p
0JL
New England Interstate
Water Pollution Control
Commission
Boott Mills South
1OO Foot of John Street
Lowell, Massachusetts
01852-1124
Bulletin 42
October
2002
LUST.
A Report On Federal & State Programs To Control Leaking Underground Storage Tanks
by Hal While, Barry Lesnik, and John Wilson
A Concise Background
on Fuel Oxygenates
Fuel oxygenates are oxygen-
containing compounds (e.g.,
ethers and alcohols) that are
added to gasoline either to boost
the octane rating, to make the
fuel burn cleaner by increas-
ing the oxygen content, or to
achieve a combination of
both. The most commonly
used oxygenates are
methyl tertiary-butyl
ether (MTBE) and /
ethanol. Other oxy- u~~
genates include ter-
tiary-amyl methyl ether (TAME), ethyl tertiary-butyl ether
(ETBE), diisopropyl ether (DIPE), tertiary-amyl ethyl ether
(TAEE), tertiary-butyl alcohol (TEA), tertiary-amyl alcohol
(TAA), and methanol. Some oxygenates have a long history
of usage in gasoline. For example, ethanol has been used in
automotive fuel blends since the 1930s. Ethers, and primarily
MTBE, have been used increasingly since the late 1970s. Ini-
tially, MTBE was used to boost the octane rating of mid- and
high-grade gasoline and was present at concentrations of
about 4 to 8 percent by volume. These fuels were transported,
stored, and used nationwide.
Amendments to the Clean Air Act in 1990 led to the
implementation of the Oxygenated Fuel (Oxyfuel) and Refor-
mulated Gasoline (RFC) programs in 1992 and 1995, respec-
tively. While these programs stipulated a minimum oxygen
content for gasoline sold in specific metropolitan areas to
reduce air pollution, the choice of which oxygenate to use was
• continued on page 2
Inside
Study Gives Thumbs Up on Direct-Push Technology
The Eleven Myths about MTBE
Collect Reliable Soil-Gas Data: Active Soil-Gas Method
Flexible Pipe Concerns
News from California
Pay for Performance: Does It Work? The Data
..Square Operators, Round Tanks, and Regulatory Hammers
California Announces BP-Amoco Settlement
OUST Announces UST Cleanup Goals
UST Systems in China
U.S. Secures Pleas in Tanknology Case
-------
LUSTLinc Bulletin 42 • October 2002
m Analytical Methods from page 1
left to the discretion of the petroleum
refining industry. Primarily for eco-
nomic and logistical reasons, the indus-
try overwhelmingly opted for MTBE,
and it is currently used in approximately
80 percent of oxygenated fuels at concen-
trations ranging from 11 to 15 percent
by volume. Ethanol-containing fuel is
used primarily in the midwestern United
States and accounts for about 15 percent
of the oxygenated fuel supply. The other
oxygenates combined account for the
remaining 5 percent.
The Down Side of Fuel
Oxygenates
Releases of oxygenated fuel into the
environment have occurred nation-
wide from leaking storage tanks and
pipelines, transportation accidents,
refueling spills, unburned fuel pre-
sent in the exhaust from watercraft,
and/or consumer misuse. Even at
very low concentrations, the pres-
ence of some of these oxygenates can
LUSTLine
Ellen Frye, Editor
| Rlckt Pappo, Layout ]
S Marcel Moreau, Technical Advisor ;
| Patricia Ellis, Ph.D., Technical Advisor ]
iHRonald Poltak, NEIWPCC Executive Director "
1 Lynn DePont, EPA Project Officer
LL L
';; LUSTLinc is a product of the New England
ilttterstale Water Pollution Control Commis- "
i ston (NEIVVPCC). It Is produced through a
cooperative agreement (#CT825782-Oi-0)
« between NEIWPCC and the U.S.
% Environmental Protection Agency.
«• LUSTLine is issued as a communication
- service for the Subtitle IRCRA
I Hazardous & Solid Waste Amendments ]
* rule promulgation process.
LUSTLine is produced to promote ,
Information exchange on UST/LUST issues. :
"'The opinions and information stated herein
: are those of the authors and do not neces- '
. sarily reflect the opinions of NEIWPCC.
; This publication may be copied.
Please give credit to NEIWPCC.
;; NEIVVPCC was established by an Act of ]
Congress in 1947 and remains the oldest
agency in the Northeast United States ;
concerned with coordination of the multi-
,-" media environmental activities ,
* of the states of Connecticut Maine, '
1 Massachusetts, New Hampshire, ;
L New York, Rhode Island, and Vermont.
- NEIWPCC
! Boott Mills South, 100 Foot of John Street
Lowell, MA 01852-1324
1 Telephone: (978) 323-7929
Fax:(978)323-7919 ,|
I lustline@neiwpcc.org
w9 LUSTUne Is printed on Recycled Paper
render water unsuitable for a partic-
ular intended purpose (e.g., drink-
ing, cooking, bathing, laundry,
watering livestock) because it is
either unsafe or unpalatable due to
objectionable taste and/or odor.
Remediation of contaminated
groundwater and treatment of conta-
minated drinking water is time-con-
suming and expensive. Detecting the
presence of fuel oxygenates and
delineating their extent in the envi-
ronment is difficult for a variety of
reasons. In fact, only a couple of
states have even started to investi-
gate the contamination of their
groundwater with oxygenates other
than MTBE. Thus, the extent and
magnitude of oxygenate contamina-
tion in the United States is largely
unknown.
Oxygenates easily dissolve into
water and tend to migrate without
significant retardation in flowing
groundwater. MTBE plumes in par-
ticular may extend farther than is the
case for the petroleum hydrocarbons
benzene, toluene, ethylbenzene, and
the three isomers of xylene (BTEX).
Because they spread more exten-
sively, oxygenate plumes are more
difficult to detect and delineate. In
LUSTLine #36 (2000), Jim Weaver and
John Wilson discuss the difficulties
of characterizing MTBE plumes in
their article "Diving Plumes and Ver-
tical Migration at Petroleum Hydro-
carbon Release Sites."
A tremendous amount of oxy-
genate data from leaking UST sites
have been generated over the past
several years, yet there is under-
standable concern as to whether
these data are valid. In general, these
concerns are related to two issues:
• Analytical obstacles, and
• Ether hydrolysis (particularly of
MTBE to TEA).
In the following sections, we'll dis-
cuss these issues and present some
new information that may help us in
dealing with oxygenates in the envi-
ronment.
Analytical Obstacles
One of the greatest impediments to
understanding the extent of contami-
nation caused by fuel oxygenates is
the perceived lack of a single analyti-
cal method for the determination of
fuel oxygenates as a group. Although
the capability to conduct the analyses
necessary to determine all of the fuel
oxygenates at the concentrations of
regulatory concern does exist in the
current marketplace, the availability
of this service is limited. It simply
isn't standard operating procedure to
calibrate for all of the oxygenates
and, until now, no single method
with this capability has iindergone a
rigorous demonstration of applicabil-
ity. Conventional analytical proce-
dures designed for petroleum
hydrocarbons (i.e., BTEX) can also
detect MTBE and the other ethers;
when properly calibrated for them,
but they have very poor sensitivity
for TEA and the other alcohols.
Of the several widely used deter-.
minative methods published in SW-
846 (U.S. EPA, 1997), the two most
appropriate for oxygenates are
Method 8260 (Volatile Organic Com-
pounds by Gas Chromatography/
Mass Spectrometry, GC/MS) and
Method 8015 ! (Nonhalogenated
Organics Using Gas Chromatogra-,
phy/Flame lonization Detector,
GC/FID). Other GC detectors (e.g.,
the electrolytic conductivity detector
[ELCD] and the photoionization
detector [PID]) are not designed to
respond well to compounds that do
not contain halogens (ELCD) or dou-
ble bonds (PID). Therefore, methods
using either of these detectors are not
recommended for the analytical
determination of oxygenates.
In particular, Method 8021 (PID
detector) cannot be regarded as a
consistently reliable analytical tool
for the analysis of oxygenates
because it is susceptible to both false
positives (misidentifying the pres-;
ence of an oxygenate) and false nega-
tives (failing to identify the presence
of an oxygenate). False positives,
often result in resources being
wasted on unnecessary investigation
and cleanup efforts. False negatives
may result in the exposure of recep-
tors to harmful levels of contami-
nants. The problems with Method
8021 are due primarily to coelution
interferences and to the high ioniza-
tion energies of many oxygenates.
Method 8021 uses a specialized
light bulb (lamp) to ionize analytes of.
concern. The lamps typically used in
a PID for Method 8021 operate at a
maximum potential of 10 eV. The
ionization potentials of ethanol and
TEA are 10.2 eV and 10.25 eV, respec-
-------
October 2002 • LUSTLine Bulletin 42
tively. As a result, ethanol and TEA
are not ionized and cannot be
detected by these lamps. The poten-
tial required to ionize MTBE is 10 eV,
which is right at the maximum
potential of these lamps. Although
the FID may respond to MTBE when
the lamp is new, the response
becomes weaker as the lamp ages
with use. If the calibration curve for
Method 8021 is not current, the
method can return false negatives for
MTBE when MTBE is present at con-
centrations above regulatory action
levels.
Method 8021 (PID) may also be
subject to coelution interferences
and generate false positive results
when real-world samples contain sig-
nificant concentrations of other
contaminants such as petroleum
hydrocarbons. Halden et al. (2001)
found that when a sample contains
petroleum contamination (as total
petroleum hydrocarbon, TPH) of
greater than about 1,000 ^g/L (1 part
per million), Method 8021 is subject
to false positive results for MTBE. He
also found that the effect is concen-
tration-dependent (i.e., the effect
increases as the concentration of
other contaminants in the sample
increases). Most laboratory QA/QC
procedures for MTBE are not set up
to identify circumstances in which
coelution and concentration effects
compromise the reliability of the
method. Without this information the
analyst may have the mistaken
impression that the analytical results
are accurate, when in fact they are
erroneous.
A more important concern in-
olves the unequivocal determination
of the presence of oxygenates. Using
either GC/MS (Method 8260) or
GC/FID (Method 8015) with an
appropriate GC column and an
appropriate sample-preparation tech-
nique, it is possible to detect oxy-
genates at concentrations of 5 ,wg/L
or less. However, GC/MS provides
positive confirmation of the chemical
identity of the analyte that is
detected, while GC/FID does not.
It is not necessary to modify
existing conventional practice for
chromatography to obtain data for all
of the oxygenates; only the sample
preparation and method calibration
steps need to be modified. If calibra-
tion curves are run for all of the other
ethers, then concentrations of all of
these oxygenates can be determined
for the same samples and in some of
the same analytical runs used to
determine BTEX and MTBE, pro-
vided that the concentrations of all
target compounds fall within the
operational calibration ranges of the
detectors used.
f It simply isn't standard operating
¥procedure to calibrate for all of the
^oxygenates and, until now, no single
^method with this capability has
^undergone a rigorous demonstration
' ; of applicability. Conventional
^analytical procedures designed for
^petroleum hydrocarbons (i.e., BTEX)
jjctjnalso detect MTBE and the other
ethers when properly calibrated for
J*K them, but they have very poor
' sensitivity for TBA and the
other alcohols.
Another important concern is the
method detection limit or the report-
ing limits of current analytical proto-
cols for the alcohols, and TBA in
particular. Analysis of the alcohol
oxygenates is a more difficult chal-
lenge than analyzing for BTEX (or
even MTBE). Many commercial labo-
ratories set reporting limits for TBA
that are much higher than reporting
limits for BTEX and MTBE. Typical
reporting limits for TBA may be as
high as 100 or 1,000 pg/L. These
reporting limits are higher than the
concentrations of TBA that are of reg-
ulatory interest to many states.
Overcoming Analytical
Obstacles
Methods 8015 (GC/FID) and 8260
(GC/MS) are appropriate for deter-
mining the presence and concentra-
tion of fuel oxygenates and BTEX.
Appropriate sample-preparation
methods include Methods 5021 (sta-
tic headspace), 5030 (purge-and-
trap), or 5032 (vacuum distillation).
TBA can also be recovered for analy-
sis using the azeotropic distillation
technique (Method 5031). If ethers
are the only target analytes of inter-
est, then using Method 5030 at ambi-
ent temperature (rather than heated)
is adequate to determine concentra-
tions of oxygenates that are greater
than 5 fig/~L. However, if alcohols (or
acetone) are analytes of concern, the
water sample must be heated to
attain adequate recovery of analytes.
If the sample is not heated, the effec-
tive limit of quantitation for TBA
using Method 5030 is near 100 ffg/L;
when the water sample is heated to
80e C the limit of quantitation is near
In response to problems identi-
fied with current analytical practice,
EPA conducted a study to determine
the optimum conditions for purge-
and-trap sample preparation of
MTBE and the other fuel oxygenates
in river water samples both with and
without BTEX interferences in the
form of gasoline spiked at 600 fig/L.
The compounds included in the
study were MTBE, TBA, DIPE, ETBE,
TAME, TAEE, and acetone. The tar-
get sensitivity was 5 ^ig/L (U.S. EPA,
2002).
The study was performed over a
five-point calibration range of 2 jig /I.
to 40 ^g/L for each target analyte.
The analytes were purged at 80s C for
seven minutes and trapped on a
Supelco H trap1, held at 35s C, dry
purged, desorbed and baked for
three minutes each, and analyzed on
a standard VOA column and a wax
column. Water samples were run
both with and without BTEX present
in the samples. An additional evalua-
tion using purge-and-trap conditions
at ambient temperature (202 C) and
the standard VOA column was also
performed.
The results of EPA's study
demonstrate that the recoveries of
low levels of MTBE and related oxy-
genates can be improved over cur-
rent practice. The most consistent
oxygenate recoveries were obtained
using the following combination of
methods: sample preparation using
Method 5030 with a heated (80s C)
purge-and-trap, then analysis by
Method 8260 using a DB-Wax capil-
lary column as the determinative
method. Use of an RTX- Volatile cap-
illary column with a heated purge
did not significantly improve the
Performance with other brands of traps
may vary from that of the present study.
If a different trap is used, its performance
must be demonstrated, not merely
assumed to be comparable to the Supelco
H trap. Silica gel is needed as a trapping
material for the trap to perform properly.
• continued on page 4
-------
LUSTLinc Bulletin 42 • October 2002
m Analytical Methods from page 3
overall oxygenate recovery com-
pared to the DB-Wax capillary col-
umn. In addition, BTEX interferences
did not adversely affect the chro-
matographic separation, quantita-
tion, and recovery of oxygenates.
For samples with high concentra-
tions of hydrocarbons and oxy-
genates, the samples will have to be
diluted so that they are within the
operating range of the instrument. As
a general rule, analysts dilute and
rerun samples when tike concentration
of any analyte exceeds 0.5 mg/L when
using Method 8260 (MS detector) or
exceeds 4 mg/L when using Method
8015 (HO). If the concentration of one
of the BTEX compounds or oxy-
genates is much higher than the other
analytes, then multiple runs will have
to be made using diluted samples.
These methods must only be
used by, or under the supervision of,
analysts experienced in the use of gas
chromatography for measurement of
organic compounds at low concentra-
tions (i.e., /
-------
October 2002 • LUSTLine Bulletin 42
Preserved with
HCL
pH = 1
HCI
pH-2
1 % trisodium
phosphate
pH>12
Time of Incubation
(minutes)
0
30
60
0
30
60
0
30
60
MTBE (ug/L)
536
196
88.5
495
401
393
476
424
432
TBA (ug/L)
<3
255
343
<3
25.2
53.8
<3
<3
<3
Percent MTBE
Hydrolyzed
57%
77%
6.1%
13%
<1%
<1%
* The hydrolysis of 1 ug/L of MTBE should yield 0.84 ug/L of TBA.
TableFXEfflECTOirlSAMPLE PlESElVAlltiNMMra
Sail*^^^
Sample ID
ML-12-16
ML-16-12
W1L-17-12
ML-19-12
ML-19-16
ML-23-16
Dilution
none
1:10
none
1:10
1:100
none
1:10
1:100
none
1:10
1:100
none
1:10
1:100
none
1:10
TBA (ug/L)
corrected for
dilution
3,230
1,065
10,40.0 .
2,644
2,006
6,170
1,483
1,405
4,640
1,309
591
5,100
1,222
740
719
260
MTBE (ug/L)
corrected for
dilution
2,953
12,669
13,273
7,216 . .. .
8,551
. 2,550
Percent MTBE
Hydrolyzed
89%
83%
5.8%
56%
0.7%
60%
. 12%
68%
7.3%
22%
and shipped to EPA's R. S. Kerr Envi-
ronmental Research Center for analy-
sis using a static headspace sampler
(Method 5021).
The water samples were brought
to 80s C for 30 minutes prior to analy-
sis of the headspace by GC/MS.
Replicates of selected groundwater
samples were diluted and then ana-
lyzed. The concentration of TBA
reported for a sample was the sum of
the concentration of TBA that was
originally present plus the concentra-
tion of TBA produced from hydroly-
sis of MTBE.
For each tenfold dilution, the
concentration of acid used
as a
preservative was diluted tenfold, the
rate of acid hydrolysis of MTBE was
reduced tenfold, and the concentra-
tion of TBA produced from hydroly-
sis was reduced. The reported
concentrations in Table 2 are cor-
rected for dilution of the sample. The
reported concentration of TBA in the
undiluted samples was much higher
than in the diluted samples.
The last column in Table 2 pre-
sents the fraction of MTBE that was
hydrolyzed during analysis. The frac-
tion was calculated by assuming that
the reported concentration of TBA at
the highest dilution was the true con-
centration of TBA that was originally
present in the sample and that the
higher concentrations of TBA in the
undiluted samples were produced by
hydrolysis of MTBE.
In 15 undiluted samples, the frac-
tion of MTBE that was hydrolyzed
during analysis varied from 22 per-
cent to 89 percent, with a median of
62 percent hydrolyzed. The hydroly-
sis of MTBE in the undiluted samples
increased the reported concentration
of TBA by a factor of four to eight.
When samples that were diluted 1:10
are compared to samples that' were
diluted 1:100, the extent of hydrolysis
in the samples that were diluted 1:10
varied from 1 percent to 18 percent
with an average of about 9 percent.
These data-quality problems
associated with the hydrolysis of
MTBE to TBA illustrate the impor-
tance of a quality assurance/quality
control program. Any significant
hydrolysis of MTBE can be detected
easily if matrix spike samples are
included in the analyses. The accu-
racy of the analysis is determined by
measuring the concentration of the
target compound present in a sam-
ple, then adding a known concentra-
tion of the target compound to a
replicate sample of the same water (a
matrix spike) and again determining
the concentration of the target com-
pound. The concentration in the
matrix spike sample should equal the
sum of the spiked concentration and
the original concentration.
Therefore, if water samples are
preserved with acid, there is an
understandable concern as to
whether or not any of these data are
valid. Unfortunately, the answer to
this can only be determined by
reviewing the reports of analytical
results from each site of interest. The
things to look for are indications
of sample-preservation methods,
method operating parameters, qual-
ity assurance/quality control results,
and whether or not confirmatory
identification of analytes is provided.
The rate constants published by
O'Reilly et al. (2001) can be used to
estimate the stability of MTBE in
water samples. Figure 1 (page 6) pre-
sents predictions for water samples
that are preserved at pH=l and
pH=2 and stored before analysis at
temperatures of 42 C, 10a C, and 20s
C. If the samples were refrigerated at
10s C or lower, less than 5 percent of
• continued on page 6
-------
LUSTLinc Bulletin 42 • October 2002
• Analytical Methods from page 5
the MTBE would be hydrolyzed in
the first 30 days of storage. If samples
were acidified to pH=l and stored at
20° C, as much as 20 percent of the
MTBE could be hydrolyzed in 30
days. If groundwater samples are
refrigerated before analysis and all
the sample preparation methods are
carried out at ambient temperature
(as opposed to an elevated tempera-
ture of 80s C), there is minimal
opportunity for hydrolysis of the
ether oxygenates.
Preventing Ether Hydrolysis
Through Improved Sample-
Preservation Technique
There are two widely used methods
of preservation: refrigeration and
chemical preservation (usually acidi-
fication). Often both methods are
used on the same samples. If acid
causes a problem with analysis of
MTBE and TBA, one might be
tempted to not use acid and rely on
refrigeration alone.
It is essential, however, to use
both a chemical preservative and
refrigeration for groundwater sam-
ples, especially if they are to be
analyzed for BTEX compounds.
Groundwater samples from perma-
nent wells typically contain micro-
organisms that are capable of
degrading BTEX relatively quickly
when oxygen is available. Contami-
nants may persist in groundwater
because the plume is devoid of dis-
solved oxygen, but groundwater
samples from wells invariably con-
tain dissolved oxygen, particularly if
samples were collected with a bailer.
In samples that have not been pre-
served, BTEX compounds may be
completely biodegraded in less than
two weeks (Wilson et al. 1994) and
MTBE and TBA may be completely
degraded within two weeks of stor-
age (Kane et al. 2001).
