NOVEMBER 1977 HUMAN POPULATION EXPOSURES TO COKE-OVENS ATMOSPHERIC EMISSIONS US. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF RESEARCH AND DEVELOPMENT WASHINGTON, D.C. 2O460 Project Offtcw: ALAN f. CARLIN Technical Monitor: JUSTICE A. MANNING CONTRACT 6*01-4314 .SRf Project EGU-5794. CENTER FOR RESOURCE AND ENVIRONMENTAL SYSTEMS STUDIES R«port No. 27 ------- NOVEMBER 1977 HUMAN POPULATION EXPOSURES TO COKE-OVENS ATMOSPHERIC EMISSIONS By: BENJAMIN E. SUTA SRI INTERNATIONAL MENLO PARK, CA 94025 Prepared for: U.S. ENVIRONMENTAL PROTECTION AGENCY OFFICE OF RESEARCH AND DEVELOPMENT WASHINGTON, D.C. 20460 Project Officer: ALAN P. CAR LIN Technical Monitor: JUSTICE A. MANNING CONTRACT 68-01-4314 SRI Project EGU-5794 CENTER FOR RESOURCE AND ENVIRONMENTAL SYSTEMS STUDIES Report No. 27 ------- NOTICE This is a preliminary draft. It has been released by the U. S. Environmental Protection Agency (EPA) for public review and comment and does not necessarily reflect Agency policy. This report was provided to EPA by SRI International, Menlo Park, California, in partial fulfillment of contract No. 68-01-4314. The contents of this report are reproduced herein as received by SRI after comments by EPA. The opinions, findings, and conclusions expressed are those of the authors and not necessarily those of EPA. Mention of company or product names is not to be considered as an endorsement by the EPA. ii ------- ACKNOWLEDGMENT It is a pleasure to acknowledge the cooperation and guidance given by Alan Carlin and Justice Manning of the U.S. Environmental Protection Agency in the preparation of this report. In addition, a number of other people generously supplied input data. They include: Mark Antell, U.S. Environmental Protection Agency Robert Armbrust, New York State Department of Environmental Conservation Thomas Au, Pennsylvania Department of Environmental Resources Bernard Bloom, U.S. Environmental Protection Agency Walter Cooney, Maryland State Environmental Health Administration Ron Dubin, Pennsylvania Department of Environmental Resources Arvid Ek, Allegheny County Health Department Clemens Lazenka, Philadelphia Air Quality Division Jim Payne, Texas Air Control Board C. B. Robison, Jefferson County, Alabama Board of Health Terry Sweitzer, Illinois Environmental Protection Agency Peter Warner, Wayne County, Michigan Health Department Robert Yuhnke, Pennsylvania Department of Environmental Resources. iii ------- PREFACE There is a substantial body of evidence, both direct and indirect, that the mixture that coke oven emissions represent is carcinogenic and toxic. Current U. S. Environmental Protection Agency (EPA) policy states that there is no zero risk level for carcinogens. To determine what regulatory action should be taken by EPA on atmospheric emissions of coke ovens, three reports have been prepared: (1) a health effects assessment, (2) a population exposure assessment, and (3) a risk assessment document based on the data in the first two assessments. This document is the human population exposure assessment and presents estimates of the numbers of people in the general population of the United States exposed to atmospheric concentrations of coke oven emissions. Estimates are provided of population exposures to ambient concentrations of benzo(a)pyrene Bap and benzene soluble organics (BSO) material caused by coke oven emissions. iv ------- CONTENTS ACKNOWLEDGMENT 11 LIST OF ILLUSTRATIONS v LIST OF TABLES vi I INTRODUCTION 1 II SUMMARY AND CONCLUSIONS 2 A. Overview 2 B. At-Risk-Populations 5 C. Population Estimation 5 D. Population Exposures to BaP Emitted by Coke-Ovens . . 7 E. Population Exposures to BSO Emitted by Coke-Ovens . . 8 F. Considerations in the Use of the Annual Average as a Measure of Exposure to Coke-Oven Emissions 12 G. Accuracy of Estimated Exposures 15 H. Other Potential Human Exposure Routes 16 III SOURCES OF COKE OVEN EMISSIONS 19 A. The Coking Process 19 B. Environmental Emissions During Coking 20 C. Coke Processing Plants 21 IV A METHOD OF ASSESSING BaP AND BSO CONCENTRATIONS IN THE VICINITY OF COKE-OVENS 30 A. General 30 B. Categorization of Coke Plants by Emission Control . . 31 C. Background Concentrations 32 D. Evaluation of Ambient Concentration Data for Coke Plant Locations 35 E. Relationship Between BaP and BSO Atmospheric Concentra- tions 40 F. Population Exposure Estimates 43 ------- Appendices A AMBIENT ATMOSPHERIC BaP AND BSO CONCENTRATIONS 45 rt A. General 45 B. Atmospheric BaP and BSO Concentration Data Recorded Near Coke Manufacturers 45 C. Ambient Background BaP and BSO Concentration Data . . 62 B STATISTICAL EVALUATION OF BaP ATMOSPHERIC CONCENTRATION DATA RECORDED IN THE VICINITY OF COKE PLANTS 80 A. General 80 B. Statistical Distribution of 24-Hour BaP Atmospheric Concentrations 80 C. Precision of Estimates Based Upon Small Sample Sizes 82 D. Evaluation of Ambient Concentration Data as a Function of Distance from Coke Plant Locations 85 C DETAILED ESTIMATES OF POPULATIONS AND BaP CONCENTRATIONS FOR INDIVIDUAL COKE FACILITIES 101 BIBLIOGRAPHY 105 vi ------- ILLUSTRATIONS II-l II-2 IV-1 IV-2 B-l B-2 B-3 B-4 B-5 B-6 B-7 B-8 B-9 B-10 B-ll B-12 B-13 B-14 Estimated Population Exposures to BaP Estimated Population Exposures to BSD Relationship Between BSD and BaP Atmospheric Concen- trations for all Locations Relationship Between BSD and BaP Atmospheric Concen- trations for Coke Oven Locations .... Statistical Distribution for Atmospheric BaP Concen- trations Atmospheric Concentrations of BaP for Johnstown, Pennsylvania Atmospheric Concentrations of BaP for Geneva, Utah Atmospheric Concentrations of BaP for Wayne County, Michigan Atmospheric Concentrations for BaP for Allegheny County, Pennsylvania Atmospheric Concentrations of BaP for Buffalo, New York Atmospheric Concentrations of BaP for Birmingham, Alabama Atmospheric Concentrations of BaP for Granite City, Illinois Atmospheric Concentrations of BaP for Sparrows Point, Atmospheric Concentrations of BaP for Cleveland, Ohio Atmospheric Concentrations of BaP for Monessen, Penn- sylvania Atmospheric Concentrations of BaP for Gadsden, Alabama Atmospheric Concentrations of BaP for Duluth, Minnesota Atmospheric Concentrations of BaP for Philadelphia, 10 13 41 42 81 86 87 88 89 90 91 92 93 94 95 96 97 Pennsylvania 93 vii ------- TABLES II-l Estimated BaP Emissions in the United States (1972) 4 II-2 Summarization of Ambient BaP and BSO DATA 6 II-3 Annual Average Exposure Concentrations for BaP Emitted by Coke Ovens 9 II-4 Summarization of Population Exposures to BaP from Coke Oven Emissions 11 II-5 Annual Average Daily BSO Inhalation for Persons Re- siding Near Coke Plants 14 II-6 Benzo(a)pyrene Concentrations in Foods 17 III-l Correlations Among PAH Compounds in the Air over Greater Birmingham, Alabama, 1964 and 1965 .... 22 III-2 Correlation Coefficients Among Log Concentrations of 13 PNA and BSO Samples Taken Within Five Coke Plants 23 III-3 By-Product Coke Plant Locations and Capacities . . 25 III-4 Estimated Size and Productive Capacity of By-Product Coke Plants in the United States on December 31, 1975 29 III-5 Directory of U.S. Beehive-Coke Plants 24 IV-1 Assumed Emission Weighting Factors for Plant Com- pliance Status 33 IV-2 Classification of Coke Plants into Emission Cate- gories (1974-1975) 34 IV-3 Estimated Annual Background Concentrations of BaP for Coke Plant Locations 36 A-l Monessen Air Study, 24-Hour Sample Characteristics 47 A-2 Ambient BaP Concentrations for Allegheny County, Pennsylvania 48 A-3 BaP Data Obtained During First Stage Alerts at Liberty BoroughSite 8790 49 A-4 Atmospheric BaP Concentrations Near the Geneva Works in Utah 49 A-5 Ambient BaP Concentrations for Wayne County, Michigan 51 A-6 Ambient BaP Concentrations for Buffalo, New York 52 A-7 Ambient BaP Concentrations for Duluth, Minnesota 53 viii ------- A-8 Ambient BaP Concentrations for Gadsden, Alabama . . 53 A-9 Ambient BaP Concentrations for Birmingham, Alabama 55 A-10 CHAMP Site Ambient Atmospheric BaP Data for the Birmingham Area (1975 Data) 55 A-ll Ambient BaP, BSO, and TSP Concentrations for Johns- town, Pennsylvania 56 A-12 Ambient BaP, BSO, and TSP Concentrations for Philadel- phia, Pennsylvania 57 A-13 Ambient BaP Concentrations for Granite City, Illinois 59 A-14 Additional Atmospheric Ambient Data for Granite City, Illinois 59 A-15 Ambient BaP Concentrations for Houston, Texas ... 60 A-16 Ambient BaP Concentrations for Cleveland, Ohio . . 61 A-17 Ambient Atmospheric BaP and BSO Concentrations for Sparrows Point, Maryland 63 A-18 Ambient BaP and BSO Concentrations for Chattanooga, Tennessee 63 A-19 Annual Average Ambient BaP Concentrations at NASN Urban Stations (ng/m3) 64 A-20 Seasonal Variations of Benzene Soluble Organic Sub- stances 66 A-21 Summarization of Ambient BaP and BSO Data 68 A-22 Annual BaP Averages for Selected Cities 68 A-23 Ambient BaP Concentrations for Pennsylvania, 1976 70 A-24 Distribution of BaP Concentrations in Ambient Air at Charleston, South Carolina 75 A-25 Ambient Atmospheric BaP and BSO Concentrations for Maryland Locations 76 A-26 Atmospheric BaP and BSO Concentrations for CHESS and CHAMP Sites (1975 Data) 79 B-l Statistical Summary for Sampling Data Taken from a Number of Locations 83 B-2 Estimated Parameter Values for Regression Approxima- tions to Ambient Data 100 C-l Detailed BaP Population Exposures (ng/m3) 102 C-2 BaP Exposures for Persons in Locations Having More than One Coke Facility 104 ix ------- LIST OF CHEMICAL ABBREVIATIONS A anthracene Ant anthanthrene or anthanthrene BaA benz(a)anthracene BaP benzo(a)pyrene BbF benzo(b)fluoranthene BcA benzo(c)acridene BeP benzo(e)pyrene BghiP benzo(g,h,i)perylene BjF benzo(j)fluoranthene BkF benzo(k)fluoranthene BSD benzene soluble organics Chr chrysene Cor coronene DBahA dibenz(a,h)anthracene Flu fluoranthene Per perylene Pyr pyrene TSP total suspended particulates ------- I INTRODUCTION The primary objective of this study has been to quantify the environ- mental atmospheric exposure of the general human population to coke-oven emissions of benzo(a)pyrene (BaP) and benzene soluble organics (BSO). To do so, we have located and characterized coke production plants, estimated atmospheric environmental concentrations of pollutants resulting from coke production, and estimated human populations exposed to various levels of these pollutant concentrations. In this report, we indicate human exposure to coke-oven emissions in terms of the average amount inhaled per day for each population subgroup. Note that this study reports exposures that took place before biological sorption occurred and that the degree of sorption is not considered. In addition, because the results of this study are intended to serve as input to another study in which health effects are to be assessed, health effects are not addressed. Another study is also being conducted to describe the chemical and physical properties of coke-oven emissions; therefore, these results are not included in this study. The main findings of this report are provided in tables and figures. The text describes the methodologies, assumptions, and data sources used. All estimates given in this report depend in large part on data reliability and availability, both of which varied widely. Some discussion of this variability is provided in Appendices A and B. ------- II SUMMARY AND CONCLUSIONS A. Overview There are 65 by-product coke plants in the United States. (Some authors list 62, omitting separate operations for three of the locations.) These plants consist of an estimated 231 coke oven batteries, containing 13,324 ovens that have a theoretical maximum annual productive capacity of 74.3 million tons of coke. The industry generally operates at about of the theoretical capacity. Environmental emissions occur in the coking operation during charging, from leaks in the oven doors and the tops of ovens, from the waste gas stack, during pushing and quenching, and from by-product processing. The various batteries are characterized by different types of control and operational procedures which affect the amount of their emissions. In general, the measurement of environmental emissions from coke-ovens has been limited to some atmospheric sampling of BaP for about one-third of the locations. Atmospheric concentrations of TSP have also been measured for many of the locations, and the BSO fraction of the TSP has been measured for a few locations. Atmospheric concentrations of other sub- stances that may be emitted by coke-ovens have generally not been recorded. In addition, very little work has been done to characterize detailed emission factors for coke-ovens. Because of these limitations, this report's estimates of nonoccupational exposures to coke-oven emissions are based on the two substances for which some atmospheric concentration data are availableBaP and BSO. These two substances might be considered as substitute or surrogate measures of total exposure. However, much more monitoring data will be required before we can conclude that concen- trations of these two substances always correlate well with other emitted substances that are important from a health viewpoint. ------- Atmospheric concentration data recorded during 1964 and 1965 for Birmingham, Alabama, with several coke plants located in the vicinity, showed that the correlation coefficient for BaP with 11 other polynuclear aromatic compounds ranged from 0.65 to more than 0.99. For BSO with 11 other substances, it ranged from 0.58 to 0.88 (U.S. EPA, 1975). In addi- tion, occupational exposure data recorded by NIOSH (1974) show correlation coefficients between BSO and 13 other polynuclear aromatic compounds to range from 0.71 to 0.94. The same study also showed correlation coeffi- cients for BaP with 12 other polynuclear aromatic compounds ranging from 0.57 to 0.95. The substances used in these correlation studies are given in Section III of this report. It is difficult to use ambient data "to assess exposures to coke-oven emissions; most communities have other sources of the same substances, generally associated with coal and other fossil fuel combustion. Hence, any evaluation of population exposures to coke-oven emissions must separate the background concentration from the coke-oven contribution. Of course, for health risk assessment, the summation of the two is important. Table II-l reports a BaP emission inventory made by the Environmental Protection Agency (EPA) for 1972. Stationary sources account for 98% of the nation- wide estimate. Estimates of BaP emissions from coke ovens range from about 0.06 ton per year to approximately 170 tons per year, depending on assumptions used. EPA (1974) used the higher value because it is based on data from the United States (using a crude emission factor of 2.5 g of BaP per ton of coal processed). The coke production is estimated to account for approximately 19% of the nationwide BaP emissions. EPA is currently working on better factors to characterize coke-oven emissions (Manning, August 1977). BaP may also have natural sources, including bituminous coal which also contains benzo(a)anthracene and other polycyclic organic matter. Two of three types of asbestos used industrially were found to contain oils with BaP. Mold may constitute another source (U.S. EPA, 1974). The National Air Surveillance Network (NASN) routinely monitors suspended particulate levels in urban and nonurban areas. This program is described in more detail in Appendix A. BaP and BSO are monitored for ------- Table II-l ESTIMATED BaP EMISSIONS IN THE UNITED STATES (1972) Emissions Source Type tonne/yr Stationary Sources Coal, hand-stoked residential furnaces 300 Coal, intermediate-size units 7 Coal, steam power plants <1 Oil, residential through steam power type 2 Gas, residential through steam power type 2 Wood, home fireplace 25 Enclosed incineration-apartment through municipal 3 Vehicle disposal 25 Forest and agriculture 11 Other open burning 10 Open burning, coal refuse 310 Petroleum, catalytic cracking 7 Asphalt air blowing <1 Coke production (0.06)-170 Mobile Sources Gasoline-powered automobiles and trucks 11 Diesel-powered trucks and buses <1 Tire degradation 11 Source: US EPA (1974). ------- 40 locations Chat include cities with and without coke-ovens and rural areas.