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.

Atmospheric PAHs in rural, urban, industrial and beach locations in Buenos Aires Province, Argentina: sources and health risk assessment.

The first atmospheric PAHs levels and associated inhalation cancer risk were assessed over southwest Buenos Aires region by deploying PUF disk PAS samplers. Eight sampling location included coastal zones, touristic beaches, and rural inland areas were considered. PUF disks were fortified with surrogate standards and extracted by automated Soxhlet prior to GC-MS analysis. Σ16 PAHs ranged from 1.13 to 44.5 ng m-3 (10.3 ± 9.8), while urban locations showed up to 10 times higher PAH levels than rural or beach locations. Direct sources of PAHs, such as intensive vehicle traffic, heating, and general combustion activities, were identified. PAHs with four to six rings (46.62%) were predominantly Flt, Pyr, BbF, and BkF, and carcinogenic risk was expressed by BaP (0.10 ± 0.07 ng m-3) and BaPTEQs (0.26 ± 0.22 ng m-3). Inhalation ECR (2.23E-5, WHO) presented the lowest risk at beach locations. Molecular ratios and PCA showed a strong dominance in pyrolytic sources, such as biomass and coal combustion, with a particular signature in fires at inland locations. Overall, this study demonstrated that PUF disk passive air sampling provided a sound and simple approach for tracking air PAHs, their sources and public health risks, bringing a cost-effective tool for pollution control measures, even at small and remote towns. This is particularly relevant in extensive countries with medium or low income, such as Argentina.

Legacy and novel flame retardants from indoor dust in Antarctica: Sources and human exposure.

The air humidity in Antarctica is very low and this peculiar weather parameter make the use of flame retardants in research facilities highly needed for safety reasons, as fires are a major risk. Legacy and novel flame retardants (nFRs) including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), Dechlorane Plus (DP), and other nFRs were measured in indoor dust samples collected at research Stations in Antarctica: Gabriel de Castilla, Spain (GCS), Julio Escudero, Chile (JES), and onboard the RRS James Clark Ross, United Kingdom (RRS JCR). The GC-HRMS and LC-MS-MS analyses of dust samples revealed ∑7PBDEs of 41.5 ± 43.8 ng/g in rooms at GCS, 18.7 ± 11.6 ng/g at JES, and 27.2 ± 37.9 ng/g onboard the RRS JCR. PBDE pattern was different between the sites and most abundant congeners were BDE-183 (40%) at GCS, BDE-99 (50%) at JES, and BDE-153 (37%) onboard the RRS JCR. The ∑(4)HBCDs were 257 ± 407 ng/g, 14.9 ± 14.5 ng/g, and 761 ± 1043 ng/g in indoor dust collected in rooms at GCS, JES, and RRS JCR, respectively. The ∑9nFRs were 224 ± 178 ng/g at GCS, 14.1 ± 13.8 ng/g at JES, and 194 ± 392 ng/g on the RRS JCR. Syn- and anti-DP were detected in most of the samples and both isomers showed the highest concentrations at GCS: 163 ± 93.6 and 48.5 ± 61.1 ng/g, respectively. The laboratory and living room showed the highest concentration of HBCDs, DPs, BTBPE. The wide variations in FR levels in dust from the three research facilities and between differently used rooms reflect the different origin of furnishing, building materials and equipment. The potential health risk associated to a daily exposure via dust ingestion was assessed for selected FRs: BDEs 47, 99, and 153, α-, ß-, and γ-HBCD, BTBPE, syn- and anti-DP. Although the estimated exposures are below the available reference doses, caution is needed given the expected increasing use of novel chemicals without a comprehensive toxicological profile.

Atmospheric Concentrations of New Persistent Organic Pollutants and Emerging Chemicals of Concern in the Group of Latin America and Caribbean (GRULAC) Region.

A special initiative was run by the Global Atmospheric Passive Sampling (GAPS) Network to provide atmospheric data on a range of emerging chemicals of concern and candidate and new persistent organic pollutants in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale data for a range of flame retardants (FRs) including polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs), and a range of alternative FRs (novel FRs) are reported over 2 years of sampling with low detection frequencies of the novel FRs. Atmospheric concentrations of the OPEs were an order of magnitude higher than all other FRs, with similar profiles at all sites. Regional-scale background concentrations of the poly- and perfluoroalkyl substances (PFAS), including the neutral PFAS (n-PFAS) and perfluoroalkyl acids (PFAAs), and the volatile methyl siloxanes (VMS) are also reported. Ethyl perfluorooctane sulfonamide (EtFOSA) was detected at highly elevated concentrations in Brazil and Colombia, in line with the use of the pesticide sulfluramid in this region. Similar concentrations of the perfluoroalkyl sulfonates (PFAS) were detected throughout the GRULAC region regardless of location type, and the VMS concentrations in air increased with the population density of sampling locations. This is the first report of atmospheric concentrations of the PFAAs and VMS from this region.

