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Microbial carbon cycling in oligotrophic regional aquifers near the Tono Uranium Mine, Japan as inferred from δ13C and Δ14C values of in situ phospholipid fatty acids and carbon sources

Microorganisms are ubiquitous in deep subsurface environments, but their role in the global carbon cycle is not well-understood. The natural abundance δ 13 C and Δ 14 C values of microbial membrane phospholipid fatty acids (PLFAs) were measured and used to assess the carbon sources of bacteria in sedimentary and granitic groundwaters sampled from three boreholes in the vicinity of the Tono Uranium Mine, Gifu, Japan. Sample storage experiments were performed and drill waters analyzed to characterize potential sources of microbial contamination. The most abundant PLFA structures in all waters sampled were 16:0, 16:1ω7 c , cy 17:0, and 18:1ω7 c . A PLFA biomarker for type II methanotrophs, 18:1ω8 c , comprised 3% and 18% of total PLFAs in anoxic sedimentary and granitic waters, respectively, sampled from the KNA-6 borehole. The presence of this biomarker was unexpected given that type II methanotrophs are considered obligate aerobes. However, a bacterium that grows aerobically with CH 4 as the sole energy source and which also produces 56% of its total PLFAs as 18:1ω8 c was isolated from both waters, providing additional evidence for the presence of type II methanotrophs. The Δ 14 C values determined for type II methanotroph PLFAs in the sedimentary (−861‰) and granite (−867‰) waters were very similar to the Δ 14 C values of dissolved inorganic carbon (DIC) in each water (∼−850‰). This suggests that type II methanotrophs ultimately derive all their carbon from inorganic sources, whether directly from DIC and/or from CH 4 produced by the reduction of DIC. In contrast, δ 13 C values of type II PLFAs in the sedimentary (−93‰) and granite (−60‰) waters indicate that these organisms use different carbon assimilation schemes in each environment despite very similar δ 13 C CH 4 "> δ13CCH4 values (∼−95‰) for each water. The δ 13 C PLFA values (−28‰ to −45‰) of non-methanotrophic bacteria in the KNA-6 LTL water do not clearly distinguish between heterotrophic and autotrophic metabolisms, but Δ 14 C PLFA values indicate that >65% of total bacteria filtered from the KNA-6 LTL water are heterotrophs. Ancient Δ 14 C values (∼−1000‰) of some PLFAs suggest that many heterotrophs utilize ancient organic matter, perhaps from lignite seams within the sedimentary rocks. The more negative range of δ 13 C PLFA values determined for the KNA-6 granitic water (−42‰ to −66‰) are likely the result of a microbial ecosystem dominated by chemolithoautotrophy, perhaps fuelled by abiogenic H 2 . Results of sample storage experiments showed substantial shifts in microbial community composition and δ 13 C PLFA values (as much as 5‰) during 2–4 days of dark, refrigerated, aseptic storage. However, water samples collected and immediately filtered back in the lab from freshly drilled MSB-2 borehole appeared to maintain the same relative relationships between δ 13 C PLFA values for sedimentary and granitic host rocks as observed for samples directly filtered under artesian flow from the KNA-6 borehole of the Tono Uranium Mine.

Tono Uranium Mine↗

Watershed Continuum Monitoring Approach: Combining multiple water quality patterns along stream and river flowpaths to track sources, pathways, and processing of pollutants

