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Modification of pure oxygen absorption equipment for concurrent stripping of carbon dioxide

The high solubility of carbon dioxide precludes significant desorption within commercial oxygen absorption equipment. This operating characteristic of the equipment limits its application in recirculating water culture systems despite its ability to significantly increase allowable fish loading rates (kg/(L min)). Carbon dioxide (DC) is typically removed by air stripping. This process requires a significant energy input for forced air movement, air heating in cold climates and water pumping. We developed a modification for a spray tower that provides for carbon dioxide desorption as well as oxygen absorption. Elimination of the air-stripping step reduces pumping costs while allowing dissolved nitrogen to drop below saturation concentrations. This latter response provides for an improvement in oxygen absorption efficiency within the spray tower. DC desorption is achieved by directing head-space gases from the spray tower (O2, N2, CO2) through a sealed packed tower scrubber receiving a 2 N NaOH solution. Carbon dioxide is selectively removed from the gas stream, by chemical reaction, forming the product Na 2CO3. Scrubber off-gas, lean with regard to carbon dioxide but still rich with oxygen, is redirected through the spray tower for further stripping of DC and absorption of oxygen. Make-up NaOH is metered into the scrubbing solution sump on an as needed basis as directed by a feedback control loop programmed to maintain a scrubbing solution pH of 11.4-11.8. The spent NaOH solution is collected, then regenerated for reuse, in a batch process that requires relatively inexpensive hydrated lime (Ca(OH)2). A by-product of the regeneration step is an alkaline filter cake, which may have use in bio-solids stabilization. Given the enhanced gas transfer rates possible with chemical reaction, the required NaOH solution flow rate through the scrubber represents a fraction of the spray tower water flow rate. Further, isolation of the water being treated from the atmosphere (1), allows for an improvement in oxygen absorption efficiency by maintaining DN well below local saturation concentrations (2), minimizes building energy requirements related to heating and ventilation and (3), reduces the potential for pathogen transmittance. We report on the performance of a test scrubber evaluated over a range of NaOH solution temperatures, pH, packing irrigation rates, and gas stream compositions. We also describe our experience with the process in a pilot scale recirculating water (trout) production system.

Conference Paper↗

Comparative performance of fixed-film biological filters: Application of reactor theory

Nitrification is classified as a two-step consecutive reaction where R1 represents the rate of formation of the intermediate product NO2-N and R2 represents the rate of formation of the final product NO3-N. The relative rates of R1 and R2 are influenced by reactor type characterized hydraulically as plug-flow, plug-flow with dispersion and mixed-flow. We develop substrate conversion models for fixed-film biofilters operating in the first-order kinetic regime based on application of chemical reactor theory. Reactor type, inlet conditions and the biofilm kinetic constants Ki (h-1) are used to predict changes in NH4-N, NO2-N, NO3-N and BOD5. The inhibiting effects of the latter on R1 and R2 were established based on the ?? relation, e.g.:{A formula is presented}where BOD5,max is the concentration that causes nitrification to cease and N is a variable relating Ki to increasing BOD5. Conversion models were incorporated in spreadsheet programs that provided steady-state concentrations of nitrogen and BOD5 at several points in a recirculating aquaculture system operating with input values for fish feed rate, reactor volume, microscreen performance, make-up and recirculating flow rates. When rate constants are standardized, spreadsheet use demonstrates plug-flow reactors provide higher rates of R1 and R2 than mixed-flow reactors thereby reducing volume requirements for target concentrations of NH4-N and NO2-N. The benefit provided by the plug-flow reactor varies with hydraulic residence time t as well as the effective vessel dispersion number, D/??L. Both reactor types are capable of providing net increases in NO2-N during treatment but the rate of decrease in the mixed-flow case falls well behind that predicted for plug-flow operation. We show the potential for a positive net change in NO2-N increases with decreases in the dimensionless ratios K2, (R2 )/K1,( R1 ) and [NO2-N]/[NH4-N] and when the product K1, (R1) t provides low to moderate NH4-N conversions. Maintaining high levels of the latter reduces the effective reactor utilization rate (%) defined here as (RNavg/RNmax)100 where RNavg is the mean reactive nitrogen concentration ([NH4-N] + [NO2-N]) within the reactor, and RNmax represents the feed concentration of the same. Low utilization rates provide a hedge against unexpected increases in substrate loading and reduce water pumping requirements but force use of elevated reactor volumes. Further ?? effects on R1 and R2 can be reduced through use of a tanks-in-series versus a single mixed-flow reactor configuration and by improving the solids removal efficiency of microscreen treatment.

