Screening Allergenic Potencies of Skin-Contact Products Using the Human-Derived THP-1 Cell Activation Test.

With the prevalence of allergic contact dermatitis (ACD) from the usage of skin-contact products, like wearable, skin care, and hair care products, screening their skin sensitizing potential is necessary, for the sake of alleviating the consequent public health impact. In the present study, a total of 77 skin-contact products classified by four categories, watch bands (WBs), skin care products (SCPs), hair care products (HCPs), and rubber gloves (RGs), were investigated, using an optimized in vitro assay of human cell line activation test (h-CLAT). Extracting the products using neutral artificial sweat simulated well the practical usage scenarios, and testing the extracts showed that 26 of them were allergy test positive, including nine WBs, six SCPs, two HCPs, and nine RGs. The allergenic response was mainly characterized by the induction of CD54 expression, and diverse paradigms of CD54 and CD86 levels were observed by analyzing dose-response curves, which could also be influenced by the compromised viability of the THP-1 cells. The data implicated the intricate regulation by different contributors to suspicious ingredients in the test samples. Altogether, a promising methodology for testing skin allergy potential was well established for commonly used commodities by neutral artificial sweat extraction coupled with h-CLAT screening. The findings would be of great help in tracing the potential allergens in practical products and improving their qualities.

Dose-Dependent Effect on Plant Growth of Exposure to Metal-Organic Framework MIL-101(Cr).

With the increasing use of metal-organic frameworks (MOFs), they will inevitably enter the environment intentionally or unintentionally. However, the effects of MOFs on plant growth are poorly understood. Here, we investigated the effects of exposure of the rhizosphere to MOFs on plant growth. MIL-101(Cr) was selected as a research model due to its commercial availability and wide use. Soybean plants at the two-leaf stage were subjected to various durations (1-7 days) and concentrations (0-1000 mg/L) of exposure in hydroculture with a control group treated with ultrapure water. We found that MIL-101(Cr) had a positive effect on soybean growth at a lower dose (i.e., 200 mg/L); however, at higher doses (i.e., 500 and 1000 mg/L), it exhibited significant toxicity to plant growth, which is evidenced by leaf damage. To investigate the mechanism of this effect, we used Cr as an indicator to quantify, track, and image MIL-101(Cr) in the plant with laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Results indicated that MIL-101(Cr) primarily accumulated in the cortex of roots (up to 40 times higher than that in stems), with limited translocation to stems and negligible presence in leaves and cotyledons. In addition, metabolomic analysis of soybeans indicated that low-dose MIL-101(Cr) could increase the sucrose content of soybean roots to promote plant growth, while a high dose could induce lipid oxidation in roots. This study provides valuable insights into the ecological toxicology of MOFs and underscores the importance of assessing their environmental impact for sustainable agricultural practices.

Rice Seedlings and Microorganisms Mediate Biotransformation of Se in CdSe/ZnS Quantum Dots to Volatile Alkyl Selenides.

Quantum dots (QDs) are widely applied and inevitably released into the environment. The biotransformation of Se in typical CdSe/ZnS QDs coated with glutathione (CdSe/ZnS-GSH) to volatile alkyl selenides and the fate of alkyl selenides in the hydroponically grown rice system were investigated herein. After a 10-day exposure to CdSe/ZnS-GSH (100 nmol L-1), seven alkyl selenides, dimethyl selenide (DMSe), dimethyl diselenide (DMDSe), methyl selenol (MSeH), ethylmethyl selenide (EMSe), ethylmethyl diselenide (EMDSe), dimethyl selenenyl sulfide (DMSeS), and ethylmethyl selenenyl sulfide (EMSeS), were detected in the exposure system using the suspect screening strategy. CdSe/ZnS-GSH was first biotransformed to DMSe and DMDSe by plant and microorganisms. The generated DMSe was volatilized to the gas phase, adsorbed and absorbed by leaves and stems, downward transported, and released into the hydroponic solution, whereas DMDSe tended to be adsorbed/absorbed by roots and upward transported to stems. The airborne DMSe and DMDSe also partitioned from the gas phase to the hydroponic solution. DMSe and DMDSe in the exposure system were further transformed to DMSeS, EMSeS, EMSe, EMDSe, and MSeH. This study gives a comprehensive understanding on the behaviors of Se in CdSe/ZnS-GSH in a rice plant system and provides new insights into the environmental fate of CdSe/ZnS QDs.

