Classes Of Contaminants Research Articles

Behavioral and molecular effects of micro and nanoplastics across three plastic types in fish: weathered microfibers induce a similar response to nanosized particles.

Micro and nanoplastics (MNPs) are ubiquitous in the environment and have been detected in most ecosystems, including remote regions. The class of contaminants under the MNP umbrella is quite broad and encompasses variable polymer types, shapes, and sizes. Fibers are the most frequently detected in the environment, followed by fragments, but still represent only a small fraction of laboratory studies. Many toxicity studies have been done using polystyrene microbeads which represent neither the polymer nor shape most present in the environment. Additionally, most of these studies are done using virgin particles when the majority of MNP pollution is from secondary microplastics which have weathered and broken down over time. To address these data gaps, we exposed the model fish Inland Silverside, Menidia beryllina, for 21-days to micro and nano cryo-milled tire particles, micro and nano polylactic acid, and polyester microfibers, both weathered and unweathered treatments were tested. We evaluated the impacts of these particles on growth, behavior, and gene expression to compare the relative toxicities of the different particles. We found that overall, the nanoparticles and weathered fibers had the greatest effect on behavior and gene expression. Gene ontology analysis revealed strong evidence suggesting MNP exposure affected pathways involved in muscle contraction and function. Unweathered microfibers decreased growth which may be a result of food dilution. Our results also suggest that under weathering conditions polyester microfibers breakdown into smaller sizes and induce toxicity similar to nanoparticles. This study highlights the variable effects of MNPs in fish and emphasizes the importance of considering particle shape and size in toxicity studies.

Introducing a prediction method for the photodegradation of p-cresol, a phenolic contaminant of emerging concern, in wastewater effluent

Despite extensive efforts to understand the photodegradation of phenolic contaminants of emerging concern (PhCECs) in aquatic systems, prediction methods, especially in waters containing effluent organic matter (EfOM), remain underdeveloped. This study introduces a prediction method for p-cresol, a representative PhCECs, based on correlations between EfOM optical parameters and p-cresol kinetic parameters. We examined p-cresol photodegradation in various EfOM samples, characterized by their optical properties, and used the reaction rate coefficient between EfOM and p-cresol, α3EfOM⁎, to quantify and predict p-cresol degradation in different wastewater effluent samples. Results showed significant correlations between p-cresol's photodegradation rate constant (0.144 to 0.441 h−1) and EfOM characteristics, with α3EfOM⁎ values ranging from 4 × 1011 to 10 × 1011 M−1 s−1. The method was validated with p-cresol at concentrations ranging from 25 to 100 μM and multiple EfOM samples. The method's applicability was further evaluated using propranolol, a pharmaceutical contaminant of emerging concern, demonstrating its versatility for predicting the degradation behavior of other contaminants in different wastewater samples. The method accurately predicted p-cresol and propranolol degradation across diverse wastewater samples, suggesting its potential for expansion to other classes of contaminants, aiding in water quality management, improving wastewater treatment processes, and enhancing environmental risk assessments.

Variability of PAH Patterns in Upper Forest Soil (Sub)horizons—A Case Study From South‐Central Poland

ABSTRACTPolycyclic aromatic hydrocarbons (PAHs) are a class of contaminants characterized by their persistent and toxic nature. This study examines the variability in PAH distribution patterns in the upper layers of forest soils, focusing on the influence of different characteristics of individual soil (sub)horizons. A total of 130 samples were collected from five forest areas in south‐central Poland and analyzed for the 16 priority PAHs. Samples were taken from the organic fermentative‐humic (Ofh), humic (A), and humic‐eluvial (AE) (sub)horizons. The highest mean concentrations of total PAHs were found in the subhorizon‐Ofh (Ofh—1547 μg kg−1, A—1103 μg kg−1, AE—109 μg kg−1). The PAH content was significantly correlated with SOM content and pH, but this correlation was only significant in the horizon‐A. The percentage contributions of 3‐, 4‐, 5‐, and 6‐ring compounds to the total PAHs varied among the investigated soil (sub)horizons. The subhorizon‐Ofh had the highest percentage contribution of 6‐ring PAHs, 4‐ and 5‐ring PAHs were most prevalent in the horizon‐A, while 3‐ring compounds in the horizon‐AE. The variability in PAH patterns was also reflected in individual PAH ratios (BaA/BaA+Chr, IcdP/IcdP+BghiP), confirming the different behavior of 4‐, 5‐, and 6‐ring compounds in these (sub)horizons. This suggests that the retention of PAHs in the investigated (sub)horizons is influenced by several factors, including pH, degree of SOM decomposition, and mineral fraction, each to a different extent. Our findings reveal significant knowledge gaps regarding the behavior and accumulation of PAHs in soil (sub)horizons, underscoring the need for further research.

