Prediction of ozone concentration in ambient air using multivariate methods

Multivariate statistical methods including pattern recognition (Principal Component Analysis--PCA) and modeling (Multiple Linear Regression--MLR, Partial Least Squares--PLS, as well as Principal Component Regression--PCR) methods were carried out to evaluate the state of ambient air in Miskolc (second largest city in Hungary). Samples were taken from near the ground at a place with an extremely heavy traffic. Although PCA is not able to determine the significance of variables, it can uncover their similarities and classify the cases. PCA revealed that it is worth to separate day and night data because different factors influence the ozone concentrations during all day. Ozone concentration was modeled by MLR and PCR with the same efficiency if the conditions of meteorological parameters were not changed (i.e. morning and afternoon). Without night data, PCR and PLS suggest that the main process is not a photochemical but a chemical one.     

Forest ecosystems and the changing patterns of nitrogen input and acid deposition today and in the future based on a scenario

A global assessment of the impact of the anthropogenic perturbation of the nitrogen and sulfur cycles on forest ecosystems is carried out for both the present-day [1980-1990] and for a projection into the future [2040-2050] under a scenario of economic development which represents a medium path of development according to expert guess [IPCC IS92a]. Results show that forest soils will receive considerably increasing loads of nitrogen and acid deposition and that deposition patterns are likely to change. The regions which are most prone to depletion of soils buffering capacity and supercritical nitrogen deposition are identified in the subtropical and tropical regions of South America and Southeast Asia apart from the well known 'hotspots' North-Eastern America and Central Europe. The forest areas likely to meet these two risks are still a minor fraction of the global forest ecosystems, though. But the bias between eutrophication and acidification will become greater and an enhanced growth triggered by the fertilizing effects of increasing nitrogen input cannot be balanced by the forest soils nutrient pools. Results show increasing loads into forest ecosystems which are likely to account for 46% higher acid loads and 36% higher nitrogen loads in relation to the 1980-1990 situation. Global background deposition of up to 5 kg N ha-1 a-1 will be exceeded at more than 25% of global forest ecosystems and at more than 50% of forest ecosystems on acid sensitive soils. More than 33% of forest ecosystems on acid sensitive soils will receive acid loads which exceeds their buffering capacity. About 25% of forest areas with exceeded acid loads will receive critical nitrogen loads.     

Net carbon flux from agricultural ecosystems: methodology for full carbon cycle analyses

Agricultural ecosystems have the potential to sequester carbon in soils by altering agricultural management practices (i.e. tillage practice, cover crops, and crop rotation) and using agricultural inputs (i.e. fertilizers and irrigation) more efficiently. Changes in agricultural practices can also cause changes in CO2 emissions associated with these practices. In order to account for changes in net CO2 emissions, and thereby estimate the overall impact of carbon sequestration initiatives on the atmospheric CO2 pool, we use a methodology for full carbon cycle analysis of agricultural ecosystems. The analysis accounts for changes in carbon sequestration and emission rates with time, and results in values representing a change in net carbon flux. Comparison among values of net carbon flux for two or more systems, using the initial system as a baseline value, results in a value for relative net carbon flux. Some results from using the full carbon cycle methodology, along with US national average values for agricultural inputs, indicate that the net carbon flux averaged over all crops following conversion from conventional tillage to no-till is -189 kg C ha(-1) year(-1) (a negative value indicates net transfer of carbon from the atmosphere). The relative net carbon flux, using conventional tillage as the baseline, is -371 kg C ha(-1) year(-1), which represents the total atmospheric CO2 reduction caused by changing tillage practices. The methodology used here illustrates the importance of (1) delineating system boundaries, (2) including CO2 emissions associated with sequestration initiatives in the accounting process, and (3) comparing the new management practices associated with sequestration initiatives with the original management practices to obtain the true impact of sequestration projects on the atmospheric CO2 pool.     

