The Juan de Fuca Ridge is a hydrothermally active, sediment covered, spreading ridge situated a few hundred kilometres off the west coast of North America in the northeastern Pacific Ocean. Sediments from seven sites drilled during the Ocean Drilling Program (ODP) Legs 139 and 168 were analyzed for total hydrolyzable amino acids (THAA), individual amino acid distributions, total organic C (TOC) and total N (TN) contents. The aim was to evaluate the effects of hydrothermal stress on the decomposition and transformation of sedimentary amino acids. Hydrolyzable amino acids account for up to 3.3% of the total organic C content and up to 12% of the total N content of the upper sediments. The total amounts of amino acids decrease significantly with depth in all drilled holes. This trend is particularly pronounced in holes with a thermal gradient of around 0.6 degrees C/m or higher. The most abundant amino acids in shallow sediments are glycine, alanine, lysine, glutamic acid, valine and histidine. The changes in amino acid distributions in low temperature holes are characterized by increased relative abundances of non-protein beta-alanine and gamma-aminobutyric acid. In high temperature holes the amino acid compositions are characterized by high abundances of glycine, alanine, serine, ornithine and histidine at depth. D/L ratios of samples with amino acid distributions similar to those found in acid hydrolysates of kerogen, indicate that racemization rates of amino acids bound by condensation reactions may be diminished.
Arsenic is a prevalent contaminant at US Superfund sites where remediation by pump and treat systems is often complicated by slow desorption of As from Fe and Al (hydr)oxides in aquifer solids. Chemical amendments that either compete with As for sorption sites or dissolve Fe and Al (hydr)oxides can increase As mobility and improve pump and treat remediation efficiency. The goal of this work was to determine optimal amendments for improving pump and treat at As contaminated sites such as the Vineland Chemical Co. Superfund site in southern New Jersey. Extraction and column experiments were performed using As contaminated aquifer solids (81 ± 1 mg/kg), site groundwater, and either phosphate (NaH(2)PO(4)·H(2)O) or oxalic acid (C(2)H(2)O(4)·2H(2)O). In extraction experiments, phosphate mobilized between 11% and 94% of As from the aquifer solids depending on phosphate concentration and extraction time (1 mM-1 M; 1-24 h) and oxalic acid mobilized between 38 and 102% depending on oxalic acid concentration and extraction time (1-400 mM; 1-24 h). In column experiments, phosphate additions induced more As mobilization in the first few pore volumes but oxalic acid was more effective at mobilizing As overall and at lower amendment concentrations. At the end of the laboratory column experiments, 48% of As had been mobilized from the aquifer sediments with 100 mM phosphate and 88% had been mobilized with 10 mM oxalic acid compared with 5% with ambient groundwater alone. Furthermore, simple extrapolations based on pore volumes suggest that chemical treatments could lower the time necessary for clean up at the Vineland site from 600 a with ambient groundwater alone to potentially as little as 4 a with 10 mM oxalic acid.
Desert mine tailings may accumulate toxic metals in the near surface centimeters because of low water through-flux rates. Along with other constraints, metal toxicity precludes natural plant colonization even over decadal time scales. Since unconsolidated particles can be subjected to transport by wind and water erosion, potentially resulting in direct human and ecosystem exposure, there is a need to know how the lability and form of metals change in the tailings weathering environment. A combination of chemical extractions, X-ray diffraction, micro-X-ray fluorescence spectroscopy, and micro-Raman spectroscopy were employed to study Pb and Zn contamination in surficial arid mine tailings from the Arizona Klondyke State Superfund Site. Initial site characterization indicated a wide range in pH (2.5 to 8.0) in the surficial tailings pile. Ligand-promoted (DTPA) extractions, used to assess plant-available metal pools, showed decreasing available Zn and Mn with progressive tailings acidification. Aluminum shows the inverse trend, and Pb and Fe show more complex pH dependence. Since the tailings derive from a common source and parent mineralogy, it is presumed that variations in pH and "bioavailable" metal concentrations result from associated variation in particle-scale geochemistry. Four sub-samples, ranging in pH from 2.6 to 5.4, were subjected to further characterization to elucidate micro-scale controls on metal mobility. With acidification, total Pb (ranging from 5 - 13 g kg(-1)) was increasingly associated with Fe and S in plumbojarosite aggregates. For Zn, both total (0.4 - 6 g kg(-1)) and labile fractions decreased with decreasing pH. Zinc was found to be primarily associated with the secondary Mn phases manjiroite and chalcophanite. The results suggest that progressive tailings acidification diminishes the overall lability of the total Pb and Zn pools.
Cape Kalamba oil seeps occur at the south end of the Ubwari Peninsula, at the intersection of faults controlling the morphology of the northern basin of the Tanganyika Rift, East Africa. Oil samples collected at the surface of the lake 3-4 km offshore from Cape Kalamba have been studied. The aliphatic hydrocarbon and biomarker compositions, with the absence of the typical suite of polynuclear aromatic hydrocarbons, indicate an origin from hydrothermal alteration of immature microbial biomass in the sediments. These data show a similarity between a tar sample from the beach and the petroleum from the oil seeps, and confirm that the source of these oils is from organic matter consisting mainly of bacterial and degraded algal biomass, altered by hydrothermal activity. The compositions also demonstrate a < 200 degrees C temperature for formation/generation of this hydrothermal petroleum, similar to the fluid temperature identified for the Pemba hydrothermal site located 150 km north of Cape Kalamba. The 14C age of 25.6 ka B.P. obtained for the tar ball suggests that Pleistocene lake sediments could be the source rock. Hydrothermal generation may have occurred slightly before 25 ka B.P., during a dry climatic environment, when the lake level was lower than today. These results also suggest that the Cape Kalamba hydrothermal activity did not occur in connection with an increased flux of meteoric water, higher water tables and lake levels as demonstrated in the Kenya Rift and for the Pemba site. Hydrothermal petroleum formation is a facile process also in continental rift systems and should be considered in exploration for energy resources in such locales.
One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1-1000 mug/L), Fe (0.01-40 mg/L), Mn (0.2-4 mg/L) and S (0.04-14 mg/L) are compared. The P-extractable (0.01-36 mg/kg) and HCl-extractable As (0.04-36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2-1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.
Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1x or (4) 10x the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.
Elevated Pb levels in humans through environmental exposure are a significant health concern requiring scientific study of the sources of, and physiological response to this toxin. This requires a simple and precise method for measuring radiogenic Pb isotopes and Pb levels in blood. Presented here is a combination of methods for separation and analysis of Pb previously used predominantly for geologic samples. This includes separation of Pb from the complex matrix of blood samples using an Fe co-precipitation method, followed by isotopic analysis by multi-collector inductively coupled plasma mass spectrometry. Evaluation of the efficacy of this procedure shows that the precision of sample preparations as measured by % difference between the (207)Pb/(206)Pb of duplicate analyses averages 0.064% (n = 48). Using the same preparation and analysis techniques to measure Pb concentrations by isotope dilution resulted in a reproducibility of better than 6%. The method was successfully used to measure uptake of ingested soil Pb in a study of the bioavailability of Pb in contaminated soils.
The transport of H2SO4 (at pH = 1.0, −1.0 and −3.0) through two mineralogically different compacted clays (Kc and Km) was examined using single-reservoir diffusion cells with constant source concentrations. At the end of the 216 day test period, geochemical analyses indicated increased depth of acid diffusion with increased reservoir acidity for both Kc and Km cells. Elevated Ca, Al, Fe and Si concentrations were associated with decreased pH values in all cells. XRD results showed that these elevated concentrations corresponded to the loss of carbonate and montmorillonite peaks and decreased peak intensities for illite and kaolinite in the Kc and Km pH −1.0 and −3.0 Km cells. Moreover, Si X-ray absorption near-edge structure (XANES) indicated dissolution of the phyllosilicate phases, a relative increase in the amount of quartz, and the potential formation of an amorphous silica phase. The results of this study showed that, despite the extreme pH values considered, movement of H2SO4 solutions with pH < 1.0 may be greatly retarded in the presence of a strongly neutralizing mineral phase, such as dolomite, within the clay.
