Bedeutung und Verhalten von Arsen in der Hydrosphäre

The redox speciation of the inorganic arsenic species As(III) and As(V) has deep influence on the element's toxicity and mobility. In groundwater sorption and redox processes occur with respect to the solid phase and the soluble arsenic species. Thereby manganese oxides and iron hydroxides play an important role. Manganese(IV) oxides are known as effective oxidants of As(III), iron(III) hydroxides surface bind both species by surface complexation. The task of this article is to give a short overview concerning the global cycling and behavior of arsenic and then focus on the redox behavior in the aquatic system influenced by manganese oxides and iron hydroxides. Results of previous investigations are shown and expanded by new findings of own studies. Studies were carried out under controlled geochemical conditions using batch systems with arsenic and MnO ₂ and FeOOH, respectively. The sorption and redox processes were investigated using extraction methods combined with solid phase surface analyses by XANES. The results indicate a slow oxidation process of As(III) at the iron hydroxide surface.     

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.     

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.     

Anoxic oxidation of arsenite linked to denitrification in sludges and sediments

In this study, denitrification linked to the oxidation of arsenite (As(III)) to arsenate (As(V)) was shown to be a widespread microbial activity in anaerobic sludge and sediment samples that were not previously exposed to arsenic contamination. When incubated with 0.5 mM As(III) and 10 mM NO₃⁻, the anoxic oxidation of As(III) commenced within a few days, achieving specific activities of up to 1.24 mmol As(V) formed g⁻¹ volatile suspended solids d⁻¹ due to growth (doubling times of 0.74-1.4 d). The anoxic oxidation of As(III) was partially to completely inhibited by 1.5 and 5 mM As(III), respectively. Inhibition was minimized by adding As(III) adsorbed onto activated aluminum (AA). The oxidation of As(III) was shown to be linked to the complete denitrification of NO₃⁻ to N₂ by demonstrating a significantly enhanced production of N₂ beyond the background endogenous production as a result of adding As(III)-AA to the cultures. The N₂ production corresponded closely the expected stoichiometry of the reaction, 2.5 mol As(III) mol⁻¹ N₂-N. The oxidation of As(III) linked to the use of common-occurring nitrate as an electron acceptor may be an important missing link in the biogeochemical cycling of arsenic.     

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.     

Preparation and evaluation of iron–chitosan composites for removal of As(III) and As(V) from arsenic contaminated real life groundwater

A study on the removal of arsenic from real life groundwater using iron–chitosan composites is presented. Removal of arsenic(III) and arsenic(V) was studied through adsorption at pH 7.0 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir adsorption models and the various model parameters were evaluated. The monolayer adsorption capacity from the Langmuir model for iron chitosan flakes (ICF) (22.47 ± 0.56 mg/g for As(V) and 16.15 ± 0.32 mg/g for As(III)) was found to be considerably higher than that obtained for iron chitosan granules (ICB) (2.24 ± 0.04 mg/g for As(V); 2.32 ± 0.05 mg/g for As(III)). Anions including sulfate, phosphate and silicate at the levels present in groundwater did not cause serious interference in the adsorption behavior of arsenate/arsenite. The column regeneration studies were carried out for two sorption–desorption cycles for both As(III) and As(V) using ICF and ICB as sorbents. One hundred and forty-seven bed volumes of As(III) and 112 bed volumes of As(V) spiked groundwater were treated in column experiments using ICB, reducing arsenic concentration from 500 to <10 μg/l. The eluent used for the regeneration of the spent sorbent was 0.1 M NaOH. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to <10 μg/l from real life arsenic contaminated groundwater samples.     

Oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol by means of Fe(III)-homogeneous photocatalysis and algal toxicity assessment of the treated solutions

Chlorophenols are used worldwide as broad-spectrum biocides and fungicides. They have half-life times in water from 0.6 to 550 h and in sediments up to 1700 h and, due to their numerous origins, they can be found in wastewaters, groundwaters or soils. Moreover, chlorophenols are not readily biodegradable.Recently, classic Advanced Oxidation Processes (AOP) have been proposed for their abatement in an aqueous solution. This paper investigates the oxidation of 2,4-dichlorophenol and 3,4-dichlorophenol, at starting concentrations of 6.1 · 10⁻⁵ mol L⁻¹, in aqueous solutions through Fe(III)/O₂ homogeneous photocatalysis under UV light (303 ÷ 366 nm). The Fe(III)/O₂ homogeneous photocatalysis is less expensive than using H₂O₂ due to the capability of Fe(III) to produce OH radicals, if irradiated with an UVA radiation, and of oxygen to re-oxidize ferrous ions to ferric ones when dissolved in solution. The results show that the best working conditions, for both compounds, are found for pH = 3.0 and initial Fe(III) concentration equal to 1.5·10⁻⁴ mol L⁻¹ although the investigated oxidizing system can be used even at pH close to 4.0 but with slower abatement kinetics. Toxicity assessment on algae indicates that treated solutions of 2,4-dichlorophenol are less toxic on algae Pseudokirchneriella subcapitata if compared to not treated solutions whereas in the case of 3,4-dichlorophenol only the samples collected during the runs at 20 and 60 min are capable of inhibiting the growth of the adopted organism.The values of the kinetic constant for the photochemical re-oxidation of iron (II) to iron (III) and for HO attack to intermediates are evaluated by a mathematical model for pH range of 2.0-3.0 and initial Fe(III) concentrations range of 1.5 · 10⁻⁵-5.2 · 10⁻⁴ mol L⁻¹.     

Adsorption and heterogeneous oxidation of As(III) on ferrihydrite

Redox transformation of arsenic strongly influences its fate and transport in the environment. It is of interest to investigate heterogeneous oxidation of As(III) on the surface of major metal oxide in sediments. Whether As(III) can be oxidized on ferrihydrite and the role ferrihydrite plays as catalyst or oxidant are inconsistent in previous researches. In this work, oxidation of As(III) on ferrihydrite was studied by analysis of dissolved and adsorbed As(III) and As(V) quantitatively and qualitatively. X-ray absorption near edge spectroscopy (XANES) and pH_pznpc (point of zero net proton charge) of ferrihydrite with adsorbed As(III) showed clear evidence for partial oxidation on ferrihydrite. Oxidation of As(III) occurred when it was brought to contact with ferrihydrite at high Fe/As molar ratio (i.e. 50, 200). The concentration of As(V) in solid phase increased gradually while adsorbed As(III) concentration dropped. Fe(II) was not detectable during the oxidation of As(III). These results showed that ferrihydrite had the catalytic effect on oxidation of As(III). Only a fraction of As(III) was oxidized even when the system was exposed to air. The effects of ferrihydrite aging, media pH, coexistence of ions on As(III) oxidation were also investigated. The results suggest that catalytic oxidation of As(III) on ferrihydrite may play a role in geochemical cycling of arsenic in environment.     

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.     

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh

Groundwater and core sediments of two boreholes (to a depth of 50 m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40 m of depth) range from 2.8 μg L⁻¹ to 462.3 μg L⁻¹. Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55 mg kg⁻¹) were found within the upper 40 m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO₃ with high concentrations of As, Fe and Mn but low levels of NO₃⁻ and SO₄²⁻. Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.     

In situ treatment of arsenic contaminated groundwater

Groundwater in a sand and gravel aquifer was contaminated by arsenic compounds. The extent and the As concentration of the polluted groundwater plume decreased from 1971 to 1975, whereas the content of free dissolved oxygen increased. High As concentrations (> 1 mg/1) occured in groundwater with typical characteristics of a “reduced” water with negative Eh values and high concentrations of dissolved iron (up to 140 mg/1 in 1971). When plotted into an As stability field diagram, the higher values (> 1 mg As/1) coincided with the fields of trivalent As species, whereas the lower values (< 0.1 mg As/1) fitted to the fields of the pentavalent arsenic species. Therefore it was concluded that an improvement of the oxygen supply should accelerate the natural precipitation processes. By injection of 29,000 kg KMnO₄ into 17 wells and piezometers the soluble As (III) species were oxidized to As (V) species, which were precipitated as FeAsO₄ or Mn₃(AsO₄)₂ or co-precipitated with Mn- and Fe-hydroxides.     

