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At least 19 recordsLinked to original sources

Characterization of humic acid fractions by C-13 nuclear magnetic resonance spectroscopy

Soil humic acids from different environments were fractionated by adsorption chromatography on Sephadex and characterized by C‐13 nuclear magnetic resonance (NMR) spectroscopy. The C‐13 NMR spectra of the fractions consist of some sharp, well‐resolved lines and some broad bands in contrast to the spectra of the unfractionated humic acids, where the bands are broader and less well‐resolved. The marked increase in resolution is apparently due to increased homogeneity of the fractions. These spectra are compared to the spectra of model compounds.

Environmental Technology Letters

A semiquantitative X-ray diffraction method to determine mineral composition in stream sediments with similar mineralogy

A semiquantitative X‐ray diffraction procedure has been developed that can be used to acquire reproducible mineralogic data from geographically unrelated stream‐sediment samples having similar mineralogy. Weight percentages for quartz, total‐feldspar, and total‐clay can be determined by direct comparison of intensities with standard‐mineral mixtures of known weight percent. Matrix effects and mass‐absorption differences are circumvented by taking the ratio of peak‐intensity, in counts per second, for quartz relative to that of other minerals being quantified. Mineral percentages generally are reproducible to within 10 percent.

Environmental Technology Letters

A comprehensive statewide spatiotemporal stream assessment of per- and polyfluoroalkyl substances (PFAS) in an agricultural region of the United States

Public concern regarding per- and polyfluoroalkyl substances (PFAS) has grown substantially in recent years. In addition, research has documented multiple potential agriculture-related release pathways for PFAS (e.g., biosolids and livestock manure). Nevertheless, little research on the environmental prevalence of PFAS has been conducted in agricultural regions of the United States. To fill this gap, we conducted the first statewide spatiotemporal assessment of PFAS in Iowa streams across a region of intense agricultural activity. At least one PFAS was detected at 19 of the 60 stream sites sampled (32%) with 10 different PFAS detected statewide. The number of PFAS detected in the stream samples ranged from one to nine. While PFAS were detected in agricultural streams, sites with the most PFAS detected and in the highest concentration were small, effluent-affected streams where wastewater treatment plant discharge is driving stream PFAS concentrations. No individual PFAS had an exposure:activity ratio (EAR) of >1.0 (exposure concentration shown to trigger observed adverse biological activity). Five stream locations, however, had at least one EAR of >0.001, a precautionary effect screening threshold. Additional targeted temporal sampling would be beneficial to specifically capture potential agricultural source applications and corresponding runoff conditions to fully characterize the prevalence of PFAS in such agricultural systems.

Iowa

Perfluorooctanesulfonate adversely affects a mayfly (Neocloeon triangulifer) at environmentally realistic concentrations

Of the emerging contaminant types thought to threaten freshwater biota, per- and polyfluoroalkyl substances appear to be particularly widespread, and limited studies conducted with these compounds thus far indicate insects may be particularly sensitive to them. This study investigated the short- and long-term effects of two commonly detected compounds on the laboratory-reared mayfly Neocloeon triangulifer in water only exposures. In acute tests, the mayfly was approximately 85-fold more sensitive to perfluorooctanesulfonate (PFOS) and 7-fold more sensitive to perfluorooctanoic acid (PFOA) than the next most sensitive species reported in the literature. In 14 day and full-life chronic PFOS toxicity tests, the lowest 10% effect concentration was 0.272 μg of PFOS/L, which is lower than any previous reports to the best of our knowledge, but consistent in demonstrating the sensitivity of insects to this compound. Conversely, N. triangulifer was not particularly chronically sensitive to PFOA. This study demonstrates the risks of environmentally relevant concentrations of PFOS to a freshwater insect and suggests that investigation of the toxicity of more compounds with different carbon-chain lengths and functional groups to freshwater insects is needed.

