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1.
《Applied Geochemistry》2006,21(11):1969-1985
Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (HgT up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO4 (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO4/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The HgT mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved HgT is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.  相似文献   

2.
Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH4 gas content and its C isotopes (δ13CCH4), and select isotope tracers (δ11B, 87Sr/86Sr, δ2H, δ18O, δ13CDIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH4 was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH4/L. The δ13CCH4 of dissolved CH4 ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH4 concentrations, with a possible minor contribution of trace amounts of thermogenic CH4. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ13CCH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO3 dominated, (3) TDS > 100 mg/L and Na–HCO3 dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (87Sr/86Sr = 0.7097–0.7166), C (δ13CDIC = −21.3‰ to −4.7‰), and B (δ11B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO3, and higher-mineralized Na–HCO3 composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH4 and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.  相似文献   

3.
A detail investigation was carried out to improve the current knowledge of groundwater salinisation processes in coastal aquifers using hydrochemical and isotopic parameters. Data of major ions for 40 wells located in the Salalah plain aquifer, Sultanate of Oman, were collected during pre-monsoon 2004 and analysed. The groundwater changes along the general flow path towards the coast from fresh (EC < 1500 μS/cm), brackish (EC: 1500–3000 μS/cm) and saline (EC > 3000 μS/cm). Results of inverse modeling simulations using PHREEQC show that dissolution of halite may be the main source of Cl and Na in the study area. Ionic delta calculation indicates that the depletion of Na and K and enrichment of Ca and Mg in groundwater were probably attributed to reverse ion exchange reactions. During a sampling campaign conducted in October 2015, 11 groundwater samples were collected for Cl, Br and isotopic analysis (2H/18O). Molar Cl/Br ratios in fresh groundwater were higher than those of seawater, indicating the impact of halite dissolution on the groundwater quality. For saline groundwater, these ratios were less than those of seawater, showing the influence of anthropogenic input from agriculture on the same. Relatively depleted isotopic signature of all groundwater samples show that the monsoon precipitation is the main source of groundwater recharge in the study area.  相似文献   

4.
New isotopic and chemical data on the sodium bicarbonate water and associated gases from the Razdolnoe Spa located in the coastal zone of Primorsky Kray of the Russian Far East, together with previous stable isotope data (δ18O, δD, δ13C), allow elucidation of the origin and evolution of the groundwater and gases from the spa. The water is characterized by low temperature (12 °C), TDS – 2.5–6.0 g/L, high contents of B (∼5 mg/L) and F (4.5 mg/L) and low contents of Cl and SO4. Water isotopic composition indicates its essentially meteoric origin which may comply with an older groundwater that was recharged under different (colder) climatic conditions. Major components of bubbling gases are CH4 (68 vol%), N2 (28%) and CO2 (4%). The obtained values δ13C and δD for CO2 and CH4 definitely indicate the marine microbial origin of methane. Thus the high methane content in the waters relates to the biochemical processes and presence of a dispersed organic matter in the host rocks. Based on the regional hydrogeology and the geological structure of the Razdolnoe Spa, Mesozoic fractured rocks containing Na–HCO3 mineral water and gases are reservoir rocks, a chemical composition of water and gases originates in different environmental conditions.  相似文献   

5.
A field experiment is being carried out at the Diavik diamond mine in northern Canada to investigate the influence of unsaturated flow behavior on the quality of drainage from mine waste rock piles in a region of continuous permafrost. This paper is part of a series describing processes affecting the weathering of waste rock and transport of reaction products at this site; here the focus is on unsaturated water flow and its role in mass loading. Two 15 m-high instrumented test piles have been built on 60 m by 50 m collection systems, each consisting of lysimeters and a large impermeable high-density polyethylene (HDPE) liner. Collection lysimeters are installed nearby to investigate infiltration in the upper 2 m of the waste rock. Porosity, water retention curves, and hydraulic conductivity functions are estimated from field measurements and for samples ranging in size from 200 cm3 to 16 m3. Net infiltration in 2007 is estimated to have been 37% of the rainfall for mean annual rainfall conditions. Early-season infiltration freezes and is remobilized as the waste rock thaws. Wetting fronts migrate at rates of 0.2–0.4 m d−1 in response to common rainfall events and up to 5 m d−1 in response to intense rainfall. Pore water and non-reactive solutes travel at rates of <10−2 to 3 × 10−2 m d−1 in response to common rainfall events and up to 0.7 m d−1 in response to intense rainfall. Time-varying SO4 mass loading from the base of the test piles is dictated primarily by the flow behavior, rather than by changes in solute concentrations.  相似文献   

