The Ins and Outs of Per- and Polyfluoroalkyl Substances in the Great Lakes: The Role of Atmospheric Deposition.

As part of the Integrated Atmospheric Deposition Network, precipitation (n = 207) and air (n = 60) from five sites and water samples (n = 87) from all five Great Lakes were collected in 2021-2023 and analyzed for 41 per- and polyfluoroalkyl substances (PFAS). These measurements were combined with other available data to estimate the mass budget for four representative compounds, PFBA, PFBS, PFOS, and PFOA for the basin. The median Σ41PFAS concentrations in precipitation across the five sites ranged between 2.4 and 4.5 ng/L. The median Σ41PFAS concentration in lake water was highest in Lake Ontario (11 ng/L) and lowest in Lake Superior (1.3 ng/L). The median Σ41PFAS concentration in air samples was highest in Cleveland at 410 pg/m3 and lowest at Sleeping Bear Dunes at 146 pg/m3. The net mass transfer flows were generally negative for Lakes Superior, Michigan, and Huron and positive for Lakes Erie and Ontario, indicating that the three most northern lakes are accumulating PFAS and the other two are eliminating PFAS. Atmospheric deposition is an important source of PFAS, particularly for Lake Superior.

Conflicts of Interest in the Assessment of Chemicals, Waste, and Pollution.

Pollution by chemicals and waste impacts human and ecosystem health on regional, national, and global scales, resulting, together with climate change and biodiversity loss, in a triple planetary crisis. Consequently, in 2022, countries agreed to establish an intergovernmental science-policy panel (SPP) on chemicals, waste, and pollution prevention, complementary to the existing intergovernmental science-policy bodies on climate change and biodiversity. To ensure the SPP's success, it is imperative to protect it from conflicts of interest (COI). Here, we (i) define and review the implications of COI, and its relevance for the management of chemicals, waste, and pollution; (ii) summarize established tactics to manufacture doubt in favor of vested interests, i.e., to counter scientific evidence and/or to promote misleading narratives favorable to financial interests; and (iii) illustrate these with selected examples. This analysis leads to a review of arguments for and against chemical industry representation in the SPP's work. We further (iv) rebut an assertion voiced by some that the chemical industry should be directly involved in the panel's work because it possesses data on chemicals essential for the panel's activities. Finally, (v) we present steps that should be taken to prevent the detrimental impacts of COI in the work of the SPP. In particular, we propose to include an independent auditor's role in the SPP to ensure that participation and processes follow clear COI rules. Among others, the auditor should evaluate the content of the assessments produced to ensure unbiased representation of information that underpins the SPP's activities.

Per- and Polyfluoroalkyl Substances in Canadian Fast Food Packaging.

A suite of analytical techniques was used to obtain a comprehensive picture of per- and polyfluoroalkyl substances (PFAS) in selected Canadian food packaging used for fast foods (n = 42). Particle-induced gamma ray emission spectroscopy revealed that 55% of the samples contained <3580, 19% contained 3580-10 800, and 26% > 10 800 µg F/m2. The highest total F (1 010 000-1 300 000 µg F/m2) was measured in molded "compostable" bowls. Targeted analysis of 8 samples with high total F revealed 4-15 individual PFAS in each sample, with 6:2 fluorotelomer methacrylate (FTMAc) and 6:2 fluorotelomer alcohol (FTOH) typically dominating. Up to 34% of the total fluorine was released from samples after hydrolysis, indicating the presence of unknown precursors. Nontargeted analysis detected 22 PFAS from 6 different groups, including degradation products of FTOH. Results indicate the use of side-chain fluorinated polymers and suggest that these products can release short-chain compounds that ultimately can be transformed to compounds of toxicological concern. Analysis after 2 years of storage showed overall decreases in PFAS consistent with the loss of volatile compounds such as 6:2 FTMAc and FTOH. The use of PFAS in food packaging such as "compostable" bowls represents a regrettable substitution of single-use plastic food packaging.

