Regulatory Toxicology and Pharmacology 47 (2007) 288–295

www.elsevier.com/locate/yrtph

Characterization of EPA’s 16 priority pollutant polycyclic

aromatic hydrocarbons (PAHs) in tank bottom solids
and associated contaminated soils at oil exploration
and production sites in Texas
Heidi K. Bojes *, Peter G. Pope
Site Remediation Section, Oil and Gas Division, Railroad Commission of Texas, 1701 N. Congress, Austin, TX 78701, USA

Received 4 April 2006

Available online 8 February 2007

Abstract

The purpose of this study was to determine the concentration and types of polycyclic aromatic hydrocarbons (PAHs), a group of
environmentally toxic and persistent chemicals, at contaminated oil exploration and production (E&P) sites located in environmentally
sensitive and geographically distinct areas throughout Texas. Samples of tank bottom solids, the oily sediment that collects at the bottom
of the tanks, were collected from inactive crude oil storage tanks at E&P sites and hydrocarbon contaminated soil samples were collected
from the area surrounding each tank that was sampled. All samples were analyzed for the 16 PAH priority pollutant listed by US EPA
and for total petroleum hydrocarbons (TPH). The results demonstrate that overall average PAH concentrations were significantly higher
in tank bottom solids than in contaminated soils. Total PAH concentrations decreased predictably with diminishing hydrocarbon con-
centrations; but the percent fraction of carcinogenic PAHs per total measured PAH content increased from approximately 12% in tank
bottom solids to about 46% in the contaminated soils. These results suggest that the PAH content found in tank bottom solids cannot
reliably be used to predict the PAH content in associated contaminated soil. Comparison of PAHs to conservative risk-based screening
levels for direct exposure to soil and leaching from soil to groundwater indicate that PAHs are not likely to exceed default risk-based
thresholds in soils containing TPH of 1% (10,000 mg/kg) or less. These results show that the magnitude of TPH concentration may
be a useful indicator of potential risk from PAHs in crude oil-contaminated soils. The results also provide credibility to the 1%
(10,000 mg/kg) TPH cleanup level, used in Texas as a default management level at E&P sites located in non-sensitive areas, with respect
to PAH toxicity.
 2006 Elsevier Inc. All rights reserved.

1. Introduction allow them to persist in the environment long after other

Hydrocarbons, primarily measured as total petroleum
hydrocarbons (TPH), comprise the majority of compo-
nents in most crude oils and contain hundreds of individual
components. Polycyclic aromatic hydrocarbons (PAHs)
are one target component of TPH and are of concern
because some are carcinogenic and may be toxic to the
environment (Zemanek et al., 1997; Harvey, 1991; ATS-
DR, 2005). PAHs also have uniquely stable structures that
*
Corresponding author. Fax: +1 512 463 2388.
E-mail address: heidi.bojes@rrc.state.tx.us (H.K. Bojes).
oil field product constituents have degraded (Sugiura
et al., 1997).
The US EPA has classified 16 of the PAHs as priority-
pollutants based on toxicity, potential for human exposure,
frequency of occurrence at hazardous waste sites, and the
extent of information available (ATSDR, 2005) (Table 1).
Of these PAHs US EPA considers seven, i.e. benzo(a)an-
thracene, chrysene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(k)fluoranthene, dibenz(a,h)anthracene, and inde-
no(1,2,3-cd)pyrene, as probable human carcinogens
(NTP, 2005). As shown in Table 1, generally, PAHs consid-
ered to be carcinogenic have higher molecular weight, i.e.

0273-2300/$ - see front matter  2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.yrtph.2006.11.007
 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295 289

