Natural and anthropogenic sources and fate of atmospheric ethylene

This study attempted to estimate the amount of ethylene emitted into the atmosphere from natural and anthropogenic sources and to determine the fate of atmospheric ethylene. The total emission from the global surface was estimated to be 18–45 × 10⁶ t y⁻¹, of which 74% was released from natural sources and 26% from the anthropogenic sources. Releases from the terrestial and aquatic ecosystems comprised 89 and 11% of the natural emissions, respectively. Biomass burning in terrestial ecosystems to clear land for agriculture was the largest anthropogenic source (77%); the combustion of various fossil fuels amounts to only a small fraction (21%) of anthropogenic emissions. The relative amounts of ethylene destroyed by reactions with OH radical and O₃ in the troposphere were estimated to be 89 and 8%, respectively. The remaining 3% of the atmospheric ethylene was transported into the stratosphere. The atmospheric lifetime of ethylene was estimated to be between 2 and 4 days. We discuss the possibility that degradation by bacteria in the soil is a sink of atmospheric ethylene. The physiological effects of elevated ethylene concentrations on plants because of large-scale destruction of the terrestial ecosystem by forest fires is also discussed.     

Physico-chemical speciation and transformation reactions of particulate atmospheric nitrogen and sulphur compounds

Using X-ray powder diffraction it is possible to identify a number of discrete compounds of nitrogen and sulphur in atmospheric aerosols. The compounds observed include ammonia neutralization products of airborne acids, including mixed ammonium nitrate-sulphate salts. Products of hydrogen halide displacement by HNO₃ and H₂SO₄ are identified both from size-differentiated ion balance studies and X-ray diffraction. A number of mixed metal-ammonium sulphate salts are attributed to reactions of ammonium sulphate subsequent to aerosol coagulation processes.     

Study of aluminium distribution and speciation in atmospheric particles of different diameters in Nanjing,China

Aluminium (Al) is one of the trace inorganic metals present in atmospheric particles. Al speciation study is essential to better evaluate the mobility, availability, and persistence of trace Al and Al species in the atmosphere. This paper reports Al distribution and speciation in atmospheric particles with aerodynamic diameters >10.0, 10.0–2.5 and <2.5 μm in the urban area of Nanjing, China. Urban particles were collected with a high-volume sampling system equipped with a cascade impactor, which effectively separates the particulate matter into three size ranges. Particulate Al was fractionated into five different forms (insoluble, oxide, organic, carbonate, and exchangeable species) by the modified five-step Tessier's sequential extraction procedure. The main points are as follows: (1) The average levels of Al in PM_2.5, PM_2.5–10 and PM_>10 are 2.02±0.35, 3.04±0.43 and 6.32±0.76 μg m⁻³, respectively, with PM_2.5, PM_2.5–10 and PM_>10 constituting respectively, 17.8±3.1%, 26.7±3.8% and 55.5±6.7% of suspended particulate matter (SPM) mass (11.38 μg m⁻³). (2) The vertical profile of airborne Al in the above three size fractions has been estimated. A significant increase in airborne Al concentrations was found for PM_2.5, PM_2.5–10 and PM_>10 as the sampling height above the ground increased from 2.5 to 17.5 m; however, there was an obvious decrease in airborne Al concentrations between 17.5 and 40.0 m. The maximum mean of total Al in PM_2.5, PM_2.5–10 and PM_>10 occurred between 12.5 and 20.0 m above the ground. (3) The distribution of Al speciation was studied. It was found that the size distribution of airborne Al species followed the order: insoluble species>oxide species>organic species>carbonate species>exchangeable species.     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

燃煤过程中微量元素砷和硒形态转化的热力学平衡模拟

砷和硒是煤中的易挥发有毒微量元素。由于砷和硒在燃煤烟气中的浓度极低以及实验条件的限制 ,目前化学热力学平衡分析已成为预报烟气中砷和硒等有毒元素形态分布的主要理论分析方法。本文综述了热力学平衡分析方法应用于砷和硒在燃煤过程中形态转化和平衡分布等方面的研究进展。首先用于热力学平衡分析的是只含有砷或硒一种微量元素和煤中主量元素及氯元素的简单体系 ,并假设烟气中只有理想气体组成的气相和纯凝聚相的理想模型。然而是否考虑砷和硒与其他微量、主量或次量元素的相互作用 ,砷和硒所有可能存在的反应 ,以及在熔融相砷和硒与熔融物的结合会严重地影响模型的预报结果 ,因此 ,目前热力学平衡体系已发展成为含有包括砷和硒在内的多个微量元素和煤中所有主量、次量元素 ,以及包括熔融相在内的非理想多相复杂体系     

