Environmental and lifestyle factors affect benzene uptake biomonitoring of residents near a petrochemical plant

Background

We monitored urinary benzene excretion to examine factors affecting benzene uptake in a sample of the general population living near a petrochemical plant.

Methods

Our study population included 143 subjects: 33 petrochemical plant workers (W) with low level occupational benzene exposure; 30 residents in a small town 2 km from the plant (2kmR); 26 residents in a second small town located 2 to 4 km from the plant (4kmR); and 54 urban residents 25 km from the plant (25kmR). Exposure to benzene was evaluated by personal air sampling during one work-shift for the W group, and from 8.00 to 20:00 for general population subgroups, and by urinary benzene (BEN-U).

Results

Median airborne benzene exposure was 25, 9, 7 and 6 μg/m³ benzene among the W, 2kmR, 4kmR, and 25kmR subgroups, respectively; the highest level was found among the workers, while there was no significant difference among the other groups. Median BEN-U was 2 to 14-fold higher in smokers compared to non-smokers; among non-smokers BEN-U was the highest in W (median 236 ng/L), and lower in the 2kmR (48 ng/L) and 4kmR (63 ng/L) subgroups than in the 25kmR (120 ng/L) subgroup. A multiple linear regression analysis, explaining up to 73% of BEN-U variability, confirmed that active smoking and airborne benzene most strongly affected BEN-U. Among the non-smoking, non-occupationally exposed study subjects, a positive association was found between BEN-U and the distance of residence from the plant. This association was explained by increased exposure to urban traffic emissions in the study group residing at a greater distance from the plant. Environmental tobacco smoke had a marginally positive role.

Conclusion

Among factors affecting benzene uptake in non-occupationally exposed individuals, urban residence contributes to benzene exposure more than residing in close proximity to a petrochemical plant.     

Evidence for enhanced dissipation of chlorpyrifos in an agricultural soil inoculated with Serratia rubidaea strain ABS 10

The insecticide ¹⁴C-chlorpyrifos was found mineralized in a Tunisian soil with repeated exposure to it. From this soil, a bacterial strain was isolated that was able to grow in a minimal salt medium (MSM) supplemented with 25 mg L^?1 of chlorpyrifos. It was characterized as Serratia rubidaea strain ABS 10 using morphological and biochemical analyses, as well as 16S rRNA sequencing. In a liquid culture, the S. rubidaea strain ABS 10 was able to dissipate chlorpyrifos almost entirely within 48 h of incubation. Although the S. rubidaea strain ABS 10 was able to grow in an MSM supplemented with chlorpyrifos and dissipate it in a liquid culture, it was not able to mineralize ¹⁴C-chlorpyrifos. Therefore, it can be concluded that the dissipation capability of this bacteria might be attributed to its capacity to adsorb CHL. It can also be ascribed to other reasons such as the formation of biogenic non-extractable residues. In both non-sterile and sterile soil inoculated with S. rubidaea strain ABS 10, chlorpyrifos was more rapidly dissipated than in controls with DT₅₀ of 1.38 and 1.05 days, respectively.

     

Trace metals used as natural markers for discriminating some karstic freshwaters near Trieste (Italy)

Some heavy metals have been determined using voltammetry in freshwaters forming part of a karstic hydrological system (the Timavo River, north of Trieste), during attempts to characterize and discriminate the different sources of the springs. The trace elements can be considered natural markers, with lead appearing to be the most discriminating variable. Non parametric statistics and cluster analysis were used to estimate the significance of the determined parameters with respect to the considered ecosystem.     

Soil-air exchange of organochlorine pesticides in the Southern United States

Soil samples were collected from 30 farms in Alabama, Louisiana and Texas during 1999-2000 to determine residues of organochlorine pesticides (OCPs). One or more of the DDT compounds (p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, o,p'-DDE) was above the quantitation limit (0.1 ng g(-1) dry weight) in every soil, and toxaphene was above the quantitation limit (3 ng g(-1)) in 26 soils. Chlordanes, dieldrin and hexachlorocyclohexane (HCH) isomers occurred less frequently (quantitation limits 0.1 ng g(-1) for dieldrin and 0.05 ng g(-1) for chlordanes and HCHs). OCPs were measured in air at 40 cm above the soil at selected farms to investigate soil-air partitioning. Concentrations of OCPs in air were positively and significantly (P<0.001-0.004) correlated to soil concentrations for toxaphene, p,p'-DDT, o,p'-DDT, p,p'-DDE, dieldrin, and trans-nonachlor. The regression was weaker (P=0.022) for cis-chlordane and not significant for trans-chlordane (P=0.43) nor gamma-HCH (P=0.80). Approach to soil-air equilibrium was assessed by calculating fugacities in the soil and air (f(s) and f(a)) for samples with quantifiable residues in both compartments. The fugacity fraction f(s)=0.5 at equilibrium and is <0.5 or >0.5 for net deposition and net volatilisation, respectively. Fugacity fractions varied greatly for different soil-air pairs, reflecting generally disequilibrium conditions. Mean fugacity fractions indicated near-equilibrium for some OCPs (p,p'-DDE, chlordanes, trans-nonachlor and dieldrin) and net volatilisation for others (p,p'-DDT, o,p'-DDT, toxaphene, gamma-HCH). Chiral analysis showed that enantioselective degradation of (+) or (-) o,p'-DDT in soil was accompanied by enrichment or depletion of the corresponding enantiomers in the overlying air, although there appeared to be some dilution by racemic o,p'-DDT from regional air transport.     

