Hydrogeochemistry of arsenic and other inorganic constituents in groundwaters from La Pampa,Argentina

Groundwaters from Quaternary loess aquifers in northern La Pampa Province of central Argentina have significant quality problems due to high concentrations of potentially harmful elements such as As, F, NO₃-N, B, Mo, Se and U and high salinity. The extent of the problems is not well-defined, but is believed to cover large parts of the Argentine Chaco-Pampean Plain, over an area of perhaps 10⁶ km². Groundwaters from La Pampa have a very large range of chemical compositions and spatial variability is considerable over distances of a few km. Dissolved As spans over 4 orders of magnitude (<4–5300 μg l⁻¹) and concentrations of F have a range of 0.03–29 mg l⁻¹, B of 0.5–14 mg l^−l, V of 0.02–5.4 mg l⁻¹, NO₃–N of <0.2–140 mg l⁻¹, Mo of 2.7–990 μg l⁻¹ and U of 6.2–250 μg l⁻¹. Of the groundwaters investigated, 95% exceed 10 μg As l⁻¹ (the WHO guideline value) and 73% exceed 50 μg As l⁻¹ (the Argentine national standard). In addition, 83% exceed the WHO guideline value for F (1.5 mg l⁻¹), 99% for B (0.5 mg l⁻¹), 47% for NO₃-N (11.3 mg l⁻¹), 39% for Mo (70 μg l⁻¹), 32% for Se (10 μg l⁻¹) and 100% for U (2 μg l⁻¹). Total dissolved solids range between 730 and 11400 mg l⁻¹, the high values resulting mainly from evaporation under ambient semi-arid climatic conditions. The groundwaters are universally oxidising with high dissolved-O₂ concentrations. Groundwater pHs are neutral to alkaline (7.0–8.7). Arsenic is present in solution predominantly as As(V). Groundwater As correlates positively with pH, alkalinity (HCO₃), F and V. Weaker correlations are also observed with B, Mo, U and Be. Desorption of these elements from metal oxides, especially Fe and Mn oxides under the high-pH conditions is considered an important control on their mobilisation. Mutual competition between these elements for sorption sites on oxide minerals may also have enhanced their mobility. Weathering of primary silicate minerals and accessory minerals such as apatite in the loess and incorporated volcanic ash may also have contributed a proportion of the dissolved As and other trace elements. Concentrations of As and other anions and oxyanions appear to be particularly high in groundwaters close to low-lying depressions which act as localised groundwater-discharge zones. Concentrations up to 7500 μg l⁻¹ were found in saturated-zone porewaters extracted from a cored borehole adjacent to one such depression. Concentrations are also relatively high where groundwater is abstracted from close to the water table, presumably because this zone is a location of more active weathering reactions. The development of groundwaters with high pH and alkalinity results from silicate and carbonate reactions, facilitated by the arid climatic conditions. These factors, together with the young age of the loess sediments and slow groundwater flow have enabled the accumulation of the high concentrations of As and other elements in solution without significant opportunity for flushing of the aquifer to enable their removal.     

Hydrogeochemistry and isotope analyses used to determine groundwater recharge and flow in low-gradient catchments of the province of Buenos Aires,Argentina

The region known as Pampa Plain, in Argentina, is a vast area characterized by slopes of less than 0.05%. The surface sediment is silty sand, mainly Aeolian, referred to as Pampean Loess, which is a phreatic aquifer unit of utmost importance for the water supply of the region. On account of the slight gradient, hydrogeological analyses using only hydraulic measurements are difficult to perform, often leading to confusing results. Thus, the study presented relies on hydrochemical modeling and isotopic determinations as well. The study area comprises three catchments in the inter-mountainous area corresponding to El Moro, Tamangueyú and Seco creeks, and covering 2,570 km² in the province of Buenos Aires. Measurements of piezometric levels and samples of groundwater, surface water and rainwater were carried out between January and March 2005. Major ion results were analyzed by means of hydrochemical graphs and hydrogeochemical modelling using NETPATH. The resulting data show that it is possible to identify local changes in recharge, flow direction and stream/groundwater relationship by using hydrochemical and isotopic information, which may become a useful and more precise tool for the study of particularly flat landscapes.     

