Speciation and uptake of arsenic accumulated by corn seedlings using XAS and DRC-ICP-MS

ICP-MS was used to investigate the uptake of As(III) and As(V) from hydroponics growth media by corn seedlings. It was found that arsenic uptake by the plant roots for the arsenic(V) and arsenic(III) treatments were 95 and 112 ppm, respectively. However, in the shoots of the arsenic (V) treatments had 18 ppm whereas arsenic(III) treatments had 12 ppm. XANES studies showed that As for both treatments arsenic was present as a mixture of an As(III) sulfur complex and an As(V) oxygen complex. The XANES data was corroborated by the EXAFS studies showing the presence of both oxygen and sulfur ligands coordinated to the arsenic. Iron concentrations were found to increase by 4 fold in the As(V) contaminated growth media and 7 fold in the As(III) treatment compared to the control iron concentration of 500 ppm. Whereas, the total iron concentration in the shoots was found to decrease by approximately the same amount for both treatments from 360 ppm in the control to approximately 125 ppm in both arsenic treatments. Phosphorus concentrations were found to decrease in both the roots and shoots compared to the control plants. The total sulfur in the roots was found to increase in the arsenic(III) and arsenic(V) treatments to 560 ppm and 800 ppm, respectively, compared to the control plants 358 ppm. In addition, the total sulfur in shoots of the plants was found to remain relatively constant at approximately 1080 ppm. The potassium concentrations in the plants were found to increase in the roots and decrease in the shoots.     

Simultaneous determination of Cd(II), Cu(II), Pb(II) and Zn(II) by derivative stripping chronopotentiometry in Pittosporum tobira leaves: a measurement of local atmospheric pollution in Messina (Sicily, Italy)

The purpose of this study is to investigate the bio-accumulation of Cd(II), Cu(II), Pb(II) and Zn(II) in Pittosporum tobira (Thunb.) Aiton leaves sampled in different zones of Messina, in order to assess the level of atmospheric metal deposition in correlation with the traffic volume. Derivative stripping chronopotentiometry was used as a practical, precise and sensitive technique to determine simultaneously Cd, Cu, Pb and Zn levels in Pittosporum leaves. In the optimised electro-chemical conditions, detection limits lower than 0.05 microg kg(-1) were achieved, whereas the accuracy, expressed as obtained recoveries from certified materials, was in the range 93.5-102.7%. The obtained data provided evidence that Cd and Pb levels significantly decreased from high to low traffic density zones (p < 0.005, ANOVA), whereas Cu and Zn are accumulated by plants particularly from the soil and their contents is not related to the traffic volume.     

Removal of arsenic(V) from aqueous solutions using iron-oxide-coated modified activated carbon.

Removal of arsenic(V) from aqueous solutions was evaluated with the following three different sorption materials: coal-based activated carbon 12 x 40 (activated carbon), iron(II) oxide (FeO)/activated carbon-H, and iron oxide. The apparent characteristics and physical chemistry performances of these adsorbents were investigated by X-ray diffraction, nitrogen adsorption, and scanning electronic microscope. Also, batch experiments for arsenic removal were performed, and the effects of pH value on arsenic(V) removal were studied. The results suggest that the main phases of the iron oxide surface are magnetite, maghemite, hematite, and goethite; fine and uniform iron oxide particles can cover activated carbon surfaces and affect the surface area or pore structures of activated carbon; adsorption kinetics obey a pseudo-first-order rate equation; and adsorption capacities of adsorbents are affected by the values of pH. The optimum value of pH for iron oxide lies in a narrow range between 4.0 and 5.5, and arsenic(V) removal by FeO/activated carbon-H is ideal and stable in the pH range 3 to 7, while activated carbon has the lowest adsorption capacity in the entire pH range. Also, the adsorption characteristics of FeO/activated carbon-H composites and virgin activated carbon match well the Langmuir adsorption model, while those of iron oxide fit well the Freundlich adsorption model.     