Chemical Upcycling of Expired Pharmaceuticals as a Source of Value-Added Chemicals for Organic Synthesis and Medicinal Chemistry.

Pharmaceutical and veterinary products are a class of contaminants of emerging concern, and their presence in the environment is due to continuous and incorrect disposal. Environmental scientists have been accumulating data on their adverse effects on animal populations since toxicological effects on wildlife were first published. Therefore, recycling strategies are needed. Valuable active ingredients can be extracted from expired pharmaceuticals and recycled according to various strategies. In an effort to reveal the potential of the chemical upcycling of expired pharmaceuticals, the active ingredients gabapentin and pregabalin were extracted and used as starting materials to prepare a small collection of promising substrates endowed with functionalities and structural three-dimensionality. Gabapentin 1 was transformed into aminoalcohol 3, spiroamine 4, and the bioactive azaspirolactam 5. The lactam analog 6 was synthesized from pregabalin 2. Due to the biological profile of 5 and the structural similarity of the N-alkylated derivatives 5l and 6b with the drug piracetam, a collection of potentially bioactive structural analogs 5a-l and 6a-b were also prepared. Simple extraction, synthesis, and purification procedures were used as a means of chemical and economic revaluation, resulting in moderate to good yields at a low cost.

Impact of Benzodiazepine Delorazepam on Growth and Behaviour of Artemia salina Nauplii.

Benzodiazepines, a significant group of newly recognised water contaminants, are psychotropic medications prescribed for common anxiety symptoms and sleep disorders. They resist efficient degradation during sewage treatment and endure in aquatic environments. Their presence in aquatic matrices is increasing, particularly after the recent pandemic period, which has led many people to systematically use benzodiazepines to manage anxiety. In previous studies, an important interference of this class of drugs on both the larval and adult stages of some aquatic species has been demonstrated, with effects on behaviour and embryonic development. This study examined the influence of delorazepam, a diazepam metabolite, on Artemia salina development to gain insight into responses in naupliar larvae. Results demonstrated that treatments (1, 5, and 10 µg/L) increase the hatching percentage and induce a desynchronisation in growth. Mortality was only slightly increased (close to 10% at six days post-hatching), but lipid reserve consumption was modified, with the persistence of lipid globules at the advanced naupliar stages. Locomotory activity significantly decreased only at 10 µg/L treatment. No teratogenic effects were observed, though modest damages were noticed in the posterior trunk and eyes, two targets of environmental toxicity. The negative impact of delorazepam on Artemia salina adds to those already reported in other species of invertebrates and vertebrates, which are not yet considered targets of these drugs. This study underscores the need for further research and immediate attention to this class of contaminants and the importance of monitoring their presence during environmental risk assessments.

Analysis of contaminant residues in honey bee hive matrices

Pollinators provide ecological services essential to maintaining our food supply and propagating natural habitats. Populations are in decline due to environmental stressors including pesticides, pathogens, and habitat loss. To better understand the impacts of pesticide exposures on colony health, a field survey in Ohio, USA was conducted to monitor the potential contamination of honey bee colonies by pesticides. Apiaries (n = 10) were situated across an agricultural gradient and samples were collected over a 4-week period encompassing corn planting. Dead bees from entrance traps (DBT), pollen, and in-hive (IH) matrices including bee bread, honey, larvae, and nurse bees were analyzed for a whole suite of pesticides. Out of 210 pesticides targeted, 68 residues were quantified across 306 samples. Neonicotinoids, miticides, and fungicides were the dominant pesticide classes identified throughout all the matrix types. Neonicotinoids were detected at higher concentrations and at higher frequencies compared to fungicides, specifically in field pollen samples. DBT also contained high concentrations of these two contaminant classes, although detection frequencies for neonicotinoids were typically lower. Overall, herbicides and non‑neonicotinoid insecticides were found with low frequency and at low concentrations. For most pesticide classes, trends for the mean concentrations were DBT > IH nurse bees > field pollen > IH larvae > IH honey. Pesticides were detected in 100 % of samples with concentrations ranging from 0.01 ppb (diphenylamine) to 2790 ppb (clothianidin). All samples were contaminated with at least two pesticide residues, while 19 samples presented over ten detects and maximum detections of 20 in DBT. Pesticide residues were positively correlated with agricultural gradients across sites and sampling periods. These findings reveal that foraging leads to the exposure of the entire colony to a wide range of pesticides. Moreover, residues determined in DBT serve as an effective proxy for monitoring hive matrices with significantly less disturbance to active hives.

