Monitoring alkylphenols in water using the polar organic chemical integrative sampler (POCIS): determining sampling rates via the extraction of PES membranes and Oasis beads

Polar organic chemical integrative samplers (POCIS) have previously been used to monitor alkylphenol (AP) contamination in water and produced water. However, only the sorbent receiving phase of the POCIS (Oasis beads) is traditionally analyzed, thus limiting the use of POCIS for monitoring a range of APs with varying hydrophobicity. Here a “pharmaceutical” POCIS was calibrated in the laboratory using a static renewal setup for APs (from 2-ethylphenol to 4-n-nonylphenol) with varying hydrophobicity (log Kow between 2.47 and 5.76). The POCIS sampler was calibrated over its 28 day integrative regime and sampling rates (Rs) were determined. Uptake was shown to be a function of AP hydrophobicity where compounds with log Kow < 4 were preferentially accumulated in Oasis beads, and compounds with log Kow > 5 were preferentially accumulated in the PES membranes. A lag phase (over a 24 h period) before uptake in to the PES membranes occurred was evident. This work demonstrates that the analysis of both POCIS phases is vital in order to correctly determine environmentally relevant concentrations owing to the fact that for APs with log Kow ≤ 4 uptake, to the PES membranes and the Oasis beads, involves different processes compared to APs with log Kow ≥ 4. The extraction of both the POCIS matrices is thus recommended in order to assess the concentration of hydrophobic APs (log Kow ≥ 4), as well as hydrophilic APs, most effectively. © 2017 Elsevier Lt

Passive sampling of wastewater as a tool for the long-term monitoring of community exposure: Illicit and prescription drug trends as a proof of concept

Embargo until 20 May 2019.A passive sampling device, the Polar Organic Chemical Integrative Sampler (POCIS), was calibrated in-situ over a 4-week period in Oslo (Norway) for 10 illicit drugs and pharmaceuticals with the goal of developing an approach for monitoring long-term wastewater drug loads. The calibrations were performed in triplicate using three different overlapping calibration sets under changing environmental conditions that allowed the uncertainty of the sampling rates to be evaluated. All 10 compounds exhibited linear uptake kinetics and provided sampling rates of between 0.023 and 0.192 L d−1. POCIS were deployed for consecutive 2-week periods during 2012 and 2013 and the calculated time-weighted average (TWA) concentrations used to define different drug use trends. The relative uncertainty related to the POCIS data was approximately 40% and, except for citalopram, 85% of all the long-term measurements of pharmaceuticals were within the confidence interval levels calculated to evaluate the effects of changing environmental conditions on the TWA estimations. POCIS was demonstrated to be sufficiently robust to provide reliable annual drug use estimates with a smaller number of samplers (n = 24) than recommended for active sampling (n = 56) within an acceptable level of sample size related uncertainty < 10%. POCIS is demonstrated to be a valuable and reliable tool for the long-term monitoring of certain drugs and pharmaceuticals within a defined population.acceptedVersio

Atrazine contamination at the watershed scale and environmental factors affecting sampling rates of the polar organic chemical integrative sampler (POCIS)

AbstractPolar organic chemical integrative samplers (POCIS) were used to estimate atrazine contamination at 24 stream/river sites located across a watershed with land use ranging from 6.7 to 97.4% annual crops and surface water nitrate concentrations ranging from 3 to 5404 μg/L. A gradient of atrazine contamination spanning two orders of magnitude was observed over two POCIS deployments of 28 d and was positively correlated with measures of agricultural intensity. The metabolite desisopropyl atrazine was used as a performance reference compound in field calibration studies. Sampling rates were similar between field sites but differed seasonally. Temperature had a significant effect on sampling rates while other environmental variables, including water velocity, appeared to have no effect on sampling rates. A performance reference compound approach showed potential in evaluating spatial and temporal differences in field sampling rates and as a tool for further understanding processes governing uptake of polar compounds by POCIS

Using Passive Samplers to Track per and Polyfluoroalkyl Substances (PFAS) Emissions From the Paper Industry: Laboratory Calibration and Field Verification

Per and polyfluoroalkyl substances (PFAS) are becoming more stringently regulated and as such, a more diverse suite of environmental monitoring methods is needed. In this work a polar organic chemical integrative sampler (POCIS) with a nylon membrane and a combination of Oasis WAX and Fluoroflash® sorbents was calibrated in the laboratory and deployed in the field. A static renewal system was used to determine sampling rates for 12 PFAS which ranged between 0.69 ± 0.27 to 5.68 ± 1.80 L/day. POCIS devices were deployed for 10 days in lake Tyrifjorden, Norway which is known to be contaminated by a closed down factory producing paper products, in order to track the evolution of the PFAS contamination in a river system draining into the lake. Th sampling campaign enabled the stretch of the river which was responsible for the emissions of PFAS to lake Tyrifjorden to be identified. Freely dissolved concentrations determined with the POCIS were lowest at the site considered to reflect a diffuse PFAS contamination and highest at the site located downstream the factory. Perfluorooctanesulfonic acid (PFOS), perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonamidoacetic acid (EtFOSAA) dominated the concentration profile at this site. Emissions of PFAS to lake Tyrifjorden were estimated to be 3.96 g/day for the sum of the 12 investigated PFAS.publishedVersio

