METHOD #: 58 (Issue July 1986)
TITLE: Coal Tar Pitch Volatiles (CTPV) Coke Oven Emissions (COE) Selected Polynuclear Aromatic Hydrocarbons (PAHs) ANALYTE: CAS #
Coal Tar Pitch Volatiles 65996-93-2
CTPV
Coke Oven Emissions
COE
Selected Polynuclear Aromatic Hydrocarbons
PAHs
INSTRUMENTATION: HPLC
Matrix: Air
Procedure: Air samples are collected by drawing known
amounts of air through casttes containing
glass fiber filters (GFF). The filters are
洗衣店加盟选赛维干洗analyzed by extracting with benzene and
gravimetrically determining the
benzene-soluble fraction (BSF). If the BSF
exceeds the appropriate PEL, then the sample
is analyzed by high performance liquid
chromatography (HPLC) with a fluorescence
(FL) or ultraviolet (UV) detector to
determine the prence of lected
polynuclear aromatic hydrocarbons (PAHs). Recommended air volume有关新年的古诗
and sampling rate: 960 L at 2.0 L/min
Special requirements: Each GFF must be transferred to a parate
scintillation vial after sampling and the
vial aled with a PTFE-lined cap. Samples
must be protected from direct sunlight.
Status of method: Evaluated method. This method that has been
subjected to the established evaluation
procedures of the Organic Methods Evaluation
Branch.
Target concentrations: 0.20 mg/m3 for Coal Tar Pitch Volatiles (PEL) 0.15 mg/m3 for Coke Oven Emissions (PEL)
8.88 ug/m3 (1.22 ppm) for phenanthrene
0.79 ug/m3 (0.11 ppm) for anthracene
9.00 ug/m3 (1.09 ppm) for pyrene
旅游发展3.27 ug/m3 (0.35 ppm) for chryne
2.49 ug/m3 (0.24 ppm) for benzo(u)pyrene Detection limits of the
overall procedure: 0.006 mg/m3 for BSF
0.427 ug/m3 (59 ppb) for phenanthrene (PHEN)
0.028 ug/m3 ( 4 ppb) for anthracene (ANTH)
0.260 ug/m3 (31 ppb) for pyrene (PYR)
0.073 ug/m3 ( 8 ppb) for chryne (CHRY)
0.045 ug/m3 ( 4 ppb) for benzo(a)pyrene (BaP) Reliable quantitation
limits: 0.034 mg/m3 for BSF
0.740 ug/m3 (100 ppb) for PHEN
0.066 ug/m3 ( 9 ppb) for ANTH
1.13 ug/m3 (140 ppb) for PYR
0.273 ug/m3 ( 29 ppb) for CHRY
0.207 ug/m3 ( 20 ppb) for BaP
Standard errors of esti-
mate at the target
concentration: 8.3% for BSF
(Section 4.6.) 6.0% for PHEN
6.8% for ANTH
6.7% for PYR
6.3% for CHRY
5.8% for BaP
1.0 General Discussion
1.1 Background
1.1.1 History
Coal tar pitch volatiles (CTPV) include the fud polycyclic
hydrocarbons which volatilize from the distillation residues of
coal, petroleum (excluding asphalt), wood, and other organic
matter (Ref. 5.1.). Coke oven emissions (COE) are the
benzene-soluble fraction (BSF) of total particulate matter
prent during the destructive distillation or carbonization of
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coal for the production of coke (Ref. 5.2.). Coal tar is obtained
by the distillation of bituminous coal (Ref. 5.3.). Coal tar
pitch is compod almost entirely of polynuclear aromatic
compounds and constitutes 48-65% of the usual grades of coal tar (Ref. 5.3.).
The purpo of this work was to evaluate the sampling and
analytical method routinely ud by OSHA, and to make appropriate modifications if necessary. That method required samples be
collected with glass fiber filters (GFF) in three-piece
polystyrene casttes. The aled casttes were shipped to the
laboratory at ambient temperature and upon receipt were stored in a refrigerator until analyzed. The GFFs were placed in test tubes
containing benzene and sonicated for 20 min. The resulting
solutions were filtered with fine fritted glass filter funnels.
The GFFs were then rind twice with benzene and the filtered
rins combined with the original extract. The benzene extracts
were concentrated to 1 mL. A 0.5-mL aliquot of each sample was
taken to dryness and the BSF was determined gravimetrically. The other half of each sample was saved to be analyzed by HPLC if the
BSF was over the PEL.
Alternate samplers were not considered becau the O~HA standard
defines CTPV and COE as a function of tho components that
collected on a GFF. However, the following modifications were
made to the previous procedure to reduce costs and improve the
nsitivity and precision:
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1. Samples are collected clod-face with a two-piece castte
containing a GFF and a backup pad. A three-piece castte is
not necessary.
2. The GFF is removed from the castte and placed in a glass
vial which is aled with a cap containing a
polytetrafluoroethylene (PTFE) liner before shipment. This
increas the recovery of the analytes over the old
procedure.
3. The total extraction volume is reduced from 10 mL to 3 mL.
This eliminates the concentration step of the old procedure
(concentration to 1 mL) and greatly improves the recovery
and precision.
4. The extracted samples are filtered through pure PTFE
membrane filters instead of fritted-glass filter funnels.
Blank corrections, which were 30-70 ug with the old
procedure, are reduced to 5-20 ug.
