.

Radioactive=Scale Formation
A.L. Smith, G SPE, consultant Summary. Natural radioactivity in the oil and gas fields has been used extensively worldwide to mo.~itor well performance for more than 30 years. 14 Since 1981, North Sea operators have been finding radioactive Wale. The chemistry and physics of this scale are detailed, and a correlation between MI gamma ray units, dose rate, and specific activity is explained. Extensive monitoring procedures, operatior.al control measures, personal radiological protection, and environmental discharge cuntrols are necessary. Introduction Since the 1970s, polonium-2 10 has been monitored in onshore terminals of the U.K. southc, n gas fields. 5 In 1981, radium-226 scale was detected in production tubing from a North Sea oil field, The production systems of several mature fields now contain deposits. 5 Operators have developed extensive procedures to ensure the health and safety of all personnel involved and compliance with all relevant legislation. This paper provides detailed information for those personnel who have operational responsibility for radiological procedures. The U.K. Offshore Operators Assn. (UKOOA) has produced a set of guidelines and a reference manualb to assist operators in gaining a clear understanding of this complex topic. Radio=Oeochemistryof Sedimentary Rooks Regional zones of mineralization, known as uranium provinces, have been formed within the lithosphere. Uranium mineral exploration indicates that there is no positive correlation between the occurrence of oil and gas and of uranium. The frequency distribution of uranium in the lithosphere derived from geologic survey coincides with the calculated uranium concentration distribution derived from the radon content of natural gas. This indicates a positive correlation with a phenomenon that is typical of sedimentary rock. 4, Sandstones and limestones from several geologic systemse,g,, Devonian, Permian, Jurassic, Cretaceous, and Tertiary-have been identified as hydrocarbon source rocks (see Fig, 1). The main radioelements in sedimentary rinks are potassium, uranium, and thorium, and the highest levels are in shales, 7 Potassium levels in shale are a result of the clay minerals illite and K-feldspar. 8 Common shales have uranium and thorium levels close to th average for the continental coast. High uranium levels iil black shales are probably a result of their increased organic content. Black shales can either absorb uranium or reduce the uranyl ion in brines to uranium oxide. Potassium levels in orthoquartzites and arkoses result from K-feldspar, K-mica, and glauconite. s Uranium in sandstones is spread mainly through the quartz grains, and the thorium is associated with resistate grains. Zircon and monazite are frequently concentrated as detrital minerals
Previously withoccidentalPetroleum(Caledonia) Ltd. copyright1SS7Olfahow Technology Confrwence Journal of Petroleum Technology, Ju,le 1987

within sedimentary deposits derived from the major igneous rocks. g On a microscopic scale, uranium is concentrated in fme-grained accessory minerals at the boundaries of the grains or crystals of the major rockformin&Mnerals, resulting in a high emsnadng power. 4 In limestones, uranium ions replace calcium ions within the crystal lattice of calcium carbonate. In phosphatic limestones, which contain uranium in several hundred parts per million, the phosphate ion is replaced, Because thorium does not enter the carbonate Mice easily, it is found mainly in the clay and heavy mineral fractions. These also contain the bulk of the potassium in limestones. In sedimentary basins, the evaporates are also a source of radioactivity. Salt deposits contain beds of the potassium chloride minerals sylvine and camallite. 9 The detrL MIsilicate mineral fraction contains traces of uranium and thorium. Transportation of Radloelementa in North Sea Hydrocarbon Deposits .SouthernGas Fields. Natural gas deposits in the southern North Sea occur in the Lower Permian Rotliegende sandstone, which unconformably overlies coal measures from the Westphalian stage of the Carboniferous period. The Rotliegende has a porous dune sand facies and is sealed by Zechstein salt deposits. The gas has been formed by the devolatilization of the coal seams, which occur in a normal-coal-measures cyclothemic sequence that, at intervals, includesbeds of dark gray to black marine shale. Similar shales occur in the British coal fields and are often radioactive because of uraniferous phosphate nodules containing up to 1,000 ppm uranium. The angular nature of the sub-Rotliegende unconformity causes both coal and marine shale horizons to come into contact with the brines that occupy the pore spaces in the lower part of the Permian sandstones. The brines will dissolve the radium-226 from the parent uranium-23l nodules in the marine s!wles and because radium-226 ha a half-life of 1,620 yearn, redon-222 will be carried by the natural gas into the reservoir. Uranium enric,.,meriis in ou!crops of the coal seams, phosphatic nodule: in the Stephanian stage of the Carboniferous, and uramum absorbed or the red iron oxides that color the grains of Rotliegende sands may also contribwe to the formation of radon-222.
697

Aas

Pd -1

1.s 1~b~v .

9VSTSM

SM12s

LzTwLoov

W?zn TennAm

65- UuEn cnETAa!.wz

135

JURAZZIC -mm EEEJ KEUPER 7NA85!C

195-

Ea
LMEZWNE hlEilh

u
1 r I 1 t

*.262 U( t? az

22s

. . . . . . . ..... ZECHZTIW :.::.::. . . . . .

Esil Eisa -

tinm
L8,4

P5MIAN

Fig, 2Prtnetpal dacay aohama of umnhmM28.

2M CAREOWFEROUZ OROLOEU

EEml

(SOURCE DEVSLOPMSNT OF THE 02L AND OAS RESOURC%SOF THE UNITED KINQOOM 1975, HMSO. UPDATSD 19S2 * 1SSS.)