Measuring the occurrence of antibiotics in surface water adjacent to cattle grazing areas using passive samplers

A wide variety of antibiotics and other pharmaceuticals are used in livestock production systems and residues passed to the environment, often unmetabolized, after use and excretion. Antibiotic residuesmay be transported frommanure-treated soils via runoff and are also capable of reaching surface and groundwater systems through a variety of pathways. The occurrence and persistence of antibiotics in the environment is a concern due to the potential for ecological effects and proliferation of environmental antibiotic resistance in pathogenic organisms. In the present study, the occurrence and seasonal variation of 24 commonly-used veterinary antibiotics was evaluated in surface water adjacent to several livestock production systems using Polar Organic Chemical Integrative Samplers (POCIS). Uptake rates for all compounds, nine of which have not been previously reported, were measured in the laboratory to permit estimation of changes in the time-weighted average (TWA) antibiotic concentrations during exposure. The antibiotics detected in POCIS extracts included sulfadimethoxine, sulfamethoxazole, trimethoprim, sulfamerazine, sulfadiazine, lincomycin, erythromycin, erythromycin anhydro- and monensin. The maximum TWA concentration belonged to sulfadiazine (25 ng/L) in the August– September sampling period and coincided with the highest number of precipitation events.With the exception of monensin that showed an increase in concentration over the stream path, none of the detected antibiotics were prescribed to livestock at the facility. The detection of antibiotics not prescribed by the facility may be attributable to the environmental persistence of previously used antibiotics, transfer by wind from other nearby livestock production sites or industrial uses, and/or the natural production of some antibiotics

Pharmaceuticals And Personal Care Products: Emerging Contaminants In Aquatic Ecosystems

In recent years, the presence of pharmaceuticals and personal care products (PPCPs) in aquatic systems has led to research on their fate and effects. PPCPs have been found in mixture in wastewater effluents, surface, ground, and drinking water at low concentrations from areas of intense urbanization. Although adverse effects to human health from the current environmental concentrations are unlikely, the impacts to ecological receptors are not clear. We performed field and laboratory studies to quantify and evaluate effects of PPCPs on fish. First, a field study was conducted at the Baca National Wildlife Refuge, Colorado (2010-2012) because a portion of the Refuge receives discharges of treated water from the Aspen Wastewater Treatment Plant (WWTP). Water and fish samples were used to quantify the presence of PPCPs in surface and wastewater effluents, and to determine the potential impact of PPCPs in fish communities (using histology and gene expression analysis). We focused on fathead minnows ( Pimephales promelas ) since they have been the subject of relevant ecotoxicological research and are a good sentinel species. A total of 120 analytes were quantified using a combination of grab samples and polar organic chemical integrative samplers (POCIS). Although no PPCPs were detected from the grab samples, POCIS allowed for the detection of PPCPs in all our fish sites. High concentrations of N,N-Diethyl-meta-toluamide (DEET) and thirteen pharmaceuticals (triclocarban, triclosan, gemfibrozil, ibuprofen, progesterone, diphenhydramine, atenolol, caffeine, trimethoprim, levorphanol, cannabidiol, tetrahydrocannabinol (THC), and naproxen) were detected in all fish sites, including the reference site. Cellular changes in gonads and livers and significant changes in gene expression (steroidogenic acute regulatory protein, star and androgen receptor, ar ) were observed from female and male fathead minnows sampled from creeks contaminated with PPCPs. However, because we could not identify a clean reference site, we cannot affirm these changes are due to PPCP exposure. We conclude that POCIS is a sensitive method for the detection and quantification of PPCPs in small streams. Additional studies at the Refuge are needed to better understand the ecological impacts of PPCPs. Next, we conducted a laboratory study using the same PPCPs found in our field study and exposed adult fathead minnows for 48 hr to the highest environmental concentration of each chemical. Our goal was to evaluate molecular changes of a suite of genes known to respond after exposure to chemicals affecting lipid metabolism, and the endocrine and nervous systems. Fish were exposed to triclocarban (1.4 μg/L), DEET (0.6 μg/L) or to a PPCP mixture consisting of: atenolol (1.5 μg/L), caffeine (0.25 μg/L), diphenhydramine (0.1 μg/L), gemfibrozil (1.5 μg/L), ibuprofen (0.4 μg/L), naproxen (1.6 μg/L), triclosan (2.3 μg/L), progesterone (0.2 μg/L), triclocarban (1.4 μg/L), and DEET (0.6 μg/L). Vitellogenin ( vtg ) was up-regulated in livers of females and males exposed to triclocarban. Also, an up-regulation of hepatic lipoprotein (lpl ) and a down-regulation of ar and star were observed in testes. The group treated with DEET only showed a significant decrease in ar in females. In contrast, the PPCP mixture down-regulated vtg in females and males, and expression of estrogen receptor alpha (erα ), star, and thyroid hormone receptor alpha 1 (thra1 ) in testes. Our results show the molecular `estrogenic\u27 effects of triclocarban are eliminated (males) or reversed (females) when dosed in conjunction with several other PPCPs, once again showing that results from single exposures could be vastly different from those observed with mixtures