From watersheds to dinner plates: Evaluating PFAS exposure through fish consumption in Southeast Michigan.

Muscle tissue and organ samples of six different fish species were collected from ten locations in Southeast Michigan's Huron and Rouge watersheds. Per- and polyfluoroalkyl substances (PFAS) were analyzed in 36 samples comprising filets, liver, gut, and eggs using targeted analysis and the direct total oxidizable precursor (dTOP) assay on a subset of six samples. The median concentrations of the ∑PFAS in filets from the Huron and Rouge watersheds were 13 and 6.3 ng/g wet weight (w.w.), respectively. Perfluorooctane sulfonate (PFOS) was the most detected and abundant compound in fish organs, with the liver having the largest overall burden of PFAS. The highest percent increase in targeted PFAS after the dTOP assay was observed in the Catfish filet (552%) while the smallest increase was in the Catfish liver (32%) accounting for 1.3 and 8.1 nMole F/g dry weight (d.w.), respectively. The positive matrix factorization (PMF) analysis revealed three distinct PFAS sources, of which the one attributed to PFOS explained 73% of the data. Results from this work have important implications for fish consumption in Michigan waterways. Among the filet samples analyzed, the calculated daily consumption limit of total PFOS was exceeded in approximately 82% and 91% of samples for adults and children over the age of seven years old, respectively.

Socio-Economic Factors Impact US Dietary Exposure to Halogenated Flame Retardants.

Although diet is an important route of exposure for brominated flame retardants (BFRs), little is known of their presence in US food. Therefore, we purchased meat, fish, and dairy product samples (n = 72) in Bloomington, IN, from 3 stores representing national retail chains at different price levels. Composite samples (n = 42) were analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), novel BFRs (NBFRs), and dechlorane plus (DP). Concentrations of total halogenated flame retardants (HFRs) ranged between 54 and 1,400 pg/g ww, with PBDEs being the predominant compounds. Concentrations of NBFRs, but not PBDEs, in US food items were significantly impacted by price, raising the issue of environmental justice. Nonorganic food generally had a higher abundance of BDE-209 than organic food items. Estimates of dietary exposure revealed that meat and cheese consumption contribute most to the overall HFR intake and that intakes are highest for children and for non-Hispanic Asians. Taking into account several caveats and limitations of this study, these results as a whole suggest that health burdens from dietary exposure to HFRs have become minimal for US citizens, highlighting the positive impact of regulatory efforts.

Associations between faecal chemical pollutants and hormones in primates inhabiting Kibale National Park, Uganda.

While anthropogenic pollutants are known to be a threat to primates, our understanding of exposure to pollutants in situ and their sub-lethal effects is still limited. We used non-invasive biomonitoring to examine associations between faecal concentrations of 97 chemical pollutants and faecal hormone metabolites of cortisol and oestradiol in four primate species inhabiting Kibale National Park, Uganda (chimpanzees-Pan troglodytes, olive baboons-Papio anubis, red colobus-Piliocolobus tephrosceles and red-tailed monkeys-Cercopithecus ascanius). Across all species (n = 71 samples), results demonstrated positive associations of organochlorine pesticides (OCPs) (ß = 0.143, p = 0.020) and organophosphate esters (ß = 0.112, p = 0.003) with cortisol in adult females. Additionally, we observed positive associations of OCPs (ß = 0.192, p = 0.013) and brominated flame retardants (ß = 0.176, p = 0.004) with cortisol in juveniles. Results suggest that cumulative pesticides and flame retardants are disruptive to endocrine function in these populations, which could have implications for development, metabolism and reproduction. Our study further demonstrates that faeces can be an important, non-invasive matrix for examining pollutant-hormone associations in wild primates and other critical wildlife populations.

Good News: Some Insecticides Have Been Virtually Eliminated in Air near the Great Lakes.

