Geochemical zones and reconstruction of late Holocene environments from shallow core sediments of the Pachapadra paleo-lake, Thar Desert, India

Lithostratigraphy, mineralogy, major and trace element concentrations, carbon and sulphur contents are investigated from a shallow depth profile from Pachapadra paleo-lake, Thar Desert, north-western India, to understand the phases of paleo-hydrology and paleo-limnology. Based on the geochemical proxies (Na/Al, Si/Al, Zr/Al and Ca/Mg) and evaporite mineralogy, the depth profile is divided into three geochemical zones of variable sediment-water interaction, evaporation and aeolian activity. The sub-recent zone (I) enriched in halite (NaCl) indicates low chemical weathering and higher aeolian input. The intermediate relatively humid zone II is enriched in major elements, trace elements and calcite (CaCO₃) and reflects higher chemical weathering in the catchments. Zone III is enriched in gypsum (CaSO₄·2H₂O) and characterised by lower chemical weathering, higher aeolian activity and evaporation.     

Redox-driven changes in porewater chemistry in the unsaturated zone of the chalk aquifer beneath unlined cattle slurry lagoons

Farm waste stores such as cattle slurry lagoons are widespread in the UK and many overly important aquifers. Stores can be serious risks to water quality because they are important sources of N species, organic C and pathogenic microbes. At two sites on the Chalk aquifer of southern England, inclined boreholes were drilled and cored to obtain aquifer material from directly beneath unlined slurry stores. Vertical boreholes were also drilled adjacent to the slurry stores to determine any lateral movement of contaminants. Interstitial porewaters were analysed for major and minor ions and S isotopes. At the second site, unsaturated zone gases were sampled from the inclined hole. Infiltration of slurry into the unsaturated zone caused significantly elevated concentrations of metals such as Cu and Ni at both sites. Sulphate reduction was occurring at Site 1, as evidenced by SO₄ concentrations decreasing from 150 to 50 mg/l and enhanced ratios of δ³⁴S–SO₄ and δ¹⁸O–SO₄. Ammonium-N also leaches along with dissolved organic C which were found 17 m below ground surface at concentrations up to 400 and 260 mg/l, respectively. Contaminant concentrations were similar in the porewaters from both the inclined and vertical boreholes. At Site 2, higher contaminant concentrations were found in the inclined borehole compared with the vertical borehole. Organic C concentrations were considerably lower than at Site 1, ranging from 10 to 70 mg/l. Ammonium–N concentrations reached a maximum concentration of 25 mg/l, however NO₃-N concentrations were up to 500 mg/l and SO₄ concentrations were generally higher than Site 1. Data for N₂/Ar and δ¹⁵N–N₂ from the gas samplers show a peak of 102 and 2.2‰, respectively, at 14 m below ground level indicating denitrification was taking place. Evidence from δ³⁴S–SO₄ and δ¹⁸O–SO₄ suggest that some SO₄ reduction was taking place simultaneously. From CH₄ and NH₃ detected at depth it is suggested that slurry contamination, emanating from early use of the store, has passed through the top 18 m of the unsaturated zone at Site 2. The presence of high concentrations of NO₃ and lower concentrations of organic C suggests that this lagoon has formed a relatively impermeable seal at its base within the first few years of its lifetime. The anoxic conditions at both sites may have mobilised U from N–P–K fertilisers. Both sites are continuing to impact on the porewater chemistry and pose a risk of groundwater contamination.     

Interpretation of undisturbed hydrogeochemical conditions in Neogene sediments of the Horonobe area, Hokkaido, Japan

