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At least 469 records · Page 26Linked to original sources

Bias and uncertainty in regression-calibrated models of groundwater flow in heterogeneous media

Groundwater models need to account for detailed but generally unknown spatial variability (heterogeneity) of the hydrogeologic model inputs. To address this problem we replace the large, m-dimensional stochastic vector ?? that reflects both small and large scales of heterogeneity in the inputs by a lumped or smoothed m-dimensional approximation ????*, where ?? is an interpolation matrix and ??* is a stochastic vector of parameters. Vector ??* has small enough dimension to allow its estimation with the available data. The consequence of the replacement is that model function f(????*) written in terms of the approximate inputs is in error with respect to the same model function written in terms of ??, ??,f(??), which is assumed to be nearly exact. The difference f(??) - f(????*), termed model error, is spatially correlated, generates prediction biases, and causes standard confidence and prediction intervals to be too small. Model error is accounted for in the weighted nonlinear regression methodology developed to estimate ??* and assess model uncertainties by incorporating the second-moment matrix of the model errors into the weight matrix. Techniques developed by statisticians to analyze classical nonlinear regression methods are extended to analyze the revised method. The analysis develops analytical expressions for bias terms reflecting the interaction of model nonlinearity and model error, for correction factors needed to adjust the sizes of confidence and prediction intervals for this interaction, and for correction factors needed to adjust the sizes of confidence and prediction intervals for possible use of a diagonal weight matrix in place of the correct one. If terms expressing the degree of intrinsic nonlinearity for f(??) and f(????*) are small, then most of the biases are small and the correction factors are reduced in magnitude. Biases, correction factors, and confidence and prediction intervals were obtained for a test problem for which model error is large to test robustness of the methodology. Numerical results conform with the theoretical analysis. ?? 2005 Elsevier Ltd. All rights reserved.

Advances in Water Resources↗

Assessing the impact of land use change on hydrology by ensemble modeling (LUCHEM). I: Model intercomparison with current land use

This paper introduces the project on 'Assessing the impact of land use change on hydrology by ensemble modeling (LUCHEM)' that aims at investigating the envelope of predictions on changes in hydrological fluxes due to land use change. As part of a series of four papers, this paper outlines the motivation and setup of LUCHEM, and presents a model intercomparison for the present-day simulation results. Such an intercomparison provides a valuable basis to investigate the effects of different model structures on model predictions and paves the ground for the analysis of the performance of multi-model ensembles and the reliability of the scenario predictions in companion papers. In this study, we applied a set of 10 lumped, semi-lumped and fully distributed hydrological models that have been previously used in land use change studies to the low mountainous Dill catchment, Germany. Substantial differences in model performance were observed with Nash-Sutcliffe efficiencies ranging from 0.53 to 0.92. Differences in model performance were attributed to (1) model input data, (2) model calibration and (3) the physical basis of the models. The models were applied with two sets of input data: an original and a homogenized data set. This homogenization of precipitation, temperature and leaf area index was performed to reduce the variation between the models. Homogenization improved the comparability of model simulations and resulted in a reduced average bias, although some variation in model data input remained. The effect of the physical differences between models on the long-term water balance was mainly attributed to differences in how models represent evapotranspiration. Semi-lumped and lumped conceptual models slightly outperformed the fully distributed and physically based models. This was attributed to the automatic model calibration typically used for this type of models. Overall, however, we conclude that there was no superior model if several measures of model performance are considered and that all models are suitable to participate in further multi-model ensemble set-ups and land use change scenario investigations. ?? 2008 Elsevier Ltd. All rights reserved.