Biotic and Abiotic Transformation Pathways of a Short-Chain Chlorinated Paraffin Congener, 1,2,5,6,9,10-C10H16Cl6, in a Rice Seedling Hydroponic Exposure System.

In this work, a typical congener of short-chain chlorinated paraffins (SCCPs) with six chlorine atoms (CP-4, 1,2,5,6,9,10-C10H16Cl6, 250 ng/mL) was selected to elaborate the comprehensive environmental transformation of SCCPs in rice seedling exposure system. CP-4 was quickly absorbed, translocated, and phytovolatilized by seedlings with a small quality of CP-4 (5.81-36.5 ng) being detected in the gas phase. Only 21.4 ± 1.6% of an initial amount (10,000 ng) of CP-4 remained in the exposure system at the end of exposure. Among the transformed CP-4, some were attributed to the degradation of the rhizosphere microorganism (9.1 ± 5.8%), root exudates (2.2 ± 4.2%), and abiotic transformation (3.0 ± 2.8%) that were proved by several transformation products found in the root exudate exposure groups and unplanted controls, and a majority was phytotransformed by rice seedlings. Here, 61 products were determined through complex transformation pathways, including multihydroxylation, -HCl elimination, dechlorination, acetylation, sulfation, glycosylation, and amide acid conjugation. The acetylated and amide acid conjugates of CPs were first observed. Phase I and Phase II phytometabolic reactions of CPs were found intertwining. These findings demonstrate that multiactive transformation reactions contribute to the overlook of CPs accumulated in plants and are helpful for the environmental and health risk assessments of SCCPs in agricultural plants.

Bromophenol Induced Multiple Stress Responses in Rice Plants: Impact of Doses and Congener Structures.

Bromophenols (BPs) have both natural and artificial sources in the environment and are frequently detected in plants. Herein, the ubiquitous 2,4,6-TriBP was hydroponically exposed to rice seedlings at two concentrations (0.2 and 2.0 mg/L) to characterize the dose-dependent abiotic stress responses of rice plants to BPs. The 2,4,6-TriBP induced oxidative damage to rice roots and subsequently inhibited plant transpiration and growth at the end of exposure in both concentrations. Moreover, the gene expression of OsUGT72B1 and the activity of glycosyltransferases of exposed rice roots were 2.36-to-4.41-fold and 1.23-to-1.72-fold higher than that of the blank controls after 24 h, following the formation of glycoconjugates in response to 2,4,6-TriBP exposure. It was notable that the glycosylation rates also showed a dose-effect relationship in rice roots. One and six glycoconjugates of 2,4,6-TriBP were detected in 0.2 and 2.0 mg/L exposure groups, respectively. Considering the detected species of glycoconjugates for four other types of BPs, the numbers of bromine atoms were found to dramatically affect their glycosylation process in rice plants. These results improve our fundamental understanding of the impact of congener structures and exposure concentrations of organic contaminants on the glycosylation process in response to phytotoxicity.

Medium- and Short-Chain Chlorinated Paraffins in Mature Maize Plants and Corresponding Agricultural Soils.

For the most complex artificial chlorinated environmental contaminants, much less is known for medium-chain CPs than short-chain CPs. In this research, the spatial distributions of MCCPs and SCCPs in farmland soil and maize leaves near a CP production facility were found marginally influenced by seasonal winds. The levels of ∑MCCPs and ∑SCCPs were in the ranges of <1.51-188 and 5.41-381 ng/g dw for soils; and 77.6-52930 and 119-61999 ng/g dw for maize leaf, respectively. Bioaccumulation and tissue distributions of the CPs within maize plants were specifically analyzed. Most of the CPs were contained in the tissues directly exposed to airborne CPs. Though the estimated risk of CPs to humans through ingestion of kernels appears to be minimal, the edible safety of MCCPs in maize plants for cattle was nearly in the designated range of adverse effects. To our knowledge, this is the first report on bioaccumulation of CPs in mature maize plants, especially in the parts eaten by humans and domestic animals. It provides a baseline reference to the edible risks of CPs in agricultural food plants and alerts us to the problematic environmental behavior of MCCPs, a probable future replacement for SCCPs commercially.

