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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


oil field product constituents have degraded (Sugiura
Hydrocarbons, primarily measured as total petroleum et al., 1997).
hydrocarbons (TPH), comprise the majority of compo- The US EPA has classified 16 of the PAHs as priority-
nents in most crude oils and contain hundreds of individual pollutants based on toxicity, potential for human exposure,
components. Polycyclic aromatic hydrocarbons (PAHs) frequency of occurrence at hazardous waste sites, and the
are one target component of TPH and are of concern extent of information available (ATSDR, 2005) (Table 1).
because some are carcinogenic and may be toxic to the Of these PAHs US EPA considers seven, i.e. benzo(a)an-
environment (Zemanek et al., 1997; Harvey, 1991; ATS- thracene, chrysene, benzo(a)pyrene, benzo(b)fluoranthene,
DR, 2005). PAHs also have uniquely stable structures that benzo(k)fluoranthene, dibenz(a,h)anthracene, and inde-
no(1,2,3-cd)pyrene, as probable human carcinogens
*
Corresponding author. Fax: +1 512 463 2388. (NTP, 2005). As shown in Table 1, generally, PAHs consid-
E-mail address: heidi.bojes@rrc.state.tx.us (H.K. Bojes). 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 analysis of variance (p < 0.05) to determine if samples represent statisti-
and odor. Together, 72 tank bottom samples, 68 heavily contaminated soil, cally different populations. Pair-wise comparisons were made using the
68 moderately contaminated soil, 68 mildly contaminated soil samples were Tukey HSD test.
collected. Nine duplicate samples, one from each district, were also collect-
ed from the heavily oil-contaminated soil.
2.5. Quality evaluations
Sampling sites were located in sensitive areas in Texas. Sites were
determined to be environmentally sensitive based on the presence of one
In a few cases, detection limits that exceeded data quality objectives
or more factors including shallow groundwater or pathways for commu-
due to dilution in PAH analyses were not achieved using modified EPA
nication with deeper groundwater, proximity to surface water, including
method 3611 and, therefore, these data were not used. The remaining data
lakes, rivers, streams, dry or flowing creeks, irrigation canals, stock tanks,
collected for this study were determined to be valid and useable for the
and wetlands, proximity to natural wildlife refuges or parks, or proximity
purpose of characterizing the concentrations and distribution of PAHs
to commercial or residential areas (RRC, 1993).
in tank bottoms and associated impacted soils.

2.2. Sampling method


3. Results and discussion
Surface grab samples were collected from tank bottom solids and soil
using a decontaminated hand trowel. Approximately, four ounces (124 g) 3.1. Characterization of hydrocarbons in tank bottom solids
of sample including duplicates were collected. Nine duplicate samples, one and contaminated soils
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, TPH, defined for this study as the sum of the >C6–C35
and Pampa RRCs districts were shipped under chain-of-custody proce- aliphatic and aromatic hydrocarbon fractions analyzed
dures to Anacon Inc., Houston, Texas, for analytical evaluation. Samples with TX 1006 Method, was measured in tank bottom solids
collected from the Corpus Christi, Kilgore, and Midland RRCs districts and contaminated soils. Summary statistics, i.e. frequency
were shipped under chain-of-custody to Alamo Analytical, San Antonio,
Texas, for analytical evaluation. Analytical methods were conducted
detected and mean concentrations, for TPH and TPH frac-
according to the existing Quality Assurance Plans (QAPs) per the analyt- tions are presented in Table 2. The average TPH concentra-
ical laboratory. tion of tank bottoms was 34% (337,154 mg/kg) and was
significantly greater, by approximately seven times, than
2.3. Sample analyses the combined average concentrations of contaminated soil
(Table 2). Average TPH levels in soils decreased predict-
Samples were evaluated for PAHs, i.e. acenaphthene, acenaphthylene, ably with decreasing visual hydrocarbon concentration
anthracene, benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene,
benzo(g,h,i)perylene, benzo(k)fluoranthene, chrysene, dibenzo(a,h)anthra-
from 7.5% (75,254 mg/kg) in heavily contaminated soils
cene, fluoranthene, fluorene, indeno(1,2,3-cd)pyrene, naphthalene, phen- to 4.2% (42,333 mg/kg) and 2.1% (21,302 mg/kg) in moder-
anthrene, and pyrene, by gas chromatography/mass spectrometry (GC/ ately and mildly contaminated soils, respectively. These
MS) operated in the select ion monitoring (SIM) mode using a modified results confirm that classification of samples based on visu-
US EPA method 8270 (EPA, 2005a). Samples heavily impacted with crude al examination of soils is reasonably accurate. The distribu-
oil were also passed through an alumina gel chromatography column to
separate the aromatic hydrocarbons using modified EPA method 3611 pri-
tion of TPH fractions across all sample types was similar in
or to PAH analyses (EPA, 2005b). This method was necessary to reduce that long-chain aliphatic hydrocarbons, i.e. >C12–C16,
elevated detection limits. >C16–C21, and >C21–C35, comprised up to 80% or more
TX Method 1006 was used to determine the distribution and concen- of the TPH content and were detected in up to 80% or
tration of hydrocarbons in the aliphatic and aromatic fractions of TPH more of the samples (Table 2). Short-chain aliphatic, i.e.
