DC
                    FIELD  TEST KIT  FOR  OIL-BRINE EFFLUENTS
                      FROM OFFSHORE DRILLING PLATFORMS
                                     by
                     R.  T.  Rewick, J. Gates, K. A,  Saho
                         T. W.  Chou, and J, H. Smith
                              SRI International
                        Menlo  Park, California  94025
                          EPA  Grant No. R8Q6091010
                               Project  Officer

                            Leo T, McCarthy, Jr.
                  Oil  and  Hazardous Materials Spills Branch
                 Municipal Environmental Research Laboratory
                          Edison, New Jersey  08817
               MUNICIPAL  ENVIRONMENTAL RESEARCH LABORATORY
                     OFFICE  OF RESEARCH AND DEVELOPMENT
                    U.S. ENVIRONMENTAL PROTECTION AGENCY
                          CINCINNATI, OHIO  45268

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                                 DISCLAIMER
     This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, Edison, New Jersey, and
approved for publication.  Approval does not signify that the contents neces-
sarily reflect the views and policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
                                     ii

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                                  FOREWORD
     The U.S. Environmental Protection Agency was created because of increas-
ing public and government concern about the dangers of pollution to the health
and welfare of the American people.  Noxious air, foul water, and spoiled land
are tragic testimonies to the deterioration of our natural environment.  The
complexity of that environment and the interplay of its components require a
concentrated and integrated attack on the problem.

     Research and development is that necessary first step in problem solution;
it involves defining the problem, measuring its impact, and searching for
solutions.  The Municipal Environmental Research Laboratory develops new and
improved technology and systems to prevent, treat, and manage wastewater and
solid and hazardous waste pollutant discharges from municipal and community
sources, to preserve and treat public drinking water supplies, and to minimize
the adverse economic, social, health, and aesthetic effects of pollution.
This publication is one of the products of that research and provides a most
vital communications link between the researcher and the user community.

     The objectives of the present research program were (1)_ to develop and
evaluate a field test kit for characterizing oil-brine effluents from offshore
drilling platforms and (2) to deliver to EPA the completely assembled kit with
detailed operating instructions for conducting each test method.
                                     iii

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                                  ABSTRACT
     This research program was initiated to evaluate test methods for charac-
terizing oil-brine effluents from offshore oil production platforms and to
package and deliver a field test kit for on-site oil-brine analyses.  After
an initial laboratory evaluation and selection of test methods and equipment,
two on-site oil-brine analyses of production water were conducted in Kenai,
Alaska—one at the AMACO Dillon Offshore Production Platform, and the other
at the Shell MGS Joint Onshore Facility.  This report describes the methods
developed for the field test site, including detailed procedures for conduct-
ing each test method, and the results from the two on-site analyses.

     This report was submitted in fulfillment of Grant No. R806091010 by SRI
International under the sponsorship of the U.S. Environmental Protection
Agency.  This report covers the period October 9, 1978 to April 8, 1981, and
work was completed as of April 8, 1981.
                                     IV

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                                  CONTENTS
Foreward	iii
Abstract	iv
Figures	vi
Tables	vi
Acknowledgments	vii

     1.    Introduction	1
     2.    Conclusions 	  3
               Methods Review and Development 	  3
               Recommended Tests for Field Test Kit 	  3
               Field Results	5
     3.    Recommendations 	  6
     4.    Experimental Results	7
               Methods Review and Development 	  7
                    Total Oil Content	7
                         Infrared Method	7
                         Gravimetric Method 	  7
                    Solvent Extraction Efficiency 	 11
                    Soluble Oil	11
                    Particle Size	11
               Field Results	12
                    Oil-in-Water Results.  ....".	 12
                    Soluble Materials 	 12
                    Suspended Solids	12
                    Physical Properties of Oil and Water	15
                    Bacterial Culture 	 20
References	,,....., 22
Appendices
     A.    Instrumentation and Materials Provided in the Field Test Kit.  . 23
     B.    Laboratory and Field Procedures 	 25

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                                   FIGURES







Number                                                                   Page




  1  Assembled Field Test Kit—Suitcase No.  1	13




  2  Assembled Field Test Kit—Suitcase No.  2	14
                                   TABLES
Number                                                                   Page




   1  Summary of OOC Test Methods	    2




   2  Recommended and Modified Procedures for the Field Test Kit ....    4




   3  Comparison of Three Oil-In-Water Analyzers 	    8




   4  Comparison of the Infrared and Gravimetric Methods 	    9




   5  Solvent Extraction Efficiency For No.  6 Oil	   10




   6  Field Test Kit Dimensions and Weight	15




   7  Physical Properties of Oil and Water 	 ,.,.,.   15




   8  Oil-In-Water Results 	  ,,,,,,.,«   16




   9  Extraction Efficiency of Freon 113 for Dillon and Shell Oils ...   17




  10  Soluble Materials Results	...,,...   18




  11  Suspended Solids CSS) Results	,.,,....,,,   19




  12  Bacterial Culture Results  	 ....   21
                                     vi

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                               ACKNOWLEGMENTS
     The assistance and counsel of the U.S. Environmental Protection Agency
Project Officer, Mr. L. T. McCarthy, Jr., of the Municipal Environmental
Research Laboratory, Edison, New Jersey, have been invaluable in this work.
The assistance of Mr. Bill H. Lamoreaux, Environmental Engineer, U.S. Environ-
mental Protection Agency, Anchorage, Alaska, in arranging the test kit evalua-
tion sites is also gratefully acknowledged.  Helpful discussions with
Dr. Michael J. Wade of Texas Instruments Ecological Services, Dallas, Texas
are appreciated.
                                    VII

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                                  SECTION 1

                                INTRODUCTION
     Offshore drilling facilities are becoming increasingly numerous as new
oil reserves are needed to replace depleted land-based sources. As a result,
the possibilities of drilling and production accidents, such as the Santa
Barbara Channel disaster, are also expected to increase.  Another pollution
concern is the presence of brine in the crude oil obtained from deep-well
drilling sites.  On offshore platforms, the crude is routinely pass through
an oil/water/gas separator, and the brine is then discharged into the ocean.
After varying degrees of additional treatment this brine contains a fine sus-
pension of oil droplets that is not removed in the separator.  Inefficient
brine treatment could results in a serious contamination source.

