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Size matters – The phototoxicity of TiO2 nanomaterials
2016
Wyrwoll, Anne J. | Lautenschläger, Petra | Bach, Alexander | Hellack, Bryan | Dybowska, Agnieszka | Kuhlbusch, Thomas A.J. | Hollert, Henner | Schäffer, Andreas | Maes, Hanna M.
Under solar radiation several titanium dioxide nanoparticles (nano-TiO2) are known to be phototoxic for daphnids. We investigated the influence of primary particle size (10, 25, and 220 nm) and ionic strength (IS) of the test medium on the acute phototoxicity of anatase TiO2 particles to Daphnia magna.The intermediate sized particles (25 nm) showed the highest phototoxicity followed by the 10 nm and 220 nm sized particles (median effective concentrations (EC50): 0.53, 1.28, 3.88 mg/L). Photoactivity was specified by differentiating free OH radicals (therephthalic acid method) and on the other hand surface adsorbed, as well as free OH, electron holes, and O2− (electron paramagnetic resonance spectroscopy, EPR). We show that the formation of free OH radicals increased with a decrease in primary particle size (terephthalic acid method), whereas the total measured ROS content was highest at an intermediate particle size of 25 nm, which consequently revealed the highest photoxicity. The photoactivities of the 10 and 220 nm particles as measured by EPR were comparable. We suggest that phototoxicity depends additionally on the particle–daphnia interaction area, which explains the higher photoxicity of the 10 nm particles compared to the 220 nm particles. Thus, phototoxicity is a function of the generation of different ROS and the particle–daphnia interaction area, both depending on particle size.Phototoxicity of the 10 nm and 25 nm sized nanoparticles decreased as IS of the test medium increased (EC50: 2.9 and 1.1 mg/L). In conformity with the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory we suggest that the precipitation of nano-TiO2 was more pronounced in high than in low IS medium, causing a lower phototoxicity.In summary, primary particle size and IS of the medium were identified as factors influencing phototoxicity of anatase nano-TiO2 to D. magna.
Show more [+] Less [-]Iron plaque formed under aerobic conditions efficiently immobilizes arsenic in Lupinus albus L roots
2016
Arsenic is a non-threshold carcinogenic metalloid. Thus, human exposure should be minimised, e.g. by chemically stabilizing As in soil. Since iron is a potential As immobiliser, it was investigated whether root iron plaque, formed under aerobic conditions, affects As uptake, metabolism and distribution in Lupinus albus plants. White lupin plants were cultivated in a continuously aerated hydroponic culture containing Fe/EDDHA or FeSO4 and exposed to arsenate (5 or 20 μM). Only FeSO4 induced surficial iron plaque in roots. LA-ICP-MS analysis accomplished on root sections corroborated the association of As to this surficial Fe. Additionally, As(V) was the predominant species in FeSO4-treated roots, suggesting less efficient As uptake in the presence of iron plaque. Fe/EDDHA-exposed roots neither showed such surficial FeAs co-localisation nor As(V) accumulation; in contrast As(III) was the predominant species in root tissue. Furthermore, FeSO4-treated plants showed reduced shoot-to-root As ratios, which were >10-fold lower compared to Fe/EDDHA treatment. Our results highlight the role of an iron plaque formed in roots of white lupin under aerobic conditions on As immobilisation. These findings, to our knowledge, have not been addressed before for this plant and have potential implications on soil remediation (phytostabilisation) and food security (minimising As in crops).
