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Impact Differentiation of Environmentally Friendly versus Standard Corrosion Inhibitor Discharged into a Tropical Marine Environment 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. Griegvei 3A N-5037 Solheimvik Norway ABSTRACT A comparative ecotoxicology investigation has been conducted using field specific parameters to assess the impact of residual corrosion inhibitor, standard versus "green ", discharged from offshore facilities. Presented is a modeled estimate of ecological impact and risk associated with produced water / corrosion inhibitor mixtures from a low salinity-high temperature discharge of 142 million L/day into an open sea environment. Impact is assessed by extrapolation of steady state indicator test species LCso critical body residue (CBR) results applied to an accurate characterization of resident organism non steady state exposure and contaminant load. This extrapolation determines the acute and chronic impact of produced water / corrosion inhibitor mixture with time. These extrapolations are possible using an empirically justified predictive computer simulation of toxicant effluent mixture discharged into an open sea environment that determines plume dispersion, degradation, dilution, and bioaccumulation. The modeled simulation furnishes non steady state CBR bioaccumulation concentrations that provide an accurate representation of acute and chronic mortality with resultant PEC/NEC risk at any given geographical location adjacent to effluent discharge location. Key words; bioaccumulation, biodegradation, inhibitor, half life, risk assessment. Introduction E and P operations and specialty chemical suppliers spend a significant amount of money and energy complying with biodegradation testing requirements or regulatory specified toxicity tests. Once completed the test results are often applied to open sea dynamics or inland estuaries. Unfortunately, the results of these testing regimes are very seldom applicable to real world bio-dynamics occurring in either biosphere. This is substantiated Copyright @2000 by NACE International.Requestsfor 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, Texas77218-8340. The material presented and the views expressed in this paper are solely those of the author(s) and are not necessarilyendorsed by the Association. Printed in U.S.A.
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Page 1: 00333: Impact Differentiation of Environmentally Friendly ... · Impact Differentiation of Environmentally Friendly versus ... that determines plume dispersion ... work for this outfall

Impact Differentiation of Environmentally Friendly versus Standard

Corrosion Inhibitor Discharged into a Tropical Marine Environment

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. Griegvei 3A N-5037 Solheimvik

Norway

ABSTRACT

A comparative ecotoxicology investigation has been conducted using field specific parameters to assess the impact of residual corrosion inhibitor, standard versus "green ", discharged from offshore facilities. Presented is a modeled estimate of ecological impact and risk associated with produced water / corrosion inhibitor mixtures from a low salinity-high temperature discharge of 142 million L/day into an open sea environment. Impact is assessed by extrapolation of steady state indicator test species LCso critical body residue (CBR) results applied to an accurate characterization of resident organism non steady state exposure and contaminant load. This extrapolation determines the acute and chronic impact of produced water / corrosion inhibitor mixture with time.

These extrapolations are possible using an empirically justified predictive computer simulation of toxicant effluent mixture discharged into an open sea environment that determines plume dispersion, degradation, dilution, and bioaccumulation. The modeled simulation furnishes non steady state CBR bioaccumulation concentrations that provide an accurate representation of acute and chronic mortality with resultant PEC/NEC risk at any given geographical location adjacent to effluent discharge location.

Key words; bioaccumulation, biodegradation, inhibitor, half life, risk assessment.

Introduction

E and P operations and specialty chemical suppliers spend a significant amount of money and energy complying with biodegradation testing requirements or regulatory specified toxicity tests. Once completed the test results are often applied to open sea dynamics or inland estuaries. Unfortunately, the results of these testing regimes are very seldom applicable to real world bio-dynamics occurring in either biosphere. This is substantiated

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.

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by the fact that in very few cases are surrogate species found in a sheltered environment or in continuous contact with representative toxicant materials for extended contact times, particularly, as biodegradation, sediment absorption and dispersion are not investigated in the specified test procedures.

The premise of this document is to provide a verified alternative environmental assessment method with subsequent application to real world dynamics that considers all the factors of environmental availability that leads to biosphere disruption and impact brought about by specialty production chemicals. The process starts by determining the base toxicity of effluent water prior to the addition of chemicals. The comparative assessment of different specialty chemicals may then be conducted to provide predictive resultant impact, acute and chronic, and biosphere risk

Discharged effluent water reviewed here are processed at one production and three satellite platforms and discharged from subsea outfalls at each platform at a combined rate of 242 million L/day, with the largest single discharge at 82 million liters per day. These effluent waters exhibit high temperature (90 °C), brackish salinity (11 ppt), and contain residual hydrocarbon and man made chemical moieties including corrosion inhibitors.

