The Paranaguá Estuarine Complex (PEC) is an important socioeconomic estuary of the Brazilian coast that is influenced by the input of pollutants like polycyclic aromatic hydrocarbons (PAHs). Because of the apparent lack of comparative studies involving PAHs in different estuarine compartments, the aim of this study was to determine and compare PAH concentrations in surface sediment and suspended particulate material (SPM) in the PEC to evaluate their behaviour, compositions, sources and spatial distributions. The total PAH concentrations in the sediment ranged from 0.6 to 63.8 ng g−1 (dry weight), whereas in the SPM these concentrations ranged from 391 to 4164 ng g−1. Diagnostic ratios suggest distinct sources of PAHs to sediments (i.e., pyrolytic sources) and SPM (i.e., petrogenic sources such as vessel traffic). Thus, the recent introduction of PAHs is more clearly indicated in the SPM since oil related-compounds (e.g., alkyl-PAHs) remain present in similar concentrations. Further, this matrix may better reflect the current state of the environment at the time of sampling because of the absence of significant degradation.

Emerging aquatic insects are important vectors of contaminant transfer from aquatic to terrestrial food webs. However, the environmental factors that regulate contaminant body burdens in nearshore terrestrial consumers remain largely unexplored. We investigated the relative influences of riparian landscape composition (i.e., land use and nearshore vegetation structure) and contaminant flux via the emergent aquatic insect subsidy on selenium (Se) and mercury (Hg) body burdens of riparian ants (Formica subsericea) and spiders of the family Tetragnathidae along 11 river reaches spanning an urban-rural land-use gradient in Ohio, USA. Model-selection results indicated that fine-scale land cover (e.g., riparian zone width, shrub cover) in the riparian zone was positively associated with reach-wide body burdens of Se and Hg in both riparian F. subsericea and tetragnathid spiders (i.e., total magnitude of Hg and Se concentrations in ant and spider populations, respectively, for each reach). River distance downstream of Columbus, Ohio – where study reaches were impounded and flow through a large urban center – was also implicated as an important factor. Although stable-isotope analysis suggested that emergent aquatic insects were likely vectors of Se and Hg to tetragnathid spiders (but not to F. subsericea), emergent insect contaminant flux did not emerge as a significant predictor for either reach-wide body burdens of spider Hg or Se. Improved understanding of the pathways and influences that control aquatic-to-terrestrial contaminant transport will be critical for effective risk management and remediation.

Understanding of xenobiotic metabolism is necessary for risk assessment as well as toxicological research. In the present study, nanoLC/LTQ-Orbitrap mass based non-targeted metabolomics method coupled with ultra-performance liquid chromatography (UPLC)/triple quadrupole mass based targeted metabolomics method was carried out to investigate the stereoselective metabolism of benalaxyl in mouse hepatic microsomes. As a result, 7 metabolites of benalaxyl were identified, including 5 previously reported and 2 newly identified metabolites in present work. Hydroxylation, oxidation and esterolysis were major biotransformation reactions of benalaxyl in mouse hepatic microsomes. For stereoselective metabolism study, (−)-R-benalaxyl degraded much faster than its antipode with the t1/2 of 81.24 and 190.38 min for (−)-R- and (+)-S-benalaxyl, respectively. More importantly, stereoselectivity was also observed in the formation of the identified metabolites. In conclusion, the combined use of the mass spectrometry based targeted and non-targeted metabolomics provided a new approach to investigate stereoselective metabolism and identify novel metabolites of chiral pesticides. This study highlights the stereoselective metabolic profile of benalaxyl enantiomers and provides reliable data for benalaxyl toxicological risk assessment in mammal.

There is limited information on the BDE-209 relative bioavailability (RBA) of indoor dust and the absorption of BDE-209 after in vitro digestion was seldom studied. In the present study, BDE-209 RBA in 6 household dust samples measured using an in vivo mouse model was compared to BDE-209 bioaccessibility determined using physiologically based extraction test (PBET) and solubility bioaccessibility research consortium method (SBRC) assays. BDE-209 RBA obtained ranged from 45.9 ± 16.1 to 96.0 ± 17.4% and exhibited a significant relationship with PBET gastric phase (r2 = 0.578, p = 0.080), small intestinal phase (r2 = 0.728, p = 0.031) and total BDE-209 bioaccessibility (r2 = 0.728, p = 0.031), which indicated PBET assay can serve as a surrogate to predict BDE-209 RBA to refine human health exposure. In addition, the absorption of BDE-209 by Caco-2 cell line was assessed. With the consideration of the corresponding bioaccessibility and absorption of BDE-209 by Caco-2 cell line, the human daily intake of BDE-209 via dust ingestion for adults and children was much lower than that estimated by total concentration.

