Noble gas isotopic composition of deep underground water in Osaka plain, central Japan: Evidence for mantle He and model for new volcanism

Abstract Elemental and isotopic compositions of noble gases extracted from the bore hole water in Osaka plain, central Japan were examined. The water samples were collected from four shallow bore holes (180-450 m) and seven deep bore holes (600-1370 m) which have been used for an urban resort hot spring zone. The water temperatures of the deep bore holes were 22-50°C and that of the shallow bore holes, 13-23°C. The elemental abundance patterns show the progressive enrichment of the heavier noble gases compared with the atmospheric noble gas composition except for He, which is heavily enriched in deep bore hole water samples. ³He/⁴He ratios from the bore holes reaching the Ryoke granitic basement were higher than the atmospheric value (1.4 × 10⁻⁶), indicating a release of mantle He through the basement. The highest value of 8.2 × 10⁻⁶ is in the range of arc volcanism. On the other hand, the bore holes in sedimentary rocks overlying the basement release He enriched in radiogenic ⁴He, resulted in a low ³He/⁴He ratio of 0.5 × 10⁻⁶. ⁴He/²⁰Ne and ⁴⁰Ar/³⁶Ar ratios indicate that the air contamination is generally larger in shallow bore holes than in deep ones from each site. The helium enriched in mantle He is compatible with the previous work which suggested up-rising magma in 'Kinki Spot', the area of Osaka and western Wakayama, in spite of no volcanic activity in the area. A model to explain an initiation of magma generation beneath this area is presented.     

The West Falmouth oil spill after 20 years: Fate of fuel oil compounds and effects on animals

The barge Florida spilled No. 2 fuel oil into Buzzards Bay, Massachusetts on 29 September 1969. Sediments from five of the original stations were sampled in August 1989 and analysed for fuel oil hydrocarbons. Two subtidal and one intertidal marsh station showed no evidence of fuel oil. One subtidal mud core had traces of biodegraded fuel oil at 10–15 cm. One marsh core contained 10⁻⁶ g g⁻¹ dry wt of weathered and biodegraded fuel oil aromatic hydrocarbons and cycloalkanes at 5–10 cm with lesser concentrations at 0–5 and 10–15 cm. Although present in trace concentrations, these hydrocarbons appear to be slightly inducing cytochrome P4501A in marsh fish (Fundulus heteroclitus).     

Ages and composition of gas trapped in Allan Hills and Byrd core ice

Gas is extracted from large (6–31 kg) Antarctic ice samples to obtain sufficient CO₂ for¹⁴C measurements with small low-level proportional counters. The¹⁴C ages of Byrd core ice are in accord with glaciological estimates ranging from (2.2_−1.1^+1.4)×10³ yr at 271 m depth to more than 8 × 10³ yr at 1071 m depth. The CO₂ abundances in gas extracted from Byrd core ice range from 0.0216 to 0.051%, with below present-day atmosphere CO₂ abundances for ice from 1068 and 1469 m depths. The CO₂ abundance in gas from Allan Hills surface ice samples ranges between four and six times the atmospheric value and the CO₂ had a specific activity three times that of contemporary carbon. A possible explanation for the anomalously high specific activity is surface melting with the incorporation into CO₂ of¹⁴C produced by cosmic ray spallation of oxygen in ice. The CO₂ abundance in gas extracted from subsurface Allan Hills ice ranged from 0.030 to 0.065%, and the specific activities are below contemporary carbon, indicating ages greater than 5×10³ yr. The¹⁸O/¹⁶O ratio of oxygen in the trapped gas is the same as that of atmospheric oxygen and differs markedly from the¹⁸O/¹⁶O ratio in the ice. The O₂, N₂, and Ar abundances and isotopic compositions are similar to those in contemporary air, except for positive¹⁵N/¹⁴N ratios in a few samples.     

