Persistent Organic Contaminants Research Articles

The emerging and legacy persistent organic contaminants in corals of the South China Sea

Seawater warming, ocean acidification and chemical pollution are the main threats to coral growth and even survival. The legacy persistent organic contaminants (POCs), such as polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), and the emerging contaminants, including polybrominated diphenyl ethers (PBDEs), dechlorane plus (DPs) and novel brominated flame retardants (NBFRs) were studied in corals from Luhuitou fringing reef in Sanya Bay and Yongle atoll in Xisha Islands, the South China Sea (SCS). Total average concentrations of ∑16PAHs, ∑23OCPs, ∑34PCBs, ∑8PBDEs, ∑2DPs and ∑5NBFRs in 20 coral species (43 samples) from the SCS were 40.7 ± 34.6, 5.20 ± 5.10, 0.197 ± 0.159, 3.30 ± 3.70, 0.041 ± 0.042 and 36.4 ± 112 ng g−1 dw, respectively. PAHs and NBFRs were the most abundant compounds and they are likely to be dangerous pollutants for future coral growth. Compared to those found in other coral reef regions, these pollutants concentrations in corals were at low to median levels. Except for PBDEs, POCs in massive Porites were significantly higher than those in branch Acropora and Pocillopora (p < 0.01), as large, closely packed corals may be beneficial for retaining more pollutant. The current study contributes valuable data on POCs, particularly for halogenated flame retardants (HFRs, including PBDEs, DPs and NBFRs), in corals from the SCS, and will improve our knowledge of the occurrence and fate of these pollutants in coral reef ecosystems.

Alps at risk: High-mountain lakes as reservoirs of persistent and emerging contaminants

Despite their remote locations, high-mountain lakes located in the Alps are vulnerable to chemical pollution. This discussion explores the important aspects of these lakes as repositories of Persistent Organic Pollutants (POPs) and Contaminants of Emerging Concern (CECs), elucidating their sources and implications for both the environment and human health. In terms of the presence of POPs in high-altitude lakes of the Alps, 14 studies have been identified examining the occurrence of polychlorinated biphenyls, dichlorodiphenyltrichloroethane an its metabolites, polybrominated diphenyl ethers, and polycyclic aromatic hydrocarbons. The bulk of research on POPs in high-mountain lakes is concentrated in the Italian Alps (63%), followed by Switzerland (22%), Austria (12%), and France (3%), respectively. Sediment is predominantly investigated (65%), followed by fish (33%) and water (2%). Similarly, in relation to the presence of CECs in high-mountain lakes of the Alps, six studies have been identified investigating the occurrence of musks, perfluorinated compounds, and microplastics. Investigations into CECs predominantly occur in Switzerland (42%), France (33%), and Italy (25%), with fish samples (muscle and liver) being the primary focus (46%), followed by sediment (17%) and water (17%). Other compartments like zooplankton, frog/tadpoles, and snow remain less explored. The discussion also shed light on various pathways through which pollutants reach these remote landscapes, including atmospheric transport, glacial meltwater, and human activities. Protecting these pristine peaks demands concerted efforts encompassing ongoing research, vigilant monitoring, and dedicated conservation initiatives.

Organic pollutants degradation by a superb MXene-based Z-scheme heterojunction Photocatalyst: Synthesize, delamination process, mechanism and toxicity assessment

In this study, a new CeO2/MXene-TiO2 photocatalyst was created using a simple and economical approach and thoroughly characterized by different techniques, including TEM, XPS, BET, XRD, Raman, and SEM. The focus of this research was to improve the degradation of tetracycline (TC), a commonly used antibiotic with known environmental and health risks. To optimize the degradation process, RSM- CCD method was used to systematically vary key parameters including initial TC concentration, photocatalyst dosage, pH and irradiation time. The trapping experiments were revealed that the hydroxyl (•OH) and superoxide anion (•O2-) radicals played a crucial role in this process. An impressive degradation efficiency of 96.60 % was achieved under optimal conditions, attributed to the Z-scheme electron transfer heterojunction, which enhances the generation and separation of oxidant species. LC-MS analysis was employed to elucidate the photodegradation pathway of TC by identifying the reaction intermediates. This analysis facilitated the proposal of a plausible mechanism for TC degradation. The demonstrated efficacy of the CeO₂/MXene-TiO₂ photocatalyst suggests its potential application in wastewater treatment for the significant degradation of persistent organic contaminants.

