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Characterization of secondary organic aerosol from photo-oxidation of gasoline exhaust and specific sources of major components Full text
2018
Ma, Pengkun | Zhang, Peng | Shu, Jinian | Yang, Bo | Zhang, Haixu
To further explore the composition and distribution of secondary organic aerosol (SOA) components from the photo-oxidation of light aromatic precursors (toluene, m-xylene, and 1,3,5-trimethylbenzene (1,3,5-TMB)) and idling gasoline exhaust, a vacuum ultraviolet photoionization mass spectrometer (VUV-PIMS) was employed. Peaks of the molecular ions of the SOA components with minimum molecular fragmentation were clearly observed from the mass spectra of SOA, through the application of soft ionization methods in VUV-PIMS. The experiments comparing the exhaust-SOA and light aromatic mixture-SOA showed that the observed distributions of almost all the predominant cluster ions in the exhaust-SOA were similar to that of the mixture-SOA. Based on the characterization experiments of SOA formed from individual light aromatic precursors, the SOA components with molecular weights of 98 and 110 amu observed in the exhaust-SOA resulted from the photo-oxidation of toluene and m-xylene; the components with a molecular weight of 124 amu were derived mainly from m-xylene; and the components with molecular weights of 100, 112, 128, 138, and 156 amu were mainly derived from 1,3,5-TMB. These results suggest that C7-C9 light aromatic hydrocarbons are significant SOA precursors and that major SOA components originate from gasoline exhaust. Additionally, some new light aromatic hydrocarbon-SOA components were observed for the first time using VUV-PIMS. The corresponding reaction mechanisms were also proposed in this study to enrich the knowledge base of the formation mechanisms of light aromatic hydrocarbon-SOA compounds.
Show more [+] Less [-]Polychlorinated biphenyl (PCB) contamination in Galveston Bay, Texas: Comparing concentrations and profiles in sediments, passive samplers, and fish Full text
2018
Oziolor, Elias M. | Apell, Jennifer N. | Winfield, Zach C. | Back, Jeffrey A. | Usenko, Sascha | Matson, Cole W.
The industrialized portion of the Houston Ship Channel (HSC) is heavily contaminated with anthropogenic contaminants, most prominent of which are the polychlorinated biphenyls (PCBs). This contamination has driven adaptive evolution in a keystone species for Galveston Bay, the Gulf killifish (Fundulus grandis). We investigated the geographical extent of PCB impacts by sampling 12 sites, ranging from the heavily industrialized upper portion of the HSC to Galveston Island. At each site, PCB concentrations and profiles were determined in three environmental compartments: sediment, water (polyethylene passive samplers), and fish tissue (resident Gulf killifish). We observed a steep gradient of PCB contamination, ranging from 4.00 to 100,000 ng/g organic carbon in sediment, 290–110,000 ng/g lipid in fish, and 4.5–2300 ng/g polyethylene in passive samplers. The PCB congener profiles in Gulf killifish at the most heavily contaminated sites were shifted toward the higher chlorinated PCBs and were highly similar to the sediment contamination profiles. In addition, while magnitude of total PCB concentrations in sediment and total fish contamination levels were highly correlated between sites, the relative PCB congener profiles in fish and passive samplers were more alike. This strong correlation, along with a lack of dependency of biota-sediment accumulation factors with total contamination rates, confirm the likely non-migratory nature of Gulf killifish and suggest their contamination levels are a good site-specific indicator of contamination in the Galveston Bay area. The spatial gradient of PCB contamination in Galveston Bay was evident in all three matrices studied and was observed effectively using Gulf killifish contamination as an environmentally relevant bioindicator of localized contamination in this environment.
