Estuaries Vol. 13, No. 1, p.

89-97

March 1990

Petroleum Drilling and Production Operations in the Gulf of Mexico

C. S. FANG

Department of Chemical Engineering University of Southwestern Louisiana Lafayette, Louisiana 70504

ABSTRACT: Decades o f offshore and inland petroleum drilling and production in the G u l f o f Mexico and on the Gulf Coast have provided the much needed energy and chemical feedstocks to the nation, and also have made an impact on the environment in the area. Our study showed deposits o f contaminated sediment on the ocean floor around offshore platforms, old reserve pits, and dump sites next to many surface facilities and compressor stations. The substances found on the ocean floor and in dump sites are simple or emulsified mixtures o f silt, hydrocarbons, and water. The cleaning o f the ocean floor and pits is an economic and technical challenge. Hydrocarbons are from crude oil and chemical additions for various operational necessities, including additions o f biocides, corrosion inhibitors, antifreezes, and coagulants. When the new government regulations lower the allowable m a x i m u m total organic carbon level to the 50 ppm range, these hydrocarbons can no longer be ignored by drilling and production operators.

Introduction

Decades of offshore and inland petroleum drilling and production operations in the Gulf of Mexico and on the Gulf Coast have provided the much needed energy and chemical feedstocks for the nation, but they also have made an impact on the environment in the area. Since the early 1980's, both the industry and the government have been working on several fronts to protect the environment while maintaining the needed oil and gas production. These fronts include t h e establishment of environmental regulations, application of new drilling practices, treatments of produced water, and evaluation of environmental impacts on offshore operations.An environmental assessment is of great interest at this time for three reasons: (1) a new round Of active drilling in the Gulf of Mexico appears to be.around the corner, (2) the Clean Water Act begins to show an impact on the oil and gas industry, and (3) communities on the Gulf Coast are considering diversifying their industrial bases.
Oil and Gas Production in the G u l f o f Mexico

From 1978 to 1982, the United States accounted for 38% of the" world-wide offshore well count.
This paper was presented at a symposium organized by Edward Overton and Louis Thib0deaux and held in conjunction with a meeting of the American Chemical Society in New Orleans, Louisiana, August 31-September 1, 1987. The paper is being published in cooperation with the Hazardous Waste Research Center, Louisiana State University, Baton Rouge, Louisiana.
9 1990 Estuarine Research Federation 89

Most U.S. offshore wells are in the Gulf of Mexico. From 1954 through 1984, 23,414 exploration and development wells were drilled in the Gulf of Mexico, an average of 755 wells per year (Nikituk and Farris 1986). No other U.S. Outer Continental Shelf region has ever had more than 100 well starts per year. Even in a lean year, from July 1985 to June 1986, 721 wells (294 exploration wells and 427 development wells) were drilled (Risotto and Collins 1986). Most (203 exploration wells and 371 development wells) were in the central Gulf of Mexico region. In 1984, there were 3,866 production platforms and 8,983 producing wells in the Gulf of Mexico (EPA 1985). These wells produce approximately 11% of the U.S. crude oil and 22.8% of natural gas. In 1985, the region's annual oil production was 57.1 million m s (0.156 million m s d -1) of crude oil and condensate, representing 92.1% of the total U.S. offsho/'e oil production. I n the same year, it produced 111.9 billion m a (3,951.8 billion ft s) of natural gas, which was 98.8% of the total U.S. offshore gas production (EPA 1985). These data are summarized in Table 1. Most of the offshore oil and gas products were from the central Gulf of Mexico region: 94.3% in oil and 77.9% in gas production. According to a recent survey, the predicted 1987 U.S. crude oil and natural gas productions were 1.32 or 1.339 million m 3 d -1 and 453 billion mS yr -~ (16,000 billion ft s yr-l), respectively (Oil and Gas Journal 1986, 1987). According to the proposed next five-year Outer Continental Shelf (OCS) oil and gas leasing program (1987-1991), the Gulf of Mexico will be the
0180-8347/90/010089-09501.50/0

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c. 8. Fang

TABLE 1. Oil and gas production in the Gulf of Mexico.

