Investigation on chemical species of arsenic, selenium and antimony in fly ash from coal fuel thermal power stations

Investigations of the existing chemical forms and the concentrations of arsenic (As), selenium (Se) and antimony (Sb) in samples of fly ash obtained from six coal-fired power stations in various countries were carried out. The concentration of As was found to vary from 5.4 to 22.3 mg kg(-1), and the most common mode of occurrence of As in the fly ashes is in association with carbonates or Fe-Mn oxides. The concentrations of Se and Sb ranged from 2.3-5.2 and 1.0-3.9 mg kg(-1), respectively. The dominant chemical forms of Se and Sb in the fly ashes were as extractable species. Also, water-soluble As, Se and Sb in the fly ashes were extracted, and the chemical species of As, Se and Sb in the extract determined using HPLC-ICP-MS. This was done as the potential release of soluble As, Se and Sb through leaching of fly ash is of environmental concern. The most abundant form of As in the extract was the low toxicity As(V). The main species of Se was Se(IV), although it was found that the ratio of Se(VI) to Se(IV) in acidic fly ashes is higher than in alkaline fly ash samples. Antimony was mostly present as Sb(III).     

氨基化有机-无机杂化整体柱分离富集环境水中五价砷

将四乙氧基硅烷(TEOS)和N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷(AEAPTES)作为共聚前体,采用在毛细管内原位聚合的方式制备得到氨基功能化的有机-无机杂化整体柱,将其作为针式固相微萃取(SPME)介质,建立了现场分离富集环境水中As(V)的SPME方法,优化了有机-无机杂化整体柱富集As(V)的实验条件,并研究了整体柱对As(V)的吸附/洗脱性能和富集能力,实现了环境水样中As(V)的高效、快速、高选择性检测。     

Speciation of inorganic arsenic in coastal seawater from Ionian and Tyrrhenian Seas (Sicily, Italy) using derivative anodic stripping chronopotentiometry

The purpose of this paper was to use derivative anodic stripping chronopotentiometry (dASCP) as a sensitive and accurate technique, to determine the concentrations of dissolved As (III) and As (V) in coastal seawater samples from the Straits of Messina, the Ionian and the Tyrrhenian seas, and to investigate the relationship between the anthropogenic activities on the coastal areas and the concentration of dissolved inorganic arsenic in seawaters. The obtained data indicated that As (V) was the most abundant species, with concentration ranging from 26.7 to 307 nM, whereas As (III) levels were lower than 48 nM in all the samples. In particular, As (III) and As (V) levels significantly decreased from high to low anthropogenic activities zones (p < 0.00001, ANOVA), with the reference samples, from a wildlife reserve, showing the lowest values. Furthermore it was observed that human activities influenced inorganic arsenic speciation, since the zones that received high human input presented the highest As(V)/As (III) ratio.     

Polycyclic aromatic hydrocarbons and trace metal contamination of coastal sediment and biota from Togo

The state of contamination of tropical environments, particularly in Africa, remains a relatively under explored subject. Here, we determined polycyclic aromatic hydrocarbon (PAH) and trace metal concentrations in coastal sediment and biota samples (fish and mussels) from Togo (West Africa). In the sediments, the ∑21 PAH concentrations ranged from <4 ng g(-1) to 257 ng g(-1), averaging 92 ng g(-1). Concentration ratios of low molecular weight PAHs (2-3 rings) versus high molecular weight PAHs (≥4 rings) were always lower than 1 (ranging from 0.08 to 0.46) indicating that high molecular weight PAHs were dominant in all sediment samples, and that PAHs originated mainly from anthropogenic combustion activities. The sediments were also analyzed for major elements and a total of 15 trace metals, which were found in elevated concentrations. The calculated enrichment factor (EF) values relative to the Earth's crust show that the contamination is extremely severe for Cd (EF = 191), severe for Cr (EF = 18) and U (EF = 17.8), moderately severe for Zr (EF = 8.8), for Ni (EF = 6.8), Sr (EF = 5.9) and Ba (EF = 5.4), and moderate for V (EF = 3.6) and Zn (EF = 3.4). Sediments sampled in areas affected by the dumping of phosphorite mine tailings showed particularly high concentrations of trace metals. Overall, concentrations of both PAHs and trace metals in sediment tend to increase from the coastline to the open sea (2 km offshore). This is attributable to the increasingly finer texture of coastal sediment found offshore, which has a terrigenous origin and appears loaded with various contaminants through adsorption processes. Such high loads of trace metals were also found in the biota (fish and mussels). The ratio of measured trace metal concentrations in biota to threshold limits set by the World Health Organization herein defined as relative health factor (RHF) was high. Average RHF values in fish were highest for Se (470), As (250), Ag (97), Ni (78), Mn (63), Fe (53), Pb (36), Cd (10), and Cr (7) while lowest for Cu (0.08) and Zn (0.03). Cd and Al did not bioaccumulate in the analyzed fish species. In mussels, the RHF values were highest for Fe (9,108), As (295), Pb (276), Se (273), Mn (186), Ni (71), Ag (70), Cd (14), and Cu (4).     

