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USGS2014

Integration of stable carbon isotope, microbial community, dissolved hydrogen gas, and 2 H H 2 O tracer data to assess bioaugmentation for chlorinated ethene degradation in fractured rocks

An in situ bioaugmentation (BA) experiment was conducted to understand processes controlling microbial dechlorination of trichloroethene (TCE) in groundwater at the Naval Air Warfare Center (NAWC), West Trenton, NJ. In the BA experiment, an electron donor (emulsified vegetable oil and sodium lactate) and a chloro-respiring microbial consortium were injected into a well in fractured mudstone of Triassic age. Water enriched in 2 H was also injected as a tracer of the BA solution, to monitor advective transport processes. The changes in concentration and the δ 13 C of TCE, cis-dichloroethene (cis-DCE), and vinyl chloride (VC); the δ 2 H of water; changes in the abundance of the microbial communities; and the concentration of dissolved H2 gas compared to pre- test conditions, provided multiple lines of evidence that enhanced biodegradation occurred in the injection well and in two downgradient wells. For those wells where the biodegradation was stimulated intensively, the sum of the molar chlorinated ethene (CE) concentrations in post-BA water was higher than that of the sum of the pre-BA background molar CE concentrations. The concentration ratios of TCE/(cis-DCE + VC) indicated that the increase in molar CE concentration may result from additional TCE mobilized from the rock matrix in response to the oil injection or due to desorption/diffusion. The stable carbon isotope mass-balance calculations show that the weighted average 13 C isotope of the CEs was enriched for around a year compared to the background value in a two year monitoring period, an effective indication that dechlorination of VC was occurring. Insights gained from this study can be applied to efforts to use BA in other fractured rock systems. The study demonstrates that a BA approach can substantially enhance in situ bioremediation not only in fractures connected to the injection well, but also in the rock matrix around the well due to processes such as diffusion and desorption. Because the effect of the BA was intensive only in wells where an amendment was distributed during injection, it is necessary to adequately distribute the amendments throughout the fractured rock to achieve substantial bioremediation. The slowdown in BA effect after a year is due to some extend to the decrease abundant of appropriate microbes, but more likely the decreased concentration of electron donor.

New Jersey↗

USGS2018

Variability of organic carbon content and the retention and release of trichloroethene in the rock matrix of a mudstone aquifer

Contaminants diffusing from fractures into the immobile porosity of the rock matrix are subject to prolonged residence times. Organic contaminants can adsorb onto organic carbonaceous materials in the matrix extending contaminant retention. An investigation of spatial variability of the fraction of organic carbon ( f oc ) is conducted on samples of rock core from seven closely spaced boreholes in a mudstone aquifer contaminated with trichloroethene (TCE). A total of 378 samples were analyzed at depths between 14 and 36 m below land surface. Mudstone units associated with deep water deposition have the largest f oc , with a maximum value of 0.0396, and units associated with shallow water deposition have the smallest f oc . Even though f oc correlates with depositional conditions, f oc still varies over more than an order of magnitude in continuous mudstone layers between boreholes, and there is large variability in f oc over short distances perpendicular to bedding. Simulations of diffusion and linear equilibrium adsorption of TCE using spatially variable f oc in the rock matrix show order of magnitude variability in the adsorbed TCE over short distances in the matrix and residence times extending to hundreds of years following remediation in adjacent fractures. Simulations using average values of f oc do not capture the range of TCE mass that can be retained in a rock matrix characterized by spatially variable f oc . Bounds on TCE mass within the rock matrix can be obtained by simulations with spatially uniform values of f oc equal to the maximum and minimum values of f oc for a given mudstone unit.

