Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0–2 cm (diagenetically new organic matter, OM) and 30–32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 μm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.2 × 103 ng g−1, respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4–6 ring PAHs, especially benzo(g,h,i) perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (Koc) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (Kow) (i.e., measured Koc > Koc predicted from Kow). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5–6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon.

The Pacific Islands carry a perception of having clean air, yet emissions from transport and burning activities are of concern in regard to air quality and health. Ultrafine particle number concentrations (PNCs), one of the best metrics to demonstrate combustion emissions, have not been measured either in Suva or elsewhere in the Islands. This work provides insight into PNC variation across Suva and its relationship with particle mass (PM) concentration and composition. Measurements over a short monitoring campaign provide a vignette of conditions in Suva. Ambient PNCs were monitored for 8 day at a fixed location, and mobile PNC sampling for two days. These were compared with PM concentration (TSP, PM10, PM2.5, PM1) and are discussed in relation to black carbon (BC) content and PM2.5 sources, determined from elemental concentrations; for the October 2015 period and longer-term data. Whilst Suva City PM levels remained fairly low, PM2.5 = 10–12 μg m⁻³, mean PNC (1.64 ± 0.02 × 10⁴ cm⁻³) was high compared to global data. PNCs were greater during mobile sampling, with means of 10.3 ± 1.4 × 10⁴ cm⁻³ and 3.51 ± 0.07 × 10⁴ cm⁻³ when travelling by bus and taxi, respectively. Emissions from road vehicles, shipping, diesel and open burning were identified as PM sources for the October 2015 period. Transport related ultrafine particle emissions had a significant impact on microscale ambient concentrations, with PNCs near roads being 1.5 to 2 times higher than nearby outdoor locations and peak PNCs occurring during peak traffic times. Further data, particularly on transport and wet-season exposures, are required to confirm results. Understanding PNC in Suva will assist in formulating effective air emissions control strategies, potentially reducing population exposure across the Islands and in developing countries with similar emission characteristics.Suva's PNC was high in comparison to global data; high exposures were related to transport and combustion emissions, which were also identified as significant PM2.5 sources.

This study aims to assess the role of Fe plaque in metal uptake and translocation by different wetland plants and examine the effects of organic acids on metal detoxification in wetland plants. It was found that although exposed to a similar level of metals in rhizosphere soil solution, metal uptake by shoots of Cypercus flabelliformis and Panicum paludosum was greatly reduced, consequently leading to a better growth under flooded than under drained conditions. This may be related to the enhanced Fe plaque in the former, but due to the decreased root permeability in the latter under anoxic conditions. The Fe plaque on root surface has potential to sequester metals and then reduce metal concentrations and translocation in shoot tissues. However, whether the Fe plaque acts as a barrier to metal uptake and translocation may also be dependent on the root anatomy. Although metal tolerance in wetland plants mainly depends upon their metal exclusion ability, the higher-than-toxic-level of metal concentrations in some species indicates that internal metal detoxification might also exist. It was suggested that malic or citric acid in shoots of P. paludosum and C. flabelliformis may account for their internal detoxification for Zn.

In order to investigate the effects of dissolved humic acid (DHA) and tourmaline on uptake of 2, 2′, 4, 4′, 5, 5′- hexabrominated diphenyl ether (BDE-153) by Lactuca sativa, different fractions of DHA, including DHA1 and DHA4, as well as different doses of tourmaline were introduced into BDE-153 contaminated solutions for plant growth. The levels of BDE-153 in L. sativa tissues were positively correlated with the Fe levels (R² = 0.9264) in seedings of the treatments with different doses of tourmaline. However, when adding DHA1 and DHA4 into the system, the correlation coefficients (R²) decreased to 0.6976 and 0.5451 from 0.9264, respectively. In contrast with the Fe contents, the presence of DHAs didn't affect the R² between the levels of BDE-153 and the lipid contents in plant tissues. Our results indicated that both DHA1 and DHA4 could severely alter the BDE-153 uptake by L. sativa through reducing the Fe uptake instead of the lipid contents. Additionally, DHA4 exhibited much stronger abilities to alter the BDE-153 accumulation than DHA1. Transmission electron microscopy (TEM) observations indicated that either DHA1 or tourmaline or co-treatment with DHA and tourmaline had no negative impact on L. sativa at the cellular level. The present study provides important information for the impacts of different fractions of DHA extracted from soil on the BDE-153 migration in plant systems. Moreover, we elucidated the importance of the iron in tourmaline for migration of the polybrominated diphenyl ethers (PBDEs) in plant systems.