Enhanced degradation of tetracycline by TiO2@MXene with peroxydisulfate under visible light irradiation

Photocatalysis and peroxydisulfate (PS) based advanced oxidation techniques are promising technologies in the field of water treatment that can be used to destroy increasingly persistent organic contaminants. The current work used a simple hydrothermal approach to synthesize a catalyst made of composites of TiO2 nanospheres and multi-layer Ti3C2Tx sheets (TiO2@MXene). Tetracycline (TC) was then effectively degraded by the TiO2@MXene material integrated with PS activation (300 mg/L). Under simulated sunlight (AM 1.5G, P = 2.8 W) irradiation, the combination method dramatically increases TC degradation. Following a 30-min treatment with 300 mg/L TiO2@MXene (wt.10 %), the optimal efficiency can reach 100 %. As the reactive functional species, holes (h+), SO4-•, •OH, and •O2− dominate the catalytic process. Furthermore, investigation was conducted into significant factors such as catalyst dosage, PS dosage, common anions, and TiO2 loading dosage. The TiO2@MXene material was demonstrated to be a feasible and sustainable strategy worth taking into consideration in the mitigation of emerging water contaminants due to its ease of recovery, stability of surface properties, and recyclability. Furthermore, the proposed degradation mechanism further demonstrated the viability of TiO2@MXene with PS in TC degradation. This, this study provides insights into the design of effective photocatalyst coupling PS activation for the efficient degradation of organic pollutants.

Ecotoxicity of perfluorooctanoic acid and perfluorooctane sulfonate on aquatic plant Vallisneria natans.

Perfluorinated compounds (PFCs) are persistent organic contaminants that are highly toxic to the environment and bioaccumulate, but their ecotoxic effects on aquatic plants remain unclear. In this study, the submerged plant Vallisneria natans was treated with short-term (7 days) and long-term (21 days) exposures to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) at concentrations of 0, 0.01, 0.1, 1.0, 5.0, and 10 mg/L, respectively. The results showed that both high concentrations of PFOA and PFOS inhibited the growth of V. natans and triggered the increase in photosynthetic pigment content in leaves. The oxidative damage occurred mainly in leaves, but both leaves and roots gradually built up tolerance during the stress process without serious membrane damage. Both leaves and roots replied to short-term stress by activating superoxide dismutase (SOD), catalase (CAT) and polyphenol oxidase (PPO), while peroxidase (POD) was involved under high concentration stress with increasing exposure time. Leaves showed a dose-effect relationship in integrated biomarker response (IBR) values under short-term exposure, and the sensitivity of roots and leaves to PFOS was higher than that of PFOA. Our findings help to increase knowledge of the toxic effects of PFCs and have important reference value for risk assessment and environmental remediation of PFCs in the aquatic ecosystem.

Characterization of persistent organic contaminants in the atmosphere of Gadani's ship breaking yards and its surrounding: Implications for sustainable ship recycling practices

