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Aliesha L. Krall

Publications and source records attributed to Aliesha L. Krall.

10 recordsLinked to original sources

Trace organic contaminants in U.S. national park surface waters: Prevalence and ecological context☆

Surface water samples were collected from 264 sites across 46 U.S national parks during the period of 2009–2019. The number of sites within each park ranged from 1 to 31 and the number of samples collected within each park ranged from 1 to 201. Samples were analyzed for up to 340 trace organic contaminants (TrOCs), including pharmaceuticals, personal care products, pesticides, and various contaminants indicative of anthropogenic influence (e.g., fragrances, surfactants, flame retardants). A total of 155 TrOCs was detected in at least one sample with concentrations ranging from the reporting level of 10 ng/L (multiple contaminants) to 11,900 ng/L (p-cresol). Except for bisphenol A, DEET, theobromine, and gabapentin, TrOCs were detected in <20% of samples. Despite the relatively low detection frequencies, when TrOCs were detected, concentrations were similar to those reported from other regional or national studies. We compared detected concentrations to bioactivity concentrations and water quality benchmarks, when available, to identify occurrences of elevated concentrations and to estimate the potential for biological effects to aquatic biota. Elevated concentrations of 27 TrOCs, mostly pesticides, were detected throughout the study. To gain insight regarding potential sources, we related watershed characteristics (e.g., land cover, presence of point sources) to the number of TrOCs detected at each site. We found that the presence of wastewater treatment plants and the proportion of the watershed classified as agricultural land were the most influential variables for describing the number of pharmaceuticals and the number of pesticides present, respectively. This study represents the largest-scale study characterizing the presence and magnitude of TrOCs in U.S. national park surface waters, to date. These data provide a baseline that can be used to inform future monitoring within the parks and to assess changes in water quality.

Environmental Pollution

Creek and quarry water quality at Pipestone National Monument and pilot study of pathogen detection methods in waterfall mist at Winnewissa Falls, Pipestone, Minnesota, 2018–19

Pipestone National Monument is a 301-acre site sacred to many Native American Tribes, providing cultural exhibits and walking trails to Pipestone Creek, Winnewissa Falls, and historical pipestone quarries for numerous visitors each year. However, the Minnesota Pollution Control Agency has determined turbidity and fecal coliform bacteria occur in Pipestone Creek in high enough numbers to be a potential health hazard. Concerns also were raised about exposure risk from waterfall mist to visitors and staff. The U.S. Geological Survey and the National Park Service collaborated on a study to collect 21 water-quality samples from 8 creek sites and 3 quarries in 2018 and analyzed them for over 250 water-quality parameters and contaminants. Additional samples were collected in August 2019 to assess the waterfall mists from Winnewissa Falls. Nutrient concentrations in the creek and quarries were elevated in 2018, indicating they are affected by agricultural inputs. All sample concentrations for nitrate and total nitrogen in Pipestone Creek exceeded Minnesota standards and U.S. Environmental Protection Agency nutrient criteria. Minnesota standards and U.S. Environmental Protection Agency nutrient criteria for total phosphorus also were exceeded in some of the quarry samples. Twenty of 210 micropollutants had measurable concentrations: 13 pesticides, 5 pharmaceuticals, and 2 other types of micropollutants. Atrazine, deethylatrazine, and metolachlor ethanesulfonic acid were detected in all 21 samples collected during the study. The five pharmaceuticals detected were acetaminophen, gabapentin, gemfibrozil, metformin, and oxycodone. Gabapentin (10 of 21 samples) and metformin (8 of 21 samples) were the most commonly detected pharmaceuticals. None of the detected micropollutant concentrations exceeded any Minnesota standards or U.S. Environmental Protection Agency aquatic life benchmarks, except the acute toxicity benchmark for nonvascular plants for atrazine. Two cyanotoxins, anatoxin-a and microcystin, were detected, but concentrations were below U.S. Environmental Protection Agency guidelines for swimming or recreation. Notably, total coliform, fecal coliform, and Escherichia coli were detected in all creek samples, and concentrations generally decreased downstream, suggesting contamination potentially occurred upstream from the monument. Mycobacterium avium ssp. paratuberculosis was not detected in any creek sediment samples but was detected in three water samples from the creek. Three organisms were detected in the 2019 water and mist sampling from Winnewissa Falls. Two of these organisms can cause illness in humans ( Cryptosporidium and Legionella ), and a third (ruminant Bacteroides ) is an indicator of manure contamination. Despite few samples, pathogen-positive water samples and air sampling demonstrated the feasibility and utility of the mist sampling approach outlined in this report.

