P. S. Fedotov

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.

Fractionation and characterization of nano- and microparticles in liquid media.

Submicron and micron particles present in liquid environmental, biological, and technological samples differ in their dimensions, shape, mass, chemical composition, and charge. Their properties cannot be reliably studied unless the particles are fractionated. Synthetic particles applied as components of analytical systems may also need preliminary fractionation and investigation. The review is focused on the methods for fractionation and characterization of nanoparticles and microparticles in liquid media, the most representative examples of their application, and the trends in developing novel approaches to the separation and investigation of particles. Among the separation techniques, the main attention is devoted to membrane filtration, field-flow fractionation, chromatographic, and capillary electrokinetic methods. Microfluidic systems employing the above-mentioned and other separation principles and providing a basis for the fabrication of lab-on-chip devices are also examined. Laser light scattering methods and other physical techniques for the characterization of particles are considered. Special attention is given to “hyphenated” techniques which enable the separation and characterization of particles to be performed in online modes.

Extraction and Fractionation Methods for Exposure Assessment of Trace Metals, Metalloids, and Hazardous Organic Compounds in Terrestrial Environments

It is demonstrated that similar methodologies are applicable to the exposure assessment of inorganic and organic pollutants in contaminated and native soils/sediments of different type and origin. A special emphasis is given to the correlation between the results of chemical extraction/fractionation and the data on the biouptake of trace metals, metalloids, and hazardous organic compounds by plants and soil organisms. Application of extraction techniques to the assessment of potentially biodegradable fractions of organic pollutants is also discussed and evaluated. Recent developments in dynamic extraction methods, which mimic natural scenarios more correctly than the batchwise counterparts, are presented in detail.

A hyphenated flow-through analytical system for the study of the mobility and fractionation of trace and major elements in environmental solid samples.

A flow-through hyphenated analytical method has been tested that enables not only the accelerated and efficient fractionation of trace elements (TE) species in environmental solids to be achieved but allows real-time studies on the leaching process to be made. Rotating coiled columns (RCC), earlier used mainly in countercurrent chromatography, have been successfully applied to the dynamic fractionation of heavy metals in soil, sediment, and sludge samples. A ground solid sample (about 0.5 g) was retained in a PTFE rotating column as the stationary phase whereas different aqueous eluents, chosen according to recent data on the selectivity of leachants, were continuously pumped through. Elements were determined in the effluent on-line by inductively coupled plasma atomic emission spectrometry (ICP-AES). Since the flow rates used in the RCC are in good agreement with those needed for cross-flow nebulization in the ICP-AES spectrometer, both devices were coupled directly without any additional interface systems. Simultaneous investigation of the elution profiles of trace and major elements has made it possible to study the elements association in separated fractions and hence to prove the efficacy of extractants and their selectivity toward targeted mineralogical phases of samples. The close association of heavy metals with Mn oxides in the sediment and sludge samples was confirmed. The time-resolved dissolution of different organic complexes of metals was observed for the sediment sample. It was found that in sediment and sludge samples the dynamics of iron release under the action of Tamms reagent is somewhat different from that of aluminium. In addition, the proposed method can also be applied to develop effective leaching schemes and in the analysis of environmental solids for risk assessment of their contaminants addressed to water quality and bioavailability.

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.

Characterization of size, morphology and elemental composition of nano-, submicron, and micron particles of street dust separated using field-flow fractionation in a rotating coiled column

For the first time, nano- and submicron particles of street dust have been separated, weighted, and analyzed. A novel technique, sedimentation field-flow fractionation in a rotating coiled column, was applied to the fractionation of dust samples with water being used as a carrier fluid. The size and morphology of particles in the separated fractions were characterized by electronic microscopy before digestion and the determination of the concentration of elements by ICP-AES and ICP-MS. The elements that may be of anthropogenic origin (Zn, Cr, Ni, Cu, Cd, Sn, Pb) were found to concentrate mainly in <0.3 and 0.3-1 μm fractions. It has been shown that the concentrations of Cr, Ni, Zn in the finest fraction (<0.3 μm) of street dust can be one order of magnitude higher than the concentrations of elements in bulk sample and coarse fractions. For example, the concentrations of Ni in <0.3, 0.3-1, 1-10, and 10-100 μm fractions were 297 ± 46, 130 ± 21, 36 ± 10, and 21 ± 4 mg/kg, correspondingly. Though the finest particles present only about 0.1 mass% of the sample they are of special concern due to their increased mobility and ability to penetrate into the deepest alveolar area of the lungs. For rare earth elements (La, Ce, Pr, Nd, Sm) that are evidently of natural source and may be found in soil minerals, in contrary, higher concentrations were observed in large particles (10-100 μm). Sc was an exception that needs further studies. The proposed approach to the fractionation and analysis of nano-, submicron, and micron particles can be a powerful tool for risk assessment related to toxic elements in dust, ash, and other particulate environmental samples.

