This study is the first quantitative report on petroleum biomarkers from the coral reefs systems of the Persian Gulf. 120 reef surface sediment samples from ten fragile coral reef ecosystems were collected and analyzed for grain size, biogenic elements, elemental ratios, and petroleum biomarkers (n-alkanes, PAHs¹ and Hopanes) to assess the sources and early diagenesis of sedimentary organic matter. The mean grain size of the reef sediments ranged from 13.56 to 37.11% (Clay), 26.92 to 51.73% (Sand) and 35.97 to 43.85% (Silt). TOC² (3.35–9.72 mg.g⁻¹) and TON³ (0.4–1.10 mg.g⁻¹) were identified as influencing factors on the accumulation of petroleum hydrocarbons, whilst BC⁴ (1.08–3.28 mg.g⁻¹) and TIN⁵ (0.13–0.86) did not exhibit any determining effect. Although BC and TIN demonstrated heterogeneous spatial distribution, TOC and TON indicated homogenous distribution with continually upward trend in concentration from the east to west ward of the Gulf. The mean calculated TOC/TN ratios vacillated according to the stations (p < 0.05) from 2.96 at Shidvar Island to 8.64 at Hengam Island. The high TOC/TN ratios were observed in the Hengam (8.64), Kharg (8.04) and Siri (6.29), respectively, suggesting a predominant marine origin. The mean concentrations of ∑C11–35n-alkanes, ∑30 PAHs and ∑9Hopanes were found in the ranges of 385–937 μg.g⁻¹dw, (overall mean:590 μg.g⁻¹dw), 326–793 ng.g⁻¹dw (499 ng.g⁻¹dw), 88 to 568 ng.g⁻¹ d (258 ng.g⁻¹dw), respectively. Higher concentrations of detected petroleum biomarkers in reef sediments were chiefly distributed near main industrial areas, Kharg, Lavan and Siri, whilst the lower concentrations were in Hormoz and Qeshm. In addition, one-way ANOVA⁶ analysis demonstrated considerably significant differences (p < 0.05) among concentration of detected total petroleum hydrocarbons between most sampling locations. Some sampling sites especially Kharg, Lavan, Siri and Lark indicated higher concentration of n-alkanes due to the higher maintenance of organic matter by high clay content in the sediments. Furthermore, most sediment samples, except for Hormoz, Qeshm and Hengam showed an even carbon preference for n-alkanes which could be correlated to bacterial input. NPMDS⁷ analysis also demonstrated that among the congeners of petroleum biomarkers, n-C12,n-C14, n-C16,n-C18 and n-C20 for n-alkanes, Phe⁸ and Naph⁹ along with their Alkyl homologues for PAHs (2–3 rings accounted for 60%) and C30αβ and C29αβ for Hopanes were discriminated from their other congeners in the whole study area. Our results based on the PCA¹⁰ analysis and diagnostic indices of AHs¹¹ and PAHs along with ring classification of PAHs, in addition, the ubiquitous presence of UCM,¹² and Hopanes revealed that the main sources of the pollution were petroleum and petroleum combustion mainly from offshore oil exploration and extraction, discharge of pollutants from shipping activities.

Northern gannet (Morus bassanus) eggs from Bonaventure Island, Québec, Canada, were collected to monitor concentrations of contaminants. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs) and non-ortho polychlorinated biphenyls (PCBs) were measured in eggs from 2004 and 2009, and several brominated and nonbrominated flame retardants (FRs) were measured every 2–5 years in eggs from 1994 to 2014. The sum (Σ) concentrations of PCDDs/Fs were significantly lower in 2009 relative to 2004, but the total toxic equivalent concentrations for PCDDs, PCDFs, and PCBs showed no significant differences (196 ng/kg wet weight (ww) in 2004 and 220 ng/kg ww in 2009). The mean ΣFR concentrations decreased significantly between 1994 and 2014, from 58 ng/g ww to 19 ng/g ww. Hexabromocyclododecane (HBCDD) was the principal nonbrominated FR detected in gannet eggs and ranged from <1.0 ng/g ww to 6.9 ng/g ww. The PCDD/F and nonortho PCB profiles were dominated by 2,3,7,8- tetrachloro-dibenzofuran (2,3,7,8-TCDF; from 26.2 ng/g ww to 34.8 ng/kg ww) and PCB-77 (from 1580 ng/g ww to 2650 ng/kg ww), respectively. Although the values of both ecological tracer stable isotopes of carbon (δ13C) and nitrogen (δ15N) showed differences among the years, no temporal trends were observed, which indicates relatively stable adults' diet and foraging area over this time period. The trends over time in concentrations of the studied contaminants likely reflect a decrease in environmental contamination. The mean 2012 eggshell thickness was 10% lower than the pre-DDT value and corresponded to a year of poor reproductive success.

