Continuous-flow separation and preconcentration of microplastics from natural waters using countercurrent chromatography.

Microplastics is known to be ubiquitous in aquatic environment. Quantification of microplastics in natural waters is an important problem of analytical chemistry, the solution of which is needed for the assessment of water quality and potential risks for water inhabitants and consumers. Separation methods play a key role in the correct quantification of microplastics in natural waters. In the present study the applicability of countercurrent chromatography to the continuous-flow separation and preconcentration of microplastics from water samples in rotating coiled column (RCC) using water-oil systems has been demonstrated for the first time. The effect of column rotation speed and mobile phase (water) flow rate on the retention of the stationary (oil) phase in RCC is studied. The retention parameters of 10 vegetable and 2 synthetic oils are determined. Castor, olive, rapeseed, soybean, linseed, sesame, and sunflower oils are found to be applicable to the separation of microplastics from water samples using RCC. Taking as example polyethylene microparticles of different size (40-63, 63-100, and 100-250 µm), the high recovery of microplastics (about 100 %) from aqueous phase into castor and rapeseed oils is shown. The method has been proven to be efficient for the separation of microplastics from simulated fresh and sea natural waters. It may be perspective not only for the quantification of microplastics in natural waters but as well as for the purification of wastewaters containing microplastics.

Novel zone elution mode in coiled tube field-flow fractionation for online separation and characterization of environmental submicron particles.

Coiled tube field-flow fractionation (CTFFF) is currently applied to environmental and material studies. In the present work, a novel zone elution mode in CTFFF has been proposed and developed. Zone elution mode is based on the separation of particles by stepwise decreasing the flow rate of the carrier fluid and their subsequent elution at a constant flow rate. The fractionation parameters were optimized using a mixture of standard silica submicron particles (150, 390, and 900 nm). Taking samples of volcanic ash as examples, it has been demonstrated that zone elution mode can be successfully used for the fractionation of environmental nano- and submicron particles. For the first time, CTFFF was coupled online with a dynamic light scattering detector for the size characterization of eluted particles. Zone elution in CTFFF can serve for the further development of hyphenated techniques enabling efficient fractionation and size/elemental characterization of environmental particles in nano- and submicrometric size ranges.

Distribution of Platinum and Palladium between Dissolved, Nanoparticulate, and Microparticulate Fractions of Road Dust.

Ageing processes of vehicle catalytic converters inevitably lead to the release of Pt and Pd into the environment, road dust being the main sink. Though Pt and Pd are contained in catalytic converters in nanoparticulate metallic form, under environmental conditions, they can be transformed into toxic dissolved species. In the present work, the distribution of Pt and Pd between dissolved, nanoparticulate, and microparticulate fractions of Moscow road dust is assessed. The total concentrations of Pt and Pd in dust vary in the ranges 9-142 ng (mean 35) and 155-456 (mean 235) ng g-1, respectively. The nanoparticulate and dissolved species of Pt and Pd in dust were studied using single particle inductively coupled plasma mass spectrometry. The median sizes of nanoparticulate Pt and Pd were 7 and 13 nm, respectively. The nanoparticulate fraction of Pt and Pd in Moscow dust is only about 1.6-1.8%. The average contents of dissolved fraction of Pt and Pd are 10.4% and 4.1%, respectively. The major fractions of Pt and Pd (88-94%) in road dust are associated with microparticles. Although the microparticulate fractions of Pt and Pd are relatively stable, they may become dissolved under changing environmental conditions and, hence, transformed into toxic species.

Nanospeciation of metals and metalloids in volcanic ash using single particle inductively coupled plasma mass spectrometry.

Volcanic activity is one of the main sources of natural nanoparticles. It has been found earlier that the concentration of toxic metals/metalloids in nanoparticles of volcanic ash may be one or two orders of magnitude higher than in bulk sample. However, fate and behavior of toxic metals/metalloids depend on the type of their binding to nanoparticles. Hence, element species adsorbed onto pyroclastic nanoparticles and individual nanophases of metal/metalloid oxides or salts should be distinguished. For the first time, the single particle inductively coupled plasma mass spectrometry has been applied to the nanospeciation of volcanic particles. Ashes of four volcanoes of Kamchatka (Russia) were under study. Nanoparticles were separated from bulk ash samples using coiled-tube field-flow fractionation. It has been shown that the nanospeciation of Ni, Zn, Ag, Cd, Tl, As, Pb, Bi, Te, and Hg is dependent on element and volcano. In most cases these elements can be found both as species absorbed onto pyroclastic nanoparticles and as individual nanophases. The ratios of individual nanophases and adsorbed species vary with the sample. In nanoparticles of Tolbachik volcano ash, Ni, Zn, Tl, and Hg are present only as individual nanophases, while Bi, As, Pb, Ag, Cd, and Te are found both as adsorbed species and individual nanophases. The results obtained open a new door into study on the chemical composition of volcanic ash nanoparticles and their fate in the environment.

