I mpact Di f f er ent i at i on of Envi r onment al l y Fr i endl y ver sus St andar d

Cor r osi on I nhi bi t or Di schar ged into a Tr opi cal Mar i ne Envi r onment
James P Smith and Ian H Gilbert
Dyno Oil Field Chemicals Asia Pacific
43 Shipyard Road
Singapore
Jan Erik Solbakken
Dyno Oil Field Chemicals Norway
Edv. Gri egvei 3A
N-5037 Sol hei mvi k
Nor way
ABS T RACT
A compar at i ve ecot oxi col ogy i nvest i gat i on has been conduct ed usi ng fi el d speci f i c par amet er s t o assess t he
i mpact of resi dual cor r osi on i nhi bi t or, st andar d ver sus "green ", di schar ged f rom of f shore f aci l i t i es. Pr esent ed is a
model ed est i mat e of ecol ogi cal i mpact and ri sk associ at ed wi t h pr oduced wat er / cor r osi on i nhi bi t or mi xt ur es f rom
a l ow sal i ni t y- hi gh t emper at ur e di schar ge of 142 million L/ day i nt o an open sea envi r onment . I mpact is assessed
by ext r apol at i on of st eady st at e i ndi cat or t est speci es LCso cri t i cal body resi due (CBR) resul t s appl i ed to an
accur at e char act er i zat i on of r esi dent or gani sm non st eady st at e exposur e and cont ami nant load. Thi s
ext r apol at i on det er mi nes t he acut e and chr oni c i mpact of pr oduced wat er / cor r osi on i nhi bi t or mi xt ur e wi t h t i me.
These ext r apol at i ons are possi bl e usi ng an empi ri cal l y j ust i f i ed pr edi ct i ve comput er si mul at i on of t oxi cant ef f l uent
mi xt ur e di schar ged i nt o an open sea envi r onment t hat det er mi nes pl ume di sper si on, degr adat i on, di l ut i on, and
bi oaccumul at i on. The model ed si mul at i on f ur ni shes non st eady st at e CBR bi oaccumul at i on concent r at i ons t hat
pr ovi de an accur at e r epr esent at i on of acut e and chroni c mor t al i t y wi t h resul t ant PEC/ NEC ri sk at any gi ven
geogr aphi cal l ocat i on adj acent to ef f l uent di schar ge l ocati on.
Key words; bioaccumulation, biodegradation, inhibitor, half life, risk assessment.
I nt r oduct i on
E and P oper at i ons and speci al t y chemi cal suppl i er s spend a si gni f i cant amount of money and ener gy
compl yi ng wi t h bi odegr adat i on t est i ng r equi r ement s or r egul at or y speci f i ed t oxi ci t y t est s. Once compl et ed t he t est
resul ts are of t en appl i ed t o open sea dynami cs or i nl and est uari es. Unf ort unat el y, t he resul t s of t hese t est i ng
regi mes are ver y sel dom appl i cabl e t o real worl d bi o- dynami cs occur r i ng in ei t her bi ospher e. Thi s i s subst ant i at ed
Copyright
@2000 by NACE International.Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Conferences Division, P.O. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in U.S.A.
00333
CORROSION
2000
Paper No.
by t he fact that in very f ew cases are sur r ogat e speci es f ound in a shel t ered envi ronment or in cont i nuous cont act
wi t h represent at i ve t oxi cant mat eri al s for ext ended cont act times, parti cul arl y, as bi odegradat i on, sedi ment
absor pt i on and di spersi on are not i nvest i gat ed in t he speci f i ed t est procedures.
The premi se of t hi s document is to provi de a verified al ternati ve envi ronment al assessment met hod wi th
subsequent appl i cat i on to real worl d dynami cs t hat consi der s all the f act ors of envi ronment al avai l abi l i ty t hat l eads
to bi ospher e di srupt i on and i mpact br ought about by speci al t y product i on chemi cal s. The pr ocess st art s by
det ermi ni ng t he base toxi ci ty of effl uent wat er pri or to the addi ti on of chemi cal s. The comparat i ve assessment of
di fferent speci al t y chemi cal s may t hen be conduct ed to provi de predi cti ve resul tant impact, acut e and chroni c, and
bi ospher e risk
Di schar ged effl uent wat er revi ewed here are pr ocessed at one product i on and t hree satel l i te pl atforms and
di schar ged from subsea outfal l s at each platform at a combi ned rate of 242 million L/day, wi t h t he l argest si ngl e
di schar ge at 82 million liters per day. These effluent wat er s exhi bi t high t emperat ure (90 C), bracki sh sal i ni t y (11
ppt), and cont ai n resi dual hydr ocar bon and man made chemi cal moi eti es
i ncl udi ng corrosi on i nhi bi tors.
