Geology Reports⌕ Search

SEARCH · Geology Reports

Results for “Analytical Sciences”

Search indexed USGS publications on groundwater, aquifers, geologic maps, mineral resources and earthquakes. Explore source records by subject and place.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 361 records · Page 20Linked to original sources

Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999-2000: A national reconnaissance

To provide the first nationwide reconnaissance of the occurrence of pharmaceuticals, hormones, and other organic wastewater contaminants (OWCs) in water resources, the U.S. Geological Survey used five newly developed analytical methods to measure concentrations of 95 OWCs in water samples from a network of 139 streams across 30 states during 1999 and 2000. The selection of sampling sites was biased toward streams susceptible to contamination (i.e. downstream of intense urbanization and livestock production). OWCs were prevalent during this study, being found in 80% of the streams sampled. The compounds detected represent a wide range of residential, industrial, and agricultural origins and uses with 82 of the 95 OWCs being found during this study. The most frequently detected compounds were coprostanol (fecal steroid), cholesterol (plant and animal steroid), N , N -diethyltoluamide (insect repellant), caffeine (stimulant), triclosan (antimicrobial disinfectant), tri(2-chloroethyl)phosphate (fire retardant), and 4-nonylphenol (nonionic detergent metabolite). Measured concentrations for this study were generally low and rarely exceeded drinking-water guidelines, drinking-water health advisories, or aquatic-life criteria. Many compounds, however, do not have such guidelines established. The detection of multiple OWCs was common for this study, with a median of seven and as many as 38 OWCs being found in a given water sample. Little is known about the potential interactive effects (such as synergistic or antagonistic toxicity) that may occur from complex mixtures of OWCs in the environment. In addition, results of this study demonstrate the importance of obtaining data on metabolites to fully understand not only the fate and transport of OWCs in the hydrologic system but also their ultimate overall effect on human health and the environment.

Environmental Science & Technology↗

Land application of biosolid, livestock, and drilling wastes to US farmland: A potential pathway for the redistribution of contaminants in the environment

In the United States (U.S.), waste byproducts generated from the treatment of municipal waste (biosolids), production of livestock (livestock waste), and drilling of oil and gas wells (drilling waste) are commonly applied to agricultural lands. Although this can be a cost-effective reuse/disposal practice, there is limited research on the potential for contaminant exposures and effects on ecosystems, wildlife, and human health from such land applications. In this study, we conducted extensive chemical, microbial, and toxicity analyses of biosolid, livestock, and drilling wastes just prior to land application on agricultural lands at 34 sites across the U.S. Twenty-two analytical methods were used to determine potential contaminant exposures profiles for 452 organic and 114 inorganic chemicals, nine microbial groups, estrogenicity, and cytotoxicity. Analytical results document unique and substantial chemical, microbial, and toxicity profiles for these land-applied wastes. Of the three waste byproducts, biosolids contained the greatest concentrations of household chemicals, pesticides, pharmaceuticals, per-/polyfluoroalkyl substances, calcium, and phosphorus. Livestock waste contained the greatest concentrations of total and leachable dissolved organic carbon, biogenic hormones, mycotoxins, plant estrogens, total inorganic nitrogen, and potassium. Drilling waste contained the greatest concentrations of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes), polycyclic aromatic hydrocarbons, rare-earth elements, barium, strontium, and uranium–thorium series radioisotopes. Biosolid and livestock wastes had greater culturable heterotrophic bacteria, halophilic bacteria, Escherichia coli ( E. coli ), enterococci, and staphylococci concentrations, and greater microbial diversity than drilling waste. Bioassay analyses indicated that exposure to contaminants in livestock wastes and biosolids could result in estrogenic effects, whereas exposure to contaminants in drilling waste could result in cytotoxic effects. Our study documents that current reuse/disposal practices for biosolid, livestock, and drilling wastes on agricultural lands could provide a potential pathway for the redistribution of unique and complex contaminant mixtures into the environment that have bioactive, endocrine disrupting, and carcinogenic characteristics. Results of this study provide a snapshot of chemical compositions and concentrations that can be used to inform the development of best-management practices to help maximize beneficial reuse of these wastes and minimize risk to the environment and human health.