non-lethal responses of the freshwater snail potamopyrgus antipodarum to dissolved arsenic

Two non-lethal responses, avoidance andimmobility, were observed for thefreshwater gastropod Potamopyrgusantipodarum on exposure to dissolvedarsenic (As) as arsenate (As(V)) orarsenite (As(III)). Two differentpopulations of P. antipodarum, onewith a long history of exposure todissolved As from geothermal fluids andthe other with minimal exposure, werecompared to test for adaptation to As. Both snail populations avoided dissolvedAs(III), the more toxic form, at lowerconcentrations than As(V). As(V), theless toxic form, was avoided by both snailpopulations at much lower concentrationsthan those at which the snails becameimmobile. In contrast, the concentrationsof As(III) which caused avoidance werealmost the same as those which causedimmobility, implying that avoidance may notbe an effective response to protect thesesnails from exposure to As(III). Snailsfrom the exposed population avoided As(V)at about 20% of the concentration thatwas avoided by the snails from theunexposed population. At higherconcentrations of As(V) which causedimmobility, this difference in sensitivitypersisted up to an exposure time of 48 hours. After 96 hours exposure, however,both populations showed similarsensitivity. Snails from the exposedpopulation were more sensitive to As(III),both avoiding the As and becoming immobileat lower concentrations than were observedfor the same responses in the snails fromthe unexposed population. We suggest thatthe differences in sensitivity between thetwo populations could have been the resultof the higher soft body As burden of theexposed snails at the start of thelaboratory experiments.     

Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism

The analysis for arsenic in hair is commonly used in epidemiological studies to assess exposure to this toxic element. However, poor correlation between total arsenic concentration in hair and water sources have been found in previous studies. Exclusive determination of endogenous arsenic in the hair, excluding external contamination has become an analytical challenge. Arsenic speciation in hair appears as a new possibility for analytical assessing in As-exposure studies. This study applied a relative simple method for arsenic speciation in human hair based on water extraction and HPLC-HG-ICP-MS. The concentration of arsenic species in human hair was assessed in chronically As(V)-exposed populations from two villages (Esqui?a and Illapata) of the Atacama Desert, Chile. The arsenic concentrations in drinking water are 0.075 and 1.25 mg L(-1), respectively, where As(V) represented between 92 and 99.5% of the total arsenic of the consumed waters. On average, the total arsenic concentrations in hair from individuals of Esqui?a and Illapata were 0.7 and 6.1 microg g(-1), respectively. Four arsenic species, As(III), DMA(V), MMA(V) and As(V), were detected and quantified in the hair extracts. Assuming the found species in extracts represent the species in hair, more than 98% of the total arsenic in hair corresponded to inorganic As. On average, As(III) concentrations in hair were 0.25 and 3.75 microg g(-1) in Esqui?a and Illapata, respectively; while, the As(V) average concentrations were 0.15 and 0.45 microg g(-1) in Esqui?a and Illapata, respectively. Methylated species represent less than 2% of the extracted As (DMA(V)+ MMA(V)) in both populations. As(III) in hair shows the best correlation with chronic exposure to As(V) in comparison to other species and total arsenic. In fact, concentrations of As(total), As(III) and As(V) in hair samples are correlated with the age of the exposed individuals from Illapata (R= 0.65, 0.69, 0.57, respectively) and with the time of residence in this village (R= 0.54, 0.71 and 0.58, respectively).     

