Bioaccumulation of Trace Elements in a Wild Grass Three Years After the Aznalcóllar Mine Spill (South Spain)

In this paper, we surveyed the concentration of nine trace elements (As, Cd, Cu, Fe, Mn, Ni, Pb, Tl and Zn) in bermudagrass (Cynodon dactylon) 3 years after the mine spill in Aznalcóllar (south Spain). The results were compared with those that had been obtained for the same species in a previous study, 18 months after the accident. Three types of soil condition were determined: i) unaffected soils (UN, control); ii) cleaned up and amended soils (A, amended); and (iii) non-amended soils, inaccessible to the clean-up and remediation operations (NA, non-amended). The trace element concentrations in the plants were lower than those reported in the first sampling for both washed (plant tissues) and unwashed plants (as consumed by herbivores). Apart from Cd, trace elements concentrations (plant tissues) were similar in the A and the UN soils. In the NA soils, the Cd, Fe, Mn, Zn and Pb levels in unwashed plants were excessive for animal consumption. This wild grass seems to be suitable as a soil stabilizer for spill affected soils and as a biomonitor for soil pollution by some trace elements (As, Cu and Zn); however, its potential for phytoextraction is negligible.     

Introduction of the Factor of Partitioning in the Lithogenic Enrichment Factors of Trace Element Bioaccumulation in Plant Tissues

Bioindicators are widely used in the study of trace elements inputs into the environment and great efforts have been conducted to separate atmospheric from soil borne inputs on biomass accumulation. Many monitoring studies of trace element pollution take into account the dust particles located in the plant surface plus the contents of the plant tissues. However, it is usually only the trace element content in the plant tissues that is relevant on plant health. Enrichment factor equations take into account the trace element enrichment of biomasses with respect soil or bedrocks by comparing the ratios of the trace element in question to a lithogenic element, usually Al. However, the enrichment equations currently in use are inadequate because they do not take into account the fact that Al (or whichever reference element) and the element in question may have different solubility-absorption-retention levels depending on the rock and soil types involved. This constrain will become critical when results from different sites are compared and so in this article we propose that the solubility factors of each element are taken into account in order to overcome this constrain. We analysed Sb, Co, Ni, Cr, Pb, Cd, Mn, V, Zn, Cu, As, Hg, and Al concentration in different zones of Catalonia (NE Spain) using the evergreen oak Quercus ilex and the moss Hypnum cupressiforme as target species. We compared the results obtained in rural and non industrial areas with those from the Barcelona Metropolitan Area. We observed differences in Al concentrations of soils and bedrocks at each different site, together with the differences in solubility between Al and the element in question, and a weak correlation between total soil content and water extract content through different sites for most trace elements. All these findings show the unsuitability of the current enrichment factors for calculating lithospheric and atmospheric contributions to trace element concentrations in biomass tissues. The trace element enrichment factors were calculated by subtracting the part predicted by substrate composition (deduced from water extracts from soils and bedrock) from total concentrations. Results showed that for most of the trace elements analysed, trace elements enrichment factors were higher inside the Barcelona Metropolitan Area than outside, a finding that indicates that greater atmospheric inputs occur in urban areas. The results show that the most useful and correct way of establishing a reference for lithospheric and atmospheric inputs into the plant tissues is, first, to analyse samples of the same plant species collected from a number of sites possessing similar environmental conditions (climate, vegetation type, soil type) and, second, to use this new enrichment factor obtained by subtracting from the total concentration in plant tissue the predicted contribution of soil or bedrock extracts instead of that of total soil or bedrock concentrations.     

Dependence of Ozone Biomonitoring on Meteorological Conditions of Different Sites in Catalonia (N.E. Spain)

Evaluation of visual symptoms of ozone damage was conducted in the network of bioindicator rural stations of Catalonia (NE Spain) every 14 days from May to October. Damage rates of ozone (and consequently, ozone biomonitoring capacity of bioindicators) were found to vary highly in time and space depending on the local environmental and meteorological conditions. Lower ozone damage to foliage was produced when meteorological conditions favour stomata resistance. Modulatory effects of meteorological conditions need to be considered in biomonitoring and when modeling plant ozone doses and damage.     