6.
This study investigated the efficiency of a constructed wetland/filter basin (CW/FB) treatment system to improve the chemical composition of waste and surface waters. The system was constructed in closed phosphate mines used for clay settling and sand tailings. Monitoring was carried out for 18 months to evaluate the CW/FB performance under a variety of climatic conditions. Water samples were taken bi-monthly. To evaluate possible groundwater input into and water leaking out of the wetland 6 monitor wells were installed along the flow path and sampled monthly. In order to estimate the change of water chemistry along the wetland flow path, water samples along a transect were taken during the dry and rainy seasons. The samples were analyzed for pH, T, oxidation–reduction potential (ORP), conductivity, total dissolved solids (TDS), dissolved oxygen (DO), Fe(II), H2S, major anions, major cations, arsenic, fecal and total coliform.The study showed the following changes in water quality between the input and output: (1) Substantial decrease of water temperature (up to 10 °C); (2) Significant change in pH from about 9 to 6.5–7; (3) Negative ORP confirming the reducing conditions of the treatment system; (4) Substantial increase of H2S (up to 1060 µg/L); (5) Reduction of As from 5 to <2 µg/L (mostly <0.5); (6) Substantial reduction of SO4, F, Cl, NO3, NO2, Br, Na, K, Ca, and Mg; (7) Reduction of fecal and total coliform from 30–730 and 1000–7000 to <2 and <100 count/100 mL, respectively. In general, the performance of the CW/FB treatment system showed great potential to improve the water quality of industrial and municipal wastewater. Despite significant seasonal variations with respect to temperature, rainfall and humidity, the chemical/microbiological composition of the wetland output remained relatively constant.  相似文献   

7.
《Applied Geochemistry》2005,20(10):1907-1919
Soil from an infiltration trench for highway runoff was leached in columns alternately with NaCl and de-ionised water to simulate the runoff of de-icing salt into the trench followed by snowmelt or rainwater. Simultaneously, two columns with the same soil were leached with de-ionised water throughout the experiment. In addition, the groundwater below the infiltration trench was sampled on some occasions. The column leachate and groundwater were split into two sub samples, one was filtered though a 0.45 μm filter; both were analysed for Pb, Cd, Zn, Fe and total organic carbon (TOC). The column experiment showed clearly that an extensive mobilisation of Pb occurred in low electrolyte water leaching following NaCl leaching. The high Pb concentration coincided with peaks in Fe and TOC concentrations and implied colloid-assisted transport. Conversely, Cd and Zn concentrations were raised in the NaCl leachate and a high correlation with Cl showed that Cl complexes are important for the mobilisation, although a pH effect and ionic exchange cannot be excluded. Only 0.15% and 0.06% of the total amount of Pb was leached from the columns leached with alternating NaCl and deionised water confirming the usual hypotheses about the high immobility of Pb in soils. However, on one occasion when the ionic strength and pH was the lowest measured the concentration of Pb in groundwater sampled from 2.5 m depth was 27 μg L−1 in the dissolved phase (<0.45 μm) and 77 μg L−1 in the particle phase (>0.45 μm). These Pb concentrations are almost 3 and 8 times above the Swedish limit for drinking water quality. Accordingly, in spite of the immobility of Pb the accumulation in roadside soils is so large that groundwater quality is threatened. In conclusion, the study suggests that roadside soils impacted by NaCl from de-icing operations contribute Pb to groundwater by colloid-assisted transport.  相似文献   

