In 2018, over 30,000 L of fluorine-free firefighting foam was used to extinguish an industrial warehouse fire of uncharacterized chemical and industrial waste. Contaminated firewater and runoff were discharged to an adjacent freshwater creek in Melbourne, Australia. In this study, we applied nontarget analysis using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QToF-MS) to 15 surface water samples to investigate the presence of legacy, novel and emerging per-and polyfluoroalkyl substances (PFAS). We identified six novel and emerging fluorotelomer-based fluorosurfactants in the Australian environment for the first time, including: fluorotelomer sulfonamido betaines (FTABs or FTSA-PrB), fluorotelomer thioether amido sulfonic acids (FTSASs), and fluorotelomer sulfonyl amido sulfonic acids (FTSAS-So). Legacy PFAS including C₆–C₈ perfluoroalkyl sulfonic acids, C₄–C₁₀ perfluoroalkyl carboxylic acids, and perfluoro-4-ethylcyclohexanesulfonate were also detected in surface water. Of note, we report the first environmental detection of ethyl 2-ethenyl-2-fluoro-1-(trifluoromethyl) cyclopropane-1-carboxylate. Analysis of several Class B certified fluorine-free foam formulations allowed for use in Australia revealed that there was no detectable PFAS. Patterns in the homologue profiles of fluorotelomers detected in surface water are consistent with environments impacted by fluorinated aqueous film-forming foams. These results provide strong evidence that firewater runoff of stockpiled fluorinated firefighting foam was the dominant source of detectable PFAS to the surrounding environment.

Biomagnification of persistent toxic substances (PTSs) in food chains is of environmental concern, but studies on biotransport of PTSs across aquatic and riparian food chains are still incomplete. In this study, biomagnification of several PTSs including methylmercury (MeHg), polybrominated diphenyl ethers (PBDEs), and 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE) was investigated in adjacent aquatic and riparian food webs. Concentrations of MeHg and PBDEs ranged from 2.37 to 353 ng/g dry weight (dw) and not detected (Nd) to 65.1 ng/g lipid weight (lw) in riparian samples, respectively, and ranged from Nd to 705 ng/g dw and Nd to 187 ng/g lw in aquatic samples, respectively. Concentrations of MeHg were significantly correlated with δ¹³C (p < 0.01) rather than δ¹⁵N (p > 0.05) values in riparian organisms, while a significant correlation was observed between concentrations of MeHg and δ¹⁵N (p < 0.01) in aquatic organisms. Biomagnification factors (BMFs) and trophic magnification factors (TMFs) of PBDE congeners were similar in riparian and aquatic food webs, while BMFs and TMFs of MeHg were much higher in aquatic food web than those in riparian food web. The results indicate the biotransport of MeHg from aquatic insects to terrestrial birds, and δ¹³C can be a promising ecological indicator for biotransport of pollutants across ecosystems.

Exposure to metals has been linked with the risk of hypertensive disorders of pregnancy (HDP), but little is known about the potential effects of exposure to metal mixtures. Thus, our study aimed to investigated the impact of a complex mixture of metals on HDP, especially the interactions among metal mixtures. We did a population-based nested case-control study from October 2013 to October 2016 in Wuhan, China, including 146 HDP cases and 292 controls. Plasma concentrations of Aluminum (Al), Barium (Ba), Cobalt (Co), Copper (Cu), Lead (Pb), Mercury (Hg), Molybdenum (Mo), Nickel (Ni), Selenium (Se), Strontium (Sr), Thallium (Tl), and Vanadium (V) were measured and collected between 10 and 16 gestational weeks. We employed quantile g-computation, conditional logistic regression models, and Bayesian Kernel Machine Regression (BKMR) to assess the association of individual metals and metal mixtures with HDP risk. In the quantile g-computation, the OR for a joint tertile increase in plasma concentrations was 3.67 (95% CI: 1.70, 7.91). Hg contributed the largest positive weights and followed by Al, Ni, and V. In conditional logistic regression models, concentrations of Hg, Al, Ni, and V were significantly associated with the risk of HDP (p-FDR < 0.05). Compared to the lowest tertiles, the ORs (95% CI) for the highest tertiles of these four metals were 2.67 (1.44, 4.95), 3.09 (1.70, 5.64), 5.31 (2.68, 10.53), and 4.52 (2.26, 9.01), respectively. In the BKMR analysis, we observed a linear positive association between Hg, Al, V, and HDP, and a nonlinear relationship between Ni and HDP. A potential interaction between Al and V was also identified. We found that exposure to metal mixtures in early pregnancy, both individually and as a mixture, was associated with the risk of HDP. Potential interaction effects of Al and V on the risk of HDP may exist.

