Index

Abbotsford-Sumas regional sand and gravel aquifer, BMPs in, 222 Abiogenic systems, 169 Abiotic and biotic processes, distinguish between, 18 Accelerator mass spectrometry (AMS), 358 Acetate fermentation and CH4 production, 171-172 by Methanosaeta thermophila, 172 Aceticlastic methanogenesis, 170 Acetylene block method, 334 Acinetobacter sp., benzene degraded by, 149 Advection-dispersion theory, 50 Advective transport of water and NAPL, 297 Aerobic benzene biodegradation, 149 Aerobic biodegradation of chlorinated hydrocarbons, 149 and chemical transformation, 90, 101-108 formaldehyde assimilation, 150 isotope fractionation of, 150-151 Aerobic respiration by microorganisms, 131 Aerobic toluene degradation, 147 Aerobic vinyl chloride degradation, 151 Air sparging/soil vapor extraction (AS/SVE) system, CO2 concentrations, study, 371 Air-water partitioning coefficient, 305 AKIE, see Apparent kinetic isotope effect (AKIE)

n-Alkanes aerobic biodegradation and chemical transformation, 85 carbon isotope enrichments during, 85 biodegradation of, 98 Alliston aquifer, carbon source presence, 179 Amazon Basin floodplain, floating mats of

C4 grass, 188 Aminobacter, methyl halides degradation, 153 Ammonia volatilization, 212 AMS, see Accelerator mass spectrometry (AMS) tert-Amyl methyl ether (TAME), 99-100 Anaerobic naphthalene degradation, 98 Analytical isotope techniques, 300 Ancyclobacter aquaticus AD20, aerobic biodegradation of 1,2-DCA, 151-152

Animal waste, 815N values, 211-212

APE, see Atom percentage excess (APE) Apparent kinetic isotope effect (AKIE), 70 calculation of, 82 of chlorinated alkanes, 75 fractionation factor and, 76 values, 86 Assimilation, 206; see also Nitrogen Assimilatory bacterial sulfate reduction, 226 Atacama Desert in Chile, natural nitrate deposits, 211 Atomic weight, 6

Atom percentage excess (APE), 13, 338 Atoms, chemical behavior, 8-9 Autotrophic acetogenesis, 172 Autotrophic respiration, 131

Bacterial biomarkers in microbial mats, 141 Bacterial dissimilatory sulfate reduction, 226-228

Belemnitella americana fossil, 13C/12C from, 11 Beneficial management practices (BMPs), 205 Benzene aerobic benzene biodegradation, 149 degradation by

Acinetobacter sp., 149 Burkholderia sp., 149 82H values, 138 Biodegradation process, 3, 15 Biomarkers as hopanoids, 140 isotopic analysis, 140-141 Biomass isotopic composition change, 142 Bioremediation process, 15, 130 Biota, 813C isotopic values in, 135 Biotransformation process, 15 Boltzmann constant, 64 Bonds stiffness, 63; see also Equilibrium isotope effect (EIE) Born-Oppenheimer approximation, 9, 57 Brownian motion of molecules, 298 BTEX (benzene, toluene, ethylbenzene, xylene) compound, 30 biodegradation and, 147 carbon isotopes, detection limits for, 32 compound specific isotope analysis of, 139 813C values of, 137 degradation, 259 in groundwater, 232

as pollutants, 94-95, 137 split injection of CO2 and gaseous, 32 Bulk fractionation factor of chlorinated alkanes, 75 Bulk isotope fractionation factor, 81 Burkholderia sp. degradation benzene, 149 methyl halides, 344 n-hexadecane and naphthalene, 147

Calcium (Ca)

and biological fractionation, 399 double-spike TIMS technique, 398-399 G. sacculifer, isotope composition, 401 isotope fractionation, carbonate and seawater,

400-402 thermometer, use of, 400 low temperature isotopic studies, 399 metabolic and ecotoxicological implications for, 399-400 range of, 403 stable isotopes, 398 California site, radiocarbon signatures in groundwater DOC from, 369 Calvin (C3) cycle of photosynthesis, 134 Canonical partition function, 61-62; see also

Equilibrium isotope effect (EIE) Capacity factors, 300-301 Carbon, 335

13C-anthraquinone, 336

13Carbon contaminant studies, 336-337

cycle, 130

813C isotopic values for atmospheric and groundwater reservoirs, 135 equilibrium isotope effects, 63 isotopic fractionation during aerobic biodegradation of MTBE, 157 natural and artificial radioisotopes, 352-353 stable and radiocarbon isotope analysis, 351-352 Carbon and hydrogen isotope enrichment factors gasoline additives, 100 mono-and polyaromatic hydrocarbons and alkanes, transformation of, 99 fractionation during

MTBE transformation, 87 Carbonates analysis, 36 Carbon dioxide (CO2)

