SPE 28945 Crystallization Process to Reduce NORM-Containing Waste C.G. Hayden,* Inst. of Gas Technology, and T.F. Kraemer, U.S. Geological Survey *9PE Member ABSTRACT ‘This paper describes a process of Naturally Occurring Radioactive Material (NORM) waste reduction for scales, sludges, and soils. The process involves dissolution and fractional ‘crystallization steps that concentrate the radioactive ‘material imo a small mass of barite. The concentration of radium in the product, barite, can bbe increased or decreased. The NORM-containing barite product is suitable for slurry injection into sandstone formations, INTRODUCTION The U.S. oil and gas industry generates up to 700,000 tons per year of waste containing NORM. The vast majority of this NORM waste is in the form of sludges and contaminated soils. ‘These are heterogeneous mixtures that contains relatively small quantities of the NORM (radium) with a carrier (usually barite), and a much fraction of NORM-free solids and fluids, Disposal costs vary from a few hundred dollars to aver $2000 per ton, depending on the quantity, the disposal process used, and other site-specific intangibles. This cost of disposal has driven the market to develop technologies to perform physical separations that can reduce the amount to be disposed by 75% to 90%. While this volume reduction is significant, it primarily involves simple separation and removal of water and oil, and occasionally some method of size and/or density differentiation that separates some of the NORM- free material from the remaining material, There is usually a considerable quantity of sand, sediments, iron products, and scales that remain with the NORM following these processes. At the same time, a small fraction of the NORM travels with the "NORM-free” waste that is often disposed of as nonhazardous oilfield waste. isnincs ME PIPEESS described herein has three istinct goals. First, it provides a quantitative separation of NORM from the NORM-free components of the waste. The process is based on dissolution followed by selective reprecipitation of the NORM and its barite carrier. Second, the process can then be used to “engineer” the waste, specifying (within limits) the NORM content of the barite product. The NORM content of the barite can be decreased by simple dilution with NORM -free barite during the dissolution phase. It is emphasized that this is a true dilution, rather than a dilution by adding filler to a heterogeneous mixture. ‘The NORM content of the barite can be increased utilizing a fractional crystallization technology. Third, the particle size of the resulting homogeneous product can be optimized to the disposal technology envisioned. ‘The process2 CRYSTALLIZATION PROCESS TO REDUCE NORM-CONTAINING WASTE SPE 28945 provides the final product in the form of small uniformly sized crystals. The crystal size can be sub-micron, which is particularly suitable for slurrying and for subsurface injection. The primary solvent used in the dissolution ‘and reprecipitation steps is concentrated or fuming sulfuric acid, This is a common acid that is used extensively in the chemical industry and is available avery modest price. This sulfuric acid is not ‘consumed in the process, but is simply diluted. ‘There are commercial plants existing in the Gulf Coast that re-concentrate sulfuric acid. Advantages of this acid over chelating agents are cost, carrying ‘capacity, and the particular characteristic that in the event of unplanned releases, the NORM will quickly precipitate from the acid back into its barite carrier. This prevents soluble radium from entering the environment and it greatly facilitates clean-up, making the process less of a threat to the environment should a mishap occur. THEORY The source of the radioactivity in scales and sludges associated with oil and gas production is primarily radium, which precipitates from produced brine. Radium has a behavior similar to calcium, strontium, and barium, ‘There is never enough radium in solution to form a traditional scale, since the solubility of radium sulfate in pure water is 2.1 mg RaSOg per liter (Harris, 1991), and such concentrations of radium in water would be difficult to achieve naturally. Radium will, however, naturally co-precipitate with barite. Though many carbonate and sulfate based scales are found in the oilfield, the two common scales are calcium carbonate (calcite) and barium sulfate (barite). There is a tendency for radium to co-precipitate with other scales, but itis primarily associated with barium sulfate. Though the brinc is a dilute source of radium, scales can be found with very high levels of radium, The role of calcite is usually not significant in accumulating NORM. The process presented in this paper can be used to treat radium in all forms of scales and heterogeneous mixtures, Barite and other scales accumulates in flow lines, equipment, and pits. In piping this scale can be reiaively pure. The