Studies have been conducted (1) on the fate and possible impact of production waters in an open sea environment by determining the physical dispersion of the effluent and its geochemical behavior. The geochemical dispersion model developed successfully simulates the chemical behavior of the produced water components by considering sediment-water partitioning, volatilization, biodegradation, and photodegradation. Laboratory experiments and field validation work for this outfall indicate that the majority of produced water components are rapidly volatilized, biodegraded, and mineralized (2). The molecularly large components are typically unaffected by the microorganisms, but often partition on to suspended solids resident in the receiving water.

An important finding of simulation modeling is concentration "ponding" at sea [2] [3]. The "ponding" effect is thought to have important implications for chronic bio-impact because it represents a region of increased exposure concentration for extended periods.

Finally, biodispersion modeling may then be applied to proven toxicology models that determine adverse effect and risk associated with mixed produced water~corrosion inhibitor discharge on adjacent biota. Where this site- specific modeling is complicated by marine diversity and species specific uptake mechanisms these factors have been investigated and field validated.

Predictive Modeling Approach

The CBR (critical body residue) approach applied in this study determines toxic response by exploiting concentration and uptake information to determine bioconcentration and toxic response. The most difficult task is relating body residue levels to concentrations known or suspected to cause an adverse response.

The magnitude of biological response caused by toxicity in response to the quantity of exposure results in two basic assumptions;

1). The concentration of a chemical at toxic response sites is proportional to exposure and concentration availability, and

2). Once a threshold magnitude is exceeded the biological response elicited is proportional to the chemical concentration at the toxic response site.

It is practically impossible to measure toxicant concentration at a response site, so surrogate measurements are applied, such as the concentration of the exposure medium. For example LCso water concentrations are often a surrogate for the toxicant at the response site of a given organism, [4]. There are limitations or short-comings to this approach. These include metabolic breakdown or activation, lipid content, temperature, and general biological factors such as species, sex, life stage, and season.

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The comparison of LCso values with CBR does have several advantages. Those include: 1. Determination of explicit bio-availability, 2. Determination of accumulation kinetics versus exposure requirements, 3. Multiple chemical mixture assessment is easily conducted, and 4. Experimental verification is possible in the lab or field.

Based on the data for CBR estimates for fish is] different modes of toxic action generally appear to be associated with differing ranges of body residues. This phenomenon is explained by noting when chemicals that act by specific modes of toxic action (i.e. non-narcotic) are present in a mixture below their threshold for toxic action they do not express a specific toxic action. They merely contribute to the narcotic activity of the mixture. In these circumstances, simple addition of the narcotic toxicity of the components of the mixture, rather than any interaction between specific modes of toxic action, produce biological response tel.

Toxicity determination

To ascertain toxicity of an effluent discharge regulatory bodies depend upon the use of surrogate indicator species toxicity tests, LCso or LD5o. These results are then extrapolated to field conditions and predictive impact imposed.

The surrogate toxicity results determined for the discharge locations and applied to CBR modeling, reviewed here, are based on acute toxicity tests (ASTM Designation: E 1192-88) applied to mysid shrimp, Mysidopsis bahia and the silverside, Menidi beryllina using samples of fresh and the biodegraded produced water.

The results of produced water toxicity presented in Table 1 indicate that acute toxicity effect appears to be consistent for both species. The degradation of the effluent water with resultant shift in chemical analyte concentration resulted in a shift in acute toxicity for effluent water tested.

Important is the fact that degradation of chemical isomers often aid in the removal of toxic contaminants, but may result in the formation of metabolites which in themselves are often more toxic than the precursor compound' (7).

Chemistry

Connate water

The fresh and biodegraded effluent water was tested for the presence of 113 EPA defined contaminants to correlate toxicity observed to chemical residual. The contaminants were categorized as monoaromatic hydrocarbons (VOC), Phenols, or Polycyclic Aromatic Hydrocarbons (PAH). A total of 76 compounds were identified. Of those 76 compounds, 24 comprise approximately 85 percent of the total concentration of contaminants identified, (Table 2)

Specialty Chemicals

In the work reported here corrosion inhibitors and other additives are added to the connate oil-water stream to solve problems encountered in the production process. Although many of these chemicals are oil soluble/water dispersible and remain with the oil following oil-water separation, some are sufficiently water-soluble that a fraction not partitioned in oil and water treatment remains with the produced water, is discharged, and becomes bioavailable.

Only a few of the chemical additives applied in the system studied here are considered sufficiently water- soluble or dispersible to be discharged in produced water (Table 3). The percent discharge values applied here were determined using the conservative formula from CHARM (per 1996 recommendation) unless product specific data was available.

