AWPA

Penta Re-Affirmation Data Package

For AWPA Standards

P8.1 and P35-08

April 9, 2010

By

Mike H. Freeman

INDEPENDENT WOOD SCIENTIST

Project Sponsor:

KMG-Bernuth and KMG Chemicals

Houston, TX

Executive Summary

In 2009, the AWPA Sub-Committee P-3 formed a Task Force for the Re-Affirmation of Pentachlorophenol (Penta or PCP) in the AWPA Book of Standards. This Task Force was chaired by Mike Freeman and contained the following TF membership:

Mike Freeman (Chair)

Dick Jackson Less Lonning Rick Blesky Jim Brient

John Falcone Denny Morgan Darryl Smith John Wilkinson

The charge of the TF was to Re-Affirm penta in the AWPA BoS utilizing AWPA Appendix I as a Guideline. The following is a summary of the Task Force findings:

Review Existing Standard

The Standard for penta in the AWPA BoS has historically been listed as Standard P8 section 1. In 2007, Freeman and Jung re-formatted the wood preservatives into the new Preservative Standard format and issued it for publication to Colin McCown, as AWPA Executive Vice President, which included a DRAFT watermark until final review and re-affirmation. This Standard has been reviewed and is now ready for full publication as AWPA Standard P-35, after removing the DRAFT watermark. AWPA Standard P8.1 is also adequate, but it is the Task Forces understanding, this Standard will soon be retired and archived under the AWPA System, much like the Use Category System replaced the Commodity Standards. The Task Force suggests both standards be re-affirmed until all P-8 Standardized wood preservatives are archived.

Efficacy Data and Reports

A complete efficacy review is attached to this Data Package and covers over six decades of testing and evaluation of penta as a wood preservative. Additionally, attached as under Appendix I to this Data Package, are the following documents:

Freeman, et al, 2005. This study is report on the 53-year exposure of penta treated wood pole stubs in southern Mississippi (AWPA Hazard Zone 5). This report and study indicates that wood treated to 0.30 PCF penta in # 2 Fuel oil has an estimated service life in AWPA Hazard Zone 5 of 74 years. It should be noted that this retention is far below the current AWPA recommendation for wood utility poles in this hazard zone.

Nicholas and Freeman, 2000. Is a Summary of over 11 years of laboratory and field testing by the authors, funded by EPRI, of penta in different carrier systems, which was also comparing these systems to penta alternatives. This study indicates that the carrier systems themselves are not particularly effective in ¾ inch stakes, but have some influence on the efficacy of the dissolved biocide in those same carrier oils.

Blew, et al, 1957, indicates that from his work at the USDA-FPL, penta is an effective biocide against Formosan Subterranean Termite attack and long term exposure to both native termites and Hazard Zone 4 & 5 decay conditions.

Product Performance

There have been no widespread failures of penta treated wood products in service, other than Cellon treated wood poles, failing to Soft Rot. Annually, sparse penta pole failures are noted by utilities, but investigation into many of these indicate either poor initial treatment, or a lack of a periodic inspection and maintenance and remedial treatment program.

MSDS’s and US EPA Product Labels

Currently, only one basic manufacturer is registered by the US EPA to sell and market penta into the USA. This company, KMG-Bernuth, a/k/a KMG Chemicals, maintains multiple EPA Restricted Use Pesticide labels with the US EPA. Penta has just recently undergone an extensive seven-year Re-registration program with the US EPA and Industry and the RED has been issued. Penta will continue to be registered by the US EPA for its intended purposes as a wood preservative. Example US EPA labels and Product MSDS’s are attached under Appendix II.

Extension of Exposure Conditions

Penta has been widely tested for use in wooden crossties for decades. Formerly, the work by Forintek Scientist Krzyzewski indicated both penta and copper Naphthenate were suitable crosstie preservatives for either creosote or creosote-petroleum solutions. In Fall 2009, the AWPA received specific proposals for penta in specialized petroleum solvent mixtures for the treatment of crossties. This new carrier system met the minimal requirements as established in the AWPA Standard P9-Type A, but also has additional favorable properties to extend wooden crosstie service life. This new system should be contained in the upcoming AWPA BoS.

Re-Affirmation Support

Letters and comments from wood treaters and wood preserving plants have been received in support of the re-affirmation of penta by the AWPA. Letters of support for the re-affirmation of penta by consumers and users of penta treated wood products have also been received. The TF chair has received no negative comments from any party, Task Force member, treater, or utility, which do not support the re-affirmation of penta in the AWPA Annual Bos. These are attached under Appendix III.

Summary and Closing Remarks

Currently in the USA, roughly 16.5 millions pound of technical penta is used annually to produce over 2 million wooden utility poles. Penta treated wooden poles make up roughly 53-55 % of the treated wood pole market in N. America according to surveys by Freeman (2009), Vlosky (2006), and Vlosky and Shupe (2007). It is the unanimous recommendation by the current AWPA Penta Task Force that penta be re-affirmed by the AWPA and continued to be listed in the AWPA Annual Book of Standards.

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PENTACHLOROPHENOL :

A Comprehensive Review of Its Efficacy and As A Wood Preservative

By

Mike. H. Freeman Independent Wood Scientist

Memphis, TN

Corresponding Author: wooddoc@aol.com

ABSTRACT

Pentachlorophenol used since the 1930’s was rated the least expensive of the three major

preservatives at least before rising cost of petroleum. Before 1987 penta was registered as

a herbicide, defoliant, molluskicide, mossicide, and disinfectant. Depending upon the

reporting country, the number of abandoned use patterns for penta ranges from all uses to

few uses. This paper reviews the properties of penta, its efficacy compared to that of older

preservatives such as creosote and chromated copper arsenates, and newer ones such as

copper naphthenate. It also reviews the factors that affect the efficacy of penta and more

especially its performance in oil-borne carriers. The performance of penta and the

properties of the treated wood are influenced by the properties of the solvent used.

Knowledge of the toxicology of penta has contributed to it being the most documented

substance in wood preservation. This paper also briefly reviews the EPA reregistration of

penta which showed that use in pressure treatment of wood did not pose an unacceptable

risk to man or the environment . Today penta remains the main wood preservative used

for utility poles in N. America with almost 55% of all poles being produced, utilizing penta in

P9-Type A oil as their preservative system.

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PCP INTRODUCTION

Pentachlorophenol, also known as penta or PCP, had its wood preserving properties

discovered in the 1930s and the production for wood preserving began on an experimental

basis then. Trade names include: Forpen®, Penta®, Pentacon®, Penwar®. Penta is a

standardized oil-borne preservative listed in the AWPA Book of Standards under P8-1.

Principal use in the United-States and Canada is now the pressure-treatment of railroad

ties, posts, cross arms, utility poles, and wharf pilings. Penta extends the functional life of

wood by at least eight times (Wilkinson 1995; Fishel 2005). It is dissolved in petroleum or

other organic solvents to allow adequate wood penetration.

Pure penta exists as colorless crystals with a sharp phenolic smell when hot but little odor

at room temperature. Impure penta is dark gray to brown and exists as dust, beads, or

flakes. The sodium salt dissolves easily in water, but penta itself does not. The two forms

have different physical properties, but are expected have similar toxic effects (ATSDR

2001). Treated wood typically contains about 130-140 �g/m3 penta corresponding to

concentrations of 0,484 mmol/L in treated wood (Pohleven and Boh 2007). Advantages of

penta are that it can be dissolved in oils having a wide range of viscosity, vapor pressure

and color, and it is clean and easy to handle and use. It is highly effective against wood

destroying organisms. In terms of cost, it is rated the least expensive of the three major

preservatives (Hatcher 1980) at least before rising cost of petroleum. Due to continual

increase in petroleum costs and possible reduced availability of petroleum in the future

there has been need to find treating processes which will keep the industry competitive

and profitable in the face of competition from other materials (Hatcher 1980).

PHYSICAL AND CHEMICAL PROPERTIES

The physical/chemical properties of penta are well characterized (Table 1). It is freely

soluble in organic solvents, slightly soluble in cold petroleum ether, carbon tetrachloride

and paraffins and is inflammable. Technical penta used in wood preservation contains

toxic impurities. Those of regulatory concern penta’s microcontaminants (FAO 1996).

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Table 1. Physicochemical properties of penta (WHO 1987)

Property Value value

Physical state Light tan to white needle-like crystals. Crystalline, aromatic

compound

Water solubility (at 20°C) 14 mg/litre (pH 5), 2 g/litre (pH 7), 8 g/litre (pH 8)

Log octanol–water partition

coefficient

3.56 (pH 6.5)

3.32 (pH 7.2)

Melting point 191ºC (anhydrous), 174ºC (monohydrous).

Vapour pressure 2 × 10-6 kPa at 20°C

Boiling point 309-310°C (decomposition)

Density 1.987 g/cm3

pKa 4.7 at 25°C

HISTORY

The wood preserving properties of penta were discovered in the 1930s. Water-repellent

solutions containing penta in solvents of the mineral spirits type, were first used in

commercial dip treatments of wood by the millwork industry in1931. Commercial pressure

treatment of poles with penta in heavy petroleum oils began in 1941, and considerable

quantities of various products soon were pressure treated. Penta became a restricted-use

pesticide in 1987 and is only available to certified applicators. It now has no registered

residential uses (Fishel 2005; EPA 2008). Before the 1987 Federal register notice that

canceled and restricted certain uses, penta was registered as a herbicide, defoliant,

mossicide, and as a disinfectant. It was then one of the most widely used biocides (EPA

2007). In 1947 nearly 3,200 metric tons of penta was reported to have been used in the

U.S. by the wood preserving industry. As of 2002, about 11 million pounds of penta was

produced. It may not be used in residential, industrial, or commercial interiors except for

laminated beams or building components in ground contact and where two coats of sealer

are applied. It may not be used in farm buildings where there may be contact with animals

or in beehives.

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Because penta was used for a wide range of domestic, agricultural, and industrial

purposes for more than 60 years, the compound is ubiquitously distributed in the

environment (Pohleven and Boh 2007). Its occurrence in aquatic and terrestrial food

chains has been established (Fishel 2005). Penta continues to be used but depending

upon the reporting country, the number of banned uses ranges from all uses to few uses.

Most reporting countries banned residential indoor uses. Austria, India, Indonesia, New

Zealand, Sweden and Switzerland have reported a total ban (FAO 1996).

In 1997 the manufacturers of penta voluntarily removed groundline/remedial treatment

applications from the U.S. EPA registered labels for the product. All non-pressure and non-

thermal treatment uses (i.e., spray uses) were deleted from the registrants' labels since

2004. This action left only pressure and thermal treatments with penta. Non-pressure/non-

thermal treatments generally lead to higher applicator exposures.

MODE OF ACTION

Penta is toxic to all forms of life because it is an inhibitor of oxidative phosphorylation.

Often used in combination with an insecticide, penta/NaPCP at low concentrations causes

significant uncoupling of oxidation and phosphorylation cycles in tissues. At high

concentrations it inhibits mitochondrial and myosin adenosine triphosphatase, inhibits

glycolytic phosphorylation, inactivates respiratory enzymes and causes gross damage to

mitochondria (Ozanne 1995). This results in accelerated aerobic metabolism and

increasing heat production. It also causes loss of membrane electrical resistance (FAO

1996).

PRODUCTION AND USE

Penta is produced by the stepwise chlorination of phenol in the presence anhydrous

aluminum or ferric chloride catalyst at 191°C. Outside of the United States, it is also

produced by the alkaline hydrolysis of hexachlorobenzene. Because the production

process is incomplete, commercial grade penta is 84-90% pure. Several contaminants

including other polychlorinated phenols, polychlorinated dibenzo-p-dioxins and

polychlorinated dibenzofurans are produced too.

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Production volumes steadily decreased from 45 million pounds in 1983 to 9.1 million

pounds in 1996 (IARC 1999). Up to 2004, Vulcan Chemicals, a division of Vulcan Materials

Co. was the only domestic manufacturer of penta. Production volumes declined due to

restriction in uses. From 1983–1986 it declined as follows: 42 million pounds in 1984; 38

million pounds in 1985; and 32 million pounds in 1986 and about 24 million pounds were

manufactured in 1987. In 2004, Vulcan Materials sold the assets of its Vulcan Chemicals,

to Basic Chemical Co. LLC, a subsidiary of Occidental Chemical Corporation but decided

against entering the penta business (vulcanmaterials.com). In 2005, KMG Chemicals, Inc.

a global provider of specialty chemicals acquired assets used in the manufacture and sale

of penta from Occidental Chemical Corporation. The equipment was used to back-up

KMG's then existing penta plant, thereby assuring security of supply for penta. KMG had

acquired the original penta distribution business in 1984 and built a penta manufacturing

plant in Matamoros, Mexico in 1986. KMG is currently the only producer of penta in North

America. Penta revenues were projected to increase by over $3 million per year. Demand

for penta and creosote was near record levels during fiscal 2007, driven by continued

strong demand for utility poles and rail ties. KMG’s penta revenues increased 2% to $28.4

million as compared to fiscal 2006. The Railway Tie Association forecasted demand for rail

ties to be relatively flat in 2008 and KMG anticipated the same for utility pole demand. The

company's penta products include penta blocks, solutions of penta concentrate, and

byproduct hydrochloric acid manufactured at its Matamoros, Mexico and Tuscaloosa,

Alabama facilities( Alabama is only a formulating plant only). In the U.S., the company

sells penta primarily in Alabama, Arkansas, Georgia, Louisiana, Mississippi and Missouri.

The penta segment constituted 17% of the company's net sales in fiscal 2008 and the

creosote segment constituted 36% of the company's net sales in fiscal 2008.

STANDARDS AND SOLVENTS FOR PENTA

The standard AWPA P8 defines the properties of penta wood preservative. Penta solutions

for wood preservation shall contain not less than 95% chlorinated phenols, as determined

by titration of the hydroxyl group and calculated as pentachlorophenol. The performance of

penta and the properties of the treated wood are influenced by the properties of the solvent

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used (Ibach 1999). AWPA P9 standard defines solvents and formulations for organic

preservative systems.

i. AWPA P9- Hydrocarbon solvent Type A- The heavy petroleum solvent included

in P9-A is preferable when the wood is used in ground contact and for bridge

applications. The solvents are petroleum oils and hydrocarbon solvents (No. 2

diesel, and blends of diesel oils with auxiliary solvents that are intended to stay in

the wood due to the high boiling characteristics. The heavy oils remain in the wood

for a long time but do not usually provide a clean or paintable surface. They are

designed to provide permanent penta solvency in wood and physical properties that

will minimize the depletion rate of penta from wood.

ii. AWPA P9- Hydrocarbon solvent Type B- Consists of a highly volatile carrier

system such as LPG, isopropyl ether, or butane with sufficient penta solvency. The

carrier must be removed in the cylinder or the preservative will migrate to the

surface and be lost after treatment. Hence the vapor pressure of the carrier must

be extremely high at ambient temperature. Butane leaves a clean surface. A

commercial process using penta/LPG was introduced in 1961, but its field

performance was found inferior thus it is no longer used. Type D is similar to B.

iii. AWPA P9- Hydrocarbon solvent Type C- A system of light naphtha (mineral oils

or VMP naphtha) with a high-boiling and non-water soluble high viscousity auxillary

solvent with ability to dissolve nearly its own weight of penta. It is used when

treating glulam before gluing. These co-solvents must have ability to prevent

migration and blooming as the light carrier solvent evaporates and migrates to the

surface. The light naphtha may be either recovered in the cylinder by a solvent

recovery process or left to evaporate from the wood.

iv. AWPA P9- Hydrocarbon solvent Type E-This is an oil dispersion in water. It is

only approved for aboveground use in lumber, bridge ties, mine ties, and plywood

(Ibach 1999).

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HEAVY PETROLEUM SOLVENTS CHARACTERISTICS

Petroleum solvents used with penta have continually changed over the years. When penta

as first used in wood preservation, only straight-run distillates having 5% solvency were

available. Later cracking, aromatization and solvent refining of diesel increased the

solvency and provided more stable oils. Hydro treating increases the stability and yields

higher grade products, stabilizes color but it lowers penta solvency through reduction of

the olefinic content. Heavy oils contribute to sludge and emulsions and do not produce

clean treatments. Sulfur compounds, olefins and nitrogen compounds in the oils are

reactive under conditions of heat, moisture, acidity and catalytic action of penta. Blending

heavy oils with oxygenated co-solvents and use of trace amounts of antioxidants and

stabilizers that prevent catalytic polymerization creates solvents meeting various needs

such as: light and uniform color, solvent power to carry preservative in wood at the

concentration used for adequate penetration into wood, permanency of treatment,

resistance to emulsification and sludging during storage and treating, lower corrosiveness,

lower cost and finally lower environmental and industrial hazard. Avoiding emulsions is

important to prevent deposits on the surface.

Loss through volatilization, leaching, blooming, bleeding, migration and decay can all be

reduced by proper design of the carrier system. AWPA P9 recognizes that the higher

boiling constituents are also the more viscous and more permanent. If the high solvency

of a carrier is combined with a tendency of the carrier to migrate due to its volatility,

viscosity and surface tension, then depletion of the preservative is considerable. Majority

of the solvency of a carrier should be in the permanent portion of the carrier. Permanency

is a function of high-boiling constituents, high viscosity and high interfacial tension

(Arsenault 1973). Loss of penta from pole sections is greater in low interfacial surface

tension oils than from high interfacial surface tension oils. If too little solvency is available

in the more permanent portions of a solvent or if the solvency power is lost by evaporation,

or leaching, after treatment, the preservative may be carried to the wood surface causing

depletion. Co-solvents for penta solvents are normally the non swelling type because

swelling agents are water miscible. Water solubility must be low enough so as not to cause

preservative drop-out before penetration is accomplished (Arsenault 1973).

8

RETENTION

Retentions required after treatment must be the amount needed to protect plus an amount

lost through migration and depletion. Studies with penta wood have shown that decay

tends to start when the outer zone has retention lower than 0.20 pcf. Pole line inspections

have confirmed this (Arsenault 1973). Penta/LPG treatment and penta-petroleum

treatment both require a minimum retention of 0.70 pcf in the outer ½-in. zone to prevent

deterioration of wood poles (DeGroot 1984). Other depletion studies have shown that initial

retentions should be 13-14 pcf creosote and 0.6-0.8 pcf penta for effective protection in

ground contact for effective protection and provide for depletion. Loading to higher levels

than those demanded by practical standards results in waste, undesirable surface

appearance, bleeding and increased depletion. Excessive final steaming will lower the

surface retentions of organic wood preservatives by steam distillation and it will also lower

the distribution gradient. It removes approximately 19% of the penta and 25% of the

solvent uniformly over the cross section resulting in a cleaner surface. The lowering of the

gradient can be adjusted for by slightly over treating or increasing the penta concentration

in treating solution. This lowers loss of penta in service by exudation and solvent

migration.

EFFICACY AND COMPARISONS TO OTHER PRESERVATIVES

Tests on poles in service and field tests on wood treated with 5% penta in a heavy

petroleum oil show efficacy similar to that of coal-tar creosote (Davidson 1977; Ibach

1999). Creosote at 4.9-5.1 Ib/ft3 and 5% penta in heavy petroleum has shown service life

of over 35 years against Formosan termites in saucier Mississippi and Lake Charles,

Louisiana. Penta had a slightly better performance in Mississippi (Crawford et al., 2000).

