NAVAL FACILITIES ENGINEERING SERVICE CENTER
Port Hueneme, CA 93043
NFESC
TECHNICAL REPORT
TR-2107-ENV
EVALUATION OF BIO-BASED INDUSTRIAL
PRODUCTS FOR NAVY AND
DOD USE
PHASE I
CITRA-SOLV餂?
NATURAL CITRUS CLEANER & DEGREASER
April 1999
Prepared by
Naval Facilities Engineering Service Center
1100 23rd Avenue
Port Hueneme, CA 93043-4370
Printed on recycled paper
1.0 INTRODUCTION
Alternative Agricultural Research and Commercialization (AARC) Corporation is a wholly owned
corporation of the U.S. Department of Agriculture (USDA). AARC is a venture capital firm that is
authorized to make investments in companies to help commercialize bio-based industrial products (non-
food, non-feed) from agricultural, forestry materials, and animal byproducts. As these bio-based
products are made from agricultural materials, they tend to be environmentally friendly. In many
instances, these products replace petroleum products or are comprised of recovered agricultural waste
material.
Since the Federal government has an equity position in these companies, Section 729 of the
1996 Federal Agricultural Improvement and Reform Act (P.L.104-127, Title VII, Subtitle A, Chapter 2,
Section 1657c) prompted an amendment of the AARC Corporation authorization. The authorization
now allows other Federal agencies to establish procurement set-asides and encourages preferences for
property that has been commercialized with assistance provided under Subtitle G of Title XVI of the
Food, Agriculture, Conservation and Trade Act of 1990. To this end, the Federal Acquisition
Regulations are in the process of being amended to encourage these preferences. In addition, both the
Secretary of Defense and the Secretary of Agriculture have signed letters expressing their support of a
partnership between Department of Defense (DoD) and USDA to increase DoD use of these bio-based
products.
Under the sponsorship of AARC Corporation, Naval Facilities Engineering Service Center (NFESC)
evaluated the potential use of a number of these bio-based products within the Navy and DoD.
Representatives from both NFESC and AARC selected eleven bio-based products to undergo a two-
phase evaluation process. This document provides the results from the first phase of the evaluation
process.
2.0 EVALUATION METHODOLOGY
The evaluation methodology consists of a two-phase approach. Details of the methodology are outlined
in the following two subsections.
2.1 Phase I: Preliminary Product Evaluation
Each vendor鈥檚 manufacturing site was visited to collect product data, discuss product usage, and to
obtain information regarding the performance claims, savings, and environmental benefits. Existing
third-party certifications and test results were also reviewed and current users of the product were
contacted and interviewed. In addition, scientific and engineering literature was researched to establish
the physical, chemical, or biological mechanisms employed by the product in achieving its claimed
performance. Potential opportunities for using the product within the Navy were identified and a
preliminary life cycle cost (LCC) analysis was performed using the Phase I product data. The evaluation
process will not proceed to Phase II if the results of the Phase I product investigation clearly indicates
that the product can not be cost-effectively employed within the Navy or that the product has no apparent
cost-effective potential for Navy
2
use. An implementation plan will be developed for those Phase I products evaluated as having cost
effective use within the Navy. Proceeding onward to Phase II product testing will be recommended
when the Phase I analysis suggests that the product has potential for cost-effective Navy use but lacks
sufficient data to conclusively validate product performance and/or LCC.
2.2 Phase II: Product Testing
For those products proceeding onto phase II of the evaluation process, a specific step-by-step test
protocol will be developed for each recommended product with the objective of providing sufficient data
to verify product utility within the Navy. The protocol will be designed to evaluate life cycle
performance of the product. Upon approval of the protocol by AARC, the product will be tested by a
certified testing facility under controlled conditions. In addition, the life cycle performance of the
product will be evaluated and the environmental, safety, and health benefits and trade-offs associated
with the product will be estimated. A LCC analysis of the product will be performed using the proven
costing techniques from the NAVFAC Economic Analysis Handbook P-442.
An implementation plan will be developed for each of the recommended products targeted for the
potential user community within the Navy and DoD. During the development of the implementation
plan, the requirements and needs of the Navy ship, aviation, and shore facilities will be considered. The
resources of the Joint Group on Acquisition Pollution Prevention (JG-APP) will also be utilized to
promote Army and Air Force implementation of the product. Product visibility may also be achieved
through various publications distributed throughout DoD and other government agencies.
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3.0 PRODUCTS EVALUATED
Table 3.1 lists the eleven products evaluated in Phase I for potential application within the DoD.
Each product evaluation is presented in a separate report.
(Table 3.1 Omitted Due To Restricted Vendor Information)
4.0 AFFIRMATIVE PROCUREMENT
Section 6002 of Resource Conservation Recovery Act (RCRA) directs government agencies to promote
recycling by increasing their purchases of products containing recovered materials. RCRA section
6002(e) requires the Environmental Protection Agency (EPA) to designate items that are or can be
produced with recovered materials and prepare guidelines to assist procuring agencies in complying with
their affirmative procurement responsibilities set forth in paragraphs
(c), (d), and (i) of section 6002. Once EPA has designated items, section 6002 requires that any
procuring agency spending more than $10,000 a year of Federal funds on an item must purchase the
highest percentage of recovered materials practicable. Procuring agencies are Federal, state, and local
agencies, and their contractors, which use appropriated Federal funds.
Executive Order 12873 reinforced RCRA鈥檚 Federal buy recycled program by directing EPA to adopt
modified procedures for designating items and providing procurement recommendations.
Under the order, EPA issued a regulation known as Comprehensive Procurement Guideline which
contains the item designations, and also prepared a guidance document known as a Recovered Materials
Advisory Notice (RMAN). The RMAN contains EPA鈥檚 recommendations to procuring agencies to
assist them in purchasing the designated items and meeting their statutory obligations. The RMAN also
provides general guidance for developing an affirmative procurement program. An affirmative
procurement program is a procuring agency鈥檚 strategy for maximizing its purchases of EPA-designated
items, and must consist of the following:
鈥? Recovered materials preference program
鈥? An agency promotion program
鈥? A program for requiring vendors to reasonably estimate, certify, and verify the recovered
materials content of their products; and
鈥? A program to monitor and annually review the effectiveness of the affirmative procurement
program
On September 16, 1998 Executive Order 12873 was replaced by Executive Order 13101 which
expanded the affirmative procurement program to include bio-based products on the EPA
designated item list. A bio-based product list will be developed and published by USDA in the
Federal Register no later than March 23, 1999. The list shall also be updated biannually after
publication to include additional items. It is assumed that the bio-based products evaluated in
this report will be included in the list.
