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377 records · Page 21Linked to original sources

History and progress of the North American Soil Geochemical Landscapes Project, 2001-2010

In 2007, the U.S. Geological Survey, the Geological Survey of Canada, and the Mexican Geological Survey initiated a low-density (1 site per 1600 km 2 , 13323 sites) geochemical and mineralogical survey of North American soils (North American Soil Geochemical Landscapes Project). Sampling and analytical protocols were developed at a series of workshops in 20032004 and pilot studies were conducted from 20042007. The ideal sampling protocol at each site includes a sample from 05 cm depth, a composite of the soil A horizon, and a sample from the soil C horizon. The <2-mm fraction of each sample is analyzed for Al, Ca, Fe, K, Mg, Na, S, Ti, Ag, Ba, Be, Bi, Cd, Ce, Co, Cr, Cs, Cu, Ga, In, La, Li, Mn, Mo, Nb, Ni, P, Pb, Rb, Sb, Sc, Sn, Sr, Te, Th, Tl, U, V, W, Y, and Zn by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry following a near-total digestion in a mixture of HCl, HNO 3 , HClO 4 , and HF. Separate methods are used for As, Hg, Se, and total C on this same size fraction. The major mineralogical components are determined by a quantitative X-ray diffraction method. Sampling in the conterminous U.S. was completed in 2010 (c. 4800 sites) with chemical and mineralogical analysis currently underway. In Mexico, approximately 66% of the sampling (871 sites) had been done by the end of 2010 with completion expected in 2012. After completing sampling in the Maritime provinces and portions of other provinces (472 sites, 7.6% of the total), Canada withdrew from the project in 2010. Preliminary results for a swath from the central U.S. to Florida clearly show the effects of soil parent material and climate on the chemical and mineralogical composition of soils. A sample archive will be established and made available for future investigations.

Earth Science Frontiers↗

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↗

Foundational uncertainties in terminal Ediacaran chronostratigraphy revealed by high-precision zircon U-Pb geochronology of the Nama Group, Namibia

The Nama Group of southern Namibia and northwestern South Africa hosts the best-dated mixed carbonate-siliciclastic foreland basin succession of the terminal Ediacaran [ca. 551 million years (Ma) ago to <538 Ma] and is key for resolving the chronology of early metazoan evolution. Numerous silicified volcanic tuff interbeds are present, but differing interpretations regarding the fidelity of their ages lead to different regional stratigraphic correlations, especially for the Urusis Formation of the Schwarzrand Subgroup. An expanded record of the Urusis Formation is found in the Swartpunt area of southern Namibia, which has yielded an important metazoan biota. But the succession in this area is preserved as a series of thrusts at the leading edge of the Gariep orogenic belt and zircon U-Pb data show systematic age repetition. We use regional stratigraphic and structural mapping, integrated with carbonate carbon isotope (δ 13 C carb ) chemostratigraphy and high-precision radioisotope U-Pb zircon geochronology from outcrop and recently acquired drill core to develop a temporally calibrated basin-wide depositional model. This integrated dataset either reflects complex zircon reworking, inheritance, or potential analytical biases (Scenario 1) or the presence of a Gariep-related cryptic décollement within the Spitskop Member that has resulted in stratigraphic repetition (Scenario 2). We investigate the evidence for and against both scenarios and consider their implications for stratigraphic and δ 13 C carb correlations between the Swartpunt area and coeval exposures along the Orange River border with South Africa. Given that these issues are in an area that hosts numerous silicified ash beds and extensive exposure, an inability to confidently discount either scenario highlights a level of compounding uncertainty in zircon U-Pb geochronology that must be considered when attempting to build global chronostratigraphic frameworks. Scenario 1 implies that some of the weighted mean ages and Bayesian eruption ages from the Swartpunt area may be >1 Myr older than the depositional age of their respective ash beds when assuming existing stratigraphic correlations. If this scenario is preferred, then a cautious approach would be to consider all weighted mean zircon U-Pb ages from ash beds to reflect maximum depositional ages. Both scenarios support deposition of the Huns Member >540 Ma in the Swartpunt area if the oldest weighted mean age reported here represents a near-depositional age, which has significant implications for the temporal calibration of important terminal Ediacaran ichnofossil assemblages and future cyclostratigraphic studies. Stratigraphic correlations common to both scenarios allow us to temporally calibrate a basin evolution model for the Nama Group. Temporal trends in initial hafnium isotope (εHf) compositions of zircon grains from ash beds throughout the succession may support progressive crustal thickening associated with underplating of the Damara orogenic belt along the northern periphery of the Kalahari craton from ca. 547 Ma to ca. 538 Ma. The compilation of new and published zircon U-Pb ages may also imply that the locus of carbonate platform development migrated from north to south (present co-ordinates), tracking the migration of foredeep subsidence.