As good practice, samples should
be packed in ice for shipment and
refrigerated during storage. The tem-
perature and general condition of the
samples upon receipt by the labora-
tory should be indicated on the
chain-of-custody. Samples should be
cold (preferably close to 4a C upon
arrival at the lab), they should be pre-
served, and they should be analyzed
within prescribed holding times.
If samples arrived at the lab
30
60 90
Days of Incubation
120
150
FIGURE 1. Predicted effect ofpH and temperature on the stability of MTBE in samples of
groundwater.
warm, if they weren't preserved, if
they were analyzed past their hold-
ing time, or if acid-preserved samples
were analyzed using a heated
preparatory method, then there is a
chance that some of the MTBE was
hydrolyzed to TBA. If hydrolysis is a
possibility, then examine the quality
assurance/quality control data pro-
vided with the analytical report. If
the recovery of MTBE (or other ether
oxygenate) from spiked samples is
near 100 percent, then hydrolysis of
MTBE during analysis was minimal
and should not be of concern.
We must reiterate that both a
chemical preservative and refrigera-
tion should be used to preserve sam-
ple integrity. Refrigeration by itself
may slow the rate of biological degra-
dation, but not to a useful extent. A
conventional refrigerator is often
near 10s C and refrigerated storage
for samples is usually near 4s C.
The temperature of groundwater
in the northern half of the United
States ranges from 102 C to 15s C. As
a consequence, the microorganisms
collected along with a groundwater
sample are already adapted to cold
conditions. Storage of samples with-
out a chemical preservative at 10a C
to 42 C will only slow the rate of bio-
logical degradation of BTEX by a fac-
tor of two to four at most. Although
refrigeration is only minimally effec-
tive in retarding biodegradation of
the sample, it is effective at inhibiting
the chemical deterioration of the
sample.
Kovacs and Kampbell (1999)
developed an alternative procedure
for chemically preserving groundwa-
ter samples that avoids hydrolysis of
ether oxygenates. Instead of using an
acid to lower the pH, samples are
preserved with a base to a pH greater
than 11. The elevated pH effectively
prevents the biodegradation of
organic compounds in the sample.
The ethers are not subject to base-cat-
alyzed hydrolysis, and a basic pH has
no adverse effect on BTEX or the
alcohol oxygenates (O'Reilly et al.
2001). The pH is elevated by adding a
salt of a weak acid (trisodium
phosphate dodecahydrate, or TSP),
instead of a solution of a strong base
such as potassium hydroxide. Table 1
compares MTBE hydrolysis in sam-
ples that were preserved with acid to
samples preserved with TSP. There
was no evidence of MTBE hydrolysis
to TBA in the samples that were pre-
served with TSP.
The Kovacs and Kampbell (1999)
procedure is safe and convenient. In
the laboratory, between 0.40 and 0.44
gram of TSP is added to each 40 mL
sample vial. Because it is more conve-
nient to measure the required
amount of TSP ori a volume basis
rather than by weight, staff of the R.S.
Kerr Center use a precalibrated
-------
October 2002 • LUSTLine Bulletin 42
spoon (Hadh. # 907-00 or equivalent).
In the field, each vial is filled with the
groundwater sample and sealed
without headspace (the same as is
done if the sample is preserved with
acid).
The salt is added to excess. If a
portion of the salt is washed out of
the vial as the vial is filled with sam-
ple, enough TSP will remain to pre-
serve the sample. As the salt
dissolves, it buffers the sample to a
pH greater than 11.
No special handling of the sam-
ples is required prior to analysis,
although they should be stored in a
refrigerator at 4s C. Water samples
preserved with TSP are 1 percent
salt by weight. If purge-and-trap
(Method 5030) is used to prepare the
water samples, it is particularly
important to prevent the transfer of
aerosols from the purged water to the
trap and GC column. This should be
no different than current good labo-
ratory practice.
It is prudent to check the pH of
the sample with indicator paper to
ensure that the pH is greater than 11
prior to introducing it into the purge
vessel or the headspace sampler for
analysis. If it is necessary to analyze
samples that have already been pre-
served with acid, the acid can be
destroyed with TSP prior to analysis.
An amount of TSP sufficient to raise
the pH of the sample to greater than
11 is added to the sample vial, which
is quickly resealed without head-
space and shaken gently to dissolve
the salt. Generally, about 0.7 gram of
TSP is sufficient for a 40 mL VOA
vial, but sometimes (depending upon
the pH of the sample) more must be
added to elevate the pH to greater
than 11.
Recommended Protocol
The protocol described in this article
enables us to determine the presence
and concentration of all of the com-
mon oxygenates and BTEX at levels
of regulatory interest. Routine use of
this protocol will greatly improve the
quality of the data that are reported,
which in turn will enable us to make
better decisions, which will ulti-
mately result in more effective uti-
lization of available resources.
Because MTBE (and potentially
any other oxygenate) may be present
at any petroleum UST site, whether
the release is new or old, virtually
anywhere in the United States, it is
also important to respond promptly
to any petroleum release. The sooner
all of the contaminants in a plume are
identified and their subsurface extent
determined, the sooner a remedy can
be selected and implemented.
Because a contaminant plume is
smaller and more easily managed
early on, the magnitude of the impact
and the overall cost of the cleanup
should be less than if the plume is
allowed to expand.
KTfte protocol described in this article \
*t- enables us to determine the ':
I presence and concentration of all of
*-*— f ^ ; ..-*• fe
Ijhg common oxygenates and BTEX at
ijeyels of regulatory interest. Routine
use of this protocol will greatly
improve the quality of the data that
f are reported, which in turn will
fenable us to make better decisions,
will ultimately result in more
effective utilization of available
resources.
Consequently, it is prudent to
analyze samples for the entire suite of
oxygenates as identified in this proto-
col (i.e., MTBE, TAME, ETBE, DIPE,
TAEE, TAA, and TEA). Samples
should be prepared for analysis,
preferably using EPA Method 5030
heated to 80s C (although either
Method 5021 or Method 5032 may be
used if the laboratory can demon-
strate appropriate performance with
these methods).
The determinative method (e.g.,
Method 8260, 8015, or other appro-
priate method) should be calibrated
for the entire suite of oxygenates, and
these analytes should be reported for
every sample analyzed. With the
understanding that ethanol and
methanol are potentially present at
fuel release sites, it is also advisable
to have samples analyzed for these
alcohol oxygenates using appropriate
preparative and determinative meth-
ods.
EPA Method 8260 (or another
method that provides confirmatory
identification of all of the fuel oxy-
genates and can be demonstrated to
meet project data quality objectives)
is the preferred determinative analyt-
ical method for fuel oxygenates (and
other contaminants of concern) when
the analyses will be used to (1) char-
acterize the three-dimensional extent
of a contaminant plume, (2) deter-
mine whether a site requires active
remediation, (3) select an active rem-
edy, (4) design an active remedy, (5)
determine whether a site has met
site-specific cleanup objectives, or (6)
determine if it is no longer necessary
to continue monitoring a site.
After all of the oxygenates (and
other contaminants of concern) pre-
sent at a site have been identified and
their concentration and extent deter-
mined, future analyses might then be
conducted using a less expensive
determinative method (e.g., 8015).
Situations that might not require con-
firmatory analysis would include
routine long-term performance moni-
toring as part of a MNA remedy or
exposure management strategy.
To properly implement this pro-
tocol, groundwater samples should
be collected from locations where
oxygenates are most likely to occur,
based on their chemical and physical
behavior. Because oxygenates are
more soluble than petroleum hydro-
carbons and can be more recalcitrant,
oxygenate plumes may be longer
than typical BTEX plumes.
Oxygenate plumes may also
"dive" beneath conventional moni-
toring wells and migrate undetected
until a drinking water source is
impacted. (See Weaver and Wilson's
article in LUSTLine #36.) To ensure
that such plumes aren't migrating
undetected, samples should be col-
lected from a series of discrete sam-
pling points that draw in
groundwater only over short vertical
intervals. There should be a sufficient
number of sampling points to cover
the entire vertical distance over
which an oxygenate plume may
migrate. Generally this means that
additional sampling points are
required at progressively greater
depths below the water table as the
downgradient distance from the
source increases. Increasing the
length of monitoring well screens is
not appropriate as this will only
dilute the concentration of contami-
nants in the sample and mask the
true concentration in the plume.
To prevent constituents in the
samples from being biodegraded
• continued on page 8
-------
LUSTLine Bulletin 42 • October 2002
• Analytical Methods from page 7
during storage and transport, sam-
ples should be preserved. To prevent
chemical hydrolysis of the ether oxy-
genates during storage, the samples
should be preserved with a base
delivered as a salt (TSP), rather than
as a strong acid, and also refriger-
ated. Preservation with TSP will also
eliminate the possibility that ethers
will be hydrolyzed during sample
preparation. Stored samples should
be refrigerated at 4a C and analyzed
within the holding period. •
References
Church, C. D., J. E. Pankow, and P. G. Trat-
nyek. 1999. Hydrolysis of ferf-Butyl Format:
Kinetics, Products, and Implications for the
Environmental Impact of Methyl tert-Butyl
Ether. Environmental Toxicology and Chemistry
18 (12): 2789-2796.
Halden, R. U, A. M. Happel, and S. R. Schoen.
2001. Evaluation of Standard Methods for the
Analysis of Methyl tert-Butyl Ether and
Related Oxygenates in Gasoline-Contaminated
Groundwater. Environmental Science & Technol-
ogy 35 (7): 1469-1474. (Additions and Correc-
tions, 35 (7): 1560.)
Kane, S. R., H. R. Beller, T.C. Legler, C. J.
Kocster, H. C. Pinkart, R. U. Halden, and A. M.
Harper. 2001. Aerobic Biodegradation of
Methyl tert-Butyl Ether by Aqufier Bacteria
from Leaking Underground Storage Tank
Sites. Applied and Environmental Microbiology 67
(12): 5824-5829.
Kovacs, D. A. and D. H. Kampbell. 1999.
Improved Method for the Storage of Ground-
water Samples Containing Volatile Organic
Annlytes. Archives of Environmental Contamina-
tion and Toxicology 36:242-247.
O'Reilly, K. T., M. E. Moir, C. D. Taylor, C. A.
Smith, and M. R. Hyman. 2001. Hydrolysis of
Methyl tert-Butyl Ether (MTBE) in Dilute
Aqueous Acid. Environmental Science & Tech-
nology 35 (19): 3954-3961.
U.S. EPA. 1997. Test Methods for Evaluating
Solid Waste, Physical/Chemical Methods (SW-846)
including updates. Office of Solid Waste.
Washington, DC
Iitlp://wwio.epa.gov/epnoswer/hazwaste/test/sw846
Mm
U.S. EPA. 2002. Development and Evaluation of
Methods for the Analysis of MTBE. EPA contract
No. 68-WO-0122 WA No. 0-08.
Wade, M. J. 1998. Acidification of Groundwa-
ter Samples for Sample Preservation and Its
Effect on Determining Methyl t-Butyl Ether
Concentration. Division of Environmental Chem-
istry Preprints of Extended Abstracts 38 (2):
246-248.
Wilson, B. H., J. T. Wilson, D. H. Kampbell,
and B. E. Blcdsoe. 1994. Traverse City: Geochem-
istry and Intrinsic Bioremediation of BTX Com-
pounds. Symposium on Natural Attenuation of
Ground Water. EPA/600/R-94/162.
8
Hal White is a hydrogeologist with the
U.S. EPA Office of Underground Stor-
age Tanks in Washington, DC. He can
be reached at white.hal@epa.gov
Barry Lesnik is Organic Methods Pro-
gram Manager with the U.S. EPA
Office of Solid Waste, Economics,
Methods, and Risk Analysis Division,
in Washington, DC. He can be reached
at lesnik.barry@epa.gov
John Wilson is a research microbiolo-
gist with U.S. EPA Office of Research
and Development, Ground Water and
Ecosystems Restoration Division in
Ada, OK. He can be reached at
wilson. j ohnt@epa.gov
For More Information
For additional information about
analytical methods, call the
Method? Information
Communication Exchange (MICE)
hotline at 703-676-4690, or visit ^
the MICE web site at *
http://www.epa.gov/SW_846/mic "
e.htm. Fgt information about the ,
Underground Storage Tank
program, visit
http://www.epa.gov/oust. For
information about either this
article or the soon-to-be-released ~m
ll EPA Fact Sheet, e-mail Hal White *
(EPA70UST)ai
il ..'i'Sl!!,: W'liiil „',!„'! 'n'p,i,'"'i:i»' ? j;!»!'!'" 'U.I1!!' ! ,','-. •! (Wii*- J *TW.i' HT5 ,.,i@
1
Disclaimer
This article was written by staff of the U.S.
Environmental Protection Agency who are
assigned to the Office of Underground Storage
Tanks, the Office of Solid Waste, and the Office
of Research and Development. It has been sub-
jected to the Agency's peer and administrative
review and has been approved for publication.
The article has not been subjected to Agency
policy review and therefore does not necessar-
ily reflect the views of the Agency, and no offi-
cial endorsement should be inferred. Mention
of trade names or commercial products in EPA
methods is for illustrative purposes only, and
does not constitute an endorsement or exclu-
sive recommendation for use by EPA. The
products and instrument settings cited in SW-
846 methods represent those products and set-
tings used during method development or
subsequently evaluated by the Agency. Glass-
ware, reagents, supplies, equipment, and set-
tings other than those listed in these methods
may be employed provided that method per-
formance appropriate for the intended applica-
tion has been documented.
Monitoring-Wei I
Comparison Study
Gives Thumbs Up
on Direct-Push
Technology
The U.S. EPA Region 5 and
Region 4 LIST programs,
together with BP Amoco and
LUST programs in Georgia and
Ohio, initiated a study several
years ago to evaluate the perfor-
mance of direct-push monitoring
wells compared to conventional
monitoring wells. Many state
agencies have been reluctant to
accept data generated from
direct-push wells because of
uncertainties about their accu-
racy or reliability. The resulting
peer-reviewed report, released in
May 2002, shows that for most
of the parameters included in the
comparison, the direct-push
wells performed just as well as
conventional wells, provided the
wells are properly developed.
This study, titled Monitoring
Well Comparison Study: An
Evaluation of Direct-Push Versus
Conventional Monitoring Wells,
is available at
www.epa.gov/reg5rcra/
wptdiv/tanks/. A separate but
very similar study that confirms
these results was recently com-
pleted by the Naval Facilities
Engineering Center in California
(www.clu-in.org/techdnct/
techpubs.asp).
Technical questions about the
EPA/BP Amoco report can be
directed to Gilberto Alvarez of
U.S. EPA Region 5 at
(312)886-6143
(alvarez.gilberto@epa.gov) or
David Ariail of U.S. EPA Region 4
at (404) 562-9464
(ariail.david@epa.gov).
Feedback on this report is
welcome. •
-------
October 2002 • LUSTLine Bulletin 42
The Eleven Myths about MTBE
myth: & fiction or half-truth, eep. one that forme part of the ideology of a society. (Webster's Dictionary)
In an article in a recent issue of Contaminated Soil, Sediment, and Water (Spring, 2001—which was just released this past
spring) authors Dick Woodward and Dick Sloan outline 11 so-called myths, misconceptions, and assumptions about MTBE. The
article, titled "Common Myths, Misconceptions and Assumptions about MTBE: Where Are We Now?" is based on presentations
from a series of seminars sponsored by Lyondell Chemicals (a major producer of MTBE) through the consulting firm ofTighe and
Bond, Inc. The seminars, many of which were led by Woodward and Sloan, were presented in dozens of cities across the United States
(and also around the world). These myths have also been immortalized in a giant, full-color, wall-sized poster.
But with all of the resources that have been poured into this information dissemination effort on behalf of Lyondell, can we safely
assume that we've been presented with the truth, the whole truth, and nothing but the truth about MTBE? I decided to explore this
question by taking a closer look at the 11 MTBE myths put forth in Woodward and Sloan's article. For consistency and ease of com-
parison, I present each myth in the same order and with the same title as it appears in the article. (See my references for a URL). My
criticjues consist of a brief summary of the major points from the article that purportedly support their classification as a myth, a com-
prehensive analysis of each major point, and finally a conclusion as to whether or not the alleged myth is in fact a myth. After examin-
ing each of the myths and determining its status as a myth, I tally up the results.
Note: In each "Major points" section below, I have quoted the text exactly as published in Contaminated Soil, Sediment, and
Water. It has not been edited for grammar or clarity of content.
MYTH #1: MTBE DEGRADES
STORAGE/HANDLING
FACILITIES
Major points: (1) "MTBE has been
an important component of unleaded
gasoline and subsequently reformu-
lated gasoline (RFC) for more than 20
years. MTBE containing formulations
have been successfully shipped
nationwide in a variety of truck
transports, pipelines and rail transfer
facilities. Historically, the materials
of these gasoline-handling facilities
have been compatible with MTBE
and have tested tight."
(2) "Several detailed reviews
over the last three years have not
revealed any specific instances where
MTBE in gasoline caused premature
failure of systems components or
resulted in material incompatibility."
Analysis: (1) At face value there's no
dispute with this point. However,
despite the title of this myth, this
point explicitly mentions "gasoline-
handling" facilities (i.e., truck trans-
ports, pipelines, and rail transfer
facilities), not "storage" facilities. The
claim that any gasoline-handling
facility has "tested tight" is not neces-
sarily an indication that there hasn't
been a release. UST systems are not
air-tight, and vapor releases in partic-
ular are not detected by most leak-
detection devices.
(2) Admittedly, definitive exam-
ples of compatibility-related UST sys-
tem failures are rare. But it is due
more to the fact that this type of
information is difficult to ascertain
and rarely collected, and not because
such problems never occur. Virtually
all UST-system compatibility studies
to-date have been conducted in the
laboratory and not in the field.
Couch and Young (1998) con-
ducted a comprehensive evaluation
of MTBE-UST compatibility issues.
Although their review of available lit-
erature found no significant threat to
most UST materials from fuels con-
taining up to 20 percent MTBE, pub-
lished data indicate that the service
life of some elastomer products is
shortened due to swelling, softening,
and permeation when in contact with
fuel containing 15 to 20 percent
MTBE or when in contact with MTBE
vapors.
Couch and Young (1998) also
concluded that despite the fact that
numerous compatibility studies had
been conducted, none were long.
term, most were qualitative rather
than quantitative in nature, and most
of the investigators were industry
purveyors or materials suppliers.
• continued on page 10
-------
LUSTLine Bulletin 42 • October 2002
I Myths from page 9
Due to this "lack of objective, inde-
pendent, and quantitative research,"
Couch and Young (1998) suggest that
further investigation is warranted,
especially with regard to elastomer
performance.
Davidson (1998) also reviewed
the available knowledge regard-
ing the compatibility of MTBE
with UST systems in an article
for LUSTLine (Bulletin #28).
Although he concluded
that there were no obvi-
ous compatibility prob-
lems, he also noted that
available information
was either limited or
contradictory. He rec-
ommended that more
research be conducted,
especially in the areas
of seal and gasket
material compatibility
with MTBE and the
effect of MTBE-
enriched vapors and
condensates on UST sys-
tem components.
Conclusion: It's no myth—there
are compatibility concerns with some
UST components, at least at present.
Even if all of the other UST system
components are eventually shown to
be compatible with gasoline that con-
tains MTBE, some data indicate that
certain elastomeric materials that are
in use today are degraded to some
extent when in contact with MTBE
(and especially vapors) and could
potentially fail sooner than antici-
pated. Until these materials are no
longer in use in UST systems, there is
still a potential for a release.
MYTH #2: MTBE ALONE
LEAKS FROM GASOLINE
TANKS
Major points: (1) "when an [UST]
fails, all of the chemical components
of the fuel are released into the sub-
surface soils and likely into the
underlying groundwater..."
(2) "Typically, gasoline may con-
tain 6% MTBE by volume, which
means that 94% of what leaks into the
soil and groundwater is other gaso-
line components..."
Analysis: (1) This point assumes that
all releases from USTs are liquid
_
releases that are the result of tank
failure. However, the majority of
releases from UST systems are low-
volume, chronic releases, not cata-
strophic tank failures. There is an
increasing body of evidence that indi-
cates that vapor releases from UST
systems may be a significant source
of groundwater contamination. For
fuels oxygenated with MTBE, vapor
releases are composed almost
entirely of MTBE, which readily dif-
fuses in soil moisture and begins a
downward migration toward
groundwater. BTEX, on the other
hand, tends to sorb to organic carbon
in soil, therefore traveling a shorter
distance, and often degrading rela-
tively close to the source area (though
there are lots of exceptions).
Even when a liquid release does
occur, and components other than
MTBE are released into the subsur-
face, MTBE will be preferentially
depleted from the residual fuel
source and dissolve into soil moisture
and groundwater. As a result of the
relatively lower solubility of BTEX,
MTBE will end up in the groundwa-
ter more quickly than will BTEX.
