UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, DC 20460

			OFFICE OF  PREVENTION, PESTICIDES,  AND TOXIC SUBSTANCES

 									Feb.14, 2008

	MEMORANDUM

Subject: 	Environmental Fate and Transport Assessment of  Creosote for the Reregistration Eligibility Decision (RED) Process.

From:	A. Najm Shamim, PhD, Chemist

	Regulatory Management Branch II

	Antimicrobials Division (7510P)

To:	Jackie McFarlane, CRM for Creosote RED

	Regulatory Management Branch I

	Antimicrobials Division (7510P)

			And

	 Timothy McMahon, PhD, Senior Toxicologist

and Risk Assessor for Creosote RED

	Risk Assessment and Science Support Branch

	Antimicrobials Division (7510P)

Thru:	Mark Hartman, Chief

	Regulatory Management Branch II

	Antimicrobials Division (7510P)

DP Barcode:  D246550

CREOSOTE - ENVIRONMENTAL FATE AND TRANSPORT RISK ASSESSMENT

I.  Executive Summary:

Creosote is an oil-based wood preservative which is primarily used for preserving wood used in railroad ties and utility poles.  Coal tar creosote or the P1/P13 and P2 fractions of  coal tar creosote are obtained from the carbonization of bituminous coal and are mixtures of organic molecules (about 200-250  identifiable substances) consisting of simple polyaromatic hydrocarbons (PAH), multi-aromatic fused rings, cyclic nitrogen-containing heteronuclear compounds, and phenolic substances.  It is estimated that about 85 percent of the creosote mixture consists of PAHs and the remainder consists of cyclic heteronuclear nitrogen and oxygen containing molecules.  Since the PAHs constitute the majority of the percent mass of the P1/P13 and P2 fractions of creosote, they weigh heavily in the environmental fate assessment.  Therefore, the Agency has carried out an open literature search for environmental fate and transport studies on the creosote mixture and has decided to make the assessment based on the PAH constituents only.

The Agency has reviewed open literature and also studies submitted by industry for the RED process and this chapter outlines the possible  environmental risks from creosote uses.

Research and literature on creosote science is huge. The experiments conducted on leaching from the treated wood and environmental fate type studies carried out by various  researchers were done under different conditions, and the data on creosote fate and transport parameters sometime contradictory. However, some general trends do emerge which help the Agency to make a few conclusions

Coal tar creosote has been used as a wood preservative pesticide for over 125 years.  According to the American Wood Preservers’ Association (AWPA,1997) statistics, an estimated 728 million cubic feet of wood was treated with preservatives, and creosote and its mixtures represent 13.3 percent of the treatments.  Nearly 100 percent of railroad crossties, switch ties and bridge timbers are pressure-treated with creosote and 14.6 percent of utility poles are treated with creosote (Webb, N.D.).

Process wastewater, dumpsite leachate, storage tank leaks, and spills are the major creosote sources to the environment (Merril and Wade, 1985). In addition, leachates from pressure treated wood can migrate out into soils, and water.  The environmental fate and transport of creosote as addressed here focuses primarily on the likely exposure of PAHs into three environmental compartments: 1) leaching of creosote mixture into surface and ground waters from the railroad ties and utility poles; 2) migration into soil/sediments from the railroad ties and utility poles, and 3) bioaccumulation into the aqueous and benthic organisms.

	Recent studies conducted by Ken Brooke ( Sooke Basin, 2001 and Railroad ties, 2004) some important trends emerge: 1) Creosote treated wood does leach out its constituents; 2) leaching process is acute at the start of the and tapers off with time; 3) leachate in water soil consists of a mixture  the PAHs ranging from low molecular weight to high molecular weight; 4) migration of PAHs from the pole or railroad ties  is limited to a short distance: maximum up to 10 meters away from the line of origin and not more than 60 cm vertically down; 5) initial mixture ratio for low to high molecular weight PAHs is 1:1 while with the passage of time (385 days),in favor of  high molecular weight PAHs.; 6) there is possibly an acute impact at short distances away from utility poles or railroad ties. 7) some high molecular weight PAH s like benzo (e)pyrene are persistent in soils.

2.  Environmental Fate and Transport of Creosote

The major uses of creosote since 1988 have been railroad ties, crossbars, decks on marinas and utility poles.  Polyaromatic hydrocarbons (PAHs) constitute the highest percent

(85%) of coal tar creosote while the phenolic substances are about 10 percent, and N– and S- containing substances represent the remainder of the mixture.  Most of the PAHs are non-volatile, therefore; creosote normally does not contaminate the air.  The major route of exposure from creosote is through water and soil, and from these environmental compartments into the aquatic and benthic organisms (bioaccumulation).

Abiotic Degradation

The PAHs are fused aromatic polycyclic rings which have no hydrolysable hydrogens and the solubility of these compounds are very low in water.  Environmentally, hydrolysis does not appear to be an important pathway for dissipation of the composite mixture of PAHs in water; however, some molecules like benzo[k]fluoranthene and benz[a]pyrene could persist in water.

Very few studies are reported in the open literature on field volatilities for PAHs present in creosote.  Gevao et al. (1998) showed that acenaphthene, fluorene, phenanthrene, anthracene, and fluoranthene volatilized at a faster rate at 30(C than at 4(C.  The study also showed that 85 percent of these components remained in the wood after seven weeks.  The rate of volatilization was slow for acenaphthene (half-life, one year) and fluoranthene (half-life, one year).  In most cases, the initial rates of dissipation are caused by partitioning between the wood and air and biodegradation in the presence of microbial populations.  Therefore, exposure to air does not appear to be an important factor in fate assessment for most PAHs.

Photooxidation is a common phenomenon, and therefore an important degradation pathway for the creosote PAHs.  The photolytic half-lives of the PAHs in aqueous medium are dependent on the season, geographical location, surface water measurements, and complexities of the parent molecules (two fused rings vs. five fused rings).  In most cases, half-lives under the conditions mentioned do not appear very long.  Because of this, and the fact that most of the PAHs are not readily soluble (except for a few low molecular weight ones), the PAHs may not be a problem in surface and groundwater runoffs.  However, it should be noted that the photooxidized products of PAHs are stable; therefore, may persist in air/water and soils and become an environmental concern as these photooxidized products are also bioaccumulative.

Mobility

Once introduced to an aquatic environment, creosote components are subjected to several fractionation processes.  Many PAHs adsorb to sediments and may persist for long periods of time.  Creosote contaminated sediments usually contain relatively higher levels of hydrophobic PAHs than whole creosote (Bieri et al., 1986).  Eventually, sediment adsorbed PAHs may dissolve or become re-suspended in the water by tides, storms, bioturbation, shipping, or dredging.  As a result, local biota may be exposed to low level PAHs over the long term (Fowler et al., 1993).  Therefore, the adsorption/desorption processes in water involved with creosote-derived PAHs are a significant consideration in fate assessments of creosote contamination.

Additionally, colloidal matter present in a creosote-contaminated environment has been found to affect the desorption rates of specific PAHs.  One study found that PAHs partitioned to course (of sizes >100 nm) colloid fractions and were linearly correlated with the PAH octanol-water partition coefficient, indicating the partitioning was hydrophobic (Villholth, 1999).

The PAHs from creosote-treated utility poles and/or railway ties tend to leach out initially in the first seven days and remain in the sediment surrounding the poles or railroad ties not migrating far from the wood.  Most of the PAHs, however, tend to stay inside the wood (~85%).  One study showed that background levels for PAHs leached from wood were attained within three months and may have been due to photolysis or biodegradation of the PAHs.  A detailed study of 200 U.S. estuaries showed that PAHs that leached from the treated wood of decks and bulkheads, 175 had muddy sediments.  Higher amounts of PAHs leached into such soil types.  No systematic work has been carried out on all the PAHs and the representative soil types to show which one would have a higher tendency of retention for the PAHs.

Migration studies of PAHs into groundwater have shown that migration of some of the PAHs have been observed.  Vertical or lateral migration of the PAHs from the utility poles indicated that at ground level the migration was not significant beyond 150 meters from the site of contamination (base of utility poles).  The vertical or downward migration of the PAHs was even more limited and the existence of the PAHs were not found below a 12 meter depth.

Biodegradation

Most of the PAHs have a tendency to biodegrade under aerobic conditions.  It has been reported that over eighty percent of biodegradation occurs in the first month after the wood preservative application, with the exception of benz[a]pyrene and benzo[k]fluoranthene, which have shown resistance to biodegradation.  A number of aerobic soil metabolism studies on PAHs conducted at various contaminated sites as well as in simulated microcosms reported that low molecular weight PAHs generally metabolized in aerobic conditions and the greater the oxic environment, the higher the  biodegradation level.

Aerobic degradation of PAHs associated with soil and groundwater often leads to a rapid depletion of dissolved oxygen which eventually decreases the redox potential.  This decrease in the redox potential can result in favorable environments for denitrifying, sulfate-reducing, or methanogenic microbes.  Therefore, anaerobic transformations may be a significant factor in oxygen-depleted habitats (Karthikeyan and Bhandari, 2001).  Under these conditions, anoxic or anaerobic degradation stimulated by denitrifying or sulfate-reducing bacteria can become an important pathway for the cleanup of contaminated sites.

