Assessment of commercially available polymeric materials for sorptive microextraction of priority and emerging nonpolar organic pollutants in environmental water samples

Among the different organic pollutants, persistent organic pollutants and emerging organic contaminants (EOCs) are of particular concern due to their potentially dangerous effects on the ecosystems and on human health. In the framework of the analysis of some of these organic pollutants in water samples, sorptive extraction devices have proven to be adequate for their monitoring. The efficiency of four commercially available and low-cost polymeric materials [polypropylene, poly(ethylene terephthalate), Raffia, and polyethersulfone (PES)] for the simultaneous extraction of 16 organic compounds from five different families from environmental water samples was evaluated in this work. Firstly, the homogeneity of the sorbent materials was confirmed by means of Raman spectroscopy. After the optimization of the parameters affecting the extraction and the liquid desorption steps, it was found that PES showed the largest efficiencies for slightly polar analytes and, to a lesser extent, for nonpolar analytes. Additionally, Raffia rendered good extraction efficiencies for nonpolar compounds. Thus sorptive extraction methods followed by large volume injection-programmable temperature vaporizer-gas chromatography-mass spectrometry were validated using PES and Raffia as sorbent materials. The validation of the method provided good linearity (0.978?r ²?r ²?-1 level). Finally, these materials were applied to the analysis of contaminants in environmental water samples.     

Antlers of Cervus elaphus as biomonitors of ⁹⁰Sr in the environment

Adequate radioprotection of the environment requires the identification of biomonitors sensitive to the variation of its radionuclide content. Due to the chemical similarities between calcium and strontium, calcified tissues of mammals are considered to be good ⁹⁰Sr biomonitors. This work considered Cervus elaphus antlers which, being shed annually, can give information about the importance of radiostrontium contamination in an ecosystem in the time period required for the growth of the antler. The samples were collected at various points of W and SW Spain. The mean value of their ⁹⁰Sr content was (70 ± 43 (S.D.)) Bq/kg d.w., range (16-218) Bq/kg d.w., and the radionuclide was evenly distributed in the different parts of the antler. There was a good correlation between the antlers’ ⁹⁰Sr content and the ⁹⁰Sr deposited in the soil. The antlers’ content of ²²⁶Ra (from the natural uranium series) and the contents of some stable elements (Ca, Mg, Sr, and K) were also determined. The values for these stable elements were practically constant in the analyzed samples, and the concentrations measured decreased in the following order:Ca » Mg > K > Sr » ⁹⁰Sr > ²²⁶Ra     

Soil moisture determines the effectiveness of two urease inhibitors to decrease N<Subscript>2</Subscript>O emission

Among the mitigation strategies to prevent nitrogen (N) losses from ureic fertilizers, urease inhibitors (UIs) have been demonstrated to promote high N use efficiency by reducing ammonia (NH₃) volatilization. In the last few years, some field experiments have also shown its effectiveness in reducing nitrous oxide (N₂O) losses from fertilized soils under conditions of low soil moisture. An incubation experiment was carried out with the aim of assessing the main biotic mechanisms behind N₂O emissions once that the UIs N-(n-butyl) thiophosphoric triamid (NBPT) and phenil phosphorodiamidate (PPDA) were applied with Urea (U) under different soil moisture conditions (40, 60 and 80 % water-filled pore space, WFPS). In the same study we tried to analyze to what extent soil WFPS regulates the effect of these inhibitors on N₂O emissions. The use of PPDA in our study allowed us to compare the effect of NBPT with that of another commercially available urease inhibitor, aiming to see if the results were inhibitor-specific or not. Based on the results from this experiment, a WFPS (i.e. 60 %) was chosen for a second study (i.e. mesocosm experiment) aiming to assess the efficiency of the UIs to indirectly affect N₂O emissions through influencing the pool of soil mineral N. The N₂O emissions at 40 % WFPS were almost negligible, being significantly lower from all fertilized treatments than that produced at 60 and 80 % WFPS. When compared to U alone, NBPT+U reduced the N₂O emissions at 60 % WFPS but had no effect at 80 % WFPS. The application of PPDA significantly increased the emissions with respect to U at 80 % WFPS whereas no significant effect was found at 60 %. At 80 % WFPS, denitrification was the main source of N₂O emissions for all treatments. In the mesocosm study, the application of NBPT+U was an effective strategy to reduce N₂O emissions (75 % reduction compared to U alone), due to a lower soil ammonium (NH₄ ⁺) content induced by the inhibitor. These results suggest that adequate management of the UI NBPT could provide, under certain soil conditions, an opportunity for mitigation of N₂O emissions from fertilized soils.     