Infant exposure to per/polyfluoroalkyl compounds is associated with immune disruption. We examined associations between neonatal concentrations of perflurooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) and immunoglobulin (Ig) isotype profiles in a prospective cohort of infants. We measured Ig isotypes, including IgA, IgE, IgM and the IgG subclasses IgG₁, IgG₂, IgG₃, and IgG₄, and PFOA and PFOS in newborn dried bloodspots from N = 3175 infants in the Upstate KIDS Study (2008–2010). We examined the association between newborn Ig isotype levels and individual PFOS and PFOA concentrations using mixed effects regression models with a random intercept to account for twins among study participants. We assessed the joint effect PFOA and PFOS with quantile-based g-computation on all singletons and one randomly selected twin (N = 2901), with Ig categorized as above or below median value. Models were adjusted for infant sex, and maternal pre-pregnancy body mass index, race, parity, age and infertility treatment. In adjusted models, PFOA was inversely associated with IgE (coefficient = −0.12 per unit increase in PFOA, 95% CI: −0.065, −0.17), whereas IgG₂, IgM, and IgA were positively associated with PFOA (coefficient for IgG₂ = 0.22, 95% CI: 0.15, 0.27; coefficient for IgM = 0.11, 95% CI: 0.08, 0.15; and coefficient for IgA = 0.15, 95% CI: 0.07, 0.18). There was no relation between PFOS and Ig isotypes. Analysis of the joint effect of PFOA and PFOS showed an OR of 1.2 (95% CI: 1.04, 1.36) for IgA and OR of 1.12 (95% CI: 1.00, 1.24) for IgG₂ levels above the median for every quartile increase. PFOA levels were significantly associated with elevated IgA, IgM, IgG₂, and reduced levels of IgE in single-pollutant models. A small but significant joint effect of PFOA and PFOS was observed. Our results suggest that early exposure to PFOA and PFOS may disrupt neonatal immunoglobulin levels.

Eyes convey important information about the external and internal worlds of animals. Individuals can follow the gaze of others to learn about the location of salient objects as well as assess eye qualities to evaluate the health, age or other internal states of conspecifics. Because of the increasing prevalence of artificial lighting at night (ALAN), urbanized individuals can potentially garner information from conspecific eyes under both daylight and ALAN. We tested this possibility using a visual modeling approach in which we estimated the maximum distance at which individuals could detect conspecific eyes under daylight and high levels of ALAN. We also estimated the minimum light level at which individuals could detect conspecific eyes. Great-tailed grackles (Quiscalus mexicanus) were used as our study species because they are highly social and are unusual among birds in that they regularly gather at nocturnal roosts in areas with high levels of ALAN. This visual modelling approach revealed that grackles can detect conspecific eyes under both daylight and ALAN, regardless of iris coloration. The grackles could detect conspecific eyes at farther distances in daylight compared to ALAN. Our results highlight the potential importance of lighting conditions in shaping social interactions.

