Distinguishing Iron-Reducing from Sulfate-Reducing Conditions

Ground water systems dominated by iron‐ or sulfate‐reducing conditions may be distinguished by observing concentrations of dissolved iron (Fe²⁺) and sulfide (sum of H₂S, HS^?, and S⁼ species and denoted here as “H₂S”). This approach is based on the observation that concentrations of Fe²⁺ and H₂S in ground water systems tend to be inversely related according to a hyperbolic function. That is, when Fe²⁺ concentrations are high, H₂S concentrations tend to be low and vice versa. This relation partly reflects the rapid reaction kinetics of Fe²⁺ with H₂S to produce relatively insoluble ferrous sulfides (FeS). This relation also reflects competition for organic substrates between the iron‐ and the sulfate‐reducing microorganisms that catalyze the production of Fe²⁺ and H₂S. These solubility and microbial constraints operate in tandem, resulting in the observed hyperbolic relation between Fe²⁺ and H₂S concentrations. Concentrations of redox indicators, including dissolved hydrogen (H₂) measured in a shallow aquifer in Hanahan, South Carolina, suggest that if the Fe²⁺/H₂S mass ratio (units of mg/L) exceeded 10, the screened interval being tapped was consistently iron reducing (H₂～0.2 to 0.8 nM). Conversely, if the Fe²⁺/H₂S ratio was less than 0.30, consistent sulfate‐reducing (H₂～1 to 5 nM) conditions were observed over time. Concomitantly high Fe²⁺ and H₂S concentrations were associated with H₂ concentrations that varied between 0.2 and 5.0 nM over time, suggesting mixing of water from adjacent iron‐ and sulfate‐reducing zones or concomitant iron and sulfate reduction under nonelectron donor–limited conditions. These observations suggest that Fe²⁺/H₂S mass ratios may provide useful information concerning the occurrence and distribution of iron and sulfate reduction in ground water systems.     

Reinterpreting the Importance of Oxygen‐Based Biodegradation in Chloroethene‐Contaminated Groundwater

Chlororespiration is common in shallow aquifer systems under conditions nominally identified as anoxic. Consequently, chlororespiration is a key component of remediation at many chloroethene‐contaminated sites. In some instances, limited accumulation of reductive dechlorination daughter products is interpreted as evidence that natural attenuation is not adequate for site remediation. This conclusion is justified when evidence for parent compound (tetrachloroethene, PCE, or trichloroethene, TCE) degradation is lacking. For many chloroethene‐contaminated shallow aquifer systems, however, nonconservative losses of the parent compounds are clear but the mass balance between parent compound attenuation and accumulation of reductive dechlorination daughter products is incomplete. Incomplete mass balance indicates a failure to account for important contaminant attenuation mechanisms and is consistent with contaminant degradation to nondiagnostic mineralization products like CO₂. While anoxic mineralization of chloroethene compounds has been proposed previously, recent results suggest that oxygen‐based mineralization of chloroethenes also can be significant at dissolved oxygen concentrations below the currently accepted field standard for nominally anoxic conditions. Thus, reassessment of the role and potential importance of low concentrations of oxygen in chloroethene biodegradation are needed, because mischaracterization of operant biodegradation processes can lead to expensive and ineffective remedial actions. A modified interpretive framework is provided for assessing the potential for chloroethene biodegradation under different redox conditions and the probable role of oxygen in chloroethene biodegradation.     

Flowpath Independent Monitoring of Reductive Dechlorination Potential in a Fractured Rock Aquifer

