IWC 12-52

MPP No. 2012-132/DTM/mt/mk

“Toxic dissolved and dispersed hydrocarbons removal and reuse

in the oil & gas industry, gas/condensate, shale gas produced water,

refinery process water and groundwater with the Macro Porous Polymer Extraction

technology”

DICK TH. MEIJER, VWS MPP Systems / VWS Oil & Gas, Veolia Water Solutions & Technologies, Ede, the Netherlands,

KENNETH SEVERING, Whittier Filtration, Veolia Water Solutions & Technologies, Brea, CA, United States

This paper was presented at the International Water Conference, San Antonio (TX), USA on November 5, 2012

PAPER NUMBER IWC-12-52

KEYWORDS

MPPE, produced water reuse, wastewater reuse, groundwater reuse, dissolved and dispersed hydrocarbons, Zero Harmful Discharge (ZHD), Environmental Impact Factor (EIF), aromatic hydrocarbons, BTEX, Poly Aromatic Hydrocarbons (PAHs).

IWC 12-52

MPP No. 2012-132/DTM/mt/mk 2

ABSTRACT

Environmental legislation worldwide is aiming at a good balance between the extent of environmental protection and spending capital on water treatment systems with the associated carbon footprint. There is a clear trend to move from integral discharge parameters like BOD, COD, AOX etc. to more risk based approaches, like the Environmental Impact Factor introduced in Norway in the beginning of this decade. In risk based approaches a division is made between harmful and non-harmful constituents present in the water. Technologies specifically removing the harmful part are searched for to aim at an optimal balance between capital costs and environmental protection. A real life experience on the disastrous effect of unknown toxic content on the biotreatment confirming the Environmental Impact model will be presented. Macro Porous Polymer Extraction is such a technology that specifically removes the toxic non polar hydrocarbons from water. More than 35 units have been installed in the past years and applied in the various areas of the oil & gas industry. Examples are given of onshore shale gas produced water, refinery process/wastewater, groundwater and offshore gas/condensate produced water on platforms and future floating LNG plants. Constituents that are removed are among others, dissolved and dispersed oil (aliphatics), BTEX, Poly Aromatic Hydrocarbons (PAHs), MTBE, THT (Tetra Hydro Tiophene, an odorant used in natural gas for leak detection). Recently it has been discovered that > 80% of Mercury is removed from produced water raising the possibility to extend scope the technology. Finally the reduction of the Environmental Impact Factor with MPPE will be illustrated versus other technologies.

The Macro Porous Polymer Extraction (MPPE) technology from Veolia Water is able to remove dissolved and dispersed hydrocarbons with 99.9999% if needed. The MPPE technology is basically a liquid/liquid extraction process where the extraction liquid is immobilized in a macro porous polymer. In addition it allows the practically pure separated hydrocarbons to be completely used as a product. No other “waste“ stream is created.

IWC 12-52

MPP No. 2012-132/DTM/mt/mk 3

INTRODUCTION

The Macro Porous Polymer Extraction Technology (MPPE) has been proven in various applications to remove the non-polar generally toxic hydrocarbons from produced, waste and groundwater. This MPPE technology makes it possible to change the discharge regulation policy from generic BOD, COD requirements to one that is more focused on the toxic content of the water to be treated. This will lead to a discharge with constituents basically non harmful to the environment. In addition, where low BOD, COD levels are required, the MPPE technology can be applied to protect the biotreatment against toxic loads. In this paper an introduction to a risk based approach vs. total COD removal is given with subsequent examples validating this alternative approach. Cases are presented in the Oil and Gas industry on Zero Harmful Discharge and on combining the MPPE with biotreatment technologies to fulfill total COD requirements where significant toxic content is present.

REASONS FOR COD AND BOD

REQUIREMENTS FOR WATER DISCHARGE REGULATIONS

Most natural waters contain small quantities of

organic compounds. Aquatic microorganisms have evolved to use some of these compounds as food. Microorganisms living in oxygenated waters use dissolved oxygen to convert the organic compounds into energy for growth and reproduction. Populations of these microorganisms tend to increase in proportion to the amount of food available, when nutrient (N, P and some minerals) concentrations are not limiting. This microbial metabolism creates an oxygen demand proportional to the amount of organic compounds useful as food. Under some circumstances, microbial metabolism can consume dissolved oxygen faster than atmospheric oxygen can dissolve into the water. Fish and aquatic insects may die when oxygen is depleted by microbial metabolism. Especially discharge of (municipal) wastewaters into rivers or lakes may lead to depletion of oxygen as the feed of organic compounds and resulting oxygen demand is higher than the natural atmospheric oxygen input (related to the available surface area between water and air) and the dilution with fresh oxygenated water (related to the flow rate of fresh water).

