of these chemicals associated with reclaimed water during managed aquifer recharge. Biodegradation experiments were conducted in microcosms with aquifer material and groundwater mixture, or with aquifer material and effluent mixture in the presence of glucose under both aerobic and anoxic conditions. All five selected compounds were degraded by microorganisms in both types of aquifer material-water mixtures under aerobic and anoxic conditions. Under aerobic conditions, EE2 was found to degrade faster in the aquifer material supplemented with effluent with a half-life of 15 days compared with that of 26 days in the aquifer material and groundwater microcosm. No significant difference between the two aquifer material-water mixtures was found for the other four compounds with half-lives ranging between 0.2 and 4.1 days. Under anoxic conditions, however, little biodegradation was observed for the selected EDCs except for E2, which degraded in the aquifer material in the presence of both water types.

The fate and removal of the estrogens 17beta-estradiol (E(2)), estrone (E(1)), and 17alpha-ethynylestradiol (EE(2)) and of the xenoestrogens bisphenol A (BPA), 4-tert-octylphenol (4-t-OP), 4-nonylphenol (4-NP), and nonylphenol mono- and diethoxylate (NPEO1 and NPEO2, respectively) were investigated in four South Australian sewage treatment plants (STPs; plants A-D) with different treatment technologies. The concentrations in the effluent from the two-year survey were similar to those reported in other studies. In the effluent, 4-NP, NPEO1, and NPEO2 had total concentrations up to 8 microg/L, which were much higher than those of BPA and 4-t-OP. Estrone had the highest concentrations among the three estrogens, ranging between 13.3 and 39.3 ng/L, whereas the concentrations for E(2) and EE(2) varied between 1.0 and 4.2 ng/L and between 0.1 and 1.3 ng/L, respectively. The removal rates for the estrogens and xenoestrogens were variable but consistent with the plant performance parameters (biochemical oxygen demand, suspended solids, and ammonia). Considering all the estrogenic compounds analyzed in the present study, plant D, with a series of anaerobic and aerobic lagoons, was the least efficient of the four STPs in the removal of these compounds. The removal rates for 4-NP, NPEO1, and NPEO2 within the plants were 92% for plant A, with conventional activated sludge treatment; 80% for plant B, with two oxidation ditches; 70% for plant C, with three bioreactors; and 64% for plant D, with 10 lagoons in series. Comparatively, the removal of estrogens was lower, with rates ranging between 47 and 68% for E(2) at the four plants. Both E(1) and EE(2) were more persistent during treatment, especially in plants C and D.

Triclosan (TCS) is an antimicrobial agent widely used in many personal care products. This study investigated the occurrence of TCS in effluents, biosolids and surface waters, and its fate in wastewater treatment plants (WWTPs). The aqueous concentrations of TCS in nineteen effluents from Australian WWTPs ranged from 23 ng/L to 434 ng/L with a median concentration of 108 ng/L, while its concentrations in nineteen biosolids ranged from 0.09 mg/kg to 16.79 mg/kg on dry weight basis with a median concentration of 2.32 mg/kg. The removal rates for TCS in five selected WWTPs were found to range between 72% and 93%. Biological degradation was believed to be the predominant removal mechanism for TCS in the WWTPs. However, adsorption onto sludge also played a significant role in the removal of TCS in the WWTPs. TCS at concentrations up to 75 ng/L was detected in surface waters (outfall, upstream, and downstream) from five rivers receiving effluent discharge from WWTPs. Preliminary risk assessment based on the worst-case scenario showed that the TCS concentrations in surface waters might lead to risks to aquatic organisms such as algae. Based on the TCS levels in the biosolids, application of biosolids on agricultural land may also cause adverse effects in the soil environment.

The recognition of pharmaceuticals as significant environmental contaminants has only been a recent phenomenon. Therefore there is a paucity of data relating to the fate and effects of pharmaceuticals once they enter an aquatic receiving system. The amount of work that needs to be done in terms of risk assessment for pharmaceuticals required by regulatory agencies is substantial. This paper has determined the environmental partitioning coefficient (K(d)) of 13 diverse human pharmaceuticals in three model systems of differing combinations of solid phases and solutions. The K(d) values were then compared with distribution values of the pharmaceuticals in the human body determined from pharmacological studies. This was done to assess the functional relationship between K(d) and distribution values in the human body (V(D)). K(d) values ranged from 3 to 2450 L kg(-1). Regression coefficients ranged from r(2)=0.62-0.72, indicating that V(D) values are a useful indicator for the K(d) values of the tested pharmaceuticals within the batch sorption systems. The relationship between K(d) and V(D) should therefore be further explored to determine whether this relationship can be applied to a broader range of pharmaceuticals in more diverse environmental systems. Exploiting available human pharmacological data in such a way would be of great benefit in prioritising human pharmaceuticals as environmental contaminants in the risk assessment process.

