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.     

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.     

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.     

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.     

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.     

Detoxification of Arsenite through Adsorption and Oxidative Transformation on Pyrolusite

Adsorption and oxidative transformation processes critically affect the mobility and toxicity of arsenic (As) in the environment. In this study, the detoxification of arsenite through adsorption and oxidation by pyrolusite was systematically investigated. Disappearance of aqueous As(III) in the solution can be efficiently achieved using pyrolusite. The As(III) oxidative transformation product arsenate or As(V) was obtained both in the solution and on the pyrolusite surface. The arsenic species adsorbed on pyrolusite exist in two forms: As(III) and As(V). Furthermore, over 64.8% of the adsorbed As cannot be desorbed. They were fixed more stably in the structure of the mineral to achieve a safer removal. Lower As(III) initial concentration increased As(III) detoxification rates. Elevating the reaction pH from 4.5 to 7.9 elicited a slight effect on the disappearance rate of As(III). Efficient As(III) detoxification can be achieved by pryrolusite within the studied pH range. The addition of low‐molecular‐weight carboxylic acids decreased the detoxification rate of As(III) through competition for active sites on pyrolusite. Co‐existing divalent metal ions, such as Ca²⁺, Ni²⁺, and Mn²⁺, also decreased the detoxification rate of As(III). However, the trivalent ion Cr³⁺ largely increased the detoxification rate through co‐precipitation and adsorption processes.     

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.     

Peroxymonosulfate Improves the Activity and Stability of Manganese Oxide for Oxidation of Arsenite to Arsenate

Manganese oxide has been widely investigated for oxidation of arsenite (As(III)) to arsenate (As(V)) due to its high redox potential; however, it becomes extremely unstable after reuse. Here, As(III) oxidation activity and stability of manganese oxide in the presence of peroxymonosulfate (PMS) is investigated. Batch experimental results reveal that manganese oxide/PMS exhibits high catalytic activity for As(III) oxidation compared to manganese oxide or PMS alone. Addition of PMS to manganese oxide not only reveals long‐term stability for As(III) oxidation, but also shows high As(III) oxidation activity in the presence of coexisting ions such as As(V) and phosphate. Quenching tests reveal that As(III) oxidation in the manganese oxide/PMS system is attributed to activation of PMS by manganese oxide at different oxidation states (Mn(III) and Mn(IV)), and the generation of sulfate radicals that are responsible for As(III) oxidation.     

MTBE in Drinking Water Production – Occurrence and Efficiency of Treatment Technologies

In Germany, the gasoline additive methyl tert‐butyl ether (MTBE) is almost constantly detected in measurable concentrations in surface waters and is not significantly removed during riverbank filtration. The removal of MTBE from water has been the focus of many studies that mostly were performed at high concentration levels and centred in understanding the mechanisms of elimination. In order to assess the performance of conventional and advanced water treatment technologies for MTBE removal in the low concentration range further studies were undertaken. Laboratory experiments included aeration, granulated activated carbon (GAC) adsorption, ozonation and advanced oxidation processes (AOP). The results show that the removal of MTBE by conventional technologies is not easily achieved. MTBE is only removed by aeration at high expense. Ozonation at neutral pH values did not prove to be effective in eliminating MTBE at all. The use of ozone/H₂O₂ (AOP) may lead to a partly elimination of MTBE. However, the ozone/H₂O₂ concentrations required for a complete removal of MTBE from natural waters is much higher than the ozone levels applied nowadays in waterworks. MTBE is only poorly adsorbed on activated carbon, thus GAC filtration is not efficient in eliminating MTBE. A comparison with real‐life data from German waterworks reveals that if MTBE is detected in the raw water it is most often found in the corresponding drinking water as well due to the poor removal efficiency of conventional treatment steps.     

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…     

Arsenic Control During Aquifer Storage Recovery Cycle Tests in the Floridan Aquifer

Implementation of aquifer storage recovery (ASR) for water resource management in Florida is impeded by arsenic mobilization. Arsenic, released by pyrite oxidation during the recharge phase, sometimes results in groundwater concentrations that exceed the 10 µg/L criterion defined in the Safe Drinking Water Act. ASR was proposed as a major storage component for the Comprehensive Everglades Restoration Plan (CERP), in which excess surface water is stored during the wet season, and then distributed during the dry season for ecosystem restoration. To evaluate ASR system performance for CERP goals, three cycle tests were conducted, with extensive water‐quality monitoring in the Upper Floridan Aquifer (UFA) at the Kissimmee River ASR (KRASR) pilot system. During each cycle test, redox evolution from sub‐oxic to sulfate‐reducing conditions occurs in the UFA storage zone, as indicated by decreasing Fe²⁺/H₂S mass ratios. Arsenic, released by pyrite oxidation during recharge, is sequestered during storage and recovery by co‐precipitation with iron sulfide. Mineral saturation indices indicate that amorphous iron oxide (a sorption surface for arsenic) is stable only during oxic and sub‐oxic conditions of the recharge phase, but iron sulfide (which co‐precipitates arsenic) is stable during the sulfate‐reducing conditions of the storage and recovery phases. Resultant arsenic concentrations in recovered water are below the 10 µg/L regulatory criterion during cycle tests 2 and 3. The arsenic sequestration process is appropriate for other ASR systems that recharge treated surface water into a sulfate‐reducing aquifer.     

