A novel label-free method for determination of inorganic mercury in environmental aqueous media using BSA-modified silver nanoparticles

A selective colorimetric sensor was developed for rapid and fast determination of highly toxic Hg²⁺ according to decolorization of unmodified silver nanoparticles (AgNPs). A simple strategy was used for providing water-soluble AgNPs. Bovine serum albumin (BSA) and sodium borohydride were used as stabilizing and reducing agents, respectively. AgNPs, prepared by BSA, were stable for 2 months. The freshly prepared bio-stabilized AgNPs were brownish yellow in color owing to the severe surface plasmon resonance (SPR) peak at 420 nm. The yellow AgNPs solution became colorless in the presence of Hg²⁺, as well as a gradual blue shift, and decrease in the intensity of absorption peak was observed with increasing the concentrations of mercury, because of aggregation of the nanoparticles. The calibration curve was linear from 5 to 80 µM (r = 0.994). The detection limit was 2.7 µM. Selective determination of mercury (II) ions was performed in the presence of other ions. To investigate the practical applications of BSA/AgNPs in real samples, mercury determination was performed in a groundwater sample and good recoveries (>94.0 %) were obtained.     

Geochemical evaluation and environmental application of Yemeni natural zeolite as sorbent for Cd<Superscript>2+</Superscript> from solution: kinetic modeling,equilibrium studies,and statistical optimization

Yemeni natural zeolite was characterized by XRD, SEM, FTIR and XRF as well as its applicability as a sorbent material for Cd²⁺ ions in aqueous solutions. The zeolitic sample is clinoptilolite-K of heulandite group with intermediate Si/Al ratio. The removal% of Cd²⁺ by natural clinoptilolite was investigated as a function of contact time, zeolite dose, pH and initial concentration of Cd²⁺ ions. Kinetic experiments indicated that sorption of Cd²⁺ follows two steps: rapid ion exchange process on the outer surface is followed by slow adsorption process on the inner surface of clinoptilolite. The equilibrium was attained after 120 min, and the results were fitted well with pseudo-second order and Elovich kinetic models. The Cd²⁺ removal% is strongly dependent on pH value and increases with the increasing pH value. Equilibrium sorption isotherm of Cd²⁺ by clinoptilolite was described well using the Langmuir, Freundlich, and Temkin isotherms models. However, the data relatively well fitted with Freundlich model (R ² = 0.97) rather than by the other models. Response surface methodology in conjunction with central composite rotatable statistical design was used to optimize the sorption process. The model F-value indicated the high significance of second-order polynomial model to represent the interaction between the operating parameters. From the Design Expert’s optimization function, the predicted optimum conditions for maximum removal% of Cd²⁺ (80.77%) are 116 min contact time, 0.27 gm dose, and pH 7 at an initial Cd²⁺ concentration of 25 mg/L.     

Weakly bound water structure,bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

Background

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Results

The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe³⁺ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe³⁺. The water molecules capping surface Fe³⁺ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe³⁺ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe³⁺ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe³⁺, those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe³⁺ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism.

Conclusions

Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe–OH₂ distances in the DFT calculations it was proposed that the surface Fe³⁺ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination.

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Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe³⁺ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe³⁺ is coordinated with only 5 neighbors.

     

Adsorption of lead, zinc and cadmium ions from contaminated water onto Peganum harmala seeds as biosorbent

Peganum harmala seeds were assessed as biosorbent for removing Pb²⁺, Zn²⁺and Cd²⁺ ions from aqueous solutions. The effects of various parameters such as the aqueous solution pH, the contact time, the initial metal concentration and the amount of adsorbent in the process were investigated. The adsorption efficiencies increased with pH. It was found that about 95 % of lead, 75 % of zinc and 90 % of cadmium ions could be removed from 45 ml of aqueous solution containing 20 mg l^?1 of each cation with 2 g of adsorbent at pH 4.5 after 15 min. The quantitative desorption of cadmium from adsorbent surface was achieved using 10 ml of a 0.5 M nitric acid solution. This condition was attained for lead and zinc ions with 10 ml of 1 M hydrochloric acid solution. Kinetic investigation of the process was performed by considering a pseudo-second-order model. This model predicts the chemisorption mechanism of the process. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich models were tested for describing the equilibrium data. It was found that the Freundlich model describes the experimental data resulting from the adsorption of lead ions. However for cadmium and zinc ions, the adsorption equilibria were interpreted with the Langmuir model.     