As the amount of dilution with fresh water is often not controllable the environmental legislation

is aimed at the reduction of BOD and COD discharge to the environment.

REASONS FOR THE EMERGENCE OF RISK BASED APPROACHES TO WATER DISCHARGE

REGULATIONS

Discharge regulations based on BOD and COD for municipal wastewater have been proven effective in practice. For the offshore industry emerging in the seventies in the North Sea these requirements were not feasible and not meaningful. Not feasible as space limitations impede the use of biotreatment systems that are needed to lower BOD or COD levels. Not meaningful as the dilution prevents oxygen depletion.

From the very beginning the discharge regulations for the North Sea were only based on dispersed oil. The aim of this regulation was to reduce the formation of oil sheens on the surface water. The discharge limit was set at < 40 ppm dispersed oil. The discharge limit was mainly based on technical/practical limitations like space, weight and economics. Given these limitations no technologies were available to achieve lower limits.

By the end of the nineties extensive research was carried out by the Norwegian Oil & Gas industry on the toxic and non-toxic constituents of produced water and their effects on the environment. The investigations were probably driven by the Norwegian government dealing with the interests of the fishing industry. It has led to a change in approach of offshore produced water treatment resulting in a focus on the removal of toxic constituents.

THE ENVIRONMENTAL IMPACT FACTOR – A PRACTICAL APPLICATION OF A RISK BASED

APPROACH

The basis of this study consists of a detailed analysis to identify molecules and groups molecules that are toxic and nontoxic. The effect of the toxicity on their natural environment was assessed. This assessment was based on the accessibility of the toxic constituents to the natural organisms in the sea (alga, fish etc.), the biodegradability and the tendency of accumulation in the environment. Mathematical models of the spreading of toxic constituents in the sea were validated by the measurements of the constituents in mussels and other species located at different distances from platforms. For example at distances of 16 km downstream from platforms

MPP No.

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IWC 12-

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-52

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IWC 12-

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-52

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2012-132/DTM

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Table 3.

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IWC 12-

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-52

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2012-132/DTM

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IWC 12-

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-52

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MPP No.

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2012-132/DTM

Photo 3. MPPGermigny so

RY WASTEWa MPPE (Maon) pilot unit wrational perio. The procescorrosion inht and treated arator, then amoval), followuctuations in

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M/mt/mk

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a pilot DGF uwed by the M

n the refinery MPPE pilot stee (3) week nce of the MPat fluctuationng the pilot plpled. Samplen. The samplfied laboratorile petroleume petroleum hcal results ar

de France, s, France.

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Sum of concentration (ppb)

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Sum of concentration (ppb)

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raph 7.

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IWC 12-

uring MPPE 

 o‐xylene

m.p‐xylene

ethylbenze

 toluene

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ring MPPE 

dodecane

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C8‐C10

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water during MPPE

-52

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MPP No.

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4000

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2012-132/DTM

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ion of MPPE PPE technolo,2,3 (Volatile ics and arom

ctable Petroleomatics) to aal efficiency wit was operatfully automatit was succet the necessi

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Graph 11.

Graph 12.

field pilot tesogy is able toPetroleum H

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IWC 12-

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-52

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2012-132/DTM

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EMEDIATIONCATION LOC

former iron curce for eneremicals. In thhole of Europfor city gas amainly replacs led to manygroundwater in these groused aliphaticatics and pheo high that thl attenuationpots is minimons. The MPpresented in

Table 9. water remedioal gasificatio

Graph 14.

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S POLYMER) TECHNOLO

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In the MPPErocarbon-conh a column particles are popecific extractliquid removents from the peither be reu

generation ofby stripping thw pressure stare then coner phase by rocarbon phaom the systemisposal.

IWC 12-

ectron macro porous

4. The porosnitially dia in medica

er treatment orous polym

oil from waterthe idea

emove by he pores of tMPPE id 1990s.

rous polymer

E water ntaminated acked with orous polymetion liquid. Thes the process watesed or

f the extractiohe eam. The densed and gravity. The

ase is m and left

-52

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MPP No.