4
In the spirit of section 6002 of RCRA and Executive Order 13101, Federal procuring agencies and
personnel should strongly consider implementing sustainable bio-based products when selecting items to
meet the goals of the affirmative procurement program.
5.0 CITRA-SOLV餂? NATURAL CITRUS CLEANER & DEGREASER
5.1 Product Description
Citra-Solv餂? Natural Citrus Cleaner & Degreaser is a revolutionary, all-purpose, household, automotive,
and industrial solvent/cleaner. This product is marketed by Shadow Lake餂?, Inc., formerly Chempoint
Products, Inc., and has been in production for nearly 10 years. Citra-Solv餂? was developed to replace
mutagenic and carcinogenic solvents in the workplace in response to Occupational Safety and Health
Administration (OSHA) regulations. Citra-Solv餂? is a concentrated d-limonene based product derived
from the extract of citrus peels. The product contains 80-95 wt% limonene fraction terpenes, 1-10 wt%
folded orange oil (the concentrated product obtained by high vacuum distillation of winterized oils of
fresh oranges), 1-10 wt% ethoxylated alcohols C9-C11 and 1-10 wt% coconut diethanolamide.
Citra-Solv餂? is a powerful, concentrated cleaner. When diluted with water, it yields gallons of
multipurpose cleaner. Not only is Citra-Solv餂? tough on grease and grime, but its active ingredient is
made from a by-product of the orange juice industry and is a completely renewable resource. The orange
scent makes it pleasant to use and its efficacy and environmental soundness have been recognized by
Green Seal, Inc., an independent, nonprofit organization dedicated to protecting the environment by
promoting the manufacture and sale of environmentally responsible consumer products. Additional
information on Green Seal鈥檚 environmental standards and recommended general-purpose cleaners, can
be found on the following Websites:
http://www.greenseal.org/index.htm (Green Seal, Inc., Home Page)
http://www.greenseal.org/chart.htm (Recommended General-purpose Cleaners)
http://www.greenseal.org/standard/h-cleanr.htm (Household Cleaner Standard)
Citra-Solv餂? is packaged in a variety of sizes ranging from a 2-ounce promotional size to 55-
gallon drums and is available in a ready-to-use spray formula. The pre-mixed product provides
the natural cleaning ingredients of the super concentrated formula, but in a dilution that makes it
perfect for most general household and shop uses. Citra-Solv餂? is available through General
Services Administration (GSA) under contract number GS07F-0113H. Citra-Solv餂? is also
available through a growing number of retailers and mail order suppliers. Appendix A includes a
GSA net price listing of Citra-Solv餂?. Tables 5.1 and 5.2 contain a list of key retailers/distributors
and mail order suppliers of Citra-Solv餂?.
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Table 5.1 Key Retailers/Distributors of Citra-Solv餂? Natural Citrus Cleaner & Degreaser
DISTRIBUTOR / RETAILER
Clements Lowes Benny鈥檚 Ames Discount Stores
Genuardis Winn Dixie Albertsons C&S Wholesale
Wegmans Food Mart Stop N Shop Spags
Food Lion Edwards Big Y Nash Finch
MDI Price Chopper BJ Wholesale Club Waldbaums
Ingles Topps Big V-Shoprite
Table 5.2 Mail Order Suppliers of Citra-Solv餂? Natural Citrus Cleaner & Degreaser
COMPANY ADDRESS PHONE
The Vermont Country Store PO Box 1108 (802) 632 2400
Manchester, VT 05255
Home Trends 1450 Lyell Avenue (716) 254-6520
Rochester, NY 14606
Walnut Acres Penns Creek Road (800) 433-3998
Penns Creek, PA 17862
Environmentally Sound 167 Main Street (800) 886-5432
Products Eldred, PA 16731
Harmony 360 Interlocken Boulevard (800) 456-1177
Suite 300
Broomfield, CO 80021
Real Goods 966 Mazzoni Road (800) 762-7325
Ukiah, CA 95482
Solutions 13700 NW Science Park Dr. (800) 547-1160
Portland, OR 97229
Down To Earth 345 Lincoln Street Alley (800) 234-5932
Eugene, OR 97401
The Added Touch 132 Trafalgar Road (800) 268-5060
Oakville, Ontario L6J 3G5
In addition to Citra-Solv餂? Natural Citrus Cleaner & Degreaser, Shadow Lake餂?, Inc. also markets other
products including oil-based air fresheners derived from natural ingredients such as citrus or vanilla and
a natural all-purpose castile soap made primarily from olive, coconut, and other essential oils.
Contact Information:
Main Office and Plant Facility:
Shadow Lake餂?, Incorporated
Mr. Mike Riordan
188 Shadow Lake Road
Ridgefield, CT 06877-1032
Phone: (203) 778-0881 E-mail: shdwlake@ix.netcom.com
(800) 343-6588 Internet: http://www.shadowlake.com/
6
5.2 Vendor Claims and Specifications
Shadow Lake餂?, Inc. claims that d-limonene, the major ingredient in Citra-Solv餂?, is one of the most
powerful solvents known to man. The manufacturer also claims that Citra-Solv餂? is so powerful that it
can replace many harsh chemical cleaners including petroleum distillate products resulting in fewer toxic
products in the workplace. In addition, the manufacturer claims that Citra-Solv餂? is biodegradable and
environmentally friendly. The following list includes many of the manufacturer鈥檚 claims regarding this
product.
鈥? Natural solvent made from the rinds of oranges
鈥? Contains no petroleum distillates
鈥? Biodegradable
鈥? Extremely low toxicity even at high concentrations
鈥? Super-concentrated multi-purpose cleaner (contains no water but is water soluble)
鈥? Reduces waste
Tables 5.3a and 5.3b list many industrial, household, and automotive applications and the recommended
dilution for Citra-Solv餂? Natural Citrus Cleaner and Degreaser. Table 5.4 lists the physical properties of
Citra-Solv餂?.