There is a growing need to improve and expand water quality monitoring approaches to more accurately track the sources, fate, and transport of multiple chemicals and pollutants holistically and quantify the effects of best management practices (BMPs) at the watershed scale. An overarching question raised by scientists, environmental managers, and the general public is: how far can water quality impacts from disturbances or benefits from watershed management and restoration propagate along stream and river flowpaths? Many studies using the classic watershed approach focus on analyzing changes in water quality over time at one or a few sampling stations, whereas theories such as the River Continuum Concept focus on predicting shifts in energy sources and biological communities along rivers but have not been directly applied to water quality. We propose to merge these concepts to create a Watershed Continuum Monitoring Approach (WCMA) that combines both spatial and temporal monitoring in order to better detect and quantify trends and transitions in multiple water quality indicators along flowpaths. Specifically, an array of multiple water quality indicators are analyzed at multiple downstream points along a watershed flowpath over time. These multiple water quality indicators are analyzed together for making comparisons to infer hydrological, biological, and geochemical processes controlling sources, transport, and attenuation of pollutants ( e.g. , analagous to stream tracer studies at the watershed scale). The WCMA leverages the natural expansion of watershed areas along a flowpath, which reflect transitions in land use, land cover, and environmental management across spatial and temporal dimensions for making direct comparisons across different stream reaches and spatial trend analysis. WCMA facilitates monitoring of multiple water quality indicators together, and identifcation of hot spots in sources and attenuation of pollutants or mixtures of pollutants. We illustrate practical applications of the WCMA to analyze water quality trends, transitions, and tradeoffs ( i.e. , a tradeoff occurs when one pollutant is reduced but another is directly or indirectly increased downstream). We explore case studies that quantify: (1) downstream reductions in concentrations of multiple pollutants along a stream flowing to a major drinking water source due to engineered and nature-based solutions, (2) downstream reductions in multiple pollutants and water quality tradeoffs along streams experiencing stormwater BMPs and stream restoration, (3) comparisons in downstream reductions of multiple pollutants and nutrient uptake along streams draining into major drinking water sources based on types of stream restoration, (4) comparisons of downstream pollutant reductions along streams experiencing riparian forest conservation vs. stream restoration, and (5) mapping and visualizing hot spots of increasing water quality problems such as hypoxia, contaminant mobilization, and freshwater salinization that extend downstream to tidal rivers of the Chesapeake Bay. We explore future applications of WCMA for tracking decreasing trends in salinity, E. coli , and other pollutants of emerging concern. WCMA can holistically inform progress towards achieving multiple water quality goals and also be used as a screening tool for selecting monitoring sites and targeting management in strategic locations. Overall, WCMA enables the simultaneous quantification and comparison of sources and transport and attenuation rates for different chemicals and pollutants across a broader range of watershed sizes and flowpath lengths, which is critical for understanding ecological, hydrological, geochemical, and biogeochemical processes along human-impacted streams and rivers.

Ecological Engineering↗

Greenhouse gas emissions from an arid-zone reservoir and their environmental policy significance: Results from existing global models and an exploratory dataset

Reservoirs in arid regions often provide critical water storage but little is known about their greenhouse gas (GHG) footprint. While there is growing appreciation of the role reservoirs play as GHG sources, there is a lack of understanding of GHG emission dynamics from reservoirs in arid regions and implications for environmental policy. Here we present initial GHG emission measurements from Lake Powell, a large water storage reservoir in the desert southwest United States. We report CO 2 -eq emissions from the shallow (< 15 m) littoral regions of the reservoir that are higher than the global average areal emissions from reservoirs (9.4 vs. 5.8 g CO 2 -eq m −2 d −1 ) whereas fluxes from the main reservoir were two orders of magnitude lower (0.09 g CO 2 -eq m −2 d −1 ). We then compared our measurements to modeled CO 2 + CH 4 emissions from the reservoir using four global scale models. Factoring these emissions into hydropower production at Lake Powell yielded low GHG emissions per MWh −1 as compared to fossil-fuel based energy sources. With the exception of one model, the estimated hydropower emissions for Lake Powell ranged from 10−32 kg CO 2 -eq MWh −1 , compared to ∼400−1000 kg CO 2 -eq MWh −1 for natural gas, oil, and coal. We also estimate that reduced littoral habitat under low water levels leads to ∼50% reduction in the CO 2 equivalent emissions per MWh. The sensitivity of GHG emissions to reservoir water levels suggests that the interaction will be an important policy consideration in the design and operation of arid region systems.

Utah↗

Use of upland and riparian areas by wintering bald eagles and implications for wind energy

Weather can shape movements of animals and alter their exposure to anthropogenic threats. Bald eagles ( Haliaeetus leucocephalus ) are increasingly at risk from collision with turbines used in onshore wind energy generation. In the midwestern United States, development of this energy source typically occurs in upland areas that bald eagles use only intermittently. Our objective was to determine the factors that cause wintering bald eagles to occupy riparian areas and riskier, upland areas. We tracked 20 bald eagles using telemetry in the Upper Midwest (MN, IA, MO, WI, IL, USA) during winter 2014–2015 and 2015–2016 and evaluated habitat use by eagles in response to variation in weather and time of year. Eagles used riparian areas more when wind speed and atmospheric pressure were low. Exclusive use of uplands was more frequent during weather systems with low pressure and high humidity and after long periods of cold weather. There was a non‐linear response to time of year (measured by days before migration) in the frequency of exclusive use of uplands or riparian areas. Probability of exclusive use of either landscape was generally constant within 95 days prior to migration. The probability of use of riparian areas, however, was markedly less during dates >100 days before migration. Our results suggest that eagles are most likely to be exposed to wind energy developments located in upland areas during low pressure systems, after long periods of cold weather, and several months before the onset of spring migration. This information helps to better understand the factors influencing bald eagle habitat use in winter and will be useful to managers and developers wishing to establish effective strategies to avoid, minimize, and mitigate take, and to survey for mortalities at wind energy developments.