Empirical, geostatistical and geochemical modeling techniques were used to determine whether chemical, isotopic and mineralogical data collected in surface-based borehole investigations at the Horonobe Underground Research Laboratory (URL) site in Hokkaido, Japan were representative of the natural environment before it was disturbed by borehole drilling, hydraulic testing and sampling. Water samples collected either by pumping groundwaters to the surface from borehole sections that had been isolated by inflatable packers or by squeezing porewaters from drillcores sampled from the same borehole and sampling depth were found to be similar in certain respects (m_Na+, m_Cl−, δ¹⁸O and δD) but not others (m_SO42−, m_Ca2+, m_Mg2+ and m_K+). The inconsistencies suggest that a majority of the porewater samples were contaminated as a result of pyrite oxidation and dissolution of carbonate minerals during sampling, storage and/or squeezing of the drillcores. Multivariate geostatistical analyses support this hypothesis, and further suggest that uncontaminated porewaters and groundwaters can be divided into three representative groups: a low salinity, low δ¹⁸O and low δD group; a moderate salinity, low Ca-Mg group; and a high salinity, high K and moderate Ca-Mg group. The groundwaters also contain high concentrations of dissolved gases, including CH₄(g), CO₂(g), H₂S(g) and various hydrocarbons, which exsolve from the groundwaters as they are pumped to the surface for sampling. The effects of such degassing on the chemistry of groundwater samples was evaluated by using a reaction-path model to simulate the titration of gases collected at the surface back into the samples. Results suggest that undisturbed groundwaters are slightly more acidic than their sampled counterparts, and contain roughly equivalent activities of dissolved CH₄(aq) and carbonate species. Redox potentials calculated using the corrected groundwater compositions and assuming equilibrium for the CH₄(aq)/CO₂(aq) redox couple are significantly more negative than those determined in situ in one borehole using a downhole chemical probe, and those that can be inferred from the ubiquitous presence of small amounts of framboidal pyrite and siderite in siliceous biogenic sediments of the Horonobe area. The empirical, geostatistical and geochemical modeling techniques considered in this study can be adapted for use in characterizing the hydrogeochemical environment of a site that will eventually be selected to host a geologic repository for high-level nuclear waste in Japan.     

State of rare earth elements in the rare earth deposits of Northwest Guizhou,China

We studied the states of rare earth elements in ore of the Xianglushan rare earth deposit. Rare earth ore samples were tested and examined by scanning electron microscope, electron probe, and chemical leaching. No independent rare earth minerals were detected by scanning electron microscope. Elements detected by the electronic probe for the in situ micro-zone of the sample included: O, Al, Si, Ca, Mg, Fe, Ti, K, Na, S, Cl, C, Cu, Cr, V, and Pt. Rare earth elements were not detected by electron probe. (NH4)₂SO₄, (NH₄)Cl, NaCl, and H₂SO₄ were used as reagents in chemical leaching experiments that easily leached out rare earth elements under the action of 10% reagent, indicating that the rare earth elements in ore are mainly in the ionic state rather than present as rare earth minerals.     

Chemistry of rainwater in the Massif Central (France): a strontium isotope and major element study

Atmospheric aerosols (sea salt, crustal dust, and biogenic aerosols) are the primary source of dissolved species in rainwater as well as one of the sources of dissolved species in river water. Chemical weathering studies require quantification of this atmospheric input. The crustal component of atmospheric input can have various origins, both distant and local. The proportions of the various inputs (marine, distant or local) are determined in this study.Strontium isotope ratios and Ca, Na, K, Mg, Al, Cl, SO₄, NO₃ and Sr concentrations were measured in rainwater samples collected in the Massif Central (France) over a period of one year. Each sample, collected automatically, represents a monthly series of rain events. Chemical composition of the rainwater samples varied considerably and the ⁸⁷Sr/⁸⁶Sr ratios ranged between 0.709198 and 0.713143.Using Na as an indicator of marine origin, and Al for the crustal input in rain samples, the proportion of marine and crustal elements was estimated from elemental ratios. A marine origin of 4 to 100% of Cl, of 0.6 to 20% of the SO₄, of <1 to 10% of Ca, <1 to 40% of K, 4 to 100% of Mg and 1 to 44% of Sr was determined.Strontium isotopes were used to characterize the crustal sources. The ⁸⁷Sr/⁸⁶Sr ratios of the crustal sources varied considerably from 0.7092 to 0.71625 and indicate the occurrence of multiple sources for the crustal component in the analysed rainwaters.     