St udi es have been conduct ed (1) on t he fate and possi bl e i mpact of product i on wat er s in an open sea
envi ronment by det ermi ni ng t he physi cal di spersi on of t he effluent and its geochemi cal behavi or. The
geochemi cal di spersi on model devel oped successf ul l y si mul at es t he chemi cal behavi or of t he pr oduced wat er
component s by consi der i ng sedi ment - wat er parti ti oni ng, volatilization, bi odegradat i on, and phot odegradat i on.
Laborat ory experi ment s and field val i dat i on wor k f or thi s outfall i ndi cate that t he maj ori ty of pr oduced wat er
component s are rapi dl y volatilized, bi odegraded, and mi neral i zed (2). The mol ecul arl y l arge component s are
t ypi cal l y unaffected by the mi croorgani sms, but often partition on to suspended sol i ds resi dent in t he recei vi ng
wat er.
An i mport ant fi ndi ng of si mul at i on model i ng is concent rat i on "pondi ng" at sea [2] [3]. The "pondi ng" effect is
t hought t o have i mport ant i mpl i cat i ons for chroni c bi o-i mpact because it represent s a regi on of i ncr eased exposur e
concent rat i on for ext ended peri ods.
Finally, bi odi spersi on model i ng may t hen be appl i ed to proven t oxi col ogy model s that det er mi ne adver se effect
and risk associ at ed wi th mi xed pr oduced water~corrosion i nhi bi tor di schar ge on adj acent biota. Where thi s si te-
speci f i c model i ng is compl i cat ed by mari ne di versi ty and speci es speci fi c upt ake mechani sms t hese f act ors have
been i nvesti gated and field val i dated.
Predi ct i ve Model i ng Appr oach
The CBR (critical body resi due) appr oach appl i ed in thi s st udy det ermi nes toxi c r esponse by expl oi ti ng
concent rat i on and upt ake i nformati on to det er mi ne bi oconcent rat i on and toxi c response. The most difficult t ask is
rel ati ng body resi due levels to concent r at i ons known or suspect ed to cause an adver se response.
The magni t ude of bi ol ogi cal r esponse caused by toxi ci ty in r esponse to t he quant i t y of exposur e resul t s in t wo
basi c assumpt i ons;
1). The concent rat i on of a chemi cal at t oxi c r esponse si t es is proport i onal to exposur e and concent rat i on
availability, and
2). Once a t hreshol d magni t ude is exceeded t he biological r esponse elicited is proport i onal to the chemi cal
concent rat i on at t he t oxi c r esponse site.
It is practi cal l y i mpossi bl e to measur e t oxi cant concent rat i on at a r esponse site, so sur r ogat e measur ement s
are appl i ed, such as t he concent rat i on of t he exposur e medi um. For exampl e LCso wat er concent rat i ons are often
a surrogat e for the t oxi cant at the r esponse si te of a given organi sm, [4]. There are limitations or short -comi ngs to
thi s approach. These i ncl ude met abol i c br eakdown or activation, lipid content, t emperat ure, and general bi ol ogi cal
factors such as speci es, sex, life stage, and season.
The compar i son of LCso val ues wi th CBR does have several advant ages. Those include:
1. Det ermi nat i on of expl i ci t bio-availability,
2. Det er mi nat i on of accumul at i on ki neti cs ver sus exposur e requi rement s,
3. Mul ti pl e chemi cal mi xture assessment is easi l y conduct ed, and
4. Experi ment al veri fi cati on is possi bl e in t he l ab or field.
Based on t he dat a for CBR est i mat es for fi sh is] di fferent modes of t oxi c acti on general l y appear to be
associ at ed wi t h di fferi ng ranges of body resi dues. Thi s phenomenon is expl ai ned by noti ng when chemi cal s t hat
act by speci f i c modes of toxi c acti on (i.e. non-narcot i c) are pr esent in a mi xture bel ow t hei r t hr eshol d for t oxi c
act i on t hey do not expr ess a speci f i c toxi c acti on. They merel y cont ri but e t o t he narcot i c activity of t he mixture. In
t hese ci r cumst ances, si mpl e addi ti on of t he narcot i c toxi ci ty of the component s of t he mixture, rather t han any
i nt eract i on bet ween speci fi c modes of toxi c acti on, pr oduce bi ol ogi cal r esponse tel.
