Effect of "black carbon" on antimony accumulation in traffic-loaded topsoil.

Traffic-loaded areas have been of increasing concern due to the potential risk of carcinogenic pollutants, including antimony (Sb), which accumulates mostly in atmospheric particles (PM) and can interact with soil organic matter (Corg). The stability of Sb in topsoils was studied via the adsorption mechanism using standard soils and Corg-reach vehicle-produced particles as the unique source of "traffic" Sb. The mixed adsorbents were prepared from loamy sand and clay standard soils, and braking abrasion dust and diesel engine soot as Sb sources in atmospheric PM. Whereas the black carbon (BC), as part of Corg, disposes of exceptional adsorption properties compared to the other Corg, all adsorption experiments were performed identically on the adsorbents prepared from the original standard soils and Sb source materials and on the adsorbents prepared from the same materials annealed at 375 °C to ensure only BC participation in adsorption processes. The concentration of the Sb model solution corresponded to the average Sb content in rainwater from traffic-loaded localities. In addition to Sb, the Corg and iron (Fe) were monitored. The sorbability of Sb on the loamy sand soil mixtures increased up to 90% compared with the pure soil due to new active surface sites for Sb binding created due to the Corg added with the source material. The clay soil mixture containing 10 times more Corg compared with the loamy sand soil accumulated the Corg from the source material, which resulted in blocking active sites and a decline in Sb sorbability by up to 20%. The processes performed identically with original and annealed materials showed the same trends and confirmed the key role of BC and soil quality in the accumulation and stability of Sb in traffic-loaded topsoils. The participation of Fe in Sb surface interactions was not observed.

Adsorption of Phosphate and Ammonium on Waste Building Sludge.

Two selected waste building sludges (WBS) were used in this study: (i) sludge from the production and processing of prestressed concrete pillars (B) and (ii) sludge from the production of technical stone (TS). The materials were used in their original and Fe-modified forms (BFe/TSFe) for the adsorption of NH4+ and PO43- from contaminated waters. The experiments were performed on a model solution simulating real wastewater with a concentration of 1.7 mmol·L-1 (NH4+) and 0.2 mmol·L-1 (PO43-). The adsorption of PO43- had a high efficiency (>99%) on B, BFe and TSFe, while for TS, the adsorption of PO43- was futile due to the high content of available P in the raw TS. The adsorption of NH4+ on all sorbents (B/BFe, TS/TSFe) had a lower efficiency (<60%), while TS proved to be the most effective. Leaching tests were performed according to the CSN EN 12457 standard for B/BFe and TS/TSFe before and after NH4+ and PO43- sorption when the contents of these ions in the leachates were affected by adsorption experiments in the cases of B and TS. For BFe and TSFe, the ion content in the leachates before and after the adsorption experiments was similar.

Effects of braking conditions on nanoparticle emissions from passenger car friction brakes.

Automobile friction brakes generate, in addition to coarse particles generated by mechanical processes, highly variable amount of nanoparticles from high temperature processes. The effects of braking conditions - speed, deceleration rate, brake rotor temperatures - on nanoparticle production were investigated here, aiming to provide practical guidance for reducing emissions through driving style and traffic management. Typical brake pads and a rotor from a common passenger car were subjected, on a brake dynamometer, to three runs of the WLTP brake cycle developed for brake wear particle measurements. Additionally, four sets of common brake pads were subjected to those parts of standardized brake performance tests believed to be reasonably realistic for common driving. Particle size distributions (5.6-560 nm electric mobility diameter, without removal of volatiles) show a dominant peak at 10 nm commensurate to the severity of braking and a non-linear increase of the total particle number at higher braking powers and higher total energy dissipated. The average emissions for three runs of the WLTP brake cycle were 3.3 × 1010 particles/km, while the harshest deceleration, 175-100 km/h at 5.28 m·s-2, has produced 8.4 to 38 × 1013 particles, corresponding to 2.5-11.5 thousands of km of WLTP-like driving. While previous studies have correlated higher PN production with higher average brake rotor temperature, a more complex relationship between nanoparticle emissions and a combination of initial rotor temperature, total energy dissipated and braking power has been observed here. From a driver behavior and regulatory perspective, it appears limiting harsh braking and braking from high speeds, possibly through improved driving practices, road design and traffic management, may potentially reduce brake wear nanoparticles. From the measurement perspective, it appears that "off-cycle" braking, even if relatively infrequent, may be associated with exponentially higher emissions and non-negligible share of the total emissions, and therefore should not be neglected.

