Table Of Contentby
James R. Payne and Charles R. Phillips
PETROLEUM
SPILLS
IN THE MARINE ENVIRONMENT
The Chemistry and Formation
of Water-In-Oil
Emulsions and Tar Balls
Boca Raton London New York
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First published 1985 by CRC Press
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Library of Congress Cataloging in Publication Data
Main entry under title:
Payne, James R.
Petroleum spills in the marine environment.
Bibliography: p.
Includes Index.
1. Oil Spills. 2. Emulsions. 3. Petroleum–
Biodegradation. I. Phillips, Charles R.
(Charles Robert), 1951– II. Title.
GC1085.P33 1985 628.1‘6833 85-13065
ISBN 0-87371-058-4
A Library of Congress record exists under LC control number: 85013065
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ISBN 13: 978-1-315-89638-0 (hbk)
ISBN 13: 978-1-351-07548-0 (ebk)
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ECAFERP
This book nsatneserp overview of the current understanding of water-
in-oil emulsion behavior. It is desab on a review originally prepared sa a
contribution to the NAS Petroleum in the Marine Envi ronment/Update
Workshop held in November, 1981. It may or may not reflect the concen-
sus of the workshop participants or the National Academy of .secneicS A
summary publication of those proceedings saw published in 1985; how-
,reve are there currently no plans to publish the background papers per .es
Reviews of recently published ,,ssgeniidtuitss and investigations ta spills-
of-opportunity, sa well sa results of recent arctic and subarctic oil weather-
ing experiments and observations on the behavior of crude oil in the
presence of ice added been have to them anuscript to provide coverage of
important hcraeser completed between 1981 and May, 1985. This new
book contains a tremendous amount of information of interest to petro-
leum companies, ,stsitn e,iscrseenigne environmentalists, chemical and
biological oceanographers, and oil spill coordinators, response and this
book reflects the authors' desire to make contents its available to a wider
audience.
When crude oi sI or refined petroleum products era released ta ,aes they
are subjected immediately to a wide variety of weathering .sessecorp
sessecorp esehT esuac significant segnahc in the rheological properties of
the oil, lareves orders of magnitude sesaercni in viscosity, factor of two
segnahc in interfacial tensions, surface apapnrde ciable (5 - 10%) segnahc
in oil density. All of eseht alterations have important implicationsf or the
subsequent spillc leanup or containment .ygetarts The increase in volume
due to incorporation of water in emulsions can esuac further problefmosr
storing the collected product.
Specific laboratory studies on water-in-oil emulsions with a variety of
crude and refined petroleum products are discussed in detail in Chapter
2. This information, along with data on the component concentrations of
,xaw ,enetlahpsa and other surface-active ,slairetam facilitates reliable
predictions on whether or not a particular crude or refined product will
form stable a emulsion. Chapter 3 covers esac histories of real spill events
with discussion of specific studies of water-in-oil emulsions and chtehme-
istry of emulsion formation and behavior. The chemical composition of
,sl lraabt their ,e t,asfecruos and globadli stribution are dessucsid in Chap
ter 4. Chapter 5 is na overview of recent attempts to model water-in-oil
emulsification behavior. Chapter 6 stneserp a summary and critical cita-
tion review for ysae reference to additional details on particular topics
presented in the other chapters.
er aeW ot lufetarg a fo rebmun ,sdnei r,fseugaelloc dna sreep who evah
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tn essteirp .mrof ehT original tfard fo tephitrcsunam saw deweiver by
s ermoasJseforP N. reltuB fo dravraH University dna Mr. drareG .P
iravenaC fo noxxE hcraeseR dna gnireenignE .ynapmoC riehT stnemmoc
dna snoitseggus era d eytlatiaceerrgppa dna eva hneeb detaroprocni
throughout eht t xeertehw .etairporppa eW tsum emussa ,ytilibisnopser
,revewoh rof yna snoissimo introduced in reviewing eht rehtar evisnetxe
efro uttnauroemtail on published eht .tcejbus
eW era ylpeed detbedni to G. Daniel ,bbaNcM ,.rJ ,h csaebmmaajL
treboR ,gniddeR dna William ykswalpaP rof sesylana of selpmas from
anstisaK ,yaB ,aksalA dessucsid in eht .koob eW would osla like to knaht