Natural silicate nanoparticles: separation, characterization, and assessment of stability and perspectives of their use as reference nanomaterials.

Natural nanomaterials, which play a very important role in environmental processes, are so far poorly studied. Firstly, the separation of nanoparticles from the bulk sample is a challenge. Secondly, the absence of reference natural nanomaterials makes it impossible to compare the results obtained by different researchers and develop a unified methodology for the separation and characterization of natural nanomaterials. Therefore, the development of reference natural nanomaterials is an urgent need of the environmental analytical chemistry. In this work, mineral nanoparticles (kaolinite, montmorillonite, muscovite, and quartz) have been studied as potential reference natural nanomaterials. A set of analytical methods including coiled-tube field-flow fractionation, scanning electron microscopy, dynamic light scattering, laser diffraction, inductively coupled plasma atomic emission, and mass spectrometry are applied to the separation and characterization of nanoparticles. It has been shown by laser diffraction that 93-98% of separated mineral nanoparticles are in the size range from about 40 to 300 nm, while 2-7% have size up to 830 nm. The size range of particles is confirmed by electron microscopy. Major (Al, Na, K, Ca, Fe), trace (Ti, Co, Cu, Zn, Tl, Pb, Bi, etc.), and rare earth elements have been determined in the suspensions of kaolinite, montmorillonite, and muscovite nanoparticles. Based on Al content, the concentration of mineral nanoparticles in suspensions is estimated. Agglomeration stability (consistency of size distribution) of nanoparticles at pH 6-8 is assessed. It has been shown that muscovite nanoparticles are stable at pH 7-8, whereas montmorillonite nanoparticles are stable only at pH 8 for at least 4 weeks. A noticeable agglomeration of kaolinite nanoparticles is observed at pH 6-8. Due to the low concentration of quartz nanoparticles, their characterization and stability assessment are hindered. The challenges of the development of reference natural nanomaterials are discussed.

Characterization of volcanic ash nanoparticles and study of their fate in aqueous medium by asymmetric flow field-flow fractionation-multi-detection.

Dimensional and elemental characterization of environmental nanoparticles is a challenging task that requires the use of a set of complementary analytical methods. Asymmetric flow field-flow fractionation coupled with UV-Vis, multi-angle laser light scattering and ICP-MS detection was applied to study the nanoparticle fraction of a volcanic ash sample, in a Milli-Q water suspension at pH 6.8. It has been shown that the separated by sedimentation nanoparticle fraction of the Klyuchevskoy volcano ash suspension contains 3 polydisperse populations for which size ranges (expressed in gyration radius, rG), hydrodynamic behaviours (evaluated via shape index) and elemental compositions are different. These 3 populations did not dissolve over the 72-h study but aggregated and settled out differently. Thus, the population of particles with gyration radii <140 nm (P1), which contained 6% Al2O3 and represented approximately 20% by mass of the nanoparticle fraction, remained in suspension without observable aggregation. The populations P2 and P3, which represented 67% and 13% by mass in the initial suspension, covered the rG range 25-250 nm and contained 17% and 15% Al2O3, respectively. Over time, populations P2 and P3 aggregated and their concentration in suspension at 72 h decreased by approximately 40% compared with the initial suspension. The decrease of these nanoparticle populations occurred either from the beginning of the temporal monitoring (P2) or after 30 h (P3). Aggregation generated a new population (P4) in suspension with rG up to 300 nm and mostly consisting of P2. This population represented only up to 6 to 7% of the nanoparticle fraction and decreased beyond 50 h. As a result, the trace elements present in the nanoparticle fraction and monitored (Cu and La) were also no longer found in the suspension. The results obtained can offer additional insights into the fate of volcanic ash nanoparticles in the environment.

Separation of nanoparticles from polydisperse environmental samples: comparative study of filtration, sedimentation, and coiled tube field-flow fractionation.