Thermal stability of arsenic complexes in soils.

The release of soil arsenic (As) in an unsaturated zone under oxidative conditions and at two temperatures simulating the seasonal effect (15 °C and 23 °C) was studied in four cultivated soils from the Elbe River catchment (Czech Republic, Central Europe). The soils with a low geogenic As background contained from 10 to 50 µg.g-1 of As, mostly originating from atmospheric deposition in the past. The temperature effect on the stability of As in soils was studied in connection with the stability of hydrated iron (Fe) oxides and dissolved organic carbon (DOC), as essential binding partners of As in soils. The temperature impact on As release was related to the actual As binding in soil determined by the sequential leaching. With predominant As binding to amorphous and poorly crystalline Fe phases the higher temperature (23 °C) increased As release up to twice compare to 15 °C. In the soils with a low total Fe and the preferential As binding to well-crystallised Fe phases the temperature effect on As release was negligible. Unlike Fe, the release of DOC is strongly temperature dependent, therefore As mobilisation was controlled by the DOC concentration. A higher experimental temperature (23 °C) supported the formation of DOC and the consequent release of As and Fe into the soil solution.

Environmental interaction of antimony and arsenic near busy traffic nodes.

Antimony (Sb) and arsenic (As) are elements with similar chemistry, toxicity and binding properties, but different environmental risks and prevailing anthropogenic sources. A significant source of Sb contamination is associated with braking in extremely loaded traffic areas, where the produced abrasion dust contains up to 5% wt. of Sb2S3. In these same exposure areas, As still originates mostly from the combustion of fossil fuels. Heavily loaded crossroads from three different regions of the Czech Republic (Central Europe) were monitored for Sb content in road dusts, topsoils and reference soils during a two-year season (2016-2017). The same samples were also tested for As content to evaluate current contamination trends of both elements in exposed urban areas. The concentration of Sb varied from 5 to 70 µg g-1 in topsoils, and from 20 to 350 µg g-1 in road dusts with the preference for binding to the fine particle fraction (<0.1 mm). The average Sb concentration was up to 60 times the background value and decreased in the order: brake abrasion (103 µg g-1) > road dust (102 µg g-1)> topsoils (101 µg g-1) >> reference soils (<1 µg g-1). The concentration of As in road dust, topsoils and reference soils had about the same level, 101 µg g-1 indicating a more regional character of As pollution. Correlation factors for Sb/As versus iron (Fe)/organic matter (OM) indicated a more robust correlations in soils compared to road dusts and generally better correlations of Sb compared to As. While arsenic contamination has recently decreased thanks to a massive decline of arsenic emissions, antimony contamination indicates a dangerous trend due to growing automotive traffic.

Waste Brick Dust as Potential Sorbent of Lead and Cesium from Contaminated Water.

Adsorption properties of waste brick dust (WBD) were studied by the removing of PbII and CsI from an aqueous system. For adsorption experiments, 0.1 M and 0.5 M aqueous solutions of Cs+ and Pb2+ and two WBD (Libochovice-LB, and Tyn nad Vltavou-TN) in the fraction below 125 µm were used. The structural and surface properties of WBD were characterized by X-ray diffraction (XRD) in combination with solid-state nuclear magnetic resonance (NMR), supplemented by scanning electron microscopy (SEM), specific surface area (SBET), total pore volume and zero point of charge (pHZPC). LB was a more amorphous material showing a better adsorption condition than that of TN. The adsorption process indicated better results for Pb2+, due to the inner-sphere surface complexation in all Pb2+ systems, supported by the formation of insoluble Pb(OH)2 precipitation on the sorbent surface. A weak adsorption of Cs+ on WBD corresponded to the non-Langmuir adsorption run followed by the outer-sphere surface complexation. The leachability of Pb2+ from saturated WBDs varied from 0.001% to 0.3%, while in the case of Cs+, 4% to 12% of the initial amount was leached. Both LB and TN met the standards for PbII adsorption, yet completely failed for any CsI removal from water systems.

Hydration of Ordinary Portland Cement in Presence of Lead Sorbed on Ceramic Sorbent.

