Antifouling booster biocides are chemicals used in protective paints to tackle the adhesion of fouling organisms to maritime artificial structures. However, they are also known to exert toxic effects on non-target organisms. Recent research developments have highlighted the potential use of engineered micro/nanomaterials (EMNMs) as carriers of antifouling booster biocides in order to control their release and to reduce the harmful effects on living biota. In the present study, we sought to assess the toxicity of two commercially-available booster biocides: (zinc pyrithione (ZnPT) and copper pyrithione (CuPT)); three unloaded engineered micro/nanomaterials (EMNMs); layered double hydroxides (LDH), silica nanocapsules (SiNC), polyurea microcapsules (PU); , and six novel EMNMs (loaded with each of the two biocides). The exposure tests were conducted on the larval stage (nauplii) of the brine shrimp Artemia salina and on two embryonic developmental stages of the European purple sea urchin Paracentrotus lividus. The findings indicate that the unloaded LDH and PU (i.e. both biocide-free EMNMs) have non/low toxic effects on both species. The unloaded SiNC, in contrast, exerted a mild toxic effect on the A. salina nauplii and P. lividus embryos. The free biocides presented different toxicity values, with ZnPT being more toxic than CuPT in the P. lividus assays. LDH-based pyrithiones demonstrated lower toxicity compared to the free forms of the state-of-the-art compounds, and constitute good candidates in terms of their antifouling efficacy.

The transport and retention of nanoplastics (NP, 200 nm nanopolystyrene) functionalized with surface carboxyl (NPC), sulfonic (NPS), low-density amino (negatively charged, NPA−), and high-density amino (positively charged, NPA+) groups in seawater-saturated sand with/without humic acid were examined to explore the role of NP surface functionalities. The mass percentages of NP recovered from the effluent (Meff) with a salinity of 35 practical salinity units (PSU) were ranked as follows: NPC (19.69%) > NPS (16.37%) > NPA+ (13.33%) > NPA− (9.78%). The homoaggregation of NPS and NPA− was observed in seawater. The transport of NPA− exhibited a ripening phenomenon (i.e., a decrease in the transport rate with time) due to the high attraction of NP with previously deposited NP, whereas monodispersed NPA+ presented a low Meff value because of the electrostatic attraction between NPA+ and negatively charged sand. Retention experiments showed that the majority of NPC, NPS and NPA+ accumulated in a monolayer on the sand surface, whereas NPA− accumulated in multiple layers. Suwannee River humic acid (SRHA) could remarkably improve the transportability of NPC, NPS, and NPA− by increasing steric repulsion. The strong attraction between NPA+ and the deposited NPA+ in the presence of SRHA triggered the weak ripening phenomenon. As seawater salinity decreased from 35 PSU to 3.5 PSU, the increase in electrostatic repulsion of NP-NP and NP-sand enhanced the transport of NPC, NPS, and NPA−, and the ripening of NPA− breakthrough curves disappeared. In deionized water, NPC, NPS, and NPA− achieved complete column breakthrough because the electrostatic repulsion between NP and sand intensified. However, the Meff values of NPA+ in 3.5 PSU seawater and deionized water presented limited increments of 15.49% and 23.67%, respectively. These results indicated that the fate of NP in sandy marine environments were strongly affected by NP surface functionalities, seawater salinity, and coexisting SRHA.

A total of 152 groundwater samples were collected around a contaminated site to evaluate the carcinogenic and noncarcinogenic risks of exposure to twelve volatile chlorinated hydrocarbons (VCHs) by oral ingestion, dermal contact and inhalation absorption during showering. Although toxicity data of some VCHs are fragmentary, the results showed that the carcinogenic and noncarcinogenic risks of exposure to VCHs in contaminated drinking groundwater for local residents needs immediate attention. The main risk contributors for the carcinogenic and noncarcinogenic risks are carbon tetrachloride and 1,1,2-trichloroethane through inhalation exposure pathway, respectively. The health risk contribution rates associated with three exposure pathways for a specific VCH were intrinsic to the compound, and the dermal contact corresponded to a negligible contribution for almost every VCH species. Although most of the evaluated VCHs had a higher risk contribution by inhalation than by oral ingestion pathway, the integrated multi-VCH health risk contributions of the three exposure pathways were mainly dependent on the VCH compositions. Drinking boiled water not only decreased the exposure risk but also affected the risk contribution rates of three exposure pathways, which indicates that it is feasible to reduce the risk of VCH exposure during daily activities based on the risk contribution of the exposure pathways. In addition to the VCHs included in the drinking water standards, species such as 1,1,2,2-tetrachloroethane and hexachloroethane also showed a remarkable exposure health risk according to the standardized health risk calculation, which implied that improved drinking water standards are urgently required.

