**UNITED STATES ENVIRONMENTAL PROTECTION AGENCY**

**WASHINGTON, DC 20460**

OFFICE OF PREVENTION, PESTICIDES, AND TOXIC SUBSTANCES

![](media/image1.png)

Memorandum Feb.14, 2008

> Subject: Product Chemistry Science Chapter for Creosote (P1/P13 and P2
> Fractions) Reregistration Eligibility Decision (RED) Process

From: A. Najm Shamim, PhD, Chemist

Regulatory Management Branch II

Antimicrobials Division (7510P)

To: Tim McMahon, PhD, Senior Toxicologist, and Risk Assessor

For Creosote RED

Antimicrobials Division (7510P)

And

Jackie McFarlane, CRM for Creosote RED

Regulatory Management Branch I

Antimicrobials Division (7510P)

Thru: Mark Hartman, Chief

Regulatory Management Branch II

Antimicrobials Division (7510P)

DP Barcode:

**Product Chemistry Science Chapter on**

**[Creosote]{.underline}**

**[Introduction:]{.underline}**

The product chemistry science chapter for Creosote is unique and
different from other Pesticides that Agency presents here. Since very
little product physical/chemical data on creosote ( PI/P13 and P2
fractions of coal tar creosote), Agency has used the data submitted by
the registrants and has used the open literature data available.

Heavy Duty Wood Preservative **Creosote** is a heterogeneous mixture of
polycyclic aromatic hydrocarbons and other heteronuclear aromatic
substances. US EPA 's document **Guidance for the Reregistration of
Pesticide Products Containing *CoalTar/Creosote***

( Document 540-RS-88-066)^1^ recognizes that "hundreds of individual
chemicals have been identified in coal tar/creosote and Lorenz &
Gjovik^2^ and McNeil^3^ have identified eight classes of compounds
commonly found in creosote and coal tar products." These are listed as
follows:

1\. Non-substituted six-membered rings

2\. Heterocyclic nitrogen bases

3\. Heterocyclic oxygen and sulfur compounds

4\. Alkyl substituted compounds( including polycyclic rings)

5\. Hydroxy compounds

6\. Aromatic amines

7\. Paraffins

8\. Naphthenes

Creosote as a pesticide used for wood preservation has no manufacturing
source. This Science Chapter deals with the Creosote mixture solution
derived from tar which is produced from carbonization of bituminous
coal. This is a coal tar fractional distillation process and from this
two fractions namely **P1/P13 and P2** are obtained. In general
fractions are collected when the temperatures are between 210 ^o^ C and
355 ^o^ C.^4^

Creosote Council, which represents the Creosote Industry, submitted the
product chemistry data for the P2 and P1/P13 creosote fractions in 1992
and resubmitted the data again in 1999 in compliance to the EPA's
Reregistration Standard and Data-Call-In issued for pesticide products
containing coal tar creosote. In the absence of EPA methodology to
determine the physical/chemical characteristics of mixtures like
creosote fractions, the Industry has supplied the data based on the
analysis performed by using the methods described by the American Wood
Preservers Association (AWPA) Standard Method for Analysis of Creosote
and Oil-Type Preservatives, specifically to analyze the creosote P2 and
P1/P13 fractions for determination of xylene insolubles, determination
of specific gravity, distillation fractions and determination of water
content in the respective fractions.

AWPA has stated that the P1/P13 and P2 (creosote)fractions for use as
heavy duty wood preservatives 'shall be a pure coal tar product, derived
entirely from tar produced by carbonization of bituminous coal.
Carbonization of coal is accomplished by distlling coal and coal tar
fraction is collected. The coal tar fraction itself consists of: light
oil, middle oil and heavy (oil) anthracene. It is the middle oil
fraction that is further distilled and various fractions from this
distillation are collected between the temperatures of 210 ^o^ and 355
^o^ C.

Open literature search shows ( James Mueller et. al )^5^ soil
contaminated with coal tar creosote consists of: 85% polycyclic aromatic
hydrocarbons (PAHs), 10% phenolic compounds and 5% N-, S-, and O-
heterocyclics. Table 1 lists some Polycyclic aromatic hydrocarbons found
in the P2 and P1/P13 fractions of creosote and have been reported by the
Creosote Council in its product chemistry data submissions. Table 2
lists the phenolic compounds and Table 3 lists the heterocyclic
compounds ^5^ . These components of Tables 1,2 and 3 represent 95% of
the total constituents in coal tar creosote. It must be pointed out that
among the PAHs listed in Table 1, sixteen are on the EPA's List of
Priority Pollutants.