Davidson (1977) gives an evaluation of the effectiveness of various wood preservatives, in

treated southern yellow pine fence posts installed at saucier Mississippi an AWPA hazard

zone 5 since 1949. In 2005 Freeman and co-workers reassessed the condition of the

treated wood posts, and statistically calculated the expected post life span (Table 2). The

study used SYP fence posts with an average diameter of 4-5 inches. In estimating service

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life prior to 100% failure, average service life was approximated by the time when 60% of

the posts in a group have failed. Freeman et al. (2005) evaluated the posts by a standard

50 Ib lateral load pull test. After 53 years many of the posts failed upon to the stress load.

Table 3 shows some of the preservatives, retention, posts remaining, and percentages of

posts that passed or failed the test. It was determined that penta in oil, creosote, and

copper naphthenate in oil, provided life spans calculated to exceed 60 years. Creosote,

with low residue, (clean creosote) did not perform as well, giving a service life of 37 years

from the 1977 inspection, and 45 years in the 2005 evaluation. Penta treated posts, in P9-

Type A oil (# 2 fuel oil) treated to a retention of 0.30 pcf penta, (75% of the AWPA

standard retention) had a typical calculated service life of 74 years in the 2005 evaluation

and an even better performance when dissolved in aromatic residue.

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Table 2. Average service life s of penta, creosote and Cu-Nap treatments in

Mississippi.

Preservative Predicted service

life

(Davidson et

al.,1977)

Predicted service

life (Freeman et al.,

2005)

Ammoniacal copper arsenate (ACA) 42 59.5

Coal-tar creosote, straight run, low residue 37 45.7

Coal-tar creosote, straight run, medium residue 40 54.0

Coal-tar creosote, medium residue, low in fraction

from 235° to 270° C, crystals removed

40 71.7

Copper naphthenate (5%)-petroleum 42 72

Pentachlorophenol (5%)-petroleum oil

(No. 2 distillate)

42 74

Pentachlorophenol (5%)-petroleum oil

(Wyoming residual)

36

Penta 5% in Petroleum Oil 55.5

Penta 5% in #4 Aromatic Res. 119.4

Penta 3% In #4 Aromatic Res. 122.1

untreated controls 3.6 2.4

Table 3. Preservative retention, posts remaining and percentages of pass, fail posts

evaluated.

Chemical Ret. % Remaining Fail Pass

Ammoniacal copper arsenate

ACA

0.34 64 4 (25%) 12 (75%)

CuNap 5% Cu in Petroleum 6 68 4 (24%) 13 (76%)

Boliden Salt B 0.7 60 1 (7%) 14 (93%)

Penta 5% in #2 Distillate 6.3 68 0 (0%) 17 (100%)

Penta 5% in #4 Aromatic Res. 5.9 88 1 (5%) 21 (95%)

Penta 3% In #4 Aromatic Res. 6 100 2 (8%) 23 (92%)

Penta 5% in Petroleum Oil 6 64 6 (38%) 10 (63%)

Penta 5% Cu Nap in Petro 6.2 92 2 (9%) 21 (91%)

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Creo Straight Run High Res 6 72 2 (11%) 16 (89%)

Creo Straight Run Low Res 5.9 28 4 (57%) 3(43%)

Control 0 0 0 0

Other efficacy studies include those by Johnson and Thornton (2000) who report data from

stakes of Pinus radiata sapwood and Eucalyptus regnans exposed for 35 years at three

Australian sites (Innisfail, Sydney, Walpeup). After 35 years, 5% penta in furnace oil (128

kg/m³) performed as well as Australian K.55 (blend) creosote oil and much better than 5%

penta in diesel fuel oil (128 kg/m³). Penta has been shown to provide adequate protection

after 18 years in roofing shingles of western wood species treated by simple dipping and

brushing (Scheffer et al., 1997). Highley et al. (1993) showed that length of dipping in

penta whether 3 or15 minutes gave similar results. No benefit of longer dipping was

observed and there was no evidence that incorporation of water repellant improves

effectiveness of penta.

Crawford et al. (2000) present results of a long term stake test initiated in 1938 by the

Forest Products Laboratory. Replicate stakes of southern pine sapwood treated with

several preservatives were installed in test sites at Saucier Mississippi, Madison

Wisconsin, Bogalusa Louisiana, Jacksonville Florida; and the Canal Zone, Panama. In

1967 another stake installation that included 11 standard wood preservatives was made in

at Lake Charles, Louisiana is infested by Coptotermes formosanus. Table 4 summarizes

the efficacy comparison at the Mississippi site. Penta in heavy oil, performed as well as

creosote and ACC with service life above 35 years. Performance of penta in mineral oils

and that of Tributyltin oxide (TBTO) was inferior with service life below 20 years. TBTO

generated a lot of attention as a possible alternative to penta but is less effective, is

detoxified by microorganisms and degrades at elevated temperatures (Johnstone 1986).

The performance of P.radiata samples impregnated with a range of light organic solvent

preservatives or CCA salt in and above ground revealed that TBTO performed poorly

compared to penta which gave relatively good protection under both hazard conditions and

that CCA was most effective. In this study TBTO contributed only slightly towards fungal

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protection when combined with penta and could be rated as relatively unsuccessful without

fortification with penta (Johnstone 1986).

Table 4. Long term stake test performance with various wood preservatives in

Missisispi. (Retention values in parentheses are based on preservative oxides or

copper metal)

PRESERVATIVE RETENTION

(Ib/ft3)

AVERAGE LIFE

(YEARS)

REMARKS

0.25 11.6

0.51 - 70% failed after 55 years

0.75 - 50% failed after 55 years

ACID COPPER CHROMATE

1.54 - 22% failed after 35 years

CHROMATED COPPER ARSENATE 0.14 No failures after 22 years

COPPER-8-QUINOLINOLATE

Stoddard Solvent (mineral oils).

0.12 7.8

0.03 27.3 COPPER-8-QUINOLINOLATE

AWPA P9 Heavy Oil 0.12 - No failures after 37 years

10.3 (0.012) 15.9

10.2 (0.029) 21.8

10.6 (0.061) 27.1

COPPER NAPHTHENATE

(No. 2 Fuel Oil).

9.6 (0.082) 29.6

4.6 21.3

8.3 50% failed after 46 years

13.2 20% failed after 54-1/2 years

CREOSOTE, COAL-TAR

16.5 10% failed after 60 years

0.38 80% failed after 38-1/2 years

4.00 13.7

PENTA

Stoddard solvent (mineral spirits)

8.00 15.5

4.10 89% failed after 50 years PENTA

Heavy gas oil (Mid-United States) 7.90 80% failed after 50 years

4.20 21 PENTA

No. 4 aromatic oil (West Coast) 8.20 70% failed after 50 years

PENTA

AWPA P9 (heavy petroleum)

0.11 90% failed after 38-1/2 years

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Nicholas and Freeman (2000) compared the performance of CuNap and penta pine stakes

against decay and termite attack at two test sites in Mississippi using four different

petroleum oils meeting AWPA P9-A as carriers. The efficacy of CuNap at a retention of

0.05 pcf Cu was found equivalent or slightly better than penta at 0.40 pcf after ten years

exposure. The type of carrier oil had an effect on the performance, but was variable for

type of preservative and test site. A summary of the results is shown in Table 5 and Figure

1. All of the CuNap formulations performed better than comparable penta formulations

except in the diesel/KB3/B11 and base oil formulations, for which the performance of

CuNap is slightly lower than for penta at the Saucier test site. The depletion rate of penta

was somewhat greater than that for CuNap. The depletion rate plays a major role in the

performance of treated wood.

Table 5. Average % Depletion of Cu-Nap and Penta in stakes treated with several different

carrier oils exposed at saucer for 2-years.

Average % loss after 2-years exposure Career oil Preservative Initial

Retention (pcf) Above ground Below ground

Cu Nap. (0.049). 20.3 30.1 Ashland

Penta (0.383) 8.4 39.2

Cu Nap. (0.045). 20.6 17.1 CA Shell

Penta (0.383) 14.7 39.4

Cu Nap. (0.049). 17.9 21.8 Base Oil L

Penta (0.396) 11.2 43.2

Cu Nap. (0.051). 8.0 18.8 Diesel/KB3/B11

Penta (0.394) 31.9 19.1

PENTA

AWPA P9 (heavy petroleum)

0.11 90% failed after 38-1/2 years

0.29 No failures after 38-1/2 years

0.29 No failures after 38-1/2 years

TRIBUTYLTIN OXIDE

0.015 6.4

0.045 7.4

Stoddard solvent

7.90 7.0

AWPA P9 (heavy petroleum) 3% 8.00 20.8

AWPA P9 (heavy petroleum) 6% 8.00 24.0

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Cu Nap retention and depletion values are based on Cu Content

Figure 1. Comparative decay ratings of Cu-Nap and Penta treated Stakes using different

carrier oils and exposed at Dorman MS. for a year.

Creosote-penta solutions were evaluated by many workers and were shown to have

superior wood preserving properties. In 1950’s utility companies used creosote that

contains about 2% w/w penta but, experience showed that the solution was highly

corrosive to storage and pressure vessels, piping, and pumps. Corrosion inhibitors such as

orthophosphoric acid and cathodic protection systems showed no significant improvement.

Removing tar base impurities from creosote prior to preparation of the formulation by

washing with a mineral acid (30% sulfuric acid) or extraction with monopyridinium sulfate

reduced corrosivity to about 15-20% of that of conventional creo-penta solutions (Albright

and Leach 1971). The formulation is not commercially used anymore.

FACTORS AFFECTING PERFORMANCE OF PENTA

Factors affecting the performance of penta in treated wood include, conditioning method,

solvent type (carrier solvent), amount of oil in solvent, presence of co-biocide, soil type and

soil chemistry of site of installation of the treated wood.

Effect of Carrier Solvent on Penta Performance

The importance of the carrier on performance of penta is well documented (DeGroot 1984,

Nicholas 1988, Nicholas et al. 1994, Lowrimore 1994 and most recently by Nicholas and

Freeman (2000 and Crawford et al., 2000). The influence of carrier oil properties on the

performance of wood preservatives serves as the basis for the AWPA P9-A. In this

standard physical property such as viscosity, specific gravity, penta solvency and

15

distillation range of the carrier oils must meet specified criteria in order to be acceptable

because they influence the plant operation and performance of the treated wood.

In a comprehensive review of stake tests installed in 1938 (Crawford et al., 2000) showed

that in stakes treated with penta at similar retention, better performance is obtained with

solvents containing heavy solvents such as heavy gas oil, lube oil extract, No. 4 aromatic

oil, and AWPA P9 heavy petroleum solvent than with volatile LPG or light oils such as

Stoddard solvent (mineral spirits). Table 5 shows results of average service life of penta

treated stakes in Mississippi and Louisiana. Tributyltin oxide and copper-8-quinolinolate

also show better performance with the heavy petroleum solvent than the light oils as

shown in Table 2.

Carrier solvent affects penetration and permanency of the preservative in wood and affects

biocide depletion rate. With regard to performance, the major factor is the effect of the

carrier on depletion rate of the biocide. In penta-mineral spirits treatments without stable

auxillary solvents, washing, vaporization and leaching could cause soft rot organisms and

basidiomycetes to penetrate deeper (Arsenault 1973). Increasing penta solvency in the

carrier oil results in a trend of improved decay resistance and less loss of penta by

volatilization (Arsenault 1973). Oils with higher distillation temperatures, higher viscosity,

higher surface tensions, and higher aromaticity perform better. The effectiveness of oil

carriers is positively correlated with boiling point and average molecular weight.

(Lowrimore 1994). Higher boiling petroleums retard but do not prevent decay. A solvent

with lower volatility is expected to provide an advantage in allowing a longer time for

penetration following treatment and in suppressing loss of a volatile preservative (Highley

et al., 1993). Table 5 is a summary of average service lives of penta stakes in various

solvents in Mississippi and Louisiana test sites from the review by Crawford et al (2000).

Inherent toxicity of the carrier oil to decay organisms influences the performance of the

preservative. Aromatic oils are more toxic than paraffinic oils and aromatic content may

make a difference in service life of treated wood. Lowrimore (1994) separated three P9-A

petroleum solvents (California shell oil, Ashland oil and Base oil L) into four fractions each

16

(saturates, neutral polycyclic, aromatics, bases and acids) by adsorption chromatography

and tested each fraction against decay fungi. California oil the most viscous had the

highest proportion to remain above 500oF. The first fraction to elute in all three carriers

was composed of saturated aliphatics and constituted more than 87% of each oil It

exhibited no appreciable fungitoxic properties.

Table 5. Condition of stakes pressure treated with penta in various petroleum oils 50

years after treatment in Mississippi (Saucier) and Louisiana (Bogalusa).

Oil or preservative Location Retentio

n

Ib/ft3

Total (%) stakes

removed after 50 years

Average life

(years)

MS 4.0 100 13.7 5% penta in Stoddard solvent

(mineral spirits). LA 4.0 100 8.8

MS 4.0 100 14.9 5% penta in fuel oil

LA 3.8 80 12.5

MS 4.0 100 14.0 5% penta in Heavy thermal side

out LA 4.0 100 10.6

MS 4.1 100 17.0 5% penta in Diesel oil

LA 4.1 50 >50

MS 4.2 100 16.3 5% penta in catalytic gas-base oil

LA 4.1 12 >50

MS 4.0 100 14.6 5% penta in No. 300 fuel oil

LA 4.1 37 -

MS 4.2 100 13.9 5% penta in No. 400 fuel oil

LA 4.2 78 12.5

MS 4.0 100 15.6 5% penta in light gas oil

LA 4.2 50 >50

MS 4.1 89 >50 5% penta in heavy gas oil

LA 4.1 - -

Untreated controls MS - 100 2.2

LA - 100 2.8

17

The second fraction (benzene eluted) was of moderate yield (7.4, 12.6 and 16.7% for

California shell, Ashland, and base oil L respectively) and contained neutral polycyclic

aromatics. This was the only fraction that reached a toxic threshold for inhibiting decay

fungi. Yields of the third and forth fractions were relatively minor and played no role in

inhibiting fungi. Overall performance of the oils were Base oil L> Ashland>>California shell.

California shell gave the poorest performance most likely because it contained the least

amount of the second fraction. Elemental analyses showed all oils were similar in carbon,

hydrogen and oxygen but differ in nitrogen and sulfur content. Sulfur has fungicidal activity

in elemental and organic forms and fungi utilize nitrogen as a food source. Base oil and

Ashland oil contain higher levels of sulfur and undetectable levels of nitrogen, another

explanation why the performance of Base oil L> Ashland>>California shell.

In the data in Figure 2 Nicholas and Freeman (2000) show the toxic threshold values (pcf)

for 8 oil types based on a pure culture basidiomyce test. Base oil gave the best

performance in this data too with the lowest threshold values of 1.7pcf against T. versicolor

and 4.2 pcf against G. trabeum.

Figure 2. Approximate Toxic Threshold Values (pcf) of Several Oils Exposed To Fungi In A Soil-Block

Test

Nicholas and Freeman (2000) report on a more recent study of the three carrier oils;

California Shell oil, Base oil L (Lillyblad Petroleum Inc), Ashland oil (Ashland Petroleum).

They also included 17% No. 2 Diesel Oil + 2% KB3 + 1% B11 (KB3 & B11 from Eastman

Chemical Products). All oils were diluted with toluene (20% oil and 80% toluene) and used

in a soil block test using SYP sapwood against brown-rot Gloeophyllum trabeum and

white-rot Trametes versicolor. Field stakes (AWPA E 7) were installed in Dorman Lake,

MS and Saucier, MS. Wood treated with the oil carriers alone initially performed

18

reasonably well against both wood decay fungi and termites, but the activity decreased

rapidly after about six years exposure. Each oil performed differently. The data in Figures 3

and 4 demonstrate that the carrier oils provided some degree of protection. At Dorman

Ashland oil had the worst performance. After the 6th year California Shell Oil had better

performance most likely because a previous study Lowrimore (1994) showed that it is the

most viscous, has the highest proportion to remain above 500oF increasing its

permanence in wood.

Figure 3. Average decay ratings-Stakes treated with

Carrier oils after exposure at Dorman.

Figure 4. Average decay ratings- Stakes treated with

Carrier oils after exposure at Saucier

Barnes et al (2007) analyzed stubs treated with penta in seven oil types labeled A to G

(Table 6) and set at a depth of 30-inches in a test plot set in DeQueen, Arkansas in 1960.

Periodically, the pole stubs were pulled, evaluated for decay and termite attack (Figure 5)

and bored for preservative assay. Steamed posts performed better than air-dried material,

presumably due to the sterilization effects of pre-treatment steaming. Type D with the

lowest aromatic fraction, gave the poorest performance irrespective of conditioning

method. Oils A and B exhibited the best performance and both had high aromatic content.

The paraffinic fraction apparently had no effect on performance.

Table 6. Composition and characteristics of treating solutions used.

Oil A B C D E F G

Composition & Properties (% by vol)

19

Aromatic light fraction 100 90 75 20 --- --- ---

Aromatic heavy fraction --- 10 25 --- --- --- ---

Paraffinic light fraction --- --- --- 80 60 100 ---

Paraffinic heavy fraction --- --- --- --- 40 --- ---

Waxy petroleum fraction with high pour

point

--- --- --- --- --- --- 100

Treating solution concentration (% w/w) 4.99 4.90 4.86 4.86 4.86 5.38 5.02

Specific gravity, oil only @ 60° F 0.982 0.982 0.965 0.882 0.881 0.863 0.908

Penta solvency, max @ RT (% w/w) 14 13 10 8.2 5.3 7.8 13.8

Figure 5. Effect of treatment solution

The penetration properties of penta and creosote oil-borne wood preservatives are

improved by adding 15-16.6% N,N-dimethylamide acid (DMA) at 100-5,000ppm of

preservative as part of the formulation (Johnston 1980). Suitable N,N-dimethylamides of

straight chain carboxylic acids are those prepared from acids containing 18 carbon atoms

and having at least one carbon to carbon double bond. Acids within this category include:

linoleic, linolenic, oleic, ricinoleic or mixed acids. Adding DMA decreases time required to

obtain adequate preservative penetration, results in less treating time and increase in

overall plant efficiency (Johnston 1980).

Comparing Oil borne and Water borne penta formulations

Due to continual increase in petroleum costs and possible reduced availability of petroleum

in the future there is need to find treating processes that keep the industry competitive and

profitable. (Hatcher 1980) presents results of laboratory tests on Dura-Treet II which is

penta dissolved in a mixture of hydrocarbon and co-solvents and a concentrate of this

20

dispersed in water at submicron levels. The dispersion is stable for months, penetrates

southern pine readily and penetrates Douglas fir as well as petro-penta. The clean

treatment reduced usage of hydrocarbon by 85% and resulted in a lighter finished product

than petro-penta. There were little or no difference in leaching rates, efficacy, point of

deposition of penta in the cellwalls, and wood strength properties when compared to petro-

penta. Dura-Treet II was found less corrosive than petro-penta and plant scale tests and

commercial usage showed it to be viable and efficient. These plus the economics of a

water carrier with potential energy savings, requiring no kiln drying indicated a system that

contributes to maintaining a strong, competitive wood preserving industry. Table 7 shows

the lowest retentions that prevented decay for each combination of carrier and test

organism (Hatcher 1980).