Cu(II)-Glyphosate system: A study by anodic stripping voltammetry and the influence on Cu adsorption by montmorillonite

The influence of the pesticide glyphosate (GPS) on the adsorption of Cu (II) on montmorillonite has been examined. The complexation of Cu(II) with GPS was studied using anodic stripping voltammetry in differential pulse mode (DPASV). It has been concluded that the complexes present a labile behaviour and GPS shows a low but noticeable degree of heterogeneity, probably due to complexation of Cu bv more than one GPS species. Cu(II) adsorption on montmorillonite is drastically decreased in the presence of GPS, due to several reasons: decrease in free Cu concentration due to formation of Cu-GPS complexes; surface loading of GPS on montmorillonite, obstructing interlamellar Cu²⁺ adsorption and competitive effect between protons and Cu²⁺ for interlamellar positions.     

Relation of dietary inorganic arsenic exposure and urinary inorganic arsenic metabolites excretion in Japanese subjects

Inorganic arsenic (InAs) is a ubiquitous metalloid that has been shown to exert multiple adverse health outcomes. Urinary InAs and its metabolite concentration has been used as a biomarker of arsenic (As) exposure in some epidemiological studies, however, quantitative relationship between daily InAs exposure and urinary InAs metabolites concentration has not been well characterized. We collected a set of 24-h duplicated diet and spot urine sample of the next morning of diet sampling from 20 male and 19 female subjects in Japan from August 2011 to October 2012. Concentrations of As species in duplicated diet and urine samples were determined by using liquid chromatography-ICP mass spectrometry with a hydride generation system. Sum of the concentrations of urinary InAs and methylarsonic acid (MMA) was used as a measure of InAs exposure. Daily dietary InAs exposure was estimated to be 0.087 µg kg^?1 day^?1 (Geometric mean, GM), and GM of urinary InAs+MMA concentrations was 3.5 ng mL^?1. Analysis of covariance did not find gender-difference in regression coefficients as significant (P > 0.05). Regression equation Log ₁₀ [urinary InAs+MMA concentration] = 0.570× Log ₁₀ [dietary InAs exposure level per body weight] + 1.15 was obtained for whole data set. This equation would be valuable in converting urinary InAs concentration to daily InAs exposure, which will be important information in risk assessment.     

Speciation of five arsenic species (arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS

A method using Ion Chromatography hyphenated to an Inductively Coupled Plasma-Mass Spectrometer has been developed to accurately determine arsenite (As(III)), arsenate (As(V)), mono-methylarsonic acid (MMAA(V)), dimethylarsinic acid (DMAA(V)) and arsenobetaine (AsBet) in different water matrices. The developed method showed a high sensitivity with detection limits for each arsenic species close to 0.4pg injected. Arsenite and arsenate were the major species found in surface and well waters, but AsBet and DMAA(V) were found in some surface waters, which has never been reported before, while in some natural mineral waters located in volcanic region, the arsenic content exceeded the maximal admissible arsenic content by European legislation standards and the predominant form was As(V).     

基于方波溶出伏安法的电化学传感器检测水体中痕量铅

基于方波溶出伏安法运用丝网印刷电极探索了一种利用电化学传感器检测水样中痕量铅的方法.得到了该检测方法的最佳参数:方波频率30 Hz,振幅80 mV,电位增量5 mV;0.5 mol/L的支持电解质(KCl);沉积电位-1.1 V,沉积时间400 s.在该优化条件下,在浓度为25 ～ 500μg/L范围内溶出峰电流与铅离子浓度呈良好的线性关系(R2=0.9945).对于几种其他金属离子的干扰实验结果表明,Mn2的存在严重抑制铅离子的峰电流.     

GC-profiles of chlorinated terpenes (Toxaphenes) in some Finnish environmental samples

The profiles of chlorinated terpenes in Finnish environmental samples were compared by GLC-SIM technique with those of toxaphene and Eastern European “dark”. The profiles in the seal blubber in the Northern and in the Eastern Baltic Sea proved to be similar. Chlorinated terpenes were found to be present in Finnish human milk.The spent bleach liquor of pine kraft pulp mill contained components having similar retention times and responses to those from toxaphene components.     