> Table 1

Polycyclic Aromatic Hydrocarbons ( PAHs) in Coal Tar Creosote

  ------------------------------------------------------------------------
  Compound                               Relative          Molecular
                                         Percentage        Weight
  -------------------------------------- ----------------- ---------------
  Naphthalene                            13                128.2

  2-Methylnaphthalene                    13                142.2

  Phenanthrene                           13                178.2

  Anthracene                             13                178.2

  1-Methylnaphthalene                    8                 142.2

  Biphenyl                               8                 154.2

  Fluorene                               8                 166.2

  2,3-Dimethyl naphthalene               4                 156.2

  2,6-Dimethyl naphthalene               4                 156.2

  Acenaphthene                           4                 154.2

  Fluoranthene                           4                 202.3

  Chrysene                               2                 228.2

  Pyrene                                 2                 202.3

  Antraquinone                           1                 208.2

  2-Methyl anthracene                    1                 192.3

  2,3-Benzo\[b\]fluorene                 1                 216.3

  Benzo\[a\]pyrene                       1                 252.3
  ------------------------------------------------------------------------

Table 2

Phenolic Constituents in Coal Tar Creosote

  -----------------------------------------------------------------------
  Compound                       Relative           Molecular Wt.
                                 Percentage         
  ------------------------------ ------------------ ---------------------
  Phenol                         20                 94.1

  o-Cresol                       10                 108.1

  m-Cresol                       10                 108.1

  p-Cresol                       10                 108.1

  Pentachlorophenol              10                 266.4

  2,5-Xylenol                    7.5                122.2

  3,5-Xylenol                    7.5                122.2

  2,3-Xylenol                    5                  122.2

  2,4-Xylenol                    5                  122.2

  2,6-Xylenol                    5                  122.2

  3,4-Xylenol                    5                  122.2

  2,3,5-Trimethylphenol          5                  136.0
  -----------------------------------------------------------------------

> Table 3
>
> Heterocyclics in Coal Tar Creosote

  -----------------------------------------------------------------------
  Compound                           Relative          Molecular Wt.
                                     Percentage        
  ---------------------------------- ----------------- ------------------
  Heterocyclics & N-Containing                         
  Aromatics:                                           

  Quinoline                          10                129.2

  Isoquinoline                       10                129.2

  Carbazole                          10                167.2

  2,4-Dimethylpyridine               10                107.2

  Acridine                           5                 179.2

  Aniline                            5                 93.1

  2-Methyl quinoline                 5                 143.2

  4-Methyl quinoline                 5                 143.2

  Pyrrole                            5                 67.1

  Pyrrolidine                        5                 71.2

  S-Heterocyclics:                                     

  Benzo\[b\]thiophene                10                134.2

  Dibenzothiophene                   10                184.3

  O-Heterocyclics:                                     

  Dibenzofuran                       10                168.2

                                                       
  -----------------------------------------------------------------------

Table 4

Analytical Results of Creosote P2 and P1/P13 Fractions

  -------------------------------------------------------------------------------------
  Molecular   Compound                               CAS \#      P2          P1/P13
  ion (M^+^)                                                     fraction%   fraction %
                                                                 (mean)      (mean)
  ----------- -------------------------------------- ----------- ----------- ----------
  117         Indole                                 120-72-9    0.20        