Persistent insecticides have been classic environmental problems for 60-70 years─perhaps starting with Rachel Carson's indictment of DDT. Both national and international regulations have been put in place over the last 20-30 years to eventually eliminate these compounds from the environment. One focus is the atmosphere, which acts as a major long-range transport route of these pollutants from their numerous sources to many ecosystems. This paper will ask, "Have we have made any progress in eliminating insecticides from the atmosphere?" We will focus only on the atmosphere around the North American Great Lakes and only on concentration measurements made once every 12 days since about 1990 for six classic insecticides. The answer is that some of these compounds (lindane, α-HCH, and endosulfans) are well on their way to being virtually eliminated, while the concentrations of others (DDT, chlordane, and hexachlorobenzene) have not changed much. We speculate that this difference in elimination is a result of soil compaction in cities (DDT, etc.) versus soil mixing in rural areas (lindane, etc.).

Amino antioxidants: A review of their environmental behavior, human exposure, and aquatic toxicity.

Amino antioxidants (AAOs), a suite of emerging organic contaminants, have been widely used in numerous industrial and commercial products to inhibit oxidation and corrosion. Recently, their environmental ubiquity, health risks, bioaccumulative and toxic potential have led to mounting public concern. This review summarizes the current state of knowledge on the production and usage, environmental occurrence, bioavailability, human exposure, and aquatic toxicity of representative AAOs, and provides suggestions for future research directions. Previous studies have revealed widespread distribution of many AAOs in various environmental matrixes, including air, water, sediment, dust, and biota. In addition to parent compounds, their degradation products, such as 2-anilino-5-(1,3-dimethylbutylamino)-1,4-benzoquinone (6PPD-Q) and 4-nitrodiphenylamine (4-NO2-DPA), have also been detected at high levels in multiple compartments. Dust ingestion and air inhalation are the two most well-investigated routes for human exposure to AAOs and their transformation products, while studies on other pathways (e.g., skin contact and dietary intake) still remain extremely limited. Moreover, AAO burdens in human tissue have been poorly documented. Toxicological data have shown that a few AAOs may cause teratogenic, developmental, reproductive, endocrinic, neuronic, and genetic toxicity to aquatic organisms, and the toxic capacities of degradation products differ from their precursors. Future studies should focus on elucidating AAO exposure for humans and associated health risks. Additionally, more attention should be given to AAO transformation products (particularly those quinoid derivatives possessing substantial affinity with DNA) and to the effects of complex mixtures of these chemicals.

Disentangling Source Profiles and Time Trends of Halogenated Flame Retardants in the Great Lakes.

Thirty-five polybrominated diphenyl ethers (PBDEs) and eight other alternative flame retardants were measured in air samples (vapor plus particles) collected at six sites near the North American Great Lakes between 2005 and 2019 as part of the Integrated Atmospheric Deposition Network (IADN). These data were analyzed using a multiple linear regression model to determine spatial and temporal trends. Overall, the levels of flame retardants remain significantly higher in urban sites compared to rural and remote sites except for pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), and total Dechlorane Plus (ΣDP). Here, we report the first findings of decreasing levels of ΣDP at Sturgeon Point, New York. The atmospheric levels of total PBDEs remain unchanged over time near Lakes Michigan and Superior and declined near Lakes Erie and Ontario, with rate constants at the latter two lakes revealing halving times of approximately 7 to 14 years. This work presents results from the first investigation of PBDE source apportionment in the Great Lakes atmosphere. Source apportionment by use of positive matrix factorization (PMF) identified two legacy commercial technical mixtures (i.e., penta-BDE and deca-BDE mixes) and elucidated a factor representing ambient degradation. Our results show that weathered local sources of technical commercial mixtures, and their photolysis contribute most to the total PBDE burden in the Great Lakes atmosphere.

Sulphurous air pollutants and exposure events of workers in thermal-mineral springs: a case study of Contursi Terme (Salerno, Italy).