Modelling the atmospheric fate and seasonality of polycyclic aromatic hydrocarbons in the UK

This paper presents the results from an exercise in atmospheric contaminant fate modelling, which had three main objectives: (1) to investigate the balance between estimated national atmospheric emissions of six selected PAHs and observed ambient measurements for the UK, as a means of testing the current emission estimates; (2) to investigate the potential influence of seasonally dependent environmental fate processes on the observed seasonality of air concentrations; and (3) after undertaking the first two objectives, to make inferences about the likely magnitude of seasonal differences in sources. When addressing objective 1 with annually averaged emissions data, it appeared that the UK PAH atmospheric emissions inventory was reasonably reliable for fluorene, fluoranthene, pyrene, benzo[a]pyrene and benzo[ghi]perylene--but not so for phenanthrene. However, more detailed analysis of the seasonality in environmental processes which may influence ambient levels, showed that the directions and/or magnitudes of the predicted seasonality did not coincide with field observations. This indicates either that our understanding of the environmental fate and behaviour of PAHs is still limited, and/or that there are uncertainties in the emissions inventories. It is suggested that better quantification of PAH sources is needed. For 3- and 4-ringed compounds, this should focus on those sources which increase with temperature, such as volatilisation from soil, water, vegetation and urban surfaces, and possible microbially-mediated formation mechanisms. The study also suggests that the contributions of inefficient, diffusive combustion processes (e.g. domestic coal/wood burning) may be underestimated as a source of the toxicologically significant higher molecular weight species in the winter. It is concluded that many signatory countries to the UNECE POPs protocol (which requires them to reduce national PAH emissions to 1990 levels) will experience difficulties in demonstrating compliance, because source inventories for 1990 and contemporary situations are clearly subject to major uncertainties.     

Differences in the responses of native and transplanted mosses to atmospheric pollution: a possible role of selenium

Native and transplanted mosses of the species Scleropodium purum were used to study the possible adaptation of the former to atmospheric contamination. A total of seven assays were carried out with transplanted moss exposed at sites around a thermal power station for 28 and 56 days, and native moss collected from the sites at the same time. Irrigated moss bags were used in order to maintain stable conditions throughout the exposure periods. Determinations were made of levels of Co, Cr, Cu, K, Ni, Pb, Se and Zn in the mosses. No significant differences were found, throughout the exposure time studied, in metal bioconcentration in the native mosses, whereas in the transplanted mosses the differences were significant for all metals except Ni. The degree of bioconcentration was higher at the start of the exposure period and later became more stable. The high levels of Se found in the native mosses compared to the transplanted mosses indicates a possible mechanism of adaptation by detoxification.     

Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation

Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg⁻¹) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO₄, PbSO₄·PbO, α-PbO and Pb⁰. Morphology investigations revealed that PM_2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl₂ extraction.     

A modelling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products

Volatile methyl siloxanes break down in the atmosphere by reacting with OH radicals to form OH-substituted silanols. As the silanols become increasingly OH substituted they are increasingly likely to be removed from the atmosphere by wet and dry deposition. A simple equilibrium partitioning model was constructed to explore the relative rates of removal by different mechanisms (reaction vs. deposition) for siloxanes and their resultant silanols. A mass balance is calculated for the parent siloxane molecule and for each silanol, characterised by the number of OH substitutions. The model includes the effect of incomplete equilibrium between the vapour, adsorbed and dissolved phases of silanols in the atmosphere using a non-equilibrium factor (epsilon) expressing relative departure from equilibrium. Model results show: (1) maximum vapour-phase concentrations for non-substituted siloxanes and single-OH-substituted silanols; (2) maximum dissolved-phase and adsorbed-phase concentrations for two-OH-substituted silanols; (3) >99% of the original material will be removed in wet deposition and <1% in dry deposition as silanols. For increasing OH-substitutions, the decreasing concentration of precursor molecules (as a consequence of combined removal processes) means that concentrations are negligible, in all phases, beyond three or four substitutions. Predictions were relatively insensitive to assumed departures from phase equilibrium. Predictions of silanol hydrolysis in liquid water droplets suggest that the mix of diol chain lengths in precipitation may not be in thermodynamic equilibrium and will depend on atmospheric residence time and pH.     

