Abiotic subsurface behaviors of As(V) with Fe(II)

Subsurface geochemical behavior of As(V) with Fe(II) was studied under strict anoxic conditions. Abiotic reduction of As(V) (0.1 mM) to As(III) by aqueous Fe(II) and sorbed Fe(II) in pH range 5.0-7.0 and Fe(II)(aq) concentration (0.6-1.2 mM) was investigated along with the effect of As(V) on the oxidation of Fe(II) by dissolved oxygen (DO). Although the reduction was thermodynamically feasible for homogeneous chemical conditions, practically no As(V) reduction by aqueous Fe(II) was observed. Similarly, no sorbed As(V) reduction was observed under the heterogeneous experimental conditions by sorbed Fe(II) onto synthetic iron oxide (hematite, α-Fe?O?). Experimental results on Fe(II) oxidation by DO in the presence of 0.1 mM As(V) showed a significantly slower Fe(II) oxidation, which might be due to the formation of Fe(II)-As(V) complex in the aqueous phase. The results of this study demonstrate that As(V) is relatively stable in the presence of Fe(II) under subsurface environment and interfere the oxidation of Fe(II).     

High-valent iron-based oxidants to treat perfluorooctanesulfonate and perfluorooctanoic acid in water

Perfluoroalkyl and polyfluoroalkyl substances are occurring in consumer and industrial products. They have been found globally in the aquatic environment including drinking water sources and treated wastewater effluents, which has raised concern of potential human health effects because these substances may be bioaccumulative and extremely persistent. The saturated carbon–fluorine bonds of the substances make them resistant to degradation by physical, chemical, and biological processes. There is therefore a need for advanced remediation methods. Iron-based methods involving high-valent compounds are appealing to degrade these substances due to their high oxidation potentials and capability to generate environmentally friendly by-products. This article presents for the first time the oxidation ability of tetraoxy anions of iron(V) (Fe^VO₄ ^3?, Fe(V)), and iron(IV) (Fe^IVO₄ ^4?, Fe(IV)), commonly called ferrates, in neutral and alkaline solutions. Solid compounds of Fe(V) (K₃FeO₄) and Fe(IV) (Na₄FeO₄) were added directly into buffered solution containing perfluorooctansulfonate and perfluorooctanoic acid at pH 7.0 and 9.0, and mixed solutions were subjected to analysis for remaining fluoro compounds after 5 days. The analysis was performed by liquid chromatography–mass spectrometry/mass spectrometry technique. Fe(IV) showed the highest ability to oxidize the studied contaminants; the maximum removals were 34 % for perfluorooctansulfonate and 23 % for perfluorooctanoic acid. Both Fe(V) and Fe(IV) had slightly higher tendency to oxidize contaminants at alkaline pH than at neutral pH. Results were described by invoking reactions involved in oxidation of perfluorooctansulfonate and perfluorooctanoic acid by ferrates in aqueous solution. The results demonstrated potentials of Fe(V) and Fe(IV) to degrade perfluoroalkyl substances in contaminated water.     

Long-term geochemical evolution of acidic mine wastes under anaerobic conditions

A nearly 5-year anaerobic incubation experiment was conducted to observe the geochemical evolution of an acidic mine waste. Long-term storage of the mine waste under strict anaerobic conditions caused marked increase in aqueous sulfur, while aqueous iron showed no remarkable change. Co-existing oxidation and reduction of elemental sulfur appeared to play a central role in controlling the evolutionary trends of aqueous sulfur and iron. Addition of organic matter increased the aqueous Fe concentration, possibly due to enhanced iron mobilization by microbial iron reduction and increased iron solubility by forming organically complexed Fe species. Further addition of CaCO₃ resulted in immobilization of aqueous iron and sulfur due to elevated pH and gypsum formation. The chemical behaviors of environmentally significant metals were markedly affected by the added organic matter; Al, Cr, Cu, Ni and Zn tended to be immobilized probably due to elevated pH and complexation with insoluble organic molecules, while As and Pb tended to be mobilized. Jarosite exhibited high stability after nearly 5 years of anaerobic incubation and even under circumneutral pH conditions. Long-term weathering of aluminosilicate through acid attack raised pH, while continuous reaction between the added CaCO₃ and mine waste-borne stored acid decreased pH.     