     As one phase of a U.S. Environmental Protection Agency (EPA), contract
with Exxon Research and Engineering, a study was made of pollution control
technology for offshore drilling and production platforms and test methods
were recommended for evaluating the efficiency of the oil-brine separation
process.  The Offshore Operators' Committee (OOC) reviewed the Exxon procedures
and recommended several modifications.   Additional changes have been proposed
and verified by field evaluation by Texas Instruments Incorporated.

     A summary of the OOC test methods is given in Table 1.  Specifically,
the work at SRI has consisted of the following tasks:

     1.   Evaluate the OOC-modified test methods (Table 1, Status 11 for
          characterizing oil-brine effluents from offshore oil production
          facilities.

     2.   Recommend and package into a field test kit suitable equipment
          and instrumentation for conducting the oil-brine characterizations.

     3.   Evaluate the field test kit at a suitable onshore or offshore oil
          production facilitiy.

     4.   Deliver the field test kit to EPA with detailed instructions for
          performing the tests.

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TABLE 1.  SUMMARY OF OOC TEST METHODS
Test
No.
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
;14.
i
i
i
Test
Oil-in-water
Suspended solids
Particle size
Surface tension
Viscosity
Specific gravity
Salinity
PH
Temperature
Brine composition
Bacterial culture
Oil separation
Soluble materials
Flow rate

*
Status 1: OOC modified
Status 2: OOC modified
Status 3: OOC approved
Method /Apparatus
Gravimetric; infrared
Filtration
Microscopy
Method^
Status
1
3
Type of Test
Field !
Lab
1 Field
Tensiometer 3 Field
Ostwald; Brookfield 3 ; Field
Centrifuge; hydrometer I 2 Field ;
Centrifuge; titration 3 Field
pH meter 3 ; Field
Thermometer 3 Field
Atomic absorption 2 Lab
API RP-38 2 Lab :
API 734-53 2 ? ;
Column and Si02 adsorption;
spectrophotometry
Shell PSM

1
2

Field
Field |
I
i
- evaluate at SRI.
- standard procedures.
- standard procedures.

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                                 SECTION  2

                                CONCLUSIONS
METHODS REVIEW AND DEVELOPMENT

     The OOC-recommended test procedures, a brief description  of  the  test  as
suggested by the Texas Instruments report  , and our recommendations and  mo-
difications to these tests are summarized in Table 2.
RECOMMENDED TESTS FOR FIELD TEST KITS

     The following tests  (Table 2) are included  in  the  field  test  kit:

     (1)  Oil in water  (IR and gravimetric)

     (2)  Soluble materials (.equilibration and filtration)

     (3)  Specific gravity

     C4)  PH

     (5)  Temperature

     (6)  Suspended solids

     (.7)  Bacterial culture (includes laboratory evaluation of  samples
          collected in  the field)

     The following tests are recommended to be performed onshore or  in  the
laboratory because vibration on the platform interferes severely with the
method.
     (.1)  Surface tension

     (2)  Viscosity

Containers for collecting the required samples are  included in  the test kit.

    The following OOC test procedures were not included in the  SRI test kit;

    (1).  IR oil-in-water, using the Horiba and Turner spectrophotometers.

    (2)  Gravimetric oil-in-water, using balance at test site.

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     (31  Particle size

     (41  Brine, composition

     (5)  Flow rate:  site specific equipment for each, platform  should be
          used for these measurements.

     (6)  Water cut

     (7)  Boiling range
FIELD RESULTS

     The test kit evaluated and assembled at SRI performed satisfactorily  at
the two test sites.  Only minor modifications to the test procedures, as out-
lined in Section 4, were required.  Approximately 8 labor-hours are required
to conduct one on-site oil-brine characterization.

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                                  SECTION 3

                              RECOMMENDATIONS
     During this study, it became apparent that the complete field test kit
is rather bulky (J.32.3 Ib) for one person to transport easily.  Therefore, we
recommend that the kit be simplified to focus only on the oil-in-water ana-
lysis.  A field test kit for measuring the oil content of the platform efflu-
ent by the infrared method would probably consist of one suitcase  (28 Ib),
the Miran spectrometer (21 Ib), and the Freon solvent bottles (40 Ib).  The
on-site analysis time required to conduct the single measurements would also
be shortened from about 8 labor-hours  (_to conduct all the tests) to about
2 labor-hours.

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                                   SECTION  4

                             EXPERIMENTAL RESULTS
METHODS REVIEW AND DEVELOPMENT

Total Oil Content

     Infrared Method—Three  spectroscopic  oil-in-water  analyzers were compared
for  field application:   the  Horiba, Model  OCMA-200;  the Wilks Miran, Model
1A-FF; and the Turner Spectronic, Model  350.  The results,  shown in Table 3,
suggest that the Miran spectrophotometer provides more  reproducible results
and  is the instrument of  choice  for the  infrared method.   It is powered by
120  VAC, can probably be  obtained as  a battery-powered  model, but  is not
explosion proof.