Show more [+] Less [-]Source apportionment of trace metals in river sediments: A comparison of three methods
2016
Chen, Haiyang | Teng, Yanguo | Li, Jiao | Wu, Jin | Wang, Jinsheng
Increasing trace metal pollution in river sediment poses a significant threat to watershed ecosystem health. Identifying potential sources of sediment metals and apportioning their contributions are of key importance for proposing prevention and control strategies of river pollution. In this study, three advanced multivariate receptor models, factor analysis with nonnegative constraints (FA-NNC), positive matrix factorization (PMF), and multivariate curve resolution weighted-alternating least-squares (MCR-WALS), were comparatively employed for source apportionment of trace metals in river sediments and applied to the Le'an River, a main tributary of Poyang Lake which is the largest freshwater lake in China. The pollution assessment with contamination factor and geoaccumulation index suggested that the river sediments in Le'an River were contaminated severely by trace metals due to human activities. With the three apportionment tools, similar source profiles of trace metals in sediments were extracted. Especially, the MCR-WALS and PMF models produced essentially the same results. Comparatively speaking, the weighted schemes might give better solutions than the unweighted FA-NNC because the uncertainty information of environmental data was considered by PMF and MCR-WALS. Anthropogenic sources were apportioned as the most important pollution sources influencing the sediment metals in Le'an River with contributions of about 90%. Among them, copper tailings occupied the largest contribution (38.4–42.2%), followed by mining wastewater (29.0–33.5%), and agricultural activities (18.2–18.7%). To protect the ecosystem of Le'an River and Poyang Lake, special attention should be paid to the discharges of mining wastewater and the leachates of copper tailing ponds in that region.
Show more [+] Less [-]Comparison of pollution indices for the assessment of heavy metal in Brisbane River sediment
2016
Duodu, Godfred Odame | Goonetilleke, Ashantha | Ayoko, G. A. (Godwin A.)
Estuarine environment is complex and receives different contaminants from numerous sources that are persistent, bioaccumulative and toxic. The distribution, source, contamination and ecological risk status of heavy metals in sediment of Brisbane River, Australia were investigated. Sediment samples were analysed for major and minor elements using LA-ICP-MS. Principal component analysis and cluster analysis identified three main sources of metals in the samples: marine sand intrusion, mixed lithogenic and sand intrusion as well as transport related. To overcome inherent deficiencies in using a single index, a range of sediment quality indices, including contamination factor, enrichment factor, index of geo-accumulation, modified degree of contamination, pollution index and modified pollution index were utilised to ascertain the sediment quality. Generally, the sediment is deemed to be “slightly” to “heavily” polluted. A further comparison with the Australian Sediment Quality Guidelines indicated that Ag, Cr, Cu, Ni, Pb and Zn had the potential to rarely cause biological effects while Hg could frequently cause biological effects. Application of potential ecological risk index (RI) revealed that the sediment poses moderate to considerable ecological risk. However, RI could not account for the complex sediment behaviour because it uses a simple contamination factor. Consequently, a modified ecological risk index (MRI) employing enrichment factor is proposed. This provides a more reliable understanding of whole sediment behaviour and classified the ecological risk of the sediment as moderate to very high. The results demonstrate the need for further investigation into heavy metal speciation and bioavailability in the sediment to ascertain the degree of toxicity.
Show more [+] Less [-]Acoustic stress responses in juvenile sea bass Dicentrarchus labrax induced by offshore pile driving
2016
Underwater sound generated by pile driving during construction of offshore wind farms is a major concern in many countries. This paper reports on the acoustic stress responses in young European sea bass Dicentrarchus labrax (68 and 115 days old), based on four in situ experiments as close as 45 m from a pile driving activity. As a primary stress response, whole-body cortisol seemed to be too sensitive to ‘handling’ bias. On the other hand, measured secondary stress responses to pile driving showed significant reductions in oxygen consumption rate and low whole-body lactate concentrations. Furthermore, repeated exposure to impulsive sound significantly affected both primary and secondary stress responses. Under laboratory conditions, no tertiary stress responses (no changes in specific growth rate or Fulton's condition factor) were noted in young sea bass 30 days after the treatment. Still, the demonstrated acute stress responses and potentially repeated exposure to impulsive sound in the field will inevitably lead to less fit fish in the wild.
