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1.
This study presents a multiphase flow and multispecies reactive transport model for the simultaneous simulation of NAPL and groundwater flow, dissolution, and reactive transport with isotope fractionation, which can be used for better interpretation of NAPL-involved Compound Specific Isotope Analysis in 3D heterogeneous hydrogeologic systems. The model was verified for NAPL-aqueous phase equilibrium partitioning, aqueous phase multi-chain and multi-component reactive transport, and aqueous phase multi-component transport with isotope fractionation. Several illustrative examples are presented to investigate the effect of DNAPL spill rates, degradation rate constants, and enrichment factors on the temporal and spatial distribution of the isotope signatures of chlorinated aliphatic hydrocarbon groundwater plumes. The results clearly indicate that isotope signatures can be significantly different when considering multiphase flow within the source zone. A series of simulations indicate that degradation and isotope enrichment compete with dissolution to determine the isotope signatures in the source zone: isotope ratios remain the same as those of the source if dissolution dominates the reaction, while heavy isotopes are enriched in reactants along groundwater plume flow paths when degradation becomes dominant. It is also shown that NAPL composition can change from that of the injected source due to the partitioning of components between the aqueous and NAPL phases even when degradation is not allowed in NAPL phase. The three-dimensional simulation is presented to mechanistically illustrate the complexities in determining and interpreting the isotopic signatures with evolving DNAPL source architecture.  相似文献   

2.
Surface‐wetting properties are an important cause of changing the groundwater and two‐phase fluid flows. Various factors affecting the surface wettability were investigated in a parallel‐walled glass fracture with non‐aqueous phase liquid (NAPL) (gasoline, diesel, trichloroethylene, and creosote) wetted surfaces. First, the effect of the duration of NAPL exposure on wettability change was considered at pre‐wet fracture surfaces using the various NAPL species, and the result showed that the surface became hydrophobic after the exposure time of NAPL exceeded 2000 min. Second, the initial wetting state of the surface affected the timing when the wettability change begins as well as the extent of the wettability change in an NAPL‐wetted rock fractures. Under the dry condition, the wettability change was completed within a very short time of exposure to NAPL (~5 min), and then it finally reached the intermediate and weakly NAPL wetting (contact angle of 118°). Under the pre‐wet condition, a relatively long time of exposure (~5000 min) was needed to observe the obvious change of the surface wettability, which was changed up to strongly NAPL wetting (contact angle of 142°). Third, the wettability changed by NAPL exposure was stable and maintained for a long time, regardless of water flushing rate and temperature. Finally, the wettability change by the exposure of NAPL on parallel fracture surfaces was evaluated at various groundwater flow velocities. Result showed that groundwater flow velocity has an important impact upon measured contact angle. Although fracture surfaces were exposed to NAPL at the low groundwater flow velocity, the wettability was not changed from hydrophilic to hydrophobic when the contact time between NAPL and mineral surfaces was not sufficient owing to the pulse‐type movement of NAPL. This implies that the variation of exposure pattern due to groundwater flow on the wettability change can be an important factor affecting the wettability change of fracture surface and migration behaviour at natural fractured rock aquifers in case of NAPL spill. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

3.
《Advances in water resources》2007,30(6-7):1618-1629
Residual dense non-aqueous liquids (NAPLs) in aquifers constitute a great challenge for groundwater cleanup. Active engineered treatment of regions that contain residual NAPLs is often required to shorten the long-term impact of NAPLs on groundwater quality. Enhanced residual NAPL cleanup can be achieved by promoting biodegradation of NAPL components in the aqueous phase, thereby increasing contaminant fluxes from the NAPL phase. Reaction-enhanced NAPL dissolution is often mathematically simulated under the assumption that lumped mass transfer coefficients, used to describe the dissolution behavior of the NAPL phase, are independent of the reactions. However, this assumption is not warranted because reactions occurring near the water–NAPL interface can reduce characteristic mass transfer lengths, which tend to enhance mass transfer over the no-reaction case.In this study, we mathematically investigated the connections between lumped mass transfer coefficients and reaction kinetics over an idealized residual NAPL domain. Since mass transfer is frequently a scale-dependent process, we also examined the influence of system extent on mass transfer coefficients. For our idealized domain with an assumed first-order decay reaction, the results show that lumped mass transfer coefficients depend on reaction kinetics and system scale. The mass transfer coefficient derived from the non-reactive case cannot properly represent the mass transfer process under the reactive conditions. When the advection time scale is long in comparison to the transverse dispersion time scale in the system, a fast reaction can increase significantly the lumped mass transfer coefficient. The mass transfer coefficient used for simulation was also found to be affected by the nature of the numerical scheme used.  相似文献   

