Importance of inner-sphere P-O-Fe bonds in natural and synthetic mineral-organic associations.

Sorption of organic molecules on mineral surfaces can occur through several binding mechanisms of varying strength. Here, we investigated the importance of inner-sphere P-O-Fe bonds in synthetic and natural mineral-organic associations. Natural organic matter such as water extracted soil organic matter (WESOM) and extracellular polymeric substances (EPS) from liquid bacterial cultures were adsorbed to goethite and examined by FTIR spectroscopy and P K-edge NEXAFS spectroscopy. Natural particles from a Bg soil horizon (Gleysol) were subjected to X-ray fluorescence (XRF) mapping, NanoSIMS imaging, and NEXAFS spectro-microscopy at the P K-edge. Inner-sphere P-O-Fe bonds were identified for both, adsorbed EPS extracts and adsorbed WESOMs. Characteristic infrared peaks for P-O-Fe stretching vibrations are present but cannot unambiguously be interpreted due to possible interferences with mono- and polysaccharides. For the Bg horizon, P was only found on Fe oxides, covering the entire surface at different concentrations, but not on clay minerals. Linear combination fitting of NEXAFS spectra indicates that this adsorbed P is mainly a mixture of orthophosphate and organic P compounds. By combining atomic force microscopy (AFM) images with STXM-generated C and Fe distribution maps, we show that the Fe oxide surfaces were fully coated with organic matter. In contrast, clay minerals revealed a much lower C signal. The C NEXAFS spectra taken on the Fe oxides had a substantial contribution of carboxylic C, aliphatic C, and O-alkyl C, which is a composition clearly different from pure adsorbed EPS or aromatic-rich lignin-derived compounds. Our data show that inner-sphere P-O-Fe bonds are important for the association of Fe oxides with soil organic matter. In the Bg horizon, carboxyl groups and orthophosphate compete with the organic P compounds for adsorption sites.

Maize Field Study Reveals Covaried Microbiota and Metabolic Changes in Roots over Plant Growth.

Plant roots are colonized by microorganisms from the surrounding soil that belong to different kingdoms and form a multikingdom microbial community called the root microbiota. Despite their importance for plant growth, the relationship between soil management, the root microbiota, and plant performance remains unknown. Here, we characterize the maize root-associated bacterial, fungal, and oomycetal communities during the vegetative and reproductive growth stages of four maize inbred lines and the pht1;6 phosphate transporter mutant. These plants were grown in two long-term experimental fields under four contrasting soil managements, including phosphate-deficient and -sufficient conditions. We showed that the maize root-associated microbiota is influenced by soil management and changes during host growth stages. We identified stable bacterial and fungal root-associated taxa that persist throughout the host life cycle. These taxa were accompanied by dynamic members that covary with changes in root metabolites. We observed an inverse stable-to-dynamic ratio between root-associated bacterial and fungal communities. We also found a host footprint on the soil biota, characterized by a convergence between soil, rhizosphere, and root bacterial communities during reproductive maize growth. Our study reveals the spatiotemporal dynamics of the maize root-associated microbiota and suggests that the fungal assemblage is less responsive to changes in root metabolites than the bacterial community. IMPORTANCE Plant roots are inhabited by microbial communities called the root microbiota, which supports plant growth and health. We show in a maize field study that the root microbiota consists of stable and dynamic members. The dynamics of the microbial community appear to be driven by changes in the metabolic state of the roots over the life cycle of maize.

Crop genetic diversity uncovers metabolites, elements, and gene networks predicted to be associated with high plant biomass yields in maize.