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Dilution and bioaccumulation determination

Difficulties addressing effluent water toxicity problems of offshore effluent plumes include the toxic composition of effluent-sea water mixtures, resultant toxic analyte bioavailability, intermittent exposure accumulation kinetics, and body residue determination.

In this study we used equilibrium partitioning theory where the lipid-water partitioning is adjusted by species- specific factors such as feeding, metabolism, growth dilution, and digestion [8-9]. Hence, the model considers surrogate marine organisms as species specific with tissue concentration and bioaccumulation of the chemical/s in aqueous solution with resultant concentration in tissue approximated by total lipids using octanol water coefficient or Kow.

For the present study, values for log Kow of petroleum hydrocarbons were obtained from Neff and Burns [10] and corrosion inhibitor values were obtained from empirical data utilizing PARCOM specified testing procedures. The lipid content of indicator species fish used in regression of log BCF/Iog Kow data is 7.6% wet weight [11] where log (BCF) = log (Ct/Cw), and Ct and Cw equal the concentrations of the chemical in tissue and dissolved in water, respectively, at equilibrium. The lipid content of Menidia and Mysidopsis, 6% and 3.3% respectively, was determined by lipid extraction from stocks utilized.

Important to real world applications is the majority of hydrocarbons and man made isomers present in produced waters require an extended contact time to reach equilibrium in tissues of aquatic animals. To model limited contact required the application of non steady state accumulation, the equations defined by Connell and Hawker [12] that express the BCF as a function of both Kowand exposure time were applied.

Finally, as noted in the introduction, effluent water plumes are subjected to dynamic shifts in direction and "ponding". Indeed, plumes subjected to open sea type hydrodynamics do not have a unidirectional flow but are subjected to many dynamic forces that result in plume redirection of up to 90 ° in 8 hours and 360 ° in a day.

This rapid movement in plume redirection results in non steady state load to resident stationary marine biota. To determine body residue concentrations associated with these movements we applied pharmacokinetic non- steady state summation of individual doses specific to a geographical location. This is accomplished by summing the contributions of each individual dose by noting the available concentration and decaying that concentration using the in body half-life defined;

t l / 2 = l n 2 / K 2= 0 .693 /K 2

Based on the compounds analyzed in fresh and degraded effluent water, we have obtained body residues (BR) (in mMoles) for the sum of all compounds determined using the BCF formula [Table 4].

The baseline CBR concentration based upon lipid concentrations as defined by McCarty is 2.87 mMol/kg for Menidia and 5.25 mMol/kg for Mysids. The estimated BR for all compounds analyzed in available effluent water denote results that are less than the literature defined CBR in spite of exposure based testing that indicates that a definable acute toxic response occurs.

To equilibrate known BR to defined toxic response a program of surrogate concentrations which combines the BRs calculated from chemical degradation analysis data correlated to the base data obtained from the toxicity tests were collated. Briefly implementation was as follows;

1 .) theoretical uptake and depuration rates (derived from Connell & Hawker) calculate the instantaneous BCFs at 24, 48 and 96 hours after exposure,

2.) From toxicity data we take the species/outfall specific mortality percentages at 24, 48 and 96 hours. For each dilution and time interval (24, 48, 96 hours) we plot this data against the estimated BR for all compounds analyzed at each corresponding time and dilution. The above noted process results in a graph of BR (total analyzed compounds) against % Mortality for each exposure interval,

4.) A best-fit line/linear regression was then plotted to provide species and outfall specific empirical equations.

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Analysis of the produced water/chemical surrogate CBR vs. 50% mortality denotes a concentration of 0.288 mmoles for Menidia and 0.725 mmoles toxicant concentration for Mysids.

Risk Determination

In a screening exercise of this type, it is appropriate (as defined by CHARM) and consistent with CBR determinations to assume that the risk (hazard indices) of all the chemicals measured in produced water are additive and definable.

As discussed above, marine organisms may bioaccumulate chemical constituents of produced water during exposure to a produced water plume. The CBR used here based on acute toxicity to aquatic animals, is definable and field verified. By applying geographically specific data from this model PEC/PNEC [Potential Environmental Concentration / Predicted No-Effect Concentration] or Van Leeuwen HC5 risk concepts have been developed that estimate risk to the impacted aquatic community during observed exposure. In this paper we only discuss the PEC/PNEC impact as it is more readily accepted.