Aquacultural Engineering↗

Design of a computerized, temperature-controlled, recirculating aquaria system

We built a recirculating aquaria system with computerized temperature control to maintain static temperatures, increase temperatures 1 ??C/day, and maintain diel temperature fluctuations up to 10 ??C. A LabVIEW program compared the temperature recorded by thermocouples in fish tanks to a desired set temperature and then calculated the amount of hot or cold water to add to tanks to reach or maintain the desired temperature. Intellifaucet?? three-way mixing valves controlled temperature of the input water and ensured that all fish tanks had the same turnover rate. The system was analyzed over a period of 50 days and was fully functional for 96% of that time. Six different temperature treatments were run simultaneously in 18, 72 L fish tanks and temperatures stayed within 0.5 ??C of set temperature. We used the system to determine the upper temperature tolerance of fishes, but it could be used in aquaculture, ecological studies, or other aquatic work where temperature control is required. ?? 2005 Elsevier B.V. All rights reserved.

Aquacultural Engineering↗

Historical deposition of mercury and selected trace elements to high-elevation National Parks in the Western U.S. inferred from lake-sediment cores

Atmospheric deposition of Hg and selected trace elements was reconstructed over the past 150 years using sediment cores collected from nine remote, high-elevation lakes in Rocky Mountain National Park in Colorado and Glacier National Park in Montana. Cores were age dated by 210 Pb, and sedimentation rates were determined using the constant rate of supply model. Hg concentrations in most of the cores began to increase around 1900, reaching a peak sometime after 1980. Other trace elements, particularly Pb and Cd, showed similar post-industrial increases in lake sediments, confirming that anthropogenic contaminants are reaching remote areas of the Rocky Mountains via atmospheric transport and deposition. Preindustrial (pre-1875) Hg fluxes in the sediment ranged from 5.7 to 42 μg m −2 yr −1 and modern (post-1985) fluxes ranged from 17.7 to 141 μg m −2 yr −1 . The average ratio of modern to preindustrial fluxes was 3.2, which is similar to remote lakes elsewhere in North America. Estimates of net atmospheric deposition based on the cores were 3.1 μg m −2 yr −1 for preindustrial and 11.7 μg m −2 yr −1 for modern times. Current-day measurements of wet deposition range from 5.0 to 8.6 μg m −2 yr −1 , which are lower than the modern sediment-based estimate of 11.7 μg m −2 yr −1 , perhaps owing to inputs of dry-deposited Hg to the lakes.

Atmospheric Environment↗

Short-term nitrogen additions can shift a coastal wetland from a sink to a source of N 2 O

Coastal salt marshes sequester carbon at high rates relative to other ecosystems and emit relatively little methane particularly compared to freshwater wetlands. However, fluxes of all major greenhouse gases (N 2 O, CH 4 , and CO 2 ) need to be quantified for accurate assessment of the climatic roles of these ecosystems. Anthropogenic nitrogen inputs (via run-off, atmospheric deposition, and wastewater) impact coastal marshes. To test the hypothesis that a pulse of nitrogen loading may increase greenhouse gas emissions from salt marsh sediments, we compared N 2 O, CH 4 and respiratory CO 2 fluxes from nitrate-enriched plots in a Spartina patens marsh (receiving single additions of NaNO 3 equivalent to 1.4 g N m −2 ) to those from control plots (receiving only artificial seawater solutions) in three short-term experiments (July 2009, April 2010, and June 2010). In July 2009, we also compared N 2 O and CH 4 fluxes in both opaque and transparent chambers to test the influence of light on gas flux measurements. Background fluxes of N 2 O in July 2009 averaged −33 μmol N 2 O m −2 day −1 . However, within 1 h of nutrient additions, N 2 O fluxes were significantly greater in plots receiving nitrate additions relative to controls in July 2009. Respiratory rates and CH 4 fluxes were not significantly affected. N 2 O fluxes were significantly higher in dark than in transparent chambers, averaging 108 and 42 μmol N 2 O m −2 day −1 respectively. After 2 days, when nutrient concentrations returned to background levels, none of the greenhouse gas fluxes differed from controls. In April 2010, N 2 O and CH 4 fluxes were not significantly affected by nitrate, possibly due to higher nitrogen demands by growing S. patens plants, but in June 2010 trends of higher N 2 O fluxes were again found among nitrate-enriched plots, indicating that responses to nutrient pulses may be strongest during the summer. In terms of carbon equivalents, the highest average N 2 O and CH 4 fluxes observed, exceeded half the magnitude of typical daily net carbon sequestration rates by salt marshes. Thus, anthropogenic additions of nitrate to coasts can substantially alter N 2 O fluxes from marshes, although substantial temporal variation in these fluxes was observed. To better assess the climatic roles of salt marshes, greenhouse gas emissions need to be studied in the context of chronic nitrogen loads that impact many coastal ecosystems.