Environmental Science: Processes & Impacts↗

Cape Romain partnership for coastal protection

This final report summarizes activities, outcomes, and lessons learned from a 3-year project titled “Climate Change Adaptation for Coastal National Wildlife Refuges” with the Cape Romain National Wildlife Refuge (NWR) and local partners in the surrounding South Carolina Lowcountry. The Lowcountry is classified as the 10-county area encompassing the coastal plain of South Carolina (this report specifically focuses on Berkeley, Charleston, and Georgetown Counties). The goals of this work, sponsored by the U.S. Geological Survey’s Southeast Climate Adaptation Science Center (SECASC), were to foster active engagement with stakeholders; to develop a comprehensive definition of adaptation problems faced by agencies, organizations, and individuals near the Cape Romain NWR that accounts for global change, local values, knowledge and perceptions; and to encourage social learning and building of effective networks and trust across South Carolina Lowcountry organizations and individuals. Although project scoping began at the scale of the Atlantic seaboard, by engaging with NWRs from Massachusetts to Florida, participating refuge personnel eventually selected the Cape Romain NWR to serve as a case study for testing our goals. The Cape Romain Partnership for Coastal Conservation was established to address global change impacts at a regional level and includes representation from Federal and State resource agencies, local conservation nongovernmental organizations, and organizations representing underserved community interests. Research topics, originating from discussions with Cape Romain Partnership for Coastal Conservation members, focused on quantifying key drivers of change including localized sea-level rise (SLR) predictions, estimates of coastal hurricane inundation as amplified by SLR, and urban growth trends and forecasts. These key drivers provided a foundation to engage stakeholders in planning exercises to begin a process of collective understanding and collaborative decision making. The goal of this process was to develop collective strategies of adaptation to enhance community and ecosystem resilience in the South Carolina Lowcountry. South Carolina’s Lowcountry is experiencing rapid environmental and social transformation because of SLR rates approaching twice the global average, chronic tidal flooding and catastrophic storm surges, erosion and loss of habitats that provide essential services to wildlife and humans, and increasing social polarization fueled by aggressive low-density urban growth and other forms of land conversion. To support characterizations of plausible future scenarios, we used available or, in some cases, developed new models to project future conditions of key environmental and social-economic drivers. Because of the imprecision of mean global SLR projections, the SECASC commissioned a climatological study to account for local conditions and multiple representative concentration pathways to project a tailored distribution of future sea levels. These projections were matched to SLR scenarios provided by existing models to anticipate the range of future coastal habitat changes in the South Carolina Lowcountry. SLR scenarios were also incorporated into existing storm-surge models, which do not account for alternate baseline sea levels, to project the local effects of future hurricanes. To evaluate the extent and effects of population growth and urban expansion, we relied on an existing urban-growth model to map the spatial distribution of land-conversion probabilities, the total area of which is predicted to increase twofold to threefold over the next 60 years. In addition to this simplified model, an econometric model is in development to account for nonlinear feedback dynamics in land value, land use, and ecosystem service production. Although not yet completed, the goals of this model are to produce more-detailed projections of growth dynamics and to allow predictions of development patterns resulting from alternate land-use planning policies and incentives. Collaborative planning for an uncertain future requires more than providing decision makers with information on future physical and ecological conditions; developing effective and consensual strategies must also integrate sociological values, multiple cultural perspectives, and an understanding of human behavior. To support broad stakeholder engagement in integrative approaches to adaptation planning, emphasis was placed on the importance of considering differences in how individuals perceive their environment and create meaning. Because cultural frameworks form the basis for perceptions and, ultimately, the behaviors of individuals and institutions, we describe a model of human behavior and how it can be used to understand the effect of cultural complexity and variation in perception on choices, behavioral change, and long-term maintenance of behaviors. We consider a model commonly used in the field of behavioral health that accommodates variation in human perception when describing stages of behavior and the dynamics of behavioral change. Tailoring communication and engagement activities to targeted stakeholders is likely to benefit from increased understanding of behavioral change processes. The complex nature of this problem limited the usefulness of a traditional decision-analytic approach, we explored alternative methods for engagement, collaborative learning and decision making. Recognizing that project partners and Lowcountry stakeholders may be at different stages of preparedness and interest level for modifying behavior as a function of global change, we facilitated a scenario-planning exercise to familiarize partners with this well-established approach for communicating the opportunities and threats arising under alternative, plausible futures. We developed narratives for four alternative South Carolina Lowcountry scenarios to be used in later strategic planning that focus on quantitative trends for three primary drivers with high impact and high uncertainty: manifestations of climate change, social-political shifts at a global level, and forces of local value and power structures. This scenario-planning exercise underscored the complex relation between the temporospatial scale of the production of ecological goods and services and the institutional scale at which they are managed. We then guided the partners through an assessment of the relevant strengths and weaknesses of the Cape Romain Partnership for Coastal Protection, using the threats and opportunities characterized by each scenario to understand how the partnership might respond when attempting to meet conservation and societal objectives. The partnership identified key strengths including partnership experience, outreach and technical capacities, a substantial conservation land base, and high social cohesion in the South Carolina Lowcountry. Limited communication expertise, institutional inertia, and insufficient staffing and funding were recognized as important weaknesses across the partnership. By examining and scoring combinations of internal strengths and weaknesses and external threats and opportunities, the partnership developed sets of prioritized strategies to consider in the context of a given scenario. Although we had insufficient time to examine all scenarios in detail, the intent was to identify a portfolio of strategic actions to address threats and opportunities represented in multiple plausible futures. Top-ranking strategies encompassed a range of actions that focused on strengthening the conservation community and communicating the benefits of nature (that is, ecosystem services) to leveraging partnerships to expand land protection. This report also details the methods and preliminary results of several models developed or applied in support of this project. Two parcel-selection algorithms were used to evaluate anticipated habitat changes and patterns of urban growth to guide decisions on optimal conservation reserve design to protect habitat communities. One approach used a widely available planning software (MARXAN) to maximize conservation benefits near the Cape Romain NWR, whereas the other approach was a novel application of economic theory to account for uncertainty in future conditions and for the risks of unanticipated habitat loss. This latter model applies modern portfolio theory to estimate the risk of investing in any portfolio of land parcels (that is, candidate “reserves”) under climate-change uncertainty by quantifying the variation and spatial correlation of conservation benefits derived from each portfolio. We expanded the range of actions beyond simply whether or not to invest in a set of land parcels, an approach commonly used in spatial conservation planning, to also include consideration of divestment from currently protected lands. Such refinements allow for better accounting of system dynamics and can evaluate the benefits of flexible conservation tools such as rolling easements. Model results were conditional on a decision maker’s risk tolerance but highlighted general strategies of land conservation to increase future habitat representation beyond what is expected under the current protected land base. We built models that may help inform coastal planning by estimating salinity dynamics and the performance of oyster reef restoration efforts to predict the combined effects of global change and management of freshwater flows on coastal habitats and the processes that contribute to their resilience. These models can support restoration decisions by evaluating the expected benefits of site locations for shoreline protection and fisheries production. Lastly, we developed a spatially explicit economic model that predicts feedback dynamics among land value, land-use change, and effects on ecosystem service provision to explore zoning policies and incentives on urban growth and ecosystem services. We summarize these efforts with insights and considerations for the Cape Romain Partnership for Coastal Protection to continue to engage stakeholders in effective adaptation planning. First, notions of place attachment (referred to as sense of place), and the role of culture in social discourse are increasingly being used to understand the complex interactions between society and the environment and how societies respond and adapt to climate change. Sense of place was a unifying theme whenever the future of the South Carolina Lowcountry was discussed. The contribution of the South Carolina Lowcountry’s environmental wealth, rich cultural heritage, and quality of life to sense of place has important implications for how adaptation planning might best be pursued. More community-based governance of the commons (in other words, natural and cultural resources held in common), in which broad stakeholder participation and power sharing are key elements, is considered important. This devolution of governance is characterized by polycentric institutions and self-organizing social networks that promote a local culture of knowledge sharing, problem solving, and learning. These so-called bridging organizations (or individuals) often provide the leadership necessary to bring together potentially disparate Government agencies and institutions, private organizations, and individuals in a collective process of problem solving. Our observations also suggest that the conservation community in the South Carolina Lowcountry views its activities as integral to the broader governance of social-ecological systems, in which responses to the forces of global change are mediated through culture, economics, and politics. Rather than directly competing with other interests, the South Carolina Lowcountry conservation community seems to embrace an interpretation of conservation in which the fundamental objective is the quality of human life rather than environmental protection. Fundamental to the types of governance reforms described above is the notion of coproduction, in which experts and users collaborate to develop a shared body of knowledge. In this approach, scientists work with stakeholders to help frame questions, design research, and collect and analyze data. Such sustained collaborations are increasingly believed to be an effective way to produce useable (or actionable) science. The emphasis on social learning, leveraging strong social networks, coordinating and deliberating among diverse stakeholders, and applying principles of adaptive management is an essential contribution to adaptive capacity. The diverse and robust set of scientific approaches, methods to help stakeholders collaborate in effective and goal-driven planning processes, and decision tools resulting from this project hopefully will assist Cape Romain NWR and its partners prepare for climatic, ecological, and social changes over the coming decades.

