Snow-Dependent Biogeochemical Cycling of Polycyclic Aromatic Hydrocarbons at Coastal Antarctica.

The temporal trend of polycyclic aromatic hydrocarbons (PAHs) in coastal waters with highly dynamic sources and sinks is largely unknown, especially for polar regions. Here, we show the concurrent measurements of 73 individual PAHs and environmental data, including the composition of the bacterial community, during three austral summers at coastal Livingston (2015 and 2018) and Deception (2017) islands (Antarctica). The Livingston 2015 campaign was characterized by a larger snow melting input of PAHs and nutrients. The assessment of PAH diagnostic ratios, such as parent to alkyl-PAHs or LMW to HMW PAHs, showed that there was a larger biodegradation during the Livingston 2015 campaign than in the Deception 2017 and Livingston 2018 campaigns. The biogeochemical cycling, including microbial degradation, was thus yearly dependent on snow-derived inputs of matter, including PAHs, consistent with the microbial community significantly different between the different campaigns. The bivariate correlations between bacterial taxa and PAH concentrations showed that a decrease in PAH concentrations was concurrent with the higher abundance of some bacterial taxa, specifically the order Pseudomonadales in the class Gammaproteobacteria, known facultative hydrocarbonoclastic bacteria previously reported in degradation studies of oil spills. The work shows the potential for elucidation of biogeochemical processes by intensive field-derived time series, even in the harsh and highly variable Antarctic environment.

Occurrence and air-water diffusive exchange legacy persistent organic pollutants in an oligotrophic north Patagonian lake.

In this study, the occurrence and diffusive air-water exchange of POPs in Panguipulli Lake (39°42'S-72°13'W), an oligotrophic lake located in northern Patagonia (Chile), were determined. Air and water samples were collected between March and August 2017 (autumn-winter) and analyzed for concentrations of OCPs (α-HCH, ß-HCH, γ-HCH and HCB) and PCBs (PCB-28,-52,-101,-118,-153,-158,-180) using gas chromatography coupled with an electron capture detector. The direction of air-water exchange direction was evaluated using a fugacity approach (ƒw ƒa-1), and net diffusive exchange fluxes (FAW, ng m-2 d-1) were also estimated. Total ∑4OCP levels in air ranged from 0.31 to 37 pg m-3, with a maximum for ß-HCH, while Σ7PCB levels ranged from 3.05 to 43 pg m-3. The most abundant congener was PCB-153, accounting for 60% of the total PCBs in air. Surface water ∑4OCPs measured in this study ranged from 1.01 to 3.9 pg L-1, with γ-HCH predominating, while surface water Σ7PCB levels ranged from 0.32 to 24 pg L-1, with PCB-101, PCB-118, and PCB-153 presenting the highest levels. Diffusive air-water exchanges of HCB, α-HCH, γ-HCH and PCBs in the form of volatilization from the lake to air predominated; in contrast, for ß-HCH net deposition dominated during the sampling period. Estimates suggested faster microbial degradation in the dissolved phase compared to atmospheric degradation for all analyzed POPs. Overall, these results could indicate that the oligotrophic lakes of northern Patagonia act as a secondary source of atmospheric POPs, mainly PCBs and some OCPs. This study is a first attempt to understand the occurrence of POPs in air and water, as well as their dynamics in oligotrophic lakes in the southern hemisphere.

Rain Amplification of Persistent Organic Pollutants.

Scavenging of gas- and aerosol-phase organic pollutants by rain is an efficient wet deposition mechanism of organic pollutants. However, whereas snow has been identified as a key amplification mechanism of fugacities in cold environments, rain has received less attention in terms of amplification of organic pollutants. In this work, we provide new measurements of concentrations of perfluoroalkyl substances (PFAS), organophosphate esters (OPEs), and polycyclic aromatic hydrocarbons (PAHs) in rain from Antarctica, showing high scavenging ratios. Furthermore, a meta-analysis of previously published concentrations in air and rain was performed, with 46 works covering different climatic regions and a wide range of chemical classes, including PFAS, OPEs, PAHs, polychlorinated biphenyls and organochlorine compounds, polybromodiphenyl ethers, and dioxins. The rain-aerosol (KRP) and rain-gas (KRG) partition constants averaged 105.5 and 104.1, respectively, but showed large variability. The high field-derived values of KRG are consistent with adsorption onto the raindrops as a scavenging mechanism, in addition to gas-water absorption. The amplification of fugacities by rain deposition was up to 3 orders of magnitude for all chemical classes and was comparable to that due to snow. The amplification of concentrations and fugacities by rain underscores its relevance, explaining the occurrence of organic pollutants in environments across different climatic regions.

