Identification of sulfate sources in groundwater using isotope analysis and modeling of flood irrigation with waters of different quality in the Jinghuiqu district of China

The main objective of this study was to identify the main sources and processes that control SO₄ ^2? groundwater concentrations in the Jinghuiqu irrigation district of China using isotope analysis. Lysimeter irrigation experiments and numerical modeling were used to assess the impact of long-term irrigation practices on sulfate transport, when different sources of irrigation water were used. SO₄ ^2? concentrations in the groundwater of the entire irrigation area increased significantly from the years 1990 (a mean value was 4.8 mmol L^?1) to 2009 (a mean value was 9.84 mmol L^?1). The δ³⁴S-SO₄ ^2? values (ranging from +5.27 to +10.69 ‰) indicated that sulfates in groundwater were initially predominantly derived from dissolution of minerals. However, no soluble sulfate minerals (gypsum and/or mirabilite) were detected after 1990. To better understand this seeming anomaly, water content and SO₄ ^2? data were collected before and after the field irrigation experiment and analyzed using the HYDRUS-1D and HP1 software packages. The experimental data were also used to assess sulfate leaching when different sources of irrigation water were used under current irrigation practices. The dissolved sulfate concentrations in the soil profile increased significantly when groundwater was used for infiltration compared to the use of surface water. Irrigation water sources had a great impact on the increase of sulfate concentrations in the shallow groundwater, especially when groundwater with elevated concentrations was used for irrigation.     

Reclamation of calcareous saline–sodic soil using different amendments: Time changes of soluble cations in leachate

Soil salinity and sodicity are escalating problems worldwide, especially in arid and semiarid regions. A laboratory experiment was conducted using soil column to investigate leaching of soluble cations during reclamation process of a calcareous saline–sodic soil (CaCO₃?=?20.7%, electrical conductivity (EC)?=?19.8 dS m^?1, sodium absorption ratio (SAR)?=?32.2[meq L^?1]^0.5). The amendments consisted of control, cattle manure (50 g kg^?1), pistachio residue (50 g kg^?1), gypsum (5.2 g kg^?1; equivalent of gypsum requirement), manure + gypsum and pistachio residue + gypsum, in three replicates which were mixed thoroughly with the soil, while sulfuric acid as an amendment was added to irrigation water. To reflect natural conditions, after incubation period, an intermittent irrigation method was employed every 30 days. The results showed that EC, SAR, and soluble cations of leachate for the first irrigation step were significantly higher than those of the subsequent leaching runs. Moreover, the concentration of removed soluble cations was lower for the control and gypsum-treated soils. It was found that among applied amendments, treatments containing cattle manure showed higher concentrations of sodium, calcium, and magnesium in the leachate, while due to pistachio residue application, further amount of potassium was removed out of soil column. The addition of pistachio residue resulted in the highest reduction in soil salinity and sodicity since the final EC and exchangeable sodium percentage dropped to 18.0% and 11.6% of their respective initial values, respectively. In the calcareous soil, solubility of gypsum found to be limited, in contrast, when it was added in conjunction with organic amendments, greater amounts of sodium were leached.     

Evaluation of soil salinization in a Mediterranean site (Agoulinitsa district—West Greece)

Soil salinization is an environmental problem having significant impacts on the soil–water–plant system. This problem is more frequent in coastal areas due to seawater intrusion into the land. Assessing the soil salinization is a critical issue for the agricultural areas situated in the Mediterranean basin. This paper examines the deterioration of soil quality in the cultivated land of a Mediterranean site (Agoulinitsa district—West Greece). Soil samples were collected in both pre-irrigation and post-irrigation seasons. Electrical conductivity (EC), pH and the ions Br^?, Ca²⁺, Cl^?, F^?, K⁺, Li⁺, Mg²⁺, Na⁺, NH₄ ⁺, NO₂ ^?, NO₃ ^?, PO₄ ^3? and SO₄ ^2? were determined by the 1:2 (soil/water ratio on weight basis) method. The salts which were present in both seasons in the soils of the area studied are KCl, MgCl₂, NaCl, CaSO₄ and K₂SO₄. The wide spatiotemporal variation of EC in the cultivated land in both seasons demonstrates that soil salinity is controlled mainly by seawater intrusion and anthropogenic factors such as the application of salt-rich water which is directly pumped from the drainage ditches. Seawater intrusion provides the affected soil with elevated contents of Ca²⁺, Cl^?, K⁺, Mg²⁺, Na⁺ and SO₄ ^2?. Classification of the soils by using criteria given by the literature is discussed. Practices to prevent, or at least ameliorate, salinization in the cultivated land of Agoulinitsa district are proposed.     