Table 7. The lowest retentions that prevented decay in Petro-penta and Dura-Treet II

G. trabeum P.monticola

Petro-penta treatment Ibs. Penta/ft3 0.330 0.330

Dura-Treet II Ibs. Penta/ft3 0.345 0.345

However, stakes treated with the water-dispersible penta formulation received

progressively lower scores for both termite attack and decay than stakes with comparable

retentions of oil-borne penta. A study reported in the review by Crawford et al (2000),

shows that water dispersible penta at a retention of 0.37Ib/ft3 gave a similar performance

as penta P9 in mineral spirits at a much lower retention of 0.09Ib/ft3 with 80% of the stakes

destroyed by termites or decay attack in the Mississippi test plot. When poles were treated

at a retention of 0.18 Ib/ft3 for both formulations, the water based formulation had 67% of

the stakes with decay and termite attack at 20years while penta P9 in mineral spirits had

only 20% stakes destroyed. In the same study while untreated controls had an average

service life of 2.3 years, penta in water and ammonia gave only 4.2 years and 9.7 years at

retentions of 0.13Ib/ft3 and 0.40Ib/ft3 respectively. Penta in P9 oil and toluene at 0.16Ib/ft3

gave a service life of over 12 years, (60% destroyed by termite and fungi), ammonium

penta at the same retention gave only 2.7 years with 88% of stakes destroyed. Penta in

21

amine water had an average service life of only 5.4 years (67% stakes destroyed) at

0.57Ib/ft3 retention compared to untreated controls at 1.1 years and over 12 years (less

than 10% destroyed) for penta in P9 oil and toluene (Crawford et al., 2000).

Decay starts earlier in stakes treated with water dispersible penta than in those treated to

comparable retentions of oil-borne penta. Termite attack was less severe but the general

pattern of better performance by oil-borne penta parallels the pattern of decay. A

significant distribution gradient exists for penta in wood treated with water-dispersible

formulations. Significantly higher retentions were detected in the outer 0.3 in. than in more

central portions of stakes treated with water-dispersible penta (DeGroot 1984).

Performance of penta is influenced by the gradient of preservative in wood. If retentions at

the exterior are lower than retentions in the internal regions, the internal reservoir of

preservative reduces the rate at which decay fungi move into the wood. With retentions

greatest at the surface, decay fungi, once they have colonized the periphery can progress

internally at a constant or increasing rate (DeGroot 1984).

Comparing Oil borne and penta in LPG formulations

The use of penta came under scrutiny because of early failures with Cellon® treated (penta

in LPG) poles. Several coastal utilities removed penta from their specifications and now the

commercial process using penta/LPG is no longer used due to inferior performance. The

data in Table 8 is from a test site at Saucier, Mississippi from the comprehensive review by

(Crawford et al., 2000). While stakes treated with heavy petroleum were still in service at

38 years, those treated with penta in LPG or paraffin failed below 20 years.

Table 8. Average service life Southern pine stakes assessed after 38 years of

service.

Oil or preservative Retention Ib/in3 Average life (years)

0.14 18.9

0.19 15.9

Penta in LPG

0.34 -*

0.14 -* 3.5% Penta in AWPA P9 Heavy

petroleum 0.22 -*

22

0.14 13.7 4% Penta in paraffin and pentalyn H

0.18 15.9

Untreated controls - 2.1

* Still in service after 38 years.

Effect of Soil chemistry on Penta Performance

Test site is important when evaluating systems. In the test reported by Nicholas and

Freeman (2000) in Mississippi, the performance of both penta and CuNap treated wood

was slightly lower at the Saucier test site. Average temperature and rainfall at the Saucier

site is higher and the soil at Dorman is silty clay loam, whereas the soil at Saucier is a

loamy sand type with good drainage. These differences resulted in higher biocide and

carrier oil depletion rates at Saucier. Soil pH has more impact on performance. A study

done in 1963 and cited by Wang et al (1998) shows that penta is leachable from alkaline

aqueous solutions or soils due to the formation of soluble penta salts. There is a good

relationship between Ca and Fe content of the soil and penta depletion (Wang et al 1998).

Sites with high Ca and alkalinity lead to greater depletion of penta from wood. Barnes et

al., (2003) compares data from matched stakes in a test site Harrison Forest (Florida)) with

that at Galveston (Texas Gulf Coast) in Figure 6 Both coastal sites are located in AWPA

Hazard Zone 5, the most severe zone.

Figure 6. Dose response curves for matched stakes treated with PCP after 5 years of

exposure in Galveston (TX) and Gainsville (Barnes et al 2003).

The Galveston site is much more severe for decay. Galveston is less than a half mile from

the coast is subject to inundation by sea water and is surrounded by sea shells used in

23

road beds and the site adjacent to the test plot has a high Ca content causing penta in

wood to convert to salt form either as calcium or sodium pentachlorophenate leachable

salts resulting in higher depletion rates. In contrast, the HF site is 20 miles from the Gulf

coast and has a sandy loam soil not subject to salt water incursion (Barnes et al., 2003).

Groundline depletion rate over five years for the TX site was 21% higher than the rate

found in the HF plot. Surface softening and superficial attack of cellon treated wood has

been attributed to soft rot in wet locations and moist soils when penta reaches below

threshold retentions in the outer annual ring (Arsenault 1973).

Effect of Solvent Oil content on Penta Performance

Increasing oil content in the solvent carrier has a positive effect on the efficacy of penta.

Barnes et al. (2003) details a five-year stake test on SYP treated with penta in a P9-A

solvent blend of No. 2 fuel oil (90%) and a still bottom ketone co-solvent KB3 (10%) oil at

various contents and installed in two Gulf Coast sites, Saucier, MS on the Gulf Coast and

Galveston, TX. Solution strength was adjusted with toluene to desired retention and target

oil content of 64, 96, 128, and 160 kg/m3. In Galveston, increases in performance with

increasing oil content were observed across all penta retentions with the effect lessening

at the higher retentions. The depletion of penta decreased with oil content for the first two

years of exposure, leveled off in year 3 and increased with increasing oil content in years 4

and 5. The impact of oil content was more critical for the Galveston plot.

Effect of Wood Species and Fungal Species on Penta Performance

Differences in performance of penta between species may be partly explained by the

magnitude of adhesion of the oily preservative to wood. In hardwoods bordered pits, and

tyloses hold oil in vessels helping retain it in wood. The narrow lumens in fibers retain

liquids better resisting internal pressure and gravitational forces that encourage migration

(Arsenault 1973).

Early soft rot attack on cellon treated poles is associated with the depletion of penta to

below threshold retentions in the outer fibres (outer annual ring). Soft rots generally

penetrate wood with the fungal hyphae lying within the thickness of the secondary walls of

24

the longitudinal wood elements. Since oil solutions do not penetrate the cellwall,

prevention of soft rot attack by oil borne preservatives must depend on high surface

concentrations of preservatives, vapor pressures of preservatives and water insolubility.

Mechanical washing, vaporization, and leaching could cause early failure in such

treatments.

Mineral solvents result in cellwall penta treatments which stabilize the preservatives so that

mechanical washing, leaching and vaporization are minimized. Thus swelling type co-

solvents such as methyl alcohol, result in better service life than isopropyl ether co-solvent.

In pine efficacy was improved with penta in a swelling system against white rot Polystictus

versicolor, but with brown rot Coniophora cerebella and soft rot Chaetomium globosum,

the swelling solvent system with penta and CuNap showed no advantage. Inhibition of

white rot would be more effective by swelling–type penta solvents systems because the

susceptible lignin deep in the cellwall would be in intimate association with the

preservative. Brown rot would be expected to attack the cellulose near the surface of the

cellwall (Arsenault 1973). Another study showed that only wood treated in the green state

with swelling agents exhibited cellwall impregnation. In the dry state the wood did not

exhibit swelling. Small amounts of water added to the swelling type solvents, increase their

ability to enter the cellwall because the water acts as the opening wedge in preceding the

larger molecular size solvent into the cellulose matrix through hydrogen and diffusion.

Swelling results in more uniform retentions and distribution (Arsenault 1973).

DISTRIBUTION OF PENTA IN WOOD

Distribution of penta in wood is affected by method of seasoning and moisture content at

the time of treatment. Redistribution of petro-penta occurs when wood is placed in service.

Vertical poles have migration of oil solution towards the groundline. Changes also take

place when poles are held in horizontal storage due to gravity. Excessive migration and

redistribution can be detrimental to service life if it depletes the above ground portion of

poles and upper surface. There is a difference in penta distribution based on seasoning

method. The drying of inner sapwood of wood treated green, creates a negative pressure

which draws in the preservative oil, preventing its outward migration as is the case of air

25

seasoned stubs where a positive residual internal pressure remains in the cells. There is

tendency for creosote and petro-penta to move from the outer zones inward with time

causing the inner sapwood to become fortified by preservative. Gains in penta retentions

have been found at radial depths 1-2 inches in pine pole stubs treated green, but losses of

penta were at all radial depths for poles air seasoned before treatment (Arsenault 1973).

This fortification is absent in the case of volatile solvents that evaporate rapidly during air

drying and redistribute the preservative to the outer zone. When xylene was used as

solvent, one month after treatment a penta xylene solution distributed the preservative by

moving outward to the outer zone and only 79% of the penta found immediately after

treatment was still present after one month. In dry unswollen wood the problem is

compounded by additional barriers such as aspirated pits, rigidity of the pit membrane, or

plugging by extractives.

Penetration, location, and retention of preservatives in cellwalls influences efficacy

(DeGroot and Kuster 1984). The extent to which penta penetrates cellwalls during

pressure treatments is markedly influenced by the carrier solvent (DeGroot and Kuster

1984). Penta in oil solutions generally coat, but do not enter cellwalls. SEM/EDXA analysis

has shown that penta is deposited within cellwalls of SYP sapwood pressure treated either

with water-dispersible penta or with penta in hydrocarbon solvent diluted with mineral

spirits. More penta enters and more uniformly penetrates cellwalls with water-dispersible

penta than with oilborne penta diluted with mineral spirits. When penta is dissolved in LPG

plus a co-solvent, it penetrates the S3 and S2 layers of the cellwalls.

The distribution pattern of water-dispersible penta was significantly affected by anatomical

characteristics of earlywood and latewood and by retention levels. Earlywood consistently

had more penta than latewood. Levels of penta in the S3 layer of tracheid cellwalls

approximate a proportional relationship with gross retention. In the S2 layers especially in

the latewood, there is relatively little gain in penta with increments of gross retention above

0.43 pcf. Thus, additional protection through increased retentions of these treatments

would come from the envelope of penta on the lumen walls and lining all the pathways

26

through which preservative is forced during the treating process (DeGroot and Kuster

1984).

Studies on location of penta in Cellon treated Douglas fir showed no crystalline penta in

the wood but found evidence of incrustations in the cellwalls, suggesting that penta may be

associated with wood extractives in a complex. Thus stabilization of penta is time

dependent and an aging effect is evident with aged wood releasing less penta than newly

treated wood. Adsorption by lignin and diffusion into the cellwalls are possible mechanisms

of stabilization. Wood that has been aged three years released only 50-60% penta upon

benzene exraction, but newly treated wood released 97%. Lignin has a strong affinity for

phenolic substances by hydrogen bonding. Penta bound to the cellwall associated with

lignin would be more resistant to depletion from mechanical depletion, leaching and

vaporization than penta in the lumens.

BLEEDING AND DEPLETION

Both vapor loss and liquid preservative loss represent depletion. In poles treated by the

cellon process, to 0.3-0.5 pcf retention, depletion of penta is significant only in the outer ½

inch zone of the pole. Little or no depletion occurs in underlying zones, presumably

because there is no oil present to promote diffusion or capillary migration.

Volatilization and leaching in oil borne penta may be simultaneous in the groundline region

and also increases with permeability of the wood and original retention. Unrealistically high

retentions result in excessive bleeding, excessive migration and preservative loss.

Aromatic oils bleed less than paraffinic oils of the same boiling range and viscosity.

Bleeding is objectionable where cleanliness is a requirement, however in railroad ties high

retentions are required and the resultant coating from bleeding adds to the surface life by

holding the oil in the wood, repels water, and prevents checking and top shattering. The

residue may also trap air in the poles in a manner similar to the aspirated pits. Mold and

fungal attack during air seasoning may increase depletion of penta-oil after treatment due

to increased permeability of the wood resulting in increased liquid and gas flow inward and

promoting bleeding and loss of preservative.

27

As both viscosity and the surface tension of carrier oil increases, the critical non bleeding

retention also increases and bleeding decreases because capillary movement is slowed

down. Bleeding is also affected by annual rings; wider annual rings result in less bleeding.

The greater the volume of latewood, the higher the retention and the greater the bleeding.

Bleeding decreses with increase in sapwood thickness. Narrow sapwood will bleed more

because the surface retentions are higher. Removal of the outer layer of wood by machine

peeling cuts the tracheids, removes accumulated resins and exposes a greater proportion

of early wood which bleed less than latewood.

Bleeding is due to migration of preservative downward and outward and is affected by

seasoning condition at time of treatment. The literature on oil borne penta and creosote

solutions from wood shows that poles treated after air seasoned poles and posts bleed

more and have more oil borne preservative loss than green steam-conditioned ones.

Wood that is treated green dries after treatment causing a negative pressure which draws

the oil deeper into the wood and reduces the tendency to bleed. During normal drying, pit

aspiration drastically reduces permeability. If wood is treated before pits aspirate, the

preservative deposits in and around the pit membranes reducing adhesion and preventing

complete pit aspiration. If pits are aspirated during treatment, kickback after pressure

release in an empty cell treatment causes preservative to be trapped by the aspirated pits

seep within the wood.

Poles treated after air seasoning suffer more penta-oil and creosote vapor loss than poles

treated green and likewise have more migration of oil downward and outward, while green-

treated poles have movement inward. Interfacial tension of the treating solution is lower in

green wood than seasoned wood because components of sap act as wetting agents.

Going from the outer toward the inner zone of a pole section, vapor loss decreases more

rapidly for green pole sections than for seasoned poles. Eight year data on penta depletion

shows that initial MC has a more profound effect on penta loss than oil properties (Table

9). Overall penta loss for air seasoned wood was 0.07 pcf for all zones assayed while,

comparable average loss from green steam conditioned poles was 0.03pcf. In the outer

28

one inch zone loss was 0.256 pcf for air seasoned and 0.187 for green steamed poles.

These is very similar to results in creosote poles (Arsenault 1973). From Table 9 the

apparent good performance of oil 6 in the air seasoned group may be attributed to high

MC. Poor performance by oil 4 and 7 may be related to low MC. In kiln drying loss of

permeability due to pit aspiration can be controlled by pre-steaming before kiln drying.

Steaming green poles reduces strength of the pit membranes by hydrolysis decreasing

tendency to aspirate. Steaming softens wood resins causing viscosity increase and

stabilizes the oil from migrating. Bleeding can be a problem in kiln dries poles just as in air

seasoned poles.

Table 9 . Penta loses (by lime ignition assay) for the outer inch of SYP in pcf for 140 pole

size stubs in a 97-month exposure period in Arkansas

Green steamed Air seasoned

Treating

solution

Average MC

(%)

Penta losss

(pcf)

Average MC (%) Penta losss (pcf) Average

penta loss

1 84 0.172 24 0.209 0.190

2 98 0.186 30 0.261 0.223

3 68 0.113 30 0.277 0.195

4 83 0.264 15 0.269 0.267

5 72 0.198 31 0.273 0.235

6 76 0.155 42 0.195 0.176

7 83 0.224 9 0.309 0.267

Final steaming of wood reduces bleeding, cleans up, or recovers solvent. Excessive final

steaming can distill penta from the outer fibres or force expansion of the oil in the outer

fibres and lower the gradient about 16%. 1-2 hour final steam periods at 240oC will not

lower the gradient significantly. Vapor drying with light petroleum has been used for

crossties and poles. Penetration of vapor-dried poles is improved over green conditioned

poles but the retention distribution is lower in the outer zone. This reduces tendency to

bleed but lowers retention at the fungus front. Migration of penta in wood treated with

volatile carriers after the carrier has left wood does not occur. The penta deposited is not

subject to loss by migration outward or gravitational movement downward although there is

some volatilization and leaching near the surface (Arsenault 1973).

29

Ingram et al., (1983) evaluated the efficacy of coatings in suppressing vaporization of

penta specimens of SYP treated with penta in mineral spirits (dip treatment), penta in P9

type A oil and penta in methylene chloride (pressure treatments). Clear film-forming

coatings polyurethane and alkyds, were greater than 90% effective for specimens dip

treated with penta in mineral spirits. Two-component (epoxy type) pigmented coatings

were effective on specimens treated with penta in P9 type A oil. Coatings compatible with

the oil in specimens with penta in P9 type A oil were effective. A bituminous coating and a

two-component epoxy paint were the most effective coatings found for reducing penta

vaporization from treated wood (Ingram et al., 1983).

ANALYSIS OF PCP IN TREATED WOOD.

In the past two decades, the use of x-ray fluorescence spectroscopy (XRF) for the

determination of chlorine for analysis of penta has become commonplace. However some

treating plants and inspection agencies still use the older Volhard chloride (lime ignition)

method (AWPA 2006). As part of a study on the effect of oil composition on the durability

of penta-treated wood, pole stubs from a forty-year-old exposure in an AWPA Hazard

Zones 3-4 (DeQueen, Arkansas installed in 1960 and decommissioned in 2000) were

analyzed for preservative content using both methods. A linear regression of lime ignition

values (LI) vs. XRF values was established for each of the seven oil carriers and for all oils

combined. The best coefficient of determination (R2) was for Oil B with a composition of

90% aromatic light fraction + 10% aromatic heavy fraction. The oil with the worst fit with an

R2 of 91% was the 80/20 mix of paraffinic light fraction to aromatic light fraction. When the

data for all oils were combined, an R2 of almost 98% was obtained. This extremely good fit

to the data over a range of oils with widely varying properties is an assurance of the

validity of XRF analysis for quality control and other purposes (Barnes et al., 2007).

Bioassays using the fungus Aspergillus niger have been shown to respond to penta and

indicated a good relationship between the amount of retained preservative in the wood and

the circular area free from sporulated mycelium around preserved specimens, observed on

agar substrate (Moreschi 1982). Penta specimens reveal an excellent correlation

coefficient between mycelia growth and preservative content. The species does not

30

respond to CCA in the same manner. Aspergillus niger as considered the most appropriate

species for this purpose because its fast growth and symmetry of the TZE presents a

reasonably accurate and easy approach to estimate amount of penta in treated wood

(Moreschi 1982).

Capillary gas chromatography method with electron capture detection is another widely

applied method of assaying penta (usually methylated or acetylated) after acid extraction

to diethyl ether. The detection limit is 0.005–0.01 �g/litre. Other methods include gas

chromatography with atomic emission detection, GC-MS using selected ion monitoring and

HPLC (WHO 1997).

CHLORODIOXINS IN PENTA AND THEIR EFFECT ON TOXICITY

Humans are generally exposed to technical-grade penta which usually contains toxic

impurities such as polychlorinated dibenzo-p-dioxins and dibenzofurans. Because of trace

impurities produced during the penta manufacturing process, the use of penta has been

subject to intense regulatory scrutiny (Wilkinson 1995). Dickson (1980) reports a study on

three groups of heifers separately given feed containing analytical penta prepared in the

lab, technical penta containing dibenzodioxin and dibenzofuran contaminants and feed

containing the mixture. Results indicated dose related effects to contaminated penta

compared to those exposed to analytical penta. Toxic effects attributed to penta were

actually due to the impurities. Some of the effects observed in humans (or the severity and

dose-response characteristics of effects) may be related to the impurities.

Alliot (1975) showed that penta does not contain 2, 3, 7, 8 TCDD the most toxic and

dangerous chlorodioxin. TCDD is tetarogenic and embryotoxic at very low doses.

