Removal of As(III) and As(V) from water by chitosan and chitosan derivatives: a review

As arsenic removal becomes a global concern, the development of removal processes for arsenic treatment is still a major challenge. With regard to environmental compatibility and cheapness, chitosan and chitosan derivatives are considered as a promising removal technology for arsenic. Chitosan and chitosan derivatives possess the properties of low cost and good sorption on the arsenic removal. The present review is concerned about the present understanding of the mechanisms involved in sorption processes. Further on, detailed discussions are given of the effects of various factors on the performance of chitosan and chitosan derivatives in arsenic treatment processes. Finally, special attention is paid to the future challenges of chitosan and chitosan derivatives utilized for industrial arsenic treatment.     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Arsenic species in ecosystems affected by arsenic-rich spring water near an abandoned mine in Korea

The objectives of this study were to quantitatively estimate the distribution of arsenic with its speciation and to identify potential pathways for transformation of arsenic species from samples of water, sediments, and plants in the ecosystem affected by the Cheongog Spring, where As(V) concentration reached levels up to 0.270 mg L⁻¹. After flowing about 100 m downstream, the arsenic level showed a marked reduction to 0.044 mg L⁻¹ (about 84% removal) without noticeable changes in major water chemistry. The field study and laboratory hydroponic experiments with the dominant emergent plants along the creek (water dropwort and thunbergian smartweed) indicated that arsenic distribution, reduction, and speciation appear to be controlled by, (i) sorption onto stream sediments in exchangeable fractions, (ii) bioaccumulation by and possible release from emergent plants, and (iii) transformation of As(V) to As(III) and organic species through biological activities.     

Sulfate and glutathione enhanced arsenic accumulation by arsenic hyperaccumulator Pteris vittata L.

This experiment examined the effects of sulfate (S) and reduced glutathione (GSH) on arsenic uptake by arsenic hyperaccumulator Pteris vittata after exposing to arsenate (0, 15 or 30 mg As L⁻¹) with sulfate (6.4, 12.8 or 25.6 mg S L⁻¹) or GSH (0, 0.4 or 0.8 mM) for 2-wk. Total arsenic, S and GSH concentrations in plant biomass and arsenic speciation in the growth media and plant biomass were determined. While both S (18-85%) and GSH (77-89%) significantly increased arsenic uptake in P. vittata, GSH also increased arsenic translocation by 61-85% at 0.4 mM (p < 0.05). Sulfate and GSH did not impact plant biomass or arsenic speciation in the media and biomass. The S-induced arsenic accumulation by P. vittata was partially attributed to increased plant GSH (21-31%), an important non-enzymatic antioxidant countering oxidative stress. This experiment demonstrated that S and GSH can effectively enhance arsenic uptake and translocation by P. vittata.     

Arsenic species and leachability in the fronds of the hyperaccumulator Chinese brake (Pteris vittata L.)

Arsenic speciation is important not only for understanding the mechanisms of arsenic accumulation and detoxification by hyperaccumulators, but also for designing disposal options of arsenic-rich biomass. The primary objective of this research was to understand the speciation and leachability of arsenic in the fronds of Chinese brake (Pteris vittata L.), an arsenic hyperaccumulator, with an emphasis on the implications for arsenic-rich biomass disposal. Chinese brake was grown for 18 weeks in a soil spiked with 50 mg As kg(-1) as arsenate (AsO4(3-)), arsenite (AsO3(3-)), dimethylarsinic acid (DMA), or methylarsonic acid (MMA). Plant samples were extracted with methanol/water (1:1) and arsenic speciation was performed using high performance liquid chromatography coupled with atomic fluorescence spectrometry. The impacts of air-drying on arsenic species and leachability in the fronds were examined in the laboratory. After 18 weeks, water-soluble arsenic in soil was mainly present as arsenate with little detectable organic species or arsenite regardless of arsenic species added to the soil. However, arsenic in the fronds was primarily present as inorganic arsenite with an average of 94%. Arsenite re-oxidation occurred in the old fronds and the excised dried tissues. Arsenic species in the fronds were slightly influenced by arsenic forms added to the soil. Air-drying of the fronds resulted in leaching of substantial amounts of arsenic. These findings can be of significance when looking at disposal options of arsenic-rich biomass from the point of view of secondary contamination.     

