Deposition of Mn from Automotive Combustion of Methylcyclopentadienyl Manganese Tricarbonyl beside the Major Highways in the Greater Toronto Area,Canada

ABSTRACT

Methylcyclopentadienyl manganese tricarbonyl (MMT) has been used in Canada since 1976 as an antiknock agent in gasoline, completely replacing Pb in 1990. An early study of much higher Mn concentrations in gasoline showed that the combustion of MMT leads to the formation of inorganic manganese oxides, especially Mn₃O₄. Recent emission testing by Lawrence Livermore National Laboratory for Ethyl Corp. has shown that Mn is primarily emitted as a phosphate or sulfate along with minor amounts of oxides. The main objective of this research was to analyze the deposition of Mn from MMT to the terrestrial environment beside the major highways in the greater Toronto area (GTA), Canada. The results were compared with Pb and other trace elements such as Al, Ca, Fe, Mg, Cu, Zn, Na, and the Cl^- ion (water extractable) to study the behavior of Mn in soil. The study area was located near major Toronto highways 401 (urban) and 400 (rural), at 43° 67′ N and 79° 37′ W (latitude and longitude) (278,560 and 47,835 cars/day), respectively. Surface soil samples (0–5 cm depth) were collected at distances up to 40 m from the roadside. Parameters evaluated included total and available Mn and other trace elements, particle size, pH, organic content, and cation exchange capacity.     

Composition,Size and Control of Automotive Exhaust Particulates

This paper on automobile exhaust particulates describes total particulate composition, size of exhausted lead particulates, and the effects of traps on total lead emitted. This study was conducted using cars manufactured during 1966-1970. Work in suspended particulate emission from several vehicles operated on a chassis dynamometer under Federal 7-mode cycle conditions has shown: (1 ) cars vary widely in the amounts and composition of their particulate emissions; (2) cold-cycle operation gives 2-8 times more particulate than hot engine operation; (3) lead compounds represent less than one-third of total particulates, the remainder being carbon compounds along with ammonium and nitrate ions and unknown materials; (4) carbon emission for stabilized cars using leaded gasoline varies widely but averages about 35% of the total; (5) suspended particulate emissions are nearly equal with new cars whether or not lead is present; (6) exhausted lead varies with the condition of the exhaust system and ranges between 7 and 30% of the lead consumed by the engine; (7) fuel additives affect the amount of emitted particulates; (8) probe sampling techniques underestimate by a large factor the amount of particulates emitted by vehicles; and (9) trapping systems offer potential for greatly reducing the emission of suspended total particulates.     

Composition of Exhaust from a Regenerative Turbine System

Particulate and hydrocarbon content of gases in a regenerative gas turbine was analyzed at several points. Particle samples were measured with a condensation nuclei counter, a light scattering single particle counter and an impactor. Hydrocarbon analyses were made using gas chromatography. The effects of operation with JP-4 and No. 2 fuel oil were noted. It was concluded that a regenerative gas turbine will not add appreciably to the burden of air pollution. In fact, particulate contamination levels in the exhaust less than those in the inlet air indicates that the high rotation rate may result in some air cleaning. Low hyd rocarbon contents in the exhaust gas were ascribed to efficient combustion under the operating conditions used in this work. In general, it was concluded that hydrocarbon levels significantly lower than those seen from gasoline or diesel engines could be expected from a well maintained and operated regenerative gas turbine.     

The Effect of Fuel Composition on Atmospheric Aerosol Due to Auto Exhaust

Aerosols attributable to automobile exhaust can be classified as two types—primary aerosol (initially present in the exhaust) and secondary aerosol (generated photochemically from hydrocarbons and nitrogen oxides in the exhaust). In this study, investigation was made of possible effects of motor-fuel composition on the formation of these aerosols. Secondary aerosol, of principal interest in this work, was produced by irradiating auto exhaust in Battelle-Columbus’ 610 ft³ environmental chamber. A limited number of determinations of primary aerosol in diluted auto exhaust was made at the exit of a 36 ft dilution runnel. Determination of both primary and secondary aerosol was based on light-scattering measurements.