* The BaP and BSD concentrations recorded for this program are sum- marized in Table II-2. The BaP concentrations are generally 0.1 ng/m for rural locations. Most urban locations without coke-ovens have aver- age concentrations of less than 1 ng/m (the average is 0.38 ng/m ); however, areas with coke-ovens generally have average concentrations in 3 3 excess of 1 ng/m (the average is 1.21 ng/m ). B. At-Risk-Populations The at-risk populations to coke-oven emissions are defined as the resident populations exposed to coke-oven atmospheric emissions. Exposure is based on the estimated average annual concentrations occurring at the place of residence of at-risk population subgroups. Average daily human exposure is calculated as the product of the average annual concentration and human daily ventilation rate. C. Population Estimation jAn evaluation of the concentration data shown in Appendix A indicates that coking operations may possibly affect atmospheric concentrations out to a radius of 15 km from the operations.I For most cases, the affected radius is considerably less than 15 km; however, for conservative analysis, population residing within a 15-km radius from each coke plant is considered as the maximum potential exposure population. For the estimation of populations at-risk to selected concentrations resulting from coke ovens, the resident populations were calculated in a series of five concentric rings about each coke plant. The spacing of the rings was based on the shape of the concentration versus distance functions illustrated in Appendix B. The distances are 0-0.5, 0.5-1.0, 1.0-3.0, 3.0-7.0, and 7.0-15 km. Geographic coordinates of most of the coke plants were obtained from the U.S. EPA NEDS data system. The remainder were obtained from consult- ing maps or by telephone conversations. The population residing in each concentric ring about each coke plant was obtained from the Urban Decision Systems, Inc., Area Scan Report, a computer data system that contains the BSO monitoring was discontinued in 1972. ------- Table II-2 SUMMARIZATION OF AMBIENT BaF AND BSO DATA Pollutant BaP (ng/m3) 1975 Data BSO (pg/m3) 1971-72 data Statistic Average Sample size Range Average Sample size Range Cities with Coke Ovens 1.2] 21 0.3-4.7 4.21 25 2.1-7.3 Cities without Coke Ovens 0.38 13 0.03-0.9 3.75 12 1.9-5.6 Rural 3 <0. 0. 2 0.8-1 Areas 1 95 .1 ------- 1970 census data in the smallest geographic area available (city blocks and census enumeration districts). The total population residing in each of these rings for all the coke plants is as follows: Distance from Resident Coke Plant (km) Population 0-0.5 32,700 0.5-1 116,000 1-3 1,644,000 3-7 7,226,000 7-15 22,200,000 |The total population residing within 15 km of the coke plants is approx- imately 31,220,000 people.I In the exposure calculations it was found -i * that only about 17,100,000 of these people were affected by coke oven emissions. D. Population Exposures to BaP Emitted by Coke-Ovens The annual average BaP atmospheric concentrations were estimated for each of the five concentric rings around each of the coke plants. Recorded ambient data were used for those locations having a sufficient number of samples and monitoring sites; otherwise, the extrapolative modeling technique described in Section IV was used. For locations with several coke plants, a procedure was devised to assess the combined atmospheric concentrations by summing the contribution for individual plants for areas in overlapping geographic rings. The population within the rings was assigned to the overlapping sections by using uniform distribution assumptions. Two calculations were made for the atmospheric concentration of each ring: the concentration resulting from only coke oven emissions and the total concentration, which includes background plus coke oven emissions. The background concentrations used are given in Section IV and range * Coke oven emissions resulted in an increase in the average annual atmospheric BaP concentrations of 0.1 ng/m^ or more. ------- 2 from 0.04 to 1.6 ng/m . The wide range In background concentrations indicates the variations of other BaP-emitting activities in the cities. Table II-3 summarizes the number of people exposed to various BaP concen- tration levels. Detailed exposure estimates are given in Appendix C. The cumulative distribution for these exposure concentrations is given on Figure II-l. Total average BaP concentrations range from a high of 3 3 100 ng/m to a low of below 1 ng/m . The median population exposure concentration is around 7 ng/m . Potential human exposures from inhalation are given in Table 11-4. 3 For these exposures a human ventilation rate of 15 m /day was assumed. This is the amount of air inhaled per 24-hr day by a standard man as defined in the Radiological Health Handbook (1960). The approximately 17,100,000 exposed people inhale between 3 to 1,500 ng BaP per day on an annual average basis. About one-half of these people inhale more than 100 ng BaP per day. E. Population Exposures to BSO Emitted by Coke-Ovens Sufficient data have not been collected near coke plants nor have emission factors been developed for adequately assessing the atmospheric BSO concentrations resulting from the plants' emissions. The approach taken here is to estimate the BSO concentrations, based on the estimated BaP concentrations. A number of problems are associated with this approach, however, and the results can, at best, be described as "ballpark estimates." Further work on assessing plant emission factors or measuring environmental concentrations should help to improve the quality of future estimates. The approach taken has been described in Section IV of this report. Three methods of estimation were tried. All three methods estimate BSO contributions attributable to coke-ovens and add this to estimated back- ground concentrations. One method involved using empirical formulas derived from data taken from coke oven areas where both BaP and BSO * 3 In a kepone assessment report, U.S. EPA (1976b) used a rate of 8.6 m /day for an average adult. The exposures given here can be converted to the 8.6 m-Vday rate by multiplying by 0.57. ------- Table II-3 ANNUAL AVERAGE EXPOSURE CONCENTRATIONS FOR BaP EMITTED BY COKE OVENS Subgroup Cumulative Number of People Exposed Concentration Range (ng/m3) 95-100 50-55 45-50 40-45 35-40 30-35 25-30 20-25 15-20 10-15 8-10 6-8 5-6 4-5 3-4 2-3 1-2 0.5-1 0.2-0.5 Background, plus Coke Oven Emissions 1,800 2,670 2,720 4,220 5,920 9,320 14,120 19,120 82,820 630,220 705,320 981,020 1,097,720 1,345,920 3,069,020 7,335,620 15,148,620 16,754,020 17,106,620 Coke Oven Emissions Only 1,800 2,670 2,720 4,220 5,920 8,320 9,920 18,920 82,620 219,920 662,620 798,920 995,220 1,182,320 1,971,620 3,216,820 8,243,520 12,923,120 17,106,620 Number exposed to indicated concentration or more. ------- 100 I i o 111 u o o 111 o tc. Ill 3 Z Q UJ i II Illlll 1I Illlll I I I I I III BACKGROUND CONCENTRATIONS ARE ASSUMED TO BE 0.04 to 1.6 ng/m3 FOR INDIVIDUAL LOCATIONS I I I I Mil I ' I I I Ml 104 106 106 NUMBER OF PEOPLE EXPOSED TO INDICATED CONCENTRATION OR MORE 107 2x107 FIGURE 11-1. ESTIMATED POPULATION EXPOSURES TO BaP (Background, plus Emissions) ------- Table II-4 SUMMARIZATION OF POPULATION EXPOSURES TO BaP FROM COKE OVEN EMISSIONS (Background Plus Coke Oven Emissions) Subgroup Concentration^ Range (ng/m3) 95-100 50-55 45-50 40-45 35-40 30-35 25-30 20-25 15-20 10-15 8-10 6-8 5-6 4-5 3-4 2-3 1-2 0.5-1 0.2-0.5 Subgroup Population Exposure (ng/day)* 1,425-1,500 750-825 675-750 600-675 525-600 450-525 375-450 300-375 225-300 150-225 120-150 90-120 75-90 60-75 45-60 30-45 15-30 7.5-15 3.0-7.5 Number of People in Subgroup 1,800 870 50 1,500 1,700 3,400 4,800 5,000 63,700 547,400 75,100 275,700 116,700 248,200 1,723,100 4,266,600 7,813,000 1,605,400 352,600 Cumulative Number of Exposed People** 1,800 2,670 2,720 4,220 5,920 9,320 14,120 19,120 82,820 630,220 705,320 981,020 1,097,720 1,345,920 3,069,020 7,335,620 15,148,620 16,754,020 17,106,620 ** Based on the annual average. Number exposed to indicated concentration or more. 11 ------- atmospheric concentrations have been measured. The other two methods involved multiplying the BaP concentration attributable to coke ovens by a constant that relates BSO to BaP and adding this to an assumed background BSO concentration. The two factors used were 1 ng BaP = 0.1 yg BSO and 1 ng BaP = 0.5 yg BSO. The 0.1 factor appears to be reasonable, based on occupational exposure data whereas the 0.5 factor should give an upper limit. An average background BSO concentration of 3.75 yg/m3 was assumed for all locations. The exposures estimated by these methods are given on Figure II-2. The results for the empirical formula and the 0.1 factor were very similar, only one of which is plotted on Figure II-2. The estimated human popula- O tion exposures based on a standard human inhalation of 15 m of air per day are given in Table II-5. Average annual BSO concentrations are estimated to range from 3 1 3.75 yg/m (assumed background) to 11 yg/m . The median population expo- 3 sure concentration is 5.4 yg/m . Based on these exposure concentrations, the exposed population would inhale an average of between 45 to 165 yg/day. If we use the upper limit estimates for BSO concentrations, the human inhalation exposure could rise to almost five times these values. F. Considerations in the use of the Annual Average as a Measure of Exposure to Coke-Oven Emissions Exposure estimates in this report are given in terms of the daily exposure averaged over a year. Statistically, this measure represents the expected daily exposure; multiplied by 365, it gives the total expected annual exposure. However, the statistical distribution of con- centrations for a specific location is not symmetrical; rather, it takes the form of many relatively small observations and a few relatively larger observations. Examples of these distributions are given in Appendix B. The averages for these types of distributions are much larger than the median and, generally, only 20 to/0% of the observations might be expected to exceed the mean in value. The geometric average rather than the arith- metic average is a better measure to characterize the central location of these distributions; however, exposure estimates based on the geometric average are difficult to interpret. The overall arithmetic average was found to be 1.8 times as large as the geometric average (Appendix B). 12 ------- 35 30 o .E o> a. I g cc UJ o § o o 01 OC UJ _ z Q IU 1 25 20 15 10 II TT i I I I I I I II I I I I I II I 1 I I I I Ml HIGH ESTIMATE, ASSUMES 0.5 fig BSO FOR 1 ng BaP EMITTED BY COKE OVENS > ESTIMATE BASED ON FUNCTIONS DERIVED FROM EMPIRICAL DATA BACKGROUND CONCENTRATION 10e IO7 2 K IO7 NUMBER OF PEOPLE EXPOSED TO INDICATED CONCENTRATION OR MORE FIGURE 11-2. ESTIMATED POPULATION EXPOSURES TO BSO (Background, plus Emissions) ------- Subgroup 1 Concentration Range Cpg/m3) 10.8-11 8-9 7-8 6-7 5-6 4-5 3-4 Table II-5 ANNUAL AVERAGE DAILY BSD INHALATION FOR PERSONS RESIDING NEAR COKE PLANTS Subgroup Exposure Range (pg/day)* 162-165 120-134 105-134 90-105 75-90 * 60-75 45-60 Number of People Exposed 1,800 2,420 8,400 54,000 1,034,000 13,900,000 2,106,000 Cumulative Number of People Exposed 1,800 4,220 12,620 66,620 1,100,620 15,000,620 17,106,620 Estimated values are based on functions derived from empirical data and include background and emissions. Exposures are based on the annual averages. 14 ------- Calculations of averages and standard deviations are given in Appendix B for BaP concentration data recorded over a number of different days at a specific location. For most of these locations, the average was found to equal the standard deviation. Thus, concentrations for an individual worst case day could easily be three times the annual average. Conversion methods given by Thuillier (1977) show that the 24-hour worst case can be expected to be four times the average. This large difference between the annual average and the worst case is quite logically explained by the variations in meteorological conditions over a year. G. Accuracy of Estimated Exposures The accuracy of the exposure estimates are difficult to assess because many relevant factors associated with the various monitoring programs are unknown (e.g., the accuracy of the monitoring data and if the monitoring days were selected at random). Another important source of error arises from using a general model based on a sampling of coke plants to represent all coke plants. The general model is not expected to give highly accurate estimates for the concentrations at any location because only limited plant-specific data went into the model. The model is, however, expected to give fairly accurate estimates of overall national exposures because it was formulated by using averages of parameters that represent a range of meteorological, geographical, and emission control conditions. The potential errors in estimated exposure concentrations were addressed by using the model to predict average annual concentrations for 1- and 3-km distances for a number of coke plants for which environ- mental BaP monitoring data are available. The differences between the observed and predicted concentrations then provide an estimate of the accuracy of the procedure. The one-standard deviation value for these differences was about 100%. This indicates that the predicted annual average concentration for any location for a specific coke plant could differ from the actual average by 100% or more. The standard deviation for the overall national estimated exposures should be considerably less than for individual locations because many sources of error are, in effect, being averaged. The one-standard deviation value of the overall national 15 ------- estimated exposure concentrations is on the order of 10 to 100% of the actual concentration. The size of the error depends primarily on the number of coke plants having exposed populations in an exposure concen- tration subgrouping. These accuracy estimates exclude potential errors associated with the monitoring data. Note that these percent errors are given relative to the actual exposure concentrations. Thus, a 100% error indicates