4.
Wettability profoundly affects not only the initial distribution of residual NAPL contaminants in natural soils, but also their subsequent dissolution in a flowing aqueous phase. Under conditions of preferential NAPL wettability, the residual NAPL phase is found within the smaller pores and in the form of continuous corner filaments and thick films on pore walls. Such films expose a much greater interfacial area for mass transfer than would be exposed by the same amount of non-wetting NAPL. Importantly, capillary and hydraulic continuity of NAPL filaments and thick films is essential for sustaining NAPL–water counterflow during the course of NAPL dissolution in flowing groundwater—a mechanism which maintains and even increases the interfacial area for mass transfer. Continued dissolution results in gradual thinning of the NAPL films, which may become unstable and rupture causing disconnection of the residual NAPL in the form of clusters. Using a pore network simulator, we demonstrate that NAPL film instability drastically modifies the microscopic configuration of residual NAPL, and hence the local hydrodynamic conditions and interfacial area for mass transfer, with concomitant effects on macroscopically observable quantities, such as the aqueous effluent concentration and the fractional NAPL recovery with time. These results strongly suggest that the disjoining pressure of NAPL films may exert an important, and hitherto unaccounted, control on the dissolution behaviour of a residual NAPL phase in oil wet systems.  相似文献   

5.
The objective of this study was to investigate whether 222Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m3 of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. 222Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of 222Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m3 below the capillary fringe. We find that 222Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.  相似文献   

6.
Flow of nonvolatile nonaqueous phase liquid (NAPL) and aqueous phases that account for mobile, entrapped, and residual NAPL in variably saturated water-wet porous media is modeled and compared against results from detailed laboratory experiments. Residual saturation formation in the vadose zone is a process that is often ignored in multifluid flow simulators, which might cause an overestimation of the volume of NAPL that reaches the ground water. Mobile NAPL is defined as being continuous in the pore space and flows under a pressure gradient or gravitational body force. Entrapped NAPL is defined as being occluded by the aqueous phase, occurring as immobile ganglia surrounded by aqueous phase in the pore space and formed when NAPL is replaced by the aqueous phase. Residual NAPL is defined as immobile, nonwater entrapped NAPL that does not drain from the pore spaces and is conceptualized as being either continuous or discontinuous. Free NAPL comprises mobile and residual NAPL. The numerical model is formulated on mass conservation equations for oil and water, transported via NAPL and aqueous phases through variably saturated porous media. To account for phase transitions, a primary variable switching scheme is implemented for the oil-mass conservation equation over three phase conditions: (1) aqueous or aqueous-gas with dissolved oil, (2) aqueous or aqueous-gas with entrapped NAPL, and (3) aqueous or aqueous gas with free NAPL. Two laboratory-scale column experiments are modeled to verify the numerical model. Comparisons between the numerical simulations and experiments demonstrate the necessity to include the residual NAPL formation process in multifluid flow simulators.  相似文献   

7.
Spatially discontinuous permafrost conditions frequently occur in the European Alps. How soils under such conditions have evolved and how they may react to climate warming is largely unknown. This study focuses on the comparison of nearby soils that are characterised by the presence or absence of permafrost (active‐layer thickness: 2–3 m) in the alpine (tundra) and subalpine (forest) range of the Eastern Swiss Alps using a multi‐method (geochemical and mineralogical) approach. Moreover, a new non‐steady‐state concept was applied to determine rates of chemical weathering, soil erosion, soil formation, soil denudation, and soil production. Long‐term chemical weathering rates, soil formation and erosion rates were assessed by using immobile elements, fine‐earth stocks and meteoric 10Be. In addition, the weathering index (K + Ca)/Ti, the amount of Fe‐ and Al‐oxyhydroxides and clay minerals characteristics were considered. All methods indicated that the differences between permafrost‐affected and non‐permafrost‐affected soils were small. Furthermore, the soils did not uniformly differ in their weathering behaviour. A tendency towards less intense weathering in soils that were affected by permafrost was noted: at most sites, weathering rates, the proportion of oxyhydroxides and the weathering stage of clay minerals were lower in permafrost soils. In part, erosion rates were higher at the permafrost sites and accounted for 79–97% of the denudation rates. In general, soil formation rates (8.8–86.7 t/km2/yr) were in the expected range for Alpine soils. Independent of permafrost conditions, it seems that the local microenvironment (particularly vegetation and subsequently soil organic matter) has strongly influenced denudation rates. As the climate has varied since the beginning of soil evolution, the conditions for soil formation and weathering were not stable over time. Soil evolution in high Alpine settings is complex owing to, among others, spatio‐temporal variations of permafrost conditions and thus climate. This makes predictions of future behaviour very difficult. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