Snow Amplification of Persistent Organic Pollutants at Coastal Antarctica.

Many legacy and emerging persistent organic pollutants (POPs) have been reported in polar regions, and act as sentinels of global pollution. Maritime Antarctica is recipient of abundant snow precipitation. Snow scavenges air pollutants, and after snow melting, it can induce an unquantified and poorly understood amplification of concentrations of POPs. Air, snow, the fugacity in soils and snow, seawater and plankton were sampled concurrently from late spring to late summer at Livingston Island (Antarctica). Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) concentrations in snow and air were close to equilibrium. POPs in soils showed concentrations close to soil-air equilibrium or net volatilization depending on chemical volatility. Seawater-air fugacity ratios were highly correlated with the product of the snow-air partition coefficient and the Henry's law constant (KSA H'), a measure of snow amplification of fugacity. Therefore, coastal seawater mirrored the PCB congener profile and increased concentrations in snowmelt due to snowpack releasing POPs to seawater. The influence of snowpack and glacier inputs was further evidenced by the correlation between net volatilization fluxes of PCBs and seawater salinity. A meta-analysis of KSA, estimated as the ratio of POP concentrations in snow and air from previously reported simultaneous field measurements, showed that snow amplification is relevant for diverse families of POPs, independent of their volatility. We claim that the potential impact of atmospheric pollution on aquatic ecosystems has been under-predicted by only considering air-water partitioning, as snow amplification influences, and may even control, the POP occurrence in cold environments.

Metatranscriptomic responses and microbial degradation of background polycyclic aromatic hydrocarbons in the coastal Mediterranean and Antarctica.

Although microbial degradation is a key sink of polycyclic aromatic hydrocarbons (PAH) in surface seawaters, there is a dearth of field-based evidences of regional divergences in biodegradation and the effects of PAHs on site-specific microbial communities. We compared the magnitude of PAH degradation and its impacts in short-term incubations of coastal Mediterranean and the Maritime Antarctica microbiomes with environmentally relevant concentrations of PAHs. Mediterranean bacteria readily degraded the less hydrophobic PAHs, with rates averaging 4.72 ± 0.5 ng L h-1. Metatranscriptomic responses showed significant enrichments of genes associated to horizontal gene transfer, stress response, and PAH degradation, mainly harbored by Alphaproteobacteria. Community composition changed and increased relative abundances of Bacteroidota and Flavobacteriales. In Antarctic waters, there was no degradation of PAH, and minimal metatranscriptome responses were observed. These results provide evidence for factors such as geographic region, community composition, and pre-exposure history to predict PAH biodegradation in seawater.

Inputs, amplification and sinks of perfluoroalkyl substances at coastal Antarctica.

The sources, biogeochemical controls and sinks of perfluoroalkyl substances, such as perfluoroalkyl acids (PFAAs), in polar coastal regions are largely unknown. These were evaluated by measuring a large multi-compartment dataset of PFAAs concentrations at coastal Livingston and Deception Islands (maritime Antarctica) during three austral summers. PFAAs were abundant in atmospheric-derived samples (aerosols, rain, snow), consistent with the importance of atmospheric deposition as an input of PFAAs to Antarctica. Such PFAAs deposition was unequivocally demonstrated by the occurrence of PFAAs in small Antarctic lakes. Several lines of evidence supported the relevant amplification of PFAAs concentrations in surface waters driven by snow scavenging of sea-spray aerosol-bound PFAAs followed by snow-melting. For example, vertical profiles showed higher PFAAs concentrations at lower-salinity surface seawaters, and PFAAs concentrations in snow were significantly higher than in seawater. The higher levels of PFAAs at Deception Island than at Livingston Island are consistent with the semi-enclosed nature of the bay. Concentrations of PFOS decreased from 2014 to 2018, consistent with observations in other oceans. The sink of PFAAs due to the biological pump, transfer to the food web, and losses due to sea-spray aerosols alone are unlikely to have driven the decrease in PFOS concentrations. An exploratory assessment of the potential sinks of PFAAs suggests that microbial degradation of perfluoroalkyl sulfonates should be a research priority for the evaluation of PFAAs persistence in the coming decade.