              Indene                                             0.5         NC

  128         Naphthalene                            91-20-3     17.3        6.2

  129         Quinoline                              91-22-5     0.50        1.0

  134         Benzo\[c\]thiophene                                0.40        NC

  142         1-Methylnaphthalene                    90-12-0     1.3         2.5

  142         2-Methylnaphthalene                    91-57-6     2.80        5.6

  154         Biphenyl                               92-52-4     0.71        1.6

  154         Acenaphthene                           83-32-9     4.40        7.7

  156         Naphthalene                            91-20-3     17.3        6.2

  156         1,3-Dimethyl naphthalene               575-41-7    0.60        0.80

  166         Fluorene                               86-73-7     4.03        6.0

  167         9H-Carbazole                           86-74-8     1.4         1.7

  168         3-Methyl biphenyl ( 3-phenyl toluene)  643-93-6    0.61        0.30

  168         Dibenzofuran                           132-64-9    2.3         4.3

              1-Ethylnaphthalene                                 0.50        0.60

  178         Phenenthrene                           85-01-8     9.60        12.8

  178         Anthracene                             120-12-7    2.90        3.1

  179         Benzoquinoline-1(7,8-benzoquinoline)   230-27-3    0.70        

  180         9H-Fluorene                                        3.5         6.0

  182         4-Methyldibenzofuran                               0.40        0.80

  184         Dibenzothiophene                       132-65-0    0.94        1.3

  190         4H-Cyclopenta\[def\]phenanthrene       203-64-5    1.74        1.5

              Pyrene                                             4.0         4.7

  192         2-Methylphenanthrenes                              0.60        

              Chrysene                                           0.10        1.4

  202         Fluoranthene                           206-44-0    4.60        5.5

  202         Pyrene(benzo\[def\]phenanthrene        129-00-00   3.64        

  204         2-Phenylnaphthalene                    \-          0.47        0.20

              Benz\[e\]pyrene                                    0.50        0.3

              Benzo\[ghi\]perylene                               0.10        \<0.1

  216         1,2-Benzofluorene(benzo\[a\]fluorene   \-          0.73        

  216         2,3-Benzofluorene                      243-17-4    0.80        0.90

              Methylpyrene                                       0.30        0.20

  228         Benz\[a\]anthracene                    56-55-3     0.20        0.40

  228         Chrysene(benz\[a\]phenanthrene)        218-01-9    1.4         

  252         Benz\[b\]fluoranthene                  205-99-2    0.51        0.80

              Benzo\[a\]pyrene                                               0.40
  -------------------------------------------------------------------------------------

Notes:

1\. As most of the creosote constituents are polyaromatic hydrocarbons
(PAHs) and solubilities in water or non-aqueous media is not high, exact
and accurate quantitation is not possible. The registrants conducted a
quantitation method for the PAHs based on the calibration curves
generated on four PAHs: naphthalene, ( two ring compound), phenanthrene
( 3 ring compound) and two four ring compounds: pyrene and chrysene.
Calibaration curves were generated for these substances over a
concentration range of 2 to 1000μg/ml. These substances work as markers
for lesser known and identified PAHs in the creosote fractions. First GC
was used to separate the components and then quadruple Mass Spectrometry
was to obtain the mass spectra of individual substances. The registrants
reported the presence of components to levels less than 0.10%. The Table
4 identifies the components that are over 0.10 % in both the P2 and
P1/P13 fractions. The list also includes the presence of non-PAH
components

*[Product Chemistry Assessment]{.underline}*

The physical and chemical properties of both distillate fractions
creosote P1/P13 and P2 are described in the following

P1/P13 Fraction

Chemical Name: Coal Tar Creosote

Molecular Wt.: No Applicable

Color: 2.5Y2/2 to 2.5Y4/2 ( Based on Munsell color scheme)

Odor: Sharp, aromatic, wood-like

Solubility: 313 μg/ml

Vapor Pressure: 11.1 mm Hg at 24.4 ^o^C

Log P: 3.247

Stability: Short term( accelerated )stability was performed on four
constituents of the mixture: naphthalene, phenanthrene pyrene and
chrysene for a period of 30 days at 60 ^o^ C. At the end of thirty day
period, naphthalene remaining was : 96.5%, phenanthrene: 87.2%, pyrene:
86.9% and chrysene: 92.4%

Viscosity; 14.60 mm/s

Storage Stability: Not determined.

Notes: 1. The P1/P13 samples, provided by the Industry to Research
Triangle Institute, were distilled, within 95% confidence limit,
residues remaining were less than 1.1% as required by the AWPA Standard
A1-91 ( This test is similar to the EPA's Certified Limit Test required
for other pesticides).

2\. Insoluble mass in Xylenes: Duplicate determinations showed that this
fraction contained between 0.21 to 0.23% insoluble materials.

3\. Specific gravity of the fraction, for the industry sample ( single
determination) is 1.0934 ( corrected to 38^o^C)

4\. Moisture ( water) content for the industry sample ( single
determination) is 0.4%.

All these results were obtained by using the AWPA Method A1-91 Series.

> P2 Fraction

Chemical Name: Coal Tar Creosote

Color: 10YR2/1 to 2.5Y5/5 ( Munsell color scheme)

Odor: Strong aromatic, Petroleum-like

Solubility: 306 μg/ml

Vapor Pressure: 8.6 mm Hg at 24.4 to 24.5 ^o^C

Log P 3.311

Stability:

Viscosity: 15.5 mm/s at 25 ^o^C

The chemical structure of sixteen PAHs ( EPA Priority Pollutants ) are
provided below in the order of increasing complexity.

Some of the physical properties of selected PAHs are listed in Table 6 (
Illustrated Handbook of Physical-Chemical Properties and Environmental
Fate for Organic Chemicals by D. Mackay et al., Lewis Publishers, 1992).
Many of these are measured and a number of them ( particularly the
K~OW~) are estimated values.

