Immobilization of laccase on magnetic PEGDA-CS inverse opal hydrogel for enhancement of bisphenol A degradation in aqueous solution.

Endocrine disruptors such as bisphenol A (BPA) adversely affect the environment and human health. Laccases are used for the efficient biodegradation of various persistent organic pollutants in an environmentally safe manner. However, the direct application of free laccases is generally hindered by short enzyme lifetimes, non-reusability, and the high cost of a single use. In this study, laccases were immobilized on a novel magnetic three-dimensional poly(ethylene glycol) diacrylate (PEGDA)-chitosan (CS) inverse opal hydrogel (LAC@MPEGDA@CS@IOH). The immobilized laccase showed significant improvement in the BPA degradation performance and superior storage stability compared with the free laccase. 91.1% of 100 mg/L BPA was removed by the LAC@MPEGDA@CS@IOH in 3 hr, whereas only 50.6% of BPA was removed by the same amount of the free laccase. Compared with the laccase, the outstanding BPA degradation efficiency of the LAC@MPEGDA@CS@IOH was maintained over a wider range of pH values and temperatures. Moreover, its relative activity of was maintained at 70.4% after 10 cycles, and the system performed well in actual water matrices. This efficient method for preparing immobilized laccases is simple and green, and it can be used to further develop ecofriendly biocatalysts to remove organic pollutants from wastewater.

Nanoparticle-specific transformations dictate nanoparticle effects associated with plants and implications for nanotechnology use in agriculture.

Nanotechnology shows potential to promote sustainable and productive agriculture and address the growing population and food demand worldwide. However, the applications of nanotechnology are hindered by the lack of knowledge on nanoparticle (NP) transformations and the interactions between NPs and macromolecules within crops. In this Review, we discuss the beneficial and toxicity-relieving transformation products of NPs that provide agricultural benefits and the toxic and physiology-disturbing transformations that induce phytotoxicities. Based on knowledge related to the management of NP transformations and their long-term effects, we propose feasible design suggestions to attain nano-enabled efficient and sustainable agricultural applications.

Lung megakaryocytes engulf inhaled airborne particles to promote intrapulmonary inflammation and extrapulmonary distribution.

Many lung immune cells are known to respond to inhaled particulate matter. However, current known responses cannot explain how particles induce thrombosis in the lung and how they translocate to distant organs. Here, we demonstrate that lung megakaryocytes (MKs) in the alveolar and interstitial regions display location-determined characteristics and act as crucial responders to inhaled particles. They move rapidly to engulf particles and become activated with upregulation in inflammatory responses and thrombopoiesis. Comprehensive in vivo, in vitro and ex vivo results unraveled that MKs were involved in particle-induced lung damages and shed particle-containing platelets into blood circulation. Moreover, MK-derived platelets exhibited faster clotting, stronger adhesion than normal resting platelets, and inherited the engulfed particles from parent MKs to assist in extrapulmonary particle transportation. Our findings collectively highlight that the specific responses of MKs towards inhaled particles and their roles in facilitating the translocation of particles from the lungs to extrapulmonary organs for clearance.

RNA-Activated CRISPR/Cas12a Nanorobots Operating in Living Cells.

Active clustered regularly interspaced short palindromic repeats (CRISPR/Cas12a) systems possess both cis-cleavage (targeted) and trans-cleavage (collateral) activities, which are useful for genome engineering and diagnostic applications. Both single- and double-stranded DNA can activate crRNA-Cas12a ribonucleoprotein (RNP) to achieve cis- and trans-cleavage enzymatic activities. However, it is not clear whether RNA can activate the CRISPR/Cas12a system and what is critical to the trans-cleavage activity. We report here that RNA can activate the CRISPR/Cas12a system and trigger its trans-cleavage activity. We reveal that the activated crRNA-Cas12a RNP favors the trans-cleavage of longer sequences than commonly used. These new findings of the RNA-activated trans-cleavage capability of Cas12a provided the foundation for the design and construction of CRISPR nanorobots that operate in living cells. We assembled the crRNA-Cas12a RNP and nucleic acid substrates on gold nanoparticles to form CRISPR nanorobots, which dramatically increased the local effective concentration of the substrate in relation to the RNP and the trans-cleavage kinetics. Binding of the target microRNA to the crRNA-Cas12a RNP activated the nanorobots and their trans-cleavage function. The repeated (multiple-turnover) trans-cleavage of the fluorophore-labeled substrates generated amplified fluorescence signals. Sensitive and real-time imaging of specific microRNA in live cells demonstrated the promising potential of the CRISPR nanorobot system for future applications in monitoring and modulating biological functions within living cells.