Polycyclic Aromatic Hydrocarbon Degradation in the Sea-Surface Microlayer at Coastal Antarctica.

As much as 400 Tg of carbon from airborne semivolatile aromatic hydrocarbons is deposited to the oceans every year, the largest identified source of anthropogenic organic carbon to the ocean. Microbial degradation is a key sink of these pollutants in surface waters, but has received little attention in polar environments. We have challenged Antarctic microbial communities from the sea-surface microlayer (SML) and the subsurface layer (SSL) with polycyclic aromatic hydrocarbons (PAHs) at environmentally relevant concentrations. PAH degradation rates and the microbial responses at both taxonomical and functional levels were assessed. Evidence for faster removal rates was observed in the SML, with rates 2.6-fold higher than in the SSL. In the SML, the highest removal rates were observed for the more hydrophobic and particle-bound PAHs. After 24 h of PAHs exposure, particle-associated bacteria in the SML showed the highest number of significant changes in their composition. These included significant enrichments of several hydrocarbonoclastic bacteria, especially the fast-growing genera Pseudoalteromonas, which increased their relative abundances by eightfold. Simultaneous metatranscriptomic analysis showed that the free-living fraction of SML was the most active fraction, especially for members of the order Alteromonadales, which includes Pseudoalteromonas. Their key role in PAHs biodegradation in polar environments should be elucidated in further studies. This study highlights the relevant role of bacterial populations inhabiting the sea-surface microlayer, especially the particle-associated habitat, as relevant bioreactors for the removal of aromatic hydrocarbons in the oceans.

Large Enrichment of Anthropogenic Organic Matter Degrading Bacteria in the Sea-Surface Microlayer at Coastal Livingston Island (Antarctica).

The composition of bacteria inhabiting the sea-surface microlayer (SML) is poorly characterized globally and yet undescribed for the Southern Ocean, despite their relevance for the biogeochemistry of the surface ocean. We report the abundances and diversity of bacteria inhabiting the SML and the subsurface waters (SSL) determined from a unique sample set from a polar coastal ecosystem (Livingston Island, Antarctica). From early to late austral summer (January-March 2018), we consistently found a higher abundance of bacteria in the SML than in the SSL. The SML was enriched in some Gammaproteobacteria genus such as Pseudoalteromonas, Pseudomonas, and Colwellia, known to degrade a wide range of semivolatile, hydrophobic, and surfactant-like organic pollutants. Hydrocarbons and other synthetic chemicals including surfactants, such as perfluoroalkyl substances (PFAS), reach remote marine environments by atmospheric transport and deposition and by oceanic currents, and are known to accumulate in the SML. Relative abundances of specific SML-enriched bacterial groups were significantly correlated to concentrations of PFASs, taken as a proxy of hydrophobic anthropogenic pollutants present in the SML and its stability. Our observations provide evidence for an important pollutant-bacteria interaction in the marine SML. Given that pollutant emissions have increased during the Anthropocene, our results point to the need to assess chemical pollution as a factor modulating marine microbiomes in the contemporaneous and future oceans.

Anthropogenic dissolved organic carbon and marine microbiomes.

Thousands of synthetic chemicals and hydrocarbons are released to the marine environment composing the anthropogenic dissolved organic carbon (ADOC). Most ADOC is disproportionally hydrophobic, and consequently, its concentrations in the cell membranes are between a thousand and hundred million fold higher than those in the dissolved phase. Marine microorganisms respond to ADOC by multiple strategies ranging from ADOC degradation to detoxifying metabolisms. We argue that the increasing concentrations of ADOC in the oceans deriving from rivers, atmospheric deposition, and plastic leachates can have an effect on the health of the oceans and influence the major biogeochemical cycles, thus influencing the Earth system during the Anthropocene.

Sources and diffusive air-water exchange of polycyclic aromatic hydrocarbons in an oligotrophic North-Patagonian lake.