Thermo-mineral springs are widely spread over the volcanic areas of Salerno, a city in southern Italy. Although the water of thermal structures provides beneficial effects on human health, the air is characterized by the presence of potentially toxic compounds, such as hydrogen sulphide (H2S) and sulphur dioxide (SO2). Exposure to sulphurous compounds may have detrimental effects on human health, with asthma being the most common. In this study, air concentrations of H2S and SO2 in the thermal springs of Contursi Terme (Salerno, Italy) were monitored for 4 months (using both active and passive sampling), along with the chemical and microclimatic characterization of thermal water, to assess workers' exposure to these pollutants. An in-depth characterization of indoor air at the springs is paramount to establish emission control limits for occupational exposure and to take protective measures. The air concentration of SO2 varied from 0.11 ± 0.02 to 0.91 ± 0.02 mg/m3, following a seasonal pattern (higher values in winter and lower in spring). Conversely, indoor H2S concentrations did not vary significantly with time, but outdoor levels (from 0.40 ± 0.03 to 1.90 ± 0.03 mg/m3) were always higher than indoor ones (from 0.11 ± 0.03 to 0.56 ± 0.03 mg/m3). Not negligible air concentrations of these pollutants were detected in this thermal spring workplace, so further investigations are needed to ensure workers' safety.

High levels of synthetic antioxidants and ultraviolet filters in children's car seats.

Forty-seven compounds among synthetic phenolic and amino antioxidants and ultraviolet filters, three suites of widely used chemical additives, were measured in eighteen popular children's car seats (fabric, foam, and laminated composites of both layers) marketed in the United States in 2018. Significantly higher levels of target compounds were found in foam and composite samples than in fabric samples. Median total concentrations of phenolic antioxidants and their transformation products ranged from 8.11 µg/g in fabric to 213 µg/g in foam In general, isooctyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (AO-1135) and 2,4-di-tert-butylphenol (24-DBP) were the most abundant among all target compounds with maximum levels of526 µg/g in composite and 13.7 µg/g, respectively. The total concentrations of amino antioxidants and their transformation products and of ultraviolet filters were at least one order of magnitude lower than those of phenolic antioxidants, with medians of 0.15-37.1 µg/g and 0.29-1.81 µg/g, respectively, in which the predominant congeners were 4-tert-butyl diphenylamine (BDPA), 4,4'-di-tert-butyl diphenylamine (DBDPA), 4-tert-octyl diphenylamine (ODPA), 2,4-dihydroxybenzophenone (BP-1), 2-hydroxy-4-methoxybenzophenone (BP-3), and 2-(2-benzotriazol-2-yl)-4-methylphenol (UV-P). Large variabilities in usage of these chemicals resulted in different compositional patterns among the car seats. These results suggest that these compounds are major polymeric additives in children's car seats as they are present at greater levels than previously measured groups of chemicals like brominated flame retardants and per- and polyfluoroalkyl substances. Given the documented toxic potentials of synthetic antioxidants and ultraviolet filters, their abundances in children products are a cause for concern.

Use and release of per- and polyfluoroalkyl substances (PFASs) in consumer food packaging in U.S. and Canada.

Numerous per- and polyfluoroalkyl substances (PFASs) occur in consumer food packaging due to intentional and unintentional addition, despite increasing concern about their health and environmental hazards. We present a substance flow analysis framework to assess the flows of PFASs contained in plant fiber-based and plastic food packaging to the waste stream and environment. Each year between 2018 and 2020, an estimated 9000 (range 1100-25 000) and 940 (range 120-2600) tonnes per year of polymeric PFASs were used in 2% of food packaging in the U.S. and Canada, respectively. At least 11 tonnes per year of non-polymeric PFASs also moved through the food packaging life cycle. Approximately 6100 (range 690-13 000) and 700 (range 70-1600) tonnes per year of these PFASs were landfilled or entered composting facilities in the U.S. and Canada, respectively, with the potential to contaminate the environment. The results suggest that minimal food packaging contains intentionally added PFASs which, nonetheless, has the potential to contaminate the entire waste stream. Further, this indicates that PFASs are not needed for most food packaging. These results serve as a benchmark to judge the effectiveness of future industry and government initiatives to limit PFAS use in food packaging.

