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USGS2016

Controls on selenium distribution and mobilization in an irrigated shallow groundwater system underlain by Mancos Shale, Uncompahgre River Basin, Colorado, USA

Elevated selenium (Se) concentrations in surface water and groundwater have become a concern in areas of the Western United States due to the deleterious effects of Se on aquatic ecosystems. Elevated Se concentrations are most prevalent in irrigated alluvial valleys underlain by Se-bearing marine shales where Se can be leached from geologic materials into the shallow groundwater and surface water systems. This study presents groundwater chemistry and solid-phase geochemical data from the Uncompahgre River Basin in Western Colorado, an irrigated alluvial landscape underlain by Se-rich Cretaceous marine shale. We analyzed Se species, major and trace elements, and stable nitrogen and oxygen isotopes of nitrate in groundwater and aquifer sediments to examine processes governing selenium release and transport in the shallow groundwater system. Groundwater Se concentrations ranged from below detection limit (< 0.5 μg L − 1 ) to 4070 μg L − 1 , and primarily are controlled by high groundwater nitrate concentrations that maintain oxidizing conditions in the aquifer despite low dissolved oxygen concentrations. High nitrate concentrations in non-irrigated soils and nitrate isotopes indicate nitrate is largely derived from natural sources in the Mancos Shale and alluvial material. Thus, in contrast to areas that receive substantial NO 3 inputs through inorganic fertilizer application, Se mitigation efforts that involve limiting NO 3 application might have little impact on groundwater Se concentrations in the study area. Soluble salts are the primary source of Se to the groundwater system in the study area at-present, but they constitute a small percentage of the total Se content of core material. Sequential extraction results indicate insoluble Se is likely composed of reduced Se in recalcitrant organic matter or discrete selenide phases. Oxidation of reduced Se species that constitute the majority of the Se pool in the study area could be a potential source of Se in the future as soluble salts are progressively depleted.

Colorado↗

USGS2018

Alternate wetting and drying decreases methylmercury in flooded rice (Oryza sativa) systems

In flooded soils, including those found in rice ( Oryza sativa L.) fields, microbes convert inorganic Hg to more toxic methylmercury (MeHg). Methylmercury is accumulated in rice grain, potentially affecting health. Methylmercury in rice field surface water can bioaccumulate in wildlife. We evaluated how introducing aerobic periods into an otherwise continuously flooded rice growing season affects MeHg dynamics. Conventional continuously flooded (CF) rice field water management was compared with alternate wetting and drying, where irrigation was stopped twice during the growing season, allowing soil to dry to 35% volumetric moisture content, at which point plots were reflooded (AWD-35). Methylmercury studies began at harvest in Year 3 and throughout Year 4 of a 4-yr replicated field experiment. Bulk soil, water, and plant samples were analyzed for MeHg and total Hg (THg), and iron (Fe) speciation was measured in soil samples. Rice grain yield over 4 yr did not differ between treatments. Soil chemistry responded quickly to AWD-35 dry-downs, showing significant oxidation of Fe(II) accompanied by a significant reduction of MeHg concentration (76% reduction at harvest) compared with CF. Surface water MeHg decreased by 68 and 39% in the growing and fallow seasons, respectively, suggesting that the effects of AWD-35 management can last through to the fallow season. The AWD-35 treatment reduced rice grain MeHg and THg by 60 and 32%, respectively. These results suggest that the more aerobic conditions caused by AWD-35 limited the activity of Hg(II)-methylating microbes and may be an effective way to reduce MeHg concentrations in rice ecosystems.

Soil Science Society of America Journal↗

USGS2023

Nitrogen-15 NMR study on the incorporation of nitrogen into aquatic NOM upon chloramination

Chloramination is being used increasingly in water treatment to lower the formation of regulated disinfection byproducts (DBPs). How monochloramine nitrogen becomes incorporated into aquatic natural organic matter (NOM) and potentially affects the formation of nitrogenous DBPs is an unresolved question in the chemistry of humic substances. To address the problem, Suwannee River NOM and Suwannee River fulvic acid were reacted with preformed 15 NH 2 Cl and analyzed by solid and liquid state 15 N NMR spectrometry. Both samples were also reacted with 15 NH 4 Cl as a control. A majority of the monochloramine nitrogen incorporated into the samples matched the structural forms resulting from the control reaction with ammonia, indicating that condensation reactions of ammonia with the carbonyl functionality can partly explain the transformation of the 15 NH 2 Cl nitrogen into the NOM. These structural forms include aminohydroquinone, 1° amide, indole, and pyridine-like nitrogens. Spectra of the samples reacted with 15 NH 2 Cl also showed possible evidence for nitrosophenol nitrogens, which would arise from the reaction of hydroxylamine or nitrite, intermediates in the chemical oxidation of the inorganic nitrogen to nitrate.

Aquatic Sciences↗

USGS2008

Effects of urbanization on stream ecosystems in the Willamette River basin and surrounding area, Oregon and Washington

This report describes the effects of urbanization on physical, chemical, and biological characteristics of stream ecosystems in 28 watersheds along a gradient of urbanization in the Willamette River basin and surrounding area, Oregon and Washington, from 2003 through 2005. The study that generated the report is one of several urban-effects studies completed nationally by the U.S. Geological Survey National Water-Quality Assessment Program. Watersheds were selected to minimize natural variability caused by factors such as geology, elevation, and climate, and to maximize coverage of different stages of urban development among watersheds. Because land use or population density alone often are not a complete measure of urbanization, a combination of land use, land cover, infrastructure, and socioeconomic variables were integrated into a multimetric urban intensity index (UII) to represent the degree of urban development in each watershed. Physical characteristics studied include stream hydrology, stream temperature, and habitat; chemical characteristics studied include sulfate, chloride, nutrients, pesticides, dissolved and particulate organic and inorganic carbon, and suspended sediment; and biological characteristics studied include algal, macroinvertebrate, and fish assemblages. Semipermeable membrane devices, passive samplers that concentrate trace levels of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons and polychlorinated biphenyls, also were used. The objectives of the study were to (1) examine physical, chemical, and biological responses along the gradient of urbanization and (2) determine the major physical, chemical, and landscape variables affecting the structure of aquatic communities. Common effects documented in the literature of urbanization on instream physical, chemical, and biological characteristics, such as increased contaminants, increased streamflow flashiness, increased concentrations of chemicals, and changes in aquatic community structure toward a more tolerant community associated with organically enriched conditions, generally were observed in this study. The strongest correlations to the UII and to many of the algal, macroinvertebrate, and fish assemblage metrics and community ordination involved water-chemistry metrics including the total pesticide concentration, toxic equivalents (extract assay from semipermeable membrane devices), and dissolved oxygen. Hydrologic variability metrics, such as flashiness, that normally are considered to be one of the main processes of urban disturbance had a strong association to the algal and fish assemblages in this study; however, the hydrologic variables for macroinvertebrates were secondary to the water-chemistry metrics mentioned above. Generally, the high urban intensity sites had high abundances of eutrophic and lower dissolved oxygen-indicating diatoms, high abundances of noninsects and tolerant insects, and high abundances of nonnative fish species. On the other hand, the low urban intensity sites had higher abundances of pollution sensitive diatoms, larger numbers of the sensitive macroinvertebrate EPT taxa (Ephemeroptera, Plecoptera and Trichoptera Orders), and fish assemblages with higher abundances of sensitive salmonids. The percent salmonid and macroinvertebrate EPT richness metrics plotted against the UII indicated a possible threshold response at about 25 on the UII, which is equivalent to an impervious surface value of about 5 percent. However, due to the added agricultural land use at sites within the 25 to 60 UII range, this possible threshold probably is not solely due to urbanization, but a combination of urban and agricultural land use. The effects of agricultural and urban land use could not be distinguished from each other, yet combined they provide a good assessment of overall watershed disturbance.