Table 5.3a Industrial Cleaner/Solvent Applications for Citra-Solv餂? Natural Citrus
Cleaner & Degreaser
CLEANING DILUTION TYPES OF CLEANING HOW TO USE
CITRA-SOLV餂欴ILUTION
APPLICATIONS
Industrial Cleaner/Solvent
10 oz full strength daily Grease traps and drain lines Add Citra-Solv, wait 1 hour and
rinse with hot water
32 oz per 30 gallons of holding Clean and deodorize chemical
tank capacity toilets Add measured amount of
Citra-Solv to holding tank
1 qt per 1000 gal capacity Sewage tanks, septic tanks, drain Dispense through drip device for
fields maximum odor control
1 oz per 16 oz water or up to full Dip tanks, remove cutting oils, Add dilution to dip tank (up to
strength lubricants, varnishes and carbon full strength)
deposits from machine parts
1 oz per 32 oz water (or up to Pressure washing For heavily soiled areas, apply
1:100 depending on pressure) full strength and let soak
1 oz per 8 oz water Grease Filters Place filter in sink or basin, spray
on and let stand for 10 minutes
1 oz per 16 oz water Smoke, soot and diesel fuel Apply solution with sprayer or
bristle brush to remove stains
from firebrick, stone walls, etc.
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Table 5.3b Household and Automotive Applications for Citra-Solv餂? Natural Citrus Cleaner &
Degreaser
CLEANING DILUTION TYPES OF CLEANING HOW TO USE
CITRA-SOLV餂? DILUTION
APPLICATIONS
Household and Automotive Use
Window & Glass Cleaner All glass surfaces, windows,
1 oz in 3 gal water windshield washer reservoirs
(384:1)
Apply pre-mixed dilution to
General Purpose Cleaner Chrome, crystal, cars, trucks,
soiled area, rinse with clean
1 oz in 1/5 gal water motor homes, boats, bicycles,
water, and wipe, buff, allow
(64:1) carpet cleaning machines,
to air dry
no-wax floors
All-Purpose Cleaner Vents, sports equipment, walls,
1 oz in 2 cups water wall coverings, appliances,
(16:1) counters, vinyl, porcelain, wood,
paneling, aluminum, stainless
steel, metal blinds, telephones
Pre-spotting and spotting fabrics, Apply dilution to spots or soiled
carpet, upholstery, and fiber area, allow to stand for 1 minute
materials brush and blot with damp cloth
until stain is gone, lightly rinse
with clean water, blot dry
Degreaser / Cleaner Vinyl car tops, fiberglass,
1 oz in 1 cup water concrete, fireplace surfaces,
(8:1) outdoor furniture, upholstery,
oven ranges, food grease build up Apply cleaner to soiled area by
any standard method, allow to
Bathroom Cleaner Tub & tile, shower curtains, soap
stand for a short period. Rinse
1 oz in 陆 cup water scum, machinery, tires, wheels,
with clean water, and dry with
(4:1) pet stains, & odors, petroleum
normal method. (wipe, buff, or
stains
allow to air dry)
Solvent / Spotter Ovens, grills, engines, greasy
Full strength parts, tar, grease, chewing gum,
blood, fresh paints, crayons,
waxes (paraffin), adhesives,
permanent marker
Table 5.4: Physical Properties of Citra-Solv餂? Natural Cleaner and Degreaser
PHYSICAL PROPERTIES VALUE
Appearance Orange liquid
Odor Strong orange odor
0.859 卤 0.001
Specific Gravity
310-330
Boiling Point (掳F)
142
Flash Point (掳F) (Cleveland Open Cup)
Vapor Pressure (mm Hg) 2
Vapor Density 0.01
Solubility in Water Miscible
% Volatile by Volume 90
Evaporation Rate >1
pH 7.0-9.0
5.3 Verification of Product Claims
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5.3.1 Third Party Testing and Results
5.3.1.1 SGS U.S. Testing Company, Incorporated
In December 1997, SGS U.S. Testing Company performed a 28 Day Shake Flask Ready
Biodegradability Test on Citra-Solv餂? Cleaner and Degreaser to determine the test substance鈥檚
biodegradability in a closed aqueous system. The test was conducted in a Gledhill Apparatus (Shake
Flask) in compliance with U.S. EPA Good Laboratory Practice Standards, as described in 40 CFR, Part
792. Test results indicate that Citra-Solv餂? degraded 75.6% as determined by Total Organic Carbon
(TOC) reduction and 209% by CO2 evolution within 28 days. According to the test procedures used,
Citra-Solv餂? met the criteria for 鈥渞eady biodegradability鈥?.
A copy of the SGS test report titled 鈥?28 Day Shake Flask Ready Biodegradability Test Versus Citra-
Solv餂氣?? is included in Appendix B.
5.3.1.2 National Institute of Environmental Health Services Toxicology and Carcinogenesis
Studies of d-Limonene (CAS No. 5989-27-5)
Under the National Toxicology Program, the National Institute of Environmental Health Sciences
conducted two-year toxicology and carcinogenesis studies of d-limonene, a naturally occurring
monoterpene found in many volatile oils, especially in citrus oils. These tests were conducted because
of widespread use of d-limonene as a flavor and fragrance additive for food and household cleaning
products and its increasing use as an industrial solvent.
Under the conditions of the two-year studies, the National Institute of Environmental Health Sciences
concluded that there was clear evidence of carcinogenic activity of d-limonene in male rats, as shown by
increased incidences of tubular cell hyperplasia, adenomas, and adenocarcinomas of the kidney. The
Institute concluded there was no evidence of carcinogenic activity of d-limonene in female rats that
received 300 or 600 mg/kg, nor was there evidence of carcinogenic activity in male mice that received
250 or 500 mg/kg or female mice that received 500 or 1000 mg/kg. Most importantly, the Institute
determined that the kidney cancer produced in male rats by d-limonene was caused by a biological
process unique to male rats. Several other chemicals and substances, such as unleaded gasoline, produce
kidney tumors in male rats by this same mechanism, which does not occur in other rodents or in humans.