Bioaccumulation in Fish

The major components of the PAHs in creosote have shown the ability to form neutral to oxidized transformation products under aerobic soil/aquatic conditions.  For example, fluorene forms hydroxy fluorene and acenaphthene converts into diacetic acid acenaphthene.  These oxidized species are stable and bioaccumulative.  Numerous studies have shown that photooxidized transformation products of these PAHs are bioaccumulative and result in adverse effects on the aqueous biota as well as on the organisms in the soils and benthic sediments.

In aquatic habitats, fish, shellfish, and crustaceans readily bioaccumulate PAHs from the environment and store these at high levels in the tissues.  Seven PAHs: naphthalene, anthracene, phenanthrene, pyrene, 9-methyl anthracene, benz[a]anthracene and perylene were shown to bioaccumulate in Daphnia pulex.  PAHs like naphthalene, biphenyl/acenaphthylene, fluorene, phenanthrene/anthracene/chrysene, and benzopyrene were found to bioaccumulate in clams (Rangia cuneate).  The most dramatic increases were in cases such as  benz[a]anthracene/chrysene which reported a bioaccumulation of 41 ppb (week zero) and increased to 190 ppb (week 4).  Similarly, benzopyrene bioaccumulated from 8 ppb (week zero) to 600 ppb (week 4).  Depuration was within two weeks.  This study was conducted after the creosote spill into the Bayou Bonfuca at the American Creosote Works Plant Site at Slidell, Louisiana.

A study on benthic invertebrates showed a bioaccumulation concentration ranging from 0.10 to  11.00 ppm.  A bioconcentration study on zebra mussels in the Great Lakes found that pre-spawning species (high lipid) bioaccumulated benzo[a] pyrene at a faster rate than the post- spawning (low lipid) species.

Bioaccumulation data on marine mammals are not readily available, and only one study on whales and seals has been reported.  That study indicated a bioaccumulation of 0.10 and 1.21 ppm in the muscles of these mammals, respectively.

Some of the PAHs, particularly those that have a high molecular mass (higher number of the fused aromatic rings) have a higher tendency to adsorb to soil organic carbon.  Such adsorption coefficients (KOC) have been reported in literature.  Some PAHs with a high Koc can bind strongly with the organic carbon of the soils/sediments and may not be bioavailable to the aquatic organisms. However, if the octanol/ water coefficients (Kow) is high, and if the PAHs are desorbed from the soils/sediments to which they are bound, some of these PAHs can become bioaccumulative to the benthic organisms.

It has been suggested that based on theoretical calculations and modeling, the half-lives of the PAHs obtained from coal tar creosote can be estimated in air, water, soils and sediments.   From these calculations and modeling, one can arbitrarily divide the PAHs into 3 distinct groups: PAHs with two fused rings, PAHs with three fused rings and PAHs that have 4 to 5 fused rings. The half-lives in the environmental compartments (air, water, and soils) for PAHs are as follows: the half-lives of two fused rings PAHs < three fused rings < 4/5 fused rings.  The Kow values lie between 3 and 4 for PAHs with two fused rings, between 4 and 5 for PAHs with 3 fused rings, and at 6 or above for the third group of the PAHs.  In general, the half-lives in air and water environmental compartments are much lower than in soils/sediments because the soil adsorption coefficients are higher.  The longer the half-life, the greater the persistence of the PAHs in soils.  Some of the 4/5 fused ring PAHs are more persistent in soils and sediments and since their Kow values are higher, they can bioaccumulate because some of them adsorb onto soils and they may not be bioavailable for benthic organisms.

The third group of PAHs show a higher degree of bioaccumulation, persistence in soils and water, resistance to biodegradation and photooxidation.  Additionally the components of these group have less of a  tendency to leach from the wood structure and have high sorption constants to soils.  On the other hand, these higher members of the PAHs (4/5 fused ring compounds) are not readily soluble in water and their percent on a mass basis in the creosote mixture is very low compared to the first group (2 fused rings) of the PAHs, and may not be available for biomagnification and migration into surface and ground waters.

B.  APPENDIX OF THE ENVIRONMENTAL FATE AND TRANSPSORT ASSESSMENT For CREOSOTE

A. Chemical Profile

Common Name(s):	Creosote, Creosote Oil, Dead Oil, Brick Oil, Coal Tar Oil, Creosote P1, Heavy Oil, Liquid Pitch Oil, Wash Oil, Creosotum, Cresylic Creosote, Naphthalene Oil, Tar Oil, AWPA #1, and Preserv-o-sote

Chemical Name:	Coal Tar Creosote

Trade Name:		Sakresote 100

Formulations:		Distillate mixture obtained from bituminous coal; oil-based

Physical/Chemical Properties:

Molecular formula:	It is a multi-component mixture. Not applicable

Molecular weight:	It is a multi-component mixture. Not applicable

Physical State:	Translucent brown to black; yellowish to dark green-brown; oily liquid

Melting Point:	Not available

Boiling Point:	194-400(C. Not possible to define a boiling point of  a multi-component mixture

Viscosity:	14.60 mm/s (P1/P13); 15.5 mm/s (P2)

Vapor Pressure:	11.1 mm Hg at 24.4(C (P1/P13); 8.6 mm Hg at 24.4 to 24.5(C (P2)

Dissociation Constant: 3.247 (pKa, P1/P13); 3.311 (pKa, P2)

Solubility: (Water)	313 µg/mL (P1/P13); 306 µg/mL (P2); temperature not specified

Henry’s Law Constant: Not available. Not possible to determine for a multi-component  mixture

Octanol/Water Partition Coefficient (log Kow): 1.0

 Studies have not been submitted to the Agency and specific guideline requirements have not been fulfilled for creosote.  Therefore, the Agency has carried out an open literature search for environmental fate studies on creosote mixtures and has decided to make the assessment based on the PAH constituents only.  The literature search on environmental fate studies provided data on the volatility, photolysis in water, aerobic/anaerobic metabolism, leaching and adsorption/desorption, bioaccumulation in aquatic and benthic organisms, and migration from poles into soils.  The following are summaries of studies obtained from the literature search.

II a.

Volatility

Lindhardt, B. and T.H. Christensen, 1996

A laboratory volatilization study was conducted on the non-steady-state fluxes of aromatic hydrocarbons from coal tar contaminated soil.  The contaminated soil samples, obtained from Holte, Denmark, were placed below a 5 cm deep layer of uncontaminated soil and monitored for 53 days.  The contaminated soil contained 50 to 840 µg/cm3 of 11 selected aromatic hydrocarbons.  In analyses where the microbial activity was inhibited, the fluxes stabilized on a semi-steady state level for monocyclic aromatic hydrocarbons, naphthalene and 1-methylnaphthalene after 10 to 20 days.  Acenaphthene and fluorene fluxes were measurable only in experiments using a soil cover with a low organic content.  When the soil cover was adapted to degrade naphthalene, the fluxes of naphthalene and 1-methylnaphthalene were approaching the detection limit at 5 to 8 days.

Gevao, B. and K.C. Jones, 1998

A volatilization study for five PAHs (acenaphthene, fluorene, phenanthrene, anthracene and fluoranthene) from treated (painted) wood was conducted in the United Kingdom.  This laboratory study was performed using glass chambers equipped with an air inlet/outlet in 4(C and 30(C environments.  Wood samples painted with 110 grams of creosote were placed in the glass chambers and the air traps were changed at each sampling interval.  Samples were stored for 2 to 4 weeks at -17(C prior to extraction.  The rate of desorption was analyzed using first order kinetics for all five PAHs and was found to be higher at 30o C than at 4oC.  The mean PAH values ranged from 2.57 ± 1.52 mg/m2 treated wood/day and 29.5 ± 6.1 mg/m2 treated wood/day at 4(C and 30(C, respectively.  From the desorption rates, the half-life at 4oC ranged from 0.70 year to 31 years for fluoranthene and acenaphthene, respectively.  When the temperature was raised to 30(C, the half-life ranged from 0.3 year to 1 year for fluroanthene and acenaphthene, respectively.  Following a long-term study at 4(C, it was observed that the volatilization rate was constant for about seven weeks after which it was estimated that >85 percent of the PAHs remained in the wood.  The authors noted that initial desorption rates were caused by partitioning between the wood and air, and by the rates of compound diffusion from the interstices of the wood.

II b. Aqueous Photolysis

Kirso, U., 1991

A photolysis study in natural sunlight in aqueous (~5 x 10-8 M) PAH, aza-PAH and benzene media was performed with selected PAHs.  Table 1 summarizes the photooxidation half-lives of these commercially available highly pure PAHs.  The study also collected data on photolysis by natural sunlight of benzo[a]pyrene under open-sea conditions at northern and southern latitudes.  In this European study, first-order photooxidation rates were measured and first-order rate constants were found.  The Agency has calculated the half-lives using the first-order rate constants from this study.  PAH appear to photolyse through oxidation processes. The results of the calculations are presented in Table 1.

