Speciation of inorganic arsenic in particulate matter by combining HPLC/ICP-MS and XANES analyses

Abstract

Inorganic arsenic species in ambient particulate matter (PM 10 and PM 2.5 ) have been determined in an urban area, in the vicinity of a metallurgical industrial plant. The developed high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC/ICP-MS) method allows monitoring of particulate As(III) and As(V)-species, with a limit of quantification of 0.34 ng m À3 As(III) and 0.23 ng m À3 As(V), respectively. Good agreement was obtained between the sum of the concentrations of As(III) and As(V) determined by HPLC/ICP-MS and the total As concentrations determined by XRF, indicating a complete extraction of the As species. During the measuring campaigns for PM 10 and PM 2.5 , a significant conversion (oxidation) up to 54% of exogenous spiked As(III) was observed. The total amount of the spiked As(III) was well-recovered (PM 10 and PM 2.5 on average 108% and 101%, respectively). The extraction of the filter in combination with the sampled air matrix is likely to induce the As(III) conversion. The average measured As concentration in PM 10 during a 40-day monitoring campaign (30 ng m À3 ) at a hot spot location is above the European target value of 6 ng m À3 . The measured As concentration in PM 2.5 was half the value of the measured concentration in PM 10 and no relative enrichment of total As was observed in either particulate matter fractions. However, in PM 10 , As(V) was the main component, while in PM 2.5 , As(III) was the dominant species. During the monitoring campaign, the fraction of particulate As(III) varied between 19 and 61% in PM 10 and a trend towards a higher fraction of As(III) with increasing concentration of total As was observed. XANES and XRD analyses were used for the identification of arsenic species in local PM sources and confirmed the presence of Ca 3 Sr 2 (AsO 4 ) 2.5 (PO 4 ) 0.5 (OH), As 2 O 3 and As 2 O 5 species.

Atomic Spectrometry Update: review of advances in elemental speciation

“…Bulk chemical analysis was carried out on the ground 63 mm fraction by ICP-OES aer lithium metaborate/ tetraborate fusion, and the composition of the near-surface region (2-10 nm) was determined XPS. 84 The HPLC-ICP-MS method offered a LOQ of 0.34 ng m À3 for As III and 0.23 ng m À3 for As V . The As compounds were found to be concentrated onto the ash surface in the form of As III -S and As V -O species.…”

Speciation of arsenic: a case study of PM1 in Zabrze

“…), concentrations of As (and their species) are shaped mainly by municipal emission or time-stable road traffic emissions [14]. X-ray analysis of PM from industrial area showed that As bound to PM occurs as: Ca 3 Sr 2 (AsO 4 )2.5(PO4)0.5(OH), As 2 O 3 and As 2 O 5 [15]. Analysis of PM has revealed that inorganic arsenic species, in particular As(V), is the predominant species in atmospheric PM [2016].…”

“…Analysis of PM has revealed that inorganic arsenic species, in particular As(V), is the predominant species in atmospheric PM [2016]. Their ambient concentrations are higher in PM from industrial areas than in PM from semi-urban sites [14][15][16][17]. For example, high concentrations of PM2.5-bound As (6.4 ng/m 3 for total As, 0.9 ng/m3 for As(III) and 5.5 ng/m 3 for As(V)) were noted in area close to Spain cooper smelter [17].…”

Research on chromium and arsenic speciation in atmospheric particulate matter: short review

“…Speciation of PMbound Cr and As in size-segregated samples has been studied only to a little extent. Inorganic arsenic species were determined for example in PM2.5-10 and PM2.5 in Tapada and Sines in Portugal [27], in PM10 and PM2.5 in Huelva in Spain [28], in Antwerp in Belgium [10] in PM2.5 and PM1 in Zabrze, Poland [29]. These studies indicate the presence of As(V) as the dominating specie in the PM samples, followed by As(III); only Tirez and coworkers [10] showed that the dominant specie in PM2.5 was As(III).…”

“…The compounds of Cr and As in PM as well as the shares of its particular species are shaped by emission sources. X-ray analysis of PM collected in industrial area showed that arsenic is present as: Ca3Sr2(AsO4)2.5(PO4)0.5(OH), As2O3 and As2O5 [10] and chromium is present in the chemical forms: Cr2O3, Cr-Fe spinel, Cr(OH)3, Cr(NO3)3, Cr2(SO4)3, and CrCl3. Most of them are not soluble in water in contrary to Cr(VI) compounds, which are water-soluble unless existing as PbCrO4, BaCrO4 and ZnCrO4 (emitted during utilization of chromate pigments and dyes).…”