Extensive studies have been conducted on the environmental degradation of multiwall carbon nanotubes (MWCNTs), but primarily focused on the extent and rate of MWCNTs mineralization. Few studies have explored possible structural changes that may occur to MWCNTs during natural or engineered processes. We systematically examined MWCNTs in oxidative coupling reactions in the presence of a common contaminant tetrabromobisphenol A (TBBPA). MWCNTs was modified by the radicals of TBBPA resulting from peroxidase-mediated coupling reaction. Interactions between TBBPA radicals and MWCNTs were definitely confirmed by analyzing the characteristic mass spectrometry response of bromine in TBBPA and the structures of MWCNTs. After reaction with TBBPA radicals for 60 min, the content of bromine contained in MWCNTs was 6.84(±0.12)%, a quantity equivalent to a 501.65(±2.19) mg loading of TBBPA per gram MWCNTs. Modified MWCNTs had better stability and smaller sizes than that of MWCNTs and TBBPA-adsorbed MWCNTs. Assessment using zebrafish embryos revealed that the modified MWCNTs passed through the chorion and entered the embryo inducing acute toxicity, while the MWCNTs/TBBPA-adsorbed MWCNTs was trapped by chorion. These findings indicated that MWCNTs was modified in peroxidase-mediated coupling reactions, and suggested that such modifications may have an influence on the ecological risks of MWCNTs.

Activation of the aryl hydrocarbon receptor (AhR)-mediated activity is one of key events in toxicity of polycyclic aromatic hydrocarbons (PAHs). Although various classes of AhR ligands may differentially activate human and rodent AhR, there is presently a lack of data on the human AhR-inducing relative potencies (REPs) of PAHs. Here, we focused on estimation of the AhR-mediated activities of a large set of environmental PAHs in human gene reporter AZ-AhR cell line, with an aim to develop the human AhR-based REP values with potential implications for risk assessment of PAHs. The previously identified weakly active PAHs mostly failed to activate the AhR in human cells. The order for REPs of individual PAHs in human cells largely corresponded with the available data from rodent-based experimental systems; nevertheless, we identified differences up to one order of magnitude in REP values of PAHs between human and rodent cells. Higher REP values were found in human cells for some important environmental contaminants or suspected carcinogens, such as indeno[1,2,3-cd]pyrene, benz[a]anthracene or benzo[b]fluoranthene, while lower REP values were determined for methyl-substituted PAHs. Our results also indicate that a different rate of metabolism for individual PAHs in human vs. rodent cells may affect estimation of REP values in human cell-based assay, and potentially alter toxicity of some compounds, such as benzofluoranthenes, in humans. We applied the AZ-AhR assay to evaluation of the AhR-mediated activity of complex mixtures of organic compounds associated with diesel exhaust particles, and we identified the polar compounds present in these mixtures as being particularly highly active in human cells, as compared with rodent cells. The present data suggest that differences may exist between the AhR-mediated potencies of PAHs in human and rodent cells, and that the AhR-mediated effects of polar PAH derivatives and metabolites in human cell models deserve further attention.

Laccase is a widely present extracellular phenoloxidase excreted by fungi, bacteria, and high plants. It is able to catalyze one-electron oxidation of phenolic compounds into radical intermediates that can subsequently couple to each other via covalent bonds. These reactions are believed to play an important role in humification process and the transformation of contaminants containing phenolic functionalities in the environment. In this study, we investigated the kinetics of triclosan transformation catalyzed by laccase. It was found that the rate of triclosan oxidation was first order to the concentrations of both substrate and enzyme. Humic acid (HA) could inhibit the reaction by quenching the radical intermediate of triclosan generated by laccase oxidation. Such inhibition was more significant in the presence of divalent metal cations. This is because that binding to metal ions neutralized the negative charge of HA molecules, thus making them more accessible to laccase molecule that is also negatively charged. Therefore, it has greater chance to quench the radical intermediate that is very unstable and can only diffuse a limited distance after being released from the enzyme catalytic center. Based on these understandings, a reaction model was developed by integration of metal-HA binding equilibriums and kinetic equations. This model precisely predicted the transformation rate of triclosan in the presence of HA and divalent metal ions including Ca2+, Mg2+, Cd2+, Co2+, Mn2+, Ba2+, and Zn2+. Overall, this work reveals important insights into laccase catalyzed oxidative coupling process.

