Acute and reproductive toxicity of nano-sized metal oxides (ZnO and TiO₂) to earthworms (Eisenia fetida)

An increase in nanomaterial applications will likely lead to an increased probability of environmental exposures, raising concerns regarding the safety of these materials. Recent studies have indicated that manufactured nanomaterials, such as metal oxides, have the potential to be harmful to aquatic and terrestrial organisms. The majority of nano-metal oxide research addressing potential toxicological issues has been focused in aquatic environments with very little terrestrial data. This study characterized the acute and reproductive toxicity of zinc oxide (ZnO) and titanium dioxide (TiO(2)) to earthworms (Eisenia fetida) in a terrestrial system. Following a 14 d exposure, nano-sized ZnO on filter paper was acutely toxic to E. fetida, while nano-sized TiO(2) did not exhibit acute toxicity. In contrast, neither nano-sized ZnO nor TiO(2) exhibited acute toxicity to earthworms in sand. Both nano-sized ZnO and TiO(2), following a 4 week exposure, caused reproductive effects in earthworms in artificial soil. Overall, nano-sized ZnO exhibited greater toxicity than nano-sized TiO(2) in Eisenia fetida.     

Behaviour of different lichen species as biomonitors of air pollution by PAHs in natural ecosystems

Six different species of lichens (Parmelia sulcata Tayl., Evernia prunastri (L.) Ach., Ramalina farinacea, Pseudevernia furfuracea (L.) Zopf., Usnea sp. and Lobaria pulmonaria (Schreb.) Hoffm.) were collected in two mountain valleys in Central Pyrenees: the Aspe and Aragon valleys. Two multivariate techniques have been applied with different purposes, ANOVA and Discriminant Analysis (DA), to evaluate the data. The PAHs spatial distribution was studied in the three more abundant and widespread species in the area: P. sulcata, E. prunastri (L.) Ach. and R. farinacea in terms of total PAHs, PAHs related to the combustion processes and toxicity. Different behaviour of each lichen species to trap PAHs was found, being P. sulcata the best one to monitor the most persistent PAHs of pyrogenic origin and E. prunastri the most appropriate to provide information about pyrogenic and petrogenic PAHs. Traffic was the most relevant influence in PAHs bioaccumulation in lichen species.     

Amplified ribosomal DNA restriction analysis as a routine tool to assess toxicant driven changes in hindgut bacterial populations of Porcellio dilatatus (Crustacea: Isopoda)

Changes in saprophytic organism's gut microbial communities may present a threat to organic matter breakdown which can ultimately lead to soil function impairment. In this study, Amplified Ribosomal DNA Restriction Analysis (ARDRA) was evaluated as a potential simple molecular tool to assess shifts in bacterial community structure in hindgut populations of Porcellio dilatatus exposed to contaminated food. This prospective tool can also be used for a variety of purposes and samples prior to the use of more specific and sophisticated methods.     

Monitoring of pharmaceutically active compounds on the Guadalquivir River basin (Spain): occurrence and risk assessment

Guadalquivir River (South of Spain) is among the major freshwater sources of the European Atlantic basin. Until now scientific efforts have been focused on contamination by heavy metals and some priority pollutants in Guadalquivir River. However, the presence of "emerging contaminants", such as pharmaceutically active compounds, has not yet been studied. In this work the occurrence and risk assessment of sixteen pharmaceutically active compounds, belonging to different therapeutic groups, in Guadalquivir River during its course through Seville city are reported. Wastewater effluents from four wastewater treatment plants discharging into Guadalquivir River and river water samples were analyzed. All studied pharmaceutically active compounds, except sulfamethoxazole, trimethoprim, estrone and clofibric acid, were detected in effluent wastewaters at concentration levels up to 28.9 μg L(-1). Among the pharmaceutically active compounds found in effluent wastewater, seven were present in Guadalquivir River samples at concentration levels up to 0.75 μg L(-1), which indicated an important dilution from effluent discharge. Environmental risk assessment reveals that potential ecotoxicological risk cannot be expected on Guadalquivir River at measured concentration levels. Only, the lipid regulator gemfibrozil showed a medium risk for the environment. The risk for acute toxic effects in the environment with the current use of active pharmaceutical ingredients is unlikely. However, the results do not rule out the potential for chronic environmental effects.     

Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants

A study has been made of the presence and reactivity of the most commonly used surfactants, both anionic (linear alkylbenzene sulfonates, LAS, and alkyl ethoxysulfates, AES) and non-ionic (alcohol polyethoxylates, AEOs, and nonylphenol polyethoxylates, NPEOs), in water and surface sediments from the middle stretch of the Guadalete River in SW Spain (12 stations). Average values were between 0.1 and 3.7 mg kg(-1) in sediment, and between 0.2 and 37 μg L(-1) in water. The sorption of surfactants was dominated by hydrophobic mechanisms, so those homologues having longer alkyl chains (e.g. C(18)AEO) showed higher relative percentages and concentrations in sediments compared with water. Local and sharply higher concentrations of these compounds were observed at three sampling stations (7, 9 and 12), indicating the occurrence of wastewater discharges into the river. By analysing the distributions of different surfactant homologues and their metabolites we were able to distinguish between sewage contamination from sources discharging treated and untreated wastewaters. Upstream (stations 1-2), LAS concentrations were below 30 μg L(-1) and the composition of their degradation intermediates (sulfophenyl carboxylic acids, SPCs) (160 μg L(-1)) was dominated by short-chain homologues (C(6)-C(9)SPCs), indicating that the degradation of this surfactant is at an advanced stage. The highest concentration (487 μg L(-1)) of SPCs was detected near the effluent outlet of a sewage treatment plant (STP) (station 12). Sampling stations (7 and 9) affected by untreated wastewater discharges were the only ones showing the presence of the most reactive and biodegradable SPC isomers and homologues (e.g. C(11)SPC). Here, LAS reached the highest concentration values measured (>2 mg L(-1)), and showed a homologue distribution closer to that of commercial mixtures than LAS found at the other stations.     

Distribution and availability of trace elements in municipal solid waste composts

Trace element contamination is one of the main problems linked to the quality of compost, especially when it is produced from urban wastes, which can lead to high levels of some potentially toxic elements such as Cu, Pb or Zn. In this work, the distribution and bioavailability of five elements (Cu, Zn, Pb, Cr and Ni) were studied in five Spanish composts obtained from different feedstocks (municipal solid waste, garden trimmings, sewage sludge and mixed manure). The five composts showed high total concentrations of these elements, which in some cases limited their commercialization due to legal imperatives. First, a physical fractionation of the composts was performed, and the five elements were determined in each size fraction. Their availability was assessed by several methods of extraction (water, CaCl(2)-DTPA, the PBET extract, the TCLP extract, and sodium pyrophosphate), and their chemical distribution was assessed using the BCR sequential extraction procedure. The results showed that the finer fractions were enriched with the elements studied, and that Cu, Pb and Zn were the most potentially problematic ones, due to both their high total concentrations and availability. The partition into the BCR fractions was different for each element, but the differences between composts were scarce. Pb was evenly distributed among the four fractions defined in the BCR (soluble, oxidizable, reducible and residual); Cu was mainly found in the oxidizable fraction, linked to organic matter, and Zn was mainly associated to the reducible fraction (iron oxides), while Ni and Cr were mainly present almost exclusively in the residual fraction. It was not possible to establish a univocal relation between trace elements availability and their BCR fractionation. Given the differences existing for the availability and distribution of these elements, which not always were related to their total concentrations, we think that legal limits should consider availability, in order to achieve a more realistic assessment of the risks linked to compost use.     

