Determination of inorganic arsenic species in soil extracts by a simple spectrophotometric method
DOI:
https://doi.org/10.54652/rsf.2011.v41.i1.139Keywords:
hydride generation, selective reduction, sequential extraction, forest soilsAbstract
UDK 631.4:546.19
This paper presents a simple and inexpensive method for speciation of inorganic arsenic in soil extracts. It is based on selective hydride generation of arsane at different pH values from the sample solution. A rather acidic pH value was used for generation of arsane from total inorganic arsenic As(III) and As(V) compounds, and only slightly acidic pH value was used for the generation of arsane only from As(III). As(V) was calculated from difference of total inorganic arsenic and As(III). Determination of total inorganic arsenic was performed with two tablets of amidosulfonic acid (1.7800 g of acid per tablet) and one tablet of sodium borohydride (3.000 g per tablet). Determination of arsenic(III) was performed in citrate buffer (0.1 mol/dm3, pH =5.5) with one tablet of the reductant. The hydride formed during reaction passed through filter paper, and reacted with mercury bromide giving a colored compound, which was optically detected with a spectrophotometric device SupraLab FD.
Soil samples were collected in two sites of Bosnia. The first site was Vareš region, near the barite, galenite and sphalerite mine (Veovača), and the second one was located at Vranica Mountain, location of Jezernica. Average concentrations of total arsenic determined in digests obtained after mineralization of soils (marked as S1 and S2) with nitric acid (65%) and hydrogen peroxide (30%) were 81.14±1.90 mg/kg and 14.18±0.62 mg/kg, respectively. Obtained recovery rates for spikes in acid digests were in the range 94.0 - 102%, for the soil S1, and 103.0 - 104% for the soil S2.
The procedure by WENZEL (ET AL., 2001) designed for arsenic fractionating in soils was adopted. The sequential procedure employed here consisted of three steps: 0.05 mol/dm3 ammonium dihydrogen phosphate, which extracts specifically sorbet arsenic from mineral surfaces; 0.2 mol/dm3 ammonium oxalate (pH = 3.25) which extracts arsenic bound to amorphous and poorly-crystalline hydrous oxides of Fe and Al; 0.2 mol/dm3 ammonium oxalate buffer + 0.1 mol/dm3 ascorbic acid (pH = 3.25) at elevated temperature (96±3oC) which extracts arsenic bound to well crystallized hydrous oxides of Fe and Al.
The total extractable arsenic in first soil was 77.4% while in second soil it was 85.9%. The highest amount of arsenic is probably bound to Fe hydroxide (amorphous and crystalline) which presents 76.3% for soil 1 and 82.6% for soil 2 of total arsenic content. Generally in two first steps of the extraction procedure only As(V) was detected. Some small amounts of As(III) were detected in the third step of extraction with both soil samples (2.8% for soil 1 and 1.5% for the soil 2) referred to the total concentration of arsenic in soils in digests with nitric acid. The concentration of As(III) measured in citrate buffer was below the detection limit in step 1 and step 2 with both soils.
The reproducibility of the extraction procedure (estimated as RSD of the three repetitive extractions for each step of extraction procedure) was less than 5%, which is in very good agreement with the literature value (WENZEL, ET AL., 2001).
Based on obtained results, the new method using this device is well suitable for trace determination of inorganic arsenic species with concentrations between 0.2 and 20 mg As/dm3. Results obtained shown that the device can be used for such investigations of soils in the laboratory at low costs in routine analysis.
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