Table 1 (10,000 mg/kg). Naphthalene was determined to be the

US EPA’s 16 priority-pollutant PAHs and selected physical–chemical only PAH that may be present at concentrations that
properties (ATSDR, 2005)
exceeded a risk level when TPH levels were less than 1%
Polycyclic aromatic Structure Molecular Solubility Vapor (10,000 mg/kg). These investigators concluded that routine
hydrocarbonsa (# of weight (mg/L) pressure
rings) (g/mole) (mm Hg)
analyses for all PAHs at E&P crude oil or condensate spill
sites are unnecessary.
Naphthalene 2 128.17 31 8.89E 02
Acenaphthene 3 154.21 3.8 3.75E 03
The application of these results to oil contamination at
Acenaphthylene 3 152.20 16.1 2.90E 02 historic E&P sites is limited in that the investigators did
Anthracene 3 178.23 0.045 2.55E 05 not consider situations where multiple oil spills have
Phenanthrene 3 178.23 1.1 6.80E 04 occurred on soils. Additionally, the impacts of weathering,
Fluorene 3 166.22 1.9 3.24E 03 a process that can diminish and alter the composition of
Fluoranthene 4 202.26 0.26 8.13E 06
Benzo(a)anthracene 4 228.29 0.011 1.54E 07
TPH (Atlas and Cerniglia, 1995), were not evaluated.
Chrysene 4 228.29 0.0015 7.80E 09 The current study addresses these limitations by determin-
Pyrene 4 202.26 0.132 4.25E 06 ing the concentrations of several specific PAHs in tank bot-
Benzo(a)pyrene 5 252.32 0.0038 4.89E 09 tom solids and in contaminated soil near the inactive
Benzo(b)fluoranthene 5 252.32 0.0015 8.06E 08 storage tanks. This study further examines whether TPH,
Benzo(k)fluoranthene 5 252.32 0.0008 9.59E 11
Dibenz(a,h)anthracene 6 278.35 0.0005 2.10E 11
a constituent routinely evaluated at contaminated E&P
Benzo(g,h,i)perylene 6 276.34 0.00026 1.00E 10 sites, can be used as an indicator of potential risk from
Indeno[1,2,3-cd] 6 276.34 0.062 1.40E 10 PAHs.
pyrene
a
US EPA has classified PAHs in italics as probable human carcinogens 2. Methods
(NTP, 2005).
2.1. Sampling sites