Polycyclic aromatic hydrocarbons (PAHs) are semivolatile organic compounds of environmental concern. This study aims to investigate the influence of local sources of anthropogenic PAHs and their air-water exchange fluxes in an oligotrophic North-Patagonian lake in Chile. The monitoring was carried out in Panguipulli Lake during a six-month period during the autumn and winter seasons (March to August 2017) using a high-volume air sampler and a pump system for water samples. We detected and quantified fifteen PAHs in the gas phase (mean ∑15PAHs = 11.6 ng m-3) and dissolved water phase (mean ∑15PAHs = 961.8 pg L-1). Methylphenanthrenes and pyrene dominated the concentrations of PAHs in the studied phases. To determine sources of PAHs we used the PAH ratios of Light Molecular Weight/Heavy Molecular Weight (∑LMW/∑HMW) and Phenanthrene/Anthracene (Phe/Ant). The PAH ratio results revealed a pyrogenic source. We estimated the air-water diffusive exchange fluxes and fugacity ratios for the studied compounds. In general, air-water diffusive exchanges of PAHs showed a net volatilization for the less hydrophobic (log KOW < 4) and lighter PAHs (MW ≤ 170 g mol-1), and a net deposition trend for the more hydrophobic (log KOW 4-7) and higher molecular weight PAHs (MW ≥ 178 g mol-1). We found a significant correlation between log water/air fugacity ratios and log KOW of PAHs. Therefore, it is suggested that this oligotrophic lake acts as a sink by accumulating hydrophobic and mid-high molecular weight PAHs derived mainly from pyrogenic sources. This study is the first attempt to understand the sources and behavior of PAHs in oligotrophic lakes in the Southern Chile where information is scarce regarding the occurrence of PAHs.

Enrichment of perfluoroalkyl substances in the sea-surface microlayer and sea-spray aerosols in the Southern Ocean.

Sea-spray (or sea-salt) aerosol (SSA) formation and their subsequent atmospheric transport and deposition have been suggested to play a prominent role in the occurrence of ionizable perfluoroalkyl substances (PFAS) in the maritime Antarctica and other remote regions. However, field studies on SSA's role as vector of transport of PFAS are lacking. Following a multiphase approach, seawater (SW), the sea-surface microlayer (SML) and SSA were sampled simultaneously at South Bay (Livingston Island, Antarctica). Average PFAS concentrations were 313 pg L-1, 447 pg L-1, and 0.67 pg m-3 in SW, the SML and SSA, respectively. The enrichment factors of PFAS in the SML and SSA ranged between 1.2 and 5, and between 522 and 4690, respectively. This amplification of concentrations in the SML is consistent with the surfactant properties of PFAS, while the large enrichment of PFAS in atmospheric SSA may be facilitated by the large surface area of SSA and the sorption of PFAS to aerosol organic matter. This is the first field work assessing the simultaneous occurrence of PFAS in SW, the SML and SSA. The large measured amplification of concentrations in marine aerosols supports the role of SSA as a relevant vector for long-range atmospheric transport of PFAS.

Seasonal variations in the occurrence of perfluoroalkyl substances in water, sediment and fish samples from Ebro Delta (Catalonia, Spain).

The main objective of this study was to assess the concentration levels and the seasonal variations of 13 poly- and perfluoroalkyl substances (PFASs) in different compartments (water, sediments and fish) of the Ebro Delta (NE Spain) and surrounding coastal areas. Perfluorooctanoic acid (PFOA) was the most frequently detected compound in waters and sediments. Perfluorocarboxylic acids (PFCAs) were the compounds found at the highest concentrations in water samples. On the other hand, sediments were more enriched in perfluorooctanesulfonate (PFOS) (range<1.02-22.6ng/g dw). Waters and sediments showed a different seasonal trend. While waters were characterised by a substantial constant level of PFASs over the year, sediments showed a progressive decrease from autumn to summer, revealing the great influence that environmental conditions exert on PFAS distribution in sediments. As regards fish samples, in spite of the ban of its production, PFOS was the most frequently detected compound in seawater fishes, in agreement with its high persistency, bioaccumulation and biomagnification. Moreover, PFASs showed to be more distributed in the skin rather than in muscle tissues. In addition, river fishes were characterised by very high PFAS levels (∑PFAS range from 63.8ng/g ww to 938ng/g ww), with perfluoroalkyl carboxylic acids being more concentrated than sulfonates. The PFASs concentrations in water, sediment, and biota revealed that one of the studied sites, Isla de Buda was the most contaminated site of the Ebro Delta. These results are consistent with its location at the final part of the estuary, where many irrigation channels are collected together.