Temporal trends (1972-2017) and spatial differences of persistent halogenated aromatic hydrocarbons in osprey eggs in Finland.

Time trends and regional differences of polychlorinated dibenzo-p-dioxins and -furans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), DDTs, polybrominated biphenyls (PBBs) and polybrominated diphenylethers (BDEs) were studied in unhatched osprey eggs collected by bird ringers in 1972-2017 from four areas in Finland. Two study areas were from Baltic Sea, Northern Quark and Finnish Archipelago Sea, while the two others were inland lake areas, eutrophicated Lake Vanajanselkä affected by industrial emissions, and Pristine SW Lake Area. The highest concentrations of most compound groups were in Lake Vanajanselkä consistent with high emissions, the predominance of bream as a prey, and higher concentrations in bream compared to other prey fish. Concentrations of all chlorinated compounds decreased significantly in all study areas. Average annual decreases were ∑PCDD/F 2.3-4.9%, ∑PCB 2.2-4.2%, ∑PCN 2.6-7.0% and ∑DDT 7.1-9.5%, primarily in line with decreased levels in prey fish. From 1972 PBBs and BDEs increased significantly until 1990s declining rapidly thereafter. PCDD/F congener profile was dominated by 2,3,4,7,8-PeCDF, except in Lake Vanajanselkä by 1,2,3,6,7,8-HxCDD. PCB congener profile was dominated by PCB 153 in all study areas, followed by PCB 180 and PCB 138. Among dioxin-like compounds PCBs contributed 82%, PCDDs 14% and PCDFs 4% to toxic equivalent quantity (∑TEQ). PCB 126 contributed most to ∑TEQ, followed by 1,2,3,7,8-PeCDD. BDE 47 being the dominant BDE congener, followed by BDE 100. ∑DDT concentrations were relatively similar across all study areas, with DDE contributing about 90%. Productivity of chicks per active nest was significantly decreased in Lake Vanajanselkä, and the likely explanation is embryotoxicity of dioxin-like compounds. It is plausible that dioxin-like compounds influenced embryonic survival among highly exposed ospreys prior to 2010, especially in Lake Vanajanselkä and Northern Quark. However, decreased survival due to DDE-induced eggshell thinning seems unlikely after 1985, and BDE levels were below those potentially causing adverse effects.

Burning question: Rethinking organohalide degradation strategy for bioremediation applications.

Organohalides are widespread pollutants that pose significant environmental hazards due to their high degree of halogenation and elevated redox potentials, making them resistant to natural attenuation. Traditional bioremediation approaches, primarily relying on bioaugmentation and biostimulation, often fall short of achieving complete detoxification. Furthermore, the emergence of complex halogenated pollutants, such as per- and polyfluoroalkyl substances (PFASs), further complicates remediation efforts. Therefore, there is a pressing need to reconsider novel approaches for more efficient remediation of these recalcitrant pollutants. This review proposes novel redox-potential-mediated hybrid bioprocesses, tailored to the physicochemical properties of pollutants and their environmental contexts, to achieve complete detoxification of organohalides. The possible scenarios for the proposed bioremediation approaches are further discussed. In anaerobic environments, such as sediment and groundwater, microbial reductive dehalogenation coupled with fermentation and methanogenesis can convert organohalides into carbon dioxide and methane. In environments with anaerobic-aerobic alternation, such as paddy soil and wetlands, a synergistic process involving reduction and oxidation can facilitate the complete mineralization of highly halogenated organic compounds. Future research should focus on in-depth exploration of microbial consortia, the application of ecological principles-guided strategies, and the development of bioinspired-designed techniques. This paper contributes to the academic discourse by proposing innovative remediation strategies tailored to the complexities of organohalide pollution.

Health risks from exposure to chemicals in clothing - Non-regulated halogenated aromatic compounds.

