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1.
Environ Int ; 146: 106233, 2021 01.
Article in English | MEDLINE | ID: mdl-33189990

ABSTRACT

Green remediation of soils highly contaminated with potentially toxic elements (PTEs) can be achieved using suitable plants. Such phytoremediation procedure often takes into consideration PTE concentrations in plants only, but not produced biomass. Phytoremediation potential of certain species of wild plants for PTEs in contaminated floodplain soils has not been assessed yet. Therefore, in this work 12 native species were tested, 3 of which (Poa angustifolia, Galium mollugo, and Stellaria holostea) to our knowledge have never been used before, in a two-year pot experiment and assessed their potential as phytoremediation species. The results showed that plant PTE concentrations were dramatically elevated for Cd and Zn in Alopecurus pratensis, Arrhenatherum elatius, Bromus inermis, Artemisia vulgaris, Achillea millefolium, Galium mollugo, Stellaria holostea, and Silene vulgaris. A. vulgaris was by far the most highly PTE absorbing plant among the 12 tested in this work, especially concerning Zn, Cd, and to a lesser degree Cu and Ni. Also, among species non-studied-before, G. mollugo and S. holostea were characterized by high Zn and Cd uptake, while P. angustifolia did not. Assessing the number of harvests necessary to decrease soil PTE to half of the initial concentrations, it was found that for Cd plants would achieve site phytoremediation within 8 (A. vulgaris) to 28 (S. holostea) and 51 (G. mollugo) harvests, while for Zn, harvests ranged from 104 (A. vulgaris) to 209 (S. holostea), and 251 (A. millefolium). A clear grouping of the tested species according to their functional type was evident. Herbaceous species were collectively more efficient than grasses in PTE uptake combined by high biomass accumulation; thus, they may act as key-species in a phytoremediation-related concept. Our approach puts phytoremediation into a practical perspective as to whether the process can be achieved within a measureable amount of time. In conclusion, A. vulgaris behaved as a hyperaccumulator plant species in our heavily contaminated soil, while never-studied-before G. mollugo and S. holostea also had a hyperaccumulator behavior, especially for Cd and Zn. Although more research is necessary for conclusive results, our study is pivotal in that it would help in assessing plant species as potential phytoremediation species in heavily contaminated soils.


Subject(s)
Metals, Heavy , Soil Pollutants , Biodegradation, Environmental , Metals, Heavy/analysis , Plants , Soil , Soil Pollutants/analysis
2.
Sci Rep ; 7: 40522, 2017 01 17.
Article in English | MEDLINE | ID: mdl-28094280

ABSTRACT

Environmental contamination of arsenic (As) and its accumulation in rice (Oryza sativa L.) is of serious human health concern. In planta speciation of As is an important tool to understand As metabolism in plants. In the present study, we investigated root to shoot As translocation and speciation in rice exposed to inorganic and methylated As. Arsenate (AsV) and methylarsonate (MAV) were efficiently reduced to arsenite (AsIII) and MAIII, respectively in rice root and shoot but no trivalent form of dimethylarsinate (DMAV) was detected. Further, up to 48 and 83% of root As in AsV and MAV exposed plants, respectively were complexed with various thiols showing up to 20 and 16 As species, respectively. Several mixed As- and MA-complexes with hydroxymethyl-phytochelatin, DesGly-phytochelatin, hydroxymethyl-GSH and cysteine were identified in rice. Despite high complexation in roots, more As was translocated to shoots in MAV exposed plants than AsV, with shoot/root As transfer factor being in order DMAV > MAV > AsV. Moreover, in shoots 78% MAIII and 71% AsIII were present as weakly bound species which is alarming, as MAIII has been found to be more cytotoxic than AsIII for human and it could also be an important factor inducing straighthead (spikelet sterility disorder) in rice.


