Gas transport below artificial recharge ponds: insights from dissolved noble gases and a dual gas (SF6 and 3He) tracer experiment

A dual gas tracer experiment using sulfur hexafluoride (SF6) and an isotope of helium (3He) and measurements of dissolved noble gases was performed at the El Rio spreading grounds to examine gas transport and trapped air below an artificial recharge pond with a very high recharge rate (approximately 4 m day(-1)). Noble gas concentrations in the groundwater were greater than in surface water due to excess air formation showing that trapped air exists below the pond. Breakthrough curves of SF6 and 3He at two nearby production wells were very similar and suggest that nonequilibrium gas transfer was occurring between the percolating water and the trapped air. At one well screened between 50 and 90 m below ground, both tracers were detected after 5 days and reached a maximum at approximately 24 days. Despite the potential dilution caused by mixing within the production well, the maximum concentration was approximately 25% of the mean pond concentration. More than 50% of the SF6 recharged was recovered by the production wells during the 18 month long experiment. Our results demonstrate that at artificial recharge sites with high infiltration rates and moderately deep water tables, transport times between recharge locations and wells determined with gas tracer experiments are reliable.     

The effects of dual-domain mass transfer on the tritium-helium-3 dating method

Diffusion of tritiated water (referred to as tritium) and helium-3 between mobile and immobile regions in aquifers (mass transfer) can affect tritium and helium-3 concentrations and hence tritium-helium-3 (3H/3He) ages that are used to estimate aquifer recharge and groundwater residence times. Tritium and helium-3 chromatographically separate during transport because their molecular diffusion coefficients differ. Simulations of tritium and helium-3 transport and diffusive mass transfer along stream tubes show that mass transfer can shift the 3H/3He age of the tritium and helium-3 concentration ([3H + 3He]) peak to dates much younger than the 1963 peak in atmospheric tritium. Furthermore, diffusive mass-transfer can cause the 3H/3He age to become younger downstream along a stream tube, even as the mean water-age must increase. Simulated patterns of [3H + 3He] versus 3H/3He age using a mass transfer model appear consistent with a variety of field data. These results suggest that diffusive mass transfer should be considered, especially when the [3H + 3He] peak is not well defined or appears younger than the atmospheric peak. 3H/3He data provide information about upstream mass-transfer processes that could be used to constrain mass-transfer models; however, uncritical acceptance of 3H/3He dates from aquifers with immobile regions could be misleading.     

Passive sampling and analyses of common dissolved fixed gases in groundwater

An in situ passive sampling and gas chromatographic protocol was developed for analysis of the major and several minor fixed gases (He, Ne, H2, N2, O2, CO, CH4, CO2, and N2O) in groundwater. Using argon carrier gas, a HayeSep DB porous polymer phase, and sequential thermal conductivity and reductive gas detectors, the protocol achieved sufficient separation and sensitivity to measure the mixing ratio of all these gases in a single 0.5 mL gas sample collected in situ, stored, transported, and injected using a gastight syringe. Within 4 days of immersion in groundwater, the simple passive in situ sampler, whether initially filled with He or air, attained an equivalent and constant mixing ratio for five of the seven detected gases. The abundant mixing ratio of N2O, averaging 2.6%, indicated that significant denitrification is likely ongoing within groundwater contaminated with uranium, acidity, nitrate, and organic carbon from a group of four closed radioactive wastewater seepage ponds at the Oak Ridge Field Research Center. Over 1000 passive gas samples from 12 monitoring wells averaged 56% CO2, 32.4% N2, 2.6% O2, 2.6% N2O, 0.21% CH4, 0.093% H2, and 0.025% CO with an average recovery of 95 +/- 14% of the injected gas volume.     

氦氩同位素对蓝宝石成因的指示

本文报道了斯里兰卡蓝宝石的氦、氩含量及同位素组成.采用真空压碎法获得蓝宝石流体包裹体中的氦、氩含量分别为3.7～4.9×10-6 cm3 STP/g和1.6～1.9×10-6 cm3 STP/g,同位素组成分别为3He/4He=0.17～0.21 Ra和40Ar/36Ar=4348.7～4457.3.该特征与含刚玉的古...     

