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W E T L AY - UP F LUID: C A N I T B E B OTH C ORROSION P REVENTIVE A N D E NVIRONMENTALLY F RIENDLY?

by R.B. Chen and E.Y. Chen R.B. Chen holds a masters degree in biology and works as a senior lab scientist in Saudi Aramcos Laboratory Research and Development Center. Prior to Saudi Aramco she was affiliated with Conocos Research and Development Department. She has published and presented several papers internationally. E.Y. Chen holds a Ph.D. in material science from Georgia Institute of Technology and is a NACE International Accredited Corrosion Specialist. He is a senior engineering consultant with Saudi Aramcos Consulting Services Department. He was a research scientist with Conoco before joining Saudi Aramco. He has published extensively in international technical societies journals. Reprinted with permission from the 1997 SPE/EPA Exploration and Production Environmental Conference, Dallas, March 35, 1997.

ABSTRACT
Pipelines must be properly laid up to prevent corrosion damage during mothballing or following a hydrostatic test prior to commissioning. Among all the lay-up procedures, wet lay-up using chemically treated water is generally considered the most cost-effective approach. This is particularly true for major sub-sea pipelines. To implement the procedure, a number of oil field chemicals, including bactericide, are added to the water. However, at the end of the lay-up period, it has become increasingly difficult to discharge bactericide-treated water because of environmental concerns.

A standard procedure for wet lay-up, which can be easily implemented in the field and is also environmentally acceptable, remains to be established. For this reason, a study was conducted to examine the efficacy and stability of different types of bactericides for wet lay-up application. Methods of removing the bactericide residuals remaining in the water at the end of lay-up were investigated using the Microtox assay system. The study was intended to demonstrate that a properly treated wet lay-up fluid could be safely discharged into the environment. This paper reviews the current practices of hydrostatic testing and lay-up for cross-country and sub-sea pipelines. The paper also presents the study results and recommendations on treatment of wet lay-up fluids.

INTRODUCTION
Among all the alternatives of laying up a pipeline for mothballing or following a hydrostatic test prior to commissioning, wet lay-up using chemically treated water is considered the most cost-effective approach. The water is usually treated with oxygen scavenger and bactericide to minimize corrosion damage. However, at the end of the lay-up period (which can be a few years), disposal of bactericide-treated water has created environmental concerns because of the potential toxic impact to the receiving environment. Procedures for disposal of such water have yet to be resolved. Bactericide used for wet lay-up application should provide adequate long-term corrosion protection and is environmentally acceptable as well. However, studies have shown that the most effective bactericides in terms of antimicrobial performance were highly toxic to marine organisms, whereas the least toxic bactericides performed poorly in microbial growth inhibition tests (Whale and Whitham 1991). These results suggest that it is unlikely to find a chemical which can meet both requirements (highly effective antimicrobially and with the lowest aquatic toxicity). A more practical approach to resolve this problem is probably to use physical or chemical methods to detoxify the bactericidetreated water, reducing the toxicity to below detectable limit prior to discharge. This approach should be more economical compared to other options, such as (1) dry lay-up; (2) reducing or eliminating bactericide treatment in the water, thereby taking the risk of corrosion damage during the lay-up period; (3) discharging bactericide-treated water into a lined evaporation pond; (4) rescheduling hydrostatic testing; or (5) using high-pH water without bactericide for wet lay-up. To render a detoxification program cost-effective in field operations, a number of criteria must be considered: 1. implementability of the procedure 2. duration of the procedure (completion should occur within a very short time period, such as minutes, not hours or days) 3. toxicity and biodegradability of the selected neutralizing agent (the neutralizing agent should be non-toxic as well as

biodegradable to minimize potential environmental impact if over-treatment takes place) 4. capability to treat a large quantity of water on site 5. cost 6. safety 7. maintenance 8. transport Many of the detoxification procedures reported in the literature (Notarfonzo and Stevens 1996; Oil & Gas Journal 1995; Beckman and Tacetta 1995) or recommended by the chemical suppliers could require weeks for significant detoxification to occur, rather than hours or minutes as desired in field operations. Others require holding tanks or additional facilities for treatment of the discharged water. This study was initiated to investigate ways for treatment of wet lay-up fluids, minimizing the environmental impact upon disposal of chemically treated water. The objectives of the study are: 1. To identify chemical treatment packages for use in wet lay-up application. 2. To examine the feasibility of removing the bactericide residuals remaining in the water following wet lay-up for safe disposal into the environment.