Red Deer antler and bone collagen complexes, recent and 11 ka BP old, were solubilized in anhydrous formic acid, cleaving the α-chains to give arrays of large stable peptides. Calf-skin collagen was also compared. The antler and bone α-chains have survived substantially through this time-span as molecular entities, under bog conditions. These arrays reveal small but meaningful differences between the main collagen components of bone and antler and skin, which could be of post-translational origin. We report here an exploratory study of some problems of molecular survival in ancient collagenous material through 11 ka and also of antler growth as compared with bone growth in vivo.
A sand filter has been built as a pilot plant with the purpose of biological precipitation of Fe from ground water polluted with mainly chlorinated aliphatics. The ground water is pumped directly from a well in a polluted ground water aquifer in Esbjerg, Denmark. The pollution includes trichlorethylene and tetrachlorethylene together with smaller amounts of pesticides. Furthermore the best conditions for Fe precipitating bacteria were not expected to be present because of a relatively high O2 content, up to 6.7 mg/l, a low Fe content, 0.2 mg/l and a pH of ∼5 in the ground water. Added FeSO4 increased the Fe content of the ground water to about 4 mg/l. These rather extreme conditions for precipitating Fe were observed over a period of 3 months. The goal of the research was to observe the mechanism of Fe precipitation in a sand filter in the above-mentioned conditions comparative to normal conditions for biotic as well as abiotic Fe mineralization in sand filters of fresh water treatment plants. The Fe precipitating bacterium Gallionella ferrugenia was found to dominate the biotic Fe oxidation/precipitation process despite the extreme conditions. A huge amount of exopolymer from Gallionella was present. The precipitated Fe oxide was determined to be ferrihydrate. The rate of the Fe oxidation/precipitation was found to be about 1000 times faster than formerly found for abiotic physico-chemical oxidation/precipitation processes. The hydrophobic pesticides and some of their degradation products were not adsorbed in the filter. An added hydrophilic pesticide was adsorbed up to 40%. Trichlorethylene was not adsorbed in the filter. The reason for the poor adsorption of the hydrophobic compounds and trichlorethylene is due to the pronounced hydrophilic property of the exopolymers of Gallionella and the precipitated ferrihydrite.
The uptake of Nd(III) by the crystalline C–S–H phases 11 Å tobermorite and xonotlite has been investigated by the combined use of wet chemistry techniques, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray diffraction (XRD) in combination with Rietveld refinement. The results from XRD and EXAFS allowed the different modes of Nd–Ca substitution in tobermorite and xonotlite to be distinguished from each other. Wet chemistry and EXAFS data showed that the formation of any Nd solid phase with fixed stoichiometry could be ruled out. XRD studies on the samples with high Nd loading (350 μmol Nd/g solid phase) further showed that Nd was bound in the structure of C–S–H phases. The EXAFS data suggested that Nd could form several species on xonotlite and tobermorite at low loadings (7–35 μmol Nd/g solid phase). Neodymium was predominantly bound on the external surface of both crystalline C–S–H phases after 1 day of reaction time and predominantly incorporated in the Ca layers of the crystalline C–S–H phases in the long run (⩾60 days reaction time). The latter process was faster at low Nd loadings and was apparently controlled by re-crystallization of the C–S–H phases. Neodymium incorporation was accompanied by the release of “zeolitic” water (water molecules in the interlayer of C–S–H) and bridging Si tetrahedra, reflected by the formation of more disordered structures in both C–S–H phases. The Nd retention model proposed in this study helps to improve understanding of the immobilization of trivalent lanthanides and actinides in cementitious materials. This knowledge is essential for long-term predictions of radionuclide retention in conjunction with a more detailed assessment of the safe disposal of actinides in the cementitious near field of a repository for radioactive waste.
A method for the in situ single spot δ11B characterisation of geological materials with laser ablation multicollector ICP mass spectrometry (LA-MC-ICPMS) has been developed. The mass spectrometer was equipped with both Faradays and multiple ion counters. Four samples with different B contents (12–31,400 ppm) and isotopic compositions (δ11B are between −8.71 and +13.6‰) were analysed. Samples include the B4 tourmaline and 3 MPI-DING glasses (StHs6/80-G, GOR132-G and GOR128-G).All sources of B isotopic fractionation during the analysis (mass bias, laser-induced isotopic fractionation and detector efficiency drift) have been evaluated and quantified. Instrumental mass bias is the major source of fractionation, altering the original isotopic ratio up to 13%. Fractionation related to laser sampling and transport to the ICP was found to be very low (less than 0.0015% s−1). Fractionation effects due to drift in ion counter efficiencies were found to be significant. Nevertheless, the “standard-sample-standard” bracketing approach could be used to correct for the above fractionation effects using NIST SRM 610 as external standard.With spot sizes of 60–80 μm in diameter, geologically meaningful results can be achieved on samples containing at least 10 ppm B, i.e., results with precisions that can discriminate between the different reservoirs on Earth. Data obtained with Faraday detectors on NIST SRM 610 and B4 tourmaline show high precision (down to 0.04‰, 1σ) and accuracy. Boron isotope ratios measured in the glass samples using multiple ion counting show significantly higher standard deviations (up to 2.5‰, 1σ), but they are very close to the values that can be expected from counting statistics. No significant variations with spot size or B contents were observed. Most of the values are within 1σ level of the reference values.The developed method was applied to a series of ashes from Mt. Etna erupted in 1995 having B contents between 14 and 20 ppm. The B isotope compositions of the ashes are between −4.8 and −10.7‰, with a weighted average value of −8.0 ± 1.9‰ (1σ).
Rock samples and the C-, B- and O-horizons of soils developed on these rocks were collected in forested areas along a 120-km south–north transect in southern Norway, passing through the city of Oslo. Forty samples (1 site/3 km) were analysed for 37 chemical elements (Ag, Al, As, Au, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Sc, Se, Sr, Te, Th, Ti, Tl, U, V, W and Zn) following an aqua regia digestion; pH (water extract) and loss on ignition were also determined. The O-horizon soils were additionally analysed for Pt. Gold is the only element that shows a clear anthropogenic peak in the O-horizon soils collected from the city of Oslo. Silver, Au, Bi, Cd, Hg, Pb, S, Sb, Se and Sr all show a strong enrichment in the O-horizon when compared to the underlying C-horizon or the bedrock along the full length of the transect. Neither geology nor anthropogenic input of elements dominate the observed patterns. The most important factors for the observed element concentrations in the O-horizon are weathering, uptake (or rejection) of elements by plants and the kinetics of decay of the organic material in the O-horizon. Climate, especially temperature and precipitation, has an important influence on the formation and decay rates of the organic soil layer. Acid precipitation will delay the decomposition of the organic layer and lead to a natural enrichment of several metals in the O-horizon. Land use change, deforestation and liming can all increase the decay kinetics of organic matter and thus result in a release of the stored element pool.
The through- and out-diffusion of HTO, 36Cl− and 125I− in Opalinus Clay, an argillaceous rock from the northern part of Switzerland, was studied under different confining pressures between 4 and 15 MPa. The direction of diffusion and the confining pressure were perpendicular to the bedding. Confining pressure had only a small effect on diffusion. An increase in pressure from 4 to 15 MPa resulted in a decrease of the effective diffusion coefficient of ∼20%. Diffusion accessible porosities were not measurably affected. The values of the effective diffusion coefficients, De, ranged between (5.6±0.4)×10−12 and (6.7±0.4)×10−12 m2 s−1 for HTO, (7.1±0.5)×10−13 and (9.1±0.6)×10−13 m2 s−1 for 36Cl− and (4.5±0.3)×10−13 and (6.6±0.4)×10−13 m2 s−1 for 125I−. The rock capacity factors, α, measured were circa 0.14 for HTO, 0.040 for 36Cl− and 0.080 for 125I−. Because of anion exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than the uncharged HTO. Unlike 36Cl−, 125I− sorbs weakly on Opalinus Clay resulting in a larger rock capacity factor. The sorption coefficient, Kd, for 125I− is of the order of 1–2×10−5 m3 kg−1. The effective diffusion coefficient for HTO is in good agreement with values measured in other sedimentary rocks and can be related to the porosity using Archie's Law with exponent m=2.5.
