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1.
The quality of water in the Upper Floridan aquifer near Valdosta, Georgia is affected locally by discharge of Withlacoochee River water through sinkholes in the river bed. Data on transient tracers and other dissolved substances, including Cl−, 3H, tritiogenic helium-3 (3He), chlorofluorocarbons (CFC-11, CFC-12, CFC-113), organic C (DOC), O2 (DO), H2S, CH4, δ18O, δD, and 14C were investigated as tracers of Withlacoochee River water in the Upper Floridan aquifer. The concentrations of all tracers were affected by dilution and mixing. Dissolved Cl−, δ18O, δD, CFC-12, and the quantity (3H+3He) are stable in water from the Upper Floridan aquifer, whereas DOC, DO, H2S, CH4, 14C, CFC-11, and CFC-113 are affected by microbial degradation and other geochemical processes occurring within the aquifer. Groundwater mixing fractions were determined by using dissolved Cl− and δ18O data, recognizing 3 end-member water types in the groundwater mixtures: (1) Withlacoochee River water (δ18O=−2.5±0.3‰, Cl−=12.2±2 mg/l), (2) regional infiltration water (δ18O=−4.2±0.1‰, Cl−=2.3±0.1 mg/l), and (3) regional paleowater resident in the Upper Floridan aquifer (δ18O=−3.4±0.1‰, Cl−=2.6±0.1 mg/l) (uncertainties are ±1σ). Error simulation procedures were used to define uncertainties in mixing fractions. Fractions of river water in groundwater range from 0 to 72% and average 10%. The influence of river-water discharge on the quality of water in the Upper Floridan aquifer was traced from the sinkhole area on the Withlacoochee River 25 km SE in the direction of regional groundwater flow. Infiltration of water is most significant to the N and NW of Valdosta, but becomes negligible to the S and SE in the direction of general thickening of post-Eocene confining beds overlying the Upper Floridan aquifer.  相似文献   

2.
Geochemical reaction models were evaluated to improve radiocarbon dating of dissolved inorganic carbon (DIC) in groundwater from confined parts of the Upper Floridan aquifer in central and northeastern Florida, USA. The predominant geochemical reactions affecting the 14C activity of DIC include (1) dissolution of dolomite and anhydrite with calcite precipitation (dedolomitization), (2) sulfate reduction accompanying microbial degradation of organic carbon, (3) recrystallization of calcite (isotopic exchange), and (4) mixing of fresh water with as much as 7% saline water in some coastal areas. The calculated cumulative net mineral transfers are negligibly small in upgradient parts of the aquifer and increase significantly in downgradient parts of the aquifer, reflecting, at least in part, upward leakage from the Lower Floridan aquifer and circulation that contacted middle confining units in the Floridan aquifer system. The adjusted radiocarbon ages are independent of flow path and represent travel times of water from the recharge area to the sample point in the aquifer. Downgradient from Polk City (adjusted age 1.7 ka) and Keystone Heights (adjusted age 0.4 ka), 14 of the 22 waters have adjusted 14C ages of 20–30 ka, indicating that most of the fresh-water resource in the Upper Floridan aquifer today was recharged during the last glacial period. All of the paleowaters are enriched in 18O and 2H relative to modern infiltration, with maximum enrichment in δ18O of approximately 2.0‰. Electronic Publication  相似文献   

3.
Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO3 (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6)—for four Ca–HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.The online version of the original article can be found at  相似文献   

4.
Large karstic springs in east-central Florida, USA were studied using multi-tracer and geochemical modeling techniques to better understand groundwater flow paths and mixing of shallow and deep groundwater. Spring water types included Ca–HCO3 (six), Na–Cl (four), and mixed (one). The evolution of water chemistry for Ca–HCO3 spring waters was modeled by reactions of rainwater with soil organic matter, calcite, and dolomite under oxic conditions. The Na–Cl and mixed-type springs were modeled by reactions of either rainwater or Upper Floridan aquifer water with soil organic matter, calcite, and dolomite under oxic conditions and mixed with varying proportions of saline Lower Floridan aquifer water, which represented 4–53% of the total spring discharge. Multiple-tracer data—chlorofluorocarbon CFC-113, tritium (3H), helium-3 (3Hetrit), sulfur hexafluoride (SF6)—for four Ca–HCO3 spring waters were consistent with binary mixing curves representing water recharged during 1980 or 1990 mixing with an older (recharged before 1940) tracer-free component. Young-water mixing fractions ranged from 0.3 to 0.7. Tracer concentration data for two Na–Cl spring waters appear to be consistent with binary mixtures of 1990 water with older water recharged in 1965 or 1975. Nitrate-N concentrations are inversely related to apparent ages of spring waters, which indicated that elevated nitrate-N concentrations were likely contributed from recent recharge.An erratum to this article can be found at  相似文献   