8.
Long‐term weathering of a quartz chlorite schist via wetting and drying was studied under a simulated tropical climate. Cubic rock samples (15 mm × 15 mm × 15 mm) were cut from larger rocks and subjected to time‐compressed climatic conditions simulating the tropical wet season climate at the Ranger Uranium Mine in the Northern Territory, Australia. Fragmentation, moisture content and moisture uptake rate were monitored over 5000 cycles of wetting and drying. To determine the impact of climatic variables, five climatic regimes were simulated, varying water application, temperature and drying. One of the climatic regimes reproduced observed temperature and moisture variability at the Ranger Uranium Mine, but over a compressed time scale. It is shown that wetting and drying is capable of weathering quartz chlorite schist with changes expected over a real time period of decades. While wetting and drying alone does produce changes to rock morphology, the incorporation of temperature variation further enhances weathering rates. Although little fragmentation occurred in experiments, significant changes to internal pore structure were observed, which could potentially enhance other weathering mechanisms. Moisture variability is shown to lead to higher weathering rates than are observed when samples are subjected only to leaching. Finally, experiments were conducted on two rock samples from the same source having only subtle differences in mineralogy. The samples exhibited quite different weathering rates leading to the conclusion that our knowledge of the role of rock type and composition in weathering is insufficient for the accurate determination of weathering rates. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

9.
ABSTRACT

India has been the subject of many recent groundwater studies due to the rapid depletion of groundwater in large parts of the country. However, few if any of these studies have examined groundwater storage conditions in all of India’s river basins individually. Herein we assess groundwater storage changes in all 22 of India’s major river basins using in situ data from 3420 observation locations for the period 2003–2014. One-month and 12-month standardized precipitation index measures (SPI-1 and SPI-12) indicate fluctuations in the long-term pattern. The Ganges and Brahmaputra basins experienced long-term decreasing trends in precipitation in both 1961–2014 and the study period, 2003–2014. Indeterminate or increasing precipitation trends occurred in other basins. Satellite-based and in situ groundwater storage time series exhibited similar patterns, with increases in most of the basins. However, diminishing groundwater storage (at rates of >0.4 km3/year) was revealed in the Ganges-Brahmaputra River Basin based on in situ observations, which is particularly important due to its agricultural productivity.  相似文献   

10.
The hydrogeochemistry of shallow groundwater has been characterized in the Allt a'Mharcaidh catchment in the Scottish Cairngorms in order to: (i) assess the spatial and temporal variation in groundwater chemistry; (ii) identify the hydrogeochemical processes regulating its evolution; and (iii) examine the influence of groundwater on the quality and quantity of stream flow. Shallow groundwater in superficial drift deposits is circumneutral (pH∽7·1) and base cation concentrations are enriched compared with precipitation and drainage water from overlying podzolic soils. Modelling with NETPATH suggests that the dominant geochemical processes that account for this are the dissolution of plagioclase, K-feldspar and biotite. Groundwater emerging as springs from weathered granite underlying high altitude (>900 m) alpine soils shows similar characteristics, though weathering rates are lower, probably as a result of reduced residence times and lower temperatures. Chemical hydrograph separation techniques using acid neutralizing capacity (ANC) and Si as tracers show that groundwater is the dominant source of baseflow in the catchment and also buffers the chemistry of stream water at high flows: groundwater may account for as much as 50–60% of annual runoff in the catchment. Climate and land use in the Cairngorms are vulnerable to future changes, which may have major implications for hydrogeological processes in the area. © 1998 John Wiley & Sons, Ltd.  相似文献   

