Treatment of Arsenic Contaminated Groundwater Using Calcium Impregnated Granular Activated Carbon in a Batch Reactor: Optimization of Process Parameters

This paper is an experimental investigation into the removal of arsenic species from simulated groundwater by adsorption onto Ca²⁺ impregnated granular activated carbon (GAC‐Ca) in the presence of impurities like Fe and Mn. The effects of adsorbent concentration, pH and temperature on the percentage removal of total arsenic (As(T)), As(III) and As(V) have been discussed. Under the experimental conditions, the optimum adsorbent concentration of GAC‐Ca was found to be 8 g/L with an agitation time of 24 h, which reduced As(T) concentration from 188 to 10 μg/L. Maximum removal of As(V) and As(III) was observed in a pH range of 7–11 and 9–11, respectively. Removal of all the above arsenic species decreased slightly with increasing temperature. The presence of Fe and Mn increased the adsorption of arsenic species. Under the experimental conditions at 30°C, the maximum percentage removals of As(T), As(III), As(V), Fe, and Mn were found to be ca. 94.3, 90.6, 98.0, 100 and 63%, respectively. It was also observed that amongst the various regenerating liquids used, a 5 N H₂SO₄ solution exhibited maximum regeneration (ca. 91%) of the spent GAC‐Ca.     

Modeling of the Removal of Arsenic Species from Simulated Groundwater Containing As,Fe, and Mn: A Neural Network Based Approach

The present paper deals with the modeling of the removal of total arsenic As(T), trivalent arsenic As(III), and pentavalent arsenic As(V) from synthetic solutions containing total arsenic (0.167–2.0 mg/L), Fe (0.9–2.7 mg/L), and Mn (0.2–0.6 mg/L) in a batch reactor using Fe impregnated granular activated charcoal (GAC‐Fe). Mass ratio of As(III) and As(V) in the solution was 1:1. Multi‐layer neural network (MLNN) has been used and full factorial design technique has been applied for the selection of input data set. The developed models are able to predict the adsorption of arsenic species with an error limit of ?0.3 to +1.7%. Combination of MLNN with design of experiment has been able to generalize the MLNN with less number of experimental points.     

Stability of arsenopyrite and As(III) in low-temperature acidic solutions

Arsenopyrite is one of the most important pri-mary arsenic mineral. In the Eh-pH diagram of the As-O2-S-H2O system, if the total arsenic concentration (TAs) is taken to be 0.75 mg/L, the total sulfur con-centration, 32 mg/L, the temperature, 25℃and the pressure, one atmosphere pressure for the discrimina-tion of arsenic species, it may be found that under hy-pergene conditions, arsenopyrite is a moderately stable mineral. Only in the strongly alkaline and reducing environment can arsenopy…     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

Mycorrhizal Colonization Affects the Survival of Vetiveria zizanioides (L.) Nash Grown in Water Containing As(III)

The presence of arsenic (As) in water is of great public concern. Arsenic exists in three common valence states viz., As(0) metalloid arsenic, As(III) (arsenite) and As(V) (arsenate). Arsenite [As(III)] is the most toxic form among arsenicals which, predominates in anaerobic conditions, generally in flooded soils and in the water with high BOD. Experiments were conducted to investigate the effect of As(III) on the mycorrhization in vetiver (Vetiveria zizanioides (L.) Nash) grass in hydroponics. Studies showed significant alteration in the mycorrhizal colonization in the roots of vetiver exposed to higher concentrations of As(III) starting from 1.0, 2.0, 3.0, 4.0 to 5.0 mg/L prepared in 5% Hoagland nutrient solution without addition of phosphate ions. Considerable reduction in the mycorrhizal intensity (M) was observed in all the treatment sets as compared to the control suggesting a negative impact of the As(III) on the mycorrhizal association. Simultaneously, the study also showed that, As(III) is toxic to the vetiver plants having mycorrhizal association however plants with non‐mycorrhizal (cleansed) roots were found to be able to survive for a longer period exposed to As(III).     

Removal of Arsenic from Simulated Groundwater Using GAC‐Ca in Batch Reactor: Kinetics and Equilibrium Studies

This paper deals with kinetics and equilibrium studies on the adsorption of arsenic species from simulated groundwater containing arsenic (As(III)/As(V), 1:1), Fe, and Mn in concentrations of 0.188, 2.8, and 0.6 mg/L, respectively, by Ca²⁺ impregnated granular activated charcoal (GAC‐Ca). Effects of agitation period and initial arsenic concentration on the removal of arsenic species have also been described. Although, most of the arsenic species are adsorbed within 10 h of agitation, equilibrium reaches after ～24 h. Amongst various kinetic models investigated, the pseudo second order model is more adequate to explain the adsorption kinetics and film diffusion is found to be the rate controlling step for the adsorption of arsenic species on GAC‐Ca. Freundlich isotherm is adequate to explain the adsorption equilibrium. However, empirical polynomial isotherm gives more accurate prediction on equilibrium specific uptakes of arsenic species. Maximum specific uptake (q_max) for the adsorption of As(T) as obtained from Langmuir isotherm is 135 µg/g.     

