4>E PA DIRECTIVE NUMBER^9523:^(84^'y.W; -\
- . " j
TITLE' Guidance on" Petroleum Refinery Waste Analyses for
• ' Land Treatment" Permit Applications (List of 89
Hazardous Constituents Possibly Present in Refinery
-'•"- ' Wastes and Column'Clean Up-Procedure) . , -
APPROVAL DATE: '5-24-84 .;. \v-;:-":,-•. •-,: ;
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EFFECTIVE DATE: 5-24-84;-,.;^: -^ _ V . :
'ORIGINATING OFFICE: office-of "soiid^3"--^ '
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D DRAFT
STATUS:
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REFERENCE (other documents):
A- Pending OMB approval
B- Pending AA-OSWER approval
C- For review &/or comment
D- In development or circulating
headquarters
DIRECTIVE DIRECTIVE L
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PART 270 SUBPART B — PERMIT APPLICATION DOC: 9523.02(84)
Key Words: Refinery Waste
Regulations: 40 CFR 270.14(b), 270.20, 270.20(a), 264.13
Subject: Guidance on PetroLeum Refinery Waste Analyses for Land Treatment
Permit Applications (List of 89 Hazardous Constituents Possibly
Present in Refinery Wastes and Column Clean Up Procedure)
Addressee: Hazardous Waste Permit Branch Chiefs, Regions I—K
Originator: John H. Skinner, Director, Office of Solid Waste
Source Doc: 1/9523.02(84)
Date: 5—24—84
Summary:
OSW developed a list of 89 hazardous constituents or groups of constituents
identified as possibly being present in petroleum refining wastes (K048—KO52):
Permit writers should use this list as a guide in determining which constituents
should be addressed in the up—front waste analysis and waste analysis plans for
Part B applications that propose land treatment of petroleum refinery wastes.
A permit applicant may refine this List by providing detailed evidence that
certain hazardous constituents are not present in the listed wastes at that
particular refinery.
OSW developed a draft document entitled “Handbook for the Analysis of
Petroleum Refinery Residues and Wastes,” which Is currently being finalized.
it includes a “draft column clean—up procedure” to assist permit writers and
applicants in analyzing for specific organic constituents in petroleum
refinery wastes. This method is used specifically to separate semivolatile
aliphatic, aromatic, and polar compounds in the waste matrix and should be used
by experienced residue analysts only. Volatile compounds are determined by
using method 8240 with PEG Extraction. Test method 3050 should be used for all
metal analyses. (Both of these are in SW—846.)
The EP toxicity test data described in the document do not have to be sub—
tnitted in the land treatment permit application. The total metal concentrations
should be reported’ in the application. Also, certain of the analytical quality
control procedures described may not be sufficient for RCRA permit waste analysis
plans.
Because it is important that waste analysis data EPA requests for permitting
and delisting be consistent, this list of 89 hazardous constituents is similar
to that used for refinery delisting actions. OSW is also collecting additional
information on non—Appendix VIII constituents. These compounds nay be added to
Appendix VIII in the future, and permit applicants are encouraged (although not
yet required) to provide information on these waste constituents.
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95fl 0’ (8’
-- o c’cU flTED STATES ENVIRONMENTAL PROTECTION AGENCY
Guidance on Petroleum Refinery Waste Analyses for Land
a Treatment Permit Applications
John Skinner,
Office of Solid Waste 71
_ hazardous Waste Permi ’JBranch Chiefs,
Regions t-X
Introduction
The purpose of tnis memo s to provLde permit writers
guidance on evaluating petroleum refinery waste analyses suomitted
in land treatnent permit aopl cations. . List of Apoenc x
VIII hazardous constituents suspected to oe present in petroleum
refinery wastes and a special analytical method for refinery
4astes are provided.