Rapid population growth and increasing demand for food, feed, and bioenergy in these times of unprecedented climate change require breeding for increased biomass production on the world's croplands. To accelerate breeding programs, knowledge of the relationship between biomass features and underlying gene networks is needed to guide future breeding efforts. To this end, large-scale multiomics datasets were created with genetically diverse maize lines, all grown in long-term organic and conventional cropping systems. Analysis of the datasets, integrated using regression modeling and network analysis revealed key metabolites, elements, gene transcripts, and gene networks, whose contents during vegetative growth substantially influence the build-up of plant biomass in the reproductive phase. We found that S and P content in the source leaf and P content in the root during the vegetative stage contributed the most to predicting plant performance at the reproductive stage. In agreement with the Gene Ontology enrichment analysis, the cis-motifs and identified transcription factors associated with upregulated genes under phosphate deficiency showed great diversity in the molecular response to phosphate deficiency in selected lines. Furthermore, our data demonstrate that genotype-dependent uptake, assimilation, and allocation of essential nutrient elements (especially C and N) during vegetative growth under phosphate starvation plays an important role in determining plant biomass by controlling root traits related to nutrient uptake. These integrative multiomics results revealed key factors underlying maize productivity and open new opportunities for efficient, rapid, and cost-effective plant breeding to increase biomass yield of the cereal crop maize under adverse environmental factors.

Temperature-induced diurnal redox potential in soil.

With the capabilities to measure redox potentials (EH) at a high temporal resolution, scientists have observed diurnal EH that occur in a distinct periodicity in soils and sediments. These patterns have been disregarded for a long time because minor fluctuations of the EH in the tens of mV range are difficult to interpret. Various explanations have been proposed for the origin of diel EH but a cohesive assessment of the temperature-dependency for field- and laboratory-based investigations is missing at present. In this study, we investigated spatiotemporal diel EH of previous long-term (up to 10 years) field- and lab-based monitoring data collected at high-temporal (every hour) and spatial (up to 6 depths) resolution. In addition, we set up a redox experiment where we manipulated the soil temperature (ST) by diel temperature cycles to assess the EH response. Diel fluctuations were absent for laboratory experiments with ΔEH of a few mV (daily EH-max - daily EH-min), but we found pronounced fluctuations up to ∼100 mV for field investigations. The spatiotemporal pattern in EH fluctuations was amplified in the topsoil during the summer months concomitant with ST. We showed for the first time that changes in ST during an incubation experiment altered the EH by -3.3 mV °C-1 and inferred that the diel EH were driven by the thermal conditions of the soil itself. This is particularly important when EH is measured close to the soil surface and underlines that minor fluctuations of the EH with a recurring periodicity should be carefully checked for its dependency with the soil and reference electrode temperature. Redox measurements should not be considered a routine determination and cautious handling of EH data by physical sound corrections is urgently needed in order to link ΔEH to daily biogeochemical cycling in soils.

Full-scale accelerated carbonation of waste incinerator bottom ash under continuous-feed conditions.

Bottom ash (BA) is the dominant residue derived from the incineration of municipal solid waste or refuse-derived fuel (RDF). Costs for the disposal of the material chiefly depend on the leachability of salts and trace metals which may be cut by ageing the BA for several months to promote carbonation via uptake of carbon dioxide (CO2). Enhanced exposure to CO2 sources has been referred to as accelerated carbonation. Here we report on the successful implementation of the accelerated carbonation of BA in a continuously fed full-scale rotating drum reactor. The reactor was operated with the fine fraction (< 20 mm) of BA from an RDF incinerator and the exhaust of a combined heat and power unit was used as the reactant gas. The system was tested in 15 experiments and the process efficiency was addressed by maximizing the reactor loading and minimizing the BA residence time. Results confirmed that the reactor loading depended on the rotation-normalized mass flow rate of BA where the slope and intercept of the characteristic varied with the design of the reactor discharge and the use of mixing tools. According to leaching test results, BA residence times as low as 60 min were sufficient to render the carbonated BA a non-hazardous waste and convert it to a material suited for geotechnical applications. This outperforms previous laboratory findings and opens new perspectives for implementing the accelerated carbonation at incinerator sites.

Leaching of hexavalent chromium from young chromite ore processing residue.

