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At least 1,081 records · Page 60Linked to original sources

Links between N deposition and nitrate export from a high-elevation watershed in the Colorado Front Range

Long-term patterns of stream nitrate export and atmospheric N deposition were evaluated over three decades in Loch Vale, a high-elevation watershed in the Colorado Front Range. Stream nitrate concentrations increased in the early 1990s, peaked in the mid-2000s, and have since declined by over 40%, coincident with trends in nitrogen oxide emissions over the past decade. Similarities in the timing and magnitude of N deposition provide evidence that stream chemistry is responding to changes in atmospheric deposition. The response to deposition was complicated by a drought in the early 2000s that enhanced N export for several years. Other possible explanations, including forest disturbance, snow depth, or permafrost melting, could not explain patterns in N export. Our results show that stream chemistry responds rapidly to changes in N deposition in high-elevation watersheds, similar to the response observed to changes in sulfur deposition.

Colorado↗

Surface complexation of carboxylate adheres Cryptosporidium parvum öocysts to the hematite-water interface

The interaction of viable Cryptosporidium parvum öocysts at the hematite (α-Fe 2 O 3 )−water interface was examined over a wide range in solution chemistry using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Spectra for hematite-sorbed öocysts showed distinct changes in carboxylate group vibrations relative to spectra obtained in the absence of hematite, indicative of direct chemical bonding between carboxylate groups and Fe metal centers of the hematite surface. The data also indicate that complexation modes vary with solution chemistry. In NaCl solution, öocysts are bound to hematite via monodentate and binuclear bidentate complexes. The former predominates at low pH, whereas the latter becomes increasingly prevalent with increasing pH. In a CaCl 2 solution, only binuclear bidentate complexes are observed. When solution pH is above the point of zero net proton charge (PZNPC) of hematite, öocyst surface carboxylate groups are bound to the mineral surface via outer-sphere complexes in both electrolyte solutions.

Environmental Science & Technology↗

Redox transformations and transport of cesium and iodine (-1, 0, +5) in oxidizing and reducing zones of a sand and gravel aquifer

Tracer tests were performed in distinct biogeochemical zones of a sand and gravel aquifer in Cape Cod, MA, to study the redox chemistry (I) and transport (Cs, I) of cesium and iodine in a field setting. Injection of iodide (I - ) into an oxic zone of the aquifer resulted in oxidation of I - to molecular iodine (I 2 ) and iodate (IO 3 - ) over transport distances of several meters. Oxidation is attributed to Mn-oxides present in the sediment. Transport of injected IO 3 - and Cs + was retarded in the mildly acidic oxic zone, with retardation factors of 1.6-1.8 for IO 3 - and 2.3-4.4for Cs. Cs retardation was likely due to cation exchange reactions. Injection of IO 3 - into a Fe-reducing zone of the aquifer resulted in rapid and complete reduction to I - within 3 m of transport. The nonconservative behavior of Cs and I observed during the tracer tests underscores the necessity of taking the redox chemistry of I as well as sorption properties of I species and Cs into account when predicting transport of radionuclides (e.g., 129 I and 137 Cs) in the environment.

Massachusetts↗

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Environmental Science & Technology↗

Identification of linear and threshold responses in streams along a gradient of urbanization in Anchorage, Alaska

We examined biotic and physiochemical responses in urbanized Anchorage, Alaska, to the percent of impervious area within stream basins, as determined by high-resolution IKONOS satellite imagery and aerial photography. Eighteen of the 86 variables examined, including riparian and instream habitat, macroinvertebrate communities, and water/sediment chemistry, were significantly correlated with percent impervious area. Variables related to channel condition, instream substrate, water chemistry, and residential and transportation right-of-way land uses were identified by principal components analysis as significant factors separating site groups. Detrended canonical correspondence analysis indicated that the macroinvertebrate communities responded to an urbanization gradient closely paralleling the percent of impervious area within the subbasin. A sliding regression analysis of variables significantly correlated with percent impervious area revealed 8 variables exhibiting threshold responses that correspond to a mean of 4.4-5.8% impervious area, much lower than mean values reported in other, similar investigations. As contributing factors to a subbasin's impervious area, storm drains and roads appeared to be important elements influencing the degradation of water quality with respect to the biota.

