1. Regulatory Issues and the EPA's Used Oil Management Standards
Use of Refrigerant Leak Detectors to Screen for Total Halogens
Alvia Gaskill, Jr.
Environmental Reference Materials, Inc.
P.O. Box 12527
Research Triangle Park, N.C. 27709
Paper in the Proceedings of the EPA/AWMA 14* International
Symposium on the Measurement of Toxic and Related Air
Pollutants, Research Triangle Park, North Carolina, September 12
14,2000
2. Regulatory Issues and the EPA's Used OH Management
Standards-Use of Refrigerant Leak Detectors to Screen
for Total Halogens
AMa GaskUl, Jr
Environmental Reference Materials, Inc.
P.O. Box 12527
ResearchTriangle Park, N.C. 27709
ABSTRACT
EPAregulations(40CFRPart279)aswellascertainstateregulations,setlimitsforthelevel
oftotal halogens in used oil to be recycled into new oil orburned as fuel. This is done to
reduce the emissions of hazardous chlorinated solvents and their by-products, including
hydrochloric acid. Although EPA and ASTM field methods developed specifically for
measuringthe total halogencontent are available, for costreasons, many oil recyclers use
hand-heldrefiigerant leakdetectorsto screentheoilbymeasuring theheadspaceabovethe
oilandusingthismeasurementtoestimatetheoilphaseconcentration. Sincetheregulations
do notrequirethattestingbeperformed, only acertification ofthe qualityoftheoil, which
maybebased onprocess orotherknowledge, anytest methodmay also be used.
Theresults ofan evaluation ofthe effectiveness of leakdetectors in screening used oil for
totalhalogensarepresented. IncomparisonwithEPAlaboratoryandfieldmethods,theleak
detectorswereunabletodetecthalogensinoilscontaminatedwithlowvolatilityhalogenated
species such as those found in cutting oils and PCBs, even at percent levels. TTie leak
detectors also produced an excessive number of false negative responses for volatile
halogenatedspeciesintestingatlowtemperatures(0-32"F)andunderwindyconditionslikely
to be found infieldsituations. Many false positives were also found due to gasoline and
oxygenated solvents frequently foimd in used oil such as acetone and MEK. Because the
leakdetectors areanuiu^liabletool forscreeningusedoil, therecyclersshouldusetheEPA
or ASTM methods. Recommendations are given for creating financial incentives to
encourage recyclers to switch to the EPAmethods.
INTRODUCTION
Morethan 1 billiongallonsofusedoil torn automotiveandindustrialsourcesareburnedas
fijel or re-refined into new lubricating oil basestock in the U.S. annually. EPA used oil
regulations limitthe level oftotal halogens (interpreted by EPA to mean total chlorine) in
these usedoilstoprotecthumansandtheenvironmentfix)mexposuretohazardousandtoxic
halogenated contaminants in the oils that might be released or formed during burning or
processing'^.
These regulations set a 1000 ppm limit for total halogens abovewhichthe oil is presumed
tobemixedwithhalogenateddegreasingor spentsolvents, e.g., chlorobenzcne, methylene
3. chloride, perchloroethylene, 1,1,1-trichloroethane. Until proven otherwise, any oil
containingmorethanthislimitisconsideredahazardouswasteandcannotbeburnedasfuel
in smallboilers or recycled into new oil.
If it can be shown that the halogens are due to salts or chlorinated parafSns, the other
principal sources of halogens, the oil may still be burned or recycled with relatively few
restrictions up to a limit of 4000 ppm. Above this limit, the oil is considered off-
specification due to the potential for excess HCl formation and can onlybebumed as fuel
in large industrial boilers and fumacK which meetother EPArequirements.
The EPAregulations allow eitherknowledge ofthehistoryofthe oil in questionor testing
to be used to determine the oil's regulatory status. No testing methods or frequency are
prescribedintheregulationsandoilrecyclingindustrypracticesapprovedbytheEPArange
from notestingtotestingofeveryloadpickedupfromtheoriginalgeneratoroftheusedoil.
Toassistrecyclersincomplymgwiththeseregulations andregulatoryagenciesin enforcing
them, EPAandtheAmericanSociety forTesting andMaterials(ASTM) developedseveral
testmethods fordeterminingtotalhalogensinusedoil". Theseincludelaboratorymethods
basedonoxygenbombcombustion/ionchromatography(EPASW-846Methods5050/9056)
and field test kit methods basedon sodium dehalogenation/mercuric nitrate titration (EPA
SW-846 9077 and ASTM D5384).