Off-site movement of pesticides from furrow-irrigated agriculture has been a concern in the Ord River Irrigation Area, Western Australia. This paper reports on the effectiveness of incorporation of pesticides by cultivator or power harrows before irrigating, and spraying pesticides only onto beds to minimise off-site transport. Incorporation of pesticides by power harrows prior to irrigation was found to be more effective in decreasing the off-site transport of a more strongly sorbed pesticide, endosulfan. The average load of total endosulfan (alpha + beta + sulfate) decreased by 74% (P < 0.01) from 11.41 g ha(-1) from the conventionally treated bays to 2.96 g ha(-1) from the incorporated irrigation bays. The total average load of atrazine leaving the irrigation bays was decreased by 81% (P < 0.05) from 87.82 g ha(-1) under the conventional practice of spraying the whole field to 16.95 g ha(-1) by spraying the beds only. A reduction of 52% in total average load of metolachlor was observed following incorporation with power harrows, but this was not significant. Incorporation by cultivator or by power harrows decreased the total load of atrazine or metolachlor leaving the irrigation bays over the whole irrigation period, but these treatments were not shown to be statistically significant, which may have been due to the limited number of field replicates. Incorporation of strongly sorbed pesticides (e.g. endosulfan) prior to irrigation significantly decreased the off-site transport of these pesticides in a furrow irrigation system and may be a useful practice to minimise off-site transport of other similar pesticides. Minimising off-site transport of weakly sorbed pesticides (e.g. atrazine and metolachlor) from a furrow irrigation system is more difficult. The nature of furrow irrigation makes it highly conducive to pesticide transport, particularly of weakly sorbed pesticides, and further work is needed to develop strategies to minimise the movement of this group of pesticides to water bodies.

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C18 cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 +/- 4.2% for thiamethoxam, 99 +/- 4.2% for imidacloprid and 94 +/- 1.4% for thiacloprid. The recoveries for water samples ranged from 87 +/- 3.4% for thiamethoxam to 97 +/- 3.9% for imidacloprid and 97 +/- 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5g), and 2, 2, 0.5, micro/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.

Sorption and degradation of the five selected endocrine disrupting chemicals (EDCs) including bisphenol A (BPA), 17 beta-estradiol (E2), 17 alpha-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP) and 4-n-nonylphenol (4-n-NP) have been investigated in the laboratory using sediment and groundwater from an aquifer in Bolivar, South Australia. The sorption coefficients measured on the sediment were in the following order: 4-n-NP>4-t-OP>EE2>E2>BPA. The sorption coefficients (Kf values) for the five EDCs were 3.89, 21.8, 24.2, 90.9 and 195, respectively. The alkylphenols 4-t-OP and 4-n-NP had strong binding on the sediment while BPA had a weak affinity. Degradation experiments of the five EDCs showed that E2 and 4-n-NP degraded quickly under aerobic conditions with a half-life of 2 and 7 days, respectively. EE2 degraded slowly with an estimated half-life of 81 days in the aquifer material under aerobic conditions while the other two chemicals (BPA and 4-t-OP) remained almost unchanged. Little or no degradation of the five EDCs except slow degradation for E2 was observed within 70 days under anaerobic conditions in native groundwater.

Hormone steroids are a group of endocrine disruptors, which are excreted by humans and animals. In this paper, we briefly review the current knowledge on the fate of these steroids in the environment. Natural estrogenic steroids estrone (E1), 17beta-estradiol (E2) and estriol (E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17alpha-ethynylestradiol (EE2) and mestranol (MeEE2) have a solubility of 4.8 and 0.3 mg/l, respectively. These steroids have a moderate binding on sediments and are reported to degrade rapidly in soil and water. Estrogenic steroids have been detected in effluents of sewage treatment plants (STPs) in different countries at concentrations ranging up to 70 ng/l for E1, 64 ng/l for E2, 18 ng/l for E3 and 42 ng/l for EE2. E2 concentrations in river waters from Japan, Germany, Italy and the Netherlands ranged up to 27 ng/l. In addition, E2 concentrations ranging from 6 to 66 ng/l have also been measured in mantled karst aquifers in northwest Arkansas. This contamination of ground water has been associated with poultry litter and cattle manure waste applied on the land. Although hormone steroids have been detected at a number of sources worldwide, currently, there is limited data on the environmental behaviour and fate of these hormone steroids in different environmental media. Consequently, the exposure and risk associated with these chemicals are not adequately understood.

A high-performance liquid chromatographic method was developed to analyse selected endocrine disrupting chemicals in water by using automated on-line solid-phase extraction with a fluorescence detector. The excitation and emission wavelengths of the fluorescence detector were 230 nm and 290 nm, respectively. The selected endocrine disrupting chemicals include hormone steroids such as estradiol (E2), estriol (E3), ethynylestradiol (EE2), and ethynylestradiol 3-methyl ether (MeEE2) as well as nonylphenols (NP), octylphenols (OP), POE(1-2) nonyl phenol (NPE) and bisphenol A (BP). Three types of on-line cartridges (C18, PLRP-s and PRP-1) were tested to pre-concentrate the endocrine disruptors in deionised water. It was found that the recoveries of these chemicals at 1 microg/L were close to 100% except for 4-octyl phenol and 4-n-nonyl phenol, which had recoveries of about 40% to 80%. The two polymer cartridges (PLRP-s and PRP-1) gave higher recoveries than the C18 cartridges. The addition of methanol at 5% to 10% in water significantly improved the recovery of 4-octyl phenol and 4-n-nonyl phenol. The addition of methanol also led to an improvement in the recovery with C18 cartridges. With the addition of methanol in water samples, these three types of cartridges gave similar recoveries for the chemicals. The detection limits of this method ranged from 20 ng/L to 50 ng/L. A river water sample spiked with these chemicals was analysed using the above method and we found no interference with the peaks of the selected endocrine disrupting chemicals. The recoveries for these chemicals were more than 92% except for 4-NP with a recovery of 61%. This relatively simple method is useful for laboratory studies on the environmental fate of these endocrine disrupting chemicals in water.