Widely used titanium dioxide (TiO2) nanoparticles are likely to accumulate ultimately in sediments and potentially pose a risk to water ecosystems. This study evaluated the effect of TiO2 nanoparticles on the photodissolution of particulate organic matter (POM) through fluorescence spectroscopy. Excitation-emission matrices and parallel factor analyses revealed that the fluorescent characteristics of produced dissolved organic matter (DOM) during photodissolution of suspended sediment and synthetic particulate organic matter (SPOM) were primarily humic-like. SPOM particles appeared to simulate well the photodissolution of suspended sediment. Quasi-complete increases in fluorescence intensity and chromophoric DOM (CDOM) abundance were reached after 90, 60, and 50 min irradiation for TiO2 concentrations of 0, 2, and 5 mg L−1, respectively. The faster increment of fluorescence intensity and CDOM abundance indicated the photocatalytic dissolution of SPOM, as opposite charges between TiO2 and SPOM at pH = 4 favored the adsorption of TiO2 onto SPOM. For sediments, the CDOM abundance and fluorescence intensity decreased with increasing TiO2 concentration, resulting from the photocatalytic degradation of photoproduced DOM from sediments. These results demonstrated that pH plays an important role in the photocatalytic dissolution of POM by TiO2. Therefore, appropriate pH controls should be implemented when TiO2 are used to treat sediments contaminated with organic pollutants. Finally, with increasing use of TiO2, its accumulation in sediments may affect the fate of carbon, nutrients, and heavy metals in shallow-water ecosystems.

Coastal upwelling prevails in the coast of Hainan Island, the northern South China Sea (SCS) during summer. We studied the influences of the upwelling on the horizontal and vertical transport of terrigenous polycyclic aromatic hydrocarbons (PAHs). PAHs in dissolved and suspended particulate phase of water samples were determined in the upper (depth < 1 m) and water column (depth > 10 m). PAH levels decreased sharply from inshore to offshore to open sea. The results showed that terrestrial input was the main source of coastal PAHs. Perylene, an important indicator of land plant-derived PAH, showed the significant correlation with PAHs (p < 0.005). This implied that fluvial transport was the primary pathway of terrigenous PAHs into the coast of northern SCS. Variations of the concentrations, compositions and diagnostic ratios of PAHs, accompanied the partition equilibrium in the water column, could indicate the selective degradation of PAHs by the plankton affected by upwelling. Different from the “traditional” transport pathway of PAHs in the water column (surface enrichment-depth depletion distribution), the upwelling could provide the original driver to elevate the upward diffusion of sediment entrained contaminants towards the intermediate even the upper waters. It could also enhance the outward diffusion of terrigenous PAHs accompanied by the offshore transport of the upper waters. Therefore, the transport pathway of PAHs can be summarized by the coastal upwelling rising PAHs with their subsequent transport offshore and settling in the adjacent open sea.

We studied seasonal and physiological influences on mercury concentrations in western grebes (Aechmophorus occidentalis) and Clark's grebes (A. occidentalis) across 29 lakes and reservoirs in California, USA. Additionally, at three of these lakes, we conducted a time series study, in which we repeatedly sampled grebe blood mercury concentrations during the spring, summer, and early fall. Grebe blood mercury concentrations were higher among males (0.61 ± 0.12 μg/g ww) than females (0.52 ± 0.10 μg/g ww), higher among Clark's grebes (0.58 ± 0.12 μg/g ww) than western grebes (0.51 ± 0.10 μg/g ww), and exhibited a strong seasonal pattern (decreasing by 60% from spring to fall). Grebe blood THg concentrations exhibited a shallow, inverse U-shaped pattern with body size, and was lowest among the smallest and largest grebes. Further, the relationship between grebe blood mercury concentrations and wing primary feather molt exhibited a shallow U-shaped pattern, where mercury concentrations were highest among birds that had not yet begun molting, decreased approximately 24% between pre-molt and late molt, and increased approximately 19% from late molt to post-molt. Because grebes did not begin molting until mid-summer, lower grebe blood mercury concentrations observed in late summer and early fall were consistent with the onset of primary feather molt. However, because sampling date was a much stronger predictor of grebe mercury concentrations than molt, other seasonally changing environmental factors likely played a larger role than molt in the seasonal variation in grebe mercury concentrations. In the time series study, we found that seasonal trends in grebe mercury concentrations were not consistent among lakes, indicating that lake-specific variation in mercury dynamics influence the overall seasonal decline in grebe blood mercury concentrations. These results highlight the importance of accounting for sampling date, as well as ecological processes that may influence mercury concentrations, when developing monitoring programs to assess site-specific exposure risk of mercury to wildlife.