5.
《Applied Geochemistry》2003,18(7):1043-1063
The Memphis aquifer in southwestern Tennessee is confined to a semi-confined unconsolidated sand aquifer and is the primary municipal water source in the Memphis metropolitan area. Past studies have identified regions in the metropolitan area in which the overlying upper Claiborne confining unit lacks significant clay and provides a hydraulic connection between the shallow aquifer and the Memphis aquifer. In this study, major solute chemistry, 3H, and 3H/3He groundwater dating are used to investigate the extent and chemical effects of leakage through the confining unit to the Memphis aquifer in the vicinity of a municipal well field. The 3H/3He dates and geochemical modeling of the chemical data are used to constrain mixing fractions and the timing of modern recharge. Tritium activities of as much as 2.8 TU are observed in shallow production wells, but deeper production wells have 3H activities that approach the detection limit. Trends in water chemistry indicate vertical mixing in the aquifer of shallow Na–SO4–Cl-rich water and deeper Ca–Mg–HCO3-rich water. Water chemistry does not vary consistently with seasonal pumping, but 3H activity generally decreases during low use periods. Stable O and H isotopes show little variation and are not useful groundwater tracers for this study. The 3H-bearing, Na–SO4–Cl-rich water is interpreted to reflect recharge of modern water through the upper Claiborne confining unit. The 3H/3He dates from 5 production wells indicate modern recharge, that infiltrated 15–20 a ago, is present in the shallow production wells. Geologic data and hydrologic boundary conditions suggest that the most likely source for continued leakage is a nearby stream, Nonconnah Creek. Geochemical reaction modeling using the NETPATH computer code suggests that proportions of shallow aquifer water leaking into the Memphis aquifer range from 6 to 32%. The 3H/3He dating and NETPATH modeling results correlate well, suggesting that these complementary analytical tools provide an effective means to evaluate proportions of modern water leaking into semi-confined aquifers. These results also indicate a need to carefully consider connections between surface water and semi-confined groundwater resources in wellhead protection programs.  相似文献   

6.
Measured concentrations of environmental tracers in spring discharge from a karst aquifer in the Shenandoah Valley, USA, were used to refine a numerical groundwater flow model. The karst aquifer is folded and faulted carbonate bedrock dominated by diffuse flow along fractures. The numerical model represented bedrock structure and discrete features (fault zones and springs). Concentrations of 3H, 3He, 4He, and CFC-113 in spring discharge were interpreted as binary dilutions of young (0–8  years) water and old (tracer-free) water. Simulated mixtures of groundwater are derived from young water flowing along shallow paths, with the addition of old water flowing along deeper paths through the model domain that discharge to springs along fault zones. The simulated median age of young water discharged from springs (5.7  years) is slightly older than the median age estimated from 3H/3He data (4.4  years). The numerical model predicted a fraction of old water in spring discharge (0.07) that was half that determined by the binary-dilution model using the 3H/3He apparent age and 3H and CFC-113 data (0.14). This difference suggests that faults and lineaments are more numerous or extensive than those mapped and included in the numerical model.  相似文献   

7.
The hydrochemical interaction between groundwater and lakewater influences the composition of water that percolates downward from the surficial aquifer system through the underlying intermediate confining unit and recharges the Upper Floridan aquifer along highlands in Florida. The 87Sr/86Sr ratio along with the stable isotopes, D, 18O, and 13C were used as tracers to study the interaction between groundwater, lakewater, and aquifer minerals near Lake Barco, a seepage lake in the mantled karst terrane of northern Florida. Upgradient from the lake, the 87Sr/86Sr ratio of groundwater decreases with depth (mean values of 0.71004, 0.70890, and 0.70852 for water from the surficial aquifer system, intermediate confining unit, and Upper Floridan aquifer, respectively), resulting from the interaction of dilute oxygenated recharge water with aquifer minerals that are less radiogenic with depth. The concentrations of Sr2+ generally increase with depth, and higher concentrations of Sr2+ in water from the Upper Floridan aquifer (20–35 μg/L), relative to water from the surficial aquifer system and the intermediate confining unit, result from the dissolution of Sr-bearing calcite and dolomite in the Eocene limestone. Dissolution of calcite [δ13C = −1.6 permil (%o)] is also indicated by an enriched δ13CDIC(-8.8 to -11.4% o) in water from the Upper Floridan aquifer, relative to the overlying hydrogeologic units (δ13CDIC < -16%o).