Fig. 1-Osmaralizad stratigmphy of tha North Sea, showing tha approximate ago of hydroewtwm

North Sea Oil Fields. The ootential fo: radioactive contamination of production ~cilities is greater in the oil fields than in the southern g~s fields. The Jurassic Khmeridgian beds are composed of dark gray to black marine shales, known as hot shales beeause of their natural radioactivity. They are strongly developed above the Kimmeridgian unconformity, which brings them into contact with all formations from the Zeehste,n to the Upper Jurassic, and may act as both seal ant! source reek to many of t!!e larger oil fields in the Viking graben. The oilfield brines also contact the Kimmeridgian shales, and leached radium-226 will concentrate in the brines and supply radon-222 into the oil reservoir. The Shetland basin comprises Jurassic sandstones that contain feldspar and mica and traces of tourmaline, chert, zircon, and glauconite pellets. There are also deposits of monazite, although the main source of radium-226 is thought to be uranite. 41** 1i The pre-Permian and Lower Permian Rotliegende geology of the North Sea shows that the majority of oil and gas fields in the North Sea could become affected. 123 Chemistry of Radioelements The radioactive decay scheme of potassium-40 is different from those of uranium and thorium, The potassium nuclide decays by either beta emission or electron capture directly into calcium-40 or argon-40; the two princi al nuclides of uranium (235U and 238 U) and thorium (2! 2Th) produce radioactive decay series. In these series the parent nuclide undergoes up to 20 successive radioactive disintegrations, changing at each step into a
698

&ughter nuclide of a different chemi :al speeies and emitting either an alpha or beta particle, often accompanied by gamma radiation (see Figs. 2 and 3). When a deeay series has been established for a period equal to several times the longest half-life, the relative proportions of the daughter nuclide$ become fixed, and the series is said to be in radbactive equilibrium. The distribution of radioactivity in the uranium-238 decay series can be divided into two parts at radhm-226. Dau ters P8Po, of this nuclide include the main strong al ha (2 214P0, and 210Po) and gamma (214Pb and ~14Bi)emitters. The strong beta emitters (2MTh, 2MPa, 214Pb, and 214 Bi) are distributed equally between radiums parents and daughters. Radium also marks a separation between certain geochemical properties of the series. Uranium and radium nuclides have opposite solubilities in sulfate and chloride groundwaters. Sulfate leaching will remove the uranium and leave most of the rrdoactive daughters insitu in radio- active equilibrium, and chloride leaching will remove the radium. Radium-226 decays by alpha emission into a nuclide of the noble gas radon, which can then eseape from the parent mineral grain and migrate through the surrounding pore spaces and fissures. This separates the strong alpha- and gamma-emitting rarh daughters from their radium parent. Radon nuclides are also present in the thorium-232 and uranium-235 decay series, but their range of migration is limited by their very short half-lives. The radioactivity of potassium and thorium remains with these elements, but uranium daughters can be carried away as radium-226 by groundwater or as radon-222 by natural gas migration. 4 Once the radium has become chemically bound within a molecular species, it will establish radioactive equilib rium with its daughters, provided that the radon does not migrate. This is confirmed by the gamma spectra obtained
Journal of Pctzolcum Tcchnoiogy, Juzw1987

Thorium

Actinium

H
~1 Ac.2ZC 6410 1.1MDv / I Ro-224 3.s4 5.7 mv I

Th-22$ 1.91 5.4 w

Tb.2W M 1 loQf 4.0 SW

#g.22@ 6.?! 0.0s G9V 1- .

Ftgo 4Cbae.u p d intwnal aeala ahowlng ~ raeryatallizatlon (bar= 55 pm),

Bismuth

Load

Ttwlliun

.U

Xlb

1.s**V

Fig. 3Prlnclpal decay aeheme of thortum-232,

from North Sea deposits of radium-bearing scale, which also indicate that they originate from the uranium-238 and thorium-232 decay series. The radon-222 decays to polonium-21:, which exists initially as a positively charged ion but rapidly oxidizes and forms a nucleus to which a cluster of water molecules become bound.4 The radon decay products become partially or totally attached to aerosol particles within the natural gas, 14which is routinely filtered to remove material greater than 1-pm aerodynamic diameter, before distribution on the inland national grid system, 15 Several radionuclides can still be found in the natural gas distributed throughout the U.K. e.g., radon-222, polonium210, and lead-210. 15 Consequences of Seawater Injection The initial production of oil and gas from a reservoir is usually dry. As the natural pressure in the formation falls, the water present in the reservoir will be produced with the oil and gas, This formation water contains dissolved mineral salts, some of which may be naturally radioactive, In the North Se~, treated seawater is injected into the reservoir to maintain pressure as the oil and gas reserves are depleted. The injected seawater, although less saline than the formation water, may dissolve additional radioactive salts from the minerals present in the various geologic strata. 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. Scale can reduce the production rate by depositing in the formation, perforations, and production string. Scale can form throughout downhole assemblies and any topside equipment through which wetoil and gas process streams pass. Technology, June1987 Journal of Petroleum

