AnnexI

GUIDELINES FOR MANAGING NATURALLY OCCURRING RADIOACTIVE MATERIALS IN PRODUCTION OPERATIONS

H. BASHAT, SENV Environmental Advisor

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Managingnaturallyoccurringradioactivematerialsinproductionoperations

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GUIDELINES FOR MANAGING NATURALLY OCCURRING RADIOACTIVEMATERIALS(NORM)INPRODUCTIONOPERATIONS SUMMARY Naturally occurring radioactive materials, NORM, have been known to be present in varying concentrations in hydrocarbon reservoirs. These NORM, under certain reservoir conditions can reach hazardous contamination levels. The recognition of NORM as a potential source of contamination to oil and gas facilities has become widely spread and gaining increased momentum from the industry. The contents of the Annex which wee extracted mainly from References 1 to 3, address the various problems with NORM and provides the recommended procedures for managing these materials. INTRODUCTION TherearetwotypesofNORMcontaminationwhicharecommonlyknowninthe oilandgasoperations: 1) Radiumcontaminationwhichiscommontoformationwaterandproduces lowspecificactivityscaleknownasLSA. 2) Radoncontaminationwhichiscommontonaturalgasproduction. Both of these elements when accumulate in significant concentration will form serious health and environmental hazard in addition to the operational problems. Therefore periodic analyses to detect and identify these contaminants at an early stage is becoming an acceptable industry practice. The following sections will address each type separately.

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I. NATURALLY OCCURRING RADIOACTIVE MATERIALS FROM PRODUCTIONWATER BACKGROUND Naturally occurring radioactive materials NORM in formation water are soluble radionuclides, may precipitate, under certain operational environment, as low specific activity scale, known as LSA scales. These scales tend to be barium sulphate and strontium sulphate which co-precipitate with naturally occurring radium leached out of the reservoir rock; such scales emit alpha, beta and gamma radiation and this, together with the physical properties of the LSAS, can give rise to a number of problems if such scales or sludges have to be removed, handled or disposed. Once LSA scales are formed within the production system two main problems are presented: the scale will tend to foul valves and restrict the well fluid stream, and secondly, the levels of radiation on the outside of the flowline or vessel may be so high that the surrounding area may have to be designated as a restricted area and be cordoned off. Scale formation can be prevented with some success by the use of scale formation inhibiting chemicals. However, if the removal of LSA scale is necessary it can be difficult and expensive because LSA scales (unlike calcium carbonate scale) are insoluble in inorganic acids. Scale will either have to be removed (by hand or mechanically), or the scaled up equipment taken out of service and put into safe storage. Therefore safe systems of work and proper procedures which recognise the hazards, protect the workers from harmful exposure, minimise interference with the environment and ensure compliance with government and international regulations are essential. 1.ORIGINANDFORMATIONOFRADIOACTIVESCALE 1.1Naturallyoccurringradioactiverocks The main radioelements found in the common sedimentary rocks include potassium, uranium and thorium and the highest concentrations are normally found in shales as indicated in Table 1.

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Table1Radioelementconcentrationinsedimentaryrocks K-40 (ppm) Sandstones a) Orthoquartzites b) Arkoses 1.7 U-238 (ppm) 0.45 1.5 Th-232 (ppm) 1.7 5.0

Shales a) b) Greyandgreen Black 0.4 2.9 3.2 8-20 2.2 <0.1 1.1 13.1

Limestones Evaporites

The potassium content of shales is a reflection of their clay mineral, particularly illite content. The high uranium concentrations in black shales are probably due to their augmented organic content. Sandstones owe their potassium values to their K-felspar, K-mica and glauconite content. The uranium content of limestones is held largely within the crystal lattice of calcium carbonate where the uranium ions substitute for the calcium. Thorium, however, does not enter the carbonate lattice easily and, in consequence, thorium values tend to be low and held mainly in the clay and heavy mineral fractions. Uranium and thorium values in evaporites are, however, very low and restricted to the small detrital silicate mineral fraction. 1.2Radioactivedeposits Generally it can be said that the radionuclide enrichment of the formation water occurs due to the concentration of uranium and thorium-bearing minerals within the source rock. Subsequent leaching by formation or injection water may result in radioactive deposits in the production train given suitable conditions. The injected seawater, being normally less saline than the formation water, may additionally dissolve radioactive salts from the minerals present in various geological strata. These deposit can take several forms: Scales Natural formation water will undergo changes of temperature and pressure as it is coproduced with the oil and gas, and may under certain conditions deposit scale within the oil production system. Depending on variations in temperature, pressure, flow and geochemical conditions, these radioactive salts selectively precipitate in a non-reversible manner on the cement, or pipe around cased wells, liners, tubings, etc. This is significant from the radiological protection aspect since the co-precipitation effectively encapsulates the radium in a minerals shield, thereby ensuring almost complete self-absorption of the alpha particles emitted during the radioactive decay. Thus, a combination of radioactive leaching by either the natural