Oregon, Washington↗

USGS2010

Status and understanding of groundwater quality in the central-eastside San Joaquin Basin, 2006: California GAMA Priority Basin Project

Groundwater quality in the approximately 1,695-square-mile Central Eastside San Joaquin Basin (Central Eastside) study unit was investigated as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001, and is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The GAMA Central Eastside study unit was designed to provide a spatially unbiased assessment of untreated-groundwater quality, as well as a statistically consistent basis for comparing water quality throughout California. During March through June 2006, samples were collected from 78 wells in Stanislaus and Merced Counties, 58 of which were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and 20 of which were sampled to evaluate changes in water chemistry along groundwater-flow paths (understanding wells). Water-quality data from the California Department of Public Health (CDPH) database also were used for the assessment. An assessment of the current status of the groundwater quality included collecting samples from wells for analysis of anthropogenic constituents such as volatile organic compounds (VOCs) and pesticides, as well as naturally occurring constituents such as major ions and trace elements. The assessment of status is intended to characterize the quality of untreated-groundwater resources within the primary aquifer system, not the treated drinking water delivered to consumers by water purveyors. The primary aquifer system (hereinafter, primary aquifer) is defined as that part of the aquifer corresponding to the perforation interval of wells listed in the CDPH database for the Central Eastside study unit. The quality of groundwater in shallower or deeper water-bearing zones may differ from that in the primary aquifer; shallower groundwater may be more vulnerable to surficial contamination. The primary aquifer is represented by the grid wells, of which 90 percent had depths to the tops of their perforations of about 80 to 330 feet and depths to bottom of about 100 to 670 feet. Relative-concentrations (sample concentration divided by benchmark concentration) were used as the primary metric for assessing the status of water quality for those constituents that have Federal and (or) California human health or aesthetic benchmarks. A relative-concentration greater than (>) 1.0 indicates a concentration above a benchmark, and less than or equal to (≤) 1.0 indicates a concentration equal to or below a benchmark. For organic and special interest constituents, relative-concentrations were classified as high (>1.0), moderate (≤1.0 and >0.1), or low (≤0.1). For inorganic constituents, relative-concentrations were classified as high (>1.0), moderate (≤1.0 and >0.5), or low (≤0.5). The threshold between low and moderate classifications was lower for organic and special interest constituents than for inorganic constituents because organic constituents generally are less prevalent and have smaller relative-concentrations than inorganic constituents. Grid-based and spatially-weighted approaches, the latter incorporating data from all CDPH wells, were used to evaluate the proportion of the primary aquifer (aquifer-scale proportions) with high, moderate, or low relative-concentrations. For individual constituents or classes of constituents, the aquifer-scale high proportion is the percentage of the area of the study unit having high relative-concentrations within the depth-zones of the primary aquifer. Aquifer-scale moderate and low proportions are defined similarly. Spatially-weighted aquifer-scale high proportions nearly always fell within the 90-percent confidence interval of grid-based aquifer-scale high proportions, indicating that the grid-based approach yielded statistically equivalent results to the spatially-weighted approach incorporating CDPH data. The status assessment for inorganic constituents showed that inorganic constituents (one or more) were high, relative to human-health benchmarks, in 18.0 percent of the primary aquifer, moderate in 44.0 percent, and low in 38.0 percent. Of inorganic constituents with human-health benchmarks, arsenic, vanadium, and nitrate were detected at high relative-concentrations in 15.6 percent, 3.6 percent, and 2.1 percent, respectively, of the primary aquifer. Of inorganic constituents with secondary maximum contaminant levels (SMCL), manganese, iron, and TDS were detected at high relative-concentrations in 4.5 percent, 2.2 percent, and 1.7 percent, respectively, of the primary aquifer. The status assessment for organic constituents showed that organic constituents (one or more) were high, relative to human-health benchmarks, in a smaller proportion of the primary aquifer (1.2 percent) than inorganic constituents (18.0 percent). Organic constituents had moderate relative-concentrations in 14.3 percent, and had low relative-concentrations or were not detected in 84.5 percent, of the primary aquifer. The proportion of the primary aquifer with high relative-concentrations of organic constituents reflected high proportions of the discontinued soil fumigant 1,2-dibromo-3-chlororopane (DBCP; 1.0 percent) and the solvent tetrachloroethene (PCE; 0.2 percent). Most of the organic and special interest constituents detected in groundwater in the Central Eastside study unit have human-health benchmarks. Of the 205 organic and special interest constituents analyzed for, 36 constituents were detected. Of these constituents, 32 were detected only at low relative-concentrations. Four constituents, chloroform, carbon tetrachloride, DBCP, and perchlorate, were detected at moderate relative-concentrations in grid wells. Nine organic and special-interest constituents were detected frequently (detected in greater than 10 percent of samples): the trihalomethanes chloroform, bromoform, bromodichloromethane, and dibromochloromethane; the solvent PCE; the herbicides atrazine, simazine, and metolachlor, and special-interest constituent perchlorate. An assessment of understanding of the groundwater quality included sampling of understanding wells, some of which were perforated in shallower or deeper portions of the aquifer system than the primary aquifer, and analysis of correlations of groundwater quality with land use, depth, age classification, and other potential explanatory factors. The understanding assessment indicated that the concentrations of many constituents were related to depth and groundwater age. However, concentrations of individual constituents or constituent classes also were sometimes related to geochemical conditions, lateral position in the flow system, or land use. High and moderate relative-concentrations of uranium, nitrate, and total dissolved solids (TDS) were detected in some wells where the tops of perforations are within the upper 200 feet of the aquifer system. In wells with the depth to the top of perforations below this depth, concentrations were low. A similar pattern occurred for the sum of herbicide concentrations. These vertical water-chemistry patterns are consistent with the hydrogeologic setting, in which return flows from agricultural and urban land use are the major source of recharge, and withdrawals for irrigation and urban supply are the major source of discharge, resulting in substantial vertical components of groundwater flow. The decrease in concentrations of many constituents with depth reflects in part that groundwater gets older with depth. Tritium, helium-isotopes, and carbon-14 data were used to classify the predominant age of groundwater samples into three categories: modern (water that has entered the aquifer in the last 50 years), pre-modern (water that entered the aquifer more than 50 years, up to tens of thousands of years, ago), and mixed (mixtures of waters with modern and pre-modern ages). Uranium, nitrate, and herbicide concentrations were significantly higher in groundwater having modern- and mixed-ages than pre-modern ages, indicating that these constituents may be affected by anthropogenic activities in the last 50 years. Other patterns in the distribution of nitrate, uranium, and TDS are evident. Isotopic and geochemical data are consistent with partial denitrification of nitrate in some reducing groundwaters in the western and deeper parts of the flow system. Uranium and TDS concentrations increase from east to west across the valley, along the direction of regional lateral groundwater flow. High and moderate relative-concentrations of arsenic can be attributed to reductive dissolution of manganese or iron oxides, or to desorption by high pH waters. Arsenic concentrations also increased with increasing depth and groundwater age. High to moderate relative-concentrations of vanadium primarily are related to high pH under oxic conditions. The frequency of detections of DBCP was greater in areas with orchard-vineyard land use >40 percent and at depths <200 feet. THMs and solvents were correlated positively with percent urban land use. Herbicide concentrations were correlated negatively with percent natural land use. Perchlorate concentrations were significantly greater in waters having modern and mixed ages than waters having pre-modern ages and were significantly and positively correlated with two land uses—percent orchard/vineyard land use and percent urban land use.