The objective of the present study was to investigate some commonly detected halogenated textile pollutants for their bioavailability and hazardous properties. Release into artificial sweat and skin absorption in vitro were examined as well as mutagenic effects by Ames test, and skin-sensitizing properties from a peptide reactivity assay combined with a cell test. All investigated compounds were shown to migrate from the textile into sweat and be absorbed by the skin, although to a different extent. The experimental values for migration were found to be up to 390 times higher compared to literature values. Two of the studied compounds, 2,5-dinitrochlorobenzene and 3,5-dinitrobromobenzene, both exhibited mutagenic effects in the Ames test, while both 2,5-dinitrochlorobenzene and 2,6-dichlorobenzene-1,4-diamine were classified as skin sensitizers. The allergenic reactivity of the latter was found to be due to an oxidized transformation product. Risks for the induction of skin allergy and other non-carcinogenic effects from dermal exposure to the individual compounds were found low, even when considering clothing with the highest reported levels. However, the complex mixtures of chemicals often present in garments may still constitute a health risk, especially when considering the many hours of daily exposure. It is important to further study the toxicity of other frequently occurring chemicals as well as the synergistic effects of chemicals that co-occur in clothing.

Research on pollution identification and safety thresholds based on the olfactory effect on a halogenated hydrocarbon contaminated site.

To effectively address odor control issues at sites contaminated with halogenated hydrocarbons, it is essential to establish an odor risk prediction system for evaluating potential risks that may impact future planning. This research focuses on a representative halogenated hydrocarbon-contaminated site, examining the spatial and temporal distribution characteristics of key pollutants in soil gas. By analyzing odor contribution rates, the study identifies significant odorants in soil gas, which enables the derivation of both probabilistic and deterministic safety thresholds for soil and groundwater based on olfactory effects. The findings indicate that 1,1-dichloroethylene, vinyl chloride, chloroform, and 1,1-dichloroethane are prevalent throughout the contaminated site, displaying elevated concentration levels and substantially influencing the overall contamination extent. These substances are highlighted as critical pollutants requiring attention. Correlation analysis (P < 0.05) reveals a strong relationship between the concentrations of vinyl chloride, 1,1-dichloroethane, and chloroform with groundwater depth and air temperature. Additionally, the analysis of odor activity values (OAV) identified 1,1-dichloroethene, 1,4-dichlorobenzene, chlorobenzene, chloroform, and vinyl chloride as key olfactory factors at the site. The corresponding probabilistic safety thresholds are 0.68, 1.65, 0.50, 7.87, and 3.72 mg kg-1 for soil, and 9.29, 3.46, and 1.09, 69.55, and 47.01 mg L-1 for groundwater, respectively. Among them, the odor risks of chlorobenzene and 1,1-dichloroethylene warrant more attention than soil contamination risks; regarding 1,4-dichlorobenzene, it is recommended to concurrently consider odor risks during human health risk assessment; as for vinyl chloride and chloroform, their odor risks can be largely eliminated based on human health-oriented pollution management.

Determining the abundance, composition and spatial distribution of organohalogens in marine sediments using combustion-ion chromatography.

Understanding the distribution of halogenated organic compounds (HOCs) in marine sediments is essential for understanding the marine carbon and halogen cycling, and also important for assessing the ecosystem health. In this study, a method based on combustion-ion chromatography was developed for determination of the composition and abundance of HOCs in marine sediments. The method showed high accuracy, precision and reproducibility in determining the content of adsorbable organic halogens (AOX), including fluorine, chlorine and bromine (AOF, AOCl, AOBr) and the corresponding insoluble organic halogens (IOF, IOCl, IOBr, IOX), as well as total organic halogen contents (TOX). Application of the method in coastal and deep-sea sediments revealed high ratios of organic halogens in the organic carbon pool of marine sediments, suggesting that organic halogen compounds represent an important yet previously overlooked stock of carbon and energy in marine sediments. Both the TOX and the proportion of organohalogens in organic carbon (X:C ratio) showed an increasing trend from the coast to the deep-sea sediments, indicating an increased significance of HOCs in deep-sea environments. The developed method and the findings of this study lay the foundation for further studies on biogeochemical cycling of HOCs in the ocean.

