Clogging of an Alpine streambed by silt-sized particles - Insights from laboratory and field experiments.

Clogging of streambeds by suspended particles (SP) can cause environmental problems, as it can negatively influence, e.g., habitats for macrozoobenthos, fish reproduction and groundwater recharge. This especially applies in the case of silt-sized SP. Until now, most research has dealt with coarse SP and was carried out in laboratory systems. The aims of this study are to examine (1) whether physical clogging by silt-sized SP exhibits the same dynamics and patterns as by sand-sized SP, and (2) the comparability of results between laboratory and field experiments. We carried out vertical column experiments with sand-sized bed material and silt-sized SP, which are rich in mica minerals. In laboratory experiments, we investigated the degree of clogging quantified by the reduction of porosity and hydraulic conductivity and the maximum clogging depth as a function of size and shape of bed material, size of SP, pore water flow velocity, and concentration of calcium cations. The SP were collected from an Alpine sedimentation basin, where our field experiments were carried out. To investigate the clogging process in the field, we buried columns filled with sand-sized quartz in the stream bed. We found that the maximal bed-to-grain ratio where clogging still occurs is larger for silt-sized SP than for sand-sized SP. The observed clogging depths and the reduction of flow rate through the column from our laboratory experiments were comparable to those from the field. However, our field results showed that the extent of clogging strongly depends on the naturally-occurring hydrological dynamics. The field location was characterized by a more polydisperse suspension, a strongly fluctuating water regime, and high SP concentrations at times, leading to more heterogeneous and more pronounced clogging when compared to laboratory results.

Thermostatted dual-channel portable capillary electrophoresis instrument.

A new portable CE instrument is presented. The instrument features the concurrent separation of anions and cations in parallel channels. Each channel has a separate buffer container to allow independent optimization of separation conditions. The microfluidics circuit is based on off-the-shelf parts, and can be easily replicated; only four valves are present in the design. The system employs a miniature automated syringe pump, which can apply both positive and negative pressures (-100 to 800 kPa). The application of negative pressure allows a semi-automatic mode of operation for introducing volume-limited samples. The separations are performed in a thermostatted compartment for improved reproducibility in field conditions. The instrument has a compact design, with all components, save for batteries and power supplies, arranged in a briefcase with dimensions of 52 × 34 × 18 cm and a weight of less than 15 kg. The system runs automatically and is controlled by a purpose-made graphical user interface on a connected computer. For demonstration, the system was successfully employed for the concurrent separation and analysis of inorganic cations and anions in sediment porewater samples from Lake Baldegg in Switzerland and of metal ions in a sample from the tailing pond of an abandoned mine in Argentina.

Arsenate uptake by Al nanoclusters and other Al-based sorbents during water treatment.

In many parts of the world, arsenic from geogenic and anthropogenic sources deteriorates the quality of drinking water resources. Effective methods of arsenic removal include adsorption and coagulation with iron- and aluminum-based materials, of which polyaluminum chloride is widely employed as coagulant in water treatment due to its low cost and high efficiency. We compared the arsenic uptake capacity and the arsenic bonding sites of different Al-based sorbents, including Al nanoclusters, polyaluminum chloride, polyaluminum granulate, and gibbsite. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed that As(V) forms bidentate-binuclear complexes in interaction with all Al-based removal agents. The octahedral configuration of nanoclusters and the distribution of sorption sites remain the same in all types of removal agents consisting of nano-scale Al oxyhydroxide particles. The obtained distances for As(V)-O and As(V)-Al agreed with previously published data and were found to be 1.69 ± 0.02 Å and 3.17-3.21 Å, respectively. Our study suggests that As(V) binds to Al nanoclusters as strongly as to Al oxide surfaces. The As sorption capacity of Al nanoclusters was found to be very similar to that of Al clusters in a polyaluminum chloride. The most efficient Al-based sorbents for arsenic removal were Al nanoclusters, followed by polyaluminum granulate.

Indium and indium tin oxide induce endoplasmic reticulum stress and oxidative stress in zebrafish (Danio rerio).