Background
The general ?art B information requirements specified
under 270.l4(b) require the suorrtittal of (1) chemical and
physical analysis data on the nazardous wastes to be handled
at tne facuLty uncludlng all data that must e known to treat,
store, or duspose of wastes properly in accordance with Part
26 , and (2) a copy of tne waste analysis o an. In addition,
cne sDecu:Lc unrormation requIrements under 27O.2O recu r an
owner/operator of any faciluty tnat includes a land treaent
un:t to suomit ‘a list of hazardous const ents reasoneoly
e’
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2
The evaluation of tnese .ppendix Vilt subsets for each Land
treatment aoplication has been difficult due to the lack of
puclished information on specific organic compounds in refinery
wastes, and also due to the variability of 4aste coaracteri.st cs
4ithLn the refinery industry. owever, 05W has gathered sufficient
information from PA research studies, in—house waste studies
and analyses, and ref nerv process evaluations to develop a
conservative List of hazardous constituents that are suspected
to be present in petroleum refinery 4astes. This list s
provided in Attachment 1. This list should ce used y permi:
writers as a guide n determining nich Constituents may and
may not e m nated from considerat:on when comoictiog 4aste
analyses for a Land treatment permit apolication. i.cdit onal
explanation of the derivation and use of this li s p’ iided
be Low.
Derivation and Use of LLs :
The list of hazardous constituents suspectea to ce present
in refinery wastes as cerived from a review of Data Ofl petroleum
refinery wastewater and sludge characteristics from the folLowing
sources: (1) literature, particularly ?A research retorts;
(2) to—house waste analyses comoleted ty ?A research laooratorias;
(3) oreiimina:v data from toe 05W refiner-i waste studi; and
(4) an evaluation of cetroleum reftoery oro:esses. AlcoOuç
r-lese four sources were used, t:ie data oase ri specific zarcc
or;anLc const t enes in sl ages as still L— ited. Corstderao e
e igh.t . as placed on astewater data as nccators of sludge
coaracteristics (e.g., ?I separator sludge..
Also, the list in ttachment 1 is a enertc List ceveio ed Dv
ComDining waste analysis data on all five listed ref Loery as :es
(<048 — 052). Due to toe lack of extensive data, no attempt
as made to differentiate bet.4een toe coaracters: cs of these
Ei;e refiner’, wastes. Until suEfic ent information is availazie
to allow development of separate lists for each waste, toe
attached List should be considered a;pl icaole to dissolved atr
fLotation float ( KO4S) , slop oil emulsion solids ( O49) , oeat
exchanger bundle cleaning sludge ( O5O) , separator slLc;e
(<051), and leaded tank Doctoms ( 52)
To compensate for the Limited data base and var:ao:Litv among
refineries, the attached list is pur oseL, comprenens ;e.
it includes a total of 39 hazardous const :uents or ;rouPs
of constituents (e.g., trichlorobenzenes). All oc these con-
stituents have teen identified as oosst’blv :eLng Present tO
toe aoove referenced wastes. Many of toe compounds on toe
list may be present at low concentrattons and otners -nay ct
te present at all in certato wastes at some ref ioer:es.
The permit writer should use the attacned L:st as a
to toe ;ppendi- ‘ittL constitjents that should te adcressec
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the up—front aste analyses arid waste analysis 1aris for ?ar 3
applications that propose land treatment oE petroleum refinery
wastes. A permit applicant may further refine this list by
providing detailed evidence that certain hazardous constituen g
cannot be present in the listed wastes at that particular
refinery. In most cases, however, waste analysis data on the
constituents listed in Attachment 1 will be necessary to make this
showing.
Analytical ‘ lethods
To assist in the analysis for specific organic ccnst:t ents
in petroleum refinery wastes, OSW has developed a column cleanup
procedure nicn s prov ced Lfl tachment 2. This draft rnet cc
is used specicicallj to se ara:e sem1volat le aliphatic, aromatic,
and polar compounds in the waste matrix. The method should oe
used only 5 y experienced residue analysts. Volatile cornpouncs
are determined using Tietnod 24O 4ith P G (tetraglyme) xtraction.
Test method 3050 shoulc be used for all metal analyses. These
methods are described in SW—846.
Relationship to DelLstL g end Listing Efforts
Finally, the attached list is consistent with the waste
analysis inEo ation chat ?A has requested from del s ing
petitioners. Many petroleum refinery operators who are re aring
Part s applications for land creac ent fac:licies also have
suomitted delist ng Petitions to trie Agenc for one or cre f
their wastes. It is mpcrtent chat the as:e analisis data
requested oy the Agency for permitting and :elisting e ccns s:en:,
although cnere may be differences in the ex:ent of cata necessary
Ln certain cases. Therefore, tne list of . ppend VIII ccnsc’ e :s
?rovided in Attachment 1 is also being used in refinery delis: ;
actions. Add t onel iriformat on on nçn—Apoendi 7111 const:tuertts,
however, is being collected as part of OSW’s new daste assessment
and listing efforts for petroleum refineries. These compounds,
h ch are 1 sted at the end of Attachment 1 for your infor ac or,
may oe added to Appendix VIII in the future. Altnough it is
not required at this time, permit applicants shoulo be encouraged
to provide information on these .4aste constituents.