11.
Egypt is currently seeking additional freshwater resources to support national reclamation projects based mainly on the Nubian aquifer groundwater resources. In this study, temporal (April 2002 to June 2016) Gravity Recovery and Climate Experiment (GRACE)-derived terrestrial water storage (TWSGRACE) along with other relevant datasets was used to monitor and quantify modern recharge and depletion rates of the Nubian aquifer in Egypt (NAE) and investigate the interaction of the NAE with artificial lakes. Results indicate: (1) the NAE is receiving a total recharge of 20.27 ± 1.95 km3 during 4/2002?2/2006 and 4/2008–6/2016 periods, (2) recharge events occur only under excessive precipitation conditions over the Nubian recharge domains and/or under a significant rise in Lake Nasser levels, (3) the NAE is witnessing a groundwater depletion of ? 13.45 ± 0.82 km3/year during 3/2006–3/2008 period, (4) the observed groundwater depletion is largely related to exceptional drought conditions and/or normal baseflow recession, and (5) a conjunctive surface water and groundwater management plan needs to be adapted to develop sustainable water resources management in the NAE. Findings demonstrate the use of global monthly TWSGRACE solutions as a practical, informative, and cost-effective approach for monitoring aquifer systems across the globe.  相似文献   

12.
We developed a new semi-analytical source zone depletion model (SZDM) for multicomponent light nonaqueous phase liquids (LNAPLs) and incorporated this into an existing screening model for estimating cleanup times for chemical spills from railroad tank cars that previously considered only single-component LNAPLs. Results from the SZDM compare favorably to those from a three-dimensional numerical model, and from another semi-analytical model that does not consider source zone depletion. The model was used to evaluate groundwater contamination and cleanup times for four complex mixtures of concern in the railroad industry. Among the petroleum hydrocarbon mixtures considered, the cleanup time of diesel fuel was much longer than E95, gasoline, and crude oil. This is mainly due to the high fraction of low solubility components in diesel fuel. The results demonstrate that the updated screening model with the newly developed SZDM is computationally efficient, and provides valuable comparisons of cleanup times that can be used in assessing the health and financial risk associated with chemical mixture spills from railroad-tank-car accidents.  相似文献   

13.
Freshwater resources in the arid Arabian Peninsula, especially transboundary aquifers shared by Saudi Arabia, Jordan, and Iraq, are of critical environmental and geopolitical significance. Monthly Gravity Recovery and Climate Experiment (GRACE) satellite‐derived gravity field solutions acquired over the expansive Saq transboundary aquifer system were analysed and spatiotemporally correlated with relevant land surface model outputs, remote sensing observations, and field data to quantify temporal variations in regional water resources and to identify the controlling factors affecting these resources. Our results show substantial GRACE‐derived terrestrial water storage (TWS) and groundwater storage (GWS) depletion rates of ?9.05 ± 0.25 mm/year (?4.84 ± 0.13 km3/year) and ?6.52 ± 0.29 mm/year (?3.49 ± 0.15 km3/year), respectively. The rapid decline is attributed to both climatic and anthropogenic factors; observed TWS depletion is partially related to a decline in regional rainfall, while GWS depletions are highly correlated with increasing groundwater extraction for irrigation and observed water level declines in regional supply wells.  相似文献   

14.
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15.
Landscapes evolve in response to external forces, such as tectonics and climate, that influence surface processes of erosion and weathering. Internal feedbacks between erosion and weathering also play an integral role in regulating the landscapes response. Our understanding of these internal and external feedbacks is limited to a handful of field‐based studies, only a few of which have explicitly examined saprolite weathering. Here, we report rates of erosion and weathering in saprolite and soil to quantify how climate influences denudation, by focusing on an elevation transect in the western Sierra Nevada Mountains, California. We use an adapted mass balance approach and couple soil‐production rates from the cosmogenic radionuclide (CRN) 10Be with zirconium concentrations in rock, saprolite and soil. Our approach includes deep saprolite weathering and suggests that previous studies may have underestimated denudation rates across similar landscapes. Along the studied climate gradient, chemical weathering rates peak at middle elevations (1200–2000 m), averaging 112·3 ± 9·7 t km–2 y–1 compared to high and low elevation sites (46·8 ± 5·2 t km?2 y?1). Measured weathering rates follow similar patterns with climate as those of predicted silica fluxes, modeled using an Arrhenius temperature relationship and a linear relationship between flux and precipitation. Furthermore, chemical weathering and erosion are tightly correlated across our sites, and physical erosion rates increase with both saprolite weathering rates and intensity. Unexpectedly, saprolite and soil weathering intensities are inversely related, such that more weathered saprolites are overlain by weakly weathered soils. These data quantify exciting links between climate, weathering and erosion, and together suggest that climate controls chemical weathering via temperature and moisture control on chemical reaction rates. Our results also suggest that saprolite weathering reduces bedrock coherence, leading to faster rates of soil transport that, in turn, decrease material residence times in the soil column and limit soil weathering. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