8.
《Applied Geochemistry》2006,21(9):1570-1592
Pollution of urban groundwater is routinely reported but the profile of contamination with depth in urban aquifers is rarely resolved. This limits understanding of the depth of penetration of urban recharge and contaminants, and use of urban groundwater. Penetration of anthropogenic solutes (major ions, trace metals) in Permo-Triassic sandstone aquifers underlying two mature conurbations in the UK was investigated through depth-specific, groundwater sampling of dedicated multilevel piezometers. Identification of solute origin and biogeochemical processes (e.g. denitrification, mineral dissolution) was aided by use of stable isotope ratios (34S/32S, 18O/16O, 15N/14N, 13C/12C) and chemical speciation modelling (PHREEQC). Depth profiles of aquifer hydrochemistry reveal penetration of anthropogenic solutes to depths of between 30 and 47 m below ground in the unconfined sandstone and confirm the contributions of faecal and industrial effluents to urban recharge. They also highlight the complexity of solute loading and difficulty resolving solute origin from the range of potential sources in urban groundwater. Faecally-derived NO3 is the most pervasive contaminant exceeding drinking-water quality guidelines and is associated with elevated concentrations of B and SO4. Elevated concentrations of Li, B, Cr and Co are observed at depth in groundwater contaminated by long-term industrial land use (metalworking). Observed penetration of anthropogenic solutes in the unconfined sandstone is consistent with post-development recharge of urban groundwater (residence times <230 a) indicated by flow modelling, and suggests tentatively that urban abstraction to depths of up to 50 m below ground in the unconfined Permo-Triassic sandstone is required to scavenge contaminated groundwater.  相似文献   

9.
The Barwon Downs Graben lies on the northern flanks of the Otway Ranges and is situated approximately 70 km southwest of Geelong, Victoria, Australia. The major lower Tertiary Barwon Downs Graben aquifer comprises highly permeable sands and gravels interbedded with clays and silts of the hydraulically interconnected Pebble Point, Dilwyn and Mepunga Formations. Groundwater flows east into the Barwon Downs Graben from the Barongarook High, and yields 14C ages up to ～20 ka implying that recharge rates are low and, consequently, that the resource could be impacted by overabstraction. The presence of three different lithological units has led to the development of localized flow systems that has resulted in a lack of regular spatial variations in groundwater chemistry. Stable isotopic data suggests that groundwater was recharged under similar climatic conditions as of today. The major ion chemistry of the freshest groundwater is dominated by Na and HCO3 while higher TDS groundwater, from the confining Narrawaturk Marl, is dominated by Na and Cl. Cl/Br ratios are close to rainfall suggesting that halite dissolution is not the principle source of salts. An excess of Na relative to Cl in fresher groundwater suggests that feldspar dissolution has occurred, however, water–rock interaction is limited. The concentrations of Ca, Mg, and SO4 are controlled by silicate dissolution and ion-exchange reactions with clays.  相似文献   

10.
A conceptual groundwater flow model was developed for the crystalline aquifers in southeastern part of the Eastern region, Ghana. The objective was to determine approximate levels of groundwater recharge, estimate aquifer hydraulic parameters, and then test various scenarios of groundwater extraction under the current conditions of recharge. A steady state groundwater flow model has been calibrated against measured water levels of 19 wells in the area. The resulting recharge is estimated to range from 8.97 × 10?5 m/d to 7.14 × 10?4 m/d resulting in a basin wide average recharge of about 9.6% of total annual precipitation, which results in a basin wide quantitative recharge of about 2.4 million m3/d in the area. This compares to recharge estimated from the chloride mass balance of 7.6% of precipitation determined in this study. The general groundwater flow in the area has also been determined to conform to the general northeast–southwest structural grain of the country. The implication is that the general hydrogeology is controlled by post genetic structural entities imposed on the rocks to create ingresses for sufficient groundwater storage and transport. Calibrated aquifer hydraulic conductivities range between 0.99 m/d and over 19.4 m/d. There is a significant contribution of groundwater discharge to stream flow in the study area. Increasing groundwater extraction will have an effect on stream flow. This study finds that the current groundwater extraction levels represent only 0.17% of the annual recharge from precipitation, and that groundwater can sustain future increased groundwater demands from population growth and industrialization.  相似文献   

