Search

A microwave-assisted extraction method for the determination of 15 alkyl, aryl, and halogenated phenols in sewage sludge and biosolids samples was developed and optimized. The effects of solvent, temperature, time, moisture content, acid, and number of extractions on the recovery of phenols were evaluated. Results indicated that extraction solvent had the greatest impact on the recovery of all phenols while pH had the largest effect on recovery of hexachlorophene and pentachlorophenol. Wet sludge samples were extracted with acetone-hexane mixture in the presence of glacial acetic acid. The extract was evaporated, acetylated by acetic anhydride and cleaned up by silica gel. For dry sludge samples, an optional procedure for the simultaneous extraction and acetylation of phenols was also proposed. Triclosan (TCS) and the alkyl and aryl phenols in sludge extracts were analyzed by gas chromatography-mass spectrometry (GC-MS) in electron-impact mode while polyhalogenated phenols were analyzed by GC-MS in negative ion chemical ionization mode. Method detection limits were ca. 200 ng/g for nonylphenol

Digestion of municipal wastewater biosolids is a necessary prerequisite to their beneficial use in land application, in order to protect public health and the receiving environment. In this study, 13 pharmaceuticals and personal care products (PPCPs), 11 musks, and 17 polybrominated diphenyl ethers were analyzed in 84 samples including primary sludge, waste activated sludge, digested biosolids, dewatered biosolids, and dewatering centrate or filtrate collected from five wastewater treatment plants with aerobic or anaerobic digestion. Aerobic digestion processes were sampled during both warm and cold temperatures to analyze seasonal differences. Among the studied compounds, triclosan, triclocarban, galaxolide, and BDE-209 were the substances most frequently detected under different treatment processes at levels up to 30,000 ng/g dry weight. Comparing aerobic and anaerobic digestion, it was observed that the levels of certain PPCPs and musks were significantly higher in anaerobically digested biosolids, relative to the residues from aerobic digestion. Therefore, aerobic digestion has the potential advantage of reducing levels of PPCPs and musks. On the other hand, anaerobic digestion has the advantage of recovering energy from the biosolids in the form of combustible gases while retaining the nutrient and soil conditioning value of this resource.

Rosuvastatin (RST) and atorvastatin (ATO) are prescription drugs and members in the statin family used for the treatment of elevated cholesterol levels. A method using solid-phase extraction and liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the determination of ATO, RST and its metabolite rosuvastatin lactone (RSTL) in sewage and surface water samples has been developed. In the influent and effluent samples collected from 11 sewage treatment plants located in Ontario, Canada, ATO, RST, and RSTL were detected in all samples with median concentrations of 166 ng L(-1) (influent) and 77 ng L(-1) (effluent) for ATO, 448 ng L(-1) (influent) and 324 ng L(-1) (effluent) for RST, as well as 158 ng L(-1) (influent) and 41 ng L(-1) (effluent) for RSTL. Due to the inter-conversion between RST and RSTL, the total concentration of RST and RSTL in a sewage sample should be reported. The median removal rate by wastewater treatment was 66% for ATO and 22% for RST and RSTL combined. These statins were quite persistent in sewage. After a storage period of 21 and 62 days, there was only a slight decrease in ATO concentration and no change in the total RST concentrations. These three compounds were also detected in a number of surface water samples at low ng L(-1) concentrations. This is the first reported occurrence and fate of RST and RSTL in the Canadian aquatic environment.

The presence of triclosan, a widely-used antibacterial chemical, is currently unknown in higher trophic-level species such as marine mammals. Blood plasma collected from wild bottlenose dolphins (Tursiops truncatus) in Charleston, SC (CHS) (n = 13) and Indian River Lagoon, FL (IRL) (n = 13) in 2005 was analyzed for triclosan. Plasma concentrations in CHS dolphins ranged from 0.12 to 0.27 ng/g wet weight (mean 0.18 ng/g), with 31% of the sampled individuals having detectable triclosan. The mean IRL dolphin plasma concentrations were 0.072 ng/g wet weight (range 0.025-0.11 ng/g); 23% of the samples having detectable triclosan. In the CHS area, triclosan effluent values from two WWTP were both 190 ng/L and primary influents were 2800 ng/L and 3400 ng/L. Triclosan values in CHS estuarine surface water samples averaged 7.5 ng/L (n = 18) ranging from 4.9 to 14 ng/L. This is the first study to report bioaccumulation of anthropogenic triclosan in a marine mammal highlighting the need for further monitoring and assessment.

Polycyclic and nitro musk (PNM) fragrances in personal care products persist and bioaccumulate in the environment following wastewater discharges and land application of biosolids. Influent and effluent concentrations, seasonal variations, and process removal efficiencies of 11 PNMs were investigated at six wastewater treatment plants representing four typical Canadian treatment processes: lagoon, oxidation ditch, extended aeration, and conventional activated sludge. Influent concentrations were as high as 40 000 ng/L for polycyclic musks and 400 ng/L for nitro musks, and showed some seasonal fluctuation. Effluent concentrations were as high as 4000 ng/L and 150 ng/L for polycyclic and nitro musks, respectively. Lagoon treatment produced the highest percent removal (>95%) and the lowest effluent concentrations of PNMs, with process temperature exerting some influence on removal. Results indicate that simple hydraulic or solids retention time are not strong predictors of PNM removals from wastewater. Effluent PNM concentrations were extrapolated to all treatment plants in the watershed to estimate concentrations along the Grand River and its tributaries.