Competitive adsorption of metal ions onto goethite–humic acid-modified kaolinite clay

A binary mixture of humic acid and geothite was prepared and used to modify kaolinite to produce geothite–humic acid (GHA)-modified kaolinite adsorbent useful for the adsorption of Pb²⁺, Cd²⁺, Zn²⁺, Ni²⁺ and Cu²⁺ from Single and Quinary (5) metal ion systems. The cation exchange capacity (CEC) and specific surface area of GHA-modified kaolinite clay adsorbent were found to be 40 meq/100 g and 13 m²/g, respectively, with the CEC being five times that of raw kaolinite clay (7.81 meq/100 g). The Langmuir–Freundlich equilibrium isotherm model gave better fit to experimental data as compared with other isotherm models. In Quinary metal ion system, the presence of Zn²⁺ and Cu²⁺ appears to have an antagonistic effect on the adsorption of Pb²⁺, Cd²⁺ and Ni²⁺, while the presence of Pb²⁺, Cd²⁺ and Ni²⁺ shows a synergistic effect on the adsorption of Zn²⁺ and Cu²⁺. The GHA-modified kaolinite showed strong preference for the adsorption of Pb²⁺ in both metal ion systems. Brouers–Weron–Sotolongo (BWS) kinetic model gave better fit to kinetic data compared with other kinetic models used. Data from BWS kinetic model indicate that adsorption of metal ions onto GHA-modified adsorbent in both metal ion systems followed strictly, diffusion-controlled mechanism with adsorption reaction proceeding to 50 % equilibrium in <2 min in the Single metal ion system and <1 min in the Quinary metal ion system. Adsorption of metal ions onto GHA-modified kaolinite is fairly spontaneous and endothermic in nature in both metal ion systems although the rate of metal ion uptake and spontaneity of reaction are reduced in the Quinary metal ion system.     

Cadmium (II)-selective electrode based on palm shell activated carbon modified with task-specific ionic liquid: kinetics and analytical applications

In this study, palm shell activated carbon modified with task-specific ionic liquid was used as a novel electrode component for the potentiometric determination of cadmium ions in water samples. The proposed potentiometric sensor has good operating characteristics, including relatively high selectivity towards the Cd (II) ion, a Nernstian response to Cd (II) ions in a working concentration range of 1.0 × 10^?9–1.0 × 10^?2 M, with a reasonable detection limit of 1 × 10^?10 M and a slope of 30.90 ± 1.0 mV/decade. No significant changes in electrode potential were observed when the pH was varied over the range of 4–9. A direct technique based on the use of ion-selective electrode potentiometry has been developed in our laboratory for the study of reaction kinetics and kinetic methods of analysis by continuous monitoring of the rate of production or consumption of an ion. The apparent adsorption rate constant was estimated assuming pseudo-second-order kinetics. Additionally, the proposed electrode has been successfully used for the determination of the cadmium content in real samples without a significant interaction from other cationic or anionic species.     

Pectin–cerium (IV) tungstate nanocomposite and its adsorptional activity for removal of methylene blue dye

Pectin–cerium (IV) tungstate composite (Pc/CT) has been prepared by sol gel method at room temperature. The composite ion exchanger has been characterized using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and Fourier infrared spectroscopy. The ion exchange capacity, pH titrations, thermal stability and distribution coefficient of composite ion exchanger were investigated. The Na⁺ ions exchange capacity of the Pc/CT has been observed higher (1.4 meq g^?1) as compared to its inorganic counterpart (0.8 meq g^?1). Pc/CT composite ion exchanger was thermally stable and retained about 60 % of its ion exchange capacity up to 400 °C. The distribution study has inferred more selective the Pc/CT for Zn²⁺ as compared to other metal ions. The adsorption efficiency of Pc/CT was tested for methylene blue removal dye from aqueous phase. The removal of dye followed pseudo-second-order kinetics.     

Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg⁰). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H₂O₂. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg⁰ to Hg²⁺, thus increasing Hg⁰ evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m^?2 h^?1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H₂O₂ to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.     

