The release of copper (Cu) and zinc (Zn) from vessels and leisure crafts coated with antifouling paints can pose a threat to water quality in semi-enclosed areas such as harbors and marinas as well as to coastal archipelagos. However, no reliable, practical and low-cost method exists to measure the direct release of metals from antifouling paints. Therefore, the paint industry and regulatory authorities are obliged to use release rate measurements derived from either mathematical models or from laboratory studies. To bridge this gap, we have developed a novel method using a handheld X-Ray Fluorescence spectrometer (XRF) to determine the cumulative release of Cu and Zn from antifouling paints. The results showed a strong linear relationship between XRF Kα net intensities and metal concentrations, as determined by ICP-MS. The release of Cu and Zn were determined for coated panels exposed in harbors located in the Baltic Sea and in Kattegat. The field study showed salinity to have a strong impact on the release of Cu, i.e. the release increased with salinity. Contrary, the effect of salinity on Zn was not as evident. As exemplified in this work, the XRF method also makes it possible to identify the governing parameters to the release of Cu and Zn, e.g. salinity and type of paint formulation. Thus, the XRF method can be used to measure environmentally relevant releases of metallic compounds to design more efficient and optimized antifouling coatings.

Quantum dots (QDs) have attracted broad attention due to their special optical properties and promising prospect in medical and biological applications. However, the process of QDs on cell membrane is worth further investigations because such process may lead to harmful effects on organisms and also important for QD application. In this study, adhesion of amino- and carboxyl-coated CdTe QDs (A-QDs and C-QDs) on cell membrane and the subsequent internalization are studied using a series of endocytosis-free model membranes, including giant and small unilamellar vesicles, supported lipid bilayers and giant plasma membrane vesicles (GPMVs). The adhered QD amounts on model membranes are quantified by a quartz crystal microbalance. The CdTe QD adhesion on model membranes is governed by electrostatic forces. Positively charged A-QDs adhere on GPMV surface and passively penetrate the plasma membrane via endocytosis-free mechanism, but negatively charged C-QDs cannot. Rat basophilic leukemia (RBL-2H3) cells are exposed to CdTe QDs to monitor the QD internalization process. Both A- and C-QDs are internalized by RBL-2H3 cells mainly via endocytosis. CdTe QDs do not accumulate on the plasma membrane of living cells due to the fast endocytosis and the weakened electrostatic attraction in biological medium, resulting in low chance of passive penetration. The suspended cells after trypsin digestion take more QDs than the adherent cells. A-QDs cause lower cell viability than C-QDs, probably because the approach of positively charged QDs to cells is favored and the smaller aggregates of A-QDs.

Due to the persistence of metals in the ecosystem and their threat to all living organisms, effects of heavy metal on soil microbial communities were widely studied. However, little was known about the interactions among microorganisms in heavy metal-contaminated soils. In the present study, microbial communities in Non (CON), moderately (CL) and severely (CH) contaminated soils were investigated through high-throughput Illumina sequencing of 16s rRNA gene amplicons, and networks were constructed to show the interactions among microbes. Results showed that the microbial community composition was significantly, while the microbial diversity was not significantly affected by heavy metal contamination. Bacteria showed various response to heavy metals. Bacteria that positively correlated with Cd, e.g. Acidobacteria_Gp and Proteobacteria_thiobacillus, had more links between nodes and more positive interactions among microbes in CL- and CH-networks, while bacteria that negatively correlated with Cd, e.g. Longilinea, Gp2 and Gp4 had fewer network links and more negative interactions in CL and CH-networks. Unlike bacteria, members of the archaeal domain, i.e. phyla Crenarchaeota and Euryarchaeota, class Thermoprotei and order Thermoplasmatales showed only positive correlation with Cd and had more network interactions in CH-networks. The present study indicated that (i) the microbial community composition, as well as network interactions was shift to strengthen adaptability of microorganisms to heavy metal contamination, (ii) archaea were resistant to heavy metal contamination and may contribute to the adaption to heavy metals. It was proposed that the contribution might be achieved either by improving environment conditions or by cooperative interactions.

The volatile metabolome of Rhizobium sp. strain E20-8 exposed to three concentrations of cadmium (2.5, 5.0 and 7.5 μM) was screened using comprehensive two-dimensional gas chromatography coupled to time of flight mass spectrometry (GC × GC–ToFMS), combined with headspace solid phase microextraction (HS-SPME). Cd exposure induced a global increase in the concentration of volatile organic compounds (VOCs) both intra and extracellularly. Peak areas of several linear alkanes, ketones, aldehydes, alcohols, terpenic and volatile sulfur compounds, and one ester (ethyl acetate), were especially increased when compared with the control condition (no Cd). These compounds might originate from the metabolization of toxic membrane peroxidation products, the proteolysis of oxidized proteins or the alteration of metabolic pathways, resulting from the oxidative stress imposed by Cd. Several VOCs are related to oxidative damage, but the production of VOCs involved in antioxidant response (menthol, α-pinene, dimethyl sulfide, disulfide and trisulfide, 1-butanol and 2-butanone) and in cell aggregation (2,3-butanedione, 3-methyl-1-butanol and 2-butanone) is also observed. These results bring new information that highlights the role of VOCs on bacteria response to Cd stress, identify a novel set of biomarkers related with metal stress and provide information to be applied in biotechnological and remediation contexts.