As(III) removal from groundwaters using fixed-bed upflow bioreactors

The application of biological oxidation of iron and manganese, as a potential treatment method for the removal of arsenic from contaminated groundwaters, was examined in this paper. This method was based on the growth of certain species of indigenous bacteria, which are capable of oxidizing the soluble iron and manganese ions; the oxidized forms can be subsequently removed from the aqueous stream by over 97%, through their transformation to insoluble oxides and separation by a suitable filter medium. Arsenic was removed by around 80%, under certain conditions, which were found to be sufficient for Fe(II) removal (dissolved oxygen 2.7 mg/l, redox 280-290 mV, pH 7.2, U 8.25 m/h). The specific treatment technique presents several advantages towards conventional physicochemical treatment methods, such as enhanced coagulation or direct adsorption since: (a) it does not require the addition of other chemicals for oxidizing and removing As(III), (b) it does not require close monitoring of a breakthrough point, as in conventional column adsorption processes and (c) it could find application for the removal of, at least, three groundwater contaminants (Fe, Mn, As).     

Timing of phosphate application affects arsenic phytoextraction by Pteris vittata L. of different ages

The effects of timing in phosphate application on plant growth and arsenic removal by arsenic hyperaccumulator Pteris vittata L. of different ages were evaluated. The hydroponic experiment consisted of three plant ages (A45d, A90d and A180d) and three P feeding regimens (P200+0, P134+66 and P66+134) growing for 45 d in 0.2-strength Hoagland-Arnon solution containing 145 microg L(-1) As. While all plants received 200 microM P, P was added in two phases: during acclimation and after arsenic exposure. High initial P-supply (P200+0) favored frond biomass production and plant P uptake, while split-P application (P134+66 and P66+134) favored plant root production. Single P addition favored arsenic accumulation in the roots while split-P addition increased frond arsenic accumulation. Young ferns (A45d) in treatment P134+66 were the most efficient in arsenic removal, reducing arsenic concentration to below 10 microg L(-1) in 35 d. The results indicated that the use of young ferns, coupled with feeding of low initial P or split-P application, increased the efficiency of arsenic removal by P. vittata.     

The chemistry and behaviour of antimony in the soil environment with comparisons to arsenic: A critical review

This article provides a critical review of the environmental chemistry of inorganic antimony (Sb) in soils, comparing and contrasting findings with those of arsenic (As). Characteristics of the Sb soil system are reviewed, with an emphasis on speciation, sorption and phase associations, identifying differences between Sb and As behaviour. Knowledge gaps in environmentally relevant Sb data for soils are identified and discussed in terms of the limitations this imposes on understanding the fate, behaviour and risks associated with Sb in environmental soil systems, with particular reference to mobility and bioavailability.     

LC–ICP–MS analysis of arsenic compounds in dominant seaweeds from the Thermaikos Gulf (Northern Aegean Sea,Greece)

The content of total arsenic and arsenic compounds in the dominant seaweed species in the Thermaikos Gulf, Northern Aegean Sea was determined in samples collected in different seasons. Total arsenic was determined by acid digestion followed by ICP–MS. Arsenic speciation was analyzed by water extraction followed by LC–ICP–MS. Total arsenic concentrations in the seaweeds ranged from 1.39 to 55.0 mg kg⁻¹. Cystoseira species and Codium fragile showed the highest total As contents, while Ulva species (U. intestinalis, U. rigida,U. fasciata) had the lowest Arsenosugars, the most common arsenic species in seaweeds, were found in all samples, and glycerol-arsenosugar was the most common form; however, phosphate-arsenosugar and sulfate-arsenosugar were also present. Inorganic arsenic was measured in seven algae species and detected in another. Arsenate was the most abundant species in Cystoseira barbata (27.0 mg kg⁻¹). Arsenobetaine was measured in only one sample. Methylated arsenic species were measured at very low concentrations. The information should contribute to further understanding the presence of arsenic compounds in dominant seaweeds from the Thermaikos Gulf.     