The effects of salinity on metal toxicity are complex: not only affecting metal bioaccumulation, but also altering the physiology and sensitivity of organisms. In this study, we used a toxicokinetic-toxicodynamic (TK-TD) model to separate and quantify the dual effects of salinity on copper (Cu) toxicity in a euryhaline clam Potamocorbula laevis. The toxicokinetics of Cu was determined using the stable isotope 65Cu as a tracer at concentrations (10–500 μg L−1) realistic to contaminated environments and at salinities ranging from 5 to 30. At low Cu concentrations (ca. 10 μg L−1), Cu bioaccumulation decreased monotonically with salinity, and the uptake rate constant (ku, 0.546 L g−1 h−1 to 0.213 L g−1 h−1) fitted well with an empirical equation, ku = 1/(1.35 + 0.116·Salinity), by treating salinity as a pseudo-competitor. The median lethal concentrations (LC50s) of Cu were 269, 224, and 192 μg L−1 at salinity 5, 15, and 30, respectively. At high Cu concentrations (ca. 500 μg L−1), elevating salinity were much less effective in decreasing Cu bioaccumulation; whereas Cu toxicity increased with salinity. The increased toxicity could be explained by the increases in Cu killing rates (kks), which were estimated to be 0.44–2.08 mg μg−1 h−1 and were presumably due to the osmotic stress caused by the deviation from the optimal salinity of the clams. The other toxicodynamic parameter, internal threshold concentration (CIT), ranged from 79 to 133 μg−1 g−1 and showed no clear trend with salinity.

Plastic debris in marine environments and its impact on wildlife species is becoming a problem of increasing concern. In pinnipeds, entanglements commonly consist of loops around the neck of non-biodegradable materials from fishing gear or commercial packaging, known as “neck collars”. These entanglements can cause injuries, death by suffocation and starvation, and therefore they may add to the overall decrease in population. Our objective was to describe the entanglement of two species of otariids (Arctocephalus australis and Otaria flavescens) in the South West Atlantic Ocean. These two species have widely different population sizes and contrasting trends, being the O. flavescens population one order of magnitude lower in abundance with a negative population trend. A total number of 47 entangled individuals and the ingestion of a fishing sinker were recorded (A. australis: n = 26; O. flavescens: n = 22). For A. australis about 40% of the objects came from industrial fishing with which this species overlap their foraging areas, although also its lost or discarded gear can travel long distances. In O. flavescens 48% of observed injuries were very severe, which might indicate that they had been entangled for a long time. More than 60% of the objects came from artisanal and recreational fishing that operates within 5 nautical miles off the coast, which is probably related to coastal foraging habits of this species. Due to the frequent interaction between artisanal fisheries and O. flavescens, it is possible that entangled nets could be active gears. An important contribution to mitigate entanglements can be the development of education programs setting the scenario for effective communication, and exchange with involved fishermen to collect and recycle old fishing nets. Returning to natural fibers or replacement of the current materials used in fishing gear for biodegradable materials can also be a recommended mitigation measure.

