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PubMed2001

Biologically-enhanced removal of PCE from NAPL source zones.

The influence of dechlorinating microorganisms on PCE and its reduction products in a residual nonaqueous phase liquid (NAPL) source zone was investigated. Experiments were conducted in upflow columns containing glass beads (diameters 500-750 microns) contaminated with a residual NAPL consisting of tridecane and labeled 14C-PCE. Three columns were inoculated with a mixed PCE-dechlorinating culture, that was fed electron donor (pyruvate) at concentrations of 25, 100, and 250 mM. Pyruvate was fermented in all columns with essentially no methanogenic activity. Comparisons between actively dechlorinating columns and abiotic-PCE columns demonstrated that dechlorination resulted in an increase in total PCE removal, up to a factor of 16 over dissolution. PCE was sequentially reduced to trichloroethene, cis-dichloroethene, and vinyl chloride without ethene formation over the experimental period in the two columns operated at the lower electron donor levels. Total chlorinated ethenes removal for the columns that retained dechlorinating populations was enhanced from 5.0 to 6.5 times over the removal that would have resulted from dissolution alone. The system fed the highest pyruvate levels, interestingly, lost dechlorinating activity early in the experiment.

Chlorine Compounds↗
PubMed2001

Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California.

The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

Amino Acids↗
PubMed2001

Kinetics of soluble chromium removal from contaminated water by zerovalent iron media: corrosion inhibition and passive oxide effects.

Permeable reactive barriers containing zerovalent iron are being increasingly employed for in situ remediation of groundwater contaminated with redox active metals and chlorinated organic compounds. This research investigated the effect of chromate concentration on its removal from solution by zerovalent iron. Removal rates of aqueous Cr(VI) by iron wires were measured in batch experiments for initial chromium concentrations ranging from 100 to 10 000 microg/L. Chromate removal was also measured in columns packed with zerovalent iron filings over this same concentration range. Electrochemical measurements were made to determine the free corrosion potential and corrosion rate of the iron reactants. In both the batch and column reactors, absolute rates of chromium removal declined with increasing chromate concentration. Corrosion current measurements indicated that the rate of iron corrosion decreased with increasing Cr(VI) concentrations between 0 and 5000 microg/L. At a Cr(VI) concentration of 10 000 microg/L, Tafel polarization diagrams showed that chromium removal was affected by its diffusion rate through a passivating oxide film and by the ability of iron to release Fe2+ at anodic sites. In contrast, water reduction was not mass transfer limited, but chromium did decrease the exchange current for the hydrogen evolution reaction. Even at the most passivating concentration of 10 000 microng/L, effluent Cr(VI) concentrations in the column reactors reached a steady state, indicating that passivation had also reached a steady state. Although chromate contributes to iron surface passivation, the removal rates are still sufficiently fast for in situ iron barriers to be effective for Cr(VI) removal at most environmentally relevant concentrations.

Carcinogens↗
PubMed2001

Synergistic effect of cationic surfactants on perchloroethylene degradation by zero-valent iron.

Zero-valent iron (ZVI) as a permeable barrier material for degradation of chlorinated organic compounds has been extensively studied recently. One of the focal areas in ZVI studies is to increase the contaminant reduction rate. In this research, batch tests were performed to evaluate the synergistic effect of sorbed cationic surfactants on degradation of perchloroethylene (PCE). Sorption of cationic surfactants on ZVI was a function of hydrophobic chain length of the surfactanttail group. Minimal counterion sorption indicated that the sorbed surfactant molecules form a patchy monolayer on ZVI. Both PCE and trichloroethylene (TCE) degradation by ZVI with and without sorbed surfactant followed pseudo-first-order reaction kinetics. In general, the PCE degradation rate increases as the chain length of sorbed surfactant increases. Compared to unmodified ZVI, both apparent rate constants of PCE degradation and TCE accumulation increased by an order of magnitude when ZVI was modified by hexadecyltrimethylammonium. The rate of PCE degradation by ZVI modified to lower surfactant loading was relatively higher than that by ZVI modified to higher surfactant loading. It was speculated that longer chain length will result in better admicelle formations, and thus, promote PCE partition and increase PCE surface concentration or surface admicelle catalysis, while low surfactant loading makes significant amounts of surface reduction sites still available. The PCE reduction rate constants were not affected by solution ionic strength, but high initial solution pH, buffered by sodium carbonate and sodium bicarbonate, significantly reduced the PCE degradation rate.