California↗

USGS1995

Toxicity and bioaccumulation of sediment-associated contaminants using freshwater invertebrates: A review of methods and applications

This paper reviews recent developments in methods for evaluating the toxicity and bioaccumulation of contaminants associated with freshwater sediments and summarizes example case studies demonstrating the application of these methods. Over the past decade, research has emphasized development of more specific testing procedures for conducting 10-d toxicity tests with the amphipod Hyalella azteca and the midge Chironomus tentans. Toxicity endpoints measured in these tests are survival for H. azteca and survival and growth for C. tentans. Guidance has also been developed for conducting 28-d bioaccumulation tests with the oligochaete Lumbriculus variegatus, including determination of bioaccumulation kinetics for different compound classes. These methods have been applied to a variety of sediments to address issues ranging from site assessments to bioavailability of organic and inorganic contaminants using field-collected and laboratory-spiked samples. Survival and growth of controls routinely meet or exceed test acceptability criteria. Results of laboratory bioaccumulation studies with L. variegatus have been confirmed with comparisons to residues (PCBs, PAHs, DDT) present from synoptically collected field populations of oligochaetes. Additional method development is currently underway to develop chronic toxicity tests and to provide additional data-confirming responses observed in laboratory sediment tests with natural benthic populations.

Environmental Toxicology and Chemistry↗

USGS2010

Status and understanding of groundwater quality in the northern San Joaquin Basin, 2005: California GAMA Priority Basin Project

Groundwater quality in the 2,079 square mile Northern San Joaquin Basin (Northern San Joaquin) study unit was investigated from December 2004 through February 2005 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001 that was passed by the State of California and is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory. The Northern San Joaquin study unit was the third study unit to be designed and sampled as part of the Priority Basin Project. Results of the study provide a spatially unbiased assessment of the quality of raw (untreated) groundwater, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 61 wells in parts of Alameda, Amador, Calaveras, Contra Costa, San Joaquin, and Stanislaus Counties; 51 of the wells were selected using a spatially distributed, randomized grid-based approach to provide statistical representation of the study area (grid wells), and 10 of the wells were sampled to increase spatial density and provide additional information for the evaluation of water chemistry in the study unit (understanding/flowpath wells). The primary aquifer systems (hereinafter, primary aquifers) assessed in this study are defined by the depth intervals of the wells in the California Department of Public Health database for each study unit. The quality of groundwater in shallow or deep water-bearing zones may differ from quality of groundwater in the primary aquifers; shallow groundwater may be more vulnerable to contamination from the surface. Two types of assessments were made: (1) status, assessment of the current quality of the groundwater resource; and (2) understanding, identification of the natural and human factors affecting groundwater quality. Relative-concentrations (sample concentrations divided by benchmark concentrations) were used for evaluating groundwater quality for those constituents that have Federal or California regulatory or non-regulatory benchmarks for drinking-water quality. Benchmarks used in this study were either health-based (regulatory and non-regulatory) or aesthetic based (non-regulatory). For inorganic constituents, relative-concentrations were classified as high (equal to or greater than 1.0), indicating relative-concentrations greater than benchmarks; moderate (equal to or greater than 0.5, and less than 1.0); or, low (less than 0.5). For organic and special- interest constituents [1,2,3-trichloropropane (1,2,3-TCP), N-nitrosodimethylamine (NDMA), and perchlorate], relative- concentrations were classified as high (equal to or greater than 1.0); moderate (equal to or greater than 0.1 and less than 1.0); or, low (less than 0.1). Aquifer-scale proportion was used as the primary metric in the status assessment for groundwater quality. High aquifer- scale proportion is defined as the percentage of the primary aquifer with relative-concentrations greater than 1.0; moderate and low aquifer-scale proportions are defined as the percentage of the primary aquifer with moderate and low relative- concentrations, respectively. The methods used to calculate aquifer-scale proportions are based on an equal-area grid; thus, the proportions are areal rather than volumetric. Two statistical approaches - grid-based, which used one value per grid cell, and spatially weighted, which used the full dataset - were used to calculate aquifer-scale proportions for individual constituents and classes of constituents. The spatially weighted estimates of high aquifer-scale proportions were within the 90-percent confidence intervals of the grid-based estimates in all cases. The understanding assessment used statistical correlations between constituent relative-concentrations and