The flowpath dependent approaches that are typically employed to assess biodegradation of chloroethene contaminants in unconsolidated aquifers are problematic in fractured rock settings, due to difficulties defining discrete groundwater flowpaths in such systems. In this study, the variation in the potential for chloroethene biodegradation with depth was evaluated in a fractured rock aquifer using two flowpath independent lines of field evidence: (1) the presence of the three biochemical prerequisites [electron donor(s), chloroethene electron acceptor(s), and chlororespiring microorganism(s)] for efficient chloroethene chlororespiration and (2) the in situ accumulation of chloroethene reductive dechlorination daughter products. The validity of this approach was assessed by comparing field results with the results of [1, 2-¹⁴C] cis -DCE microcosm experiments. Microcosms were prepared with depth-specific core material, which was crushed and emplaced in discrete packer intervals for 1 year to allow colonization by the indigenous microbial community. Packer intervals characterized by significant electron donor concentrations, elevated numbers of chlororespiring microorganisms, and high reductive dechlorination product to parent contaminant ratios correlated well with the production of ¹⁴C-labeled reductive dechlorination products in the microcosm experiments. These results indicate that, in the absence of information on discrete groundwater flowpaths, a modified approach emphasizing flowpath independent lines of evidence can provide insight into the temporal and spatial variability of contaminant biodegradation in fractured rock systems.     

Biostimulation and Bioaugmentation to Enhance Reductive Dechlorination of TCE in a Long‐Term Flow Through Column Study

Large laboratory columns (15.2 cm diameter, 183 cm long) were fed with groundwater containing trichloroethylene (TCE), were biostimulated and bioaugmented, and were monitored for over 7.5 years. The objective of the study was to observe how the selection of the carbon and energy source, i.e., whey, Newman Zone^® standard surfactant emulsified oil and Newman Zone nonionic surfactant emulsified oil, affected the rate and extent of dechlorination. Column effluent was monitored for TCE and its degradation products, redox indicators (nitrate‐N, Fe(II), sulfate), and changes in iron mineralogy. Total bacteria and Dehalococcoides mccartyi strains were quantified using q‐PCR. Complete dechlorination was only observed in the whey treated columns, occurring 1 year after bioaugmentation with addition of a culture known to dechlorinate TCE to ethene, and 3 years later in the non‐bioaugmented column. The addition of the emulsified oils with or without bioaugmentation resulted in dechlorination only through cis‐DCE and vinyl chloride. While Dehalococcoides mccartyi strains are the only known bacteria that can fully dechlorinate TCE, their presence, either natural or augmented, was not the sole determiner of complete dechlorination. The establishment of a supporting microbial community and biogeochemistry that developed with continuous feeding of whey, in addition to the presence of D. mccartyi, were necessary to support complete reductive dechlorination. Results confirm that careful selection of a biostimulant is critical to the success of TCE dechlorination in complex soil environments.     

Potentially Bioavailable Natural Organic Carbon and Hydrolyzable Amino Acids in Aquifer Sediments

This study evaluated the relationship between concentrations of operationally defined potentially bioavailable organic ‐carbon (PBOC) and hydrolyzable amino acids (HAAs) in sediments collected from a diverse range of chloroethene‐‐contaminated sites. Concentrations of PBOC and HAA were measured using aquifer sediment samples collected at six selected study sites. Average concentrations of total HAA and PBOC ranged from 1.96 ± 1.53 to 20.1 ± 25.6 mg/kg and 4.72 ± 0.72 to 443 ± 65.4 mg/kg, respectively. Results demonstrated a statistically significant positive relationship between concentrations of PBOC and total HAA present in the aquifer sediment (p < 0.05). Higher levels of HAA were consistently observed at sites with greater levels of PBOC and first‐order decay rates. Because amino acids are known to be readily biodegradable carbon compounds, this relationship suggests that the sequential chemical extraction procedure used to measure PBOC is a useful indicator of bioavailable carbon in aquifer sediments. This, in turn, is consistent with the interpretation that PBOC measurements can be used for estimating the amount of natural organic carbon available for driving the reductive dechlorination of chloroethenes in groundwater systems.     