11.
《Applied Geochemistry》1998,13(5):651-671
Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m3 Ca–Na–Cl brines with about 68 g l−1 total dissolved solids (TDS) and some 270 m3 associated gases, mainly N2 and CH4 were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high 36Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of 36Cl. The Na–Cl–(K-, SO4) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.  相似文献   

12.
Between March 2008 and August 2009, 65,445 tonnes of ∼75 mol% CO2 gas were injected in a depleted natural gas reservoir approximately 2000 m below surface at the Otway project site in Victoria, Australia. Groundwater flow and composition were monitored biannually in two overlying aquifers between June 2006 and March 2011, spanning the pre-, syn- and post-injection periods. The shallower (∼0–100 m), unconfined, porous and karstic aquifer of the Port Campbell Limestone and the deeper (∼600–900 m), confined and porous aquifer of the Dilwyn Formation contain valuable fresh to brackish water resources. Groundwater levels in either aquifer have not been affected by the drilling, pumping and injection activities that were taking place, or by the rainfall increase during the project. In terms of groundwater composition, the Port Campbell Limestone groundwater is brackish (electrical conductivity = 801–3900 μS cm−1), cool (temperature = 12.9–22.5 °C), and near-neutral (pH = 6.62–7.45), whilst the Dilwyn Aquifer groundwater is fresher (electrical conductivity = 505–1473 μS cm−1), warmer (temperature = 42.5–48.5 °C), and more alkaline (pH = 7.43–9.35). Carbonate dissolution, evapotranspiration and cation exchange control the composition of the groundwaters. Comparing the chemical and isotopic composition of the groundwaters collected before, during and after injection shows no statistically significant changes; even if they were statistically significant, they are mostly not consistent with those expected if CO2 addition had taken place. The monitoring program reveals no impact on the groundwater resources attributable to the C storage demonstration project.  相似文献   

13.
《Applied Geochemistry》2006,21(2):289-304
Mineral springs from Daylesford, Australia discharge at ambient temperatures, have high CO2 contents, and effervesce naturally. Mineral waters have high HCO3 and Na concentrations (up to 4110 and 750 mg/L, respectively) and CO2 concentrations of 620–2520 mg/L. Calcium and Mg concentrations are 61–250 and 44–215 mg/L, respectively, and Si, Sr, Ba, and Li are the most abundant minor and trace elements. The high PCO2 of these waters promotes mineral dissolution, while maintaining low pH values, and geochemical modelling indicates that the CO2-rich mineral water must have interacted with both sediments and basalts. Amorphous silica concentrations and silica geothermometry indicate that these waters are unlikely to have been heated above ambient temperatures and therefore reflect shallow circulation on the order of several hundreds of metres. Variations in minor and trace element composition from closely adjacent spring discharges indicate that groundwater flows within relatively isolated fracture networks. The chemical consistency of individual spring discharges over at least 20 a indicates that flow within these fracture networks has remained isolated over long periods. The mineral water resource is at risk from mixing with potentially contaminated surface water and shallow groundwater in the discharge areas. Increased δ2H values and Cl concentrations, and lower Na concentrations indicate those springs that are most at risk from surface contamination and overpumping. Elevated NO3 concentrations in a few springs indicate that these springs have already been contaminated during discharge.  相似文献   