Groundwater downgradient from Lake Barco was enriched in 18O and D relative to groundwater upgradient from the lake, indicating mixing of lakewater leakage and groundwater. Downgradient from the lake, the 87Sr/86Sr ratio of groundwater and aquifer material become less radiogenic and the Sr2+ concentrations generally increase with depth. However, Sr2+ concentrations are substantially less than in upgradient groundwaters at similar depths. The lower Sr2+ concentrations result from the influence of anoxic lakewater leakage on the mobility of Sr2+ from clays. Based on results from mass-balance modeling, it is probable that cation exchange plays the dominant role in controlling the 87Sr/86Sr ratio of groundwater, both upgradient and downgradient from Lake Barco. Even though groundwater from the three distinct hydrogeologic units displays considerable variability in Sr concentration and isotopic composition, the dominant processes associated with the mixing of lakewater leakage with groundwater, as well as the effects of mineral-water interaction, can be ascertained by integrating the use of stable and radiogenic isotopic measurements of groundwater, lakewater, and aquifer minerals.  相似文献   


8.
In response to concerns about the steady increase in nitrate concentrations over the past several decades in many of Floridas first magnitude spring waters (discharge 2.8 m3/s), multiple isotopic and other chemical tracers were analyzed in water samples from 12 large springs to assess sources and timescales of nitrate contamination. Nitrate-N concentrations in spring waters ranged from 0.50 to 4.2 mg/L, and 15N values of nitrate in spring waters ranged from 2.6 to 7.9 per mil. Most 15N values were below 6 per mil indicating that inorganic fertilizers were the dominant source of nitrogen in these waters. Apparent ages of groundwater discharging from springs ranged from 5 to about 35 years, based on multi-tracer analyses (CFC-12, CFC-113, SF6, 3H/3He) and a piston flow assumption; however, apparent tracer ages generally were not concordant. The most reliable spring-water ages appear to be based on tritium and 3He data, because concentrations of CFCs and SF6 in several spring waters were much higher than would be expected from equilibration with modern atmospheric concentrations. Data for all tracers were most consistent with output curves for exponential and binary mixing models that represent mixtures of water in the Upper Floridan aquifer recharged since the early 1960s. Given that groundwater transit times are on the order of decades and are related to the prolonged input of nitrogen from multiple sources to the aquifer, nitrate could persist in groundwater that flows toward springs for several decades due to slow transport of solutes through the aquifer matrix.  相似文献   

9.
The northern section of the Bohemian Cretaceous Basin has been the site of intensive U exploitation with harmful impacts on groundwater quality. The understanding of groundwater flow and age distribution is crucial for the prediction of the future dispersion and impact of the contamination. State of the art tracer methods (3H, 3He, 4He, 85Kr, 39Ar and 14C) were, therefore, used to obtain insights to ageing and mixing processes of groundwater along a north–south flow line in the centre of the two most important aquifers of Cenomanian and middle Turonian age. Dating of groundwater is particularly complex in this area as: (i) groundwater in the Cenomanian aquifer is locally affected by fluxes of geogenic and biogenic gases (e.g. CO2, CH4, He) and by fossil brines in basement rocks rich in Cl and SO4; (ii) a thick unsaturated zone overlays the Turonian aquifer; (iii) a periglacial climate and permafrost conditions prevailed during the Last Glacial Maximum (LGM), and iv) the wells are mostly screened over large depth intervals.Large disagreements in 85Kr and 3H/3He ages indicate that processes other than ageing have affected the tracer data in the Turonian aquifer. Mixing with older waters (>50 a) was confirmed by 39Ar activities. An inverse modelling approach, which included time lags for tracer transport throughout the unsaturated zone and degassing of 3He, was used to estimate the age of groundwater. Best fits between model and field results were obtained for mean residence times varying from modern up to a few hundred years. The presence of modern water in this aquifer is correlated with the occurrence of elevated pollution (e.g. nitrates).An increase of reactive geochemical indicators (e.g. Na) and radiogenic 4He, and a decrease in 14C along the flow direction confirmed groundwater ageing in the deeper confined Cenomanian aquifer. Radiocarbon ages varied from a few hundred years to more than 20 ka. Initial 14C activity for radiocarbon dating was calibrated by means of 39Ar measurements. The 14C age of a sample recharged during the LGM was further confirmed by depleted stable isotope signatures and near freezing point noble gas temperature. Radiogenic 4He accumulated in groundwater with concentrations increasing linearly with 14C ages. This enabled the use of 4He to validate the dating range of 14C and extend it to other parts of this aquifer. In the proximity of faults, 39Ar in excess of modern concentrations and 14C dead CO2 sources, elevated 3He/4He ratios and volcanic activity in Oligocene to Quaternary demonstrate the influence of gas of deeper origin and impeded the application of 4He, 39Ar and 14C for groundwater dating.  相似文献   