Evaluation of hydrogeochemistry and water quality in Bist-Doab region,Punjab, India

Agricultural activities act as dominant polluter of groundwater due to increased fertilizers and pesticides usage. Bist-Doab region, Punjab, India, is one such region facing deterioration of groundwater quality due to usage of fertilizers. This study aims in delineating and evaluating the groundwater quality in the region. Water samples are collected from canals, reservoir, and shallow and deep groundwater. Water types in canal and reservoir in Kandi region are Mg²⁺HCO₃ ^? and Mg²⁺Ca²⁺Na⁺HCO₃ ^?, respectively. While water types of shallow and deep groundwaters are found to be of two types: Na⁺Mg²⁺Ca²⁺HCO₃ ^? and Ca²⁺Mg²⁺Na⁺HCO₃ ^?. Presence of Mg²⁺ in groundwater at locations adjoining canals indicates recharge due to canal. The major ion (Na⁺, Mg²⁺, Ca²⁺, HCO₃ ^?) chemistry of the region is due to weathering of rocks that are rich in sodic minerals and kankar. Deep groundwater quality in the region meets BIS and WHO standards for drinking purpose, unlike shallow groundwater which is of poor quality at many locations. Both shallow and deep groundwater with high sodium concentration (>1.5 meq/l) affect cropping yield and permeability of soil matrix. High concentration of SO₄ ^2? and NO₃ ^2? (>1 meq/l) in shallow groundwater at few locations indicates influence of anthropogenic (fertilizer) activity. Factor analysis indicates that the major cations, bicarbonate and chloride are derived from weathering/dissolution of source rocks. Higher concentration of nitrate and presence of sulphate in shallow groundwater at few locations is due to usage of fertilizers and pesticides.     

Spatial variability of groundwater quality and its suitability for drinking and irrigation in the Amik Plain (South Turkey)

In this study, it is determined physicochemical properties of the groundwater and the spatial variability of physicochemical properties of the groundwater in the Amik plain and as well as assess its suitability for drinking and irrigation. A total 92 groundwater samples were collected from drilled well in June 2012. In addition, the 42 of 92 drilled wells were also sampled in September 2012 to evaluate the changes of groundwater properties. According to t test values, the mean Ca²⁺, SO₄ ^2?, Mg²⁺ and TH values in the June period were significantly lower than those of the September period. On the other hand, the mean (CO ₃ ^2?  + HCO₃ ^?) and RSC and MR values in the June period were significantly higher than those of the September period. The order of relative abundance of major cations in the groundwater (in mg L^?1) is in order Na⁺ > Mg²⁺ > Ca²⁺ > K⁺. The order of the anions abundance (mg L^?1) is SO₄ ^2? > Cl^? > HCO₃ ^? > CO₃ ^2? in this research. Log and square-root transformation were carried out for the most of the water properties before the calculation of semivariance. The nugget ratio showed all the variables were strongly spatial dependent except for K⁺ and Mg²⁺ and (CO₃ ^2? + HCO₃ ^?) which showed moderate spatial dependence (ratio ranging from 28 to 49.9 %). Spatial distribution analysis of groundwater quality indicated that The EC, TDS values and Na and Cl^? contents which is important water quality parameters increase from northern towards southern. The total hardness values increase also from northwestern towards southwestern.     