Show more [+] Less [-]Two forage fishes as potential conduits for the vertical transfer of microfibres in Northeastern Pacific Ocean food webs Full text
2018
Hipfner, J Mark | Galbraith, Moira | Tucker, Strahan | Studholme, Katharine R. | Domalik, Alice D. | Pearson, Scott F. | Good, Thomas P. | Ross, Peter S. | Hodum, Peter
We assessed the potential role played by two vital Northeastern Pacific Ocean forage fishes, the Pacific sand lance (Ammodytes personatus) and Pacific herring (Clupea pallasii), as conduits for the vertical transfer of microfibres in food webs. We quantified the number of microfibres found in the stomachs of 734 sand lance and 205 herring that had been captured by an abundant seabird, the rhinoceros auklet (Cerorhinca monocerata). Sampling took place on six widely-dispersed breeding colonies in British Columbia, Canada, and Washington State, USA, over one to eight years. The North Pacific Ocean is a global hotspot for pollution, yet few sand lance (1.5%) or herring (2.0%) had ingested microfibres. In addition, there was no systematic relationship between the prevalence of microplastics in the fish stomachs vs. in waters around three of our study colonies (measured in an earlier study). Sampling at a single site (Protection Island, WA) in a single year (2016) yielded most (sand lance) or all (herring) of the microfibres recovered over the 30 colony-years of sampling involved in this study, yet no microfibres had been recovered there, in either species, in the previous year. We thus found no evidence that sand lance and herring currently act as major food-web conduits for microfibres along British Columbia's outer coast, nor that the local at-sea density of plastic necessarily determines how much plastic enters marine food webs via zooplanktivores. Extensive urban development around the Salish Sea probably explains the elevated microfibre loads in fishes collected on Protection Island, but we cannot account for the between-year variation. Nonetheless, the existence of such marked interannual variation indicates the importance of measuring year-to-year variation in microfibre pollution both at sea and in marine biota.
Show more [+] Less [-]One-century sedimentary record of heavy metal pollution in western Taihu Lake, China Full text
2018
Li, Yan | Zhou, Shenglu | Zhu, Qing | Li, Baojie | Wang, Junxiao | Wang, Chunhui | Chen, Lian | Wu, Shaohua
Long-term trends of sediment compositions are important for assessing the impact of human activities on the sediment and protecting the sediment environment. In this study, based on the contents of heavy metals and the Pb isotope ratios in lake sediments, atmospheric dustfall and soil in Yixing, China, the representative heavy metals (Zn, Pb, Cr and Cd) in lake sediments from western Taihu Lake were studied. The evolution history of heavy metals in the local environment was constructed for the past 100 years. From 1892 to the 1990s, the anthropogenic fluxes of the representative heavy metals were negligible, indicating minimal anthropogenic emissions of heavy metals. Since the 1990s, anthropogenic fluxes of the representative heavy metals began to increase, concurrent with the economic growth and development in the western Taihu Lake Basin after the Chinese economic reform. The maximum flux percentage of the heavy metals in the sediments, caused by human activities, is 23.0% for Zn, 31.6% for Pb, 39.5% for Cr and 85.3% for Cd, indicating that most of the Cd comes from human activities. The Cd content in the western Taihu Lake Basin was significantly higher than that in the other areas, and the rapid development of the industry in the western Taihu Lake Basin and ceramics in Yixing led to the enrichment of heavy metals in local sediments. Since the 21st century, measures have been taken to control the pollution of heavy metals, including the increase in local government attention and the deployment of environmental monitoring technology. However, heavy metal content remains high, and the Pb content is still increasing. The ratios of Pb isotopes show that the main sources of heavy metals in the western Taihu Lake sediments, the local soil of Yixing and the atmospheric dustfall are coal combustion, leaded gasoline combustion, industrial wastewater and domestic sewage.
Show more [+] Less [-]Biota monitoring under the Water Framework Directive: On tissue choice and fish species selection Full text
2018
Fliedner, Annette | Rüdel, Heinz | Lohmann, Nina | Buchmeier, Georgia | Koschorreck, Jan
The study addresses the topic of suitable matrices for chemical analysis in fish monitoring and discusses the effects of data normalization in the context of the European Water Framework Directive (WFD). Differences between species are considered by comparing three frequently monitored species of different trophic levels, i.e., chub (Squalius cephalus, n = 28), (bream, Abramis brama, n = 11), and perch (Perca fluviatilis, n = 19) sampled in the German Danube. The WFD priority substances dioxins, furans and dioxin-like polychlorinated biphenyls (PCDD/F + dl-PCB), polybrominated diphenyl ethers (PBDE), α-hexabromocyclododecane (α-HBCDD), hexachlorobenzene (HCB), mercury (Hg), and perfluorooctane sulfonic acid (PFOS) as well as non-dioxin-like (ndl)-PCB were analyzed separately in fillet and carcass and whole body concentrations were calculated. Hg was analyzed in individual fish fillets and carcasses, all other substances were determined in pool samples, which were compiled on the basis of fish size (3 chub pools, 1 bream pool, 2 perch pools). The data were normalized to 5% lipid weight (or 26% dry mass in the case of Hg and PFOS) for comparison between matrices and species.Hg concentrations were generally higher in fillet than in whole fish (mean whole fish-to-fillet ratio: 0.7) whereas all other substances were mostly higher in whole fish. In the case of lipophilic substances these differences leveled after lipid normalization.Significant correlations (p ≤ .05) were detected between Hg and fish weight and age. Hg concentrations varied least among younger fish. PCDD/F, dl-PCB, ndl-PCB, PBDE, α-HBCDD and HCB correlated significantly (p ≤ .05) with lipid concentrations. Fillet-to-whole fish conversion equations and/or conversion factors were derived for all substances except α-HCBDD. Although more data also for individual fish would be desirable the results are nevertheless a step on the way to translate fillet concentrations of priority substances to whole fish concentrations.
