Impact of arsenic on uptake and bio-accumulation of antimony by arsenic hyperaccumulator Pteris vittata.

Individual uptake of As and Sb species in Pteris vittata have been investigated, but little information is available how uptake is affected if both metalloids are simultaneously present in different amounts. We investigated the uptake of antimony and its speciation in Pteris vittata cultivated in quartz substrate with, versus without, co-contamination with arsenic and a contaminated soil for 7 weeks. Applying HPLC-ICP-MS technique Sb(V), Sb(III), As(III), and As(V) could be identified as main species in aqueous extracts of roots and fronds with up to 230 mg kg(-1) of total Sb in the roots. Adding increasing amounts of As to the quartz substrate resulted in increasing uptake of Sb. In contrast to As, which is readily transferred to the fronds, Sb is primarily accumulated in the roots with Sb(V) being the dominant species (>90% of Sb). The addition of As doesn't result in enhanced translocation of Sb into the fronds.

Fractionation of Sb and As in soil and sludge samples using different continuous-flow extraction techniques.

The fractionation of Sb and As in soil and sludge samples had been comparably studied using two continuous-flow systems: a microcolumn (MC) and a rotating coiled column (RCC). The leachants were applied in correspondence with a five-step sequential extraction scheme addressing water-soluble, non-specifically sorbed, specifically sorbed, and bound to amorphous and crystalline Fe/Al oxide fractions of Sb and As. Inductively coupled plasma atomic emission spectroscopy was applied to determine antimony, arsenic, and major elements in the effluent and in the residual fractions after their digestion. Resemblances and discrepancies of the two methods were evaluated by the fractionation of Sb and As in forest soil, river sludge, and dumped waste (soil) samples. For the forest soil sample, which is very poor in organic matter, RCC and MC extractions yielded similar quantitative values of As and Sb contents in individual leachable fractions. However, for the river sludge sample with a moderate concentration of C (org) (3.3 %), the results obtained by both continuous-flow methods are in satisfactory agreement. RCC extraction enabled water-soluble and non-specifically sorbed As fractions to be recovered, whereas after MC leaching, these environmentally relevant forms of As were not detected. For the soil rich in organic matter (C(org) = 11.5 %), the discrepancy between the data of RCC and MC fractionations is significant. RCC extraction provides about six times higher recoveries of As and Sb bound to amorphous Fe/Al oxides. More efficient leaching of As and Sb in RCC may be attributed to the migration of organic-rich particles with low density inside the column that might enhance the mixing of the solid and liquid phases.

Sorption of aqueous antimony and arsenic species onto akaganeite.

Two akaganeite materials were tested for the removal of antimonate, trimethyl antimonate, arsenate, arsenite, and dimethyl arsenate from water: a commercial product (GEH) and a synthesized akaganeite. The two materials show similar q(max) values, but differ in their K(L) values. This could be a result of their different crystal sizes indicated by sharper XRD reflections of the synthesized akaganeite compared with GEH. Batch experiments were carried out using all species to investigate the influence of the pH on their sorption onto the commercial material. The best results for the removal of antimonate and arsenate were achieved under acidic conditions, while the sorption of arsenite has an optimum at pH 7. The maximum loadings vary from 450 mg g(-1) (antimonate at pH 2.2.) to 2 mg g(-1) (trimethyl antimonate at pH 7). Competition reactions (up to a 10-fold excess of the competitor ion) were studied with antimonate, arsenate, and phosphate. The sorption capacity of arsenate decreases up to 12.5% by adding phosphate (ratio 1:10), but the addition of antimonate did not influence the sorption of arsenate. Conversely, the sorption of antimonate decreases due to the addition of 10-fold concentration of arsenate (31%) or phosphate (27%).

In situ and ex situ study of the enhanced modification with iron of clinoptilolite-rich zeolitic tuff for arsenic sorption from aqueous solutions.