Indium and indium tin oxide (ITO) are extensively used in electronic technologies. They may be introduced into the environment during production, use, and leaching from electronic devices at the end of their life. At present, surprisingly little is known about potential ecotoxicological implications of indium contamination. Here, molecular effects of indium nitrate (In(NO3)3) and ITO nanoparticles were investigated in vitro in zebrafish liver cells (ZFL) cells and in zebrafish embryos and novel insights into their molecular effects are provided. In(NO3)3 led to induction of endoplasmic reticulum (ER) stress response, induction of reactive oxygen species (ROS) and induction of transcripts of pro-apoptotic genes and TNF-α in vitro at a concentration of 247 µg/L. In(NO3)3 induced the ER stress key gene BiP at mRNA and protein level, as well as atf6, which ultimately led to induction of the important pro-apoptotic marker gene chop. The activity of In(NO3)3 on ER stress induction was much stronger than that of ITO, which is explained by differences in soluble free indium ion concentrations. The effect was also stronger in ZFL cells than in zebrafish embryos. Our study provides first evidence of ER stress and oxidative stress induction by In(NO3)3 and ITO indicating a critical toxicological profile that needs further investigation.

Early diagenetic processes generate iron and manganese oxide layers in the sediments of Lake Baikal, Siberia.

Distinct layers of iron(III) and manganese(IV) (Fe/Mn) oxides are found buried within the reducing part of the sediments in Lake Baikal and cause considerable complexity and steep vertical gradients with respect to the redox sequence. For the on-site investigation of the responsible biogeochemical processes, we applied filter tube samplers for the extraction of sediment porewater combined with a portable capillary electrophoresis instrument for the analyses of inorganic cations and anions. On the basis of the new results, the sequence of diagenetic processes leading to the formation, transformation, and dissolution of the Fe/Mn layers was investigated. With two exemplary cores we demonstrate that the dissolution of particulate Fe and Mn is coupled to the anaerobic oxidation of CH4 (AOM) either via the reduction of sulphate (SO4(2-)) and the subsequent generation of Fe(II) by S(-II) oxidation, or directly coupled to Fe reduction. Dissolved Fe(II) diffuses upwards to reduce particulate Mn(IV) thus forming a sharp mineral boundary. An alternative dissolution pathway is indicated by the occurrence of anaerobic nitrification of NH4(+) observed at locations with Mn(IV). Furthermore, the reasons and consequences of the non-steady-state sediment pattern and the resulting redox discontinuities are discussed and a suggestion for the burial of active Fe/Mn layers is presented.

Sediment porewater extraction and analysis combining filter tube samplers and capillary electrophoresis.

Careful extraction and analysis of porewater from sediment cores are critical for the investigation of small-scale biogeochemical processes. Firstly, small sample volumes and high spatial resolution are required. Secondly, several chemical species in the anaerobic porewater are sensitive to oxidation when brought in contact with ambient air. Here we present the combination of a special sampling technique and an analytical method for the porewater extraction of a varved sediment core from Lake Baldegg in central Switzerland, using MicroRhizon samplers and a portable capillary electrophoresis (CE) instrument. MicroRhizon filter tubes of 1 mm diameter and 20 mm length are suitable for fast retrieval of particle-free porewater samples directly from the sediment core. Since the time-span between sampling and analysis is less than 20 seconds, oxygen-sensitive Fe(ii) can be analyzed in one go together with Na(+), K(+), Ca(2+), Mg(2+), NH4(+), and Mn(ii) without splitting, acidification or dilution of the sample. The major inorganic cations and anions of the sediment porewater can be determined in less than 15 minutes. Detection limits are in the sub-micromolar concentration range. The capillary electrophoresis instrument used in this study requires sample volumes of only 20 µL. These remarkable small sample volumes allow the minimization of disturbance of the sediment cores and a high spatial resolution of the sediment profile, even in sediments with low water content. The equipment is inexpensive, easy to handle, fully portable and therefore suitable for environmental on-site applications.

Adsorption of arsenic on polyaluminum granulate.

The kinetics and efficiencies of arsenite and arsenate removal from water were evaluated using polyaluminum granulates (PAG) with high content of aluminum nanoclusters. PAG was characterized to be meso- and macroporous, with a specific surface area of 35 ± 1 m(2) g(-1). Adsorption experiments were conducted at pH 7.5 in deionized water and synthetic water with composition of As-contaminated groundwater in the Pannonian Basin. As(III) and As(V) sorption was best described by the Freundlich and Langmuir isotherm, respectively, with a maximum As(V) uptake capacity of ~200 µmol g(-1) in synthetic water. While As(III) removal reached equilibrium within 40 h, As(V) was removed almost entirely within 20 h. Micro X-ray fluorescence and electron microscopy revealed that As(III) was distributed uniformly within the grain, whereas As(V) diffused up to 81 µm into PAG. The results imply that As(V) is adsorbed 3 times faster while being transported 10(5) times slower than As(III) in Al hydroxide materials.