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formation water or the injected seawater together with the occurrence of injection water "breakthrough" may lead to deposits of mineral scale containing measurable quantities of natural radioactivity concentrated by this scaling process. Sandandsiltdeposits These are potentially a greater problem in topside equipment (e.g. production separators). This material can act as an absorbtive surface for radionuclides present in the production fluid. An exchange mechanism between cations can then give rise to radioactive sludges and deposits. Radon-222 gas is part of the decay chain of radium-226. In most cases where radioactive scale is produced radium-226 as well as some of its daughter nuclides including radon-222 may be found entrapped within the scale. Normally, radon-222 would be carried away with the normal gas. There are fears that where sludges are formed, the entrapped radon-222 gas may be given off in relatively large quantities, particularly when this sludge is being disturbed. Therefore precautions must be taken to protect the people working with such materials. Iron(rust)deposits It has been noted that occasionally a matrix like iron oxide in oily-water separators has exhibited low levels of radiation. The mechanism is unclear, but there is some speculation that radium-226 could be locked into rust itself. Leaddeposits In some cases lead deposits occur which have high Pb 210 contents. They can occur with gas wells producing from carboniferous strata. Often they are characterised by high sodium chloride concentrations in the formation water. The deposits are usually found in well tubing and well heads. 2.ENVIRONMENTALPROBLEMS Radioactive scales and sludges or contaminated equipment may have to be removed at some time for storage or disposal. Since this could cause environmental problems strict precautions have to be taken to prevent the irradiationandcontaminationofpeople,animals,plantsandothermaterials. Theproblemsinvolvedare: 2.1 Radioactivescalestendtobehighlyinsolubleinacids.Theycontrastwith mostcommonnonactiveshales(e.g.calciumcarbonate)whicharereadily solubleinacids.Difficultiesexperiencedindissolvingscalewithinorganic acidshouldprompttocheckforthepresenceofradioactivity. 2.2 LSA scales invariably emit alpha and beta particles and gamma rays. Their presence in production systems and equipment can give rise to occupationalhygieneproblems.Aparticularconcerniswithdustparticles whichcanbereleasedincleaningoperations.Thisdustcanbetrappedin thetissuesofthelungandemitalphaparticleswhichcancauselongterm

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healthproblems. WhereLSAscaleispresentinproductiontrainsorin itemssuchastubularsorwellheads,concernmainlycentresonanyeffect thatthegammaradiationcouldhaveonthoseworkingcloseby. 2.3 Radioactivescaleontheinsidesofthetubingstringsmayinterferewiththe naturalradioactivelevelsofthesurroundingstrata,causinganomaliesin thereadingsfromgammaraylogs. Theobservationofsuchgammaray anomaliescanbeanearlyindicatorofthepresenceofradioactivescales. 3.UNITSOFMEASUREMENT The units used for Activity, Absorbed Dose and Dose Equivalent have recently changed following the introduction of SI units and are: 3.1Activity Theactivityofanamountofradioactivenuclideatagiventimeisthenumber ofspontaneousnucleartransformationsinthetimeunit.TheSIunitofactivity isthebecquerel(Bq)equalto1nucleartransformationpersecond. 3.7x1010Bqequals1Curie(Ci)exactly 37 M Bq equals 1mCi (millicurie) 37 k Bq equals 1Ci (microcurie) The units generally used for measurement are Bq/g for solids and Bq/l for liquids and gases. 3.2Dose A term denoting the quantity of radiation energy absorbed by a medium. Althoughtheterms"dose"or"radiationdose"areoftensuedinageneralsense, theyshouldusuallybequalified,forexampleasabsorbeddose,doseequivalent, etc.ThedoseisstillusuallymeasuredinpreSIunits.ThreepreSIunitsare used,viz: 3.2.1 theRoentgenwhichmeasurestheradiationdoseinairandissometimes calledtheexposuredose; 3.2.2 theRadwhichisameasureoftheabsorbedradiationdose,and 3.2.3 theRemwhichistheunitofdoseequivalent.Forallpracticalpurposes, it is assumed that doses measured in Roentgen are equal to doses measuredinradsatthesamepositionintheradiationfield. Onlydosimetersformeasuringneutronsarenormallycalibratedinremunits. The unit of dose equivalent takes into account the fact that some types of radiation,particularlyalphaparticlesandneutrons,aremuchmoreefficientat killingordamagingcellsperunitamountofabsorbeddose. Theremdoseis relatedtotheraddosebythefollowingrelationship:

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Dose in rem = Dose in rad x QF (dose equivalent) (absorbed dose) (quality factor) The value of the quality factor can be as high as 20 for alpha particles and 10 for neutrons. For gamma and beta particles, it is 1. These units are large and for operational purposes measurements are made in mR, m rad or mrem, which are 1/1000 of the principal unit. Under SI units, the Roentgen does not have an equivalent. The unit of absorbeddosereplacingtheradisoftheGrayorJoulekg1andtheunitofdose equivalentreplacingtheremistheSievert.TheseSIunitsarerelatedinthe samewayastheradandtherem,i.e.: Dose in Sieverts (Sv) = Dose in Grays (Gy) x QF Bydefinition: 1 Gray = 100 rad 1 Sievert = 100 rem The SI unit is thus even larger than the existing unit and measurements will be made in Gy or Sv (1/1,000,000th of the principal unit). 4.FIELDEQUIPMENTFORRADIATIONDETECTION Generally there are two broad types of detectors available; contamination meters for measuring surface radiation such as alpha and beta, and the dose rate meters for measuring gamma radiation. There are also devices capable of measuring both beta and gamma radiation simultaneously. 4.1Contaminationmeters These are very sensitive devices for measuring surface radiation. They indicate level of radiation in "counts per second" and should be able to measure alpha, alpha and beta, and beta radiation. The ability to measure these three ranges is necessary because if the LSA scale is damp, if there is moisture in the atmosphere or LSA scale is overlayed with calcium carbonate scale, then the alpha particles may be absorbed. However, by measuring alpha and beta emissions together the alpha emissions of the LSA scale may be inferred, i.e. as far as LSA scale is concerned alpha and beta particles are always emitted together. If an indication of LSA scale contamination is given by such a meter it must be confirmed by radiochemical analysis or gamma spectrometry. Contamination meters should be calibrated against a range of sources of known activity and of similar isotopic composition; the calibration chart then produced will enable, say, a reading of five counts per second to be converted to 0.37 Bq/cm2 which would only be true for that particular meter. However, personnel trained in the use of such meters will soon become adept at interpreting readings correctly. Contamination meters, if treated with care, will give an early indication of a contamination problem, provided that the scale is not shielded. 4.2Radiationmonitorsordoseratematers These meters are reasonably robust and are used to measure radiation levels throughout industry. Generally they indicate measurements in Sievert/hr and measure gamma radiation. They are not as sensitive as contamination meters at measuring levels near