Earth-Science Reviews↗

Occurrence of cyanazine compounds in groundwater: Degradates more prevalent than the parent compound

A recently developed analytical method using liquid chromatography/mass spectrometry was used to investigate the occurrence of cyanazine and its degradates cyanazine acid (CAC), cyanazine amide (CAM), deethylcyanazine (DEC), and deethylcyanazine acid (DCAC) in groundwater. This research represents some of the earliest data on the occurrence of cyanazine degradates in groundwater. Although cyanazine was infrequently detected in the 64 wells across Iowa sampled in 1999, cyanazine degradates were commonly found during this study. The most frequently detected cyanazine compound was DCAC (32.8%) followed by CAC (29.7%), CAM (17.2%), DEC (3.1%), and cyanazine (3.1%). The frequency of detection for cyanazine or one or more of its degradates (CYTOT) was more than 12-fold over that of cyanazine alone (39.1% for CYTOT versus 3.1% for cyanazine). Of the total measured concentration of cyanazine, only 0.2% was derived from its parent compound - with DCAC (74.1%) and CAC (18.4%) comprising 92.5% of this total. Thus, although DCAC and CAC had similar frequencies of detection, DCAC was generally present in higher concentrations. No concentrations of cyanazine compounds for this study exceeded water-quality criteria for the protection of human health. Only cyanazine, however, has such a criteria established. Nevertheless, because these cyanazine degradates are still chlorinated, they may have similar toxicity as their parent compound - similar to what has been found with the chlorinated degradates of atrazine. Thus, the results of this study documented that data on the degradates for cyanazine are critical for understanding its fate and transport in the hydrologic system. Furthermore, the prevalence of the chlorinated degradates of cyanazine found in groundwater suggests that to accurately determine the overall effect on human health and the environment from cyanazine its degradates should also be considered. In addition, because CYTOT was found in 57.6% of the samples collected from alluvial aquifers, about 2-5 times more frequently than the other major aquifer types (glacial drift, bedrock/karst, bedrock/nonkarst) under investigation, this finding has long-term implications for the occurrence of CYTOT in streams. It is anticipated that low-level concentrations of CYTOT will continue to be detected in streams for years after the use of cyanazine has terminated (scheduled for the year 2000 in the United States), primarily through its movement from groundwater into streams during base-flow conditions.

Iowa↗

Insights and strategic opportunities from the USGS 2024 Per- and Polyfluoroalkyl Substances (PFAS) Interagency Workshop

Introduction In 2021, the U.S. Geological Survey (USGS) published Circular 1490 titled, “Integrated Science for the Study of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in the Environment: A Strategic Science Vision for the U.S. Geological Survey” (Tokranov and others, 2021). Circular 1490 was created to be a resource for USGS scientists prioritizing and planning research related to per- and polyfluoroalkyl substances (PFAS) and to be a guide for developing partnerships with other scientists, State and Federal agencies, and stakeholders engaged in PFAS research and management and mitigation of the environmental and human-health effects of PFAS. This USGS PFAS Strategic Science Vision document was intended to be the foundation for a “living strategic vision,” periodically providing updates on the state of USGS PFAS research, emerging PFAS data gaps and needs, and progress on interagency and stakeholder PFAS partnerships and priorities. To meet this objective, the USGS planned to host an Interagency and Stakeholder PFAS Workshop every 2–3 years. During September 10–12, 2024, the USGS hosted the first Interagency and Stakeholder PFAS Workshop in Reston, Virginia. The Workshop brought together experts from other Federal agencies (U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, Food and Drug Administration, Department of Defense [Air Force, Army]), State agencies (Washington Fish and Wildlife, Virginia Department of Transportation), and academia (Harvard University, University of Maryland) to address key challenges relating to the measurement and modeling of PFAS and the implications for environmental health. Participants engaged in in-depth discussions centered around six pivotal topics related to PFAS: (1) sampling protocols, methods and interpretation; (2) environmental sources, source apportionment, and occurrence; (3) environmental fate and transport; (4) human and wildlife exposure routes and risk; (5) bioconcentration, bioaccumulation, and biomagnification; and (6) ecotoxicology and effects. Each topic had three breakout sessions. A recurrent theme of workshop discussions was how data on a nationwide scale for PFAS occurrence in various environmental matrices, including air, water, food crops, biota, soil, and streambed sediment could help to advance scientific understanding. Participants noted significant geospatial data gaps, particularly in the midwestern and southern United States and the Pacific Northwest. PFAS data collection tends to be more robust along the eastern seaboard and in California. Participants stressed how enhancing the integration of large and small datasets across various agencies could help to support national scale understanding of PFAS. To address these gaps, attendees suggested leveraging datasets from Federal entities like the USGS and the U.S. Department of Defense, State agencies, and municipal utility services to develop predictive contaminant detection and transport models. Improved coordination between water quality programs and USGS research could help to facilitate access to valuable data, leading to comprehensive databases that inform PFAS point (wastewater treatment plants and landfills) and nonpoint (runoff from land, atmospheric deposition, food packaging) sources, environmental transport mechanisms, environmental detection and concentrations, potential exposure routes, and health effects on different biota, including humans. A specific request was made to develop a map demarking the depth of modern (1953 or later) groundwater, which is susceptible to surface-derived anthropogenic (that is, human-made) contamination, based on tritium-age dating. Emphasis was placed on incorporation of hydrology, groundwater flow paths, groundwater–surface water interactions, and landscape factors in predictive statistical models as a step to improve contaminant source identification and tracking. Molecular fingerprinting approaches garnered attention as techniques to link specific PFAS mixtures detected in a sample to environmental sources and levels in biota (Dávila-Santiago and others, 2022). Integrating data from abiotic (that is, water, soil, and air) and biotic (that is, living organisms) systems identified as a research opportunity. For example, understanding the composition of soils and sediments, which include a mixture of mineral, plant, and animal components, could advance understanding of exposure pathways. The discussions highlighted opportunities to explore and understand the potential redistribution and biotic exposures of PFAS from biosolid and wastewater treatment plant effluent land application practices, in addition to atmospheric releases and discharges from landfill and wastewater treatment plants. Participants identified research gaps surrounding how these sources may contribute to contamination and may affect surrounding ecosystems, including a better definition of anthropogenic background concentrations. Moving forward, the collection of co-occurrence data was noted as a means to improve understanding of complex mixtures and to leverage companion modeling efforts focused on areas with high and low contamination levels to identify areas of concern and unaffected resources. Participants emphasized how centralized USGS databases and the establishment of sample-metadata archives can help to ensure that samples are preserved and accessible for future research. In conclusion, the workshop participants identified opportunities to bridge data gaps and improve measurement techniques, modeling frameworks, databases, and communication, to enhance the understanding of PFAS and their effects on environmental and human health. Upon completion of the workshop, participants indicated an interest in developing strategic data collection, modeling, and analytical approaches to address these challenges.

