Characterization of the Fugitive Particulate Emissions from Construction Mud/Dirt Carryout

Abstract

Although the fugitive dust associated with construction mud/dirt carryout can represent a substantial portion of the particulate matter (PM) emissions inventory in non-attainment areas, it has not been well characterized by direct sampling methods. In this paper, a research program is described that directly determined both PM₁₀ and PM_2.5 (particles ≤10 and 2.5 μm in classical aerodynamic diameter, respectively) emission factors for mud/dirt carryout from a major construction project located in metropolitan Kansas City, MO. The program also assessed the contribution of automotive emissions to the total PM_2.5 burden and determined the baseline emissions from the test road. As part of the study, both time-integrated and continuous exposure-profiling methods were used to assess the PM emissions, including particle size and elemental composition. This research resulted in overall PM₁₀ and PM_2.5 emission factors of 6 and 0.2 g/vehicle, respectively. Although PM₁₀ is within the range of prior U.S. Environmental Protection Agency (EPA) guidance, the PM_2.5 emission factor is far lower than previous estimates published by EPA. In addition, based on both the particle size and chemical data obtained in the study, a major portion of the PM_2.5 emissions appears to be attributable to automotive exhaust from light-duty, gasoline-powered vehicles and not to the fugitive dust associated with re-entrained mud/dirt carryout.     

Characterization of fugitive material within a primary lead smelter.

The primary production of Pb via the sinter plant-blast furnace method resulted in a large number of Pb and other phases, reflecting the complex reactions occurring within each of the processes. Optical microscopy and X-ray diffraction (XRD) techniques have been used to characterize fugitive emissions and dusts generated during sintering, smelting, Cu drossing, refining, and slag fuming at a primary Pb-Zn smelter. The results displayed a complex array of phases, with the mineralogy of the dusts and fume reflecting conditions of the particular metallurgical operation. The principal Pb species followed a transformation from PbS through PbSO4 and PbO to Pb(o) (metal) from raw materials to the refinery. The fugitive emissions generated by the blast furnace were of a finer size with more complex chemistry than fugitive material from other source areas. XRD identified a mixture of PbS, ZnO, and ZnS, associated with one or more of the Cl-bearing phases Pb(OH)Cl, PbCl2, Pb4O3Cl2, Na3Pb2(SO4)3Cl, Pb10(SO4)Cl2O8, Pb4SCl6, and Pb7S2Cl10. The presence of Cl-bearing phases in the fume has possible health implications.     

Direct Measurement of Fugitive Emissions of Hydrocarbons from a Refinery

Abstract

Refineries are a source of emissions of volatile hydrocarbons that contribute to the formation of smog and ozone. Fugitive emissions of hydrocarbons are difficult to measure and quantify. Currently these emissions are estimated based on standard emission factors for the type and use of equipment installed. Differential absorption light detection and ranging (DIAL) can remotely measure concentration profiles of hydrocarbons in the atmosphere up to several hundred meters from the instrument. When combined with wind speed and direction, downwind vertical DIAL scans can be used to calculate mass fluxes of the measured gas leaving the site. Using a mobile DIAL unit, a survey was completed at a Canadian refinery to quantify fugitive emissions of methane, C₂₊ hydrocarbons, and benzene and to apportion the hydrocarbon emissions to the various areas of the refinery. Refinery fugitive emissions as measured with DIAL during this demonstration study were 1240 kg/hr of C₂₊ hydrocarbons, 300 kg/hr of methane, and 5 kg/hr of benzene. Storage tanks accounted for over 50% of the total emissions of C₂₊ hydrocarbons and benzene. The coker area and cooling towers were also significant sources. The C₂₊ hydrocarbons emissions measured during the demonstration amounted to 0.17% of the mass of the refinery hydrocarbon throughput for that period. If the same loss were repeated throughout the year, the lost product would represent a value of US$3.1 million/yr (assuming US$40/bbl). The DIAL-measured hourly emissions of C₂₊ hydrocarbons were 15 times higher than the emission factor estimates and gave a different perspective on which areas of the refinery were the main source of emissions. Methods, such as DIAL, that can directly measure fugitive emissions would improve the effectiveness of efforts to reduce emissions, quantify the reduction in emissions, and improve the accuracy of emissions data that are reported to regulators and the public.     