bare in tanks and especialy in pits is a heterogeneous mixture of numerous other solids and liquids. The average of 17 NORM- containing sludges is shown in Table 1 (Fisher and Hammond, 1994), The quantity of barite in these sludges averaged 19% of the total mass and 8% of the total volume. If the NORM is indeed in the barite scale fraction, then removing NORM-free 10 components would result in a reduction of mass of ghout 819% and a reduction of volume of about ‘Table 1, Composition of 17 NORM-Containing Sludges, Major Components, Weight % Mean Median Water 16.0 ol 55 SiOz 46.9 62.0 Ba(S1)S04 192 174 ALO3 47 12 CaCO; 3.8 18 NaCl 19 09 Fe3 aT 1.6 FeO 24 09 ‘The process described herein makes use of the relative insolubility of barite in common acids and ditute sulfuric acid and the surprisingly solubility of barite in concentrated sulfuric acid. ‘The solubility of baritc in various acids is presented in Table 2 (Linke, 1958). Treatment with an acid such as hydrochloric acid plus surfactants would Temove carbonates, iron, salts, water, and oil from a typical sludge, but would dissolve only a Table 2, Solubility of Barite in Common Acids Linke, 1958) HCl A 0.09 HCL 2 0.15 HCl 54 0.09 HNO3 1 0.24 HINO3 2 0:39 HpS04 149 0.88 HpS04 17.9 137 igible fraction of the barite. For a typical oil field sludge, this would leave sand, NORM- containing barite, a fraction of the non-barite sulfate scales, and some sediments, Barite is very soluble in concentrated sulfuric acid. There is essentially no free sulfate (80,2) in concentrated sulfuric acid, but rather H2SO,, H30+ and HSO,” (Garrels and Christ, 1965). As the barium sulfate dissolves, the sulfateSPE 28945 is converted to HSO," at the expense of one H2SO,. ‘The solubility is governed by the solubility of BaSO,*(H,SO,), where the "n" value changes with the water content of the acid but is most often given the value of 1 (Linke, 1958, and Jacobson, 1946). ‘The NORM-containing barite can be separated from these other components by dissolving the barite in concentrated sulfuric acid, followed by removing the remaining solids. The solubility of barite is high in pure sulfuric acid but falls quickly as the water content, and consequently the 8O,-2 content, of the solution is increased. The solubility of other sulfate scales in sulfuric acid follow similar pattems, though barite shows the ‘greatest sensitivity to water. The solubility of barite and the other common sulfate scales in sulfuric acid- water mixtures is shown in Figure 1 (Linke, 1958). The solubility of barite in pure sulfuric acid is about 285 grams per liter, while the solubility of barite in 4 solution of sulfuric acid containing 20% by weight water is 0.3 grams per liter. 1000 0 10 20 30 40 ‘Water in Sulfuric Acid. Weight % Figure 1, Solubility of Sulfate Scales in Sulfuric Acid ‘The barite and other sulfate scales are dissolved in very concentrated or fuming sulfuric acid. In the unlikely event the solution is not saturated with barite, for instance if the NORM had accumulated in a calcium sulfate scale, NORM-free barite can be added. The dissolved barite and NORM are separated from the NORM-free solids that remain undissolved in the sulfuric acid. The barite and NORM are then precipitated by adding ‘water. The amount of water added should range from 20% to 40% by weight. There is a tradeoff " CHRISTOPHER G. HAYDEN AND THOMAS F. KRAEMER 3 between adding more water, which results in a ter precipitation of the radium in solution, and ‘energy requirements to regenerate (dehydrate) the sulfuric acid, Itis possible during the reprecipitation stage tp change the concentration of NORM in the bars. ution necessary to keep the waste within regulatory ext-ofh pereridigs depin accomplished by dissolving NORM-free barite in sulfuric acid, mixing the resulting solution with the NORM- containing acid, and then simultaneously precipitating both by adding water. The quantity of NORM-containing barite will naturally be increased in this step. Concentration of the radium into a smaller ‘quantity of barite is possible through a fractiunal crystallization step. Experimental evidence has shown that, under controlled partial precipitation steps, the bal ofthe bate that precipitates from solution is contains 30% to 40% less radium that the barite that was used to make the feed solution, The last fraction of barite to precipitate contains several times the radium content that was in the barite used to make the feed. Numerous precipitation experiments show that at water concentrations below about 8% by weight, the solid that forms is deficient relative to the feed stock in radium. The solid formed under these conditions is BaSO,*(H,SO,) or Ba(HSO,), (Linke, 1958). Material that precipitates out of solution after the water content exceeds about 10% is enriched in radium, This material is traditional barium sulfate. This data suggest that the Ba(HSO,), has a lower affinity for radium that barium