**Table 6**

  --------------------------------------------------------------------------------------
  SELECTED                                                              
  PHYSICO-CHEMICAL                                                      
  PROPERTIES OF PAHs AT                                                 
  25^O^C                                                                
  ------------------------ ---------- ----------- ------------ -------- ----------------
  Compound                 v.p (s),   Log K~OC~   Solubility   Log      Henry Law
                           mm Hg                  mg/L         K~OW~    constant Pa
                                                                        m^3^/mol

  Indan                    15.1       \-          0.10         3.33     232.82

  Naphthalene              7.8 x      3.29        3.1x10^-2^   3.37     43.01
                           10^-2^                                       

  1-Methyl Naphthalene     6.6 x      2.96        2.8x10^-2^   3.87     44.90
                           10^-2^                                       

  2-Methyl Naphthalene     6.7        3.93        2.5x10^-2^   3.86     51.19
                           x10^-2^                                      

  Biphenyl                 9.97 x     3.57-3.77   7x10^-3^     3.90     28.64
                           10^-3^                                       

  Bibenzyl                 3.0 x      \-          4.3x10^-3^   4.70     16.93
                           10^-3^                                       

  Acenaphthene             2.2 x      3.79        3.8x10^-3^   3.92     12.17
                           10^-3^                                       

  Acenaphthylene           6.7        3.75, 3.83  1.6x10^-2^   4.00     8.40
                           x10^-3^                                      

  Fluorene                 6.7 x      3.76        1.9x10^-3^   4.18     7.87
                           10^-4^                                       

  Phenanthrene             1.5        4.42        1.1x10^-3^   4.57     3.24
                           x10^-4^                                      

  Anthracene               7.5        4.42        4.5x10^-5^   4.54     3.96
                           x10^-6^                                      

  Pyrene                   4.5 x      4.92        1.3x10^-4^   5.18     0.92
                           10^-6^                                       

  Fluoranthene             9.0 x      4.74        2.6x10^-4^   5.22     1.037
                           10^-6^                                       

  Benzo\[a\]fluorene       \-         \-          4.5x10^-5^   5.40     

  Benzo\[b\]fluorene       \-         \-          2.0x10^-6^   5.75     

  Chrysene                 4.2 x      4.89        \-           1.649    5.86
                           10^-9^                                       

  Benz\[a\]anthracene      2.0 x      4.57        1.1x10^-5^   5.91     0.581
                           10^-5^                                       

  Benzo\[a\] pyrene        5.2 x      5.48        3.8x10^-6^   6.04     0.046
                           10^-9^                                       

  Benzo\[e\] pyrene        5.5 x      4.00        4.0x10^-6^            0.020
                           10^-9^                                       

  Perylene                 1.0 x      \-          4.0x10^-7^   6.25     0.003
                           10^-9^                                       

  Benzo\[b\]fluoranthene   \-         5.74        1.5x10^-6^   5.80     \-

  Benzo\[k\]fluoranthene   3.9 x      5.92        8.0x10^-7^   6.00     0.016
                           10^-9^                                       

  Benzo\[ghi\]perylene                6.20        2.6x10^-7^   6.50     0.075

  Dibenz\[ah\]anthracene   2.7 x      6.52        6.0x10^-7^   6.75     \-
                           10^-12^                                      
  --------------------------------------------------------------------------------------

[Product Chemistry Chapter References]{.underline}

[MRID]{.underline} [CITATION]{.underline}

None American Wood Preservers' Association Standards, 1998, pp 3-4.

None MacKay D. et al., 1992. Illustrated Handbook of Physical-Chemical
Properties and Environmental Fate for Organic Chemicals, Lewis
Publishers.

None Mueller J.G. et al., 1989. Environ. Sci. Technol., Volume 23(10):
1197-1201.

None USEPA Document 540-RS-88-066. Guidance for the Registration of
Pesticide Products containing Coal Tar/Creosote.

None Cited in reference 4 above.

None Cited in reference 4 above.

44141101 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. Analysis and Certification of Product
Ingredients: Aristech Creosote P1/P13. Pesticide Assessment Guidelines
Reference Series 62. U.S.E.P.A. Pesticide Assessment Guidelines
Subdivision D: Product Chemistry. Unpublished study prepared by
Geochemical and Environmental Research Group, Texas A&M University, for
Aristech Chemical Corporation and John H. Butala, Technical Advisor,
Creosote Council II. July 23, 1992.

