US EPA Health Advisory Research Articles

Microcystins at the tap: A closer look at unregulated drinking water contaminants

AbstractThis case study compared microcystins in tap water from 18 public water systems (PWSs) and 46 households with private intakes or nearshore wells (called self‐supplied water systems [SSWS]) from Clear Lake, California during a major cyanobacterial bloom in 2021. Microcystin concentrations were below the US EPA health advisory (HA; 0.3 μg/L) for PWS with Clear Lake intakes and for SSWS drawing from wells. However, for SSWS with Clear Lake intakes (intake SSWS), 24 of 79 microcystin samples collected were at or above the HA (maximum 3.9 μg/L). Further, microscopy showed that 20 of 28 tap samples (post‐treatment) from intake SSWS contained either cyanobacteria or algal cells. This demonstrates that robust multi‐barrier treatment systems at PWS reliably removed microcystins, while the less sophisticated treatment systems at intake SSWS were compromised during a major cyanobacterial bloom. Intake SSWS should consider alternative sources of drinking water, including physically connecting to an adjacent PWS or drilling a well.

An evaluation of health-based federal and state PFOA drinking water guidelines in the United States

Perfluorooctanoic acid (PFOA) is a synthetic, perfluorinated organic acid previously used in fluoropolymer production in the United States. PFOA has been a recent focal point for regulation because of its ubiquitous presence in drinking water throughout the United States. In 2016, the United States Environmental Protection Agency (US EPA) issued a lifetime drinking water Health Advisory (HA) for PFOA of 0.07 μg/L; several states have also implemented their own drinking water guidelines for PFOA. The current study aimed to evaluate the basis and derivation of state and federal guidelines for PFOA in drinking water, with particular emphasis on the exposure parameters utilized. Twelve distinct PFOA drinking water standards were identified ranging from 0.0051 to 2 μg/L. The US EPA HA assumptions were evaluated using a Monte Carlo analysis that included distributions for drinking water intake (DWI) rate and the relative source contribution (RSC). We determined that US EPA's HA of 0.07 μg/L is protective of 99% of the population of lactating women. We also demonstrated that the health-based guidelines were highly variable across states and that the actual RSC of PFOA from drinking water is likely greater than 20%, based on studies of actual PFOA exposures from dust, water, and food. A sensitivity analysis was performed using the same equations as the US EPA, while substituting the RSC and DWI variables; resulting in HAs ranging from 0.074 to 0.346 μg/L. We also evaluated the contribution of PFOA in drinking water to the systemic PFOA body burden of the general population using an available biokinetic model. We conclude that more rigorous efforts are warranted to establish consistent health-based drinking water guidelines for PFOA, given that drinking water is a primary source of human exposure to PFOA in the United States.

Prevalence of per- and polyfluoroalkyl substances (PFASs) in drinking and source water from two Asian countries

The present study focuses on the determination of the occurrence and levels of per- and polyfluoroalkyl substances (PFASs) in the drinking and source water from the Philippines and Thailand. A total of 46 samples (18 commercial bottled waters, 5 drinking water from vending machine (re-fill stations) and 23 source water) were analyzed using liquid chromatography with tandem high-resolution mass spectrometry. Using the targeted method, 12 different PFASs were detected in the drinking water samples with total quantifiable PFASs (∑PFASs) levels ranging from 7.16 to 59.49 ng/L; 15 PFASs were detected in source water with ∑PFASs ranging from 15.55 to 65.65 ng/L. A 100% detection frequency was observed for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorosulfonic acid (PFOS) in all water samples. Six other PFASs, not included in the targeted analysis, were detected using the suspect screening approach. For the first time, the presence of 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA) in drinking water is reported, and 3 novel PFASs (C5H5OF8, C6H4O2F6, and C9H2O2F16) were detected using suspect screening in source water. Combined results from target and suspect screening analysis showed that PFASs detected were predominantly (52%) short-chain (with fluorinated alkyl chain of ≤6) which could be explained by their high mobility in the environment. The detected PFASs levels in drinking water will not likely pose immediate health risk to consumers according to US EPA health advisory for PFOS and PFOA of 70 ng/L, but inclusion of bottled and drinking water from re-fill stations in monitoring programs is warranted.

