EPA-600/3-84-067
May 1984
ACUTE TOXICITY OP EIGHT LABORATORY-PREPARED
GENERIC DRILLING FLUIDS TO MYSIDS (Mysidopsis bahia)
by
T.W. Duke, P.R. Parrish,, R.M. Montgomery,
S.D. Macauley, J.M. Macauley, and G.M. Gripe
Environmental Research Laboratory
Sabine Island
Gulf Breeze, Florida 32561
ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
GULF BREEZE, FLORIDA 32561
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ERRATA
ACUTE TOXICITY OF EIGHT LABORATORY-PREPARED
GENERIC DRILLING FLUIDS TO MYSIDS (Mysidopsis bahia)
by
T.W. Duke, P.R. Parrish, R.M. Montgomery,
S.D. Macauley, J.M. Macauley, and G.M. Cripe
EPA-600/3-84-067
May 1984
Page 6, line 6. "...same as those "
Page 10, line 10. "...oil-free drilling fluids,...."
Page 12, line 5. "CENTEC3"
Page 12, line 18. "aCentec Analytical Service "
Page 14, line 9. "Polyanionic Cellulose"
Page 18, line 11. "Definitive #2 5% 18% 18% - 42 80%
100% - - - -"
OCT * 5189!
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DISCLAIMER
The InforM-tion In this document has been funded by the U.S. Environmental
Protection Agency. It has been subject to the Agency's peer and administrative
review and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the U.S. Environmental
Protection Agency; nor does mention of trade names or cornnercial products
constitute endorsement or reconmendation for use.
ii
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FOREWORD
The protection of our estuarine and coastal areas from damage caused
by toxic organic pollutants requires that regulations restricting the
introduction ot these compounds into the marine environment be formulated
on a sound scientific basis. Accurate information describing concentration-
response relationships for organisms and ecosystems under varying conditions
is required. The Environmental Research Laboratory, Gulf Breeze, contributes
to satisfying this information requirement through research programs aimed
at determining:
o the effects of toxic organic pollutants on individual species
and communities of organisms.
o the effects of toxic organics on ecosystems processes and components.
o the significance of chemical carcinogens in the estuarine and marine
environments.
This report addresses the acute toxicity of eight generic drilling
fluids to mysids, Mysidopsis bafaia, and the toxicity of two of the
fluids containing a mineral oil to these organisms. The tests were conducted
in response to a request from the Office of Water Regulations and Standards
and tested according to procedures prescribed by the Office.
/r,
7s A "i t
ftenry F. Knos
Director
Environmental Research Laboratory
Gulf Hrpeze. Florida
iii
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ABSTRACT
Acute toxicity tests were conducted during August-September 1983 with
eight laboratory-prepared generic drilling fluids (also called muds) and
mysids (Mysidopsis bahia) at the U.S. Environmental Protection Agency's
Environmental Research Laboratory. Gulf Breeze, Florida. Two of the drilling
fluids were tested at the Environmental Research Laboratory, Narragansett,
Rhode Island, to confirm the validity of the tests conducted at Gulf Breeze.
The test material was the suspended participate phase (SPP) of each
drilling fluid. The SPP was prepared by mixing volumetrically 1 part
drilling fluid with 9 parts seawater and allowing the resulting slurry to
settle for one hour. The material that remained in suspension was the SPP.
Tbxicity of the SPP of the drilling fluids ranged from a 96-hour LC50
(the concentration lethal to 50% of the test animals after 96 hours of
exposure) of 2.7% for a KC1 polymer mud to 65.4% for a lightly treated
lignosulfonate mud. No median effect (50% mortality) was observed in
three drilling fluids — a non-dispersed mud, a spud mud, and a seawater-
freshwater gel mud.
Two of the generic drilling fluids to which mineral oil had been
purposely added were also tested at Gulf Breeze. The addition of the
mineral oil increased the acute toxicity of each fluid to mysids. When 1%
mineral oil was added, the 96-hour LC50 changed from Ti.6% to 13.5% for
fluid #2, a seawater lignosulfonate mud, and from 29.3*5 to 7.1% for fluid
*8, a freshwater lignosulfonate mud. Addition of 5? and u)% mineral oil
further increased toxicity.