     The Miran analyzer has  definite  advantages over the Horiba instrument
and  some advantages over  the Turner.  The  Miran's reproducibility, range, and
easily cleaned sample cell are similar to  the Turner analyzer; it  also gives
similar extinction coefficients  for the  same oils.   The largest difference in
extinction coefficients found on the  Miran was 30% between No. 2 fuel oil and
light Arabian crude.  The Turner instrument uses visible and near  UV light
and  requires different wavelengths for No. 2 and No.  6  fuel oils.

     The requirement to adjust the wavelength for different oils could cause
errors in the total oil measurements from small variations  in the oil composi-
tion during a sampling period.   For optimum results,  all three instruments
require calibration with  an  oil  that  is  similar to the  oil being sampled.  A
critical review of the Horiba  recommended that the  automatic extractor should
not  be used.  The Miran performs the  same  measurement as the Horiba and uses
the  extraction procedure  recommended  in  the review.

     Gravimetric Method—Table 4 compares  the infrared  and gravimetric methods
for  analysis of oil in seawater.  For the  comparison, we chose to  use No. 6
fuel oil because of the unavailability of  crude samples with similar properties
to the oil from the Alaskan production sites.  It seemed reasonable that
methods developed with No. 6 fuel oil should be applicable to crude oil
samples.  For a sample of Freon  113 containing a known weight of No. 6 fuel
oil, the gravimetric method, which involved evaporation of the Freon and
weighing the residuals, gives 95% recovery of the oil.  These results suggest
that some volatiles (5%1  are lost during evaporation.   In  extraction experi-
ments, however, the oil recovery by both the infrared (extraction  and measure-r
ment by the Miran) and gravimetric (extraction, evaporation, and weighing),
methods is significantly  lower,  presumably because of the  poor extraction
efficiency of Freon 113.

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           TABLE 3.  COMPARISON OF THREE OIL-IN-WATER ANALYZERS
— — 	 ^_I^TRUMENT
FEATURE " ~~ 	 ' 	 -— _
Weight (kg)
Wavelength (nm)
Solvent
ppm oil measured
directly on scale
A
Oil analysis Cppm) 1.
2.
3.
4.
5.
6.
Average deviation
Horiba
8.9
3400-3500
CC1, or Freon
0-100
592 ± 12
640 ± 12
656 ± 10
490 ± 40
562 ± 10
516 ± 10
+ 16
Mir an
6.5
3400-3500
CC14 or Freon
0-3500
588 ± 5
552 ± 6
648 ± 6
536 ± 0
488 ± 0
576 ± 10
+ 5
Turner
7.4
620 for No. 6 oil
340 for No. 2 oil
CHC13
0-4000
656 ± 16
676 ± 5
664 ± 0
582 ± 2
478 ± 2
526 ± 14
+ 7
Oil-in-water samples from six different EPA dispersant effectiveness
tests^ were analyzed on all three instruments.  Each test was dupli-
cated, and the average and the deviation are reported.

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TABLE 4.  COMPARISON OF THE INFRARED AND GRAVIMETRIC METHODS
Infrared Method
No. 6 Oil
Added
(mg)

-
A
41
32
38
Average
Std. Dev.
% Std. Dev
No. 6 Oil
Recovered
(mg)
Recovery
(%)


i

34 82
27 85
31 : 80
82
-
-
3
4
Gravimetric Method
No. 6 Oil
Added
(mg)
No. 6 Oil
Recovered
(mg)
42+ 40
Recovery
(%)

95
4
* ;
41 36
32 25
38
-
-

26
-
-
- 1

87
78
68
78
10
13
 Oil extracted from 500 ml seawater with Freon 113 + 3 ml 12M HC1.




 Oil dissolved directly in Freon 113.

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   TABLE 5.  SOLVENT EXTRACTION EFFICIENCY  FOR. No.  6 OIL
* Oil
Extractant Added (mg)
CC14 57
53
62
56
j
Average \ -
Std. Dev.
% Std. Dev.
Freon 113 j 43
34
44
Average • -
Std. Dev. ;
% Std. Dev. |
Freon 113 * 41
32
38
Average -
Std. Dev.
% Std. Dev.
i
Oil
Recovered (mg)
54
52
59
54
-
-
-
31
29
25
-
-
34
27
31
-
-
-
Percent
Recovery
95
98
95
96 i
96 j
1
1
72
85
57
71
14
20
83
84
82
83
1
1
Oil extracted from 500 ml  seawater.
   ml 6M..HC1
                              10

-------
 Solvent  Extraction Efficiency

     As  shown  in  Table  5,  CC1,  is  more  efficient  than Freon 113  in dissolving
 No.  6  fuel  oil suspended  in seawater.   With  Freon 113,  small black flakes  of
 residual material remain  undissolved.
     We also observed that the purity of the Freon used in the extraction
process affects, the oil analysis results.  The ahsorhance- background for
Freon TF (an impure grade of Freon 113) was considerably greater than spectral
grade Freon 113; a nonlinear calibration curve for No. 6 fuel oil was observed
with the impure solvent.  Since the nonlinear calibration is less sensitive
to small differences in oil content, we suggest that more accurate results
can be obtained using the higher priced Freon 113.
Soluble Oil

     There has been some concern that a water-soluble fraction of the oil
might cause an inaccuracy in the oil measurement since the composition  and,
therefore, the extinction coefficients of dispersed and dissolved oils are
expected to be different.  A sample of No. 6 fuel oil was shaken vigorously
for four days in the presence of 400 ml of synthetic seawater.  The aqueous
phase was centrifuged to bring any dispersed oil to the surface, and the re-
sultant film of oil was skimmed off the water surface.  Microscopic analysis
of the water showed that no oil droplets remained.  A sample of the aqueous
phase was extracted with CC14 and analyzed for oil content with the Miran
lA-FF.  The results showed that only 3 ppm soluble oil was present.  This
suggests that the major fractions measured by the oil-in-water analyses are
dispersed oil, not dissolved oil.