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: Divergent reactions in the presence of organic ligands

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H₂O₂, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA < 1:1), contrasting with the rapid oxidation of Fe(II) by O₂ and H₂O₂ at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.     

Arsenic accumulation and phosphorus status in two rice (Oryza sativa L.) cultivars surveyed from fields in South China

The consumption of paddy rice (Oryza sativa L.) is a major inorganic arsenic exposure pathway in S.E. Asia. A multi-location survey was undertaken in Guangdong Province, South China to assess arsenic accumulation and speciation in 2 rice cultivars, one an Indica and the other a hybrid Indica. The results showed that arsenic concentrations in rice tissue increased in the order grain < husk < straw < root. Rice grain arsenic content of 2 rice cultivars was significant different and correlated with phosphorus concentration and molar ratio of P/As in shoot, being higher for the Indica cultivar than for the hybrid Indica, which suggests altering shoot phosphorus status as a promising route for breeding rice cultivars with reduced grain arsenic. Speciation of grain arsenic, performed using HPLC-ICP-MS, identified inorganic arsenic as the dominant arsenic species present in the rice grain.     

Enhanced coagulation with polyaluminum chlorides: role of pH/alkalinity and speciation

Enhanced coagulation is considered to be among the best available techniques (BAT) for disinfection by-product (DBP) precursor removal in water treatment. Improving existing understanding requires further consideration of nuances of chemical speciation relative to source water chemistry. In this paper, the effect of alkalinity/pH and speciation on inorganic polymer flocculants, polyaluminum chlorides (PACls) for enhanced particle and natural organic matter (NOM) removal was investigated. Three kinds of well-characterized typical source waters in China with low, moderate, and high alkalinity were selected. Performance of coagulants is controlled not only by preformed species but also by those formed in situ. At neutral and basic pH values, PACls with higher basicity (ratio of OH(-)/Al), which have more stable preformed Alb (the rapid reacted species as in ferron assay), are more efficient for turbidity and NOM removal. At slightly acidic pH, PACls with lower basicity are more efficient since more Alb can be formed in situ. Optimal NOM removal was achieved at pH 5.5-6.5 for all PACls. Basicity, speciation, and dosage of coagulant should be optimized based on raw water alkalinity to enhance the removal efficiency of NOM.     

The Analysis of Airborne Sulfate

This report reviews the current state of analytical methodology for sulfate in airborne particles. Methods for determination of total aerosol sulfate and total soluble sulfate are assessed. A more detailed review of the relatively new techniques for quantitative speciation of airborne sulfate then follows. Size distribution methodology and filter sampling difficulties relating to the collection of airborne sulfate-containing particles are enumerated. Experiments are suggested which use new, improved, and potentially applicable sulfate speciation techniques to obtain a better understanding of the generation, transport, transformation and removal processes that, in turn, determine the identity and concentrations of sulfate species in ambient air.     

Arsenic speciation of atmospheric particulate matter (PM10) in an industrialised urban site in southwestern Spain