Novel tropane analogues as Hsp90 inhibitors targeting colon cancer: Synthesis, biological estimation, and molecular docking study.

New derivatives of tropane scaffold were prepared from the reaction of their thione or thioamide derivatives with α-halocarbonyl compounds. The structures of all new derivatives were assured and proved with their spectral data. The novel tropane derivatives were examined for their cytotoxicity on two colon tumor cell lines; Caco2 and HCT116 cells. The most active compounds 3, 4, 5, 9d and 14a displayed significant antitumor activities with IC50 range of 9.50 - 30.15 µM compared to doxorubicin. Moreover, they revealed reduced cytotoxic effect on WI-38 normal ones, signifying their great safety. With the aim of better understanding the inhibitory potential of such compounds on heat-shock protein 90 (Hsp90), there activities were assessed against such enzyme demonstrating high inhibitory activities with IC50 range of 56.58-78.85 nM. Western blotting was carried out to ensure the inhibitory activity on Hsp90, results showed that 3 markedly suppressed Hsp90 expression on Caco2 cell line. Additionally, a molecular docking analysis of the most potent derivatives at the Hsp90 binding site was carried out in order to approve the performed in vitro assays.

A Class Act? Regulating Organohalogen Flame Retardants in Groups versus Singly.

Regulating chemicals by class based on chemical similarities may help reduce risk of regrettable substitutions while enhancing health protection. A new Commentary summarizes OFR toxicity and exposure research to inform this effort.

Variations in thyroid hormone levels in endangered St. Lawrence Estuary belugas: Potential linkage with stress and organohalogen contaminant exposure.

The St. Lawrence Estuary (SLE) beluga (Delphinapterus leucas) population is highly exposed to an array of contaminants that were identified as one of the causes to the non-recovery of this endangered and declining population. In the last decade, an increasing number of parturition-associated complications and calf mortality has been reported in this population. It was suggested that elevated exposure to organohalogens (e.g., the halogenated flame retardants polybrominated diphenyl ethers [PBDEs]) and stress could play a role in this phenomenon by perturbing thyroid hormones. The objective of this study was to investigate the impact of concentrations of organohalogen contaminants and stress (cortisol levels) on thyroid hormone variations in adult male and female SLE belugas. Because plasma could not be collected in SLE belugas for ethical reasons, skin biopsy (n = 40) was used as a less-invasive alternative matrix to determine organohalogens (PBDEs and other halogenated flame retardants, polychlorinated biphenyls, and organochlorine pesticides), cortisol, and thyroid hormones (triiodothyronine [T3] and thyroxine [T4]), and their metabolites reverse T3 and 3,5-diiodothyronine [3,5-T2]). Cortisol and thyroid hormones were analyzed by ultra-performance liquid chromatography-multiple reactions monitoring mass spectrometry (UPLC-MRM/MS). This method was compared using skin and plasma samples obtained from Arctic belugas. Comparisons of linear models showed that cortisol was a weak predictor for T4, rT3 and 3,5-T2. Specifically, there was a weak significant negative association between T4 and cortisol levels. Moreover, in male SLE belugas, a weak significant positive association was found between T3 and Σ34PBDE concentrations in skin. Our findings suggest that stress (i.e., elevated skin cortisol levels) along with organohalogen exposure (mainly PBDEs) may be associated with thyroid hormone level perturbations in skin of cetaceans.

Polycyclic aromatic hydrocarbons and their halogenated derivatives in soil from Yellow River Delta: Distribution, source apportionment, and risk assessment.

