Polar Organic Chemical Integrative Samplers Extracts Research Articles

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes.

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of invitro bioassays (focused on estrogenic activity) and invivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total invitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Complex mixtures of Pesticides in Midwest U.S. streams indicated by POCIS time-integrating samplers

The Midwest United States is an intensely agricultural region where pesticides in streams pose risks to aquatic biota, but temporal variability in pesticide concentrations makes characterization of their exposure to organisms challenging. To compensate for the effects of temporal variability, we deployed polar organic chemical integrative samplers (POCIS) in 100 small streams across the Midwest for about 5 weeks during summer 2013 and analyzed the extracts for 227 pesticide compounds. Analysis of water samples collected weekly for pesticides during POCIS deployment allowed for comparison of POCIS results with periodic water-sampling results. The median number of pesticides detected in POCIS extracts was 62, and 141 compounds were detected at least once, indicating a high level of pesticide contamination of streams in the region. Sixty-five of the 141 compounds detected were pesticide degradates. Mean water concentrations estimated using published POCIS sampling rates strongly correlated with means of weekly water samples collected concurrently, however, the POCIS-estimated concentrations generally were lower than the measured water concentrations. Summed herbicide concentrations (units of ng/POCIS) were greater at agricultural sites than at urban sites but summed concentrations of insecticides and fungicides were greater at urban sites. Consistent with these differences, summed concentrations of herbicides correlate to percent cultivated crops in the watersheds and summed concentrations of insecticides and fungicides correlate to percent urban land use. With the exception of malathion concentrations at nine sites, POCIS-estimated water concentrations of pesticides were lower than aquatic-life benchmarks. The POCIS provide an alternative approach to traditional water sampling for characterizing chronic exposure to pesticides in streams across the Midwest region.

A simple recirculating flow system for the calibration of polar organic chemical integrative samplers (POCIS): Effect of flow rate on different water pollutants

A calibration system for POCIS was developed and used to calculate the sampling rates of eight analytes belonging to pesticides, non-steroidal anti-inflammatory drugs and perfluorinated compounds: atrazine, propazine, terbutylazine, diclofenac, ibuprofen, ketoprofen, perfluorooctanoic acid and perfluorooctanesulfonate. Experiments with a linear velocity of 2.0, 5.1, 10.2 and 15.3 cm/s were carried out for 96 h using two different analyte concentrations. POCIS extracts were analyzed by liquid chromatography-tandem mass spectrometry (LC-MS/MS), using multiple reaction monitoring to maximize sensitivity. Results highlighted that the calculated sampling rates are rather constant at the considered concentrations and flow rates. Obtained values of sampling rates were then employed to calculate Time-Weighted Average concentration of the analytes in river and drinking waters.

Point sources of emerging contaminants along the Colorado River Basin: Source water for the arid Southwestern United States

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 samples 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 chemicals 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 30ng/L to 2800ng/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 irrigation along the Colorado River) were in the region of the limit-of-detection (e.g., 10ng/L), but most were below detection limits.

Occurrence and endocrine effects of agrichemicals in a small Nebraska, USA, watershed

The Bow Creek watershed (Nebraska, USA) is dominated by the production of beef cattle and row crops; therefore, surface waters are likely to receive runoff containing steroid hormones and pesticides. The goal of the present study was to determine the occurrence and endocrine effects of agrichemicals in this watershed. To accomplish this, four sites within the watershed-Pearl, Bow, and East Bow Creeks and a site at the confluence with the Missouri River-were selected. In June of 2008, polar organic chemical integrative samplers (POCIS) were deployed at each site, whereas in June of 2009, water and sediment samples were collected. Caged fathead minnows (Pimephales promelas) were deployed at all of the selected sites in both years. Analysis of these samples revealed that steroid hormones were not present; however, pesticides were present in POCIS extracts and water samples. In general, the amount of pesticides was higher in POCIS retrieved from Pearl and Bow Creeks than in POCIS from East Bow Creek and the confluence. This variation between sites appeared to be related to row crop density, as row crop land cover surrounding the Pearl and Bow Creek sites was higher than that surrounding the East Bow and confluence sites. To determine the endocrine effects of agrichemicals within this watershed, the hepatic mRNA expression of vitellogenin and estrogen receptor α (ERα), as well as the gonadal expression of P450 aromatase A, was determined for the caged minnows. Females deployed at East Bow Creek and the confluence experienced decreases in the expression of ERα, suggesting that these females had been defeminized; however, this defeminization could not be attributed to any of the pesticides detected at these sites.