     In a similar test, little change was observed in the apparent oil content
of a standard No. 6 oil sample in CC14 before and after treatment with Si02
gel.  Since a similar low level of soluble oil is expected with a crude oil,
the OOC-recommended silica gel adsorption task is not necessary.

Particle Size

     Particle size distribution of dispersed oil was measured using a photo-
graphic method.  A sample of oil dispersed in water was placed on a capillary
slide.  At least three representative areas in the sample were photographed
within 15 minutes at a magnification great enough to distinguish the sizes of
the smaller particles.  Statistical analysis requires more than 100 particles
to be counted from each sample; when fewer particles are present, more photo-
graphs should be taken.

     To calibrate the photographs of the oil droplets, we placed a transpa-
rent reticule on the photographs for size determination.   The reticule had
been calibrated on a picture of a stage micrometer taken at the same magnifi-
cation as the oil droplets.   A log normal distribution best described the
data, allowing the median to be found graphically.  Using this technique, we


                                      11

-------
found that the median particle diameter decreased 10% in one hour, probably
because the larger particles rise to the surface of the capillary slide and
out of focus of the camera.  This introduces an uncertainty in the measurement.
The simple and portable method we have developed can best be used to document
the presence of droplets, but is probably not useful for measuring the abso-
lute size distribution.

FIELD RESULTS

     The assembled suitcase portion of the field test kit is shown in Figures
1 and 2.  The approximate weight and volume of the entire kit is given in
Table 6.  The tests, conducted on July 7, 1980, at the Dillon offshore Produc-
tion Platform, Kenai, Alaska, and on July 8, 1980, at the Shell MGS Joint
Onshore Facility, Kenai, Alaska, are outlined in Table 2.  Water samples were
withdrawn for analysis from the final production water stream before discharge
into the ocean.  Field results were generally replicated three times during
the 8-hour testing period.  A complete listing of the instruments and materials
provided in the field test kit is given in Appendix A.  The experimental pro-
cedures for each test are given in Appendix B.

Oil-in-Water  Results

     Table  8  summarizes  the  total  oil  content of  the  Dillon and  Shell  produc-
tion water  effluents  using the  infrared  and  gravimetric methods.  The  results
have been corrected  for  the  extraction efficiency of  Freon  113 for  the
Dillon  and  Shell  oils in seawater  (Table 9).   As  shown in Table  8,  the oil
concentration (ppm, w/w) measured  by the infrared method for  the Dillon pro-
duction water is  higher  than that  for  the  Shell water (47.9 versus  38.2 ppm).
The gravimetric results  for  both samples are  appreciably lower than the in-
frared  data,  suggesting  that oil is lost during the solvent evaporation pro-
cedure  (Appendix  A).   Similar low  results  for the gravimetric method for
No. 6 oil have been previously  noted  (Table  4).
 Soluble Materials

      Table  10  gives  the  results  for  soluble  materials.   The  field method
 gives comparable results using the infrared  and  gravimetric  techniques, des-
 pite a large statistical spread.   The  laboratory results are somewhat  lower,
 suggesting  a loss  of material during transportation of  the samples to  SRI.


 Suspended Solids

      Suspended solids results are  shown  in Table 11.  For an unexplained
 reason, the total  suspended  solids results for the  Shell samples  are in
 better agreement than those for the Dillon  samples.  Other  suspended  solids
 results shown  in Table 11 are perhaps  10%  low because of a filtration  problem.
 Since the original procedure did not call  for adequate  drying of  the filter
 paper following solvent  rinsing, the wet paper adhered  to the holder and  a
 small portion  was  lost for weighing.   This difficulty has been corrected  in
 the  revised procedure given  in Appendix  B.

                                     12

-------
                     (a) TOP
                  (b) BOTTOM
FIGURE 1  ASSEMBLED FIELD TEST KIT — SUITCASE NO. 1
                        13

-------
               TABLE 6.  FIELD TEST KIT DIMENSIONS AND WEIGHT
Item
Suitcase no. 1
Suitcase no. 2
Miran spectrometer
and container
Freon 113 sample bottles
and container
Bacterial culture
bottles and container
Two gallons Freon 113
and container
Total Weight
Dimensions
(.cm)
70 x 50 x 21
70 x 50 x 21

29 x 28 x 24

36 x 25 x 29

25 x 18 x 12

40 x 25 x 40

Weight
(kg)
12.6
11.0

9.5

7.4

1.4

18.1
60.0 (132.3 Ib)
Physical Properties of Oil and Water

     The physical properties (temperature, pH, salinity, density, and viscos-
 ity) of the water and oil samples taken at the Dillon and Shell sites are
given in Table 7.
               TABLE 7.  PHYSICAL PROPERTIES OF OIL AND WATER
^v Test
Site ^v
Dillon
Shell
Production Water
Tern. (°C)
48
34
PH
7.45
8.03
c o / *
b /OO
30.6
25.7
Density
(g/cc, 20°C)
Water Oil
1.015
1.012
0.8605
0.8430
Viscosity
Ccp, 20°C)
Oil
9.3
6.5
    Salinity calculated from Standard Methods for the Examination of Water
    and Wastewater.  14th edition, M. C. Rand, A. E. Greenberg, and M. J.
    Taras,  editors,  American Public Health Assoc., Washington, D.C., 1976.
                                      15

