United States
                    Environmental Protection
Industrial Environmental
Research Laboratory
Research Triangle Park NC 27711
                    Research and Development
EPA-600/S7-84-072  Aug. 1984
&ER&          Project  Summary
                    Waste  Crankcase  Oil  Heater
                    Study:  Phase  II.   Organic  and
                    Inorganic  Speciation  Analyses
                    M. Cooke, W. E. Bresler, T. L Hayes, R. L. Livingston, C. T. Litsey, B. Paris, and
                    A. K. Wensky
                      This  study  involved  measuring
                     specific chemical species in emissions
                     from  two waste-oil-fired  commercial
                     heaters: one utilized a vaporizing pot;
                     and the other, an air atomization com-
                     bustion chamber. Polynuclear aromatic
                     hydrocarbons (PAHs) were analyzed in
                     the gaseous emissions of both units.
                     Elemental analyses (including Pb, Fe,
                     Cd, Zn, Cl, and Br) were performed on
                     the  air  atomization  discharges. In
                     addition, several waste crankcase oils
                     were tested for baseline levels of these
                     species and to determine the effect on
                     metal concentrations of both filtration
                     and  sedimentation  during  storage.
                     Tests were also performed on emissions
                     from  the air atomization burner to
                     measure the amount of organometallic
                     lead  species  discharged from  the
                     burner, and to  determine the distribu-
                     tion of iron oxidation states (Fe[IIJ
                     versus Fe[lll]) in gaseous emissions.
                      This Project Summary was developed
                     by EPA 'a Industrial Environmental Re-
                     search Laboratory, Research Triangle
                     Park.  NC, to announce key findings of
                     the  research  project  that is  fully
                     documented in a separate report of the
                     same title (see Project Report ordering
                     information at back}.

                      This study is an extension  of earlier
                     work on residential appliances designed
                     specifically for waste oil combustion. In
                     that investigation, two reference waste
                     crankcase oils were burned in residential
                     waste heaters  and a Level 1 analysis
performed on the fuels, combustion
residues, and gaseous  emissions. The
two types  of space  heaters tested,  a
vaporizing  pot and an  air atomization
heater, were found to produce high levels
of metallic discharges. The air atomizer
generated the highest gas-phase metal
discharges, and the vaporizing pot pro-
duced high levels of organic discharges
along  with a  metal-rich pot residue.
Among the metallic species identified for
further study were Pb,  Fe, Cd, and Zn:
they were produced in high amounts and
(in certain forms) are potentially harmful
to humans. Since several researchers
have proposed the use  of waste oil as
either a direct fuel or a blending agent to
lower  the cost of primary fuels,  it  is of
great interest to investigate the environ-
mental impacts of expanded waste oil
  In this study, detailed investigations
were performed on the species identified
or suspected from the Level  1  data
generated in the earlier  program. In this
study, samples were  taken from both a
vaporizing pot unit (Kroll) and a residential
air atomization heater (Dravo). The experi-
mental portion of this study consisted of:

  (1) Analysis of five  fuels to determine
    their metal content as a function of
     storage, batch differences, and fuel

  (2) Analysis of vaporizing pot and air
     atomization discharges for poly-
     nuclear   aromatic  hydrocarbons

  (3) Analysis  of  air  atomization
     gaseous discharges for organolead

  (4) Analysis of the Fe(ll)/Fe(lll) ratio in
     the air atomizer gaseous effluent.

  (5) X-ray fluorescence analysis of the
     air atomizer particulate discharges
     to show concentration of inorganic
     species including Br, I, Fe, Cd, Pb,
     and Zn.

  Figure  1   shows  the two  heaters
schematically. The principal difference is
the way the flame is sustained in each
heater's firebox. The air atomization unit
injects aerosolized oil vapor into the burn
chamber, and the combustion gases are
discharged in the gas phase into the flue.
By  contrast the vaporizing  pot  heater
operates through volitilization of heated
oil: the vapors are burned, and a heavy pot
residue is left behind. In the initial study,
this residue was found to contain a major
portion of the metallic species from the
fuel oil.
Experimental Procedures
  PAHs were measured in both heaters
by collecting Modified Method 5 samples
and performing high-resolution capillary
gas chromatography/ mass spectrometry
(HRGC/MS)  analysis on combustion
sample  extracts.  An  example  of the
complex organic matrix observed in these
samples is shown in Figure 2, the total ion

   Damper  —«-\
         Low Pressure Air
        Atomization Burner

Figure 1.    Test combustion systems.