A copy of the National Institute of Environmental Health Sciences report TR-347, 鈥淭oxicology and
Carcinogenesis Studies of d-Limonene (CAS No. 5989-27-5) in F344/N Rats and B6C3F1 Mice (Gavage
Studies)鈥?, is included in Appendix C. This, as well as additional information regarding d-limonene, is
also available at the following web sites:
http://ntp-server.niehs.nih.gov/htdocs/LT-Studies/TR347.html
http://ntp-server.niehs.nih.gov/htdocs/Results_status/ResstatL/10071-T.html
It should also be noted that d-limonene is not listed in the Chemical Abstracts Service (CAS)
Registry Number (CASRN) index which lists the chemical names and registry numbers for all
entries in the National Toxicology Program鈥檚 Eighth Report on Carcinogens. The Report on
9
Carcinogens discusses individual substances, mixtures of chemicals, or exposure circumstances
associated with technological processes that are known to be human carcinogens or which may
reasonably be anticipated to be human carcinogens. The report also contains information
received from other Federal agencies relating to estimated exposures and exposure standards or
guidelines. The National Toxicology Program鈥檚 Eighth Report on Carcinogens and CASRN
index can be found at the following web sites:
http://ntp-server.niehs.nih.gov/Main_pages/NTP_8RoC_pg.html
http://ntp-server.niehs.nih.gov/htdocs/8_RoC/CAS_AppG.html
5.3.1.3 Green Seal
Green Seal has recognized Citra-Solv餂? Natural Citrus Cleaner & Degreaser as being an environmentally
responsible cleaner. Citra-Solv餂? received honorable mentions for recommended general purpose
cleaners in the March 1998 issue of Green Seal鈥檚 鈥淐hoose Green Report鈥? featuring general purpose
cleaners. The March 1998 issue of the 鈥淐hoose Green Report鈥? is included in Appendix D. Green Seal
is an independent, nonprofit organization dedicated to protecting the environment by promoting the
manufacture and sale of environmentally responsible consumer products. Green Seal鈥檚 mission is to
achieve significant environmental benefit by encouraging organizations and individuals to choose
environmentally responsible products and services. This goal is accomplished in two ways. First, they
set rigorous environmental standards for products and services and award a seal of approval to those that
meet the standard. When consumers select products bearing the Green Seal, they know they are buying
products that have a lessened impact on the environment, without sacrificing performance. Second,
through the Green Seal Environmental Partners Program and the Choose Green Reports, they help large
and small institutions become environmentally sensitive shoppers. Green Seal also provides detailed
guidance on how organizations can protect the environment while saving money.
Contact Information:
GREEN SEAL
1400 Sixteenth Street, NW
Suite 300
Washington, DC 20036-2215
(202) 588-8400
(202) 588-8465 - FAX
http://www.greenseal.org/index.htm (Green Seal Home Page)
http://www.greenseal.org/chart.htm (Recommended General-Purpose Cleaners)
http://www.greenseal.org/standard/h-cleanr.htm (Environmental Standards for Household Cleaners)
To be recognized by Green Seal requires more than having the words 鈥渂iodegradable鈥? or 鈥渘on-toxic鈥?
printed on the product label. Products must also meet the environmental criteria listed below:
鈥? Product is non-toxic to aquatic life and humans. Green Seal requires that cleaning products
pass specific aquatic toxicity tests, which are listed in the Green Seal environmental
10
standards for household cleaners. A copy of this standard (GS-08) is included in Appendix
E.
鈥? Product is biodegradable.
鈥? Phosphate and phosphonate concentrations are less than 0.5% by weight.
鈥? Product works optimally when diluted with cold water.
鈥? Product is packaged as a concentrate in recyclable/refillable containers with post-consumer
recycled content.
Additionally, products must perform not only to maintain consumer faith in green products but also help
the environment. Less efficient cleaners that require excessive amounts of product to clean surfaces are
not considered beneficial to the environment and would not be recognized favorably by Green Seal.
Green cleaners identified in Table 5.5 meet these environmental criteria.
Green Seal is a nonprofit, environmental-labeling organization and views themselves as an
environmental version of 鈥淐onsumer Reports鈥?. Their goal is to develop stringent environmental
standards for various products and serve to certify products that meet these standards. A 鈥淕reen Seal of
Approval鈥? is awarded to products that meet stringent environmental standards, that cause less harm to
the environment than other similar products, and have been certified by Green Seal.
Green Seal also publishes a monthly 鈥淐hoose Green Report鈥?. This report consists of a comprehensive
look at environmentally responsible 鈥済reen鈥? products with a comparative list of manufacturers and
sources. Products that have been awarded the 鈥淕reen Seal of Approval鈥? are identified with the seal in
the 鈥渃ertified鈥? column. Green products, such as Citra-Solv餂? Natural Citrus Cleaner & Degreaser, which
meet the Green Seal environmental standard for household cleaners, but have not been tested by Green
Seal, are also included. These products do not possess the seal of approval but are nevertheless
considered environmentally responsible or 鈥済reen鈥?.
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(Table 5.5 Omitted Due To Restricted Vendor Information)
5.3.1.4 Citra-Solv餂? Natural Citrus Cleaner & Degreaser Third Party Product/Performance
Testing
Shadow Lake餂?, Inc. has not performed independent third party testing to validate product performance
of Citra-Solv餂? Natural Citrus Cleaner & Degreaser. Vendor claims of product performance are based on
case studies provided by Shadow Lake鈥檚 supplier of the main ingredient (d-limonene) used in Citra-
Solv餂?. Materials compatibility is a key issue with any solvent or cleaner to be used with equipment such
as parts washers, dip tanks and pressure washers. The supplier has compiled a d-limonene compatibility
chart as shown in Table 5.6.