Influence of sulfide (S2-) on preservation and speciation of inorganic arsenic in drinking water

Generally, H2SO4, HNO3, HCl or the combination of ethylenediaminetetraacetate with acetic acid (EDTA-HAc) have been used to preserve arsenite and arsenate species prior to analysis. When these acidic preservatives are added in sulfidic water, instantaneous precipitation of poorly crystalline orpiment, As2S3(am), occurs, thereby lowering the total arsenic, As(Tot), analysis. A new method for the determination of As(Tot) was developed in which acid-preserved sulfidic water samples were oxidized with NaOCl, converting As2S3(am) and thioarsenic species to arsenate. A new method was also developed for the separation of uncharged arsenite and charged thioarsenic species in fresh, unpreserved sulfidic water by adsorbing the charged thioarsenic species while allowing uncharged arsenite to pass through a strong-base resin unhindered. The adsorbed thioarsenic species could be eluted efficiently with 0.16 M NaOCl solution.     

Speciation of arsenic and chromium metal ions by reversed phase high performance liquid chromatography

The speciation of arsenic [As(III) and As(V)] and chromium [Cr(III) and Cr(VI)] was carried out by high performance liquid chromatography. The column used was Econosil C18 (250 x 4.6 mm i.d., particle size 10 microm). The mobile phases consisted of water-acetonitrile (80:20, v/v) for arsenic and 10 mM ammonium acetate buffer (6.0 pH)-acetonitrile (10:90, v/v) for chromium speciation separately and respectively. The detection was carried out by UV-Vis at 410 nm and atomic absorption spectrometer (AAS) respectively and separately. The values of alpha and Rs of As(III) and As(V) species were 1.4 and 1.5 respectively while the values of alpha and Rs for Cr(III) and Cr(VI) were 1.35 and 0.2 respectively. The effect of the acetonitrile percentages was also carried out on the speciation of arsenic only. The relative standard deviation and limit of detection were in the range of 0.01-0.02 and 0.4-1.0 microg/ml respectively.     

Removal of fluoride from water by using a coagulant (inorganic polymeric coagulant)

Environmental Science and Pollution Research - Excess fluoride (F) ion of drinking water is a major problem in many areas of India and causes harmful effects such as dental and skeletal fluorosis....     

Remediation of organic and inorganic arsenic contaminated groundwater using a nanocrystalline TiO2-based adsorbent

A nanocrystalline TiO₂-based adsorbent was evaluated for the simultaneous removal of As(V), As(III), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) in contaminated groundwater. Batch experimental results show that As adsorption followed pseudo-second order rate kinetics. The competitive adsorption was described with the charge distribution multi-site surface complexation model (CD-MUSIC). The groundwater containing an average of 329 μg L^?1 As(III), 246 μg L^?1 As(V), 151 μg L^?1 MMA, and 202 μg L^?1 DMA was continuously passed through a TiO₂ filter at an empty bed contact time of 6 min for 4 months. Approximately 11 000, 14 000, and 9900 bed volumes of water had been treated before the As(III), As(V), and MMA concentration in the effluent increased to 10 μg L^?1. However, very little DMA was removed. The EXAFS results demonstrate the existence of a bidentate binuclear As(V) surface complex on spent adsorbent, indicating the oxidation of adsorbed As(III).     

Determination of total arsenic content in water by atomic absorption spectroscopy (AAS) using vapour generation assembly (VGA)