Coarse Particulate Matter Apportionment around a Steel Smelter Plant

Abstract

The results from a study carried out in the urban area of Genoa, Italy, where a large steel smelter recently shut down are presented. We had the opportunity to sample particulate matter (PM) before and after plant closure and, therefore, to measure the changes in concentration and composition of PM₁₀ (atmospheric PM with aerodynamic diameter <10 µm). Elemental concentrations of Na to Pb were obtained through energy dispersive X-ray fluorescence (ED-XRF), and the contributions of specific sources of PM₁₀ were calculated by positive matrix factorization (PMF). The PM₁₀ average concentration turned out to be surprisingly similar before and after closing of the smelter. Nevertheless, the comparison among data collected in the two periods (plant operating and closed), even with the limited information provided by ED-XRF, allowed us to single out two sources of PM related to the smelter activities, to extract their emission profile, and to quantify the impact of the plant on PM₁₀ levels.     

Estimating Fugitive Emissions of Volatile Compounds from Equipment Leaks

This paper is directed to those concerned with estimating releases to the air of volatile compounds from equipment component leaks. We compared emission rates for equipment component leaks using EPA’s Average Emission Factor Method, Leak/No-Leak Emission Factor Method, and Stratified Emission Factor Method. The latter two methods may be used if there are concentration measurements about the components. An organic vapor analyzer was applied with the appropriate response factor to measure the concentrations around each equipment component using EPA Method 21. We analyzed this data to determine mass emission rates. Results show that the Average Emission Factor Method substantially overstates the emission rates calculated using these other two methods. We conclude that use of Method 21 concentration measurements with the Leak/No Leak or Stratified Emission Factor Method may increase the accuracy and reduce significantly the estimated releases to the air of volatile compounds from equipment component leaks for many facilities.     

Chromium Analysis at a Ferrochrome Smelter,a Chemical Plant and a Refractory Brick Plant

Techniques were developed to sample and analyze the Cr content of participate samples with emphasis on determining the concentration of the carcinogen Cr⁺⁶. Cr⁺⁶ is extracted to alkaline solution and analyzed colorimetrically. Residual particles are extracted with acid solution to remove soluble Cr⁺³, which is determined by atomic absorption spectrometry. This methodology was tested on samples from three diverse types of sources: a ferrochrome smelter, a chemical plant, and a refractory brick plant. Identical quadruplicate samples were collected to determine accuracy and precision of the collection and analysis procedures, and extraction of Cr⁺⁶ and Cr⁺³. A statistical analysis revealed that the precision of Cr⁺⁶ analysis is comparable to that of the particulate mass determination. The stability of Cr⁺⁶ In particulate form and in solution was determined. Size resolved particulate samples were collected to determine the particle size versus the Cr⁺⁶ content. At the ferrochrome smelter and the chemical plant the majority of the Cr⁺⁶ was contained in the respirable particles. The accuracy and completeness of the chemical methods employed were verified by neutron activation analysis, x-ray photoelectron spectroscopy, and scanning electron microscopyenergy dispersive x-ray analysis.     

Lead in a Suburban Environment

The lead content of air, rainfall, and dry-fallout samples taken at several sites in Palo Alto, Calif, are reported and discussed. The high-speed high-density freeway traffic in the area appears to be the major source of lead pollution. The natural atmospheric cleansing processes of sedimentation and raindrop scavenging remove large quantities of lead particulate matter. It is suspected that nucleation occurs on the submicronic lead compound particles in the exhaust stream, producing droplets which may impact on the larger airborne particles. This could explain the wide range of size distributions reported in the literature as well as the large amounts of lead found in the samples analyzed.     