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-
>C6–C8 and >C8–C10, and aromatic hydrocarbons, i.e.
ated, i.e. separated into aliphatic and aromatic hydrocarbon fractions, >C7–C8 and >C8–C10, made up about 10% of the TPH
using a silica gel column procedure SW-846 US EPA Method 3630 content in tank bottom solids and in contaminated soils.
(EPA, 1996a). Aliphatic and aromatic hydrocarbon fractions were ana- The detection frequency of short-chain aliphatic and aro-
lyzed separately using gas chromatography (GC) (HP 5890 GC equipped matic hydrocarbons decreased from 25% in waste to 1%
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
in mildly contaminated soils.
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 3.2. Characterization of PAHs in tank bottom solids and
GC/FID was calibrated with standard compounds at five different concen-
contaminated soils
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 Total PAH, defined as the sum of the concentrations of
fraction. Aromatic hydrocarbons were defined in this method as those the 16 PAHs that were detected in a sample, and individual
compounds detected from n-heptane (C7) to the retention time of n-pento- PAH concentrations were pooled into four categories: tank
triacontane (C35) in the chromatogram of the aromatic fraction.
bottom solids; heavily contaminated soil; moderately con-
taminated soil; and mildly contaminated soil. Summary sta-
2.4. Data analysis
tistics, i.e. frequency detected and mean concentrations, for
Data were grouped according to level of contamination, i.e. tank bot- total PAH and individual PAHs are presented in Table 3.
tom solids, heavily contaminated soil, moderately contaminated soil, and The average total PAH concentration of tank bottom solids
mildly contaminated soil, and data groups were evaluated using one-way 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 Fig. 2. The mean total concentration of carcinogenic (h) and non-
evaluated; while high molecular weight PAHs, i.e. carcinogenic (n) PAHs in tank bottom solids and heavily, moderately,
benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranth- and mildly oil-contaminated soil. Letters indicate significant difference at
p < 0.05. Results compared using one-way analysis of variance. Pair-wise
ene, benzo(k)fluoranthene, dibenz(a,h)anthracene, ben- comparisons were made using the Tukey HSD test.
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 Fig. 3. Percent fraction of carcinogenic (h) and non-carcinogenic (n)
are more volatile and soluble than the higher molecular PAHs per total PAH content in tank bottom solids and heavily,
weight PAHs, volatilization and leaching of the lower moderately, and mildly oil-contaminated soil.
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 in soils depends on many factors, including soil properties
content of low molecular weight PAHs in tank bottom sol- such as pH, particle size, moisture content and organic
ids suggests that the hydrocarbons in tank bottom solids matter. Other studies have shown that the chemical extract-
are less weathered relative to contaminated soils. The dis- ability and bioavailability of hydrophobic compounds like
tribution of PAHs in tank bottom solids is consistent with PAHs from soil decrease with increasing time (Nam and
what was found in a previous study conducted in crude oils Alexander, 1998; Alexander, 1995, 2000; Chung and
from production sites, which are unlikely to have under- Alexander, 1999, 1998; Macleod and Semple, 2000). There-
gone significant weathering (Kerr et al., 2001). For exam- fore, assimilation and possible toxicity of PAHs may be
ple, Kerr et al. detected low molecular weight PAHs such limited based on their hydrophobic characteristics. Addi-
as naphthalene and phenanthrene at highest levels, i.e. tional studies need to be conducted to determine the bio-
422 and 176 mg/kg, and most frequently in fresh crude oils. availability and risk of PAHs in soils containing TPH.