Illinois, Iowa, Minnesota, Missouri, Wisconsin↗

Examination of Bathymodiolus childressi nutritional sources, isotopic niches, and food-web linkages at two seeps in the US Atlantic margin using stable isotope analysis and mixing models

Chemosynthetic environments support distinct benthic communities capable of utilizing reduced chemical compounds for nutrition. Hundreds of methane seeps have been documented along the U.S. Atlantic margin (USAM), and detailed investigations at a few seeps have revealed distinct environments containing mussels, microbial mats, authigenic carbonates, and soft sediments. The dominant mussel, Bathymodiolus childressi , contains methanotrophic endosymbionts but is also capable of filter feeding, and stable isotope analysis (SIA) of mussel-shell periostracum suggests that these mussels are mixotrophic, assimilating multiple food resources. However, it is unknown whether mixotrophy is widespread or varies spatially and temporally. We used SIA (δ 13 C, δ 15 N, and δ 34 S) and an isotope mixing model (MixSIAR) to estimate resource contribution to B. childressi and characterize food webs at two seep sites (Baltimore Seep; 400 m and Norfolk Seep; 1500 m depths) along the USAM, and applied a linear mixed-effects model to explore the role of mussel population density and tissue type in influencing SIA variance. After controlling for location and temporal variation, isotopic variability was a function of proportion of live mussels present and tissue type. Isotopic differences were also spatially discrete, possibly reflecting variations in the underlying carbon source at the two sites. Low mussel δ 13 C values (∼−63‰) are consistent with a dependence on microbial methane. However, MixSIAR results revealed mixotrophy for mussels at both sites, implying a reliance on a mixture of methane and phytoplankton-derived particulate organic material. The mixing model results also reveal population density-driven patterns, suggesting that resource use is a function of live mussel abundance. Mussel isotopes differed by tissue type, with gill having the lowest δ 15 N values relative to muscle and mantle tissues. Based on mass balance equations, up to 79% of the dissolved inorganic carbon (DIC) of the pore fluids within the anaerobic oxidation of the methane zone is derived from methane and available to fuel upper slope deep-sea communities, such as fishes ( Dysommina rugosa and Symphurus nebulosus ), echinoderms ( Odontaster robustus , Echinus wallisi , and Gracilechinus affinis ), and shrimp, ( Alvinocaris markensis ). The presence of these seeps thereby increases the overall trophic and community diversity of the USAM continental slope. Given the presence of hundreds of seeps within the region, primary production at seeps may serve as an important, yet unquantified, energy source to the USAM deep-sea environment.

Delaware, Maryland, North Carolina, Virginia↗

Evaluation of a roughness length parametrization accounting for wind–wave alignment in a coupled atmosphere–wave model