Groundwater Discharge as a Source of Dissolved Carbon and Greenhouse Gases in a Subtropical Estuary

Groundwater may be highly enriched in dissolved carbon species, but its role as a source of carbon to coastal waters is still poorly constrained. Exports of deep and shallow groundwater-derived dissolved carbon species from a small subtropical estuary (Korogoro Creek, Australia, latitude ?31.0478°, longitude 153.0649°) were quantified using a radium isotope mass balance model (²³³Ra and ²²⁴Ra, natural groundwater tracers) under two hydrological conditions. In addition, air-water exchange of carbon dioxide and methane in the estuary was estimated. The highest carbon inputs to the estuary were from deep fresh groundwater in the wet season. Most of the dissolved carbon delivered by groundwater and exported from the estuary to the coastal ocean was in the form of dissolved inorganic carbon (DIC; 687 mmol m^?2 estuary day^?1; 20 mmol m^?2 catchment day^?1, respectively), with a large export of alkalinity (23 mmol m^?2 catchment day^?1). Average water to air flux of CO₂ (869 mmol m^?2 day^?1) and CH₄ (26 mmol m^?2 day^?1) were 5- and 43-fold higher, respectively, than the average global evasion in estuaries due to the large input of CO₂- and CH₄-enriched groundwater. The groundwater discharge contribution to carbon exports from the estuary for DIC, dissolved organic carbon (DOC), alkalinity, CO₂, and CH₄ was 22, 41, 3, 75, and 100 %, respectively. The results show that CO₂ and CH₄ evasion rates from small subtropical estuaries surrounded by wetlands can be extremely high and that groundwater discharge had a major role in carbon export and evasion from the estuary and therefore should be accounted for in coastal carbon budgets.     

Effects of the external carbon sources on the microbes in the simultaneous biological removal of SO2 and NO x process

Effects of sodium acetate and glucose on the microbes from the simultaneous flue gas desulfurization and denitrogenation tandem biotrickling process were respectively investigated. For the acidophiles, although the impacts of the carbon sources on the total microbial growth and nitrogen conversion in the medium were slight, the sulfite oxidation rate was obviously improved. The highest sulfite ion oxidation ratio in 48 h was up to 47.2 % as 258.08 mmol L^?1 sodium acetate was added in the medium. For the neutrophiles, the two carbons promoted the total microbial growth, but only sodium acetate could enhance the nitrite consumption significantly. The best nitrite consumption rate in 48 h could reach to 86.7 % with 258.08 mmol L^?1 sodium acetate. It provides valuable information for the development of biological SO₂ and NO _x simultaneous purification process.     

Using chemical analysis and modeling to enhance the understanding of soil solution of some calcareous soils

The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca²⁺ > Mg²⁺ > Na⁺ > K⁺. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $  > Cl $ ^{ - } $  > SO $ _{4}^{2 - } $  > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K⁺ in soil solutions were in the range of 6.8–307.5 mg l^?1 (mean 63.2 mg l^?1), 5.0–10.4 mg l^?1 (mean 5.9 mg l^?1), and 2.8–54.6 mg l^?1 (mean 11.3 mg l^?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO₂ (g), N₂ (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca²⁺, Mg²⁺, K⁺ and Na⁺ occurred with Mg²⁺ and K⁺ into the solution, and Ca²⁺ and Na⁺ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration.     

Potassium leaching in undisturbed soil cores following surface applications of gypsum