Analysis of arsenic in water is important in view of contamination of ground water with arsenic in some parts of the world including West Bengal in India and neighboring country Bangladesh. WHO has fixed the threshold for arsenic in drinking water to 10ppb (microg/l) level, hence the methodology for determination of arsenic is required to be sensitive at ppb level. Atomic absorption spectrophotometry with vapour generation assembly (AAS-VGA) is well known technique for the trace analysis of arsenic. However, total arsenic analysis [As(III)+As(V)] is very crucial and it requires reduction of As(V) to As(III) for correct analysis. As(III) is reduced to AsH3 vapours and finally to free As atoms, which are responsible for absorption signal in AAS. To accomplish this the vapour generation assembly attached to AAS has acid channel filled with 10 M HCl and the reduction channel with sodium borohydride. Further sample can be reduced either before aspiration for analysis, using potassium iodide (KI) or the sample can be introduced in the instrument directly and KI can be added in the reduction channel along with the sodium borohydride. The present work shows that samples prepared in 3 M HCl can be reduced with KI for 30 min before introduction in the instrument. Alternatively samples can be prepared in 6 M HCl and directly aspirated in AAS using KI in VGA reduction channel. The latter methodology is more useful when the sample size is large and time cycle is difficult to maintain. It is observed that the acid concentration of the sample in both the situations plays an important role. Further reduction in acid concentration and analysis time is achieved for the arsenic analysis by using modified method. Analysis in both the methods is sensitive at ppb level.     

Modelling of phosphorus removal from aqueous and wastewater samples using ferric iron

Batch laboratory scale experiments were conducted to investigate the removal of phosphate from aqueous and municipal wastewater samples by addition of FeCl(3).6H(2)O. The effect of pH, Fe-dose and initial phosphate concentration were assessed. Optimum phosphate removal, 63% for 1:1 molar addition of Fe(III) was observed at pH 4.5. However, a 155% excess of Fe-dose was necessary for complete phosphorus removal. Phosphorus removal from municipal wastewater was slightly higher than that observed for the aqueous solutions. A chemical precipitation mathematical model was developed and tested with the available experimental data. The model included a total of 15 chemical reactions and 4 solid phases with the option of single-phase precipitation or two-phase co-precipitation. The resulting system of non-linear algebraic equations was solved numerically, using the Wijngaarden-Dekker-Brent method.     

Adsorption of arsenic(V) by iron-oxide-coated diatomite (IOCD)

Purposes and aims  

Economically efficient methods for removing arsenic from the drinking water supply are urgently needed in many parts of the world. Iron oxides are known to have a strong affinity for arsenic in water. However, they are commonly present in the forms of fine powder or floc, which limits their utility in water treatment. In this study, a novel granular adsorbent, iron-oxide-coated diatomite (IOCD), was developed and examined for its adsorption of arsenic from water.     

Enhanced solubilization of arsenic and 2,3,4,6 tetrachlorophenol from soils by a cyclodextrin derivative

The application of extracting aqueous solutions with cyclodextrins in several soil remediation technologies has been increasingly studied but little is known about their removal capacities toward the inorganic species. Herein, the effectiveness of cyclodextrins (CDs) in extracting arsenic, copper, and iron from a mining soil is presented. In a preliminary test of four types of CD aqueous solutions, only the addition of carboxylmethyl-beta-cyclodextrin CMCD (a cyclodextrin derivative) led to a significant enhancement in arsenic removal. An increase in the concentration of copper and iron in the leachates was also observed with CMCD. Kinetic study of arsenic release was carried out at two temperatures (20 and 35 degrees C). The arsenic concentration in the leachates increases with increasing cyclodextrin concentration. At an 80 mM CMCD concentration, arsenic, copper, and iron released in filtrates were about 20-, 1,000-, and 4,000-fold greater, respectively, than that obtained using deionized water. In the soil system, the CMCD capacity removal was found to be higher for cations than for arsenic. Because the tetrachlorophenol can co-occur with arsenic and copper in several contaminated sites, its solubilization by CMCD was also investigated. Extraction experiments were performed to extract 2,3,4,6 tetrachlorophenol (TeCP) in spiked soil with CMCD. The results of batch experiments have shown that CMCD could significantly increase the TeCP extraction from soil. CD sorption on soils as quantified by a fluorescence technique was low, indicating no significant loss of CD during the leaching experiments. The use of CMCD as a flushing agent to enhance the removal of both inorganic and organic pollutants from mixed-contaminated soils appears as a promising remediation method.