Cations↗
PubMed2001

Regeneration of perchlorate (ClO4-)-loaded anion exchange resins by a novel tetrachloroferrate (FeCl4-) displacement technique.

Selective ion exchange is one of the preferred treatment technologies for removing low levels of perchlorate (ClO4-) from contaminated water because of its high efficiency and minimal impact on water quality through the addition or removal of chemicals and nutrients. However, the exceptionally high affinity of ClO4- for type I anion-exchange resins makes regeneration with conventional NaCl brine extremely difficult and costly for practical applications. The present study entails the development of a novel regeneration methodology applicable to highly selective anion-exchange resins. Tetrachloroferrate (FeCl4-) anions, formed in a solution of ferric chloride and hydrochloric acid (e.g., 1 M FeCl3 and 4 M HCl), were found to effectively displace Cl04- anions that were sorbed on the resin. A mass-balance analysis indicated that a nearly 100% recovery of ion-exchange sites was achieved by washing with as little as approximately 5 bed volumes of the regenerant solution in a column flow-through experiment There was no significant deterioration of the resin's performance with respect to ClO4- removal after repeated loading and regeneration cycles. Thus, the new methodology may offer a cost-effective means to regenerate ClO4- -loaded resins with improved regeneration efficiency, recovery, and waste minimization in comparison with conventional brine regeneration techniques.

Anion Exchange Resins↗
PubMed2001

Formation of chloropyromorphite in a lead-contaminated soil amended with hydroxyapatite.

Conversion of soil Pb to pyromorphite [Pb5(PO4)3Cl] was evaluated by reacting a Pb contaminated soil collected adjacent to a historical smelter with hydroxyapatite [Ca5(PO4)3OH]. In a dialysis experiment where the soil and hydroxyapatite solids were placed in separate dialysis bags suspended in 0.01 M NaNO3 solution a crystalline precipitate, identified as chloropyromorphite, formed on the dialysis membrane containing the soil. The aqueous composition of the solution indicated that dissolution of solid-phase soil Pb was the rate-limiting step for pyromorphite formation. Addition of hydroxyapatite to the soil caused a decrease in each of the first four fractions of sequential extractable Pb and a 35% increase in the recalcitrant extraction residue. After a 240-d incubation at field-moisture content there was a further increase in the recalcitrant extraction residue fraction of the hydroxyapatite-amended soil to 45% of the total soil Pb. The increase in the extraction residue fraction in the hydroxyapatite amended 0-d incubated soil as compared to the control soil illustrates that the chemical extraction procedure itself caused changes in extractability. Thus, the chemical extraction procedure cannot easily be utilized to confirm changes occurring in amended soils. The further increase after the 240-d incubation implies that the reaction also occurs in the soil during incubation. Extended X-ray absorption fine structure (EXAFS) spectroscopy indicated that after the 240-d incubation the hydroxyapatite treatment caused a change in the average, local molecular bonding environment of soil Pb. Low-temperature EXAFS spectra (chi data and radial structure functions--RSFs) showed a high degree of similarity between the chemical extraction residue and synthetic pyromorphite, providing additional evidence that the change of soil Pb to pyromorphite is possible by simple amendments of hydroxyapatite to soil.

Absorptiometry, Photon↗
PubMed2001

Effects of quartz addition on the mechanochemical dechlorination of chlorobiphenyl by using CaO.

Grinding a mixture of 3-chlorobiphenyl (BP-Cl) and CaO with or without the addition of quartz was conducted in air by a planetary ball mill to investigate the mechanochemical dechlorination of BP-Cl. The dechlorinating reaction proceeds with an increase in grinding time, and over 99% of BP-Cl is decomposed at 360 min. Washing the ground sample with different solvents results in different products. Addition of quartz to the grinding mixture facilitates dechlorination efficiency, especially in the case of a high weight ratio of BP-Cl to CaO.

Biomechanical Phenomena↗
PubMed2001

Kinetic modeling of homogeneous mercury oxidation: the importance of NO and H2O in predicting oxidation in coal-derived systems.