(2) MTBE may be present in oxy-
genated fuels at volumes from 11 to
15 percent (much higher than the 6
percent stated in the article). While
this still means that 85 to 89 percent of
the total volume of the fuel is com-
posed of other chemical constituents,
it also means that for every seven to
nine gallons of oxygenated gasoline
released into the environment, one
gallon of MTBE is also released. If this
one gallon of MTBE is evenly distrib-
uted in groundwater at a concen-
tration of 20 ppb, a volume of
more than 4 million gallons of
water would be polluted.
Another point that the article
doesn't make is that MTBE is
increasingly found in fuels other
than gasoline (e.g., diesel fuel,
heating oil, and jet fuel). Since
these fuels consist primarily of
heavier, less-soluble constituents
than gasoline and sorb to soils
more readily, it is entirely possi-
ble that a plume originating
from one of these releases could
be composed solely of MTBE.
Conclusion: It's no myth. It is
possible that MTBE may be the
only fuel component released to
the environment in any signifi-
cant quantity, especially in the
case of vapor-only releases or
releases of fuels other than
gasoline.
MYTH #3: MTBE TRAVELS
FAR BEYOND BTEX
PLUMES
Major points: (1) "Dissolved chemi-
cals cannot travel faster than the
groundwater but they may travel
slower if their movement is retarded
by adsorption to the soil."
(2) "The net result is that MTBE
will tend to exist on the leading edge
of a typical groundwater plume,
however the other gasoline compo-
nents, e.g. BTEX, will tend to exist
immediately behind the leading edge
of the plume."
(3) "Several recent studies of
groundwater plumes associated with
gasoline releases have confirmed that
MTBE and BTEX plumes generally
coincide."
Analysis: (1) No hydrogeologist
would say that dissolved chemicals
travel faster than groundwater. What
can be said, however, and what may
be misinterpreted as meaning the
same thing as the preceding state-
ment, is that some dissolved chemi-
cals travel faster than the average
-------
October 2002 • LUSTLine Bulletin 42
linear velocity o£ the groundwater. As
groundwater flows through the
aquifer matrix, water molecules twist
around individual grains and pass
through interconnected pore spaces
at differing velocities. Some water
molecules, therefore, reach a given
point faster than others.
Dissolved chemical molecules
also travel at differing velocities but
none faster than the fastest water
molecule. At any given point in
space, a breakthrough curve—a plot
of concentration versus time—has
the shape of an elongated "S." The
inflection point of this curve repre-
sents the hypothetical arrival time of
an undiluted slug of contaminant
that is moving at the average linear
groundwater velocity. The upper and
lower tails of the "S" represent the
effect of dispersion—the lower tail
represents molecules that travel
faster than the average linear
groundwater velocity, the upper tail
represents molecules that travel
slower.
For a perfectly nonreactive chem-
ical (i.e., one whose movement is not
"retarded"), the breakthrough curve
would be a step function; that is, the
concentration would be zero until
first arrival and then it would jump
(step) to 100 percent concentration
instantaneously. While the move-
ment of BTEX is retarded, the
movement of MTBE is relatively
unimpeded such that its movement
through the aquifer is generally at a
velocity that is higher than that of
BTEX, although no faster than
groundwater.
(2) All other conditions being
equal, if BTEX and MTBE are
released into flowing groundwater at
the same time, MTBE will almost cer-
tainly jump out ahead of BTEX in the
plume that forms and be present as
the leading edge. Because of its
greater solubility, MTBE will be pref-
erentially depleted from the residual
source sooner than will BTEX. Once
the source is exhausted, both BTEX
and MTBE plumes may detach and
continue to migrate downgradient as
slugs of contaminants rather than as
an attached plume. However, BTEX
sources tend to persist for longer
periods of time than do MTBE
sources because the MTBE is
depleted more quickly from the
source, and BTEX source areas tend
to be anaerobic, so biodegradation is
slower. In groundwater environ-
ments that are not conducive to
biodegradation of MTBE, given
enough time the MTBE slug will
eventually migrate farther downgra-
dient than will BTEX.
(3) The degree of plume separa-
tion is dependent upon many other
factors in addition to time. One factor
that is frequently overlooked is the
adequacy of the monitoring network
from which groundwater data are
derived. Because MTBE behaves dif-
ferently than BTEX, MTBE often will
not be detected in the same wells as
those with BTEX, especially with
increasing downgradient distance
from the source.
Perhaps the best-recognized
example of MTBE moving indepen-
dently of BTEX is the plume at East
Patchogue, New York. The MTBE
plume is about 20 feet below the
water table with a leading edge
("toe") that is over 6,000 feet from the
source; the trailing edge ("heel") is
nearly 4,000 feet from the source. On
the other hand (or perhaps a better
word in this case would be "foot"),
the toe of the benzene plume is over
5,000 feet from the source and still
attached to the source area. LUSTLine
#36 (November 2000, pp.12-15) con-
tains an article by Jim Weaver and
John Wilson (EPA/ORD) that pre-
sents this example along with a com-
prehensive discussion of plume
diving and the inadequacy of con-
ventional monitoring well networks
for detecting MTBE plumes.
Conclusion: It's no myth. MTBE
does have the potential to migrate
farther (and faster) than BTEX. There
are numerous examples from around
the country that support this obser-
vation. For example, several MTBE
plumes on Long Island are up to sev-
eral thousand feet ahead of BTEX
plumes. From the 2000 NEIWPCC
survey, 27 states reported that MTBE
plumes were often or sometimes
longer than BTEX plumes, and 19
states indicated that they had MTBE
plumes in excess of 1,000 feet in
length. But it is also important to real-
ize that this won't necessarily be the
case at every site.
MYTH #4: MTBE PLUMES
SINK (OR DIVE)
Major points: (1) "MTBE and the
other components of gasoline have a
specific gravity of less than 1, conse-
quently free phase gasoline, with
MTBE or without, floats on the
groundwater water table."
(2) "If recharge occurs from the
surface, older aquifer water and its
dissolved constituents may be
pushed downward in the formation."
(3) "Likewise, pumping of an
aquifer at depth may pull the water
table and constituents dissolved in
the groundwater to deeper locations
in the formation."
(4) "...it is important to conduct
complete, three-dimensional charac-
terization of plumes prior to remedial
action."
Analysis: (1) No disagreement here.
Free-phase LNAPLs will certainly
float on the water table. But it's the
dissolved phase, not the free phase,
that's of concern with regard to
MTBE plumes.
(2) No disagreement here. This is
one of the three mechanisms by
which MTBE plumes have been
observed to sink (or "dive").
(3) No disagreement here either.
This is the second of the three mecha-
nisms by which MTBE plumes have
been observed to sink (or dive). The
third mechanism can be referred to as
"stratigraphically" or "structurally"
induced. In this situation, preferen-
tial pathways that occur in the sub-
surface act as conduits that allow
contaminants to migrate deeper into
the aquifer than they might other-
wise have were the aquifer composed
of media that was homogeneous and
isotropic.
(4) Absolute, 100 percent agree-
ment with this statement, especially
in the context of the article as a
whole, which is that there is essen-
tially no difference between an MTBE
site and a BTEX site—both need a
comprehensive, three-dimensional
site characterization.
Conclusion: It's no myth. Curiously,
the arguments made in the journal
article fully support the observation
that MTBE plumes do sink (or dive),
thus this behavior is no myth.
(Regardless of whether or not I agree
with any of the other arguments pre-
sented in the journal article, I
couldn't agree more with their state-
ment: "...it is important to conduct
complete, three-dimensional charac-
terization of plumes...")
• continued on page 12
ti
-------
LUSTLinc Bulletin 42 • October 2002
I Myths from page 11
MYTH #5: MTBE CAUSES
CANCER
Main points: (1) "Several studies
have shown the formation of tumors
in animals exposed to high concen-
trations of MTBE."
(2) "However, there is some
doubt about the relevance of these
data to assessing the carcinogenicity
of MTBE to humans and whether the
doses are environmentally realistic."
(3) "Furthermore, human epi-
demiology studies failed to support
the classification of MTBE as a car-
cinogen."
(4) "No national or inter-national
regulatory agency has classified
MTBE as a human carcinogen, and
the available genptoxicity data sug-
gest that MTBE is not mutagenic."
(5) "The weight of evidence sug-
gests that ingestion of water [contain-
ing MTBE] below or dose to the taste
threshold is unlikely to result in
adverse health effects.
(6) "...MTBE has been used to
treat gall stones both in the UK and
die US..."
Analysis: (1) Oddly, this first point
succinctly refutes the argument that
MTBE does not cause cancer—MTBE
does cause cancer, Both benign and
malignant (cancer) tumors have been
observed in two animal species at
multiple organ sites in long-term
studies. Generally this is sufficient for
a substance to be classified as a
potential human carcinogen at the
very least.
(2) The relevance of animal car-
cinogenicity studies to humans is
always uncertain. But, in the world of
toxicological testing, the use of ani-
mals under strict protocols is a neces-
sity for a variety of reasons. First, and
probably foremost, is that if s gener-
ally prohibitively expensive to use
human subjects. It is also difficult to
get human volunteers to be willingly
exposed to substances that stand a
chance of giving them cancer.
Humans also live considerably
longer than laboratory animals and
die time required for cancer to mani-
fest is generally a significant portion
of the lifespan of an organism. To
compensate, lab animals with shorter
life spans are given higher doses of
toxicants in die hope of inducing can-
cer in them before they would die
12
naturally. So while if s easy to belittle
animal studies, there are good rea-
sons why they are conducted the way
they are. The fact remains, MTBE is
an animal carcinogen.
(3) While no known studies of
human MTBE epidemiology have
conclusively demonstrated that
MTBE is a human carcinogen, neither
have they removed all doubt as to
whether or not it is in fact carcino-
genic in humans. EPA presented can-
cer slope factors associated with
MTBE in the 1997 publication:
"Drinking Water Advisory: Con-
sumer Acceptability Advice and
Health Effects Analysis on MTBE."
The National Science and Technology
Council (NTSC) concluded that
MTBE is an animal carcinogen and
has carcinogenic potential for humans
(National Toxicology Program 1998).
Considering the fact that the best
possible (least likely to cause cancer)
rating on the scale used by the Inter-
national Association of Research on
Cancer (IARC) is Group 4, which
indicates that a substance is "proba-
bly not carcinogenic to humans,"
even extremely long-term studies are
unlikely to completely vindicate
MTBE or any other potentially haz-
ardous chemical. Human studies take
decades to complete, and the wise
course of action in the interim is to
assume that a chemical is dangerous
rather than expose entire populations
(especially our children) and wait to
see what happens. Have our experi-
ences with lead, arsenic, mercury,
asbestos, cigarette smoke, coal dust,
and silica dust (to name but a few)
taught us nothing?
(4) The same points made in #3
apply here. But, the half of the story
that is not being told is that such deci-
sions are done by committee vote
and that generally the votes are not
unanimous—they're usually a nar-
row majority. For example, when the
National Toxicology Program voted
on whether or not to list MTBE as rea-
sonably anticipated to be a human car-
cinogen, the final vote was six to five
against listing after two subgroups
split four to three in favor of listing
and three to four against listing.
The fact that a committee as a
whole has not supported a resolution
declaring that MTBE is reasonably
anticipated to be a human carcinogen
obscures the fact that there is a great
deal of disagreement about MTBE
not being classified as a potential
human carcinogen. Further, these
votes have been against declaring
that MTBE is a human carcinogen
because there is insufficient evidence
that it is positively a human carcino-
gen, not because there is evidence
that MTBE is a noncarcinogen.
This is a very important distinc-
tion, as such rulings are a far cry from
concluding that MTBE is noncarcino-
genic. In fact, the body of data is suf-
ficiently persuasive for some
regulatory bodies.1 For example, the
California Office of Environmental
Health Hazard Assessment (OEHHA)
concluded in March 1999 that the
data on the carcinogenicity of MTBE
were sufficient to propose a Public
Health Goal (PHG) of 13 ppb for
MTBE, based on the carcinogenic
effects observed in animals. And, as
indicated in the analysis of point #3
above, the NTSC has concluded that
MTBE has carcinogenic potential in
humans.
(5) It is unclear which taste
threshold Woodward and Sloan are
talking about here. Several studies
have been conducted, and there has
been a wide range of results. But, lef s
play it safe and assume that the taste
threshold we're talking about is the
one that Campderi Food and Drink
Research Association of Chipping
Campden, England, conducted in
1993 at the request of Arco Chemi-
cals.
This study (which only grudg-
ingly became part of the public
record as a result of the lawsuit that
South Lake Tahoe Public Utility Dis-
trict recently won against the petro-
leum industry) established a taste
threshold of between 0.04 and 0.06
ppb!!! That's right, parts per billion!
This threshold is nearly three orders
of magnitude lower than EPA's cur-
rent drinking water advisory (which
is based on policy, not science). So,
I'd tend to agree with this point at
face value—if concentrations in our
drinking water are lower than 0.04
ppb, then there probably wouldn't be
any adverse health effects.
But, I'm only comfortable with
this concession if there is absolutely
nothing else in the water. There have
been no studies published that pre-
sent incontrovertible evidence that
small (even minute) amounts of
MTBE (or any other potentially toxic
chemical) in drinking water are safe
-------
October 2002 • LUSTLine Bulletin 42
to consume if any other potentially
toxic chemicals are also present.
Study of the toxic effects of mixtures
has largely been ignored, and the
data do not exist (at least not in the
public record.)
(6) Whether the pure phase of an
environmental contaminant has been
used for medical purposes isn't really
germane to this debate. Doubtless,
countless examples could be pre-
sented where toxic compounds have
been used (not wholly without risk)
to remedy an ill that may be immi-
nently debilitating (if not fatal) if not
treated immediately. Obviously in
such a case the mere chance of con-
tracting cancer (or manifesting other
long-term adverse effects) is greatly
outweighed by the necessity of treat-
ment with the potentially toxic sub-
stance.
Conclusion: It's no myth. MTBE is
an animal carcinogen, and while there
is disagreement over its classification
as a potential human carcinogen, the
best that can be said right now is that
we just don't know for sure. But, in
deference to the "precautionary prin-
ciple," if a substance is known to
cause cancer in animals, why in the
world would human beings want to
be unnecessarily exposed to it?
MYTH #6: MTBE IS A THREAT
TO DRINKING WATER
RESOURCES
Main points: (1) "Any chemicals,
metals or other toxic substances are a
potential threat to drinking water
supplies..."
(2) "MTBE is not toxic to human
beings."
(3) "The presence of MTBE in
spilled or leaked gasoline does not
increase the treat [sic] that the gaso-
line poses to drinking water
resources."
Analysis: (1) General agreement
with this point; however, any sub-
stance present in water can be consid-
ered to be a "contaminant." Whether
or not the substance is a "pollutant"
(and therefore a "threat") depends on
the concentration and the question of
whether the usability of the water has
been diminished. The presence of
any pollutant that renders a drinking
water supply undrinkable for any
reason is most certainly a threat. And
even low levels of MTBE render
water supplies undrinkable.
(2) This statement is false. MTBE
exhibits quite a number of toxic
effects on human beings; just check
any Material Safety Data Sheet
(MSDS) or EPA's Drinking Water
Advisory (U.S. EPA 1997). Docu-
mented symptoms include irritation
of the eyes, nose, and throat; dizzi-
ness; nausea; weakness; and potential
kidney damage. The carcinogenic
potential of MTBE in humans has not
yet been definitively established. (See
the discussion of Myth # 5.) Whether
any of these effects will occur
depends on the concentration, length
of exposure, route of exposure, and
sensitivity of the receptor. And, let's
not ignore metabolites of MTBE; in
particular TBA and TBF (tertiary-
butyl formate). Both of these are toxic
substances with known toxic effects
on humans.
(3) This statement is also false.
Lef s look at it from two different per-
spectives: (a) water resources, and (b)
drinking water supplies.
(a) MTBE has had an impact on
water resources—both groundwater
and surface water—at tens of thou-
sands of sites nationwide. In fact,
anywhere MTBE is detected in water
in the environment is an impact (and
not a positive one). At a significant
number of sites, no gasoline con-
stituent except MTBE has been
detected. This is directly attributable
to the properties of MTBE that enable
it to move more rapidly through the
environment than other non-ether
gasoline constituents.
(b) Consider the financial
impacts to drinking water supplies:
conservatively hundreds of millions
of dollars have been spent nation-
wide remediating and treating
MTBE-contaminated groundwater.
At all of the major, headline-grabbing
MTBE cases (e.g., Santa Monica; Lake
Tahoe; Long Island—too many sites
to list; Pascoag, RI; and most recently
Roselawn, IN) MTBE is the only sig-
nificant contaminant detected in the
drinking water.
The U.S. Geological Survey
(U.S.G.S.) reported (2001) on the
occurrence and distribution of MTBE
and other volatile organic compounds
in drinking water in the Northeast
and Mid-Atlantic regions. From 1993
to 1998, MTBE was detected in nearly
seven times as many drinking water
supplies as was benzene. A recent
U.S.G.S. study of 30 public water sup-
plies in Delaware found four wells
with benzene detections and 17 with
MTBE detections. Two of the MTBE
detections were above regulatory lev-
els, but none of the benzene levels
were above the MCL.
Conclusion: It's no myth. Clearly,
the statement that MTBE in gasoline
poses no additional threat to drink-
ing-water resources is false.
MYTH #7: MTBE CAN'T BE
REMEDIATED
Main points: (1) "MTBE responds to
the same types of physical, chemical
and biological treatment processes
effective with other hydrocarbon
contamination. Gasoline plumes con-
taining MTBE can be managed by
traditional approaches of hydraulic
control, impermeable barriers, reac-
tive barriers and excavation. The
same in-situ chemical oxidation or
bioremediation processes used for
other hydrocarbons can destroy
MTBE."
(2) "Indeed, the physical proper-
ties and resulting behavior of MTBE
expedite remediation by conven-
tional, physical processes. Classic
treatment technology like pump and
treat is particularly effective at
removing MTBE from the saturated
zone due to the high solubility, low
Henry's constant and low adsorption
coefficient of MTBE in groundwater.
In the unsaturated zone, the low
vapor pressure of MTBE makes soil
vapor extraction (SVE) a particularly
effective approach to removing the
components of gasoline and MTBE."
(3) "A variety of processes
including, air stripping, adsorption
of activated carbon or resins, biologi-
cal treatment and advance [sic] oxi-
dation have been used to remove
MTBE from groundwater brought to
the surface."
Analysis: (1) As MTBE is seldom the
remediation driver, it is often treated
along with other petroleum con-
stituents in systems designed for
treatment of the other constituents
alone. Of the four "traditional"
approaches listed in the article as
being effective in managing MTBE
plumes, only one, reactive barriers, is
anything more than a containment
method, and it is hardly "tradi-
• continued on page 14
_
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LUSTLine Bulletin 42 • October 2002
m Myths from page 13
tional." Permeable reactive barriers
(PRBs) are cutting-edge science and
the optimization of these systems for
MTBE in all subsurface environments
is a long way off.
There's no dispute that chemical
oxidation and bioremediation (see
also the discussion of Myth #8) may
be effective in remediating MTBE
contamination. The problem with
bioremediating MTBE is the rate of
the reaction and the question of
whether it will be fast enough to
achieve remediation objectives in a
reasonable period of time. In many
environments, even where the conta-
minant source has been removed,
bioremediation can be expected to
take years, even decades, to meet reg-
ulatory levels.
(2) These statements are deceiv-
ing, as almost all of MTBE's proper-
ties make it more difficult and
expensive than BTEX to remediate,
not easier and less expensive. While
pump-and-treat may be very effec-
tive in pumping MTBE out of the
ground (assuming that the plume is
captured by the extraction wells), the
process generates large volumes of
groundwater that must be treated.
Technologies that force MTBE out of
the dissolved phase and into the
vapor phase (e.g., air-stripping) gen-
erally require multiple passes
through the system, plus off-gas
treatment, and these expenses may
significantly increase the overall cost
of remediation. Let's look at how
MTBE's properties would affect
remediation costs in both the satu-
rated and unsaturated zones.
In the saturated zone, the high
solubility of MTBE is one of the pri-
mary reasons it creates such difficult
(and expensive) groundwater reme-
diation problems in the first place.
MTBE plumes may be significantly
larger than BTEX plumes, meaning a
larger volume of water must be
treated, and more wells will probably
be required to capture the plume.
MTBE's low Henry's law constant
means that once dissolved in water,
MTBE will tend to stay in the water—
air sparging and air stripping are not
nearly as effective for MTBE as they
are for BTEX. And its low adsorptive
coefficient means that although
MTBE will move virtually unretarded
through the subsurface, treatment by
14
granular-activated carbon is much
less cost-effective because MTBE
exhausts carbon much more quickly
than does BTEX, so the carbon must
be changed more frequently.
In the unsaturated zone, the
effectiveness of SVE is dependent
upon properties other than just vapor
pressure. If a release is acted on
immediately, while it is still in the
vadose zone, and if the vadose zone
has relatively low soil moisture, then
SVE can be very effective. But,
MTBE's affinity for soil moisture and
it's low Henry's law constant mean
that MTBE will tend to dissolve
quickly in soil moisture where it isn't
as amenable to SVE. In fact, SVE per-
formance is significantly reduced by
high soil moisture.