Hydrogeological processes controlling the release of arsenic in parts of 24 Parganas district,West Bengal

A study was conducted to understand the hydrogeological processes dominating in the North 24 Parganas and South 24 Parganas based on representative 39 groundwater samples collected from selected area. The abundance of major ions was in the order of Ca²⁺ > Na⁺ > Mg²⁺ > K⁺ > Fe²⁺ for cations and HCO₃ ^? > PO₄ ^3? > Cl^? > SO₄ ^2? > NO₃ ^? for anions. Piper trilinear diagram was plotted to understand the hydrochemical facies. Most of the samples are of Ca-HCO₃ type. Based on conventional graphical plots for (Ca + Mg) vs. (SO₄ + HCO₃) and (Na + K) vs. Cl, it is interpreted that silicate weathering and ion exchange are the dominant processes within the study area. Previous studies have reported quartz, feldspar, illite, and chlorite clay minerals as the major mineral components obtained by the XRD analysis of sediments. Mineralogical investigations by SEM and EDX of aquifer materials have shown the occurrence of arsenic as coating on mineral grains in the silty clay as well as in the sandy layers. Excessive withdrawal of groundwater for irrigation and drinking purposes is responsible for fluctuation of the water table in the West Bengal. Aeration beneath the ground surface caused by fluctuation of the water table may lead to the formation of carbonic acid. Carbonic acid is responsible for the weathering of silicate minerals, and due to the formation of clay as a product of weathering, ion exchange also dominates in the area. These hydrogeological processes may be responsible for the release of arsenic into the groundwater of the study area, which is a part of North 24 Parganas and South 24 Parganas.     

Assessment of groundwater quality for irrigation purposes and identification of hydrogeochemical evolution mechanisms in Pengyang County, China

Groundwater is an important water source for agricultural irrigation in Penyang County. Some traditional methods such as irrigation coefficient, sodium adsorption ratio, total alkalinity, total salinity and total dissolved solids were employed to assess groundwater quality in this area. In addition, an improved technique for order preference by similarity to ideal solution model was applied for comprehensive assessment. The origin of major ions and groundwater hydrogeochemical evolution was also discussed. Groundwater in Penyang County contains relative concentrations of dominant constituents in the following order: Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ for cations and HCO₃ ^? > SO₄ ^2? > Cl^? > CO₃ ^2? for anions. Groundwater quality is largely excellent and/or good, suggesting general suitability for agricultural use. Calcite and dolomite are found saturated in groundwater and thus tend to precipitate out, while halite, fluorite and gypsum are unsaturated and will dissolve into groundwater during flow. Groundwater in the study area is weathering-dominated, and mineral weathering (carbonate and silicate minerals) and ion exchange are the most important factors controlling groundwater chemistry.     

Modification of PPTA-based polymeric waste and adsorption properties for metal ions

Novel composite adsorbents PPTA-AOx were synthesized by grafting polyacrylonitrile onto poly(p-phenylene terephthalamide) (PPTA) followed by converting the acrylonitrile into the amidoxime (AO) groups. Their structures were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, transmission electron microscopy, etc. Scanning electron microscopy analysis and pore structure analysis manifested that PPTA-AOx adsorbents are all composed of nanoparticles aggregation. The as-synthesized PPTA-AOx adsorbents showed good adsorption capacity for Hg²⁺ with a maximum adsorption capacity of 2.50 mmol g^?1. The pseudo-second-order model can reasonably describe the adsorption kinetics of the three adsorbents for Hg²⁺. Langmuir model provided better fit for the isothermal adsorption of Hg²⁺ on PPTA-AO₁ and PPTA-AO₂, while the Freundlich model was better for PPTA-AO₃. The adsorption process might involve both chemisorption and physisorption. According to the calculated thermodynamic parameters, it can be concluded that the adsorption is an endothermic, spontaneous and entropy-driven process.     

Assessment of raw clays from Maghnia (Algeria) for their use in the removal of Pb<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> ions from industrial liquid wastes: a case study of wastewater treatment