This paper develops and evaluates an elementary reaction mechanism for homogeneous Hg0 oxidation that accounts for major interactions among Cl-species and other pollutants in coal-derived exhausts. Most importantly, interactions among NO and Cl-species were found to exert a strong and previously unrecognized impact on homogeneous Hg0 oxidation under some but not all conditions. The proposed oxidation mechanism is subjected to quantitative evaluations against all the available laboratory datasets that characterize homogeneous Hg0 oxidation when HCl is the primary chlorinated species. The simulations depict the reported extents of oxidation for broad ranges of HCl and temperature within useful quantitative tolerances without any heuristic parameter adjustments. The predicted pool of Cl-atoms was found to be governed by the chemistries of moist CO oxidation, Cl-species transformations, and NO production. However, an artificial initiation scheme was needed to depict the temperature dependence observed in one set of literature data. This indicates that either the kinetic mechanisms are incomplete or that heterogeneous initiation came into play under these test conditions. The evaluations further show that Hg oxidation is primarily through a Cl atom recycle process, with Cl and Cl2 concentrations both playing an important role. Oxygen weakly promotes homogeneous Hg oxidation, whereas moisture is a stronger inhibitor. NO can promote or inhibit homogeneous Hg oxidation, depending on its concentration. In the presence of NO, extents of Hg oxidation increased for progressively faster quenching. Conversely, without NO, extents of oxidation diminished for faster quenching.

Air Pollutants↗
PubMed2001

Disinfection byproduct relationships and speciation in chlorinated nanofiltered waters.

The formation and speciation of disinfection byproducts (DBPs) resulting from chlorination of nanofilter permeates obtained from various source water locations and membrane types are examined. Specific ultraviolet absorbance and bromide utilization are shown to decrease following nanofiltration. Both dissolved organic carbon (DOC) concentration and ultraviolet absorbance at 254 nm were found to correlate strongly with trihalomethane (THM), haloacetic acid (HAA), and total organic halide (TOX) concentrations in chlorinated nanofilter permeates, suggesting that they can be employed as surrogates for DBPs in nanofiltered waters. Because smooth curves were obtained for individual THM and HAA species as well as bromine and chlorine incorporation into THMs and HAAs as a function of Br-/DOC molar ratio, it is likely that mole fractions of these DBPs are more strongly influenced by chlorination conditions, Br-, and DOC concentrations than NOM source and membrane type. Mole fractions of mono-, di-, and trihalogenated HAAs were found to be independent of Br-/DOC. Even at a very low Br-/DOC of 2.9microM/mM, the mixed bromochloro- and tribromoacetic acids constituted 20% of total HAAs on a molar basis. This increased to approximately 50% as Br-/DOC increased to approximately 25microM/mM or more, proving that a large fraction of HAAs may not be covered under existing federal regulations. Total THM and HAA9 concentrations decreased in permeate waters with increasing Br-/DOC suggesting that nanofilter permeates are limited with respect to DBP precursors.

Absorption↗
PubMed2002

Carbon tetrachloride transformation in a model iron-reducing culture: relative kinetics of biotic and abiotic reactions.

Contributions of biotic (cell-mediated) and abiotic (mineral-mediated) reactions to carbon tetrachloride (CT) transformation were studied in a model iron-reducing system that used hydrous ferric oxide (HFO) as the electron acceptor, acetate as the substrate, and Geobacter metallireducens as a representative dissimilative iron-reducing bacteria (DIRB). Over a period of 2-3 weeks, nanoscale magnetite particles, Fe3O4, were consistently formed as a product of iron respiration in this system. CT transformation rates were measured independently in resting cell suspensions of G. metallireducens or in suspensions of washed magnetite particles recovered from spent cultures. Protein and surface area-normalized expressions were derived for the biotic and abiotic reaction rates, respectively. Using the yield of total protein and magnetite surface area formed during growth in the model system as a basis for comparison, the mineral-mediated (abiotic) reaction was estimated to be 60-260-fold faster than the biotic reaction throughout the incubation period. We conclude that G. metallireducens induces CT transformation in this system primarily through the formation of reactive mineral surfaces rather than via co-metabolic mechanisms. The findings indicate that reactive biogenic minerals could play a significant role in the natural attenuation of chlorinated solvents in iron-reducing environments. A novel approach for stimulating reductive transformation of contaminants may be to enhance the formation of reactive biogenic minerals in situ.

Biotransformation↗
PubMed2002

Assessment of chlorinated dibenzo-p-dioxin and dibenzofuran trends in sediment and crab hepatopancreas from pulp mill and harbor sites using multivariate- and index-based approaches.

