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LUSTLine Bulletin 42 • October 2002
<br /> ■Analytical Methods from page 1 render water unsuitable for a partic- the capability to conduct the analyses
<br /> ular intended purpose (e.g., drink- necessary to determine all of the fuel
<br /> left to the discretion of the petroleum ing, cooking, bathing, laundry, oxygenates at the concentrations of
<br /> refining industry. Primarily for eco- watering livestock) because it is regulatory concern does exist in the
<br /> nomic and logistical reasons, the indus- either unsafe or unpalatable due to current marketplace, the availability
<br /> try overwhelmingly opted for MTBE, objectionable taste and/or odor. of this service is limited. It simply
<br /> and it is currently used in approximately Remediation of contaminated isn't standard operating procedure to
<br /> 80 percent of oxygenated fuels at concen- groundwater and treatment of conta- calibrate for all of the oxygenates
<br /> trations ranging from 11 to 15 percent minted drinking water is time-con- and, until now, no single method
<br /> by volume. Ethanol-containing fuel is suming and expensive.Detecting the with this capability has undergone a
<br /> used primarily in the midwestern United presence of fuel oxygenates and rigorous demonstration of applicabil-
<br /> States and accounts for about 15 percent delineating their extent in the envi- ity. Conventional analytical proce-
<br /> of the oxygenated fuel supply. The other ronment is difficult for a variety of dures designed for petroleum
<br /> oxygenates combined account for the reasons. In fact, only a couple of hydrocarbons (i.e., BTEX) can also
<br /> remaining 5 percent. states have even started to investi- detect MTBE and the other ethers
<br /> gate the contamination of their when properly calibrated for them,
<br /> The Down Side of Fuel groundwater with oxygenates other but they have very poor sensitivity
<br /> Oxygenates than MTBE. Thus, the extent and for TBA and the other alcohols.
<br /> Releases of oxygenated fuel into the magnitude of oxygenate contamina- Of the several widely used deter-
<br /> environment have occurred nation- tion in the United States is largely minative methods published in SW-
<br /> wide from leaking storage tanks and unknown. 846 (U.S. EPA, 1997), the two most
<br /> pipelines, transportation accidents, Oxygenates easily dissolve into appropriate for oxygenates are
<br /> refueling spills, unburned fuel pre- water and tend to migrate without Method 8260(Volatile Organic Com-
<br /> sent in the exhaust from watercraft, significant retardation in flowing pounds by Gas Chromatography/
<br /> and/or consumer misuse. Even at groundwater.MTBE plumes in par- Mass Spectrometry, GC/MS) and
<br /> very low concentrations, the pres- ticular may extend farther than is the Method 8015 (Nonhalogenated
<br /> ence of some of these oxygenates can case for the petroleum hydrocarbons Organics Using Gas Chromatogra-
<br /> benzene, toluene, ethylbenzene, and phy/Flame Ionization Detector,
<br /> the three isomers of xylene (BTEX). GC/FID). Other GC detectors (e.g.,
<br /> a Because they spread more exten- the electrolytic conductivity detector
<br /> LUST
<br /> Even E ye,Li� sively, oxygenate plumes are more [ELCD] and the photoionization
<br /> Ediror difficult to detect and delineate. In detector [PID]) are not designed to
<br /> z le Pappo,Laymit - LUSTLine #36 (2000), Jim Weaver respond well to compounds that do
<br /> Marcel Moreau,Tedwicat advisor and John Wilson discuss the difficul- not contain halogens (ELCD)or dou-
<br /> Panicia Ellis,PhD,Technical Advisor r ties of characterizing MTBE plumes ble bonds (PID).Therefore, methods
<br /> Ronald Pollak,NErKrPCC Executive Director in their article "Diving Plumes and using either of these detectors are not
<br /> Lynn DePont,EPA Project Officer
<br /> Vertical Migration at Petroleum recommended for the analytical
<br /> LUSTLine is a product of the New England`r Hydrocarbon Release Sites." determination of oxygenates.
<br /> Interstate water Pollution control Commis- A tremendous amount of oxy- In particular, Method 8021 (PID
<br /> cion(NEIveagre It is produced through a,p enate data from leakingUST sites detector) cannot be regarded as a
<br /> cooperative agreement(U and
<br /> the 82-OI-0) g
<br /> between NEnvpcc and the U.S. - have been generated over the past consistently reliable analytical tool
<br /> Environmental Protection Agency. several years, yet there is under- for the analysis of oxygenates
<br /> LUSTLine is issued as a cummunication standable concern as to whether because it is susceptible to both false
<br /> s'crvice for the Subtitle i RCRA
<br /> Hazardous&Solid waste.amendments these data are valid.In general,these positives (misidentifying the pres-
<br /> rule promulgation process. concerns are related to two issues: ence of an oxygenate)and false nega-
<br /> LUSTLine is produced to romote tives(failing to identify the presence
<br /> information exchange rn,usrTILusT issues. , Analytical obstacles,and of an oxygenate). False positives
<br /> The o inions and information stated herein . Ether hydrolysis articular) of
<br /> are hose of the authors and do not neces- (particularly often result in resources being
<br /> sadly reflect the opinions of NEIWPCC. t MTBE to TBA). wasted on unnecessary investigation
<br /> This publication may be coded. and cleanup efforts.False negatives
<br /> Please give credit to NEIWPCC. In the following sections, we'll dis-
<br /> NEIWPCC was established b an Act of is may result In the exposure co tami-
<br /> Y cuss these issues and present some tors to harmful levels of contami-
<br /> agencss in 1947 and remains the oldest new information that may help us in
<br /> agency in the Northeast united States "�, nants. The problems with Method
<br /> concerned with coordination of the multi- dealing with oxygenates in the envi-
<br /> media environmental activities 8021 are due primarily to coelution of the states of Connecticut,Maine, ronment. interferences and to the high ioniza-
<br /> Massachusetts,New Hampshire, _
<br /> New York Rhode Island,and Vermont. tion energies Of many oxygenates.
<br /> Analytical Obstacles Method 8021 uses a specialized
<br /> NEIWPCC One of the greatest impediments to light bulb(lamp)to ionize analytes of
<br /> Boott Mills South,100 Foot of John Street' $ P g
<br /> Lovell,MA 01852-1124 understanding the extent of contami- concern.The lamps typically used in
<br /> Tel It (978)3237929 nation caused b fuel oxygenates is a PID for Method 8021 operate at a
<br /> Fax:1978)78)-2919 = Y Yg P
<br /> Iustlinecneiwpcc.ing the perceived lack of a single analyti- maximum potential of 10 eV. The
<br /> tusruae is Printed on Recyaed Paper cal method for the determination of ionization potentials of ethanol and
<br /> fuel oxygenates as a group.Although TBA are 10.2 eV and 10.25 eV,respec-
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