Contribution of vehicular traffic and industrial facilities to PM10 concentrations in a suburban area of Caserta (Italy)

PM10 levels have been recorded in the suburban area of Caserta (Italy) from February to October 2012. The daily limit was exceeded in 13 % of the determinations, with no significant difference between weekdays and weekends. Benzo[a]pyrene concentrations were in the range 0.01–0.46 ng/m³, thus, never exceeding the National Standard. The B(a)P-eq was 0.20 ng/m³. PM10 peaks were associated with wind from east–northeast. The same was observed for Ca concentrations, whereas no relation with wind direction was observed for organic pollutants. The results point to a local limestone quarry and cement factory as the likely major source of PM10 pollution in the area investigated.     

Vulnerability and risk evaluation of agricultural nitrogen pollution for Hungary's main aquifer using DRASTIC and GLEAMS models

In recent years, the significant improvement in point source depuration technologies has highlighted problems regarding, in particular, phosphorus and nitrogen pollution of surface and groundwater caused by agricultural non-point (diffuse) sources (NPS). Therefore, there is an urgent need to determine the relationship between agriculture and chemical and ecological water quality.This is a worldwide problem, but it is particularly relevant in countries, such as Hungary, that have recently become members of the European Community. The Italian Foreign Ministry has financed the PECO (Eastern Europe Countries Project) projects, amongst which is the project that led to the present paper, aimed at agricultural sustainability in Hungary, from the point of view of NPS. Specifically, the aim of the present work has been to study nitrates in Hungary's main aquifer. This study compares a model showing aquifer intrinsic vulnerability to pollution (using the DRASTIC parameter method; Aller et al. [Aller, L., Truman, B., Leher, J.H., Petty, R.J., 1986. DRASTIC: A Standardized System for Evaluating Ground Water Pollution Potential Using Hydrogeologic Settings. US NTIS, Springfield, VA.]) with a field-scale model (GLEAMS; Knisel [Knisel, W.G. (Ed.), 1993. GLEAMS—Groudwater Leaching Effects of Agricultural Management Systems, Version 3.10. University of Georgia, Coastal Plain Experimental Station, Tifton, GA.]) developed to evaluate the effects of agricultural management systems within and through the plant root zone. Specifically, GLEAMS calculates nitrate nitrogen lost by runoff, sediment and leachate.Groundwater monitoring probes were constructed for the project to measure: (i) nitrate content in monitored wells; (ii) tritium (³H) hydrogen radioisotope, as a tool to estimate the recharge conditions of the shallow groundwater; (iii) nitrogen isotope ratio δ¹⁵N, since nitrogen of organic and inorganic origin can easily be distinguished.The results obtained are satisfactory, above all regarding the DRASTIC evaluation method, which is shown to satisfactorily explain both low and high aquifer vulnerability, and furthermore proves to be a good tool for zoning hydrogeological regions in terms of natural system susceptibility to pollution. The GLEAMS model, however, proves not to be immediately usable for predictions, above all due to the difficulty in finding sufficient data for the input parameters. It remains a good tool, but only after an accurate validation, for decision support systems, in the specific case to integrate intrinsic vulnerability, from DRASTIC (or similar methods), with land use nitrate loads from GLEAMS, or similar methods.The PECO project has proved a positive experience to highlight the fundamental points of a decision support system, aimed to mitigate the nitrate risk for groundwater coming from Hungarian agricultural areas.     

Reduced activity of alkaline phosphatase due to host–guest interactions with humic superstructures