Nanoparticles (NPs) in the environment have a potential risk for human health and the ecosystem due to their ubiquity, specific characteristics, and properties (extreme mobility in the environment, abilities to accumulate of toxic elements and penetrate into living organisms). There is still a gap in studies on the chemical composition of natural NPs. The main reason is the difficulty to recover NPs, which may represent only one-thousandth or less of the bulk environmental sample, for further dimensional and quantitative characterization. In the present study, a methodology for the recovery of the nanoparticle fraction from polydisperse environmental samples was developed taking as example volcanic ashes from different regions of the world. For the first time, three separation methods, namely, filtration through a 0.45-µm membrane, sedimentation, and coiled tube field-flow fractionation (CTFFF), were comparatively studied. The separated fractions were characterized by laser diffraction and scanning electron microscopy and then analyzed by inductively coupled plasma atomic emission and mass spectrometry. It has been shown that all three methods provide the separation of NPs less than 400 nm from the bulk material. However, the fraction separated by sedimentation also contained a population (5% in mass) of submicron particles (~ 400-900 nm). The filtration resulted in low recovery of NPs. The determination of most trace elements was then impossible; the concentration of elements was under the limit of detection of the analytical instrument. The sedimentation and CTFFF made it possible to determine quantifiable concentrations for both major and trace elements in separated fractions. However, the sedimentation took 48 h while CTFFF enabled the fractionation time to be decreased down to 2 h. Hence, CTFFF looked to be the most promising method for the separation of NPs followed by their quantitative elemental analysis.

Assessment of elemental composition and properties of copper smelter-affected dust and its nano- and micron size fractions.

A comprehensive approach has been developed to the assessment of composition and properties of atmospherically deposited dust in the area affected by a copper smelter. The approach is based on the analysis of initial dust samples, dynamic leaching of water soluble fractions in a rotating coiled column (RCC) followed by the determination of recovered elements and characterization of size, morphology and elemental composition of nano-, submicron, and micron par ticles of dust separated using field-flow fractionation in a RCC. Three separated size fractions of dust (<0.2, 0.2-2, and >2 µm) were characterized by static light scattering and scanning electron microscopy, whereupon the fractions were analyzed by ICP-AES and ICP-MS (after digestion). It has been evaluated that toxic elements, which are characteristics for copper smelter emissions (As, Cu, Zn), are accumulated in fraction >2 µm. At the same time, up to 2.4, 3.1, 8.2, 6.7 g/kg of As, Cu, Zn, Pb, correspondently, were found in nanoparticles (<0.2 µm). It has been also shown that some trace elements (Sn, Sb, Ag, Bi, and Tl) are accumulated in fraction <0.2, and their content in this fraction may be one order of magnitude higher than that in the fraction >2 µm, or the bulk sample. It may be assumed that Sn, Sb, Ag, Bi, Tl compounds are adsorbed onto the finest dust particles as compared to As, Cu, Zn compounds, which are directly emitted from the copper smelter as microparticles.

A novel combined countercurrent chromatography - inductively coupled plasma mass spectrometry method for the determination of ultra trace uranium and thorium in Roman lead.

The concentration of uranium and thorium in lead shields, which are used in underground particle physics research, should be monitored at sub-ppt levels. A combination of extraction chromatography and inductively coupled plasma mass spectrometry can resolve this analytical task. However, a multi-step complicated separation procedure and clean room are required. Besides, the recovery yields for U and Th do not exceed 80% and 60%, correspondingly. We propose an alternative approach. U and Th were pre-concentrated and separated from Pb by countercurrent chromatography, which is a support-free liquid-liquid chromatography. A series of two-phase extraction systems were tested. Under the optimized conditions, U and Th were extracted using a system 1 M HNO3/0.01 M tetraphenylmethylenediphosphine dioxide in chloroform and then eluted by 0.01 M aqueous solution of etidronic acid and determined by inductively coupled plasma mass spectrometry. The separation is performed in one chromatographic run, takes less than 1 h, and provides the quantitative recovery of U and Th. The limits of detection are 3 and 1 ppt for U and Th, correspondingly. The concentrations of U and Th in Roman lead, which was raised from the sea bottom, were lower than the limits of detection. It sounds unbelievable, nevertheless, the antique lead manufactured by Romans can indeed serve as a high-purity low-background material for the construction of Pb shields. Apart from the analysis of antique lead, the proposed approach can be easily extended to the determination of ultra trace impurities in different materials due to a very wide variety of two-phase extraction systems, which can be used in countercurrent chromatography.

A contribution of nanoscale particles of road-deposited sediments to the pollution of urban runoff by heavy metals.