Contamination Profile of DDTs in the Shark Somniosus microcephalus from Greenland Seawaters.

DDT isomers were detected in all the liver and muscle samples of Greenland sharks Somniosus microcephalus (n = 15) caught in Greenland seawaters. The mean concentrations of ΣDDTs (sum of o,p' and p,p' DDT, DDD, and DDE isomers) were 1094 ± 818 ng/g lipid weight (lw) in the muscle and 761 ± 416 ng/g lw in the liver. The p,p'-DDE accounted for 48% ± 41% and 53% ± 54% of the total DDT residue in the white muscle and liver, respectively. The lipid content was 48% ± 10% in the muscle and 43% ± 17% in the liver. Female sharks showed the highest concentrations of ΣDDTs. The youngest shark showed higher concentrations of ΣDDTs in the liver than the older sharks. To our knowledge, this is one of the few investigations on DDT levels in S. microcephalus where concentrations were correlated to lipid content and sex/size.

Current challenges in air sampling of semivolatile organic contaminants: sampling artifacts and their influence on data comparability.

With current science and policy needs, more attention is being given to expanding and improving air sampling of semivolatile organic contaminants (SVOCs). However, a wide range of techniques and configurations are currently used (active and passive samplers, different deployment times, different sorbents, etc.) and as the SVOC community looks to assess air measurements on a global scale, questions of comparability arise. We review current air sampling techniques, with a focus on sampling artifacts that can lead to uncertainties or biases in reported concentrations, in particular breakthrough, degradation, meteorological influences, and assumptions regarding passive sampling. From this assessment, we estimate the bias introduced for SVOC concentrations from all factors. Due to the effects of breakthrough, degradation, particle fractions and sampler uptake periods, some current passive and active sampler configurations may underestimate certain SVOCs by 30-95%. We then recommend future study design, appropriateness of sampler types for different study goals, and finally, how the SVOC community should move forward in both research and monitoring to best achieve comparability and consistency in air measurements.

Spatial distribution and characteristics of plastic pollution in the salt marshes of Bahía Blanca Estuary, Argentina.

This study delves into the magnitude and attributes of plastic pollution in the salt marshes of the Bahía Blanca Estuary, Argentina, with a specific focus on its spatial distribution. The investigation included the evaluation of microplastics (1-5 mm), mesoplastics (5-25 mm) and macroplastics (25-100 mm), discovering elevated levels along the high salt marsh strandline compared to low salt marsh and mudflat areas. Notably, the abundance of plastic reached staggering levels, reaching up to 20,060 items/m2 in the vicinity of an illegal dumpsite. Microplastics, particularly in the 2-4 mm range, were dominant, and the main plastic components were high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), and polystyrene (PS). Plastic films emerged as the predominant plastic type, while the presence of pellets hinted at potential sources such as illegal dumping and port-related activities. This contamination could be largely attributed to inappropriate waste management practices and urban runoff, which pose a substantial ecological threat to these ecosystems. Urgent remedial action is essential to protect these marshes, underscoring the critical need for comprehensive wetland management and educational initiatives to ensure their long-term sustainability.

Detection of plastic, cellulosic micro-fragments and microfibers in Laternula elliptica from King George Island (Maritime Antarctica).

