SPE 80593
Development Practices and Achievements for Reducing the Risk of Oilfield Chemicals
Donald G. Hill, SPE; Keith Dismuke, SPE; William Shepherd; Irena Witt, SPE; Henk Romijn; Wayne Frenier, SPE; Mike
Parris; Schlumberger
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE/EPA/DOE Exploration and Production
Environmental Conference held in San Antonio, Texas, U.S.A., 10–12 March 2003.
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Abstract
An effective approach to the global issue of chemical
management, based on Gulf Coast and North Sea experience
in wellbore stimulation, is described. This paper presents the
results of aggressive chemical development and replacement
programs for stimulation chemicals for worldwide application.
Development of more environmentally acceptable products
requires working with regulatory agencies, clients, and
chemical suppliers to achieve regulatory compliance for
MSDS, labels, and environmental testing protocol. This paper
recognizes that international environmental statutes and
guidelines combined with clear corporate goals to minimize
environmental impact are key requirements in regulating
industrial use and discharge of environmentally harmful
chemicals. The development of more environmentally
acceptable products requires a thorough screening of
environmental fitness and status of compliance with relevant
laws and regulations.
Oilfield chemicals have primary active ingredients that
may be harmful if discharged to the environment. Improving
the characteristics of these products to reduce risk or damage
to marine life requires changes in previously acceptable
products, such as elimination of restricted materials and
incorporation of components with improved
ecotoxicity values.
Details are given on the aggressive programs developed to
address a wide range of environmental opportunities and
issues. International environmental statutes and guidelines are
the strongest driving force to restrict industrial use and
discharge of environmentally harmful chemicals. The primary
tool of environmental risk reduction is an aggressive product
development program incorporating more environmentally
friendly chemical solutions. The paper will also present three
years of field results achieved using environmentally
improved stimulation products.
Introduction
This paper describes an improved product development
process that emphasizes health, safety and environmental
(HSE) awareness throughout the entire product lifecycle.
Various international regulations that impact product
development will be reviewed. Two new products that were
developed using the improved process resulted in technically
superior formulations and a smaller HSE footprint than the
chemical products replaced.
Product Development Process
Oilfield chemical products are incorporated into a fluid design
to solve a specific technical wellbore or matrix problem in a
well, such as stimulation; water, sand and scale control; or
damage removal. These products may have primary active
ingredients that may be harmful if discharged to the
environment. Improving the characteristics of these products
to reduce the risk of damage to marine life requires changes in
previously acceptable products, such as eliminating restricted
materials and incorporating components with improved
ecotoxicity values.
The development of chemical products is a well-known
process that has improved over time; however, increased
awareness of HSE factors and regulations has refined the
process. This new process is a further refinement of the HSE
assessment process described by Purinton and Manning and
Hill for applications in the North Sea.1, 2
The Chemical Product Lifecycle Management Process (C-
PLMP). A well-defined process, known as C-PLMP, covers
the “cradle-to-grave” lifecycle of a chemical product. Each
step of the process offers guidelines for critical product
development activities. The process implemented contains the
following major component phases (also shown in Fig. 1):
Concept. The most fundamental questions are answered
through research, laboratory experiments and computer
simulation before undertaking the expense of developing field-
worthy products. It must be agreed that the underlying science
and technology are sound, that no major regulatory, safety or
environmental obstacles are anticipated, and that the proposed
product addresses a well-defined market need.
Feasibility. The technical basis for the product, based on
initial user specifications, is proven. At the end of this phase,
management should know the product definition, the markets
addressed, the product risks and potential benefits, the product
cost and potential revenue, and profitability. There should be
no remaining uncertainties about the underlying chemistry or
2 SPE 80593
physics. An initial risk assessment is completed to identify
environmental, safety, operational and regulatory issues. The
performance and reliability of key chemical components
should be proven with a thorough testing program.
Development. All performance and environmental testing
plus analytical characterization are completed to allow
successful introduction and implementation of the product in
the field. This phase includes laboratory studies, product
quality assurance/quality control procedures, and compati-
bility with field equipment. A final data acceptability review
for process modeling and equipment is performed to
determine readiness for the field-testing phase.
Field Test. The technical and marketing components set
out in previous phases are validated, which include chemical
system performance versus specifications, manufacturing
scale-up, quality assurance, logistics, safety, applications,
operational issues, perceived value, and related HSE factors.
Validation is done through customer testing in a representative
set of commercial environments.
Commercialization. The first phase of commercialization
is completed with conformation that the technology is ready
for deployment and technical documentation is completed.
The final major checkpoint, the decision to launch a product,
is made. No major changes to the product are permitted at this
time. The marketing plan, including the business and product
introduction plans, is implemented. The product is transferred
to the Sustaining group.
Sustaining. Key efforts are made to guarantee that
continued manufacture maintains the product specifications
and supports product application in the field. The Sustaining
effort maintains the product, including replacing with more
cost effective or improved performance products, and
updating the documentation.
Obsolescence. Eventually, the product may no longer be
commercially or environmentally viable. This situation occurs
when a newer product addresses the same market needs, or the
market changes and the original product is no longer required
or allowed.
The HSE Guidelines of the C-PLMP Process. Through