An overview of BORIS: Bioavailability of Radionuclides in Soils

The ability to predict the consequences of an accidental release of radionuclides relies mainly on the level of understanding of the mechanisms involved in radionuclide interactions with different components of agricultural and natural ecosystems and their formalisation into predictive models. Numerous studies and databases on contaminated agricultural and natural areas have been obtained, but their use to enhance our prediction ability has been largely limited by their unresolved variability. Such variability seems to stem from incomplete knowledge about radionuclide interactions with the soil matrix, soil moisture, and biological elements in the soil and additional pollutants, which may be found in such soils. In the 5th European Framework Programme entitled Bioavailability of Radionuclides in Soils (BORIS), we investigated the role of the abiotic (soil components and soil structure) and biological elements (organic compounds, plants, mycorrhiza, and microbes) in radionuclide sorption/desorption in soils and radionuclide uptake/release by plants. Because of the importance of their radioisotopes, the bioavailability of three elements, caesium, strontium, and technetium has been followed. The role of one additional non-radioactive pollutant (copper) has been scrutinised in some cases. Role of microorganisms (e.g., K(d) for caesium and strontium in organic soils is much greater in the presence of microorganisms than in their absence), plant physiology (e.g., changes in plant physiology affect radionuclide uptake by plants), and the presence of mycorrhizal fungi (e.g., interferes with the uptake of radionuclides by plants) have been demonstrated. Knowledge acquired from these experiments has been incorporated into two mechanistic models CHEMFAST and BIORUR, specifically modelling radionuclide sorption/desorption from soil matrices and radionuclide uptake by/release from plants. These mechanistic models have been incorporated into an assessment model to enhance its prediction ability by introducing the concept of bioavailability factor for radionuclides.     

Plant uptake of radiocaesium from artificially contaminated soil monoliths covering major European soil types

Uptake of ¹³⁷Cs was measured in different agricultural plant species (beans, lettuce, barley and ryegrass) grown in 5 undisturbed soil monoliths covering major European soil types. The first cultivation was made three years after soil contamination and plants were grown during 3 successive years. The plant–soil ¹³⁷Cs transfer factors varied maximally 12-fold among soils and 35-fold among species when grown on the same soil. Single correlations between transfer factors and soil properties were found, but they varied widely with plant type and can hardly be used as a predictive tool because of the few soils used. The variation of ¹³⁷Cs concentrations in plants among soils was related to differences in soil solution ¹³⁷Cs and K concentrations, consistent with previous observations in hydroponics and pot trials. Absolute values of transfer factors could not be predicted based on a model validated for pot trials. The ¹³⁷Cs activity concentration in soil solution decreased significantly (11- to 250-fold) for most soils in the 1997–1999 period and is partly explained by decreasing K in soil solution. Transfer factors of lettuce showed both increasing and decreasing trends between 2 consecutive years depending on soil type. The trends could be explained by the variation in ¹³⁷Cs and K concentrations in soil solution. It is concluded that differences in ¹³⁷Cs transfer factors among soils and trends in transfer factors as a function of time can be explained from soil solution composition, as shown previously for pot trials, although absolute values of transfer factors could not be predicted.     

Sensitivity of Mediterranean woody seedlings to copper, nickel and zinc

The restoration of heavy metal contaminated areas requires information on the response of native plant species to these contaminants. The sensitivity of most Mediterranean woody species to heavy metals has not been established, and little is known about phytotoxic thresholds and environmental risks. We have evaluated the response of four plant species commonly used in ecological restoration, Pinus halepensis, Pistacia lentiscus, Juniperus oxycedrus, and Rhamnus alaternus, grown in nutrient solutions containing a range of copper, nickel and zinc concentrations. Seedlings of these species were exposed to 0.048, 1 and 4 microM of Cu; 0, 25 and 50 microM of Ni; and 0.073, 25 and 100 microM of Zn in a hydroponic silica sand culture for 12 weeks. For all four species, the heavy metal concentration increased in plants as the solution concentration increased and was always higher in roots than in shoots. Pinus halepensis and P. lentiscus showed a higher capacity to accumulate metals in roots than J. oxycedrus and R. alaternus, while the allocation to shoots was considerably higher in the latter two. Intermediate heavy-metal doses enhanced biomass accumulation, whereas the highest doses resulted in reductions in biomass. Decreases in shoot biomass occurred at internal concentrations ranging from 25 to 128 microg g-1 of Zn, and 1.7 to 4.1 microg g( -1) of Cu. Nickel phytoxicity could not be established within the range of doses used. Rhamnus alaternus and J. oxycedrus showed higher sensitivity to Cu and Zn than P. halepensis and, especially, P. lentiscus. Contrasted responses to heavy metals must be taken into account when using Mediterranean woody species for the restoration of heavy metal contaminated sites.     