Alaska↗

Using fish communities to assess streams in Romania: Initial development of an index of biotic integrity

Multimetric biotic indices increasingly are used to complement physicochemical data in assessments of stream quality. We initiated development of multimetric indices, based on fish communities, to assess biotic integrity of streams in two physiographic regions of central Romania. Unlike previous efforts to develop such indices for European streams, our metrics and scoring criteria were selected largely on the basis of empirical relations in the regions of interest. We categorised 54 fish species with respect to ten natural-history attributes, then used this information to compute 32 candidate metrics of five types (taxonomic, tolerance, abundance, reproductive, and feeding) for each of 35 sites. We assessed the utility of candidate metrics for detecting anthropogenic impact based on three criteria: (a) range of values taken, (b) relation to a site-quality index (SQI), which incorporated information on hydrologic alteration, channel alteration, land-use intensity, and water chemistry, and (c) metric redundancy. We chose seven metrics from each region to include in preliminary multimetric indices (PMIs). Both PMIs included taxonomic, tolerance, and feeding metrics, but only two metrics were common to both PMIs. Although we could not validate our PMIs, their strong association with the SQI in each region suggests that such indices would be valuable tools for assessing stream quality and could provide more comprehensive assessments than the traditional approaches based solely on water chemistry.

Hydrobiologia↗

Using chemical, hydrologic, and age dating analysis to delineate redox processes and flow paths in the riparian zone of a glacial outwash aquifer‐stream system

A combination of chemical and dissolved gas analyses, chlorofluorocarbon age dating, and hydrologic measurements were used to determine the degree to which biogeochemical processes in a riparian wetland were responsible for removing NO 3 − from groundwaters discharging to the Otter Tail River in west central Minnesota. An analysis of river chemistry and flow data revealed that NO 3 − concentrations in the river increased in the lower half of the 8.3 km study reach as the result of groundwater discharge to the river. Groundwater head measurements along a study transect through the riparian wetland revealed a zone of groundwater discharge extending out under the river. On the basis of combined chemical, dissolved gas, age date, and hydrologic results, it was determined that water chemistry under the riparian wetland was controlled largely by upgradient groundwaters that followed flow paths up to 16 m deep and discharged under the wetland, creating a pattern of progressively older, more chemically reduced, low NO 3 − water the farther one progressed from the edge of the wetland toward the river. These findings pose challenges for researchers investigating biogeochemical processes in riparian buffer zones because the progressively older groundwaters entered the aquifer in earlier years when less NO 3 − fertilizer was being used. NO 3 − concentrations originally present in the groundwater had also decreased in the upgradient aquifer as a result of denitrification and progressively stronger reducing conditions there. The resulting pattern of decreasing NO 3 − concentrations across the riparian zone may be incorrectly interpreted as evidence of denitrification losses there instead of in the upgradient aquifer. Consequently, it is important to understand the hydrogeologic setting and age structure of the groundwaters being sampled in order to avoid misinterpreting biogeochemical processes in riparian zones.

Water Resources Research↗

Comment on "Coral reef calcification and climate change: The effect of ocean warming"

McNeil et al. [2004] attempt to address an important question about the interactions of temperature and carbonate chemistry on calcification, but their projected values of reef calcification are based on assumptions that ignore critical observational and experimental literature. Certainly, more research is needed to better understand how changing temperatures and carbonate chemistry will affect not only coral reef calcification, but coral survival. As discussed above, the McNeil et al. [2004] analysis is based on assumptions that exclude potentially important factors and therefore needs to be viewed with caution. Copyright 2005 by the American Geophysical Union.

Geophysical Research Letters↗

Surface water acidification responses and critical loads of sulfur and nitrogen deposition in Loch Vale watershed, Colorado

We evaluated the sensitivity of The Loch, a subalpine lake in Rocky Mountain National Park in Colorado, to acidification in response to increased atmospheric loading of sulfur (S) and nitrogen (N) using the Model of Acidification of Groundwater in Catchments (MAGIC). Lake water acid‐base chemistry was moderately sensitive to changes in both S and N deposition. However, the loads of S deposition that would drive chronic lake water acid neutralizing capacity (ANC) to below 0 or 20 μeq L −1 were estimated to be 11 and 8 kg S ha −1 yr −1 , respectively, assuming constant future N deposition at current levels. Comparable loads for N deposition, assuming constant future S deposition, were estimated to be 21 and 12 kg N ha −1 yr −1 , respectively. Modeling results for Andrews Creek, an alpine tributary to The Loch, suggested critical loads for surface water acidification that averaged about one third lower. Surface water ANC = 50 μeq L −1 was projected to occur in 50 years in The Loch if S or N deposition increased by a moderate amount (<40%) but could not be achieved in Andrews Creek by reducing either S or N deposition to zero. On the basis of the results of synoptic surveys of lake water chemistry, about one fifth of the wilderness lakes in the Colorado Front Range are more acid‐sensitive than The Loch. This modeling exercise suggests the need for a regional analysis of critical loads for the larger population of acid‐sensitive aquatic resources in order to provide part of the scientific foundation for federally mandated land management decisions.