The importance of wind energy as an alternative energy source has increased over the latest years with more focus on offshore winds. A good estimation of the offshore winds is thus of major importance for this industry. Up to now the effect of the wind–wave (mis)alignment has not yet been taken into account in coupled atmosphere–wave models to study the vertical wind profile and power production estimations of offshore wind farms. In this study the roughness length parametrization of Drennan et al . in 2003, and its extension addressing the wind–wave (mis)alignment proposed by Porchetta et al . in 2019, are investigated in the Coupled Ocean–Atmosphere–Wave–Sediment Transport (COAWST) model. This study shows that the yearly mean wind estimation at hub height (100 m) is improved by the roughness length parametrization of Porchetta et al . compared to Drennan. This is mainly due to the increased roughness of the former parametrization compare to the latter, even in aligned wind–wave conditions. This difference in roughness is caused by the dataset used to obtain the constants, deep‐water conditions versus mixed offshore conditions. Moreover, the roughness length parametrization of Porchetta et al . performs better in two of three alignment categories. Furthermore, similar model performances are obtained if we exclude the wind directions from the wind shadow zone of the measurement mast or the wind directions from the recently built Alpha Ventus wind farm, which is in close vicinity of the measurement mast. Investigating different wind conditions shows that the new roughness length parametrization of Porchetta et al . performs best for both offshore and onshore winds. Additionally, we show that the coupled model estimations of the vertical wind are only slightly affected by significant wave height estimations. Similar model performances for different accuracies of significant wave height estimations are presented. One exception is the perpendicular alignment category where the new roughness length of Porchetta et al . outperforms the roughness length of Drennan when investigating the wind estimations related to significant wave heights with a higher accuracy. The roughness length parametrization of Porchetta et al . reduced the power production overestimation of the coupled model from 5.7 to 2.8%. We also show that the standalone atmospheric model including the roughness length of Charnock in 1955 has a degraded performance compared to the coupled model including the roughness length parametrization of Porchetta et al . for yearly average wind profiles.

Quarterly Journal of the Royal Meteorological Soci↗

Contribution of fish community metrics to the index of biotic integrity in two Ozark rivers

Flow regime, energy source, water quality, and habitat structure within stream systems play major roles in controlling the structure of resident fish communities (Gorman and Karr, 1978; Karr and Dudley, 1981; Schlosser, 1982). Based on the hypothesis that there are predictable relationships between stream variables and fish community structure, overall stream condition has been assessed using indices such as the Index of Biotic Integrity (IBI) (Karr, 1981; Karr et al., 1986). The IBI integrates a wide range of information pertaining to fish community structure that reflects the prevailing chemical, physical, and biological condition of the stream. Assessments made using the IBI have been correlated to actual stream conditions and appear to be sensitive to a wide range of environmental degradation (Fausch et al., 1990).

Ecological Indicators↗

Integrating human impacts and ecological integrity into a risk-based protocol for conservation planning

Conservation planning aims to protect biodiversity by sustainng the natural physical, chemical, and biological processes within representative ecosystems. Often data to measure these components are inadequate or unavailable. The impact of human activities on ecosystem processes complicates integrity assessments and might alter ecosystem organization at multiple spatial scales. Freshwater conservation targets, such as populations and communities, are influenced by both intrinsic aquatic properties and the surrounding landscape, and locally collected data might not accurately reflect potential impacts. We suggest that changes in five major biotic drivers—energy sources, physical habitat, flow regime, water quality, and biotic interactions—might be used as surrogates to inform conservation planners of the ecological integrity of freshwater ecosystems. Threats to freshwater systems might be evaluated based on their impact to these drivers to provide an overview of potential risk to conservation targets. We developed a risk-based protocol, the Ecological Risk Index (ERI), to identify watersheds with least/most risk to conservation targets. Our protocol combines risk-based components, specifically the frequency and severity of human-induced stressors, with biotic drivers and mappable land- and water-use data to provide a summary of relative risk to watersheds. We illustrate application of our protocol with a case study of the upper Tennessee River basin, USA. Differences in risk patterns among the major drainages in the basin reflect dominant land uses, such as mining and agriculture. A principal components analysis showed that localized, moderately severe threats accounted for most of the threat composition differences among our watersheds. We also found that the relative importance of threats is sensitive to the spatial grain of the analysis. Our case study demonstrates that the ERI is useful for evaluating the frequency and severity of ecosystemwide risk, which can inform local and regional conservation planning.

Tennessee↗

Temporal and spatial variability in stable isotope compositions of a freshwater mussel: Implications for biomonitoring and ecological studies