14.
The radioactive isotope 36Cl, with a half-life of 301 ka, is a valuable chronometer for estimation of groundwater residence time up to 2 millions of years. Aerial thermonuclear fission bomb tests, performed during the late 1950s, injected a massive amount of this isotope into the atmosphere, which exceeded the natural fallout signal. Since this bomb pulse, atmospheric 36Cl deposition tends to return to natural fallout rate. The monitoring of this attenuation can provide a good opportunity to extend the use of this chronometer to shorter time spans. Venice’s lagoon alimentation zone shows groundwaters with residence times distributed over last fifty years. This permits the estimation of a continuous 36Cl deposition curve, free from latitudinal and seasonal variations of the signal. Three old groundwater samples, with residence times comprised in the range −900 to −8000 BP, allow the estimation of a mean natural deposition of 49 at m−2 s−1 and are in good agreement with 36Cl fallout observed for the last 40,000 years by (Plummer et al., 1997). For the bomb pulse period, a fallout of 5300 at m−2 s−1 was calculated. This was followed by a strong attenuation period, taking place until the 1980s, during which the fallout reached values ranging between 167 and 354 at m−2 s−1. The attenuation reached then a plateau: it experienced a slower lowering until the actual deposition, with fallout values calculated between 124 and 252 at m−2 s−1. This persistence of high deposition rate was classically attributed to biological and atmospherical recycling processes or underestimation of the natural atmospheric production of the 36Cl. Additional source of 36Cl production has been envisaged through the activation of chlorine radicals from stratospherical CFCs, leading to a 36Cl production rate comparable with that of Ar spallation from the first approximation. Lastly, the latitudinal factor of the attenuation of the fallout rate is discussed and the impact of the jet streams is proposed as an explanation for the discrepancies in the attenuation rate.  相似文献   

15.
300 MW Baspa II is India’s largest private hydroelectric facility, located at the Baspa River which is an important left-hand tributary to the Sutlej River in the NW Himalaya (India). In this valley the Sangla palaeo-lake has been dammed around 8200 yr BP behind a rock-avalanche dam and Baspa II is located exactly on top of this palaeo-lake. This special location represents a very rare possibility to evaluate the short-term, river load and hydrological parameters measured during the planning and operational stages of Baspa II with the long-term parameters gained from the palaeo-lake sediments from the catchment. Sedimentological and geomorphological investigations of the lacustrine sediments have been used to reconstruct environmental changes during >2500 years of its existence. The Mid-Holocene erosion rates of the Baspa catchment estimated from the volume and duration of deposition of the exposed lake sediments are at 0.7–1.0 mm yr−1, almost identical with the modern erosion rates calculated from river gauge data from Baspa II. Several charcoal layers and charcoal pieces from the uppermost palaeo-lake levels around 5000 cal yr BP might be related to woodland clearance and they possibly represent one of the oldest evidences for human presence in the Baspa Valley during Neolithic time.  相似文献   

16.
Stratigraphical, mineralogical, geochemical and optical dating methods were used to reconstruct paleo-hydrological changes in two playas (Phulera, 500 mm/a and Pokharan, 200 mm/a) in near extremum climatic regions of the Thar Desert. Sediment successions in shallow profiles from Phulera and Pokharan contain three and four stratigraphic units, respectively, each with characteristic geochemical properties. These units reflect changes in chemical weathering, detrital input, salinity and provide a measure of the changes in precipitation (i.e. monsoon) through time.Sediments from Pokharan suggest short rainfall events during ca. 6.6–4 ka, relatively stable fresh water (higher and persistent rainfall) regime during 4–2.3 ka, and a hyper saline (low rainfall) condition during 2.3–1.1 ka. Sediments at Phulera, record hyper saline (low rainfall) lacustrine conditions during <2.3 ka to >1.4 ka. Higher abundance of gypsum in Pokharan (2.3–1.1 ka) and proto-dolomite in Phulera (2.3–1.4 ka) are nearly synchronous and reflect enhancement of salinity. Selenite crystals in Pokharan and large desiccation cracks in buried horizons at Phulera reflect desiccation of playas at ca. 2 ka. Both playas progressively became less saline after 1.4 ka. Given the regional nature of this record, these changes are attributed to fluctuation of the monsoon over the Indian sub continent.  相似文献   