Mill process changes and source controls instituted in the late 1980s at pulp and paper mills along the British Columbia (BC) coast produced dramatic reductions in both the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and the TEQ (2,3,7,8-TCDD toxic equivalents). Nevertheless, questions remained as to whether the sediments were acting as contaminant sources or sinks, whether crab uptake pathways have stayed the same since the mills ceased producing PCDD/Fs, and whether improvement was faster at some sites than others. To examine the processes governing the changes in PCDD/F composition, PCDD/F sources and compositional trends for the coastal BC sites were interpreted using sediment and crab PCA (principal components analysis) models and two indices based on the three main groups of PCDD/Fs that covary in all PCA models. One index measured the relative inputs of chlorine bleaching PCDFs and PCP (pentachlorophenol)-related PCDDs at each mill and harbor site whereas the other measured the relative inputs of PCP wood preservatives and pulp mill effluents. Results indicated that PCDFs produced during chlorine bleaching accumulate from sediments to crabs more readily than the PCDDs but that the chlorine bleaching TCDFs have generally decreased in importance at all mill sites. In the years just before 1995, little change was observed in either the proportion of toxic 2,3,7,8-chlorinated congeners or the PCDD/F concentrations, and the improvements seemed to have largely ceased by 1995. The lack of change in PCA composition for the harbors provided a further, disturbing indication that ecosystem recovery may have stalled. Results also implied that the main route of PCDD/Fs into crabs shifted from uptake via a pelagic food web incorporating effluent-borne PCDD/Fs associated with suspended particulate matter to uptake via a benthic food web.

Animals↗
PubMed2003

Formation of chlorinated aromatics by reactions of Cl*, Cl2, and HCl with benzene in the cool-down zone of a combustor.

Conversion of benzene to chlorobenzenes and monochlorophenols by reaction with chlorine radicals (Cl*) in the cool-down zone of a plug-flow combustor has been studied, and a mechanistic analysis of the initial steps of the oxy-chlorination process is proposed. Superequilibrium concentrations of Cl* are formed during combustion of chlorocarbon species and persist at significant concentration levels even after a substantial reduction in the flue gas temperature (T = 500-700 degrees C). At these temperatures, Cl* attack on benzene present in trace concentrations (initial benzene concentration of 300 ppmv or 1080 ppmv were used for the experiments) in the post-flame gas is shown to result in stable chlorinated products (chlorobenzenes and chlorophenols) and loss of benzene. These results suggest that Cl* attack on trace level aromatics and possibly other organic species may be the initial step in the formation of a broad class of chlorinated and oxy-chlorinated pollutants in the post combustion zone.

Air Pollutants↗
PubMed2001

Interpreting nonracemic ratios of chiral organochlorines using naturally contaminated fish.

Although reports of nonracemic proportions of chiral organochlorine pollutants in the environment are widespread, the interpretation of such data is not well developed. Using GC/MS and a chiral stationary phase consisting of 25% tert-butyldimethylsilylated beta-cyclodextrin in PS086 (beta-BSCD), we followed the change in the enantiomeric signature of 2-exo,3-endo,6-exo,8,9,10-hexachlorobornane (B6-923) in naturally contaminated fish maintained under toxaphene-free conditions. Whereas the enantiomeric ratio (ER) of B6-923 was near racemic at the start of the elimination experiment, it had increased severalfold by the end of 60 d. On the basis of first-order kinetics, one enantiomer of B6-923 was eliminated twice as fast as its mirror image, resulting in half-lives of 7 and 13 d, respectively. Enantioselective elimination by our test fish (Fundulus sp.) strongly suggests active biotransformation of B6-923; however, bioprocessing throughput estimates suggest a very low in situ rate of natural attenuation. These results confirm that the relatively constant ERs observed for chiral organochlorines in a given species are the result of competing processes, e.g., uptake vs elimination. Our experiments also further illustrate the utility of enantioselective analysis in characterizing the biotransformation of persistent organochlorine pollutants.

Animals↗
PubMed2003

Monitoring oxidation of chlorinated ethenes by permanganate in groundwater using stable isotopes: laboratory and field studies.

Permanganate injection is increasingly applied for in situ destruction of chlorinated ethenes in groundwater. This laboratory and field study demonstrates the roles that carbon isotope analysis can play in the assessment of oxidation of trichloroethene (TCE) by permanganate. In laboratory experiments a strong carbon isotope fractionation was observed during oxidation of TCE with similar isotopic enrichment factors (-25.1 to -26.8 per thousand) for initial KMnO4 concentrations between 67 and 1,250 mg/L. At the field site, a single permanganate injection episode was conducted in a sandy aquifer contaminated with TCE as dense nonaqueous liquid (DNAPL). After injection, enriched delta13C values of up to +204% and elevated Cl- concentrations were observed at distances of up to 4 m from the injection point. Farther away, the Cl- increased without any change in delta13C of TCE suggesting that Cl- was not produced locally but migrated to the sampling point Except for the closest sampling location to the injection point, the delta13C rebounded to the initial 613C again, likely due to dissolution of DNAPL Isotope mass balance calculations made it possible to identify zones where TCE oxidation continued to occur during the rebound phase. The study indicates that delta13C values can be used to assess the dynamics between TCE oxidation and dissolution and to locate zones of oxidation of chlorinated ethenes that cannot be identified from the Cl- distribution alone.