Although alternative Flame Retardant (FR) chemicals are expected to be safer than the legacy FRs they replace, their risks to human health and the environment are often poorly characterized. This study used a small volume, fish embryo system to reveal potential mechanisms of action and diagnostic exposure patterns for TBPH (bis (2-ethylhexyl)-tetrabromophthalate), a component of several widely-used commercial products. Two different concentration of TBPH were applied to sensitive early life stages of an ecologically important test species, Fundulus heteroclitus (Atlantic killifish), with a well-annotated genome. Exposed fish embryos were sampled for transcriptomics or chemical analysis of parent compound and primary metabolite or observed for development and survival through larval stage. Global transcript profiling using RNA-seq was conducted (n = 16 per treatment) to provide a non-targeted and statistically robust approach to characterize TBPH gene expression patterns. Transcriptomic analysis revealed a dose-response in the expression of genes associated with a surprisingly limited number of biological pathways, but included the aryl hydrocarbon receptor signal transduction pathway, which is known to respond to several toxicologically-important chemical classes. A transcriptional fingerprint using Random Forests was developed that was able to perfectly discriminate exposed vs. non-exposed individuals in test sets. These results suggest that TBPH has a relatively low potential for developmental toxicity (at least in fishes), despite concerns related to its structural similarities to endocrine disrupting chemicals and that the early life stage Fundulus system may provide a convenient test system for exposure characterization. More broadly, this study advances the usefulness of a biological testing and analysis system utilizing non-targeted transcriptomics profiling and early developmental endpoints that complements current screening methods to characterize chemicals of ecological and human health concern.

A field study was conducted to clarify sources of atmospheric black carbon and related carbonaceous components at Rishiri Island, Japan. We quantified equivalent black carbon (eBC) particle mass and the absorption Ångström exponent (AAE), atmospheric CO and CH₄, in addition to levoglucosan in total suspended particles, a typical tracer of biomass burning. Sixteen high eBC events were identified attributable to either anthropogenic sources or biomass burning in Siberia/China. These events were often accompanied by increases of co-emitted gases such as CH₄ and CO. Specifically, we observed pollution events with elevated eBC, AAE, levoglucosan, and CH₄CO slope in late July 2014, which were attributed to forest fires in Siberia by reference to the FLEXPART model footprint and fire hotspots. In autumn, drastic increases of eBC, AAE, and levoglucosan were observed, accompanied by an eBC–CO slope of >15 ng m⁻³/ppb, resulting from long-range transport of emissions from extensive burning of crop residue on the Northeast China Plain. Other than the sources of fossil fuel combustion in China and forest fires in Siberia, we report for the first time that pollution events in northern Japan are caused by crop residue burning in China. This study elucidated valuable information that will improve understanding of the effects of biomass burning in East Asia on atmospheric carbonaceous components.

Crops are prone to various types of stress, such as caused by heavy metals, drought and pest/disease, during their life cycle. Heavy metal stress in crops poses a serious threat to crop quality and human health. However, differentiating between heavy metal and non-heavy metal stress presents a great challenge, since responses to environmental stress in crops are complex and uncertain, with different stressors possibly triggering similar canopy reflectance responses. This study aims to infer the occurrence probability of heavy metal stress (i.e., Cd stress) on a regional scale by integrating satellite-derived vegetation index and spatio-temporal characteristics of different stressors with a Bayesian method. The study area is located in the Hunan Province, China. Seven scenes of Sentinel-2 satellite images from 2016 to 2017 were collected, as well as Cd concentrations in the soil. First, the probability of rice being stressed was screened using the normalized difference red-edge index (NDRE) at all the growth stages of rice. Further, the stressed rice was used as input, along with the coefficients of spatio-temporal variation (CSTV) derived from NDRE, for a Bayesian method to infer rice exposed to Cd pollution. The results demonstrated that NDRE was a sensitive indicator for assessing stress levels in rice crops. The CSTV with a threshold of 2.7 successfully detected rice under Cd as well as abrupt stress on a regional scale. A high map accuracy for Cd induced stress in rice was achieved with an accuracy of 81.57%. This study suggests that vegetation index obtained from satellite images can assist in capturing crop stress, and that the used Bayesian method can be very useful for distinguishing a specific stressor in crops by incorporating temporal-spatial characteristic of different stressors in crops into satellite-derived vegetation index.