Soil H<Subscript>2</Subscript> and CO<Subscript>2</Subscript> Surveys at Several Active Faults in Japan

Soil H₂ and CO₂ surveys were carried out along seven active faults and around the aftershock region of the 2000 Tottori-ken Seibu earthquake in Japan. Diffuse CO₂ effluxes were also measured along one fault and around the 2000 aftershock region. The results show highly variable H₂ concentration in space and time and it seems that the maximum H₂ concentration at each active fault correlates with fault activity as exemplified by the time of the latest big earthquakes. Even though observed H₂ concentrations in four faults were markedly lower than those collected previously in the latter half of the 1970s, it is evident that the higher H₂ concentrations in this study are due to the addition of the fault gases. Comparing the chemical composition of trapped gases (H₂: 5–20% and CO₂/H₂: 0.5–12) in fractured rocks of drill cores bored at the Nojima fault, a soil gas sample with the highest H₂ concentration showed large amounts of the trapped fault gas, diluted with atmospheric component. The profile experiment across a fracture zone at the Yamasaki fault showed higher H₂ concentrations and lower CO₂/H₂ ratios as was observed in soil gas from the fracture zone. A few days after the 2000 Tottori-kei Seibu earthquake, no CO₂ effluxes related to the occurrence of earthquakes were observed at the aftershock region. However, only above the epicenter zone, relatively high H₂ concentrations in soil gases were observed.     

Statistical Analysis of Secondary Water Quality Impacts from Enhanced Reductive Bioremediation

Enhanced reductive bioremediation (ERB) is effective for treating a broad range of groundwater contaminants, but does result in secondary water quality impacts (SWQIs). Monitoring data from 47 ERB projects were analyzed to gain a better understanding of the formation and extent of SWQIs. The database analysis revealed that SWQIs occur at virtually every site, including reduced levels of background aqueous electron acceptors (O₂, NO₃^?, and SO₄^2?), increases in dissolved‐phase metals (Fe and Mn), and the production of CH₄. However, the SWQI “plume” that is produced is usually confined within the original contaminant plume. As a result, SWQIs from ERB are unlikely to adversely impact potable water supplies. SWQIs do attenuate with distance downgradient, with concentrations often returning to near background levels. The results of the database analysis were combined with previous research to develop a general conceptual model (CM) of SWQI production, mobilization, and attenuation. This CM can assist in identifying conditions where SWQIs may pose a concern. These can include sites with low iron/high sulfate (H₂S mobilization), high groundwater velocity (SWQIs at distances far downgradient), and sites with low CH₄ anaerobic oxidation rates (CH₄ migration).     

Spatial variability of N2O concentrations and of denitrification-related factors in the surficial groundwater of a catchment in Northern Germany

N₂O concentrations and denitrification-related factors (NO₃, SO₄, dissolved organic carbon (DOC) and CO₂) were investigated in the surface groundwater of a catchment in northern Germany, the Fuhrberger Feld Aquifer (FFA). We sampled 79 plots that were selected according to the three criteria of land use, historical land use conversion (1954–1995) and groundwater level. We sampled three sites within each plot. The sampling depth was 0.5 m below the groundwater surface.We found no indication for the occurrence of autotrophic denitrification in the surface groundwater. Heterotrophic denitrification was identified as the main process for N₂O accumulation. The variability of N₂O concentrations on the plot-scale was extremely high and was poorly explained by the three sampling criteria. Other denitrification-related variables such as NO₃, SO₄ and DOC were less variable. The selection criteria land use and groundwater level clearly influenced the order of magnitude of N₂O concentrations in the surface groundwater. Under arable land, high NO₃ concentrations resulted in high N₂O concentrations. The surface groundwater under forest and pasture was almost NO₃-free and had also very small N₂O concentrations. Plots where the distance from the soil surface to the groundwater surface was large (>1 m up to 3.4 m) showed higher N₂O concentrations in the surface groundwater than plots where the distance was small (<1 m). A larger distance from the soil surface to the groundwater leads to a longer residence time and more decomposition of DOC in the soil. Consequently the less bioavailable DOC could inhibit the efficiency of the heterotrophic denitrification in the groundwater, yielding more N₂O. Elevated organic carbon levels in plots with historic land use conversion (pasture to arable) were very stable and did not influence N₂O concentrations. The high within plot variability showed that an upscaling of N₂O from the plot-scale to the catchment-scale is possible as long as the groundwater level regime and the land use do not change.     