Removal of As(III) and As(V) by Tin(II) compounds

The retention capacity for arsenic species of new nanomaterials based on tin(II) inorganic oxides or hybrid (inorganic and organic) materials was studied. The synthesis of a polymer-metal complex was performed with poly(acrylic acid) and tin(II) chloride. Poly(AA)-Sn(II) with 10 and 20 wt% of tin and a structure with a mol ratio tin:carboxylate group of 1:1, were characterized. These compounds with 10 and 20 wt% of tin content were used to compare the arsenic removal capability through the liquid-phase polymer-based retention, (LPR), technique. Also, tin oxide was prepared by adding alkaline solution to tin(II) chloride salt. The intermediate tin compound was studied by UV-Vis spectroscopy at different pH values and quantified by potentiometric titration. The solid structure is characterized by Fourier transformed infrared spectroscopy, X-ray diffraction, and specific area BET (N₂). Removal of arsenite and arsenate species from solution by hydrolysated tin was carried out by LPR technique with ultrafiltration membranes and a fixed-bed column unsupported or supported on SiO₂. In all these cases, a washing method at constant pH was applied. The arsenic retention ability depended on the class of tin compounds prepared, with a higher efficiency for arsenic being observed at basic pH for soluble complex poly(AA)-Sn(II) than that for tin hydroxide or hydrolysate of Sn⁺².     

Natürliche Schadstoffrückhalteprozesse für Arsen und Kupfer am Standort einer ehemaligen Buntfarbenfabrik

The sharply confined pattern of arsenic groundwater contamination at the site of a historic dye factory suggests that natural attenuation processes are active and efficient. The supporting data included sequential soil extractions combined with analyses of other soil properties like carbonate content, the loss of ignition and cation exchange capacity and the extraction characteristics of the original dye pigment. The results point to iron oxides and iron hydroxides as the most important adsorbers for copper and arsenic. The attenuation of copper can be estimated to be very efficient mainly due to its pH-controlled low solubility. Besides the specific adsorption to iron oxides, however, arsenic exhibits a rather large, loosely bound and easily exchangeable fraction. The speciation of arsenic in groundwater is dominated by As(V). The oxidation state of the original pigment is As(III). In some parts of the aquifer where suboxic conditions prevail, this oxidation state is conserved. In oxic zones of the aquifer, oxidation to the pentavalent form As(V) takes place.     

Speciation and distribution of vanadium in drinking water iron pipe corrosion by-products

Vanadium (V) when ingested from drinking water in high concentrations (> 15 μg L^− 1) is a potential health risk and is on track to becoming a regulated contaminant. High concentrations of V have been documented in lead corrosion by-products as Pb₅(V⁵⁺O₄)₃Cl (vanadinite) which, in natural deposits is associated with iron oxides/oxyhydroxides, phases common in iron pipe corrosion by-products. The extent of potential reservoirs of V in iron corrosion by-products, its speciation, and mechanism of inclusion however are unknown. The aim of this study is to assess these parameters in iron corrosion by-products, implementing synchrotron-based μ-XRF mapping and μ-XANES along with traditional physiochemical characterization. The morphologies, mineralogies, and chemistry of the samples studied are superficially similar to typical iron corrosion by-products. However, we found V present as discrete grains of Pb₅(V⁵⁺O₄)₃Cl likely embedded in the surface regions of the iron corrosion by-products. Concentrations of V observed in bulk XRF analysis ranged from 35 to 899 mg kg^− 1. We calculate that even in pipes with iron corrosion by-products with low V concentration, 100 mg kg^− 1, as little as 0.0027% of a 0.1-cm thick X 100-cm long section of that corrosion by-product needs to be disturbed to increase V concentrations in the drinking water at the tap to levels well above the 15 μg L^− 1 notification level set by the State of California and could adversely impact human health. In addition, it is likely that large reservoirs of V are associated with iron corrosion by-products in unlined cast iron mains and service branches in numerous drinking water distribution systems.     