Show more [+] Less [-]Occurrence of microplastics in the water column and sediment in an inland sea affected by intensive anthropogenic activities Full text
2018
Dai, Zhenfei | Zhang, Haibo | Zhou, Qian | Tian, Yuan | Chen, Tao | Du, Zhen | Fu, Chuancheng | Luo, Yongming
Microplastics may lose buoyancy and occur in deeper waters and ultimately sink to the sediment and this may threaten plankton inhabiting in various water layers and benthic organisms. Here, we conduct the first survey on microplastics in the water column and corresponding sediment in addition to the surface water in the Bohai Sea. A total of 20 stations covering whole Bohai Sea were selected, which included 6 stations specified for water column studying. Seawater was sampled every 5 m, with maximal depth of 30 m in the water column using Niskin bottles coupled with a ship-based conductivity, temperature and depth sensor (CTD) system and surface sediment samples were collected using box corer. The results indicated that higher microplastic levels accumulated at a depth range of 5–15 m in the water column in some stations, suggesting the surface water survey was not sufficient to reflect microplastics loading in a water body. Fibers predominated microplastic types in both seawater and sediment of the Bohai Sea, which accounted for 75%–96.4% of the total microplastics. However the relatively proportion of the fibers in the deeper water layers and sediment was lower than that in the surface water. Microplastic shapes are more diverse in the sediment than in the seawater in general. The microplastic sizes changed with depth in the water column and the proportion of the size-fraction < 300 μm increased with depth, probably as a result of rapid biofouling on the small microplastics due to their higher specific surface area. Such depth distribution also implied that sampling with manta net (>330 μm) that commonly used in the oceanographic survey might underestimate microplastics abundance in the water column. Further studies are recommended to focus on the sinking behavior of microplastics and their effects on marine organisms.
Show more [+] Less [-]Measuring log Kow coefficients of neutral species of perfluoroalkyl carboxylic acids using reversed-phase high-performance liquid chromatography Full text
2018
Xiang, Qian | Shan, Guoqiang | Wu, Wei | Jin, Hangbiao | Zhu, Lingyan
Accurate measuring n-octanol/water partition coefficients (log Kₒw) of perfluoroalkyl carboxylic acids (PFCAs) using experimental approach has been proven to be very difficult due to their special properties. The ionizable carboxyl groups in PFCAs make their log Kₒw dependent on pH. In this study, the log Kₒw values of neutral species of PFCAs (C₄≤ₙ≤₁₄) were measured based on reversed-phase high-performance liquid chromatography (RP-HPLC) with the mobile phase pH varying in the range of 1.09–5.00. The relationship between log Kₒw and retention times was established using some reference compounds (including agrochemicals, polycyclic aromatic hydrocarbons) with known log Kₒw values, and then validated with alkyl fatty acids, which have similar chemical structures as PFCAs. The apparent log Kₒw (i.e., log Dₒw) of the C₄–₁₄ PFCAs were calculated based on their retention times using the established model, and they displayed a negative linear relationship with the mobile phase pH in the range of 1.09–4.00. Consequently, the log Dₒw values were converted to the corresponding log Kₒw values (1.05–7.19) based on the relationship of log Dₒw = log Kₒw + pKₐ – pH. The log Kₒw increased with perfluorinated carbon chain length with a greater rate for C₄ to C₅ PFCAs than for C₅–₁₄ PFCAs.
