Processes releasing arsenic to groundwater in the Caldes de Malavella geothermal area, NE Spain

Arsenic concentrations exceeding the World Health Organization drinking water guideline (10 μg/L) have been measured in thermal and non-thermal groundwaters from the Caldes de Malavella geothermal area (La Selva graben, NE Spain). The CO₂-rich Na-HCO₃ thermal waters (up to 60 °C at the spring) have elevated arsenic concentrations ([As_T] from 50 to 80 μg/L). The non-thermal waters are of Ca-Na-HCO₃-Cl type and have [As_T] between <1 and 200 μg/L, defining a hot-spot distribution. The present-day contribution of As from CO₂-rich thermal waters to non-thermal aquifers is very limited, as shown by the concentration of geothermal tracers such as Li and B. Redox-controlling processes appear to govern the mobility of As in the non-thermal waters. Arsenate is clearly predominant in most oxidizing groundwaters (>85% of As(V) over total As), whereas reducing, high-As groundwater reaches up to 100% in arsenite. The reductive dissolution of Fe(III) oxyhydroxides and the coupled release and reduction of adsorbed As explain the elevated dissolved arsenite (up to 190 μg/L) and Fe (up to 14 mg/L) content in the more reducing non-thermal groundwater. Conversely, the high levels of nitrate (up to 136 mg/L) ensure an oxidizing environment in most non-thermal groundwaters ([As_T] between <1 and 60 μg/L). Under these conditions, Fe(III) oxyhydroxides are stable and As release to groundwater is not related to their dissolution. Instead, dissolved arsenate concentrations up to 60 μg/L are explained by a competition for sorption sites with other species, mainly bicarbonate and silicic acid, while arsenate desorption due to pH increase is not considered a major process.     

Hybrid adsorbents based on hydrated oxides of Zr(IV), Ti(IV), Sn(IV), and Fe(III) for arsenic removal

Synthesized are hybrid organoinoragnic adsorbents based on organic resins Dowex SBR-P, Dowex Marathon II and hydrated oxides Zn(IV), Ti(IV), Sn(IV) and Fe(III). Specific conductivity was measured of the specified resins and hybrid organoinorganic adsorbents in the initial form and after absorption of ions As(V) from 10^–2 M aqueous solution of NaH₂AsO₄. Introduction of hydrated tin oxide increases ionic conductivity of organic resin Dowex SBR-P by 2.5 times. During the conversion to the arsenate form the conductivity of hybrid adsorbents changes insufficiently at the adsorption from the solution with pH 7 and increased by 2–10 times at adsorption from the solution with pH 2.     

Iron amendment and Fenton oxidation of MTBE-spent granular activated carbon

Fenton-driven regeneration of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) involves an Fe amendment step to increase the Fe content and to enhance the extent of MTBE oxidation and GAC regeneration. Four forms of iron (ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate) were amended separately to GAC. Following Fe amendment, MTBE was adsorbed to the GAC followed by multiple applications of H₂O₂. Fe retention in GAC was high (83.8-99.9%) and decreased in the following order, FeSO₄·7H₂O > Fe₂(SO₄)₃·9H₂O > Fe(NO₃)₃·9H₂O > FeCl₃. A correlation was established between the post-sorption aqueous MTBE concentrations and Fe on the GAC for all forms of Fe investigated indicating that Fe amendment interfered with MTBE adsorption. However, the mass of MTBE adsorbed to the GAC was minimally affected by Fe loading. Relative to ferric iron amendments to GAC, ferrous iron amendment resulted in lower residual iron in solution, greater Fe immobilization in the GAC, and less interference with MTBE adsorption. MTBE oxidation was Fe limited and no clear trend was established between the counter-ion (SO₄²⁻, Cl⁻, NO₃⁻) of the ferric Fe amended to GAC and H₂O₂ reaction, MTBE adsorption, or MTBE oxidation, suggesting these processes are anion independent.     

Chemical reactions between arsenic and zero-valent iron in water

Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen.     