(3) The term "removal" is mis-
leading, as it is probably very rare
indeed that contaminants are actually
completely removed from ground-
water as opposed to merely "reduced
in concentration." For example, if a
treatment system is 99 percent effec-
tive at "removing" MTBE, then to
achieve a final concentration of 10
ppb, the influent water cannot have a
concentration greater than 1 mg/L.
As stated in #2 of this section, air
stripping, adsorption, and biological
treatment all have limitations.
Advanced oxidation techniques may
be highly effective, but some of them
aren't without significant risk. For
instance, use of Fenton's Reagent on
gasoline releases has resulted in cata-
strophic explosions and loss of life.
Advanced oxidation processes also
generate degradation products (e.g.,
tertiary-butyl alcohol, tertiary-butyl
formate, formaldehyde) whose toxic-
ity is greater than that currently
ascribed to MTBE.
Conclusion: It is a myth. MTBE can
be remediated. However, the situa-
tion is not nearly as rosy as the jour-
nal article (and poster and seminars)
would have one believe.
MYTH #8: MTBE DOESN'T
BIODEGRADE
Main points: (1) "Increasing evidence
is being found and reported on the
biological natural attenuation of MTBE
in gasoline contaminated aquifers."
(2) "While defined biodegrada-
tion pathways are predominantly
aerobic, recent evidence indicates
that some organisms indigenous to
the subsurface can utilize MTBE as a
carbon and energy source by reduc-
ing iron in the presence of humates or
under methanogenic conditions."
Analysis: (1) No disagreement here.
The body of literature supporting
biodegradation of MTBE is indeed
increasing in volume. This is not to
say, however, that MTBE will biode-
grade in every subsurface environ-
ment at a rate that is sufficient to
achieve remediation objectives in a
reasonable period of time. It is impor-
tant to note that MTBE-degrading
microorganisms are not nearly as
ubiquitous as are! BTEX degraders
(Deeb and Kavanaugh 2002).
In some environments, MTBE
biodegradation occurs very quickly,
about as quickly as benzene
biodegradation (this is usually in sit-
uations where the groundwater is
sufficiently oxygenated such that
oxygen is not the limiting factor). In
other environments, the rate is so
slow as to be almost nonexistent. The
problem is that researchers are cur-
rently unable to predict a -priori for
any given environment whether
MTBE biodegradation will be fast or
slow. Such a determination can only
be made in real time (a -posteriori) and
with field data, not laboratory data.
(2) There is no disagreement as to
whether MTBE biodegrades anaero-
bically. Kolhatkar et al. (2000) studied
MTBE (and TEA) plumes at 74 gas
stations in the U.S. They found that
natural biodegradation of MTBE
could be demonstrated only under
strongly anaerobic conditions
(methanogenic with or without sul-
fate) but not weakly anaerobic/
anoxic conditions! (weakly meth-
anogenic and sulfate available, or
nitrate depleted and sulfate avail-
able). :
This study also presents a compi-
lation of MTBE biodegradation rates
from the literature.'It points out that
MTBE biodegradation under iron-
reducing conditions in the field is
very slow, and biodegradation under
sulf ate-reducing conditions had not
yet been demonstrated.
Deeb and Kavanaugh (2002) cite
four more recent studies of anaerobic
biodegradation under a variety of
conditions. These studies support the
observation that anaerobic biodegra-
dation of MTBE is highly site-specific
and that microorganisms capable of
-------
October 2002 • LUSTLine Bulletin 42
degrading MTBE in the absence of
oxygen have not yet been cultured.
Therefore, the mechanisms of anaero-
bic biodegradation have not yet been
identified and hence can't be opti-
mized until cultures have been iso-
lated for study.
Conclusion: It is a myth. MTBE is
biodegradable; however, not in all
environments and not always at rates
that are fast enough for remediation
objectives to be met in a reasonable
period of time or within a reasonable
distance from the source so that
receptors are protected.
MYTH #9: IMTBE WON'T
NATURALLY ATTENUATE
Main points: (1) "...the process of
natural attenuation includes both
destructive (mass reduction) and
nondestructive processes. Destruc-
tive processes include biological
degradation and abiotic chemical
degradation. Nondestructive
processes include dilution, adsorp-
tion, dispersion and volatilization."
(2) "Aerobic biodegradation of
MTBE occurs when the concentration
of other degradable substrates
becomes limited and sufficient dis-
solved oxygen is present. Conse-
quently, biologically based natural
attenuation at the leading edge of the
plume has been used to explain
many mature, static plumes."
(3) "Recent investigations into bio-
logical degradation of MTBE under
anaerobic conditions have verified
biodegradation by ferric iron reduc-
tion in the laboratory and by
methanogenic conditions... in the
field."
Analysis: (1) For petroleum hydro-
carbons, biodegradation is the most
important (and preferred) attenua-
tion mechanism because it is the only
natural process that results in actual
reduction in the mass of petroleum
hydrocarbon contamination. Neither
dispersion nor dilution are particu-
larly effective since many docu-
mented MTBE plumes are several
thousand feet in length and at con-
centrations that are high enough to
cause adverse impacts on drinking
water supplies. In the subsurface,
there are no significant abiotic trans-
formation processes for MTBE.
MTBE does not sorb well to soil
organic carbon nor mineral surfaces,
and once dissolved into water it
doesn't tend to volatilize readily, so
neither of these mechanisms are very
helpful in-situ.
(2) Aerobic biodegradation con-
sumes available oxygen, resulting in
anaerobic conditions in the core of
the plume and a zone of oxygen
depletion along the outer margins.
The anaerobic zone is typically more
extensive than the aerobic zone due
to the abundance of anaerobic elec-
tron acceptors relative to dissolved
oxygen (Weidemeier et al. 1999). For
this reason, anaerobic biodegradation
is typically the dominant process.
For both aerobic and anaerobic
processes, the rate of contaminant
degradation is limited by the rate of
supply of the electron acceptors, not
the rate of utilization of the electron
acceptors by the microorganisms. As
long as there is a sufficient supply of
the electron acceptors, the rate of
metabolism does not make any prac-
tical difference in the length of time
required to achieve remediation
objectives.
(3) So as not to reiterate, see the
analysis of point #2 in myth #9. It is
also extremely important to realize
that laboratory-derived rates of
biodegradation are almost never
comparable to rates observed in the
field. Almost without exception, lab-
oratory rates are much higher, and
estimations (or simulations) of the
time required to reach remediation
objectives should never be based on
laboratory-derived rates.
Conclusion: It is a myth. However,
this entire point is really a continua-
tion of the preceding myth about
biodegradability of MTBE. It is not a
discussion of other natural attenua-
tion mechanisms. And, in fact,
biodegradation is the only significant
natural attenuation process for MTBE
in most subsurface environments.
MYTH #10: MTBE
REMEDIATION COSTS
SIGNIFICANTLY MORE THAN
BTEX REMEDIATION
Main points: (1) "It is true that some
gasoline spills and leaks were
ignored in the past, but today all
leaks and spills must be assessed and
remediated."
(2) "...gasoline does not belong
in groundwater."
(3) "Numerous case studies over
the last few years have confirmed
that the presence of MTBE in gasoline
does not significantly impact the cost
for assessment and remediation."
(4) "The site assessment, design
and remediation — are generally inde-
pendent of the gasoline compo-
nents."
Analysis: (1) In theory anyway, this
should be the case. But, the fact of the
matter is that we're leaving ever
larger masses of contaminants in the
ground at increasing numbers of
sites. And in many cases, site charac-
terization data are too sparse, and of
such poor quality, that the real mag-
nitude of the problem at the site isn't
adequately defined. Comprehensive
three-dimensional site characteriza-
tion hasn't been universally imple-
mented and not all states routinely
require appropriate sampling and
analysis for MTBE (and even fewer
for the other common oxygenates).
(2) I agree 100 percent with this
point. The trouble is that UST sys-
tems do leak, and they will continue
to leak. With a leak detection thresh-
old of a mere 0.1 gallon per hour, a
"tight" system could potentially leak
about 900 gallons of fuel per year,
which means about 50 to 135 gallons
of MTBE would be released into the
environment.
(3) One of the many factors
affecting cleanup costs is target
cleanup standards. In the survey that
NEIWPCC conducted in 2000, 16
states that had (at that time) ground-
water standards or cleanup and/or
action levels for MTBE reported that
MTBE had made a noticeable impact
on the cost of remediation; seven of
these states indicated that cost
increases at some sites were 20 per-
cent to more than twice as expensive.
Of the 25 states that indicated that
MTBE had no noticeable impact on
the cost of remediation, 15 either had
no cleanup standards for MTBE or
didn't require analysis for MTBE.
Undoubtedly the picture has
changed somewhat over the past two
years. More states have cleanup stan-
dards, action levels, or require analy-
sis for MTBE (and other oxygenates).
(4) Hopefully, the days of long-
screened, three- to four-well site
characterizations are gone (and just
as hopefully not simply replaced by
• continued on page 16
15
-------
LUSTLine Bulletin 42 • October 2002
I Myths from page 15
the drive-by site/risk assessment).
The presence of MTBE in groundwa-
ter has opened up our eyes to the fact
that "conventional" monitoring wells
are particularly poorly suited for
three-dimensional site characteriza-
tion.- Far more data, and data analy-
sis, are required to adequately
characterize contaminant plumes,
especially those made up of MTBE,
which can be deeper and longer than
previously envisioned for BTEX
(although the vision of relatively
well-behaved BTEX plumes is in seri-
ous need of "revision"). And, none of
this is cheap. So, site characterization
costs more, remediation costs more,
and performance monitoring is gen-
erally required for a longer period of
time and, hence, costs more. The bot-
tom line is that dealing with MTBE
plumes appropriately will cost more
than dealing with BTEX plumes.
Conclusion: It's no myth. The
assessment and remediation of an
MTBE plume has the potential to cost
significantly more than a BTEX-only
plume.
MYTH #11: MTBE ALWAYS
DRIVES REMEDIATION
DESIGN, PROGRESS, AND
COST
Main points: (1) "...remediation
technology selection; progress and
costs are very site specific."
(2) "Remediation progress and
costs are primarily driven by the: A.
Amount and duration of the release,
B. Physical nature of the subsurface,
C. Concentrations of the gasoline
components in the soils and ground-
water, D. Rates and direction of
chemical migration, E. Nearest recep-
tors and exposure pathways, F.
Required cleanup objectives."
(3) "However, benzene, due to its
toxicity, has driven progress and
costs at some sites."
Analysis: (1) I agree 100 percent.
This point is too often glossed over. It
is folly to assume that, if the same
type of remediation technology were
implemented at multiple sites with-
out first conducting comprehensive,
three-dimensional site characteriza-
tion, each of the systems would oper-
ate optimally. Remediation is site-
specific.
16
(2) All of the listed factors cer-
tainly affect remediation costs. A cou-
ple of critical factors that are not on
this list are contaminant "treatabil-
ity" and system performance. If an
inappropriate treatment technology
is selected for a specific site, then it
will operate inefficiently, if at all. The
remediation time frame will be
extended, and long-term perfor-
mance monitoring costs will increase.
Likewise, if the system isn't designed
optimally for the site, it will operate
inefficiently and ineffectively,
thereby increasing the cost of remedi-
ation.
(3) According the NEIWPCC
(2000) MTBE survey, 37 states indi-
cated that BTEX and free product are
the two factors that are their primary
remediation drivers. However, 10
states indicated that MTBE drives
remediation at greater than 20 per-
cent of their LUST sites.
As more states establish action
levels and cleanup levels or MCLs,
this percentage will probably
increase.
Conclusion: It is a myth, though
perhaps only because of the word
"always," which covers a lot of bases.
It should also be noted that regula-
tory levels for MTBE in groundwater
(and drinking water) have been
decreasing, and that it is possible that
MTBE will drive many more cleanups
in the future, especially as more
states adopt regulatory levels.
The Score
Now that we've analyzed each of the
11 myths, what's the score? I count 4
myths and 7 nonmyths. Thus, more
than half of what Woodward &
Sloan's article claims are myths, are,
in fact, not myths. Or stated another
way, the article presents "half-truths"
and as a whole the article itself can,
by definition, be considered a myth!
Hmm, does that make it 12 myths? •
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Methyl Tertiary-Butyl Ether (MtBE). EPA-822-
F-97-009, Office of Water, December.
Woodward, D., and D. Sloan. 2001. Common
Myths, Misconceptions and Assumptions
about MTBE: Where Are We Now. Contami-
nated Soil, Sediment, and Water, Spring Special
Issue, pp. 16-19. ;
http://wwiv.aehsmag.com/issues/2001/spring/
myths.htm
Hal White is a hydrogeologist and reg-
istered professional geologist. His work
experience includes nine years as an
environmental consultant, one year as
a laboratory technician, and eight years
as a regulator with the U.S.EPA Office
of Underground Storage Tanks. He can
be reached at hal90Q7@juno.com. Hal
welcomes feedback on this or any
article, as well as suggestions for
future articles.
This article was written by the author in his
private capacity, and the conclusions and opin-
ions drawn are solely!those of the author.
Although the article has been reviewed for
technical accuracy, it has not been subjected to
U.S. EPA review and therefore does not neces-
sarily reflect the views of the agency, and no
official endorsement should be inferred.
-------
October 2002 • LUSTLine Bulletin 42
How to Collect Reliable Soil-Gas Data for
Risk-Based Applications
Part 1: Active Soil-Gas Method
by Blayne Hartman
In July 2002,1 attended a confer-
ence held by the Indiana
Department of Environmental
Management (IDEM) in Indianapolis
with special emphasis on the
upward-vapor risk-assessment path-
way. Issues raised repeatedly during
the conference pertained to the
advantages of using soil-gas data in
making risk assessments and the
need for having established proto-
cols and guidance for soil-gas sur-
veys to ensure high-enough quality
data. After making a brief statement
to the audience and then being
swarmed by interested parties, it was
clear to me that the environmental
community would be well served by
an article addressing this topic.
Contrary to Popular Belief...
Before diving into the meat of the
topic, let me make three points to
address some of the misconceptions
raised at the IDEM meeting:
• Contrary to popular belief, soil-gas
techniques that yield reliable data
have been in existence for many
years, and published regulatory
protocols do exist. (I list applicable
Web sites later.)
• Contrary to the prevailing opinion
that soil-gas data is so variable that
it can not be trusted for risk-
assessment purposes, soil-gas data
collected in a careful, consistent
manner typically show repro-
ducibility of +/- 25 percent. This
margin of error is on the same
order as indoor air measurements
and is a much smaller error than
that introduced by many of the
assumptions in the Johnson-
Ettinger (J-E) model using ground-
water data.
• Contrary to popular belief, soil-gas
data should be significantly less
expensive (by at least a factor of
two) than indoor air measure-
ments.
Why Use Soil-Gas Data for
Upward-Vapor Risk
Assessment?
As was pointed out repeatedly at the
Indianapolis conference, even by Dr.
Paul Johnson himself, the use of
actual soil-gas values, rather than
values calculated from models, is
preferred. The reason for this is that
the measured values account for
processes that are currently hard to
quantify with risk models, such as
volitalization from groundwater,
transport across the capillary fringe,
and bioattenuation. In addition, mea-
sured values will take into account
the presence of vapors in the vadose
zone from sources other than
groundwater, such as contaminated
soil or lateral vapor transport (i.e.,
vapor clouds).
Experience has documented that
the potential error in calculated soil-
gas values versus measured soil-gas
values can be several orders of mag-
nitude. If calculated soil-vapor values
can differ from actual values by fac-
tors of 10 to 1,000, then the calculated
vapor fluxes and in turn, the calcu-
lated room concentrations using any
version of the J-E model, will be off
by a similar factor. In other words,
the error introduced by using calcu-
lated soil-vapor data is likely to be far
greater than the errors introduced by
all of the other parameters used in
the model (e.g., porosity, advection,
multi-layers).
Some History and Current
Status of Regulatory Soil-Gas
Guidance
Historically, soil-gas surveys have
been used primarily for site assess-
ment purposes to identify soil and
groundwater contamination. Part of
the motive for employing such sur-
veys was that the methods were inex-
pensive and quick. In the absence of
published U.S. EPA methods, soil-
gas surveys were conducted using a
variety of protocols, depending on
the operator. Indeed, in their simplest
form, soil-gas surveys have been con-
ducted by hammering a piece of gal-
vanized water pipe into the ground
and hooking up a hand-held meter.
No wonder soil-gas methods got
such a bad rap for data quality.
In the early 1990s, the Los Ange-
les Regional Water Quality Control
Board (L.A. Water Board), under con-
tract to U.S. EPA Region 9, began
investigating the sources of chlori-
nated solvent contamination in
groundwater in parts of the Los
Angeles Basin. The board preferred
to use soil-gas surveys as its initial
investigatory method on the basis
that the technique had a greater
chance of detecting vadose-zone con-
tamination.
Recognizing the lack of pub-
lished protocols and noting a wide
variability in techniques by firms
offering the service, the L.A. Water
Board, with input from many of the
soil-gas firms, wrote a set of analyti-
cal guidelines for soil-gas surveys for
the purpose of bringing some consis-
tency to the data. The original docu-
ment, written in 1992, has been
revised several times by the L.A.
Water Board (most recent version:
February 1997), and adapted as
recently as 2000 by the San Diego
County Department of Environmen-
tal Health (DEH) for its site assess-
ment manual (http://www.co.
sandiego.ca.us/deh/lwq/sam/pdf_
files/SoilGas.PDF).
As years passed, these protocols
became the "standard" for most of
southern California and parts of
northern California. However, they
focused primarily on the analysis of
soil-gas samples and gave little infor-
mation on the collection of these sam-
ples. Since collection methods are
also extremely varied among opera-
tors and can introduce large errors,
the San Diego County DEH decided
that additional guidelines were
needed to bridge this gap, especially
• continued on page 18
_
-------
LUSTLine Bulletin 42 • October 2002
• Active Soil-Gas Method
from page 17
in light of the increased emphasis on
health risks resulting from, vapor
intrusion.
In 2001, the DEH commissioned
a technical work group to write a set
of collection guidelines for all soil-gas
applications, including upward
vapor risk. Those guidelines were
completed in August 2002 and are
now available in the San Diego County
Site Assessment Manual (http://www.
co.san-diego.ca.us/cnty/cntydepts/
landuse/env_health/lwq/sam/pdf_
files/presentations/soilvapor_guide
.pdf).
These guidelines are not step-by-
step protocols, but they present gen-
eral topics/issues that need to be
considered and fulfilled. Currently,
CA-EPA, in conjunction with the L.A.
Water Board and many of the local
soil-gas firms, is finalizing a set of
step-by-step collection protocols.
These should be available on-line
before the end of this year, perhaps
as early as November.
Which Soil-Vapor Method
to Use?
Three methods are commonly
employed to measure soil-vapor/gas
contamination: active, passive, and
surface-flux chambers. A full discus-
sion of the various measurement
techniques is beyond the scope of this
article; however, some summary
thoughts will be presented here.
Helpful overviews can be found in
the San Diego County Site Assessment
Manual and the Standard Encyclopedia
of Environmental Science, Health &
Technology, Chapters 11.8 and 11.9
(ISBN#0-07-038309-X).
Active soil vapor methods con-
sist of the withdrawal of the soil
vapor from the subsurface and subse-
quent analysis of the vapor. These
methods give concentration data
(e.g., //g/rnr), which are required for
calculating the contaminant flux
using Pick's first law or with various
versions of the Johnson-Ettinger
model. Vertical profiles of the soil-
vapor concentrations can be obtained
to aid in determining the direction
and magnitude of the flux. Active
soil-vapor data can be collected and
measured in real time, enabling deci-
sions to be made in the field. The
problem most often raised with
18
active soil-vapor data is whether the
concentrations measured at any
given time and day are representa-
tive of normal conditions (i.e., how
"stable" are active soil-vapor data?).
We'll tackle this issue in the sections
ahead.
Passive soil vapor methods
consist of the burial of an adsorbent
in the ground with subsequent
retrieval and measurement of the
adsorbent. These methods give a
time-integrated measurement and
therefore reduce the uncertainty
caused by temporal variations. How-
ever, passive soil-vapor methods
only yield soil-vapor data in terms of
mass (e.g., micrograms [fig] or some
other form of relative units), not con-
centration, because the amount of
vapor that comes into contact with
the adsorbent is unknown. To miti-
gate this problem, a "conversion" of
the data from mass units to concen-
tration units is sometimes attempted,
which requires knowledge of the vol-
ume of vapor that passed by the
buried adsorbent during the burial
time period. There is no practical way
to estimate this volume; therefore
passive soil-vapor data cannot be
used for quantitative upward vapor-
migration assessment. For this rea-
son, this method will not be
discussed further in this article.