17.
The Korba aquifer on the east coast of Cape Bon has been overexploited since the 1960s with a resultant reversal of the hydraulic gradient and a degradation of the quality due to seawater intrusion. In 2008 the authorities introduced integrated water resources planning based on a managed aquifer recharge with treated wastewater. Water quality monitoring was implemented in order to determine the different system components and trace the effectiveness of the artificial recharge. Groundwater samples taken from recharge control piezometers and surrounding farm wells were analyzed for their chemical contents, for their B isotopes, a proven tracer of groundwater salinization and domestic sewage, and their carbamazepine content, an anti-epileptic known to pass through wastewater treatment and so recognized as a pertinent tracer of wastewater contamination. The system equilibrium was permanently disturbed by the different temporal dynamics of continuous processes such as cation exchange, and by threshold processes linked to oxidation–reduction conditions. The B isotopic compositions significantly shifted back-and-forth due to mixing with end-members of various origin. Under the variable contribution of meteoric recharge, the Plio-Quaternary groundwater (δ11B of 35–40.6‰, a mean B concentration of 30 μmol/L, no carbamazepine, n = 7) was subject to seawater intrusion that induced a high δ11B level (δ11B of 41.5–48.0‰, a mean B concentration of 36 μmol/L, and n = 8). Fresh groundwater (δ11B of 19.89‰, B concentration of 2.8 μmol/L, no carbamazepine) was detected close to the recharge site and may represent the deep Miocene pole which feeds the upper Plio-Quaternary aquifer. The managed recharge water (δ11B of 10.67–13.8‰, n = 3) was brackish and of poor quality with a carbamazepine content showing a large short term variability with an average daily level of 328 ± 61 ng/L. A few piezometers in the vicinity of the recharge site gradually acquired a B isotopic composition close to the wastewater signature and showed an increasing carbamazepine content (from 20 to 910 ng/L). The combination of B isotopic signatures with B and carbamazepine contents is a useful tool to assess sources and mixing of treated wastewaters in groundwaters. Effluent quality needs to be greatly improved before injection to prevent further degradation of groundwater quality.  相似文献   

18.
《Applied Geochemistry》2006,21(4):580-613
To quantify and explain the contributions by pollution and chemical weathering to their composition, we studied the chemistries of springs and surface waters in the mountainous part of the Vouga River basin. Water samples were collected during a number of consecutive summer campaigns. Recharge rates were derived from monitored discharge rates within the basin. Very large contributions by meteoric, agricultural and domestic sources to the water chemistries were found, identified by the chloride, sulfate and nitrate concentrations: on average only 1/4 to 1/3 of the solutes could be attributed to chemical weathering. Two petrologic units characterize the river basin: granites and metasediments. The waters collected within metasediment units are distinct from those in granite terrain by a higher magnesium concentration. On that basis, it could be estimated that the Rio Vouga, when leaving the mountainous part of the basin, has for some 2/5 a signature determined by chemical weathering in the metasediments. The dominant primary minerals subject to chemical weathering are plagioclase (Pl) and biotite (in granite) or Pl and chlorite (in metasediment). Kaolinite, gibbsite and vermiculite are the major weathering products where annual precipitation (P) > 1000 mm y−1, and kaolinite, vermiculite and smectite where P was lower. Using an algorithm based on the ratio of dissolved silica to bicarbonate, the contributions of chemical weathering of primary minerals could be unraveled. The results show that in granite the export rate (as mol ha−1 y−1 wt%mineral−1) of oligoclase (Pl with An10–30) was 5.0 ± 2.6 and of biotite 3.2 ± 2.6, while in metasediment these rates for albite (Pl with An0–10) are 16.5 ± 8.9 and for chlorite are 0.5 ± 0.5. The observed decrease of dissolved silica in surface waters relative to springs was ascribed to (summer) uptake by aquatic biota.  相似文献   

