Compounds In Wastewater Effluents Research Articles

Identification of antimicrobial and glucocorticoid compounds in wastewater effluents with effect-directed analysis

Pharmaceuticals, such as glucocorticoids and antibiotics, are inadequately removed from wastewater and may cause unwanted toxic effects in the receiving environment. This study aimed to identify contaminants of emerging concern in wastewater effluent with antimicrobial or glucocorticoid activity by applying effect-directed analysis (EDA). Effluent samples from six wastewater treatment plants (WWTPs) in the Netherlands were collected and analyzed with unfractionated and fractionated bioassay testing. Per sample, 80 fractions were collected and in parallel high-resolution mass spectrometry (HRMS) data were recorded for suspect and nontarget screening. The antimicrobial activity of the effluents was determined with an antibiotics assay and ranged from 298 to 711 ng azithromycin equivalents·L−1. Macrolide antibiotics were identified in each effluent and found to significantly contribute to the antimicrobial activity of each sample. Agonistic glucocorticoid activity determined with the GR-CALUX assay ranged from 98.1 to 286 ng dexamethasone equivalents·L−1. Bioassay testing of several tentatively identified compounds to confirm their activity revealed inactivity in the assay or the incorrect identification of a feature. Effluent concentrations of glucocorticoid active compounds were estimated from the fractionated GR-CALUX bioassay response. Subsequently, the biological and chemical detection limits were compared and a sensitivity gap between the two monitoring approaches was identified. Overall, these results emphasize that combining sensitive effect-based testing with chemical analysis can more accurately reflect environmental exposure and risk than chemical analysis alone.

Calibration of a microporous polyethylene tube passive sampler for polar organic compounds in wastewater effluent

Water resources are vulnerable to contamination from polar organic compounds (POCs) originating from sources such as wastewater effluent. Two configurations of a microporous polyethylene tube (MPT) passive sampler were investigated for the time-integrative detection and quantification of POCs in effluent. One configuration contained the polymeric reversed phase sorbent Strata-X (SX) and the other Strata-X suspended in agarose gel (SX-Gel). These were deployed for up to 29 days and analysed for forty-nine POCs including pesticides, pharmaceuticals and personal care products (PPCPs) together with illicit drugs. Complementary composite samples were collected on days 6, 12, 20 and 26 representing the previous 24 h. Thirty-eight contaminants were detected in composite samples and MPT extracts, with MPT sampling rates (Rs) for 11 pesticides and 9 PPCPs/drugs ranging from 0.81 to 10.32 mL d−1 in SX and 1.35–32.83 mL d−1 in SX-Gel. Half-times to equilibrium of contaminants with the SX and SX-Gel equipped samplers ranged from two days to >29 days. MPT (SX) samplers were also deployed at 10 wastewater treatment effluent discharge sites across Australia for 7 days (again with complementary composite samples), to validate the sampler performance under varying conditions. Extracts from these MPTs detected 48 contaminants in comparison with 46 in composite samples, with concentrations ranging from 0.1 to 138 ng mL−1. An advantage of the MPT was preconcentration of contaminants, resulting in extract levels often markedly above instrument analytical detection limits. The validation study demonstrated a high correlation between accumulated contaminant mass in the MPTs and wastewater concentrations from composite samples (r2 > 0.70, where concentrations in composite samples were > 3× LOD). The MPT sampler shows promise as a sensitive tool for detecting POCs at trace levels in wastewater effluent and also quantifying these levels if temporal concentration variations are not significant.