COPD-Like Phenotypes in TBC-Treated Mice Can be Effectively Alleviated via Estrogen Supplement.

Tris(2,3-dibromopropyl) isocyanurate (TBC), recognized as an endocrine disruptor, can cause inflammatory injury to the lung tissue of mice. To investigate the specific respiratory effects of TBC, male C57BL/6J mice were administered a daily dose of 20 mg/kg of TBC over 14 days. Postexposure, these mice developed chronic obstructive pulmonary disease (COPD)-like symptoms characterized by inflammatory lung damage and functional impairment. In light of the antiestrogenic properties of TBC, we administrated estradiol (E2) to investigate its potential protective role against TBC-induced damage and found that the coexposure of E2 notably mitigated the COPD-like phenotypes. Immunohistochemical analysis revealed that TBC exposure reduced estrogen receptor alpha (ERα) expression and increased nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) expression, while E2 treatment rebalanced the expression levels of ERα and NF-κB to their normative states. Our findings indicate that TBC, as an antiestrogenic agent, may contribute to the pathogenesis of COPD through an ERα-mediated inflammatory pathway, but that E2 treatment could reverse the impairment, providing a potentially promising remedial treatment. Given the lung status as a primary target of air pollution, the presence of antiestrogenic compounds like TBC in atmospheric particulates presents a significant concern, with the potential to exacerbate respiratory conditions such as COPD and pneumonia.

Widespread mercurous [Hg(I)] species in mercury droplet impacted environments: Evidence from an abandoned Hg smelting plant in Xunyang, China.

Mercury (Hg) emissions from Hg smelting (roasting HgS ores) and artisanal small-scale gold mining predominantly include elemental Hg, in either liquid [Hg(0)l] or gaseous [Hg(0)g] form. The oxidation of Hg(0) into Hg(I) is the first step during Hg(0) oxidation, which enables Hg to enter the food web. However, this oxidation process remains poorly understood, particularly in Hg(0)l/Hg(0)g-impacted environments. Herein, we show the widespread occurrence of Hg(I) in Hg(0)l/Hg(0)g-exposed environmental matrices near an abandoned Hg smelting plant in Xunyang, Shaanxi, China, including water, sediment, soil, plant, fish, and insect. This plant produced elemental Hg by roasting HgS ore, leaving Hg(0)l in the factory area after abandonment, which continuously released Hg(0)l/Hg(0)g into the surrounding environment. In Hg(0)-impacted water, Hg(I) was one of the primary Hg species, with an average concentration of 876 (not detected to 6109) ng L-1 and an average Hg(I) to total dissolved Hg ratio of 46% (0-92%), exhibiting a decrease with increasing distance from the plant. Elevated levels of Hg(I) were observed when the upstream sample was simultaneously exposed to Hg(0)l and Hg(0)g, arising from aqueous Hg(0)l oxidation and comproportionation between Hg(II) (mainly from Hg(0)l oxidation) and dissolved Hg(0) (i.e., Hg2+ + Hg0 → Hg22+). These findings highlight the impact of Hg(0) (as Hg(0)l and Hg(0)g) on the environment, emphasizing the comproportionation formation of Hg(I) in natural waters.

Organophosphate esters in terrestrial environments of Fildes Peninsula, Antarctica: Occurrence, potential sources, and bioaccumulation.

