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.     

Seasonal patterns of non-terpenoid C6-C10 VOC emission from seven Mediterranean woody species

The seasonal pattern of non-terpenoid C6-C10 VOC emission by seven Mediterranean woody species (Bupleurum fruticosum, Cistus albidus, Pinus halepensis, Arbutus unedo, Erica arborea, Quercus coccifera, and Q. ilex) was studied under field conditions. Branch chamber samples were sorbed on carbotrap and analyzed by thermal desorption in combination with GC-MS. These non-terpenoid C6-C10 VOC emissions were large, almost of similar magnitude to those of terpenes. Overall, maximum values were recorded in spring and summer (up to 12 microg g(-1) DM h(-1) in Q. ilex) and minimum values in autumn and winter (up to 5 microg g(-1) DM h(-1) in Q. ilex). These C6-C10 VOC emissions represented 2.82% of the photosynthetic C fixation in summer and 0.22% in winter. Some compounds such as 2-ethoxyethyl acetate were emitted by most species, others such as 3-hexen-1-ol, phenol or decanal were significantly emitted only by few species. The greatest diversity of emitted non-terpenoid C6-C10 VOCs was observed in spring and in Q. ilex. Temperature seemed a strong driver of these seasonal changes but other species-specific and seasonal factors seem involved. These results indicate that C6-C10 non-terpenoid VOCs contribute a rather significant fraction of the total biogenic VOC flux from these Mediterranean species, especially in spring and summer, and therefore should be considered in VOC emission inventories and in model predictions of tropospheric chemistry.     

Food sources of arsenic in pregnant Mediterranean women with high urine concentrations of this metalloid

Seafood consumption provides a significant amount of arsenic, although in its organic, nontoxic forms. Mediterranean populations may incorporate high levels of this metalloid as a consequence of seafood consumption. In the present study, the significance of this input among pregnant women from a Mediterranean city (Sabadell, Catalonia, Spain) is assessed. Total urinary arsenic was analyzed in 489 pairs of urine samples, corresponding to the 12th and 32th weeks of pregnancy. Association of arsenic content with seafood and other dietary items were studied. Geometric mean concentrations were 34 and 37 μg/g creatinine during the first and third trimesters, respectively. The observed concentrations were similar to those reported in studies from other Mediterranean countries. The differences between both periods were not statistically significant. The only dietary factor significantly and positively associated with total urinary arsenic in both series of samples was seafood, particularly lean fish. Moreover, lean fish consumption during both periods was found to be the main determinant for differences in levels of arsenic between the first and third trimesters, which confirms the association between high levels of total urinary arsenic and seafood consumption.     

Measurement of arsenic compounds in littoral zone algae from the Western Mediterranean Sea. Occurrence of arsenobetaine

The determination of arsenic compounds in algae collected on the Catalan coast (Western Mediterranean) is reported. Ten algae species and the seagrass Posidonia oceanica were analyzed. Total arsenic in the samples was determined by microwave digestion and inductively coupled plasma mass spectrometry (ICPMS). Arsenic speciation in water extracts of samples was analyzed by liquid chromatography with both anionic and cationic exchange with ICPMS detection (LC-ICPMS). The total arsenic content of the algae samples ranged from 2.96 to 39.0mg As kg(-1). The following compounds were detected: arsenite (As(III)), arsenate (As(V)), methylarsonate (MA), dimethylarsinate (DMA), sulfonate sugar (SO3-sug), sulfate sugar (SO4-sug), phosphate sugar (PO4-sug), arsenobetaine (AB), arsenocholine (AC), trimethylarsine oxide (TMAO) and glycerol sugar (Gly-sug). The main arsenic species found were arsenosugars. Significant percentages of arsenobetaine (0.54 mg As kg(-1), 28% of the extractable arsenic and 0.39 mg As kg(-1), 18% of the extractable arsenic) were found in Ulva rigida and Enteromorpha compressa. These results are discussed in relation to the presence of epiphytes.     

