Factors controlling the emissions of volatile organic acids from leaves of Quercus ilex L. (Holm oak)

Direct emissions and emission of precursor compounds of acetic and formic acid from higher plants are a significant source of these acids in the atmosphere. To travel from the plant cell to the atmosphere, a gas molecule must first leave the liquid phase and then enter the internal leaf gas phase. The apoplast (cell wall) is the last barrier before the molecule can escape through the stomata. During field experiments we monitored the gas exchange (H₂O, CO₂, organic acids) of Quercus ilex L. leaves. The exchange rates of acetic and formic acid under field conditions followed a typical diurnal pattern and ranged between −10 (uptake) and 52 (emission) nmol m^-2 leaf area min^-1 with the maximum around noon. Growth chamber experiments indicate that the emission is related to the stomatal conductance. We discussed the exchange rate of organic acids between the cell wall and the atmosphere in connection with Henry’s law, and the physicochemical conditions in the cell wall. The evaluation showed that for apoplastic pH values between 4 and 5, 26–130% of the measured acetic acid emission based on leaf area could be predicted.     

Polycyclic aromatic hydrocarbon contamination in an urban area assessed by Quercus ilex leaves and soil

We investigated the PAH contamination of Naples urban area, densely populated and with high traffic flow, by analyses of environmental matrices: soil and Quercus ilex leaves. Being some PAHs demonstrated to have hazardous effects on human health, the accumulation of carcinogenic and toxic PAHs (expressed as B(a)Peq) was evaluated in the leaves and soil. The main sources of the PAHs were discriminated by the diagnostic ratios in the two matrices. The urban area appeared heavily contaminated by PAHs, showing in soil and leaves total PAH concentrations also fivefold higher than those from the remote area. The soil mainly accumulated heavy PAHs, whereas leaves the lightest ones. Median values of carcinogenic PAH concentrations were higher in soil (440 ng g^?1 d.w.) and leaves (340 ng g^?1 d.w.) from the urban than the remote area (60 and 70 ng g^?1 d.w., respectively, for soil and leaves). Also, median B(a)Peq concentrations were higher both in soil and leaves from the urban (137 and 63 ng g^?1 d.w., respectively) than those from the remote area (19 and 49 ng g^?1 d.w., respectively). Different from the soils, the diagnostic ratios found for the leaves discerned PAH sources in the remote and urban areas, highlighting a great contribution of vehicular traffic emission as main PAH source in the urban area.     

Removal of toxic metals from solution by leaf, stem and root phytomass of Quercus ilex L. (holly oak)

Increased consciousness for safeguarding the aqueous environment has prompted a search for alternative technologies for the removal of toxic metal ions from aqueous solutions. In this regard, a wide variety of biomass is being considered as adsorbents of heavy metals for treatment of industrial and domestic wastewaters as well as natural waters, including drinking water. In the present investigation, the potential of Quercus ilex phytomass from stem, leaf and root as an adsorbent of chromium (Cr), nickel (Ni), copper (Cu), cadmium (Cd) and lead (Pb) at ambient temperature was investigated. The metal uptake capacity of the root for different metals was found to be in the order: Ni>Cd>Pb>Cu>Cr; stem Ni>Pb>Cu>Cd>Cr; and leaf Ni>Cd>Cu>Pb>Cr. The highest amount adsorbed was Ni (root>leaf>stem). Data from this laboratory demonstrated that Ni is sequestered mostly in the roots, where concentrations can be as high as 428.4 ng/g dry wt., when 1-year-old seedlings were treated with Ni (2000 mg/l) in pot culture experiments, compared to 7.63 ng/g dry wt., control (garden and greenhouse soil) topsoil where Ni was present in trace amounts. This proves that the root biomass of Q. ilex has the capacity for complexing Ni. Cr exhibited the least adsorption values for all the three types of phytomass compared to other metals. The trend of adsorption of the phytomass was similar for Ni and Cd, i.e. root>leaf>stem. Desorption with 10 mM Na(4) EDTA was effective (55-90%) and, hence, there exists the possibility of recycling the phytomass. The biosorption results of recycled phytomass suggest that the selected adsorbents are re-usable. The advantages and potential of the Q. ilex phytomass as a biofilter of toxic trace metals, the scope and need for enhancing the efficiency of the Q. ilex phytomass as an adsorbent of metals are presented.     