16.
Kangjoo Kim 《水文研究》2002,16(9):1793-1806
The weathering rate of plagioclase was estimated in the groundwater system of a sandy, silicate aquifer formed after the Wisconsin Glacial Stage. The study area is an isthmus lying between Crystal and Big Muskellunge Lakes in northern Wisconsin, USA. Plagioclase occupies 3% of the quartz and K‐feldspar dominated sediments. Groundwater in the study area is recharged in part by precipitation through the isthmus soils and in part by seepage from Crystal Lake, which is of low ionic strength and chemically in steady state. Water analysis revealed that the chemistry of groundwater recharged from Crystal Lake is regulated by mineral dissolution reactions. The rate constant for plagioclase was estimated using mass balances for sodium concentrations along a groundwater flowline from Crystal Lake. For this calculation, various kinds of hydrological/mineralogical information were used: groundwater flow path from oxygen isotope analysis, groundwater travel times from flow modelling, mineral composition from microprobe analysis and surface area of minerals from BET (Brunauer–Emmett–Teller) analysis. The overall range of the estimation was less than an order of magnitude (3·5 × 10?16 to 3·4 × 10?15 mol/m2/s). The result is up to three orders of magnitude slower than the previous field estimates, which applied geometric methods in measuring mineral surface areas. However, this result is somewhat higher than the estimates reported by other BET area‐based studies, which were undertaken on soil profiles having different hydrological conditions. This rate difference is interpreted as a result of higher mineral reactivity owing to younger sediment age. The rate difference is smaller when this result is compared with the estimates from the soils of similar age, indicating that the differences in hydrological condition are not sufficient to explain the weathering rate discrepancy between the laboratory and field studies, which is up to five orders of magnitude. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   

17.
There are several key data gaps in our understanding of Natural Source Zone Depletion (NSZD) processes at sites impacted by light nonaqueous phase liquid (LNAPL), and quantifying NSZD rates can be challenging due to the inherent differences in measurement methods. In this study, four different NSZD measurement methods (oxygen influx measured by the Gradient Method, long-term carbon dioxide efflux measured with Carbon Traps, instantaneous carbon dioxide efflux measured with Dynamic Closed Chambers (DCC LI-COR), and the long-term heat flux from biodegradation measured by Thermal NSZD monitoring), as well as LNAPL composition and dissolved gas sampling, were applied at a site in Southern California. These techniques were used to evaluate key questions such as: (1) how do different NSZD rate measurement methods compare, and what causes variability in NSZD results?; (2) to what extent NSZD processes are occurring in LNAPL within the saturated zone?; and (3) how is NSZD related to LNAPL composition change over time? Carbon Traps and Thermal NSZD monitoring measurement methods provided the most consistent NSZD data at this geologically heterogeneous site, with two location average NSZD rates of 540 and 480 gal/acre/year, respectively. Overall, comparisons of NSZD rates between methods were challenging due to different measurement timeframes, significant temporal and spatial heterogeneity, and operational challenges with two of the NSZD methods. Finally, samples of subsurface LNAPL were collected for analysis in 2007 and 2016; results indicated that diesel-range constituents were already very degraded and anaerobic degradation of gasoline-range constituents was ongoing. A LNAPL depletion model (Douglas et al. 1996) applied to the measured LNAPL composition change appeared to greatly overestimate the amount of LNAPL depletion compared to the measured NSZD rate, but did provide an independent semiqualitative line of evidence that LNAPL was being depleted by active NSZD processes at the site.  相似文献   

