Impact of saponification and silver-nitrate purification on lacustrine alkenone distributions and alkenone-based indices.

A growing interest in lacustrine alkenones as a proxy for continental paleotemperature reconstructions accompanied important methodological improvements over the past two decades. New gas chromatography (GC) columns were used for alkenone analysis, that drastically improved alkenone separation, especially for freshwater lakes. However, these recent advances are sometimes not sufficient in separating compounds that interfere with alkenones in the resulting chromatograms and concurrently, new chemical procedures were implemented to further clean up the samples. Here we investigate the impact of two clean-up procedures, saponification and silver-nitrate purification, on alkenone distribution, alkenone quantification, and C37 alkenone-based indices, including the U37K index. The silver-nitrate purification modified the C37 alkenone distribution and thus the C37 alkenone-based indices, especially the U37K index, in 6 out of the 9 studied samples by further retaining alkenones with more double bonds. These changes would result on an average error of 3 °C in reconstructed temperatures. Saponification also influenced the C37 alkenone distribution mainly by removing co-eluting compounds, thereby improving the quality of the results. Both saponification and purification resulted in the reduction of the C37 alkenone concentration by almost half. Clean-up steps should thus be used carefully, paying particular attention to any change in alkenone distribution and concentration. Limiting the use of additional clean-up steps reduces the risk of modifying the alkenone distribution.

High-Resolution Historical Record of Plant Protection Product Deposition Documented by Target and Nontarget Trend Analysis in a Swiss Lake under Anthropogenic Pressure.

A multiproxy workflow was used to assess >60 plant protection products (PPPs) in sediment samples from a Swiss lake under heavy agricultural pressure. The results show the appearance of PPPs for the first time in the early 1960s with an overall detection of 34 PPPs and with herbicides and fungicides found in equal proportions. Paleolimnological data [e.g., chronology, hyperspectral imaging of sedimentary green pigments, and semiquantitative elemental composition (µXRF scans)] suggest that PPP concentrations and fluxes to the sediment over time are not related to land surface processes such as soil erosion or lake biogeochemistry but are attributed mainly to PPP application (inferred from sales) or regulatory measures (bans). Additional compounds with similar sources of contamination as the target PPPs captured by nontarget trend analysis (≥2000 unknown profiles) reveal significant inputs of contaminants to the lake starting in the 1970s, followed by a decrease of contamination at the beginning of the 1990s and a constant increase by ∼28% of the unknown compounds since the year 2000. An ecological risk assessment conducted on detected PPPs indicates that since the 1980s, the sediment quality is insufficient with risk quotient values displaying maximum levels in the most recent sediments (∼2010) despite bans of specific PPPs and environmental regulations.