continuous improvement, the process has been refined with
special emphasis placed on technical robustness and risk
analysis. HSE considerations are also significant for effective
product application development. HSE issues are recognized
as a critical part of corporate citizenship, lifecycle
management and risk reduction.
HSE Assessment. An HSE assessment, including a
regulatory assessment, is initiated in the Concept phase. HSE
issues are reviewed frequently at each step of the process,
from Concept through Obsolescence.
Restricted Chemicals. In general, certain chemicals
should be avoided because they are likely to cause
unacceptable HSE liability and regulatory risks. As a result,
customer acceptance will be poor. These are chemicals that
are highly toxic to animals or aquatic species, carcinogens,
organohalogens (nonpolymeric), ozone depletors, US
Environmental Protection Agency (EPA) listed Extremely
Hazardous Materials, listed Marine Pollutants and arms
control substances. The key regulatory listings depend on
geographic area. Table 1 provides a list of
reviewed documents.
Environmental Fate. The product’s toxicity to mammal,
fresh water or marine species must be known to assess its
effect on personnel health and environmental health. The
product’s persistence in the environment is a critical issue.
The tendency of the chemical to bioaccumulate or its ability to
biodegrade in the use environment must be determined, and
are critical to product acceptance.
Physical/Chemical Properties. Flammability, corrosive-
ness and reactivity are also keys to product robustness. Each
of these factors affects personnel safety while handling the
chemical. Alternatives to minimize flammability and
corrosiveness must be explored. Use of products with
spontaneous chemical reactivity must be avoided.
Exposure Hazards. Health hazards are equally important.
Inhalation, ingestion, and skin absorption are evaluated.
Regulatory Assessment. The C-PLMP recognizes that
regulations vary between geographic areas. Compliance within
each geographic area must be met, although North Sea
requirements are the most detailed in the process. The need for
verification of environmental data may increase when
individual countries design test protocols to meet their
geographic needs. Compliance very quickly becomes a costly
issue because of the number and variability of tests required.
Efforts to harmonize testing requirements for product
registration and acceptance are desirable. Failure to comply
with individual country registrations may result in heavy fines
and exclusion from that market.
Country Registrations. Many countries require that a
chemical or product be registered before it can be used. Proof
of product toxicity to designated species and environmental
fate must be provided prior to review and acceptance. This
paper reviews the registration USA, Canada, and the European
Union (EU), including the North Sea countries.
Implementation of HSE Guidelines. The C-PLMP
process follows HSE guidelines for product development
activities (see Fig. 2). HSE concerns are identified at the
beginning. For each phase of development, environmental
robustness is reviewed.
Concept. Determine whether any major HSE or regulatory
obstacles are anticipated for candidate components.
Feasibility. A formal HSE and regulatory assessment
identifies the detailed requirements.
Development. The HSE and regulatory assessment are
reviewed, and a follow-up plan is created to address the
requirements of the chemical. An HSE justification must also
be prepared to address the following questions. These
questions must be answered before completing the
environmental fate testing required for the product:
• Are all the chemical components required?
• Why was this/these chemical(s) selected?
• In what environments will the chemical(s) be used?
• What happens with the chemical(s) in the environment?
• Is the environmental impact reduced when compared to
similar products used in oilfield applications?
• Does this product enhance the technology?
SPE 80593
Field Testing. HSE and regulatory follow-up plans are
implemented. No field test is permitted where regulatory
compliance is not completed.
Commercialization. Verify completion of HSE and
regulatory plans to ensure there are no surprises. Regulatory
compliance is completed and MSDSs and labels are provided.
Sustaining. Respond to changes in regulations or new
regulations as needed.
Obsolescence. Deplete chemical inventory and implement
waste disposal procedure for any remaining material,
if needed.
Regulatory Guidelines
Since the 1970s, regulations have noticeably shifted emphasis
when major environmental statutes were established in
response to ecosystem pollution by man-made chemicals.
Stringent laws and regulations, followed by investments in
developing cleaner and dedicated environmental technologies,
mitigated the most severe effects of soil and air pollution in
industrialized countries. In the past two decades, regulatory
bodies and scientific communities have confronted new
aspects of environmental issues: 3
• global impact of pollution
• pollution prevention through applications of less toxic,
“greener” chemicals
• development of new computer modeling tools for
assessing environmental impact.
Several US and international events have made the
general public aware of the global impact of pollution and the
use of greener chemicals to mitigate damage. Less well known
is the use of computer modeling by regulators in
characterizing the impact of chemical exposure while
assessing new chemicals for release to the market.
To illustrate the complex web of international regulations
for the protection of marine ecosystems, this paper will cite
differences among the three major international environmental
jurisdictions of the EU, USA and Canada.
The EU. The Oslo Paris Commission (OSPAR) regulates the
offshore use of chemicals. Although the regulations are often
referred to as North Sea regulations, OSPAR actually is the
Convention for the Protection of the Marine Environment of
the Northeast Atlantic, which is much wider than just the
North Sea.
OSPAR developed programs and measures to identify,
prioritize, monitor and control the emissions, discharges and
losses of hazardous substances that reach, or could reach, the
marine environment. To this end, OSPAR implemented the
Harmonized Mandatory Control Scheme (HMCS).
HMCS. The use of offshore chemicals in North Sea
countries is strictly regulated. All chemicals that are used and
discharged to the sea must be tested in accordance with the
requirements that are specified in the HMCS.4 The results of
the tests are reported using the Harmonized Offshore
Chemical Notification Format (HOCNF). This format requires
the determination of the toxicity of the product on three
different marine species, as well as assessing the potential for