Chromite ore processing residue (COPR) is a waste derived from the chromate extraction from roasted ores and is deposited in some countries in landfills. The objective of this study was to investigate the leaching characteristics of hexavalent Cr [Cr(VI)] from two COPR samples obtained from unlined landfills in the Kanpur area of northern India. Column experiments were conducted under water-saturated conditions to simulate Cr release from the wastes caused by tropical heavy-rain events. Leached Cr(VI) decreased from 1,800 to 300 mg L-1 (Rania site) and 1,200 to 163 mg L-1 (Chhiwali site) during exchange of 12 pore volumes, which approximately corresponds to 2 yr of monsoon precipitation. Flow interruptions for 10, 100, and 1,000 h had little effect on Cr(VI) concentrations in the leachate, suggesting that Cr(VI) leaching was not limited by slow release kinetics. Calcium aluminum chromium oxide hydrates (CAC), and highly soluble phases such as Na2 CrO4 may play a role in controlling Cr(VI) concentration in the leachates. The amount of Cr(VI) leached from the columns accounted for 16% of the total Cr(VI) present in both COPR samples. A decrease in the solid-phase Cr(VI)/Crtotal ratio along the column was identified by X-ray absorption near edge structure (XANES) spectroscopy. Consistently, the smallest Cr(VI)/Crtotal ratios were found in the lower column section closest to the inflow. Our results suggest that Cr(VI) leaching from the unlined COPR landfills will continue for centuries, highlighting the urgent need to remediate these dumpsites.

Soil Organic Matter and Phosphate Sorption on Natural and Synthetic Fe Oxides under in Situ Conditions.

Iron (Fe) oxides in soils are strong sorbents for environmentally important compounds like soil organic matter (SOM) or phosphate, while sorption under field conditions is still poorly understood. We installed polyvinyl chloride plastic bars which have been coated either with synthetic Fe or manganese (Mn) oxides for 30 days in a redoximorphic soil. A previous study revealed the formation of newly formed ("natural") Fe oxides along the Mn oxide coatings. This enables us to differentiate between sorption occurring onto the surfaces of synthetic versus natural Fe oxides. After removal of the bars, they were analyzed by nanoscale secondary ion mass spectrometry (NanoSIMS) to study the distribution of Fe (56Fe16O-), SOM (12C14N-), and phosphorus (31P16O2-) at the microscale. Image analysis of individual Fe oxide particles revealed a close association of Fe, SOM, and P resulting in coverage values up to 71%. Furthermore, ion ratios between sorbent (56Fe16O-) and sorbate (12C14N- and 31P16O2-) were smaller along the natural oxides when compared with those for synthetic Fe oxides. We conclude that both natural and synthetic Fe oxides rapidly sequester SOM and P (i.e., within 30 days) but that newly, natural formed Fe oxides sorbe more SOM and P than synthetic Fe oxides.

Site-specific distribution of oak rhizosphere-associated oomycetes revealed by cytochrome c oxidase subunit II metabarcoding.

The phylum Oomycota comprises important tree pathogens like Phytophthora quercina, involved in central European oak decline, and Phytophthora cinnamomi shown to affect holm oaks among many other hosts. Despite the importance to study the distribution, dispersal and niche partitioning of this phylum, metabarcoding surveys, and studies considering environmental factors that could explain oomycete community patterns are still rare. We investigated oomycetes in the rhizosphere of evergreen oaks in a Spanish oak woodland using metabarcoding based on Illumina sequencing of the taxonomic marker cytochrome c oxidase subunit II (cox2). We developed an approach amplifying a 333 bp long fragment using the forward primer Hud-F (Mycologia, 2000) and a reverse primer found using DegePrime (Applied and Environmental Microbiology, 2014). Factors reflecting topo-edaphic conditions and tree health were linked to oomycete community patterns. The majority of detected OTUs belonged to the Peronosporales. Most taxa were relatives of the Pythiaceae, but relatives of the Peronosporaceae and members of the Saprolegniales were also found. The most abundant OTUs were related to Globisporangium irregulare and P. cinnamomi, both displaying strong site-specific patterns. Oomycete communities were strongly correlated with the environmental factors: altitude, crown foliation, slope and soil skeleton and soil nitrogen. Our findings illustrate the significance of small scale variation in habitat conditions for the distribution of oomycetes and highlight the importance to study oomycete communities in relation to such ecological patterns.

Continuous-feed carbonation of waste incinerator bottom ash in a rotating drum reactor.

