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At least 811 records · Page 45Linked to original sources

USGS1991

Vanadium accumulation in carbonaceous rocks: A review of geochemical controls during deposition and diagenesis

Published data relevant to the geochemistry of vanadium were used to evaluate processes and conditions that control vanadium accumulation in carbonaceous rocks. Reduction, adsorption, and complexation of dissolved vanadium favor addition of vanadium to sediments rich in organic carbon. Dissolved vanadate (V(V)) species predominate in oxic seawater and are reduced to vanadyl ion (V(IV)) by organic compounds or H2S. Vanadyl ion readily adsorbs to particle surfaces and is added to the sediment as the particles settle. The large vanadium concentrations of rocks deposited in marine as compared to lacustrine environments are the result of the relatively large amount of vanadium provided by circulating ocean water compared to terrestrial runoff. Vanadium-rich carbonaceous rocks typically have high contents of organically bound sulfur and are stratigraphically associated with phosphate-rich units. A correspondence between vanadium content and organically bound sulfur is consistent with high activities of H2S during sediment deposition. Excess H2S exited the sediment into bottom waters and favored reduction of dissolved V(V) to V(IV) or possibly V(III). The stratigraphic association of vanadiferous and phosphatic rocks reflects temporal and spatial shifts in bottom water chemistry from suboxic (phosphate concentrated) to more reducing (euxinic?) conditions that favor vanadium accumulation. During diagenesis some vanadium-organic complexes migrate with petroleum out of carbonaceous rocks, but significant amounts of vanadium are retained in refractory organic matter or clay minerals. As carbon in the rock evolves toward graphite during metamorphism, vanadium is incorporated into silicate minerals. ?? 1991.

Chemical Geology↗

USGS1983

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO 2 initially, and open to organic carbon at more distant points down gradient.

Geochimica et Cosmochimica Acta↗

USGS1998

Predictive double-layer modeling of metal sorption in mine-drainage systems

Previous comparison of predictive double-layer modeling and empirically derived metal-partitioning data has validated the use of the double-layer model to predict metal sorption reactions in iron-rich mine-drainage systems. The double-layer model subsequently has been used to model data collected from several mine-drainage sites in Colorado with diverse geochemistry and geology. This work demonstrates that metal partitioning between dissolved and sediment phases can be predictively modeled simply by knowing the water chemistry and the amount of suspended iron-rich particulates present in the system. Sorption on such iron-rich suspended sediments appears to control metal and arsenic partitioning between dissolved and sediment phases, with sorption on bed sediment playing a limited role. At pH > 5, Pb and As are largely sorbed by iron-rich suspended sediments and Cu is partially sorbed; Zn, Cd, and Ni usually remain dissolved throughout the pH range of 3 to 8.

Book chapter↗

USGS2023

Rivers of the Lower Mississippi Basin

Discussed in this chapter are seven significant tributaries of the Lower Mississippi River and its major distributary. As a group, these eight rivers and their basins encompass substantial variation in physical form, hydrology, biota, ecology, and human impacts. The Current River, Ouachita River, and Saline River, flow to the Mississippi out of the U.S. Interior Highlands. The Cache River basin, centered in Arkansas, contains a vast expanse of bottomland hardwood forest and is famous for wintering waterfowl. The Hatchie River, flowing west out of Tennessee, is the longest free-flowing tributary of the Lower Mississippi River and famous for its rich diversity of mussels and fishes. The Wolf River of Tennessee supports a magnificent bald cypress-tupelo swamp and is notable as a protected urban river that flows through Memphis. The Big Sunflower River begins and ends in the alluvial floodplain of the Mississippi River and flows through a basin of intense agriculture and historical human conflict. The Atchafalaya River, the primary distributary of the Mississippi River, supports the nation's largest expanse of bottomland hardwood forest and swamp wetlands. In this chapter, we review the physiography, geomorphology, hydrology, water chemistry, land use, biological diversity, ecological processes, human impacts, and areas of need for research and management of each of these eight rivers and their basins.