Regional integration and local change: road paving, community connectivity, and social–ecological resilience in a tri-national frontier, southwestern Amazonia

Initiatives for global economic integration increasingly prioritize new infrastructure in relatively remote regions. Such regions have relatively intact ecosystems and provide valuable ecosystem services, which has stimulated debates over the wisdom of new infrastructure. Most prior research on infrastructure impacts highlights economic benefits, ecological damage, or social conflicts. We suggest a more integrative approach to regional integration by appropriating the concepts of connectivity from transport geography and social?Cecological resilience from systems ecology. Connectivity offers a means of observing the degree of integration between locations, and social?Cecological resilience provides a framework to simultaneously consider multiple consequences of regional integration. Together, they offer a spatial analysis of resilience that considers multiple dimensions of infrastructure impacts. Our study case is the southwestern Amazon, a highly biodiverse region which is experiencing integration via paving of the Inter-Oceanic Highway. Specifically, we focus on the ??MAP?? region, a tri-national frontier where Bolivia, Brazil, and Peru meet and which differs in the extent of highway paving. We draw on a tri-national survey of more than 100 resource-dependent rural communities across the MAP frontier and employ indicators for multiple dimensions of connectivity and social?Cecological resilience. We pursue a comparative analysis among regions and subregions with differing degrees of community connectivity to markets in order to evaluate their social?Cecological resilience. The findings indicate that connectivity and resilience have a multifaceted relationship, such that greater community connectivity corresponds to greater resilience in some respects but not others. We conclude by noting how our findings integrate those from heretofore largely disparate literatures on infrastructure. The integration of transport geography with resilience thought thus stands to advance the study of infrastructure impacts.     

Occurrence of cyclophosphamide and epirubicin in wastewaters by direct injection analysis–liquid chromatography–high-resolution mass spectrometry

Background, aim, and scope

According to the high incidence of cancer worldwide, the amount of cytostatic drugs administered to patients has increased. These compounds are excreted to wastewaters, and therefore become potential water contaminants. At this stage, very little is known on the presence and elimination of cytostatic compounds in wastewater treatment plants (WWTP). The aim of this study was to develop a liquid chromatography?Chigh-resolution mass spectrometry (LC?COrbitrap?CMS) method for the determination of cyclophosphamide and epirubicin in wastewaters. These compounds represent two outmost used cytostatic agents.

Materials and methods

Extraction and analytical conditions were optimized for cyclophosphamide and epirubicin in wastewater. Both solid-phase extraction using Oasis 200?mg hydrophilic?Clipophilic balanced (HLB) cartridges and direct injection analysis were evaluated. Mass spectral characterization and fragmentation conditions were optimized at 50,000 resolving power (full width at half maximum, m/z 200) to obtain maximum sensitivity and identification performance. Quality parameters (recoveries, limits of detection, and repetitivity) of the methods developed were determined, and best performance was obtained with direct water analysis of the centrifuged wastewater. Finally, this method was applied to determine the presence of cyclophosphamide and epirubicin in wastewaters from a hospital effluent, an urban effluent, and influents and effluents from three WWTP.

Results and discussion

Cyclophosphamide and epirubicin were recovered after 50?mL preconcentration on solid-phase extraction 200?mg Oasis HLB cartridges (87% and 37%, respectively), and no breakthrough was observed by extracting 500?mL of water. Limits of detection were of 0.35 and 2.77?ng/L for cyclophosphamide and epirubicin, respectively. On the other hand, direct injection of water spiked at 1???g/L provided recoveries of 107% for cyclophosphamide and 44% for epirubicin and limits of detection from 3.1 to 85?ng?L^?1, respectively. The analysis of wastewaters using direct injection analysis revealed the presence of cyclophosphamide and epirubicin in WWTP influents and hospital and urban effluents at levels ranging from 5.73 to 24.8???g?L^?1.

Conclusions

The results obtained in this study demonstrate the capability of LC?COrbitrap?CMS for accurate trace analysis of these very polar contaminants. This method permitted to identify cyclophosphamide and epirubicin in wastewaters and influents of WWTP, but no traces were detected in WWTP effluents. The methodology herein developed is sensitive and robust and applicable for screening of a large number of samples since no preconcentration is needed.     