sulfate. If a 100% sulfuric acid solution is saturated with barite, and then water is added to bring the final water concentration to 8%, roughly 250 of the original 280 grams per liter of barite will have precipitated out of solution. This 250 grams of barite would contain only about 60% of the radium concentration of the 280-gram feed stock. The third goal of the process is to provide the NORM in a form amenable to various disposal methodologies. The most popular disposal method is entombment in casing within a plugged and abandoned well. Slurrying the NORM is one preferred method of handling it. There has been a strong interest in downhole injection as a disposal mechanism. Typical disposal formations have pore throat openings near twenty microns in diameter. ‘The rule of thumb is that particles smaller than one seventh the pore throat diameter will not cause plugging. Therefore, particles must be only a few4 CRYSTALLIZATION PROCESS TO REDUCE NORM-CONTAINING WASTE. ‘microns redial ST eels to pass through a disposal formation without plugging. Capsaicin proceeee re ideally suited for particle size control and for making very small particles. Slurries with particle sizes smaller than. ‘one micron have been formed by this technique. This suggests the NORM containing barite may be injected into subsurface formations without forming a fracture, EXPERIMENTAL PROCEDURE A sample of NORM that exhibited hi activity was obtained from an East Texas field. The activity values are higher than normally observed, but using this sample allowed us to contemporaneously follow the experiments with a scintillation meter without having to wait for laboratory analyses. The sample was a heterogeneous mixture of iron corrosion products, ‘rains of scale that included both carbonate and sulfate scales, sand, and presumably clays, No analyses of this material was performed prior to treatment, but the appearance suggested there was a large excess of iron corrosion products. The sample was treated with an excess of a 2:1 by volume mixture of concentrated hydrochloric acid and nitric acid. Roughly 60% of the solids were dissolved in the acid over a period of about 24 hours with no stirring. The acid was removed. ‘The solid sample was dried, split into several fractions, and then treated with various mixtures of concentrated sulfuric acid and fuming sulfuric acid, The amount of acid used was between 10% and 40% more than would be required to dissolve all ofthe solid assuming the solid was barite. The samples were left stirring for Shours. Between 8% and 20%, depending on the sample, of the remaining solids did not dissolve in the sulfuric acid. Additional sulfuric acid was added, and the material was allowed to stir overnight, There was no apparent additional dissolution of the solid material that had been observed after 8 hours of stirring. This solid material had no measurable activity using a scintillation counter. The liquid samples were split into several fractions for various precipitation tests. Water was added, the solution stirred, allowed to settle, and then the acid was decanted from the solids. ‘This. procedure was then repeated on the same sample until the water content equalled at least 40%. ‘The amount of radium and barium containing acid adhering to the solids afier decanting, was considerable, as the precipitate is a fine powder 12 ‘SPE 28945 and the acid is viscous. The solids were washed with water, which allowed the barium and radium present in the acid that was not separated from the solids to precipitate. The quantity of barite and NORM precipitated aftr te imperfect separation was considerable but was not measured. A rough cstimate is that there remained 4 times the solids volume of acid after decanting. This acid could add as much as 9% more barite to the solids during water washing. Fortunately, the amount of solids carried over with the adhering acid declines rapidly with subsequent precipitations as the carrying capacity of the acid was decreased. ‘An efficient solid/liquid separation step - via filtration or centrifugation - is a prerequisite to a commercial process. Carryover affected all experiments, and for this reason the partial precipitation studies provide minimum values for radium depletion/enrichment of the product. E Jpintion Experi This study tried to combine scientific investigation with engineering design. Most of the procedures ‘were performed relatively quickly in a manner that emulated the envisioned commercial process. Tests with reagent grade barite and reagent grade sulfuric acid clearly showed that supersaturation, and hence 8 lack of precipitation, was a problém for processing times of less than one hour using small concentration changes, no stirring beyond the initial mixing after each water aliquot is added, and no seed crystals present. Figure 2 graphically shows the results of four such experiments, where horizontal movement from left wo right indicated the