Surface-flux chambers are
enclosures that are placed directly on
the surface (e.g., ground, floor) for a
period of time (generally a few hours
to a few days), and the resulting cont-
aminant concentration in the enclo-
sure is measured. By dividing the
measured concentration by the incu-
bation time, a direct value for the flux
is determined. This method offers
advantages over the other two meth-
ods because it yields the actual flux of
the contaminant out of the ground,
which eliminates some of the
assumptions required when calculat-
ing the flux with a model. However,
this technique is not as fast or easy to
implement as the other two, it is sub-
ject to near-surface effects (i.e., are the
measured fluxes "stable"?), and it
gives us no idea of what may be "hid-
ing below."
Which method to use on a given
site depends upon your site-specific
goals and the logistical limitations.
The active soil-vapor method offers
less uncertainty and more versatility
than the surface-flux chamber
method for most situations. For this
reason, we'll start with the active soil-
gas method and tackle the surface-
flux chamber method in the next
issue of LUSTLine.
Collecting Active Soil-Gas
Samples
Reported soil-vapor data depends
greatly on the collection protocols.
This section presents a brief descrip-
tion of the primary factors that can
influence the measured results. Refer
to the previously referenced docu-
ments for more details.
Volume of Sample Withdrawn
In my opinion, this is perhaps the
most important issue influencing the
integrity and composition of soil-gas
samples, so I will address it first. In a
nutshell, the larger the quantity of
soil vapor that is: withdrawn, the
greater the uncertainty about the
exact location from which the soil
vapor came. For example, if near the
surface, large extraction volumes
increase the potential that atmos-
pheric air might be, drawn down the
outside of the probe body. If at depth,
large extraction volumes increase the
potential that samples might be from
a different depth or location. In addi-
tion, large purge volumes can create
vacuum conditions that cause conta-
minant partitioning ;from the soil into
the soil gas. All of these issues
increase the potential that the col-
lected soil-gas sample is not repre-
sentative of in-situ soil vapor at the
target depth. Lastly, the larger the
sample volume required, the larger
and more complex the sample collec-
tion system required (e.g., vacuum
pumps, larger sample containers).
For all of these reasons, sampling sys-
tems with small, internal dead vol-
umes offer advantages over systems
with larger, internal dead volumes,
although reliable samples can be col-
lected with the latter.
Sample Collection Through a
Driven Rod versus Burial of
Tubing Two techniques are most
commonly used to collect samples:
• Driving a hard rod to a given depth
(e.g., using hand equipment,
direct-push systems) with the sub-
sequent removal of the rod.
• Burying a small-diameter (1 / 8" to
1/4" outer diameter) inert tube to
a given depth with subsequent
-------
October 2002 • LUSTLine Bulletin 42
sampling after a short "equilibra-
tion" time period (20 to 30 min-
utes). The tubing may be buried in
holes created with hand-driven
rods, direct-push systems, hand
augers, or drill rigs.
Both methods have been shown
to give reliable, reproducible data. If
the drive-rod method is used, the
sample integrity is optimized if the
rod is drawn through small-diameter
inert tubing that runs down the cen-
ter of the drive rod, as opposed to the
drive rod itself.
Purge Volume The sample-collec-
tion equipment has an internal vol-
ume that is filled with air or some
other inert gas prior to insertion into
the ground. This internal volume,
often called the dead volume, must
be completely purged and filled with
soil vapor to ensure that a representa-
tive soil-vapor sample is collected.
Different opinions exist on the opti-
mum amount of vapor to be purged.
Some believe that, at a minimum,
enough vapor should be withdrawn
prior to sample collection to purge
the probe and collection system of all
ambient air or purge gas (one purge
volume). Others believe that a mini-
mum of three system volumes
should be purged, similar to a
groundwater monitoring well. Most
experienced soil-vapor personnel
purge a minimum of one and a maxi-
mum of five system volumes before
collecting a sample. CA-EPA requires
that a site-specific purge volume test
be conducted at the start of a survey.
In my opinion, this test is only neces-
sary when large volumes are being
collected (>500 cc). Most important is
that the purge volume is consistent
for all samples collected from the
same site.
Excessive Vacuums Applied Dur-
ing Collection Soil-vapor samples
that are collected under high-vacuum
conditions or under a continuous
vacuum may contain contaminants
that have partitioned from the sorbed
and dissolved phase into soil gas cre-
ated by the collection process, rather
than the contaminants present in the
undisturbed soil vapor. For collection
systems employing vacuum pumps,
the vacuum applied to the probe
should be kept to the minimum nec-
essary to collect the sample and
should be measured and recorded.
Probe Seals For collection systems
that have large purge volumes or that
are designed to collect large sample
volumes, it is often necessary to seal
the probe at the surface. Seals may
also be necessary for small-volume
systems if the soils are extremely
porous and the sampling depth is
close to the surface (<3 feet). Most
common sealing techniques involve
packing the upper contact of the
probe at the surface with grout or
using an inflatable seal. Seal integrity
can be tested easily by allowing a
tracer gas (e.g., propane or butane) to
flow around the probe at the contact
with the ground surface and then
analyzing the collected soil-vapor
samples for the tracer gas. CA-EPA
requires tracer-gas tests on at least 50
percent of the probes. In my opinion,
this test is only necessary at very
shallow depths (<3 feet bgs), or when
larger volumes are being collected
(>500 cc) at <5 feet bgs, or when it is
visually apparent that the surface
seal is poor.
Systems with Vacuum Pumps Soil-
vapor samples from collection sys-
tems that employ vacuum pumps
should be collected on the intake side
of the pump to prevent potential con-
tamination from the pump. Further,
because the pressure on the intake
side of the pump is below atmos-
pheric, soil-vapor samples must be
collected with appropriate collection
devices, such as gas-tight syringes
and valves, to ensure that the sam-
ples are not diluted by outside air.
Sample Containers and Sample
Storage The rule of thumb here is
the shorter the time between collec-
tion and analysis, the better. While
on-site analysis is advantageous to
ensure sample integrity, soil-vapor
samples can be collected and ana-
lyzed off-site. To minimize potential
effects on the sample integrity, follow
these recommended practices:
• Maximum storage time should not
exceed 48 hours after collection.
• Samples should not be chilled dur-
ing storage, as is common with soil
and water samples.
• Gas-tight vials or canisters may be
used if stored samples are to be
subjected to changes in ambient
pressure (e.g., shipping by air).
Tedlar bags are not advised.
• For fuel-related compounds (e.g.,
TPHv, BTEX) and biogenic gases
(e.g., CH^ CO2, and O2), allowable
containers include Tedlar bags,
gas-tight vials (glass or stainless
steel), and Summa canisters.
• For halogenated compounds (e.g.,
TCE, TCA, PCE), allowable con-
tainers should be gas tight and
also dark to eliminate potential
effects due to photodestruction.
Tedlar bags are generally not con-
sidered to be reliable for low-cont-
aminant levels for storage times
exceeding a few hours. For higher-
contaminant levels (>1 ^g/L-
vapor), storage in Tedlar bags for
up to 24 hours may be okay.
Collection of Soil Vapor Samples
with Summa Canisters Because
Summa canisters are typically large-
volume containers (e.g., three to six
liters) under high vacuum, extra care
should be exercised during sample
collection to ensure that air from the
surface is not being inadvertently
sampled or that desorption of conta-
minants from the soil does not take
place. The possibility of break-
through from the surface increases
the closer to the surface the samples
are collected (i.e., less than five feet
below grade). To minimize the poten-
tial of surface breakthrough, there
should be seals around the probe rod
at the surface. To minimize the
potential desorption of contaminants
from the soil, Summa canisters
should be filled at a rate that mini-
mizes the vacuum applied to the soil
and the turbulent flow at the probe
tip. CA-EPA's guidance requires this
rate to be less than 200 mL/min,
although the technical basis for this
specific value is unclear.
Transient Effects Influencing
Measured Soil-Gas Values
There are four transient effects that
can influence soil-gas values: temper-
ature, barometric pressure, precipita-
tion, and gravitational effects. So let's
look at each of these.
• Temperature This can have an
effect on soil vapor concentrations,
since both the vapor pressure and
water solubility of compounds are
temperature dependent. However,
temperature variations decrease
with depth in the soil column and
• continued on page 20
19
-------
LUSTLinc Bulletin 42 • October 2002
• Active Soil-Gas Method
from page 19
are unlikely to have large influ-
ences on concentrations at five feet
below grade or greater. In areas
with large seasonal temperature
variations, the most conservative
values will be collected in the
warmer months. Measurement of
temperature at collection depth is
easy and can help to quantitate
any expected variation. In areas
with small temperature variation,
the variation at typical collection
depths (>3 feet bgs) is typically
less than 2& C. This level of temper-
ature variation will not create a
measurable effect.
• Barometric Pressure Changes in
barometric pressure can lead to a
pressure gradient between the soil
vapor and the atmosphere, creat-
ing a flow of soil vapors out of the
vadose zone during barometric
lows and into the vadose zone
during barometric highs. The
potential effects decrease with
increased sampling depth and are
generally less than a factor of two
at depths of five feet below grade
or greater. Measurement of baro-
metric pressure is advised for sam-
ples collected at depths shallower
than five feet below grade for risk-
based applications.
• Precipitation Infiltration from
rainfall can potentially impact soil
vapor concentrations by displac-
ing the soil vapor, dissolving
volatile organic compounds, and
by creating a "cap" above the soil
vapor. In practice, infiltration from
large storms only penetrates into
the soil on the order of inches.
Hence soil-vapor samples col-
lected at depths greater than three
feet below grade are unlikely to be
significantly affected. Soil vapor
samples collected closer to the sur-
face (<3') may be affected, and it is
recommended that measurements
of percent moisture of the soil be
taken if shallow sampling is per-
formed during or shortly after sig-
nificant rainfall (>!").
• Gravitational Effects (Earth
Tides) Earth tides (movement of
soil vapor in response to variations
of the earth's geometric shape due
to gravitational pull) have been
20
promoted as a factor on soil-vapor
movement. However, in reality,
fluctuations in water levels during
periods of maximum gravitational
pull (new and full moons) are less
than 0.1 foot. Hence, earth tides do
not have a significant effect on
soil-vapor movement and concen-
tration.
Analysis of Active Soil-Gas
Samples
As stated previously, regulatory
guidance for soil-gas samples has
existed since 1992. This guidance is
similar to the U.S. EPA analytical
methods for water and soils in SW-
846 and yields equivalent-quality
data. The largest modification from
SW-846 methods is the limited num-
ber of target compounds (22 in total)
chosen to cover the most common
aromatic and solvent compounds.
The San Diego County version
expands and divides the target com-
pound list into three different
groups: fuels, solvents, or mixed-use
(http://vvww.co.san-diego.ca.us/deh/
lwq/sam/pdf_files/SoilGas.PDF).
Primary analysis-related factors
that can have an effect on soil-vapor
data are:
• Instrumentation The typical
instruments used for the analysis
for most compounds are gas chro-
matographs that are equipped
with a variety of detectors. VOCs
are detected and quantified with
photoionization detectors (PIDs),
electron capture detectors (ECDs),
electrolytic conductivity detectors
(ElCDs), and mass selective detec-
tors (GC/MSs). In some cases,
depending on the project goals,
simple flame ionization detectors
(FIDs) may be suitable. The
GC/MS provides more selectivity
and is advantageous at sites where
a variety of compounds may be
present and cause interferences. At
gasoline sites, the GC/MS is the
preferred instrument for risk
assessments due to the high poten-
tial for the alkanes to interfere
with benzene and the oxygenates.
• On-Site versus Off-Site Analy-
sis On-site analysis offers signifi-
cant advantages over off-site
analysis, especially for risk assess-
ments since the real-time data
enables additional locations to be
added, either spatially or vertically.
Laboratory-grade instruments,
including mass spectrometers, are
capable of being transported into
the field, and they can fulfill the
analytical protocols referenced
previously.
• Detection Limits Most analytical
instruments can readily reach
detection levels'of 0.1 fig/1 (100
^g/m3) in the vapor (beware, 1
,wg/L-vapor is not equivalent to 1
ppbv) using 10 cc to 40 cc of sam-
ple. Programs :requiring lower
detection limits (1 to 10 ^g/m3)
typically require larger sample
volumes (>1000.cc) and are usu-
ally performed by collecting sam-
ples in a Summa canister, with
subsequent analysis off-site by an
air-concentration method (e.g.,
TO-14 or TO-15). Because soil-gas
concentrations can be 1,000 to
100,000 times higher than indoor
air concentrations, the potential
for carryover from "hot" samples
is much greater. To avoid this,
every Summa canister used for
soil-gas samples should be cleaned
and verified clean by analysis
when used for risk assessments.
An alternative approach for very
low detection limits that elimi-
nates the use of Summas is to use
on-site analysis with the GC/MS
in SIM mode or, depending on the
VOCs of concern, by Method 8021
(PID/E1CD/ECD).
Issues Specifically Related to
Risk Assessments
Sample Location and Spacing
Enough samples should be collected
to allow a representative estimate of
the average flux to the base of the
existing or future structure. At a min-
imum, samples should be collected at
the location of highest vadose-zone
contamination near or under the
structure and at each corner, or along
each side, of the structure (inside if
logistics allow, immediately outside
if not). Real-time results can be
extremely advantageous, because
additional locations can be added
around or inside the structure to bet-
ter define the most reasonable value
to use in the risk calculation. How the
sample results are averaged (e.g.,
straight average, average plus two
standard deviations) needs to be
specified by the regulatory group
-------
October 2002 • LUSTLim Bulletin 42
that has jurisdiction.
Sampling Depths For sites where
near-surface sources are not sus-
pected (e.g., fuel sites with USTs), I
recommend that samples initially be
collected at a depth of five feet below
the structure/basement or ground
surface. The logic here is two-fold: (a)
this depth is generally deep enough
to minimize any near-surface and
transient effects on the soil-vapor val-
ues as discussed previously and (b)
measured soil-vapor values at this
depth will be more representative of
values near the enclosure than
deeper samples.
At sites where there is reason to
suspect shallower contamination
(e.gv dry cleaners, sites with solvent
usage at the surface), or where condi-
tions don't allow deeper samples
(e.g., high water table or gravelly
soils), or where the data from five
feet fail the risk calculation, the col-
lection of shallower samples (<5 feet)
may be appropriate. If soil-vapor
data from depths less than five feet
below grade are collected, additional
sampling events may be appropriate
to ensure representative values, espe-
cially if the measured values yield
risks that are near acceptable levels.
In such cases, the burial of mini-
vapor monitoring probes (implants)
is an easy and inexpensive way to get
repetitive data (see below).
I want to point out that the latest
version of the U.S. EPA vapor-intru-
sion guidance implies a preference
for deeper samples (i.e., 15 feet). My
recommendation is not in agreement
with this preference. If deeper sam-
ples are desired, all the collection
methods/issues described in this
article apply. In addition, it is impor-
tant that you remember that the
potential for vacuum stripping of
contaminants out of the pore
water/groundwater will increase as
the percent water content goes up
(i.e., in the capillary fringe and near
the water table).
Sample Frequency/Reproducibil-
ity of Data Typically, a single sam-
pling event should be sufficient to
assess this risk pathway, especially if
collected at deeper depths (>5 feet
bgs). In some situations, additional
sampling events may be appropriate;
for example, where the calculated
risk from the first sampling event is
close to acceptable levels, or for shal-
low sampling depths, or if sampling
takes place during the winter in areas
with large seasonal temperature vari-
ations. In such situations, the burial
of mini-vapor monitoring probes
(implants) is an easy and inexpensive
way to get repetitive data (see
below). One simple and inexpensive
approach is to measure the soil-gas
values in the morning and again at
the end of the day. If the results
match up well, then you can con-
clude the sampling. If not, return the
next day and repeat the procedure
until the variability can be assessed.
Mini-Vapor Monitoring Probes/
Implants Mini-vapor monitoring
probes (implants) consist of small
diameter (e.g., 1/8" or 1/4" outer
diameter) inert tubing with a perfo-
rated tip at the bottom (refer to Fig-
ure 1). The tubing allows for a
seamless installation to depths of
hundreds of feet and low internal
dead volumes for easy sampling.
Mini-vapor probes can be emplaced
using hand augers, hand soil-vapor
equipment, or direct-push systems,
or can be lowered down the open
drill pipe of hollow-stem and percus-
sion drilling rigs. Several choices of
perforated tips are available, includ-
ing stainless-steel screens, slotted
PVC pipe, and aluminum or ceramic
tips.
The tube and tip are emplaced to
the target depth, buried with 6 to 12
inches of sand, and then sealed to the
surface with bentonite. The small
tubing enables multiple tubes to be
buried in the same borehole when
vertical vapor gradients are desired
("nested vapor wells"). The surface
end of the vapor tube is capped with
a gas-tight Swagelok nut and cap or
with a gas-tight valve as desired. The
mini-vapor probe can be terminated
at the surface with a variety of com-
pletions, such as locking well covers.
Recommended Sampling
Protocol for Determining
Upward Vapor Migration Risk
I recommend the following proce-
dure for collecting near-surface soil-
gas data with the intent of
determining the upward-vapor flux
into an existing or future room/
building. This protocol is based upon
the approach we have been using in
Southern California for some time:
Figure 1
EXAMPLE OFA MULTI-DEPTH,
VAPOR MONITORING WELL
SURFACE
6"-12"
sand
rA
1
i
1/8" or 1/4"
inert tubing
_ vapor
inlet
1. Collect active soil-vapor data at
five feet below grade at enough
sampling points under or near the
building to give a reasonable esti-
mate of the subsurface soil-gas
concentration under the building
footprint. At a minimum, samples
should be collected at the corners
or sides of the existing or future
building and the location of high-
est contaminant concentration
under the building (if determined
previously). If the location of the
future building is unknown,
• continued on page 22
21
-------
LUSTLine Bulletin 42 • October 2002
m Active Soil-Gas Method
from page 21
collect soil-vapor data at five feet
below grade spatially across the
site to identify the location of high-
est concentration. If a surface
source of contaminants is sus-
pected, collect at least one or two
samples closer to the base of the
building (one to two feet below) to
validate that the five-foot samples
are representative of the subbuild-
ing soil-gas concentration.
2. Determine the health risk from the
soil-vapor value using the method
allowed by the local oversight
agency (e.g., J-E model, default
attenuation factor). If the risk cal-
culation indicates that upward
vapors pose no threat to human
health, then submit a formal
request for closure to the govern-
ing agency.
3. If die risk calculation indicates that
upward vapors may pose a threat
to human health, then either add
more sampling locations spatially
under the building or repeat steps
1 and 2 at a shallower depth. The
logic behind this recommendation
is that additional spatial samples
under the footprint will yield a
more representative subbuilding
value, and shallower samples
might show lower concentrations
due to bioattenuation- and trans-
port-related factors (especially in
the case of nonchlorinated com-
pounds). Alternatively, consider
an approach such as collection of
indoor-air data or direct measure-
ment of flux with surface-flux
chambers. ;
4. If soil-vapor data are to be col-
lected at depths less than five feet
below grade, or if the risk calcula-
tion from the initial set of data is
borderline, repeated measure-
ments may be appropriate to
ensure that the measured soil-gas
values are representative.
5. Vertical profiles of the soil gas
may be useful to document bio-
attenuation and to reduce near-
surface variability. In such
situations, it is recommended that
data be collected at a minimum of
three locations vertically from one
foot to five feet to ensure that ver-
tical variations are characterized
adequately. Measurements of oxy-
gen and carbon dioxide should be
included if bioattenuation is being
assessed.
For subsurface enclosures, such
as basements or utility trenches, the
same protocol can be used; however,
soil gas samples should be collected
from three to five feet below the floor
(rather than bgs). Additionally, it
may be necessary to also consider the
potential flux through the walls in
addition to the floor. Assuming a
contaminant source deeper than the
enclosure, the most conservative
assumption is to assume the flux
through the walls is equal to the flux
through the floor. In this case, the
total flux into the room would be
equal to the flux through the floor
times the combined surface area of
the floor and the walls.
For near-surface sources, this
assumption is not safe as horizontal
permeability is often much greater
than vertical permeability. In such
situations, a soil-vapor measurement
should be made on each side of the
wall (i.e., three to five feet away) and
the flux through the wall should be
computed separately. The total flux
into the room would then be com-
puted by summing the individual
fluxes through the floor and walls. •
Blayne Hartman, Ph.D., is a principal
of HP Labs and. the founder of TEG. He
has lectured on soil-vapor methods and
data interpretation to over 20 state
agencies and to all of the U.S. EPA
regions. Blayne has contributed
numerous articles to LUSTLine and
authored chapters in three textbooks on
soil-vapor methods and analysis.
For more information, either e-mail
Blayne directly at
bhartman@hplabsonsite.com
or check out his web page at
www.hplabspnsite.com.
Uh Oh! Striker plate's out of line with the drop tube. The dip stick punched a hole in this tank.
If you hove any UST/LUST-related snapshots from the field that you would like to share with our readers, please send them to Ellen Frye do NEIWPCC.