A comparative study of As(III) and As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy

The sorption of the arsenite (AsO₃³⁻) and the arsenate (AsO₄³⁻) ions and their conjugate acids onto iron oxides is one of main processes controlling the distribution of arsenic in the environment. The present work intends to provide a large vibrational spectroscopic database for comparison of As(III) and As(V) speciation in aqueous solutions and at the iron oxide - solution interface. With this purpose, ferrihydrite, feroxyhyte, goethite and hematite were firstly synthesized, characterized in detail and used for adsorption experiments. Raman spectra were recorded from As(III) and As(V) aqueous solutions at various pH conditions selected in order to highlight arsenic speciation. Raman Scattering and Diffuse Reflectance Infrared Fourier Transform (DRIFT) studies were carried out to examine the respective As-bonding mechanisms. The collected data were curve-fitted and discussed according to molecular symmetry concepts. X-ray Absorption Near Edge Spectroscopy (XANES) was applied to confirm the oxidation state of the sorbed species. The comprehensive spectroscopic investigation contributes to a better understanding of arsenic complexation by iron oxides.     

The effect of crude oil on arsenate adsorption on goethite

This study reports the adsorption of arsenate, As(V), on goethite (α-FeO(OH)) and oil-coated goethite at experimental conditions chosen to mimic settings of wastewater from oil fields being released into marine and freshwater bodies. Similarities are evident between the As(V)–goethite and As(V)–oil–goethite systems: i) Adsorption is fast and saturation is achieved within 180 min, ii) Reaction rates approximate to a pseudo second order rate expression and range between 6.5 and 52.3 × 10^?4 g/μmol/min, iii) Adsorption mechanisms are best described with a Langmuir model, and iv) Adsorption capacity rises with decreasing pH reflecting the increase of positive charges on the goethite surface. A difference is discernable in that the adsorption of As(V) is reduced significantly when the goethite is coated with oil. The similar experimental macroscopic observations for both systems, i.e., Langmuir model fits, reaction rates, and the effect of pH and ionic strength (I), suggest that the oil reduces the effective and/or reactive surface area. The zeta potential (ζ) indicates that the oil coating also changes the surface charge of the goethite, shifting the pH point of zero charge from 9.8 to about 3, thus contributing to the reduced As(V) adsorption. FTIR spectra show that As(V) interacts with the carbonyl functional groups of the oil. Our results suggest that oil-covered goethite significantly reduces the adsorption of As(V) and this points to a potentially significant indirect effect of oil on the cycling of As(V) and other oxyanions in oil polluted waters.     

Removal of arsenic from water: Effect of calcium ions on As(III) removal in the KMnO4–Fe(II) process

A novel KMnO₄–Fe(II) process was developed in this study for As(III) removal. The optimum As(III) removal was achieved at a permanganate dosage of 18.6 μM. At the optimum dosage of permanganate, the KMnO₄–Fe(II) process was much more efficient than the KMnO₄–Fe(III) process for As(III) removal by 15–38% at pH 5–9. The great difference in As(III) removal in these two processes was not ascribed to the uptake of arsenic by the MnO₂ formed in situ but to the different properties of conventional Fe(III) and the Fe(III) formed in situ. It was found that the presence of Ca²⁺ had limited effects on As(III) removal under acidic conditions but resulted in a significant increase in As(III) removal under neutral and alkaline conditions in the KMnO₄–Fe(II) process. Moreover, the effects of Ca²⁺ on As(III) removal in the KMnO₄–Fe(II) process were greater at lower permanganate dosage when Fe(II) was not completely oxidized by permanganate. This study revealed that the improvement of As(III) removal at pH 7–9 in the KMnO₄–Fe(II) process by Ca²⁺ was associated with three reasons: (1) the specific adsorption of Ca²⁺ increased the surface charge; (2) the formation of amorphous calcium carbonate and calcite precipitate that could co-precipitate arsenate; (3) the introduction of calcium resulted in more precipitated ferrous hydroxide or ferric hydroxide. On the other hand, the enhancement of arsenic removal by Ca²⁺ under acidic conditions was ascribed to the increase of Fe retained in the precipitate. FTIR tests demonstrated that As(III) was removed as arsenate by forming monodentate complex with Fe(III) formed in situ in the KMnO₄–Fe(II) process when KMnO₄ was applied at 18.6 μM. The strength of the “non-surface complexed” As–O bonds of the precipitated arsenate species was enhanced by the presence of Ca²⁺ and the complexation reactions of arsenate with Fe(III) formed in situ in the presence or absence of Ca²⁺ were proposed.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