This work constitutes the first survey of I isotope ratios for Scottish sea water including the first data for the west of Scotland. These data are of importance because of the proximity to the world’s second largest emission source of 129I to the sea, the Sellafield nuclear reprocessing plant, because of the increasing importance of the sea to land transfer of 129I and also as input data for dose estimates based on this pathway of 129I. 129I/127I ratios in SW Scotland reached 3 × 10−6 in 2004. No strong variation of I isotope ratios was found from 2003 to 2005 in Scottish sea waters. Iodine isotope ratios increased by about a factor of 6 from 1992 to 2003 in NE Scotland, in agreement with the increase of liquid 129I emissions from Sellafield over that time period. It is demonstrated that 129I/127I ratios agree better than 129I concentrations for samples from similar locations taken in very close temporal proximity, indicating that this ratio is more appropriate to interpret than the radionuclide concentration.
This paper highlights an analytical method based on mass measurement that can be used to directly quantify 129I in groundwater samples at concentrations below the maximum contaminant level (MCL) without the need for sample pre-concentration or extraction. Samples were analyzed on a Perkin Elmer ELAN DRC II ICP-MS after minimal dilution using O2 as the reaction gas. Analysis of continuing calibration verification standards indicated that the dynamic reaction cell (DRC) mode could be used for quantitative analysis of 129I in samples below the MCL (0.0057 ng/mL or 1 pCi/L). The low analytical detection limit of 129I analysis in the DRC mode coupled with minimal sample dilution (1.02x) resulted in a final estimated quantification limit of 0.0051 ng/mL. Subsequent analysis of three groundwater samples containing 129I resulted in fully quantitative results in the DRC mode, and spike recovery analyses performed on all three samples confirmed that the groundwater matrix did not adversely impact the analysis of 129I in the DRC mode. This analytical approach has been proven to be a cost-effective, high-throughput technique for the direct, quantitative analysis of 129I in groundwater samples at environmentally relevant concentrations that reach below the current MCL.
Fluid migration in subduction zones is one of the key phenomena to understand the global mass transfer system. While active volcanoes provide the most recognizable conduits for fluid flow in active margins, the existence of a large number of active fluid seepages demonstrates that other forms of fluid release are also important in subduction zone settings. The authors collected fluid samples from springs and wells across the forearc area in Kyushu, a southwestern island of Japan, covering hot spring activities associated with active volcanism and the Median Tectonic Line (MTL), a major fault system present in the southwestern part of Japan. In order to determine sources of these fluids, halogen concentrations as well as 129I/I and 36Cl/Cl ratios were measured in samples from several locations. While Cl concentrations of the forearc fluids in Kyushu range between seawater and meteoric water value, I concentrations are considerably higher than seawater value. Fluids in the Miyazaki area are much higher in I, and somewhat higher in Br, than waters in the Oita area, which is closely associated with the MTL. The differences between those two areas are also pronounced in 129I/I ratios, which range between 800 and 900 × 10−15 in the Oita area and between 100 and 360 × 10−15 in the Miyazaki area. The 129I/I ratios obtained from the Oita area are compatible with an I derivation from subducting marine sediments, similar to findings from an earlier investigation of fluids collected from Satsuma-Iwojima, an active volcano south of Kyushu Island. In the Miyazaki area, on the other hand, I ages are too old to be derived from currently subducting marine sediments and point to a derivation from old organic-rich materials in the upper plate of the forearc region. The results demonstrate the presence of very different fluid systems in the forearc area of Kyushu: old CH4-rich fluids dominate in the seaward side of the forearc, while fluids close to the MTL and the Quaternary Volcanic Front demonstrate derivations from subducting marine sediments. The latter fluids in the MTL area probably are transported through the fractures associated with the fault activities, suggesting that this fault system reaches the transition zone between upper and lower plates in this region.
Data are presented here on the anthropogenic 129I inventory in regions that have been strongly affected by releases from European reprocessing facilities which, to the authors’ knowledge, presently account for >90% of the global isotope source in the Earth’s surface environment. The results show that >90% of the isotope inventory occurs in marine waters with the Nordic Seas and Eurasian basin of the Arctic Ocean containing most of the 129I. Within the terrestrial environment of Europe, soils contain the largest part of the isotope inventory. However, the inventory of the terrestrial system did not provide clues on the most plausible atmospheric source of 129I to Europe, thus supply from both gaseous and marine releases is proposed. The sum of the total inventory in both the marine and terrestrial environments did not match the estimated releases. This imbalance is likely to relate to unconstrained inventory estimates for marine basins (Irish Sea, English Channel and North Sea) close to the facilities, but also to the occurrence of 129I in the biosphere, and possible overestimated releases from the nuclear reprocessing facilities. There is no doubt that the available data on 129I distribution in the environment are far from representative and further research is urgently needed to construct a comprehensive picture.
The long-lived halogen radioisotopes 129I and 36Cl provide valuable information regarding the source of fluids in hydrocarbon systems and in localized areas where infiltration of younger meteoric water has occurred. Despite the utility of these two isotopes in providing time-signatures for fluid end-members, considerable uncertainty remains regarding the interpretation of “intermediate-age” waters in hydrologic systems. These waters are likely the result of the combination of two or more halogen sources at some time in the past, each with its own characteristic concentration and isotopic composition. In order to unravel the evolution of these “intermediate-age” waters, the effect that infiltration of meteoric water has on the isotopic composition of older formation waters is modeled. Also evaluated is the effect that the timing of dilution has on 129I and 36Cl signatures observed in the present, specifically, the hypothesis that halogen isotopic signatures imparted by the mixing of brine and meteoric waters early in the development of a sedimentary basin are quantitatively different from those imparted by the mixing of old brines with recent meteoric waters.
Iodine is a biophilic element, with one stable isotope, 127I, and one long-lived radioisotope, 129I. Radioiodine originates in the surface environment almost entirely from anthropogenic activities such as nuclear fuel reprocessing in Europe and thus provides a unique point source tracer. Very few studies have evaluated the geochemical behavior of I isotopes in the subsurface. In this study, the concentrations of 129I and 127I were measured in wells fed by a series of artificial recharge ponds in the Forebay Area of the Orange County ground water basin (California, USA) to evaluate their potential use as hydrological tracers. To substantiate interpretation of 129I and 127I concentration data, the aquifer system was evaluated using the literature values of aquifer water mass age based on 3H/3He, Xe and δ18O tracer data. The aquifer data demonstrate the nearly conservative behavior of 129I with 129I/127I ratios likely reflecting variations in source functions as well as climatic conditions, and with inferred particle-water partition coefficients (Kd) of 0.1 cm3 g−1 or less.
This study presents the characterization of Pu-bearing precipitates and the results from uptake studies of Np and Pu on inorganic colloidal particulates in J-13 water from the Yucca Mountain site. Plutonium solubilities determined experimentally at pH values of 6, 7, and 8.5 are about two orders of magnitude higher than those calculated using the existing thermodynamic database indicating the influence of colloidal Pu(IV) species. Solid phase characterization using X-ray diffraction revealed primarily Pu(IV) in all precipitates formed at pH 6, 7, and 8.5. The solubility controlling Pu-bearing solids precipitated at ambient temperature consisted of amorphous Pu(OH)4(s) with several Pu–O distances between 2.3 and 2.7 Å that are characteristic for Pu(IV) colloids. High temperature (90 °C) increased solid phase crystallinity and produced Pu(IV) solids that contained Pu oxidation state impurities. X-ray absorption spectroscopic studies revealed diminished Pu–O and Pu–Pu distances that were slightly different from those in crystalline PuO2(s). A Pu–O bond of 1.86 Å was identified that is consistent with the plutonyl(V) distance of 1.81 Å in PuO2+(aq). Hematite, montmorillonite, and silica colloids were used for uptake experiments with 239Pu(V) and 237Np(V). The capacity of hematite to sorb Pu significantly exceeded that of montmorillonite and silica. A low desorption rate was indicative of highly stable Pu-hematite colloids, which may facilitate Pu transport to the accessible environment. Neptunium uptake on all mineral phases was far less than Pu(V) uptake suggesting that a potential Pu(V)–Pu(IV) reductive sorption process was involved. The temperature effect on Pu solubility and pseudocolloid formation is also discussed.
Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ13C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ13C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C3 and C4 plants and can be distinguished from that in the patchy forest areas where exclusive C3 trees yield a narrow δ13C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ13C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C3 and C4 contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.
This paper reports the results of determinations of137Cs and other radionuclides in bottom sediments and suspended matter collectedin a coastal zone of the northern Adriatic off the lagoon of Venice and at the estuary of the Adige River. The activity, behaviour and distribution of137Cs and some natural radionuclides were determined in materials sampled up to 1984. Various artificial radionuclides (134Cs,103Ru,106Ru, together with137Cs introduced by the accident Chernobyl) were detected samples collected in 1986. The study of the distribution of137Cs as a function of sediment properties showed that this radionuclide preferentially accumulates in the finest particles (6–12 phi, i.e. 16-0.24 μm range) and is taken up by adsorpion surface processes. This radioisotope has been used as tracer for recent sedimentary processes occurring in the study area and also as a tracer for predicting the fate of other inorganic and organic pollutants reaching the sediments by natural process. Exceptionally high values of radioactivity were observed after the Chernobyl accident in the estuary of the Adige River, particularly in suspended matter.
The Chernobyl radionuclides distribution and mobility in soils and uptake by plants have been studied in seminatural and agricultural moraine and in fluvioglacial landscapes typical for the areas of the Bryansk region affected by the accident.The major part of the Chernobyl 137Cs accumulated in the topsoil is insoluble in water, 40 to 93% of this radionuclide is strongly fixed by soil, while 70 to 90% of the 90Sr is present in water soluble, exchangeable and weak-acid soluble forms. Radionuclide vertical migration is most pronounced in local depressions with organic and gley soils in which both radionuclides are detected to the depth of 30–40 cm.In woodlands, most of the 137Cs is still fixed in litter and the upper mineral soil layer. The concentration peak in litter has moved to the lower AOF layer. Concentration in topsoil leads to high radionuclide uptake by forest species with shallow root systems (bilberry, mushrooms, fern). Contaminated forest products may contribute considerably to the internal irradiation doses of the local population. On flood plain grasslands traditionally used by local populations for haycrops and grazing, radionuclides are more strongly fixed in soils with fine texture. Radioisotope uptake by plants decreases in the order: legumes>herbs>grasses. Transfer to grasses in local depressions is usually higher compared with the dry levees. Observed exclusions are assumed to be due to comparatively low mobility of 137Cs and relatively high K content in soil. 137Cs accumulation in potato tubers grown on sandy soddy podzolic watershed soils mainly corresponds to its total amount in soils; uptake of 90Sr depends upon the percentage of its most mobile fraction.Pronounced relief is proved to cause different patterns in distribution and migration of radionuclides in soils and local food chains. The study showed it to be true for private farms situated in different landscape positions within the same settlement.The forest litter, topsoil and products, and flood plain pastures, especially localities in depressions are critical materials for the long-term radioecological monitoring of the contaminated landscapes of the study area and those of similar conditions. Population of the areas within the zone of contamination exceeding 15Ci/km2 (555kBq/m2) should be recommended to exclude local forest products from their diets and to avoid cattle grazing on wet flood plain meadows without remediation.
Geochemical and isotopic studies of pore fluids and solid phases recovered from the Dead Dog and Bent Hill hydrothermal sites in Middle Valley (Ocean Drilling Program Leg 169) have been compared with similar data obtained previously from these sites during Ocean Drilling Program Leg 139. Although generally the hydrothermal systems reflect non-steady state conditions, the data allow an assessment of the history of the hydrothermal processes. Sediment K/Al ratios as well as the distribution of anhydrite in the sediments suggest that the Dead Dog hydrothermal field has been, and still is, active. In contrast, similar data in the Bent Hill hydrothermal field indicate a waning of hydrothermal activity. Pore fluid and hydrothermal vent data in the Dead Dog hydrothermal field are similar in nature to the data collected during ODP Leg 139. In the area of the Bent Hill sulfide deposit, however, the pore water data indicate that recent wholesale flushing of the sediment column with relatively unaltered seawater has obliterated a previous record of hydrothermal activity in the pore fluids. Data from the deepest part of Hole 1035A in the Bent Hill locality show the presence of hydrothermal fluids at greater depths in this area. This suggests the origin of the hydrothermal fluids found to be emanating from Hole 1035F, which constitutes one of the first man made hydrothermal vents in the Middle Valley hydrothermal system. Similarly, CORKed Hole 858G, because of seal failures, has acted as a hydrothermal vent, with sulfide deposits forming inside the CORK.
Thermal analyses (TG–DTA), elemental composition and isotope analyses (13C and 15N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ13C and δ15N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.
Humic substances (HS) isolated from swamp water, surface soil, peat and brown coal were characterized using elemental composition, solid state 13C CP/MAS NMR and Py-GC/MS analysis. A substantial amount of information with regard to the source, maturity, depositional environment and degree of degradation of humic substances was obtained. The elemental composition, atomic ratio, 13C NMR spectra and Py-GC/MS results indicated that vascular plant matter is the main contributor to humic substances. Humic substances from swamp water and from soil in the surrounding area of the swamp were found to be identical, suggesting that the swamp humic substances are derived from surrounding soils. Humic substances from brown coal were characterized by a higher degree of humification, including loss of polysaccharides, degradation in lignin content and increase in aromaticity. Compared with humic substances from brown coal, the humic substances from peat showed a lower degree of humification and were considerably more aliphatic in nature.
Radiolabelled assays and compound-specific stable isotope analysis (CSIA) were used to assess methyl tert-butyl ether (MTBE) biodegradation in an unleaded fuel plume in a UK chalk aquifer, both in the field and in laboratory microcosm experiments. The 14C-MTBE radiorespirometry studies demonstrated widespread potential for aerobic and anaerobic MTBE biodegradation in the aquifer. However, δ13C compositions of MTBE in groundwater samples from the plume showed no significant 13C enrichment that would indicate MTBE biodegradation at the field scale. Carbon isotope enrichment during MTBE biodegradation was assessed in the microcosms when dissolved O2 was not limiting, compared with low in situ concentrations (2 mg/L) in the aquifer, and in the absence of O2. The microcosm experiments showed ubiquitous potential for aerobic MTBE biodegradation in the aquifer within hundreds of days. Aerobic MTBE biodegradation in the microcosms produced an enrichment of 7‰ in the MTBE δ13C composition and an isotope enrichment factor (ε) of −1.53‰ when dissolved O2 was not limiting. However, for the low dissolved O2 concentration of up to 2 mg/L that characterizes most of the MTBE plume fringe, aerobic MTBE biodegradation produced an enrichment of 0.5–0.7‰, corresponding to an ε value of −0.22‰ to −0.24‰. No anaerobic MTBE biodegradation occurred under these experimental conditions. These results suggest the existence of a complex MTBE-biodegrading community in the aquifer, which may consist of different aerobic species competing for MTBE and dissolved O2. Under low O2 conditions, the lower fractionating species have been shown to govern overall MTBE C-isotope fractionation during biodegradation, confirming the results of previous laboratory experiments mixing pure cultures. This implies that significant aerobic MTBE biodegradation could occur under the low dissolved O2 concentration that typifies the reactive fringe zone of MTBE plumes, without producing detectable changes in the MTBE δ13C composition. This observed insensitivity of C isotope enrichment to MTBE biodegradation could lead to significant underestimation of aerobic MTBE biodegradation at field scale, with an unnecessarily pessimistic performance assessment for natural attenuation. Site-specific C isotope enrichment factors are, therefore, required to reliably quantify MTBE biodegradation, which may limit CSIA as a tool for the in situ assessment of MTBE biodegradation in groundwater using only C isotopes.Highlights► Carbon isotope fractionation for MTBE varies with dissolved oxygen concentration. ► Carbon isotope fractionation can underestimate MTBE biodegradation at plume fringes. ► Fractionation factors must be for specific biodegradation mechanisms and conditions. ► Specific microbial populations influence carbon isotope fractionation in groundwater.