Stable isotopes can be used to elucidate ecological relationships in community and trophic studies. Findings are calibrated against baselines, e.g. from a producer or primary consumer, assumed to act as a reference to the isotopic context created by spatio-temporal attributes such as geography, climate, nutrient, and energy sources. The ability of an organism to accurately represent a community base depends on how, and over what time-scale, it assimilates ambient materials. Freshwater mussels have served as references for trophic studies of freshwater communities and as indicators of change in nutrient pollution load or source. Their suitability as reference animals has not yet been fully explored, however. We conducted a series of studies examining the suitability of freshwater mussels as isotopic baselines, using their ability to reflect variation in ambient nutrient loads as a case scenario. (1) We analyzed bivalve foot tissue ??15N and ??13C from 22 stream reaches in the Piedmont region of North Carolina, USA to show that compositions varied substantially among locations. Site mean bivalve ??13C values correlated with site ambient particulate organic matter (POM) ??13C values, and site mean bivalve ??15N values correlated with site ambient water dissolved ??15N-NO3 values. (2) Similarity of results among sample types demonstrated that the minimally invasive hemolymph sample is a suitable substitute for foot tissue in ??15N analyses, and that small sample sizes generate means representative of a larger population. Both findings can help minimize the impact of sampling on imperiled freshwater mussel populations. (3) In a bivalve transplantation study we showed that hemolymph ??15N compositions responded to a shift in ambient dissolved ??15N-NO3, although slowly. The tissue turnover time for bivalve hemolymph was 113 days. We conclude that bivalves serve best as biomonitors of chronic, rather than acute, fluctuations in stream nutrient loads, and provide initial evidence of their suitability as time-integrated isotopic baselines for community studies. ?? 2006 Springer-Verlag.

Oecologia↗

Irrigation as a fuel pump to freshwater ecosystems

We generated a detailed time series of total dissolved hydrolyzable amino acids (DHAA) in a watershed dominated by irrigated agriculture in northern California, USA to investigate the roles of hydrologic and seasonal changes on the composition of dissolved organic matter (DOM). DHAA are sensitive indicators of the degradation state and reactivity of DOM. DHAA concentrations ranged from 0.55 to 9.96 μM (median 3.51 ± 1.80 μM), with expected peaks during high-discharge storms and unexpected high values throughout the low-discharge irrigation season. Overall, summer irrigation was a critical hydrologic regime for DOM cycling since it mobilized DOM similar in concentration and reactivity to DOM released during storms. Together, irrigation and storm flows exported DOM with (1) the largest DHAA contributions to the dissolved organic carbon and the dissolved organic nitrogen pools, (2) the largest proportion of basic amino acids, and (3) the lowest degradation extent based on multiple indices. In this highly disturbed terrestrial system, UV–vis absorbance did not correlate with DHAA concentrations, while classic interpretations of common amino acid indicators (e.g., proportion of basic amino acids, degradation index, percent of non-protein amino acids) were prone to conflicting characterizations of DOM reactivity. Therefore, a new parameter (processing ratio, PR) derived from individual amino acid concentrations was developed that demonstrated a strong potential for mechanistic-driven characterization of the extent of DOM diagenesis in freshwaters. Irrigated agriculture altered stream biogeochemistry by releasing a continuous supply of reactive DOM (lowest PR values), thereby providing an additional energy source to downstream ecosystems.

California↗

Shifts in the trophic base of intermittent stream food webs

Understanding spatial and temporal variation in the trophic base of stream food webs is critical for predicting population and community stability, and ecosystem function. We used stable isotope ratios ( 13 C/ 12 C, and 15 N/ 14 N) to characterize the trophic base of two streams in the Ozark Mountains of northwest Arkansas, U.S.A. We predicted that autochthonous resources would be more important during the spring and summer and allochthonous resources would be more important in the winter due to increased detritus inputs from the riparian zone during autumn leaf drop. We predicted that stream communities would demonstrate increased reliance on autochthonous resources at sites with larger watersheds and greater canopy openness. The study was conducted at three low-order sites in the Mulberry River Drainage (watershed area range: 81-232 km 2 ) seasonally in 2006 and 2007. We used circular statistics to examine community-wide shifts in isotope space among fish and invertebrate consumers in relation to basal resources, including detritus and periphyton. Mixing models were used to quantify the relative contribution of autochthonous and allochthonous energy sources to individual invertebrate consumers. Significant isotopic shifts occurred but results varied by season and site indicating substantial variation in the trophic base of stream food webs. In terms of temporal variation, consumers shifted toward periphyton in the summer during periods of low discharge, but results varied during the interval between summer and winter. Our results did not demonstrate increased reliance on periphyton with increasing watershed area or canopy openness, and detritus was important at all the sites. In our study, riffle-pool geomorphology likely disrupted the expected spatial pattern and stream drying likely impacted the availability and distribution of basal resources.

