Mass scans from a proton transfer mass spectrometry analysis of air over Mediterranean shrubland browsed by horses

Plants usually emit large amount and varieties of volatiles after being damaged by herbivores. However, analytical methods for measuring herbivore-induced volatiles do not normally monitor the whole range of volatiles and the response to large herbivores such as large mammals is much less studied than the response to other herbivores such as insects. In this paper we present the results of using a highly sensitive proton transfer reaction-mass spectrometry (PTR-MS) technique that allows simultaneous monitoring of leaf volatiles in the pptv range. The resulting mass scans in air over Mediterranean shrubland browsed by horses show 70 to 100% higher concentrations of the masses corresponding to mass fragments 57, 43 and 41 (mostly hexenals, acetone and acetic acid) than scans over control non-browsed shrubland. These compounds are biogeochemically active and they are significant components of the volatile organic carbon found in the atmosphere. They influence the performance of living organisms and, the chemical and physical processes of Earth's atmosphere.     

Testing a new model of aphid abundance with sedentary and non-sedentary predators

Aphid population dynamics has been thoroughly investigated, especially in tree-dwelling aphids. Among the controls of the aphid rate of increase are the negative effects of antagonists, the positive effects of mutualists, the density-dependence of the aphid dynamics, and the non-stationary quality of plant tissues. Here we present a mechanistic model of aphid growth that considers most of these governing factors using a simple formulation. What is new in this model is that it considers two kinds of antagonists. The first kind is a guild of aphid predator specialists that includes ladybirds (Coleoptera: Coccinellidae), but also species of some families of Hemiptera, Diptera, and Neuroptera. The second kind of antagonists consists of omnivores or generalist predators and in this particular setting is exemplified by the European earwig Forficula auricularia (Dermaptera: Forficulidae). The model developed here compared the effects of these two different kinds of aphid predators, the second one always at the site (sedentary predators) and the first one that arrives in important numbers only once the aphid population has already developed to some degree (non-sedentary predators). Multiple model parameter sets, representing different hypotheses about controls on aphid populations, were evaluated within the Generalised Likelihood Uncertainty Estimation (GLUE) methodology. The model correctly reproduced the experimental data obtained in an organic citrus grove showing the important effect that sedentary predators as earwigs can have on the aphid populations. Low densities of sedentary predators or even low predation rates can have a disproportionate effect on the final aphid density, as they prey on small populations, when the per capita effect on the aphid population is higher. During the main spring peak of aphids the role of non-sedentary predators is secondary, as they track the aphid density rather than control it. However, these non-sedentary predators are important within the proposed model to keep the second autumn peak of aphids at low values.     

Increasing interannual and altitudinal ozone mixing ratios in the Catalan Pyrenees

Interannual, seasonal, daily and altitudinal patterns of tropospheric ozone mixing ratios, as well as ozone phytotoxicity and the relationship with NO_x precursors and meteorological variables were monitored in the Central Catalan Pyrenees (Meranges valley and Forest of Guils) over a period of 5 years (2004–2008). Biweekly measurements using Radiello passive samplers were taken along two altitudinal transects comprised of thirteen stations ranging from 1040 to 2300 m a.s.l. Visual symptoms of ozone damage in Bel-W3 tobacco cultivars were evaluated biweekly for the first three years (2004–2006). High ozone mixing ratios, always above forest and vegetation protection AOT40 thresholds, were monitored every year. In the last 14 years, the AOT40 (Apr–Sept.) has increased significantly by 1047 μg m^?3 h per year. Annual means of ozone mixing ratios ranged between 38 and 67 ppb_v (38 and 74 ppb_v during the warm period) at the highest site (2300 m) and increased at a rate of 5.1 ppb_v year^?1. The ozone mixing ratios were also on average 35–38% greater during the warm period and had a characteristic daily pattern with minimum values in the early morning, a rise during the morning and a decline overnight, that was less marked the higher the altitude. Whereas ozone mixing ratios increased significantly with altitude from 35 ppb_v at 1040 m–56 ppb_v at 2300 m (on average for 2004–2007 period), NO₂ mixing ratios decreased with altitude from 5.5 ppb_v at 1040 m–1 ppb_v at 2300 m. The analysis of meteorological variables and NO_x values suggests that the ozone mainly originated from urban areas and was transported to high-mountain sites, remaining aloft in absence of NO. Ozone damage rates increased with altitude in response to increasing O₃ mixing ratios and a possible increase in O₃ uptake due to more favorable microclimatic conditions found at higher altitude, which confirms Bel-W3 as a suitable biomonitor for ozone concentrations during summer time. Compared to the valley-bottom site the annual means of ozone mixing ratios are 37% larger in the higher sites. Thus the AOT40 for the forest and vegetation protection threshold is greatly exceeded at higher sites. This could have substantial effects on plant life at high altitudes in the Pyrenees.     