The distribution of polycyclic aromatic hydrocarbons (PAHs) and halogenated PAHs (HPAHs) in surface soils from the petroleum industrial area of the Yellow River Delta (YRD) in China were investigated. The total concentrations of 16 PAHs ranged from 19.6 to 1560 ng/g, while 22 HPAHs ranged from 2.44 to 14.9 ng/g. Moreover, a high degree of spatial distribution heterogeneity was observed for both PAHs and HPAHs, which is likely attributed to the distinct industrial activities in studied area. The combustion of biomass and petroleum were identified as primary sources of soil PAHs and HPAHs in the YRD. Furthermore, benzo[b]fluoranthene, benzo[k]fluoranthene, and benzo[g,h,i]perylene exhibited high ecological risks (with risk quotients of 1.47, 1.44, and 1.02, respectively) in specific sites within the YRD. Considering the high toxicity of HPAHs and their potential joint environmental effects with PAHs, continuous attention should be directed towards the environmental risks associated with both PAHs and HPAHs.

Association between Ambient Volatile Organic Compounds Exposome and Emergency Hospital Admissions for Cardiovascular Disease.

The limited research on volatile organic compounds (VOCs) has not taken into account the interactions between constituents. We used the weighted quantile sum (WQS) model and generalized linear model (GLM) to quantify the joint effects of ambient VOCs exposome and identify the substances that play key roles. For a 0 day lag, a quartile increase of WQS index for n-alkanes, iso/anti-alkanes, aromatic, halogenated aromatic hydrocarbons, halogenated saturated chain hydrocarbons, and halogenated unsaturated chain hydrocarbons were associated with 1.09% (95% CI: 0.13, 2.06%), 0.98% (95% CI: 0.22, 1.74%), 0.92% (95% CI: 0.14, 1.69%), 1.03% (95% CI: 0.14, 1.93%), 1.69% (95% CI: 0.48, 2.91%), and 1.85% (95% CI: 0.93, 2.79%) increase in cardiovascular disease (CVD) emergency hospital admissions, respectively. Independent effects of key substances on CVD-related emergency hospital admissions were also reported. In particular, an interquartile range increase in 1,1,1-trichloroethane, methylene chloride, styrene, and methylcyclohexane is associated with a greater risk of CVD-associated emergency hospital admissions [3.30% (95% CI: 1.93, 4.69%), 3.84% (95% CI: 1.21, 6.53%), 5.62% (95% CI: 1.35, 10.06%), 8.68% (95% CI: 3.74, 13.86%), respectively]. We found that even if ambient VOCs are present at a considerably low concentration, they can cause cardiovascular damage. This should prompt governments to establish and improve concentration standards for VOCs and their sources. At the same time, policies should be introduced to limit VOCs emission to protect public health.

Discovery of JNJ-1802, a First-in-Class Pan-Serotype Dengue Virus NS4B Inhibitor.

Dengue is a global public health threat, with about half of the world's population at risk of contracting this mosquito-borne viral disease. Climate change, urbanization, and global travel accelerate the spread of dengue virus (DENV) to new areas, including southern parts of Europe and the US. Currently, no dengue-specific small-molecule antiviral for prophylaxis or treatment is available. Here, we report the discovery of JNJ-1802 as a potent, pan-serotype DENV inhibitor (EC50's ranging from 0.057 to 11 nM against the four DENV serotypes). The observed oral bioavailability of JNJ-1802 across preclinical species, its low clearance in human hepatocytes, the absence of major in vitro pharmacology safety alerts, and a dose-proportional increase in efficacy against DENV-2 infection in mice were all supportive of its selection as a development candidate against dengue. JNJ-1802 is being progressed in clinical studies for the prevention or treatment of dengue.

A Survey of Recently Discovered Naturally Occurring Organohalogen Compounds.

The discovery of naturally occurring organohalogen compounds has increased astronomically in the 55 years since they were first discovered─from fewer than 50 in 1968 to a combined 7,958 described examples in three comprehensive reviews. The present survey, which covers the period 2021-2023, brings the number of known natural organohalogens to approximately 8,400. The organization is according to species origin, and coverage includes marine and terrestrial plants, fungi, bacteria, marine sponges, corals, cyanobacteria, tunicates, and other marine organisms.

