This study explored the effect of different bulk organic carbon matrices on the fate of trace organic chemicals (TOrC) during managed aquifer recharge (MAR). Infiltration through porous media was simulated in biologically active column experiments under aerobic and anoxic recharge conditions. Wastewater effluent derived organic carbon types, differing in hydrophobicity and biodegradability (i. e., hydrophobic acids, hydrophilic carbon, organic colloids), were used as feed substrates in the column experiments. These carbon substrates while fed at the same concentration differed in their ability to support soil biomass growth during porous media infiltration. Removal of degradable TOrC (with the exception of diclofenac and propyphenazone) was equal or better under aerobic versus anoxic porous media infiltration conditions. During the initial phase of infiltration, the presence of biodegradable organic carbon (BDOC) enhanced the decay of degradable TOrC by promoting soil biomass growth, suggesting that BDOC served as a co-substrate in a co-metabolic transformation of these contaminants. However, unexpected high removal efficiencies were observed for all degradable TOrC in the presence of low BDOC concentrations under well adopted oligotrophic conditions. It is hypothesized that removal under these conditions is caused by a specialized microbial community growing on refractory carbon substrates such as hydrophobic acids. Findings of this study reveal that the concentration and character of bulk organic carbon present in effluents affect the degradation efficiency for TOrC during recharge operation. Specifically aerobic, oligotrophic microbiological soil environments present favorable conditions for the transformation of TOrC, including rather recalcitrant compounds such as chlorinated flame retardants.

3-iodothyronamine (3-T1AM) and thyronamine (T0AM) are novel endogenous signaling molecules that exhibit great structural similarity to thyroid hormones but apparently antagonize classical thyroid hormone (T3) actions. Their proposed biosynthesis from thyroid hormones would require decarboxylation and more or less extensive deiodination. Deiodinases (Dio1, Dio2 and Dio3) catalyze the removal of iodine from their substrates. Since a role of deiodinases in thyronamine biosynthesis requires their ability to accept thyronamines as substrates, we investigated whether thyronamines are converted by deiodinases. Thyronamines were incubated with isozyme specific deiodinase preparations. Deiodination products were analyzed using a newly established method applying liquid chromatography and tandem mass spectrometry (LC-MS/MS). Phenolic ring deiodinations of 3,3',5'-triiodothyronamine (rT3AM), 3',5'-diiodothyronamine (3',5'-T2AM), 3,3'-diiodothyronamine (3,3'-T2AM) as well as tyrosyl ring deiodinations of 3,5,3'-triiodothyronamine (T3AM) and 3,5-diiodothyronamine (3,5-T2AM) were observed with Dio1. These reactions were completely inhibited by the Dio1 specific inhibitor 6n-propyl-2-thiouracil (PTU). Dio2 containing preparations also deiodinated rT3AM and 3',5'-T2AM at the phenolic rings but in a PTU-insensitive fashion. All thyronamines with tyrosyl ring iodine atoms were 5(3)-deiodinated by Dio3 containing preparations. In functional competition assays, the newly identified thyronamine substrates inhibited an established iodothyronine deiodination reaction. By contrast, thyronamines which had been excluded as deiodinase substrates in LC-MS/MS experiments, failed to show any effect in the competition assays, thus verifying the former results. These data support a role for deiodinases in thyronamine biosynthesis and contribute to confining the biosynthetic pathways for 3-T1AM and T0AM.

High-pressure membranes, encompassing reverse osmosis (RO), nanofiltration (NF), and low-pressure RO, may provide an effective treatment barrier for trace organic compounds including disinfection by-products (DBPs), pesticides, solvents, endocrine disrupting compounds (EDCs) and pharmaceutically active compounds (PhACs). The objective is to develop a mechanistic understanding of the rejection of trace organic compounds by high-pressure membranes, based on an integrated framework of compound properties, membrane properties, and operational conditions. Eight trace organic compounds, four DBPs and four chlorinated (halogenated) solvents, are being emphasized during an initial study, based on considerations of compound properties, occurrence, and health effects (regulations). Four polyamide FilmTec membranes; three reverse osmosis/RO (BW-400, LE-440, XLE-440) and one nanofiltration/NF (NF-90); are being characterized according to pure water permeability (PWP), molecular weight cutoff (MWCO), hydrophobicity (contact angle), and surface charge (zeta potential). It is noteworthy that rejections of compounds of intermediate hydrophobicity by the candidate membranes were observed to be less than salt rejections reported for these membranes, suggesting that transport of these solutes through these membranes is facilitated by solute-membrane interactions. We are continuing with diffusion cell measurements to describe solute-membrane interactions by estimation of diffusion coefficients through membranes pores, either hindered or facilitated.