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background but are a very useful tool to establish whether or not LSA scale with higher levels of radiation is present inside pipelines, wellheads, vessels, etc. This is because the steel will stop the alpha and beta particles but allow a certain percentage of the gamma ray to pass; levels of radiation inside a steel pipeline or vessels may be in excess of two to three times those indicated outside, depending on the thickness of the steel. 4.3Availabledevices The available devices to measure gamma and beta radiation in the field equipmentandfacilitiesduringoperationsandmaintenanceare: sodiumiodidescintillationcounters(SC); energycompensatedgeigermueller(GM); thinwindowgeigermuellerPancake(PK). 4.4Generalconsiderations Bothtypesofmeterareavailablefromanumberofmanufacturersworldwide buttherearesomebasicprecautionswhichmustbetakenwheneitherorboth areused: themetersshouldbecalibratedbyasuitablelaboratoryandeither,inthe case of a contamination meter, a conversion chart supplied for that particularmeteror,inthecaseofadoseratemeter,themeteradjustedto readasaccuratelyaspossibleacrosstherange; metersshouldbeoverhauledandcalibratedatleastonceayear; ifameterisdroppedordamageditshouldberecalibrated; metersshouldnotbeabusedandshouldbeswitchedoffandkeptsecurely whennotinuse; personnelwhousesuchmetersshouldbetrainedintheiroperation,beable tointerpretreadingsproperlyandbeabletorecognisewhenmetersmaynot beworkingproperly; indicationsofLSAscaleshouldbeconfirmedbyradiochemicalanalysisof gammaspectrometry sothat acompletely accurate record ofthe levels of radiationmaybekept. Note: LSA scales with high levels of contamination, and therefore posing potentially high health risks of inhaled/ingested, may not register as such on dose rate meters and ideally, if the presence of LSA scale is suspected, both kinds of meter should be used together.

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5.RECOMMENDEDLIMITS 5.1Doselimits The basic recommendations of the International Commission on Radiological Protection (ICPR) are laid down in its publications No. 26 and 30. However the "dose equivalent limit" recommended by ICPR is 50 mSv over one year according to the defined working conditions. Table 2 summarises these recommendations. 5.2Activitylimits When radioactive materials are handled, they should be classed as a radioactive substance when the specific activity level (the activity per unit of mass) is greater than 100 Bq/g. This limit only refers to the activity level of the material itself. This must be clearly distinguished from the limit that is used for decontamination purposes: the allowable contamination level for alpha emitters on a surface is usually 2 Bqcm-2. Therefore, when either of these limits is exceeded, proper operation, handling and disposal are required. 6.OPERATIONALPROCEDURESDISPOSALASPECTS 6.1Scalehandling Whenhandlingscaleorscaleditems,duringsuchoperations,aswhenpulling tubing,enteringproductionseparatorsorproducedwaterskimmers,removalof Xmastrees,valves,metersandflowlines,etc.Thefollowingmeasuresshould beconsidered: containcontaminationasnearaspossibletoitssiteorproduction; limitthepossibilityofingestionorinhalation; controlandrestrictdirectexposureofworkers; measureandrecordthelevelsofactivitywherescaleisfound; followtherecommendedmethodofdisposal.

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Table2Activityandradiationdoselimits
Involvement Term Dose limits (1) (2) for whole body for individual organs/tissues Classified Working condition 'A' Controlled area 50 mSvYr-1 500 mSvYr-1 workers Non-classified (1) (2) workers Public and workers with no involvement (special Working condition 'B' (1) requirements for Supervised area (2) transportation)** 3/10 3/10 x -1 15 mSvYr x 150 mSvYr-1 50mSv 500 mSv = 1/10 = 1/10 x 5 mSvYr-1 x 50 mSvYr-1 mSv 5 = 7.5 Svh-1 mSv = 2.5 Svh-1 50 500 mSv mSv = =

Derived levels Hourly limit for external 2000 Sv h-1 (recommended 15 expose of the whole body (2) maximum for radiographers) 2000 hours

2000 hours "Annual limit of intake"* ALI Radium 226 by inhalation is 3/10 ALI, e.g. for Radium 226 1/10 ALI, e.g. for Radium 226 of radioactive material (1) 20 kBq Yr-1 by inhalation 3/10 x 20 kBq by inhalation 1/10 x 20 kBq Radium 226 by ingestion is Yr-1 = 6 kBq Yr-1 Yr-1 = 2 kBq Yr-1 -1 70 kBq Yr Surface contamination level ALI (2), likely to result -2 for Ra 226 8 Bq cm Airborne contamination+ Radioactive substance Specific activity ALI (2), -3 for Ra 226 3 Bqm e.g. 3/10 ALI (2), -2 for RA 226 2.4 Bq cm ALI -3 for Ra 226 e.g. 1 Bqm e.g. 1/10 ALI (2), e.g. 0.8 Bq cm-2 for Ra 226 (2), 1/10 e.g. 0.3 Bqm-3 for Ra 226 ALI,

e.g. 3/10

Precautions

100 Bq g-1 and any other substance having a lower activity 0.4 Bqg-1 used for pollution concentration that cannot be disregarded for the radiological control and disposal protection of persons at work (2). authorisations. Use only classified workers or ALARA***. Regular ALARA*** and 'not non classified workers working monitoring of affected areas. significantly above background to a strictly controlled written Contain surface contamination. levels'. Controls on radioactive system of work (dose limit Prevent airborne substances as pollutants. 15 mSv per annum, i.e. 500 hrs contamination. per year at 30 Sv-hr); contain contamination. Controlled disposal of radioactive substances. Occupational hygiene precautions to prevent inhalation and/or ingestion.