that the actual concentration may range from one-half to twice the estimated value. H. Other Potential Human Exposure Routes There are potential human exposure routes for coke-oven emissions other than inhalation. These include ingestion of contaminated food and water and dermal contact. In addition, family members of occupational workers might be exposed through particulates brought home on clothing and other equipment such as lunch pails and automobiles. An assessment of potential human exposures via these routes was excluded from the scope of this study because they either appear to be much less significant than the inhalation route or because of the lack of available data. The dermal exposure would result from contamination of clothing or the skin directly from atmospheric concentrations. Hence, the atmospheric concentration estimates given in the summary tables of this report can be used to provide estimates of dermal exposures. Foods can become contaminated because of atmospheric fallout of parti- culates or by way of contaminated water released by the coke plant. The contamination may be on the surface of plants from fallout or included by root-uptake. Animals can become contaminated by drinking contaminated water, eating contaminated foods, or breathing contaminated air. Con- tamination may also result from other man-made or natural sources. Processed foods may contain additional contaminations from the combustion of fuels used in smoking, roasting, or broiling. Foods in general have been found to contain concentrations of polynuclear aromatic hydrocarbons such as benz(a)anthracene, chrysene, and benzo(a)pyrene (Radding et al., 1976). Table II-6 lists concentration levels of BaP in some foods. As 16 ------- Table II-6 BENZO(A)PYRENE CONCENTRATIONS IN FOODS Concentration Food Cereals Potato peelings Potato tubers Barley, wheat, rye Cabbage Spinach Lettuce Tomatoes Fruits Refined fats and oils Fresh fish Broiled meat and fish Smoked fish Smoked meat/sausage Roasted coffee Roasted coffee Teas Whiskey (ug/ke) 0.3-0.8 0.36 0.09 0.2-4.1 24.5 7.4 2.8-12.8 0.22 2.0-8.0 0.9-15 <0.1 0.2-0.6 1.0-78.0 0.02-107.0 0.3-0.5 * 0.1-4.0 * 3.7-3.9 * 0.04 Reference A A A B B C B B C C D C E C B C B B A - Shabad (1972) B - Grummer (1968) C - IRAC (1973) D - Gorelova (1971) E - Andelman (1970) 17 ------- expected, the BaP concentration of certain prepared foods is higher than for other foods. At present, insufficient information is available to assess the potential contamination of foods by coke-oven emissions. Polynuclear aromatic hydrocarbons find their way into waterways already absorbed onto aerosols or bacteria. Although their solubility in pure water is essentially zero, they may exist in water in association with organic matter or colloids (Radding et al., 1975). The IRAC (1973) report lists BaP concentrations in drinking water of 0.0001 to 0.023 yg/1. 18 ------- Ill SOURCES OF COKE OVEN EMISSIONS A A. The Coking Process Coke is a porous cellular residue from the destructive distillation or carbonization of coal. It is used as a fuel and reducing agent in blast furnace operations, and in foundries as a cupola fuel. Of the approximately 60 million tons of coke produced annually in the United States, 92% is used in blast furnaces, 5% in foundry operations, and 3% in other types of industrial plants. Of the total coke production, approx- imately 90% is produced by steel industry plants, 8% by foundry plants, and 1% by beehive ovens. Two basic processes are used in the production of coke: One recovers vapors and other by-products from the coking process (by-product ovens), and one does not (beehive ovens). The beehive oven, an older design, that has been steadily replaced by the newer by-product design is excluded from this analysis. A by-product coke battery consists of 10 to 100 ovens made up of chambers for heating, coking, and regeneration. Heating and coking flues alternate with each other so that there Is a heating flue on either side of a coking flue; the regenerative flues are located underneath. The coking cycle begins with the introduction of coal into the coke oven. This operation, called "charging," is carried out with a mechanical "larry car" on rails on the top of the battery. The larry car receives a load of coal from the coal bunker at the end of the battery. The car moves down the battery to the pven to be charged. The lids on the oven charging holes are removed, the larry car ±s positioned over the holes, and the hoppers are emptied. During the charge, the oven is aspirated The material contained in this section is summarized from the Federal Register (October 22, 1976). 19 ------- by steam jets in the standpipes connecting the by-product gas collector main with the oven. This operation, called "charging the main" is designed to limit the escape of gas from the oven during the charging process. After charging is completed, the lids are replaced and the aspiration system is shut off. The "coking time," the time required to produce coke from coal, is governed by numerous factors, including the condition and design of the oven heating system, width of the coking chamber, coal moisture, and the nature of the coals being coked. The coking time for blast furnace coke varies from 16 to 20 hours. Coking times for foundry coke are longer than for blast furnace coke because coke of different physical character- istics is required for foundry operations. When the coal is coked, the doors on each side of the oven are re- moved and the coke is pushed out. A large mechanically operated ram attached to a pusher machine moves the coke out the opposite side of the oven called the "coke side," through the "coke-guide" attached to the door machine and into a railroad car called the "hot car" or "quench car." The quench car moves down the battery to a "quench tower" where the hot coke is cooled with water. The quenched coke is then dumped onto the coke wharf, from which it is conveyed to the screening station for sizing, then to the blast furnace, or removed for other purposes. When the doors on the oven are replaced, the oven is ready to be charged again. B. Environmental Emissions During Coking Environmental emissions can occur during charging; during coking from leaks in the doors and on the top of the oven; from the waste gas stack; and during pushing and quenching, and from by-product processing. Coke-oven emissions are described as a complex mixture of particulates, vapors, and gases (Federal Register, October 22, 1976). (A detailed assessment of the chemical and physical properties of these emissions is being prepared as a separate document and, therefore, is not included here.) 20 ------- Because of the effort and complexity that would be required in characterizing all of the constituents of coke-oven emissions, various surrogate measures have been used in the past. These usually are of three types: TSP, BSD, and BaP. TSP is generally considered not to be a specific enough measure for assessing total occupational health effects (Federal Register, October 22, 1976). The concept of a surrogate measure would be valid if it could be shown that that measure correlates well with the presence of other emitted substances known to have adverse health effects. Atmospheric concentration data recorded during 1964 and 1965 for Birmingham, which has several coke plants in the surrounding area, showed that the correlation coefficient for BaP with 11 other substances ranged form 0.65 to more than 0.99. For BSO with 11 other substances the coefficient ranged from 0.58 to 0.88 (U.S. EPA, 1975), indicating a fairly good association. These are given in Table III-l. In an occupational exposure study, the atmospheric concentrations of 13 polynuclear aromatics (PNAs) and the total benzene soluble organics were recorded. A correlation study was made of these data using logarithmic transformations because the data followed a log-normal distribution (NIOSH, 1974). The correlation of the PNAs with BaP and BSO are given in Table III-2. Except for one case, all the correlation coefficients exceeded 0.7, thus indicating a fairly good correlation. The correlation of BSO with the 13 PNAs was generally better than the similar correlations for BaP. The occupational and the Birmingham correlation studies provide some justification for using a surrogate measure rather than trying to identify and control each of the PNA compounds emitted by coke-ovens. C. Coke Processing Plants In 1975, 57.2 million tons of coke were produced in the United States. By-product ovens produced 98.7% of the total production, with beehive ovens accounting for the remaining 1.3%. Approximately 90% of the coke is used in blast furnace plants, whereas 2% is exported. The remainder is primarily used in foundries. The yield of coke from coa], which averaged 68.4% in 1975, has remained fairly constant during the past decade (Sheridan, 1976). * TSP - total suspended particulates. 21 ------- Table III-l CORRELATIONS AMONG PAH COMPOUNDS IN THE AIR OVER GREATER BIRMINGHAM, ALABAMA, 1964 AND 1965 Compound Flu Pyr BaA Chr BeP BaP Per BghiP A Cor TSP BSO BaP 0.916 0.935 0.988 0.980 0.998 1.000 0.985 0.966 0.971 0.815 0.789 0.651 Compound BSO 0.582 0.684 0.597 0.746 0.677 0.651 0.689 0.804 0.672 0.867 0.880 1.000 TSP 0.668 0.730 0.742 0.842 0.823 0.789 0.830 0.839 0.716 0.856 1.000 0.880 Source: U.S. EPA (1975). 22 ------- Table III-2 CORRELATION COEFFICIENTS AMONG LOG CONCENTRATIONS OF 13 PNA AND BSO SAMPLES TAKEN WITHIN FIVE COKE PLANTS Compound Flu Pyr BcA Chr BaA BbF BjF BkF BeP BaP DBahA BghiP Ant BSO BaP 0.797 0.740 0.569 0.857 0.824 0.776 0.768 0.813 0.950 1.000 0.694 0.855 0.892 0.914 BSO 0.914 0.862 0.713 0.936 0.909 0.884 0.894 0.915 0.922 0.914 0.725 0.875 0.905 1.000 Source: NIOSH (1974). 23 ------- In the United States, 65 plants produce coke. (Some authors list only 62 by combining three pairs of closely co-located plants, where each pair of plants are owned by the same corporation.) The 65 plants are listed in Table III-3 which also lists the coal capacity and the 1974 coal consumption on a plant-by-plant basis. The plants consist of an estimated 231 coke-oven batteries containing 13,324 ovens that have a theoretical maximum annual productive capacity of 74.3 million tons of coke. Because of depressed economic activity in 1975, the industry operated at only 76% of this capacity. Coke production on a state-by- state basis is given in Table III-4. The Keystone Coal Industries Manual (1975) lists six beehive-coke plants. These operate in two states (Pennsylvania and Virginia). Although excluded from this analysis, they are listed in Table III-5. Table III-5 DIRECTORY OF U.S. BEEHIVE-COKE PLANTS Name or Location of Plant Pennsylvania 1. Mahoning 2. Daugherty 3. Laughead Virginia 5. Vansant 6. Esserville County Company Armstrong Caipentown Coal & Coke Co. Fayette Bortz Coal Company Fayette Ruane Coal & Coke Company Buchanan Wise Jewell Smokeless Coal Corp. Christie Coal & Coke Source: Keystone Coal Industries Manual (1975). 24 ------- Table III-3 BY-PRODUCT COKE PLANT LOCATIONS AND CAPACITIES State. City N) Alabama 1. Tarrant 2. Holt 3. Woodward 4. Gadsden 5. Thomas 6. Birmingham 7. Fairfield California 8. Fontana Colorado 9. Pueblo Illinois 10. Granite City 11. Chicago 12. Chicago 13. South Chicago Indiana 14. Chesterton 15. Indianapolis 16. Terre Haute 17. East Chicago 18. East Chicago 19. Gary 20. Indiana Harbor Plant Name Company Tarrant Plant Holt Plant Woodward Plant Gadsden Plant- Thomas Plant Birmingham Plant Fairfield Plant Fontana Plant Pueblo Plant Granite City Steel Div. Chicago Plant Wisconsin Steel Works South Chicago Plant Burns Harbor Plant Prospect Street Plant Terre Haute Plant Plant No. 2 Plant No. 3 Gary Plant Indiana Harbor Plant Alabama By-Products Co. Empire Coke Co. Koppers Company, Inc. Republic Steel Corp. Republic Steel Corp. U.S. Pipe and Foundry Co. U.S. Steel Corp. Kaiser Steel Corp. CF&I Steel Corp. National Steel Corp. Interlake, Inc. International Harvester Co., Wisconsin Steel Div. Republic Steel Corp. Bethlehem Steel Corp. Citizens Gas & Coke Utility Indiana Gas and Chemical Corp. Inland Steel Co. Inland Steel Co. U.S. Steel Corp. Youngstown Sheet and Tube Co. Annual Coal Capacity (tons) 1,200.000 150,000 800,000 820,000 185,000 1,175,000 2,500,000 2,336,000 1,332,000 1,132,000 949,000 991,000 590,000 1974 Coal Consumption (tons) 1,760,000 900,000 643,000 2,630,000 675,000 204,000 3,102,000 1,642,000 3,700,000 2,100,000 2,525,000 584,838 193,000 3,096,000 1,258,000 1,750,000 Sources: Keystone Coal Industries Manual (1975) and Varga (1974). ------- Table III-3 (Continued) State. City Kentucky 21. Ashland Maryland 22. Sparrows Point Michigan 23. Detroit 24. Dearborn 25. Zug Island (Detroit) Minnesota 26. St. Paul 27. Duluth Missouri' 28. St. Louis flew York 29. Buffalo 30. Lackawana 31. Buffalo Ohio 32. Iron ton 33. Hew Miami 34. Mlddletown 35. Painesville Plant Name Company Annual Coal 1974 Capacity Coal Consumption (tons) (tons) Seraet Sparrows Point Plant Semet Steel Plant Zug Island Plant St. Paul Plant Duluth Plant St. Louis Plant Harriet Plant Lackawana Plant Donner-Hanna Plant Ironton Plant Hamilton Plant Hiddletown Plant Painesville Plant Solvay Dlv., Allied Chemical Corp. 1,600,000 Bethlehem Steel Corp. 4,820,000 Solvay Div., Allied Chemical Corp. 900,000 Ford Motor Co. 1,800,000 Great Lakes Steel Dlv., National Steel Corp- 2,850,000 Koppers Company, Inc. 250,000 U.S. Steel Corp. 850,000 Great Lakes Carbon Corp., Missouri 450,000 Coke & Chem Div. Seraet-Solvay Div., Allied Chemical Corp. 400,000 Bethlehem Steel Corp. 4,250,000 Donner-Hanna Coke Corp. 1,387,000 Semet-Solvay Div., Allied Chemical Corp. 1,230,000 Annco Steel Corp. 934,000 Arnco Steel Corp. 748,000 Diamond Shamrock Corp. 215,000 4,100,000 3,385,000 210,000 ------- State. City 36. Portsmouth 37. Toledo 38. Cleveland 39. Massilon 40. Warren 41. Youngstown 42. Lorain 43. Campbell Pennsylvania 44. Swedeland 45. Bethlehem 46. Johnstown 47. Johnstown 48. Midland 49. Aliquippa 50. Pittsburgh 51. Erie 52. Philadelphia 53. Pittsburgh 54. Clairton 55. Fairleas Hills 56. Moneseen Tennessee 57. Chattanooga Texas 58. Houston 59. Lone Star Utah 60. Provo Plant Name Empire Toledo Plant Cleveland Plant Massilon Plant Warren Plant Youngstown Plant Lorain Cuyahoga Works Campbell Plant Alan Wood Plant Bethlehem Plant Rosedale Div. Franklin Div. Alloy & Stainless Steel Div. Aliquippa Plant Pittsburgh Plant Erie Plant Philadelphia Plant Neville Island Plant Clairton Plant Fairless Hills Plant Wheeling Chattanooga Plant Houston Plant E. B. Germany Plant Geneva Works Table III-3 (Continued) Annual Coal Capacity Company (tons) Detroit Steel Div. of Cyclops Corp- 600,000 Interlake Inc. 438,000 Republic Steel Corp. 2,220,000 Republic Steel Corp. 250,000 Republic Steel Corp. 650,000 Republic Steel Corp. 1,500,000 U.S. Steel Corp. 2,700,000 Youngstown Sheet and Tube Co. 2,300,000 Alan Wood Steel Co. 803,000 Bethlehem Steel Corp. 2,210,000 Bethlehem Steel Corp. 550,000 Bethlehem Steel Corp. 1,680,000 Crucible Inc., Div. Colt Industries 657,000 Jones and Laughlln Steel Corp. 2,250,633 Jones and Laughlin Steel Corp. 2,587,404 Hoppers Company, Inc. 290,000 Philadelphia Coke Division 715,400 Shenango Inc. 1,022,000 U.S. Steel Corp. 9,670,000* U.S. Steel Corp. 1,800,000 Pittsburgh Steel Corp. 750,000 Chattanooga Coke and Chemicals Co. 204,400 Armco Steel Corp. 584,000 Lone Star Steel Co. 498,000 U.S. Steel Corp. 2.000,000 1974 Coal Consumption (tons) 1,895,116 2,105,000 545,000 1,645,000 630,000 385,000 823,900 492,000 Based on a 1973 emission inventory. ------- Table III-3 (Concluded) West 61. 