Advances in Water Resources↗

Effect of spatial and temporal scale on simulated groundwater recharge investigations

Hydrologic model input datasets such as climate, land use, elevation, soil, and geology information are available in a range of scales for use in water resources investigations. Smaller spatial and temporal scale input data allow groundwater recharge models to simulate more physically realistic processes and presumably result in more accurate estimates of groundwater recharge. Projected climate data are, therefore, often downscaled to smaller spatial and temporal scales for use in these models. It is unknown, however, if increasingly smaller-scale climate data produce substantially different simulated recharge results, either in magnitude or trend. Also, even if simulated recharge results are different at a higher space and time resolution, simulation at coarser resolution might be adequate to provide recharge information at decision scales (e.g., meeting Colorado River compact requirements on a ten-year moving average basis). Historical climate datasets at three spatial (∼800 m, ∼4 km, and ∼12 km) and two temporal (daily and monthly) scales were used in a Soil Water Balance (SWB) model of the upper Colorado River basin (UCRB) to simulate groundwater recharge over the water-year 1982–2014 time period. The magnitude of annual and moving ten-year annual average recharge results for daily climate data were within 5% and 7% of ∼4 km results for ∼800 m and ∼12 km climate data, respectively, with deviations from 1982 to 2014 means within 1% and 3% (median), respectively. Comparison of simulated recharge results using the coarsest spatial and temporal climate data with results from the finest scale data indicated similar small differences over ten-year moving annual averages, over water years, and during high recharge months. While differences in simulated groundwater recharge magnitude, which may be important for groundwater-flow simulations, were substantial during some seasonal comparisons, trends in recharge were almost identical across scales, leading to similar conclusions about change from “normal”. Considering the uncertainty inherent in projected climate data, coarser spatial and longer temporal scale input data may be sufficient for water resources managers who need to understand changes in trends in groundwater recharge over water-year or longer time periods.

Upper Colorado River Basin↗

A regional soil and sediment geochemical study in northern California

Regional-scale variations in soil geochemistry were investigated in a 20,000-km 2 study area in northern California that includes the western slope of the Sierra Nevada, the southern Sacramento Valley and the northern Coast Ranges. Over 1300 archival soil samples collected from the late 1970s to 1980 in El Dorado, Placer, Sutter, Sacramento, Yolo and Solano counties were analyzed for 42 elements by inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry following a near-total dissolution. These data were supplemented by analysis of more than 500 stream-sediment samples from higher elevations in the Sierra Nevada from the same study site. The relatively high-density data (1 sample per 15 km 2 for much of the study area) allows the delineation of regional geochemical patterns and the identification of processes that produced these patterns. The geochemical results segregate broadly into distinct element groupings whose distribution reflects the interplay of geologic, hydrologic, geomorphic and anthropogenic factors. One such group includes elements associated with mafic and ultramafic rocks including Cr, Ni, V, Co, Cu and Mg. Using Cr as an example, elevated concentrations occur in soils overlying ultramafic rocks in the foothills of the Sierra Nevada (median Cr = 160 mg/kg) as well as in the northern Coast Ranges. Low concentrations of these elements occur in soils located further upslope in the Sierra Nevada overlying Tertiary volcanic, metasedimentary and plutonic rocks (granodiorite and diorite). Eastern Sacramento Valley soil samples, defined as those located east of the Sacramento River, are lower in Cr (median Cr = 84 mg/kg), and are systematically lower in this suite compared to soils from the west side of the Sacramento Valley (median Cr = 130 mg/kg). A second group of elements showing a coherent pattern, including Ca, K, Sr and REE, is derived from relatively silicic rocks types. This group occurs at elevated concentrations in soils overlying volcanic and plutonic rocks at higher elevations in the Sierras (e.g. median La = 28 mg/kg) and the east side of the Sacramento Valley (median 20 mg/kg) compared to soils overlying ultramafic rocks in the Sierra Nevada foothills (median 15 mg/kg) and the western Sacramento Valley (median 14 mg/kg). The segregation of soil geochemistry into distinctive groupings across the Sacramento River arises from the former presence of a natural levee (now replaced by an artificial one) along the banks of the river. This levee has been a barrier to sediment transport. Sediment transport to the Valley by glacial outwash from higher elevations in the Sierra Nevada and, more recently, debris from placer Au mining has dominated sediment transport to the eastern Valley. High content of mafic elements (and low content of silicic elements) in surface soil in the west side of the valley is due to a combination of lack of silicic source rocks, transport of ultramafic rock material from the Coast Ranges, and input of sediment from the late Mesozoic Great Valley Group, which is itself enriched in mafic elements. A third group of elements (Zn, Cd, As and Cu) reflect the impact of mining activity. Soil with elevated content of these elements occurs along the Sacramento River in both levee and adjacent flood basin settings. It is interpreted that transport of sediment down the Sacramento River from massive sulfide mines in the Klamath Mountains to the north has caused this pattern. The Pb, and to some extent Zn, distribution patterns are strongly impacted by anthropogenic inputs. Elevated Pb content is localized in major cites and along major highways due to inputs from leaded gasoline. Zinc has a similar distribution pattern but the source is tire wear.