Minnesota

Water-surface profile maps for the Mississippi River near Prairie Island, Minnesota, 2019

Digital water-surface profile maps for a 14-mile reach of the Mississippi River near Prairie Island, Minnesota, from the confluence of the St. Croix River at Prescott, Wisconsin, to upstream from the U.S. Army Corps of Engineers Lock and Dam No. 3 (U.S. Army Corps of Engineers National Inventory of Dams number MN00595) in Welch, Minnesota, were created by the U.S. Geological Survey (USGS) in cooperation with the Prairie Island Indian Community in the State of Minnesota. The water-surface profile maps depict estimates of the areal extent and depth of water inundation corresponding to selected water levels (stages) at the USGS streamgage Mississippi River at Prescott, Wisconsin (USGS station number 05344500). Current conditions for estimating near-real-time areas of inundation by use of USGS streamgage information may be obtained from the National Water Information System on the internet at https://doi.org/10.5066/F7P55KJN . In this study, water-surface profiles were computed for the stream reach by means of a one-dimensional step-backwater model. The model was calibrated by using the most current stage-discharge relations at the USGS streamgage Mississippi River at Prescott, Wisconsin (USGS station number 05344500). The hydraulic model was then used to determine four water-surface profiles for stream stages at 37.00, 39.00, 40.00, and 41.00 feet (ft) referenced to the streamgage datum and ranging from bankfull to approximately 2 ft below the highest recorded stage at the streamgage, which is 43.11 ft. The simulated water-surface profiles were then combined with a geographic information system digital elevation model (derived from light detection and ranging data having a 0.35-ft vertical and 1.97-ft root mean square error horizontal resolution) in order to delineate the area inundated at each stage. The combination of maps provided in this report and real-time stage data from the upstream USGS streamgage provide emergency management personnel and residents with information that is critical for flood response activities such as evacuations and road closures as well as for post flood recovery efforts.

Minnesota

Comparison of the results of enzyme-linked immunosorbent assay (ELISA) to mass-spectrometry based analytical methods for six unregulated contaminants in source water and finished drinking-water samples