Decadal geochemical and isotopic trends for nitrate in a transboundary aquifer and implications for agricultural beneficial management practices

Nitrate contamination of aquifers is a global agricultural problem. Agricultural beneficial management practices (BMPs) are often promoted as a means to reduce nitrate contamination in aquifers through producer optimized management of inorganic fertilizer and animal manure inputs. In this study, decadal trends (1991-2004) in nitrate concentrations in conjunction with 3H/3He groundwater ages and nitrate stable isotopes (delta15N, delta18O) were examined to determine whether BMPs aimed at reducing aquifer-scale nitrate contamination in the transboundary Abbotsford-Sumas aquifer were effective. A general trend of increasing nitrate concentrations in young groundwater (< approximately 5 yr) suggested that voluntary BMPs were not having a positive impact in achieving groundwater quality targets. While the stable isotope data showed that animal manure was and still is the prevalent source of nitrate in the aquifer, a recent decrease in delta15N in nitrate suggests a BMP driven shift away from animal wastes toward inorganic fertilizers. The coupling of long-term monitoring of nitrate concentrations, nitrate isotopes, and 3H/3He age dating proved to be invaluable, and they should be considered in future assessments of the impact of BMPs on nutrients in groundwaters. The findings reveal that BMPs should be better linked to groundwater nutrient monitoring programs in order to more quickly identify BMP deficiencies, and to dynamically adjust nutrient loadings to help achieve water quality objectives.     

Demonstrating a natural origin of chloroform in groundwater using stable carbon isotopes

Chloroform has been for a long time considered only as an anthropogenic contaminant. The presence of chloroform in forest soil and groundwater has been widely demonstrated. The frequent detection of chloroform in groundwater in absence of other contaminants suggests that chloroform is likely produced naturally. Compound-specific isotope analysis of chloroform was performed on soil-gas and groundwater samples to elucidate whether its source is natural or anthropogenic. The δ(13)C values of chloroform (-22.8 to -26.2‰) present in soil gas collected in a forested area are within the same range as the soil organic matter (-22.6 to -28.2‰) but are more enriched in (13)C compared to industrial chloroform (-43.2 to -63.6‰). The δ(13)C values of chloroform at the water table (-22.0‰) corresponded well to the δ(13)C of soil gas chloroform, demonstrating that the isotope signature of chloroform is maintained during transport through the unsaturated zone. Generally, the isotope signature of chloroform is conserved also during longer range transport in the aquifer. These δ(13)C data support the hypothesis that chloroform is naturally formed in some forest soils. These results may be particularly relevant for authorities' regulation of chloroform which in the case of Denmark was very strict for groundwater (<1 μg/L).     

Measurement of dissolved H2, O2, and CO2 in groundwater using passive samplers for gas chromatographic analyses

A simple in-situ passive dissolved gas groundwater sampler, comprised of a short length of silicone tubing attached to a gastight or other syringe, was adapted and tested for in-situ collection of equilibrium gas samples. Sampler retrieval after several days of immersion in groundwater allowed the direct injection of the sample onto a gas chromatograph (GC), simplifying field collection and sample handling over the commonly used "bubble stripping" method for H2 analyses. A GC was modified by sequencing a thermal conductivity (TC) detector followed by a reductive gas (RG) detector so that linear calibration of H2 over the range 0.2-200,000 ppmv was attained using a 0.5-mL gas sample; inclusion of the TC detector allowed the simultaneous quantification of other fixed gases (O2, CO2, He, and Ne) to which the RG detector was not responsive. Uptake kinetics for H2 and He indicated that the passive sampler reached equilibrium within 12 h of immersion in water. Field testing of these passive samplers revealed unusually large equilibrium gas-phase H2 concentrations in groundwater, ranging from 0.1 to 13.9%, by volume, in 11 monitoring wells surrounding four former radiological wastewater disposal ponds at the Y-12 plant in Oak Ridge, Tennessee.     