Toxi ci t y det er mi nat i on
To ascer t ai n t oxi ci t y of an effluent di schar ge regul at ory bodi es depend upon t he use of sur r ogat e i ndi cat or
speci es t oxi ci t y t est s, LCso or LD5o. These resul ts are then ext rapol at ed to field condi t i ons and predi ct i ve i mpact
i mposed.
The sur r ogat e t oxi ci t y resul t s det ermi ned for t he di schar ge l ocat i ons and appl i ed to CBR model i ng, revi ewed
here, are based on acut e toxi ci ty t est s (ASTM Desi gnat i on: E 1192-88) appl i ed t o mysi d shri mp, Mysidopsis bahia
and t he si l versi de, Menidi beryllina usi ng sampl es of f resh and t he bi odegr aded pr oduced wat er.
The resul t s of pr oduced wat er toxi ci ty present ed in Tabl e 1 i ndi cate that acut e toxi ci ty effect appear s to be
consi st ent for both speci es. The degradat i on of t he effl uent wat er wi t h resul t ant shi ft in chemi cal anal yt e
concent rat i on resul t ed in a shi ft in acut e toxi ci ty for effl uent wat er tested.
Important is t he fact that degradat i on of chemi cal i somers often ai d in t he removal of t oxi c cont ami nant s, but
may resul t in t he f ormat i on of met abol i t es whi ch in t hemsel ves are often more toxi c t han t he pr ecur sor compound'
( 7 ) .
Chemi st r y
Connat e wat er
The f resh and bi odegr aded effl uent wat er was t est ed for the pr esence of 113 EPA defi ned cont ami nant s to
correl at e toxi ci ty obser ved to chemi cal resi dual . The cont ami nant s wer e cat egori zed as monoaromat i c
hydr ocar bons (VOC), Phenol s, or Pol ycycl i c Ar omat i c Hydr ocar bons (PAH). A total of 76 compounds wer e
identified. Of t hose 76 compounds, 24 compr i se approxi mat el y 85 percent of t he total concent rat i on of
cont ami nant s i denti fi ed, (Tabl e 2)
Speci al t y Chemi cal s
In t he wor k report ed here corrosi on i nhi bi tors and ot her addi ti ves are added to t he connat e oi l -wat er st ream to
sol ve probl ems encount er ed in the product i on process. Al t hough many of t hese chemi cal s are oil sol ubl e/ wat er
di spersi bl e and remai n wi t h the oil f ol l owi ng oi l -wat er separat i on, some are sufficiently wat er - sol ubl e t hat a f ract i on
not parti ti oned in oil and wat er t reat ment remai ns wi th t he pr oduced water, is di scharged, and becomes
bioavailable.
Onl y a f ew of t he chemi cal addi ti ves appl i ed in t he syst em st udi ed here are consi der ed suffi ci entl y wat er-
sol ubl e or di sper si bl e to be di schar ged in pr oduced wat er (Tabl e 3). The percent di schar ge val ues appl i ed here
wer e det ermi ned usi ng t he conservat i ve f ormul a from CHARM (per 1996 recommendat i on) unl ess product
speci fi c dat a was avai l abl e.
Di l uti on and bi oaccumul at i on det ermi nat i on
Di ffi cul ti es addr essi ng effl uent wat er toxi ci ty probl ems of of f shore effluent pl umes i ncl ude t he t oxi c composi t i on
of ef f l uent -sea wat er mi xtures, resul t ant toxi c anal yt e bioavailability, i ntermi ttent exposur e accumul at i on ki neti cs,
and body resi due det ermi nat i on.
In thi s st udy we used equi l i bri um parti ti oni ng t heory wher e t he l i pi d-wat er parti ti oni ng is adj ust ed by speci es-
speci f i c f act ors such as f eedi ng, met abol i sm, growt h dilution, and di gest i on [8-9]. Hence, t he model consi der s
sur r ogat e mari ne or gani sms as speci es speci fi c wi th t i ssue concent rat i on and bi oaccumul at i on of t he chemi cal / s in
aqueous sol uti on wi t h resul t ant concent rat i on in t i ssue appr oxi mat ed by total lipids usi ng oct anol wat er coef f i ci ent
or Kow.
For t he pr esent study, val ues f or l og Kow of petrol eum hydr ocar bons wer e obt ai ned from Neff and Burns [10] and
cor r osi on i nhi bi tor val ues wer e obt ai ned from empi ri cal data uti l i zi ng PARCOM speci f i ed t est i ng pr ocedur es. The
lipid cont ent of i ndi cat or speci es fi sh used in regressi on of log BCF/ I og Kow dat a is 7. 6% wet wei ght [11] wher e log
(BCF) = log (Ct/Cw), and Ct and Cw equal t he concent rat i ons of t he chemi cal in t i ssue and di ssol ved in wat er,
respecti vel y, at equi l i bri um. The lipid cont ent of Menidia and Mysidopsis, 6% and 3. 3% respecti vel y, was
det er mi ned by lipid ext ract i on from st ocks utilized.
