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At least 1,639 records · Page 91Linked to original sources
USGS2019

Effects of ferric sulfate and polyaluminum chloride coagulation enhanced treatment wetlands on Typha growth, soil and water chemistry

Land surface subsidence is a concern in many deltas worldwide as it contributes to water quality degradation, loss of fertile land and increased potential for levee failure. As a possible solution to these concerns, on-site coagulation enhanced treatment wetlands(CETWs), coagulation water treatment followed by wetland passage serving as a settling basin, were implemented in a field-scale study located on a subsided island of the Sacramento-San Joaquin Delta in northern California under three treatments; coagulation with polyaluminum chloride (PAC), coagulation with ferric sulfate and an untreated control. Because CETWs offer a relatively novel solution for water quality improvement and subsidence reversal due to its low-infrastructure requirements and in-situ nature, effects from these systems remain uncharted and they may have adverse effects on plant biomass production that also contribute to sediment accretion. This study focuses on the effect CETWs had on the growth of Typha spp .; the dominant vegetation in the wetlands. Plant growth parameters and nutrient content were measured in conjunction with soil, pore waterand surface water chemistry. Soil analysis indicated there was no intermixing of newly formed flocs and original soil material. Where there was significant deposition of floc, PAC treatment reduced phosphate concentrations and ferric sulfate treatment increased total Fe concentrations in surrounding water compared to the control. Results indicated coagulation treatments had no negative effects on Typha leaf nutrient content, Typha growth or allometric parameters. Additionally, no signs of plant toxicity such as necrosis, wilting or chlorosis were observed in any of the treatments. Overall, this study suggests that CETWs are viable treatment option for water quality improvement and sediment accretion while having no negative impact on the growth of Typha plants.

Science of the Total Environment↗
USGS2020

Spatial variability of phytoplankton in a shallow tidal freshwater system reveals complex controls on abundance and community structure

Estuaries worldwide are undergoing changes to patterns of aquatic productivity because of human activities that alter flow, impact sediment delivery and thus the light field, and contribute nutrients and contaminants like pesticides and metals. These changes can influence phytoplankton communities, which in turn can alter estuarine food webs. We used multiple approaches-including high-resolution water quality mapping, synoptic sampling, productivity and nitrogen uptake rates, Lagrangian parcel tracking, enclosure experiments and bottle incubations-over a short time period to take a “spatial snapshot” of conditions in the northern region of the San Francisco Estuary (California, USA) to examine how environmental drivers like light availability, nutrients, water residence time, and contaminants affect phytoplankton abundance and community attributes like size distribution, taxonomic structure, and nutrient uptake rates. Zones characterized by longer residence time (15–60 days) had higher chlorophyll-a concentrations (9 ± 4 µg L −1 ) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ± 8%), lower ammonium concentrations (1 ± 0.8 µM), higher nitrate uptake rates, and higher rates of potential carbon productivity. Conversely, zones characterized by shorter residence time (1–14 days) had higher ammonium concentration (13 ± 5 µM) and lower chlorophyll-a concentration (5 ± 1 µg L −1 ) with diatoms making up a larger percent contribution. Longer residence time, however, did not result in the accumulation of large (>5 µm) cells considered important to pelagic food webs. Rather, longer residence time zones had a phytoplankton community comprised primarily of small cells, particularly picocyanobacteria that made up 38 ± 17% of the chlorophyll-a – nearly double the concentration seen in shorter residence time zones (22 ± 7% picocyanobacterial of chlorophyll-a). Our results suggest that water residence time in estuaries may have an effect as large or larger than that experimentally demonstrated for light, contaminants, or nutrients.

California↗
USGS2021

Evaluating the dynamics of groundwater, lakebed transport, nutrient inflow and algal blooms in Upper Klamath Lake, Oregon, USA