addition of water to acid 20 | No ppt. observed © ppt. observed published solubility om ym a0 @ <-Experiment 1 Grams BaSO4/100 Grams H2S04 0 10 (Grams Water/1U0 Grams H2S04 Figure 2, Evidence of Supersaturation During Fast Precipitation StepsSPE 28945 solutions, Adding water in small increments, with stirring, resulted in the liquid becoming supersaturated. A series of fast precipitation experiments were run where water (ice) was added incrementally at 15 10 60 minute imervals until a precipitate was observed. Water was added in relatively larger aliquots. ‘Mixing occurred as the ice melted. Precipitates were observed forming near the ice during melting. The precipitate was partially separted from the Liquor by decanting and was washed with water. The solids were then pu into sitar geometries and the activity of the samples was measured using a sodium iodide crystal scintillator. This provides areal time clue about the relative magnitude of the radium enrichment in sequential samples. This data was not considered definitive because there is a nonlinear relationship between sample size versus the radioactivity measured. Relative activities have an error of about plus or ‘minus 20%. Selected data is shown in Table 3, ‘where the symbol before the dash is the run number and the number after the dash is the precipitation ‘Table 3, Activity of Barite Fractions in Fast Precipitation Experiments RunSample Mass, Activity, grams uRAlg Ad 1 5.8 423 114 114 Ad 035 123 Bl 131 3.2 B-2 1.29 3.3 B3 135 43 B-4 1.47 6.3 c1 1.61 37 C2 161 5.0 C3 0.26 6.7 Dit 1,52 4.6 D2 0:30 85 D3e 021 13 D4 0.14 2B El 1.31 5.2 E2 0.63 10 E3 0.23 ul + -- Run Dat 80°C, all others at ambient temp. 13 CHRISTOPHER G. HAYDEN AND THOMAS F. KRAEMER 5 step within that run, Radium enrichment in the later precipitation steps was apparent despite the crude measurement technique used. ‘One problem with these fast experiments. was there would be regions of very high supersaturation as the ice melted due to poor mixing. Very high supersaturations result in essentially instantaneous precipitation of barite. For very fast runs, barite that initially precipitated " probably did not have time to equilibrate with the mixture after stirring. Slow equilibrium-dominated precipitation traditionally provide the greatest enrichment- depletion in fractional crystallization processes. Of course, such processes may be too slow for a commercial waste treatment process. A balance is needed between slow and fast precipitation. For these experiments 4 to 16 hours digestion time was allowed for each step. ‘The supersaturation problems were resolved when larger concentration steps, equivalent to between 4 and 8 weight percent water, were made. One reason may be tat poor mixing for a few sevonds after aa no TEE ‘volumes of water ave regions st . Grysullation, escalally nptntaneous at dese conditions, may have provided seed crystals. After the sample was well mixed, it was allowed to age for at least 4 hours prior to decanting of the acid. Presumably, the crystals approached equilibrium with the mixture during this time. Two representative experiments are described below. The first test involved only two sequential precipitation steps. Water was added to a saturated solution of NORM-containing scale dissolved in ‘concentrated sulfuric acid so that approximately half of the barite would precipitate. After separating the solids from the acid, both ‘samples were washed with large excesses of water. Again, the decanting process was noted to provide a poor solid-liquid separation. Dissolved barite in the acid remaining with the solids after decanting precipitated during subsequent washing processes. The steps of this test are described below. 1) Start with 68 grams of solution (61.6 g of 100% sulfuric acid, 1.6 g water, and 4.7 g scale). 2) Add 3.5 grams of water. Let sit overnight at room temperature. 3) Separate precipitate from acid by decanting, labeling the solid F-1.6 CRYSTALLIZATION PROCESS TO REDUCE NORM-CONTAINING WASTE, 4) Add 25 grams water to the acid. Separare the ipitate, designated F-2, that forms. 5) Wash sampies with water, collect om a filter. The daa ig reseed in Table 4. Raum analyses were perfe ‘Mass balance calculations ahr the orig Ussolved sete sample contained 22 700 it radium (15,700 pCi radium-226 and 7, ‘adiuan-228) per gram of barte. ‘This first faction contained 45% less radium than did the barite used tomake the feed stock. The second fraction precipitated contained 54% of the barium and 74% Pfthe radium, ‘This second fraction could have undergone another fractional crystallization step to recover more radium deficient scale, but this was not in the test plan. Table 4, Activity of Two Sequential Partial Precipitations of Barite From an Acid Solution ‘Sample No. Fl F2 Mass, grams 2.17 2.55 A pRg 5.5 98 Ra-226,pCi/g 9050-21400 Ra-228,pC/g 3770S 9780 ‘The next experiment involved precipitating 4 solid fractions from a solution of sulfuric acid, ‘water, and barium sulfate. ‘This precipitation 1t was performed at 80° C. The procedure followed, which was similar in most respects to the procedure in the previous test, is described below. 