Adsorption methods have been developed for the removal of arsenic from solution motivated by the adverse health effects of this naturally occurring element. Iron exchanged natural zeolites are promising materials for this application. In this study we introduced iron species into a clinoptilolite-rich zeolitic tuff by the liquid exchange method using different organic and inorganic iron salts after pretreatment with NaCl and quantified the iron content in all trials by XRF spectroscopy. The materials were characterized by XRD, FTIR, FTIR-DR, UV-vis, cyclic voltammetry, ESR and Mössbauer spectroscopies before and after adsorption of arsenite and arsenate. The reached iron load in the sample T+Fe was %Fe(2)O(3)-2.462, n(Fe)/n(Al)=0.19, n(Si)/n(Fe)=30.9 using FeCl(3), whereby the iron leachability was 0.1-0.2%. The introduced iron corresponded to four coordinated species with tetrahedral geometry, primarily low spin ferric iron adsorbing almost 12 mug g(-1) arsenite (99% removal) from a 360 mug(As(III)) L(-1) and 6 mug g(-1) arsenate from a 230 mug(As(V)) L(-1). Adsorption of arsenite and arsenate reached practically a plateau at n(Fe)/n(Si)=0.1 in the series of exchanged tuffs. The oxidation of arsenite to arsenate in the solution in contact with iron modified tuff during adsorption was observed by speciation. The reduction of ferric iron to ferrous iron could be detected in the electrochemical system comprising an iron-clinoptilolite impregnated electrode and was not observed in the dried tuff after adsorption.

Analytical investigations of phenyl arsenicals in groundwater.

Phenylic arsenic compounds are the main contaminants in groundwater at abandoned sites with a history of arsenic containing chemical warfare agents (CWA). A fast and sensitive HPLC-ICP-MS method was developed to determine inorganic arsenic compounds like arsenite and arsenate as well as the degradation products of the arsenic containing warfare agents (phenylarsonic acid, phenylarsine oxide, diphenylarsinic acid). Beside these arsenic species the groundwater samples contained also high iron contents (up to 23 mg/l as Fe(II)) which led to precipitates in the samples after coming into contact with the atmosphere. Preservation immediately after sampling by phosphoric acid has shown that a successful avoidance of any losses of any arsenic species between sampling and analysis was possible. The suggested analytical method was applied to groundwater samples taken from different depths at a polluted site. The main contaminant in the water samples was diphenylarsinic acid (up to 2.1 mg/l) identified by ESI-MS, but also elevated concentrations of inorganic arsenic (up to 240 microg/l) were found.

Aquatic hyphomycete communities as potential bioindicators for assessing anthropogenic stress.

With a profound knowledge of how physico-chemical parameters affect these communities, microbial communities could be used as indicators for environmental changes and for risk assessment studies. We studied aquatic hyphomycete communities in rivers and aquifers from sites shaped by intense mining activities (namely the "Mansfeld region") and chemical industry (cities of Halle and Bitterfeld) in Central Germany. Environmental stress factors such as high concentrations of heavy metals, sulphate, and nitrate as well as low concentrations of oxygen significantly reduced the diversity and biomass of hyphomycetes in the investigated samples. Redundancy analysis (RDA) indicates that variations in water chemistry cause a significant proportion of the change in fungal community structure (86.2%). Fungi were negatively correlated with high metal and nutrient concentrations. RDA also showed a strong influence of organic matter on individual species, with Anguillospora longissima (Sacc. et Syd.), Clavatospora longibrachiata (Ingold), Clavariopsis aquatica (De Wild), Flagellospora curvula (Ingold), Heliscus lugdunensis (Sacc. et Thérry), Tumularia aquatica (Ingold) and Lemonniera aquatica (De Wild) being most sensitive. We propose that aquatic hyphomycete communities can be used as sensitive and integrative indicators for freshwater quality.

Chemically modified maize cobs waste with enhanced adsorption properties upon methyl orange and arsenic.

The surface chemistry of maize naturasorbent was altered in this work by the modifying agents: phosphoric acid and different amines (triethanolamine, diethylenetriamine and 1,4-diaminobutane). Removal of methyl orange (25 mg l(-1)) was <50% by maize corn cobs modified by phosphorylation and higher by the quaternized samples: 68% with the 1,4-diaminobutane and 73% with the diethylenetriamine modificators. Adsorption of arsenite by the samples modified with phosphoric acid/ammonia was 11 microg g(-1), which corresponds to 98% removal from a 550 microg As l(-1) solution for an adsorbent dose of 50 mg ml(-1). The samples modified by phosphoric acid/urea removed 0.4 microg g(-1) arsenate from a 300 mug As l(-1) solution. Adsorption of methyl orange, arsenite and arsenate was superior by the chemically modified maize cobs judged against the initial naturasorbent. For comparison, removal by the commercial anion exchanger was 100% for methyl orange, 45% (5 microg g(-1)) for arsenite and 99% (5 microg g(-1)) for arsenate.

Mass fluxes and spatial trends of xenobiotics in the waters of the city of Halle, Germany.