Thefieldtest kit methods have been widely used due to their ability to provide an on-site
measurement of the total halogen content in about 10 minutes, thus allowing recyclers to
make on the spot decisions about the regulatory classification of a load ofused oilfroma
particulargenerator, before it is combinedwith loads from other generators.
However,manyrecyclcrsdo notusethetestkitsoronlyusethemoncertainsamples,citing
thecost pertest ($5) andthetime requiredtoperform thetest as excessivewhenapphedto
all loads. Instead, theserecyclers usehand-heldbatterypoweredelectronicrefiigerant leak
detectors to screen used oil samples for total halogens by measuring the headspace
atmosphereabovetheoilsamples andattemptingtorelatethegasphasemeasurementtothe
oil phase concentration. The leak detectors cost on average $150-200 each and are often
used for years. Thus, they are much less expensive than the test kits on aper loadbasis,
explaining their popularitywith oil recyclers.
Although static headspace testing for volatile organics is a well established technique
approvedbytheEPA,itistypicallydoneeitherforqualitativeidentificationorquantification
of individual volatile organic compounds, imder carefully controlled conditions in the
laboratory using gas chromatogr^hy (GC) or gas chromatography/mass spectrometry
(GC/MS)^. The applicability of refiigerant leak detectors as either qualitative or
quantitativefieldscreening tools fortotal halogens mused oils by static headspace testing
hasnotbeenevaluatedorapprovedbyEPAnorhavethevendorsofthesedetectorsprovided
applications guidance.
This work describes an evaluation ofthe type of electronic leak detector most commonly
4. usedbyoilrecyclers. Theobjectivewas to determine ifsuchleakdetectors areappropriate
screening tools for total halogens in used oil. The performance of several models was
compared to that of the EPA field method SW-846 Method 9077C and the laboratory
methods SW-846Methods 5050/9056 usingformulated samples andcommercialproducts.
The ability of this technology to detect all of the halogenated species in used oil and its
detection threshold, operating range, accuracy, precision and sensitivity to potential
interferences Hkely to be found in used oils (gasoline, water, antifi'eeze) was determined.
The effect on results of conditions likely to vary in a field envirormient (temperature,
headspace volume, wind and equilibration time) was also evaluated.
LEAK DETECTORS
The intendeduse ofleakdetectorsintheHVAC andrefiigeration maintenanceindustriesis
toidentify thepresence,locationandifpossible, intensityofaleakofarefiigerant gas fi-om
a sealed system. This is accomplished by moving aprobe connected to atest meterin the
areaofthesuspectedleak. Refiigerant gas intheairistransportedtothedetectorlocatedin
theprobetipbyeitherdiffusion orasmallairpump. Modelsbasedonpumptechnologyare
inherentlymore sensitivethanonesbasedon diffusion. Sensitivities areratedonthebasis
oftheprojectedweightperyearleakrate oftherefiigerant beingmonitored, e.g. 0.5 oz./yr.
Theseprobablycorrespondtoppmlevelsinambientair,butdetectionthresholdsinairhave
notbeenreported. Becausethedetectorsarenotcompound-specific,thespecific refiigerant
gas being monitored must be known to properly interpret the meter output, which may
consistofanaudiblealarmorboththe alarm and anilluminatedvisual Ughtemittingdiode
(LED) display, typicallyup to 7 LEDs.
A survey of the oil recycling industry determined that only leak detectors based on the
negativecoronadischargeprinciplehavebeenusedtoscreenusedoilfortotalhalogensand
that these type detwtors havebeen used for this purpose since 1985. The negative corona
discharge type detectors consist of a sensing tip and in most models, an air pump, both
located in a flexible probe handle"-"". These are connected to a meter, which contains
electronic circuitry forconverting the signalfromtheprobe into audibleand visualalarms.
The sensing tips are composed of an anode and a cathode exposed to ambient air. The
applicationof2000volts(V)totheelectrodescreatesacoronaorcloudofelectronsbetween
them with aknown current flow. The electronic circuitry converts this currentflowinto a
proportionalvoltagepotentialwhichismeasuredandstoredforreferencewhenthemeteris
turned on. Any reduction in the currratflowresults in a decreaseinthe measuredvoltage
potential. If the potaitial falls below the stored value, the audible and visual alarms are
produced.