Environmental Science & Technology Letters

Environmental surveillance and detection of infectious highly pathogenic avian influenza virus in Iowa wetlands

Avian influenza viruses (AIVs) infect both wild birds and domestic poultry, resulting in economically costly outbreaks that have the potential to impact public health. Currently, a knowledge gap exists regarding the detection of infectious AIVs in the aquatic environment. In response to the 2021–2022 Eurasian strain highly pathogenic avian influenza (HPAI) A/goose/Guangdong/1/1996 clade 2.3.4.4 lineage H5 outbreak, an AIV environmental outbreak response study was conducted using a One Health approach. An optimized method was used to temporally sample (April and May 2022) and analyze (culture and molecular methods) surface water from five water bodies (four wetlands and one lake used as a comparison location) in areas near confirmed HPAI detections in wild bird or poultry operations. Avian influenza viruses were isolated from water samples collected in April from all four wetlands (not from the comparison lake sample); HPAI H5N1 was isolated from one wetland. No virus was isolated from the May samples. Several factors, including increased water temperatures, precipitation, biotic and abiotic factors, and absence of AIV-contaminated fecal material due to fewer waterfowl present, may have contributed to the lack of virus isolation from May samples. Results demonstrate surface water as a plausible medium for transmission of AIVs, including the HPAI virus.

Iowa

Chemical composition of leachates from hydraulic fracturing proppants from surficial releases in southeastern New Mexico

Resin-coated proppants (RCPs) are used in hydraulic fracturing of oil and gas wells to improve well performance; however, these proppants could be a cause for environmental concern if they are disposed of improperly. In this study, we investigate the water-leachable organic and inorganic constituents from proppants collected from surficial releases of RCPs in southeastern New Mexico. Significant concentrations of nonvolatile dissolved organic matter (>100 mg C/L) and phenolic compounds (>50 mg phenol/L) were identified in one of the proppant leachates, with further gas chromatography–mass spectrometry analysis identifying isomers of bisphenol F, a known endocrine disruptor analogous to bisphenol A, as the main organic constituents within this leachate. Fluorescence excitation–emission matrices analyses of proppant leachates identified several peaks associated with phenolic compounds, similar to previously studied oilfield wastewaters. Precursors of polyurethane production, including the inhalation sensitizer methylene diphenyl diisocyanate, were identified in the leachate from another proppant sample. An understanding of leachable compounds from RCPs is vital to management of environmental contamination from surficial releases, protecting the public and industry workers from associated hazards, and identifying the sources of organic compounds in oilfield wastewaters.

New Mexico

PFAS river export analysis highlights the urgent need for catchment-scale mass loading data

Source apportionment of per- and polyfluoroalkyl substances (PFAS) requires an understanding of the mass loading of these compounds in river basins. However, there is a lack of temporally variable and catchment-scale mass loading data, meaning identification and prioritization of sources of PFAS to rivers for management interventions can be difficult. Here, we analyze PFAS concentrations and loads in the River Mersey to provide the first temporally robust estimates of PFAS export for a European river system and the first estimates of the contribution of wastewater treatment works (WwTWs) to total river PFAS export. We estimate an annual PFAS export of 68.1 kg for the River Mersey and report that the yield of perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in the catchment is among the highest recorded globally. Analysis of river and WwTW loads indicates approximately one-third of PFOA emitted from WwTWs is potentially stored in the catchment and approximately half of PFOS transported by the River Mersey may not originate from WwTWs. As governments move toward regulation of PFAS in WwTW effluents, our findings highlight the complexity of PFAS source apportionment and the need for catchment-scale mass loading data. This study indicates that strategies for reducing PFAS loading that focus solely on WwTW effluents may not achieve river water quality targets.

Environmental Science & Technology Letters

Use of stable isotope signatures to determine mercury sources in the Great Lakes

Sources of mercury (Hg) in Great Lakes sediments were assessed with stable Hg isotope ratios using multicollector inductively coupled plasma mass spectrometry. An isotopic mixing model based on mass-dependent (MDF) and mass-independent fractionation (MIF) (δ 202 Hg and Δ 199 Hg) identified three primary Hg sources for sediments: atmospheric, industrial, and watershed-derived. Results indicate atmospheric sources dominate in Lakes Huron, Superior, and Michigan sediments while watershed-derived and industrial sources dominate in Lakes Erie and Ontario sediments. Anomalous Δ 200 Hg signatures, also apparent in sediments, provided independent validation of the model. Comparison of Δ 200 Hg signatures in predatory fish from three lakes reveals that bioaccumulated Hg is more isotopically similar to atmospherically derived Hg than a lake’s sediment. Previous research suggests Δ 200 Hg is conserved during biogeochemical processing and odd mass-independent fractionation (MIF) is conserved during metabolic processing, so it is suspected even is similarly conserved. Given these assumptions, our data suggest that in some cases, atmospherically derived Hg may be a more important source of MeHg to higher trophic levels than legacy sediments in the Great Lakes.