Inorganic As speciation and bioavailability in estuarine sediments of Todos os Santos Bay, BA, Brazil

The spatial distribution of As (total As, As (III) and As (V)) in estuarine sediments from the main tributaries of Todos os Santos Bay, BA, Brazil, was evaluated under high and low flow conditions. The concentrations of As were determined using a slurry sampling procedure with hydride generation atomic absorption spectrometry (HG-AAS). The highest concentrations were observed at estuary mouths, and exceeded conservative lower threshold value (Threshold Effects Level; TEL). Due to the oxic conditions and abundance of Mn and Fe (oxyhydr)oxides in the sediments, most inorganic arsenic in the Subaé and Paraguaçu estuaries was present as As (V). Nevertheless, the concentration of As (III) at several locations along the Jaguaripe River were also above the TEL value, suggesting that As may be toxic to biota. In the Subaé estuary, antropogenic activities are the main source of As. At the Jaguaripe and at Paraguaçu estuaries, nevertheless, natural sources of As need to be considered to explain the distribution patterns.     

Arsenic — a Review. Part I: Occurrence,Toxicity, Speciation,Mobility

In natural waters arsenic concentrations up to a few milligrams per litre were measured. The natural content of arsenic found in soils varies between 0.01 mg/kg and a few hundred milligrams per kilogram. Anthropogenic sources of arsenic in the environment are the smelting of ores, the burning of coal, and the use of arsenic compounds in many products and production processes in the past. A lot of arsenic compounds are toxic and cause acute and chronic poisoning. In aqueous environment the inorganic arsenic species arsenite (As(III)) and arsenate (As(V)) are the most abundant species. The mobility of these species is influenced by the pH value, the redox potential, and the presence of adsorbents such as oxides and hydroxides of Fe(III), Al(III), Mn(III/IV), humic substances, and clay minerals.     

Arsenic — a Review. Part II: Oxidation of Arsenic and its Removal in Water Treatment

In natural waters arsenic normally occurs in the oxidation states +III (arsenite) and +V (arsenate). The removal of As(III) is more difficult than the removal of As(V). Therefore, As(III) has to be oxidized to As(V) prior to its removal. The oxidation in the presence of air or pure oxygen is slow. The oxidation rate can be increased by ozone, chlorine, hypochlorite, chlorine dioxide, or H₂O₂. The oxidation of As(III) is also possible in the presence of manganese oxide coated sands or by advanced oxidation processes. Arsenic can be removed from waters by coprecipitation with Fe(OH)₃, MnO₂ or during water softening. Fixed‐bed filters have successfully been applied for the removal of arsenic.The effectiveness of arsenic removal was tested in the presence of adsorbents such as FeOOH, activated alumina, ferruginous manganese ore, granular activated carbon, or natural zeolites. Other removal technologies are anion exchange, electrocoagulation, and membrane filtration by ultrafiltration, nanofiltration or reverse osmosis.     

Adsorption of As on hydroxy-Fe-montmorillonite complexes

DOI: 10.1360/03yd0553 Arsenic, a toxic element, is ubiquitous in the earth’s crust and may lead to health risks for humans. This may come about as a result of oxidative weathering and dissolution of As-containing minerals, use of ar-senical pesticides, excess use of some fertilizers and from mine drainage, smelter wastes and agricultural drainage water from certain arid regions. The dis-solved inorganic arsenic is transported in surface or2156 Science in China Ser. D Earth Sciences groun…     

Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration

Pyrite is a common sulfide mineral, particularly abundant in mining waste. It is a focus of mine envi-ronmental concern because the oxidation of exposed pyrite may lead to acid drainage and poisonous mate-rials (like As and heavy metals) release. In the United States, approximately $1000000 per day is spent in alleviating acid mine drainage[1], while the Canadian mining community has environmental liabilities that exceed $2 billion for disposal, management, and rec-lamation of mine waste[2]. …     

Effective Precipitation of Arsenic from Aqueous Solution by Iron(III) Sulfate

A study of the removal of As(V) from aqueous solution by Fe₂(SO₄)₃ has been carried out to establish optimum parameters for the process. Optimum arsenic removal is obtained at pH = 5, and mole ratio Fe(III)/As(V) = 7. Minimum arsenate solubility is obtained from sediments precipitated at pH = 5 and Fe/As = 7…8.     