Lead, a highly toxic element, is frequently present in various solid wastes as well as in industrial effluents. Sorption with a low cost sorbent is a simple way of Pb removal from liquid streams, but stabilization of spent sorbent has to be ensured in order to prevent Pb leaching out and possible environmental contamination. In previous research, ceramic sorbent, generated as waste product in brick industry, was tested as sorbent and proved high sorption capacity for lead. Lead was sorbed partially as hydrocerussite and partially as adsorbed surface layer. The Pb leaching from sorbent was very high and thus further immobilization of sorbent was necessary. Lead, as well as other heavy metals, is known as retarder of the hydration process of Ordinary Portland Cement (OPC), used for the immobilization. In this paper, influence of sorbed Pb and PbO, as reference compound, on cement hydration was studied by calorimetry, thermogravimetry and Magic Angle Spinning Nuclear Magnetic Resonance Spectroscopy (MAS NMR). The sorbed lead was found to be less detrimental to hydration retardation due to the lower solubility of precipitated hydrocerussite in basic environment compared to PbO, which forms plumbate anion.

Removal of arsenate and antimonate by acid-treated Fe-rich clays.

Iron impurities in clays degrade the quality in many aspects, but available Fe oxides can significantly improve adsorption affinity of clays to anionic particles. Two natural Fe-rich clays (kaolin and bentonite) were treated in 0.5 M HCl (pH = 1.1) and 0.15 M (COOH)2 (pH = 1.2), and then used to adsorb AsV/SbV oxyanions from model solutions. After acid leaching, the equilibrium sorption capacities (qmax) increased from 2.3 × 10-3 to 39.2 × 10-3 mmol g-1 for AsV and from 2.4 × 10-3 to 40.1 × 10-3 mmol g-1 for SbV, more than doubling the adsorption yields (≈95%) of both oxyanions. Leaching in 0.5 M HCl enhanced both AsV and SbV adsorption, whereas leaching in 0.15 M (COOH)2 mainly improved the adsorption of SbV. Bentonite, which contained fewer crystalline forms of Fe, exhibited better sorption properties for both oxyanions. The leaching of Fe followed first-order kinetics, whereas the adsorption of AsV/SbV followed second-order kinetics. Acid leaching of Fe-rich clays can be used for the preparation of highly selective anionactive sorbents.

Interface Induced Growth and Transformation of Polymer-Conjugated Proto-Crystalline Phases in Aluminosilicate Hybrids: A Multiple-Quantum (23)Na-(23)Na MAS NMR Correlation Spectroscopy Study.

Nanostructured materials typically offer enhanced physicochemical properties because of their large interfacial area. In this contribution, we present a comprehensive structural characterization of aluminosilicate hybrids with polymer-conjugated nanosized zeolites specifically grown at the organic-inorganic interface. The inorganic amorphous Al-O-Si framework is formed by alkali-activated low-temperature transformation of metakaoline, whereas simultaneous copolymerization of organic comonomers creates a secondary epoxide network covalently bound to the aluminosilicate matrix. This secondary epoxide phase not only enhances the mechanical integrity of the resulting hybrids but also introduces additional binding sites accessible for compensating negative charge on the aluminosilicate framework. This way, the polymer network initiates growth and subsequent transformation of protocrystalline short-range ordered zeolite domains that are located at the organic-inorganic interface. By applying an experimental approach based on 2D (23)Na-(23)Na double-quantum (DQ) MAS NMR spectroscopy, we discovered multiple sodium binding sites in these protocrystalline domains, in which immobilized Na(+) ions form pairs or small clusters. It is further demonstrated that these sites, the local geometry of which allows for the pairing of sodium ions, are preferentially occupied by Pb(2+) ions during the ion exchange. The proposed synthesis protocol thus allows for the preparation of a novel type of geopolymer hybrids with polymer-conjugated zeolite phases suitable for capturing and storage of metal cations. The demonstrated (23)Na-(23)Na DQ MAS NMR combined with DFT calculations represents a suitable approach for understanding the role of Na(+) ions in aluminositicate solids and related inorganic-organic hybrids, particularly their specific arrangement and clustering at interfacial areas.

Leaching effect on arsenic mobility in agricultural soils.