Chlorodioxins that might be found in penta are OCDD at 3-1000ppm representing the most

abundant impurity. OCDD is practically non-toxic at the doses at which it is found in penta.

A small proportion of HxCDD (1-100ppm) is found in penta but it is 1,000-10,000 times

less toxic and less teratogenic than TCDD. DCDD and OCDD are not very toxic, have no

teratogenic, embryotoxic or acnegenic action and can therefore be considered as being of

no danger even at highest proportions which have been found in certain penta samples

31

(Alliot (1975). The acute toxicity of HxCDD is nearly the same as that of penta, hence this

is the impurity that most influences penta health effects. In the 1970’s Dow Chemical

company introduced a preservative, Dowicie EC7 in which dioxin levels had been reduced

two orders of magnitude using more expensive production techniques but the product was

uncompetitive against rival non-decontaminated brands (Dickson 1980).

EPA RE-REGISTRATION AND REGULATIONS FOR PENTA

Regulations on penta such as pure ban in certain countries have been triggered by various

events such as emotional and political pressures to provide satisfaction to pressure

groups. An enormous amount of work has been carried out in many countries on penta

and its derivatives (Ozanne 1995). The increased knowledge of the toxicology of penta has

contributed to penta being the most documented substance in wood preservation.

Regulations only based on intrinsic properties of substances, may appear totally blind. The

risk/benefit approach applied to penta has involved specifications on impurities,

classification of the dangers, identification of the most suitable form to minimize the risk,

voluntary limitations of use for sensitive applications, rules of destruction and finally a

standard of specifications socially acceptable worldwide (Ozanne 1995).

In 1978, the US-EPA instituted a regulatory proceeding that considered cancellation of all

penta pesticide registrations but, after extensive review, declined to take such action.

Instead in 1986, EPA limited the HxCDD levels to no more 2 ppm and 1ppb TCDD for all

batches shipped per month. Additional mearsures to ensure penta in wood preservation

would not cause risks to the public or environments were enforced (Wilkinson 1995). The

Canadian Government adopted an identical regulatory program. Since then a number of

new studies have further confirmed that penta can be safely and responsibly used for

wood preservation. The US. Penta taskforce organized in 1988 was in response to the

FIFRA act that required registrants of older pesticides to develop certain data on their

products. In 2005 the three heavy duty wood preservatives (penta, CCA, and creosote)

underwent the re-registration process. Re-registration involves a thorough review of the

scientific database of a pesticide and additional information received through the public

docket before a Reregistration Eligibility Decision (RED) is published containing the risk

32

assessment and regulatory decision (Elkassabany 2005). The process ensures that older

pesticides meet current standards for health and environmental risks based on existing

labels and uses.

In 2008, the EPA completed the human health and environmental risk assessments for

penta. The review for penta determined that the pesticide meets the ‘no unreasonable

adverse effects’ criteria of FIFRA and that the data and information available was sufficient

to support re-registration for the professional use as wood preservative. EPA required that

risk mitigation measures be implemented, label amendments made and data gaps and

confirmatory data requirements satisfied. Safe design and operation of timber treatment

plants minimizes release into the environment. Use in wood preservation did not pose an

unacceptable risk to man or the environment because of the contained exposure

(Fitzpatrick and Mackie 1995). EPA determined that such use will not present risks

inconsistent with FIFRA and that the economic and societal benefits of penta to society

outweigh risks. Eliminating these uses could result in reliance on products with greater

safety risks, reduced effectiveness and higher costs that could be passed on to the general

public. The appropriate mechanism for addressing penta concerns is not to ban the

important uses, but to ensure that those uses are properly managed to minimize

exposures (Ozanne 1995).

Other sources of Penta and its contaminants in the Environment

Current releases of penta are limited, as indicated by the Toxics Release Inventory (TRI).

Levels of penta in environmental media have decreased. Laboratory studies on penta in

wood have shown that OCDD, HpCDD and HxCDD are formed when wood is irradiated or

exposed to sunlight. Formation of OCDD is reduced when hydrocarbon oil was utilized as

the carrier solvent in place of methylene chloride. Other environmental contaminants,

including chlorobenzenes, pentachloronitrobenzene, and hexachlorocyclohexane isomers, are

known to be metabolized to penta.

Penta is released into the atmosphere via volatilization from treated wood and can be

transported back to surface waters and soils via wet and dry deposition. Chemicals with a

log Kow value greater than 4.0 are likely to bioaccumulate in organisms and food chains.

33

The log Kow for penta is 5.01. Bioaccumulation of penta in in the food chains has been

demonstrated. Penta is readily and completely absorbed following inhalation, oral and

dermal exposure.

Summary and Conclusions

Penta remains a very viable wood preservative today. It continues to be the favored wood

preservative for wooden poles in the USA and in N. America. Its recent re-registration by

the US EPA has recently been completed. Penta provides long service life for properly

treated, preserved and quality controlled wooden items, especially for the utility industry.

34

References Albright, D.M and Leach, C.W. 1971. Penta-creosote wood-preservative. US. Patent 3930025.

Alliot, H. 1975. Chlorodioxins in penta. Int. Res. Group on Wood Protection. IRG/WP 346 E.

Arsenault, R.D. 1973. Factors influencing the effectiveness of preservative systems. In: Wood Deterioration and its Prevention by Preservative Treatments. Vol. II. D.D. Nicholas, Ed. Syracuse Univ. Press. Syracuse, N.Y. pp. 121-278.

ATSDR. Agency for Toxic Substances and Disease Registry. 2001. Toxicological profile for Pentachlorophenol.

Barnes, H.M., Amburgey, T.L & Sanders, M.G . 2003. Effect of oil content on the performance of wood treated with pentachlorophenol.

Int. Res. Group on Wood Protection. IRG/WP 03-30324.

Barnes, H.M., McIntyre, C.M., Bullock, D. W., Freeman, M.H and Lindsey, G.B. 2007. Assaying Penta-treated Wood Using XRF. Int. Res. Group on Wood Protection. IRG/WP 07-20362.

Crawford, D.M., Woodward, B. M., Hatfield, C. A. 2000. Comparison of wood preservatives in stake tests. Progress Report. Res. Note FPL-RN-02. Davidson H. L. 1977. Comparison of Wood Preservatives In Mississippi Post Study. (1977 Progress Report). USDA. Forest Service. Research Note FPL-01. DeGroot, R.C. 1984. Water-Dispersible Penta: a preliminary report on field tests with Southern Pine Stakes. Proceedings, 1984 American Wood-Preservers' Association meeting. Pages 1-14. DeGroot, R.C. and Kuster, T. A. 1984. SEM-X-Ray Microanalysis of Pentachlorophenol in Tracheid Cell Walls of Southern Pine Sapwood. Holzforschung 38 (313-318).

Dickson, D. 1980. PCP dioxins found to pose health risks. Int. Res. Group on Wood Protection. IRG/WP 3152

Elkassabany, N. 2005. Wood Preservatives Science Issues: US EPA’s Perspective. Int. Res. Group on Wood Protection. IRG/WP 05-50224-2

EPA. 2008. Reregistration Eligibility Decision for Pentachlorophenol.

FAO 1996. Pentachlorophenol and its salts and esters. Operation of the prior informed consent procedure for banned or severely restricted chemicals in international trade. decision guidance documents. FAO/UNEP program.

35

Fitzpatrick, M. and Mackie, C. 1995. Pentachlorophenol, its salts and esters; UK review of its uses in wood preservation and surface biocides. Int. Res. Group on Wood Protection. IRG/WP 95-50040-27.

Fishel, F.M . 2005. Pesticide Toxicity Profile: Wood Treatment Pesticides. Publication #PI-92. opics: Pesticide Toxicity Profiles series.

Freeman, M.H., Crawford, D., Lebow, P and Brient, J.A 2005. A Comparison of Wood Preservatives in Posts in Southern Mississippi: Results from a half-Decade of Testing. American Wood Preservers' Association. Volme 101. pages 136-143. Hatcher, D.B. 1980. Dura-Treet II, A Water Dispersible pentachlorophenol. Int. Res. Group on Wood Protection. IRG/WP/80-3165.

Highley, T.L. and Scheffer, T.C. 1993. Thirty-four year test of on-site preservative treatments to control decay in wood above ground. Int. Res. Group on Wood Protection. IRG/WP 93-30015.

Ibach, R.E and Rowell, R.M. 1995. Low polymer levels containing bioactive monomer polymerized in situ provide resistance to Gloeophyllum trabeum. Int. Res. Group on Wood Protection. IRG/WP 95-30066.

Ingram, L. L., McGinnis, G. D., Pope, P. M., Feist, W. C. 1983. Effect of coating systems on the vaporization of pentachlorophenol from treated wood. American Wood-Preservers' Association. Proceedings of the 79th annual meeting. Stevensville, MD : 1983: pages 32-41.

Johnston, T. M. 1980. Oil-borne creosote and pentachlorophenol wood preservative compositions containing dimethylamide. United States Patent 4234665.

Johnstone, R.S. 1986. Pentachlorophenol and tributyltin oxide - the performance of treated Pinus radiata after 12 years' exposure. Int. Res. Group on Wood Protection. IRG/WP 3361

Johnson, G.C and Thornton, J.D. 2000. An Australian test of wood preservatives. IV. The condition, after 35 years’ exposure, of stakes treated with creosote oils and oilborne preservatives. Int. Res. Group on Wood Protection. IRG/WP 00-30241

Lowrimore J.T. 1994. The Physical, biological and chemical characteristics of wood preservative carrier oils. A dissertation. Mississipi State University.

McBain, A., Cui, F., Ruddick, J.N.R. 1993. The microbiological treatment of chlorophenolic preservative in spent utility poles. Int. Res. Group on Wood Protection. IRG/WP 93-50001-24

Moreschi, J.C. 1982. A bioassay to determine preservative retention in hardwoods and southern pines. Int. Res. Group on Wood Protection. IRG/WP 2183.

36

Nicholas, D.D and Freeman, F.H. 2000. Comparative performance of penta and copper naphthenate in a long term field stake test. Int. Res. Group on Wood Protection. IRG/WP 00-30243.

Ozanne, G. 1995. Pentachlorophenol: The non-emotional approach. Second draft: A discussion document. Int. Res. Group on Wood Protection. IRG/WP 95-50040-07. Pohleven, F. and Boh, B. 2007. The influence of pentachlorophenol on mycelial growth of wood decay fungi Trametes versicolor, Grifola frondosa, Hypoxylon fragiforme, and Coniophora puteana. Int. Res. Group on Wood Protection. IRG/WP 07- 30437.

Scheffer, T.C., Miller, D.J and Morell, J.J. 1997. After 18 years, preservative Dipping and Brush treating continue to provide protection to shingles of western wood species. Int. Res. Group on Wood Protection. IRG/WP 97-30156.

Wang H-H., Nicholas, D.D., Sites, L.S and Pettry, D.E. 1998. Effect of soil Chemistry and physical properties of Wood preservative leaching. Int. Res. Group on Wood Protection. IRG/WP/98-50111.

Wilkinson, J. 1995. Pentachlorophenol - The US and Canadian experience. Int. Res. Group on Wood Protection. IRG/WP 95-50040-26.

APPENDIX I

PROCEEDINGS

One Hundred First Annual Meeting

of the

AMERICAN WOOD-PRESERVERS’

ASSOCIATION

Royal Sonesta Hotel New Orleans, Louisiana

May 15-17, 2005

VOLUME 101

AMERICAN WOOD-PRESERVERS’ ASSOCIATION P.O. BOX 361784 BIRMINGHAM, ALABAMA 35236-1784 USA

ISSN 0066-1198 COPYRIGHT, 2005 BY AMERICAN WOOD-PRESERVERS’ ASSOCIATION

P.O. BOX 361784 BIRMINGHAM, ALABAMA 35236-1784

USA Rights to republish papers and reports published herein, in whole or in part, or by reference are granted to all persons, provided that reference to the authors and to the AWPA Proceedings are made. Statements made or opinions expressed in this publication shall not be the responsibility of the American Wood-Preservers' Association.

Colin McCown, Editor Pamela Leigh Wise, Assistant Editor

A Comparison of Wood Preservatives in Posts in Southern Mississippi: Results from A Half-Decade of Testing

Mike H. Freeman

Independent Wood Scientist

Douglas Crawford USDA Forest Products Lab

Patricia Lebow

USDA Forest Products Lab

James A. Brient Merichem

Abstract: Wood preservatives extend the useful service life of all wooden commodities used above ground and in ground contact. Over 50 years ago, the USDA-Forest Products Lab established tests in a high decay and high termite hazard zone in southern Mississippi. During the last five decades, periodic reports have been issued by researchers located at the USDA-FPL, in Madison, WI, on the efficacy and performance of southern pine fence posts treated with a variety of wood preservatives. Since 1977, no report has been issued by the USDA-FPL on the performance of these various preservatives in southern pine posts. This study was undertaken to evaluate the long-term efficacy of over 50 wood preservatives in southern pine wood in ground contact.

This study reassessed the condition of the treated wood posts in southern Mississippi, and statistically calculated the new expected post life span. It was determined that commercial wood preservatives, like pentachlorophenol in oil, creosote, and copper naphthenate in oil, provided excellent protection for posts, with life spans now calculated to exceed 60 years. Surprisingly, creosote and penta treated posts at 75% of the recommended AWPA retention, and Copper Naphthenate at 50% of the required AWPA retention, gave excellent performance in this AWPA Hazard Zone 5 site. Untreated southern pine posts lasted 2 years in this test site. Keywords: preservatives, posts, efficacy, performance, life span Introduction: The objective of the original study was to evaluate the efficacy and performance of over 100 wood preservatives and wood preservative systems in southern pine posts in a severe hazard site. The test site, in southern Mississippi in AWPA Hazard Zone 5 contains severe decay potential and severe termite exposure. The purpose of this evaluation was to evaluate the performance of the 50 remaining wood preservatives in test, and update the average service life expectancy data from the previously issued report, USDA FPL-01, from 1977.

Materials and Methods Southern Pine posts (SYP), with an average 4-5 inches in diameter, were air dried, and then were

treated with a variety of over 100 different preservative systems by Rueping or Lowry processes for the oil-borne or oil-type systems, or full cell for the water borne systems at the United States Dept. of Agriculture facility in Madison, WI. These resultant treated posts were shipped to the MSP test plot located in Harrison, MS and planted approximately one-third of their length in the soil.

After 53 years of exposure in southern Mississippi, posts were stressed to a possible failure point by the use of a 50 lb. (22.73 Kgm) pull test (see example photo in Figure 3). Many of the posts failed upon

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exposure to the stress load, and the data was tabulated for further statistical evaluation. Many treated posts had failed to the point of unable to hold their own weight after 53 years.

The data from the evaluation was statistically analyzed using a variety of techniques (including assuming a Wiebull lifetime distribution and calculating 90% confidence intervals at the 60th percentile) and the results illustrate typical life spans for many of the preservative treated pine posts. The typical treated and untreated pine posts life span as approximated by the 60th percentile can be seen in the Tables 2 and 3 and Figure 2.

Example of 50 lb Pull test

Results from 1977 Inspection and FPL-01 Progress Report

Figure 1. Predicted typical service life of treated and untreated southern pine posts as given by the estimated 60th percentile for each treatment group taken directly from FPL-01 1977 Progress Report. (Note: An error in this printed Table is that the penta concentration was at 0.5% in the treating solution, and it was actually 5.0% w/w).

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Results from 2003 Inspection Summary of Data from February Inspection of MSP 29 Published data has been reported on this plot as part of the 1977 Progress Report titled “Comparison

of Wood Preservatives in Mississippi Post Study” by U.S.D.A. Forest Service, Research Note FPL-01, July 1977.

This summary will include only the posts which are remaining after a subsequent inspection in 1990. Table 1 will show the percentage of posts remaining for each preservative and retention. The method

used to evaluate the posts is the one that uses the 50-lb load lateral pull test as prescribed in the Research Paper RMRS-RP17, “Service Life of Fence Posts Treated by Double-Diffusion Methods” by Donald C. Markstrom & Lee R. Gjovik. Table 1. Preservative, solution retention, posts remaining from plot MSP 29 and percentages of pass, fail and missing of those posts evaluated. 53 years of exposure %

Inspection February 17-2003

CHEMICAL RET. REMAINING After 1990

Fail Pass Missing

ACA 0.34 64 4 12 0 Boliden Salt B 0.7 68 1 14 2 Carbosota (C-T Creo) 6.00 80 8 12 0 CZA 0.7 84 3 17 1 CZC (Copperized) 0.98 20 0 4 1 CZC (F. R.) 3.25 48 4 8 0 CuNap .5%Cu in Pet 6.00 72 4 13 1 Creo Straight Run Low Res. 5.9 32 4 3 1 Creo Straight Run Med Res. 5.6 56 4 8 2 Creo Straight Run High Res. 6 72 2 16 0 Creo Med Res Low Tar Acid 5.7 84 7 13 1 Creo Med Res Low Naph 6.1 84 6 13 2 Creo Med Res Low Tar Acid/Nap 6 68 2 15 0 Creo Low Res Low Tar Acid/ Nap 6 52 5 8 0 Creo High Res Low Tar Acid/ Nap 6.1 100 1 24 0 Creo Med Res Low Frac. 235- 270 6.1 72 6 9 3 Creo High Res Crystals Removed 6 96 2 22 0 Creo Low Temp 6.3 60 3 11 1 Creo English Vert. Ret. 6.3 64 6 9 1 Creo English Coke Oven 6 48 6 5 1 Creo Eng Vert Ret 50%/Coke Oven 6 76 5 12 2 Creo Med Res w/2 1/2% Penta 6 92 2 21 0 Creo 70% & C-T 30% 6.1 84 5 16 0 Creo 50% & Petro. Oil #2 50% 5.9 24 5 1 0

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Creo 50% & Petro. Oil 50% 6 76 4 13 2 Creo 50% & Petr. Oil 50%/ 2 1/2% 6 92 0 23 0 Creosote, Oil Tar (Gasco) 5.9 40 3 6 1 GASCO In 2% PENTA 5.8 88 5 17 0 LIGNITE C-T CREOSOTE 6.3 16 3 1 0 Lignite CT Creo 50% & CT Creo 6.3 84 7 13 1 Lignite CT Creo 50% & Petro. Oil 6.4 24 5 1 0 Penta 5% in #2 Distillate 6.3 72 0 17 1 Penta 5% in #4 Aromatic Res. 5.9 96 1 21 2 Penta 3% In #4 Aromatic Res. 6 100 2 23 0 Penta 5% in Petroleum Oil 6 64 6 10 0 Penta 5% Cu Nap in Petro 6.2 96 2 21 1 Pertoleum Oil Aromatic High Res 6.1 60 6 7 2 Pertoleum Oil Aromatic Low Res 6.1 36 3 5 1 Petroleum Oil Highly Aromatic 6 4 1 0 0 Petroleum Oil High Aromatic Res 6.1 16 2 1 1 Petroleum Oil #2 Distillate 5.9 0 Petroleum Oil #4 Aromatic Res 5.9 24 1 4 1 Petroleum Oil Wyoming Res 5.8 0 PETROLEUM TERMITEOL 6.1 8 1 1 0 CONTROL 0 0

Statistical Analysis Analysis of the FPL-01 Post Series (1949 posts) Several statistical analyses were conducted on the pass/fail data, including the parametric analysis

described here. In estimating service life prior to 100% failure, it is noted that typical life is approximated by the time when 60% of the posts in a group have failed; this was assumed in prior reviews of this data and is referred to as the average service life. In prior reports, a mortality table was used for estimates of service life (the 60th percentile) when between ten percent and close to 100% (but not 100%) of the posts had failed. If 100% of the posts had failed, then a formulaic average was calculated. Unfortunately, since several posts were lost for known and unknown reasons (eg., tree falling on posts) throughout the course of this exposure period, use of a mortality curve based on percentage failed or a formulaic average does not incorporate knowledge that these posts had survived for at least a known period of time. If we can assume an underlying parametric distribution for service life, we can better accommodate the censoring process. For this analysis, we assumed Weibull distributions, whereby the typical service life is then predicted by estimating the 60th percentile.