Delineation of spatial redox zones using discriminant analysis and geochemical modelling in arsenic‐affected alluvial aquifers

This study characterized the redox conditions in arsenic‐affected groundwater aquifers of the Lanyang plain, Taiwan. Discriminant analysis was adopted to delineate three redox zones (oxidative, transitional and reductive zones) in different aquifers and yielded 92·3% correctness on groundwater quality data. Arsenic is mainly distributed in the reductive zone, and arsenic distribution in the shallow aquifer is mainly affected by surface activities. According to PHREEQC modelling results, possible mechanisms for arsenic release to groundwater in Lanyang plain are explored. Arsenic released to groundwater in the oxidative zone (zone 1) is primarily caused by the oxidations of arsenic‐bearing pyrite minerals, and arsenate is the predominant species. While the reductive dissolution of Fe‐oxides are responsible for the high arsenic concentration found in the transitional and reductive zones (zones 2 and 3), arsenite is the predominant species. The reduction potential of groundwater rises as the depths and zones increase. Some sulphates may be reduced to form sulphide ions, which then react with arsenic to form arseno‐sulphide deposits (such as realgar, orpiment) and then slightly lower groundwater arsenic concentrations. A conceptual diagram which summarized the possible release processes of arsenic in different redox zones along groundwater flow in Lanyang plain is postulated. Arsenic‐bearing pyrite and arsenopyrite (FeAsS) are oxidized as they are exposed to the infiltrated oxygenated rainwater, releasing soluble arsenate Fe(II) and SO₄^2? into zone 1. The dissolution of arsenic‐rich Fe‐oxides due to the onset of reducing conditions in zones 2 and 3 is responsible for the mobility of arsenic and likely to be the primary mechanism of arsenic release to groundwater in the Lanyang plain Copyright © 2007 John Wiley & Sons, Ltd.     

Interactions between groundwater seepage and sediment porewater sulphate concentration profiles in lake anna,Virginia

Most sulphur diagenesis models predict that SO₄^2- concentrations decrease exponentially with increasing sediment depth and are lower than that of the overlying water throughout the sediments. Low SO₄^2- concentrations (less than 0.2 mM) are common in the sediments of Lake Anna that receive acid mine drainage; however, sediment with as much as 20 mM SO₄^2- at about 20cm below the sediment surface is also seen in this section of the lake. A decision tree was proposed to investigate the cause of the high SO₄^2- concentrations at depth (HSD) in the sediment. The first possibility proposed was that an increase in the quantity of groundwater flowing through Lake Anna sediments may increase groundwater advection of SO₄^2- or oxygen which would induce sulphide oxidation. This hypothesis was tested by measuring groundwater flow. HSD profiles were found in a discrete region of the lake; however, stations having these profiles did not have higher groundwater flow than other sites sampled. Alternate explanations for the HSD profiles were that the region in which they occurred had: (1) unusual sediment chemical compositions; (2) a different source of regional groundwater, or (3) a lateral intrusion of high SO₄^2- groundwater. There were no differences in sulphide and organic matter concentrations between the two regions. The area which has HSD in the sediment covers a large area in the middle of the lake, so it is unlikely that it has a unique source of regional groundwater. The third alternative was supported by the fact that in all three sample years, HSD stations were located in the preimpoundment stream channel, which is a likely lateral flow path for groundwater containing high SO₄^2- concentrations.     

Controls of Geochemical and Hydrogeochemical Factors on Arsenic Mobility in the Hetao Basin,China

