Mine water geochemistry and metal flux in a major historic Pb-Zn-F orefield, the Yorkshire Pennines, UK

Recent studies have shown up to 6 % of rivers in England and Wales to be impacted by discharges from abandoned metal mines. Despite the large extent of impacts, there are still many areas where mine water impact assessments are limited by data availability. This study provides an overview of water quality, trace element composition and flux arising from one such area; the Yorkshire Pennine Orefield in the UK. Mine drainage waters across the orefield are characterised by Ca–HCO₃–SO₄-type waters, with moderate mineralization (specific electrical conductance: 160–525 μS cm^?1) and enrichment of dissolved Zn (≤2003 μg?L^?1), Ba (≤971 μg?L^?1), Pb (≤183 μg?L^?1) and Cd (≤12 μg?L^?1). The major ion composition of the waters reflects the Carboniferous gritstone and limestone-dominated country rock, the latter of which is heavily karstified in parts of the orefield, while sulphate and trace element enrichment is a product of the oxidation of galena, sphalerite and barite mineralization. Contaminant flux measurements at discharge sites highlight the disproportionate importance of large drainage levels across the region, which generally discharge into first-order headwater streams. Synoptic metal loading surveys undertaken in the Hebden Beck sub-catchment of the river Wharfe highlight the importance of major drainage levels to instream baseflow contamination, with diffuse sources from identifiable expanses of waste rock becoming increasingly prominent as river flows increase.     

Assessing the enrichment of heavy metals in surface soil and plant (Digitaria eriantha) around coal-fired power plants in South Africa

Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr, and Zn) were determined in soil and Digitaria eriantha plants within the vicinity of three coal power plants (Matla, Lethabo, and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05?±?0.02 to 1836?±?70 μg g^?1, 0.08?±?0.05 to 1744?±?29 μg g^?1, and 0.07?±?0.04 to 1735?±?91 μg g^?1 in Matla, Lethabo, and Rooiwal, respectively. Total metal concentration in the plant (D. eriantha) ranged from 0.005?±?0.003 to 535?±?43 μg g^?1 in Matla, 0.002?±?0.001 to 400?±?269 μg g^?1 in Lethabo, and 0.002?±?0.001 to 4277?±?201 μg g^?1 in Rooiwal. Accumulation factors (A) of less than 1 (i.e., 0.003 to 0.37) at all power plants indicate a low transfer of metal from soil to plant (excluder). Enrichment factor values obtained (2.4–5.0) indicate that the soils are moderately enriched with the exception of Pb that had significant enrichment of 20. Geo-accumulation index (I-geo) values of metals indicate that the soils are moderately polluted (0.005–0.65), except for Pb that showed moderate to strong pollution (1.74–2.53).     

Characterization of carbonaceous aerosols over Delhi in Ganga basin: seasonal variability and possible sources

The mass concentration of carbonaceous species, organic carbon (OC), and elemental carbon (EC) using a semicontinuous thermo-optical EC-OC analyzer, and black carbon (BC) using an Aethalometer were measured simultaneously at an urban mega city Delhi in Ganga basin from January 2011 to May 2012. The concentrations of OC, EC, and BC exhibit seasonal variability, and their concentrations were ～2 times higher during winter (OC 38.1?±?17.9 μg m^?3, EC 15.8?±?7.3 μg m^?3, and BC 10.1?±?5.3 μg m^?3) compared to those in summer (OC 14.1?±?4.3 μg m^?3, EC 7.5?±?1.5 μg m^?3, and BC 4.9?±?1.5 μg m^?3). A significant correlation between OC and EC (R?=?0.95, n?=?232) indicate their common emission sources with relatively lower OC/EC ratio (range 1.0–3.6, mean 2.2?±?0.5) suggests fossil fuel emission as a major source of carbonaceous aerosols over the station. On average, mass concentration of EC was found to be ～38 % higher than BC during the study period. The measured absorption coefficient (b_abs) was significantly correlated with EC, suggesting EC as a major absorbing species in ambient aerosols at Delhi. Furthermore, the estimated mass absorption efficiency (σ_abs) values are similar during winter (5.0?±?1.5 m² g^?1) and summer (4.8?±?2.8 m² g^?1). Significantly high aerosol loading of carbonaceous species emphasize an urgent need to focus on air quality management and proper impact assessment on health perspective in these regions.     