The fate of effluent organic matter (EfOM) during groundwater recharge was investigated by studying the removal behavior of four bulk organic carbon fractions isolated from a secondary effluent: Hydrophilic organic matter (HPI), hydrophobic acids (HPO-A), colloidal organic matter (OM), and soluble microbial products (SMPs). Short-term removal of the bulk organic fractions during soil infiltration was simulated in biologically active soil columns. Results revealed that the four organic fractions showed a significantly different behavior with respect to biological removal. HPI and colloidal OM were prone to biological removal during initial soil infiltration (0-30 cm) and supported soil microbial biomass growth in the infiltrative surface. Additionally, colloidal OM was partly removed by physical adsorption or filtration. HPO-A and SMPs reacted recalcitrant towards biological degradation as indicated by low soil biomass activity responses. Adsorbability assessment of the biologically refractory portions of the fractions onto powered activated carbon (PAC) indicated that physical removal is not likely to play a significantly role in further diminishing recalcitrant HPO-A, HPI and SMPs during longer travel times in the subsurface.

The objective of this study was to determine the primary removal mechanisms of endocrine disruptors such as steroidal hormones present in reclaimed water, specifically 17beta-estradiol, estriol, and testosterone, during groundwater recharge via soil aquifer treatment (SAT). Steroidal hormones were quantified using enzyme-linked immunosorbent assays. Bench-scale studies and laboratory-scale soil column experiments were employed to determine what mechanisms (i.e., adsorption, biodegradation, photolytic degradation) dominate the removal of the three compounds of interest during SAT. Findings of these studies revealed that the dominating removal mechanism for the compounds of interest during SAT is adsorption to the porous media matrix and additional attenuation to below the detection limit occurred in the presence of bioactivity. This additional removal occurred regardless of dominating redox conditions (aerobic vs. anoxic) or the type of organic carbon matrix present (hydrophobic acids, hydrophilic carbon vs. colloidal carbon).

Solid-phase extraction at an acidic pH is used as a common sample preparation method for analyzing residues of the analgesic drug diclofenac (2-[(2,6-dichlorophenyl)amino] benzeneacetic acid) in environmental water samples. This paper describes the matrix-dependent formation of an artifact of diclofenac during sample preparation resulting in an up to 40% underestimation of diclofenac concentrations especially in matrix-prone samples such as sewage effluents or surface water. The artifact most likely being formed during acidification of the sample was unequivocally identified as 1-(2,6-dichlorophenyl)indolin-2-one by capillary gas chromatography-mass spectrometry. To avoid an underestimation of the analytical results quantification of both diclofenac and its artifact is recommended.

Recently, the occurrence and fate of pharmaceutically active compounds (PhACs) in the aquatic environment was recognized as one of the emerging issues in environmental chemistry and as a matter of public concern. Residues of PhACs have been found as contaminants in sewage, surface, and ground- and drinking water samples. Since June 2000, a new long-term monitoring program of sewage, surface, ground- and drinking water has been carried out in Berlin, Germany. Samples, collected periodically from selected sites in the Berlin area, are investigated for residues of PhACs and related contaminants. The purpose of this monitoring is to investigate these compounds over a long time period to get more reliable data on their occurrence and fate in the different aquatic compartments. Moreover, the surface water investigations allow the calculation of season-dependent contaminant loads in the Berlin waters. In the course of the monitoring program, PhACs and some other polar compounds were detected at concentrations up to the microg/L-level in all compartments of the Berlin water cycle. The monitoring is accompanied and supported by several other investigations such as laboratory column experiments and studies on bank filtration and drinking water treatment using conventional or membrane filtration techniques.