Hydrobiologia↗

The viability of a nonenzymatic reductive citric acid cycle - Kinetics and thermochemistry

The likelihood of a functioning nonenzymatic reductive citric acid cycle, recently proposed as the precursor to biosynthesis on early Earth, is examined on the basis of the kinetics and thermochemistry of the acetate → pyruvate → oxaloacetate → malate sequence. Using data derived from studies of the Pd-catalyzed phosphinate reduction of carbonyl functions it is shown that the rate of conversion of pyruvate to malate with that system would have been much too slow to have played a role in the early chemistry of life, while naturally occurring reduction systems such as the fayalite–magnetite–quartz and pyrrhotite–pyrite–magnetite mineral assemblages would have provided even slower conversions. It is also shown that the production of pyruvate from acetate is too highly endoergic to be driven by a naturally occurring energy source such as pyrophosphate. It is thus highly doubtful that the cycle can operate at suitable rates without enzymes, and most unlikely that it could have participated in the chemistry leading to life.

Origins of Life and Evolution of the Biosphere↗

Oxygen isotope exchange kinetics of mineral pairs in closed and open systems: Applications to problems of hydrothermal alteration of igneous rocks and Precambrian iron formations

The systematics of stable-isotope exchange between minerals and fluids are examined in the context of modal mineralogical variations and mass-balance considerations, both in closed and in open systems. On mineral-pair ??18O plots, samples from terranes that have exchanged with large amounts of fluid typically map out steep positively-sloped non-equilibrium arrays. Analytical models are derived to explain these effects; these models allow for different exchange rates between the various minerals and the external fluids, as well as different fluid fluxes. The steep arrays are adequately modelled by calculated isochron lines that involve the whole family of possible exchange trajectories. These isochrons have initially-steep near-vertical positive slopes that rotate toward a 45?? equilibrium slope as the exchange process proceeds to completion. The actual data-point array is thus analogous to the hand of an "isotopic clock" that measures the duration of the hydrothermal episode. The dimensionless ratio of the volumetric fluid flux to the kinetic rate parameter ( u k) determines the shape of each individual exchange trajectory. In a fluid-buffered system ( u k ??? 1), the solutions to the equations: (1) are independent of the mole fractions of the solid phases; (2) correspond to Taylor's open-system water/rock equation; and (3) yield straight-line isochrons that have slopes that approach 1 f, where f is the fraction reacted of the more sluggishly exchanging mineral. The isochrons for this simple exchange model are closely congruent with the isochrons calculated for all of the more complex models, thereby simplifying the application of theory to actual hydrothermal systems in nature. In all of the models an order of magnitude of time (in units of kt) separates steep non-equilibrium arrays (e.g., slope ??? 10) from arrays approaching an equilibrium slope of unity on a ??-?? diagram. Because we know the approximate lifetimes of many hydrothermal systems from geologic and heat-balance constraints, we can utilize the 18O 16O data on natural mineral assemblages to calculate the kinetic rate constants (k's) and the effective diffusion constants (D's) for mineral-H2O exchange: these calculated values (kqtz ??? 10-14, kfeld ??? 10-13-10-12) agree with experimental determinations of such constants. In nature, once the driving force or energy source for the external infiltrating fluid phase is removed, the disequilibrium mineral-pair arrays will either: (1) remain "frozen" in their existing state, if the temperatures are low enough, or (2) re-equilibrate along specific closed-system exchange vectors determined solely by the temperature path and the mineral modal proportions. Thus, modal mineralogical information is a particularly important parameter in both the open- and closed-system scenarios, and should in general always be reported in stable-isotopic studies of mineral assemblages. These concepts are applied to an analysis of 18O 16O systematics of gabbros (Plagioclase-clinopyroxene and plagioclase-amphibole pairs), granitic plutons (quartz-feldspar pairs), and Precambrian siliceous iron formations (quartz-magnetite pairs). In all these examples, striking regularities are observed on ??-?? and ??-?? plots, but we point out that ??-?? plots have many advantages over their equivalent ??-?? diagrams, as the latter are more susceptible to misinterpretation. Using the equations developed in this study, these regularities can be interpreted to give semiquantitative information on the exchange histories of these rocks subsequent to their formation. In particular, we present a new interpretation indicating that Precambrian cherty iron formations have in general undergone a complex fluid exchange history in which the iron oxide (magnetite precursor?) has exchanged much faster with low-temperature (< 400??C) fluids than has the relatively inert quartz. ?? 1989.