METHODS
Microtox assay system
The Microtox toxicity analysis system (Model 2055) utilizes a bioluminescent marine bacterium (Vibrio fischeri) as the test organism. The system is designed for quick assessment of acute toxicity of aqueous samples, or extracts of solid samples. The toxicity of a sample is assessed based on changes in the bioluminescent activity of the test bacteria following exposure to toxicants for five to 15 minutes. The reduction in light output from these organisms is directly related to the toxicity of the sample. Results are expressed as Gamma values (Light-Loss Effect); higher Gamma values represent higher toxicity. Based on Gamma values measured at various dilutions of the sample, an EC50 (Effective Concentration resulting in 50% reduction in light output, i.e., Gamma = 1.0) can be determined for a specified exposure time. Higher EC50 values represent lower toxicity. EC50 concentrations with statistical information (95% confidence range) are calculated by the Microtox data reduction software provided by the manufacturer.

Bactericide performance evaluation


To select a chemical treatment package for wet lay-up applications, a number of requirements have to be considered: (1) effectiveness of the chemical for long-term corrosion protection, (2) compatibility with oxygen scavenger, (3) chemical stability and (4) environmental acceptability. The antimicrobial performance of the selected treatment packages was assessed in a laboratory planktonic time-kill test. The test

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was conducted at ambient temperature in deoxygenated Arabian Gulf water (total dissolved solids in the range of 42,000 mg/L). Each chemical was tested at 50, 100, 250 and 500 ppm (as received) in the presence of 50 ppm oxygen scavenger. Either ammonium bisulfite scavenger or liquid carbonhydrazide was used based on recommendations from the chemical suppliers. The test inocula consist of General Aerobic Bacteria (GAB) and Sulfate-Reducing Bacteria (SRB) cultures isolated from the scraping solids in Saudi Aramcos seawater injection system. Prior to inoculation into the test water, the bacteria were sub-cultured successively at three-day intervals by transferring them into fresh growth media. One corrosion coupon (half of the regular strip type, 2 7/8 in 7/16 in 1/8 in) was added to each test bottle containing 300 mL test water. This produced a volume-to-surface area ratio of 6 in, which would simulate a 24-in-diameter pipeline. Multiple sets of test bottles were prepared for each test condition for analysis at time zero, and following three months and eight months of incubation. Controls for this test program contained oxygen scavenger only, with no bactericide added. All test bottles were kept at ambient temperature and covered with foil to prevent photodegradation. The analysis program after three months exposure included SRB and GAB populations, Microtox toxicity, bactericide residuals concentration, and corrosion coupon weight-loss measurements. After eight months, toxicity and bactericide residuals for selected chemicals were determined to study bactericide stability. SRB and GAB populations were determined by the triplicate decimal serial dilution method using growth media prepared in Arabian Gulf water. Results are expressed as Most Probable Number (MPN) SRB or GAB per mL. The toxicity of test water was assessed by the Microtox assay at 20C using Arabian Gulf water as the receiving water. Results are expressed as EC50-5 minute concentrations or Gamma-5 minute values. The residual concentration of quaternary phosphonium-based bactericide was analyzed by titration. Biguanide concentration was determined using a colorimetric method. The corrosion rate was determined based on corrosion coupon weight-loss measurements.

Each method was tested with a 10 mL aliquot from bottles showing effective microbial control. The overall toxicity remaining in the aliquot following the detoxification treatment was determined by the Microtox assay. Each sample was analyzed immediately following the treatment. The results are expressed as 5-minute Gamma values (light-loss effect). Data are compared with controls which received no neutralization treatment, i.e., direct discharge. The impact of each treatment and the toxicity of the neutralizing agent (chlorine) in Arabian Gulf water were also assessed. For sand and activated carbon treatments, the time allowed for each reaction was kept to a minimum (minutes). Each 10 mL aliquot was treated with 1 g sandy soil collected from a nearby land farm site. For carbon adsorption, 0.01 g activated carbon was used for each treatment. Because of the color, turbidity and particulates present in the treated sample (which would interfere with Microtox bacteria bioluminescence measurements), the aliquot was filtered through a glass-fiber filter prior to toxicity determination. The effect of filtration alone on the overall toxicity of the test water was also examined. Neutralization of bactericide residuals by chlorine was evaluated at chlorine concentrations ranging from 0.5 ppm to 20 ppm. The contact time for each treatment was kept to a minimum (minutes). Chlorine concentration was determined by Hach DREL/2000 spectrophotometer. In addition to toxicity measurement, the effectiveness of chlorine neutralization of biguanide and quaternary phosphonium residuals was also monitored by chemical analysis as described previously.