Identification of Antimicrobial and Glucocorticoid Compounds in Wastewater Effluents with Effect-Directed Analysis

Identification of Antimicrobial and Glucocorticoid Compounds in Wastewater Effluents with Effect-Directed Analysis

Detection of anticancer drugs in wastewater effluents: Grab versus passive sampling

The occurrence of six anticancer drugs was evaluated in wastewater effluents. Several grab samples from wastewater effluent were collected throughout a year. Capecitabine, cyclophosphamide and ifosfamide were detected at concentrations ranging from 8 to 46 ng·L−1. Capecitabine was detected in all the sampling events whereas cyclophosphamide and ifosfamide were detected less frequently.Additionally, the suitability of using pharmaceutical-polar organic chemical integrative samplers (POCIS) to monitor the target drugs in wastewater effluents was assessed. Capecitabine, ifosfamide and cyclophosphamide were detected with POCIS and showed a linear uptake over 15 days. The sampling rates, determined in situ, were used to estimate time-weighted average concentrations. A good correlation was found between the concentration of capecitabine detected with POCIS deployed during five days (32 ± 1 ng·L−1) and the average concentrations obtained in grab samples. The use of passive samplers has advantages over grab samples: easier analysis, less time and costs associated with the analytical method. Passive samplers also provide a time-weighted information about the concentration of pollutants in the aquatic environment. However, information may be lost when the concentration of the target compounds in wastewater effluents is low and the passive samplers are deployed for a short time.

Occurrence, removal and environmental risk of markers of five drugs of abuse in urban wastewater systems in South Australia.

The occurrence and fate of five drugs of abuse in raw influent and treated effluent wastewater were investigated over a period of 1year in the Adelaide region of South Australia. Four wastewater treatment plants were chosen for this study and monitored for five drugs which included cocaine in the form of its metabolite benzoylecgonine (BE), methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA) and two opioids (codeine and morphine) during the period April 2016 to February 2017. Alongside concentrations in raw sewage, the levels of drugs in the treated effluent were assessed and removal efficiencies were calculated. Drug concentrations were measured by mixed-mode solid phase extraction and liquid chromatography coupled to a quadrupole mass spectrometer. Drug concentrations detected in the raw wastewater ranged from 7 to 6510ng/L and < LOD to 4264ng/L in treated effluent samples. Drug removal rates varied seasonally and spatially. The mass loads of drugs discharged into the environment were in descending order: codeine > methamphetamine > morphine > MDMA > BE. Results showed that all the targeted drugs were on average incompletely removed by wastewater treatment, with removal performance highest for morphine (94%) and lowest for MDMA (58%). A screening-level environmental risk assessment was subsequently performed for the drugs based on effluent wastewater concentrations. Based on calculated risk quotients, overall environmental risk for these compounds appears low, with codeine and methamphetamine likely to pose the greatest potential risk to receiving environments. Given the recognised limitations of current ecotoxicological models and risk assessment methods for these and other pharmaceutical drugs, the potential for environmental impacts associated with the continuous discharge of these compounds in wastewater effluents should not be overlooked.

Identification of residual non-biodegradable organic compounds in wastewater effluent after two-stage biochemical treatment

AbstractThe main non-biodegradable compounds (soluble microbial product – SMP) of wastewater from the Maotai aromatic factories, located in the Chishui river region, were analyzed by UV spectroscopy, and by solid-phase extraction followed by gas chromatography coupled to mass spectrometry, after a two-stage biochemical treatment. The UV-Vis spectra revealed that the wastewater contained two double-bonds in conjugated systems (conjugated diene or α, β- unsaturated ketone, etc.) and simple non-conjugated chromophores containing n electrons from carbonyl groups or the like. The residual organic non-biodegradable substances were identified using SPE-GC/MS analysis as complex polymers containing hydroxyl, carbonyl, and carboxyl functional groups with multiple connections to either benzene rings or heterocyclic rings. As these compounds are difficult to remove by conventional biochemical treatments, our findings provide a scientific basis for the design of efficient new strategies to remove SMP from wastewater.

Rapid direct injection LC-MS/MS method for analysis of prioritized indicator compounds in wastewater effluent

Trace organic compounds (TOrCs) have been detected in drinking water sources for several years, raising concerns due to their potential risks to public health.