Displacement studies on leaching of potassium (K⁺) were conducted under unsaturated steady state flow conditions in nine undisturbed soil columns (15.5 cm in diameter and 25 cm long). Pulses of K⁺ applied to columns of undisturbed soil were leached with distilled water or calcium chloride (CaCl₂) at a rate of 18 mm h⁻¹. The movement of K⁺ in gypsum treated soil leached with distilled water was at a similar rate to that of the untreated soil leached with 15 mM CaCl₂. The Ca²⁺ concentrations in the leachates were about 15 mM, the expected values for the dissolution of the gypsum. When applied K⁺ was displaced with the distilled water, K⁺ was retained in the top 10–12.5 cm depth of soil. In the undisturbed soil cores there is possibility of preferential flow and lack of K⁺ sorption. The application of gypsum and CaCl₂ in the reclamation of sodic soils would be expected to leach K⁺ from soils. It can also be concluded that the use of sources of water for irrigation which have a high Ca²⁺ concentration can also lead to leaching of K⁺ from soil. Average effluent concentration of K⁺ during leaching period was 30.2 and 28.6 mg l⁻¹ for the gypsum and CaCl₂ treated soils, respectively. These concentrations are greater than the recommended guideline of the World Health Organisation (12 mg K⁺ l⁻¹).     

Hydrogeochemistry and quality of groundwater of coastal unconfined aquifer in Amol–Ghaemshahr plain,Mazandaran Province,Northern Iran

Groundwater of the unconfined aquifer (1,100 sq. km) of a two-tier coastal aquifer located in the Amol–Ghaemshahr plain, Mazandaran Province, Northern Iran, is classified into fresh and brackish water types. Fresh groundwater (FGW) samples (n = 36) are characterized by Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ and HCO₃ ^? > Cl^? > SO₄ ^2? > NO₃ ^?. Spearman’s rank correlation coefficient matrices, factor analysis data, values of the C-ratio (av. = 0.89) and CAI and values of the molar ratios of Ca²⁺/HCO₃ ^?, Ca²⁺/SO₄ ^2?, Mg²⁺/HCO₃ ^? and Mg²⁺/SO₄ ^2? indicate that the ionic load in the FGW is derived essentially from carbonic acid-aided weathering of carbonates and aluminosilicates, saline/sea water trapped in the aquifer sediments (now admixed with the groundwater) and ion exchange reactions. Values of the CAI and Na⁺/Cl^? molar ratio suggest that the part of the Ca²⁺ (±Mg²⁺) content in 23 FGW samples is derived from clay minerals of the aquifer matrix, and part of the Na⁺ content in 20, 12, and 3 FGW samples is derived, respectively, from alkali feldspar weathering, clay minerals of the aquifer matrix and rain water and/or halite. Brackish groundwater (BGW) samples (n = 4) contain Cl^? as the dominant anion and their average total ionic concentration (38.65 meq/L) is 1.79 times higher than that of the FGW samples (21.50 meq/L). BGW pockets were generated by non-conservative mixing of FGW with the upconed saline water from the underlying saline groundwater zone of the semi-confined aquifer along bore wells involved in excessive extraction of groundwater from the unconfined aquifer. Groundwater belongs essentially to “high salinity, low sodium” irrigation water class.     

Geochemistry and quality of groundwater of Gummanampadu sub-basin, Guntur District, Andhra Pradesh, India

Groundwater survey has been carried out in the area of Gummanampadu sub-basin located in Guntur District, Andhra Pradesh, India for assessing the factors that are responsible for changing of groundwater chemistry and consequent deterioration of groundwater quality, where the groundwater is a prime source for drinking and irrigation due to non-availability of surface water in time. The area is underlain by the Archaean Gneissic Complex, over which the Proterozoic Cumbhum rocks occur. The results of the plotting of Ca²⁺ + Mg²⁺ versus HCO₃ ^? + CO₃ ^2?, Ca²⁺ + Mg²⁺ versus total cations, Na⁺ + K⁺ versus total cations, Cl^? + SO₄ ^2? versus Na⁺ + K⁺, Na⁺ versus Cl^?, Na⁺ versus HCO₃ ^? + CO₃ ^2?, Na⁺ versus Ca²⁺ and Na⁺: Cl^? versus EC indicate that the rock–water interaction under alkaline condition is the main mechanism in activating mineral dissociation and dissolution, causing the release of Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO₃ ^?, CO₃ ^2?, SO₄ ^2? and F^? ions into the groundwater. The ionic relations also suggest that the higher concentrations of Na⁺ and Cl^? ions are the results of ion exchange and evaporation. The influences of anthropogenic sources are the other cause for increasing of Mg²⁺, Na⁺, Cl^?, SO₄ ^2? and NO₃ ^? ions. Further, the excess alkaline condition in water accelerates more effective dissolution of F^?-bearing minerals. Moreover, the chemical data plotted in the Piper’s, Gibbs’s and Langelier–Ludwig’s diagrams, computed for the chloro-alkaline and saturation indices, and analyzed in the principal component analysis, support the above hypothesis. The groundwater quality is, thus, characterized by Na⁺ > Ca²⁺ > Mg²⁺ > K⁺: HCO₃ ^? + CO₃ ^2? > Cl^? > SO₄ ^2? > NO₃ ^? > F^? facies. On the other hand, majority of groundwater samples are not suitable for drinking with reference to the concentrations of TDS, TH, Mg²⁺ and F^?, while those are not good for irrigation with respect to USSL’s and Wilcox’s diagrams, residual sodium carbonate, and magnesium hazard, but they are safe for irrigation with respect to permeability index. Thus, the study recommends suitable management measures to improve health conditions as well as to increase agricultural output.     