Noble gases in submarine pillow basalt glasses from the Lau Basin: Detection of a solar component in backarc basin basalts

Noble gas elemental and isotopic abundances have been analysed in eight samples of youthful basaltic glass dredged from three different locations within the Lau Backarc Basin: (1) the King's Triple Junction, (2) the Central Lau Spreading Centre at 18°S and (3) the Eastern Lau Spreading Centre at 19°S. Samples from the Lau central and eastern spreading centres have MORB-like helium isotopic ratios of approximately 1.2 × 10⁻⁵ (8.5 R/R_A). In contrast, the samples from the King's Triple Junction yield helium isotopic ratios averaging 9.4 (±0.8) × 10⁻⁶ (6.7 ± 0.6 R/R_A), systematically lower than the MORB-like value, which may be reflecting the addition of radiogenic ⁴He released from the descending slab. Neon isotopic ratios are enriched in ²⁰Ne and ²¹Ne with respect to atmospheric ratios by as much as 23% and 62% respectively. These observations further confirm that non-atmospheric neon is a common characteristic of samples derived from the mantle. The helium and neon isotopic signatures in the samples can be explained by mixing of a primordial solar component, radiogenic and nucleogenic components produced by radioactive processes inside the Earth, and an atmospheric component. This reconnaissance survey of noble gases in a backarc basin indicates that current volcanism is dominated by magmas from the mantle wedge, a source similar to that from which MORBs are derived. The heavier noble gases (argon, krypton and xenon), however, show more atmosphere-like compositions, either indicating strong interaction of the magmas with the atmosphere or the presence of a recycled component derived from the underlying subducting slab.     

Dynamics of the gas flux from shallow gas hydrate deposits: interaction between oily hydrate bubbles and the oceanic environment

Decomposition of methane hydrates on the continental margins is a potentially significant source of atmospheric methane, but the input depends upon the poorly understood fate of the hydrocarbon bubbles rising from the sea floor. During a field trip to the Gulf of Mexico, three different seepages were imaged and analyzed. Three different imaging techniques were tried (side, front, and back illumination), of which back illumination produced the best results. The images were analyzed and the size-dependent bubble distribution, mass flux, and rise speeds determined. The total observed gas flux was 62.3×10⁻³ mol s⁻¹, primarily methane, of which a single vent produced seven times the next largest vent. Of this major vent, 50% of the bubble mass was contained in the largest bubbles, r>5500 μm. The vertical velocities demonstrated that these bubbles were heavily contaminated with oil, which was also corroborated by bubble shape and oscillation observations.     

Noble gases in pillow basalt glasses from the northern Mariana Trough back-arc basin

Noble gas concentrations and isotopic compositions have been measured in eight samples of pillow basalt glasses collected from seven different localities along 250 km of the Mariana Trough spreading and rifting axis. The samples have uniform and mid-ocean ridge basalt (MORB)-like ³He/⁴He values of 9–12 × 10^–6 (6.4–8.6 times atmospheric) despite large variations in ⁴He. Concentrations of the noble gases Ne, Ar, Kr, and Xe show much smaller variations between samples, but larger variations in isotopic compositions of Ne, Ar, and Xe. Excess radiogenic ²¹Ne is observed in some samples. ⁴⁰Ar/³⁶Ar varies widely (atmospheric to 1880). Kr is atmospheric in composition for all samples. Some samples show a clear excess ¹²⁹Xe, which is a well-known MORB signature. Isotopic compositions of the heavier noble gases (Ar, Kr, and Xe) in some samples, however, show more atmospheric components. These data reflect the interaction of a MORB-like magma with an atmospheric component such as seawater or of a depleted mantle source with a water-rich component that was probably derived from the subducting slab.     

Interpretation of Gas Chromatographic Data in Subsurface Hydrocarbon Investigations

Capillary column gas chromatography (GC) is extremely useful in investigations of subsurface contamination by petroleum hydrocarbons. Fluid samples collected from observation wells are evaluated by GC methods to detect and analyze petroleum hydrocarbons in dissolved and liquid phases. The presence, types and concentrations of many petroleum-derived hydrocarbons dissolved in ground water can be determined. GC analysis can also be used to determine the composition of liquid hydrocarbon products, including gasoline, distillates and heavier oils. The degree of degradation of sampled liquid hydrocarbon product can be estimated from GC information, and this information can be helpful in estimating the length of time the product has been in the subsurface. Determination of the hydrocarbon source and migration path can be made from GC analysis of fluid samples collected at two or more locations.
This paper is intended to demonstrate interpretative techniques that can be used by hydrogeologists to facilitate the detection, identification and mitigation of subsurface hydrocarbons.     