Annual limit of intake (ALI): an ALI is the amount of radioactive material which if taken into the body would delivery a committed dose equivalent to the annual dose limit for either the whole body or individual tissues whichever is the more restrictive. Each isotope has its own ALI, e.g. Radium 226 by inhalation is 20 BqYr-1. Transport packages contain limit. On external surfaces of transport packages/containers the limit is 4 Bqcm -2 (3). 70 Bqg-1 is limit used in transport regulations (3) (but check with national regulations for applicable limits). ALARA: as low as is reasonably achievable. Airborne contamination: very different limits can apply to different isotopes, e.g. 3 Bq m-3 Ra 226; 0.01 Bq m-3 natural thorium Internal commission on radiological protection limits for intakes of radionuclides by workers, ICRP Publication No. 30, Part 2, Pergamon Press, Oxford, 1980. EURATOM Directive of the Council about radiation protection of workers and the public. International Atomic Energy Agency, Safety Series No. 6, Regulations for the Safe Transport of Radioactive Materials 1973, Revised Edition (as amended), Vienna 1979.

** *** + (1) (2) (3)

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6.2Containment,disposalandtheenvironment DisposalofLSAscaleandsludgescanbedifficultandexpensive,duetothe occupational hygiene and environmental protection considerations discussed earlier.Thefollowingcoursesofactionshouldbeconsidered: containment; disposal. 6.2.1Containment If tubulars are pulled and are found to be scaled, then provided that the scale is thin, hard, tenacious and smooth and offers little resistance to well fluid production, and provided that the tubing does not need to be reworked, then the scaled tubulars can be re-run back into the well. Similarly if a vessel is opened up for inspection and is found to contain LSA scales or sludges which are not interfering with production and the material does not have to be removed, then the vessel can be closed up again. 6.2.2Disposal The decision logic for disposal is presented in Figure 1. Method of disposal include: Disposaltothesea Scales exhibiting levels of activity above background may be disposed of to the sea either from offshore installations or from onshore facilities with their own direct flushed outfall. Generally a maximum particle size (say 1 mm) could be specified together with a limit on the total activity (specific activity times weight) expressed in Gigabecquerels. Because particles of this size will obey Stokes Law, if this method is employed where there are reasonably strong tides and currents, there should be no detectable increase in the level of radioactivity in the sea or the surrounding seabed. In such instances, however, seabed surveys (much like those for oil-based mud cuttings) may be required. Disposalonland Listedbelowaremethodsofdisposalonland: In specially dug pits, abandoned mines and oil wells: where such facilitiesareavailable,burialofscaleinmines,pitsorabandonedwellsare possiblemethodsofdisposal. Storage in secure yards or warehouses: in many cases where it is consideredtoodifficultorexpensivetodescalesuchitemsastubulars,filter baskets,valves,etc.,itmayappearcosteffectivetoputthemintolongterm securestorage. Suchstoragemustonlybeusedwiththeagreementofthe relevantauthorities.

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However,thefollowingproducedoffshore,shouldbeconsidered: therisksofexposingotherworkerstothehazardsofLSAscaleareincreased (e.g.seamen,dockers,transportworkers); if LSA scales are stored onshore, thought must be given to keeping such storessecureforgenerationsinordertopreventworkersfrombeingexposed toriskinthefuturethehalflifeofRadium226is1620years; ifmethodssuchasmixing'concentrated'LSAscalewithcementandthen pumpingtheslurryintodrumsordownabandonedwellsareusedthenagain additionalrisksareincurredbytheworkershandlingthescale. 6.3Scaleinhibitionandscaledissolution 6.3.1Inhibition Generally, it can be said that scale inhibition of Ba/SrSO4 using the correct programmes, appropriate solutions and clean suitable equipment, will be successful. Scale inhibitor squeezes will usually be performed when it is known that barium is present in the formation water following the first indication of injection water breakthrough. An increasing sulphate ion count in the produced water is the usual indicator of the onset of breakthrough.

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Otherwise, the produced water must be monitored closely for other indications. Inhibitors can also be injected into the well fluid stream in the production train to help prevent scale formation in valves and production manifolds, etc. 6.3.2Dissolution Scale dissolution, usually in the production train manifolds, has been attempted, most often using organic chemicals. Some of these organic chemicals show promise, but dissolution of the salts has still to be proven effective, due to their almost chemically inert nature. 7.PROCEDUREFORAFIELDSURVEY The initial survey for a NORM at a site is typically performed along the exterior of on-line intact equipment such as vessels, piping, compressors, and other production equipment. Of the three types of radiation present in NORM (alpha, beta and gamma), gamma rays alone can penetrate the steel and be detected outside the equipment. As discussed in the detection equipment section (section 4.3), the SC probe is used to identify areas of potential concern and the GM probe is used to quantify potential human doses. Both measurements can be made during the same survey using a meter that can support the two probes. The results of the survey should be documented and assigned one of the four categories (A, B, C, D) described in Table 3. Cut-offs of 2.5, 25 and 500 microSieverts/hour (uSv/hr) are used to define requirements needed to ensure a safe work environment9 such as limiting access, posting of signs, and other follow-up actions. (Note: 10 uSv/hr = 1 mR/hr). It is recommended that sites with NORM contamination be resurveyed every two years to identify changing conditions.
Table3DeterminationofareaNORMcategory uSv/hr (GM) <2.5 2.5-5 Category A B Definition Public access area Limited access area Requirements None Limitpublicaccess Documentfindings Informmaintenance Limitworkeraccess PostwithNORMsign Trainworkers Personaldosimetry Limitworkeraccess Postwith"highradiation"sign Trainworkers Personaldosimitry Workpermitrequired NotifyEA

25-500

Regulated area

>500

High radiation

8.DECONTAMINATION Any equipment, tools, or personal protective equipment (PPE) that has contacted NORM or

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LSAS contaminated surfaces needs to be evaluated to determine whether they have been contaminated. Similarly areas where NORM-related work has led to possible contamination also need to be evaluated. The decontamination decision logic is presented in Figure 2. Measurements are made using the GM probe and the PK probe (direct measurement or a wipe sample depending on the configuration of the surface). If both measurements are less than the criteria, the material is not considered to be NORM contaminated. For materials that do not meet the stated criteria, decontamination and repeat monitoring are one possible option. The other option is packaging for disposal.

