Sulfate,chloride and fluoride retention in Andosols exposed to volcanic acid emissions

The continuous emissions of SO(2), HCl and HF by Masaya volcano, Nicaragua, represent a substantial source of atmospheric S-, Cl- and F-containing acid inputs for local ecosystems. We report on the effects of such acid depositions on the sulfate, chloride and fluoride contents in soils (0-40 cm) from two distinct transects located downwind from the volcano. The first transect corresponds to relatively undifferentiated Vitric Andosols, and the second transect to more weathered Eutric Andosols. These soils are exposed to various rates of volcanogenic acid addition, with the Vitric sites being generally more affected. Prolonged acid inputs have led to a general pH decrease and reduced exchangeable base cation concentrations in the Andosols. The concentrations of 0.5 M NH(4)F- and 0.016 M KH(2)PO(4)-extractable sulfate (NH(4)F-S and KH(2)PO(4)-S, respectively) indicate that volcanic S addition has increased the inorganic sulfate content of the Vitric and Eutric soils at all depths. In this process, the rate of sulfate accumulation is also dependent on soil allophane contents. For all soils, NH(4)F extracted systematically more (up to 40 times) sulfate than KH(2)PO(4). This difference suggests sulfate incorporation into an aluminum hydroxy sulfate phase, whose contribution to total inorganic sulfate in the Vitric and Eutric Andosols is estimated from approximately 34 to 95% and approximately 65 to 98%, respectively. The distribution of KH(2)PO(4)-extractable chloride in the Vitric and Eutric Andosols exposed to volcanic Cl inputs reveals that added chloride readily migrates through the soil profiles. In contrast, reaction of fluoride with Al and Fe oxyhydroxides and allophanes is an important sink mechanism in the Masaya Andosols exposed to airborne volcanic F. Fluoride dominates the anion distribution in all soil horizons, although F is the least concentrated element in the volcanic emissions and depositions. The soil anion distribution reflects preferential retention of fluoride over sulfate and chloride, and of sulfate over chloride. The primary acidifying agent of the Andosols subject to the volcanic acid inputs is HCl.     

An estimation of the spatial and temporal distribution of biogenic non-methane hydrocarbon emissions in Greece

The present study presents the first detailed inventory for non-methane hydrocarbon emissions from vegetation over Greece. The emission inventory, based on a Geographic Information System (GIS), has a spatial resolution of 5×5 km² and a time resolution of 1 h. For the area under study, the calculated yearly monoterpene emissions are higher than the corresponding isoprene ones. In addition to the methodology presented here, the CORINAIR methodology was also applied for the calculation of emission rates. This resulted in orders of magnitude differences in the calculated emission rates. The CORINAIR methodology is judged to lead to unrealistically high values of biogenic NMHC emission rates. The temperature dependence of the CORINAIR correction factors seems to affect most the emissions, together with grazing land emission factors.     

An application of a puff dispersion model on power plant emissions in Yatagan region, Turkey

The present paper describes the application of the CALMET meteorological model and CALPUFF plume dispersion model to the Yatagan district to study the impact of Yatagan Power Plant emissions on the SO₂ levels on December 2000 in the region. Results indicate that SO₂ concentrations over the city depend strongly on advected emissions from the power plant and on the local variation of the wind field and limited vertical mixing conditions. It is found that South Westerly and light winds and the night time surface inversion layers lead to accumulation of pollutants coming from the power plant over the Yatagan district. The results are compared with the observations obtained from Local Environmental Authorities of Mugla. The simulation results indicate that the maximum ground level concentrations were found northeast from the source, which agrees with the measurements, but differ in terms of magnitudes.     