RESULTS
Selection of bactericide
1. Identification of current technology for wet lay-up To identify current treatment technology, nine chemical and oil companies were contacted worldwide. Based on their recommendations, six bactericide/oxygen scavenger packages were selected for evaluation. The active ingredient of these products and the recommended detoxification procedures are summarized in table 1. The performance of these treatment packages is compared with polymeric biguanide hydrochloride, a bactericide which has previously been used in Saudi Aramcos mothballing operations. 2. Bactericide ecotoxicity The acute toxicity data of the bactericides included in the test program are summarized in table 2. The data were generated by the manufacturers or independent laboratories using a wide range of marine and freshwater organisms (i.e., fish, shrimp, crustaceans, mussels, etc.) as the test species. Toxicity of these products assessed based on responses from the Microtox bacteria are presented in table 3. All bactericides are ranked from the least toxic (1) to the most toxic (6) based on their LC50-96 hours or EC50-5 minute values; higher LC50 or EC50 values

Detoxification
Detoxification of the bactericide-treated water after three months exposure was evaluated using the following methods: dilution with seawater (1:2, 1:10, 1:50, 1:250) aeration for one hour at ambient temperature exposure to sunlight for one hour raising water pH to 9 and 10 filtration with glass-fiber filter adsorption by activated carbon followed by filtration with glass-fiber filter adsorption by sand followed by filtration with glass-fiber filter use of oxidizing agent (chlorine)

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TABLE 1. BACTERICIDES INCLUDED IN THE TEST PROGRAM Active Ingredient Glyoxal Quaternary Phosphonium Salt Combination Package Dialdehyde THPS Biguanide /oxy.scavenger /corr.inhibitor PHMB DBNPA Detoxification Procedures Recommended No treatment Hydrolysis, oxidation, UV sunlight, dilution Dilution, adsorption, co-precipitation Adsorption, co-precipitation, oxidizing agent Raising pH, hydrolysis, photodegradation, chemical reactions, soil Raising pH

Polymeric Biguanide Organobromide

Thiocyanate

MBT

THPS, tetrakishydroxymethyl phosphonium sulfate PHMB, polyhexamethylene biguanide hydrochloride DBNPA, dibromonitrilopropionamide MBT, methylene bisthiocyanate

represent lower toxicity. Data show that despite the wide range of species tested and the test protocols used in these bioassays, the Microtox toxicity results correlate reasonably well with fish/shrimp bioassay results. 3. Bactericide antimicrobial performance and toxic impact The results of the planktonic time-kill test following three months exposure are presented in fig. 1. Two bactericides (quaternary phosphonium salt and polymeric biguanide) provided complete kill of General Aerobic Bacteria (GAB) and SulfateReducing Bacteria (SRB) at the lowest concentration tested (50 ppm as received). Two other chemicals (organobromide and thiocyanate) also showed complete kill, but only at much higher concentrations (500 and 250 ppm, respectively). The other two chemicals either resulted in no kill at the highest concentration tested or were effective against SRB but not GAB. The minimum effective concentration for each chemical producing a complete kill is summarized in table 4. The toxicity, bactericide residuals, and corrosion-rate data determined after three months are shown in table 5. The results show that biguanide-treated waters were the most toxic of all the waters tested, as indicated by the lowest EC50 values (EC50-5 minute concentrations ranging from 12.2 to 1.5%). The glyoxal-, combination-package- and organobromide-treated waters were relatively nontoxic (EC50-5 minute concentrations approaching or greater than 50%). The corrosion rates observed after the three-month incubation period were all within acceptable limits (<1 mpy). In general, the toxicity levels of the test waters correlated with the antimicrobial performance of the chemicals. The most effective chemical in terms of antimicrobial performance was highly toxic to the Microtox bacteria; the chemicals with the lowest toxicity were ineffective for controlling bacteria growth. The antimicrobial performance of the bactericides, however, did not necessarily correlate with the acute toxicity of the neat chemicals determined initially. For example, organobromideand thiocyanate-based bactericides were the two most toxic
TABLE 4. BACTERICIDE PERFORMANCE EVALUATION RESULTS: MINIMUM EFFECTIVE CONCENTRATION AGAINST BACTERIA Effective Concentration, ppm1 GAB SRB <50 <50 >500 <50 <50 50

TABLE 2. BACTERICIDE ECOTOXICITY DATA SUPPLIED BY CHEMICAL COMPANIES Fish/Shrimp LC50-96 hrs ppm Glyoxal Quaternary Phosphonium Salt Combination Package Polymeric Biguanide Organobromide Thiocyanate
1

Rank1 1 2 2 4 5 6

760 3 340 23 110 1 100 49 0.6 2.2

from least toxic (1) to most toxic (6)