Use of sedimentary metals to predict metal concentrations in black mussel (Mytilus galloprovincialis) tissue and risk to human health (Sydney estuary, Australia)

Filter-feeding bivalves have been used extensively as an indicator of ecosystem condition and in management of estuarine environments. The current study aimed to determine whether sedimentary metals could predict metal concentrations in tissue of filter-feeding mussels (Mytilus galloprovincialis) and to identify areas of the estuary where mussel consumption posed a human health risk. Mussel tissue Cu and Zn concentrations (wet weight) were below guideline values for human consumption in all parts of the waterway, whereas Pb tissue concentrations exceed these guidelines (2.0 μg?g^?1 wet weight) in the upper reaches of some embayments of the estuary. Concentrations of Cu and Pb in the fine fraction (<62.5 μm) of bottom sediment reasonably predicted concentrations (dry weight) of these metals in mussel tissue (r ²?=?0.460 and p?=?0.001 and r ²?=?0.669 and p?<?0.0001, respectively) as these materials are resuspendable and available to filter-feeding estuarine animals, whereas total sediment and mussel tissue were poorly related. Lead concentrations (>350 μg?g^?1) in fine sediments indicated areas of this estuary where human health was at risk due to high tissue concentrations of this metal. These results give encouragement for the use of the metal concentration in fine sediments as an indicator of estuarine condition and risk to human health in this waterway. Mussels were distributed in all parts of the estuary, even in areas where metal concentrations exceeded sediment quality guidelines.     

Establishment of reference conditions for nutrients in an intensive agricultural watershed,Eastern China

Nutrient enrichment from nonpoint source pollution is one of the main causes of poor water quality and biotic impairment in many streams and rivers worldwide. The establishment of reference nutrient conditions in a river system is an essential but difficult task for water quality control. In the present study, the reference concentrations of total nitrogen (TN) and total phosphorus (TP) were estimated in an intensive agricultural watershed, the Cao-E River system of Eastern China. Based on a 3-year water quality monitoring data in the river system, three approaches were adopted to establish the reference concentrations of TN and TP, those are the 75th percentile of frequency distribution of nutrient concentrations in reference streams, the 25th percentile of frequency distribution of nutrient concentration in general streams (including reference and non-reference streams) and regression modeling. Results showed that the nutrient reference concentrations were slightly different from different approaches. By the three approaches, the average reference concentrations for TN and TP in the study system were 1.73?±?0.13 mg l^?1 and 55.23?±?4.77 μg l^?1 with CV of 7.39 % and 8.63 %, respectively. Accordingly, the reference concentrations for TN and TP were recommended to be 1.70 mg l^?1 and 55 μg l^?1, respectively. In the mountainous and intensive agricultural watershed, the major anthropogenic impacts to river water quality were the urban area percentage cover, cropland area with slopes 0–8°, and livestock and poultry waste loads density. These variables could account for 89.7 % and 80.3 % of the total variations for TN and TP concentration, respectively.     

Distributions, sources, and ecological risks of hexachlorocyclohexanes in the sediments from Haihe Plain, Northern China

The levels of hexachlorocyclohexanes (HCHs) in the sediments from Haihe Plain, China, were measured by a gas chromatograph with a ⁶³Ni microelectron capture detector. The spatial distributions, possible sources, and potential ecological risks of these compounds were analyzed. The residual level of total HCHs was 33.84?±?173.37 ng?g^?1 dry weight (d.w.) with ranges of 0.13?～?1,107.41 ng?g^?1 d.w. Much higher ΣHCH contents were found in the lower reaches of some rivers and in the mouth of the main stream receiving tributaries. The predominance of β-HCH (36 %) in the sediments was similar to that in the soils from Haihe Plain. The high percentages of γ-HCH (23–41 %) could be detected at 25 % of the sampling sites in the seven river systems. There were statistically significant positive relationships between the contents of HCHs and total organic carbon. Lindane was identified as the primary source of HCHs in the sediments, and it seemed that recent illegal lindane inputs still existed in some areas in Haihe Plain, as indicated by the α-/γ-HCH and β-/(α?+?γ)-HCH ratios. Severe potential ecological risks of γ-HCH to benthic organisms at some sampling sites were found based on the consensus-based sediment quality guidelines.     