High arsenic (As) groundwater is frequently found in inland basins, but little is known about As pools in sediments and their influences on aqueous As distributions. The Hetao Basin is a typical inland basin, where groundwater As concentrations generally increase from alluvial fans to flat plain. Two sites are only 1700 m apart, but groundwater As concentrations at the depth range of 15 to 80 m are quite different, ranging from 7.0 to 31.7 μg/L at site B1 and from 5.2 to 99.8 μg/L at site B2. Sediment geochemistry and groundwater hydrochemistry at two sites were characterized. No distinct differences were observed in the bulk geochemistry of sediments. Sequential extractions of 39 sediments were conducted to determine why As was easily released to groundwater at one site and not the other. Results showed that at site B1 most of solid As was associated with amorphous Fe-(oxyhydr)oxides, whereas at site B2 the strong adsorption pool dominated. Furthermore, higher dissolved Fe²⁺ and lower ORP in groundwater at site B2 suggested more strongly reducing conditions compared to site B1. High concentrations of NH₄⁺ and HCO₃⁻ at site B2 were consistent with As release coupled to microbially induced reductive dissolution of Fe-(oxyhydr)oxides. Other processes, such as the competitive adsorption of HCO₃⁻, As desorption under weakly alkaline pH conditions, may also influence the partitioning of As between groundwater and sediments. This study highlights the differences in how As is associated with sediments between high and low As aquifers and the contribution of chemical characteristics to As release.     

Identification of Pathways for Hydrogen Gas Migration in Fault Zones with a Discontinuous,Heterogeneous Permeability Structure and the Relationship to Particle Size Distribution of Fault Materials

Previous studies have reported that high concentrations of H₂ gas are released from active fault zones. Experimental studies suggest that the H₂ gas is derived from the reaction of water with free radicals formed when silicate minerals are fractured at hypocenter depths during fault activities. However, the pathways for migration of deep-seated fluids to surface are still unknown. In this study we performed quick, multipoint H₂ gas measurements across a fault zone using a portable gas monitor and a hand drill. The fault zone studied includes a smectite-rich fault core dividing two clearly distinguishable damage zones: granite cataclasite and welded tuff fault breccia. The measurements show that H₂ gas emissions collected in 2–3 h sampling periods from start of measurement range from 320.3 to 446.2 ppm/min in the granite cataclasite and 60.5 to 137.8 ppm/min in the welded tuff fault breccias. Negligible quantities of H₂ gas could be collected from the fault core. Particle size distribution analyses of fault rocks indicate that the granite cataclasite tends to be rich in particles that are finer, i.e., less cohesive and easy to disaggregate, which leads to the inference that the granite cataclasite has high permeability. Based on the H₂ gas measurements and the particle size distribution analyses, the H₂ gas is considered to have migrated in permeable damage zones mostly by advection with groundwater. Multipoint H₂ gas measurement will be effective in qualitative delineation of variations in permeability of regional structures.     

Optimization of the Sampling Technique for the Determination of Dissolved Hydrogen in Groundwater

In this study a field‐sampling technique for dissolved hydrogen (H₂) in groundwater will be presented which allows the transport of gaseous samples into the laboratory for further analysis. The method consists of transferring the headspace trapped in a gas‐sampling bulb which is continuously purged by groundwater into previously evacuated vials using a gas‐tight syringe. Three transfer steps with preceding evacuation of the vial led to a H₂‐recovery of 100 % in laboratory experiments. The method has been applied to determine H₂ concentrations in an aquifer contaminated with chlorinated solvents. Tests concerning the effect of different pumping techniques on H₂ concentrations revealed that most reliable values were obtained with a bladder pump, while an electrically driven submersible pump generated considerable amounts of hydrogen due to electrochemical interactions with the sampled water. Concentrations of dissolved hydrogen in field and laboratory samples were about two orders of magnitude higher when sampling was performed with the electrically driven submersible pump compared to sampling with the bladder pump and a peristaltic pump. Lab experiments with a Plexiglas reservoir to produce H₂‐enriched water were used to study the effect of two tubing materials (PVC, polyamide) on H₂ losses. PVC tubing turned out to allow transfer of H₂‐enriched water over 25 m without significant losses, while PA‐tubing was not suitable for sampling of H₂.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

Hydrogeologic characterization of the abandoned mining site of Castelejo,Portugal by VLF-EM & RMT-R geophysical surveying