AgCl and Ag2S prevalently exist in the environment as minerals and/or the chlorination and sulfidation products of ionic silver and elemental silver nanoparticles (AgNPs). In this work, we investigated the chemical transformation of AgCl and Ag2S under simulated sunlight (in water) and incineration (in sludge and simulated municipal solid waste, SMSW). In the presence of natural organic matter, AgCl in river water was observed to be transformed into AgNPs under simulated sunlight, while photo-reduction of Ag2S could not take place under the same experimental conditions. During the course of incineration, pure Ag2S was transformed into elemental silver while AgCl remained stable; however, both Ag2S in sludge and AgCl in SMSW can be transformed to elemental silver under incineration, evident by the results of X-ray absorption spectroscopy and scanning electron microscopy measurements. Incineration temperature played an important role in the transformation of Ag2S and AgCl into elemental silver. These results suggest that chemical transformations of Ag2S and AgCl into elemental silver could be a possible source of naturally occurring or unintentionally produced AgNPs, affecting the fate, transport, bioavailability and toxicity of silver. Therefore, it is necessary to include the contributions of this transformation process when assessing the risk of ionic silver/AgNPs and the utilization and management of incineration residues.

Total Suspended Particulate (TSP) samples were collected at Huaniao Island in northern East China Sea (ECS) from March 2012 to January 2013. Chemical analysis were conducted to measure the concentration of total particulate mercury (TPM) and speciated particulate mercury including HCl-soluble particulate mercury (HPM), elemental particulate mercury (EPM) and residual particulate mercury (RPM). The bromine (Br) and iodine (I) on particles were also detected. The mean concentration of TPM during the study period was 0.23 ± 0.15 ng m⁻³, while the obviously seasonal variation was found that the concentrations of TPM in spring, summer, fall and winter were 0.34 ± 0.20 ng m⁻³, 0.15 ± 0.03 ng m⁻³, 0.15 ± 0.05 ng m⁻³ and 0.27 ± 0.26 ng m⁻³, respectively. The statistically strong correlation of bromine and iodine to HPM was only found in spring with r = 0.81 and 0.77 (p < 0.01), respectively. While the strongest correlations between EPM and bromine and iodine were found in winter with r = 0.92 (Br) and 0.96 (I) (p < 0.01), respectively. The clustered 72-h backward trajectories of different seasons and the whole sampling period were categorized into 4 groups. In spring, the clusters passed a long distance across the East China Sea and brought about low concentration of mercury due to the deposition of mercury over the sea. The cluster of air mass across the sea had low concentration of HPM in winter, which suggested that the oxidation of mercury in winter might be related to other oxidants. During the whole sampling period, the air mass from the north of China contributed to the higher concentration of TPM in Huaniao Island.

Exposure of fine particulate matter (PM2.5) to pregnant dams has been shown to be strongly associated with adverse cardiovascular outcomes in offspring at adulthood, however, effects evident during neonatal periods are unclear. We designed this study to examine cardiac function of neonatal mice (14 days old) exposed to in utero PM2.5.Pregnant FVB female mice were exposed either to filtered air (FA) or PM2.5 at an average concentration of 91.78 μg/m3 for 6 h/day, 5 days/wk (similar to exposure in a large industrial area) throughout the gestation period (21 days). After birth, animals were analyzed at day 14 of life.Fourteen day old mice exposed to PM2.5 during the in utero period demonstrated decreased fractional shortening (%FS, 41.1 ± 1.2% FA, 33.7 ± 1.2% PM2.5, p < 0.01) and LVEDd (2.87 ± 0.08 mm FA, 2.58 ± 0.07 mm PM2.5, p < 0.05) compared to FA exposed mice. Contractile kinetics and calcium transients in isolated cardiomyocytes from PM2.5 exposed mice illustrated reduced peak shortening (%PS, 16.7 ± 0.5% FA, 14.7 ± 0.4% PM2.5, p < 0.01), negative contractile velocity (-dL/dT, −6.91 ± 0.3 μm/s FA, −5.46 ± 0.2 μm/s PM2.5, p < 0.001), increased time to relaxation 90% (TR90, 0.07 ± 0.003 s FA, 0.08 ± 0.004 s PM2.5, p < 0.05), decreased calcium transient amplitude (Δ340/380, 33.8 ± 3.4 FA, 29.5 ± 2.8 p.m.2.5) and slower fluorescence decay rate (τ, 0.72 ± 0.1 s FA, 1.16 ± 0.15 s PM2.5, p < 0.05). Immunoblotting studies demonstrated alterations in expression of Ca2+ handling proteins- SERCA-2A, p-PLN, NCX and CaV1.2 in hearts of 14 day old in utero PM2.5 exposed mice compared to FA exposed hearts.PM2.5 exposure during the critical in utero period adversely affects the developing mouse fetus leading to functional cardiac changes that were evident during the very early (14 days) stages of adolescence. These data demonstrated that exposure to PM2.5 during the gestation period significantly impacts cardiovascular outcomes early in life.