Carbonation is a key process in the aging of waste incinerator bottom ash (BA). The reaction with CO2 decreases the BA alkalinity and lowers the leachability of amphoteric trace metals. Passive ageing over several months is usually performed in intermittently mixed BA heaps. Here we aimed at accelerating the process in a rotating drum reactor continuously fed with the BA and the reactant gas (10 vol-% CO2, volumetric flow rate 60 L/min). In one test, the gas was heated and humidified. Since carbonation depends on the specific CO2-supply, experiments were conducted at varied BA residence time (60, 80, and 100 min). Residence time was calculated by mass balancing and confirmed by the breakthrough time of two tracers. Leachates and solid phase properties of the treated BA served to evaluate the carbonation performance. The residence time of BA could be adequately controlled by the reactor loading and feed rate. A residence time of 80 min was sufficient to reduce the BA leachability such as to comply with the German regulatory standards for non-hazardous waste, whereas the untreated BA was hazardous waste. Decreased alkalinity was indicated by lower leachate pH and Ca(OH)2 contents of the BA as compared to the input. Leachate concentrations of amphoteric trace metals (Pb, Zn, Cu) decreased by at least one order of magnitude while oxyanions became slightly more mobile upon carbonation. In view of relatively short residence times and stable process performance, the rotating drum reactor seems promising for a full-scale implementation of BA carbonation.

Sequential extraction of chromium, molybdenum, and vanadium in basic oxygen furnace slags.

Basic oxygen furnace slags (BOS) are by-products of basic oxygen steel production. Whereas the solubility of some elements from these slags has been well investigated, information about the mineralogy and related leaching, i.e., availability of the environmentally relevant elements chromium (Cr), molybdenum (Mo), and vanadium (V), is still lacking. The aim of this study was to investigate these issues with a modified, four-fraction-based, sequential extraction procedure (F1-F4), combined with X-ray diffraction, of two BOS. Extractants with increasing strength were used (F1 demineralized water, F2 CH3COOH + HCl, F3 Na2EDTA + NH2OH·HCl, and F4 HF + HNO3 + H2O2), and after each fraction, X-ray diffraction was performed. The recovery of Cr was moderate (66.5%) for one BOS, but significantly better (100.2%) for the other one. High recoveries were achieved for the other elements (Mo, 100.8-107.9% and V, 112.6-87.0%), indicating that the sequential extraction procedure was reliable when adapted to BOS. The results showed that Cr and Mo primarily occurred in F4, representing rather immobile elements under natural conditions, which were strongly bound into/onto Fe minerals (srebrodolskite, magnetite, hematite, or wustite). In contrast, V was more mobile with proportional higher findings in F2 and F3, and the X-ray diffraction results reveal that V was not solely bound into Ca minerals (larnite, hatrurite, kirschsteinite, and calcite), but also bound to Fe minerals. The results indicated that the total amount of recovery was a poor indicator of the availability of elements and did not correspond to the leaching of elements from BOS.

A fast and simple method to monitor carbonation of MSWI bottom ash under static and dynamic conditions.

Accelerated carbonation may be employed to improve the leaching behaviour and the geotechnical properties of MSWI bottom ash (BA). Here we report on a novel method to monitor and evaluate the progress of carbonation in both static and dynamic reactor systems. The method is based on following the pressure drop in the gas phase induced by the CO2-uptake of BA and was benchmarked against carbonate contents as measured by thermogravimetry. Laboratory results demonstrated the serviceability and reproducibility of the method. Complementary logging of relative humidity and temperature showed constant moisture conditions and self-heating induced by the exothermal carbonation reaction, respectively. Under dynamic conditions BA carbonation was higher than in the static reactor. Consistently, the self-heating was more pronounced. After a reaction time of 120 min the pressure records indicated a CO2-uptake of 1.5 g CO2/100 g BA (static tests) and of 2.6 g CO2/100 g BA (dynamic tests). The proposed method is suited to study carbonation processes at minimum analytical expense and integrates over the small-scale heterogeneity of BA.

Traffic-related distribution of antimony in roadside soils.