The removal and/or partitioning (to sludge) of six polycyclic and five nitro musks through the liquid treatment train of a conventional Canadian secondary activated sludge wastewater treatment plant is characterized. Raw influent, primary effluent, secondary effluent, primary sludge, and waste activated sludge concentrations were correlated to seasonal process temperatures (warm, 22°C; cold, 15°C). Maximum influent concentrations of polycyclic and nitro musks were 7,030 ± 2,120 ng/L for Galaxolide (HHCB) and 158 ± 89 ng/L for musk ketone respectively. Maximum secondary effluent concentrations were 2,000 ± 686 ng/L for HHCB and 51 ± 14 ng/L for musk ketone. Temperature appeared to influence the degree of removal of musks from wastewater during primary clarification (40% median removal at warm temperatures and 9% at cold temperatures) and overall treatment (82% median removal at warm temperatures and 74% at cold temperatures) but not secondary activated sludge treatment (71% median removal at warm temperatures and 70% at cold temperatures). In primary sludge, polycyclic musks were found at concentrations up to 35,000 ng/g for HHCB, and nitro musks were found at concentrations up to 490 ng/g for musk ketone. In waste activated sludge, polycyclic musks were found at concentrations up to 52,000 ng/g (HHCB), and nitro musks were found at concentrations up to 1,100 ng/g (musk ketone). The hydraulic retention time and the suspended solids of the treatment process appeared to influence the degree of partitioning of musks to sludge.

An efficient microwave-assisted extraction (MAE) procedure has been optimized for the determination of polycyclic and nitro musks in sewage sludge. A centrifuged sludge cake sample (from 1 to 2.5 g ), mixed with 10 g of anhydrous sodium sulfate in a Teflon cell, was extracted with 30 mL of a 1:1 (v/v) mixture of acetone and hexane for 35 min, including a 15-min ramp with a 20-min hold at a controlled temperature of 110°C. After 30 min of cooling, the extract was evaporated and cleaned up on a silica gel column. A concentrated sample extract was then analyzed by gas chromatography/mass spectrometry (GC/MS) in the electron impact mode for the polycyclic musks and in negative ion chemical ionization mode for the nitro musks. This new method has been validated by comparing it to an established accelerated solvent extraction (ASE) method, with method detection limits ranging from 27 to 41 ng/g for the polycyclic musks, and approximately 4 ng/g for the nitro musks. Recoveries of most compounds in spiked samples ranged from 80 to 105%, although the MAE method produced lower recoveries for the nitro musks than the ASE method in archived sludge samples. The results generated by this MAE method were consistent with those prepared by previously reported techniques such as supercritical fluid extraction.

A solid-phase extraction (SPE) and liquid chromatographic (LC) method was developed for the determination of selected fluoroquinolone (FQ) drugs including ofloxacin, norfloxacin, and ciprofloxacin in municipal wastewater samples. Extraction of the FQs was carried out with a weak cation exchanger SPE cartridge, the Oasis WCX. The cartridge was washed with water and methanol as a cleanup before the FQs were eluted by a mixture of methanol, acetonitrile, and formic acid. Separation of the FQs was achieved by using a Zorbax SB-C8 column under isocratic condition at a flow rate of 0.2mL/min. Recoveries of the FQs in spiked final effluent samples were between 87 and 94% with a relative standard deviation of less than 6%. Several techniques have been evaluated for the detection of FQs in sewage extracts; they included fluorescence detection and electrospray ionization (ESI) mass spectrometry using either mass-selective detection or tandem mass spectrometry (MS/MS). When they were applied to sewage influent and effluent samples, the LC-MS/MS technique operating in the multiple reaction monitoring (MRM) mode proved to be best suited for the determination of FQs in sewage samples as it provided the highest sensitivity (limit of quantification 5ng/L) and selectivity. The observation of signal suppression (matrix effect) for some FQs in ESI LC-MS and LC-MS/MS is discussed and a solution is proposed. The three FQs were detected in all the sewage samples tested in this work, with median concentrations between 34 and 251ng/L.

Thirty-five sewage sludge samples collected across Canada were analyzed for 18 polycyclic aromatic hydrocarbons (PAHs), 17 congeners of polychlorinated biphenyls (PCBs) and seven selected chlorinated compounds. Samples were prepared by accelerated solvent extraction and standard column cleanup procedures using silica gel and Florisil. Gas chromatography with electron-capture detection was used for the determination of PCBs. Gas chromatography/mass spectrometry with electron-impact ionization and methane negative ion chemical ionization were used for the detection of PAHs and the chlorinated compounds, respectively. PAHs were detected in nearly all samples, with a total concentration ranging from 0.14 to 209 µg/g (median 3.65 µg/g) on a dry weight basis. Phenanthrene, fluoranthene and pyrene were present at the highest concentrations, with medians ranging from 0.56 to 0.58 µg/g. PCBs were also found in all samples, with a total PCB concentration ranging from 31 to 323 ng/g. The most abundant PCBs (congeners 52, 101 and 110) had median concentrations of 12 ng/g or above. While pentachlorobenzene and hexachlorobenzene were observed in all sludge, at low ng/g levels, no other less chlorinated benzenes have been detected in the same samples. Octachlorostyrene was only found in the Ontario samples, with concentrations ranging from 0.3 to 11.5 ng/g (median 0.9 ng/g). For the chlorinated insecticides, only p,p'-DDE, α- and γ-chlordane were found on a more regular basis, with median concentrations of 12.0, 0.4 and 0.8 ng/g, respectively. These results suggest that the above toxic chemicals are occurring in Canadian sewage samples and are persistent enough to survive the existing sewage treatment processes.