Table 1.  Photochemical Oxidation and Half Lives of Selected PAHs

Compound

Half-life in Water (minutes)

Half-life in Benzene (minutes)

Fluorene

119.97

2.05

Anthracene

8.06

*

Phenanthrene

64.95

107.05

Triphenylene

93.93

136.80

Pyrene

19.99

97.47

Chrysene

25.88

100.54

Benz[a]anthracene

20.92

41.72

Benz[b]anthracene

3.56

0.68

Dibenz[a,c]anthracene

25.57

55.06

Dibenz[a,h]anthracene

22.94

55.06

Dibenz[a,j]anthracene

16.58

41.04

Dibenzo[a]pyrene

15.5

34.20

Dibenzo[e]pyrene

22.94

117.99

Perylene

374.94

51.98

Coronene

312.01

63.95

Benzo[k]fluoranthene

110.98

171.00

Benzo[b]fluoranthene

312.01

190.15

Notes:	1.  Not all the PAHs used in the study are present in the P1/P13 and P2 fractions of the creosote.

2.  PAHs with high molar masses have longer  photooxidation half-lives than smaller PAHs with small molar masses.

3.  * =  Could not be determined under the experimental conditions.

Table 2.  Rate Constants and Half-lives of Photooxidation of Benzo[a]pyrene by Sunlight in Sea Water

Region

Water Temperature

(oC)

Initial Concentration

(10-8 M)

Rate Constant

(k x 10-4) 1/s

Half-life

(minutes)

Bering Sea

14

1.47

1.69

68.3

Bering Sea

16

4.20

1.60

72.2

Tropical Pacific

26

6.59

2.84

40.6

Tropical Pacific

27

2.06

1.60

72.2

Lagune Caroline Atoll

27

1.90

2.99

38.61

Lagune Caroline Atoll

27

0.70

4.20

27.50

Baltic Sea

6

15.6

0.70

146.2

Notes:	1.  ‘K’ is a first-order rate constant.

2.  The Rate constants of photooxidation of benzo[a]pyrene (and half lives) are higher in tropical longitudes than in northern and temperate climatical zones.

Experimental and calculated data on the photolysis of most of the PAHs present in the P1/P13 and P2 fractions of creosote can be found in the international scientific literature.  These data are summarized in the Table 3 below.

Table 3.  Photolysis of Selected PAHs Found in P1/P13 and P2 Fractions of Coal Tar Creosote

Compound

Description

Half lives

Naphthalene

Direct sunlight, 40(N, midday, midsummer (calculated)

71 Hours (Harris, 1982)

Distilled water at 25 o C

25 Hours (Fukuda, 1988)

Quinoline

Sunlight at 40(N, aqueous hydrolysis, pH 6.9

3851 Hours, summer

535 Hours, winter (Mill et al., 1981)

1-Methyl naphthalene

Summer sunlight in surface water

180 Days (Miller, 1985)

2-Methyl naphthalene

Summer sunlight in surface water

410 Days (Mill et al., 1981)

Distilled water

16.4 Hours (Fukuda, 1988)

Acenaphthene

Determined by rotary photoreactor technique on different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

2.0 Hours (Behymer & Hites, 1985)

2.2 Hours (Ibid.)

44 Hours (Ibid.)

Distilled water(irradiated light at wavelength 290 nm)

3 Hours (Fukuda, 1988)

Fluorene

Determined by rotary photoreactor technique on different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

110 Hours (Behymer & Hites, 1985)

62 Hours (Ibid.)

37 Hours (Ibid.)

Anthracene

Midsummer sunlight:

-- deep, slow, somewhat turbid water

-- deep, slow and muddy water

-- deep, slow and clear water

-- Shallow, fast and clear water

-- shallow, very fast and clear water

173.2 hours (Southworth, 1977)

693 hours (Ibid.)

38.5 hours (Ibid.)

8.1 hours (Ibid.)

2.91 hours

At 35( on latitude

-- summer

-- winter

1.6 hours (Ibid.)

4.8 hours (Ibid.)

At 35( N, winter

-- in water

4.62 hours (Callahan, 1979)

Different atmospheric particulate substrate:

-- silica gel

-- alumina

-- fly ash

-- distilled water

2.9 hours (Beymer & Hites,1985)

0.50 hours (Ibid.)

48 hours (Ibid.)

1.0 hour (Fukuda, 1988)

Carbazole

40(N , midday, sunlight in late Jan. and river (calc.)

6.0 hours (Smith, 1978)

In eutrophic pond and eutrophic lake

15.0 hours (Ibid.)

In oligotrophic lake

3.0 hours (Ibid.)

Aqueous medium

1.0 hours (Ibid.)

Fluoranthene

Atmospheric/aqueous photolysis, based on the measured sunlight photolysis rate constant in water

-- summer sunlight, surface water

21 hours (Howard, 1991)

160 days (Mabey, 1982)

Different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

74 hours (Behymer & Hites, 1985)

23 hours (Ibid.)

44 hours (Ibid.)

Chrysene

Different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

100 hours (Behymer & Hites, 1985)

78 hours (Ibid.)

38 hours (Ibid.)

Acenaphthylene

Different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

0.7 hours (Behymer & Hites, 1985)

2.2 hours (Ibid.)

44 hours (Ibid.)

Benz[a]anthracene

Aquatic

10-50 hours (Callahan, 1979)

Stream

20 hours (Smith, 1978)

Eutrophic pond or lake

50 hours (Ibid.)

Oligotrophic lake

10 hours (Ibid.)

Aquatics

0.58 hours (EPA Report 600/7-78-074)

Early March

0.2 days (Zepp, 1980)

-- 1% acetonitrile in filter-sterilized natural water at 313 nm wave length

5 hours

Different atmospheric particulate substrates:

-- silica gel

-- alumina

-- fly ash

4.0 hours (Behymer & Hites)

2.0 hours (Ibid.)

38 hours (Ibid.)

IIc. Aerobic/anaerobic Metabolism

Mueller, J.G. et al., 1993

This laboratory study was designed to evaluate the ability of a sequential inoculation process using selected microorganisms to enhance the bioremediation technologies for the treatment of groundwater contaminated with creosote and PCP.  The contaminated groundwater was obtained from a monitoring well at the American Creosote Works site in Pensacola, Florida.  Both 1.2 L (bench scale) and 454 L (pilot scale) bioreactors were utilized for the analysis.  The bench scale study showed that after 32 days of continuous-flow operation, the majority of the monitored creosote components were degraded.  Overall, for groups 1, 2, and 3 PAHs, the biodegradation values were determined to be 98.0, 96.2, and 89.4 percent, respectively.  The amount of group 2 and 3 PAHs found in the bioreactor residues were 3.5 and 9.2 percent, respectively.  In the pilot scale study, the system was effective in treating the contaminated water in a two-step process.  Since the pattern of degradation favored the low molecular weight components, an additional inoculum of microorganisms selected for their ability to degrade this components were added.  As a result, >98 percent of all the monitored creosote components were removed.  A mass balance distribution analysis showed that of the various routes of removal (adsorption, volatilization, and biodegradation), biodegradation was the primary mechanism for the removal of the creosote components.

National Oceanic and Atmospheric Administration, 1988

The National Oceanic and Atmospheric Administration (NOAA) conducted a detailed study on the analysis of PCBs, PAHs, and 12 trace metals present in surface water sediments of 200 estuaries.  One hundred seventy-five estuaries were contaminated with PAHs.  These estuaries have muddy rather than sandy sediments with the exception of two estuaries in Long Island, where the sediments were predominantly sandy.  The results of the study indicated that PAH contamination was higher in the muddy sediment.

Bouwer, E.J., W. Zhang, L.P. Wilson, and N.D. Durant, 1996

A four-week aerobic study was conducted on the sediment and groundwater of an abandoned manufactured gas plant (MGP) site which was contaminated with creosote PAHs .  The experiment was conducted to assess the ability of the bacteria in sediment to mineralize

14C-labeled benzene, naphthalene, and phenanthrene under simulated field conditions.  The results of this study showed that the bacteria present in the aquifer sediments were able to degrade low molecular weight PAHs.  The study also determined that the higher the concentration of oxygen, the greater the biodegradation of these molecules.  Mineralization for anthracene and phenanthrene ranged from 4 to 23 percent, ranged from 4 to 42 percent for benzene, and from 8 and 55 percent for naphthalene.

Chapman, P.J., M. Shelton, M. Grifoll, and S. Selifonov, 1995

In this study, bacterial cultures were obtained from washing creosote-contaminated soils at lumber treatment facilities.  These cultures were to be utilized as an enrichment for biodegradation studies.  Purified PAHs were used as the sole carbon sources (0.1%) and were inoculated with the bacterial cultures.  Increases in turbidity and color changes were monitored to determine growth and biological activity, respectively.  Low molecular weight PAHs were easily degraded by the bacterial enrichments.  Approximately 72 percent of the measured PAH were degraded, which accounted for 52.5 percent of the weight of the initial PAHs.  These aerobic degradation processes of creosote PAHs have shown that biodegradation in the presence of certain bacteria is accompanied with the formation of neutral and acidic oxidized products.

Schocken, M.J. and D.T. Gibson, 1984

The metabolism of acenaphthene and acenaphthylene by two strains of bacteria was examined in this study.  Biejerinckia species and a mutant strain Biejerinckia species B8/36 bacteria were found to oxidize the two PAHs.  The study was carried out with large-scale incubations at 30(C. Acenaphthene oxidized into 1-acenaphthenone, 1,2-acenaphthenediol, acenapthenequinone and 1-acenaphthenol; acenaphthylene oxidized into acenapthenequinone.  The results indicated that even though these PAHs were both oxidized to acenapthenequinone, the pathways to form this product are quite different.