Comparison of arsenic content in pelletized poultry house waste and biosolids fertilizer

Managers of human biosolids have been incorporating the practice of waste pelletization for use as fertilizer since the mid 1920s, and waste pelletization has recently been embraced by some poultry producers as a way to move nutrients away from saturated agricultural land. However, the presence of arsenic in pelletized poultry house waste (PPHW) resulting from the use of organoarsenical antimicrobial drugs in poultry production raises concerns regarding additional incremental population exposures. Arsenic concentrations were determined in PPHW and pelletized biosolids fertilizer (PBF) samples. Pellets were processed using strong acid microwave digestion and analyzed by graphite furnace atomic absorption spectroscopy. The mean arsenic concentration in PPHW (20.1 ppm) fell within the lower part of the range of previously report arsenic concentrations in unpelletized poultry house waste. Arsenic concentrations in PBF, the source of which is less clear than for PPHW, were approximately a factor of 5 times lower than those in PPHW, with a mean concentration of 4.1 ppm. The pelletization and sale of these biological waste fertilizers present new pathways of exposure to arsenic in consumer populations who would otherwise not come into contact with these wastes. Arsenic exposures in humans resulting from use of these fertilizer pellets should be quantified to avoid potential unintended negative consequences of managing wastes through pelletization.     

Comparison of toxicological impacts of integrated and chemical pest management in Mediterranean greenhouses

The goal of this paper is to assess the relative impacts of pest-control methods in greenhouses, based on current LCA tools. As a case study, the relative impacts of two tomato production methods, chemical pest management (CPM) and integrated pest management (IPM), are assessed. The amount of the active ingredients applied, the fate of the ingredients in the various greenhouse and environmental compartments, the human exposure routes via the various compartments and the inherent toxicity of the ingredients were taken into account in the relative impact calculations. To assess the importance of model selection in the assessment, pesticide-specific fate and exposure factors for humans and aquatic and terrestrial ecosystems, used to aggregate pesticide emissions, were calculated with two different models: (1) the USES-LCA model, adapted in order to calculate the pesticide transfer from greenhouse air and soil to fruits, and (2) the empirical model critical surface time (CST). Impact scores have in general shown a higher level of potential contamination in greenhouses treated with CPM compared to IPM (a factor of 1.4 to 2.3). Relative impacts have been shown highly dependent on the selection of specific pesticides and crop stage development at the moment of pesticide application. This means that both CPM and IPM could be improved by a careful selection of pesticides. In order to improve the relative impact calculations, future research in pesticide transfer to food will be necessary.     

Comparison of solubility databases used for HLW performance assessment

Elemental solubility limits are employed in many performance assessment studies of the disposal of high-level radioactive waste. A comparison of solubility databases used in a number of recent assessments from Canada, Finland, Japan, Sweden, Switzerland and the U.S.A. is presented. Despite similarities in the chemical conditions under which such solubilities are defined, there are very large ranges in the values selected for most elements (several orders of magnitude). In some cases, differences in solubilities can be attributed to differences in the thermodynamic databases used but, due to generally incomplete documentation, both of such databases and the criteria for data selection, detailed analysis of the reason for such discrepancies is precluded. A key factor, however, is the fairly subjective choice of the solid phase considered to be “solubility-limiting”. Procedures are recommended which would increase the transparency of solubility database compilation in future analyses.     

Comparison of in vivo and in vitro methodologies for the assessment of arsenic bioavailability in contaminated soils

