Simultaneous separation and speciation of inorganic As(III)/As(V) and Cr(III)/Cr(VI) in natural waters utilizing capillary microextraction on ordered mesoporous Al2O3 prior to their on-line determination by ICP-MS

In this paper, a system of flow injection (FI) capillary microextraction (CME) on line coupled with inductively plasma mass spectrometry (ICP-MS) was proposed for simultaneous separation and speciation of inorganic As(III)/As(V) and Cr(III)/Cr(VI) in natural waters. Ordered mesoporous Al2O3 coating was prepared by sol-gel technology and used as CME coating material. Various experimental parameters affecting the capillary microextraction of inorganic arsenic and chromium species have been investigated and optimized. Under the optimized conditions, the limits of detection were 0.7 and 18 ng L(-1) for As(V) and Cr(VI), 3.4 and 74 ng L(-1) for As(III) and Cr(III), respectively, with an enrichment factor of 5 and a sampling frequency of 8h(-1). The relative standard deviations (R.S.D.) were 3.1, 4.0, 2.8 and 3.9% (C=1 ng mL(-1), n=7) for As(V), As(III), Cr(VI) and Cr(III), respectively. The proposed method was successfully applied for the analysis of inorganic arsenic and chromium species in mineral water, tap water and lake water with the recovery of 94-105%. In order to verify the accuracy of the method, two certified reference of GSBZ50027-94 and GSBZ50004-88 water samples were analyzed and the results obtained were in good agreement with the certified values. The ordered mesoporous Al2O3 coated capillary showed an excellent solvent and thermal stability and could be re-used for more than 30 times without decreasing extraction efficiency.     

Separation and preconcentration of inorganic arsenic species in natural water samples with 3-(2-aminoethylamino) propyltrimethoxysilane modified ordered mesoporous silica micro-column and their determination by inductively coupled plasma optical emission spectrometry

A simple and sensitive method using micro-column packed with 3-(2-aminoethylamino) propyltrimethoxysilane (AAPTS) modified ordered mesoporous silica combined with inductively coupled plasma optical emission spectrometry (ICP-OES) for the speciation of inorganic arsenic (As(III) and As(V)) has been developed. The adsorption behaviors of As(III) and As(V) on AAPTS modified ordered mesoporous silica were investigated. It was found that As(V) can be selectively adsorbed on the micro-column within pH of 3-9, while As(III) could not be retained in the studied pH range and passed through the micro-column directly. Total inorganic arsenic was extracted after the oxidation of As(III) to As(V) with 50.0 micromol L(-1) KMnO(4). The assay of As(III) was based on subtracting As(V) from total As. The effect of various parameters on the separation/preconcentration of As(III) and As(V) have been investigated and the optimal experimental conditions were established. The adsorption capacity of AAPTS modified ordered mesoporous silica for As(V) was found to be 10.3 mg g(-1). The detection limit of the method for As(V) was 0.05 microg L(-1) with an enrichment factor of 100, and the relative standard deviation (R.S.D.) was 5.7% (n=7, C=1.0 microg L(-1)). In order to validate the developed method, a certified reference material GSBZ50004-88 environmental water sample was analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in natural water samples.     

Porous graphitic carbon as stationary phase for LC-ICPMS separation of arsenic compounds in water

A new liquid chromatographic separation method was developed for the speciation of the four main arsenic compounds present in water. Arsenite (As(III)), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate (As(V)) were separated on a recently introduced stationary phase: porous graphitic carbon (PGC). The separation was first obtained under formic acid gradient conditions, but an adsorption phenomenon of As(V) on PGC was observed. To overcome this problem, As(V) was backflushed, and an efficient separation of the four solutes was achieved within 10 min. Extremely low detection limits (ranging from 10 to 70 ng x L(-1)) were obtained by coupling LC with an ICPMS. The method was successfully applied to different spiked mineral waters and a naturally arsenic-containing freshwater.     

