A membrane inlet mass spectrometry system for noble gases at natural abundances in gas and water samples.

RATIONALE: Noble gases dissolved in groundwater can reveal paleotemperatures, recharge conditions, and precise travel times. The collection and analysis of noble gas samples are cumbersome, involving noble gas purification, cryogenic separation and static mass spectrometry. A quicker and more efficient sample analysis method is required for introduced tracer studies and laboratory experiments. METHODS: A Noble Gas Membrane Inlet Mass Spectrometry (NG-MIMS) system was developed to measure noble gases at natural abundances in gas and water samples. The NG-MIMS system consists of a membrane inlet, a dry-ice water trap, a carbon-dioxide trap, two getters, a gate valve, a turbomolecular pump and a quadrupole mass spectrometer equipped with an electron multiplier. Noble gases isotopes (4)He, (22)Ne, (38)Ar, (84)Kr and (132)Xe are measured every 10 s. RESULTS: The NG-MIMS system can reproduce measurements made on a traditional noble gas mass spectrometer system with precisions of 2%, 8%, 1%, 1% and 3% for He, Ne, Ar, Kr and Xe, respectively. Noble gas concentrations measured in an artificial recharge pond were used to monitor an introduced xenon tracer and to reconstruct temperature variations to within 2 °C. Additional experiments demonstrated the capability to measure noble gases in gas and in water samples, in real time. CONCLUSIONS: The NG-MIMS system is capable of providing analyses sufficiently accurate and precise for introduced noble gas tracers at managed aquifer recharge facilities, groundwater fingerprinting based on excess air and noble gas recharge temperature, and field and laboratory studies investigating ebullition and diffusive exchange.

Movement of water infiltrated from a recharge basin to wells.

Local surface water and stormflow were infiltrated intermittently from a 40-ha basin between September 2003 and September 2007 to determine the feasibility of recharging alluvial aquifers pumped for public supply, near Stockton, California. Infiltration of water produced a pressure response that propagated through unconsolidated alluvial-fan deposits to 125 m below land surface (bls) in 5 d and through deeper, more consolidated alluvial deposits to 194 m bls in 25 d, resulting in increased water levels in nearby monitoring wells. The top of the saturated zone near the basin fluctuates seasonally from depths of about 15 to 20 m. Since the start of recharge, water infiltrated from the basin has reached depths as great as 165 m bls. On the basis of sulfur hexafluoride tracer test data, basin water moved downward through the saturated alluvial deposits until reaching more permeable zones about 110 m bls. Once reaching these permeable zones, water moved rapidly to nearby pumping wells at rates as high as 13 m/d. Flow to wells through highly permeable material was confirmed on the basis of flowmeter logging, and simulated numerically using a two-dimensional radial groundwater flow model. Arsenic concentrations increased slightly as a result of recharge from 2 to 6 µg/L immediately below the basin. Although few water-quality issues were identified during sample collection, high groundwater velocities and short travel times to nearby wells may have implications for groundwater management at this and at other sites in heterogeneous alluvial aquifers.

Evaluation of noble gas recharge temperatures in a shallow unconfined aquifer.

Water table temperatures inferred from dissolved noble gas concentrations (noble gas temperatures, NGT) are useful as a quantitative proxy for air temperature change since the last glacial maximum. Despite their importance in paleoclimate research, few studies have investigated the relationship between NGT and actual recharge temperatures in field settings. This study presents dissolved noble gas data from a shallow unconfined aquifer heavily impacted by agriculture. Considering samples unaffected by degassing, NGT calculated from common physically based interpretive gas dissolution models that correct measured noble gas concentrations for "excess air" agreed with measured water table temperatures (WTT). The ability to fit data to multiple interpretive models indicates that model goodness-of-fit does not necessarily mean that the model reflects actual gas dissolution processes. Although NGT are useful in that they reflect WTT, caution is recommended when using these interpretive models. There was no measurable difference in excess air characteristics (amount and degree of fractionation) between two recharge regimes studied (higher flux recharge primarily during spring and summer vs. continuous, low flux recharge). Approximately 20% of samples had dissolved gas concentrations below equilibrium concentration with respect to atmospheric pressure, indicating degassing. Geochemical and dissolved gas data indicate that saturated zone denitrification caused degassing by gas stripping. Modeling indicates that minor degassing (<10% DeltaNe) may cause underestimation of ground water recharge temperature by up to 2 degrees C. Such errors are problematic because degassing may not be apparent and degassed samples may be fit by a model with a high degree of certainty.

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.

Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer.

Evidence of seepage from animal waste holding lagoons at a dairy facility in the San Joaquin Valley of California is assessed in the context of a process geochemical model that addresses reactions associated with the formation of the lagoon water as well as reactions occurring upon the mixture of lagoon water with underlying aquifer material. Comparison of model results with observed concentrations of NH4+, K+, PO4(3-), dissolved inorganic carbon, pH, Ca2+, Mg2+, SO4(2-), Cl-, and dissolved Ar in lagoon water samples and groundwater samples suggests three key geochemical processes: (i) off-gassing of significant quantities of CO2 and CH4 during mineralization of manure in the lagoon water, (ii) ion exchange reactions that remove K+ and NH4+ from seepage water as it migrates into the underlying anaerobic aquifer material, and (iii) mineral precipitation reactions involving phosphate and carbonate minerals in the lagoon water in response to an increase in pH as well as in the underlying aquifer from elevated Ca2+ and Mg2+ levels generated by ion exchange. Substantial off-gassing from the lagoons is further indicated by dissolved argon concentrations in lagoon water samples that are below atmospheric equilibrium. As such, Ar may serve as a unique tracer for lagoon water seepage since under-saturated Ar concentrations in groundwater are unlikely to be influenced by any processes other than mechanical mixing.

Sorption and transport of iodine species in sediments from the Savannah River and Hanford Sites.

Iodine is an important element in studies of environmental protection and human health, global-scale hydrologic processes and nuclear nonproliferation. Biogeochemical cycling of iodine is complex, because iodine occurs in multiple oxidation states and as inorganic and organic species that may be hydrophilic, atmophilic, and biophilic. In this study, we applied new analytical techniques to study the sorption and transport behavior of iodine species (iodide, iodate, and 4-iodoaniline) in sediments collected at the Savannah River and Hanford Sites, where anthropogenic (129)I from prior nuclear fuel processing activities poses an environmental risk. We conducted integrated column and batch experiments to investigate the interconversion, sorption and transport of iodine species, and the sediments we examined exhibit a wide range in organic matter, clay mineralogy, soil pH, and texture. The results of our experiments illustrate complex behavior with various processes occurring, including iodate reduction, irreversible retention or mass loss of iodide, and rate-limited and nonlinear sorption. There was an appreciable iodate reduction to iodide, presumably mediated by the structural Fe(II) in some clay minerals; therefore, careful attention must be given to potential interconversion among species when interpreting the biogeochemical behavior of iodine in the environment. The different iodine species exhibited dramatically different sorption and transport behavior in three sediment samples, possessing different physico-chemical properties, collected from different depths at the Savannah River Site. Our study yielded additional insight into processes and mechanisms affecting the geochemical cycling of iodine in the environment, and provided quantitative estimates of key parameters (e.g., extent and rate of sorption) for risk assessment at these sites.