Exhaust was generated with seven full-boiling motor gasolines, both leaded and nonleaded, in a 1967 Chevrolet which was not equipped with exhaust-emission control devices. Changes in fuel composition produced a maximum factor of three difference in light scattering due to primary aerosol. Aerosol yields, for consecutive driving cycles on the same fuel, vary considerably; as a result, ranking the fuels on the basis of average primary aerosol yield was not very meaningful. In addition to fuel composition, the more important independent variables are initial SO₂ concentration, relative humidity and initial hydrocarbon concentration. Statistical analysis of the data indicates that the seven test fuels can be divided into two arbitrary groups with regard to secondary aerosol-forming potential. The fuels in the lower light-scattering group had aromatic contents of 15 and 21%, while those in the higher light-scattering group had aromatic contents of 25, 48, and 55%. Although the fuels can be grouped on the basis of a compositional factor, the grouping of fuels with aromatic content ranging from 25 to 55% indicates that this compositional factor cannot be equated simply with aromatic content. In an associated study of the aerosol-forming potential of individual hydrocarbons prominent in auto exhaust, it was observed that aromatics produce substantially more photochemical aerosol than olefins and paraffins. However, experiments with binar/hydrocarbon mixtures containing aromatjcs, as well as in these exhaust experiments, a strong dependence of aerosol yield on the aromatic components is is not observed. Thus, the data indicate that the dependence of secondary aerosol formation on fuel factors is a complex one and cannot be predicted solely on the basis of a sirigle hydrocarbon component reactivity scale.

The two types of automobile aerosol did not have the same dependence on fuel, composition. The variation in total light scattering attributable to primary plus secondary aerosol was less than that due to either component alone. It therefore was concluded that the light scattering due to automobile exhaust emissions in these experiments was not significantly affected by changing fuel composition.     

Use of Diisobutylene Fuel in a Single Cylinder Engine: Effects of Equivalence Ratio on Exhaust Composition

This study describes the variations in the chemical composition of the exhaust at various equivalence ratios (air-fuel ratios) when pure diisobutylene (2,4,4-trimethyl-l-pentene) is used as a fuel in a Labeco single cylinder engine. The exhaust hydrocarbon products from diisobutylene consist of two types: those which decrease as the equivalence ratio is increased: methane, ethylene, acetylene, diisobutylene; and those which exhibit a maximum near an equivalence ratio of 1, then decrease: propylene, propadiene, isobutyl-ene, ethane, 2-methyl-l-butene. The combustion of diisobutylene produces two olefins in low yield which are not observed in the combustion of isooctane fuel. These are 2,4-dimethyl-l,3-pentadiene, probably derived from pyrolytic decomposition of C₇-alkyl radicals, and 3,5,5-trimethyl-2-hexene, probably arising from methyl radical addition to the alpha carbon of the parent fuel molecule. Comparison of the photochemical reactivity of dissobutylene exhaust to that of isooctane at a fuel-lean condition, indicates that diisobutylene, surprisingly, exhibits lower total photochemical reactivity.     

The Fate of Hydrogen Peroxide as an Oxygen Source for Bioremediation Activities within Saturated Aquifer Systems

ABSTRACT

In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H₂O₂ with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H₂O₂ into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H₂O₂ within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H₂O₂. The decomposition rates of H₂O₂ were determined using both equilibrated water samples and soil slurries. Results showed H₂O₂ decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.     

Effect of Methanol on Exhaust Composition of a Fuel Containing Toluene,n-Heptane,and Isooctane

This study describes the variations in the chemical composition of the exhaust from a single cylinder engine when up to 25% methanol is added to a fuel blend of toluene, isooctane, and n-heptane. Under fuel-rich conditions, and with increasing methanol concentration, it is observed that unburned fuel and benzene emissions increase, exhaust acetylene remains constant, and propylene, isobutylene, methane, ethylbenzene, and styrene concentrations decrease. As oxygen becomes more available, the effects of methanol are reduced, and at an equivalence ratio of 1.25—excess oxygen now is present—methanol no longer affects the concentration of exhaust hydrocarbons. These observations are explained by the reactions of formaldehyde—an incomplete combustion product of methanol— with alkyl radicals derived from the fuel. The photochemical reactivity of the exhaust is unchanged when up to 15% of methanol is present in the fuel at an equivalence ratio of 0.85, but increases at higher methanol contents because of the increase in unburned toluene in the exhaust.     