Agrichemicals in nebraska, USA, watersheds: Occurrence and endocrine effects

The objective of the present study was to determine the occurrence and endocrine effects of agrichemicals in four Nebraska, USA, watersheds--the Elkhorn, Platte, Niobrara, and Dismal rivers. Land use in the Elkhorn River and Platte River watersheds is characterized by intense agriculture, including row crop and beef cattle production. In contrast, land within the Niobrara River and Dismal River watersheds consists primarily of grasslands. Polar organic chemical integrative samplers (POCIS) and caged fathead minnows were deployed at a site within each watershed for 7 d. The POCIS were analyzed for pesticides and hormones, while the caged minnows were analyzed for the expression of estrogen- and androgen-responsive genes. Amounts of pesticides recovered in POCIS extracts from the Elkhorn and Platte rivers were higher than those recovered from the Niobrara and Dismal rivers. Furthermore, female minnows deployed in the Elkhorn River experienced significant reductions in expression of two estrogen-responsive genes (vitellogenin and estrogen receptor α) relative to females deployed at the other sites, indicating alterations in endocrine function. However, the defeminization of these females could not be definitely linked to any of the agrichemicals detected in the POCIS recovered from the Elkhorn River.

Reductions in hepatic vitellogenin and estrogen receptor alpha expression by sediments from an agriculturally impacted waterway

Previous studies have reported alterations in the endocrine function of fathead minnows ( Pimephales promelas) collected and deployed in the Elkhorn River. The goal of the current study was to determine whether sediment from the Elkhorn River watershed could act as a source of endocrine-active compounds. To accomplish this, four aquaria containing sexually mature fathead minnows and polar organic chemical integrative samplers (POCIS) were established. The aquaria contained either: (1) laboratory water only, (2) Elkhorn River water only, (3) laboratory water and Elkhorn River sediment or (4) Elkhorn River water and Elkhorn River sediment. Steroid hormones were not detected in the extracts of POCIS or sediment. Pesticides were detected in POCIS extracts from tanks containing Elkhorn River water, but were not detected in the extracts of sediment or POCIS suspended in the tank containing laboratory water and Elkhorn River sediment suggesting that sediments do not act as a significant source of the 14 steroid hormones or 24 pesticides that were analyzed for in the current study. The hepatic mRNA expression of vitellogenin (vtg) and estrogen receptor α (ERα) in fathead minnows from each group was assessed. Female minnows exposed simultaneously to sediment and water collected from the Elkhorn River experienced defeminization as indicated by significant reductions in both vtg and ERα expression. Significant reductions in vtg mRNA expression were also observed in females exposed to laboratory water and Elkhorn River sediment, but not in females exposed to Elkhorn River water only. This finding suggests that exposures to sediments, rather than water, collected from the Elkhorn River lead to the defeminization of females. However, the compound(s) responsible for this effect have yet to be determined.

Estrogenic Compounds Downstream From Three Small Cities in Eastern Nebraska: Occurrence and Biological Effect1

Abstract: 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.

Occurrence and biological effect of exogenous steroids in the Elkhorn River, Nebraska, USA

Recent studies of surface waters in North America, Japan and Europe have reported the presence of steroidogenic agents as contaminants. The current study has three objectives: 1) to determine if steroidogenic compounds are present in the Elkhorn River, 2) to determine if sediments collected from the Elkhorn River can act as a source of steroidogenic compounds to aquatic organisms, and 3) to determine if site-specific biological effects are apparent in the hepatic gene expression of fathead minnows. Evidence was obtained using three approaches: 1) deployment of polar organic chemical integrative samplers (POCIS), 2) deployment of caged fathead minnows, and 3) a laboratory experiment in which POCIS and fish were exposed to sediments from the deployment sites. Deployment sites included: the Elkhorn River immediately downstream from a Nebraska wastewater treatment plant, two waterways (Fisher Creek and Sand Creek) likely to be impacted by runoff from cattle feeding operations, and a reference site unlikely to be impacted by waste water inputs. The POCIS extracts were analyzed for a number of natural steroids and metabolites, as well as four different synthetic steroids: ethinylestradiol, zearalonol, 17β-trenbolone and melengestrol acetate. Estrogenic and androgenic metabolites, as well as progesterone and trace levels of melengestrol acetate were detected in POCIS deployed at each site. POCIS deployed in tanks containing field sediments from the four sites did not accumulate the synthetic steroids except for ethinylestradiol, which was detected in the aquarium containing sediments collected near the wastewater treatment plant. Fish deployed in Sand Creek and at the wastewater treatment plant experienced significantly elevated levels of gene expression for two genes (StAR and P450scc) relative to those deployed in Fisher Creek. Fish exposed to the sediments collected from Sand Creek had significantly higher levels of hepatic StAR and P450scc gene expression than did fish exposed to sediments from the two other field sites, as well as the no-sediment control tank. In conclusion: 1) detectable levels of steroidogenic compounds were detected in passive samplers deployed in the Elkhorn River, 2) sediments do not appear to be a significant source for steroidogenic compounds, and 3) site-specific differences were found in mRNA expression among the different treatment groups of fish; however, a functional explanation for these differences is not readily forthcoming.