Über die Bestimmung von Aminopolycarbonsäuren durch Ionenpaarchromatographie

Determination of aminopolycarboxylic acids by ion pair chromatography. A method for the determination of aminopolycarboxylic acids, especially NTA and EDTA, is described, based on ion pair chromatography. The detection is done in UV at about 260 nm. The analytes are transformed into the Fe(III)-complexes before separation. For lower concentrations this can automatically be achieved by injecting the analyte into the Fe(III)-containing eluent. For higher concentrations, Fe(III) has to be added separately. Determination is possible down to 10 μg/1 concentration.     

Determination of arsenic(III) for the investigation of the microbial oxidation of arsenic(III) to arsenic(V)

Recent evaluations of acute and chronical toxicity of arsenic resulted in a reduction of the standard value for total arsenic from 40 μg/L to 10 μg/L in drinking water which will be valid in Germany after a transition period as from January 1996. Arsenic is well known as substance of deep groundwaters, mainly of geogenic origin and normally found as As(III) or As(V). As(V) is well removable by flocculation and filtration after adding iron salts. As(III), however, has to be oxidized first to As(V). Therefore, it is important for treatment techniques to be able to distinguish between As(III) and As(V). A modified determination of As(III) using flow injection analysis was installed and optimized in order to investigate whether As(III) may be oxidized to As(V) by bacteria in natural waters. The results showed that at 4°C, no As(III)-oxidation was observed within 14 days. At room temperature, however, in the bacteria-containing samples, an As(III)-oxidation was found starting after 3 to 7 days. After 14 days, no As(III) was left over. In contrast, in the sterile samples, no As(III)-oxidation could be observed within 14 days. These results demonstrated that microbial processes influence the oxidation of As(III) to As(V) in natural waters.     

Use of the Anion‐Exchange Resin Amberlite IRA‐93 for the Separation of Arsenite and Arsenate in Aqueous Samples

The method described uses the separation of As(III) and As(V) species in aqueous samples by means of the anion‐exchange resin Amberlite IRA‐93. The samples were acidified using acetic acid and passed through a glass column filled with pre‐treated Amberlite IRA‐93 resin. As(III) was poorly adsorbed on the anionic exchanger material, whereas As(V) was retained. The arsenic concentration was measured in the column effluent by graphite furnace AAS (GF‐AAS). The retained As(V) was eluted from the column using 1 M NaOH. Prior to the determination of the As(V) concentration in the NaOH eluate, the eluate was passed through a glass column filled with a cation‐exchange resin (Amberlite 200) to remove sodium ions and minimize the Na⁺ interference with the AAS determination. After calibration the method was applied to the separation of As(III) and As(V) species in two aqueous extracts of arsenic contaminated soils. The results were compared with those obtained from an on‐line separation and determination of As(III) and As(V) in the aqueous soil extracts using a state of the art HPLC‐ICP‐MS system.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Reconstructing the iron cycle from the horizontal distribution of metals in the sediment of Baldeggersee

In Baldeggersee, the distributions of solid phase Fe, Mn, V, Cr, As and Mo were determined in different sediment strata, deposited under various deep-water oxygen conditions. Iron concentrations are correlated with water depth when an anoxic sediment is in contact with an oxic water column. Benthic redox gradients trigger iron transport towards the deepest site (geochemical focusing) and loss of iron from the shallower parts through the outflow. Fe cycling in the lake is inhibited by oxygen penetration into the sediment. Vanadium and arsenic can be used as tracers for the internal Fe cycle. Their distribution patterns are highly correlated with iron. In case of a stable oxycline in the deep water, Mo is enriched in the sediment and correlates with Mn. The horizontal distribution patterns of Fe, V, As and the correlation of Fe and Mn with trace metals are promising proxy indicators for the reconstruction of deep-water oxygen conditions during deposition.     

The enrichment and removal of arsenic (III) from water samples using HFSLM

At specific concentrations oxyanions such as arsenic pose a major threat to human beings and to the environment because of their ability to biomagnify. The World Health Organization has set the drinking water standard at 10 μg l⁻¹ for arsenic. It is in this regard that novel and cheaper methods to detect oxyanions and remove them from the environment are developed. In this work, we have developed sample preparation methods involving solid phase and liquid membrane for the extraction and enrichment of these oxyanions in aqueous environments. Various parameters which govern their optimal extraction and enrichment have been optimised. The manipulation of the liquid membrane extraction process was utilised to selectively extract arsenic (III) which is more toxic as compared to arsenic (V). The liquid membrane consisted of a combination of two organic solvents, and n-undecane and di-n-hexyl ether were used in a combination at various ratios of the two liquid membranes. The means of detection was by graphite furnace atomic absorption spectroscopy (GFAAS) as well as inductively coupled plasma optical emission spectroscopy (ICP-OES). The applicability of the method was tested in real wastewater samples where it was able to remove at least 50% of As (III) with enrichment factors of up to 20.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.