The stability of soil arsenic during long-term leaching was studied in four soils from an agricultural area. Two identical columns simulating soil profiles of three layers were leached with As-free natural rainwater (<3.10(-3)mgL(-1) As) to test As mobility and the same rainwater enriched with As(V) (2.5mgL(-1) As) for the study of As accumulation. The relative As flow (µgg(-1)day(-1)) showed a comparable run for all soils, with the peak corresponding to maximum As release in the first leaching stage, and then with a tendency to equilibrate. The amount of released As was controlled by the saturated hydraulic conductivity Ksat and free Fe oxides, and the kinetics of the leaching process correlated with the content of organic matter (OM). An overall stability and accumulation of soil arsenic were mostly affected by soil properties (Ksat, particle size, clay fraction), while the chemical composition (Fe, OM content) and surface properties (specific surface area SBET, theoretical adsorption capacity Qt) were of marginal significance. The distribution of As forms was performed by sequential extraction (SEP), which indicated negligible transformation (<12%) of As species in upper soil layers.

Adsorption behavior of arsenic relating to different natural solids: soils, stream sediments and peats.

The sorption of anthropogenically derived arsenic to natural solids plays an important role in the mobility and fate of this toxic metalloid in the environment. The adsorption affinity of dissolved As(V) and As(III) to contrasting natural solids was investigated using model solutions of As(V)/As(III) and homogenized samples of soils, stream sediments and peat cores. The adsorption of As(III) and As(V) on investigated sorbents ran mostly according to the Langmuir model, with high correlation factors (>0.7). Sorption capacities varied from 3.5×10(-3) to 2.0×10(-1) mmol/g of As, whereas As(III) achieved a higher adsorption affinity due to the presence of Fe ions in the model solution. The lower horizons of soils and the intact peat, characterized by high enrichment factors of As content (R>1), represented a more stable system with decreased adsorption/desorption dynamics of As transport. A higher surface activity of solids associated with R<1, and an increased As mobility in the solid-water interface, prevailed in upper horizons of the soil and intact peat, where the contact with atmospheric deposition was expected. Stream sediments proved to be a well-balanced system with R≈1. A strong As-Fe correlation in the natural solids confirmed As affinity to Fe particles.

Modified aluminosilicates as low-cost sorbents of As(III) from anoxic groundwater.

The utilization of low-grade clay materials as selective sorbents represents one of the most effective possibilities of As removal from contaminated water reservoirs. The simple pre-treatment of these materials with Fe (Al, Mn) salts can significantly improve their sorption affinity to As oxyanions. The natural kaolin calcined at 550 degrees C (mostly metakaolin) and raw bentonite (mostly montmorillonite) pre-treated with Fe(II), Fe(III), Al(III) and Mn(II) salts were used to remove of As from the model anoxic groundwater with As(III) concentration about 0.5 and 10 mg L(-1). All the pre-treating methods were appropriate for bentonite; the efficiency of As(III) sorption varied from 92 to >99%, by the sorption capacity higher than 4.5 mg g(-1). In the case of metakaolin, Fe(II)- and Mn(II)-treatments proved the high sorption efficiency (>97%), while only <50% of As was removed after Fe(III) and Al(III) pre-treatment. The sorption capacities of treated metakaolin ranged from 0.1 to 2.0 mg g(-1).

Export of arsenic from forested catchments under easing atmospheric pollution.

Massive lignite burning in Central European power plants peaked in the 1980s. Dissolved arsenic in runoff from upland forest ecosystems is one of the ecotoxicological risks resulting from power plant emissions. Maxima in As concentrations in runoff from four forest catchments have increased 2-5 times between 1995 and 2006, and approach the drinking water limit (10 microg L(-1)). To assess the fate of anthropogenic As, we constructed input/output mass balances for three polluted and one relatively unpolluted forest catchment in the Czech Republic, and evaluated the pool size of soil As. The observation period was 11 years, and the sites spanned a 6-fold As pollution gradient. Two of the polluted sites exhibit large net As export via runoff solutes (mean of 4-5 g As ha(-1) yr(-1) for the 11-year period; up to 28 g As ha(-1) yr(-1) in 2005). This contrasts with previous studies which concluded that forest catchments are a net sink for atmogenic arsenic both at times of increasing and decreasing pollution. The amount of exported As is not correlated with the total As soil pool size, which is over 78% geogenic in origin, but correlates closely with water fluxes via runoff. Net arsenic release is caused by an interplay of hydrological conditions and retreating acidification which may mobilize arsenic by competitive ligand exchange. The effects of droughts and other aspects of climate change on subsequent As release from soil were not investigated. Between-site comparisons indicate that most pollutant As may be released from humus.