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The c

the systecontinuoand regeextractioshows a

2012-132/DTM

Photo 5. T

unit at LBC

condensed aem. The applous operationeneration. A ton and one ho

simplified flo

M/mt/mk

The MPPE p

Photo 6. Rotterdam, t

queous phaslication of two

n with simultatypical cycle our of regeneow-sheet of t

rocess.

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11

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CHEMICALMPPE - Aftdeveloped,actually on of Elf AquitTotal, then

The MP99% at 3,00beginning fthe results Petroleum 1998). At thspecific ste1997), but

d photo 6 is allation.

PPE technolosed hydrocar(BTEX), polyd) hydrocarbtimes reductechnology caoduced water and groundcluding the ocoatings and PPE technoloons in practicnot create a wcan withstandnts containinnhibitors, scas, demulsifierheavy) meta

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L CONSTITUter the MPPE the first appa gas offshoaine in HarlinVermilion; p

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a photo of a

gy can reducrbons such aaromatic andons with 99.9tion), if requian be used foer, process wdwater in a wffshore gas apharmaceutgy separates

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ble 10.

UENTS REDUE technology plication in 19ore producedngen (which hoto 7). on performanent levels fro compounds

published in aonference (PAquitaine had(Kloppenburgned that tech

IWC 12-

full-scale

ce dissolved as aliphatics, d halogenate9999% remored. or treatment

water, ide variety ofand oil, ical industries the m for (re)use

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-52

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producedoperation

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require aor polyarwhile befby the ofgovernm(Kaa and2004) anTest cenCenter, 1dissolvedproducedcarried oNetherlamonth tepresenteConferenSome mgas/condNorway) of succe1990s angovernmto the ins

2012-132/DTM

d water treatnal/maintena

o 7. MPPE u the

gislation at tha reduction inromatic hydrofore the MPPffshore indus

ments (NOGEd Petrusevki,nd the oil andnter) (ERT/Or1997), were ad aromatics ad water. The out by NAM (ands’ part of test with exceled at the 200nce (Meijer aore offshore densate prod and Shell (inssful offshorend beginning

mental pressustallation of t

M/mt/mk

ment due to ance reasons

unit at VermilNetherlands

hat time did nn dissolved aocarbons (PAPE technologstry (Dalen). NEPA study on, 1988), OSPd gas industryrkney Water addressing thand PAHs em first offshoreShell/Exxon)the North Sellent results, 1 Offshore T

and Kuijvenhofield tests we

duced water bn Malaysia). e field tests a

g of this centuure in the Nethe first comm

costs and s.

ion, Harlinges.

not formally romatics (BTAHs), it took gy was requeNevertheless

n 55 technoloPAR (OSPARy (Orkney WTechnology he issue of mission in e field test wa) on L2 in thea. It was a 4 which were

Technology oven, 2001).ere carried oby Statoil (in The combinaat the end of ury and therlands hasmercial MPPE

12

en,

TEX) a

ested s both ogies R,

Water

as e

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ation the

s led E

units offshoDutch part K15A and Koperation sseparation and aliphatconcentratistarted up iand Woodsare include(FPSO) offsDelta.

Due to fregarding tPAHs emisout on requNAM and Textensive oHydro on Ttests a conobserved fobelow C20 removal watotal alipha91–95% fo

REA

An examshown in greal life anaMPPE unit mono ethylThe design1,500 ppm BTEX (disp1,400–7,70dissolved oas a total to

Graph 15

ore, on the mof the North K15B). Thesesuccessfully sperformance

tics at 300–8ions. Statoil/Sin 2007 (Shoside Pluto in ed in Prelude shore Austra

further develohe issue of d

ssion, a formauest of OSPATotal (Meijer offshore field Troll B (Pollessistent reducor BTEX anda consistent

as measuredtics removal r Total and >

AL LIFE ROB

mple of the roraph 15 whealyses since treating gas ene glycol (M

n was to reduto < 1 ppm.

persed and d00 ppm and aoil) from 150–o 3–0.5 ppm

5. A real life actual MPP

most critical pSea (Total Fe units have since 2002 we of > 99% of00 ppm influShell Ormen otun; Salevik;2011. Recen(Floating LN

alia and in the

opments in Odissolved aroal investigatio

AR on oil prodet al, 2004). test was car

stad, 2005). Iction of > 99%d PAHs. For at reduction at in all field tethe picture w

> 95% for Tro

USTNESS O

obustness of re the design1994 are givproduced wa

MEG) regeneuce dissolvedIn practice inissolved arom

aliphatics (dis–1,437 ppm win the outlet.

example of dPE performan

IWC 12-

latforms in thF15A, NAM

been in with a f BTEX, PAHent Lange was

; Silverstone)ntly MPPE unNG), Ichthys e West Nile

OSPAR omatics and on was carrieduced water Later an

rried out by In these field% was aliphatics t 95–99% ests. For the was mixed: oll B.

