René P. Schwarzenbach

Swiss Academy of Sciences

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Philip M. Gschwend

Woods Hole Oceanographic Institution

Kai‐Uwe Goss

Helmholtz Centre for Environmental Research

Dieter M. Imboden

ETH Zurich

Thomas B. Hofstetter

Swiss Federal Institute of Aquatic Science and Technology

Stefan B. Haderlein

University of Tübingen

S. Müller

Klinikum Bielefeld

Beate I. Escher

Helmholtz Centre for Environmental Research

Michael Berg

Swiss Federal Institute of Aquatic Science and Technology

Michael Sander

ETH Zurich

Heinz Singer

Swiss Federal Institute of Aquatic Science and Technology

Cooperative Institutions

Swiss Federal Institute of Aquatic Science and Technology

132

ETH Zurich

115

École Polytechnique Fédérale de Lausanne

University of Zurich

Agroscope

University of Minnesota

University of Bern

Helmholtz Centre for Environmental Research

University of Basel

Board of the Swiss Federal Institutes of Technology

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Contaminated environments in the subsurface and bioremediation: organic contaminants

FEMS Microbiology Reviews (1997)

Christof Holliger Sarra Gaspard Guy Glod Cornelis G. Heijman Wolfram Schumacher

Due to leakages, spills, improper disposal and accidents during transport, organic compounds have become subsurface contaminants that threaten important drinking water resources. One strategy to remediate such polluted subsurface environments is to make use of the degradative capacity of bacteria. It is often sufficient to supply the subsurface with nutrients such as nitrogen and phosphorus, and aerobic treatments are still dominating. However, anaerobic processes have advantages such as low biomass production and good electron acceptor availability, and they are sometimes the only possible solution. This review will focus on three important groups of environmental organic contaminants: hydrocarbons, chlorinated and nitroaromatic compounds. Whereas hydrocarbons are oxidized and completely mineralized under anaerobic conditions in the presence of electron acceptors such as nitrate, iron, sulfate and carbon dioxide, chlorinated and nitroaromatic compounds are reductively transformed. For the aerobic often persistent polychlorinated compounds, reductive dechlorination leads to harmless products or to compounds that are aerobically degradable. The nitroaromatic compounds are first reductively transformed to the corresponding amines and can subsequently be bound to the humic fraction in an aerobic process. Such new findings and developments give hope that in the near future contaminated aquifers can efficiently be remediated, a prerequisite for a sustainable use of the precious-subsurface drinking water resources.

Electron acceptor

Reductive Dechlorination

10.1111/j.1574-6976.1997.tb00334.x

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Citations (175)

FATTY ACID DYNAMICS IN THALASSIOSIRA PSEUDONANA (BACILLARIOPHYCEAE): IMPLICATIONS FOR P HYSIOLOGICAL ECOLOGY^1,^2,³

Journal of Phycology (1978)

Nicholas S. Fisher René P. Schwarzenbach

ABSTRACT The growth dry weight, fatty acid weight and fatty acid composition of two clones of Thalassiosira pseudonana Hasle & Heimdal were measured under several growth conditions. Determinations of total cellular fatty acids were made using chemical ionization mass spectrometry. Both clones had the same fatty acids, dominated by C14:0, C16:0, C16:1, C16:3, C16:4, C18:4 and C20:5, though in different relative amounts. Fatty acids typically represented 5–10% the dry weight of a cell during log Phase growth and up to 22% during stationary Phase. The C16 fatty acids of both clones changed as the cultures aged, though much more markedly in the Sargasso Sea done (13–1) than in the estuarine one (3H). The C16:0 and C16:1 acids of both clones declined sharply in the dark and were replenished in the light. Cells maintained in constant illumination, but with no cell division. produced large quantities of these acids. Cells of done 13–1 treated with polychlorinated biphenyl (PCB) initially grew more slowly than control cells, weighed more, and had higher relative amounts of C16:0 and C16:1. Fatty acid studies may provide useful indicators of ecologically important energy reserves and membrane adaptations in the algae .