Godsy, E.M., D.F. Goerlitz, and D. Grbic-Galic, 1992

(Anaerobic Study) The US Geological Survey selected an abandoned wood preserving site once used for creosote and pentachlorphenol pressure treatments to analyze and identify the contaminants in groundwater from plant waste.  This waste had been discharged into the unlined surface impoundments that were in direct hydraulic contact with groundwater. The groundwater was determined to be anaerobic and showed the presence of methane and hydrogen sulfide (indicating the presence of methanogenic and sulfuryl microbes).  To conduct the study, holes were bored to a depth of 6.1 meters at various sites on a downward slope from the contamination source ponds.  Table 4 lists the concentrations of PAHs at the various sites.  The results indicated that lateral migration of most of the PAHs became undetectable 150 meters from the source of contamination.  However, the study authors did not indicate the age of the wood and how long the preserving plant had been abandoned before testing began.

Table 4.  Amounts of PAHs in the Water Samples From 6.1 Meter Wellsa

Compoundb

Site 1c

(uncontam.)

Site 3

(6.0 m)

Site 39

(53 m)

Site 40

(99 m)

Site 4

(122 m)

Site 37

(150 m)

Indene

ND

1.25

0.24

ND

ND

ND

Naphthalene

ND

9.38

3.39

2.89

0.93

1.54

1-Methylnaphthalene

ND

0.41

0.32

0.25

0.06

0.11

2-Methylnaphthalene

ND

0.99

0.32

0.54

0.10

0.10

Acenaphthene

ND

0.52

0.29

0.33

0.05

ND

Indole

ND

ND

ND

ND

ND

ND

Quinoline

ND

11.2

0.01

ND

ND

ND

Benzothiophene

ND

0.83

0.31

0.22

0.16

0.16

Dibenzofuran

ND

0.30

0.04

0.16

ND

ND

ND = Not detected

a - Water samples collected from wells on these sites.

b - Analyzed and quantified  through GC/MS methods.

c - Uncontaminated site

Goerlitz, D.F. et al., 1985

A similar study was conducted by the US Geological Survey at the same wood preserving plant that was used in the study of Godsy et al. (1992).  Results showed that on Site 3 at a 30-meter well, naphthalene (15.60 ppm) was detected 6 meters from the source of contamination and the level of naphthalene progressively decreased with an increase in well depth.  At 24 meters, only 0.60 ppm of naphthalene was detected.  PAHs were not detected at a depth greater than 12 meters.

Genther, B.R., et al., 1997

A year long study on anaerobic soil biodegradation was conducted at the American Creosote Works Superfund site located in Pensacola, Florida using soil samples collected from the creek bed sediment.  Samples were collected at a depth of 5 to 8 cm and 12 meters, which was below the main discharge pond.  These soil samples were selected because they represented bacterial populations exposed to minimum and maximum concentrations of the PAHs in situ.  The PAHs used were from an artificial mixture simulating the PAH components of creosote.  Various batches of the artificial mixture were made and consisted of the following components: naphthalene (36 mg), 1-methylnaphthalene (10.8 mg), 2-methylnaphthalene (10.8 mg), 2,6-dimethylnaphthalene (10.8 mg), biphenyl (5.4 mg), acenaphthene (5.4 mg), fluorene (10.8 mg), phenanthrene (18.0 mg), anthracene (18.0 mg), 2-methylanthracene (9.0 mg), anthraquinone (3.6 mg), fluoranthene (9.0 mg), pyrene (3.6 mg), chrysene (3.6 mg), 2,3-benzo[b]fluorene (3.6 mg), and benzo[a]pyrene (3.6 mg).  Various batches of this artificial PAH mixture were inoculated with the contaminated soil samples under methanogenic, sulfidogenic, and nitrate-reducing conditions.

The majority of the PAHs did not degrade in the soil samples collected from the creek bed (5-8 cm depth).  Loss of some bicyclic and tricyclics were observed; however, 4- and 5-membered PAHs did not degrade under methanogenic, sulfidogenic, or nitrate-reducing conditions.  By 16 weeks, under methanogenic conditions, the maximum loss of naphthalene was 47 percent (similar to naphthalene loss under an abiotic control (40 percent)).  Among the tricyclics, anthraquionone was the only substance where any loss under methanogenic conditions was  reported.  Anthraquinone loss reached 48 percent and about 65 percent by weeks 28 and 52, respectively.  Two other tricyclics, anthracene and acenaphthene, degraded 22 percent under the same conditions. Under nitrate-reducing conditions, only degradation for 2-methylanthracene was observed and the concentration of this chemical was below the detection limit between weeks 8 to 28.  Under sulfidogenic conditions, only anthraquinone degraded 22 percent by week 8.  Under these conditions, no other PAHs showed any biodegradation up to week 52.  For the 12-meter soil samples, no appreciable biodegradation processes were observed for most of the PAHs under all three anaerobic conditions.

III Miscellaneous Studies

Anaerobic soil metabolism studies for individual PAHs have been conducted over a period of time using the three anaerobic conditions.  For nitrate reducing conditions, the studies conducted were Bouwer and McCarty, 1983; Al-Bashir, et al., 1990; Ehrlich et al., 1982a; Flyvberg et al. 1993; Hambrick et al., 1980; Kuhn et al., 1988; and Mihelcic and Luthy, 1988a, 1988b.  The study was conducted for sulfidogenic conditions by Flyvjberg et al., 1993.  The studies  for methanogenic conditions include Ehrlich et al. 1982a; and Godsy et al., 1992.  Other in situ studies for biodegradation of PAHs at creosote contaminated sites are: Ehrlich et al. 1982a, 1982b; Godsy et al. 1992; Goerlitz et al., 1985; and Mattraw and Frank, 1986.

Bauer, J.E. and D.G. Capone, 1985

Microorganisms present in the intertidal sediments were investigated for the degradation of anthracene and naphthalene.  No mineralization was observed under anaerobic conditions.  However, mineralization did show dependence on the amounts of the polyaromatics present, oxygen level, and pre-exposure time.  Maximum mineralization of these two PAHs occurred after one or two weeks of pre-exposure.  A similar study conducted by the same authors (in 1988) showed that the pre-exposure of anthracene and naphthalene under aerobic conditions (marine sediments collected from 0 to 1 cm depth) to benzene and other PAHs accelerated their mineralization.

Mueller, J.G. et al., 1991

Groundwater samples collected from a depth of 7 meters from the American Creosote Works superfund site in Pensacola, Florida were examined for biodegradation (aerobic aquatic metabolism) of PAHs from coal-tar creosote.  Creosote-contaminated soil from the site was collected and used to prepare the microbial inoculum.  Groundwater samples and the microbial inoculum were incubated for 14 days at 30(C.  The groundwater samples contained the PAHs present in coal-tar derived creosote and in the phenolic components (which constituted 5% of the creosote sample).  In addition, PCP was also present.  Table 5 summarizes the results of the 14-day incubation experiment.  The analysis showed that bicyclic PAHs and phenolics are metabolized readily by the microorganisms in the aquatic soil while the PAHs with a higher number of fused rings biodegrade more slowly.  By Day 8 most of the biodegradation was complete.  A few nitrogenous heterocyclics like quinoline, isoquinoline, and acridine readily metabolized while quinaldine, carbazole, and pentachlorphenol showed resistance to the metabolic process under the conditions of the experiment.

Table 5.  Aquatic Soil Metabolism (Biodegradation) Results for Creosote/PCP Contaminants  In Groundwater Samples From Pensacola, Florida Superfund Site

Compound

Concentration (µg/mL) After Incubation

Initial Conc.