10.
Corrected groundwater 14C ages from the carbonate aquifer in Yucca Flat at the former Nevada Test Site (now the Nevada National Security Site), USA, were evaluated by comparing temporal variations of groundwater 36Cl/Cl estimated with these 14C ages with published records of meteoric 36Cl/Cl variations preserved in packrat middens (piles of plant fragments, fecal matter and urine). Good agreement between these records indicates that the groundwater 14C ages are reasonable and that 14C is moving with chloride without sorbing to the carbonate rock matrix or fracture coatings, despite opposing evidence from laboratory experiments. The groundwater 14C ages are consistent with other hydrologic evidence that indicates significant basin infiltration ceased 8,000 to 10,000 years ago, and that recharge to the carbonate aquifer is from paleowater draining through overlying tuff confining units along major faults. This interpretation is supported by the relative age differences as well as hydraulic head differences between the alluvial and volcanic aquifers and the carbonate aquifer. The carbonate aquifer 14C ages suggest that groundwater velocities throughout much of Yucca Flat are about 2 m/yr, consistent with the long-held conceptual model that blocking ridges of low-permeability rock hydrologically isolate the carbonate aquifer in Yucca Flat from the outlying regional carbonate flow system.  相似文献   

11.
We report measurements of pH, total dissolved inorganic carbon (DIC), total or titration alkalinity (TAlk), Ca2+, Mg2+, sulfate, and sulfide data at the seawater-freshwater interface in a shallow groundwater aquifer in North Inlet, South Carolina. These measurements and a diagenetic modeling analysis indicate that the groundwaters at North Inlet are mixtures of seawater and freshwater end-members and are seriously modified by carbon dioxide inputs from organic carbon degradation via SO42− reduction across the entire salinity range and fermentation and CaCO3 dissolution in the low-salinity region. DIC and TAlk are several times higher than the theoretical dilution line, whereas Ca2+ is slightly higher and SO42− is somewhat lower than the dilution line. Partial pressure of CO2 in the groundwater is extremely high (0.05 to 0.12 atm). These deviations are consistent with theoretical predictions from known diagenetic reactions. Estimated groundwater DIC fluxes to the South Atlantic Bight from either the surficial aquifer (via salt marshes) or the Upper Floridan Aquifer (direct input) are significant when compared to riverine flux in this area.  相似文献   

12.
Tracer data can serve to derive parameters related to groundwater systems or can be used in the calibration of transport and flow models. Temperature, 3H/3He (age dating) and hydrochemical data, together with head measurements, borehole logs and an aquifer test, were used to obtain insight into the flow and transport of a Quaternary aquifer system located in the Belgian polder area. Flow and transport model code SEAWAT acted as the integration medium for the different data. Each type of data has its own interpretation technique and adds components to the model. Additionally, different types of data aid in verification of the results. For instance, fluxes from temperature logs (used with the SEAWAT model), and water quality and age dating all provide information on flow to and velocities in the vicinity of drainage ditches. Different data also provide information on different scales. Temperature logs and aquifer tests act on a small scale, groundwater age is influenced by larger-scale flow, and water quality is determined by the general flow of the area. Integration of different kinds of geological, hydrological, geophysical and geochemical data is shown to be an important way forward in the efforts to model real-world cases.  相似文献   