South Carolina↗

Characterizing pyrethroid and fipronil concentrations in biosolids

Pesticides are prevalent in wastewater, yet few studies have measured pesticides in biosolids and aqueous media from samples collected concurrently. Seventeen California wastewater treatment plants (WWTPs) were sampled in May 2020. Biosolids samples were analyzed for 27 analytes, and paired aqueous samples (influent and effluent) were analyzed for 23 analytes. Analytes included fipronil and its transformation products (fiproles), pyrethroids, novaluron, and several other pesticides with down-the-drain transport potential. Of the 27 compounds analyzed in biosolids samples, 16 were detected in at least one sample, and 10 had a detection frequency (DF) of at least 25 %. Fipronil sulfone, fipronil sulfide, and fipronil were the most frequently detected fiproles (DF = 100 %, 94 %, and 67 %, respectively); permethrin was the most frequently detected pyrethroid (DF = 100 %), followed by bifenthrin (DF = 94 %), cyhalothrin (DF = 89 %), and etofenprox (DF = 78 %). To elucidate fipronil transformation pathways within the treatment system, data from the three sample types were compared; findings were generally consistent with transformation pathways reported previously (e.g., some fiproles were rarely detected in influent or biosolids, but frequently detected in effluent, indicating their formation during the treatment process). No correlations were found between WWTP characteristics and pesticide concentrations in biosolids. The fraction of organic carbon ( f OC ) of each biosolids sample was measured, and a statistically significant negative correlation was observed between f OC and some fiproles, but not fipronil; possible explanations are discussed. Additional analysis for two major agricultural pesticides (bifenthrin and permethrin) indicated that estimated mass loads of these pesticides in biosolids applied to land as a soil amendment are minimal (approximately 2 to 3 orders of magnitude lower) compared to inputs from agricultural applications. This study provides insight on the magnitude of pesticides entering the environment via land-applied biosolids; existing regulations surrounding agricultural pesticide applications are expected to also be protective of the relatively low inputs from biosolids.

Science of the Total Environment↗

Dissolved organic carbon dynamics and fluxes in Mississippi-Atchafalaya deltaic system impacted by an extreme flood event and hurricanes: A multi-satellite approach using Sentinel-2/3 and Landsat-8/9 data

Transport of riverine and wetland-derived dissolved organic carbon (DOC) spanning tidal wetlands, estuaries, and continental shelf waters functionally connects terrestrial and aquatic carbon reservoirs, yet the magnitude and ecological significance of this variable and its spatiotemporal linkage remains uncertain for coastal deltaic regions, such as Mississippi River Delta Plain, which includes Mississippi (MR) and Atchafalaya (AR) rivers and estuaries with vast expanses of wetlands and coastal forests. We examined DOC dynamics and fluxes in this large river-dominated wetland-estuarine system for the period between 2019 and 2021 that included an extreme river flood event in 2019, two major hurricanes (Barry in 2019 and Ida in 2021), and cold front passage using an improved adaptive quasi-analytical algorithm (QAA-AD) applied to multi-satellite sensors (Sentinel 3A/B OLCI, Landsat-8/OLI and Sentinel-2A/B MSI) with varying spectral and spatial (10/30/300 m) resolutions. The DOC estimates from multi-satellite sensors in combination with water fluxes were used to assess DOC fluxes from two large rivers (MR and AR) and small channels across the delta plain. Overall, this system delivered a total of 6.7 Tg C yr -1 (1 Tg = 10 12 g) into the estuarine zone and the northern Gulf of Mexico (nGoM) during 2019. High DOC fluxes from the AR (1.3 Tg C yr -1 ) and MR (4.5 Tg C yr -1 ) were associated with the extreme flood event in 2019. Hurricanes that occurred in the study period also contributed to the wetland and estuarine DOC fluxes into continental shelf waters; for example, the passage of Hurricane Barry in July 2019, delivered over a 3-day period ~1.33 ×10 9 g DOC from Barataria Basin into the nGoM. Sentinel 2-MSI land and water classification revealed that Hurricane Ida eroded a total of 1.34×10 8 m 2 of marshes in middle Barataria Basin, converting those habitats into open water with 3.0 m inundation depth and high DOC concentrations (16.4 mg L -1 ), a potentially large DOC source to the coastal waters. Overall, storms and flood events are major sources of DOC flux that facilitate transport of upstream carbon as well as transformation of carbon in the wetlands, through the conversion of vegetated wetland to open water.