The modified procedure resulting from this evaluation requires
that the GFFs be removed from the polystyrene casttes before
shipment and placed in aled vials. Three milliliters of benzene
are added to the sample vials and then the vials are placed in a
mechanical shaker and shaken for 1 h. The resulting solutions are
filtered through pure PTFE membrane filters. One and one-half
milliliters of the benzene extract are taken to dryness and the
BSF is determined gravimetrically. The rest of the sample is
saved to be analyzed by HPLC if the BSF is over the PEL.
The lected PAHs ud in this evaluation are phenanthrene
(PHEN), anthracene (ANTH), pyrene (PYR), chryne (CHRY), and benzo(a)pyrene (BaP). The compounds are analyzed by HPLC and are marker compounds to indicate the prence of PAHs. The
prence of BaP, identified by GC/MS, is ud to confirm the
prence of CTPV or COE when the BSF exceeds the appropriate PEL.
1.1.2 Toxic effects (This ction is for information only and should
not be taken as a basis for OSHA policy.)
The following information was reported in "Occupational Health
Guidelines for Chemical Hazards". (Ref. 5.4.)
Coal tar pitch volatiles (CTPV) are products of the destructive
distillation of bituminous coal and contain polynuclear aromatic
hydrocarbons (PNA's). The hydrocarbons sublime readily, thereby
increasing the amounts of carcinogenic compounds in the working
areas. Epidemiologic evidence suggests that workers intimately
expod to the products of combustion or distillation of
bituminous coal are at risk of cancer at many sites. The
include cancer of the respiratory tract, kidney, bladder, and
skin. In a study of coke oven workers, the level of exposure to
CTPV and the length of time expod were related to the
development of cancer. Coke oven workers with the highest risk of cancer were tho employed exclusively at topside jobs for 5 or
more years, for whom the incread risk of dying from lung cancer was 10-fold; all coke oven workers had a 71/2-fold increa in
risk of dying from kidney cancer. Although the causative agent or
agents of the cancer in coke oven workers is unidentified, it is
suspected that veral PNA's in the CTPV generated during the
coking process are involved. Certain industrial populations
expod to coal tar products have a demonstrated risk of skin
农村三资cancer. Substances containing PNA's which may produce skin cancer also produce contact dermatitis; examples are coal tar, pitch and
cutting oils. Although allergic dermatitis is readily induced by
PNA's in guinea pigs, it is only rarely reported in humans from
occupational contact with PNA's; the have resulted largely from
therapeutic u of coal tar preparations. Components of pitch and
coal tar produces cutaneous photonsitization; skin eruptions
are usually limited to areas expod to the sun or ultraviolet
light. Most of the phototoxic agents will induce hypermelanosis
室内团建游戏of the skin; if chronic photodermatitis is vere and prolonged,
leukoderma may occur. Some oils containing PNA's have been
associated with changes of follicular and baceous glands which
commonly take the form of acne. There is evidence that exposure
to emissions at coke ovens and gas retorts may be associated with
an incread occurrence of chronic bronchitis. Coal tar pitch
volatiles may be associated with benzene, an agent suspected of
causing leukemia and known to cau aplastic anemia.
1.1.3 Operations where exposure may occur
In 1970, there were over 13,000 coke ovens in operation in the
United States. It is estimated that approximately 10,000 persons
are potentially expod to COE. (Ref. 5.5.)
Coal tar pitch is ud in metal and foundry operations,
electrical equipment installations, pipe coating operations, and
at construction sites. About 145,000 people are potentially
expod to CTPV. (Ref. 5.6. )
The PAHs that were studied in this evaluation have been found in
many substances. The include coke oven emissions, coal tar
pitch, creosote, exhaust of internal combustion engines, and
cooked meats. Benzo(a)pyrene and chryne have also been isolated from cigarette smoke. (Refs. 5.5.-5.7. )
1.1.4 Physical properties (Ref. 5.8.)
Phenanthrene
CAS no.: 85-01-8
MW: 178.22
bp: 340-C at 760 mm Hg
mp: 100-C
color: white crystals
structure: Figure 1.1.4.
Anthracene
CAS no.: 120-12-7
MW: 178.22
bp: 342-C at 760 mm Hg
mp: 218-C
color: colorless crystals
structure: Figure 1.1.4.
Pyrene
CAS no.: 129-00-0
MW: 202.24
bp: 404-C at 760 mm Hg
mp: 156-C
color: colorless crystals
synonyms: benzo(def)phenanthrene
structure: Figure 1.1.4.
Chryne
CAS no.: 218-01-9
MW: 228.28
bp: 448-C at 760 mm Hg
英语电影台词mp: 254-C
color: white crystals
synonyms: 1,2-benzophenanthrene;
benzo(a)phenanthrene
structure: Figure 1.1.4.
Benzo(alpha)pyrene
CAS no.: 50-32-8
MW: 252.30
bp: 311-C at 10 mm Hg
mp: 179-C
color: yellow needles
synonyms: 3,4-benzopyrene; 6,7-benzopyrene
structure: Figure 1.1.4.
Benzene-soluble fraction (The sum of tho components collected on a GFF and soluble in benzene.)
color: brownish-yellow to black tar
1.2 Limit defining parameters (The analyte air concentrations listed
throughout this method are bad on an air volume of 960 L and a solvent extraction volume of 3 mL. Air concentrations listed in ppm are referenced to 25-C and 760 mm Hg.)
1.2.1 Detection limits of the analytical procedure
1.2.1.1 Benzene-soluble fraction
The detection limit of the analytical procedure is 6 ug per
sample and is bad on the precision of the analytical
balance ud. This is the weight which corresponds to twice the standard deviation of the precision data for a 50-mg
weight, which is the approximate weight of an average PTFE