Removal of arsenic by Acidothiobacillus ferrooxidans bacteria in bench scale fixed-bed bioreactor system

In the present study arsenic contaminated simulated water and groundwater was treated by the combination of biological oxidation of tri-valent arsenite [As (III)] to penta-valent arsenate [As (V)] in presence of Acidothiobacillus ferrooxidans bacteria and its removal by adsorptive filtration in a bioreactor system. This method includes the immobilisation of A.ferrooxidans on Granulated Activated Carbon (GAC) capable of oxidising ferrous [Fe (II)] to ferric [Fe (III)]. The Fe (III) significantly converts the As (III) to As (V) and ultimately removed greater than 95% by the bed of GAC, limestone, and sand. The significant influence of Fe (II) concentration (0.1–1.5?gL^?1), flowrate (0.06–0.18?Lh^?1), and initial As (III) concentration (100–1000?µgL^?1) on the arsenic removal efficiency was investigated. The simulated water sample containing the different concentration of As (III) and other ions was used in the study. The removal of other co-existing ions present in contaminated water was also investigated in column study. The concentration of arsenic was found to be <10?µgL^?1 which is below Maximum Contaminant Level (MCL) as per WHO in treated water. The results confirmed that the present system including adsorptive-filtration was successfully used for the treatment of contaminated water containing As (III) ions.     

Assessment of heavy metals in a soil contaminated by oil spill: a case study in Nigeria

Surface and subsurface soil samples contaminated with crude oils were collected from an impacted site at Bodo City in the Niger Delta, Nigeria, after a field reconnaissance survey. An uncontaminated soil sample collected 100 m from the impacted site, but within the same geographical area, was used as a control. Trace elements such as, As, Cu, Cr, Cd, Fe, Pb, Ba, Ni, V, Hg and cation-exchange capacity constituents of the contaminated and uncontaminated soils were determined by atomic absorption spectroscopy. Trace element concentrations were: Cu, 0.5–13.4 mg kg^{? 1}; Cr, 0.2–0.8 mg kg^{? 1}; Fe, 6.2–8.7 mg kg^{? 1}; Ba 80.0–108.0 mg kg^{? 1}; Ni, 0.6–4.8 mg kg^{? 1}; and V, 4.0–9.4 mg kg^{? 1}; cation-exchange capacity ranged from 43.6 to 57.2 mg kg^{? 1} in surface and subsurface soils. Results showed that eigenvalues for the two first principal components represent up to 49% of the total variance. A positive correlation of the first principal component with Cu, Cr and cation-exchange capacity shows pollution from oil spillage, while a positive correlation of the second principal component with Cr, Fe, V, and dissolved oxygen (DO) shows both oil pollution and allochthonous inputs.     

Simultaneous measurements of arsenic and sulfide using diffusive gradients in thin films technique (DGT)