Regulatory entities, such as the Minnesota Department of Health, monitor public water systems for conformance with Federal and State monitoring requirements and water-quality standards. Although some contaminants have Federal and (or) State regulations and guidance values, many contaminants, such as pesticides and pharmaceuticals, are unregulated in that only non-enforceable health-based guidance values have been assigned to them. Furthermore, because these contaminants are not regulated, commonly only limited resources are available to public water systems or regulatory entities to monitor them in drinking water. Focused screening efforts on contaminants that are frequently detected in the environment can provide information to help monitoring entities prioritize their sampling efforts. Here we assess the use of enzyme-linked immunosorbent assay (ELISA) method, a rapid, inexpensive screening method, as an alternative to more expensive methods to analyze source and finished drinking-water samples collected from public water systems throughout Minnesota for three commonly detected pesticides (atrazine, imidacloprid, and pyrethroids) and three commonly detected pharmaceuticals (caffeine, carbamazepine, and sulfamethoxazole). The ELISA results were compared to results provided by more advanced mass-spectrometry analytical methods at the U.S. Geological Survey National Water Quality Laboratory (NWQL) and SGS AXYS Analytical Services Ltd. (AXYS). Overall, these datasets are highly censored (>80 percent) and contain multiple reporting limits within and between laboratories. To discern agreement between paired contaminant group results (target contaminant plus immunologically similar contaminants) by ELISA and the advanced analytical methods at NWQL and AXYS, presence-absence agreement analysis was coupled with false negative and false positive analysis. Analysis of presence-absence agreement shows that ELISA has generally good agreement (77.9 to 100 percent) with both NWQL and AXYS for all unregulated contaminant groups. Imidicloprid, pyrethroids, and caffeine contaminant groups have relatively low false positivity rates (16, 6, and 5 percent, respectively) when analyzed by ELISA, which indicates the ELISA method, for these contaminant groups, could be experiencing low-level interference attributed to the detection of immunologically similar contaminants. Similarly, sulfamethoxazole has a low false positivity rate (0.8 percent), which indicates ELISA is likely not overestimating results for this contaminant group. Analyses for carbamazepine and sulfamethoxazole by ELISA resulted in low false negativity rates (1.6 and 0.8 percent, respectively), which indicates the ELISA method is likely not underestimating the results for this contaminant group. Conversely, the atrazine contaminant group has a high false negativity rate (84 percent), which indicates the method has a strong negative bias and that ELISA underestimates results for this contaminant. These qualitative results indicate that the ELISA method could potentially serve as a reliable and cost-effective screening method to help drinking water monitoring entities prioritize sampling efforts for analyzing carbamazepine and sulfamethoxazole in source and finished drinking-water samples collected from public water systems. At the same time, although ELISA did not prove to be a good screening method for atrazine, evaluation of ELISA results indicated that its use for screening imidacloprid, pyrethroids, and caffeine could be beneficial for water testing.

Minnesota

Quantifying relations between altered hydrology and fish community responses for streams in Minnesota

Altered hydrology is a stressor on aquatic life for several streams in Minnesota, but quantitative relations between specific aspects of streamflow alteration and biological responses have not been developed on a statewide scale in Minnesota. Best subsets regression analysis was used to develop linear regression models that quantify relations among five categories of hydrologic explanatory metrics (i.e., duration, frequency, magnitude, rate-of-change, and timing) computed from streamgage records and six categories of biological response metrics (i.e., composition, habitat, life history, reproductive, tolerance, trophic) computed from fish community samples, as well as fish-based indices of biotic integrity (FIBI) scores and FIBI scores normalized to the an impairment threshold of the corresponding stream class (FIBI_BCG4). Three hydrologic datasets were used to examine rRelations between altered hydrology and fish community responses were examined at three different temporal scalesusing three hydrologic datasets that represented periods of record, long-term changes, and short-term changes to flow regimes in streams of Minnesota.

Minnesota

Assessing the influence of natural copper-nickel-bearing bedrocks of the Duluth Complex on water quality in Minnesota, 2013–15

The U.S. Geological Survey, in cooperation with the University of Minnesota-Duluth Natural Resources Research Institute, completed an assessment of regional water quality in areas of potential base-metal mining in Minnesota. Bedrock, soil, streambed sediment, and surface-water samples were collected in three watersheds that cross the basal part of the Duluth Complex with different mineral-deposit settings: (1) copper-nickel-platinum group element mineralization (Filson Creek), (2) iron-titanium-oxide mineralization (headwaters of the St. Louis River), and (3) no identified mineralization (Keeley Creek). At least 10 bedrock, 30 soil (2 each from 15 sites), and as many as 13 streambed sediment samples were collected in each watershed and analyzed for 44 major and trace elements, total and inorganic carbon, and 10 loosely bound metals (when possible). Surface-water samples were collected at four to nine locations in each watershed three to four times per year for 2 years (total of 141 environmental samples). Surface-water samples were analyzed for 10 trace metals (total and dissolved concentrations), 8 trace elements, 8 major ions (dissolved concentrations), alkalinity, and total and dissolved organic carbon. Metal and element concentrations in solid media varied by watershed, representing local geology. Copper-nickel sulfide mineralization in the Filson Creek watershed was evidenced in bedrock, soil, and streambed sediments. In the Keeley Creek watershed, silicate mineralogy of underlying bedrock contributed metals to streambed sediments. Thick glacial cover masked potential bedrock contributions to solid media in the St. Louis River watershed. Water-quality data indicate that waters in all three watersheds are dilute. Water quality is more similar between the Filson and Keeley Creek watersheds, compared to the St. Louis River watershed, because of the difference in glacial cover. Metal concentrations (copper and nickel, in particular) in surface-water samples follow similar patterns of concentrations in solid media, indicating the influence of bedrock on water quality in Filson and Keeley Creeks. Data from this study provide a baseline of metal concentrations and general water quality within an area of active mineral exploration.