Compartmentalization and Excretion of 2,4,6-Tribromophenol Sulfation and Glycosylation Conjugates in Rice Plants.

The most environmentally abundant bromophenol congener, 2,4,6-tribromophenol (2,4,6-TBP, 6.06 µmol/L), was exposed to rice for 5 d both in vivo (intact seedling) and in vitro (suspension cell) to systematically characterize the fate of its sulfation and glycosylation conjugates in rice. The 2,4,6-TBP was rapidly transformed to produce 6 [rice cells (3 h)] and 8 [rice seedlings (24 h)] sulfated and glycosylated conjugates. The predominant sulfation conjugate (TP408, 93.0-96.7%) and glycosylation conjugate (TP490, 77.1-90.2%) were excreted into the hydroponic solution after their formation in rice roots. However, the sulfation and glycosylation conjugates presented different translocation and compartmentalization behaviors during the subsequent Phase III metabolism. Specifically, the sulfated conjugate could be vertically transported into the leaf sheath and leaf, while the glycosylation conjugates were sequestered in cell vacuoles and walls, which resulted in exclusive compartmentalization within the rice roots. These results showed the micromechanisms of the different compartmentalization behaviors of 2,4,6-TBP conjugates in Phase III metabolism. Glycosylation and sulfation of the phenolic hydroxyl groups orchestrated by plant excretion and Phase III metabolism may reduce the accumulation of 2,4,6-TBP and its conjugates in rice plants.

Metal Oxide/Nitrogen-Doped Carbon Nanosheet Heteronanostructures as Highly Efficient Electromagnetic Wave Absorbing Materials.

In this paper, we will discuss the excellent broadband microwave absorption behaviors of Cu/CuO/carbon nanosheet composites: traces of copper and oxide embedded in a carbon nano-sheet not only cut down the high permittivity of adsorbs but also induce more interfacial polarization centers. The results showed that at a cracking temperature of 900 °C, the fabricated material has a unique ripple-like structure, which promotes the hierarchical interfacial polarization. The prepared material has a maximum absorption bandwidth of 4.48 GHz at an exceedingly thin thickness of 1.7 mm and a maximum reflection loss of -25.3 dB at a thickness of 2 mm. It is a relatively ideal material for electromagnetic wave absorption.

Metabolism of SCCPs and MCCPs in Suspension Rice Cells Based on Paired Mass Distance (PMD) Analysis.

Short-chain and medium-chain chlorinated paraffins (SCCPs and MCCPs) are mixtures of complex chemical compounds with intensive usage. They are frequently detected in various environmental samples. However, the interaction between CPs and plants, especially the biotransformation behaviors of CPs within plants, is poorly understood. In this study, 1,2,5,6,9,10-hexachlorodecane (CP-4, a typical standard of individual SCCP congeners) and 52%-MCCP (a commercial mixture standard of MCCPs with 52% chlorine content by mass) were selected as representative chemicals to explore the metabolic behaviors of SCCPs and MCCPs using suspension rice cell culture exposure systems. Both 79.53% and 40.70% of CP-4 and 52%-MCCP were metabolized by suspension rice cells, respectively. A complementary suspected screening strategy based on the pair mass distances (PMD) analysis algorithm was used to study the metabolism of CPs mediated by the plant cells. Forty and 25 metabolic products for CP-4 and 52%-MCCP, respectively, were identified, including (multi-) hydroxylation, dechlorination, -HCl- elimination metabolites, (hydroxylation-) sulfation, and glycosylation conjugates. Here, we propose a comprehensive metabolic molecular network and provide insight on degradation pathways of SCCPs and MCCPs in plants for the first time, aiding in further understanding of the transformation behaviors of CPs.

Carbon Chain Decomposition of Short Chain Chlorinated Paraffins Mediated by Pumpkin and Soybean Seedlings.