each component in the product to bioaccumulate
or biodegrade.
3
Recently OSPAR has decided that also the toxicity tests
should be preformed on the components rather than on the
complete products. The regulation will be in force as of
January 2004 for new chemicals. By 2007 component data
must be available for all products.
The HMCS has two important tools for evaluating
environmental properties of chemicals: the Prescreening
Scheme (Fig. 3) and the Chemical Hazard and Risk
Management (CHARM) model (Fig. 4). Prescreening schemes
allow authorities to identify substances used in offshore
chemicals with the aim of
• substituting, and ultimately phasing out, those
substances that are hazardous
• regulating and controlling the other substances,
where necessary.
It should be noted that prescreening applies only to
chemicals used or discharged as a result of offshore activities.
The criteria used in the prescreening are acute toxicity to
marine species, the biodegradation and the bioaccumulation
potential, or a combination of these properties. It appears that
biodegradation and bioaccumulation play dominant roles.
Based on the outcome of prescreening, the regulatory agencies
may decide to
• give permission to use
• request substitution
• give temporary permission
• refuse permission.
Products that pass the prescreening scheme must be
ranked using CHARM (Fig. 4). This model, developed under
the sponsorship of both the regulating authorities and the
European Oilfield Specialty Chemicals Association (EOSCA),
calculates the Hazard Quotient (HQ), which is the ratio
between the Predicted Environmental Concentration (PEC)
and the Predicted No-Effect Concentration (PNEC): 6
HQ = PEC/PNEC .......................................................... (1)
When the ratio is 1 or less, no effect on the environment
is to be expected. The HQ is calculated for an “average
platform” under “realistic worst case conditions.” Many
default values are used, and safety factors and worst cases
have been built in. There are on-going discussions on how
CHARM will be applied.
The use of the CHARM model for assessment of the
chemical products was phased in for use after March 2002.
The HMCS regulations are implemented differently for the
countries within the North Sea sector. Until March 2002, the
UK classified the products into Group A through E.5 Group A
represents the most environmentally hazardous products
whereas Group E represents the products with least
environmental hazard based on marine toxicity,
biodegradation and bioaccumulation. The Groups are often
reviewed and used by other countries. They give a ready
indication of the environmental hazard; however they do not
indicate the potential risk of the product.
Norway interprets the regulations similarly. Based on the
criteria for chemical products containing organic components
with low biodegradation and high bioaccumulation (log Pow),
the compounds are restricted in the following order (according
to OECD test guidelines): 4
4 SPE 80593
• biodegradation <20% and Log Pow >3 and MW < 600
• biodegradation 20%−60% and Log Pow > 3
• biodegradation < 20%.
Recognition is growing that health factors play a
secondary role in the OSPAR regulations, as they exist today.
Health factors should receive more attention and,
consequently, should be seriously considered when developing
chemical products. Starting in 2003 The Netherlands have
introduced legislation that combines the human health factors
with the HMCS.
The USA. Regulations concerning the use of chemicals in
offshore oil and gas operations focus on controlling the
pollutant properties and contents in effluent discharges
resulting from well chemical treatments. Prescribed toxicity
testing methods specify organisms that are indigenous to
US regions.
Highlights of the NPDES Permit. Offshore waste
discharges are regulated by National Pollutant Discharge
Elimination System (NPDES), pursuant to section 402 of the
Clean Water Act (CWA), which is administered by the EPA.
In addition, discharges of drilling cuttings must comply with
requirements of Ocean Discharge Criteria of section 403(c) of
the CWA.
The EPA’s approach with regard to oil and gas exploration
and production is regulating flow back offshore discharges
that originate from these processes.7, 8 Assessing
environmental impact is based on discharge volumes; a
discharge permit is issued with prescribed monitoring
requirements and effluent limitations. In short, for well
treatment fluids, completion fluids and work over fluids, the
following limitations apply:
• Free oil. No free oils shall be discharged. Monitoring
shall be performed using the static sheen test.
• Oil and grease. A daily maximum of 42 mg/L, and
monthly maximum of 29 mg/L must not be exceeded.
• Priority pollutants. Prohibition of discharge of toxic
pollutants, pursuant to statute 40, Code of Federal
Regulations (CFR), Part 401.15 list of 65 chemicals.
(This Code is published by the Federal Register.)
The CWA prohibits discharges of chemical pollutants into
navigable waters, except in compliance with statute 40 CFR,
Part 401.15. The list specifies 65 toxic pollutants that are
prohibited from being released into navigable waters of the US
except in trace amounts. The Act also focuses on establishing
restrictions on the types and amounts of any other chemical
pollutants discharged.
Canada. Regulations of offshore drilling and production
activities under jurisdiction of Newfoundland and Nova
Scotia, the most prominent Canadian offshore oil and gas
activity regions, were promulgated and executed by the
National Energy Board (NEB), the Canada-Newfoundland
Offshore Petroleum Board (C-NOPB) and the Canada-Nova
Scotia Offshore Petroleum Board (C-NSOPB). Generally
speaking, these regulations combine elements of EU and USA
offshore effluent discharge regulations: they include selection
of chemicals, as well as waste ocean disposal guidelines. Two
fundamental guidelines cover recommended practices and
standards: the Offshore Chemical Selections Guidelines and
the Offshore Waste Treatment Guidelines in Canada.9, 10
Offshore Chemical Selections Guidelines, January
1999. These Guidelines provide a consistent framework for
chemical selection as part of the environmentally responsible
management of chemicals used in offshore drilling
and production.
The regulatory framework specified by the Guidelines is
based on the legislation of all three previously mentioned
authorities, which are collectively referred to as the Energy
Legislation. The Guidelines include general regulatory
requirements under Canadian laws and recognition of the
obligations set forth by international marine
protection agreements.
The process of obtaining authorization requires operators
to demonstrate results of their selection of chemicals
equivalent to those achieved when applying the Guidelines.
Selection criteria include a number of steps, which are listed in