If you have any questions on tne l st ng of spec f:c
hazardous constituents n Attacrirnent 1 or on cne recommencec
test methods, please contact Ben Smic (382— 179l) of the Jaste
Identification Branch. Other questions pertaining to tne se
of the above ;uidance in permLttlng land treatment fac:lit es
should e directed to ‘dike Elynn (382—4489) of t. e Land Dis csal
Branch.
Attachmets
cc: Jack Lehman Matt Straus
Fred Lindsey Bruce Weddle
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ATTACHMENT I
Appendix ‘it [ I Hazardous Constituents SusDected to be Present in efinery astes
W*Acetonitrile (Ethanenitrile)
**Acroleln (2-?ropenal)
Acry1oni tn le (2-Propenerii tn le)
Ani ii ne (Benzenarni ne)
Antimony
Arsenic
Ba ri urn
Benz (c) acnidine (3, —Benzacricine)
Benz (3) anthr3cene (1,2- enzantnr3c3ne)
r*Benzene (Cyclohexatniene)
Benzenethiol (T:iioohenol
Benzidine (I,l-Bipnenyl-4,AThiamine)
3enzo(o)f1uor ntnerie (2,3-8enzof1uor nthene)
Benzc(j)fluor3nthene (7,.3- enzof1’jorantnene)
Benzc(a)oyrene (3,4—BenzoDyrene)
BerTzyl cnlonice (Benzene, (criloromet. y1)-)
Beryi 1 iuni
Bis (2-chloroethyi ) etner (Etnane, I ,I.-oxybis (2-cnloro—)
Bis (2—cnioroisopropyl) etner (ProDane, 2,2-o
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2
**Di chi oropropane
Dichioropropanol
Diethyti ohthalate (1,2—Benzenedicarooxylic acid, diethyl ester)
7 ,12-Oimethyl -benz(a)anthracene
2,4—Dimethyiphenol (Phenol, 2,4—dirnethyl-)
Dimethyl phthalate (1,2-Benzenedicarboxylic acid, dimethyl ester)
4 ,6—Dinitro—o—cresol
2,4—Dinitrophenol (ohenol, 2, t —nitro—)
2,4—Din,trotoluene (Benzene, l.-rnethyl -2, —dinitro—)
Di-n—octyl phthalate (1,2-Benzenedicarboxylic acid, dioctyl ester)
**1,4_Dioxane (1,4—Diethylene oxi e)
1,2-Dipnenylhydrazine ( ydrazine, 1,2-dionenyl-)
* cthyl eim,ne ( zr idine)
‘Ethylene oxiae (Oxirane)
Fluorantnene ( enzo (j,k) fluorene)
* Forrna 1 dehyde
ydrogen sulfide (Sulfur hydride)
!ndeno (1,2,3-cd)Dyrene ( i0(1,2-pnenylene)pyrene)
Lead
4ercu ry
Metnanetniol (Thiometnanol
3-Metnylcrilolanthrene (Senz(j )aceantnrylene, 1. ,2-dihydro—3-methyl-)
W Methyl ethyl etone (ME:<) (2-3utanone)
Naontnal ene
Ni c el
D-Ni roanilhne (Benzenarnine, - —rii:ro—)
Nltrooenzene :senzene, nitro-)
- —NitrooT1enol ( henol,pentacn oro-)
?entacnloroonenol (?henol, oentacnloro-)
Phenol (3enzeie, nydroxy-)
yri i ne
Sc len i urn
‘ etrach]oroern, ar es
vrr.etracnloroetnylene (tnene, 1,1,2,2—tetra chioro-)
Toluene (Benzene, rnetriyl-)
Tri cr1 orooenzenes
T?Tri cr1 oroethaies
**Trichloroetnene (Tricriloroethylene)
*Tr, chiorophenols
Vanadium -
V any of these grouos of CCrnDOundS are found, tie specific
isomers listed in Appenaix ‘u N snould be identified.
Use Test ‘ ethod 32 0 for tiese volatile compounds.
