Enhanced retention of linuron, alachlor and metalaxyl in sandy soil columns intercalated with wood barriers

A study has been made of the effect a reactive barrier made of pine (softwood) or oak (hardwood) wood intercalated in a sandy soil column has on the retention of linuron, alachlor and metalaxyl (pesticides with contrasting physicochemical characteristics). The leaching of pesticides has been carried out under a saturated flow regime and breakthrough curves (BTCs) have been obtained at flow rates of 1 mL min⁻¹ (all pesticides) and 3 mL min⁻¹ (linuron). The cumulative curves in the unmodified soil indicate a leaching of pesticides >80% of the total amount of compound added. After barrier intercalation, linuron leaching decreases significantly and a modification of the leaching kinetics of alachlor and metalaxyl has been observed. The theoretical R factors increased ∼2.6-3.3, 1.2-1.6-fold, and 1.4-1.7-fold and the concentration of the maximum peak decreased ∼6-12-fold, 2-4-fold and 1.2-2-fold for linuron, alachlor and metalaxyl, respectively. When considering the three pesticides, significant correlations have been found between the theoretical retardation factor (R) and the pore volume corresponding to the maximum peaks of the BTCs (r = 0.77; p < 0.05) or the total volume leached (r = −0.78; p < 0.05). The results reveal the efficacy of reactive wood barriers to decrease the leaching of pesticides from point sources of pollution depends on the type of wood, the hydrophobicity of the pesticide and the adopted water flow rate. Pine was more effective than oak in decreasing the leaching of hydrophobic pesticide linuron or in decreasing the maximum peak concentration of the less hydrophobic pesticides in soils. Efficacy of these wood barriers was limited for the least hydrophobic pesticide metalaxyl.     

Immunosuppression in the infaunal bivalve Scrobicularia plana environmentally exposed to mercury and association with its accumulation

This study aimed to test the hypothesis whether mercury (Hg) activates or suppresses inappropriately the immunity of the bivalve Scrobicularia plana inhabiting a Hg contaminated area (Laranjo basin, Ria de Aveiro, Portugal). Immunity endpoints, as well as lipid peroxidation (LPO) as a sign of damage, were evaluated in parallel with total Hg burden. Bivalves from both moderately (MO) and highly (HI) contaminated sites displayed higher haemolymph Hg load and reduced plasma agglutination. Increased haemocytes density and decreased phagocytosis were observed at HI, whereas increased oxidative burst activity (OBA) was observed at MO, pointing out that the immunotoxicity is a result of Hg direct contact involving no ROS intervention. OBA observed at MO was concomitantly associated to peroxidative damage as depicted by LPO increase in haemocytes and haemolymph plasma. Thus, S. plana can be suggested as a suitable bioindicator of metal pollution in coastal areas on the basis of Hg bioaccumulation and immunotoxicity responses.     

Nonparametric functional data estimation applied to ozone data: prediction and extreme value analysis

The study of extreme values and prediction of ozone data is an important topic of research when dealing with environmental problems. Classical extreme value theory is usually used in air-pollution studies. It consists in fitting a parametric generalised extreme value (GEV) distribution to a data set of extreme values, and using the estimated distribution to compute return levels and other quantities of interest. Here, we propose to estimate these values using nonparametric functional data methods. Functional data analysis is a relatively new statistical methodology that generally deals with data consisting of curves or multi-dimensional variables. In this paper, we use this technique, jointly with nonparametric curve estimation, to provide alternatives to the usual parametric statistical tools. The nonparametric estimators are applied to real samples of maximum ozone values obtained from several monitoring stations belonging to the Automatic Urban and Rural Network (AURN) in the UK. The results show that nonparametric estimators work satisfactorily, outperforming the behaviour of classical parametric estimators. Functional data analysis is also used to predict stratospheric ozone concentrations. We show an application, using the data set of mean monthly ozone concentrations in Arosa, Switzerland, and the results are compared with those obtained by classical time series (ARIMA) analysis.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Inside-sediment partitioning of PAH, PCB and organochlorine compounds and inferences on sampling and normalization methods

Comparability of sediment analyses for semivolatile organic substances is still low. Neither screening of the sediments nor organic-carbon based normalization is sufficient to obtain comparable results. We are showing the interdependency of grain-size effects with inside-sediment organic-matter distribution for PAH, PCB and organochlorine compounds. Surface sediment samples collected by Van-Veen grab were sieved and analyzed for 16 PAH, 6 PCB and 18 organochlorine pesticides (OCP) as well as organic-matter content. Since bulk concentrations are influenced by grain-size effects themselves, we used a novel normalization method based on the sum of concentrations in the separate grain-size fractions of the sediments. By calculating relative normalized concentrations, it was possible to clearly show underlying mechanisms throughout a heterogeneous set of samples. Furthermore, we were able to show that, for comparability, screening at <125 μm is best suited and can be further improved by additional organic-carbon normalization.     