It is generally acknowledged that microplastic pollutants are prevalent in ocean waters and sediments across a range of tropical, temperate, subpolar, and polar regions. The waters surrounding King George Island are significantly impacted by human activities, particularly those related to scientific stations, fishing, and tourism. Organisms, such as Laternula elliptica, can be used as environmental monitors due to the likelihood that they will bioaccumulate pollutants. The goal of this study was to quantify and identify plastic and cellulosic micro-fragments and microfibers present in the soft body of clams (n = 21), collected from Fildes Bay near sewage and wastewater discharges. Plastic and cellulose microfragments and microfibers were counted, and their compositions were determined using FT-IR. All 21 individuals sampled contained fragments and fibers, with a total of 900 items detected (42.86 ± 25.36 mean ± SD items per individual), or 1.82 items g.wet mass-1. 58 % of items were cellulose and 22 % plastic. Considering the plastic polymer compositions, 28.57 % were polyethylene terephthalate (PET), 21.43 % acrylic, 14.29 % high-density polyethylene (HDPE), 14.29 % Polypropylene (PP), 7.14 % ultra-high drawn polyethylene filament (UHMWPE), 7.14 % polyester and 7.14 % Polyethylene. The quantities and prevalence of MP in L. elliptica were higher than those found in other Antarctic marine species, and even in bivalves from populated regions of the world. Our work assessed the pollution status of L. elliptica near an effluent of wastewater plants and found that 95 % of individuals displayed MP and 100 % microfibers that could impact their population.

Novel flame retardants detected in marine plastic litter in coastal areas in Central Chile.

Flame retardants (FRs) are released throughout the plastic life cycle, potentially impacting the environment, biodiversity, and human health. This study analyzed novel flame retardants (NFR) in marine plastic litter (MPL) from six coastal areas in central Chile in November 2017. Target chemicals (n = 19) were analyzed using ultrasonic extraction with hexane, gas chromatography, and mass spectrometry (GC-MS). From all nineteen NFRs analyzed, only ten (53 %) were routinely detected. BTBPE (1,2-bis(2,4,6-tribromophenoxy) ethane) showed the highest concentrations at the Bellavista site (618 to 424,000 pg g-1), and HBB (Hexabromobiphenyl), banned since 1970, was detected in Coliumo (2630 to 13,700 pg g-1). These results show emerging transport patterns and underscore the critical need for enhanced waste management practices for MPL in coastal regions to prevent adverse impacts on marine biodiversity.

Marine litter pollution in a subantarctic beach of the Strait of Magellan, Punta Arenas, Chile.

This study assessed the presence of marine litter along the beach of the city of Punta Arenas, Chile. The sampling period coincided with the COVID-19 pandemic. A total of 239 plastic waste items were identified out of a total of 638 litter items. The Clean Coast Index reported within this study ranged from Clean (CCI 2-5) to Extremely dirty (CCI >20), especially near the port. The majority of litter items has been classified as originating from varied origins, as it is not possible to pinpoint a precise origin in most items. The results indicate that the predominant plastic litter in Punta Arenas is PVC. The results are discussed in relation to the sources and composition of the residues, the morpho dynamics of the coast, and the CCI is compared with other locations around the globe.

Occurrence of marine plastic litter and plasticizers from touristic beaches of Arauco Gulf in Central Chile.

Marine plastic litter (MPL) was collected from beaches (n = 3) of the Arauco Gulf in central Chile in spring 2021 and summer 2022. MPL was analyzed for physical and chemical characteristics, and plasticizers were also screened using FTIR-ATR. Three hundred seventeen plastic items with an accumulated weight of 226.8 g were found. MPL densities ranged from 0.4 to 17.1 items m-2. Significant differences (p < 0.05) between seasons were observed for Arauco and Maule beaches, being ∼ten times higher in summer compared to spring. Solid pieces were the predominant shape, macroplastics were the most abundant (>2.5 cm), and white and blue colors were dominant. Polypropylene (52 %) and polyethylene (31 %) were the predominant polymers. Plasticizers (n = 3) were detected in the MPL in the study area (dioctyl phthalate, polybutene, and alpha-methylstyrene) for the first time. This study contributes new information related to MPL in coastal areas of central Chile and their chemical composition.

Microplastics in Seabird Feces from Coastal Areas of Central Chile.

Pollution from plastic waste thrown into the ocean affects all levels of the food chain. Marine species of birds are affected by plastic particles of different sizes, especially the mesoplastics (1 to 10 mm) found in their digestive tract, which mainly cause obstructions. In the case of microplastics (1.000 µm to 1 mm), their presence in the digestive tract of these species has been widely reported. We studied fecal samples of the Dominican gull (Larus dominicanus) (n = 14), Magellanic penguins (Spheniscus magellanicus) (n = 8), and Humboldt penguin (Spheniscus humboldti) (n = 1) obtained from the Wildlife Rehabilitation Center of the Biobío region, Chile. Microfibers of various colors were present in the feces of Dominican gulls and Magellanic penguins, corresponding mainly in composition to polypropylene (PP) (83%) and rayon (77%). These results demonstrate that microplastic particles occur in the coastal environments of central Chile and suggest that they are probably circulating in the food chain.