Subject(s)
Arsenic/metabolism , Oryza/metabolism , Plant Shoots/metabolism , Sulfhydryl Compounds/metabolism , Chromatography, Ion Exchange , Humans , Mass Spectrometry , Metabolomics/methods , Oryza/growth & development
3.
Anal Chim Acta ; 847: 44-8, 2014 Oct 17.
Article in English | MEDLINE | ID: mdl-25261899

ABSTRACT

The stability of antimonite in iron rich water samples is rather poor. The aim of the study was to find a simple procedure by using preservation agents to keep the speciation information from sampling till analysis. Species analysis of antimony traces (lower µg L(-1) range) was done by HPLC-ICP-MS. Phosphoric acid, tartrate, and EDTA were tested as preservation agents in comparison to no addition. The use of EDTA as the preservation agent provided the best results. The suggested procedure is to add 20 mM EDTA as final concentration immediately during sampling and store them at dark and cool (6 °C) as usual. Using this procedure, the stability of Sb(III) as well as of Sb(V) was proven for at least 7 days, even for high iron concentrations.

4.
Environ Pollut ; 165: 59-66, 2012 Jun.
Article in English | MEDLINE | ID: mdl-22406842

ABSTRACT

The mobilization behaviour of metalloids and metals when leached by water from highly polluted soil/sediment samples was studied using static and dynamic approaches employing batch methodology and rotating coiled columns (RCC), respectively. Increasing the solution-to-solid ratios during batch leaching resulted in different enhanced mobilization rates, which are element-specific and matrix-specific. When dynamic leaching is employed with continuous replacement of the eluent, a higher portion is mobilized than when using batch elution with an identical solid-to-water ratio. Using RCC the time-resolved leaching of the elements was monitored to demonstrate the leaching patterns. For the majority of elements a significant decrease could be shown in the mobilized portion of the elements with ongoing leaching process. The data were discussed targeted at solid liquid partitioning coefficients of the metal(loid)s. The capabilities in application of K(d) values was demonstrated for dynamic leaching which is relevant for environmental processes.


Subject(s)
Metalloids/chemistry , Metals/chemistry , Models, Chemical , Soil Pollutants/chemistry , Metalloids/analysis , Metals/analysis , Soil/chemistry , Soil Pollutants/analysis , Water/chemistry
5.
Talanta ; 88: 369-74, 2012 Jan 15.
Article in English | MEDLINE | ID: mdl-22265512

ABSTRACT

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


Subject(s)
Geologic Sediments/chemistry , Selenium/analysis , Soil Pollutants/analysis , Trace Elements/analysis , Adsorption , Buffers , Centrifugation , Chemical Fractionation/instrumentation , Chemical Fractionation/methods , Environmental Monitoring , Quaternary Ammonium Compounds/chemistry , Spectrophotometry, Atomic , Sulfites/chemistry , Water/chemistry
6.
Talanta ; 85(4): 2089-93, 2011 Sep 30.
Article in English | MEDLINE | ID: mdl-21872062

ABSTRACT

The remobilization of antimony and vanadium from previously loaded commercial granular ferric-hydroxide GEH material (intended for water treatment) was examined by using a sequential extraction procedure and three different leaching systems to evaluate their physicochemical mobility and potential availability under different simulated environmental conditions. A classical batch extraction, an extraction cell (EC) and rotating-coiled columns (RCC) were used as extraction systems. For each system it could be shown that the content of ion-exchangeable antimony and vanadium in previously loaded material is negligible (<1.5%). The oxyanions were sorbed strongly and could be predominantly remobilized through reducing agents, which means through dissolution of the iron (hydr)oxide matrix. The major advantages of dynamic systems in comparison to batchwise fractionation technique are the drastically reduced extraction time and the possibility of generating information to the leaching kinetics. It is shown that the efficiency of the three leaching systems is quite different employing Wenzel's sequential fractionation protocol. Only by working with RCC, the iron (hydr)oxide matrix was completely dissolved within four steps resulting in the total mobilization of antimony and vanadium. EC seems to be less suitable for leaching studies of Sb and V sorbed on iron(hydr)oxide. The remobilizable proportion of the several fractions was lower in comparison to batch and RCC and seems to be a result of an agglomeration of the GEH in the EC device.