Rapid industrialization has led to high levels of mercury (Hg) releases from anthropogenic sources in China. When deposited to terrestrial ecosystems, Hg has a high affinity for natural organic carbon. This means that Hg concentrations will vary naturally as a function of the total organic carbon (TOC) content of different soils and sediment. Thus, Hg to TOC ratios in topsoil and surface sediment provides a useful normalized tracer of the anthropogenic impact on Hg contamination. We compiled literature-documented Hg and total organic carbon (TOC) data for topsoil (n = 957) and surface sediment (n = 1142) in China. Topsoil samples (n = 100) were also collected in this study to broaden the spatial coverage. We found large differences in Hg:TOC ratios among topsoil from background sites, agricultural and urban areas, and mining sites and surface sediment from fluvial, coastal, and marine environments. Specifically, a significant increase in Hg:TOC ratios occurred between soils from background sites (median: Hg:TOC = 21.1; Inter-Quartile Range (IQR): 9.67 to 40.7) and agricultural areas (median: 34.1; IQR: 22.1 to 58.7), urban areas (median: 62.1 ng g−1; IQR: 34.2 to 154) and mining sites (median: 2780; range: 181 to 43500). Urban and mining sites show the largest increase in Hg:TOC ratios, reflecting elevated anthropogenic Hg inputs in these areas. Fluvial sediment showed higher Hg:TOC ratios (median: 197; IQR: 109 to 389) than coastal (median: 88.3; IQR: 46.8 to 168) and marine sediment (median: 89.7; IQR: 53 to 138), indicating decreased anthropogenic Hg input from rivers to coastal and marine regions. Results of our study suggest Hg:TOC ratios are a useful normalized indicator of the influence of anthropogenic Hg releases on Hg enrichment in topsoil and surface sediment.

Release of fluoride from Quaternary sediments produces F-contaminated groundwater which threatens the health of millions of people worldwide. Despite the mechanisms of fluoride release from sediments are documented by numerous studies, it remains poorly understood that whether indigenous microbes participate in or not for the formation of F-rich groundwater by releasing fluoride from aquifer sediments. A microcosm-based approach, geochemistry and techniques of microbiology and molecular ecology were conducted together to investigate these mechanisms. Results show that microbes are abundant in high [F] groundwater containing at least 1129 operational taxonomic units (OTUs), and indigenous microbes can have an essential role in the mobilization of fluoride in sediments collected from aquifers in a typical fluorosis area in China. It also shows that for the sediments in this study, fluoride release (ca. 2 mg/L) is coupled with elevated concentrations of Ca (△ = 75 mg/L), Mg (△ = 33 mg/L), Al (△ = 0.2 mg/L) and Mn (△ = 1.4 mg/L). This suggests that the fluoride may source from the dissolution of F-bearing carbonate minerals and/or Al-Mn hydroxides in a local acidic environment. The findings provide additional insights into the biogeochemical circulation of fluoride in natural environment, especially in groundwater system and the development of effective strategies for the management of F-contaminated groundwater worldwide.

Efficient containment and capture of uranium (U(VI)) from aqueous solution is an essential component to ensure socially and environmentally sustainable development. Herein, the three-dimensional graphene/titanium dioxide composite (3D GA/TiO₂) was synthesized and applied as an effective adsorbent to remove U(VI) from wastewater as a function of contact time, temperature, pH and ion strength. The 3D GA/TiO₂ material was characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The batch experiments results indicated that the adsorption of U(VI) on materials were fitted with the pseudo-second order kinetics and Langmuir models. More specifically, 3D GA/TiO₂ (441.3 mg/g) was observed to outperform the GO (280.0 mg/g), rGO (140.9 mg/g) and TiO₂ (98.5 mg/g) at pH 5.0, which was attributable to the excellent cooperative effects. Furthermore, XPS analyses and DFT calculations confirmed the formation of surface complexes between oxygen-containing group and U(VI) with the U–O bonds length of 2.348 Å (U–O1) and 2.638 Å (U–O2). Meanwhile, the adsorption energy was calculated to be 1.60 eV, which showed a very strong chemisorption during the interaction process. It is believed that the 3D GA/TiO₂ revealed good removal performance for uranyl ions, which showed a great potential application to control the nuclear industrial pollution.

Synthetic dyes are toxic and carcinogenic in nature, which also causes environmental pollution. The present study was aimed to decolorize various commercial dyes using purified recombinant bacterial laccases. Laccase gene from Yersinia enterocolitica strain 8081 (yacK), Y. enterocolitica strain 7 (yacK) and Bacillus pumilus DSKK1 was cloned in vector pET28a and overproduced in host Escherichia coli BL21. The high yield of recombinant laccase protein resulted in the formation of inclusion bodies, which were further solubilized, refolded, and purified. The purified recombinant laccases were alkali-tolerant and thermostable, with pH optima at 7–8, temperature optima at 60–70 °C and low redox potential. For in silico studies, laccase protein models of B. pumilus DSKK1, Y. enterocolitica strain 7 and Y. enterocolitica strain 8081 were docked with commercial dyes. This is the first and foremost study where the stability of docked complexes of pathogenic and non-pathogenic microorganism has been explored via molecular dynamics (MD) simulations using Gromacs version 4.5.5 with the gromos96 43a force field. Finally, the in silico results were validated experimentally and it was found that purified laccases from B. pumilus DSKK1 and Y. enterocolitica strain 7 efficiently decolorized rose bengal (90.4%), malachite green (77.7%), and congo red (74.5%) dyes.