This study investigated the occurrence of pharmaceuticals, emphasizing triiodinated benzene derivatives used as X-ray contrast media, in domestic effluents and their fate during subsequent groundwater recharge. Organic iodine measurements were used as a surrogate for triiodinated benzene derivatives. Seven wastewater treatment facilities in Texas, Arizona and California were studied and organic iodine concentrations at these facilities varied between 5 and 40 microg iodine/L. The highest concentrations were observed on weekdays reflecting the common practice of employing X-ray examinations between Monday and Friday. Organic iodine compounds in secondary treated effluents were not removed by advanced wastewater treatment using ozone. However, organic iodine was efficiently removed by reverse osmosis membrane treatment. Based on laboratory biodegradation experiments and field studies negligible removal occurred under aerobic redox conditions while anoxic conditions led to partial removal of organic iodine. However, a concentration range of 8-15 microg iodine/L was observed in groundwater recharge systems after travel times of 8 to 10 years. Beside appropriate redox conditions, bioavailable organic carbon seems to be a key factor for organic iodine biodegradation in the environment. No environmental risk is expected from the parent compounds of triiodinated contrast media, however, toxicological effects associated with the metabolites are unknown.

Water quality transformations during soil aquifer treatment at the Mesa Northwest Water Reclamation Plant (NWWRP) were evaluated by sampling a network of groundwater monitoring wells located within the reclaimed water plume. The Mesa Northwest Water Reclamation Plant has used soil aquifer treatment (SAT) since it began operation in 1990 and the recovery of reclaimed water from the impacted groundwater has been minimal. Groundwater samples obtained represent travel times from several days to greater than five years. Samples were analyzed for a wide range of organic and inorganic constituents. Sulfate was used as a tracer to estimate travel times and define reclaimed water plume movement. Dissolved organic carbon concentrations were reduced to approximately 1 mg/L after 12 to 24 months of soil aquifer treatment with an applied DOC concentration from the NWWRP of 5 to 7 mg/L. The specific ultraviolet absorbance (SUVA) increased during initial soil aquifer treatment on a time-scale of days and then decreased as longer term soil aquifer treatment removed UV absorbing compounds. The trihalomethane formation potential (THMFP) was a function of the dissolved organic carbon concentration and ranged from 50 to 65 micrograms THMFP/mg DOC. Analysis of trace organics revealed that the majority of trace organics were removed as DOC was removed with the exception of organic iodine. The majority of nitrogen was applied as nitrate-nitrogen and the reclaimed water plume had lower nitrate-nitrogen concentrations as compared to the background groundwater. The average dissolved organic carbon concentrations in the reclaimed water plume were less than 50% of the drinking water dissolved organic concentrations from which the reclaimed water originated.

The scope of this study was to develop a model to assess the impact of source water quality on reclaimed water used for indirect potable reuse. The source water impact model (SWIM) considered source water qualities, water supply distribution data, water use and the impact of wastewater treatment to calculate reclaimed water quality. It was applied for sulfate, chloride, and dissolved organic carbon (DOC) at four water reuse sites in Arizona and California. SWIM was able to differentiate between the amount of salts derived by drinking water sources and the amount added by consumers. At all sites, the magnitude of organic residuals in reclaimed water was strongly effected by the concentration of organics in corresponding water sources and effluent-derived organic matter. SWIM can be used as a tool to predict reclaimed water quality in existing or planned water reuse systems.

Soil aquifer treatment (SAT) and bank filtration use natural attenuation processes to purify water for subsequent use. Soil aquifer treatment may constitute both unsaturated and saturated flow conditions, while bank filtration systems are primarily saturated flow. This analysis focuses on the saturated zone, where the majority of residence time occurs, in both SAT and bank filtration systems. Sustainable removal mechanisms during subsurface flow are primarily surface-mediated and therefore depend on surface area. By analyzing saturated subsurface flow hydraulics in granular media, a relationship between surface area and travel time was developed. For saturated subsurface flow, the ratio of surface area-to-travel time varied by approximately a factor of 3, for common aquifer materials subject to identical hydraulic gradients. Because travel time criteria often are used to regulate SAT and bank filtration systems, these criteria also may determine the surface area and associated surface-mediated reactions for water purification. The ratio of surface area-to-travel time increases with increasing hydraulic gradient, implying that surface area is relatively constant for specific travel times, even if the hydraulic gradient changes; however, the increasing hydraulic gradient will increase the distance from the recharge zone to the recovery well. Therefore, travel time assessments based on maximum possible hydraulic gradients increase surface area and could provide a conservative limit for surface-mediated reactions. This analysis demonstrates that travel time criteria for SAT and bank filtration systems indirectly provide a minimum surface area that may support sustainable removal mechanisms.