Atmospheric Environment↗

A radiogenic isotope tracer study of transatlantic dust transport from Africa to the Caribbean

Many studies have suggested that long-range transport of African desert dusts across the Atlantic Ocean occurs, delivering key nutrients and contributing to fertilization of the Amazon rainforest. Here we utilize radiogenic isotope tracers – Sr, Nd and Pb – to derive the provenance, local or remote, and pathways of dust transport from Africa to the Caribbean. Atmospheric total suspended particulate (TSP) matter was collected in 2008 on quartz fibre filters, from both sides of the Atlantic Ocean at three different locations: in Mali (12.6°N, 8.0°W; 555 m a.s.l.), Tobago (11.3°N, 60.5°W; 329 m a.s.l.) and the U.S. Virgin Islands (17.7°N, 64.6°W; 27 m a.s.l.). Both the labile phase, representative of the anthropogenic signal, and the refractory detrital silicate fraction were analysed. Dust deposits and soils from around the sampling sites were measured as well to assess the potential contribution from local sources to the mineral dust collected. The contribution from anthropogenic sources of Pb was predominant in the labile, leachate phase. The overall similarity in Pb isotope signatures found in the leachates is attributed to a common African source of anthropogenic Pb, with minor inputs from other sources, such as from Central and South America. The Pb, Sr and Nd isotopic compositions in the silicate fraction were found to be systematically more radiogenic than those in the corresponding labile phases. In contrast, Nd and Sr isotopic compositions from Mali, Tobago, and the Virgin Islands are virtually identical in both leachates and residues. Comparison with existing literature data on Saharan and Sahelian sources constrains the origin of summer dust transported to the Caribbean to mainly originate from the Sahel region, with some contribution from northern Saharan sources. The source regions derived from the isotope data are consistent with 7-day back-trajectory analyses, demonstrating the usefulness of radiogenic isotopes in tracing dust provenance and atmospheric transport.

Africa;Atlantic Ocean;Caribbean;Sahara;Sahel↗

Identifying marine Important Bird Areas using at-sea survey data

Effective marine bird conservation requires identification of at-sea locations used by populations for foraging, staging, and migration. Using an extensive database of at-sea survey data spanning over 30 years, we developed a standardized and data-driven spatial method for identifying globally significant marine Important Bird Areas in Alaska. To delineate these areas we developed a six-step process: binning data and accounting for unequal survey effort, filtering input data for persistence of species use, using a moving window analysis to produce maps representing a gradient from low to high abundance, drawing core area boundaries around major concentrations based on abundance thresholds, validating the results, and combining overlapping boundaries into important areas for multiple species. We identified 126 bird core areas which were merged into 59 pelagic sites important to 45 out of 57 species assessed. The final areas included approximately 34–38% of all marine birds in Alaska waters, within just 6% of the total area. We identified globally significant Important Bird Areas spanning 20 degrees of latitude and 56 degrees of longitude, in two different oceans, with climates ranging from temperate to polar. Although our maps did suffer from some data gaps, these gaps did not preclude us from identifying sites that incorporated 13% of the assessed continental waterbird population and 9% of the assessed global seabird population. The application of this technique over a large and productive region worked well for a wide range of birds, exhibiting a variety of foraging strategies and occupying a variety of ecosystem types.