Signals are generatedby compounds thatremoveelectronsfix)mthe electron cloud,based
on the principle ofelectron affinity. The electron affinities ofthe halogens are among the
greatest of all elements and halogen-containing compounds are among the most easily
detected usingthis technique. However, anycompound that can accept electrons &omthe
corona (e.g., oxygen-containing species), will also generate a measurable signal ifpresent
in high enoughconcentrations.
5. Detectors manufactured by TIF Instruments, Inc. (TIF) ofMiami, FL arethe onesusedby
oil recyclers. These detectors, (the 5000 series), include the features akeady described (7
LEDs), plus two separate measxirement modes for reporting signals due to
chlorofluorocarbons(CFCs)andhydrochlorofluorocarbons (HCFCs)andforthenewerclass
ofchlorine-free refrigerants, the hydrofluorocarbons (HFCs), which only contain fluorine.
Because the response tofluorineis 20 to 100 times less than for chlorine, a separate, more
sensitive circuit is used for HFC measurement. However, the user must know which
compound is beingmeasured for the signalfromeithercircuit to be meaningful. The next
generationofthesedetectors,whichhaverecentlybecomeavailable,containasinglecircuit
andprovide somewhatgreatersensitivity. The XP-1, also known as the Halogen Hawk, is
themost advancedofthese andcandisplayup to 18 LEDs over6 levelsofsensitivity, each
saidtobetwice as sensitive astheonebefore it". It isnotknown ifanyoftheseredesigned
models are being used by recyclcrs and there are no data available comparing their
performance with the 5000 scries.
Thereiscontroversyabouttheapplicabilityofthesedetectorstomom, .ringnonrefrigerants.
TIF reports that they respond to ethylene (500 ppm) and isooctane, but not common
halogenatedandnonhalogenatedsolventsincludingacetone,benzene,carbontetrachloride,
chlorobenzene, ethanol, gasoline, methylene chloride and perchloroethylene". However,
theyalsoreportthatgasolineleavesadetectableresiduethatdesensitizestheprobetipshould
itcontact aliquidcontaininggasoUneandthat anyhalogen-containing gas canbedetected,
including perchloroethylene"". A vendor forthe detectors states that the detectors canbe
used to determine ethylene inoil to be recycled".
STUDY DESIGN
Equipment Tested
Five leak detectors believed to be representative of those used by oil recyclers were
evaluated. Three model 5650 units (audible and visual alarm), one Model 5550 (audible
alarm only) and one XP-1 Halogen Hawk were either purchased new or recertified as
properly functioning byTIF Instruments. TheXP-1 wasincludedbecauseitrepresentsthe
most advanced and sensitive version of this type detector and provides a more detailed
rqjorting ofthe signal (up to 18 LEDs). For these reasons, it was expected to aid in the
analysis and explanation ofresults using the 5000 series detectors.
Two ofthe 5650 units had been in service for several years and malfimctioned repeatedly,
alarming inthe absenceofknown analytes. Oneofthesewasclearlyless sensitivethanthe
othersforunknownreasons. However,afterbeingservicedbytheOEMforthesecondtime
in 90 days, the performance ofboth wasjudged to be acceptable for the purposes of this
study. Malfunctions such as these are j^parently conunoi^lace according to the oil
recyclers, bringing into question the reliability ofthe units.
Samples were also tested using EPA SW-846 Method 9077C, aquantitative methodbased
on the Clor-D-Tcct Q4000 test kit ofthe Dexsil Corp. with arange of200 to 4000 ppm as
total halogens, andby EPA SW-846 Methods 5050/9056*".
6. Samples Tested
A variety of halogenated and nonhalogenated compounds and matrices representative of
those encountered inusedoilrecyclingweretested. Samples ofvirgin engine oil (Western
Auto lOW-40) were formulated to contain 0 to 5000 ppm as total halogens of 6 of the
regulated halogenated solvents (methylene chloride, chlorobenzene, 1,1,1-trichloroethane,
carbon tetrachloride, trichloroethylene and perchloroethylene), chlorinated parafBns from
cutting oils and engine oil additives, inorganic chloride, and PCBs, as Aroclor 1242 and
Askarel A, a mixture ofPCBs and trichlorobenzene sometimes found in transformer oil.