Table 2.
Offshore Waste Treatment Guidelines, September 1996.
General provisions of the Waste Treatment Guidelines reduce
the volume of waste being discharged and the concentrations
of contaminants. Discharge permit requirements target the
following discharges containing chemicals:
• Produced water and dispersed oil content. Up to 40
mg/L, as averaged over a 30-day period, are allowed,
and a strict monitoring schedule applies.
• Drilling muds. Water-based or synthetic-based muds
are preferred.
• Drilling solids. Particles generated by drilling into
geological formations and carried to the surface with
drilling muds.
• Well treatment fluids. Fluids containing diesel oil or
other highly aromatic oils are not allowed. Strongly
acidic fluids require neutralizing prior to discharge.
Detailed chemical and toxicological information is submitted
to the appropriate regulatory representative, and a monitoring
schedule of pollutant levels is set in place.
Developing Chemicals for Worldwide Application
Companies that operate in offshore waters around the world
are faced with the difficult task of developing products that
• perform the job that they are designed to do
• meet environmental requirements in various parts of
the world
• have the lowest possible risk to human health
and safety.
Meeting all environmental requirements is difficult
because of the lack of harmonization of the regulations.
Nevertheless, an HSE assessment process has been designed
that covers most of the issues discussed in this paper. Before
starting a product development project that includes the use of
chemical products, an assessment is made of those products.
The results play an important role in the decision on whether
the development project can continue.
In Norway, the regulations set clear targets for operators
to phase out chemicals that will not naturally biodegrade or
have the potential to bioaccumulate in the food chain.
Chemical components that are suspected of having endocrine
SPE 80593
disrupting effects, such as certain alkyl phenols, are prohibited
from discharge. Clients have also set aggressive targets for
minimizing discharges to the North Sea, including the "zero
discharge" strategy in Norway, replacing harmful chemicals
with more environmentally friendly alternatives.
For many applications, this is technically very
challenging; it requires a commitment from chemical suppliers
to drive the development in a greener direction.
Achievements of Improved Guidelines. HSE considerations
affect the selection of chemical components at project
initiation. These considerations reduce the risk of
environmental and regulatory noncompliance and thereby
minimize the need for product replacement. Increasingly
proactive product development allows logical product line
extensions based on environmental improvements. Reduced
safety and environmental risks are also realized for short-term
and long-term application.
An HSE mindset leads to improved efficiency of product
development resources; it also avoids developing products that
are undesirable for HSE reasons. Examples of several products
developed through this continual improvement process
are discussed.
Development of a Biodegradable Chelant. The
development and field-testing of formulations containing
hydroxyethyliminodiacetate (HEIDA) salts for use in oilfield
stimulation fluids is described. Chelating agents are materials
that are used to control undesirable reactions of metal ions. In
oilfield chemical treatments, chelating agents are frequently
added to stimulation acids to prevent precipitation of solids as
the acid spends on the formation being treated.11 These
precipitates include iron hydroxide and iron sulfide. In
addition, chelating agents are used as components in many
scale removal/prevention formulations. This current study is
related to development of improved and biodegradable
polyaminocaboxylic acid chelating agent formulations.
Chelating formulations based on
ethylenediaminetetraacetic acid (EDTA) have been used
extensively to control iron precipitation and to remove scale.
Formulations based on nitrilotriacetic acid (NTA) and
diethylenetriaminepentaacetic acid (DTPA) also are in use. 12,
13
Each of these materials has problems: 1) EDTA and DTPA
have low solubility in hydrochloric acid and are not
biodegradable. 2) NTA is acid soluble and biodegradable, but
has a lower stability constant for iron than EDTA (or DTPA)
and may be classified as an animal carcinogen.
Sodium HEIDA has been proposed 14, 15 for all of the
formulations requiring EDTA-type chelating agents, including
those for iron control during acidizing, scale removal
treatments, and well cleanout operations. HEIDA biodegrades
much more easily than EDTA or DTPA and has a much
smaller environmental footprint than these chemicals. HEIDA
is more soluble in HCl than EDTA, and therefore can control
more Fe3+ than EDTA. The new formulation can be used to
dissolve calcite and gypsum scale. It also can be used in acidic
or alkaline well cleanout formulations with surfactants and
mutual solvents. Field trials have shown that HEIDA
formulations can be 1:1 substitutes for EDTA in oil and gas
well treatments.
5
Previous work4 has proven that the solubility of the sodium
salts of HEIDA in mineral acids are much higher than for
those of EDTA .A major use for chelating agents is to stabilize
iron in solution during matrix acidizing treatments. A number
of “recovery” tests were run. Solutions containing various
amounts of Fe3+ and concentrations of EDTA or HEIDA were
spent by addition of calcium carbonate to pH 3.5-3.8. The
slurries were aged at various temperatures from ambient to
190°F for 6 hr. At the end of the tests, the iron concentration
was determined using ICP and the percentage of the expected
iron concentration (percent recovery) was calculated. The
volumes of chelating agents listed are the optimal
concentrations for the particular test. The recovery values
were usually >80%, even at 190°F. The HEIDA formulation
controlled iron as effectively (using less chemical) as the
EDTA formulation. Fig. 5 shows the recommended volume
concentrations of sodium HEIDA and sodium EDTA at
various ferric iron concentrations. Note that EDTA is not
listed in the graphic at 5,000 ppm because the amount of this
chelating agent needed to control 5,000 ppm Fe3+ will cause a
precipitate to form at temperatures <70°F. This characteristic
will cause surface-handling problems for use of high
concentrations of EDTA in many locations worldwide.
Biodegradation tests4 run on the sodium salts of the
chelating agents, using several different protocols, as shown in
Table 3, HEIDA was found to be biodegradable in 8 of 8
standard laboratory tests performed, including Organization
for Economic Cooperation and Development (OECD) 306
protocols run by the closed-bottle method in North Sea water.
HEIDA also passed an OECD 306 test performed in Gulf of