Arsenic distribution in soils and plants of an arsenic impacted former mining area

A mining area affected by the abandoned exploitation of an arsenical tungsten deposit was studied in order to assess its arsenic pollution level and the feasibility of native plants for being used in phytoremediation approaches. Soil and plant samples were collected at different distances from the polluting sources and analysed for their As content and distribution. Critical soil total concentrations of As were found, with values in the range 70-5330 mg kg⁻¹ in the uppermost layer. The plant community develops As tolerance by exclusion strategies. Of the plant species growing in the most polluted site, the shrubs Salix atrocinerea Brot. and Genista scorpius (L.) DC. exhibit the lowest bioaccumulation factor (BF) values for their aerial parts, suggesting their suitability to be used with revegetation purposes. The species Scirpus holoschoenus L. highlights for its important potential to stabilise As at root level, accumulating As contents up to 3164 mg kg⁻¹.     

Spectral estimation of global levels of atmospheric pollutants

Underlying levels of atmospheric pollutants, assumed to be governed by smoothing mechanisms due to atmospheric dispersion, can be estimated from global emissions source databases on greenhouse gases and ozone-depleting compounds. However, spatial data may be contaminated with noise or even missing or zero-valued at many locations. Therefore, a problem that arises is how to extract the underlying smooth levels. This paper sets out a structural spatial model that assumes data evolve across a global grid constrained by second-order smoothing restrictions. The frequency-domain approach is particularly suitable for global datasets, reduces the computational burden associated with two-dimensional models and avoids cumbersome zero-inflated skewed distributions. Confidence intervals of the underlying levels are also obtained. An application to the estimation of global levels of atmospheric pollutants from anthropogenic emissions illustrates the technique which may also be useful in the analysis of other environmental datasets of similar characteristics.     

Substituting missing data in compositional analysis

Multivariate analysis of environmental data sets requires the absence of missing values or their substitution by small values. However, if the data is transformed logarithmically prior to the analysis, this solution cannot be applied because the logarithm of a small value might become an outlier. Several methods for substituting the missing values can be found in the literature although none of them guarantees that no distortion of the structure of the data set is produced. We propose a method for the assessment of these distortions which can be used for deciding whether to retain or not the samples or variables containing missing values and for the investigation of the performance of different substitution techniques. The method analyzes the structure of the distances among samples using Mantel tests. We present an application of the method to PCDD/F data measured in samples of terrestrial moss as part of a biomonitoring study.     

Impacts of atmospheric pollution on the plant communities of British acid grasslands

Air pollutants are recognised as important agents of ecosystem change but few studies consider the effects of multiple pollutants and their interactions. Here we use ordination, constrained cluster analysis and indicator value analyses to identify potential environmental controls on species composition, ecological groupings and indicator species in a gradient study of UK acid grasslands. The community composition of these grasslands is related to climate, grazing, ozone exposure and nitrogen deposition, with evidence for an interaction between the ecological impacts of base cation and nitrogen deposition. Ozone is a key agent in species compositional change but is not associated with a reduction in species richness or diversity indices, showing the subtly different drivers on these two aspects of ecosystem degradation. Our results demonstrate the effects of multiple interacting pollutants, which may collectively have a greater impact than any individual agent.     

Trees as bioindicator of heavy metal pollution in three European cities

Concentrations of four heavy metals were determined in tree leaves and bark collected from polluted and non-polluted areas of three European cities (Salzburg, Belgrade and Thessaloniki) for a comparative study. Platanus orientalis L. and Pinus nigra Arn., widespread in urban northern and southern Europe, were tested for their suitability for air quality biomonitoring. Leaves and barks were collected uniformly of an initial quantity of about 30 g of each sample. Analysis was accomplished by electrothermal atomic absorption spectrometry after total digestion. Site-dependent variations were found with the highest concentration level measured in Belgrade, followed by Thessaloniki and Salzburg. A higher accumulation of heavy metals was found in bark compared to leaves. Pine tree bark, accumulating higher concentrations of trace metals compared to plane tree bark, shows a higher efficiency as bioindicator for urban pollution. Both indicator species are suitable for comparative studies on bioindication of urban air pollution.