Lake Erie, Lake Huron, Lake Michigan, Lake Ontario

Metformin and other pharmaceuticals widespread in wadeable streams of the southeastern United States

Pharmaceutical contaminants are growing aquatic-health concerns and largely attributed to wastewater treatment facility (WWTF) discharges. Five biweekly water samples from 59 small Piedmont (United States) streams were analyzed for 108 pharmaceuticals and degradates using high-performance liquid chromatography and tandem mass spectrometry. The antidiabetic metformin was detected in 89% of samples and at 97% of sites. At least one pharmaceutical was detected at every site (median of 6, maximum of 45), and several were detected at ≥10% of sites at concentrations reported to affect multiple aquatic end points. Maximal cumulative (all detected compounds) concentrations per site ranged from 17 to 16000 ng L –1 . Watershed urbanization, water table depth, soil thickness, and WWTF metrics correlated significantly with in-stream pharmaceutical contamination. Comparable pharmaceutical concentrations and detections at sites with and without permitted wastewater discharges demonstrate the importance of non-WWTF sources and the need for broad-scale mitigation. The results highlight a fundamental biochemical link between global human-health crises like diabetes and aquatic ecosystem health.

Environmental Science & Technology Letters

Nitrapyrin in streams: The first study documenting off-field transport of a nitrogen stabilizer compound

Nitrapyrin is a bactericide that is co-applied with fertilizer to prevent nitrification and enhance corn yields. While there have been studies of the environmental fate of nitrapyrin, there is no documentation of its off-field transport to streams. In 2016, 59 water samples from 11 streams across Iowa were analyzed for nitrapyrin and its degradate, 6-chloropicolinic acid (6-CPA), along with three widely used herbicides, acetochlor, atrazine, and metolachlor. Nitrapyrin was detected in seven streams (39% of water samples) with concentrations ranging from 12 to 240 ng/L; 6-CPA was never detected. The herbicides were ubiquitously detected (100% of samples, 28–16000 ng/L). Higher nitrapyrin concentrations in streams were associated with rainfall events following spring fertilizer applications. Nitrapyrin persisted in streams for up to 5 weeks. These results highlight the need for more research focused on the environmental fate and transport of nitrapyrin and the potential toxicity this compound could have on nontarget organisms.

Environmental Science & Technology Letters

Assessing pesticide application contributions of per- and polyfluoroalkyl substances (PFAS) in agricultural streams

Research has documented per-and polyfluoroalkyl substances (PFAS) to be prevalent in streams impacted by urban sources; less is known regarding PFAS contributions via pesticide applications: PFAS coming from pesticide containers and “inert” ingredients not listed on pesticide formulation labels. To better understand co-occurrence of pesticides and PFAS in agricultural streams, 10 streams were sampled in two agricultural valleys in northern California, USA during two periods of pesticide application (May and July of 2024). Water samples were analyzed for 183 pesticides and 57 PFAS. Sixty pesticides were detected: 23 herbicides, 18 insecticides, 18 fungicides, and 1 synergist. Overall detection frequencies (DF) ranged from 0 to 100%, and concentrations ranged from non-detect (ND) to 782 ng/L (fluxapyroxad). Fourteen PFAS were detected: 6 perfluoroalkyl carboxylates, 5 perfluoroalkyl sulfonates, 2 perfluoroalkyl acid precursors, and 1 perfluoroalkyl phosphinic acid with DFs ranging from 0 to 60% (PFOA) and concentrations ranging from ND to 20 ng/L (PFBA). Co-occurrence of PFAS and pesticides was observed in 80% of samples. Adopting the global definition of PFAS (includes fluorinated pesticides), pesticide applications are a likely source of instream PFAS. Examination of total organic fluorine and transformations to terminal and ultra-short PFAS could further elucidate pesticide contributions to environmental PFAS.

