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Selenium in surface waters of the lower Athabasca River watershed: Chemical speciation and implications for aquatic life
2018
Donner, Mark W. | Cuss, Chad W. | Poesch, Mark | Sinnatamby, R Nilo | Shotyk, William | Siddique, Tariq
Selenium in the lower Athabasca River (Alberta, Canada) is of concern due to potential inputs from the weathering of shallow bitumen deposits and emissions from nearby surface mines and upgraders. Understanding the source of this Se, however, is complicated by contributions from naturally saline groundwater and organic matter-rich tributaries. As part of a two-year multi-disciplinary study to assess natural and anthropogenic inputs, Se and its chemical speciation were determined in water samples collected along a ∼125 km transect of the Athabasca River and associated tributaries. Selenium was also determined in the muscle of Trout-perch (Percopsis omiscomaycus), a non-migratory fish species, that were sampled from selected locations. Dissolved (<0.45 μm) Se in the Athabasca River was consistently low in 2014 (0.11 ± 0.02 μg L⁻¹; n = 14) and 2015 (0.16 ± 0.02 μg L⁻¹; n = 21), with no observable increase from upstream to downstream. Selenate was the predominant inorganic form (∼60 ng L⁻¹) and selenite was below detection limits at most locations. The average concentration of Se in Trout-perch muscle was 2.2 ± 0.4 mg kg⁻¹ (n = 34), and no significant difference (p > 0.05) was observed between upstream and midstream (industrial) or downstream reaches. Tributary waters contained very low concentrations of Se (typically < 0.1 μg L⁻¹), which was most likely present in the form of dissolved organic colloids.
Mostrar más [+] Menos [-]Tackling nitric oxide emissions from dominant diesel vehicle models using on-road remote sensing technology
2018
Huang, Yuhan | Yam, Yat Shing | Lee, Casey K.C. | Organ, Bruce | Zhou, John L. | Surawski, Nic C. | Chan, Edward F.C. | Hong, Guang
Remote sensing provides a rapid detection of vehicle emissions under real driving condition. Remote sensing studies showed that diesel nitrogen oxides emissions changed little or were even increasing in recent years despite the tightened emission standards. To more accurately and fairly evaluate the emission trends, it is hypothesized that analysis should be detailed for individual vehicle models as each model adopted different emissions control technologies and retrofitted the engine/vehicle at different time. Therefore, this study was aimed to investigate the recent nitric oxide (NO) emission trends of the dominant diesel vehicle models using a large remote sensing dataset collected in Hong Kong. The results showed that the diesel vehicle fleet was dominated by only seven models, accounting for 78% of the total remote sensing records. Although each model had different emission levels and trends, generally all the dominant models showed a steady decrease or stable level in the fuel based NO emission factors (g/kg fuel) over the period studied except for BaM1 and BdM2. A significant increase was observed for the BaM1 2.49 L and early 2.98 L models during 2005–2011, which we attribute to the change in the diesel fuel injection technology. However, the overall mean NO emission factor of all the vehicles was stable during 1991–2006 and then decreased steadily during 2006–2016, in which the emission trends of individual models were averaged out and thus masked. Nevertheless, the latest small, medium and heavy diesel vehicles achieved similar NO emission factors due to the converging of operation windows of the engine and emission control devices. The findings suggested that the increasingly stringent European emission standards were not very effective in reducing the NO emissions of some diesel vehicle models in the real world.
Mostrar más [+] Menos [-]Fatty acid composition, enzyme activities and metallothioneins in Donax trunculus (Mollusca, Bivalvia) from polluted and reference sites in the Gulf of Annaba (Algeria): Pattern of recovery during transplantation
2018
Rabei, Amina | Hichami, Aziz | Beldi, Hayet | Bellenger, Sandrine | Khan, Naim Akhtar | Soltani, Noureddine
The gulf of Annaba, the most important touristic and economic coastal zone located in Northeast Algeria, is contaminated by several pollutants from urban, agricultural, harbor and industrial activities. Elevated levels of heavy metals were detected in a locally prevalent edible mollusk Donax trunculus (Bivalvia, Donacidae) widely used as a sentinel species for the assessment of marine pollution. The present work aims to measure the difference between two localities, one being full of different pollutants (Sidi Salem) and the other being relatively clean (El Battah) and to evaluate the ability of D. trunculus to overcome the environmental stress during a transplantation experiment by a determination of fatty acid profile, the enzymes activities and the level of metallothioneins (MTs), a biomarker of metallic contamination. Adults of D. trunculus were collected at Sidi Salem (contaminated site) and transplanted into El Battah (reference site) for 21 days in cages (60 × 60 × 60 cm with a 2 mm mesh). Biochemical analyzes were conducted at different times (0, 7, 14 and 21 days). At 0-day experiment: the rate of the fatty acids, the enzymes activities and MT levels at the site of Sidi Salem (polluted site) were significantly different from those of El Battah. During the transplantation a gradual restoration of fatty acids rates, enzymes activities and MT levels was observed. At the end of the period of transplantation, the values are comparable to those of El Battah. A two-way ANOVA (time, site) on data revealed significant effects of time and site. Overally, D. trunculus is able to induce its detoxification system and to restore relatively rapidly the status of individuals from the reference site (El Battah).
