Geology topics

Brett R. Blackwell

Publications and source records attributed to Brett R. Blackwell.

15 recordsLinked to original sources

USGS2025

A high efficiency method for the extraction and quantitative analysis of 45 PFAS in whole fish

This study describes and validates a new method for extracting perfluoroalkyl and polyfluoroalkyl substances (PFAS) from whole-body fish tissue, demonstrates that freeze-dry preservation of tissue conserves bioaccumulative PFAS, and details a method demonstration on Lake Michigan fish. While fish filets are more commonly analyzed for their significance to human health, whole fish are useful to determine ecological impacts, but published methods such as EPA 1633 do not produce reliable results for this more challenging matrix. Here we show that lipid removal technology produces clean extracts without the need for solid-phase extraction or evaporative concentration, which often lead to loss of some PFAS. This method achieves an accuracy of 96 ± 9% for the detection of 45 PFAS while also offering benefits of a simple procedure, reduced processing time, and decreased waste generation compared to multistep cleanup and concentration methods. A test of freeze-drying demonstrated that compounds detected in Great Lakes fish were retained, but volatile compounds including sulfonamide precursors and ethanols were lost. To demonstrate field performance, the entire method was applied to whole-fish composites from Lake Michigan. Results from these samples reveal that the PFAS concentration was driven by collection location, while the distribution of PFAS was dictated by fish species.

Environmental Science & Technology↗

USGS2025

Prioritizing chemicals of emerging concern in the Great Lakes Basin using covariance of chemical concentrations and diverse biological responses from a variety of species

The Great Lakes Restoration Initiative aims to protect and restore the nation’s largest freshwater resource, in part, by furthering our understanding of the effects of contaminants of emerging concern (CECs) and chemical mixtures on aquatic and terrestrial organisms. To address this goal, an interagency team conducted field studies at sites along the Maumee River in Ohio, USA, in 2016–2017, monitoring CEC levels along with diverse in vitro and in vivo biological effects in ecologically relevant species (fathead minnows, tree swallows, and golden clams). The objective of the present work was to prioritize the CECs in these studies for further monitoring and assessment by determining if there are patterns in chemical–bioeffect relations across data sets, species, and response types that indicate relatively high or low hazard to aquatic life from CEC exposure. Of the 748 monitored chemicals, 425 were detected and were analyzed for covariance with bioeffects. All 748 chemicals were placed into 10 bins based on their frequencies of monitoring, detection, and covariance with bioeffects across studies and species. We describe how chemicals can be prioritized across bins to aid monitoring and assessment efforts. Our approach using effects-based monitoring data is especially useful for prioritizing chemicals with little or no traditional toxicity testing data. Similar evidence-based prioritizations will allow agencies to more efficiently allocate limited resources to improve the ability to protect aquatic and terrestrial organisms from adverse impacts due to contaminant exposure.

Ohio↗

USGS2025

Public, bottled, and private drinking water: Shared contaminant-mixture exposures and effects challenge

BACKGROUND: Humans are primary drivers of environmental contaminant exposures worldwide, including in drinking-water (DW). In the United States (US), point-of-use DW (POU DW) is supplied via private tapwater (TW, predominantly private wells), public-supply TW, and bottled water (BW). Differences in management, monitoring, and messaging and lack of directly intercomparable exposure data influence the actual and perceived quality and safety of different DW supplies and directly impact consumer decision making. OBJECTIVES: The purpose of this paper is to provide a meta-analysis (quantitative synthesis) of POU DW contaminant mixture exposures and corresponding potential human health effects of private-TW, public-TW, and BW by aggregating exposure results and harmonizing apical health benchmark weighted and bioactivity weighted effects predictions across previous studies by this research group. DISCUSSION: Simultaneous exposures to multiple inorganic and organic contaminants of known or suspected human-health concern are common across all three DW supplies, with substantial variability observed in each and no systematic difference in predicted cumulative risk between supply chains. Differences in contaminant or contaminant class exposures (e.g., trace metals, disinfection byproducts), with important implications for DW quality improvements, were observed and attributed to corresponding differences in regulation and compliance monitoring. CONCLUSION: The results indicate that human-health risks from contaminant exposures are common to and comparable in all three DW supplies, including BW. Importantly, this study’s target analytical coverage, which exceeds that currently feasible for water purveyors or homeowners, nevertheless is a substantial underestimation of the full breadth of contaminant mixtures in the environment and potentially present in DW. Thus, the results emphasize the need for improved understanding of the adverse human-health implications of long-term exposures to low level inorganic /organic contaminant mixtures across all three distribution pipelines and do not support commercial messaging of BW as a systematically safer alternative to public-TW. Regardless of the supply, increased engagement in source-water protection and drinking-water treatment, including consumer point of use treatment, is necessary to reduce risks associated with long-term DW contaminant exposures, especially in vulnerable populations, and to reduce environmental waste and plastics contamination.