Transport of nutrients to lakes can occur via surface-water inflow, atmospheric deposition, groundwater (GW) inflow and benthic processes. Identifying and quantifying within-lake nutrient sources and recycling processes is challenging. Prior studies in hypereutrophic Upper Klamath Lake, Oregon, USA, indicated that ~60% of the early summer phosphorus (P) load to the lake was internal and hypothesized to be lakebed sediment release. Dynamic nutrient transport processes were examined to better characterize the nutrient sources. One-dimensional heat transport models calibrated to observed lakebed temperatures and a cross-sectional GW flow model provided estimates of GW-inflow rates that were greatest in spring and decreased through summer. One-dimensional solute transport models calibrated to observed lakebed pore-water dissolved silica (Si) and dissolved phosphate-phosphorus (DP) concentrations indicated that nutrients were transported from the lakebed by advection, diffusion, and enhanced mixing by benthic organisms and waves, and that DP removal occurred near the lakebed interface. Estimated water, Si, DP and total-phosphorus (TP) budgets indicated that GW contributed 21% of lake water inflow and at least 26, 20 and 16% of total Si, DP and TP inflow, respectively, when conservatively assuming background GW nutrient concentrations. However, lakebed GW (LGW) is enriched in nutrients during flow through lakebed sediment and the estimated GW contribution increased to 29 (33), 49 (67) and 43% (61%) of total Si, DP and TP inflow, respectively, if 20% (50%) of GW inflow to the lake was assumed to have LGW concentrations. Net nutrient inflow to the lake was greatest in spring and coincident with the annual diatom bloom. Inflowing dissolved nutrients appear to be assimilated by diatoms during the spring and become available for the summer Aphanizomenon flos-aquae bloom when the diatoms senesce. Thus, nutrient-enriched GW inflow and nutrient recycling by successive algal blooms must be considered when evaluating internal nutrient loading to lakes.

Oregon↗
USGS2021

Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

Science of the Total Environment↗
USGS2021

Groundwater development leads to decreasing arsenic concentrations in the San Joaquin Valley, California

In the San Joaquin Valley (SJV), California, about 10% of drinking water wells since 2010 had arsenic concentrations above the US maximum contaminant level of 10 μg/L. High concentrations of arsenic are often associated with high pH (greater than 7.8) or reduced geochemical conditions. Although most wells have low arsenic (<3 μg/L) and do not have changing arsenic concentrations, this study found that most wells with concentrations above 10 μg/L had arsenic trends. Overall, about 24% of wells had time-series trends since 2010 and 59% had paired-sample trends since 2000. Most wells had decreasing arsenic trends, even in wells with higher arsenic concentrations. These wells often had co-detections of increasing nitrate and sulfate trends that reflect oxic groundwater likely derived from agricultural recharge. Wells with increasing arsenic trends were deeper or located in the valley trough where aquifer materials are more fine-grained and where reducing conditions favor arsenic mobility. Wells with arsenic trends also tend to be clustered near areas of higher well density. Groundwater pumping in these areas has likely increased the contribution of younger, more oxic groundwater in wells with declining arsenic or, less frequently, increased the contribution of higher pH or reduced groundwater in wells with rising arsenic. Projections of arsenic trends indicate that 37 wells with high arsenic presently will be below 10 μg/L in ten years. Unfortunately, these improvements will be largely offset by 31 wells that are expected to increase above 10 μg/L in addition to expected rises in nitrate in wells where arsenic decreased. This study shows how human-altered flow systems can impact the natural geochemical character of water in both beneficial and deleterious ways.

California↗
USGS2021

Influence of redox gradients on nitrate transport from the landscape to groundwater and streams

Increases in nitrogen applications to the land surface since the 1950s have led to a cascade of negative environmental impacts, including degradation of drinking water supplies, nutrient enrichment of aquatic ecosystems and contributions to global climate change. In this study, groundwater, streambed porewater, and stream sampling were used to establish trends in nitrate concentrations and how redox gradients influence nitrate transport across diverse glacial terranes. Decadal sampling has found that elevated nitrate concentrations in shallow groundwater beneath cropland have been sustained for decades. Redox gradients established in the saturated zone using dissolved O 2 , iron, nitrate and excess N 2 from denitrification suggest that nitrate-bearing zones are thin in glacial terranes dominated by fine materials. These thin nitrate-bearing zones lead to suboxic, low nitrate streambed porewater and limit the contributions of nitrate to streams from slow-flow groundwater. In contrast, thick oxic zones in more coarse-grained glacial terranes allow nitrate to reach deeper groundwater, resulting in streambed porewater with elevated nitrate concentrations and causing a large portion of stream nitrate to be derived from slow-flow groundwater. Groundwater age tracer data indicate that denitrification occurs more quickly in the terrane dominated by fine material than in the more coarse-grained terrane. The quicker depletion of nitrate in the more fine-grained terrane suggests that the thinner oxic zone in this terrane is due, in part, to the greater availability and reactivity of electron donors in this terrane than in the more coarse-grained terrane. Groundwater age tracer data and hydrograph separation analysis suggest that saturated zone lag times between when changes in land use practices occur and when changes in stream water are fully observed may vary widely across hydrogeologic settings.