Temporal variation of fluoride concentration in antlers of roe deer (Capreolus capreolus) living in an area exposed to emissions from iron and steel industry, 1948-2000

Temporal changes of environmental fluoride concentration in the industrialized area of Siegen, western Germany were assessed by studying the fluoride content of antlers (n=116) collected between 1948 and 2000 from the resident roe deer (Capreolus capreolus) population. During the analyzed period, major fluoride emission sources in the study area have been iron- and steelworks. Fluoride concentrations in the antlers ranged between 118 and 5428 mg/kg of bone ash. There was an overall increase in antler fluoride content from the late 1940s/early 1950s to the late 1950s/mid-1960s. Thereafter, antler fluoride levels overall steadily declined. For statistical analysis, the data were grouped into five periods (1948–1959, 1960–1969, 1970–1979, 1980–1989, and 1990–2000). Geometric mean fluoride concentrations of the samples ranged from 323 (period 1990–2000) to 2096 mg/kg of bone ash (period 1960–1969). Sample means for the periods 1980–1989 and 1990–2000, respectively, were always significantly lower than those of older samples. The decrease in antler fluoride concentrations during recent decades suggests a drop of ambient fluoride levels, that is hypothetically attributed to a reduction in the number of emission sources in the area and a decline of fluoride discharges from both local and more distant sources due to improved emission control measures. Comparison with antler fluoride data for other roe deer populations from western Germany further suggests that the roe deer from the Siegen area were recently exposed to an only moderate additional fluoride load from industrial sources. Studying antler fluoride concentrations is a convenient and cost-effective method of monitoring temporal changes in ambient fluoride levels.     

The application of predictive models in the environmental risk assessment of ECONOR

Environmental risk assessment of products requires information on the physico-chemical properties, persistence and ecotoxicity of the product, its constituents and possible metabolic and degradation products. Experimental investigations are usually required to generate this information and consequently risk assessment can be costly and time consuming. One possible approach to minimising the amount of experimental testing is to supplement experimental data with data predicted using models such as quantitative structure-activity relationships (QSARs). Using these models, information can be generated based primarily on the knowledge of the chemical structure of the substance(s) under investigation. In this study predictive models were used to assess the environmental risk of the veterinary medicine, ECONOR which contains the active ingredient valnemulin. Available experimental data on the properties, degradability and ecotoxicity of valnemulin was supplemented with predicted data. Where possible, experimental data was used to validate the predicted approaches and this indicated that the predictions were accurate. Information on usage, properties and degradability was input to fate models to predict environmental concentrations (PECs) of valnemulin in soil, pore water and groundwater. Comparison of PECs with experimental and predicted ecotoxicity data for valnemulin indicated that that even under 'worst case' scenarios the environmental risk posed by valnemulin was low.     

An assessment of operations of oil-exporting countries in terms of energy consumption and carbon dioxide emissions

Energy consumption and carbon dioxide emissions from 16 oil-exporting countries are studied using Data Envelopment Analysis using indicators representing economic growth, energy consumption and emissions. The analysis for 1996 shows that Norway, Gabon and Nigeria are efficient and that Russia is inefficient. Malmquist Productivity Index analysis shows that there is progress in achieving higher values of GDP and non-fossil fuel consumption and in achieving lower values of fossil fuel consumption and carbon emissions in the year 1996 when compared with 1992 for Norway, Russia, Mexico, Algeria, Libya, Gabon and Oman.     

An analysis of extinction coefficients of particles and water moisture in the stack after flue gas desulfurization at a coal-fired power plant