U.S. Total U.S. Offshore Gulf of Mexico

No. of wells drilled 1954-1984 July 1985-June 1985 Producing wells 1984 Production platforms 1984 Crude oil, million m ~ d -~ 1985 1987 Natural Gas 1985, bcm" 1987, bcm 1985, mmcm d -tb ' bcm" billion cubic meters. b mmcm d-a: million cubic feet per day. c bcf: billion cubic feet. a 11.1% of the U.S. total. 22.8% of the U.S. total.

m m m m

-11,000 3,896 1.412 1.32,1.339 0.1696

23,414 721 8,983 3,866 0.156 (11.1%) ~

490.0 (17,304 bcf) c 453.1 (16,000 bcf) 1,343 (47,410 mmcf d -t)

113.30 (4,001.0 bcf) --310.41 (10,962 mmcf d- 0

111.90 (22.8%) e (3,951.8 bc 0 --306.6 (10,827 mmcf d -~)

most interesting and active region among all offshore regions (U.S. Dept. of Interior 1986). ] ' h e total funding by the Mineral Management Service, Department of Interior, for the Environmental Studies Program from 1973 through 1984 was $373.1 million (Nikituk and Farris 1986). T h e Gulf of Mexico region dominates the U.S. offshore oil and gas production, as indicated above, but it draws only 14.1% of OCS environmental study funds. The funds for Alaska and the Atlantic and Pacific regions are, respectively, 49.5%, 21.8%, and 11.3%.

Operations in Oil and Production Oil and gas production is more than the releasing of oil and gas from a subsurface reservoir to the
TABLE 2. Operations in oil and gas production.
Operations

surface. Various operations are needed to support the production and to maintain the equipment. In these operations, a broad range of chemicals are used, and some of them have important environmental implications. Table 2 shows various operations, including exploratory drilling, production operation, produced water treatment, and transport of oil to the refinery plant and gas to the gas processing plant. Also shown are chemicals used in these operations. Biocides and corrosion inhibitors are used in both drilling and production operations. Surface equipment and their operations are shown in Fig. 1. They may be installed on an offshore platform. If the platform is not far from the shore, equipment for gas-liquid separation and

Chemicals Used

A. Production 1. Corrosion control 2. Scale control 3. Scale removal 4. Microorganism control 5. Produced water treatment B. Transport 1. Gas compression 2. Flow control and deposit removal C. Drilling (exploratory and development) 1. Drilling fluid control 2. Disposal of drill cutting and brine D. Utility Generation Electricity, cooling water, and domestic water generation

Corrosion inhibitor Scale inhibitor Scale solvent Biocide Demulsifier, flotation aid Antifoamer Lubrication oil Antifreeze, solvent Weighting agent, lubricant, corrosion inhibitor, biocide, etc.

Drilling and Production

91

produced water treatment may be installed onshore. Raw produced fluid from a well is fed to one or several stages of gas-liquid separation. T h e produced water is treated before it is discharged overboard. The treatment is gravity oil separation (water skimmer) or flotation, or both (Arnol d 1983; Arnold and Stewart 1986). Skim pipe is also reported in some cases as a part of produced water treatment. Chemicals, such as demulsifier and flotation aids, are used in produced water treatment (Petrazzuolo et al. 1985). According to the U.S. Environmental Protection Agency's Gulf of Mexico Sampling Program (EPA 1985), which was a survey conducted from October 9 through October 30, 1981, for 30 oil and gas platforms, the average flow rates of natural gas, oil, and produced water from a platform are as follows: oil and condensate--551.9 m s d -~, natural gas--0.6066 million m s d -~ (21.42 million ft s d-J), and produced w a t e r - - 1 5 1 5 m s d Because of these operations, many chemicals are added to the operating system, and more than a dozen discharges are made constantly or intermittently. The major discharges are 1) produced water, 2) drilling fluid, and 3) drill cuttings and associated wash water. These discharges will be discussed later. According to Petrazzuolo et al. (1985) and an EPA report (EPA 1985), there are 13 additional discharges, but they are small in volume and therefore are considered minor ones.
Produced Water The largest discharge by volume from an offshore platform is produced water. Produced water mostly is formation water, but it can be water condensed from flowing gas mixture in the production tubing string. The rate of produced water generation depends on a number of factors, including reservoir characteristics and the age of a well. Five surveys on the rate of produced water generation in the Gulf of Mexico (EPA 1985) show different results. On the average, they are 884, 514, 227,302, and 1,515 m s d -1 platform-L A similar value, 884 m s d -1 platform -1, was reported by Menzie (1982). These are averages of very broad ranges. For example, the range for 1,515 m s d -~ platform, is 21.0 to 23,800 m s d -~ platform-L Based on the data given by the Gulf of Mexico Sampling Program (EPA 1985), the ratio of produced water to oil production is 2.74 by volume. Then, assuming that 11% of the U.S. oil production in 1987 (same as in 1985) is from the Gulf of Mexico, the rate of produced water generation is 1.32 x 0.11 x 2.744 = 0.398 million m ~ d -1. All of this is directly or indirectly discharged to the Gulf of Mexico. This figure is greater than that reported by Hileman (1981).