1) Start with a solution containing 5.69 grams of. NORM-containing scale. 2.35 grams of water. and 60.77 grams of sulfuric acid. 2) Add 1.5 grams of water tothe a id soluti acid from the precipitate, designated Orit hours later 3) Add 1.5 grams of water to the acid solution, Decant the acid from the precipitate, designated G-2, 18 hours later. 4) Add 1.5 grams of water to the acid solution, Decant ‘the acid from the precipitate, designated G-3, 4 hours later. 5) Add excess water to the acid solution, Separate this dilute acid from the precipitate that forms, designated G-4, 4 hours later. ©) Water wash and dry the four solid samples. ‘The data is shown in Table 5. The ratio of radium-226 and radium-228 was determined by gamma spectroscopy. A fraction of each sample SPE 28945 was dissolved and the radium-226 content was determined by radon emanation. The increased activity of the sequentially precipitated samples show obvious enrichment in the sequential steps, Table 5, Activity of Four Sequential Partial Precipitations of Barite From an Acid Solution at 80°C SampleNo. G1 G-2 G3 G4 Water content, wt. % 56 7.9 101 22 Mass, 1.72 2.36 115 0.22 Activity, aR /hig 35 35° 7.3 17 Re-226, pC/e 5900 6000 13900 20100 Ra-228, pCi/g 2350 2250 5000 7300 The quantity of scale not recovered was 0.24 grams out of 5.69 grams, or 4%. The activity of te bane orignally pur in solution was 6.3 300 iin 5.69 grams or 10,800 pCi per first two samples contained 24% es eat than did the barite used to make the feed stock. Greater separation is apparently achieved at room temperature than at 80°C. ‘The precipitate in G-1 and G-2 should have been (prior to water washing) Ba(HSO,)z. The G-3 sample should have been a mixture ‘Pina(H80,)y and and BaSQ,. The G-4 sample should have been exclusively BaSO,. These 4 samples were analyzed by x-ray diffraction. The first three samples were very pure barite. Due to the small sample size of G-4 it was not possible to determine if any minor components were present. The samples were also analyzed for uranium and thorium isotopes. None were found (ess than 0.5 ig/g uranium-238, less than 42 thorium-230, and less than 6 g/g thorium-232), but if any of these nuclides were present in the original scale, they could have remained in the solution phases during processing. ee sulfuric Ack ‘The radium content of the sulfuric acid, as opposed to the solids, was measured in a third experiment. The barite scale was from the same stock as for the Slow Precipitation Experiment aoe above, and it originally contained 10,800 Br gram of radio (7 per gram of Feaiton 226) The dan presented in Table 6, The radium content of the acid is negligible at 38% by ‘weight water. Traditionally, scales found in the oilfield have less than 1000 pCi radium per gram of scale. If this process is used for these lower activitySPE 28945 scales, the radium content of the acid at any water saturation should be proportionately lower. The acid used to treat barite that contains 1000 pCi radium per gram may contain only 12 pCi per iter after dilution to 40% by weight water. Table 6, Radium-226 Content of Sulfuric Acid - Water Mixtures With Dissolved Scale Water content of -Radium-226, pCi/L acid, weight % Test #1 20.4 35,8004900 29:8 3,0704177 39.8 129821 378 150416 Test #2 16. 31,70041100 20.5 4,3604320 24.4 1,140£110 Particle Size Distribution of the Product A fourth experiment was performed where the barite was precipitated in a manner to minimize particle size ~ with a large excess of water and constant stirring. The sample was then run through Coulter Counter to measure particle sizes. The sample was allowed to settle and age for three hours and the analysis was repeated. The data, shown in Table 7, show that sub-micron particles can be formed but they will grow over time. The particle size of the crystals can be varied by changing conditions - temperature, supersaturation ratio, agitation, aging, and a host of other factors - within a range of 0.7 microns to about 5 microns. In contrast, pore openings in unconsolidated sands are ‘Table 7, Particle Size Distribution of Fresh and Aged (3 hours) Precipitates Diameter Fresh ‘Aged Gm) (wr. %) (mt. %) 22.00 ° 0 >1.59 0 0.8 71,26 0.6 10.5 31.00 78 36.8 20.79 30.0 65.6 30.63 668 88.8 70.50 100 100 30.30 100 100 CHRISTOPHER G. HAYDEN AND THOMAS F. KRAEMER 7 ‘generally greater than 20 microns. The barite Should be able to be injcted into sandstone formations as a slury without bridging or plugging the formation, jroscope: The prices were too sal microscope. The particles were too small to get a clear picture - diffraction of light becomes significant a this size. ‘The partces did appear to be small rectangular shapes, with s similar to the ‘orthorhombic