22
-------
October 2002 • LUSTLine Bulletin 42
Flexible-Pipe Concerns Drive Home the Need
for Tank-Owner Vigilance
It probably comes as no surprise to
any of our readers that piping and
associated sumps have been and
continue to be the sticklers in
our quest to achieve UST-system
integrity nirvana. Over the past year,
several states, particularly Missis-
sippi and Florida, have reported that
certain types of flexible-piping sys-
tems have been failing and with
increasing frequency—and we don't
hear that about tanks.
. John Mason, U.S. EPA Region 4
UST Program Manager, says he has
received reports from several states
regarding several different genera-
tions of polyethylene flexible piping
exhibiting unusual physical changes.
"Some of the changes appear to be an
'elongation' of the pipe resulting in
torn containment sump boots, com-
pressed test boots, contorted flex con-
nectors, and splitting of the pipe as it
grows over metal fittings. There are
other reports where the outer layer
has wrinkled, softened, and split,"
says Mason.
"The reports described changes
that occurred sometimes within
weeks, or even days of installation,"
notes Mason. "There seem to be more
and more reported incidents as
inspectors and owner/operators
become more familiar with what to
look for in the piping and dispenser
sumps. The majority of the piping
incidents have been detected in time,
and within secondary containment;
however, there have been some cata-
strophic failures resulting in releases
to the environment of several thou-
sand gallons of product."
Now I know there has been some
discussion about the definition of
"failure." And the federal UST rule
does not specifically define what con-
stitutes a failure. So, for the purpose
of this discussion, let's say that a
product that fails to perform accord-
ing to reasonable customer expecta-
tions is a failure. I don't think there is
a regulator (or tank owner) out there
who reasonably expects that as a
"normal" occurrence, flex pipe will
swell and tear out penetration fit-
tings, thus destroying the integrity of
the secondary containment system.
Fortunately, most of the flex-pipe
failures that have been reported
recently have not resulted in releases
into the environment.
Although a thorough assessment
of the facts has not yet been made,
the New England Interstate Water
Pollution Control Commission, the
organization that produces this pub-
lication, feels it is important that we
give our readers a heads-up on this
issue, so that steps can be taken to
avoid any potential releases to the
environment and threats to human
health and safety. It is likely that
most systems will not have a prob-
lem, but vigilance is always well
advised with any UST system.
Failure Modes
Tom Schruben, an independent risk-
management consultant who has
reviewed reports of close to 200 fail-
ures in double-walled flexible pipe
systems in 11 states, says that there
are two distinct failure modes/which
sometimes operate in tandem:
• The most common failure mode is
one where the outer layers of the
primary pipe soften, swell, and
split. The pipe often feels sticky
and spongy. The swelling can
cause the pipe to grow several
inches in length. This growth
sometimes tears the secondary
containment boot at the sump
wall. Swelling can also seal off the
interstice of the coaxial pipe
against the coupling ferrule, mask-
ing a leak in the primary pipe.
• The second mode of failure
involves the end fittings of the pri-
mary pipe. The swaged fittings
sometimes split or loosen, allow-
ing the pipe to slip off of the end
fitting. This can happen at either
end of the pipe run.
"These failures are not limited to
a particular manufacturer or even a
particular generation of pipe," says
John Mason. He explains that the
total amount of pipe in the ground of
each brand is not known, so it is
impossible at this point to determine
if a particular brand of pipe is failing
more frequently than another. The
amount of flexible piping being used
in new installations has increased by
50 percent since 1995. Mason says it is
not clear whether the failures are the
result of installation error, shipping
damage, poor quality control, design
flaws, fuel incompatibility, or poor
maintenance and monitoring of
sumps—or a combination of these
things.
Preemptive Actions
One aspect of the failures that is dear
to regulators and owners alike is that
the piping failures are too often com-
pounded by leaks in sumps. Not only
do sump leaks allow the petroleum
to discharge to the environment, they
can also defeat the release-detection
system because the product does not
fill the sump to the trip level of the
liquid sensor.
UST owners, state regulators,
and state fund administrators are
approaching this problem in different
ways around the country. Several
states are looking into the problem to
determine what actions will be
appropriate. Pipe vendors are work-
ing with the states and tank owners
to try to resolve these issues.
One conclusion is clear, how-
ever—both UST regulators and tank
owners need to increase their vigi-
lance for potential failures of flexible
piping, and they should be ready to
take swift action when failed (or fail-
ing) piping is discovered. The good
news is that many of the piping
abnormalities are easily visible if you
know what to look for and where to
look. Here are some preemptive
actions that we have gleaned from
discussions with regulators, consul-
tants, and flex-pipe vendors.
• Inspect the piping sumps for
any of the following signs of
compromised integrity:
• continued, on page 34
23
-------
LUSTLine Bulletin 42 • October 2002
NEWS FROM CALIFORNIA
New Legislation Requires
New UST Systems to be
Vapor Tight and Fully
Contained!
On September 28, 2002, California
Governor Gray Davis signed into law
Assembly Bill (AB) 2481, strengthen-
ing the law related to USTs in that
state. The findings of the Field-Based
Research Project (see related article
below), which revealed vapor
releases at 80 percent of facilities
tested, were a major driving force for
the new construction and testing
standards in the bill.
Major provisions of AB 2481:
• Allow local agencies to prohibit
fuel delivery to USTs that have
significant violations by affixing a
red tag to the fill pipe.
• Require USTs installed after July 1,
2003, to be liquid and vapor tight.
• Require licensed tank testers to
sign tank or piping integrity-test
reports under penalty of perjury.
• Modify enhanced leak-detection
(ELD) testing requirements to
include a one-time testing require-
ment for double-walled UST sys-
tems within 1,000 feet of a public
drinking water well. (Previous leg-
islation required that all single-
walled facilities within 1,000 feet
of a public drinking water perform
ELD every three years. This is
above and beyond all other
required routine monitoring. The
new bill expands this requirement
to include a one-time ELD test for
double-walled systems.)
• Create a single, consistent, admin-
istrative enforcement authority
(orders and/or penalties) for Cer-
tified Unified Program Agencies'
(CUPA's) use in enforcing UST
requirements and other CUPA
requirements.
• Permit a claimant to be eligible for
reimbursement from the UST
Cleanup Fund despite having
acquired the site from an ineligible
person, as long as the claimant is
not affiliated with the ineligible
person.
ELD is a method of leak detec-
tion that we have defined to be able
to detect both vapor and liquid
24
releases and it is third-
party certified to detect a
leak rate of 0.005 gallons
per hour. AB 2481
requires that all UST sys-
tems installed after July 1,
2003, be constructed in a
manner that is both liquid
and vapor tight. Addi-
tionally, the bill requires
that a post-installation
test be conducted to ver-
ify that the system meets
these requirements before
it is placed in service.
Currently, the only third-party
approved leak-detection method cur-
rently available for this purpose is the
Tracer-Tight® test method at a detec-
tion sensitivity of 0.005 gallons per
hour. The bill allows for alternative
test methods that are approved by
the California State Water Resources
Control Board.
The new construction standards
also require that all UST components,
including vapor return lines, risers,
and tank-top connections, be secon-
darily contained. Note that according
to current California law, all sec-
ondary containment components
must be tested upon installation, six
months after installation, and every
three years thereafter.
For more information about this
new law, contact Shahla Farahnak at
farahnas@cwp.swrcb.ca.gov.
Vapor Releases from UST
Systems
California's Field-Based
Research Findings Put the Blame
on Vapors
A recent study completed for the Cal-
ifornia State Water Resources Control
Board (SWRCB), known as the Field-
Based Research (FBR) Project, indi-
cates that liquid leaks from
underground storage tank systems
are rare; however, vapor leaks are
abundant. Results from the FBR Pro-
ject suggest that the 1998 UST
upgrade requirements were effective
at reducing liquid leaks from UST
systems.
The research focused on UST sys-
tems at 55 randomly selected UST
facilities in three areas of California—
Sacramento and Yolo Counties, San
Diego County, and the City of
Service technician removes a sump sensor for testing.
Temecula. The systems were tested
using the Enhanced TracerTight®
test, a very sensitive leak-detection
method" offered by Tracer Research
Corporation. The method is capable
of detecting both liquid and vapor
leaks as small as 0.005 gallons per
hour. Results of the 182 UST systems
evaluated indicated more than 60
percent of the systems had vapor
releases, while approximately 1 per-
cent of the systems indicated a liquid
release.
The majority of vapor releases
identified were associated with tank-
top fittings and connections. In con-
trast to the liquid releases of the past,
which were typically associated with
product piping, the vapor releases
were identified near the tanks. The
two liquid releases found as part of
the FBR Project were associated with
single-walled piping.
To obtain a copy of the FBR Pro-
ject report, please visit the SWRCB
Web site at http://www.swrcb.ca
.gov/cwphome/ust/docs/fbr/index
.html. For more information about
the project, contact Erin Ragazzi at
ragazzie@cwp.swrcb.ca.gov.
California's Field Evaluation
of Leak-Detection Sensors
The California State Water Resources
Control Board's (SWRCB) UST
program staff have conducted a com-
prehensive evaluation of the effec-
tiveness of leak-detection sensors,
which are the primary form of leak
detection in double-walled UST sys-
tems. Leak-detection sensors are typi-
cally located in tank interstitial
spaces, piping sumps, under-dis-
penser containment, and monitoring
wells within excavation liners. They
-------
October 2002 • LUSTLine Bulletin 42
may also be located in groundwater
monitoring wells or soil-vapor moni-
toring wells surrounding the tank
system, although no such facilities
were included in this field evaluation.
California regulations require that all
leak-detection equipment be func-
tionally tested and certified by an
authorized service technician on an
annual basis. The field evaluation was
based on data collected from 789 sen-
sors at 124 UST facilities during rou-
tine annual testing and certification.
The data collected in this field
evaluation demonstrate that sensors
can be a reliable form of leak detec-
tion only when properly installed,
programmed, maintained, and oper-
ated. Most problems observed in this
field evaluation were due to
improper installation and program-
ming of sensors, poor or infrequent
maintenance at UST facilities, ignor-
ing alarms, and tampering with mon-
itoring equipment. Poor design,
construction, and maintenance of sec-
ondary containment systems were
also common.
Approximately 12 percent of the
sensors had one or more problems at
the time of testing. The most common
problems observed were sensors
raised from the low point of the sec-
ondary containment, sensors failing
to alarm when tested, and sensors
failing to shut down the turbine
pump in the event of an alarm (when
programmed to do so). Secondary
containment must be kept clean and
dry in order for sensors to perform
properly; however, water was found
in over 10 percent of the secondary-
containment systems. Liquid product
was present in an additional 3.5 per-
cent of the systems. Overall, 31 per-
cent of the facilities visited in this
field evaluation had water or product
in one or more areas of the sec-
ondary-containment system. One can
only assume that the problems iden-
tified in this field evaluation would
be significantly more common if
there were no requirement for annual
certification of monitoring equip-
ment.
Based on the findings of this
evaluation, SWRCB UST program
staff have concluded that the effec-
tiveness of sensors as a leak detection
method can be improved with peri-
odic visual and functional inspection
of sensors and secondary contain-
• continued on page 27
Pay for Performance:
Does It Work? The Data
by Robert S. Cohen
Pay for Performance1 (PFP) has produced remarkable results in many
states with faster and less expensive cleanups. Yet, there has been a lack
of comparative data to "prove" the case. I have experienced this frustra-
tion many times in the course of moderating over a dozen PFP workshops and
two dozen training sessions. At each event the same questions were raised:
Does it really work? Where's the data? The questions come from regulators and
consultants, both of whom are reasonably skeptical of change.
At the Florida Department of Environmental Protection's (FDEP's) 16th
Annual Storage Tanks/Preapproval Program Meeting (August 2002, St. Peters-
burg), two papers were presented with unequivocal results comparing PFP
with Time and Materials (T&M):
• A Comparative Study of the Relative Success of Site Cleanups Under Preapproval
and Pay for Performance Contracting. Draft. August 2002 by Brian Dougherty
and Ferda Yilmaz of the Florida DEP, and
• Comparison of Price and Time in Pay for Performance and Time and Materials
Cleanup Contracting. (South Carolina and Florida) Draft. April 2002. By Dana
Hayworth of U.S. EPA Region 4, with major contributions by William Fos-
kett of the U.S. EPA Office of Underground Storage Tanks.
What follows is a discussion of the results of these papers along with my
own private-sector observations. In discussing the Florida program, I use the
terms T&M and preapproval interchangeably. The Florida petroleum cleanup
program currently operates under a variant of T&M in which costs are preap-
proved for a specific scope of work. The preapproved costs are paid in a lump
sum, and the basis of the costs is traditional time and materials build-ups. In
contrast, PFP is a market-based lifecycle cost to completion, which may be
determined by bidding or negotiating. A key element to PFP is the fixed price—
no change orders are allowed. After presenting the data, I'll briefly discuss why
PFP provides such dramatic results. A future article will explore the reasons for
success in more detail.
The Data
As the data in Table 1 and Figures la
and Ib demonstrate, PFP cleanups
are considerably less expensive (28,
or 64%) and remarkably faster (39, or
67%). That is, the environmental
results are achieved faster, with a
greater leveraging of the financial
resources. These studies are signifi-
cant in that they cover a large num-
ber of sites with a variety of
geological settings. The factors that
could affect the results were consid-
ered and normalized.
Discussion of Data
The Florida DEP study compared 57
preapproval sites with 57 PFP sites.
The EPA study (Florida and South
Carolina) compared 28 PFP sites with
35 T&M sites. Some of the differences
in results between the studies may
reflect the smaller sampling of the
EPA study. In Florida, both preap-
proval and PFP are active programs.
In South Carolina, PFP has fully
replaced T&M, and therefore the
South Carolina comparison includes
two generations of data. The PFP
data represents the more recent
cleanup efforts.
The EPA study shows more dra-
matic differences between PFP and
T&M than the DEP study; however,
the Florida study, being of contempo-
raneous sites, may be a more accurate
statement. Nevertheless both studies
show the same trends at the same
order of magnitude.
• continued on page 26
Pay for Performance is a contractual mechanism by which the cleanup consultant is paid upon
achieving agreed-upon environmental milestones. The cleanups are typically faster and cheaper than
the ordinary time and materials approach. PFP has been described in previous LUSTLine articles and
more information is available at the EPA Web site: http:ffwurw.epa.gov/siverustl/pfp/index.htm
_
-------
LUSTLinc Bulletin 42 • October 2002
I PFP from page 25
Data I collected on a recent
Florida PFP bidding project (see
LUSTLine #39) produced savings of a
similar degree on 70 sites. Using PFP
bidding techniques, an owner/opera-
tor was able to save at least $3 million
over the anticipated preapproval
cleanup costs.
Florida has one of the nation's
largest cleanup programs and has for
many years studied the most effec-
tive measures for cleanup, based on
cost and environmental results. The
Florida study concluded that PFP
cleanups consistently produce better
results than those performed under
preapproval when those results are
measured by the amount of contami-
nation removed, time for that
removal, and cost.
The EPA study looked at similar
T&M and PFP sites in Florida and
South Carolina. The study concluded
that PFP cleanups are significantly
faster and less costly than the cus-
tomary T&M cleanups in the study's
sample of ordinary UST cleanups. By
reviewing sites in both Florida and
South Carolina, the EPA study cov-
ered a range of lithologies (e.g.,
coastal plain to bedrock), depths to
water, and standards. The study con-
cluded that the most significant fac-
tor for determining the speed and
cost of cleanup is the contractual
mechanism (i.e., PFP vs. T&M).
Factors Considered
The EPA study posed two key ques-
tions: Could other factors account for
speed and low prices of PFP
cleanups? Could the superiority of
PFP over T&M in the cleanups stud-
ied be due to something other than
PFP (e.g., lower baseline concentra-
tion levels, smaller plumes, less
stringent goals, less difficult hydro-
geological conditions)?
The study determined that none
of these factors seems likely to
account for the differences in PFP
and T&M cleanup prices and time
frames. PFP site baseline-concentra-
tion levels averaged 16 percent
higher than those at the T&M sites to
which they were compared. South
Carolina PFP sites dealt with the
same size plumes on average as did
the T&M sites.
Within each state, goals for PFP
and T&M cleanups were set follow-
26
COIPARISPN OF COSTAND TIME QE PEEMlI&l, J
PFP
T&M/
Preapproval
Difference
Between T&M
and PFP
EPA South Carolina
Average
Cost
$78,351
$215,110
64%
Average
Time (Yrs.)
2.3
67%
EPA Florida
Average
Cost
Average
Time (Yrs.)
$176,021
$376,308
53%
4.1
6.7
39%
Florida PEP Study
Average
Cost
$215,427
$300,255
28%
Average
Time (Yrs.)
3.5
43%
Time of Cleanup Comparison
Cost of Cleanup Comparison
EPA Florida
EPA DEP Study
EPA South Carolina
ing similar procedures, essentially
requiring that all key wells at PFP
sites reach the goals set for the site.
Within each state, the hydrogeologi-
cal differences between individual
sites varied somewhat, but overall,
T&M and PFP sites in each state were
hydrogeologically similar to each
other and relatively ordinary.
Both studies analyzed the follow-
ing factors:
• plume size :
• hydrogeological conditions / soil
type
• treatment technology
• cleanup standards
-------
October 2002 • LUSTLine Bulletin 42
• plume concentration (BTEX)
• depth to groundwater
• size of consulting firm
• operating vs. nonoperating facility
• cleanup progress (most of the sites
are work in progress)
Each of these items was exam-
ined and compared to assure that the
distribution of PFP versus T&M sites
were comparable in difficulty. The
comparisons were demonstrated to
be unbiased in any significant man-
ner. The Florida study included
extensive statistical analysis of the
risk factors for time and cost, which is
too voluminous to include herein.
Why Does PFP Work So Well?
The data in the Florida study clearly
show that sites do get cleaned up
under both PFP and preapproval.
Therefore the knowledge and ability
to do so is obviously present in the
industry. The key difference between
the two types of cleanup is incentive.
Under a preapproval cleanup there is
no incentive to succeed and no
penalty for failure. A contractor is
paid regardless of progress made
toward meeting the cleanup goal.
Under PFP, only success toward
meeting the cleanup goal is
rewarded, and therefore an incentive
is provided to ensure the greatest
possible success in the least amount
of time. This study demonstrates that
if the right incentive is provided, then
the sites will be cleaned up faster and
1 for a lower cost.
The Florida study also looked at a
common question regarding PFP: Are
some companies too small to take the
risk associated with PFP? The study
data suggests that a PFP cleanup is
not as risky a venture as it is some-
times portrayed to be. The majority of
the PFP sites (39, or 68%) in this study
achieved the 90 percent contamina-
: tion reduction milestone in a year or
less, compared with only 10 sites
(18%) under preapproval. This mile-
stone corresponds to a 75 percent
payment of the total cleanup price.
Not all PFP cleanups proceed this
»well, and there are some PFP
cleanups in this data set that are not
going well, but overall it is possible to
succeed under a PFP cleanup and to
do so on a regular basis regardless of
' company size.
The studies both concluded that
PFP motivates consultants to achieve
results while simultaneously provid-
ing the latitude to do so. Successful
PFP consultants understand the
nature of risk and spread that risk
over groups of sites. They also take
advantage of the "volume discount"
of LUST sites and reuse equipment,
coordinate field events, template
reports, and incorporate various
other cost-saving devices that are not
encouraged in the T&M approach.
Thumbs Up!
PFP cleanups are superior to those
performed under T&M (or the preap-
proval variety of T&M). This was
demonstrated by all reasonable crite-
ria of concern—the time and the costs
to achieve targets. Could other fac-
tors account for these phenomena?
Based on the 175-plus sites reviewed
in these studies, the results of PFP are
genuine and are not due to sampling
prejudice. •
Robert S. Cohen, BS, MS, is a profes-
sional geologist specializing in LUST
cost-containment issues. He is a con-
sultant to both the public and private
sectors. He has conducted over 30 PFP
workshops and studies on behalf of the
EPA and various states. For more
information, contact Bob at
bob cohen@ivs.edu
A PFP Toolbox Update
EPA's Office of Underground Storage
Tanks (OUST) has developed an online
resource for people interested in per-
formance-based contracting for LUST
cleanups. OUST's Pay for Perfor-
mance (PFP) Toolbox contains valu-
able information provided by states
and others using performance-based
contracting. The PFP Toolbox is
designed to assist state regulators in
developing and maintaining a PFP pro-
gram in their state. After six months
online, OUST is now revising and edit-
ing some portions of the toolbox. In
the coming weeks, OUST will be inter-
viewing states currently using PFP to
include their experiences in a "Making
Your Opportunity" section of the tool-
box. In addition, an online user ques-
tionnaire has been posted so that
OUST can receive feedback on the
usefulness of this tool. The PFP
Toolbox can be seen at
www.epa.gov/oust/pfp/tooibox.htm.
"We've Shown 'Em Our
Backs Long Enough!"
I found the excellent article by G.