Response of Holm oak (Quercus ilex subsp. ballota) and mastic shrub (Pistacia lentiscus L.) seedlings to high concentrations of Cd and Tl in the rhizosphere

The impairment of root growth and photosynthetical functioning are the main impacts of trace elements on woody plant seedlings. In this work, we assessed the response of Holm oak (Quercusilex subsp. ballota) and mastic shrub (Pistacia lentiscus) seedlings to high concentrations of Cd and Tl in the rhizosphere. These are non-essential trace elements, with a potential high mobility in the soil-plant system. Seedlings of these species are frequently used in the afforestation of degraded soils in mining areas. Plants were exposed to different levels of Cd (20, 80 and 200 mg L⁻¹) and Tl (2, 10 and 20 mg L⁻¹) in a sand culture. Biomass allocation, growth rates, chlorophyll fluorescence and gas exchange were studied. Both metals affected root biomass. Cadmium produced an increase in the root mass ratio and a decrease in the specific leaf area of the plants in oak seedlings, while Tl did not provoke such response. Mastic plants were more sensitive to Tl and Cd than oak plants. Between elements, Tl provoked more severe toxic effects in the plants, affecting the antennae complexes and reaction centers of the photosystem II. Both elements decreased net assimilation rates (down to a 20% of the control plants) and stomatal conductance (5-10% of the values for the control plants). Cadmium was highly retained in the roots of both species, while Tl was highly translocated into the leaves. In general, Holm oak showed a higher tolerance for Cd than for Tl, and a higher resistance to both metals than mastic shrub, due to a high capacity for Cd retention at the root level. However, such accumulation in roots may induce water stress in the seedling exposed to Cd.     

Temporal and spatial variation in C, N, S and trace element contents in the leaves of Quercus ilex within the urban area of Naples

This paper presents a comparative analysis of the concentrations of C, N and S and several trace elements (Fe, Mn, Na, Zn, Cu, V, Pb, Ni, Cr, Cd) in leaves of Quercus ilex, an evergreen oak, collected in the urban area of Naples in 1989 and 1996. The samplings were carried out from 25 urban sites (roads with different traffic flows as well as urban and suburban parks) and from two remote areas as controls. Relative to 1989, the values measured in 1996 denote a strong decrement of S, Fe, Na, Pb, and Cr, with the exception of S in control sites. By contrast, C, N and Cd contents were higher in 1996 than in 1989. Cu and Ni showed a conspicuous increment in control sites as well as in urban sites facing the sea and in the parks, while in all the other urban sites these elements decreased remarkably. No significant difference was found in the leaf contents of Mn, Zn and V measured in 1989 relative to 1996. Both in 1989 and 1996 the contents of N, S, Fe, Na, Cu, Pb, V, Ni, Cr and Cd were significantly higher in leaves from urban sites than in the controls, reflecting the high degree of contamination of the urban area. Concentration factors expressed as the ratio of road/control values for most of the elements were still very high in leaves collected in 1996, though remarkably lower than in 1989.     

Leaves of Quercus ilex L. as biomonitors of PAHs in the air of Naples (Italy)

Polycyclic aromatic hydrocarbons (PAHs) were determined by the GC-MS chromatography in the leaves of Quercus ilex L., an evergreen Mediterranean oak, to monitor the degree of pollution in the urban area of Naples compared to remote areas. Leaf samples were collected in July 1998 from four urban parks, six roadsides and two sites in remote areas. The total PAH contents in Q. ilex leaves ranged from 106.6 in a control site to 4607.5 ng/g d.w. along a road with a high traffic flow. The mean concentration factors (urban/control) were 3.8 for the parks and 15 for the roads. The contribution of carcinogenic PAHs (benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, indeno[1,2,3-c,d]pyrene) was higher in urban area and differed according to the site, ranging from 6.7% to 21.3%. The total PAH burden in control sites was dominated by the low molecular weight PAHs, whilst along the urban roads fluoranthene, pyrene and benz[a]anthracene among the measured PAHs showed the highest values. PAHs were positively correlated (P<0.01) to trace metals measured in a previous study.     