Implications of organic matter on arsenic mobilization into groundwater: Evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca²⁺, Mg²⁺, K⁺, Na⁺), anions (Cl⁻, NO₃⁻, SO₄²⁻), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 μg/L (mean 62.4 ± 93.1 μg/L, n = 20), 16.4-73.7 μg/L (mean 28.5 ± 22.4 μg/L, n = 10) and 4.6-215.4 μg/L (mean 30.7 ± 62.1 μg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m⁻¹ mg⁻¹ L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R² = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.     

Adsorption of arsenic from a Nova Scotia groundwater onto water treatment residual solids

Water treatment residual solids were examined in batch adsorption and column adsorption experiments using a groundwater from Halifax Regional Municipality that had an average arsenic concentration of 43 μg/L (±4.2 μg/L) and a pH of 8.1. The residual solids studied in this paper were from five water treatment plants, four surface water treatment plants that utilized either alum, ferric, or lime in their treatment systems, and one iron removal plant. In batch adsorption experiments, iron-based residual solids and lime-based residual solids pre-formed similarly to GFH, a commercially-available adsorbent, while alum-based residual solids performed poorly. Langmuir isotherm modeling showed that ferric residuals had the highest adsorptive capacity for arsenic (Q_max = 2230 mg/kg and 42,910 mg/kg), followed by GFH (Q_max = 640 mg/kg), lime (Q_max = 160 mg/kg) and alum (Q_max = <1 mg/kg and 3 mg/kg). Similarly, the maximum arsenic removal was >93% for the ferric and lime residuals and GFH, while the maximum arsenic removal was <49% for the alum residuals under the same conditions. In a column adsorption experiment, ferric residual solids achieved arsenic removal of >26,000 bed volumes before breakthrough past 10 μg As/L, whereas the effluent arsenic concentration from the GFH column was under the method detection limit at 28,000 bed volumes. Overall, ferric and lime water treatment residuals were promising adsorbents for arsenic adsorption from the groundwater, and alum water treatment residuals did not achieve high levels of arsenic adsorption.     

Anchorage of iron hydro(oxide) nanoparticles onto activated carbon to remove As(V) from water

The adsorption of arsenic (V) by granular iron hydro(oxides) has been proven to be a reliable technique. However, due to the low mechanical properties of this material, it is difficult to apply it in full scale water treatment. Hence, the aim of this research is to develop a methodology to anchor iron hydro(oxide) nanoparticles onto activated carbon, in which the iron hydro(oxide) nanoparticles will give the activated carbon an elevated active surface area for arsenic adsorption and also help avoid the blockage of the activated carbon pores. Three activated carbons were modified by employing the thermal hydrolysis of iron as the anchorage procedure. The effects of hydrolysis temperature (60-120 °C), hydrolysis time (4-16 h), and FeCl₃ concentration (0.4-3 mol Fe/L) were studied by the surface response methodology. The iron content of the modified samples ranged from 0.73 to 5.27%, with the higher end of the range pertaining to the carbons with high oxygen content. The materials containing smaller iron hydro(oxide) particles exhibited an enhanced arsenic adsorption capacity. The best adsorbent material reported an arsenic adsorption capacity of 4.56 mg As/g at 1.5 ppm As at equilibrium and pH 7.     