Modelling the Ecological Vulnerability to Forest Fires in Mediterranean Ecosystems Using Geographic Information Technologies

Forest fires represent a major driver of change at the ecosystem and landscape levels in the Mediterranean region. Environmental features and vegetation are key factors to estimate the ecological vulnerability to fire; defined as the degree to which an ecosystem is susceptible to, and unable to cope with, adverse effects of fire (provided a fire occurs). Given the predicted climatic changes for the region, it is urgent to validate spatially explicit tools for assessing this vulnerability in order to support the design of new fire prevention and restoration strategies. This work presents an innovative GIS-based modelling approach to evaluate the ecological vulnerability to fire of an ecosystem, considering its main components (soil and vegetation) and different time scales. The evaluation was structured in three stages: short-term (focussed on soil degradation risk), medium-term (focussed on changes in vegetation), and coupling of the short- and medium-term vulnerabilities. The model was implemented in two regions: Aragón (inland North-eastern Spain) and Valencia (eastern Spain). Maps of the ecological vulnerability to fire were produced at a regional scale. We partially validated the model in a study site combining two complementary approaches that focused on testing the adequacy of model’s predictions in three ecosystems, all very common in fire-prone landscapes of eastern Spain: two shrublands and a pine forest. Both approaches were based on the comparison of model’s predictions with values of NDVI (Normalized Difference Vegetation Index), which is considered a good proxy for green biomass. Both methods showed that the model’s performance is satisfactory when applied to the three selected vegetation types.     

An inhibitor of urease activity effectively reduces ammonia emissions from soil treated with urea under Mediterranean conditions

Urea is an important source of ammonia (NH₃) emissions to the atmosphere from agricultural soils. Abatement strategies are necessary in order to achieve NH₃ emission targets by reducing those emissions. In this context, a field experiment was carried out on a sunflower crop in spring 2006 with the aim of evaluating the effect of the N-(n-butyl) thiophosphoric triamide (NBPT) in the mitigation of volatilized NH₃ from a urea-fertilised soil. Ammonia emission was quantified, using the integrated horizontal flux (IHF) method, following application of urea with and without the urease inhibitor NBPT. Urea and a mixture of urea and NBPT (0.14%, w/w) were surface-applied at a rate of 170 kg N ha⁻¹ to circular plots (diameter 40 m). The soil was irrigated with 10 mm of water just after the application of urea to dissolve and incorporate it into the upper layer of soil. Over the duration of the measurement period (36 days) three peaks of NH₃ were observed. The first peak was associated with hydrolysis of urea after irrigation and the others with the increase of ammonia in soil solution after changes in atmospheric variables such as wind speed and rainfall. The total NH₃ emission during the whole experiment was 17.3 ± 0.5 kg NH₃–N ha⁻¹ in the case of urea treated soils and 10.0 ± 2.2 kg NH₃–N ha⁻¹ where NBPT was included with the urea (10.1 and 5.9%, respectively, of the applied urea–N). The lower NH₃ emissions from plots fertilised with urea + NBPT, compared with urea alone, were associated with a reduction in urease activity during the first 9 days after inhibitor application. This reduction in enzymatic activity promoted a decrease in the exchangeable NH₄⁺ pool.     

Use of an inverse dispersion technique for estimating ammonia emission from surface-applied slurry

Ammonia (NH₃) emission from land application of manure is typically measured using the integrated horizontal flux (IHF) micrometeorological method. However, there are some situations in which alternative techniques (such as an inverse dispersion modelling technique) might be preferable, for example when measuring from large or irregularly shaped source areas. In this study, an inverse dispersion technique using the backward Lagrangian stochastic (bLS) model, with 2 different experimental configurations, was compared with the Integrated Horizontal Flux method (i.e. IHF), which was used as reference technique. Pig slurry was surface-applied at 125 kg N ha^?1 to bare soil on a large plot (80 × 125 m). Cumulative emissions were 19.3, 21.2 and 18.4 kg N ha^?1 from the IHF and the bLS technique (experimental configurations I and II), respectively. Mean flux within each sampling period as estimated by the two techniques compared extremely well, with a slope not significantly different from 1 and r² of 0.99. Although limited in extent, this dataset agree with a previous study in demonstrating the use of the bLS technique with longer period time-averaged concentration measurements.     

Multivariate Statistical Analysis of Meteorological and Air Pollution Data in the ‘Campo De Gibraltar’ Region, Spain

A complete statistical analysis of meteorological and air pollution data was carried out in the ‘Campo de Gibraltar’ region (in the South of Spain) from 1999 to 2002. This is a heavy industrialized area where, up to date, very few air pollution studies have been made. The main objectives of the study presented here have been the characterization of the meteorological and (gaseous and particulate) air pollution conditions in the area, and the relations between them. Multivariate statistical techniques, such as Principal Component Analysis (PCA), have been applied to the data. The results show that air quality in the area is highly dependent on meteorological conditions such as wind persistence and direction, dispersion capability of the atmosphere, and humidity content. On average, sulphur dioxide and nitrogen oxide air pollution, mainly caused by fuel-oil combustion and traffic, respectively, is not very high. However, an important number of exceedences of the limits established by the EU Directive 1999 for PM10 (particulate matter with a diameter less than 10 μm) have been observed in some points of the area. A significant percentage of these exceedences (about 22% on average) are likely caused by African dust intrusions, which usually take place from May to August. From gaseous and particulate air correlations, it seems that anthropogenic activities contribute with about 19% on average.