Patterns of mercury and methylmercury bioaccumulation in fish species downstream of a long-term mercury-contaminated site in the lower Ebro River (NE Spain)

Since the 19th century, large amounts of industrial waste were dumped in a reservoir adjacent to a chlor-alkali plant in the lower Ebro River (NE Spain). Previous toxicological analysis of carp populations inhabiting the surveyed area have shown that the highest biological impact attributable to mercury pollution occurred downstream of the discharge site. However, mercury speciation in fish from this polluted area has not been addressed yet. Thus, in the present study, piscivorous European catfish (Silurus glanis) and non-piscivorous common carp (Cyprinus carpio) were selected, to investigate the bioavailability and bioaccumulation capacities of both total mercury (THg) and methylmercury (MeHg) at the discharge site and downstream points. Multiple Correspondence Analysis (MCA) was applied to reduce the dimensionality of the data set, and Multiple Linear Regression (MLR) models were fitted in order to assess the relationship between both Hg species in fish and different variables of interest. Mercury levels in fish inhabiting the dam at the discharge site were found to be approximately 2-fold higher than those from an upstream site; while mercury pollution progressively increased downstream of the hot spot. In fact, both THg and MeHg levels at the farthest downstream point were 3 times greater than those close to the waste dump. This result clearly indicates downstream transport and increased mercury bioavailability as a function of distance downstream from the contamination source. A number of factors may affect both the downstream transport and increased Hg bioavailability associated with suspended particulate matter (SPM) and dissolved organic carbon (DOC).     

Identifying the origin of atmospheric inputs of trace elements in the Prades Mountains (Catalonia) with bryophytes, lichens, and soil monitoring

The biomonitors Hypnum cupressiforme and Xanthoria parietina were used to assess the deposition of trace elements and their possible origin in the Prades Mountains, a protected Mediterranean forest area of NE Spain with several pollution sources nearby. Al, As, Cd, Co, Cu, Cr, Ni, Pb, Sb, Ti, V, and Zn were determined in 16 locations within this protected area. Soil trace element concentrations were also ascertained to calculate enrichment factors (EF) and use them to distinguish airborne from soilborne trace element inputs. In addition, lichen richness was measured to further assess atmospheric pollution. EF demonstrated to be useful not only for the moss but also for the lichen. Cd, Cr, Cu, Ni, and Zn presented values higher than three in both biomonitors. These trace elements were also the main ones emitted by the potential sources of pollutants. The distance between sampling locations and potential pollution sources was correlated with the concentrations of Cu, Sb, and Zn in the moss and with Cr, Ni, and Sb in the lichen. Lichen richness was negatively correlated with lichen Cu, Pb, and V concentrations on dry weight basis. The study reflected the remarkable influence that the pollution sources have on the presence of trace elements and on lichen species community composition in this natural area. The study highlights the value of combining the use of biomonitors, enrichment factors, and lichen diversity for pollution assessment to reach a better overview of both trace elements’ impact and the localization of their sources.     