18.
Quantifying anthropogenic contributions to elemental cycles provides useful information regarding the flow of elements important to industrial and agricultural development and is key to understanding the environmental impacts of human activity. In particular, when anthropogenic fluxes reach levels large enough to influence an element's overall cycle the risk of adverse environmental impacts rises. While intensive groundwater pumping has been observed to affect a wide-range of environmental processes, the role of intensive groundwater extraction on global anthropogenic element cycles has not yet been characterized. Relying on comprehensive datasets of groundwater and produced water (groundwater pumped during oil/gas extraction) chemistry from the U.S. Geological Survey along with estimates of global groundwater usage, I estimate elemental fluxes from global pumping, consumptive use, and depletion of groundwater. I find that groundwater fluxes appreciably contribute to a number of elements overall cycles and thus these cycles were underestimated in prior studies, which did not recognize groundwater pumping's role. I also estimate elemental loadings to agricultural soils in the United States and find that in some regions, groundwater may provide a significant portion (more than 10%) of crop requirements of key nutrients (K, N). With nearly 40% of globally irrigated land under groundwater irrigation, characterizing nutrient and toxic element fluxes to these soils, which ultimately influence crop yields, is important to our understanding of agricultural production. Thus, this study improves our basic understanding of anthropogenic elemental cycles and demonstrates that quantification of groundwater pumping elemental fluxes provides valuable information about the potential for environmental impacts from groundwater pumping.  相似文献   

19.
Natural source zone depletion (NSZD) refers to processes within chemically impacted vadose and saturated zones that reduce the mass of contaminants remaining in a defined source control volume. Studies of large petroleum hydrocarbon release sites have shown that the depletion rate by vapor phase migration of degradation products from the source control volume through the vadose zone (V‐NSZD) is often considerably higher than the rate of depletion from the source control volume by groundwater flow carrying dissolved petroleum hydrocarbons arising from dissolution, desorption, or back diffusion, and degradation products arising from biodegradation (GW‐NSZD). In this study, we quantified vadose zone and GW‐NSZD at a small unpaved fuel release site in California typical of those in settings with predominantly low permeability media. We estimated vadose zone using a dense network of efflux monitoring locations at four sampling events over 2 years, and GW‐NSZD using groundwater monitoring data downgradient of the source control volume in three depth intervals spanning up to 9 years. On average, vadose zone was 17 times greater than GW‐NSZD during the time interval of comparison, and vadose zone was in the range of rates quantified at other sites with petroleum hydrocarbon releases. Estimating vadose zone and GW‐NSZD rates is challenging but the vadose zone rate is the best indicator of overall source mass depletion, whereas GW‐NSZD rates may be useful as baselines to quantify progress of natural or engineered remediation in portions of the saturated zone in which there are impediments to loss of methane and other gases to the vadose zone.  相似文献   

20.
The composition of crude oil in a surficial aquifer was determined in two locations at the Bemidji, MN, spill site. The abundances of 71 individual hydrocarbons varied within 16 locations sampled. Little depletion of these hydrocarbons (relative to the pipeline oil) occurred in the first 10 years after the spill, whereas losses of 25% to 85% of the total measured hydrocarbons occurred after 30 years. The C6‐30 n‐alkanes, toluene, and o‐xylene were the most depleted hydrocarbons. Some hydrocarbons, such as the n‐C10–24 cyclohexanes, tri‐ and tetra‐ methylbenzenes, acyclic isoprenoids, and naphthalenes were the least depleted. Benzene was detected at every sampling location 30 years after the spill. Degradation of the oil led to increases in the percent organic carbon and in the δ 13C of the oil. Another method of determining hydrocarbon loss was by normalizing the total measured hydrocarbon concentrations to that of the most conservative analytes. This method indicated that the total measured hydrocarbons were depleted by 47% to 77% and loss of the oil mass over 30 years was 18% to 31%. Differences in hydrocarbon depletion were related to the depth of the oil in the aquifer, local topography, amount of recharge reaching the oil, availability of electron acceptors, and the presence of less permeable soils above the oil. The results from this study indicate that once crude oil has been in the subsurface for a number of years there is no longer a “starting oil concentration” that can be used to understand processes that affect its fate and the transport of hydrocarbons in groundwater.  相似文献   

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