Normal-approximation 90% confidence intervals on the 60th percentiles were calculated (Meeker and Escobar, 1998). Table 1 lists these statistics in alphabetical treatment order, while Table 2 and Figure 2 lists treatments in order of predicted typical service life (note this is the 60th percentile estimate and not the estimate of the average for the Weibull distribution).

Statistical calculations were made in SAS version 8.2 (SAS Institute Inc. 1999), while SPLUS version 6.1 (Insightful Corporation 2001) was used for graphing confidence intervals with dotplots. Note on several of the treatments, for graphing purposes, the upper limits of the confidence intervals were truncated. Please refer to Table 2 for the appropriate confidence interval values.

Further details will be available in a forth-coming Forest Products Lab report.

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Table 2. Predicted typical service life of treated and untreated southern pine posts as given by the estimated 60th percentile for each treatment group.

Treatment

Estimated 60th

Percentile Service Life

Estimated Standard

Error Asymptotic Normal 90%

Confidence Limits Lower Upper ACA 59.5 5.53 51.1 69.3

Boliden Salt B 73.1 9.29 59.4 90.1 CONTROL 2.4 0.16 2.1 2.7

CZA 76.7 9.75 62.3 94.5

CZC (Copperized) 39.2 2.94 34.7 44.3 CZC (F. R.) 52.3 4.38 45.6 60.0

Carbosota (C-T Creo) 62.5 5.81 53.6 72.8

Creo 50% & Petr. Oil 50%/ 2 1/2% 119.2 28.39 80.7 176.2 Creo 50% & Petro. Oil #2 50% 40.8 2.85 36.4 45.7

Creo 50% & Petro. Oil 50% 66.1 7.01 55.5 78.6

Creo 70% & C-T 30% 74.0 8.79 60.9 89.9 Creo Eng Vert Ret 50%/Coke Oven 64.0 6.47 54.2 75.5

Creo English Coke Oven 50.9 3.91 44.9 57.7

Creo English Vert. Ret. 56.6 4.90 49.1 65.2 Creo High Res Crystals Removed 105.4 20.50 76.6 145.0

Creo High Res Low Tar Acid/ Nap 154.0 51.82 88.7 267.4

Creo Low Res Low Tar Acid/ Nap 53.7 4.50 46.8 61.6 Creo Low Temp 58.2 5.41 49.9 67.7

Creo Med Res Low Frac. 235- 270 58.3 5.42 50.1 67.9

Creo Med Res Low Naph 67.6 7.17 56.8 80.4 Creo Med Res Low Tar Acid 66.4 6.72 56.3 78.4

Creo Med Res Low Tar Acid/Nap 66.8 7.10 56.2 79.6

Creo Med Res w/2 1/2% Penta 95.4 16.07 72.4 125.8 Creo Straight Run High Res. 71.7 8.52 59.0 87.1

Creo Straight Run Low Res. 45.7 3.42 40.4 51.6

Creo Straight Run Med Res. 54.0 4.67 46.9 62.3 Creosote, Oil Tar (Gasco) 48.8 3.85 42.9 55.5

CuNap 0.5%Cu in Petroleum 65.2 6.91 54.8 77.5

GASCO In 2% Penta 78.0 9.91 63.3 96.1 LIGNITE C-T CREOSOTE 37.8 2.64 33.7 42.4

Lignite CT Creo 50% & CT Creo 66.4 6.72 56.3 78.4

Lignite CT Creo 50% & Petro. Oil 39.4 2.70 35.2 44.0 Penta 5% in #2 Distillate 74.0 9.40 60.1 91.2

PETROLEUM TERMITEOL 32.4 2.32 28.8 36.4

Penta 3% In #4 Aromatic Res. 122.1 29.09 82.6 180.5 Penta 5% Cu Nap in Petro 105.0 20.44 76.3 144.5

Penta 5% in #4 Aromatic Res. 119.4 28.44 80.8 176.4

Penta 5% in Petroleum Oil 55.5 4.79 48.1 63.9 Petroleum Oil Aromatic High Res 54.4 4.55 47.4 62.4

Petroleum Oil Aromatic Low Res 47.7 3.66 42.0 54.1

Petroleum Oil #2 Distillate 7.7 0.53 6.9 8.6 Petroleum Oil #4 Aromatic Res 43.0 3.22 38.0 48.6

Petroleum Oil High Aromatic Res 34.0 2.44 30.2 38.2

Petroleum Oil Highly Aromatic 29.9 2.05 26.7 33.4 Petroleum Oil Wyoming Res 11.3 0.77 10.1 12.7

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Table 3. Treatments ordered by increasing predicted typical service life. (Same as Table 1, but order by 60th percentile estimate.)

Treatment Estimated 60th Percentile

Average Service Life Untreated SYP CONTROL 2.4 Petroleum Oil #2 Distillate 7.7 Petroleum Oil Wyoming Res 11.3 Petroleum Oil Highly Aromatic 29.9 PETROLEUM TERMITEOL 32.4 Petroleum Oil High Aromatic Res 34.0 LIGNITE C-T CREOSOTE 37.8 CZC (Copperized) 39.2 Lignite CT Creo 50% & Petro. Oil 39.4 Creo 50% & Petro. Oil #2 50% 40.8 Petroleum Oil #4 Aromatic Res 43.0 Creo Straight Run Low Res. 45.7 Petroleum Oil Aromatic Low Res 47.7 Creosote, Oil Tar (Gasco) 48.8 Creo English Coke Oven 50.9 CZC (F. R.) 52.3 Creo Low Res Low Tar Acid/ Nap 53.7 Creo Straight Run Med Res. 54.0 Petroleum Oil Aromatic High Res 54.4 Penta 5% in Petroleum Oil 55.5 Creo English Vert. Ret. 56.6 Creo Low Temp 58.2 Creo Med Res Low Frac. 235- 270 58.3 ACA 59.5 Carbosota (C-T Creo) 62.5 Creo Eng Vert Ret 50%/Coke Oven 64.0 CuNap 0.5%Cu in Pet 65.2 Creo 50% & Petro. Oil 50% 66.1 Creo Med Res Low Tar Acid 66.4 Lignite CT Creo 50% & CT Creo 66.4 Creo Med Res Low Tar Acid/Nap 66.8 Creo Med Res Low Naph 67.6 Creo Straight Run High Res. 71.7 Boliden Salt B 73.1 Creo 70% & C-T 30% 74.0 Penta 5% in #2 Distillate 74.0 CZA 76.7 GASCO In 2% Penta 78.0 Creo Med Res w/2 1/2% Penta 95.4 Penta 5% Cu Nap in Petro 105.0 Creo High Res Crystals Removed 105.4 Creo 50% & Petr. Oil 50%/ 2 1/2% 119.2 Penta 5% in #4 Aromatic Res. 119.4 Penta 3% In #4 Aromatic Res. 122.1 Creo High Res Low Tar Acid/ Nap 154.0

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CONTROLPetroleum Oil #2 Distillate

Petroleum Oil Wyoming ResPetroleum Oil Highly Aromatic

PETROLEUM TERMITEOLPetroleum Oil High Aromatic Res

LIGNITE C-T CREOSOTECZC (Copperized)

Lignite CT Creo 50% & Petro. OilCreo 50% & Petro. Oil #2 50%

Petroleum Oil #4 Aromatic ResCreo Straight Run Low Res.

Pertoleum Oil Aromatic Low ResCreosote, Oil Tar (Gasco)Creo English Coke Oven

CZC (F. R.)Creo Low Res Low Tar Acid/ Nap

Creo Straight Run Med Res.Pertoleum Oil Aromatic High Res

Penta 5% in Petroleum OilCreo English Vert. Ret.

Creo Low TempCreo Med Res Low Frac. 235- 270

ACACarbosota (C-T Creo)

Creo Eng Vert Ret 50%/Coke OvenCuNap .5%Cu in Pet

Creo 50% & Petro. Oil 50%Creo Med Res Low Tar Acid

Lignite CT Creo 50% & CT CreoCreo Med Res Low Tar Acid/Nap

Creo Med Res Low NaphCreo Straight Run High Res.

Boliden Salt BCreo 70% & C-T 30%

PENTA 5% in #2 DistillateCZA

GASCO In 2% PENTACreo Med Res w/2 1/2% Penta

Penta 5% Cu Nap in PetroCreo High Res Crystals RemovedCreo 50% & Petr. Oil 50%/ 2 1/2%

Penta 5% in #4 Aromatic Res.Penta 3% In #4 Aromatic Res.

Creo High Res Low Tar Acid/ Nap

0 50 100 150

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90% CI for the 60th Percentile of Lifetime (years)

Figure 2. 90% confidence intervals for the 60th percentile of lifetime of posts impregnated with various treatments.

Results and Conclusions Forty-four of the original preservatives still had serviceable posts in the MSP 29 Harrison, MS test plot after over 53 years of service when evaluated by a standard 50 pound lateral load pull test. Of note, were four systems, in particular, that are still in wide spread use today. Untreated southern pine fence post with an average diameter of 4-5 inches, failed in two years or less (estimated 60th percentile of 2.4 years) in the AWPA Hazard Zone 5 test plot. Posts treated with a highly aromatic # 4 fuel oil, ranged in service life, from 29 to 43 years, when treated to an average retention of 6 pounds per cubic foot (in the sapwood). Creosote, with low residue, what today is marketed, as “clean creosote” did not significantly extend its treated posts service life from the 1977 inspection, and that value increased from an average service life of 37 years, to a typical service life of 45 years. Penta treated posts, in P9-Type A oil (# 2 fuel oil) treated to a retention of 0.30 pcf penta, or 75% of the AWPA standard retention, had a typical calculated service life of 74 years. Surprisingly, copper naphthenate treated SYP posts, at roughly half of their specified AWPA retention for fence posts, have a calculated service life of 65 years. Copper naphthenate SYP poles used in AWPA Hazard Zone 5 require a retention of 0.13 pcf ( Cu as metal), and these posts treated to less than one-quarter of that specified retention, in this severe exposure hazard zone have a calculated service life > 65 years.

Acknowledgement The author wish to kindly acknowledge the partial funding of this evaluation of the southern pine posts in the Harrison Test Plot in southern Mississippi, by Merichem Chemicals and Refinery Services, Houston, TX..

AMERICAN WOOD-PRESERVERS' ASSOCIATION

142

Bibliography

Anon. 1956. AWPA Standard M8-56. American Wood Preservers’ Assoc., Stevensville, MD. 3 pp. Anon. 1944. ASTM Standard Method D-2278. American Society of Testing and Materials. Philadelphia,

PA. 4 pp. Blew, J. O. 1947.Comparison of Preservatives in Mississippi Fence-Post Study After 10 Years of Service.

Proceedings of the American Wood-Preservers' Association, vol. 43, pp. 26-41. Davidson, H.L. 1977. Comparison of Wood Preservatives in Mississippi Post Study (1977 Progress

Report). FPL-RN-01. USDA Forest Service, Forest Products Laboratory. Madison, WI. 17 p. Insightful Corporation. 2001. S-PLUS 6 for Windows Programmer’s Guide. Insightful Corporation.

Seattle, WA. 986 pp. Markstron, D.C. and L.R. Gjovik. 1999. Service Life of Fence Posts Treated by Double-Diffusion

Methods. RMRS-RP-17. USDA Forest Service, Rocky Mountain Research Station, Ogden, Utah. 8 p. Markstrom, Donald C. 1984. Service Life Of Treated And Untreated Rocky Mountain Area Fence Posts: A

Progress Report. Res. Note RM-436, Fort Collins, CO: U.S. Department of Agriculture, ForestService, Rocky Mountain Forest and Range Experiment Station. 5 p.

Meeker, W. Q, Escobar, L. A. 1998. Statistical Methods for Reliability Data. John Wiley & Sons, Inc. New York, NY. 680 pp.

SAS Institute Inc. 1999. SAS/STAT® User’s Guide, Version 8. SAS Institute Inc. Cary, NC. 3884 pp. Stokes, M. E., Davis, C. S., Koch, G. G. 2000. Categorical Data Analysis Using the SAS® System, Second

Edition. SAS Institute Inc. Cary, NC. 626 p. Wirka, R. M. 1941. Comparison of Preservatives in Mississippi Fence-Post Study, Proceedings of the

American Wood-Preservers' Association, vol. 37, pp. 365-379.

AMERICAN WOOD-PRESERVERS' ASSOCIATION

143

IRG/WP 00-30243

THE INTERNATIONAL RESEARCH GROUP ON WOOD PRESERVATION

Section 3 Wood protecting chemicals

COMPARATIVE PERFORMANCE OF PENTACHLOROPHENOL AND COPPER NAPHTHENATE IN A LONG TERM FIELD STAKE TEST

by

Darrel D. Nicholas1 and Michael H. Freeman2

Forest Products Laboratory1 Forest & Wildlife Research Center

Mississippi State University Mississippi State, MS 39762

7421 Hunters Tree Cove2 Memphis, TN 38125

Paper prepared for the 31st Annual Meeting Kona, Hawaii, USA 14-19. May 2000

IRG Secretariat KTH

SE-100 44 Stockholm Sweden

COMPARATIVE PERFORMANCE OF PENTACHLOROPHENOL AND COPPER

NAPHTHENATE IN A LONG TERM FIELD STAKE TEST

Darrel D. Nicholas1 and Michael H. Freeman2

Forest Products Laboratory1 Forest & Wildlife Research Center

Mississippi State University Mississippi State, MS 39762

7421 Hunters Tree Cove2 Memphis, TN 38125

ABSTRACT In this study the performance of copper naphthenate (Cu-Nap) and pentachlorophenol (Penta) treated pine stakes against decay and termite attack were compared at two test sites in Mississippi. Four different petroleum oils meeting AWPA Standard P9-A were used as carriers for these wood preservatives. After ten years exposure, the efficacy of Cu-Nap at a retention level of 0.05 pcf Cu was equivalent or slightly better than Penta at a retention level of 0.40 pcf. The type of carrier oil had an effect on the performance, but this was variable for both the type of preservative and test site. In comparing the two test sites, the performance of both preservatives was consistently better at the Dorman Lake test site. Wood treated with the oil carriers alone initially performed reasonably well against both wood decay fungi and termites, but the activity decreased rapidly after about six years exposure. Like the preservatives, the performance of the oils was consistently better at the Dorman Lake test site. INTRODUCTION Cu-Nap was developed in Denmark in 1911 and has been used as a preservative for a variety of wood and textile products over the years. Cu-Nap is generally prepared by reacting copper or copper salts with napthenic acid or with sodium naphthenate. The three commercial methods of producing copper naphthenate are direct metal, melt (fusion), or double decomposition methods. Naphthenic acid is a by-product of petroleum refining and contains a mixture of monocarboxylic acids which have cyclopentane and cyclohexane groups with an acid number ranging from 150 to 300. The proposed chemical structure for Cu-Nap is (2):

R C

O Cu O

CO

C

R O

O

C

O R

O Cu O

R

1 Approved for publication as Journal Article No. FP163 of the Forest & Wildlife Research Center, Mississippi State University.

The use of Cu-Nap as a commercial wood preservative in the United States has been limited, but recent environmental concerns with CCA, Penta, and Creosote has stimulated its use in utility poles and other wood products. In the mid-1980's, the Electrical Power Research Institute (EPRI) reviewed their own use of oil-borne preservatives within their member systems and determined that they should investigate possible safer and more environmentally benign preservatives and funded a research project to investigate alternatives to pentachlorophenol. Since there was limited data available on the performance of Cu-Nap treated wood exposed to soil contact, this study1 was initiated. The objective of this study was to evaluate the comparative performance of Cu-Nap and Penta formulated with several different commercial carrier oils. EXPERIMENTAL Preservatives Technical grade Penta (>96% active ingredient) and Cu-Nap (8% Copper as metal) were obtained from various manufacturers within the United States. Carrier Oils A total of four carrier oils that met AWPA Standard P9-A were selected for this study. These were: 1. California Shell Oil from Shell Chemical Company 2. Base Oil L from Lillyblad Petroleum Inc. 3. Ashland Oil from Ashland Petroleum Company 4. #2 Diesel Oil + KB3 + B11 (KB3 & B11 from Eastman Chemical Products Company). The physical properties of these oils are shown in Table 1. Oils 1-3 were diluted with toluene (20% oil and 80% toluene) before using them to treat the fungus cellar and field stake test specimens. The treating solution for Oil 4 was formulated with 17% diesel + 2% B11 + 1% KB3 + 80% toluene before treatment of these test specimens. Soil Block Test This test was carried out in accordance with AWPA Standard M10-77, using kiln-dried southern yellow pine (SYP)(Pinus sp.) sapwood. The oils were diluted with toluene to provide appropriate concentrations. The treated cubes were exposed to a brown-rot fungus (Gloeophyllum trabeum) and a white-rot fungus (Trametes versicolor). Fungus Cellar Test The test specimens measuring 0.5 x 0.75 x 10 inches long were prepared from kiln-dried SYP sapwood. A total of five replicate stakes were treated with each of the four different levels of Penta (ranging from 0.09 to 0.80 pcf) and Cu-Nap (ranging from 0.010 to 0.090 pcf copper metal) using the four carrier oils listed above. After allowing the toluene to evaporate, the stakes