Despite growing concerns regarding the long-range transport (LRT) and ecological risks of organophosphate esters (OPEs), information on the environmental behaviors of OPEs in polar terrestrial ecosystems remains inadequate. In the present study, 10 OPEs were analyzed in soil and vegetation samples collected from Fildes Peninsula, Antarctica. The OPE concentrations in Antarctic soils, mosses, and lichens ranged from 0.87 to 15.7 ng/g dry weight (dw), 9.8 to 113 ng/g dw, and 3.6 to 75.2 ng/g dw, respectively. Non-chlorinated OPEs predominated in terrestrial matrices, accounting for approximately 76 % of the OPE composition. Source identification indicated that OPE contamination in Antarctica likely resulted from local anthropogenic sources and LRT. Moreover, the bioaccumulation behavior of OPEs from soil to vegetation was assessed using bioconcentration factors (BCFs), revealing a significant non-linear trend of initial increase and subsequent decrease in BCFs relative to the lipophilicities of the octanol-air partition coefficient (log KOA) and octanol-water partition coefficient (log KOW). While low levels of OPEs in Antarctic terrestrial environments were reported in this study, their sustained inputs and potential ecological risks in polar regions warrant further attention.

Nationwide Investigation on Organophosphate Flame Retardants in Tea from China: Migration from Packaging Materials and Implications for Global Risk Assessment.

In this study, we measured 15 common organophosphate flame retardants (OPFRs) in six categories of tea samples across China. OPFRs were found in all the tea samples, with the total concentrations of OPFRs (∑OPFRs) at 3.44-432 ng/g [geometric mean (GM): 17.6 ng/g]. Triphenyl phosphate (TPhP) was the dominant OPFR, accounting for 39.0-76.2% of ∑OPFRs across all tea categories. The potential factors influencing the residual OPFRs in tea were thoroughly examined, including the agricultural environment, fermentation, and packaging of teas. Tea packaging materials (TPMs) were then identified as the primary sources of OPFRs in teas. The migration test revealed that OPFRs with lower molecular weights and log Kow values exhibited a higher propensity for facilitating the migration of OPFRs from TPMs to teas. The estimated daily intakes of OPFRs from teas were relatively higher for the general populations in Mauritania, Gambia, Togo, Morocco, and Senegal (3.18-9.79 ng/kg bw/day) than China (3.12 ng/kg bw/day). The health risks arising from OPFRs in Chinese teas were minor. This study established a baseline concentration and demonstrated the contamination sources of OPFRs in Chinese tea for the first time, with an emphasis on enhancing the hygiene standards for TPMs.

Unveiling the Presence of Short- and Medium-Chain Chlorinated Paraffins in the Hadal Trenches of the Western Pacific Ocean.

This study delves into the unexplored distribution and accumulation of chlorinated paraffins (CPs), pervasive industrial contaminants used as flame retardants and plasticizers, within the hadal trenches, some of Earth's most isolated marine ecosystems. Analysis of sediments from the Mussau (MS) and Mariana trench (MT) reveals notably high total CP concentrations (∑SCCPs + ∑MCCPs) of 10,963 and 14,554 ng g-1 dw, respectively, surpassing those in a reference site in the western Pacific abyssal plain (8533 ng g-1 dw). In contrast, the New Britain Trench (NBT) exhibits the lowest concentrations (2213-5880 ng g-1 dw), where CP distribution correlates with clay content, δ13C and δ15N values, but little with total organic carbon and depth. Additionally, amphipods from these trenches display varying CP levels, with MS amphipods reaching concerning concentrations (8681-16,138 ng g-1 lw), while amphipods in the MT-1 site show the lowest (4414-5010 ng g-1 lw). These bioaccumulation trends appear to be primarily influenced by feeding behaviors (δ13C) and trophic levels (δ15N). Utilizing biota-sediment accumulation factor values and principal component analysis, we discern that CPs in sediment may come from surface-derived particulate organic matters, while those in amphipods may come from the above carrion. Our findings elucidate the profound impacts of the emerging pollutants on the Earth's least explored marine ecosystems.

Impacts of chloride ions on the electrochemical decomplexation and degradation of Cr(III)-EDTA: Reaction mechanisms of HO• and RCS.