These results suggest that the PAH content found in tank
bottom solids, and fresh crude, cannot be used to reliably 3.3. Does the presence of PAHs in soils confer toxic levels to
determine the PAH content in associated contaminated human health and the environment?
soil.
One reason PAHs are of concern is due to the ability of Comparing the concentrations to chemical-specific risk-
some to cause cancer (Zemanek et al., 1997; Harvey, 1991; based screening levels (RBSLs) constitutes one method that
ATSDR, 2005). The average total carcinogenic PAH con- the potential risk from exposure to chemicals in the envi-
centrations were detected at highest levels in tank bottom ronment can be first assessed at E&P contaminated-sites.
solids and decreased with decreasing hydrocarbon contam- RBSLs are threshold concentrations in site media, e.g. soil,
ination in soils (Fig. 2). But, the percent fraction of carcin- at or below which little or no likelihood of unacceptable
ogenic PAHs per total PAH content increased from risk, e.g. one-in-a-hundred thousand (1 · 10 5) for carcin-
approximately 12% in tank bottom solids to about 46% ogens or hazard quotient (HQ) of one for non-carcinogens,
in the contaminated soil samples, indicating that the car- is expected. RBSLs are often derived by state and federal
cinogenic component is greater in affected soils than in regulatory agencies using conservative default exposure
the waste (Fig. 3). These results are consistent with the assumptions that follow protocol established by the US
findings from other studies that have shown that carcino- EPA for evaluating potential human health effects at Com-
genic PAHs generally exist in the environment longer than prehensive Environmental Response, Compensation, and
non-carcinogenic PAHs (Shuttleworth and Cerniglia, Liability Act (CERCLA) sites (EPA, 2000, 1996b). In
1995); however, the environmental persistence of PAHs 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 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-
residential screening levels for both direct exposure to soil
rene per percent total petroleum hydrocarbons. PAHs were compared to
by up to 59 times and leaching from soil to groundwater the lowest risk-based screening levels. The risk-based screening level for
protective concentration levels by up to four times. Addi- benzo(a)anthracene, benzo(b)fluoranthene and indeno(1,2,3-cd)pyrene is
tionally, indeno(1,2,3-cd)pyrene exceeded the residential 5.7 mg/kg and is shown as a dashed line. The risk-based screening level for
protective concentration level for direct exposure pathway benzo(a)pyrene and dibenzo(a,h)anthracene is 0.55 mg/kg and is shown as
a solid line.
by three times. These results show that some carcinogenic
PAHs may be present in oil-contaminated soils at levels
that exceed screening criteria. RBSL. Furthermore, benzo(a)pyrene was detected in
In the present study, concentrations of the PAH constit- approximately 7% of the soil samples containing TPH of
uents, such as benzo(a)anthracene, benzo(a)pyrene, 1% (10,000 mg/kg) or less. Collectively, these results show
benzo(b)fluoranthene, dibenz(a,h)anthracene, and inde- that although the carcinogenic fraction of PAHs may
no(1,2,3-cd)pyrene, which exceeded risk thresholds were increase as the hydrocarbon contamination in soils dimin-
compared to TPH levels in soils to determine if TPH is a ishes, the potential risk of the PAHs is expected to be below
reliable indicator of potential risk from PAHs (Fig. 4). With acceptable levels at TPH concentrations less than 1%
the exception of benzo(a)pyrene, maximum concentrations (10,000 mg/kg). These results show that the magnitude of
of PAHs were well below direct contact to soil and soil TPH concentration may be a useful indicator of potential
leaching to groundwater RBSLs at TPH concentrations of risk from PAHs in crude oil-contaminated soils.