19.
About a century of exploitation of the galena-arsenopyrite deposit of Baccu Locci in Sardinia (Italy) has caused a severe, persistent arsenic contamination that extends downstream from the mine for several kilometres. Differently from As, the contamination of lead in surface waters is only localised in the upper part of the mine despite very high Pb concentrations in geologic materials (waste rocks, tailings, stream sediments, soils) over the whole Baccu Locci stream catchment. The aqueous and solid speciation of Pb in various environmental media of the Baccu Locci system was determined by means of a combined analytical (ICP-MS, SEM-EDX, TEM-EDX, chemical extraction) and thermodynamic approach (PHREEQC). The study has pointed out that relatively little Pb (up to 30 µg/L) is initially released to surface waters (pH = 7–8, Eh = 0.4–0.6 V) very rapidly due to dissolution of anglesite that is the first product of galena oxidation. Subsequently, Pb is removed (down to 0.6 µg/L) by probable sorption onto hydrous ferric oxides (e.g. ferrihydrite) and/or possible precipitation of As-containing plumbojarosite that is the main secondary Pb-bearing phase in stream sediments/tailings along the Baccu Locci stream course. The latter hypothesis is controversial since it is reported from the literature that plumbojarosite is formed under acidic conditions, although there is contrary field evidence as well. Bearing in mind the uncertainties introduced from thermodynamic and analytical data, the solubility calculations indicate strong undersaturation of surface waters with respect to plumbojarosite (SI: ? 19.9 to ? 3.7). On the contrary arsenatian plumbojarosite is at or close to saturation (SI: ? 0.6 to 3.2) in most surface waters and beudantite is clearly above saturation (SI: 4.1 to 12.7). This suggests that the incorporation of As might increase the stability of plumbojarosite, extending it up to near-neutral conditions. As a consequence, Pb is prevented from being released downstream to surface waters, and dissolved Pb concentrations remain definitely below the Italian and WHO limits for drinking waters (50 µg/L and 10 µg/L, respectively).  相似文献   

20.
The relatively stable concentrations of calcium (42.2–122.3 mg/l) and magnesium (48.9–88.1 mg/l) between 2012 and 2013 and their possible weathering paths identified by mass balance models for both soil solutions and stream water from a small salted (regular applications of winter road deicing salt) watershed in New Jersey, USA indicate that the weathering of feldspars and dissolution of carbonates are the primary sources for these cations. However, the relatively stable and lower concentrations of sodium and chloride in soil solutions (19.6–46.1 mg/l for Na and 12.7–88.3 mg/l for Cl) and their fluctuating and higher concentrations in stream water (14.6–103.1 mg/l for Na and 15.2–260.4 mg/l)) from the same watershed during the same period also indicate that road deicing salt is the primary source for sodium and chloride in stream water. Furthermore, positive correlations between calcium and sulfur concentrations (correlation coefficient r = 0.77) and magnesium and sulfur concentrations (r = 0.73) in stream water between 2009 and 2013, as well as positive correlations between sulfur and iron concentrations in soil compositions (r = 0.27), indicate that both the dissolution of gypsum and the oxidation of pyrite into hematite might be the primary sources of sulfate in the watershed. Analyses of water chemistry from the related and much larger Delaware River Watershed (DRW) show that sodium and chloride concentrations have increased steadily (2.7 times for Na and 4.56 times for Cl for 10-year average) due to the regular application of winter deicing salt from 1944 to 2011 for which data are available. The greater increase of stream water chloride concentrations compared with sodium concentrations also results in the steady decline of Na+/Cl− molar ratios from 1.51 to 0.92 for the 10-year average during that time in the DRW and approximately 78% of the chloride in the DRW now being anthropogenic. In addition, the decline of sulfate concentration from 22.08 to 14.59 mg/l (∼34%) for the 10-year average from 1980 to 2011 in the DRW stream water may be attributed to the decline of sulfate levels in atmospheric deposition resulting from enhanced national and state environmental regulations and a shift in local economic activities. There also are more periods of low silica stream water concentrations in the DRW than in the past, perhaps as a result of recent increases in summer stream temperatures combined with an increase of impervious surface area in the region. Warmer stream water might cause the temporary bloom of biota requiring silica, particularly plankton, increasing its uptake from stream water, while an expanded impervious surface area increases the contribution of low-silica runoff water to total stream discharge, thereby lowering the silica concentration in stream water. The combined results of this study illustrate the possible changing anthropogenic factors that can control stream water chemistry in salted watersheds and that these factors need to be taken into account when future water quality regulations and policy are considered.  相似文献   

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