Table 5.6: D-Limonene Compatibility Chart
D-LIMONENE COMPATIBILITY CHART
Material Compatibility
Aluminum Very Good
Carbon/Ceramic Very Good
Carbon/Graphite Very Good
Carpenter 20 Very Good
Cast Bronze Very Good
Ceramagnet A Very Good
Ceramic Very Good
CPVC Very Good
Epoxy Very Good
Kel-F (Reg TM E.I. du Pont de Nemous & Co.) Very Good
Kynar (PVDF)(Reg TM Pennwalt Co.) Very Good
Nylon Very Good
Phenolic Very Good
Very Good
Ryton to 200掳F (Reg TM Phillips Petroleum Co)
Stainless Steel (304) Very Good
Stainless Steel (316) Very Good
Stainless Steel (440) Very Good
Teflon (Reg TM E.I. du Pont de Nemous & Co.) Very Good
Titanium Very Good
Hastalloy Very Good
Viton (Reg TM E.I. du Pont de Nemous & Co.) Very Good
Buna N Fair
Cycolac (ABS)(Reg TM Borg-Warner Co.) Fair
PVC Fair
Polyethylene Not Recommended
Polypropylene Not Recommended
Natural Rubber Not Recommended
Neoprene Not Recommended
Nitrll Not Recommended
Tygon (Reg TM 3M Co.) Not Recommended
12
The supplier also recommends that one should avoid contacting d-limonene with materials that can rust.
Where rust may be a concern, Shadow Lake餂?, Inc., can increase the concentration of orange oil, a rust
inhibitor, in the Citra-Solv餂? formula.
In addition to the above material compatibility information, case studies provided by the supplier give
insight into the performance of d-limonene based cleaners such as Citra-Solv餂?. Several case studies
involving d-limonene-based cleaners are presented in the following sections. These case studies
demonstrate that d-limonene based cleaners such as Citra-Solv餂? have been successfully used to replace
cleaners such as 1,1,1-trichloroethane (TCA), methyl ethyl ketone (MEK), methanol, and
chlorofluorocarbons (CFC) in various industrial applications. Several of the case studies indicate
significant savings in operating expenses and reduced hazardous waste disposal costs. In addition, d-
limonene based cleaners such as Citra-Solv餂? provide a safer work environment for employees through
reduced exposure to hazardous chemicals.
5.3.1.4.1 Case 1: Martin Marietta Astronautics
Martin Marietta Astronautics has replaced TCA and MEK with a terpene cleaner for hand wiping
operations. The terpene cleaner was decided upon after 16 months of extensive testing of citrus and
alkaline-based compounds. Workers prefer the citrus-based cleaner because it is more efficient. The
terpene cleaner leaves less residue resulting in higher coating bond strength. Martin Marietta estimates
the change has reduced toxic emissions by thousands of pounds per year. Research costs were $350,000
to find a suitable replacement for TCA and MEK. Estimated savings are $250,000 per year.
Dykema, Kevin J., and George R. Larson, 1993. 鈥淪hifting the Environmental Paradigm at Martin
Marietta Astronautics鈥?, Pollution Prevention Review, Spring: 205.
5.3.1.4.2 Case 2: EPA and APS Materials, Incorporated
In a joint research effort, the U.S. EPA and APS Materials, Inc. have investigated the use of a limonene
cleaner to replace TCA and methanol. APS Materials, Inc. is a metal finishing company that applies
plasma coating to parts for use in hostile environments. In the biomedical parts division, cobalt,
molybdenum and titanium parts are coated with a porous titanium layer for use as orthopedic implants.
APS Materials has converted to the terpene cleaner as a result of the investigation. Cleaning efficacy is
excellent with a slight increase in bonding strength for the limonene-cleaned parts. Changing to the
aqueous system required the addition of rinse and dry stations. The new system cost $1,800 to install
with annual operating expenses of $850. Net savings are $4,800 per year.
Brown, Lisa M., Johnny Springer, and Matthew Bower, 1992. 鈥淐hemical Substitution for 1,1,1-
Trichloroethane and Methanol in an Industrial Cleaning Operation鈥?, Journal of Hazardous Materials,
29:179-188, Elsevier Science Publishers.
13
5.3.1.4.3 Case 3: GE Medical Systems of Waukesha, WI
GE Medical Systems of Waukesha, Wisconsin, is a manufacturer of medical diagnostic equipment.
Spray cleaning (degreasing) of parts using TCA resulted in fugitive air emissions. GE Medical Systems
eliminated the fugitive TCA emissions by changing to a terpene cleaner for degreasing. Degreasing with
TCA required the purchase of 800 gallons of solvent per year, all of which was lost to the atmosphere.
The terpene cleaner is much less volatile, requiring the purchase of only 30 gallons per year. The
terpene cleaner is recycled. There was no capital expenditure required to implement the change in
cleaning solution.
Wisconsin Department of Natural Resources, Case Study: GE Medical Systems; 鈥淩eplacing 1,1,1-
tricholroethane with Citrus-Based Solvents鈥?, PUBL-SW-168 92, Hazardous Waste Minimization
Program (SW/3). Madison, WI.
5.3.1.4.4 Case 4: Northern Precision Casting of Lake Geneva, WI
Northern Precision Casting of Lake Geneva, Wisconsin, switched to a citrus-based solvent for cleaning
the wax patterns used in making molds. Previously, they used TCA, which evaporated as fugitive
emissions. TCA fugitive emissions amounted to 18,000 pounds in 1988. The terpene solvent is water-
soluble and is discharged to a publicly owned treatment works. No capital costs were incurred for the
change. Maintenance and operating costs are approximately the same.
Wisconsin Department of Natural Resources, Case Study: Northern Precision Casting; 鈥淩eplacing
1,1,1-Trichloroethane (TCA) with Citrus-Based Solvents鈥?, PUBL-SW-161 92, Hazardous Waste
Minimization Program (SW/3). Madison, WI.
5.3.1.4.5 Case 5: Marine Corps Air Station Naval Aviation Depot, Cherry Point, NC
The Marine Corps Air Station Naval Aviation Depot, Cherry Point, NC, is responsible for the complete
maintenance/rebuilding of naval aircraft. In 1990 the depot used 8,000 gallons of CFC-113 and 15,600
gallons of 1,1,1-trichloroethane. By the end of 1992, CFC-113 usage had been reduced to 500 gallons
annually, and TCA usage had been cut to approximately 4,800 gallons. The replacements included: soap
bubbles for leak checks, aqueous power washers for electronics, motor, and engine shop use; terpene
cleaners for hand wiping; steam cleaning or wet sodium bicarbonate blasting for soil and carbon
removal; and plastic media blasting for paint removal.