Groundwater pollution risk, health effects and sustainable management of halocarbons in typical industrial parks.

As important chemical raw materials and organic solvents, halogenated hydrocarbons not only play an important role in economic development, but are also the main source of environmental pollution. This study proposed an improved groundwater risk assessment model system, aimed at identifying and treating contaminants at leak sites. Groundwater ubiquity score (GUS) was used to evaluate the leachability of organic pollutants. The entropy-weighted water quality index (EWQI) method was used to assess the comprehensive quality of groundwater at the site. An improved groundwater health risk assessment model was constructed to analyze the health risks of groundwater. The sources of organic pollutants were identified based on the positive matrix factorization (PMF) model. Self-organizing mapping (SOM) and the K-means algorithm were integrated to classify and manage pollution source areas. The results showed that groundwater in the study area was strongly affected by human activities. The pollution source was located in a factory near S05. Different organic pollutants were highly leachable and had high potential to contaminate surrounding groundwater. 1,2-dichloropropane and 1,2,3-trichloropropane caused the largest range of contamination. The groundwater pollution index in the study area was high, and 72% of the monitoring points were non-drinkable. Both the carcinogenic and non-carcinogenic indexes of groundwater far exceeded the international standard limits and had a great impact on human health. 1,2,3-trichloropropane and 1,2-dichloropropane were major non-carcinogenic risk factors. The leakage of pollutants and pesticide solvents were the main causes of groundwater pollution. Cluster areas III and II were areas with significant pollution impacts and needed to be monitored intensively. Most areas were cluster I, with relatively low risk. This study can provide technical support for groundwater pollution risk assessment and management in similar industrial parks.

Rapid Release of Halocarbons from Saline Water by Iron-Based Photochemistry.

Methyl halides play important roles in stratospheric ozone depletion, but their formation mechanisms are not well defined. This study demonstrated that iron-based photochemistry significantly enhanced alkyl halide production by promoting the reaction of the representative monomer of lignin with halide ions in saline water under solar light irradiation. The methyl chloride (CH3Cl) emission from the light/Fe(III) process was 2 orders of magnitude higher than dark treatment and in the absence of iron. In addition, bromide and iodide showed better reactivity in the formation of the corresponding methyl bromide (CH3Br) and methyl iodide (CH3I). Alkyl halides identified from seawater, brackish water, and salt pan water under sunlight irradiation were positively correlated with the Fe(III) concentrations, indicating that iron-based photochemistry is ubiquitous. This work suggested that the photoinduced formation of methyl radical and redox cycling of iron triggered by the Fenton-like reaction are responsible for the enhanced release of alkyl halides. This study represents an abiotic formation pathway of alkyl halides, which accounts for a portion of the unidentified sources of halocarbons in the ocean.

Design, Synthesis, and Antitumor Activity Evaluation of 2-Arylmethoxy-4-(2,2'-dihalogen-substituted biphenyl-3-ylmethoxy) Benzylamine Derivatives as Potent PD-1/PD-L1 Inhibitors.

Novel 2-arylmethoxy-4-(2,2'-dihalogen-substituted biphenyl-3-ylmethoxy) benzylamine derivatives were designed, synthesized, and evaluated in vitro and in vivo against cancers as PD-1/PD-L1 inhibitors. Through the computer-aided structural optimization and the homogeneous time-resolved fluorescence (HTRF) assay, compound A56 was found to most strongly block the PD-1/PD-L1 interaction with an IC50 value of 2.4 ± 0.8 nM and showed the most potent activity. 1H NMR titration results indicated that A56 can tightly bind to the PD-L1 protein with KD < 1 µM. The X-ray diffraction data for the cocrystal structure of the A56/PD-L1 complex (3.5 Å) deciphered a novel binding mode in detail, which can account for its most potent inhibitory activity. Cell-based assays further demonstrated the strong ability of A56 as an hPD-1/hPD-L1 blocker. Especially in an hPD-L1 MC38 humanized mouse model, A56 significantly inhibited tumor growth without obvious toxicity, with a TGI rate of 55.20% (50 mg/kg, i.g.). In conclusion, A56 is a promising clinical candidate worthy of further development.