Gadani is internationally renowned for its extensive ship-breaking operations, positioning it as one of the globe's primary ship-breaking hubs. A comprehensive study was conducted to evaluate the presence of organic contaminants in the air within Gadani, encompassing the areas surrounding ship-breaking facilities, proximate residential settlements, and adjacent roadways. Passive air samplers were employed to collect a total of 30 air samples. The analytical results unveiled a notably elevated concentration of specific organic compounds, with a pronounced prevalence of polycyclic aromatic hydrocarbons (PAHs), short-chain chlorinated paraffins (SCCPs), and polychlorinated biphenyls (PCBs) at the ship-breaking yard. Notably, dichlorodiphenyltrichloroethanes (DDTs) and DDE were detected at substantially lower levels. In particular, sites in close proximity to ship-breaking activities exhibited elevated concentrations of PCBs (Σ7PCB 0.065429 to 7.345714 ng/sample), PAHs (Σ8PAH 2.44 to 134.23 ng/sample), and SCCPs (0.18 to 25.6 ng/sample). Conversely, DDTs and DDE demonstrated higher concentrations near residential settlements. The evaluation of Molecular Diagnostic Ratios for PAHs revealed anthracene/anthracene + phenanthrene ratios of 0.88, 0.69, and 0.5 for ship-breaking areas, roadside locations, and community surroundings, respectively. Furthermore, the benz[a]anthracene/benz-[a]anthracene + chrysene molecular ratios were measured at 0.77 (ship-breaking sites), 0.82 (roadside), and 0.83 (community), respectively. The molecular ratio of fluoranthene/fluoranthene + pyrene at ship-breaking sites was 0.23, while roadside and community ratios were 0.36 and 0.89, respectively. These findings underscore the significant contribution of ship-recycling activities to the atmospheric release of SCCPs, PCBs, and PAHs, emphasizing the global imperative for responsible ship recycling practices.

Unveiling the oxidation mechanism of persistent organic contaminants via visible light-induced dye-sensitized reaction by red mud suspension with peroxymonosulfate

A dye-sensitized photocatalysis system was developed for degrading persistent organic contaminants using solid waste (i.e., red mud, RM) and peroxymonosulfate (PMS) under visible light. Complete degradation of acid orange 7 (AO7) was achieved in RM suspension with PMS, where the co-existence of amorphous FeO(OH)/α-Fe2O3 was the key factor for PMS activation. The experimental results obtained from photochemical and electrochemical observations confirmed the enhanced PMS activation due to the Fe-OH phase in RM. DFT calculations verified the acceleration of PMS activation due to the high adsorption energy of PMS on FeO(OH) and low energy barrier for generating reactive radicals. Compared to the control experiment without AO7 showing almost no degradation of other organic contaminants (phenol, bisphenol A, 4-chlorophenol, 4-nitrophenol, and benzoic acid), photo-sensitized AO7* enhanced electron transfer in the FeIII/FeII cycle, dramatically enhancing the degradation of organic contaminants via radical (•OH, SO4•−, and O2•−) and non-radical (dye*+ and 1O2) pathways. Therefore, the novel finding of this study can provide new insights for unique PMS activation by heterogeneous Fe(III) containing solid wastes and highlight the importance of sensitized dye on the interaction of PMS with Fe charge carrier for the photo-oxidation of organic contaminants under visible light.

Ozonation of dioxolanes in water: Kinetics, transformation mechanism, and toxicity

Dioxolanes, which are structural analogs to dioxane, are emerging persistent mobile organic contaminants. These compounds are frequently detected in water and wastewater, but their removal has been rarely addressed in the literature. This work systematically investigated the ozonation of two representative dioxolanes, i.e., 1,3-dioxolane (1,3-D) and 2-methyl-1,3-dioxolane (2-M-1,3-D). The degradation rates of two dioxolanes exhibited a positive correlation with both ozone dosage and solution pH increment. Specifically, direct ozone oxidation dominates the degradation of dioxolanes at slightly acidic pH, while hydroxyl radical (•OH) becomes the primary oxidant under weak alkaline condition. The second-order reaction rate constants of ozone with 1,3-D and 2-M-1,3-D were determined to be 5.48 and 8.00 M−1s−1, respectively. The reaction rate constants with •OH were 9 orders of magnitude higher, reaching (3.75-8.18) × 109 and (2.65-5.78) × 109 M−1s−1 for 1,3-D and 2-M-1,3-D, respectively. A kinetic model involving 112 reactions well simulated the degradation of 1,3-D and 2-M-1,3-D under various conditions accordingly. Eight transformation products were identified totally, and seven of them (i.e., formic acid, acetic acid, oxalic acid, formaldehyde, acetaldehyde, glyoxylic acid, and 1,2-ethanediol monoacetate) were quantified. The observed evolution of these identified degradation products concludes that the degradation of 1,3-D and 2-M-1,3-D during ozonation mainly involves H-abstraction, dimerization, ring opening, disproportionation, and hydrolysis. This work not only provides essential kinetic data of dioxolanes, but also sheds light on their potential transformation mechanisms and aquatic environment risks during ozonation process.