number of aromatic rings, and lower vapor pressure and Sampling sites were identified in 48 Texas counties and in each of the
nine geographically distinct Railroad Commission of Texas (RRC) districts
solubility constants compared to the non-carcinogenic (Fig. 1). A sampling site typically consisted of an abandoned 210–500 bar-
PAHs. The physical–chemical characteristics of PAHs also rel tank with tank bottom solids and associated contaminated soils within a
contribute directly to their recalcitrant nature in the envi- 25 foot radius of the tank. A sample was collected from tank bottom solids,
ronment (Kanaly and Harayama, 2000). the oily sediment that collects at the bottom of the tanks, and three oil-con-
Oil exploration and production (E&P) processes can taminated soil samples were collected from the area surrounding each tank.
Contaminated soil samples are soils where oil has spilled on the ground and
contribute to localized loadings of PAHs into the environ- mixed with the native soil to varying degrees. Highest concentrations of oil
ment through accidental spillage or leaks of oil from were collected in soils nearest the tank and increasingly less contaminated
producing wells, storage tanks, gathering lines, transporta- soils were collected at increasing distances from the tank. Soil was catego-
tion lines and pits. However, limited information exists on rized as heavily contaminated soil, moderately contaminated soil, and
the content and relative concentrations of PAHs in tank
bottom solids, the oily sediment that collects at the bottom
of the tank, or in soils surrounding tanks that have been
subjected to multiple oil spills and environmental condi-
tions. For example, the American Petroleum Institute
(API) analyzed crude oil-containing soils and tank bottom
solids for PAHs including chrysene, naphthalene, phenan-
threne, and 1-methyl naphthalene; and the US EPA Office
of Solid Waste evaluated crude oil tank bottom wastes for
PAHs and other semi-volatile organic compounds includ-
ing naphthalene, phenanthrene, fluorene, and chrysene
(API, 1996; EPA, 1994). Both groups found relatively
low concentrations of PAHs in oil-contaminated soils
and tank bottom solids, e.g. maximum concentrations ran-
ged from 5.1 mg/kg for chrysene to 268 mg/kg for naph-
thalene. These results are limited in that only four PAHs
were evaluated.
PAHs were also evaluated in crude oils and condensates
collected from crude oil production sites around the world
Fig. 1. Samples were collected from 68 sensitive E&P Sites (black dots) in
(Kerr et al., 2001). It was demonstrated that the potential
48 different counties and in all RRC’s districts. Numbers refer to RRC’s
risk from direct soil exposure and leaching of chemicals districts: 1&2, San Antonio; 3, Houston; 4, Corpus Christi; 5&6, Kilgore;
to groundwater for 15 of the 16 priority pollutant PAHs 7B, Abilene; 7Cl, San Angelo; 8&8A, Midland; 9, Wichita Falls; and,
is not significant as long as TPH levels are less than 1% 10, Pampa.
290 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295
mildly contaminated soil based on field screening by visual examination
and odor. Together, 72 tank bottom samples, 68 heavily contaminated soil,
68 moderately contaminated soil, 68 mildly contaminated soil samples were
collected. Nine duplicate samples, one from each district, were also collect-
ed from the heavily oil-contaminated soil.
Sampling sites were located in sensitive areas in Texas. Sites were
determined to be environmentally sensitive based on the presence of one
or more factors including shallow groundwater or pathways for commu-
nication with deeper groundwater, proximity to surface water, including
lakes, rivers, streams, dry or flowing creeks, irrigation canals, stock tanks,
and wetlands, proximity to natural wildlife refuges or parks, or proximity
to commercial or residential areas (RRC, 1993).
2.2. Sampling method
Surface grab samples were collected from tank bottom solids and soil
using a decontaminated hand trowel. Approximately, four ounces (124 g)
of sample including duplicates were collected. Nine duplicate samples, one
from each district, were collected. Samples were placed in laboratory-
supplied containers and chilled to approximately 4 C. Samples collected
from the San Antonio, Houston, Abilene, San Angelo, Wichita Falls,
and Pampa RRCs districts were shipped under chain-of-custody proce-
dures to Anacon Inc., Houston, Texas, for analytical evaluation. Samples
collected from the Corpus Christi, Kilgore, and Midland RRCs districts
were shipped under chain-of-custody to Alamo Analytical, San Antonio,
Texas, for analytical evaluation. Analytical methods were conducted
according to the existing Quality Assurance Plans (QAPs) per the analyt-
ical laboratory.
2.3. Sample analyses
Samples were evaluated for PAHs, i.e. acenaphthene, acenaphthylene,
anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthra-
cene, fluoranthene, fluorene, indeno(1,2,3-cd)pyrene, naphthalene, phen-
anthrene, and pyrene, by gas chromatography/mass spectrometry (GC/
MS) operated in the select ion monitoring (SIM) mode using a modified
US EPA method 8270 (EPA, 2005a). Samples heavily impacted with crude
oil were also passed through an alumina gel chromatography column to
separate the aromatic hydrocarbons using modified EPA method 3611 pri-
or to PAH analyses (EPA, 2005b). This method was necessary to reduce
elevated detection limits.
TX Method 1006 was used to determine the distribution and concen-
tration of hydrocarbons in the aliphatic and aromatic fractions of TPH
within the approximate size range of >C6–C35 (TCEQ, 2005). The sam-
ples (10 g) were first extracted using n-pentane (10 mL) and then fraction-
ated, i.e. separated into aliphatic and aromatic hydrocarbon fractions,
using a silica gel column procedure SW-846 US EPA Method 3630
(EPA, 1996a). Aliphatic and aromatic hydrocarbon fractions were ana-
lyzed separately using gas chromatography (GC) (HP 5890 GC equipped
with a 30-m DB-5 capillary column and a flame ionization detector (FID).
The injection port was operated in the splitless mode at 275 C. The initial
oven temperature of 10 C was maintained for five minutes and then
increased to a final temperature of 320 C at a rate of 4 C/min. The
GC/FID was calibrated with standard compounds at five different concen-
tration levels ranging from 20 to 1000 ppm. Aliphatic hydrocarbons were
defined in this method as those compounds detected from n-hexane (C6) to
n-pentatriacontane (C35 inclusive) in the chromatogram of the aliphatic
fraction. Aromatic hydrocarbons were defined in this method as those
compounds detected from n-heptane (C7) to the retention time of n-pento-
triacontane (C35) in the chromatogram of the aromatic fraction.
2.4. Data analysis
Data were grouped according to level of contamination, i.e. tank bot-
tom solids, heavily contaminated soil, moderately contaminated soil, and
mildly contaminated soil, and data groups were evaluated using one-way
analysis of variance (p < 0.05) to determine if samples represent statisti-
cally different populations. Pair-wise comparisons were made using the
Tukey HSD test.
2.5. Quality evaluations
In a few cases, detection limits that exceeded data quality objectives
due to dilution in PAH analyses were not achieved using modified EPA
method 3611 and, therefore, these data were not used. The remaining data
collected for this study were determined to be valid and useable for the
purpose of characterizing the concentrations and distribution of PAHs
in tank bottoms and associated impacted soils.
3. Results and discussion
3.1. Characterization of hydrocarbons in tank bottom solids
and contaminated soils
TPH, defined for this study as the sum of the >C6–C35
aliphatic and aromatic hydrocarbon fractions analyzed
with TX 1006 Method, was measured in tank bottom solids
and contaminated soils. Summary statistics, i.e. frequency
detected and mean concentrations, for TPH and TPH frac-
tions are presented in Table 2. The average TPH concentra-
tion of tank bottoms was 34% (337,154 mg/kg) and was
significantly greater, by approximately seven times, than
the combined average concentrations of contaminated soil
(Table 2). Average TPH levels in soils decreased predict-
ably with decreasing visual hydrocarbon concentration
from 7.5% (75,254 mg/kg) in heavily contaminated soils
to 4.2% (42,333 mg/kg) and 2.1% (21,302 mg/kg) in moder-
ately and mildly contaminated soils, respectively. These
results confirm that classification of samples based on visu-
al examination of soils is reasonably accurate. The distribu-
tion of TPH fractions across all sample types was similar in
that long-chain aliphatic hydrocarbons, i.e. >C12–C16,
>C16–C21, and >C21–C35, comprised up to 80% or more
of the TPH content and were detected in up to 80% or
more of the samples (Table 2). Short-chain aliphatic, i.e.
>C6–C8 and >C8–C10, and aromatic hydrocarbons, i.e.
>C7–C8 and >C8–C10, made up about 10% of the TPH
content in tank bottom solids and in contaminated soils.
The detection frequency of short-chain aliphatic and aro-
matic hydrocarbons decreased from 25% in waste to 1%
in mildly contaminated soils.
3.2. Characterization of PAHs in tank bottom solids and
contaminated soils
Total PAH, defined as the sum of the concentrations of
the 16 PAHs that were detected in a sample, and individual
PAH concentrations were pooled into four categories: tank
bottom solids; heavily contaminated soil; moderately con-
taminated soil; and mildly contaminated soil. Summary sta-
tistics, i.e. frequency detected and mean concentrations, for
total PAH and individual PAHs are presented in Table 3.
The average total PAH concentration of tank bottom solids
was significantly greater by approximately eight times than
 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295 291