December 2008 marked the completion of Stage 2B of the Western Corridor Recycled Water (WCRW) Project in South East Queensland, Australia. With a maximum combined production capacity of 232 million litres of purified recycled water a day, it is the third largest recycled water scheme in the world and the largest in southern hemisphere. A seven-barrier approach has been used to ensure very highest quality, safe water is produced at all times for the purpose of indirect potable reuse. Three of these barriers occur in the advanced water treatment section of the WCRW Project: micro- or ultra-filtration (MF), reverse osmosis (RO), and H(2)O(2)/UV advanced oxidation. In addition to providing very efficient disinfection, the advanced oxidation process specifically aims at destroying compounds not fully rejected by RO that are potential health hazards. This includes N-nitrosodimethylamine (NDMA), which is a potential carcinogenic product likely to be formed by chlorination or chloramination of wastewaters. As in many other countries, Australia has adopted a stringent guideline limit for this compound of 10 ng/L in purified recycled water. After 16 months of operations of the WCRW Project's first plant, the advanced oxidation system has been proven effective in removing NDMA and ensuring 100% compliance with the regulation at a controlled cost.

A comparison of time-weighted average pharmaceutical concentrations, loadings and enantiomer fractions (EFs) was made among treated wastewater from one rural aerated lagoon and from two urban tertiary wastewater treatment plants (WWTPs) in Alberta, Canada. Passive samplers were deployed directly in treated effluent for nearly continuous monitoring of temporal trends between July 2007 and April 2008. In aerated lagoon effluent, concentrations of some drugs changed over time, with some higher concentrations in winter likely due to reduced attenuation from lower temperatures (e.g., less microbially mediated biotransformation) and reduced photolysis from ice cover over lagoons; however, concentrations of some drugs (e.g. antibiotics) may also be influenced by changing use patterns over the year. Winter loadings to receiving waters for the sum of all drugs were 700 and 400g/day from the two urban plants, compared with 4g/day from the rural plant. Per capita loadings were similar amongst all plants. This result indicates that measured loadings, weighted by population served by WWTPs, are a good predictor of other effluent concentrations, even among different treatment types. Temporal changes in chiral drug EFs were observed in the effluent of aerated lagoons, and some differences in EF were found among WWTPs. This result suggests that there may be some variation of microbial biotransformation of drugs in WWTPs among plants and treatment types, and that the latter may be a good predictor of EF for some, but not all drugs.

Eight different sewage treatment works were sampled in the North West of England. The effectiveness of the conventional treatment processes (primary sedimentation and biological trickling filters) as well as various tertiary treatment units in terms of both total and dissolved copper removal was evaluated. The removal of total copper across primary sedimentation averaged 53% and were relatively consistent at all sites, however, at three sites the removal of dissolved copper also occurred at this stage of treatment. Removal of total copper by the biological trickling filters averaged 49%, however, substantial dissolution of copper occurred at two sites, which highlighted the unpredictability of this treatment process in the removal of dissolved copper. Copper removal during tertiary treatment varied considerably even for the same treatment processes installed at different sites, primarily due to the variability of insoluble copper removal, with little effect on copper in the dissolved form being observed. The proportion of dissolved copper increased significantly during treatment, from an average of 22% in crude sewages to 55% in the final effluents. There may be the potential to optimise existing, conventional treatment processes (primary or biological treatment) to enhance dissolved copper removal, possibly reducing the requirement for installing any tertiary processes specifically for the removal of copper.

Pharmaceutically active compounds (PhACs) and drugs of abuse (DAs) are two important groups of emerging environmental contaminants that have raised an increasing interest in the scientific community. A number of studies revealed their presence in the environment. This is mainly due to the fact that some compounds are not efficiently removed during wastewater treatment processes, being able to reach surface and groundwater and subsequently, drinking waters. This paper reviews the data regarding the levels of pharmaceuticals and illicit drugs detected in wastewaters and gives an overview of their removal by conventional treatment technologies (applying activated sludge) as well as advanced treatments such as membrane bioreactor. The paper also gives an overview of bank filtration practices at managed aquifer recharge sites and discusses the potential of this approach to mitigate the contamination by PhACs and DAs.