1 This research was funded by the Electrical Power Research Institute under Contract No. WO2797-01. of the soil water-holding capacity. The fungus cellar room was maintained at a temperature of approximately 80 F with a humidity of 90%. The stakes were removed at three month intervals and evaluated for decay, using a 10 to 0 rating scale with 10 denoting sound and 0 denoting failure. Field Stake Test The field stake test was performed in accordance with AWPA Standard E 7, using 1 x 2 x 22 inch southern pine sapwood stakes. A total of 20 replicate stakes were treated with each of the field stake formulations listed in Table 2. After air drying, a 4-inch section was cut from the end of each stake and reserved for possible depletion analysis. The field stakes were installed at the following sites on the dates indicated: Dorman Lake, MS May 2, 1988 Saucier, MS April 22, 1988 These field stakes were pulled and evaluated for decay and termite damage annually, using the AWPA E7-93 rating system where 10 denotes sound and 0 denotes failure. Biocide Depletion from Field Stakes The field stake depletion test was carried out with 1 ½-inch square by 22-inch long southern pine sapwood stakes. Before exposure in the test plot, these stakes were treated with Penta and Cu-Nap formulations using the oil carriers listed above. After air drying, a 4-inch section was cut from the end of each stake and reserved for the initial retention analysis. These 18-inch long stakes were then installed at the Saucier test plot by inserting them vertically into the ground to a depth of 14 inches. A total of 5 stakes were installed for each retention level and these were removed after two years. After cleaning, a section was removed from the stakes at two locations- 1-inch below the top of the stake and at a location slightly below the ground line. These wafers were ground in a Wiley mill and analyzed on an Asoma XRF unit. RESULTS AND DISCUSSION The importance of carrier oil properties on the performance of organic wood preservatives is well known and serves as the basis for the AWPA Standard P9-A. In this standard physical properties such as viscosity, specific gravity, penta solvency and distillation range of the carrier oils must meet specified criteria in order to be acceptable because they influence the plant operation and performance of the treated wood product. With regard to performance, the major factor is the effect of the carrier oil on depletion rate of the biocide (1). Another possible factor that may influence the performance of wood preservative systems is the inherent toxicity of the carrier oils to wood decay fungi. The data in Figure 1, which includes the oils used in this study as well as others, clearly shows that some of the oils are toxic to wood decay fungi. However, it should be pointed out that this data is based on a pure culture basidiomyce test which does not necessarily predict the performance of treated wood in service. Nevertheless, the data in Figures 2 and 3 demonstrate that the carrier oils provided some degree of protection to exposed wood in

soil contact. However, the performance is limited and most of the oil treated wood was heavily degraded after a few years exposure. A summary of the results is shown in Table 2 and Figure 4. It is apparent from this data that all of the Cu-Nap formulations performed better than comparable penta formulations. Results for the field stake test after 11 years exposure at two test sites in Mississippi are presented in Table 3. This data clearly shows that both penta and Cu-Nap performed very well against both decay fungi and termite attack. Comparative data for Cu-Nap at a copper retention level of 0.05 pcf and penta at a retention level of 0.4 pcf at both test sites are shown in Figures 5 and 6. From this data it is apparent that overall the performance of Cu-Nap at 0.05 pcf is somewhat better than that of penta at 0.04 pcf. The only exceptions are the diesel/KB3/B11 and base oil formulations, for which the performance of Cu-Nap is slightly lower than for penta at the Saucier test site. Consequently, on the basis of this data it can be concluded that wood treated at a copper retention level of 0.05 pcf will perform satisfactorily. In reviewing the data in Figures 5 and 6 it is of interest to note that the performance of both penta and Cu-Nap treated wood is slightly lower at the Saucier test site. There are two possible explanations for this difference. First, the average temperature and rainfall at the Saucier site is somewhat greater than that experienced at the Dorman test site. Secondly, the soil types at the two test sites are quite different. The soil at Dorman is high in clay content and is classified as silty clay loam, whereas the soil at Saucier is characterized as a loamy sand type soil. These differences may possibly result in different oil carrier and biocide depletion rates. The fact that the Saucier test site has higher rainfall and soil with good drainage properties may possibly result in higher biocide and carrier oil depletion rates. This possibility, at least for the carrier oil, is supported by the data for stakes treated with carrier oils alone. That is to say, the stakes treated with the oils have somewhat higher decay ratings at the Dorman test site than at the Saucier test site. In addition to the broad spectrum efficacy of biocides against microorganisms and insects, the depletion rate of biocides plays a major role in the performance of treated wood. Hence, a biocide depletion analysis was included in this study and the results are presented in Table 4. In general, the biocide loss from the above ground section of these field stakes is lower than the below ground section. Furthermore, on a percentage basis the loss of penta is somewhat greater than that for Cu-Nap. However, it should be emphasized that due to the relatively small sample size this data does not represent statistically significant differences. Nevertheless, this data does suggest that the depletion rate of Cu-Nap compares favorably to that of penta. CONCLUSIONS This long term study clearly shows that oil-borne Cu-Nap is an effective wood preservative. When treated pine sapwood was compared with penta in four different P9-A oil carriers, Cu-Nap at a copper retention of 0.05 pcf provides approximately the same level of protection as penta at 0.04 pcf. Although wood treated with the carrier oils alone exhibited some degree of efficacy against fungi and termites, they did not provide long term protection for field stakes.

REFERENCES 1. Arsenault, R.D. 1973. Factors influencing the effectiveness of preservative systems. In: Wood deterioration and its prevention by preservative treatment. (D.D. Nicholas, ed.) Vol. II, pp. 121-278. 2. Nicholas, D.D., W.P. Henry, and R.C. Vasishth. 1996. The role of copper in wood preservation. In: Handbook of Copper Compounds and Applications. W. Richardson (ed.). Marcel Dekker, Inc.

TABLE 1. PHYSICAL PROPERTIES OF CARRIER (P9-A) OILS

PROPERTY CALIFORNIA SHELL BASE OIL L ASHLAND #2 DIESEL (90%)/ KB3 (10%)

Specific Gravity @ 72 F .9548 .9740 .9452 .9124

Whole Oil 46 37 35 35

Fract ion above 500º F 53 40 37 -- Viscosi ty Sus @ 100º F (A S T M D -88)

Bot tom 25% -- 67 47 --

0% a.i . 49.4 39.7 37.6 35.5 Viscosity Sus @ 100º F with Pen ta 7% a.i . 54.1 40.8 37.5 36.8 Interfacial Surface Tension Dynes/cm (ASTM D1871) Frac t ion above 500 F 24.3 23.5 24.5 --

Whole Oil 15 18.4 8.15 15

Fract ion above 500º F 16 10 8 -- Penta Solvency-AWPA P-5(%)

Bot tom 25% 14.4 12.5 9.2 --

Dis t i l la t ion Temperature of Various Fract ions

Initial Boiling Point 464º F 480º F 470º F 410º F

10% 492º F 515º F 500º F 456º F 20% 516º F 532º F 520º F 480º F

30% 530º F 545º F 532º F 495º F

40% 548º F 560º F 545º F 514º F

50% 575º F 575º F 558º F 530º F

60% 604º F 595º F 575º F 550º F

70% 637º F 610º F 595º F 568º F

75% 650º F 625º F 604º F 577º F

80% 666º F 640º F 618º F 590º F

Volume Dist i l led (ASTM D -86)

90% 673º F 670º F 648º F 623º F

Above 500º F 86 95 90 68

Table 2. Comparative Decay Ratings for Stakes Treated with Cu Nap and Penta in Four Different Oils and Exposed in a Fungus Cellar.

Decay Ratings Ashland CA Shell Base Oil L Diesel/KB3/B11 Exposure

Time (mo) Cu Nap. Retn (pcf) 0.048

Penta Retn (pcf) 0.372

Cu Nap. Retn (pcf) 0.046

Penta Retn (pcf) 0.398

Cu Nap. Retn (pcf) 0.052

Penta Retn (pcf) 0.390

Cu Nap. Retn (pcf) 0.057

Penta Retn (pcf) 0.439

3 10 9.7 10 10 10 10 10 10 6 10 9.9 10 10 9.7 9.8 7.2 7.4 9 9.9 9.7 9.9 9.0 9.9 9.2 4.6 3.7 12 2.9 2.3 8.4 4.0 5.5 3.1 4.0 3.6 15 2.8 2.3 8.0 3.6 5.2 2.2 40 3.4 18 2.9 2.2 8.1 3.6 5.4 2.2 4.0 3.0 21 2.5 2.0 7.8 3.2 5.4 1.8 3.4 1.8 24 2.5 1.8 6.6 2.8 5.0 1.8 2.4 1.4

Table 3. Average Decay and Termite Ratings for Field Stakes Located at Saucier and Dorman After 11-Years Exposure.

Average Decay and Termite Ratings at Saucier and Dorman with Different C arrier Oils. Ashland CA Shell Base Oil Diesel/KB3/B11

Dorman Saucier Dorman Saucier Dorman Saucier Dorman Saucier Treatment

Retention (pcf)

Decay Termite Decay Termite Decay Termite Decay Termite Decay Termite Decay Termite Decay Termite Decay Termite 0.0251 9.1 9.6 7.9 8.2 9.9 10 9.7 9.9 8.6 8.8 8.2 8.2 8.2 8.4 5.3 5.7 0.050 9.7 9.9 9.0 8.6 9.7 9.9 9.6 9.6 9.2 9.7 8.2 8.6 9.0 9.3 7.3 7.4 Cu Nap. 0.100 9.7 10 9.5 9.2 9.9 9.9 9.8 9.9 10 10 9.8 9.6 9.7 9.9 9.2 9.1 0.20 8.2 8.3 8.1 7.7 8.2 8.3 6.6 6.9 8.0 8.3 7.7 7.4 7.5 8.0 6.9 6.6 0.40 8.9 9.1 8.7 8.6 9.3 9.7 7.8 7.7 8.7 8.8 8.6 8.3 8.4 8.3 7.6 7.5 Penta 0.80 9.7 9.8 9.8 9.6 8.9 9.3 8.5 8.6 9.7 9.8 9.5 8.9 9.0 9.2 8.5 7.9

Carrier Oil 0.00 2.6 5.3 2.7 2.0 7.8 8.7 3.4 3.6 4.4 7.4 2.4 3.0 4.1 7.6 1.6 2.3 Untreated 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

1 Based on Copper

Table 4. Average Percent Depletion of Cu Nap and Penta from Above and Below Ground Sections of 1½-inch Square Stakes Treated with Several Different Carrier Oils, and exposed at Saucier for 2-years.

Average Percent Loss After 2-Years Exposure1 Carrier Oil Preservative Initial Retention (pcf) Above Ground Below Ground Cu Nap. (0.049) 20.3 30.1 Ashland Penta (0.383) 8.4 39.2 Cu Nap. (0.045) 20.6 17.1 CA Shell Penta (0.383) 14.7 39.4 Cu Nap. (0.049) 17.9 21.8 Base Oil Penta (0.396) 11.2 43.2 Cu Nap. (0.051) 8.0 18.8 Diesel/KB3/B11 Penta (0.394) 31.9 19.1

1Cu Nap retention and depletion values are based on Cu content.

Figure 1.Approximate Toxic Threshold Values (pcf) Of Several OilsExposed To Fungi In A Soil-Block Test.

0

2

4

6

8

10

12

14

T. Versicolor G. Trabeum

5.5

3.5

7.1

1.7 1.9

4.2

>12.1

>8.9

>11.8

4.6 4.3

5.8

>11.1

>9.4>8.9

7.6

Ashland Husky Base Oil CA Shell Certrex #2 Diesel KB3 B11

Figure 2.Average Decay Ratings For Stakes Treated With Carrier Oils/Toluene(20% / 80%) After Exposure At Dorman.

0123456789

10

0 2 4 6 8 10 12

Ashland Oil CA Shell Oil Base Oil L #2 Diesel/KB3/B-11

Decay Ratings

Time (years)

Figure 3.Average Decay Ratings For Stakes Treated With Carrier Oils/Toluene(20% / 80%) After Exposure At Saucier.

0123456789

10

0 2 4 6 8 10 12

Ashland Oil CA Shell Oil Base Oil L #2 Diesel/KB3/B-11

Decay Ratings

Time (years)

Figure 4.Comparative Decay Ratings For Stakes Treated With Cu Nap And PentaIn Four Different Oils And Exposed In A Fungus Cellar.

0123456789

10

0 3 6 9 12 15 18 21 24

Ashland/Cu Nap 0.048 (pcf) Ashland/Penta 0.372 (pcf) CA Shell/Cu Nap (0.046 pcf)

CA Shell/Penta (0.398 pcf) Base Oil/Cu Nap (0.052 pcf) Base Oil/Penta (0.390 pcf)

Diesel/Cu Nap (0.057 pcf) Diesel/Penta (0.439 pcf)

Decay Ratings

Time (Months)

Figure 5.Comparative Decay Ratings For Cu Nap And Penta TreatedStakes Using Several Different Carrier Oils And Exposed AtDorman For 11-Years.

0

2

4

6

8

10

Cu Nap (0.05 pcf Cu) Penta (0.40 pcf)

Decay Ratings9.7

8.9 9.3 9.28.7 9.0

8.4

9.7

Ashland CA Shell Base Oil Diesel/KB3/B11

Figure 6.Comparative Decay Ratings For Cu Nap And Penta TreatedStakes Using Several Different Carrier Oils And Exposed AtSaucier For 11-Years.

0

2

4

6

8

10

Ashland CA Shell Base Oil Diesel/KB3/B11

Cu Nap (0.05 pcf Cu) Penta (0.40pcf)

Decay Ratings

9.0 8.77.8

8.2 8.6

7.3 7.6

9.6

APPENDIX II

RESTRICTED USE PESTICIDE DUE TO FETOTOXICITY AND ONCOGENICITY IN LABORATORY ANIMALS

For retail sale and use only by Certified Applicators or by persons under their direct supervision and only for those uses covered by the Certified Applicator’s certification.

KMG-B

PENTA OL TECHNICAL PENTA RQ/PENTACHLOROPHENOL

UN3155 Protects against termites, wood rotting, fungi, lyctus powder

post beetles and other wood degrading organisms

Active Ingredients: Pentachlorophenol……………………..80.0 % Other Chlorophenols………………..…10.0 % Other Ingredients……………………………… 4.0 % Total ………………………………………….100.0 %

EPA Reg. No. 61483 - 3 EPA Est. No. 54816 - 1

KEEP OUT OF REACH OF CHILDREN

DANGER POISON

FIRST AID IF SWALLOWED: Call a poison control center or doctor immediately for treatment advice. Have person sip a glass of water if able to swallow. Do not give anything by mouth to an unconscious person. Do not induce vomiting unless told to by a poison control center or doctor. IF IN EYES: Hold eye open and rinse slowly and gently with water for 15-20 minutes. Remove contact lenses, if present, after the first 5 minutes, then continue rinsing. Call a poison control center or doctor for treatment advice. IF ON SKIN OR CLOTHING: Take off contaminated clothing. Rinse skin immediately with plenty of water for 15-20 minutes. Call a poison control center or doctor for treatment advice. IF INHALED: Move person to fresh air. If person is not breathing, call 911 or an ambulance, then give artificial respiration, preferably mouth-to-mouth if possible. Call a poison control center or doctor for further treatment advice. NOTE TO PHYSCIAN: This product is a metabolic stimulant. Treatment is supportive. Forced Diuresis may be effective to reduce total body-burden. Treat hyperthermia with physical measures. Do not administer aspirin, phenothiazines or atropine since they may enhance toxicity. Have the product container or label with you when calling a poison control center or doctor, or going for treatment. You may also contact 1-800-424-9300 for emergency medical treatment. Net Contents:______________ KMG-BERNUTH, INC. 10611 Harwin Drive, Suite 402 Houston, Texas 77036

Page 2 of 5 Penta OL TECH

9/17/03

CONDITIONS OF SALE AND LIMITATION OF WARRANTY AND LIABILITY

NOTICE: Read the entire Directions for Use and Conditions of Sale and Limitation of Warranty and Liability before buying or using this product. If the terms are not acceptable, return the product at once, unopened, and the purchase price will be refunded. The Directions for Use of this product should be followed carefully. It is impossible to eliminate all risks inherently associated with the use of this product. Crop injury, ineffectiveness or other unintended consequences may result because of such factors as manner of use or application, weather or crop conditions, presence of other materials or other influencing factors in the use of the product, which are beyond the control of KMG-BERNUTH, INC or Seller. All such risks shall be assumed by Buyer and User, and Buyer and User agree to hold KMG-BERNUTH, INC and Seller harmless for any claims relating to such factors. KMG-BERNUTH, INC warrants that this product conforms to the chemical description on the label and is reasonably fit for the purposes stated in the Directions for Use, subject to the inherent risks referred to above, when used in accordance with directions under normal use conditions. This warranty does not extend to the use of this product contrary to label instructions, or under abnormal conditions or under conditions not reasonably foreseeable to or beyond the control of Seller or KMG-BERNUTH, INC, and Buyer and User assume the risk of any such use. KMG-BERNUTH, INC MAKES NO WARRANTIES OF MERCHANTABILITY OR OF FITNESS FOR A PARTICULAR PURPOSE NOR ANY OTHER EXPRESS OR IMPLIED WARRANTY EXCEPT AS STATED ABOVE. In no event shall KMG-BERNUTH, INC or Seller be liable for any incidental, consequential or special damages resulting from the use or handling of this product. THE EXCLUSIVE REMEDY OF THE USER OR BUYER, AND THE EXCLUSIVE LIABILITY OF KMG-BERNUTH, INC AND SELLER FOR ANY AND ALL CLAIMS, LOSSES, INJURIES OR DAMAGES (INCLUDING CLAIMS BASED ON BREACH OF WARRANTY, CONTRACT, NEGILIGENCE, TORT, STRICT LIABILITY OR OTHERWISE) RESULTING FROM THE USE OR HANDLING OF THIS PRODUCT SHALL BE THE RETURN OF THE PURCHASE PRICE OF THE PRODUCT OR, AT THE ELECTION OF KMG-BERNUTH, INC OR SELLER, THE REPLACEMENT OF THE PRODUCT. KMG-BERNUTH, INC and Seller offer this product, and Buyer and User accept it, subject to the foregoing conditions of sale and limitations of warranty and of liability, which may not be modified except by written agreement signed by a duly authorized

representative of KMG-BERNUTH, INC.

Page 3 of 5 Penta OL TECH

9/17/03

PRECAUTIONARY STATEMENTS

HAZARDS TO HUMANS AND DOMESTIC ANIMALS DANGER Maybe fatal if swallowed, inhaled, or absorbed through skin. Causes skin and eye irritation. Causes delayed chemical burns. Do not get in eyes, on skin or on clothing. Do not breathe vapors, spray mist, or dust. Use with adequate ventilation. Do not take internally. Wash thoroughly after skin contact, before eating, drinking, use of tobacco products, or using restrooms. The U. S. EPA has determined that pentachlorophenol can produce defects in the offspring of laboratory animals. Exposure to pentachlorophenol during pregnancy should be avoided. Applicators must not eat, drink, or use tobacco products during those parts of the application process that may expose them to the wood treatment formulation (e.g., manually opening/closing cylinder doors, moving trams out of cylinders, mixing chemicals, and handling freshly treated wood). Individuals who manually open cylinder doors must wear gloves and a respirator. Individuals who enter pressure treatment cylinders and other related equipment that is contaminated with wood treatment formulation (e.g., cylinders that are in operation or are not free of the treatment solution) must wear protective clothing (including overalls, jackets, gloves, and boots) impervious to the wood treatment formulation, and a respirator. Protective clothing must be changed when it shows signs of contamination. Applicators must leave all protective clothing, workshoes or boots, and equipment at the plant. Worn-out protective clothing and workshoes or boots must be left at the treatment plant and disposed of in any general landfill, in the trash, or in any other manner approved for pesticide disposal. NOTE TO USE: As used on this label, the term “respirators” means properly fitting, well-maintained, half-mask canister or cartridge respirators which are MSHA/NIOSH-approved for organic vapors and acid gases. Examples of acceptable materials for protective clothing (e.g., gloves, overalls, jackets, and boots) required during application and handling of pentachlorophenol are polyvinyl acetate (PVA), polyvinyl chloride (PVC), neoprene, NBR (Buna-N), and nitrile. In addition, plastic-coated disposable coveralls impervious to dust are acceptable for dust protections.