Genetic geochemical model for mining affected groundwaters of the Lusatian post-mining district

Using groundwater quality data from the Lusatian post-mining district a hydrogeochemical model is derived for the evolution of mining affected groundwaters in pyrite-rich dumps which consist mainly of silicates and variable amounts of calcite. Pyrite oxidation paralleled by buffer processes leads to gypsum saturation in a significant portion of the water. Gypsum precipitation controls SO₄ and Ca concentrations in groundwaters above an ionic strength (I) of 60 mM. It has been found that there is always a clear relationship between I, SO₄ and Ca concentrations. In particular, there is a tendency that Ca concentrations decrease with increase in ionic strength above I = 60 mM and a striking rareness of samples with SO₄ concentrations between 20 and 30 mM above an ionic strength of 100 mM. These observations are explained by a genetic model. This model also explains the observed relationship between the c(Fe)/c(SO₄)-ratio, the ionic strength, and the observed pH-values. Based on the field data and supported by geochemical equilibrium calculations, it is shown that silicate weathering along with calcite dissolution must be a significant buffering process at least in some areas.     

Lake water geochemistry on the western Kola Peninsula,north-west Russia

Water samples were taken from 120 lakes spread over the western half of the Kola Peninsula, NW Russia. The samples were analysed for 37 elements, pH and electrical conductivity. Lake water chemistry appears in most cases to be dominated by a Ca/Na–HCO₃ signature, characteristic of natural carbonate/silicate weathering. Input of elements from marine derived salts and from the Ni industry (roasting plant at Zapoljarnij, smelter at Nikel and smelter/refinery at Monchegorsk) emissions are restricted to limited regions. Considering that 3 of the world's largest point source emitters of SO₂ are located within the area, the median lake water pH is surprisingly close to neutral (6.6, range 4.2–7.4). Indeed some of the apparently SO₄ contaminated lakes nearest to the smelters yield the highest pH values. Changes in climate and vegetation from north to south within the survey area probably have an influence on element concentrations and pH as observed in the lake waters. Proton displacement by sea salt cation input provides an explanation of low pH lakes in coastal areas.     

Identification of major sources controlling groundwater chemistry from a hard rock terrain — A case study from Mettur taluk,Salem district,Tamil Nadu,India

The study area Mettur forms an important industrial town situated NW of Salem district. The geology of the area is mainly composed of Archean crystalline metamorphic complexes. To identify the major process activated for controlling the groundwater chemistry an attempt has been made by collecting a total of 46 groundwater samples for two different seasons, viz., pre-monsoon and post-monsoon. The groundwater chemistry is dominated by silicate weathering and (Na + Mg) and (Cl + SO₄) accounts of about 90% of cations and anions. The contribution of (Ca + Mg) and (Na + K) to total cations and HCO₃ indicates the domination of silicate weathering as major sources for cations. The plot for Na to Cl indicates higher Cl in both seasons, derived from Anthropogenic (human) sources from fertilizer, road salt, human and animal waste, and industrial applications, minor representations of Na also indicates source from weathering of silicate-bearing minerals. The plot for Na/Cl to EC indicates Na released from silicate weathering process which is also supported by higher HCO₃ values in both the seasons. Ion exchange process is also activated in the study area which is indicated by shifting to right in plot for Ca + Mg to SO₄ + HCO₃. The plot of Na-Cl to Ca + Mg-HCO₃-SO₄ confirms that Ca, Mg and Na concentrations in groundwater are derived from aquifer materials. Thermodynamic plot indicates that groundwater is in equilibrium with kaolinite, muscovite and chlorite minerals. Saturation index of silicate and carbonate minerals indicate oversaturation during pre-monsoon and undersaturation during post-monsoon, conforming dissolution and dilution process. In general, water chemistry is guided by complex weathering process, ion exchange along with influence of Cl ions from anthropogenic impact.     