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CONTENTS
Foreword lii
Abstract iv
Tables vi
Acknowledgment. vii
Introduction 1
Materials and Methods
A. Drilling Fluids 2
B. Reference Toxicant 3
C. Methods for Drilling Fluid Tests 3
D. Methods for Reference Toxicant
(Positive Control) Tests ..... 5
E. Test Animals 6
F. Statistical Analyses 6
Results and Discussion
A. Generic Drilling Fluids 8
B. Mineral dl-Contaminated Drilling Fluids 9
Literature Cited 11
Appendices
A. Chemical and Physical Characteristics of the
Mineral Oil Used 23
B. Mortality Data 24
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TABLES
Nunber Page
1 Treatment of eight generic drilling fluids 12
2 Source and composition of eight generic
drilling fluids 13
3 Results of acute toxicity tests with eight
generic drilling fluids and raysids (Mysidopsis
bahia), Gulf Breeze 15
4 Generic drilling fluid concentrations 16
5 Relationship of the weight of suspended material
in the suspended particulate phase of eight
generic drilling fluids to toxicity 17
6 Results of three acute toxicity tests with generic
drilling fluid #1, Gulf Breeze 18
7 Results of acute toxicity tests with two generic
drilling fluids, Gulf Breeze and Narragansett 19
8 Comparative toxicity of two generic drilling
fluids without and with mineral oil 20
9 Results of acute toxicity tests with two generic
drilling fluids containing mineral oil 21
10 Results of three acute toxicity tests with generic
drilling fluid #8-05, Gulf Breeze 22
vi
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ACKNOWLEDGMENTS
The cooperation of the Environmental Research Laboratory. Narragansett,
Rhode Island, is gratefully acknowledged. Mr. S. Schimmel, U.S. Environmental
Protection Agency, served as coordinator for the two tests conducted
there; Messrs. T. Coffee and D. Wayne of the Edgerton Research Laboratory,
New England Aquarium, Boston, Massachusetts, performed the tests under
contract to the Narragansett laboratory.
At Gulf Breeze, personnel support was provided by Georgia State
University, Cooperative Agreement CR809370, for Mr. R. Parrish during most
of the testing program and by the University of West Florida, Cooperative
Agreement CR807417, for Mr. R. Montgomery and Mrs. S. Macauley during the
entire testing program.
vii
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INTRODUCTION
The purpose of this study was to determine the acute toxicity of eight
laboratory-prepared generic drilling fluids to mysids (Mysidopsis bahia)
according to methodology prescribed by the Effluent Guidelines Division,
Office of Water Regulations and Standards, U.S. Environmental Protection
Agency (EPA). Toxicity tests with all fluids were conducted at the EPA
Environmental Research Laboratory, Gulf Breeze (ERL/GB), Florida, during
August-September 1983, and two confirmatory tests were conducted at the EPA
Environmental Research Laboratory, Narragansett, Rhode Island, during the
same time period.
Acute toxicity tests were also conducted at ERL/GB during September-
October 1983 with two of the generic drilling fluids that had been
purposely contaminated with mineral oil. The purpose was to determine the
toxicity of mineral oil in representative drilling fluids.
The generic drilling fluid concept was developed jointly by EPA's
Region II and industry to provide EPA information on the impact of drilling
fluids and components of the fluids released into the environment without
requiring each drilling operator to perform repetitious toxicity tests and
chemical analyses. The eight generic drilling fluids include virtually all
water-based fluids used on the U.S. Outer Continental Shelf. Only major
components of the generic fluids are specified and additional information
concerning the effects of speciality additives must be submitted to EPA
prior to their discharge (Petrazzulo, 1983). The generic fluid concept is
now being employed by EPA Regional Offices involved In the permitting
process (EPA, 1983).
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MATERIALS AND METHODS
A. Drilling Fluids
The eight laboratory-prepared generic drilling fluids to be tested
were received at ERL/GB during June and July 1983. They were sent via
connercial airlines by each femulator. Bach drilling fluid was contained
in four 3.5-gallon plastic buckets with lids tightly sealed. The buckets
were shipped in plastic ice chests, sane of which contained wet ice or
"blue ice." All buckets were cool to the touch when they arrived at ERL/GB.
Upon receipt, each bucket of fluid was immediately placed in a large walk-in
cooler with temperature maintained at approximately 4°C until the contents
of each bucket were combined, mixed, and recontainerized. The purpose of
mixing was to assure homogeneous samples for testing and/or chemical analyses.
Mixing was accomplished by emptying each bucket of a fluid into a large
plastic container. The fluid was stirred by hand with a large Teflon*
paddle as approximately half of the contents of each bucket were alternately
emptied. The fluid was then stirred for an additional 2-5 minutes, and was
poured back into three of the original buckets that had been washed with
tap water (except for the first fluid received, EPA-83-00800, which was put
into new buckets). Drilling fluid equivalent to the contents of approximately
one bucket (about 11 liters) was placed in new 1-liter plastic jars. All
containers were labeled and capped (new lids were used on buckets because
the original lids were destroyed when opened) after the air space above the
fluid was flooded with nitrogen. The caps/lids were securely fastened, and
the containers were placed in the walk-in cooler.
A detailed account of the treatment of each drilling fluid from the
date of receipt to testing and/or transshipment is given in Table I; the
source and composition of each fluid are listed in Tible 2. Appendix A
2
-------
contains a description of the physical and chemical characteristics of the
mineral oil added to two of the generic drilling fluids.
B. Reference Toxicant
Sodiun lauryl sulfate (dodecyl sodium sulfate) was used as a reference
toxicant for the positive control. The chemical used was manufactured by
Sigma Chemical Company, No. L-5750, Lot. 42F-0039, and was approximately
95% pure. Chemical from the same lot was used in the positive control
tests at Gulf Breeze and Narragansett.
