Sea spray as a secondary source of chlorinated persistent organic pollutants? - Conclusions from a comparison of seven fresh snowfall events in 2019 and 2021.

Secondary sources of persistent organic pollutants (POPs) gain in importance worldwide as primary sources decline. In this work, we aim to determine whether sea spray may be a secondary source of chlorinated POPs to the terrestrial Arctic, since a similar mechanism was proposed there only for the more water-soluble POPs. To this end, we have determined polychlorinated biphenyls and organochlorine pesticides concentrations in fresh snow and seawater collected in the vicinity of the Polish Polar Station in Hornsund in two sampling periods covering spring 2019 and 2021. To support our interpretations, we include also metal and metalloid, and stable hydrogen and oxygen isotopes analysis in those samples. A significant correlation was found between the concentrations of POPs and the distance from the sea at the sampling point, yet the confirmation of sea spray impact lies more in capturing an event with negligible long-range transport influence where the detected chlorinated POPs (Cl-POPs) matched in composition the compounds enriched in the sea surface microlayer, which is both a source of sea spray and a seawater microenvironment rich in hydrophobic substances.

Rainwater chemistry composition in Bellsund: Sources of elements and deposition discrepancies in the coastal area (SW Spitsbergen, Svalbard).

Discrepancies in rainfall chemistry in Bellsund were found to be influenced by the orographic barrier and related to the variability in the inflow of air masses as well as to the distance of sampling sites from the sea and thus the extent of sea spray impact. This study covers measurements of rainfall (P) and air temperature (T), physicochemical parameters (pH, specific electrolytic conductivity (SEC), major ions (Cl-, NO3-, SO42-) and elements (Na, Ca, Mg,K), as well as trace elements (i.a. As, Cd, Cr, Fe, Co, Pb, Ni, Zn) and dissolved organic carbon (DOC) in 22 rainfall samples collected in August on the Calypsostranda marine terrace and in the forefield of a land-terminating glacier (NW Wedel Jarlsberg Land). The comparison of chemical parameters in the samples revealed major discrepancies, including statistically significant higher rainwater pH and SEC, and the levels of Ag, As, Bi, Ca, Co, Fe, Li, Mn, Mo, Ni, Pb, Sb, and V, deposited near the seashore (Calypsostranda) than in the glacier forefield. Cluster analysis (CA) showed that elements deposited in lower concentrations at the glacier forefield site came from predominately anthropogenic sources. Conversely, CA results of metals and metalloids deposited on the Calypsostranda marine terrace indicate both natural and anthropogenic sources. A correlation matrix and principal component analysis (PCA) permitted identifying two primary factors affecting rainfall chemistry at each of the study sites. In Calypsostranda, these were the inflow of relatively unpolluted cold air (F1 = 35.1%) and sea spray (F2 = 27.6%), while in the glacier forefield the factors were an orographic barrier (F1 = 37.3%) and the inflow of polluted warm air (F2 = 25.2%).

Local variability in snow concentrations of chlorinated persistent organic pollutants as a source of large uncertainty in interpreting spatial patterns at all scales.

Single point sampling, a widespread practice in snow studies in remote areas, due to logistical constraints, can present an unquantified error to the final study results. The low concentrations of studied chemicals, such as chlorinated persistent organic pollutants, contribute to the uncertainty. We conducted a field experiment in the Arctic to estimate the error stemming from differences in the composition of snow at short distances (1-3 m), including 13 single organochlorine pesticides and 6 polychlorinated biphenyls, thus providing the most detailed published dataset on the subject. We contrasted this variability with the uncertainty at larger spatial scales, both within one valley (regional scale, this study) and as described in the worldwide literature. The range of values for the coefficient of variation for local samples was 20-58% for single organochlorine pesticides (OCPs) and 33-54% for polychlorinated biphenyls (PCBs), and for regional samples it was 21-69% for OCPs and 65-93% for PCBs. We suggest that, to observe the actual changes in the concentration of selected compounds in snow, they should vary at the level of 40-60%, depending on the compound in question. The uncertainty margin remains much smaller than the current discrepancy between observation data and atmospheric deposition models considering snow, deeming field data on snow concentrations a useful ground-truthing dataset. However, field observations on spatial differences at all scales need to be interpreted with caution, and the dataset provided here on the local sampling uncertainty helps define the margins of such interpretations.

Chemical hazard in glacial melt? The glacial system as a secondary source of POPs (in the Northern Hemisphere). A systematic review.

Toxicity of compounds belonging to persistent organic pollutants (POPs) is widely known, and their re-emission from glaciers has been conclusively demonstrated. However, the harmful effects associated with such secondary emissions have yet to be thoroughly understood, especially in the spatial and temporal context, as the existing literature has a clear sampling bias with the best recognition of sites in the European Alps. In this review, we elaborated on the hazards associated with the rapid melting of glaciers releasing organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs). To this end, we collated knowledge on: (1) the varying glacier melt rate across the Northern Hemisphere, (2) the content of POPs in the glacial system components, including the less represented areas, (3) the mechanisms of POPs transfer through the glacial system, including the importance of immediate emission from snow melt, (4) risk assessment associated with POPs re-emission. Based on the limited existing information, the health risk of drinking glacial water can be considered negligible, but consuming aquatic organisms from these waters may increase the risk of cancer. Remoteness from emission sources is a leading factor in the presence of such risk, yet the Arctic is likely to be more exposed to it in the future due to large-scale processes shifting atmospheric pollution and the continuous supply of snow. For future risk monitoring, we recommend to explore the synergistic toxic effects of multiple contaminants and fill the gaps in the spatial distribution of data.