13.
《Applied Geochemistry》2005,20(3):599-609
36Cl produced by thermonuclear bomb testing has been proposed as an additional tool to date or at least to identify recent groundwater components. In order to investigate the behaviour of 36Cl in shallow groundwater a multi-tracer approach (3H/3He, SF6, CFC-12 and 85Kr) was used to characterise and date the groundwater of a quaternary sands aquifer which is located on the Island of Funen near the city of Odense, Denmark. Recharge to the semi-confined shallow aquifer occurs through permeable sand windows and fractured tills at the surface. Locally, however, mixing with older pre-bomb water from the underlying limestone aquifer may occur. The integrated analyses of the available tracer data allowed a well constrained age structure determination of the investigated water system.The 36Cl/Cl ratios measured in groundwater were used to reconstruct the fallout rates for radioactive 36Cl at Odense. The calculated fallout values exceeded the fallout estimated based on data from the Dye-3 ice core in Greenland. Recycling of the bomb peak fallout seems to be the most probable reason of the high values measured. The local extent of this process is difficult to quantify, which impedes the use of 36Cl for dating.  相似文献   

14.
Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l−1, and the following groundwater types are recognized: Ca2+–Mg2+–HCO3−, Ca2+–Mg2+–SO42− and Ca2+–Mg2+–Cl−. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ18O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ18O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.  相似文献   

15.
Sources of groundwater recharge to the Badain Jaran Desert in China have been investigated using geochemical and isotopic techniques. Stable isotope compositions (δ18O and δ2H) of shallow groundwater and surface water from oasis lakes evolve from a starting composition considerably depleted compared to local unsaturated zone moisture, confirming inferences from chloride mass balance that direct infiltration of precipitation is not a volumetrically important source of recharge to the shallow aquifer in the study area. Shallow phreatic and deeper confined groundwater bodies appear unconnected based on chemical composition and radiocarbon activities. Hydrogeologic evidence points toward a bordering mountain range (Yabulai) as a likely recharge zone, which is consistent with tracer results. A mean residence time in the range of 1–2 ka for the desert’s southeastern margin is inferred from radiocarbon. These results reveal that some replenishment to the desert aquifer is occurring but at a rate much lower than previously suggested, which is relevant for water resources planning in this ecologically sensitive area.  相似文献   

16.
The use of radionuclides as clocks for groundwater dating and as probes to investigate the geometry and spatial extent of the contact area between rocks and water is reviewed. Subsurface production rates for222Rn37Ar,85Kr,39Ar,36CI,3He,4He and40Ar in various rock types are listed. Measured Rn fluxes from the surface of sandstone grains and from pieces of granite point to scale-dependent diffusion coefficients. The temporal evolution of subsurface-produced222Rn-,37Ar-,85Kr- and39Ar-activities in groundwaters yields radionuclide escape factors between 0.1 % and 9% for the Stripa granite (Sweden) and between 1% and 4% for the Milk River sandstone (Canada). The combination of3H,85Kr,39Ar,14C,36CI,4He in the UK Triassic sandstone aquifer allows groundwater dating up to 40 000 a. Very old groundwaters can be studied using Cl,36Cl and4He evolution as demonstrated in the Milk River aquifer in Canada.  相似文献   

17.
The chemical and isotopic composition of groundwater from 52 sites in the London (U.K.) area was determined as part of a project aimed at assessing the spatial variation in the age of Chalk groundwater, and in determining the relationship between fracture and matrix groundwater in this dual porosity system.Systematic changes in groundwater chemistry take place in the downgradient direction in response to several chemical processes. These processes include early concentration by evaporation and congruent dissolution of calcite followed by widespread incongruent dissolution and ion exchange in addition to local oxidation-reduction reactions, gypsum dissolution and saline intrusion. As a result of the above processes, Chalk groundwater follows an evolutionary path from Ca bicarbonate type to Na bicarbonate type.The age of Chalk groundwater was modelled using14C, δ13C,3H, δ2H and δ180. There is a general increase in the groundwater age in a downgradient direction with the oldest water found in N central areas of the basin. Groundwater in the unconfined zones and in areas S of the Greenwich fault is almost entirely of unevolved, modem composition. Carbon-14 modelling suggests that Chalk groundwater in the S basin is generally less than 10000 a old while that in the north is generally between 10000 and 25000 a old. The presence of3H in concentrations of up to 7 TU in groundwater which yields ages of several 1000 a, however, indicates that mechanisms exist for the rapid introduction of recent groundwater to the confined aquifer. Results of palaeorecharge temperature determinations using δ2H, δ180 and noble gas analytical results suggest that significant Devensian recharge did indeed occur in the aquifer.A model of the development of the Chalk recognizes that it is a classic dual porosity aquifer in which groundwater flow occurs predominantly in the fracture system. The upper 50 m of the aquifer was flushed with fresh water during the 2–3 × 106 a of the Quaternary and therefore meteoric water largely replaced the Tertiary and Cretaceous marine water that previously saturated the system. Most processes which control the chemistry of the groundwater occur in the matrix where the surface area is exceptionally high. Although fracture flow dominates the flow regime, diffusion from the matrix into the fracture porosity controls the chemistry of Chalk groundwater.  相似文献   