Thalassiosira pseudonana

Dry weight

Chlorophyceae

10.1111/j.1529-8817.1978.tb02439.x

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Citations (77)

Corrinoid-Mediated Reduction of Tetrachloroethene, Trichloroethene, and Trichlorofluoroethene in Homogeneous Aqueous Solution: Reaction Kinetics and Reaction Mechanisms

Environmental Science & Technology (1996)

Guy Glod Werner Angst Christof Holliger René P. Schwarzenbach

It is shown that in homogeneous aqueous solution containing titanium(III) citrate or titanium(III)−NTA as bulk electron donor, cobalamin, cobinamide, and cobamide are effective electron transfer mediators for the reduction of tetrachloroethene (PCE), trichloroethene (TCE), and trichlorofluoroethene (TCFE). For a given chlorinated ethene, the reaction rate varied only slightly with pH and type of corrinoid present and was about 5 and 50 times faster for PCE as compared to TCFE and TCE, respectively. Evidence is presented that the first and rate-limiting step of the reduction of PCE, TCE, and TCFE by super-reduced corrinoids is a dissociative one-electron transfer yielding the corresponding vinyl radicals. Furthermore, the elimination of a chloride radical from the 1,1-dichlorovinyl radical yielding chloroacetylene and subsequently acetylene is proposed to account for the direct formation of acetylene out of TCE. Finally, it is demonstrated that at higher reduction potentials the corrinoid mediators may be blocked by the formation of addition products.

Corrinoid

Acetylene

10.1021/es9603867

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Citations (154)

Adsorption of a Diverse Set of Organic Vapors on the Bulk Water Surface

Journal of Colloid and Interface Science (2002)

Christine M. Roth Kai‐Uwe Goss René P. Schwarzenbach

10.1006/jcis.2002.8446

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Citations (75)

Appendix E: Properties of The Earth

René P. Schwarzenbach Philip M. Gschwend Dieter M. Imboden

10.1002/0471649643.app5

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Citations (0)

Appendix A: Mathematics

René P. Schwarzenbach Philip M. Gschwend Dieter M. Imboden

10.1002/0471649643.app1

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Citations (0)

pH Dependence of the Partitioning of Triphenyltin and Tributyltin between Phosphatidylcholine Liposomes and Water

Environmental Science & Technology (2001)

René Hunziker Beate I. Escher René P. Schwarzenbach

Triorganotin compounds are very toxic contaminants. The site of their basic mechanism of action of acute toxicity is the biomembrane. Liposome−water distribution ratios of triphenyltin and tributyltin were determined between pH 3 and pH 8 with the equilibrium dialysis method in the micromolar concentration range, which is the concentration range where acute toxicity is observed. In addition, biomembrane−water distribution ratios of tributyltin were determined with chromatophores of Rhodobacter sphaeroides that contain approximately 70% protein intercalated in the lipid bilayer. The liposome−water distribution of both compounds showed only weak pH dependence. For tributyltin, the apparent distribution ratio decreased from 4100 at low pH to 2000 at high pH, while this ratio decreased from 70 000 to 22 000 for TPT. The distribution ratio of the triorganotin cation exceeded that of the neutral hydroxo complex by a factor of 2. The distribution ratio of both the cation and the hydroxo complex of triphenyltin exceeded that of tributyltin by a factor of 10. It is postulated that the sorption of the cation is governed by complex formation with ligands in the phospholipids, presumably the phosphate group. The biomembrane−water distribution ratio of tributyltin was found to be lower than the liposome−water distribution ratio at high pH. The hydroxo complex appears to partition only to the lipid fraction of the biomembrane. Yet, at low pH the biomembrane−water distribution ratio exceeded the liposome−water distribution ratio, which is attributed to complex formation of the cationic species with ligands of the protein fraction.