First Atmospheric Measurements and Emission Estimates of HFO-1336mzz(Z).

For the past few years, short-lived unsaturated halocarbons have been marketed as environmentally friendly replacements for long-lived halogenated greenhouse gases and ozone-depleting substances. The phase-in of unsaturated halocarbons for various applications, such as refrigeration and foam blowing, can be tracked by their emergence and increase in the atmosphere. We present the first atmospheric measurements of the hydrofluoroolefin (HFO) HFO-1336mzz(Z) ((Z)-1,1,1,4,4,4-hexafluoro-2-butene, cis-CF3CH═CHCF3), a newly used unsaturated hydrofluorocarbon. HFO-1336mzz(Z) has been detected in >90% of all measurements since 2018 during multi-month campaigns at three Swiss and one Dutch location. Since 2019, it is found in ∼30% of all measurements that run continuously at the Swiss high-altitude Jungfraujoch station. During pollution events, mole fractions of up to ∼10 ppt were observed. Based on our measurements, Swiss and Dutch emissions were estimated at 2-7 Mg yr-1 (2019-2021) and 30 Mg yr-1 (2022), respectively. Modeled spatial emission distributions only partly conform to population density in both countries. Monitoring the presence of new unsaturated halocarbons in the atmosphere is crucial since long-term effects of their degradation products are still debated. Furthermore, the production of HFOs involves climate-active substances, which may leak to the atmosphere─in the case of HFO-1336mzz(Z), for example, the ozone-depleting CFC-113a (CF3CCl3).

Reaction Behavior of [1,3-Diethyl-4,5-diphenyl-1H-imidazol-2-ylidene] Containing Gold(I/III) Complexes against Ingredients of the Cell Culture Medium and the Meaning on the Potential Use for Cancer Eradication Therapy.

The reactivities of halido[1,3-diethyl-4,5-diphenyl-1H-imidazol-2-ylidene]gold(I) (chlorido (5), bromido (6), iodido (7)), bis[1,3-diethyl-4,5-diphenyl-1H-imidazol-2-ylidene]gold(I) (8), and bis[1,3-diethyl-4,5-diphenyl-1H-imidazol-2-ylidene]dihalidogold(III) (chlorido (9), bromido (10), iodido (11)) complexes against ingredients of the cell culture medium were analyzed by HPLC. The degradation in the RPMI 1640 medium was studied, too. Complex 6 quantitatively reacted with chloride to 5, while 7 showed additionally ligand scrambling to 8. Interactions with non-thiol containing amino acids could not be detected. However, glutathione (GSH) reacted immediately with 5 and 6 yielding the (NHC)gold(I)-GSH complex 12. The most active complex 8 was stable under in vitro conditions and strongly participated on the biological effects of 7. The gold(III) species 9-11 were completely reduced by GSH to 8 and are prodrugs. All complexes were tested for inhibitory effects in Cisplatin-resistant cells, as well as against cancer stem cell-enriched cell lines and showed excellent activity. Such compounds are of utmost interest for the therapy of drug-resistant tumors.

Study on the degradation and pyrolysis of 2-fluoromethcathinone.