Multi-Heteroatom Doped Fe@CN Activation Peroxomonosulfate for the Removal of Trace Organic Contaminants from Water: Optimizing Fabrication and Performance

Modification of catalysts by multi-heteroatom doping (S, P, B) is an effective way to improve the peroxomonosulfate activation performance of catalysts. In recent years, highly toxic and persistent trace organic contaminants have been frequently detected in water. Consequently, we proposed the advanced oxidation processes of peroxomonosulfate activated by multi-heteroatom doped Fe@CN (X-Fe@CN) to eliminate trace organic contaminants. The physical phases of X-Fe@CN and its precursors were characterized by X-ray diffraction and scanning electron microscopy. In evaluating the catalytic properties and iron ion leaching of X-Fe@CN-activated PMS for the removal of dicamba and atenolol, B-Fe@CN and PB-Fe@CN were selected and optimized. The active sites of the catalysts were characterized by X-ray photoelectron spectroscopy and Raman. The pathways of PMS activation by B-Fe@CN and PB-Fe@CN were identified in combination with electron paramagnetic resonance and electrochemical experiments. Defects, O-B-O and pyrrolic nitrogen on the surface of B-Fe@CN could adsorb and activate PMS to produce SO4•−, ·OH and 1O2. Further doping with P enhanced the electron transfer on the catalyst surface, thus accelerating the activation of peroxomonosulfate. This study compared the effects of multi-heteroatom modifications and further demonstrated the synergistic effect between P and B, which can provide a theoretical basis for the selection of multi-heteroatom doped catalysts in water treatment.

Effects of short and long-term thermal exposure on microbial compositions in soils contaminated with mixed benzene and benzo[a]pyrene: A short communication

Polycyclic aromatic hydrocarbons (PAHs) and benzene, toluene, ethylbenzene, and xylene (BTEX) are the most persistent and toxic organic contaminants often found co-contaminated in anthropogenic and petrochemical industrial sites. Therefore, an experiment was performed for the safe biodegradation of benzene and benzo[a]pyrene (BaP) through thermally-enhanced biodegradation, and to explore the influence of elevated thermal treatments on microbial diversity and composition. The results revealed that elevated thermal treatments (15 to 45 °C) significantly enhanced the diversity of both bacteria and fungi. The composition analysis revealed that short-term and long-term elevated temperature conditions can directly enhance the specificity of microorganisms that play a crucial role in the biodegradation of benzene and BaP co-contaminated soil. Moreover, the indirect role of elevated temperature conditions on microbial compositions was through the fluctuations of soil properties, especially soil pH, moisture, TOC, potassium, phosphorous, total Fe, Fe(II), and Fe(III). In addition, the correlation analyses revealed that thermal exposure enhances the synergistic association (fungal-fungal, fungal-bacterial, bacterial-bacterial) of microbes to degrade the toxic contaminants and to cope with harsh environmental conditions. These results concluded that the biodegradation of benzene and BaP co-contamination was efficiently enhanced under the thermally-enhanced biodegradation approach and the elevation of temperature can affect the microbial compositions directly via microbial specificity or indirectly by influencing the soil properties.