Influence of short-time imidacloprid and acetamiprid application on soil microbial metabolic activity and enzymatic activity

The influence of two neonicotinoids, i.e., imidacloprid (IMI) and acetamiprid (ACE), on soil microbial activities was investigated in a short period of time using a combination of the microcalorimetric approach and enzyme tests. Thermodynamic parameters such as Q _T (J g^?1 soil), ?H _met (kJ mol^?1), J _Q/S (J g^?1 h^?1), k (h^?1), and soil enzymatic activities, dehydrogenase, phosphomonoesterase, arginine deaminase, and urease, were used to evaluate whole metabolic activity changes and acute toxicity following IMI and ACE treatment. Various profiles of thermogenic curves reflect different soil microbial activities. The microbial growth rate constant k, total heat evolution Q _T (expect for IMI), and inhibitory ratio I show linear relationship with the doses of IMI and ACE. Q _T for IMI increases at 0.0–20 μg g^?1 and then decreases at 20–80 μg g^?1, possibly attributing to the presence of tolerant microorganisms. The 50 % inhibitory ratios (IC₅₀) of IMI and ACE are 95.7 and 77.2 μg g^?1, respectively. ACE displays slightly higher toxicity than IMI. Plots of k and Q _T against microbial biomass-C indicate that the k and Q _T are growth yield-dependent. IMI and ACE show 29.6; 40.4 and 23.0; and 23.3, 21.7, and 30.5 % inhibition of dehydrogenase, phosphomonoesterase, and urease activity, respectively. By contrast, the arginine deaminase activity is enhanced by 15.2 and 13.2 % with IMI and ACE, respectively. The parametric indices selected give a quantitative dose-response relationship of both insecticides and indicate that ACE is more toxic than IMI due to their difference in molecular structures.     

Toxicity of atrazine and its bioaccumulation and biodegradation in a green microalga,Chlamydomonas mexicana

This study evaluated the toxicity of herbicide atrazine, along with its bioaccumulation and biodegradation in the green microalga Chlamydomonas mexicana. At low concentration (10 μg L^?1), atrazine had no profound effect on the microalga, while higher concentrations (25, 50, and 100 μg L^?1) imposed toxicity, leading to inhibition of cell growth and chlorophyll a accumulation by 22 %, 33 %, and 36 %, and 13 %, 24 %, and 27 %, respectively. Atrazine 96-h EC50 for C. mexicana was estimated to be 33 μg L^?1. Microalga showed a capability to accumulate atrazine in the cell and to biodegrade the cell-accumulated atrazine resulting in 14–36 % atrazine degradation at 10–100 μg L^?1. Increasing atrazine concentration decreased the total fatty acids (from 102 to 75 mg g^?1) and increased the unsaturated fatty acid content in the microalga. Carbohydrate content increased gradually with the increase in atrazine concentration up to 15 %. This study shows that C. mexicana has the capability to degrade atrazine and can be employed for the remediation of atrazine-contaminated streams.     

Distribution and ecological risk of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in surface sediments from the Bizerte lagoon,Tunisia

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were determined in 18 surface sediment samples collected from Bizerte lagoon, Tunisia. The total concentrations of ten PCBs (∑PCBs) and of four OCPs (∑OCPs) in the sediments from this area ranged from 0.8 to 14.6 ng g^?1 dw (average value, 3.9 ng g^?1 dw) and from 1.1 to 14.0 ng g^?1 dw (average value, 3.3 ng g^?1 dw), respectively. Among the OCPs, the range of concentrations of dichlorodiphenyltrichloroethane and its metabolites (DDTs) and hexachlorobenzene (HCB) were 0.3–11.5 ng g^?1 dw (1.9 ng g^?1 dw) and 0.6–2.5 ng g^?1 dw (1.4 ng g^?1 dw), respectively. Compositional analyses of the POPs indicated that PCB 153, 138 and 180 were the predominant congeners accounting for 60 % of the total PCBs. In addition, p,p′-DDT was found to be the dominant DDTs, demonstrating recent inputs in the environment. Compared with some other regions of the world, the Bizerte lagoon exhibited low levels of PCBs and moderate levels of HCB and DDTs. The high ratios ΣPCBs/ΣDDTs indicated predominant industrial versus agricultural activities in this area. According to the established guidelines for sediment quality, the risk of adverse biological effects from such levels of OCPs and PCBs, as recorded at most of the study sites, was insignificant. However, the higher concentrations in stations S1 and S3 could cause biological damage.     