Are light curve classification metrics good proxies for SN Ia cosmological constraining power?

When selecting a lc classifier for use as part of a photometric supernova Ia (SN Ia) cosmological analysis, it is common to make decisions based on metrics of classification performance, such as the contamination within the photometrically classified SN Ia sample, rather than a measure of cosmological constraining power. If the former is an appropriate proxy for the latter, this practice would save those designing an analysis pipeline from eliminate the computational expense of a full cosmology forecast in the analysis pipeline design process This study tests the assumption that lc classification metrics are an appropriate proxy for cosmology metrics. We emulated photometric SN Ia cosmology lc samples with controlled contamination rates of individual contaminant classes and evaluated each of them under a set of classification metrics. We then derived cosmological parameter constraints from all samples under two common analysis approaches and quantified the impact of contamination by each contaminant class on the resulting cosmological parameter estimates. We observe that cosmology metrics are sensitive to both the contamination rate and the class of the contaminating population, whereas the classification metrics are shown to be insensitive to the latter. Based on these findings, we discourage any exclusive reliance on classification-based metrics for analysis design decisions, which (counterintuitively) include but are not limited to the classifier choice. Instead, we recommend optimising science analysis pipeline design choices using a metric of the information gained about the physical parameters of interest.

Prenatal exposure to environmentally relevant levels of PAHs inhibits spermatogenesis in adult mice and the mechanism involved

Polycyclic aromatic hydrocarbons (PAHs) are a class of contaminants that cannot be banned. Exposure to PAHs has been reported to alter spermatogenesis in mammals, but little is known about prenatal exposure to a mixture of PAHs on the reproductive toxicity of adult offspring. In this study, we investigated the associations between prenatal exposure to environmentally relevant levels of PAHs in mice and testicular dysfunction, including impaired spermatogenesis and steroid hormone dysfunction in male offspring on postnatal day 180. The percentage of testicular apoptotic cells was significantly increased, which was further verified by the up-regulated BAX protein. The expression of Ar and the Leydig cell marker Cyp11a1 was down-regulated, suggesting an impairment in the synthesis of steroid hormones. DNA hypermethylation of the Tnp1 and Sohlh2 promoters suppresses transcriptional expression, consequently altering the sperm production process. This study shows that prenatal exposure to PAHs may induce long-term reproductive toxicity.

From detection methods to risk prevention: Control of N-nitrosamines in foods and the role of natural bioactive compounds.

Food processing unavoidably introduces various risky ingredients that threaten food safety. N-Nitrosamines (NAs) constitute a class of food contaminants, which are considered carcinogenic to humans. According to the compiled information, pretreatment methods based on solid-phase extraction (SPE) were widely used before the determination of volatile NAs in foods. The innovation of adsorbents and hybridization of other methods have been confirmed as the future trends of SPE-based pretreatment methods. Moreover, technologies based on liquid chromatography and gas chromatography were popularly applied for the detection of NAs. Recently, sensor-based methods have garnered increasing attention due to their efficiency and flexibility. More portable sensor-based technologies are recommended for on-site monitoring of NAs in the future. The application of artificial intelligence can facilitate data processing during high-throughput detection of NAs. Natural bioactive compounds have been confirmed to be effective in mitigating NAs in foods through antioxidation, scavenging precursors, and regulating microbial activities. Meanwhile, they exhibit strong protective activities against hepatic damage, pancreatic cancer, and other NA injuries. Further supplementation of data on the bioavailability of bioactives can be achieved through encapsulation and clinical trials. The utilization of bioinformatics tools rooted in various omics technologies is suggested for investigating novel mechanisms and finally broadening their applications in targeted therapies.