There are about 175 abandoned mining sites in Portugal, of which about 60 are old uranium workings. The Castelejo mine is an old uranium located about 2 km W of Vila Cortês da Serra, in Guarda district, on the River Mondego basin. In geologic terms, the mine is located in medium-grained two-mica monzonitic granite, with porphyroidal tendency. Exploitation started with two open cast mines between 1979 and 1990 which produced about 132 tonnes U₃O₈. From 1992, production started to be carried out through the in situ H₂SO₄ leaching of the mine’s low-grade materials. The superficial and groundwater circulation are structurally conditioned by the intense fracturing in the area. Two exploratory geophysical field campaigns were conducted in order to characterize the fracturing. The first was a VLF survey that allowed us to identify major fault systems that may provide paths for groundwater flow. From the second campaign, which was an RMT survey conducted at a fault gauge which records the mine natural gradient flow, we obtained the resistivities and thicknesses of the weathered granite material. The profiles obtained show that resistivity declines with increasing depth. This fact may arise from natural causes – the material which fills the fault gauge is more weathered at depth than on the surface – or it may indicate contamination at depth, due to acid mine drainage.     

Degradation of Aqueous Atrazine and Metazachlor Solutions by UV and UV/H2O2 — Influence of pH and Herbicide Concentration Abbau von Atrazin und Metazachlor in wäßriger Lösung durch UV und UV/H2O2 — Einfluß von pH und Herbizid-Konzentration

The degradation of two pesticides: atrazine and metazachlor was investigated in aqueous solution under UV-irradiation with and without H₂O₂. Rate constants of the photochemical degradation were determined applying a first order kinetics and quantum yields of the processes were calculated. This approach leads to an apparent decrease of the quantum yield with increasing initial pesticide concentration. At low H₂O₂ initial concentrations, the pesticide degradation was shown to be much more efficient than the degradation under UV-irradiation only. However, at high H₂O₂ concentrations (>2 mmol L^?1), the efficiency of the UV/H₂O₂ system dropped down and the quantum yields of degradation were lower than for the direct photolysis. In the absence of H₂O₂, no influence of the pH value on the photodegradation of the pesticides could be noticed in a range between pH 3 and pH 11. At low H₂O₂ initial concentrations, the photochemical degradation of the pesticides was much faster at pH 3 and pH 7 compared with the degradation at pH 11. The results emphasize the potential of optimized reaction conditions in advanced oxidation.     

Fumarole compositions and mercury emissions from the Tatun Volcanic Field,Taiwan: Results from multi-component gas analyser,portable mercury spectrometer and direct sampling techniques

Gas emissions from Tatun volcanic group, northern Taiwan, were studied for the first time using a multi-component gas analyser system (Multi-GAS) in combination with Giggenbach flask methods at fumaroles and mud pools at Da-you-keng (DYK) and Geng-tze-ping (GZP). CO₂/S molar ratios observed at DYK ranged from 3–17, similar ratios were observed using a Multi-GAS sensor box of 8–16. SO₂ at GZP was low, higher concentrations were observed at DYK where SO₂/H₂S ratios were close to 1 for both methods. A lower CO₂/H₂S ratio was measured via Giggenbach flask sampling (7.2) than was found in the plume using the gas sensor at GZP (9.2). This may reflect rapid oxidation of H₂S as it mixes with background air. Gaseous elemental mercury (GEM) levels were observed in the fumarole gases using a portable mercury spectrometer. These are the first such measurements of mercury at Tatun. Mean GEM concentrations in the fumarole plumes were ∼ 20 ng m^− 3, with much higher concentrations observed close to the ground (mean [GEM] 130 and 290 ng m^− 3 at DYK and GZP, respectively). The GEM in the fumarole plume was elevated above concentrations in industrial/urban air in northern Taiwan and the increase in GEM observed when the instrument was lowered suggests high levels of mercury are present in the surrounding ground surface. The GEM/CO₂ (10^− 8) and GEM/S (10^− 6) ratios observed in the fumarole gases were comparable to those observed at other low-temperature fumaroles. Combining the Hg/CO₂ ratio with a previous CO₂ flux value for the area, the annual GEM flux from the Tatun field is estimated as 5–50 kg/year.     