Use Test Method 3050 in SW—a46 for all metals; see
Attachment 2 for semivolatile organic compounds.
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1ori-Accendix 11 _ NI Constituents of Concern (may be added to 4oo. vt:fl
Cobalt Indene
1-Methylnapt ia1ene 5 -Nitro acenaphtherie
Stjrerie uirio1ine
Hydroquinone Phenanthrene
Antnracene Pyrene
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.ATT? C MENT 2
Column Cleanu of ?etroleum c’Jastes
Introduct ion
The Eollow ng procedure is intended for appL cat on to tne
analysis of semivo1at le organic compounds ifl oilj waste
samples. tts app1 cation s necessary n those cases nere
the conventional cleanuo procedures Hethods 3510, 3520,
3540, 3550) faiL to orov ce suitaole cecection ii i s (aoorox—
mate1y 100Dm) for the sem:iotac:Le co ounds scecLfLec Ln
Aachmen 1. Analysis of ne ciear.ec—UD e
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a) In Section 7.6, the organic and aqueous pneses are both
treated as containing com ounds; and
5) Section 7.15 i11 not be necessary.
The aqueous phase, when transferred to organic solvent after
Section 7.13, will contain acidic compounds. The organic
phase contains basic and neutral compounds. I-i most Lnstances,
the acidic fraction will oe clean enougri for GC/MS analysis.
The base/neutral extract, however, may require further cleanup.
Thus, a cleanup procedure has been devised for oase/neutral
extracts that minimizes tne nterferences caused oy h ;h
concentrations of ali natic and polimeric ater als.
lthougn the cleanup procecure is thoroughly ‘tescrioec i
the next section, one generally roceeds as follows. The samo.e
is subjected to cleanup oy lac ng a re resentative aliquot
of the sample on an alumina column and su cessively eluting
with hexane, metnylene cnlor de, and 5 iiethy.I. ether to yie d
3 fractions containing the al nat c (hexane fraction), aromatic
(methylene chloride fraction) and polar compounds (ether
fraction). The methylene cloride fraction is then concentrated
to aoout 1 1. and then iS analyzed oy GC/MS for the cornoouncs
of interest. The nexane concentrate can be screened oy
CC/MS to deter iine if ccmoounds were eluted into the he ane
fraction. owever, t is usuallj s ilt not ce rec utrec.
o1ar coripounds are of nteres , tne ether rac: on s aiso
an a I /ze c.
Quantitation of tne semivolatile consti:.ents i t:ac me t L
is to oe pe for ed using the reverse searc :ec inicue.
Additionally, tentative identification snoulc oe attemotec
for the ten organic compounds detected at tne highest concerL—
trations. Ident ifications should oe made via a for ar
search of cne ?A/Nt mass soectral liorary. Concentratiors
should be ap rcx mated by comoar son of the com ound resoo se
to tnat of toe closest eluted inter-ial standard. Procecural
olank, rnatrix soike, and duplicate should ce analyzed for
every batch of samples.
ccuracy and precision control cr.arts snoul: :e a:- ta ec
for indicator constituents. The oercent recovertes of soi .ec
Lurrogate standards for a given sample type sncu o oe plott c
versus sample identification numoer. Tacle 1 ccnta ns 1 st
of the surrogate compounds to oe employed for t e anaLysis of
semivolat le organic compounds, anc recovery limits. ecoveri
limits are oased upon obtaining a final extract suffic entl,
clean, suco that the surrogate compounds snould oe present at
50 pm or higher in the extract. if dilution of tne sample
still required, detection of the surrogates may oe : ff cul:
and the associated recovertes imorecise or non—ex:stant.
Such samples snould oe sPiKed with higner surrogate Leve
anc resuojecteo to toe cLeaflup rocecure.
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Table 1. Surrogate Standards for Semivolatile Organic
Compound Analysis
Recovery Limits
Acid surrogates
phenol—d 5 40—115%
2_f luorophertol
2,4, 6—trioromoonenol
3ase/neutra 1 surrogates
mu. trooenzene—d 5
3—Eluorooi neny1 50—120%
ter ohertyl—d14
acrid e—dg
ovrene—d 10
The precision control chart should consist of the ercenc
difference for LncLcator constLtuent concentration determined
vi dupLicate sam les of a ;:1e1 sample tv e versus sam 1e
enc f cat or nu oe rs.