PCBs were included because, although limited byregulations to <2 ppm in used oil, high
level contamination (>2000 ppm PCBs) from mixing with transformer oil could still be
expected to be identified using the 1000 ppm threshold.
Samples containing water, antifi^eze, gasoline, alcohols, and acetone were also tested to
determine ifthese common used oil contaminants were detectable and couldresuhin false
positive classification of the oil. Fuels and neat commercial products (cutting oils and
solvents)werealsotestedtodeterminetheirabsolutedetectability. Commerciallyavailable
usedoil standardscertified forchlorinecontentwerealsotested. Usedengineoilsobtained
directly bom engine crankcases were tested to determine ifcontamination due to gasoline
resultingfromnormalusecouldbedetectedandresultinexcessivefalsepositives. Nineteen
virgininternalcombustionanddieselengineoilsfrommajorrefiners(Chevron,Mobil,Shell,
Quaker State, Motor Craft, Havoline, Castrol, etc.) were tested to determine if the
components in virgin oil contributeto anypositiveresults.
Samples were tested at least in triplicate and in the case ofthe 5650 leak detectors, using
both the HFC and CFC/HCFC modes. The HalogenHawk was tested at sensitivity levels
4 and5 on all samples andatall levelsoncertainsamples. Levels4 and 5 weredetermined
to provide the most usefiil comparative datavs. the otherdetectors.
Test Conditions Evaluated
The EPAmethods were performed on all sampleswithout deviationfromthe methods. A
smallsampleofoil (<0.5 g)wasremovedScorneachcontainerandanalyzed. Becausethere
is no standard procedure for testing used oil using the leak detectors, a procedure was
developed forthepurpose ofthisevaluation. Anecdotalinformationprovidedbyrecyclers
suggests tiiat field use practices mvolve either inserting the leak detector probe into the
headspaceofatankordrum andnotingtheresponseorremovingsamples andtestingthem
in 4 oz. open top glassjars'*.
RecognizingthattherearemanyconcernsaboutsampleheadspaceintegrityandstabiUtyin
vessels open to the atmosphere, anopen vessel procedure was employed, sincethisiswhat
recyclers who remove samples for testing are using and would probably continue to use.
Developing closed top vessels in which the probe (the diameter ofapencil) can easily be
inserted through the cap and removed was investigated and found to be impractical due to
the need to mix samples before testing, which can contaminate the probethroughdroplets
that adhere to the undersideofthecap. Use oflargervessels, withnarrowa:openings, hke
7. 8or16oz.Bostonroundbottles,wouldlimitheadspacewashoutby windanddrafts,but tiiie
possibility ofprobe contamination would still exist.
Theprocedurefollowedwastotestthesamplesin4oz.wide-mouthglassbottles(either50%
or 85%ftill)after equilibration for 12 hourswithout anymixing and after shaking forafew
seconds. These conditions roughlymodel those encoxmtered infieldsamples inwhichthe
static headspaceofatankordrum istestedor asampleremovedandmixedonthe spot and
theheadspacetested. Thetestingprocedureconsistedofquicklyinsertingtheprobeintothe
headspace above the sample and recording the signal observed (no. of LEDs, audible
alarms). It was not possible to differentiate sound levels with regard to intensity, so the
audiblealarmresponseswererecordedas eitherayes orano. BecauseevensKghtdraftsin
room air appeared to reduce theheadspaceconcentrationofsome samples, as measured by
thenumberofLEDsrecorded, alltestswerecarriedoutwiththeHVACturnedoff Outside
testingresultedin 50-100% lossofsignal, even inrelatively Ughtwinds. Disruptionofthe
headspacebytheprobeitselfwas sometimes alsonoted, andwheneverlowresultsbelieved
due to this were obsa-ved, the sample was reanalyzed. Due to the very low pmnp rates
(estimated to be <0.1 mL/min), the leak detectors themselves are believed to remove an
insignificant amount of the headspace gas due to pumping. Thus, r^eated testing ofthe
sameheadspaceispossibleaslongasitisnotphysicallydilutedbytheinsertionandremoval
oftheprobe.
The effect oftemperature, a known variable in headspace testing ofviscous liqmds', was
evaluated by testing samples at 0', 32* and 75-80"F, the laboratory temperature. Previous
work suggested a significant decrease inthe niunberofLEDs reported for the 5000 series
detectors at 45'F compared to room temperature". Since much of the used oil is collected
fromoutside unheatedtanks and drums inthenortheasternandmidwestemU.S., the effect
of low ambient temperatures on the headspace concentration of total halogens must be
considered in evaluating the apphcabilityofthe leakdetectors.
