Laboratory Assessment Of Potential Hydrocarbon Emissions From Land Treat- Ment Of Refinery Oily Sludges


                    United States
                    Environmental Protection
                    Agency
Robert S. Kerr Environmental
Research Laboratory
Ada OK 74820
                    Research and Development
EPA-600/S2-84-108 July 1984
c/ERA          Project  Summary
                    Laboratory Assessment of
                    Potential  Hydrocarbon  Emissions
                    from Land  Treatment of Refinery
                    Oily  Sludges

                    R.G. Wetherold, J.L. Randall, and K.R. Williams
                      Volatile organic emissions were
                    characterized when oily petroleum
                    sludges from refineries were incorpo-
                    rated in soils under controlled  labora-
                    tory conditions. The  sludges tested
                    included three of the five listed hazard-
                    ous wastes  for the refining industry:
                    dissolved air flotation float, slop oil
                    emulsion solids, and API separator
                    sludge. The volatile components of the
                    sludges were first identified. Then the
                    effects of air temperature and humidity,
                    wind speed, soil type, temperature and
                    moisture, sludge loading and volatility,
                    and method  of waste application were
                    studied. The volatile components iden-
                    tified in the sludge were also present in
                    the emissions from  the soil-waste
                    mixtures. The quantity of emissions
                    was most affected by the sludge volatil-
                    ity, sludge loading, application method,
                    and atmospheric humidity; the cumula-
                    tive emissions at a given period of time
                    could  be correlated with these opera-
                    tional  variables. The emission  rate  or
                    level was not significantly affected by
                    soil type or soil moisture. An expression
                    for estimating the rate of emissions as a
                    function of elapsed  time after applica-
                    tion could not be developed from the
                    data. Although every effort was made
                    to simulate actual land  treatment
                    conditions, it was not possible to apply
                    these  laboratory findings  directly to
                    predict full-scale results.
                      This Project Summary was developed
                    by EPA's Robert S. Kerr Environmental
                    Research Laboratory. Ada, OK, to an-
                    nounce 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). The research effort was jointly
funded by the US EPA and the American
Petroleum Institute.

Introduction
  Land treatment has been used exten-
sively by the petroleum refining industry
to attenuate oily sludges, predominantly
on company property.  In the current
process of renewing  land treatment
permits, there has been an increasing
interest in addressing the characteristics
and magnitude of volatile organic emis-
sions occurring in land treatment opera-
tions.
  This laboratory study was performed to
assess the atmospheric emissions from
the land treatment of refinery sludges,
particularly those listed as hazardous
wastes for petroleum refining in 40 CFR
261.32 and which are routinely land
treated by the  industry. The  wastes
studied were API separator sludge, slop
oil emulsion solids, and dissolved air
flotation (DAF) float. The magnitude and
characteristics of the emissions and the
variables affecting them were  investi-
gated using sludges and soils collected
from participating refineries.

Procedures
  The volatile organic constituents of the
sludges were identified by using a
purging device, trapping the emitted
organics, and performing analyses by gas
chromatography 'mass spectrometry

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(GC/MS). A laboratory land treatment
simulator apparatus was constructed to
measure air emissions from soil/waste
mixtures while controlling and mea-
suring air velocity, humidity, and tem-
perature, and soil temperature and mois-
ture. A series of tests was conducted with
this simulator using eight soil samples
and nine sludges obtained from eight
participating refineries. Initially, nine
variables were evaluated with the
simulator (Table 1). Based on these
preliminary studies, the five variables
indicated by asterisks in Table 1 were
chosen for further intensive study. Table
2 is the experimental matrix for evaluating
these variables, where one variable was
studied while holding the four others
constant. The remaining variables in
Table 1 were held constant: air and soil
temperatures at 90°F, wind velocity 3
mph, and sludge application mode being
to the surface. Emissions measurements
consisted of total hydrocarbons as
measured by a Byron Instruments 401
Total Hydrocarbon Analyzer and indivi-
dual compound identification by collec-
tion in steel cylinders and dual detector
GC analysis using normalized toluene
response as the indicator of the compound
present.1

Results and Discussion
The sludge characteristics are presented
in Table 3 (nonspecific organic content)
and in Table 4 (specific organic compounds
identified). Fifty-two runs were made
with the land treatment simulator. Statis-
tical interpretation identified the param-