The oxidation of Fe(II) is apparently the rate-limiting step in passive treatment of coal mine drainage. Little work has been done to determine the kinetics of oxidation in such field systems, and no models of passive treatment systems explicitly consider iron oxidation kinetics. A Stella II™ model using Fe(II)init concentration, pH, temperature, Thiobacillus ferrooxidans and O2 concentration, flow rate, and pond volume is used to predict Fe(II) oxidation rates and concentrations in seventeen ponds under a wide range of conditions (pH 2.8 to 6.8 with Fe(II) concentrations of less than 240 mg L−1) from 6 passive treatment facilities. The oxidation rate is modeled based on the combination of published abiotic and biological laboratory rate laws. Although many other variables have been observed to influence Fe(II) oxidation rates, the 7 variables above allow field systems to be modeled reasonably accurately for conditions in this study.Measured T. ferrooxidans concentrations were approximately 107 times lower than concentrations required in the model to accurately predict field Fe(II) concentrations. This result suggests that either 1) the most probable number enumeration method underestimated the bacterial concentrations, or 2) the biological rate law employed underestimated the influence of bacteria, or both. Due to this discrepancy, bacterial concentrations used in the model for pH values of less than 5 are treated as fit parameters rather than empirically measured values.Predicted Fe(II) concentrations in ponds agree well with measured Fe(II) concentrations, and predicted oxidation rates also agree well with field-measured rates. From pH 2.8 to approximately pH 5, Fe(II) oxidation rates are negatively correlated with pH and catalyzed by T. ferrooxidans. From pH 5 to 6.4, Fe(II) oxidation appears to be primarily abiotic and is positively correlated with pH. Above pH 6.4, oxidation appears to be independent of pH. Above pH 5, treatment efficiency is affected most by changing design parameters in the following order: pH>temperature≈influent Fe(II)>pond volume≈O2. Little to no increase in Fe(II) oxidation rate occurs due to pH increases above pH 6.4. Failure to consider Fe(II) oxidation rates in treatment system design may result in insufficient Fe removal.
Distilled water was percolated for 38 days through Soultz granite (France) from the candidate site of the future Hot Dry Rock (HDR) geothermal exchanger at 180°C and 14 bars in a dynamic experimental system (plug-flow system with Ti reaction cell: I.D. 50 mm and L. 120 mm). The amplitude of dissolution and precipitation reactions was estimated after fluid analysis, and scanning electron microscope observations of the minerals were done following the percolation experiment. There were well developed etch pits on the surface of the feldspars. These were, therefore, the most reactive minerals. Dissolution and precipitation are distributed in zones along the flow path of the reacting fluid. Newly precipitated calcite is observed along the fluid flow path. Ferromagnesian saponite precipitates only at the outlet part of the system. The following mobility order was observed: SiO2 > HCO3 > F ∼ Na > Ca > Al > Li > Cs > Mg > Ba > Rb > B > Sr.By combining dissolution reaction kinetics, according to the law of the transition state theory, for the granite minerals, and the local chemical equilibrium approach for the precipitation of the secondary minerals and for the reactions of aqueous complexation, we were able to simulate the first reaction pathway of this experiment using the geochemical code EQ3/6 with the ‘fluid-centred flow-through' calculation mode.The experimental results (observations of minerals and chemial composition of theoutlet fluid) provided model constraints. Particular attention was paid to the effectively reactive surface of the minerals. The correction of the reactive surface in relation to the total measured surface was necessary so that calculated results would be in agreement, at least qualitatively, with observations. A good agreement is obtained only if the effective reactive surface of the minerals is taken to be from 0.03 to 3.2% of the total surface measured by the BET-N2 method.
Compositional data from published sources, environmental monitoring and new analyses demonstrate that for a wide range of water types (oilfield water, coal mine water, landfill leachate) NH4+ is present in amounts up to 2200 mg/L. Oilfield waters from Alberta, Canada contain 1–1000 mg/L NH4+, coal mine water (UK) surface discharges 1–45 mg/L NH4+, and landfill leachates (UK) up to 2200 mg/L NH4+. Ammonium contents generally show a positive correlation with K, and increase with increasing salinity. Geochemical modelling of sufficiently complete data using SOLMINEQ88 demonstrates that NH4+ activities vary systematically, and are consistent with a mineralogical control. Sodium–K exchange divides the entire sample suite into at least 4 groups, controlled by reaction temperature and reaction with either albite/K-feldspar or illitic clay minerals. In contrast, comparison of NH4+ and K divides the sample suite into 2 groups. On the basis of geological setting, these correspond to K–NH4+ exchange involving illitic (illite-muscovite) clays (and possibly feldspars) for samples from natural sources, and to exchange involving smectitic clays for samples from landfill sites. This study demonstrates the importance of NH4+ as a constituent of natural groundwaters, requiring that this reservoir of N is taken into account in detailed discussion of hydrological components of the N cycle.
4He concentrations in excess of the solubility equilibrium with the atmosphere by up to two to three orders of magnitude are observed in the Carrizo Aquifer in Texas, the Ojo Alamo and Nacimiento aquifers in the San Juan Basin, New Mexico, and the Auob Sandstone Aquifer in Namibia. A simple 4He accumulation model is applied to explain these excess 4He concentrations in terms of both in situ production and a crustal flux across the bottom layer of the aquifer. Results from the model simulations suggest variability in the 4He fluxes, ranging from 6×10−6 cm3 STP cm−2 yr−1 for the Auob Sandstone Aquifer to 3.6×10−7 cm3 STP cm−2 yr−1 for the Carrizo aquifer. For the Ojo Alamo and Nacimiento aquifers an intermediate value of 3×10−6 cm3 STP cm−2 yr−1 was estimated. The contribution of in-situ produced 4He to the measured concentrations was also estimated. This contribution is negligible for the Auob Sandstone Aquifer as compared with both the concentrations measured at the top and bottom of the aquifer for most of the pathway. In the Carrizo aquifer, in-situ produced 4He contributes 27.5% and 15.4%, to the total 4He observed at the top and bottom of the aquifer, respectively. For both aquifers of the San Juan Basin in-situ production almost entirely dominates the 4He concentrations at the top of the aquifer for most of the pathway. In contrast, the internal production is negligible as compared with the measured concentrations at the bottom of these aquifers, reaching, at most, 1.1%. The model simulations require an exponential decrease in the horizontal velocity of the water with increasing recharge distance to reproduce the distribution of 4He in these aquifers. For the Auob Sandstone Aquifer the highest range in the velocity values is obtained (25 to 0.4 m yr−1). The simulations for the Carrizo aquifer and both aquifers located in the San Juan Basin require velocities varying from 4 to 0.1 m yr−1, and from 2 to 0.3 m yr−1, respectively. For each aquifer, average permeability values were also estimated. They are generally in agreement with results obtained from pumping tests, hydrodynamic modeling and previous 14C measurements. On the basis of the results obtained by calibrating the model with the measured 4He concentrations, the mean water residence times were estimated. They agree reasonably well with 14C ages. When applied as chronologies for noble gas temperatures in the same aquifers, the calculated 4He ages allow the identification of three different climate periods similar to those previously identified using 14C ages: (1) the Holocene period (0–10 Ka BP), (2) the Last Glacial Maximum (≈18 Ka BP), and (3) the preceeding period (30–150 Ka BP).
