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This contribution to the American Chemical Society Symposium Series presents a collection of chapters focused on several critical issues involving endocrine-disrupting chemicals (EDCs). Some of these issues include the sources of EDCs, their presence in the environment, strategies for screening by the use of bioassays, and the quantitative measurement and identification of EDCs in various environmental media. By intention, this book is not comprehensive by any means. For example, there is little discussion of the possible toxic effects on exposed organisms. Such have been presented in great detail elsewhere and would only dilute the important focus on analytical approaches. For the most part, the authors do a very credible job in succinctly presenting the historical development of the concerns, the important questions, proposed and ongoing research approaches, and, to some degree, the possible significance of these in risk assessment and regulatory policies. The initial chapter nicely presents in a very straightforward manner most of the critical policy issues …

Extraction and chromatographic techniques for analyzing pharmaceutically active compounds necessitate large quantities of organic solvents, resulting in a high volume of hazardous waste. The concept of green solvents focuses on protecting the environment by reducing or even eliminating the use of toxic solvents. The main objective of this critical review article is to build a framework for choosing green solvents for antibiotic analyses. The article briefly discusses the chemical properties of ciprofloxacin, sulfamethoxazole, tetracycline, and trimethoprim, and the current state of methodologies for their analyses in water and wastewater. It evaluates the greenness of solvents used for antibiotic analyses and includes insights on the comparison between conventional and green solvents for the analyses. An economic and environmental health and safety analysis combined with a Conductor-like Screening Model for Real Solvent (COSMO-RS) molecular simulation technique for predicting extraction efficiency was used in the evaluation. Methyl acetate and propylene carbonate tied for the greenest solvents from an environmental and economic perspective, whereas the COSMO-RS approach suggests dimethyl sulfoxide (DMSO) as the most suitable candidate. Although DMSO ranked third environmentally and economically, after methyl acetate and propylene carbonate, it would be an ideal replacement of hazardous solvents if it could be manufactured at a lower cost. DMSO showed the highest extraction capacity, as it can interact with antibiotics through hydrophobic interaction and hydrogen bonding. This article can be used as a green solvent selection guide for developing sustainable processes for antibiotic analyses.

The use of biochar to recover nitrogen and phosphorus from wastewater especially source-separated human urine is attractive from both economic and environmental standpoints. The widespread use of pharmaceuticals has raised concerns as they are not fully metabolized and ended up in human urine. The objective of this study is to examine adsorption of antibiotics (azithromycin, ciprofloxacin, sulfamethoxazole, trimethoprim, and tetracycline) and nutrients (ammonium and phosphate) in source-separated human urine by biochar and subsequent desorption. Batch adsorption experiments were conducted using biochar prepared from oak wood (OW) and paper mill sludge (PMS) to elucidate the effects of adsorption time, pH, and adsorbent dose. The desorption of adsorbed nutrients and antibiotics was also investigated. While the nutrient adsorption was more favorable by the PMS biochar, antibiotic adsorption was more prolific by the OW biochar. Hydrogen bonding and π-π interaction were identified as potential adsorption mechanisms. Experimental results agree with the Freundlich isotherm and pseudo-second order models (except the OW biochar for the kinetics). The findings suggest that biochar can adsorb both nutrients (43.30-266.67 mg g

Biochar (BC) is an inexpensive and widely available carbon-based material with a variety of applications. Zero valent iron nanoparticles (nZVI), on the other hand, are highly reactive species. However, agglomeration and difficulty of separation from the treated media are the major reported drawbacks associated with nZVI application for water treatment. In this study, BC was modified by a simple heat-treatment, producing hydrophilic heat-treated biochar (HBC) with enhanced absorptive features, and was impregnated with nZVI, producing BC/nZVI composite for efficient organic contaminant removal. Synthesis conditions of BC/nZVI composite were optimized by evaluating p-nitrosodimethylaniline (pNDA) bleaching efficiency of various BC/nZVI samples synthesized under different conditions of pH, ultrasonication amplitude, and iron concentration. Variously-synthesized HBCs were then used to synthesize HBC/nZVI composites, and were characterized for surface morphology, surface chemistry, and elemental composition. The best-performing HBC/nZVI for pNDA bleaching was then used for trichloroethylene (TCE) removal from water. Using HBC/nZVI or BC/nZVI composites, the pseudo-second order model fit indicated a chemisorption mechanism for organic contaminants removal. Using 250 mg L−1 of the best-performing HBC/nZVI, an 88% TCE reduction (initial concentration of 40 μg L−1) was achieved after 20 min at pH = 3.0, with a rate of 3.318 g mg−1 min−1.

