Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K_ow values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g⁻¹, with detection limits below pg g⁻¹ levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain).     

Solanum nigrum L. weed plants as a remediation tool for metalaxyl-polluted effluents and soils

In this work, the phytoremediation potential of metalaxyl, a commonly used persistent, mobile and leachy fungicide, by Solanum nigrum L. plants was studied. The study revealed that this plant species can be used as an excellent metalaxyl phytoremediation tool, thus providing a cost effective and environmentally friendly clean technology for the decontamination of sites and effluents. As it can be sowed directly in the remediation site, is able to complete its life cycle without suffering major stress. Because it accumulates high amounts of the fungicide in the aboveground tissues, enables its concentration and proper disposal by cutting off the corresponding plant part. The study also suggests that the tolerance to metalaxyl is due to a suitable antioxidant response comprising proline accumulation and guaiacol peroxidase and glutathione-S-transferase enhanced activities, that reduce oxidative damage to the plant organs.     

Heterogeneous photocatalytic oxidation of cyprodinil and fludioxonil in leaching water under solar irradiation

The efficiency of ZnO and TiO₂ suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na₂S₂O₈) to the ZnO or TiO₂ increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t_30W = 18 min) when treated with illuminated ZnO. The disappearance time (DT₇₅), when referred to the normalized illumination time (t_30W), was lower than 40 and 550 min (t_30W = 2 and 40 min) for both fungicides using ZnO or TiO₂, respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO₂ probably due to its nonstoichiometry.     

Assessment of oxidative stress and metabolic changes in common carp (Cyprinus carpio) acutely exposed to different concentrations of the fungicide tebuconazole

The aim of this research is to determine the lethal concentration (LC(50-96 h)) of fungicide tebuconazole for common carp (Cyprinus carpio) and to investigate the occurrence of oxidative stress and metabolic changes after acute exposure to different concentrations of tebuconazole. For this purpose, several parameters were assessed as whole-body levels of thiobarbituric acid-reactive substance (TBARS), protein carbonyl, catalase, superoxide dismutase, glutathione S-transferase, nonprotein thiols, ascorbic acid, glycogen, glucose, lactate, protein, amino acids and ammonia in tebuconazole-exposed fish. The calculated LC(50-96 h) was 2.37 mg L(-1). Fish exhibited significant increase in TBARS levels in all concentrations used while the enzymatic and nonenzymatic antioxidants were decreased. Among the metabolic parameters, glycogen and glucose increased at 1.19 mg L(-1) and protein levels decreased at 1.78 and 2.37 mg L(-1). In conclusion, the fish health was adversely affected by exposure to tebuconazole, and those changes can compromise animal survival in the natural environment. The results indicate that the some of the parameters measured like a possible biomarkers of exposure to tebuconazole for this species of fish.     

Long term remediation of highly polluted acid mine drainage: a sustainable approach to restore the environmental quality of the Odiel river basin

During 20 months of proper operation the full scale passive treatment in Mina Esperanza (SW Spain) produced around 100 mg/L of ferric iron in the aeration cascades, removing an average net acidity up to 1500 mg/L as CaCO₃ and not having any significant clogging problem. Complete Al, As, Cd, Cr, Cu, Ti and V removal from the water was accomplished through almost the entire operation time while Fe removal ranged between 170 and 620 mg/L. The system operated at a mean inflow rate of 43 m³/day achieving an acid load reduction of 597 g·(m² day)⁻¹, more than 10 times higher than the generally accepted 40 g·(m² day)⁻¹ value commonly used as a passive treatment system designing criteria. The high performance achieved by the passive treatment system at Mina Esperanza demonstrates that this innovative treatment design is a simple, efficient and long lasting remediation option to treat highly polluted acid mine drainage.     

Determinants of efficiency in the provision of municipal street-cleaning and refuse collection services

Effective waste management systems can make critical contributions to public health, environmental sustainability and economic development. The challenge affects every person and institution in society, and measures cannot be undertaken without data collection and a quantitative analysis approach. In this paper, the two-stage double bootstrap procedure of Simar and Wilson (2007) is used to estimate the efficiency determinants of Spanish local entities in the provision of public street-cleaning and refuse collection services. The purpose is to identify factors that influence efficiency. The final sample comprised 1072 municipalities. In the first stage, robust efficiency estimates are obtained with Data Envelopment Analysis (DEA). We apply the second stage, based on a truncated-regression, to estimate the effect of a group of environmental factors on DEA estimates. The results show the existence of a significant relation between efficiency and all the variables analysed (per capita income, urban population density, the comparative index of the importance of tourism and that of the whole economic activity). We have also considered the influence of a dummy categorical variable - the political sign of the governing party - on the efficient provision of the services under study. The results from the methodology proposed show that municipalities governed by progressive parties are more efficient.     