To illustrate chemical characteristic of PM2.5 emission and assess inhalational carcinogenic risk of domestic Chinese cooking, 5 sets of duplicate cooking samples were collected, using the most used 5 types of oil. The mass abundance of 14 elements, 5 water-soluble ions, organic carbon (OC), elemental carbon (EC) and 11 polycyclic aromatic hydrocarbons (PAHs) were calculated; the signature and diagnostic ratio of cooking in the domestic kitchen were analyzed; and carcinogenic risks of heavy metals and PAHs via inhalation were assessed in two scenarios. The analysis showed that OC was the primary composition in the chemical profile; Na was the most abundant element that might be due to the usage of salt; Cr and Pb, NO3− and SO42-, Phe, FL and Pyr were the main heavy metals/water-soluble ions/PAHs, respectively. Phe and FL could be used to separate cooking and stationary sources, while diagnostic ratios of BaA/(BaA + CHR), BaA/CHR, BaP/BghiP and BaP/BeP should be applied with caution, as they were influenced by various cooking conditions. Carcinogenic risks of heavy metals and PAHs were evaluated in two scenarios, simulating the condition of cooking with no ventilation and with the range hood on, respectively. The integrated risk of heavy metals and PAHs was 2.7 × 10−3 and 5.8 × 10−6, respectively, during cooking with no ventilation. While with the usage of range hood, only Cr(VI), As and Ni might induce potential carcinogenic risk. The difference in the chemical abundance in cooking sources found between this and other studies underlined the necessity of constructing locally representative source profiles under real conditions. The comparison of carcinogenic risk suggested that the potentially adverse health effects induced by inorganic compositions from cooking sources should not be ignored. Meanwhile, intervention methods, such as the operation of range hood, should be applied during cooking for health protection.

The broad application of triclosan (TCS) and triclocarban (TCC) as antimicrobials in household and personal care products has led to the concerns regarding their human health risk and environmental impact. Although many studies have examined the toxicological effects of these compounds to a wide range of aquatic organisms from algae to fish, their potential toxicity to an important model organism the nematode Caenorhabditis elegans has never been systematically investigated. Here we assessed the toxicological effects of TCS and TCC in C. elegans using endpoints from organismal to molecular levels, including lethality, reproduction, lifespan, hatching, germline toxicity, and oxidative stress. L4 stage or young adult worms were exposed to TCS or TCC and examined using above-mentioned endpoints. Both TCS and TCC showed acute toxicity to C. elegans, with 24-h LC50s of 3.65 (95% CI: 3.15, 4.3) mg/L and 0.91 (95% CI: 0.47, 1.53) mg/L, respectively. TCS at 0.1–2 mg/L and TCC at 0.01–0.5 mg/L, respectively, induced concentration dependent reduction in the worm's reproduction, lifespan, and delay in hatching. Using a DAF-16:GFP transgenic strain, we found both compounds induced oxidative stress in the worm, indicated by the relocalization of DAF-16:GFP from cytoplasm to the nucleus upon exposure. Germline toxicity of the two compounds was also demonstrated using a xol-1:GFP transgenic strain. These findings suggest that TCS and TCC induce systemic toxic effects in C. elegans. Further studies are needed to elucidate the potential mechanisms of toxicity of these antimicrobials in the model organism, especially their potential endocrine disruption effects.