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II. RADIOACTIVEELEMENTSINNATURALGAS Occurrenceofradon Natural gas contains small quantities of the gaseous radioactive nuclide Radon-222 formed from the decay of Radium-226, which is a daughter nuclide of naturally occurring Uranium238. Radon enters natural gas in the earth by diffusion from a formation. Uranium minerals are often associated with carbonaceous deposits, therefore radon can be expected to occur in natural gas. Radon-222 has a half life of 3.8 days and produces upon decay a series of short and long lived daughter nuclides as shown in Figure (1). When propane is separated from natural gas, radon tends to be concentrated in the propane process stream since the boiling point of radon is close to that of propane. Consequently, it is typically enriched in propane by a factor of the order of 10. In natural gas condensate the long lived daughters of radon (particularly Lead-210 and Polonium-210) are generally present.

Figure (1) Decay scheme of the 238U natural series Notes: 1) Halflivesareindicatedinyearsa,daysd,minutesmin,andseconds. 2) Thenatureoftheradiationisindicatedby , ,and (onlyenergetic radiationswithhighyield). Recent reports of radon contaminated buildings through out the world, attest to the wide distribution of radon in the environment. Once formed by the radioactive decay of radium-226, radon is free to migrate as a gas or dissolve in water without being trapped or removed by chemical reaction. Migration through rocks and soil, radon is produced with natural gas at the wellhead. Table 1 shows that radon contamination of natural gas is a worldwide problem, and particularly high concentrations of radon are reported in the US and Canada.

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Table 1 - Radon concentrations in natural gas at the wellhead * Location of Well Radon concentration (pCi/L) Borneo 1 to 3 Canada Alberta 10 to 205 British Columbia 390 to 540 Ontario 4 to 800 Germany 1 to 10 The Netherlands 1 to 45 Nigeria 1 to 3 North Sea 2 to 4 US Colorado, New Mexico 1 to 160 Texas, Kansas, Oklahoma 1 to 1,450 Texas Panhandle 10 to 520 Colorado 11 to 45 California 1 to 100 *) From "Radon Concentration in Natural Gas at the Well, UN Scientific Committee on the Effects of Atomic Radiation; Sources and Effects of IonizingRadiation,UnitedNations,NewYorkCity(1977). When radon-contaminated produced gas is processed to remove the NGL's, much of the radon is removed also. Radon's boiling (or condensing) point is intermediate between the boiling points of ethane and propane. Upon subsequent processing, radon tends to accumulate further in the propylene distillation stream. Table 2 shows the boiling points of radon, the lighter NGL's, and propylene. As expected radon usually is recovered more completely in plants with high ethane recovery. The radon is concentrated in the lighter NGL's and is detected relatively easily with radiation survey meters.

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Table 2 - Boiling points at 760 mm Mercury F Methane -258.0 Ethane -124.0 Radon -79.2 Propylene -53.9 Propane -44.4 Butane +31.1 As long as it is contained and controlled within vessels, equipment, and piping, radon generally is not a health hazard to employees and the public. Even if radon-contaminated propane were released, the threat of fire or asphyxiation would far outweigh the hazard of a short-lived radiation exposure. NORMinNGLfacilities Although entire natural-gas and NGL systems may be contaminated with NORM, some facilities will be contaminated to the extent that they present significant decontamination and disposal problems. Gasoline plants and other NGL facilities will be among the most highly contaminated areas in a system. During processing in a gasoline plant, the levels of external radiation from radon in propane 1 ft from a liquids pump may be as high as 25 milli-roentgens (mR)/hr. Radiation levels up to 6 mr/hr have been detected at outer surfaces of storage tanks containing fresh propane. Sludges in gasoline plants are often contaminated with several thousand picocuries of lead210 per gram. Table 3 shows vessels and equipment in NGL service that may be significantly contaminated with NORM. Although NORM contamination will be general throughout an NGL facility, the contamination usually will be greatest in areas of high turbulence, such as in pumps and valves. Table 3 - Priority areas of concern for high radon and radon decay product contamination NGL facilities De-ethanizers Stills Fractionators Product condensers Flash tanks Pumps in liquid service Piping in liquid service NGL storage tanks Truck terminals Filter separators Dessicants Waste pits Pipelines Filters Pig receivers Machine shops

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In-house Contract When employees open equipment and vessels, precautions must be taken to prevent exposure to radioactive contamination. Maintenance procedures should include the use of respirators and good hygiene to prevent inhalation of radioactive dust. Grinding, if necessary, should be done wet to minimise dust. Occasionally, a plant or other facility that has been processing light hydrocarbons, particularly ethane and propane, is taken out of service and the facility sold or dismantled. Any equipment with internal surface deposits of NORM must receive special consideration when scrapped, sold, transferred, or otherwise disposed of, particularly when the facility is being released for unrestricted use. Analyses for lead-210 usually will be required to verify the extent of contamination and to determine if special handling is needed. Particularly care must be used to prevent employee exposure to NORM contamination. There are potential liabilities involved if contaminated equipment, vessels, and other parts of the facility are released or sold for unrestricted use without first being cleaned and tested to be essentially free of NORM contamination according to state and federal regulations. Much of the material wastes from a facility contaminated with NORM must be handled as low-level radioactive waste and disposed of accordingly. Contaminated wastes should be consolidated and separated from non-contaminated waste to keep radioactive waste volumes as low as possible. Consolidated contaminated wastes should be stored in a controlled-access area. The area should be surveyed with a radiation survey meter and, if required, should be posted. Theinvestigationlevel Normally, the amount of radioactivity in the natural gas and its products is insufficient to cause health hazards during handling and subsequent use by consumers. However, it is recommended that the radon content of natural gas and Polonium-210 in the condensate of wells should be monitored prior to production. A record should also be kept of radon and polonium in gas and condensate from reservoirs which have been in production for a long period. The results of such measurements should be compared with a 'Derived Investigation Level'. A derived investigation level, as defined by the international Commission on Radiological Protection (ICRP), is a value of concentration of radioactive material. It is usually set in relation to a single measurement, which is the resulting radiation dose to humans sufficiently important to justify further investigation. It is important to recognise that an investigation level is not intended to be a limit. Should an investigation level be exceeded, this should be reported to the Central Offices EP Health, Safety and Environment Department (SIPM-EPO/6) who will contact the radiological specialists for advice. A close investigation of the (local) circumstances will be required. The investigation will often be no more than a recognition that the circumstances will not cause any hazard as the investigation level is based on a 'worst case' estimate. Below the investigation level, the information need not be further studied by experts. Calculationoftheinvestigationlevel Two types ofradioactiveexposuretohumansresulting from radioactivityin naturalgasorcondensatecanbeidentified: a) Duringtheuseofthenaturalgasbyconsumers,e.g.heatingandcooking. b) Relatingtogashandlingatgasprocessingstations.