Two important factors that affect in-stack opacity--light extinction by emitted particles and that by water moisture after a flue gas desulfurization (FGD) unit--are investigated. The mass light extinction coefficients for particles and water moisture, k(p) and k(w), respectively, were determined using the Lambert-Beer law of opacity with a nonlinear least-squares regression method. The estimated k(p) and k(w) values vary from 0.199 to 0.316 m2/g and 0.000345 to 0.000426 m2/g, respectively, and the overall mean estimated values are 0.229 and 0.000397 m2/g, respectively. Although k(w) is 3 orders of magnitude smaller than k(p), experimental results show that the effect on light extinction by water moisture was comparable to that by particles because of the existence of a considerable mass of water moisture after a FGD unit. The mass light extinction coefficient was also estimated using Mie theory with measured particle size distributions and a complex refractive index of 1.5-ni for fly ash particles. The k(p) obtained using Mie theory ranges from 0.282 to 0.286 m2/g and is slightly greater than the averaged estimated k(p) of 0.229 m2/g from measured opacity. The discrepancy may be partly due to a difference in the microstructure of the fly ash from the assumption of solid spheres because the fly ash may have been formed as spheres attached with smaller particles or as hollow spheres that contained solid spheres. Previously reported values of measured k(p) obtained without considering the effects of water moisture are greater than that obtained in this study, which is reasonable because it reflects the effect of extinction by water moisture in the flue gas. Additionally, the moisture absorbed by particulate matter, corresponding to the effect of water moisture on the particulates, was clarified and found to be negligible.     

The role of multiple regression and exploratory data analysis in the development of leukemia incidence risk models for comparison of radionuclide air stack emissions from nuclear and coal power industries

Risks associated with power generation must be identified to make intelligent choices between alternate power technologies. Radionuclide air stack emissions for a single coal plant and a single nuclear plant are used to compute the single plant leukemia incidence risk and total industry leukemia incidence risk. Leukemia incidence is the response variable as a function of radionuclide bone dose for the six proposed dose response curves considered. During normal operation a coal plant has higher radionuclide emissions than a nuclear plant and the coal industry has a higher leukaemia incidence risk than the nuclear industry, unless a nuclear accident occurs. Variation of nuclear accident size allows quantification of the impact of accidents on the total industry leukemia incidence risk comparison. The leukemia incidence risk is quantified as the number of accidents of a given size for the nuclear industry leukemia incidence risk to equal the coal industry leukemia incidence risk. The general linear model is used to develop equations that relate the accident frequency required for equal industry risks to the magnitude of the nuclear emission. Exploratory data analysis revealed that the relationship between the natural log of accident number versus the natural log of accident size is linear.     

An operational assessment of the application of the relative reduction factors in the demonstration of attainment of the 8-hr ozone National Ambient Air Quality Standard

The U.S. Environmental Protection Agency in 1997 revised the 1-hr ozone (O3) National Ambient Air Quality Standard (NAAQS) to one based on an 8-hr average, resulting in potential nonattainment status for substantial portions of the eastern United States. The regulatory process provides for the development of a state implementation plan that includes a demonstration that the projected future O3 concentrations will be at or below the NAAQS based on photochemical modeling and analytical techniques. In this study, four photochemical modeling systems, based on two photochemical models, Community Model for Air Quality and the Comprehensive Air Quality Model with extensions, and two emissions processing models, Sparse Matrix Optimization Kernel for Emissions and Emissions Modeling System, were applied to the eastern United States, with emphasis on the northeastern Ozone Transport Region in terms of their response to oxides of nitrogen and volatile organic carbon-focused controls on the estimated design values. With the 8-hr O3 NAAQS set as a bright-line test, it was found that a given area could be termed as being in or out of attainment of the NAAQS depending upon the modeling system. This suggests the need to provide an estimate of model-to-model uncertainty in the relative reduction factor (RRF) for a better understanding of the uncertainty in projecting the status of an area's attainment. Results indicate that the model-to-model differences considered in this study introduce     

The sensitivity of the CHIMERE model to emissions reduction scenarios on air quality in Northern Italy