Fig. I. Flow diagram of oil and gas production. I producing well, 2 produced fluid, 3 gas-liquid separator, 4 FWKO, 5 bulk treator, 6 water skimmer, 7 dry oil tank, 8 gas compressor, 9 glycol contactor, 10 recycle pump, 11 skim pipe, 12 oil, 13 gas, 14 slops, 15 produced water, 16 natural gas, 17 crude oil, 18 treated produced water, 19 flotation cell.

Hileman's figure is 74,400 m s d -~ for the 19751978 period. Produced water contains organic and inorganic compounds, and some of these compounds are of environmental concern. Three sources of these compounds are 1) organic compounds extracted from crude oil and inorganic compounds in formation water, 2) chemicals added to produced water or injected into a producing well for operations given in Table 2, and 3) impurities in chemicals used. Some of the paraffins and aromatics in crude oil have moderate solubility in water. As oil, gas, and water flow upward together in a long production tubing string, a small portion of paraffins and aromatics are dissolved in water. At the same time, a small amount of crude oil may disperse in water. As a result, a heater and long retention time are needed to separate the water and oil. In recent produced water discharge permits, the oil and grease in water is kept as low as 72 mg I-L T h e r e are discussions to keep the T O C (total organic carbon) at 50 mg 1-~ or less. A new separation technology may be needed for such a low T O C concentration. The T O C includes oil, grease, and dissolved hydrocarbons. Benzene, toluene, ethylbenzene, phenol, naphthalene, and 2,4-dimethylphenol are found in produced water (EPA 1985; Petrazzuolo et al. 1985). They are priority pollutants. Their concentrations are skown in Table 3. In some cases, bis(2-ethylhexyl) phthalate, di-n-butyl phthalate, fluorene, and diethyl phthalate are also found in produced water (EPA 1985).

92

C.S. Fang

TABLE 3. Estimatedpollutants discharged via produced water.

Concentration, rag 1-: Pollutant Range [3] Average [3] One Platform" Discharge Gulf of Mexicob

Oil and grease 7-514 75.5 0.114 m3 d -1 Organic compounds kg d-* lb d-1 Benzene 0.140-12.040 2.389 3.18 (7.0 i) Ethylbenzene 0.019-6.010 0.406 0.531 (1.17) Naphthalene 0.026-1.179 0.183 0.317 (0.699) Phenol 0.065-20.812 2.174 3.52 (7.77) Toluene 0.104-12.00 1.967 2.58 (5.69) 2,4 DMP 0-2.294 0.184 0.269 (0.592) Metals Zinc 0.137 0.207 (0.457) Copper 0.0649 0.0984 (0.217) Nickel 0.0158 0.0239 (0.0527) Lead 0.413 0.626 (1.38) Cadmium 0.00327 0.00494 (0.0109) Based on 9,526 bbl d-1 platform-~ of produced water and average concentration. b Based on 2.27 mmbbl d-~ of produced water and average concentration: " 1 ton (short) = 2,000 Ibm. In most cases, produced water is from formation water, which contains inorganic compounds. When it is checked for dissolved metals, zinc and copper are found 81% and 19% of the time, respectively (EPA 1985). Nickel, lead, and cadmium are found occasionally.
Corrosion Control

9,950 m3 yr-~ 305 ton yr-k 51 30.5 338 248 25.8 19.9 ton yr-l 9.43 2.30 60.0 0.475

Corrosion of production and casing tubings, surface equipment, and drilling equipment is an acute problem, particularly in offshore operation. Efforts are constantly being made to mitigate the problem (EnDean 1976; Narain et al. 1985). Corrosion inhibitor, diluted with diesel oil, propanol, or fresh water, is applied regularly to oil and gas production wells. Recently produced oil is preferred over diesel oil. T h e r e are three different methods of applying corrosion inhibitor solution (NACE 1979): 1) continuous m e t h o d - - p u m p i n g corrosion inhibitor continuously t h r o u g h a tubing in the casing to the bottom hole; 2) squeeze technique--periodically, the gas well is shut off, and corrosion inhibitor is p u m p e d to the reservoir; when the gas well resumes production, corrosion inhibitor is released from the formation water and adsorbed on the tubing wall; and 3) batch treatment--periodically, the gas well is shut off, and corrosion inhibitor is pumped to the tubing to coat the tubing wall. Corrosion inhibitor and its diluent flow back to the surface along with oil and gas. A part of them ends up in produced water. Corrosion inhibitor usually is a polar molecule capable of adsorbing on the metal surface to form a protective film. It can be either an inorganic or organic compound. Corrosion inhibitors used in oil fields are given by Ostroff (1979). Most corrosion inhibitors used in oil fields are reportedly organic (DiStasio 1981; Pat-