Short chain chlorinated paraffins (SCCPs) are a group of complex emerging persistent organic pollutants. In this study, the uptake, translocation, and transformation of four constitutionally defined SCCP isomers were studied using whole pumpkin ( Cucurbita maxima × C. moschata) and soybean ( Glycine max L. Merrill) seedlings via hydroponic exposure. Results showed that the daughter SCCPs were C10Cl5-8 and C11-13Cl5-6. The metabolic transformation of all tested isomers included dechlorination and chlorine rearrangement. In addition, carbon chain decomposition products were found for isomers with trichlorinated carbon atoms (CCl3-groups) in both pumpkin and soybean seedlings. This study provides the first evidence of carbon chain decomposition of SCCPs in whole plants, and it suggests new metabolism pathways of SCCPs in the environment. The influence of carbon chain length and degree of chlorination of SCCPs on their fate and behavior within different plant species were also investigated. Bioaccumulation of SCCPs in pumpkin and soybean increased with increasing carbon chain length and degree of chlorination. In comparison, soybean translocated and degraded parent SCCPs faster and to a greater extent than pumpkin, but pumpkin accumulated parent SCCPs to a greater extent than soybean. After 10 days exposure, less than 4% of the initial mass of exposed chemicals remained in solution of exposure groups. The parent chemicals accumulated in roots ranging from 23.6% to 59.9% for pumpkin and 1.98% to 54.5% for soybean and in stems ranging from 0.7% to 3.81% for pumpkin and 0.50% to 2.54% for soybean. These results give new perspectives on the transport, transformation, and fate of SCCPs in the environment.

Glycosylation of Tetrabromobisphenol A in Pumpkin.

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant (BFR), and it bioaccumulates throughout the food chains. Its fate in the first trophic level, plants, is of special interest. In this study, a four-day hydroponic exposure of TBBPA at a concentration of 1 µmol L-1 to pumpkin seedlings was conducted. A nontarget screening method for hydrophilic bromine-containing metabolites was modified, based on both typical isotope patterns of bromine and mass defect, and used to process mass spectra data. A total of 20 glycosylation and malonyl glycosylation metabolites were found for TBBPA in the pumpkin plants. Representative glycosyl TBBPA reference standards were synthesized to evaluate the contribution of this glycosylation process. Approximately 86% of parent TBBPA was metabolized to form those 20 glycosyl TBBPAs, showing that glycosylation was the most dominant metabolism pathway for TBBPA in pumpkin at the tested exposure concentration.

Synthetic Phenolic Antioxidants and Their Metabolites in Sediments from the Coastal Area of Northern China: Spatial and Vertical Distributions.

Synthetic phenolic antioxidants (SPAs) are widely used in foodstuffs, cosmetics, plastics, and rubber products. Little is known about their spatiotemporal distribution in the marine environment. In this study, a total of 144 surface sediments and three sediment cores were collected from the coastal areas of northern China to determine the spatial and vertical distributions of SPAs. For surface sediments, the total concentrations of five SPAs and their four metabolites (∑9SPAs) ranged from 133 to 4800 (mean: 588) ng/g dry weight (dw). The ∑9SPAs in surface sediments showed a decrease trend with the distance from the coast to the open sea. For sediment core samples, the ∑9SPAs in the inner-shelf mud (core-1 and core-3) showed a slight increase trend from the bottom to upper layers, whereas that in the central-shelf mud (core-2) did not. The principal component analysis suggests that the composition profiles of SPAs in both surface sediment and sediment core samples were similar, while the sediments close to the coast were obviously affected by the human activities. This is the first study to report the spatial and vertical distributions of SPAs and their metabolites in sediments from the coastal marine environment.

Synthetic Phenolic Antioxidants and Their Metabolites in Mollusks from the Chinese Bohai Sea: Occurrence, Temporal Trend, and Human Exposure.