The sensitivity of the CHIMERE model to emission reduction scenarios on particulate matter PM2.5 and ozone (O₃) in Northern Italy is studied. The emissions of NO_x, PM2.5 SO₂, VOC or NH₃ were reduced by 50% for different source sectors for the Lombardy region, together with 5 additional scenarios to estimate the effect of local measures on improving the air quality for the Po valley area. Firstly, we evaluate the model performance by comparing calculated surface aerosol concentrations for the standard case (no emission reductions) with observations for January and June 2005. Calculated monthly mean PM10 concentrations are in general underestimated. For June, modelled PM10 concentrations slightly overestimate the measurements. Calculated monthly mean SO₄, NO₃^?, NH₄⁺ concentrations are in good agreement with the observations for January and June. Secondly, the model sensitivity of emission reduction scenarios on PM2.5 and O₃ calculated concentrations for the Po valley area is evaluated. The most effective scenarios to abate PM2.5 concentration are based on the SNAP2 (non-industrial combustion plants) and SNAP7 (road traffic) sectors, for which the NO_x and PM2.5 emissions are reduced by 50%. The number of days that the 2015 PM2.5 limit value of 25 μg m^?3 in Milan is exceeded by reducing primary PM2.5 and NO_x emissions for SNAP2 and 7 by 50%, does not change in January when compared to the standard case for the Milan area. It appears that 40% of the PM2.5 concentration in the greater Milan area is caused by the emissions surrounding the Lombardy region and from the model boundary conditions.This study also showed that a more effective pollutant reduction (emissions) per ton of pollutant reduced (concentrations) for the greater Milan area is obtained by reducing the primary PM2.5 emissions for SNAP7 by 50%. The most effective scenario on PM2.5 decrease for which precursor emissions are reduced is achieved by reducing SO₂ emissions by 50% for SNAP7.Our study showed that during summer time, the largest reductions in O₃ concentrations are achieved for SNAP7 emission reductions, when volatile organic compounds (VOCs) are reduced by 50%.     

Changes in levels of essential elements in suckling rats exposed to zinc and mercury

The effect of mercury and its interaction with zinc on the content of essential metals in tissues from neonate rats was investigated. Three-day-old Wistar rats were treated with saline or 27 mg kg(-1)d(-1) ZnCl2 (s.c.) for five consecutive days. From the 8th to the 12th day of life, the rats received one daily dose of saline or 5.0 mg kg(-1) HgCl2 (s.c). Twenty-four hours after the last injection liver, kidneys and blood were collected for metal quantification. The HgCl(2) exposure induced alterations on metal levels, such as increase of Fe, Hg and Zn in liver, decrease of Fe and Mg and increase of Cu and Hg contents in kidneys. The Hg exposure also increased Hg levels in the blood. The treatment with ZnCl2, administered previously to HgCl2, partially prevented the increase of Fe in the liver, and not only prevented the decrease of renal Mg but also increased it to levels higher than those found in control group. The Zn-Hg rats also presented higher renal Cu levels, and showed partially lower blood and hepatic Hg levels and higher renal Hg levels. The pre-administration of Zn caused no severe alterations in levels of essential metals (Cu, Fe, Mg and Mn). In short, Zn appears to be an alternative treatment of Hg poisoning in young animals in comparison to chelating drugs since these have low metal selectivity.     

The use of olive-mill waste compost to promote the plant vegetation cover in a trace-element-contaminated soil

The applicability of a mature compost as a soil amendment to promote the growth of native species for the phytorestoration of a mine-affected soil from a semi-arid area (SE Spain), contaminated with trace elements (As, Cd, Cu, Mn, Pb and Zn), was evaluated in a 2-year field experiment. The effects of an inorganic fertiliser were also determined for comparison. Bituminaria bituminosa was the selected native plant since it is a leguminous species adapted to the particular local pedoclimatic conditions. Compost addition increased total organic-C concentrations in soil with respect to the control and fertiliser treatments, maintained elevated available P concentrations throughout the duration of the experiment and stimulated soil microbial biomass, while trace elements extractability in the soil was rather low due to the calcareous nature of the soil and almost unaltered in the different treatments. Tissue concentrations of P and K in B. bituminosa increased after the addition of compost, associated with growth stimulation. Leaf Cu concentration was also increased by the amendments, although overall the trace elements concentrations can be considered non-toxic. In addition, the spontaneous colonisation of the plots by a total of 29 species of 15 different families at the end of the experiment produced a greater vegetation cover, especially in plots amended with compost. Therefore, the use of compost as a soil amendment appears to be useful for the promotion of a vegetation cover and the phytostabilisation of moderately contaminated soils under semi-arid conditions.     