Water Resources Research↗

Reproducibility of geochemical and climatic signals in the Atlantic coral Montastraea faveolata

Monthly resolved, 41-year-long stable isotopic and elemental ratio time series were generated from two separate heads of Montastraea faveolata from Looe Key, Florida, to assess the fidelity of using geochemical variations in Montastraea, the dominant reef-building coral of the Atlantic, to reconstruct sea surface environmental conditions at this site. The stable isotope time series of the two corals replicate well; mean values of ??18O and ??13C are indistinguishable between cores (compare 0.70??? versus 0.68??? for ??13C and -3.90??? versus - 3.94??? for ??18O). Mean values from the Sr/Ca time series differ by 0.037 mmol/mol, which is outside of analytical error and indicates that nonenvironmental factors are influencing the coral Sr/ Ca records at Looe Key. We have generated significant ?? 18O-sea surface temperature (SST) (R = -0.84) and Sr/ Ca-SST (R = -0.86) calibration equations at Looe Key; however, these equations are different from previously published equations for Montastraea. Variations in growth parameters or kinetic effects are not sufficient to explain either the observed differences in the mean offset between Sr/Ca time series or the disagreement between previous calibrations and our calculated ??18O-SST and Sr/Ca-SST relationships. Calibration differences are most likely due to variations in seawater chemistry in the continentally influenced waters at Looe Key. Additional geochemical replication studies of Montastraea are needed and should include multiple coral heads from open ocean localities complemented whenever possible by seawater chemistry determinations. Copyright 2006 by the American Geophysical Union.

Paleoceanography↗

Source water controls on the character and origin of dissolved organic matter in streams of the Yukon River basin, Alaska

Climate warming and permafrost degradation at high latitudes will likely impact watershed hydrology, and consequently, alter the concentration and character of dissolved organic carbon (DOC) in northern rivers. We examined seasonal variation of DOC chemistry in 16 streams of the Yukon River basin, Alaska. Our primary objective was to evaluate the relationship between source water (shallow versus deep groundwater flow paths) and DOC chemical composition. Using base cation chemistry and principal component analysis, we observed high contributions of deep groundwater to glacial and clearwater streams, whereas blackwater streams received larger contributions from shallow groundwater sources. DOC concentration and specific ultraviolet absorbance peaked during spring snowmelt in all streams, and were consistently higher in blackwater streams than in glacial and clearwater streams. The hydrophobic acid fraction of DOC dominated across all streams and seasons, comprising between 35% and 56% of total DOC. The hydrophilic acid fraction of DOC was more prominent in glacial (23% ± 3%) and clearwater streams (19% ± 1%) than in blackwater streams (16% ± 1%), and was enriched during winter base flow (29% ± 1%) relative to snowmelt and summer base flow. We observed that an increase in the contribution of deep groundwater to streamflow resulted in decreased DOC concentration, aromaticity, and DOC-to-dissolved organic nitrogen ratio, and an increase in the proportion of hydrophilic acids relative to hydrophobic acids. Our findings suggest that future permafrost degradation and higher contributions of groundwater to streamflow may result in a higher fraction of labile DOM in streams of the Yukon basin.

Journal of Geophysical Research G: Biogeosciences↗

Predicting geogenic arsenic in drinking water wells in glacial aquifers, north-central USA: Accounting for depth-dependent features