Lower Mississippi River basin↗

USGS2014

Mobilization of selenium from the Mancos Shale and associated soils in the lower Uncompahgre River Basin, Colorado

This study investigates processes controlling mobilization of selenium in the lower part of the Uncompahgre River Basin in western Colorado. Selenium occurs naturally in the underlying Mancos Shale and is leached to groundwater and surface water by limited natural runoff, agricultural and domestic irrigation, and leakage from irrigation canals. Soil and sediment samples from the study area were tested using sequential extractions to identify the forms of selenium present in solid phases. Selenium speciation was characterized for nonirrigated and irrigated soils from an agricultural site and sediments from a wetland formed by a leaking canal. In nonirrigated areas, selenium was present in highly soluble sodium salts and gypsum. In irrigated soils, soluble forms of selenium were depleted and most selenium was associated with organic matter that was stable under near-surface weathering conditions. Laboratory leaching experiments and geochemical modeling confirm that selenium primarily is released to groundwater and surface water by dissolution of highly soluble selenium-bearing salts and gypsum present in soils and bedrock. Rates of selenium dissolution determined from column leachate experiments indicate that selenium is released most rapidly when water is applied to previously nonirrigated soils and sediment. High concentrations of extractable nitrate also were found in nonirrigated soils and bedrock that appear to be partially derived from weathered organic matter from the shale rather than from agricultural sources. Once selenium is mobilized, dissolved nitrate derived from natural sources appears to inhibit the reduction of dissolved selenium leading to elevated concentrations of selenium in groundwater. A conceptual model of selenium weathering is presented and used to explain seasonal variations in the surface-water chemistry of Loutzenhizer Arroyo, a major tributary contributor of selenium to the lower Uncompahgre River.

Colorado↗

USGS2015

Baseline and premining geochemical characterization of mined sites

A rational goal for environmental restoration of new, active, or inactive mine sites would be ‘natural background’ or the environmental conditions that existed before any mining activities or other related anthropogenic activities. In a strictly technical sense, there is no such thing as natural background (or entirely non-anthropogenic) existing today because there is no part of the planet earth that has not had at least some chemical disturbance from anthropogenic activities. Hence, the terms ‘baseline’ and ‘pre-mining’ are preferred to describe these conditions. Baseline conditions are those that existed at the time of the characterization which could be pre-mining, during mining, or post-mining. Protocols for geochemically characterizing pre-mining conditions are not well-documented for sites already mined but there are two approaches that seem most direct and least ambiguous. One is characterization of analog sites along with judicious application of geochemical modeling. The other is reactive-transport modeling (based on careful synoptic sampling with tracer-injection) and subtracting inputs from known mining and mineral processing. Several examples of acidic drainage are described from around the world documenting the range of water compositions produced from pyrite oxidation in the absence of mining. These analog sites provide insight to the processes forming mineralized waters in areas untouched by mining. Natural analog water-chemistry data is compared with the higher metal concentrations, metal fluxes, and weathering rates found in mined areas in the few places where comparisons are possible. The differences are generally 1–3 orders of magnitude higher for acid mine drainage.

Applied Geochemistry↗

USGS2021

Interactive PHREEQ-N-AMDTreat water-quality modeling tools to evaluate performance and design of treatment systems for acid mine drainage

The PHREEQ-N-AMDTreat aqueous geochemical modeling tools described herein simulate changes in pH and solute concentrations resulting from passive and active treatment of acidic or alkaline mine drainage (AMD). The “user-friendly” interactive tools, which are publicly available software, utilize PHREEQC equilibrium aqueous and surface speciation models and kinetics models for O 2 ingassing and CO 2 outgassing, iron and manganese oxidation and precipitation, limestone dissolution, and organic carbon oxidation combined with reduction of nitrate, sulfate, and ferric iron. Reactions with synthetic caustic chemicals (CaO, Ca(OH) 2 , NaOH, Na 2 CO 3 ) or oxidizing agents (H 2 O 2 ) also may be simulated separately or combined with sequential kinetic steps. A user interface facilitates input of water chemistry data for one or two (mixed) influent AMD solutions and adjustment of kinetic variables. Graphical and tabular output indicates the changes in pH, metals and other solute concentrations, total dissolved solids, and specific conductance of treated effluent plus the cumulative quantity of precipitated solids as a function of retention time or the amount of caustic agent added. By adjusting kinetic variables or chemical dosing, the effects of independent or sequential treatment steps that have different retention time (volume/flow rate), aeration rate, quantities of reactive solids, and temperature can be simulated for the specified influent quality. The size (land area) of a treatment system can then be estimated using reaction time estimates (volume for a corresponding treatment step is the product of reaction time and flow rate; area is volume divided by depth). Given the estimated system size, the AMDTreat cost-analysis model may be used to compute approximate costs for installation (capital) and annual operations and maintenance. Thus, various passive and/or active treatment strategies can be identified that could potentially achieve the desired effluent quality, but require different land area, equipment, and costs for construction and operation.