Theoretical calculations of scaling !endency are performed on formation waters as part of normal reservoir engineering practice. Although kinetic factors are important in determining whether precipitation occurs, it is necessary to calculate the activity products with respect to the various scaling minerals to estimate the thetiynamic driving forces for scale formation. 16+ 7 Although injection-waterbreakthrough is undesirati!cad essentially unpredictable, it can be detected by uaretid monitoring of increases in the scalifig potential, Radioactive leaching by natural formation water or injected seawater, together with injection-water breakthrough, may result in deposits of mineral scale with various levels of mtural radioactivity. Certain oil fields also have detectable levels of natural uranium in their well fluids. 3 The produced water consisting of formation water, with or without injection water, contains various ionic species in solutione.g., Group HA cations: calcium, strontium, and barium, as well as sulfate and carbonate anions. These particular cations and anions are the soluble components of some very common, sparingly soluble inorganic salts, such as barium sulfate, calcium carbonate, and strontium sulfate. 3 When the volubility product for a pair of ions, e.g., barium and sulfate, is exceeded, precipitation or deposition occurs. Temperature, pressure, pH, and iofiic strength influence the volubility of any pair of ionic species. 17*1C Simole salts (barium sulfate and strontium sulfate) or comp~x salts (barium strontium sulfate) can be formed, depending on the relative concentrations of the ionic species present in the produced water, Radium is also a Group 11Aelement. The chemistry of its inorganic salts is similar to that of the other Group 11A elementscalcium, strontium, and bariumand consequently will coprecipitate easily to form complex inorganic sulfates and carbonates. The complex radioactive sulfates have barium: strontium ratios varying from 5:1 to 1:10, with either strontium or barium being isomorphically substituted in the main sulfate lattice. Scale formation may involve both the crystallization and dissolution of crystalline deposits in the fluctuating-concentration environment of the bathing fluids, For the sulfates of barium and strontium, the rate of dissolution appears to be surface-controlled, with the
699

.!

Bouroa strength units CIJAIES to SECOUERELS 1 pci ~Gm 37 maq 1 ncl

37

1 pa
37

1 Mel

f cl

Bq

kaq

la
~ 27 ICI

BECQUERELS TO CURIES 1 Qaq 1 kSq 1 Mea

27 nCi 27 pCi

1 TSq
27 CI

k M Q T

klla msga @w lam .

Prefixes m rm!lti thousand p mkro millbn thcussnd million n nend miilicm mlllbn P PW

- Ihousan$itl . millionth - thousmd-millkmth

- mlllkm millionth

Dose units (D) absorbed does, RALS to GRAYS (H) does aquivelent, REMS to SIEVERTS red mrad mrad mrad (D) prsd mm mrcm mmm (H)I#Sm ~ 10 ;:; ~;
psv

1%
psv

1 m5y
m$v

10 mQy
mSv

per unit length of track, release their erorgy more slowly, and travel fatir in dense media; e.g., they ean penetrate about 0.1 in. [2.5 mm] of aluminum. When beta particles are slowed rapidly by dense media, they emit energy in the form of secondary X-rays. This is known as bremsstrahlung, or braking radiation, and is of practical importance with beta radiation. Gamma radiation loses its energy by interacting with atomic electrons and travels very long distanem in dense media. As a tieam of gamma photons passes through thicker layers of absorbing materials, the intensity of the beam is gradually reduced, The thickness of the layer that reduces the beam intensity to half its original value is known as the half-value thickness. This process is similar to the law that governs radioactive deeay. An important property of ionizing radiation relates to the depth of tissue penetration. Alpha particles have difficulty pmetrating the dead outer layer of the skin, and
radionuclides that emit them are not hazardous unless tliey

Relationship between dose equivalent (H) and absorbed doee(D) (II) - (DI x OL@itv Faclof W radation FOI redialion PM, ths folkwingvalues h Pwwee, tha ICRP recommends of elfectivaOuelii Fectoc ~ Sete pdclss, dectrom gsmmaradint!c.n, X-rays, bremutrehtung Neutrons k nlphepeltlclaa F=IW

1 10 20

are taken into the body by inhalation, ingestion, or contamination of a wound. Beta particles can penetrate about 0.375 in. [10 mm] of tissue, and radionuclides that emit them are hazardous to super!lcisl tissue but not to internal organs unless they are incorporated in them, Gamma rays can pass through the body, and radionuclides that emit them are hazardous whether on the outside or the inside. The level of risk from ingested radioactivity is almost exactly opposite to that from sources external to the body. Monitoring Radioactive sod, Well-trained, competent personnel should use sensitive gamma-radiation monitors for the detection of radioactive scale; otherwise, it may not be distinguishable from natural background levels. When radioactive scale has been found in oil and water production systems, routine surveys that use isometric drawings can be used to establish the extent of deposition. Gamma-radiationdose-rate meters, used to monitor radioactive scale, should be able to detect the difference in background radiation between onshore and offshore. The presence of granite containing natural radioactivity results in typical background dose rates in Scotland of 15 to 20 microrems/hr [0,15 to 0.2 @v/h]. Offshore, the background dose rates from cosmic radiation are typically 4 to 6 microrems/hr [0.04 to 0.06 @v/h]. The offshore installations are situated in water depths that shield them from the natural radiation within the earths crust, Low background levels of gamma radiation should be detectable before determination of whether the oil and water proecss equipment has been contaminated with radioactive scale. Levels of gamma radiation detected externally at the surface of praess equipment vary from 1 or 2 microrems/hr [0.01 or 0.02 @3v/h]over background up to 1 milIirem/hr [0.01 mSv/h]. Where deposits of scale exist externally on production tubulars, surface dose rates of 12 millirems/hr [120 mSv/h] have occasionally been noted, When radioactive scale has been confirmed, all the internal surfaces of process equipment should be monitored intemall y for the presence of radioactive contamination when the equipment is opened. A wide range of radiation contamination monitors are available that efficiently
kwrutl of Petroleum Technology, June t 987

Fig.