62. 63. 64. State, City Virginia Weirton Weirton Fairmont Follonsbee Plant Name Weirton Mainland Plant Weir tor's Brown's Island Plant Fairmont Plant East Steubenville Plant Company Weirton Steel Dlv., National Steel Corp. Weirton Steel Dlv., National Steel Corp. Sharon Steel Corp. Wheeling-Pittsburgh Steel Corp. Annual Coal Capacity (tons) 2,500,000 1,825,000 300,000 2,500,000 1974 Coal Consumption (tons) 284,000 Wisconsin 65. Milwaukee Milwaukee Solvay Coke Co. A Division of Picklands Mather and Co. 347,000 INJ 00 ------- Table III-4 ESTIMATED SIZE AND PRODUCTIVE CAPACITY OF BY-PRODUCT COKE PLANTS IN THE UNITED STATES ON DECEMBER 31, 1975 ro vo State Alabama California Colorado Illinois Indiana Kentucky Maryland Michigan Minnesota Missouri New York Ohio Pennsylvania Tennessee Texas Utah West Virginia Wisconsin Undistributed Total Number of Plants 7 1 1 4 6 (7) 1 1 3 2 1 3 12 12 (13) 1 2 1 3 (4) 1 - 62 (65) Number of Batteries 28 7 4 9 31 2 12 10 5 3 10 35 51 2 3 4 13 2 - 231 Number of Ovens 1,401 315 206 424 2,108 146 758 561 200 93 648 1,795 3,391 44 140 252 742 100 - 13,324 Maximum Annual Theoretical Productive Capacity (tons) 6,961,000 1,547,000 1,261,000 2,523,000 11,925,000 1,050,000 3,857,000 3,774,000 784,000 257,000 4,053,000 9,960,000 18,836,000 216,000 839,000 1,300,000 4,878,000 245,000 74,266,000 Coke Production in 1974 (tons) 5,122,000 C1) 1,912,000 9,073,000 C1 C1) 3,259,000 C1) C1) C1) 8,842,000 16,318,000 C1) J1) 3,555,000 12,656,000 60,737,000 Included in Undistributed. Source: Sheridan (1976). ------- IV A METHOD OF ASSESSING BaP AND BSO CONCENTRATIONS IN THE VICINITY OF COKE-OVENS A. General All available ambient concentration data recorded for BaP and BSO in the vicinity of coke-ovens are presented in Appendix A and analyzed in Appendix B. These data (mostly for BaP) have been recorded in 15 locations, some of which contain several coke plants; as a result, approx- imately one-third of the coke plants are represented. However, in many cases, the data were recorded for only a few days and for only a few sampling stations, thus making exposure estimates based solely upon them unreliable. Moreover, it was necessary to devise some method of predicting ambient concentrations for coke plant areas in which no atmospheric data have been recorded. A procedure for doing this is given here. One approach considered was to model the concentrations mathematically, basing it in part on emission factors, amount of coal processed, and local meteorology. When this approach was tried by the EPA (Youngblood, 1977), it was con- cluded that, because of the uncertainties in characterizing the sources themselves, definitive estimation of air quality impact of coke-ovens by means of dispersion calculations is impossible at this time. The EPA is currently working on developing better emission factors for coke-ovens. Because these will not be available for some time, however, it was decided to develop a procedure to extrapolate the available ambient data that have been recorded in the vicinity of coke plants to other locations for which no data has been recorded. When possible and when they seem reliable, the actual recorded ambient concentration data have been used to estimate population exposures. The procedure that was devised required the following steps, which are described in more detail in subsequent sections of this report: 30 ------- (1) Information on the type of environmental controls at coke plants is evaluated to determine if facilities can be grouped by their degree of control. (2) The background concentrations estimated for each coke plant location are those that would exist if the batteries were not in operation. (3) Existing ambient concentration data are evaluated to determine if atmospheric concentrations can be expressed as a function of distance from the coke plants. (4) These concentration functions are evaluated to determine if relationships can be derived from them, based on the amount of coal processed and the degree of environmental controls. (5) The functions are then used to estimate atmospheric concen- trations in the vicinity of coke plants, with subsequent estimation of human population exposures. B. Categorization of Coke Plants by Emission Control Emission factors are not well-developed for coking operations. Among other factors, they are thought to be a function of process equipment, environmental controls, and operating procedures. In theory, a different set of emission factors exists for each battery. These battery emission factors would be composed of emission factors for such sources as charging, door leaks, pushing, topside leaks, by-product processing, quenching, and the waste gas combustion stack. The most detailed source of information on coke battery pollution control compliance is based on a survey conducted by PEDCo during September 1974 to April 1975 (Kuliyian, 1976). Among other items reported in this survey was the compliance status of each plant or battery with regard to charging, doors, waste gas combustion stacks, pushing, and quenching. Compliance or noncompliance provide only a general indication of environmental emissions. In addition, some of the batteries have reduced their emissions since 1975. However, this time frame is consistent with the dates when much of the environmental concentration data were recorded. 31 ------- Weighting factors were assigned to each compliance status listed in the PEDCo survey (in, out, at least one battery out, under a legal plan, undetermined). These weighting factors are based on work performed by EPA personnel, who were familiar with coke operations, to roughly estimate BaP emission factors (Manning, March 18, 1977). This assignment of weights assumes that an in-compliance status indicates low emissions and that an out-compliance status indicates high emissions. Because the EPA work gives emission factors for clean and dirty operations, the clean factor was assigned to the in-compliance status and the dirty factor was assigned to the out-compliance status. Plants having at least one battery out of compliance and at least one battery in compliance were assigned a weighting factor half-way between the out and in factors. These weight- ing factors are given in Table IV-1. Note that the quenching weighting factors dominate those for all other sources. Individual weights were assigned to each compliance status within plants and summed to give a total for each plant. These sums formed the basis for classifying plants into two groupings. Plants for which no compliance data are available are assigned to a separate group. Plant assignments are shown in Table IV-2. This method of assignment can, and obviously has, led to some misclassi- fications. At best, it should be regarded as a technique to be used to form strata for statistical sampling. In theory, stratified samples usually have increased precision over simple samples. As will be later shown, atmospheric concentration versus distance from the coke plant relationships for the two strata, when scaled for plant production, were different. This indicates that the stratification method did, in this case, provide increased precision. C. Background Concentrations Because substances emitted to the atmosphere by coke ovens can also be emitted by other sources, it is necessary to consider atmospheric concentrations as a sum of background plus coke-oven emissions. The coke plants should only be assigned responsibility for their contribution to the total. 32 ------- Table IV-1 ASSUMED EMISSION WEIGHTING FACTORS FOR PLANT COMPLIANCE STATUS Compliance Status Emission Source Charging Doors Pushing Topside Quenching Waste gas stacks In 1.5 16 * N 1.6 175 N Out 80 130 3 65 350 0.7 Undetermined 80 130 3 65 350 0.7 At Least One Battery Out 40 73 1.5 33 260 0.4 Under a Legal Plan 40 73 1.5 33 260 0.4 N - Negligible. Topside compliance was assumed to be the same as door compliance. 33 ------- Table IV-2 CLASSIFICATION OF COKE PLANTS INTO EMISSION CATEGORIES (1974-1975) Plant Number * 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Classification ** K F K K F F F F F F F K F F F F K X K K K F Plant Number 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 Classification F F F F K F K K F K K K F K K K F X F F F F Plant Number 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 Classification F F F F F F F X F K X K F K F F X X X F F ** Plant numbers correspond to plant names given in Table II1-3. F indicates clean and K indicates dirty. The X indicates that insufficient data were available to classify the plant. 34 ------- Background concentrations are difficult to assess because ambient concentrations are seldom measured in an area when the coke-ovens are not in operation. Moreover, upwind ambient concentrations, recorded near coke plants, appear to have been influenced by the coking operations. In fact, ambient atmospheric concentrations of BaP or BSD have not been measured at all for many of the coke-oven locations. It is therefore necessary to estimate background concentration by using data recorded at a sufficient distance from the coke plant or by using data recorded at "similar" locations. Either of these methods has inherent error. In addition, background concentrations have been shown to vary with location within a city and with season. The available BaP atmospheric concentration data for cities without coke plants are given in Appendix A. They were reviewed to identify a "similar" noncoke plant location for each coke plant location. For example, the average BaP concentration over Montgomery, Jacksonville, and Charleston was used to represent Birmingham. The assumed annual average BaP backgrounds are given in Table IV-3. They vary from 0.04 ng/m3 for Houston to 1.6 ng/m3 for Pittsburgh. D. Evaluation of Ambient Concentration Data for Coke Plant Locations Available ambient data that were recorded in the vicinity of coke plants have been evaluated to determine if it is possible to represent the relationship of concentration mathematically as a function of distance from a coke plant. An analysis of the results of the dispersion calcula- tions performed by EPA (Youngblood, 1977) indicate that such a procedure should be possible. An analysis of data given in Appendix B shows that the BaP atmospheric concentration versus distance relationship about coke plants can be represented by a double logarithmic function (power curve). The procedure taken here is to modify the power curve formulation to include allowances for background concentrations and for coke plant capacities. The function selected is as follows: 35 ------- Table IV-3 ESTIMATED ANNUAL BACKGROUND CONCENTRATIONS OF BaP FOR COKE PLANT LOCATIONS Plant Number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 BaP (ng/m3) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 1.2 0.6 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.4 0.8 1.1 1.1 1.1 0.4 0.3 ** Remarks Montgomery, Jacksonville, Montgomery, Jacksonville, Montgomery, Jacksonville, Montgomery, Jacksonville, Montgomery, Jacksonville, Montgomery, Jacksonville, Montgomery, Jacksonville, Average of 5 sites in the area Spokane Hammond Hammond Hammond Hammond Hammond Hammond Hammond Hammond Hammond Hammond Hammond Norfolk, Charleston Riviera Beach, MD Site 30 km away Site about 30 km away Site about 30 km away NASN site NASN site Charleston Charleston Charleston Charleston Charleston Charleston Charleston Los Angeles * Plant numbers correspond to plant names given in Table III-3. Cities on locations used for reference concentrations. 36 ------- Table IV---3 (continued) Plant A Number 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 BaP (ng/m3) 0.3 0.8 0.8 0.8 0.6 0.6 0.6 0.6 0.6 0.4 0.5 0.6 0.6 0.8 0.6 0.6 0.8 0.8 0.8 0.8 0.8 0.8 1.6 0.8 0.8 1.6 1.6 0.8 0.8 0.4 ** Remarks NASN site Site about 30 km away Site about 30 km away Site about 30 km away Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites NASN site Site about 12 km away Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites Average of several Pennsylvania basins Average of Pennsylvania and Ohio sites Average of Pennsylvania and Ohio sites Average of several Pennsylvania basins Average of several Pennsylvania basins Average of several Pennsylvania basins Average of several Pennsylvania basins Average of several Pennsylvania basins Average of several Pennsylvania basins Sites about 10 km away Average of several Pennsylvania basins Average of several Pennsylvania basins Sites about 10 km away Sites about 10 km away Average of several Pennsylvania basins Average of several Pennsylvania basins Montgomery, Jacksonville, Charleston 37 ------- Table IV-3 (concluded) Plant t BaP Number (ng/m3) Remarks 58 0.04 Austin and Brownwood 59 0.04 Austin and Brownwood 60 0.5 Sites 20 to 30 km away 61 0.5 Charleston 62 0.5 Charleston 63 0.5 Charleston 64 0.5 Charleston 65 0.7 Hammond 38 ------- B + V A D* (1) where, C is the atmospheric BaP at some distance (D) from the coke plant. B is the location's nominal background concentration. V is the amount of coal processed annually by the coke plant. A and x are constants determined by regression. D is the distance from the plant. Least squares techniques were used to fit the available data to this function to estimate values for A and x. To extrapolate these functional representations from areas where data are available to areas where data are not available, it is first necessary to determine if the functional parameters (A and x) are consistent within the emission control grouping given in Table IV-2. If they are found to be consistent within groupings, average values can be used to represent a group. The parameter designated as A in Equation (1) relates to the atmospheric concentration resulting from coke-oven emissions at a distance of 1 km from the plant. It could be estimated for more plants than the slope parameter (x) because of the type of available data. For five plants representing the better control classification group, the A parameter had an average value of 2.8 x 10~6, whereas for eight plants representing the poorer control group, the average was 7.3 x 10~6. There were not enough data to show a difference in the slope parameter (x) for the two control groupings. The average value for five locations was found to be approximately -1.0. This is consistent with the dispersion modeling data, which gave values of about -0.9 to -1.0. The average based on the data will be used. Hence, this analysis suggests that Equation (1) be used with a value of -1.0 for the parameter x. The value of the parameter A will depend upon the grouping in which the plant is placed. For the F grouping a value of 2.8 x 10~6 will be used, and for the K grouping a value of 7.3 x 10~6 will be used. 39 ------- E. Relationship Between BaP and BSO Atmospheric Concentrations Because so few data are available for BSO