An in vivo swine assay was utilised for the determination of arsenic (As) bioavailability in contaminated soils. Arsenic bioavailability was assessed using pharmacokinetic analysis encompassing area under the blood plasma-As concentration time curve following zero correction and dose normalisation. In contaminated soil studies, As uptake into systemic circulation was compared to an arsenate oral dose and expressed as relative As bioavailability. Arsenic bioavailability ranged from 6.9+/-5.0% to 74.7+/-11.2% in 12 contaminated soils collected from former railway corridors, dip sites, mine sites and naturally elevated gossan soils. Arsenic bioavailability was generally low in the gossan soils and highest in the railway soils, ranging from 12.1+/-8.5% to 16.4+/-9.1% and 11.2+/-4.7% to 74.7+/-11.2%, respectively. Comparison of in vivo and in vitro (Simplified Bioaccessibility Extraction Test [SBET]) data from the 12 contaminated soils and bioavailability data collected from an As spiked soil study demonstrated that As bioavailability and As bioaccessibility were linearly correlated (in vivo As bioavailability (mgkg(-1))=14.19+0.93.SBET As bioaccessibility (mgkg(-1)); r(2)=0.92). The correlation between the two methods indicates that As bioavailability (in vivo) may be estimated using the less expensive, rapid in vitro chemical extraction method (SBET) to predict As exposure in human health risk assessment.     

Comparison of models used for the determination of odor thresholds

Several methods of data analysis used for the evaluation of odor detection thresholds have been examined through application to two samples of n-butanol. Panels of seven-ten people, working with a six level, IITRI, ternary forced choice olfactometer, were presented with initial concentrations of 99.5 and 52.1 ppm n-butanol during three trials. The ranking-plotting and ASTM E-679 methods were applied to the evaluation of discrimination-recognition thresholds of the odorous samples. It was found that single evaluations of detection or discrimination-recognition thresholds by either method were always ± 50%of the mean of six trials.The effects of successful guessing on the magnitudes of detection thresholds were examined in terms of a model based on the principle of maximum likelihood estimation of one, two and three trials of panel response. The magnitude of the discrimination threshold obtained by this method always fell between the detection and discrimination-recognition thresholds evaluated by the currently used models. The mean discrimination threshold of n-butanol for six trials was found to be 0.65 ± 0.25 ppm. It appears that the magnitude obtained from one trial with seven panel members would be sufficiently reliable for regulatory purposes when only one field sample is available, since any subsequent trials did not produce threshold values better than ± 40 % of the mean of six tests involving seven and ten panel members exposed to two different initial concentrations.     

Comparison of real-time instruments used to monitor airborne particulate matter

Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakersfield, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 microns (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of approximately 3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.     

Autoradiographic studies of ethylenediurea distribution in woody plants

Carbon-14-labelled ethylenediurea (EDU), synthesised from diethylenetriamine and (14)C-urea, was stem-injected into 2-year-old seedlings of sugar maple, white ash, flowering dogwood and flowering crabapple. At time intervals ranging from 1 h to 42 days after treatment, macroautoradiographs of leaf, stem and root tissue were made to determine relative distribution patterns of labelled chemical. Translocation of (14)C-EDU was very rapid and predominantly acropetal, especially after the first few hours. Maximum quantities of (14)C were found in leaf tissue approximately 7-10 days following injection, after which the intensity of the labelled chemical declined over the remainder of the study (42 days). Distribution patterns of (14)C-EDU were correlated with observed levels of protection afforded most plants when the chemical is injected 7 days before fumigation with ozone.     

Effects of arsenic on nitrate metabolism in arsenic hyperaccumulating and non-hyperaccumulating ferns

This study investigated the effects of arsenic on the in vitro activities of the enzymes (nitrate reductase and nitrite reductase) involved in nitrate metabolism in the roots, rhizomes, and fronds of four-month old Pteris vittata (arsenic – hyperaccumulator) and Pteris ensiformis (non-arsenic--hyperaccumulator) plants. The arsenic treatments (0, 150, and 300 μM as sodium arsenate) in hydroponics had adverse effects on the root and frond dry weights, and this effect was more evident in P. ensiformis than in P. vittata. Nitrate reductase and nitrite reductase activities of arsenate-treated plants were reduced more in P. ensiformis than in P. vittata. This effect was accompanied by similar decreases in tissue NO₃^? concentrations. Therefore, this decrease is interpreted as being indirect, i.e., the consequence of the reduced NO₃^? uptake and translocation in the plants. The study shows the difference in the tolerance level of the two Pteris species with varying sensitivity to arsenic.     