C. Methods for Drilling Fluid Tests
Test methods followed those proposed by Petrazzuolo (1983) with the
following exceptions:
(1) Natural seawater from the ERL/GB seawater system was used
instead of artificial seawater. The natural seawater was pumped from Santa
Rosa Sound and filtered through sand and a 5-micrometer fiber filter;
salinity was controlled at 20*2 parts per thousand by the addition of
deionized water, and temperature was controlled by a commercial chiller;
(2) 5*l-day-old mysids were used instead of 4±lday-old mysids;
(3) Test mixtures were aerated; and
(4) For the mineral oil tests, glassware was washed with petroleum
ether to assure removal of the oil.
At the outset, one or more 1-liter jars of the drilling fluid(s) to be
tested were selected impartially. The fluid was mixed in the jar for at
least 30 minutes by using a 1,600-rpm electric stirrer which turned a four-
blade stainless steel stirrer. While the fluid was stirring, seawater was
aerated in a container in an ice-bath.
To prepare the suspended particulate phase of the drilling fluid.
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800 railliliters of the chilled seawater was added to a 2-liter Erlenmeyer
flask. Then, 200 ndlliliters of the well-etirred drilling fluid was added
to the flask, ifare seawater (1,000 mililiters) was added to bring the
contents of the flask to the 2-liter mark. This 1-part fluid:9-part seawater
slurry was placed on a magnetic stirrer and mixed for at least 5 minutes.
The pH was measured and, if necessary, glacial acetic acid was added to
bring the pH of the slurry within 0.2 pH units of the seawater, as directed
by the test method. (If too much acid was added, sodiun hydroxide was
added as needed to increase pH.) The slurry was mixed for an additional 5
minutes if acid was added and then allowed to settle for 1 hour. The
suspended phase (that is, all the liquid and suspended particulate above
the settled or solid phase) was then decanted into a separate container,
and pH and dissolved oxygen (DO) concentration were measured. If necessary,
pH was again adjusted. Also, if DO was less than 65% of saturation, the
suspended particulate phase was aerated, usually for 5 minutes. The
appropriate volune of this 100% suspended particulate phase or seawater or
both was added to a 2-liter Carolina culture dish (the total volune in each
dish was 1 liter) to prepare the test and control mixtures. The mixtures
were then stirred for approximately 30 minutes; the DO, pH, temperature and
salinity were measured; and test animals were added to the dishes.
The number of animals exposed to a drilling fluid and the number of
replicates varied. For range-finding tests, 10 mysids were added to each
of 4 concentrations (100%, 50%, 10%, and 1% suspended particulate phase)
and a seawater control, none of which was replicated. For definitive tests,
20 mysids were added to a seawater control and each of 5 concentrations
(except only 3 concentrations were tested in those cases where no median
effect, that is, 50% mortality, occurred in 100% suspended particulate
-------
phase in the range-finding test). Three replications of each treatment gave
a total of 60 animals per treatment. For all tests, the animals in each
dish were placed in holding cups fabricated by gluing a collar of 363-fliicrometer
mesh nylon screen to a 15-centimeter wide glass Petri dish with silicone
sealant. The nylon screen collar was approximately 5 centimeters high.
After measurement of water quality characteristics (DO, pH, salinity,
and temperature) and addition of animals, the dishes were stacked three-high,
with a cover on the top dish, and placed in an incubator. The temperature
controller was set at 21°C and the light controller at 14 hours light:10
hours dark. All treatments were aerated at a volume estimated to be 50-140
cubic centimeters/minute during the tests. Air was delivered to each dish
through polyethylene tubing (0.045-inch inner diameter and 0.062-inch outer
diameter) by a small aquarium pump.
Water quality was measured at 24-hour intervals, but the turbidity of
most fluids prevented 24-hour observations of test animals. After 96 hours,
the test was terminated. If the solution was turbid, the cups were flushed
with seawater until the animals became visible. Live animals were then
removed by pipette and counted. Quality assurance was ensured by counting
the control animals, placing them back in the holding cup and flushing them
with seawater, and then recounting them.
Test methods used at Narragansett also followed Petrazzuolo's (1983)
proposed methods. A report on the Narragansett tests is maintained at the
Environmental Research Laboratories, Gulf Breeze and Narragansett.
D. Methods for Reference Toxicant (Positive Control) Tests
Test methods were those used for the drilling fluid tests, except that
the test material was prepared by weighing one gram of -sodium lauryl sulfate
on an analytical balance, adding the chemical to a I00-miHi liter volumetric
5
-------
flask, and bringing the flask to volune with deionized water. The test
mixtures were prepared by adding 0.1 milliliter of the stock solution for
each part per million desired to one liter of seawater. The mixtures were
stirred briefly, water quality was measured, animals were added to holding
cups, and the test was begun. Incubation and monitoring procedures were
the same as these for the drilling fluids.