Geochemical patterns in soils in and around Siddipet, Medak District, Andhra Pradesh, India

This paper reports the first results of geochemical survey carried out in and around Siddipet, taking soil (topsoil 0–25 cm and subsoil 70–95 cm) as the sampling media. The data were obtained in a consistent way from 61 sites. The samples were analyzed for 29 elements (As, Ba, Cd, Co, Cr, Cu, F, Mo, Ni, Pb, Rb, Se, Sr, Th, U, V, Y, Zn, Zr, Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, and P) by X-ray fluorescence spectrometer, and baseline levels for these elements are presented. Results reveal that the correlation between the geochemical patterns in the soils developed on different litho-variants is not straight forward, but some general trends can be observed. Regional parent materials and pedogenesis are the primary factors influencing the concentrations of trace elements while anthropogenic activities have secondary influence.     

Metal pollution and ecological risk assessment in marine sediments of Karachi Coast, Pakistan

Concentrations of 12 metals (Fe, Mn, Cr, Mo, Ni, Pb, Se, Sr, U, V, Zn, and Zr) in surface sediments of Karachi Coast, Pakistan were determined to evaluate their distribution and pollution assessment. The measured metals in the sediments were found to be in the range of Fe, 0.84–6.96 %; Mn, 300–1,300 μg/g; Cr, 12.0–319.84 μg/g; Mo, 0.49–2.03 μg/g; Ni, 1.53–58.86 μg/g; Pb, 9.0–49.46 μg/g; Se, 0.25–.86 μg/g; Sr, 192–1185 μg/g; U, 0.19–1.66 μg/g; V, 15.80–118.20 μg/g; Zn, 15.60–666.28 μg/g; and Zr, 44.02–175.26 μg/g. The mean contents of the metal studied were: Fe, 3.07 %, Mn, 0.05 %; Cr, 96.75 μg/g; Mo, 1.34 μg/g; Ni, 31.39 μg/g; Pb, 23.24 μg/g; Se, 0.61 μg/g; Sr, 374.83 μg/g; U, 0.64 μg/g; V, 61.75 μg/g; Zn, 204.75 μg/g; and Zr:76.27 μg/g, and arrangement of the metals from higher to lower mean content in this area is: Fe?>?Zn?>?Mn?>?Sr?>?Zn?>?Cr?>?Zr?>?V?>?Ni?>?Pb?>?Mo?>?U?>?Se. There is no significant correlation among most of these metals, indicating different anthropogenic and natural sources. To assess ecotoxic potential of marine sediments, Numerical Sediment Quality Guidelines were also applied. The concentration of Pb in all the sediments except one was lower than the threshold effect concentration (TECs) showing that there are no harmful effects to marine life from Pb. On the other hand, the concentrations of Cr, Ni, and Zn exceeded TEC in three stations, indicating their potential risk. The degree of pollution in sediments for metals was assessed by calculating enrichment factor (EF) and pollution load index (PLI). The results indicated that sediments of Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are highly enriched with Cr and Zn (EF?>?5). Sediments of Layari River Outfall Zone were moderately enriched with Ni and Pb (EF?>?2). The pollution load index was found in the range of 0.98 to 1.34. Lower values of PLI (≤1) at most of sampling locations imply no appreciable input from anthropogenic sources. However, relatively higher PLI values (>1) at Layari River Mouth Area, Fish Harbour, and KPT Boat Building Area are attributed to increased human activity in the area.     

Comparison of PoraPak Rxn RP and XAD-2 adsorbents for monitoring dissolved hydrophobic organic contaminants

Accurate determination of the levels of dissolved hydrophobic organic contaminants (HOCs) is an important step in estimating the dynamics of their inputs and losses in aqueous systems. This study explores an alternative method for efficiently sampling dissolved HOCs while mitigating a number of sampling artifacts associated with traditional methods. The adsorption characteristics of a new polymeric resin, PoraPak Rxn RP (PPR), were assessed using sorption isotherm experiments and fixed bed adsorption studies. The adsorption capacities and breakthrough times for four model contaminants (phenol, p-nitrophenol, naphthalene, and 2,4,6-tribromophenol) were proportional to the contaminant’s hydrophobicity. The ability of PPR to isolate dissolved polychlorinated biphenyls (PCBs) in real samples was compared with that of XAD-2, a well-known macroporous polymer that suffers from high background contamination. The results indicated that the PPR resin can be effectively used for monitoring HOCs, with low ∑PCB levels in blanks, decreasing solvent use, and reducing extraction times.     