Results of experiments investigating geochemical changes during artificial recharge of treated wastewater at a coastal sandfill, reclaimed with sand dredged from the seabed, are reported in this paper. Laboratory batch experiments were conducted using secondary effluent (SE) and SE treated with an additional ultrafiltration process (UF), and wastewater treated by reverse osmosis (RO) process, mixed with surface sand obtained from the sandfill. Experiments with RO showed a net increase of 0.41 meq/L, 0.12 meq/L and 0.31 meq/L for Ca(2 +), Mg(2 +) and HCO(3)(-), respectively. UF and SE also exhibited net increase in Ca(2 +), Mg(2 +) and HCO(3)(-) indicating carbonate mineral dissolution. All three waters were found to be over-saturated with respect to calcite. Carbonate dissolution reactions were observed in the field experiments. However, the presence of imported clays from the borrow source gave rise to ion exchange reactions where Na(+) attached to the clay particles were exchanged for Ca(2 +) and Mg(2 +) inducing mineral dissolution, driven by sub-saturation conditions. This resulted in an increase in pH with maximum values in excess of 9.0. It was also found that the sodium adsorption ratio remained high (>10) even after the groundwater had been diluted sufficiently to freshwater levels (ionic strength, I<0.015) indicating a potential for the dispersion of clay particles. This could have a deleterious consequence on porosity and hydraulic conductivity.

The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant, insect repellent and antipsychotic, were investigated in four wastewater treatment plants (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Most of the target compounds were detected, with the concentrations of 4.4ngL(-1)-6.6mugL(-1) and 2.2-320ngL(-1) in the influents and secondary effluents, respectively. These concentrations were consistent with their consumptions in China, and much lower than those reported in the USA and Europe. Most compounds were hardly removed in the primary treatment, while their removal rates ranging from -12% to 100% were achieved during the secondary treatment. In the tertiary treatment, different processes showed discrepant performances. The target compounds could not be eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO) processes employed in two WWTPs were very effective to remove them, showing their main contributions to the removal of such micro-pollutants in wastewater treatment.

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.

Increasing attention has been given to pollution of the water environment by pharmaceutical compounds discharged from wastewater treatment plants. High-pressure driven membranes such as a nanofiltration (NF) membrane and a reverse osmosis (RO) membrane are considered to be effective for control of pharmaceuticals in wastewater treatment. In practical applications of NF/RO membranes to municipal wastewater treatment, feed water for the membranes always contains organic macromolecules at concentrations of up to 10mg-TOC/L, which are mainly composed of soluble microbial products (SMPs) produced during biological wastewater treatment such as an activated sludge process. In this study, influence of these organic macromolecules on removal of six pharmaceuticals by NF/RO membranes (UTC-60 and LF10) was investigated. Two types of biological treatment (conventional activated sludge process followed by media filtration (i.e., tertiary treatment) and treatment with a membrane bioreactor (MBR)) were examined as pretreatments for NF/RO membranes in this study. In the filtration tests with wastewater effluents, removal of the pharmaceuticals was higher than that seen with deionized pure water spiked with the pharmaceuticals. The increase was significant in the case of the NF membrane. Both alteration of membrane surface properties due to membrane fouling and association of the pharmaceuticals with organic macromolecules contributed to the increase in removal of pharmaceuticals by the membranes. Characteristics of the organic macromolecules contained in the wastewater effluents differed depending on the type of treatment, implying that removal of pharmaceuticals by NF/RO membranes is influenced by the type of pretreatment employed.

A solid-phase extraction (SPE) LC-MS/MS method for 18 commercial drugs in secondary wastewater and product water from water recycling plants using microfiltration (MF) and reverse osmosis (RO) has been developed, optimised and validated. The method incorporates a range of multi-class pharmaceuticals including lipid lowering agents, analgesics, antipyretics, non-steroidal anti-inflammatory drugs, antidepressants, anticoagulants, tranquilizers, cytostatic agents, and antiepileptics. Method limits of quantitation (MLQs) in secondary wastewater ranged from 15 to 250ng/L, while MLQs in post-RO water ranged from 1 to 25ng/L. Results from analysis of secondary wastewater from Western Australia are presented, and represent the largest survey of non-antibiotic pharmaceuticals within Australia to date. Analysis of post-RO water from two MF/RO water recycling facilities also demonstrate that MF/RO treatment removes most pharmaceuticals to below the analytical limits of detection, and more importantly, up to seven orders of magnitude below health-based guideline values.