Arsenic (III,V) removal from aqueous solution by ultrafine α-Fe2O3 nanoparticles synthesized from solvent thermal method

Ultrafine iron oxide (α-Fe₂O₃) nanoparticles were synthesized by a solvent thermal process and used to remove arsenic ions from both lab-prepared and natural water samples. The α-Fe₂O₃ nanoparticles assumed a near-sphere shape with an average size of about 5 nm. They aggregated into a highly porous structure with a high specific surface area of ∼162 m²/g, while their surface was covered by high-affinity hydroxyl groups. The arsenic adsorption experiment results demonstrated that they were effective, especially at low equilibrium arsenic concentrations, in removing both As(III) and As(V) from lab-prepared and natural water samples. Near the neutral pH, the adsorption capacities of the α-Fe₂O₃ nanoparticles on As(III) and As(V) from lab-prepared samples were found to be no less than 95 mg/g and 47 mg/g, respectively. In the presence of most competing ions, these α-Fe₂O₃ nanoparticles maintained their arsenic adsorption capacity even at very high competing anion concentrations. Without the pre-oxidation and/or the pH adjustment, these α-Fe₂O₃ nanoparticles effectively removed both As(III) and As(V) from a contaminated natural lake water sample to meet the USEPA drinking water standard for arsenic.     

Desulfurization from thiophene by SO(4)(2-)/ZrO(2) catalytic oxidation at room temperature and atmospheric pressure

Thiophene, due to its poison, together with its combustion products which causes air pollution and highly toxic characteristic itself, attracted more and more attention to remove from gasoline and some high concentration systems. As the purpose of achieving the novel method of de-thiophene assisted by SO(4)(2-)/ZrO(2) (SZ), three reactions about thiophene in different atmosphere at room temperature and atmospheric pressure were investigated. SO(4)(2-)/ZrO(2) catalyst were synthesized and characterized by X-ray photoelectron spectroscopy (XPS), Fourier transformation infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscope (SEM). The products were detected by gas chromatography-mass spectrometry (GC-MS). XP spectra show that ozone-catalyst system (SZO) have two forms of sulfur element (S(6+) and S(2-)) on the catalyst surface, which distinguished from that of air-catalyst system (SZA) and blank-catalyst system (SZB) (S(6+)). And the results of GC-MS exhibited that some new compounds has been produced under this extremely mild condition. Especially, many kinds of sulfur compounds containing oxygen, that is easier to be extracted by oxidative desulfurization (ODS), have been detected in the SZA-1.5h and SZB-3h system. In addition, some long chain hydrocarbons have also been detected. While in SZO-0.5h system, only long chain hydrocarbons were found. The results show that total efficiency of desulfurization from thiophene with ozone near to 100% can be obtained with the SO(4)(2-)/ZrO(2) catalytic oxidation reaction.     

Determination of (Oxy)thioarsenates in sulfidic waters

Although it has long been known that soluble arsenic-sulfur (As-S) compounds exist in sulfidic waters and may play significant roles in several important processes in the biogeochemical arsenic cycle, no suitable analytical methods exist for their determination. We provide evidence that the four homologue (oxy)thioarsenates, mono-, di-, tri-, and tetrathioarsenate (AsO3S3-, AsO2S23-, AsOS33- and AsS43-), can be formed in geochemical model reactions between arsenite and sulfide under anoxic conditions (through currently unknown reaction mechanisms) and that these compounds appear to be major As species in natural sulfidic waters. These As-S species are quantified by anion-exchange chromatography-inductively coupled plasma mass spectrometry (AEC-ICPMS) with instrumental detection limits of approximately 0.1 nmol of As L(-1) in undiluted samples; arsenite, arsenate, and monomethylarsenate are quantified as well, but dimethylarsenate cannot be analyzed by this technique. Sulfur in the eluting peaks can be measured as SO+ with detection limits of approximately 0.1 micromol of S L(-1). The (oxy)thioarsenates were synthesized in solution and characterized by electrospray-tandem mass spectrometry (ES-MS-MS). In geochemical model solutions, we confirmed that both the AEC-ICPMS retention times and the ES-MS-MS spectra of the reaction products of sulfide and arsenite matched the synthesized (oxy)thioarsenate standards; for natural waters, the mass spectrometric confirmation was unsuccessful, due to matrix interferences.     