Applied Geochemistry↗

Late Quaternary eolian dust in surficial deposits of a Colorado Plateau grassland: Controls on distribution and ecologic effects

In a semi-arid, upland setting on the Colorado Plateau that is underlain by nutrient-poor Paleozoic eolian sandstone, alternating episodes of dune activity and soil formation during the late Pleistocene and Holocene have produced dominantly sandy deposits that support grass and shrub communities. These deposits also contain eolian dust, especially in paleosols. Eolian dust in these deposits is indicated by several mineralogic and chemical disparities with local bedrock, but it is most readily shown by the abundance of titaniferous magnetite in the sandy deposits that is absent in local bedrock. Magnetite and some potential plant nutrients (especially, P, K, Na, Mn, and Zn) covary positively with depth (3-4 m) in dune-crest and dune-swale settings. Magnetite abundance also correlates strongly and positively with abundances of other elements (e.g., Ti, Li, As, Th, La, and Sc) that are geochemically stable in these environments. Soil-property variations with depth can be ascribed to three primary factors: (1) shifts in local geomorphic setting; (2) accumulation of relatively high amounts of atmospheric mineral dust inputs during periods of land-surface stability; and (3) variations in dust flux and composition that are likely related to changes in dust-source regions. Shifts in geomorphic setting are revealed by large variations in soil texture and are also expressed by changes in soil chemical and magnetic properties. Variable dust inputs are indicated by both changes in dust flux and changes in relations among magnetic, chemical, and textural properties. The largest of these changes is found in sediment that spans late Pleistocene to early Holocene time. Increased dust inputs to the central Colorado Plateau during this period may have been related to desiccation and shrinkage of large lakes from about 12 to 8 ka in western North America that exposed vast surfaces capable of emitting dust. Soil properties that result from variable dust accumulation and redistribution in these surficial deposits during the late Quaternary are important to modern ecosystem dynamics because some plants today utilize nutrients deposited as long ago as about 12-15 ky and because variations in fine-grained (silt) sediment, including eolian dust, influence soil-moisture capacity.

Catena↗

Trace metal records of regional paleoenvironmental variability in Pennsylvanian (Upper Carboniferous) black shales

Regional geochemical differences within a laterally continuous, cyclic Pennsylvanian (Upper Carboniferous) shale in midcontinent North America are interpreted in light of models of glacioeustatic forcing and new views on water-column paleoredox stability and trace-metal behavior in black shale environments. Specifically, we characterize differences in transition metal (Fe, Mn, Mo, V, Ni, Zn, Pb and U) concentrations in black shales of the Hushpuckney Shale Member of the Swope Limestone in Iowa and equivalent black shale beds of the Coffeyville Formation in Oklahoma. Although C-S-Fe systematics and uniform 34S-depleted isotope ratios of pyrite indicate pervasive euxinic deposition (anoxic and sulfidic bottom waters) for these shales, regional variations can be inferred for the efficiency of Mo scavenging and for the rates of siliciclastic sedimentation as expressed in spatially varying Fe/Al ratios. Black shales in Iowa show Mo enrichment roughly five times greater than that observed in coeval euxinic shales in Oklahoma. By contrast, Fe/Al ratios in Oklahoma shales are as much as five times greater than the continental ratio of 0.5 observed in the over- and underlying oxic facies and in the coeval black shales in Iowa. Recent work in modern marine settings has shown that enrichments in Fe commonly result from scavenging in a euxinic water column during syngenetic pyrite formation. In contrast to Fe, the concentrations of other transition metals (Mo, V, Ni, Pb, Zn, U) are typically more enriched in the black shales in Iowa relative to Oklahoma. The transition metal trends in these Paleozoic shales are reasonably interpreted in terms of early fixation in organic-rich sediments due to euxinic water-column conditions. However, regional variations in (1) rates of siliciclastic input, (2) organic reservoirs, including relative inputs of terrestrial versus marine organic matter, and (3) additional inputs of metals to bottom waters from contemporaneous hydrothermal vents are additional key controls that lead to geographic variation in the extent of metal enrichments preserved in ancient organic-rich sediments. Published by Elsevier B.V.