Deep groundwater in the crystalline basement of the Black Forest region

Two major types of groundwater can be readily distinguished in the Variscian crystalline basement of the Black Forest in S–W Germany. Saline thermal water utilized in spas has its origin in 3–4 km deep reservoirs and developed its composition by 3 component mixing of surface freshwater, saltwater (of ultimately marine origin) and a water–rock reaction component. In contrast to the thermal water, CO₂-rich mineral water, tapped and bottled from many wells in the Black Forest, has low salinities but a TDS distribution similar to that of thermal water. It developed its chemical composition entirely by reaction of CO₂-rich water with the gneissic or granitic aquifer rock matrix. Particularly important is the contribution of various plagioclase dissolution and weathering reactions that may, at some locations, involve precipitation and dissolution of secondary calcite. Sodium/Ca ratios of water and of rock forming plagioclase in the basement rocks suggests that plagioclase weathering is strongly incongruent. Calcium is released to the water, whereas Na remains fixed to the albite feldspar component.The major element composition of 192 water samples used in this study also indicates a clear vertical stratification of the type of water chemistry; Ca–HCO₃ near the surface, Na–Ca–HCO₃–SO₄ at intermediate depth and Na–Ca–Cl at great depth.The mean permeability of Black Forest granite is about K=10⁻⁶ m/s; it is significantly lower in gneisses (gneiss: mean K=5×10⁻⁸ m/s) leading to focused flow through granite. Highly permeable fracture and fault zones, particularly in granite, are utilized by high-TDS saline deep groundwater as ascent channels and flow paths. Although spatially closely associated, the topography driven upwelling system of saline deep water and the near-surface flow system of CO₂-rich mineral waters are hydraulically and chemically unconnected.     

Mineralogical and geochemical characteristics of coal ash from the Northwest Thrace region,Turkey: a case study

The first combined mineralogical and geochemical investigation of coal ashes from the Northwest Thrace Coal Basin, Turkey, was performed as a case study. The coal ash samples were obtained at 525 °C (group I), 750 °C (group II), and 1000 °C (group III) ashing temperatures from coal samples from the basin and were studied in terms of their mineralogical and geochemical composition using XRD and ICP-MS methods. The determination of the mineralogical composition was done for all of the groups; the geochemical analysis was carried out only for group II. In accordance with the high SiO₂, Fe₂O₃, CaO, and SO₃ content of the ash, quartz (SiO₂), hematite (Fe₂O₃), and anhydrite (CaSO₄) are the major crystalline phases for all of the ash groups. The other minerals are muscovite, thenardite, tridymite, calcite, wollastonite, anorthite, cristobalite, gibbsite, ternesite, mullite, nahcolite, and nacrite. High-temperature phases such as mullite, wollastonite, and anorthite were observed at 750 and 1000 °C. According to the (Fe₂O₃ + CaO + MgO+ K₂O+ Na₂O)/(SiO₂ + Al₂O₃+ TiO₂) ratios varying from 0.19 to 5.65, the ashes are highly prone to slagging. Compared to average values of low-rank coal ashes, the contents of V, Cr, Co, Ni, Zn, As, Rb, Sr, Mo, Cs, W, and U of the ash are higher, whereas the total content of rare earth elements (REEs) (Σ 163.7 ppm) are lower. Based on upper continental crust normalization, As, Se, Th, and U are enriched in all of the samples. The higher trace element contents in the ashes might be considered as a possible health hazard. The correlation analyses indicated that Ca is associated with anhydrite and As with hematite. The correlation analyses also showed that newly formed Al and Ca silicates may contain the elements such as Ti, K, Na, Cr, Sn, and Pb.     

Multivariate statistics and hydrogeochemical modeling for source identification of major elements and heavy metals in the groundwater of Qareh-Ziaeddin plain,NW Iran