Vehicular emissions have become one of the main source of pollution of urban soils; this highlights the need for more detailed research on various traffic-related emissions and related distribution patterns. Since the banning of asbestos in the European Union, its substitution with antimony (Sb) in brake linings has led to increased inputs of this toxic metalloid to environmental compartments. The objective of this study was to provide detailed information about the spatial distribution patterns of Sb and to assess its mobility and bioavailability. Roadside soils along an arterial road (approx. 9000 vehicles per day) in Cologne (Germany) were studied along five transects, at four soil depths and at seven sampling points set at varying distances from the road (n = 140). For all samples, comprehensive soil characterization was performed and inverse aqua regia-extractable trace metal content was determined being pseudo-total contents. Furthermore, for one transect, also total Sb and a chemical sequential extraction procedure was applied (n = 28). Pseudo-total Sb for all transects decreased significantly with soil depth and distance from the road, reflecting a distribution pattern similar to that of other trace metals associated with brake lining emissions. Conversely, metals associated with exhaust emissions showed a convex distribution. The geochemical fractionation of Sb revealed the following trends: i) non-specifically sorbed Sb was <5%; ii) specifically sorbed Sb was only detected within 1 m distance from the road and decreased with depth; iii) Sb associated with poorly-crystalline Fe oxides decreased with distance from the road; and iv) content of Sb bounded to well-crystalline Fe oxides, and Sb present in the residual fraction remained relatively constant at each depth. Consequently, roadside soils appear to inhibit brake lining-related Sb contamination, with significant but rather low ecotoxicological potential for input into surface and groundwater.

Environmental status of groundwater affected by chromite ore processing residue (COPR) dumpsites during pre-monsoon and monsoon seasons.

Chromite ore processing residue (COPR) is generated by the roasting of chromite ores for the extraction of chromium. Leaching of carcinogenic hexavalent chromium (Cr(VI)) from COPR dumpsites and contamination of groundwater is a key environmental risk. The objective of the study was to evaluate Cr(VI) contamination in groundwater in the vicinity of three COPR disposal sites in Uttar Pradesh, India, in the pre-monsoon and monsoon seasons. Groundwater samples (n = 57 pre-monsoon, n = 70 monsoon) were taken in 2014 and analyzed for Cr(VI) and relevant hydrochemical parameters. The site-specific ranges of Cr(VI) concentrations in groundwater were <0.005 to 34.8 mg L-1 (Rania), <0.005 to 115 mg L-1 (Chhiwali), and <0.005 to 2.0 mg L-1 (Godhrauli). Maximum levels of Cr(VI) were found close to the COPR dumpsites and significantly exceeded safe drinking water limits (0.05 mg L-1). No significant dependence of Cr(VI) concentration on monsoons was observed.

Chromium Release from a COPR-Contaminated Soil at Varying Water Content and Redox Conditions.

Many soils in the region of Kanpur, North India, are heavily affected by the leather industry and its upstream supplier sector, as indicated by elevated chromium (Cr) contents. Under reducing conditions-for instance, at water saturation after monsoon rain or flood irrigation-the dynamic and species distribution of Cr may be affected due to changes in redox potential (E). In this study, the influence of E on the speciation and release of Cr from a contaminated agricultural soil was investigated. A soil sample that was affected by hyperalkaline leachate from chromite ore processing residue, was taken and packed in soil columns, and subjected to a saturation-drainage-saturation cycle. After initial water saturation, the E dropped slowly to minimum values of around ‒100 mV (calculated to pH 7), while E was controlled by CrO/CrO(s), or CrO/(Fe,Cr)OOH redox couples. Soil drainage resulted in a quick return to oxidizing conditions; i.e., E > 300 mV. The Cr species distribution and release showed a clear trend with E. At the beginning of the experiment, under oxidizing and weakly reducing conditions (E range from >100 to 300 mV), Cr(VI) was released in particular. However, under moderately reducing conditions (E range from 100 to -100 mV), Cr was gradually immobilized and irreversible sequestered via reductive precipitation. The results presented in this study provide an improved understanding of the mobility of Cr(VI) in contaminated soils at varying water contents, which is essential for the evaluation of environmental risks in this region.

Isotopic Fingerprints of Iron-Cyanide Complexes in the Environment.