TABLE 3. BACTERICIDE TOXICITY AS DETERMINED BY THE MICROTOX ASSAY SYSTEM (20C) EC50-5 min. ppm Glyoxal Quaternary Phosphonium Salt Combination Package Polymeric Biguanide Organobromide Thiocyanate 1610 (1566 1655)1 87.5 (81.7 93.7) 50.5 (46.2 55.3) 11.0 (10.9 11.2) 2.2 (2.1 2.3) 0.5 (0.3 0.8) EC50-15 min. ppm 771 (760 781)1 44.8 (42.7 46.9) 38.8 (38.2 39.3) 5.6 (5.0 6.3) 2.1 (1.8 2.5) 0.2 (0.1 0.3) Rank2 1 2 3 4 5

Glyoxal Quaternary Phosphonium Salt Combination Package Polymeric Biguanide

>500 50 >500 <50 250 500 100 250

Organobromide Thiocyanate

1 2

95% confidence range in parenthesis from least toxic (1) to most toxic (6)

Bactericide concentrations (as received)

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chemicals of all products tested, according to the ecotoxicity data (tables 2 and 3). But these two bactericides were not the most effective chemicals against bacteria at the end of the three-month exposure period. The toxicity rank of all bactericidetreated waters after three months was different compared to the ecotoxicity rank of the neat chemicals. The changes of toxicity in the waters during the three-month incubation based on Microtox assessment and chemical analysis are discussed in Section 5, Bactericide Stability. Based on the bactericidal effectiveness test results, four chemicals (quaternary phosphonium, biguanide, organobromide

and thiocyanate) were selected for further evaluations of their compatibility with oxygen scavenger, chemical stability and bactericide neutralization. 4. Compatibility with oxygen scavenger The toxicity of quaternary phosphonium-, biguanide-, organobromide- and thiocyanate-based bactericides tested as bactericide alone, and also in the presence of oxygen scavenger, by the Microtox assay is shown in table 6. Data show that the presence of the oxygen scavenger could affect the toxicity of the bactericides. For quaternary phosphonium-, biguanide- and thiocyanate-based products, the presence of oxygen scavenger

GAB 8 7 GAB (Log MPN/mL) 6 5 4 3 2 1 0 -1 Glyoxal Q. Phosphonium Combination Control (0 ppm) Glyoxal Q. Phosphonium Combination Biguanide Organobromide Thiocyanate 3.36 3.97 4.23 3.97 5.36 5.36 Biguanide Organobromide Thiocyanate Control (0 ppm) 50 ppm 100 ppm 250 ppm 500 ppm

50 ppm 5.36 -0.4 4.97 -0.4 4.18 4.63

100 ppm 5.88 -0.4 2.63 -0.4 3.63 1.63

250 ppm 3.97 0.36 3.97 -0.4 3.97 -0.4

500 ppm 2.88 0.36 4.36 -0.4 -0.4 -0.4

SRB 8 7 SRB (Log MPN/mL) 6 5 4 3 2 1 0 -1 Glyoxal Q. Phosphonium Combination Control (0 ppm) Glyoxal Q. Phosphonium Combination Biguanide Organobromide Thiocyanate 5.36 3.63 4.32 3.63 3.97 3.97 Biguanide Organobromide Thiocyanate Control (0 ppm) 50 ppm 100 ppm 250 ppm 500 ppm