Mexico water using CO2 evolution for measuring degradation.
NTA was included in the Gulf of Mexico water test, but did
not reach a passing level of degradation within the 28-day test
period. As can be seen from the various test method results
summarized in Table 6, HEIDA tends to show a more rapid
rate of degradation than NTA.
The acute toxicity values for sodium HEIDA with various
aquatic and marine species15 are compared in Table 4. Note
that toxicity is inversely proportional to the concentrations
required to cause a certain effect. The tests on mammals are
used as a model for human exposure. The acute toxicity values
for the rats are very low. Irritation tests using rabbits and
guinea pigs (data not shown) concluded that the skin and eye
irritation of sodium HEIDA would be minimal. Aquatic
species that model response of fresh water and seawater
organisms also were tested. The lethal concentrations (LC)
and effect concentrations (EC) were all above 100 mg/L,
indicating that there should be minimal impact on the aquatic
environment. Note that rainbow trout and daphnia magna are
used to determine the response in fresh water, and the other
organisms are used to gauge the effect on saltwater (especially
North Sea) creatures.
The use of chelating agent formulation with small
amounts of inhibitors (compared with concentrated HCl with
large amounts of inhibitors) significantly lowers the exposure
of well site personnel to toxic or very irritating chemicals.
Development of “Green” Polymer Slurry System. To meet
stringent environmental guidelines in both the U.K. North Sea
and in the Gulf of Mexico (GOM), a new environmentally
improved polymer slurry system was produced that delivers
6 SPE 80593
consistent, nondamaging performance. The slurry system
developed for use in fracturing and gravel-packing operations
in environmentally sensitive regions features a unique carrier
fluid that delivers a polymer into the mix water for ease of
mixing and use. This systems may be used for applications
where dry polymer or polymer slurried in hydrocarbon fluids
were previously used. These slurried polymer systems may be
used offshore and land environments where continuous and
batch-mix operations are employed.
Traditional fracturing fluids are made of biodegradable
guar polymer slurried and transported in a hydrocarbon base.
Diesel fluid is commonly used as the hydrocarbon carrier;
however diesel is hazardous to handle and is environmentally
undesirable. Diesel is the most commonly used carrier fluid
used and therefore poses problems in ecologically sensitive
areas The novel carrier fluid eliminates metering and issues of
environmental conformance associated with the use of diesel.
Fluid description. The environmentally improved fluids
consist of a fast hydrating (80% hydration within 2 to 3 min),
high-yield polymer. These polymers may be guar,
hydroxypropyl guar (HPG) or carboxymethylhydroxypropyl
guar (CMHPG). The rate of hydration is independent of
polymer loading, as shown in Fig. 6. The application of these
environmentally improved fluids dramatically reduces or
eliminates the use and generation of hazardous substances.
Field performance. The fluid was field-tested on land
and in the GOM; the environmentally improved slurry system
gave equivalent, and sometimes better, well performance
when compared with traditional fluids. On land, foam fluid
half-life depending on surfactant, increased from 20 to 100%
than normally found with typical land-based fluid systems.
Marine conformance. Data requirements for drilling
fluids and additives vary according to location and legislation,
but may be based on the result of a single species test or a
suite of tests covering many toxicity levels.
The environmentally improved slurry system is already in
compliance with Minerals Management Service (MMS)
discharge regulations8 now planned for enforcement in the
GOM. The MMS discharge requirements for stimulation
fluids in the GOM include:
• Oil and grease limits of 42 mg/l maximum on a daily
basis or 29 mg/l monthly average, and
• Absolutely no sheen, iridescence, gloss or
increased reflectance.
Note that a fracturing fluid made from a polymer / diesel-
based slurry will give oil and grease tests results significantly
higher than observed for the new slurry system. Diesel
slurries result in oil and grease values greater than 1600 mg/l,
and will also fail the static sheen test, as shown in Table 5.
Alternate oils, such as the use of alternate, more
environmentally improved diesels, result in similar oil and
grease values, significantly higher than the acceptable limit
and also fail the static sheen test.
Linear gels made from the slurry system have passed a
number of tests for toxicity for application in the Gulf of
Mexico as well as the North Sea.5, 8 For North Sea application,
the slurry suspension must also pass toxicity tests in addition
to strict guidelines on biodegradation and bioaccumulation.
The shrimp species is indigenous to the warm waters of the
Gulf of Mexico, and is routinely used in toxicity bioassays of
drilling fluids. Tests have been completed for:
• Acartia-tonsa (copepod)
• Skeletonema costatum (diatom)
• Sheepshead minnow (fish)
• Mysidopsis bahia (Mysid shrimp)
The fluids utilizing this technology have received the
highest gold band rating for use in the North Sea, where
requirements for use and discharge are considered to be the
most demanding, and in the Gulf of Mexico. The uniform
slurry system can be pumped in marine environments
throughout the world and in other environmentally sensitive
areas on land.
Conclusions
1. A well-defined chemical development process, referred to
as a C-PLMP, covers the “cradle-to-grave” lifecycle of a
chemical product and identifies the potential
HSE-related issues.
2. HSE considerations affect selection of chemical
components at project initiation, resulting in reduced risk
of environmental and regulatory noncompliance.
3. The increasingly proactive product development process
allows logical product line extensions based on
environmental improvements.
4. Reduced safety and environmental risks are also realized
for short-term and long-term application.
5. The HSE mindset of developers leads to improved
efficiency of product development resources.
6. Numerous products deployed to the field have illustrated
the benefits of this program.
7. The continuous improvement program has resulted in
products that offer improved environmental performance
without compromising technical performance. In fact,
technical performance has often significantly improved.
Acknowledgments
The authors appreciate the support from Schlumberger
Oilfield Services for the completion of this work and their
permission to publish this report.
Metric Conversion Factors
m x 3.281 = ft
°C x 1.8 + 32 = °F
kg/cm2 x 14.223 = psi
ml = cm3 = 0.061 inch3
ppm = 8.34 lb/1,000 gal
SPE 80593 7

