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@ARTICLE{Gao:16500,
author = {Gao, Z. and Green, J.W. and Vanderborght, J. and Schmitt,
W.},
title = {{I}mproving {U}ncertainty {A}nalysis in {K}inetic
{E}valuations {U}sing {I}teratively {R}eweighted {L}east
{S}quares},
journal = {Environmental toxicology and chemistry},
volume = {30},
issn = {0730-7268},
address = {Lawrence, KS},
publisher = {SETAC [u.a.]},
reportid = {PreJuSER-16500},
pages = {2363 - 2371},
year = {2011},
note = {Record converted from VDB: 12.11.2012},
abstract = {Kinetic parameters of environmental fate processes are
usually inferred by fitting appropriate kinetic models to
the data using standard nonlinear least squares (NLS)
approaches. Although NLS is appropriate to estimate the
optimum parameter values, it implies restrictive assumptions
on data variances when the confidence limits of the
parameters must also be determined. Particularly in the case
of degradation and metabolite formation, the assumption of
equal error variance is often not realistic because the
parent data usually show higher variances than those of the
metabolites. Conventionally, such problems would be tackled
by weighted NLS regression, which requires prior knowledge
about the data errors. Instead of implicitly assuming equal
error variances or giving arbitrary weights decided by the
researcher, we use an iteratively reweighted least squares
(IRLS) algorithm to obtain the maximum likelihood estimates
of the model parameters and the error variances specific for
the different species in a model. A study with simulated
data shows that IRLS gives reliable results in the case of
both unequal and equal error variances. We also compared
results obtained by NLS and IRLS, with probability
distributions of the parameters inferred with a Markov-Chain
Monte-Carlo (MCMC) approach for data from aerobic
transformation of different chemicals in soil. Confidence
intervals obtained by IRLS and MCMC are consistent, whereas
NLS leads to very different results when the error variances
are distinctly different between different species. Because
the MCMC results can be assumed to reflect the real
parameter distribution imposed by the observed data, we
conclude that IRLS generally yields more realistic estimates
of confidence intervals for model parameters than NLS.},
keywords = {Algorithms / Confidence Intervals / Kinetics /
Least-Squares Analysis / Likelihood Functions / Markov
Chains / Models, Chemical / Monte Carlo Method / Uncertainty
/ J (WoSType)},
cin = {IBG-3},
ddc = {690},
cid = {I:(DE-Juel1)IBG-3-20101118},
pnm = {Terrestrische Umwelt},
pid = {G:(DE-Juel1)FUEK407},
shelfmark = {Environmental Sciences / Toxicology},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:21786313},
UT = {WOS:000295309400024},
doi = {10.1002/etc.630},
url = {https://juser.fz-juelich.de/record/16500},
}