Gas chromatography-mass spectrometry (GC-MS) is the first choice for law enforcement agencies in various countries to analyze new psychoactive substances (NPS) because of its advantages and complete databases. For synthetic cathinone-type NPS (SCat), alkalization and extraction processes before GC-MS analysis are essential. However, the base form of SCat is unstable, causing it to quickly degrade in solution and cause pyrolysis at the GC-MS injection inlet. In this study, we investigated the degradation of ethyl acetate and pyrolysis at the GC-MS injection inlet of 2-fluoromethcathinone (2-FMC), the most unstable SCat. Using gas chromatography-quadruple/time-of-flight mass spectrometry (GC-Q/TOF-MS) combined with the predicted data from theoretical calculations and the analysis of mass spectrometry (MS) fragmentation, the structures of 15 2-FMC degradation and pyrolysis products were identified. Among them, 11 products were produced during degradation, and six products were obtained from pyrolysis (two of which were the same as the degradation products). At the same time, the degradation and pyrolysis pathways of 2-FMC were provided. The balance between keto-enol and enamine-imine tautomerism triggered the primary degradation pathway of 2-FMC. The subsequent degradation started from the tautomer with a hydroxyimine structure, including imine hydrolysis, oxidation, imine-enamine tautomerism, intramolecular ammonolysis of halobenzene, and hydration to generate a series of degradation products. The secondary degradation reaction was the ammonolysis of ethyl acetate to yield N-[1-(2'-fluorophenyl)-1-oxopropan-2-yl]-N-methylacetamide and the byproduct, N-[1-(2'-fluorophenyl)-1-oxopropan-2-yl]-N-methylformamide. In the pyrolysis of 2-FMC, the major reactions were dehydrogenation, intramolecular ammonolysis of halobenzene, and defluoromethane. The achievements of this manuscript not only study 2-FMC degradation and pyrolysis but also lay the foundation for the study of SCat stability and their accurate analysis by GC-MS.

Natural short-lived halogens exert an indirect cooling effect on climate.

Observational evidence shows the ubiquitous presence of ocean-emitted short-lived halogens in the global atmosphere1-3. Natural emissions of these chemical compounds have been anthropogenically amplified since pre-industrial times4-6, while, in addition, anthropogenic short-lived halocarbons are currently being emitted to the atmosphere7,8. Despite their widespread distribution in the atmosphere, the combined impact of these species on Earth's radiative balance remains unknown. Here we show that short-lived halogens exert a substantial indirect cooling effect at present (-0.13 ± 0.03 watts per square metre) that arises from halogen-mediated radiative perturbations of ozone (-0.24 ± 0.02 watts per square metre), compensated by those from methane (+0.09 ± 0.01 watts per square metre), aerosols (+0.03 ± 0.01 watts per square metre) and stratospheric water vapour (+0.011 ± 0.001 watts per square metre). Importantly, this substantial cooling effect has increased since 1750 by -0.05 ± 0.03 watts per square metre (61 per cent), driven by the anthropogenic amplification of natural halogen emissions, and is projected to change further (18-31 per cent by 2100) depending on climate warming projections and socioeconomic development. We conclude that the indirect radiative effect due to short-lived halogens should now be incorporated into climate models to provide a more realistic natural baseline of Earth's climate system.

Electrocatalytic hydro-dehalogenation of halogenated organic pollutants from wastewater: A critical review.

Halogenated organic pollutants are often found in wastewater effluent although it has been usually treated by advanced oxidation processes. Atomic hydrogen (H*)-mediated electrocatalytic dehalogenation, with an outperformed performance for breaking the strong carbon-halogen bonds, is of increasing significance for the efficient removal of halogenated organic compounds from water and wastewater. This review consolidates the recent advances in the electrocatalytic hydro-dehalogenation of toxic halogenated organic pollutants from contaminated water. The effect of the molecular structure (e.g., the number and type of halogens, electron-donating or electron-withdrawing groups) on dehalogenation reactivity is firstly predicted, revealing the nucleophilic properties of the existing halogenated organic pollutants. The specific contribution of the direct electron transfer and atomic hydrogen (H*)-mediated indirect electron transfer to dehalogenation efficiency has been established, aiming to better understand the dehalogenation mechanisms. The analyses of entropy and enthalpy illustrate that low pH has a lower energy barrier than that of high pH, facilitating the transformation from proton to H*. Furthermore, the quantitative relationship between dehalogenation efficiency and energy consumption shows an exponential increase of energy consumption for dehalogenation efficiency increasing from 90% to 100%. Lastly, challenges and perspectives are discussed for efficient dehalogenation and practical applications.