Relationship between leaf life-span and photosynthetic activity of Quercus ilex in polluted urban areas (Rome)

Anatomical, morphological and physiological leaf traits of Quercus ilex in response to different traffic levels (high traffic level, type A sites; average traffic level, type B sites; control sites, type C sites) were analysed in Rome. Superficial leaf deposits were analysed comparing unwashed and washed leaf samples. Washing lowered Pb 61% in A, 54% in B and 27% in C. Sr, Fe, Cu, Zn and Al showed the same trend as Pb. The higher photosynthetic activity of 1-year-old leaves (Pn=7.0+/-2.9 micromol m(-2 )s(-1), average value) in A sites with respect to B sites (6.7+/-2.4 micromol m(-2 )s(-1)) and C sites (6.7+/-1.8 micromol m(-2 )s(-1)) seems to be related to higher stomatal conductance (g(s)=0.13+/-0.06 mol m(-2 )s(-1)), higher total chlorophyll content (Chl=1.57 mg g(-1)) and higher leaf thickness (L(T)=218.9 microm), particularly palisade parenchyma thickness (109.4 microm). Q. ilex showed, on average, 95% of 1-year-old leaves and rarely 2-year-old leaves in A and B sites; 77% 1-year leaves, 20% previous-year leaves and sporadic 3-year leaves in C sites. The enhanced leaf senescence in A sites is compensated by a stimulated shoot production (18% higher with respect to C sites); 25% increased specific leaf area seems to be compensatory growth occurring in order to increase the size of the assimilatory area. The inverse trend of leaf life-span and Pn seems to be Q. ilex' adaptive strategy in polluted areas.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.     

PAHs associated with the leaves of Quercus ilex L.: Extraction,GC–MS analysis,distribution and sources: Assessment of air quality in the Palermo (Italy) area

In this study, the leaves of Quercus ilex L. were selected as possible bioaccumulators of polycyclic aromatic hydrocarbons (PAHs). Quercus is an evergreen plant that occurs widely in both urban and rural areas. Several sites (urban roadside, urban, urban park, suburban and rural) in and around Palermo city were investigated.The purpose of this research was to optimize analytical method for quercus leaves, investigate the degree of contamination in the urban area of Palermo by comparing PAH concentration in leaves of quercus from the several sites, establish distribution patterns and relate them to possible sources of PAHs. To this aim, the 16 recommended as priority pollutants by the Environmental Protection Agency (EPA) and perylene were analyzed. PAHs were positively correlated to atmospheric particulate gravimetrically determined on filters aspiring a known volume of air in the various stations.The analyses have been performed by gas chromatography coupled to mass spectrometry (GC–MS) in selected ion monitoring (SIM) mode. The total PAH content in the samples ranged from 92 to 1454 μg kg⁻¹ d.w. The higher amounts of PAHs detected in leaves of quercus from the urban area of Palermo compared with the control site are diagnostic of air contamination, in particular in the zones with heavy traffic. The determination of PAHs in the leaves of quercus allows us, with very simple and fast procedures, to assess the quality of the air over a longer period, since PAHs are accumulated over the whole lifetime of the leaves, irrespective of atmospheric conditions at the moment of sampling.     

Photosynthetic responses to elevated CO(2) and O(3) in Quercus ilex leaves at a natural CO(2) spring

Photosynthetic stimulation and stomatal conductance (Gs) depression in Quercus ilex leaves at a CO(2) spring suggested no down-regulation. The insensitivity of Gs to a CO(2) increase (from ambient 1500 to 2000 micromol mol(-1)) suggested stomatal acclimation. Both responses are likely adaptations to the special environment of CO(2) springs. At the CO(2)-enriched site, not at the control site, photosynthesis decreased 9% in leaves exposed to 2x ambient O(3) concentrations in branch enclosures, compared to controls in charcoal-filtered air. The stomatal density reduction at high CO(2) was one-third lower than the concomitant Gs reduction, so that the O(3) uptake per single stoma was lower than at ambient CO(2). No significant variation in monoterpene emission was measured. Higher trichome and mesophyll density were recorded at the CO(2)-enriched site, accounting for lower O(3) sensitivity. A long-term exposure to H(2)S, reflected by higher foliar S-content, and CO(2) might depress the antioxidant capacity of leaves close to the vent and increase their O(3) sensitivity.     