Widespread occurrence of neuro-active pharmaceuticals and metabolites in 24 Minnesota rivers and wastewaters

Concentrations of 17 neuro-active pharmaceuticals and their major metabolites (bupropion, hydroxy-bupropion, erythro-hydrobupropion, threo-hydrobupropion, carbamazepine, 10,11,-dihydro-10,11,-dihydroxycarbamazepine, 10-hydroxy-carbamazepine, citalopram, N-desmethyl-citalopram, fluoxetine, norfluoxetine, gabapentin, lamotrigine, 2-N-glucuronide-lamotrigine, oxcarbazepine, venlafaxine and O-desmethyl-venlafaxine), were measured in treated wastewater and receiving surface waters from 24 locations across Minnesota, USA. The analysis of upstream and downstream sampling sites indicated that the wastewater treatment plants were the major source of the neuro-active pharmaceuticals and associated metabolites in surface waters of Minnesota. Concentrations of parent compound and the associated metabolite varied substantially between treatment plants (concentrations±standard deviation of the parent compound relative to its major metabolite) as illustrated by the following examples; bupropion and hydrobupropion 700±1000ngL−1, 2100±1700ngL−1, carbamazepine and 10-hydroxy-carbamazepine 480±380ngL−1, 360±400ngL−1, venlafaxine and O-desmethyl-venlafaxine 1400±1300ngL−1, 1800±2300ngL−1. Metabolites of the neuro-active compounds were commonly found at higher or comparable concentrations to the parent compounds in wastewater effluent and the receiving surface water. Neuro-active pharmaceuticals and associated metabolites were detected only sporadically in samples upstream from the effluent outfall. Metabolite to parent ratios were used to evaluate transformation, and we determined that ratios in wastewater were much lower than those reported in urine, indicating that the metabolites are relatively more labile than the parent compounds in the treatment plants and in receiving waters. The widespread occurrence of neuro-active pharmaceuticals and metabolites in Minnesota effluents and surface waters indicate that this is likely a global environmental issue, and further understanding of the environmental fate and impacts of these compounds is warranted.

Priority organic compounds in wastewater effluents from the Mediterranean and Atlantic basins of Andalusia (Spain)

A comprehensive survey of the occurrence of organic compounds in 30 wastewater (WW) effluent samples from 21 urban wastewater treatment plants (WWTPs) from both secondary and tertiary treatments was carried out in the Mediterranean and Atlantic basins of the Andalusia region (south of Spain). For each sample, a total of 226 compounds including pesticides and some transformation products, polycyclic aromatic hydrocarbons (PAHs), phenolic compounds and volatile organic compounds (VOCs) were monitored with the aim of evaluating their occurrence in urban WW effluents. Compounds belonging to each class were detected. Among pesticides, insecticides such as clorfenvinphos and diazinon as well as herbicides such as diuron, sebuthylazine, terbuthylazine and terbuthylazine desethyl were the most frequently detected. The ubiquity of some compounds such as fluorene, phenanthrene and pyrene was also demonstrated. The compounds evaluated were detected at low concentrations (in general below 1 μg L(-1)), except 4-tert-octylphenol, which was detected at extremely high concentrations (up to 443 μg L(-1)). PAHs and VOCs were the compounds most frequently detected in the assayed samples, and they are the main sources of contamination in WWTPs, as well as some herbicides and transformation products.

Parts per trillion level determination of endocrine-disrupting chlorinated compounds in river water and wastewater effluent by stir-bar-sorptive extraction followed by gas chromatography–triple quadrupole mass spectrometry

A new analytical method using stir-bar-sorptive extraction (SBSE) followed by liquid desorption (LD) and gas chromatography with triple-quadrupole mass spectrometric detection (GC-QqQ-MS-MS) has been used for quantitative determination of 25 chlorinated endocrine-disrupting compounds (EDCs) in river water and wastewater. The experimental conditions affecting the SBSE-LD performance were studied and are discussed in detail. Results from systematic assay revealed that a 100-mL water sample, stir bars coated with 47 μL PDMS, an extraction time of 14 h (at 900 rpm), 5 % MeOH as modifier and 10 % NaCl resulted in the best analytical recovery of all the target compounds studied. Use of 1:1 ACN-MeOH as back-extraction solvent and two successive sonication steps, each for 5 min, resulted in the best performance for monitoring EDCs in water matrices. The method detection limits for most of the target compounds were very good- ≤ 2 ng L(-1) and ≤10 ng L(-1) for river water and wastewater effluents respectively. Experimental recovery for all the compounds was >70 %, with the exception of simazine for which recovery from the matrix was 65 %. Signal enhancement observed for a few of the compounds in wastewater effluents was managed by use of matrix-matched standards and different injection liners. The method was successfully used for analysis of river water samples from Henares River (Spain) and wastewater effluent samples from wastewater-treatment plants (WWTP). Eleven of the 25 compounds studied were detected in both river water and wastewater effluents. Terbutylazine and methoxychlor were detected in almost all the river water and effluent samples; amounts varied between 37-58.5 ng L(-1) and 15.2-46.8 ng L(-1), respectively. This method was shown enable reliable, effective, and sensitive monitoring of chlorinated EDCs at nanogram levels in surface water and wastewater effluent.