The Effectiveness of Arsenic Remediation from Groundwater in a Private Home

Private wells are the source of drinking water for approximately 15% of households in the United States, but these wells are not regulated or monitored by government agencies. The well waters can contain arsenic, a known carcinogen that occurs in groundwater throughout the nation at concentrations that can exceed the Maximum Contaminant Level defined by the U.S. Environmental Protection Agency (10 ppb). In order to reduce arsenic exposure, homeowners can either rely on bottled water for drinking or install in-house water treatment systems for arsenic removal. Here, we document the arsenic levels associated with these options. We examined 24 different major bottled water brands and found that all have arsenic levels <1.5 parts per billion (ppb), and more than half have levels below our measurement detection limit of 0.005 ppb. For in-house treatment systems, we examined the performance of arsenic removal by point-of-use reverse osmosis filtration, and by whole-house and point-of-use filters containing granulated ferric oxide. Our results show that long-term (2 years) filtration with granulated ferric oxide reduced arsenic in well water from an initial concentration of 4 to 9 ppb down to <0.005 ppb, validating this technology as an effective form of arsenic remediation for private homes.     

Pump‐and‐Treat Groundwater Remediation Using Chlorine/Ultraviolet Advanced Oxidation Processes

Comparative studies of the use of chlorine/ultraviolet (Cl₂/UV) and hydrogen peroxide/ultraviolet (H₂O₂/UV) Advanced oxidation processes (AOPs) to remove trichloroethylene (TCE) from groundwater in a pump‐and‐treat application were conducted for the first time at the full‐scale operational level at two water treatment facilities in Northern California. In these studies, aqueous chlorine replaced hydrogen peroxide in the AOP treatment step, where the oxidant is exposed to UV light to produce highly reactive radical species that degrade groundwater contaminants. TCE removal rates as a function of initial chlorine dose and pH were then determined. At the site where the natural pH of the water was 7.1, TCE was removed (to a concentration of less than 0.5 µg/L) for nearly every chlorine dose point tested, and pH adjustment slightly enhanced the treatment process at this facility. The second site had a high natural pH of 7.7, and here, TCE was not completely removed for any chlorine dose up to 5.7 mg/L, although TCE removal did increase when the chlorine dose increased between 0.9 and 3.6 mg/L. Residual TCE remaining in the water post‐Cl₂/UV was readily removed using active carbon filtration, which is part of the overall treatment train at this facility. These studies also verified that Cl₂/UV AOP did not interfere with the photolysis of N‐nitrosodimethylamine or result in an effluent acutely toxic toward Ceriodaphnia dubia. Comparative economic analysis revealed that the chemical costs associated with Cl₂/UV AOP were 25 to 50% of the costs associated with in place H₂O₂/UV AOP treatment.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Arsenic Removal from Natural Groundwater Using Cupric Oxide

Groundwater is a main source of drinking water for some rural areas. People in these rural areas are potentially at risk from elevated levels of arsenic (As) due to a lack of water treatment facilities. The objectives of this study were to (1) measure As concentrations in approximately 50 groundwater samples from rural domestic wells in the western United States, (2) explore the potential of cupric oxide (CuO) particles in removal of As from groundwater samples under natural conditions (i.e., without adding competing anions and adjusting the pH or oxidation state), and (3) determine the effects of As removal on the chemistry of groundwater samples. Forty‐six groundwater well samples from rural domestic areas were tested in this study. More than 50% of these samples exceeded the U.S. Environmental Protection Agency Maximum Contaminant Limit (US EPA MCL) of 10 µg/L for As. CuO particles effectively removed As from groundwater samples across a wide range of pH (7.11 and 8.95) and concentrations of competing anions including phosphate (<0.05 to 3.06 mg/L), silica (<1 to 54.5 mg/L), and sulfate (1.3 to 735 mg/L). Removal of As showed minor effects on the chemistry of groundwater samples, therefore most of the water quality parameters remained within the US EPA MCLs. Overall, results of this study could help develop a simple one‐step process to remove As from groundwater.     