An arsenic speciation study has been performed in PM10 samples collected on a fortnight basis in the city of Huelva (SW Spain) during 2001 and 2002. The arsenic species were extracted from the PM10 filters using a NH2OH x HCl solution and sonication, and determined by HPLC-HG-AFS. The mean bulk As concentration of the samples analyzed during 2001 and 2002 slightly exceed the mean annual 6 ng m(-3) target value proposed by the European Commission for 2013, arsenate [As(V)] being responsible for the high level of arsenic. The speciation analyses showed that As(V) was the main arsenic species found, followed by arsenite [As(III)] (mean 6.5 and 7.8 ng m(-3) for As(V), mean 1.2 and 2.1 ng m(-3) for As(III), in 2001 and 2002, respectively). The high levels of arsenic species found in PM10 in Huelva have a predominant industrial origin, such as the one from a nearby copper smelter, and do not present a seasonal pattern. The highest daily levels of arsenic species correspond to synoptic conditions in which the winds with S and SW components transport the contaminants from the main emission source. The frequent African dust outbreaks over Huelva may result in an increment of mass levels of PM10, but do not represent a significant input of arsenic in comparison to the anthropogenic source. The rural background levels of arsenic around Huelva are rather high, in comparison to other rural or urban areas in Spain, showing a relatively high atmosphere residence time of arsenic. This work shows the importance of arsenic speciation in studies of aerosol chemistry, due to the presence of arsenic species [As(III) and As(V)] with distinct toxicity.     

Arsenic Uptake and Accumulation in Curly Endives (Cichorium endivia L.) Irrigated with Contaminated Water

Arsenic accumulation in vegetables for direct human consumption represents a concern for food safety purposes. This potential problem can be of economic importance particularly in much appreciated, high-quality horticultural products. In this work, a greenhouse set of experiments were conducted to evaluate possible phytotoxic effects and arsenic accumulation in the production of curly endives with arsenic contaminated water.

Two concentration levels (0.5 mg/L and 1.0 mg/L) and two arsenic species (As⁺³ and As⁺⁵) were considered. Dry mass production tended to be reduced as As⁺³ concentration increased in irrigation water. However, As⁺⁵ treatments did not show significant dry mass production differences with a blank (control experiment). As accumulation in plant increased with As concentration in irrigation waters, following a linear trend. Nevertheless, the increase of accumulated As was not statistically significant for As⁺⁵ at 0.5 mg/L. Calculated biological absorption coefficients resulted in higher than previous values reported in the literature, which was attributed here to the source of arsenic (irrigation water). Considering field values for As⁺⁵/As⁺³ ratio and averaged concentrations in water, the obtained results support that there is not a short-or medium-term risk to food safety in the curly endive crop in the region of Castilla y León (Spain).     

Metal and metalloid removal in constructed wetlands, with emphasis on the importance of plants and standardized measurements: A review

This review integrates knowledge on the removal of metals and metalloids from contaminated waters in constructed wetlands and offers insight into future R&D priorities. Metal removal processes in wetlands are described. Based on 21 papers, the roles and impacts on efficiency of plants in constructed wetlands are discussed. The effects of plant ecotypes and class (monocots, dicots) and of system size on metal removal are addressed. Metal removal rates in wetlands depend on the type of element (Hg > Mn > Fe = Cd > Pb = Cr > Zn = Cu > Al > Ni > As), their ionic forms, substrate conditions, season, and plant species. Standardized procedures and data are lacking for efficiently comparing properties of plants and substrates. We propose a new index, the relative treatment efficiency index (RTEI), to quantify treatment impacts on metal removal in constructed wetlands. Further research is needed on key components, such as effects of differences in plant ecotypes and microbial communities, in order to enhance metal removal efficiency.     