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In both cases, a derived investigation level will be specified. NaturalgasandLPGforDomesticConsumption When natural gas or LPG is burned in domestic appliances (cooking and heating) radon will be emitted into the atmosphere and contribute to the radiation level already naturally present. Radon (and its daughter nuclides which are formed by decay) become attached to aerosol particles and may subsequently be inhaled. Tocalculatethederivedinvestigationlevelforradoninrawnaturalgas,the following'worstcase'conditionsareassumed: Minimal ventilation and maximal invented appliances of LPG in which radonisenriched. The combustion productswill allcontributeto the radon concentrationin indoorair. The maximum permissible yearly dose to members of the public is 5 mSv/a (milliSievert per year, a unit for the ionising radiation dose to human beings). As a base for the derived investigation level, one twentieth of this dose equivalent is taken, i.e. 0.25 mSv/a. This dose equivalent is not exceeded when the concentration in the natural gas is below 2 kBq/m3 (50 pCi/dm3). For comparison, the average yearly dose from the natural background and medical radiation is around 3 mSv/a. This level can be considered as the derived investigation level for radon in raw natural gas taking into account the use of recoverable LPG when converted into fuel gas. For use of natural gas as an industrial fuel gas, the same investigation level should be used, provided that the investigation level for surface contamination is not exceeded. ContaminationofGasProcessingEquipment Inner parts of gas processing equipment may be contaminated with the long lived daughter products of Radon-222 as a result of deposition of the solid daughters (particularly the long lived Pb-210 and Po-210) at places where the stream is dispersed over a large surface or where high turbulence occurs. An additional effect is the enrichment in the propane stream (see 3.8.1) which causes an increased chance of contamination in the propane stream equipment. Similarly, Polonium-210 present in the condensate may be deposited in pumps, distillation columns, heat exchangers, etc. The chance of contamination above a certain level is related to the initial concentration of radon or polonium in natural gas or natural gas condensate. However, possible enrichment and the throughput of gas or condensate are also important factors. The long lived daughters of radon (e.g. Polonium-210) mainly emit alpha radiation which cannot penetrate steel walls of equipment. Only the short lived Bismuth-214 may be detectable at the outside of the equipment. In view of the short half-life, however, the external radiation level will always be minimal and will disappear after shut-down of the installation. Thus, radiation hazards, if present, may only occur when opening equipment, by inhalation or ingestion of the contamination. Before workers enter equipment which has been exposed to condensate containing polonium or propane containing radon, it may be advisable to

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monitor the inner surfaces to avoid the risk of contamination of the personnel involved. For a derived investigation on surface contamination of equipment, 4 kBq/m3 (10 pCi/cm2) should be used. Since the mechanism for deposition of solid daughters of radon (e.g. Polonium-210) cannot be quantitatively described, it is not possible to calculate investigation levels for liquid concentration of radon or Polonium-210 resulting in contamination. However, from experience, contamination of inner surfaces of equipment is unlikely when the level of Polonium-210 in natural gas condensate is below 20 kBq/m3 (0.5 pCi/cm3). Monitoring Radon-222 in natural gas can be detected using an ionisation chamber. Radon concentration determination is usually carried out as one of the routine tests during production testing of new gas reservoirs. Several methods for determination of Polonium-210 in natural gas condensate are available. One of the accurate methods consists of extraction of Po-210 from the condensate and acid destruction followed by plating Po-210 on a silver disc. The alpha activity on the silver surface is determined using, for example, a surface barrier detector. For detection of contamination of inner surfaces of equipment, a simple technique developed by KSLA of applying a film sensitive to alpha radiation is available. SuggestedprogrammeforthecontrolofNORM The following are suggestions for use in establishing a programme for the control of NORM contamination. 1) DeterminewhetherthereisaNORMcontaminationproblem. 2) DetermineareasofpotentialNORMexposureandcontamination. a) Makegammaradiationsurveysoffacilitiesandequipment. b) Makewipetestsonaccessibleinteriorsurfacesofselectedequipment andvessels,especiallyanyinNGLservice. c) Obtainsamplesofsludgesandscaleandanalyseforradiumandlead 210.

d) Obtainsamplesofotherwastematerials,suchasdessicantsandfilters. e) Analyseproducedwaterandwastepondwaterforradium.

3) Establish programmes to ensure personnel safety, products quality, customersatisfaction,andprotectionoftheenvironment. a) Establish policy on periodic surveys, inspection and maintenance procedures,productcontrols,andrecordkeeping. b) Provide safetymanual material that informs employees and details

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requiredprocedures,particularlyformaintenancepersonnel. c) Recommendamanagementandauditsystem.

