Assessment of sources, environmental, ecological, and health risks of potentially toxic elements in urban dust of Moscow megacity, Russia.

Potentially toxic elements (PTEs) in urban dust of Moscow megacity and related risks have been studied. 78 samples were collected in the Moscow downtown in sites with different anthropogenic load, namely, major highways, residential area, and recreation zones. The concentrations of PTEs in urban dust were determined by ICP-MS and ICP-AES. Then, environmental, ecological and health risks of PTEs in urban dust were assessed. In addition, potential sources of PTEs in dust were identified. It is shown that Moscow dust is mainly contaminated by Sb, Zn, Pb, Cd, Cu, Sn, and Mo, which according to the data of principal component and correlation analyses can be attributed to anthropogenic sources (non-exhaust vehicle emissions). Potential ecological risk factor demonstrates that Cu, Mo, and Cd have moderate potential ecological risks in 13% of studied area, while Sb has this risk in 62% of area. Potential ecological risk indices indicate that 41% of studied territory is of moderate ecological risk. Concerning the human risks through ingestion, dermal contact, and inhalation pathways, PTEs in Moscow dust have no significant non-carcinogenic risks for adults. However, the value of total hazard index for children is 1.8 showing that non-carcinogenic risks may occur. Moreover, possible carcinogenic risks caused by Cr are evaluated. The finding of the present study can be used for ecological management in the megacity to reduce both ecological and human risks. A special attention should be given to periods of hot and dry weather and to traffic-related emissions.

Fractionation of Sb and As in soil and sludge samples using different continuous-flow extraction techniques.

The fractionation of Sb and As in soil and sludge samples had been comparably studied using two continuous-flow systems: a microcolumn (MC) and a rotating coiled column (RCC). The leachants were applied in correspondence with a five-step sequential extraction scheme addressing water-soluble, non-specifically sorbed, specifically sorbed, and bound to amorphous and crystalline Fe/Al oxide fractions of Sb and As. Inductively coupled plasma atomic emission spectroscopy was applied to determine antimony, arsenic, and major elements in the effluent and in the residual fractions after their digestion. Resemblances and discrepancies of the two methods were evaluated by the fractionation of Sb and As in forest soil, river sludge, and dumped waste (soil) samples. For the forest soil sample, which is very poor in organic matter, RCC and MC extractions yielded similar quantitative values of As and Sb contents in individual leachable fractions. However, for the river sludge sample with a moderate concentration of C (org) (3.3 %), the results obtained by both continuous-flow methods are in satisfactory agreement. RCC extraction enabled water-soluble and non-specifically sorbed As fractions to be recovered, whereas after MC leaching, these environmentally relevant forms of As were not detected. For the soil rich in organic matter (C(org) = 11.5 %), the discrepancy between the data of RCC and MC fractionations is significant. RCC extraction provides about six times higher recoveries of As and Sb bound to amorphous Fe/Al oxides. More efficient leaching of As and Sb in RCC may be attributed to the migration of organic-rich particles with low density inside the column that might enhance the mixing of the solid and liquid phases.

Continuous-flow fractionation of trace metals in environmental solids using rotating coiled columns. Some kinetic aspects and applicability of three-step BCR leaching schemes.

The applicability of the three-step BCR leaching scheme to the continuous-flow fractionation of trace metals (TM) using rotating coiled columns (RCC) has been investigated taking soil and sediment reference samples (SRM-2710, CRM-601, BCR-701) as examples. A particulate sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents, used according to the original and optimised BCR protocols, were continuously pumped through. The whole procedure required 3-4 h instead of at least 50 h needed for the traditional sequential extraction. It has been shown that in comparison with batch sequential extraction procedures (SEP), the recoveries of Cd, Zn, Cu, and Pb at the first stage (most mobile and potentially dangerous acid soluble forms) are somewhat higher, if a dynamic extraction in RCC is used. Nevertheless, the distribution patterns for TM in the first two leachable fractions (acid soluble and reducible forms) are similar in most cases. Since no heating is used in RCC, the recoveries of TM at the third stage (when hydrogen peroxide is applied to oxidize the organic matter) may be incomplete and matrix-dependent. The effect of eluent volume and flow rate on the recovery of TM in different forms has been investigated. It has been shown that the kinetics of heavy metal leaching vary significantly with samples. Hence, investigating the elution profiles can provide additional important information for risk assessment of TM mobilization.

Accelerated fractionation of heavy metals in contaminated soils and sediments using rotating coiled columns.

A new approach to performing an accelerated sequential extraction of trace elements from solid samples has been proposed. It has been shown that rotating coiled columns (RCC) earlier used in counter-current chromatography can be successfully applied to the dynamic leaching of heavy metals from soils and sediments. A solid sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents (aqueous solutions of complexing reagents, mineral salts and acids) were continuously pumped through. The procedure developed is time saving and requires only 4-5 h instead of the several days needed for traditional sequential extraction (TSE), complete automation being possible. Losses of solid sample are minimal. In most cases the recoveries of readily bioavailable and leachable forms of Pb, Zn, and Cd are higher, if a dynamic extraction in RCC is used. Since naturally occurring processes are always dynamic, continuous extraction in RCC may help to estimate the contents of leachable forms and their potential risk for the environment more correctly than batch TSE. The Kersten-Foerstner and McLaren-Crawford leaching schemes have been compared, the former has been found to be preferable.