Low-Cost Apparatus for On-Site Monitoring of Methane in Ground Water

An upsurge in oil- and gas-well drilling in northwestern Pennsylvania and western New York has been accompanied by several incidents of contamination of ground water by methane. Determining which well is causing the contamination is extremely difficult if more than one gas or oil well is present in the area.
The fact that the solubility of methane decreases as the pressure on ground water decreases provides a quantitative basis for monitoring changes in the amount of methane in the ground water. Quantitative measurements of the volume of methane given off by ground water pumped from a well as the water enters atmospheric pressure permit detection of temporal changes in the gas content which are too subtle to be detected visually. These gas volume changes may, in some cases, be correlated with variations in the pressure of methane in the annulus of nearby individual gas/oil wells and thus may provide a means of pinpointing the gas/oil well that is causing the methane contamination.
The basic principle of the gas-volume monitoring apparatus (GVMA) described in this paper is that as a measured amount of ground water enters atmospheric pressure the gas which comes out of solution is trapped and measured. The GVMA can be constructed of materials costing less than $100 and requires no special skills to assemble or operate. In a recent study conducted in a western New York village, four homeowners were able to collect quantitative gas-volume data from their household water wells daily in about one-half hour. Unlike laboratory analyses for dissolved methane, there is no cost involved in monitoring with the GVMA beyond the initial instrument cost and operator time. Another advantage is that the data are available immediately.     

Bacterial Production Stimulated Across the Zone of Influence of a Ground Water Circulation Well in a BTEX-Contaminated Aquifer

Benzene, toluene, ethylbenzene, and xylene (BTEX) hydrocarbons are typically the most abundant carbon source for bacteria in gasoline-contaminated ground water. In situ bioremediation strategies often involve stimulating bacterial heterotrophic production in an attempt to increase carbon demand of the assemblage. This may, in turn, stimulate biodegradation of contaminant hydrocarbons. In this study, ground water circulation wells (GCWs) were used as an in situ treatment for a fuel-contaminated aquifer to stimulate bacterial production, purportedly by increasing oxygen transfer to the subsurface, circulating limiting nutrients, enhancing bioavailability of hydrocarbons, or by removing metabolically inhibitory volatile organics. Bacterial production, as measured by rates of bacterial protein synthesis, was stimulated across the zone of influence (ZOI) of a series of GCWs. Productivity increased from ∼10² to >10⁵ ng C/L hour across the ZOI, suggesting that treatment stimulated overall biodegradation of carbon sources present in the ground water. However, even if BTEX carbon met all bacterial carbon demand, biodegradation would account for <4.3% of the total estimated BTEX removed from the ground water. Although bacterial productivity measurements alone cannot prove the effectiveness of in situ bioremediation, they can estimate the maximum amount of contaminant that may be biodegraded by a treatment system.     

Infiltration of river water to a shallow aquifer investigated with H/He, noble gases and CFCs

Noble gas isotopes (³He, ⁴He, Ne, Ar, Kr, Xe), tritium (³H), chlorofluorocarbons (CFCs) and dissolved oxygen (O₂) were seasonally measured in a small groundwater system recharged by infiltration of river water at Linsental, northeastern Switzerland. All Groundwater samples contained an excess of atmospheric noble gases (‘excess air’) usually with an elemental composition equal to air. The concentrations of atmospheric noble gases in the groundwater were used to calculate the excess air component and the water temperature at recharge. The noble gas temperatures (NGTs) in the boreholes close to the river vary seasonally, however, the average NGT of all samples lies close to the mean annual temperature of the river water. Groundwater ages were calculated using the tritium/helium-3 (³H/³He) dating method. The water ages of the samples obtained near the river depend on the amount of recently infiltrated river water and are young during times of active river discharge. In contrast, the mean water age of about 3 years of the deep aquifer remained nearly constant over the sampling period. The observed CFC-11 (CFCl₃) and CFC-12 (CF₂Cl₂) concentrations are significantly higher than the atmospheric equilibrium concentrations and therefore CFCs do not provide any direct information on the residence time of the groundwater. Nevertheless, the CFC excess in the groundwater shows a linear increase with the ³H/³He age. Additionally, both accumulation of radiogenic He (⁴He_rad) and O₂ consumption are strongly correlated with residence time. All these correlations can be interpreted either in terms of mixing of recently infiltrated river water with older groundwater or in terms of accumulation/consumption rates.     