Saturated zone denitrification: potential for natural attenuation of nitrate contamination in shallow groundwater under dairy operations

We present results from field studies at two central California dairies that demonstrate the prevalence of saturated-zone denitrification in shallow groundwater with 3H/ 3He apparent ages of < 35 years. Concentrated animal feeding operations are suspected to be major contributors of nitrate to groundwater, but saturated zone denitrification could mitigate their impact to groundwater quality. Denitrification is identified and quantified using N and O stable isotope compositions of nitrate coupled with measurements of excess N2 and residual NO3(-) concentrations. Nitrate in dairy groundwater from this study has delta15N values (4.3-61 per thousand), and delta18O values (-4.5-24.5 per thousand) that plot with delta18O/delta15N slopes of 0.47-0.66, consistent with denitrification. Noble gas mass spectrometry is used to quantify recharge temperature and excess air content. Dissolved N2 is found at concentrations well above those expected for equilibrium with air or incorporation of excess air, consistent with reduction of nitrate to N2. Fractionation factors for nitrogen and oxygen isotopes in nitrate appear to be highly variable at a dairy site where denitrification is found in a laterally extensive anoxic zone 5 m below the water table, and at a second dairy site where denitrification occurs near the water table and is strongly influenced by localized lagoon seepage.     

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.     

Impact of artificial recharge on dissolved noble gases in groundwater in California

Dissolved noble gas concentrations in groundwater can provide valuable information on recharge temperatures and enable 3H-3He age-dating with the use of physically based interpretive models. This study presents a large (905 samples) data set of dissolved noble gas concentrations from drinking water supply wells throughout California, representing a range of physiographic, climatic, and water management conditions. Three common interpretive models (unfractionated air, UA; partial re-equilibration, PR; and closed system equilibrium, CE) produce systematically different recharge temperatures or ages; however, the ability of the different models to fit measured data within measurement uncertainty indicates that goodness-of-fit is not a robust indicator for model appropriateness. Therefore caution is necessary when interpreting model results. Samples from multiple locations contained significantly higher Ne and excess air concentrations than reported in the literature, with maximum excess air tending toward 0.05 cm3 STP g(-1) (deltaNe approximately 400%). Artificial recharge is the most plausible cause of the high excess air concentrations. The ability of artificial recharge to dissolve greater amounts of atmospheric gases has important implications for oxidation-reduction dependent chemical reactions. Measured gas concentration ratios suggest that diffusive degassing may have occurred. Understanding the physical processes controlling gas dissolution during groundwater recharge is critical for optimal management of artificial recharge and for predicting changes in water quality that can occur following artificial recharge.     

Integrated sampling and analytical approach for common groundwater dissolved gases

A novel passive gas diffusion sampler (PGDS) combines sampling, storage and direct injection into a single gas chromatograph (GC). The sampler has a 4.5 mL internal volume when deployed, is easy to operate, and eliminates sample-partitioning. The associated GC method analyzes for a large, dynamic sampling range from a single, small volume injection. Dissolved gases were separated on parallel Rt-Molsieve 5A and Rt-Q-PLOT columns and eluted solutes were quantified using a pulse discharge helium ionization detector (PD-HID). The combined sampling and analytical method appears to be less prone to systematic bias than conventional sampling and headspace partitioning and analysis. Total dissolved gas pressure used in tandem with the PGDS improved the accuracy of dissolved gas concentrations. The incorporation of routine measurements of dissolved biogeochemical and permanent gases into groundwater investigations will provide increased insight into chemical and biological processes in groundwater and improve chemical mass balance accuracy.     

棉织物的常压等离子体拒水改性处理

以六氟丙烯(C3F6)为处理气体,以氦气(He)为载气,在常压下实现等离子体准辉光放电.以此对棉织物进行表面改性处理,研究放电时间、功率、浓度等条件对拒水性能的影响.结果表明:织物与水接触角不随实验条件变化而明显变化,说明粗糙度相同时,水的接触角主要受织物的表面能影响;润湿时间随处理条件增强而增加,说明润湿时间主要受沉...     