Calibrationofthedetectorstoonlyrespondat levels>1000ppmtotalhalogensbyblanking
them against a known standard has been reported as have attempts to blank the detectors
against oils containing suspected false positive interferences (the oil matrix, gasoline,
water)*,butwefoimdthatnoneofthedetectorscanretainasignalfiromonediscretesample
to the next. The only blanking c£q)ability is that ofre-zeroing the detector in acontinuum
ofconcentrationinambientair, eitherbyuse ofaresetbutton orbyturningthedetectoron
inagivenatmosphere, soastomoreeasilytrackdovmasourceofleakingrefiigerant. Thus,
theonlywaytorelatethedetectorsignaltoaconcentrationintheoilisbydirectcomparison
to aknovm standard. This was the approach followed in this study.
RESULTS
The results of tests performed on the formulated samples using the EPA methods showed
that the recoveries ofthe spiked analytes were greater than 90% for boththe bomb/IC and
the test kitmethods forthehalogenated solvents, chlorinatedparaffins, inorganic chloride,
and PCBs. No false positives due to non-halogenated solvents, water, ethylene glycol or
gasoline were observed nor were any false negatives due to the non-volatile chlorinated
8. compounds(paraffins, inorganicchloride,PCBs). Thesametypeperformancewasachieved
onthe analyses ofcommercial products.
Resultsobtainedusingthe5000 series leakdetectorswerenearlyidentical forboththeHFC
and CFC/HCFC modes. About one third of the virgin oils produced a positive response
usingthe 5550 detector, includingtheWesternAuto oil used as thebase forthe formulated
samples. The Halogen Hawk registered an average of 0.2±0.4 and 1.0±1.0 LEDs,
respectively at levels 4 and 5 for the virgin oil vs. 8.0±0.0. and 17.7±0.6 for 500 ppm
methylene chloride. Thus, itcanbeconcluded thatthe virgin oil matrix has Uttle effect on
the signal obtained and attempts to account orcorrect for it are unnecessary.
Although all the detectors responded to the volatile halogenated solvents, the sensitivity
varied greatly, suggesting that boththe volatiUty and the number ofchlorine atoms onthe
molecule contribute to the signal intensity. For example, the maximum no. of LEDs
observed for methylene chloride using the 5650 detectors was 3, while nearly 5 were
measured for carbon tetrachloride and only 2 for chlorobenzene, the least volatile of the
solvents tested. At the sample level closest to the regulatory threshold, 1200 ppm,
chlorobenzene was notdetected at all. Some ofthe morehighly chlorinated solvents, e.g.,
carbon tetrachloride, were detected at levels as low as 50 ppm, but the lower limit of
detectionwas generally severalhundredppm intheoil. The precisionwas generallybetter
than 10% CV forthetriplicate analyses, but evenso, theoccasional zero LED responsefor
aknown positive sample would notbeconsidered acceptable for aregulatory testmethod.
The intensity vs. concentration relationship for the most volatile solvents appears
logarithmic, with arapid initial response, which becomes linearor evenflatbetween 1000
and 5000 ppm. (Figures 1 and 2). As noted, although the response spears related to both
the compound's vapor pressure and degree ofhalogenation (Table 1), the relationship is a
complex one.
Figure 1
AwrageResponseof5650 Detectors To CUorinatedSfdwiits
* 5
0 1000 2000 3000 4000 5000 6000
Cblorine Concentration (ppn)
— M o t h y l e n e Chtorida
- - » « - - Trichloroolhyleno
111-Trichtoro9than« — Carbon Tetrachloride
l^rchloroethyleno Chlorobenzene
10. 1 KPa = 7.501 nimHg, 0.987 x lO^* atm
the EPA hazardous waste regulations also apply to any other chlorinated fluorocarbons used in degreasing
operations
""CAS no. given is for 1,2,4-trichlorobenzene
'these compounds decompose at >300*C, with the release ofHCl
NA « not available
Theresponserelationship showninFigure 2 fortheHalogenHawk isbasedonthe average
response ofthe meter, measured at all sensitivity settings and normalized to an equivalent
level 1 reading. The quantitative relationship between the LED response of the Halogen
Hawk to the 5650 meters has also not been established. Thus, its resuUs should only be
considered as assisting in explaining the qualitative differences in response of different
compounds, especiallythe factthat the saisitivitieswereinthe sameorder as forthe 5650
detectors.