Isotopic fractionation of a loosely held atmospheric argon component in the Picture Gorge Basalts

Seven lava flows from the Picture Gorge “type section”, central Oregon, U.S.A., have been dated at 15.2 ± 0.6 m.y. by the K-Ar method. The preparation of the samples for the argon extraction work strongly affects the ages obtained, due to the presence of very large quantities of atmospheric argon held “loosely” within most of the rocks. Use of single large pieces of rock results in incomplete removal of this gas, argon isotopic fractionation and grossly incorrect ages. When powdered samples are used, the increase in surface area per unit mass helps in the removal of the “loosely” held atmospheric argon. The Picture Gorge Basalts contain traces of clays of the montmorillonite group; on hydration these clays swell up and apparently shut off minute cracks in the rocks, thereby trapping substantial amounts of atmospheric argon. It is recommended that when K-Ar dating of whole-rock samples showing traces of alteration has to be attempted, the specimens be crushed to approximately 10–30 mesh size prior to the argon extraction work.     

Contamination from Sand-Bentonite Seal in Monitoring Wells Installed in Aquitards

A six year field experiment has shown that a sand-bentonite mixture used to seal monitoring wells in aquitards contributes solutes to the ground water sampled from these wells. Monitoring wells were installed at field sites with hydraulic conductivity (K) ranging from 5 × 10 ^-9 m/s to 3 × 10¹¹ m/s. In most cases the boreholes remained dry during installation which allowed the placement of a dry powdered bentonite/sand mixture tagged with potassium bromide (KBr) to seal and separate sampling points. Over six years, wells were sampled periodically and ground-water samples were analyzed for Br and Cl and other major ions. Typical Br results ranged from 10 mg/1 to 35 mg/1 in the first 700 days, as compared to an estimated initial concentration in the seal material of about 75 mg/1. After six years the bromide concentrations had decreased to between 3 mg/1 and 5 mg/1. The total mass of Br removed in six years is less than 50% of that placed; therefore the contamination effects, although considerably diminished, persist. The trends of Br, Cl, Na, and SO₄ indicate that varying degrees of contamination occur. These data show that the materials used to seal monitoring wells in aquitards can have a significant and long-lasting impact on the chemistry of the water in the wells.     

PCBs and chlorinated pesticides in the atmosphere and aquatic organisms of Ross Island, Antarctica

PCBs, p,p′-DDT, p,p′-DDE and lindane (γ-hexachlorocyclohexane) were monitored in the lower atmosphere of Ross Island, in Antarctica for 2 yr. Geometrical means were 15.2 pg m⁻³ for PCBs, 2.0 pg m⁻³ for p,p′-DDT, 1.0 pg m⁻³ for p,p′-DDE and 25.8 pg m⁻³ for lindane. Atmospheric levels of lindane were positively correlated with temperature, and a significant difference was found between spring-summer and summer-winter concentrations. No season related differences were found for the other chlorinated hydrocarbons, possibly owing to their lower vapour pressure and the cold climate. Periods with increased atmospheric levels of PCBs and DDT compounds were recorded. Lindane, p,p′-DDE and PCBs were present in fish and zooplankton sampled close to Ross Island. Pollutant levels in the zooplankton (on an extractable fat basis) were highest during the Antarctic spring and autumn and were inversely correlated to their fat content.     

Generation of Hydrogen Gas as a Result of Drilling Within the Saturated Zone

Hydrogen gas was discovered within the steel casing above standing water in a percussion-drilled borehole on the Hanlord Site in south-central Washington state. In situ measurements of the borehole fluids indicated anoxic, low-Eh (<-400 mV) conditions. Ground water sampled from adjacent wells in the same formation indicated that the ground water was oxygenated. H₂ was generated during percussion drilling, due to the decomposition of borehole waters as a result of aqueous reactions with drilled sediment and steel from the drilling tools or casing. The generation of H₂ within percussion-drilled boreholes that extend below the water table may be more common than previously realized. The ambient concentration of H₂ produced during drilling was limited by microbial activity within the casing-resident fluids. H₂ was generated abiotically in the laboratory, whereby sterilized borehole slurry samples produced 100 times more H₂ than unsterilizcd samples. It appears that H₂ is metabolized by microorganisms and concentrations might be significantly greater if not for microbial metabolism.     