Spodic Material for In Situ Treatment of Arsenic in Ground Water

The leaching of chromium-copper-arsenic salts from old wood preservation sites is a threat to ground water at many places in Sweden. The installation of in situ reactive barriers is an attractive "passive' technique to prevent the further spreading of contaminants. The use of peat as a reactive barrier material has been suggested for heavy metals, but this material was expected to be unsatisfactory for arsenic (As). Therefore, the feasibility of using spodic B horizon material for the retention of arsenic was tested in laboratory column experiments. Contaminated soil was taken from an old preservation site and leached under conditions designed to imitate the field conditions. The arsenic load during the three-month duration of the test corresponded to a load at the field site during three years. The B horizon material proved to be efficient for retention of arsenic, despite the observation that As(III) dominated the As speciation. The As(III) concentration was reduced from 1 to 3 mg dm⁻³ to < 0.02 mg dm⁻³. Pure peat was, as expected, not suited as a reactive barrier for As, and a mixed B horizon/peat reactive barrier also proved unsatisfactory for the removal of As. It is therefore important to separate the B horizon material from any peat that is used to sorb heavy metals. Before applying the B horizon reactive barrier technique in the field, the effect of the naturally occurring variability of the reactive compounds should be tested. The inclusion of oxidizing agents in the barrier could possibly improve the lifetime considerably. Furthermore, the influence of the flow rate should be evaluated since the kinetics of the arsenic adsorption is relatively slow.     

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).     

Recovery of Gallium and Arsenic from Gallium Arsenide Waste in the Electronics Industry

Gallium arsenide (GaAs) has both high saturated electron velocity and high electron mobility, making it useful as a semiconductor material in a variety of applications, including light‐emitting diodes (LEDs), integrated circuits (ICs), and microwave appliances. A side effect of the use of gallium (Ga) is the production of a relatively large amount of hazardous waste. This study aimed at the recovery of Ga and arsenic (As) from GaAs waste using hydrometallurgical methods involving leaching and coagulation and a dry annealing process that involves annealing, vacuum separation, and sublimation by heating. Our research has shown that GaAs can be leached using nitric acid (HNO₃) to obtain 100% Ga and As with a leaching solution at pH 0.1, with subsequent adjustment of the leaching solution to pH 3 with sodium hydroxide (NaOH). Another method used a leaching solution at pH 2, then adjusting to pH 11 using NaOH. Ferric hydroxide (FeO(OH)) was added at 90°C after NaOH was added to the leaching solution. At pH 2 and 11, 55.5 and 21.9% of the As could be removed from the hazardous waste, respectively. The Ga could also be precipitated. When GaAs powder was heated to 1000°C over 3 h, 100% As removal was achieved, and 92.6% of the Ga was removed by formation of 99.9% gallium trioxide (Ga₂O₃). Arsenic was vaporized when the temperature was elevated to 1000°C, allowing arsenic trioxide (As₂O₃) to condense with 99.2% purity. The Ga₂O₃ powder produced was then dissolved and electrolyzed, allowing for 95.9% recovery of Ga with a purity of 99.9%.     

The behaviors and sources of dissolved arsenic and antimony in Bohai Bay

In this paper, we determined the concentrations of antimony species (antimonite (Sb(III)), antimonate (Sb(V)) and dissolved inorganic antimony (DISb)) and arsenic, in Bohai Bay seawaters, as well as the relationships of the analytes with environmental factors such as seawater characteristics (e.g., suspended particulate material (SPM), salinity and total organic carbon (TOC)), heavy metals, nutrients and phytoplankton species, and evaluated the sources of arsenic and antimony. Dissolved arsenic and antimony concentrations in the surface waters were ranging spatially from 1.03 to 1.26 ng/ml and 0.386 to 1.075 ng/ml, with mean values of 1.18 and 0.562 ng/ml, respectively. Sb(V) as the prominent chemical species constituted about 89%. Regarding arsenic concentrations in the surface waters, there was a tendency for a small variation. However, antimony species concentrations were much variable than arsenic. The highest arsenic and antimony concentrations were found near the Haihe Estuary. These distribution patterns were controlled mainly by environmental factors, biological activities and sources. In this region, DISb and Sb(V) negatively correlated with salinity. Besides, arsenic and antimony correlated well with the nutrients, chlorophyll a and phytoplankton, implying that arsenic and antimony had been involved in biological cycling. In addition, according to our estimate, about 333.5×10⁸ mg/year of arsenic and 454.2×10⁸ mg/year of antimony reached Bohai Bay via rivers.     

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.