Some recyclers claim that the intensity vs. concentration relationship allows the use of3
LEDs asthe cutoff forrejecting loads, sincemostofthe aliphatichalogenatedsolventswill
produceareadingof3 LEDs athalogenlevels greaterthan 1000ppm. However,notevery
detector evaluated in this study produced 3 LEDs for samples containing 1200 ppm of
aliphatichalogenatedsolventsandchlorobenzene. Oilscontaining 1200ppmchlorinelevels
due to solvents even less volatile, e.g., o-dichlorobenzene, would notbe expected to meet
this criterion either.
The detectors were unable to detect the non-volatile halogenated compounds (parafBns,
inorganic chloride, PCBs) even at levels as high as 1% PCBs as Aroclor 1242 or 3%
chlorinated paraffins (as chlorine). The detectors were also generally unable to detect
relativelynon-volatileoxgen-containmgspecieslikeglycolsandwater,butdidexhibitstrong
sensitivitytovolatileoxygraiated solvents likemethyl ethyl ketone and acetone, dueto the
electronaffinity oftheoxygen. Virginoils spikedwithgasolineat levels typicallyfoundin
used oil not exposed to halogenated solvents (1000 ppm) and used oils obtained torn
gasoline engines produced signal intensities of aroimd 1 LED for the 5650 detectors and
equivalent to the signals observed for 1200 ppm methylene chloride using the Halogen
Hawk.
Littledifferencewasobservedbetweenresultsfiwmsamplesequilibrated 12hoursandthose
freshly shaken. However, once the headspace was removed, more than 30 minutes was
requiredtoreestabUshtheequilibriumlevelwithoutmixing. SincetheequiUbriumstatusof
bulkcontainers inthefieldcannotbe known in advance, a direct analysis oftheheadspace
is not appropriate and a sample must be collected and mixed before the headspace is
analyzed.
The volume ofheadspace in the bottles did not significantly influence the results (results
obtained fiom 50%fiilljars were about the same as those obtained torn 85%fiillbottles).
Areduction in temperature torn 75*to 32F didresultinadecreaseinthe signal formostof
11. thehalogenated solvents, reducmg it to zero formethylene chloride andperchloroethylene
at 1200 ppm for one ofthe detectors. At 0"F, the signalfromall ofthe 5650 detectors was
reducedto zero forperchloroethyleneat 1200ppmandforchlorobenzeneat 5000ppm, and
for one detectorthe signal was also reduced to zero for methylene chloride at 5000 ppm.
The effect of temperature and headspace volume on the results can be explained by the
theoryofheadspacetesting. Thebasis forheadspace orvaporequilibration analysisisthat
the analyte partitions between two phases (in this case oil and air) at a constantratio once
equilibrium between these phases has been attained. The factors affecting the air level
include the analyte's solubility in the oil and thevaporpressure ofthepure confound at a
given temperature".
Forviscous liquids hke oils, inwhichthe analyte is more or less miscible as in the case of
halogenated organics, the organics prefers to stay in the oil, so that the volume of the
headspace relative to the oil layer is largely irrelevant to the headspace concentration of
analytes". By raisingthe temperature, the headspace concentration ofvolatileorganics can
beiiKreasedand, likewise,byloweringthetemperature,theheadspaceconcentrationcanbe
decreased. However,largelynonvolatilechemicalsUkePCBs,chlorinatedparafBnsandsalts
willnotpartitionintotheheadspacetoanydetectabledegree, evenatelevatedtemperatures,
rendering their detection using headspace techniques impossible.
CONCLUSIONS AND RECOMMENDATIONS
Althoughrefrigerant leakdetectors areclearly sensitiveto someofthevolatilehalogenated
solvents,fromaregulatorystandpoint, theirinabilityto detect thenonvolatilehalogens and
chlorobenzeneattheregulatorythresholdof1000ppm,theirsusceptibilitytofalsenegatives
due to low temperatures, and vapor losses during field testing, make them unsuitable as a
screeningtool fortotal halogens inused oil. Limitingthe Ustofcompounds tobe screened
to the mostvolatile solvents is unacceptable, since theregulations are intendedto limitthe
total halogens that enter the used oil management system. It is likely that the use ofthese
typesofleakdetectorstocertify loadsofusedoilasmeetingthehalogenlimithaveactually
done the opposite and allowed greater contamination than EPA or the recyclers intended.