Effects of Air-Fuel Ratio on Composition of Hydrocarbon Exhaust from Toluene,Toluene-n Heptane Mixture and Isooctane

This study describes the variations in the chemical composition of the exhaust at various air-fuel ratios when toluene, toluene-n-heptane mixture, and isooctane are used as fuels in a Labeco single cylinder engine. The exhaust products from toluene are divided into three groups: those which decrease as the equivalence ratio is increased: toluene, benzene, methane, and dimethylacetylene; those which increase with increasing equivalence ratio: benzaldehyde, and products which exhibit a maximum at an equivalence ratio of 1, then decrease: acetylene, ethyl acetylene, ethyl benzene, and styrene. Combustion of the mixture of 25 volume percent n-heptane in toluene reveals interesting information, compared to emissions from pure toluene: concentrations of ethyl benzene, styrene, and dimethylacetylene surprisingly are increased by factors of 1.9, 1.9, and 2.1 respectively, probably because reactive radicals derived from heptane interact with toluene to form unsaturated molecules. Ethyl acetylene, benzene, and benzaldehyde remained unchanged but the fractional mole concentration of unreacted toluene decreased. These results show that fuels rich in aromatics may produce less unsaturates than when diluted with aliphatic fuels. For isooctane fuel, methane, and isooctane in the exhaust decrease as the equivalence ratio is increased, while isobutylene, propylene, ethylene, and propadiene concentrations exhibit maxima at an equivalence ratio of 1.     

The Hygienic Aspects of the Production and Use of Lead Antiknock Compounds

Hydrogen sulfide and other sulfides can be determined in the part per billion range in air if the air is bubbled through an absorption mixture of an alkaline suspension of cadmium hydroxide contained in a macro impinger. Rates as high as 1 cubic foot per minute can be used, or 0.1 cubic foot per minute with a midget impinger. The concentration of the trapped sulfides is then estimated by the methylene blue method. A colorimetric method and a spectrophotometric method are described.     

Fate of zinc in an electroplating sludge during electrokinetic treatments

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.     

The Fate of Vanadium in an Urban Air Shed: The Lower Delaware River Valley

Vanadium compounds are toxic pollutants which require engineering control in the design stage. In the lower Delaware River Valley, the main sources are presently the combustion of vanadium rich fuel oils and the catalytic processing of high vanadium crudes. These and other Industrial emissions, result in atmospheric vanadium concentrations which have varied from 0.133 μg/m³ to 0.557 μg/m³ between 1958 and 1969. Compounds of vanadium, principally with oxygen and sulfur, are considered. The dominance of oxygen compounds over sulfur compounds as derived from equilibrium data, and the tendency of vanadium oxides to move toward vanadium’s maximum valence of +5, indicate the prevalence of V₂0₅ as the emission compound.     

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH₂N-C(N-NO₂)-CHN-CHO or its isomer N(NO₂)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.     

Manganese and other trace elements in urban snow near an expressway

The Mn contamination arising from the combustion of MMT (methylcyclopentadienyl manganese tricarbonyl) in unleaded gasoline was assessed using snow collected at different distances 15, 25, 125 and 150 m from an expressway (Montreal, Canada) in February 1993. The snow samples were analyzed by atomic absorption and by neutron activation for total Mn, Mg, Cu, V, Al, Zn, Fe, Na, and Ca concentrations in the soluble (<0.4 microm) and particulate fractions. ANOVA with ranked values was performed to compare element concentrations and soluble/particulate ratios among receptor sites and depths. Principal component analysis was used to describe the spatiotemporal variations of the deposition rates and the influence of meteorological factors. The average concentration of all trace elements, except Mg, Cu, and V, decreased significantly (p<0.05) from receptor sites near the road (15-25 m) to those farther away (125-150 m). The deposition rates of all metals and ions, except Cu, were highly positively correlated (tau = 0.5-0.9) with each other and inversely correlated with snowfalls. Wind frequency showed no correlation with deposition rate. The spatial trend was similar for all these elements making it difficult to distinguish Mn arising from the combustion of MMT from that due to other sources, such as road dust. Only the soluble/particulate ratio calculated for Mn seemed higher than that for the other metals, which might be explained by the particle size of Mn from MMT (0.2-0.4 microm). The present study only indicates a direct contamination of the snow by road activities and substantial deposition of trace elements near the roadway; no clear link can be established between motor vehicle emissions and the concentration of Mn in snow.     