New Jersey↗

USGS2021

Telemetry evaluation of carbon dioxide as a behavioral deterrent for invasive carps

Carbon dioxide (CO 2 ) mixed into water is being explored as a possible management strategy to deter the upstream movements of invasive carps through navigation locks and other migratory pinch-points. This study used two-dimensional acoustic telemetry to assess the effectiveness of dissolved CO 2 as a chemosensory deterrent to two carp species in a large U-shaped pond. Free-swimming movements of telemetered bighead carp ( Hypophthalmichthys nobilis ) and grass carp ( Ctenopharyngodon idella ) were documented 24 h before treatment and 24 h during treatments at 60, 121 and 213 mg/L CO 2 (mean concentrations in pond water). Several behavioral endpoints were then quantified and compared to evaluate deterrence efficacy. In general, results showed that both carp species responded similarly to CO 2 treatments. Carps consistently relocated into areas away from the injection site and made fewer attempts to re-enter CO 2 treated areas. On average, CO 2 treatments reduced mid-line crosses between untreated and treated sides of the pond by 58% at 121 mg/L CO 2 and 78% at 213 mg/L CO 2 relative to normal swimming movements recorded before treatment. Fish swim speeds increased significantly when inside the CO 2 plume during treatments during 213 mg/L CO 2 trials relative to swim speeds outside the plume, possibly indicative of active searching and avoidance responses. Overall, this study found that CO 2 altered the behavior of bighead carp and grass carp. Natural resource agencies could consider the CO 2 concentrations identified in this study to inform future applications to deter invasive carps from locations where they are at-risk to move upstream.

Journal of Great Lakes Research↗

USGS2013

Export of dissolved organic carbon from the Penobscot River basin in north-central Maine

Dissolved organic carbon (DOC) flux from the Penobscot River and its major tributaries in Maine was determined using continuous discharge measurements, discrete water sampling, and the LOADEST regression software. The average daily flux during 2004–2007 was 71 kg C ha −1 yr −1 (392 Mt C d −1 ), an amount larger than measured in most northern temperate and boreal rivers. Distinct seasonal variation was observed in the relation between concentration and discharge (C–Q). During June through December (summer/fall), there was a relatively steep positive C–Q relation where concentration increased by a factor of 2–3 over the approximately 20-fold range of observed stream discharge for the Penobscot River near Eddington, Maine. In contrast, during January through May (winter/spring), DOC concentration did not increase with increasing discharge. In addition, we observed a major shift in the C–Q between 2004–2005 and 2006–2007, apparently resulting from unprecedented rainfall, runoff, and soil flushing beginning in late fall 2005. The relative contribution to the total Penobscot River basin DOC flux from each tributary varied dramatically by season, reflecting the role of large regulated reservoirs in certain basins. DOC concentration and flux per unit watershed area were highest in tributaries containing the largest areas in palustrine wetlands. Tributary DOC concentration and flux was positively correlated to percentage wetland area. Climatic or environmental changes that influence the magnitude or timing of river discharge or the abundance of wetlands will likely affect the export of DOC to the near-coastal ocean.

Maine↗

USGS2006

Drowned coralline algal dominated deposits off Lanai, Hawaii; carbonate accretion and vertical tectonics over the last 30 ka

We present detailed bathymetry, remotely operated vehicle (ROV) and submersible observations, and sedimentary and radiocarbon age data from carbonate deposits recovered from two submerged terraces at − 150 m (T1) and − 230 m (T2) off Lanai, Hawaii. The tops of the terraces are veneered by relatively thin (<5 m) in situ accumulations of coralline algal nodule, coralgal nodule, Halimeda and a derived oolitic facies deposited in intermediate (30–60 m) to deep fore-reef slope settings (60–120 m). The data are used to develop a sedimentary facies model that is consistent with eustatic sea-level variations over the last 30 ka. Both nodule facies on T1 and T2 initiated growth 30–29 ka following a fall in sea level of &sim;50 m and increase in bottom currents during the transition from Marine Isotope Stage 3 to 2. The nodules accreted slowly throughout the Last Glacial Maximum when sea-level was relatively stable. Drowning occurred during the early deglaciation (17–16 ka) and was marked by the complete drowning of coralline algal nodules facies on T2 and incipient drowning of coralgal facies on T1. Abrupt sea-level rise during the middle deglaciation, perhaps associated with global meltwater pulse 1A (14–15 ka), finally drowned the coralgal facies on T1, which in turn was overlain by a deep-water Halimeda facies or an oolitic facies derived from upslope. Our data indicates that Lanai has experienced relatively little vertical tectonic movement over the last 30 ka. Using paleobathymetric data derived from the sedimentary facies, age vs. depth relationships, and published sea-level curves, we estimate that Lanai could be either slowly uplifting or subsiding, but at rates <0.1 m/kyr (uplift) or <0.4 m/kyr (subsidence) over this 30 kyr period.