So, although recyclers cannot be prohibitedfromusing the leak detectors, they must still
provideEPAwithind^endentknowledgebasedonthehistoryoftheoil'suseorresults from
testing using EPA or ASTMmethods in orderto meet the regulatory requirements.
As noted at thebeginning, recyclers claim that the cost ofthetest kits andthe time ittakes
to perform the tests are prohibitively expensive given the dynamic nature ofthe used oil
recycling industry (many locations, many discrete containers of used oil, which must be
collected and processed daily). EPA also assumed that the cost of reqmred testing of all
loadsfromevery generator before they are collected and enter the used oil management
system would force recyclers out of business and discourage recycling by used oil
generators. Thus, they did notrequiretesting, but still insistedonacertification oftheoil's
qualitywithrespecttotheregulatorylimitsfortotalhalogens. Thisleadtotherecycler'suse
ofthe leak detectors and theproblems described in this paper.
12. Onewayto makecertainthatused oil cleanliness is ensured withoutdisruptingthepresent
commercial market system is by offering tax credits to qualified recyclers and generators,
hireturnforperformingtestingoftheusedoilbys^provedEPAorASTMmethodsinstead
ofbythe leakdetectorsornotatallas isalsocommon,theywouldreceiveadollarperdollar
tax credit fortestingcosts, including laborand administrative costs. EPAand stateswould
then have the option of inspecting the testing records kept by the mdtistry to ensure that
compliance is occurring and the oil quality is withinthe limits fortotal halogens.
REFERENCES
1. Code ofFederal Regulations (40 CFR), Part 279, Standards for the Management
ofUsed Oil, publishedby the OflBce ofthe Federal Register, 1995.
2. Federal Register, Hazardous Waste Management System; Burning ofWasteFuel
andUsed Oil Fuel in Boilers and Industrial Furnaces, Vol. 50, No. 230, Friday
Nov. 29, 1985, pp. 49164-49211.
3. Gaskill, A., Jr., E.D. Estes, D.L. Hardison, L.E. Myers andB. Lesnik. Vahdation
ofAnalytical Methods forDetermining Total Chlorine inUsed Oils and OilFuels.
Presented atthe FourthAimual U.S. EPA Syn^osium on SoUd Waste Testing and
Quality Assurance, Washington, D.C., July 11-15,1988.
4. Gaskill, A., Jr., E.D. Estes, D.L. Hardison, L.E. Myers and W.M. Yeager.
ValidationofTestKit Methods for DeterminingTotal Chlorine inUsed Oils and
Oil Fuels. Presented at the Fifth AnnualU.S. EPA Symposium on SoUd Waste
Testing and QualityAssurance, Washington, D.C., July24-28,1989.
5. Gaskill, A., Jr., E.D. Estes, D.L. Hardison andP.H. Friedman. Development and
Evaluation ofAnalytical Techniques forTotal Chlorine inUsedOils andOil
Fuels.
In: Symposium on Waste TestingandQualityAssurance: 2nd Volume, ASTM
STP1062, David Friedman, editor, American Society for Testing andMaterials,
Philadelphia, 1989.
6. U.S. EPA, Test Methods for Evaluating SoUd Waste, Physical/Chemical Methods,
(SW-846), Third Edition, Office ofSoUd Waste, Update n, September 1994.
7. ASTMD5384-96, Standard Test Methods forChlorine inUsedPetroleum
Products (FieldTest KitMethod), American Society for Testing andMataials,
West Conshohocken, PA.
8. B. Kolb and L.S. Ettre, StaticHeadspace-Gas Chromatography Theoryand
Practice, Wiley-VCH, Inc., New York, 1997.
9. EPA Method D-l-VOA: QuickTurnaround Method for Contract Laboratory
Practice (CLP): Static Headspace Method for Volatile Organic Analytes (VOA)
14. Figare 1
Average Respooceof5650 Detectors To Chlorinated Solvents
5 T , 1 . , ,
6000
Clilorine Concentration (ppm)
—•—Methylene Chloride —•—111-Trtchloroethane — * — C a r t » n Tetrachloride
-•K-Trichloroethylene —K—Perchloroelhylene — C h k x o b e n z a n e