Scott Deshefy, "We've Shown 'Em
Our Backs Long Enough!" in the June
2002 LUSTLine extremely well writ-
ten, and conning from someone who's
been around this program long
enough to appreciate the history and
evolution of the UST effort. 1 think
Scott is absolutely correct in many of
his observations. I imagine the con-
cerns Scott expressed resonated with
many veteran UST regulators.
As Scott points out, greater
involvement of UST operators will
prove particularly challenging for us,
S.1850 notwithstanding. S.1850 man-
dates that implementing agencies
address the operator training issue,
albeit four years after S.1850 finally
becomes law. That time frame seems
extremely long to me. S.1850 doesn't
help define the "operator" for whom
implementing agencies are to provide
a strategy for training.
Perhaps, as Scott suggests in his
article, agencies should focus on who
should be accountable for an UST
operation. In some cases it might be
the owner, in other cases the opera-
tor, while still in others an owner/
operator, and for some locations, a
trained UST professional might be the
"accountable party." The journey
should prove interesting.
Lamar Bradley
Assistant Director
Tennessee Division of UST
ICA News from page 25
ment. Many of the problems ob-
served in the study can be addressed
with more thorough training of per-
sonnel who install, service, and oper-
ate UST leak detection equipment.
Manufacturers should also continue
to improve sensor design and field-
testing procedures.
A complete report of the sensor
field evaluation, including detailed
findings and recommendations, can
be found on the SRWCB Web site at
http://www.swrcb.ca.gov/cwphome/
ust. For more information about
this study, contact Scott Bacon at
bacons@cwp.swrcb.ca.gov. •
_
-------
LUSTUne Bulletin 42 • October 2002
Square Operators, Round Tanks, and Regulatory
Hammers: A Petroleum Marketer's Perspective
by Ron Man
LUSTLine Bulletins 40 and 41 are
interesting reading to anyone
involved with underground
storage tanks. Marcel Moreau's arti-
cle, "Of Square Pegs and Round
Tanks/' dealing with the lack of
involvement by UST owners in oper-
ating their tanks, and G. Scott
Deshefy's article, "We've Shown 'Em
Our Backs Long Enough," express-
ing frustration with getting USTs
into compliance, pretty much detail
both ends of today's UST environ-
ment. But interestingly, neither
writer is addressing the compliance
issue from the underground tank
owner's perspective.
As the state executive of the
Petroleum Marketers and Conve-
nience Stores of Iowa, I have been
involved in the UST regulatory and
lawmaking process since its incep-
tion in the early 1980s, both as a mar-
keter and as a representative of
Iowa's regulated tank owners. In
Iowa, as in most other states, tank
owners have witnessed extremes in
the enforcement of the regulations
that govern their underground stor-
age systems.
Over the past 20 years, I have
learned that it takes an awful lot of
heavy regulatory hammer blows to
force many of our "square" operators
to operate their "round" tank sys-
tems properly. But I have also come
to realize that there is a "lubricant"
out there that really eases the regula-
tor's hammer blows and helps get the
square operators into operating their
round tanks properly. Surprisingly to
many regulators, that lubricant is
called enforcement of the financial
responsibility (FR) requirements in
the UST regulations, or, as it's more
commonly referred to in our indus-
try, underground storage tank insur-
ance.
As nearly any reader of LUST-
Line will concede, business owners
are motivated by economic incentive.
Show a business owner a way to
increase sales, decrease costs, or
increase profits, and he or she'll
bite—you've got a player. Frankly,
28
just trying to be environmentally
friendly doesn't cut the mustard. The
only thing that most tank operators
saw when faced with the federal UST
regulations was increased operating
costs.
The shiny new, environmentally
friendly USTs weren't going sell
more product, and they weren't
going to increase sales and profits.
But, and this is the big but, if the tank
owner could find a way to reduce the
costs associated with the tank system
and comply with the regulations at
the same time, he or she would be
much more likely to get on board.
Thaf s a way to increase profits.
The FR Hitch
Most states provide some form of the
needed financial responsibility to
their UST owners through a state
fund program. At first blush, this
seems to be a logical approach
because it ensures that sites will be
cleaned up sooner than later. In real-
ity, however, I believe that providing
tank owners with a financial respon-
sibility option that leaves them pretty
much off tihe hook with regard to cost
and responsibility is the Achilles'
heel in terms of getting them to oper-
ate their UST systems properly.
Think about it for a minute. If
you are getting FR coverage at little
or no cost for simply being in "sub-
stantial compliance" or in some cases
for doing nothing, what is your
incentive to do more? If you have a
leak, who cares? The state fund will
clean it up. And how's the program
financed? Typically through some
sort of per gallon or per barrel fee
that is passed on to the gasoline con-
sumer.
Now keep in mind that I repre-
sent private Iowa UST owners. And
I've been through the legislative dog-
fights and the stress (applied by our
petroleum marketers) of dealing with
cleaning up leaking underground
storage tanks and upgrading existing
USTs and finding government fund-
ing solutions for both. And I've
found two things to be true: "You can
lead a horse to water, but you can't
make it drink" and you need both a :
carrot and a stick to get the horse to
drink, or in this case, to get the tank
owner to comply with the regula-
tions. And, as I'll explain, here in
Iowa we've found that insurance is
the carrot and the threat of losing that
insurance or having higher premi-
ums is the stick.
Covering the Future
In 20-20 hindsight, Iowa's initial deci-
sion to split out the leaking under-
ground storage system scenario into '.
two distinct pieces—one to clean up
past leaks and the other to provide
the required financial responsibility
for future leaks—has been a blessing
not only for the environment but also
for the regulated tank community. ;
In 1989 the Iowa legislature and
the governor created Iowa's LUST
cleanup fund. They called for two
distinct funding programs—a \
cleanup assistance program (past
leaks), funded through a one cent per
gallon environmental fee placed on
product deposited into regulated
USTs and paid for by the consumer,
and a financial responsibility pro-
gram (future leaks), funded by tank
owner fees and "insurance" premi-
ums. The initial few years of premi-;
ums were at rates [prescribed by the
state. :
Iowa's law also required that the
premiums to be actuarially sound
and reflect the exposure of the UST
system to the environment. By Octo-
ber 1990, all owners and operators of
regulated USTs had to conduct soil
and groundwater tests at their facili-:
ties to discover any contamination in
order to access state cleanup assis-
tance. If a contaminated site was not
reported to the Iowa Department of
Natural Resources (IDNR) by this
date, that UST site was ineligible for .
cleanup assistance from the state.
Furthermore, the insurance program
would not provide coverage for
future releases if the site had not been
tested for contamination. This testing
deadline for determining eligibility
-------
October 2002 • LUSTLine Bulletin 42
for the Iowa, cleanup program
became the single critical keystone of
Iowa's UST program.
By creating this deadline, a
demarcation point of prior existing
contamination and future contamina-
tion caused by a new release was cre-
ated. This allowed Iowa's cleanup
program to begin to get its arms
around the potential cost of remedi-
ating existing contamination. The
creation of the demarcation point
also helped draw a line in the sand
between past and future for future
financial responsibility program lia-
bility. Releases discovered prior to
the October 1990 were the responsi-
bility of the state cleanup program;
releases after that deadline were the
responsibility of the insurance pro-
gram. The owners wrote checks for
the insurance. Suddenly owners were
more concerned about stopping
future leaks and became more effec-
tive at doing so than the regulators
were.
Foiling the Raiders
During the late 1990s the Iowa legis-
lature, like many other state legisla-
tures, began scooping cleanup
monies from existing fund balances
in order to meet budget demands.
Tired of the seemingly endless strug-
gle to prevent the Iowa legislature
from raiding money from the insur-
ance fund—a fund that the UST own-
ers were financing—the Petroleum
Marketers and Convenience Stores of
Iowa, along with other interested
parties, began the process of privatiz-
ing the state-run UST insurance fund.
In 1995 legislation had been
passed that allowed the insurance
portion of Iowa's program to priva-
tize itself if and when the state-spon-
sored insurance program could meet
the requirements of a fully state-
admitted nonprofit mutual insurance
company. A new nonprofit, mar-
keter-owned mutual insurance com-
pany was proposed.
Boiler Insurance
As part of the proposed business
plan, the proposed insurance com-
pany adopted a loss-control philoso-
phy usually associated with boiler
insurance. Part of the philosophy of
boiler insurance is that frequent
equipment inspections are required
to make sure that the insured equip-
ment (originally boilers) is main-
tained and operating properly. If the
insured equipment is operated and
maintained correctly, the chance of
loss is greatly reduced, and insurance
premiums reflect this decreased loss.
This new UST insurance com-
pany is called the Petroleum Mar-
keters Mutual Insurance Company
(PMMIC), and policy owners are the
owners of the company. The owners
have dictated through their represen-
tatives on the Board of Directors of
PMMIC that compliance with techni-
cal regulations is to be the foundation
of the PMMIC's loss-control inspec-
tion program.
Iowa tank owners are now expe-
riencing frequent loss-control inspec-
tions of their UST equipment by the
UST insurance company that they
own. IDNR's UST equipment and
operating regulations provide the
baseline for these inspections. But
what is different about these inspec-
tions is the climate in which they are
conducted.
k In fact, the legislature took
^k $30 million from the insurance
^m fund in 2002, and the governor
^m has proposed taking $99 million
V from the revenue source, which
W would put the fund at zero balance.
The Inspection Climate
PMMIC inspections are conducted
with the owner or operator of the
tank as an educational and informa-
tional experience for the owners and
are as detailed as a regulatory inspec-
tion. Instead of issuing a notice of
violation (NOV), as a regulator
would if the system were out of com-
pliance, PMMIC allows the owner up
to 60 days to correct any deficiency
identified. If the deficiency is not
addressed, insurance can be can-
celled or premiums increased. If the
insurance is cancelled, then the regu-
latory agency can shut down the
operator for not maintaining FR cov-
erage.
Compliance is a business issue.
PMMIC members meet the standards
because they have to and because it is
their money that is spent on cleanup
if any of the tanks leak. By taking tax
dollars and politicians out of the pic-
ture, PMMIC is able to obtain compli-
ance at every site it insures and its
rates are less than $1,000 per site.
PMMIC is protecting its members'
money and focusing its efforts on
leak prevention. The system works.
The Owners Reap the
Benefits
PMMIC is currently evaluating a rat-
ing program that will eventually
offer UST operation credits to
insured's premiums for the best sys-
tems and the best operators if the
operator demonstrates that state-of-
the-art, environmentally safe equip-
ment or enhanced daily operation of
the system is in place.
The real beauty of the system
today is that owners know they have
coverage for a new release while their
policy is in effect. They don't find out
after the fact that they were not in
compliance and therefore the cleanup
won't be covered. The inspections
document compliance with the terms
of the policy.
Theoretically, Iowa tank owners
insured by PMMIC may reap another
benefit. If their UST equipment
fails, PMMIC has the ability to
address UST equipment manufac-
tures through legal avenues in order
to recoup cleanup costs expended by
the insurance company.
Finally, if PMMIC encounters a
tank owner who fails to meet IDNR's
baseline standards for equipment
and operations, PMMIC will cancel
his or her UST insurance policy. In
Iowa, it's the law that an owner must
have viable FR to operate an under-
ground tank system.
If Regulators Could Choose?
When the only avenue a regulator
has to enforce UST regulations is to
catch a noncompliant operator, a
huge game of cat and mouse begins.
In states that provide "free" FR for
owners in "substantial compliance,"
the tank owner doesn't have an eco-
nomic risk position in operating the
UST improperly. They .might think:
"If I'm not caught, or even if I have a
release, it is someone else's problem.
My tank premium won't be going up.
There is no economic hardship.
What's my incentive to properly
operate my UST?"
• continued on page 30
29
-------
LUSTLiiie Bulletin 42 • October 2002
m Square Operators from page 29
I'm sure that that many regula-
tors welcome the idea of a force of
private UST inspectors who have
hard money on the line in doing their
job. If you wonder how accurate or
effective these private inspections
are, remember that the inspector's
primary mission is to ensure that
they prevent losses from occurring—
losses that eat up hard-earned premi-
ums whenever a cleanup takes place.
Looking over the shoulder of
PMMIC is the Iowa Insurance Com-
missioner, who is responsible for
making sure that proper capital
reserve levels are kept in place,
underwriting standards adhered to,
and so on. That level of supervision
and the assurance to the public that
the insurance company is indeed sol-
vent is surely better than dealing
with most state legislatures that are
simply looking at budget expense
numbers.
Getting Installers on Board
One more tidbit we've picked up in
our journey: Obtaining a petroleum
equipment installer's technical in-
sight is crucial when assisting owners
to become better tank managers.
Again, financial incentives are the
key. In Iowa, every installer is
required to have a license and to
demonstrate pollution liability cover-
age.
If the installer installs a system
improperly, or if a component of an
existing system leaks due to
improper installation, PMMIC repre-
sents the owner in subrogation
claims against the installer. Since
they are truly responsible for their
work product, Iowa's installers have
established a high standard of care,
which is evident in the reduced fre-
quency of leaks found in the insured
population.
If Ya Can't Take the Heat...
The Petroleum Marketers and Con-
venience Stores of Iowa, as an organi-
zation, has realized that any owner
who cannot afford to upgrade his or
her UST system or to operate it in
compliance with all technical operat-
ing standards should not stay in busi-
ness. Members demand a level
playing field when dealing with reg-
ulators and the cost of complying
with those regulations. Society can-
not afford to pay the costs associated
with environmental damage caused
by those who canriot meet, or refuse
to meet, minimum technical stan-
dards.
Requiring owners and operators
to obtain and maintain FR coverage is
the most cost-effective method to
obtain compliance throughout the
industry. The provider of FR has a
significant incentive to reduce leaks
or to shut down those sites that are
too risky. As soon as states stop pro-
viding free FR coverage that absolves
tank owners and operators of respon-
sibility, the owners and operators
will become better educated as to
what is required to maintain private
FR and continue to operate their UST
systems properly. •
Ron Man is Executive Vice President
of the Petroleum Marketers and Conve-
nience Stores of Iowa, a trade associa-
tion that represents about 1,000
members that distribute, wholesale or
retail, about 85 percent of the diesel
and about 70 percent of the gasoline
used in the state. Ron can be reached at
ron@pmofiowa.com.
LEGAL UPDATE
by Patricia Ellis
California Announces
BP-Amoco Settlement
In June, 2002, California officials
announced a $45.8 million settlement
in a case against Atlantic Richfield
Company (ARCO). (Note: BP-Amoco
merged with ARCO in April 2000
and is now called BP, and is Califor-
nia's largest gas seller with about 20
percent of the market share.) The
company was accused of failing to
make required safety improvements
in underground tank systems at 59
service stations throughout the state.
The first signs of trouble for
ARCO came in mid-1998 from San
Joaquin County. County regulators
suspected inadequate tank improve-
ments at five or six stations. In dig-
ging up systems at eight stations,
each of the stations had some tanks
and piping that were found to be
substandard. According to David
30
Irey, the lead deputy in the environ-
mental prosecution unit of the county
district attorney's office, "Eight for
eight stations had problems. We
thought that it would be highly
unlikely that there wouldn't be simi-
lar problems throughout the state."
The district attorney's office filed
a lawsuit in 1999, which ARCO set-
tled in 2000. The San Joaquin officials
contacted the state, prompting agen-
cies to begin looking for similar prob-
lems in Los Angeles and Sacramento
counties. They found the same pat-
tern of inadequate tanks or pipes.
Ultimately, inspectors found substan-
dard components at 59 ARCO sta-
tions in 13 counties. ARCO had about
1,000 stations operating in California
during the 2000-2001 investigation.
Unfair Competition
In preparing the case, the attorney
general's office used the state's
Unfair Competition Act. ARCO had a
financial advantage, the state alleged,
because it kept selling gas while
other companies shut down to
replace tanks, pipes, and other parts
of the system.
The state also used the 1988 law
that required tank systems to be
upgraded by December 22, 1998.
State law, after the deadline, pre-
vented oil companies from delivering
fuel to stations that did not have a
blue-and-white upgrade placard.
Violators faced fines of $5,000 per
tank.
In the late 1990s, when the tank
upgrade deadline approached, then-
Governor Pete Wilson signed a bill
that allowed oil companies to self-
-------
October 2002 • LUSTLine Bulletin 42
certify completion of the upgrade
work. The bill was in response to
industry concerns that delays in gov-
ernment inspection of the upgrades
could result in service station clo-
sures. ARCO sponsored the legisla-
tion allowing self-certification, and in
1998, the oil company sued several
local regulatory agencies in Califor-
nia who would not issue the upgrade
certification without actual site
inspections.
The state's investigation found
that ARCO falsely self-certified some
of its own stations, claiming that they
had fiberglass tanks and piping
when, in fact, they had bare steel.
Prosecutors argued that ARCO's
actions provided the company with
an unfair business advantage. While
other companies were shutting down
service stations to meet the deadline
for underground tank improvements,
ARCO continued selling gasoline at
59 stations, postponing upgrade costs
and hiring contractors to do the work
after the rush by other companies
seeking to meet the state deadline.
The suit does not allege that
ARCO "falsified" its applications for
the upgrade certificates it needed to
stay in business. The suit says local
agencies issued the certificates based
on "incorrect" information from
ARCO, which does not imply crimi^
nal intent or constitute a violation of
state law.
The Settlement
About $18 million of the settlement
money will go to a state water pollu-
tion fund for cleaning up spills where
no responsible party is found liable.
The remaining money will go to
reimburse state and local agencies for
the cost of the ARCO investigation
and to state environmental enforce-
ment training and actions. Techni-
cally, the settlement totals $45.8
million—$25 million in cash, plus
$20.8 million that the state will credit
BP for tank system improvements
that exceed state requirements. The
company says it had made such
improvements at dozens of stations
since April 2000. BP must demon-
strate that the work was done, or pay
the difference. As further assurance,
BP agreed to give state inspectors
access to ARCO stations and to
immediately close stations with tank
violations until improvements are
made.
The settlement does not affect
local enforcement actions against BP
in Orange County or the case settled
in San Joaquin County, where the
pattern of alleged noncompliance
was first uncovered. State Attorney
General Bill Lockyer said that the
enforcement action was necessary
even though investigators found no
evidence that gasoline had leaked
from the substandard storage tanks
and pipes. "They were obligated to
replace these kinds of steel pipes that
would corrode underground, and
they didn't. The goal (of the $25 mil-
lion cash settlement) was to compel
ARCO to disgorge profits that they
made because they didn't...make
improvements at these sites."
Despite the settlement, state offi-
cials say that some of the 59 sites
have been or are still contaminated.
Nothing in the settlement "closes the
book" on ARCO's potential liability if
leakage is found to have occurred
from delays in tank improvements at
the 59 sites. According to Bill
Rukeyser, spokesman of CalEPA,
"The complaint was about failure to
upgrade. We didn't have to prove
leaks, and the settlement does not let
anyone off the hook if there are
leaks."
Lake Tahoe Suit
Finally Settled
In August, a settlement with Shell Oil
Company ended nearly a year-long
trial in which the South Lake Tahoe
Public Utility District sued oil compa-
nies, refiners, MTBE manufacturers,
gas stations, and distributors for con-
cealing the dangers of MTBE when
they marketed it as a gasoline addi-
tive. The agreement includes Shell
Oil Co., Shell Products Co., Equilon
Enterprises LLC, and Texaco, Inc.
Shell reached its settlement as the
jury was about to decide the com-
pany's share of damages to the util-
ity. Damages resulted in the closure
of 13 of the utility's 34 wells, which
were tainted or immediately threat-
ened by the fuel additive. Fourteen
companies settled with the district
before the trial began, including
Exxon and Chevron, which agreed to
pay $12 million and $10 million,
respectively.
Lyondell Chemical Company
agreed to a $4 million settlement in
July after a jury said Lyondell and
Shell knew about the dangers of
MTBE-blended gasoline but withheld
that information.
David Harpole, a Lyondell
spokesman said "We feel that it is in
the best interest of our shareholders
to settle at this time, as mistrials,
retrials, and appeals could create
costs larger than this settlement."
In all, the 16 settlements totaled
just over $69 million. Shell agreed to
pay $28 million to cover the costs of
cleaning up eight drinking water
wells contaminated by MTBE. The
companies maintain that they aren't
liable, despite the settlement. Accord-
ing to Shell spokesman Cameron
Smyth, "We felt that settling now
was the best thing to do to no longer
deal with protracted litigation costs."
According to South Lake Tahoe
Public Utility District spokesman
Dennis Cocking, "When we started
out down this road, we set out to
recover enough money to fix the sys-
tem and pay the bills, so our cus-
tomers didn't have to pay for it out of
their pockets. With the total settle-
ment ($69 million), we are able to do
that." Estimates of cleanup costs
range from $35 to $45 million.
What the Industry Knew
During the discovery phase of the
trial, thousands of documents
revealed that the oil industry knew of
the dangers of MTBE before it
became heavily used to make gaso-
line burn cleaner.