The behaviour and the effects of xenobiotics including pharmaceuticals and fragrances in the environment are widely unknown. In order to improve our knowledge, field investigations and modelling approaches for the entire area of the city of Halle/Saale, Germany, were performed. The distribution of the concentration values and mass fluxes are exemplified using indicators such as Bisphenol A, t-Nonylphenol, Carbamacepine, Galaxolide, Tonalide, Gadolinium and isotopes. Concentrations at a magnitude of ng/L to microg/L were found ubiquitously in the ground and surface waters. Using the concentration values, the impact of the city concerning the indicators was not always evident. Only the assessment of the mass fluxes shows significant urban impacts along the city passage. The calculation of the mass fluxes shows increasing values for all investigated xenobiotics during the city passage; only Bisphenol A stagnates. A balance model of water and indicator mass fluxes was built up for the entire city area.

Preservation of arsenic species in water samples using phosphoric acid--limitations and long-term stability.

The preservation of arsenic species in water samples is an indispensable method to avoid their changes during storage, if it is not possible to analyse them immediately. The aim of this investigation was to demonstrate the limitations of the suggested method by using phosphoric acid as a preservation agent. The samples remain stable for 3 months, even if they show evidence of high concentrations of iron or manganese. Critical is an increasing pH>3. Theoretically, a precipitation of strengite (Fe(3)(PO(4))(2)) could occur, which should be avoided. Phosphoric acid with a final concentration of 10mM is recommended as a preservation agent, combined with keeping the samples cool (6 degrees C) and dark. Filtration of samples before preservation may be carried out with respect to the analytical aim to distinguish between the total and soluble fraction (without colloids). It was shown that filtered and non-filtered samples can be preserved by utilising the above mentioned scheme.

Continuous-flow fractionation of trace metals in environmental solids using rotating coiled columns. Some kinetic aspects and applicability of three-step BCR leaching schemes.

The applicability of the three-step BCR leaching scheme to the continuous-flow fractionation of trace metals (TM) using rotating coiled columns (RCC) has been investigated taking soil and sediment reference samples (SRM-2710, CRM-601, BCR-701) as examples. A particulate sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents, used according to the original and optimised BCR protocols, were continuously pumped through. The whole procedure required 3-4 h instead of at least 50 h needed for the traditional sequential extraction. It has been shown that in comparison with batch sequential extraction procedures (SEP), the recoveries of Cd, Zn, Cu, and Pb at the first stage (most mobile and potentially dangerous acid soluble forms) are somewhat higher, if a dynamic extraction in RCC is used. Nevertheless, the distribution patterns for TM in the first two leachable fractions (acid soluble and reducible forms) are similar in most cases. Since no heating is used in RCC, the recoveries of TM at the third stage (when hydrogen peroxide is applied to oxidize the organic matter) may be incomplete and matrix-dependent. The effect of eluent volume and flow rate on the recovery of TM in different forms has been investigated. It has been shown that the kinetics of heavy metal leaching vary significantly with samples. Hence, investigating the elution profiles can provide additional important information for risk assessment of TM mobilization.

Aquatic hyphomycetes in polluted groundwater habitats of central Germany.

Polluted groundwater wells located in a former copper shale mining district (11 sites; Mansfelder Land, Central Germany) and in meadows of the Mulde and Elbe rivers (2 sites) were assessed for occurrence and species richness of aquatic hyphomycetes. Water temperatures at all sites were relatively low and fluctuated less than in surface waters. Oxygen concentrations were always below saturation, whereas sulfate, nitrate, and phosphate levels reached extremely high values in several of the wells. Relatively high levels of Pb, Mn, and Fe were found in some of the wells, but overall few concentrations of individual metals and metalloids exceeded European guidelines for drinking water. Pollen tube growth inhibition, used to assess cytotoxicity of the water, ranged between 4 and 50%. Between 1 and 10 distinct species of aquatic hyphomycetes colonized sterile Alnus glutinosa leaves exposed at the Mansfelder Land sites; for the meadow sites, 8-20 species were found. Heliscus lugdunensis and Anguillospora sp. were the two most widespread species. Fungal colonization occurred much more slowly than in surface water, as demonstrated by scanning electron microscopy and the release of conidia from recovered leaves. The conidial output from exposed alder leaves ranged from 0.2 to 95 conidia mg (-1) dry mass, corresponding to 10% of the values for contaminated surface waters in the same region. Overall, groundwater appears to be a marginal habitat for aquatic hyphomycetes, but may nevertheless play a vital role as long-term reservoir facilitating rapid recolonization following a collapse in fungal communities in surface waters.