Improved sea rice yield and accelerated di-2-ethylhexyl phthalate (DEHP) degradation by straw carbonization returning in coastal saline soils

Di-2-ethylhexyl phthalate, a persistent organic contaminant, is widely distributed in the environment and poses substantial threats to human health; however, there have been few investigations regarding the risks and remediation of DEHP in coastal saline soils. In this work, we studied the influences of straw carbonization returning on sea rice yield and DEHP degradation. Straw carbonization returning significantly increased soil nutrients and reduced salt stress to improve sea rice yield. DEHP degradation efficiency was enhanced to a maximum of 78.27% in straw carbonized return with 60% sea rice, mainly attributed to the high pH value, high soil organic matter and enriched potential DEHP degraders of Nocardioides, Mycobacterium and Bradyrhizobium. Some key genes related to metabolism (esterase and cytochrome P450) and DEHP-degradation (pht4, pht5, pcaG, dmpB, catA and fadA) were elevated and explained the accelerated DEHP degradation, shifting from the benzoic acid pathway to the protocatechuate pathway in straw carbonization returning. The results obtained in this study provide a deep and comprehensive understanding of sea rice yield improvement and DEHP degradation mechanisms in coastal paddy soil by a straw carbonization returning strategy.

Electro-oxidation of persistent organic contaminants at graphene sponge electrodes using intermittent current

Borophene (Bph) and hexagonal boron nitride (hBN)-modified graphene sponge anode coupled to N-doped graphene sponge cathode were applied for electrochemical degradation of persistent organic contaminants using intermittent current. Three different ON-OFF pulse cycles were tested using low-conductivity supporting electrolyte in flow-through mode. Functionalization of the reduced graphene oxide (RGO) with Bph and hBN improved the ability of the double layer to store electrical charge, thus maintaining the generation of H2O2, O3, and ·OH even during the OFF cycles. Both anodes tested showed enhanced contaminant removal during shorter OFF periods (e.g. 52.5 s/52.s and 75 s/30 s ON/OFF), due to the improved retention of anode charge during the shorter OFF stages. Electrochemical removal of the target contaminants required 24 kWh m−3 in continuous current mode for both hBN-RGO and Bph-RGO anodes at 231 A/m−2, which was lowered to 11.7 and 13.5 kWh m−3 respectively, using ON-OFF pulse cycles. Electrochemical degradation pathways were elucidated in both systems using carbamazepine as a representative persistent contaminant. Flow-through reactors with both Bph- and hBN-RGO anodes removed ≥60 % of the target contaminants in a single pass using continuous current, whereas intermittent current led to somewhat decreased removal efficiencies (43–58 %) due to the scavenging effect of the wastewater matrix. Thus, halving the current ON time led to less than 20 % decrease in the removal efficiencies due to the capacitive properties of RGO. Given that switching to intermittent current decreased the energy consumption from 9.3 kWh m−3 to 4.4 kWh m−3 (Bph-RGO anode) and from 6.9 kWh m−3 to 3.6 kWh m−3 (hBN-RGO anode), higher removal of the target contaminants can be achieved by coupling sequential reactors in the intermittent current mode.

Persistent Trace Organic Contaminants Are Transformed Rapidly under Sulfate- and Fe(III)-Reducing Conditions in a Nature-Based Subsurface Water Treatment System.

Subsurface treatment systems, such as constructed wetlands, riverbank filtration systems, and managed aquifer recharge systems, offer a low-cost means of removing trace organic contaminants from treated municipal wastewater. To assess the processes through which trace organic contaminants are removed in subsurface treatment systems, pharmaceuticals and several major metabolites were measured in porewater, sediment, and plants within a horizontal levee (i.e., a subsurface flow wetland that receives treated municipal wastewater). Concentrations of trace organic contaminants in each wetland compartment rapidly declined along the flow path. Mass balance calculations, analysis of transformation products, microcosm experiments, and one-dimensional transport modeling demonstrated that more than 60% of the contaminant removal could be attributed to transformation. Monitoring of the system with and without nitrate in the wetland inflow indicated that relatively biodegradable trace organic contaminants, such as acyclovir and metoprolol, were rapidly transformed under both operating conditions. Trace organic contaminants that are normally persistent in biological treatment systems (e.g., sulfamethoxazole and carbamazepine) were removed only when Fe(III)- and sulfate-reducing conditions were observed. Minor structural modifications to trace organic contaminants (e.g., hydroxylation) altered the pathways and extents of trace organic contaminant transformation under different redox conditions. These findings indicate that subsurface treatment systems can be designed to remove both labile and persistent trace organic contaminants via transformation if they are designed and operated in a manner that results in sulfate-and Fe(III)-reducing conditions.