Evaluation of the Spanish hot dip galvanising sector as a source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

A survey to estimate the polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) emissions of Spanish hot dip galvanising sector was carried out during 2002. This investigation is the first presenting Spanish experimental data related to this industrial sector. Three different matrices: flue gas, ash and filter dust were tested to quantify the PCDD/Fs generated during the galvanising process. The organic source of PCDD/F formation could be from the insufficient degreasing o from inhibitors or additives used in the pickling steps such as quinoline, isoquinoline, 8-methylquinoline or polyether phosphoric acid. Low levels PCDD/Fs were achieved in air emissions when air control devices are used. On the contrary, filter dusts are highly contaminated; indicating that the absence of air control devices would increase the risk of fugitive emissions. Homologue profiles and Principal Component Analysis demonstrate there are differences in the formation mechanisms in the bath zone (ashes) compared to the stack location (filter dusts and air emissions), related to the de novo synthesis and reaction time. The annual PCDD/F emission to the atmosphere for this sector during 2002 has been estimated in 0.023g I-TEQ. The emission factor of plants with air control devices has been calculated at 0.030microg I-TEQ/ton of galvanised steel.     

Performance evaluation of a biotrickling filter treating a mixture of oxygenated VOCs during intermittent loading

Laboratory scale-studies on the biodegradation of a 1:1:1 weight mixture of three oxygenated volatile organic compounds (VOCs), ethanol, ethyl acetate, and methyl-ethyl ketone (MEK) in a biotrickling filter (BTF) were carried out using two identically sized columns, filled with different polypropylene rings. The performance of the BTFs was examined for a period of 10 months applying several operational strategies. Similar performance was obtained for both supports. Intermittent flow rate of trickling liquid was shown beneficial to improve the removal efficiency (RE). Continuous feeding of VOC resulted in an excessive accumulation of biomass so high pressure drop was developed in less than 20-30 d of operation. Intermittent VOC loading with night and weekend feed cut-off periods passing dry air, but without addition of water, was shown as a successful operational mode to control the thickness of the biofilm. In this case, operation at high inlet loads (ILs) was extended for more than 75 d maintaining high REs and low pressure drops. Outlet emission concentrations lower than 100 mg Cm(-3) were obtained for ILs up to 100 g Cm(-3)h(-1) working at 15s of empty bed residence time. The most easily biodegradable compounds ethanol and ethyl acetate were used primarily than MEK. After a 3-wk-starvation period, the system performance was almost restored since the first d of operation, being the removal of the less biodegradable compound, MEK, partially deteriorated.     

Ten years measuring PCDDs/PCDFs in ambient air in Catalonia (Spain)

This work summarizes the results of a ten year surveillance programme on PCDD/F in ambient air carried out in Catalonia (Spain). The study has been conducted by the Dioxin Laboratory of Spanish Council for Scientific Research (CSIC) in collaboration with the Environment Department of the Catalonian Government. 175 samples have been collected throughout Catalonia from 1994 to 2004. Different sampling locations classified as industrial, traffic, urban, suburban and rural sites have been monitored in order to find the most contaminated zones as well as the ones with expected background concentrations. The highest concentrations found in this study were determined at the industrial locations. Concentrations ranging from 5 to 1196 fg I-TEQ/m3, with a mean value of 140 fg I-TEQ/m3 and from 10 to 357 fg I-TEQ/m3, with a mean value of 72 fg I-TEQ/m3 were determined in industrial and traffic sampling points, respectively. In contrast, the lowest concentrations were found in rural stations, ranging from 5 to 45 fg I-TEQ/m3, with a mean value of 28 fg I-TEQ/m3. The PCDD/F concentration trend in Catalonian ambient air shown a clear drop of the median values occurred during the study sampling period. A decline of about 70% was observed from 1997-1998 to 2003-2004.     

Distribution of polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT) in Barcelona harbour sediments and their impact on benthic communities

Sediments have long been recognised as a sink for many contaminants like polycyclic aromatic hydrocarbons (PAHs) and tributyltin (TBT), which by virtue of their nature can strongly adsorb onto sediments affecting the benthic community inhabiting them. Using geographical information systems, this study reports and combines the results of several already existing studies along Barcelona harbour in order to assess the potential ecological impacts of these contaminants on the benthos of the harbour ecosystem. Chemical analysis indicated low to moderate contents of PAHs and high contents of TBT in sediments in Barcelona harbour. Comparison against existing sediment quality guidelines (SQGs) indicated that acutely toxic effects would not be expected for PAHs but for TBT, which represents a serious environmental threat for the benthic community. Benthos surveys revealed a deterioration of the benthic community throughout the harbour, especially in the inner port.