Seasonal variations and trends in concentrations of filter-collected polycyclic aromatic hydrocarbons (PAH) and mutagenic activity in the San Francisco Bay area

Air monitoring in the San Francisco Bay Area was carried out to measure outdoor community air concentrations of polycyclic aromatic hydrocarbons (PAH) and mutagenic activity (mutagenicity) in particulate organic matter (POM). Monitoring began in 1979 and is currently conducted at six stations. PAH and mutagenicity tests were performed on organic extracts prepared from high volume (hi-vol) filters composited every four months, by meterological season. PAH were determined by high pressure liquid chromatography (HPLC) with fluorescence and ultraviolet detection. Mutagenicity was measured in the Ames Salmonella bioassay using strain TA98 with and without metabolic activation. The nine-year mean concentration of benzo(a)pyrene (BaP) was 0.4 ng/m3. The mutagenicity of this amount of BaP accounted for only about 0.2% of the observed mutagenicity in POM and other measured PAH accounted for even less. Concentrations of PAH and mutagenicity were three to nine times higher during the winter than during other seasons. Year-to-year wintertime trends in several PAH were also seen. Early in the 1980s, winter concentrations of BaP and benzo (g,h,i)perylene increased. However since the mid-1980's, their concentrations have fallen. The decrease in PAH concentrations may be the result of an increasing proportion of vehicles with relatively low organic emissions. In contrast to PAH, mutagenicity did not show significantly year-to-year time trends.     

Foliar antioxidant status of adult Mediterranean oak species (Quercus ilex L. and Q. pubescens Willd.) exposed to permanent CO2-enrichment and to seasonal water stress.

Foliar antioxidants were measured in adult individuals of holm oak (Quercus ilex L.) and white oak (Q. pubescens Willd.) growing in the field either within the vicinity of natural CO2 springs or at a nearby control site under ambient CO2, which had been previously exposed to either daily irrigation or no irrigation. In oak trees permanently exposed to elevated CO2 the activities of antioxidant enzymes tended to be lower and the ascorbate pool was larger and more in reduced form, suggesting an attenuation of the oxidative risk in the CO2-enriched trees. In the enriched individuals of both species. the imposition of water shortage significantly increased the size of the glutathione pool and the total superoxide dismutase activity in a species-specific manner. Moreover, water-stressed trees exposed to elevated CO2 tended to have higher catalase and ascorbate peroxidase activities than water-stressed control trees. Such changes may reflect the need for an enhanced compensatory effort when trees acclimated to elevated CO2 are exposed to oxidative stress-promoting environmental factors, such as water shortage.     

Temporal and spatial changes of PAH concentrations in Mytilus galloprovincialis from Ria de Vigo (NW Spain)

The aim of this study was to establish the temporal trends and spatial distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Ria de Vigo by means of studying the PAH burden in wild mussels. The samples were collected in eight sites along the margins of the Ria de Vigo during November from 1998 to 2008 and Polycyclic Aromatic Hydrocarbon contents were determined using high performance liquid chromatography–fluorescence derivatization (HPLC–FLD). Quality of chemical analysis was guaranteed by participation in QUASIMEME intercalibration exercises carried out during the period of analysis. The concentrations for the sum of 13 PAHs were in the range 24–480 μg/kg dw, typical of an urban and industrialized area (50–500 μg/kg dw) except for a punctual input in La Guía in 1998 that led to a concentration above 1,000 μg/kg dw. In general, the sites in the outermost section of the estuary (ría) showed the lowest values, with an increasing gradient in the medium and inner parts of the ría. Temporal patterns show, in general, a downward trend. The relative proportion of 3 and 4 ring PAHs also varies with the site, the former being predominant in the outermost area and the latter in the medium and inner parts of the ría. This is consistently related with the sources and processes taking place in different areas of the estuary.     