Magnetic binary oxide particles (MBOP): a promising adsorbent for removal of As (III) in water

Magnetic binary oxide particles (MBOP) synthesized using chitosan template has been investigated for uptake capacity of arsenic (III). Batch experiments were performed to determine the rate of adsorption and equilibrium isotherm and also effect of various rate limiting factors including adsorbent dose, pH, optimum contact time, initial adsorbate concentration and influence of presence cations and anions. It was observed that uptake of arsenic (III) was independent of pH of the solution. Maximum adsorption of arsenic (III) was ∼99% at pH 7.0 with dose of adsorbent 1 g/L and initial As (III) concentration of 1.0 mg/L at optimal contact time of 14 h. The adsorption equilibrium data fitted well to Langmuir and Freundlich isotherm. The maximum adsorption capacity of adsorbent was 16.94 mg/g. With increase in concentration of Ca²⁺, Mg²⁺ from 50 mg/L to 600 mg/L, adsorption of As (III) was significantly reduced while for Fe³⁺ the adsorption of arsenic (III) was increased with increase in concentration. Temperature study was carried out at 293 K, 303 K and 313 K reveals that the adsorption process is exothermic nature. A distinct advantage of this adsorbent is that adsorbent can readily be isolated from sample solutions by application of an external magnetic field. Saturation magnetization is a key factor for successful magnetic separation was observed to be 18.78 emu/g which is sufficient for separation by conventional magnate.     

Comparative study of arsenic removal by iron using electrocoagulation and chemical coagulation

This research studied As(III) and As(V) removal during electrocoagulation (EC) in comparison with FeCl₃ chemical coagulation (CC). The study also attempted to verify chlorine production and the reported oxidation of As(III) during EC. Results showed that As(V) removal during batch EC was erratic at pH 6.5 and the removal was higher-than-expected based on the generation of ferrous iron (Fe²⁺) during EC. As(V) removal by batch EC was equal to or better than CC at pH 7.5 and 8.5, however soluble Fe²⁺ was observed in the 0.2-μm membrane filtrate at pH 7.5 (10-45%), and is a cause for concern. Continuous steady-state operation of the EC unit confirmed the deleterious presence of soluble Fe²⁺ in the treated water. The higher-than-expected As(V) removals during batch mode were presumed due to As(V) adsorption onto the iron rod oxyhydroxides surfaces prior to the attainment of steady-state operation. As(V) removal increased with decreasing pH during both CC and EC, however EC at pH 6.5 was anomalous because of erratic Fe²⁺ oxidation. The best adsorption capacity was observed with CC at pH 6.5, while lower but similar adsorption capacities were observed at pH 7.5 and 8.5 with CC and EC. A comparison of As(III) adsorption showed better removals during EC compared with CC possibly due to a temporary pH increase during EC. In contrast to literature reports, As(III) oxidation was not observed during EC, and As(III) adsorption onto iron hydroxides during EC was only 5-30% that of As(V) adsorption. Also in contrast to literature, significant Cl₂ was not generated during EC, in fact, the rods actually produced a significant chlorine demand due to reduced iron oxides on the rod. Although Cl₂ generation and As(III) oxidation are possible using a graphite anode, a combination of graphite and iron rods in the same EC unit did not produce As(III) oxidation. However, a two-stage process (graphite anode followed by iron anode in separate chambers) was effective in As(III) oxidation and removal. The competing ions, silica and phosphate interfered with As(V) adsorption during both CC and EC. However, the degree of interference depends on the concentration and presence of other competing ions. In particular, the presence of silica lowered the effect of phosphate with increasing pH due to silica’s own significant effect at high pHs.     

Geochemistry of redox-sensitive elements and sulfur isotopes in the high arsenic groundwater system of Datong Basin, China