Provisional molecular weights and chemical formulas were assigned to 4 significant previously unidentified contaminants present during active fish kills in the Red River region of Oklahoma. The provisional identifications of these contaminants were determined using high-resolution liquid chromatography-time-of-flight mass spectrometry (LC-TOFMS), LC-Fourier transform ion cyclotron resonance mass spectrometry (LC-FTICRMS), and LC-ion trap mass spectrometry (LC-ITMS). Environmental water samples were extracted using a solid-phase extraction (SPE) method, and sediment samples were extracted using a modified sonication liquid extraction method. During screening of the samples, 2 major unknown chromatographic peaks were detected at m/z 624.3 and m/z 639.3. The peak at m/z 639.3 was firmly identified, through the use of an authentic standard, as a porphyrin, specifically chlorin-e6-trimethyl ester, with m/z 639.31735 (M + H)+ and molecular formula C37 H43 N4 O6 . The other major peak, at m/z 624.3 (M + H)+ , was identified as an amide-containing porphyrin. It was discovered that the amide compound was an artifact created during the SPE process by reaction of ammonium hydroxide at 1 of 3 potential reaction sites on chlorin-e6-trimethyl ester. Other unique nontargeted chemicals were also detected and the importance of their identification is discussed. Environ Toxicol Chem 2018;37:336-344. Published 2017 Wiley Periodicals Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

The prevalence of cyanobacteria is increasing in freshwaters due to climate change, eutrophication, and their ability to adapt and thrive in changing environmental conditions. In response to various environmental pressures, they produce toxins known as cyanotoxins, which impair water quality significantly. Prolonged human exposure to cyanotoxins, such as microcystins, cylindrospermopsin, saxitoxins, and anatoxin through drinking water can cause severe health effects. Conventional water treatment processes are not effective in removing these cyanotoxins in water and advanced water treatment processes are often used instead. Among the advanced water treatment methods, adsorption is advantageous compared to other methods because of its affordability and design simplicity for cyanotoxins removal. This article provides a current review of recent developments in cyanotoxin removal using both conventional and modified adsorbents. Given the different cyanotoxins removal capacities and cost of conventional and modified adsorbents, a future outlook, as well as suggestions are provided to achieve optimal cyanotoxin removal through adsorption.

The commenter’s key argument is that Diamond Lake’s problem is strictly one of biomass, i.e., introduction of the invasive Tui Chub fish. There are a few things to note in that respect. The Tui Chub is a bait fish. It is a lower-order prey fish for higher-order trout/salmonid species. Tui Chub is zooplanktivorous. Since the Tui Chub feed on zooplankton, if they themselves are prey for other species (or are being “culled” by artificial means), and there is no other entity to feed on the plankton and algae, the result would be a mass of plankton/algae bloom (i.e., harmful algal blooms (HABs)). This would lead to anoxic conditions in the euphotic zone, which puts even more stress on the higher-order trout/salmonid species. Our work found that the biological community (i.e., invertebrates and fish) are lagging indicators (i.e., response indicators).