Hawai'i↗

USGS2006

Carbon isotopic fractionation of CH4 and CO2 during canister desorption of coal

Canister desorption of coal gas from freshly sampled coal is commonly used for exploratory assessment of the coalbed methane (CBM) potential of a basin or prospect, as well as for the sampling of gas for isotopic determination of the gas origin. Compositional and ??13C isotopic time-series of desorbing CBM and carbon dioxide (CO2) over 3-4 months demonstrate considerable compositional and isotopic shifts over time. Non-stationary chemical and isotopic characteristics are due to differences in diffusivity and adsorbance behavior of gas molecules and must be taken into account when attempting to reproducibly sample coal gases. Off-line gas processing on a vacuum line and on-line GC/MS analyses were performed on coal gas samples from the Springfield and Seelyville Coal Members of the Pennsylvanian age that were cored in the SE Illinois Basin in SW Indiana, USA. The coals cover a narrow range of maturity from 0.54% to 0.64% vitrinite reflectance. Methane initially desorbed faster than CO2, resulting in a 50% increase of the CO 2 content in bulk desorbing gas on the 50th day relative to the first day of desorption. After 50 days of desorption, about 90% of all coal gas was desorbed. Over the same time period, ??13C values of incrementally sampled coal gas increased by 2??? and 9???, for CH 4 and CO2, respectively, testifying to the greater retention of 13CH4 and 13CO2 relative to 12CH4 and 12CO2. An isotopic mass balance of the individual, sequentially desorbed and sampled gas amounts yielded weighted mean ??13CCH4 and ??13CCO2 values for characterizing the cumulatively desorbed gas. The overall mean ??13C values were equivalent to ??13C values of gases that desorbed at a time when half of the potentially available gas had been desorbed from coal, corresponding in this study to a time between day 5 and day 12 of canister desorption at 15-18??C. The total expected gas volume and the ???50% midpoint can thus be approximated for a desorbing coal gas sample, based on a dynamic prediction after the first five days of canister desorption. ?? 2005 Elsevier Ltd. All rights reserved.

Organic Geochemistry↗

USGS2010

Carbon and hydrogen isotopic reversals in deep basin gas: Evidence for limits to the stability of hydrocarbons

During studies of unconventional natural gas reservoirs of Silurian and Ordovician age in the northern Appalachian basin we observed complete reversal of the normal trend of carbon isotopic composition, such that ??13C methane (C1) >??13C ethane (C2) >??13C propane (C3). In addition, we have observed isotopic reversals in the ??2H in the deepest samples. Isotopic reversals cannot be explained by current models of hydrocarbon gas generation. Previous observations of partial isotopic reversals have been explained by mixing between gases from different sources and thermal maturities. We have constructed a model which, in addition to mixing, requires Rayleigh fractionation of C2 and C3 to cause enrichment in 13C and create reversals. In the deepest samples, the normal trend of increasing enrichment of 13C and 2H in methane with increasing depth reverses and 2H becomes depleted as 13C becomes enriched. We propose that the reactions that drive Rayleigh fractionation of C2 and C3 involve redox reactions with transition metals and water at late stages of catagenesis at temperatures on the order of 250-300??C. Published ab initio calculated fractionation factors for C-C bond breaking in ethane at these temperatures are consistent with our observations. The reversed trend in ??2H in methane appears to be caused by isotopic exchange with formation water at the same temperatures. Our interpretation that Rayleigh fractionation during redox reactions is causing isotopic reversals has important implications for natural gas resources in deeply buried sedimentary basins. ?? 2010.