Nopalea cochenillifera, a potential chromium (VI) hyperaccumulator plant

Hexavalant chromium [Cr(VI)] tolerance and accumulation in in vitro grown Nopalea cochenillifera Salm. Dyck. plants was investigated. A micropropagation protocol was establish for a rapid multiplication of N. cochenillifera and [Cr(VI)] tolerance and accumulation was studied in in vitro grown cultures. Cr concentration was estimated by atomic absorption spectroscopy in roots and shoots to confirm plant’s hyperaccumulation capacity. Plants showed tolerance up to 100 μM K₂Cr₂O₇ without any significant changes in root growth after 16 days treatment; whereas, chlorophyll content in plants treated with 1 and 10 μM K₂Cr₂O₇ were not so different than the control plant. The levels of lipid peroxidation and protein oxidation increased significantly (p?<?0.01) with increasing concentration of chromium. Exposures of N. cochenillifera to lower concentrations of K₂Cr₂O₇ (≤10 μM) induced catalase (CAT) and superoxide dismutase (SOD) significantly (p?<?0.001) but higher concentrations of K₂Cr₂O₇ (>100 μM) inhibited the activities of CAT and SOD. Roots accumulated a maximum of 25,263.396?±?1,722.672 mg?Cr?Kg^?1 dry weight (DW); while the highest concentration of Cr in N. cochenillifera shoots was 705.714?±?32.324 mg?Cr?Kg^?1?DW. N. cochenillifera could be a prospective hyperaccumulator plant of Cr(VI) and a promising candidate for phytoremediation purposes.     

Metal content in caviar of wild Persian sturgeon from the southern Caspian Sea

Caviar (fish roe of sturgeon) may contain high levels of contaminants. An inductively coupled plasma-optical emission spectrometer and a direct mercury analyzer were used to assess the contents of four heavy metals (Hg, Se, Sn, and Ba) in caviar of wild Persian sturgeon sea foods. The levels of Hg ranged from 1.39 to 1.50 μg?g^?1, Se from 0.90 to 1.10 μg?g^?1, Sn from 0.23 to 0.33, and Ba from 0.71 to 1.17 μg?g^?1. Evaluation of these levels showed that except for Hg, the average concentrations of other metals are significantly lower than adverse level for the human consumption when compared with Food and Agricultural Organization of the United Nations and World Health Organization permissible limits. Therefore, their contribution to the total body burden of these heavy metals can be considered as negligibly small given that caviar is a luxury product.     

Effects of nitrogen application rate and a nitrification inhibitor dicyandiamide on methanotroph abundance and methane uptake in a grazed pasture soil

Methane-oxidizing bacteria (methanotrophs) in the soil are a unique group of methylotrophic bacteria that utilize methane (CH₄) as their sole source of carbon and energy which limit the flux of methane to the atmosphere from soils and consume atmospheric methane. A field experiment was conducted to determine the effect of nitrogen application rates and the nitrification inhibitor dicyandiamide (DCD) on the abundance of methanotrophs and on methane flux in a grazed pasture soil. Nitrogen (N) was applied at four different rates, with urea applied at 50 and 100 kg N ha^?1 and animal urine at 300 and 600 kg N ha^?1. DCD was applied at 10 kg ha^?1. The results showed that both the DNA and selected mRNA copy numbers of the methanotroph pmoA gene were not affected by the application of urea, urine or DCD. The methanotroph DNA and mRNA pmoA gene copy numbers were low in this soil, below 7.13?×?10³ g^?1 soil and 3.75?×?10³ μg^?1 RNA, respectively. Daily CH₄ flux varied slightly among different treatments during the experimental period, ranging from ?12.89 g CH₄ ha^?1 day^?1 to ?0.83 g CH₄ ha^?1 day^?1, but no significant treatment effect was found. This study suggests that the application of urea fertilizer, animal urine returns and the use of the nitrification inhibitor DCD do not significantly affect soil methanotroph abundance or daily CH₄ fluxes in grazed grassland soils.     