Enhancement of In Situ Bioremediation of BTEX-Contaminated Ground Water by Oxygen Diffusion from Silicone Tubing

A field study of oxygen-enhanced biodegradation was carried out in a sandy iron-rich ground water system contaminated with gasoline hydrocarbons. Prior to the oxygen study, intrinsic microbial biodegradation in the contaminant plume had depleted dissolved oxygen and created anaerobic conditions. An oxygen diffusion system made of silicone polymer tubing was installed in an injection well within an oxygen delivery zone containing coarse highly permeable sand. During the study, this system delivered high dissolved oxygen (DO) levels (39 mg/L) to the ground water within a part of the plume. The ground water was sampled at a series of monitors in the test zone downgradient of the delivery well to determine the effect of oxygen on dissolved BTEX, ground water geochemistry, and microbially mediated biodegradation processes. The DO levels and Eh increased markedly at distances up to 2.3 m (7.5 feet) downgradient. Potential biofouling and iron precipitation effects did not clog the well screens or porous medium. The increased dissolved oxygen enhanced the population of aerobes while the activity of anaerobic sulfate-reducing bacteria and methanogens decreased. Based on concentration changes, the estimated total rate of BTEX biodegradation rose from 872 mg/day before enhancement to 2530 mg/day after 60 days of oxygen delivery. Increased oxygen flux to the test area could account for aerobic biodegradation of 1835 mg/day of the BTEX. The estimated rates of anaerobic biodegradation processes decreased based on the flux of sulfate, iron (II), and methane. Two contaminants in the plume, benzene and ethylbenzene, are not biodegraded as readily as toluene or xylenes under anaerobic conditions. Following oxygen enhancement, however, the benzene and ethylbenzene concentrations decreased about 98%, as did toluene and total xylenes.     

Fugitive emissions from Norwegian oil and gas production

Fugitive hydrocarbon emissions from oil and gas production, always a safety concern, are currently a growing environmental and economic concern. Fugitive emissions from the offshore industry comprise mainly methane, which has an atmospheric warming contribution of approximately 14 times that of CO₂, and Volatile Organic Compounds (VOCs), which have an atmospheric warming contribution of around twice that of CO₂.

Current studies indicate that fugitive emissions are approximately equivalent to 0.02% of the total gas produced in 1992 on the Norwegian Continental Shelf. A positive downward trend in fugitive emissions from oil and gas production has been identified and attributed to advances in technology and changes in design and operating philosophy.     

Oxidation of fugitive methane in ground water linked to bacterial sulfate reduction

When fugitive methane migrates upward along boreholes of oil and gas wells, it may migrate into shallow ground water or pass through overlying soil to the atmosphere. Prior to this study, there was little information on the fate of fugitive methane that migrates into ground water. In a field study near Lloydminster, Alberta, Canada, we found hydrogeochemical evidence that fugitive methane from an oil well migrated into a shallow aquifer but has been attenuated by dissimilatory bacterial sulfate reduction at low temperature ( approximately 5 degrees C) under anaerobic conditions. Evidence includes spatial and temporal trends in concentrations of methane and sulfate in ground water and associated trends in concentrations of bicarbonate and sulfide. Within 10 m of the oil well, sulfate concentrations were low, and sulfate was enriched in both 34S and 18O. Sulfate concentrations had a strong positive correlation with delta13C values of bicarbonate, and sulfide was depleted in 34S compared to sulfate. These data indicate that bacterial sulfate reduction occurred near the production well. Near the oil well, elevated concentrations of bicarbonate were observed, and the bicarbonate was depleted in 13C. Modeling indicates that the main source of this excess 13C-depleted bicarbonate is oxidized methane. In concert with the sulfate concentration and isotope data, these results support an interpretation that in situ bacterial oxidation of methane has occurred, linked to bacterial sulfate reduction. Bacterial sulfate reduction may play a major role in bioattenuation of fugitive natural gas in ground water in western Canada.     