The emphasis of this research project was to develop and optimize a solid-phase extraction method and high-performance liquid chromatography-electrospray ionization-mass spectrometry method, such that a linkage between the detection of endocrine-active pharmaceuticals (EAPs) in the aquatic environment and subsequent effects on fish populations could eventually be studied. Four EAPs were studied: tamoxifen (TAM), exemestane (EXE), letrozole (LET), anastrozole (ANA); and three TAM metabolites: 4-hydroxytamoxifen, e/z endoxifen, and n-desmethyl tamoxifen. In aqueous matrices, the use of isotopically labeled standards for the EAPs allowed for the generation of good recoveries, greater than 80 %, and low relative standard deviations (% RSDs) (3 to 27 %). TAM metabolites had lower recoveries in the spiked water matrices: 35 to 93 % in waste/source water compared to 58 to 110 % in DI water. The precision in DI water was acceptable ranging from 8 to 38 % RSD. However, the precision in real environmental wastewaters could be poor, ranging from 15 to 120 % RSD, dependent upon unique matrix effects. In plasma, the overall recoveries of the EAPs were acceptable: 88 to 110 %, with %RSDs of 6 to 18 % (Table 3). The spiked recoveries of the TAM metabolites from plasma were good, ranging from 77 to 120 %, with %RSDs ranging from 27 to 32 %. Two of the TAM metabolites, 4-hydroxytamoxifen and n-desmethyl tamoxifen, were confirmed in most of the environmental aqueous samples. The discovery of TAM metabolites demonstrates that the source of the TAM metabolites, TAM, is constant, introducing a pseudo-persistence of this chemical into the environment.

In 2008, Lake Havasu City, Arizona, began a treated wastewater subsurface recharge program at its North Regional Wastewater Treatment Plant (NRP) to store treated wastewater, which is planned to be seasonally recovered for irrigation during the summer months. As a proactive measure, the city decided to monitor a suite of pharmaceuticals and other emerging contaminants (PECs) along with required regulatory constituents, e.g., nitrate. Potential contributing sources of PECs throughout the water system were identified, resulting in only six constituents detected in the untreated drinking water and treated drinking water, all at concentrations less than 50 ng/L. Thirty-three of 40 PECs analyzed were identified in the city9s treated wastewater streams, with concentrations ranging from just above the detection level to 9000 ng/L (pseudoephedrine), clearly showing the dominating local urban use of these compounds. NRP treated wastewater is recharged via vadose zone injection wells. It migrates through alluvial fans sediments, some containing interstitial clays, forming a water mound and blending with groundwater of the Colorado River Aquifer. Sixteen of 33 PECs present in the NRP treated wastewater have concentrations above detection limits (>10 ng/L) within 150 m (492 ft) of the injection wells. Six PECs (sulfamethoxazole, carbamazepine, primidone, phenytoin, N,N-diethyl-meta-toluamide [DEET], and meprobamate) remained above their respective detection limit in monitoring wells that penetrate sediments largely free of clay more than 560 m (1,840 ft) away from the injection wells.

Nanoparticle (NP) determination has recently gained considerable interest since a growing number of engineered NPs are being used in commercial products. As a result, their potential to enter the environment and biological systems is increasing. In this study, we report on the development of a hyphenated analytical technique for the detection and characterization of metal-containing NPs, i.e., their metal mass fraction, size, and number concentration. Hydrodynamic chromatography (HDC), suitable for sizing NPs within the range of 5 to 300 nm, was coupled online to inductively coupled plasma mass spectrometry (ICPMS), providing for an extremely selective and sensitive analytical tool for the detection of NPs. However, a serious drawback when operating the ICPMS in its conventional mode is that it does not provide data regarding NP number concentrations and, thus, any information about the metal mass fraction of individual NPs. To address this limitation, we developed single particle (SP) ICPMS coupled online to HDC as an analytical approach suitable for simultaneously determining NP size, NP number concentration, and NP metal content. Gold (Au) NPs of various sizes were used as the model system. To achieve such characterization metrics, three calibrations were required and used to convert ICPMS signal spikes into NPs injected, NP retention time on the HDC column to NP size, and ions detected per signal spike or per NP to metal content in each NP. Two calibration experiments were required in order to make all three calibrations. Also, contour plots were constructed in order to provide for a convenient and most informative viewing of this data. An example of this novel analytical approach was demonstrated for the analysis of Au NPs that had been spiked into drinking water at the ng Au L(-1) level. The described technique gave limits of detection for 60 nm Au NPs of approximately 2.2 ng Au L(-1) or expressed in terms of NP number concentrations of 600 Au NPs mL(-1). These were obtained while the 60 nm NPs exhibited a retention time of 771 s at a mobile phase flow rate of 1 mL min(-1).