The occurrence, fate, and effects of phenols with endocrine-disrupting properties as well as some pharmaceuticals and personal-care products in the environment have frequently been discussed in recent literature. In many cases, these compounds were determined by using individual methods which can be time-consuming if results for multiple parameters are required. Using a solid-phase extraction procedure with an anion exchanger in this work, we have developed and optimized a multi-residue method for the extraction of 21 phenols and acids in sewage influent and effluent. The phenols and acids were then selectively eluted in separate fractions and were converted into pentafluoropropionyl (PFP) and tert-butyldimethylsilyl (TBDMS) derivatives, respectively, for gas chromatography-mass spectrometric (GC/MS) determination. When applied to the sewage samples under study, the results for nonylphenol, bisphenol A (BPA), triclosan (TCS), 17ss-estradiol (E2), estrone (E1), salicylic acid, ibuprofen, naproxen, diclofenac, and a few other acidic drugs were consistent with those determined previously by individual methods. Using the same procedure, we also report, for the first time, the occurrence of 2-phenylphenol and parabens in those sewage samples.

The relative estrogenicity of nonylphenol and its ethoxylates has not been clearly demonstrated in the literature, despite the importance of this information for interpreting the environmental risk of these chemicals. There appears to be a discrepancy between the relative acute/chronic toxicity and estrogenicity reported in previous studies. These studies have suggested that the relatively higher concentrations of nonylphenol polyethoxylate metabolites (NPnEO, NPnEC) in municipal effluents may represent a risk to the environment. However, there is considerable uncertainty associated with the estimates of relative estrogenicity of these metabolites. Plasma vitellogenin (Vg) was measured in rainbow trout (Oncorhynchus mykiss) after a 21-d flow-through exposure to concentrations of 1–250 μ g · L− 1 nonylphenol (NP), 1–280 μ g · L− 1 nonylphenol 1-ethoxylate (NP1EO), or 24–1450 μ g · L− 1 nonylphenol 1-ethoxycarboxylate (NP1EC). All three chemicals induced plasma Vg to varying degrees, their relative...

A solid-phase extraction, chemical derivatization, and gas chromatography/mass spectrometry (GC/MS) method has been developed for the determination of trace 3,3'-dichlorobenzidine (DCB) in industrial wastewater samples. Instead of an octadecylsilane (ODS) cartridge, a Porapak RDX cartridge was used since the latter could be optimized for the extraction of DCB. After the pre-concentration, interfering coextractives in the sample were selectively removed from the cartridge by elution with a 1:1 mixture of acetonitrile and water. DCB was then eluted with acetonitrile and derivatized with pentafluoropropionic acid anhydride. The product was subsequently analyzed by GC/MS in either the electron impact or negative ion chemical ionization mode. Recoveries of DCB and the surrogate, DCB-d6, were better than 90% at spiking levels of 10, 1, and 0.1 µg/L. Based on a concentration factor of 100, the detection limits for DCB in wastewater samples were determined to be 0.1 µg/L by electron impact GC/MS detection, and 0.01 µg/L by negative ion chemical ionization GC/MS detection, respectively. This method has been successfully applied to wastewater samples collected in the Toronto area.

In recent years, many anthropogenic chemicals occurring in the environment have been shown to mimic the action of endogenous hormones. These endocrine-disrupting chemicals (EDCs) can potentially lead to a host of adverse effects on wildlife, such as the feminization of fish, the lack of reproductive success of some species, birth defects, and the development of physical abnormality. In an attempt to establish the levels of contamination by EDCs in municipal sewage and sludge, we have collected samples in the Toronto area and analyzed them for alkylphenols, alkylphenol ethoxylates and carboxylates, 17ß-estradiol and its metabolites, testosterone, bisphenol A, as well as butyltin species. Previously developed methods using solvent extraction, solid-phase extraction, supercritical fluid extraction, GC/MS, and HPLC determination have been used for such samples. Levels of these chemicals varied from 500 µg/g for nonylphenol to

Fragrances such as synthetic musk compounds are commonly used as additives in a wide range of consumer and personal-care products. At the end of their life cycle, most of these compounds will end up in municipal sewage systems. In this work, we report the occurrence of selected polycyclic and nitro musk compounds in sewage sludge, influent, effluent, as well as some industrial wastewater samples collected in Canada. A newly developed supercritical carbon dioxide extraction technique was used for the extraction of residual musk fragrances in the sludge. Final analysis was performed by gas chromatography/ mass spectrometry (GC/MS) using electron-impact and methane negative ion chemical ionization techniques. The results indicated that Galaxolide® (HHCB), Tonalide® (AHTN), musk xylene (MX), and musk ketone (MK) were the most common musk compounds in the Canadian environment, as they were found in every sample in this study. In the same sludge sample, levels of HHCB and AHTN (ranging from 1.3 to 26.7 μg/g) were often found to be about 1000 times higher than those of MX and MK (ranging from 1.4 to 422 ng/g). Similarly, in the sewage influent and effluent collected in Ontario, the levels of HHCB and AHTN (ranging from 159 to 2411 ng/L) were much higher than those of MX and MK (ranging from 1 to 84 ng/L). The levels of musk compounds varied widely in industrial wastewaters. In one sample collected from a detergent manufacturer, the levels of HHCB, AHTN, MX, and MK were found to be 54,200, 13,300, 5480, and 2.2 ng/L, respectively. It was also noted that the levels of MX and MK observed in the samples collected from the commercial laundries in Toronto were significantly higher than those found in domestic sewage.