Enhanced Biodegradation of Carbamazepine after UV/H2O2 Advanced Oxidation

Carbamazepine is one of the most persistent pharmaceutical compounds in wastewater effluents due to its resistance to biodegradation-based conventional treatment. Advanced oxidation can efficiently degrade carbamazepine, but the toxicity and persistence of the oxidation products may be more relevant than the parent. This study sets out to determine whether the products of advanced oxidation of carbamazepine can be biotransformed and ultimately mineralized by developing a novel methodology to assess these sequential treatment processes. The methodology traces the transformation products of the (14)C-labeled carbamazepine during UV/hydrogen peroxide advanced oxidation and subsequent biotransformation by mixed, undefined cultures using liquid scintillation counting and liquid chromatography with radioactivity, mass spectrometry, and UV detectors. The results show that the oxidation byproducts of carbamazepine containing a hydroxyl or carbonyl group can be fully mineralized by a mixed bacterial inoculum. A tertiary treatment approach that includes oxidation and biotransformation has the potential to synergistically mineralize persistent pharmaceutical compounds in wastewater treatment plant effluents. The methodology developed for this study can be applied to assess the mineralization potential of other persistent organic contaminants.

Occurrence and persistence of organic emerging contaminants and priority pollutants in five sewage treatment plants of Spain: Two years pilot survey monitoring

This work summarized all results obtained during almost two-years of a monitoring programme carried out in five municipal sewage treatment plants (STPs) located in the north, centre and south-east of Spain. The study evaluated the occurrence and persistence of a group of 100 organic compounds belonging to several chemical groups (pharmaceuticals, personal care products, pesticides and metabolites). The average removal efficiencies of the STPs studied varied from 20% (erythromycin) to 99% (acetaminophen). In analysed samples, we identified a large number of compounds at mean range concentrations between 7–59,495 ng/L and 5–32,720 ng/L for influent and effluent samples, respectively. This study also identified 20 of the mostly detected and persistent compounds in wastewater effluent, of which hydrochlorothiazide, atenolol, gemfibrozil, galaxolide and three metabolites (fenofibric acid, 4-AAA and 4-FAA), presented the highest average contribution percentages, in relation to the total load of contaminants for the different STPs effluent studied.

Odorous Compounds in Municipal Wastewater Effluent and Potable Water Reuse Systems

The presence of effluent-derived compounds with low odor thresholds can compromise the aesthetics of drinking water. The potent odorants 2,4,6-trichloroanisole and geosmin dominated the profile of odorous compounds in wastewater effluent with concentrations up to 2 orders of magnitude above their threshold values. Additional odorous compounds (e.g., vanillin, methylnaphthalenes, 2-pyrrolidone) also were identified in wastewater effluent by gas chromatography coupled with mass-spectrometry and olfactometry detection. Full-scale advanced treatment plants equipped with reverse osmosis membranes decreased odorant concentrations considerably, but several compounds were still present at concentrations above their odor thresholds after treatment. Other advanced treatment processes, including ozonation followed by biological activated carbon and UV/H(2)O(2) also removed effluent-derived odorants. However, no single treatment technology alone was able to reduce all odorant concentrations below their odor threshold values. To avoid the presence of odorous compounds in drinking water derived from wastewater effluent, it is necessary to apply multiple barriers during advanced treatment or to dilute wastewater effluent with water from other sources.