CO2-reduction pathway, 170 613C-CO2 values, 144 isotope composition change, 142

signature of, 143 variations of, 295 from soil organic matter, 295 Carbon isotopes aerobic degradation of perchloroethylene, 144 anaerobic biodegradation, 85 analysis, 18, 139, 141 composition, 188 data for, 180 detection limits for, 32 and dissolved CO2 in ground water, 17 enrichment factors and aerobic biodegradation and chemical transformation, 90, 101-108 biotic and abiotic transformation of chlorinated hydrocarbons, 90-91 evolution during dichloroelimination, 279 reactant and product, 278 fractionation, 92

and monooxygenation, 97 polyaromatic hydrocarbons, biodegradation of, 97-98 during vaporization, 54 models for description of, 295 o-xylene forms subdivision, 269 ratio of chlorinated hydrocarbons, 283 PCE downgradient of DNAPL source zone, 284-285 use, 280 at reactive positions, 299 separation, 186 as tracers, 7

during transformation of chlorinated ethenes, 281 Carbon tetrachloride (CT) biodegradation at contaminated field, 144 14C atmospheric production from 14N, 15 13C/"C ratio calculation of, 39 international standard for, 11 VPDB scale, 12 CERCLA, see U.S. Environmental Protection Agency's Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) Chemical and molecular tracer in radioisotope and stable isotope labeling studies, 19; see also Isotopes Chemical inhibition technique, 334 Chlorinated contaminants identification using dual isotopic analysis, 139 Chlorinated hydrocarbons aerobic biodegradation, 149

and chemical transformation, 90, 101-108 formaldehyde assimilation, 150 isotope fractionation of, 150-151 transformation, isotope fractionation of chlorinated, 87 benzenes, 94 ethanes, 93 ethenes, 88-89 methanes, 93-94 Chlorine (Cl)

chlorinated solvents to natural environments, release, 395 cis-1,2-dichloroethene (cDCE), 398 dichloromethane (DCM), 397

613C values, 398 isotope composition of materials determination, 397 kinetic isotope fractionation factors for,

397-398 PCB extraction, 398 range of, 396

theoretical isotope fractionation relations for, 395

TIMS and IRMS instrumentation, 395 Chlorine isotopes ratio, 283 Chloroflexus growth by photoheterotrophy, 141 Chromium (Cr)

cosmochemical studies, 405 groundwater, values in, 405-406 isotope fractionation during, 406 Clastic rocks and sediments, 87Li values, 393 37Cl/35Cl ratio international standard for, 12-13 CND, see Coupled nitrification-denitrification (CND) Coet-Dan catchment, groundwater study in, 217 Combined isotopic analysis of 13C and 18O, 158 Cometabolism, 131-132

Commission of International Union of Pure and Applied Chemistry (IUPAC) isotopic compositions of elements, 11 Compound analysis in environment, 17; see also Isotopes

Compound-specific isotope analysis (CSIA), 139 coupling with gas chromatography (GC), 27-30 liquid chromatography, 30 organic contaminants in field, biodegradation of, 144 attenuating processes, 145 enzymatic reaction, 146 isotopic fractionation, 145 physical processes and biodegradation, distinguish between, 146

sample preparation, 30-32

sampling and preservation, 32-33

Concentration-based methods, 267 Conservative tracer concentration, 258 Contaminants carbon isotopic composition in, 137 chlorinated contaminants identification, 139 degradation, isotope trends during, 250 mass flux of, 266-267 nitrate, 204 sources of, 138-139 Contaminated environments radiocarbon and stable carbon studies, 366 combined 14C and 13C analysis for gaseous end products, 367-377 combined 14C and 13C analysis for specific contaminants, 367-378 Continuous-flow isotope ratio mass spectrometry (CF-IRMS), 26 development and testing, 36-38 uncertainties for, 38 Correction multiple reactive sites, 74 for nonreactive positions, 72-74 Cosmic rays, 14C from 14N atmospheric production, 15 Coupled nitrification-denitrification

(CND), 332 C3 plants photosynthetic pathways, 134-135 Cross-calibrated standards for oxygen isotopes, 34 Current Opinions in Biotechnology, 341

Dehalococcodies sp., trichlorobenzene degradation, 154 Dehalorespiration, 88 Delta-notation for stable isotope, 10-13 Denaturing gradient gel electrophoresis

(DGGE), 343 Denitrification, 207; see also Nitrogen Thiobacillus denitrificans and, 208 DGGE, see Denaturing gradient gel electrophoresis (DGGE) Diatomic molecule, potential energy, 58-59 DIC, see Dissolved inorganic carbon (DIC) Dichloroelimination of 1,1,2-trichloroethane

(1,1,2-TCA) evolution, concentration and carbon isotope, 279 Dichloroethene (DCE), 88

1,2-dichloroethane (1,2-DCA)

aerobic biodegradation pathways, 152 Ancyclobacter aquaticus AD20, biodegradation by, 151-152 bimodal distribution of, 153 biodegradation, 93 Xanthobacter autotrophicus, biodegradation by, 151-152

cis-1,2-dichloroethene (cDCE) isomer, 88

PCE and TCE dechlorination, 398 1, 1-dichloroethene (1,1-DCE), 88 Dichloromethane (DCM), 397 degradation, 154 613C values, 398 Diesel degradation, 159

Diffusion coefficient in liquids by power law, 52-53 Diffusion-dominated transport of subspecies, 305 Diffusion models, 308-309 Diffusion-reaction models, 295 DI-IRMS, see Dual inlet isotope ratio mass spectrometer (DI-IRMS) Dilution of isotope fractionation, 81-84 DIN, see Dissolved inorganic nitrogen (DIN) Dispersion coefficient, 51; see also Fractionation of isotopes Disproportionation of elemental sulfur, 229 Dissimilatory nitrate reduction to NH4+

ammonium (DNRA), 209; see also Nitrogen

Dissimilatory reduction (DIR), 412 Dissolved inorganic carbon (DIC), 178, 354-355

analysis, 36 Dissolved inorganic nitrogen (DIN), 332 Dissolved organic carbon (DOC), 178, 354-355 Dissolved organic matter (DOM), 136 Dissolved oxygen analysis, 36 Dissolved (sMMO), 150; see also Methane monooxygenases (MMO) Dissolved organic carbon/total organic carbon