Chemical Geology↗

The freshwater transport and dynamics of the western Maine coastal current

Observations in the Gulf of Maine, USA, were used to characterize the freshwater transport, temporal variability and dynamics of the western Maine coastal current. These observations included moored measurements, multiple hydrographic surveys, and drifter releases during April–July of 1993 and 1994. There is a strong seasonal signal in salinity and along-shore velocity of the coastal current, caused by the freshwater inputs of the rivers entering the western Gulf. Surface salinity within the coastal current during the spring freshet is typically 2 psu below ambient, and along-shore currents in the surface layer are directed southwestward at speeds of 0.10–0.20 m s −1 , occasionally reaching 0.50 m s −1 . The plume thickness is typically 10–20 m in water depths of 50–100 m, thus it is well isolated from the bottom over most of its areal extent. The along-coast freshwater transport within the plume varies considerably due to variations in wind stress, but on time scales of weeks to months it follows the variations of riverine input, with a time lag consistent with the advective velocity. Less than half of the transport of the coastal current is explained by the baroclinic gradient; the barotropic forcing associated with the larger-scale dynamics of the Gulf of Maine accounts for about 60% of the transport. The volume of freshwater transport in the coastal current exceeds the local riverine input of fresh water by 30%, suggesting a significant contribution of freshwater transport from the St. John River, 500 km northeastward. The measurements within the western Maine coastal current, however, indicate a significant decrease in the baroclinic transport of fresh water along the coast, with an e-folding scale of approximately 200 km.

Gulf of Maine↗

Authigenesis of trace metals in energetic tropical shelf environments

We evaluated authigenic changes of Fe, Mn, V, U, Mo, Cd and Re in suboxic, periodically remobilized, tropical shelf sediments from the Amazon continental shelf and the Gulf of Papua. The Cd/Al, Mo/Al, and U/Al ratios in Amazon shelf sediments were 82%, 37%, and 16% less than those in Amazon River suspended sediments, respectively. Very large depletions of U previously reported in this environment were not observed. The Cd/Al ratios in Gulf of Papua sediments were 76% lower than measurements made on several Papua New Guinea rivers, whereas U/Al ratios in the shelf sediments were enriched by approximately 20%. Other metal/Al ratios in the Papua New Guinea river suspended sediments and continental shelf sediments were not distinguishably different. Comparison of metal/Al ratios to grain size distributions in Gulf of Papua samples indicates that our observations cannot be attributed to differences in grain size between the river suspended sediments and continental shelf sediments. These two shelves constitute a source of dissolved Cd to the world ocean equal to 29–100% of the dissolved Cd input from rivers, but only 3% of the dissolved Mo input and 4% of the dissolved U input. Release of Cd, Mo, and U in tropical shelf sediments is likely a result of intense Fe and Mn oxide reduction in pore waters and resuspension of the sediments. Since we do not observe depletions of particulate Fe and Mn in the shelf sediments most of these dissolved metals must reoxidize in the overlying waters and reprecipitate. As Cd exhibits the largest losses on these tropical shelves, we examined the ability of newly formed Fe and Mn oxides to adsorb dissolved Cd using a geochemical diffuse double-layer surface complexation model and found the oxide surfaces are relatively ineffective at readsorbing Cd in seawater due to surface-site competition by Mg and Ca. If the remobilization and reoxidation of Fe and Mn occurs frequently enough before sediment is buried significant amounts of Cd may be removed from the oxide surfaces. Because a much greater percentage of Mn than Fe becomes remobilized in these shelf sediments, metals closely associated with Mn oxides (like Cd) are more likely to show losses during deposition.