Spatial and Temporal Variability of the CO2 Fluxes in a Tropical, Highly Urbanized Estuary

The spatial and temporal variations of the flux of CO₂ were determined during 2007 in the Recife estuarine system (RES), a tropical estuary that receives anthropogenic loads from one of the most populated and industrialized areas of the Brazilian coast. The RES acts as a source of nutrients (N and P) for coastal waters. The calculated CO₂ fluxes indicate that the upstream inputs of CO₂ from the rivers are largely responsible for the net annual CO₂ emission to the atmosphere of +30 to +48 mmol m^?2 day^?1, depending on the CO₂ exchange calculation used, which mainly occurs during the late austral winter and early summer. The observed inverse relationship between the CO₂ flux and the net ecosystem production (NEP) indicates the high heterotrophy of the system (except for the months of November and December). The NEP varies between ?33 mmol m^?2 day^?1 in summer and ?246 mmol m^?2 day^?1 in winter. The pCO₂ values were permanently high during the study period (average ~4,700 μatm) showing a gradient between the inner (12,900 μatm) and lower (389 μatm) sections on a path of approximately 30 km. This reflects a state of permanent pollution in the basin due to the upstream loading of untreated domestic effluents (N/P?=?1,367:6 μmol kg^?1 and pH?=?6.9 in the inner section), resulting in the continuous mineralization of organic material by heterotrophic organisms and thereby increasing the dissolved CO₂ in estuarine waters.     

Hydrochemical characteristics and quality assessment of regolith aquifers in Enugu metropolis, southeastern Nigeria

Twenty groundwater samples were collected from Enugu metropolis over two seasonal periods in order to characterize the groundwater and to determine its quality for domestic and irrigation purposes. The results show that groundwater of the area is strongly acidic to slightly alkaline in nature and varied from “soft water” to “moderately hard” water type. The major ionic trend is in the order Cl^? > Na⁺ > HCO₃ ^? > K⁺ > Mg²⁺ > Ca²⁺ > SO₄ ^2?and Mg²⁺ > Cl^? > Na⁺ > K⁺ > Ca²⁺ > HCO ₃ ^?  > SO₄ ^2? in abundance for dry and rainy seasons, respectively. The results also reveal that there is an increase in trend of the ionic concentrations during the dry season, which arises from weathering of the host rocks and anthropogenic activities. Two hydrochemical facies were identified, namely, Na⁺ –K⁺ –Cl^? –SO₄ ^2?and Ca²⁺ –Mg²⁺ –Cl^? –SO₄ ^2? _, with Na⁺ –K⁺ –Cl^? –SO₄ ^2? as the dominant facies for the two seasons. Groundwater quality ranges from “very poor water” to “good water” and “water unsuitable for drinking purposes” to “good water” for the dry season and rainy season investigations, respectively. The groundwater is suitable for irrigation purposes for the two seasons.     