An assessment of the aggregate impacts of the proposed reduction in the motor fuels tax in the United States

The analysis in this paper examines the impact of reducing the excise tax on gasoline and diesel fuel on the United States economy. The analytical approach used consists of a computable general equilibrium model composed of fourteen producing sectors, fourteen consuming sectors, six household categories classified by income and the government. The effects of a 4.3 cents per gallon reduction in the excise tax on gasoline and diesel fuel on prices and quantities are examined. The results suggest, for example, that a decrease in the tax would result in higher output by the producing sectors (by about $2.86 billion), and expansion in the consumption of goods and services (by about $3.48 billion), and an increase in welfare (by about $3.59 billion). The government would realise a decrease in revenue of about $2.37 billion. When subjected to a sensitivity analysis, the results are reasonably robust with regard to the assumption of the values of the substitution elasticities.     

A design of two simple models to predict PCDD/F concentrations in vegetation and soils

The vegetation and soil levels of the 17 polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) toxic congeners were calculated by means of a vegetation and a soil model, respectively. Both models predicted the levels of the 17 PCDD/F congeners in quite good agreement with the observed results although the soil model was more accurate than the vegetation model. Four different pathways of contribution to the vegetation concentrations were taken into account: vapour-phase absorption, dry particle deposition, wet particle deposition and uptake by root. The most important pathway was the vapour-phase absorption and the less was the uptake by root. In the soils model four pathways were considered: background soil concentration, dry particle deposition, wet particle deposition and uptake by root. After the background concentration, the most important pathway was the wet deposition.     

Overview and assessment of techniques to measure ammonia emissions from animal houses: the case of the Netherlands

In order to comply with the ammonia (NH(3)) emission reduction assigned to the Netherlands development of new measures are needed, which should be supported by fast and accurate measurements to arrive at new estimates of the NH(3) emission from each agricultural source. This paper gives an overview of the current methods used in the Netherlands to measure NH(3) emissions from animal houses, and provides alternative methods for some particular situations. For mechanically ventilated animal houses, passive flux samplers placed in the ventilation shafts of the animal house are presented as alternative to measure a larger number of animal houses (replicates) with the same housing system at a low price. For naturally ventilated animal houses, when mixing in the animal house is not good enough to allow measurements within the animal house (internal tracer gas ratio method), two measurement methods are discussed: the Gaussian plume dispersion model, which is usually not suitable for agricultural situations, and the flux frame method, which is not always applicable because of distortion of the flow around the building. Finally, for animal houses with outside yards for the animals, there are at this moment no methods available to measure the NH(3) emissions from these complex situations, although quick box methods (for the outside yards) and a combination of a backward Lagrangian stochastic model with open-path concentration measurements with a tunable diode laser (TDL), look promising.     

Comparing lifetime emissions of natural gas and conventional fuel vehicles: an application of the generalized ANCOVA model

New regulations and incentives are encouraging the use of clean, alternative fuel vehicles (AFVs) in urban areas. These vehicles are seen as one option for reducing air pollution from mobile sources. However, because of the limited number of AFVs on the road, little is known about actual lifetime emissions characteristics of in-use AFVs. This study describes the use of a generalized analysis of covariance model to evaluate and compare the emissions from natural gas vehicles with emissions from reformulated gasoline vehicles. The model describes fleet-wide emissions deterioration, while also accounting for individual vehicle variability within the fleet. This ability to measure individual vehicle variability can then be used to provide realistic bounds for the emissions deterioration in individual vehicles and the fleet as a whole. In order to illustrate the use of the model, the carbon monoxide, oxides of nitrogen (NOx), non-methane hydrocarbon (NMHC), and carbon dioxide emissions characteristics of a fleet of dedicated natural gas Dodge Ram vans and a fleet of dedicated reformulated gasoline Dodge Ram vans operating in the U.S. government fleet are explored. The analysis demonstrates the utility of the statistical method and suggests a potential for natural gas Dodge Ram vans to be generally cleaner than their conventional fuel counterparts. However, in the case of NOx and NHMCs, the analysis also suggests that these emissions benefits might be reduced over the vehicle lifetime due to higher emissions deterioration rates for natural gas vehicles. As this paper is aimed at illustrating the analysis of the covariance model, the results reported herein should be considered within the context of a more comprehensive study of these data before general conclusions are possible. Generalization of these findings to other vehicle models and alternative fuel technologies is not justified without further study.     