Synthesis,characterization, and systematic studies of a novel aluminum selective chelating resin

A procedure is detailed for the selective analysis of trace aluminum by flame atomic absorption spectrophotometer coupled with off-line column separation and preconcentration. Chelating resin was synthesized by covalent functionalization of Amberlite XAD-16 by 2-(2-hydroxyphenyl) benzoxazole. The modified resin was characterized using FT-IR spectroscopy, energy dispersive x-ray analysis, elemental analysis, thermogravimetric analysis/differential thermal analysis, and minimum energy run. The optimum sorption was at pH 9?±?0.1 with corresponding t _1/2 of only 7 min. Many competitive anions and cations studied did not interfere at all in the selective determination of Al(III), at the optimized conditions. The resin shows maximum sorption capacity of 21.58 mg g^?1 and can be regenerated up to 75 cycles without any discernible capacity loss. The Langmuir isotherm model provides the better correlation of the experimental data (r ²?=?0.999) in comparison to Freundlich isotherm model, while the Scatchard analysis revealed homogeneous binding sites in the chelating resin. Analytical figures of merit were evaluated by accuracy (standard reference materials and recovery experiment), precision (RSD <5 %), and detection limit (2.8 μg L^?1). The applicability was demonstrated by analysis of trace aluminum in biological, environmental, and food samples.     

Heavy metals concentration in soils of southeastern part of Ranga Reddy district, Andhra Pradesh, India

There is a growing concern over the potential accumulation of heavy metals in soils owing to rapid industrial and urban development and increasing reliance on agrochemicals in the last several decades. These metals can infiltrate through the soil thereby causing groundwater pollution. Surface soil samples (5 to 15 cm) collected from southeastern part of Ranga Reddy district were analyzed for 14 heavy metals (As, Ba, Co, Cr, Cu, Mo, Ni, Pb, Rb, Sr, V, Y, Zn and Zr) using Philips PW 2440 X-ray fluorescence spectrometer. Results for heavy and trace elements are reported for the first time in soils for this region. The contamination of the soils was assessed on the basis of enrichment factor (EF), geoaccumulation index (I (geo)), contamination factor and degree of contamination. The results reveal that variations in heavy element concentrations in the soil analyzed have both geogenic and anthropogenic contribution, due to the long period of constant human activities in the study area. The concentration of the metals Ba, Rb, Sr, V, Y and Zr were interpreted to be mainly inherited from parent materials (rocks) and the As, Co, Cr, Cu, Mo, Ni, Pb and Zn concentrations show contribution from geogenic and anthropogenic sources. The major element variations in soils are determined by the composition of the parent material predominantly involving granites.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Solid phase extraction of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions with 1-(2-thiazolylazo)-2-naphthol loaded Amberlite XAD-1180

A new method for separation and preconcentration of trace amounts of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) ions in various matrices was proposed. The method is based on the adsorption and chelation of the metal ions on a column containing Amberlite XAD-1180 resin impregnated with 1-(2-thiazolylazo)-2-naphthol (TAN) reagent prior to their determination by flame atomic absorption spectrometry (FAAS). The effect of pH, type, concentration and volume of eluent, sample volume, flow rates of sample and elution solutions, and interfering ions have been investigated. The optimum pH for simultaneous retention of all the metal ions was 9. Eluent for quantitative elution was 20 ml of 2 mol l(-1) HNO(3). The optimum sample and eluent flow rates were found as 4 ml min(-1), and also sample volume was 500 ml, except for Mn (87% recovery). The sorption capacity of the resin was found to be 0.77, 0.41, 0.57, and 0.30 mg g(-1) for Cu(II), Ni(II), Cd(II), and Mn(II), respectively. The preconcentration factor of the method was 200 for Cu(II), 150 for Pb(II), 100 for Cd(II) and Ni(II), and 50 for Mn(II). The recovery values for all of the metal ions were > or = 95% and relative standard deviations (RSDs) were < or = 5.1%. The detection limit values were in the range of 0.03 and 1.19 microg l(-1). The accuracy of the method was confirmed by analysing the certified reference materials (TMDA 54.4 fortified lake water and GBW 07605 tea samples) and the recovery studies. This procedure was applied to the determination of Cu(II), Ni(II), Pb(II), Cd(II) and Mn(II) in waste water and lake water samples.     