atmospheric concentrations taken in the vicinity of coke production plants, an analysis has been made to determine if the BaP data can be used to predict BSO atmospheric concentrations, that is, to determine if some mathematical relationship exists between BaP and BSO concentrations. Some of the potential hindrances to establishing this type of relationship are that BaP and BSO are emitted from other sources besides coke ovens and that the precise relationship of BSO to BaP for coke battery emissions is unknown. The available BSO concentration data (Appendix A) have been plotted against the BaP data on Figure IV-1 for sampling sites that collected both types of data. Average values were used. Data sources included the 1972 NASN urban data, data recorded at sampling sites near coke plants, and Maryland data. The data from the various sources appear to form an increasing function with the cities without coke-ovens representing the lower end of the scale and the data recorded near coke plants repre- senting the upper scale. Figure IV-2 is a plot of only data found near the coke plants. Statistical regression techniques were used to fit mathematical functions to various selected combinations of data given in Figures IV-1 and 2. The functional equation used was of the type: BSO = A BaPX (2) where, BSO is the atmospheric BSO concentration (ug/m3) BaP is the atmospheric BaP concentration (ng/m3) A, x are constants. The values of the constants were found to be as follows: Parameter Data Set All data Data for noncoke locations Data for coke locations A 3.80 3.82 3.93 X 0.19 0.15 0.15 Data for coke locations with BaP greater than 5 ng/m3 2.20 0.35 40 ------- 40 "5 =L I § u 8 o E i I I I I I I I 1 I I I 1 I I I I I I I I 1 II IIIIIT 0.1 ALL DATA DATA FOR NON-COKE OVEN CITIES ONLY I I 1 I I I I I 1 I I I 1 1 I I I I I I I I 1 1 I 1 I I I < I 1 10 -1 10" 10' ATMOSPHERIC B*P CONCENTRATION - 10' 10" FIGURE IV-1. RELATIONSHIP BETWEEN BSO AND BaP ATMOSPHERIC CONCENTRATIONS FOR ALL LOCATIONS ------- 100 I o H in u § o in at o UJ a. I I I 1 I I I I I 1 1 I I I I I 1 I I I | I I I 1I I I I I L Q NASN DATA FOR COKE OVEN CITIES 0 DATA TAKEN NEAR COKE PLANT LOCATIONS DATA WITH BaP> 5 DATA FOR NON-COKE OVEN CITIES II I 1 ATMOSPHERIC BaP CONCENTRATION - ng/m3 FIGURE IV-2. RELATIONSHIP BETWEEN BSO AND BaP ATMOSPHERIC CONCENTRATIONS FOR COKE OVEN LOCATIONS ------- The regression coefficients (R2) were found to be around 0.4, indicating a less than good fit to the data. The equation fit to all of the data appears to underestimate the BSD concentrations for the higher BaP concentrations. Consequently, an equation was fit to the data for coke oven locations having BaP concentrations in excess of 5 ng/m3; this equation had a higher slope. Based on occupational exposure data taken within coke plants, there is evidence that the slope would continue to increase as the BaP concentration increases (Antell, 1977). The occupa- tional data indicate that 1 ng of BaP might correspond to 0.1 pg of BSO with an upper bound of around 0.5 yg of BSO. However, due to a number of possible chemical and physical processes and to dilution due to back- ground, the relationship in the outside environment may not be the same as in the occupational environment. Three procedures are suggested for estimating atmospheric BSO concentrations based on BaP concentrations. The first, which should give an upper limit, follows: The estimated background BSO concentration is added to 500 the BaP concentration that is due solely to coke- oven emissions. The second procedure is similar to the first, except the BaP concentrations due solely to coke-ovens are multiplied by 100 and added to background concentrations. The third procedure is based on the empirical functions fit to the data. All three of these procedures were tried. The empirical procedure and the procedure in which 1 ng of BaP corresponds to 0.1 pg of BSO were found to give almost identical results. The results of the empirical procedure were used in the exposure estimates. F. Population Exposure Estimates The estimated population exposures to coke-oven emissions are given in the summary section of this report and are not repeated here. However, a general discussion of the approach is included. Resident populations were estimated for five concentric geographic rings about each plant. The radii of the rings were taken as 0 to 0.5, 0.5 to 1, 1 to 3, 3 to 7, and 7 to 15 km. These spacings were selected to correspond to the shape of the concentration versus distance curves 43 ------- shown in Appendix B. Resident population for each of the geographic rings was obtained from the Urban Decision Systems, Inc., Area Scan Report, a computer data system that contains the 1970 census data in the smallest geographic area available (city blocks and census enumeration districts). Average annual BaP concentrations for each geographic ring were estimated by using the empirical model for those coke plants for which questionable or no monitoring data were available. This model was used for 45 of the 65 coke plants. The plant specific best fit equations given in Appendix B were used for locations for which sufficient monitoring data were available. On a few locations, the monitoring data were used to fix the concentration at a distance of 1 km from the plant and the empirical model slope of -1.0 was used to estimate concentrations at other distances. In all, some monitoring data were used in making exposure estimates for 20 of the coke plants. For locations with more than one coke plant, the population residing in overlaps of the geographic rings was estimated by assuming a uniform population distribution. BaP concentrations for the overlapping rings were estimated as the sum of the applicable concentrations for individual coke plants. Concentration subgroups were then developed, based on the range of concentrations for the estimated exposures, and the total number of residents for each exposure subgroup were calculated. The population residing within a subgroup was excluded if its average annual BaP con- centration due only to coke-oven emissions was less than 0.1 ng/m3. These subgroupings were made for exposures to coke-oven emissions only and to coke-oven emissions plus background concentrations. Population exposures to BSO were calculated using che procedures given in Section IV-E. These procedures estimate BSO exposures based on estimated BaP exposures. 44 ------- Appendix A AMBIENT ATMOSPHERIC BaP AND BSD CONCENTRATIONS A. General This appendix presents BaP and BSO atmospheric concentration data recorded in the vicinities of coke manufacturing plants. Data are also presented that give background concentrations for locations that contain and do not contain coke ovens. All data used in this report are based on high-volume filter samples. In addition, many of the sampling pro- grams were conducted over a relatively few days within 1 or 2 consecutive months; thus, they may not be entirely representative of an area's average annual concentration. The implications of this sampling approach in es- timating population exposures is described in further detail in Appendix B. B. Atmospheric BaP and BSO Concentration Data Recorded Near Coke Manufacturers Atmospheric data that have been recorded near coke manufacturers are described in the following paragraphs. 1. Monessen Area Air Quality Study, Pennsylvania The Pennsylvania Department of Environmental Resources conducted an air quality study to determine the distribution and magnitude of total suspended particulates (TSP), benzene soluble organics (BSO), and benzo (a)pyrene (BaP) concentrations in the Monessen area. The impact and extent of air pollution due to sources at the Wheeling-Pittsburgh Steel Corporation, Monessen, were evaluated, with sampling conducted from April 6 to June 21, 1976, at three sites near the steel plant. Meteoro- logical and selective sector actuator techniques were included in the sampling program (DER, 1977A). 45 ------- A statistical summary of the data for the three sites is given 3 in Table A-l. The average TSP concentrations ranged from 79 to 166 yg/m , 3 average BaP concentrations from 2.7 to 40.8 ng/m , and the average BSD from 2.6 to 9.2 ng/m . Selective sector actuator sampling and a concen- tration-wind direction frequency weighting technique all confirmed that the steel plant is the major source of TSP and BaP. The average concen- trations found in areas in the direction of winds coming from the plant are between 1.5 and 3 times the average concentrations for winds from all other directions (DER, 1977A). 2. Allegheny County, Pennsylvania Three coke batteries are located in Allegheny County: U.S. Steel Corporation in Clairton, Jones and Laughlin in Hazelwood, and Shenango, Inc. on Nevell- Island. From April to September 1976, high- volume particulate samples taken from 11 sites were analyzed for BaP. The sampling schedule included two 10-week periods of four and two samples per week, respectively (Ek, 1977). Table A-2 shows the results obtained during the sampling. The average BaP concentrations for the 11 locations varied between 1.64 3 and 51.95 ng/m . Eight additional samples were collected during first- stage alerts at Liberty Borough in April and June 1976. Four were collected over 24 hours and four over 8 to 12 hours. These data which are given in Table A-3, show average BaP concentrations about six times higher than for the regular sampling given in Table A-2. 3. Geneva Works, Utah The data collected for BaP concentrations near the U.S. Steel Geneva Works located near Prpvo, Utah, are summarized in Table A-4. Eight stations within 4 km of the coke batteries showed average BaP concentrations of 1.47 to 3.81 ng/m . Two background stations 20 to 3 30 km away showed average BaP concentrations of 0.12 and 0.83 ng/m . 46 ------- Table A-l MONESSEN AIR STUDY, 24-HOUR SAMPLE CHARACTERISTICS TSP Station 2 Station 6 Station 7 BaP (ng/m3) Station 2 Station 6 Station 7 BSD (Mg/m3) Station 2 Station 6 Station 7 Sample Size 29 28 31 29 28 31 29 28 31 Average 166.0 79.0 113.0 40.8 2.7 22.8 9.2 3.3 2.6 Range 27.0-360.0 22.0-165.0 26.0-300.0 0.3-206.4 0.2- 10.8 0.4-100.3 1.5- 25.4 0.6- 9.1 0.9- 19.3 Geometric Mean 145.0 71.0 93.0 10.0 1.6 10.1 6.5 2.6 3.8 Standard Deviation 1.76 1.64 1.91 7.60 2.78 4.57 2.34 2.01 2.36 Station 2 is 1 km ESE of the coke ovens. Station 6 is 2.1 km NW of the coke ovens. Station 7 is 1.8 km ENE of the coke ovens. Source: DER (1977A). ------- Table A-2 AMBIENT BaP CONCENTRATIONS FOR ALLEGHENY COUNTY, PENNSYLVANIA (ng/m3) CO Site Number 7102 5702 8601 8704 5802 7570 8602 6903 8790 5602 7004 Site Location* 10.5 km N of USS, 8 km E of J&L, 21.5 km SE of S 18 km NW of USS, 4.5 km N of J&L, 12 km ESE of S 0.5 km SE of USS, 14 km SE of J&L, 28 km SE of S 2.0 km NE of USS, 12 km SE of J&L, 27 km SE of S 18 km NW of USS, 6 km NW of J&L, 10 km SW of S 8.5 km NNE of USS, 9.5 km ESE of J&L, 24 km SE of S 1.5 km NNW of USS, 12 km SE of J&L, 26 km SE of S 12 km NW of USS, 1 km SSE of J&L, 16 km SE of S 2 km NE of USS, 13 km SE of J&L, 27.5 km SE of S 16 km NNW of USS, 5 km NNE of J&L, 15 km ESE of S 12.5 km N of USS, 6 km E of J&L, 18.5 km SE of S Sample Size 2 2 6 5 2 5 4 10 20 2 2 Average 1.64 2.62 13.63 15.00 2.29 6.12 28.17 3.95 51.95 3.78 1.66 Range 0.2- 3.1 0.3- 4.9 0.9- 67.7 0.3- 40.4 1.8- 2.8 0.9- 20.1 2.8- 83.5 0.5- 19.0 0.4-310.0 3.1- 4.5 1.4- 1.9 USS is U.S. Steel, J&L is Jones and Laughlin, and S is Shenango. Source: Ek (1977). ------- Table A-3 BaP DATA OBTAINED DURING FIRST STAGE ALERTS AT LIBERTY BOROUGHSITE 8790 (ng/m3) Sample Number 1 2 3 4 24-Hour Data 427.9 277.8 320.4 171.0 Average 299.3 8-12 Hour 405.8 458.8 189.8 155.6 302.3 Data Table A-4 ATMOSPHERIC BaP CONCENTRATIONS Station Number 1 2 3 4 5 6 7 8 9 10 GENEVA WORKS (ng/rn^) Location in Relation to Battery 2.0 km NW 2.7 km NW 2.4 km NW 1.8 km N 1.3 km NE 2.4 km SE 4.0 km NW 2.6 km S 30.0 km S 20.0 km N IN UTAH Sample Size ' 9 6 9 11 11 11 3 11 11 9 NEAR THE Average 2.08 3.81 3.15 2.41 3.13 1.63 2.10 1.47 0.12 0.83 Range 0.40-4.42 2.52-5.27 0.97-6.30 0.44-5.85 0.54-6.29 0.46-3.44 0.87-3.53 0.38-3.35 0.01-0.32 0.05-2.77 49 ------- 4. Wayne County, Michigan Three companies operating coke batteries are located in Wayne County, Michigan: Solvay, Ford, and Great Lakes Steel. Ambient atmo- spheric BaP concentration data were reported annually for seven sites in the general area for 1971 to 1975 and are given in Table A-5. Annual BaP concentrations for the various sites varied between 0.34 to 14.72 ng/m . 5. Buffalo. New York Three companies operate coke batteries near Buffalo, New York: Semet-Solvay, Bethlehem Steel, and Donner-Hanna. Atmospheric BaP con- centration data were recorded from 1973 to 1974 on 13 sites, in addition to data recorded at the National Air Surveillance Network (NASN) site. These data, which are given in Table A-6, indicate the average BaP con- 3 centrations ranged from 0.45 to 27.10 ng/m . 6. Duluth, Minnesota Thirty-eight samples for ambient BaP concentrations were ob- tained from two sites within 3 km of the U.S. Steel coke batteries in Duluth, Minnesota. These data are summarized in Table A-7. Average 3 BaP concentrations of 0.22 and 1.45 ng/m were found for the two sites. When most of the samples were collected, the wind was blowing in the gen- eral direction of the collection sites from the plant. 7. Gadsden, Alabama The Republic Steel Corporation operates coke ovens in Gadsden, Alabama. Atmospheric BaP concentrations were sampled at two sites within 1.6 km of the coke ovens during 1974, 1975, and 1976. The data from this sampling which are summarized in Table A-8, indicate the annual atmo- 3 spheric BaP concentrations varied from 0.44 to 5.06 ng/m . 50 ------- Table A-5 AMBIENT BaP CONCENTRATIONS FOR WAYNE COUNTY, MICHIGAN (ng/m3) Site Number 02 04 05 06 08 11 NASN 1971 3.00 2.97 9.32 3.62 2.39 1.30 1.40 1972 2.44 3.14 5.95 2.62 2.56 1.32 1.90 1973 3.02 4.16 11.78 3.12 2.70 2.00 1.00 1974 1.46 1.70 10.83 0.52 0.44 0.34 1975 3.43 4.85 14.72 1.47 2.54 0.73 1.00 Average 2.67 3.36 10.52 2.27 2.13 1.14 1.33 No. 2 is 14 km NE of Solvay, 14.5 km NE of G.L.*, and 18 km ENE of Ford. No. 4 is 7.2 km NNE of Solvay, 9.3 km NE of G.L., and 9 km NE of Ford. No. 5 is 1.6 km N of Solvay, 4 km NNE of G.L., and 4.4 km E of Ford. No. 6 is 15.3 km NNW of Solvay, 16.5 km NNW of G.L., and 11.7 km NNW of Ford. No. 8 is 10.5 km SW of Solvay, 8.5 km SW of G.L. , and 9.3 km SSW of Ford. No. 11 is 30 km SW of Solvay, 29 km SW of G.L., and 30 km SW of Ford. G.L. - Great Lakes Steel. 51 ------- Table A-6 AMBIENT BaP CONCENTRATIONS FOR BUFFALO, NEW YORK Ul 10 Sice Number 1 2 3 4 5 6 7 8 9 10 11 12 13 NASN Site Location 3.1 km E of Beth, and 3.4 km SE of D-H* 1.9 km ESE of Beth, and 3.8 km S of D-H 3.8 km NE of Beth, and 1.5 km SE of D-H 1 km'ENE of Beth, and 2.8 km S of D-H 3 km N of Beth, and 1.4 km WNW of D-H 4.3 km NE of Beth, and 1.1 km ENE of D-H 5.6 km NE of Beth, and 2.1 km NNE of D-H 0.6 km W of Allied 1.2 km ESE of Allied 2.4 km NE of Allied 30 km SW of Beth, and 34 km SW of D-H 3.2 km NW of Allied 4 km SW of Beth, and 6.2 km S of D-H 8.8 km NNW of Beth, and 5.6 km N of D-H Sample Size 37 81 48 7 78 65 41 73 76 44 44 28 7 Average 5.99 8.99 11.38 27.10 2.78 9.10 7.29 1.29 3.80 3.74 0.82 0.45 1.29 0.70** Range 0.27-30.5 0.26-48.7 0.06-68.4 2.76-48.8 0.05-23.8 0.20-65.6 0.07-46.2 0.05-21.2 0.13-81.4 0.01- 9.3 0.04-24.5 0.06- 3.1 0.40- 3.7 ** Beth, is Bethlehem Steel; D-H is Donner-Hanna. Two-year composite. ------- Site Number 1 2 Table A-7 AMBIENT BaP CONCENTRATIONS'FOR DULUTH, MINNESOTA (ng/ra3) Distance from Coke Ovens 2.1 km SW . 