I mport ant to real worl d appl i cat i ons is t he maj ori ty of hydr ocar bons and man made i somer s pr esent in pr oduced
wat er s requi re an ext ended cont act ti me to reach equi l i bri um in t i ssues of aquat i c ani mal s. To model limited
cont act requi red t he appl i cat i on of non st eady state accumul at i on, t he equat i ons def i ned by Connel l and Hawker
[12] t hat expr ess t he BCF as a f unct i on of both Kowand exposur e ti me wer e appl i ed.
Finally, as not ed in t he i ntroducti on, effl uent wat er pl umes ar e subj ect ed to dynami c shi fts in di rect i on and
"pondi ng". Indeed, pl umes subj ect ed to open sea t ype hydr odynami cs do not have a uni di recti onal f l ow but are
subj ect ed t o many dynami c f orces that resul t in pl ume redi rect i on of up to 90 in 8 hours and 360 in a day.
Thi s rapi d movement in pl ume redi recti on resul ts in non st eady st at e load to resi dent st at i onary mari ne biota.
To det er mi ne body resi due concent r at i ons associ at ed wi t h t hese movement s we appl i ed phar macoki net i c non-
st eady st at e summat i on of individual doses speci fi c to a geogr aphi cal location. Thi s is accompl i shed by summi ng
t he cont ri but i ons of each i ndi vi dual dose by noting t he avai l abl e concent rat i on and decayi ng t hat concent r at i on
usi ng t he in body half-life defi ned;
t l / 2 = l n 2 / K 2= 0 . 6 9 3 / K 2
Based on t he compounds anal yzed in f resh and degr aded effl uent wat er, we have obt ai ned body r esi dues (BR) (in
mMol es) for t he sum of all compounds det ermi ned usi ng t he BCF f ormul a [Tabl e 4].
The basel i ne CBR concent rat i on based upon lipid concent r at i ons as defi ned by McCart y is 2.87 mMol / kg for
Menidia and 5.25 mMol / kg for Mysids. The est i mat ed BR for all compounds anal yzed in avai l abl e effl uent wat er
denot e resul t s t hat are l ess t han t he l i terature defi ned CBR in spi t e of exposur e based t est i ng t hat i ndi cates that a
def i nabl e acut e toxi c r esponse occurs.
To equi l i brat e known BR to def i ned toxi c r esponse a program of sur r ogat e concent r at i ons whi ch combi nes t he
BRs cal cul at ed from chemi cal degradat i on anal ysi s dat a correl at ed to the base dat a obt ai ned from the toxi ci ty
t est s wer e col l ated. Briefly i mpl ement at i on was as fol l ows;
1 .) t heoret i cal upt ake and depurat i on rates (derived from Connel l & Hawker) cal cul at e t he i nst ant aneous BCFs at
24, 48 and 96 hours after exposure,
2.) From toxi ci ty dat a we t ake t he speci es/ out f al l speci fi c mortal i ty per cent ages at 24, 48 and 96 hours. For each
di l uti on and ti me interval (24, 48, 96 hours) we plot thi s data agai nst t he est i mat ed BR for all compounds anal yzed
at each cor r espondi ng ti me and dilution. The above noted process resul ts in a graph of BR (total anal yzed
compounds) agai nst % Mortal i ty for each exposur e interval,
4.) A best-fi t l i ne/l i near regressi on was then plotted to provi de speci es and outfall speci fi c empi ri cal equat i ons.
Anal ysi s of t he pr oduced wat er / chemi cal sur r ogat e CBR vs. 50% mortal i ty denot es a concent r at i on of 0. 288
mmol es for Meni di a and 0. 725 mmol es t oxi cant concent rat i on for Mysi ds.
Ri sk Det ermi nat i on
In a scr eeni ng exer ci se of thi s t ype, it is appropri at e (as defi ned by CHARM) and consi st ent wi t h CBR
det ermi nat i ons to assume t hat the ri sk (hazard indices) of all the chemi cal s measur ed in pr oduced wat er are
addi ti ve and defi nabl e.