Comparative Inhibitor Modeling

Presented below is the environmental impact and associated risk, as defined by PEC/PNEC [, of three different corrosion inhibitor types. These products are used for corrosion inhibition in three phase pipeline systems that discharge effluent water into a tropical marine environment. These corrosion inhibitors and the ancillary treatment products are used at treat rates, adjusted respectably, that provided less than 0.051 mm/y corrosion rate and an overboard oil in water effluent, where possible, of less than 20 ppm. The above-described model using observed effluent discharge parameters and empirical analytical data defines the environmental impact of that effluent. Defined is comparative impact of each product for based upon known toxicity and applied to a chronic PEC/PNEC risk assessment.

Akyl pyridine quaternary salt.

The first corrosion inhibitor investigated is an alkyl pyridine quaternary salt corrosion inhibitor commonly applied throughout Southeast Asia. This type inhibitor chemistry is long established, very effective but known to cause adverse environmental impact. For this specific formulation the PARCOM defined toxicity data is 5.5 ppm for Skeletonema and 16 ppm for Acartia Tonsa. To define the observed consequences of application (dirty water overboard, increased demulsifier and water clarifier requirements), as environmental impact we have applied field results to the model to ascertain environmental impact and risk. This product was applied at 12 ppm, which resulted in an increase to residual oil in water overboard (15 ppm to 40 ppm), increased demulsifier application (6 ppm to 15 ppm) and increased water clarifier application (6 to 20 ppm). As noted in the discussion above, these changes are additive to the base toxicity noted for connate water and result in a more toxic mixture to the environment.

The comparative results of the base connate water and connate water with alkyl pyridine quaternary salt model runs are presented in Figs 1 - 2. Immediately obvious is the increased area of adverse impact (21 km 2 [connate water] to 107.2 km 2 [water plus inhibitor]) when comparing 61 -day accumulation in Mysid shrimp and applying the PEC: PNEC ratio. This increase occurs as the toxicant concentration, attributed to the use of alkyl pyridine quaternary salt, increases residual hydrocarbon levels by a factor of 2.7 with corrosion inhibitor carryover of 17.1 per cent. The important factor to note is that the major portion of the toxic response noted is not directly caused by corrosion inhibitor, but rather indirectly caused by increased residual hydrocarbon carryover and increased levels of other production chemicals to improve water quality. Hence, improvements in corrosion inhibitor biodegradation ability and/or reduced product toxicity are less important than the ancillary overall effect caused by the use of this corrosion inhibitor. Once the water quality problems are resolved the bioavailabilty and resultant toxicity of the product must be addressed to reduce toxic impact.

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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 toxicity for this formulation, per PARCOM, is 0.3 for Skeletonema and 2.1 ppm for Acartia 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 toxicity 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 toxicity 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 toxicity is more important. Finally, in this comparison improvements in biodegradation ability are far less important than the overall toxic 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 toxicity for this formulation, per PARCOM, at 63 ppm for Skeletonema and 180 ppm for Acartia 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 toxicity 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 toxicant 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 toxicity 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 toxicity 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

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of residual inhibitor carryover. These results indicate that observed toxicity caused by increased residual oil carryover and inhibitor residual is of primary importance.

Fundamentally, these results refute the emphasis placed on biodegradation alone, as biodegradation does not address the overall impact of a product. In fact, a product with a lesser biodegradability may result in a reduction in environmental impact as exhibited by second generation products. Finally, it is important when comparing overall toxicity that any increase in residual oil and increased ancillary product application is considered as part of a product's overall toxicity and geographical risk.

Conclusions

The use of short term, exposure based, toxic response assessment correlated with rigorous chemical analyses of fresh and biodegraded effluent waters has resulted in the derivation of an "in body" residue model for toxic response and geographical risk. Application of this model to effluent waters containing residual corrosion inhibitors allows the comparative assessment of different specialty chemicals applied to the production stream for determination of toxic impact and geographical risk.

A comparison of three different types of corrosion inhibitors using this modeling process demonstrated a reduction in overall toxicity as defined by PEC:PNEC risk analysis when applying "green" inhibitor chemistry. Importantly the area of impact continues to be reduced with improvements in chemistry but product toxicity caused by increased inhibitor residuals remains problematic even where biodegradability improves. This indicates that an emphasis on biodegradation alone does not address the overall impact of a product in the environment. In fact, a product with less than optimal biodegradability may result in limited environmental impact as exhibited by second generation "green" products.

What appears to be of greatest importance when comparing overall corrosion inhibitor toxicity is that any increases in residual oil and increased requirement for ancillary product application must be considered as part of the proposed product overall toxicity and resultant geographical risk.