Continental Shelf Research↗

234Th, 210Pb, 210Po and stable Pb in the central equatorial Pacific: Tracers for particle cycling

Samples were collected during the 1992 US JGOFS EqPac Survey I and II cruises from 12??N to 12??S at 140??W in the central equatorial Pacific for water column profiles of dissolved, particulate and total 234Th, 210Pb and 210Po and total acid soluble stable Pb and sediment trap fluxes of 234Th, 210Pb and 210Po. Survey I occurred in February/March with moderate El Nino conditions while Survey II was conducted in September/October when there was a well developed cold-tongue. 234Th, 210Pb and 210Po are all particle reactive yet they partition differently between dissolved and particulate phases. Fractionation factors (the ratios of the distribution coefficients) show that the selectivity for suspended and sediment trap particles follows Th>Po>Pb. Scavenging residence times (??) for 234Th, 210Pb and 210Po ranged from 25 to 100 d, 3 to 8 years and 100 to 500 d, respectively. These particle reactive tracers have very different distributions in the water column, which reflect differences in their sources and sinks. The deficiency of 234Th relative to 238U was fairly uniformly distributed meridionally, though deficiencies were higher during Survey II when there was higher new production. Excess 210Pb relative to 226Ra was very asymmetrical with much higher excess values north of the equator. The distributions were similar for Surveys I and II. The deficiency of 210Po relative to 210Pb had a symmetrical distribution about the equator for both Survey I and II but the deficiencies were larger during Survey I when upwelling was smaller. Stable Pb was generally higher at the surface than at 250 m and there was no meridional trend from 12??N to 12??S. A mass balance for 210Pb was used to determine the atmospheric input of 210Pb. The average values for Surveys I and II were 0.12 and 0.32 dpm cm-2 year-1, respectively. There was no general increase in atmospheric input of 210Pb north of the equator but there was a strong maximum at 2-3??N during Survey I coincident with the location of the intertropical convergence zone (ITCZ), suggesting a large role for wet deposition. A mass balance for stable Pb was used to determine the atmospheric input of stable Pb. Results ranged from 110 to 140 pmol cm-2 year-1. This flux was low in the southern hemisphere and increased steadily north of the equator. We evaluated use of 210Po as a tracer for export of particulate organic matter during Survey I. Organic carbon and 210Po were highly correlated in suspended matter and sediment trap samples. Average values of organic carbon fluxes determined from the deficiencies of 210Po times the orgC/210Po ratio agreed well with those determined from the deficiencies of 234Th times the organic carbon/234Th ratio and 15N-new production, but had a much larger variability because of the more variable advection corrections. ?? 2005 Elsevier Ltd. All rights reserved.

Deep-Sea Research Part I: Oceanographic Research P↗

The influence of tree canopy cover data choices on urban ecosystem accounting

Because urban landscapes are heterogeneous, the methods and spatial resolution used to depict the land surface greatly influence the representation of urban features. Land cover products such as tree canopy cover (TCC) are particularly sensitive to the methodology and resolution used in their creation. Differences in TCC mapping have implications on the outcomes of ecosystem service (ES) models, including those underlying natural capital accounting. Here, we quantify the sensitivity of physical rainfall interception and local climate regulation ES models for 189 U.S. cities to TCC inputs from four TCC products: a) National Land Cover Database (NLCD), b) Enhanced NLCD TCC, c) aggregated city-specific composite, and d) global tree canopy height dataset. We find both city-level and aggregate differences in TCC estimates, from a 38% decrease to a 3% increase relative to an aggregated high-resolution product. These differences result in up to 3% overestimations and 27% underestimation of rainfall interception and 2–56% underestimation of local climate regulation ES. City size, population, and greenness in addition to climatic variation drove differences between TCC products, and this variation requires users to carefully consider the choice of input data for any planned analysis. Though high-resolution data can offer greater nuance and accuracy, more limited spatiotemporal availability can hinder their usefulness for long-term monitoring applications such as natural capital accounting. The differences found in this study provide valuable insights for making informed decisions on data inputs for use in urban ecosystem research and for contextualizing model outcomes.

