Effects of organic removal techniques prior to carbonate stable isotope analysis of lacustrine marls: a case study from palaeo‐lake Fucino (central Italy)

RATIONALE: The suitability of organic matter (OM) removal pre-treatments in isotopic studies of lacustrine carbonates is currently under debate. Naturally occurring OM seems to have a negligible effect on the bulk isotopic composition of carbonates compared with changes induced by pre-treatments. This study provides further insights into the possible effects induced by commonly used pre-treatments on natural lacustrine carbonates. METHODS: Sixteen samples from the Fucino F1-F3 lacustrine succession (Abruzzo, central Italy) were characterised for their mineralogical and geochemical composition and split in three identical aliquots. One aliquot was left untreated while the remaining two were treated with NaOCl and H2O2 dilutions. The same treatment was applied to an internal standard consisting of pure Carrara marble. The treated and untreated samples were analysed for their carbon (δ 13C values) and oxygen (δ18O values) isotope compositions using an Analytical Precision AP2003 isotope ratio mass spectrometer. RESULTS: The samples had variable proportions of endogenic and detrital components, the detrital portion being more (less) abundant during colder (warmer) climate phases. We observed that neither the NaOCl nor the H 2O2 treatment were able to completely remove OM and therefore there was selective removal of compounds within the OM pool. A possible effect of pre-treatment is the loss of carbonates intimately interspersed within the OM, as suggested by the evolution of isotopic ratios towards the local detrital array. CONCLUSIONS: Our study highlights sample-specific changes in geochemistry associated with sample pre-treatments; however, such changes do not seem to lead to either systematic and/or predictable isotopic shifts. We suggest that the suitability of NaOCl or H2O2 pre-treatments for OM removal should be evaluated on a case-bycase basis. In the specific case of lacustrine marls from palaeo-lake Fucino containing relatively low amounts of OM and in which both detrital and endogenic carbonates occur, both pre-treatments should be avoided.

Rationale: The suitability of organic matter (OM) removal pre-treatments in isotopic studies of lacustrine carbonates is currently under debate. Naturally occurring OM seems to have a negligible effect on the bulk isotopic composition of carbonates compared with changes induced by pre-treatments. This study provides further insights into the possible effects induced by commonly used pre-treatments on natural lacustrine carbonates. Methods: Sixteen samples from the Fucino F1–F3 lacustrine succession (Abruzzo, central Italy) were characterised for their mineralogical and geochemical composition and each was split into three identical aliquots. One aliquot was left untreated while the remaining two were treated with NaOCl and H2O2 dilutions. The same treatment was applied to an internal standard consisting of pure Carrara marble. The treated and untreated samples were analysed for their carbon (δ13C values) and oxygen (δ18O values) isotope compositions using an Analytical Precision AP2003 isotope ratio mass spectrometer. Results: The samples had variable proportions of endogenic and detrital components, the detrital portion being more (less) abundant during colder (warmer) climate phases. We observed that neither the NaOCl nor the H2O2 treatment was able to completely remove OM and therefore there was selective removal of compounds within the OM pool. A possible effect of pre-treatment is the loss of carbonates intimately interspersed within the OM, as suggested by the evolution of isotopic ratios towards the local detrital array. Conclusions: Our study highlights sample-specific changes in geochemistry associated with sample pre-treatments; however, such changes do not seem to lead to either systematic and/or predictable isotopic shifts. We suggest that the suitability of NaOCl or H2O2 pre-treatments for OM removal should be evaluated on a case-by-case basis. In the specific case of lacustrine marls from palaeo-lake Fucino containing relatively low amounts of OM and in which both detrital and endogenic carbonates occur, both pre-treatments should be avoided.