Per- and Polyfluoroalkyl Substances in North American School Uniforms.

We analyzed 72 children's textile products marketed as stain-resistant from US and Canadian stores, particularly school uniforms, to assess if clothing represents a significant route of exposure to per- and polyfluoroalkyl substances (PFAS). Products were first screened for total fluorine (total F) using particle-induced γ-ray emission (PIGE) spectroscopy (n = 72), followed by targeted analysis of 49 neutral and ionic PFAS (n = 57). PFAS were detected in all products from both markets, with the most abundant compound being 6:2 fluorotelomer alcohol (6:2 FTOH). Total targeted PFAS concentrations for all products collected from both countries ranged from 0.250 to 153 000 ng/g with a median of 117 ng/g (0.0281-38 100 µg/m2, median: 24.0 µg/m2). Total targeted PFAS levels in school uniforms were significantly higher than in other items such as bibs, hats, stroller covers, and swimsuits, but comparable to outdoor wear. Higher total targeted PFAS concentrations were found in school uniforms made of 100% cotton than synthetic blends. Perfluoroalkyl acids (PFAAs) precursors were abundant in school uniforms based on the results of hydrolysis and total oxidizable precursor assay. The estimated median potential children's exposure to PFAS via dermal exposure through school uniforms was 1.03 ng/kg bw/day. Substance flow analysis estimated that ∼3 tonnes/year (ranging from 0.05 to 33 tonnes/year) of PFAS are used in US children's uniforms, mostly of polymeric PFAS but with ∼0.1 tonne/year of mobile, nonpolymeric PFAS.

Polychlorinated Biphenyls (PCBs) in the Environment: Occupational and Exposure Events, Effects on Human Health and Fertility.

In the last decade or so, polychlorinated biphenyls (PCBs) garnered renewed attention in the scientific community due to new evidence pointing at their continued presence in the environment and workplaces and the potential human risks related to their presence. PCBs move from the environment to humans through different routes; the dominant pathway is the ingestion of contaminated foods (fish, seafood and dairy products), followed by inhalation (both indoor and outdoor air), and, to a lesser extent, dust ingestion and dermal contact. Numerous studies reported the environmental and occupational exposure to these pollutants, deriving from building materials (flame-retardants, plasticizers, paints, caulking compounds, sealants, fluorescent light ballasts, etc.) and electrical equipment. The highest PCBs contaminations were detected in e-waste recycling sites, suggesting the need for the implementation of remediation strategies of such polluted areas to safeguard the health of workers and local populations. Furthermore, a significant correlation between PCB exposure and increased blood PCB concentrations was observed in people working in PCB-contaminated workplaces. Several epidemiological studies suggest that environmental and occupational exposure to high concentrations of PCBs is associated with different health outcomes, such as neuropsychological and neurobehavioral deficits, dementia, immune system dysfunctions, cardiovascular diseases and cancer. In addition, recent studies indicate that PCBs bioaccumulation can reduce fertility, with harmful effects on the reproductive system that can be passed to offspring. In the near future, further studies are needed to assess the real effects of PCBs exposure at low concentrations for prolonged exposure in workplaces and specific indoor environments.

An Innovative Filtering System for the Handling of Asbestos-Based Products: Improvement of Safety and Quality of Work in Analysis Laboratories.