Dolomite Versus Calcite Weathering in Hydrogeochemically Diverse Watersheds Established on Bedded Carbonates (Sava and So?a Rivers, Slovenia)

The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg²⁺/Ca²⁺ ratios to the local bedrock lithology and the HCO₃ ^? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg²⁺/Ca²⁺ ratio of the main channel of the Sava River indicates that the HCO₃ ^? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg²⁺/Ca²⁺ mole ratio of 0.33). The HCO₃ ^? concentration and pCO₂ values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO₃ ^? from the alpine to the dinaric karst regions. Streams in general do not change in HCO₃ ^?, Mg²⁺/Ca²⁺, or Mg²⁺/HCO₃ ^? concentrations down course, but warming and degassing of CO₂ produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km²-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO₃ ^?, Ca²⁺, and Mg²⁺ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.     

Assessment of groundwater quality with special reference to arsenic in Nawalparasi district,Nepal using multivariate statistical techniques

Groundwater is a precious resource for humankind not only in Nepal but also across the globe due to its diverse functions. A total of 48 groundwater samples were collected from three villages of Nawalparasi district, Nepal, during pre-monsoon and monsoon to estimate the overall groundwater quality and to identify the sources of contamination with emphasis on arsenic (As). The average concentrations of all tested groundwater quality parameters (temp., pH, EC, ORP, Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^?, F^?,SO₄ ^2?, PO₄ ^3?, HCO₃ ^?, NO₃ ^?, Cu, Ni, Mn, Cd, Pb, Fe, Zn, Cr, and As) were well within permissible limits of WHO for drinking water, except for Ni, Cd, Pb, Cr, and As. Concentration of As ranged from 60 to 3,100 μg L^?1 and 155 to 1,338 μg L^?1 in pre-monsoon and monsoon, respectively. The Piper diagram of the groundwater chemistry showed groundwater of Nawalparasi belongs to Ca–Mg–HCO₃ and Mg–HCO₃ water type with HCO₃ ^? as dominant ions. As content in the study area was negatively correlated with Fe in pre-monsoon, while it was positively correlated in monsoon. Furthermore, As was negatively correlated with oxidation reduction potential suggesting reducing condition of groundwater. Principal component analysis revealed seven major factors that explained 81.996 and 83.763 % of total variance in water quality in pre-monsoon and monsoon, respectively. The variance of water quality was related mainly with the degree of water–rock interaction, mineralization, and anthropogenic inputs.     

Hydrogeochemistry of coal mine water of North Karanpura coalfields,India: implication for solute acquisition processes,dissolved fluxes and water quality assessment

Mine water samples collected from different mines of the North Karanpura coalfields were analysed for pH, electrical conductivity, total dissolved solids (TDS), total hardness (TH), major anions, cations and trace metals to evaluate mine water geochemistry and assess solute acquisition processes, dissolved fluxes and its suitability for domestic, industrial and irrigation uses. Mine water samples are mildly acidic to alkaline in nature. The TDS ranged from 185 to 1343 mg L^?1 with an average of 601 mg L^?1. Ca²⁺ and Mg²⁺ are the dominant cations, while SO₄ ^2? and HCO₃ ^? are the dominant anions. A high concentration of SO₄ ^2? and a low HCO₃ ^?/(HCO₃ ^? + SO₄ ^2?) ratio (<0.50) in the majority of the water samples suggest that either sulphide oxidation or reactions involving both carbonic acid weathering and sulphide oxidation control solute acquisition processes. The mine water is undersaturated with respect to gypsum, halite, anhydrite, fluorite, aluminium hydroxide, alunite, amorphous silica and oversaturated with respect to goethite, ferrihydrite, quartz. About 40% of the mine water samples are oversaturated with respect to calcite, dolomite and jarosite. The water quality assessment shows that the coal mine water is not suitable for direct use for drinking and domestic purposes and needs treatment before such utilization. TDS, TH, F^?, SO₄ ^2?, Fe, Mn, Ni and Al are identified as the major objectionable parameters in these waters for drinking. The coal mine water is of good to suitable category for irrigation use. The mines of North Karanpura coalfield annually discharge 22.35 × 10⁶ m³ of water and 18.50 × 10³ tonnes of solute loads into nearby waterways.     