California↗

USGS2011

Hydrogeology, chemical characteristics, and water sources and pathways in the zone of contribution of a public-supply well in San Antonio, Texas

In 2001, the National Water-Quality Assessment (NAWQA) Program of the U.S. Geological Survey initiated a series of studies on the transport of anthropogenic and natural contaminants (TANC) to public-supply wells (PSWs). The main goal of the TANC project was to better understand the source, transport, and receptor factors that control contaminant movement to PSWs in representative aquifers of the United States. Regional- and local-scale study areas were selected from within existing NAWQA study units, including the south-central Texas Edwards aquifer. The local-scale TANC study area, nested within the regional-scale NAWQA study area, is representative of the regional Edwards aquifer. The PSW selected for study is within a well field of six production wells. Although a single PSW was initially selected, because of constraints of well-field operation, samples were collected from different wells within the well field for different components of the study. Data collected from all of the well-field wells were considered comparable because of similar well construction, hydrogeology, and geochemistry. An additional 38 PSWs (mostly completed in the confined part of the aquifer) were sampled throughout the regional aquifer to characterize water quality. Two monitoring well clusters, with wells completed at different depths, were installed to the east and west of the well field (the Zarzamora and Timberhill monitoring well clusters, respectively). One of the monitoring wells was completed in the overburden to evaluate potential hydrologic connectivity with the Edwards aquifer. Geophysical and flowmeter logs were collected from one of the well-field PSWs to determine zones of contribution to the wellbore. These contributing zones, associated with different hydrogeologic units, were used to select monitoring well completion depths and groundwater sample collection depths for depth-dependent sampling. Depth-dependent samples were collected from the PSW from three different depths and under three different pumping conditions. Additionally, selected monitoring wells and one of the well-field PSWs were sampled several times in response to a rainfall and recharge event to assess short-term (event-scale) temporal variations in water quality. For comparison purposes, groundwater samples were categorized as being from regional aquifer PSWs, from the well field (wellhead samples), from the monitoring wells (excluding the overburden well), from the overburden well, from the PSW depth-dependent sampling, and from temporal sampling. Groundwater samples were analyzed for inorganic, organic, isotopic, and age-dating tracers to characterize geochemical conditions in the aquifer and provide understanding of the mechanisms of mobilization and movement of selected constituents from source areas to a PSW. Sources, tracers, and conditions used to assess water quality and processes affecting the PSW and the aquifer system included (1) carbonate host rock composition; (2) physicochemical constituents; (3) major and trace element concentrations; (4) saturation indices with respect to minerals in aquifer rocks; (5) elemental ratios, such as magnesium to calcium ratios, that are indicative of water-rock interaction processes; (6) oxidation-reduction conditions; (7) nutrient concentrations, in particular nitrate concentrations; (8) the isotopic composition of nitrate, which can point to specific nitrate sources; (9) strontium isotopes; (10) stable isotopes of hydrogen and oxygen; (11) organic contaminant concentrations, including pesticides and volatile organic compounds; (12) age tracers, apparent-age distribution, and dissolved gas data used in age interpretations; (13) depth-dependent water chemistry collected from the PSW under different pumping conditions to assess zones of contribution; and (14) temporal variability in groundwater composition from the PSW and selected monitoring wells in response to an aquifer recharge event. Geochemical results indicate that the well-field and monitoring well samples were largely representative of groundwater in the regional confined aquifer. Constituents of concern in the Edwards aquifer for the long-term sustainability of the groundwater resource include the nutrient nitrate and anthropogenic organic contaminants. Nitrate concentrations (as nitrogen) for regional aquifer PSWs had a median value of 1.9 milligrams per liter, which is similar to previously reported values for the regional aquifer. Nitrate-isotope compositions for groundwater samples collected from the well-field PSWs and monitoring wells had a narrow range, with values indicative of natural soil organic values. A comparison with historical nitrate-isotope values, however, suggests that a component of nitrate in groundwater from biogenic sources might have increased over the last 30 years. Several organic contaminants (the pesticide atrazine, its degradate deethylatrazine, trichloromethane (chloroform; a drinking-water disinfection byproduct), and the solvent tetrachloroethene (PCE)) were widely distributed throughout the regional aquifer and in the local-scale TANC study area at low concentrations (less than 1 microgram per liter). Higher concentrations of PCE were detected in samples from the well-field PSWs and Zarzamora monitoring wells relative to the regional aquifer PSWs. The urban environment is a likely source of contaminants to the aquifer, and these results indicate that one or more local urban sources might be supplying PCE to the Zarzamora monitoring wells and the well-field wells. Samples from the well field also had high concentrations of chloroform relative to the monitoring wells and regional aquifer PSWs. For samples from the regional aquifer PSWs, the most frequently detected organic contaminants generally decreased in concentration with increasing well depth. Deeper wells might intercept longer regional flow paths with higher fractions of older water or water recharged in rural recharge areas in the western part of the aquifer that have been less affected by anthropogenic contaminants. A scenario of hypothetical contaminant loading was evaluated by using results from groundwater-flow-model particle tracking to assess the response of the aquifer to potential contamination. Results indicate that the aquifer responds quickly (less than 1 year to several years) to contaminant loading; however, it takes a relatively long time (decades) for concentrations to reach peak values. The aquifer also responds quickly (less than 1 year to several years) to the removal of contaminant loading; however, it also takes a relatively long time (decades) to reach near background concentrations. Interpretation of geochemical age tracers in this well-mixed karst system was complicated by contamination of a majority of measured tracers and complexities of extensive mixing. Age-tracer results generally indicated that groundwater samples were composed of young, recently recharged water with piston-flow model ages ranging from less than 1 to 41 years, with a median of 17 years. Although a piston-flow model is typically not valid for karst aquifers, the model ages provide a basis for comparing relative ages of different samples and a reference point for more complex hydrogeologic models for apparent-age interpretations. Young groundwater ages are consistent with particle-tracking results from hydrogeologic modeling for the local-scale TANC study area. Age-tracer results compared poorly with other geochemical indicators of groundwater residence time and anthropogenic effects on water quality, indicating that hydrogeologic conceptual models used in groundwater age interpretations might not adequately account for mixing in this karst system. Groundwater samples collected from the well field under a variety of pumping conditions were relatively homogeneous and well mixed for numerous geochemical constituents (with the notable exception of age tracers). Groundwater contributions to the PSW were dominated by well-mixed, relatively homogeneous groundwater, typical of the regional confined aquifer. Zones of preferential flow were determined for the PSW, but groundwater samples from different stratigraphic units were not geochemically distinct. Variations in chemical constituents in response to a rainfall and aquifer recharge event occurred but were relatively minor in the PSW and monitoring wells. This observation is consistent with the hypothesis that the response to individual recharge events in the confined aquifer, unless intersecting conduit flow paths, might be attenuated by mixing processes along regional flow paths. Results of this study are consistent with the existing conceptual understanding of aquifer processes in this karst system and are useful for water-resource development and management practices.