Louisiana↗

Methylmercury exposure in wildlife: A review of the ecological and physiological processes affecting contaminant concentrations and their interpretation

Exposure to methylmercury (MeHg) can result in detrimental health effects in wildlife. With advances in ecological indicators and analytical techniques for measurement of MeHg in a variety of tissues, numerous processes have been identified that can influence MeHg concentrations in wildlife. This review presents a synthesis of theoretical principals and applied information for measuring MeHg exposure and interpreting MeHg concentrations in wildlife. Mercury concentrations in wildlife are the net result of ecological processes influencing dietary exposure combined with physiological processes that regulate assimilation, transformation, and elimination. Therefore, consideration of both physiological and ecological processes should be integrated when formulating biomonitoring strategies. Ecological indicators, particularly stable isotopes of carbon, nitrogen, and sulfur, compound-specific stable isotopes, and fatty acids, can be effective tools to evaluate dietary MeHg exposure. Animal species differ in their physiological capacity for MeHg elimination, and animal tissues can be inert or physiologically active, act as sites of storage, transformation, or excretion of MeHg, and vary in the timing of MeHg exposure they represent. Biological influences such as age, sex, maternal transfer, and growth or fasting are also relevant for interpretation of tissue MeHg concentrations. Wildlife tissues that represent current or near-term bioaccumulation and in which MeHg is the predominant mercury species (such as blood and eggs) are most effective for biomonitoring ecosystems and understanding landscape drivers of MeHg exposure. Further research is suggested to critically evaluate the use of keratinized external tissues to measure MeHg bioaccumulation, particularly for less-well studied wildlife such as reptiles and terrestrial mammals. Suggested methods are provided to effectively use wildlife for quantifying patterns and drivers of MeHg bioaccumulation over time and space, as well as for assessing the potential risk and toxicological effects of MeHg on wildlife.

Science of the Total Environment↗

Routine determination of sulfonylurea, imidazolinone, and sulfonamide herbicides at nanogram-per-liter concentrations by solid-phase extraction and liquid chromatography/mass spectrometry

Sulfonylurea (SU), imidazolinone (IMI), and sulfonamide (SA) herbicides are new classes of low-application-rate herbicides increasingly used by farmers. Some of these herbicides affect both weed and crop species at low dosages and must be carefully used. Less is known about the effect of these compounds on non-crop plant species, but a concentration of 100 ng/l in water has been proposed as the threshold for possible plant toxicity for most of these herbicides. Hence, analytical methods must be capable of detecting SUs, IMIs, and SAs at concentrations less than 100 ng/l in ambient water samples. The authors developed a two-cartridge, solid-phase extraction method for isolating 12 SU, 3 IMI, and 1 SA herbicides by using high-performance liquid chromatography/electrospray ionization-mass spectrometry (HPLC/ESI-MS) to identify and quantify these herbicides to 10 ng/l. This method was used to analyze 196 surface- and ground-water samples collected from May to August 1998 throughout the Midwestern United States, and more than 100 quality-assurance and quality-control samples. During the 16 weeks of the study, the HPLC/ESI-MS maintained excellent calibration linearity across the calibration range from 5 to 500 ng/l, with correlation coefficients of 0.9975 or greater. Continuing calibration verification standards at 100-ng/l concentration were analyzed throughout the study, and the average measured concentrations for individual herbicides ranged from 93 to 100 ng/l. Recovery of herbicides from 27 reagent-water samples spiked at 50 and 100 ng/l ranged from 39 to 92%, and averaged 73%. The standard deviation of recoveries ranged from 14 to 26%, and averaged 20%. This variability reflects multiple instruments, operators, and the use of automated and manual sample preparation. Spiked environmental water samples had similar recoveries, although for some herbicides, the sample matrix enhanced recoveries by as much as 200% greater than the spiked concentration. This matrix enhancement was sample- and compound-dependent. Concentrations of herbicides in unspiked duplicate environmental samples were typically within 25% of each other. The results demonstrate the usefulness of HPLC/ESI-MS for determining low-application-rate herbicides at ambient concentrations.

Science of Total Environment↗

40Ar/39Ar and 18O/16O studies of the Chegem ash-flow caldera and the Eldjurta Granite: Cooling of two late Pliocene igneous bodies in the Greater Caucasus Mountains, Russia

Volcanic and intrusive rocks of the Chegem caldera and the nearby Eldjurta (Eldzhurtinskiy) Granite record a late Pliocene episode of silicic magmatism in the north-central Caucasus Mountains. Surface exposures, created by the recent rapid uplift and erosion of the Caucasus Mountains, span a 2 km vertical section of Chegem caldera fill and 1150 m of the Eldjurta Granite; cored mineral-exploration drillholes in the Eldjurta Granite extend the sampling to a depth of 4 km. The unique sampling range available in these two young igneous bodies affords an excellent opportunity to study their denudation and cooling histories, which we examine by means of 40 Ar/ 39 Ar and 18 O/ 16 O measurements on an extensive sample suite. Total-fusion biotite and sanidine ages from eight Chegem Tuff samples, both intracaldera and outflow, are analytically indistinguishable with a weighted mean of 2.82 ± 0.02 Ma. A cross-cutting granodiorite porphyry intrusion has a sanidine total fusion age of 2.84 ± 0.03 Ma, and whole-rock incremental heating of a post-caldera andesite flow, which caps the caldera fill, yields an age of 2.82 ± 0.02 Ma. Thus, caldera formation and post-caldera resurgence and volcanism all occurred within a very short time (< 50,000 yr). Biotite total-fusion ages of ten Eldjurta Granite samples, including seven from ∼ 500 m intervals in the 4 km deep drillhole, show a systematic linear decrease in age with depth from 1.90 Ma near the roof contact of the granite to 1.56 Ma at a depth of 3700 m. Assuming these ages were set at the same temperature, this age/depth gradient implies an isotherm migration rate of 13 mm/yr between 1.90 and 1.56 Ma. This migration rate is due to a combination of rapid denudation and downward relaxation of isotherms, with cooling rates between 200 and 500°C/Ma during this period. Oxygen isotopic compositions of quartz, K-feldspar, plagioclase and biotite from the drillhole samples below the 800 m depth are fairly uniform and record primary igneous δ 18 O values with little evidence for subsolidus hydrothermal activity. However, in surface outcrop samples and in the shallowest drillhole sample, mineral δ 18 O values have been lowered by up to 3‰ by interaction with an external (meteoric-hydrothermal?) fluid. The primary mineral δ 18 O values of the Eldjurta Granite are distinctly higher than the corresponding phenocryst δ 18 O values in the Chegem volcanic rocks, indicating that the two bodies evolved as separxate magma batches.