Sonophotolytic degradation of azo dye reactive black 5 in an ultrasound/UV/ferric system and the roles of different organic ligands

The sonophotolytic advance oxidation system (US/UV/Fe³⁺) could achieve synergistic degradation of reactive black 5 (RB5), as compared to UV/Fe³⁺ and US/Fe³⁺ systems. A synergy factor of 2.5 based on the pseudo-first-order degradation rate constant (k_obs) was found, along with enhancements in organic detoxification and mineralization. The presence of organic ligands could affect the US/UV/Fe³⁺ system differently. Oxalate, citrate, tartrate and succinate could enhance the RB5 degradation, while NTA and EDTA exhibited strong inhibitions. The influence of these ligands on k_obs(RB5) in the US/UV/Fe(III)-ligand systems followed the sequence of oxalate > tartrate > succinate > citrate > without ligand > NTA > EDTA, while they could be degraded simultaneously with the k_obs(ligand) order of oxalate > citrate > tartrate > succinate > NTA > EDTA. Monitoring of iron species and the generated H₂O₂ and •OH revealed that the ligands in the US/UV/Fe(III)-ligand system could play different mechanistic roles: (1) promoting H₂O₂ production, (2) accelerating Fenton reaction, and (3) competing with RB5 for reacting with •OH. Among the ligands, oxalate exhibited the most significant enhancement of RB5 oxidation in the sonophotolytic system, and the process was pH-dependent. An initial reaction lag in RB5 degradation was observed when Fe²⁺ was used in lieu of Fe³⁺ as the catalyst in the sonophotolytic system.     

Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron

The kinetics of Se(IV) removal by zero valent iron (ZVI) open to the air as a function of pH and the involved mechanisms were investigated in this study. The specific rate constants of Se(IV) removal by ZVI decreased from 92.87 to 6.87 L h⁻¹ m⁻² as pH increased from 4.0 to 7.0. The positive correlation between the removal rate of Se(IV) and the generation rate of Fe(II) and the depression of Se(IV) removal in the presence of 1,10-phenanthroline indicated that both ZVI and adsorbed Fe(II) on ZVI surface contributed to the reductive removal of Se(IV). The soft X-ray STXM measurement confirmed the adsorption of Fe(II) on the surface of ZVI and freshly formed ferric (hydr)oxides. Se(IV) was removed by adsorption followed by reduction to Se(0) on ZVI surface at pH 4.0–7.0, as revealed by XANES spectra. A core-shell structure was observed when ZVI reacted with Se(IV)-containing solution for 3 h at pH 6.0. Se(IV) was reduced to Se(0) and co-precipitated with the freshly formed Fe(III), forming the shell surrounding the iron core. After reaction for 24 h, the generated Se(0) was surrounded by multiple layers of Fe(III) oxides/hydroxides. SEM images and XRD patterns revealed that the corrosion products of ZVI at pH 6.0 transformed from amorphous iron hydroxides to lepidocrocite (γ-FeOOH) as reaction proceeded. The final corrosion products of ZVI contained both lepidocrocite and goethite at pH 5.0 while they were X-ray amorphous at pH 4.0 and 7.0.     

Mobilization of arsenic and other naturally occurring contaminants in groundwater of the Main Ethiopian Rift aquifers