As di scussed above, mari ne or gani sms may bi oaccumul at e chemi cal const i t uent s of pr oduced wat er duri ng
exposur e to a pr oduced wat er plume. The CBR used here based on acut e toxi ci ty to aquat i c ani mal s, is def i nabl e
and fi el d verified. By appl yi ng geogr aphi cal l y speci fi c data from thi s model PEC/ PNEC [Potential Envi ronment al
Concent rat i on / Predi ct ed No-Effect Concent rat i on] or Van Leeuwen HC5 ri sk concept s have been devel oped t hat
est i mat e ri sk t o the i mpact ed aquat i c communi t y duri ng obser ved exposure. In t hi s paper we onl y di scuss t he
PEC/ PNEC i mpact as it is more readi l y accept ed.
Comparative Inhibitor Modeling
Present ed bel ow is t he envi ronment al i mpact and associ at ed risk, as def i ned by PEC/ PNEC [, of t hr ee di fferent
corrosi on i nhi bi tor t ypes. These pr oduct s are used for corrosi on inhibition in t hree phase pi pel i ne syst ems t hat
di schar ge effl uent wat er into a tropi cal mari ne envi ronment. These corrosi on i nhi bi tors and t he anci l l ary t r eat ment
pr oduct s are used at t r eat rates, adj ust ed respect abl y, t hat provi ded l ess than 0.051 mm/y cor r osi on rate and an
overboard oil in wat er effluent, wher e possi bl e, of l ess than 20 ppm. The above- descr i bed model usi ng obser ved
effl uent di schar ge par amet er s and empi ri cal anal yti cal data defi nes the envi ronment al i mpact of t hat effluent.
Defi ned is comparat i ve i mpact of each product for based upon known toxi ci ty and appl i ed to a chr oni c PEC/ PNEC
risk assessment .
Akyl pyri di ne quat er nar y salt.
The fi rst corrosi on i nhi bi tor i nvest i gat ed is an alkyl pyri di ne quat ernary sal t corrosi on i nhi bi tor commonl y appl i ed
t hr oughout Sout heast Asi a. Thi s t ype i nhi bi tor chemi st ry is long est abl i shed, very effective but known to cause
adverse envi ronment al i mpact. For t hi s speci f i c f ormul at i on t he PARCOM def i ned toxi ci ty dat a is 5.5 ppm for
Skel etonema and 16 ppm for Acarti a Tonsa. To defi ne t he observed consequences of appl i cat i on (di rty wat er
overboard, i ncreased demul si f i er and wat er cl ari fi er requi rement s), as envi ronment al i mpact we have appl i ed field
resul t s to t he model to ascert ai n envi ronment al i mpact and risk.
Thi s product was appl i ed at 12 ppm, whi ch resul ted in an i ncr ease to resi dual oil in wat er overboard (15 ppm to 40
ppm), i ncreased demul si f i er appl i cat i on (6 ppm to 15 ppm) and i ncreased wat er cl ari fi er appl i cat i on (6 to 20 ppm).
As noted in t he di scussi on above, t hese changes are addi ti ve to the base toxi ci ty noted for connat e wat er and
resul t in a more t oxi c mi xture to t he envi ronment.
The comparat i ve resul t s of t he base connat e wat er and connat e wat er wi t h al kyl pyri di ne quat er nar y sal t model
runs are pr esent ed in Figs 1 - 2. I mmedi at el y obvi ous is the i ncreased ar ea of adverse i mpact (21 km 2 [ connat e
water] to 107.2 km 2 [ wat er pl us inhibitor]) when compari ng 61 -day accumul at i on in Mysi d shri mp and appl yi ng t he
PEC: PNEC ratio. Thi s i ncrease occur s as t he t oxi cant concent rat i on, attri buted to t he use of al kyl pyri di ne
quat ernary salt, i ncr eases resi dual hydr ocar bon levels by a f act or of 2.7 wi th corrosi on i nhi bi tor car r yover of 17.1
per cent. The i mportant f act or to note is that t he maj or porti on of t he toxi c r esponse noted is not di rectl y caused by
cor r osi on inhibitor, but rather i ndi rectl y caused by i ncreased resi dual hydr ocar bon carryover and i ncr eased levels
of ot her product i on chemi cal s t o i mprove wat er quality. Hence, i mprovement s in corrosi on i nhi bi tor bi odegradat i on
ability and/ or reduced product toxi ci ty are l ess i mportant than t he anci l l ary overall effect caused by t he use of thi s
corrosi on inhibitor. Once t he wat er qual i ty probl ems are resol ved t he bi oavai l abi l ty and resul tant toxi ci ty of t he
product must be addr essed to reduce toxi c impact.
First generation corrosion "green" inhibitor, salted imidazoline.