Use of qPCR and RT-qPCR for monitoring variations of microcystin producers and as an early warning system to predict toxin production in an Ohio inland lake

Public concern over cyanobacterial blooms has increased due to their higher frequency of occurrence and their potential ecological and health impacts. Detection of microcystin (MC) producers (MCPs) using qPCR and RT-qPCR allows for the rapid identification of blooms by combining specificity and sensitivity with a relatively high throughput capability. Investigation of MCP population composition (correlation, dominance), toxin gene expression, and relationship to MC concentration was conducted using a panel of qPCR assays targeting mcyA, E and G on weekly and daily water samples collected from an Ohio inland reservoir lake. Further, these data were used to develop early warning thresholds for prediction of MC concentrations exceeding the US EPA Health Advisory cutoff value (>0.3 μg L−1) using receiver operating characteristic curves and tobit regression. MCP Microcystis genomic copy number made up approximately 35% of the total Microcystis spp. and was the dominant toxic subpopulation of MCPs. The expressed MCPs were 0.2% of the extant genomic copy numbers, while toxic Microcystis had higher expressed proportion (0.5%) than that of toxic Planktothrix (0.04%). Microcystis toxin genes increased in June and July but decreased in August and September along with similar trends of cell replication. Quantities of both RT-qPCR and qPCR followed the same trend and were highly correlated with MC-ADDA, while RT-qPCR not only reflected the active toxin genes or toxic species, but also indicated the beginning and ending of toxin production. A one-week early warning of MC exceedance over the EPA Health Advisory was based on signaling of qPCR and RT-qPCR using receiver operating characteristic curves. This study illustrates the potential use of qPCR or RT-qPCR as an early warning system of extant and MC producing potentials during a toxic algal bloom, with predictive powers of 50%–60% and 30%–40% (p < 0.001), respectively, and false positive rates of about 70% for both LC-MS/MS or ELISA.

Perfluorooctanoic Acid (PFOA): Environmental Sources, Chemistry, Toxicology, and Potential Risks

ABSTRACT Attention regarding perfluoroalkyl and polyfluoroalkyl substances (PFAS) has increased in recent years, due to recognition of widespread environmental presence, recognition of a chemical structure that confers resistance to degradation, and reported health concerns. Historical common exposure sources include food, drinking water, occupational circumstances, and products in commerce (e.g., carpeting, clothing, paper products). Early-2000’s data showed perfluorooctanoic acid (PFOA) was present in blood samples from nearly all the U.S. general population (>99%). Alterations in industrial manufacturing processes, increased regulatory scrutiny, and advanced water treatment options have reduced the reported human body burden of PFAS in the U.S., including for PFOA. Human serum concentrations of PFOA, which do not identify the source(s) of exposure, have exhibited a substantial decrease (~63%) between the 1999–2000 and the 2013–2014 NHANES monitoring by the Centers for Disease Control and Prevention (CDC). With respect to both noncancer and potential cancer effects that may be associated with reported serum levels of PFOA, conclusions regarding an absence of effects, or insufficient information to suggest adverse effects, prevent a consistent conclusion about the occurrence and magnitude of human health effects. In the last several years, a number of state and federal agencies have developed health advisories or guideline values for drinking water exposure that are in the sub-ppb range. In 2016, a USEPA Health Advisory of 0.07 ppb was released, which stands in contrast to 2016 Health-based Values from Health Canada ranging from 0.2 ppb (PFOA) to 30 ppb, and a few other U.S. states with values even less than that of USEPA (e.g., MN, NJ, VT). Further work is necessary to distinguish in transparent fashion between drinking water levels that intentionally are set on a conservative basis to protect human health vs exposure levels that may be associated with tangible adverse effects.

Monthly Variations in Perfluorinated Compound Concentrations in Groundwater.

Large-scale manufacturing of poly- and perfluorinated compounds in the second half of the 20th century has led to their ubiquity in the environment, and their unique structure has made them persistent contaminants. A recent drinking water advisory level issued by the United States Environmental Protection Agency lowered the advisory level concentration of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) from 200 nanograms per liter and 400 nanograms per liter, respectively, to 70 nanograms per liter separately or combined. Small temporal variations in PFOS and PFOA concentrations could be the difference between meeting or exceeding the recommended limit. In this study, newly sampled data from a contaminated military site in Alaska and historical data from former Pease Air Force Base were collected. Data were evaluated to determine if monthly variations within PFOS and PFOA existed. No statistically significant temporal trend was observed in the Alaska data, while the results from Pease, although statistically significant, showed the spread of observed contaminant concentrations around the fitted line is broad (as indicated by the low R2 values), indicating that collection date has little value in predicting contaminant concentrations. Though not currently the subject of a US EPA health advisory, data on perfluorobutanesulfonic acid (PFBS), perfluorohexane sulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA) were collected for each site and their average concentrations evaluated.