E. Test Animals
Mysids (Mysidopsis bahia) for the drilling fluid and reference toxicant
tests were cultured at the Gulf Breeze and Narragansett laboratories. In
addition, seme mysids used for testing at Gulf Breeze were purchased from a
connerical supplier, the origin of whose stock was the same as the laboratory
stock. All raysids (5±1 days old) were fed Artemia salina nauplii
(32-48 hours post-hydration) during holding and testing.
F. Statistical Analyses
Mortality data from the drilling fluid tests and the reference toxicant
(positive control) tests were subjected to statistical analyses. A 96-hour
LC50 (the concentration lethal to 50% of the test animals after 96 hours of
exposure) was calculated for each drilling fluid (if the mortality data
were amenable) and for each reference toxicant test by using the moving average
method (Kendall and Stuart, 1973, and Stephan, 1977). The 95% confidence
limits were also calculated. For tests where control mortality was £10%, no
correction was made and the uncorrected data were used to compute LCSO's and
95% confidence limits. For one mineral oil-contaminated drilling fluid and
three reference toxicant tests at Gulf Breeze, the control mortality was >10%
and data were corrected by using Abbott's formula (Abbott, 1925). The data
used in drilling fluid LC50 calculations are contained in Appendix B.
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Data froai the Gulf Breeze testa with the eight generic drilling fluids
(Appendix B) were also analyzed by SAS*, based on the probit method (Plnney,
1971). A correction was made for all tests in which there was control
mortality.1
To estimate the association between the mineral oil content and toxicity.
data were analyzed by using Spearman's coefficient of rank correlation
(Steel and Torrie, 1980).
1 Analyses performed by R. Clifton Bailey, U.S. E?A, ^rr^ram Integration
and Evaluation Staff (WH-586), Office of Water Hen-iiations and Standards,
Washington, DC 20460.
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RESULTS AND DISCUSSION
A. Generic drilling fluids
The range of toxicity of eight laboratory-prepared generic drilling
fluids to mysids was considerable. The 96-hour LCSO's were from 2.7%
suspended particulate phase (fluid #1) to 65.4* (fluid #7). An LC50 could
not be calculated for three fluids — #4, #5, and #6 — because no median
effect (50* mortality) occurred (Table 3). It should be noted that these
tests were not designed to identify the constituents in drilling fluid #1
that caused it to be more toxic than the other fluids.
The acute toxicity of the drilling fluids was generally related to the
weight of the suspended material in the suspended particulate phase of each
fluid, except for fluid #1. For example, fluid *7 contained 17.12 grams of
suspended particulate matter per liter of the suspended particulate phase
and the 96-hour LC50 was 65.4%. The more toxic fluid #3 contained 25.12
grams of suspended matter per liter, with a 96-hour LC50 of 16.3% (Tables 4
and 5).
The response of the mysids to the reference toxicant, sodium lauryl
sulfate, showed that the test animal populations were in suitable condition
for the toxicity tests. In five tests, the 96-hour LCSO's were from 3.4 ppm
to 7.5 ppn (Table 3). These are in accord with the literature and with
unpublished data from Gulf Breeze and a commercial testing laboratory.
The reference toxicant LCSO's obtained at Gulf Breeze and Narragansett were
similar even though the brood stocks and natural seawater were different.
Water quality was generally acceptable. The most serious problem was
dissolved oxygen (DO) concentration. The oxygen demand of some drilling
fluids (#3 and #8, for example) was high. The suspended particulate phase
had to be aerated before testing began, and even with aeration during
8
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the test, DO concentrations were low. In only a few instances, however,
was DO less than the minimally acceptable 65% of saturation. (NOTE: Raw
data sheets are maintained at ERL/GB).
Heproducibility of results from test to test at Gulf Breeze was
excellent. With drilling fluid #1, for example, three different tests were
conducted: a range-finding test, a definitive test (which was repeated
because of an unacceptable reference toxicant test), and a second definitive
test. The results showed similar concentration-response relationships in
all three tests (Table 6).
The interlaboratory agreement of test data from Gulf Breeze and
Narragansett was equally good. The validity of the Gulf Breeze
tests were confirmed by tests with two drilling fluids (#1 and *S) at
Narragansett. The 96-hour LC50 for fluid #1 was almost exactly the same at
both laboratories (Table 7). The results of the tests with fluid *S were
similar: Narragansett observed no mortality in 100% suspended participate
phase, whereas Gulf Breeze recorded 12% mortality in that concentration.
Considering the nature of the test material and other possible sources of
variability, this represents a more than satisfactory duplication of test
results.
The slight differences in computed median effect concentrations 'J^ere
not considered significant. Whether there was correction for control
mortality or not, and whether the moving average method or the probit method
was used, there was excellent agreement among the toxicity test results.
B. Mineral oil-contaminated drilling fluids
The addition of mineral oil to laboratory-prepared generic drilling
fluids #2 and #8 dramatically increased their acute toxicity to mysids.
When 1% mineral oil was added, the 96-hour LC50 changed from 51.6% to 13.4%
9
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for fluid #2 and from 29.3% to 7.1% for fluid #8. Addition of 5% and 10%
mineral oil further increased toxicity (Table 8).