Fate of DDT and parathion in grapes processed into Arak,an alcoholic beverage

Abstract

Arak, the national alcoholic drink in Lebanon, was prepared from grapes to which either DDT or parathion had been added. Samples of the nine fractions produced from the fermentation and distillation steps were analyzed for DDT and parathion and their respective metabolites.

DDT degraded to DDD during the fermentation step resulting in a sharp decrease in DDT level. The two distillation steps contributed to a further decrease in the DDT level so that the final product contained less than 2% of the amount found in the fresh grape juice. Although the concentration of DDD increased sharply during fermentation, it also decreased to a negligible level during the subsequent distillation procedure.

Parathion was more stable than DDT during the fermentation and first distillation steps. However, the second distillation process caused a share decline in its level and the Arak contained only about 6% of the residues present in the fresh juice, paranitrophenol being the only metabolite detected.     

Fate of seven pesticides in an aerobic aquifer studied in column experiments

The fate of selected pesticides (bentazone, isoproturon, DNOC, MCPP, dichlorprop and 2,4-D) and a metabolite (2,6-dichlorobenzamide (BAM)) was investigated under aerobic conditions in column experiments using aquifer material and low concentrations of pesticides (approximately 25 microg/l). A solute transport model accounting for kinetic sorption and degradation was used to estimate sorption and degradation parameters. Isoproturon and DNOC were significantly retarded by sorption, whereas the retardation of the phenoxy acids (MCPP, 2,4-D and dichlorprop), BAM and bentazone was very low. After lag periods of 16-33 days for the phenoxy acids and 80 days for DNOC, these pesticides were degraded quickly with 0.-order rate constants of 1.3-2.6 microg/l/day. None of the most probable degradation products were detected.     

Fate estimation of estrogenic substances in an urban river by flux calculation.

This study investigated the fate of estrogenic substances in an urban river receiving discharge from wastewater treatment plants (WTPs) by flux calculation, focusing on the middle reaches of the Tama River in Tokyo, which is one of the most urbanized rivers in Japan. The level of estrogenic activity flux was almost negligibly small at the upstream station. The level was considerably raised after inflows from the WTPs and then the level declined in the lower reaches of the river. When contributions of estrogenic substances to estrogenic activity were estimated, estrone (E1) was the primary contributor to the total estrogenic activity in all the sampling stations, followed by estradiol (E2). The contribution of nonylphenol to estrogenic activity was small. The E1 and E2 accounted for approximately 90% or more of estrogenic activity in the Tama River. As for the total fluxes of the estrogenic substances in the study area in the Tama River, the proportion of flux associated with WTP discharge was approximately 100% of the total fluxes, and the effects of the tributaries flowing into the river were almost negligible. When the reduction ratios of estrogenic activity were calculated by the flux, the ratios were found to increase toward the lower reaches of the river. Similar changes were observed for E1. Meanwhile, the change of reduction ratios for E2 was different from that observed for estrogenic activity.     

Proportional Sampling System for the Collection of an Integrated Auto Exhaust Gas Sample

Carbon baking process involves evolution of fumes containing hydrocarbons and soot particles which cannot be discharged directly into the atmosphere. An incinerator can be used to clean these fumes. However, length of the baking cycle, nature of the fumes and variations in fume volume and temperature may result in excessive auxiliary fuel usage and inefficient incineration, if the incinerator is not designed properly. This paper describes the application of fundamental knowledge of aerodynamics, reaction kinetics and combustion, together with clear understanding of the process, in design of a highly efficient, fully automated incinerator. The design incorporates a unique but simple control system which results in reduction of auxiliary fuel usage without endangering the safety and efficiency of the incineration process. Operations and economics of the incinerator are described by illustrating a typical baking cycle and comparing actual fuel usage with the thermal ratings of the incinerator. Operating experience from a number of installations in the U. S. and Canada is also noted.