1 Day

3 Days

5 Days

8 Days

14 Days

Sterile Control

Naphthalene

28.7

17.2

0.1

U

0.1

U

25.6

2-Methylnaphthalene

4.7

3.0

U

U

0.1

U

4.5

1-Methylnaphthalene

9.5

5.7

2.1

1.5

U

U

8.2

Biphenyl

3.0

1.7

1.2

U

U

U

2.6

2,6-Dimethylnaphthalene

2.4

1.4

1.2

1.2

1.0

0.3

2.1

2,3-Dimethylnaphthalene

1.3

0.8

0.5

0.8

0.7

0.2

1.0

Acenaphthalene

0.6

0.3

0.4

0.6

0.6

0.2

0.4

Acenaphthene

13.6

9.0

8.3

9.6

9.7

1.8

11.9

Fluorene

11.6

7.8

8.0

5.2

1.8

0.1

9.9

Phenanthrene

32.8

23.5

23.1

15.4

0.3

U

27.7

Anthracene

4.7

3.2

3.0

2.7

2.2

0.5

3.9

2-Methylanthracene

5.2

3.7

3.7

4.0

4.2

1.5

4.4

Anthraquinone

3.3

2.7

1.9

U

U

U

2.9

Fluoranthene

16.2

11.5

11.5

13.3

13.5

7.6

14.4

Pyrene

10.4

7.8

7.3

8.2

8.3

4.7

9.8

Benzo[b]fluorene

2.5

1.7

1.7

1.8

2.0

1.2

2.0

Chrysene

2.7

1.8

1.8

2.0

2.1

1.2

2.4

Benzo[a]pyrene

2.1

0.5

U

U

U

0.9

2.0

Benz[a]anthracene

2.9

2.0

2.0

2.0

2.2

1.3

2.7

Benzo[b]fluoranthene/benzo[k]-

fluoranthene

2.9

2.8

2.0

2.1

2.1

1.7

2.8

Indeno[1,2,3-c,d]pyrene

1.9

1.3

1.4

1.4

1.2

0.9

1.8

2,6-Xylenol

1.1

0.6

0.2

0.1

0.1

U

0.8

o-Cresol

4.2

2.7

0.3

0.2

0.2

U

4.9

2,5-Xylenol

0.1

U

U

U

U

U

0.1

2,4-Xylenol

0.2

U

U

U

U

U

0.2

p-Cresol

2.0

0.1

U

U

U

U

2.3

m-Cresol

2.5

1.9

U

U

U

U

2.3

2,3-Xylenol

0.2

0.1

U

U

U

U

0.1

3,5-Xylenol

1.3

0.5

0.2

0.1

U

U

1.1

3,4-Xylenol/2,3,5-trimethylphenol

0.4

0.1

0.1

0.1

U

U

0.3

PCP

0.1

0.3

0.1

0.1

0.1

0.1

0.1

2-Picoline

0.3

0.2

0.2

0.2

0.1

U

U

3-Picoline/4-picoline

U

U

U

U

U

U

U

Lutidine

0.9

0.7

0.6

0.5

0.5

0.6

0.8

Thianaphthene

20.3

12.5

2.6

1.2

0.5

0.3

23.4

Quinoline

4.3

1.7

0.5

0.2

0.2

0.2

3.6

Isoquinoline

1.5

0.9

0.3

0.3

0.1

U

1.4

Quinaldine

3.4

3.2

2.8

2.4

0.6

0.3

4.9

Lepidine

0.7

0.6

0.4

0.3

0.3

0.2

0.7

Dibenzofuran

5.5

5.9

5.8

3.4

1.0

0.7

6.1

Dibenzothiophene

3.8

2.8

3.1

2.0

1.3

1.2

3.1

Acridine

22.5

18.2

14.1

1.9

2.0

2.0

26.2

Carbazole

2.9

2.1

1.2

0.9

0.8

1.0

3.0

Note:	Reported data are averages of duplicate samples.

U - Below the detection limit.

Hurst, C.J. et al., 1996

An aerobic and anaerobic soil metabolism study was conducted at the Champion International superfund site in Libby, Montana.  The contaminated soil samples were spiked with for analysis.  Biodegradation for 14C-pyrene and seventeen PAHs (including pyrene) was followed by 0 percent, 2 percent, and 21 percent oxygen as soil gas.  The PAHs chosen for the study were: naphthalene, acenaphthylene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a] pyrene, dibenzo[a,h] anthracene, benzo[g,h,i]perylene, and indeno(1,2,3-cd).  After 70 days, 45 to 55 percent of the 14C-pyrene was mineralized in 2 percent  and 21 percent oxygen.  At 0 percent oxygen, no statistically significant mineralization was observed.  For eight of the non-radiolabeled PAHs, biodegradation in an oxygen atmosphere ranged from 6.2 percent (naphthalene) to 57 percent (pyrene).  The remaining PAHs were below the limit of detection.

IV Leaching and Adsorption/Desorption

Villholth, K.G., 1999

The objective of this study was to determine the amount of colloids in the groundwater of two creosote-contaminated aquifers in Denmark and to determine the in situ distribution of the PAHs between the dissolved and colloidal phases in the water.  The colloids identified at the sites were clay minerals, iron-oxides, iron-sulfides, and quartz particles containing significant amounts of organic carbon.  The results of a two-step fractionation procedure, showed that the PAHs partitioned to the course (>100 nm) colloid fraction (log Koc) and was linearly correlated with the PAH octanol-water partition coefficient (log Kow), indicating the partitioning was hydrophobic.  This suggested a potential for colloid-facilitated transport of PAHs.  The lack of PAH partitioning to colloids <100 nm, indicates a weaker binding to the smaller, more hydrophilic colloids in the groundwater.

Rutherford, P.M., et al., 1997

This study was designed to determine if a 10-week slurry phase bioremediation treatment altered the desorptive properties of two-creosote-contaminated soils.  Soil samples were collected from an inactive wood preserving facility in Edmonton, Alberta (EDM site) and Prince Albert, Saskatchewan (PAA site).  For bioremediation, soil samples were combined with aqueous nutrient media under aerobic conditions in a bioreactor.  Desorption of 14C-naphthalene from the contaminated soils was measured before and after bioremediation in a sequential batch experiment.  The contributions of the contaminant organic phase and the soil organic matter to desorption were determined by experiments on soils with and without nonaqueous phase liquid contaminants.  Results showed that total extractable organics were 43 to 31 percent lower in the bioremediated soils for both sites.  This reduction in total organic carbon content lowered the sorption capacity of the soils.  The desorptive partition coefficient (Kd) for the nonbioremediated EDM soil was significantly (p = 0.022) greater than the nonbioremediated PAA soil.  However, after bioremediation, no significant difference was found between the two soils (p = 0.11).  Although the Kd decreased due to bioremediation, the carbon-based partition coefficients on the nonaqueous phase liquid did not change significantly once the changes in the overall composition of the soil had been accounted for.

Priddle, M.W. and K.T.B. MacQuarrie, 1994

A laboratory study was conducted to evaluate the dissolution of industrial creosote in water using a generator column to determine the impacts on groundwater quality and the kinetics of the dissolution process.  The laboratory results were also compared to an equilibrium model and a quasi-kinetic model.  For the laboratory study, the generator column was packed with a 10 percent creosote effluent obtained from Carbochem Inc. (Hamilton, Ontario, Canada).  The study focused on 10 specific PAHs including naphthalene, phenanthrene and benzo[a]pyrene.  A mass-transfer rate test was conducted to evaluate the rate the creosote components reached equilibrium concentrations.  Additionally, two long-term dissolution tests were conducted by passing water through the column for a designated period of time.  The mean contact time in the column was 0.56 and 1.02 hours during the two testing periods.  The results of the mass transfer test indicated that the creosote components reached equilibrium with the aqueous phase in about 60 hours.  The two long-term tests found that the concentrations of the targeted PAHs detected in the effluent all decreased steadily throughout the monitoring period.  The initial concentrations of the components were approximately 40 percent of the calculated effective solubilities.  The higher molecular weight compounds were not detected which was expected due to the low effective solubilities (<0.002 mg/L-1).  Overall, the ratios of these concentrations were in proportion to their effective solubilities which were calculated using Raoult’s law and the creosote composition data.

Padma, T.V. et al., 1999

A study was conducted to monitor the effects that various processes (tides, storms, bioturbation, shipping, and dredging) may have in the dissolution and resuspension of sediment-associated PAHs.  These environmental processes were mimicked by creating a water-soluble fraction from the creosote-contaminated sediment and artificial estuarine water.  Creosote-contaminated sediment samples were collected near Atlantic Wood Industries on the Southern Branch of the Elizabeth River in Virginia.  The results showed that the creosote-contaminated sediment source  contained more intermediate weight (three aromatic rings) and high molecular weight (more than three aromatic rings) PAHs, in contrast to the water-soluble fraction, which contained high levels of low molecular weight (less than three aromatic rings) and heterocyclic compounds.  These differences were the result of fractionation and degradation of creosote in the water soluble fraction.

EPRI, 1992

EPA’s toxicity characteristic (TC) rule declares three phenolic isomers (o-, m-, and p-cresol) are highly toxic, and therefore, regulated substances.  The Electric Power Research Institute (EPRI) used the TCLP technique, a leaching method (EPRI, 1992), to determine the concentrations of the three phenolic isomers that leached from treated wood poles and crossarms when nearing disposal.  The EPA regulation requires that the leachates should not contain >200 mg/L; otherwise, the treated wood is classified as hazardous and can not be disposed of as solid waste into landfills.  Fifty four samples from seventeen poles and six crossarms, (ages 7 to 53 years) were chosen from the Northeast, Mid-Atlantic, Southeast, Midwest, North Central and Western regions of the United States.  Southern Pine, Douglas Fir, Western Red Cedar, and Cedar woods were chosen for the study.  Total cresol concentration (all three isomers) present in the leachates ranged from below the detection limit (0.01 mg/mL) to 14.95 mg/mL, and the mean concentration was 1.63 mg/mL.  This was below the Agency’s toxic characteristic regulatory level of 200 mg/mL.

Gile, J.D. et al., 1982

Seven blocks of Ponderosa pine blocks (3.3 x 2.6 x14 cm) pressure-treated with radiolabeled phenanthrene, acenaphthene, and bis(tri-n-butyl oxide) were tested in a terrestrial microcosm chamber (TMC-II).  This microcosm contained Williamette Valley topsoil, ryegrass, invertebrates, and a gravid gray-tailed vole.  The impregnation mixture contained dieldrin as a reference compound.  The study was conducted for 2.5 months at which time it was found that 95 percent of the pesticides remained in the wood and most of the materials that leached remained in the upper soil layer immediately surrounding the pine blocks.  In the plants of the microcosm,

0.7 ppm of dieldrin was detected while phenanthrene was detected at a 8.8 ppm.  Bioaccumulation in the invertebrates was variable and the concentration of phenanthrene in the vole body was 7.2 ppm, while acenaphthene was detected at 37.0 ppm.