Show more [+] Less [-]Paper-disc method: An efficient assay for evaluating metal toxicity to soil algae
2016
The probabilistic ecological risk assessment using terrestrial toxicity data has been mainly based on microfauna or mesofauna. Soil algae, which are food source for microfauna and mesofauna, may be alternatively used for assessing soil toxicity. However, there are no internationally recommended guidelines for soil algal bioassays, and the collection of algae from the test soils has some limitations. In this study, we suggested the paper-disc method as an easy-to-use alternative. This method has been widely used for testing the antibacterial toxicity of various chemicals in agar media by measuring the diameter of the inhibition zone around the disc. We adapted the paper-disc method for screening the toxicity of copper (Cu) and nickel (Ni) to the soil alga Chlorococcum infusionum using various evaluation endpoints, such as growth zone, chlorophyll fluorescence, and photosynthetic activity. Chlorophyll fluorescence and photosynthetic activity decreased with the increasing concentrations of Cu+2 or Ni+2 contaminated soils. Algal growth zone was analyzed visually and showed similar results to those of chlorophyll fluorescence. The direct ethanol extraction method and indirect culture medium extraction method were similarly effective; however, the former was easier to perform, while the latter might facilitate the analysis of additional endpoints in future studies. Overall, the results suggested that the paper-disc method was not only a user-friendly assay for screening soil toxicity, but also effective due to its association with indirect soil quality indicators.
Show more [+] Less [-]Phthalate monoesters as markers of phthalate contamination in wild marine organisms
2016
The level of phthalate esters (PAEs) alone is not considered to be a sufficient indicator of PAE pollution due to the quick metabolism of PAEs in the biota. The primary metabolites of PAEs, monoalkyl phthalate esters (MPEs), may also be an important indicator. However, PAE metabolism has scarcely been documented in wild marine organisms. We analysed five PAEs [dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), di(2-ethylhexyl) phthalate (DEHP), and di-n-octyl phthalate (DNOP)] and their corresponding MPEs [mono-methyl phthalate (MMP), mono-ethyl phthalate (MEP), mono-n-butyl phthalate (MBP), mono-2-ethylhexyl phthalate (MEHP), and mono-n-octyl phthalate (MNOP)] in 95 wild aquatic marine samples (including fish, prawns and molluscs) collected from the Yangtze River Delta area of the East China Sea. The species-dependent distribution of these compounds was associated with the food habits, living patterns and trophic levels of the biota. Slightly higher levels of hydrophobic PAEs (DBP and DEHP, logKOW 4.27 and 7.33, respectively) were observed in fish species consuming benthic organisms or in demersal fish species, suggesting the importance of benthic organisms and sediment. Trophic dilution of both PAEs and MPEs implies further metabolic transformation at higher trophic levels. MPE tissue distributions in fish demonstrate that the highest concentrations were always observed in bile. Metabolism via the kidney and gill is a probable main way for the relatively less hydrophobic MPEs (logKOW = <4.73, from MMP to MEHP), whereas metabolism via the liver is likely the main way for the most hydrophobic MNOP (logKOW 5.22). Generally, higher detection frequencies of MPEs were observed than those of parent PAEs. Significant liner correlations were observed between the levels of short-branched (carbon atom per chain = <4) MPEs and the sum of PAEs and MPEs (n = 95, p < 0.01), demonstrating that short-branched MPEs can be used as biomarkers of exposure to quantitatively reflect parent PAE contamination in wild marine organisms.
Show more [+] Less [-]Extensive study of potential harmful elements (Ag, As, Hg, Sb, and Se) in surface sediments of the Bohai Sea, China: Sources and environmental risks
2016
Li, Li | Cui, Jingjing | Liu, Jihua | Gao, Jingjing | Bai, Yazhi | Shi, Xuefa
This study analyzed 405 surface sediment samples, obtained from across the Bohai Sea, for concentrations of five potentially harmful elements (Ag, As, Hg, Sb, and Se) and several ancillary parameters (Al, Fe, Mn, total organic carbon (TOC), and grain size). Statistically, the spatial distributions of these elements were correlated positively with Al, Fe, TOC, and grain size, indicating natural sources for these elements or common accumulation mechanisms. The assessment of potential environmental risk with empirical sediment quality guidelines showed that a significant proportion of the samples had As and Sb concentrations that exceeded the effects range low (ERL) or T20 values in the Bohai Sea, indicating the potential for adverse biological effects. However, the assessment results differed when using evaluation methods that considered background values. Based on the geoaccumulation index (Igeo), Hg and Ag were found to have the highest percentages (35% and 60%, respectively) in samples that were moderately contaminated. The estimated contamination degree (Cd) suggested higher contamination levels for the entire area, with 69% of the samples being moderately contaminated. Generally, except for some local hotspots, such as Jinzhou Bay, the contamination levels of these elements in the Bohai Sea were established as slight to moderate. Samples from the Jinzhou Bay area had concentrations that were 10–100 times higher than in the rest of the Bohai Sea, indicating severe contamination.