Natural attenuation processes for remediation of arsenic contaminated soils and groundwater

Arsenic (As) contamination presents a hazard in many countries. Natural attenuation (NA) of As-contaminated soils and groundwater may be a cost-effective in situ remedial option. It relies on the site intrinsic assimilative capacity and allows in-place cleanup. Sorption to solid phases is the principal mechanism immobilizing As in soils and removing it from groundwater. Hydroxides of iron, aluminum and manganese, clay and sulfide minerals, and natural organic matter are commonly associated with soils and aquifer sediments, and have been shown to be significant As adsorbents. The extent of sorption is influenced by As speciation and the site geochemical conditions such as pH, redox potential, and the co-occurring ions. Microbial activity may catalyze the transformation of As species, or mediate redox reactions thus influencing As mobility. Plants that are capable of hyperaccumulating As may translocate As from contaminated soils and groundwater to their tissues, providing the basis for phytoremediation. However, NA is subject to hydrological changes and may take substantial periods of time, thus requiring long-term monitoring. The current understanding of As NA processes remains limited. Sufficient site characterization is critical to the success of NA. Further research is required to develop conceptual and mathematical models to predict the fate and transport of As and to evaluate the site NA capacity. Engineering enhanced NA using environmentally benign products may be an effective alternative.     

Chemical speciation of nickel in fly ash by phase separation and carbon paste electrode voltammetry

In a risk-based approach to cost-effective management of power plant emissions, chemical speciation of fly ash is required. A quantitative but indirect separation of nickel phases by sequential extraction was undertaken in conjunction with direct analysis of the sulfidic nickel phase by carbon paste electrode voltammetry (CPEV). Four ash samples produced in a laboratory combustion system from burning high- and low-sulfur residual oil at excess O(2) of 1 and 2-3 mol% were studied. The extractions yielded five phases of nickel. The CPEV analysis of sulfidic nickel in the ash and extraction residues was performed in pH 5 acetate. The anodic peak (-0.1 V) unique to Ni(3)S(2), distinguishing it from NiS and NiS(2), was found to be absent from these ash samples. The CPEV method was consistent with phase extraction, which showed NiSO(4) being predominant with very low proportions of sulfidic nickel.     

Removal of As(V) and As(III) by reclaimed iron-oxide coated sands

This paper aims at the feasibility of arsenate and arsenite removal by reclaimed iron-oxide coated sands (IOCS). Batch experiments were performed to examine the adsorption isotherm and removal performance of arsenic systems by using the IOCS. The results show that the pH(zpc) of IOCS was about 7.0 +/- 0.4, favoring the adsorption of As(V) of anion form onto the IOCS surface. As the adsorbent dosage and initial arsenic concentration were fixed, both the As(V) and As(III) removals decrease with increasing initial solution pH. Under the same initial solution pH and adsorbent dosage, the removal efficiencies of total arsenic (As(V) and As(III)) were in the order as follows: As(V)>As(V)+As(III)>As(III). Moreover, adsorption isotherms of As(V) and As(III) fit the Langmuir model satisfactorily for the four different initial pH conditions as well as for the studied range of initial arsenic concentrations. It is concluded that the reclaimed IOCS can be considered as a feasible and economical adsorbent for arsenic removal.     

Effect of humic acid on sorption of technetium by alumina

Sorption of technetium by alumina has been studied in absence as well as in presence of humic acid using ⁹⁵Tc^m as a tracer. Measurements were carried out at fixed ionic strength (0.1 M NaClO₄) under varying pH (3-10) as well as redox (aerobic and reducing anaerobic) conditions. Under aerobic conditions, negligible sorption of technetium was observed onto alumina both in absence and in presence of humic acid. However, under reducing conditions (simulated with [Sn(II)] = 10⁻⁶ M), presence of humic acid enhanced the sorption of technetium in the low pH region significantly and decreased at higher pH with respect to that in absence of humic acid. Linear additive as well as surface complexation modeling of Tc(IV) sorption in presence of humic acid indicated the predominant role of sorbed humic acid in deciding technetium sorption onto alumina.     