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erew osla latnemurtsni in obtaining hcum of e hetrutaretil cited dna in
compiling eht suoirav secnerefer rof eht bibliography. naJ seehroV si
rof deknaht reh ecneitap dna ecnetsisrep in waiting eh trof original -unam
eh trof tpircs SAN weiver dna rof reh tnemegaruocne in prompting PRJ ot
dna etadpu publish tner reuhct noisrev fsoiht .txet
Oil gnirehtaew smargorp hcraeser detaler to eht tcejbus of siht review
evah neeb dednuf (wholly ro in trap ) yb NOANOffice of Pollu- Marine
tion ,tnemssessA tcartnoC No. CAR08AN 1000 ,3 evitarepooC hcraeseR
in eht gnitagitsevnI COTXI I ;tuowolB NOANOuter latnenitnoC flehS
latnemnorivnE tnemssessA ,margorP tcartnoC No. 253-200-7-30 1 ,3 -perP
fo noitara a weiv eeRrutaretiL on eht etaF dna gnirehtaeW of muelorteP
sllipS in eht Marine ;tnemnorivnE yb eht uaeruB fo dnaL tnemeganaM
hguorht ycnegaretni tnemeerga with eht National cinaecO dna -omtA
cirehps ,noitartsinimdA sa trap of eht Outer latnenitnoC flehS -norivnE
latnem tnemssessA ,margorP tcartnoC .oN ,81000CAR08AN Multivariate
sisylanA of Oil gnirehtaeW in eht Marine uS-tnemnorivnE b ;citcrA dna
yb NOANOuter latnenitnoC flehS latnemnorivnE tnemssessA ,margorP
tcartnoC No. 18 ,26000-CBA-3 tnempoleveD of a evitciderP Model eht rof
fo gnirehtaeW Oil in eht ecneserP fo aeS .ecI
semaj R. ,enyaP ,.D.hP dna selrahC .R Phillips
April ,8 1 985
Division fo Applied latnemnorivnE secneicS
ecneicS noitaroproC lan osintoaintraectinlIppA
aL ,alloj California
semaJ .R enyaP si a roineS roineS/tsimehC tcejorP reganaM in eht Divi-
nois fo Applied latnemnorivnE ,secneicS ecneicS snoitacilppA -anretnI
tional ,noitaroproC aL Jolla, California. He deviecer sih .D.hP in -simehC
yrt eht morf University nisnocsiW fo - ,nosidaM dna a .A.B with sronoh in
yrtsimehC California from etatS University- e.HnotrelluF saw National a
setutitsnI fo htlaeH larotcoderP wolleF ta nisnocsiW dna desuc osfih
hcraeser stseretni on emyzneoc/emyzneopa snoitcaretni dna eht sisehtnys
fo emyzneoc ,sgolana including dehcirne-C31 vitamin ,6-B rof C" raelcun
citengam ecnanoser seiduts of emyzneoc/emyzne evitca etis .sexelpmoc
retfA etaudarg ,l oeohhcs deviecer a sdooW Hole cihpargonaecO itsnI -ut
tion larotcoD-tsoP ,pihsralohcS erehw eh kootrednu hcraeser on eniram
humic ,sdica incorporation of muelortep snobracordyh into eniram -llehs
,hsif dna eht ecnetsisrep dna msilobatem of sBCP in eht retaw column fo
eht North .citnaltA
retaL hcraeser sah deretnec on tnempoleved of yrotarobal sdohtem dna
emulov-egral retawaes gnilpmas smetsys rof noitceted fo level-ecart
,scinagro particularly muelortep ,snobracordyh in retawaes dna seussit of
detceles eniram .seiceps He snaaw invited tsitneics on eht NOAA pihs
,REHCRAESER gnitagitsevni eht COTXI I oilwell blowout in eht yaB fo
dna ,ehcepmaC lapicnirP rotagitsevnI of a raey-eerht yrotarobal dna field
dengised margorp multivariate a to provide sisylana dna retupmoc model
gnirehtaew m ufeolortep in .tnemnorivne eenhitram More ,yltnecer .rD
s'enyaP latnemirepxe dna modeling stroffe evah neeb dednapxe ot
include efho tsnoitcaretni spilled muelortep with aes eci rednu citcra
.snoitidnoc Other hcraeser stseretni include tnempolev efdo lacimehc
dna lairetcab serusaemretnuoc rof in situ punaelc of detanimatnoc ios ,sI
fo snoitaulave oil tnasrepsid ssenevitceffe in low wollerutarepmet ytinilas
,stnemnorivne dna SMICG sesylana of ecart level stnatullop deretnuocne
in enahtem sag yrevocer morf deppac landfills.
Charles .R Phillips is a ffatS tsitneicS with eht Division of Applied Environ-
mental ,secneicS ecneicS Applications International Corporation in La
Jolla, California. He received a B.A. in biological secneics from the Uni-
ytisrev of California, atnaS arabraB dna na .A.M in marine secneics from
naS ocsicnarF etatS University. Graduate hcraeser ta ssoM Landing Marine
desuc oyfrotarobaL on measuring dna the characterizing vertical flux of
organic particulate material in eht latsaoc environment. marine
hcraeser tneceR includes participation in Dr. s'enyaP oil weathering in
the environment, marine oil-in-ice dna experimental and oil-SPM model-
i ng ,smargorp ssenevitceffe tnasrepsid ,seiduts dna environmental moni-
toring and impact tnemssessa .smargorp Mr. ihP l lips sah CO-authored -ves
lare recent srepap on the environmental oil, of weathering na oil pollution
,xedni and the etaf of from hydrocarbons SCO oil dna sag development
smargorp in the marine environment.