同位素技术释解苏锡常地区浅层地下水水循环机制

本文利用同位素量值及常规指标含量在不同赋存介质下所表现出的规律，垂向上选取河水、潜水、微承压水进行分析，释解苏锡常地区浅层地下水水循环系统运移机制，为合理开发利用苏锡常地区浅层地下水提供理论依据。全区浅层水的补给资源量十分可观，但地域间存有差异，其中东部苏州地区补给量大于西部常州地区，沿江地带大于东部地区。     

Modeling stream-aquifer interactions in a shallow aquifer, Choele Choel Island, Patagonia, Argentina

A groundwater/surface-water interaction model was developed for the shallow alluvial aquifer of the Choele Choel Island in Patagonia, Argentina. In this semiarid climate, agriculture is sustained by an irrigation/drainage system. During the irrigation season, seepage losses through unlined distribution canals in irrigated fields contribute to elevated groundwater levels, jeopardizing fruit productivity in some areas. Moreover, high stream stages during the irrigation season interfere with groundwater drainage. The model utilized MODFLOW and its stream package, and was successfully calibrated for a historical irrigation season. Modeling results indicate that drainage through streams is significantly higher than drainage through artificial drains. The stream/aquifer relationship proved very responsive to water table rises caused by irrigation. This response manifested as changes in the gaining/losing character of stream reaches. A synthetic run aimed at isolating the effect of streamflow changes on groundwater levels showed that the effect of higher streamflows dissipates toward the interior of the island, disappearing completely at the island center. Even though some results were qualitative, the model helped to provide a better understanding of the coupled system to elucidate some of the causes of a rising water table on the island.

Prediction of seasonal water-table fluctuations in La Pampa and Buenos Aires, Argentina

The fluctuation of the water table east of La Pampa province and northwest of Buenos Aires province, Argentina, influences agricultural production in the region because it is closely related to the alternation of dry and wet periods. Sea-surface temperature (SST) anomalies have been used as predictors to forecast atmospheric variables in different regions of the world. The objective of this work is to present a simple model to forecast seasonal rainfall using SST distribution in the Pacific Ocean as a predictor. Once the relationship between precipitation and water-table fluctuations was established, a methodology for the prediction of water-table fluctuations was developed. A good agreement between observed and predicted water-table fluctuations was found when estimating water-table fluctuations in the summer and autumn seasons. Electronic Publication     

Late Quaternary paleosols, stratigraphy and landscape evolution in the Northern Pampa, Argentina

The field properties, micromorphology, grain-size, geochemistry, and optically stimulated luminescence (OSL) ages of two late Quaternary sections have been used to reconstruct the sequence of pedosedimentary processes and to provide insights into landscape evolution in part of the Northern Pampa of Argentina. Paleosols developed in paludal sediments adjacent to the Paraná river at Baradero and in loess at Lozada can both be correlated and linked to other sites, thus enabling for the first time the tentative recognition and tracing of a diachronous soil stratigraphic unit that probably spans the equivalent of at least part of marine oxygen isotope stage (OIS) 5. The paleosol at Lozada was truncated and buried beneath fluvial sediments during the time span of OIS 4 and 3. Eolian gradually replaced paludal inputs at Baradero over this period, and there were also two clearly defined breaks in sedimentation and development of paleosols. The period corresponding to OIS 2 was marked by significant loess accumulation at both sites with accretion continuing into the mid-Holocene only at Lozada. The more developed nature of the surface soil at Baradero probably reflects a combination of a moister climate and a longer soil-forming interval.     

Hydrogeochemistry and water quality assessment of shallow aquifers in the western flanks of Southern Western Ghats,SW India