There was a significant negative correlation between mineral oil
content and the 96-hour LC50 for each fluid; Spearmans's r » -0.976 with
a probability <0.0001.
The response of the mysids to the reference toxicant was within an
acceptable range, demonstrating that the test animals were in suitable
condition (Table 9).
While the reproducibility of results from test to test was not as good
as with oil-free drilling fluid, the test results did show similar
concentration-response relationships (Table 10). The variation was probably
caused by the volatility of the mineral oil and the need to aerate the
suspended particulate phase before testing to achieve acceptable dissolved
oxygen concentrations.
The presence of mineral oil in the generic drilling fluids did not
adversely affect water quality. The DO, pH, salinity, and temperature were
all within acceptable ranges during the tests.
10
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LITERATURE CITED
Abbott, W.S. 1925. A Method of Computing the Effectivenesss of an
Insecticide. J. Econ. Entoraol. 18: 265-267.
Finney. D.J. 1978. Statistical Methods in Biological Assay, 3rd ed.
Griffin Press, London. 508 pp.
Kendall, M.G. and Stuart, A. 1973. The Advanced Theory of Statistics,
Vol. 3, 3rd ed., Hafner Publishing Co., New York, NY, pp. 342-430.
Petrazzuolo, G. 1983. Proposed Methodology: Drilling Fluids Toxicity
Test for the Offshore Subcategory; Oil and Gas Extraction Industry.
Technical Resources, Inc., Bethesda, MD 20817. DRAFT dated May 19.
1983.
Steel, R.G. and J.H. Torrie. 1980. Principles and Procedures of Statistics,
2nd ed. McGraw-Hill, New York, NY. 633 pp.
Stephan, C.E. 1977. Methods for Calculating an LC50. In: Aquatic Toxicity
and Hazard Evaluation. ASTM STP 634, F.L. Mayer and J.L. Hamelink, Eds.,
American Society for Testing and Materials, Philadelphia, PA, pp. 65-84.
U.S. Environmental Protection Agency. 1983. Issuance of Final General NPDES
Permits for Oil and Gas Operations on the Outer Continental Shelf (CCS) of
Alaska; Norton Sound and Beaufort Sea. Federal Register Vol. 48, No. 236,
December 7, 1983, pp. 54881-54897.
11
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TABLE 1. Treatment of eight generic drilling fluids received at U.S. EPA, Gulf Breeze, Florida.
TRANSSHIPPED
CENTIC*
GENKKIC MUDS
EPA-83-O01
EPA-83-002
EPA-83-003
KPA-83-4XM
KPA-83-005
KPA-H3-4XKi
LPA-83-OO7
KPA-83-OOB
KtiCfcllVKD
13 July 83
ti July 83
16 July 83
19 July 83
8 July 83
8 July 83
ti July 83
28 June 83
MIXED
14 July 83
8 July 83
18 July 83
20 July 83
11 July 83
14 July 83
8 July 83
29 June 83
SHIPPED
14 July 83
12 July 83
21 July 83
21 July 83
14 July 83
14 July 83
12 July 83
7 July 83
RECEIVED
15 July 83
13 July 83
22 July 83
22 July 83
15 July 83
15 July 83
13 July 83
8 July 83
NARRAGANSETT
SHIPPED RECEIVED
1 August 83 2 August 83
18 July 83 19 July 83
18 July 83 19 July 83b
iL- Analytical Son/ice, Salem, Virginia, for chemical analyses.
NOI. tested at Nurrttganuctt.
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TABLE 2. Source and reported composition of eight generic drilling fluids received at U.S.
EPA, Gulf Breeze, Florida.
Composition
Drilling Fluid Source
EPA-83-001, Chrcmalloy
KC1 Polymer Mud
Component
KC1
Drispac (Super-Lo)
X-C Polymer
Barite
Starch
Sea water
Concentration
50.0
0.5
1.0
283.2
2.0
257.6
grains (g)
g
g
g
g
milliliters
(ml)
EPA-83-002,
Seawater
Lignosulfonate Mud
IMCO Services
Lime Mud
Hughes
KPA-83-004,
Non-dispersed mud
Newpurk Drilling Fluids
Attapulgite
Chrome Lignosulfonate
Lignite
Polyanionic Cellulose
Caustic
Barite
Seawater
Benitonite
Lime
Barite
Chrome Lignosulfonate
Caustic
Lignite
Distilled water
Bentonlte
Acrylic Polymer (for
suspension)
Acrylic Polymer (for
fluid loss control)
Harite
Deionlzed .Water
30.0 pounds per barrel
(ppbbl)
15.0 ppbbl
10.0 ppbbl
0.25 ppbbl
To pH 10.5-11.0
To bring mud weight to 17-18 pounds
per gallon (ppg)
As needed
20.06
5.01
281.81
15.04
1.00
8.02
257.04
g
g
g
g
ml
13.0 ppbbl
0.5 ppbbl
0.25 ppbbl
190.7 ppbbl
299.6 ppbbl
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Table 2, continued.