The removal of Cr(III)-organic complexes, encompassing both decomplexation and ligand degradation, presents significant challenges in industrial wastewater treatment. As one of the most common anions in wastewater, Cl- significantly improves the efficiency of electrochemically removing Cr(III)-organic complexes through generated reactive chlorine species (RCS). In the electrochemical chlorine (EC/Cl2) process, extensive experimentation revealed that ClO• plays a dominant role in the degradation of Cr(III)-EDTA, surpassing the effects of free chlorine, direct electrooxidation, HO•, and other RCS. Density functional theory calculations indicated that RCS, primarily Cl• and ClO•, preferentially oxidize the ligand in Cr(III)-EDTA via H-abstraction, whereas HO• trends to attack the Cr atom through electron transfer. The influential factors on the degradation efficiency of Cr(III)-EDTA, Cr(VI) yield, and total organic carbon removal in EC/Cl2 were also assessed, including Cl- concentration, current density, and pH. Real industrial wastewater was employed as a reaction matrix to evaluate the application of the EC/Cl2 process for treating Cr(III)-EDTA, accompanied by energy efficiency calculations. Additionally, a two-chamber reactor was established to simultaneously oxidize Cr(III)-EDTA at the anode and reduce Cr(VI) at the cathode. This study provided insight into developing RCS-dominated AOPs to effectively decomplex and decompose organic Cr(III)-complexes in Cl--containing industrial wastewater.

Towards a better understanding of ethylmercury in the environment: Addressing propylation derivatization artifact and verifying its occurrence in Chinese wetlands.

Ethylmercury (EtHg), similar to methylmercury (MeHg), is highly neurotoxic and bioaccumulative. Although recent studies suggested its occurrence in natural soils and sediments, the common propylation derivatization for EtHg analysis might generate EtHg artifacts, potentially leading to its overestimation in environmental samples. Furthermore, the extensive environmental prevalence of EtHg remains unverified, keeping its importance largely uncertain. This study investigated the formation of EtHg artifacts during propylation derivatization, evaluating artifacts formation and recoveries under different extraction methods with real samples, and confirmed the widespread occurrence of EtHg in Chinese wetlands. EtHg artifacts were obviously present during the propylation derivatization and strongly dependent on the levels of Hg2+ (0.1-10 ng) in the derivatization solution (R² = 0.99), accounting for 1.38-2.14% of Hg2+. CuSO4-HNO3CH2Cl2 extraction (effectively removing Hg2+) combined with propylation derivatization offers excellent recovery (81-86%) and low artifacts (< LOD: 1.98 × 10-4 ng/g) for EtHg measurement in soils/sediments, with results aligning with those from online solid phase extraction-high performance liquid chromatography-inductively coupled plasma mass spectrometry (R2 = 0.99). Additionally, we observed the occurrence of EtHg in soil and sediment samples across 14 Chinese wetlands, with concentrations varying from 6.08 to 171 pg/g, similar to MeHg concentrations at some sites. EtHg positively correlates with MeHg, total Hg, and total organic carbon across all samples, indicating a possible biological formation. These findings help better understand and predict the prevalence of EtHg in wetlands and its key role in environmental Hg cycle.

Rapid determination of toxic and essential metal binding proteins in biological samples by size exclusion chromatography-inductively coupled plasma tandem mass spectrometry.

Metalloproteins binding with trace elements play a crucial role in biological processes and on the contrary, those binding with exogenous heavy metals have adverse effects. However, the methods for rapid, high sensitivity and simultaneous analysis of these metalloproteins are still lacking. In this study, a fast method for simultaneously determination of both essential and toxic metal-containing proteins was developed by coupling size exclusion chromatography (SEC) with inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). After optimization of the separation and detection conditions, seven metalloproteins with different molecular weight (from 16.0 to 443.0 kDa) were successfully separated within 10 min and the proteins containing iron (Fe), copper (Cu), zinc (Zn), iodine (I) and lead (Pb) elements could be simultaneously detected with the use of oxygen as the collision gas in ICP-MS/MS. Accordingly, the linear relationship between log molecular weight and retention time was established to estimate the molecular weight of unknown proteins. Thus, the trace metal and toxic metal containing proteins could be detected in a single run with high sensitivity (detection limits in the range of 0.0020-2.5 µg/mL) and good repeatability (relative standard deviations lower than 4.5 %). This method was then successfully used to analyze metal (e.g., Pb, Zn, Cu and Fe) binding proteins in the blood of Pb-intoxicated patients, and the results showed a negative correlation between the contents of zinc and lead binding proteins, which was identified to contain hemoglobin subunit. In summary, this work provided a rapid and sensitive tool for screening metal containing proteins in large number of biological samples.