t o n 1986). T h e y i n c l u d e f o r m a l d e h y d e , f a t t y amines, fatty amine salts, fatty acid amides, substituted pyridines, and t e t r a m e t h y l a m m o n i u m azide (Ostroff 1979; DiStasio 1981; Petrazzuolo 1985). Sometimes a weighting agent, such as ZnCI~, is added to the corrosion inhibitor solution in the squeeze and batch treatments to speed up the fall of solution, and consequently, shorten the shut-in time (Patton et al. 1970). Corrosion inhibitor, its diluent and weighting agent are foreign substances to the offshore environment, but they are not necessarily hazardous. However, they contribute to environmental monitoring parameters, BOD, and T O C . T h e concentration o f corrosion inhibitor in produced water is of interest in the study of chemical discharge from an offshore platform, but it is not available, except in the following case. In a study of the squeeze technique, it was found that the concentration of corrosion inhibitor in produced fluid (oil and produced water) needed to provide adequate protection is 10 ppm by volume (Kerver 1965). T h e r e f o r e , the concentration varies from 60 to 10 ppm depending on the time since injection. If the inhibitor is oil soluble but water insoluble, it may not show up in produced water. On the other hand, if it is water soluble, the situation will be reversed. Scale C o n t r o l Formation water is rich with various dissolved solids, such as calcium, barium, and ferrous ions, which can easily develop undesirable scale on tubing wall and down-hole pore space, when temperature, pressure, and pH value change. T h e first line of defense against scaling is application of scale inhibitor to prevent its formation.

Drilling and Production TABLE 4. Examples of biocides used in oilfield.

Biocides Reference

93

K-31 (Pentanedialdehyde) Champion Chemical Co. KC-14 (alkyldimethyl benzyl chloride) Champion Chemical Co. Magnacide B (acrolein) Magna Corp. Surfactron DQ44 (a surfactant) Tretolite X-CIDE XC-102, glutaraldehyde Tretolite X-CIDE XC-370 (alkyl dimethyl ammonium chloride) Coco primary amine acetate Coco trimethylene diamine 1-phenyl-4,4-dimethyl imidazoline Sodium tetrachlorphenate Peracetic acid Acetic acid Formic acid Chlorine

Petrazzuolo (1985) and Middleditch (1980)

Petrazzuolo (1985) Ostroff (1979)

Fang (personal communication)

Scale inhibitor usually is applied to a producing well and surface equipment by continuous injection. In some cases, it is applied to a water producing formation by the squeeze technique, similar to corrosion inhibitor. ]'he concentration of scale inhibitor for effective scale prevention is in the range of 5 to 15 ppm by volume in clean water (Patton 1986). It was found that one squeeze j o b will provide adequate scale prevention for a dolomite reservoir well for 2,385 to 3,180 m ~ (15,000 to 20,000 bbl) of produced water. The protection is ten times for a sandstone reservoir: 23,850 m s (150,000 bbl) of produced water (Ostroff 1979). Most scale inhibitors used in oil fields are organic scale inhibitors. They are (Ostroff 1979; Petrazzuolo et al. 1985; Patton 1986) 1) organic phosphate esters, example, Tretolite Scale Preventive SP-175 (a solution of polyphosphate esters of oxyalkylated polyols and alkanolamines in water and methanol); 2) organic phosphonates, examples, Tretolite Scale Preventive SP-246 (a solution of an organic phosphonate in water), Tretolite Fludex WF-123 (a solution of salts of acylated amines and organic phosphonates in water and methanol); 3) organic acids, examples, Tretolite Scale Preventive SP-36 (a sulfamic acid coated with a quaternized amine and a oxyalkylatedphenol), EDTA (Ethylene diamine tetraacetic acid); and 4) organic polymers such as polyacrylic polymer. These scale inhibitors can contribute significantly to BOD and TOC. When the new discharge regulation on the T O C standard is lowered to the 50 mg 1-1 range, the T O C of scale inhibitor, as well as corrosion inhibitor, can no longer be ignored by drilling and production operators.