Organic Geochemistry↗

USGS2017

Constraining the thermal history of the North American Midcontinent Rift System using carbonate clumped isotopes and organic thermal maturity indices

The Midcontinent Rift System (MRS) is a Late Mesoproterozoic (∼1.1 Ga) sequence of volcanic and sedimentary rocks exposed in the Lake Superior Region of North America. The MRS continues to be the focus of much research due to its economic mineral deposits as well as its archive of Precambrian life and tectonic processes. In order to constrain the post-depositional thermal history of the MRS, samples were analyzed for carbonate clumped isotope composition and organic thermal maturity. Clumped isotope values from sedimentary/early-diagenetic samples were partially reset during burial to temperatures between 68 and 75 °C. Solid-state reordering models indicate that maximum burial temperatures of 125–155 °C would reset the clumped isotope values to the observed temperature range prior to the onset of regional cooling and uplift. Clumped isotope results from late-stage veins in the White Pine Mine encompass a greater temperature range (49–116 °C), indicative of spatially variable hydrothermal activity and vein emplacement after burial temperatures fell below 100 °C during regional cooling and uplift. Clumped isotope and organic thermal maturity data do not indicate significant spatial differences in thermal history along the MRS. Observed variability in bulk organic matter composition and biomarker indices are therefore more likely a result of shifts in primary productivity or early-degradation processes. These results demonstrate that the MRS experienced a spatially consistent, relatively mild thermal history (125–155 °C) and is therefore a valuable archive for understanding the Late Mesoproterozoic environment.

Lake Superior↗

USGS2009

Geochemical evidence for African dust and volcanic ash inputs to terra rossa soils on carbonate reef terraces, northern Jamaica, West Indies

The origin of red or reddish-brown, clay-rich, "terra rossa" soils on limestone has been debated for decades. A traditional qualitative explanation for their formation has been the accumulation of insoluble residues as the limestone is progressively dissolved over time. However, this mode of formation often requires unrealistic or impossible amounts of carbonate dissolution. Therefore, where this mechanism is not viable and where local fluvial or colluvial inputs can be ruled out, an external source or sources must be involved in soil formation. On the north coast of the Caribbean island of Jamaica, we studied a sequence of terra rossa soils developed on emergent limestones thought to be of Quaternary age. The soils become progressively thicker, redder, more Fe- and Al-rich and Si-poor with elevation. Furthermore, although kaolinite is found in all the soils, the highest and oldest soils also contain boehmite. Major and trace element geochemistry shows that the host limestones and local igneous rocks are not likely source materials for the soils. Other trace elements, including the rare earth elements (REE), show that tephra from Central American volcanoes is not a likely source either. However, trace element geochemistry shows that airborne dust from Africa plus tephra from the Lesser Antilles island arc are possible source materials for the clay-rich soils. A third, as yet unidentified, source may also contribute to the soils. We hypothesize that older, more chemically mature Jamaican bauxites may have had a similar origin. The results add to the growing body of evidence of the importance of multiple parent materials, including far-traveled dust, to soil genesis.