Extinguishing Petroleum Vapor Intrusion and Methane Risks for Slab-on-ground Buildings: A Simple Guide

The occurrence of aerobic biodegradation in the vadose zone between a subsurface source and a building foundation can all-but eliminate the risks from methane and petroleum vapor intrusion (PVI). Understanding oxygen availability and the factors that affect it (e.g., building sizes and their distribution) are therefore critical. Uncovered ground surfaces allow oxygen access to the subsurface to actively biodegrade hydrocarbons (inclusive of methane). Buildings can reduce the net flux of oxygen into the subsurface and so reduce degradation rates. Here we determine when PVI and methane risk is negligible and/or extinguished; defined by when oxygen is present across the entire sub-slab region of existing or planned slab-on-ground buildings. We consider all building slab sizes, all depths to vapor sources and the effect of spacings between buildings on the availability of oxygen in the subsurface. The latter becomes critical where buildings are in close proximity or when increased building density is planned. Conservative assumptions enable simple, rapid and confident screening should sites and building designs comply to model assumptions. We do not model the aboveground “building” processes (e.g., air exchange), and assume the slab-on-ground seals the ground surface so that biodegradation of hydrocarbons is minimized under the built structure (i.e., the assessment remains conservative). Two graphs represent the entirety of the outcomes that allow simple screening of hydrocarbon vapors based only on the depth to the source of vapors below ground, the concentration of vapors within the source, the width of the slab-on-ground building, and the gap between buildings; all independent of soil type. Rectangular, square, and circular buildings are considered. Comparison with field sites and example applications are provided, along with a simple 8-step screening guide set in the context of existing guidance on PVI assessment.     

Spatial Variability of Soil-Gas Concentrations near and beneath a Building Overlying Shallow Petroleum Hydrocarbon–Impacted Soils

Data requirements for assessing the significance of the soil vapor intrusion pathway are evolving, and the collection and interpretation of subslab and near-slab soil-gas samples are under discussion. The potential for different assessment paradigms for aerobically biodegradable and recalcitrant chemicals is also frequently debated. In this work, the soil-gas distribution beneath and around a slab-on-grade building overlying shallow (0.5 to >1.5 m below ground surface) petroleum hydrocarbon–impacted coarse alluvial soils was studied. The study spanned about 12 months, including the sampling of soil-gas hydrocarbon and oxygen concentrations, subslab soil vs. building pressure differentials and included weather conditions. Three-dimensional soil-gas concentration "snapshots" using samples from 79 soil-gas sampling points are presented here. Significant spatial variability was observed with hydrocarbon and oxygen concentrations ranging from about <0.01 to 200 mg/L and 0 to 21% v/v, respectively. The presence of oxygen and the depth to petroleum-impacted soils appeared to be the dominant factors in controlling the soil-gas distribution; the depletion of hydrocarbons over short lateral and vertical distances (<2 m) was observed in the well-oxygenated regions. Composition data suggest preferential biodegradation of lighter compounds at some points, as reflected in the ratio of the masses of chemicals eluting on the gas chromatography between methane and pentane (C1 and C5) and all others after pentane (>C5).     

Shallow gas in the muddy sediments of Eckernförde Bay, Germany

The seafloor of central Eckernförde Bay is characterised by soft muddy sediments that contain free methane gas. Bubbles of free gas cause acoustic turbidity which is observed with acoustic remote sensing systems. Repeated surveys with subbottom profiler and side scan sonar revealed an annual period both of depth of the acoustic turbidity and backscatter strength. The effects are delayed by 3–4 months relative to the atmospheric temperature cycle. In addition, prominent pockmarks, partly related to gas seepage, were detected with the acoustic systems. In a direct approach gas concentrations were measured from cores using the gas chromatography technique. From different tests it is concluded that subsampling of a core should start at its base and should be completed as soon as possible, at least within 35 min after core recovery. Comparison of methane concentrations of summer and winter cores revealed no significant seasonal variation. Thus, it is concluded that the temperature and pressure influences upon solubility control the depth variability of acoustic turbidity which is observed with acoustic remote sensing systems. The delay relative to the atmospheric temperature cycle is caused by slow heat transfer through the water column. The atmospheric temperature cycle as ‘exiting function’ for variable gas solubility offers an opportunity for modelling and predicting the depth of the acoustic turbidity. In practice, however, small-scale variations of, e.g., salinity, or gas concentration profile in the sediment impose limits to predictions. In addition, oceanographic influences as mixing in the water column, variable water inflow, etc. are further complications that reduce the reliability of predictions.