Minnesota

Predicting geogenic arsenic in drinking water wells in glacial aquifers, north-central USA: Accounting for depth-dependent features

Chronic exposure to arsenic (As) via drinking groundwater is a human health concern worldwide. Probabilities of elevated geogenic As concentrations in groundwater were predicted in complex, glacial aquifers in Minnesota, north‐central USA, a region that commonly has elevated As concentrations in well water. Maps of elevated As hazard were created for depths typical of drinking water supply and with well construction attributes common for domestic wells. Conventional variables describing aquifer properties and materials, position on the hydrologic landscape, and soil geochemistry were among the most influential for predicting the probability of elevated As. We also found that certain well construction attributes were influential in predicting As hazard. Smaller distances between the top of the well screen and overlying aquitard (proximity) and shorter well screen lengths were each associated with higher probabilities of elevated As. Influential predictor variables, which are either mapped across the region or are well construction attributes, are proxies in the model for measurable physical or geochemical causes of elevated As (e.g., redox condition, till or aquifer sediment chemistry, and water chemistry), which are not mapped across the region. Our setting shares some important characteristics with deltaic and other high‐As aquifers in Southeast Asia: late Quaternary age, complex layering of coarse‐ and fine‐grained materials, low‐As sediment concentrations, and geochemical controls on As mobilization. Translating three‐dimensional geologic and geochemical understanding of As mobility to quantifiable variables for modeling with powerful, flexible statistical tools could improve predictions and help identify safer groundwater supply options in the USA, Southeast Asia, and elsewhere.

Minnesota

Concentrations of pharmaceuticals and other micropollutants in groundwater downgradient from large on-site wastewater discharges

Large subsurface treatment systems (LSTS) and rapid infiltration basins (RIB) are preferred onsite wastewater treatments compared to direct discharge of treated wastewater to streams and adjacent facilities. Discharge of these wastewater treatments may result in contaminant loading to aquifers that also serve as drinking water sources downgradient from the discharge site. Until recently, few studies have characterized the contribution of micropollutants (e.g. pharmaceuticals, fragrances, flame retardants, etc.) to receiving aquifers. We conducted a pilot project to characterize the occurrence of micropollutants in groundwater downgradient from 7 on-site treatment systems in Minnesota, USA: 5 community LSTS and 2 municipal RIB. One downgradient monitoring well was sampled three times at each facility over one year. Of 223 micropollutants analyzed, 35 were detected. Total sample concentrations ranged from 90 to 4,039 ng/L. Sulfamethoxazole (antibiotic) was detected in all samples at concentrations from 7 to 965 ng/L. Other pharmaceuticals (0.12–1,000 ng/L), organophosphorus flame retardants (10–500 ng/L), and other anthropogenic chemicals (4–775 ng/L) were also detected. The numbers and concentrations of micropollutants detected were inversely related to dissolved oxygen and depth to water. Ratios of pharmaceutical concentrations to human-health screening values were <0.10 for most samples. However, concentrations of carbamazepine and sulfamethoxazole exceeded screening values at two sites. Study results illustrate that large on-site wastewater systems designed to discharge to permeable soil or shallow groundwater effectively deliver pharmaceuticals and other micropollutants to groundwater aquifers and could contribute micropollutants to drinking water via water supply wells.