Dynamic fractionation of trace metals in soil and sediment samples using rotating coiled column extraction and sequential injection microcolumn extraction: a comparative study.

Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps. A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min(-1) prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry. Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilizable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.

Untraditional applications of countercurrent chromatography

ABSTRACT Rotating coiled columns (RCC) have been traditionally applied to the separation and purification of organic solutes by countercurrent chromatography (CCC). The technique is based on the retention of one phase (stationary) of a two-phase solvent system in a rotating column without solid support under the action of centrifugal forces, while the other liquid phase (mobile) is being continuously pumped through. Solutes are subjected to a partition process between two phases and eluted in order of their partition coefficients. Within the last several years, some fundamentals and methods of inorganic separations by CCC in two-phase liquid systems, with different solvents and extracting reagents, have been developed. Procedures for the group pre-separation of rare earth and some rare (Zr, Hf, Nb, Ta) elements from multi-component matrices were proposed. The application of CCC to the purification and analysis of salt solutions has also been investigated. Recently, it has been shown that rotating columns can be used for the separation of both solutes and particles, not only in liquid–liquid systems but in liquid–solid–liquid and liquid–solid systems as well. Procedures for the direct extraction of polynuclear aromatic hydrocarbons from a sewage sludge medium, and continuous fractionation of trace elements in soils were developed; suspensions and powdered solid samples being applied as the stationary phase in the column. It has been demonstrated, that RCC can be successfully used for the fractionation of micro particles. There is no stationary phase in this case. The centrifugal forces acting on RCC provide different migration speeds of the suspended sample components in one carrier fluid.

Methods for continuous flow fractionation of microparticles: Outlooks and fields of application

The development of new methods for fractionating particles of a different nature is becoming more important in solving some scientific and technological problems. This paper presents a brief review in the theory and practice of the most common techniques for microparticle fractionation (0.1–100 μm). These are dry and wet sieving, elutriation, sequential filtration, split-flow thin fractionation (SPLITT system), field-flow fractionation (FFF), membrane filtration, and capillary electrophoresis. Special attention is paid to the FFF technique, which offers a unique potential for the separation of different materials, from biopolymers and microorganisms to colloidal and solid particles, and the estimation of their physical properties. An alternative version of sedimentation FFF is described, namely, the fractionation of microparticles in rotating coiled columns. The main advantages and limitations of the methods are revealed and their outlooks and fields of applications are envisaged.

DIRECT EXTRACTION AND SEPARATION OF SOME POLYNUCLEAR AROMATIC HYDROCARBONS (PAHs) FROM COMPLEX MIXTURES (SEWAGE SLUDGES) BY COUNTERCURRENT CHROMATOGRAPHY

The present work is the first attempt to use countercurrent chromatography for xenobiotics extraction and separation from complex natural matrices without sample pretreatment. A procedure has been developed for the direct extraction and separation of some PAHs from a sewage sludge medium being in fact a concentrated suspension. The sewage sludge and aqueous solutions containing the trace amounts (0.01–10 μg/mL) of PAHs were used as the stationary phase in the column whereas organic solvents (n-heptane, dichloromethane) or their mixture were used as mobile phase. Taking pyrene as an example it has been shown that the recovery of PAHs can be quantitative. When no PAHs was added to the sewage sludge, pyrene was found in the sample investigated at the level of 0.24 μg/mL. The possibility of the subsequent separation of naphthalene, pyrene, and benzo(g,h,i)perylene from the sewage sludge medium also has been demonstrated.