Environment International↗

USGS2024

Potential hazards of polycyclic aromatic hydrocarbons in Great Lakes tributaries using water column and porewater passive samplers and sediment wquilibrium partitioning

The potential for polycyclic aromatic hydrocarbon (PAH)-related effects in benthic organisms is commonly estimated from organic carbon-normalized sediment concentrations based on equilibrium partitioning (EqP). Although this approach is useful for screening purposes, it may overestimate PAH bioavailability by orders of magnitude in some sediments, leading to inflated exposure estimates and potentially unnecessary remediation costs. Recently, passive samplers have been shown to provide an accurate assessment of the freely dissolved concentrations of PAHs, and thus their bioavailability and possible biological effects, in sediment porewater and overlying surface water. We used polyethylene passive sampling devices (PEDs) to measure freely dissolved porewater and water column PAH concentrations at 55 Great Lakes (USA/Canada) tributary locations. The potential for PAH-related biological effects using PED concentrations were estimated with multiple approaches by applying EqP, water quality guidelines, and pathway-based biological activity based on in vitro bioassay results from ToxCast. Results based on the PED-based exposure estimates were compared with EqP-derived exposure estimates for concurrently collected sediment samples. The results indicate a potential overestimation of bioavailable PAH concentrations by up to 960-fold using the EqP-based method compared with measurements using PEDs. Even so, PED-based exposure estimates indicate a high potential for PAH-related biological effects at 14 locations. Our findings provide an updated, weight-of-evidence–based site prioritization to help guide possible future monitoring and mitigation efforts.

Illinois, Indiana, Michigan, Minnesota, New York, ↗

USGS2023

Pesticide prioritization by potential biological effects in tributaries of the Laurentian Great Lakes

Watersheds of the Great Lakes Basin (USA/Canada) are highly modified and impacted by human activities including pesticide use. Despite labeling restrictions intended to minimize risks to nontarget organisms, concerns remain that environmental exposures to pesticides may be occurring at levels negatively impacting nontarget organisms. We used a combination of organismal-level toxicity estimates (in vivo aquatic life benchmarks) and data from high-throughput screening (HTS) assays (in vitro benchmarks) to prioritize pesticides and sites of concern in streams at 16 tributaries to the Great Lakes Basin. In vivo or in vitro benchmark values were exceeded at 15 sites, 10 of which had exceedances throughout the year. Pesticides had the greatest potential biological impact at the site with the greatest proportion of agricultural land use in its basin (the Maumee River, Toledo, OH, USA), with 72 parent compounds or transformation products being detected, 47 of which exceeded at least one benchmark value. Our risk-based screening approach identified multiple pesticide parent compounds of concern in tributaries of the Great Lakes; these compounds included: eight herbicides (metolachlor, acetochlor, 2,4-dichlorophenoxyacetic acid, diuron, atrazine, alachlor, triclopyr, and simazine), three fungicides (chlorothalonil, propiconazole, and carbendazim), and four insecticides (diazinon, fipronil, imidacloprid, and clothianidin). We present methods for reducing the volume and complexity of potential biological effects data that result from combining contaminant surveillance with HTS (in vitro) and traditional (in vivo) toxicity estimates. Environ Toxicol Chem 2022;00:1–18. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes↗

USGS2023

Changes in chemical occurrence, concentration, and bioactivity in the Colorado River before and after replacement of the Moab, Utah wastewater treatment plant