Worldwide drinking water occurrence and levels of newly-identified perfluoroalkyl and polyfluoroalkyl substances

In the last decade or so, concerns have arisen with respect to the widespread occurrence of perfluoroalkyl acids (PFAAs) in the environment, food, drinking water, and humans. In this study, the occurrence and levels of a large range of perfluoroalkyl and polyfluoroalkyl substances (PFASs) were investigated in drinking water (bottled and tap water samples) from various locations around the world. Automated off-line solid phase extraction followed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was used to analyze PFASs of various chain lengths and functional groups. In total, 29 target and 104 suspect-target PFASs were screened in drinking water samples (n=97) from Canada and other countries (Burkina Faso, Chile, Ivory Coast, France, Japan, Mexico, Norway, and the USA) in 2015–2016. Out of the 29 PFASs quantitatively analyzed, perfluorocarboxylates (PFCAs: C4/14), perfluoroalkane sulfonates (PFSAs: C4, C6, C8), and perfluoroalkyl acid precursors (e.g., 5:3 fluorotelomer carboxylate (5:3 FTCA)) were recurrently detected in drinking water samples (concentration range: <LOD to 39ngL−1). Tap water samples from Canada showed noteworthy differences depending on their source; for instance, ∑29PFASwas significantly greater in those produced from the Great Lakes/St. Lawrence River ecosystem than those produced from other types of sources (14 versus 5.3ngL−1, respectively). A suspect-target screening approach indicated that other perfluoroalkane sulfonamides (FBSA, FHxSA), perfluoroethyl cyclohexane sulfonate (PFECHS), ultrashort chain (C2–C3) PFSAs (PFEtS, PFPrS), and two additional PFSAs (PFPeS (C5) and PFHpS (C7)) were repeatedly present in tap water samples (concentration ranges: <LOD to 4.0ngL−1). To the authors' best knowledge, this constitutes the first observation of a cyclic perfluoroalkane sulfonate (PFECHS) and C4–C6 perfluoroalkane sulfonamides (FBSA, FHxSA) in drinking water. According to the newly updated US EPA health advisory for PFOS and PFOA (70ngL−1), the drinking water samples collected in the present monitoring would not pose a health risk to consumers as regards PFAA levels.

Pre-drilling water-quality data of groundwater prior to shale gas drilling in the Appalachian Basin: Analysis of the Chesapeake Energy Corporation dataset

Unconventional natural gas production in the Marcellus and Utica formations of the Northeastern United States raises concerns about potential impacts to shallow groundwater. We examined and interpreted 13,040 analyses from pre-drilling groundwater samples from domestic water wells in northeastern (NE) Pennsylvania and 8004 samples from water wells in the “Western Area” which includes southwest Pennsylvania, eastern Ohio, and north-central West Virginia. These samples were acquired on behalf of Chesapeake Energy Corporation as part of its local pre-drilling water supply monitoring program. We evaluated concentrations of major ions and metals relative to federal drinking-water-quality standards upon which regulatory decisions are often based. Chesapeake’s dataset, the most comprehensive for these areas, shows that exceedance of at least one water-quality standard occurs in 63% of water well samples in NE Pennsylvania and 87% in the Western Area. In NE Pennsylvania, 10% of the samples exceeded one or more of the United States Environmental Protection Agency’s (USEPA) primary maximum contaminant levels (MCLs) for drinking-water supplies, 46.1% of the samples exceeded one or more of USEPA secondary maximum contaminant levels (SMCLs), and another 7% exceeded one or more of USEPA health advisory or regional screening levels for tap water.In the Western Area 8% of samples exceeded one or more MCLs, 65% exceeded one or more SMCLs, and 15% exceeded one or more health advisory or regional screening levels for tap water. Chesapeake’s dataset, orders of magnitude larger than any in previously published literature, shows that water-quality exceedances relate to factors such: as where the sample occurs within the groundwater flow system, the natural groundwater chemical type (hydrochemical facies), the geologic unit producing the water, and/or the topographic position (valley versus upland). Our comparison of these results to historical groundwater data from NE Pennsylvania, which pre-dates most unconventional shale gas development, shows that the recent pre-drilling geochemical data is similar to historical data. We see no broad changes in variability of chemical quality in this large dataset to suggest any unusual salinization caused by possible release of produced waters from oil and gas operations, even after thousands of gas wells have been drilled among tens of thousands of domestic wells within the two areas studied. Our evaluation also agrees with early researchers such as Piper (1933) and Lohman (1939, 1937) who found that the saline waters in both areas underlie fresher groundwater. The saline water is naturally-occurring connate brine or salt water which has not been flushed by circulating meteoric water; rather than vertical migration of salt water from deep strata such as the Marcellus shale as suggested by Warner et al. (2012). Elevated metals concentrations, particularly iron and manganese, partly relate to sample turbidity; dissolved metals would provide a more accurate measurement of metals in shallow groundwater than does the total metals analysis typically required by regulations.