References
1. Purinton, R. J., Manning, T. S.: “The Role of HSE in Chemical
Product Development,” SPE 35822 presented at the 1996
International Conference on Health Safety and Environment,
New Orleans, Louisiana, June 9-12.
2. Hill, D.G., et al.: “The Role of HSE in Chemical Product
Development,” SPE 74085 presented at the 2002 International
Conference on Health Safety and Environment, Kuala Lumpur,
Malaysia, March 2002.
3. Schuurmann, G., and Markert, B. (ed): Ecotoxicology:
Ecological Fundamentals, Chemical Exposure, and Biological
Effects, New York, NY, John Wiley & Sons (1998), and
Heidelberg, Germany, Spectrum Akademischer Verlag (1998).
4. OECD “OECD Guidelines for the Testing of Chemicals”, Paris,
France (1993).
5. UK CEFAS, “Guidelines for the UK Revised Offshore
Chemical Notification Scheme”, Burnham-on-Crouch, Essex,
UK, January 2001.
6. Thatcher, M., Robson, M., Henriquez, L. R., and Karman, C. C.,
“A User Guide for the Evaluation of Chemicals Used and
Discharged Offshore”, EOSCA (August 1999).
7. US EPA, Office of Pollution Prevention and Toxics: “Pollution
Prevention (P2) Framework,” EPA-748-B-00-001 (June 2000).
8. Federal Register: “EPA: Final NPDES General Permit for New
and Existing Sources and New Discharges in the Offshore
Subcategory of Oil and Gas Extraction Category for the Western
Portion of the Outer Continental Shelf of the Gulf of Mexico
(GMG290000) and Notice of a Proposed Modification to That
Permit” 64, No. 74 (April 19, 1999).
9. National Energy Board, Canada-Newfoundland Offshore
Petroleum Board, Canada-Nova Scotia Offshore Petroleum
Board: “Guidelines Respecting the Selection of Chemicals
Intended to be Used in Conjunction with Offshore Drilling &
Production Activities in Frontier Lands,” (January 1999).
10. National Energy Board, Canada-Newfoundland Offshore
Petroleum Board, Canada-Nova Scotia Offshore Petroleum
Board: “Offshore Waste Treatment Guidelines,”
(September 1996).
11. Crowe, C.W.: “Method of Preventing Precipitation of Ferrous
Sulfide and Sulfur During Acidizing,” US Patent No. 4633949
(1987).
12. Taylor, K.C., et al.: “A Systematic Study of Iron Control
Chemicals used During Well Stimulation- Part 2,” SPE paper
50772 (1999).
13. Paul, J.M. and Fieler, E.R.: “A New Solvent for Oilfield
Scales,” SPE Paper 24847 presented at the Annual Conference
and Exposition held in Washington D.C. (October 1992).
14. Frenier W. W., et al.: “Use of Highly Acid-Soluble Chelating
Agents in Well Stimulation Services”, SPE 63242 (2000).
15. Frenier W. W., et al.: “A Biodegradable Chelating Agent is
Developed for Stimulation of Oil and Gas Formations”, SPE
80597 (2003). Will be presented at the SPE/EPA/DOE
Exploration and Production Environmental Conference held
in San Antonio, Texas, U.S.A., March 2003.
8 SPE 80593