Treated wastewater effluent from Las Vegas, Nevada and surrounding communities' flow through Las Vegas Wash (LVW) into the Lake Mead National Recreational Area at Las Vegas Bay (LVB). Lake sediment is a likely sink for many hydrophobic synthetic organic compounds (SOCs); however, partitioning between the sediment and the overlying water could result in the sediment acting as a secondary contaminant source. Locating the chemical plumes may be important to understanding possible chemical stressors to aquatic organisms. Passive sampling devices (SPMDs and POCIS) were suspended in LVB at depths of 3.0, 4.7, and 6.7 (lake bottom) meters in June of 2008 to determine the vertical distribution of SOCs in the water column. A custom sediment probe was used to also bury the samplers in the sediment at depths of 0-10, 10-20, and 20-30cm. The greatest number of detections in samplers buried in the sediment was at the 0-10cm depth. Concentrations of many hydrophobic SOCs were twice as high at the sediment-water interface than in the mid and upper water column. Many SOCs related to wastewater effluents, including fragrances, insect repellants, sun block agents, and phosphate flame retardants, were found at highest concentrations in the middle and upper water column. There was evidence to suggest that the water infiltrated into the sediment had a different chemical composition than the rest of the water column and could be a potential risk exposure to bottom-dwelling aquatic organisms.

article i nfo Emerging contaminants (ECs) (e.g., pharmaceuticals, illicit drugs, personal care products) have been detected in waters across the United States. The objective of this study was to evaluate point sources of ECs along the Colorado River, from the headwaters in Colorado to the Gulf of California. At selected locations in the Colorado River Basin (sites in Colorado, Utah, Nevada, Arizona, and California), waste stream tributaries and receiving surface waters were sampled using either grab sampling or polar organic chemical integrative samplers (POCIS). The grab sam- ples were extracted using solid-phase cartridge extraction (SPE), and the POCIS sorbents were transferred into empty SPEs and eluted with methanol. All extracts were prepared for, and analyzed by, liquid chromatography- electrospray-ion trap mass spectrometry (LC-ESI-ITMS). Log DOW values were calculated for all ECs in the study and compared to the empirical data collected. POCIS extracts were screened for the presence of estrogenic chemi- cals using the yeast estrogen screen (YES) assay. Extracts from the 2008 POCIS deployment in the Las Vegas Wash showed the second highest estrogenicity response.In the grab samples, azithromycin (an antibiotic) was detected in all but one urban waste stream, with concentrations ranging from 30 ng/L to 2800 ng/L. Concentration levels of azithromycin, methamphetamine and pseudoephedrine showed temporal variation from the Tucson WWTP. Those ECs that were detected in the main surface water channels (those that are diverted for urban use and irriga- tion along the Colorado River) were in the region of the limit-of-detection (e.g.,10 ng/L), but most were below de- tection limits. Published by Elsevier B.V.

Over the last 40 years, many organometallic compounds have been synthesized and used in a variety of consumer, agricultural, and industrial products. Including wastewater effluents, leaching, and direct land and water applications, there are many pathways that can disperse organometallics to the environment. Many of these compounds reach environmental compartments unchanged while others are transformed into chemical entities having different availability or toxicity to living organisms. Differences in the toxicological, biochemical, and environmental behavior of the various chemical forms of a trace element often make the determination of the total element concentration inadequate. Considerable analytical progress in organometallic speciation has been made over the past decade, when hyphenated techniques involving highly efficient separation and sensitive detection have become the techniques of choice. Methods based on liquid chromatographic separation with mass spectrometric detection have revealed new organometallic compounds in environmental and biological matrices, contributing to a better understanding of biological effects and environmental fate of organometallics. This article surveys recent applications of liquid chromatography–mass spectrometry (LC–MS) and liquid chromatography–mass spectrometry–mass spectrometry (LC–MS2) for the determination of organometallic compounds in environmental matrices.

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.