Chlorine Compounds↗
PubMed2002

Polychlorinated naphthalene levels, distribution, and biomagnification in a benthic food chain in the Baltic Sea.

The scientific literature contains little information regarding bioaccumulation and biomagnification of polychlorinated naphthalenes (PCNs) in food webs. Here we present new information on the food chain transfer of PCNs within a food chain in a subarctic environment PCNs (tetra- to hepta-chloro congeners) were measured in surface sediments and in a marine benthic food chain, comprising amphipods, isopods, and fourhorned sculpins. Samples were collected from five locations in the Gulf of Bothnia, northern Baltic Sea. PCN concentrations in the sediments were similar to background levels determined previously in sediments from the northern hemisphere. Measurement of the carbon content of the sediments allowed the calculation of biota to sediment accumulation factors (BSAFs). Tetra- and penta-CNs exhibited BSAF values greater than one, while BSAFs for the more chlorinated PCNs were less than one. This suggests more efficient assimilation, by amphipods, of the less chlorinated PCNs. A decrease in sigmaPCN concentrations from the lowest to the highest trophic level was demonstrated (amphipods: 10-69 ng/g lw, isopods: 3.9-16 ng/g lw; fourhorned sculpins: 0.54-1.5 ng/g lw). Biomagnification factors (BMFs) were calculated based on the concentrations of the congeners. These indicated that a few congeners biomagnified significantly: the highest BMFs (0.09-1.4) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms.

Amphipoda↗
PubMed2002

Effect of UV irradiation on organic matter extracted from treated Ohio River water studied through the use of electrospray mass spectrometry.

Ohio River water was treated by settling, sand filtration, and granular activated carbon filtration. It was then irradiated by low-pressure (monochromatic) and medium-pressure (polychromatic) UV lamps to investigate the effects of UV irradiation on the extracted organic matter (EOM). When the EOM, collected by solid phase extraction cartridges, was analyzed by conventional UV spectroscopy and size exclusion chromatography (SEC), no significant changes in the EOM were revealed for various UV doses. Positive and negative electrospray ionization mass spectrometry (ESI-MS) of the EOM produced mass spectra that vary significantly with UV dose. The UV dosage conditions also appear to affect the reactivity of the EOM to subsequent chlorination. The magnitude of the spectral changes is generally greater for medium-pressure lamps than for low pressure and increases with UV exposure. Based on the observed MS peaks, the changes may be due to the presence of lignin, resulting perhaps from photooxidation and/or photo rearrangement of macromolecules in the sample. When chlorination is used for secondary disinfection, these results suggest that it may be important to consider the effects of UV irradiation on the organic matter in the water before applying UV disinfection technology to a particular source water.

Chlorine Compounds↗
PubMed2002

Chlorine isotope fractionation during reductive dechlorination of chlorinated ethenes by anaerobic bacteria.

Chlorine isotope fractionation during reductive dechlorination of trichloroethene (TCE) and tetrachloroethene (PCE) to cis-1,2-dichloroethene (cDCE) by anaerobic bacteria was investigated. The changes in the 37Cl/35Cl ratio observed during the one-step reaction (TCE to cDCE) can be explained by the regioselective elimination of chlorine accompanied by the Rayleigh fractionation. The fractionation factors (alpha) of the TCE dechlorination by three kinds of anaerobic cultures were approximately 0.994-0.995 at 30 degrees C. The enrichment of 37Cl in the organic chlorine during the two-step reaction (PCE to cDCE) can be explained by the random elimination of one chlorine atom in the PCE molecule followed by the regioselective elimination of one chlorine atom in the TCE molecule. The fractionation factors for the first step of the PCE dechlorination with three kinds of anaerobic cultures were estimated to be 0.987-0.991 at 30 degrees C using a mathematical model. Isotope fractionation during the first step would be the primary factor for the chlorine isotope fractionation during the PCE dechorination to cDCE. The developed models can be utilized to evaluate the fractionation factors of regioselective and multistep reactions.

Bacteria, Anaerobic↗