Chemical Geology↗

The concept of stress in fish

The general physiological response of fish to threatening situations, as with all vertebrates, is referred to as stress . A stress response is initiated almost immediately following the perception of a stressor. Mildly stressful situations can have beneficial or positive effects (eustress), while higher severities induce adaptive responses but also can have maladaptive or negative consequences (distress). The stress response is initiated and controlled by two hormonal systems , those leading to the production of corticosteroids (mainly cortisol) and catecholamines (such as adrenaline and noradrenaline and their precursor dopamine). Together these regulate the secondary stress response factors that alter the distribution of necessary resources such as energy sources and oxygen to vital areas of the body, as well as compromise hydromineral imbalance and the immune system. If fish can resist death due to a stressor, they recover to a similar or somewhat similar homeostatic norm. Long-term consequences of repeated or prolonged exposures to stress are maladaptive by negatively affecting other necessary life functions (growth, development, disease resistance, behavior, and reproduction), in large part because of the energetic cost associated with mounting the stress response (allostatic load). There is considerable variation in how fish respond to a stressor because of genetic differences among different taxa and also within stocks and species. Variations within the stress response are introduced by the environmental history of the fish, present ambient environmental conditions, and the fish's present physiological condition. Currently, fish physiology has progressed to the point where we can easily recognize when fish are stressed, but we cannot always recognize when fish are unstressed because the lack of clinical signs of stress does not always correspond to fish being unstressed. In other words, we need to be aware of the possibility of false negatives regarding clinical signs of stress. In addition, we cannot use clinical data to precisely or accurately infer severity of a stressor.

Fish Physiology↗

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development, north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH 4 gas content and its C isotopes (&delta; 13 C CH4 ), and select isotope tracers (&delta; 11 B, 87 Sr/ 86 Sr, &delta; 2 H, &delta; 18 O, &delta; 13 C DIC ) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH 4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH 4 /L. The &delta; 13 C CH4 of dissolved CH 4 ranged from &minus;42.3&permil; to &minus;74.7&permil;, with the most negative values characteristic of a biogenic source also associated with the highest observed CH 4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH 4 . The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (&delta; 13 C CH4 = &minus;35.4&permil; to &minus;41.9&permil;). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca&ndash;HCO 3 dominated, (3) TDS > 100 mg/L and Na&ndash;HCO 3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr ( 87 Sr/ 86 Sr = 0.7097&ndash;0.7166), C (&delta; 13 C DIC = &minus;21.3&permil; to &minus;4.7&permil;), and B (&delta; 11 B = 3.9&ndash;32.9&permil;) isotopes clearly reflect water&ndash;rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca&ndash;HCO 3 , and higher-mineralized Na&ndash;HCO 3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na&ndash;Cl type Fayetteville flowback/produced waters (TDS &sim;10,000&ndash;20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH 4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.

Applied Geochemistry↗

Cadmium isotope fractionation during coal combustion: Insights from two U.S. coal-fired power plants

Coal combustion, one of the principal energy sources of electricity in the United States, produces over 100 million tons of coal combustion products (CCPs) per year in the U.S. The reuse and disposal of CCPs has the potential to release toxic trace elements, including cadmium (Cd), into the environment. In this study, we investigated CCPs, including bottom ash (BA), economizer fly ash (EFA), and fly ash (FA), as well as feed coal (FC) and pulverized coal (PC) collected from two U.S. coal-fired power plants in New Mexico and Ohio with different coal supplies. The New Mexico plant uses high volatile C bituminous, low-sulfur coals mined from the San Juan Basin (Cretaceous Fruitland Formation) and the Ohio plant uses high volatile A bituminous, high-sulfur central Appalachian Basin coals (Upper Pennsylvanian Monongahela Formation). Mineralogical and elemental analysis showed that these CCP samples consist of ∼70% amorphous Al-Si-rich glasses and ∼30% mineral phases of quartz (SiO 2 ) and mullite (Ai 6 Si 2 O 13 ). The Cd isotope compositions (δ 114 Cd, normalized to NIST Cd standard 3108) of FA and EFA samples (ranging from −0.51 to +0.47‰) are distinctively heavier than those of BA samples (−0.75 to −0.52‰) in both power plants. We interpret this Cd isotope difference as a result of Cd condensation from the gas phase during flue gas cooling, instead of evaporation of Cd phase during coal combustion. Cd condensation is the main process to generate the isotopically heavy Cd signatures that preferentially partition on the fine FA particles. We also investigated Cd isotope compositions in different leachate products from a series of batch-leaching experiments with these CCPs, using diluted acetic acid, hydroxyl ammonium chloride, hydrogen peroxide followed by ammonium acetate, and 5% nitric acid, as a possible means to identify CCP-released Cd in the environment. Unusually and significantly heavier Cd isotope compositions were observed in each leachate of FA samples (+1.10 to +7.09‰), which fall far outside from the range of Cd isotope ratios observed in natural soils and rocks, but less so for the EFA samples (−0.43 to +1.18‰). Such an observation is consistent with the interpretation that isotopically heavy Cd preferentially partitions on the fine FA particles after coal combustion and is readily to be released during these leaching experiments. This study demonstrates that high-temperature coal combustion can lead to a very large degree of fractionation of Cd isotopes that can be used as a unique tracer for identifying anthropogenic metal inputs in the environment. The major Cd isotope fractionation process occurs as the Cd gas phase condenses on fine FA particles during the flue gas cooling stage after coal combustion.

