Conservative behavior of arsenic and other oxyanion-forming trace elements in an oxic groundwater flow system

Groundwater samples were collected along a flow path in a shallow, fractured tuffaceous aquifer from the Oasis Valley–Beatty Wash region of southern Nevada, USA, and analyzed for a number of oxyanion-forming trace elements including arsenic (As), antimony (Sb), selenium (Se), molybdenum (Mo), and tungsten (W). In addition, ancillary geochemical parameters, including pH, major solute compositions, dissolved silica, dissolved oxygen, and iron and manganese concentrations were quantified in the groundwaters. Arsenic concentrations range from 70 nmol/kg up to 316 nmol/kg in groundwaters of the Oasis Valley–Beatty Wash flow system, and generally exhibit increasing concentrations with flow down-gradient along the flow path. Antimony, W, and to a lesser extent, Mo, exhibit similar increasing concentration trends with flow down-gradient in the aquifer, albeit, at lower concentrations levels (e.g., mean ± SD for Sb, W, and Mo are 2.3 ± 0.9 nmol/kg, 7.4 ± 3.7 nmol/kg, and 101 ± 19 nmol/kg, respectively). Selenium concentration, which range between 4 and 11 nmol/kg, generally decrease in groundwaters with flow down-gradients in the Oasis Valley–Beatty Wash groundwater flow systems. Inverse modeling of groundwater chemistry evolution from the lower reaches of the Oasis Valley flow path using PHREEQC indicate that the groundwater composition is consistent with mixing of nearly equal proportions of groundwater from upper reaches of Oasis Valley and Beatty Wash groundwater, along with dissolution of volcanic glass, potassium feldspar, and gypsum, followed by calcite precipitation, and formation of secondary zeolites (analcime), clay minerals (Ca-montmorillonite), and cristobalite. The geochemical modeling indicates that the concentrations of As and the other oxyanion-forming trace elements are controlled by dissolution of volcanic glass, water–rock interaction with mineralized zones within the aquifer (i.e., sulfide oxidation), desorption from aquifer surface sites, and mixing of Oasis Valley and Beatty Wash groundwaters.     

Predicting saturation‐excess runoff distribution with a lumped hillslope model: SWAT‐HS

Saturation‐excess runoff is the major runoff mechanism in humid well‐vegetated areas where infiltration rates often exceed rainfall intensity. Although the Soil and Water Assessment Tool (SWAT) is one of the most widely used models, it predicts runoff based mainly on soil and land use characteristics, and is implicitly an infiltration‐excess runoff type of model. Previous attempts to incorporate the saturation‐excess runoff mechanism in SWAT fell short due to the inability to distribute water from one hydrological response unit to another. This paper introduces a modified version of SWAT, referred to as SWAT‐Hillslope (SWAT‐HS). This modification improves the simulation of saturation‐excess runoff by redefining hydrological response units based on wetness classes and by introducing a surface aquifer with the ability to route interflow from “drier” to “wetter” wetness classes. Mathematically, the surface aquifer is a nonlinear reservoir that generates rapid subsurface stormflow as the water table in the surface aquifer rises. The SWAT‐HS model was tested in the Town Brook watershed in the upper reaches of the West Branch Delaware River in the Catskill region of New York, USA. SWAT‐HS predicted discharge well with a Nash‐Sutcliffe Efficiency of 0.68 and 0.87 for daily and monthly time steps. Compared to the original SWAT model, SWAT‐HS predicted less surface runoff and groundwater flow and more lateral flow. The saturated areas predicted by SWAT‐HS were concentrated in locations with a high topographic index and were in agreement with field observations. With the incorporation of topographic characteristics and the addition of the surface aquifer, SWAT‐HS improved streamflow simulation and gave a good representation of saturated areas on the dates that measurements were available. SWAT‐HS is expected to improve water quality model predictions where the location of the surface runoff matters.     

Pleistocene stratigraphy in the Devils Hole Area,Central North Sea: Foraminiferal and amino-acid evidence

A detailed study of the foraminiferal assemblages from the 229.1-m-deep core 81/34 in the central North Sea has been combined with a series of measurements of the isoleucine epimerisation of foraminiferal tests. A total of 17 foraminiferal zones have been established and both the faunal compositions and the amino-acid values suggest that a major part of the sequence represents deposits of early and middle Pleistocene age. Only the uppermost zone is referred to the late Pleistocene. The sequence mainly comprises a series of marine zones from cold periods, but with some barren, possibly non-marine intervals in between. Only two of the foraminiferal zones can be referred to interglacial periods. The oldest one of these, defined here as the Devils Hole Interglacial, may belong to the latter part of the Cromerian Complex, while the upper warm interval is correlated with the Holsteinian of northwest Europe on the basis of its amino-acid values. A detailed stratigraphical correlation between core 81/34 and the neighbouring core 81/29 is suggested on the basis of their foraminiferal content, palaeomagnetic evidence and amino-acid measurements from both cores. A characteristic feature of both sequences is that most of the Quaternary record is missing. Similar episodic patterns of deposition and erosion have been reported previously from the North Sea area.     