This study investigates the mechanisms of arsenic (As) and other naturally occurring contaminants (F⁻, U, V, B, and Mo) mobilization from Quaternary sedimentary aquifers of the Main Ethiopian Rift (MER) and their enrichment in the local groundwater. The study is based on systematic measurements of major and trace elements as well as stable oxygen and hydrogen isotopes in groundwater, coupled with geochemical and mineralogical analyses of the aquifer rocks. The Rift Valley aquifer is composed of rhyolitic volcanics and Quaternary lacustrine sediments. X-ray fluorescence (XRF) results revealed that MER rhyolites (ash, tuff, pumice and ignimbrite) and sediments contain on average 72 wt. % and 65 wt. % SiO₂, respectively. Petrographic studies of the rhyolites indicate predominance of volcanic glass, sanidine, pyroxene, Fe-oxides and plagioclase. The As content in the lacustrine sediments (mean = 6.6 mg/kg) was higher than that of the rhyolites (mean: 2.5 mg/kg). The lacustrine aquifers of the Ziway-Shala basin in the northern part of MER were identified as high As risk zones, where mean As concentration in groundwater was 22.4 ± 33.5 (range of 0.60–190 μg/L) and 54% of samples had As above the WHO drinking water guideline value of 10 μg/L. Field As speciation measurements showed that most of the groundwater samples contain predominantly (∼80%) arsenate-As(V) over arsenite-As(III) species. The As speciation together with field data of redox potential (mean Eh = +73 ± 65 mV) and dissolved-O₂ (6.6 ± 2.2 mg/L) suggest that the aquifer is predominantly oxidative. Water-rock interactions, including the dissolution of volcanic glass produces groundwater with near-neutral to alkaline pH (range 6.9–8.9), predominance of Na–HCO₃ ions, and high concentration of SiO₂ (mean: 85.8 ± 11.3 mg/L). The groundwater data show high positive correlation of As with Na, HCO₃¯, U, B, V, and Mo (R² > 0.5; p < 0.001). Chemical modeling of the groundwater indicates that Fe-oxides and oxyhydroxides minerals were saturated in the groundwater, suggesting that the As reactivity is controlled by adsorption/desorption processes with these minerals. The data show that As and other oxyanion-forming elements such as U, B, Mo, and V had typically higher concentrations at pH > ∼8, reflecting the pH-dependence of their mobilization. Based on the geochemical and stable isotope variations we have established a conceptual model for the occurrence of naturally occurring contaminants in MER groundwater: 1) regional groundwater recharge from the Highland, along the Rift margins, followed by lateral flow and water–rock interactions with the aquifer rocks resulted in a gradual increase of the salinity and naturally occurring contaminants towards the center of the valley; and (2) local δ¹⁸O-rich lake water recharge into adjacent shallow aquifers, followed by additional mobilization of As and other oxyanion-forming elements from the aquifer rocks. We posit that the combined physical-chemical conditions of the aquifers such as oxidizing state, Na–HCO₃ composition, and pH>∼8 lead to enhanced mobilization of oxyanion-forming elements from Fe-oxides and consequently contamination of local groundwater. These geochemical conditions characterize groundwater resources along the Eastern African Rift and thus constitute a potential threat to the quality of groundwater in larger areas of Eastern Africa.     

As(V) removal using carbonized yeast cells containing silver nanoparticles

The present study involves the development of adsorbent containing silver nanoparticles for arsenate removal using silver reducing property of a novel yeast strain Saccharomyces cerevisiae BU-MBT-CY1 isolated from coconut cell sap. Biological reduction of silver by the isolate was deduced at various time intervals. The yeast cells after biological silver reduction were harvested and subjected to carbonization at 400 °C for 1 h and its properties were analyzed using Fourier Transform Infra-Red spectroscopy, X-ray diffraction, scanning electron microscope attached with energy dispersive spectroscopy and transmission electron microscope. The average size of the silver nanoparticles present on the surface of the carbonized silver containing yeast cells (CSY) was 19 ± 9 nm. The carbonized control yeast cells (CCY) did not contain any particles on its surface. As(V) adsorption efficiency of CCY and CSY was deduced in batch mode by varying parameters like contact time, initial concentration, and pH. Desorption studies were also carried out by varying the pH. The experimental data were fitted onto Langmuir and D-R Isotherms and Lagergren and pseudo second order kinetic models. The CSY was more efficient in arsenate removal when compared to CCY.     

Removal of arsenite and arsenate ions from aqueous solution by basic yttrium carbonate

A new method has been developed to remove arsenite and arsenate ions from aquatic systems by using basic yttrium carbonate (BYC). Various parameters such as pH, anion concentration and reaction time were studied to establish optimum conditions. The removal by adsorption of arsenite and arsenate ions was found to be > 99% depending on initial concentration in the pH range of 9.8–10.5 and 7.5–9.0, respectively. The arsenate was also removed by precipitation at pH lower than 6.5 due to dissolution of BYC. The kinetic study shows that the adsorption follows the first order reaction. The adsorption isotherms of these anions were also studied at different temperatures. The equilibrium data fit well in the Langmuir model of adsorption. The Langmuir constants were calculated at different temperatures and the adsorption capacity for both anions increases with temperature. Anions such as Cl⁻, Br⁻, I⁻, NO⁻₃ and SO²⁻₄ have no interference in the removal process. The mechanism of the removal by adsorption was interpreted in terms of the surface charge and ligand orientation of BYC. The method was applied on synthetic wastewaters. Arsenite was oxidized to arsenate by 3% hydrogen peroxide. The yttrium was regenerated as basic yttrium carbonate.     