50 ppm -0.4 -0.4 4.63 -0.4 -0.4 -0.4

100 ppm -0.4 -0.4 4.36 -0.4 -0.4 -0.05

250 ppm -0.4 -0.4 5.18 -0.4 -0.4 -0.4

500 ppm -0.4 -0.4 3.97 -0.4 -0.4 -0.4

Fig. 1. Bactericide performance evaluation results after 3 months exposure

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TABLE 5. BACTERICIDE PERFORMANCE EVALUATION RESULTS AFTER THREE MONTHS EXPOSURE-TOXICITY, CHEMICAL RESIDUALS, CORROSION RATES TIME 0 EC50-5 min. (%) Control 11 2 3 Glyoxal 50 ppm2 100 ppm 250 ppm 500 ppm Quaternary Phosphonium 50 ppm 100 ppm 250 ppm 500 ppm Combination Package 50 ppm 100 ppm 250 ppm 500 ppm Polymeric Biguanide 50 ppm 100 ppm 250 ppm 500 ppm Organobromide 50 ppm 100 ppm 250 ppm 500 ppm Thiocyanate 50 ppm 100 ppm 250 ppm 500 ppm 16.2 6.1 11.4 3.2 8.8 3.6 6.4 1.9 35.9 25.5 42.6 18.9 23.1 17.7 30.9 16.6 0.20 0.14 0.15 0.30 >50 >50 2.1 1.1 >50 >50 1.5 0.7 >50 55.0 48.7 55.1 >50 37.2 38.6 39.8 0.45 0.49 0.45 0.76 7.7 5.4 2.6 1.5 4.6 3.5 1.5 1.0 12.2 5.3 2.5 1.5 6.7 3.0 1.8 1.0 46 0.56 0.51 0.46 0.35 >50 43.1 13.1 7.8 >50 30.6 9.6 5.9 >50 42.9 28.6 >50 >50 32.9 18.7 >50 0.56 0.50 0.47 0.64 35.9 34.2 27.5 13.8 12.8 22.0 14.6 9.8 39.1 47.0 21.0 21.6 28.0 41.3 11.8 9.3 15 60 0.67 0.88 0.72 0.74 >50 >50 >50 >50 >50 >50 >50 >50 36.2 49.0 >50 >50 22.8 26.3 >50 19.9 0.42 0.74 0.40 0.50 >50 >50 >50 TIME 0 EC50-15 min. (%) >50 >50 >50 3 MONTHS EC50-5 min. (%) 33.6 >50 48.5 3 MONTHS EC50-15 min. (%) 24.3 >50 35.6 3 MONTHS Res. Rem. (ppm) 3 MONTHS Corr. Rate (mpy) 0.50 0.53 0.42

1 2

Controls 1, 2, 3 contain oxygen scavenger only (no bactericide). All oxygen scavengers are tested at 50 ppm. Bactericide concentrations (as received).

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enhanced the acute toxicity of the chemicals, as indicated by higher Gamma values. For organobromide-based bactericide, the toxicity was significantly reduced when oxygen scavenger (carbonhydrazide) was mixed with the bactericide. Similar observations have been reported by other investigators when organobromide biocide was mixed with ammonium bisulfite oxygen scavenger (Whale and Whitman 1991). It is also indicated in the literature that DBNPA (dibromonitrilopropionamide, the active ingredient of the organobromide biocide tested) was degraded by a number of sulfur-containing species such as sulfite, bisulfite, thiosulfate and sulfide (Exner, Burk and Kyriacou 1973). These compounds debrominated DBNPA instantaneously to form cyanoacetamide. Because of the incompatibility with oxygen scavengers, organobromide-based bactericide at present is not recommended for wet lay-up applications.

TABLE 6. COMPARISON OF BACTERICIDE TOXICITY WITH AND WITHOUT OXYGEN SCAVENGER1 Bactericide + Bactericide Bisulfite Oxygen Bactericide + Alone Scavenger2 Carbonhydrazide2 Seawater Quaternary Phosphonium (50 ppm) Polymeric Biguanide (10 ppm) Organobromide (2.5 ppm) Thiocyanate (1.0 ppm)
1

0.38 8.01 5.54 1.41

2.30 1.54 95

0.10 0.58 1.83

All results presented as Gamma-5 min. values (light-loss effect); higher values represent higher toxicity. Oxygen scavengers are tested at 50 ppm.

TABLE 7. BACTERICIDE STABILITY DURING EIGHT MONTHS EXPOSURE RESIDUAL REMAINING2 3 Months RESIDUAL REMAINING2 8 Months

TOXICITY1 Time 0 Control 1 2 3 Quaternary Phosphonium 50 ppm 100 ppm 250 ppm 500 ppm Polymeric Biguanide 50 ppm 100 ppm 250 ppm 500 ppm Organobromide 50 ppm 100 ppm 250 ppm 500 ppm Thiocyanate 50 ppm 100 ppm 250 ppm 500 ppm
1

TOXICITY1 3 Months 33.6 >50 48.5

TOXICITY1 8 Months 23.8 33.8 43.5

>50 >50 >50

35.9 34.2 27.5 13.8

39.1 47.0 21.0 21.6

31.2 24.1 >50 20.6

15 ppm (30%) 60 ppm (12%)

8 ppm (16%) 9 ppm (9%) 17 ppm (7%) 24 ppm (5%)

7.7 5.4 2.6 1.5

12.2 5.3 2.5 1.5

6.4 5.4 2.1 1.2

46 ppm (92%)

44 ppm (88%) 67 ppm (67%) 155 ppm (62%) 270 ppm (54%)

>50 >50 2.1 1.1

>50 55.0 48.7 55.1

>50 36.4 47.0 46.7

16.2 6.1 11.4 3.2


2

35.9 25.5 42.6 18.9

>50 >50 >50 >50

All toxicity results presented as EC50-5 min. (%).