Quantitative identification of nitrate (NO3−-N) sources is critical to the control of nonpoint source nitrogen pollution in an agricultural watershed. Combined with water quality monitoring, we adopted the environmental isotope (δD-H2O, δ18O-H2O, δ15N-NO3−, and δ18O-NO3−) analysis and the Markov Chain Monte Carlo (MCMC) mixing model to determine the proportions of riverine NO3−-N inputs from four potential NO3−-N sources, namely, atmospheric deposition (AD), chemical nitrogen fertilizer (NF), soil nitrogen (SN), and manure and sewage (M&S), in the ChangLe River watershed of eastern China. Results showed that NO3−-N was the main form of nitrogen in this watershed, accounting for approximately 74% of the total nitrogen concentration. A strong hydraulic interaction existed between the surface and groundwater for NO3−-N pollution. The variations of the isotopic composition in NO3−-N suggested that microbial nitrification was the dominant nitrogen transformation process in surface water, whereas significant denitrification was observed in groundwater. MCMC mixing model outputs revealed that M&S was the predominant contributor to riverine NO3−-N pollution (contributing 41.8% on average), followed by SN (34.0%), NF (21.9%), and AD (2.3%) sources. Finally, we constructed an uncertainty index, UI90, to quantitatively characterize the uncertainties inherent in NO3−-N source apportionment and discussed the reasons behind the uncertainties.

In this study, we aimed to identify the toxic effects of chlorpyrifos exposure on the tissues of common carp. For this purpose, we evaluated histopathological changes in the brain, gills, liver, kidney, testis, and ovaries after 21 days of chlorpyrifos exposure. Activation of 8-OHdG, cleaved caspase-3, and iNOS were assesed by immunofluorescence assay in chlorpyrifos-exposed brain and liver tissue. Additionally, we measured the expression levels of caspase-3, caspase-8, iNOS, MT1, CYP1A, and CYP3A genes in chlorpyrifos-exposed brain tissue, as well as the expression levels of FSH and LH genes in chlorpyrifos-exposed ovaries, using qRT-PCR. We observed severe histopathological lesions, including inflammation, degeneration, necrosis, and hemorrhage, in the evaluated tissues of common carp after both high and low levels of exposure to chlorpyrifos. We detected strong and diffuse signs of immunofluorescence reaction for 8-OHdG, iNOS, and cleaved caspase-3 in the chlorpyrifos-exposed brain and liver tissues. Furthermore, we found that chlorpyrifos exposure significantly upregulated the expressions of caspase-3, caspase-8, iNOS, and MT1, and also moderately upregulated CYP1A and CYP3A in the brain tissue of exposed carp. We also noted downregulation of FSH and LH gene expressions in chlorpyrifos-exposed ovary tissues. Based on our results, chlorpyrifos toxication caused crucial histopathological lesions in vital organs, induced oxidative stress, inflammation, and apoptosis in liver and brain tissues, and triggered reproductive sterility in common carp. Therefore, we can propose that chlorpyrifos toxication is highly dangerous to the health of common carp. Moreover, chlorpyrifos pollution in the water could threaten the common carp population. Use of chlorpyrifos should be restricted, and aquatic systems should be monitored for chlorpyrifos pollution.