Contiguous United States↗

Nitrogen budgets of the Long Island Sound estuary

Nitrogen (N) inputs to coastal ecosystems have significant impacts on coastal community structure. In N limited systems, increases in N inputs may lead to excess productivity and hypoxia. Like many temperate estuaries, Long Island Sound (LIS), a major eastern U.S. estuary, is a N limited system which has experienced seasonal hypoxia since the 1800s. This study is the first effort to constrain the total N cycle in this estuary. The approach utilizes data collected over the last two decades in the LIS time series with hydrodynamic model results to generate both monthly and annual N budgets between 1995 and 2016. Of the total N that is delivered to LIS through rivers and atmospheric inputs, 40% is exported to the adjacent continental shelf on the order of 10.8 ± 8.9 × 10 6 kg N/year. Of this export, 41% is dissolved organic N, 29% is particulate organic N, 32% is nitrate + nitrite, and −3% is ammonium. The remaining 60% of the N delivered to LIS is either buried in sediments or lost through denitrification. This inferred internal loss rate is equivalent to 5.4 g N/(m 2 year). This study serves as an example of the significant inter-annual variations that estuarine budgets undergo as efforts to understand coastal biogeochemical cycles move forward.

Connecticut, New York↗

Linking stream-reach nitrogen loads and groundwater “reachsheds” to inform wastewater-nitrogen management actions, Cape Cod, Massachusetts

Study Region Cape Cod, Massachusetts, U.S.A. Study Focus Anthropogenic nitrogen (N) is a key factor in degrading groundwater and surface-water quality, particularly in coastal New England where onsite wastewater systems are prevalent. This study evaluated whether direct N-load measurements in streams on Cape Cod, Massachusetts, coupled with flow-path information from groundwater-flow models, can effectively identify potential land areas where nitrogen mitigation could substantially reduce loads to receiving waters. Nitrogen fluxes were measured along 63 stream reaches during winter and summer and paired with simulated groundwater recharge areas to identify and rank potential areas for reduction of nonpoint-source N inputs. New Hydrologic Insights for the Region Reach-scale nitrate-N loads ranged from −39.1–1182 kg-N/yr per 100 m of stream, indicating spatially variable groundwater inputs across seasons. “Reachsheds” — areas contributing groundwater recharge to specific stream reaches — were delineated using a regional groundwater-flow model. Strong correlations were found between observed N loads and land-use characteristics, especially the number of septic systems and total N inputs from the sum of considered sources. Observed N loads were moderately correlated with recharge area size and wastewater flow estimates. Correlating reach-specific groundwater N loads with land use and parcel-scale nitrogen-yield data identified reachsheds with the highest potential for N load reduction. This approach enables targeted implementation of restoration efforts to optimize nutrient management and support regional load reduction.

Massachusetts↗

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

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

Environmental Pollution↗

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California. Part II: Solute profiles, gradients and the comparisons of contemporary and long-term weathering rates

The spatial and temporal changes in hydrology and pore water elemental and 87 Sr/ 86 Sr compositions are used to determine contemporary weathering rates in a 65- to 226-kyr-old soil chronosequence formed from granitic sediments deposited on marine terraces along coastal California. Soil moisture, tension and saturation exhibit large seasonal variations in shallow soils in response to a Mediterranean climate. These climate effects are dampened in underlying argillic horizons that progressively developed in older soils, and reached steady-state conditions in unsaturated horizons extending to depths in excess of 15 m. Hydraulic fluxes (q h ), based on Cl mass balances, vary from 0.06 to 0.22 m yr -1 , resulting in fluid residence times in the terraces of 10-24 yrs. As expected for a coastal environment, the order of cation abundances in soil pore waters is comparable to sea water, i.e., Na > Mg > Ca > K > Sr, while the anion sequence Cl > NO 3 > HCO 3 > SO 4 reflects modifying effects of nutrient cycling in the grassland vegetation. Net Cl-corrected solute Na, K and Si increase with depth, denoting inputs from feldspar weathering. Solute 87 Sr/ 86 Sr ratios exhibit progressive mixing of sea water-dominated precipitation with inputs from less radiogenic plagioclase. While net Sr and Ca concentrations are anomalously high in shallow soils due to biological cycling, they decline with depth to low and/or negative net concentrations. Ca/Mg, Sr/Mg and 87 Sr/ 86 Sr solute and exchange ratios are similar in all the terraces, denoting active exchange equilibration with selectivities close to unity for both detrital smectite and secondary kaolinite. Large differences in the magnitudes of the pore waters and exchange reservoirs result in short-term buffering of the solute Ca, Sr, and Mg. Such buffering over geologic time scales can not be sustained due to declining inputs from residual plagioclase and smectite, implying periodic resetting of the exchange reservoir such as by past vegetational changes and/or climate. Pore waters approach thermodynamic saturation with respect to albite at depth in the younger terraces, indicating that weathering rates ultimately become transport-limited and dependent on hydrologic flux. Contemporary rates R solute are estimated from linear Na and Si pore weathering gradients b solute such that R solute = frac(q h , b solute ?? S v ) where S v is the volumetric surface area and ?? is the stoichiometric coefficient. Plagioclase weathering rates (0.38-2.8 ?? 10 -15 mol m -2 s -1 ) are comparable to those based on 87 Sr/ 86 Sr mass balances and solid-state Na and Ca gradients using analogous gradient approximations. In addition, contemporary solute gradients, under transport-limited conditions, approximate long-term solid-state gradients when normalized against the mass of protolith plagioclase and its corresponding aqueous solubility. The multi-faceted weathering analysis presented in this paper is perhaps the most comprehensive yet applied to a single field study. Within uncertainties of the methods used, present day weathering rates, based on solute characterizations, are comparable to average long-term past rates as evidenced by soil profiles.