Charged Fog Technology Part II: Prototype Tests of a New Charged Fog Generator for Fugitive Emission Control

The prototype charged fog generator described in a preceding paper¹ was field tested on a fugitive emission source at a bentonite ore processing plant in Worland, Wyoming, during 1981. Participate matter samples were collected as fine and coarse fractions under three different test scenarios: with no control, with partial control (uncharged fog), and with full control (charged fog). Measured particulate matter sample concentrations were normalized for each test day with respect to the background values so that particle control efficiency of the device could be evaluated without any bias during the entire test program.

These tests have shown that mean value of the inhalable particle control efficiency of charged fog measured under all instrument settings and field conditions is increased by 78% when compared with uncharged fog. In particular, fine particle control efficiencies of over 90% were recorded under optimum instrument settings and ideal field conditions. The bentonite particles seemed to carry a net positive charge. The optimum instrument settings were found to be: 60 L/h water flow rate, an applied voltage of 10-15 kV and a spray pattern which covers maximum volume of dust-laden air. Ideal field conditions are high relative humidity and calm or low winds.

Charged fog technology appears to be an effective and economically feasible method to control sources of fugitive particle emission in the inhalable size range. Further research is needed to evaluate the inhalable particle control efficiency of the device for emissions of various chemical compositions.     

The Impact of Gold Smelter Emissions on Vegetation and Soils of a Sub-Arctic Forest-Tundra Transition Ecosystem

Gold smelters near Yellowknife in Canada's Northwest Territories have emitted large quantities of sulfur dioxide and arsenic since inception of roasting in 1941. Although particulate wastes are well contained by baghouse fitters in the one remaining operating smelter, significant gaseous emissions continue. Soil and vegetation were sampled at 52 sites over an area of about 40 km radius from the source. Plant ecology was studied at 43 of those sites. After preliminary multi-element screening that indicated only arsenic was a serious persistent contaminant, x-ray fluorescence was used to measure arsenic content in sampled materials. The plant ecology data were synthesized into an Index of Vitality with numerical ratings of pertinent factors. In the marginal forests and rocky outcrops of the area, indicator species of vegetation permitted a division into zones of severe, moderate, mild, or no impact in order of increasing distance from the current center of emissions. Severe impact, including killing of trees, is local only. Analyses of foliage indicate little uptake of arsenic which, together with the presence of S0₂ symptoms, point to S0₂ as the main factor causing decline of vegetation. A separate study, abstracted here, supports this view by providing data that show a frequency of at least 2 significant fumigation episodes per growing season. Soil analyses indicate extremely high arsenic contamination near the stack. A monotonie pattern of dispersion yielded a function explainable in terms of rapid condensation of gaseous emissions. The relationship of arsenic in surface soil and vegetation to distance is approximately an inverse square.     

A Comparative Study of Aluminum Smelter Roof Vent Sampling Methods

Abstract

The purpose of the study was to quantify the impact of traffic conditions, such as free flow and congestion, on local air quality. The Borman Expressway (I-80/94) in Northwest Indiana is considered a test bed for this research because of the high volume of class 9 truck traffic traveling on it, as well as the existing and continuing installation of the Intelligent Transportation System (ITS) to improve traffic management along the highway stretch. An empirical traffic air quality (TAQ) model was developed to estimate the fine particulate matter (PM_2.5) emission factors (grams per kilometer) based solely on the measured traffic parameters, namely, average speed, average acceleration, and class 9 truck density. The TAQ model has shown better predictions that matched the measured emission factor values more than the U.S. Environmental Protection Agency (EPA)-PART5 model. During congestion (defined as flow-speeds <50 km/hr [30 mi/hr]), the TAQ model, on average, overpredicted the measured values only by a factor of 1.2, in comparison to a fourfold underprediction using the EPA-PART5 model. On the other hand, during free flow (defined as flow-speeds >80 km/hr [50 mi/hr]), the TAQ model was conservative in that it overpredicted the measured values by 1.5-fold.     