The present study aims to evaluate the possible source of major and some minor elements and heavy metals in the groundwater of Qareh-Ziaeddin plain, NW Iran with respect to chemical elements, saturation index, and multivariate statistics including correlation coefficient, cluster analysis, and factor analysis. Groundwater samples were collected in Jun 2016 and measured with respect to EC, pH, major and some minor elements and heavy metals including Fe, Mn, Zn, Cr, Pb, Cd, Al, and As. Among all the measured parameters, some of the samples exceed the World Health Organization (WHO) guideline value for EC, Na, Mg, HCO₃, SO₄, Cl, NO₃, F, As, Zn, and Pb. The results of correlation analysis show that weathering and dissolution of minerals especially evaporites and silicates, water-rock interaction, and cation exchange are dominant occurred processes in the groundwater of the study area. Also, denitrification process is occurred in the groundwater system. Cluster analysis categorizes the samples into three distinct groups which are different based on their EC and dependent variables, e.g., Na, Ca, Cl, SO₄ and pH, Pb, Cd, and As. It can be found that volcanic, evaporite, and clay formations have the least impact on the chemistry of the cluster 1 samples while clay and evaporite formations have the highest impact on the cluster 3 and also calcareous formations on cluster 2. Factor analysis shows that five factors, with total variance of 83%, are effective in the release of heavy metals and groundwater chemistry which are mostly geogenic.     

Arsenic associations in sediments from the loess aquifer of La Pampa,Argentina

Groundwater from the Quaternary loess aquifer of La Pampa, central Argentina, has significant problems with high concentrations of As (up to 5300 μg L⁻¹) as well as other potentially toxic trace elements such as F, B, Mo, U, Se and V. Total As concentrations in 45 loess samples collected from the aquifer have a range of 3–18 mg kg⁻¹ with a mean of 8 mg kg⁻¹. These values are comparable to world-average sediment As concentrations. Five samples of rhyolitic ash from the area have As concentrations of 7–12 mg kg⁻¹. Chemical analysis included loess sediments and extracted porewaters from two specially cored boreholes. Results reveal a large range of porewater As concentrations, being generally higher in the horizons with highest sediment As concentrations. The displaced porewaters have As concentrations ranging up to 7500 μg L⁻¹ as well as exceptionally high concentrations of some other oxyanion species, including V up to 12 mg L⁻¹. The highest concentrations are found in a borehole located in a topographic depression, which is a zone of likely groundwater discharge and enhanced residence time. Comparison of sediment and porewater data does not reveal unequivocally the sources of the As, but selective extract data (acid-ammonium oxalate and hydroxylamine hydrochloride) suggest that much of the As (and V) is associated with Fe oxides. Primary oxides such as magnetite and ilmenite may be partial sources but given the weathered nature of many of the sediments, secondary oxide minerals are probably more important. Extract compositions also suggest that Mn oxide may be an As source. The groundwaters of the region are oxidising, with dissolved O₂, NO₃ and SO₄ normally present and As(V) usually the dominant dissolved As species. Under such conditions, the solubility of Fe and Mn oxides is low and As mobilisation is strongly controlled by sorption–desorption reactions. Desorption may be facilitated by the relatively high-pH conditions of the groundwaters in the region (7.0–8.8) and high concentrations of potential competitors (e.g. V, P, HCO₃). PHREEQC modelling suggests that the presence of V at the concentrations observed in the Pampean porewaters can suppress the sorption of As to hydrous Fe(III) oxide (HFO) by up to an order of magnitude. Bicarbonate had a comparatively small competitive effect. Oxalate extract concentrations have been used to provide an upper estimate of the amount of labile As in the sediments. A near-linear correlation between oxalate-extractable and porewater As in one of the cored boreholes investigated has been used to estimate an approximate K_d value for the sediments of 0.94 L kg⁻¹. This low value indicates that the sediments have an unusually low affinity for As.     

Temporal trends of dissolved weathering products released from a high Arctic coal mine waste rock pile in Svalbard (78°N)