OF MPPE

f MPPE is n values and ven for an ater and a eration streamd BTEX from nfluent levelsmatics) from spersed and were reduced.

design versusnce.

-52

he

Hs

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d

m.

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d

s

MPP No.

M

In recthat MPPgas/condphenomecases whfindings 1999 in tBelow ingiven. Thbetweenppb. Leadetectab

Gra

BOD,

parametewastewa

Induscontents

2012-132/DTM

MERCURY R

cent benchmPE also remodensate prodenon was cohere Mercuryconfirm the fthe NAM field graph 16 thehe observed 82 and 99%

ad, cadmium ble.

aph 16. Merc

CO

, COD, TOC ers are effec

aters. strial wastewas are present

M/mt/mk

REMOVAL W

ark studies itoves Mercuryduced water. onsistently oby was measufirst time this d test (Kuijvee results of sremoval effe

% at inlet leveand nickel w

cury removal

NCLUSIONS

and other “inctive in munic

aters where srisk based a

WITH MPPE

t was discovey from This

bserved in allured. These was measur

enhoven et alsuch a seriesectiveness vaels from 5 to 1were hardly

l with MPPE.

S

ntegral” dischcipal and non

significant toapproaches a

13

ered

red in l).

s are aries 120

.

harge ntoxic

oxic are

emerging. Ttoxic conte

Risk basthan dischaparameters

The conFactor as aoffshore prorecognition

Extractiotechnologieas has beeproduced w

The remissue to be are to be mfunction of biotreatmenloads.

MPPE hEnvironmewater.

The MPthe removaand ground

The % sMPPE unit concentratioperation.

MPPE ron various water bencplanned to so as to coremoval.

They focus ont to create ased approacarge policies s like COD. ncept of the Ea form of a risoduced wate worldwide. on technologes to implemeen proven in owater treatmemoval of toxic addressed w

met and toxic the biotreatmnt against hig

has proven antal Impact F

PPE technoloal of toxic condwater with leseparation peis independe

ion of the targ

removes Mergas/condens

chmark studiefurther substme to a “con

on selective ra Zero Harmfhes are morebased on int

Environmentask based apper goals is ga

gies like MPPent risk baseoffshore gas/ent. c hydrocarbowhen COD recontent thre

ment. MPPE gh and chang

95 to 99% reFactor in offs

gy has consintents in prodevels arounderformance oent of the inleget compoun

rcury with 81 sate Offshorees. Further sttantiate this p

ntrolled” and p

IWC 12-

removal of thful Dischargee cost efficientegral

al Impact proach to aining

PE are effectied approache/condensate

ns is a speciequirements atens the protects ging toxic

eduction of thore produce

istently showduced-, waste 99%.

of an installedet nds during

to 99% basee produced tudies are phenomenonpredictable

-52

e e. nt

ive es

fic

he ed

wn e-

d

ed

n

IWC 12-52

MPP No. 2012-132/DTM/mt/mk 14

Annexes

ACKNOWLEDGEMENTS

The basis of this paper is the series of field tests carried out on request of Oil and Gas companies and the data provided by them of running MPPE units since 1994. This has resulted in a wealth of information that has been used in this paper together with the publications mentioned in the reference list.

This paper would not have been possible without the help and support of Peter Nekeman, making the graphs based on the labtest and pilot test figures and Mrs Marijke Kuntzel for consuming the continuous stream of new drafts and her constructive comments. I would like to thank Jan Bart Kok for his contribution to the COD and BOD paragraphs of this paper.

REFERENCES

BERGERSEN, L. AND JACOBSSON, J. 2006—New Offshore Tie-ins and impact on Onshore Facilities, Field Case Kollsnes. Tekna Produced Water Management Conference, Stavanger, Norway.

BERGERSEN, L., JACOBSSON, J. AND MEIJER D.TH. 2006—Solving the Impact of High Toxic Loads in the Produced Water at the Kollsnes Gas Terminal by Applying the MPPE technology. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.

BULLER, A. T., JOHNSEN, S. AND FROST, K. 2003—Offshore produced water management—knowledge, tools and procedures for assessing environmental risk and selecting remedial measures. Memoir 3. Stavanger, Norway: Statoil Research and Technology Offshore.