Caucasus Mountains, Chegem Caldera↗

Global review reveals how disparate study motivations, analytical designs, and focal ions limit understanding of salinization effects on freshwater animals

Global salinization of freshwaters is adversely affecting biotic communities and ecosystem processes. We reviewed six decades (1960–2020) of literature published on animal responses to increased salinities across different taxonomic and ecological contexts and identified knowledge gaps. From 585 journal articles, we characterized 5924 responses of mollusks, crustaceans, zooplankton, non-arthropod invertebrates (NAI), insects, fishes, and amphibians to salinization. Insects and fishes were the most studied taxa; Na + and Cl − were the most studied ions − . Collectively, concentrations of the ions examined typically spanned five orders of magnitude. Species' invasiveness was a key motivation for studying mollusks, crustaceans, and fishes; threats of urbanization and road salts were key motivations for studying NAI, zooplankton, and amphibians. Laboratory studies were more common than field studies for most taxa. Focal life stages in laboratory studies varied widely but juveniles and adults were represented similarly in field studies. Studies of mollusks, NAI, and crustacean focused on adults; studies of zooplankton, insects, fishes, and amphibians focused on juveniles. Organismal- and population-level responses measuring solute uptake, internal chemistry, body condition, or ion concentrations predominated laboratory studies; population- and assemblage-level responses measuring abundance, spatial distribution, or assemblage composition predominated field studies. Negative responses to salinization predominated but positive and unimodal responses were apparent across all taxa and organizational levels. Key topics for further research include a) salinity responses by more taxa, b) responses to especially toxic ions (i.e., potassium, bicarbonate, sulfate, magnesium), c) mechanisms causing positive and unimodal responses, d) traits underpinning responses, e) effects transcending organizational levels, f) ion-specific response thresholds, and g) interactions between salinity and other stressors. Our review suggests inter-taxa variation in sensitivity to salinization reflects occurrence of certain biological traits, including gill-breathing, semi-permeable skin, multiple life stages, and limited mobility. We propose a traits-based framework to predict salinization sensitivity from shared traits. This evolutionary approach could inform management aimed at preventing or reducing adverse impacts of freshwater salinization.

Science of the Total Environment↗

New zircon (U-Th)/He and U/Pb eruption age for the Rockland tephra, western USA

Eruption ages of a number of prominent Quaternary volcanic deposits remain inaccurately and/or imprecisely constrained, despite their importance as regional stratigraphic markers in paleo-environment reconstruction and as evidence of climate-altering eruptions. Accurately dating volcanic deposits presents challenging analytical considerations, including poor radiogenic yield, scarcity of datable minerals, and contamination of crystal populations by magma, eruption, and transport processes. One prominent example is the Rockland tephra, which erupted from the Lassen Volcanic Center in the southern Cascade arc. Despite a range in published eruption ages from 0.40 to 0.63 Ma, the Rockland tephra is extensively used as a marker bed across the western United States. To more accurately and precisely constrain the age of the Rockland tephra-producing eruption, we report U/Pb crystallization dates from the outermost ∼2 μm of zircon crystal faces (surfaces) using secondary ion mass spectrometry (SIMS). Our new weighted mean 238 U/ 206 Pb age for Rockland tephra zircon surfaces is 0.598 ± 0.013 Ma (2σ) and MSWD = 1.11 (mean square weighted deviation). As an independent test of the accuracy of this age, we obtained new (U-Th)/He dates from individual zircon grains from the Rockland tephra, which yielded a weighted mean age of 0.599 ± 0.012 Ma (2σ, MSWD = 5.13). We also obtained a (U-Th)/He age of 0.628 ± 0.014 Ma (MSWD = 1.19) for the Lava Creek Tuff member B, which was analyzed as a secondary standard to test the accuracy of the (U-Th)/He technique for Quaternary tephras, and to evaluate assumptions made in the model-age calculation. Concordance of new U/Pb and (U-Th)/He zircon ages reinforces the accuracy of our preferred Rockland tephra eruption age, and confirms that zircon surface dates sample zircon growth up to the time of eruption. We demonstrate the broad applicability of coupled U/Pb zircon-surface and single-grain zircon (U-Th)/He geochronology to accurate dating of Quaternary tephra, and highlight the challenges and opportunities of this technique.

Quaternary Science Reviews↗

Monitoring population-level foraging distribution of a marine migratory species from land: Strengths and weaknesses of the isotopic approach on the Northwest Atlantic loggerhead turtle aggregation

Assessing the linkage between breeding and non-breeding areas has important implications for understanding the fundamental biology of and conserving animal species. This is a challenging task for marine species, and in sea turtles a combination of stable isotope analysis (SIA) and satellite telemetry has been increasingly used. The Northwest Atlantic (NWA) loggerhead ( Caretta caretta ) Regional Management Unit, one of the largest sea turtle populations in the world, provides an excellent opportunity to investigate key biological patterns as well as methodological aspects related to the use of stable isotopes to infer spatial distribution of turtles in foraging areas. We provide the first comprehensive assessment of the annual distribution of NWA adult female loggerheads among foraging areas and investigate the efficacy of various analytical approaches as well as the effect of sample size in these types of studies. A total of 5168 individual females were sampled from seven Management Units (MUs) between 2013-2018. We provide the first estimate of the proportion of females originating from each MU that uses each foraging area and show how this proportion varies over time. We also estimate the relative importance (in terms of number of turtles) of each foraging area to the overall loggerhead breeding aggregation nesting in Florida and in the NWA for each year of the study. The foraging area used by reproductively active females differs considerably across MUs. One of these, the Subtropical NWA, is by far the most important foraging area in terms of both number of individuals and genetic diversity, and therefore this region may be considered as a conservation priority. Through simulations, we show that limited sizes of sample groups (unknowns; training; priors) may result in false geographic differentiation and consequently mislead interpretations. We provide thresholds and methodological recommendations for future studies. This study establishes a fundamental baseline for monitoring the annual contribution of foraging area to a terrestrial-based breeding aggregation of a marine animal in a cost-effective way. This type of monitoring allows for early detection of changes in foraging distributions—a possible effect of climate change on marine ecosystems or of area-specific anthropogenic threats.