Therefore, biocides are added to drilling fluid and produced water. Some biocides are toxic, and require some planning and caution in their applications. Examples of biocides used in oil and gas production are acrolein and glutaraldehyde. More examples are shown in Table 4. Sodium chromate was popular in the past, but it is no longer used because of the environmental concern. The required biocide concentration depends on the individual biocide used. T h e concentration can be as low as 5 to 25 mg 1-1, and also can be higher than 100 mg 1-1 (Ostroff 1979). In one case, produced water was found to have formic acid (75100 nag 1-~) and acetic acid (650-800 mg 1-1), which were reportedly used as biocides. In the Buccaneer Field Study, acrolein was used, but it was not found in produced water (Middleditch 1980). The Gulf of Mexico Sampling Program, which covers 30 platforms, also found no acrolein (EPA 1985). Acrolein is a volatile organic compound. It is possible that acrolein is evaporated from produced water in the flotation unit.

Other Chemical Additions

There are other chemicals added to produced fluid, such as methanol and ethanol, as antifreeze agents, lsopropanol is reported in produced water. It is used as coupling solvent, or hydrocarbon control ag.ent, assisting the performance of other added organic chemicals. Since chemicals used in drilling and production are industrial grade, they usually contain impurities. Two examples are acetone in organic chemicals and trace metals in barite. After their applications, fates of these chemicals and their impurities are not clear at this time. Some of them were found in produced water. In one produced water treatment facility, produced water was found to have methanol (80-100 mg 1-1), eth-

Control of Microorganisms Microorganism growth in drilling and surface equipment can cause corrosion or fouling, or both.

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O.S. Cang

"FABLE 5. Scale solvents. Scale Calcium carbonate Iron sulfide and oxides Iron oxides Silicon dioxide Calcium sulfate ScaleSolvent Hydrochloric acid Citric acid Hydrofluoric acid Ammonium bifluoride Sodium hydroxide Sodium gluconate Potassium hydroxide Potassium gluconate EDTA Polyphosphate Nitrotriacetic acid Toluene, xylene
Reference

Ostroff (1979) William et al. (1979) Ostroff (1979)

Asphaltenic and paraffinic deposits

DiStasio (1981)

anol (90-120 mg l-l), isopropanol (5-20 mg l-~), and acetone (1-2 mg 1-1).

Discharge Via Produced Water

After a quick scan of various operations in oil and gas production, which include corrosion, scale, and microorganism controls, it is clear that a detailed inventory of substances discharged along with produced water to the Gulf of Mexico from 3,866 platforms is not an easy task. In the Buccaneer Field Study, 115 components (114 organic compounds and sulfur) were identified in produced water (Middleditch 1980). Priority pollutants in produced water were studied by the Gulf of Mexico SamplingProgram (EPA 1985; Petrazzuolo et al. 1985). The study found that the concentrations of priority pollutants in produced water are low, as shown in Table 3. T h e amounts of discharge for each component are calculated based on the average concentrations, 1,5-I 5 m ~ (9,256 bbl) d -] platform -1 of produced water and 0.399 million m s (2.51 mmbbl) d -] of produced water discharged to the Gulf of Mexico. T h e amounts of discharge of priority pollutants shown in Table 3 raise the question: How well are they dispersed and distributed in the Gulf after discharge? A number of organic compounds, such as acetic acid, formic acid, methanol, and ethanol, were not analyzed in the Gulf of Mexico Sampling Program and Buccaneer Field Study. They are not priority pollutants, but they are part of BOD and T O C in produced water, which are regulated by environmental regulations.

For corrosive scale solvents, such as hydrochloric acid, corrosion inhibitor is added to the scale solvent. Since scale is often coated with hydrocarbons, a pretreatment is needed before application of scale solvent. The pretreatment can be either a simple flush of a hydrocarbon solvent or a hot oil wash (Ostroff 1979). Production is hindered by deposits ofasphaltenic and paraffinic compound on tubing walls and in formation pore space. Organic solvents, such as amines, toluene, and xylene, are used to remove these organic deposits (DiStasio 1981), or soften them before the "pigging" operation. "Pigging" is an operation to clean a service line or pipeline by pushing a rubber, bullet-shape object through the line. This operation may be completed as often as once every month.