The present study deals with the hydrogeochemistry and water quality of shallow aquifers in two important river basins—the Ithikkara and Kallada river basins—draining the south western flanks of Western Ghats in Kerala, South West India. Well water samples were collected from 20 dug wells with a depth range of 1 m below ground level (mbgl) to 18.2 mbgl during pre-monsoon, monsoon, and post-monsoon seasons of the year 2011–2012. These samples were analyzed for various physico-chemical parameters following standard methods and were evaluated for their interrelations and drinking water suitability. The pH of the water samples shows wide variation from highly acidic to highly alkaline water. About 80% of pre-monsoon samples recorded Fe²⁺ concentration above the permissible limit of drinking water standard. Water Quality Index (WQI) shows that majority of the well water samples fall in the category of excellent–good for drinking purpose. The results of the irrigation suitability assessment using the procedures like Percent Sodium, Sodium Absorption Ratio, Residual Sodium Carbonate, Kelly Index, Permeability Index, and Magnesium Hazard reveal that the well waters of the study area are fit for irrigation purpose. Na⁺/Cl^? ratio reflects the release of sodium to water due to silicate weathering. The samples have a Ca²⁺/Mg²⁺ ratio equal or greater than 2 indicating the effect of silicate minerals in contributing Ca²⁺ and Mg²⁺ ions to the well water. The saturation indices reveal that groundwater is supersaturated with SiO₂. Among the causative factors that determine the hydrochemical quality of well water samples, silicate weathering plays a pivotal role with significant input of ions from anthropogenic sources.     

Mineral chemistry and chemical zoning in tourmalines, Pampa del Tamboreo, San Luis, Argentina

Tourmalinites that are distally associated with tungsten deposits of the Pampa del Tamboreo area, San Luis, Argentina, contain tourmalines retaining evidence for its origin and evolution. Tourmaline grains uncommonly contain small grains of detrital tourmaline. Analysis of a single detrital tourmaline grain reveals that it is a Ca-rich “oxy-dravite”. Proximal to the detrital cores there are inner domains of asymmetric tourmaline overgrowths that developed during low grade metamorphism. Volumetrically dominant tourmaline overgrowths in the outer domain are concentrically zoned aluminous dravite and “oxy-dravite” with Al/(Al + Fe + Mg) = 0.71–0.74 and Mg/(Mg + Fe) = 0.64–0.71. Variability of Al is primarily controlled by the deprotonation substitution R + OH⁻ = Al + O²⁻ (where R = Fe + Mg), and is a function of the activity of H₂O. A likely evolutionary scenario is one in which volcanogenic material is altered by hydrothermal fluids in the sea floor resulting in an aluminous and magnesian residuum. With further hydrothermal circulation and incipient metamorphism, boron-rich fluids are expelled from metasedimentary and metavolcanic basement rocks and develop Mg-rich tourmalinites in the aluminous, magnesian host rocks. The tourmalinization process occurs over a range of metamorphic conditions and with fluids of variable activity of H₂O.     

Hydrogeochemistry and cation-exchange processes in the coastal aquifer of Mar Del Plata,Argentina

The aquifer of Mar del Plata is unconfined and composed of silt and fine sand. The sand fraction is mainly quartz, potassium feldspars, chalcedony, and gypsum. Volcanic-glass shards (40–60%) dominate the silt fraction, and the clays are of the smectite and illite groups. Calcium carbonate, in caliche form, constitutes about 10–20% of the sediment. Groundwater flow is from west to east, and discharge is in the Atlantic Ocean. Because of overexploitation, the flow direction was reversed in a coastal belt about 3.5 km wide, and this has resulted in seawater intrusion. The groundwater is the CaHCO₃ type in the recharge zone, and becomes NaHCO₃ type towards the discharge area. Salinization by marine intrusion and seawater/fresh-water mixing produces an increase in the major-ion concentrations of the groundwater. The calcium content of the groundwater is higher and the sodium content is lower than those that would be expected if the mixing is considered as just the addition of seawater and fresh water in determined proportions without reactive processes taking place. Hydrogeochemical modeling was applied to the study of hydrogeochemical processes, mainly cation exchange, using the codes NETPATH and PHREEQM. Calcite and gypsum equilibrium, together with cation exchange, are the main hydrogeochemical processes. Cation-exchange capacity of the solid phase was determined by empirical calculations and experimental methods. The affinity order for the groundwater in contact with the aquifer matrix is Ca>Mg>Na in the regional-flow system, but the order is reversed in the salinization process. Reactive transport modeling using the code PHREEQM is useful for analyzing cation exchange in a marine-intrusion process. Electronic Publication     

Comparison of metal(loid) concentrations in water, sediments and fish from two large shallow lakes