Long-term (2010–19) water-quality monitoring on the Colorado River downstream from Moab Utah indicated the persistent presence of Bioactive Chemicals (BC), such as pesticides and pharmaceuticals. This stream reach near Canyonlands National Park provides critical habitat for federally endangered species. The Moab wastewater treatment plant (WWTP) outfall discharges to the Colorado River and is the nearest potential point-source to this reach. The original WWTP was replaced in 2018. In 2016–19, a study was completed to determine if the new plant reduced BC input to the Colorado River at, and downstream from, the outfall. Water samples were collected before and after the plant replacement at sites upstream and downstream from the outfall. Samples were analyzed for as many as 243 pesticides, 109 pharmaceuticals, 20 hormones, 51 wastewater indicator chemicals, 20 metals, and 8 nutrients. BC concentrations, hazard quotients (HQs), and exposure activity ratios (EARs) were used to identify and prioritize contaminants for their potential to have adverse biological effects on the health of native and endangered wildlife. There were 22 BC with HQs >1, mostly metals and hormones; and 23 BC with EARs >0.1, mostly hormones and pharmaceuticals. Most high HQs or EARs were associated with samples collected at the WWTP outfall site prior to its replacement. Discharge from the new plant had reduced concentrations of nutrients, hormones, pharmaceuticals, and other BC. For example, all 16 of the hormones detected at the WWTP outfall site had maximum concentrations in samples collected prior to the WWTP replacement. The WWTP replacement had less effect on instream concentrations of metals and pesticides, BC whose sources are less directly tied to domestic wastewater. Study results indicate that improved WWTP technology can create substantial reductions in concentrations of non-regulated BC such as pharmaceuticals, in addition to regulated contaminants such as nutrients.

Utah↗

USGS2022

Prioritizing pharmaceutical contaminants in Great Lakes tributaries using risk-based screening techniques

In a study of 44 diverse sampling sites across 16 Great Lakes tributaries, 110 pharmaceuticals were detected of 257 monitored. The present study evaluated the ecological relevance of detected chemicals and identified heavily impacted areas to help inform resource managers and guide future investigations. Ten pharmaceuticals (caffeine, nicotine, albuterol, sulfamethoxazole, venlafaxine, acetaminophen, carbamazepine, gemfibrozil, metoprolol, and thiabendazole) were distinguished as having the greatest potential for biological effects based on comparison to screening-level benchmarks derived using information from two biological effects databases, the ECOTOX Knowledgebase and the ToxCast database. Available evidence did not suggest substantial concern for 75% of the monitored pharmaceuticals, including 147 undetected pharmaceuticals and 49 pharmaceuticals with screening-level alternative benchmarks. However, because of a lack of biological effects information, screening values were not available for 51 detected pharmaceuticals. Samples containing the greatest pharmaceutical concentrations and having the highest detection frequencies were from Lake Erie, southern Lake Michigan, and Lake Huron tributaries. Samples collected during low-flow periods had higher pharmaceutical concentrations than those collected during increased-flow periods. The wastewater-treatment plant effluent content in streams correlated positively with pharmaceutical concentrations. However, deviation from this correlation demonstrated that secondary factors, such as multiple pharmaceutical sources, were likely present at some sites. Further research could investigate high-priority pharmaceuticals as well as those for which alternative benchmarks could not be developed.

Indiana, Michigan, Minnesota, New York, Ohio, Wisc↗

USGS2022

Risk-based prioritization of organic chemicals and locations of ecological concern in sediment from Great Lakes tributaries

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For this study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations to established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and to high-throughput toxicity screening data from the U.S. Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several polycyclic aromatic hydrocarbons (PAHs). Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. Results provide a screening level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur.

Illinois, Indiana, Michigan, Minnesota, New York, ↗

USGS2020

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment↗

USGS2018

Potential toxicity of complex mixtures in surface waters from a nationwide survey of United States streams: Identifying in vitro bioactivities and causative chemicals