7.
J Environ Monit ; 13(6): 1672-7, 2011 Jun.
Article in English | MEDLINE | ID: mdl-21503335

ABSTRACT

This study investigates the stabilization of As in the contaminated sludge after treatment with MnO(2) or Ca(OH)(2), and the influence of the stabilizing materials on the leachability of the co-existing elements Pb and Zn. By exploiting a continuous-flow assembly facilitating a modified Wenzel's sequential extraction scheme (designed for the fractionation of arsenic), it is possible to ascertain the leachability, mobility and fractional alteration of these elements under stimulated natural (flow-through) leaching conditions. The fractionation data show that more than 80% of As, Pb and Zn in the untreated sludge are bound in the amorphous Fe oxides fraction and residual fraction. The addition of MnO(2) has only an insignificant effect on As fractional transformation, while Ca(OH)(2) caused an increase in As mobility. For Pb, the decrease in leachability was clearly visible. The extractable Pb was reduced by 18% and 40% in stabilized MnO(2) and Ca(OH)(2) sludge samples, respectively. Unlike that of Pb, the mobility of Zn was not affected by the additives used. Their fractional distribution patterns before and after the stabilization process remained the same. The ability to produce detailed leaching profiles for As and other elements (Pb, Zn, Ca, Mn and Fe) meant that elemental associations in individual fractions could be examined. From the MnO(2)-treated sludge, the coincidence of the As, Pb, Zn, Fe, and Mn peaks seems to indicate a close association of these elements in the Fe-oxides-bound fraction. Furthermore, the leaching profiles may be used as evidence of a strong affinity between these elements and added MnO(2).


Subject(s)
Arsenic/analysis , Metals, Heavy/chemistry , Sewage/chemistry , Soil Pollutants/analysis , Arsenic/chemistry , Calcium Hydroxide/chemistry , Manganese Compounds/chemistry , Models, Chemical , Oxides/chemistry , Soil Pollutants/chemistry
8.
J Hazard Mater ; 186(2-3): 1328-34, 2011 Feb 28.
Article in English | MEDLINE | ID: mdl-21194836

ABSTRACT

Sorption of phenylarsenicals including 4-hydroxy-3-nitrophenylarsonic acid (roxarsone), an animal feed additive widely used for growth stimulation, on soils was investigated in batch systems. Phenylarsonic acid, o-arsanilic acid and roxarsone were retained differently by unpolluted, non-sterilized soils. Sorption isotherms were analyzed by the Henry, Tóth and Langmuir-Freundlich equations. The saturation capacity of the Acrisol soil was 3.4 for o-arsanilic acid, 10.9 for phenylarsonic acid and 1.9 g(As) kg(soil)(-1) (dry mass) for roxarsone. The iron content in the soil was not the only factor determining retention of the studied phenylarsenicals. The order of retention on the three soils after 24 h was: roxarsone>o-arsanilic acid>phenylarsonic acid. Besides arsenite and arsenate, new arsenic-containing compounds were detected.


Subject(s)
Arsenicals/chemistry , Soil Pollutants/analysis , Volcanic Eruptions/analysis , Adsorption , Algorithms , Arsanilic Acid/chemistry , Arsenic/chemistry , Chromatography, High Pressure Liquid , Desiccation , Humidity , Kinetics , Mass Spectrometry , Roxarsone/chemistry , Soil/analysis , Spectrophotometry, Ultraviolet , Thermodynamics
9.
Anal Bioanal Chem ; 399(6): 2211-7, 2011 Feb.
Article in English | MEDLINE | ID: mdl-21107821

ABSTRACT

Calibration of analytical methods using laser ablation for sample introduction is often problematic. The availability of matrix-adapted standard materials is a crucial factor in the analysis of biological samples in particular. In this work a method for preparation of thin-film references for LA-ICP-MS is presented which is inexpensive, relatively simple and generally practicable. Aqueous solutions of agarose spiked with defined amounts of the analytes were cast on a carrier and then dried. When the thin-film references were characterized the average thickness of the films was 0.03 mm in the centre of the film and the relative standard deviation was 8%. Nebulization ICP-MS analysis after acid digestion of the agarose film was used to investigate the effectiveness of the spiking procedure. Recovery of the spiked elements was frequently in the range 90-110% (for rare earth elements 97-102%). Laser ablation ICP-MS analysis was used to investigate the distribution of the spiked elements in the film. When the laser was scanned across the gel the measured intensities were not constant, but had a peak-shaped profile with a flat top. Use of this flat-top region for analytical purposes, after its characterization by laser ablation ICP-MS, is proposed. Analysis of cell cultures was carried out by direct laser ablation-ICP-MS with the calibration method described. The results were in accordance with values previously achieved by nebulization ICP-MS.