Perfluorooctanoic acid induces behavioral impairment and oxidative injury in Nauphoeta cinerea nymphs.

Perfluorooctanoic acid (PFOA) is a persistent organic contaminant with potential health threats to both animals and humans. However, the impact of PFOA on insects, which play significant roles in ecosystems, is understudied. We evaluated the toxicological impact of ecologically relevant concentrations of PFOA (0, 25, 50, 100, and 200µg L-1) on Nauphoeta cinerea nymphs following exposure for 42 consecutive days. We analyzed the behavior of the insects with automated video-tracking software and processed the head, midgut, and fat body for biochemical assays. PFOA-exposed insects exhibited significant reductions in locomotory abilities and an increase in freezing time. Furthermore, PFOA exposure reduced acetylcholinesterase activity in the insect head. PFOA exposure increased the activities of superoxide dismutase, glutathione peroxidase, and catalase in the head and midgut, but decreased them in the fat body. PFOA also significantly increased glutathione-S transferase activity, while decreasing glutathione levels in the head, midgut, and fat body. Additionally, PFOA exposure increased reactive oxygen and nitrogen species, nitric oxide, lipid peroxidation, and protein carbonyl contents in the head, midgut, and fat body of the insects. In conclusion, our findings indicate that PFOA exposure poses an ecological risk to Nauphoeta cinerea.

A new perspective on predicting the reaction rate constants of hydrated electrons for organic contaminants: Exploring molecular structure characterization methods and ambient conditions

Hydrated electrons (eaq−) exhibit rapid degradation of diverse persistent organic contaminants (OCs) and hold great promise as a formidable reducing agent in water treatment. However, the diverse structures of compounds exert different influences on the second-order rate constant of hydrated electron reactions (keaq−), while the same OCs demonstrate notable discrepancies in keaq− values across different pH levels. This study aims to develop machine learning (ML) models that can effectively simulate the intricate reaction kinetics between eaq− and OCs. Furthermore, the introduction of the pH variable enables a comprehensive investigation into the impact of ambient conditions on this process, thereby improving the practicality of the model. A dataset encompassing 701 keaq− values derived from 351 peer-reviewed publications was compiled. To comprehensively investigate compound properties, this study introduced molecular descriptor (MD), molecular fingerprint (MF), and the integration of both (MD + MF) as model variables. Furthermore, 60 sets of predictive models were established utilizing two variable screening methodologies (MLR and RF) and ten prominent algorithms. Through statistical parameter analysis, it was determined that descriptors combined with MD and MF, the RF screening method, and the symbolism algorithm exhibited the best predictive efficacy. Importantly, the combination of descriptor models exhibited significantly superior performance compared to individual MF and MD models. Notably, the optimal model, denoted as RF - (MF + MD) - LGB, exhibited highly satisfactory predictive results (R2tra = 0.967, Q2tra = 0.840, R2ext = 0.761). The mechanistic explanation study based on Shapley Additive Explanations (SHAP) values further elucidated the crucial influences of polarity, pH, molecular weight, electronegativity, carbon–carbon double bonds, and molecular topology on the degradation of OCs by eaq−. The proposed modeling approach, particularly the integration of MF and MD, alongside the introduction of pH, may furnish innovative ideas for advanced reduction or oxidation processes (ARPs/AOPs) and machine learning applications in other domains.