Alaska↗

Citizen science can improve conservation science, natural resource management, and environmental protection

Citizen science has advanced science for hundreds of years, contributed to many peer-reviewed articles, and informed land management decisions and policies across the United States. Over the last 10 years, citizen science has grown immensely in the United States and many other countries. Here, we show how citizen science is a powerful tool for tackling many of the challenges faced in the field of conservation biology. We describe the two interwoven paths by which citizen science can improve conservation efforts, natural resource management, and environmental protection. The first path includes building scientific knowledge, while the other path involves informing policy and encouraging public action. We explore how citizen science is currently used and describe the investments needed to create a citizen science program. We find that: Citizen science already contributes substantially to many domains of science, including conservation, natural resource, and environmental science. Citizen science informs natural resource management, environmental protection, and policymaking and fosters public input and engagement. Many types of projects can benefit from citizen science, but one must be careful to match the needs for science and public involvement with the right type of citizen science project and the right method of public participation. Citizen science is a rigorous process of scientific discovery, indistinguishable from conventional science apart from the participation of volunteers. When properly designed, carried out, and evaluated, citizen science can provide sound science, efficiently generate high-quality data, and help solve problems.

Biological Conservation↗

Modeling coupled dynamics of an empirical predator-prey system to predict top predator recovery

Limited data, time, and funding lead conservation managers to make difficult choices in managing species recovery. Coupled dynamical models are relied upon for decision support, but their application to empirical predator-prey systems has generally been restricted to small, tractable species. To broaden their use in conservation decision-making, we developed a model suitable for predicting the population dynamics of a larger apex carnivore and its prey. We selected southern sea otters ( Enhydra lutris nereis ) and their primary estuarine prey as our case study and parameterized the dynamical model with data on sea otter, clam, and crab abundances; predator-prey interactions; and sea otter bioenergetics collected from Elkhorn Slough, CA. Our model, having integrated all these salient factors, was able to successfully reproduce trends in taxa abundance as well as shifts in sea otter diet composition and energy intake rates. Rich data inputs allow the model to predict population dynamics over realistic temporal scales not only for the site of data collection, but also for similar estuaries uncolonized by sea otters. Based on model projections parameterized with prey survey data from two such estuaries, Tomales Bay and Drakes Estero, we predict the sites could support over 160 sea otters and may hold potential to further species recovery. In systems with good data availability, the model has high predictive power and can provide multi-taxa projections useful for making informed management decisions.

California↗

A visual basic program to generate sediment grain-size statistics and to extrapolate particle distributions

Measures that describe and summarize sediment grain-size distributions are important to geologists because of the large amount of information contained in textural data sets. Statistical methods are usually employed to simplify the necessary comparisons among samples and quantify the observed differences. The two statistical methods most commonly used by sedimentologists to describe particle distributions are mathematical moments (Krumbein and Pettijohn, 1938) and inclusive graphics (Folk, 1974). The choice of which of these statistical measures to use is typically governed by the amount of data available (Royse, 1970). If the entire distribution is known, the method of moments may be used; if the next to last accumulated percent is greater than 95, inclusive graphics statistics can be generated. Unfortunately, earlier programs designed to describe sediment grain-size distributions statistically do not run in a Windows environment, do not allow extrapolation of the distribution's tails, or do not generate both moment and graphic statistics (Kane and Hubert, 1963; Collias et al., 1963; Schlee and Webster, 1967; Poppe et al., 2000) 1 . Owing to analytical limitations, electro-resistance multichannel particle-size analyzers, such as Coulter Counters, commonly truncate the tails of the fine-fraction part of grain-size distributions. These devices do not detect fine clay in the 0.6–0.1 μm range (part of the 11-phi and all of the 12-phi and 13-phi fractions). Although size analyses performed down to 0.6 μm microns are adequate for most freshwater and near shore marine sediments, samples from many deeper water marine environments (e.g. rise and abyssal plain) may contain significant material in the fine clay fraction, and these analyses benefit from extrapolation. The program (GSSTAT) described herein generates statistics to characterize sediment grain-size distributions and can extrapolate the fine-grained end of the particle distribution. It is written in Microsoft Visual Basic 6.0 and provides a window to facilitate program execution. The input for the sediment fractions is weight percentages in whole-phi notation (Krumbein, 1934; Inman, 1952), and the program permits the user to select output in either method of moments or inclusive graphics statistics (Fig. 1). Users select options primarily with mouse-click events, or through interactive dialogue boxes.