Quaternary International↗

USGS2008

The effects of land use on fluvial sediment chemistry for the conterminous U.S. - Results from the first cycle of the NAWQA Program: Trace and major elements, phosphorus, carbon, and sulfur

In 1991, the U.S. Geological Survey (USGS) began the first cycle of its National Water Quality Assessment (NAWQA) Program. The Program encompassed 51 river basins that collectively accounted for more than 70% of the total water use (excluding power generation), and 50% of the drinking water supply in the U.S. The basins represented a variety of hydrologic settings, rock types (geology), land-use categories, and population densities. One aspect of the first cycle included bed sediment sampling; sites were chosen to represent baseline and important land-use categories (e.g., agriculture, urban) in each basin. In total, over 1200 bed sediment samples were collected. All samples were size-limited (< 63????m) to facilitate spatial and/or temporal comparisons, and subsequently analyzed for a variety of chemical constituents including major (e.g., Fe, Al,) and trace elements (e.g., Cu, Zn, Cd), nutrients (e.g., P), and carbon. The analyses yielded total (??? 95% of the concentrations present), rather than total-recoverable chemical data. Land-use percentages, upstream underlying geology, and population density were determined for each site and evaluated to asses their relative influence on sediment chemistry. Baseline concentrations for the entire U.S. also were generated from a subset of all the samples, and are based on material collected from low population (??? 27??p km- 2) density, low percent urban (??? 5%), agricultural or undeveloped areas. The NAWQA baseline values are similar to those found in other national and global datasets. Further, it appears that upstream/underlying rock type has only a limited effect (mostly major elements) on sediment chemistry. The only land-use category that appears to substantially affect sediment chemistry is percent urban, and this result is mirrored by population density; in fact, the latter appears more consistent than the former.

Science of the Total Environment↗

USGS2015

Patterns and predictability in the intra-annual organic carbon variability across the boreal and hemiboreal landscape

Factors affecting total organic carbon (TOC) concentrations in 215 watercourses across Sweden were investigated using parameter parsimonious regression approaches to explain spatial and temporal variabilities of the TOC water quality responses. We systematically quantified the effects of discharge, seasonality, and long-term trend as factors controlling intra-annual (among year) and inter-annual (within year) variabilities of TOC by evaluating the spatial variability in model coefficients and catchment characteristics (e.g. land cover, retention time, soil type). Catchment area (0.18–47,000 km 2 ) and land cover types (forests, agriculture and alpine terrain) are typical for the boreal and hemiboreal zones across Fennoscandia. Watercourses had at least 6 years of monthly water quality observations between 1990 and 2010. Statistically significant models (p < 0.05) describing variation of TOC in streamflow were identified in 209 of 215 watercourses with a mean Nash-Sutcliffe efficiency index of 0.44. Increasing long-term trends were observed in 149 (70%) of the watercourses, and intra-annual variation in TOC far exceeded inter-annual variation. The average influences of the discharge and seasonality terms on intra-annual variations in daily TOC concentration were 1.4 and 1.3 mg l − 1 (13 and 12% of the mean annual TOC), respectively. The average increase in TOC was 0.17 mg l − 1 year − 1 (1.6% year − 1 ). Multivariate regression with over 90 different catchment characteristics explained 21% of the spatial variation in the linear trend coefficient, less than 20% of the variation in the discharge coefficient and 73% of the spatial variation in mean TOC. Specific discharge, water residence time, the variance of daily precipitation, and lake area, explained 45% of the spatial variation in the amplitude of the TOC seasonality. Because the main drivers of temporal variability in TOC are seasonality and discharge, first-order estimates of the influences of climatic variability and change on TOC concentration should be predictable if the studied catchments continue to respond similarly.

Science of the Total Environment↗

USGS2018

Wetlands receiving water treated with coagulants improve water quality by removing dissolved organic carbon and disinfection byproduct precursors