A 1981 ARCO document shows
that the company learned that 20 per-
cent of USTs leak, leading to the
"possibility of groundwater contami-
nation by MTBE."
A 1983 Shell document showed
that Shell found a taste and odor
threshold of 7-15 ppb, and that "even
if not a factor to health, it still had to
be removed below detectable amount
in order to use the water."
A 1983 API report indicated inef-
fective remediation of MTBE. API
members indicated in 1984 that
MTBE had potential for rapid migra-
tion and noticeable taste and odor,
and an Exxon researcher predicted
that fate, transport, remediation, and
taste/odor issues would lead to
higher cleanup costs and "adverse
public exposure."
In 1985, an Exxon researcher rec-
ommended that "MTBE not be con-
• continued on page 32
31
-------
LUSTLmcBn/telm42 • October 2002
m Settlement from page 31
sidered an additive to Exxon gasoline
on a blanket basis throughout the
United States because of "environ-
mental risk."
In 1986, ARCO told the Intera-
gency Testing Committee that MTBE
is "slightly soluble... minimal possi-
bility of spills,...extremely small
losses." By 1987, EPA found that
"MTBE contamination found in four
states.... problem could mushroom."
Komex H2O Science, a consulting
company that has assisted on a num-
ber of the MTBE litigation cases, has
created a timeline of MTBE informa-
tion, much of it based on documents
submitted during the discovery phase
of the trial. During this period, thou-
sands of confidential company
records were unearthed, showing that
America's biggest oil companies
knew about MTBE's risk to drinking
water years before domestic refiners
more than tripled the amount of the
additive in gasoline.
The timeline tracks regulatory
action, industry developments, major
spills, and research developments.
The timeline reveals that oil compa-
nies knew of the environmental risks
of MTBE but fought efforts to correct
it. The chronology, a display of who
knew what and when, is titled "From
Tank to Tap: A Chronology of
Methyl Tertiary Butyl Ether (MTBE)
in Groundwater." The chronology
can be viewed at http://www.blue
waternetwork.org/reports/rep_ca_
mtbe_history.pdf. An available-for-
purchase computer-based version of
the timeline allows you to click on an
event in the timeline and view an
electronic version of the original doc-
ument, report, or memo.
Lessons Learned?
The water utility's attorney, Duane
Miller of Sacramento, said, "It's
going to set a precedent. The oil
industry has to continue getting
MTBE out of gasoline sooner rather
than later unless they want to face a
jury again with these issues." Miller,
who also represents officials in Din-
uba, California, who have a similar
case pending against Unocal, Tosco
(now Phillips), and Chevron Corp.,
said "I think if s very clear to defen-
dants that if they go to trial, there's a
real risk of losing."
Oil companies say that the Lake
32
Tahoe settlement does not mean that
other similar cases will turn out the
same. According to Unocal spokesman
Batty Lane, "We evaluate every law-
suit on its individual merits."
The South Lake Tahoe trial began
in October 2001, in Superior Court in
San Francisco. In the mid-April ver-
dict in the product liability case, the
jury said Shell Oil Company, Lyon-
dell Chemical Co. (formerly Atlantic
Richfield Chemical Co.), and Tosco
Corp. (now part of Phillips Petro-
leum) had placed a defective product
on the market when they began sell-
ing gasoline with MTBE.
The jury also found that Shell
and Lyondell acted with malice when
they withheld information about the
chemical. Tosco was found liable for
pollution, but not for withholding
information. The verdict in the first
part of the trial came after seven
weeks of deliberation in a five-month
trial.
The penalty phase of the trial
began in April 2002, when the Tahoe
utility district sought tens of millions
of dollars in cleanup costs and puni-
tive damages. It wanted to force the
companies to "disgorge" profits
made from MTBE manufacturing and
sales. The settlement was reached
with Shell before the court had com-
pleted the penalty phase of the trial.
According to Scott Summy, a
Texas lawyer who is handling MTBE
cases in a number of states, "Very
similar evidence presented to the jury
in Tahoe will be presented in these
other cases. The jury was presented
with ample evidence that these com-
panies had early knowledge that pre-
dicted these problems. They failed to
disclose the information they had
and also promoted the additive in
gasoline despite the fact that it had
inherent problems."
Michael Hawley, the jury fore-
man, said he found the records of
early knowledge among the most
compelling evidence that he recorded
in 635 pages of handwritten notes.
"There were lessons to be learned,
but [Shell] didn't [learn them]
because it saw money to be made in
selling the product."
Wouldn't you love to know what
kind of dollar settlement that the jury
had in mind for each of the defen-
dants?
The South Lake Tahoe Public
Utility District recently held an open
house at the Arrowhead well in Mey-
ers to allow neighbors a tour of the
well, which is equipped with an
innovative $1.4 million water treat-
ment system being paid for with part
of the settlement money. The system
is an ozone and hydrogen peroxide
system that has been online since the
end of June, treating drinking water
at 800 gallons per minute.
Santa Monica Settles
with Chevron Texaco
and ExxonMobil
Six years after Santa Monica discov- ;•
ered MTBE in its drinking water
wells, the Santa Monica City Council
has approved a proposed settlement.
with two oil companies that the city
said were partly responsible for cont-
aminating its municipal water sup-
ply. (The court still has to agree to
accept the settlement.)
Under the settlement agreement,
Chevron Products Co., a subsidiary
of Chevron Texaco Corp. and Exxon-
Mobil Corp. will pay to design, build,
and operate a facility to treat the
city's water—a venture that is
expected to cost more than $200 mil- '••
lion over the years.
The companies will also pay the
city $30 million in cash to cover dam-',
ages. In 1996, Santa Monica detected
MTBE in 7 of its 11 drinking water
wells. The city had to scramble to
find replacement water. Two years
ago, Santa Monica sued seven major;
oil companies and 11 other manufac-
turers, suppliers, refiners, and
pipeline operators, claiming that they
had tainted much of the city's drink-
ing water with MTBE.
Chevron Texaco, Shell Oil Co.,
and ExxonMobil voluntarily agreed
to help the city deal with the contam-
ination, but the agreement expired in
January 2000. Five months later, the
city sued. In the interim, Shell had
been paying Santa Monica $3.25 mil-
lion per year to pover the cost of
importing water, because federal and
regional environmental officials had
designated Shell as the company pri-
marily responsible for the contamina-;
tion.
As part of its settlement, the city
has agreed to cease legal action
against ExxonMobil and Chevron
Texaco. If the city is successful in liti-
gation against companies not
-------
October 2002 • LUSTLine Bulletin 42
involved in fne settlement, then
ExxonMobil and Chevron Texaco
might be able to recover a portion of
the money they have agreed to spend
to restore the city's drinking water. It
is expected to take five years before
the facility to treat all the city's water
opens, according to Craig Perkins,
city director of environmental and
public works management.
According to Rod Spackman,
Chevron Texaco manager of govern-
ment and public affairs in the Los
Angeles area, "It is our strong belief
that our facilities have in no way con-
tributed to the contamination. Pro-
tracted litigation around these issues
we think is unproductive, and you
draw resources away from fixing the
problem."
NAFTA Rejects
Methanex Free-Trade
Complaint
On August 7,2002, a North American
Free Trade Agreement (NAFTA) tri-
bunal rejected most of the claims of
the Canadian methanol producer
Methanex over California's decision
to ban MTBE. The panel said it
needed more evidence to support
Methanex's claim that it was the vic-
tim of a political deal between Cali-
fornia Governor Gray Davis and
ethanol producer Archer Daniels
Midland Company.
Methanex claimed that California
violated free-trade rules when it
banned MTBE. Methanex claimed
that the governor imposed the ban to
eliminate a competitor of ADM and
pointed to a $200,000 campaign con-
tribution from ADM to Mr. Davis as
evidence. The tribunal expressed
skepticism that the governor was
aiming specifically at Methanex
when he imposed the ban. It said that
the tribunal could not "identify a sin-
gle or predominant purpose," such as
targeting Methanex, in what Mr.
Davis did. The tribunal offered
Methanex a final chance to prove its
claim by submitting a new legal brief
within 90 days.
NAFTA prohibits unfair protec-
tion of domestic industries, and
Methanex's original complaint
alleged U.S. officials acted improp-
erly to protect the U.S. ethanol indus-
try, which competes against MTBE as
a fuel oxygenate. Methanex later
amended its complaint with the
claim that Davis and ADM officials
held a secret meeting during the 1998
campaign at ADM's Illinois head-
quarters and ADM made over
$200,000 in contributions to his cam-
paign.
Aids to the governor scoffed at
the charges and said that the dangers
of MTBE were clear. Davis spoke-
sman Davi Chai also argued that
ADM and the ethanol industry have
not won any special favors in Califor-
nia. He said that Davis has fought
attempts to make ethanol the pre-
ferred clean-air additive in the
nation. He said, "It is extremely clear
that ethanol has found no friend with
California and the Davis administra-
tion."
In the lawsuit, filed in June 1999
against the U.S. government, Meth-
anex demanded $970 million in dam-
ages. The State Department defends
the United States in NAFTA cases. If
Methanex were to win, the federal
government would have to pay the
claim, or California could be forced
to revoke the ban.
Methanex has announced it will
file a new trade complaint against
California, arguing that a backroom
deal had been cut between Davis and
ADM.
Well Cleanup Class-
Action Status Denied
A Southern District judge ruled in
July 2002 in a suit in which it was
charged that the major oil companies
polluted groundwater. The judge
rejected the arguments of plaintiffs
from New York and three other states
who sought class-action status to
obtain an injunction that would
ensure the safety of their well water.
Judge Shira Scheindlin said that the
individual circumstances of each
case, and several other factors, made
certification impractical and
improper in the Methyl Tertiary
Butyl Ether (MTBE) Products Liabil-
ity Litigation.
The plaintiffs wanted class-action
status to seek an injunction on well
cleanup that costs billions of dollars,
with individual trials on damages to
follow. The judge said that the plain-
tiffs, despite making "every conceiv-
able argument to persuade this Court
that class-action treatment is appro-
priate in this hybrid environmen-
tal/products liability action," did not
meet the standards for certification
under Rule 23 of the Federal Rules of
Civil Procedure. "Such treatment
would stretch the decidedly elastic
class-action device beyond its break-
ing point—causing it to snap."
The plaintiffs, some of whom
lived adjacent to or near gas stations,
claimed the oil companies conspired
to mislead the public and the EPA as
part of an effort to increase concen-
trations of MTBE in gasoline and
block demands for additional testing
and safety measures.
The judge ruled that the claims
failed to meet the requirement of
"typicality." The judge stated that
"while the named plaintiffs made the
same legal arguments as the pro-
posed class, their claims must also
derive from the same course of con-
duct. Yet, the contamination of each
plaintiff's well comes through a fac-
tually unique set of circumstances,
such as a burst pipeline or a leaking
container." The plaintiffs were also
unable to show that the proposed
class action would "adequately and
fairly protect the interests of the
class."
An additional concern of the
judge was that the named plaintiffs'
stake in the action was substantial
enough "to prosecute this action vig-
orously on behalf of absent class
members. The named plaintiffs actu-
ally claim no personal injury,"
adding they complain instead of bad-
tasting or bad-smelling water.
The judge said that "this case
presents a novel issue: whether a
hybrid environmental/products lia-
bility class seeking mandatory injunc-
tive relief in the form of clean water
and well remediation may be certi-
fied" where class members are geo-
graphically diverse, a large group of
actors made the product, the effect of
the contamination is dramatically dif-
ferent among classes, and the contam-
ination stems from diverse causes. •
Pat Ellis is a kydrologist with the
Delaware DNREC UST Branch and
served as member of EPA's Blue Rib-
bon Panel on MTBE. She is a technical
advisor and regular contributor to
LUSTLine and can be reached at
pellis@dnrec.state.de.us.
-------
LUSTLine Bulletin 42 • October 2002
m Flexible Pipe from page 23
- Sticky and deformed pipe in the
sumps and cracked or loose end
fittings
- Misaligned piping tees, ells, and
riser pipes
-Pipe that is bent at an unusual
angle where it is terminated into
the submersible pump housing or
metallic fittings underneath the
dispensers
-Pinched, buckled, or elongated
piping
- Any signs of swelling or growth of
the secondary jacket of coaxial
piping over the coupling ferrules
- Compression, swelling, or distor-
tion of the rubber boots that may
be installed on the pipe in coaxial
systems where the metallic fitting
is installed at the pipe termina-
tions
- Stretching or tearing of the rubber
boots that are installed in the walls
of the containment sump, or boot
damps that are out of place
-A visible crack or leaking fuel at
the swaged area of the end fitting
-Fractures or cracks in the outer
layers of the primary pipe
• Test the secondary contain-
ment and release-detection
system to confirm that it is
working properly. As with all'
pressurized piping, release detec-
tion is critical to preventing
releases to the environment. Prop-
erly functioning secondary con-
tainment and rapid response to
release alarms have kept a number
of flex-piping failures from becom-
ing major releases to the environ-
ment.
- Check that sumps are liquid-tight
and that sensors and alarms are
working.
- Consider adding additional,
redundant piping release-detec-
tion systems to minimize any
release that might occur from a
failure of the primary pipe. There
are a variety of release-detection
systems that can be used in combi-
nation with pressurized piping,
including liquid sensors in the
sumps, mechanical line-leak detec-
tors, or electrical interlocks from
the leak-detection system to the
34
pumps.
Do not allow any fuel to re-
main in the secondary contain-
ment system for any length of
time. For purposes of this discus-
sion, secondary containment re-
fers to the outermost jacket of the
coaxial pipe, secondary contain-
ment conduit pipe, sumps, and
the various boots. What is not
clear to investigators is exactly
how long an exposure to product
constitutes too long.
If you find compromised flexi-
ble piping, take it out of ser-
vice immediately. Investigate
and preserve the evidence of
the failure so that an effective
examination of the failure can
be made and we all can gain a
better understanding of the
causes of the failures. Have an
independent expert at the site
when removing failed equipment
or investigating suspicious re-
leases. Many state inspectors,
insurance adjusters, and installa-
tion experts, such as installers,
have the experience and the quali-
fications for this task. Notify the
manufacturer and other parties
concerned and work closely with
them to investigate the causes of
the failure. The manufacturers
EPA HQ UPDATE
OUST Announces LUST Cleanup Goals
On October 1, 2002, OUST announced new national and regional annual
LUST cleanup goals. OUST established a national goal of completing
between 18,000 and 23,000 cleanups each year for fiscal years 2003-2007.
The aim is to reduce the current (FY02) national backlog of petroleum
release sites by one-half or more in the next five years and improve the
overall performance of the UST cleanup program.
OUST has provided each U.S. EPA region with a range of goals that
are based on historical and recent cleanup performance data and the
existing cleanup backlog. Each region has been encouraged to consider
state-specific circumstances when planning for cleanup progress with
each of its state UST programs. The regions have also been encouraged to
maintain or exceed the FY02 level of cleanups initiated at 90 percent of all
confirmed release sites.
To step up the pace of cleanups, OUST highlighted the importance of
encouraging the use of a wider array of programmatic tools, such as
multi-site cleanup agreements, pay-for-performance contracting, and
risk-based decision making. OUST indicated that it would support efforts
to obtain a better understanding of the progress being made to clean up
leaking tank sites. (For more information, contact Richard Mattick at
(703) 603-7154.) •
and marketers of flexible piping
need to be involved in the investi-
gation if the owner intends to
make a warranty claim. Many
owners are preserving samples of
failed piping for independent test-
ing. Document the condition of the
system as it is jbeing uncovered
and removed with photographs.
Vigilance, Vigilance,
Vigilance!
The bright spot in1 this flexible-pipe
situation is that many of the failures
have been discovered and caught by
vigilant UST owners and regulators
before they resulted in releases to the
environment. With further analysis
of these failures arid improved com-
munication, we can gain a clearer
understanding of the root causes of
these failures and manage the risks.
EPA's Office of Underground
Storage Tanks (QUST) has work
underway to collelct quality data to
determine the cause, scope, and mag-
nitude of the problems described
above. OUST intends to work with
Underwriters Laboratory (UL), the
manufacturers of flexible pipe sys-
tems, the states, and EPA's Office of
Research and Development to gather
needed information on flexible pipe
issues. 11
-------
October 2002 « LUSTLine Bulletin 42
from Robert N. Renkes, Executive Vice President, Petroleum Equipment Institute
UST Systems in China—Yesterday, Today, and Tomorrow
I attended China's Petroleum.
Distribution and Retail Summit
on August 27-28, 2002, in Bei-
jing, China. It was hard to turn
down the invitation, since China is
the most dynamic retail petroleum
market in the world today. With 1.4
billion people and only 80,000 ser-
vice stations, China will soon be a
force to be reckoned with.
Today, only one person in one
hundred owns a motor vehicle in
China. But that's about to change,
as the middle class grows and vehi-
cle ownership increases. And
change is definitely in the air—the
number of new driver's licenses in
China has quadrupled since the
beginning of the year.
Throughout China, thousands
of new stations are either planned
or awaiting government approval.
So far, most of the new stations are
the result of joint ventures with
Western oil company giants like BP,
Shell, and ExxonMobil. Thousands
more will be modernized in the
next few years as Chinese oil com-
panies and their Western partners
attempt to build a network of
"world-class" retail refueling sites.
Some of the newer stations I
visited in the Beijing area appear
similar to newer service stations in
the United States from the ground
up—electronic dispensers, good
lighting, uniformed attendants
(full-service only in China). And in
metropolitan areas where air pollu-
tion is a substantial problem, Stage I
and Stage II vapor recovery equip-
ment will soon be required to clean
up the air.
You begin to get a good feeling
about where China is headed with
their refueling stations until you
ask about what's underground. It's
then that you think you are back to
the United States in the early 1960s,
when we buried bare steel tanks
and forgot about them. All tanks
and almost all product lines in
China are bare steel. I couldn't find
a person at the conference who
knew of a fiberglass or cathodically
protected tank that was buried on
the mainland.
The big question regarding
China's underground storage sys-
tems is what kind will be installed
in the future? Will the Western oil
company partners demand systems
similar to those they now install in
North America and Europe, will
they do only what Chinese govern-
mental regulators require (what-
ever that is), or will they take the
easy way out and bury bare-steel
tanks and forget them? I hope it's a
decision the Chinese are willing to
live with for decades to come. •
LU.S.T.I.INE
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We welcome your suggestions and comments on any of our articles.
35
-------
U.S. Secures Pleas to
10 Felony Counts in
Tanknology Case
On July 24, 2002, U.S. EPA and the
Department of' Justice jointly
announced that the United States
had filed criminal charges against
Tanknology-NDE International,
Inc. On the same day, the United
States also filed a plea agreement
wherein Tanknology agreed to
plead guilty to 10 felony counts of
presenting false claims and making
false statements to federal agencies.
The guilty pleas were for false UST-
testing services performed by Tan-
knology employees at federal
facilities located in the states of
Texas, California, Arizona, Illinois,
Florida, South Carolina, New Jer-
sey, and the Commonwealths of
Pennsylvania and Massachusetts.
In pleading guilty at the federal
Western Texas District in August
2002, Tanknology admitted that the
investigation provided evidence to
a number of improper and/or
fraudulent practices carried out by
its employees at federal facilities
across the country, including U.S.
postal facilities, military bases, and
a NASA facility.
Under the plea agreement, Tan-
knology has agreed to pay a crimi-
nal fine of $1 million and pay
restitution of $1.29 million to the
United States for the cost of retesting
the tanks. In addition, Tanknology
will serve five years probation and
implement a quality management
system to ensure that false and
improper testing practices do not
occur again. Tanknology is the
largest UST testing company in the
United States, with four regional
offices and six field offices located
across the country. Its corporate
headquarters are in Austin, Texas.
The case was filed under the
criminal provision of 18 U.S.C. Sec-
tions 287 and 1001 (false claims and
false statements) subsequent to the
federal government conducting an
investigation from July 1998 through
December 1999. During this period,
federal agents observed Tanknology
testers at federal facilities across the
country. Investigators found evi-
dence that Tanknology employees
failed to properly perform tank tight-
ness testing and leak detection test-
ing at U.S. Department of Defense,
U.S. Postal Service, and National
Aeronautics and Space Administra-
tion (NASA) facilities.
The false tests ranged from fail-
ing to follow required test protocols
to "drive-by" tests, where a Tank-
nology tester was videotaped dri-
ving up to a federal facility, driving
away after a few minutes, and then
submitting false data.
The investigations were con-
ducted by the U.S. EPA Criminal
Investigation Division along with
the investigative arms of seven
other federal agencies with the
assistance of personnel from the
Texas Natural Resources and Con-
servation Commission (TNRCC)
and the Pennsylvania Department
of Environmental Protection. The
United States has no evidence that
the environment was harmed due
to the company's violations. •
For more information on this
case, visit the EPA OUST Web
site at www.epa.gov/oust.
2002
THE YEAR OF
CLEAN WATER
LU.SJ.LINE
New England Interstate Water
Pollution Control Commission
Boott Mills South
100 Foot of John Street
Lowell, MA 01852-1124
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