Show more [+] Less [-]Evidence for differential effects of reduced and oxidised nitrogen deposition on vegetation independent of nitrogen load
2016
van den Berg, Leon J.L. | Jones, Laurence | Sheppard, Lucy J. | Smart, S. M. (Simon M.) | Bobbink, Roland | Dise, Nancy B. | Ashmore, M. R. (Mike R.)
Nitrogen (N) deposition impacts natural and semi-natural ecosystems globally. The responses of vegetation to N deposition may, however, differ strongly between habitats and may be mediated by the form of N. Although much attention has been focused on the impact of total N deposition, the effects of reduced and oxidised N, independent of the total N deposition, have received less attention. In this paper, we present new analyses of national monitoring data in the UK to provide an extensive evaluation of whether there are differences in the effects of reduced and oxidised N deposition across eight habitat types (acid, calcareous and mesotrophic grasslands, upland and lowland heaths, bogs and mires, base-rich mires, woodlands). We analysed data from 6860 plots in the British Countryside Survey 2007 for effects of total N deposition and N form on species richness, Ellenberg N values and grass:forb ratio. Our results provide clear evidence that N deposition affects species richness in all habitats except base-rich mires, after factoring out correlated explanatory variables (climate and sulphur deposition). In addition, the form of N in deposition appears important for the biodiversity of grasslands and woodlands but not mires and heaths. Ellenberg N increased more in relation to NHx deposition than NOy deposition in all but one habitat type. Relationships between species richness and N form were habitat-specific: acid and mesotrophic grasslands appear more sensitive to NHx deposition while calcareous grasslands and woodlands appeared more responsive to NOy deposition. These relationships are likely driven by the preferences of the component plant species for oxidised or reduced forms of N, rather than by soil acidification.
Show more [+] Less [-]Acute phenanthrene toxicity to juvenile diploid and triploid African catfish (Clarias gariepinus): Molecular, biochemical, and histopathological alterations
2016
Karamī, ʻAlī | Romano, Nicholas | Hamzah, Hazilawati | Simpson, Stuart L. | Yap, Chee Kong
Information on the biological responses of polyploid animals towards environmental contaminants is scarce. This study aimed to compare reproductive axis-related gene expressions in the brain, plasma biochemical responses, and the liver and gill histopathological alterations in diploid and triploid full-sibling juvenile African catfish (Clarias gariepinus). Fish were exposed for 96 h to one of the two waterborne phenanthrene (Phe) concentrations [mean measured (SD): 6.2 (2.4) and 76 (4.2) μg/L]. In triploids, exposure to 76 μg/L Phe increased mRNA level of fushi tarazu-factor 1 (ftz-f1). Expression of tryptophan hydroxylase2 (tph2) was also elevated in both ploidies following the exposure to 76 μg/L Phe compared to the solvent control. In triploids, 76 μg/L Phe increased plasma alkaline phosphatase (ALP) and lactate dehydrogenase (LDH) levels compared to the other Phe-exposed group. It also elevated lactate and glucose contents relative to the other groups. In diploids, however, biochemical biomarkers did not change. Phenanthrene exposures elevated glycogen contents and the prevalence of histopathological lesions in the liver and gills of both ploidies. This study showed substantial differences between diploids and triploids on biochemical and molecular biomarker responses, but similar histopathological alterations following acute Phe exposures.
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