Constructed wetlands are used worldwide to improve water quality while also providing critical wetland habitat. However, wetlands have the potential to negatively impact drinking water quality by exporting dissolved organic carbon (DOC) that upon disinfection can form disinfection byproducts (DBPs) like trihalomethanes (THMs) and haloacetic acids (HAAs). We used a replicated field-scale study located on organic rich soils in California's Sacramento-San Joaquin Delta to test whether constructed flow-through wetlands which receive water high in DOC that is treated with either iron- or aluminum-based coagulants can improve water quality with respect to DBP formation. Coagulation alone removed DOC (66–77%) and THM (67–70%) precursors, and was even more effective at removing HAA precursors (77–90%). Passage of water through the wetlands increased DOC concentrations (1.5–7.5 mg L − 1 ), particularly during the warmer summer months, thereby reversing some of the benefits from coagulant addition. Despite this addition, water exiting the wetlands treated with coagulants had lower DOC and DBP precursor concentrations relative to untreated source water. Benefits of the coagulation-wetland systems were greatest during the winter months (approx. 50–70% reduction in DOC and DBP precursor concentrations) when inflow water DOC concentrations were higher and wetland DOC production was lower. Optical properties suggest DOC in this system is predominantly comprised of high molecular weight, aromatic compounds, likely derived from degraded peat soils.

Science of the Total Environment↗

USGS2020

Fates and fingerprints of sulfur and carbon following wildfire in economically important croplands of California, U.S.

Sulfur (S) is widely used in agriculture, yet little is known about its fates within upland watersheds, particularly in combination with disturbances like wildfire. Our study examined the effects of land use and wildfire on the biogeochemical “fingerprints,” or the quantity and chemical composition, of S and carbon (C). We conducted our research within the Napa River Watershed, California, U.S., where high S applications to vineyards are common, and ~ 20% of the watershed burned in October 2017, introducing a disturbance now common across the warmer, drier Western U.S. We used a laboratory rainfall experiment to compare unburned and low severity burned vineyard and grassland soils. We then sampled streams draining sub-catchments with differing land use and degrees of burn and burn severity to understand combined effects at broader spatial scales. Before the laboratory experiment, vineyard soils had 2–3.5 times more S than grassland soils, while burned soils—regardless of land use—had 1.5–2 times more C than unburned soils. During the laboratory experiment, vineyard soil leachates had 16–20 times more S than grassland leachates, whereas leachate C was more variable across land use and burn soil types. Unburned and burned vineyard soils leached S with δ 34 S values enriched 6–15‰ relative to grassland soils, likely due to microbial S processes within vineyard soils. Streams draining vineyards also had the fingerprint of agricultural S, with ~2–5 fold higher S concentrations and ~ 10‰ enriched δ 34 S-SO 4 2− values relative to streams draining non-agricultural areas. However, streams draining a higher fraction of burned non-agricultural areas also had enriched δ 34 S values relative to unburned non-agricultural areas, which we attribute to loss of 32 S during combustion. Our findings illustrate the interacting effects of wildfire and land use on watershed S and C cycling—a new consideration under a changing climate, with significant implications for ecosystem function and human health.

California↗

USGS2021

Ongoing increases in dissolved organic carbon are sustained by decreases in ionic strength rather than decreased acidity in waters recovering from acidic deposition

Dissolved organic carbon (DOC) has received considerable attention in freshwater research, particularly since the early 2000s when increasing trends became apparent. However, remaining questions need to be resolved to address future effects of DOC on surface waters. This study was undertaken to determine (1) the relative importance of acidity and ionic strength in driving DOC increases in waters recovering from acidification and (2) the role played by long-term acid rain effects on soil. Data obtained from temporal and spatial monitoring of 142 headwater streams throughout the Adirondack region of New York (USA) were used to evaluate chemical relationships involving DOC. Year-round monitoring of three streams of differing acidification status were combined with intermittent stream surveys during spring snowmelt throughout this 24,243 km 2 region that is recovering from acidification of soils and surface waters. Despite acidic deposition decreases reaching levels estimated for the early 1900s, DOC concentrations exhibited linear increases from the early 2000s through 2019. Ionic strength or conductivity showed consistent inverse relationships with DOC in all data comparisons from 2004‐05 to 2018‐19. In contrast, relationships between pH and DOC did not support increasing pH as an important factor in DOC increases. Inconsistent relationships between pH and DOC were due to strongly acidic organic acids that remain unprotonated throughout the pH range of these waters and limited weak-acid deprotonation below pH 6.2. Decreasing ionic strength increases DOC solubility by expanding the diffuse double layer, which fosters disaggregation of organic matter and dispersion of colloids. This affect controlled DOC solubilization below a pH of approximately 6.2. Distinguishing between ionic strength and pH effects is important because further large reductions in acidic deposition are not expected but continued soil-water dilution is likely from soil-Ca 2+ depletion and the decreasing rate of Ca 2+ leaching by SO 4 2− and NO 3 − , which are still being released from soil organic matter.