Chronic exposure to arsenic (As) via drinking groundwater is a human health concern worldwide. Probabilities of elevated geogenic As concentrations in groundwater were predicted in complex, glacial aquifers in Minnesota, north‐central USA, a region that commonly has elevated As concentrations in well water. Maps of elevated As hazard were created for depths typical of drinking water supply and with well construction attributes common for domestic wells. Conventional variables describing aquifer properties and materials, position on the hydrologic landscape, and soil geochemistry were among the most influential for predicting the probability of elevated As. We also found that certain well construction attributes were influential in predicting As hazard. Smaller distances between the top of the well screen and overlying aquitard (proximity) and shorter well screen lengths were each associated with higher probabilities of elevated As. Influential predictor variables, which are either mapped across the region or are well construction attributes, are proxies in the model for measurable physical or geochemical causes of elevated As (e.g., redox condition, till or aquifer sediment chemistry, and water chemistry), which are not mapped across the region. Our setting shares some important characteristics with deltaic and other high‐As aquifers in Southeast Asia: late Quaternary age, complex layering of coarse‐ and fine‐grained materials, low‐As sediment concentrations, and geochemical controls on As mobilization. Translating three‐dimensional geologic and geochemical understanding of As mobility to quantifiable variables for modeling with powerful, flexible statistical tools could improve predictions and help identify safer groundwater supply options in the USA, Southeast Asia, and elsewhere.

Minnesota↗

Planktic foraminiferal test size and weight response to the late Pliocene environment

Atmospheric carbon dioxide ( p CO 2 atm ) is impacting the ocean and marine organisms directly via changes in carbonate chemistry and indirectly via a range of changes in physical parameters most dominantly temperature. To assess potential impacts of climate change on carbonate production in the open ocean, we measured size and weight of planktic foraminifers during the late Pliocene at p CO 2 atm concentrations comparable to today and global temperatures 2 to 3 °C warmer. Size of all foraminifers was measured at Atlantic Ocean Deep Sea Drilling Project (DSDP) Site 610, Ocean Drilling Program (ODP) Site 999, and Integrated Ocean Drilling Program (IODP) Site U1313. Test size was smaller during the Pliocene than in modern assemblages under the same environmental conditions. During the cold marine isotope stage (MIS) M2, size increased at Site 999, potentially linked to intensified stratification of the surface ocean in response to the closure of the Central American Seaway. At Site U1313, test size tracks the warming throughout the late Pliocene. Size-normalized weight (SNW) of Globigerina bulloides at Site U1313 decreased during warmer temperature intervals. SNW of Globigerinoides ruber (white) at Site 999 displays high-frequency variability not correlated to temperature. Yet during the glacial period within MIS M2, test weight was higher during higher temperatures. Our results support studies in the modern ocean, which challenge the view that carbonate chemistry is the primary driver for calcification. To better understand processes driving changes in SNW, computer tomography was used to quantify calcite to volume ratios. During interglacial periods, lower calcite volume but higher test volume suggests less suitable conditions for calcification. As this signal is not evident in SNW, subtle changes in calcification might not be observed by the weight-based method.

Paleoceanography and Paleoclimatology↗

Direct observation of the depth of active groundwater circulation in an alpine watershed

The depth of active groundwater circulation is a fundamental control on stream flows and chemistry in mountain watersheds, yet it remains challenging to characterize and is rarely well constrained. We collected hydraulic conductivity, hydraulic head, temperature, chemical, noble gas, and 3 H/ 3 He groundwater age data from discrete levels in two boreholes 46 and 81 m deep in an alpine watershed, in combination with chemical and age data from shallow groundwater discharge, to discern groundwater flow rates at different depths and directly observe active and inactive groundwater. Vertical head gradients are steep (average of 0.4) and thermal profiles are consistent with typical linear conductive continental geotherms. Groundwater deeper than ∼20 m is distinct from shallow groundwater and creek water in its chemistry, noble gas signature, and age (dominantly >65 years compared to <9 years). Together these results suggest low vertical groundwater flow velocities and a relatively shallow active circulation depth of ∼20 m. This hypothesis is tested with a simple 2‐D numerical fluid flow and heat transport model representing a hillslope transect through the two boreholes. The modeling indicates that the subhorizontally bedded sedimentary rocks underlying the basin are highly anisotropic with low vertical hydraulic conductivity, and at most ∼10% of bedrock recharge (equivalent to <2% of stream baseflow) flows below a depth of 20 m. The study demonstrates the considerable value of discrete‐depth hydrogeologic, chemical, and age data for determining active circulation depth, and illustrates an approach for maximizing the utility of individual boreholes drilled for mountain bedrock aquifer characterization.