Illinois, Indiana, Iowa, Michigan, Minnesota, Wisc↗
USGS2023

Understanding ecological response to physical characteristics in side channels of a large floodplain-river ecosystem

Side channels in large floodplain rivers serve a variety of important ecological roles, particularly in reaches where habitat conditions have been degraded or diminished. We developed hypotheses regarding side channel ecological structure whereby we expected species richness of young-of-year fishes to generally be higher in shallower, more physically heterogeneous side channels with lower velocities, with differences based on reproductive guild. We also hypothesized species richness of adult fishes to be higher in side channels with greater heterogeneity that could support diverse foraging resources and provide refugia during extreme flow conditions. To test these hypotheses, we used a 28-year fish community dataset from the Upper Mississippi and Illinois Rivers. Across six study reaches, we assessed metrics of side channel physical size, heterogeneity, and connectivity that were hypothesized to explain variance of fish community response, while accounting for site-level factors across 52 side channels using multilevel models. We then used these side channel-level characteristics in a K-means cluster analysis to classify 1126 side channels across 32 reaches of the river system. Our results indicated that the relative explanatory contributions of physical metrics varied by response variable, providing varying evidence in support of our hypotheses, and indicating that different forms of heterogeneity matter in different ways. Side channel-level factors were more explanatory of fish community responses in side channels of upstream reaches compared to downstream reaches and percent wet forest was the most explanatory side channel-level factor of fish community responses across all models. Our classification of side channels indicated strong spatial contrasts in the abundance and diversity of side channels across reaches. Scaling up to understand how the diversity and abundance of different types of side channels contributes to landscape-scale ecological functions and processes would be useful for establishing targets for reach-scale physical heterogeneity.

Upper Mississippi River and Illinois River↗
USGS2023

Mercury sources and budget for the Snake River above a hydroelectric reservoir complex

Understanding sources of mercury (Hg) and methylmercury (MeHg) to a water body is critical for management but is often complicated by poorly characterized Hg inputs and in situ processes, such as inorganic Hg methylation. In this study, we determined inorganic Hg and MeHg concentrations and loads (filter-passing and particulate fractions) for a semi-arid 164-kilometer stretch of the Snake River above the Hells Canyon Complex, a Hg-impaired hydroelectric reservoir complex on the Idaho-Oregon border, and used water quality measurements and Hg stable isotope ratios to create a comprehensive Hg source budget for the river. Results show that whereas most of the streamflow to the study reach comes from the main branch of the Snake River (i.e., the upstream watershed), major tributaries within the study reach contribute a greater proportion of inorganic Hg and MeHg loads. Mercury stable-isotope analyses highlight that Hg within the tributaries is predominantly associated with geologic deposits and snowmelt sources, the latter reflecting wet deposition. Surprisingly, irrigation return drains contribute 40–50 % of particulate inorganic Hg loads despite being ≤4.3 % of the overall water budget. Together, tributaries and irrigation return drains account for 97–100 % of the inorganic Hg and streamflow to the study reach, but ~65 % of the MeHg, indicating in-stream and riparian methylation may be an important and previously unrecognized source of MeHg. Streamflow, total suspended solids, dissolved organic carbon, and agricultural land cover were found to be important controls on the mobilization and transport of different Hg species and fractions. This study represents the first fluvial budget for Hg in the Snake River that accounts for particulate and filter-passing Hg species from both major tributaries and irrigation return drains, and expands our understanding of Hg sources and methylation processes within semi-arid environments. This information is critical to inform management decisions related to elevated Hg burdens in biota.