Computers & Geosciences↗

An efficient Matlab script to calculate heterogeneous anisotropically elastic wave propagation in three dimensions

We have created a second-order finite-difference solution to the anisotropic elastic wave equation in three dimensions and implemented the solution as an efficient Matlab script. This program allows the user to generate synthetic seismograms for three-dimensional anisotropic earth structure. The code was written for teleseismic wave propagation in the 1-0.1 Hz frequency range but is of general utility and can be used at all scales of space and time. This program was created to help distinguish among various types of lithospheric structure given the uneven distribution of sources and receivers commonly utilized in passive source seismology. Several successful implementations have resulted in a better appreciation for subduction zone structure, the fate of a transform fault with depth, lithospheric delamination, and the effects of wavefield focusing and defocusing on attenuation. Companion scripts are provided which help the user prepare input to the finite-difference solution. Boundary conditions including specification of the initial wavefield, absorption and two types of reflection are available. ?? 2005 Elsevier Ltd. All rights reserved.

Computers & Geosciences↗

A Visual Basic program to plot sediment grain-size data on ternary diagrams

Sedimentologic datasets are typically large and compiled into tables or databases, but pure numerical information can be difficult to understand and interpret. Thus, scientists commonly use graphical representations to reduce complexities, recognize trends and patterns in the data, and develop hypotheses. Of the graphical techniques, one of the most common methods used by sedimentologists is to plot the basic gravel, sand, silt, and clay percentages on equilateral triangular diagrams. This means of presenting data is simple and facilitates rapid classification of sediments and comparison of samples. The original classification scheme developed by Shepard (1954) used a single ternary diagram with sand, silt, and clay in the corners and 10 categories to graphically show the relative proportions among these three grades within a sample. This scheme, however, did not allow for sediments with significant amounts of gravel. Therefore, Shepard's classification scheme was later modified by the addition of a second ternary diagram with two categories to account for gravel and gravelly sediment (Schlee, 1973). The system devised by Folk (1954, 1974)\ is also based on two triangular diagrams, but it has 21 categories and uses the term mud (defined as silt plus clay). Patterns within the triangles of both systems differ, as does the emphasis placed on gravel. For example, in the system described by Shepard, gravelly sediments have more than 10% gravel; in Folk's system, slightly gravelly sediments have as little as 0.01% gravel. Folk's classification scheme stresses gravel because its concentration is a function of the highest current velocity at the time of deposition as is the maximum grain size of the detritus that is available; Shepard's classification scheme emphasizes the ratios of sand, silt, and clay because they reflect sorting and reworking (Poppe et al., 2005). The program described herein (SEDPLOT) generates verbal equivalents and ternary diagrams to characterize sediment grain-size distributions. It is written in Microsoft Visual Basic 6.0 and provides a window to facilitate program execution. The inputs for the sediment fractions are percentages of gravel, sand, silt, and clay in the Wentworth (1922) grade scale, and the program permits the user to select output in either the Shepard (1954) classification scheme, modified as described above, or the Folk (1954, 1974) scheme. Users select options primarily with mouse-click events and through interactive dialogue boxes. This program is intended as a companion to other Visual Basic software we have developed to process sediment data (Poppe et al., 2003, 2004).

Computers & Geosciences↗

Methods for simulating solute breakthrough curves in pumping groundwater wells

In modeling there is always a trade-off between execution time and accuracy. For gradient-based parameter estimation methods, where a simulation model is run repeatedly to populate a Jacobian (sensitivity) matrix, there exists a need for rapid simulation methods of known accuracy that can decrease execution time, and thus make the model more useful without sacrificing accuracy. Convolution-based methods can be executed rapidly for any desired input function once the residence-time distribution is known. The residence-time distribution can be calculated efficiently using particle tracking, but particle tracking can be ambiguous near a pumping well if the grid is too coarse. We present several embedded analytical expressions for improving particle tracking near a pumping well and compare them with a finely gridded finite-difference solution in terms of accuracy and CPU usage. Even though the embedded analytical approach can improve particle tracking near a well, particle methods reduce, but do not eliminate, reliance on a grid because velocity fields typically are calculated on a grid, and additional error is incurred using linear interpolation of velocity. A dilution rate can be calculated for a given grid and pumping well to determine if the grid is sufficiently refined. Embedded analytical expressions increase accuracy but add significantly to CPU usage. Structural error introduced by the numerical solution method may affect parameter estimates.