Pattern of elemental release during the granite dissolution can be changed by aerobic heterotrophic bacterial strains isolated from Damma Glacier (central Alps) deglaciated granite sand.

Colonisation and weathering of freshly deglaciated granite are key processes in initial soil formation and development. We have obtained 438 isolates from granite sand covering glacial toe, 284 isolates at 22°C and 154 at 4°C incubation temperatures, respectively, to obtain cultures for the investigation of their weathering capabilities under laboratory conditions. The isolation of bacteria from granite sand was performed on rich-, intermediate- and low-nutrient-content solid media. Isolates were identified by 16S rRNA gene sequencing. According to the genera-associated weathering capabilities described in the literature and according to their abundance in our culture collection, we selected eight strains to analyse their effects on the weathering dynamics of granite sand during the batch culture experiment. Analysis of culturable bacteria showed higher species richness among isolates from 22°C than from 4°C incubations. In the R2A and 1/100 Ravan media, we observed the highest species richness of isolates obtained at 22°C and 4°C incubation temperatures, respectively. The obtained 16S rRNA sequences revealed the presence of alpha-, beta- and gamma-proteobacteria, Firmicutes, Actinobacteria and Bacteroidetes. The most numerous group of isolates was distantly related to Collimonas representatives, and according to the sequences of the 16S rRNA genes, they can form a new genus. Isolates from this group had the capability of causing increased dissolution rates for Fe, W, Ni and Rb. In general, at each sampling during the 30-day experiment, every strain showed a unique weathering profile resulting from differential rates of the dissolution and the precipitation of different minerals in the batch culture. Consequently, the presence of different strains, their growth stage and changes in proportions of strains in the bacterial community can affect further soil development and the successive colonisation by plants.

Polyaluminum chloride with high Al30 content as removal agent for arsenic-contaminated well water.

Polyaluminum chloride (PACl) is a well-established coagulant in water treatment with high removal efficiency for arsenic. A high content of Al(30) nanoclusters in PACl improves the removal efficiency over broader dosage and pH range. In this study we tested PACl with 75% Al(30) nanoclusters (PACl(Al30)) for the treatment of arsenic-contaminated well water by laboratory batch experiments and field application in the geothermal area of Chalkidiki, Greece, and in the Pannonian Basin, Romania. The treatment efficiency was studied as a function of dosage and the nanoclusters' protonation degree. Acid-base titration revealed increasing deprotonation of PACl(Al30) from pH 4.7 to the point of zero charge at pH 6.7. The most efficient removal of As(III) and As(V) coincided with optimal aggregation of the Al nanoclusters at pH 7-8, a common pH range for groundwater. The application of PACl(Al30) with an Al(tot) concentration of 1-5mM in laboratory batch experiments successfully lowered dissolved As(V) concentrations from 20 to 230 µg/L to less than 5 µg/L. Field tests confirmed laboratory results, and showed that the WHO threshold value of 10 µg/L was only slightly exceeded (10.8 µg/L) at initial concentrations as high as 2300 µg/L As(V). However, As(III) removal was less efficient (<40%), therefore oxidation will be crucial before coagulation with PACl(Al30). The presence of silica in the well water improved As(III) removal by typically 10%. This study revealed that the Al(30) nanoclusters are most efficient for the removal of As(V) from water resources at near-neutral pH.

Weathering-associated bacteria from the Damma glacier forefield: physiological capabilities and impact on granite dissolution.

Several bacterial strains isolated from granitic rock material in front of the Damma glacier (Central Swiss Alps) were shown (i) to grow in the presence of granite powder and a glucose-NH(4)Cl minimal medium without additional macro- or micronutrients and (ii) to produce weathering-associated agents. In particular, four bacterial isolates (one isolate each of Arthrobacter sp., Janthinobacterium sp., Leifsonia sp., and Polaromonas sp.) were weathering associated. In comparison to what was observed in abiotic experiments, the presence of these strains caused a significant increase of granite dissolution (as measured by the release of Fe, Ca, K, Mg, and Mn). These most promising weathering-associated bacterial species exhibited four main features rendering them more efficient in mineral dissolution than the other investigated isolates: (i) a major part of their bacterial cells was attached to the granite surfaces and not suspended in solution, (ii) they secreted the largest amounts of oxalic acid, (iii) they lowered the pH of the solution, and (iv) they formed significant amounts of HCN. As far as we know, this is the first report showing that the combined action of oxalic acid and HCN appears to be associated with enhanced elemental release from granite, in particular of Fe. This suggests that extensive microbial colonization of the granite surfaces could play a crucial role in the initial soil formation in previously glaciated mountain areas.