Effects of pollutants on laccase activities of Marasmius quercophilus, a white-rot fungus isolated from a Mediterranean schlerophyllous litter

Marasmius quercophilus is a white-rot fungus involved in carbon recycling in Mediterranean ecosystems because of its laccase production. Here we described the effect of metal ions and halide salts, on laccase activity in order to point out the action of such environmental pollutants on this enzyme of major importance. Furthermore we tested organic solvent effects on laccase reaction since reaction mixture including solvent can be used in the transformation of xenobiotics. In the case of metal ions, we found that chloride ions were responsible for inhibition while CuSO(4) and MnSO(4) enhanced laccase activity. When halides were tested, we showed the following degree of inhibition: F(-)>Cl(-)>Br(-). Furthermore we found that I(-) was oxidized by laccase with I(2) as the product of the reaction. With ABTS, 50% of the laccase activity remains for solvent concentration ranging from 40% to 60% depending on the solvent used while with syringaldazine solvent concentration ranged from 50% to 70%. The organic solvent effects observed were probably a result of enzyme denaturation and of both enhancement of oxidised product solubilisation and of substrate solubilisation (for syringaldazine). These results show that laccase from M. quercophilus is not rapidly inhibited by certain environmental pollutants which sustains its role in carbon turnover under pertubation. However the strong effect of chloride ion on laccase activity should be further investigated with in situ studies since this could drastically influence carbon recycling in litters from Mediterranean littoral locations.     

Effects of plant arsenic uptake and heavy metals on arsenic distribution in an arsenic-contaminated soil

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200mg kg(-1) Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8weeks using NH(4)Cl (water-soluble plus exchangeable, WE-As), NH(4)F (Al-As), NaOH (Fe-As), and H(2)SO(4) (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8weeks of plant growth, the Al-As and Fe-As fractions were significantly (p<0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p=0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic.     

Comparison of models used for national agricultural ammonia emission inventories in Europe: Litter-based manure systems

Six N-flow models, used to calculate national ammonia (NH₃) emissions from agriculture in different European countries, were compared using standard data sets. Scenarios for litter-based systems were run separately for beef cattle and for broilers, with three different levels of model standardisation: (a) standardized inputs to all models (FF scenario); (b) standard N excretion, but national values for emission factors (EFs) (FN scenario); (c) national values for N excretion and EFs (NN scenario). Results of the FF scenario for beef cattle produced very similar estimates of total losses of total ammoniacal-N (TAN) (±6% of the mean total), but large differences in NH₃ emissions (±24% of the mean). These differences arose from the different approaches to TAN immobilization in litter, other N losses and mineralization in the models. As a result of those differences estimates of TAN available at spreading differed by a factor of almost 3. Results of the FF scenario for broilers produced a range of estimates of total changes in TAN (±9% of the mean total), and larger differences in the estimate of NH₃ emissions (±17% of the mean). The different approaches among the models to TAN immobilization, other N losses and mineralization, produced estimates of TAN available at spreading which differed by a factor of almost 1.7. The differences in estimates of NH₃ emissions decreased as estimates of immobilization and other N losses increased. Since immobilization and denitrification depend also on the C:N ratio in manure, there would be advantages to include C flows in mass-flow models. This would also provide an integrated model for the estimation of emissions of methane, non-methane VOCs and carbon dioxide. Estimation of these would also enable an estimate of mass loss, calculation of the N and TAN concentrations in litter-based manures and further validation of model outputs.     