A gas chromatography/mass spectrometry (GC/MS) method for the determination of 11 selected acidic pharmaceuticals in sewage influent and effluent at trace levels has been developed. The drugs studied were salicylic acid, clofibric acid, ibuprofen, acetaminophen, gemfibrozil, fenoprofen, naproxen, ketoprofen, diclofenac, fenofibrate, and indomethacin, which are commonly used as analgesic/anti-inflammatory agents or lipid regulators. The antibacterial agent triclosan was also included in this study. A solid-phase extraction procedure using the Waters Oasis HLB (hydrophilic-lipophilic balance) cartridge was optimized for the extraction and elution of these compounds. The acids were then converted into their trimethylsilyl (TMS) derivatives. Final analysis was performed with a Mass Selective Detector in the EI/SIM (electron impact/selected ion monitoring) mode. Recoveries of the drugs in spiked distilled water samples at 1 and 0.1 μ/L levels were better than 80%. Similar recoveries of the drugs were obtained from fortified final effluent samples except for acetaminophen, which could not be recovered even if the extraction was performed immediately. The detection limits for the drugs, based on a concentration factor of 1000, were between 10 and 20 ng/L. A stability study indicated that, except for salicylic acid and acetaminophen, the other acidic pharmaceuticals were better than 75% recovered after the samples had been stored at 4°C in the dark for up to seven days. This method has been applied to quantify acidic drugs in wastewater samples collected from several sewage treatment plants in Ontario. While clofibric acid, acetaminophen, fenoprofen, and fenofibrate have never been detected, the other eight compounds were found in nearly all the influent and effluent samples, from low μ/L to low ng/L levels. Eight sewage treatment plants removed from 0 to 98% of these drugs from the influent.

Nonylphenol ethoxylates (NPEs) are a group of surfactants that are widely used for industrial, commercial, institutional and household purposes in Canada. Ethoxylation of nonylphenol (NP) occurs upon reaction with ethylene oxide, producing NPEs, although NP is also used in the production of the antioxidant tris(nonylphenol)phosphite. NP and NPEs are not produced naturally, and the primary route of environmental exposure to NP and NPEs is via textile mill, pulp and paper mill and municipal wastewater treatment plant effluents. NPEs occur as complex mixtures and are described by the average ethoxylate chain length, which ranges from 1 to 100. The environmental fate of NPEs is strongly dependent on the effluent and, the degree and type of treatment to which the effluent is subjected. An ecological risk assessment was performed to determine if exposure to NP and NPEs results in effects on the Canadian environment, based on current use patterns. The Canadian ecological risk assessment found that adverse effect...

The occurrence of toxic or endocrine-disrupting chemicals such as nonylphenol ethoxylates (NPEO), 4-nonylphenol (NP), 4-tert-octylphenol (OP), bisphenol A (BPA), triclosan (TCS), pentachlorophenol (PCP), hexachlorophene (HCP), and tetrabromobisphenol A (TBBPA) in 35 sewage sludge samples collected from cities across Canada is documented. Samples were extracted by supercritical carbon dioxide and the phenols were converted into their acetyl derivatives using published methods. The ethoxylates were analyzed by HPLC with a fluorescence detector. The other extracts, after silica gel column cleanup, were analyzed by GC/MS in either the electron impact or negative-ion chemical ionization mode. With minor exceptions, the above-mentioned compounds were present in all samples. The levels of these contaminants varied widely in the samples. The more abundant chemicals were NP as well as its mono- and di-ethoxylates, with median concentrations of 232, 69.4, and 26.4 µg/g (dry weight), respectively. Triclosan, a common antibacterial agent, BPA, and HCP were also ubiquitous in the sludge samples, with median concentrations of 12.5, 0.45, and 0.37 µg/g, respectively. Also present, albeit at much lower concentrations, were PCP and TBBPA, with median concentrations of 27.7 and 12.4 ng/g, respectively. Except for the last two compounds, all the chemicals are components or additives in various formulations of household and industrial detergents and personal care products. The potential risk of these toxic chemicals reaching the aquatic environment as a result of land spreading of sewage sludge should be investigated.

The occurrence of endocrine-disrupting chemicals (EDCs) such as bisphenol A (BPA), 4-tert-octylphenol (OP), nonylphenol (NP) and its ethoxylates (NPEO) in wastewater generated in the Toronto area has been studied. In all, 97 samples from 40 facilities in ten different industry classes have been collected and analyzed. Widely divergent concentrations have been observed in these samples. They ranged from

Two wetland plant species (Mimulus ringens L. [monkey-flower] and Bidens cernua L. [bur-marigold]), two terrestrial species (Sinapis arvensis L. [wild mustard] and Phaseolus vulgaris L. [beans-variety, Kentucky blue]), and one species found in both wet and dry habitats (Echinochloa crusgalli [L.] Beauv. [barnyardgrass]) were exposed to 1% (0.045 g a.i./ha) and 10% (0.45 g a.i./ha) of recommended label rate of metsulfuron methyl, a sulfonylurea herbicide used in western Canada. The objective of the study was to investigate the effect of metsulfuron methyl on these plant species and to determine the most sensitive phenological stage. Chemical analyses of herbicide residues showed that there was good correspondence between the quantity measured in the tank mix compared with that detected on glass fiber papers, the latter representing the dose reaching the test plants during the spray event. All species exhibited marked effects on the vegetative growth and reproductive performance when sprayed at 10% label rate. Less pronounced but significant effects were shown at 1% label rate. Seed weight was reduced for B. cernua and S. arvensis. The seedling stage was the most sensitive period for all species tested, although surviving plants sprayed at later stages showed considerable effects on the reproductive parts. All species tested would be at risk from small doses of metsulfuron methyl drifting away from the sprayed areas. This study highlights the shortcomings of the current testing schemes required prior to pesticide registration.