Lead sorption by a Mexican,clinoptilolite-rich tuff

Goal, Scope and Background The retention of lead by a Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) at different pH values was evaluated and the lead sorption mechanisms on the zeolitic material in this work were discussed. Methods Isotherms were determined using lead nitrate solutions (initial pH values between 2 and 5) at 303 K. After the equilibrium was reached, the content of lead in the liquid phases was determined by atomic absorption spectrometry. The elemental composition of the clinoptilolite-rich tuff before and after the lead sorption process was evaluated by electron microscopy. Results The maximum ion exchange capacity of the Mexican, clinoptilolite-rich tuff for lead was 1.4 meq/g at pH 3, considering an ion exchange mechanism in the absence of any precipitated or hydrolyzed lead species in the sorption process or any change in the zeolite network. Langmuir and Freundlich isotherms were also considered in this work for comparison purposes. Discussion It is important to consider the nature of the sorption processes before choosing a model to describe the interaction between the metal ions and the sorbent. Conclusions The chemical lead speciation, the pH, as well as the characteristics of the clinoptilolite-rich tuff are important factors to be considered on the lead sorption process by natural zeolites. The chemical species involved in that process are Na⁺ from the zeolite and Pb²⁺ from the aqueous solution at pH 2 and 3, so that the ion exchange mechanism explains the lead sorption processes by the clinoptilolite-rich tuff through the ion exchange isotherms. The sodium, Mexican, clinoptilolite-rich tuff is a potential adsorbent for lead from aqueous solutions. Recommendations and Perspectives The natural zeolite-rich tuffs are very important as ion exchangers for the treatment of polluted water due to their sorption properties and low cost. The sorption behavior of each natural material depends on their composition. Mexican, clinoptilolite-rich tuff from Oaxaca (Mexico) could be used for the treatment of waste water contaminated with lead. It would be important to propose this material as an alternative as waste water treatment, because it shows good selectivity for the removal of heavy metals from water.     

Silver Valley Lead Study: Further Analysis of the Relationship between Blood Lead and Air Lead

Blood lead and air lead levels of children who lived within 32 km of a smelter in Kellogg, ID were measured in 1974 and 1975. While an analysis of the 1974 survey has appeared, the results of the 1975 survey and an evaluation of the change in blood lead levels of those children who participated in both the 1974 and 1975 surveys has not previously been discussed in the literature. It Is concluded that, for these data, in the air lead range of 0.5–5 μg/m³, the blood lead-air lead relationship can be adequately described by blood lead-air lead slope which is approximately 1.0 and at most 1.4. This slope was also found to be Independent of children’s age. It Is shown that an accurate estimate of the blood lead-air lead relationship cannot be obtained without taking proper account of selected environmental variables; specifically, pica, sex, age, father’s work status, education, and home cleanliness.     

Lead poisoning of passerines at a trap and skeet range

Our objective was to determine if ground foraging passerines in a woodland surrounding a trap and skeet range were subject to lead poisoning. Lead availability to birds was determined by shot counts and soil and earthworm analysis. Avian exposure to lead was identified by measuring free-erythrocyte protoporphyrin levels in blood and lead in tissues of three passerine species. Results showed that most shot were found in the top 3 cm of soil. Lead measurements ranged from 110 to 27,000 ppm (dry wt) in soil and were 660 and 840 ppm in earthworms. Sparrows held in an aviary at the range (p=0.02) and free-flying juncos (p=0.0005) mist-netted at the range displayed significantly higher protoporphyrin levels than those at an uncontaminated site. Sparrow and cowbird carcasses from the aviary carried 37 and 39 ppm lead (dry wt), respectively, whereas a junco liver contained 9.3 ppm lead.     