Selective enrichment of sulfides, thiols and methylthiophosphates from water samples on metal-loaded cation-exchange materials for gas chromatographic analysis.

The suitability of using metal-loaded sorbents for solid-phase extraction to enrich organic sulfur compounds from water samples was studied. To test the retention behavior of a number of sulfides, thiols and methylthiophosphates, a cation-exchanger was loaded with various metal ions. The elution behavior of sulfur compounds was investigated with different solvents. A combination of Pb2+-modified cation-exchanger as sorbent and CS2 (1%, v/v) in toluene proved to be the most suitable approach for the given problem. Using GC with a pulsed flame photometric detector yielded detection limits of between 0.6 and 2.9 microg/l. The results showed good reproducibility with relative standard deviations of 2-11%.

Accelerated fractionation of heavy metals in contaminated soils and sediments using rotating coiled columns.

A new approach to performing an accelerated sequential extraction of trace elements from solid samples has been proposed. It has been shown that rotating coiled columns (RCC) earlier used in counter-current chromatography can be successfully applied to the dynamic leaching of heavy metals from soils and sediments. A solid sample was retained in the rotating column as the stationary phase under the action of centrifugal forces while different eluents (aqueous solutions of complexing reagents, mineral salts and acids) were continuously pumped through. The procedure developed is time saving and requires only 4-5 h instead of the several days needed for traditional sequential extraction (TSE), complete automation being possible. Losses of solid sample are minimal. In most cases the recoveries of readily bioavailable and leachable forms of Pb, Zn, and Cd are higher, if a dynamic extraction in RCC is used. Since naturally occurring processes are always dynamic, continuous extraction in RCC may help to estimate the contents of leachable forms and their potential risk for the environment more correctly than batch TSE. The Kersten-Foerstner and McLaren-Crawford leaching schemes have been compared, the former has been found to be preferable.

Species-specific isotope-ratio measurements of volatile tin and antimony compounds using capillary GC-ICP-time-of-flight MS.

The analytical performance of an axial inductively-coupled-plasma time-of-flight mass spectrometer (ICP-TOFMS) as a detector for fast transient chromatographic signals resulting from the coupling to capillary gas chromatography (CGC) was investigated. A cryotrapping GC-ICP-TOFMS method for the determination of volatile metal(loid) compounds (VOMs) in gases was used and the suitability of the TOF mass analyzer for multielemental speciation analysis and multi-isotope ratio determinations was studied in terms of accuracy and precision. Isotope ratios 118Sn/120Sn and 121Sb/123Sb have been determined in in-house gas standard atmospheres in Tedlar bags at two different levels (100 pg and 1 ng) for different elemental species (SnH4, MeSnH3, Me2SnH2, Me3SnH, BuSnH3, SbH3, and MeSbH2). A limitation arising from counting statistics in both detection modes could be shown. A solution containing rhodium (10 ng mL(-1)) and cadmium (40 ng mL(-1)) was introduced simultaneously to the GC outlet. Rhodium acts as a continuous internal standard and Cd is used for mass-bias correction (by measuring the 111Cd/113Cd ratio). The detection system in both pulse counting and analog mode was examined. The best attainable precision was established for Me2SnH2 (analog mode, 12 replicates, 1 ng, RSD 0.34%, accuracy 0.31%) whereas most other species ranged between 0.4 and 0.5% RSD if higher concentrations were used. The limitations of the pulse counting system are clearly seen, with peak heights of more than 2000 counts reaching saturation (for an integration time of 100 ms), which reduces the accuracy of isotope ratio determinations. A dozen VOM could be detected in an aged landfill gas sample; several unidentified Sn compounds were present. Although their isotope ratios are within the confidence value of the standards, it is not yet clear if the acquired precision is good enough to identify isotopic fractionation of metal(loid)s through biovolatilization processes. With the precision achieved, the combination of cryotrapping GC and ICP-TOFMS is a powerful tool for monitoring volatile multi-element species in multi-tracer experiments and isotope dilution methodology.

Application of natural zeolites for preconcentration of arsenic species in water samples.