5Radlologlcal unltei S1converelons.

formation of art etch pit being rate-determining. According to Nancollas,7 this may be especially important in understanding scale formation in the oil field because it is quite possible that scale crystals may form and subsequently dissolve in the overall fouling process. Scanning electron micrographs of the radioactive scales have confirmed this hypothesis. Cross-sectional views clearly show the tubercular nature with relatively large, well-defined tubular or lath-like crystals resulting from secondary recrystallization (see Fig, 4). Well-defined crystalline deposits have also occurred in gas-lift production wells. Ionizing Radiations From Radioactive Soale The nuclides in each of the radioactive series decay by emitting a charged particle, e.g., an alpha particle (a helium nucleus) or a beta particle (an electron). Some of these nuclides also decay with the emission of gamma ray photons of discrete energies. Gamma rays are physically identictd to X-rays and are the mechanism by which a decaying nucleus releases excess energy, Alpha particles are massive by nuclear standards, travel relatively slowly through matter, 19 and have a high chance of interacting wi[h atoms along their path. In each of these interactions, an alpha particle will release some of its energy. In dense media, the energy loss is rapid and alpha particles will travel very short distances; for example, they are unable to penetrate anythi~g more than a thin sheet of paper. Beta particles are very much smaller than alpha particles and travel much faster. They have fewer interactions 700

0) Q > ---____ -- -10. ~

3 g z fB a

.10.4

I I I I
10.3

10.2

10.1 DOSE RATE mrem/h

Fig. 6-Radloaetlvtty correlation of a fow-9poelflc.oetfvftyscale.

ries/cm 2 [370 mBq/cm2], The radioactive scale contains radium-226 in equilibrium with its daughters, and alpha, beta, and gamma radiation will all be detectable. For all practical purposes, alpha particles will be selfabsorbed by the scale, which is in effect a mineral shield, except when deposited as a very thin film a few micrometers in depth. * An alpha count can also be detected from items contaminated with the dust associated with the radioactive scale wherever deposits arise through decontamination procedures. Petroleum engineers use gamma ray logging for delineating the sand-bearing strata frori the natural shales and thereby establishing, in conjunction with other wireline logs, the potential oil-bearing formation. The logging tool detects the natural gamma ray radioactivity emitted by the strata, which passes through the walls of the production string. Production geology studies before developmentaldrilling are able to establish whether observed lag deposits of radioactive sands are random effects or correlatable events assignable to specific oilbearing sands, Thermal-decay-time logging in cased holes will delineate these radioactive sands and indicate whether rare-earth elements with high-abmption cross sections are present, e.g., gadolinium, Microprobe arudysesof material isolated from core and sidewall samples have iden. Personal communication with Dr. Mausharl of the Laboralorium Professor Dr. Sarlhold, Wik2bad, FederalR.publkcof Germany,July 1SS1.

Any internal deposits of scale containing natural radioactive material can severely interfere with the interpretation of the natural strata. To provide the petroleum industry with standard units for gamma ray log measurements, API has adopted the API gamma ray unit. One API gamma ray unit is defined as l/200th of the difference in log deflection between zones of low and high radiation in the gamma ray calibration pit. The low-radiation zones consist of very-lowactivity concrete containing 20/40-radium Ottawa silica sand and low-activity cement. The high-radiation zone contains 13 ppm uranium (radium Ottawa silica sand), 24 ppm thorium (monazite sand), and 4% potassium (mica), which together give the zone twice the gamma ray radiation level of the average midcontinent shale. 20 An API rnit is an arbitrary material standard of radiation dose rate derived from empirical geologic properties. Levels of several hundred API units are usually observed downhole, although levels of several thousand API units may be found, indicating high levels of radioactive scale. !lecause the radioactive scale could be monitored by gamma ray logging, a conversion factor into S1 units of radiation dose rate was required (see Fig. 5). A sensitive, wide-range radiation monitor was calibrated against a standard gamma source of radium-226 and compared to a standard test monitor for accuracy and
701

Journal of Petroleum Technology,

June 1987

los-

~fo4

1o4m ~ z > g
g

-10S

103.

CALIBRATION RESPONSE OF G -M LOGGINO TOOL (V) RADIUM - 226

z 4 :

lo2-

----

----

----

_ -

a ~ n a
,.1.

