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.

Selection processes of Arctic seasonal glacier snowpack bacterial communities.

BACKGROUND: Arctic snowpack microbial communities are continually subject to dynamic chemical and microbial input from the atmosphere. As such, the factors that contribute to structuring their microbial communities are complex and have yet to be completely resolved. These snowpack communities can be used to evaluate whether they fit niche-based or neutral assembly theories. METHODS: We sampled snow from 22 glacier sites on 7 glaciers across Svalbard in April during the maximum snow accumulation period and prior to the melt period to evaluate the factors that drive snowpack metataxonomy. These snowpacks were seasonal, accumulating in early winter on bare ice and firn and completely melting out in autumn. Using a Bayesian fitting strategy to evaluate Hubbell's Unified Neutral Theory of Biodiversity at multiple sites, we tested for neutrality and defined immigration rates at different taxonomic levels. Bacterial abundance and diversity were measured and the amount of potential ice-nucleating bacteria was calculated. The chemical composition (anions, cations, organic acids) and particulate impurity load (elemental and organic carbon) of the winter and spring snowpack were also characterized. We used these data in addition to geographical information to assess possible niche-based effects on snow microbial communities using multivariate and variable partitioning analysis. RESULTS: While certain taxonomic signals were found to fit the neutral assembly model, clear evidence of niche-based selection was observed at most sites. Inorganic chemistry was not linked directly to diversity, but helped to identify predominant colonization sources and predict microbial abundance, which was tightly linked to sea spray. Organic acids were the most significant predictors of microbial diversity. At low organic acid concentrations, the snow microbial structure represented the seeding community closely, and evolved away from it at higher organic acid concentrations, with concomitant increases in bacterial numbers. CONCLUSIONS: These results indicate that environmental selection plays a significant role in structuring snow microbial communities and that future studies should focus on activity and growth. Video Abstract.

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.

Ion Chromatography with Pulsed Amperometric Detection for Determining Cyanide in Urine and Meconium Samples.

The parents' addictions and eating habits have a significant influence on the child's growth. The first stool of a newborn baby provides a large amount of information about xenobiotics transmitted by the mother's body. The analytical technique used in the study is ion chromatography with pulsed amperometric detection (IC-PAD). The biological samples, which were obtained from women staying in a maternity ward and their partners, revealed cyanide concentrations in urine samples spanning 1.30-25.3 µg L-1. Meanwhile, the results of the meconium samples were in the range of 1.54 µg L-1 to 24.9 µg L-1. Under the optimized chromatographic conditions, the IC-PAD system exhibited satisfactory repeatability (R < 3%, n = 3) and good linearity in the range of 1-100 µg L-1. Thus, it proved to be an effective tool for monitoring trace cyanide concentration in a series of human body fluid matrices, including meconium. Based on the literature review, this is the first application of the IC-PAD analytical technique for the determination of cyanide ions in meconium samples.

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.

A High-Arctic flow-through lake system hydrochemical changes: Revvatnet, southwestern Svalbard (years 2010-2018).

Lake ecosystems are strongly coupled to features of their surrounding landscapes such as geomorphology, lithology, vegetation and hydrological characteristics. In the 2010-2018 summer seasons, we investigated an Arctic flow-through lake system Revvatnet, located in the vicinity of the coastal zone of Hornsund fjord in Svalbard, characterising its hydrological properties and the chemical composition of its waters. The lake system comprises of a small upper lake and a large lower one, the latter cone-shaped, with -29.1 m maximum depth. With near-neutral pH (full range 6.5-8.4) and low EC (7-147 µS cm-1), the lake has rather similar characteristics to many Arctic lakes. Metal and metalloid concentrations were either similar across the lake system or increased downstream (except Zn, which has important ore-bearing veins in the upper part of the catchment), which is consistent with the likely slow dissolution of suspended particles within the lakes. The ∑PAHs concentrations ranged from

Application of ion chromatography with pulsed amperometric detection for the determination of trace cyanide in biological samples, including breast milk.

Cyanide (CN) is the biomarker of exposure to the components of tobacco smoke, although its presence in biological samples is also due to the consumption of products containing cyanogenic glycosides. In this work, we determine the concentration of the free cyanide in urine, saliva and breast milk matrices, using ion chromatography with pulsed amperometric detection (IC-PAD). IC-PAD is an emerging method, with only few documented applications in urine and saliva, and the presented determination in breast milk is its first published report for any method. The biological samples, which were obtained from women staying in a maternity ward, showed cyanide concentrations spanning 1.82-98.47 µg L-1. Under the optimized chromatographic conditions, the IC-PAD system exhibited satisfactory repeatability (R < 3%, n = 3) and good linearity in the range of 1-100 µg L-1. Thus, it proved to be an effective tool for monitoring trace cyanide concentration in a series of human body fluid matrices, including breast milk. This last matrix is especially important due to the possible effect on infant health related to the mothers' smoking habits.