Diffusive gradients in thin films technique (DGT) is a dynamically passive sampling technique which has been applied increasingly to the environmental monitoring field. In the preliminary period, the DGT with zirconium hydroxide-silver iodide as the binding phase (ZrO-AgI DGT) has been developed for the determination of sulfide (S(II)). On this basis, this paper developed its determination method for inorganic arsenite (As(III)) to further realize the simultaneous and high-resolution measurements of labile inorganic As and S(II) in sediments. ZrO-AgI binding gel had a strong ability in adsorbing and fixing As(III), showing a linear increase in the initial 12.5 min. After saturation of S(II) on ZrO-AgI binding gel, the adsorption rate and adsorption capacity of As(III) reduced by 8 and 14%, respectively. A stable elution rate (89.1 ± 2.2%) was obtained by extraction of As(III) on the binding gel using a mixture solution of 1.0 M NaOH and 1.0 M H₂O₂ (1:1). The DGT capacity of As(III) determined by the ZrO-AgI DGT was 23.6 μg cm^?2. DGT uptakes of As(III) were independent of pH (4.0–9.0) and ionic strength (0.01–100 mM), and they did not interfere with each other during the uptake process. Simultaneous measurements of labile As and S(II) in four sediment cores of Taihu Lake (China) with ZrO-AgI DGT showed that they had similarly vertical distributions in the top 16-mm layer in one core and in the whole profile up to the 35 mm depth in two cores. It likely reflected a simultaneous release of As and S(II) in sediments by synchronous reduction of As-hosted oxidized iron and sulfate, respectively. The simultaneous decreases of labile As and S(II) from their co-precipitation (e.g., As₂S₃) were not obvious in deeper sediment layer through the measurement with ZrO-AgI DGT.     

As(III) adsorption onto Fe-impregnated food waste biochar: experimental investigation,modeling, and optimization using response surface methodology

Biochar derived from food waste was modified with Fe to enhance its adsorption capacity for As(III), which is the most toxic form of As. The synthesis of Fe-impregnated food waste biochar (Fe-FWB) was optimized using response surface methodology (RSM), and the pyrolysis time (1.0, 2.5, and 4.0 h), temperature (300, 450, and 600 °C), and Fe concentration (0.1, 0.3, and 0.5 M) were set as independent variables. The pyrolysis temperature and Fe concentration significantly influenced the As(III) removal, but the effect of pyrolysis time was insignificant. The optimum conditions for the synthesis of Fe-FWB were 1 h and 300 °C with a 0.42-M Fe concentration. Both physical and chemical properties of the optimized Fe-FWB were studied. They were also used for kinetic, equilibrium, thermodynamic, pH, and competing anion studies. Kinetic adsorption experiments demonstrated that the pseudo-second-order model had a superior fit for As(III) adsorption than the pseudo-first-order model. The maximum adsorption capacity derived from the Langmuir model was 119.5 mg/g, which surpassed that of other adsorbents published in the literature. Maximum As(III) adsorption occurred at an elevated pH in the range from 3 to 11 owing to the presence of As(III) as H₂AsO₃^? above a pH of 9.2. A slight reduction in As(III) adsorption was observed in the existence of bicarbonate, hydrogen phosphate, nitrate, and sulfate even at a high concentration of 10 mM. This study demonstrates that aqueous solutions can be treated using Fe-FWB, which is an affordable and readily available resource for As(III) removal.

     

Kinetics of the oxidation of endocrine disruptor nonylphenol by ferrate(VI)

The kinetics of the oxidation of endocrine disruptor nonylphenol (NP) by potassium ferrate(VI) (K₂FeO₄) in water as a function of pH 8.0–10.9 at 25°C is presented. The observed second-order rate constants, k _obs, decrease with an increase in pH 269–32 M^?1 s^?1. The speciation of Fe(VI) (HFeO ₄ ^? and FeO ₄ ^2? ) and NP (NP–OH and NP–O^?) species was used to explain the pH dependence of the k _obs values. At a dose of 10 mg L^?1 (50 μM) K₂FeO₄, the half-life for the removal of NP by Fe(VI), under water treatment conditions, is less than 1 min.     

Pilot-scale tests to optimize the treatment of net-alkaline mine drainage

A pilot-scale plant consisting of an oxidation basin (OB), a neutralization basin (NB), a reaction basin (RB), and a settling basin (SB) was designed and built to conduct pilot-scale experiments. With this system, the effects of aeration and pH on ferrous oxidation and on precipitation of the oxidized products were studied systemically. The results of pilot-scale tests showed that aeration at 300 L/min was optimum for oxidation of Fe(II) in the OB, and the efficiency of oxidation of Fe(II) increased linearly with increasing retention time. However, Fe(II) was still present in the subsequent basins—NB, RB, and SB. Results from pilot-scale tests in which neutralization was excluded were used to obtain rate constants for heterogeneous and homogeneous oxidation. Oxidation of Fe(II) reached almost 100% when the pH of the mine drainage was increased to more than 7.5, and there was a linear relationship between total rate constant, log (K _total), and pH. Absorbance changes for samples from the NB under different pH conditions were measured to determine the precipitation properties of suspended solids in the SB. Because ferrous remained in the inflow to the SB, oxidation of Fe(II) was dominant initially, resulting in increased absorbance, and the rate of precipitation was slow. However, the absorbance of the suspension in the SB rapidly dropped when pH was higher than 7.5.     