Hulun Lake and Taihu Lake are both large shallow lakes in China. In summer and winter of 2009, water, sediments and fish samples were collected from the two lakes and the concentrations of metal(loids) were analyzed. The results demonstrated that aqueous concentrations of arsenic (As), chromium (Cr), cadmium (Cd), nickel (Ni) and copper (Cu) in Hulun Lake were significantly higher than those in Taihu Lake. Especially, the As concentrations (about 130 μg/L) in Hulun Lake dramatically exceeded the permissible level of drinking water. Compared with Taihu Lake, metal(loid) concentrations in the sediments of Hulun Lake were significantly lower, which might have less impacts on the metal exchanges between water and sediments. In contrast, concentrations of the measured metal(loids) (including As) in fish from Hulun Lake and Taihu Lake were comparable, suggesting that the dramatic difference in aqueous and sediment metal(loid) concentrations had less influence on the metal(loid) bioavailability. The higher concentrations of dissolved organic carbon (DOC) and cations (e.g., Na⁺, K⁺ and Mg²⁺) in lake water might contribute to the reduced metal(loid) bioavailability to fish in Hulun Lake.     

Geochemical variations in Cenozoic back-arc basalts at the border of La Pampa and Mendoza provinces,Argentina

Back-arc volcanism was active in central-western Argentina (provinces of Mendoza and La Pampa) from the Miocene through historic times. The rocks of 39 monogenetic volcanoes located in this area were studied in order to define their geochemical characteristics. The dominant rock texture is porphyritic, with intergranular, pilotaxitic and hyalophitic groundmasses. The most frequent phenocrysts are olivine followed by olivine–plagioclase–clinopyroxene. Their SiO₂ content varies between 42.3 and 51.2 wt.%, the most abundant rocks are trachybasalts, followed by basalts and basanites, all of them alkaline. The rocks display enrichment of incompatible elements that varies according to the geographic location and age. There is an increase in incompatible element concentrations from the southern and central to the northern zones. Also, in the northern part of the study area, the behavior of incompatible elements varies with time; the incompatible element ratios of the Plio–Pleistocene rocks show arc signature, while the rocks of the Miocene De la Laguna volcano show intraplate affinity. We conclude for this sector that the mantle source region was modified after the generation of Miocene magmas by subduction-related fluids. These fluids are related to a late Miocene episode of subhorizontal subduction, i.e., after the generation of the rocks of De la Laguna volcano.     

Surface and groundwater pollution by organochlorine compounds in a typical soybean system from the south Pampa,Argentina

Organochlorine pesticides (OCPs) use has been restricted or forbidden in Argentina since 1998 and technical endosulfan is the last currently used OCPs on the soybean-wheat production. As they persist in soil for several years after application, OCPs constitute a source of environmental pollution. This work aims to assess OCPs contamination of groundwater (Gw) and streamwater (Sw) in the Quequén Grande River watershed from south Argentinean Pampas in relation to the hydrogeological characteristics. OCPs were analyzed in Sw, Gw, surface bottom sediments, soils and borehole cutting sediments (Cs) by gas chromatograph-electron capture detector. Pesticide distribution in Cs was dependent on the characteristic of the non-saturated zone. Leached pesticides over 3 m in Cs showed the pattern: HCHs = endosulfan > chlordanes > DDTs, and from 3 to 6 m heptachlor was the main group as a consequence of the past use of this compound in the area, mainly on potato crops. Endosulfan reaches Gw during application season as well as during flooding events while a retard effect was observed for Sw. Levels of α- and β-isomers were in certain cases above national (7 ng L⁻¹) and international (3 ng L⁻¹) limits for aquatic biota protection. As the endosulfan sulfate metabolite was present in Gw and Sw and due to its high toxicity, it should be considered in the establishment of water quality criteria for human and environmental protection.     