Although being banned or restricted in many countries since the early 1990s, large quantities of asbestos are still used or present in building materials all over the world and its removal or handling requires specific systems that limit exposure to airborne fibers The exposure to asbestos causes chronic diseases such as asbestosis and lung cancer with an incubation period of 20 to 50 years. Among the operators most exposed to contamination are those who handle and analyze the materials in laboratories. For this reason, our work focused on an innovative method for removing a filter unit from a laboratory extraction hood, in order to improve the safety conditions for the operators and the surrounding environment. The hood has a particular construction technology with a mechanism that allows the spraying of a special encapsulating liquid on the ULPA filters below the work-bench, which is capable of forming a film and blocking the fibers on the surface of the same filter. The fibers are irreversibly bounded and can no longer be released into the surrounding environment. The monitoring of activity highlighted the absence of asbestos fibers in the air after installation of the filter and workers feel safer performing their activities. The introduction of an innovative filtering system enhanced the safety of work activities involving asbestos exposure, moreover, the time spent on the hood's maintenance and the risk perception of workers were improved.

Plastic Additives in Ambient Fine Particulate Matter in the Pearl River Delta, China: High-Throughput Characterization and Health Implications.

Elucidation of the chemical components of airborne fine particulate matter (PM2.5) facilitates the characterization of atmospheric contamination sources and associated human exposure risks. In the present study, we employed a high-throughput analytical approach to investigate the abundance and distribution of 163 plastic additives in ambient PM2.5 collected from 94 different sites across the Pearl River Delta region, China. These chemicals are from six categories, including organophosphate esters (OPEs), phthalate esters (PAEs), PAE replacements, bisphenol analogues, UV stabilizers, and antioxidants. Ninety-three of them exhibited a detection frequency greater than 50% in PM2.5, while the combined concentrations of target plastic additives ranged from 610 to 49,400 µg/g (median: 3500 µg/g) across sites. By category, concentrations of PAEs (median: 2710 µg/g) were one to three orders of magnitude greater than those of other groups, followed by PAE replacements (540 µg/g) and OPEs (76.2 µg/g). Chemical-dependent exposure risks to PM2.5-bound plastic additives were characterized via the estimated daily intake and hazard quotient (HQ) approaches, which resulted in two different risk prioritization systems. Although the HQ approach suggested no or very low health concerns when considering individual chemicals, the complexity of co-concurrent chemicals in PM2.5 raises the concern on potential health risks from exposure to airborne particles and a cocktail of chemical components.

Occurrence, Spatial, and Seasonal Variations, and Gas-Particle Partitioning of Atmospheric Current-Use Pesticides (CUPs) in the Great Lakes Basin.

There is very little information on the gas-particle partition and spatial and seasonal variations of current-use pesticides (CUPs) in the Great Lakes basin. The atmospheric concentrations of 36 CUPs were measured in 24 h gas and particle samples collected in 2017 at six sites in the Great Lakes basin. Thirteen individual CUPs were detected at least once in both gas- and particle-phase samples, with chlorothalonil, trifluralin, metolachlor, λ-cyhalothrin, cypermethrin, and chlorpyrifos detected in >50% samples. The gas-particle partitioning analysis suggests that gas-phase chemicals like trifluralin and chlorpyrifos were not influenced by either temperature or relative humidity while particle-phase chemicals like metolachlor were marginally and negatively correlated with relative humidity. Median total CUP concentrations were 339, 238, 84, 33, 60, and 6.0 pg/m3 at Chicago, Cleveland, Sturgeon Point, Point Petre, Sleeping Bear Dunes, and Eagle Harbor, respectively. The concentrations of total CUPs and most individual CUPs were generally higher at the urban sites of Chicago and Cleveland than at the rural/remote sites of Sturgeon Point, Point Petre, Sleeping Bear Dunes, and Eagle Harbor. Chlorothalonil, trifluralin, bifenthrin, and chlorpyrifos were the most abundant individual CUPs among fungicides, herbicides, pyrethroid insecticides, and other insecticides, respectively. The spatio-seasonal variation suggests that fungicides at Sturgeon Point and Sleeping Bear Dunes, with the highest fraction of agricultural land use, were associated with agricultural activities, while pyrethroid insecticides were generally driven by human activities.