UV-VIS spectroscopy of 2,4,6-trinitrotoluene-hydroxide reaction

Contamination of groundwater, surface water and soil by explosives has occurred at military sites throughout the world as a result of manufacture of explosive compounds, assembly of munitions, and deployment of explosives containing devices. Due to the adverse effects of explosives on humans and other natural receptors, a low cost means of decontaminating these areas of contamination is needed. Base-induced transformation of explosives has shown promise as a rapid, low cost, and minimally resource-intensive technology for detoxifying explosives in soil and water. In order to understand the reaction mechanism, a reaction mixture of 2:1:1 (water:2,4,6-trinitrotoluene (TNT):1 N KOH) was analyzed by UV/VIS spectrometry from 190 to 1,100 nm. Time course measurements were conducted at 25, 20, 15, and 12 degrees C. A factor analysis program was used to analyze the spectral data. Principal component analysis indicated that six principal components explained the spectra to within experimental error, with four factors explaining the majority of the variance. Test spectral vectors for four components were developed, including TNT, two intermediates, and the final product, and were tested against the abstract vectors. Two possible reaction mechanisms were suggested and tested to explain the spectral data.     

Chemical composition and ecophysiological responses of Empetrum nigrum to aboveground element application

Empetrum nigrum L. (crowberry) is one of the plants surviving near the Cu-Ni smelters in Finland and Russia. According to field observations, the fine roots of E. nigrum are situated below 40 cm depth and the root biomass is reduced in the polluted sites. This could cause a reduced root uptake of macronutrients and trace elements in the field and, therefore, the possible element uptake by aboveground parts of E. nigrum was studied in a greenhouse. Six different treatment solutions containing various heavy metal and macronutrient concentrations were applied to the stems and leaves of E. nigrum and the chemical composition and ecophysiological parameters were measured. Heavy metal concentrations in the leaves and stem bark, and Cu concentrations in the stems, increased with increasing metal concentrations in the spraying solutions. The bark and leaves had higher heavy metal concentrations than the stems of comparable age classes. The macronutrient and Mn concentrations in E. nigrum did not change significantly with increasing element concentrations in the spraying solution. Neither the stem water potential nor the leaf chlorophyll concentrations showed any clear response to element applications. Therefore, the element uptake by aboveground parts of E. nigrum was not confirmed by this study. However, there was a tendency to a decrease in CO2 exchange rate and increase in foliar abscisic acid content in plants treated with the highest element concentrations.     

Detection of organic pollutants in sandy soils via TDR and eigendecomposition

In this study, organic pollutants in sandy soils are detected using a time domain relectrometry (TDR) probe system and eigendecomposition technique. As a demonstration, four types of organic fluids (motor oil, diesel oil, methanol and ethanol) were examined. Samples were prepared with different combinations of deionized water and organic fluid contents. For each experiment, reflected signals were captured by an oscilloscope, and their characteristics were identified using eigendecomposition technique. Autoregressive modeling and singular value decomposition methods were utilized for calculating the eigenvalues. The most significant eigenvalues were then identified based on their relative magnitude. Experimental results indicated that the presented system is sensitive to both water and pore fluid organic contents. For saturated conditions, signature curves were determined for identification of organic and/or water contents in soil pore fluids.     

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.     

Oxidative dealkylation of five phenylurea herbicides by the fungus CunninghamellaechinulataThaxter

Microorganisms isolated from soil degrade phenylurea herbicides via two major pathways: (i) direct hydrolysis by an amidase leading to N,O-dimethylhydroxylamine, CO₂ and aniline¹ and (ii) N-dealkylation, which has been described as the first step in urea herbicide degradation by a variety of organisms including mammals, plants and microbial systems (for a review see reference 2).Until now no attempts have been made to investigate the mechanism of N-demethylation of substituted ureas in soil microorganisms, due to the instability of the N-hydroxymethyl intermediates. This reaction mechanism has only been described in detail in green plants^3–5. As among soil fungi Phycomycetes are known to demethylate phenylurea herbicides^6,7 this study has been made to identify intermediate hydroxymethyl compounds from urea herbicides, when incubated with the fungus $\text{Cunninghamella echinulata Thaxter}$.