(DOC/TOC) analyzer, 27 DNA-SIP process, 341-343; see also Stable isotope probing (SIP) DNRA, see Dissimilatory nitrate reduction to

NH4+ ammonium (DNRA) DOC, see Dissolved organic carbon (DOC) DOC/TOC, see Dissolved organic carbon/total organic carbon (DOC/TOC) analyzer Dole effect, 296, 314 Double-spike TIMS technique, 398-399 Dual inlet isotope ratio mass spectrometer

(DI-IRMS), 25 Dual isotopic analysis, 139 Dual-labeled amino acid, 339 Dual-labeled substrate technique, 340

Elemental analyzer-isotope ratio mass spectrometer (EA-IRMS) for C, N and S isotope analysis, 33-34 Earth's crust bulk-earth composition, 399 87Li value, 393

634S value, 223 freshwater wetlands, 185 microbial activity within, 169 natural organic and inorganic carbon, isotopic compositions of, 130 nitrogen abundance, 205 c/s-radioisotopes use for dating, 353 Ebullition, 189

EIE, see Equilibrium isotope effect (EIE) Electron energy, 57

Elemental sulfur disproportionation, 229 Elements defined, 5

isotopic composition measurement, 24 Elk River Valley, microbial origin for CH4, 181 Ellergower Moss 813C values of dissolved CO2

and CH4 in, 186 End-member mixing model, 362-363 Enrichment factors for kinetic isotope effect, 303 Enskog kinetic theory, 52 Environmental systems aerobic biodegradation, 141-144 isotope application in, 129-131 soil and sediment, 149-150 aquatic carbon sources in, 136 aquifers in urban and rural, 213 carbon isotopes at reactive positions in, 299

chlorinated methanes as pollutants, 93-94 fate of pollutants in, 5 hazards associated with landfills, 181 isotopes abundances of, 355 defined, 3 isotopomers in, 7 marine and freshwater, 172 methanogenic pathway in, 170 microorganisms in, 328 14N and 15N, 7 N-contaminated, 335 nitrate contamination, 215 nitrogen cycling in, 331 organic compounds in, 43 organic matter in anoxic, 170 pollutants, degradation pathways of, 18 radiocarbon, 359-361

and stable carbon isotopes in contaminated, 366-377 and stable carbon isotopes in uncontaminated, 361-366 radioisotopes use for studies, 6 radiolabeled chemicals, release of, 328-329 radionuclide concentrations, 14 stable isotope analysis in, 329

terrestrial and marine, methane in, 168-169 tracers in, 7

tritium activities, 15

water-unsaturated/saturated, 226 Equilibrium isotope effect (EIE), 44, 298 approximation, 62 bond properties, 63 stiffness and, 64 canonical partition function, 61 equation for, 62

ZPE and, 61 ETBE, see Ethyl tert-butyl ether (ETBE) Ethylcobalamin, 92 Ethyl tert-butyl ether (ETBE), 99-100 Euxinic sediments, Mo isotope in, 420 EXC, see Excitation of higher-energy vibrational levels (EXC) Excitation of higher-energy vibrational levels (EXC), 62

Faraday cups, 24

Fassel-type torch, 390; see also Multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) Fick's law, 298

First-order kinetic rate law, 301 Floridian coastal aquifer, source of water for recharge, 365 Fluoranthene biodegradation, 97-98 Foraminiferal species, 400 Formaldehyde assimilation, 150; see also

Chlorinated hydrocarbons Fractionation of isotopes expression and quantification enrichment factor, 46 expression and quantification factor of, 45

first-order rate expressions, 47 linearized form, 49-50 Rayleigh equation, 48 magnitude, factors affecting, 80 dilution of, 81-84 masking of, 84 reaction mechanisms, 85-87 phase transfer processes during, 53-56 principles and mechanisms, 43-44 transformation processes during, 53-54 case study, 74-75

energies inherent in molecules, 57-59 equilibrium isotope effect (EIE), 61-64 fractionation factors estimation, 75-76 heavy isotopes position corrections, 71-74

kinetic isotope effect (KIE), 64-71

molecular energy during reaction, changes in, 59-61 during transport process advection and dispersion, 50 dispersion coefficient, 51 Freundlich sorption isotherm, 300 Fungi use in enzymatic degradation pathways, 131

Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), 5 sample extraction methods in, 31 Gaseous ammonia, 815N values, 211 Gaseous compounds in unsaturated zone isotopes analytical reactive transport models, 305-306

boundary conditions, 306-307, 310

compositions, 295-297

compound properties and division into subspecies, 302-304 diffusion and degradation, fractionation factors for, 304-305 implementation of model, 311 model, 301 steady-state diffusion of VOC curtain source with first-order degradation, 315-316 from saturated zone to atmosphere with first-order degradation, 314-315 steady-state O2 flux into biotic sand mesocosm with zero-order degradation, 313-314 transient CO2 diffusion in abiotic sand column, 311-313 transient diffusion of VOC

from spherical source with first-order degradation, 316-317

Gasoline additives transformation, isotope fractionation during, 99-100 biodegradation, 143 MTBE as antiknocking agent in, 99 source zone and contaminant plume, 260 Gas-phase diffusion, 297-298 and degradation, effect on isotopic signals in gaseous compounds in unsaturated zone, 318 Gas transport mechanisms, 188-189 Gas-water interface, 300 GC-C-IRMS, see Gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS)