Radiological and elemental composition of cryoconite and glacier mice from Vatnajökull, Iceland

Cryoconite has been demonstrated to be an efficient accumulator of some classes of contaminants on glaciers in both mountain and polar environments, however the accumulation of contaminants in cryoconite in Iceland has received very little attention to date. To understand the spatial variability of natural and anthropogenic fallout radionuclides and metals on glaciers in Iceland, we present the first study of this region including both cryoconite from three glaciers: Virkisjökull; Skaftafellsjökull; and Falljökull, together with moss balls (‘glacier mice’) from Falljökull. The cryoconite samples and glacier mice were analysed using XRF spectrometry to assess their elemental composition and gamma spectrometry to identify, and quantify, fallout radionuclides, primarily 7Be, 137Cs, 241Am, excess 210Pb, and 40K. The results revealed that the cryoconite samples had similar compositions, influenced by local geology and natural sources of volcanic ash and dust. Higher concentrations of radionuclides and heavy metals were found in both cryoconite and glacier mice compared to control samples comprising nearby proglacial sediments. In comparison to other glaciers in the Northern Hemisphere, however, cryoconite from Icelandic glaciers contains some of the lowest activity concentrations of key radionuclides. Consequently, cryoconite deposits that are released and diluted during the melt and retreat of Icelandic glaciers are unlikely to be of environmental concern following transport to proglacial areas.

Bi2MoO6/MWCNTs-COOH/GCE electrochemical probe for ultrasensitively and selectively detecting antibiotic norfloxacin

Antibiotics have emerged as a class of contaminants of concern globally, raising widespread worry and unease, primarily because of their inappropriately use and endless migration in food chains. Electrochemical ultrasensitive and selective determination of norfloxacin (NOR) using bismuth-based bimetallic salt bismuth molybdate (Bi2MoO6) and carboxylated multi-walled carbon nanotube (MWCNTs-COOH) hybrid electrode as sensing platforms is presented hereby. The electrocatalytic ability of the electrodes was verified to be enhanced by the synergy effect of both Bi2MoO6 and MWCNTs-COOH using cyclic voltammetry and electrochemical impedance spectroscopy. Linear scan voltammetry was applied to detect NOR. The oxidation peak current was linearly correlated with NOR concentration of 0.03–10 μM and the low limit detection of the optimized method was 6.7 nM (S/N = 3). In addition, it was verified that Bi2MoO6/MWCNTs-COOH/GCE probe had good stability, reproducibility, repeatability and selectivity. The spiked recovery method for NOR in milk and lake water samples showed recoveries of 94.8 – 96.9% and 90.2 – 98.3%, respectively, which can be used to determine NOR in real samples with high sensitivity. The preparation of Bi2MoO6/MWCNTs-COOH/GCE provides a new prototype for probing NOR detection at nanomolar concentration and safeguarding antibiotic contamination in environmental and food chains.

Molecular Insights into the Binding and Conformational Changes of Hepcidin25 Blood Peptide with 4-Aminoantipyrine and Their Sorption Mechanism by Carboxylic-Functionalized Multiwalled Carbon Nanotubes: A Comprehensive Spectral Analysis and Molecular Dynamics Simulation Study.

In this work, the main purpose is to analyze and understand the mechanism and thermodynamic interactions of carboxylic acid-functionalized multiwalled carbon nanotubes (cf-MWCNTs) and 4-aminoantipyrine (AAP) with human hepcidine25 (Hep25) using multispectroscopic and molecular docking modeling methods, binding free energy calculations, and molecular dynamics (MD) simulations under physiological conditions. AAP belongs to a class of persistent environmental contaminants, and its residue is a potential hazard to human health, exhibiting a high binding affinity with blood peptides. Hepcidin is a 25-residue peptide hormone with four disulfide bonds that regulates the iron balance in vertebrates and contributes to host immunity as a cysteine-rich antimicrobial peptide. Due to their diverse properties and pollutant absorption capabilities, CNTs demonstrate important biological effects in biological applications, particularly in the noncovalent interactions with blood peptides. A comprehensive molecular dynamics simulation integrated with molecular docking methodologies was employed to explore the binding free energy between AAP and Hep25, identify binding sites, elucidate thermodynamic characteristics, and evaluate the binding forces governing their interaction. The investigation delved into elucidating the precise binding site of AAP within the Hep25 protein and thoroughly analyzed the impact of AAP on the microenvironment and conformational dynamics of Hep25. The circular dichroism (CD) experimental results highlight a reduction in β-sheet composition following the introduction of AAP and cf-MWCNT. In addition, outcomes from fluorescence spectroscopy demonstrate that both cf-MWCNT and AAP significantly attenuated Hep-25 fluorescence via a static quenching mechanism. According to the MD simulations, the presence of AAP induces changes in the secondary structure of Hep25 and enhances its hydrophobicity. Additionally, our findings demonstrated that alongside the alteration in protein structure and functionality induced by contaminants, cf-MWCNTs possess the capability to mitigate the contaminant-induced effects on Hep25 activity while preserving the overarching structural integrity of Hep25. Based on the distance and RDF data, we found that during the simulation the presence of the cf-MWCNT causes the AAP to move away from the Hep25, and as a result fewer and weaker interactions of the AAP with the Hep25 will be observed. Likewise, free energy calculations indicate that the binding of Hep25 to AAP and cf-MWCNT involves electrostatic, π-cationic, and π-π stacking interactions. The research findings offer invaluable insights into the intricate influence of pollutants and carbon nanotubes on protein functionality within the circulatory system and their toxicity in vivo for prospective investigations.