Colorado↗

Local topography and streambed hydraulic conductivity influence riparian groundwater age and groundwater-surface water connection

The western U.S. is experiencing increasing rain to snow ratios due to climate change, and scientists are uncertain how changing recharge patterns will affect future groundwater-surface water connection. We examined how watershed topography and streambed hydraulic conductivity impact groundwater age and stream discharge at eight sites along a headwater stream within the Manitou Experimental Forest, CO USA. To do so, we measured: (a) continuous stream and groundwater discharge/level and specific conductivity from April to November 2021; (b) biweekly stream and groundwater chemistry; (c) groundwater chlorofluorocarbons and tritium in spring and fall; (d) streambed hydraulic conductivity; and (e) local slope. We used the chemistry data to calculate fluorite saturation states that were used to inform end-member mixing analysis of streamflow source. We then combined chlorofluorocarbon and tritium data to estimate the age composition of riparian groundwater. Our data suggest that future stream drying is more probable where local slope is steep and streambed hydraulic conductivity is high. In these areas, groundwater source shifted seasonally, as indicated by age increases, and we observed a high fraction of groundwater in streamflow, primarily interflow from adjacent hillslopes. In contrast, where local slope is flat and streambed hydraulic conductivity is low, streamflow is more likely to persist as groundwater age was seasonally constant and buffered by storage in alluvial sediments. Groundwater age and streamflow paired with characterization of watershed topography and subsurface characteristics enabled identification of likely controls on future stream drying patterns.

Colorado↗

Sulfur-to-iron ratio as a proxy for degree of organic sulfurization

The degree of organic sulfurization is broadly relevant yet underreported. We present a statistically significant correlation between whole rock S/Fe and the measured degree of organic sulfurization in the thermally immature Cenomanian–Turonian Eagle Ford Group. This relationship shows a sink switch for sulfur from pyrite to organic matter. Excess iron and excess sulfur relative to pyrite, which are mathematically related to S/Fe, provide better insights into organic sulfurization than previous approaches that calculate excess iron relative to detrital iron based on aluminum concentrations. Organic sulfurization and S/Fe are tightly coupled in the Eagle Ford partially due to limited sulfur- and iron-bearing components. Similar relationships could exist in other thermally immature, organic-rich, anoxia-prone, calcareous mudstones. The degree of organic sulfurization was estimated from S/Fe, which was used to map stratigraphic and regional variations of organic sulfurization across the Eagle Ford and to investigate how organic sulfurization relates to organic enrichment, organic preservation, and depositional redox chemistry. The extent of organic sulfurization is more tightly linked to organic preservation than enrichment. Together, organic sulfurization and Mo provide concordant evidence for depositional euxinia. The relationship between Mo and degree of organic sulfurization could indicate that sulfurized organic matter provides a pathway for Mo enrichment, but future work needs to disentangle direct mechanisms from indirect covariations between Mo, organic content, and degree of organic sulfurization. Whole rock elemental chemistry and programmed pyrolysis provide insights into organic sulfurization variations that can be upscaled and can guide subsequent detailed organic sulfur analyses.

Arkansas, Louisiana, Oklahoma, Texas↗

Physicochemical properties and bioreactivity of sub-10 µm geogenic particles: Comparison of volcanic ash and desert dust

Exposure to ambient particulate matter (PM) with an aerodynamic diameter of <10 μm (PM 10 ) is a well-established health hazard. There is increasing evidence that geogenic (Earth-derived) particles can induce adverse biological effects upon inhalation, though there is high variability in particle bioreactivity that is associated with particle source and physicochemical properties. In this study, we investigated physicochemical properties and biological reactivity of volcanic ash from the April 2021 eruption of La Soufrière volcano, St. Vincent, and two desert dust samples: a standardized test dust from Arizona and an aeolian Gobi Desert dust sampled in China. We determined particle size, morphology, mineralogy, surface texture and chemistry in sub-10 μm material to investigate associations between particle physicochemical properties and observed bioreactivity. We assessed cellular responses (cytotoxic and pro-inflammatory effects) to acute particle exposures (24 hr) in monocultures at the air-liquid interface using two types of cells of the human airways: BEAS-2B bronchial epithelial cells and A549 alveolar type II epithelial cells. In acellular assays, we also assessed particle oxidative potential and the presence of microorganisms. The results showed that volcanic ash and desert dust exhibit intrinsically different particle morphology, surface textures and chemistry, and variable mineralogical content. We found that Gobi Desert dust is more bioreactive than freshly erupted volcanic ash and Arizona test dust, which is possibly linked to the presence of microorganisms (bacteria) and/or nanoscale elongated silicate minerals (potentially clay such as illite or vermiculite) on particle surfaces.

GeoHealth↗

Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where p H (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as p H increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

Massachusetts↗