There is a growing body of evidence that toxic organotins are making their way into terrestrial and aquatic mammals including humans. In the United States, one possible route of environmental exposure to organotins (specifically dibutyltin and triphenyltin) is via fresh surface waters and fish taken from those waters. A unique methodology was used for quantitative and speciation of the organotins. This green-chemistry method combines two extraction techniques (solid-phase extraction for waters; hexane/tropolone extraction for fish) with micro-liquid chromatography-electrospray/ion trap mass spectrometry (micro-LC-ES/ITMS) as the detection method. A small survey looking for organotins in fresh surface waters across the United States, and fish from those waters, was conducted. Various concentrations of dibutyltin and triphenyltin were detected in fresh water, ranging from nondetect to 2 ppb, and nondetect to 6 ppb, respectively. In fish dibutyltin and triphenyltin were detected from nondetect to 200 ppb, and nondetect to 400 ppb, respectively.

This paper describes the application of a micro-liquid chromatography-electrospray-ion trap mass spectrometry (μ-LC-ES-ITMS) method for separation and detection of organotin compounds leached from potable-water polyvinyl chloride (PVC) pipe. Dibutyltin (DBT) is added as a heat stabilizer to PVC. DBT was determined in 11 water samples that had remained static in PVC pipes over several days (totaling 96 h). Other organotin compounds in the leachate were screened for, by using μ-LC-ES-ITMS. An initial level of approximately 1 μgl -1 of DBT resulted within 24 h, with a subsequent drop and then a rise in DBT levels over the next 96 h to 0.8 μgl -1 . Published in 2001 by John Wiley & Sons, Ltd.

International awareness of the potential hazards posed by endocrine disrupting compounds has led to several programs to optimize the selection, sampling, and analysis of a wide variety of media. The interpretation of analytical results and any subsequent regulatory changes can only be as reliable as the weakest link in the protocol. The U.S. Environmental Protection Agency (EPA) is currently engaged in a multi-disciplinary project to ensure that the analytical methods used are sufficient for the task. The Neuse River in North Carolina was chosen for a pilot study because of its geographic scale, contaminant spectrum, and potential for human and ecological exposure. Methods are being developed or modified for the study. Samples taken in 1998 are being analyzed to determine contaminant levels, compare analytical method results, build a working database, and observe any correlation among analyte groups. Samples include water, sediment, soil, fish, clams, mammals, and certain agricultural crops. This ambitious research project is a concerted effort of the EPA Office of Research and Development and the United States Geological Survey. It combines technological innovation, biological interpretation, and data analysis to strengthen the analytical protocol used to measure trace contaminants in various environmental matrices.

Due to the varying toxicity the species of organotins in their widespread applications, it is important for analytical methods to address their speciation. Traditional methods call for the hydrolysis and subsequent derivatization of the organotins before analysis. These methods can be time-consuming, derivatization can be incomplete and high levels of background interference produce difficulties in identification and quantification. The use is described of a non-derivatization and non-hydrolysis micro-liquid chromatography–electrospray/ion trap mass spectrometry for separation and detection of the organotins. Copyright © 1999 John Wiley & Sons, Ltd.

Studies have shown the detection of emerging contaminants (ECs), of which pharmaceuticals are a subset, in surface waters across the United States. The objective of this study was to develop methods, and apply them, to evaluate the potential for food chain transfer when EC-containing waters are used for crop irrigation. Greenhouse experiments were performed in which select food crops were irrigated with water spiked with three antibiotics. Field experiments, at two different sites, were conducted. Select crops were irrigated with wastewater effluent known to contain ECs, EC-free well water, and Colorado River water containing trace-level ECs. The results of the greenhouse studies show the potential for uptake of one or more of the antibiotics evaluated, albeit at very low levels. In those food crops watered with wastewater effluent, only an industrial flavoring agent, N,N'-dimethylphenethylamine (DMPEA), was consistently found. None of the evaluated contaminants were found in crops irrigated with Colorado River water.

Dibutyltin (DBT) compounds are used primarily as stabilizers for polyvinyl chloride (PVC) plastics. Small quantities can be released from PVC containers into stored liquids. The neurotoxicological potential of DBT was tested in aggregating brain cell cultures after a 10-day treatment with concentrations ranging from 10−10 to 10−6 m , either during an early developmental period, or during a phase of advanced maturation. Changes in protein content, DNA labelling and cell type-specific enzyme activities were measured as end points. DBT caused general cytotoxicity at 10−6 m in both immature and differentiated cultures. At 10−7 m , it affected the myelin content and the cholinergic neurons in both states of maturation, while GABAergic neurons remained unchanged. Astrocyte and oligodendrocyte markers were diminished at 10−7 m of DBT exclusively in immature cultures. DBT uptake by undifferentiated and differentiated cells was similar at this concentration. Whereas trimethyltin (TMT) is known to induce gliosis and triethyltin (TET) to cause demyelination and affect GABAergic neurons, DBT appeared to be more toxic than TMT, and to present a distinct toxicological pattern.