Computers & Geosciences↗

MTpy: A Python toolbox for magnetotellurics

We present the software package MTpy that allows handling, processing, and imaging of magnetotelluric (MT) data sets. Written in Python, the code is open source, containing sub-packages and modules for various tasks within the standard MT data processing and handling scheme. Besides the independent definition of classes and functions, MTpy provides wrappers and convenience scripts to call standard external data processing and modelling software. In its current state, modules and functions of MTpy work on raw and pre-processed MT data. However, opposite to providing a static compilation of software, we prefer to introduce MTpy as a flexible software toolbox, whose contents can be combined and utilised according to the respective needs of the user. Just as the overall functionality of a mechanical toolbox can be extended by adding new tools, MTpy is a flexible framework, which will be dynamically extended in the future. Furthermore, it can help to unify and extend existing codes and algorithms within the (academic) MT community. In this paper, we introduce the structure and concept of MTpy . Additionally, we show some examples from an everyday work-flow of MT data processing: the generation of standard EDI data files from raw electric ( E -) and magnetic flux density ( B -) field time series as input, the conversion into MiniSEED data format, as well as the generation of a graphical data representation in the form of a Phase Tensor pseudosection.

Computers & Geosciences↗

Fingerprinting historical tributary contributions to floodplain sediment using bulk geochemistry

Sediment deposition on floodplains is essential for the development and maintenance of riparian ecosystems. Upstream erosion is known to influence downstream floodplain construction, but linking these disparate processes is challenging, especially over large spatial and temporal scales. Sediment fingerprinting is thus a robust tool to establish process linkages between downstream floodplain development and sediment production in distal headwater basins. Here we use sediment geochemistry to connect historical erosion in several tributaries of the Yampa River in Colorado and Wyoming, USA, to the construction of downstream floodplains on which extensive cottonwood forests established. Using a combination of conventional techniques and the relatively novel machine-learning random forest algorithm, we build multiple fingerprints of diagnostic geochemical tracers that are then input into a Bayesian mixing model to apportion provenance of floodplain sediment. Sediment samples for provenance analysis were collected from an excavated floodplain in Deerlodge Park on the Yampa River at the rooting surface of the surrounding cottonwood forest and dominantly comprised of very fine (4Φ) sand. Fingerprinting analysis of the 4Φ fraction of collected floodplain sink (n = 38) and tributary source (n = 218) samples revealed floodplain sediment to be dominantly sourced from the tributaries of Muddy Creek (45 ± 4%) and Sand Wash (42 ± 6%). Dendrochronology results moreover indicate the Deerlodge floodplain sediment was deposited in ∼1912, which falls squarely within the time (1880–1940) these tributaries were actively eroding. Taken together, study results indicate a demonstrable link between historical tributary erosion and downstream floodplain construction and concomitant forest establishment. Our findings suggest processes operating in tributary watersheds play an important role in the dynamics of large rivers and emphasize both the need for holistic, collaborative management of sediment as an essential resource and the potential to utilize sediment fingerprinting to inform and direct river ecosystem management.

Colorado, Wyoming↗

Chemical openness and potential for misinterpretation of the solute environment of coastal sabkhat

Sabkha deposits in the geologic record are commonly used to interpret the environmental conditions of deposition. Implicit in this use is the assumption that the solute system is chemically closed, that is, the authigenic minerals represent the composition of the fluids in their environment of origin. Thermodynamic and mass-balance calculations based on measurements of water and solute flux of contemporary Abu Dhabi coastal sabkha system, however, demonstrate that the system is open for sodium and chloride, where nearly half of the input is lost, but closed for sulfur, where nearly 100% is retained. Sulfur and chloride isotopes were consistent with this observation. If these sabkha deposits were preserved in the geologic record, they would suggest a solute environment rich in sulfate and poor in chloride; yet the reverse is true. In most coastal-sabkha environments, capillary forces bring solutes and water to the surface, where the water evaporates and halite, carnallite, sylvite, and other soluble minerals are precipitated. Retrograde minerals, such as anhydrite, calcite, dolomite, and gypsum, however, precipitate and accumulate in the capillary zone beneath the surface of the coastal sabkha. Because they possess relatively low solubility and are below the surface, these retrograde minerals are protected from dissolution and physical erosion occurring from infrequent but intense rainfall events. Thus, they are more likely to be preserved in the geological record than highly soluble minerals formed on the surface. ?? 2004 Elsevier B.V. All rights reserved.