Mostrar más [+] Menos [-]Detecting sulfamethoxazole and carbamazepine in groundwater: Is ELISA a reliable screening tool?
2018
Diekoff, Aliesha L. | Elliott, Sarah M. | Erickson, Melinda L. | Adams, Byron A.
In recent years, numerous studies have reported the prevalence of organic micropollutants in natural waters. There is an increasing interest in assessing the occurrence and transport of these contaminants in groundwater because a large number of people in the United States rely on groundwater for their drinking water. However, commonly used mass-spectrometry-based analytical methods are expensive and time-consuming. The enzyme-linked immunosorbent assay (ELISA) method offers an inexpensive analytical alternative that provides semi-quantitative results in a relatively quick timeframe. We investigated the use of ELISA for two commonly detected micropollutants, sulfamethoxazole (SMX) and carbamazepine (CBZ), in groundwater collected as part of two different studies, one in Minnesota and the other in Iowa. The ELISA results were compared with two mass-spectrometry-based methods: (1) direct aqueous injection-high performance liquid chromatography/tandem mass spectrometry (HPLC) and (2) online solid-phase extraction with liquid chromatography/electrospray ionization-mass spectrometry (SPE LC). Differences in SMX and CBZ observations between ELISA and both HPLC and SPE LC were analyzed using the Paired Prentice-Wilcoxon test. Estimates of bias and limits of agreement between paired observations also were calculated. The SMX determinations by ELISA yielded results that were 30 and 14% greater than HPLC and SPE LC, respectively. The CBZ determinations by ELISA yielded results that were 25 and 9% greater than HPLC and SPE LC, respectively. The ELISA determinations were in presence-absence agreement with HPLC for 83% of samples for SMX and CBZ; and with SPE LC for 76 and 80% of samples for SMX and CBZ, respectively. Results indicate that ELISA for SMX and CBZ is a reliable and cost effective screening-tool alternative to more commonly used mass spectrometry-based analytical methods.
Mostrar más [+] Menos [-]Ferric-enhanced chemical remediation of dredged marine sediment contaminated by metals and petroleum hydrocarbons
2018
Yoo, Jongchan | Jeon, Pilyong | Tsang, Daniel C.W. | Kwon, Eilhann E. | Baek, Kitae
Sediments nearby harbors are dredged regularly, and the sediments require the stringent treatment to meet the regulations on reuse and mitigate the environmental burdens from toxic pollutants. In this study, FeCl₃ was chosen as an extraction agent to treat marine sediment co-contaminated with Cu, Zn, and total petroleum hydrocarbons (TPH). In chemical extraction process, the extraction efficiency of Cu and Zn by FeCl₃ was compared with the conventional one using inorganic acids (H₂SO₄ and HCl). Despite the satisfactory level for extraction of Cu (78.8%) and Zn (73.3%) by HCl (0.5 M) through proton-enhanced dissolution, one critical demerit, particularly acidified sediment, led to the unwanted loss of Al, Fe, and Mg by dissolution. Moreover, the vast amount of HCl required the huge amounts of neutralizing agents for the post-treatment of the sediment sample via the washing process. Despite a low concentration, extraction of Cu (70.1%) and Zn (69.4%) was done by using FeCl₃ (0.05 M) through proton-enhanced dissolution, ferric-organic matter complexation, and oxidative dissolution of sulfide minerals. Ferric iron (Fe³⁺) was reduced to ferrous iron (Fe²⁺) with sulfide (S²⁻) oxidation during FeCl₃ extraction. In consecutive chemical oxidations using hydrogen peroxide (H₂O₂) and persulfate (S₂O₈²⁻), the resultant ferrous iron was used to activate the oxidants to effectively degrade TPH. S₂O₈²⁻ using FeCl₃ solution (molar ratio of ferrous to S₂O₈²⁻ is 19.8–198.3) removed 42.6% of TPH, which was higher than that by H₂O₂ (molar ratio of ferrous to H₂O₂ is 1.2–6.1). All experimental findings suggest that ferric is effectively accommodated to an acid washing step for co-contaminated marine sediments, which leads to enhanced extraction, cost-effectiveness, and less environmental burden.