Quaternary phosphonium determined by titration; biguanide determined colorimetrically.

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5. Bactericide stability Comparing the three-month and eight-month EC50 data with the initial toxicity determined at time zero, no significant changes have been observed in the biguanide- and quaternary phosphonium-treated waters during the eight-month incubation period (table 7). Further analyses of the active ingredients of the bactericides using chemical methods show that significant amounts of PHMB (polyhexamethylene biguanide) remained after three months and eight months, which support the Microtox toxicity results. In quaternary phosphonium-treated waters, however, only a small amount of THPS (tetrakishydroxymethyl phosphonium sulfate) could be detected analytically, but the overall toxicity of the water remains relatively unchanged. These results suggest that the active ingredient THPS has converted or degraded to some intermediate products which are no longer measurable by chemical method, but remain toxic. For organobromide- and thiocyanate-treated waters, the overall toxicity has been reduced significantly, with EC50 values increasing over the eight-month incubation period (see table 7). According to the literature, organobromide is a fast-acting chemical designed to provide a rapid kill of a wide variety of microorganisms (Exner, Burk and Kyriacou 1973). It is generally used in industrial recirculating and once-through cooling water systems, paper mills, metalworking fluids, and air washer systems. It decomposes relatively fast by a number of chemical and biological mechanisms, such as hydrolysis, photodegradation and reaction with sulfur-containing compounds.

Detoxification of bactericide-treated water


Results of detoxification of quaternary phosphonium, biguanide, organobromide and thiocyanate residuals remaining in the water following the three-month incubation period are summarized in table 8. The effect of the detoxification treatments on seawater itself is also shown in table 8. For direct discharge with no further detoxification treatment, the four waters showed various degrees of toxic impact on the Microtox bacteria, with Gamma-5 minute values ranging from 0.68 to 9.76. The toxicity levels were reduced to below the detection limit (Gamma-5 minutes 0.05 or EC5, the concentration giving a 5% reduction in light output) when the waters were diluted by approximately a factor of 50. Data in table 8 also show that although biguanide-treated water is highly toxic to the Microtox bacteria, biguanide residuals appear to be the most adsorbable of the four chemicals evaluated. Compared to the untreated control, treatment with glass-fiber filter significantly reduced the toxicity of the residual. Further treatment with sand or activated carbon resulted in additional reduction of the toxicity in the water. Aeration/oxidation or exposure to sunlight had only a slight effect on detoxification of the water. It appears that in addition to dilution, biguanide residual can be effectively removed by precipitation and/or adsorption onto carbon, sand/clay particles or other inert materials, presumably due to its cationic nature. For quaternary phosphonium, organobromide and thiocyanate residuals, the only treatment that effectively eliminated the toxicity in the water was carbon adsorption (Gamma-5 minute values reduced to <0.05). All other detoxification treatments appeared to

TABLE 8. DETOXIFICATION OF BACTERICIDE RESIDUALS FOLLOWING THREE MONTHS EXPOSURE (MICROTOX TOXICITY ANALYSIS RESULTS1) SEAWATER No Treatment Dilution3 Aeration Sunlight Raising pH to 9 Raising pH to 10 Filtration Carbon/Filtration Sand/Filtration Chlorine 0.5 ppm 1.0 ppm 2.0 ppm 5.0 ppm
1 2 3

Q. PHOSPHONIUM2 0.68 50X 0.70 0.70 1.06 0.71 0.05 0.72

BIGUANIDE2 9.76 50X 7.03 4.70 >100 1.54 0.13 0.94

ORGANOBROMIDE2 1.22 50X 0.94 1.10 1.40 3.69 1.35 0.06 1.41

THIOCYANATE2 1.09 50X 0.95 0.96 1.03 10.7 1.12 0.04 0.96

0.55 2.88 <0.05 <0.05 0.07

1.04 44.0 94.0 >100

0.72 0.77 0.88 >100

17.8 22.8 46.5 >100

1.47 1.69 2.71 9.94

14.0 41.5 94.2 100

All results (except dilution factors) presented in Gamma-5 min. values (light-loss effect); higher values represent higher toxicity. Each bottle tested at 50% dilution. Initial treatment concentrations at time zero: Q. phosphonium, 50 ppm; biguanide, 50 ppm; organobromide, 500 ppm; thiocyanate, 250 ppm. Gamma-5 min. values reduced to <0.05.