Integrated approach for the quality assessment of freshwater resources in a vineyard area (South Portugal)

An integrated chemical and biological approach for the quality assessment of freshwater resources in a vineyard area of the 'Alentejo' region (South Portugal) is presented. This includes analysis to 11 pesticide compounds and whole toxicity testing on algae and crustaceans. Simazine, terbuthylazine, terbutryn, desethylatrazine and chlorpyrifos were the most frequently detected pesticides in water collected from wells and drainage channels. Mixtures of up to three compounds in different qualitative combinations were also found. The quality standards for individual pesticides (0.1 μg L(-1)) and pesticides-total (0.5 μg L(-1)) were exceeded in some samples. However, their maximum concentrations were lower than the WHO guidelines, the USEPA health advisory values and the environmental quality standards for priority substances applicable to surface water. In five samples, the herbicides terbuthylazine and terbutryn and the insecticide chlorpyrifos did not pass the toxicity exposure ratio (TER) trigger values specified for aquatic organisms (algae, Daphnia and fish). Maximum toxic effects on Daphnia magna (100%) and Pseudokirchneriella subcapitata (82.56%) were determined in groundwater samples, while in surface water, no toxicity was observed. Concerning effects on Heterocypris incongruens in sediment samples collected at the drainage channels, mortality and growth inhibition values were below 38%. Pro-active management of the use of pesticides is recommended for implementing at the farm and catchment level to reduce inputs into ground- and surface water.

Development of health-based drinking water guidance for PFOA

Perfluorooctanoic acid (PFOA) is a synthetic, perfluorinated organic acid previously used in fluoropolymer production in the United States. PFOA has been a recent focal point for regulation because of its ubiquitous presence in drinking water throughout the United States. In 2016, the United States Environmental Protection Agency (US EPA) issued a lifetime drinking water Health Advisory (HA) for PFOA of 0.07 μg/L; several states have also implemented their own drinking water guidelines for PFOA. The current study aimed to evaluate the basis and derivation of state and federal guidelines for PFOA in drinking water, with particular emphasis on the exposure parameters utilized. Twelve distinct PFOA drinking water standards were identified ranging from 0.0051 to 2 μg/L. The US EPA HA assumptions were evaluated using a Monte Carlo analysis that included distributions for drinking water intake (DWI) rate and the relative source contribution (RSC). We determined that US EPA's HA of 0.07 μg/L is protective of 99% of the population of lactating women. We also demonstrated that the health-based guidelines were highly variable across states and that the actual RSC of PFOA from drinking water is likely greater than 20%, based on studies of actual PFOA exposures from dust, water, and food. A sensitivity analysis was performed using the same equations as the US EPA, while substituting the RSC and DWI variables; resulting in HAs ranging from 0.074 to 0.346 μg/L. We also evaluated the contribution of PFOA in drinking water to the systemic PFOA body burden of the general population using an available biokinetic model. We conclude that more rigorous efforts are warranted to establish consistent health-based drinking water guidelines for PFOA, given that drinking water is a primary source of human exposure to PFOA in the United States.

Laboratory studies on the leaching of aldicarb through a tropical soil from Belize, Central America

Studies in temperate regions indicate that the carbamate insecticide aldicarb and its metabolites leach readily through agricultural soils into groundwater. However, little is known about the fate of this nematicide in tropical regions, where its leaching potential may be even greater because of high annual rainfall and the acidic nature and low organic content of many tropical soils. Examination of the leaching behaviour of aldicarb and its metabolites in columns containing soil from Belize, Central America, indicated that total carbamate residues (TCR) could rapidly reach concentrations > 15 mg L−1 in porewater 1 m below the soil surface within 70 days of application. These values are well in excess of the US EPA Health Advisory level of 0.01 mg L−1. TCR retention within a given depth interval in the soil columns relative to incoming TCR flux was greatest between 0 and 0.1 m, reflecting high organic matter contents in the upper soil. Retention below 0.1 m was relatively consistent with depth, while differences in relative retention between columns were due to a greater duration of leaching for the second column. Aldicarb was rapidly oxidized to aldicarb sulfoxide and aldicarb sulfone in these soils. The high concentration and mobility of TCR in this acidic soil is attributed to the transformation of the parent compound to the sulfoxide metabolite, which has a lower degradation rate and organic carbon partioning coefficient than aldicarb.