Mostrar más [+] Menos [-]Environmental transformations and ecological effects of iron-based nanoparticles
2018
Lei, Cheng | Sun, Yuqing | Tsang, Daniel C.W. | Lin, Daohui
The increasing application of iron-based nanoparticles (NPs), especially high concentrations of zero-valent iron nanoparticles (nZVI), has raised concerns regarding their environmental behavior and potential ecological effects. In the environment, iron-based NPs undergo physical, chemical, and/or biological transformations as influenced by environmental factors such as pH, ions, dissolved oxygen, natural organic matter (NOM), and biotas. This review presents recent research advances on environmental transformations of iron-based NPs, and articulates their relationships with the observed toxicities. The type and extent of physical, chemical, and biological transformations, including aggregation, oxidation, and bio-reduction, depend on the properties of NPs and the receiving environment. Toxicities of iron-based NPs to bacteria, algae, fish, and plants are increasingly observed, which are evaluated with a particular focus on the underlying mechanisms. The toxicity of iron-based NPs is a function of their properties, tolerance of test organisms, and environmental conditions. Oxidative stress induced by reactive oxygen species is considered as the primary toxic mechanism of iron-based NPs. Factors influencing the toxicity of iron-based NPs are addressed and environmental transformations play a significant role, for example, surface oxidation or coating by NOM generally lowers the toxicity of nZVI. Research gaps and future directions are suggested with an aim to boost concerted research efforts on environmental transformations and toxicity of iron-based NPs, e.g., toxicity studies of transformed NPs in field, expansion of toxicity endpoints, and roles of laden contaminants and surface coating. This review will enhance our understanding of potential risks of iron-based NPs and proper uses of environmentally benign NPs.
Mostrar más [+] Menos [-]Photodegradation of fluorotelomer carboxylic 5:3 acid and perfluorooctanoic acid using zinc oxide
2018
Abada, Bilal | Alivio, Theodore E.G. | Shao, Yiru | O'Loughlin, Thomas E. | Klemashevich, Cory | Banerjee, Sarbajit | Jayaraman, Arul | Chu, Kung-Hui
Occurrence of per- and poly-fluoroalkyl substances (PFASs) in the environment and biota has raised a great concern to public health because these compounds are persistent, bioaccumulative, and toxic. Biodegradation of polyfluoroalkyl substances, particularly long-chain fluorotelomer-based products, can lead to production of various short-chain PFASs, with 5:3 fluorotelomer carboxylic acid (referred as 5:3 FTCA hereafter) as a dominant polyfluoroalkyl metabolite. Perfluoroalkyl acids, particularly perfluorooctanoic acid (PFOA), are toxic and current removal methods are not cost-effective. This study reports the photodegradation of 5:3 FTCA and PFOA using ZnO as a photocatalyst under neutral pH and room temperature conditions. Under long UV wavelength (365 nm), both tetrapod and commercial ZnO can photodegrade 5:3 FTCA. Five removal products—perfluorohexanoic acid, perfluoropentanoic acid, perfluorobutyric acid, 5:2 fluorotelomer carboxylic acid (5:2 FTCA), and inorganic fluoride—were identified, with PFBA and F⁻ as dominant end products. SEM and XPS high-resolution scans on the surface of the utilized ZnO showed less units of CF₂ than that in 5:3 FTCA, supporting occurrence of photodegradation of 5:3 FTCA by ZnO. Defluorination of PFOA was not observed with ZnO only, but at pH 5 and in the co-presence of Fe-citrate. PFOA defluorination increased from 0.93% after 3 days of UV light exposure to 3.9% after additional 135 h under direct sunlight exposure. To the authors’ best knowledge, this is the first report studying ZnO-catalyzed photodegradation of 5:3 FTCA, and examining the Fe co-addition for PFOA defluorination.