CALIBRATION RESPONSE OF n

II II .,00

103

102

10
DOSE
RATE

mrem/h

Fig. 7-APi gamms ray

Crwrd8tionchart.

reliability, When the radiation dose rates from several A correlation is now possible between the levels of rasamples of various specific activities were plotted, a linear dioactivity meastwedduring a gamma-logging suwey from relationship was observed for samples of similar chemi- both strata and scale and the levels of radioactivity that cal composition (see Fig. 6). The gradient depends on the can be expected to be observed once the tubing string has degree of self-absorption resulting from the variation in been pulled during a workover. This information can be chemical composition, used to ensure that the appropriate radiological protecCurrent gamma ray logging tools use scintillation de- tion procedures are used by the work force. tectors, which are sensitive to normal low levels of radiFrom the data currently available, the correlation obation but saturate easily at higher levels in the region of tained will be specific for each particular type of mineral 1,000 API units. To overcome this, old-style Geiger- scale because of the different absorbance characteristics Muller (GM) tube detectors are required because they of the cations present. have a higher operating range. A new GM gamma ray The empirical correlation between API units and the logging tool was calibrated against a standard gamma radiation dose rate or specific activity of radioactive scale source of radium-226, and the response in counts per sec- is derived graphically. For a linear GM tube response, ond was plotted vs. the radiation dose rate. A second the radation dose rate (in microrexdhr) is found by dividcalibration with scaled tubulars of various specific activity ing API units by four, and the radiation dose rate (in was performed, and the response in counts per second microsieverts per hour) can be determined by dividing -wasplotted vs. the radiation dose rate. The response to API units by 400. For example, to derive API equivalent radioactive scale was paraHel to the response from the scale dose rate for 480 API units (see Fig. 7), pure gamma source (see Fig. 7). This occurs because the 480 API units (scale free) = 120 microrems/hr radioactive scale emits both gamma and beta radiation; [1.2 @v/h], radiation monitors, which would more accurately measand ure all the emitted radiation, were used, but the logging tool will respond otiy to gamma radiation because the steel 480 API units (active scale) = 180 microrems/hr casing absorbs all !he beta radiation from the scale. [1.8#sv/~ The response of the new logging tool was then comTo derive specific activity of radioactive scale (see pared with the response of other commercial gamma ray logging tools and a radium-226 calibration logging source, Fig. 6), which enabled a calibration factor to be derived to per180 microrems/hr -2x 103 microcuries/g mit downhole gamma ray logs to be run in API units. [1.8 pSv/h~74 Bq/g]. 702
Joumai of Petroieum Technology,

June1987

When contamination is confirmed, samples of scale should be obtained and sent for immediate radiochemical

TASLE l-NEW

SPECtFIGACTIVITV LEVEL$

analysis. Industrial organizations cnd ademic hStiNtiOfLS can &termine the specific activity of the scale. 2i Analysts and regulatory authorities agreed that all the different radioactive nuclides could be represented as a total value known as the ;adktm equivalent. Increased levels of the thorium-232 decay scheme have required the specific activity of radium-226 and actinium-228 to be identified separately. Leglsi~?Wo Controls in tho U.K. In the U. K., a number of statutory acts, codes, and regulations exist to control ionizing radiations and radioactive substances. The statute with strict application to the control of ionizing radiations and radioactive substances on offshore installations is the 1960 Radioactive Substances Act. In this act, a solid radioactive substance is one having a specific activity greater than 1x 105 microcuries/g [370 mBq/g]. An installation where radioactive contamination is known to exist has to comply with this act, and joint authorizations we necessary for the accumulation and disposal of both liquid and solid radioactive waste, whether directly to the sea or as contaminated items consigned to shore facilities. The,si,itites do not give any specific guidance on how safe working procedures should be achieved when working with radioactive substances. Until Jan. 1, 1986, the 1%8 Ionising Radiation (Unsealed Radioactive Substances) Regulations made under the Factories Act gave specific guidance but did not apply to offshore instaHations. In the context of these regulations, a radioactive substance was defined as having a specific activity great-

Dust Bulk Nuclldas mkrocurladg Sq/g mkrocuriaa/g Sq/g Thoriunl-232 8,1 xlo-~ 1.35XI0-4 T IE(Aetiniurn-228) 8,1 XIO- 0.3 1,35x 10-4 6 Uranium-233 2.7x10-5 1 2.43% 10-4 9 (Radium-226) 2.7 X1O-5 1 2.43 XI0-4 9 (Polonium-210) 2,7 x 106 1 2.43 X1O-4 9

er than ? x 103 microcuries/g [74 Bq/g]. This low level of activity was the origin of the generic term low specific activity for items containing radium-226 and its daughters. 22 These regulations introduced the concept of adequate shielding, which for nonradiation workers meant shielding sources of ionizing radiations so that the external dose rate was less than 0.75 millirems/hr [7.5 @v/h], and specified limits for the total amount of removable surface contamination-i .e., loose, unsealed material. To provide a safe system of work for operations involving radioactive scale, the operator of the installation had a choice of which approach to take, The 1968 Ionising Radiation (Unsealed Radioactive Substances) Regulations required that personnel who carried out maintenance functions be designated as classified workers where radiation areas existed. Thq operat-r could have developed a scheme of work where !imited exposure of nonclassified personnel to higher dose rates and higher contamination levels was permitted, This ensured that the overall exposures were kept well within the appropriate annual limits. From Jan. 1, 1986, the 1985 Ionising Radiation Regulations and their Approved Code of Practice made under the 1974 Health and Safety at Work Act give specific guidance for both onshore and offshore, Now radioactive substances are those having a specific activity greater than 2.7x 103 microcuries/g [100 Bq/g]. The new definition also includes natural materials with lower concentrations (e.g., zircon and monmite sands), which can create both internal and external radiological hazards. These minerrds are otlen found as deposits