Relation between ozone levels and NOx and VOC emissions in the Sao Paulo Metropolitan Area for an episode of August, 1998

At present, major efforts in air pollution control for urban areas are oriented to reduce ozone levels to below standards. Models are a useful tool for air quality assessment and they can help to select the best strategy plan to reduce ozone levels in a polluted area. Like other large cities in the world, Sao Paulo Metropolitan Area (SPMA) has registered high levels of ozone and particulate matter for several decades. In order to establish appropriate strategy plans, a photochemical model has been used for an episode that occurred in 1999. Simple emission control strategies have been examined.     

Atmospheric deposition of PCDD/Fs near an old municipal solid waste incinerator: levels in soil and vegetation

The levels of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in soil and vegetation samples taken from 24 sites in the vicinity of an old municipal solid waste incinerator (San Adrià del Besòs, Barcelona, Spain). Duplicate samples were collected within a radius of 3 km from the stack. PCDD/F concentrations in soils ranged from 1.22 to 34.28 ng I-TEQ/kg (d.m.) with median and mean values of 9.06 and 12.24 ng I-TEQ/kg, respectively. In turn, the levels of PCDD/Fs in vegetation samples ranged from 0.33 to 1.98 ng I-TEQ/kg (d.m.), with median and mean values of 0.58 and 0.70 ng I-TEQ/kg, respectively. Although the present PCDD/F concentrations in soil samples were higher than those recently found in soils taken near other incinerators from Catalonia, they are of the same order of magnitude than the levels of these pollutants found in incinerators from other countries. By contrast, the concentrations of PCDD/Fs in herbage samples were comparable to those found in recent surveys carried out in Catalonia.     

Dioxin analysis in stack emissions, slags and the wash water circuit during high-temperature incineration of chlorine-containing industrial wastes; Part 2

PCB's and polychlorobenzene sumps have been incinerated in a high-temperature installation. The working conditions, wastes, sampling methods and analysis of the stack emissions, slag and wash water are described. No 2,3,7,8-TCDD and only ppt-traces of some PCDD congeners were detected in the stack emission. The performance criteria of the incinerator and the more important sampling procedures are discussed.     

Fate of imidacloprid in soil and plant after application to cotton seeds

This study aimed to investigate the persistence of imidacloprid in soil after application to cotton seeds and to obtain a complete picture on the mass balance of this compound in soil and cotton plants. The study was carried out as a pot culture experiment under laboratory conditions using a Gaucho formulation containing ¹⁴C-labeled imidacloprid. Three treatments of cotton seeds were made in sandy loamy soil: live seeds grown in autoclaved soil, dead seeds put in live soil and live seeds grown in live soil. Results showed that total ¹⁴C recoveries decreased by time ranging 93.8–96.2, 77.1–88.4 and 53.5–62.4% of the applied radioactivity at 7, 14, and 21 d after application, respectively. The reduction in the extracted ¹⁴C from soil coincided with the increase of non-extracted ones. Levels of bound ¹⁴C was always less in autoclaved soil than in live ones. Results revealed also that only 1.8–6.8% of the applied ¹⁴C was taken up by the plants and fluctuated within the test period. ¹⁴C levels were higher in plants grown in autoclaved soil than those in live ones and the radioactivity tended to accumulate on the edges of cotton leaves. Most of the radioactivity in the soil extracts was identified as unchanged ¹⁴C-imidacloprid.