Removal mechanisms and kinetics of trace tetracycline by two types of activated sludge treating freshwater sewage and saline sewage

Understanding the removal mechanisms and kinetics of trace tetracycline by activated sludge is critical to both evaluation of tetracycline elimination in sewage treatment plants and risk assessment/management of tetracycline released to soil environment due to the application of biosolids as fertilizer. Adsorption is found to be the primary removal mechanism while biodegradation, volatilization, and hydrolysis can be ignored in this study. Adsorption kinetics was well described by pseudo-second-order model. Faster adsorption rate (k ₂?=?2.04?×?10^?2?g?min^?1?μg^?1) and greater adsorption capacity (q _e?=?38.8 μg?g^?1) were found in activated sludge treating freshwater sewage. Different adsorption rate and adsorption capacity resulted from chemical properties of sewage matrix rather than activated sludge surface characteristics. The decrease of tetracycline adsorption in saline sewage was mainly due to Mg²⁺ which significantly reduced adsorption distribution coefficient (K _d) from 12,990?±?260 to 4,690?±?180 L?kg^?1. Species-specific adsorption distribution coefficients followed the order of $ K_{\mathrm{d}}^{{ + 00}} \gg K_{\mathrm{d}}^{{ + - 0}} > K_{\mathrm{d}}^{{ + - - }} $ . Contribution of zwitterionic tetracycline to the overall adsorption was >90 % in the actual pH range in aeration tank. Adsorption of tetracycline in a wide range of temperature (10 to 35 °C) followed the Freundlich adsorption isotherm well.     

Organochlorine pesticides and polychlorinated biphenyls in soils surrounding the Tanggu Chemical Industrial District of Tianjin, China

The spatial distribution of persistent organic pollutants (POPs) was examined in soils surrounding the Tanggu Chemical Industrial District in Tianjin, China. The concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzenes (HCBs), and polychlorinated biphenyls (PCBs) were determined in 70 surface soils using accelerated solvent extraction and gas chromatography with electron capture detection. The results showed that the ranges of ∑HCH, ∑DDT, ΣHCB, and ∑PCB concentrations in soils were 2.1–12,549 μg?kg^?1 (average, 965 μg?kg^?1), n.d.–2,033 μg?kg^?1 (average, 88.4 μg?kg^?1), n.d.–1,924 μg?kg^?1 (average, 349 μg?kg^?1), and n.d.–373 μg?kg^?1 (average, 46.2 μg?kg^?1), respectively. Of these, HCHs were the dominant POPs, accounting for 75 % of the total organochlorine pesticide (OCP) residues. Overall, the spatial distribution of OCP concentrations showed a decreasing trend from the center of the Tanggu District to the surrounding areas. Two major pollution sources were Tianjin Dagu Chemical Co., Ltd. in the district center and the Tianjin Chemical Plant in Hangu District. In contrast, PCB concentrations were relatively high in the Haihe estuary to the east and low to the west of the study area. Component analysis of OCPs in these soils showed that they mainly came from industrial point sources. Compared with soils in other regions, soil DDT pollution was at a medium level in the Tanggu Chemical Industrial District, but associated HCH, HCB, and PCB pollution was relatively heavy. By multivariate statistical analyses, Tianjin Dagu Chemical Co., Ltd. was recognized as the main source of POPs, and soil properties were clarified to play an important role on the distribution and composition of POPs, especially the organic carbon content.     

Residues levels of organochlorine pesticide in cow's milk from industrial farms in Hidalgo,Mexico

A survey was carried out from 2008 to 2010 to determine the concentrations of 16 organochlorine pesticide residues (OPRs) from Tizayuca, Hidalgo, Mexico. Organochlorine residue determinations were made from milk fat, using chromatographic cleanup and analysis by gas chromatography with an electron capture detector. The OPR concentrations found were from below the detection limit (DL) to 0.91 ng g^?1 in 2008, DL to 0.38 ng g^?1 in 2009 and DL to 0.59 ng g^?1 in 2010. In general concentrations of organochlorine pesticides were higher in the wet season (3.37 ng g^?1 and 4.79 ng g^?1) than the dry season (1.92 ng g^?1 and 2.71 ng g^?1) for 2009 and 2010, due to control of pests in the pasture and sheds. According to Codex Alimentarius regulations, individual pesticides did not exceed the permissible limits, which for example were 10 μg kg^?1 for alpha hexachlorocyclohexane (HCH) and endosulfan I, 20 μg kg^?1 for p,p’-DDT, and 6 μg kg^?1 for dieldrin, endrin and heptachlor. A reduction of organochlorine pesticide concentrations in cow's milk was noted, indicating that the Mexican government has achieved reduction or elimination of some organochlorine pesticides in response to global agreements on persistent organic pollutants.     