Wendt, P.H., 1996

In a six-week two-phase field study, private, residential docks located on ten tidal creeks at South Carolina’s Charleston Harbor Estuary treated recently with CCA, but originally treated with creosote were studied.  Samples were collected from sediments and oysters (Crassostrea virginica) <1 meter, and >10 meters from the docks.  Reference samples were also collected.  Mean concentrations of the 12 PAHs monitored from the sediment were 978.3 µg/kg (dry wt.), 690.0 µg/kg (dry wt.), and 1183.8 µg/kg (dry wt.) for the <1 m, >10 m, and the reference samples, respectively.  Mean PAH concentrations from the oysters were 3547.3 µg/kg (dry wt.), 2057.6 µg/kg (dry wt.), and 2173.1 µg/kg (dry wt.) for the <1 m, >10 m, and reference samples, respectively.  The study author reported that these concentrations were generally within the range of values found at nearby marinas.  Most concentrations of PAHs in whole sediments were generally below Long et al.’s (1995) “ER-L” (Effects Range-Low) levels, suggesting that these values reported were insufficient to cause any adverse biological/toxic effects.

Bestari K.T. Jim et al., 1998a

 water were 7.3 μg/L (0.06 ppm  application) and 5,803.2 μg/L (109 ppm application).  By Day 84, total PAHs remaining in the water were 0.80 μg/L and 13.9 μg/L from the 0.06 ppm and 109 ppm applications, respectively.  In sediments, total PAHs ranged from 0.91 μg/g to 63.9 μg/g at Day 28, then declining thereafter.  A similar trend of declining concentrations was shown by the PAHs on the PVC strips.  A mass balance calculation reported a loss of 88.3 percent of PAHs from the  microcosms after one month.  Based on the total PAH concentrations, the half-life of most PAHs in water was reported to be approximately one week.

Bestari, K.T. Jim et al., 1998b

Marine-grade Douglas fir pilings (15 to 20 cm diameter and 1.2 m length) were pressure-treated with creosote using the same concentrations (0.06 ppm to 109 ppm) as in Bestari K.T. Jim et al. (1998a) in a similar simulated microcosm.  This microcosm contained sediment, rooted and floating macrophytes, and fish and invertebrate communities which consisted of phytoplankton, zooplankton, and benthos.  The total organic content was 5.1 percent in water that had been  circulated in the microcosm through a holding tank for four weeks to maximize the chemical and biological compositions.  The pressure-treated pilings were suspended vertically in each microcosm in such a way that they were just above the water surface and not touching the sediment.

 7 after the treatment (7.3 μg/L to 97.2 μg/L) and then declined to concentrations close to the background (0.80 to 6.7 μg/L) by the end of the study (Day 84).  Total PAHs from the leachates did bind to the PVC liner, concentrations on Day 31 ranged from 0.3 to 2.4 μg/cm2, and ranged from 0.2 to 2.2 μg/cm2 58 days after the treatment.  The rate of loss of creosote from the pilings was 50 μg/cm2/day.  The study suggested that the rapid loss of creosote was primarily due to degradation processes like photolysis and microbial decomposition, and partial adsorption to PVC liners.  The PAHs identified in this and previous experiments were: naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]pyrene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene and dibenz[a,h]anthracene.  These are fifteen of the sixteen PAHs that EPA has recognized as EPA Priority Pollutants.

Wan, M.T., 1994

In this study, runoff water from pressure-treated utility and telephone wood poles was collected from fourteen utility and six railway ditches.  The utility and telephone poles were initially pressure-treated with pentachlorophenol and later in situ treated with a mixture of creosote and chlorophenols.  The treatment was typically at the base up to 0.5 m above and below soil level, and these applications were either used as wrappings or painted with a creosote/chlorophenol mixture.  The runoff water was analyzed for the presence of 15 PAHs.  These right of way (ROW) ditches which were sampled flow into salmon streams in the Lower Mainland and Vancouver Island of British Columbia, Canada.  Ditches of parklands, farmlands, and railway ROWs were also sampled to establish background and reference PAH concentrations.  PAHs were not detected in the parkland ditches; however, they were found in farmlands and in utility and railway ROW ditches.  The data from this study showed that the maximum concentrations of the PAHs are in the wood and the PAHs that leach out of the wood were mostly present around the base of the poles.  Tables 6 through 8 summarize the presence/absence of the PAHs in various environmental compartments.

Table 6.  PAHs in Treated Wood

Compound

Poles

 (mg/kg)

Railway Ties (mg/kg)

Acenaphthene

3,566

1,238

Acenaphthylene

244

77

Anthracene

17,686

5,100

Benz[a]anthracene

1,938

465

Benz[b+k]fluoranthene

811

254

Benz[a]pyrene

1,116

461

Benz[ghi]perylene

69

37

Chrysene

1,093

383

Dibenz[a,h]anthracene

7

16

Fluoranthene

7,832

1,880

Fluorene

5,313

1,141

Indeno[1,2,3-cd]pyrene

36

40

Naphthalene

1,514

342

Phenanthrene

15,378

3,173

Pyrene

5,289

1,487

Total PAHs

61,182

16,094

Note:  These PAHs were extracted from a sample of wood chips/scraps which were collected and made into a composite mixture of 25 poles or 25 railway ties.

Table 7.  PAHs in Ditch Water of Parklands, Farmlands and Railway Rights-of-Way  in the Lower Mainland of British Columbia

Compound

Parkland Ditches (μg/L)

Farm Ditches (μg/L)

Railway Ditches (w/poles, μg/L)

Railway Ditches (w/o poles, μg/L)

Acenaphthene

ND

1.04

206

0.57

Acenaphthylene

ND

1.72

5.5

1

Anthracene

ND

0.16

81

01.3

Benz[a]anthracene

ND

0.10

195

0.12

Benz[b+k]fluoranth-ene

ND

0.19

144

0.19

Benz[a]pyrene

ND

0.10

43

0.10

Benz[g,h,i]perylene

ND

0.19

12.2

0.14

Chrysene

ND

0.10

228

0.17

Dibenz[a,h]anthracene

ND

0.26

4.1

0.10

Fluoranthene

ND

0.30

2035

0.26

Fluorene

ND

0.30

116

0.22

Indeno[1,2,3-cd]pyrene

ND

0.16

17.6

0.15

Naphthalene

ND

0.35

8.5

0.19

Phenanthrene

ND

0.40

1027

0.44

Pyrene

ND

0.19

1233

0.19

Total PAHs

ND

5.56

5,356.3

3.97

Note:  In all cases the number of sample sites was never more than two.

ND = Not detected.

Table 8.    PAH Concentrations in Utility ROW Sediments in the Lower Mainland of British Columbia

Compound

Concentration (µg/L)

Base of Pole

Ditches 4 m

Upstream of Pole

Ditches Adjacent to Pole (0.1-0.3 m)

Ditches 4 m Downstream of Pole

Acenaphthene

221

0.11

1.03

ND

Acenaphthylene

36

ND

1.37

ND

Anthracene

706

0.16

2.12

0.09

Benz[a]anthracene

93

0.05

0.46

0.25

Benz[b+k] fluoranthene

71

ND

0.65

0.73

Benz[a]pyrene

67

0.11

0.41

0.64

Benz[g,h,i]perylene

73

ND

0.43

0.20

Chrysene

92

0.11

0.41

0.17

Dibenz[a,h]anthracene

91

ND

0.20

0.27

Fluoranthene

211

0.19

1.24

0.24

Fluorene

469

0.10

1.58

ND

Indeno[1,2,3-cd]pyrene

75

0.25

0.71

0.34

Naphthalene

34

0.12

0.08

ND

Phenanthrene

666

0.07

3.29

0.12

Pyrene

171

0.06

1

0.22

Total PAHs

3076

1.33

15

3.27

Note:  Sampling size varied from 5 to a maximum of 8 samples.

ND = Not detected

Middaugh, D.P. et al., 1991

An Agency sponsored study was conducted on the leaching of creosote components from an abandoned American Creosote Works Site, a freshwater stream that flows into the Florida Pensacola Bay.  This site also utilized pentachlorophenol (PCP) and chromated copper arsenate (CCA).  Adjacent to the site, a well was dug to a depth of 21 meters and the ground water was analyzed.  The PAH concentrations in groundwater were reported as follows: phenanthrene (32.8 mg/kg), naphthalene (28.8mg/kg), fluoranthene (16.1 mg/kg), acenaphthene (13.6 mg/kg), fluorene(11.6 mg/kg), pyrene (10.4 mg/kg), 1-methyl naphthalene(9.5 mg/kg), and 2-methylanthracene (5.2 mg/kg).  The concentrations of other PAHs detected were either less than 5 percent of the ones noted above or were very low.

V  Bioaccumulation

Stegman and Teal, 1973 and Varsani, et al., 1978

Studies on bioaccumulation showed that in an aquatic habitat, organisms such as fish, shellfish, and crustaceans readily accumulate PAHs from the environment and store them at a high level in their tissues.