Applied Geochemistry↗

USGS2017

Ecology of the macrophyte Podostemum ceratophyllum Michx. (Hornleaf riverweed), a widespread foundation species of eastern North American rivers

Podostemum ceratophyllum , commonly called Hornleaf Riverweed, occurs in mid-order montane and piedmont rivers of eastern North America, where the plant grows submerged and attached to rocks and stable substrates in swift, aerated water. Multiple studies, mostly conducted in the southern portions of the plant’s range, have shown that Podostemum can variously influence benthic communities in flowing waters. However, a synthetic review of the biology and ecology of the plant is needed to inform conservation, particularly because P. ceratophyllum is reported to be in decline in much of its range, for mostly unknown reasons. We have thus summarized the literature showing that Podostemum provides substantial habitat for invertebrates and fish, may be consumed by invertebrates, turtles, and other vertebrates, removes and sequesters dissolved elements (i.e., nitrogen, phosphorus, calcium, zinc, etc.) from the water column, and contributes organic matter to the detrital pool. Podostemum may be tolerant to some forms of pollution but appears vulnerable to sedimentation, epiphytic over-growth, and hydrologic changes that result in desiccation, and possibly increased herbivory pressure. Much remains unknown about Podostemum , including aspects of morphological variation, seed dispersal, and tolerance to changes in temperature and water chemistry. Nonetheless, Podostemum may be considered a foundation species, whose loss from eastern North American rivers is likely to affect higher trophic levels and ecosystem processes.

Aquatic Botany↗

USGS2009

In situ measurements of microbially-catalyzed nitrification and nitrate reduction rates in an ephemeral drainage channel receiving water from coalbed natural gas discharge, Powder River Basin, Wyoming, USA

Nitrification and nitrate reduction were examined in an ephemeral drainage channel receiving discharge from coalbed natural gas (CBNG) production wells in the Powder River Basin, Wyoming. CBNG co-produced water typically contains dissolved inorganic nitrogen (DIN), primarily as ammonium. In this study, a substantial portion of discharged ammonium was oxidized within 50 m of downstream transport, but speciation was markedly influenced by diel fluctuations in dissolved oxygen (> 300 µM). After 300 m of transport, 60% of the initial DIN load had been removed. The effect of benthic nitrogen-cycling processes on stream water chemistry was assessed at 2 locations within the stream channel using acrylic chambers to conduct short-term (2–6 h), in-stream incubations. The highest ambient DIN removal rates (2103 µmol N m − 2 h − 1 ) were found at a location where ammonium concentrations > 350 µM. This occurred during light incubations when oxygen concentrations were highest. Nitrification was occurring at the site, however, net accumulation of nitrate and nitrite accounted for < 12% of the ammonium consumed, indicating that other ammonium-consuming processes were also occurring. In dark incubations, nitrite and nitrate consumption were dominant processes, while ammonium was produced rather than consumed. At a downstream location nitrification was not a factor and changes in DIN removal rates were controlled by nitrate reduction, diel fluctuations in oxygen concentration, and availability of electron donor. This study indicates that short-term adaptation of stream channel processes can be effective for removing CBNG DIN loads given sufficient travel distances, but the long-term potential for nitrogen remobilization and nitrogen saturation remain to be determined.

Chemical Geology↗

USGS2022

Evaluating acid-aluminum stress in streams of the Northeastern U.S. at watershed, fish community and physiological scales

In spite of overall improvements in air and water quality, biological stress from low pH and high concentrations of inorganic aluminum continue to impact fish and fish habitat in northeastern North America, with independent and interactive effects on individuals, populations and communities. Integrative indicators can therefore be useful in monitoring both impact and recovery across multiple scales. Using coupled water chemistry (pH, conductivity, and base cation and inorganic aluminum concentration), geographic (site elevation and watershed area) and biological (fish diversity, fish abundance, gill aluminum concentration and gill physiology) data, we developed an integrated indicator of acid aluminum stress across the White and Green mountains in central New England, USA. As has been established in a number of previous studies, preliminary analysis clearly indicated that across all sites, inorganic aluminum concentration was consistently greatest during the spring season. Structural Equation modelling (SEM) revealed that toxic conditions (concurrent low pH and high concentrations of inorganic aluminum) were well summarized with an integrated toxicity score, related to both base cation concentrations and elevation, with sites at higher elevations more likely to experience toxic conditions as well as low base cation concentrations. As hypothesized, fish diversity and abundance were negatively related to toxicity score. In spite of considerable variation among individuals, gill aluminum was positively related to toxicity score for both Atlantic salmon and brook trout. Observed elevated gill aluminum levels associated with reduced gill metabolic activity in Atlantic salmon smolts from impacted systems likely result in impaired osmoregulatory function and seawater tolerance. Overall, our results suggest that the integrated toxicity score metric is strongly associated with a syndrome of physiological stress, reduced abundance, and low species diversity for stream fishes in New England and can likely serve as a reliable indicator of continued impairment or recovery of acid-aluminum vulnerable systems in this ecoregion.