Comparing the response of biochemical indicators (biomarkers) and biological indices to diagnose the ecological impact of an oil spillage in a Mediterranean river (NE Catalunya, Spain)

Three biomarkers of hydrocarbon exposure, liver 7-ethoxyresourfin-O-deethylase activity (EROD), fluorescent hydrocarbon compounds (FACs) in bilis, and the liver antioxidant enzyme catalase (CAT) were examined in the autochthonous fish species Barbus meridionalis collected in the river Fluvià (NE Catalunya, Spain) after an oil spillage. Four different locations were sampled, including the impacted site, upstream and downstream sites and a reference site. Biomarker responses were compared with diatom and macroinvertebrate community assemblage metrics (Specific Pollution Sensitivity index - IPS, and Iberian Biological Monitoring Working Party - IBMWP, respectively). Chemical analyses denoted that polycyclic aromatic hydrocarbon levels in sediment were much higher at the impacted site than in downstream reaches. Four fold increase of EROD activity together with increased levels of biliary FACs in barbs collected at the spilled site indicated exposure of inhabiting fish to the oil. Additionally, CAT activity was significantly depressed (four fold) when compared to other stations, thus suggesting that fish collected from the impacted sites could be more susceptible to suffer oxidative stress. Biological indices (particularly that of the diatom community IPS) showed slight significant effects between control and impacted sites, indicating that more tolerant taxa were favoured because of the oil spillage. These results support the need to include biochemical responses measured in local species in monitoring programmes aimed to diagnose specific pollution effects in stressed river ecosystems.     

Ecological risk assessment of organic waste amendments using the species sensitivity distribution from a soil organisms test battery

Safe amendment rates (the predicted no-effect concentration or PNEC) of seven organic wastes were estimated from the species sensitivity distribution of a battery of soil biota tests and compared with different realistic amendment scenarios (different predicted environmental concentrations or PEC). None of the wastes was expected to exert noxious effects on soil biota if applied according either to the usual maximum amendment rates in Europe or phosphorus demands of crops (below 2 tonnes DM ha⁻¹). However, some of the wastes might be problematic if applied according to nitrogen demands of crops (above 2 tonnes DM ha⁻¹). Ammonium content and organic matter stability of the studied wastes are the most influential determinants of the maximum amendment rates derived in this study, but not pollutant burden. This finding indicates the need to stabilize wastes prior to their reuse in soils in order to avoid short-term impacts on soil communities.     

Comparison of solid-phase and eluate assays to gauge the ecotoxicological risk of organic wastes on soil organisms

Development of methodologies to assess the safety of reusing polluted organic wastes in soil is a priority in Europe. In this study, and coupled with chemical analysis, seven organic wastes were subjected to different aquatic and soil bioassays. Tests were carried out with solid-phase waste and three different waste eluates (water, methanol, and dichloromethane).Solid-phase assays were indicated as the most suitable for waste testing not only in terms of relevance for real situations, but also because toxicity in eluates was generally not representative of the chronic effects in solid-phase.No general correlations were found between toxicity and waste pollutant burden, neither in solid-phase nor in eluate assays, showing the inability of chemical methods to predict the ecotoxicological risks of wastes. On the contrary, several physicochemical parameters reflecting the degree of low organic matter stability in wastes were the main contributors to the acute toxicity seen in collembolans and daphnids.     

Proposal for an Integral Quality Index for Urban and Urbanized Beaches

A composite index, based on function analysis and including thirteen sub-indices, was developed to assess the overall quality of urban and urbanized beaches in the Mediterranean area. The aggregation of components and sub-indices was based on two questionnaires completed by beach users and experts. Applying the new Beach Quality Index (BQI) demonstrated that the quality of beaches could be improved. In general, the strongest aspects of the beaches assessed were those related to short-term user demand, and the weakest were those related to the consequences of human pressure on the area, in particular, erosion problems. The composite index is intended to be used together with Environmental Management Beach Systems (EMBs) as a hierarchical management scorecard and in monitoring programs. This new tool could also make planning more proactive by synthesizing the state of the most important beach processes.     

Diet and environment 1.2 million years ago revealed through analysis of dental calculus from Europe’s oldest hominin at Sima del Elefante,Spain

Sima del Elefante, Atapuerca, Spain contains one of the earliest hominin fragments yet known in Europe, dating to 1.2 Ma. Dental calculus from a hominin molar was removed, degraded and analysed to recover entrapped remains. Evidence for plant use at this time is very limited and this study has revealed the earliest direct evidence for foods consumed in the genus Homo. This comprises starchy carbohydrates from two plants, including a species of grass from the Triticeae or Bromideae tribe, meat and plant fibres. All food was eaten raw, and there is no evidence for processing of the starch granules which are intact and undamaged. Additional biographical detail includes fragments of non-edible wood found adjacent to an interproximal groove suggesting oral hygiene activities, while plant fibres may be linked to raw material processing. Environmental evidence comprises spores, insect fragments and conifer pollen grains which are consistent with a forested environment.