within production separators. Substances that contain uranium-238, thorium-232, or any nuclides from this particular decay series are also included. Low-specificactivity scale contains both radium-226 and actinium-228 in equilibrium, and polonium-210 r-.~ybe deposited within gas-condensate systems both onshore and offshore, Table 1 shows the new levels, Personnel exposure has been restricted further by the introduction of supervised areas at a third the level of controlled (radiation) areas. Safe systems of work requiring the provision of personnel protective equipment are necessary for work in both areas. Restriction of exposure through engineering controls and ddgn features-includhg shielding, ventilation, containment, and minimization of contamination-in addition to the provision and use of safety features and warning devices, is essential because now no level of contamination is acceptable. When an operator uses contractors for decontamination, they should be classified workers and subject to stan&rd radiological and medical supervision because their work may take them to different installations that may not be operating in accor&nce with a universal safe system of work. Implications of Radioactive-SoaIe Formation Mineral scale in oilfield operations has been an operational roblem on production installations for many years. 1! When mineral deposits containing naturally occurring radioactivity progressively build up in the oil and water process equipment in the form of scale or sludge, two potential hazards may exist: external radiation and internal contamination. A potential external radiation hazard exists at or near any pipe, vai ~e, or vesw.~containing internal deposits because,of the transmission of gamma radiation through its walls. On several platforms, the amounts of radioactivity that accumulate within these areas can produce external radiation dose rates that require remedial measures to be taken. External and internal hazards may also exist during maintenance or workover, when it is necessary to pull production tubing, to enter process vessels, or to remove process equipment that may be contaminated by radioactive scale. Radium has a gaseous radioactive daughter, radon, which is unlikely to cause any significant hazard on an installation, because a period of 20 days is required before radon reaches equilibrium with its parent radium within a sealed system, *
Personal communication with P. E.$cott, NRPB, Glasgow, seri 1SSS.

703

The specific acivity of scale on offshore installations is known to vary from less than 1 X 10-5 to 4X 10-1 microcuries/g [370 to 14 S00 mBq/g], covering the range from not being radioactive for disposal purposes to those requiring the implementation of personnel protective measures. Dose rates outside closed vessels and pipes are usually less than 0.75 millirem/hr [7,5 @W/h]. Dose rates within vessels will be higher than those measured outside Ae vessel by a factor of at least 5, and possibly by a much larger factor, depending on the extent and configuration of the contamination, Detailed radiation SUI veys to measure the dose rates are required before the necessary protective measures are implementede.g., safety barriers, adequate shielding, restricted access, and restricted exposure time,
When dose rates above the natural background level are measured externally, an amount of radioactivity will be present inside that will produce a significant level of contamination, 23 When in the form of scale, this contami-

nation may not be readily removable because of its tenacious character. Intact hard scale may form loose
pieces or flakes once the surface continuity is broken, or it may become friable as it dries and pose a serious dust

problem. Contaminated sand or sludge should be flushed from the inside of flowlines and vessels before any process equipment is opened. The potential to cause an internal hazard is governed by the quantity of removable contamination. A controlled area around access points where process equipment has been opened will prevent the spread of contamination. Airborne contamination will be eliminated if the scaie is kept moist. ?4 The controlled area should be designed so that contamination is contained and prevented from spreading except by designated drainage systems or flowlines, Protective clothing should be worn by all personnel entering vessels or working on process equipment. Initial cleaning of a vessel should be performed from the access points. Radiation and contamination surveys of a vessels interior should be made to determine the existence of scale and the precautions necessary. The interior should be cleaned bj a wet method to prevent airborne contamination. Internal components and personnels protective clothing should be washed to remove loose contamination before they are removed from a vessel, Protective clothing should be monitored and removed and the personnel should wash before leaving the controlled area. To prevent ingestion, the chewing of gum or tobacco should be prohibited. Contaminated items should be identified and packaged before they leave the controlled area. Contaminated waste should be disposed of according to the license, and when the work has been completed, the controlled area should be decontaminated. Contaminated equipment or waste sent ashore for decontamination andlor disposal under license should be packaged, labeled, manifested, and transported in accordance with the regulations. 22 Environmental Aapaots
Contaminated equipment should not be dispatched either unmarked, unsealed, or without due notice, or to unoffi704