Effects of three low-molecular-weight organic acids (LMWOAs) and pH on the mobilization of arsenic and heavy metals (Cu, Pb, and Zn) from mine tailings

Natural organic acids may play an important role in influencing the mobility of toxic contaminants in the environment. The mobilization of arsenic (As) and heavy metals from an oxidized Pb–Zn mine tailings sample in the presence of three low-molecular-weight organic acids, aspartic acid, cysteine, and succinic acid, was investigated at a mass ratio of 10 mg organic additive/g mine tailings in this study. The effect of pH was also evaluated. The mine tailings sample, containing elevated levels of As (2,180 mg/kg), copper (Cu, 1,100 mg/kg), lead (Pb, 12,860 mg/kg), and zinc (Zn, 5,075 mg/kg), was collected from Bathurst, New Brunswick, Canada. It was found that the organic additives inhibited As and heavy metal mobilization under acidic conditions (at pH 3 or 5), but enhanced it under neutral to alkaline conditions (at pH above 7) through forming aqueous organic complexes. At pH 11, As, Cu, Pb, and Zn were mobilized mostly by the organic additives, 45, 46, 1,660, and 128 mg/kg by aspartic acid, 31, 28, 1,040, and 112 mg/kg by succinic acid, and 53, 38, 2,020, and 150 mg/kg by cysteine, respectively, whereas those by distilled water were 6, 16, 260, and 52 mg/kg, respectively. It was also found that the mobilization of As and the heavy metals was closely correlated, and both were closely correlated to Fe mobilization. Arsenic mobilization by the three LMWOAs was found to be consistent with the order of the stability of Fe–, Cu–, Pb–, and Zn–organic ligand complexes. The organic acids might be used potentially in the natural attenuation and remediation of As and heavy metal–contaminated sites.     

Dynamic changes in radial oxygen loss and iron plaque formation and their effects on Cd and As accumulation in rice (Oryza sativa L.)

Temporal variations and correlations between radial oxygen loss (ROL), iron (Fe) plaque formation, cadmium (Cd) and arsenic (As) accumulation were investigated in two rice cultivars at four different growth stages based upon soil pot and deoxygenated solution experiments. The results showed that there were significant differences in ROL (1.1–16 μmol O₂ plant^?1 h^?1), Fe plaque formation (4,097–36,056 mg kg^?1), Cd and As in root tissues (Cd 77–162 mg kg^?1; As 49–199 mg kg^?1) and Fe plaque (Cd 0.4–24 mg kg^?1; As 185–1,396 mg kg^?1) between these growth stages. ROL and Fe plaque increased dramatically from tillering to ear emergence stages and then were much reduced at the grain-filling stage. Furthermore, significantly positive correlations were detected between ROL and concentrations of Fe, Cd and As in Fe plaque. Our study indicates that increased Fe plaque forms on rice roots at the ear emergence stage due to the increased ROL. This stage could therefore be an important period to limit the transfer and distribution of Cd and As in rice plants when growing in soils contaminated with these toxic elements.     