Southworth, G.R., etal., 1978

A study was designed to investigate the bioaccumulation of seven selected PAHs in Daphnia pulex.  The PAHs selected were: naphthalene, anthracene, phenanthrene, pyrene, 9-methylanthracene, benz[a]anthracene, and perylene.  Bioaccumulation corresponded to the  octanol/water partition coefficients (KOW).  The benz[a]anthracene bioaccumulation factor was 10,000 fold higher and about 100 fold higher for naphthalene.

A bioaccumulation study on clams (Rangia cuneate) was also conducted after a creosote spill into Bayou Bonfuca at the American Creosote Works Plant site at Slidell, Louisiana.  Results showed that the levels of PAHs increased gradually for two weeks and increased dramatically by week four at the monitoring station closest to the spill site.  The PAH results are shown in Table 9.

Another station (control station) in the same study showed evidence of depuration after two weeks and equilibration after four weeks.  The concentration of PAHs in water was very low at the site close to the spill (13 ppb in two weeks and 26 ppb after four weeks).  Among the PAHs, benzopyrenes were detected at a very high level of 600 ppb at the station closest to the spill site. Other studies (Politzer, 1985; Neff, 1976) also showed that depuration of PAHs in bivalves vary from a couple of weeks to a few months.  These studies support the possibility of bioavailability of PAHs and contamination of the food chain.

Table 9.  Amounts of PAHs Detected in Clams at the Closest Station to the Spill Site

PAH Component

Week 0 - Pre-exposure (ppb)

Week 2

(ppb)

Week 4

(ppb)

Naphthalene

43

60

120

Biphenyl/Acenapthylene

17

13

42

Fluorene

7

5

11

Phenanthrene/ Anthracene

34

10

28

Fluoranthene/Pyrene

120

88

130

Benz[a]anthracene/Chrysene

41

81

190

Benzopyrenes

87

132

600

Spacie, A., et al., 1983

Bluegill sunfish were used to investigate the uptake (bioaccumulation), biotransformation, and depuration rates of anthracene and benzo[a]pyrene.  The uptake half-life for anthracene was 0.019 hours and did not appear to be affected by the exposure concentration and humics.  The uptake half-life of benzo[a]pyrene was also similar, but was affected by the presence of humics.  Biotransformation for anthracene was determined to be 0.22 nmol/hr while for benzo[a]pyrene  varied from 0.044 nmol/hr to 0.088 nmol/hr, between 1 and 2 hours of exposure.  The depuration half-life for anthracene was 17 hours and 67 hours for benzo[a]pyrene.  Due to the  biotransformation, the bioconcentrations for both anthracene and benzo[a]pyrene were lower than predicted from the Kow.

Tay, K.L., et al., 1992

A detailed bioassessment study was conducted in Canada on the Halifax Harbor Sediment. Bioaccumulation of PAHs and other organic and inorganic contaminants were investigated on the bivalve mollusk (Macoma balthica).  The exposure of the species to the contaminated sediment was 30 days.  The study authors suggested that the duration of 30 days may have been too short for uptake of the PAHs into the Macoma system.  Organic content in the Tuft’s Cove sediment was high and that may have prevented the bioaccumulation process.  Table 10 summarizes the results.

Table 10.  Bioaccumulation of PAHs in Macoma balthica

Station

PAHs in Tissues

(mg/kg wet wt.)

Walton (Control sediment)

0.11

Drakes Gut 1 (Reference sediment)

0.13

Tuft’s Cove (Contaminated sediment)

ND

Original tissues (not exposed to test sediment)

0.01

J.F. Elder and P. Dresler, 1988

A study on bioaccumulation was conducted on mollusk species at the Pensacola Bay, 500 m from the creosote wood-preserving facility in Pensacola, Florida.  Only four PAH compounds (phenanthrene, fluoranthene, pyrene, and naphthalene) were found in the mollusk species studied.  Depuration rates were not reported.  The same study also estimated the PAH presence in water and the surface layer of estuarine sediments.  The study, conducted on seven sites, found that the sediments of the drainage streams were heavily contaminated with PAHs.  The analysis of sediments at the sites showed very little contamination with PAHs except at one site (Site 4).  This site was closest to the wood-preserving facility.  The same study also reported that the bioaccumulation of fluoranthene, pyrene and phenanthrene in both species of mollusks was ten times higher at the test site than at the control site.  Table 11 summarizes the results.

Most of the PAHs were insoluble in water and the solubilities were inversely related to the molecular weights of the polyaromatics.  Bioaccumulation of a pesticide depended on many external factors such as resistance to biodegradation, chemical degradation, photolysis, tendency for migration, and bioavailability.  The data on bioaccumulation of PAHs are not extensive; however, a few generalities emerged from the existing data.  First, molecules with lower molar masses had a tendency to bioaccumulate more than high molar mass substances.  Second, bioaccumulation was also dependent on the concentrations of a substance.  For example, between naphthalene (two fused-ring compound) and phenanthrene (three fused-ring compound), it is the later which was found to bioaccumulate more than naphthalene because in the original mixture of PAHs, phenanthrene was 20 percent of the mixture while naphthalene was 3 percent.

Table 11.  Concentrations of PAHs in the Sediment and Discharge Stream at Pensacola Bay

PAH

Stream Site 3 (g/kg)

Stream Site 2 (g/kg)

Pensacola Bay

Site 4 (g/kg)

Pensacola Bay/ Other Sites (g/kg)

Naphthalene

300

200

ND

ND

Phenanthrene

ND

12000

ND

ND

Fluoranthene

62000

17000

190

ND

Pyrene

32000

11000

160

ND

Benzoanthracene

15000

5000

75

ND

Chrysene

10000

7000

100

ND

Acenaphthene

19000

5000

ND

ND

Fluorene

32000

3000

ND

ND

Anthracene

140000

3000

ND

ND

ND - Not detected.  The limit of detection was 40 g/kg.

Bruner, K.A. et al., 1994

To measure PAH bioconcentration factors, a study was conducted on pre-spawning (high lipid) and post-spawning (low lipid) mussel populations of zebra mussel in the Great Lakes.  Pre-spawning mussels had greater bioconcentration factors and a faster rate of accumulation for benzo[a]pyrene than post-spawning mussels.  Lipid content, however, did not influence bioconcentration factors or the rates of accumulation.  Rates of depuration were not influenced by either factor (high or low lipid contents).

Hellou, J.G., et al., 1990

A study was conducted on the bioaccumulation of PAHs in marine mammals.  Four species of seals and six species of whales from the waters around Newfoundland and Labrador were utilized as test subjects.  Accumulated values, when expressed in terms of chrysene-equivalents were 0.10 to 1.21 ppm in the muscles of these mammals on a dry weight basis.

Howard, P.H. et al., 1991

It was suggested, based on theoretical calculations and modeling, that the half-lives of the PAHs can be estimated in air, water, soil and sediments.  This data are presented in Table 12.  From the table, one can arbitrarily divide the PAHs into three groups: PAHs with two aromatic fused rings, with three aromatic fused rings, and 4-5 aromatic fused rings.  The study authors came to the following conclusions: 1) The half-lives of the PAHs in these environmental compartments increased as the complexity of the molecules increased.  Generally, half-lives of 2 aromatic fused rings < 3 aromatic fused rings < 4/5 aromatic fused rings; 2) Kow values also show a similar trend: three sets of Kows were observed.  The Kow values ranged from 3 to 4, from 4 to 5, and 6 and above.  As noted for the half-lives, the Log Kow increased as the complexity of the molecule increased;  3) In general, the half-lives in air and water environmental compartments were lower than in soils/sediments, since the adsorption constant in these two compartments were larger than in air and water media.  Those molecules with a longer half-life also exhibited persistence in that environmental compartment.  PAHs were more persistence in soils/sediments than in other environmental compartments; and 4) The 4/5 aromatic-fused ring molecules were persistent and because they also had high Kows, they were also bioaccumulative in the organisms present in the soil/sediments.

Table 12.  Estimated/Modeled PAH Half-lives in Air, Water, Soil and Sediment

Compound

Air/

Class

Half- live

Water/Class

Half-life

Soil/Class

Half-life

Sediment/Class

Half-life

Kow

Indan

2

1 day

4

1 wk.

6

2 mos.

7

8 mos.

3.33

Naphthalene

2

1 day

4

1 wk.

6

2 mos.

7

8 mos.

3.37

1-methyl naphthalene

2

1 day

4

1 wk.

6

2 mos.

7

8 mos.

3.87

Acenaphthalene

3

2 days

5

3 wks.

7

8 mos.

8

2 yrs.

3.92

Fluorene

3

2 days

5

3 wks.

7

8 mos.

8

2 yrs.

4.12

Phenathrene

3

2 days

5

3 wks.

7

8 mos.

8

2 yrs.

4.57

Anthracene

3

2 days

5

3 wks.

7

8 mos.

8

2 yrs.

4.54

Pyrene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

5.18

Fluoranthene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

5.22

Chrysene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

1.65

Benz[a]anthracene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

5.91

Benzo[k]flouranthene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

6.00

Benzo[a]pyrene

4

1 wk.

6

2 mos.

8

2 yrs.

9

~ 6 yrs.