Sources of submicron aerosol during fog-dominated wintertime at Kanpur

The main objective of this atmospheric study was to determine the major sources of PM₁ (particles having aerodynamic diameter <1.0 μm) within and near the city of Kanpur, in the Indo-Gangetic Plain. Day and night, 10 h long each, filter-based aerosol samples were collected for 4 months (November 2009 to February 2010) throughout the winter season. These samples were subjected to gravimetric and quantitative chemical analyses for determining water-soluble ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) using an ion chromatograph and trace elements using an inductively coupled plasma–optical emission spectrometer. The mean PM₁ mass concentrations were recorded as 114?±?71 μg/m³ (day) and 143?±?86 μg/m³ (night), respectively. A significantly higher diurnal contribution of ions (NH₄ ⁺, F^?, Cl^?, NO₃ ^?, and SO₄ ^2?) in PM₁ mass was observed during the fog-affected days and nights throughout the winter season, for which the average values were recorded as 38.09?±?13.39 % (day) and 34.98?±?12.59 % (night), respectively, of the total PM₁ mass. This chemical dataset was then used in a source-receptor model, UNMIX, and the model results are described in detail. UNMIX provided a maximum number of five source factors, including crustal material, composite vehicle, secondary aerosol, coal combustion, and iron/steel production and metallurgical industries, as the dominant air pollution sources for this study.     

The capability of estuarine sediments to remove nitrogen: implications for drinking water resource in Yangtze Estuary

Water in the Yangtze Estuary is fresh most of the year because of the large discharge of Yangtze River. The Qingcaosha Reservoir built on the Changxing Island in the Yangtze Estuary is an estuarine reservoir for drinking water. Denitrification rate in the top 10 cm sediment of the intertidal marshes and bare mudflat of Yangtze Estuarine islands was measured by the acetylene inhibition method. Annual denitrification rate in the top 10 cm of sediment was 23.1 μmol m^?2 h^?1 in marshes (ranged from 7.5 to 42.1 μmol m^?2 h^?1) and 15.1 μmol m^?2 h^?1 at the mudflat (ranged from 6.6 to 26.5 μmol m^?2 h^?1). Annual average denitrification rate is higher at mashes than at mudflat, but without a significant difference (p?=?0.084, paired t test.). Taking into account the vegetation and water area of the reservoir, a total 1.42?×?10⁸ g N could be converted into nitrogen gas (N₂) annually by the sediment, which is 97.7 % of the dissolved inorganic nitrogen input through precipitation. Denitrification in reservoir sediment can control the bioavailable nitrogen level of the water body. At the Yangtze estuary, denitrification primarily took place in the top 4 cm of sediment, and there was no significant spatial or temporal variation of denitrification during the year at the marshes and mudflat, which led to no single factor determining the denitrification process but the combined effects of the environmental factors, hydrologic condition, and wetland vegetation.     

Single and combined effects of aluminum (Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) and zinc (ZnO) oxide nanoparticles in a freshwater fish, <Emphasis Type="Italic">Carassius auratus</Emphasis>

The increasing use of nanoparticles (NPs) worldwide has raised some concerns about their impact on the environment. The aim of the study was to assess the toxicity of metal oxide nanoparticles, singly or combined, in a freshwater fish (Carassius auratus). The fish were exposed for 7, 14, and 21 days to different concentrations of NPs (10 μg Al₂O₃.L^?1, 10 μg ZnO.L^?1, 10 μg Al₂O₃.L^?1 plus 10 μg ZnO.L^?1, 100 μg Al₂O₃.L^?1, 100 μg ZnO.L^?1, and 100 μg Al₂O₃.L^?1 plus 100 μg ZnO.L^?1). At the end of each exposure period, antioxidant enzyme activity (catalase, glutathione-S-transferase, and superoxide dismutase), lipid peroxidation, and histopathology were assessed in the gills and livers of C. auratus. The results show an increase in catalase (CAT) and superoxide dismutase (SOD) activity in the gills and livers of fish, especially after 14 days of exposure to single and combined NPs, followed by a reduction at 21 days. An increase in glutathione S-transferase (GST) was observed in gills after 7 days for all tested NP concentrations (single and combined); while in livers, a significant increase was determined after 14 days of exposure to 100 μg.L^?1 of both single ZnO and Al₂O₃ NPs. Lipid peroxidation (LPO) significantly increased in gills after 7 days of exposure to 100 μg.L^?1 Al₂O₃ NPs (single or combined). In livers, LPO increased significantly after 7 days of exposure to all tested concentrations of both single ZnO and Al₂O₃ (except for 10 μg Al₂O₃.L^?1), and after 14 days of exposure to ZnO (10 and 100 μg.L^?1) and Al₂O₃ (100 μg.L^?1)_. The results from histological observations suggest that exposure to metal oxide NPs affected both livers and gills, presenting alterations such as gill hyperplasia and liver degeneration. However, the most pronounced effects were found in gills. In general, this study shows that the tested NPs, single or combined, are capable of causing sub-lethal effects on C. auratus, but when combined, NPs seem to be slightly more toxic than when added alone.     