Drilling Fluid and Drill Cutting

In exploration and development drilling for oil and gas, drilling fluid is used for a number of reasons, including carrying drill cutting to the surface. As a result, a portion of drilling fluid is discharged overboard along with the drill cutting. Because of a broad range of materials and chemicals used in the drilling fluid, its discharge to the ocean floor is of environmental concern (Nesbitt and Sanders 1981; Ayers et al. 1985; EPA 1985). The base of a drilling fluid can be fresh water, brine, or diesel oil (Gray and Darley 1980). Recently, the use of diesel oil in offshore drilling has been discouraged. Major additives in various types of drilling fluid are illustrated by Ayers et al. (1985). They include barite, bentonite, and caustic. Based on a 96-hour LCs0 value test, these major additives are found to be practically nontoxic. Recently, eight basic types of drilling muds were developed by the U.S. Environmental Protection Agency. Their generic mud systems were reported by Ayers et al. (1985). However, the other additives, such as emulsifier,

Well and Pipeline Treatments

From time to time a producing well or pipeline will use treatments, because of the scaling or fouling in the production tubing or down-hole formation. As shown in Table 5, hydrochloric acid and other scale solvents are used to remove undesirable scales and organic deposits.

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95

corrosion inhibitor, lubricant, and biocide, are not as simple and require f u r t h e r examination. Drill cutting, wet solid particles removed from the formation in drilling, contains hydrocarbon and dissolved metals, as found by Menzie (1982), Nesbitt and Sanders (1981), EPA (1985), Petrazzuolo et al. (1985), and many others. Dissolved metals in drill cutting d e p e n d on the location of the well and the depth of drilling. Table 6 shows conventional environmental parameters, hydrocarbons, and dissolved metals found in drill cutting in the Gulf of Mexico (Petrazzuolo et al. 1985). Dissolved metals with the concentration less than 1 mg kg -~ are not included in the table. T h e list of hydrocarbons and dissolved metals is long; some are priority pollutants.

TABLE 6. Pollutants in drill cuning, b Range Conventional parameters Oil and grease, mg kg -1 BOD~, mg kg -~ TOC, mg kg -~ Hydrocarbons, mg kg -t Acenaphthene" Naphthalene* 4-Nitrophenol* n-Nitrosodipbenylamine" bis(2-ethylhexyl) Phthalate Phenanthrene* Pyrene* Dibenzothiophene Dibenzofuran n-Dodecane Diphenylamine Alphaterpincol Biphenyl 54,200-130,000 325-3,970 58,300-61,300 0.677-38.8 3.582-149 30.4 2.87-56.5 17.3 25.8-145 7.86-18.9 15-37.3 2.15-33.7 1.62-403 5.9-56.5 6.31 1.17-69.4

Discharge from Drilling Operation According to Petrazzuolo et al. (1985), the rate of drilling fluid and drill cutting discharges to the Gulf of Mexico are, respectively, 18.4 m s (116 bbl) and 7.4 m s (47 bbl) d -1 well -1. T h e average depth of the wells drilled in the area is 3,170 m (10,400 ft) and the average length of drilling time is 61 d. Based on these figures, the average drilling fluid and drill cutting discharges are 1,125 m s (7,076 bbl) well -1 and 455.8 m s (2,867 bbl) well -1, respectively. T h e total discharge is 1,582 m 3 (9,943 bbl) well -1. Not all of the 1,581 m 3 (9,943 bbl) of discharge is hazardous material. However, if it contains any environmentally sensitive substance and if it remains in a small areas near the platform after discharge, 1,581 cubic meters can make a significant environmental impact. Sediment on the Ocean Floor Standing on a production platform in the morning, one can see every few minutes a graceful rise of an oil bubble or a fish to the water surface. T h e oil bubble makes a shining circular sheen u n d e r the m o r n i n g sun, indicating sediment contamination on the ocean floor beneath. T h e sediment sample from the ocean floor near the platform smells like a mixture of diesel oil and rotten eggs. These platforms have been in operation for years, and yet, the sediment contamination left behind in the time of drilling is still intense. T h e Buccaneer Field Study found that the T O C concentration in sediment near the platform is higher than that in the surrounding ocean floor (Middleditch 1980). However, without a survey, it is difficult to say how many platforms are surrounded by hydrocarbon-rich sediment. In an ocean floor cleaning project, the sediment is sucked from the sea bed, along with sea water, and is fed to a shale shaker and desander on a barge

Dissolved metals, mg kg -t (dry basis) Zn" 107-2,710 A1 7,810-10,900 Ba 34-84.8 Fe 16,600-30,800 Cd* 0.402-15.4 Cr* 9.40-11.7 Cu" 20.6-55.3 Ni* less than 6-12.1 Pb* 21.4-298 As" 7.07-10.3 * Priority pollutants. b From Petrazzuolo et al. (1985).