Diurnal variations of ozone and other pollutants in an urban area

A theoretical model is used to describe the diurnal variations of primary and secondary pollutants, with emphasis on ozone. This is done for an urban basin with anthropogenic sources of nitrogen oxides and hydrocarbons. We propose a scheme for the decomposition of aromatic compounds. According to this scheme, each aromatic molecule gives rise to six transfers of NO to NO₂ without consumption of odd oxygen. It is concluded that it is not a good approximation to represent urban hydrocarbon emissions by one single species, neither in short term (a few hours) nor multiday simulations. Species with both high and low reactivity ought to be included. We show that the nocturnal minimum in ozone often observed in urban areas, is mainly induced by gas chemistry. It is not a good approximation to omit the chemical development during the night-time in a theoretical analysis of urban photochemical pollution. Such an omission introduces errors also in the day-time chemistry. Application of constant dissociation rate coefficients over the day gives rise to false morning and evening ozone maxima.     

Temporal variability of airborne bacterial community structure in an urban area

Temporal airborne bacterial genetic community structure and meteorological factors were analysed above an urban area in the northwest of France from December 2003 to April 2004 with a sampling strategy considering different time intervals (from an hour to a month). Principal component analysis (PCA) of B-ARISA (Bacterial-Automated Ribosomal Intergenic Spacer Analysis) profiles revealed a hierarchy in the temporal variability of bacterial community: daily<weekly<seasonal. Co-inertia analysis between B-ARISA data and meteorological factors demonstrated the correlation between the seasonal variability in the bacterial community and climatic conditions such as temperature and relative humidity, whereas daily and weekly variability seemed likely to be managed by other factors such as anthropogenic activities.     

Trace metal contents in Parmelia caperata (L.) Ach. compared to bulk deposition,throughfall and leaf-wash fluxes in two holm oak forests in Montseny (NE Spain)

The metal concentrations of V, Cr, Co, Ni, Cu, Zn, Cd, Hg and Pb were analysed in distilled water extracts of Parmelia caperata and in bulk deposition, throughfall and an experimental in situ washing of leaves at two forests at Montseny (NE Spain) submitted to differential exposure to the industrial and traffic activities around Barcelona. Lichen concentrations of Zn, Cu, V, and Cd were higher at the site of greater exposure to pollutants. Consistently, there was higher dry deposition of these metals at the more exposed site. The order of abundance of trace metals in the lichen was similar to that in the deposition variables, although Pb and Cu had intermediate concentrations in the lichen but were very low in the deposition measurements. This indicated the higher affinity of Pb and Cu for the exchange sites in the lichen cell wall and the fact that lichens accumulated Pb for the last 12–18 y when emissions were much higher than today. The ability of Parmelia caperata to indicate the deposition of heavy metals, together with its easy sampling and handling, its broad distribution and its easy identification suggest that the lichen extract procedure described here could be used to establish gradients of atmospheric deposition of heavy metals at a general geographic level.     

A hybrid modeling approach to resolve pollutant concentrations in an urban area

A modeling tool that can resolve contributions from individual sources to the urban environment is critical for air-toxics exposure assessments. Air toxics are often chemically reactive and may have background concentrations originated from distant sources. Grid models are the best-suited tools to handle the regional features of these chemicals. However, these models are not designed to resolve pollutant concentrations on local scales. Moreover, for many species of interest, having reaction time scales that are longer than the travel time across an urban area, chemical reactions can be ignored in describing local dispersion from strong individual sources making Lagrangian and plume-dispersion models practical. In this study, we test the feasibility of developing an urban hybrid simulation system. In this combination, the Community Multi-scale Air Quality model (CMAQ) provides the regional background concentrations and urban-scale photochemistry, and local models such as Hybrid Single Particle Lagrangian Integrated Trajectory model (HYSPLIT) and AMS/EPA Regulatory Model (AERMOD) provide the more spatially resolved concentrations due to local emission sources. In the initial application, the HYSPLIT, AERMOD, and CMAQ models are used in combination to calculate high-resolution benzene concentrations in the Houston area. The study period is from 18 August to 4 September of 2000. The Mesoscale Model 5 (MM5) is used to create meteorological fields with a horizontal resolution of 1×1 km². In another variation to this approach, multiple HYSPLIT simulations are used to create a concentration ensemble to estimate the contribution to the concentration variability from point sources. HYSPLIT simulations are used to model two sources of concentration variability; one due to variability created by different particle trajectory pathways in the turbulent atmosphere and the other due to different flow regimes that might be introduced when using gridded data to represent meteorological data fields. The ensemble mean concentrations determined by HYSPLIT plus the concentrations estimated by AERMOD are added to the CMAQ calculated background to estimate the total mean benzene concentration. These estimated hourly mean concentrations are also compared with available field measurements.     