Sources and historical record of tin and butyl-tin species in a Mediterranean bay (Toulon Bay,France)

Concentrations of inorganic tin (Sn_inorg), tributyltin (TBT) and its degradation products dibutyltin (DBT) and monobutyltin (MBT) were measured in surface sediments and in two cores from the Toulon Bay, hosting the major French military harbour. Anticipating planned dredging, the aim of the present work is to map and evaluate for the first time the recent and historic contamination of these sediments by inorganic and organic Sn species derived from antifouling paints used for various naval domains including military, trade, tourism and leisure. Tin and butyl-Sn concentrations in the bay varied strongly (4 orders of magnitude), depending on the site, showing maximum values near the shipyards. The concentrations of total Sn (1.3–112 μg g^?1), TBT (<0.5–2,700 ng g^?1), DBT (<0.5–1,800 ng g^?1) and MBT (0.5–1,000 ng g^?1) generally decreased towards the open sea, i.e. as a function of both distance from the presumed main source and bottom currents. Progressive degradation state of the butyl-Sn species according to the same spatial scheme and the enrichment factors support the scenario of a strongly polluted bay with exportation of polluted sediment to the open Mediterranean. Low degradation and the historical records of butyl-Sn species in two ²¹⁰Pb-dated sediment cores, representative of the Northern Bay, are consistent with the relatively recent use of TBT by military shipyards and confirm maximum pollution during the 1970s, which will persist in the anoxic sediments for several centuries. The results show that (a) degradation kinetics of butyl-Sn species depend on environmental conditions, (b) the final degradation product Sn_inorgBT is by far the dominant species after 10–12 half-life periods and (c) using recent data to reliably assess former TBT contamination requires the use of a modified butyl-Sn degradation index BDI_mod. Resuspension of extremely contaminated subsurface sediments by the scheduled dredging will probably result in mobilization of important amounts of butyl-Sn species.     

Organic and elemental carbon associated to PM10 and PM2.5 at urban sites of northern Greece

Organic carbon (OC) and elemental carbon (EC) concentrations, associated to PM₁₀ and PM_2.5 particle fractions, were concurrently determined during the warm and the cold months of the year (July–September 2011 and February–April 2012, respectively) at two urban sites in the city of Thessaloniki, northern Greece, an urban-traffic site (UT) and an urban-background site (UB). Concentrations at the UT site (11.3?±?5.0 and 8.44?±?4.08 14 μg m^?3 for OC₁₀ and OC_2.5 vs. 6.56?±?2.14 and 5.29?±?1.54 μg m^?3 for EC₁₀ and EC_2.5) were among the highest values reported for urban sites in European cities. Significantly lower concentrations were found at the UB site for both carbonaceous species, particularly for EC (6.62?±?4.59 and 5.72?±?4.36 μg m^?3 for OC₁₀ and OC_2.5 vs. 0.93?±?0.61 and 0.69?±?0.39 μg m^?3 for EC₁₀ and EC_2.5). Despite that, a negative UT-UB increment was frequently evidenced for OC_2.5 and PM_2.5 in the cold months possibly indicative of emissions from residential wood burning at the urban-background site. At both sites, cconcentrations of OC fractions were significantly higher in the cold months; on the contrary, EC fractions at the UT site were prominent in the warm season suggesting some influence from maritime emissions in the nearby harbor area. Secondary organic carbon, being estimated using the EC tracer method and seasonally minimum OC/EC ratios, was found to be an appreciable component of particle mass particularly in the cold season. The calculated secondary contributions to OC ranged between 35 and 59 % in the PM₁₀ fraction, with relatively higher values in the PM_2.5 fraction (39–61 %). The source origin of carbonaceous species was investigated by means of air parcel back trajectories, satellite fire maps, and concentration roses. A local origin was mainly concluded for OC and EC with limited possibility for long range transport of biomass (agricultural waste) burning aerosol.