The Geochemistry of Non-Traditional Stable

Isotopes, 386 Gibbs reaction enthalpies, 59 Ginkgo biloba and 813C values, 135 Global carbon cycling models, 296 Globigerinoides sacculifer, calcium isotope composition, 400-401 Grand Cayman Island, 815N-NO3 values, 215 Gravity-driven advection, 297 Groundwater BTEX in, 330 carbonates in, 362 carbon cycle and, 130 14C in CH4 activity from landfills, 183 contaminant chlorinated solvents, 356 gasoline, 143

microbial degradation, 130 organic, 131 plumes in, 19 contamination anthropogenic chemicals by, 15 evaluation by isotopes, 287 Cr plumes, 405 S13C-DIC of, 143-144 denitrification studies in, 208 deuterium concentration in, 330 discharge rates and redox conditions, 280 dissolved chloroethene in, 17 dissolved CO2 in, 17 dissolved oxygen concentrations, 375 S7Li values, 393 S15N-NO3 values, 214 environmental impact of agricultural nutrients on, 222 Fe isotope, 413 flow velocity, 50-51

using Darcy's Law, 264 LNAPL floating on, 314 methane in, 177-179 MTBE in, 18 nitrate, 205, 212

attenuation, 216-219 denitrification studies in, 208 as indicator of contamination, 365 industrial and organic fertilizers, 213 industrial processes and sources, 212, 216 nitrogen cycle in, 209 N2O concentrations, 209 sewage, 215-216 sewage, impact of, 215-216 soil nitrogen, 214-215 surface water interaction, 219-221 origin and age, 356 oxidation in, 178 oxygen isotope composition, 223 petroleum sources in, 319

Rayleigh equation in, 18

retardation factor, organic carbon content, 264

sulfate in, 230

transport and reaction in one dimension flowing, equation for, 269 tritium concentrations in, 15

Hansenula polymorpha, chlorinated aliphatic hydrocarbons degradation, 153 Hatch-Slack (C4) photosynthetic pathway, 134 Heavy isotope presence effect on diffusion coefficient of organic compounds, 53 Heisenberg's uncertainty principle, 57 Henry's law, 300 Heterotrophic respiration, 131 Heterotrophy, 141 Hexachloroethane (HCA)

dichloroelimination, 93 n-Hexadecane degradation by Burkholderia sp.

BS3702, 147 steady-state diffusion, 315 Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in soil, 18

2H/1H and 18O/16O ratio international standard for, 12 High performance liquid chromatography (HPLC) system with IRMS, 27 Hopanoids as biomarkers, 140 Hydrocarbons, isotope fractionation due to gas-phase diffusion, 52 Hydrogen isotopes analysis of chlorinated solvents, 138 fractionation, 155

during aerobic biodegradation of MTBE, 157 ratio of chlorinated hydrocarbons, 283 Hyphomicrobium, methyl halides degradation, 153

IAEA International Atomic Energy Agency (IAEA)

international standards for stable isotope, 10-11 ICP-MS, see Inductively coupled plasma mass spectrometers (ICP-MS) Immobilization, 226-227 Indiana site, 813C-CO2 values, 181 Inductively coupled plasma mass spectrometers (ICP-MS), 390 MC-ICP-MS, 391 Industrial and organic fertilizers, 213 Instrumental mass bias methods, 390

Instrumentation accelerator mass spectrometry (AMS), 358 compound-specific isotope analysis (CSIA), 139 continuous-flow isotope ratio mass spectrometry (CF-IRMS), 26 dual inlet isotope ratio mass spectrometer

(DI-IRMS), 25 gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), 5 high performance liquid chromatography

(HPLC) system with IRMS, 27 inductively coupled plasma mass spectrometers (ICP-MS), 390 MC-ICP-MS, 391 isotope ratio mass spectrometers (IRMSs),

24, 387-388 mass bias correction in multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), 391 mass spectrometry (MS), 388-390 Internal normalization of isotope ratios, 390; see also instrumental mass bias International references and abundance ratios of stable isotopes, 11 International Union for Pure and Applied

Chemistry, 393 Intrinsic isotope effect, 70 Inverse isotope effect, 54, 298 IRMSs, see Isotope Ratio Mass

Spectrometers (IRMSs) Iron (Fe) isotope data, 406

measurements, 406-407 microbiological pathways dissimilatory reduction (DIR), 412 fractionation in higher order organisms, 411 iron oxidation, effects of, 413-414 iron oxides and fluids, composition, 414-415

origin experimental results for, 409 fractionation between, 408-409 oceanic crust, composition of, 410 partial dissolution experiments, 409-410 pyrite prediction, 408 redox processes, experiments and calculation methods, 410-411 stable isotope compositions for, 407 Isotope ratio mass spectrometers (IRMSs), 24, 387-388 instrumental mass fractionation (mass bias), 389