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have very little effect compared to the untreated controls, suggesting that these procedures can not be completed within minutes or seconds as desired by field operations. Use of an oxidizing agent such as chlorine has been proposed as a potential method for removal of bactericide residuals. Results in table 9 show that the addition of chlorine was able to neutralize quaternary phosphonium and biguanide residuals based on chemical analysis of the active ingredient of freshly prepared bactericide solutions. However, the water remained toxic following chlorine treatment (table 8). The toxicity could be a result of the toxic effect of the neutralizing agent itself, as shown in table 8 (tested with seawater alone). The toxicity could also suggest that the by-products formed from the oxidation reactions are toxic.

TABLE 9. NEUTRALIZATION OF BACTERICIDE RESIDUALS BY CHLORINE (CHEMICAL ANALYSIS RESULTS1) Q. Phosphonium (ppm) No Treatment2 Chlorine 0.5 ppm 1 ppm 2 ppm 5 ppm 10 ppm 20 ppm
1

Biguanide (ppm) 41 39 36 25 <5

48 48 50 50 50 8 <5

DISCUSSIONS
Treatment of wet lay-up fluid
Selection of bactericide for use in the treatment of wet lay-up fluid should be based on the following criteria: (1) effectiveness of the chemical for providing long-term microbial control, (2) compatibility with all chemicals used, (3) chemical stability and (4) environmental acceptability. In this study, environmental acceptability was evaluated based on Microtox acute toxicity assessment of the neat chemicals and the chemical residuals remaining after three months and eight months exposure. It is recognized that toxicity of a chemical is only one aspect of environmental acceptability; other factors (biodegradability, bioaccumulation potential) also play a role in the overall assessment of environmental impact. However, the most common acute impact is toxicity. Toxicity is widely used in the industry as a standard parameter for chemical characterization. It is one of the prime requirements of many regulatory schemes (Whale and Whitman). Results of this study show that the long-term performance of the bactericides against oil field bacteria generally correlates with the toxicity assessment of the chemicals based on short-term responses from the Microtox bacteria, except in chemicals with low stability. The most effective chemicals with the best bactericidal efficacy and chemical stability are toxic to the Microtox bacteria; the chemicals with the lowest toxicity are ineffective in terms of bacteria control. It appears that bactericide detoxification (chemically and physically) would have to be included as part of the wet lay-up chemical treatment package, if all four chemical selection criteria are to be met. The final procedure selected to treat wet lay-up fluid should be a balance based on both cost and environmental considerations.

Q. phosphonium determined by titration; biguanide determined colorimetrically. Bactericide solutions freshly prepared in Arabian Gulf water (TDS 42,000 mg/L) at a concentration of 50 ppm.

Detoxification of bactericide-treated water


A number of procedures have been recommended in the literature and by chemical suppliers for detoxification of the bactericides tested in this program. These include raising pH, oxidation/ aeration, exposure to sunlight, hydrolysis and degradation to

transform the active ingredients to less toxic components. Results of this study suggest that these methods would require days and weeks of time for significant detoxification to occur, rather than minutes or seconds as desired by field operations. Additional facilities such as holding tanks are also required for aeration, oxidation or photodegradation reactions. Furthermore, the potential environmental impact of the final degradation products, including algal bloom, eutrophication, etc., is largely unknown. These factors should be considered in the selection of a treatment package and its detoxification procedure for wet lay-up. Based on responses from the Microtox bacteria, carbon adsorption appears to be the most promising of all the detoxification methods evaluated. This method effectively removed the residual toxicity of all four bactericide-containing waters tested within a short period of time (minutes). Liquid-phase purification with carbon adsorption has long been cost-effectively applied to process streams, drinking water, groundwater and municipal and industrial wastewater (Beckman and Tacetta). Activated carbon adsorption systems have also been used to treat pipeline hydrotest water containing BTEX (benzene, toluene, ethylbenzene and xylene) on site for surface discharge (Oil and Gas Journal). This technology reportedly has a number of advantages: effective, relatively low cost, safe, portable, durable, simple to operate and easy to maintain. However, because of the large quantity of water to be treated in most of Saudi Aramcos operations and the types of organic molecules to be removed, the feasibility of implementing such system on site, and the cost required, should be further investigated. Use of an oxidizing agent such as chlorine for detoxification does not appear to be a viable option, since chlorine is highly toxic to the Microtox organisms, and the reaction products may also be toxic. In evaluating chemical neutralization procedures, it is important that the selected neutralizing chemicals are relatively nontoxic and biodegradable. Otherwise, overtreatment would

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create a new problem. Based on these considerations, it appears that bactericide detoxification by chlorination is unlikely to be easily implemented in the field.