A large-scale study on bisphenol A (BPA) contamination in Canadian municipal and industrial wastewater and sludge has been completed. A total of about 200 samples were collected, including those from 31 sewage treatment plants and 15 pulp and paper mills across Canada, as well as 13 industrial facilities in the Toronto area. The samples were extracted by previously developed solid-phase and supercritical carbon dioxide extraction procedures and were analyzed by gas chromatography-mass spectrometry. BPA contamination was detected in all of the 72 sewage samples, with concentrations ranging from 0.080 to 4.98 µg/L (median 0.329 µg/L) for the influent, and from 0.010 to 1.08 µg/L (median 0.136 µg/L) for the effluent. Of the 36 influent/effluent sample pairs studied, BPA in the influent is removed by the sewage treatment process at a median reduction rate of 68%. Levels of BPA accumulation in sewage sludge, for the 50 samples tested, ranged from 0.033 to 36.7 µg/g, on a dry weight basis. A wide range of BPA concentrations, from 0.23 to 149.2 µg/L, were observed for the wastewater collected from selected industrial facilities in the Toronto area. The more contaminated samples came from the sectors of chemicals and chemical products, commercial dry cleaning, as well as packaging and paper products. Based on these data, on-site releases of BPA by industrial facilities seem to be much more widespread than the National Pollutant Release Inventory (NPRI) database has suggested. While relatively high levels of BPA were found in some of the primary treated effluent collected from the deinking mills, BPA concentrations in the secondary treated effluent of all pulp and paper mills were low, with a range from < 0.005 to 0.0406 µg/L. Except for the samples derived from a few deinking mills, BPA contaminication in pulp and paper mill sludge was either low or undetected.

Methods have been developed for the determination of bisphenol A (BPA) residues in municipal sewage and sludge samples. BPA in wastewater samples was enriched with a C18 solid-phase extraction cartridge, eluted with acetone, and converted to the pentafluoropropionyl derivative. For sludge samples, BPA was acetylated and extracted with supercritical carbon dioxide. In both cases, BPA-d16 was used as a surrogate to monitor extraction efficiency. Final analyses of derivatized sample extracts were performed by gas chromatography/mass spectrometry operating in the electron impact mode. For water samples, mean recoveries and standard deviations were 89 ± 6, 94 ± 4, and 85 ± 7% at fortification levels of 1, 0.1, and 0.025 μg/L, respectively, with a method detection limit of 0.006 μg/L. For solid waste samples, mean recoveries and standard deviations were 93 ± 5 and 92 ± 6% at fortification levels of 2.5 and 0.25 μg/g, respectively, and the method detection limit was 0.05 μg/g. For the Canadian samples under investigation, concentrations of BPA ranged from 49.9 to 0.031 μg/L in sewage influent and effluent, and from 36.7 to 0.104 μg/g in sludge.

A survey of the concentrations of nonylphenol ethoxylates (NPnEO) and their metabolites in the primary and secondary treated effluent and sludge samples collected from pulp and paper mills was conducted. Through the coordination of the Pulp and Paper Research Institute of Canada (PAPRICAN), 19 Canadian and one U.S. mill of various process types and waste treatment methods supplied samples in this study. Previously developed solid-phase extraction, supercritical fluid extraction, high performance liquid chromatography and gas chro-matography/mass spectrometry methods were used for the determination of NPnEO and their metabolites, nonylphenol (NP) and the carboxylates (NPEC), in effluent and sludge samples. The levels of NPnEO ranged from

Analytical methods published in the last 20 years for the extraction, chromato-graphic separation, and quantification of alkylphenol ethoxylates (APEO) and related compounds in environmental samples are reviewed. Examples of various isolation and preconcentration techniques for water, effluent, sediment and sludge are presented. This includes procedures from the classical liquid-liquid and Soxhlet extraction to the up-to-date solid phase and supercritical fluid extraction. Chromatographic separation of APEO by normal and reversed phase liquid chromatography (LC) and capillary column gas chromatography (GC) is compared. A variety of quantification methods involving the common LC and GC detectors as well as various mass spectrometric techniques are also discussed.

The paper describes a simple and quantitative method for monitoring non-conjugated 17β-estradiol (E2) and its metabolites estrone (E1) and estriol (E3) as environmental contaminants in municipal sewage effluents. Estrogens were preconcentrated and cleaned up by solid-phase extraction using a reversed-phase c18cartridge. They were derivatized with pentafluoropropionic acid anhydride, and the products were analyzed by gas chromatography/mass spectrometry. Recoveries from spiked distilled water and sewage were better than 87% at fortification levels of 100 and 20 ng/L. For a 1 L sewage sample and a concentration factor of 5000, detection limits were 5 ng/L for E1 and E2 and 10 ng/L for E3. In a brief survey of Canadian wastewater, these estrogens were detected in many raw sewage and effluent samples at concentrations ranging from 6 to 109 ng/L for E1, from

A survey of the concentrations of nonylphenol ethoxylates (NPnEO) and their metabolites in wastewater samples collected from a Canadian sewage treatment plant using primary and secondary treatment is presented. Twenty-four-hour composite raw sewage, primary effluent and final effluent samples were collected monthly over a one-year period. Levels of NPnEO (n = 1 to 17) and their metabolites, nonylphenol (NP) and nonylphenoxy carboxylic acids (NPnEC), in these samples were determined by HPLC and GC/MS methods. While ca. 85% of the total alkylphenolics in raw sewage are ethoxylates, the major component (nearly 80%) in the final effluent was in the form of carboxylic acids. During this study period, the median total alkylphenolic concentrations in raw sewage and final effluent were 526 and 248 nmol/L, respectively, representing an overall elimination rate of 53%. The estimated daily discharge of the nonylpheno-lics to the aquatic environment varied from 15 to 44 moles, with a median value of 20 moles. These data suggested that conventional sewage treatments are ineffective in the removal of the surfactant-derived metabolites.