Page 4 of 5

Penta OL TECH 9/17/03

ENVIRONMENTAL HAZARDS This product is toxic to fish and wildlife. Do not apply directly to water or to areas where surface water is present or to intertidal areas below the mean high water mark. Do not contaminate water by cleaning of equipment or disposal of wastes. Do not discharge effluent containing this product into lakes, streams, ponds, estuaries, oceans or other waters unless and in accordance with requirements of a National Pollutant Discharge Elimination System (NPDES) permit, and that the permitting authority has been notified in writing prior to discharge. Do not discharge effluent containing this product to sewer systems without previously notifying a local sewage treatment plant authority. For guidance, contact your State Water Board or Regional Office of the EPA. PHYSICAL AND CHEMICAL HAZARDS Do not use or store near heat or open flames. In case of fire, use water spray, foam CO2, or dry chemical. Plants or shrubs should be removed within 3 feet of treatment or protected with tar paper. Treated sawdust and other wood waste should not come in contract with domestic animals or be used so they may come in contact with useful living plants. Close container after each use. The registrant has complied with all terms and conditions of the registration governing the composition of this product as approved by the United State Environmental Protection Agency under section 3 of the Federal Insecticide, Fungicide, and Rodenticide Act. The use of this product for any purpose other than those stated on the label, including use of this product in the manufacture or formulation of other pesticide products or in repackaging of the product, is prohibited. DIRECTIONS FOR USE It is a violation of Federal law to use this product in a manner inconsistent with its label. This product: is intended for exterior use. is not intended for home and farm use. must not be used for pressure or dip treating logs used in the construction of log homes except laminated beams or building components which are in ground contact and are subject to decay or insect infestation and where two coats of an appropriate sealer are applied. Urethane, shellac, latex, epoxy, enamel and varnish are acceptable sealers for pentachlorophenol treated wood.

Page 5 of 5 Penta OL TECH

9/17/03 This product is used for the preparation of fungicidal and insecticidal solutions. Recommended concentrations for such solutions vary according to the end uses and methods of applying solutions to obtain the desired efficacy. This product is intended for commercial use only for the preparation of wood preservations formulations and must be dissolved before use. Add one part or more of this product to 20 arts of fuel oil, kerosene, or other hydrocarbons with the desired volatility, and mix well. Pressure treatment in a commercial pressure facility allows for the attainment of proper retention and penetration levels and makes the treated wood products suitable for ground contact. To protect dry and/or seasoned lumber, timbers, posts, poles and other wooden members before construction and before placing in contact with the soil, the wood should be treated in a commercial vessel capable of physically (by pressure, temperature or time) impregnating the wood and providing adequate penetration and retention. If temperature or time is used as the treating parameter, treat for 12 to 48 hours or until effective retention and penetration is achieved. All wooden members should be free of bark before receiving treatment.

STORAGE AND DISPOSAL Do not contaminate water, food, or feed by storage or disposal. STORAGE: KEEP AWAY FROM FIRE. DO NOT STORE NEAR OPEN FLAME. Storage of this product in unheated vessels is possible. Viscosity increases as temperature decreases. Avoid temperatures above 150 F. Containment areas are required. Observe all safety precautions. Do not contaminate with other materials. Do not mix with other pesticides or preservatives. Wear protective clothing, gloves and goggles when handling. PESTICIDE DISPOSAL: Pesticide wastes are toxic. Improper disposal of excess pesticide, spray mixture, or rinsate is a violation of Federal law. If these wastes cannot be disposed of by use according to label instructions, contact your State Pesticide or Environmental Control Agency, or the Hazardous Waste representative at the nearest EPA Regional Office for guidance. CONTAINER DISPOSAL: Triple rinse or equivalent. Then offer for recycling or reconditioning, or puncture and dispose of in a sanitary landfill, or by other procedures approved by state and local authorities.

Material Safety Data Sheet KMG-B Penta OL Technical Pentachlorophenol

Version: 3 Date Issued: 11/06/2009 MSDS No. 6148303

SECTION 1. CHEMICAL PRODUCT AND COMPANY IDENTIFICATION

COMPANY: KMG- Bernuth, Inc.

9555 W. Sam Houston Parkway S., Suite 600

Houston, Texas 77099

PHONE NUMBER: 713-600-3800

EMERGENCY PHONE: CHEMTREC: 1-800-424-9300

NAME USED ON LABEL: KMG-B Penta OL Technical Pentachlorophenol

PRODUCT USE: Wood Preservative

SECTION 2: COMPOSITION/INFORMATION ON INGREDIENTS

IDENTITY CAS NUMBER TYPICAL % OTHER INFORMATION Pentachlorophenol 87-86-5 86.0 %

Other Chlorophenols Mixture 10.0 %

Hexachlorodibenzo-8-dioxin 34465-46-8 4.0 ppm max

Hexachlorobenzene 118-74-1 5.0 ppm max

Ingredients not precisely identified are proprietary or non-hazardous.

Values are not product specifications.

SECTION 3: HAZARDS IDENTIFICATION

PHYSICAL AND CHEMICAL HAZARDS Do not use or store near heat or open flames. In case of fire, use water spray, foam CO2, or dry chemical.

Plants or shrubs should be removed within 3 feet of treatment or protected with tar paper. Treated

sawdust and other wood waste should not come in contract with domestic animals or be used so they may

come in contact with useful living plants. Close container after each use.

The registrant has complied with all terms and conditions of the registration governing the composition of

this product as approved by the United State Environmental Protection Agency under section 3 of the

Federal Insecticide, Fungicide, and Rodenticide Act. The use of this product for any purpose other than

those stated on the label, including use of this product in the manufacture or formulation of other pesticide

products or in repackaging of the product, is prohibited.

HAZARDS TO HUMANS AND DOMESTIC ANIMALS

DANGER

Maybe fatal if swallowed, inhaled, or absorbed through skin. Causes skin and eye irritation. Causes

delayed chemical burns. Do not get in eyes, on skin or on clothing. Do not breathe vapors, spray mist, or

dust. Use with adequate ventilation. Do not take internally. Wash thoroughly after skin contact, before

eating, drinking, use of tobacco products, or using restrooms.

Page 1 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 3: HAZARDS IDENTIFICATION (Continued)

The U. S. EPA has determined that pentachlorophenol can produce defects in the offspring of laboratory

animals. Exposure to pentachlorophenol during pregnancy should be avoided.

Applicators must not eat, drink, or use tobacco products during those parts of the application process that

may expose them to the wood treatment formulation (e.g., manually opening/closing cylinder doors,

moving trams out of cylinders, mixing chemicals, and handling freshly treated wood).

Individuals who manually open cylinder doors must wear gloves and a respirator.

Individuals who enter pressure treatment cylinders and other related equipment that is contaminated with

wood treatment formulation (e.g., cylinders that are in operation or are not free of the treatment solution)

must wear protective clothing (including overalls, jackets, gloves, and boots) impervious to the wood

treatment formulation, and a respirator.

Protective clothing must be changed when it shows signs of contamination. Applicators must leave all

protective clothing, workshoes or boots, and equipment at the plant. Worn-out protective clothing and

workshoes or boots must be left at the treatment plant and disposed of in any general landfill, in the trash,

or in any other manner approved for pesticide disposal.

NOTE TO USER: As used on this label, the term “respirators” means properly fitting, well-maintained,

half-mask canister or cartridge respirators which are MSHA/NIOSH-approved for organic vapors and acid

gases. Examples of acceptable materials for protective clothing (e.g., gloves, overalls, jackets, and boots)

required during application and handling of pentachlorophenol are polyvinyl acetate (PVA), polyvinyl

chloride (PVC), neoprene, NBR (Buna-N), and nitrile. In addition, plastic-coated disposable coveralls

impervious to dust are acceptable for dust protections.

SECTION 4: FIRST AID MEASURES

IF SWALLOWED: Call a poison control center or doctor immediately for treatment advice. Have

person sip a glass of water if able to swallow. Do not give anything by mouth to an unconscious person.

Do not induce vomiting unless told to by a poison control center or doctor.

IF IN EYES: Hold eye open and rinse slowly and gently with water for 15-20 minutes. Remove contact

lenses, if present, after the first 5 minutes, then continue rinsing. Call a poison control center or doctor for

treatment advice.

IF ON SKIN OR CLOTHING: Take off contaminated clothing. Rinse skin immediately with plenty of

water for 15-20 minutes. Call a poison control center or doctor for treatment advice.

IF INHALED: Move person to fresh air. If person is not breathing, call 911 or an ambulance, then give

artificial respiration, preferably mouth-to-mouth if possible. Call a poison control center or doctor for

further treatment advice.

NOTE TO PHYSCIAN: This product is a metabolic stimulant. Treatment is supportive. Forced

Diuresis may be effective to reduce total body-burden. Treat hyperthermia with physical measures. Do

not administer aspirin, phenothiazines or atropine since they may enhance toxicity.

Have the product container or label with you when calling a poison control center or doctor, or

going for treatment. You may also contact 1-800-322-8177 for emergency medical treatment.

Page 2 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 5: FIREFIGHTING MEASURES

FLASH POINT: Nonflammable

AUTOIGNITION TEMPERATURE: Not applicable

FLAMMABLE LIMITS (STP): Noncombustible

EXTINGUISHING MEDIA: Small Fires: Use dry chemical, carbon dioxide or water spray. Large

Fires: Use dry chemical, carbon dioxide, alcohol-resistant foam or water spray. Use water to cool fire

exposed containers but do not get water inside containers.

PROTECTIVE EQUIPMENT: Fire fighters should wear MSHA/NIOSH approved self-contained

positive-pressure breathing apparatus and full protective clothing. Avoid exposing the skin to the

product.

NFPA RATING: Health 3 Fire 0 Reactivity 0

SPECIAL HAZARDS: Unusual Fire and Explosion Hazards – Fumes and vapors from the hot or

burning product may contain hydrogen chloride (HCl), carbon monoxide (CO) and carbon dioxide (CO2

Contact with metals may evolve flammable hydrogen gas. Containers my explode when heated.

SECTION 6: ACCIDENTAL RELEASE MEASURES

In Case of Spill or Leak: Wear long-sleeved shirt and long pants, rubber boots over shoes and socks,

chemical resistant waterproof gloves, protective chemical safety goggles and a NIOSH-approved pesticide

respirator or Air-supplied respirator. For small spills, absorb on absorbent material, sweep up and place

in an approved chemical container. Use non-sparking tools and remove ignition sources.

Wash the spill area with a solution of water and household bleach (1:2), absorb on absorbent material ,

sweep up and place in a disposal container. Wash area with detergent and absorb liquid and sweep up and

place into container. Seal the container and handle in an approved manner.

Flush the area with water to remove any residue. Contain any washwaters. Do not allow washwaters to

contaminate surface waters and don not flush to sewer systems.

For disposal, refer to Section 13, Disposal Considerations.

SECTION 7: HANDLING AND STORAGE SECTION

Do not contaminate water, food, or feed by storage or disposal.

STORAGE: KEEP AWAY FROM FIRE. DO NOT STORE NEAR OPEN FLAME.

Storage of this product in unheated vessels is possible. Viscosity increases as temperature decreases.

Avoid temperatures above 150 F. Containment areas are required. Observe all safety precautions. Do

not contaminate with other materials. Do not mix with other pesticides or preservatives. Wear protective

clothing, gloves and goggles when handling.

Page 3 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION

DANGER

Maybe fatal if swallowed, inhaled, or absorbed through skin. Causes skin and eye irritation. Causes

delayed chemical burns. Do not get in eyes, on skin or on clothing. Do not breathe vapors, spray mist, or

dust. Use with adequate ventilation. Do not take internally. Wash thoroughly after skin contact, before

eating, drinking, use of tobacco products, or using restrooms.

The U. S. EPA has determined that pentachlorophenol can produce defects in the offspring of laboratory

animals. Exposure to pentachlorophenol during pregnancy should be avoided.

Applicators must not eat, drink, or use tobacco products during those parts of the application process that

may expose them to the wood treatment formulation (e.g., manually opening/closing cylinder doors,

moving trams out of cylinders, mixing chemicals, and handling freshly treated wood).

Individuals who manually open cylinder doors must wear gloves and a respirator.

Individuals who enter pressure treatment cylinders and other related equipment that is contaminated with

wood treatment formulation (e.g., cylinders that are in operation or are not free of the treatment solution)

must wear protective clothing (including overalls, jackets, gloves, and boots) impervious to the wood

treatment formulation, and a respirator.

Protective clothing must be changed when it shows signs of contamination. Applicators must leave all

protective clothing, workshoes or boots, and equipment at the plant. Worn-out protective clothing and

workshoes or boots must be left at the treatment plant and disposed of in any general landfill, in the trash,

or in any other manner approved for pesticide disposal.

NOTE TO USER: As used on this label, the term “respirators” means properly fitting, well-maintained,

half-mask canister or cartridge respirators which are MSHA/NIOSH-approved for organic vapors and acid

gases. Examples of acceptable materials for protective clothing (e.g., gloves, overalls, jackets, and boots)

required during application and handling of pentachlorophenol are polyvinyl acetate (PVA), polyvinyl

chloride (PVC), neoprene, NBR (Buna-N), and nitrile. In addition, plastic-coated disposable coveralls

impervious to dust are acceptable for dust protections.

OCCUPATIONAL EXPOSURE LIMITS:

ACGIH TLV TWA (8 hour) 0.5 mg/m3 OSHA PEL TWA (8 hour) 0.5 mg/m

3

VENTILATION: Do not use in closed or confined space. Open door and/or windows. Provide exhaust

ventilation or other engineering controls to keep the airborne concentration below 0.5 mg/m3.

BODY PROTECTION: Wear PVC, neoprene, nitrile latex or equivalent gloves and tightly woven

clothing including long sleeve shirt when handling pentachlorophenol. When mixing penta solutions,

wear protective clothing, gloves, boots or shoes, which are suitable for the solvent used.

HYGIENE: Avoid contact with skin and breathing dust. Do not eat, drink or smoke in work area. Wash

hands prior to eating, drinking or using restroom. Shower and change into uncontaminated clothing

before leaving work premises. Page 4 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION (Continued)

EYE PROTECTION: Use protective eyewear. Do not wear contact lenses. When mixing penta

solutions, wear chemical goggles and/or face shield.

RESPIRATORY PROTECTION: Where concentrations of pentachlorophenol exceed or are likely to

exceed

0.5 mg/m3, a NIOSH/MSHA approved organic vapor-dust filter type respirator is acceptable. A

NIOSH/MSHA approved self-contained breathing apparatus or air line respirator with full face piece, is

required for concentrations above 150.0 mg/m3, or during emergency and spills. Follow applicable

respirator use standards and regulations.

OTHER PROTECTIVE EQUIPMENT: Safety shower and eye wash stations should be available.

Monitoring should be performed regularly to determine exposure levels.

SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES

CHEMICAL FORMULA C6Cl5OH

MOLECULAR WEIGHT 266.32

FORMULATION: Technical concentrate

PHYSICAL STATE: Solid

COLOR: Brownish- grey

ODOR: Phenolic

BOILING POINT: 310ºC @ 760 mm Hg

MELTING POINT: 190º C

FREEZING TEMPERATURE: Not applicable

VAPOR PRESSURE: 40 mm Hg @ 211.2º C

VAPOR DENSITY: 9.2

EVAPORATION RATE: Not applicable

SPECIFIC GRAVITY: 1.98 (Water = 1.0)

BULK DENSITY: 123.6 lb/ft3 @ 20º C

SOLUBILITY IN WATER: 14 ppm @ 20º C

SECTION 10: STABILITY AND REACTIVITY

Chemical Stability: Stable under normal conditions.

Conditions to avoid: Excessive heat, sunlight, contact with open flames, electrical arcs or

hot surfaces which may cause decomposition.

Materials to avoid: Strong oxidizers and alkalis.

Hazardous Decomposition

Products: Hydrogen chloride, chlorine, chlorinated hydrocarbons.

Hazardous Polymerization: Not known to polymerize.

Page 5 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 11: TOXICOLOGICAL INFORMATION

Acute Oral LD50 (rat): 27 mg/kg

Acute Dermal LD50 (rat): 96 mg/kg

Acute Inhalation (rat – 4 hr): 200 mg/kg

Primary Eye Irritation (rabbit): Not a primary irritant

Primary Dermal Irritation (rabbit): Slight irritant

Dermal Sensitization: Not expected to cause sensitization

EFFECTS OF OVEREXPOSURE: Acute overexposure symptoms include sneezing, weakness,

excessive sweating, headache, nausea, vomiting, difficulty in breathing, unconsciousness, convulsions

and death. Chronic exposure has caused toxic liver and kidney effects in lab animals. Exposure to

pentachlorophenol during pregnancy should be avoided.

SECTION 12: ECOLOGICAL INFORMATION

This product is toxic to fish and wildlife. Do not apply directly to water or to areas where surface water is

present or to intertidal areas below the mean high water mark. Do not contaminate water by cleaning of

equipment or disposal of wastes.

Do not discharge effluent containing this product into lakes, streams, ponds, estuaries, oceans or other

waters unless and in accordance with requirements of a National Pollutant Discharge Elimination System

(NPDES) permit, and that the permitting authority has been notified in writing prior to discharge. Do not

discharge effluent containing this product to sewer systems without previously notifying a local sewage

treatment plant authority. For guidance, contact your State Water Board or Regional Office of the EPA.

SECTION 13: DISPOSAL CONSIDERATIONS

PESTICIDE DISPOSAL: Pesticide wastes are toxic. Improper disposal of excess pesticide, spray

mixture, or rinsate is a violation of Federal law. If these wastes cannot be disposed of by use according to

label instructions, contact your State Pesticide or Environmental Control Agency, or the Hazardous Waste

representative at the nearest EPA Regional Office for guidance.

CONTAINER DISPOSAL: Triple rinse or equivalent. Then offer for recycling or reconditioning, or

puncture and dispose of in a sanitary landfill, or by other procedures approved by state and local

authorities.

SECTION 14: TRANSPORT INFORMATION

DOT DESCRIPTION: RQ, Pentachlorophenol, 6.1, UN 3155, PG II, Marine Pollutant

FREIGHT DESCRIPTION: Toxic, 3155, Class 6 (PLACARD REQUIRED)

EMERGENCY RESPONSE GUIDE (ERG): Page 256 Guide 154

Page 6 of 7

MATERIAL SAFETY DATA SHEET

KMG-B Penta OL Technical Pentachlorophenol

SECTION 15: REGULATORY INFORMATION

UNITED STATES EPA: EPA Reg. No. 61483-3

EPA Signal Word: DANGER - POISON

OTHER: SARA 313 Inventory Ingredients – Subject to reporting requirements

CERCLA REPORTABLE QUANTITY – 10 Lbs/4.54 KG

CALIFORNIA PROPOSITION 65 – Listed as known carcinogen

OTHER RIGHT TO KNOW STATES - New Jersey, Pennsylvania, Minnesota,

Massachusetts

SECTION 16: OTHER INFORMATION

This Material Safety Data Sheet may be used to comply with OSHA’s Hazardous Communication

Standard, 29 CFR 1910.1200, and the Standard must be consulted to ensure full compliance.

KMG-Bernuth, Inc. believes that the information and recommendations contained herein (including data

and statements) are accurate as of the date thereon. NO WARRANTY OF FITNESS FOR ANY

PARTICULAR PURPOSE, WARRANTY OR MERCHANTABILITY, OR ANY OTHER

WARRANTY, EXPRESSED OR IMPLIED, IS MADE CONCERNING THE INFORMATION

PROVIDED HEREIN. The information provided herein relates to the specific product designated and

may not be valid where such product is used in combination with any other materials or in any process.

Further, since the conditions and methods of use of the product and of the information referred to herein

are beyond the control of KMG-Bernuth, Inc, KMG-Bernuth, Inc. expressly disclaims any and all liability

as to any results obtained or arising from any use of the product or reliance on such information..

MSDS No.: 6148303

Revision No.: 3

Supersedes: August 30, 2007

Date: November 6, 2009

Approved by: R. Jackson

Page 7 of 7

Material Safety Data Sheet Dura-Treat 40 Wood Preserver®

Version: Revision 4 Date Issued: 11/6/09 MSDS No. 6148302

SECTION 1. CHEMICAL PRODUCT AND COMPANY IDENTIFICATION

COMPANY: KMG- Bernuth, Inc.