New York↗

USGS2024

Recent, widespread nitrate decreases may be linked to persistent dissolved organic carbon increases in headwater streams recovering from past acidic deposition

Long-term monitoring of water quality responses to natural and anthropogenic perturbation of watersheds informs policies for managing natural resources. Dissolved organic carbon (DOC) and nitrate (NO 3 − ) in streams draining forested landscapes provide valuable information on ecosystem function due to their biogeochemical reactivity and solubility in water. Here we evaluate a 20-year record (2001−2021) of biweekly stream-water samples ( n > 3000) and continuous discharge in three forested catchments in the Adirondack region of New York to investigate and interpret long-term trends in DOC and NO 3 − concentrations. Results from the intensively monitored catchments were compared with data from synoptic surveys of streams throughout the Adirondack region. A weighted regressions on time, discharge, and season (WRTDS) model, used to estimate daily flow-normalized concentrations, determined that DOC increased by ~30 to 50 % while NO 3 − decreased by ~50 to 70 % over the study period. The large amount of data from catchments with different soil properties permitted us to assess the relative effects of hydrology, season, and land cover factors on temporal trends in DOC and NO 3 − concentrations. We found weak evidence of climatic forcing of long-term increases in DOC, and instead contend that declining ionic strength in precipitation linked to declining anthropogenic acid deposition is driving DOC trends in stream waters. Nitrate concentrations were more variable but clearly decreased in recent years possibly related to declining N deposition. The recent increase in DOC:NO 3 − in all catchments indicates a major shift in stream stoichiometry that reflects changes in ecosystem functioning that may have important biogeochemical implications for terrestrial as well as aquatic ecosystems.

Science of the Total Environment↗

USGS2024

Habitat and dissolved organic carbon modulate variation in the biogeochemical drivers of mercury bioaccumulation in dragonfly larvae at the national scale

We paired mercury (Hg) concentrations in dragonfly larvae with water chemistry in 29 U.S. national parks to highlight how ecological and biogeochemical context (habitat, dissolved organic carbon [DOC]) influence drivers of Hg bioaccumulation. Although prior studies have defined influences of biogeochemical variables on Hg production and bioaccumulation, it has been challenging to determine their influence across diverse habitats, regions, or biogeochemical conditions within a single study. We compared global (i.e., all sites), habitat-specific, and DOC-class models to illuminate how these controls on biotic Hg vary. Although the suite of important biogeochemical factors across all sites (e.g., aqueous Hg, DOC, sulfate [SO42−], and pH) was consistent with general findings in the literature, contrasting the restricted models revealed more nuanced controls on biosentinel Hg. Comparing habitats, aqueous (filtered) total mercury (THg) and SO42− were important in lentic systems whereas aqueous (filtered) methylmercury (MeHg), DOC, pH, and SO42− were important in lotic and wetland systems. The ability to identify important variables varied among habitats, with less certainty in lentic (model weight (W) = 0.05) than lotic (W = 0.11) or wetland habitats (W = 0.23), suggesting that biogeochemical drivers of bioaccumulation are more variable, or obscured by other aspects of Hg cycling, in these habitats. Results revealed a contrast in the importance of aqueous MeHg versus aqueous THg between DOC-classes: in low-DOC sites (<8.5 mg/L), availability of upstream inputs of MeHg appeared more important for bioaccumulation; in high-DOC sites (>8.5 mg/L) THg was more important, suggesting a link to in-situ controls on bioavailability of Hg for MeHg production. Mercury bioaccumulation (indicated by bioaccumulation factor) was more efficient in low DOC-class sites, likely due to reduced partitioning of aqueous MeHg to DOC. Together, findings highlight substantial variation in the drivers of Hg bioaccumulation and suggest consideration of these factors in natural resource management and decision-making.