Evaluation of the use of reindeer droppings for monitoring essential and non-essential elements in the polar terrestrial environment.

Excess or toxic metals, non-metals and metalloids can be eliminated from the organism by deposition in inert tissue (e.g. fur) or excretion with body secretions, urine and faeces. Droppings are one of the main routes for the elimination of multiple elements and they can be collected without direct contact with the animal. Contaminant concentration has been examined in non-lethally collected tissues of several species (especially reptilian, avian and mammalian). However, studies on species residing in polar areas are still limited, especially of mammals from the European Arctic. Reindeers are the only large herbivores living in Svalbard, being an essential part of the Arctic terrestrial ecosystem. Although reindeer presence has a high impact on their surroundings, those huge mammals are rarely part of ecotoxicological studies regarding metal pollution. In this paper, the droppings of Svalbard reindeer were used as a non-invasively collected tissue to examine the excretion pathway of 30 elements. Samples were collected in mesic and moss tundra, representing summer, winter and winter-transitional excretion. For more than a half of the studied elements, significant differences occurred between the samples collected in the two tundra types. The feasibility of older and fresh samples was assessed based on summer droppings, and significant differences were found for K, As, Mn, Na, Ni, and Sb concentrations. No relevant differences in element levels were observed for samples collected from adult females, adult males and calves, except for zinc and potassium. Results show that reindeer droppings are an important vector for the transfer of many metals, non-metals and metalloids including calcium, phosphorus, zinc, aluminium and lead. As a sedentary species, feeding on local food sources, Svalbard reindeer is a valuable indicator of trace element presence in the polar terrestrial ecosystem.

Environmental characteristics of a tundra river system in Svalbard. Part 2: Chemical stress factors.

Bacterial communities in the Arctic environment are subject to multiple stress factors, including contaminants, although typically their concentrations are small. The Arctic contamination research has focused on persistent organic pollutants (POPs) because they are bioaccumulative, resistant to degradation and toxic for all organisms. Pollutants have entered the Arctic predominantly by atmospheric and oceanic long-range transport, and this was facilitated by their volatile or semi-volatile properties, while their chemical stability extended their lifetimes following emission. Chemicals present in the Arctic at detectable and quantifiable concentrations testify to their global impact. Chemical contamination may induce serious disorders in the integrity of polar ecosystems influencing the growth of bacterial communities. In this study, the abundance and the types of bacteria in the Arctic freshwater were examined and the microbial characteristics were compared to the amount of potentially harmful chemical compounds in particular elements of the Arctic catchment. The highest concentrations of all determined PAHs were observed in two samples in the vicinity of the estuary both in June and September 2016 and were 1964 ng L-1 (R12) and 3901 ng L-1 (R13) in June, and 2179 ng L-1 (R12) and 1349 ng L-1 (R13) in September. Remarkable concentrations of the sum of phenols and formaldehyde were detected also at the outflow of the Revelva river into the sea (R12) and were 0.24 mg L-1 in June and 0.35 mg L-1 in September 2016. The elevated concentrations of chemical compounds near the estuary suggest a potential impact of the water from the lower tributaries (including the glacier-fed stream measured at R13) or the sea currents and the sea aerosol as pollutant sources. The POPs' degradation at low temperature is not well understood but bacteria capable to degrading such compounds were noted in each sampling point.

Environmental characteristics of a tundra river system in Svalbard. Part 1: Bacterial abundance, community structure and nutrient levels.

The Arctic hosts a set of unique ecosystems, characterised by extreme environmental conditions and undergoing a rapid change resulting from the average temperature rising. We present a study on an aquatic ecosystem of the Revelva catchment (Spitsbergen), based on samples collected from the lake, river and their tributaries, in the summer of 2016. The landscape variety of the study site and the seasonal change in the hydrological regime modify the availability of nutrients. In general, the upper part of the catchment consists of the mountain rocky slopes which are especially abundant in iron minerals, sulphides and phosphorus minerals. The lower part of the catchment is covered by plants - lichens, saxifrages and bryophytes, which are a different source of nutrients. In the analysed water samples, the maximum concentrations of nutrients such as iron, boron and phosphorus were 0.28 µg L-1, 4.52 µg L-1 and 1.91 µg L-1, respectively, in June, while in September, Fe and B reached the concentrations of 1.32 µg L-1 and 2.71 µg L-1, respectively. The concentration of P in September was below the detection limit of 1.00 µg L-1, which may be explained by the necessity of bacteria to consume it immediately on current needs. We noted also an increase in TOC concentration between the June and September samples, which could originate both from the biomass accumulation in the catchment and the permafrost melting contributing to the hydrological regime of the river. The bacterial community developed in this environment consisted mainly of Proteobacteria, Actinobacteria, Bacteroidetes and Firmicutes phylum, while the presence of Acidobacteria was less pronounced than in other tundra-related environments. The described catchment shows that despite the relatively small amount of bioavailable nutrients, the Revelva system is biodiverse and one of the most significant biogeochemical changes occurs there in response to seasonally switching water sources.