The first generation of "green" corrosion inhibitors investigated were salted imidazolines that exhibited limited
environmental impact improvement after application. Improvements in biodegradation testing are marked when
compared to alkyl pyridine quaternary salt, 15% vs. 42 % but toxi ci ty for this formulation, per PARCOM, is 0.3 for
Skel et onema and 2.1 ppm for Acarti a Tonsa. The emphasis with this type product is to reduce the products long-
term environmental persistency. What was not addressed was the product chronic accumulation ability associated
with continuous discharge. This particular product was applied at 12 ppm resulting in an increase to residual oil in
water overboard (15 ppm to 25 ppm), increased demulsifier application (6 ppm to 12 ppm) but no increase to
water clarifier application. As noted in the introductory discussion, these changes are additive to the base toxi ci ty
noted for connate water and resulted in a more toxic mixture.
The comparative results of the base connate water and connate water with "green" inhibitor model runs are
presented in Figs 1 and 3. Immediately obvious is the increased area of impact (21 km 2 to 78.3 km 2) when
comparing 61 -day accumulation in Mysid shrimp and applying the PEC:PNEC ratio. This is a significant increase
in area of environmental impact when compared to the untreated water but a marked improvement [27%] to akyl
pyridine quaternary salt use. The observed increase in impact occurs when toxicant concentration attributed to
"green" inhibitor increases the residual hydrocarbon levels by a factor of 1.5 combined with a residual corrosion
inhibitor carryover of 33.8 per cent. The important factor to note is that the corrosion inhibitor is largely responsible
for causing increased toxi ci ty as compared to the indirect actions of the akyl pyridine quaternary salt product.
Indeed, residual hydrocarbon carryover and increased usage of demulsifier to improve water quality are
problematic, but overall product toxi ci ty is more important. Finally, in this comparison improvements in
biodegradation ability are far less important than the overall toxi c effect caused by inhibitor residuals.
Second generation "green" inhibitors, mixture of salted mono-amines.
The second generation of "green" corrosion inhibitors investigated showed marked improvement as compared
to the previous products. Improvements in biodegradation are noted when compared to alkyl pyridine, 15% vs. 32
% with reductions in toxi ci ty for this formulation, per PARCOM, at 63 ppm for Skel etonema and 180 ppm for
Acart i a Tonsa. In addition, the observed consequences of application exhibited no significant increase in residual
oil carry over resulting in no ancillary chemical addition requirements. This particular product was applied at 20
ppm resulting in an increase to residual oil in water overboard (15 ppm to 20 ppm), with no increased demulsifier
application or water clarifier application. Again, as noted in the introductory discussion, all changes in chemical
addition are additive to the base toxi ci ty noted for connate water and result in a more toxic mixture.
The comparative results of the base connate water and connate water with second "green" inhibitor are
presented in Figs 1 and 4. Immediately obvious is the increased area of impact (21 km 2 to 38.3 km 2) when
comparing 61-day accumulation in Mysid shrimp and applying the PEC:PNEC ratio. But when this product is
compared to its predecessors the area of adverse impact is greatly reduced, a reduction of 64.3% for alkyl
pryridine quaternary salt and 51.1% for salted imidazoline. The observed increase in toxic response occurs as the
toxi cant concentration, attributed to the "green inhibitor", increases residual hydrocarbon levels by a factor of 1.3
with residual corrosion inhibitor carryover of 50.7 per cent. The most important factor to note is that the corrosion
inhibitor is causing increased toxicity. Indeed, residual hydrocarbon carryover is not a problem rather the overall
increase in toxi ci ty is result of increased inhibitor concentration in the effluent water. It must not be construed that
improvements in inhibitor chemistry are not occurring, indeed the opposite is apparent. When the second-
generation product is compared to its predecessors the toxi ci ty test results show an order of magnitude
improvement to akyl pryidine quaternary salt and approximately 2 orders of magnitude improvement to the salted
imidazolines. This results in the ability to discharge a factor of three increase in corrosion inhibitor residual in
effluent water and have a reduction in chronic PEC/PNEC affected area of 68.9 kms 2 or a factor of 2.8
improvement.
Discussion
Immediately apparent from the analysis of these three products is the fact that improvements in corrosion
inhibitor chemistry have resulted in a reduction in overall toxic impact as defined by PEC:PNEC risk analysis.
Importantly, the area of adverse environmental impact continues to be reduced, even with increased concentration
of resi dual i nhi bi tor carryover. These resul ts i ndi cate that observed toxi ci ty caused by i ncreased resi dual oil
car r yover and i nhi bi tor resi dual is of pri mary i mport ance.