TSlL FO SERUGIF
erugiF
1 Rheological Data Properties on the Prudhoe yaB Crude Oil Weath-
ering in the Wave knaT smetsyS 1 7
2 emalF lonization Detector-Temperature Programmed saG Chro-
matographic Analysis of depparT-xaneT Volatile Compounds tsoL
From hserF Prudhoe yaB Crude Oil After 1 Hour of Weathering
(With Turbulence) on retawaeS 26
3 Flame lonization Detector-Temperature Programmed saG Chro-
matographic Analysis of depparT-xaneT Volatile Compounds tsoL
From hserF Prudhoe yaB Mousse (80% Water) After 1.5 Hours of
Weathering (With Turbulence) on retawaeS 2 7
4 pxaarnTeT FID-GC Data on Sub-Arctic Volatile Component ssoL
From Prudhoe yaB Crude Oil and Mousse on Flow-Through -aeS
water serusolcnE in anstisaK ,yaB aksalA 28
5 Computer Generated stolP of Capillary FID-GC Data on Intermedi-
eta Molecular Weight Components Remaining in Prudhoe yaB
Crude Oil and Weathering Mousse Under Sub-Arctic Conditions on
Flow-Through retawaeS serusolcnE ta anstisaK ,yaB aksalA 29
6 Computer Generated stolP of Capillary FID-GC Data on Higher
Molecular Weight Components Eemaining in Prudhoe yaB Crude
Oil and Mousse Weathering Under Sub-Arctic Conditions on Flow-
Through retawaeS serusolcnE ta anstisaK yaB aksalA 31
7 Location of the IXTOC-I Blowout and Direction of Oil Slick -snarT
port in the Gulf of Mexico 58
8 Campeche IXTOC-I Oil Spill ;es iduerdCnapxE Wellhead Region
Showing Location of Turbid Water Boundary 62
9 Abundance Relative of Alkyl-Substituted Polynuclear Aromatic
Hydrocarbons in IXTOC Crude Oil Collected 211 Mile from the
Wellhead 71
10 Abundance of N-Alkanes (Relative to nC-20) in dehcaeB Mousse
from anugaL Madre ,)32-XIR( Mousse sekalF Collected 1 6 - 1 8 Miles
from the Wellhead 1-P( 3) during the GW ecreiP Down-Plume -narT
,tces and IXTOC Crude Collected 211 Mile from the Wellhead 72
11 Mousse/Oil Relative Viscosity of Ratio xiS tseT Crude Oils sa a
Function of Water Content 101
1 2 Corn puter Model-Predicted and Observed Time-Dependent Uptake
of Water into Ekofisk Oil sa a Function of Wind deepS and -aeS
etatS 103
TSIL FO SELBAT
Table
1 essuoM Formation stnemirepxE using a Variety fo hserF and Artifi-
cially Crude Weathered (Topped) Oils in ,yrotarobaL Outdoor tseT
,knaT and Field Experimental Spills 6
2 Other Oils Which Have Demonstrated Water-in-Oil Emulsion -neT
dency 9
3 seireS-emiT Water Column Concentrations of Dissolved and Dis-
desrep Hydrocarbons from hserF Prudhoe yaB Crude Oil and
Mousse Weathering on Flow-Through retawaeS serusolcnE (Turbu-
lent )emigeR ta anstisaK ,yaB aksalA 34
4 Inhibition of elbatS Mousse Formation by the Addition of Chemical
stnasrepsiD 36
S Chemical seidutS of Oil/Mousse Behavior in Major Oceanic Spills
and Blowouts 42
6 detceleS Component soitaR for the Dissected e lepsmsauSoM
dehcaeB a ntuagaL Madre (Station XIR 23) 73
7 Summary of raT Ball Distributions and Concentrations on the World
Oceans 84
8 yrammuS of dednartS raT Ball Distributions and Concentrations on
hcaeB secafruS 95
TABLE OF CONTENTS
Chapter
1. INTRODUCTION
2. LABORATORY STUDIES OF FORMATION AND STABILITY
OF WATER-IN-OIL EMULSIONS 3
Background 3
Specific Studies 5
Mousse Formation in the Presence of Ice 18
Identification of Emulsifying Agents Responsible for Mousse
Formation 21
Physical and Behavioral Properties of Water-in-Oil Emulsions 25
Evaporation 25
Combustibility 30
Breaking and Interaction of Laboratory Mousse with
Dispersants 33
Bacterial Utilization of Laboratory Generated Mousse 40
3. SELECTED CASE HISTORIES OF THE MORE DETAILED
CHEMISTRY STUDIES o): MOUSSE BEHAVIOR AND LONG
TERM FATE IN NEAR::eOASTAL AND OPEN OCEAN OIL
SPILLS/BLOWOUTS 41
Torrey Canyon 41
Tanker Arrow 43
Metula 46
Ekofisk Bravo Blowout 47
US/NS Potomac in Melville Bay, Greenland 50
Amoco Cadiz 51
IXTOC I Blowout, Bay of Campeche, Gulf of Mexico 57
Background 57
Observations at the Wellhead 61
Subsurface Transport and Weathering of IXTOC Oil 66
Personal Observations of Micro-Scale Mousse
Agglomeration 67
Fate of Stranded IXTOC Mousse Along the Southeast Texas
Coastline 7 4
Burmah Agate 76
Alvenus 77
Open Ocean Field Tests of Spilled Petroleums 78
Conclusions 81
ix