10.1021/es010043v

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Citations (40)

Adsorption of Organic Vapors to Air-Dry Soils: Model Predictions and Experimental Validation

Environmental Science & Technology (2004)

Kai‐Uwe Goss Johanna Buschmann René P. Schwarzenbach

Soil/air equilibrium partitioning has an important impact on the environmental distribution and fate of many organic chemicals. Modeling approaches that cover this process commonly assume that sorption in soil only occurs in soil organic matter. However, many researchers have already shown that this is not even correct for nonpolar compounds in air-dry soils. Here, we extend the existing data set on sorption in air-dry soils by using a large and very diverse set of organic compounds covering many different functional groups for two standard soils and for relative humidity between 50 and 90%. The experimental data presented here as well as those from the literature are then used to examine two different modeling approaches: one that only considers absorption in soil organic matter and one that also considers adsorption to mineral surfaces. The results clearly show that sorption in air-dry soil cannot be explained when adsorption to mineral surfaces is ignored. Only the model that considers both sorbing phases, organic matter and mineral surfaces, gives good agreement for all experimental data. Our model for predicting adsorption to mineral surfaces does not require any further fitting with experimental data; thus, it can readily be incorporated into existing fate models in order to improve the description of the soil/air partition process.

10.1021/es035388n

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Citations (68)

Complete Reduction of TNT and Other (Poly)nitroaromatic Compounds under Iron-Reducing Subsurface Conditions

Environmental Science & Technology (1999)

Thomas B. Hofstetter Cornelis G. Heijman Stefan B. Haderlein Christof Holliger René P. Schwarzenbach

Contamination of soils and aquifers with (poly)nitroaromatic compounds ((P)NACs) is a widespread problem. This work demonstrates that (P)NACs such as the explosive 2,4,6-trinitrotoluene (TNT) can be completely reduced to the corresponding aromatic polyamines by Fe(II) present at the surface of Fe(III)(hydr)oxides or, less efficiently, by hydroquinone moieties of (natural) organic matter in the presence of H2S. The reduction kinetics of (P)NACs were investigated in sterile batch systems as well as in columns containing either FeOOH-coated sand and a pure culture of the iron-reducing bacterium Geobacter metallireducens or ferrogenic consortia in aquifer sediments. The relative reactivities as well as the competition behavior of (P)NACs in batch and column systems, respectively, correlated well with their one-electron reduction potentials, ', which we determined for TNT and its aminonitrotoluene transformation products. A similar reactivity pattern of (P)NACs was found irrespective of the processes that (re)generated the surface-bound Fe(II), i.e., adsorption of Fe(II) from aqueous solution or microbial reduction of Fe(III)(hydr)oxides. The apparent stability of the toxic arylamine products under ferrogenic conditions may compromise intrinsic attenuation as an acceptable remediation option for (P)NAC contaminated anoxic aquifers. Iron-reducing conditions would, however, be favorable as a first step in a two-stage anaerobic/aerobic treatment of PNAC contaminated sediments since aromatic polyamines are biodegradable and/or bind irreversibly to the solid matrix under oxic conditions.

Reductive Dechlorination

Hydroquinone

Dithionite

Reducing agent

Zerovalent iron

10.1021/es9809760

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Citations (280)

Oxidation of Substituted Anilines by Aqueous MnO₂: Effect of Co-Solutes on Initial and Quasi-Steady-State Kinetics

Environmental Science & Technology (1997)

Jörg Klausen Stefan B. Haderlein René P. Schwarzenbach

The effect of pH, Mn(II), and humic acid (HA) concentration as well as aromatic ring substituents on initial and quasi-steady-state rates of oxidation of monosubstituted anilines by MnO2 has been investigated in batch and completely mixed flow-through reactors. The reaction rates were strongly pH-dependent and increased with decreasing pH. Mn(II), Ca(II), HA, and other organic solutes inhibited the oxidation of substituted anilines. Inhibition by adsorbed Mn(II) was due to blocking of reactive Mn(IV) surface sites. The inhibitory effect of HA and some other organic solutes was in part due to reductive dissolution of MnO2 and, thus, due to formation of adsorbed Mn(II). Initial rates of oxidation of a series of substituted anilines were linearly correlated to polarographic half-wave oxidation potentials, E1/2, indicating that electron-transfer kinetics were relevant for the overall rate of oxidation. However, results from flow-through experiments demonstrate that such correlations may change or disappear, subject to changing solution composition. Quasi-steady-state rates were generally significantly smaller than initial rates, indicating that the ability of MnO2 to efficiently oxidize organic pollutants may be impaired by long-term exposure of the mineral surface to inorganic and organic co-solutes.

Oxidation state

10.1021/es970053p

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Citations (136)