Table 2
Mean concentration and detection frequency of TPH in tank bottom solids and associated oil-contaminated soilsa,b
Total petroleum Sample type
hydrocarbons (C)
Tank bottom solids Oil-contaminated soil
Heavily Moderately Mildly
Mean conc. Detection Mean conc. Detection Mean conc. Detection Mean conc. Detection
(mg/kg) Frequency (%) (mg/kg) frequency (%) (mg/kg) frequency (%) (mg/kg) frequency (%)
Aliphatics
>6–8 15270 25 1195 3 309 9 503 1
>8–10 12949 54 949 13 558 16 657 9
>10–12 21544 77 2047 35 1058 26 784 15
>12–16 73298 99 6869 94 4479 90 1801 71
>16–21 83879 100 21948 100 12362 94 5790 85
>21–35 86773 100 32380 100 18310 93 8932 87
Aromatics
>7–8 1111 5 226 1 31 1 0 0
>8–10 2160 11 230 1 37 1 71 3
>10–12 3351 19 570 4 103 4 202 4
>12–16 6932 73 854 65 489 56 170 41
>16–21 12833 86 2625 79 1547 72 799 62
>21–35 17054 89 5362 18 3051 78 1593 63
Total TPH 337154A 100 75254B 100 42333C 100 21302D 100
a
Mean conc. (concentration) of all detected TPH. Detection limits ranged from 0.02 to 500 mg/kg.
b
Letters indicate significant difference at p < 0.05. Results compared using one-way analysis of variance. Pair-wise comparisons were made using the
Tukey HSD test.