New Hampshire, Vermont↗

USGS2024

Temporal variability and sources of PFAS in the Rio Grande, New Mexico through an arid urban area using multiple tracers and high-frequency sampling

Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in the environment but sources are not well defined for temporal and spatial aspects within an urban environment, and especially for an arid urban environment subject to seasonal short term high-intensity precipitation events. A focused diel sampling was conducted in the summer of 2021 to assess the temporal and spatial variability of PFAS in the Rio Grande near Albuquerque, New Mexico and showed an order of magnitude increase of PFAS as it flows through the Albuquerque urban area. Discrete samples were collected at two different locations on the Rio Grande in addition to wastewater treatment plant (WWTP) effluent that discharges directly to the Rio Grande between the sampling locations. Short-term high-intensity precipitation events occurred during the study period and mobilized PFAS from urban runoff. Dissolved organic matter composed of tryptophan-like organic substances and refined fuel and fuel byproducts, characteristic of an urban signature, were also related to the precipitation events. The PFAS in discharge from the WWTP was consistent over a 24-h period with slight differences in some compounds. Wastewater presence on the Rio Grande downstream of the WWTP was evidenced by a gadolinium anomaly as well as increases in several other trace elements, total dissolved nitrogen, and fluorescence indicators, in addition to PFAS. PFAS varied depending on source contribution, where urban runoff was associated with PFOA, PFOS, and PFBA, whereas PFHxA and PFPeA were associated with wastewater effluent. In addition, passive polar organic chemical integrative samplers (POCIS) using hydrophilic-lipid balance (HLB) sorption media were deployed for a month at two locations on the Rio Grande to assess longer term PFAS concentrations. The POCIS results show some compounds (PFPeA and PFHpA) were greater than the average concentration from discrete samples, whereas other compounds (PFHxA, PFOA, PFDA, and PFNA) were lower in the POCIS, and PFOS was very similar between the two. The POCIS did not detect PFBA, which may be related to the HLB media not performing well for short chain PFAS compounds. The results show promise for integrative samplers utilizing sorbent media. More detailed investigation of the spatial and temporal variability of water chemistry on the Rio Grande as it flows through Albuquerque could provide information applicable to urban areas worldwide.

New Mexico↗

USGS2018

Contaminants of emerging concern presence and adverse effects in fish: A case study in the Laurentian Great Lakes

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

Environmental Pollution↗

USGS2019

Decreased atmospheric nitrogen deposition in eastern North America: Predicted responses of forest ecosystems

Historical increases in emissions and atmospheric deposition of oxidized and reduced nitrogen (N) provided the impetus for extensive, global-scale research investigating the effects of excess N in terrestrial and aquatic ecosystems, with several regions within the Eastern Deciduous Forest of the United States found to be susceptible to negative effects of excess N. The Clean Air Act and associated rules have led to decreases in emissions and deposition of oxidized N, especially in eastern U.S., representing a research challenge and opportunity for ecosystem ecologists and biogeochemists. The purpose of this paper is to predict changes in the structure and function of North American forest ecosystems in a future of decreased N deposition. Hysteresis is a property of a system wherein output is not a strict function of corresponding input, incorporating lag, delay, or history dependence, particularly when the response to decreasing input is different from the response to increasing input. We suggest a conceptual hysteretic model predicting varying lag times in recovery of soil acidification, plant biodiversity, soil microbial communities, forest carbon (C) and N cycling, and surface water chemistry toward pre-N impact conditions. Nearly all of these can potentially respond strongly to reductions in N deposition. Most responses are expected to show some degree of hysteresis, with the greatest delays in response occurring in processes most tightly linked to “slow pools” of N in wood and soil organic matter. Because experimental studies of declines in N loads in forests of North America are lacking and because of the expected hysteresis, it is difficult to generalize from experimental results to patterns expected from declining N deposition. These will likely be long-term phenomena, difficult to distinguish from other, concurrent environmental changes, including elevated atmospheric CO 2 , climate change, reductions in acidity, invasions of new species, and long-term vegetation responses to past disturbance.