Geochimica et Cosmochimica Acta↗

Modeling the influence of organic acids on soil weathering

Biological inputs and organic matter cycling have long been regarded as important factors in the physical and chemical development of soils. In particular, the extent to which low molecular weight organic acids, such as oxalate, influence geochemical reactions has been widely studied. Although the effects of organic acids are diverse, there is strong evidence that organic acids accelerate the dissolution of some minerals. However, the influence of organic acids at the field-scale and over the timescales of soil development has not been evaluated in detail. In this study, a reactive-transport model of soil chemical weathering and pedogenic development was used to quantify the extent to which organic acid cycling controls mineral dissolution rates and long-term patterns of chemical weathering. Specifically, oxalic acid was added to simulations of soil development to investigate a well-studied chronosequence of soils near Santa Cruz, CA. The model formulation includes organic acid input, transport, decomposition, organic-metal aqueous complexation and mineral surface complexation in various combinations. Results suggest that although organic acid reactions accelerate mineral dissolution rates near the soil surface, the net response is an overall decrease in chemical weathering. Model results demonstrate the importance of organic acid input concentrations, fluid flow, decomposition and secondary mineral precipitation rates on the evolution of mineral weathering fronts. In particular, model soil profile evolution is sensitive to kaolinite precipitation and oxalate decomposition rates. The soil profile-scale modeling presented here provides insights into the influence of organic carbon cycling on soil weathering and pedogenesis and supports the need for further field-scale measurements of the flux and speciation of reactive organic compounds.

California↗

Animating the biodynamics of soil thickness using process vector analysis: A dynamic denudation approach to soil formation

This paper expands the dynamic denudation framework of landscape evolution by providing new process insights and details on how soil and its signature morphological feature, the biomantle, form and function in the environment. We examine soils and their biomantles from disparate parts of the world, from the tropics through midlatitudes and hyperarid through perhumid, a range that exhibits varying environments for, and of, life. We then explicate the process pathways that cause soils to thicken and thin, and to even disappear, then reform. We do this by examining thickness relationships, where soil thickness stand biomantle thickness bt are functions of upbuilding u and deepening d minus removal r processes, hence st/bt=f(u+d-r). Upbuilding has two subsets, u1, which includes all exogenous (allochthonous-outside) mineral and/or organic inputs to the soil system, and u2, which includes all endogenous (autochthonous-in situ) processes and productions, including weathering. Exogenous u1 inputs include eolian and slopewash inputs (sedimentations) of mineral and organic materials, mass wasting accumulations and the like. Endogenous u2 processes and productions include the sum of in situ bioturbations, biosynthetic productions, organic accumulations, biovoid productions, weathering and volume increases caused by their sum. Endogenous upbuildings, which dominantly occur in the biomantle, are basically biodynamic bd processes and productions, hence u2=bd. Therefore, if exogenous upbuildings u1 are minimal or zero, then biomantle thickness bt is expressed by bt=f(u2-r) or bt=f(bd-r). Drawing on these relationships, we employ a graphic-conceptual device called process vector analysis in a digital animation (see supplementary materials or cf. https://netfiles.uiuc.edu/jdomier/www/temp/ biomantle.html) that illustrates the main pathways that form both Earth's soil and its unique epidermis, the biomantle. We then discuss the main elements of the animation using still frames that represent thickness turning points. We end by encouraging researchers, instructors and students to view Earth's landforms and soils as integrated dynamic entities that are constantly coevolving elements of a global subaerial-subaqueous continuum. ?? 2004 Elsevier B.V. All rights reserved.