Geogenic sources of benzene in aquifers used for public supply, california

Statistical evaluation of two large statewide data sets from the California State Water Board's Groundwater Ambient Monitoring and Assessment Program (1973 wells) and the California Department of Public Health (12?417 wells) reveals that benzene occurs infrequently (1.7%) and at generally low concentrations (median detected concentration of 0.024 μg/L) in groundwater used for public supply in California. When detected, benzene is more often related to geogenic (45% of detections) than anthropogenic sources (27% of detections). Similar relations are evident for the sum of 17 hydrocarbons analyzed. Benzene occurs most frequently and at the highest concentrations in old, brackish, and reducing groundwater; the detection frequency was 13.0% in groundwater with tritium <1 pCi/L, specific conductance >1600 μS/cm, and anoxic conditions. This groundwater is typically deep (>180 m). Benzene occurs somewhat less frequently in recent, shallow, and reducing groundwater; the detection frequency was 2.6% in groundwater with tritium ≥1 pCi/L, depth <30 m, and anoxic conditions. Evidence for geogenic sources of benzene include: higher concentrations and detection frequencies with increasing well depth, groundwater age, and proximity to oil and gas fields; and higher salinity and lower chloride/iodide ratios in old groundwater with detections of benzene, consistent with interactions with oil-field brines.     

The effect of sample grinding procedures after processing on gas production profiles and end‐product formation in expander processed barley and peas

Grinding is a technological process widely applied in the feed manufacturing industry and is a prerequisite for obtaining representative samples for laboratory procedures (e.g. gas production analysis). When feeds are subjected to technological processes other than grinding (e.g. expander treatment), grinding afterwards may disturb the effect of processing, both in practice and when laboratory techniques are applied. Therefore, this study aimed to establish the possible effects of different grinding procedures and sample preparation on the degradative behaviour of expander processed barley and peas. Samples of expander processed barley and peas were subjected to six different sample preparation procedures (intact sample, dissolved sample, samples ground stepwise over 6 and 3 mm sieves, samples ground stepwise over 6, 3 and 1 mm sieves, samples ground over a 3 mm sieve and samples ground over a 1 mm sieve). The patterns of gas production in these samples were studied over a period of 72 h incubation using an automated in vitro gas production system. The particle size distribution determined by dry sieve analysis and the Coulter counter method changed due to the different grinding procedures. Grinding the samples of expander processed barley and peas changed the kinetics of gas production and led to a faster degradation, most pronounced after stepwise grinding. However, the formation of the fermentation end‐product was not affected by the method of sample preparation. In expander processed barley, the difference in the degradation pattern due to the different grinding procedures was small. Copyright © 2007 Society of Chemical Industry     

Chemical-specific representation of air--soil exchange and soil penetration in regional multimedia models

In multimedia mass-balance models, the soil compartment is an important sink as well as a conduit for transfers to vegetation and shallow groundwater. Here a novel approach for constructing soil transport algorithms for multimedia fate models is developed and evaluated. The resulting algorithms account for diffusion in gas and liquid components; advection in gas, liquid, or solid phases; and multiple transformation processes. They also provide an explicit quantification of the characteristic soil penetration depth. We construct a compartment model using three and four soil layers to replicate with high reliability the flux and mass distribution obtained from the exact analytical solution describing the transient dispersion, advection, and transformation of chemicals in soil layers with different properties but a fixed boundary condition at the air-soil surface. The soil compartment algorithms can be dynamically linked to other compartments (air, vegetation, groundwater, surface water) in multimedia fate models. We demonstrate and evaluate the performance of the algorithms in a model with applications to benzene, benzo[a]pyrene, MTBE, TCDD, and tritium.     