It is well known that oxidation of sulphide-containing coal mine waste has considerable environmental impacts due to generation of acid mine drainage (AMD) containing high dissolved metal concentrations. This study is the first to evaluate seasonal trends in the release of AMD from high arctic coal mine waste rock. Runoff from an abandoned coal mine waste pile in Svalbard (78°N) was studied during the entire 3–4 month period with running water in 2005. Temporal variation in concentrations and fluxes of dissolved elements were quantified based on daily water sampling and used to evaluate weathering processes and estimate element budgets on a daily, seasonal and annual basis. Apart from alkali- and alkaline earth metals; Fe, Al, Mn, Zn and Ni were found to be the most abundant metals in the runoff. Element concentrations were highly correlated and suggest that the processes of sulphide oxidation, ion exchange and silicate weathering occurring within the waste pile were linked throughout the measuring period. Observed pH values varied from 2.8 to 5.2 and SO₄ concentrations from 21 to 1463 mg L⁻¹. Manganese and Al concentrations were observed above phytotoxic levels (up to 4 and 23 mg L⁻¹, respectively) and were considered the most critical elements in terms of environmental impact. Throughout the summer a total dissolved quantity of 58 kg Mn, 238 kg Al and 13,700 kg SO₄ was released from the pile containing approximately 200,000 m³ of pyritic waste material (<1% FeS₂). The highest concentrations of metals, lowest pH values and a very high daily release of H₂SO₄ (up to twice as high as the following month) were observed during the first week of thaw. This is considered a result of an accumulation of weathering products, generated within the waste pile during winter and released as a pollution-flush during early spring. Similar accumulation/flush sequences were observed later in the summer where rain events following relatively long dry periods caused high daily metal fluxes and on some occasions also elevated dissolved metal concentrations. Despite highly variable weather/climate conditions during the rest of the summer the investigated waste rock pile acted like a relative constant pollution-source during this period. Future investigations regarding the environmental impact of mine waste in the region should include measurements of bioavailable metals in order to provide further details on the seasonal trends in environmental impact.     

Long-term brine impacted fly ash,Part II: Mobility of major species in the ash residues

The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO₄ leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.     

Effect of agricultural land use on the chemistry of groundwater from basaltic aquifers, Jeju Island, South Korea

Geochemical processes were identified as controlling factors of groundwater chemistry, including chemical weathering, salinization from seawater and dry sea-salt deposition, nitrate contamination, and rainfall recharge. These geochemical processes were identified using principal component analysis of major element chemistry of groundwater from basaltic aquifers in Jeju Island, South Korea, a volcanic island with intense agricultural activities. The contribution of the geochemical processes to groundwater chemistry was quantified by a simple mass-balance approach. The geochemical effects due to seawater were considered based on Cl contributions, whereas the effects due to natural chemical weathering were based on alkalinity. Nitrogenous fertilizers, and especially the associated nitrification processes, appear to significantly affect groundwater chemistry. A strong correlation was observed between Na, Mg, Ca, SO₄ and Cl, and nitrate concentrations in groundwater. Correspondingly, the total major cations, Cl, and SO₄ in groundwater were assessed to estimate relative effect of N-fertilizer use on groundwater chemistry. Cl originates more from nitrate sources than from seawater, whereas SO₄ originates mostly from rainwater. N-fertilizer use has shown the greatest effect on groundwater chemistry, particularly when nitrate concentrations exceed 6–7 mg/L NO₃–N. Nitrate contamination significantly affects groundwater quality and 18% of groundwater samples have contamination-dominated chemistry.     

Tracing ionic sources and geochemical evolution of groundwater in the Intermountain Una basin in outer NW Himalaya,Himachal Pradesh,India

The present research aims to identify sources of ions and factors controlling the geochemical evolution of groundwater in an intermountain basin, comprising hill and valley fill region, of Outer Himalaya in Himachal Pradesh, India. The groundwater samples collected from 81 tubewells and handpumps are analyzed for major ions, trace metals and stable isotopes (δ¹⁸O and δD). Geochemically the dominant hydrochemical facies in the Una basin are Ca–HCO₃, Ca–Mg–HCO₃ and Na–Cl types at few locations. A relatively lower ionic concentration in the valley fills indicates dilution and low residence time of water to interact with the aquifer mass due to high porosity and permeability. The ionic ratios of 0.9, 0.8 and 3.8 to 5.7, respectively, for (Ca?+?Mg): HCO₃, (Ca?+?Mg): (HCO₃?+?SO₄) and Na: Cl, suggests that ionic composition of groundwater is mainly controlled by rock weathering of, particularly by dissolution/precipitation of calcrete and calcite hosted in rock veins and Ca–Na feldspar hosted in conglomerate deposits derived from the Higher and Lesser Himalaya during the formation of Siwalik rocks. Although Na, K, NO₃ and SO₄ are introduced in the groundwater through agricultural practices, Na has also been introduced through ion exchange processes that have occurred during water–rock interaction, as indicated by negative CAI values. Factor analysis further suggests three major factors affecting the water chemistry of the area. The first two factors are associated with rock weathering while the third is anthropogenic processes associated with high nitrate and iron concentration. High concentrations of Fe and Mn ions that are exceeded that of WHO and BIS standards are also present at few locations. The recharge of groundwater in the Outer Himalaya is entirely through Indian Southwest Monsoon (ISM) and depleted ratios of δ¹⁸O/δD in valley region indicate infiltration from irrigation in recharging the groundwater and fractionation of isotopes of precipitation due to evaporation before infiltration. High d-excess values and inverse relation with δ¹⁸O are indicative of secondary evaporation of precipitation during recharge of groundwater.     