Long-Term Evaluation of Mulch Biowall Performance to Treat Chlorinated Solvents

Permeable reactive barriers (PRBs), such as mulch biowalls, have been installed at numerous groundwater cleanup sites, and laboratory and field studies have demonstrated biotic and abiotic processes that degrade chlorinated volatile organic compounds (CVOCs) in groundwater passing through these engineered remedies. However, the longevity of mulch biowalls remains a fundamental research question. Soil and groundwater sampling at seven mulch biowalls at Altus Air Force Base (AFB) approximately 10 years after installation demonstrated the ongoing degradation of CVOCs. Trichloroethene was not detected in five of seven groundwater samples collected from the biowall despite upgradient detections above federal drinking water standards. Microbial sampling established the presence of key dechlorinating bacteria and the abundance of genes encoding specific enzymes for degradation, high methane concentrations, low sulfate concentrations, and negative oxidation-reduction potential, all indicative of highly reducing conditions within the biowalls and favorable conditions for CVOC destruction via microbial reductive dechlorination. High cellulose content (>79%) of the mulch, elevated total organic carbon (TOC) content in groundwater, and elevated potentially bioavailable organic carbon (PBOC) measurements in soil samples further supports an ongoing, long-lived source of carbon. These results demonstrate the ongoing and long-term efficacy of the mulch biowalls at Altus AFB. In addition, concentrations of bacteria, TOC, PBOC, and other geochemical parameters suggest a modest impact of the biowalls downgradient. The continued presence of CVOCs downgradient may be attributable to back diffusion from low-permeability shale. However, the biowalls continue to provide benefits by removing CVOCs in groundwater, thus reducing further CVOC loading to the downgradient, low-permeability strata.     

Numerical simulation of transport and sequential biodegradation of chlorinated aliphatic hydrocarbons using CHAIN_2D

Microbiological degradation of perchloroethylene (PCE) under anaerobic conditions follows a series of chain reactions, in which, sequentially, trichloroethylene (TCE), cis‐dichloroethylene (c‐DCE), vinylchloride (VC) and ethene are generated. First‐order degradation rate constants, partitioning coefficients and mass exchange rates for PCE, TCE, c‐DCE and VC were compiled from the literature. The parameters were used in a case study of pump‐and‐treat remediation of a PCE‐contaminated site near Tilburg, The Netherlands. Transport, non‐equilibrium sorption and biodegradation chain processes at the site were simulated using the CHAIN_2D code without further calibration. The modelled PCE compared reasonably well with observed PCE concentrations in the pumped water. We also performed a scenario analysis by applying several increased reductive dechlorination rates, reflecting different degradation conditions (e.g. addition of yeast extract and citrate). The scenario analysis predicted considerably higher concentrations of the degradation products as a result of enhanced reductive dechlorination of PCE. The predicted levels of the very toxic compound VC were now an order of magnitude above the maximum permissible concentration levels. Copyright © 1999 John Wiley & Sons, Ltd.     

Relation between hydrogen emission and seismic activities

Measurements of chemical composition of bubbles from a mineral spring at Yuya Spa situated close to the Median Tectonic Line, the longest active fault in Japan, showed that the periods of increased H₂ emission coincided with occurrences of the Ohno earthquake swarm nearby. Four cases of the coincidence without exception were observed in the last three years. The fluctuation of H₂ concentration ranges between <0.5 and 200 ppm, whereas other gases such as He, Ar, N₂, and CH₄ do not fluctuate much. The H₂ concentration is correlated with the energy released by the seismic activity. This field evidence, together with the results of laboratory experiments conducted bySugisaki et al. (1983), leads to the conclusion that H₂ observed at the mineral spring was produced by the reaction between groundwater and rock fractured in the seismic activities. The observation that H₂ in the mineral spring tends to appear prior to an earthquake suggests that microcracks may occur in rocks prior to earthquakes. The precursory emission of H₂ may be useful for earthquake prediction.