Application of cold-induced aggregation microextraction as a fast,simple, and organic solvent-free method for the separation and preconcentration of Se(IV) in rice and various water samples

The developed method is based on cold-induced aggregation microextraction of Se(IV) using the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as an extractant followed by spectrophotometry determination. The extraction of Se(IV) was performed in the presence of dithizone as the complexing agent. In this method, a very small amount of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the sample solution containing Se-dithizone complex. Then, the solution was kept in a thermostated bath at 50 °C for 4 min. Subsequently, the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Some important parameters that might affect the extraction efficiency were optimized (HCl, 0.6 mol L^?1; dithizone, 4.0?×?10^?6 mol L^?1; ionic liquid, 100 μL). Under the optimum conditions, good linear relationship, sensitivity, and reproducibility were obtained. The limit of detection (LOD) (3S_b/m) was 1.5 μg L^?1, and the relative standard deviation (RSD) was 1.2 % for 30 μg L^?1 of Se(IV). The linear range was obtained in the range of 5–60 μg L^?1. It was satisfactory to analyze rice and various water samples.     

A new voltammetric method for the simultaneous monitoring of heavy metals in sea water,sediments, algae and clams: application to the Goro Bay ecosystem

Arsenic(III), selenium(IV), copper(II), lead(II), cadmium(II),zinc(II) have been determined in sea water, sediments, algae andclams by differential pulse cathodic (DPCSV) and anodic (DPASV)stripping voltammetry. The voltammetric measurements are carriedout using a conventional three-electrode cell and the ammonia-ammonium chloride buffer pH 9.2 as supporting electrolyte.The analytical procedure has been verified by the analysisof the standard reference materials (Estuarine SedimentBCR-CRM 277, Ulva Lactuca BCR-CRM 279 and Mussel Tissue BCR-CRM278). The precision and the accuracy are less than 5%. Thisprocedure is utilized for the monitoring of heavy metals inthe Po river mouth area (Italy).     

Investigation of arsenic speciation on drinking water treatment media utilizing automated sequential continuous flow extraction with IC-ICP-MS detection

Three treatment media, used for the removal of arsenic from drinking water, were sequentially extracted using 10 mM MgCl2(pH 8), 10 mM NaH2PO4(pH 7) followed by 10 mM (NH4)2C2O4(pH 3). The media were extracted using an on-line automated continuous extraction system which allowed the arsenic in each of the extraction fluids to be speciated on-line using IC-ICP-MS. The 10 mM MgCl2 preferentially extracted As(III) from each of the media. The percentage of the arsenic extracted by the MgCl2, relative to a HNO3/H2O2 digestion of the media, ranged from 0.1-2.3% for the three solids. The next sequential extraction fluid, 10 mM NaH2PO4, extracted some of the residual As(III) remaining on each of the media but the predominant species extracted was As(V). The 10 mM NaH2PO4 extracted 15.3 to 42.8% of the total arsenic relative to a total digested concentration for each of the media. The As(III) and As(V) stability studies conducted in these two extraction fluids indicated that conversion between As(III) and As(V) was not significant for the short extraction fluid sample contact time associated with the on-line continuous flow extraction cell. Finally, the 10 mM (NH4)2C2O4 extraction fluid was utilized in an off-line analysis mode because the Fe and As concentrations extracted from the media were not compatible with direct ICP-MS detection. The (NH4)2C2O4 extracted 2.9-29% As(III) for all three media and caused an oxidation of As(III) to As(V) during the extraction period for one of the three media. The sum of the arsenic from each of the three extraction fluids represented 92%, 44% and 53% of the available total arsenic for the three media, respectively. The speciation results for each media were obtained by adding all the speciation results from all three extraction fluids together and the resulting distribution of As(III)/As(V) compared well with the speciation results obtained via XANES.     