Environmental Pollution↗

USGS2008

Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO 4 2- are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO 4 2- is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions ( HSO 4 - ) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of " HSO 4 - relative to SO 4 2- . However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO 4 - is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as SO 4 2- , aqueous calcium sulfate ([CaSO 4 ] (aq) ), and aqueous magnesium sulfate ([MgSO 4 ] (aq) ). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions ( HSO 4 - ) and/or magnesium sulfate contact ion-pairs ([MgSO 4 ] CIP ) rather than ‘free’ sulfate ions ( SO 4 2- ) or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.

Geochimica et Cosmochimica Acta↗

USGS2010

Hydrated mineral stratigraphy of Ius Chasma, Valles Marineris

New high-resolution spectral and morphologic imaging of deposits on walls and floor of Ius Chasma extend previous geomorphic mapping, and permit a new interpretation of aqueous processes that occurred during the development of Valles Marineris. We identify hydrated mineralogy based on visible-near infrared (VNIR) absorptions. We map the extents of these units with CRISM spectral data as well as morphologies in CTX and HiRISE imagery. Three cross-sections across Ius Chasma illustrate the interpreted mineral stratigraphy. Multiple episodes formed and transported hydrated minerals within Ius Chasma. Polyhydrated sulfate and kieserite are found within a closed basin at the lowest elevations in the chasma. They may have been precipitates in a closed basin or diagenetically altered after deposition. Fluvial or aeolian processes then deposited layered Fe/Mg smectite and hydrated silicate on the chasma floor, postdating the sulfates. The smectite apparently was weathered out of Noachian-age wallrock and transported to the depositional sites. The overlying hydrated silicate is interpreted to be an acid-leached phyllosilicate transformed from the underlying smectite unit, or a smectite/jarosite mixture. The finely layered smectite and massive hydrated silicate units have an erosional unconformity between them, that marks a change in surface water chemistry. Landslides transported large blocks of wallrock, some altered to contain Fe/Mg smectite, to the chasma floor. After the last episode of normal faulting and subsequent landslides, opal was transported short distances into the chasma from a few m-thick light-toned layer near the top of the wallrock, by sapping channels in Louros Valles. Alternatively, the material was transported into the chasma and then altered to opal. The superposition of different types of hydrated minerals and the different fluvial morphologies of the units containing them indicate sequential, distinct aqueous environments, characterized by alkaline, then circum-neutral, and finally very acidic surface or groundwater chemistry. ?? 2009 Elsevier Inc. All rights reserved.

Icarus↗

USGS2012

Cyclic biogeochemical processes and nitrogen fate beneath a subtropical stormwater infiltration basin

A stormwater infiltration basin in north–central Florida, USA, was monitored from 2007 through 2008 to identify subsurface biogeochemical processes, with emphasis on N cycling, under the highly variable hydrologic conditions common in humid, subtropical climates. Cyclic variations in biogeochemical processes generally coincided with wet and dry hydrologic conditions. Oxidizing conditions in the subsurface persisted for about one month or less at the beginning of wet periods with dissolved O 2 and NO 3 - showing similar temporal patterns. Reducing conditions in the subsurface evolved during prolonged flooding of the basin. At about the same time O 2 and NO 3 - reduction concluded, Mn, Fe and SO 4 2 - reduction began, with the onset of methanogenesis one month later. Reducing conditions persisted up to six months, continuing into subsequent dry periods until the next major oxidizing infiltration event. Evidence of denitrification in shallow groundwater at the site is supported by median NO 3 -–N less than 0.016 mg L -1 , excess N 2 up to 3 mg L -1 progressively enriched in δ 15 N during prolonged basin flooding, and isotopically heavy δ 15 N and δ 18 O of NO 3 - (up to 25&permil; and 15&permil;, respectively). Isotopic enrichment of newly infiltrated stormwater suggests denitrification was partially completed within two days. Soil and water chemistry data suggest that a biogeochemically active zone exists in the upper 1.4 m of soil, where organic carbon was the likely electron donor supplied by organic matter in soil solids or dissolved in infiltrating stormwater. The cyclic nature of reducing conditions effectively controlled the N cycle, switching N fate beneath the basin from NO 3 - leaching to reduction in the shallow saturated zone. Results can inform design of functionalized soil amendments that could replace the native soil in a stormwater infiltration basin and mitigate potential NO 3 - leaching to groundwater by replicating the biogeochemical conditions under the observed basin.