EPA-83-005,
Spud mud
ML Uaroid
EPA-83-006, Ul Ichem
Seawater/Freshwater
Gel Mud
EPA-83-007,
Lightly Treated
Llgnosulfonate Mud
EPA-83-008,
Freshwater
Lignosulfonate Mud
Magobar Dresser
Dowel1
Bentonlte
Lime
Barite
Seawater/Freshwater
Caustic
Bentonite
Polyaninic Cellulose
Sodium Carboxymethyl
Cellulose
Barite
Sodium Hydroxide
To pH
12.5
0.5
50.0
1.0
10.0
ppbbl
ppbbl
ppbbl
bbl
20.0 ppbbl
0.50 ppbbl
0.25
20.0
To pH 9.5
ppbbl
ppbbl
Seawater/Freshwater, 1:1 As needed
Bentonite
Chrome Lignosulfonate
Lignite
Soda Ash
Carboxymethyl Cellulose
Barite
Bentonite
Chrome Lignosulfonate
Lignite
Carboxymethyl Cellulose
Sodium Bicarbonate
Barite
Deionized Water
20.0
5.0
3.0
1.0
0.5
178.5
15.0
15.0
10.0
0.25
1.0
487.0
187.0
ppbbl
ppbbl
ppbbl
ppbbl
ppbbl
ppbbl
g
g
g
g
g
g
ml
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TABLE 3. Results of acute toxicity tests with eight generic drilling fluids and mysids (Mysidopsis bahia),
The tests were conducted at U.S. EPA, Gulf Breeze, Florida, during August-September 1983.
Drilling Kange-finding Test
Fluid (median effect)
HI >1% <10% SPPC
ff2 >50% <100% SPP
03 >10% <50% SPP
//4 No median effect
in 100% SPP
//5 1(K)% SPP
06 No median et'tect
in HXJ% SPP
Definitive Testa
(96-h LC50 & 95% CL)
2.7% SPP
(2.5-2.9)
51.6% SPP
(47.2-56.5)
16.3% SPP
(12.4-20.2)
12% mortality in
100% SPP
12% mortality in
100% SPP
20% mortality in
100% SPP
Positive Controla
(96-h LC50 & 95% CL)
5.8 ppirf1
(4.3-7.6)
7.5 ppm
(6.9-8.1)
7.3 ppm
(6.6-8.1)
3.4 ppm
(2.8-4.1)
Same as for ffl
6.O ppm
(5.4-6.6)
Definitive Testb
(96-h LC50 & 95% CL)
3.3% SPP
(3.0-3.5)
62.1% SPP
(58.3-65.4)
20.3% SPP
(15.8-24.3)
B
>50v < I 001. SPP
>\C& <50/0 SPP
ti5.4% SPP
(M.-1-80.-I)
2H.3'i SPP
(27.2-31.5)
Sante as for (tti
SuJiie as for #3
68.2% SPP
(55.0-87.4)
30.0% SPP
(27.7-32.3)
H calculations hy
rui'.e; no correction for control mortality unless stated.
'' i it h.'ului. mns l>v SAS"01 pruhit; coi'rv CL ton lor all control mortality. Analyses pt-rformed H. Clifton Duiley,
U.S. I'.PA, Pny.niiM inu.'gniLion uini l>!vul nation Staff (WM-586), Office of Water Itegulations and Standards,
W.islu n^ Li >n , IK' ',i(t Uil).
c ']'li«..- t>iis|K.-ii(ti.'il |»art iculuLe pliabo (SPl') was profiartxl hy mixing 1 part drilling fluid with y parts sea water.
There lore, ihcse valuet, should be multiplied hy 0.1 in order to relate the l;y dilution tested to the SPP
l he whole drilling fluid.
(l Corrected for 13% control mortality.
-------
TABLE 4. Generic drilling fluid concentrations, based on volumetric preparations
of the suspended particulate phase (SPP); and weight of suspended
material in the SPP in tests at U.S. EPA, Gulf Breeze, Florida.
Fluid
#1
#2
#3
#4
#5
#6
#7
#8
Date
SPP prepared
15 Aug 83
25 Aug 83
22 Aug 83
18 Aug 83
15 Aug 83
29 Aug 83
29 Aug 83
22 Aug 83
SPP (g/t)
10.54
18.66
25.12
0.0018
0.1570
0.866
17.12
32.19
SPP 96-h LC50
uA/i;ppn* u£/i;ppnk
27,000 2,700
516,000 51,600
163,000 16,300
e
c
c
654,000 65,400
293,000 29,300
a Based on 1:9 dilution.
b Corrected for 1:9 dilution.
c No median effect (50% mortality) occurred in 100% SPP.
16
-------
Table 5. Relationship of the weight of suspended material in the suspended
particulate phase of eight generic drilling fluids to toxicity
teats conducted at U.S. EPA, Gulf Breeze, Florida.