Intensive exploitation and transport of oil and derivatives are increasing the risk of coastal contamination by either dramatic disasters or diffuse sources. Tools for monitoring diffuse contamination, such as diesel oil that leaks from marine vessels are much needed. We experimentally tested the efficiency of antioxidant biomarkers as indicators of chronic exposure to diesel oil in a mudflat from the subtropical Bay of Paranaguá, in southern Brazil. We examined the effects of three successive diesel oil spills, with two weeks of recovery time between exposures, on the edible clam Anomalocardia flexuosa. Previous studies have highlighted its potential as a bioindicator species for diesel oil contamination in subtropical and tropical ecosystems. Endpoints measured in gill and digestive gland homogenates included the activity of antioxidant enzymes SOD, GPx, GST and levels of lipid peroxides. PAHs concentration in sediments and soft tissue were also quantified. GST and SOD were the most responsive biomarkers to the exposure. There were significant but non–cumulative departures from control levels in organisms from treated samples, which were, in all cases, more common 48 h after each experimental spill. Biomarker responses were more evident in the digestive gland than in gills. This work validated the short–term responsiveness of biomarkers as measures of repeated pulsed in situ exposure to low concentrations of diesel oil. For their routine implementation into monitoring programs for tropical estuaries our general recommendations are 1) to include several reference sites, 2) to analyze biomarker data using a logarithmic–scale and 3) to interpret deviations from “normal” activity as multiplicative interval differences.

Previous studies worldwide have suggested the potential role of bioaerosols as ice-nuclei and cloud-condensation nuclei. Furthermore, their participation in regulating the global carbon cycle urges systematic studies from different environmental conditions throughout the globe. Towards this through one-year study, conducted from June 2015–May 2016, we report on atmospheric abundance and variability of viable bioaerosols, organic carbon (OC) and particles number and deduced mass concentrations from Indo-Gangetic Plain (IGP; at Kanpur). Among viable bioaerosols, the highest concentrations of Gram-positive bacteria (GPB), Gram-negative bacteria (GNB) and Fungi were recorded during December–January (Avg.: 189 CFU/m³), November (244 CFU/m³) and September months (188 CFU/m³), respectively. Annual average concentration of GPB, GNB and Fungi were 105 ± 58, 144 ± 82 and 116 ± 51 CFU/m³. Particle number concentration (PNC) associated with fine-fraction aerosols (FFA) predominates throughout the year. However, mineral dust (coarser particle) remains a perennial constituent of atmospheric aerosols over the IGP. Temporal variability records and significant positive linear relationship (p < 0.05) of GPB and GNB with OC and biomass burning derived potassium (K⁺BB) indicates their association with massive emissions from paddy-residue burning (PRB) and bio-fuel burning. Influence of meteorological parameters on viable bioaerosols abundance has been rigorously investigated herein. Accordingly, ambient temperature seems to be more affecting the bacteria (anti-correlation), whereas wet-precipitation (1–4 mm) relates to higher abundance of Fungi. High abundance of GNB during large-scale biomass burning emissions has implications to endotoxin exposure on human health. Field-based data-set of bioaerosols, OC, PNC and deduced mass concentrations reported herein could serve to better constraint their role in human health and climate relevance.

A gas chromatography tandem mass-spectrometry method dedicated to the analysis of 50 metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) was applied to urine specimens collected from female Long Evans rats under controlled exposure to a mixture of PAHs (at 7 doses ranging from 0.01 to 0.8 mg/kg, by gavage, 3 times per week for 90 days). On four occasions (day 1, 28, 60 and 90), urine samples were collected over a 24 h period. Among these 50 OH-PAHs, 41 were detected in urine samples. Seven additional OH-PAHs were identified for the first time: 1 corresponding to metabolite of pyrene and 3 of anthracene.Strong linear dose versus urinary concentration relationships were observed for 25 of the 41 OH-PAHs detected in rat urine, confirming their suitability for assessing exposure to their respective parent compound. In addition, some isomers (e.g. 1-OH-pyrene, 3-OH-/4-OH-chrysene, 10-OH-benz[a]anthracene, 8-OH-benzo[k]fluoranthene, 11-OH-benzo[b]fluoranthene and 3-OH-benzo[a]pyrene) that were detected starting from the lowest levels of exposure or even in controls were considered particularly relevant biomarkers compared to metabolites only detected at higher levels of exposure. Finally, on the basis of the excretion profiles (on days 1, 28, 60 and 90) and urinary elimination kinetics of each OH-PAH detected at days 1 and 60, this study highlighted the fact that sampling time may influence the measurement of metabolites in urine.Taken together, these results provide interesting information on the suitability of the analysis of OH-PAHs in urine for the assessment of PAH exposure, which could be taken into consideration for the design of epidemiological studies in the future.