(Fang and Smith 1986). T h e solids collected from the shale shaker and desander are b r o u g h t back onshore for incineration, while the water effluent from the desander is released back to the ocean. Table 7 gives hydrocarbons and relative concentrations found in the sediment. Cleaning a contaminated ocean floor is a timeconsuming and costly process. It takes a team of four men 1 wk to recover, 1,918 m s (12,000 bbl) of contaminated sediment from the ocean floor. T h e cost is $30,000 per week. An attempt was made to find trace metals in the ocean floor sediment near a platform in the Buccaneer Field (Middleditch 1980). Elements targeted for analysis in this study were Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, and Zn. It was found that e x p l o r a t i o n / p r o d u c t i o n activities have a negligible effect on the level of trace metals in sediment, except cadmium and barium. However, cadmium may be due to the corrosion of the platform structure. Barium is from barite used in drilling fluids.

Oil Pits T h e r e are many produced water t r e a t m e n t facilities and compressor stations on the Gulf Coast which receive and treat oil, produced water, and

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c.s. F ~

TABLE 7. Hydrocarbons in sediment from the ocean floor." Aromatics Benzene Toluene m-Xylene o-Xylene Propyl-benzene Mesitylene Butyl-benzene Hexyl-benzene Octyl-benzene Decyl-benzene Subtotal Priority pollutants (Benzene and Toluene) 18.84% 0.93 0.78 0.89 1.21 0.21 0.10 0.07 0.45 2.66 26.16% (220.0 ppm) 19.77% (166.3 ppm) Tetracosane Heptane Octane Nonane Decane Undecane Dodecane Tridecane Tetradecane Pentadecane Hexadecane Heptadecane Octadecane Nonadecane Eicosane Heneicosane Docosane Tricosane Hexacosane Octacosane Subtotal Para~ns 17.83%
1.43

4.59 0.32
1.07

0.01 0.01 0.23 0.05 0.55 0.76 4.54 2.08 3.04

11.41

6.48 7.93 11.12 0.14 0.08 73.84% (621.1 ppm)

Total hydrocarbons: 100% (841.1 ppm by wt.) 9From Fang and Smith (1986). natural gas From offshore platforms. Old pits and d u m p sites are often f o u n d n e x t to these facilities. T h e s e pits and n u m e r o u s pits left b e h i n d by inland drilling operations have b e c o m e an e n v i r o n m e n t a l c o n c e r n on the G u l f Coast because they are filled with oil- and metal-rich sludge. Physical characteristics o f offshore sediment and pit sludge are different in most cases, but their chemical compositions are similar. T h e y are mixtures o f silt, barite, h y d r o c a r b o n s , and water. T h e consistency o f pit sludge varies broadly. A f t e r years o f evaporation, it can be a slurry, gel, or cake-like. Pit sludge often is an emulsion and its separation into oil and water can be a difficult task. T h e cost o f hauling away pit sludge is $20 per cubic yard. T h e present on-site t r e a t m e n t o f ocean sediment and pit sludge is basically a mechanical separation, or a combination o f different mechanical separations. In some cases, chemical demulsifiers and coagulants are used. Mechanical separations are sedimentation, centrifuge, cyclone separation, and filtration. Mechanical separations are not effective in r e m o v i n g dissolved hydrocarbons. T h e results o f on-site t r e a t m e n t in Louisiana are regulated by the "Statewide O r d e r No. 29-B," which monitors, a m o n g o t h e r factors, total organic c a r b o n ( T O C ) and oil and grease (O&G).
Conclusions

U.S. In this study o f e n v i r o n m e n t a l impacts o f past and present operations in oil and gas production, the following observations and conclusions are made. Both g o v e r n m e n t and industry are c u r r e n t l y doing m o r e to p r o t e c t the e n v i r o n m e n t than they did in the 1960's and 1970's. Many chemicals are used in various operations to support oil and gas production. Some o f them, such as biocides, are environmentally m o r e sensitive than the naturally occurring h y d r o c a r b o n s in p r o d u c e d water. W h e n the new g o v e r n m e n t regulations lower the allowable m a x i m u m T O C level to the 50 mg 1-1 range, the T O C o f a d d e d corrosion inhibitor, scale inhibitor, biocide, demulsifier, and o t h e r specialty chemicals can no longer be i g n o r e d by drilling and p r o d u c t i o n operators. O n c e c o n t a m i n a t e d discharge reaches the ocean floor, it takes contaminants a long time to disperse into the ocean. Production and drilling o f the past decades have left a substantial a m o u n t o f oil- and barium-rich sediment and pit sludge in the G u l f o f Mexico and the coast area. LITERATURE CITED ARNOLD,K. 1983. Design concepts for offshore produced-water treating and disposal systems.J. Petrol. Technol. 35:276-283. ARNOLV,K. ANDM. STEWART. 1986. Surface Production Operations, Vol. 1. Gulf Publishing, Houston, Texas. 414 p. AVERS,R. C.,JR., T. C. SAUER, JR., ANDP. W. ANDERSON. 1985. The generic mud concept for NPDES permitting of offshore drilling discharges.J. Petrol. Technol. 37:475-480. DISTASIO,J. I. 1981. Chemicals for Oil Field Operations, Re-