Characteristics of disinfection byproducts from dissolved organic matter during chlor(am)ination of source water in Tibetan Plateau, China.

The Tibetan Plateau, a typical high-altitude area, is less affected by human activities such as industrial development, and the external pollution to water sources is extremely low. Then it is also an important source of water samples for exploring the molecular characteristics of precursors in the dissolved organic matter (DOM) of disinfection byproducts (DBPs) in drinking water. Research data on DBPs in drinking water on the Tibet Plateau remains insufficient, leading to uncertainty about DBP contamination in the area. This study explores the formation potential of 35 typical DBPs, including 6 trihalomethanes (THMs), 9 haloacetic acids (HAAs), 2 halogenated ketones (HKs), 9 nitrosamines (NAs), and 9 aromatic DBPs, during chlorination and chloramination of typical source water samples in the Tibet Plateau of China. Moreover, in order to further investigate the characteristics of the generation of DBPs, the molecular composition of DOM in the collected water samples was characterized by Fourier transform ion cyclotron resonance mass spectrometry. The findings reveal that, for chlorination and chloramination, the average concentration of the five classes of DBPs was ranked as follows (chlorination, chloramination): HAAs (268.1 µg/L, 54.2 µg/L) > THMs (44.0 µg/L, 2.0 µg/L) > HKs (0.7 µg/L, 1.8 µg/L) > NAs (26.5 ng/L, 74.6 ng/L) > Aromatics (20.4 ng/L, 19.5 ng/L). The dominant compounds in THMs, HAAs, and NAs are trichloromethane, dichloroacetic acid, trichloroacetic acid, and nitrosopyrrolidine, respectively. This study highlights a significant positive correlation between DBP generation and UV254, SUV254, and the double bond equivalents of DOM in the source water. It systematically elucidates DOM molecular composition characteristics and DBP formation potential in high-altitude water sources, shedding light on key factors influencing DBP generation at the molecular level in high-altitude areas.

Atmospheric emissions of particulate matter-bound heavy metals from industrial sources.

Although industrial activities are significant contributors to atmospheric releases of particulate matter (PM) and associated toxic substances that lead to adverse human health effects, a knowledge gap exists concerning the human health risk resulting from such activities owing to lack of evaluation of industrial emissions. Here, we comprehensively characterized and quantified PM from 118 full-scale industrial plants. The dominant (97.9 %) PM showed diameters of <2.5 µm; 79.0 % had diameters below 1 µm. Annual atmospheric releases of Fe and heavy metals (As, Cd, Cr, Cu, Ni, Pb, Zn) contained in fine PM from these global industrial activities are estimated to be 51,161 t and 69,591 t, respectively. Emissions of heavy metals from these industries cause increased cancer risk, estimated to range from 1461 % to 50,752 %. Five crystalline compounds (ZnO, PbSO4, Mn3O4, Fe3O4, Fe2O3) that can indicate specific industrial sources are identified. Global annual emissions of these toxic compounds in fine PM from the industrial sources are estimated to be 78,635 t. The Global South displayed higher emissions than the Global North. These results are significant for recognizing regional health risks of industrial emissions.

In Vivo Exposure Pathways of Ambient Magnetite Nanoparticles Revealed by Machine Learning-Aided Single-Particle Mass Spectrometry.

Nanosized ultrafine particles (UFPs) from natural and anthropogenic sources are widespread and pose serious health risks when inhaled by humans. However, tracing the inhaled UFPs in vivo is extremely difficult, and the distribution, translocation, and metabolism of UFPs remain unclear. Here, we report a label-free, machine learning-aided single-particle inductively coupled plasma mass spectrometry (spICP-MS) approach for tracing the exposure pathways of airborne magnetite nanoparticles (MNPs), including external emission sources, and distribution and translocation in vivo using a mouse model. Our results provide quantitative analysis of different metabolic pathways in mice exposed to MNPs, revealing that the spleen serves as the primary site for MNP metabolism (84.4%), followed by the liver (11.4%). The translocation of inhaled UFPs across different organs alters their particle size. This work provides novel insights into the in vivo fate of UFPs as well as a versatile and powerful platform for nanotoxicology and risk assessment.