44141102 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. American Wood Preservers Association (AWPA)
Standard Physical Characteristics: Aristech Creosote P1/P13. AWPA
Standard Methods for Analyses of Creosote and Oil-Type Preservatives
(A1-89). U.S.E.P.A. Pesticide Assessment Guidelines Subdivision D:
Product Chemistry. Unpublished study prepared by Geochemical and
Environmental Research Group, Texas A&M University, for Aristech
Chemical Corporation and John H. Butala, Technical Advisor, Creosote
Council II. August 29, 1992.

44141103 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. Analyses of Physical and Chemical
Characteristics: Aristech Creosote P1/P13. Pesticide Assessment
Guidelines Reference Series 63. U.S.E.P.A. Pesticide Assessment
Guidelines Subdivision D: Product Chemistry. Unpublished study prepared
by Geochemical and Environmental Research Group, Texas A&M University,
for Aristech Chemical Corporation and John H. Butala, Technical Advisor,
Creosote Council II. September 15, 1992.

44141104 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. Analysis and Certification of Product
Ingredients: Aristech Creosote P2. Pesticide Assessment Guidelines
Reference Series 62. U.S.E.P.A. Pesticide Assessment Guidelines
Subdivision D: Product Chemistry. Unpublished study prepared by
Geochemical and Environmental Research Group, Texas A&M University, for
Aristech Chemical Corporation and John H. Butala, Technical Advisor,
Creosote Council II. July 23, 1992.

44141105 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. American Wood Preservers Association (AWPA)
Standard Physical Characteristics: Aristech Creosote P2. AWPA Standard
Methods for Analyses of Creosote and Oil-Type Preservatives (A1-89).
U.S.E.P.A. Pesticide Assessment Guidelines Subdivision D: Product
Chemistry. Unpublished study prepared by Geochemical and Environmental
Research Group, Texas A&M University, for Aristech Chemical Corporation
and John H. Butala, Technical Advisor, Creosote Council II. August 29,
1992.

44141106 Wade, Terry L. 1992. Product Chemistry Methods Development and
Validation for Creosote. Analyses of Physical and Chemical
Characteristics: Aristech Creosote P2. Pesticide Assessment Guidelines
Reference Series 63. U.S.E.P.A. Pesticide Assessment Guidelines
Subdivision D: Product Chemistry. Unpublished study prepared by
Geochemical and Environmental Research Group, Texas A&M University, for
Aristech Chemical Corporation and John H. Butala, Technical Advisor,
Creosote Council II. September 15, 1992.

45355601 Sparacino, Charles M. 2000. Product Chemistry for North
American CTM Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45355602 Sparacino, Charles M. 2000. Product Chemistry for North
American CTM Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45355701 Sparacino, Charles M. 2000. Product Chemistry for Western Tar
Products Corp. Creosote P1 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45355702 Sparacino, Charles M. 2000. Product Chemistry for Western Tar
Products Corp. Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45355801 Sparacino, Charles M. 2000. Product Chemistry for KMG-Bernuth,
Inc. Creosote P2 Storage Stability and Corrosion Characteristics.
Unpublished study prepared by Research Triangle Institute. March 31,
2000.

45355802 Sparacino, Charles M. 2000. Product Chemistry for KMG-Bernuth,
Inc. Creosote P1/P13 Storage Stability and Corrosion Characteristics.
Unpublished study prepared by Research Triangle Institute. March 31,
2000.

45355901 Sparacino, Charles M. 1998. Product Chemistry for Trenton
Sales, Inc. Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. October 15, 1998.

45356001 Sparacino, Charles M. 2000. Product Chemistry for Coopers Creek
Chemical Corp. Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45356002 Sparacino, Charles M. 2000. Product Chemistry for Coopers Creek
Chemical Corp. Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45356101 Sparacino, Charles M. 2000. Product Chemistry for Koppers
Industries, Inc. Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45356102 Sparacino, Charles M. 1999. Product Chemistry for Koppers
Industries, Inc. Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. October 26, 1999.

45356201 Sparacino, Charles M. 2000. Product Chemistry for Reilly
Industries, Inc. Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45356202 Sparacino, Charles M. 2000. Product Chemistry for Reilly
Industries, Inc. Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45363901 Sparacino, Charles M. 2000. Product Chemistry for Allied Signal
Incorporated Creosote P1/P13 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.

45363902 Sparacino, Charles M. 2000. Product Chemistry for Allied Signal
Incorporated Creosote P2 Storage Stability and Corrosion
Characteristics. Unpublished study prepared by Research Triangle
Institute. March 31, 2000.