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produced formation waters in the Weat Java Sea, Indonesia. SPE 35846. Pages 683-689 In: Proceedings of the

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Science, Ann Arbor, MI, USA, P. 269 - 282

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Table 1

Percentage produced water required to cause acute toxicity

Menidia Mysids

LCso ,re 15.9% 33.7%

LCzl ~ve 6.8% 18.4%

Ta b l e 2. Concentration of contaminants 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%

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Table 3. Percent discharge and toxicity of additives used in production process

Add i t i ve Type Percent D ischarged A c u t e Tox ic i ty Range (mg/L)

Biocides 3.1 0.22 - > 1000 Corrosion Inhibitors 8.7 0.9 - 1055 Scale Inhibitors 66 600 - >10,000 Demulsifiers 2.0 10 - >10,000 Coagulant 85 15 - 14,800

Table 4

Equations for estimating body residue accumulation for analytes with the greatest concentration

Analyte B ioconcentra t ion data

I LOg R o w ~ l a n d a r d In fo rmat ton per lex t L o g B c f Per Vedh and Kosian Log BCF=O.79* logKow-0 .4 E q u i l . BCF l O ' L o g BCF k l Conne l l and Hawke r Ecotox. & Env i ron Safety #16 1988 ; k l = 10^(2.92 - 986*(Log Kow-5 8 7 ) ' 2 k2 Conne l l and Hawker Ecotox. & Env=ron, Sa le ty #16 1988

k2 = 1 /10^ (0 .0069* logKow^4 - 185* logKow^3~ 1.65*1og K o w ~ 2 - 5 . 3 4 * l o g K o w + 5 . 2 7 24 h r BCF K1;K2 * ( 1 -EXP(k2 *T lme (days ) )

• H a l f l i fe o r T 1/2 O 693/k2

P A H L o g K o w L o g B c f

51 -oenZo(bJtn lophenes 4.~6 3 4 4 D2 -benzo (b ) th l ophenes 5.5 3.95 ~aph tha lene 3.37 2.26 331 -naph tha lenes 3 8 7 2.66 332-naphthalenes 4.37 3.05 D3*naph tha lenes 5 3 5 5 D4-naph tha lenes 5 55 3.98 = luorene 4.18 2 9 0 D1 . f luorenes 4,97 3 53 2,2-f luorenes 5 2 3 71 ~henan th rene 4.57 3 21 ~nth racene 4.54 3 19 3enz {a )an th racene 6.75 4.93 Dhrysene 5.86 4.23

k l k2 T 112 T 1/2 Equ i l . BCF days days 24h r BCF days hrs

Z . IbU.43 6~9,B1 0,13 (520.2~ ~.~q~ 133.U 8,B 10.49 806 31 0.04 788.45 15.41 369.8

182,94 201.26 1.50 104.05 0.461 11.1 454,26 335 43 0.72 238.83 0.950 23.0

1.127.98 499 06 0 3 0 430 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 7 9 5 8 4 16 ,52 396 5 798.36 434,90 0.42 354 57 1.637 39 3

3 . 3 5 9 7 0 692.04 0 1 0 657.46 6.7 160.8 5,105 05 751.17 0 0 7 725.23 9.801 235.2 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 24 .41 585.9

P h e n o l L o g K o w L o g B c J

C1 -Pheno ls 2 06 1 2 3 C 2 - P h e n o l s 2.34 1 4 5 C3 -Pheno l s 2.95 1 93 C4 Pheno ls 3 1 2 05 o/m -Cresol 2 1 18

cresol 1 9 7 1 1 6

E q u i l . BCF k l k2 24h r BCF T 1/2 T 1/2 b .6 / lO,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 1 2 0 0 3 2 24 47 84 0.309 7,4 111.94 145.70 2 0 0 6 2 9 3 0.346 8.3 15 14 27.75 1 51 1431 0.458 11 0 14,33 2 6 3 2 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

To luene 2 69 1,73 E thy lbenzene 3 45 2,33 m / o / p - X y l e n e 3 13 2 07

E q u i l . BCF k l k2 24hr BCF 3" 1;2 T 1/2

19.1/ 34 /4 1 64 l b � U 0 ,311 9.11

I 53.10 B3 74 2.48 30 92 0.279 6.7

211,59 223 07 1 3 6 120.34 0.51 12.2 118.22 ~51 27 1 9 5 66.55 0.355 6.5

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Figure 1

Baseline risk of Connate water.

~" 36' S

Area of adverse impact 21 km2

I06° 42 ' 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.

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Figure 2

Akyl Pyridine Quaternary Compound

./,r

16' S

\ A ~ a of adverse impoct

1 0 7 . 2 kin2

J

42' S 106"36 ' E

" ./,,,r

106"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

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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

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F I G . 4

Second Generation

/

Area of adverse impact 38.3 kmZ

o," 42' S

106"38 ' E lOB" 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