Anaerobic digestion of the liquid fraction of dairy manure in pilot plant for biogas production: residual methane yield of digestate

The performance of the only dairy manure biogas plant in Cantabria (Northern coast of Spain) was evaluated in terms of liquid-solid separation and anaerobic digestion of the liquid fraction. Screened liquid fraction was satisfactorily treated in a CSTR digester at HRTs from 20 to 10 days with organic loading rates ranging from 2.0 to 4.5 kg VS/(m(3)d). Stable biogas productions from 0.66 to 1.47 m(3)/(m(3)d) were achieved. Four anaerobic effluents collected from the digester at different HRTs were analyzed to measure their residual methane potentials, which ranged from 12.7 to 102.4 L/gVS. These methane potentials were highly influenced by the feed quality and HRT of the previous CSTR anaerobic digestion process. Biomethanization of the screened liquid fraction of dairy manure from intensive farming has the potential to provide up to 2% of total electrical power in the region of Cantabria.     

Antioxidant responses and reactive oxygen species generation in different body regions of the estuarine polychaeta Laeonereis acuta (Nereididae)

The aim of this study was to analyze the total antioxidant capacity (TOSC), generation of reactive oxygen species (ROS) and lipid peroxidation (LPO) in the different body regions of the estuarine polychaeta Laeonereis acuta (Nereididae) sampled at non-polluted (NOPOL) and polluted (POL) sites from Lagoa dos Patos (Southern Brazil). Organisms collected at POL during summer showed similar (p>0.05) TOSC values along the body, but worms collected at NOPOL presented higher (p<0.05) TOSC values in the posterior (P) region in respect of anterior (A) region and middle (M) region. TOSC in the P region at NOPOL was higher (p<0.05) compared with the same body region of worms at POL. In summer, ROS concentration was higher in A and M regions of worms at POL in respect of the organisms at NOPOL. During winter all the regions showed higher ROS in worms sampled at POL. It was registered absence of season influence on LPO content, but in the P region at NOPOL in summer there were lower LPO levels compared with the others regions (p<0.05). In vitro assays showed that P region, despite a higher basal ROS, presented a higher competence to cope with pro-oxidants compared with A and M regions (p<0.05), corroborating the field results. A lower proteic sulfhydril content was observed in P in respect of the other regions (p<0.05) supporting the idea of a highest oxidant condition in this region. The results indicate that worms collected at the POL site are confronted to higher ROS concentrations, affecting its antioxidant capacity, a result that depends of body regions.     

Fine and coarse particulate matter chemical characterization in a heavily industrialized city in central Mexico during Winter 2003

This paper presents the results of the first reported study on fine particulate matter (PM) chemical composition at Salamanca, a highly industrialized urban area of Central Mexico. Samples were collected at six sites within the urban area during February and March 2003. Several trace elements, organic carbon (OC), elemental carbon (EC), and six ions were analyzed to characterize aerosols. Average concentrations of PM with aerodynamic diameter of less than 10 microm (PM10) and fine PM with aerodynamic diameter of less than 2.5 microm (PM2.5) ranged from 32.2 to 76.6 [g m(-3) and 11.1 to 23.7 microg m(-3), respectively. OC (34%), SO4= (25.1%), EC (12.9%), and geological material (12.5%) were the major components of PM2.5. For PM10 geological material (57.9%), OC (17.3%), and SO4= (9.7%) were the major components. Coarse fraction (PM,, -PM2.5), geological material (81.7%), and OC (8.6%) were the dominant species, which amounted to 90.4%. Correlation analysis showed that sulfate in PM2.5 was present as ammonium sulfate. Sulfate showed a significant spatial variation with higher concentrations to the north resulting from predominantly southwesterly winds above the surface layer and by major SO2 sources that include a power plant and refinery. At the urban site of Cruz Roja it was observed that PM2.5 mass concentrations were similar to the submicron fraction concentrations. Furthermore, the correlation between EC in PM2.5 and EC measured from an aethalometer was r(2) = 0.710. Temporal variations of SO2 and nitrogen oxide were observed during a day when the maximum concentration of PM2.5 was measured, which was associated with emissions from the nearby refinery and power plant. From cascade impactor measurements, the three measured modes of airborne particles corresponded with diameters of 0.32, 1.8, and 5.6 microm.     

Dissipation of fenoxycarb and pyriproxyfen in fresh and canned peach

The objective of this work was to determine the dissipation of fenoxycarb and pyriproxyfen in fresh and canned peaches in order to know the levels of residues that can reach consumers in real circumstances. Two field dissipation studies were carried out, one of them at the pre-harvest interval (PHI) with good agricultural practice (GAP) and the other one in a situation of critical agricultural practice (CAP). Two canning dissipation studies were carried out for samples from both agricultural situations in an industrial pilot plant and the dissipation was determined in each relevant step. An analytical methodology was used including acetone-dichloromethane extraction, purification and analysis by liquid chromatography and diode array detection (LC-DAD) with a limit of quantification (LOQ) of 0.05 mg/kg. It was validated under SANCO/10232/2006 Guidelines. These pesticides complied with the official maximum residue limits (MRLs) in peaches at the PHI with good agricultural practices. In hypothetical situation of a second application at the PHI, fenoxycarb and pyriproxyfen residues were above the MRLs in peaches. The canning study reduced the residues to no detectable levels in the cans for consumers.