Table 3
Mean concentration and detection frequency of PAHs in tank bottom solids and associated oil-contaminated soilsa,b,c
Polycyclic aromatic Sample type
hydrocarbonsb Tank bottom solids Oil-contaminated soil
Heavily Moderately Mildly
Mean conc. Detection Mean conc. Detection Mean conc. Detection Mean conc. Detection
(mg/kg) frequency (%) (mg/kg) frequency (%) (mg/kg) frequency (%) (mg/kg) frequency (%)
Naphthalene 254.5 59 3.9 24 1.6 19 2.8 9
Acenaphthene 34.8 30 2.5 19 1.3 12 1.9 7
Acenaphthylene 24.2 27 2.4 13 0.4 7 0.5 9
Anthracene 24.8 37 3.2 26 2.3 10 0.5 6
Phenanthrene 19.9 67 12.0 53 4.1 40 5.2 29
Fluorene 80.6 54 13.6 44 2.5 24 3.1 19
Fluoranthene 15.5 33 3.4 28 3.2 16 1.8 7
Benzo(a)anthracene 9.4 10 13.4 4 11.0 3 3.2 3
Chrysene 24.5 80 4.5 74 3.2 65 1.9 54
Pyrene 19.9 46 4.3 43 3.4 28 2.1 19
Benzo(a)pyrene 8.4 6 5.4 10 4.0 10 1.6 6
Benzo(b)fluoranthene 8.2 8 3.4 18 5.1 7 1.6 7
Benzo(k)fluoranthene 7.3 6 3.3 19 5.1 6 1.7 4
Dibenz(a,h)anthracene 4.1 1 2.6 3 3.0 1 0.6 3
Benzo(g,h,i)perylene 5.9 3 2.9 6 14.9 19 1.1 4
Indeno[1,2,3-cd]pyrene 5.8 3 5.6 3 7.3 12 1.3 3
Total PAHs 547.7A 100 86.4B 100 72.5B 100 31.0B 100
a
Mean conc. (concentration) of all PAHs detected. Detection limits ranged from 0.02 to 0.33 mg/kg.
b
US EPA has classified PAHs in italics as probable human carcinogens (NTP, 2005).
c
Letters indicate significant difference at p < 0.05. Results compared using one-way analysis of variance. Pair-wise comparisons were made using the
Tukey HSD test.