Costs,Emissions Reductions,and Vehicle Repair: Evidence from Arizona

ABSTRACT

The Arizona inspection and maintenance (I/M) program provides one of the first opportunities to examine the costs and effectiveness of vehicle emission repair. This paper examines various aspects of emission reductions, fuel economy improvements, and repair costs, drawing data from over 80,000 vehicles that failed the I/M test in Arizona between 1995 and the first half of 1996. We summarize the wealth of data on repair from the Arizona program and highlight its limitations. Because missing or incomplete cost information has been a serious shortcoming for the evaluation of I/M programs, we develop a method for estimating repair costs when they are not reported. We find surprising evidence that almost one quarter of all vehicles that take the I/M test are never observed to pass the test. Using a statistical analysis, we provide some information about the differences between the vehicles that pass and those that do not. Older, more polluting vehicles are much more likely never to pass the I/M test, and their expected repair costs are much higher than those for newer cars.

This paper summarizes the evidence on costs and emission reductions in the Arizona program, comparing costs and emissions reductions between cars and trucks. Finally, we examine the potential for more cost-effective repair, first through an analysis of tightening I/M cut points and then by calculating the cost savings of achieving different emission reduction goals when the most cost-effective repairs are made first.     

A Probabilistic Production Costing Analysis of SO2 Emissions Reduction Strategies for Ohio: Emissions,Cost, and Employment Tradeoffs

A new approach for state- and utility-level analysis of the cost and regional economic impacts of strategies for reducing utility SO₂ emissions is summarized and applied to Ohio. The methodology is based upon probabilistic production costing and economic input-output analysis. It is an improvement over previous approaches because it: (1) accurately models random outages of generating units, “must-run” constraints on unit output, and the distribution of power demands; and (2) runs quickly on a microcomputer and yet considers the entire range of potential control strategies from a systems perspective. The input-output analysis considers not only the economic effects of utility fuel use and capital investment, but also those of increased electric rates. Two distinct strategies are found to be most attractive for Ohio. The first, more flexible one, consists of emissions dispatching (ED) alone to meet short run emissions reduction targets. A 75 percent reduction can then be achieved by the turn of the century by combining ED and fuel switching (FS) with flue gas desulfiirization, limestone Injection multistage burners, and physical coal cleaning at selected plants. The second is a scrubber-based strategy which includes ED. By the year 2000, energy conservation becomes a cost effective component of these strategies. In order to minimize compliance costs, acid rain legislation which facilitates emissions trading and places regional tonnage limits on emissions is desirable.     

Geochemistry of inorganic arsenic and selenium in a tropical soil: effect of reaction time, pH, and competitive anions on arsenic and selenium adsorption

Factors that can affect As and Se adsorption by soils influence the bioavailability and mobility of these elements in the subsurface. This research attempted to compare the adsorption capacities of As(III), As(V), Se(IV), and Se(VI) on a tropical soil commonly found in Singapore in a single-species system. The effect of reaction time, pH, and competitive anions at different concentrations on the adsorption of both As and Se species were investigated. The As and Se adsorption isotherm were also obtained under different background electrolytes. The batch adsorption experiments showed that the sequence of the As and Se adsorption capacities in the soil was As(V) > Se(IV) > As(III) > Se(VI). The adsorption kinetics could be best described by the Elovich equation. The adsorption of As(V), Se(IV), and Se(VI) appeared to be influenced by the variable pH-dependent charges developed on the soil particle surfaces. Phosphate had more profound effect than SO4(2-) on As and Se adsorption in the soil. The competition between PO4(3-) and As or Se oxyanions on adsorption sites was presumably due to the formation of surface complexes and the surface accumulation or precipitation involving PO4(3-). The thermodynamic adsorption data for As(V) and Se(IV) adsorption followed the Langmuir equation, while the As(III) and Se(VI) adsorption data appeared to be best-represented by the Freundlich equation.     

Biomonitoring selenium,mercury, and selenium:mercury molar ratios in selected species in Northeastern US estuaries: risk to biota and humans

Environmental Science and Pollution Research - The mutual mitigation of selenium and mercury toxicity is particularly interesting, especially for humans. Mercury is widely recognized as a pantoxic...     