Frontiers in Marine Science↗

In vitro effects-based method and water quality screening model for use in pre- and post-distribution treated waters

Recent urban public water supply contamination events emphasize the importance of screening treated drinking water quality after distribution. In vitro bioassays, when run concurrently with analytical chemistry methods, are effective tools to evaluating the efficacy of water treatment processes and water quality. We tested 49 water samples representing the Chicago Department of Water Management service areas for estrogen, (anti)androgen, glucocorticoid receptor-activating contaminants and cytotoxicity. We present a tiered screening approach suitable to samples with anticipated low-level activity and initially tested all extracts for statistically identifiable endocrine activity; performing a secondary dilution-response analysis to determine sample EC 50 and biological equivalency values (BioEq). Estrogenic activity was detected in untreated Lake Michigan intake water samples using mammalian (5/49; median: 0.21 ng E2Eq/L) and yeast cell (5/49; 1.78 ng E2Eq/L) bioassays. A highly sensitive (anti)androgenic activity bioassay was applied for the first time to water quality screening and androgenic activity was detected in untreated intake and treated pre-distribution samples (4/49; 0.93 ng DHTEq/L). No activity was identified above method detection limits in the yeast androgenic, mammalian anti-androgenic, and both glucocorticoid bioassays. Known estrogen receptor agonists were detected using HPLC/MS-MS (estrone: 0.72-1.4 ng/L; 17α-estradiol: 1.3-1.5 ng/L; 17β-estradiol: 1.4 ng/L; equol: 8.8 ng/L), however occurrence did not correlate with estrogenic bioassay results. Many studies have applied bioassays to water quality monitoring using only relatively small samples sets often collected from surface and/or wastewater effluent. However, to realistically adapt these tools to treated water quality monitoring, water quality managers must have the capacity to screen potentially hundreds of samples in short timeframes. Therefore, we provided a tiered screening model that increased sample screening speed, without sacrificing statistical stringency, and detected estrogenic and androgenic activity only in pre-distribution Chicago area samples.

Illinois, Indiana↗

Formation of nanocolloidal metacinnabar in mercury-DOM-sulfide systems

Direct determination of mercury (Hg) speciation in sulfide-containing environments is confounded by low mercury concentrations and poor analytical sensitivity. Here we report the results of experiments designed to assess mercury speciation at environmentally relevant ratios of mercury to dissolved organic matter (DOM) (i.e., <4 nmol Hg (mg DOM) −1 ) by combining solid phase extraction using C 18 resin with extended X-ray absorption fine structure (EXAFS) spectroscopy. Aqueous Hg(II) and a DOM isolate were equilibrated in the presence and absence of 100 μM total sulfide. In the absence of sulfide, mercury adsorption to the resin increased as the Hg:DOM ratio decreased and as the strength of Hg-DOM binding increased. EXAFS analysis indicated that in the absence of sulfide, mercury bonds with an average of 2.4 ± 0.2 sulfur atoms with a bond length typical of mercury-organic thiol ligands (2.35 Å). In the presence of sulfide, mercury showed greater affinity for the C 18 resin, and its chromatographic behavior was independent of Hg:DOM ratio. EXAFS analysis showed mercury–sulfur bonds with a longer interatomic distance (2.51–2.53 Å) similar to the mercury–sulfur bond distance in metacinnabar (2.53 Å) regardless of the Hg:DOM ratio. For all samples containing sulfide, the sulfur coordination number was below the ideal four-coordinate structure of metacinnabar. At a low Hg:DOM ratio where strong binding DOM sites may control mercury speciation (1.9 nmol mg –1 ) mercury was coordinated by 2.3 ± 0.2 sulfur atoms, and the coordination number rose with increasing Hg:DOM ratio. The less-than-ideal coordination numbers indicate metacinnabar-like species on the nanometer scale, and the positive correlation between Hg:DOM ratio and sulfur coordination number suggests progressively increasing particle size or crystalline order with increasing abundance of mercury with respect to DOM. In DOM-containing sulfidic systems nanocolloidal metacinnabar-like species may form, and these species need to be considered when addressing mercury biogeochemistry.

Environmental Science & Technology↗

Tapwater exposures, residential risk, and mitigation in a PFAS-impacted-groundwater community

Tapwater (TW) safety and sustainability are priorities in the United States. Per/polyfluoroalkyl substance(s) (PFAS) contamination is a growing public-health concern due to prolific use, widespread TW exposures, and mounting human-health concerns. Historically-rural, actively-urbanizing communities that rely on surficial-aquifer private wells incur elevated risks of unrecognized TW exposures, including PFAS, due to limited private-well monitoring and contaminant-source proliferation in urbanizing landscapes. Here, a broad-analytical-scope TW-assessment was conducted in a hydrologically-vulnerable, Mississippi River alluvial-island community, where PFAS contamination of the shallow-alluvial drinking-water aquifer has been documented, but more comprehensive contaminant characterization to inform decision-making is currently lacking. In 2021, we analyzed 510 organics, 34 inorganics, and 3 microbial groups in 11 residential and community locations to assess (1) TW risks beyond recognized PFAS issues, (2) day-to-day and year-to-year risk variability, and (3) suitability of the underlying sandstone aquifer as an alternative source to mitigate TW-PFAS exposures. Seventy-six organics and 25 inorganics were detected. Potential human-health risks of detected TW exposures were explored based on cumulative benchmark-based toxicity quotients ( ∑ TQ ). Elevated risks ( ∑ TQ ≥ 1) from organic and inorganic contaminants were observed in all alluvial-aquifer-sourced synoptic samples but not in sandstone-aquifer-sourced samples. Repeated sampling at 3 sites over 52–55 h indicated limited variability in risk over the short-term. Comparable PFAS-specific ∑ TQ for spatial-synoptic, short-term (3 days) temporal, and long-term (3 years quarterly) temporal samples indicated that synoptic results provided useful insight into the risks of TW-PFAS exposures at French Island over the long-term. No PFAS detections in sandstone-aquifer-sourced samples over a 3 year period indicated no PFAS-associated risk and supported the sandstone aquifer as an alternative drinking-water source to mitigate community TW-PFAS exposures. This study illustrated the importance of expanded contaminant monitoring of private-well TW, beyond known concerns (in this case, PFAS), to reduce the risks of a range of unrecognized contaminant exposures.