Fundament al l y, t hese resul t s refute t he emphasi s pl aced on bi odegradat i on al one, as bi odegradat i on does not
addr ess t he overal l i mpact of a product. In fact, a product wi th a l esser bi odegradabi l i t y may resul t in a reduct i on in
envi ronment al i mpact as exhi bi ted by second generat i on products. Finally, it is i mport ant when compar i ng overal l
toxi ci ty t hat any i ncr ease in resi dual oil and i ncr eased anci l l ary product appl i cat i on is consi der ed as part of a
product ' s overal l toxi ci ty and geographi cal risk.
Conclusions
The use of shor t term, exposur e based, toxi c r esponse assessment correl at ed wi t h ri gorous chemi cal anal yses
of f resh and bi odegr aded effl uent wat er s has resul t ed in t he deri vati on of an "in body" resi due model for t oxi c
r esponse and geogr aphi cal risk. Appl i cat i on of t hi s model to effl uent wat er s cont ai ni ng resi dual corrosi on i nhi bi tors
al l ows t he comparat i ve assessment of di fferent speci al t y chemi cal s appl i ed to t he product i on st ream f or
det ermi nat i on of t oxi c i mpact and geographi cal risk.
A compar i son of t hree di fferent t ypes of cor r osi on i nhi bi tors usi ng thi s model i ng pr ocess demonst r at ed a
reduct i on in overal l toxi ci ty as defi ned by PEC: PNEC ri sk anal ysi s when appl yi ng "green" i nhi bi tor chemi st ry.
Importantl y t he ar ea of i mpact cont i nues to be reduced wi th i mprovement s in chemi st r y but product toxi ci ty caused
by i ncr eased i nhi bi tor resi dual s remai ns probl emat i c even wher e bi odegradabi l i t y i mproves. Thi s i ndi cat es t hat an
emphasi s on bi odegradat i on al one does not addr ess t he overall i mpact of a product in t he envi ronment. In fact, a
pr oduct wi t h l ess t han opti mal bi odegradabi l i t y may resul t in limited envi ronment al i mpact as exhi bi ted by second
generat i on "green" product s.
What appear s to be of gr eat est i mport ance when compari ng overall cor r osi on i nhi bi tor toxi ci ty is that any
i ncr eases in resi dual oil and i ncreased requi rement for anci l l ary product appl i cat i on must be consi der ed as part of
t he pr oposed product overall toxi ci ty and resul t ant geographi cal risk.
1.
2.
3.
4.
5.
6.
Bibliography
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Tabl e 1
Percentage produced water required to cause acute toxicity
Meni di a Mysi ds
LCso ,re 15. 9% 33. 7%
LCzl ~ve 6. 8% 18. 4%
Tabl e 2.
Concent rat i on of cont ami nant s found in produced water with and without degradation
Produced Water
PAH Phenol VOC
Fresh 16.5% 70.6% 13.9%
24hr deg. 29.5% 58.7% 11,8%
48hr deg. 41.1% 53.4% 5.5%
96hr deg. 83.7% 15.8% 0.4%
Ta bl e 3.
Per cent di schar ge and toxicity of addi ti ves used in producti on process
A d d i t i v e T y p e P e r c e n t D i s c h a r g e d A c u t e T o x i c i t y R a n g e
( m g / L )
Bi oci des 3.1 0 . 2 2 - > 1000
Corrosi on Inhibitors 8 . 7 0 . 9 - 1 0 5 5
Sc a l e Inhibitors 66 6 0 0 - > 1 0 , 0 0 0
Demul si f i er s 2 . 0 10 - > 1 0 , 0 0 0
Coagul ant 85 15 - 1 4 , 8 0 0
Tabl e 4
Equat i ons f or est i mat i ng body resi due accumul at i on f or anal yt es wi th t he gr eat est concent r at i on
A n a l y t e B i o c o n c e n t r a t i o n d a t a
I