Nonylphenol polyethoxylates and their refractory metabolites, including nonylphenol, are on the second Priority Substances List (PSL2) to determine if they are "toxic" as defined under the Canadian Environmental Protection Act. This study addresses the need for data on their occurrence in raw sewage, final effluents and sludge in Canada. Samples of raw sewage, final effluent and sludge were collected from 16 wastewater treatment plants across Canada in 1995 and 1996. These samples were analyzed for 4-nonylphenol (4-NP), nonylphenol ethoxylate (NP1EO), nonylphenol diethoxylate (NP2EO) and 4-4-tert-octylphenol (4-t-OP). Measurable quantities of these chemicals were found in almost all raw sewage and sludge samples. In the raw sewage, concentrations ranged from

Alkylphenoxyacetic acids such as 4-tert-octylphenoxyacetic acid (OP1EC) and nonylphenoxyacetic acid (NF1EC) are metabolites of non-ionic surfactants derived from the ethoxylation of 4-tert-octylphenol (OP) and nonylphenol (NP). Although the occurrence of OP1EC and NP1EC was suspected in many Canadian sewage treatment plant effluents due to the extensive use of the alkylphenol ethoxylate surfactants and their degradation under sewage treatment conditions, the acids have never been reported due to the lack of authentic standards. In this work, OP1EC and NP1EC were synthesized by the condensation of OP and NP, respectively, with chloroacetic acid in the presence of a base. With these standards, the occurrence of OP1EC and NP1EC in Canadian sewage treatment plant effluents was confirmed for the first time. The level of OP1EC ranged from 0.18 to 1.2 μg/L and from 0.45 to 6.8 μg/L, in the primary and final effluents, respectively. In contrast, the level of NP1EC in the same sample was much higher and it ranged from 2.4 to 17.7 μg/L in the primary effluents and from 3.2 to 703 μg/L in the final effluents.

A supercritical fluid extraction (SFE) method was developed for the extraction of nonylphenol polyethoxylate (NPnEO) non-ionic surfactants from dried sewage treatment plant sludge. Extraction was carried out at 80°C and 5100 p.s.i. with carbon dioxide using water as a modifier. The ethoxylates were analyzed by gradient high-performance liquid chromatography (HPLC) with an APS Hypersil column and a fluorescence detector (230 nm excitation and 300 nm emission). This SFE method was more time-efficient and it produced higher recovery than the traditional Soxhlet extraction and steam distillation techniques used for NPnEO in sewage sludge. The same procedure was also applicable to the coextraction of nonylphenoxyacetic (NP1EC) and nonylphenoxyethoxyacetic (NP2EC) acids, which were metabolites of the ethoxylates under aerobic conditions. Following an off-line methylation, analysis of the acids was achieved by GC-MS in selected ion monitoring mode. In a brief survey of sludge samples collected from nine sewage treatment plants across Canada, very high levels of nonylphenol mono- (NP1EO, 28–304 μg/g) and di-ethoxylates (NP2EO, 4–118 μg/g) were found. In contrast, the total polyethoxylate concentration (from 3 to 17 ethoxy units) was generally less than 50% of the sum of NP1EO and NP2EO in the same sample. NP1EC and NP2EC were found in only three of the seven samples tested, with concentrations ranging from 4 to 38 μg/g.

Nonylphenol and its ethoxylates are on the second priority substances list (PSL2) to determine if they are ‘toxic’ as defined under the Canadian Environmental Protection Act. This study addresses the need for data on their occurrence in surface waters and sediments in Canada. Samples of surface water from 35 sites in the Laurentian Great Lakes basin and the upper St. Lawrence River were analyzed for 4-nonylphenol (4-NP), nonylphenol ethoxylate (NPE1), nonylphenol diethoxylate (NPE2) and 4-tert-octylphenol (4-t-OP). Bottom sediment samples from nine heavily industrialized sites were also analyzed for the same chemicals. Measurable quantities of 4-NP and 4-t-OP were found in 24% of all water samples. Values ranged from

The occurrence of triclosan (TCS), a general purpose antibacterial agent contained in numerous consumer and personal-care products, in the aquatic environment is well known. To a lesser degree, the formation of chlorinated and brominated derivatives of TCS during the chlorination of the antibacterial has also been reported. Presumably due to the lack of authentic standards, very few reports have been published on the levels of these halogenated TCSs in the environment. For this purpose, we have synthesized six selected halogenated derivatives of TCS, namely, 3-Cl-, 5-Cl-, 3,5-Cl2-, 3-Br-, 5-Br-, and 3,5-Br2- TCSs, with supporting (1)H-NMR (nuclear magnetic resonance) and GC-MS (gas chromatography-mass spectrometry) data for their structural assignments. Using these model compounds together with sensitive analytical methods, we were able to identify and quantify the above compounds together with their precursor compound TCS in Canadian municipal wastewater and biosolid samples for the first time. While detected in all influent (range from 1.4 to 24.1 ng L(-1)) and biosolid (range from 7.7 to 274 ng g(-1)) samples, the concentrations of these chlorinated TCS were generally from 100- to 1,000-fold lower than TCS in the same sample. Even lower levels (

A method for the determination of nitrilotriacetic (NTA), ethylenediaminetetraacetic (EDTA) and diethylene-triaminepentaacetic (DTPA) acids in sewage treatment plant (STP) and paper mill effluents has been developed. The chelating acids were extracted by solid-phase extraction cartridges packed with strong anion-exchange resins and were eluted by a small volume of 16 M formic acid. After conversion into their 1-propyl esters, the acids were quantified by gas chromatography using a nitrogen-phosphorus-selective detector and confirmed by GC-MS with a mass selective detector. At a pH of 3.5, the recovery of these acids varied from 83 to 104% in water and STP effluent samples fortified to levels from 1 to 1000 μg/1. Based on a concentration factor of 100, the detection limit for these acids was 0.5 μg/1. All three acids were found in STP effluents, although the concentrations were relatively low for EDTA ( 1000 μg/1) of NTA were observed for nearly all primary STP effluents. A large variation in the levels of these acids was observed in the paper recycling mill effluents collected. Although their concentrations were mostly 2500 μg/1) in the effluents obtained from two mills that use this chelating agent to remove metal ions. DTPA was not detected and the concentrations for NTA and EDTA were