TABLE 1—HAZARD LIST

EU Land-Banned Material
North Sea Banned List
Organohalogens (Non-Polymeric)
CERCLA*/CWA Hazardous Substance Table 302.4
with Reportable Quantity (RQ) 100 lb or less
EPA Extremely Hazardous Materials
Marine Pollutants
RCRA** Waste Code U or P
California Proposition 65
Process Safety Management Chemicals List
ACDA Schedule (Arms Control Substances)
US Health Department Annual Carcinogen Report
Toxic Metals List
* CERCLA – Comprehensive Environmental Response, Compensation and Liability Act
**RCRA – Resource Conservation and Recovery Act

TABLE 2—CANADIAN SELECTION CRITERIA

Step Concern / Action Description
1 Propose chemical for application Determines the overall chem ical acceptability
2 Chemical used as a biocide?
3 Listed on Dom estic Substance List (DSL)?
4 Hazardous to humans? Criterion of carcinogenicity or mutagenicity
5 Discharge to environm ent?
6 Canadian Environm ental Protection Act (CEPA) listed? Prohibited, Toxic, and Restricted List?
7 OSPAR HOCNF Product on Tint List?
8 OSPAR List A or B Product on List A or B?
9 PARCOM (Paris Commission) OCNS Hazard Rating
10 Microtox EC50(15) >75%?
11 Discharge quantity?
12 Hazard analysis? The chemical will be approved or rejected.
13 Hazard analysis process
SPE 80593 9

TABLE 3—TYPICAL BIODEGRADATION DATA IN STANDARD LAB TESTS

(times required for listed degradation rates of <28 days are found in parentheses)

Test for Chelant: EDTA HEDTA NTA HEIDA

OECD 306
1
(28-day) 7
Not tested 0% Not tested 63%
North Sea Water

OECD 306 89% (reached

(28-day)2 Not tested Not tested 54% passing level
Gulf of Mexico Water within 20 days)