Stabilization of thioarsenates in iron-rich waters

In recent years, thioarsenates have been shown to be important arsenic species in sulfidic, low-iron waters. Here, we show for the first time that thioarsenates also occur in iron-rich ground waters, and that all methods previously used to preserve arsenic speciation (acidification, flash-freezing, or EDTA addition) fail to preserve thioarsenates in such matrices. Laboratory studies were conducted to identify the best approach for stabilizing thioarsenates by combination and modification of the previously-applied methods. Since acidification was shown to induce conversions between thioarsenates and precipitation of arsenic-sulfide minerals, we first conducted a detailed study of thioarsenate preservation by flash-freezing. In pure water, thioarsenates were stable for 21 d when the samples were flash-frozen and cryo-stored with a minimal and anoxic headspace. Increasing headspace volume and oxygen presence in the headspace were detrimental to thioarsenate stability during cryo-storage. Addition of NaOH (0.1 M) or EtOH (1% V/V) counteracted these effects and stabilized thioarsenates during cryo-storage. Addition of Fe(II) to thioarsenate solutions caused immediate changes in arsenic speciation and a loss of total arsenic from solution during cryo-storage. Both effects were largely eliminated by addition of a neutral EDTA-solution, and thioarsenates were significantly stabilized during cryo-storage by this procedure. Neutralization of EDTA was required to prevent alteration of thioarsenate speciation through pH change. With the modified method (anoxic cryo-preservation by flash-freezing with minimal headspace after addition of neutralized EDTA-solution), the fractions of mono- and dithioarsenate, the two thioarsenates observed in the iron-rich ground waters, remained stable over a cryo-storage period of 11 d. Further modifications are needed for the higher SH-substituted thioarsenates (tri- and tetrathioarsenate), which were not encountered in the studied iron-rich ground waters.     

Effects of macrophytes and external carbon sources on nitrate removal from groundwater in constructed wetlands

Several microcosm wetlands unplanted and planted with five macrophytes (Phragmites australis, Commelina communis, Penniserum purpureum, Ipomoea aquatica, and Pistia stratiotes) were employed to remove nitrate from groundwater at a concentration of 21-47 mg NO3-N/l. In the absence of external carbon, nitrate removal rates ranged from 0.63 to 1.26 g NO3-N/m2/day for planted wetlands. Planted wetlands exhibited significantly greater nitrate removal than unplanted wetlands (P<0.01), indicating that macrophytes are essential to efficient nitrate removal. Additionally, a wetland planted with Penniserum showed consistently higher nitrate removal than those planted with the other four macrophytes, suggesting that macrophytes present species-specific nitrate removal efficiency possibly depending on their ability to produce carbon for denitrification. Although adding external carbon to the influent improved nitrate removal, a significant fraction of the added carbon was lost via microbial oxidation in the wetlands. Planting a wetland with macrophytes with high productivity may be an economic way for removing nitrate from groundwater. According to the harvest result, 4-11% of nitrogen removed by the planted wetland was due to vegetation uptake, and 89-96% was due to denitrification.     

Phytoextraction by arsenic hyperaccumulator Pteris vittata L. from six arsenic-contaminated soils: Repeated harvests and arsenic redistribution

This greenhouse experiment evaluated arsenic removal by Pteris vittata and its effects on arsenic redistribution in soils. P. vittata grew in six arsenic-contaminated soils and its fronds were harvested and analyzed for arsenic in October, 2003, April, 2004, and October, 2004. The soil arsenic was separated into five fractions via sequential extraction. The ferns grew well and took up arsenic from all soils. Fern biomass ranged from 24.8 to 33.5 g plant(-1) after 4 months of growth but was reduced in the subsequent harvests. The frond arsenic concentrations ranged from 66 to 6,151 mg kg(-1), 110 to 3,056 mg kg(-1), and 162 to 2,139 mg kg(-1) from the first, second and third harvest, respectively. P. vittata reduced soil arsenic by 6.4-13% after three harvests. Arsenic in the soils was primarily associated with amorphous hydrous oxides (40-59%), which contributed the most to arsenic taken up by P. vittata (45-72%). It is possible to use P. vittata to remediate arsenic-contaminated soils by repeatedly harvesting its fronds.     

Monitoring and assessing processes of organic chemicals removal in constructed wetlands

Physical, chemical and biological processes interact and work in concert during attenuation of organic chemicals in wetland systems. This review summarizes the recent progress made towards understanding how the various mechanisms attributed to organic chemicals removal interact to form a functioning wetland. We also discuss the main degradation pathways for different groups of contaminants and examine some of the key characteristics of constructed wetlands that control the removal of organic chemicals. Furthermore, we address possible comprehensive approaches and recent techniques to follow up in situ processes within the system, especially those involved in the biodegradation processes.