Isotopes aerobic environments, application in, 129-131

analysis of bulk samples, 33-36 principle, 24-25 13C/12C abundance ratio, 9 chemical compounds, distribution in, 7 concentration and isotope evolution, 258 data interpretation, 288 discovery of, 4-5 enrichment factors, 82, 259

biotic and abiotic transformation of gasoline additives, 116-117 biotic transformation of aromatic and aliphatic hydrocarbons, 109-115 fractional abundance of, 39-40 fractionation enrichment factor, 46 factor of, 45

first-order rate expressions, 47 linearized form, 49-50 magnitude, factors affecting, 80-87 phase transfer processes during, 53-56 principles and mechanisms, 43-44 Rayleigh equation, 48 transformation processes during, 54, 57 transport process during, 50-53 information types, 17-19 measurement of, 16 measurements, 3 nuclide chart of, 6-7 pairing technique, 335 product evolution, 277-278 ratios calculation, 38-40 evolution of, 49 quantitative evaluation of, 259 techniques, 5 Isotopic composition method, 390; see also

Instrumental mass bias Isotopologues, 7

of 1,3-dichloropropane, 72 Isotopomers, 7

IUPAC, see Commission of International Union of Pure and Applied Chemistry (IUPAC)

KIE, see Kinetic isotope effect (KIE) Kinetic isotope, 387 fractionation, 301 Kinetic isotope effect (KIE), 44, 80; see also Apparent kinetic isotope effect (AKIE) expression of, 64-65 magnitude of, 66-69 partition functions, 64 position-specific isotope fractionation factors, 76

ranges for, 68 rate laws, effect of, 69-71 Streitwieser semiclassical limits, 67 values, 86 Kinetic isotope theory, 151

Landfilling, 181-185 Leachate in modern landfills, 183 Landfill gases, 132 Linear partition coefficient, 300 Liquid-phase diffusion, 298 Lithium (Li) isotope anthropogenic sources, 393 distributions, 392 mid-ocean ridge basalts (MORBS) range of, 393-394 Lithospheric sulfur in sedimentary rocks, 225 Livermore Valley, groundwater study, 215 Long-term changes evaluation in management practices, 221-222 Low temperature isotopic studies, 399 Lysobacter, methyl halides degradation, 344

Maple 9.01 software, 310

Masking of isotope fractionation, 84-85

Mass and moments of inertia (MMI), 62

Mass balance approach, 133

Mass bias correction in multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), 391 Mass flux reduction, 258 Mass-independent reactions, 387 Mass number, see Atomic weight Mass spectrometry (MS)

thermal ionization, technique, 388-389 types, 388

ICP-MS, 390-391 IRMSs, 389 TIMS, 389-390 Mathematical model for profiles of 818O in O2, 296

MC-ICP-MS, see Mass bias correction in multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) Meadows area, nitrate concentrations in, 217 Mechanical dispersion, 50 Medical tracer studies of human physiology, 13 Methane (CH4)

and anthropogenic greenhouse gas emissions, 168 in atmosphere, 167-168

613C values of, 173 82H values of, 174-177 in environmental systems coalbeds, 180-181 groundwater, 178-179 landfills, 181-185 wetlands, 185-189 global and anthropogenic sources, 168 isotopic values, 373 methanogenic pathways, 170-173 in anoxic environments, 173 C and H isotopes, 174-177 oxidation in natural systems, 178 production abiogenic/geological, 169 acetate fermentation, 171-172 microbial, 169-170 radiocarbon and, 177 total global (Tg) budget of flux, 168 Methane monooxygenases (MMO), 150 C-isotope fractionation during methanotrophy, 178 Methanosaeta thermophila, acetate fermentation by, 172 Methanotrophic bacteria serine and ribulose monophosphate pathways, 150 trans-1,2-dichloroethylene (t- DCE)

degradation, 152 trichloroethylene biodegradation, 151 Methylcyclohexane grouping, 302-303 Methyl halides degradation by, 154

Burkholderia sp., 344 Hyphomicrobium, 153 Methylobacterium, 153 Nocardiodes, 344 Methylobacterium, methyl halides degradation, 153 Methylomonas methanica Oak Ridge, t-DCE

degradation, 152 Methylosinus trichosporium OB3b, t-DCE

degradation, 152 2-Methylphenanthrene biodegradation, 97-98 Methyl tertiary-butyl ether (MTBE), 33 aerobic biodegradation of carbon and hydrogen isotope analysis, 155 carbon isotopic fractionation during, 157 613C and 62H data from, 157-158 hydrogen isotopic fractionation during, 157 metabolic pathway, 155-156 as antiknocking agent in gasoline, 99 biotic and abiotic transformation mechanisms, 86

carbon and hydrogen isotope fractionation during transformation, 87 as contaminants in environment, 137 degradation under oxic and anoxic conditions, 267 and diffusive isotope fractionation, 53 dual isotope plot for aerobic and anaerobic biodegradation, 268 in groundwater, 18 isotope fractionation pattern, 80 vaporization, 54 Michaelis-Menton kinetics, 147 Mid-ocean ridge basalts (MORBS) Li isotopes, range of, 393-394 Millington-Quirk relationship, 306 Mineralization, 226-227 MMI, see Mass and moments of inertia (MMI) MMO, see Methane monooxygenases (MMO) Modern carbon (mC), 14 Moldrup relationship, 306 Molybdenum (Mo) isotope environmental research, 415-416 fractionation processes effects during, 418-419 in seawater and ferromanganese, 418 small magnitude between, 419 isotope systematics, 416

natural mass dependent, 416-417 natural variations in in seawater, 418 warm fluids emerging, 417-418 stable isotope compositions for, 417 synthesis and applications ancient ocean redox variations, study, 419-420 biological utilization, studies of, 420-421 caveats, 419 paleorecords, 420 variations in oceanographic settings crustal materials, 417 Mono-and polyaromatic hydrocarbons transformation, 95-96 Monod kinetics, 301