Glyphosate and other plant protection products in size-segregated urban aerosol: Occurrence and dimensional trend

Plant protection products (PPPs) play a fundamental role in the maintenance of agricultural fields and private/public green areas, however they can contaminate zones nearby the application point due to wind drift, resuspension, and evaporation. Several studied have deepened the relationship between PPPs and living beings’ health, suggesting that these products might have a negative influence. Some PPPs belong to the class of Emergent Contaminants, which are compounds whose knowledge on the environmental distribution and influence is limited. These issues are even more stressed in urban aerosol, due to the high residential density that characterizes this area. Therefore, this study assessed the contamination caused by polar PPPs, such as herbicides (i.e., Glyphosate), fungicides (i.e., Fosetyl Aluminium), and growth regulators (i.e. Maleic Hydrazide), in size-segregated urban aerosol and evaluated their concentration variability with respect to atmospheric parameters (humidity, temperature, rain). Moreover, hypotheses on possible sources were formulated, exploiting also back-trajectories of air masses. A total of six PPPs were found in the samples: glyphosate was more present in the coarse fraction (2.5–10 μm), Fosetyl Aluminium, chlorate and perchlorate were more present in the coarse/fine fractions (10-1 μm), while cyanuric acid and phosphonic acid were mostly concentrated in the fine/ultrafine fractions (<1 μm). While for the first four we suspect of local sources, such as private gardening, the two latter might derive from the entire Po Valley, a highly polluted area in the North of Italy, and from degradation of other substances.

Diverse PFAS produce unique transcriptomic changes linked to developmental toxicity in zebrafish.

Per- and polyfluoroalkyl substances (PFAS) are a widespread and persistent class of contaminants posing significant environmental and human health concerns. Comprehensive understanding of the modes of action underlying toxicity among structurally diverse PFAS is mostly lacking. To address this need, we recently reported on our application of developing zebrafish to evaluate a large library of PFAS for developmental toxicity. In the present study, we prioritized 15 bioactive PFAS that induced significant morphological effects and performed RNA-sequencing to characterize early transcriptional responses at a single timepoint (48h post fertilization) after early developmental exposures (8h post fertilization). Internal concentrations of 5 of the 15 PFAS were measured from pooled whole fish samples across multiple timepoints between 24-120h post fertilization, and additional temporal transcriptomics at several timepoints (48-96h post fertilization) were conducted for Nafion byproduct 2. A broad range of differentially expressed gene counts were identified across the PFAS exposures. Most PFAS that elicited robust transcriptomic changes affected biological processes of the brain and nervous system development. While PFAS disrupted unique processes, we also found that similarities in some functional head groups of PFAS were associated with the disruption in expression of similar gene sets. Body burdens after early developmental exposures to select sulfonic acid PFAS, including Nafion byproduct 2, increased from the 24-96h post fertilization sampling timepoints and were greater than those of sulfonamide PFAS of similar chain lengths. In parallel, the Nafion byproduct 2-induced transcriptional responses increased between 48 and 96h post fertilization. PFAS characteristics based on toxicity, transcriptomic effects, and modes of action will contribute to further prioritization of PFAS structures for testing and informed hazard assessment.