The interaction between bacterial abundance and selected pollutants concentration levels in an arctic catchment (southwest Spitsbergen, Svalbard).

Persistent organic pollutants (POPs) have been a topic of interest in environmental sciences for >60years. POPs in the Arctic have been investigated since the 1970s, when first atmospheric measurements revealed the presence of these pollutants in the polar regions. Major contaminant transport routes to the Arctic include atmospheric and oceanic transport, as well as inflow from rivers and sea ice. The sources of pollutants, such as industry, power generators, vehicle and ship exhausts, introduce the PAHs, phenols, formaldehyde or metals into the Arctic. Transport via sea currents, however, can take several years. The highest concentration levels of total PAHs were observed in two samples from the tributaries in July 2015 and were 1069ngL-1 and 3141ngL-1 and in September 2015, the highest concentrations were observed in samples collected from Revvatnet lake and were 978ngL-1 and 1823ngL-1. The highest concentrations of trace elements in both months were 41µgL-1 in the sample from the highest tributary (July 2015) and 79µgL-1 in the same sample (September 2015). The purpose of this study was also to determine abundance of bacteria in the Arctic freshwater of different types. Microbes are omnipresent and represent diverse biological communities. In the freshwater ecosystems, microorganisms form the base of the food chain supporting higher trophic levels. Although microbes are generally thought to live in the warm regions of Earth, many of them develop in cold climates. In the Revelva catchment, the biggest number of bacteria were detected at the river estuary in July 2015 and at the sampling point located in the Revvatnet lake in September 2015. Generally, the bacterial abundance indices depended on nutrient levels to a small extent, showing the environment of the Revelva catchment not to be nutrient limited, which is in accordance with its rich biological life also in macroscale.

Hydrophobic and hydrophilic properties of pollutants as a factor influencing their redistribution during snowpack melt.

Glaciers accumulate organic pollutants delivered by snow. However, our understanding of the exact dynamics of organic pollutants in the snowpack relies primarily on laboratory experiments and mathematical models. To fill the gap related to the detailed field data, we have conducted observations of melting snow profiles in two locations and three different stages of melting on one High Arctic glacier, as well as in superimposed ice. We monitored the chemical concentrations of formaldehyde, phenols, short-chain carboxylic acids, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) and snow water equivalents to derive chemical loads. The obtained organic contaminant redistribution patterns are compared to the meltwater removal model by Meyer and Wania (2011), in order to link the behaviour of chemicals to their hydrophilic or hydrophobic properties. Both the later snowpits and the superimposed ice layer were generally more abundant in particulate organics and hydrophobic compounds, despite the initial prevalence of hydrophilic organic chemicals. The chemical species with high water solubility also showed less predictable elution patterns, due to their chemical reactivity and possible photochemical reactions in the snowpack. Finally, ice layers in the snowpack showed very different chemical characteristics to the underlying superimposed ice, so one cannot be used as a chemical proxy for another. In order to interpret the ice core records correctly, the temporal changes in concentration of different pollutant types should be considered, as glaciers may preferentially accumulate hydrophobic organics that tarry in the snow cover.

Organic pollution in surface waters from the Fuglebekken basin in Svalbard, Norwegian Arctic.

The Fuglebekken basin is situated in the southern part of the island of Spitsbergen (Norwegian Arctic), on the Hornsund fjord (Wedel Jarlsberg Land). Surface water was collected from 24 tributaries (B1-B24) and from the main stream water in the Fuglebekken basin (25) between 10 July 2009 and 30 July 2009. The present investigation reveals the results of the analysis of these samples for their PAH and PCB content. Twelve of 16 PAHs and seven PCBs were determined in the surface waters from 24 tributaries and the main stream. Total PAH and PCB concentrations in the surface waters ranged from 4 to 600 ng/L and from 2 to 400 ng/L respectively. The highest concentrations of an individual PCB (138-308 ng/L and 123 ng/L) were found in samples from tributaries B9 and B5. The presence in the basin (thousands of kilometres distant from industrial centres) of PAHs and PCBs is testimony to the fact that these compounds are transported over vast distances with air masses and deposited in regions devoid of any human pressure.