d) Developplansandproceduresforthedisposalofcontaminatedwaste materials,equipment,andfacilities. REFERENCES 1. Lowspecificactivityscale:origin,treatmentanddisposal E&PForumReportNo.6.6/127,1988 2. E.C.ThayerandL.M.Racioppi Naturallyoccurringradioactivematerials:thenextstep SPE23500,1991 3. P.R. Gray "NORM contamination in Petroleum Industry" JPT Jan. 1993. 4. G.E.Jackson Formationandinhibitionofscaleinoffshoreoilproductivesystems OffshoreRadioactivitySeminar,OYEZLondon,1983 5. K.S.Johnson Waterscalingproblemsintheoilproductionindustry inChemicalsintheOilIndustry,Ed.P.H.Ogden,1983 6. UKOOAReferenceManualonnaturallyoccurringradioactivesubstanceson offshoreinstallations UKOOA,London,1985 7. W.A.KolbandM.Wojcik Enhancedradioactivityduetonaturaloilandgasproductionandrelated radiologicalproblems ScienceoftheTotalEnvironment45,7784,1985 8. A.L.Smith Radioactivescaleformation OTC5081,OffshoreTechnologyConference,Houston,1985 9. 10. 11. 12. P.R. Gray "Radioactive materials could pose problems for the gas industry" Oil & Gas J. (June 25, 1990) 45-48. J. Summerlin Jr. and H.M. Prichard "Radiological Health Implications of Lead-210 and Polonium-210 Accumulations in LPG Refineries" J. American Industrial Hygiene Assn. (1985) 46, No. 4, 202-05. E&P Form Report no. 6.6/127, 1988. Low Specific Activity Scale. E.C. Tayler & C.M. Raciopi NORM; "The Next Step", SPE 23500, 1991.

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RADIOLOGICALUNITSSICONVERSIONS CONVERSIONTABLE
Activityunits 1pCi 1nCi 1Ci 1mCi 1 Ci 1KCi = = = = = 37mBq 37 Bq 37KBq 37MBq 37GBq (37E+09Bq) 37TBq 1mBq 1 Bq 1KBq 1MBq 1GBq 1TBq = = = = = = 0.027pCi 27pCi 27 nCi 27Ci 27mCi 27Ci = 27fCi

Curiestobecquerels 1 pCi 37 mBq 1 nCi 37 Bq 1 Ci 37 KBq 1m Ci 37 MBq 1 Ci 37 GBq

Becquerelstocuries 1 Bq 27 pCi 1 kBq 27 nCi 1 MBq 27 Ci 1 GBq 27 mCi 1 TBq 27 Ci

Absorbeddoseunits 1rad 1mrad 1 rad 1Krad 1Mrad = = = = = 0.01Gy 0.01mGy 0.01 Gy = 10mGy 10 Gy 10 KGy 1Gy 1mGy 1 Gy 10 KGy 1MGy = = = = = 100rad 100mrad 100 rad 0.1Mrad 100 Mrad

Doseequivalentunits 1rem 1mrem 1 rem 1Krem 1Mrem (H)rem 1 1 (H)Sv Prefixes k M G T kilo mega giga tera thousand (103) million (106) thousand million (109) million million (1012) m n p milli micro nano pico thousandth (10-3) millionth (10-6) thousand-millionth (10-9) million-millionth (10-12) = = = = = 0.01Sv 0.01mSv=10Mv 0.01 Sv=10mSv 10 Sv 10 KSv mrem 1 10 Sv 1Sv 1mSv 1 Sv 1KSv 1MSv mrem 10 100 Sv = 100 rem = 100 mrem = 100 rem = 0.1Mrem = 0.1Grem mrem 10 1 mSv

mrem 1 10 mSv

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GLOSSARY
Activity ALARA Alphaparticle( ) Thequantityofaradionuclidedescribedbythenumberofnuclear transformationsoccurringperunittime(seebecquerelandcurie). Aslowasisreasonablyachievable. Achargedparticleemittedfromthenucleusofanatomhavinga massandchargeequalinmagnitudetothatofaheliumnucleus, i.e.twoprotonsandtwoneutrons. TheSIunitofactivity.OneBecquerel(symbolBq)equalsone nucleartransformationpersecond. Chargedparticleemittedfromthenucleusofanatom,withamass andchargeequalinmagnitudetothatoftheelectron. Ba/Sr(Ra)SO4solidsolutionofRaSO4inBa/SrSO4. Radioactivematerialinanyplacewhereitisnotdesired particularlywhereitspresencemaybeharmful.Theharmmaybe ininhalingoringestingtheradioactivematerialwhichmaycause internalradiationdose. Adefinedareainwhichtheoccupationalexposureofpersonnel(to radiation)isunderthesupervisionoftheSafety/RadiationAdviser andthedoserateisabove7.5Sv/hr. Aglassormetalenvelopecontainingagasandtwoelectrodes. Ionisingradiationcausesdischarges,whichareregisteredas electricpulsesinacounter.Thenumberofpulsesisrelatedtothe dose. AsimilardeviceasaGeigerMullercountingtube;theintensityof theelectricpulsesproducedisproportionaltotheenergyofthe primaryionisingparticles. Adevicecontainingmaterialthatemitslightflasheswhenexposed toionisingradiation.Theflashesareconvertedintoelectricpulses byaphotomultiplier. ThepreSIunitofactivity.Onecurie(abbreviatedCi)equals3.7x 1010nucleartransformationspersecond,i.e.itequals37 gigabecquerel. Decay Disintegrationofthenucleusofanunstablenuclideby spontaneousemissionofchargedparticlesand/orphotons.It causesthedecreaseinactivityorradioactivesubstances.

Becquerel Betaparticle( ) Coelestobarite Contamination (radioactive)

Controlledarea

Counter(GeigerMuller)

Counter(Proportional)

Counter(Scintillation)

Curie

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Detector(Radiation)

Anydeviceforconvertingradiantenergytoaformmoresuitable forobservation.Aninstrumentusedtodeterminethepresence, andsometimestheamount,ofradiation. Ageneraltermdenotingthequantityofradiationorenergy absorbed.Forspecialpurposesitmustbeappropriatelyqualified. Ifunqualified,itreferstoabsorbeddose. Thequantityobtainedbymultiplyingtheaverageeffectivedose equivalentbythenumbersofpersonsexposedtoagivensourceof radiation.Expressedinmansievert.Frequentlyabbreviatedto collectivedose.