2% (20,000 mg/kg) or less. The maximum benzo(a)pyrene A 1% (10,000 mg/kg) TPH concentration is used in sev-
concentration exceeded the RBSL by approximately two eral states, including Texas, as a default management level
times at TPH concentrations of 1% (10,000 mg/kg) or less; at E&P sites (RRC, 1993; Hamilton et al., 2001). Studies
however, the average benzo(a)pyrene level was below the 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 Chung, N., Alexander, M., 1998. Differences in sequestration and
plant yields (Deuel, 1991; Chaı̂neau et al., 1997; Salanitro bioavailability of organic compounds aged in dissimilar soils. Envi-
ronmental Science and Technology 32, 855–860.
et al., 1997). Other studies demonstrated 1% (10,000 mg/ Chung, N., Alexander, M., 1999. Effect of concentration on sequestration
kg) to be below the minimum level required for hydrocar- and bioavailability to polycyclic aromatic hydrocarbons. Environmen-
bon mobility, i.e. less than the residual soil saturation tal Science and Technology 33, 3605–3608.
(Hamilton et al., 2001). The current study’s results provide Deuel Jr. L.E., 1991. Evaluation of limiting constituents suggested for
credibility to the 1% (10,000 mg/kg) TPH cleanup level in land disposal of exploration and production wastes. No. 4527,
American Petroleum Institute.
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Crude Oil Tank Bottoms and Oily Debris. US EPA, Office of Solid
4. Conclusion Waste, Washington, DC.
Environmental Protection Agency (EPA) (1996a), Method 3600C: Clean-
up, US EPA, Washington, DC. <http://www.epa.gov/epaoswer/
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Environmental Protection Agency (EPA), 2000. Region IX Preliminary
tank bottom solids, collected from E&P sites located in
Remediation Goals (PRGs). US EPA, Washington, DC.
environmentally sensitive and geographically distinct areas Environmental Protection Agency (EPA), 2005a. Method 8270C: Semi-
throughout Texas, cannot reliably be used to determine the volatile Organic Compounds by Gas Chromatography/Mass Spec-
PAH content in contaminated soil. Also, these results dem- trometry (GC/MS). US EPA, Washington, DC. <http://www.epa.gov/
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Environmental Protection Agency (EPA), 2005b. Method 3611B: Alumina
a useful indicator of potential risk from PAHs in crude oil-
Column Cleanup and Separation of Petroleum Wastes. US EPA,
contaminated soils and provide credibility to the 1% Washington, DC. <http://www.epa.gov/epaoswer/hazwaste/test/
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Acknowledgments Decision-Making for Assessing Petroleum Impacts at Exploration and
Production Sites. Department of Energy and Petroleum Environmen-
We thank the following RRC district cleanup coordinator tal Research Forum, Tulsa, OK, pp. 36–45.
operators for their help and knowledge of the oilfield: Steve Harvey, R.G., 1991. Environmental occurrence and cancer. In: Combs,
M.M., Ashby, J., Hicks, R.M., Baxter, H. (Eds.), Polycyclic Aromatic
Graham, Rodney Moore, Ron Smelley, Adam Taylor, Roy Hydrocarbons—Chemistry and Carcinogenicity. Cambridge Univer-
Staiger, Kevin Shomette, Jeff Lauman, Paul Harris, Olin sity Press, Cambridge, pp. 11–25.
MacNamara, Nick Davis, Brian Floyd, Joe Guerra, Tim Kanaly, R.A., Harayama, S., 2000. Biodegradation of high-molecular
Prude, Rollen Nunley, Ray Horton, and Joe Kitchens. weight polycyclic aromatic hydrocarbons by bacteria. Journal of
A Brownfields Training, Research, and Technical Assis- Bacteriology 182, 2059–2067.
Kerr, J.M., McMillen, S.J., Magaw, R.I., Melton, H.R., Naughton, G.,
tance Grant from US EPA (TR-831279010) supported this 2001. Risk-based soil screening levels for crude oil: the role of
work. polyaromatic hydrocarbons. In: McMillen, S.J., Magaw, R.I., Caro-
The views and opinions found in the contents of this villano, R.L. (Eds.), Risk-Based Decision-Making for Assessing
document are those of the authors and do not necessarily Petroleum Impacts at Exploration and Production Sites. Department
reflect those of the RRC. Mention of trade names or com- of Energy and Petroleum Environmental Research Forum, Tulsa, OK,
pp. 142–155.
mercial entities does not constitute their endorsement by Macleod, C.J.A., Semple, K.T., 2000. Influence of contact time on
the RRC. extractability and degradation of pyrene in Soils. Environmental
Science and Technology 34, 4952–4957.
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