Noble Gas Analyses to Distinguish Between Surface and Subsurface Brine Releases at a Legacy Oil Site.

Attributing the sources of legacy contamination, including brines, is important to determine remediation options and to allocate responsibility. To make sound remediation decisions, it is necessary to distinguish subsurface sources, such as leaking oil and gas ("O&G") wells or natural upward fluid migrations, from surface releases. While chemical signatures of surface and subsurface releases may be similar, they are expected to imprint specific dissolved noble gas signatures, caused by the accumulation of terrigenic noble gases in subsurface leaks or re-equilibration of noble gases following surface releases. We demonstrate that only a historic surface release influenced the dissolved noble gas signature of groundwater in monitoring wells contaminated with brine near an abandoned O&G well, rather than subsurface leakage from the well. Elevated brine concentrations were associated with lower terrigenic helium concentrations, indicating re-equilibration with atmospheric helium at the surface during the release. Geophysical surveying indicating elevated salinity in surficial soils upgradient of the wells further supported the interpretation of the noble gas data. Eliminating the possibility that subsurface leakage was the source of the plume was critical to selecting the proper remedial action at the site, which otherwise may have included an unnecessary and costly well re-abandonment. This study demonstrates the use of noble gas analysis to compare potential sources of brine contamination in groundwater and to exclude subsurface leakage as a potential source in an oilfield.

Simplified Method for the In Situ Collection and Laboratory Analysis of Cosmogenic Tracers (Sulfur-35 and Sodium-22) to Determine Residence Time Distributions and Water Ages.

The use of cosmogenically produced sulfur-35 (T1/2 = 87 days) and sodium-22 (T1/2 = 2.6 years) as intrinsic tracers can provide valuable information on catchment hydrology, flow paths, and subsurface storage. A new and straightforward method was created to determine the activities of both 35S and 22Na in various water sources by pumping large volumes (up to 1000 L) of water through cation- and anion-exchange resin columns in the field to collect sodium and sulfate ions and simple chemistry in the lab. Samples are counted for 35S using liquid scintillation counting (LSC) and for 22Na via γ spectroscopy. Our novel in situ method provides faster sample throughput as well as better counting statistics and lower detection limits. Both methods were successfully applied at the Southern Sierra Critical Zone Observatory.

Effect of Groundwater Age and Recharge Source on Nitrate Concentrations in Domestic Wells in the San Joaquin Valley.

Nitrate is one of the most abundant contaminants in groundwater globally, in the United States, and in California (CA). We studied well construction information, water chemistry, stable isotopes, and noble gases to understand how groundwater travel time and recharge source and mechanism control nitrate concentrations in domestic wells in the San Joaquin Valley (SJV), CA, a large semiarid, irrigated agricultural region. Using nonparametric statistics, we find a decreasing trend in nitrates with groundwater travel time and well depth. Samples collected from wells that are closer to rivers and that show indications of river water recharge, either low recharge temperature or low δ18O signature, have lower concentrations of nitrates than samples with isotopic signatures indicating mixed source or local precipitation recharge. The curbing effect of river water recharge on nitrate concentrations in domestic wells is similar for direct river recharge and water applied as irrigation. This suggests that irrigation with river water also has a diluting effect that reduces the concentration of nitrate found in groundwater. This conclusion supports the idea that flood-managed aquifer recharge may be considered for remediation of groundwater nitrate when designing replenishment of aquifers.

Analysis of air mass trajectories to explain observed variability of tritium in precipitation at the Southern Sierra Critical Zone Observatory, California, USA.

Understanding the behavior of tritium, a radioactive isotope of hydrogen, in the environment is important to evaluate the exposure risk of anthropogenic releases, and for its application as a tracer in hydrology and oceanography. To understand and predict the variability of tritium in precipitation, HYSPLIT air mass trajectories were analyzed for 16 aggregate precipitation samples collected over a 2 year period at irregular intervals at a research site located at 2000 m elevation in the southern Sierra Nevada (California, USA). Attributing the variation in tritium to specific source areas confirms the hypothesis that higher latitude or inland sources bring higher tritium levels in precipitation than precipitation originating in the lower latitude Pacific Ocean. In this case, the source of precipitation accounts for 79% of the variation observed in tritium concentrations. Air mass trajectory analysis is a promising tool to improve the predictions of tritium in precipitation at unmonitored locations and thoroughly understand the processes controlling transport of tritium in the environment.

Dissolved atmospheric gas in xylem sap measured with membrane inlet mass spectrometry.