Idaho, Nevada, Oregon↗
USGS2024

Nitrate exposure from drinking water and dietary sources among Iowa farmers using private wells

Nitrate levels are increasing in water resources across the United States and nitrate ingestion from drinking water has been associated with adverse health risks in epidemiologic studies at levels below the maximum contaminant level (MCL). In contrast, dietary nitrate ingestion has generally been associated with beneficial health effects. Few studies have characterized the contribution of both drinking water and dietary sources to nitrate exposure. The Agricultural Health Study is a prospective cohort of farmers and their spouses in Iowa and North Carolina. In 2018–2019, we assessed nitrate exposure for 47 farmers who used private wells for their drinking water and lived in 8 eastern Iowa counties where groundwater is vulnerable to nitrate contamination. Drinking water and dietary intakes were estimated using the National Cancer Institute Automated Self-Administered 24-Hour Dietary Assessment tool. We measured nitrate in tap water and estimated dietary nitrate from a database of food concentrations. Urinary nitrate was measured in first morning void samples in 2018–19 and in archived samples from 2010 to 2017 (minimum time between samples: 2 years; median: 7 years). We used linear regression to evaluate urinary nitrate concentrations in relation to total nitrate, and drinking water and dietary intakes separately. Overall, dietary nitrate contributed the most to total intake (median: 97 %; interquartile range [IQR]: 57–99 %). Among 15 participants (32 %) whose drinking water nitrate concentrations were at/above the U.S. Environmental Protection Agency MCL (10 mg/L NO 3 -N), median intake from water was 44 % (IQR: 26–72 %). Total nitrate intake was the strongest predictor of urinary nitrate concentrations (R 2 = 0.53). Drinking water explained a similar proportion of the variation in nitrate excretion (R 2 = 0.52) as diet (R 2 = 0.47). Our findings demonstrate the importance of both dietary and drinking water intakes as determinants of nitrate excretion.

Iowa↗
USGS2025

Spatially resolved source apportionment of per- and polyfluoroalkyl substances (PFAS) within a post-industrial river catchment

Source apportionment of per- and polyfluoroalkyl substances (PFAS) in rivers is typically based on water concentrations, which cannot quantify PFAS loads or define geographical source areas. This study applied a river catchment-scale approach to identify PFAS source zones and assess the relative importance of industrial PFAS sources in the River Mersey, UK – a post-industrial, densely populated catchment with diverse PFAS sources. Synoptic sampling and PFAS river load analysis identified key sub-catchments and river stretches contributing the majority of PFAS. Notably, the highest PFAS concentrations did not always correspond to the greatest loads. Most PFOS (64 %), PFOA (49 %), 6:2FTS (46 %) and PFHxS (56 %) were exported from the Upper Mersey sub-catchment, despite higher concentrations in northern sub-catchments, emphasising the importance of load-based monitoring. Mass balance analysis of loads highlighted substantial inputs from specific river stretches, notably the Lower Irwell (Bolton to Manchester City Centre), River Tame (Marple Bridge to Stockport), and Upper Mersey (Stockport to Urmston). While PFAS loads generally scaled with catchment area, yield (load per unit area) analysis identified disproportionately high exports from small headwater catchments, notably the upper River Roch (PFOA, PFHpA and PFHxA) and Glaze Brook (PFBS). Industrial sources in these sub-catchments (a waste management facility and landfills, respectively) were confirmed using gadolinium anomaly analysis and consented discharge records. More widely, gadolinium data suggested industrial discharges may contribute to PFAS occurrence at 62 % of our sample sites throughout the catchment. These findings demonstrate that spatial analysis of PFAS loads, rather than concentrations alone, is critical for identifying PFAS source areas. We present a scalable monitoring framework for PFAS source apportionment applied at the river catchment-scale that can be used by environmental managers to target and prioritise PFAS source areas for detailed monitoring and remediation.

River Mersey↗
USGS2025

Global recreational consumption of non-native inland fish: Higher economic benefits, but lower nutritional value and climate resilience

Inland recreational fisheries are globally significant leisure pursuits, with well-documented benefits to human health and well-being, but also one of the principal drivers of non-native fish introductions to enhance fishing opportunities, whether for sport or sustenance. In this study, we assess the relative reliance of global inland recreational fisheries on non-native versus native species for harvest. We further examine how this reliance varies by economic and nutritional value as well as the climate vulnerability of the species involved. We demonstrate that, of the 1,325,851 t of inland recreational fishes recreationally harvested for consumption worldwide in 2021, non-native fish were a small proportion (4 %; 53,651 t). On a global scale, non-native fish contributed a net positive 38.2 % economic value to inland recreational harvest. However, they also contributed a net negative −21.9 % nutritional value to inland recreational harvest. Non-native fishes were also more climate vulnerable (i.e., higher average climate vulnerability index values) and thus proportionally increased overall estimates of climate vulnerability with a net positive of 70.9 %. Our results quantitatively demonstrate that non-native species play a more important role in inland consumptive recreational fisheries than their mere harvest volume would suggest. However, many nuances were seen on the continent and country scale, which reflect the complexity of fisher behavior, fish distribution and socio-economic factors. Our findings help unravel the complex effects of non-native species on human activities and underscore the need to evaluate their global impacts holistically.