Wisconsin↗

Rapid simulation of wave runup on morphologically diverse, reef-lined coasts with the BEWARE-2 (Broad-range Estimator of Wave Attack in Reef Environments) meta-process model

Low-lying, tropical, coral-reef-lined coastlines are becoming increasingly vulnerable to wave-driven flooding due to population growth, coral reef degradation, and sea-level rise. Early-warning systems (EWSs) are needed to enable coastal authorities to issue timely alerts and coordinate preparedness and evacuation measures for their coastal communities. At longer timescales, risk management and adaptation planning require robust assessments of future flooding hazard considering uncertainties. However, due to diversity in reef morphologies and complex reef hydrodynamics compared to sandy shorelines, there have been no robust analytical solutions for wave runup to allow for the development of large-scale coastal wave-driven flooding EWSs and risk assessment frameworks for reef-lined coasts. To address the need for fast, robust predictions of runup that account for the natural variability in coral reef morphologies, we constructed the BEWARE-2 (Broad-range Estimator of Wave Attack in Reef Environments) meta-process modeling system. We developed this meta-process model using a training dataset of hydrodynamics and wave runup computed by the XBeach Non-Hydrostatic process-based hydrodynamic model for 440 combinations of water level, wave height, and wave period with 195 representative reef profiles that encompass the natural diversity in real-world fringing coral reef systems. Through this innovation, BEWARE-2 can be applied in a larger range of coastal settings than meta-models that rely on a parametric description of the coral reef geometry. In the validation stage, the BEWARE-2 modeling system produced runup results that had a relative root mean square error of 13% and relative bias of 5% relative to runup simulated by XBeach Non-Hydrostatic for a large range of oceanographic forcing conditions and for diverse reef morphologies (root mean square error and bias 0.63 and 0.26 m, respectively, relative to mean simulated wave runup of 4.85 m). Incorporating parametric modifications in the modeling system to account for variations in reef roughness and beach slope allows for systematic errors (relative bias) in BEWARE-2 predictions to be reduced by a factor of 1.5–6.5 for relatively coarse or smooth reefs and mild or steep beach slopes. This prediction provided by the BEWARE-2 modeling system is faster by 4–5 orders of magnitude than the full, process-based hydrodynamic model and could therefore be integrated into large-scale EWSs for tropical, reef-lined coasts and used for large-scale flood risk assessments.

Natural Hazards and Earth System Sciences↗

Estimating black bear density in New Mexico using noninvasive genetic sampling coupled with spatially explicit capture-recapture methods

During the 2004–2005 to 2015–2016 hunting seasons, the New Mexico Department of Game and Fish (NMDGF) estimated black bear abundance (Ursus americanus) across the state by coupling density estimates with the distribution of primary habitat generated by Costello et al. (2001). These estimates have been used to set harvest limits. For example, a density of 17 bears/100 km2 for the Sangre de Cristo and Sacramento Mountains and 13.2 bears/100 km2 for the Sandia Mountains were used to set harvest levels. The advancement and widespread acceptance of non-invasive sampling and mark-recapture methods, prompted the NMDGF to collaborate with the New Mexico Cooperative Fish and Wildlife Research Unit and New Mexico State University to update their density estimates for black bear populations in select mountain ranges across the state. We established 5 study areas in 3 mountain ranges: the northern (NSC; sampled in 2012) and southern Sangre de Cristo Mountains (SSC; sampled in 2013), the Sandia Mountains (Sandias; sampled in 2014), and the northern (NSacs) and southern Sacramento Mountains (SSacs; both sampled in 2014). We collected hair samples from black bears using two concurrent non-invasive sampling methods, hair traps and bear rubs. We used a gender marker and a suite of microsatellite loci to determine the individual identification of hair samples that were suitable for genetic analysis. We used these data to generate mark-recapture encounter histories for each bear and estimated density in a spatially explicit capture-recapture framework (SECR). We constructed a suite of SECR candidate models using sex, elevation, land cover type, and time to model heterogeneity in detection probability and the spatial scale over which detection probability declines. We used Akaike’s Information Criterion corrected for small sample size (AICc) to rank and select the most supported model from which we estimated density. We set 554 hair traps, 117 bear rubs and collected 4,083 hair samples. We identified 725 (367 M, 358 F) individuals; the sex ratio for each study area was approximately equal. Our density estimates varied within and among mountain ranges with an estimated density of 21.86 bears/100 km2 (95% CI: 17.83 – 26.80) for the NSC, 19.74 bears/100 km2 (95% CI: 13.77 – 28.30) in the SSC, 25.75 bears/100 km2 (95% CI: 13.22 – 50.14) in the Sandias, 21.86 bears/100 km2 (95% CI: 17.83 – 26.80) in the NSacs, and 16.55 bears/100 km2 (95% CI: 11.64 – 23.53) in the SSacs. Overall detection probability for hair traps and bear rubs, combined, was low across all study areas and ranged from 0.00001 to 0.02. We speculate that detection probabilities were affected by failure of some hair samples to produce a complete genotype due to UV degradation of DNA, and our inability to set and check some sampling devices due to wildfires in the SSC. Ultraviolet radiation levels are particularly high in New Mexico compared to other states where NGS methods have been used because New Mexico receives substantial amounts of sunshine, is relatively high in elevation (1,200 m – 4,000 m), and is at a lower latitude. Despite these sampling difficulties, we were able to produce density estimates for New Mexico black bear populations with levels of precision comparable to estimated black bear densities made elsewhere in the U.S. Our ability to generate reliable black bear density estimates for 3 New Mexico mountain ranges is attributable to our use of a statistically robust study design and analytical method. There are multiple factors that need to be considered when developing future SECR-based density estimation projects. First, the spatial extent of the population of interest and the smallest average home range size must be determined; these will dictate size of the trapping array and spacing necessary between hair traps. The number of technicians needed and access to the study areas will also influence configuration of the trapping array. We believe shorter sampling occasions could be implemented to reduce degradation of DNA due to UV radiation; this might help increase amplification rates and thereby increase both the number of unique individuals identified and the number of recaptures, improving the precision of the density estimates. A pilot study may be useful to determine the length of time hair samples can remain in the field prior to collection. In addition, researchers may consider setting hair traps and bear rubs in more shaded areas (e.g., north facing slopes) to help reduce exposure to UV radiation. To reduce the sampling interval it will be necessary to either hire more field personnel or decrease the number of hair traps per sampling session. Both of these will enhance detection of long-range movement events by individual bears, increase initial capture and recapture rates, and improve precision of the parameter estimates. We recognize that all studies are constrained by limited resources, however, increasing field personnel would also allow a larger study area to be sampled or enable higher trap density. In conclusion, we estimated the density of black bears in 5 study areas within 3 mountains ranges of New Mexico. Our estimates will aid the NMDGF in setting sustainable harvest limits. Along with estimates of density, information on additional demographic rates (e.g., survival rates and reproduction) and the potential effects that climate change and future land use may have on the demography of black bears may also help inform management of black bears in New Mexico, and may be considered as future areas for research.

