submicrometer particles emitted to the atmosphere that are not present at stack gas temperature.
“Instruction Manual for a Stack Sampler with Dilution,” CAES No. 477-77, 1978. ( 5 ) Hedges, K. R.; Hill, P. G. “Compressible Flow Ejectors, Part I-Development of a Finite Difference Flow Model,” presented at the Annual Meeting of the ASME, Paper No. 74-FE-1, 1974. (6) Hedges, K. R.; Hill, P. G. “Compressible Flow Ejectors, Part 11-Flow Measurements and Analysis,” presented a t the Annual Meeting of the ASME, Paper No. 74-FE-2,1974. (7) Razinsky, E.; Brighton, J. A. J . Basic Eng. 1971,93, 333-47. ( 8 ) Hidy, G. M.; Friedlander, S. K. A I C h E J . 1964,10, 115-24. (9) Friedlander, S. K. “Smoke, Dust and Haze”; Wiley: New York, 1977; pp 209-62. (10) Heisler, S. L.; Friedlander, S. K. Atmos. Enuiron. 1977, 11, 157-68. (11) Higuchi, W. I.; O’Konski, C. T. J . Colloid Sci. 1960, 15, 1449. (12) Delaitre, P.; Friedlander, S. K. Ind. Eng. Chem. Fundam. 1978, 17, 189-94. (13) Khatri, N. J.; Johnson, J. H.; Leddy, D. G. “The Characteristics of Hydrocarbon and Sulfate Fractions of Diesel Particulate Matter,” a SAE Paper 780111, presented a t annual meeting, 1978. (14) Lipkea, W. H.; Johnson, J. H.; Vuk, C. T. “The Physical and Chemical Characteristics of Diesel Particulate Emissions-Measurement Techniques and Fundamental Considerations,” SAE Publication SP-430, 1978.
Nomenclature
D , = particle diameter (pm) md, m, = mass flow rate of dilution air, sample (g/s) M = cumulative mass distribution Pi, Pm, PO,Psat = pressure of supply air, pressure of diluted sample, control pressure, vapor saturation pressure (N/ m2) AP, = pressure difference across the sample orifice (N/ m2) Qd, Q, = volumetric flow rate of dilution air and gas sample (m3/min) r = dilution ratio (Qd/Q,), each corrected to standard conditions Td, T,, T , = temperature of dilution air, diluted sample, sample (K) t = time (s) &, = relative humidity of diluted sample Literature Cited (1) Heinsohn, R. J.; Davis, J. W.; Anderson, G. W.; Kopetz, E. A., Jr.
Received for review December 11,1978. Accepted May 21,1980. This research was supported by Grant Nos. R803560 and R805738 from t h e Environmental Protection Agency administered through the Center for Air Environment Studies of T h e Pennsylvania State University (CAES No. 521-78).A longer version of this research was presented at T h e Second Symposium on Advances i n Particle Sampling and Measurement, sponsored by the Process Measurements Branch of the Industrial Environmental Research Laboratory, E P A . T h e symposium was held Oct 8-10, 1979.
Proc., Annu. Meet.-Air Pollut. Control Assoc. 1976, Paper No. 76-37.3. (2) Heinsohn, R. J.; Wehrman, J. G.; Davis, J. W.; Anderson, G. W. Proc., Annu. Meet.-Air Pollut. Control Assoc. 1977, Paper No. 77-12.1. ( 3 ) Heinsohn, R. J.; Davis, J. W. “Design of Stack Sampling System with Dilution,” CAES No. 494-78, 1978. (4) Wehrman, J. G.; Heinsohn, R. J.; Davis, J. W.; Anderson, G. W.
Chlorinated Paraffins and the Environment. 1. Environmental Occurrence Ian Campbell* and George McConnell Imperial Chemical Industries Limited, Research and Development Department, Mond Division, The Heath, Runcorn, Cheshire, P.O. Box No. 8, WA7 4QD, United Kingdom
Studies have been in progress since 1974 to measure the distribution and persistence of chlorinated paraffins in the environment, to determine their pathways through the environment, and to measure their concentrations in animal and vegetable life, including human tissue and human foodstuffs. The studies have used a newly developed sensitive and selective method of analysis for chlorinated paraffins in water, sediment, organic material, etc. Results are presented showing actual chlorinated paraffin levels measured in river and sea water and their sediments, in marine and land birds and their eggs, in fresh and saltwater fish and other aquatic vertebrates and invertebrates, in domesticated animals and foodstuffs derived from them, in foodstuffs of vegetable origin, and on human hands and in human tissues and organs from 24 subjects including a neonate. The results form a basis, in conjunction with toxicology studies by other workers, for an evaluation of the consequences of the use of chlorinated paraffins. 1. Introduction
1.1. Current Position. Chlorinated n-paraffins, widely used throughout the world, are relatively chemically stable, and this paper describes studies whose aim is to measure their distribution and persistence in the environment, to determine 0013-936X/80/0914-1209$01 .OO/O
their pathways through the environment, and to measure their concentrations in animal and vegetable life. Past studies of chlorinated hydrocarbon inputs to the environment ( I ) showed that they do not all have the same behavior patterns and characteristics and that not all chlorinated hydrocarbon classes exert harmful effects. Simple chlorinated olefins such as perchloroethylene and trichloroethylene appear a t low levels in the biosphere but do not accumulate because they are rapidly degraded. Polychlorinated biphenyls however, and some pesticides such as DDT, are very stable and widely distributed in the biosphere, where they bioaccumulate and may show toxicity. 1.2. Manufacture and Uses of Chlorinated Paraffins. Chlorinated paraffins as defined here and abbreviated hereafter to CP are made by chlorinating a number of different straight-chain paraffins oils and waxes in the C ~ O - Crange. ~O These feedstocks are typically chlorinated to varying degrees in the range 40-70% w/w to produce a range of products which are used as fire retardants and plasticizers in PVC, rubber, other plastics, varnishes, sealants, and adhesives and as extreme pressure additives in lubricants and metal cutting oils. World CP consumption in 1977 is estimated at 230 kton/yr with a compound annual growth rate of 5% p.a. over the past 5 yr. The main uses are as indicated in Chart I. Where CP is used as a fire retardant or plasticizer in PVC, elastomers or
@ 1980 American Chemical Society
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other plastics, sealants, paints, adhesives, etc., it is effectively bound into a polymer system and will, therefore, find its way into the environment from such products only very slowly, if a t all. The disposal of oils containing CP could present a more rapid route into the environment if these products are not properly disposed of or factory effluents are not correctly treated, and this may have been the major route for CP into the environment. Use of CP in oil probably represents about 20% of the total, viz., 45 000 ton world wide. 1.3. Structure and Properties of CPs. A CP contains a range of carbon chain lengths with varying numbers of chlorine atoms in positional isomeric distribution, mainly secondary and nonvicinal, e.g., -CHZCHClCH2-. CPs have very mmHg at 20 "C for a low vapor pressures, e.g., (1-2) X C14-17 paraffin with 52% chlorine. (Note: the percentage chlorine in a CP is lOOX the fraction of chlorine in the product molecular weight.) Water solubility is very low, and radioactive tracer measurements gave the values in Chart 11. Except for the c20-30 C P with high chlorine content, CPs are viscous, pale-colored dense oils, with the properties listed in Chart 111. The C20-30 C P with 70% chlorine is a solid with density 1.63 g/mL and softening point 90 "C. CPs are stable up to ca. 200 "C, and then they begin to dehydrochlorinate. CPs are completely destroyed by incineration and cannot volatilize in exhaust gases from an incinerator. Marketed CPs contain low levels of stabilizers (typically