10.
J Hazard Mater ; 184(1-3): 849-854, 2010 Dec 15.
Article in English | MEDLINE | ID: mdl-20870353

ABSTRACT

A dynamic flow-through extraction system was applied for the first time to ascertain the fractional transformation and inter-element associations of arsenic in stabilized environmental solids, as exemplified by the partitioning of soil and sludge stabilized with three additives, namely MnO(2), Ca(OH)(2) and FeSO(4). The extraction system used not only gave fractionation data, but also the extraction profiles (extractograms) which were used for investigation of the breaking down of phases, kinetic releasing of As and elemental association between As and inorganic additives. Five geochemical fractions of As were elucidated by accommodation in the flow manifold of a modified Wenzel's sequential extraction scheme, well established for fractionation of arsenic. The results revealed that MnO(2) and FeSO(4) have a slight effect on As phase transformation for soil and sludge samples amended for one week whereas the addition of Ca(OH)(2) increases As mobility due to the desorption of As from the solid Fe-oxides phase. The significant change in fractional transformation after 8 weeks of incubation can be seen in MnO(2)-treated soil. There was an increase of 17% in the non-mobilizable As fraction in MnO(2)-treated soil. From extractograms, arsenic in untreated soil was found to be rapidly leached and concurrently released with Fe. This may be evidence that the release of As is dependent on the dissolution of amorphous Fe oxides. In MnO(2)-treated soil, a strong affinity was observed between Mn and As in the amorphous Fe/Al oxides fraction, and this plays an important role in slowing down the kinetics of As releasing.


Subject(s)
Arsenic/chemistry , Sewage/chemistry , Soil Pollutants/chemistry , Calcium Hydroxide/chemistry , Kinetics , Manganese Compounds/chemistry , Oxides/chemistry
11.
Talanta ; 82(1): 38-43, 2010 Jun 30.
Article in English | MEDLINE | ID: mdl-20685432

ABSTRACT

Arsenic is a metalloid well known to be potentially toxic depending of its species. Lipid-soluble arsenicals (arsenolipids) are present in a wide range of biological samples in which they could play a role in the biosynthesis of organoarsenic compounds from inorganic arsenic compounds. Arsenolipids have recently attracted considerable interest. In order to gain deeper insights into the impact of arsenolipids new analytical approaches for reliable determination of this class of arsenic-containing hydrocarbons in various matrices are needed. High concentrations of arsenolipids were found in seafood which served as sample material in this study. We report the investigation of three arsenolipids found in canned cod liver from which they were extracted and purified by solid phase extraction (SPE) using a silica gel column and ethyl acetate/methanol as eluent. Analytical studies were conducted by means of gas chromatography coupled with ICP-MS, MIP-AES and EI-qMS and by TOF-MS. The results obtained by GC-ICP-MS and GC-MIP-AES showed the existence of numerous arsenic compounds in the SPE fractions collected. Three major peaks were found within a retention time window between 10 and 25 min. The presence of arsenic compounds in the fish tissue could be confirmed using GC-EI-qMS analysis. Corresponding information of the molecular weights of the major arsenic species were provided by TOF-MS which allows highly accurate mass determinations. The results showed the presence of the arsenic-containing hydrocarbons with the following molecular formulas: C(17)H(37)AsO (calculated for [M+H](+) 333.2133; found 333.2136; Deltam=0.90 ppm); C(19)H(41)AsO (calculated for [M+H](+) 361.2446; found 361.2446; Deltam=0.00 ppm); C(23)H(37)AsO (calculated for [M+H](+) 405.2133; found 405.2145; Deltam=2.96 ppm). Suggestions for the corresponding structures are discussed.