Sources and migration of plutonium in groundwater at the Savannah River site

The isotopic composition, size distribution, and redox speciation of plutonium (Pu) in the groundwater in the vicinity of the F-area seepage basins at the U.S. Department of Energy Savannah River Site (SRS) were examined. A low 240Pu/239Pu ratio in the upstream control well signifies a Pu source otherthan global fallout and indicates reactor-produced Pu. Elevated 240Pu/239Pu atom ratios downstream from the seepage basins are due to the decay of transplutonium isotopes, mainly 244Cm to 240Pu, which were generated at the SRS. Evidence suggests that the migration of basin-released Pu isotopes is minor. Rather, it is the transplutonium isotopes that migrate preferentially downstream and in the process decay to yield progeny Pu isotopes. Size fractionation studies with cross-flow ultrafiltration show that <4% of the 239Pu or 240Pu is found in the colloidal fraction, a finding that is consistent with the higher Pu oxidation states observed in the SRS groundwater. The observation of a low abundance of colloid-associated Pu in SRS groundwater cannot be extrapolated to all sites, but is in contrast to the conclusions of prior groundwater Pu studies at the SRS and elsewhere. This work is unique in its application of a novel combination of sampling and processing protocols as well as its use of thermal ionization mass spectrometry for the detection of Pu isotopes. This allows quantification of the Pu source terms and better determination of the ambient Pu size and redox speciation representative of in situ conditions.     

Cryogenic laser induced fluorescence characterization of U(VI) in Hanford Vadose Zone pore waters

Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)2(2-), UO2(CO3)3(4-), and (UO2)2(OH)3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)3(4-) along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.     

Reconstructing tritium exposure using tree rings at Lawrence Berkeley National Laboratory, California

Annual tritium exposures were reconstructed using tree cores from Pinus jeffreyi and Eucalyptus globulus near a tritiated water vapor release stack. Both tritium (3H) and carbon-14 (14C) from the wood were measured from milligram samples using accelerator mass spectrometry. Because the annual nature of the eucalyptus tree rings was in doubt, 14C measurements provided growth rates used to estimate the age for 3H determinations. A 30-yr comparison of organically bound tritium (OBT) levels to reported 3H release data is achieved using OBT measurements from three trees nearthe stack. The annual average 3H, determined from atmospheric water vapor monitoring stations, is comparable to the OBT in proximal trees. For situations without adequate historical monitoring data, this measurement-based historical assessment provides the only independent means of assessing exposure as compared to fate and transport models that require prior knowledge of environmental conditions and 3H discharge patterns.     

Differentiation of dietary regimene of Iberian swine by means of isotopic analysis of carbon and sulphur in hepatic tissue

The aim of this work was to differentiate the feed received by Iberian swine during fattening (acorns, feed) and their breed (Iberian or White) using analysis of the stable isotopes of carbon (δ(13)C) and sulphur (δ(34)S) in liver tissue samples. The results obtained in the determination of δ(34)S, using a procedure in which organic and inorganic sulphur are converted into BaSO(4) and the procedure that measures δ(34)S in samples of dried ground liver tissue were compared. Joint analysis of carbon (δ(13)C) and sulphur (δ(34)S) permits the differentiation of swine of different breeds receiving different diets (acorns or feed).     

Ecohydrological factors affecting nitrate concentrations in a phreatic desert aquifer in northwestern China

Aerobic conditions in desert aquifers commonly allow high nitrate (NO3-) concentrations in recharge to persist for long periods of time, an important consideration for N-cycling and water quality. In this study, stable isotopes of NO3- (delta15N(NO3) and delta18O(NO3)) were used to trace NO3- cycling processes which affect concentrations in groundwater and unsaturated zone moisture in the arid Badain Jaran Desert in northwestern China. Most groundwater NO3- appears to be depleted relative to Cl- in rainfall concentrated by evapotranspiration, indicating net N losses. Unsaturated zone NO3- is generally higher than groundwater NO3- in terms of both concentration (up to 15 476 microM, corresponding to 3.6 mg NO3(-)-N per kg sediment) and ratios with Cl-. Isotopic data indicate that the NO3- derives primarily from nitrification, with a minor direct contribution of atmospheric NO3- inferred for some samples, particularly in the unsaturated zone. Localized denitrification in the saturated zone is suggested by isotopic and geochemical indicators in some areas. Anthropogenic inputs appear to be minimal, and variability is attributed to environmental factors. In comparison to other arid regions, the sparseness of vegetation in the study area appears to play an important role in moderating unsaturated zone NO3- accumulation by allowing solute flushing and deterring extensive N2 fixation.