Groundwaters from the Tithonian/Kimmeridgian, Oxfordian and Upper Dogger aquifers, within the eastern part of the Paris basin (France), were characterised using 3H, 14C and 36Cl, and noble gases tracers, to evaluate their residence times and determine their recharge period. This information is an important prerequisite to evaluating the confinement properties of the Callovo-Oxfordian clay formation sandwiched between the Oxfordian aquifer and the Dogger aquifer, currently being investigated by the French nuclear waste management agency (Andra) for radioactive waste disposal. Data presented in this paper are used to test 4 hypotheses.
Thirteen water-production wells in glacial sediments in and around Waterloo, Ontario, (Canada) were sampled for major ions, 3H, 13C, 14C and 18O in 1976 and again in 1988 to gauge the movement of bomb-spike tritium and 14C through the Waterloo aquifer and also to assess the reliability of a hydrogeochemical interpretation of the dynamic character of an aquifer based only on single sampling episode.The suite of samples collected in 1976 was not able to indicate how fast the tritium spike was moving or even if each well-screen was intercepting the front end or tail end of the bomb-spike peak corresponding to infiltration of mid-1960s precipitation. The second sampling event portrayed movement which, qualitatively at least, gave information relating to the more permeable zones of the aquifer and direction of water movement.Water from all but one of the 13 wells sampled in 1988 registered a drop in tritium relative to the 1976 sampling. A well is deemed to be intercepting the front end of the peak of the bomb-spike if its 1988 tritium activity (±2 TU analytical uncertainty) is greater than one half that of the tritium activity of well water measured in 1976 (±8 TU uncertainty). Only one well and two shallow piezometers met this criterion. Ten wells had TU1988/TU1976 ratios which could be interpreted as either greater than or less than 0.5, if the analytical uncertainties of both analyses in this ratio are rigorously applied. Screens of two wells intercept the tail end of the spike because both their uncertainty-adjusted TU1988/TU1976 ratios range from 0.29 to 0.41.Carbon-14 activity for individual wells varied by no more than 6 Per cent Modern Carbon (PMC) between 1976 and 1988. Bomb-spike 14C is not so easily detected as tritium in passage through aquifers because the thermonuclear input of 14C into the atmosphere was much less intense (relative to pre-bomb, background levels) than that for tritium. Also, incongruent dissolution of dolomite, coupled with differing dissolution kinetics between dolomite and calcite, precipitates 14C-bearing calcite in the saturated zone.Although the chemistry of an aquifer can be reasonably characterized by a single sampling episode, the recharge rate and groundwater flow paths are best delineated from a geochemical perspective by multiple samplings in which a persistent chemical and/or isotopic tracer is sought out and repeatedly analyzed. In the Waterloo aquifer, these are tritium and Cl. The sameness of 14C activity in waters sampled 12 a apart makes this a poor candidate to use in this scheme.
Stable isotopes of O (δ18O) in water and N (δ15N) in have been used as natural indigenous groundwater tracers for sources of water and of at two riverbank filtration (RBF) water supply systems. Both RBF systems (Skorkov and Sojovice) have wells in unconsolidated Quaternary sediments close to the Jizera River (Czech Republic) that have been affected by increasing concentrations. The area is underlain by Turonian sandstones and marls that form a deeper bedrock aquifer. Sources of are local sewerage systems and landfills (point sources) and seasonal application of manure and inorganic fertilizers (diffuse sources).At RBF Skorkov recharge to wells can be modelled using a two-component model with 60% river water contribution and 40% of very shallow groundwater with an average residence time of one month. During periods of abundant precipitation, groundwater originates entirely from the unsaturated zone of the Quaternary aquifer; extensive pumping for over 40 a has created new, bypassing flow paths that preferentially drain the contaminated unsaturated zone. During dry periods, wells are recharged by longer residence time groundwater from the Quaternary aquifer.At RBF Sojovice there is an additional recharge component of groundwater from the Turonian aquifer, which is sandier at this locality; this contains denitrified with highly positive δ15N values.
Geochemical studies of pore fluids and solid phases in two Ocean Drilling Program (ODP) drill sites (Sites 1037 and 1038) in the Escanaba Trough off Northern California have provided further data on the hydrothermal processes associated with the spreading of the Gorda Ridge. Previous work in the area of ODP Site 1038 includes the discovery of a hydrothermal system and associated sulfide deposits centered around an uplifted sediment hill in this sedimented extensional environment. This earlier work provided some insights into the present nature of venting; however, only deep drilling investigations can provide the means to fully understand the genesis and evolution of this system and associated hydrothermal deposits. ODP Leg 169 is the third deep drilling operation to explore the magnitude, genesis, and evolution of hydrothermal systems on sedimented ridges. Previous studies centered on the Guaymas Basin in the Gulf of California and the Middle Valley in the NE Pacific Ocean. Pore water studies in the reference ODP Site 1037 and in the hydrothermally active area of ODP Site 1038 have revealed the presence of a complex system of hydrothermally originated fluids. Whereas the data in the reference site indicate recent hydrothermal activity in the basal part of the drill site, the evidence in Site 1038 suggests that fluids of hydrothermal origin spread out at shallow depths around the central hill, causing substantial sediment alteration as well as deposition of hydrothermal sulfides in the near surface zone of the sediments. A second major discovery at Site 1038 was the evidence for fluid phase separation at depth at temperatures possibly in excess of 400 °C. This conclusion is based on the presence of both low Cl and high Cl fluids. The latter appear to be advected rapidly towards the surface, presumably along cracks and faults. The low Cl fluids, however, appear to be transported laterally along sandy horizons in the sediments, thus signifying two very different migration pathways for high Cl and low Cl hydrothermally phase separated fluids. Studies of the organic geochemistry of dissolved gases and matured organic matter corroborate these findings of extensive hydrothermal alteration of the sediments.
The detailed understanding of in situ biodegradation of petroleum hydrocarbons in porous aquifers requires knowledge on biogeochemical gradients, the distribution of individual redox species and microorganisms. The generally limited spatial resolution of conventional monitoring wells, however, hampers appropriate characterization of small-scale gradients and thus localization of the relevant processes. Groundwater sampling across a BTEX plume in a sandy aquifer by means of a novel high-resolution multi-level well (HR-MLW) is presented here. The presence of distinct and steep biogeochemical gradients is demonstrated in the centimeter and decimeter scale, which could not be resolved with a conventional multi-level well. The thin BTEX plume with a vertical extension of only 80 cm exhibited a decline of contaminant concentrations by two orders of magnitude within a few centimeters in the upper and lower fringe zone. The small-scale distribution of sulfate, sulfide and Fe(II) in relation to the contaminants and elevated δ34S and δ18O values of groundwater sulfate strongly indicated sulfate and iron reduction to be the dominant redox processes involved in biodegradation. High microbial activities and biomass especially at the plume fringes and the slope of chemical gradients supported the concept that the latter are regulated by microbial processes and transverse dispersion, i.e. vertical mixing of electron donors and acceptors. Transverse dispersion therefore was suggested to be a driving factor controlling biodegradation in porous aquifers, but not exclusively limiting natural attenuation processes at this site. Broad overlapping zones of electron donors and electron acceptors point towards additional factors limiting anaerobic biodegradation in situ. The identification of small-scale gradients substantially contributed to a better understanding of biodegradation processes and hence is a prerequisite for the development of reliable predictive mathematical models and future remediation strategies.