A new method is described for measuring dissolved gas concentrations in small volumes of xylem sap using membrane inlet mass spectrometry. The technique can be used to determine concentrations of atmospheric gases, such as argon, as reported here, or for any dissolved gases and their isotopes for a variety of applications, such as rapid detection of trace gases from groundwater only hours after they were taken up by trees and rooting depth estimation. Atmospheric gas content in xylem sap directly affects the conditions and mechanisms that allow for gas removal from xylem embolisms, because gas can dissolve into saturated or supersaturated sap only under gas pressure that is above atmospheric pressure. The method was tested for red trumpet vine, Distictis buccinatoria (Bignoniaceae), by measuring atmospheric gas concentrations in sap collected at times of minimum and maximum daily temperature and during temperature increase and decline. Mean argon concentration in xylem sap did not differ significantly from saturation levels for the temperature and pressure conditions at any time of collection, but more than 40% of all samples were supersaturated, especially during the warm parts of day. There was no significant diurnal pattern, due to high variability between samples.

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.

Climate change impacts on the leaching of a heavy metal contamination in a small lowland catchment.

The Keersop catchment (43km(2)) in the south of The Netherlands has been contaminated by the emissions of four zinc ore smelters. The objective of this study was to assess the effects of future projected climate change on the hydrology and the leaching of heavy metals (i.e. Cd and Zn) in the catchment. The numerical, quasi-2D, unsaturated zone Soil Water Atmosphere Plant model was used with 100-year simulated daily time series of precipitation and potential evapotranspiration. The time series are representative of stationary climates for the periods 1961-1990 ("baseline") and 2071-2100 ("future"). The time series of future climate were obtained by downscaling the results of eight regional climate model (RCM) experiments, driven by the SRES A2 emissions scenario, using change factors for a series of climate statistics and applying them to stochastic weather generator models. The time series are characterized by increased precipitation in winter, less precipitation in summer, and higher air temperatures (between 2°C and 5°C) throughout the year. Future climate scenarios project higher evapotranspiration rates, more irrigation, less drainage, lower discharge rates and lower groundwater levels, due to increased evapotranspiration and a slowing down of the groundwater system. As a result, lower concentrations of Cd and Zn in surface water are projected. The reduced leaching of heavy metals, due to drying of the catchment, showed a positive impact on a limited aspect of surface water quality.

Comparison of methods for the detection and extrapolation of trends in groundwater quality.

Land use changes and the intensification of agriculture since the 1950s have resulted in a deterioration of groundwater quality in many European countries. For the protection of groundwater quality, it is necessary to (1) assess the current groundwater quality status, (2) detect changes or trends in groundwater quality, (3) assess the threat of deterioration and (4) predict future changes in groundwater quality. A variety of approaches and tools can be used to detect and extrapolate trends in groundwater quality, ranging from simple linear statistics to distributed 3D groundwater contaminant transport models. In this paper we report on a comparison of four methods for the detection and extrapolation of trends in groundwater quality: (1) statistical methods, (2) groundwater dating, (3) transfer functions, and (4) deterministic modeling. Our work shows that the selection of the method should firstly be made on the basis of the specific goals of the study (only trend detection or also extrapolation), the system under study, and the available resources. For trend detection in groundwater quality in relation to diffuse agricultural contamination, a very important aspect is whether the nature of the monitoring network and groundwater body allows the collection of samples with a distinct age or produces samples with a mixture of young and old groundwater. We conclude that there is no single optimal method to detect trends in groundwater quality across widely differing catchments.

Degassing of 3H/3He, CFCs and SF6 by denitrification: measurements and two-phase transport simulations.

The production of N2 gas by denitrification may lead to the appearance of a gas phase below the water table prohibiting the conservative transport of tracer gases required for groundwater dating. We used a two-phase flow and transport model (STOMP) to study the reliability of 3H/3He, CFCs and SF6 as groundwater age tracers under agricultural land where denitrification causes degassing. We were able to reproduce the amount of degassing (R2=69%), as well as the 3H (R2=79%) and 3He (R2=76%) concentrations observed in a 3H/3He data set using simple 2D models. We found that the TDG correction of the 3H/3He age overestimated the control 3He/3He age by 2.1 years, due to the accumulation of 3He in the gas phase. The total uncertainty of degassed 3H/3He ages of 6 years (+/-2 sigma) is due to the correction of degassed 3He using the TDG method, but also due to the travel time in the unsaturated zone and the diffusion of bomb peak 3He. CFCs appear to be subject to significant degradation in anoxic groundwater and SF6 is highly susceptible to degassing. We conclude that 3H/3He is the most reliable method to date degassed groundwater and that two-phase flow models such as STOMP are useful tools to assist in the interpretation of degassed groundwater age tracer data.