Quantitative and efficient methods for the determination of 4-nonylphenol (4-NP) in sewage treatment plant (STP) effluent and sludge samples were developed. For effluent, the 4-NP was converted, in situ, into its acetyl derivative with acetic anhydride in the presence of a base. In the case of sewage sludge, 4-NP was subjected to supercritical carbon dioxide extraction and on-line acetylation during the extraction stage. After a silica gel column cleanup, sample extract was analyzed by capillary column gas chromatography/mass spectrometry in the selected ion monitoring mode. Recoveries of 4-NP in spiked samples (1 and 10 μg/L for effluent and 5 and 50 μg/g for sludge) were 93% or above with relative standard deviations better than 5%. Detection limits for 4-NP were 0.1 μg/L for effluent and 0.1 μg/g for sludge. These methods were applied to the determination of 4-NP in samples collected from Toronto and vicinity STPs. Concentrations of 4-NP from 100 μg/g in sludge were found.

A method for the simultaneous extraction of polychlorinated biphenyls (PCBs) and chlorinated benzenes in sediments using supercritical fluid extraction (SFE) technique was developed. The best recovery of the above chlorinated pollutants was obtained by using non-modified carbon dioxide at 35 MPa and an extraction temperature of 100°C with a sediment moisture content in the 11 to 50% range. Cleanup of SFE extract was performed on a miniature Florisil column followed by sulfur removal with mercury. PCB levels were quantitated by a mixture of selected PCB congeners using a mass-selective detector so that the level of each PCB homologue series as well as the total PCB concentration in the sample extract could be evaluated. Under the optimized conditions, an extraction time of only 21 minutes was needed to produce PCB results comparable to a 7-h Soxhlet extraction. Meanwhile, the SFE recovery of chlorinated benzenes was up to 50% higher than for the Soxhlet results due to lower evaporative losses in the former procedure.

A supercritical fluid extraction (SFE) method using carbon dioxide was developed for the determination of the 16 US Environmental Protection Agency pol

Rainbow trout (Oncorhynchus mykiss) were exposed to nine resin acids that included abietic, dehydroabietic, chlorodehydroabietic, dichlorodehydroabietic, neoabietic, pimaric, isopimaric, sandaracopimaric, and palustric acids. Bioconcentration factors (BCFs) for these acids ranged from

An in situ supercritical fluid extraction and derivatization procedure for the determination of pentachlorophenol (PCP) and related compounds from soil samples is described. Phenols are extracted from soil and acetylated in situ with supercritical carbon dioxide in the presence of triethylamine and acetic anhydride at a temperature of 80°C. Quantitative recovery of di-, tri-, tetra- and penta-chlorophenols was obtained by a 10-min extraction with carbon dioxide at 37.2 MPa (365 bar, 0.8 g/ml density) from soil samples fortified to 0.5 and 5 ωg/g levels. In a comparison study, the supercritical fluid extracton and the steam distillation methods both produced very similar results for pentachlorophenol and other chlorophenols in a reference sample. When this method is applied to contaminated soils samples collected in a wood treatment plant, results for chlorophenols in a sample can be obtained in approximately 90 min.

A rapid and efficient method for the extraction of resin and fatty acids commonly found in sediments collected from pulp mill locations was developed by using modified supercritical carbon dioxide. In the presence of a 1:1 mixture of methanol and formic acid, quantitative recovery of all acids except for palustric and neoabietic acids was achieved with a 5 min static and 10 min dynamic extraction with carbon dioxides at 365 bar and 80°C. Although the above two resin acids were only 40% recovered from spiked samples, these values were at least 250% better than those obtained by the classical Soxhlet technique. The cleaner supercritical fluid extract permitted a less stringent cleanup after the off-line derivatization of the acids, thus it further reduced analytical time and the use of solvent. An in situ extraction and on-line derivatization of the resin and fatty acids also proved feasible for the semi-quantitative screening of the toxic acids in sediments near pulp mill locations.

A procedure for the determination and confirmation of acidic herbicides In water Is described. This method is applicable to 13 commonly used herbicides, including the monochlorinated ones, at μg/L and sub-μg/L levels. The water sample is acidified to pH < 2 and extracted by dichloromethane. The herbicides are converted into their pentafluorobenzyl (PFB) derivatives and the products are cleaned up on a silica gel column. A gel permeation cleanup using a Bio-Beads S-X3 column is included to remove the PFB esters of fatty acids, which are the major Interferences in the final analysis using electron capture detection (ECD). Confirmation of herbicides employing electron Impact and negative ion chemical lonlzatlon/ mass spectrometry (NICI/MS) is discussed and applied to river water samples. The mean recoveries of herbicides for water samples fortified at 1 and 0.1 μg/L range from 45 to over 90%. The detection limit of herbicides in natural water samples is 0.05 μg/L with ECD and 0.02 μg/L with NICI/MS.