Boosting degradation of C4mim cation by metal alkoxide-derived Co4S3-activated Oxone: Yolk-Shell-Engineered enhancement and DFT-assisted toxic evaluation

The low bio-degradability of room-temperature ionic liquids (RTILs) makes RTILs a new class of persistent contaminants. It is urgent to develop useful technology to eliminate RTILs to prevent their presence in the environment. Sulfate-radical advanced oxidation processes (SR-AOPs) are particularly suitable for degrading such low-biodegradability pollutants. This study introduces a novel SR-AOP aimed at eliminating the representative RTIL, 1-butyl-3-methylimidazolium chloride (C4M), using an enhanced catalyst to activate Oxone. Traditionally, cobalt (Co) has been used for Oxone activation, but homogeneous catalysis with Co ions poses recovery challenges and secondary pollution risks. Recent studies suggest that cobalt sulfides (CSs) are more promising due to their superior redox properties, which are critical for effective Oxone activation. In this work, we developed a catalyst composed of cobalt sulfide (CS) with a unique yolk-shell (YS) structure, termed YSCS, to maximize catalytic activity. YSCS was easily fabricated from Co-Glycerate (CoG) precursors through a self-destruction/reconstruction process during sulfidization, resulting in a YS structure covered by self-assembled Co4S3 nanoplates. This morphology provides a highly mesoporous structure, enhanced electrochemical properties, and expanded active sites. Consequently, YSCS demonstrated significantly higher catalytic activity for Oxone activation compared to its precursor CoG and the benchmark Co3O4, with a reaction rate constant (k) of 0.108 min-1, surpassing those of Co3O4 NP + Oxone (0.007 min-1) and CoG + Oxone (0.023 min-1). Additionally, YSCS + Oxone exhibited a lower activation energy (Ea) of 17.8 kJ/mol for C4M degradation. The degradation pathway of C4M by YSCS + Oxone was thoroughly investigated using Fukui indices and analyzing the degradation by-products. Toxicity assessments showed that YSCS + Oxone significantly reduces the acute toxicity and bioconcentration factor of C4M, as well as potential mutagenicity and developmental toxicity risks. These findings confirm that YSCS is a highly effective catalyst for Oxone activation and RTIL degradation in water.

Mountaintop Removal Coal Mining Contaminates Snowpack across a Broad Region.

Mountaintop removal coal mining is a source of downstream pollution. Here, we show that mountaintop removal coal mining also pollutes ecosystems downwind. We sampled regional snowpack near the end of winter along a transect of sites located 3-60 km downwind of coal mining in the Elk River valley of British Columbia, Canada. Vast quantities of polycyclic aromatic compounds (PACs), a toxic class of organic contaminants, are emitted and transported atmospherically far from emission sources. Summed PAC (ΣPAC) snowpack concentrations ranged from 29-94,866 ng/L. Snowpack ΣPAC loads, which account for variable snowpack depth, ranged from <10 μg/m2 at sites >50 km southeast of the mines to >1000 μg/m2 at sites in the Elk River valley near mining operations, with one site >15,000 μg/m2. Outside of the Elk River valley, snowpack ΣPAC loads exhibited a clear spatial pattern decreasing away from the mines. The compositional fingerprint of this PAC pollution matches closely with Elk River valley coal. Beyond our study region, modeling results suggest a depositional footprint extending across western Canada and the northwestern United States. These findings carry important implications for receiving ecosystems and for communities located close to mountaintop removal coal mines exposed to air pollution elevated in PACs.

First data on polybrominated diphenyl ethers and temporal trend of polychlorinated biphenyls in European brown bear as a bioindicator species

The contamination status on persistent organic pollutants (POPs) in the Croatian terrestrial ecosystem was investigated by analyzing two classes of contaminants in adipose tissue of male European brown bear (Ursus arctos, N = 27) collected in 2021 and 2022. In addition to seven indicator polychlorinated biphenyls (PCBs), for the first time seven polybrominated diphenyl ethers (PBDEs) were analyzed in terrestrial species from this region. Sum of mass fractions detected in adipose tissue ranged from 0.011 to 0.463 ng g−1 lipid weight (lw) for the PBDEs, and from 0.652 to 30.17 ng g−1 lw for PCBs, with two orders of magnitude difference in the median value for these two groups of POPs (PBDEs: 0.022 ng g−1 lw; PCBs: 2.307 ng g−1 lw). PCBs dominated over PBDEs with a share of over 94 % of the total mass fractions of both groups of analyzed POPs. Results of the comparison of the PCB levels in the adipose tissue of brown bears reported here and in previous investigation from this region showed decrease in PCB-28, but increase of PCB-118 and PCB-180, while other congeners seemed to have reached a steady-state level in the environment over a ten-year period. Among the compounds analyzed in this study, BDE-47, PCB-153 and PCB-180 were the dominant congeners. Somewhat higher sum of PCBs was measured in April compared to October, although not statistically significant, indicating possible impact of winter hibernation causing concentration of lipophilic compounds due to body fat loss. Revealed POP levels in brown bears are consistent with the data on the low contamination of the Croatian terrestrial ecosystem in general.