Subject(s)
Arsenic/analysis , Food Analysis/methods , Food Contamination/analysis , Food, Preserved/analysis , Gadus morhua , Hydrocarbons/chemistry , Liver/cytology , Animals , Arsenic/chemistry , Gas Chromatography-Mass Spectrometry , Lipids/chemistry , Solubility
12.
Environ Pollut ; 158(11): 3439-44, 2010 Nov.
Article in English | MEDLINE | ID: mdl-20667635

ABSTRACT

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16mgL(-1) and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400µgL(-1)) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.


Subject(s)
Arsenic/analysis , Chemical Warfare Agents/analysis , Environmental Monitoring , Water Pollutants, Chemical/analysis , Arsenates/analysis , Arsenates/chemistry , Arsenic/chemistry , Arsenicals/analysis , Arsenicals/chemistry , Arsenites/analysis , Arsenites/chemistry , Chemical Warfare Agents/chemistry , Water Pollutants, Chemical/chemistry
13.
J Sep Sci ; 33(6-7): 817-25, 2010 Mar.
Article in English | MEDLINE | ID: mdl-20222073

ABSTRACT

Zwitterionic hydrophilic interaction chromatography (ZIC-HILIC) was used to study the retention of selected organoarsenicals. The retention behavior of nine organic arsenic species on ZIC-HILIC was investigated to elucidate which is the driving force for their separation, hydrophilic partitioning or adsorption driven by hydrogen bonds with surface H-donor/acceptor groups of the stationary phase. For this, the retention factor of the compounds k was correlated with log P(O/W) and with the calculated strength of hydrogen bonding of the analytes. By examining aliphatic and phenylic compounds separately, improved correlation was received. This indicates that both phenomena contribute to the separation of these arsenic species on ZIC-HILIC. The results obtained evidence that considerable electrostatic interactions also occur on ZIC-HILIC. Retention behavior of arsenic species was investigated by varying the separation conditions, which shows that the composition of the eluent has a strong influence on the retention behavior. It is highly dependent on water/acetonitrile ratio, pH value and salt additives. Dissociation degree and polarity of arsenic species, which are varying with pH, regulate the distribution of arsenic species between stationary and mobile phases in HILIC. Increase in the ammonium acetate concentration leads to shortened or to prolonged retention depending on the structure of the arsenic species.


Subject(s)
Arsenic/chemistry , Chromatography, Liquid/methods , Spectrometry, Mass, Electrospray Ionization
14.
Environ Pollut ; 158(1): 308-18, 2010 Jan.
Article in English | MEDLINE | ID: mdl-19646800

ABSTRACT

Environmental pollution by mercury (Hg) is a considerable environmental problem world-wide. Due to the occurrence of Hg volatilization from their soils, floodplains can function as an important source of volatile Hg. Soil temperature and soil water content related to flood dynamics are considered as important factors affecting seasonal dynamics of total gaseous mercury (TGM) fluxes. We quantified seasonal variations of TGM fluxes and conducted a laboratory microcosm experiment to assess the effect of temperature and moisture on TGM fluxes in heavily polluted floodplain soils. Observed TGM emissions ranged from 10 to 850 ng m(-2) h(-1) and extremely exceeded the emissions of non-polluted sites. TGM emissions increased exponentially with raised air and soil temperatures in both field (R(2): 0.49-0.70) and laboratory (R(2): 0.99) experiments. Wet soil material showed higher TGM fluxes, whereas the role of soil water content was affected by sampling time during the microcosm experiments.


Subject(s)
Mercury/analysis , Water Pollutants, Chemical/analysis , Wetlands , Environmental Monitoring , Germany , Temperature
15.
Talanta ; 79(4): 1081-8, 2009 Sep 15.
Article in English | MEDLINE | ID: mdl-19615513

ABSTRACT

Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps. A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min(-1) prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry. Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilizable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.