Prenatal Exposure of PFAS in Cohorts of Pregnant Women: Identifying the Critical Windows of Vulnerability and Health Implications.

Cohorts of pregnant women in 2018 and 2020 were selected to explore prenatal exposure to perfluoroalkyl and polyfluoroalkyl substances (PFAS). Maternal serum during the whole pregnancy (first to third trimesters) and matched cord serum were collected for the analysis of 50 PFAS. Perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), and 6:2 fluorotelomer sulfonic acid (6:2 FTS) were the dominant PFAS in both the maternal and cord serum. The median ∑PFAS concentration was 14.18 ng/mL, and the ∑PFAS concentration was observed to decline from the first trimester to the third trimester. The transplacental transfer efficiencies (TTE) of 29 PFAS were comprehensively assessed, and a "U"-shaped trend in TTE values with increasing molecular chain length of perfluoroalkyl carboxylic acid (PFCA) was observed in this study. Moreover, the maternal concentrations of 9-chlorohexadecafluoro-3-oxanonane-1-sulfonic acid (6:2 Cl-PFESA), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluoroundecanoic acid (PFUdA), perfluorododecanoic acid (PFDoA), PFOS, and hexafluoropropylene oxide dimer acid (HFPO-DA) in the 2020 cohort were significantly lower than those in the 2018 cohort, declining by about 23.85-43.2% from 2018 to 2020 (p < 0.05). Higher proportions of emerging PFAS were observed in fetuses born in 2020. This birth cohort was collected during the COVID-19 epidemic period. The change in the PFAS exposure scene might be in response to the different exposure profiles of the 2018 and 2020 cohorts, which are attributed to the impact of COVID-19 on the social activities and environment of pregnant women. Finally, by application of a multiple informant model, the third trimester was identified as the critical window of vulnerability to PFAS exposure that affects birth weight and birth length.

High-Efficiency Degradation of PET Plastics by Glutathione S-Transferase under Mild Conditions.

Plastic pollution is a significant environmental concern globally. Plastics are normally considered chemically inert and resistant to biodegradation. Although many papers have reported enzyme-induced biodegradation of plastics, these studies are primarily limited to enzymes of microbial origin or engineered enzymes. This study reveals that poly(ethylene terephthalate) (PET, ∼6000 Da and 100 kDa) particles and plastic bottle debris (PBD, 24.9 kDa) can be efficiently degraded by a mammal-origin natural phase II metabolic isozyme, glutathione S-transferase (GST), under mild conditions. The degradation efficiency of PET plastics reached 98.9%, with a degradation rate of 2.6 g·L-1·h-1 under ambient or physiological conditions at 1 atm. PET plastics can be degraded by GST with varying environmental or biological factors (i.e., temperature, light irradiation, pH, and presence of humic acid or protein). We suggest a novel mechanism for PET degradation other than hydrolysis, i.e., the mechanism of cleavage and release of PET plastic monomers via nitridation and oxidation. This finding also reveals a novel function of GST, previously thought to only degrade small molecules (<1000 Da). This method has been successfully applied in real human serum samples. Additionally, we have tested and confirmed the ability to degrade PET of a mammal-origin natural digestive enzyme (trypsin) and a human-derived natural metabolic enzyme (CYP450). Overall, our findings provide a potential new route to plastic pollution control and contribute to our understanding of the metabolism and fate of plastics in organisms.

Competitive Binding Kinetics of Methylmercury-Cysteine with Dissolved Organic Matter: Critical Impacts of Thiols on Adsorption and Uptake of Methylmercury by Algae.