cial locations, because any of these events can cause considemble trouble for both the operators and the authorities, When these items have been transported ashore to an operators premises, they must be transported to authorized decontamination sites. Otdy operators with authorized sites are permitted to dispose of radioactive scale. Only beta- and gamrna+mitting nuclides can be disposed of at general landfill sites. All items contaminated with alpha-emitting nuclides, such 7Aradium-226 and its daughters, must be decontaminated before the radioactive waste is disposed of into the sea. Contaminated personnels protective clothing is an exception; it can be disposed of at general landfill sites, and contaminated sludge, sand, and scale debris can be disposed of directly offshore. Items contaminated with low-specific-activity material must be decontaminated to 1 x 104 microcuries/cm2 [3.7 Bq/cm2] before they are returned to service and to 1x 10s microcuries/cm2 ~370 ni3q/cm2] before they are scrapped, sent to external contractors, or undergo dry operations. 232s The main disposal route is to the sea, and strict controls are maintained by the authorities to ensure compliance by both the operators offshore and the current decontamination contractor onshore. A particle-size specification of 250pm exists for discharge from onshore operations and of 1$00-pm-size particles for discharge from offshore operations. This 1,(KM-pmsize may be raised once additional data on the efficiency of particle-size distribution in plumes have been evaluated with data on the size distribution of seabed sand particles. 26 The ocean contains large quantities of natural radionuclides. Currently available data provide useful background information for use when radioactive waste disposal is considered. 27 Both radium-226 and its parent, thorium-230, are scavenged from seawater and returned to the sediments by mechanisms not fully understood. 27 The continuing study of marine radioecology over many years by the IntL Commission on Radiological Protection (ICRP) has embled tkir recommendations about the protection of humans from the detrimental effects of ionizing radiation to become widely accepted as the basis for radiological protection by national authorities and international organizations. These recommendations evolved into the l%ft Radioactive Substances Act, which indicates the concentrations of certain radionuclides that are acceptable when discharged as solid, liquid, or gas/vapor. ICRI tibles are available of the current permissible levels for continuous exposure over a working lifetime at occupational levels or continuous exposure for a lifetime at nonoccupational levels. 28 Soda Inhibitors Gnd $oale Ramover8 A variety of chemical types have been used to inhibit scale deposition and a number of mechanisms proposed to explain their action. Most inhibitors act by some type of surface mechanism at levels much lower than that required to chelate cr quester the scaling ions. Current indications are that the primary step in the inhibition process is the adsorption of the inhibitor or newly formed crystal nuclei on existing surfaces or any active growth site. 1617 With radioactive scale, the most efficient types are the aminoethylene phosphoric acids:
Journal of Petroleum Technology, June 1987

F..

OH

I
R-NCH2 -P=O.

I
OH Phosphoric acids of this general formula and their salts are excellent scale inhibitors for all major types ofs :ale encountered, and a number of such inhibitors are available commercially. The structure influences the adsorption densities and rates of adsorption; the inhibition activity is pHdependent. Phosphoric acids are more thermally and hydrolytically stable than the polyphosphate or phosphate ester type of inhibitor. They are ideal for downhole squeeze treatment. An additional advantage is that extremely low levels of inhibitor can be measured accurately, enabling feedback of the inhibitor to be perfo~med reliably. One acid of particular interest altered the overall deposition of the complex barium strontium sulfate scaIe from a hard deposit to a soft, friable fir. The specific activity of the scale did not change significantly, but after radiochemical analysis, an organic-soluble fraction was fouf:1.: to contain a significant proportion of radioactivity. Further samples of this type of deposit are needed so that the soluble radioactive components can be analyzed. This may lead to the creation of the next generation of scale inhibitors. The alternative is to dissolve the scale that has already precipitated. The current scale removers are based on ethylenediaminetetraacetic acid, and the process of dissolving scale is one of either chelation or sequestration. The cations are chemically bound by a chelating agent
to produce water-soluble complexes, which prevents the cations from reacting with available anions and precipitating. Stoichiometric quantities of chelating agent are neces-

SoabCm&ol Meaeuree Physical means of decontaminationare more cost-effective than chemical means, High-pressure water jetting at up to 14,000 psi [95 MPa] is extremely efficient, but it is considered expensive. The cost of soaking a contaminated tubing string with scale dissolvers, which do not totally decontaminate the ,tubulars, is not justified by economics alone, because additional high-pressure water jetting will still be required to decontaminate the tubulars filly. The development of extremely efficient and costeffective scale inhibitors for use in the squeeze treatment of oil- and gas-producing zones will be of primary importance to all operators. An interesting point to conclude with is that wells treated with scale dissolvers appear to have benefited from a high degree of scale inhibition for a considerable time after treatment, even though the chemicals are not surface active. 29 Acknowlod@monts I thank the management of Occidental Petroleum Ltd. for permission to present the original paper at the Second Intl. Chemicals in the Oil Industry Symposium in Manchester, March 25-27, 1985, for the Royal Society of Chemistry, and at the 17th Offshore Technology Conference in Houston, May 6-9, 1985, for 3PE. I also acknowledge the contributions of the UKOOA Safety Committee, the Nat]. Radiological Protection Board (NRPB), the Industrial Pollution Inspectorate, the Dept. of Energy, the British Geological Swvey, and the Oil Industry Exploration and Production FotUm. Additionally, I acknowledge SAI Tubular Services Ltd. and the Biomedical Physics Dept., Aberdeen U., for their constructive comments. The scanning electron micrographs are courtesy of LD.F. Production Chemicals Ltd. References 1.Campbell, J. L. P.:

sary to remove the scale before contamination can be reduced to manageable levels.

Radioactive

Well Logging Anomalies.

PeI.

Outlook Around the World Several operators on the U.K. Continental Shelf and in other regions of the North Sea are experiencing radioactive scale. As the mature fields within the North Sea become depleted, the deposition of sctile will place an increasing burden on the prodw rive I;fe of a field. This phenomenon is also known in Vmezuela, the U. S., the U.S.S.R., the Demmratic Republic of Germany, the Federal Republic of Germany, Egypt, and the Persian Gulf, among others. Some operators and countries may currcrvly be aware of this phenomenon. The ICRP principle~and recommendations applied in the U.K. also exte:ld worldwide and do more than merely propose exposure limits. 27 1. No practice shall be adopted unless its introduction produces a positive net benefit. 2. All exposures shall P kept as low as reasonably achievable, economic A social factors being taken into
accoufk