Dose

Collectiveeffective dose

Cumulativeradiation Thetotaldoseresultingfromrepeatedexposurestodose. dose(radiation) Doseequivalent (symbolH) Aquantityusedinradiationprotection.Itexpressedallradiation onacommonscaleforcalculatingtheeffectiveabsorbeddosesuch thatbiologicaleffectscanbecompared.Itisdefinedastheproduct oftheabsorbeddoseandthequalityfactor(seeQualityfactorand Sievert). Thequantityobtainedbymultiplyingthedoseequivalentsto varioustissuesandorgansbytheriskweightingfactorappropriate toeachandsummingtheproduct.Thisproceduremakesit possibletocomparethisnumberwithawholebodydose equivalent. Thegreatestdoseequivalentthatapersonorspecifiedpartthereof shallbeallowedtoreceiveinagivenperiodoftime.Thisquantity hasbeenrejectedinICRP26. Absorbeddosedeliveredperunitoftime. Instrumenttodetectadmeasureadosereceived.Forexample,a pencilsizeionisationchamberwithaselfreadingelectrometer, usedforpersonnelmonitoring. AmeasureoftheionisationproducedinairbyXorgamma radiation(seeRoentgen). Shortwavelengthelectromagneticradiationofnuclearorigin (rangeofenergyfrom10KeVto9MeV)emittedfromthenucleus. Theunitofabsorbeddose.Onegrayequalsonejouleper kilogramme. Timerequiredforaradioactivesubstancetolosehalfofitsactivity bydecay.Eachradionuclidehasauniquehalflife.

Effectivedose equivalent

Maximum permissibledose equivalent(MPD) Doserate Dosimeter

Exposure Gammaray( ) Gray(symbolGy) Halflife(radioactive) (symbolt1/2)

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IAEA ICRP Ionisingradiation Irradiation Isotopes

InternationalAtomicEnergyAuthority. InternationalCommissiononRadiologicalProtection. Radiationthatproducesionisationinmatter.Examplesarealpha particles,betaparticles,gammarays,Xraysandneutrons. Exposuretoradiation. Nuclideshavingthesamenumberofprotonsintheirnuclei,and hencethesameatomicnumber,butdifferinginthenumberof neutrons,andthereforeinthemassnumber.Almostidentical chemicalpropertiesexistbetweenisotopesofaparticularelement. Thetermshouldnotbeusedasaanonymfornuclide. Theunitforworkandenergy,equaltooneNewtonexpendedalong adistanceofonemetre(IJ=1Nx1m). Periodicorcontinuousdeterminationoftheamountofionising radiationorradioactivecontaminationpresent. Aspeciesofatomcharacterisedbythenumberofprotonsand neutrons,andtheenergycontent. ThepreSIunitofabsorbeddose;equalto0.01J/kg(seeGray). Theemissionandpropagationofenergythroughspaceorthrough amaterialmediumintheformofwaves;forinstance,theemission andpropagationofelectromagneticwaves.Thetermradiationor radiantenergy,whenunqualified,usuallyreferstoelectromagnetic radiation.Suchradiationcommonlyisclassified,accordingto frequency,ashertzian,infraredvisible(light),ultraviolet,Xray, andgammaray(seePhoton). Radiationarisingfromradioactivematerialotherthantheone directlyunderconsideration.Backgroundradiationduetocosmic raysandnaturalradioactivityisalwayspresent.Theremayalso bebackgroundradiationduetothepresenceofradioactive substancesinotherpartsofthebuilding,inthebuildingmaterial itself,etc. Radiationfromasourceoutsidethehumanbody. Radiationfromasourcewithinthebody(asaresultof incorporationanddepositionofradionuclidesinbodytissues). Thepropertyofcertainnuclidesofspontaneouslyemitting particlesorelectromagneticradiation. Anunstablenuclidethatemitsionisingradiation.

Joule Monitoring Nuclide Rad Radiation

Background

External Internal Radioactivity Radionuclide

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Radon

InthecontextofthisreportRadonistakentomeaneitherRadon 222orRadon220radioactivegasesproducedbydecayofRa226 orRa224. ThepreSIunitofdoseequivalent;equalto0.01J/kg(seeSievert). Inconnectionwithionisingradiation,theprobabilityofcancerand leukaemiaorgeneticdamageperunitdoseequivalent.Usually referstofatalmalignantdiseasesandseriousgeneticdamage. ExpressedinSv. ThepreSIunitofexposure.OneRoentgenisthedosegivenbya radiationfieldthatproducesionisation,duetosecondaryelectrons, ofoneelectrostaticunitofchargepercm3(NTP)ofair.Itisequal to2.58x106coulombperkilogrammeofair.

Rem Riskfactor

Roentgen(R)

Sealedsubstance (orsource)

Aradioactivesubstancesealedinanimperviouscontainerwhich hassufficientmechanicalstrengthtopreventcontactwithand dispersionoftheradioactivesubstanceundertheconditionsofuse andwearforwhichitwasdesigned. Abodyofmaterialusedtopreventorreducethepassageof particlesorradiation. Abbreviationof"SystmeInternationald'Unites",theInternational SystemofUnits,recommendedforgeneraluse. Theunitof(effective)doseequivalent.Thesieverthasthe dimensionsofjouleperkilogramme.Thedoseequivalentin sievertsisnumericallyequaltotheabsorbeddoseingrays multipliedbythequalityfactor(seeGrayandQualityfactor). Totalactivityofagivennuclideperunitmassofthespecific material. Theisotopeornonnaturalmixtureofisotopesofanelementwhich maybeincorporatedintoasampletopermitobservationofthe courseofthatelement,aloneorincombination,througha chemical,biological,orphysicalprocess. Thehydrogenisotopewithoneprotonandtwoneutronsinthe nucleus.(Symbol3HorH3,sometimesT). Electromagneticradiationofwhichthewavelengthsareshorter thanthoseofvisiblelight.Theyareusuallyproducedby bombardingametallictargetwithfastelectronsinahighvacuum, asoccursinanXraymachine.

Shield SI Sievert(symbolSv)

Specificactivity Tracer(isotopic)

Tritium Xrays

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