es0504587_si_002.xls (45.5 kB)
A New Concept Linking Observable Stable Isotope Fractionation to Transformation Pathways of Organic Pollutants
dataset
posted on 2005-09-15, 00:00 authored by Martin Elsner, Luc Zwank, Daniel Hunkeler, René P. SchwarzenbachMeasuring stable isotope fractionation of carbon, hydrogen,
and other elements by Compound Specific Isotope
Analysis (CSIA) is a new, innovative approach to assess
organic pollutant degradation in the environment. Central to
this concept is the Rayleigh equation which relates
degradation-induced decreases in concentrations directly
to concomitant changes in bulk (= average over the
whole compound) isotope ratios. The extent of in situ
transformation may therefore be inferred from measured
isotope ratios in field samples, provided that an appropriate
enrichment factor (εbulk) is known. This εbulk value,
however, is usually only valid for a specific compound
and for specific degradation conditions. Therefore, a direct
comparison of εbulk values for different compounds and
for different types of reactions has in general not been
feasible. In addition, it is often uncertain how robust and
reproducible εbulk values are and how confidently they can
be used to quantify contaminant degradation in the field.
To improve this situation and to achieve a more in-depth
understanding, this critical review aims to relate fundamental
insight about kinetic isotope effects (KIE) found in the
physico(bio)chemical literature to apparent kinetic isotope
effects (AKIE) derived from εbulk values reported in
environmentally oriented studies. Starting from basic rate
laws, a quite general derivation of the Rayleigh equation
is given, resulting in a novel set of simple equations that take
into account the effects of (1) nonreacting positions and
(2) intramolecular competition and that lead to position-specific
AKIE values rather than bulk enrichment factors.
Reevaluation of existing εbulk literature values result in
consistent ranges of AKIE values that generally are in good
agreement with previously published data in the (bio)chemical literature and are typical of certain degradation
reactions (subscripts C and H indicate values for carbon
and hydrogen): AKIEC = 1.01−1.03 and AKIEH = 2−23 for
oxidation of C−H bonds; AKIEC = 1.03−1.07 for SN2-reactions; AKIEC = 1.02−1.03 for reductive cleavage of
C−Cl bonds; AKIEC = 1.00−1.01 for CC bond epoxidation;
AKIEC = 1.02−1.03 for CC bond oxidation by permanganate.
Hence, the evaluation scheme presented bridges a gap
between basic and environmental (bio)chemistry and provides
insight into factors that control the magnitude of bulk
isotope fractionation factors. It also serves as a basis to
identify degradation pathways using isotope data. It is shown
how such an analysis may be even possible in complex
field situations and/or in cases where AKIE values are smaller
than intrinsic KIE values, provided that isotope fractionation
is measured for two elements simultaneously (“two-dimensional isotope analysis”). Finally, the procedure is
used (1) to point out the possibility of estimating approximate
εbulk values for new compounds and (2) to discuss the
moderate, but non-negligible variability that may quite
generally be associated with εbulk values. Future research
is suggested to better understand and take into account
the various factors that may cause such variability.