California

Microplastics undergo fragmentation during pressurized membrane filtration

Low-micrometer microplastics (<10 μm) have been detected in drinking water, driving growing interest in using pressure-driven membrane filtration to remove these particles and ensure drinking water safety. However, little attention is paid to the fate of microplastics concentrated in the filtration byproduct. In this study, using well-defined polystyrene (PS) and poly(methyl methacrylate) microspheres as model particles, we observed microplastic fragmentation during nanofiltration and the subsequent release of smaller fragments. After operating for 3 h at 20 bar, 67.9 ± 8.0% of the PS spheres in the concentrate, based on particles counted in selected fields of view, were transformed into fractured particles. The characteristic Raman band signals of microplastics were significantly weakened after fragmentation, leading to detection challenges. To address this, a data processing algorithm was developed to identify PS fragments as small as 1 μm. Preliminary statistical analysis reveals that within the tested pressure range, operation time has a stronger influence on fragmentation than pressure magnitude alone and that fragmentation is further governed by the intrinsic mechanical properties of the tested model polymers. This work provides direct evidence that pressure-driven membrane processes induce microplastic fragmentation and highlights the environmental risks associated with the discharge of fragmented microplastics into the concentrate.

Environmental Science & Technology Letters

Occurrence of neonicotinoid insecticides in finished drinking water and fate during drinking water treatment

Neonicotinoid insecticides are widespread in surface waters across the agriculturally-intensive Midwestern US. We report for the first time the presence of three neonicotinoids in finished drinking water and demonstrate their general persistence during conventional water treatment. Periodic tap water grab samples were collected at the University of Iowa over seven weeks in 2016 (May-July) after maize/soy planting. Clothianidin, imidacloprid, and thiamethoxam were ubiquitously detected in finished water samples and ranged from 0.24-57.3 ng/L. Samples collected along the University of Iowa treatment train indicate no apparent removal of clothianidin and imidacloprid, with modest thiamethoxam removal (~50%). In contrast, the concentrations of all neonicotinoids were substantially lower in the Iowa City treatment facility finished water using granular activated carbon (GAC) filtration. Batch experiments investigated potential losses. Thiamethoxam losses are due to base-catalyzed hydrolysis at high pH conditions during lime softening. GAC rapidly and nearly completely removed all three neonicotinoids. Clothianidin is susceptible to reaction with free chlorine and may undergo at least partial transformation during chlorination. Our work provides new insights into the persistence of neonicotinoids and their potential for transformation during water treatment and distribution, while also identifying GAC as an effective management tool to lower neonicotinoid concentrations in finished drinking water.

Environmental Science & Technology Letters

Occurrence of dichloroacetamide herbicide safeners and co-applied herbicides in midwestern U.S. streams

Dichloroacetamide safeners (e.g., AD-67, benoxacor, dichlormid, and furilazole) are co-applied with chloroacetanilide herbicides to protect crops from herbicide toxicity. While such safeners have been used since the early 1970s, there are minimal data about safener usage, occurrence in streams, or potential ecological effects. This study focused on one of these research gaps, occurrence in streams. Seven Midwestern U.S. streams (five in Iowa and two in Illinois), with extensive row-crop agriculture, were sampled at varying frequencies from spring 2016 through summer 2017. All four safeners were detected at least once; furilazole was the most frequently detected (31%), followed by benoxacor (29%), dichlormid (15%), and AD-67 (2%). The maximum concentrations ranged from 42 to 190 ng/L. Stream detections and concentrations of safeners appear to be driven by a combination of timing of application (spring following herbicide application) and precipitation events. Detected concentrations were below known toxicity levels for aquatic organisms.