Science of the Total Environment↗

USGS2006

Evidence for hydraulic heterogeneity and anisotropy in the mostly carbonate Prairie du Chien Group, southeastern Minnesota, USA

In southeastern Minnesota, Paleozoic bedrock aquifers have typically been represented in groundwater flow simulations as isotropic, porous media. To obtain a more accurate hydrogeologic characterization of the Ordovician Prairie du Chien Group, a new approach was tested, combining detailed geologic observations, particularly of secondary porosity, with hydraulic data. Lithologic observations of the depositional and erosional history of the carbonate-dominated bedrock unit constrained characterization of both primary (matrix) and secondary porosity from outcrops and core. Hydrostratigraphic data include outcrop and core observations along with core plug permeability tests. Hydrogeologic data include discrete interval aquifer tests, borehole geophysics, water chemistry and isotope data, and dye trace studies. Results indicate that the Prairie du Chien Group can be subdivided into the Shakopee aquifer at the top, consisting of interbedded dolostone, sandstone and shale, and the underlying Oneota confining unit consisting of thickly bedded dolostone. The boundary between these two hydrogeologic units does not correspond to lithostratigraphic boundaries, as commonly presumed. Groundwater flow in the Shakopee aquifer is primarily through secondary porosity features, most commonly solution-enlarged bedding planes and sub-horizontal and vertical fractures. Regional scale preferential development of cavernous porosity and permeability along specific stratigraphic intervals that correspond to paleokarst were also identified, along with a general depiction of the distribution of vertical and horizontal fractures. The combination of outcrop and core investigations, along with borehole geophysics, discrete interval aquifer tests, water chemistry and isotope data and dye trace studies show that the Prairie du Chien Group is best represented hydrogeologically as heterogeneous and anisotropic. Furthermore, heterogeneity and anisotropy within the Prairie du Chien Group is mappable at a regional scale (>15,000 km2). ?? 2005 Elsevier B.V. All rights reserved.

Sedimentary Geology↗

USGS2016

Long-term reactive nitrogen loading alters soil carbon and microbial community properties in a subalpine forest ecosystem

Elevated nitrogen (N) deposition due to increased fossil fuel combustion and agricultural practices has altered global carbon (C) cycling. Additions of reactive N to N-limited environments are typically accompanied by increases in plant biomass. Soil C dynamics, however, have shown a range of different responses to the addition of reactive N that seem to be ecosystem dependent. We evaluated the effect of N amendments on biogeochemical characteristics and microbial responses of subalpine forest organic soils in order to develop a mechanistic understanding of how soils are affected by N amendments in subalpine ecosystems. We measured a suite of responses across three years (2011–2013) during two seasons (spring and fall). Following 17 years of N amendments, fertilized soils were more acidic (control mean 5.09, fertilized mean 4.68), and had lower %C (control mean 33.7% C, fertilized mean 29.8% C) and microbial biomass C by 22% relative to control plots. Shifts in biogeochemical properties in fertilized plots were associated with an altered microbial community driven by reduced arbuscular mycorrhizal (control mean 3.2 mol%, fertilized mean 2.5 mol%) and saprotrophic fungal groups (control mean 17.0 mol%, fertilized mean 15.2 mol%), as well as a decrease in N degrading microbial enzyme activity. Our results suggest that decreases in soil C in subalpine forests were in part driven by increased microbial degradation of soil organic matter and reduced inputs to soil organic matter in the form of microbial biomass.

Soil Biology and Biochemistry↗