the combined average PAH concentration of contaminated decreased significantly with decreasing visual evidence of
soil. Of the PAHs detected, low molecular weight PAHs, hydrocarbon-impact from 86.4 mg/kg in heavily contami-
such as naphthalene at 254.5 mg/kg, were detected at high- nated soils to 72.5 and 31.0 mg/kg in moderately and mildly
est levels in tank bottom solids. Average total PAH values contaminated soils, respectively. Benzo(a)anthracene at
292 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295
13.4 mg/kg and fluorene at 13.6 mg/kg were detected at
greatest levels in heavily contaminated soils.
Generally, the detection frequency of PAHs decreased
with decreasing hydrocarbon concentration. Of the PAHs
detected, low molecular weight PAHs were detected more
frequently than the higher molecular weight PAHs (Table
3). For example, low molecular weight PAHs, i.e. naphtha-
lene, phenanthrene, fluorene and chrysene, were detected
in greater than 54% of the tank bottom solid samples
evaluated; while high molecular weight PAHs, i.e.
benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranth-
ene, benzo(k)fluoranthene, dibenz(a,h)anthracene, ben-
zo(g,h,i)perylene, and indeno(1,2,3-cd)pyrene, were
detected in less than 8% of the tank bottom samples. In heav-
ily contaminated soils, low molecular weight PAHs, i.e.
phenanthrene and chrysene, were detected in greater than
53% of the soil samples while high molecular weight PAHs,
i.e. benzo(b)fluoranthene and benzo(k)fluoranthene, were
detected in approximately 18% of the soil samples.
These results show that the concentrations and compo-
sition of PAHs in tank bottom solids varies from the con-
centrations and composition of PAHs found in
contaminated soils. As the lower molecular weight PAHs
are more volatile and soluble than the higher molecular
weight PAHs, volatilization and leaching of the lower
molecular weight PAHs might be responsible for some of
the decrease in total PAH concentration observed in con-
taminated soils (Kanaly and Harayama, 2000). The high
content of low molecular weight PAHs in tank bottom sol-
ids suggests that the hydrocarbons in tank bottom solids
are less weathered relative to contaminated soils. The dis-
tribution of PAHs in tank bottom solids is consistent with
what was found in a previous study conducted in crude oils
from production sites, which are unlikely to have under-
gone significant weathering (Kerr et al., 2001). For exam-
ple, Kerr et al. detected low molecular weight PAHs such
as naphthalene and phenanthrene at highest levels, i.e.
422 and 176 mg/kg, and most frequently in fresh crude oils.
These results suggest that the PAH content found in tank
bottom solids, and fresh crude, cannot be used to reliably
determine the PAH content in associated contaminated
soil.
One reason PAHs are of concern is due to the ability of
some to cause cancer (Zemanek et al., 1997; Harvey, 1991;
ATSDR, 2005). The average total carcinogenic PAH con-
centrations were detected at highest levels in tank bottom
solids and decreased with decreasing hydrocarbon contam-
ination in soils (Fig. 2). But, the percent fraction of carcin-
ogenic PAHs per total PAH content increased from
approximately 12% in tank bottom solids to about 46%
in the contaminated soil samples, indicating that the car-
cinogenic component is greater in affected soils than in
the waste (Fig. 3). These results are consistent with the
findings from other studies that have shown that carcino-
genic PAHs generally exist in the environment longer than
non-carcinogenic PAHs (Shuttleworth and Cerniglia,
1995); however, the environmental persistence of PAHs
Fig. 2. The mean total concentration of carcinogenic (h) and non-
carcinogenic (n) PAHs in tank bottom solids and heavily, moderately,
and mildly oil-contaminated soil. Letters indicate significant difference at
p < 0.05. Results compared using one-way analysis of variance. Pair-wise
comparisons were made using the Tukey HSD test.
Fig. 3. Percent fraction of carcinogenic (h) and non-carcinogenic (n)
PAHs per total PAH content in tank bottom solids and heavily,
moderately, and mildly oil-contaminated soil.
in soils depends on many factors, including soil properties
such as pH, particle size, moisture content and organic
matter. Other studies have shown that the chemical extract-
ability and bioavailability of hydrophobic compounds like
PAHs from soil decrease with increasing time (Nam and
Alexander, 1998; Alexander, 1995, 2000; Chung and
Alexander, 1999, 1998; Macleod and Semple, 2000). There-
fore, assimilation and possible toxicity of PAHs may be
limited based on their hydrophobic characteristics. Addi-
tional studies need to be conducted to determine the bio-
availability and risk of PAHs in soils containing TPH.
3.3. Does the presence of PAHs in soils confer toxic levels to
human health and the environment?
Comparing the concentrations to chemical-specific risk-
based screening levels (RBSLs) constitutes one method that
the potential risk from exposure to chemicals in the envi-
ronment can be first assessed at E&P contaminated-sites.
RBSLs are threshold concentrations in site media, e.g. soil,
at or below which little or no likelihood of unacceptable
risk, e.g. one-in-a-hundred thousand (1 · 10 5) for carcin-
ogens or hazard quotient (HQ) of one for non-carcinogens,
is expected. RBSLs are often derived by state and federal
regulatory agencies using conservative default exposure
assumptions that follow protocol established by the US
EPA for evaluating potential human health effects at Com-
prehensive Environmental Response, Compensation, and
Liability Act (CERCLA) sites (EPA, 2000, 1996b). In
Texas, the protective concentration levels (PCLs) used in
 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295 293