Rate Equations and an Ion-pair Mechanism for Batch Dissolution of Gypsum: Repositioning the Shrinking Object Model at the Core of Hydrodynamic Modelling

Recent improvements to experiments and modelling of batch dissolution in a turbulent reactor, based upon the shrinking object model, are extended to middle loadings of gypsum, that is, in the region between low and high loadings, which lead, respectively, to high under-saturation or saturation with a great excess of solid left undissolved. Dissolved calcium sulphate concentration was monitored by change in electrical conductivity. This investigation uses an improved, ion-pair model for CaSO ₄ ⁰ to allow for the presence of calcium or sulphate added as common ions. The study demonstrates that the full dissolution curve for 5.82 mM loadings of 106-μm particles of gypsum (~1.00 g L^?1) in de-ionised water barely changed in the presence of either 4.64 or 8.09 mM calcium chloride, or 4.39 mM sodium sulphate. However, this masked a doubling of dissolution rate imposed by comparable increases in ionic strength from sodium chloride. The results are consistent with the ion pair, CaSO ₄ ⁰ , being the key species in the rate-determining step of the back-reaction, and perhaps all salt dissolutions, including calcium carbonate. In this case, the rate equation is as follows: \( {\frac{{{\text{d}}c}}{{{\text{d}}t}}} = \frac{S}{V} \cdot (k_{1} - k_{2}^{\prime } \cdot [{\text{CaSO}}_{ 4}^{0} ]) \), where k ₁ and k ₂′ are rate constants. The reported observations are interpreted as effects of ionic strength and common ion concentrations upon the formation equilibrium for the ion pair. This rate equation readily transforms mathematically to one involving the product of [Ca²⁺] and [SO₄ ^2?] in the back-reaction. The parallel of this with the well-known PWP equation used in calcium carbonate dissolution is discussed, with the CaHCO₃ ⁺ ion pair of the equation being replaced by that of CaCO ₃ ⁰ . Meanwhile, the earlier use of the product, [Ca²⁺]^½ × [CO₃ ^2?]^½, in the back-reaction term of another dissolution rate equation for calcite is shown to be incorrect. Finally, it is argued that the shrinking object model should be repositioned as a logical derivative of the hydrodynamical approach to dissolution.     

Effects of cations and anions on iron and manganese sorption and desorption capacity in calcareous soils from Iran

This study investigated the effect of cations and anions on the sorption and desorption of iron (Fe) and manganese (Mn) in six surface calcareous soil samples from Western Iran. Six 10 mM electrolyte background solutions were used in the study, i.e., KCl, KNO₃, KH₂PO₄, Ca(NO₃)₂, NaNO₃, and NH₄NO₃. NH₄NO₃ and NaNO₃ increased the soil retention of Fe and Mn, whereas Ca(NO₃)₂ decreased the soil retention of Fe and Mn. Iron and Mn sorption was decreased by NO₃ ^? compared with H₂PO₄ ^? or Cl^?. The Freundlich equation adequately described Fe and Mn adsorption, with all background electrolytes. The Freundlich distribution coefficient (K _F) decreased in the order H₂PO₄ ^? > Cl^? > NO₃ ^? for Mn and H₂PO₄ ^? > NO₃ ^? > Cl^? for Fe. The highest sorption reversibility was for Fe and Mn in competition with a Ca²⁺ background, indicating the high mobility of these two cations. A MINTEQ speciation solubility model showed that Fe and Mn speciation was considerably affected by the electrolyte background used. Saturation indices indicated that all ion background solutions were saturated with respect to siderite and vivianite at low and high Fe concentrations. All ion background solutions were saturated with respect to MnCO_3(am), MnHPO₄, and rhodochrosite at low and high Mn concentrations. The hysteresis indices (HI) obtained for the different ion backgrounds were regressed on soil properties indicating that silt, clay, sand, and electrical conductivity (EC) were the most important soil properties influencing Fe adsorption, while cation exchange capacity (CEC), organic matter (OM), and Mn-DTPA affected Mn adsorption in these soils.     