Table 1. Operational Variables Studied
with the Land Treatment Simula-
tion Apparatus
Table 3. Nonspecific Organic Composition of Sludges
*Sludge Volatility
Application Mode
"So/1 Loading
Air Temperature
Soil Temperature
*Soil Type
*Soil Moisture
*Air Humidity
Air Flow
Sludge
SL-11
SL-12
SL-13
SL-14
Type
API Sludge
DAF Float
Slop Oil
API Sludge
Oil &
Grease
(wt. %)
22
1
2
2
Volatilized
hydrocarbons"
(PPM /ml sludge)
820
70
125
103
Sum of volatilized
compounds
identified''
(ug/gm)
6,100
760
2,910
850
"A verage total hydrocarbon concentration in vapor phase over 4 hrs. nitrogen purging using 1 ml
sludge (expressed as hexane).
"Total concentration of emitted compounds identified by GC/MS (see Table 4).
Table 4. Major Organic Compounds Identified in Sludges

Sludges
SL-11
SL-12
SL-13
SL-14
Compound
Benzene
Toluene
M/P-Xylene
0-Xylene
CyBenzene
CyBenzene
Napthalene
Anthr./Phen.
C9-H.C.
(alkane)
Ciz-H.C.
(alkane)
C,i-H.C.
(alkane)
Cn-H.C.
(alkanej
(pristane)
Cig-MC.
Cso-H.C.
540
1,700
7OO
330
/, 7OO
890
230
150
13O

140

31
2
32
58
58
28
150
120
34
20
30

26
NM
18
98
11O
SO
4OO
40O
350
1,100
14

210

4O ^
16
5
14
30
16
160
140
64
92
36

J2O

28
14
eters having the most significant affects
on emission levels: sludge volatility,
sludge loading, and air humidity. The
emission rate or level is not significantly
affected by type of soil or its moisture
content. In general, the results showed
that the more volatile components
identified in the sludges are emitted to the
air, specifically C9 - Ci2 alkanes, xylenes.
C3-benzenes, toluene, and benzene. The
more volatile compounds were present in
Table 2.
Experimental Matrix for Evaluating Operational Variables

Sludge ID
Sludge Volatility:
Low
Medium
High
SL-12
SL-13. SL-14
SL-11
Soil ID
Soil Type:
Sludge Loadings:

Soil Moisture:
Air Relative Humidity:
D-1
D-8
D-7
Silty sand
Silty clay
Sandy Silt
5 levels (0.05 - 2.0 Ib oil/ft2 soil)

5 levels (5 - 25 wt. %)
3 levels (30 - 80%)
the emissions at relatively higher con-
centrations compared to the concentra-
tions in the sludges that were the
respective sources of the emissions. The
cumulative emissions at a given period
in time (four to seven hours after
application) can be correlated with sludge
volatility, sludge loading, and atmospheric
humidity. During the two phases of the
study, the hydrocarbon volatilization
ranges, expressed as % oil content in
sludges applied, were 0 - 3.6% after 30
minutes and 0-6% after 4 hours applied.
An expression for estimating rate of
emissions as a function of elapsed time
after sludge application could not be
developed from the data obtained.
Alt of the specific organic compounds
identified in the emissions from each of
the runs is tabulated in the report to-
gether with the measured concentra-
tions in parts per million by volume
expressed as carbon (ppmv-C).

References
1Cox, R.D. and R.D. Earp "Determination
of Trace Level-Organics in Ambient Air

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by High-Resolution Gas Chromatogra-
phy  with  Simultaneous Photoioniza-
tion  and Flame lonization Detection,"
Anal. Chem. 54 (13) 2266, November,
1982.
R. G. Wetherold, J. L Randall, and K. R. Williams are with Radian Corporation.
  Austin, TX 78766.
Fred M. Pfeffer is the EPA Project Officer (see below).
The complete report, entitled "Laboratory Assessment of Potential Hydrocarbon
  Emissions from Land Treatment of Refinery Oily Sludges," (Order No. PB 84-
  209 766; Cost: $13.00, subject to change) will be available only from:
          National Technical Information Service
          5285 Port Royal Road
          Springfield, VA22161
          Telephone: 703-487-4650
  The EPA Project Officer can be contacted at:
          Robert S. Kerr Environmental Research Laboratory
          U.S. Environmental Protection Agency
          Ada, OK 74820
                                                                            U S. GOVERNMENT PRINTING OFFICE, 1984 — 759-015/7755

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