Hazardous Minimization-Saving Time, Money, and the Environment, Fennell, Mary Beth and Roberts,
James Mark/Naval Aviation Depot, Proceeding of the Aerospace Symposium, January 1993, Lake
Buena Vista, Florida, pp. 39-46.
14
5.3.1.4.6 Case 6: AT&T Reduces CFC-113 Usage
AT&T has reduced its usage of CFC-113 by switching to a semi-aqueous chemistry for cleaning surface
mount assemblies. Parts are fed by conveyor into a power washer consisting of wash and rinse/dry
modules. Low and high-pressure sprays of a terpene cleaner are followed by nitrogen knives which
reduce cleaning solution loss and blanket the washer with an inert atmosphere. In the second module,
the parts are rinsed with low, then high-pressure water sprays to remove the terpene cleaner. Rinsing is
followed by water removal by air knives within the same module. Care must be taken in selecting
surface mount components because the terpene cleaner swells some plastic and elastomers. AT&T has
found that the new cleaning method is more economical than the previous CFC-113 method.
鈥淭erpene Cleaning of Surface Mount Assemblies, Aqueous and Semi-Aqueous Alternatives for CFC-113
and Methyl Chloroform Cleaning of Printed Circuit Board Assemblies鈥?, EPA/400/1-91/016, June 1991,
pp. 51-60.
5.3.1.4.7 Case 7: Motorola Corporation Active Flux Removal Cleaning Systems
In 1998 the Motorola Corporation had 29 active flux removal cleaning systems using 250,000 pounds of
CFC-113 annually. By August 1991, Motorola had eliminated CFC-113 usage. Many of their printed
circuit board assemblies are now made with a no-clean flux. Assemblies which require cleaning are now
cleaned using terpenes and water. Benefits reported include cleaner assemblies, less production
downtime, and decreased cleaning cost. Cleaning costs are now about $8/hr with the terpene/water
versus $38/hr for the CFC-113.
鈥淭erpene Cleaning of Printed Circuit Board Assemblies, Aqueous and Semi-Aqueous Alternatives for
CFC-113 and Methyl Chloroform Cleaning of Printed Circuit Board Assemblies鈥?, EPA/400/1-91/016,
June 1991, pp. 61-62.
5.3.1.4.8 Case 8: Crown Equipment Corporation, New Bremen, OH
Crown Equipment Corporation, New Bremen, OH, manufactures electric lift and television antennae
rotors. Mild steel, aluminum, cast iron, and copper are all used and cleaned at the plant. In 1988 Crown
used 208,000 pounds of TCA in cold cleaning (dipping) and vapor degreasing operations. Hand dipping
now uses a water-based cleaner with rust inhibitor added for corrosion resistance. 100% d-limonene
spray cleaner has replaced TCA for hand wiped parts. An alkaline aqueous immersion cleaner has
replaced one degreaser (with inhibitor added for ferrous parts). The other degreaser was replaced with
an aqueous power washer which uses heat, agitation, and forced air drying to produce clean parts. The
payback period for the capital expenses was 10 months. In 1989 Crown saved $100,000 in chemical
costs. Crown Equipment has switched to water-based cleaning with no decrease in production.
Employees prefer the water-based cleaner for hand dipping.
Case Studies: 鈥淢ulti-Industry Success Stories to Reduce TCA Use in Ohio鈥? Kohler, Kurt, and Anthony
Sasson, Pollution Prevention Review, Autumn 1993, pp. 407-409.
5.3.1.4.9 Case 9: Bureau of Engraving, Inc., Industrial Division
15
The Bureau of Engraving, Industrial Division, manufactures printed circuit boards. In 1990 the company
decided to eliminate the use of methylene chloride and TCA, which were being used at the rate of
681,000 pounds per year. Several changes in the manufacturing process were necessary to accomplish
this goal, including the use of water-based and terpene-based cleaners. The Bureau of Engraving,
Industrial Division, is saving $250,000 annually in purchase cost and another $20,000 in maintenance,
energy, and disposal costs.
William T. Currie, Vice President, Facilities and Environmental Affairs, Bureau of Engraving, Inc.,
Industrial Division, 500 Fourth Street, Minneapolis, MN, 55415, MNTAP, 1993 Governor鈥檚 Awards for
Excellence in Pollution Prevention.
5.3.2 Review of Material Safety Data Sheet
The material safety data sheet for Citra-Solv餂? Natural Citrus Cleaner & Degreaser was prepared
internally by Shadow Lake餂?, Inc. This product is formulated from 80-95 wt% d-limonene (CAS 5989-
27-5), 1-10% folded orange oil (CAS 8028-48-6), 1-10% ethoxylated alcohols C9-C11 (CAS 68439-46-
3), and 1-10 wt% coconut diethanolamide (CAS 61790-63-4) and has been shown to be readily
biodegradable. The product is not considered to be a carcinogen by the National Toxicology Program
(NTP), the International Agency for Research on Cancer (IARC), or the Occupational Safety and Health
Administration (OSHA). Citra-Solv餂? does not contain, as an ingredient, chlorine, phenols, nitrites,
heavy metals, arsenic, PCB, PCT, TCCD, or other dioxin related substances. Citra-Solv餂? Natural Citrus
Cleaner & Degreaser may be harmful by inhalation, ingestion, skin absorption. Vapor or mist is
irritating to the eyes, mucous membranes and upper respiratory tract. Certain individuals may develop
contact dermatitis after exposure. A copy of the MSDS is included in Appendix F.
5.4 Military Specifications
Military specification MIL-C-29602 establishes the requirements for cleaning compounds used in
power washers and spray cabinets for cleaning aircraft components. This document states that the
flashpoint of the undiluted cleaning compound shall be greater than 212 0F. Since that flashpoint
of Citra-Solv餂? was determined at 142 0F, Citra-Solv餂? would not meet the requirements of MIL-
C-29602.
Military specification MIL-DTL-24800 establishes the cleaning compound to be used in
immersion, ultrasonic, spray, and pumped cleaning of oxygen system piping and components.
This document specifies that an aqueous inorganic cleaning compound shall be used for the
above cleaning operations. Since Citra-Solv餂? is based on an organic material, it would not meet
the requirements of MIL-DTL-24800.