Science of the Total Environment↗
USGS2004

Reconstruction of the Upper Jurassic Morrison Formation extinct ecosystem - A synthesis

A synthesis of recent and previous studies of the Morrison Formation and related beds, in the context of a conceptual climatic/hydrologic framework, permits reconstruction of the Late Jurassic dinosaurian ecosystem throughout the Western Interior of the United States and Canada. Climate models and geologic evidence indicate that a dry climate persisted in the Western Interior during the Late Jurassic. Early and Middle Kimmeridgian eolian deposits and Late Kimmeridgian alkaline, saline wetland/lacustrine deposits demonstrate that dryness persisted throughout the Kimmeridgian. Tithonian-age coal reflects lower evaporation rates associated with a slight cooling trend, but not a significant climate change. With a subtropical high over the Paleo-Pacific Ocean and atmospheric circulation generally toward the east, moisture carried by prevailing winds "rained out" progressively eastward, leaving the continental interior-and the Morrison depositional basin-dry. Within the basin, high evaporation rates associated with the southerly paleolatitude and greenhouse effects added to the dryness. Consequently, the two main sources of water-groundwater and surface water-originated outside the basin, through recharge of regional aquifers and streams that originated in the western uplands. Precipitation that fell west of the basin recharged aquifers that underlay the basin and discharged in wetlands and lakes in the distal, low-lying part of the basin. Precipitation west of the basin also fed intermittent and scarce perennial streams that flowed eastward. The streams were probably "losing" streams in their upstream reaches, and contributed to a locally raised water table. Elsewhere in the basin, where the floodplain intersected the water table, small lakes dotted the landscape. Seasonal storms, perhaps in part from the Paleo-Gulf of Mexico, brought some precipitation directly to the basin, although it was also subjected to "rain out" en route. Thus, meteoric input to the basin was appreciably less than groundwater and surface water contributions. The terrestrial Morrison ecosystem, which can be likened to a savannah, expanded with the northward retreat of the Late Jurassic Western Interior Seaway. The ecosystem was a complex mosaic, the components of which shifted through time. Riparian environments probably were the most diverse parts of the ecosystem, where a multi-storeyed canopy supported a diverse fauna, from insects to dinosaurs. Equable conditions also existed in wetlands, lakes, and elsewhere on the floodplain when seasonal rainfall brought an herbaceous groundcover to life. Eolian environments and alkaline, saline wetlands were inhospitable to life.Large herbivorous dinosaurs were adapted to this semi-arid landscape. Their size was an adaptive asset based on considerations of food requirements associated with a low metabolism and was also an advantage for migration during drought. Some of the large sauropods were adapted to browsing the higher vegetation associated with riparian environments; others to grazing the herbaceous groundcover on the floodplain and charophytes in the wetlands. The extensive distal wetlands may, in fact, have been refugia for some of these herbivores during the dry season and droughts. Extended periods of drought account for some of the dinosaur death assemblages; yet, the ecosystem could also sustain the most unusual life forms that ever roamed the Earth. ?? 2004 Elsevier B.V. All rights reserved.

Sedimentary Geology↗
USGS2011

Geological effects and implications of the 2010 tsunami along the central coast of Chile