Sorption of arsenite and arsenate on ferrihydrite: effect of organic and inorganic ligands

We studied the sorption of As(III) and As(V) onto ferrihydrite as affected by pH, nature and concentration of organic [oxalic (OX), malic (MAL), tartaric (TAR), and citric (CIT) acid] and inorganic [phosphate (PO(4)), sulphate (SO(4)), selenate (SeO(4)) and selenite (SeO(3))] ligands, and the sequence of anion addition. The sorption capacity of As(III) was greater than that of As(V) in the range of pH 4.0-11.0. The capability of organic and inorganic ligands in preventing As sorption follows the sequence: SeO(4) ≈ SO(4) < OX < MAL ≈ TAR < CIT < SeO(3) ? PO(4). The efficiency of most of the competing ligands in preventing As(III) and As(V) sorption increased by decreasing pH, but PO(4) whose efficiency increased by increasing pH. In acidic systems all the competing ligands inhibited the sorption of As(III) more than As(V), but in alkaline environments As(III) and As(V) seem to be retained with the same strength on the Fe-oxide. Finally, the competing anions prevented As(III) and As(V) sorption more when added before than together or after As(III) or As(V).     

Speciation of Cr(III) and Cr(VI) in environmental samples determined by selective separation and preconcentration on silica gel chemically modified with niobium(V) oxide

In this study a new method for chromium speciation in water using solid phase extraction coupled to a flow injection system and flame atomic absorption spectrometry was developed. The adsorption behavior of Cr(III) and Cr(VI) on Nb2O5-SiO2 allowed the selective separation of Cr(III) from Cr(VI) in the pH range of 6-9. Thus, a method for Cr(III) preconcentration and extraction using Nb2O5-SiO2 was developed. Total chromium was determined after the reduction of Cr(VI) to Cr(III) using sodium sulfite in acidic medium. The operational variables of the preconcentration and reduction procedures were optimized through full factorial and Doehlert designs. The limit of detection for Cr(III) was 0.34microgL(-1) and the precision was below 4.6%. Results for recovery tests using different environmental samples were between 90 and 105%. Certified reference materials (NIST 1640 and NIST 1643e) were analyzed in order to check the accuracy of the proposed method, and the results were in agreement with the certified values.     

Simultaneous removal of chromium and leather dye from simulated tannery effluent by photoelectrochemistry

The feasibility of the photobleaching of a leather acid dye, acid red 151, simultaneously to degradation of anionic surfactant, Tamol^®, and reduction of Cr(VI) to the less toxic Cr(III) was investigated by photoelectrocatalytic oxidation. The best experimental conditions were found to be pH 2.0 and 0.1 mol L⁻¹ sodium sulfate when the nanoporous Ti/TiO₂ photo anode was biased at +1.0 V and submitted to UV-irradiation. The photoelectrocatalytic oxidation promotes 100% discoloration, reducing around 98–100% of Cr(VI) and achieving an abatement of 95% of the original total organic carbon. The effect of pH, the applied potential, the Cr(VI) concentration and the complexation reaction between Cr(VI) and acid red dye were evaluated as to their effect on the kinetics of the reaction.     

Arsenic localization and speciation in the root-soil interface of the desert plant Prosopis juliflora-velutina

The bioavailability and mobility of arsenic (As) in soils depends on several factors such as pH, organic matter content, speciation, and the concentration of oxides and clay minerals, among others. Plants modify As bioavailability in the rhizosphere; thus, the biogeochemical processes of As in vegetated and non-vegetated soils are different. Changes in As speciation induced by the rhizosphere can be monitored using micro-focused synchrotron-based X-ray fluorescence (μXRF) combined with μX-ray absorption near-edge spectroscopy (μXANES). This research investigated As speciation in the rhizosphere of mesquite (Prosopis juliflora-velutina) plants grown in a sandy clay loam treated with As(III) and As(V) at 40 mg kg(-1). Rhizosphere soil and freeze-dried root tissues of one-month-old plants were analyzed by bulk XAS. Bulk XAS results showed that As(V) was the predominant species in the soil (rhizosphere and non-vegetated), whereas As(III) was dominant in the root tissues from both As(V) and As(III) treated plants. μXAS and μXRF studies of thin sections from resin embedded soil cores revealed the As(III)-S interactions in root tissues and a predominant As-Fe interaction in the soil. This research demonstrated that the combination of bulk XAS and μXAS techniques is a powerful analytical technique for the study of As speciation in soil and plant samples.     