A universal method to assess the potential of phosphorus loss from soil to aquatic ecosystems.

BACKGROUND, AIM, AND SCOPE: Phosphorus loss from terrestrial to the aquatic ecosystems contributes to eutrophication of surface waters. To maintain the world's vital freshwater ecosystems, the reduction of eutrophication is crucial. This needs the prevention of overfertilization of agricultural soils with phosphorus. However, the methods of risk assessment for the P loss potential from soils lack uniformity and are difficult for routine analysis. Therefore, the efficient detection of areas with a high risk of P loss requires a simple and universal soil test method that is cost effective and applicable in both industrialized and developing countries. MATERIALS AND METHODS: Soils from areas which varied highly in land use and soil type were investigated regarding the degree of P saturation (DPS) as well as the equilibrium P concentration (EPC(0)) and water-soluble P (WSP) as indicators for the potential of P loss. The parameters DPS and EPC(0) were determined from P sorption isotherms. RESULTS: Our investigation of more than 400 soil samples revealed coherent relationships between DPS and EPC(0) as well as WSP. The complex parameter DPS, characterizing the actual P status of soil, is accessible from a simple standard measurement of WSP based on the equation [Formula: see text]. DISCUSSION: The parameter WSP in this equation is a function of remaining phosphorous sorption capacity/total accumulated phosphorous (SP/TP). This quotient is independent of soil type due to the mutual compensation of the factors SP and TP. Thus, the relationship between DPS and WSP is also independent of soil type. CONCLUSIONS: The degree of P saturation, which reflects the actual state of P fertilization of soil, can be calculated from the easily accessible parameter WSP. Due to the independence from soil type and land use, the relation is valid for all soils. Values of WSP, which exceed 5 mg P/kg soil, signalize a P saturation between 70% and 80% and thus a high risk of P loss from soil. RECOMMENDATIONS AND PERSPECTIVES: These results reveal a new approach of risk assessment for P loss from soils to surface and ground waters. The consequent application of this method may globally help to save the vital resources of our terrestrial and aquatic ecosystems.

Effect of iron and phosphate on bacterial cyanide formation determined by methemoglobin in two-dimensional gradient microcultivations.

Cyanide formation by microorganisms is typically observed during early stationary growth phase and is facilitated by the presence of iron(III) and inorganic phosphate. Extracellular free cyanide in aqueous solutions might readily react with methemoglobin added and can be determined by UV/VIS spectroscopy. As alternative to existing methods, this provided the basis for an analytical method which has not been used previously for the determination of cyanide in bacterial cultivations. We successfully applied the technique to study the combined effect of both iron(III) and phosphate on the cyanide formation by Pseudomonas fluorescens, which we used as model organism known for its ability to form HCN. Information on the combined effect of iron and phosphate was obtained by using commercially available 24-well microtiter plates as two-dimensional gradient systems. After its reaction with methemoglobin, cyanide was measured reproducibly at the wavelength of 427 nm. We found a combined effect of both iron and phosphate. In the absence of inorganic phosphate, cyanide formation was stimulated considerably by increasing concentrations of iron(III), although the effect on the bacterial growth of P. fluorescens was almost insignificant. This suggests that iron is more important than inorganic phosphate for the cyanogenesis by P. fluorescens.

Plant uptake of trace elements on a Swiss military shooting range: uptake pathways and land management implications.

Over 400tons of Pb enters Swiss soils annually at some 2000 military shooting ranges (MSRs). We measured elements in the leaves of 10 plant species and associated rhizospheric soil on the stop butt of a disused MSR. The geometric mean concentrations of Pb, Sb, Cu, Ni in rhizospheric soils were 10,171mg/kg, 5067mg/kg, 4125mg/kg and 917mg/kg. Some species contained Pb, Cu and Ni, above concentrations (30mg/kg, 25mg/kg and 50mg/kg) shown to be toxic to livestock. Most contaminants in leaves resulted from surface deposition. However, at soil Pb concentrations >60,000mg/kg, Equisetum arvense and Tussilago farfara took up >1000mg/kg Pb into the leaves. These plants are not hyperaccumulators, having <100mg/kg Pb in leaves at lower soil concentrations. Removal of soil with more than 30,000 Pb, from which one could smelt this metal to offset remediation costs, followed by revegetation, would minimise dust and hence leaf-borne contaminants.