New Mexico↗

Case studies in groundwater contaminant fate and transport

A case study of groundwater contamination is a detailed study of a single site contaminated with a chemical or mixture that is known to be a problem at many sites. The goal of case studies is to provide insights into the physical, chemical, and biological processes controlling migration, natural attenuation, or remediation of common groundwater contaminants. Ideally, processes occurring at a case study site are representative of other sites so that knowledge gained from these intensive studies can be applied at thousands of sites where fewer data are available. Several characteristics of case studies contribute to their value. First, they may have tens to hundreds of monitoring wells, compared to fewer than ten wells at some contaminated sites. Second, some case studies continue for many years or even decades, providing insights into temporal progression of slow processes. Third, analytical methods prohibitively expensive for routine use or under development may be tested at case study sites. Finally, the ongoing characterization typical of case study sites builds a foundation of knowledge that facilitates sophisticated experimental design and testing of new methods. This article is divided into sections based on the contaminant type because the chemical and biological processes required for remediation vary for each contaminant. Most importantly, some contaminants can be biodegraded whereas metals and radionuclides cannot be destroyed but can be immobilized or rendered less toxic. The emphasis is on case studies of natural processes that control the fate and transport of contaminants in groundwater rather than on active remediation methods. The principles learned from these studies may form the basis for design of remedial strategies. The organic contaminants are divided into: petroleum hydrocarbons, fuel oxygenates, coal tar and wastes from manufactured gas plants, and chlorinated solvents. The inorganic contaminants covered are metals and radionuclides, arsenic, and nitrate. Case studies of mixed waste plumes from landfills are also described. Experimental sites where contaminants have been introduced into an aquifer as an emplaced source or a controlled release may not meet the above definition of case studies, but some are included because the overall goal is to impart lessons learned from detailed field studies. It is impossible to cover all case studies in this short format. Conversely, focusing on one or two does not convey the breadth of research results in entire range of case studies. Instead, the strategy is to describe the evolution of knowledge for each contaminant class while providing citations of relevant case studies. Much of the progress in understanding of the fate of contaminants in groundwater is based on laboratory studies; thus whenever possible, papers that included both field and laboratory results have been included among the citations. Two topics of growing importance have not been covered. These are the fate of pharmaceuticals in groundwater and discharge of contaminant plumes to surface water. These topics merit coverage in the future as knowledge grows and case studies increase in number.

Environmental Science↗

Accuracy and precision of U–Pb zircon geochronology at high spatial resolution (7–20 μm spots) by laser ablation-ICP-single-collector-sector-field-mass spectrometry

Use of small spots (≤20µm) for laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) U-Pb zircon geochronology is of increasing interest in the Earth sciences because the temporal record of geologic processes is often preserved on a fine-scale within zircon grains. However the systematic biases and external sources of uncertainity of U-Pb ages is poorly defined when measured on small spots by LA-ICP-single-collector-sector-field (SF)-MS instrumentation. This study addresses the accuracy and precision for small spots and specifically the extent to which short ablation times limit Pb/U Down-Hole Fractionation (DHF), which largely controls the accuracy of the U-Pb ages. Six zircon reference materials (91500, FC-1, R33, Temora 2, Plešovice and Fish Canyon Tuff) were measured on spot sizes of 20, 15, 10 and 7 µm diameter. Laser fluence was increased from 3 to 6 J/cm2 with decreasing spot size to compensate partially for decreasing U and Pb signals. 91500 zircon was the calibration reference material. Raw count rate data were processed using Iolite version 3.63 software with the U-Pb Common Approach data reduction scheme and smoothed cubic spline DHF correction model. Samples were ablated for 30 seconds and results processed for the first 28, 15, 10 and 7 seconds of ablation (masking the initial 2 seconds) in order to assess the accuracy and precision of U-Pb ages as a function of ablation time. Measured 206Pb/238U ratios for the six zircon reference materials increase steadily with ablation time, reflecting DHF, but exhibit somewhat different patterns of increase for different zircons, producing the major source of uncertainty for the U-Pb ages. A secondary source of uncertainty is differences between the 206Pb/238U (normalized to their accepted values) for different zircons near the start of ablation, which may reflect matrix-dependent instrumental mass bias in the ICP. Nonetheless, processing data from only the first 10 to 15 seconds of ablation (50 to 75 laser pulses) restricts the extent of DHF and time-resolved Pb/U variations between different zircons to a sufficient degree to give concordant U-Pb ages on 20 to 7 µm spots that are accurate and precise to better than 1.4% using LA-ICP-single-collector-SF-MS instrumentation.

Journal of Analytical Atomic Spectrometry↗