Although organic compounds in marine atmospheric aerosols have significant effects on climate and marine ecosystems, they have rarely been studied, especially in the coastal regions of East China. To assess the origins of the organic aerosols in the East China coastal atmosphere, PM2.5 samples were collected from the atmospheres of the Yellow Sea, the East China Sea, and Changdao Island during the CAPTAIN (Campaign of Air PolluTion At INshore Areas of Eastern China) field campaign in the spring of 2011. The marine atmospheric aerosol samples that were collected were grouped based on the backward trajectories of their air masses. The organic carbon concentrations in the PM2.5 samples from the marine and Changdao Island atmospheres were 5.5 ± 3.1 μgC/m3 and 6.9 ± 2.4 μgC/m3, respectively, which is higher than in other coastal water atmospheres. The concentration of polycyclic aromatic hydrocarbons (PAHs) in the marine atmospheric PM2.5 samples was 17.0 ± 20.2 ng/m3, indicating significant continental anthropogenic influences. The influences of fossil fuels and biomass burning on the composition of organic aerosols in the coastal atmosphere of East China were found to be highly dependent on the origins of the air masses. Diesel combustion had a strong impact on air masses from the Yangtze River Delta (YRD), and gasoline emissions had a more significant impact on the “North China” marine atmospheric samples. The “Northeast China” marine atmospheric samples were most impacted by biomass burning. Coal combustion contributed significantly to the compositions of all of the atmospheric samples. The proportions of secondary compounds increased as samples aged in the marine atmosphere indicating that photochemical oxidation occured during transport. Our results quantified ecosystem effects on marine atmospheric aerosols and highlighted the uncertainties that arise when modeling marine atmospheric PM2.5 without considering high spatial resolution source data and meteorological parameters.

Carbazole in source water is a potential precursor for toxic chlorocarbazoles in drinking water when chlorine is used as a disinfection agent in drinking water treatment plants. However, the reactivity of carbazole and the specific structures and predominant analogues of chlorocarbazoles produced during aqueous chlorination remain unknown. In this study, the aqueous chlorination of carbazole was performed to characterize its reactivity and the chlorinated products. Chlorocarbazoles generated from carbazole were identified by a comprehensive two-dimensional gas chromatography-mass spectrometry method, and their molecular structures were predicted by the Fukui index of electrophilic attack, f−1(r). As a result, the comprehensive chlorination pathway of carbazole was extrapolated with a total of nine chlorocarbazoles identified, including two monochlorocarbazoles (3-chlorocarbazole and 1-chlorocarbazole), four dichlorocarbazoles (3,6-dichlorocarbazole, 1,6-dichlorocarbazole, 1,3-dichlorocarbazole and 1,8-dichlorocarbazole), two trichlorocarbazoles (1,3,6-trichlorocarbazole and 1,3,8-trichlorocarbazole) and one tetrachlorocarbazole (1,3,6,8-tetrachlorocarbazole). The f−1(r) value indicates that the C1, C3, C6 and C8 atoms of carbazole were the favored positions for electrophilic attack, with the C3 and C6 atoms being the predominant sites for chlorine substitution. 3-Chlorocarbazole, 3,6-dichlorocarbazole, 1,3,6-trichlorocarbazole and 1,3,6,8-tetrachlorocarbazole were the major analogues of each chlorocarbazole group; however, the production of minor analogues such as 1-chlorocarbazole and 1,6-dichlorocarbazole should not be overlooked. The chlorination of carbazole was a pseudo first order reaction with a reaction rate of 0.1836 nmol/(L· h) and half-life of 3.77 h (pH = 6.4, Cl2 = 4.7 mg/L), and the chlorination rate of carbazole was approximately 5 times faster than that of an known chlorination precursor pyrene. These results showed that Fukui index was efficacious to predict the chlorination sites of aromatic compounds, and that carbazole is readily transformed into toxic chlorocarbazoles in drinking water treatment plants that use chlorine as a disinfection agent.

Walleye (Sander vitreus) are a commercially important North American fish species that inhabit the Athabasca River. This river flows through the Athabasca oil sands where natural sources of bitumen erode from the McMurray formation. Little information is available on responses of walleye embryos to oil sands tailings pond sediments in a laboratory setting. The current study describes the design and implementation of a daily-renewal bioassay to assess the potential effects of tailings pond sediments from the Athabasca oil sands area on walleye development. Developing walleye embryos were exposed to increasing concentrations of two tailings pond sediments (collected in the Athabasca oil sands area) until the completion of yolk absorption in control fish. Sediments from the tailings pond represent a mixture of polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs. During the 31 day exposure, the walleye were examined for mortalities, weight, length and developmental abnormalities to provide an initial evaluation of the effects of the oil sands tailings pond sediments. Walleye embryo survival differed between the tailings pond sediments, and survival decreased with increasing sediment concentration. Alkylated PAH content differed between the two tailings pond sediments and lower embryo survival corresponded to higher total and alkylated PAH content. Tailings pond sediment-exposed walleye exhibited a delay in development, as well as increased percentages of larvae with heart and yolk sac edema, and cranial and spinal malformations. These abnormalities in development are often associated with PAH and alkylated PAH exposure. This study provides an exposure design that can be used to assess sediment toxicity to early developmental stages of a fish species not commonly tested in the lab, and lays the groundwork for future studies with this and other difficult-to-culture species. These results offer information on the potential effects of tailings pond sediments containing PAH/alkylated PAH mixtures on walleye development and survival.