OECD 301 B
3 ≥ 80% (~3 ≥ 90% (~ 2
(28-day) < 5% < 5%
wks) wks)
Fresh Water

1
Pass level for ready biodegradability is 60% of theoretical oxygen demand (from OECD Guidelines for Testing of Chemicals,
Section 306, pages 1/27 and 2/27, adopted 17.07.92). This OECD 306 test was performed using North Sea water with no
added inoculums.
2
This OECD 306 test was performed using Gulf of Mexico water using CO2 evolution to measure degradation with no added
inoculums
3
Pass level for ready biodegradability is 60% of theoretical CO2 production (from OECD Guidelines for Testing of Chemicals,
Section 301, page 3/62, and adopted 17.07.92). This test is performed with nonacclimated municipal water.

TABLE 4—TOXICITY TESTS, Na2HEIDA

Turbot
Skeletonema Acratia Rainbow Daphnia Rats Acute Rats Acute
(Scophthalmus
Chemical costatum tonsa trout magna Toxicity Toxicity
maximus)
EC50-48 LC50-48 LC50-96 LC50-48 LD50 orally skin LD50
LC50-48
40% 2,434 > 101 > 100 > 2,000 > 2,000
>1,800 mg/L 3,228 mg/L
Na2HEIDA mg/L mg/L mg/L mg/kg mg/kg
Male, 24
SOP OECD Female,
Protocol SOP E312 SOP E209 OECD 203 hour
E207 202 gavage
application

TABLE 5 — ENVIRONMENTAL PERFORMANCE

Bio-Diesel
Regulated New Slurry Fluid Diesel Slurry
Requirements Slurry Fluid
Parameter Properties Fluid Properties
Properties
MMS 42 mg/l
Oil and Grease 12 mg/L 1,600 mg/L 4,100 mg/L
daily max
Sheen MMS: No sheen Pass: No sheen Fail Fail
Toxicity Mysid Low
> 30,000 ppm No Data No Data
shrimp, LC50 96 hr > 208,000 ppm
10 SPE 80593

Idea Concept Summary - Preliminary Business Plan

Concept
A
Feasibility l
Requirements / Specifications - Business & Design Plans

Project
Launch
Development Technical Audit

Field Test Plan and Launch

Field Test
Complete Field Test & Review

Review Product Specifications

Commercialization Commercialization Plan & Review

Mature Sustaining Transfer

Obsolescence Obsolescence Plan Review

Fig. 1— Chemical Lifecycle Management Process (C-PLMP)

Idea HSE Concerns Identified

Concept
Feasibility
HSE Regulatory Assessment
Project
L
Development h HSE Justification (if needed)

HSE / Regulatory Follow-up

Field Test
Well-site Delivery Review

HSE / Regulatory Review

Commercialization HSE / Regulatory Review

Mature Maintain Product

Obsolescence Product Disposal (if needed)

Fig. 2—HSE Impact on C-PLMP.

SPE 80593 11

Start Develop new product

y
A. Permission
Expert
PLONOR list
y Judgment n
D. Permission Refused
no
Substance Hazardous of Special Concern?
(Annex 2 of the OSPAR Strategy) yes

no
Substance inorganic? yes LC50 or EC50 <1 yes

IS SUBSTITUTE AVAILABLE?
Full HOCNF needed C. Temporary Permission
Or
no
D. Permission Refused *
Biodegradation <20% in 28 days? yes n
no

Does the substance meet two of the three following

• Biodegradation
• <70% in 28 days (OECD 301A, 301E) or B. Substitution*
• <60% in 28 days (OECD 301B, 301C, 301F, 306) y
• Bioaccumulation log Pow ≥3 or is BCF >100 and
considering molecular weight *(CHARM may be
• Toxicity LC50 or EC50 < 10mg/L used as
yes a decision-
n
Ranking According to CHARM Management Decision

Fig. 3—The harmonized prescreening scheme (shaded) as part of the whole harmonized
mandatory control system for offshore substances set out in the applicable OSPAR decision.

Exposure Toxicity
Models Evaluation

PEC PNEC
Predicted Environmental Predicted No Effect
Concentration Concentration

PEC: PNEC

HQ

Fig.4—Process for calculating the Hazard Quotient (HQ) via the CHARM Model
12 SPE 80593

Iron Control

70
Recommended Chelating
Agent Volumes, gal/1000

Na4EDTA
60
Na2HEIDA
50
40
30
20
10
0
1000 1500 2000 2500 5000
Fe3+, ppm

Fig. 5 — Recommended chelating agent amounts for stabilization of various amounts

of ferric iron at ambient temperatures to 250°F

120

100 20 lbm/Mgal
% Polymer Hydration

30 lbm/Mgal
80

60

40

20

0
0 1 2 3 4 5
Mixing Time (min)
Fig. 6 — Linear gel hydration performance