Effect of arsenic on chloroplast ultrastructure and calcium distribution in arsenic hyperaccumulator Pteris vittata L

This study investigated the impacts of arsenic (As) on the chloroplast ultrastructure and calcium (Ca) distribution in Chinese brake (Pteris vittata L.) mainly by histochemical methods, with an emphasis on the possible function of Ca in As detoxification and accumulation in P. vittata. P. vittata was grown in an artificially contaminated soil added with different concentrations of Na(2)HAsO(4) (0, 100, 300 and 800 mg kg(-1) As dry soil) for 24 weeks in a greenhouse. The addition of As did not affect the chloroplast ultrastructure of young pinna, meanwhile most of the membrane systems of chloroplasts in mature pinna were severely damaged under high As condition. Calcium concentration in the fronds of P. vittata was not significantly affected by the addition of As, but Ca concentration in the mature pinna significantly increased by As addition, consistent with the position appearing As toxicity. When no As was added, most of calcium precipitates distributed around the inner membrane of vacuole. But when the pinna appeared plasmolysis, more calcium precipitates resided outside the cell membrane and bigger particles evenly distributed in the cytoplasm. All the results indicated that Ca had a close relation with As toxicity in P. vittata.     

Relation of dietary inorganic arsenic exposure and urinary inorganic arsenic metabolites excretion in Japanese subjects

Inorganic arsenic (InAs) is a ubiquitous metalloid that has been shown to exert multiple adverse health outcomes. Urinary InAs and its metabolite concentration has been used as a biomarker of arsenic (As) exposure in some epidemiological studies, however, quantitative relationship between daily InAs exposure and urinary InAs metabolites concentration has not been well characterized. We collected a set of 24-h duplicated diet and spot urine sample of the next morning of diet sampling from 20 male and 19 female subjects in Japan from August 2011 to October 2012. Concentrations of As species in duplicated diet and urine samples were determined by using liquid chromatography-ICP mass spectrometry with a hydride generation system. Sum of the concentrations of urinary InAs and methylarsonic acid (MMA) was used as a measure of InAs exposure. Daily dietary InAs exposure was estimated to be 0.087 µg kg^?1 day^?1 (Geometric mean, GM), and GM of urinary InAs+MMA concentrations was 3.5 ng mL^?1. Analysis of covariance did not find gender-difference in regression coefficients as significant (P > 0.05). Regression equation Log ₁₀ [urinary InAs+MMA concentration] = 0.570× Log ₁₀ [dietary InAs exposure level per body weight] + 1.15 was obtained for whole data set. This equation would be valuable in converting urinary InAs concentration to daily InAs exposure, which will be important information in risk assessment.     

二段铁盐沉淀深度脱除高浓度含砷废水中的砷

探索高浓度含砷废水中砷的深度脱除方法及脱除机理。采用预氧化-二段铁盐沉淀的方法脱除炼铅烟尘浸出液中的砷,研究影响砷脱除效率的控制条件和因素,砷脱除机理。结果表明,用双氧水氧化原料液中的低价铁和砷,加FeCl3调节铁砷比=1,在pH=4~5、T=60~70℃反应60 min,砷的脱除率达到99.95%,XRD分析结果表明,沉淀物为非晶态砷酸铁形态;在二段除砷中,控制铁砷比=5、pH=7~8,除砷后液中的砷含量小于0.014 mg/L,远低于允许的排放限值。采用二段铁盐脱砷工艺可以将高砷溶液中的砷深度脱除。     

Testing the resistance of fullerenes to chemothermal oxidation used to isolate soots from environmental samples

We tested the resistance of five different fullerenes (C₆₀, C₇₀, C_76/78 mix, and C₈₄) to chemothermal oxidation at 375 °C (CTO-375), a method that has been used and tested for quantifying black carbon (BC) and CNTs in soils and sediments. C₆₀ survived CTO-375 the most (50%), while C₇₀ was the fullerene with the lowest survival rate (<1%). Standard additions of C₆₀ to soil and sediment reference materials yielded recoveries between 18 and 36%. Although lower than recoveries previously observed for soot and CNTs, these results demonstrate the capability of CTO-375 to partially isolate C₆₀ from solid environmental matrices. Standard additions of C₇₀, C_76/78, and C₈₄ yielded slightly higher survival rates when added to soil and sediment than in their pure form. These results indicate that the mineral matrices of these samples probably had a catalytic effect towards C₆₀ and a protective effect towards C₇₀, C_76/78, and C₈₄ during CTO-375.