Removal of heavy metals from mine waters by natural zeolites.

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.

Adsorption of Pb and Cd by amine-modified zeolite.

Natural zeolites, known for their excellent sorption properties towards metal cations, are widely used for the purification of wastewaters. The selectivity of clinoptilolite, a common zeolite mineral, for Pb is known to be particularly high, whereas its selectivity for Cd is often lower. Extraordinarily high sorption capacities for soft metal cations were observed in the case of thiol-functionalized silica gels and clays. In order to enhance the zeolites' sorption capacity for Cd, we treated natural heteroionic and Na-clinoptilolite in aqueous suspensions with cysteamine and propylamine solutions and investigated the sorption of Cd and Pb to amine-modified zeolite by a series of batch experiments. Stability constants for amine sorption on all zeolite samples at room temperature and 50 degrees C were obtained. Partial dimerization of cysteamine explains the enhanced sorption of this compound. In contrast, amine treatment did not enhance the adsorption capacity or selectivity of the clinoptilolite towards Cd and Pb. Instead, the amounts of adsorbed heavy metals decreased stoichometrically with increasing sorption of cysteamine and propylamine. This reduction can be explained by the blockage of channels by amine molecules and revealed that the modification of zeolites with mercaptoamines does not enhance the sorption capacity of zeolite for Cd and Pb.

Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material.

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column. The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))). In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction. The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).

The origin of aluminum flocs in polluted streams.

About 240,000 square kilometers of Earth's surface is disrupted by mining, which creates watersheds that are polluted by acidity, aluminum, and heavy metals. Mixing of acidic effluent from old mines and acidic soils into waters with a higher pH causes precipitation of amorphous aluminum oxyhydroxide flocs that move in streams as suspended solids and transport adsorbed contaminants. On the basis of samples from nine streams, we show that these flocs probably form from aggregation of the epsilon -Keggin polyoxocation AlO4Al12(OH)24(H2O)12(7+)(aq) (Al13), because all of the flocs contain distinct Al(O)4 centers similar to that of the Al13 nanocluster.

Influence of biodegradation processes on the duration of CaCO3 as a pH buffer in municipal solid waste incinerator bottom ash.

The long-term leachability of heavy metals from municipal solid waste incinerator (MSWI) bottom ash is of concern because of its potential use as a secondary construction material. Calcite is the most important long-term buffer in MSWI bottom ash as it buffers solutions during percolation and is an important factor in the control of heavy-metal mobility. It has been argued that biodegradation of residual organic material in the MSWI is a significant source of acidity. Model calculations have therefore been carried out to determine the influence of biodegradation on the longevity of the calcite buffer. Using the program STEADYQL, which couples thermodynamic equilibrium with kinetically controlled reactions, solution composition was estimated at steady state. The concentration of Ca dissolved from calcite was estimated in the presence and absence of gypsum as a function of the reaction rate of a number of slow reactions: aerobic, ferrogenic, sulfogenic, and methanogenic biodegradation; diffusion of O2 into the system; degassing of CO2 out of the system; and dissolution of Ca silicate. It was found that, independent of the rate, the biodegradation of organic matter had little influence on the longevity of the calcite buffer (between 2,000 and 3,000 yr for a deposit of 1 m in depth), that anaerobic biodegradation may have a slight retarding effect, and that calcite dissolution due to acid input via precipitation was negligible (around 3% of the total at reference conditions for rainwater with a pH value of 4.3).

On the acid-base chemistry of the Keggin polymers: GaAl12 and GeAl12.

The acid-base properties of GaAl12 and GeAl12 molecules have been investigated and compared to those of the Al13 molecule using alkalimetric titration at two concentrations of the Keggin complex. As in the case of Al13, the positive charge of both GaAl13 and GeAl12 is entirely lost within half a pH unit if the concentration of the Keggin molecules is low (1.25 microM). We find that GeAl12 is significantly more acidic than either the GaAl12 or the Al13 molecules. As positive charge is removed from the Keggin complexes by deprotonation, they tend to aggregate, resulting in titration curves that flatten out at higher Z values. Molecule-molecule interactions appear to be more distinct at elevated concentrations of the Keggin complexes (12.5 microM).