Illinois, Iowa

Mercury isotopes reveal an ontogenetic shift in habitat use by walleye in lower Green Bay of Lake Michigan

In general, fish residing in rivers differ from fish residing in lakes in their mercury (Hg) isotope ratios. Specifically, fish residing in lakes typically show enriched values for the isotope ratios of δ 202 Hg (mass-dependent fractionation of isotope 202 Hg) and Δ 199 Hg (mass-independent fractionation of isotope 199 Hg) compared with fish residing in rivers, because photochemical effects acting on Hg isotope ratios are stronger in lakes than in rivers. Whole-fish determinations of Hg isotope ratios in age-0 and adult (ages 4–11) walleye ( Sander vitreus ) caught in the Fox River, the main tributary to lower Green Bay of Lake Michigan, were dissimilar. Age-0 fish exhibited a river signature for δ 202 Hg and Δ 199 Hg, with means equal to 0.00 and 0.26‰, respectively. Significantly elevated levels of δ 202 Hg and Δ 199 Hg were observed in adult fish, indicating that adult fish primarily resided in the bay. Our results implied that the Fox River serves as a nursery area for juvenile walleye in the Fox River–lower Green Bay ecosystem. Moreover, corrections for photochemical fractionation of δ 202 Hg revealed that age-0 and adult walleye shared the same source of Hg in this ecosystem. In addition, Hg isotope ratios did not significantly differ between the sexes of adult walleye, suggesting that these ratios did not fractionate during the Hg elimination process.

Environmental Science & Technology Letters

Chlorinated byproducts of neonicotinoids and their metabolites: An unrecognized human exposure potential?

We recently reported the initial discovery of neonicotinoid pesticides in drinking water and their potential for transformation through chlorination and alkaline hydrolysis during water treatment. The objectives of this research were: (1) to determine if neonicotinoid metabolites are relevant to drinking water exposure and (2) to identify the products formed from chlorination of neonicotinoids and their metabolites. Desnitro-imidacloprid and imidacloprid-urea, two known metabolites of imidacloprid, are documented for the first time in drinking water. Desnitro-imidacloprid was present above the lower level of detection (0.03 ng/L) in 67% of samples (six of nine) from drinking water systems but detectable in all samples (up to 0.6 ng/L). Although concentrations of desnitro-imidacloprid were lower than concentrations of the parent neonicotinoids, desnitro-imidacloprid exhibits significantly greater mammalian toxicity than imidacloprid. Using LC-HR-ToF-MS/MS analysis of results from laboratory experiments, we propose structures for novel transformation products resulting from the chlorination of clothianidin, imidacloprid, desnitro-imidacloprid, imidacloprid-urea, and hydrolysis products of thiamethoxam. Formation of chlorinated neonicotinoid byproducts occurs at time scales relevant to water treatment and/or distribution for the imidacloprid metabolites ( t 1/2 values from 2.4 min to 1.0 h) and thiamethoxam hydrolysis products (4.8 h). Neonicotinoid metabolites in finished drinking water and potential formation of novel disinfection byproducts during treatment and/or distribution are relevant to evaluating the exposure and potential impacts of neonicotinoids on human health.

Environmental Science & Technology Letters

Tracing the uptake of Hg(II) in an iron-reducing bacterium using mercury stable isotopes

Anaerobic microorganisms play a key role in the biological mercury (Hg) cycle due to their ability to produce bioaccumulative neurotoxic methylmercury (MeHg). However, despite recent advances, how bacteria accumulate inorganic Hg [Hg(II)] prior to methylation is largely unknown. In this study, we applied Hg stable isotopes to measure changes in cellular compartments of Geobacter sulfurreducens and a nonmethylating mutant strain to investigate intracellular transport of Hg(II). Both strains accumulated intracellular Hg(II) that was lower in δ 202 Hg relative to dissolved extracellular Hg(II), demonstrating mass-dependent fractionation during uptake. Hg reduction by the mutant strain (50% Hg concentration loss in 24 h) resulted in higher δ 202 Hg values of cellular Hg than in wild-type cells. Further observations showed increasing δ 202 Hg values in dissolved extracellular MeHg and Hg(II) but decreasing δ 202 Hg values of intracellular Hg(II) in wild-type G. sulfurreducens suggesting that external Hg pools may be the proximate source of Hg for methylation in this bacterium. This investigation demonstrates that cellular uptake is comprised of multiple processes and transformations that influence Hg(II) prior to methylation, which can impart distinct isotopic signatures to Hg(II) and MeHg pools in the environment.

Environmental Science and Technology Letters

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout

Lake trout ( Salvelinus namaycush ), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0–6.9 kg L –1 ) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon ( Oncorhynchus nerka ) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicates niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of the contaminant source to the receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Alaska