Mostrar más [+] Menos [-]Factors dominating 3-dimensional ozone distribution during high tropospheric ozone period
2018
Chen, Xiaoyang | Liu, Yiming | Lai, Anqi | Han, Shuangshuang | Fan, Qi | Wang, Xuemei | Ling, Zhenhao | Huang, Fuxiang | Fan, Shaojia
Data from an in situ monitoring network and five ozone sondes are analysed during August of 2012, and a high tropospheric ozone episode is observed around the 8th of AUG. The Community Multi-scale Air Quality (CMAQ) model and its process analysis tool were used to study factors and mechanisms for high ozone mixing ratio at different levels of ozone vertical profiles. A sensitive scenario without chemical initial and boundary conditions (ICBCs) from MOZART4-GEOS5 was applied to study the impact of stratosphere-troposphere exchange (STE) on vertical ozone. The simulation results indicated that the first high ozone peak near the tropopause was dominated by STE. Results from process analysis showed that: in the urban area, the second peak at approximately 2 km above ground height was mainly caused by local photochemical production. The third peak (near surface) was mainly caused by the upwind transportation from the suburban/rural areas; in the suburban/rural areas, local photochemical production of ozone dominated the high ozone mixing ratio from the surface to approximately 3 km height. Furthermore, the capability of indicators to distinguish O3-precursor sensitivity along the vertical O3 profiles was investigated. Two sensitive scenarios, which had cut 30% anthropogenic NOX or VOC emissions, showed that O3-precursor indicators, specifically the ratios of O3/NOy, H2O2/HNO3 or H2O2/NOZ, could partly distinguish the O3-precursor sensitivity between VOCs-sensitive and NOx-sensitive along the vertical profiles. In urban area, the O3-precursor relationship transferred from VOCs-sensitive within the boundary layer to NOx-sensitive at approximately 1–3 km above ground height, further confirming the dominant roles of transportation and photochemical production in high O3 peaks at the near-ground layer and 2 km above ground height, respectively.
Mostrar más [+] Menos [-]Alginate affects agglomeration state and uptake of 14C-labeled few-layer graphene by freshwater snails: Implications for the environmental fate of graphene in aquatic systems
2018
Su, Yu | Huang, Ji | Lu, Fenxiao | Tong, Xin | Niu, Junfeng | Mao, Liang
Understanding of the interaction of graphene with natural polysaccharides (e.g., alginate) is crucial to elucidate its environmental fate. We investigated the impact of alginate on the agglomeration and stability of ¹⁴C-labeled few-layer graphene (FLG) in varying concentrations of monovalent (NaCl) and divalent (CaCl₂) electrolytes. Enhanced agglomeration occurred at high CaCl₂ concentrations (≥5 mM) due to the alginate gel networks formation in the presence of Ca²⁺. FLG enmeshed within extended alginate gel networks was observed under transmission electron microscope and atomic force microscope. However, background Na⁺ competition for binding sites with Ca²⁺ at the alginate surfaces shielded the gelation of alginate. FLG was readily dispersed by alginate under environmentally relevant ionic strength conditions (i.e., <200 mM Na⁺ and <5 mM Ca²⁺). In comparison with the bare FLG, the slow sedimentation of the alginate-stabilized FLG (158 μg/L) caused continuous exposure of this nanomaterial to freshwater snails, which ingested 1.9 times more FLG through filter-feeding within 72 h. Moreover, surface modification of FLG by alginate significantly increased the whole-body and intestinal levels of FLG, but reduced the internalization of FLG to the intestinal epithelial cells. These findings indicate that alginate will act as a stabilizing agent controlling the transport of FLG in aqueous systems. This study also provides the first evidence that interaction of graphene with natural polysaccharides affected the uptake of FLG in the snails, which may alter the fate of FLG in aquatic environments.
Mostrar más [+] Menos [-]Historical legacies of river pollution reconstructed from fish scales
2018
Morán, Paloma | Cal, Laura | Cobelo-García, Antonio | Almécija, Clara | Caballero, Pablo | Garcia de Leaniz, Carlos
Many rivers have been impacted by heavy metal pollution in the past but the long-term legacies on biodiversity are difficult to estimate. The River Ulla (NW Spain) was impacted by tailings from a copper mine during the 1970–1980s but absence of baseline values and lack of subsequent monitoring have prevented a full impact assessment. We used archived fish scales of Atlantic salmon to reconstruct levels of historical copper pollution and its effects on salmon fitness. Copper bioaccumulation significantly increased over baseline values during the operation of the mine, reaching sublethal levels for salmon survival. Juvenile growth and relative population abundance decreased during mining, but no such effects were observed in a neighbouring river unaffected by mining. Our results indicate that historical copper exposure has probably compromised the fitness of this Atlantic salmon population to the present day, and that fish scales are suitable biomarkers of past river pollution.
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