Synthetic phenolic antioxidants (SPAs) are a group of chemicals widely used in various daily necessities and industrial supplies. Little is known about the occurrence and bioaccumulation potential of SPAs in marine biota. In this study, five commonly used SPAs and their four metabolites were detected in mollusk samples ( n = 274) collected from the Chinese Bohai Sea during 2006-2016 and the spatiotemporal distribution and bioaccumulation of SPAs in mollusks were examined. The concentrations of 2,6-di- tert-butyl-4-hydroxytoluene (BHT) ranged from 383 to 501000 ng/g (geometric mean: 3450 ng/g), accounting for 79.4% of the total concentrations of SPAs and their metabolites (∑9SPAs). The mollusk species, Rapana venosa (RAP), contained higher levels of BHT than other species, suggesting that Rap could be used as a potential bioindicator for monitoring of the BHT pollution in the investigated region. The ∑9SPAs concentrations in mollusks gradually increased with years and a significant positive correlation ( r = 0.900, p < 0.05) was found between ∑9SPAs concentration and trophic level of the mollusks. The trophic magnification factor value of ∑9SPAs was calculated as 16.1, suggesting a high biomagnification potential of SPAs in mollusks in the Chinese Bohai Sea. The estimated daily intake of ∑9SPAs through dietary ingestion of mollusks was up to 602 and 789 ng/kg bw/day for adults and children and teenagers, respectively. The principal component analysis result suggests that there exists a common source for three gallates (OG, DG, and PG), and BHT metabolites in mollusks were mainly derived from degradation of BHT. This is the first study to report the occurrence and bioaccumulation potentials of SPAs and their metabolites in invertebrate species from coastal marine environments.

Distribution, Bioaccumulation, Trophic Transfer, and Influences of CeO2 Nanoparticles in a Constructed Aquatic Food Web.

In view of the final destination of nanomaterials, the water system would be an important sink. However, the environmental behavior of nanomaterials is rather confusing due to the complexity of the real environment. In this study, a freshwater ecosystem, including water, sediment, water lettuce, water silk, Asian clams, snails, water fleas, Japanese medaka, and Yamato shrimp, was constructed to study the distribution, bioaccumulation, and potential impacts of CeO2 nanoparticles (CeO2 NPs) via long-term exposure. The results demonstrated most of the CeO2 NPs deposited in the sediment (88.7%) when the partition approached to the constant 30 days later. The bioaccumulated Ce in six tested biota species was negatively correlated with its trophic level, showing no biomagnification of CeO2 NPs through this food web. CeO2 NP exposure induced visual abnormalities in hydrophytes, including chlorophyll loss in water silk and water lettuce, ultrastructural changes in pyrenoids of water silk, and root elongation in water lettuce. The generation of hydroxyl radical (·OH) and cell-wall loosening induced by CeO2 NP exposure might mediate the root growth in water lettuce. The findings on the environmental behavior of CeO2 NPs in water system have provided useful information on the risk assessment of nanomaterials.

Simultaneous determination of 19 bromophenols by gas chromatography-mass spectrometry (GC-MS) after derivatization.

Bromophenols (BPs) are a class of ubiquitous emerging halogenated pollutants. Their 19 congeners are problematically separated and detected. This work described the separation and detection of 19 BP congeners by gas chromatography-mass spectrometry (GC-MS). Investigations into the derivatization of bromophenols were carried out using two silylation reagents (N,O-bis(trimethylsilyl)trifluoroacetamide and N-methyl-N-(trimethylsily)trifluoroacetamide), two alkylation reagents (methyl iodide and trimethylsilyldiazomethane) and acetic anhydride prior to GC-MS analysis. Optimal chromatographic separation, sensitivity, and linearity were achieved after BP derivatization using acetic anhydride, featuring the equipment detection limits of 0.39-1.26 pg and correlation coefficients of 0.9948-0.9999 (linear range: 0.5-250 ng mL-1) for all 19 BP congeners. Furthermore, the simultaneous determination of 19 bromophenols and 19 bromoanisoles, common environmental transformation products of BPs, is also demonstrated. The improved analytical performance on GC-MS after derivatization would benefit investigations on the environmental origins, behaviors and fates of BPs and their environmental metabolites.

Ryegrass uptake behavior and forage risk assessment after exposing to soil with combined polycyclic aromatic hydrocarbons and cadmium.