Tracing the origin of iron-cyanide complexes in the environment is important because these compounds are potentially toxic. We determined the stable isotopic compositions of cyanide-carbon (CCN) and cyanide-nitrogen (NCN) in 127 contaminated solids and 11 samples of contaminated groundwater from coal carbonization sites, blast furnace operations, and commercial cyanide applications. Coal-carbonization-related cyanides had unique high mean δ(13)CCN values of -10.5 ± 3.5‰ for the solids and -16.1 ± 1.2‰ for the groundwater samples, while the values for blast furnace sludge (-26.9 ± 1.5‰), commercial cyanides (-26.0 ± 3.0‰), and their corresponding groundwaters were significantly lower. Determination of δ(13)CCN is a promising tool for identifying the source of cyanide contamination. However, for coal carbonization sites, historical research into the manufacturing process is necessary because a nonconventional gas works site exhibited exceptionally low δ(13)CCN values of -22.7 ± 1.7‰. The δ(15)NCN values for samples related to coal carbonization and blast furnaces overlapped within a range of +0.1 to +10.3‰, but very high δ(15)NCN values seemed to be indicative for a cyanide source in the blast furnace. In contrast, commercial cyanides tend to have lower δ(15)NCN values of -5.6 to +1.9‰ in solids and -0.5 to +3.0‰ in the groundwater.

Long-term ferrocyanide application via deicing salts promotes the establishment of Actinomycetales assimilating ferrocyanide-derived carbon in soil.

Cyanides are highly toxic and produced by various microorganisms as defence strategy or to increase their competitiveness. As degradation is the most efficient way of detoxification, some microbes developed the capability to use cyanides as carbon and nitrogen source. However, it is not clear if this potential also helps to lower cyanide concentrations in roadside soils where deicing salt application leads to significant inputs of ferrocyanide. The question remains if biodegradation in soils can occur without previous photolysis. By conducting a microcosm experiment using soils with/without pre-exposition to road salts spiked with (13) C-labelled ferrocyanide, we were able to confirm biodegradation and in parallel to identify bacteria using ferrocyanide as C source via DNA stable isotope probing (DNA-SIP), TRFLP fingerprinting and pyrosequencing. Bacteria assimilating (13) C were highly similar in the pre-exposed soils, belonging mostly to Actinomycetales (Kineosporia, Mycobacterium, Micromonosporaceae). In the soil without pre-exposition, bacteria belonging to Acidobacteria (Gp3, Gp4, Gp6), Gemmatimonadetes (Gemmatimonas) and Gammaproteobacteria (Thermomonas, Xanthomonadaceae) used ferrocyanide as C source but not the present Actinomycetales. This indicated that (i) various bacteria are able to assimilate ferrocyanide-derived C and (ii) long-term exposition to ferrocyanide applied with deicing salts leads to Actinomycetales outcompeting other microorganisms for the use of ferrocyanide as C source.

Chemical and mineralogical characterization of chromite ore processing residue from two recent Indian disposal sites.

Chromite ore processing residue (COPR) is a hazardous waste. Nevertheless, deposition of COPR in uncontrolled surface landfills is still common practice in some countries. Whereas old (between at least 40 and 180 years) COPR from the temperate zone has been intensively investigated, information on COPR in other regions is restricted. Relatively young (<25 years) COPR samples obtained from two abandoned landfill sites in India were investigated by a modified total microwave digestion method, X-ray powder diffraction (XRPD), and scanning electron microscopy (SEM) in order to determine their chemical and mineralogical nature. By the use of microwave digestion with acid mixtures of HNO3, H3PO4, and HBF4 (5:3:2 vol), COPR was completely dissolved and element contents similar to those obtained by X-ray fluorescence were found. Total Cr contents of the two COPR accounted for 81 and 74 g kg(-1), of which 20 and 13% were present in the carcinogenic hexavalent form (CrVI). Apart from the common major mineral phases present in COPR reported earlier, a further Cr host mineral, grimaldiite [CrO(OH)], could be identified by XRPD and SEM. Additionally, well soluble Na2CrO4 was present. Improving the effectiveness of chromite ore processing and preventing the migration of Cr(VI) into water bodies are the main challenges when dealing with these COPR.