Fluid
*4
#5
#6
#1
#7
*2
#3
#8
SPP (g/l)
0.0018
0.1570
0.866
10.54
17.12
18.66
25.12
32.19
96-hour SPP* LC50
b
b
b
2.71
65.4
51.6%
16.3%
29.3%
a The suspended participate phase (SPP) was prepared by mixing 1 part
drilling fluid with 9 parts seawater. Therefore, these values should be
multiplied by O'.l in order to relate the 1:9 dilution tested to the SPP
of the whole drilling fluid.
b No median effect (50% mortality) occurred in 100% SPP.
17
-------
TABLE 6. Results of three acute toxicity tests conducted with mysids (Mysidopsis
and generic drilling fluid #1 at U.S. EPA, Gulf Breeze, Florida.
'" data are given as percentages.
Exposure Concentration (SPP4)
Test
Range-finding
Definitive #1
Definitive #2
Control
10*
8%
5%
1
10%
15%
11%
2 2.5 3 4 5
_
18% 100%
11% - 42% 80% 100%
7.5 10 50
100% 100%.
100% 100% -
-
100
100%
-
-
a The suspended participate phase (SPP was prepared by mixing 1 part drilling fluid
with 9 parts seawater). Therefore, these values should be multiplied by 0.1 In
order to relate the 1:9 dilution tested to the SPP of the whole drilling fluid.
18
-------
TABLE 7. Results of acute toxicity tests with mysids (Mysidopsia bahia) and two
generic drilling fluids conducted at U.S EPA, Gulf Breeze, Florida,
and Narraganaett, Rhode Island, during August-September 1983.
Test Location
Gulf Breeze
Drilling Fluid 96-hour SPP* LC50
#1 2.7%
#5 No Median Effect15
95% Confidence Limits
2.5-2.9%
Narragansett
#1
#5
2.8%
No Median Effect5
2. 5-3. Ot
a The suspended particulate phase (SPP) was prepared by mixing 1 part drilling
fluid with 9 parts seawater. Therefore, these values should be multiplied by
0.1 in order to relate the 1:9 dilution tested to the SPP of the whole drilling
fluid.
b No median effect (50% mortality) occurred in 100% SPP.
19
-------
TABLE 8 Comparative acute toxicity of two generic drilling fluids without
and with mineral oil tested with raysids (Mysidopsis bahia) at U.S.
EPA, Gulf
Drilling Fluid*
#2
#2-01
#2-05
#2-10
#8
#8-01
#8-05
#8-10
Breeze, Florida, during August-October, 1983.
96-hour SPP15 LC50
51.6%
13.5%
1.3%
0.49%
29.3%
7.1%
0.90
0.76%
95% Confidence Limits
47.2-56.5%
11.1-16.9%
1.4-2.2%
0.39-0.62%
27.2-31.5%
5.7-9.0%
0.74-1.1%
0.63-0.87%
a The two digits following the generic drilling fluid nunber indicate the
percentage of mineral oil in the fluid.
b The suspended particulate phase (SPP) was prepared by mixing 1 part drilling
fluid with 9 parts seawater. Therefore, these values should be multiplied
by 0.1 in order to relate the 1:9 dilution tested to the SPP of the whole
drilling fluid.
20
-------
TABLE 9. Results of acute toxicity tests with mysids (Mysidopsis bahia) and
two generic drilling fluids containing mineral oil. The tests were
conducted at U.S. EPA, Gulf Breeze, Florida, during September-October
1983. All LCSO's and 95% confidence limits were calculated by the
moving average method.
Drilling
Fluid
2-01
2-05
2-10
8-01
8-05
8-10
Range-finding
Test (median effect)
>10 <50% SPP*
>1 <10% SPP
<1% SPP
>1 <10% SPP
>1 <10% SPP
<1% SPP
Definitive Test
(96-h LC50 4 95% CL)
13.5% SPP
(11.1-16.9)
1.8% SPP5
(1.4-2.2)
0.49% SPP
(0.39-0.62)
7.1% SPP
(5.7-9.0)
0.90% SPP
(0.74-1.1)
0.76% SPPC
(0.63-0.87)
Positive Control
(96-h LC50 4 95% CL)
5.3 ppn
(4.6-6.1)
7.1 ppmc
(6.4-7.9)
7.1 ppmc
(6.4-7.9)
4.3 ppm
(3.7-4.9)
5.6 ppmc
(5.0-6.4)
5.3 ppm
(4.6-6.1)
a The suspended particulate phase (SPP) was prepared by mixing 1 part drilling
fluid with 9 parts seawater. Therefore, these values should be multiplied by
0.1 in order to relate the 1:9 dilution tested to the SPP of the whole drilling
fluid.
b Corrected for 13% control mortality.
c Corrected for 15% control mortality.
21
-------
TABLE 10. Results of three acute toxicity tests conducted with mysids (Mysidopsis bahia) and
generic drilling fluid #8-05 (5% mineral oil) at U.S. EPA, Gulf Breeze, Florida.
Mortality data are given as percentages.