Characterization of PM10-bound polycyclic aromatic hydrocarbons in the ambient air of Spanish urban and rural areas

Urban areas constitute major pollution sources due to anthropogenic activities located in these areas. Among the legislated air pollutants, the particulate matter with an aerodynamic diameter less than or equal to 10 microns (PM10) and polycyclic aromatic hydrocarbons (PAH) are controlled under Directive 2008/50/EC and Directive 2004/107/EC, respectively due to their adverse health effects. A study was carried out at four urban and rural Spanish areas during the warm and cold seasons in 2008-2009 to quantify 19 PAH associated with the atmospheric PM10 by gas chromatography-mass spectrometry-mass spectrometry detection (GC-MS-MS) with the internal standard method. The particle-bound composition of the analysed PAH was 5 and 10 times greater in industrial and urban areas, respectively when compared to those measured in rural areas. The highest PAH concentrations during the cold period were possibly due to the additional contribution of domestic heating sources and meteorological conditions such as low temperature and solar irradiation. The use of molecular diagnostic ratios indicated that the possible, major PAH pollution sources in the most polluted areas were pyrogenic sources, mainly attributed to petroleum combustion sources (motor vehicle emissions and crude oil combustion). Petrogenic sources related to evaporative emissions also seemed to contribute in the most polluted area during the warm period. Those dates with high carcinogenic character according to the benzo(a)pyrene equivalent (BaP-eq) were also possibly attributed to petroleum combustion sources.     

Okadaic acid induces morphological changes, apoptosis and cell cycle alterations in different human cell types

Okadaic acid (OA) is a marine toxin produced by dinoflagellate species which is frequently accumulated in molluscs usual in the human diet. The exact action mechanism of OA has not been described yet and the results of most reported studies are often conflicting. The aim of this work was to evaluate the OA effects on morphology, cell cycle and apoptosis induction by means of light microscopy and flow cytometry, in three different types of human cells (leukocytes, HepG2 cells and SHSY5Y cells). Cells were treated with a range of OA concentrations in the presence and absence of S9 fraction. OA induced morphological changes in all the cell types studied, and cell cycle disruption only in leukocytes and neuronal cells. SHSY5Y cells were the most sensitive to OA assault. Results obtained in the presence and absence of metabolic activation were similar, suggesting that OA acts both directly and indirectly. Furthermore, OA was found to increase the subG(1) region in the flow cytometry cell cycle analysis, suggesting induction of apoptosis. These results were confirmed by the employment of specific methodologies for studying apoptosis such as caspase 3 activation and annexin V staining. Increases in the apoptosis rate were obtained in all the cells treated in the absence of S9 fraction, accompanied by increases in caspase 3 activation, suggesting that apoptosis induced by OA is a caspase 3-dependent process. Nevertheless, in the presence of S9 fraction no apoptosis was detected, indicating a metabolic detoxifying activity, although necrosis was observed in neuroblastoma cells.     

Development of a sampling method for the simultaneous monitoring of straight-chain alkanes, straight-chain saturated carbonyl compounds and monoterpenes in remote areas

Studies have shown that biogenic compounds, long chain secondary compounds and long lifetime anthropogenic compounds are involved in the formation of organic aerosols in both polluted areas and remote places. This work aims at developing an active sampling method to monitor these compounds (i.e. 6 straight-chain saturated aldehydes from C6 to C11; 8 straight-chain alkanes from C9 to C16; 6 monoterpenes: α-pinene, β-pinene, camphene, limonene, α-terpinene, & γ-terpinene; and 5 aromatic compounds: toluene, ethylbenzene, meta-, para- and ortho-xylenes) in remote areas. Samples are collected onto multi-bed sorbent cartridges at 200 mL min(-1) flow rate, using the automatic sampler SyPAC (TERA-Environnement, Crolles, France). No breakthrough was observed for sampling volumes up to 120 L (standard mixture at ambient temperature, with a relative humidity of 75%). As ozone has been shown to alter the samples (losses of 90% of aldehydes and up to 95% of terpenes were observed), the addition of a conditioned manganese dioxide (MnO(2)) scrubber to the system has been validated (full recovery of the affected compounds for a standard mixture at 50% relative humidity--RH). Samples are first thermodesorbed and then analysed by GC/FID/MS. This method allows suitable detection limits (from 2 ppt for camphene to 13 ppt for octanal--36 L sampled), and reproducibility (from 1% for toluene to 22% for heptanal). It has been successfully used to determine the diurnal variation of the target compounds (six 3 h samples a day) during winter and summer measurement campaigns at a remote site in the south of France.