9555 W. Sam Houston Parkway S., Suite 600

Houston, Texas 77099

PHONE NUMBER: 713-600-3800

EMERGENCY PHONE: CHEMTREC: 1-800-424-9300

NAME USED ON LABEL: Dura-Treat 40 Wood Preserver

PRODUCT USE: Wood Preservative

SECTION 2: COMPOSITION/INFORMATION ON INGREDIENTS

IDENTITY CAS NUMBER TYPICAL % OTHER INFORMATION Pentachlorophenol 87-86-5 38.0-42.0

Other Chlorophenols Mixture 1.0-2.0

Aliphatic Esters and Aldehydes Mixture 57.0-61.0 Ingredients not precisely identified are proprietary or non-hazardous.

Values are not product specifications.

SECTION 3: HAZARDS IDENTIFICATION

HEALTH HAZARDS: Primary Exposure Routes via inhalation and skin absorption.

Inhalation: Pentachlorophenol may be fatal if inhaled. Symptoms of over-exposure include sneezing,

weakness, excessive sweating, headache, nausea, vomiting and difficult breathing. High concentrations

can cause unconsciousness, convulsions and death. Concentrations greater than 1 mg/m3 can cause nasal

irritation.

Skin: Pentachlorophenol can be harmful or fatal if absorbed through the skin. It causes skin burns on

prolonged or repeated contact. An allergic reaction may develop in a limited number of persons.

Eyes: Pentachlorophenol causes irritation to the eye at 1 mg/m3. If exposure is prolonged, slight

transient corneal damage may occur.

Ingestion: Pentachlorophenol may be fatal if ingested. Symptoms of overexposure include sneezing,

weakness, excess sweating, headache, nausea, vomiting and difficult breathing. High concentrations can

cause unconsciousness, convulsions and death.

Chloracne: Human exposure to pentachlorophenol may result in the development of chloracne. The

usual symptoms of chloracne are the formation of blackheads, whiteheads and yellow cysts over the

temples and around the ears. Mild cases resemble other forms of acne or skin changes observed with

aging. Symptoms reverse upon removal of exposure source.

Page 1 of 6

MATERIAL SAFETY DATA SHEET

Dura-Treat 40 Wood Preserver

SECTION 3: HAZARDS IDENTIFICATION (Continued)

Chronic Toxicity: Chronic overexposure of lab animals to pentachlorophenol has cause toxic effects of

liver and kidneys.

Reproductive Toxicitiy: Pentachlorophenol has been determined to be embryo and fetotoxic to rats but

not to hamsters. Pentachlorophenol has not been found to cause teratogenic effects (birth defects) in lab

animals, but can cause delays in normal fetal development. EPA has expressed an opinion that

pentachlorophenol may produce defects in the offspring of lab animals. Exposure to pentachlorophenol

during pregnancy should be avoided.

Carcinogenicity: The National Toxicology Program (NTP) has evaluated pentachlorophenol for possible

cancer causing effects in lab animas and has indicated s statistically significant increase in benign liver

tumors. Vascular tumors were seen in female mice but not males. Increased medulla tumors were

observed in both sexes of mice. To other carcinogenicity studies, one in mice and one in rats, failed to

show increased incidence of tumors. The International Agency for Research on Cancer (IARC) has

concluded there is sufficient evidence of carcinogenicity to lab animals and inadequate evidence of

carcinogenicity to humans, resulting in a classification as a 2B animal carcinogen.

SECTION 4: FIRST AID MEASURES

IF SWALLOWED: Call a poison control center or doctor immediately for treatment advice. Have person sip a

glass of water if able to swallow. Do not give anything by mouth to an unconscious person. Do not induce

vomiting unless told to by a poison control center or doctor.

IF IN EYES: Hold eye open and rinse slowly and gently with water for 15-20 minutes. Remove contact lenses, if

present, after the first 5 minutes, then continue rinsing. Call a poison control center or doctor for treatment advice.

IF ON SKIN OR CLOTHING: Take off contaminated clothing. Rinse skin immediately with plenty of water for

15-20 minutes. Call a poison control center or doctor for treatment advice.

IF INHALED: Move person to fresh air. If person is not breathing, call 911 or an ambulance, then give artificial

respiration, preferably mouth-to-mouth if possible. Call a poison control center or doctor for further treatment

advice.

NOTE TO PHYSCIAN: This product is a metabolic stimulant. Treatment is supportive. Forced Diuresis may be

effective to reduce total body-burden. Treat hyperthermia with physical measures. Do not administer aspirin,

phenothiazines or atropine since they may enhance toxicity.

Have the product container or label with you when calling a poison control center or doctor, or going for

treatment. You may also contact 1-800-322-8177 for emergency medical treatment.

SECTION 5: FIREFIGHTING MEASURERS

FLASH POINT: ~150 - ~200 ºF (ASTM D-93, Pensky-Martens Closed Cup)

AUTOIGNITION TEMPERATURE: Not Determined

FLAMMABLE LIMITS (LEL/UEL): Not Determined

EXTINGUISHING MEDIA: Use dry chemical, carbon dioxide or foam.

Page 2 of 6

MATERIAL SAFETY DATA SHEET

Dura-Treat 40 Wood Preserver

SECTION 5: FIREFIGHTING MEASURERS (Continued)

PROTECTIVE EQUIPMENT: Fire fighters should wear MSHA/NIOSH approved self-contained positive-

pressure breathing apparatus and full protective clothing. Avoid exposing the skin to the product.

NFPA RATING: Health 3 Fire 2 Reactivity 0

SPECIAL HAZARDS: Unusual Fire and Explosion Hazards – Fumes and vapors from the hot or burning product

may contain hydrogen chloride (HCl), carbon monoxide (CO) and carbon dioxide (CO2).

SPECIAL FIRE FIGHTING PROCEDURES: Use blanketing effect to smother fire. Avoid spraying water

directly into stored containers because of the danger of boil-over of contaminated water.

SECTION 6: ACCIDENTAL RELEASE MEASURES

METHODS FOR CLEANING UP: Do not dispose of spilled material in streams or waterways. Improper

disposal of excess pesticide, spray mixture, spills or rinsate is a violation of Federal law

Spills: Restrict access to the spill area. Ventilate the spill area. Wear suitable protective clothing. For small spills,

absorb the liquid on clay or vermiculite. Sweep up absorbent material and place in an approved container for

disposal according to the applicable State and Federal laws. For large spills, eliminate all sources of ignition, stop

the flow of product from the spill source, restrict access to the spill area, dike the area to prevent spreading, collect

all pumpable quantities into a recovery vessel, absorb the remaining liquid on clay or vermiculite, sweep up ab-

sorbent material and place in an approved container for disposal according to the applicable State and Federal laws.

Reportable Quantity: Reportable quantity (RQ) is 10 lbs. which is approximately 2.5 gallons of this product.

Spills in excess of the reportable quantity must be reported to the United States Environmental Protection Agency’s

National Response Center at 800-424-8802.

Waste Disposal: Pesticide wastes are toxic. Dispose of wastes and residues of this product in accordance with

state and federal regulation. If these wastes or residues cannot be disposed of in accordance with label directions,

contact your state Pesticide or Environmental Control Agency, or the Hazardous Waste Representative of the

United States Environmental Protection Agency for guidance. It is the responsibility of the user to determine which

state and federal regulations apply to the user’s facility.

SECTION 7: HANDLING AND STORAGE SECTION

REQUIREMENTS FOR STORAGE ROOMS: Store away from food or feed is a secure, well-ventilated area

protected from extremes of temperature. Avoid bringing this product into contact with open flames, electric arcs or

hot surfaces which can cause thermal decomposition. Store only in tightly closed original container.

SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION

OCCUPATIONAL EXPOSURE LIMITS:

ACGIH TLV TWA (8 hour) 0.5 mg/m3 OSHA PEL TWA (8 hour) 0.5 mg/m

3

VENTILATION: Do not use in closed or confined space. Open door and/or windows. Provide exhaust

ventilation or other engineering controls to keep the airborne concentration below 0.5 mg/m3.

Page 3 of 6

MATERIAL SAFETY DATA SHEET

Dura-Treat 40 Wood Preserver

SECTION 8: EXPOSURE CONTROLS/PERSONAL PROTECTION (Continued)

BODY PROTECTION: Wear PVC, neoprene, NBR(Buna-N), nitrile latex or equivalent gloves and tightly

woven clothing including long sleeve shirt when handling pentachlorophenol. When mixing penta solutions, wear

protective clothing, gloves, boots or shoes, which are suitable for the solvent used.

HYGIENE: Avoid contact with skin and breathing mist or fumes. Do not eat, drink or smoke in work area. Wash

hands prior to eating, drinking or using restroom. Shower and change into uncontaminated clothing before leaving

work premises. Wash clothing before re-use. Do not wash with household laundry.

EYE PROTECTION: Use protective eyewear. Do not wear contact lenses. When mixing penta solutions, wear

chemical goggles and/or face shield.

RESPIRATORY PROTECTION: Where concentrations of pentachlorophenol exceed or are likely to exceed

0.5 mg/m3, a NIOSH/MSHA approved organic vapor-dust filter type respirator is acceptable. A NIOSH/MSHA

approved self-contained breathing apparatus or air line respirator with full face piece, is required for concentrations

above 150.0 mg/m3, or during emergency and spills. Follow applicable respirator use standards and regulations.

OTHER PROTECTIVE EQUIPMENT: Safety shower and eye wash stations should be available. Monitoring

should be performed regularly to determine exposure levels.

SECTION 9: PHYSICAL AND CHEMICAL PROPERTIES

CHEMICAL FORMULA C6Cl5OH

MOLECULAR WEIGHT 266.32

FORMULATION: 40 % Solution

PHYSICAL STATE: Liquid

COLOR: Dark

ODOR: Phenolic

BOILING POINT: ≥ 214º F

MELTING POINT: Not applicable

FREEZING TEMPERATURE: Not applicable

VAPOR PRESSURE: > 0.4 mm Hg @ 60º F

VAPOR DENSITY: 4.5 (Air = 1.0)

EVAPORATION RATE: < 1 (n-BuAc = 1)

SPECIFIC GRAVITY: 1.15 – 1.17 (Water = 1.0)

BULK DENSITY: 9.60 – 9.76 lb/gal @ 20º C

SOLUBILITY IN WATER: Insoluble

SECTION 10: STABILITY AND REACTIVITY

HAZARDOUS REACTIONS (CONDITIONS TO AVOID): Stability: Stable under normal conditions. Avoid contact with open flames, electric arcs or hot surfaces.

Incompatibility: Avoid contact with strong oxidizers.

Hazardous polymerization: Material is not known to polymerize.

HAZARDOUS DECOMPOSITION PRODUCTS: Hydrogen chloride, chlorine, carbon monoxide, carbon

dioxide, polychlorinated dibenzodioxins and polychlorinated dibenzofurans.

Page 4 of 6

MATERIAL SAFETY DATA SHEET

Dura-Treat 40 Wood Preserver

SECTION 11: TOXICOLOGICAL INFORMATION

Acute Oral LD50 (rat): 1.58 g/kg

Acute Dermal LD50 (rabbit): 4.20 g/kg

Acute Inhalation (rat – 4 hr): >20 mg/kg

Primary Eye Irritation (rabbit): Not a primary irritant

Primary Dermal Irritation (rabbit): Slight irritant

Dermal Sensitization : Not expected to cause sensitization

EFFECTS OF OVEREXPOSURE: Acute overexposure symptoms include sneezing, weakness, excessive

sweating, headache, nausea, vomiting, difficulty in breathing, unconsciousness, convulsions and death. Chronic

exposure has caused toxic liver and kidney effects in lab animals. Exposure to pentachlorophenol during pregnancy

should be avoided.

SECTION 12: ECOLOGICAL INFORMATION

ECOTOXICITY ASSESSMENT: Maybe toxic to aquatic wildlife.

OTHER ECOLOGY INFORMATION: Toxic to wildlife.

SECTION 13: DISPOSAL CONSIDERATIONS

DISPOSAL METHOD: Wastes resulting from the use of this product may be disposed of on site or at an

Approved waste disposal facility. Do not contaminate waterways by cleaning of equipment or by disposal of

wastes.

CONTAINER DISPOSAL: Empty containers retain product residue. Triple rinse, or equivalent, empty

container, return rinse water to dilution mixture, and dispose of dilution mixture as hazardous waste if it cannot be

disposed of by use according to label instructions. Do not ruse container. Offer it for recycling or reconditioning,

or puncture and dispose of in properly permitted landfill.

SECTION 14: TRANSPORT INFORMATION

DOT PROPER SHIPPING NAME: UN 1306, Wood Preservatives, Liquid, Flammable, 3, PG II, Marine

Pollutant (pentachlorophenol), RQ (pentachlorophenol)

PLACARD: FLAMMABLE

EMERGENCY RESPONSE GUIDE (ERG): Guide 129

SECTION 15: REGULATORY INFORMATION

UNITED STATES EPA: EPA Reg. No. 61483-2

EPA Signal Word: DANGER - POISON

OTHER: SARA 313 Inventory Ingredients – Subject to reporting requirements

CERCLA REPORTABLE QUANTITY – 10 Lbs/4.54 KG

CALIFORNIA PROPOSITION 65 – Listed as known carcinogen

OTHER RIGHT TO KNOW STATES - New Jersey, Pennsylvania, Minnesota,

Massachusetts Page 5 of 6

MATERIAL SAFETY DATA SHEET

Dura-Treat 40 Wood Preserver

SECTION 16: OTHER INFORMATION

This Material Safety Data Sheet may be used to comply with OSHA’s Hazardous Communication

Standard, 29 CFR 1910.1200, and the Standard must be consulted to ensure full compliance.

KMG-Bernuth, Inc. believes that the information and recommendations contained herein (including data

and statements) are accurate as of the date thereon. NO WARRANTY OF FITNESS FOR ANY

PARTICULAR PURPOSE, WARRANTY OR MERCHANTABILITY, OR ANY OTHER

WARRANTY, EXPRESSED OR IMPLIED, IS MADE CONCERNING THE INFORMATION

PROVIDED HEREIN. The information provided herein relates to the specific product designated and

may not be valid where such product is used in combination with any other materials or in any process.

Further, since the conditions and methods of use of the product and of the information referred to herein

are beyond the control of KMG-Bernuth, Inc, KMG-Bernuth, Inc. expressly disclaims any and all liability

as to any results obtained or arising from any use of the product or reliance on such information..

MSDS No.: 6148302

Revision No.: Revision 4

Supersedes: November 20, 2007

Date: November 6, 2009

Approved by: R. Jackson

Page 6 of 6

APPENDIX III

March 30th, 2010 American Wood Preservers’ Association Subject: Reaffirmation of Pentachlorophenol (PENTA) in the Wood Pole Industry AWPA Representatives: Central Power is an electric cooperative which has facilities that spread over the

central and southeastern parts of North Dakota. Central Power has used wood

poles as their primary support structure on the transmission lines throughout its

territory. It has been Central Power’s experience that even though the wood

species (WRC, DF, LP) may have changed from project to project, the treatment

to those poles has not. Pentachlorophenol (Penta) has been Central Power’s

main wood pole preservative used in its wood pole specification and guidelines.

Central Power is proud to say that the wood poles with PENTA preservative have

performed extremely well during its routine groundline inspection program over

the last 50-plus years. Central Power’s wood pole rejection rate over the last 4

years of annual groundline inspections has been less than 1%. Central Power is

very confident that Penta pressure treatment to the wood poles installed in our

system has provided an extended service life to our transmission lines. Central

Power supports the use of pentachlorophenol (Penta) preservative in utility wood

poles and strongly urges AWPA to reaffirm the wood preservative.

Sincerely,

525 20th Avenue Southwest - Minot, ND 58701 Phone 701/852-4407 – Headquarters Fax 701/852-4401 – Operations & Engineering Fax 701/852-4402 www.centralpwr.com

Central Power Electric Cooperative, Inc.

Ryan Callahan

Ryan Callahan, P.E. Chief Transmission Engineer Central Power Electric Cooperative, Inc.

April 5, 2010 Dear American Wood Preservers’ Association Distribution Engineering, an agency within American Electric Power is completely behind the reaffirmation of pentachlorophenol (Penta). Distribution Engineering has been specifying Penta in its material specification for wood pole and crossarms, along with pressure treating requirements for many years. On average 97% of poles (southern yellow pine) and 100% of crossarms (douglas fir) purchased for distribution structures are penta treated. Penta has been proven to provide excellent service life and is accepted as the treatment of choice amongst our line personnel. Distribution Engineering believes that penta needs to be reaffirmed. Sincerely, Dale Thompson Senior Technician Distribution Engineering American Electric Power

Subject: RE: AWPA PENTA TASK FORCE Date: Monday, April 5, 2010 12:34 PM From: LesL@ldm.com To: Mike Freeman <wooddoc@aol.com> Mike Thanks for forwarding me a copy of the paper and Poster both you and John did. I fully support the reaffirmation of pentachlorophenol in the AWPA Book of Standards. As the primary preservative requested by our customers it is vitally important for us to have this preservative system reaffirmed. Regards Les Lonning LESL@LDM.com 800-841-7809 From: wooddoc@aol.com [mailto:wooddoc@aol.com] Sent: Tuesday, March 23, 2010 1:55 AM To: Les Lonning; dennis.morgan@fprl.com; rick.bleskey@blpole.com; jbrient@comcast.net; JFalcone@stella-jones.com; dick.jackson@pacificwood.com; WilkinsonJ@verizon.net; jeff_miller@treated-wood.org; drs@conradFP.com; drs@conradwp.com Cc: navnit.upadhyay@lanxess.com; Futong.Cui@ruetgers-organics.de Subject: AWPA PENTA TASK FORCE Dear AWPA Penta Task Force Members: It is my intent to bring a motion to Re Affirm Penta in the old P-8 Standards and the new Stand Alone Penta Standard( new as a Draft) using the attached Penta Product and efficacy review as the Penta Re-Affirmation Data Package backbone. As Task Force Chair, the project sponsor, KMG-B/KMG Chemicals asked me to also present the Data Package in the form a formal written paper and a Tech Forum as the recent SE Pole Conf held last month here in Memphis. Both the full paper and the poster session is attached for your info and files. I would like to hear from all of you, as soon as possible, as I would like the recommendation to Re Affirm Penta in the AWPA Standards to come not just from me, but from the entire Task Force, if possible. Best regards, Mike Mike H. Freeman AWPA Penta TF Chair-Subcommittee P-3

March 29, 2010 Re: Pentachlorophenol

To: Whom it May Concern The Pacific Wood Preserving Companies utilize the Pentachlorophenol to produce a variety of treated wood products, primarily treated wood utility poles. This preservative is the most often requested and widely accepted preservative for the treatment of Douglas Fir Utility Poles. It is important that this preservative be reaffirmed in the American Wood Protection Association Standards. Best regards,

Elaina Jackson Chief Operating Officer The Pacific Wood Preserving Companies

To: Dan Imholte Bell Lumber & Pole From: Bob Akers Purchasing Supervisor East Central Energy Re: Pentachlorphenol Wood Preservative East Central Energy is in support of the use Pentachlorphenol as an AWPA standardized wood preservative in the treatment of utility poles. We have used distribution class poles treated with this preservative for several years without any issues. 4/9/10