18.
Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study   总被引：3，自引：0，他引：3  
Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (SbT) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg−1; in the Upper Floridan aquifer, SbT concentrations range from 8.1 to 1,462 pmol kg−1; and for the Aquia aquifer, SbT concentrations range between 23 and 512 pmol kg−1. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO4 reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)30 species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)6− species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb2S4 − and Sb2S4 2−, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO4, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO4 couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.  相似文献   

19.
The alluvial aquifer of the Guadalquivir River comprises shallow Quaternary deposits located in the central-eastern part of the Province of Jaén in southern Spain, where groundwater resources are used mainly for crop irrigation in an important agricultural area. In order to establish the baseline hydrochemical conditions and processes determining the groundwater quality, groundwater and river water samples were collected as part of an integrated investigation that coupled multivariate statistical analysis with hydrochemical methods to identify and interpret the groundwater chemistry of the aquifer system. Three main hydrochemical types (Mg–Ca–HCO3, Ca–Mg–SO4–HCO3–Cl and Na–Ca–Mg–Cl–SO4) were identified. Further interpretation, using R-mode principal components analysis (PCA) conducted with 13 hydrochemical variables, identified two principal components which explain ⅔ of the variance in the original data. In combination with the hydrochemical interpretation, mineralogical analyses of the aquifer sediment together with inverse geochemical modelling using NETPATH showed that dedolomitization (calcite precipitation and dolomite dissolution driven by gypsum dissolution) is the principal hydrochemical process controlling the regional groundwater chemistry. Other processes such as silicate weathering, ion exchange, mixing between river water and groundwater, and agricultural practices also affect the groundwater chemistry.  相似文献   

20.
 A karst-fissured aquifer in the Upper Jurassic carbonate rocks of the Krakow Upland shows a very high yield (safe yield 117 000 m3/day) and belongs to the major groundwater basins (MGBs) of Poland. The uncovered character of the aquifer and its hydraulic structure favor the intensive infiltration and migration of anthropogenic pollutants from the surface. This pollution is caused by agriculture and industry in the proximity of Krakow and the Upper Silesian agglomeration. Progressive degradation of groundwater quality on a regional scale results. Evaluation of the endangering of the aquifer studied is based on the analysis of the time interval of vertical water percolation from the surface, the time interval of groundwater horizontal flow through the aquifer and the duration of water residence in the aquifer derived from tritium data. Quaternary and Cretaceous overburden occur in the Krakow Upland in addition to numerous outcrops of limestones. The time interval of vertical water percolation in highly permeable limestones does not exceed 3 years and in the areas covered by overburden it is from several to 50 years. The mean effective time interval of horizontal groundwater flow through the Upper Jurassic rocks along the flow paths ranges from several months in the areas of direct drainage to over 15 years in the elevated areas of local groundwater divides. The age of water in the rock matrix was determined using tritium data interpreted according to an exponential model and it ranges from 70 years to over 130 years. In karst-fissured systems with a high retardation index (Rp=21) the effective time of water circulation in local drainage basins does not exceed 7 years. The Krakow-Wieluń Upland is the most extensive and uniform karst region in Poland. It is a belt of Upper Jurassic limestone extending from Krakcow in the southeast to Wieluń in the northwest on the northeast slope of the Silesian Upland. Residual hills of Paleogene age separated by infilled karst depressions are the most characteristic features of the Krakow-Wieluń Upland. More than 800 small caves are known in this area, but only two of them reach 1 km of aggregate passage length (Gazek and others 1992). Received: 4 December 1996 · Accepted: 29 April 1997  相似文献   

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