Road-deposited sediments (RDS) present a sink for traffic-related pollutants including heavy metals (HMs). HMs associated with RDS particles enter the urban aquatic environment during rainfall events and have adverse effects for biota. RDS nanoscale particles (NSPs) require special consideration due to their specific properties, extremely high mobility in the environment, and ability to penetrate into living organisms. In the present work, the contribution of NSPs of RDS to the pollution of urban runoff by HMs has been evaluated for the first time. It has been shown that bulk RDS samples are polluted by HMs as compared to background urban soils (geo-accumulation indexes of Cu and Zn may attain 2-3). Meanwhile, NSPs of RDS are enriched by HMs as compared to bulk samples; concentration factor for Ni, Cu, Zn, Cd, Sn, and Pb in NSPs being varied from 2 to 10. The water-soluble fractions of RDS samples were also analyzed. Results have shown that the content of water-soluble HMs in RDS is insignificant and rarely exceeds 0.5% of the total contents of HMs in the bulk samples; the highest contents are identified for Cu and Pb. It should be noted that the water-soluble fraction is nearly free from Zn and this element is almost entirely present as particulate matter (NSPs). In general, the overall contribution of NSPs and water-soluble fraction of HMs to the pollution of urban runoff is comparable.

Nanoparticles of volcanic ash as a carrier for toxic elements on the global scale.

At present, there is concern about engineered nanoparticles in the environment, whereas natural nanoparticles (NPs) and their impact are often neglected. In our paper, we demonstrate the important role of nanoparticles of volcanic ash in transport of toxic elements on a global scale. A single volcanic eruption can eject millions of tons of ash. NPs of volcanic ash reach the upper troposphere and the stratosphere and may "travel" around the world for years affecting human health, environment, and even climate. So far, there is a gap in exposure assessment of volcanic ash NPs since their chemical composition remains largely unknown. Here we show for the first time that volcanic ash NPs can serve as an important carrier for potentially toxic elements. The concentrations of Ni, Zn, Cd, Ag, Sn, Se, Te, Hg, Tl, Pb, Bi in volcanic ash NPs (<100 nm) were found to be 10-500 times higher than total contents of these elements in bulk samples. This is valid for volcanoes from different regions of the world (Kamchatka, Far East of Russia and Andes, Chile). The work opens a new door into studies on biogeochemical impact of volcanic ash.

Assessment of elemental composition and properties of copper smelter-affected dust and its nano- and micron size fractions.

A comprehensive approach has been developed to the assessment of composition and properties of atmospherically deposited dust in the area affected by a copper smelter. The approach is based on the analysis of initial dust samples, dynamic leaching of water soluble fractions in a rotating coiled column (RCC) followed by the determination of recovered elements and characterization of size, morphology and elemental composition of nano-, submicron, and micron particles of dust separated using field-flow fractionation in a RCC. Three separated size fractions of dust (<0.2, 0.2-2, and >2 µm) were characterized by static light scattering and scanning electron microscopy, whereupon the fractions were analyzed by ICP-AES and ICP-MS (after digestion). It has been evaluated that toxic elements, which are characteristics for copper smelter emissions (As, Cu, Zn), are accumulated in fraction >2 µm. At the same time, up to 2.4, 3.1, 8.2, 6.7 g/kg of As, Cu, Zn, Pb, correspondently, were found in nanoparticles (<0.2 µm). It has been also shown that some trace elements (Sn, Sb, Ag, Bi, and Tl) are accumulated in fraction <0.2, and their content in this fraction may be one order of magnitude higher than that in the fraction >2 µm, or the bulk sample. It may be assumed that Sn, Sb, Ag, Bi, Tl compounds are adsorbed onto the finest dust particles as compared to As, Cu, Zn compounds, which are directly emitted from the copper smelter as microparticles.

Continuous-flow leaching in a rotating coiled column for studies on the mobility of toxic elements in dust samples collected near a metallurgic plant.

Continuous-flow (dynamic) leaching in a rotating coiled column has been applied to studies on the mobility of Zn, Cd, Cu, Pb, Ni, Sb, As, S, and other potentially toxic elements in atmospherically deposited dust samples collected near a large copper smelter (Chelyabinsk region, Russia). Water and simulated "acid rain" (pH 4) were used as eluents. The technique enables not only the fast and efficient leaching of elements but as well time-resolved studies on the mobilization of heavy metals, sulphur, and arsenic in environmentally relevant forms to be made. It is shown that up to 1.5, 4.1, 1.9, 11.1, and 46.1% of Pb, As, Cu, Zn, and S, correspondingly, can be easily mobilized by water. Taking into consideration that the total concentrations of these elements in the samples under investigation are surprisingly high and vary in the range from 2.7 g/kg (for arsenic) to 15.5 g/kg (for sulphur), the environmental impact of the dust may be dramatic. The simulated acid rain results in somewhat higher recoveries of elements, except Cu and Pb. The proposed approach and the data obtained can very useful for the risk assessment related to the mobility of potentially toxic elements and their inclusion in the biogeochemical cycle.