Homogenized samples of raw clays resulting from two (2) different lots of natural clays from Maghnia (Algeria) have been assessed for their potential use in the removal of Pb²⁺ and Zn²⁺ ions from industrial liquid wastes (LW). Raw and acid-activated samples have been characterized by powder X-ray diffraction, FT-IR spectroscopy, electron microscopy (SEM), and X-ray fluorescence (XRF) and used as adsorbents for the removal of Pb²⁺ and Zn²⁺ ions from aqueous system using adsorption method under different conditions. The effect of factors including contact time, pH, and dosage on the adsorption properties of Pb²⁺ and Zn²⁺ ions onto clays was investigated at 25 °C. The obtained results revealed that the removal percentages of Pb²⁺ and Zn²⁺ ions, from both aqueous solution (AS) and LW, were varying between 90 and 98% for 40 min and optimal pH values ranged from 5 to 6 for Pb²⁺ and Zn²⁺ ions, respectively. The kinetics of both Pb²⁺ and Zn²⁺ ion adsorption fitted well with the pseudo-second-order model. Langmuir, Freundlich, and Temkin adsorption isotherms were used, and their constants were evaluated. The values of thermodynamic parameters, ΔH°, ΔS°, and ΔG° indicated that the adsorption of Pb²⁺ and Zn²⁺ ions was spontaneous and exothermic process in nature. The adsorption and desorption isotherms indicated that Pb²⁺ and Zn²⁺ adsorption to raw clays was reversible. The experimental results obtained showed that the raw clays from Maghnia (Algeria) had a great potential for removing Pb²⁺ and Zn²⁺ ions from industrial liquid wastes using adsorption method.     

Improvement of cadmium ion electrochemical removal from dilute aqueous solutions by application of multi-stage electrolysis

Improvement of cadmium ion electrochemical removal from dilute aqueous solutions in a spouted bed reactor was investigated. Enlargement of cathode surface area from 1,000 to 1,500 cm² resulted in a decrease of nearly 30 % in both of the process time and the specific energy consumption. Application of a three-stage electrolysis process for a solution containing initial concentration of 270 ppm cadmium ion, resulted in the removal of 99.9 % cadmium ion in 135 min with the specific energy consumption of 2.29 kWh/kg, 23 % less than the value of a single-stage process. For a solution with cadmium ion initial concentration of 180 ppm, 99.9 % of cadmium ion was removed in 135.5 min by application of a two-stage electrolysis process, while the specific energy consumption was 2.82 kWh/kg, 30 % less than that of a single-stage process. For a solution with cadmium ion initial concentration of 90 ppm, 99.5 % of cadmium ion was removed in 100.2 min with the specific energy consumption of 3.78 kWh/kg in a single-stage electrolysis process.     

Biosorption of cadmium(II), lead(II) and cobalt(II) from aqueous solution by biochar from cones of larch (<Emphasis Type="Italic">Larix decidua</Emphasis> Mill. <Emphasis Type="Italic">subsp. decidua</Emphasis>) and spruce (<Emphasis Type="Italic">Picea abies</Emphasis> L. H. Karst)

Because of their physicochemical properties, biochars can be used as sorption materials for removal of toxic substances. The purpose of the present study was to determine whether biochar obtained from cones of larch (Larix decidua Mill. subsp. decidua) and spruce (Picea abies L. H. Karst) could be used as a sorbent for Cd²⁺, Pb²⁺ and Co²⁺ in aqueous solutions. So far, this feedstock had not been tested in this respect. The material was subjected to pyrolysis at 500 and 600 °C for the duration of 5, 10 and 15 min. The obtained pyrolysates were found to differ in terms of pH and the contents of the essential macroelements. The different values of these parameters were determined for varying temperature, duration of the pyrolysis process and type of feedstock. Sorption capacities of the biochars for removal of Cd²⁺, Pb²⁺ and Co²⁺ were examined using simulated contamination of aqueous solutions with salts of these metals. The findings showed the highest, nearly complete, removal for Pb²⁺ were maximum 99.7%, and almost three times lower value for Cd²⁺ and Co²⁺ (respectively, 35.7 and 24.8%). It was demonstrated that pyrolysis of conifer cones produced optimum sorption capacities when the process was conducted at a temperature of 500 °C for the duration of 5 min. It was shown that products of spruce cone pyrolysis were characterized by better sorption capacity in comparison with products of larch cone pyrolysis. The properties of conifer cone biochar create the possibility of using it as an adsorbent in water and wastewater treatment as well as in production of filters and activated carbon.     