Show more [+] Less [-]Joining empirical and modelling approaches to estimate dry deposition of nitrogen in Mediterranean forests Full text
2018
García-Gómez, Héctor | Izquieta-Rojano, Sheila | Aguillaume, Laura | González-Fernández, Ignacio | Valiño, Fernando | Elustondo, David | Santamaría, Jesús M. | Àvila, Anna | Bytnerowicz, Andrzej | Bermejo, Victoria | Alonso, Rocío
In Mediterranean areas, dry deposition is a major component of the total atmospheric N input to natural habitats, particularly to forest ecosystems. An innovative approach, combining the empirical inferential method (EIM) for surface deposition of NO₃⁻ and NH₄⁺ with stomatal uptake of NH₃, HNO₃ and NO₂ derived from the DO₃SE (Deposition of Ozone and Stomatal Exchange) model, was used to estimate total dry deposition of inorganic N air pollutants in four holm oak forests under Mediterranean conditions in Spain. The estimated total deposition varied among the sites and matched the geographical patterns previously found in model estimates: higher deposition was determined at the northern site (28.9 kg N ha⁻¹ year⁻¹) and at the northeastern sites (17.8 and 12.5 kg N ha⁻¹ year⁻¹) than at the central-Spain site (9.4 kg N ha⁻¹ year⁻¹). On average, the estimated dry deposition of atmospheric N represented 77% ± 2% of the total deposition of N, of which surface deposition of gaseous and particulate atmospheric N averaged 10.0 ± 2.9 kg N ha⁻¹ year⁻¹ for the four sites (58% of the total deposition), and stomatal deposition of N gases averaged 3.3 ± 0.8 kg N ha⁻¹ year⁻¹ (19% of the total deposition). Deposition of atmospheric inorganic N was dominated by the surface deposition of oxidized N in all the forests (means of 54% and 42% of the dry and total deposition, respectively). The relative contribution of NO₂ to dry deposition averaged from 19% in the peri-urban forests to 11% in the most natural site. During the monitoring period, the empirical critical loads provisionally proposed for ecosystem protection (10–20 kg N ha⁻¹ year⁻¹) was exceeded in three of the four studied forests.
Show more [+] Less [-]Antibiotic and heavy metal resistance in enterococci from coastal marine sediment Full text
2018
Vignaroli, Carla | Pasquaroli, Sonia | Citterio, Barbara | Di Cesare, Andrea | Mangiaterra, Gianmarco | Fattorini, Daniele | Biavasco, Francesca
Sediment samples from three coastal sites - two beach resorts (Beach 1 and Beach 2 sites) and an area lying between an oil refinery and a river estuary (Estuarine site) - were analyzed for antibiotic- and heavy metal (HM)-resistant enterococci.A total of 123 enterococci, 36 E. faecium, 34 E. casseliflavus, 33 E. hirae, 5 E. faecalis, 3 E. durans, 3 E. gallinarum, and 9 Enterococcus spp, were recovered. Strains resistant to erythromycin, tetracycline and quinupristin/dalfopristin (Q/D) were recovered from all sites, whereas multidrug-resistant isolates were recovered only from “Beach 2” (14%) and “Estuarine” (3.7%). As regards HM resistance, the strains showed a high frequency (68%) of cadmium and/or copper resistance and uniform susceptibility to mercury. The prevalence of cadmium-resistant strains was significantly higher among erythromycin-resistant than among erythromycin-susceptible strains. A significant association between cadmium or copper resistance and Q/D resistance was also observed at “Estuarine” site. The levels of the two HMs in sediment from all sites were fairly low, ranging from 0.070 to 0.126 μg/g, for cadmium and from 1.00 to 7.64 μg/g for copper. Mercury was always undetectable. These findings are consistent with reports that low HM concentrations may contribute to co-selection of antibiotic-resistant bacterial strains, including enterococci.
Show more [+] Less [-]Comparative toxicity of pristine graphene oxide and its carboxyl, imidazole or polyethylene glycol functionalized products to Daphnia magna: A two generation study Full text
2018
Liu, Yingying | Han, Wenli | Xu, Zhizhen | Fan, Wenhong | Peng, Weihua | Luo, Shenglian
To investigate the chronic toxicity of graphene oxide (GO) and its functionalized products (GO-carboxyl, GO-imidazole and GO-polyethylene glycol), a two-generation study was conducted using the aquatic model species Daphnia magna. Each generation of daphnids were exposed for 21 days to 1.0 mg L−1 graphene material, with body length, neonate number, time of first brood and the intrinsic rate of natural increase (r) assessed as endpoints. Chronic exposure to GO, GO-carboxyl, and GO-imidazole had no adverse effect on body length or offspring number in the daphnid F0 generation, however, this exposure paradigm led to significant growth or reproduction inhibition in the following generation. Meanwhile, GO was found to show the strongest inhibitory effect, sequentially followed by GO-carboxyl and GO-imidazole. With exposure to GO-polyethylene glycol, no significant effects on growth or reproduction were observed for both F0 and F1 generation daphnids. These results reveal that carboxyl, imidazole and polyethylene glycol functional attachments alleviate the bio-toxicity of GO, especially polyethylene glycol. The increased C/O atomic ratio present in GO-carboxyl, GO-imidazole and GO-polyethylene glycol due to functionalization may mainly explain the reduced toxicity.
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