Nuclear Magnetic Resonance (NMR) spectroscopy was applied to directly study the interactions between the alkaline phosphatase enzyme (AP) and two different humic acids from a volcanic soil (HA-V) and a Lignite deposit (HA-L). Addition of humic matter to enzyme solutions caused signals broadening in ¹H-NMR spectra, and progressive decrease and increase of enzyme relaxation (T₁ and T₂) and correlation (τ_C) times, respectively. Spectroscopic changes were explained with formation of ever larger weakly-bound humic–enzyme complexes, whose translational and rotational motion was increasingly restricted. NMR diffusion experiments also showed that the AP diffusive properties were progressively reduced with formation of large humic–enzyme complexes. The more hydrophobic HA-L affected spectral changes more than the more hydrophilic HA-V. ¹H-NMR spectra also showed the effect of progressively greater humic–enzyme complexes on the hydrolysis of an enzyme substrate, the 4-nitrophenyl phosphate disodium salt hexahydrate (p-NPP). While AP catalysis concomitantly decreased NMR signals of p-NPP and increased those of nitrophenol, addition of humic matter progressively and significantly slowed down the rate of change for these signals. In agreement with the observed spectral changes, the AP catalytic activity was more largely inhibited by HA-L than by HA-V. Contrary to previous studies, in which humic–enzyme interactions were only indirectly assumed from changes in spectrophotometric behavior of enzyme substrates, the direct measurements of AP behavior by NMR spectroscopy indicated that humic materials formed weakly-bound host–guest complexes with alkaline phosphatase, and the enzyme catalytic activity was thereby significantly inhibited. These results suggest that the role of extracellular enzymes in soils may be considerably reduced when they come in contact with organic matter dissolved in the soil solution.     

Influence of fenamidone, indoxacarb, pyraclostrobin, and deltamethrin on the population of natural yeast microflora during winemaking of two sardinian grape cultivars

The influence of fenamidone ((S)-1-anilino-4-methyl-2-methylthio-4-phenylimidazolin-5-one), pyraclostrobin (methyl 2-[1-(4-chlorophenyl)pyrazol-3-yloxymethyl]-N-methoxycarbanilate), indoxacarb (methyl 7-Chloro-2,5-dihydro-2-[[(methoxycarbonyl) [4- (trifluoromethoxy) phenyl] amino] carbonyl] indeno[1,2-e][1,3,4] oxadiazine-4a(3H)-carboxylate), and deltamethrin ([cyano-[3-(phenoxy)phenyl]methyl] 3-(2,2-dibromoethenyl)-2,2-dimethylcyclopropane-1-carboxylate) on spontaneous fermentation carried out by natural yeast grapes microflora, was studied during the wine-making process. Aliquots of pesticide standard solutions were added to the grapes before crushing, to reach a concentration equal or half the maximum residue limit (MRL). Vinifications were performed, with maceration (R), or without maceration (W). During the wine-making process, samples were taken at the beginning (one hour after grapes crushing), at the middle and at the end of the spontaneous fermentation process. At half the MRL concentration, deltamethrin affected Pichia sp. population with a decrease of almost 50 %, while fenamidone decreased Candida sp., Candida stellata at 83, and 36%, respectively. Metschnikowia pulcherrima population decreased in all samples when compared to the control. Experiments at MRL levels showed a strong reduction for all non-Saccharomyces yeast species, when grapes had been treated with pyraclostrobin, fenamidone, and deltamethrine, except for Candida sp. which was found to have been affected only by fenamidone residues. Growth zone inhibition test showed only an in vitro activity of pyraclostrobin over Kloeckera spp., C. stellata, and M. pulcherrima. Microvinification experiments produced wines with no differences concerning S. cerevisiae population as well as production of ethanol and residual sugars. Experiments showed that at the end of the fermentation process pesticides were adsorbed by the lees and grape skins, and no pesticides residue was detectable in wine.     

Modification of Sulfur Dioxide Injury to Tobacco and Tomato by Varying Nitrogen and Sulfur Nutrition

The body of information presented in this paper is directed to plant scientists who are concerned with factors which modify the susceptibility of plants to air pollutants.

Tobacco and tomato plants grown in sand-solution culture with varying levels of nitrogen or sulfur were exposed to injurious levels of sulfur dioxide. Plants of both species which were deficient in either nutrient exhibited decreased susceptibility to the gas compared with plants grown at optimal levels of each nutrient. Foliage of these plants was also found to have increased stomatal resistance as measured by a porometer and decreased total sulfur accumulations. Plants grown at optimum levels of each nutrient showed increased susceptibility over that of the deficient plants. Stomatal resistance was lower and sulfur accumulation was greater than in the deficient plants. At the supra-optimal nitrogen and sulfur levels, there were differences in susceptibility. Over-abundant nitrogen appeared to decrease susceptibility whereas over-supplies of sulfur increased it.

The response of plants with deficient or optimal supplies of either nutrient might be explained by the effects of nutrition on stomatal activity and hence on ability to absorb SO₂S from the atmosphere, mineral deficiency being known to increase stomatal resistance, and mineral sufficiency, to decrease stomatal resistance by virtue of increased efficiency of water use. The difference in response between plants overfertilized with respect to nitrogen or sulfur is explained by the fact that sulfur is both nutrient and phytotoxicant at the same time. Having already been oyersupplied with sulfur by absorption from the nutrient substrate, the high-sulfur plants were unable to withstand additional sulfur accumulation from the atmosphere and hence were more severely injured.

Increased carbohydrate accumulation in the nitrogen- and sulfur-deficient plants might play an additional role in protection from SO2-injury.