Geomorphology↗

Microbial source tracking and evaluation of best management practices for restoring degraded beaches of Lake Michigan

Attempts to mitigate shoreline microbial contamination require a thorough understanding of pollutant sources, which often requires multiple years of data collection (e.g., point/nonpoint) and the interacting factors that influence water quality. Because restoration efforts can alter shoreline or beach morphology, revisiting source inputs is often necessary. Microbial source tracking (MST) using source-specific molecular markers, genomic community analyses, and physical modeling was used to identify contamination sources along three Lake Michigan beaches of the Laurentian Great Lakes with historically high fecal indicator bacteria (FIB, E. coli ) concentrations. Genetic markers for human (Bacteroides HF183) and mixed gull species ( Catellicoccus marimammalium ) fecal sources were tested from water and sediment. Gene sequencing (16S rRNA) was used to identify similarities in bacterial communities in nearshore water, river inputs, sand, sediment, and groundwater. Synoptic surveys of water exchange were conducted to determine nearshore-offshore interactions of FIB. In addition to these MST studies, best management practices to mitigate FIB, including gull deterrence, slope grading, wetland establishment, and shoreline plantings, were reviewed for their effectiveness at reducing FIB concentrations over time. Using multiple tools for MST helped identify primary and secondary sources of FIB (gulls, stormwater inputs) and the physical processes that exacerbate FIB concentrations (onshore currents, limited circulation). Management actions were successful in the short-term at reducing FIB, but scope of success was temporally limited, with FIB concentrations often rebounding. Results highlight the usefulness of MST to inform best management practices and the need for a sustained adaptive approach that adjusts for changes in the coastal system.

Illinois, Wisconsin↗

Seasonal groundwater contribution to crop-water use assessed with lysimeter observations and model simulations

Groundwater evaporation can play an important role in crop-water use where the water table is shallow. Lysimeters are often used to quantify the groundwater evaporation contribution influenced by a broad range of environmental factors. However, it is difficult for such field facilities, which are operated under limited conditions within limited time, to capture the whole spectrum of capillary upflow with regard to the inter-seasonal variability of climate, especially rainfall. Therefore, in this work, the method of combining lysimeter and numerical experiments was implemented to investigate seasonal groundwater contribution to crop-water use. Groundwater evaporation experiments were conducted through a weighing lysimeter at an agricultural experiment station located within an irrigation district in the lower Yellow River Basin for two winter wheat growth seasons. A HYDRUS-1D model was first calibrated and validated with weighing lysimeter data, and then was employed to perform scenario simulations of groundwater evaporation under different depths to water table (DTW) and water input (rainfall plus irrigation) driven by long term meteorological data. The scenario simulations revealed that the seasonally averaged groundwater evaporation amount was linearly correlated to water input for different values of DTW. The linear regression could explain more than 70% of the variability. The seasonally averaged ratio of the groundwater contribution to crop-water use varied with the seasonal water input and DTW. The ratio reached as high as 75% in the case of DTW=1.0. m and no irrigation, and as low as 3% in the case of DTW=3.0. m and three irrigation applications. The results also revealed that the ratio of seasonal groundwater evaporation to potential evapotranspiration could be fitted to an exponential function of the DTW that may be applied to estimate seasonal groundwater evaporation. In this case study of multilayered soil profile, the depth at which groundwater may evaporate at potential rate was 0.60-0.65. m, and the extinction depth of groundwater evaporation was approximately 3.8. m. ?? 2010 Elsevier B.V.

Journal of Hydrology↗