Application of the Lime/Limestone Flue Gas Desulfurization Process to Smelter Gases

In this presentation, adaptation of the lime/limestone process for flue gas desulfurization (FGD) is discussed and how this process can be adapted to applications in the nonferrous smelting industry such as fugitive gases, copper reverberatory furnace gases, lead sintering gases, molybdenum roasting plant tail gases, and other weak SO₂ smelter gases. Different methods for particulate removal are also discussed with emphasis on how the particulate removal process can be integrated with the desulfurization process.     

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

Lead Contamination of Urban Soils and Vegetation by Emissions from Secondary Lead Industries

The degree and extent of lead contamination of urban soils and vegetation in the vicinity of secondary lead industries are provided. These urban industries, a secondary smelter reprocessing lead from used batteries and scrap metal and a manufacturer of new storage batteries, were located near residential communities. Levels as high as 21,000 ppm of lead in the upper 5 cm of soil (based on air dried weight) and 3500 and 2700 ppm in willow foliage (not washed and washed, respectively, based on dry weight) were found adjacent to the secondary smelter, with the levels decreasing exponentially from the sources. The data on lead contamination of soils and vegetation at various distances and directions from the urban secondary lead industries were compared with levels of lead found in control urban and highway locations. In addition, arsenic levels in soil were examined as a tracer for the source of industrial lead emissions. High levels of lead found In both vegetation and soil in the vicinity of the urban industries reflected both historical and current emissions of lead in those areas. These studies were conducted for industrial abatement purposes; to assist medical related epidemiology studies; to define the areas of severe contamination for soil cleanup purposes; and to formulate guidelines for excessive levels of lead in soil and vegetation. Since lead in soil is persistent, concern arises with respect to pica for small children, contamination of edible vegetables grown in high-lead soil, and reentrainment of leaded particulate matter into the air.     

Lead shot from hunting as a source of lead in human blood

This study investigates the relationship between the intake of birds hunted with lead shot and the lead concentration in human blood. Fifty adult men from Nuuk, Greenland took part in the study. From September 2003 to June 2004 they regularly gave blood samples and recorded how many birds they ate. We found a clear relationship between the number of bird meals and blood lead and also a clear seasonal variation. The concentration was highest in mid-winter when bird consumption is at its highest. Blood lead was low (15 microg/L, mean concentration) among the participants reporting not eating birds. Among those reporting to eat birds regularly, blood lead was significantly higher, up to 128 microg/L (mean concentration). Concentrations depended on the frequency of bird meals: the more the bird meals, the higher the resulting blood lead. This clear relationship points to lead shot as the dominating lead source to people in Greenland.     

An Assessment of Mercury Emissions from the Afton Copper Smelter,British Columbia,Canada

The Afton Copper Smelter adjacent to Kamloops, British Columbia, Canada commenced operation in 1978 and employed a mercury scrubbing system. Two years of preproduction studies, which included monitoring for mercury in ambient air, water, soli, and vegetation were performed. The results from similar studies conducted during four full years (1978–81) and two partial years (1982–83) of production are presented in the data analysis. These programs illustrated that the most frequent ground impingement occurred within a 1.6–3.2- km radius of the source, and that the levels decreased with increasing distance from the source to a maximum radius of 8 km. The results of a comprehensive source monitoring program illustrated that the average mercury emission levels ranged from 3.2 to 6.8 kg/calendar day during 1979–81, and that the majority of the emissions were in a vapour form. The ambient monitoring data acquired when smelter operations were significantly reduced indicate a quick recovery to preproduction levels in virtually all monitored parameters and at most monitored sites. The integrated results from all mercury monitoring programs illustrate the environmental impact from mercury emissions which were two to four times the permit standard of 1.8 kg/day.     

Lead removal from synthetic leachate matrices by a novel ion-exchange material

This paper discusses the application of a novel polyacrylate-based ion-exchange material for the removal of Pb ions from water. Preliminary testing includes the establishment of the operating pH range, capacity information, and the effect of Ca2+ and anions in the matrix. Batch testing with powder indicates slightly different optimal operational conditions from those used for column testing. The ion-exchanger is excellent for removing Pb from aqueous solutions.