Solid phase extractive preconcentration of silver from aqueous samples

N,N-dibutyl-N1-benzoylthiourea (DBBT) impregnated onto a polymeric matrix, Amberlite XAD-16 was prepared. The separation and enrichment of Ag(I) from solution was investigated. Effective extraction conditions were optimized in column methods prior to determination by atomic absorption spectrometry. The optimum pH range for quantitative adsorption is 2-5. Quantitative recovery of Ag was achieved by stripping with 1 mol L(-1) thiourea in 1 mol L(-1) HCl. The sorption capacity of resin is 0.115 mmol Ag+ g(-1) resin. The relative standard deviation and detection limit was 3.1% for 1 microg Ag+ mL(-1) solution and 0.11 microg L(-1), respectively. The method was used for the determination of silver in geological water samples.     

Chemical Composition and Sources of PM10 and PM2.5 Aerosols in Guangzhou, China

Aerosol samples of PM10 and PM2.5 are collected in summertime at four monitoring sites in Guangzhou, China. The concentrations of organic and elemental carbons (OC/EC), inorganic ions, and elements in PM10 and PM2.5 are also quantified. Our study aims to: (1) characterize the particulate concentrations and associated chemical species in urban atmosphere (2) identify the potential sources and estimate their apportionment. The results show that average concentration of PM2.5 (97.54 μg m⁻³) in Guangzhou significantly exceeds the National Ambient Air Quality Standard (NAAQS) 24-h average of 65 μg m⁻³. OC, EC, Sulfate, ammonium, K, V, Ni, Cu, Zn, Pb, As, Cd and Se are mainly in PM2.5 fraction of particles, while chloride, nitrate, Na, Mg, Al, Fe, Ca, Ti and Mn are mainly in PM2.5-10 fraction. The major components such as sulfate, OC and EC account for about 70–90% of the particulate mass. Enrichment factors (EF) for elements are calculated to indicate that elements of anthropogenic origins (Zn, Pb, As, Se, V, Ni, Cu and Cd) are highly enriched with respect to crustal composition (Al, Fe, Ca, Ti and Mn). Ambient and source data are used in the multi-variable linearly regression analysis for source identification and apportionment, indicating that major sources and their apportionments of ambient particulate aerosols in Guangzhou are vehicle exhaust by 38.4% and coal combustion by 26.0%, respetively.     

Occurrence and sorption properties of arsenicals in marine sediments

The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6?±?7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118?±?76 L/kg DM and for depths >70 m, salinity >11 %, DO?<?9 mg/L and muddy sediments the Kd was 513?±?233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.     

Speciation of As(III) and As(V) in water and sediment using reverse-phase ion-pair high-performance liquid chromatography-neutron activation analysis (HPLC-NAA)

Total As content and the As species distribution in water and sediments from the Kwabrafo stream, a major water body draining the Obuasi gold mining community in southwestern Ghana, have been investigated. Total As content was determined by instrumental neutron activation analysis (INAA). Ion-pair reverse phase high-performance liquid chromatography-neutron activation analysis (HPLC-NAA) was used for speciation of As species. Solid phase extraction with phosphate buffer was used to extract soluble As species from lyophilized sediment. The mass balance after phosphate extraction of soluble As species in sediment varied from 89 to 96 %. Compositionally appropriate reference material International Atomic Energy Agency (IAEA)-Lake Sediment (SL)-1 was used to check the validity of INAA method for total As determination. The measured values are in good agreement with the IAEA recommended value and also within the 95 % confidence interval. The accuracy of the measurement in terms of relative deviation from the IAEA recommended value was ±0.83 %. “In-house” prepared As(III) and As(V) standards were used to validate the HPLC-INAA method used for the As species determination. Total As concentration in the water samples ranged from 1.15 to 9.20 mg/L. As(III) species in water varied from 0.13 to 0.7 mg/L, while As(V) species varied from 0.79 to 3.85 mg/L. Total As content in sediment ranged from 2,134 to 3,596 mg/kg dry mass. The levels of As(III) and As(V) species in the sediment ranges from 138 to 506 mg/kg dry mass and 156 to 385 mg/kg dry mass, respectively.