Critical levels for ozone effects on vegetation in Europe

The evidence of detrimental effects of ozone on vegetation in Europe, and the need to develop international control policies to reduce ozone exposures which are based on the effects of the pollutant, has led to attempts to define so-called critical levels of ozone above which adverse effects on trees, crops and natural vegetation may occur. This review is a critical assessment of the scientific basis of the concepts used to define critical levels for ozone and identifies the key limitations and uncertainties involved. The review focuses on the Level I critical level approach, which provides an environmental standard or threshold to minimise the effects of ozone on sensitive receptors, but does not seek to quantify the impacts of exceeding the critical level under field conditions. The concept of using the AOT (accumulated exposure over a threshold) to define long-term ozone exposure is demonstrated to be appropriate for several economically important species. The use of 40 ppb (giving the AOT40 index) as a threshold concentration gives a good linear fit to experimental data from open-top chambers for arable crops, but it is less certain that it provides the best fit to data for trees or semi-natural communities. Major uncertainties in defining critical level values relate to the choice of response parameter and species; the absence of data for many receptors, especially those of Mediterranean areas; and extrapolation to field conditions from relatively short-term open-top chamber experiments. The derivation of critical levels for long-lived organisms, such as forest trees, may require the use of modelling techniques based on physiological data from experimental studies. The exposure-response data which have been applied to derive critical levels should not be used to estimate the impacts of ozone over large areas, because of the uncertainties associated with extrapolation from the open-top chamber method, especially for forest trees, and because of spatial variation in atmospheric and environmental conditions, which may alter ozone uptake.     

Gas/particle partitioning behaviour of azaarenes in an urban atmosphere

The gas/particle partitioning of azaarenes in the Liverpool urban atmosphere was measured from May 1995 to April 1996. This period included one of the hottest summers and coldest winters recorded in the UK. The changes of the relative proportions of particulate and vapour phases showed a strong seasonal variation in which over 80% of azaarene compounds are associated with the particles in the winter and over 60% of azaarene compounds exist as vapour phase during the summer. The results are fitted into a gas/particle partitioning equation. Calculated vapour pressures, vaporization and desorption enthalpies are also given. Azaarene partitioning behaviour is modelled at a variety of aerosol concentrations and over a temperature range which includes normal ambient temperatures. It is hypothesised that three ring azaarene species are more likely to undergo changes in the relative proportions of particle and vapour phase material than either two or four ring compounds.     

Particle size relationships at the Fresno Supersite

Aerosol size distributions are presented for a winter intensive study at the Fresno Supersite. The size distributions were consistent with and predictive for continuous PM2.5 measured by beta attenuation. They varied temporally with respect to source type and intensity, with the smallest mean diameters associated with high NOx concentrations during weekday morning rush hours. Conversely, small and large particle and black carbon (BC) concentrations were higher during Sunday and weekday evenings in response to traffic and residential wood combustion emissions. Ambient PM2.5 light scattering (Bsp) was precisely but systematically underestimated during winter, probably because of heating in the sample shelter.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).     

Investigation of new indirect spectrophotometric method for the determination of carbofuran in carbamate pesticides

A new spectrophotometric method has been investigated for the determination of Carbofuran pesticide. The method was based on the hydrolysis of the pesticides. The hydrolyzed products, methylamine on reaction with sodium nitroprusside solution in acetone medium gives a purple colored solution. The absorbance of the resulting solution was measured at 530 nm. Conditions for the complete hydrolysis of pesticides and quantitative determination of methylamine were optimized. From the standard calibration plot of methylamine, the amount of pesticides was calculated. The amount of active ingredients in commercial products was determined from the amount of methylamine found. It was observed that lower concentration of the active ingredients were present in the commercial products. The limit of detection and quantification was calculated and found to be 0.804 and 2.68 ppm respectively.     

Glutathione S-transferase cytosolic isoform in the pink-shrimp, Farfantepenaeus brasiliensis, from Conceição Lagoon, Santa Catarina Island, SC, Brazil

Contaminant input into the environment can affect the biochemical responses of exposed organisms. Activity of conjugation enzymes, such as glutathione S-transferase (GST) has been proposed as a biomarker of susceptibility to the presence of potentially damaging xenobiotics. The aim of the present study was to evaluate the activity of total and Pi-class GST in the hepatopancreas of pink-shrimp Farfantepenaeus brasiliensis. The shrimp were caught at a single site at Concei??o Lagoon and transplanted to another site (Canto da Lagoa - CA) in the same lagoon, and to the laboratory (LAB), where they were kept for 15 days. This experiment was carried out in winter 2003 and in summer 2004. Shrimp were sampled before the exposure, at a zero time (t0), and after 15-days at CA site and LAB. The activity of total GST and Pi-isoform were analyzed using CDNB and ethacrynic acid (EA) as substrates, respectively. Shrimp caught in winter showed higher levels of Pi-class GST than those caught in summer, for both t0 and CA groups. Moreover, differences in the activity of this GST isoform between groups were observed only in winter, where the animals from t0 and CA groups presented higher activity when compared to those kept in the laboratory. This difference could be associated either to changes in the contaminant input or to other water quality parameters in this ecosystem. The elevated GST Pi activity observed in the shrimp of both t0 and CA groups sampled in winter could be related to salinity, since it was higher in winter than in summer. We could also suggest a possible association of this finding to a seasonal metabolic variation in this penaeid. If that is the case, one should take into account these alterations when considering the use of this GST isoform as biomarker in F. brasiliensis in environmental monitoring programs.     