Geological effects of the 2010 Chilean tsunami were quantified at five near-field sites along a 200 km segment of coast located between the two zones of predominant fault slip. Field measurements, including topography, flow depths, flow directions, scour depths, and deposit thicknesses, provide insights into the processes and morphological changes associated with tsunami inundation and return flow. The superposition of downed trees recorded multiple strong onshore and alongshore flows that arrived at different times and from different directions. The most likely explanation for the diverse directions and timing of coastal inundation combines (1) variable fault rupture and asymmetrical slip displacement of the seafloor away from the epicenter with (2) resonant amplification of coastal edge waves. Other possible contributing factors include local interaction of incoming flow and return flow and delayed wave reflection by the southern coast of Peru. Coastal embayments amplified the maximum inundation distances at two sites (2.4 and 2.6 km, respectively). Tsunami vertical erosion included scour and planation of the land surface, inundation scour around the bases of trees, and channel incision from return flow. Sheets and wedges of sand and gravel were deposited at all of the sites. Locally derived boulders up to 1 m in diameter were transported as much as 400 m inland and deposited as fields of dispersed clasts. The presence of lobate bedforms at one site indicates that at least some of the late-stage sediment transport was as bed load and not as suspended load. Most of the tsunami deposits were less than 25 cm thick. Exceptions were thick deposits near open-ocean river mouths where sediment supply was abundant. Human alterations of the land surface at most of the sites provided opportunities to examine some tsunami effects that otherwise would not have been possible, including flow histories, boulder dispersion, and vegetation controls on deposit thickness.

Central Coast↗
USGS1997

Use of ungulates by Yellowstone grizzly bears Ursus arctos

Previous results of fecal analysis from the Yellowstone area and the known abilities of grizzly bears Ursus arctos to acquire and digest tissue from vertebrates suggested that grizzlies in this ecosystem obtained substantial energy from ungulates. This issue was addressed using observations from radio-marked grizzly bears, 1977–1992. Ungulates potentially contributed the majority of energy required for activity during the non-denning season for both adult female and male grizzlies. Most of this energy (95%) was estimated to come from the largest-bodied ungulate species (elk Cervus elaphus , bison Bison bison , and moose Alces alces ), with greatest proportional contributions by scavenged adult male bison (16%), scavenged calf and yearling elk (10%) and adult female elk that were killed (8%) or scavenged (8%). Grizzlies acquired 30% of total edibles from ungulates by predation, of which 13% (or 4% of the total) came from predation on elk calves. Most scavenging occurred during the spring and was associated with the abundance and relative availability of different types of carrion. Predation and scavenging did not appear to be compensatory. Rather, total consumption of ungulates varied inversely with consumption of whitebark pine Pinus albicaulis seeds. The relative frequency of predation to scavenging increased with ungulate density. Contrary to previous suppositions, neither total ungulate use nor frequency of predation increased during the study, despite large increases in some ungulate populations. As expected by the identified trade-offs, Yellowstone grizzlies seemed to prey selectively upon moose, probably because of their solitary habits and forested surroundings, but otherwise favored vulnerable smaller-bodied ungulates such as elk calves. No predation on adult bison was observed.

Idaho, Montana, Wyoming↗
USGS2001

Determination of the sources of nitrate contamination in karst springs using isotopic and chemical indicators

The sources of nitrate (NO-3) in groundwater of the shallow karst aquifer in southwestern Illinois' sinkhole plain were investigated using chemical and isotopic techniques. The groundwater in this aquifer is an important source of potable water for about half of the residents of the sinkhole plain area. Previous work has shown that groundwater from approximately 18% of the wells in the sinkhole plain has NO-3 concentrations in excess of the USEPA's drinking water standard of 10 mg N/1. Relative to background levels, the NO-3 concentrations in water from 52% of the wells, and probably all of the springs in the study area, are anomalously high, suggesting that sources other than naturally occurring soil organic matter have contributed additional NO-3 to groundwater in the shallow karst aquifer. This information, and the dominance of agriculture in the study area, suggest that agrichemical contributions may be significant. To test this hypothesis, water samples from 10 relatively large karst springs were collected during four different seasons and analyzed for inorganic constituents, dissolved organic carbon, atrazine, and ??15N and ??18O of the NO-3 ions. The isotopic data were most definitive and suggested that the sources of NO-3 in spring water are dominated by N-fertilizer with some possible influence of atmospheric NO-3 and, to a much lesser extent, human and/or animal waste. Differences in the isotopic composition of NO-3 and some of the chemical characteristics were observed during the four consecutive seasons in which spring water samples were collected. Isotopic values for ??15N and ??18O of the NO-3 ranged from 3.2??? to 19.1??? and from 7.2??? to 18.7???, respectively. The trend of ??15N and ??18O data for NO-3 also indicated that a significant degree of denitrification is occurring in the shallow karst hydrologic system (within the soil zone, the epikarst and the shallow karst aquifer) prior to discharging to springs. ?? 2001 Elsevier Science B.V. All rights reserved.