16.
Talanta ; 78(3): 820-6, 2009 May 15.
Article in English | MEDLINE | ID: mdl-19269435

ABSTRACT

Antimony is a common contaminant at abandoned sites for non-ferrous ore mining and processing. Because of the possible risk of antimony by transfer to plants growing on contaminated sites, it is of importance to analyze antimony and its species in such biota. A method based on high performance liquid chromatographic separation and inductively coupled plasma mass spectrometric detection (HPLC-ICP-MS) was developed to determine inorganic antimony species such as Sb(III) and Sb(V) as well as possible antimony-organic metabolisation products of the antimony transferred into plant material within one chromatographic run. The separation is performed using anion chromatography on a strong anion exchange column (IonPac AS15/AG 15). Based on isocratic optimizations for the separation of Sb(III) and Sb(V) as well as Sb(V) and trimenthylated Sb(V) (TMSb(V)), a chromatographic method with an eluent gradient was developed. The suggested analytical method was applied to aqueous extracts of Chinese break fern Pteris vittata samples. The transfer of antimony from spiked soil composites into the fern, which is known as a hyperaccumulator for arsenic, was investigated under greenhouse conditions. Remarkable amounts of antimony were transferred into roots and leaves of P. vittata growing on spiked soil composites. Generally, P. vittata accumulates not only arsenic (as shown in a multiplicity of studies in the last decade), but also antimony to a lower extent. The main contaminant in the extracts was Sb(V), but also elevated concentrations of Sb(III) and TMSb(V) (all in microg L(-1) range). An unidentified Sb compound in the plant extracts was detected, which slightly differ in elution time from TMSb(V).


Subject(s)
Antimony/analysis , Plant Extracts/chemistry , Pteris/chemistry , Soil Pollutants , Chromatography, High Pressure Liquid , Ion Exchange , Mass Spectrometry
17.
Anal Bioanal Chem ; 390(7): 1707-15, 2008 Apr.
Article in English | MEDLINE | ID: mdl-18259734

ABSTRACT

Combined detection by inductively coupled mass spectrometry (ICP-MS) for elemental information (quantification) and electrospray ionization mass spectrometry (ESI-MS) for molecular information (identification) by means of splitting of the eluent after chromatographic separation is a suitable means of analysis for unknown and not commercially available arsenic species. Simultaneous parallel ESI-MS and ICP-MS detection was applied to identify possible metabolites during the interaction of arsenobetaine (AsB) with natural zeolites. AsB, mainly produced by freshwater and marine organisms, is known to be a candidate of low toxicity. To estimate the possible toxicological risk originating from AsB in contact with natural and synthetic zeolites, small particles of a naturally occurring zeolite were mixed with an AsB solution. After a contact time of 56 days the degradation of AsB proceeded with different yields in the case of the natural Mexican zeolites. In contrast, no additional components were detected in the control samples. It was possible to clearly identify the degradation products dimethylarsinate (m/z 139) and dimethylarsinoylacetate (m/z 181) by comparison of the peaks monitored by ESI-MS and ICP-MS. In some other cases the unknown arsenic species could not be identified so clearly from their molecular masses.


Subject(s)
Arsenicals/analysis , Arsenicals/metabolism , Mass Spectrometry/methods , Spectrometry, Mass, Electrospray Ionization/methods , Zeolites/chemistry , Arsenicals/chemistry , Chromatography, High Pressure Liquid/methods , Mass Spectrometry/instrumentation , Nitric Acid/chemistry , Reproducibility of Results , Sensitivity and Specificity , Time Factors
18.
Sci Total Environ ; 389(2-3): 486-96, 2008 Jan 25.
Article in English | MEDLINE | ID: mdl-17928036

ABSTRACT

Fungal growth on alder leaves was studied in two heavy metal polluted streams in central Germany. The aim of the study was to examine previously observed differences in leaf decomposition rates, heavy metal precipitation and fungal involvement in these processes at the microscopic level. Ergosterol analyses indicated that neither habitat was optimal for fungi, but leaves exposed at the less polluted site (H8) decomposed rapidly and were colonized externally and internally by fungi and other microorganisms. Leaves exposed at the more polluted site (H4) decomposed very slowly and fungal colonization was restricted to external surfaces. An amorphous organic layer, deposited within 24 h of exposure, quickly became covered with a pale blue-green crystalline deposit (zincowoodwardite) with significant amounts of Al, S, Cu and Zn, determined by energy dispersive X-ray spectroscopy (EDS). Scanning electron microscopy (SEM) analysis of the precipitate revealed a branching arrangement of the precipitated particles caused by the presence of fungal hyphae growing on the surface. Hyphae that were not disturbed by handling were usually completely encased in the precipitate, but hyphae did not contain EDS-detectable amounts of precipitate metals. Elemental analysis using inductively coupled plasma (ICP) atomic emission spectrometry and ICP mass spectrometry revealed continuing accumulation of Zn, Cu and several other metals/metalloids on and in leaves. The formation of metal precipitates on various artificial substrates at site H4 was much reduced compared to leaves, which we attribute to the absence of fungal colonization on the artificial substrates. We could not determine whether fungi accelerate the precipitation of heavy metals at site H4, but mycelial growth on leaves continues to create new surfaces and therefore thicker layers of precipitate on leaves compared to artificial substrates.