New Mexico, Ohio↗

Intra-strain dioxin sensitivity and morphometric effects in swim-up rainbow trout ( Oncorhynchus mykiss )

Inter and intra-specific differences in sensitivity of early life stage salmonids to 2,3,7,8-TCDD exposure have been reported, but intra-strain differences have not been found in the literature. Our results indicate that intra-strain variability in terms of embryo mortality (LD50) is small in Eagle Lake strain of rainbow trout, LD50 values ranging from 285 to 457 pg TCDD egg g −1 . These results confirm Eagle Lake as a less sensitive strain within rainbow trout, and do not indicate overlap with reported LD50 values for brook or lake trout. Our results also demonstrate that although generalized edema in regions including the yolk-sac are frequently associated with mortality following dioxin exposure, not all edematous fish die. We detected dose-dependent decreases in cranial length, eye diameter, mass, and total length ( P <0.05) in viable swim-up rainbow trout. These effects are presumed to indicate more subtle dose-dependent disruptions of the viteline vein vasculature and, therefore, in access to energy sources. A tendency for dose-dependent decrease in liver glycogen reserves concurred with previous results on salmonids and with the well described TCDD-induced alterations in intermediate metabolism of rats and chicken embryos (wasting syndrome). This syndrome could be contributing to the reduced growth that we observed.

Comparative Biochemistry and Physiology, Part C: T↗

Pathways of productivity and influences on top consumers in forested streams

Forested stream ecosystems involve complex physical and biotic pathways that can influence fish in numerous ways. Consequently, the responses of fish communities to disturbance can be difficult to understand. In this study, we employed a food web model that links biotic (e.g., physiology, predator–prey interactions) and abiotic (e.g., temperature, sunlight) attributes to address fish responses to changes in stream-riparian ecosystems. We modeled responses to food web dynamics in four streams, using scenarios that included responses to riparian disturbance, climate change, and shifts in top consumers. The two consumers we focused on were coastal cutthroat trout ( Oncorhynchus clarkii clarkii ) and sculpin ( Cottus spp., collectively treated as a functional group) . We found the responses to environmental changes varied by fish species and among streams, and that responses were not independent due to exploitative interspecific competition. Simulations based on long-term data indicated that coastal cutthroat trout were responsive to changes in allochthonous resources including terrestrial detritus and invertebrates, whereas sculpin were more responsive to changes to autochthonous resources that included, periphyton and aquatic invertebrates. These results may be, in part, a consequence of species-specific foraging behavior. Trout have a higher propensity to drift feed and therefore receive a substantial subsidy from terrestrial invertebrates, whereas sculpin feed mostly on aquatic insects on the streambed. Simulations of changes in summer temperature and stream discharge suggest decreased biomass of both fish species because of physiological constraints on invertebrate prey which reduce fish foraging opportunities. Exploitative competition also may be important in fish responses: when one fish taxon was removed, the other showed increased biomass. Although the pattern of simulation results was consistent across the four streams, the magnitude of change varied among streams. Streams with food webs fueled by multiple energy sources may be more resilient to changes to riparian forests and climate. Through application of a systems model, we gained insights into pathways of productivity for fish in forested stream ecosystems that provide understanding of processes that influence fish and streams, as well as implications for management of both.

Forest Ecology and Management↗