Microplastic and associated polyaromatic hydrocarbons in surface waters feeding Beyşehir Lake in Türkiye

&lt;p&gt;The detection of microplastics, defined as tiny plastics particles having a size from 1 µm to 5 mm, in aquatic environments has become a serious concern worldwide. Microplastics may be introduced either directly to water bodies or indirectly to the aquatic systems. In particular, microplastics may interact with persistent organic pollutants and inorganic contaminants and they transfer these pollutants to organisms in the aquatic environment. In this study, microplastics and their sorbed polyaromatic hydrocarbons (PAHs) in the surface water feeding Beyşehir Lake in Türkiye were investigated. The abundance of microplastics in the surface water was determined in the range of 2830-6860 particles/m3. While five shapes (fiber, foam, film, fragment, pellet) of microplastics were determined in surface waters, fiber and fragment form microplastics were predominantly observed. The detected polymer types were cellophane, polyethylene, polypropylene. The transparent/white color microplastics were the most dominant (42-81%). The total concentration of the seventeen PAHs associated with microplastics in surface waters ranged from 1924 to 7970 ng/g. According to the diagnostic ratios of the PAH isomers (fluoranthane/pyrene &amp;lt; 1 and phenanthrene/antracene &amp;gt;10), the source of the PAHs all surface waters can be pyrogenic and petrogenic origins. These findings indicate that high concentrations of microplastics and PAHs sorbed microplastics were carried into the lake by the surface waters feeding Beyşehir Lake. These pollutants may pose a risk to the use of water for irrigation and potable purposes and to aquatic organisms in the lake.&lt;/p&gt;&#x0D;

Persistent Organic Contaminants in Dust from the International Space Station.

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), "novel" brominated flame retardants (NBFRs), organophosphate esters (OPEs), polycyclic aromatic hydrocarbons (PAH), perfluoroalkyl substances (PFAS), and polychlorinated biphenyls (PCBs) were measured in a composite sample of dust from the International Space Station (ISS). Notwithstanding the unique environment from which the dust originated, while concentrations of all target compound classes frequently exceeded the median values in terrestrial indoor microenvironments in the US and western Europe, ISS dust concentrations were generally within the terrestrial range. The relative abundance of the three HBCDD diastereomers is dominated by γ-HBCDD (96.6% ΣHBCDD). This matches very closely with the commercial mixture added to materials and contrasts with the diastereomer distribution observed in most terrestrial indoor dust samples (in which γ-HBCDD is typically ∼60-70% ΣHBCDD). This suggests conditions inside the ISS do not favor the previously reported photolytically mediated formation in dust of α-HBCDD. Also of note, the concentration of perfluorooctanoic acid (PFOA) in ISS dust (3300 ng/g) exceeds the maximum reported (1960 ng/g) in a 2008 survey of dust from US child daycare centers and homes. This may reflect the widespread use of waterproofing treatments in the ISS to prevent microbial growth. Our findings can inform future material choices for manned spacecraft such as the ISS.

Sustainable toxic dye removal and degradation from wastewater using novel chitosan-modified TiO2 and ZnO nanocomposites