Hydrogeochemical assessment of surface and groundwater resources of Korba coalfield,Central India: environmental implications

The present study assesses the impact of coal mining on surface and groundwater resources of Korba Coalfield, Central India. Accordingly, water samples collected from various sources are analyzed for major ions, trace elements, and other mine effluent parameters. Results show that the groundwater samples are slightly acidic, whereas river water and mine water samples are mildly alkaline. Elevated concentrations of Ca²⁺, Na⁺, HCO₃ ^?, and SO₄ ^2? alongside the molar ratios (Ca²⁺+Mg²⁺)/(SO₄ ^2?+HCO₃ ^?) <1 and Na⁺/Cl^? >1 suggest that silicate weathering (water-rock interaction) coupled with ion exchange are dominant solute acquisition processes controlling the chemistry of groundwater in the study area. The overall hydrogeochemistry of the area is dominated by two major hydrogeochemical facies (i.e., Ca–Cl–SO₄ and Ca–HCO₃). Analysis of groundwater and river water quality index (GRWQI) elucidates that majority (82%) of samples are of “excellent” to “good” category, and the remaining 12% are of “poor” quality. Similarly, the effluent water quality index (EWQI) indicates that 6 out of 8 samples belong to excellent quality. Concentration of trace element constituents such as As, Zn, Cu, Cr, and Cd is found to be well within the stipulated limits for potable use, except for Fe, Mn, and Pb. Suitability of water samples for irrigation purpose, established using standard tools like Wilcox and USSL diagrams, reveal “excellent to permissible” category for majority of the samples. The present study also substantiates the effectiveness of the measures implemented for the treatment of mine effluent water.     

Francolite geochemistry—compositional controls during formation,diagenesis, metamorphism and weathering

Francolite in unaltered Tertiary phosphorites is highly substituted with about 1.2% Na, 0.25% Sr, 0.36% Mg and 2.7% SO₄ within the structure in substitution for Ca and PO₄. These substitutions reflect the composition of the solution from which francolite forms and are not influenced by the mechanism, rate or redox conditions of formation. The remarkably constant composition for a wide range of samples reflects the relative constant composition of sea water, during Tertiary times. Francolite in sulphate-reducing sediments forms in an uppermost zone where bioturbation maintains the concentrations of Na, Sr, Mg and SO₄ at sea water concentrations. The structura-CO₂ content of unaltered francolites vary from 1.4% to 6.3%, in response to variations in pH. The maximum level of carbonate substitution is limited by the disruption of the francolite structure at levels above 6.3% CO₂. For the samples considered here F/P₂O₅ ratios vary with X-ray CO₂ contents showing that PO₄^3? is replaced by (CO₃^2? + F?) and not by CO₃^2? alone. In Phosphoria Formation francolite the Na/P₂O₅ ratios and X-ray CO₂ contents show areal trends related to burial depth and thermal metamorphism. These two processes together with weathering and fresh water diageneses explain all observed variation in francolite composition.     