2.7 km N Sample Size Average 18 20 Range 1.45 0.22 BDM-7.02* BDM-1.25 BDM - below detectable minimum. Source: Jungers (1977A). Site Number 1 2 NASN Table A-8 AMBIENT BaP CONCENTRATIONS FOR GADSDEN, ALABAMA (ng/m3) Average Concentrations* Distance from Coke Ovens 1974 1975 1976 3-Year 1.6 km E 1.1 km SW Same as Station 1 5.06(0.44) 0.75 0.58 2.13(0.60)** 0.97 0.44 1.89 1.10 0.50 0.60 0.55 Sample size for each year for Sites 1 and 2 was 5. ** i O Excludes one high observation of 23.55 ng/m . Source: Jungers (1977B). 53 ------- 8. Birmingham, Alabama, Area Five coke battery facilities, which are within about 20 km of Birmingham, are located at Tarrant, Woodward, Thomas, Birmingham, and Fairfield. Atmospheric BaP concentrations were sampled at Tarrant and Fairfield during 1976, and NASN data are available for Birmingham. These data are given in Table A-9. The average BaP concentrations ranged from 2.5 to 4.5 ng/m . BaP data were also recorded for five CHAMP sites in the Birmingham area. These data are given in Table A-10. 9. Johnstown Air Basin, Pennsylvania Two coke plants are located near Johnstown, Pennsylvania (Bethlehem Steel's Franklin and Rosedale Divisions). An air quality study was conducted from August through November 1975 to determine the distribution and magnitude of TSP, BSO, and BaP concentrations in the Johnstown area. Concentration data were obtained for eight sampling sites 0.6 to 7.8 km from the Franklin Works (Table A-ll). BaP concen- trations ranged from 85.3 ng/m for the site nearest the Franklin plant to 3.6 ng/m for the site farthest from the plant. Wind-actuated sampling was also conducted for TSP, BSO, and BaP. For all three, in-sector sample concentrations were almost double the out-sector concentrations. 10. Philadelphia, Pennsylvania One coke facility is situated in Philadelphia (Philadelphia Coke Diviison), and another two coke facilities are within 12 km of the city at Alan Wood and Fairless Hills. Air quality data were collected at four different times from November 1976 to January 1977 to determine the distribution and magnitude of TSP, BSO, and BaP in Philadelphia. Concentration data were obtained for 13 sampling stations about 2 to 14 km from Philadelphia Coke Division. These data are summarized in Table A-12. The average BaP concentrations for the 13 sampling sites j ranged from 0.97 to 4.70 ng/m . BSO average concentrations ranged from 3 3.05 to 8.56 ug/m . 54 ------- Table A-9 AMBIENT BaP CONCENTRATIONS FOR BIRMINGHAM, ALABAMA (ng/ra3) Site Number 1 2 NASN* Distance from Coke Plants Tarrant (0.5 km NW) Fairfield (0.5 km ESE) Sample Size 2 3 Average 4.46 2.79 2.50 Range 0.06-8.86 1.10-5.31 __ 1974 sample composite. Source: Jungers (1977B). Table A-10 CHAMP SITE AMBIENT ATMOSPHERIC BaP DATA FOR THE BIRMINGHAM AREA (1975 Data) Site Number 304 305 306 307 323 331 Distance from Batteries (km) Fairfield 11.4 25.8 10.3 4.9 16.4 13.4 Birmingham 3.8 5.0 10.8 18.4 2.4 3.2 Tarrant 2.4 13.0 13.4 21.4 1.9 5.4 Sample Size* 6 12 12 6 12 12 BaP (ng/m3) Average 4.2 1.8 1.5 2.4 2.9 3.5 Range 0.7-9.2 0.6-3.7 0.4.-4.0 0.9-4.3 1.2-6.6 1.4-5.5 Number of months for which data are available; for individual months data were generally collected for 25 to 31 days. 55 ------- Ln O> Table A-ll AMBIENT BaP, BSO, AND TSP CONCENTRATIONS FOR JOHNSTOWN, PENNSYLVANIA Site Discance from Franklin Number of Number Coke Ovens Samples 1 7.8 2 3.8 3 2.9 4 1.0 5 4.6 6 3.4 7 0.6 8 1.9 km km km km km km km km WSW W SW NNE SSW SSW ESE SE 30 32 33 32 28 31 34 31 BaP Average 3.6 13. 7. 23. 6. 6. 85. 19. 8 7 4 0 8 3 9 (ng/mj) Range 0. 2. 0. 3. 1. 1. 1. 1. 5- 15. 0-110. 9- 41. 6-246. 5- 11. 4- 24. 5-575. 2-102. 4 9 8 6 0 5 9 9 Average TSP* 32 70 71 142 55 58 179 70 (pg/mj) BSO 2. 5. 5. 9. 3. 4. 14. 5. 2 5 4 7 9 1 1 6 * Geometric mean. Source: DER (1977B), ------- U1 Table A-12 AMBIENT BaP, BSO, AND TSP CONCENTRATIONS FOR PHILADELPHIA, PENNSYLVANIA Site Location from Philadelphia Number of Number Coke Ovens Samples 1 14.1 km SW 4 2 3.5 km SW 3 3 19 km SW 4 4 12.5 km WSW 4 5 13.7 km WNW 4 6 9.3 km NNE 4 7 5.8 km W 4 8 10 km SW 4 9 2 km WNW 4 10 8.8 km SW 4 11 13 km SSW 3 12 10 km SW 3 13 5.2 km SW 4 NASN BaP Average 3.82 1.61 2.27 0.97 1.34 2.54 4.24 1.96 2.78 4.42 3.68 4.70 4.10 2.10 (ng/m3) Range 2.09-8.81 0.82-2.26 1.09-5.35 0.21-1.81 0.35-2.31 1.38-4.53 1.90-6.29 1.38-2.31 1.26-4.46 2.28-7.15 1.55-6.70 2.44-8.06 1.57-9.90 _ Average TSP 76.5 130.5 102.5 44.8 36.3 48.0 85.5 60.3 60.0 109.7 133.3 95.0 102.3 _ (pg/m3) BSO 5.44 4.00 5.75 3.05 3.11 4.15 7.22 4.77 6.42 7.76 8.05 8.56 6'.59 4.66 Source: Lazenka (1977). ------- 11. Granite City. Illinois BaP was measured at eight sampling sites between 0.5 to 3.5 km from the National Steel coke ovens in Granite City, Illinois. The data obtained during this sampling, which are summarized in Table A-13, indi- cate that average atmospheric BaP concentrations for the stations ranged from 2.6 to 12.2 ng/m . More recently TSP, BSO, and BaP data have been obtained for 3 days on two sites within 0.8 km of the coke batteries (Table A-14). BaP measurements from individual observations ranged from 1.6 to 278 ng/m . 12. Houston, Texas Atmospheric BaP samples were obtained from seven sites located up to 5.5 km from the Armco Steel coke ovens situated in Houston, Texas. Samples were recorded at various times from 1973 to 1976. The data summarized in Table A-15 show that average concentrations by site varied 3 from 0.03 to 0.28 ng/m . These concentrations are much lower than those recorded at similar distances from other coke-oven locations, perhaps indicating any of the following factors: Good emission control. Faulty measurement techniques. All samples recorded upwind. Ovens not in operation when measurements were recorded. 13. Cleveland. Ohio King et al. (1976) have reported on atmospheric BaP concen- trations for a number of sites in Cleveland, Ohio. These data are summarized in Table A-16. The geometric means are given rather than the arithmetic means. 14. Sparrows Point, Maryland The Maryland State Division of Air Quality Control measures ambient BaP and BSO concentrations for many sites within the state, 58 ------- Table A-13 AMBIENT BaP CONCENTRATIONS FOR GRANITE CITY, ILLINOIS (ng/m3) Site Number LN1 NW2 008 006 007 009 010 Oil Distance from Sample Coke Ovens Size 0.7 km N 3 0.6 km SSW 3 1.1 km NE 2 2.4 km WNW 2 1.8 km NW 2 1.5 km W 1 3.5 km WNW 2 2.9 km WSW 2 Table A- 14 Average 8.60 4.83 2.65 8.15 5.20 3.50 12.15 7.15 Range 1.1-16.5 0.6- 9.5 1.8- 3.5 8.0- 8.3 3.9- 6.5 - 1.8-22.5 3.9-10.4 ADDITIONAL ATMOSPHERIC AMBIENT DATA FOR GRANITE CITY, ILLINOIS Station 1 2 Distance from Coke Ovens Pollutant 1 0.8 km N TSP (gg/m3) 113 BSD (pg/m3) 4.9 BaP (ng/m3) 2.1 0.5 km S TSP (yg/m3) 193 .BSO (pg/m3) 17 BaP (ng/m3) 124 Day 2 3 344 268 18 14 278 202 113 83 4.2 0.5 2.6 1.6 Average 238 12 161 130 7 43 59 ------- Table A-15 AMBIENT BaP CONCENTRATIONS FOR HOUSTON, TEXAS (ng/m ) Site Number 256034 256015 233006 256017 256019 256028 256005 Distance from Coke Ovens 1.0 km NW 0.9 km NNW 2.2 km NE 0.8 km W 2.2 km WSW 0.8 km SSE 5.4 km SW Sample Size Average 6 5 4 6 4 7 1 0.17 0.15 0.05 0.03 0.33 0.28 0.16 Range 0.05-0.62 0.07-0.35 0.02-0.11 0.02-0.05 0.04-1.00 0.05-0.34 60 ------- Table A-16 AMBIENT BaP CONCENTRATIONS FOR CLEVELAND, OHIO Site Location from Number Coke Battery* 1 0.8 km N 3 4.8 km SW 4 4.4 km NE 5 4.4 km SE 6 12.0 km NE 7 7.2 km W 8 6.8 km SW 9 1.0 km SE 10 6.0 km NNE 12 13.2 km ESE 13 4.4 km S 14 9.6 km SE 15 3.2 km W 17 6.4 km NE 20 16.8 km NE 21 4.0 km NNW Sample Size 21 37 23 28 22 38 28 30 33 32 23 22 21 32 19 22 BaP Geometric Mean** 1.40 0.62 0.64 0.58 0.71 0.46 0.44 3.60 0.74 0.43 0.85 0.47 0.51 0.91 0.50 1.10 (ng/m3) Maximum 41.0 3.1 15.0 3.3 3.0 2.1 2.3 130.0 7.2 2.0 14.0 3.7 3.5 49.0 6.9 17.0 Locations are only approximate. ** Arithmetic mean not reported. Source: King et al. (1976). 61 ------- four of which are located within approximately 12 km of the coke batteries. Data are given in Table A-17. 15. Chattanooga, Tennessee As part of the CRESS and CHAMP programs, BaP samples were collected for nine sites in the Chattanooga area. These data are sum- marized in Table A-18. C. Ambient Background BaP and BSO Concentration Data Because coke ovens are not the only sources of BaP and BSO concen- trations in the atmosphere, the coke oven contributions must be placed in perspective with each area's nominal background concentrations. Data are presented here for ambient background concentrations measured in cities in which coke ovens are located, cities without coke ovens, and remote rural areas. 1. NASN Air Quality System Data NASN routinely monitors suspended particulate concentration levels in urban and nonurban areas, generally reporting them as quarterly composites for stations in the network. The composite, which pools all samples collected during the quarter, assists in generating sufficient material for laboratory analysis. Before 1971, BaP analysis was made for more than 120 sites per year. For 1971 and subsequent years, the sites were limited to 40 because of time and resource restrictions. These 40 sites were selected to update BaP concentrations in cities with and without coke ovens. Three sites were selected in National Parks to provide nunurban back- ground readings (U.S. EPA, 1974). Annual average BaP concentrations for 1967 to 1975 are given in Table A-19 for the 40 NASN sites. Table A-20 gives BSO data recorded at these sites for 1971 and 1972. The BaP and BSO concentrations are summarized in Table A-21. The BaP concentrations are generally less than 0.1 ng/m for rural locations. Most urban locations without coke 3 ovens have average concentrations of less than 1 ng/m (the average 62 ------- Table A-17 AMBIENT ATMOSPHERIC BaP AND BSD CONCENTRATIONS FOR SPARROWS POINT, MARYLAND Distance from Coke Batteries* 12 km N 7 km NNW 3 km W 4 km SSW Sample Size** 2 12 10 10 BaP (ng/m3) Average 1.4 1.4 1.9 2.4 Range 1.1-1.7 0.2-4.4 0.1-2.6 0.4-5.4 ** Locations are only approximate. k Number of months for which data are available. BSO Average 6.5 5.4 4.8 Range 6.3-6.8 3.0-8.0 2.6-8.7 Table A-18 AMBIENT BaP AND BSO CONCENTRATIONS FOR CHATTANOOGA, TENNESSEE Site Number 621 622 631 632 633 634 635 641 642 Distance from Coke Ovens 7.6 km 8.9 km 20.2 km 15.2 km 16.4 km 23.8 km 14.3 km 13.0 km 15.1 km Number of Samples 12 12 12 12 12 12 12 10 12 BaP (ng/m3) Mean 3.83 3.49 1.63 1.85 1.55 0.82 1.23 2.35 2.66 Range 1.0-8.4 0.4-8.5 0.2-3.6 0.2-5.9 0.1-4.2 0.0-2.7 0.1-3.0 0.2-8.6 0.2-5.6 BSO Mean 3.69 4.51 3.04 2.93 2.33 1.73 2.66 3.26 3.60 (pg/m3) Range 2.2-6.5 2.6-9.1 1.4-5.2 1.1-6.4 0.6-4.6 0.3-2.7 1.5-4.1 1.8-5.3 1.5-7.0 Number of months for which data are available; for individual months data were generally collected for 20 to 31 days. 63 ------- Table A-19 ANNUAL AVERAGE AMBIENT BaP CONCENTRATIONS AT NASN URBAN STATIONS (ng/m3) Location Montgomery AL Chicago , IL Detroit, MN New York, NY Toledo, OH Philadelphia, PA Pittsburgh, PA Shenandoah Park, VA Charleston, WV Grand Canyon, AZ Gads den, NM Gary, IN Indianapolis, IN Baltimore, MD Trenton, NJ St. Louis, MO Youngs town, OH Chattanooga, TN Spokane , WA 1967 2.3 3.0 5.4 3.9 1.9 5.9 7.0 0.3 - 0.2 - - 5.7 3.8 - 2.3 8.2 22.9 1968 2.9 3.1 5.1 - 1.8 2.9 6.3 0.3 4.6 0.2 2.4 - 4.1 2.3 1.4 - 5.6 7.4 - 1969 2.0 3.9 3.9 3.6 1.5 4.0 13.8 0.3 2.6 0.2 1.8 - 5.2 2.8 1.6 3.3 9.9 4.2 - 1970 1.3 2.0 2.6 3.0 1.4 2.4 5.9 0.2 2.1 0.1 2.5 - 2.3 2.1 0.8 - 7.1 5.5 - 1971 0.5 2.5 1.4 2.3 0.8 2.3 6.1 - 0.9 - 1.2 1.6 0.9 2.8 0.7 0.8 3.7 - 1.7 1972 0.5 1.3 1.9 1.8 0.4 0.9 10.6 0.1 0.7 - 1.2 1.2 4.9 1.3 0.5 0.6 3.2 9.9 1.5 1973 0.3 0.4 1.0 0.7 0.4 0.6 - 0.1 0.2 >0.1 0.8 0.3 0.4 0.4 0.1 0.2 1.1 - 0.4 1974 0.4 - - 0.9 0.2 0.8 1.3 - 0.5 >0.1 0.5 0.5 - 0.5 - 0.3 1.9 - - 1975 0.3 1.0 1.0 0.9 0.4 0.6 2.1 - 0.5 - 0.6 2.2 - 0.6 - 0.3 2.1 0.8 0.6 ------- Table A-19 (Concluded) Ul Location 1967 Milwaukee, WI Birmingham, AL Jacksonville, FL Honolulu, HI 0.5 Terre Haute, IN 3.7 Ashland, KY Baton Rouge, LA New Orleans, LA 1.8 Dearborn, MI Duluth, MN Buffalo, NY Cleveland, OH 2.9 Bethlehem, PA 2.9 Erie, PA Houston, TX Newport News , RI Norfolk, VA 3.5 Seattle, WA 1.8 St. Paul, MN 2.3 Arcadia National PK, ME Hammond , IN 2.5 1968 it. 7 - 2.9 0.6 - 9.3 - 1.6 - 2.7 - 3.0 2.1 - - - 4.9 2.0 1.8 0.3 2.1 1969 4.0 - 2.3 0.6 4.0 10.9 - 1.5 - 2.1 - 3.8 2.0 - - - 3.9 1.6 1.8 0.1 3.3 1970 2.5 - 1.4 0.2 2.8 6.7 - 1.1 - 1.1 - 2.8 2.7 - 1.2 - 1.8 1.5 1.0 0.2 1.7 1971 1.8 4.0 2.2 0.2 9.0 0.4 0.9 4.8 0.9 1.5 0.5 0.4 1.2 0.5 0.5 3.8 1972 3.6 2.3 0.4 0.1 1.1 8.5 0.2 0.4 0.6 19.1 1.5 1.3 0.8 2.4 0.4 0.3 0.6 0.5 0.5 0.3 1.4 1973 0.6 1.5 0.2 0.2 2.9 0.1 0.3 1.0 0.3 0.6 0.5 0.7 0.4 0.2 0.4 0.3 0.1 0.2 1974 2.5 0.4 0.3 0.1 0.3 1.7 0.2 0.8 0.1 0.6 0.2 0.2 0.5 0.1 0.4 1975 1.1 0.4 0.03 0.6 4.7 0.1 0.2 3.1 0.3 0.5 0.4 0.2 0.2 0.4 0.4 0.1 0.7 ------- Table A-20 Birmingham, AL Gadsden, AL Montgomery, AL Grand Canyon, AZ Jacksonville, PL Honolulu, HI Chicago, IL Gary, IN Hammond, IN Indianopolis, IN Terre Haute, IN Ashland, KY Batan Rouge, LA New Orleans, LA Baltimore, MD Dearborn, MI Detroit, MI Trenton, NJ Duluth, MN KL VARIATIONS OF BENZENE SOLUBLE ORGANIC SUBSTANCES (u 1971 1 3.1 2.9 3.4 1.2 4.3 2.3 4.3 4.7 3.8 2.6 4.1 6.8 2 JE> 4.0 7.3 - 2.6 1.7 1.8 2 6.7 3.6 4.2 0.9 3.0 0.1 5.7 2.7 4.7 3.1 7.4 1.9 3.5 4.5 3.2 3.0 3.0 2.5 3 - 2.1 2.4 - 2.1 1.2 - - 6.0 3.2 3.6 4.0 - 3.1 - 3.1 2.4 2.6 2.1 4 4.8 4.5 3.4 - 2.2 1.4 4.5 5.7 7.0 3.7 8.3 3.4 3.5 4.3 - 3.9 2.8 3.6 1 3.6 2.7 3.3 - 2.3 1.4 3.4 2.7 2.1 2.9 2.5 7.8 3.2 3.7 5.0 3.6 3.2 1.8 2.0 g/m ) 1972 2 7.5 4.2 2.9 - 5.4 2.3 2.5 4.1 9.4 4.9 5.7 7.2 4.1 4.9 3.6 7.3 3.3 1.7 5.9 3 4.0 2.4 2.2 - 4.4 3.3 2.7 3.0 6.3 3.0 4.0 7.9 3.5 5.5 - 4.6 3.4 2.0 4.5 4 5.2 2.3 2.6 - 6.0 3.0 3.9 2.5 5.0 - 6.3 9.2 5.3 4.2 4.5 4.5 3.0 1.5 12.5 Average 4.99 3.09 3.05 1.05 3.71 1.88 3.86 3.63 5.54 3.34 4.37 7.33 3.43 4.05 4.87 4.38 3.10 2.14 4.36 ------- Table A-20 (Concluded) 1971 1972 St. Paul, UN St. Louis, MO Buffalo, NY New York, NY Cleveland, OH Toledo, OH Youngstown, OH Bethlehem, PA Erie, PA Philadelphia, PA Chattanooga, TN Houston, TX Newport News, VA Norfolk, VA Shennandoah, VA Pittsburgh, PA Seattle, WA Spokane, WA Charleston, WV Milwaukee, WI 1 - 5.5 - 5.5 3.6 2.1 2.9 3.8 2.6 6.0 4.8 3.5 2.7 4.9 - 3.8 5.6 3.5 - 2 2.8 3.1 - 6.2 3.6 2.4 4.9 3.8 2.5 4.0 5.1 3.2 2.9 4.0 0.7 4.4 4.1 4.4 5.0 3.8 3 2.2 2.0 2.9 - - - 3.5 3.6 - 3.8 - 3.8 3.1 3.5 0.9 - 5.3 3.5 2.0 3.8 4 3.0 - 3.6 4.5 - 3.1 6.4 3.8 4.2 7.4 - 5.7 4.5 4.2 - 6.9 5.4 3.6 3.6 4.8 1 2.9 2.9 3.0 4.5 3.1 1.8 4.1 2.9 1.3 4.7 4.1 4.5 1.3 2.5 1.0 6.1 1.6 3.8 2.8 3.0 2 7.9 3.7 9.3 5.3 6.5 - 3.9 5.2 6.8 3.8 11.0 5.9 3.3 3.8 0.9 4.9 4.2 3.1 2.7 6.5 3 5.6 2.3 3.4 4.7 - 2.9 4.2 4.2 5.8 4.3 3.7 5.9 4.4 3.8 0.8 4.7 3.9 4.6 3.6 3.2 4 4.6 2.6 7.8 3.9 4.6 2.7 4.6 4.6 - 3.3 - 4.9 3.7 3.2 0.6 6.6 5.4 4.0 2.8 3.4 Average 4.14 3.16 5.00 4.94 4.28 2.50 4.31 3.99 3.87 4.66 5.74 4.68 3.24 3.74 0.81 5.34 4.44 3.81 3.21 4.07 ------- Table A-21 SUMMARIZATION OF AMBIENT BaP AND BSO DATA Cities Cities With Without Rural Pollutant BaP (ng/m3) 1975 data BSO (yg/m3) 1971-72 data ANNUAL Year 1966 1967 1968 1969 1970 1971 1972 1975 Statistic Coke Ovens Coke Ovens Areas Average Sample size Range 0 Average Sample size Range 2 Table A-22 BaP AVERAGES FOR (ng/m3) Cities With Coke Ovens 4.74 (15)* 5.34 (15) 3.75 (18) 4.41 (23) 3.02 (21) 2.18 (11) 2.14 (19) 1.21 (21) 1.21 0.38 <0.10 21.00 13.00 3.00 .3-4.7 0.03-0.9 <0.10 4.21 3.75 0.95 25.00 12.00 2.00 .1-7.3 1.9-5.6 0.8-1.1 SELECTED CITIES Cities Without Coke Ovens 2.76 ( 7) 2.29 ( 8) 2.64 ( 8) 2.14 (11) 1.41 (11) 1.22 ( 8) 0.64 (11) 0.38 (13) Number of cities included in average. Source of 1966-1972 data: U.S. EPA (1974). 