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TABLE 10.  SOLUBLE MATERIALS RESULTS
^\. Method
Sample ^^>^
Dillon No. 1
No. 2
No. 3
Average
Std. Dev.
% Std. Dev.
Shell No. 1
No. 2
No. 3
Average
Std. Dev.
% Std. Dev.
Infrared
mg/£ (ppm)
Field
21.0
23.8
16.4
20.4
3.7
18.1
17.2
13.2
12.8
14.4
2.4
16.7
Lab
9.0
7.5
-
8.3
1.1
13.3
5.3
13.0
17.8
12.0
6.3
52.5
Gravimetric
mg/2, (ppm)
Field
11.6
35.2
11.2
19.3
13.7
71.0
18.6
11.0
10.6
13.4
4.5
33.6
                   18

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-------
Bacterial Culture

     Table 12 gives the bacterial culture test results, expressed in terms of
the sulfate-reducing bacteria count.  Because of a delay in the air shipment
of the samples to SR.I, incubation was not initiated wi.thin the recommended
24-hour period.  As a result, some of the samples arrived at the laboratory
indicating an initial positive test.  Subcultures were taken of the positive
samples and incubated for 1 week at 49°C.  Samples, regardless  of  their
condition upon arrival, were also incubated for the prescribed 5-week period
at 49°C.  The results, however, may not accurately represent the actual mi-
crobial content of the production water at the time of sampling, since testing
procedures were not initiated within 24 hours.
                                     20

-------
                   TABLE 12.  BACTERIAL CULTURE RESULTS
Sample
Dillon No.l





Bacteria/ml
Shell No. 1






Bacteria/ml
Shell No. 1


Bacteria/ml
Shell No. 3



Bacteria/ml
Dilution
10
102
io3
io4
IO5
IO6

10
2
10
IO3
IO4
IO5
io6

10
io2
io3

10
io2
IO3
io4

Original Condition
on Arrival
+
_
_
—
_
-

+

-
_
_
_
-

+
+
+

+
+
_
_

After Incubation
5 Weeks at 49 °C
+
+
_
_
_
—
IO2 - IO3
+

+
_
_
^
—
2 1
10 - 10J
+
+
+
ca. IO3
+
+
_
_
IO2 - IO3
*
Subculture
+






+







+
+
+

+
+



 Subcultures were made of any culture that arrived at the lab already
 indicating a positive result.  These subcultures were made after the
 original culture was incubated for 1 week at 49°C.

+ Positive test, sulfate-reducing bacteria present.

- Negative test, no bacteria present.
                                      21

-------
                                 REFERENCES
1.   "Study of Pollution Control Technology for Offshore Oil Drilling and
     Production Platforms," Exxon Research and Engineering, Linden, New
     Jersey, EPA Contract No. 68-03-2337 (February 1977).

2.   Offshore Operators' Committee Comments on:  "Study of Pollution Control
     Technology for Offshore Oil Drilling and Production Platforms," EPA
     Contract No. 68-03-2337 (June 1977).

3.   "Field Verification of Pollution Control Rationale for Offshore Oil and
     Gas Production Platforms," Texas Instruments, Inc., Ecological Services,
     Dallas, Texas, EPA Contract No. 7-3-002-8 (May 30, 1979).

4.   T. S. Yu and W. H. Coleman, "Evaluation of the Horiba Model OCMA-200 Oil
     Content Analyzer," David W. Taylor Naval Ship Research and Development
     Center, Report MAT-77-63 (November 1977)

5.   L. T. McCarthy, I. Wilder,  and J.  S. Dorrler, "Standard EPA Dispersant
     Effectiveness and Toxicity Tests,"  EPA-R2-73-201, May 1973.
                                     22

-------
                                  APPENDIX A
         INSTRUMENTATION AND MATERIALS PROVIDED IN THE FIELD TEST KIT

 2 Separatory funnels, 1 liter, Teflon
 4 Erlemneyer flasks,  125 ml, glass
 4 Volumetric flasks,  100 ml, glass
 2 Funnels, small, glass
 1 Repipet, 10 ml
 1 Ring stand, metal
 2 Rings,  metal
 1 Miran spectrophotometer,  oil analyzer
 1 Graduated cylinder, 1000  ml, plastic
 1 Graduated cylinder, 500 ml, plastic
 1 Graduated cylinder, 100 ml, plastic
 1 Box disposable pipets, glass
 1 Package disposable  pipet  bulbs
 1 Buchner funnel
 2 Buchner support rings (.Filter-vac)
 2 Hand vacuum pumps
 1 Box filter paper, 7 cm, Whatman No.l
 1 Filter  flask
12 Glass filters in holders
 1 Forceps
 1 Wash bottle for distilled water, 500 ml
 2 Liters  distilled water
 1 Portable pH meter
 2 pH electrodes
 3 Buffer  solutions, pH 4, 7, and 10
 2 Beakers, 100 ml, polyethylene
                                      23

-------
 2 Beakers, 500 ml, polyethylene
 1 Mercury thermometer, -20 to +100°C
 1 Dial thermometer, 0 to 100°C
25 Disposable sterile syringes, 1 cc
 1 Insulated sample box
24 Sample bottles for bacterial culture medium, 10 ml
 1 Hydrometer set
 6 Square glass bottles,  250 ml
24 Glass bottles with Teflon-lined caps, 2 oz
 1 Pair gloves, neoprene
 1 Box large Kimwipes
 1 Box small Kimwipes
 100-g Alconox cleaner
 500-ml Hand cleaner
 1 Sponge
 1 Pack Kimtowels
 2 Bottle brushes
 1 Roll electrical tape
 1 Box labels
                                    24