Cigarette smoke-triggered inflammatory cascades and consequent tissue damage are the main causes of chronic obstructive pulmonary disease (COPD). There is no effective therapy and the key mediators of COPD are not identified due to the lack of translational animal models with complex characterization. This integrative chronic study investigated cardiopulmonary pathophysiological alterations and mechanisms with functional, morphological and biochemical techniques in a 6-month-long cigarette smoke exposure mouse model. Some respiratory alterations characteristic of emphysema (decreased airway resistance: Rl; end-expiratory work and pause: EEW, EEP; expiration time: Te; increased tidal mid-expiratory flow: EF50) were detected in anaesthetized C57BL/6 mice, unrestrained plethysmography did not show changes. Typical histopathological signs were peribronchial/perivascular (PB/PV) edema at month 1, neutrophil/macrophage infiltration at month 2, interstitial leukocyte accumulation at months 3–4, and emphysema/atelectasis at months 5–6 quantified by mean linear intercept measurement. Emphysema was proven by micro-CT quantification. Leukocyte number in the bronchoalveolar lavage at month 2 and lung matrix metalloproteinases-2 and 9 (MMP-2/MMP-9) activities in months 5–6 significantly increased. Smoking triggered complex cytokine profile change in the lung with one characteristic inflammatory peak of C5a, interleukin-1α and its receptor antagonist (IL-1α, IL-1ra), monokine induced by gamma interferon (MIG), macrophage colony-stimulating factor (M-CSF), tissue inhibitor of matrix metalloproteinase-1 (TIMP-1) at months 2–3, and another peak of interferon-γ (IFN-γ), IL-4, 7, 13, 17, 27 related to tissue destruction. Transient systolic and diastolic ventricular dysfunction developed after 1–2 months shown by significantly decreased ejection fraction (EF%) and deceleration time, respectively. These parameters together with the tricuspid annular plane systolic excursion (TAPSE) decreased again after 5–6 months. Soluble intercellular adhesion molecule-1 (sICAM-1) significantly increased in the heart homogenates at month 6, while other inflammatory cytokines were undetectable. This is the first study demonstrating smoking duration-dependent, complex cardiopulmonary alterations characteristic to COPD, in which inflammatory cytokine cascades and MMP-2/9 might be responsible for pulmonary destruction and sICAM-1 for heart dysfunction.

Although in vitro and in vivo laboratory studies have demonstrated androgen and anti-androgen effects on male reproduction from phthalate exposures, human studies still remain inconsistent. Therefore, a case-control study (n = 289) was conducted to evaluate the associations between phthalate exposures, male infertility risks, and changes in metabolomic biomarkers. Regional participants consisted of fertile (n = 150) and infertile (n = 139) males were recruited from Nanjing Medical University’ affiliated hospitals. Seven urinary phthalate metabolites were measured using HPLC-MS/MS. Associations between levels of phthalate metabolites, infertility risks, and infertility-related biomarkers were statistically evaluated. MEHHP, one of the most abundant DEHP oxidative metabolites was significantly lower in cases than in controls (p = 0.039). When using the 1st quartile range as a reference, although statistically insignificant for odds ratios (ORs) of the 2nd, 3rd, and 4th quartiles (OR (95% CI) = 1.50 (0.34–6.48), 0.70 (0.14–3.52) and 0.42 (0.09–2.00), respectively), the MEHHP dose-dependent trend of infertility risk expressed as OR decreased significantly (p = 0.034). More interestingly, most of the phthalate metabolites, including MEHHP, were either positively associated with fertile prevention metabolic biomarkers or negatively associated with fertile hazard ones. Phthalate metabolism, along with their activated infertility-related biomarkers, may contribute to a decreased risk of male infertility at the subjects’ ongoing exposure levels. Our results may be illustrated by the low-dose related androgen effect of phthalates and can improve our understanding of the controversial epidemiological results on this issue.