Open-File Report↗

ChemCam activities and discoveries during the nominal mission of the Mars Science Laboratory in Gale crater, Mars

At Gale crater, Mars, ChemCam acquired its first laser-induced breakdown spectroscopy (LIBS) target on Sol 13 of the landed portion of the mission (a Sol is a Mars day). Up to Sol 800, more than 188 000 LIBS spectra were acquired on more than 5800 points distributed over about 650 individual targets. We present a comprehensive review of ChemCam scientific accomplishments during that period, together with a focus on the lessons learned from the first use of LIBS in space. For data processing, we describe new tools that had to be developed to account for the uniqueness of Mars data. With regard to chemistry, we present a summary of the composition range measured on Mars for major-element oxides (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O) based on various multivariate models, with associated precisions. ChemCam also observed H, and the non-metallic elements C, O, P, and S, which are usually difficult to quantify with LIBS. F and Cl are observed through their molecular lines. We discuss the most relevant LIBS lines for detection of minor and trace elements (Li, Rb, Sr, Ba, Cr, Mn, Ni, and Zn). These results were obtained thanks to comprehensive ground reference datasets, which are set to mimic the expected mineralogy and chemistry on Mars. With regard to the first use of LIBS in space, we analyze and quantify, often for the first time, each of the advantages of using stand-off LIBS in space: no sample preparation, analysis within its petrological context, dust removal, sub-millimeter scale investigation, multi-point analysis, the ability to carry out statistical surveys and whole-rock analyses, and rapid data acquisition. We conclude with a discussion of ChemCam performance to survey the geochemistry of Mars, and its valuable support of decisions about selecting where and whether to make observations with more time and resource-intensive tools in the rover's instrument suite. In the end, we present a bird's-eye view of the many scientific results: discovery of felsic Noachian crust, first observation of hydrated soil, discovery of manganese-rich coatings and fracture fills indicating strong oxidation potential in Mars' early atmosphere, characterization of soils by grain size, and wide scale mapping of sedimentary strata, conglomerates, and diagenetic materials.

Journal of Analytical Atomic Spectrometry↗

Pharmaceutical pollution of the world’s rivers

Environmental exposure to active pharmaceutical ingredients (APIs) can have negative effects on the health of ecosystems and humans. While numerous studies have monitored APIs in rivers, these employ different analytical methods, measure different APIs, and have ignored many of the countries of the world. This makes it difficult to quantify the scale of the problem from a global perspective. Furthermore, comparison of the existing data, generated for different studies/regions/continents, is challenging due to the vast differences between the analytical methodologies employed. Here, we present a global-scale study of API pollution in 258 of the world’s rivers, representing the environmental influence of 471.4 million people across 137 geographic regions. Samples were obtained from 1,052 locations in 104 countries (representing all continents and 36 countries not previously studied for API contamination) and analyzed for 61 APIs. Highest cumulative API concentrations were observed in sub-Saharan Africa, south Asia, and South America. The most contaminated sites were in low- to middle-income countries and were associated with areas with poor wastewater and waste management infrastructure and pharmaceutical manufacturing. The most frequently detected APIs were carbamazepine, metformin, and caffeine (a compound also arising from lifestyle use), which were detected at over half of the sites monitored. Concentrations of at least one API at 25.7% of the sampling sites were greater than concentrations considered safe for aquatic organisms, or which are of concern in terms of selection for antimicrobial resistance. Therefore, pharmaceutical pollution poses a global threat to environmental and human health, as well as to delivery of the United Nations Sustainable Development Goals.

Proceedings of the National Academy of Sciences↗