Minnesota

Wastewater indicators, hormones, sterols, antibiotics, and pharmaceuticals in soil at an agricultural field irrigated with domestic septage, central Minnesota, September 2014

Treated domestic septage can be used to irrigate agricultural fields as a disposal method or as a means to reuse water. Because traditional on-site treatment systems are not designed to remove wastewater indicators, hormones, sterols, antibiotics, and pharmaceuticals, land application of septage potentially results in soil contamination. Soils were collected and analyzed from four sites in a central Minnesota agricultural field irrigated with domestic septage. Soil samples were analyzed for 111 unique contaminants, including wastewater indicators, hormones, sterols, antibiotics, and pharmaceuticals. In total, 32 contaminants were detected in soil samples. Several wastewater indicators were detected in soil, including fragrances, alkylphenols, and flame-retardants, at concentrations ranging from 1 (2,6-dimethylnaphthalene at soil site 4) to 1,550 (β-sitosterol at soil site 1) micrograms per kilogram. Relative to the number of contaminants analyzed, steroid hormones had the most frequent detections in soil samples (33 percent), and androgens were more prevalent compared to estrogens (50 and 22 percent, respectively). Androgens and estrogens were detected at concentrations ranging from 0.21 (estrone at soil site 3) to 3.9 (dihydrotestosterone at soil site 1) micrograms per kilogram. Quantifiable concentrations of antibiotics and pharmaceuticals ranged from 1.4 (carbamazepine at soil site 1) to 540 (azithromycin at soil site 3) micrograms per kilogram. Two antibiotics, ciprofloxacin and ofloxacin, were detected at concentrations above the limit of quantification (greater than 1,000 micrograms per kilogram at soil sites 2 and 3). This pilot sampling indicates that soils may be a repository for some contaminants introduced to the environment through land application of domestic septage.

Minnesota

Detecting sulfamethoxazole and carbamazepine in groundwater: Is ELISA a reliable screening tool?

In recent years, numerous studies have reported the prevalence of organic micropollutants in natural waters. There is an increasing interest in assessing the occurrence and transport of these contaminants in groundwater because a large number of people in the United States rely on groundwater for their drinking water. However, commonly used mass-spectrometry-based analytical methods are expensive and time-consuming. The enzyme-linked immunosorbent assay (ELISA) method offers an inexpensive analytical alternative that provides semi-quantitative results in a relatively quick timeframe. We investigated the use of ELISA for two commonly detected micropollutants, sulfamethoxazole (SMX) and carbamazepine (CBZ), in groundwater collected as part of two different studies, one in Minnesota and the other in Iowa. The ELISA results were compared with two mass-spectrometry-based methods: (1) direct aqueous injection-high performance liquid chromatography/tandem mass spectrometry (HPLC) and (2) online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry (SPE LC). Differences in SMX and CBZ observations between ELISA and both HPLC and SPE LC were analyzed using the Paired Prentice-Wilcoxon test. Estimates of bias and limits of agreement between paired observations also were calculated. The SMX determinations by ELISA yielded results that were 30 and 14% greater than HPLC and SPE LC, respectively. The CBZ determinations by ELISA yielded results that were 25 and 9% greater than HPLC and SPE LC, respectively. The ELISA determinations were in presence-absence agreement with HPLC for 83% of samples for SMX and CBZ; and with SPE LC for 76 and 80% of samples for SMX and CBZ, respectively. Results indicate that ELISA for SMX and CBZ is a reliable and cost effective screening-tool alternative to more commonly used mass spectrometry-based analytical methods.

Environmental Pollution