Geochemical characteristics of water and sediment from the Dal Lake, Kashmir Himalaya: constraints on weathering and anthropogenic activity

Two hundred and forty water samples (in four seasons) and seventeen sediment samples have been analyzed to monitor the natural and anthropogenic influences on the water and sediment chemistry of the Dal Lake, Kashmir Himalaya. The scatter diagrams [(Ca+Mg)/total cations (TZ⁺), (Ca+Mg)/HCO₃, (Ca+Mg)/(HCO₃₊SO₄), (Na+K)/TZ⁺; (Ca+Mg)/(Na+K)] and the geological map of the study area suggest predominance of carbonate and silicate weathering. Lower pH and high total dissolved solids, electrical conductivity and values in the Gagribal basin and in some patches of other basins reflect anthropogenic inputs in the form of sewage from surrounding population, houseboats, hotels, etc. The Dal Lake is characterized by high chemical index of alteration (CIA: 87–95), reflecting extreme weathering of the catchment area. Relative to the average carbonates, the lakebed sediments are enriched in Al, Ti, Zn, Cu and Co and depleted in Ni and Mn. Compared to the post-Archean Shale the sediments have higher Al, Zn and Cu contents and lower Ni and Co. There are distinct positive anomalies of Al, Mn, Zn and Cu and negative anomalies of Ni and Pb with respect to the upper continental crust. Geoaccumulation index (I _geo) and the US Environmental Protection Agency sediment quality standards indicate that the Gagribal basin and some patches of the Nagin basin are polluted with respect to Zn, Cu and Pb. These data suggest that the Dal Lake is characterized by differential natural and anthropogenic influences.     

The effect of organic matter on chemical weathering: study of a small tropical watershed: nsimi-zoétélé site,cameroon

The effect of organic matter during soil/water interaction is still a debated issue on the controls of chemical weathering in a tropical environment. In order to study this effect in detail, we focused on the weathering processes occurring in a small tropical watershed (Nsimi-Zoetélé, South Cameroon). This site offers an unique opportunity to study weathering mechanisms in a lateritic system within a small basin by coupling soil and water chemistry.The lateritic cover in this site can reach up to 40 m in depth and show two pedological distinct zones: unsaturated slope soils on the hills and/or elevated areas; and water-saturated soils in the swamp zone which represent 20% of the basin surface. The study present chemical analysis performed on water samples collected monthly from different localities between 1994–1997 and on soil samples taken during a well drilling in December 1997. The results suggest the existence of chemical and spatial heterogeneities of waters in the basin: colored waters flooding the swamp zone have much higher concentrations of both organic matter (i.e., DOC) and inorganic ions (e.g., Ca, Mg, Al, Fe, Th, Zr) than those from springs and groundwater from the hills. Nevertheless, these organic-rich waters present cation concentrations (Na, Ca, Mg, K) which are among the lowest compared to that of most world rivers. The main minerals in the soils are secondary kaolinite, iron oxi-hydroxides, quartz, and accessory minerals (e.g., zircon, rutile). We mainly focused on the mineralogical and geochemical study of the swamp zone soils and showed through SEM observations the textural characterization of weathered minerals such as kaolinite, zircon, rutile, and the secondary recrystallization of kaolinite microcrystals within the soil profile. Water chemistry and mineralogical observations suggest that hydromorphic soils of the swamp zone are responsible for almost all chemical weathering in the basin. Thus, in order to explain the increase of element concentration in the organic-rich waters, we suggest that organic acids enhance dissolution of minerals such as kaolinite, goethite, and zircon and also favors the transport of insoluble elements such as Al, Fe, Ti, Zr, and REE by chemical complexation. SiO₂(aq) concentrations in these waters are above saturation with respect to quartz. Dissolution of phytholithes (amorphous silica) may be responsible for this relatively high SiO₂(aq.) concentration. Al/Mg ratios obtained for the soil and the Mengong river waters show that a significant amount of Al does not leave the system due to kaolinite recrystallisation in the swamp zone soils. Geochemical data obtained for this watershed show the important contribution of vegetation and organic matter on chemical weathering in the swamp zone. Quantitatively we propose that the increasing amount in total dissolved solid (TDS) due to organic matter and vegetation effect is about 35%. In summary, this interaction between soils and waters occurs mostly in soils that are very depleted in soluble elements. Thus, the low concentration of major elements in these water is a direct consequence of the depleted nature of the soils.