Chlorinated phenolic derivatives are important chemical constituents that are present in pulp and paper mill effluents. Subadult rainbow trout (Salmo gairdneri) were exposed to six dichloroto terachloroguaiacols, two chlorinated vanillins and trichlorosyringol through waterborne and dietary exposure. Equilibrium concentrations were attained within 2 d in waterborne exposed fish, and bioconcentration factor (BCF) values ranged from 1 to 270 among the guaiacols, less than 5 for the chlorovanillins and 125 for trichlorosyringol. Dietary exposure indicated these chemicals are poorly absorbed and have half-lives of less than several days. The kinetics of these chemicals are consistent with residue levels reported in fish collected from waters receiving mill effluents where waterborne uptake appears to be the primary mode for accumulation.

A method using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for the determination of 12 beta-blockers and beta(2)-agonists in wastewater samples. Extraction of the drugs was effected by an Oasis MCX cartridge with a strong cation resin adsorbent. Matrix coextractives were removed from the SPE cartridge by methanol prior to the elution of the drugs with a mixture of dichloromethane, 2-propranol, and ammonium hydroxide. The extract was analyzed by LC-MS/MS with electrospray ionization operating in the positive mode. Recovery of the 12 compounds was in most cases better than 85% at the fortification levels of 500 and 50 ng/L, with standard deviations between 3 and 7%. Based on a concentration factor of 250, the method detection limits ranged from 6 to 11 ng/L for the target compounds. No degradation of these drugs in spiked sewage effluent samples was observed over a storage period of 7 days at 4 degrees C in the dark. Many beta-blockers were detected in the 14 wastewater samples collected from seven Canadian sewage treatment plants; those occurring at the highest concentrations were atenolol, acebutolol, sotalol, and metroprolol, with overall median concentrations of 1370, 339, 282, and 257 ng/L, respectively. However, there was only a small decrease in the median concentrations of these beta-blockers between the primary and final effluent, suggesting that these drugs are not easily removed by the sewage treatment processes. As a result of selective extraction and effective removal of coextractives, no matrix effect was observed for the samples during LC-MS/MS analyses.

Ten acidic and two neutral pharmaceuticals were detected in the effluents of eight sewage treatment plants (STPs) from across Atlantic Canada. Concentrations varied between nondetectable and 35 microg/L. The analgesic, nonsteroidal anti-inflammatory drugs ibuprofen and naproxen were predominant. Carbamazepine, a neutral compound used as an antiepileptic drug, was observed consistently at a median concentration of 79 ng/L. Acetaminophen was found in the effluents of the three largest mechanical STPs at a median concentration of 1.9 microg/L, but not in the lagoon treatment systems. The substantially longer hydraulic retention times may have contributed to more effective removal of acetaminophen in the lagoon treatment systems. Drugs generally were not detected at significant concentrations in the larger bodies of receiving water (Saint John River, Hillsborough River, and Bedford Bay, Canada). However, drug residues in the small receiving streams were 15 to 30% of the effluent median concentrations. Six compounds (caffeine, naproxen, salicylic acid, carbamazepine, metoprolol, and sotolol) were found to persist in a small stream for a distance of at least 17 km, suggesting that small stream exposure to pharmaceutically active residues may be relatively greater than that in large bodies of water. Bioassays assessing acute and chronic effects on four organisms were conducted on four high-use drugs: Acetaminophen, ibuprofen, naproxen, and salicylic acid (metabolite of acetyl salicylic acid). Results indicated no negative effects except for the chronic algal (Selanastrum capricornutum) growth test on ibuprofen (no-observed-effect concentration, 10 microg/L; lowest-observed-effect concentration, 32 microg/L). Effects of these four compounds on invertebrates and plants in the receiving environments are unlikely based on the concentrations measured.

Analytical technology is continuously improving, developing better methods for isolating and concentrating trace compounds in environmental samples. Polycyclic and nitro musks (PNMs) are one group of emerging trace compounds detected in municipal wastewater. Differences in sample storage, preparation, and extraction methods for their measurement have led to variability in results. We analyzed 11 PNMs by GC/MS and compared the results of different storage times and extraction methods (supercritical fluid (SFE) or microwave-assisted (MAE)) for 202 samples of primary sludge, waste activated sludge (WAS), raw sludge, and aerobically/anaerobically digested biosolids collected from Canadian municipal wastewater treatment plants. Sixty-three air-dried samples were extracted by SFE, and 139 air-dried, centrifuged, or filtered samples were extracted by MAE. The mean surrogate recoveries were 89% (standard deviation (SD)=11%) for d(10)-anthracene by SFE and 88% (SD=14%) for d(10)-phenanthrene by MAE. Storage study results showed that PNM concentrations changed by a mean of 7% and 9% for primary sludge and WAS respectively after four weeks and decreased up to 25% after 13.5 months of storage in amber glass containers at -18 degrees C. Air-drying of sludge at room temperature caused losses of about 50% of PNM concentrations compared to centrifugation. The proportions of PNMs present in the liquid phase of sludge samples were less than 5% compared to proportions in the sludge solids. The most complete liquid-solid separation was achieved by filtration of frozen/thawed sludge samples, producing a liquid phase that contained less than 1% of the total musk content of the sample.

A gas chromatographic method for the determination of resin and fatty acids in sediments is described. In this procedure, the sediment sample was air-dried and soxhlet-extracted with a mixture of acetone—methanol (88:12, v/v) in the presence of hydrochloric acid. The acids extracted were converted into their pentafluorobenzyl esters and were then cleaned up on a deactivated silica gel column. Final analysis was performed on either a DB-17 or a DB-5 capillary column with electron-capture detection. Quantitative recovery was obtained from fortified sediments for all acids except palustric, neoabietic and levopimaric acids. The detection limit of all acids in this method was 0.1 μg/g based on 1 g of sample. This procedure has been successfully applied to the monitoring of resin and fatty acids in sediment samples collected in the vicinity of several Canadian pulp mill locations.