Aromatic protonation. V. Secondary hydrogen isotope effects on hydrogen ion transfer from the hydronium ion

1968 ◽  
Vol 90 (25) ◽  
pp. 6982-6988 ◽  
Author(s):  
A. Jerry. Kresge ◽  
D. P. Onwood ◽  
S. Slae
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Effects ◽  
Hydrogen Ion ◽  
Ion Transfer ◽  
Hydronium Ion

scholarly journals Unravelling the process of petroleum hydrocarbon biodegradation in different filter materials of constructed wetlands by stable isotope fractionation and labelling studies

2021 ◽  
Author(s):  
Andrea Watzinger ◽  
Melanie Hager ◽  
Thomas Reichenauer ◽  
Gerhard Soja ◽  
Paul Kinner
Keyword(s):  
Stable Isotope ◽  
Constructed Wetlands ◽  
Hydrogen Isotope ◽  
Petroleum Hydrocarbon ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Filter Material ◽  
Hydrocarbon Biodegradation ◽  
Stable Isotope Fractionation ◽  
Filter Materials

AbstractMaintaining and supporting complete biodegradation during remediation of petroleum hydrocarbon contaminated groundwater in constructed wetlands is vital for the final destruction and removal of contaminants. We aimed to compare and gain insight into biodegradation and explore possible limitations in different filter materials (sand, sand amended with biochar, expanded clay). These filters were collected from constructed wetlands after two years of operation and batch experiments were conducted using two stable isotope techniques; (i) carbon isotope labelling of hexadecane and (ii) hydrogen isotope fractionation of decane. Both hydrocarbon compounds hexadecane and decane were biodegraded. The mineralization rate of hexadecane was higher in the sandy filter material (3.6 µg CO2 g−1 day−1) than in the expanded clay (1.0 µg CO2 g−1 day−1). The microbial community of the constructed wetland microcosms was dominated by Gram negative bacteria and fungi and was specific for the different filter materials while hexadecane was primarily anabolized by bacteria. Adsorption / desorption of petroleum hydrocarbons in expanded clay was observed, which might not hinder but delay biodegradation. Very few cases of hydrogen isotope fractionation were recorded in expanded clay and sand & biochar filters during decane biodegradation. In sand filters, decane was biodegraded more slowly and hydrogen isotope fractionation was visible. Still, the range of observed apparent kinetic hydrogen isotope effects (AKIEH = 1.072–1.500) and apparent decane biodegradation rates (k = − 0.017 to − 0.067 day−1) of the sand filter were low. To conclude, low biodegradation rates, small hydrogen isotope fractionation, zero order mineralization kinetics and lack of microbial biomass growth indicated that mass transfer controlled biodegradation.

CO2 and H+ Excretion by Swimming Coho Salmon, Oncorhynchus Kisutch

1983 ◽  
Vol 107 (1) ◽  
pp. 169-180
Author(s):  
GUIDO VAN DEN THILLART ◽  
DAVID RANDALL ◽  
LIN HOA-REN
Keyword(s):  
High Speed ◽  
Coho Salmon ◽  
Sea Water ◽  
Oncorhynchus Kisutch ◽  
Hydrogen Ion ◽  
Ion Transfer ◽  
Bicarbonate Concentration ◽  
Seawater Ph ◽  
External Conditions ◽  
Co2 Excretion

Coho salmon, Oncorhynchus kisutch (Walbaum), were swum at constant speed in a ‘Brett-type’ tunnel respirometer. Blood PO2, PCO2 and pH as well as total CO2 content and red blood cell pH were unchanged during swimming. The RE (respiratory exchange ratio) was slightly less than 0.7 when the fish was swimming in normal sea water, indicating that some CO2 retained by the fish. Lowering seawater bicarbonate concentration increased HCO3− transfer, presumably because of passive bicarbonate loss. A reduction in seawater pH from 7.95 to 7.1 sharply reduced both CO2 and hydrogen ion transfer, resulting in very low RE values of about 0.2. Hydrogen ion excretion was elevated during prolonged swimming following high speed swimming activity. It would appear that CO2 and hydrogen ion transfer by fish need not be matched and changing internal and external conditions can have a marked and separate effect on hydrogen ion and CO2 excretion and therefore on the RE value.

scholarly journals Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl

2018 ◽  
Author(s):  
Frank Keppler ◽  
Enno Bahlmann ◽  
Markus Greule ◽  
Heinz Friedrich Schöler ◽  
Julian Wittmer ◽  
...  
Keyword(s):  
Hydrogen Isotope ◽  
Isotope Fractionation ◽  
Isotope Effects ◽  
Isotope Analysis ◽  
Isotope Ratio Mass Spectrometry ◽  
Detailed Knowledge ◽  
Mass Spectrometric Measurement ◽  
Isotopic Analyses ◽  
Chlorine Radicals ◽  
Stable Hydrogen Isotope

Abstract. Chloromethane (CH3Cl) is an important provider of chlorine to the stratosphere but yet lacks detailed knowledge of its budget. Stable isotope analysis is potentially a powerful tool to constrain CH3Cl flux estimates. The largest degree of isotope fractionation is expected to occur for deuterium in CH3Cl in the hydrogen abstraction reactions with its main sink reactant tropospheric OH and its minor sink reactant Cl atoms. We determined the isotope fractionation by stable hydrogen isotope analysis of the fraction of CH3Cl remaining after reaction with hydroxyl and chlorine radicals in a 3.5 m3 Teflon smog-chamber at 293 ± 1 K. We measured the increasing stable hydrogen isotope values of the unreacted CH3Cl using compound specific thermal conversion isotope ratio mass spectrometry. The isotope fractionations of CH3Cl for the reactions with hydroxyl and chlorine radicals were found to be −242 ± 7 mUr (or ‰) and −280 ± 11 mUr, respectively. For comparison, we performed similar experiments using methane (CH4) as the target compound with OH and obtained a fractionation constant of −205 ± 6 mUr which is in good agreement with values previously reported. The observed large kinetic isotope effects are helpful when employing isotopic analyses of CH3Cl in the atmosphere to improve our knowledge of its atmospheric budget.

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