Cadmium adsorption in freshwaters — a quantitative appraisal of the literature

Information from 33 studies of cadmium adsorption on amorphous and crystalline hydrous iron oxides, clays, silica, humic solids, manganese oxides and natural sediments has been collated. The results have been transferred to a unified data base using a surface complexion model, and are presented in terms of conditional adsorption constants as a function of pH. The adsorption constants for a given substrate at a fixed pH generally agree within an order of magnitude. This is reasonable given the wide range of experimental conditions employed. The affinity of the substrates (on a weight basis) for cadmium appears to follow the order Mn > Fe_am > chlorite (montmorillonite?) > Fe_cryst. = illite = humics > kaolinite > silica.Application of the experimental conditional adsorption constants for the individual substrates to a model suspended sediment predicts adsorption levels similar to those found in experiments with real sediments. The results confirm the potentially important role played by hydrous oxides of iron and manganese. They also emphasise that cadmium is in a very dynamic regime with respect to adsorption in many freshwaters. Deficiencies in our present information on cadmium adsorption are highlighted and suggestions made for future studies.     

Microbial transformations of arsenic: mobilization from glauconitic sediments to water

In the Inner Coastal Plain of New Jersey, arsenic (As) is released from glauconitic sediment to carbon- and nutrient-rich shallow groundwater. This As-rich groundwater discharges to a major area stream. We hypothesize that microbes play an active role in the mobilization of As from glauconitic subsurface sediments into groundwater in the Inner Coastal Plain of New Jersey. We have examined the potential impact of microbial activity on the mobilization of arsenic from subsurface sediments into the groundwater at a site on Crosswicks Creek in southern New Jersey. The As contents of sediments 33-90 cm below the streambed were found to range from 15 to 26.4 mg/kg, with siderite forming at depth. Groundwater beneath the streambed contains As at concentrations up to 89 μg/L. Microcosms developed from site sediments released 23 μg/L of As, and active microbial reduction of As(V) was observed in microcosms developed from site groundwater. DNA extracted from site sediments was amplified with primers for the 16S rRNA gene and the arsenate respiratory reductase gene, arrA, and indicated the presence of a diverse anaerobic microbial community, as well as the presence of potential arsenic-reducing bacteria. In addition, high iron (Fe) concentrations in groundwater and the presence of iron-reducing microbial genera suggests that Fe reduction in minerals may provide an additional mechanism for release of associated As, while arsenic-reducing microorganisms may serve to enhance the mobility of As in groundwater at this site.     

Effects of hardness and alkalinity on the removal of arsenic(V) from humic acid-deficient and humic acid-rich groundwater by zero-valent iron

The effects of hardness (Ca²⁺) and alkalinity (HCO₃⁻) on arsenic(V) removal from humic acid (HA)-deficient and HA-rich groundwater by zero-valent iron (Fe⁰) were investigated using batch experiments. Arsenic, in general, is removed from groundwater possibly by adsorption and co-precipitation with the iron corrosion products. However, in the co-presence of HCO₃⁻ and Ca²⁺, the removal rate of arsenic increased with increasing concentrations of either Ca²⁺ or HCO₃⁻. It was observed that the removal of arsenic was significantly enhanced by the formation of CaCO₃ as a nucleation seed for the growth of large iron (hydr)oxide particles. In the co-existence of Ca²⁺, HCO₃⁻ and HA, the presence of HA diminished the positive role of Ca²⁺ due to the formation of Fe-humate complexes in solution and delaying of the formation of CaCO₃. As a result, the formation of the large iron (hydr)oxide particles was inhibited in the earlier stage which, in turn, affected the removal of arsenic. However, after the formation of CaCO₃ and the subsequent growth of such particles, the presence of large iron (hydr)oxide particles resulted in the rapid removing of arsenic and Fe-humate by adsorption and/or co-precipitation.