Texas↗

USGS1991

Weathering processes and the composition of inorganic material transported through the Orinoco River system, Venezuela and Colombia

The composition of river-borne material in the Orinoco River system is related primarily to erosion regime, which in turn is related to tectonic setting; especially notable is the contrast between material derived from tectonically active mountain belts and that from stable cratonic regions. For a particular morpho-tectonic region, the compositional suites of suspended sediment, bed material, overback deposits, and dissolved phases are fairly uniform are are typically distinct from whose of other regions. For each region, a consistent set of chemical weathering reactions can be formulated to explain the composition of dissolved and solid loads. In developing these formulations, erosion on slopes and storage of solids in soils and alluvial sediments are important considerations. Compositionally verymature sediment is derived from areas of thick soils where erosion is transport limited and from areas where sediments are stored for extended periods of time in alluvial deposits. Compositionally immature sediments are derived from tectonically active mountain belts where erosion is weathering limited. Weathering-limited erosion also is important in the elevated parts of the Guayana Shield within areas of sleep topography. Compared to the mountain belts, sediments derived from elevated parts of the Shield are more mature. A greater degree of chemical weathering seems to be needed to erode the rock types typical of the Shield. The major-element chemistry and mineral composition of sediment delivered by the Orinoco River to the ocean are controlled by rivers that have their headwaters in mountain belts and cross the Llanos, a region of alluvial plains within the foreland basin. The composition of sediments in rivers that drain the Shield seems to be established primarily at the site of soil formation, whereas for rivers that drain the mountain belts, additional weathering occurs during s episodes of storage on alluvial plains as sediments are transported across the Llanos to the main stem of the Orinoco. After mixing into the main stem, there seems to be little subsequent alteration of sediment.

Orinoco River↗

USGS2010

Effects of altered groundwater chemistry upon the pH-dependency and magnitude of bacterial attachment during transport within an organically contaminated sandy aquifer

The effects of a dilute (ionic strength = 5 × 10 −3 M) plume of treated sewage, with elevated levels (3.9 mg/L) of dissolved organic carbon (DOC), upon the pH-dependency and magnitude of bacterial transport through an iron-laden, quartz sand aquifer (Cape Cod, MA) were evaluated using sets of replicate, static minicolumns. Compared with uncontaminated groundwater, the plume chemistry diminished bacterial attachment under mildly acidic (pH 5.0–6.5) in-situ conditions, in spite of the 5-fold increase in ionic strength and substantively enhanced attachment under more alkaline conditions. The effects of the hydrophobic neutral and total fractions of the plume DOC; modest concentrations of fulvic and humic acids (1.5 mg/L); linear alkyl benzene sulfonate (LAS) (25 mg/L); Imbentin (200 μg/L), a model nonionic surfactant; sulfate (28 mg/L); and calcium (20 mg/L) varied sharply in response to relatively small changes in pH, although the plume constituents collectively decreased the pH-dependency of bacterial attachment. LAS and other hydrophobic neutrals (collectively representing only ∼3% of the plume DOC) had a disproportionately large effect upon bacterial attachment, as did the elevated concentrations of sulfate within the plume. The findings further suggest that the roles of organic plume constituents in transport or bacteria through acidic aquifer sediments can be very different than would be predicted from column studies performed at circumneutral pH and that the inorganic constituents within the plume cannot be ignored.

Water Research↗

USGS2014

Nitrogen deposition effects on diatom communities in lakes from three National Parks in Washington State

The goal of this study was to document if lakes in National Parks in Washington have exceeded critical levels of nitrogen (N) deposition, as observed in other Western States. We measured atmospheric N deposition, lake water quality, and sediment diatoms at our study lakes. Water chemistry showed that our study lakes were ultra-oligotrophic with ammonia and nitrate concentrations often at or below detection limits with low specific conductance (−1 year −1 and were variable both within and across the parks. Diatom assemblages in a single sediment core from Hoh Lake (Olympic National Park) displayed a shift to increased relative abundances of Asterionella formosa and Fragilaria tenera beginning in the 1969–1975 timeframe, whereas these species were not found at the remaining (nine) sites. These diatom species are known to be indicative of N enrichment and were used to determine an empirical critical load of N deposition, or threshold level, where changes in diatom communities were observed at Hoh Lake. However, N deposition at the remaining nine lakes does not seem to exceed a critical load at this time. At Milk Lake, also in Olympic National Park, there was some evidence that climate change might be altering diatom communities, but more research is needed to confirm this. We used modeled precipitation for Hoh Lake and annual inorganic N concentrations from a nearby National Atmospheric Deposition Program station, to calculate elevation-corrected N deposition for 1980–2009 at Hoh Lake. An exponential fit to this data was hindcasted to the 1969–1975 time period, and we estimate a critical load of 1.0 to 1.2 kg N ha −1 year −1 for wet deposition for this lake.

