Fingerprinting and tracing the sources of soils and sediments: Earth and ocean science, geoarchaeological, forensic, and human health applications

publisher: Elsevier articletitle: Fingerprinting and tracing the sources of soils and sediments: Earth and ocean science, geoarchaeological, forensic, and human health applications journaltitle: Earth-Science Reviews articlelink: http://dx.doi.org/10.1016/j.earscirev.2016.08.012 content_type: article copyright: © 2016 Elsevier B.V. All rights reserved

Diverse soil carbon dynamics expressed at the molecular level

The stability and potential vulnerability of soil organic matter (SOM) to global change remains incompletely understood due to the complex processes involved in its formation and turnover. Here we combine compound-specific radiocarbon analysis with fraction-specific and bulk-level radiocarbon measurements in order to further elucidate controls on SOM dynamics in a temperate and sub-alpine forested ecosystem. Radiocarbon contents of individual organic compounds isolated from the same soil interval generally exhibit greater variation than those among corresponding operationally-defined fractions. Notably, markedly older ages of long-chain plant leaf wax lipids (n-alkanoic acids) imply that they reflect a highly stable carbon pool. Furthermore, marked 14C variations among shorter- and longer-chain n-alkanoic acid homologues suggest that they track different SOM pools. Extremes in SOM dynamics thus manifest themselves within a single compound class. This exploratory study highlights the potential of compound-specific radiocarbon analysis for understanding SOM dynamics in ecosystems potentially vulnerable to global change

An extended Bayesian sediment fingerprinting mixing model for the full Bayes treatment of geochemical uncertainties

Recent advances in sediment fingerprinting research have seen Bayesian mixing models being increasingly employed as an effective method to coherently translate component uncertainties into source apportionment results. Here, we advance earlier work by presenting an extended Bayesian mixing model capable of providing a full Bayes treatment of geochemical uncertainties. The performance of the extended full Bayes model was assessed against the equivalent empirical Bayes model and traditional frequentist optimisation. The performance of models coded in different Bayesian software (‘JAGS’ and ‘Stan’) was also evaluated, alongside an assessment of model sensitivity to reduced source representativeness and non-conservative fingerprint behaviour. Results revealed comparable accuracy and precision for the full and empirical Bayes models across both synthetic and real sediment geochemistry datasets, demonstrating that the empirical treatment of source data here represents a close approximation of the full Bayes treatment. Contrasts in the performance of models coded in JAGS and Stan revealed that the choice of software employed can impact significantly upon source apportionment results. Bayesian models coded in Stan were the least sensitive to both reduced source representativeness and non-conservative fingerprint behaviour, indicating Stan as the preferred software for future Bayesian sediment fingerprinting studies. Whilst the frequentist optimisation generally yielded comparable accuracy to the Bayesian models, uncertainties around apportionment estimates were substantially greater and the frequentist model was less effective at dealing with non-conservative behaviour. Overall, the effective performance of the extended full Bayes mixing model coded in Stan represents a notable advancement in source apportionment modelling relative to previous approaches. Both the mixing model and the software comparisons presented here should provide useful guidelines for future sediment fingerprinting studies

Sediment source fingerprinting: benchmarking recent outputs, remaining challenges and emerging themes

Abstract: Purpose: This review of sediment source fingerprinting assesses the current state-of-the-art, remaining challenges and emerging themes. It combines inputs from international scientists either with track records in the approach or with expertise relevant to progressing the science. Methods: Web of Science and Google Scholar were used to review published papers spanning the period 2013–2019, inclusive, to confirm publication trends in quantities of papers by study area country and the types of tracers used. The most recent (2018–2019, inclusive) papers were also benchmarked using a methodological decision-tree published in 2017. Scope: Areas requiring further research and international consensus on methodological detail are reviewed, and these comprise spatial variability in tracers and corresponding sampling implications for end-members, temporal variability in tracers and sampling implications for end-members and target sediment, tracer conservation and knowledge-based pre-selection, the physico-chemical basis for source discrimination and dissemination of fingerprinting results to stakeholders. Emerging themes are also discussed: novel tracers, concentration-dependence for biomarkers, combining sediment fingerprinting and age-dating, applications to sediment-bound pollutants, incorporation of supportive spatial information to augment discrimination and modelling, aeolian sediment source fingerprinting, integration with process-based models and development of open-access software tools for data processing. Conclusions: The popularity of sediment source fingerprinting continues on an upward trend globally, but with this growth comes issues surrounding lack of standardisation and procedural diversity. Nonetheless, the last 2 years have also evidenced growing uptake of critical requirements for robust applications and this review is intended to signpost investigators, both old and new, towards these benchmarks and remaining research challenges for, and emerging options for different applications of, the fingerprinting approach

The challenges and opportunities of addressing particle size effects in sediment source fingerprinting: A review

publisher: Elsevier articletitle: The challenges and opportunities of addressing particle size effects in sediment source fingerprinting: A review journaltitle: Earth-Science Reviews articlelink: http://dx.doi.org/10.1016/j.earscirev.2017.04.009 content_type: article copyright: © 2017 Elsevier B.V. All rights reserved

Isotope mixing models require individual isotopic tracer content for correct quantification of sediment source contributions

The use of isotopic tracers for sediment source apportionment is gaining interest with recent introduction of compound-specific stable isotope tracers. The method relies on linear mixing of source isotopic tracers, and deconvolution of a sediment mixture initially quantifies the contribution of sources to the mixture's tracer signature. Therefore, a correction to obtain real sediment source proportions is subsequently required. As far as we are aware, all published studies to date have used total isotopic tracer content or a proxy (e.g., soil carbon content) for this post-unmixing correction. However, as the relationship between the isotopic tracer mixture and the source mixture is different for each isotopic tracer, post-unmixing corrections cannot be carried out with one single factor. This contribution presents an isotopic tracer model structurethe concentration-dependent isotope mixing model (CD-IMM)to overcome this limitation. Herein, we aim to clarify why the conventional approach to converting isotopic tracer proportions to source proportions using a single factor is wrong. In an initial mathematical assessment, error incurred by not using CD-IMM (NCD-IMM) in unmixing two sources with two isotopic tracers showed a complex relation as a function of relative tracer contents. Next, three artificial mixtures with different proportions of three soil sources were prepared and deconvoluted using C-13 of fatty acids using CD-IMM and NCD-IMM. Using NCD-IMM affected both accuracy (mean average error increased up to a threefold compared with the CD-IMM output) and precision (interquartile range was up to 2.5 times larger). Finally, as an illustrative example, the proportional source contribution reported in a published study was recalculated using CD-IMM. This resulted in changes in estimated source proportions and associated uncertainties. Content of isotopic tracers is seldom reported in published work concerning use of isotopic tracers for sediment source partitioning. The magnitude of errors made by miscalculation in former studies is therefore difficult to assess. With this contribution, we hope the community will acknowledge the limitations of prior approaches and use a CD-IMM in future studies

Divergent synthetic approach to 6??-modified ?-GalCer analogues

A synthetic approach is presented for the synthesis of galacturonic acid and D-fucosyl modified KRN7000. The approach allows for late-stage functionalisation of both the sugar 6??-OH and the sphingosine amino groups, which enables convenient synthesis of promising 6??-modified KRN7000 analogue