Formation of cinnabar--estimation of favourable conditions in a proposed Swedish repository

A deep repository for permanent storage of mercury will be designed and built in Sweden. The preferred chemical state for mercury in such a repository would be the sulphide HgS (cinnabar), which is a highly insoluble and the dominating natural mercury mineral. The possible formation of HgS from HgO or Hg(0) by reaction with a sulphur source (S, FeS or FeS(2)) is discussed from thermodynamic considerations, and pe-pH-diagrams are constructed by using the computer code MEDUSA to illustrate under which conditions HgS would dominate. Calculations of the speciation (PHREEQE) under varying conditions (S/Hg-ratios, presence of chloride) are given. Long-term laboratory experiments are performed, where the formation of HgS from the basic components is demonstrated (after mixing under various conditions and storage at room temperature for up to 3 years). The feasibility of HgS-formation with time in a geologic repository under conditions representative of deep granitic bedrock (calcium-bicarbonate buffered to pH 7-8.5) is discussed, as well as effects of alkaline conditions (concrete environment, pH 10.5-12.5). Formation of soluble polysulphides is not expected as long as the S/Hg mole ratio is within 1-1.3 and pH is below 10.5-11. Concrete should be used with caution. Suitable ballast materials could be introduced that would reduce porewater-pH that otherwise would be above 12.     

Chemical vapor generation of arsane in the presence of L-cysteine. Mechanistic studies and their analytical feedback

The complex reactivity of the system As-AH-RSH-THB (As=As(III), As(V); AH=HCl, HClO4, CH3COOH; RSH=L-cysteine (Cys); THB=NaBH4) was investigated using continuous flow (CF) hydride generation (HG) coupled either with atomic absorption (AAS) or atomic fluorescence spectrometry (AFS). AsH3 generation was examined in the presence of Cys by varying acidity and the type of acid, the mixing sequence, and the reaction time of reagents. The strong depression of arsane generation, which is typically observed in the range of acidity of 0.2-2 M HCl, can be addressed to the low reaction rate of thiol-borane, hydroboron complexes, or both toward those As(III) substrates that are formed in the same reaction environment. The simultaneous presence of Cys-borane and As(III)-Cys species is at the origin of the gap of the arsane generation efficiency in the 0.2-2 M HCl acidity range. The selective formation of Cys-borane complexes, which are formed faster than As(III)-thiol complexes, can be achieved by a careful choice of the mixing sequence of the reagents. The simultaneous mixing of sample, Cys, and THB is able to reduce substantially the gap of the arsane generation efficiency in the 0.2-2 M HCl acidity range. These properties were employed to implement a simple method for selective determination of As(III) in samples containing inorganic arsenic: (i) Total inorganic arsenic is determined by sample treatment with 0.2 M Cys for 30 min, acidity 0.1 M HCl, followed by CF-HG-AFS; (ii) As(III) is selectively determined in 0.005 M CH3COOH in the presence of Cys using a chemifold setup allowing the simultaneous mixing of sample, 0.2 M Cys and 0.1 M THB. The selectivity, measured from the ratio between the slopes of calibration graphs As(III)/As(V), is 220. The interference effects of Cu(II), Fe(III), Ni(II), Co(II), Ag(I), Pd(II), and Pt(IV) can be kept under control using the simultaneous mixing of all the reagents. The tolerance toward the interferences was almost the same as that obtained by allowing the formation of As(III)-Cys complexes (offline sample pretreatment with Cys for 30 min). The method was tested with the application to the natural waters and mineral well waters analysis employing CF-HG-AFS.     

Perfluorosulfonated ionomer-modified diffusive gradients in thin films: tool for inorganic arsenic speciation analysis

A new concept in speciation analysis based on the diffusive gradients in thin films (DGT) technique is described. By use of two sets of DGT devices, one set with perfluorosulfonated ionomer (Nafion) diffusive membranes and the other with polyacrylamide, anionic and uncharged analytes can be fractionated on the basis of charge. The dual device method is applied to speciation analysis of dissolved inorganic arsenic species. Over the environmentally significant pH range, inorganic As(III) exists as neutral H(3)AsO(3), whereas As(V) is present as anionic H(2)AsO(4)(-) and HAsO(4)(2-). The measured diffusion coefficient of As(III) through the negatively charged Nafion membrane is significantly larger than that of the As(V) species, whereas diffusion rates are similar through polyacrylamide diffusive gels. Hence, after simultaneously deploying DGT devices with and without Nafion membranes, measurement of the amount of accumulated As in each type of device enables the concentration of both oxidation states to be determined.     