Washington↗

USGS2025

Quality of groundwater used for domestic supply in the Gilroy-Hollister basin and surrounding areas, California, 2022

More than 2 million Californians rely on groundwater from domestic wells for drinking-water supply. This report summarizes a 2022 California Groundwater Ambient Monitoring and Assessment Priority Basin Project (GAMA-PBP) water-quality survey of 33 domestic and small-system drinking-water supply wells in the Gilroy-Hollister Valley groundwater basin and the surrounding areas, where more than 20,000 residents are estimated to utilize privately owned domestic wells. The study area includes the Llagas subbasin in the north, the North San Benito subbasin in the south, and the surrounding uplands. The study was focused on groundwater resources used for domestic drinking-water supply, which are mostly drawn from shallower parts of aquifer systems rather than those of groundwater resources used for public drinking-water supply in the same area. This assessment characterized the quality of ambient groundwater in the aquifer before filtration or treatment, rather than the quality of drinking water delivered to the tap. To provide context, the measured concentrations of constituents in groundwater were compared to Federal and California State regulatory and non-regulatory benchmarks for drinking-water quality. A grid-based method was used to estimate the areal proportions of groundwater resources used for domestic drinking wells that have water-quality constituents present at high concentrations (above the benchmark), moderate concentrations (between one-half of the benchmark and the benchmark for inorganic constituents, or between one-tenth of the benchmark and the benchmark for organic constituents), and low concentrations (less than one-half or one-tenth the benchmark for inorganic and organic constituents, respectively). This method provides statistically representative results at the study-area scale and permits comparisons to other GAMA-PBP study areas. In the study area, inorganic constituents in groundwater were greater than regulatory benchmarks (U.S. Environmental Protection Agency [EPA] or State of California maximum contaminant levels [MCLs]) for public drinking-water quality in 24 percent of domestic groundwater resources. The inorganic constituents present at concentrations greater than MCLs for drinking water were nitrate (as nitrogen), barium, chromium, and selenium. Total dissolved solids (TDS) or manganese were present at concentrations greater than the secondary maximum contaminant levels (SMCLs) that the State of California uses as aesthetic-based benchmarks in 48 percent of domestic groundwater resources. No volatile organic compounds or pesticide constituents were present at concentrations greater than regulatory benchmarks. Total coliform bacteria and enterococci were detected in 4 percent of domestic groundwater resources. Per- and polyfluoroalkyl substances (PFAS) were detected in 19 percent of domestic groundwater resources, and 10 percent had concentrations greater than recently enacted (April 2024) EPA MCLs. Physical and chemical factors from natural and anthropogenic sources that could affect the groundwater quality were evaluated using results from statistical testing of associations between constituent concentrations and potential explanatory variables. In this study, relevant physical factors include well construction characteristics, groundwater age, site proximity to groundwater recharge or discharge zones, and potential sources of contamination. Relevant chemical factors include the initial chemistry of the recharge water, the mineralogy of the aquifer sediments, and the subsequent shifts in chemistry as biologic and geologic reactions alter groundwater in the subsurface. Nitrate concentrations were correlated to agricultural land use, distance from the boundary of the Gilroy-Hollister Valley groundwater basin, and the proportion of modern (post-1950s) water captured by the well. Denitrification under anoxic redox conditions can mitigate some nitrate derived from fertilizer application. Total dissolved solids primarily were derived from water-rock interactions with soils and aquifer materials in the study area, but there were high concentrations where agricultural practices contributed additional TDS. Mineralogy of aquifer sediments and rocks also affect barium, selenium, boron, and chromium concentrations in the Gilroy-Hollister Valley groundwater basin. PFAS were positively correlated with urban land use and the proportion of modern water captured by the well.

California↗

USGS2003

Reconnaissance of mercury in lakes, wetlands, and rivers in the Red River of the North Basin, North Dakota, March through August 2001

Devils Lake rose dramatically during the 1990's, causing extensive flood damages. Because of the potential for continued flooding, the U.S. Army Corps of Engineers has been conducting studies to evaluate the feasibility of constructing and operating an outlet from Devils Lake. The occurrence of mercury in lakes, wetlands, and rivers and the potential for increased loading of mercury into the Sheyenne River as a result of a Devils Lake outlet needed to be evaluated as part of the studies. Sixteen lake, wetland, and river sites in the Devils Lake, Sheyenne River, Red River of the North, and Red Lake River Basins were sampled and analyzed for mercury constituents and other selected properties and constituents relevant to mercury aquatic chemistry. For the lake and wetland sites, whole-water methylmercury concentrations ranged from less than 0.04 to 3.53 nanograms per liter and whole-water total mercury concentrations ranged from 0.38 to 7.02 nanograms per liter. Conditions favorable for methylation of mercury generally exist at the lake and wetland sites, as indicated by larger dissolved methylmercury concentrations in near-bottom samples than in near-surface samples and by relatively large ratios of methylmercury to total mercury (generally greater than 10 percent for the summer sampling period). Total mercury concentrations were larger for the summer sampling period than for the winter sampling period for all lake and wetland sites. A wetland site in the upper Devils Lake Basin had the largest mercury concentrations for the lake and wetland sites. For the river sites, whole-water methylmercury concentrations ranged from 0.15 to 1.13 nanograms per liter and whole-water total mercury concentrations ranged from 2.00 to 26.90 nanograms per liter. Most of the mercury for the river sites occurred in particulate inorganic phase. Summer ratios of whole-water methylmercury to whole-water total mercury were 35 percent for Starkweather Coulee (a wetland-dominated site), near or less than 10 percent for the Sheyenne River sites, and less than 8 percent for the Red River of the North and Red Lake River sites. Although the number of samples collected during this investigation is small, results indicated an outlet from Devils Lake probably would not have adverse effects on mercury concentrations in the Sheyenne River upstream from Lake Ashtabula. However, because discharges in the Sheyenne River would increase during some periods, loads of mercury entering Lake Ashtabula also would increase. Lake Ashtabula probably serves as a sink for suspended sediment and mercury. Thus, a Devils Lake outlet probably would not have substantial effects on mercury concentrations and loads in the downstream part of the Sheyenne River or in the Red River of the North. More substantial effects could occur for Lake Ashtabula.