In situ formation of AgNPs on <Emphasis Type="Italic">S. cerevisiae</Emphasis> surface as bionanocomposites for bacteria killing and heavy metal removal

Novel bionanocomposites, S. cerevisiae–AgNPs, were synthesized by in situ formation of AgNPs on S. cerevisiae surface using fulvic acids as reductants under simulated sunlight. S. cerevisiae–AgNPs were characterized using UV–Vis spectroscopy, scanning electron microscope, transmission electron microscope and Fourier transform infrared spectroscopy. These analyses showed that AgNPs were distributed on the surface of S. cerevisiae. The application of S. cerevisiae–AgNPs in bacteria killing and heavy metal removal was studied. S. cerevisiae–AgNPs effectively inhibited the growth of E. coli with increasing concentrations of S. cerevisiae–AgNPs. E. coli was killed completely at high concentration S. cerevisiae–AgNPs (e.g., 100 or 200 µg mL^?1). S. cerevisiae–AgNPs as excellent heavy metal absorbents also have been studied. Using Cd²⁺ as model heavy metal, batch experiments confirmed that the adsorption behavior fitted the Langmuir adsorption isotherms and the Cd²⁺ adsorption capacity of S. cerevisiae–AgNPs was 15.01 mg g^?1. According to adsorption data, the kinetics of Cd²⁺ uptake by S. cerevisiae–AgNPs followed pseudo second-order kinetic model. Moreover, S. cerevisiae–AgNPs possessed ability of different heavy metals’ removal (e.g., Cr⁵⁺, As⁵⁺, Pb²⁺, Cu²⁺, Mn²⁺, Zn²⁺, Hg²⁺, Ni²⁺). The simulated contaminated water containing E. coli, Cd²⁺ and Pb²⁺ was treated using S. cerevisiae–AgNPs. The results indicated that the bionanocomposites can be used to develop antibacterial agents and bioremediation agents for water treatment.     

Adsorption of copper (II) on mesoporous silica: the effect of nano-scale confinement

Nano-scale spatial confinement can alter chemistry at mineral–water interfaces. These nano-scale confinement effects can lead to anomalous fate and transport behavior of aqueous metal species. When a fluid resides in a nanoporous environments (pore size under 100 nm), the observed density, surface tension, and dielectric constant diverge from those measured in the bulk. To evaluate the impact of nano-scale confinement on the adsorption of copper (Cu²⁺), we performed batch adsorption studies using mesoporous silica. Mesoporous silica with the narrow distribution of pore diameters (SBA-15; 8, 6, and 4 nm pore diameters) was chosen since the silanol functional groups are typical to surface environments. Batch adsorption isotherms were fit with adsorption models (Langmuir, Freundlich, and Dubinin–Radushkevich) and adsorption kinetic data were fit to a pseudo-first-order reaction model. We found that with decreasing pore size, the maximum surface area-normalized uptake of Cu²⁺ increased. The pseudo-first-order kinetic model demonstrates that the adsorption is faster as the pore size decreases from 8 to 4 nm. We attribute these effects to the deviations in fundamental water properties as pore diameter decreases. In particular, these effects are most notable in SBA-15 with a 4-nm pore where the changes in water properties may be responsible for the enhanced Cu mobility, and therefore, faster Cu adsorption kinetics.     

Evaluation of hydrogeochemical characteristics of phreatic alluvial aquifers in southeastern coastal belt of Prakasam district, South India

The assessment of hydrogeochemical processes that govern the water quality of inland freshwater aquifers in coastal environment, especially in Indian sub-continent, is occasionally attempted. To bridge the gap, a detail hydrochemical evaluation of groundwater occurring in coastal alluvium is attempted. Single set of high-density water sampling is done from a limited area to gain an in-depth knowledge of the processes that govern the water chemistry of the sandy aquifers. The water is of weak alkaline nature and less mineralized, EC being < 1,000 μS/cm in many samples. Major ion composition indicates that water is contaminated with excess concentration of nitrates. Ionic abundance is in the order of Cl^? > Na⁺  > Ca²⁺ > HCO₃ ^? > SO₄ ^2? > Mg²⁺  > NO₃ ^?. Na⁺ and Cl^? are almost in similar proportions implying the influence of coastal climate on water quality. The water shows modest variation in their ionic assemblage among different sample points as evident from Schoeller scheme. Groundwater can be classified into three distinct facies viz. Cl^?–Ca²⁺–Mg²⁺, Na⁺–Cl^? and Ca²⁺–Mg²⁺–HCO₃ ^? types. The ionic assemblages, their indices, ratios and cross-plots substantiate that multiple processes were involved in the evolution of the water chemistry. Among them, silicate weathering, halite dissolution, ion exchange and base exchange played prominent role in the ion enrichment of groundwater. The aquatic chemistry is further influenced and modified by marine environment, evapotranspiration and anthropogenic inputs which is authenticated by good correlation (r ² = 1) among the Na⁺–Cl^?, EC–Mg²⁺, Na⁺ and Cl^?. Gibbs plots established that evaporation is more responsible for contribution of minerals to the groundwater than aquifer material. Nitrate contamination can be attributed for poor sewerage disposal mechanism which is aggravated by fertilizer inputs, irrigation practices and agriculture activity. A contrasting correlation (r ² ≥90 to <0.40) among select pairs of ions reassures dissimilar source of those ions, involvement of multiple processes and limited interaction of formation water with aquifer material.     