T h e Gulf o f Mexico has been and will continue, in the foreseeable future, to be the most i m p o r t a n t region o f offshore oil and gas p r o d u c t i o n in the

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cent Developments. Noyes Data Corp., Park Ridge, New Jersey. 307 p. ENDZAN, EJ. 1976. Corrosion control in the well bore. Petrol. Eng. Aug. 1976:50-62. EPA. 1985. Development Document for Proposed Effluent Limitations Guidelines and New Source Performance Standards for the Offshore Subcategory of the Oil and Gas Extraction Point Source Category. EPA 440/1-85/055. Washington, D.C. 408 p. FANG, C. S. AND S. A. SMITH,JR. 1986. Cleaning of the ocean floor near off-shore platforms in the Gulf Coast. Energy Prog. 6:37-39. GRAY, G. R. AND H. C. H. DARLEY. 1980. Composition and Properties of Oil Well Drilling Fluids, 4th ed. Gulf Publishing, Houston. 630 p. HILEMAN, B. 1981. Offshore oil drilling. Environ. Sci. Technol. 15:1259-1263. KERVER,J. K. 1965. Corrosion inhibitor squeeze technique-Field evaluation of engineered squeeze.J. Petrol. Technol. 17: 5O-57. MENZIE, C. A. 1982. The environmental implications of offshore oil and gas activities. Environ. Sci. Technol. 16:454A472A. MIDDLEDITCH, B. S. 1980. Environmental Effects of Offshore Oil Production. Plenum Publishing Corp., New York. 446 p. NARAIN, S., S. ASSAD, K. V. D. P. RAO, AND M. R. BARAKAT. 1985. Case histories of corrosion problems in a wastewater treatment plant. Material 8ci. 23-27. NATIONALASSOCIATIONOF CORROSIONENGINEERS. 1979. Corrosion Control in Petroleum Production. N A C E / T P C No. 5. Houston, Texas. 84 p. NESmTT, L. E. ANDJ. A. SANDERS. 1981. Drilling fluid disposal. J. Petrol. Technol. 31:2377-2381.

NIKITUK, P. M. AND V. A. FARRIS. 1986. OCS National Compendium. OCS Information Report, MMS86-0017. Reston, Virginia. 172 p. OIL ANn GAS JOURNAL. March 10, 1986. Worldwide crude oil and gas production, p. 80. OIL AND GAS JOURNAL. April 13, 1987. Worldwide crude oil and gas production, p. 32. OST~OrF, A. G. 1979. Introduction to Oilfield Water Technology. NACE. Houston, Texas. 394 p. PATRON, C. C. 1986. Applied Water Technology. Campbell Petroleum, Norman, Oklahoma. 364 p. PATRON, C. C., D. A. DEEMER,AND H. M. HILLIARD,JR. 1970. Oilwell liquid inhibitor effectiveness. Material Protect. Feb. 1970:37-41. PETRAZZUOLO, G., A. D. MICHAEL, C. A. MENZIE, H. PLUGGE, E.J. ZIMMERMAN,R. G. ROLAN, T. A. MORES, L. A. SMITH, W. K. PARLAND,ANn S. E. ROTH. 1985. Assessment of Environmental Fate of Effects of Discharges from Offshore Oil and Gas Operations. EPA 440/4-85/002. Washington, D.C. 384 p. RISOTRO, S. P. ANOJ. H. COLLINS. 1986. Gulf of Mexico Summary Report/Index, Nov. 1984-June 1986. OCS Information Report, MMS86-0084. Reston, Virginia. 102 p. U.S. DEPT. OF INTERIOR, MINERALMANAGEMENTSERVICE.1986. Proposed Program, 5-year Outer Continental Shelf Oil and Gas Leasing Program for January 1987-December 1991. Washington, D.C. WILLIAMS, B. B., J. L. GIDLEY, AND R. S. SCHECHTER. 1979. Acidizing Fundamentals. Society of Petroleum Engineers, Dallas, Texas. 124 p.

Received for consideration, June 14, 1988 Accepted for publication, May 24, 1989