Multiresidue method for the analysis of emerging contaminants in wastewater by ultra performance liquid chromatography–time-of-flight mass spectrometry

A multiresidue method for screening of emerging contaminants in aquatic environments was developed. The method was based on sample pretreatment with solid phase extraction (SPE) and analysis with an ultra performance liquid chromatograph–time-of-flight mass spectrometer (UPLC–TOF-MS). The method was optimized and tested with standard solutions of model compounds containing 84 pesticides and pharmaceuticals. Four different SPE sorbents were evaluated to gain maximum recovery for the analytes. For the final procedure a combination of two different sorbents was chosen. In spite of high matrix suppression, the method quantification limits (MQLs) were acceptable. Therefore, the method can be used for screening known target compounds. The applicability of the method for posttarget and nontarget screening will be reported later. To preliminarily assess the quantitative performance of the method, some compounds in wastewater effluent were quantified using the standard addition method. Three pesticides and eight pharmaceuticals were found in concentrations up to ∼2200 ng/L.

Determination of 19 volatile organic compounds in wastewater effluents from different treatments by purge and trap followed by gas-chromatography coupled to mass spectrometry

A rapid and simple methodology based on purge and trap with gas-chromatography coupled to triple quadrupole mass spectrometry has been developed for the analysis of 19 volatile organic compounds (VOCs) in wastewater (WW) effluents from four different treatments. The determination was carried out in the raw WW effluents, which were not submitted to any pre-treatment (e.g., filtration). A matrix effect study was also performed, concluding that solvent calibration was adequate to quantify VOCs in WW effluent samples containing a variety of suspended particulate matter. Adequate validation parameters were obtained with recovery values in the range 73-124% and precision values lower than 24%. Limits of quantification were established at 0.1 μg L(-1) for all VOCs. The proposed method was applied to the analysis of WW samples, detecting chloroform and toluene at concentrations ranging from 0.1 to 4.80 μg L(-1).

Are Reuse Quality Standards Too High, or Are Potable Water Quality Standards Too Lax?

When reports about nanogram/liter concentrations of compounds in wastewater effluent are published, the public expresses concern and raises questions about health effects of the concentrations. A utility must attempt to define potential human health effects from compounds at concentrations several orders of magnitude lower than currently established maximum contaminant levels (MCLs) in community potable water. This article examines public perception and offers suggestions to utility staff responsible for providing answers to the public. It also discusses the “system” that evaluates risk and establishes MCLs and Candidate Contaminant Lists for potable water.

Identification of estrogenic compounds in wastewater effluent

In order to identify the dominant contributors to estrogenic activity in environmental waters, a comprehensive fractionation method using silica gel column chromatography, combined with recombinant yeast assay for detecting estrogenic activity and with gas chromatography-mass spectrometry for quantifying endocrine disruptors and natural estrogens, was developed. The method was applied to the municipal sewage treatment plant (STP) secondary effluent discharged to the Tamagawa River in Tokyo, Japan, where endocrine disruption was observed in wild carp. The instrumental analysis demonstrated that averaged concentrations of nonylphenol, bisphenol A, estrone (E1), and 17beta-estradiol (E2) were 564 +/- 127, 27 +/- 19, 33 +/- 11, and 4.6 +/- 3.0 ng/L, respectively. Based on the concentration and relative potency of these compounds, the natural estrogens E1 and E2 represented more than 98% of the total estrogen equivalent concentration (EEQ) in the STP effluent, while the contribution of phenolic compounds to total EEQ was less than 2%. Estrogenic activities associated with the dissolved phase of the effluent samples were detected by a recombinant yeast assay. By using silica gel column chromatography, the dissolved phase was separated into several fractions that were subjected to the bioassay. The polar fractions exhibited estrogenic activity. The greatest estrogenic activity was found in a polar fraction containing E1 and E2 and represented 66 to 88% of the total estrogenic activities estimated from the bioassay data. These results lead to the conclusion that E1 and E2 were the dominant environmental estrogens in the STP effluent, but a significant contribution to estrogenic activities stems from unidentified components in the effluents.