Scan Time (mini
Figure 2.   HRGC/MS chromatogram of vaporizing pot emission sample.
chromatogram  from   the   HRGC/MS
analysis of a vaporizing pot sample.
  Volatile lead  (alkyllead)  compounds
were  analyzed by collecting cryogenic
samples from the air atomization heater


                                                            Waste Oil
               ' Pot Residue

 Vaporizing Pot Burner
                   gas-phase discharges. High lead levels in
                   engine waste oil probably arise from lead
                   antiknocking agents added to gasoline.
                   Analyzing  volatile  lead  compounds in
                   combustion emissions was important to
                   determine  if  organolead  compounds
                   were stable in crankcase oil and subse-
                   quent combustion, or if ionic  lead is
                   converted to appreciable organometallic
                   discharges during combustion. Figure 3
                   shows the  cryogenic  sampling  train
                   developed for this study. Samples were
                   extracted with isooctane and analyzed by
                   combined  gas chromatography/atomic
                   absorption spectrophotometry.
                     Metal species were analyzed by X-ray
                   fluorescence (XRF) on filter samples of
                   combustion gas from the air atomization
                   heater, and  also on  raw crankcase oil
                   samples. The  XRF data were used to
                   confirm the presence of metallic species
                   that ostensibly arise  from engine wear
                   (e.g., Fe) and elements that are present in
                   waste  oil  via  contamination  from fuel
                   additives (e.g.,  Br). The fuel  data  also
                   revealed comparative resuIts for waste oil
                   handling techniques; e.g., sedimentation
                   and filtration.
                     Iron speciation was performed to deter-
                   mine  which  oxidation state (Fefll] or
                   Fe[lll]) predominated   in  the  ain
                   atomization  discharges.  Fe(ll) was*
                   analyzed  by  photometric  analysis of

                                                        Trap 2
                                        extended period of time (11 months) had
                                        little or no effect on the level of metallic
                                        species in  fuel obtained from the top of
                                        the tank.

                                        Iron Speciation
                                          The iron speciation tests indicated that
                                        most of the air atomizer iron emissions
                                        existed as Fe(lll). This is a cause for great
                                        concern due to the presence of benzo(a)
                                        pyrene (BaP) in the PAH emissions. There
                                        is  a  documented  synergistic  effect
                                        between Fe(lll) and BaP which promotes
                                        certain types of mammalian cancers and
                                        is believed to magnify the dangers asso-
                                        ciated with Fe(lll) emissions.
Figure 3.    Cryogenic sampling train.

ferrous bathophenanthroline complex.
Since ferric compounds and benzo(a)py-
rene are known to produce a synergistic
promotion of certain tumors, these two
species were important to this study.

  This study provided specific speciation
data on major constituents indicated as
being  potentially  harmful pollutants in
the previous Level  1 analysis of vaporizing
pot and air atomizer residential  heater
emissions. Conclusions of this study are
summarized by chemical specie.
Polynuclear Aromatic
  Several PAH compounds were found at
elevated  levels  in  the  gas-phase
emissions  from the  two  combustion
systems. As predicted from Level 1 data,
the vaporizing pot system produced ap-
preciably higher emissions than either
the air atomizer heater or (based  on
literature estimates) residential heaters
fired with commercial fuel oil.
Lead Species
  No organolead species were detected
in the  cryogenic samples  from  the air
atomization heater, indicating that  lead
exists  essentially as  Pbfll)  in  the air
atomization emissions.

  X-ray fluorescence analysis of  panicu-
late emissions from the air atomization
heater particulate matter confirmed the
elevated Pb, Zn, and Fe found in earlier
Level 1 analyses. In addition, high Br and
Cl levels were found in gas-phase emis-
sions. The Br level was several times the
Cl level, indicating that Br from gasoline
antiknocking additives exists as  a major
constituent of crankcase oil, and consti-
tutes a major air contaminant from this

Fuel Studies
  Filtration was shown to be effective for
lowering metallic species (such as iron) in
waste  crankcase oil and  should  be a
beneficial  pretreatment procedure  for
this  fuel.  Settling by gravity over an

       M. Cooke. W. E. Bresler. T. L Hayes, ft. L Livingston, C. T. Litsey, B. Paris, and A. K.
         Wenskyare with Battelle-Columbus Laboratories, Columbus, OH 43201.
       Robert £. Hall is the EPA Project Officer (see below).
       The complete report,  entitled "Waste Crankcase Oil Heater Study: Phase II.
         Organic and Inorganic Speciation Analyses," {Order No. PB 84-212 224; Cost:
         $10.00, subject to change) will be available only from:
              National Technical Information Service
              5285 Port Royal Road
              Springfield, VA 22161
              Telephone: 703-487-4650
       The EPA Project Officer can be contacted at:
              Industrial Environmental Research Laboratory
              U.S. Environmental Protection Agency
              Research Triangle Park, NC 27711
                                        •ft U.S GOVERNMENT PRINTING OFFICE; 1984 — 759-015/7773
United States
Environmental Protection
Center for Environmental Research
Cincinnati OH 45268
Official Business
Penalty for Private Use $300