Passive Sampling of Organic Contaminants as a Novel Approach to Monitor Seawater Quality in Aquarium Ocean Tanks

The determination of trace pollutants in seawater is challenging, and sampling is a crucial step in the entire analytical process. Passive samplers combine in situ sampling and preconcentration, thus limiting the tedious treatment steps of the conventional sampling methods. Their use to monitor water quality in confined marine environment could bring several advantages. In this work, the presence of organic contaminants at trace and ultra-trace levels was assessed in the Genoa Aquarium supply-and-treated water using Polar Organic Integrative Samplers (POCIS). Both untargeted gas chromatography-mass spectrometry and targeted liquid chromatography-tandem mass spectrometry were employed. The untargeted approach showed the presence of hydrocarbons, diphenyl sulfone and 2,4-di-tert-butyl-phenol. Only hydrocarbons were detected in all the samples. Nineteen emerging contaminants, belonging to different classes (pharmaceuticals, UV-filters, hormones and perfluorinated compounds), were selected for the target analysis. Thirteen analytes were detected, mainly in supply water, even though the majority of them were below the quantitation limit. It is worthy to note that two of the detected UV-filters had never been reported in seawater using the POCIS samplers. The comparison of the analytes detected in supply and treated water indicated a good performance of the Aquarium water treatment system in the abatement of seawater contaminants

Current-Use Pesticides in New Zealand Streams: Comparing Results From Grab Samples and Three Types of Passive Samplers

New Zealand uses more than a ton of pesticides each year; many of these are mobile, relatively persistent, and can make their way into waterways. While considerable effort goes into monitoring nutrients in agricultural streams and programs exist to monitor pesticides in groundwater, very little is known about pesticide detection frequencies, concentrations, or their potential impacts in New Zealand streams. We used the ‘Polar Organic Chemical Integrative Sampler’ (POCIS) approach and grab water sampling to survey pesticide concentrations in 36 agricultural streams in Waikato, Canterbury, Otago and Southland during a period of stable stream flows in Austral summer 2017/18. We employed a new approach for calculating site-specific POCIS sampling rates. We also tested two novel passive samplers designed to reduce the effects of hydrodynamic conditions on sampling rates: the ‘Organic-Diffusive Gradients in Thin Films’ (o-DGT) aquatic passive sampler and microporous polyethylene tubes (MPTs) filled with Strata-X sorbent. Multiple pesticides were found at most sites; two or more were detected at 78% of sites, three or more at 69% of sites, and four or more at 39% of sites. Chlorpyrifos concentrations were the highest, with a maximum concentration of 180 ng/L. Concentrations of the other pesticides were generally below 20 ng/L. Mean concentrations of individual pesticides were not correlated with in-stream nutrient concentrations. The majority of pesticides were detected most frequently in POCIS, presumably due to its higher sampling rate and the relatively low concentrations of these pesticides. In contrast, chlorpyrifos was most frequently detected in grab samples. Chlorpyrifos concentrations at two sites were above the 21-day chronic ‘No Observable Effect Concentration’ (NOEC) values for fish and another two sites had concentrations greater than 50% of the NOEC. Otherwise, concentrations were well-below NOEC values, but close to the New Zealand Environmental Exposure Limits in several cases

Estrogenic Compounds Downstream from Three Small Cities in Eastern Nebraska: Occurrence and Biological Effect

Recent studies have detected estrogenic compounds in surface waters in North America and Europe. Furthermore, the presence of estrogenic compounds in surface waters has been attributed, in some cases, to the discharge of wastewater treatment plant (WWTP) effluent. The primary objective of the current study was to determine if WWTP effluent contributes estrogens to the surface waters of Nebraska. A second objective of this study was to determine if estrogens were found in concentrations sufficient enough to manifest feminizing effects on fish. These objectives were satisfied by deploying polar organic chemical integrative samplers (POCIS) and caged fathead minnows at eight field sites. Deployment sites included: three reference sites (Pawnee Creek, the Little Blue River, and the Middle Loup River), two sites upstream of the WWTPs at Grand Island and Columbus, and three sites downstream of the WWTPs at Grand Island, Columbus, and Hastings. Following the seven day deployments, POCIS extracts were analyzed for estrone, 17β-estradiol, estriol and 17α-ethinylestradiol using liquid chromatography tandem mass spectrometry (LC/MS/MS). 17β-estradiol was detected in POCIS from six of the eight field sites with the greatest quantities recovered in POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrone was detected only in the POCIS deployed downstream from the Grand Island and Hastings WWTPs. Estrogenic effects were detected in caged minnows analyzed for the hepatic mRNA expression of two estrogen- responsive genes, vitellogenin (vg1) and estrogen receptor α (ERα). Fish deployed at the site where the greatest quantities of estrogens were recovered (Hastings) had significantly higher expression of both vg1 and ERα than fish deployed at any of the other sites. These results confirm that WWTP effluent contributes biologically significant levels of estrogens to Nebraska surface waters