MORBS, see Mid-ocean ridge basalts (MORBS) MTBE, see Methyl tertiary-butyl ether (MTBE) Multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS), 388-389 main parts, 390 Multistep sorption/desorption cycles, 300 Multistep transformation, 278-280

Naphthalene biodegradation, 97-98

degradation by Burkholderia sp. BS3702, 147

NAPL, see Nonaqueous phase liquid (NAPL) National Institute of Standards and Technology (NIST) international standards for stable isotope, 10-11 Natural abundance measurements, 334 Natural nitrate deposits in Atacama Desert in Chile, 211

Natural systems, natural organic matter in, 134 15N-DON and 13C uptake in plant roots and shoots, 339-340 Nebulizer, 390; see also Multicollector inductively coupled plasma mass spectrometer (MC-ICP-MS) Net ecosystem productivity (NEC), 188 NIST, see National Institute of Standards and

Technology (NIST) Nitrification, 206-207; see also Nitrogen Nitrogen case studies in groundwater nitrate attenuation in, 216-219 sources of nitrate in, 212-216 surface water interaction with, 219-221 compounds, isotopic composition of, 210 cycle assimilation, 206 denitrification, 207-208 dissimilatory nitrate reduction to NH4+

ammonium (DNRA), 209 in environment, 332 isotope pairing technique, 335 N2:Ar method, 335 nitrification, 206-207 nitrifying bacteria in, 334 nitrous oxide, 209 isotope fingerprint of nitrate sources animal and domestic waste, 211-212 fertilizers, 210-211 soils, 210 isotope fundamentals, 205 nitrate as contaminants, 204 in aquifers, 205 attenuation, 216-219 denitrification studies in, 208 in groundwater, 205 as indicator of contamination, 365 industrial and organic fertilizers, 213 industrial processes and sources, 212, 216 nitrogen cycle in, 209 N2O concentrations, 209 818O and 815N values, relationship between, 211 sewage, impact of, 215 -216 soil nitrogen, 214-215 surface water interaction, 219-221 13N, 331

nitrogen-fixing vegetation, 214

Nitrous oxide, 209; see also Nitrogen 15N/14N ratio international standard for, 12 Nocardiodes, methyl halides degradation, 344 Nonaqueous phase liquid (NAPL), 296 Nontracer technique, 334 Nottingham city aquifer study, 217 15N pool dilution technique, 330 Nuclides, 6

as tool for archeological dating, 14 NW Black Sea slope carbonate chimneys, radiocarbon age, 363

Octanol-water partition coefficient, 32, 137 Old Banford area, nitrate concentrations in,

215-216 One-dimensional diffusion, 318 Ontario wetland, Canada, nitrate attenuation in, 220 Orbulina universa, abiotic carbonate precipitation, 400 Organic compounds, isotopic composition atmospheric CO2, 132-133 environmental organic contaminants, 137-138

natural organic matter (OM ), 133-136 Organic contaminants in field biodegradation, 144; see also Compound-specific isotope analysis (CSIA) attenuating processes, 145 isotopic fractionation, 145 physical processes and biodegradation, distinguish between, 146 Organic matter (OM) microbial respiration, 130 Organism-specific amino sugars ratio, 338 Oxalic acid, 357; see also Radiocarbon Oxidoreductases, 132 Oxygen isotope chemical and bacterial oxidation of sulfur compounds, 228 Oxygen isotopes cross-calibrated standards for, 34

Particulate organic carbon (POC), 364 Particulate (pMMO), 150; see also Methane monooxygenases (MMO) PDB, see Pee Dee Belemnite (PDB) Pee Dee Belemnite (PDB), 11 Pentachloroethane (PCA)

dehydrohalogenation, 93 Percent modern carbon (pMC), 14

units of, 358 Periodic table of elements, 6

Petroleum-contaminated aquifer

14C and 13C CO2, inverse correlation between, 373 Petroleum hydrocarbons, 355 aerobic biodegradation, 146

marine bacterial degradation, 147 anaerobic degradation study radiocarbon and stable carbon isotopes using, 371 S13C values, 137

transformation, isotope fractionation during, 94-95

monoaromatic hydrocarbons, 96-97 n-alkanes and cyclic alkanes, 98-99 polyaromatic hydrocarbons, 97-98 Phase transfer processes, 32 Phosphoenolpyruvate (PEP) carboxylase, 134 Phospholipids fatty acids (PLFAs), 341

as biomarkers, 140 Photoheterotrophy, 141 Planck constant, 64 Plating techniques, 337 PLFAs, see Phospholipids fatty acids (PLFAs) POC, see Particulate organic carbon (POC) Pollutant degradation from natural process, 17;

see also Isotopes Polychlorinated biphenyls (PCBs), 137 Polycyclic aromatic hydrocarbons (PAHs) anaerobic biodegradation, 97-98 as contaminants, 137 S13C values, 137 in sediment, 378 Position-specific isotope fractionation factors, 76 Potential energy profile, 60 Potentially responsible party (PRP), 138 Poultry manure stockpile, S15N values, 212 Pressure-induced advective soil gas transport, 297 Primary kinetic isotope effect, 130; see also