Emissions Variability Processor (EMVAP): Design,evaluation, and application

Emissions of pollutants such as SO₂ and NOx from external combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup, shutdown, and maintenance/malfunction. While monitoring will automatically reflect variability from both emissions and meteorological influences, dispersion modeling has been typically conducted with a single constant peak emission rate. To respond to the need to account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, we have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates. Based upon initial AERMOD modeling of from 1 to 5 years of actual meteorological conditions, EMVAP is used as a postprocessor to AERMOD to simulate hundreds or even thousands of years of concentration predictions. This procedure uses emissions varied hourly with a Monte Carlo sampling process that is based upon the user-specified emissions distribution, from which a probabilistic estimate can be obtained of the controlling concentration. EMVAP can also accommodate an advanced Tier 2 NO₂ modeling technique that uses a varying ambient ratio method approach to determine the fraction of total oxides of nitrogen that are in the form of nitrogen dioxide. For the case of the 1-hr National Ambient Air Quality Standards (NAAQS, established for SO₂ and NO₂), a “critical value” can be defined as the highest hourly emission rate that would be simulated to satisfy the standard using air dispersion models assuming constant emissions throughout the simulation. The critical value can be used as the starting point for a procedure like EMVAP that evaluates the impact of emissions variability and uses this information to determine an appropriate value to use for a longer term (e.g., 30-day) average emission rate that would still provide protection for the NAAQS under consideration. This paper reports on the design of EMVAP and its evaluation on several field databases that demonstrate that EMVAP produces a suitably modest overestimation of design concentrations. We also provide an example of an EMVAP application that involves a case in which a new emission limitation needs to be considered for a hypothetical emission unit that has infrequent higher-than-normal SO₂ emissions.

ImplicationsEmissions of pollutants from combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup and shutdown. While monitoring will automatically reflect this variability on measured concentrations, dispersion modeling is typically conducted with a single peak emission rate assumed to occur continuously. To realistically account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, the authors have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates.     

Hydroxylated polychlorinated biphenyls in the environment: sources,fate, and toxicities

Hydroxylated polychlorinated biphenyls (OH-PCBs) are produced in the environment by the oxidation of PCBs through a variety of mechanisms, including metabolic transformation in living organisms and abiotic reactions with hydroxyl radicals. As a consequence, OH-PCBs have been detected in a wide range of environmental samples, including animal tissues, water, and sediments. OH-PCBs have recently raised serious environmental concerns because they exert a variety of toxic effects at lower doses than the parent PCBs and they are disruptors of the endocrine system. Although evidence about the widespread dispersion of OH-PCBs in various compartments of the ecosystem has accumulated, little is currently known about their biodegradation and behavior in the environment. OH-PCBs are, today, increasingly considered as a new class of environmental contaminants that possess specific chemical, physical, and biological properties not shared with the parent PCBs. This article reviews recent findings regarding the sources, fate, and toxicities of OH-PCBs in the environment.     

Ecological effects, transport, and fate of mercury: a general review

Mercury at low concentrations represents a major hazard to microorganisms. Inorganic mercury has been reported to produce harmful effects at 5 μg/l in a culture medium. Organomercury compounds can exert the same effect at concentrations 10 times lower than this. The organic forms of mercury are generally more toxic to aquatic organisms and birds than the inorganic forms. Aquatic plants are affected by mercury in water at concentrations of 1 mg/l for inorganic mercury and at much lower concentrations of organic mercury. Aquatic invertebrates widely vary in their susceptibility to mercury. In general, organisms in the larval stage are most sensitive. Methyl mercury in fish is caused by bacterial methylation of inorganic mercury, either in the environment or in bacteria associated with fish gills or gut. In aquatic matrices, mercury toxicity is affected by temperature, salinity, dissolved oxygen and water hardness. A wide variety of physiological, reproductive and biochemical abnormalities have been reported in fish exposed to sublethal concentrations of mercury. Birds fed inorganic mercury show a reduction in food intake and consequent poor growth. Other (more subtle) effects in avian receptors have been reported (i.e., increased enzyme production, decreased cardiovascular function, blood parameter changes, immune response, kidney function and structure, and behavioral changes). The form of retained mercury in birds is more variable and depends on species, target organ and geographical site. With few exceptions, terrestrial plants (woody plants in particular) are generally insensitive to the harmful effects of mercury compounds.     