The effect of pre-ozone oxidation on acute toxicity and inert soluble COD fractions of a textile finishing industry wastewater

The present work evaluates pre-ozonation for removal of acute toxicity, color and COD as well as reduction of inert soluble COD fractions in two wastewater samples (S1 and S2) taken from a textile finishing industry, located in Istanbul (Turkey). The wastewater samples were oxidized at original pH of 8.6-8.8 under 18.5-24 mg/L of applied ozone doses. Acute toxicity was monitored using Daphnia magna. The results showed that pre-ozonation improved the biodegradability and reduced the acute toxicity. Acute toxicity in raw wastewaters was reduced by 80-90% using 129-200 mg/L transferred ozone (TrO(3)) concentrations. At this point, 86-96% of color, 33-39% of soluble COD and 57-64% of total COD were removed from wastewaters. Both color and COD parameters were found related to the acute toxicity of the wastewater. Pre-ozonation decreased the inert soluble COD fraction (S(I)) of raw wastewater while soluble product formation (S(P)) increased slightly (5-10 mg/L). However, residual COD (the sum of S(I) and S(P)) remained below discharge limit.     

Effect of contact order on the adsorption of inorganic arsenic species onto hematite in the presence of humic acid

The speciation of aqueous and adsorbed As forms of arsenic (As) is a major environmental concern in the presence of humic acid (HA). The speciation during As adsorption process by the effect of contact order were evaluated in various equilibrated ternary systems consisting of As, HA and hematite. One ternary system was composed of the preequilibrated As(III)- or As(V)-HA complex, with the subsequent addition of hematite ((As-HA)-hematite system), and the other consisted of the preequilibrated HA-hematite, with the addition of As(III) or As(V) (As-(HA-hematite) system). The presence of HA led to a decrease in the As adsorption, opposite to cationic adsorption. The order of the amounts of As adsorption were found to follow as: As(V)-hematite>hematite-(As(V)-HA)>As(V)-(HA-hematite)>As(III)-hematite>hematite-(As(III)-HA)>As(III)-(HA-hematite). Free As(V) and As-HA complex were preferentially adsorbed onto the hematite surface. The immobilization of As can come from adsorbed HA on mineral surfaces, and formation of As-HA complex, following their slow kinetics.     

Effects of pH and dissolved oxygen on Cr(VI) removal in Fe(0)/H2O systems

The effects of pH and dissolved oxygen (DO) on aqueous Cr(VI) removal by micro-scale zero-valent iron (Fe(0)/H(2)O system) were investigated. Batch experiments were conducted at pH 4.0, 5.0 and 6.0 under oxic and anoxic conditions. Column experiments were performed at pH 5.0 and 7.5 under oxic condition. Spectroscopic analyses were applied to explain the mechanism of Cr(VI) removal using X-ray absorption near-edge structure (XANES), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results showed that the kinetics of Cr(VI) removal were fastest at pH 5 under both oxic and anoxic conditions. As a rule, Cr(VI) removal were faster under oxic conditions than under anoxic conditions. Column experiments showed that Cr(VI) removal was about 1.7-fold higher at pH 5 than at pH 7.5. XANES (X-ray absorption near edge structures) results showed that Fe(0) reduced Cr(VI) to Cr(III) under both oxic and anoxic conditions. X-ray diffraction patterns of the Cr(VI)-Fe(0) reaction products suggested partial formation of chromite (FeCr(2)O(4)) at pH 5 and 6 under oxic conditions. However, nano-sized clusters of Cr(III)/Fe(III) hydroxide/oxyhydroxide were formed on the surface of Fe(0) under anoxic conditions. These results indicate that the presence of oxygen in solution plays an important role in control of the kinetic of Cr(VI) removal and in development of various Cr(VI) reduction products.