TiO2 and ZnO-embedded chitosan-based nanocomposites were prepared, immobilized on borosilicate glass, and applied for the degradation of the binary dye mixture of methylene blue and methyl orange under solar irradiation. XRD of the nanocomposites showed the existence of the anatase phase of TiO2 in the nanocomposites with crystalline sizes ranging from 13.92 nm to 17.82 nm. The FESEM results showed disintegration of the agglomerated TiO2 due to Chitosan resulting in the reduction of particle size (20.6 ± 4.6 µm to 2.9 ± 0.9 µm). BET specific surface area of TiO2/ZnO/Chitosan was 2.29 times that of pure TiO2 in addition to the reduction of bandgap energy from 3.17 eV to 2.84 eV. The photocatalytic experiment for TiO2, TiO2/Chitosan, TiO2/ZnO, and TiO2/ZnO/Chitosan showed the degradation of Methylene Blue to be 78.48%, 83.65%, 86.06%, and 91.22%, respectively and 72.53%, 80.18%, 84.3%, and 88.9%, respectively for methyl orange under solar irradiation for 5 h. The formation of heterojunction with ZnO and the enhanced adsorption capacity of Chitosan resulted in enhanced photocatalytic degradation. The reusability test of the nanocomposites showed no substantial reduction in the degradation percentage after 5 cycles of use. The reaction kinetic study suggested that the first-order model was the best-fitted kinetic model. The first order rate constant for TiO2/ZnO/Chitosan was found to be 7.88 × 10−3 min−1 and 7.10 × 10−3 min−1 for degradation MB and MO, respectively. Thus, the outcome of the experiment suggests that the application of TiO2 doped with ZnO and Chitosan results in enhanced degradation of persistent organic contaminants in textile wastewater.

Bioaccumulation and potential impacts of persistent organic pollutants and contaminants of emerging concern in guitarfishes and angelsharks from Southeastern Brazil

The present study aimed to determine persistent organic pollutants (POPs) and contaminants of emerging concern in endangered angelshark and guitarfish species from southeastern Brazil, and to investigate potential impacts of these compounds on morphometric indexes. Pesticides of emerging concern, pharmaceutical and personal care products (PPCPs), polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenyl ethers (PBDEs) were determined in hepatic and muscular tissues of Pseudobatos horkelii, P. percellens, Squatina guggenheim, and Zapteryx brevirostris obtained from artisanal and industrial fisheries operating in southeastern Brazil. Accumulation profiles and effects of contaminants on condition factor and hepatosomatic index were investigated. No differences were detected regarding species contaminant concentration, potentially due to similarities in habits, occurrence and trophic position shared by guitarfishes and angelsharks. Polycyclic aromatic hydrocarbons (23.2–495.3 ng g −1), and PPCPs such as diclofenac (<LOQ – 448.4 ng g−1) and methylparaben (<LOQ – 645.5 ng g−1) presented the highest concentrations, regardless of the species. Effects of elasmobranch size were not significant on contaminant levels, indicating the lack of bioaccumulation over time. We suggest that the exposure to contaminants in elasmobranchs inhabiting this region is highly dependent on the economic activities and high urban development in southeastern Brazil. Regarding potential impacts of such exposure, the condition factor was only negatively influenced by PBDEs concentrations, whereas the hepatosomatic index was not influenced by any contaminant. Despite this, our results indicate that guitarfishes and angelsharks are exposed to POPs and contaminants of emerging concern potentially toxic to aquatic organisms. In this context, more refined biomarkers should be used to predict potential impacts of these contaminants on elasmobranch's health.

Optimized Cu2O-{100} facet for generation of different reactive oxidative species via peroxymonosulfate activation at specific pH values to efficient acetaminophen removal

Abstract Activation of peroxymonosulfate (PMS) to degrade persistent organic contaminants has received increasing attention in wastewater purification. In this study, Cu2O catalysts with different exposed crystal facets were prepared, characterized, and evaluated for acetaminophen (ACE) degradation through PMS activation. The experimental results showed that cubic Cu2O with {100} facets exhibited remarkable activity on ACE removal by PMS activation in wide pH range of 3–11. DFT calculations indicated that Cu2O-{100} displayed higher electron transfer efficiency and PMS adsorption ability, further improving PMS activation. The radicals quenching experiments and electron paramagnetic resonance (EPR) results illustrated that singlet oxygen (1O2) was dominant reactive oxidative species (ROSs) during oxidation reactions and the relevant generation pathways were distinctly elucidated. Finally, the possible PMS activation mechanisms were discussed for ACE degradation in a wide pH range. This study will provide new insights to disclose PMS-based advanced oxidation processes (AOPs), and offer a new approach for wastewater purification by non-radical reactions.