Trace element accumulation in the moss Hypnum cupressiforme Hedw. and the trees Quercus ilex L. and Pinus halepensis Mill. in Catalonia

We studied trace element accumulation in the moss Hypnum cupressiforme and the widely distributed Mediterranean trees Quercus ilex and Pinus halepensis located at increasing distances from the Barcelona Metropolitan Area. Hypnum cupressiforme, Quercus ilex and, to a somewhat lesser extent, Pinus halepensis, have proved to be adequate as possible accumulative monitoring species in relation to trace elements pollution. No significant effects of crown orientation were found. One-year old leaves generally accumulated more trace elements than current-year leaves. All the studied trace elements showed greatest concentrations in the Barcelona Metropolitan Area, with lead, cadmium and arsenic concentrations being especially high. In general, trace element concentrations in biomass were similar or higher than the values reported from other Mediterranean urban areas of Europe. The top soil-layer concentrations were also higher in the Barcelona Metropolitan Area indicating the existence of mechanisms of atmospheric deposition and/or concentration in the soil. The lower values of Pb of airborne origin relative to other elements such as Cd, Cu, Zn and Sb suggest that traffic exhausts are not the only important focus of pollutants in this area. The results of biomass concentrations and of enrichment factor of biomasses respect to bedrock and soils show that atmospheric inputs account for the higher trace element concentrations in the Barcelona Metropolitan Area.     

The cytotoxic effect of wastewater from the phosphoric gypsum depot on common oak (Quercus robur L.) and shallot (Allium cepa var. ascalonicum)

The effect of wastewater from a phosphoric gypsum depot on common oak, Quercus robur L., at cytogenetical level was studied. Allium-test was used as a control. The treatment of common oak seedlings with wastewater under laboratory conditions caused mitodepressive effect. Chromosome aberrations and mitotic irregularities were found. Cytogenetic analysis of common oak seedlings grown from acorns collected near the depot did not show changes in mitotic activity in comparison to control but the number of aberrations was higher than in control. In comparison to Alliumtest common oak was found to be more tolerant to wastewater from the phosphoric gypsum depot.     

Chemical composition of fogwater in an urban area: Strasbourg (France)

To investigate the acidity and to identify the predominant compounds, this work presents the chemical analysis of 18 fogwater samples collected during the year 1991 in Strasbourg, in the east of France. For each fog event, two droplet size categories (2-6 microm and 5-8 microm) have been separately collected and 16 ionic components have been analysed. These two fraction sizes were chosen because they correspond approximately to the size range that can penetrate the human lung and they may have possible health effects. The dominant species were NH4+, NO3-, SO4(2-) and Cl-, with a maximum level of 12,640, 17,270, 21,620 and 13,540 microeq litre(-1), respectively. For most of the fog events the highest concentrations of all analysed species were observed in the 2-6 microm droplets. pH values ranged between 2.79 and 5.70 and the fogwater acidity was governed by three strong acids, H2SO4, HNO3 and HCl and was partially neutralised by NH3 and probably by the presence of CaCO3 in the 'loess', which is the major constituent of soils in the upper Rhine valley. In other respects the acetate/formate ratio (methanoate/ethanoate), generally lower than 1, indicates an important pollution due to automobile exhaust, although the Pb concentrations are moderate due to the general use of unleaded gasoline in France since 1989.