Some of the earliest initial reports from Europe and the United States demonstrated that a variety of pharmaceuticals and hormones could be found in surface waters, source waters, drinking water, and influents and effluents from wastewater treatment plants (WWTPs). It is unknown though, at this time, what ecotoxicological effects can be had from pharmaceuticals and hormones that are essentially designed for one purpose (e.g., treatment of human and domestic livestock for illness and disease) and their possible adverse effects on terrestrial wildlife, aquatic organisms, bacteria, and ultimately humans, through unintentional environmental exposure. One of the challenges the analytical chemistry community faces is the development of robust and standardized analytical methods and technologies that can easily be transferred to laboratories worldwide. While today's analysts can detect picograms per liter and nanograms per liter concentrations of numerous pharmaceuticals, hormones, and their metabolites, in a variety of environmental matrices, there are still analytical gaps that are necessary to fill. We hope that this article will add to the body of knowledge of environmental analytical chemistry techniques regarding pharmaceuticals and hormones, giving environmental scientists a good overview of those analytical techniques that are currently available, and where possible, of improvements and new methodologies that can be developed in support of this important, and relevant, environmental issue. Keywords: environmental chemistry; pharmaceuticals; hormones; analytical chemistry; solid-phase extraction; sampling; mass spectrometry; pressurized liquid extraction; green chemistry

Information is limited regarding sources, distribution, environmental behavior, and fate of prescribed and illicit drugs. Wastewater treatment plant (WWTP) effluents can be one of the sources of pharmaceutical and personal care products (PPCP) into streams, rivers and lakes. The objective of this study was to determine the contamination profiles and mass loadings of urobilin (a chemical marker of human waste), macrolide antibiotics (azithromycin, clarithromycin, roxithromycin), and two drugs of abuse (methamphetamine and ecstasy), from a small (19 mega liters day(-1), equivalent to5 million gallons per day) wastewater treatment plant in southwestern Kentucky. The concentrations of azithromycin, clarithromycin, methamphetamine and ecstasy in wastewater samples varied widely, ranging from non-detects to 300 ng L(-1). Among the macrolide antibiotics analyzed, azithromycin was consistently detected in influent and effluent samples. In general, influent samples contained relatively higher concentrations of the analytes than the effluents. Based on the daily flow rates and an average concentration of 17.5 ng L(-1) in the effluent, the estimated discharge of azithromycin was 200 mg day(-1) (range 63-400 mg day(-1)). Removal efficiency of the detected analytes from this WWTP were in the following order: urobilinmethamphetamineazithromycin with percentages of removal of 99.9%, 54.5% and 47%, respectively, indicating that the azithromycin and methamphetamine are relatively more recalcitrant than others and have potential for entering receiving waters.

Publisher Summary The development of the polar organic chemical integrative sampler (POCIS) provides environmental scientists and policy makers a tool for assessing the presence and potential impacts of the hydrophilic component of these organic contaminants. The POCIS provides a means for determining the time-weighted average (TWA) concentrations of targeted chemicals that can be used in risk assessments to determine the biological impact of hydrophilic organic compounds (HpOCs) on the health of the impacted ecosystem. Field studies have shown that the POCIS has advantages over traditional sampling methods in sequestering and concentrating ultra-trace to trace levels of chemicals over time resulting in increased method sensitivity, ability to detect chemicals with a relatively short residence time or variable concentrations in the water, and simplicity in use. POCIS extracts can be tested using bioassays and can be used in organism dosing experiments for determining toxicological significance of the complex mixture of chemicals sampled. The POCIS has been successfully used worldwide under various field conditions ranging from stagnant ponds to shallow creeks to major river systems in both fresh and brackish water.