Volatilization of elemental mercury from fresh blast furnace sludge mixed with basic oxygen furnace sludge under different temperatures.

Blast furnace sludge (BFS) is a waste with elevated mercury (Hg) content due to enrichment during the production process of pig iron. To investigate the volatilization potential of Hg, fresh samples of BFS mixed with basic oxygen furnace sludge (BOFS; a residue of gas purification from steel making, processed simultaneously in the cleaning devices of BFS and hence mixed with BFS) were studied in sealed column experiments at different temperatures (15, 25, and 35 °C) for four weeks (total Hg: 0.178 mg kg(-1)). The systems were regularly flushed with ambient air (every 24 h for the first 100 h, followed by every 72 h) for 20 min at a flow rate of 0.25 ± 0.03 L min(-1) and elemental Hg vapor was trapped on gold coated sand. Volatilization was 0.276 ± 0.065 ng (x m: 0.284 ng) at 15 °C, 5.55 ± 2.83 ng (x m: 5.09 ng) at 25 °C, and 2.37 ± 0.514 ng (x m: 2.34 ng) at 35 °C. Surprisingly, Hg fluxes were lower at 35 than 25 °C. For all temperature variants, an elevated Hg flux was observed within the first 100 h followed by a decrease of volatilization thereafter. However, the background level of ambient air was not achieved at the end of the experiments indicating that BFS mixed with BOFS still possessed Hg volatilization potential.

Sequential extraction of inorganic mercury in dumped blast furnace sludge.

Blast furnace sludge (BFS) is an industrial waste with elevated mercury (Hg) contents due to the enrichment during the production process of pig iron. To investigate the potential pollution status of dumped BFS, 14 samples with total Hg contents ranging from 3.91 to 20.8 mg kg(-1) from five different locations in Europe were sequentially extracted. Extracts used included demineralized water (fraction 1, F1), 0.1 mol L(-1) CH3COOH + 0.01 mol L(-1) HCl (F2), 1 mol L(-1) KOH (F3), 7.9 mol L(-1) HNO3 (F4), and aqua regia (F5). The total recovery ranged from 72.3 to 114 %, indicating that the procedure was reliable when adapted to this industrial waste. Mercury mainly resided in the fraction of "elemental" Hg (48.5-98.8 %) rather being present as slightly soluble Hg species associated with sludge particles. Minor amounts were found as mercuric sulfide (F5; 0.725-37.3 %) and Hg in crystalline metal ores and silicates (F6; 2.21-15.1 %). The ecotoxically relevant fractions (F1 and F2) were not of significance (F1,

Manganese-oxide-coated redox bars as an indicator of reducing conditions in soils.

Identification of reducing conditions in soils is of concern not only for pedogenesis but also for nutrient and pollutant dynamics. We manufactured manganese (Mn)-oxide-coated polyvinyl chloride bars and proved their suitability for the identification of reducing soil conditions. Birnessite was synthesized and coated onto white polyvinyl chloride bars. The dark brown coatings were homogenous and durable. As revealed by microcosm devices with adjusted redox potentials (E), under oxidizing conditions (E ∼450 mV at pH 7) there was no Mn-oxide removal. Reductive dissolution of Mn-oxides, which is expressed by the removal of the coatings, started under weakly reducing conditions (E ∼175 mV) and was more intensive under moderately reducing conditions (∼80 mV). According to thermodynamics, the removal of Mn-oxide coatings (225 mm d) exceeded the removal of iron (Fe)-oxide coatings (118 mm d) in soil column experiments. This was confirmed in a soil with a shallow and strongly fluctuating water table where both types of redox bars were inserted. Consequently, it was possible to identify reducing conditions in soils using Mn-oxide-coated bars. We recommend this methodology for short-term monitoring because tri- and tetravalent Mn is the preferred electron acceptor compared with trivalent Fe, and this additionally offers the possibility of distinguishing between weakly and moderately reducing conditions. If dissolved Fe is abundant in soils, the possibility of nonenzymatic reduction of Mn has to be taken into account.