While chemical analysis of contaminant mixtures remains an essential component of environmental monitoring, bioactivity-based assessments using in vitro systems increasingly play a role in the detection of biological effects. Historically, in vitro assessments focused on a few biological pathways, e.g., aryl hydrocarbon receptor (AhR) or estrogen receptor (ER) activities. High-throughput screening (HTS) technologies have greatly increased the number of biological targets and processes that can be rapidly assessed. Here we screened extracts of surface waters from nationwide survey of United States (US) streams for bioactivities associated with 69 different endpoints using two multiplexed HTS assays. Bioactivity of extracts from 38streams was evaluated and compared with concentrations of over 700 analytes to identify chemicals contributing to observed effects. Eleven primary biological endpoints were detected. Pregnane X receptor and AhR-mediated activities were the most commonly detected. Measured chemicals did not completely account for AhR and PXR responses. Surface waters with AhR and PXR effects were associated with low intensity, developed land-cover. Likewise, elevated bioactivities frequently associated with wastewater discharges included endocrine related endpoints— ER and glucocorticoid receptor (GR). These results underscore the value of bioassay-based monitoring of environmental mixtures for detecting biological effects that could not be ascertained solely through chemical analyses.

Environmental Science & Technology↗

USGS2018

Year-round presence of neonicotinoid insecticides in tributaries to the Great Lakes, USA

To better characterize the transport of neonicotinoid insecticides to the world's largest freshwater ecosystem, monthly samples (October 2015–September 2016) were collected from 10 major tributaries to the Great Lakes, USA. For the monthly tributary samples, neonicotinoids were detected in every month sampled and five of the six target neonicotinoids were detected. At least one neonicotinoid was detected in 74% of the monthly samples with up to three neonicotinoids detected in an individual sample (10% of all samples). The most frequently detected neonicotinoid was imidacloprid (53%), followed by clothianidin (44%), thiamethoxam (22%), acetamiprid (2%), and dinotefuran (1%). Thiacloprid was not detected in any samples. The maximum concentration for an individual neonicotinoid was 230 ng L −1 and the maximum total neonicotinoids in an individual sample was 400 ng L −1 . The median detected individual neonicotinoid concentrations ranged from non-detect to 10 ng L −1 . The detections of clothianidin and thiamethoxam significantly increased as the percent of cultivated crops in the basins increased (ρ = 0.73, P = .01; ρ = 0.66, P = .04, respectively). In contrast, imidacloprid detections significantly increased as the percent of the urbanization in the basins increased (ρ = 0.66, P = .03). Neonicotinoid concentrations generally increased in spring through summer coinciding with the planting of neonicotinoid-treated seeds and broadcast applications of neonicotinoids. More spatially intensive samples were collected in an agriculturally dominated basin (8 sites along the Maumee River, Ohio) twice during the spring, 2016 planting season to provide further information on neonicotinoid inputs to the Great Lakes. Three neonicotinoids were ubiquitously detected (clothianidin, imidacloprid, thiamethoxam) in all water samples collected within this basin. Maximum individual neonicotinoid concentrations was 330 ng L −1 and maximum total neonicotinoid concentration was 670 ng L −1 ; median detected individual neonicotinoid concentrations were 7.0 to 39 ng L −1 .

Great Lakes↗

USGS2018

Bioactive contaminants of emerging concern in National Park waters of the northern Colorado Plateau, USA

Pharmaceuticals and personal care products (PPCPs), wastewater indicators (WWIs), and pesticides (herein, Contaminants of Emerging Concern [CECs]) have been documented in surface waters throughout the world and have associated risks to aquatic life. While much research has focused on temperate and urbanized watersheds, less is known about CEC presence in semi-arid landscapes, where water availability is limited and populations are low. CEC presence in water and sediment is reported for 21 sites in eight U.S. national parks in the northern Colorado Plateau region. From 2012 to 2016, at least one PPCP and/or WWI was detected at most sites on over half of sampling visits, indicating that CECs are not uncommon even in isolated areas. CEC detections were generally fewer and at lower concentrations than in urbanized or agricultural watersheds. Consistent with studies from other U.S. regions, the most frequently detected CECs in this study include DEET, caffeine, organophosphorus flame retardants, and bisphenol A in water and fecal indicators and polycyclic aromatic hydrocarbons in sediment. Maximum concentrations in this study were generally below available water quality benchmarks, sediment quality guidelines, and risk assessment thresholds associated with vertebrates. Additional work is needed to assess the potential activity of hormones, which had high reporting limits in our study, and potential bioactivity of environmental concentrations for invertebrates, microbial communities, and algae. Potential sources of CEC contamination include upstream wastewater effluent discharges and National Park Service invasive-plant-control herbicide applications. CEC occurrence patterns and similarities between continuous and isolated flow locations suggest that direct contamination from individual visitors may also occur. While our data indicate there is little aquatic health risk associated with CECs at our sites, our results demonstrate the ubiquity of CECs on the landscape and a continued need for public outreach concerning resource-use ethics and the potential effects of upstream development.