Halogenated acetaldehydes: analysis, stability and fate in drinking water

In our previous studies, chloral hydrate has been the only chlorinated acetaldehyde determined in drinking water because authentic standards of other related haloacetaldehydes were not available. Recently, standards of dichloroacetaldehyde, bromochloroacetaldehyde, dibromoacetaldehyde, bromodichloroacetaldehyde, chlorodibromoacetaldehyde, and tribromoacetaldehyde have become available commercially. They were obtained and verified for purity and stability using a dual-column GC-ECD system. Each commercial standard was found to contain small amounts of the other target haloacetaldehydes (HAs). The stability of the HAs stock solutions was solvent dependent: in acetone, the brominated species partially degraded to bromoacetone, while all target HAs were stable in MTBE for up to 8 months. The analytical parameters, required for the quantification of HAs in water, were determined and used to evaluate the stability of the HAs in water. Under the conditions of the sampling protocol (field pH adjustment to pH 4.5 and storage at 4 degrees C), the target HAs were stable in water for up to 14 days. However, at typical drinking water pH and temperature conditions, the stability varied with the HA species, pH, temperature and storage period. The trihalogenated acetaldehydes degraded, in part, to their corresponding trihalomethanes (THMs) at increasing pH and temperature. Most target HAs were detected in drinking water samples collected from various Canadian drinking water systems, and the speciation was dependent on water parameters (e.g. bromide concentration) and treatment processes. From the water samples analysed, chloral hydrate ranged between 7% and 51% of the total HAs (w/w). The weigh ratio of total HAs to total THMs (10-46%) indicated that HAs contributed significantly to the pool of DBPs in drinking water.     

Auto Emissions,Engine Size,and Fuel Economy

EPA Reference Method 25 for measurement of total gaseous nonmethane organics as carbon in source emissions was evaluated in the laboratory and through field testing. Laboratory evaluation included development and testing of a nonmethane organic analyzer. In addition, a series of tests was performed on the condensate trap recovery system. The tests involved evaluation of two different condensate trap recovery system designs. The first design was very similar to the Federal Register design and the second design was a modified system for minimizing interference from trapped carbon dioxide. Field testing of the method was performed at two different printing plants. Both plants used carbon bed adsorption for solvent recovery and control of VOC emissions. Samples were collected from the inlet and outlet streams of adsorption units at both plants. In addition to Method 25 samples, Method 18 samples were collected for analysis by gas chromatography with flame ionization detection. The results of all the laboratory and field test samples are described.     

Effects of Operating Variables on PAH Emissions and Mutagenicity of Emissions from Woodstoves

As part of the Integrated Air Cancer Project, the U.S. Environmental Protection Agency (EPA) has conducted field emission measurement programs in Raleigh, North Carolina, and Boise, Idaho, to identify the potential mutagenic Impact of residential wood burning and motor vehicles on ambient and indoor air. These studies included the collection of emission samples from chimneys serving wood burning appliances. Parallel projects were undertaken in Instrumented woodstove test laboratories to quantify woodstove emissions during operations typical of in-house usage but under more controlled conditions.

Three woodstoves were operated In test laboratories over a range of burnrates, burning eastern oak, southern yellow pine, or western white pine. Two conventional stoves were tested at an altitude of 90 m. One of the conventional stoves and a catalytic stove were tested at an altitude of 825 m.

Decreasing burnrate increased total paniculate emissions from the conventional stoves while the catalytic stove's total particulate emissions were unaffected. There was no correlation of total particulate emissions with altitude whereas total polynuclear aromatic hydrocarbon (PAH) emissions were higher at the lower altitude. Mutagenicity of the catalytic stove emissions was higher than emissions from the conventional stove. Emissions from burning pine were more mutagenic than emissions from oak.     

Influence of bacteria on Pb and Zn speciation, mobility and bioavailability in soil: A laboratory study

A soil column experiment was carried out to investigate the effects of inoculation of bacteria on metal bioavailability, mobility and potential leachability through single chemical extraction, consequential extraction and in situ soil solution extraction technologies. Results showed that bacteria inoculated, including Azotobacter chroococcum, Bacillus megaterium and Bacillus mucilaginosus, may pose both positive and negative impacts on bioavailability and mobility of heavy metals in soil, depending on the chemical nature of the metals. The activities of bacteria led to an increase of water dissolved organic carbon (DOC) concentration and a decrease of pH value, which enhanced metal mobility and bioavailability (e.g. an increase of water-soluble and HOAc-soluble Zn). On the other hand, bacteria could immobilize metals (e.g. a great reduction of water-soluble Pb) due to the adsorption by bacterial cell walls and possible sedimentation reactions with phosphate or other anions produced through bacterial metabolism.