High arsenic groundwater in the Quaternary aquifers of Datong Basin, northern China contain As up to 1820 µg/L and the high concentration plume is located in the slow flowing central parts of the basin. In this study we used hydrochemical data and sulfur isotope ratios of sulfate to better understand the conditions that are likely to control arsenic mobilization. Groundwater and spring samples were collected along two flow paths from the west and east margins of the basin and a third set along the basin flow path. Arsenic concentrations range from 68 to 670 µg/L in the basin and from 3.1 to 44 µg/L in the western and eastern margins. The margins have relatively oxidized waters with low contents of arsenic, relatively high proportions of As(V) among As species, and high contents of sulfate and uranium. By contrast, the central parts of the basin are reducing with high contents of arsenic in groundwater, commonly with high proportions of As(III) among As species, and low contents of sulfate and uranium. No statistical correlations were observed between arsenic and Eh, sulfate, Fe, Mn, Mo and U. While the mobility of sulfate, uranium and molybdenum is possibly controlled by the change in redox conditions as the groundwater flows towards central parts of the basin, the reducing conditions alone cannot account for the occurrence of high arsenic groundwater in the basin but it does explain the characteristics of arsenic speciation. With one exception, all the groundwaters with As(III) as the major As species have low Eh and those with As(V) have high Eh. Reductive dissolution of Fe-oxyhydroxides or reduction of As(V) are consistent with the observations, however no increase in dissolved Fe concentration was noted. Furthermore, water from the well with the highest arsenic was relatively oxidizing and contained mostly As(V). From previous work Fe-oxyhydroxides are speculated to exist as coatings rather than primary minerals.The wide range of δ³⁴S_[SO4] values (from − 2.5 to + 36.1‰) in the basin relative to the margins (from + 8‰ to + 15‰) indicate that sulfur is undergoing redox cycling. The highly enriched values point to sulfate reduction that was probably mediated by bacteria. The presence of monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) is also evidence of microbial reactions. The depleted signatures indicate that some oxidation of depleted sulfide occurred in the basin. It must be noted that the samples with depleted sulfur isotope values have very low sulfate concentrations and therefore even a small amount of sulfide oxidation will bias the ratio. No significant correlation was observed between δ³⁴S_[SO4] values and total arsenic contents when all the samples were considered. However, the wells in the central basin do appear to become enriched in δ³⁴S_[SO4] as arsenic concentration increases. Although there is evidence for sulfate reduction, it is clear that sulfate reduction does not co-precipitate or sequester arsenic. The one sample with high arsenic that is oxidizing cannot be explained by oxidation of pyrite and is likely an indication that there are multiple redox zones that control arsenic speciation but not necessarily its mobilization and contradict the possibility that Fe-oxyhydroxides sorb appreciable amounts of arsenic in this study area. It is evident that this basin like other two young sedimentary basins (Huhhot and Hetao in Inner Mongolia) of northern China with high arsenic groundwater is transporting arsenic at a very slow rate. The data are consistent with the possibility that the traditional models of arsenic mobilization, namely reductive dissolution of Fe-oxyhydroxides, reduction of As(V) to more mobile As(III), and bacteria mediated reactions, are active to varying degrees. It is also likely that different processes control arsenic mobilization at different locations of the basin and more detailed studies along major flow paths upgradient of the high arsenic aquifers will shed more light on the mechanisms.     

Off-line coupled electrocatalytic oxidation and liquid phase polymer based retention (EO-LPR) techniques to remove arsenic from aqueous solutions

Electrochemistry and membrane ultrafiltration methods (electro-oxidation and liquid phase polymer based retention technique, LPR, respectively) were off-line coupled to remove As(III) inorganic species from aqueous solutions. Our main objective was to achieve an efficient extraction of arsenic species by associating a polymer-assisted liquid phase retention procedure, based on the As(V) adsorption properties of cationic water-soluble polymers, with an electrocatalytic oxidation process of As(III) into its more easily removable analogue As(V). The electrocatalytic oxidation of As(III) to As(V) was performed in the presence of different water-soluble poly(quaternary ammonium) salts acting also as supporting electrolyte, i.e. poly(vinylbenzyl)trimethyl ammonium chloride, P(ClVBTA), poly[3-(methacryloylamine)propyl]trimethyl ammonium chloride, P(ClMPTA), and poly(4-vinyl-1-methylpyridinium bromide), P(BrVMP). After complete electrocatalytic conversion of As(III) into As(V), the mixtures were introduced into an LPR cell to remove the As(V)-polymer adducts. Using P(ClMPTA), P(ClVBTA), or P(BrVMP) ammonium salts in a 20:1 polymer:As(III) mol ratio at pH 8, complete (100%) retention of the arsenic was achieved. Moreover, the As(V) retention efficiency turned out to be directly related to the net charge consumed during the electrochemical conversion of As(III) to As(V).     

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.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.