Colorado Plateau↗

USGS2018

Contaminants of emerging concern in the environment: Where we have been and what does the future hold?

In 1962, Rachel Carson’s book Silent Spring alerted the nation to the dangers of manmade chemicals and indiscriminate use of pesticides. DDT was the culprit and its use threatened a variety of wildlife, including the national bird, bald eagles. In 1969, pressured by scientists and the public, the United States banned almost all uses of DDT; however, DDT was just the tip of the chemical iceberg. In 1996, Theo Colborn’s book, Our Stolen Future, again alerted the public to the dangers of chemical exposure. Endocrine-disrupting chemicals were identified as concerns because exposure to extremely small concentrations can have adverse effects on people and wildlife by interfering with chemical messaging systems, affecting things like sexual development and reproduction.

Water Resources Impact↗

USGS2017

An “EAR” on environmental surveillance and monitoring: A case study on the use of Exposure–Activity Ratios (EARs) to prioritize sites, chemicals, and bioactivities of concern in Great Lakes waters

Current environmental monitoring approaches focus primarily on chemical occurrence. However, based on concentration alone, it can be difficult to identify which compounds may be of toxicological concern and should be prioritized for further monitoring, in-depth testing, or management. This can be problematic because toxicological characterization is lacking for many emerging contaminants. New sources of high-throughput screening (HTS) data, such as the ToxCast database, which contains information for over 9000 compounds screened through up to 1100 bioassays, are now available. Integrated analysis of chemical occurrence data with HTS data offers new opportunities to prioritize chemicals, sites, or biological effects for further investigation based on concentrations detected in the environment linked to relative potencies in pathway-based bioassays. As a case study, chemical occurrence data from a 2012 study in the Great Lakes Basin along with the ToxCast effects database were used to calculate exposure–activity ratios (EARs) as a prioritization tool. Technical considerations of data processing and use of the ToxCast database are presented and discussed. EAR prioritization identified multiple sites, biological pathways, and chemicals that warrant further investigation. Prioritized bioactivities from the EAR analysis were linked to discrete adverse outcome pathways to identify potential adverse outcomes and biomarkers for use in subsequent monitoring efforts.

Great Lakes↗

USGS2015

Pathway-based approaches for assessment of real-time exposure to an estrogenic wastewater treatment plant effluent on fathead minnow reproduction

Wastewater treatment plant (WWTP) effluents are known contributors of chemical mixtures into the environment. Of particular concern are endocrine-disrupting compounds, such as estrogens, which can affect the hypothalamic-pituitary-gonadal axis function in exposed organisms. The present study examined reproductive effects in fathead minnows exposed for 21 d to a historically estrogenic WWTP effluent. Fathead minnow breeding pairs were held in control water or 1 of 3 effluent concentrations (5%, 20%, and 100%) in a novel onsite, flow-through system providing real-time exposure. The authors examined molecular and biochemical endpoints representing key events along adverse outcome pathways linking estrogen receptor activation and other molecular initiating events to reproductive impairment. In addition, the authors used chemical analysis of the effluent to construct a chemical-gene interaction network to aid in targeted gene expression analyses and identifying potentially impacted biological pathways. Cumulative fecundity was significantly reduced in fish exposed to 100% effluent but increased in those exposed to 20% effluent, the approximate dilution factor in the receiving waters. Plasma vitellogenin concentrations in males increased in a dose-dependent manner with effluent concentration; however, male fertility was not impacted. Although in vitro analyses, analytical chemistry, and biomarker responses confirmed the effluent was estrogenic, estrogen receptor agonists were unlikely the primary driver of impaired reproduction. The results provide insights into the significance of pathway-based effects with regard to predicting adverse reproductive outcomes.

Environmental Toxicology and Chemistry↗