Internalization of chemicals and the forage risks of ryegrass under the combined exposure to PAHs and Cd at environmental concentrations were studied here. The effect of soil pH was also concerned due to the widely occurred soil acidification and general alkali remediation for acidification soil. Unexpectedly, as same as the acid-treated group (pH 6.77), the alkali-treatment (pH 8.83) increased Cd uptake compared with original soil pH group (pH 7.92) for the reason of CdOH+ and CdHCO3+ formed in alkali-treated group. Co-exposure to PAHs induced more oxidative stress than Cd exposure alone due to PAHs aggregated in young root regions, such as root tips, and consequently, affecting the expression of Cd-transporters, destroying the basic structure of plant cells, inhibiting the energy supply for the transporters, even triggering programmed cell death, and finally resulting in decreased Cd uptake. Even under environmental concentrations, combined exposure caused potential risks derived from both PAHs and Cd. Especially, ryegrass grown in alkali-treated soil experienced an increased forage risks despite the soil meeting the national standards for Cd at safe levels. These comprehensive results reveal the mechanism of PAHs inhibiting Cd uptake, improve the understanding of bioavailability of Cd based on different forms, provide a theoretical basis to formulate the safety criteria, and guide the application of actual soil management.

Mollusks reveal the temporal-spatial variations and trophic transferring of ongoing bromophenols in the Bohai Sea, China.

Bromophenols (BrPs) are artificial precursors of some flame retardants and important substances with natural marine- or ocean-like flavors. This study studied the temporal variations and spatial distributions of BrPs in 150 mollusk samples (12 species) collected from 9 cities around the Bohai Sea from 2009 to 2019. Only 3 B.P. among the tested 19 congeners, 4-monobromophenol (4-mBrP), 2,4-dibromophenol (2,4-diBrP), and 2,4,6-tribromophenol (2,4,6-triBrP), were extensively detected with the detection frequency of 98.7 %, 86.7 %, and 98.0 %. The median concentration of 2,4,6-triBrP was 4.27 ng/g dw, followed by 4-mBrP (1.89 ng/g dw) and 2,4-diBrP (0.625 ng/g dw). The concentration of 3 detectable congeners, ∑3BrPs' ranged from 0.152 to 703 ng/g dw with a median value of 8.08 ng/g dw. The highest concentrations of ∑3BrPs and 2,4,6-triBrP all occurred in Rapana venosa (49.2 and 45.1 ng/g dw) which belongs to Muricidae (2009 to 2019) that was at a relatively higher trophic level among the tested mollusks. The concentration of BrPs in Gastropoda is much higher than that in Bivalvia. The median concentrations of 2,4-diBrP, 2,4,6-triBrP, and ∑3BrPs in Gastropoda and Bivalvia from Shandong Province were higher than those in other administrative divisions at the provincial level because of the large volume of BrP production and brominated flame retardants. Temporal variations in Gastropoda and Bivalvia from Weihai showed that concentrations of ∑3BrPs, 2,4,6-triBrP, 4-mBrP, and 2,4-diBrP declined slowly from 2009 to 2019. Our results provide a systematic insight into the environmental occurrence and fate of BrPs in the Bohai Sea.

Sensitive method for simultaneous determination of TBBPA and its ten derivatives.

Tetrabromobisphenol A (TBBPA) and its derivatives are regarded as new contaminants, raising much attention on their environmental occurrence and fates. However, the sensitive detection of TBBPA and its main derivatives is still a great challenge. This study investigated a sensitive method for simultaneous detection of TBBPA and its ten derivatives using high-performance liquid chromatography coupled with triple quadrupole mass spectrometry (HPLC-MS/MS) with atmospheric pressure chemical ionization (APCI) source. The method exhibited much better performance than previously reported methods. Furthermore, it was successfully applied in determining complicated environmental samples, including sewage sludge, river water and vegetable samples with concentration range from undetected (n.d.) to 25.8 ng g-1 dry weight (dw). For sewage sludge, river water and vegetable samples, the spiking recoveries of TBBPA and its derivatives ranged from 69.6 ± 7.0% to 86.1 ± 12.9%, 69.5 ± 13.9% to 87.5 ± 6.6%, and 68.2 ± 5.6% to 80.2 ± 8.3%, respectively; the accuracy ranged from 94.9 ± 4.6% to 113 ± 5%, 91.9 ± 10.9% to 112 ± 7%, and 92.1 ± 5.1% to 106 ± 6%, and the method quantitative limits ranged from 0.00801 to 0.224 ng g-1 dw, 0.0104-0.253 ng L-1, and 0.00524-0.152 ng g-1 dw, respectively. Moreover, the present manuscript describes for the first time the simultaneous detection of TBBPA and ten derivatives from various environmental samples, providing fundamental work for further research on their environmental occurrences, behaviors and fates.