68 ------- 3 is 0.38 ng/m ); however, areas with coke ovens generally have average 3 3 concentrations in excess of 1 ng/m with Ashland's 4.7 ng/m the highest and Dearborn's 3.1 ng/m the next highest. Coke ovens are located in both Ashland and Dearborn. The overall average for cities with coke 3 ovens is 1.21 ng/m . The BSO concentrations were generally less than 5 pg/m . The 3 average concentrations of most urban locations range from 1 to 4 vg/m . Ashland, Chattanooga, Pittsburgh, Buffalo, and Hammond have concentra- 3 tions exceeding 5 yg/m . Table A-22 shows the change from 1966 to 1975 in BaP concen- trations in the atmospheres for cities with and without coke ovens. Both classes of cities have shown a reduction; however, the atmospheric difference between the two types of cities has been fairly constant since 1968. 2. Pennsylvania Air Quality System The Pennsylvania Division of Technical Services and Monitoring, Bureau of Air Quality and Noise Control has systematically surveyed air quality since 1970. As part of this program, the division monitors sus- pended and settleable particulates at 91 locations. Suspended particu- lates are collected on a glass fiber filter with a high-volume air sampler. Each sample represents the particulate matter filtered from approximately 3 2000 m of air over 24 hours. Samples are taken from midnight to mid- night every 6 days (DER, 1977). During 1976, samples taken by this surveillance system were also analyzed for BaP concentrations. The yearly average for these data, based on one day sampled per month, are given in Table A-23 by sampling location within the air basin. The highest average annual concentration 3 3 was 56.38 ng/m for Montessen and the next highest was 17.10 ng/m for Johnstown. Both locations have coking operations. The lowest average 3 concentration was 0.40 ng/m for Hanover Green. 69 ------- Table A-23 AMBIENT BaP CONCENTRATIONS FOR PENNSYLVANIA, 1976 (ng/m^) Allentown-Eastern Air Basin Allentown Tatamy Bethlehem Easton Bethlehem East Emmaus Allen Twp. Northampton (Basin average) Beaver Valley Air Basin New Castle Bessemer Koppel Beaver Falls Vanport Rochester Ambridge Baden Midland Brighton (Basin average) Erie Air Basin Millcreek Twp. Erie Central Erie South Erie East 'early Lverage* 0.71 0.80 1.11 1.86 1.46 1.29 0.55 0.76 1.08 3.06 1.41 9. -43 5.03 2.27 4.19 6.18 9.00 3.13 2.42 4.73 0.45 2.04 1.16 1.62 Monthly Range 0.09- 2.30 0.11- 2.74 0.22- 4.15 0.39- 9.28 0.24- 6.34 0.10- 7.62 0.06- 2.24 0.10- 3.43 0.13-11.36 0.46- 2.21 0.30-78.08 0.42-12.65 0.16- 5.44 0.35-13.96 0.75-31.96 0.40-43.48 0.31- 8.60 0.34- 9.74 0.12- 0.87 0.26- 7.13 0.21- 3.77 0.23- 6.33 Based on one sample per month for 12 months. Source: Dubin (1977). 70 ------- Table A-23 (Continued) Yearly Monthly Average Range Harborcreek Twp. 0.60 0.13- 3.40 (Basin average) 1.20 Harrisburg Air Basin Middletown 0.83 0.12- 2.10 Swatara Twp. 0.65 0.18- 1.42 Steelton 1.03 0.32- 2.98 Lemoyne 0.92 0.28-2.38 Susquehanna Twp. 0.90 0.13- 2.55 Harrisburg 0.81 0.15- 2.00 Summerdale 0.61 0.14- 1.60 (Basin average) 0.82 Johnstown Air Basin Westmont 1.00 0.15-5.05 Johnstown North ' 17.14 0.31-75.54 Johnstown Central 4.41 0.24-10.69 E. Conemaugh 16.30 1.21-50.74 Johnstown South 4.78 0.32-23.01 Hornerstown 3.17 0.13- 8.16 (Basin average) 7.51 Lancaster Air Basin Lancaster Twp. 0.54 0.15- 1.77 Lancaster General 1.01 0.21- 2.74 Lancaster East 10.82 0.19-122.7 Lancaster North 0.72 0.27- 2.53 Lancaster West 0.91 0.25- 3.10 Neffsville 0.68 0.11- 1.81 Manheim Twp. 0.73 0.12- 2.75 (Basin average) 2.28 71 ------- Table A-23 (Continued) Yearly Monthly Average Range Monessen Valley Air Basin New Eagle 2.78 0.31-7.51 Monessen 56.38 1.05-206.3 Lover 2.61 0.61- 9.66 Elco 0.96 0.12- 3.94 Brownsville 9.05 0.59-57.00 Charleroi 2.47 0.13- 6.99 (Basin average) 12.69 Reading Air Basin Leesport 0.56 0.07- 1.-60 Reading South 0.94 0.18- 3.20 Shillington 1.02 0.10- 4.09 Sinking Spring 0.73 0.05- 2.26 Reading Central 0.83 0.17- 2.67 Temple 0.90 0.15- 3.73 Laureldale 0.94 0.20- 3.32 (Basin average) 0.85 Scranton-Wilkes-Barre Air Basin Hanover Green 0.40 0.09- 1.04 Dickson City 1.35 0.18- 3.32 Jessup 2.00 0.15-13.70 Pittston 1.49 0.14- 3.60 Swoyersville 1.67 0.42- 3.67 Nanficoke 0.94 0.11- 3.26 Wilkes-Barre 1.82 0.19-9.00 Scranton 2.06 0.28- 4.25 Dupont 1.30 0.27- 2.41 Avoca 0.44 0.11- 0.97 West Nanticoke 0.79 0.14- 2.05 (Basin average) 1.32 72 ------- Table A-23 (Continued) Yearly Monthly Average Range Southeast Pennsylvania Air Basin Pottstown 1.06 0.36- 3.09 Bristol 0.91 0.20- 3.03 Willow Grove 1.05 0.32- 3.93 Dowingtown 0.69 0.19- 2.48 Doylestown 0.76 0.12- 3.21 Media 1.00 0.24- 3.11 Chester 0.56 0.14- 1.78 Perkasie 0.73 0.16- 2.53 Quakertown 0.48 0.08-1.84 West Chester 0.81 0.11- 2.62 Lansdale 1.36 0.18- 4.57 Conshohocken 2.06 0.40- 3.24 Phoenixville 0.80 0.12- 2.47 Morrisville 0.79 0.07- 2.55 Coatsville 0.64 0.07- 1.42 (Basin average) 0.92 York Air Basin York East 0.98 0.17- 2.59 York Central 0.96 0.17- 3.13 West Manchester Twp. 0.78 0.12- 3.38 Manchester Twp. 0.41 0.07- 1.12 West York 0.77 0.19- 2.16 Springettsbury 1.15 0.11- 7.49 (Basin average) 0.84 Altoona Area Altoona Central 3.49 0.29-17.10 Altoona East 5.80 0.31-22.20 (Area average) 4.64 73 ------- Table A-23 (Concluded) Yearly Monthly Average Range Farrell-Sharon Area Farrell 2.46 0.44- 8.54 Sharon 2.45 0.24- 9.22 (Area average) 2.46 Williamsport Area Williamsport Central 1.02 0.23-4.14 Williamsport East 1.28 0.15- 8.56 (Area average) 1.15 74 ------- 3. Charleston, South Carolina BaP was analyzed for three collection sites in Charleston, South Carolina, which has no coke ovens. The data are summarized in 3 Table A-24. The average concentration tor the city was 0.69 ng/m . Table A-24 DISTRIBUTION OF BaP CONCENTRATIONS IN AMBIENT AIR AT CHARLESTON, SOUTH CAROLINA* (ng/m3) Site Number 1 2 3 Location Radio Station WTMA Queen St. Fire Station Mt. Pleasant, Post Office Sample Size 22 22 22 Average 0.5711 0.7441 0.7448 Range 0.0028-1.2409 0.1693-1.6787 0.1995-1.9767 Total 66 0.6866 0.0028-1.9767 There are no coke ovens in Charleston. Source: Spangler and de Nevers (1975). '*. Maryland Atmospheric Data The Maryland State Division of Air Quality Control reports monthly composite BaP and BSO concentrations for many sites throughout the state. Data, primarily for 1976, are summarized in Table A-25. The Average annual BaP concentrations ranged from 0.43 ng/m for Harwood to 6 ng/m for Catonsville. 5. CHESS and CHAMP Site Data Atmospheric BaP and BSO data have been recorded for a number of CHESS and CHAMP sites through out the country. These data are sum- marized in Table A-26. Average annual concentrations ranged from 0.63 ng/m for Thousand Oaks, California to 4.2 ng/m for one site in Birmingham, Alabama. ------- Table A-25 AMBIENT ATMOSPHERIC BaP AND BSD CONCENTRATIONS FOR MARYLAND LOCATIONS Location Cumberland Hagerstown Adams town Frederick Myersville Buckeystown Glen Burnie Harmons Harwood Linthicum Odenton Riviera Beach Annapolis Baltimore Lexington and Gay Sun Avenue 1900 Argonne 5700 Reisterstown 5700 Eastern Samp le Size* 12 12 7 12 7 8 11 12 12 12 12 12 11 12 12 12 12 12 BaP Average 4.48 1.40 0.83 1.29 0.17 0.80 1.03 0.54 0.43 0.96 0.71 0.80 0.75 1.95 2.03 1.21 1.37 1.92 (ng/mj) Range 0.40-20.22 0.20- 3.87 0.31- 2.12 0.18- 3.55 0.05- 0.55 0.16- 2.52 0.15- 2.82 0.09- 2.10 0.04- 1.13 0.15- 2.18 0.08- 1.75 0.10- 2.79 0.10- 1.83 0.41- 4.46 0.50- 4.43 0.27- 3.51 0.42- 4.76 0.38- 5.36 Sample Size* 12 12 - 12 - - 12 - 12 12 12 12 12 12 12 12 12 12 BSO 1 Average 8.44 4.74 - 4.80 - - 4.84 - 2.93 3.99 3.69 4.25 3.76 6.27 6.88 4.21 5.26 6.38 'Mg/m ) Range 6.03-18.14 3.34- 7.40 - 3.48- 6.77 - - 2.67- 7.76 - 1.52- 4.51 2.21- 7.49 1.93- 5.74 2.50- 6.14 2.29- 4.93 4.34- 8.64 3.35- 9.50 2.51- 7.24 3.25- 8.11 4.25-10.06 ------- Table A-25 (Continued) Sample Location Size* Baltimore (Continued) Fonthill St Cockeysville Ind Pk Cockeysville Police Station Police Barracks 3001 Eastern Blvd Catonsville Dundalk (8801 Wise Ave) Edge me re Essex Fort Howard Towson Middle River Dundalk (Kavanaugh Rd) Dundalk (Reg. Voc. Training) Westminster Gaithersburg Silver Spring (1901 Randolph) Kensington 12 11 8 12 11 12 10 10 12 10 10 2 11 10 12 10 10 11 BaP Average 1.66 0.80 0.50 0.78 1.29 5.98 1.10 1.85 1.37 2.39 0.75 1.43 1.61 3.30 0.49 0.62 1.14 0.59 (ng/m3) Range 0.37- 4.80 0.09- 4.83 0.12- 1.76 0.10- 2.06 0.18- 3.97 0.09- 2.08 0.56- 2.42 0.07- 2.60 0.19- 4.36 0.38- 5.41 0.09- 2.95 1.14- 1.71 0.53- 4.60 0.31-10.35 0.09- 1.49 0.09- 2.13 0.09- 5.80 0.09- 2.07 Sample Size* 12 - 8 12 11 12 - - 12 10 3 2 - - 12 10 11 11 BSD Average 5.24 - 4.11 4.79 4.89 4.02 - - 5.35 4.79 5.48 6.52 - - 3.07 3.60 4.83 4.26 (ug/mj) Range 3.01- 8.68 - 2.15- 9.99 2.35- 7.40 3.27- 6.60 2.53- 6.22 - - 3.00- 7.98 2.64- 8.66 4.16- 6.41 6.25- 6.79 - - 1.95- 4.78 2.00- 5.17 2.51-11.69 3.05- 7.56 ------- 00 Sample Table A-25 (Concluded) BaP (ng/m3) Sample BSO (yg/m3) Location Poolesville Silver Spring (Rock Creek Forest) Rockville Bethesda Accokeek Cheverly Largo Laurel Orme Oxon Hill Laplata Elkton Cambridge Salisbury Size* 11 4 12 4 2 11 1 10 10 8 10 12 11 9 Average 0.46 1.83 0.96 1.25 1.06 0.65 1.30 0.52 0.49 0.70 0.34 1.02 0.62 0.58 Range 0.06- 1.40 0.58- 3.93 0.07- 4.57 0.71- 1.68 0.73- 1.38 0.17- 1.50 - 0.09- 1.37 0.08- 1.90 0.17- 1.50 0.17- 1.68 0.18- 2.73 0.18- 1.58 0.10- 1.59 Size* 12 - 12 - - 11 - 10 10 8 10 12 11 10 Average 3.36 - 4.51 - - 4.57 - 3.56 3.56 4.03 3.27 4.60 4.05 4.46 Range 1.89- 5.18 - 2.56- 8.89 - - 3.45- 6.24 - 1.90- 5.31 2.51- 5.33 3.08- 5.80 2.38- 4.95 3.55- 6.76 2.55- 5.80 3.03- 5.50 Number of months of data used in calculating the average and range. ------- Table A-26 ATMOSPHERIC BaP AND BSO CONCENTRATIONS FOR CHESS AND CHAMP SITES (1975 DATA) Location * Charlotte, NC (1) Charlotte, NC (2) Riverhead, NY Queens, NY Brooklyn, NY Bronx, NY Ogden, Ut Salt Lake City, Ut Kearns, Ut Magna, Ut Vista, CA Santa Monica, CA Thousand Oaks, CA Garden Grove, CA Glendora, CA West Covina, CA Anaheim, CA Sample Size** 6 6 12 12 12 12 12 12 12 12 12 6 12 12 12 12 12 BaP Mean 1.44 2.36 0.66 1.07 1.57 2.11 2.05 2.37 1.20 1.09 1.03 1.46 0.63 2.42 0.91 1.98 2.36 (ng/m ) Range 0.3-2.7 0.5-4.4 0.0-3.6 0.1-3.1 0.3-4.0 0.2-4.3 0.0-7.2 0.2-5.0 0.1-3.6 0.1-2.9 0.1-4.9 0.2-3.5 0.1-1.4 0.3-7.5 0.1-2.2 0.2-5.0 0.4-7.1 BSO Mean 1.79 2.91 1.29 1.99 3.70 3.24 2.41 3.26 1.43 1.48 2.07 3.91 2.31 3.86 4.13 5.85 4.77 (ug/m3) Range 1.1-2.3 2.2-3.8 0.6-2.0 0.9-2.8 1.1-7.6 2.0-3.6 0.7-8.8 1.6-7.7 0.7-3.2 0.5-3.4 0.8-6.7 1.1-6.1 1.1-4.8 0.8-11.9 0.5-6.5 2.6-9.5 1.6-11.2 * Data for Birmingham and Chattanooga are given with the city coke oven data in Tables A-8 and A-15, respectively. ** Number of months for which data are available; sample size for individual months generally ranged from 20 to 31 days. 79 ------- Appendix B STATISTICAL EVALUATION OF BaP ATMOSPHERIC CONCENTRATION DATA RECORDED IN THE VICINITY OF COKE PLANTS A. General This appendix presents a statistical evaluation of the BaP atmospheric concentration data recorded in the vicinity of coke plants. Factors addressed here include the following: What is the statistical distribution for atmospheric BaP concentrations over time at a given location? What errors are introduced by using estimated annual atmospheric concentrations, based on a small sample size? Can the average BaP concentrations around a coke plant be described as a mathematical function relating average concentration to distance from the plant? B. Statistical Distribution of 24-Hour BaP Atmospheric Concentrations Because of changes in meteorological conditions and other factors, the atmospheric BaP concentration at a specified location in the vicinity of a coke plant will vary from day to day. The day-to-day variations in the recorded 24-hour concentrations form a statistical distribution. The long-term concentration for a specified location is generally characterized by some central parameter for the distribution like the arithmetic or geometric mean or the median. Obviously, the atmospheric concentration data have been found to follow a distribution having rela- tively many small values, with a few observations ranging to fairly high values. These are called skewed distributions, as contrasted with symmetricaJ distributions. They are sometimes found to follow what is known as two- or three-parameter lognormal distributions. Figure B-l illustrates the cumulative statistical distribution for BaP atmospheric concentrations from some sampling locations. Because the 80 ------- 1000 i r \ I r n i i i i r n E O DC z UJ O § O £ U £ UJ i 100 10 O JOHNSTOWN STATION No. 7 H MONESSEN STATION No. 2 © CD j i 2% 10 20 40 60 PERCENTAGE 80 90 95 98% FIGURE B-1. STATISTICAL DISTRIBUTION FOR ATMOSPHERIC BaP CONCENTRATIONS 81 ------- plotted points approximate a straight line, the statistical distributions might be approximated by a lognormal distribution. The central measure that best characterizes this type of distribution is the geometric rather than the arithmetic average. The geometric average for these types of distributions is smaller than the arithmetic average. The properties of the lognormal distribution should be used when describing the probability that a particular BaP atmospheric concentra- tion will occur at a specified location. However, the arithmetic average should be used when estimating expected population exposures. That is, the arithmetic average concentration when used with daily human ventilation rates gives the expected daily inhalation exposure. This expected daily inhalation exposure multiplied by 365 gives the estimated total annual exposure. The point here is that the arithmetic average should be used in estimating expected population exposures, and the properties of the lognormal distribution should be used in estimating the probability of a specified exposure. Table B-l summarizes the arithmetic and geometric average and standard deviations for samples recorded at a number of stations. It is of interest and potentially useful that the coefficient of variation (standard deviation divided by the average) has a value near 1 (i.e., the standard deviation generally equals the average). C. Precision of Estimates Based Upon Small Sample Sizes Most of the ambient sampling data available for this study are based on 24-hour samples collected during limited sampling days. The ambient concentrations recorded for these dates, for a given location, are averaged and used as an estimate of the annual average concentration for that loca- tion. It is, therefore, desirable to know how well an estimated average annual concentration approximates the actual annual concentration. From a statistical viewpoint, it