Application of the Microtox assay system


The Microtox assay is designed for quick assessment of acute toxicity (typically for an exposure time of five to 15 minutes) based on changes in luminescence activities from a marine bacterium. The one problem often faced in interpreting Microtox data is the correlation of toxic responses between bacteria and other biological species indigenous to the local environment. As indicated in the literature (Bulich, Greene and Isenberg 1981; and Indorato, Snyder and Usionowicz 1984), the Microtox results are generally considered comparable to standard fish/shrimp kill test results. In this study the acute toxicity of the test bactericides determined by the Microtox system and those reported by the chemical suppliers based on a wide range of marine and freshwater species correlate reasonably well. The Microtox assay results also correlate with the antimicrobial performance of the bactericides observed in the planktonic time-kill test. As mentioned previously, the Microtox assay measures the overall/ combined toxicity of a water sample, including the bactericide residual and any degradation by-products formed during the lay-up period. Compared to chemical analysis of bactericide residuals, this provides a more accurate assessment of the potential environmental impact. The Microtox analysis system is especially suitable for measuring the relative changes in aquatic toxicity of an environment because it is quick and simple to use. The results of this study have demonstrated that the Microtox assay system is an invaluable tool in assessing the toxicity of bactericide-treated waters, the effectiveness of chemical treatment in lay-up operations, and in developing toxicity-reduction strategies.

In addition to carbon adsorption, the toxicity of biguanide residuals can also be reduced by sand or glass-fiber filter treatments. While biguanide-treated water is the most toxic of all bactericides tested, the residuals appear to have the highest adsorption capacity. To remove the toxicity by dilution, a factor of approximately 1:50 is required for safe discharge of bactericide-treated water following lay-up. Bactericide detoxification by hydrolysis, oxidation, pH adjustment and/or photodegradation cannot be accomplished within minutes or seconds as desired by field operations. Bactericide detoxification by chlorine does not appear to be a viable option for field application because of the toxic nature of chlorine and/or its oxidation products. The Microtox assay system is an invaluable tool in assessing the overall environmental impact of bactericide-treated waters and developing toxicity reduction strategies.

ACKNOWLEDGMENTS
The authors would like to thank Mahfoud A. Al-Ghamdi of Saudi Aramco Lab R&D Center for his significant contributions to this study.

REFERENCES
Beckman, W.K. and J.J. Tacetta. 1995. Pretreatment Is a Crucial First Step: An introduction to physical and chemical treatment processes. International Ground Water Technology (December). Bulich, A.A.; M.W. Greene; and D.L. Isenberg. 1981. Reliability of the bacterial luminescence assay for determination of the toxicity of pure compounds and complex effluents. Aquatic Toxicity and Hazard Assessment: Fourth Conference, ASTM STP 737. D.R. Branson and K.L. Dickson, eds., American Society for Testing and Materials, p338. Exner, J.H.; G.A. Burk; and D. Kyriacou. 1973. Rates and products of decomposition of 2,2-dibromo-3-ditrilopropionamide. J. Agr. Food Chem. v.21, p838. Indorato, A.M.; K.B. Snyder; and P.J. Usionowicz. 1984. Toxicity screening using Microtox analyzer. Toxicity Screening Procedures Using Bacterial Systems, D. Liu and B.J. Dutka, eds., New York:Marcel Dekker Inc. p37. Notarfonzo, R. and R.D.S. Stevens. 1996. UV/oxidation is a quiet, clean destroyer: Contaminated water is detoxified with no need for secondary disposal. International Ground Water Technology. April. Oil & Gas Journal. 1995. Pipeline treats hydrotest water on site with carbon adsorption, January. p92. Whale, G.F. and T.S. Whitham. 1991. Methods for assessing pipeline corrosion prevention chemicals on the basis of antimicrobial performance and acute toxicity to marine organisms. Paper presented at the First International Conference on Health, Safety and Environment, The Netherlands, Nov. 10-14.

CONCLUSION
Laboratory evaluation of wet lay-up treatment packages indicates that the most effective chemicals in terms of bactericidal effectiveness and chemical stability are most toxic based on Microtox assay results. An effective bactericide detoxification procedure is required as part of the wet lay-up chemical treatment package. The final treatment procedure should be based on both cost and environmental considerations. On an equal concentration basis, biguanide- and quaternary phosphonium-based bactericides are the most effective of all chemicals tested. Biguanide is also found to be most stable during the eight-month study. Carbon adsorption is an effective way to rapidly remove the toxicity of bactericide residuals. Of all methods evaluated, this is the only technology which effectively detoxified all four chemically treated waters.

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