Geological factors controlling occurrence and distribution of arsenic in groundwaters from the southern margin of the Duero Basin,Spain

Groundwater from springs and boreholes on the southern edge of the Cenozoic Duero Basin (DB) of Spain has concentrations of arsenic (As) which are commonly above the EC drinking-water limit of 10 μg/L and reach observed values up to 241 μg/L. Groundwater compositions within the sedimentary aquifer vary from Ca–HCO₃ type, variably affected by evaporation and agricultural pollution at shallow levels, to Na–HCO₃ compositions in deeper boreholes of the basin. Groundwater conditions are mainly oxidising, but reducing groundwaters exist in sub-basins within the aquifer, localised flow paths likely being influenced by basement structure. Arsenic concentrations are spatially variable, reaching up to 38 μg/L in springs of the Spanish Central System (SCS) basement aquifer and up to 62 μg/L in springs from the DB. Highest As concentrations are associated with the Na–HCO₃ compositions in deep boreholes (200–450 m depth) within the DB. These have high pH values (up to 9.6) which can give rise to associated elevated concentrations of V and U (up to 64 and 30 μg/L, respectively). In the deep borehole waters of the DB, oxidising flows derived from the mineralised igneous–metamorphic basement and discharging via major faults, and are considered the origin of the higher concentrations. Compositions are consistent with desorption of As and other anionic species from metal oxyhydroxides in an oxic environment. Under locally reducing conditions prevalent in some low-flow parts of the DB, an absence of detectable dissolved As is coincident with low or undetectable SO₄ concentrations, and consistent with loss via formation of authigenic sulphide minerals. Mitigation measures are needed urgently in this semi-arid region where provision of alternative sources of safe drinking water is logistically difficult and expensive.     

Investigation of severe water problem in urban areas of a developing country: the case of Dhaka,Bangladesh

The present study evaluated water supply geochemistry in Dhaka City, Bangladesh, to provide detailed trace level (subppb) water quality data that include major ions, low dissolved oxygen (DO) and toxic trace metals for sustainable development. Dhaka Groundwater, which almost uniformly meets the World Health Organization guideline, has become the preferred source. Due to groundwater depletion and an ever-increasing need to meet water demands by city residents, Dhaka water supply and sewerage authority has initiated the treatment of river water, despite the fact that very little is known about the geochemical structure, and trace metal content in the Dhaka water supply. Major ion composition of water samples was determined, and the results used to generate Stiff diagrams. The diagrams served to visually compare water from different sources based on units of mass/volume. Hydrochemical facies analysis showed supply ground and surface waters are comprised predominately of Ca–Na–Mg–HCO₃ and Ca–Na–Mg–HCO₃–Cl types. Spatial distribution of ions, and Na/Cl and Na/SiO₂ molar ratio indicated that silicate weathering is the dominant geochemical process. Chemical data revealed that toxic Cr metal mobilization is associated with chemical hazards from the leather industry. The vulnerability of deep wells to contamination by As is governed by the geometry of induced groundwater flow paths and the geochemical conditions encountered between the shallow and deep regions of the aquifer. Quantifying total arsenic (As) and As from interlocking geochemical cycles (Fe, Mn) may assist in interpreting As dynamics in Dhaka well water. The surface source water was hypoxic to anoxic low DO associated with very high concentrations of biological oxygen demands, and electrical conductivity compared to industrial and non-industrial urban processes and standard activity guidelines. The results of this study should be applied to future research focused on the potential to improve water quality in urban and surrounding areas.     

Efficient oxidation of bisphenol A with oxysulfur radicals generated by iron-catalyzed autoxidation of sulfite at circumneutral pH under UV irradiation

There is actually a need for efficient methods to clean waters and wastewaters from pollutants such as the bisphenol A endocrine disrupter. Advanced oxidation processes currently use persulfate or peroxymonosulfate to generate sulfate radicals. There are, however, few reports on the use of sulfite to generate sulfate radicals, instead of persulfate or peroxymonosulfate, except for dyes. Here we studied the degradation of the bisphenol A using iron(III) as catalyst and sulfite as precursor of oxysulfur radicals, at initial pH of 6, under UV irradiation at 395 nm. The occurrence of radicals was checked by quenching with tert-butyl alcohol and ethanol. Bisphenol A degradation products were analyzed by liquid chromatography coupled with mass spectrometry (LC–MS). Results reveal that iron(III) or iron(II) have a similar oxidation efficiency. Quenching experiments show that the oxidation rate of bisphenol A is 47.7 % for SO ₄ ^·? , 37.3 % for SO ₅ ^·? and 15 % for HO^·. Bisphenol A degradation products include catechol and quinone derivatives. Overall, our findings show that the photo-iron(III)–sulfite system is efficient for the oxidation of bisphenol A at circumneutral pH.     

Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography

A simple and totally organic-free (green) method, viz. headspace water-based liquid-phase microextraction combined with high-performance liquid chromatography-ultraviolet detection has been successfully developed for analysis of formic acid and acetic acid in environmental water samples. A microdrop of an aqueous solution of sodium hydroxide was suspended from the tip of a microsyringe needle over the headspace of the stirred sample solution containing the analytes at pH 1.0 for a given time. The microdrop was then retracted into the microsyringe, diluted with HPLC mobile phase, and injected to HPLC. Optimum efficiency has been achieved for: 3.0 µL NaOH microdrop (0.1 mol L^?1) exposed for 15 min over the headspace of an aqueous sample of 6.5 mL at 55 °C, containing 15% w/v of Na₂SO₄, adjusted to pH = 1.0 and stirred at 750 rpm. Under these conditions, enrichment factors of 162 and 187, limits of detection of 0.3 and 0.1 µg L^?1 (S/N = 3) with dynamic linear ranges of 1–500 and 0.5–500 µg L^?1 were obtained for formic acid and acetic acid, respectively. A reasonable repeatability (5.8% ≤ RSD ≤ 8.8%, n = 6) and satisfactory linearity (r² ≥ 0.997) illustrated the performance of the method.     

Biogeochemical cycling of ferric oxyhydroxide affecting As partition in groundwater aquitard

High arsenic (As) concentration in groundwater potentially poses a serious threat to the health of local residents in southwestern Taiwan. Although the As release to groundwater is responsible for the reducing bacteria-mediated reductive dissolution of As-rich Fe hydroxides, the influences of FeRB and different organic substrates on As and Fe mobility and transformation were rarely discussed. An experiment that involved As-adsorbed synthetic amorphous Fe(III) hydroxide (HFO) and the inoculation of in situ Fe-reducing bacteria (FeRB) was performed to evaluate the contribution of FeRB to the As mobility and transformation. The batched experiment of As-free HFO showed that the reducing bacteria rapidly induced the reduction of amorphous Fe oxyhydroxide to Fe(II) by reductive dissolution of HFO and formation of Fe-citrate complexation. For aqueous As(V) reduction experiment, arsenate was effectively reduced to As(III) by the facultative anaerobic bacterium in the cultured FeRB. In the experiment of As-containing HFO reduction, the aqueous As(V) acts as an electron acceptor and reduced to As(III) after the reductive dissolution of Fe(III) on HFO. However, the increase in the As(III) concentrations with time for various organic substrates in the As-adsorbed HFO-reducing experiment differ from the rates of As(V) reduction with various organic substrates in the As(V)-reducing experiment. The decrease in sorption sites by coupled reductive dissolution of HFO and the competitive desorption of small molecular organic carbon is apparently the important factor of As mobility. For large molecular organic carbon (i.e., citrate), the significant contribution of citrate on As mobility is the complexation of iron citrate. A working hypothesis model of As biogeochemical cycling is proposed to illustrate the relevant processes in the groundwater aquitard of southwestern Taiwan.     