Military specifications A-A-50425 and A-A-50427 establish the requirements for cleaning
compounds used to clean oxygen system components and oxygen systems. Historically, TCA,
CFC-113, 1,1-dichloro-1-fluoroethane, and HCFC-141B have been used to clean these items.
The specification calls for a colorless, non-flammable cleaning compound. Although Citra-
Solv餂? in its diluted form would be non-flammable, however it is not a colorless fluid and,
therefore, would not meet the requirements of
16
A-A-50425 and A-A-50427.
5.5 Current Users
Citra-Solv餂? Natural Citrus Cleaner & Degreaser has been in production for nearly 10 years. This
product is available from various distributors, retailers and mail order suppliers (Tables 5.1 and 5.2) to a
wide variety of consumers. Table 5.7 is a list of major industrial users.
Table 5.7: Citra-Solv餂? Major Industrial Users
INDUSTRIAL USER INDUSTRIAL USE
Char-Broil餂? Citra-Solv餂? used as degreaser and parts cleaner in their manufacturing
process
Coca-Cola餂? Citra-Solv餂? used to remove adhesive over-sprays from two-liter
bottling line. Also helps reduce the quantity of hazardous chemicals in
bottling plant thereby keeping facility in compliance with government
regulations.
Fisher Price餂? Citra-Solv餂? used to clean plastic residue from toy molds in the
manufacturing process.
Citra-Solv餂? used in the Transmission Division in Livonia, MI.
Ford Motor Company
Citra-Solv餂? used as a degreaser and parts cleaner in the manufacturing
Vibratech
of automotive parts.
Citra-Solv餂? used to remove excess soldering flux from assembled
Wentworth Laboratories
circuit boards during manufacturing process.
5.6 Product Comparisons
(Section 5.6 Omitted Due To Restricted Vendor Information)
5.7 Preliminary Life Cycle Costs
(Section 5.7 Omitted Due To Restricted Vendor Information)
5.8 Potential Navy / DoD Users
5.8.1 Federal Supply Listings
The Federal Government buys, stocks, and uses over 7 million items. The supply system catalog assigns
National Stock Numbers (NSNs) to each item the Government uses. The NSN is a 13-digit number
assigned by the Defense Logistics Service Center (DLSC), Battle Creek, Michigan. The first four digits
identify the Federal Supply Class (FSC) of the product. The next nine numbers represent the National
Item Identification Number (NIIN). The first two numbers of the NIIN identifies the country of origin.
The remaining seven digits identifies the specific item. A summary and detailed FSC listing can be
found at the following web site:
http://www.compnet.com/fsc.html (FSC listing)
17
The FSC system is most important in connection with DoD acquisitions of supplies and equipment. The
identification is either by two-digit groups or by four-digit individual codes. Sometimes only the two-
digit code is used which means that, in general; the same major buying offices buy most of the products
in the group. In other cases, some or all of the four-digit codes are listed which means that there are
differences in buying patterns.
Although Citra-Solv餂? Natural Citrus Cleaner & Degreaser has not been assigned a NSN, FSC codes
identified in the Federal Supply System that could potentially include this product are 7910-7930. This
range of code numbers is defined as 鈥淐leaning Equipment & Supplies鈥?. Based on similar products
currently available through the Federal Supply System, the most appropriate FSC code for Citra-Solv餂? is
7930. This code is defined as 鈥淐leaning/Polishing Compounds and Preparations鈥?.
5.8.2 Potential Military Specific Uses for Citra-Solv餂?
The military uses a variety of cleaners, solvents and degreasers for maintenance and repair work. Citra-
Solv has not been assigned a NSN and is currently not available through the Federal Supply System.
Table 5.11 lists historical purchase data information for FSC Code 7930. This information is available
at http://www.acq.osd.mil/sadbu under 鈥淟inks鈥? to estimate the potential market for products and
services within DoD.
18
Table 5.11: FY97 Purchase Data for FSC Code 7930, 鈥淐leaning/Polishing Compounds and
Preparations鈥? Contract Awards by FSC/SVC and Purchasing Office (in Thousands of
Dollars)
Dept State City Purchase Total Total US US Small Small
Office Acts. Dollars Bus. Bus. Bus. Bus.
Acts. Dollars Acts. Dollars
Army KY Fort Directorate of 1 46 0 0 0 0
Campbell Contracting
Army CA San HQ, EUSA, 1 68 0 0 0 0
Francisco ASST COFS
ACQ. MGT.
Army MD Aberdeen USA 1 48 0 0 0 0
Proving Aberdeen
Ground Proving Ground
Navy CA San Diego Fleet & Industrial 1 32 0 0 0 0
NSC Supply Center
Navy VA Norfolk Fleet & Industrial 1 32 0 0 0 0
Supply Center
Navy FL Jacksonville Fleet & Industrial 1 57 0 0 0 0
Supply Center
Navy MD Patuxent Naval Air 1 100 1 100 0 0
River Warfare Center,
NAS Aircra
Navy NY New York Naval Regional 2 259 0 0 0 0
Contracting
Center
Air CA San CONS/LGC 2 84 1 28 1 28
Force Francisco Mgmt Anly &
Spt Flgt
Air OH Wright ASC/PKWT 1 139- 0 0 0 0
Force Patterson
AFB
Air OK Tinker AFB Oklahoma City 1 26 0 0 0 0
Force ALC/PKO
OCE CA Sacramento USA Engineer 1 27 1 27 1 27
Dist Sacramento
FSC 14 639 3 155 2 55
TOTAL
19
5.9 Conclusions
Citra-Solv餂? is predominantly derived from a sustainable renewable resource.
鈥?
Citra-Solv餂? is biodegradable.
鈥?
Citra-Solv餂? is not considered to be a carcinogen by the NTP, the IARC, or OSHA. Citra-
鈥?
Solv餂? does not contain, as an ingredient, chlorine, phenols, nitrites, heavy metals, arsenic,
PCB, PCT, TCCD, or other dioxin related substances. However, Citra-Solv餂? may cause eye,
respiratory, or skin irritations.
Since Citra-Solv餂? is composed of up to 95% terpenes, Citra-Solv餂? can present a severe fire
鈥?
hazard and, therefore, not suitable for use in open pressurized spray cleaning systems without
blanketing the system with an inert atmosphere (i.e. nitrogen).