Field-flow fractionation of nano- and microparticles in rotating coiled columns.

Field-flow fractionation (FFF) is a very powerful and versatile set of liquid chromatography-like elution methods. However, conventional FFF separations occur in thin channels and the sample weight injected is usually less than 1 mg to avoid overloading. The fractionation in a rotating coiled column (RCC), which can be attributed to sedimentation FFF, enables the handling sample weight to be increased at least up to 1 g. An uneven distribution of particles in RCC was first observed by Y. Ito et al. in 1966. The work in this direction was continued by P.S. Fedotov et al. in 2000. Regularities of the behaviour of nano- and microparticles of different size and origin in RCCs with different design parameters were systematically studied taking as example silica particles, latex beads, quartz sand, clay minerals, and other samples. The basic principles of the new FFF method were established. The developed method was applied to the speciation analysis of polydisperse environmental samples, in particular, for the separation of soils into silt, clay and sand fractions. For the first time, nano- and submicron particles of street dust have been separated, weighted, characterized by electronic microscopy, and quantitatively analyzed by ICP-MS (after digestion). 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. The fractionation in RCC was also used for the recovery of a nearly monodisperse fraction (4.5 µm) of a chromatographic sorbent based on polystyrene-divinylbenzene; impurities remaining from the synthesis and smaller particles (1-2 µm) being removed. Study on the fractionation of synthetic samples has demonstrated the applicability of the method to the preparative separation and purification of polydisperse materials.

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.

Continuous-flow fractionation of selenium in contaminated sediment and soil samples using rotating coiled column and microcolumn extraction.

Dynamic fractionation is considered to be an attractive alternative to conventional batch sequential extraction procedures for partitioning of trace metals and metalloids in environmental solid samples. This paper reports the first results on the continuous-flow dynamic fractionation of selenium using two different extraction systems, a microcolumn (MC) packed with the solid sample and a rotating coiled column (RCC) in which the particulate matter is retained under the action of centrifugal forces. The eluents (leachants) were applied in correspondence with a four-step sequential extraction scheme for selenium addressing "soluble", "adsorbed", "organically bound", and "elemental" Se fractions extractable by distilled water, phosphate buffer, tetramethylammonium hydroxide, and sodium sulphite solutions, respectively. Selenium was determined in the effluent by using an inductively coupled plasma atomic emission spectrometer. Contaminated creek sediment and dumped waste (soil) samples from the abandoned mining area were used to evaluate resemblances and discrepancies of two continuous-flow methods for Se fractionation. In general, similar trends were found for Se distribution between extractable and residual fractions. However, for the dumped waste sample which is rich in organic matter, the extraction in RCC provided more effective recovery of environmentally relevant Se forms (the first three leachable fractions). The most evident deviation was observed for "adsorbed" Se (recoveries by RCC and MC are 43 and 7 mg kg(-1), respectively). The data obtained were correlated with peculiarities of samples under investigation and operational principles of RCC and MC.

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.

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.

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 Tamm's 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.

Dynamic studies on the mobility of trace elements in soil and sediment samples influenced by dumping of residues of the flood in the Mulde River region in 2002.

In the analysis of soil samples, batch sequential extraction procedures are traditionally used for the fractionation of trace elements to access their mobility and potential risk for the contamination of groundwater. In the present work a continuous-flow technique has been used that enables not only the fast and efficient leaching of trace elements but as well as time-resolved studies on the mobilization of arsenic and selected heavy metals in different forms to be made. Rotating coiled columns (RCC) earlier used mainly in countercurrent chromatography have been successfully applied to the dynamic leaching of heavy metals from soils contaminated by flooding sludge's. The sample was retained in a PTFE rotating column as the stationary phase whereas aqueous solutions were continuously pumped through. The contents of elements were determined by on-line coupling of RCC and inductively coupled plasma atomic emission spectrometry (ICP-AES). This enables real-time data on the leaching process to be obtained. Dynamic and traditional batch procedures were compared. It has been shown that the aqueous elution under centrifugal forced conditions is much more effective for the mobilization of heavy metals. Hence, the dynamic leaching is characterized by a substantially more intensive interaction between solid and water and is besides substantially more time-saving than the conventional batch procedure. The RCC procedure was also employed for preliminary leaching studies with a simulated "acid rain". In comparison with the water leaching, the mobilization of heavy metals and arsenic from soil samples with employment of simulated acid rain as eluent was less effective.