Complexes with low-molecular-weight thiols are crucial species of methylmercury (MeHg) excreted by anaerobic Hg-methylating microbes, notably, MeHg-cysteine (MeHg-Cys). As MeHg-Cys diffuses into surface water, it would undergo a ligand exchange process with dissolved organic matter (DOM) under nonsulfidic conditions, inevitably altering MeHg speciation and bioavailability to phytoplankton. In this study, we investigated the competitive binding kinetics between MeHg-Cys and Suwannee River natural organic matter, and their influence on the adsorption and uptake of MeHg by the cyanobacterium, Synechocystis sp. PCC6803. Liquid chromatography-inductively coupled plasma mass spectrometry was employed to monitor the kinetics processes involving competition of DOM with Cys for MeHg binding, which revealed that competitive binding kinetics were dictated by the abundance of thiol moieties in DOM. Thiol concentrations of 0.97 and 49.34 µmol of thiol (g C)-1 resulted in competitive binding rate constant (k values) of 0.30 and 3.47 h-1, respectively. Furthermore, the time-dependent competitive binding of DOM toward MeHg-Cys significantly inhibited MeHg adsorption and uptake by cyanobacteria, an effect that was amplified by an increased thiol abundance in DOM. These findings offer valuable insights into the kinetic characteristics of MeHg's fate and transport, as well as their impact on bioconcentration in aquatic organisms within natural aquatic ecosystems.

Phytoavailability, translocation, and accompanying isotopic fractionation of cadmium in soil and rice plants in paddy fields.

Rice consumption is a major pathway for human cadmium (Cd) exposure. Understanding Cd behavior in the soil-rice system, especially under field conditions, is pivotal for controlling Cd accumulation. This study analyzed Cd concentrations and isotope compositions (δ114/110Cd) in rice plants and surface soil sampled at different times, along with urinary Cd of residents from typical Cd-contaminated paddy fields in Youxian, Hunan, China. Soil water-soluble Cd concentrations varied across sampling times, with δ114/110Cdwater lighter under drained than flooded conditions, suggesting supplementation of water-soluble Cd by isotopically lighter Cd pools, increasing Cd phytoavailability. Both water-soluble Cd and atmospheric deposition contributed to rice Cd accumulation. Water-soluble Cd's contribution increased from 28-52% under flooded to 58-87% under drained conditions due to increased soil Cd phytoavailability. Atmospheric deposition's contribution (12-72%) increased with potential atmospheric deposition flux among sampling areas. The enrichment of heavy Cd isotopes occurred from root-stem-grain to prevent rice Cd accumulation. The different extent of enrichment of heavy isotopes in urine indicated different Cd exposure sources. These findings provide valuable insights into the speciation and phytoavailability changes of Cd in the soil-rice system and highlight the potential application of Cd isotopic fingerprinting in understanding the environmental fate of Cd.

Screening (ant)agonistic activities of xenobiotics on the retinoic acid receptor alpha (RARα) using in vitro and in silico analysis.

Retinoic acid receptors (RARs) are known as crucial endocrine receptors that could mediate a broad diversity of biological processes. However, the data on endocrine disrupting effects of emerging chemicals by targeting RAR (ant)agonism are far from sufficient. Herein, we investigated the RARα agonistic or antagonistic activities for 75 emerging chemicals of concern, and explored their interactions with this receptor. A recombinant two-hybrid yeast assay was used to examine the RARα activities of the test chemicals, wherein 7 showed effects of RARα agonism and 54 exerted potentials of RARα antagonism. The representative chemicals with RARα agonistic activities, i.e. 4-hydroxylphenol (4-HP) and bisphenol AF (BPAF), significantly increased the mRNA levels of CRABP2 and CYP26A1, while 4 select chemicals with RARα antagonistic potentials, including bisphenol A (BPA), tetrabromobisphenol A (TBBPA), 4-tert-octylphenol (4-t-OP), and 4-n-nonylphenol (4-n-NP), conversely decreased the transcriptional levels of the test genes. The in silico molecular docking analysis using 3 different approaches further confirmed the substantial binding between the chemicals with RARα activities and this nuclear receptor protein. This work highlights the promising strategy for screening endocrine-disrupting effects of emerging chemicals of concern by targeting RARα (ant)agonism.