-------
                                 APPENDIX B

                       LABORATORY AND FIELD PROCEDURES
OIL-IN-WATER

Field Equipment
      Graduated cylinders,500 ml, 100 ml
      Separatory funnel, 1 liter
      Freon 113
      Ring stand
      Erlenmeyer flask, 250 ml
      Volumetric flask, 100 ml
      Miran spectrophotometer
      Sample bottle with Teflon-lined cap
      Disposable pipets
Field Procedure
      (1)  Purge sample port.  Fill 500-ml graduated cylinder from sample port.
      (2)  Transfer sample directly to a 1-liter Teflon separatory funnel,
           rinse, graduate with 25 ml of Freon 113.  Add Freon rinse to
           separatory funnel along with the sample.
      (3)  Swirl separatory funnel about 5 times and invert 10 times to extract
           the oil from the brine.  Place separatory funnel upright in the
           ring stand and allow layers to separate completely.
      (4)  Drain lower Freon layer into a 250-ml Erlenmeyer flask, being
           careful not to include any brine.  Repeat extraction two more times
           with 25-ml aliquots of Freon.
      (5)  Transfer solvent sample from Erlenmeyer to a 100-ml volumetric
           flask.  Rinse the Erlenmeyer with more Freon and add it to the
           volumetric flask; then add enough Freon to fill the flask to the
           mark.
      (6)  Zero spectrophotometer using Freon from the same batch used for
           the extraction of the oil.  Place the cell in the Iliran spectro-
           photometer and zero the reading at all sensitivities.  Zeroing
           should be done every time the spectrophotometer is turned on
           and once every few hours, if used continuously.

      (7)  Use a disposable pipet to transfer the Freon extract to a spectral
           cell and place the cell in the Miran.  Adjust the range to obtain
           the highest reading without going off scale.  Record this meter
           reading and the setting of the spectrophotometer.
                                      25

-------
      (8)  Save sample for lab analysis.  Rinse a sample bottle with Freon.
           Transfer the sample in the cuvette and the volumetric flask into
           the sample bottle.  Rinse both the cuvette and volumetric with
           additional Freon and add to sample.
      (9)  Seal the bottle and label it with the sample no., where and when
           the sample was taken, and who performed the analysis.


Laboratory Procedure (1R Method)

      (1)  To calibrate the spectrophotometer, obtain a sample of the crude
           oil produced on the platform of interest.  Draw 200-yl of crude oil
           into a syringe and weigh it on an analytical balance to the
           nearest 0.001 g; record the weight.  Empty the contents of the
           syringe into a 500-ml volumetric and reweigh the empty syringe.
           Record this weight below the previous weight and subtract to obtain
           the actual weight of the oil.  Fill the volumetric to the mark with
           Freon 113.  Pipet 10-, 25-, 50-, and 75-ml aliquots into four 100-
           ml volumetrics and bring them to the mark with Freon.

      (2)  Measure the absorbance of each of the solutions by the same method
           cited in the field procedure.  Plot these data to determine the
           curve for  oil concentration (mg/cc) versus absorbance.
Correction Factor for Extraction Efficiency

      (1)  Prepare 2 liters of synthetic brine of the same salinity and pH
           reported on the platform by dissolving NaCl in distilled water
           (see specific gravity and pH sections).  Adjust pH with NaOH or
           HC1.
      (2)  Place 500 ml of brine into four separatory funnels; then use the
           same procedure used in the spectrophotometer calibration section
           to weigh  a  known  amount of oil.  This amount should be the
           average amount of oil that was found on the platform.  Record
           the absorbance, setting, and the weight of the oil added to each
           separatory funnel for calculation.  Extract with Freon as described
           in the field procedure.


Laboratory Procedure (Gravimetric Method)

      (1)  Pour a Freon sample into a tared 250-ml Erlenmeyer flask.  Rinse
           the sample bottle with 10 ml of Freon and add this to the flask.
           Peel off the label and tape it into the lab book.
      (2)  Place the flask in a thermostated water bath at 50°C and allow
           almost all of the Freon to evaporate.  Remove the flask from the
           bath and run clean N« gas over the surface at room temperature
           until no more Freon is visible.  Place in a vacuum desiccator
           overnight to remove any water present.  Weigh the flask with the
           residue and record the weight.
                                      26

-------
Calculations

      (1)  Oil-ln-Water (IR Method)

                    (  la \   mg oil in Freon x ml Freon sample
                               original brine sample volume  (£)

      (2)  Oil-in-Water (Gravimetric Method)


                    ,  ,.-. _  	mg oil residue	
                              original brine sample volume (£)

      (3)  Extraction Efficiency


                „ _..,  ^          mg/cc oil in Freon x ml Freon sample    , _n
                % Oil Recovery = —="	rq	, ,  ,	-—  x 100
                                           mg oil added


SOLUBLE MATERIALS [(FILTRATION AND EQUILIBRATION)]

Field Equipment

      Buchner funnel
      Filter papers, 7 cm
      vacuum filtration apparatus
      Graduated cylinder, 1 liter
      Separatory funnel,  1 liter
      Freon 113
      Ring stand
      Erlenmeyer flask, 250 ml
      Volumetric flask, 100 ml
      Miran spectrophotometer
      Sample bottles with Teflon-lined caps
Field Procedure