Factors impacting on pharmaceutical leaching following sewage application to land

Sewage effluent application to land is a treatment technology that requires appropriate consideration of various design factors. Soil type, level of sewage pre-treatment and irrigation rate were assessed for their influence on the success of soil treatment in removing pharmaceuticals remaining after conventional sewage treatment. A large scale experimental site was built to assess treatment performance in a realistic environment. Of the factors investigated, soil type had the biggest impact on treatment performance. In particular, carbamazepine was very efficiently removed (>99%) when irrigated onto a volcanic sandy loam soil. This was in contrast to irrigation onto a sandy soil where no carbamazepine removal occurred after irrigation. Differences were likely caused by the presence of allophane in the volcanic soil which is able to accumulate a high level of organic matter. Carbamazepine apparent adsorption distribution coefficients (K(d)) for both soils when irrigated with treated sewage effluent were determined as 25 L kg(-1) for the volcanic soil and 0.08 L kg(-1) for the sandy soil. Overall, a volcanic soil was reasonably efficient in removing carbamazepine while soil type was not a major factor for caffeine removal. Removal of caffeine, however, was more efficient when a partially treated rather than fully treated effluent was applied. Based on the investigated pharmaceuticals and given an appropriate design, effluent irrigation onto land, in conjunction with conventional sewage treatment may be considered a beneficial treatment for pharmaceutical removal.     

Unusual products of the aqueous chlorination of atenolol

The reaction of the drug atenolol with hypochlorite under conditions that simulate wastewater disinfection was investigated. The pharmaceutical reacted in 1h yielding three products that were separated by chromatographic techniques and characterized by spectroscopic features. Two unusual products 2-(4-(3-(chloro(2-chloropropan-2-yl)amino)-2-hydroxypropoxy)phenyl) acetamide and 2-(4-(3-formamido-2-hydroxypropoxy)phenyl) acetamide were obtained along with 2-(4-hydroxyphenyl) acetamide. When the reaction was stopped at shorter times only 2-(4-(3-amino-2-hydroxypropoxy)phenyl) acetamide and the dichlorinated product were detected. Tests performed on the seeds of Lactuca sativa show that chlorinated products have phytotoxic activity.     

Associations of fat mass and lean mass with bone mineral density differ by levels of persistent organic pollutants: National Health and Nutrition Examination Survey 1999-2004

Persistent organic pollutants (POPs), xenobiotics that accumulate in fat tissue, may impair bone metabolism. We studied (1) the association of bone mineral density (BMD) with POPs and (2) whether associations of fat mass (FM) or lean mass (LM), two components of body composition, with BMD differed depending on levels of POPs. Participants aged ?20 in the National Health and Nutrition Examination Survey 1999-2004 were included (n = 2769). Eight POPs with detection rate ?80% and three skeletal subregions (left arm, pelvis, and right leg) were selected. All analyses were stratified by gender and age (cutpoint 50 years or more). POPs at background concentrations were mostly unassociated with BMD. However, the associations of FM and LM with BMD depended on POPs concentrations, in particular with BMD of the left arm (usually not weight-bearing) in postmenopausal women. When POPs concentrations were low, FM showed inverse associations with BMD while LM showed positive associations. However, when POPs levels were high, FM showed positive associations with BMD while the positive associations between LM and BMD weakened. POPs may biologically modify the associations of FM and LM with BMD, especially among postmenopausal women, possibly explaining inconsistent associations between FM and BMD in previous epidemiological studies.     

Bacterial stimulation of copper phytoaccumulation by bioaugmentation with rhizosphere bacteria

Copper contaminated areas pose environmental health risk to living organisms. Remediation processes are thus required for both crop production and industrial activities. This study employed bioaugmentation with copper resistant bacteria to improve phytoremediation of vineyard soils and copper mining waste contaminated with high copper concentrations. Oatmeal plant (Avena sativa L.) was used for copper phytoextraction. Three copper resistant bacterial isolates from oatmeal rhizosphere (Pseudomonas putida A1; Stenotrophomonas maltophilia A2 and Acinetobacter calcoaceticus A6) were used for the stimulation of copper phytoextraction. Two long-term copper contaminated vineyard soils (Mollisol and Inceptisol) and copper mining waste from Southern Brazil were evaluated. Oatmeal plants substantially extracted copper from vineyard soils and copper mining waste. As much as 1549 mg of Cu kg?1 dry mass was extracted from plants grown in Inceptisol soil. The vineyard Mollisol copper uptake (55 mg Cu kg?1 of dry mass) in the shoots was significantly improved upon inoculation of oatmeal plants with isolate A2 (128 mg of Cu kg?1 of shoot dry mass). Overall oatmeal plant biomass displayed higher potential of copper phytoextraction with inoculation of rhizosphere bacteria in vineyard soil to the extent that 404 and 327 g ha?1 of copper removal were respectively observed in vineyard Mollisol bioaugmented with isolate A2 (S. maltophilia) and isolate A6 (A. calcoaceticus). Results suggest potential application of bacterial stimulation of phytoaccumulation of copper for biological removal of copper from contaminated areas.