Zeolites of the clinoptilolite type produced in Mexico and Hungary were investigated with respect to their sorption efficiency for various redox species of arsenic. Long-term experiments showed that arsenate remains stable for a long period in spiked deionised water and drinking water, as well as in the surface water of the Biela valley in Saxony, Germany. Both clinoptilolites are able to decrease the initial arsenic concentration of 200 microg l(-1) by more than 75% in deionised, drinking, ground and surface waters. In the case of the Mexican zeolite, both the arsenite and the arsenate concentrations (200 microg l(-1)) can be lowered from 200 microg l(-1) to 10 microg l(-1), which is the World Health Organisation's (WHO's) recommended maximum level. It was found that the presence of cations and anions in the natural waters of Biela, Germany, and Zimapán, Mexico, did not reduce the efficiency of the selected zeolites. The Hungarian zeolite removed 75% of the arsenate in the Zimapán water and only 50% when the sample was first acidified. This zeolite totally desorbed the fixed arsenic into a water volume that was half the volume in the adsorption experiment.

Evaluation of extraction procedures for the ion chromatographic determination of arsenic species in plant materials.

The determination of arsenic species in plants grown on contaminated sediments and soils is important in order to understand the uptake, transfer and accumulation processes of arsenic. For the separation and detection of arsenic species, hyphenated techniques can be applied successfully in many cases. A lack of investigations exists in the handling (e.g., sampling, pre-treatment and extraction) of redox- and chemically labile arsenic species prior to analysis. This paper presents an application of pressurized liquid extraction (PLE) using water as the solvent for the effective extraction of arsenic species from freshly harvested plants. The method was optimized with respect to extraction time, number of extraction steps and temperature. The thermal stability of the inorganic and organic arsenic species under PLE conditions (60-180 degrees C) was tested. The adaptation of the proposed extraction method to freeze-dried, fine-grained material was limited because of the insufficient reproducibility in some cases.

Urease inhibition: a tool for toxicity identification in sediment elutriates.

A method for the detection and confirmation of heavy metal toxicants in sediment elutriates based on a urease inhibition assay, ICP-AES analysis and EDTA chelation in the frame of toxicity identification evaluation (TIE) is presented. Zinc was identified as the major toxicant in pHstat elutriates of sediments of the river Saale (Germany). Implications of natural and anthropogenic chelating agents, which are frequently present in environmental samples, on toxicity confirmation of heavy metals based on the toxic unit approach are discussed.

Separation of unmodified polystyrene nanosphere standards by capillary zone electrophoresis.

Size separation of five unmodified polystyrene nanosphere standards with diameters between 50 and 600 nm has been achieved in phosphate buffer solutions as carrier electrolyte. The electrophoretic mobility increases with particle diameter. Optical spectra was shown to be different for particles of different size. Effects of injection time, applied voltage, pH, and phosphate concentration in carrier electrolyte on particle separation were studied. Under optimal conditions the peak efficiency ranged from 600 to 10,500 theoretical plate numbers depending on nanosphere diameter was achieved.

Bioleaching of heavy metal-contaminated sediments by indigenous Thiobacillus spp: metal solubilization and sulfur oxidation in the presence of surfactants.

The efficiency of surfactant application to improve or inhibit metal solubilization and sulfur oxidation kinetics during the bioleaching of heavy metal-contaminated sediments was studied in suspension-leaching experiments. The river sediment used contained large amounts of fine particles and organic matter. Three types of surfactants were tested: sodium dodecylsulfate (SDS), a C(12/14)-alkanolethoxylate (Präwozell F1214/5N), and a wettable sulfur (Netzschwefel 80 WP). Adding 10 mmol SDS/l led to transient inhibition of acidification, metal solubilization and sulfur oxidation. Inhibiting bioleaching for just 14 days required about ten times more SDS than the amount used for mine waste mitigation. The use of Präwozell resulted in poor inhibition; and using of wettable sulfur did not improve leaching efficiency. The bulk of these surfactants was sorbed onto the solid particles immediately on application, while the remainder in the aqueous phase disappeared within a few days.

Determination of arsenic species in water, soils and plants.

Ion chromatographic separation coupled with ICP-MS was used to determine arsenic species in plant and soil extracts. A scheme for growth, harvesting, sample pre-treatment and analysis was developed for the arsenic species to enable determination. Preliminary results obtained with ten herb plants grown on arsenic-contaminated soil compared to non-contaminated soil show a heterogeneous pattern of accumulation rate, metabolization and detoxification mechanisms in monocots and dicots. Arsenite appears to be the major component in plants with good growth. Organic arsenic species were even detected at very low concentrations (< 150 microg kg(-1) (dry mass)).