Toxicity of Cu and Cu-based nanoparticles (NPs) to aquatic biota is usually mitigated in natural freshwater compared to organics-free artificial freshwater. The main aim of this study was to evaluate whether mitigated toxicity is accompanied by lower total copper body burden in the freshwater crustacean Daphnia magna and whether CuO NPs are more hazardous in this aspect than soluble Cu salts.Total copper body burden in different media (OECD202 artificial freshwater and two natural freshwaters) was measured by a relatively novel technique - total reflection X-ray fluorescence (TXRF) spectroscopy - which proved suitable for the analysis of individual juvenile daphnids. Mean copper body burden was 2.8–42 times higher in daphnids exposed to CuO NPs (0.05 mg Cu/L and 1 mg Cu/L) than in daphnids exposed to equal or equitoxic concentrations (0.025 mg Cu/L and 0.05 mg Cu/L) of CuSO4. Using natural freshwater instead of artificial one resulted in increased copper burden after exposure to CuO NPs but not after exposure to Cu salt. After 24 h post-exposure depuration in the presence of algae Raphidocelis subcapitata, total copper body burden in daphnids exposed to CuO NPs sharply decreased while in daphnids exposed to Cu salt it did not. Despite the CuO NP toxicity mitigating effect of natural freshwater, total copper body burden of aquatic crustaceans in natural waterbodies may be greater than could be predicted based on the results obtained using artificial freshwater as the test medium.

Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO2 nanomaterials (TiO2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO2-NMs and their state during/after potential release is currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m2 of cement after 168 h of leaching. TiO2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO2-NM release mechanism is suspected to start from freeing of TiO2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO2-NM release was not solely related to the cement degradation rate.

Pharmaceuticals and personal care products are released into aquatic environments, largely as a result of ineffectual removal during wastewater treatment. Here we present a screening strategy based on the use of three commercially available mass spectral databases, combined into a single searchable entity and parallelized by cluster computing. In addition to this, a targeted solid phase extraction method with Ultra High Pressure Liquid Chromatography coupled to quadrupole time of flight mass spectrometry (UHPLC-QTOF) was used to quantify 99 pharmaceuticals in South African surface water on a national level. Limits of quantification were in the low ng/L range for the majority of the compounds and it was found that nationally both Lamotrigine and Nevirapine occurred most often. Prednisolone and Ritonavir were present at the highest average concentration; 623 and 489 ng/L respectively. It is however shown that more than 50% of the targets chosen for analysis are not detectable in any of the samples, which highlights the utility of untargeted, database driven screening; prior to the use of costly analytical standards. Untargeted screening detected 45% of the compounds detected in targeted mode, and furthermore tentatively identified a total of 4273 unique compounds across the samples. Automatically triggered MS/MS analyses yielded 92 unique hits with greater than 95% confidence. It is therefore suggested that untargeted screening should precede the targeted approach as a matter of economy and to guide the selection of targets for quantification. There is however great room for improvement in current commercial database search methodologies as a large bottleneck exists due to processing time.

The Catskill Mountains have been adversely impacted by decades of acid deposition, however, since the early 1990s, levels have decreased sharply as a result of decreases in emissions of sulfur dioxide and nitrogen oxides. This study examines trends in acid deposition, stream-water chemistry, and soil chemistry in the southeastern Catskill Mountains. We measured significant reductions in acid deposition and improvement in stream-water quality in 5 streams included in this study from 1992 to 2014. The largest, most significant trends were for sulfate (SO42−) concentrations (mean trend of −2.5 μeq L−1 yr−1); hydrogen ion (H+) and inorganic monomeric aluminum (Alim) also decreased significantly (mean trends of −0.3 μeq L−1 yr−1 for H+ and −0.1 μeq L−1 yr−1 for Alim for the 3 most acidic sites). Acid neutralizing capacity (ANC) increased by a mean of 0.65 μeq L−1 yr−1 for all 5 sites, which was 4 fold less than the decrease in SO42− concentrations. These upward trends in ANC were limited by coincident decreases in base cations (−1.3 μeq L−1 yr−1 for calcium + magnesium). No significant trends were detected in stream-water nitrate (NO3−) concentrations despite significant decreasing trends in NO3− wet deposition. We measured no recovery in soil chemistry which we attributed to an initially low soil buffering capacity that has been further depleted by decades of acid deposition. Tightly coupled decreasing trends in stream-water silicon (Si) (−0.2 μeq L−1 yr−1) and base cations suggest a decrease in the soil mineral weathering rate. We hypothesize that a decrease in the ionic strength of soil water and shallow groundwater may be the principal driver of this apparent decrease in the weathering rate. A decreasing weathering rate would help to explain the slow recovery of stream pH and ANC as well as that of soil base cations.