Florida↗

USGS2018

Geochemical characterization and modeling of regional groundwater contributing to the Verde River, Arizona between Mormon Pocket and the USGS Clarkdale gage

We use synoptic surveys of stream discharge, stable isotopes, and dissolved noble gases to identify the source of groundwater discharge to the Verde River in central Arizona. The Verde River more than doubles in discharge in Mormon Pocket over a 1.4 km distance that includes three discrete locations of visible spring input to the river and other diffuse groundwater inputs. A detailed study of the Verde River between Mormon Pocket and the USGS Clarkdale Gage was conducted to better constrain the location of groundwater inputs, the geochemical signature and constrain the source of groundwater input. Discharge, water quality parameters (temperature, pH, specific conductance, and dissolved oxygen), stable isotopes (δ18O and δ2H), noble gases (He, Ne, Ar, Kr and Xe), and radon (222Rn) from river water were collected. Groundwater samples from springs and wells in the area were collected and analyzed for tracers measured in the stream along with some additional analytes (major ions, strontium isotopes (87Sr/86Sr), carbon-14, δ13C, and tritium). Groundwater isotopic signature is consistent with a regional groundwater source. Groundwater springs discharging to the river have a depleted stable isotopic signature indicating recharge source up to 1000 m higher than the discharge location in the Verde River and are significantly fresher than stream water. Spring water has a radiocarbon age of several thousand years and some areas have tritium less than the laboratory reporting level or low concentrations of tritium (1.5 TU). The strontium isotopes indicate groundwater interaction with tertiary volcanic rock and Paleozoic sedimentary rocks. Along the study reach with distance downstream, Verde stream water chemistry shows increased 222Rn, freshening, increased 4He, and isotopic depletion with distance downstream. We estimated total groundwater discharge by inverting a stream transport model against 222Rn and discharge measured in the stream. The salinity, 4He, and stable isotope composition of discharging groundwater was then estimated by fitting modeled values to observed in-stream values. Estimated groundwater inflow to the stream was well within the ranges observed in springs, indicating that the main source of streamflow is deep, regional groundwater. These results show that synoptic surveys of environmental tracers in streams can be used to estimate the isotopic composition and constrain the source of groundwater discharging to streams. Our data provide direct field evidence that deep, regional groundwater discharge can be a significant source of streamflow generation in arid, topographically complex watersheds.

Arizona↗

USGS2024

A new species of benthic ostracod Tuberoloxoconcha: A proxy for glacioeustatic sea-level changes in the Gulf of Corinth

In 2017, sediment cores were retrieved from sites M0080, M0079, and M0078 in the Corinth basin during IODP Expedition 381. This study focuses on the Holocene and middle Pleistocene ostracod assemblages retrieved from sites M0080, in the Gulf of Alkyonides, and M0078 in the Corinth Gulf. It explores the paleoenvironmental constraints that affected the Tuberoloxoconcha species' distribution in these two sites and investigates the stratigraphic appearance of the new species Tuberoloxoconcha aielloi in the Corinth basin during deglacial and glacial periods over the last 400,000 years. In the Gulf of Corinth, fossil assemblages dominated by T. aielloi n. sp. have identified brackish shallow water environments corresponding to deglacial and glacial phases, when the basin was likely semi-isolated from Mediterranean waters, with high fluvial input lowering the salinity of the waterbody. The study highlights the discontinuous occurrence of T. aielloi and its morphotypes, identifying cold phases during MIS 10 and MIS 7d, and warmer phases during MISs 2–3-4-5a. The variability in ornamentation potentially reflects different water chemistry in the two sites. The post-400 ky appearance of T. aielloi , coinciding with the development of the marine connection through the Rion Strait, implies a Mediterranean/Atlantic origin for the genus. This study provides insights into the environmental conditions and evolutionary history of T. aielloi species in the Corinth basin, contributing to a broader understanding of benthic species' responses to past and future sea level changes.

Gulf of Corinth↗