Chemical Geology↗
USGS2003

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153]

In a recent contribution [1] , Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ; [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH) x(aq) and Fe(II) (aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4] , but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Earth and Planetary Science Letters↗
USGS2002

Hydrogeologic processes in saline systems: Playas, sabkhas, and saline lakes

Pans, playas, sabkhas, salinas, saline lakes, and salt flats are hydrologically similar, varying only in their boundary conditions. Thus, in evaluating geochemical processes in these systems, a generic water and solute mass-balance approach can be utilized. A conceptual model of a coastal sabkha near the Arabian Gulf is used as an example to illustrate the various water and solute fluxes. Analysis of this model suggests that upward flux of ground water from underlying formations could be a major source of solutes in the sabkha, but contribute only a small volume of the water. Local rainfall is the main source of water in the modeled sabkha system with a surprisingly large recharge-to-rainfall ratio of more than 50%. The contribution of seawater to the solute budget depends on the ratio of the width of the supratidal zone to the total width and is generally confined to a narrow zone near the shoreline of a typical coastal sabkha. Because of a short residence time of water, steady-state flow is expected within a short time (<100 years), while steady state for solutes may take much longer (>50,000 years). The solute composition of the brine in a closed saline system depends largely on the original composition of the input water. The high total ion content in the brine limits the efficiency of water-rock interaction and absorption. Because most natural systems are hydrologically open, the chemistry of the brines and the associated evaporite deposits may be significantly different than that predicted for hydrologically closed systems. Seasonal changes in temperature of the unsaturated zone cause precipitation of minerals in saline systems undergoing evaporation. Thus, during the hot dry season months, minerals exhibit retrograde solubility so that gypsum, anhydrite and calcite precipitate. Evaporation near the surface is also a major process that causes mineral precipitation in the upper portion of the unsaturated zone (e.g. halite and carnallite), provided that the relative humidity of the atmosphere is less than the activity of water. The slope of the fresh/brine-water interface in saline lake systems is shallower than in fresh/seawater interface because of the greater density difference between the fresh/brine-water bodies. The interface between sabkha brines and seawater slopes seaward, unlike normal marine-fresh water systems that slope landward. Moreover, the brine/seawater interface does not achieve steady state because it is pushed toward the sea by the sabkha's brine. ?? 2002 Elsevier Science B.V. All rights reserved.

Earth-Science Reviews↗
USGS1999

Chemical weathering in a tropical watershed, Luquillo Mountains, Puerto Rico III: Quartz dissolution rates

The paucity of weathering rates for quartz in the natural environment stems both from the slow rate at which quartz dissolves and the difficulty in differentiating solute Si contributed by quartz from that derived from other silicate minerals. This study, a first effort in quantifying natural rates of quartz dissolution, takes advantage of extremely rapid tropical weathering, simple regolith mineralogy, and detailed information on hydrologic and chemical transport. Quartz abundances and grain sizes are relatively constant with depth in a thick saprolite. Limited quartz dissolution is indicated by solution rounding of primary angularity and by the formation of etch pits. A low correlation of surface area (0.14 and 0.42 m2 g-1) with grain size indicates that internal microfractures and pitting are the principal contributors to total surface area. Pore water silica concentration increases linearly with depth. On a molar basis, between one and three quarters of pore water silica is derived from quartz with the remainder contributed from biotite weathering. Average solute Si remains thermodynamically undersaturated with respect to recently revised estimates of quartz solubility (<180 ??M) but exceeds estimated critical saturation concentrations controlling the initiation of etch pit formation (>17-81 ??M). Etch pitting is more abundant on grains in the upper saprolite and is associated with pore waters lower in dissolved silica. Rate constants describing quartz dissolution increase with decreasing depth (from 10-14.5-10-15.1 mol m-2 s-1), which correlate with both greater thermodynamic undersaturation and increasing etch pit densities. Unlike for many aluminosilicates, the calculated natural weathering rates of quartz fall slightly below the rate constants previously reported for experimental studies (10-12.4-10-14.2 mol m-2 s-1). This agreement reflects the structural simplicity of quartz, dilute solutes, and near-hydrologic saturation.

Geochimica et Cosmochimica Acta↗