Geochemical characterisation of shallow aquifer sediments of Matlab Upazila, Southeastern Bangladesh - implications for targeting low-As aquifers.

High arsenic (As) concentrations in groundwater pose a serious threat to the health of millions of people in Bangladesh. Reductive dissolution of Fe(III)-oxyhydroxides and release of its adsorbed As is considered to be the principal mechanism responsible for mobilisation of As. The distribution of As is extremely heterogeneous both laterally and vertically. Groundwater abstracted from oxidised reddish sediments, in contrast to greyish reducing sediments, contains significantly lower amount of dissolved arsenic and can be a source of safe water. In order to study the sustainability of that mitigation option, this study describes the lithofacies and genesis of the sediments within 60 m depth and establishes a relationship between aqueous and solid phase geochemistry. Oxalate extractable Fe and Mn contents are higher in the reduced unit than in the oxidised unit, where Fe and Mn are present in more crystalline mineral phases. Equilibrium modelling of saturation indices suggest that the concentrations of dissolved Fe, Mn and PO(4)(3-)-tot in groundwater is influenced by secondary mineral phases in addition to redox processes. Simulating As(III) adsorption on hydroferric oxides using the Diffuse Layer Model and analytical data gave realistic concentrations of dissolved and adsorbed As(III) for the reducing aquifer and we speculate that the presence of high PO(4)(3-)-tot in combination with reductive dissolution results in the high-As groundwater. The study confirms high mobility of As in reducing aquifers with typically dark colour of sediments found in previous studies and thus validates the approach for location of wells used by local drillers based on sediment colour. A more systematic and standardised colour description and similar studies at more locations are necessary for wider application of the approach.

Arsenic in atmospheric deposition at the Czech-Polish border: two sampling campaigns 20 years apart.

Arsenic (As) occurs in atmospheric deposition both in soluble and insoluble forms, mainly bound to fine aerosol particles (less than 2.5 microm). Interception deposition (i.e. fog, dew and ice accretion) represents a specific type of atmospheric deposition, which has been much more contaminated with As than bulk deposition. This study compares the As amount and its binding forms in bulk and interception deposition in the winters of 1984-1986 and 2003-2005 in the Orlické hory mountains (Adlergebirge) near the Czech-Polish border; sampled and analysed by the same methodology. The As concentrations in ice accretions decreased 16 times over the twenty year period (from 50 microg L(-1) to 3 microg L(-1)), while the pH values increased by 0.8 units. As concentrations in snow decreased from 15 microg L(-1) in 1984-1986 to <2 microg L(-1) in 2003-2005. This decline mirrored the considerable decrease in industrial emissions in Central Europe. Higher acidity of interception deposition (about 1 pH unit) in comparison with the bulk deposition was observed in both sampling periods. The quantity of bulk deposition (snowfall) also influenced the As concentration in interception deposition. Dry periods resulted in higher As-amounts in interception deposition due to limited washing of atmospheric aerosol particles by wet deposition. The As concentration and stability in atmospheric deposition are important for the study of subsequent As-migration and/or accumulation in soil -- groundwater -- surface water.

Sorption of As(V) on aluminosilicates treated with Fe(II) nanoparticles.

Adsorption of arsenic on clay surfaces is important for the natural and simulated removal of arsenic species from aqueous environments. In this investigation, three samples of clay minerals (natural metakaoline, natural clinoptilolite-rich tuff, and synthetic zeolite) in both untreated and Fe-treated forms were used for the sorption of arsenate from model aqueous solution. The treatment of minerals consisted of exposing them to concentrated solution of Fe(II). Within this process the mineral surface has been laden with Fe(III) oxi(hydroxides) whose high affinity for the As(V) adsorption is well known. In all investigated systems the sorption capacity of Fe(II)-treated sorbents increased significantly in comparison to the untreated material (from about 0.5 to >20.0 mg/g, which represented more than 95% of the total As removal). The changes of Fe-bearing particles in the course of treating process and subsequent As sorption were investigated by the diffuse reflectance spectroscopy and the voltammetry of microparticles. IR spectra of treated and As(V)-saturated solids showed characteristic bands caused by Fe(III)SO(4), Fe(III)O, and AsO vibrations. In untreated As(V)-saturated solids no significant AsO vibrations were observed due to the negligible content of sorbed arsenate.