Plastic debris, persistent organic pollutants and their toxicity impacts in coastal areas in Central Chile.

The chemical components of plastic wastes have made their disposal a major economic, social, and environmental problem worldwide. This study evaluated the acute toxicity and genotoxicity of marine plastic debris on the beaches of Concepción Bay, Central Chile, taken during three periods (spring, summer, and winter). An integrated approach was used, including chemical and toxicological data, using the Microtox® test with Vibrio fischeri and SOS chromotest with Escherichia coli and concentrations of polychlorinated biphenyls (PCBs), Organochlorine Pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs). The results presented here exclusively include the novel data obtained from the winter campaign, revealing high concentrations of PBDEs (238 ± 521 ng g-1). In addition, the genotoxicity and acute toxicity tests were sensitive for most of the samples studied. This investigation is the first attempt to analyse the toxicity of plastic debris in coastal areas along the Chilean coast.

Beached microplastics at the Bahia Blanca Estuary (Argentina): Plastic pellets as potential vectors of environmental pollution by POPs.

Microplastics (MPs) from the coastal areas of a highly anthropised estuary were sampled to assess their distribution in coastal sediments and their role as potential vectors of pollution. The average MP density was 1693 ± 2315 MPs/kg, which mainly accumulated in the high tide and storm berm areas of the beach. The Microplastic Pollution Index (MPPI), Microplastic Impact Coefficient (CMPI), Hierarchical Cluster Analysis and Principal Component Analysis revealed spatial variation in MPs pollution. High-density polyethylene plastic pellets were abundant at two beaches (192 ± 218 MPs/kg sediment). Furthermore, the presence of sorbed chemicals on pellets was assessed through GC-MS, showing 0.95 ± 0.09 ng/g of ∑7OCPs, 4.03 ± 0.89 ng/g of ∑7PCBs, 108.76 ± 12.88 ng/g of ∑16 PAHs and 122.79 ± 11.13 g/g of ∑29 PAHs. The sorption capacity of plastics, combined with their abundance, poses an environmental concern and also highlights their suitability as indicators of chemical exposure.

Environmental signature and health risk assessment of polybrominated diphenyl ethers (PBDEs) emitted from a landfill fire in Santiago de Chile.

Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in building materials, electronics, furnishings, vehicles, airplanes, plastics, polyurethane foams, and textiles for many years. Currently, the primary commercial mixtures, penta-, octa-, and deca-BDE, are globally restricted. Still, products containing PBDEs are expected to impact waste management and the environment for many years. In January 2016, an open fire in the Santa Marta landfill close to Santiago de Chile affected the city and surroundings. The fire caused several acute health effects and an increase in emergency hospitalizations. We measured PBDE levels in the areas affected by the fire in the air (gaseous and particulate) and soil, and PBDE emissions were estimated using a dispersion model. The results showed an increase in PBDE concentrations by a factor of 2-4 one day after the start of the fire. However, PBDE concentrations measured after the fire in PM10 and the gas phase were considered low compared to other regions. Interestingly, PBDEs' patterns differed across the sites; however, BDE209 was the dominant congener for all environmental matrices. A preliminary risk assessment was conducted using the daily exposure dose (DED) by air inhalation estimation. The results showed low DED values for adults and children and suggested no direct health risk due to PBDE exposure. This study brings new data useful for future solid waste management initiatives in the country.

Preliminary characterization of polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic hydrocarbons and polychlorinated dibenzo-p-dioxins and furans in atmospheric PM10 of an urban and a remote area of Chile.

The composition of particulate organic fraction was determined in atmospheric aerosols emitted in two sites of central and southern Chile. In particular, polycyclic aromatic hydrocarbons (PAHs), nitrated-PAHs (N-PAHs) and polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) were investigated in both the urban site of Concepcion and the remote site of Coyhaique. The sampling was carried out with an active device during March and April 2007, and organic compounds adsorbed in air particles, having an aerodynamic diameter lower than 10 microm (PM10), were characterized using gas chromatography coupled with mass spectrometric detection (GC-MS). Aerosol contents varied from 0.004 to 3.4 ng m(-3) for PAH, from 0.007 to 3.5 pg m(-3) for N-PAH, from 0.002 to 355.7 fg Nm(-3) for PCDDs and from 0.04 to 15 fg Nm(-3) for PCDFs. As expected, the lowest values were found in the remote area. In Concepcion city, despite the low number of samples, PAH levels and diagnostic ratios of some marker compounds suggested the diesel emissions, probably coming from trucks, as the major source of particulate organic pollutants associated with direct emission. Another important source of atmospheric pollution in the urban site was likely represented by the steel industry existing in this area, outlined both by the analysis of PAH and PCDD/F levels. In the samples collected in the remote air of Coyhaique (located in the southern part of Chile), the concentration of pollutants characterized by a long lifetime, as PCDD/Fs, could be related to long-range transport phenomena, instead of local sources.

Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part I - Levels and patterns after the 2010 tsunami.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) were determined in abiotic samples from Concepción Bay in Central Chile. Samples were soxhlet extracted and injected in gas chromatography-mass spectrometry (GCMS). Polybrominated diphenyl ethers (PBDEs) showed the highest levels in air (3-1100 pg m-3), in water (2-64 pg L-1), in sediment, and soil (1-78 ng g-1 (dw)). PAHs were also high in the air (1-6 ng m-3), in water (1-7 ng L-1), in sediment (90-300 ng g-1 (dw)), and in soil (15-2300 ng g-1 (dw)). The polychlorinated biphenyls (PCBs) and chlorinated pesticides were generally low and did not show clear trends along the water column, with exception of PAHs. New data are presented in this work to assess the health status of a relevant coastal area in central Chile.

Multicompartmental analysis of POPs and PAHs in Concepciόn Bay, central Chile: Part II - Air-sea exchange during Austral summer.

Air-sea exchange of POPs and PAHs was assessed in Concepción Bay during January, summer 2015. Results showed low levels, in air and water, for POPs (1-20 pg m-3, and 6-50 pg L-1, respectively) and for ΣPAHs (1-2 ng m-3 and 1-2 ng L-1, respectively). The highest levels were found for PBDEs (200-20,000 pg L-1) in the water samples (3-fold times higher than PCBs and OCP) and PBDE209 accounted for 90% of total ΣPBDEs. Air-sea exchange fluxes (ng m-2 d-1) were low in general, with exception of PBDEs showing values up to 40,000 ng m-2 d-1. Net deposition was found for PAHs, HCB and some PBDEs; while, BDE99, and BDE100 showed net volatilization. These findings contribute with new data of diffusive air-sea exchange on the southern hemisphere Pacific coast.

Using large amounts of firefighting foams releases per- and polyfluoroalkyl substances (PFAS) into estuarine environments: A baseline study in Latin America.

We analyzed per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) used to extinguish a major fire in a petrochemical terminal from the Port of Santos (Brazil). Eight AFFFs from seven known commercial brands and one unknown sample (AFFF-1 to AFFF-8) were evaluated. 17 PFAS were identified and quantified using high performance liquid chromatography (LC/MS). The concentrations of Σ17 PFAS in the AFFFs ranged from 500 to 9000 ng/g, with prevalence of short chain PFAS (~85 %), followed by long chain PFAS. Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), included in the global treaty of the Stockholm Convention, were also detected. We estimated that at least 635.96 g of PFAS were introduced in the estuary, representing a massive input of these substances. This investigation reports the PFAS composition of AFFFs used in firefighting in the GRULAC Region (Group of Latin American and Caribbean countries).

Occurrence of perfluoroalkyl substances (PFASs) in marine plastic litter from coastal areas of Central Chile.

Perfluorinated alkyl substances (PFASs) were determined in marine plastic litter (MPL) on six beaches of central Chile. MPL was characterized physically and chemically, showing an abundance of macroplastic (size >2.5 cm). The polypropylene (PP) (47%) was the predominant polymer found. The Desembocadura beach, located at the mouth of the Biobio River, recorded the highest abundance of MPL (3.7 items m-2). PFAS detected (n = 15/21) ranged from 279 to 1211 pg g-1 and accounted for MeFOSE (46%) > PFHxS (14%) > PFPA (11%) > PFBS (6%) > PFOA (4%) and > PFOS (4%). Long-chain PFAS were prevalent, which can be metabolically degraded into PFOS (new POPs). This study i) highlights the need to further investigate the occurrence of chemicals in the MPL to reduce their impact on the environment; and ii) points out the need to improve future coastal management strategies for the elimination of solid waste along the coast of the country.