Chemical Geology↗

High arsenic concentrations and enriched sulfur and oxygen isotopes in a fractured-bedrock ground-water system

Ground water with high arsenic concentrations (up to 26.6????mol L- 1) has sulfate enriched in 34S and 18O in the fractured-bedrock, ground-water system of the Kelly's Cove watershed, Northport, Maine, USA. The ranges of sulfur and oxygen isotope values in aqueous sulfate, ??34S[SO4] and ??18O[SO4], at the Kelly's Cove watershed are + 3.4 to + 4.9??? and - 2.0 to + 6.7???, respectively. These isotope values are strikingly similar to those of the Goose River, Maine watershed which has ??34S[SO4] and ??18O[SO4] ranges of + 3.7 to + 4.6 ??? and - 2.6 to + 7.5???, respectively. In both systems, high arsenic concentrations occur with high ??34S[SO4] and ??18O[SO4] values, yet redox conditions and underlying rock types are quite different. The isotope values of sulfide minerals, ??34S[min], from four bedrock cores vary over short distances and range from - 5.1 to + 7.5???. The ??34S[SO4] values are controlled by the ??34S[min] values with minor input of atmospheric SO4. The much narrower range in ??34S[SO4] values than ??34S[min] values is probably due to sufficient ground-water mixing at a scale greater than the ??34S[min] variability. The ??34S[SO4] values are about 2??? higher than the average ??34S[min] value and fall within the range of ??34S[min] values, indicating only minor fractionation due to bacterial reduction of SO4. The highest ??18O[SO4] values were measured in the downgradient, confined, arsenic-rich ground water. High ??18O[SO4] values there cannot be due to aeration by atmospheric oxygen, but may arise from reoxidation of reduced SO4 products. The enrichment factors of ??18O in SO4 compared to H2O, + 7.2 to + 15.5???, in the Kelly's Cove ground water and the negligible 34S enrichment is very similar to those derived from experimental data of anaerobic sulfide oxidation in the presence of Mn and Fe oxides. Sea level at the Kelly's Cove watershed was approximately 80??m above present sea level about 13 000??years before present, imposing reducing conditions on that area of the watershed. Sea level dropped approximately 60??m below present sea level about 11 000??years before present, allowing for possible oxidation of sulfide minerals and precipitation of arsenic in ferric oxyhydroxides during aeration of the ground-water system. Under present redox conditions, there is evidence that bacteria reduction of ferric oxyhydroxides releases arsenic. The fractionation of 18O in the SO4 during anaerobic oxidation of sulfide in the presence of Mn and Fe oxides and subsequent release of arsenic during Mn and Fe oxide reduction may explain the relationship between high arsenic concentrations and elevated 18O[SO4] at Kelly's Cove. ?? 2007 Elsevier B.V. All rights reserved.

Chemical Geology↗

Changing sources of strontium to soils and ecosystems across the Hawaiian Islands

Strontium isotope ratios assist ecosystem scientists in constraining the sources of alkaline earth elements, but their interpretation can be difficult because of complexities in mineral weathering and in the geographical and environmental controls on elemental additions and losses. Hawaii is a "natural laboratory" where a number of important biogeochemical variables have either limited ranges or vary in systematic ways, providing a unique opportunity to understand the impact of time, climate, and atmospheric inputs on the evolution of base cation sources to ecosystems. There are three major sources of strontium (Sr) to these ecosystems, each with distinct isotopic compositions: basalt lava, Asian dust, and rainfall. We present Sr isotope and concentration data on both bulk soil digests and NH 4 Ac extracts from soil profiles covering a wide range of environments and substrate ages. Bulk soil material from dry climates and/or young substrate ages with > 80????g g - 1 Sr retain basalt-like Sr isotopic signatures, whereas those with Sr concentrations < 80????g g - 1 can have isotope signatures that range from basalt-like values to the more radiogenic values associated with continental dust. Although both dust accumulation and lava weathering are time- and rainfall-dependent, the overall concentration of Sr drops with increasing leaching even as quartz and mica derived from continental dust sources increase to > 40% by mass. At elevated dust levels, lava-derived Sr is low and dust-derived Sr is the dominant control of 87 Sr/ 86 Sr in bulk soils; however, 87 Sr/ 86 Sr of NH 4 Ac-extractable Sr largely reflects atmospheric deposition of marine aerosol in these situations. Overall, whole-soil Sr isotope values are controlled by complex interactions between Sr provided by lava weathering but partially lost by leaching, and Sr provided by dust but held in more resistant minerals. The isotopic composition of NH 4 Ac-extractable Sr and of the biota is controlled by lava weathering and rainfall contribution of Sr with only minor contributions from radiogenic dust sources. ?? 2009 Elsevier B.V.

Chemical Geology↗

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