Modern sanitary practices result in large volumes of human waste, as well as domestic and industrial sewage, being collected and treated at common collection points, wastewater treatment plants (WWTPs). In recognition of the growing use of sewage sludge as fertilizers and soil amendments, and the scarcity of current data regarding the chemical constituents in sewage sludge, the US National Research Council (NRC) in 2002 produced a report on sewage sludge. Among the NRC’s recommendations was the need for investigating the occurrence of pharmaceuticals and personal care products (PPCPs) in sewage sludge. PPCPs are a diverse array of non-regulated contaminants that had not been studied in previous sewage sludge surveys but which are likely to be present. The focus of this paper will be to review the current analytical methodologies available for investigating whether pharmaceuticals are present in WWTP-produced sewage sludge, to summarize current regulatory practices regarding sewage sludge, and to report on the presence of pharmaceuticals in sewage sludge.

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log K(ow)s < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

This volume breaks new ground in applying the current body of knowledge in the study of pharmaceauticals, personal care products and their environmental impact to the assessment of the magnitude and extent of the use of illicit drugs at the local community level. It offers new insights on the use of environmental monitoring and includes discussion on waste treatment, ecotoxicological issues, and risk assessment.

Giving public water authorities another tool to monitor and measure levels of human waste contamination of waters simply and rapidly would enhance public protection. Most of the methods used today detect such contamination by quantifying microbes occurring in feces in high enough densities that they can be measured easily. However, most of these microbes, for example E. coli, do not serve as specific markers for any one host species and many can have origins other than feces. As an alternative, chemicals shed in feces and urine might be used to detect human waste contamination of environmental waters. One potential chemical marker of human waste is the compound urobilin. Urobilin is one of the final by-products of hemoglobin breakdown. Urobilin is excreted in both the urine and feces from many mammals, particularly humans. Source waters from 21 sites in New England, Nevada, and Michigan were extracted using hydrophilic-lipophilic balance (HLB) cartridges and then analyzed by high performance liquid chromatography-electrospray mass spectrometry (HPLC-ES-MS). As a marker of human waste, urobilin was detected in many of the source waters at concentrations ranging from not detectable to 300 ng L(-1). Besides urobilin, azithromycin, an antibiotic widely prescribed for human use only in the US, was also detected in many of these waters, with concentrations ranging from not detectable to 77 ng L(-1). This methodology, using both urobilin and azithromycin (or any other human-use pharmaceutical) could be used to give public water authorities a definitive method for tracing the sources of human waste contamination. The analysis and detection of urobilin in surface waters by HPLC-ES-MS has not been previously reported in the peer-reviewed literature.

Introduction, Yuncong Li and Kati W. Migliaccio Water Quality Regulations and Policy Development, Kati W. Migliaccio and Mary Jane Angelo Water Quality Standards: Designated Uses and Numeric Criteria Development, Brian E. Haggard and J. Thad Scott Project Planning and Quality System Implementation for Water Quality Sampling Programs, Delia Ivanoff Surface Water Quality Sampling in Streams and Canals, Kati W. Migliaccio, Daren Harmel, and Peter C. Smiley, Jr. Groundwater Sampling, Qingren Wang, Rafael Munoz-Carpena, Adam Foster, and Kati W. Migliaccio Sampling Pore Water from Soil and Sediment, Yuncong Li, Kati W. Migliaccio, Meifang Zhou, and Nicholas Kiggundu Field Measurements, David Struve and Meifang Zhou Laboratory Qualifications for Water Quality Monitoring, Yuncong Li, Meifang Zhou, and Jianqiang Zhao Laboratory Analyses, Yuncong Li, Renuka R. Mathur, and Lena Q. Ma Sampling and Analysis of Emerging Pollutants, David A. Alvarez and Tammy L. Jones-Lepp Uncertainty in Measured Water Quality Data, Daren Harmel, Patricia Smith, and Kati W. Migliaccio Water Quality Statistical Analysis, Kati W. Migliaccio, Joffre Castro, and Brian E. Haggard Examples of Water Quality Monitoring, Qingren Wang and Yuncong Li Training Video for Water Quality Sampling and Analysis, Pamela J. Fletcher and Sapna Mulki