Subject(s)
Environmental Monitoring/methods , Fresh Water , Fungi/growth & development , Metals, Heavy/analysis , Water Microbiology , Water Pollutants, Chemical/analysis , Alnus/chemistry , Alnus/microbiology , Alnus/ultrastructure , Chemical Precipitation , Fresh Water/analysis , Fresh Water/microbiology , Germany , Microscopy, Electron, Scanning , Mining , Plant Leaves/chemistry , Plant Leaves/microbiology , Plant Leaves/ultrastructure
19.
Water Res ; 41(15): 3259-70, 2007 Aug.
Article in English | MEDLINE | ID: mdl-17575997

ABSTRACT

In this study, we used isotopic (delta18O, delta2H, delta34S-SO4) and chemical tracers (boron) to assess the sources and transport processes of the micropollutants carbamazepine, galaxolide, and bisphenol A in groundwater underlying the city of Halle (Saale), Germany. Their ubiquitous presence in urban groundwater results from a combination of local river water infiltration, sewer exfiltration, and urban stormwater recharge. Attenuation during transport with infiltrating river water increased from carbamazepine (0-60%) to galaxolide (60-80%) in accordance with their increasing sorption affinity and decreasing recalcitrance against biodegradation. Distinctly higher attenuation during transport was found for carbamazepine (85-100%) and galaxolide (95-100%) if micropollutants originated from sewer exfiltration. Most likely, this is related to higher contents of organic matter and higher transit times of the respective flow paths. Although attenuation undoubtedly also affects the transport of bisphenol A, quantification is limited due to additional contributions from the urban stormwater recharge. As a consequence, micropollutant loads in groundwater indicate that groundwater discharge may dominate the export of bisphenol A from urban areas.


Subject(s)
Benzopyrans/analysis , Carbamazepine/analysis , Phenols/analysis , Water Pollutants, Chemical/analysis , Water Supply/analysis , Benzhydryl Compounds , Boron/analysis , Cities , Deuterium/analysis , Environmental Monitoring , Germany , Oxygen Isotopes/analysis , Sulfates/analysis , Sulfur Isotopes/analysis , Water Movements
20.
Chemosphere ; 68(2): 253-8, 2007 Jun.
Article in English | MEDLINE | ID: mdl-17316755

ABSTRACT

Arsenic predominantly occurs in natural ground and surface waters as arsenate and arsenite. Other arsenic species can also be present in anthropogenically influenced waters. By means of a newly-developed speciation technique an arsenic compound was identified as hexafluoroarsenate at high concentration (about 0.8mgl(-1) as As) in a lake polluted by waste water from a former crystal glass factory. This compound shows a completely different behavior than common arsenite and arsenate in waters. However, respective literature data were little found regarding its environmental behavior as well as the applicable remediation technologies. Conventional arsenic treatment mechanisms, such as the well-known sorption to iron hydroxides, can not be used to remediate water with this compound. Hence, an effective method to remove hexafluoroarsenate from water was developed using its strong affinity to anion exchangers (strong basic exchangers with quaternary ammonium groups). The sorption can be described by a Langmuir isotherm and first-order kinetics with a half-life of about 10min. Interferences by sulphate and fluoride, present at much higher concentrations in the polluted lake water, might be expected due to the anion exchange mechanism, but were shown to be of minor importance.


Subject(s)
Arsenates/isolation & purification , Environmental Restoration and Remediation/methods , Water Pollutants, Chemical/isolation & purification , Arsenates/chemistry , Fresh Water/chemistry , Germany , Ion Exchange Resins/chemistry
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