CHEN, G.Z. AND EBENEZER T.I. 2012—Produced water treatment technologies. Faculty of Engineering, Department of Chemical and Environmental Engineering, and Energy and Sustainability Research Division, University of Nottingham, Nottingham NG7 2RD, United Kingdom. 4 July.

DALEN, A.V. 2004—Produced Water Regulations in the Netherlands. NEL Oil-in-Water Monitoring Workshop, Aberdeen, United Kingdom, 22–23 September.

ERT/ORKNEY WATER TECHNOLOGY CENTER, 1997— The removal of dissolved and dispersed organic components from produced water. ERT F92/178, requested by Exxon Mobil, Total, Amarada Hess.

GRINI, P.G., HJELSVOLD, M. AND JOHNSEN, S. 2002— Choosing produced water treatment technologies based on environmental impact reduction. HSE Conference, Kuala Lumpur, Malaysia, 20–22 March, SPE paper 74002.

ITHNIN, I.B. AND CHRISTOPHER, G. 2006—The discharge of produced water from oil and gas production: Legislation requirement in Malaysia. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.

KAA, C.C.R. VAN DER AND PETRUSEVKI, B. 1988— Inventarisation of removal techniques to reduce the benzene heavy metal emissions from offshore platforms. (In Dutch). NOGEPA (Netherlands Oil and Gas Exploration and Production Association) and Dutch Government, Report 61944-00-32-301-2.

KLOPPENBURG, M.F.C. AND VENEMA, W. 1997—De-oiling condensed glycol regenerator overhead vapours by steam stripping. 1997 SPE/UKOOA European Environmental Conference, Aberdeen, United Kingdom, 15–16 April, SPE paper no. 37846.

LOWE, I. 2006—Shaping a sustainable future—challenges for Australia’s oil and gas industry. APPEA Environment Conference, Coolum, Australia, 19–21 November.

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MPP No. 2012-132/DTM/mt/mk 15

MEIJER D.TH. AND KUIJVENHOVEN COR A.T. 2001— Field-Proven Removal of Dissolved Hydrocarbons from Offshore Produced Water by the Macro Porous Polymer Extraction Technology. SPE Offshore Technology Conference, Houston, Texas, USA, 30 April–3 May, OTC 13217.

MEIJER D.TH., KUIJVENHOVEN COR A.T. AND KARUP, H. 2004—Results from the latest MPPE field trials at NAM and Total Installations. NEL Produced Water Workshop, Aberdeen, United Kingdom, 21–22 April.

MINISTRY OF ECONOMIC AFFAIRS, 1995—Declaration of Intent, Implementation of Environmental Policy for the Oil and Gas Industry. NOGEPA (Dutch Oil & Gas Exploration and Production Association), The Hague, the Netherlands, 2 June.

OSPAR DENMARK, 2004—Definition of a data collection strategy for aromatic hydrocarbons by OSPAR Contracting Parties in 2004, OSPAR Background Document concerning Best Available Techniques and Best Environmental Practice for the Management of Produced Water from Offshore Installations. OSPAR meeting of the Offshore Industry Committee (OIC), Dublin, Ireland, 15–19 March.

PARS, H.M. and MEIJER D.TH. 1998—Removal of dissolved hydrocarbons from production water by Macro Porous Polymer Extraction (MPPE). SPE International Conference on Health, Safety and Environment in Oil and Gas Exploration and Production, Caracas, Venezuela, June, SPE paper no. 46577.

PHILLIPS, R., RIOS, A. AND CAYMO, A. 2006—Assessing the Risk from Discharging Produced Water to the Marine Environment. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.

POLLESTAD, A. 2005—The Troll Oil Case—Practical Approach towards Zero Discharges, Troll Projects. Tekna Produced Water Management Conference, Stavanger, Norway, 18 January.

SALEVIK, P. 2009—Onshore Water Treatment, Experience from Ormen Lange, Nyhamna. Tekna Produced Water Management Conference, Stavanger, Norway.

SILVERSTONE, M. and Vik, E. 2012—Application of whole effluent assessment (WEA): evaluating the performance of the Ormen Lange produced water treatment plant. Tekna International Produced Water Management Conference, Stavanger, Norway, 24-25 January.

SJØTHUN, S., 2002—The Process of Developing a Total Effluent Water Handling System for Ormen Lange. Tekna Produced Water Management Conference, Stavanger, Norway.