North Dakota↗

USGS2020

Thermokarst amplifies fluvial inorganic carbon cycling and export across watershed scales on the Peel Plateau, Canada

As climate warming and precipitation increase at high latitudes, permafrost terrains across the circumpolar north are poised for intensified geomorphic activity and sediment mobilization that are expected to persist for millennia. In previously glaciated permafrost terrain, ice-rich deposits are associated with large stores of reactive mineral substrate. Over geological timescales, chemical weathering moderates atmospheric CO 2 levels, raising the prospect that mass wasting driven by terrain consolidation following thaw (thermokarst) may enhance weathering of permafrost sediments and thus climate feedbacks. The nature of these feedbacks depends upon the mineral composition of sediments (weathering sources) and the balance between atmospheric exchange of CO 2 vs. fluvial export of carbonate alkalinity ( Σ [ HCO 3 - "> HCO − 3 , CO 3 2 - "> CO 2 − 3 ]). Working in the fluvially incised, ice-rich glacial deposits of the Peel Plateau in northwestern Canada, we determine the effects of slope thermokarst in the form of retrogressive thaw slump (RTS) activity on mineral weathering sources, CO 2 dynamics, and carbonate alkalinity export and how these effects integrate across watershed scales ( ∼ 2 to 1000 km 2 ). We worked along three transects in nested watersheds with varying connectivity to RTS activity: a 550 m transect along a first-order thaw stream within a large RTS, a 14 km transect along a stream which directly received inputs from several RTSs, and a 70 km transect along a larger stream with headwaters that lay outside of RTS influence. In undisturbed headwaters, stream chemistry reflected CO 2 from soil respiration processes and atmospheric exchange. Within the RTS, rapid sulfuric acid carbonate weathering, prompted by the exposure of sulfide- and carbonate-bearing tills, appeared to increase fluvial CO 2 efflux to the atmosphere and propagate carbonate alkalinity across watershed scales. Despite covering less than 1 % of the landscape, RTS activity drove carbonate alkalinity to increase by 2 orders of magnitude along the largest transect. Amplified export of carbonate alkalinity together with isotopic signals of shifting DIC and CO 2 sources along the downstream transects highlights the dynamic nature of carbon cycling that may typify glaciated permafrost watersheds subject to intensification of hillslope thermokarst. The balance between CO 2 drawdown in regions where carbonic acid weathering predominates and CO 2 release in regions where sulfides are more prevalent will determine the biogeochemical legacy of thermokarst and enhanced weathering in northern permafrost terrains. Effects of RTSs on carbon cycling can be expected to persist for millennia, indicating a need for their integration into predictions of weathering–carbon–climate feedbacks among thermokarst terrains.

Biogeosciences↗

USGS2006

Unusual Holocene and late Pleistocene carbonate sedimentation in Bear Lake, Utah and Idaho, USA

Bear Lake (Utah-Idaho, USA) has been producing large quantities of carbonate minerals of varying mineralogy for the past 17,000 years. The history of sedimentation in Bear Lake is documented through the study of isotopic ratios of oxygen, carbon, and strontium, percent organic carbon, percent CaCO3, X-ray diffraction mineralogy, HCl-leach inorganic geochemistry, and magnetic properties on samples from three piston cores. Historically, the Bear River, the main source of water for Great Salt Lake, did not enter Bear Lake until it was artificially diverted into the lake at the beginning of the 20th century. However, during the last glacial interval, the Bear River did enter Bear Lake depositing red, calcareous, silty clay. About 18,000 years ago, the Bear River became disconnected from Bear Lake. A combination of warmer water, increased evaporation, and increased organic productivity triggered the precipitation of calcium carbonate, first as calcite. As the salinity of the lake increased due to evaporation, aragonite began to precipitate about 11,000 years ago. Aragonite is the dominant mineral that accumulated in bottom sediments of the lake during the Holocene, comprising an average of about 70 wt.% of the sediments. Aragonite formation in a large, cold, oligotrophic, high latitude lake is highly unusual. Lacustrine aragonite usually is found in small, saline lakes in which the salinity varies considerably over time. However, Bear Lake contains endemic ostracodes and fish, which indicate that the chemistry of the lake has remained fairly constant for a long time. Stable isotope data from Holocene aragonite show that the salinity of Bear Lake increased throughout the Holocene, but never reached highly evolved values of ??18O in spite of an evaporation-dominated water balance. Bear Lake hydrology combined with evaporation created an unusual situation that produced large amounts of aragonite, but no evaporite minerals.