shape normally attributed to barite. ‘No long needles or other structures which might plug pore throats in sand was observed. CONCLUSIONS: This crystallization processes has the pporential to be Commercially useful for both tainimizing the quantity of NORM containing scale that must be disposed of and for getting the scale into form suitable for direct slurry injection into disposal formations. The process quantitatively separates NORM-free components including salts, sand, clays, carbonates, iron, calcium and suontium from the NORM-containing barite, The process allows an operator to "engincer” the waste by specifying the particle size and the final activi ‘The safety inherent in keeping the radium in a barite matrix, where radon emanation and to a large extent radium exposure to people in the event of a spill is minimized, is maintained by the process. Crystallization procedures have been developed to dissolve the NORM-containing barite and, through partial precipitations, refine - containing barite into a high-graded fraction and a low graded fraction. The process can concemmare: the NORM into a small fraction of the available barite. For a given dissolution/precipiuation step, the radium content of the bulk of the scale can be reduced by 40%. The data suggest the optimum cae ‘may be several precipitation steps formed at ambient ‘temperature. This has applicability when the barite contains very lit NORM, and the client requests that the majority of, the NORM.-bearing scale be treated to reduce NORM levels to a level below regulatory concern. ‘The end product would be a small quantity of barium sulfate that contains elevated but specified level of NORM, and a much larger quantity of ‘material that can be disposed of as nonhazardous ‘waste or reused in drilling mud. Scales that have very high concentrations of NORM, in the tens of thousands of picocuries per gram, can be “diluted” with barite, The NORM is actually dissolved and re-precipitated, so the8 CRYSTALLIZATION PROCESS TO REDUCE NORM-CONTAINING WASTE dilution occurs in individual crystals. This is not a false dilution such as would be the case if barite was added to NORM-containing barite and the two solid phases were inixed together. ‘This dilution has applicability when concentrations of radium pose a substantial health risk to workers. Another benefit of the crystallization procedure is that the barite crystals formed can have very small, uniform particle sizes. This is desirable in circumstances where subsurface injection of NORM into sandstone formations is a disposal method under consideration. Particle sizes smaller than one micron in diameter have been generated in the crystallization experiments. Particles smaller than 4 microns can often be injected into sandstone formations with minimal plugging. There are few additional waste streams generated by this process. The sulfuric acid is not ‘consumed in the process, and can be dehydrated and re-used in the process. It is a very inexpensive acid, and is available at costs between $50 and $75 per ton. Commercial sulfuric acid regeneration plants exist and recycle acid for about twice the cost of virgin acid. The sand and clays should have all the NORM removed, and hence should be non- hazardous oilfield waste. The hydrochloric acid will have some metals, primarily calcium and iron, and will require disposal. Typically, a few gallons of hydrochloric acid is needed to treat a barrel of sludge. The radium ends up in a barium sulfate mutrix, The barium sulfate crystal structure is essentially inert to digestion and inhibits radon emanation. Radon is trapped in the crystal structure, and the alpha recoil that occurs during the tion of a radon atom can only kick the radon molecule a few tenths of a micron, There is litle radon emanation from even very small particles. ‘The end result is that NORM contained in barit contains built in safeguards against human ion. In the event of a spill of NORM- containing acid, the acid will react with available water to form barite crystals, thereby trapping the NORM in a form where it is possible to easily recapture during subsequent cleanup. ACKNOWLEDGEMENTS The authors would like to thank our respective employers. The majority of the work described was funded by the Institute of Gas Technology. 16 SPE 28945 REFERENCES Harris, D. C.: Quantitative Chemical Analysis, 3rd Ed., W. H. Freeman and Company, New York 1991). Fisher, J.B. and Hammond, M.: "Characterization ‘of NORM Vessel Solids," Proceedings of the International Petroleum Environmental Conference, Houston (March 1994), Linke, W.F.: Solubilities, Inorganic and Metal- Organic Compounds, Volume 1, 4th Ed.,D. Van Nostrand Company, inc., Princeton, NJ (1958). Jacobson, C.A. Ed.: Encyclopedia of Chemical Reactions, Volume 1, Reinholt Publishing Corporation, New York City (1946), Garrels, R.M, and Christ, C.L.: Solutions, Minerals, and Equilibria, Harper and Roe Inc., New York (1965).