Iron reduction is one of the important organic matter (OM) mineralization pathway in sediments. Here we investigated the rates and the relative contribution of iron reduction to OM mineralization in Zhushan bay (ZSB, cyanobacterial bloom biomass (CBB)-dominated habitats) and East Taihu Lake (ETL, submerged macrophypes (SM)-dominated habitats) of Lake Taihu, China. Anaerobic microcosm incubation revealed that the rate of iron reduction at ZSB (4.42 μmol cm−3 d−1) in summer was almost 1.5 times higher than at ETL (3.13 μmol cm−3 d−1). Iron reduction accounted for 66.5% (ZSB) and 31.8% (ETL) of total anaerobic carbon mineralization, respectively. No detectable methanogenesis was found at ZSB, while methanogenesis was responsible for 16.7% of total anaerobic respiration in sediments of ETL. Geochemical analysis of solid phase constituents indicated that ZSB surface sediments experienced highly oxidizing conditions with much higher amorphous Fe(III) (71 mmol m−2) than ETL (11 mmol m−2). Conversely, AVS inventories at ETL (38 mmol m−2) were up to 30 times higher than at ZSB (1.27 mmol m−2), indicating significant sulfate reduction in sediments of ETL. Overall results suggested that varying carbon sources and distinct geochemical characterizations of the sediments in contrasting habitats significantly influenced the rate of iron reduction and the pathway of C mineralization in a large freshwater lake.

Within the framework of the Spanish monitoring program, this study reports on air concentration of DDTs, HCB, HCHs, NDL-PCBs, DL-PCBs, PCDD/Fs and PBDEs measured during the five-year sampling period 2008–2013. Spanish coastal remote and urban locations were studied using PUF disk passive air samplers which were deployed and collected every three months. Despite the wide range of concentrations measured for most contaminants, a common pattern of relative abundance (median values): NDL-PCBs (36.6 pg/m³) > HCB (24.8 pg/m³) ≈ HCHs (17.9 pg/m³) ≈ DDTs (16.6 pg/m³) > PBDEs (3.65 pg/m³) > DL-PCBs (2.99 pg/m³) >> PCDD/Fs (0.060 pg/m³) was found fairly consistent across most seasons and locations. Nevertheless, important variations in yearly concentrations were measured for different POPs. In general, higher levels of DDTs, HCHs, NDL-PCBs, DL-PCBs and PCDD/Fs were found in urban sites highlighting important differences between remote and urban sampling locations for most target contaminants. Greater concentrations of the banned organochlorine pesticides in urban locations suggested the existence of unexpected pointed sources that need to be further investigated and characterized. The limited dataset collected thus far rendered no clear temporal trends for most study target compounds, which emphasizes the necessity of the Spanish monitoring program future maintenance in time.

The behavior of photoactive TiO2 nanoparticles in an aquatic environment under UV irradiation was investigated. When there was no UV light irradiation, the attachment of humic acid (HA) onto the TiO2 nanoparticles improved their stability due to an increase in the electrostatic and steric repulsions between the particles. However, our study demonstrated that UV light clearly influenced the aggregation of TiO2 nanoparticles. Half an hour of UV irradiation caused the particles to aggregate from 331.0 nm to 1505.0 nm at a pH of 3.0. Similarly, the particles aggregated from 533.2 nm to 1037.0 nm at a pH of 6.5 and from 319.0 nm to 930.0 nm at a pH of 9.0. The aggregation continued with increased irradiation time, except for the condition at pH 3.0, which demonstrated disaggregation. Furthermore, we determined that the photocatalytic degradation of the HA dominated the behavior of TiO2 in our study. From the results of HA removal and 3DEEM fluorescence spectra data for the solution, a change in the HA was in accordance with the size change of the TiO2. The results illustrated that the UV irradiation affected the behavior of light-active nanomaterial (such as TiO2) in an aquatic system, thus influencing their bioavailability and reactivity.