LOg Row ~l andar d I nf or mat t on per l ext
LogBcf Per Vedh and Kosi an Log BCF=O. 79* l ogKow- 0. 4
Equi l . BCF l O' Log BCF
k l Connel l and Hawker Ecot ox. & Envi r on Saf et y #16 1988 ; kl = 10^( 2. 92 - 986* ( Log Kow-5 87) ' 2
k2 Connel l and Hawker Ecot ox. & Env=ron, Sal et y #16 1988
k2 = 1/ 10^( 0. 0069* l ogKow^4 - 185*l ogKow^3~ 1.65*1og K o w ~ 2 - 5 . 3 4 * l o g K o w + 5 . 2 7
2 4 hr BCF K1; K2 * ( 1- EXP( k2* Tl me( days) )

H a l f l i f e o r T 1/ 2 O 693/ k2
PAH Log Kow LogBcf
51 - oenZo( bJt nl ophenes 4.~6 344
D2 - benzo( b) t hl ophenes 5.5 3. 95
~apht hal ene 3.37 2. 26
331- napht hal enes 387 2. 66
332-napht hal enes 4. 37 3. 05
D3* napht hal enes 5 355
D4- napht hal enes 5 55 3. 98
=l uor ene 4. 18 2 90
D1 . f l uor enes 4,97 3 53
2, 2-f l uorenes 5 2 3 71
~henant hr ene 4. 57 3 21
~nt h r acene 4.54 3 19
3enz{ a) ant hr acene 6.75 4. 93
Dhr ysene 5.86 4. 23
kl k2 T 112 T 1/ 2
Equi l . BCF days days 24hr BCF days hrs
Z. I bU. 43 6~9,B1 0,13 (520.2~ ~. ~q~ 133.U
8,B 10.49 806 31 0 . 0 4 788.45 15.41 369. 8
182,94 201. 26 1.50 104.05 0.461 11.1
454, 26 335 43 0 . 7 2 238. 83 0. 950 23.0
1. 127. 98 499 06 030 430 97 2 . 3 0 3 55 3
3, 548, 13 700.44 0.10 667 12 7.051 169 2
9, 649 39 812. 65 0.04 79584 1 6 , 5 2 396 5
798. 36 434, 90 0.42 354 57 1.637 39 3
3. 35970 692. 04 010 657. 46 6.7 160.8
5, 105 05 751.17 007 725.23 9 . 8 0 1 235. 2
1, 622 93 666 72 071 511. 29 3. 300 79.4
1 536. 74 556. 66 0 2 2 499. 39 3. 133 75.2
85, 605 17 697. 66 0,01 692. 54 46. 96 1126. 9
16,958 99 831. 74 0,03 820. 05 2 4 . 4 1 585. 9
P h e n o l Log Kow LogBcJ
C1 - Phenol s 2 06 1 23
C 2 - P h e n o l s 2.34 1 45
C3- Phenol s 2.95 1 93
C4 Phenol s 3 1 2 05
o/ m -Cresol 2 1 18
cresol 1 97 116
Equi l . BCF kl k2 24hr BCF T 1/2 T 1/2
b. 6/ l O, U6 o 3b ~.4b 1.U3~ 4~5.b I
I
16.88 30,81 1.67 15.00 0 . 4 1 6 10 0
28 09 49. 13 2.26 19 46 0 . 3 0 6 7 4
8521 12003 2 24 47 84 0. 309 7, 4
111.94 145.70 200 6293 0. 346 8.3
15 14 27. 75 1 51 1431 0. 458 11 0
14,33 2632 1 43 13.98 0. 483 11.6
V O C L o g K o w L o g a c |
F
enzene Z 13 1.~6
Tol uene 2 69 1,73
Et hyl benzene 3 45 2,33
m/ o / p - X y l e n e 3 13 2 07
Equi l . BCF kl k2 24hr BCF 3" 1;2 T 1/2
19. 1/ 34 / 4 1 64 l b U 0 , 3 1 1 9.11
I
53. 10 B3 74 2.48 30 92 0. 279 6.7
211, 59 223 07 1 36 120.34 0.51 12.2
1 1 8 . 2 2 ~51 27 195 66. 55 0. 355 6.5
Figure 1
Baseline risk of Connate water.
~" 36' S
Area of adverse impact
21 km2
I06 4 2 ' E
Risk as defined by PEC/PNEC
All solid areas in black denote adverse impact as defined by BCF and CBR accumulated over a 60 day period.
Fi gur e 2
Akyl Pyridine Quaternary Compound
. / , r
16' S
\
A~a of adverse impoct
1 0 7 . 2 ki n2
J
42' S
1 0 6 " 3 6 ' E
" . / , , , r
1 0 6 " 4 2 ' E
Risk as defined by PEC/NEC
All solid areas in black denote adverse impact as defined by BCF and CBR accumulated over a 60 day period
Figure 3
First Generation Inhibitor
36' S
Area of Adverse Impact
/
78. 3 kin2
m
108" 42' E
Risk as defined by PEC/NEC
All solid areas in black denote adverse impact as defined by BCF and CBR accumulated over a 60 day period
F I G. 4
Second Generation
/
Area of adverse impact
38. 3 kmZ
o," 42' S
1 0 6 " 3 8 ' E l OB" 42' E
Ri s k as def i ned by PEC/ NEC
Al l sol i d ar eas in bl a c k denot e adver s e i mpact as def i ned by BCF and CBR a c c umul a t e d over a 60 day per i od