Geochemical alterations in surface waters of Govind Ballabh Pant Sagar,Northern Coalfield,India

Major ions showed high concentrations, ionic strength and chemical activity in the surface waters of Govind Ballabh Pant Sagar reservoir. Various geochemical ratios showed the dominance of silicate over carbonate weathering and major ions such as Na⁺ + K⁺ account for about 52 % of the cation budget. The high Na⁺ and K⁺ showed sedimentation of rock/coal particles consisting of highly weathered silicate minerals contributed by the discharge of mine water, fly ash mixing during transportation, etc. Further, Ca²⁺ + Mg²⁺/Na⁺ + K⁺ ratio was <1 (0.92) indicating the occurrence of silicate weathering in the reservoir catchment. The comparative assessment showed that the proportion of Ca²⁺ + Mg²⁺/Na⁺ + K⁺ tends to be lower along the coal mining belts compared to non-coal mining regions in the world. The Ca²⁺/SO₄ ^2? ratio <1 revealed not only H₂CO₃ but H₂SO₄ also acting as a source of protons for rock weathering. The cause underlying these differences can be related directly to geological substrate and anthropogenic activities.     

Hydrochemistry of groundwater (GW) and surface water (SW) for assessment of fluoride in Chinnaeru river basin,Nalgonda district, (AP) India

Hydrochemical studies were conducted in Chinnaeru river basin of Nalgonda district, Andhra Pradesh, India, to explore the causes of high fluorides in groundwater and surface water causing a widespread incidence of fluorosis in local population. The concentration of fluoride in groundwater ranges from 0.4 to 2.9 and 0.6 to 3.6 mg/l, stream water ranges from 0.9 to 3.5 and 1.4 to 3.2 mg/l, tank water ranges from 0.4 to 2.8 and 0.9 to 2.3 mg/l, for pre- and post-monsoon periods, respectively. The modified Piper diagram reflects that the water belongs to Ca²⁺–Mg²⁺–HCO₃ ^? to Na⁺–HCO₃ ^? facies. Negative chloroalkali indices in both the seasons prove that ion exchange between Na⁺ and K⁺ in aquatic solution took place with Ca²⁺ and Mg²⁺ of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water–rock interaction is responsible for major ion chemistry of groundwater/surface water. High fluoride content in groundwater was attributed to continuous water–rock interaction during the process of percolation with fluorite bearing country rocks under arid, low precipitation, and high evaporation conditions. The low calcium content in rocks and soils, and the presence of high levels of sodium bicarbonate are important factors favouring high levels of fluoride in waters. The basement rocks provide abundant mineral sources of fluoride in the form of amphibole, biotite, fluorite, mica and apatite.     

Optimization of ammonia removal by ion-exchange resin using response surface methodology

The ability of ion-exchange resin for ammonia removal from aqueous solution was studied. The results showed that Amberlite ion-exchange resin was effective in removing ammonia from aqueous solution. Factorial design and response surface methodology were applied to evaluate and optimize the effects of pH, resin dose, contact time, temperature and initial ammonia concentration. Low pH condition was preferred with the optimum pH found to be 6. High resin dose generated high removal rate and low exchange capacity. Results of factorial design and response surface methodology showed that temperature was not a significant parameter. The model prediction was in good agreement with observed data (R ² = 0.957). The optimum Q _e was 28.78 mg/g achieved at pH = 6 and initial TAN concentration of 3000 mg/L. The kinetics followed the pseudo-second-order kinetic model (R ² = 0.999). Equilibrium data were fitted to Langmuir and Freundlich isotherm models with Langmuir model providing a slightly better predication (R ² = 0.996). The resin was completely regenerated by 2 N H₂SO₄.