Exposure Concentration (frSPt^)
Test Control 0.5 0.625 1.0 1.25 2.0 2.5 4.0 5.0 8.0 10 5O 100
Hange-finding 0 - -20%-- -- -- 100% 100% 100%
Definitive til 17% - 40% 63% 72% - 95% - 100% - -
Definitive *2 1UX 30% - 48% - 88% - 95% - 100% - -
* __
a The sus|*-nded particulute phase (SPP) was prepared by mixing 1 part drilling fluid with 9
parts seawater. Therefore, these values should be multiplied by 0.1 in order to relate the
1:9 dilution tested to the SPP of the whole drilling fluid.
ro
ro
-------
APPENDIX A
CHEMICAL AND PHYSICAL CHARACTERISTICS OP THE MINERAL OIL USED IN THE
LABORATORY-PREPARED GENERIC DRILLING FLUID TESTS
1. Mineral oil analysis reported by IMOO Services, drilling fluid #2
Boiling range (IBP-FBP)
Vapor pressure
Vapor density
Solubility in water 9100°F
Specific gravity
Percent volatile by volume (%)
Evaporation rate
Flash point (Pensky-Martens)
500-610°P
0.008
>8
30 ppn
0.845
100
<0.01
255° P
2. Mineral oil analysis reported by Dowell, drilling fluid #8
op
op
ppn
Chemical name
Chemical family
Formula
Boiling point, IBP,
FBP,
Vapor pressure (mm Hg) , 20°C
Vapor density (air § 1)
Solubility in water § 100° P,
Specific gravity (water » 1)
Percent volatile by volume, %
Evaporation rate (n-Butyl acetate
Appearance and odor
Gravity, °API at 60° F
Flash point, COC, °F
Pour point, °P
Color, ASTM D 1500, Saybolt color
Viscosity. cSt at 40°C
SSU at 100 °P
1)
Paraffin - base oil
Petroleum hydrocarbon
Complex misture of petroleum hydrocarbons
500
610
0.008
>8
30
0.845
100; evaporates slowly at 100°F
<0.01
Clear light color. Slight kerosenic odor
35.8
258 (Pensky - Martens 255°F)
5
28
4.2
41.0
This oil is stable, but strong oxidants such as liquid chlorine, concentrated
oxygen, and sodium or calcium hypochlorite should be avoided.
23
-------
APPENDIX B
MORTALITY DATA
Test Drilling SPP* Test
Location Fluid Concentration
Gulf Breeze #1 Control
1%
2%
3%
4%
5%
#2 Control
10%
30%
50%
70%
90%
#3 Control
10%
20%
30%
40%
50%
Mysids
Exposed
60
60
60
60
60
60
60
60 -
60
60
60
40
60
60
60
60
60
60
Mysids
Killed
3
11
11
25
48
60
4
3
9
9
49
39
6
15
39
39
45
53
Percentage
Mortality
5
18
18
42
80
100
7
5
15
15
82
98
10
25
65
65
75
88
(continued)
a The suspended particulate phase (SPP) was prepared by mixing 1 part drilling
fluid with 9 parts seawtaer. Therefore, these values should be multiplied by
0.1 in order to relate the 1:9 dilution tested to the SPP of the whole drilling
fluid.
24
-------
APPENDIX B, continued.
Test Drilling
Location Fluid
Gulf Breeze #7
#9
Narragansett #1
Sppa Test
Concentration
Control
20%
40%
60%
80%
100%
Control
10%
20%
30%
40%
50%
Control
1.0%
2.5%
5.0%
7.5%
10%
Mysids
Exposed
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
Mysids
Killed
2
13
21
21
37
41
1
0
11
31
42
56
1
1
5
5
60
HO
Percentage
Mortality
3
22
35
35
62
68
2
0
18
52
70
93
2
2
8
100
LOO
100
(continued)
25
-------
APPENDIX B, continued.
Test Drilling SPP* Test
Location Fluid Concentration
Gulf Breeze #2-01 Control
2.5%
5%
10%
20%
40%
#2-05 Control
1%
2%
4%
3%
16%
#2-10 Control
0.25%
0.5%
1%
2%
4%
Mysids
Exposed
60
60
60
60
60
60
60
60
60
60
60
60
60
GO
60
60
60
60
Mysids
Killed
1
12
16
21
26
56
8
22
37
50
57
60
4
17
29
46
49
60
Percentage
Mortality
2
20
27
35
43
93
13
37 '
62
83
95
100
7
28
48
77
32
100
26
-------
APPENDIX Bf continued.
Test Drilling SPP* Test
Location Fluid Concentration
Gulf Breeze #8-01 Control
1.9%
3.2%
5.4%
9%
15%
i^S-05 Control
0.5%
1%
2%
4%
8%
#8-10 Control
0.5%
1%
2%
4%
8%
Mysids
Exposed
60
60
60
60
60
60
60
60
60
60
60
60
60
60
60
tfO
60
60
Mysids
Killed
5
6
15
28
31
44
6
18
29
53
57
60
9
23
43
57
60
60
Percentage
Mortality
8
10
25
47
52
73
10
30
48
88
95
100
15
38
72
95
100
100
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