Kinetic isotope effect (KIE) Pseudomonas putida contaminant identification, 132

phenol and benzoate fractionation, 141-142

P51, 1,2,4-trichlorobenzene (TCB) aerobic biodegradation, 94 strain F1, aerobic toluene degradation by, 147 strain mt-2, aerobic toluene degradation by, 147 Pyrite oxidation experiments, 231 Pyrolysis IRMS (PY-IRMS) for O and

H isotope analysis, 34 Pyrolysis with stable isotope analysis, 34

Radioactivity, 357 Radiocarbon in atmosphere, concentrations, 359 and human activities, 359

location-dependent, 359 Suess effect, 361 variations in, 361 14CO2 in atmosphere and radioactive decay, 353 contaminants biodegradation, identification, 355 contaminant tracer in, 354 DOC and DIC in, 354-355 fractionation processes, 356 and methane, 177 naturally occurring, 362 notation count rates, 357 fractionation, 358 before present (BP), 357 tree ring counting, 358 U/Th method, accuracy of, 358 oxalic acid as standard, 357 petroleum and contaminants generation from, 355 production in, 353-354 radioisotopes, use of, 353 signatures in groundwater DOC, 369 and stable carbon studies in contaminated environments,

366-378 in uncontaminated environments, 361-366 techniques, 354 values, 356 Radioisotopes, 13

in biodegradation and bioremediation, 14 Radionuclides, 6

Ralstonia pickettii strain PKO1, aerobic toluene degradation by, 147 Raoult's law, 307 Rapid transport mechanisms, 189 Rayleigh equation; see also Isotopes degradation and dilution percentage of, 262-263 quantification, 262 first-order degradation rate constants,

263-266 isotope data evaluation, 257 isotope distillation model, 294 mass loss, quantification of, 266-267 plot for, 259

biodegradation and dilution, 261-262 field isotope data, 261 reaction mechanisms using dual isotope plots, 267-268 use in groundwater, 18 Reactive-diffusive transport, 307 Reactive-position specific fractionation factor of chlorinated alkanes, 75

Reactive transport models; see also Isotopes isotope fractionation, incorporation of, 268 advection-dispersion model, 275 biodegradation rate, 274 compounds division, 270 concentration and isotope evolution, 274 concentrations, simulation of, 270-271 conceptual model of solute transport, 275 Damkohler number, 275 first-order kinetics, 273 fraction remaining estimation, 275-276 gasoline spill case study for, 273-274 isotope data, 269 light and heavy isotopes, reaction rate, 271 Peclet number, 275 plume cores, rate constants for, 275 reacting compounds, isotope ratio of, 271

subspecies approach, 270, 272-273 transport velocities, 277 verification, 19 Reductive transformation of chlorinated ethenes, 92 Residual ammonium pool, 206 Respiration, 131

microbial respiration and O2, 296 Rhodobacter, methyl halides degradation, 344 Rhodococcus sp., phenol and benzoate fractionation, 141-142 Ribulose monophosphate pathway, 150 Ring dioxygenase enzyme for toluene degradation, 148 Ring oxidation, 302

RNA-SIP process, 343-344; see also Stable isotope probing (SIP) Robust method, 390; see also instrumental mass bias RuBisCo enzyme, 134

Sample preparation carbon and nitrogen isotopes, 34-35 nitrate and ammonia isotopes, 35 sulfate and sulfide isotopes, 35-36 Sampling strategies, 255 Sandy aquifer, concentration distribution and isotope ratios of PCE in, 282, 284 Santiago city, Chile aquifer, nitrate concentration, 216 Santrock correction, 40 Saskatchewan soil and porosity, 313 Seawater, 87Li values, 393

Secondary kinetic isotope effects, 130; see also Kinetic isotope effect (KIE) gas transport mechanisms, 188-189 methane oxidation and transport effects, 177-178 Sedimentary rocks, lithospheric sulfur in, 225 Selected field studies, isotopes use for assess reactive processes, 251-254 Selenium (Se)

anthropogenic sources of, 402 fractionation of, 402 range of, 403 reduction, inorganic biological processes, 404 inorganic oxidation and sorption, 404-405 kinetic isotope fractionation, 404 waters and sediments, isotope composition, 404 Semivolatile organic compounds (SVOCs)

837Cl values, 138 Septic system plume concentration and isotope evolution along, 256 isotope and concentration patterns for nitrate in, 219 PCE release event, 285 Serine pathway, 150

Silurian Salina Formation, 834S values, 230 SIP, see Stable isotope probing (SIP) 29Si/28Si and 30Si/28Si ratio international standard for, 13 Site-specific natural isotope fractionation— nuclear magnetic resonance (SNIFNMR), 81 SLAP, see Standard Light Antarctic

Precipitation (SLAP) SMOW, see Standard Mean Ocean Water (SMOW)

SNIFNMR, see Site-specific natural isotope fractionation-nuclear magnetic resonance (SNIFNMR)

Soil

14CO2 signature of, 364-365 S13C measurements of CO2 in, 295 813C of methane, 374 hexahydro-1,3,5-trinitro-1,3,5-triazine