      (1)  Assemble vacuum filtration apparatus.  Place filter paper in a
           Buchner funnel and wet it with distilled water.
      (2)  Purge sample port.  Fill 1-liter graduated cylinder with brine
           sample.
      (3)  Fill Buchner funnel with brine; filter and discard filtrate.
           Filter 500 ml of sample.  Extract this filtrate sample with
           Freon 113 as described in the oil-in-water field procedure
           and measure the absorbance accordingly.
      (4)  Transfer sample to Teflon-capped bottle.  Label with sample number,
           date, location, time, volume, and person who performed test.  Then
           transport samples to the lab for gravimetric analysis.
                                      27

-------
Laboratory Procedure

      (1)  Place 400 ml of synthetic brine  (use the same salinity and pH
           described in the lab procedure of the oil-in-water test) in a
           500-ml stoppered Erlenmeyer flask.
      (2)  Syringe 5 ml of the crude oil from the platform of interest
           into each of the brine solutions.  Shake the flasks vigorously
           for 4 days.
      (3)  Transfer to a separatory funnel  and drain the aqueous phase into
           centrifuge tubes.  Set up a vacuum trap with a disposable pipet
           at the end and siphon off any oil film present.  Centrifuge this
           solution at 3.8 x 10-^ g for 1 hr.
      (4)  Remove the oil film again.  Measure 200 ml of the brine in a
           volumetric and transfer it to a  separatory funnel.  Rinse the
           volumetric flask with Freon and  add to separatory funnel.
           Extract the sample with three 10-ml aliquots of Freon and fill
           to the mark of a 50-ml volumetric flask.  Measure and record the
           absorbance from the spectrophotometer.
Calculations
      (1)  Soluble materials (IR field method)
                   ..  /n,   mg/cc oil in Freon x sample volume
               ppm (mg/A) = -^ - — - n  -  . - % - -
                                 original brine sample volume (.£)

      (2)  Soluble materials (Lab Method)


                   ,  ,.,   mg/cc oil in Freon x sample volume
               ppm (mg/£) = — ^ - : — : - =— T — : - — «- - = - 7T\
                               original brine sample volume  (£)
TEMPERATURE AND pH

Field Equipment

      pH meter
      Buffer solutions (pH 4, 7, 10)
      Dial thermometer
      Mercury thermometer
      Graduated cylinder, 1 liter


Field Procedure

      (1)  Calibrate the pH meter immediately before each use.  Immerse
           the combination electrode into pH 7 buffer.  Adjust temperature
           knob to the temperature of the sample.  Adjust the calibration
           knob to pH 7 reading.  Remove electrode, rinse with deionized
           water, and wipe clean.  See operator's manual for additional

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           information regarding pH meter.
      (2)  Calibrate the dial thermometer against a mercury thermometer once
           a day.  Record any difference in the readings.
      (3)  Purge sample port.  Collect 1 liter of sample in a graduated
           cylinder and immediately insert the dial thermometer.  Wait 1
           min until the thermometer has equilibrated and read the temperature.
           NOTE - If the sample site has a temperature well, place the
           thermometer directly into the port, wait 1 min, and read the
           temperature.
      (4)  Immerse combination electrode in sample and agitate gently for 30
           sec.  Read pH after steady state has been achieved.  Remove
           electrode, rinse with deionized or clean tap water, and wipe clean.
           If the pH is > 10, calibrate using the pH 10 buffer.


SPECIFIC GRAVITY (OIL AND WATER), SALINITY

Field Equipment

      Graduated Cylinder, 1 liter
      Thermometer, mercury, -20 to +100°C
      Hydrometer Set
      3 Square sample bottles, 250 ml
      2 polyethylene bottles, 1 liter


Field Procedure

      (1)  Fill square sample bottles with crude oil to be used in laboratory
           analysis.  Also, fill polyethylene bottles with production water
           for laboratory determination of salinity.  Label and seal all
           samples for transport.
      (2)  Purge sample port.  Fill a 1-liter graduated cylinder from sample
           port without splashing, to avoid the formation of air bubbles.
      (3)  Insert a thermometer into the sample and allow time for equilibra-
           tion.  Record the temperature after gently stirring the sample
           with the thermometer.
      (4)  Lower the hydrometer into the sample.  Take care to avoid wetting
           the stem above the level to which it will be immersed in the
           liquid.  Depress the hydrometer about two scale divisions into
           the liquid, and with a slight spin, release it.  When the hydro-
           meter has come to rest, floating freely away from the walls of
           the cylinder, estimate the scale reading to the nearest 0.0001 sp.gr.
      (5)  Immediately after observing the hydrometer scale value, stir the
           sample with the thermometer and record the temperature.  Should
           this temperature differ from the previous reading by more than
           0.5 °C, repeat the measurement until the temperature is stable
           within 0.5°C.
      (6)  With an opaque liquid, take a reading by observing, with the eye
           slightly above the plane of the surface of the liquid,  the point
           on the hydrometer scale to which the sample rises.   Correct this
                                      29

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           reading based on the meniscus calibration for the particular
           hydrometer being used.
Laboratory Procedure

      (1)  Follow the field procedure for measuring specific gravity, and
           determine the density of the production water obtained in the
           field.
      (2)  Convert findings to salinity (°/oo) from the tables included in
           No. 209B "Hydrometrie Method for Salinity Determination," in
           Standard Methods for the Examination of Water and Wastewater,
           14th Edition (American Public Health Association, Washington,
           D.C., 1976).
VISCOSITY

Laboratory Equipment

      Brookfield Model LVF Spindle Viscometer
      U.S. Bureau of Standards calibrated oils for viscosity testing
      Beaker, 600 ml
      Thermometer, 0 to 11Q°C
      Oil Sample from platform of interest