Column Clean N of ?etroleum astes
Scooe and op1icat on
This -nethod is used to cLeanup samples conta rting h ;
Levels of al onat c hydrocaroons, suc as 9astes from etro1eum
refic ing. tt is used specifically :o seoarate aliohatLcs,
aromatics, and polar compouncs in the . aste rnatri . This
method is aooL caole to AP separator sludges, rag oils, slop
oil emulsion, and other oily ‘wastes derived from oetroLeLm
re 1n1ng. This method is recommended for use only oy or
under close supervision of exoer enced analysts.
Summary of 1ethod
Take a 200 -ng aliquot of tne ‘4aste/etnyierte chiorice
concentrate from step 7.13 of 1 etnod 3530. Dissolve tne
aliquot in hexane and sci’ e 4it 10mg each of d 9 —acr c ne,
d 5 —rtitrooerizene, d 5 —ohenol, 2—Eluorob ionenvi, tr:oromcDnertoi,
d14—terphenyl, 2—fluoroohenol, and clo—pyrerte. Aool t .e ixture
directly to the alumina column.
The column s eLuted secuentiail7 .qlth he
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GC/MS. If pyrene or terphenyl is recovered at less than 30%,
the orocedure should be reoeated.
I nterferences
Matrix interferences sill li’ ely be coextracted from the
sample. The extent of these interferences will vary consideraoly
from waste to waste depending on tr e nature and divers j of
the particular waste being analyzed. The use of adoitional
cleanup extractions can be used as iecessary for spec fic
compound Ldentificat on and quantLtation.
? .oparatus
Glass Column: 30 cm long ‘< i cm I.D. with glass frit or
;lass wool anc stop clock.
luminum eighiig ooats: Approximately 2 in. in diameter.
nalytical Balance; Capable of weighing to r0•5 mg.
Concentrator Tube, KD, 10 ml
Eia orat v FLask,
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Procedure
Weigh out 10.0 gm of alumina arid ado to t e chr:matcgraoh c column
that is filled to about 20 .rnL with hexane.
Allow the alumina to settle arid then add 0.5 gm sodium sulfate.
Let the solvent flow such that the head of li ui in trte column
is about 1. cm above the sodium sulfate layer. Stop the flow.
Add tne alicuot ecu va1ent to 100—200 mg of matar l.
start the fI and elute :t 13 ml of eane. Collect the
fluent vi a 50 oeaker. Laoel tnis Eract on ‘ 1 al pnac cs’.
1ute the column . ‘itn 100 ml of methylene ch1or oe and collect
the effluent n a 250 ml oeaker. Laoel ‘arornac.ics”.
lute the column itn 100 ml of diethyl etner and collect the
effluent n 3 250 ml oeaker. Laoel ‘7olars’.
4ei;h three sample ooats to the nearest 0.5 mg. Reduce tne
;olume of eacn fraction using tne KDs to Detween 1. and 5 ml.
ecord tne volume of each and Dlace 1/2 of each sam Le in
r SDeC t IJe boat.
vaoora-e-e : e IL:uic in each ooac under a ntle stream of
nitrogen. ewei;h eacn joat and recoro t eighc of eacn ctor.
Calculate the dei;ht of eacn fraction as a orooortion of :ne
total sample. For example, frac: cn I :s 5 .3 mc, fraction 2
is 25.4 mg, and fraction 3 is 35.3 trig.
Calculate the amount of sampLe in the fractons anc adjust
the volumes so irijectlon dill permit determination of var:ous
components on scale
12.7 mg/2500 ii = 5.1 ug/uL
Dilute each of the three fractions oo at ed ov a ratio so
t at the sample enter:ng :ne cacillary column :ces not e’ceec
2.5 ug. or example, Lf tne calculated deL;nt of the fract on
as a proportion of the total samole :s 12.7, anc tne amount of
sample in the fractions is 5.1 ug/ul as in the above e’
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chronic labor3tory contamination. The blank samole shoula be
carried through all stages of the sample eparat1cn and measure—
rnent. Standard quality assurance practices should be used
with this method. Laboratory replicates should be analyzed
to validate the precision of the analysis. Eortif ed samples
should be carried througn all stages of sample preDaratlon
and measurement; tney should ce anlayzed to validate the
sensitivity and accuracy of the analysis.
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