is first necessary to know if the sampling dates or period of dates were selected at random. In fact, sampling was probably conducted when people get around to it or are forced to do it and not because of any particular meteorological or 82 ------- Table B-l STATISTICAL SUMMARY FOR SAMPLING DATA TAKEN FROM A NUMBER OF LOCATIONS Arithmetic Sampling Location Monessen, 2 Monessen, 6 Monessen, 7 Johnstown, 1 Johnstown, 2 Johnstown, 3 Johnstown, 4 Johnstown, 5 Johnstown, 6 Johnstown, 7 g Johnstown, 8 Utah, 1 Utah, 2 Utah, 3 Utah, 4 Utah, 5 Utah, 6 Utah, 7 Utah, 8 Utah, 9 Utah, 10 Gadsden, 1 Gadsden, 2 Duluth, 1 Duluth, 2 Sample Size 29 28 31 30 32 33 32 28 31 34 31 9 6 9 11 11 11 3 11 11 9 5 5 18 20 Average 40.8 2.7 22.8 3.6 13.8 7.7 23.4 6.0 6.8 85.3 19.7 2.1 3.8 3.2 2.4 3.1 1.6 2.1 1.5 0.1 0.8 0.6 1.9 1.5 0.2 Standard Deviation 58.9 2.8 26.3 3.3 19.8 7.5 43.2 3.0 5.0 112.0 28.0 1.3 0.9 2.0 1.6 1.9 1.0 1.3 1.0 0.1 0.8 0.6 1.4 2.0 0.3 Coefficient of Variation* 1.4 1.0 1.2 0.9 1.4 1.0 1.8 0.5 0.7 1.3 1.4 0.6 0.2 0.6 0.7 0.6 0.6 0.6 0.7 1.0 1.0 1.0 0.7 1.3 1.5 Geometric Average 10.0 1.0 10.1 2.6 8.6 5.7 13.2 5.2 5.6 44.5 8.3 1.7 3.7 2.6 2.0 2.5 1.4 1.8 1.2 0.1 0.5 0.3 1.6 0.3 0.1 Standard Deviation 7.6 2.8 4.6 2.3 2.5 2.2 2.5 1.8 1.9 3.6 3.9 2.2 1.3 1.9 2.0 2.2 1.9 2.0 2.2 2.9 3.4 1.8 1.9 13.2 17.7 *The standard deviation divided by the average. ------- seasonal reasons. If this is the case, it might be assumed that the sampling period was selected in a quasirandom manner. The next point has to do with weighting the samples for individual dates by the fraction of time the meteorological condition on that date occurs during the year. This generally is not done because in some cases the meteorological conditions at the time of sampling are not reported or because representative sampling is not available for a range of probable meteorological conditions. If it can be assumed that the sampling period is taken at random and that no weighting of the samples is to be made, the estimation reduces to a simple statistical random sampling problem. In this case, the average of the available data becomes an unbiased estimate of the average concentration over the year. However, the number of dates for which data are available greatly affects the precision of the estimated annual -average. The precision of an estimated value is measured by its standard deviation. For a simple random sampling problem, the standard deviation for an estimated annual average is given by: P = Sf, where P = the standard deviation of the estimated annual average. S = the calculated standard deviation for the sampling data. f = /365-n V 365n n = the sample size. The factor labeled as f is called the finite sample correction factor, some values of which follow: Finite Sample Sample Size Correction Factor 1 0.999 5 0.444 10 0.319 20 0.217 30 0.175 50 0.131 100 0.085 200 0.048 365 0.000 84 ------- Note that the finite sample correction factor reduces in size rapidly with additional sampling when the sample size is small. Depending on the standard deviation for the sampling data, one might reasonably want sample sizes in excess of 30. Estimates based on sample sizes of less than 10 might be suspected of being quite imprecise. D. Evaluation of Ambient Concentration Data as a Function of Distance from Coke Plant Locations Available ambiend data that have been recorded in the vicinity of coke plants (Appendix A) are evaluated to determine if it is mathematically possible to represent the relationship of BaP concentration as a function of distance from the coke plant. To investigate the feasibility of an approach using recorded ambient concentrations, the average atmospheric concentrations have been plotted as a function of distance from the coke plants (Figures B-2 through B-14). As might be expected, the atmospheric concentrations decrease with increasing distance from the coke plants, thus indicating that the coke plants are a possible source of BaP. The moderate amount of scatter in these relationships is probably due to such factors as the location of the sampling site with respect to the coke plant, local meteorological conditions, and local geography. In addition, because many of the areas have several coke plants, it is difficult to characterize the contribution to the environment for an individual plant. If ambient data are to be used to characterize human exposure, it would be desirable to have data from many monitoring sites located at different directions from the coke plant and to have data recorded for each monitoring site over a large number of days. Much of the recorded data do not meet these requirements; the number of sampling stations by plant ranged from 1 to 16. The relationship of average atmospheric concentration to distance does appear to follow a mathematical function of the type: C = ADB> where 85 ------- DISTANCE PROM COKE PLANT - km FIGURE 8-2. ATMOSPHERIC CONCENTRATIONS OF BaP FOR JOHNSTOWN. PENNSYLVANIA 86 ------- 10 w& '?, U. s B ±ttt n- -rf ii I ffl H-i H H-rrt m ^ m^ -Hn 4-U H-T - 1 § 8 w DC ui X m rn r ±t i I: -t r , 1 ; fit T rr m ~ ;" I _L t ir^S^^E :r EH --r -2 ti i Uj: mf ai ttlttt ^ j I i rr 1 0.1 DISTANCE FROM COKE PLANT - km FIGURE B-3. ATMO»»HERIC CONCENTRATIONS OF BaP FOR GENEVA. UTAH ------- too RELATION TO SOLVAY RELATION TO GREAT LAKES A RELATION TO FORD DISTANCE FROM COKE PLANT - km FIGURE B-4. ATMOSPHERIC CONCENTRATIONS OF BaP FOR WAYNE COUNTY, MICHIGAN ------- 100 oo i ^.L^L^I ITS * . \ n&t ; i H RELATION IB UX STEEL RELATION TO J&L DISTANCE PROM COKE PLANT - km FIGORE B-5. ATMOSPHERIC CONCENTRATIONS FOR BaP FOR ALLEGHANY COUNTY. PENNSYLVANIA ------- I | ; 3T ft-r rm H- lit Traq.':a.i z^iJi-' M .., . ^ .. . LJ..J..I.I * - -. «-* i.. ,.,,,,!*,..,1 ,.:...., ...in _ O RELATSO TO MTHf LEM D RELATED TO BONNER-HANNA A RELATED TO ALLIED XI1 _ij ,i -,d i i : I Ml!T TT- ^-t-14' " _ w F I It rr - t "ft 1 r i Lffl Pffl \ ALLIED T^ t f p:; I if 4 f -t " ±- * 0.1 u 0.1 : jfTtft: i '- m, I 1.0 DISTANCE FROM COKE PLANT -km -L^ ... 10 FIGURE B-fl. ATMOSPHERIC CONCENTRATIONS OF BaP FOR BUFFALO, NEW YORK 90 ------- RELATIVE TO TARRENT D MCIATIVC TO A RELATIVE TO BIRMINGHAM 0.1 DISTANCE FROM COKE PLANT - km FIGURE B-7. ATMOSPHERIC CONCENTRATIONS OF BaP FOR BIRMINGHAM. ALABAMA ------- 1« ; : Pip 0.1 I I M I 1L g - I ; r -i i H- ± Tft *L c:: fi O SMMKftM PflNOB 2 [J SAMPLING PERIOD 1 4 if t r = = =Ff T I t JX +1 jj^. a H -HI tttt ! 4 fr tm B i 1 ! FT! t A I 6.1 1.0 DISTANCE FROM COKE PLANT - km FIGURE B-8. ATMOSPHERIC CONCENTRATIONS OF BaP FOR GRANITE CITY, ILLINOIS 92 ------- » « o IT DISTANCE FROM COKE PLANT - km FIGURE B-9. ATMOSPHERIC CONCENTRATIONS OF BaP FOR SPARROWS POINT, MARYLAND ------- C4 -f~U- DISTANCE FROM COKE PLANT - km FIGURE B-10. ATMOSPHERIC CONCENTRATIONS OF BaP FOR CLEVELEND, OHIO 94 ------- tT.[_- :JR '"';' 1 iff i« r.'j i 1 = . t & I i-it f I! T ttt tt 1 H-- T I _ T ± I i u- ffi i i 5-t" T I i t- ! , H -fl r \ - I s I ^ P r i ±: .« i m 0.1 0.1 f- R ; !: 1.0 10 DISTANCE FROM COKE PLANT - km FIGURE B-11. ATMOSPHERIC CONCENTRATIONS OF BaP FOR MONESSEN. PENNSYLVANIA 95 ------- DISTANCE FROM COKE PLANT - km f IGURE i-12. ATMOSPHERIC CONCENTRATIONS OF BaP FOR GADSDEN, ALABAMA 96 ------- m l;;!!l S: a i Jii .1 i i i r n- " : j :. f ftt ur IT l-t- a ! tr i : ai '!tf lit DISTANCE FROM COKE PLANT - km FIGURE B-13. ATMOSPHERIC CONCENTRATIONS OF BaP FOR DULUTH, MINNESOTA 97 ------- 00 oc UJ (J 8 y ALL UPWIND STATIONS 0.1 t DISTANCE FROM COKE PLANT - km FIGURE B-14. ATMOSPHERIC CONCENTRATIONS OF BaP FOR PHILADELPHIA. PENNSYLVANIA ------- C = the average concentration at some distance from the coke plant. A,B = model parameters fit by regression techniques. D = the distance from the plant. Least squares regression techniques have been used to fit the data to this mathematical function for each coke plant for which data are avail- able. The results of this evaluation are given in Table B-2. The regres- sion coefficients given in Table B-2 indicate how well the data fit the function. For most cases, the regression coefficients ranged from 0.5 to 1.0, suggesting fairly good approximations. The coke plants with only two monitoring stations showed, as expected, regression coefficients with a value of 1. The model parameters based on actual ambient data can be compared to similar fits to the atmospheric modeling data conducted by Youngblood (1977). Two conditions are given in Table B-2 for comparison (one for a dirty plant and one for a clean plant). The magnitude of the model parameter A relates to the amount of BaP emitted from the source, and the model parameter B relates to decay in the concentration versus distance function. Note that for all coke loca- tions with more than sampling stations on Table B-2 the B parameter varies between -0.32 to -1.42 with an average of -0.9. When locations that have more than one coke plant are a]so excluded, the parameter has an average value of -1.0. This compares favorably with the modeling data, which give a value of B of about -0.95. 99 ------- Table B-2 ESTIMATED PARAMETER VALUES FOR REGRESSION APPROXIMATIONS TO AMBIENT DATA Location Johnstown Gadsden Duluth Monessen Utah Wayne County Buffalo - Beth. Buffalo - D.H. Buffalo - Allied Cleveland Pittsburgh - USS Pittsburgh - J&L Tarrant Granite City Sparrows Point Fairfield Dirty Plant Model Clean Plant Model* Number of Stations 8 2 2 3 10 6 5 7 4 16 5 6 4 10 4 2 5 4 Model Parameters Regress: A 42.86 1.28 379.39 49.99 4.70 13.09 15.96 8.40 1.96 12.42 22.00 4.32 3.98 11.50 3.07 2.67 135.84 60.66 B -1.22 -1.62 -7.50 -2.92 -0.84 -0.69 -0.99 -0.75 -0.33 -1.42 -0.32 -0.37 -0.33 -0.57 -0.33 -0.07 -0.96 -0.95 Coefficii 0.96 1.00 1.00 0.64 0.76 0.92 0.79 0.60 0.06 0.72 0.16 0.52 0.75 0.10 0.61 1.00 0.99 0.98 Uses only data for distances of 1 km and greater. 100 ------- Appendix C DETAILED ESTIMATES OF POPULATIONS AND BaP CONCENTRATIONS FOR INDIVIDUAL COKE FACILITIES This appendix includes the detailed population and BaP concentration estimates for each defined geographic population ring (i.e., 0 to 0.5, 0.5 to 1, 1 to 3, 3 to 7, and 7 to 15 km) about each coke facility. These estimates are given in Tables C-l and C-2. The concentrations include the summation of atmospheric concentrations from both the coke- ovens and background. The population within a geographic ring was con- sidered not to be excessivly exposed to coke-oven emissions if its i estimated average annual BaP concentration was less than 0.1 ng/m . For some locations, several separate coke facilities are located within 15 km of each other. In these cases, it was necessary to estimate geographic population ring overlaps and total ring BaP concentrations. 101 ------- Table Ol DETAILED BaP POPULATION EXPOSURES (ng/m ) Coke Emissions Plus Background Distance from Coke Facility (km) Site No.' 1 2 3 4 5 6 7 B 9 10 11 12 13 14 IS 17-18** 19 20 21 22 23 24 23 26 27 28 29 30 31 32 33 34 0 - Population 388 0 0 478 1,656 975 0 0 0 0 827 0 2,618 0 57 512 0 0 99 552 11 0 0 0 991 0 3,368 P 0 1,184 0 6 0 0.5 Concentration F 1.5 15.0 6.0 1.7 F 5.0 19.0 10.0 2.0 7.3 19.0 4.8 19.0 5.4 2.1 87.0 68.0 39.0 30.0 4.3 F F F 2.2 4.2 3.9 2.7 F F 23.0 18.0 14.0 0.5 Population 1.756 0 0 916 532 5,279 0 1,416 0 7,244 7,307 0 2.494 0 8,176 3.059 53 33 482 0 3,416 3,008 2,197 51 3.901 0 2.450 202 3.113 2.537 2,373 2,608 0 - 1 Concentrat ion F 0.9 8.2 2.0 1.1 F 4.2 10.0 5.6 i.4 4.2 10.0 2.9 11.0 3.2 1.5 47.0 37.0 21.0 16.0 3.5 F F F 1.3 2.0 2.0 2.1 F F 13.0 9.7 7.9 1 Population 13.880 0 21,495 19.693 36,497 28.195 22.105 9,493 0 30,475 58,244 0 27,666 0 71,661 36,083 21,279 26,829 25,740 15,511 15,948 37,283 46,224 33,878 61,720 4,219 30,734 7,874 17,140 58,527 11,701 8,567 455 - 3 Concentration F 0.6 3.3 0.7 F 3.1 4.5 2.5 2.0 '4.3 1.4 4.4 1.7 1.0 18.0 14.0 8.4 6.2 2.5 F F F 0.8 O.B 0.9 1.6 F F 5.1 3.7 3.3 3 Population 114,873 5,843 80,440 36,345 158,506 120,414 120,356 51,629 0 46,890 248,247 2,828 187.310 16,253 207.269 42.851 51,533 122,882 70,004 35,072 97,933 289,066 322.403 172,788 255,071 7,036 224,719 111,218 138,521 257,202 55,346 57.955 749 - 7 Concentration F 1.6 F 2.4 2.5 1.4 1,2 2.2 -- 2.2 1.1 7.6 6.1 3.8 2.7 1.9 F F F ~ 0.6 1.2 F F 2.4 2.0 1.7 7 - Population 278,354 7,802 196,316 21,099 283.180 297.002 256.857 161.178 52 704,796 1,153,057 14.649 1.223.577 73.329 444,465 24,392 520.919 265.439 637,625 90,904 481.929 1,190.455 1,274.124 892,126 727.327 76.894 714,782 601.056 531,748 533.320 37,066 83,131 17,189 15 Concentration F 0.9 -- F F 1.8 0.9 1.4 0.9 3.9 3.2 2.1 1.5 - F F F -- - F r 1.4 1.2 1.1 ------- Table C-l (Concluded) Distance from Coke Facility (km) Site Ho.* 35 36 37 38 39 40 41 42 43 44 45-46** 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61-62** 63 64 65 0 - Population 0 0 663 1.530 0 0 0 13 0 0 3,960 1,804 0 0 0 2.628 2,433 0 1,024 2,374 0 1,185 6 0 19 0 0 3 1,300 0.5 Concentration 2.1 12.0 8.4 42.0 2.4 13.0 11.0 20.0 18.0 6.4 16.0 100.0 5.4 16.0 F 2.8 14.0 F F 34.0 50.0 1.8 11.0 3.5 10.0 79.0 6.0 18.0 3.1 0.5 Population 0 0 1,597 4,228 71 0 1,986 2,858 4,074 0 1,593 870 0 0 10,170 10,041 4,526 75 1,365 1,757 1.559 5.483 0 0 0 0 0 0 4,100 - 1 Concentration 1.4 6.4 4.7 25.0 1.5 6.9 6.4 11.0 9.2 3.8 9.1 50.0 3.3 9.2 F 1.9 7.8 F F 18.0 38.0 1.2 5.7 1.9 5.8 - 43.0 3.4 9.8 2.0 1 Population 10,963 5,352 22.961 73,580 17,663 20,260 45,234 72,578 33,723 26,142 42,961 35.460 573 19.922 115,372 56.243 54.405 31,991 16.819 30,671 22,763 16,595 4.866 1,046 3.044 0 0 20,971 43,000 - 3 Concentration 0.9 2.8 2.0 4.5 1.0 3.0 2.9 4.4 3.8 1>9 3.9 17.0 1.7 4.0 F 1.2 3.4 F F 7.4 10.0 0.7 2.1 1.0 2.6 16.0 1.6 4.0 1.2 3 Population 30,503 34,067 155,445 399,565 40,897 82,028 147,771 378,615 115,698 110,829 64,472 51.502 12,276 61,371 396,226 87,797 486,896 122,412 83,779 117,606 42,498 81 , 104 99,968 2.219 28,887 3,570 0 39,901 219,000 - 7 Concentration ^ 1.5 1.0 2.3 1.6 1.6 2.1 1.9 1.3 2.0 5.2 1.2 2.1 F 1.0 1.8 F F 3.4 2.0 -- 0.9 0.3 1.2 6.9 0.9 1.9 0.9 7 - Population 50.851 24,213 258,780 859,264 152,877 96,129 133,429 860.216 164,425 734,938 229,293 38,180 91,115 116.901 748,696 40.701 1,685,267 632,088 407,475 354,575 80.359 117.888 350,402 8,902 72,123 8,598 1.410 65.031 HE 15 Concentration __ 1.0 0.7 1.0 1.2 1.3 1.2 1.0 1.4 2.2 1.0 1.4 F 1.3 F F 2.0 0.4 3.4 0.7 1.1 Site numbers correspond to coke facilities listed in Table III-3. Indicates that the two facilities were treated as though they were colocated. F - Indicates that one or more coke facilities are located within 15 km of that facility. Estimated concentrations are given in Table C-2. Indicates that the atmospheric BaP concentration due to the coke facility was less than 0.1 ng/m3. ------- Table C-2 BaP EXPOSURES FOR PERSONS IN LOCATIONS HAVING MORE THAN ONE COKE FACILITY Location Birmingham, Alabama Detroit, Michigan Buffalo, New York Pittsburg, Pennsylvania Exposed Population 975 388 14,025 7,035 28,054 110,000 135,893 51 5,000 2,197 41,000 3,008 19,900 330,000 14,913 1,274,124 3,113 1,184 19,000 2,537 11,300 39,000 533,000 1,024 1,365 83,800 407,500 10,170 147,363 396,226 16,819 Exposure Concentration (ng/m3) 8.2 5.8 5.6 4.5 3.0 2.6 1.6 12.0 8.1 7,8 6.7 4.5 4.0 3.6 3.4 2.1 22.0 17.0 12.0 10.0 8.0 5.0 1.6 30.0 24.0 13.0 10.0 4.8 3.0 2.0 1.8 104 ------- BIBLIOGRAPHY Andelman, J. B. and M. J. 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