(RDX) in, 18 N cycling, 209 nitrogen in, 214-215 petroleum sources in, 319 Soil vapor extraction (SVE), 143-144 Solid phase micro extraction (SPME), 32 Solid-water partitioning coefficient, 305 Sorption process, 54

sorption-affected diffusion coefficient, 306 Source decay rate, 310 Source fingerprinting, 280 organic contaminants dual isotope approach for, 285 isotope composition variability of, 281-282 sampling strategy and data interpretation, 286-288 sources of, 282, 285-286 TCE contamination, 285 Southern Ontario discharge rates and redox conditions, 280 sulfate concentrations in groundwater study, 230-231 sulfur isotope composition of, 232 Southwest United States arid, study on root respired S13CO2 values, 370 Space charge effects, 390 Spartina alterniflora and S13C values, 136 SPME, see Solid phase micro extraction (SPME) 34S/32S ratio international standard for, 12 Stable isotope probing (SIP), 328, 340 DNA-SIP process, 341-343 and PLFAs, 341 RNA-SIP process, 343-344 Stable isotopes in biogeochemistry, 5 cellular components, use of, 337 delta-notation and international standards, 10-13 elementary particles, 386 fractionation, 9 instrumentation mass spectrometers, types, 388-391 multicollection, 388 mass fractionation processes molecules, vibrational frequencies for,386 natural abundance of, 8-10 natural materials, isotope composition of, 387 notations and conventions instrumental mass discrimination, 388 systematics of, 391 calcium, 398-402 chlorine, 395-398 chromium, 405-406 iron, 406-415 lithium, 392-394 molybdenum, 415-421 selenium, 402 terrestrial abundance of, 8 Standard Light Antarctic Precipitation

(SLAP), 12 Standard Mean Ocean Water (SMOW), 12 Steady-state diffusion, 319

of VOC; see also Gaseous compounds in unsaturated zone curtain source with first-order degradation, 315-316 from saturated zone to atmosphere with first-order degradation, 314-315 Steady-state diffusive transport, 305 Steady state enzyme kinetics, 147 Stefan-Maxwell equations, 298 35S-thiopurine in tracer studies, 328 Stockholm area, PAH percentage study, 378 Streitwieser semiclassical limits, 67; see also

Kinetic isotope effect (KIE) Suess effect, 361 Sulfur case studies abiotic and microbial sulfide oxidation,

230-231 denitrification coupled to pyrite oxidation, 232 in-situ bioremediation involving bacterial sulfate reduction, 231-232 souring control, 233 tracing sulfate during recharge, 229 cycle, 223

isotopic composition, 224 isotopic fingerprint of sulfate sources, 224-225

634S and 618O values of sulfate, 224-225 isotope fundamentals, 222 isotopes, abundance ratio of, 223 microbially mediated sulfur transformation, 226 microbial sulfur transformation processes, isotope effects during, 226-227 bacterial dissimilatory sulfate reduction, 227-228 disproportionation of sulfur intermediate compounds, 229 immobilization, 227 mineralization, 227 sulfide oxidation, 228-229 from volcanic emissions, 224 Superfund, see U.S. Environmental Protection Agency's Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) SVOCs, see Semivolatile organic compounds (SVOCs) Synthetic fertilizers, 210

TAME, see tert-Amyl methyl ether (TAME) Taxon-specific biomarkers, 140 Terminal restriction fragment length polymorphism (T-RFLP), 343

Terrestrial CO2 uptake and release, isotopic measurements, 133 tert-butyl-alcohol (TBA)

and diffusive isotope fractionation, 53 1,1,2,2-Tetrachloroethane (1,1,2,2-TeCA)

dehydrohalogenation, 93 Thermal conversion IRMS (TC-IRMS), 33 Thermal ionization mass spectrometers (TIMS) instrumental mass bias, 389

methods, 390 wet chemical techniques, 389 Thiobacillus denitrificans and denitrification, 207-208 Tills sediments, 834S values, 230-231 TIMS, see Thermal ionization mass spectrometers (TIMS)

Toluene aerobic biodegradation and isotopic fractionation, 148-149 pathways, 148 aerobic degradation, 147

Pseudomonas putida strain

F1 by, 147 Pseudomonas putida strain mt-2 by, 147 Ralstonia pickettii strain

PKO1 by, 147 ring dioxygenase enzyme for, 148 13C-enrichment of, 329 toluene dioxygenase reaction (TDO), 96-98 Torgau aquifer groundwater study, 221 Tortuosity coefficient, 306 Tracers studies, notations used in, 13 trans-1,2-dichloroethene (tDCE), 88 degradation by methanotrophic bacteria, 152 Methylomonas methanica Oak

Ridge, 152 Methylosinus trichosporium OB3b, 152 Transformation pathways assessment, 17-18;

see also Isotopes Transient diffusion of VOC

from spherical source with first-order degradation, 316-317 Transient diffusive transport, 306 Transition state theory (TST), 64 Transport equations for subspecies, 311 T-RFLP, see Terminal restriction length polymorphism (T-RFLP) Trichlorobenzene, aerobic and anaerobic degradation, 154 Trichloroethene (TCE) biodegradation, 151

at contaminated field, 144 at industrial site, carbon and chlorine isotope ratio, 286

Tritium radioisotope concentrations of, 15 TST, see Transition state theory (TST) Tunneling phenomenon, 65 Typha latifolia and 813C values, 136

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