this study have been developed as Tier 1 RBSLs for com-

mercial/industrial and residential scenarios and exposure
pathways including direct contact to soil, such as exposure
to soil by incidental ingestion, inhalation of vapors, dermal
contact, and leaching from soil to groundwater ingestion
(TCEQ, 2001).
As depicted in Table 4, maximum concentrations of
several carcinogenic PAHs, i.e. benzo(a)anthracene,
benzo(a)pyrene, benzo(b)fluoranthene, and dibenz(a,h)an-
thracene, found in heavily, moderately and mildly contam-
inated soils exceeded the commercial/industrial and
residential screening levels for both direct exposure to soil
by up to 59 times and leaching from soil to groundwater
protective concentration levels by up to four times. Addi-
tionally, indeno(1,2,3-cd)pyrene exceeded the residential
protective concentration level for direct exposure pathway
by three times. These results show that some carcinogenic
PAHs may be present in oil-contaminated soils at levels
that exceed screening criteria.
In the present study, concentrations of the PAH constit-
uents, such as benzo(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene, dibenz(a,h)anthracene, and inde-
no(1,2,3-cd)pyrene, which exceeded risk thresholds were
compared to TPH levels in soils to determine if TPH is a
reliable indicator of potential risk from PAHs (Fig. 4). With
the exception of benzo(a)pyrene, maximum concentrations
of PAHs were well below direct contact to soil and soil
leaching to groundwater RBSLs at TPH concentrations of
2% (20,000 mg/kg) or less. The maximum benzo(a)pyrene
concentration exceeded the RBSL by approximately two
times at TPH concentrations of 1% (10,000 mg/kg) or less;
however, the average benzo(a)pyrene level was below the
Fig. 4. Maximum concentration of benzo(a)anthracene, benzo(a)pyrene,
benzo(b)fluoranthene, dibenzo(a,h)anthracene, and indeno(1,2,3-cd)py-
rene per percent total petroleum hydrocarbons. PAHs were compared to
the lowest risk-based screening levels. The risk-based screening level for
benzo(a)anthracene, benzo(b)fluoranthene and indeno(1,2,3-cd)pyrene is
5.7 mg/kg and is shown as a dashed line. The risk-based screening level for
benzo(a)pyrene and dibenzo(a,h)anthracene is 0.55 mg/kg and is shown as
a solid line.
RBSL. Furthermore, benzo(a)pyrene was detected in
approximately 7% of the soil samples containing TPH of
1% (10,000 mg/kg) or less. Collectively, these results show
that although the carcinogenic fraction of PAHs may
increase as the hydrocarbon contamination in soils dimin-
ishes, the potential risk of the PAHs is expected to be below
acceptable levels at TPH concentrations less than 1%
(10,000 mg/kg). These results show that the magnitude of
TPH concentration may be a useful indicator of potential
risk from PAHs in crude oil-contaminated soils.
A 1% (10,000 mg/kg) TPH concentration is used in sev-
eral states, including Texas, as a default management level
at E&P sites (RRC, 1993; Hamilton et al., 2001). Studies
have shown that 1% (10,000 mg/kg) TPH or less, assuming

Table 4
Comparison of the maximum detected PAHs in oil-contaminated soils to Tier 1 risk-based screening levelsa,b

a
Tier 1 risk-based screening levels, i.e. protective concentration levels, for commercial/industrial and residential scenarios for the direct contact to soil
and protection of groundwater exposure pathways (TCEQ, 2001).
b
Bold values and shaded squares indicate an exceedance of a Tier 1 risk-based screening level.
294 H.K. Bojes, P.G. Pope / Regulatory Toxicology and Pharmacology 47 (2007) 288–295
acceptable salt and pH levels, did not significantly reduced
plant yields (Deuel, 1991; Chaı̂neau et al., 1997; Salanitro
et al., 1997). Other studies demonstrated 1% (10,000 mg/
kg) to be below the minimum level required for hydrocar-
bon mobility, i.e. less than the residual soil saturation
(Hamilton et al., 2001). The current study’s results provide
credibility to the 1% (10,000 mg/kg) TPH cleanup level in
terms of PAHs and toxicity.
4. Conclusion
This study fills in some data gaps regarding PAH con-
tent in oil at E&P contaminated sites where multiple oil
spills have occurred and oil contaminated soil has been
weathered. The results show that PAH content found in
tank bottom solids, collected from E&P sites located in
environmentally sensitive and geographically distinct areas
throughout Texas, cannot reliably be used to determine the
PAH content in contaminated soil. Also, these results dem-
onstrate that the magnitude of TPH concentration may be
a useful indicator of potential risk from PAHs in crude oil-
contaminated soils and provide credibility to the 1%
(10,000 mg/kg) TPH cleanup level with respect to PAH
toxicity.
Acknowledgments
We thank the following RRC district cleanup coordinator
operators for their help and knowledge of the oilfield: Steve
Graham, Rodney Moore, Ron Smelley, Adam Taylor, Roy
Staiger, Kevin Shomette, Jeff Lauman, Paul Harris, Olin
MacNamara, Nick Davis, Brian Floyd, Joe Guerra, Tim
Prude, Rollen Nunley, Ray Horton, and Joe Kitchens.
A Brownfields Training, Research, and Technical Assis-
tance Grant from US EPA (TR-831279010) supported this
work.
The views and opinions found in the contents of this
document are those of the authors and do not necessarily
reflect those of the RRC. Mention of trade names or com-
mercial entities does not constitute their endorsement by
the RRC.
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