Tracking the history of polycyclic aromatic compounds in London through a River Thames sediment core and ultrahigh resolution mass spectrometry

Polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and heteroatom-containing analogues, constitute an important environmental contaminant class. For decades, limited numbers of priority PAHs have been routinely targeted in pollution investigations, however, there is growing awareness for the potential occurrence of thousands of PACs in the environment. In this study, untargeted Fourier transform ion cyclotron resonance mass spectrometry was used for the molecular characterisation of PACs in a sediment core from Chiswick Ait, in the River Thames, London, UK. Using complex mixture analysis approaches, including aromaticity index calculations, the number of molecular PAC components was determined for eight core depths, extending back to the 1930s. A maximum of 1676 molecular compositions representing PACs was detected at the depth corresponding to the 1950s, and a decline in PAC numbers was observed up the core. A case linking the PACs to London’s coal consumption history is presented, alongside other possible sources, with some data features indicating pyrogenic origins. The overall core profile trend in PAC components, including compounds with oxygen, sulfur, nitrogen, and chlorine atoms, is shown to broadly correspond to the 16 priority PAH concentration profile trend previously determined for this core. These findings have implications for other industry-impacted environments.

Unique hepatic maternal transfer pattern of trace metals and perfluoroalkyl substances (PFAS) in a bluntnose sixgill shark (Hexanchus griseus)

The fate and distribution of environmental contaminants includes bioaccumulation within marine organisms. A deceased 4-m long adult female bluntnose sixgill shark, pregnant with 72 pups, was recovered from Coles Bay on Vancouver Island, BC, Canada in 2019. This specimen provided a unique opportunity to examine maternal transfer of contaminants in a yolk-sac viviparous shark species. Liver subsamples of the adult and offspring were analyzed for 18 targeted inorganic elements by inductively coupled plasma optical emission spectroscopy (ICP-OES) and 21 targeted perfluoroalkyl substances (PFAS) by liquid chromatography-electrospray ionization-high resolution mass spectrometry (LC-ESI-Orbitrap MS). The maternal-offspring transfer efficiencies in liver tissue were subsequently examined for both contaminant classes. Concentrations of all detectable metals apart from calcium and magnesium were found to be higher in the mother compared to the offspring, including substantial levels of toxic cadmium (6 ± 2 mg kg−1 dw) and lead (7 ± 3 mg kg−1 dw). Conversely, high maternal transfer efficiencies were observed for PFAS (i.e., ΣPFAS = 71 ± 9 ng g−1 ww in offspring compared to 13 ± 9 ng g−1 ww in the mother). This study highlighted the unique maternal transfer characteristics of PFAS in bluntnose sixgill sharks depending on the structure of the polar head group, with greater liver-to-liver transfer efficiencies observed for perfluorocarboxylic acids (PFCAs) than perfluorosulfonic acids (PFSAs) of the same fluorocarbon chain length.

Evaluation of the Pathway of Contaminants in the Environment: A Case Study of Different Aquatic Environmental Compartments

The occurrence of contaminants of emerging concern (CECs) in several environmental compartments has raised significant concern given the extensive array of compounds and their consistent detection across various environmental matrices. Monitoring all potentially harmful compounds and identifying their sources is nearly impossible. However, providing data on their occurrence is crucial and lays the groundwork for decision makers to craft mitigation strategies toward a more sustainable water policy. Hence, the primary aim of this study was to conduct an evaluation study on CECs occurrence in the environment. The main novelty relies on understanding their specific pathway in three different environmental aquatic compartments. For that, a combined study of a systematic review and systemic analysis was performed. Initially, the five most common types of CECs found in aquatic ecosystems (groundwater and surface water) and wastewater were considered. For each group of CECs, five contaminants were identified. A bibliographic portfolio was generated through the application of a systematic review. Finally, a systemic analysis of the bibliographic portfolio was conducted. All classes of contaminants studied were identified in the environmental compartments evaluated. Except for pesticides, the degree of contamination by CECs followed a sequence based on the aquatic compartment (i.e., WW–SW–GW).