Laboratory Procedure


      (1)  Follow the operating instructions for the viscometer.
      (2)  Calibrate the viscometer with a certified standard having
           a specific gravity close to that of the oil in question.
      (3)  The temperature of the test oil should be controlled to
           within ± 0.02°C.
      (4)  Report results in units of centipoise (cps).
SUSPENDED SOLIDS

Field Equipment

      Preweighed glass fiber filters/holders
      Vacuum filtration apparatus
      Forceps
      Distilled water
      Graduated cylinder, 1 liter
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Field Preparation
      (1)  Desiccate filters overnight before field expedition.
      (2)  Weigh filters, using an analytical balance, and then place each
           filter in a holder.  Label the holders numerically, recording
           the weight of each respective filter.
Field Procedure
      (1)  Purge sample port and fill a 1-liter graduated cylinder with brine.
      (2)  Assemble the vacuum filtration apparatus.  Place a previously
           weighed glass filter in a Buchner funnel with forceps  and wet it
           with distilled water.
      (3)  Apply a vacuum and filter the brine until the paper begins to clog.
           If there are few solids present, use the full liter. Record the
           volume of brine filtered.
      (4)  Rinse the filter with 100 ml of distilled water; then draw air
           through to partially dry it.  Replace filter in its holder with
           forceps; close the lid.
      (5)  Record the date on the holder and the conditions under which the
           sample was taken.  At the end of the sampling period, all the
           filter holders should be firmly taped together so that they do
           not open during transport back to the lab.
Laboratory Procedure

      (1)  Remove the tops of the filter holders and dry the filters in a
           vacuum desiccator overnight; then weigh the filter and record
           the weight (A).
      (2)  Assemble the vacuum filtration apparatus.  Place the filter in
           the buchner funnel right side up, and wash with three 25-ml
           aliquots of CHC1 .  Dry the filters with air; then return to
           the desiccator overnight.  IMPORTANT - Do not place filters
           into the plastic holders to desiccate because the CHC1_ will
           cause the filter to adhere to the holder.  Remove the following
           day, reweigh, and record the weight (B).
      (3)  Wash the filter with 100 ml 6N HC1 and vacuum dry.  Desiccate
           the filter overnight.  Weigh the filter for a final time and
           record this weight (C).
Calculations

      Using the original weight of the filter as T, calculate the following:

          Total suspended solids         = A - T
          Organic suspended solids       = A - B
          Acid-soluble suspended solids  = B - C
          Fixed suspended solids         = C - T
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Convert findings to parts per million (mg/£):

       „  /„„/,) \ -  	weight (mg)	
      ppm (mg/£) -  total volume filtered (A)
BACTERIAL CULTURE:  SULFATE-REDUCING BACTERIA

Field Equipment

      Serum bottles containing culture medium, 10 ml
      Disposable, presterilized syringes, 1 ml
      Sterile sample bottle
      Insulated sample box.


Field Preparation

      (1)  Before expedition, prepare the following medium by dissolving
           the ingredients with gentle heating.  Adjust the pH to 7.3
           with NaOH.  If excessive precipitation occurs, the medium
           should be discarded.
               Sodium lactate, USP,               4.0  ml
               Yeast extract                      1.0  g
               Ascorbic acid                      0.1  g
               MgSO,«7H20                         0.2  g
               K HPO, (anhydrous)                 0.01 g
               Fe(S07)9(NH,) •6H90                0.2  g
               NaCl                              10.0  g
               Distilled water                1,000.0  ml
      (2)  Add reduced iron powder, reagent grade, to the serum bottle and
           fill with 9 ml of hot broth.  Flush the bottles with N« gas.
           Use butyl-type rubber to stopper them; then cap with disposable
           metallic covers.  Sterilize the bottles and contents at 15 psi
           steam pressure for 15 min.


Field Procedure

      (1)  Purge sample port.
      (2)  Use sterile bottle to collect sample.  Record time, date, tempera-
           ture, and water appearance at this time.
      (3)  All work should be done in duplicate.  Using a sterile, disposable
           syringe, transfer 1 ml of sample to a serum bottle containing the
           culture medium.  Agitate the bottle to mix the inoculum; then
           using a new syringe, aseptically transfer 1 ml from this bottle
           to a second one and mix as before.  Continue this serial transfer
           until a dilution of 1 to 1,000,000 is reached (6 bottles).
      (4)  Place the inoculated bottles in the insulated sample box for
           transport to the laboratory.  Note any bottles that turn black
           within 2 hours.  These should not be considered positive since
           this probably is due to the presence of sulfide ion in the sample


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           Subcultures of these false positive samples may be made after
           1 week.
Laboratory Procedure

      (1)  Incubate all bottles at the temperature of the water at the time
           of sampling, ±5°C, for a minimum of 4 weeks.
      (2)  Examine the bottles on the third day and at the end of each week
           for the appearance of sulfate-reducing bacteria, indicated by
           intense black color.  After 1 week, make any necessary subcultures
           (See Field Procedure, Step 4).
Calculations

      (1)  Report the data as the highest dilution indicating growth, as
           compared with the lowest dilution showing no growth.  The data
           are reported as a range in numbers (i.e., 100-1,000 sulfate-
           reducing bacteria per ml).
      (2)  The maximuum time between sampling and examination should not
           exceed 24 hr.  If an examination cannot be initiated within this
           period, include the following statement in the report:  "These
           results do not necessarily represent the actual microbial content
           of the water at the time of sampling."
Reference

American Petroleum Institute, API Recommended Practice for Biological Analysis
of Subsurface Injection Water (American Petroleum Institute, Dallas, Texas,
1975), p. 7.
                                                                  U..U
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