Efficient oxidation of sulfides into sulfoxides catalyzed by a chitosan–Schiff base complex of Cu(II) supported on supramagnetic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles

Sulfoxides are versatile synthetic intermediates for the preparation of biological products. Therefore, there is a need for efficient methods to oxidize sulfides into sulfoxides. Such oxidation may be catalyzed by magnetic nanocatalysts due to their good stability, easy synthesis, high surface area, low toxicity and easy separation by magnetic forces. Here we prepared a nanocatalyst by immobilization of the chitosan–Schiff base complex on supramagnetic Fe₃O₄ nanoparticles. The chitosan–Schiff base complex has been previously prepared by functionalization of chitosan with 5-bromosalicylaldehyde and metalation with copper(II) acetate. The catalyst was characterized by Fourier transform infrared, powder X-ray diffraction, transmission electron microscope, scanning electron microscopy, energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Results show that the Fe₃O₄ nanoparticles and nanocatalyst were spherical in shape with an average size of 20 nm. Upon the covalently anchoring of chitosan–Schiff base Cu complex on the magnetic Fe₃O₄ nanoparticles, the average size increased to 60 nm. The prepared Fe₃O₄–chitosan–Schiff base Cu complex catalyzed very efficiently the oxidation of sulfides to sulfoxides with 100 % selectivity in all cases under green reaction conditions and excellent yields. Additionally, ease of recovery and reusability up to four cycles without noticeable loss of catalytic activity make the present protocol beneficial from industrial and environmental viewpoint.     

Removal of arsenate from water by adsorbents: a comparative case study

Laboratory and field filtration experiments were conducted to study the effectiveness of As(V) removal for five types of adsorbent media. The media included activated alumina (AA), modified activated alumina (MAA), granular ferric hydroxide (GFH), granular ferric oxide (GFO), and granular titanium dioxide (TiO₂). In laboratory batch and column experiments, the synthetic challenge water was used to evaluate the effectiveness for five adsorbents. The results of the batch experiments showed that the As(V) adsorption decreased as follows at pH 6.5: TiO₂ > GFO > GFH > MAA > AA. At pH 8.5, however, As(V) removal decreased in the following order: GFO = TiO₂ > GFH > MAA > AA. In column experiments, at pH 6.5, the adsorbed As(V) for adsorbents followed the order: TiO₂ > GFO > GFH, whereas at pH 8.5 the order became: GFO = TiO₂ > GFH when the challenge water containing 50 μg/L of As(V) was used. Field filtration experiments were carried out in parallel at a wellhead in New Jersey. Before the effluent arsenic concentration increased to 10 μg/L, approximately 58,000 and 41,500 bed volumes of groundwater containing an average of 47 μg/L of As(V) were treated by the filter system packed with GFO and TiO₂, respectively. The As(V) adsorption decreased in the following sequence: GFO > TiO₂ > GFH > MAA > AA. Filtration results demonstrated that GFO and TiO₂ adsorbents could be used as media in small community filtration systems for As(V) removal.     

Natural and synthesised iron-rich amendments for As and Pb immobilisation in agricultural soil

The immobilisation of heavy metals in contaminated soils is a promising alternative to conventional remediation techniques. Very few studies have focused on the use of iron-rich nanomaterials and natural materials for the adsorption of toxic metals in soils. Synthesised iron-rich nanomaterials (Fe and Zr–Fe oxides) and natural iron-rich materials (natural red earth; NRE) were used to immobilise As and Pb in contaminated agricultural soil. Total concentrations of As and Pb in the initial soil (as control) were 170.76 and 1945.11 mg kg^?1, respectively. Amendments were applied into the soil at 1, 2.5 and 5% (w/w) in triplicate and incubated for 150 days. Except for the NRE-amended soil, soil pH decreased from 5.6 to 4.9 with increasing application rates of Fe and Zr–Fe oxides. With addition of Fe and Zr–Fe oxides at 5%, the ammonium acetate (NHO₄Ac)-extractable Pb was greatly decreased by 83 and 65% compared with NRE addition (43%). All subjected amendments also led to a decrease in NHO₄Ac-extractable As in the soils, indicating the high capacity of As immobilisation. Soil amended with NRE showed a lower ratio of cy19:0 to 18:1ω7c, indicating decreased microbial stress. The toxicity characteristic leaching procedure produced results similar to the NHO₄Ac extraction for As and Pb. The NRE addition is recommended for immobilising heavy metals and maintaining biological soil properties.