Development and testing of an efficient micropollutant monitoring strategy across a large watershed.

In recent decades, extensive monitoring programmes have been conducted at the national, international, and project levels with the objective of expanding our understanding of the contamination of surface waters with micropollutants, which are often referred to as hazardous substances (HS). It has been demonstrated that HS enter surface waters via a number of pathways, including groundwater, atmospheric deposition, soil erosion, and urban systems. Given the ever-growing list of substances and the high resource demand associated with laboratory analysis, it is common practice to quantify the listed pathways based on emission factors derived from temporally and spatially constrained monitoring programmes. The derivation calculations are subject to high uncertainties, and substantial knowledge gaps remain regarding the relative importance of the unique pathways, territories, and periods. This publication presents a monitoring method designed to quantify the unique emission pathways of HS in large geographical areas characterized by differences in land use, population, and economic development. The method will be tested for a wide range of HS (ubiquitous organic and inorganic pollutants, pesticides, pharmaceuticals) throughout small sub-catchments located on tributaries. The results of the test application demonstrate a high diversity of both emission loads and instream concentrations throughout different regions for numerous substances. Riverine concentrations are found to be highly dependent on the flow status. Soil concentration levels of polycyclic aromatic hydrocarbons (PAH) and perfluoroalkyl substances (PFAS) are found to be in proportion, whereas that of potentially toxic elements (PTE) in a reverse relationship with economic development. In many instances, concentration levels are also contingent upon land use. The findings of this study reinforce the necessity for the implementation of harmonised and concerted HS monitoring programmes, which should encompass a diverse range of substances, emission sources, pathways and geographical areas. This is essential for the reliable development of emission factors.

Fine Endmesolithic fish caviar meal discovered by proteomics in foodcrusts from archaeological site Friesack 4 (Brandenburg, Germany).

The role of aquatic resources in ancient economies and paleodiet is important for understanding the evolution of prehistorical societies. Charred food remains from ancient pottery are valuable molecular evidence of dietary habits in antiquity. However, conventional archaeometric approaches applied in their analysis lack organismal specificity, are affected by abundant environmental contaminants, do not elucidate food processing recipes and are limited in the inland regions where diverse dietary resources are available. We performed proteomics analysis of charred organic deposits adhered on early ceramics from Mesolithic-Neolithic inland site Friesack 4 (Brandenburg, Germany). One of pots-a small coarse bowl radiocarbon dated to the end of the 5th millennium BC-was attributed to Endmesolithic pottery. Proteomics of foodcrust from this vessel identified fine carp roe meal and revealed details of a prehistorical culinary recipe. Ancient proteins were unequivocally distinguished from contemporary contaminants by computing deamidation ratios of glutamine residues. These data paint a broader picture of the site-specific exploitation of aquatic resources and contribute to better understanding of the dietary context of Neolithic transition in European inland.

Shotgun Lipidomics Combined with Laser Capture Microdissection: A Tool To Analyze Histological Zones in Cryosections of Tissues.

Shotgun analysis provides a quantitative snapshot of the lipidome composition of cells, tissues, or model organisms; however, it does not elucidate the spatial distribution of lipids. Here we demonstrate that shotgun analysis could quantify low-picomole amounts of lipids isolated by laser capture microdissection (LCM) of hundred micrometer-sized histological zones visualized at the cryosections of tissues. We identified metabolically distinct periportal (pp) and pericentral (pc) zones by immunostaining of 20 µm thick cryosections of a healthy mouse liver. LCM was used to ablate, catapult, and collect the tissue material from 10 to 20 individual zones covering a total area of 0.3-0.5 mm2 and containing ca. 500 cells. Top-down shotgun profiling relying upon computational stitching of 61 targeted selective ion monitoring ( t-SIM) spectra quantified more than 200 lipid species from 17 lipid classes including glycero- and glycerophospholipids, sphingolipids, cholesterol esters, and cholesterol. Shotgun LCM revealed the overall commonality of the full lipidome composition of pp and pc zones along with significant ( p < 0.001) difference in the relative abundance of 13 lipid species. Follow-up proteomics analyses of pellets recovered from an aqueous phase saved after the lipid extraction identified 13 known and 7 new protein markers exclusively present in pp or in pc zones and independently validated the specificity of their visualization, isolation, and histological assignment.