The objective of this study was to determine the prevalence of Staphylococcus in urban wastewater treatment plants (UWTP) of La Rioja (Spain), and to characterize de obtained isolates. 16 wastewater samples (8 influent, 8 effluent) of six UWTPs were seeded on mannitol-salt-agar and oxacillin-resistance-screening-agar-base for staphylococci and methicillin-resistant Staphylococcus aureus recovery. Antimicrobial susceptibility profile was determined for 16 antibiotics and the presence of 35 antimicrobial resistance genes and 14 virulence genes by PCR. S. aureus was typed by spa, agr, and multilocus-sequence-typing, and the presence of immune-evasion-genes cluster was analyzed. Staphylococcus spp. were detected in 13 of 16 tested wastewater samples (81%), although the number of CFU/mL decreased after treatment. 40 staphylococci were recovered (1–5/sample), and 8 of them were identified as S. aureus being typed as (number of strains): spa-t011/agr-II/ST398 (1), spa-t002/agr-II/ST5 (2), spa-t3262/agr-II/ST5 (1), spa-t605/agr-II/ST126 (3), and spa-t878/agr-III/ST2849 (1). S. aureus ST398 strain was methicillin-resistant and showed a multidrug resistance phenotype. Virulence genes tst, etd, sea, sec, seg, sei, sem, sen, seo, and seu, were detected among S. aureus and only ST5 strains showed genes of immune evasion cluster. Thirty-two coagulase-negative Staphylococcus of 12 different species were recovered (number of strains): Staphylococcus equorum (7), Staphylococcus vitulinus (4), Staphylococcus lentus (4), Staphylococcus sciuri (4), Staphylococcus fleurettii (2), Staphylococcus haemolyticus (2), Staphylococcus hominis (2), Staphylococcus saprophyticus (2), Staphylococcus succinus (2), Staphylococcus capitis (1), Staphylococcus cohnii (1), and Staphylococcus epidermidis (1). Five presented a multidrug resistance phenotype. The following resistance and virulence genes were found: mecA, lnu(A), vga(A), tet(K), erm(C), msr(A)/(B), mph(C), tst, and sem. We found that Staphylococcus spp. are normal contaminants of urban wastewater, including different lineages of S. aureus and a high diversity of coagulase-negative species. The presence of multiple resistance and virulence genes, including mecA, in staphylococci of wastewater can be a concern for the public health.

Oxidative potential (OP) of particulate matter (PM) − defined as the capacity of PM to oxidize target molecules generating reactive oxygen species (ROS) − has been proposed as a more health relevant metric than PM mass. In this study two cell-free methods were used to assess the OP of PM filters collected at an urban site and to evaluate correlation with PM mass and PM composition.Among the different assays existing, two inexpensive and user-friendly methods were used both based on spectrophotometric measurements of depletion rate of target reagents oxidized by redox-active species present in PM. One assay measures the consumption of dithiothreitol (OPDTT) and the other the ascorbate (OPAA).Although both assays respond to the same redox-active species, i.e., quinones and transition metals, no correlations were found between OPDTT and OPAA responses to compounds standard solutions as well as to ambient samples. When expressed in relation to air volume, OPDTT m−3 strongly correlates with PM2.5 mass whereas no correlation was found for OPAA m−3 with PM2.5. When expressed on mass basis, both OPDTT μg−1 and OPAA μg−1 show a strong dependence on the sample composition, with higher OP for summer samples. OPDTT m−3 were highly correlated with the determined metals (Cu, Zn, Cr, Fe, Ni, Mn) whereas OPAA m−3 showed only moderate correlation with Cu and Mn.Thus, the two assays could potentially provide complementary information on oxidative potential characteristic of PM. Consequently, the combination of the two approaches can strengthen each other in giving insight into the contribution of chemical composition to oxidative properties of PM, which can subsequently be used to study health effects.

Pesticide pollution from agricultural field run-off or spray drift has been documented to impact river ecosystems worldwide. However, there is limited data on short- and long-term effects of repeated pulses of pesticide mixtures on biotic assemblages in natural systems. We used reported pesticide application data as input to a hydrological fate and transport model (Soil and Water Assessment Tool) to simulate spatiotemporal dynamics of pesticides mixtures in streams on a daily time-step. We then applied regression models to explore the relationship between macroinvertebrate communities and pesticide dynamics in the Sacramento River watershed of California during 2002–2013. We found that both maximum and average pesticide toxic units were important in determining impacts on macroinvertebrates, and that the compositions of macroinvertebrates trended toward taxa having higher resilience and resistance to pesticide exposure, based on the Species at Risk pesticide (SPEARpesticides) index. Results indicate that risk-assessment efforts can be improved by considering both short- and long-term effects of pesticide mixtures on macroinvertebrate community composition.