Palaeontology and taphonomy of Late Quaternary fossil assemblages at Somersham,Cambridgeshire, England,and the problem of reworking

Assemblages of foraminifers, ostracods and molluscs from temperate Ipswichian Stage (last temperate stage) sediments and overlying cold Devensian Stage (last cold stage) sediments at Somersham in the southern Fenland of Cambridgeshire have been analysed. The Ipswichian sediments contain faunas consistent with temperate brackish water conditions under tidal influence. The Devensian assemblages were recovered from a series of sands and gravels laterally accreting in a channel cutting into Ipswichian sediments. In contrast to the Ipswichian faunas, the faunas of particular Devensian samples show a complex mixture of temperate freshwater, brackish and marine taxa. The molluscs are mainly freshwater, with few land snails; they occur together with foraminifers and ostracods. Freshwater, brackish water and marine ostracods are present with foraminifers. A sample of Devensian fine laminated sediment in the channel was analysed for pollen; only abundant pre-Quaternary spores were present, with abundant foraminifers in the same sample. The taphonomy of the assemblages and the difficulties of their interpretation in environmental terms are discussed. The importance of taphonomy in assessing environments, climate, range of taxa and dating is stressed.     

Quantifying and testing differences among means of compositional data suites

Commonly, geological studies compare mean values of two or more compositional data suites in order to determine if, how, and by how much they differ. Simple approaches for evaluating and statistically testing differences in mean values for open data fail for compositional (closed) data. A new parameter, an f-value, therefore has been developed, which correctly quantifies the differences among compositional mean values and allows testing those differences for statistical significance. In general, this parameter quantifies only therelative factor by which compositional variables differ across data suites; however for situations where, arguably, at least one component has neither increased nor decreased, anabsolute f-value can be computed. In situations where the compositional variables have undergone many perturbations, arguments based upon thef-values and the central limit theorem indicate that logratios of compositional variables should be normally distributed.     

Geochemical processes during five years of aquifer storage recovery

A key factor in the long-term viability of aquifer storage recovery (ASR) is the extent of mineral solution interaction between two dissimilar water types and consequent impact on water quality and aquifer stability. We collected geochemical and isotopic data from three observation wells located 25, 65, and 325 m from an injection well at an experimental ASR site located in a karstic, confined carbonate aquifer in South Australia. The experiment involved five major injection cycles of a total of 2.5 x 10(5) m3 of storm water (total dissolved solids [TDS] approximately 150 mg/L) into the brackish (TDS approximately 2400 mg/L) aquifer. Approximately 60% of the mixture was pumped out during the fifth year of the experiment. The major effect on water quality within a 25 m radius of the injection well following injection of storm water was carbonate dissolution (35 +/- 6 g of CaCO3 dissolved/m3 of aquifer) and sulfide mineral oxidation (50 +/- 10 g as FeS2/m3 after one injection). < 0.005% of the total aquifer carbonate matrix was dissolved during each injection event, and approximately 0.2% of the total reduced sulfur. Increasing amounts of ambient ground water was entrained into the injected mixture during each of the storage periods. High 14C(DIC) activities and slightly more negative delta13C(DIC) values measured immediately after injection events show that substantial CO2(aq) is produced by oxidation of organic matter associated with injectant. There were no detectable geochemical reactions while pumping during the recovery phase in the fifth year of the experiment.     

Potential contaminants at a dredged spoil placement site,Charles City County,Virginia, as revealed by sequential extraction

Backfills of dredged sediments onto a former sand and gravel mine site in Charles City County, VA may have the potential to contaminate local groundwater. To evaluate the mobility of trace elements and to identify the potential contaminants from the dredged sediments, a sequential extraction scheme was used to partition trace elements associated with the sediments from the local aquifer and the dredged sediments into five fractions: exchangeable, acidic, reducible, oxidizable, and residual phases. Sequential extractions indicate that, for most of the trace elements examined, the residual phases account for the largest proportion of the total concentrations, and their total extractable fractions are mainly from reducible and oxidizable phases. Only Cd, Pb, and Zn have an appreciable extractable proportion from the acidic phase in the filled dredged sediments. Our groundwater monitoring data suggest that the dredged sediments are mainly subject to a decrease in pH and a series of oxidation reactions, when exposed to the atmosphere. Because the trace elements released by carbonate dissolution and the oxidation (e.g., organic matter degradation, iron sulfide and, ammonia oxidation) are subsequently immobilized by sorption to iron, manganese, and aluminum oxides, no potential contaminants to local groundwater are expected by addition of the dredged sediments to this site.     

Surface sediment carbonate mineralogy and water column chemistry: Nicaragua Rise versus the Bahamas

Periplatform surface sediments were studied for carbonate mineralogy in conjunction with analyses of the water column for carbonate chemistry on the eastern Northern Nicaragua Rise (NNR) in the Caribbean Sea. The results show a strong correspondence between variations and disappearance, with increasing water depth, of metastable carbonate minerals (fine aragonite and magnesian calcite) and their respective saturation levels in the overlying waters. Similar correspondence between variations in sediment proportions of fine aragonite and magnesian calcite and their respective saturation levels has previously been established in the Bahamas. There are, however, significant differences between the two areas. The sharp decrease in aragonite content and the measured aragonite saturation level occur at 4000 m in the Bahamas, compared to 1800 m on the eastern NNR. In both areas, magnesian calcite minima correspond to the in situ PCO₂ maxima in the water column. The magnesian calcite minimum, however, is at 950 m in the Bahamas and 750 m on the eastern NNR. Magnesian calcite disappears in the Bahamas at 3800 m and at 2000 m on the eastern NNR. These results demonstrate the importance of the influence of overlying water chemistry on the preservation of metastable carbonate minerals in off-bank periplatform sediments, and they clearly demonstrate the difference in terms of carbonate preservation between the poorly ventilated waters of the Caribbean Sea and the well-oxygenated waters of the adjacent Atlantic Ocean. They also open the possibility of obtaining paleoceanographic information on the depth of the CO₂ maximum (O₂ minimum) and its separation from the aragonite saturation depth in at least some areas.