This paper deals with chemical and isotope analyses of 21 springs, which were monitored 3 times in the course of 2001; the monitoring program was focused on the groundwater of the Gran Sasso carbonate karst aquifer (Central Italy), typical of the mountainous Mediterranean area.Based on the hydrogeological setting of the study area, 6 groups of springs with different groundwater circulation patterns were distinguished. The hydrogeochemistry of their main components provided additional information about groundwater flowpaths, confirming the proposed classification. The spatial distribution of their ion concentrations validated the assumptions underlying the hydrogeological conceptual model, showing diverging groundwater flowpaths from the core to the boundaries of the aquifer. Geochemical modelling and saturation index computation elucidated water–carbonate rock interaction, contribution by alluvial aquifers at the karst aquifer boundaries, as well as impacts of human activities.The analysis of 18O/16O and 2H/H values and their spatial distribution in the aquifer substantiated the hydrogeology-based classification of 6 groups of springs, making it possible to trace back groundwater recharge areas based on mean isotope elevations; the latter were calculated by using two rain monitoring stations. 87Sr/86Sr analyses showed seasonal changes in many springs: in winter–spring, the changes are due to inflow of new recharge water, infiltrating into younger rocks and thus increasing 87Sr/86Sr values; in summer–autumn, when there is no recharge and spring discharge declines, changes are due to base flow groundwater circulating in more ancient rocks, with a subsequent drop in 87Sr/86Sr values.The results of this study stress the contribution that spatio-temporal isotope monitoring can give to the definition of groundwater flowpaths and hydrodynamics in fissured and karst aquifers, taking into account their hydrogeological and hydrogeochemical setting.
The Pecos River, situated in eastern New Mexico and western Texas, receives water from a drainage area of 91 000 km2. There are primarily two major water inputs, namely snowmelt from winter storms in the headwater region of the southern Rocky Mountains and runoff from warm-season monsoonal rainfall in the lower valley. The Pecos River suffers from high levels of total dissolved solids (TDS >5000 mg L−1) under normal flow conditions. This not only poses serious problems for agricultural irrigation and safe drinking water supply, but also results in a permanent loss of biodiversity. This study examines changes in stream flow and water chemistry of the Pecos River over the last 70 a to better understand the long-term variability in stream salinity and the role of agricultural practices in salt transfer. A TDS record from the lower Pecos River near Langtry (Texas) back to 1935 was extracted to show a distinct pattern of decadal variability similar to the Pacific Decadal Oscillation (PDO), in which stream salinity is overall above average when the PDO is in positive (warm) phase and below average when the PDO is in negative (cold) phase. This is due to: (1) the dissolved salts contributed to the river are largely from dissolution of NaCl and CaSO4-bearing minerals (e.g., halite and gypsum) in the upper basin, (2) the amount of the dissolved salts that reach the lower basin is mainly determined by the stream flow yield in the upper basin and (3) the stream flow yield from the upper basin is positively correlated with the PDO index. This further attests that large-scale climatic oscillation is the major source of long-term changes in stream flow and salinity of the Pecos River. On the other hand, there is also a strong indication that the rate of salt export has been affected by reservoir operations and water diversions for agricultural practices.
The potentially toxic elements Hg and As are found at high concentrations in surface/near-surface sediments from Arctic ocean cores collected from the Voronin Trough, Kara Sea, during 1965. The levels reach 2045 ppb for Hg and 270 ppm for As. Manganese high values (up to 1.27%) are also found in the cores’ surface/near-surface sections. Other heavy metals tracked by the Arctic Monitoring and Assessment Program (e.g., Cu, Ni, Pb, Sb, Ti, Zn) have baseline concentrations in the cores. The cores average >57% clay-size and >35% silt-size in their textural composition. The elevated contents may result from anthropogenic input for Hg and As with diagenesis adding to the As concentration. Possible sources for these elements are emissions and effluents from industry such as mining and smelting operations, and burning of fossil fuels in Siberia and the Urals. When discharged into the Kara Sea from Siberian catchments, the As and Hg likely attach to charged particulate surfaces of Fe oxy/hydroxides (for As) and particulate organic matter or clay minerals (for Hg). These are transported, entrained in ocean currents or adhered to pack ice, to the Voronin Trough where they deposit according to size and specific gravity.
A regional geochemical survey using soils, stream sediment and stream water sampling revealed multi-element geochemical anomalies, though of low environmental mobility, associated with Mesozoic sedimentary ironstones in Lincolnshire, UK. The most prominent of these anomalies were of As and V in soils and sediments, but elevated levels of elements such as Cr, La, Ce and Th were also observed. These were initially thought to be part of a residual resistate element or heavy-mineral suite, but careful examination suggests that these too may be primarily associated with the process of Fe oxide precipitation during the initial formation of the ironstones.
Atmospheric heavy metal deposition in Finland from 1985 to 1990 was monitored by the moss technique. The objectives were to examine the change in the heavy metal deposition with time and to produce information about the deposition and the emission sources.Samples were collected from the permanent sampling network systematically covering the country as a whole. The total number of samples was 4883 and the concentrations of Cd, Cr, Cu, Pb, Ni and V were determined.Some important emission sources cause local enhancements of the concentrations in moss. High metal concentrations were found around the Harjavalta smelters, around the Tornio steel mill and in the north-eastern parts of Lapland near the Finnish-Russian border close to heavy metal industry in the Kola Peninsula. Elevated levels were also found around the Raahe smeleter and around the oil refineries in Naantali and Porvoo. The effect of long-range transport from the Central and East Europe can be seen especially for Cd, Pb and V. Significant decrease in the concentrations of some elements was found from 1985 to 1990.
At present, the terms Environmental Geochemistry and Applied Geochemistry are poorly defined in English. In fact they usually mean just what a particular geochemist, or geochemist(s), wishes them to mean.There is a less common term, Landscape Geochemistry, which describes a holistic scientific discipline aimed at the geochemistry of the environment. Although little known outside the U.S.S.R., the basics of landscape geochemistry were first described more than 60 a ago. Since then, landscape geochemistry has had a history pertinent to all scientists who participate in environmental geochemistry today.This review traces the evolution of landscape geochemistry, and related disciplines, over the past 90 a and shows how they all relate to the development of modern environmental geochemistry worldwide.In landscape geochemistry, the term “landscape” refers to both the horizontal stratification of land (e.g. into terrestial, bog and aquatic ecosystems which co-exist in an area of country) and to the vertical stratification within these units (e. g. into vegetation, soils etc.). In these respects landscape geochemistry resembles Landscape Ecology, which is currently a discipline of growing importance in environmental science.Landscape geochemistry differs from landscape ecology because it focuses attention on all aspects of the behaviour of chemical entities (e. g. isotopes, elements and ions), in both living and dead matter in landscapes of all kinds.From the viewpoint of general geochemistry, landscape geochemistry focusess on the interaction of the lithosphere with the hydrosphere, atmosphere and biosphere. This holistic approach provides a common theoretical background for both “pure” and “applied” environmental geochemistry worldwide.An important aspect of landscape geochemistry, particularly pertinent to environmental geochemistry in the non-Soviet world today, is that the subject provides a link between modern exploration geochemistry and modern environmental science, including geochemistry.Historically, landscape geochemistry stems from the Russian school of “Landscape Science”. This developed from the ideas of V. V. Dokuchaev (1846–1903) around the turn of the century. Concepts unique to landscape geochemistry were first described in the 1920s by one of Dokuchaev's students, B. B. Polynov (1867–1952). A. I. Perel'man (1909- ), a student of Polynov, began to teach landscape geochemistry at Moscow University in 1952. Since then, the subject has become firmly established as the focus for fundamental and applied environmental geochemistry in the U.S.S.R.This review traces the development of landscape geochemistry from its origins around 1920 until 1990. The volume of literature pertinent to the review is voluminous. For this reason, attention is usually focused on the basic concepts and principles of landscape geochemistry and related scientific disciplines. Readers who require more detailed information on subjects covered in this review should consult the references cited.The review is organized in four parts. The first three trace the historical development of landscape geochemistry, and related disciplines, in three time periods. These are: (1) pre-1950; (2) between 1950 and 1980; and (3) 1980–1990. Part 4 uses paradigms to summarize the historical evolution of landscape geochemistry and indicates how a Global Landscape Geochemistry might develop in the future.