6.04

VI  Migration of PAHs From Poles to Soils

Mississippi State University, 1981

Fifty-six soil samples were collected radially around fourteen creosote-treated poles and analyzed for migration of creosote components into the surrounding soils.  The concentrations of naphthalene, 2-methylnaphthalene, 1-methylnapthalene, and biphenyl varied from 25 to 50 ηg/g. Acenaphthylene, acenaphthene, dibenzofuran, fluorene, phenanthrene, and anthracene were present at lower concentrations than in the original mixture of creosote.  The author suggested that vaporization, water solubility, and biological degradation might be contributing factors for reduction in the concentrations of these polycyclic components of creosote.  Fluoranthene, pyrene, carbazole, 1,2-benzanthracene, and chrysene were persistent in the soil around the poles and the concentration of all the components decreased as the distance from the poles increased.

McGroddy, S.E. and J.W. Farrington, no date available

In a study on sediment porewater partitioning of PAHs in Boston Harbor, it was shown that the PAH concentrations measured in sediments and porewaters from three cores were notably lower than the amounts of the PAHs predicted by two- and three-phase equilibrium partitioning models.  The study author suggested lower amounts might have been available for partitioning in sediment porewaters.

K. Brooks’  Study, 2004:  “Polycyclic Aromatic Hydrocarbon Migration From Creosote-Treated Railway ties into Ballast and Adjacent Wetlands

A simulated mesocosm on a wetland was created in Will County, Illinois.

Newly Treated, untreated and weathered-treated railroad ties were placed in this simulated wetland.

The study was conducted for two years. Samples were  analyzed  from ballast ( surface on which ties are placed),  wetland sediments, groundwater, stormwater, and soil cores.

The detection and analysis of the PAHs was done:  by examining  direct contamination from surface stormwater, PAHs infiltration into shallow ground water, and lateral distance from the railroad ties (adjacent wetland soils). PAHs were detected up to 60 cm  vertically down  into the ballast. Mesocosm soil type was: Romeo Silty clay loam.

Baseline PAH concentrations were determined using EPA’s Method 8310. The samples were extracted by Soxhlet extraction method.

p-Terphenyl was used as a surrogate for PAH determinations. Baseline PAH levels in the surface soils on this simulated wetland was measured at 0.00 to 0.17 µg/g.

 Retentions for new  railway ties varied from 28 to 57.28 kg/m3 and for the old railway ties it varied from 39.36 to 55.52 kg/m3 Each number represents an average of 12 borings.

13 stormwater samples which included newly treated, untreated and weathered ties were analyzed using EPA’s Method 2003a( GC/MS technique).

229 samples collected form the surface soils of the wetland at a distance of 0, 0.25, 0.50 and 0.75 meters were collected and analyzed using EPA’s Method 2003b(HPLC technique)

174 samples of ballast (rock) from around (east/west) the railway ties at the distance of 5, 20 and 30 cm were collected and analyzed using modified EPA method 8310 (HPLC technique).

 36 core samples of  ballast rock and  11 sediments) collected at a distance 10 cm form each other (up to 60 cm)  were collected and analyzed  using EPA’s method 8310.

LOD of the analytical methods used  was set between 0.20 to 0.100 µg/g.

 First sample analysis was done 10 days after the construction of the simulated wetland.

Thereafter the sample analysis and data collections were done at 3, 6, 9, 12 ,15 and 18 months.

The  measured concentrations of  PAHs form new, weathered  generally declined progressively from  5 cm to 30 cm distances for all samples taken after 10 days, 3, 6, 9, 12, 15, and 18 months.

 Similarly, core samples at 10-cm depth increment  up to 60 cm down, showed that the concentration decreased from 1.207 µg/g  at 0 cm to 0.482 µg/g at 60 cm depth.

 From stormwater samples collected after 18 months, two PAHs were detected from newly treated railway ties; Benzo(a)anthracene (0.00019 mg/L) and phenanthrene (0.00066 mg/L). This was observed in only one out of 16 samples that were collected.

Fluoranthene, phenanthrene and pyrene were detected from weathered railway ties.

Because in this particular simulated site the ballast did not have organic carbon and therefore the likelihood of microbes in such an environment were not likely to survive,. no biodegradation study was conducted.

Sooke Basin Study, 1999, and 2001: A Joint Study sponsored by Environmental Canada,  and Canadian  Governamental Subsidiaries,  Canadian Institute of Treated wood (CITW) and Creosote Council II. Study Director: K. Brooks.

It is a field study on treated Douglas fir wood. The study was carried out in Sooke Basin, Vancouver, Canada. Duration of the study was 584 days.

Two six-pilings of treated Douglas fir  dolphins were placed about 60 meters  from shoreline. One piling consisted of freshly treated wood and the second of the weathered treated wood. Third piling of untreated wood and constituted a blank. The retention for the freshly treated wood was 27 pounds per cubic foot, higher than usual retention used for wood treatment and it represented a worst case scenario. Study and results were based on: 1) Site characterization which included: sediment total organic carbon content, grain size, background PAHs, benthic infuana, and water temperature, salinity, current profile, total suspended solids and total volatile solids;  and 2) results/data collected: quantitative determination of 16 EPA Priority PAHs + benzo(e)pyrene and alkylated PAHs in the various sections of  upstream  and downstream  sediments, as a function of time and distance,  concentration of PAHs within the water column as a function of distance from both freshly treated and weathered treated woods, impact on the infuana  as a function of time and distance, impact on the mussel (survival, growth, bioaccumulation  into different tissues and reproductive impact form the freshly treated wood and the weathered treated wood.

There a surge to higher concentration immediately after the study commenced. Insoluble PAHs were found at the surface or subsurface of the  benthic sediment. Elevated concentration of PAHs were found up to 7.5 meters away from the piling site and to much lesser extent at about 10 meters. The overall ratio of the PAHs initially in the benthic samples was 1:1 for the low to high molecular wt PAHs; by day 384 of the study that ratio changed to 8:2 for the low to high molecular weight PAHs.

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Southworth, R.G.  1977.  Aquatic Toxicology, ASTM ATP 667.  L.L. Marking, R.A. Kimerle, Eds., American Society for Testing and Materials: 359-380, Philadelphia.

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Webb, D.A.  No date available.  Creosote, its use as a wood preservative in the railroad transportation industry with environmental considerations.  American Wood Preserver’s Association.

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 PAGE  10

 PAGE  40

Table 3.  Photolysis of Selected PAHs Found in P1/P13 and P2 Fractions of Coal Tar Creosote (Cont’d)

Table 5.  Aquatic Soil Metabolism (Biodegradation) Results for Creosote/PCP Contaminants  In Groundwater Samples From Pensacola, Florida Superfund Site (Cont’d)


[Federal Register Volume 87, Number 101 (Wednesday, May 25, 2022)]
[Notices]
[Pages 31872-31873]
[FR Doc No: 2022-11224]

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

DEPARTMENT OF ENERGY

Federal Energy Regulatory Commission

[Docket No. EL22-44-000]

Grand River Dam Authority; Notice of Institution of Section 206
Proceeding and Refund Effective Date

    On May 19, 2022, the Commission issued an order in Docket No. EL22-
44-000, pursuant to section 206 of the Federal Power Act (FPA), 16
U.S.C. 824e, instituting an investigation into whether Grand River Dam
Authority's formula rate protocols are unjust, unreasonable, unduly
discriminatory or preferential, or otherwise unlawful. Grand River Dam
Authority, 179 FERC ] 61,109 (2022).
    The refund effective date in Docket No. EL22-44-000, established
pursuant to section 206(b) of the FPA, will be the date of publication
of this notice in the Federal Register.
    Any interested person desiring to be heard in Docket No. EL22-44-
000 must file a notice of intervention or motion to intervene, as
appropriate, with the

Federal Energy Regulatory Commission, in accordance with Rule 214 of
the Commission's Rules of Practice and Procedure, 18 CFR 385.214
(2021), within 21 days of the date of issuance of the order.
    In addition to publishing the full text of this document in the
Federal Register, the Commission provides all interested persons an
opportunity to view and/or print the contents of this document via the
internet through the Commission's Home Page (http://www.ferc.gov) using
the ``eLibrary'' link. Enter the docket number excluding the last three
digits in the docket number field to access the document. At this time,
the Commission has suspended access to the Commission's Public
Reference Room, due to the proclamation declaring a National Emergency
concerning the Novel Coronavirus Disease (COVID-19), issued by the
President on March 13, 2020. For assistance, contact FERC at
[email protected] or call toll-free,<PHONE_NUMBER> or TYY,
(202) 502-8659.
    The Commission strongly encourages electronic filings of comments,
protests and interventions in lieu of paper using the ``eFile'' link at
http://www.ferc.gov. In lieu of electronic filing, you may submit a
paper copy. Submissions sent via the U.S. Postal Service must be
addressed to: Kimberly D. Bose, Secretary, Federal Energy Regulatory
Commission, 888 First Street NE, Room 1A, Washington, DC 20426.
Submissions sent via any other carrier must be addressed to: Kimberly
D. Bose, Secretary, Federal Energy Regulatory Commission, 12225 Wilkins
Avenue, Rockville, Maryland 20852.

    Dated: May 19, 2022.
Debbie-Anne A. Reese,
Deputy Secretary.
[FR Doc. 2022-11224 Filed 5-24-22; 8:45 am]
BILLING CODE 6717-01-P