Sedimentary Geology↗

USGS2016

Baseline assessment of groundwater quality in Wayne County, Pennsylvania, 2014

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, geologic formations which have potential for natural gas development, underlie Wayne County and neighboring counties in northeastern Pennsylvania. In 2014, the U.S. Geological Survey, in cooperation with the Wayne Conservation District, conducted a study to assess baseline shallow groundwater quality in bedrock aquifers in Wayne County prior to potential extensive shale-gas development. The 2014 study expanded on previous, more limited studies that included sampling of groundwater from 2 wells in 2011 and 32 wells in 2013 in Wayne County. Eighty-nine water wells were sampled in summer 2014 to provide data on the presence of methane and other aspects of existing groundwater quality throughout the county, including concentrations of inorganic constituents commonly present at low levels in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. Depths of sampled wells ranged from 85 to 1,300 feet (ft) with a median of 291 ft. All of the groundwater samples collected in 2014 were analyzed for bacteria, major ions, nutrients, selected inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, selected man-made organic compounds (including volatile organic compounds and glycols), dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Results of the 2014 study show that groundwater quality generally met most drinking-water standards, but some well-water samples had one or more constituents or properties, including arsenic, iron, pH, bacteria, and radon-222, that exceeded primary or secondary maximum contaminant levels (MCLs). Arsenic concentrations were higher than the MCL of 10 micrograms per liter (µg/L) in 4 of 89 samples (4.5 percent) with concentrations as high as 20 µg/L; arsenic concentrations were higher than the Health Advisory level of 2 µg/L in 27 of 89 samples (30 percent). Total iron concentrations exceeded the secondary maximum contaminant level (SMCL) of 300 µg/L in 9 of 89 samples (10 percent). The pH ranged from 5.4 to 9.3 and did not meet the SMCL range of greater than 6.5 to less than 8.5 in 27 samples (30 percent); 22 samples had pH values less than 6.5, and 5 samples had pH values greater than 8.5. Total coliform bacteria were detected in 22 of 89 samples (25 percent); Escherichia coli were detected in only 2 of those 22 samples. Radon-222 activities ranged from 25 to 7,400 picocuries per liter (pCi/L), with a median of 2,120 pCi/L, and exceeded the proposed drinking-water standard of 300 pCi/L in 86 of 89 samples (97 percent); radon-222 activities were higher than the alternative proposed standard of 4,000 pCi/L in 12 of 89 samples (13.5 percent). Water from 8 of the 89 wells (9 percent) had concentrations of methane greater than the reporting level of 0.24 milligrams per liter (mg/L) with the detectable methane concentrations ranging from 0.74 to 9.6 mg/L. Of 16 replicate samples submitted to another laboratory with a lower reporting level of 0.0002 mg/L, 15 samples had detectable methane concentrations that ranged from 0.0011 to 9.7 mg/L. Of these 15 samples, low levels of ethane (0.00032 to 0.0017 mg/L) were detected in 6 of 7 samples with methane concentrations greater than 0.75 mg/L. The isotopic composition of methane in 6 of 8 samples with sufficient dissolved methane (about 1 mg/L) for isotopic analysis is consistent with a predominantly thermogenic methane source (sample carbon isotopic ratio δ13C CH4 values ranging from -56.36 to -45.97 parts per thousand (‰) and hydrogen isotopic ratio δD CH4 values ranging from -233.1 to -141.1 ‰). However, the low levels of ethane relative to methane indicate that the methane may be of microbial origin and subsequently underwent oxidation. Isotopic compositions indicated a possibly mixed thermogenic and microbial source (carbon dioxide reduction process) for the methane in 1 of the 8 samples (δ 13 C CH4 of -63.72 and δD CH4 of -192.3 ‰) and potential oxidation of microbial and (or) thermogenic methane in the remaining sample (δ 13 C CH4 of -46.56 and δD CH4 of -79.7 ‰). Groundwater samples with relatively elevated methane concentrations (near or greater than 1 mg/L) had a chemical composition that differed in some respects (pH, selected major ions, and inorganic trace constituents) from groundwater with relatively low methane concentrations (less than 0.75 mg/L). The seven well-water samples with the highest methane concentrations (from about 1 to 9.6 mg/L) also had among the highest pH values (8.1 to 9.3, respectively) and the highest concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide. Relatively elevated concentrations of some other constituents, such as barium, strontium, and chloride, commonly were present in, but not limited to, those well-water samples with elevated methane. Groundwater samples with the highest methane concentrations had chloride/bromide ratios that indicate mixing with a small amount of brine (0.02 percent or less, by volume) similar in composition to that reported for gas and oil well brines in Pennsylvania. Most other samples with low methane concentrations (less than about 1 mg/L) had chloride/bromide ratios that indicate predominantly man-made sources of chloride, such as road salt, septic systems, and (or) animal waste. Although naturally occurring brines may originate from deeper parts of the aquifer system, the man-made sources are likely to affect shallow groundwater. Geochemical modeling showed that the water chemistry of samples with elevated pH, sodium, lithium, bromide, and alkalinity could result from dissolution of calcite (calcium carbonate) combined with cation exchange and mixing with a small amount of brine. Through cation exchange reactions (which are equivalent to processes in a water softener) calcium ions released by calcite dissolution are exchanged for sodium ions on clay minerals. The spatial distribution of groundwater compositions generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands along the western border of Wayne County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can occur in deep wells in uplands but most frequently occur in stream valleys, especially at low elevations (less than about 1,200 ft above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River. Thus, the baseline assessment of groundwater quality in Wayne County prior to gas-well development shows that shallow (less than about 1,000 ft deep) groundwater is generally of good quality, but methane and some constituents present in high concentrations in brine (and produced waters from gas and oil wells) may be present at low to moderate concentrations in some parts of Wayne County.

Pennsylvania↗

USGS2012

Arsenic speciation in food chains from mid-Atlantic hydrothermal vents

Arsenic concentration and speciation were determined in benthic fauna collected from the Mid-Atlantic Ridge hydrothermal vents. The shrimp species, Rimicaris exoculata, the vent chimney-dwelling mussel, Bathymodiolus azoricus, Branchipolynoe seepensis, a commensal worm of B. azoricus and the gastropod Peltospira smaragdina showed variations in As concentration and in stable isotope (δ 13 C and δ 15 N) signature between species, suggesting different sources of As uptake. Arsenic speciation showed arsenobetaine to be the dominant species in R. exoculata, whereas in B. azoricus and B. seepensis arsenosugars were most abundant, although arsenobetaine, dimethylarsinate and inorganic arsenic were also observed, along with several unidentified species. Scrape samples from outside the vent chimneys covered with microbial mat, which is a presumed food source for many vent organisms, contained high levels of total As, but organic species were not detectable. The formation of arsenosugars in pelagic environments is typically attributed to marine algae, and the pathway to arsenobetaine is still unknown. The occurrence of arsenosugars and arsenobetaine in these deep sea organisms, where primary production is chemolithoautotrophic and stable isotope analyses indicate food sources are of vent origin, suggests that organic arsenicals can occur in a foodweb without algae or other photosynthetic life.

Environmental Chemistry↗

USGS2016

Viral lysis of photosynthesizing microbes as a mechanism for calcium carbonate nucleation in seawater

Removal of carbon through the precipitation and burial of calcium carbonate in marine sediments constitutes over 70% of the total carbon on Earth and is partitioned between coastal and pelagic zones. The precipitation of authigenic calcium carbonate in seawater, however, has been hotly debated because despite being in a supersaturated state, there is an absence of persistent precipitation. One of the explanations for this paradox is the geochemical conditions in seawater cannot overcome the activation energy barrier for the first step in any precipitation reaction; nucleation. Here we show that virally induced rupturing of photosynthetic cyanobacterial cells releases cytoplasmic-associated bicarbonate at concentrations ~23-fold greater than in the surrounding seawater, thereby shifting the carbonate chemistry toward the homogenous nucleation of one or more of the calcium carbonate polymorphs. Using geochemical reaction energetics, we show the saturation states (Ω) in typical seawater for calcite (Ω = 4.3), aragonite (Ω = 3.1), and vaterite (Ω = 1.2) are significantly elevated following the release and diffusion of the cytoplasmic bicarbonate (Ω calcite = 95.7; Ω aragonite = 68.5; Ω vaterite = 25.9). These increases in Ω significantly reduce the activation energy for nuclei formation thresholds for all three polymorphs, but only vaterite nucleation is energetically favored. In the post-lysis seawater, vaterite's nuclei formation activation energy is significantly reduced from 1.85 × 10 −17 J to 3.85 × 10 −20 J, which increases the nuclei formation rate from highly improbable (<<1.0 nuclei cm −3 s −1 ) to instantaneous (8.60 × 10 25 nuclei cm −3 s −1 ). The proposed model for homogenous nucleation of calcium carbonate in seawater describes a mechanism through which the initial step in the production of carbonate sediments may proceed. It also presents an additional role of photosynthesizing microbes and their viruses in marine carbon cycles and reveals these microorganisms are a collective repository for concentrated and reactive dissolved inorganic carbon (DIC) that is currently not accounted for in global carbon budgets and carbonate sediment diagenesis models.

Frontiers in Microbiology↗