In this study, the phototoxicity of cadmium sulfide (CdS), molybdenum disulfide (MoS2), and tungsten disulfide (WS2) nanoparticles (NPs) toward Escherichia coli (E. coli) under UV irradiation (365 nm) was investigated. At the same mass concentration of NPs, the toxicity of three NPs decreased in the order of CdS > MoS2 > WS2. For example, the death rates of E. coli exposed to 50 mg/L CdS, MoS2, and WS2 were 96.7%, 38.5%, and 31.2%, respectively. Transmission electron microscope and laser scanning confocal microscope images of E. coli exposed to three NPs showed the damage of cell walls and release of intracellular components. The CdS-treated cell wall was more extensively damaged than those of MoS2-treated and WS2-treated bacteria. WS2 and MoS2 generated superoxide radical (O2⁻), singlet oxygen (¹O2), and hydroxyl radical under UV irradiation, CdS produced only O2⁻ and ¹O2. CdS and WS2 released ions under UV irradiation, while MoS2 did not. Reactive oxygen species (ROS) generation and toxic ion release jointly resulted in the antibacterial activities of CdS and WS2. ROS generation was the dominant toxic mechanism of MoS2 toward the bacteria. This study highlighted the importance of considering the hazardous effect of sulfide NPs after their release into natural waters under light irradiation condition.

Noise is associated with poor reproductive health. A number of animal studies have suggested the possible effects of exposure to high noise levels on fertility; to date, a little such research has been performed on humans.We examined an association between daytime and nocturnal noise exposures over four years (2002–2005) and subsequent male infertility.We used the National Health Insurance Service-National Sample Cohort (2002–2013), a population-wide health insurance claims dataset. A total of 206,492 males of reproductive age (20–59 years) with no history of congenital malformations were followed up for an 8-year period (2006–2013). Male infertility was defined as per ICD-10 code N46. Data on noise exposure was obtained from the National Noise Information System. Exposure levels of daytime and night time noise were extrapolated using geographic information systems and collated with the subjects' administrative district code, and individual exposure levels assigned.During the study period, 3293 (1.6%) had a diagnosis of infertility. Although there was no association of infertility with 1-dB increments in noise exposure, a non-linear dose-response relationship was observed between infertility and quartiles of daytime and night time noise after adjustment for confounding variables (i.e., age, income, residential area, exercise, smoking, alcohol drinking, blood sugar, body mass index, medical histories, and particulate pollution). Based on WHO criteria, adjusted odds for infertility were significantly increased (OR = 1.14; 95% CI, 1.05–1.23) in males exposed to night time noise ≥ 55 dB.We found a significant association between exposure to environmental noise for four years and the subsequent incidence of male infertility, suggesting long-term exposure to noise has a role in pathogenesis of male infertility.

Polybrominated dibenzo-p-dioxins (PBDDs) and hydroxylated polybrominated diphenyl ethers (OH-PBDEs) can be formed from bromophenols (BPs) by thermal degradation, biosynthesis or phototransformation. However, it is unknown whether PBDDs and OH-PBDEs can be formed during the chemical production processes that utilize BPs as raw materials. 2,4,6-tribromophenol (2,4,6-TBP) is an important raw material for the synthesis of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant. In this study, PBDDs, polybrominated dibenzofurans (PBDFs) and OH-PBDEs have been identified and quantified in commercially available BTBPE and 2,4,6-TBP. Furthermore, their formation as unintentional by-products during the laboratory synthesis of BTBPE from 2,4,6-TBP and 1,2-dibromoethane in the presence of sodium carbonate has also been investigated. 2,3,7,8-substituted PBDDs and PBDFs (2,3,7,8-PBDD/Fs) were undetectable in commercial samples of BTBPE and present in low levels (nanogram per gram) in 2,4,6-TBP. Two tetrabrominated dibenzo-p-dioxins (TeBDDs), namely 1,3,6,8- and 1,3,7,9-TeBDD, and three hydroxylated pentabrominated diphenyl ethers (OH-pentaBDEs), namely 4′-OH-BDE121, 2′-OH-BDE121, and 6′-OH-BDE100, were identified or tentatively identified, and quantitatively estimated to be at concentrations in the range of undetectable to several thousands of nanograms per gram in commercial BTBPE and 2,4,6-TBP. TeBDDs and OH-pentaBDEs were formed as by-products from 2,4,6-TBP during BTBPE synthesis. Further studies need to be conducted in order to determine whether PBDD/Fs and OH-PBDEs are also formed during the industrial synthesis of other chemical compounds that utilize BPs as raw materials or intermediates.