基于氢氧同位素的华北平原降水入渗过程

华北平原地下水浅埋区水循环主要以垂直方向上的入渗、蒸发和蒸腾的方式存在,同位素可以作为一种有效"示踪剂"揭示降水入渗补给地下水的过程。选择华北平原中、东部地下水浅埋区的衡水和沧州为典型实验点,研究不同降水特征、土壤质地和植被条件下入渗过程的差异性。结果表明,土壤非均质条件下(沧州),降水入渗补给过程中伴随着蒸发、植被蒸腾作用以及与土壤前期水分的强烈混合作用,活塞流入渗的同时土壤100 cm深度可能还存在大孔隙优先流;土壤均质条件下(衡水),降水向下均匀入渗,入渗速度较快,土壤水运动以新水基本代替老水的活塞流为主要形式,并经过强烈的蒸发浓缩作用补给地下水。     

Identifying interactions between river water and groundwater in the North China Plain using multiple tracers

Interactions between river water and groundwater have been used to help understand the movement of water and to evaluate water quality in the semi-arid area of the North China Plain (NCP). Stable isotopes, chlorofluorocarbons (CFCs) and hydrochemistry were used to study the influence of surface water from the Xiao River on regional groundwater. Using a mass balance approach based on chloride concentrations, hydrogen and oxygen isotope ratios, the average fraction of surface water recharging to groundwater was 50–60 %. CFC results indicated that the groundwater recharge age varied from 22.5 to 39.5 years. The vertical flow velocity of groundwater was estimated at about 1.8–3.5 m year^?1. Nitrate concentrations in groundwater varied from 9.42 to 156.62 mg L^?1, and exceeded 50 mg L^?1 in most aquifers shallower than 80 m bordering the Xiao River. The δ ¹⁵N-NO₃ data indicate that the major sources of nitrogen in groundwater are human sewage and animal excreta. Because groundwater is the main source of drinking water, there should be concern about public health related to the elevated nitrate concentrations in the NCP.     

Silicate oxygen isotope geochemistry: History,principles, techniques,and application to petrological problems

The importance of oxygen isotope geochemistry in studies of terrestrial and extra-terrestrial silicate rocks was recognized nearly sixtyeight years ago soon after the discovery of O¹⁸ and O¹⁷. As early as 1934, the significance of oxygen isotope variations in rocks and minerals was stressed by Russian geochemists who also pioneered the discipline of silicate oxygen isotope geochemistry. It is now known that processes involving isotopic interaction between rock and water, magmatic differentiation, and metamorphic recrystallization fractionate oxygen isotopes in the lithosphere. δO¹⁸ (the conventional notation for reporting O¹⁸/O¹⁶ ratios in rocks and minerals) is highest in sedimentary rocks (17 to 35 ‰) and lowest in igneous rocks (4 to 12‰). Metamorphic rocks have intermediate values. δO¹⁸ in mafic minerals (1 to 8‰) is lower than in felsic minerals (8 to 16‰). In igneous and metamorphic rocks, quartz is most enriched in O¹⁸ (10 to 16‰) and magnetite the least (1 to 2‰). An important application of O¹⁸/O¹⁶ techniques is in geothermometry, where these are capable of elucidating several petrological processes.     

Modelling the response of shallow groundwater levels to combined climate and water-diversion scenarios in Beijing-Tianjin-Hebei Plain,China

A three-dimensional groundwater flow model was implemented to quantify the temporal variation of shallow groundwater levels in response to combined climate and water-diversion scenarios over the next 40 years (2011–2050) in Beijing-Tianjin-Hebei (Jing-Jin-Ji) Plain, China. Groundwater plays a key role in the water supply, but the Jing-Jin-Ji Plain is facing a water crisis. Groundwater levels have declined continuously over the last five decades (1961–2010) due to extensive pumping and climate change, which has resulted in decreased recharge. The implementation of the South-to-North Water Diversion Project (SNWDP) will provide an opportunity to restore the groundwater resources. The response of groundwater levels to combined climate and water-diversion scenarios has been quantified using a groundwater flow model. The impacts of climate change were based on the World Climate Research Programme’s (WCRP’s) Coupled Model Intercomparison Project phase 3 (CMIP3) multi-model dataset for future high (A2), medium (A1B), and low (B1) greenhouse gas scenarios; precipitation data from CMIP3 were applied in the model. The results show that climate change will slow the rate of decrease of the shallow groundwater levels under three climate-change scenarios over the next 40 years compared to the baseline scenario; however, the shallow groundwater levels will rise significantly (maximum of 6.71 m) when considering scenarios that combine climate change and restrictions on groundwater exploitation. Restrictions on groundwater exploitation for water resource management are imperative to control the decline of levels in the Jing-Jin-Ji area.