Land use regression (LUR) models have been widely used in epidemiological studies and risk assessments related to air pollution. Although efforts have been made to improve the performance of LUR models so that they capture the spatial heterogeneity of fine particulate matter (PM₂.₅) in high-density cities, few studies have revealed the vertical differences in PM₂.₅ exposure. This study proposes a three-dimensional LUR (3-D LUR) assessment framework for PM₂.₅ exposure that combines a high-resolution LUR model with a vertical PM₂.₅ variation model to investigate the results of horizontal and vertical mobile PM₂.₅ monitoring campaigns. High-resolution LUR models that were developed independently for daytime and nighttime were found to explain 51% and 60% of the PM₂.₅ variation, respectively. Vertical measurements of PM₂.₅ from three regions were first parameterized to produce a coefficient of variation for the concentration (CVC) to define the rate at which PM₂.₅ changes at a certain height relative to the ground. The vertical variation model for PM₂.₅ was developed based on a spline smoothing function in a generalized additive model (GAM) framework with an adjusted R² of 0.91 and explained 92.8% of the variance. PM₂.₅ exposure levels for the population in the study area were estimated based on both the LUR models and the 3-D LUR framework. The 3-D LUR framework was found to improve the accuracy of exposure estimation in the vertical direction by avoiding exposure estimation errors of up to 5%. Although the 3-D LUR-based assessment did not indicate significant variation in estimates of premature mortality that could be attributed to PM₂.₅, exposure to this pollutant was found to differ in the vertical direction. The 3-D LUR framework has the potential to provide accurate exposure estimates for use in future epidemiological studies and health risk assessments.

To evaluate the chemical status of groundwater bodies (GWB) according to the European Groundwater Directive, EU Member States are required to take into account natural background levels (NBLs) where needed. Assessing the NBLs in coastal GWBs is complicated by seawater intrusion which can be amplified by groundwater withdrawals increasing the salinization of such groundwater systems. This paper proposes a new method for the NBLs assessment in coastal areas based on a double pre-selection (PS) with fixed/dynamic limits. A case study in the Apulia region, located in southeastern Italy, is proposed, where we investigated four adjacent GWBs which form the complex karst, fractured Murgia aquifer, hosted in the Jurassic-Cretaceous carbonate platform, bounded by two seas and sustained by saltwater of marine intrusion in the coastal areas. Data related to 139 monitoring stations (MSs) of the regional groundwater monitoring network were used. The first PS, “static”, based on a fixed limit of anthropogenic contamination markers (NO₃ and NH₄), allows for the elimination of MSs impacted by human activities. On these, the second PS, “dynamic”, based on the identification of Cl anomalous values, allows for the identification of additional MSs affected by saline contamination. The residual dataset of MSs was used for the definition of NBLs of Cl, SO₄, F and B. A statistical comparison with historical Cl observations finally allowed us to verify if the salinity of current groundwater is representative of pristine conditions. The calculated NBLs of salinity parameters are higher for the two coastal GWBs, with chloride values between 0.8 and 2 mg/L. Conversely, fluorides always show very low NBLs. The double PS approach seems more effective for NBLs calculation in coastal aquifers affected by saline contamination, where the use of a fixed Cl limit fails. It may respond to the international needs for a standardized procedure for NBL assessment.

The deployment of aqueous film forming foams (AFFF) used for firefighting during emergencies and training often releases per- and polyfluoroalkyl substances (PFAS) into the environment. In October 2018, first responders in Providence, RI, USA applied an AFFF during a fuel spill. Due to the proximity of the incident to the upper reaches of Narragansett Bay (NB), an unknown quantity of gasoline and AFFF entered the estuary via surface runoff and stormwater drains. Water samples near the spill were collected approximately 15 h after the incident and analyzed for 24 PFAS. Minor increases in measured PFAS concentrations were observed relative to pre- and post-spill samples at monitoring sites near the incident, except 6:2-fluorotelomer sulfonate (6:2-FTS) that peaked post-spill (max 311 ng/L). After performing the total oxidizable precursor (TOP) assay on water samples and the AFFF concentrate, significant increases in perfluorocarboxylic acids (PFCAs) were observed. One compound, 6:2 fluorotelomer mercaptoalkylamido sulfonate (6:2-FTSAS), was identified as a major component of the AFFF used. Peak areas of 6:2-FTSAS and the degradation product 6:2-FTSAS-sulfoxide corresponded to observed increases in the TOP assay results and were useful as tracers of AFFF in surrounding waters. Elevated levels of PFAS at the time of sampling were limited to a confined area of the Providence River due to river flow and tidal action. Observed concentrations were also compared to hydrodynamic model results, and results confirmed rapid dissipation of AFFF components with distance from the spill. However, modeled results did not capture possible secondary releases of AFFF from local municipal stormwater and sewer infrastructure, as observational data suggest. The multiple lines of evidence of PFAS present in surface waters permitted a better assessment of the potential environmental impacts from products such as AFFF for which the chemical composition is largely unknown.