Enc. (1951) 23. B7. 2. ~o;t, G.B. arsdHill. J. W.: -Radioactivity in Some OWields of Southern Kansas. Bu//., USGS( 1953) 988.69. 3. Fertl, W. H.: Gamma Ray Spectral Logging: A New Ewduation Frontier, Wor/d Oi/ (Nov. 1983) 11, 85. 4. van der Heijde, H. B,, Bcens. H., and de Monchy, A. R.: Ecotoxicoiogy and Environntentul .$ofcty (1977) 1, 49-87. of Radioactive Contamination on 5. Escon. P.: The Occurrence for the Dept. of Energy. NRPB report Offshore Installations, London (1984). 6. Guidelines for Operators on Naturally Gccuring Radioactive Substances on Offshore Installations. and UKOOA Reference Maad, UK(3GA ( 1985). 7. Miller, J. M.: Geological Sources of Radioactive Materials, British Geological Survey, Oflshore Radiowivin, OYEZ Scientific & Technical services Ltd,, London (April 1983). r3.Deer, W. A., Howie. R. A., and Zussman. J.: An hnroducrion M Rock-Forming Minerals, Longman publishing, London ( 1966) 13, 193, 207, 260, 281, 510, 514. Bo-ner, R.: Minerals, Rocks and Genrsrones, Oliver and Boyd.

10! Maber.

the limits rwommended by the commission.

3. The dose equivalent to individuals shall not exceed for the appropriate circumstances

(1%2)52. 62, 122. C. E.: Dcvelop?wnt Geology of the P@r OWield,Ocenn Management (198 I) 7, 133-65. 11. Dixon, D. W.: Radiation Hazards to Collectors of Geological Specimens containing Natural Radioactivity. NRPB reportR131. H. M. S. O., Lorsdon.(t9fU). 12. Pegrssm, R. M., Rees, G., and Naylor, D.: Geoks off~ ~orI~West European Continental .$he~, Graham Trotman Dudley

wrdon

Publishing; London (1975) 2. 705

Journal of Petroleum Technology, June1987

.. ..

13, Map supplement, O@rore Engineer, U.K. Continental Shelf, London (Sept. 1984). 14. Cliff, K.D. and Miles, J.C.H.: TIw Measurement of the .%x Distribution of Sub-micron Environmental Aerosols,. NRPB report RSD4, H. M. S. O., London (1984). 15. Wilkins, B. T.: The Assessment of Radon and its Decay Products in North Sea Gas, NRPB report RSD4, H. S. M. O., Lmsdorr (1982). 16. Jackson, G. E.: Formation and Inhibition of Scale irr Offshore 0]1 Production Systems, QWrore Rodioacriviry, Pefrolite Ltd., OYEZ Scientific & Technical Services Ltd., London (April 1983). Chemical Studies of 17. Nancollas, G. H.: Oiltield Scale-Physical its Formation and Prevention, presented al the 1985 Second hut. Chemicals in the Oil Industry Symposium, Royal Society of Chemistry, Manchester, March 25-27. 18. Ham:&ok of Chemis/ry and Physics, 64th ed~ion, R.C. Weast (cd.) C.R.C. ?ress, Flmidrr (1983). 19. Living wkh Radiation, NRPB, H. M! S. O., London (1981). 20, Standard Calibration and Format for Nuclear L08s, API FcP33, third edition, Washington, DC (April 1974). 21, Green, D.: The Measurement of Radioactivity in Scale, Imperial Chemical Industries Ltd. report GFR 84/6/NAA, London (1984). 22. Regulations for the Safe Transport of Radioactive Materials, lntl. Atomic Energy Authority safety series, No. 6, Safety Standards, Vienna ( 19S4). 23, Ionising Radiations Regulations 1985, S.1. 1985, No. 1333. Approved Cede of Practice, H. M. S. O., London (Sept. 1985).

24. Brrsirws.s Commurricatii, H.M, Inapecfm of Factories (Aug. 1981) Health arsd Safety Exeeutive, Fkfirrburgh. 25, Schedule 2. IOrrizing Radiations (Urwcaid Radbcrive Substarr@ Regulations 1%8, S.1. 1968, No. 780, H, M, S. O., London (May 1963). 26. Little, D. I., Sfaggs, M. F., and Woodmarr, S. S. C.: Trarrefer Processes in Cohes&e Sedhnerst Systems, W .R. Parker and D.J .J. Kirtnermsm (de.), Plenum Press, New York City (1984) 47-74. 27. Control of Rad&ctive Waste Disposal into the Marir~ Envimrrrrtertt, Safety Series, No. 61, Intl. Atomic Energy Authority, Vienna (1983). 28. Sax, N. I.: Dangerous Properties of Industrial Materials, fifth edition, VarrNostrand Reinhold Publishing, New York City (1979) (Map. 5A. 29. Marszoni, J.: M. SC. thesis, Imprial C., U. of London (1983).

SI Metrio Conversion Faotors E+1O = J3q curie x 3.7* rad x 1.O* E02 = Gy rem x 1,0* E-02 = Sv
.Conversion faeror ie ex&cf. W1

Ori@nal manuscript ~ inthe&scbfye4Perroteum EnDI,~~~~~ l%Peraox915dt e4@ksWOnJuly7,1 ~,Rsvi@~

Paper (SPE 1458S) first presented at the 1SS5 hnusl mca hetd in Houston, May S-9. OffsWe Tocfr&

;%
t+onfer:

706

Journal of Petroieum Technology, Jurre 1987