The foundations of geochemistry and health are associated with work in Canada, U.S.A., C.I.S. and U.K. in the 1960s and parallel studies in geomedicine in Scandinavia. The development of geochemical mapping techniques and compilation of geochemical atlases have led to innovative multidis-ciplinary research into their applications in the areas of agriculture and land use, fresh water quality for irrigation and potable supplies, estuarine and coastal waters and fisheries, medicine and public health, and environmental pollution. Recent developments have concerned the influence of geochemistry in wildlife nutrition. Research in urban geochemistry has been applied to the modification of the chemical environment in towns and cities arising from urban and industrial development.The paper illustrates this research with some specific case histories and presents the author's opinion as to those priority areas that will require both national and international input in the present decade and beyond.
Radon concentrations were continuously monitored in hot spring water in a 200-m-deep well in the Yugano hot spring area, Izu Peninsula, Japan from July to December 1995. Concentrations of Cl− and SO42− were measured in the hot spring water about once a month from May to December 1995. The Rn concentrations in the hot spring water increased significantly in September and October 1995, when the 1995 earthquake swarm off the E coast of the Izu Peninsula occurred at a distance of about 30 km from the observation well. The 1995 earthquake swarm began on 11 September and became most active from the end of September to the beginning of October. The Rn concentration rose gradually from 8 September, 3 days before the onset of the swarm activity, increasing by about 50% by 17 September. It remained high in October but had returned to normal by the end of November. However, Cl− and SO42− concentrations doubled suddenly from 22 to 23 September and remained high until the end of November. A good correlation between Cl− and SO42− concentrations suggests the same mechanism for their anomalous increases, probably mixing of water with high Cl− and SO42− concentrations caused by crustal deformation related to the seismic swarm activity. However, the anomalous increase in Rn concentration, which began 15 days before these anion increases, cannot be explained by the same water mixing mechanism. A possible mechanism for the anomalous Rn increase is the formation of microcracks caused by compressional stress, which preceded the onset of the earthquake swarm.
Despite the widespread occurrence of chlorophenols as groundwater contaminants, the aqueous solubilities of the chlorophenols are not well-characterized. In this study, the authors report the solubility of 2,4,6-trichlorophenol (2,4,6-TCP) and pentachlorophenol (PCP) based on experiments conducted as a function of pH, ionic strength and temperature, and a speciation-based model for estimating the solubilities of other chlorophenols is derived.Narrow constraints on the aqueous solubility of both chlorophenols were made possible by conducting experiments in pure water and in 0.1 NaCl at 25°C and 55°C, from both under- and over-saturation. The solubility of the chlorophenols is pH-independent under low pH conditions, but at higher pH values it increases with increasing pH. The concentration of the protonated chlorophenol species determines the low pH solubility and, at 25°C, the log molality of the protonated species of 2,4,6-TCP is −2.8±0.1, whereas for PCP the value is −5.1±0.3. Two other properties were used to model the solubility as a function of pH: the acidity constant (Ka) and the stability constant for a Na-chlorophenolate complex. The pKa and Na-chlorophenolate log stability constant values that best fit the solubility data for 2,4,6-TCP are 6.1±0.3 and 1.0±0.5, respectively; the values for PCP are 4.5±0.3 and 1.0±0.5, respectively. At 55°C, the log molality of protonated PCP increases to −4.7±0.2 and the pKa and log stability constant value are 4.1±0.3 and 0.9±0.5, respectively. The log stability constant for NaPCP° at 55°C is equal to 0.9±0.5.The experimental solubility measurements are used to construct a theoretical model which defines the solubility of a chlorophenol in terms of its acidity constant and its low pH minimum solubility. This approach enables estimations of the aqueous solubility of other chlorophenol molecules as a function of pH, ionic strength and temperature. In order to facilitate application of this model to other chlorophenol molecules, the authors compile and critically review the solubility data for 20 chlorophenols from the literature. The results of the experiments and review enable estimations of chlorophenol solubilities under a wide range of conditions of environmental interest.
The reactive behavior of supercritical CO2 under conditions relevant to geologic storage and sequestration of C is largely unknown. Experiments were conducted in a flexible cell hydrothermal apparatus to determine the extent of fluid–rock reactions, in addition to carbonate mineral precipitation, that may occur in a brine aquifer–aquitard system that simulates a saline aquifer storage scenario. The system was held at 200 °C and 200 bars for 59 days (1413 h) to approach steady state, then injected with CO2 and allowed to react for another 80 days (1924 h). In addition to magnesite precipitation, silicate minerals (quartz, plagioclase, microcline and biotite) in the aquifer and the aquitard display textures (etch pits, mineralization) indicating significant reaction. Changes in elemental abundances in the brine following addition of CO2 include pH decrease and enrichment in Cl−, partly due to supercritical CO2 desiccation of the brine. Geologic sequestration systems have potential for geochemical reactions that extend beyond simple aqueous dissolution of CO2 and precipitation of carbonate. These reactions may produce geochemical and geotechnical consequences for sequestration and provide important characteristics for monitoring and evaluation of stored CO2. An understanding of multi-phase equilibrium relationships between supercritical CO2 and aquifer–brine systems also raises new questions for a variety of geologic systems. Multi-phase fluid equilibria may, for example, account for the large amounts and heterogeneous distributions of calcite cement in a wide variety of geologic systems, particularly in sedimentary basin sandstones.
In January and March 2000 two tailings dam failures in Maramureş County, northwest Romania, resulted in the release of 200,000 m3 of contaminated water and 40,000 tonnes of tailings into tributaries of the Tisa River, a major tributary of the Danube. The high concentrations of cyanide and contaminant metals released by these dam failures resulted in pollution and fish deaths not only in Romania, but also downstream in the Tisa and Danube rivers within Hungary, Serbia and Bulgaria. Following these accidents, a research programme was initiated in northwest Romania to establish metal levels in rivers affected by the tailings dam failures and to compare these to metal values in river systems contaminated by historic mining and industrial activity. In July 2000, 65 surface water, 65 river sediment and 45 floodplain sediment samples were collected from trunk streams and principal tributaries of the Lapuş/Someş rivers (affected by the January 2000 spill) and the Vişeu/Tisa rivers (affected by the March 2000 Novat spill) down to the Hungarian and Ukrainian borders, respectively. Sample analyses for Pb, Zn Cu and Cd show that metal contamination in surface water and river sediment decreases rapidly downstream away from presently active mines and tailings ponds. Concentrations of heavy metals in water and sediment leaving Romania, and entering Hungary and the Ukraine, generally fall below EC imperative and Dutch intervention values, respectively. However, Zn, Cu and Cd concentrations in river sediments approach or exceed intervention values at the Romanian border. The results of this survey are compared with earlier surveys to ascertain the long-term fate and environmental significance of contaminant metals released by mine tailings dam failures in Maramureş County.
NOAA AVHRR images have clearly shown anomalous changes in land surface temperature associated with earthquakes in the past two decades. Soon after the Gujarat earthquake of January 26, 2001, an anomalous increase in land surface temperature was inferred from MODIS satellite data a few days prior to the main earthquake event. The cause of such an anomalous change in surface temperature prior to the earthquake is attributed to many probable phenomena, but no definite cause has been identified. In the present study, changes of a complementary nature were found of land surface temperature associated with the emission of CO from the epicentral region. The observed changes on land and atmosphere associated with the Gujarat earthquake of 26 January, 2001, show the existence of strong coupling between land, atmosphere and ionosphere.
The shells of marine and fresh water mollusks can serve as effective archives in retrieving information on natural and anthropogenic environmental changes. The advantage of using bivalves is that they integrate water chemistry changes into their shells during their life span. Retrospective study of environmental changes and pollutants using bivalve shells requires precise determination of the time of incorporation into the abiotic environmental matrix (here after age) of the specimen. For the first time, a set of archived bivalve samples (for which date of the death/collection is known) has been analyzed to establish the ages of mollusk shells using the 210Pb–226Ra disequilibrium method. In addition, Sr and 90Sr were analysed. The ages obtained using the 210Pb/226Ra disequilibrium dating method agrees well with the calendar years calculated from the date of death/collection. The ages obtained can be utilized to reconstruct the 90Sr levels in the water column at sites where the mollusk shells were collected.