Assessment of groundwater quality in and around Vedaraniyam,South India

Groundwater from 47 wells were analyzed on the basis of hydrochemical parameters like pH, electric conductivity, total dissolved solids, Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^?, CO₃ ^2?, HCO₃ ^?, NO₃ ^?, PO₄ ^3? and F^? in the Cauvery delta of Vedaraniyam coast. Further, water quality index (WQI), sodium percentage (Na %), sodium absorption ratio, residual sodium carbonate, permeability index and Kelley’s ratio were evaluated to understand the suitability of water for drinking and irrigation purposes. The result shows significant difference in the quality of water along the coastal stretch. The order of dominance of major ions is as follows: Na⁺ ≥ Mg²⁺ ≥ Ca²⁺ ≥ K⁺ and Cl^? ≥ HCO₃ ^? ≥ CO₃ ^2? ≥ PO₄ ^3? ≥ F^?. Na/Cl, Cl/HCO₃ ratio and Revelle index confirmed that 60–70 % of the samples were affected by saline water intrusion. WQI showed that 36 % of the samples were good for drinking and the remaining were poor and unsuitable for drinking purpose. The degradation of groundwater quality was found to be mainly due to over-exploitation, brackish aquaculture practice, fertilizer input from agriculture and also due to domestic sewage.     

Arsenic mobilization in alluvial soils of Punjab, North–West India under flood irrigation practices

A laboratory investigation was carried out to examine the mechanism of arsenic (As) mobilization under flooded conditions (24 and 240 h) in 18 alluvial soils of Punjab, North–West India. Total dissolved As increased from a range of 3–16 μg L^?1 (mean 9 μg L^?1) to a range of 33–1,761 μg L^?1 (mean 392 μg L^?1) with the increase in flooding period from 24 to 240 h. The amount of As mobilization varied depending upon redox potential (pe) created by flooding conditions. After 24 h of flooded conditions, pe of soil water suspension ranged from ?1.75 to 0.77 (mean ?0.24). Increasing the flooding period to 240 h, pe of soil water suspension decreased in the range of ?4.49 to ?2.74 (mean ?3.29). Pourbaix diagram identified arsenate (HAsO₄ ^2?) as predominant species in most of the alluvial soil–water suspensions under oxidized conditions, after 24 h of equilibration period, which ultimately transformed to arsenite (H₃AsO₃ ⁰) after 240 h of anaerobic condition due to more reduced status. The solid phase identified was orpiment (As₂S₃). Identification of iron and manganese species in alluvial soil water suspension by Pourbaix diagram indicated decline in both soluble Fe²⁺ and SO₄ ^2? concentration due to the formation of iron sulfide mineral phase after 240 h under anaerobic conditions. In these soils, decline in soluble Fe was also due to the precipitation of vivianite [Fe₃(PO₄)₂·8H₂O]. Elevated arsenic content and low pe value were measured in aquifers located in paddy growing fields comparative to aquifers of other sites. Large degree of variability in As concentrations was recorded in aquifers located at same sites. Thus, it is better to analyze each aquifer for their As content rather than to depends on the prediction on As content of neighbouring wells. The present investigation elucidates that flood irrigation practices in Punjab for growing paddy crop could induce the geochemical conditions favorable to mobilize arsenic from surface soils which could eventually elevate its content in the underlying shallow aquifers. Water abstracted from these aquifers by hand pumps or tube wells for drinking purposes could create hazards for local population due to loading with arsenic concentration above the safe limits. Thus, to avoid further contamination of shallow aquifers with arsenic, it is advisable to shift the flooded rice cultivation to other upland crops having lesser water requirement.