Research over the last three decades showed that chromium, particularly the oxyanion chromate Cr(VI) behaves as a toxic environmental pollutant that strongly damages plants due to oxidative stress, disruption of nutrient uptake, photosynthesis and metabolism, and ultimately, represses growth and development. However, mild Cr(VI) concentrations promote growth, induce adventitious root formation, reinforce the root cap, and produce twin roots from single root meristems under conditions that compromise cell viability, indicating its important role as a driver for root organogenesis. In recent years, considerable advance has been made towards deciphering the molecular mechanisms for root sensing of chromate, including the identification of regulatory proteins such as SOLITARY ROOT and MEDIATOR 18 that orchestrate the multilevel dynamics of the oxyanion. Cr(VI) decreases the expression of several glutamate receptors, whereas amino acids such as glutamate, cysteine and proline confer protection to plants from hexavalent chromium stress. The crosstalk between plant hormones, including auxin, ethylene, and jasmonic acid enables tissues to balance growth and defense under Cr(VI)-induced oxidative damage, which may be useful to better adapt crops to biotic and abiotic challenges. The highly contrasting responses of plants manifested at the transcriptional and translational levels depend on the concentration of chromate in the media, and fit well with the concept of hormesis, an adaptive mechanism that primes plants for resistance to environmental challenges, toxins or pollutants. Here, we review the contrasting facets of Cr(VI) in plants including the cellular, hormonal and molecular aspects that mechanistically separate its toxic effects from biostimulant outputs.

The occurrence of organic pollutants in soil is a major environmental concern. These compounds can reach the soil in different ways. Point sources, related to pesticides that are used intentionally, can be applied directly to the soil, or reach the soil indirectly due to application to the aerial parts of crops. On the other hand, non-point sources, which reach soils collaterally during irrigation and/or fertilization, or due to the proximity of plots to industrialized urban centers. Long-range transport of global organic pollutants must also be taken into account. In this study, 218 pesticides, 49 persistent organic pollutants, 37 pharmaceutical active compounds and 6 anticoagulant rodenticides were analyzed in 139 agricultural soil samples collected between 2018 and 2020 in the Macaronesia. This region comprised four inhabited archipelagos (Azores, Canary Islands, Cape Verde, and Madeira) for which agriculture is an important and traditional economic activity. To our knowledge, this is the first study on the levels of organic compound contamination of agricultural soils of the Macaronesia. As expected, the most frequently detected compounds were pesticides, mainly fungicides and insecticides. The Canary Islands presented the highest number of residues, with particularly high concentrations of DDT metabolites (p,p’ DDE: 149.5 ± 473.4 ng g⁻¹; p,p’ DDD: 16.6 ± 35.6 ng g⁻¹) and of the recently used pesticide fenbutatin oxide (302.1 ± 589.7 ng g⁻¹). Cape Verde was the archipelago with the least contaminated soils. Very few pharmaceutical active compounds have been detected in all archipelagos (eprinomectin, fenbendazole, oxfendazole and sulfadiazine). These results highlight the need to promote soil monitoring programs and to establish maximum residue limits in soils, which currently do not exist at either continental or local level.