Citra-Solv餂? appears to be compatible with metals and most plastics. However, contact with
鈥?
polyethylene or polypropylene parts should be avoided.
The Citra-Solv餂? formula with the rust inhibitor (orange oil) is better suited for applications
鈥?
where rust is a concern.
鈥? Based on case studies provided by Shadow Lake鈥檚 supplier of d-limonene, it is felt that Citra-
Solv餂? is at least as effective as other d-limonene based products and could be included under
FSC 7930 with other all-purpose cleaners and degreasers.
Citra-Solv餂? does not meet the military specifications MIL-C-29602, MIL-DTL-24800, CID
鈥?
A-A-50425, or CID A-A-50427 for use as a cleaning compound in power washers and spray
cabinets for cleaning aircraft components or as a cleaner for oxygen equipment, components,
or systems.
In some cleaning operations, degreasers such as Citra-Solv餂? have been successfully used to
鈥?
replace solvents such as TCA, MEK, methanol, and CFC-113 in various industrial
applications.
5.10 Recommendations
Based upon the case studies of material substitutions with very similar citrus-based cleaners, no
additional testing on Citra-Solv餂? Natural Citrus Cleaner & Degreaser as a general all-purpose
cleaner is considered necessary. However, Citra-Solv餂? does not meet military specifications
MIL-C-29602, CID A-A-50425, or CID A-A-50427 and, therefore, Citra-Solv餂? shall not be used
or promoted as a cleaning compound in power washers and spray cabinets for cleaning aircraft
components or as a cleaner for oxygen equipment or systems.
20
5.11 Implementation
5.11.1 Points of Contact
The DoD is ready to do business, on a competitive basis, with competent firms that can supply the
products or services it needs. Manufacturers and marketing groups must familiarize themselves by
learning how the DoD conducts business, and by seeking out those military purchasing offices that buy
the products and services they can supply.
The Internet provides a valuable tool for businesses to obtain information on selling their products to the
military. A comprehensive 6-Part handbook titled 鈥淪elling To The Military鈥? is maintained on the World
Wide Web by the Office of the Secretary of Defense, in Washington, DC
(http://www.acq.osd.mil/sadbu/publications/selling/). This handbook is intended to provide firms,
which have little or no experience in selling to DoD, with basic information about how the DoD
conducts its business, and with specific information for locating sales opportunities. Part 2 addresses
products and services bought by major military purchasing offices and is divided into two sections. The
first section lists the major military purchasing offices of the Army, Navy, Air Force, and Defense
Logistics Agency (DLA). The accompanying description summarizes the procurement responsibilities
of each of these offices. The second section of this part lists the products and services purchased by the
major military purchasing offices. It is easier to locate sales opportunities for specific items from this
list. These items are listed in the numerical sequence of their FSC codes. This document includes
information regarding historical purchases of goods and services by various military organizations. The
information identifies the purchasing office, includes number of procurement actions performed, and
specifies the total dollars spent on acquiring products and services.
Part 6 of the handbook contains additional information on offices providing assistance to small
businesses for defense procurement. The contract management commands can assist in identifying DoD
contracting offices likely to buy specific products or services. In addition, several publications are
available to assist businesses with defense procurement. These publications include:
"U.S. Government Purchasing and Sales Directory"
This document provides a listing of products and services bought by all Federal agencies, and is
keyed to the purchasing offices that buy them. The DoD Stock Number is 045-000-00272-1 and is
available from the Superintendent of Documents, U.S. Government printing office, Washington,
D.C. 20402.
"Small Business Specialists"
On a nationwide basis, this document lists DoD specialists by name, location, and phone number,
and is available from the Superintendent of Documents, U.S. Government Printing Office,
Washington, D.C. 20402. The DoD reference number is DoD 4205.1-H. These regulations can also
be found on the Internet at: http://www.acq.osd.mil/sadbu, click on "Publications".
Table 5.12 lists the major buying offices or procuring agencies within the military that have a history of
purchasing items identified by FSC Code 7930.
21
Table 5.12: Purchasing Offices for Items Identified by FSC Code
MILITARY AND GOVERNMENT PRUCHASING OFFICES FSC
Directorate of Contracting 7930
2174 13 陆 ST
Fort Campbell KY 42223-5358
(502) 798-7126
A-2 U. S. Army Chemical Biological Defense Command 7930
AMSCB-SBA(A)
Aberdeen Proving Ground, MD 21010-5423
(410) 671-3136
Fleet and Industrial Supply Center 7930
Code COA
937 N. Harbor Drive
San Diego, CA 92132 -5075
(619) 532-3439
Fleet and Industrial Supply Center 7930
Code 04, Bldg W-143, Suite 600
1968 Gilbert Street
Norfolk, VA 23511-3392
(757) 443-1435
Naval Air Warfare Center 7930
Aircraft Division, Code 20C00W
22347 Cedar Point Road, Unit 6
Patuxent River, MD 20670-1161
(301) 342-7567 Ext. 103
Aeronautical Systems Center (ASC/BC) 7930
2196 D Street
Wright-Patterson AFB, OH 45433-7201
(937)255-5422
Oklahoma City Air Logistics Center 7930
3001 Staff Dr, Suite 1AJ84A
Tinker AFB, OK 73145-3009
(405)739-2601
One obstacle to the implementation of Citra-Solv餂? is that people tend to resist change. It is difficult to
persuade consumers to try a new product when they feel comfortable with what they are currently using.
Therefore, procuring agencies must actively advertise their desire to purchase non-toxic and
environmentally safe products within their organizations. This goal can be attained through internal
promotion. The process is a broad-based employee education program that will affirm the procurement
policy of an agency through advertising, workshops, agency newsletters, and technical and staff manuals.
Section 6.0 contains detailed implementation methods and additional procurement contacts applicable to
Shadow Lake餂?, Inc. products.
22
5.11.2 Additional Implementation Processes
Product visibility is crucial to product implementation. The following processes will assist Shadow
Lake餂?, Inc. product visibility within the military:
鈥? The Defense Technical Information Center (DTIC) will receive a final copy of this report. Joint-
Service users can search for specific information using a 鈥渒ey words or phrases鈥? search engine.
鈥? Citra-Solv will be logged into the Joint Service Pollution Prevention Technical Library. This library
exists as a Web site and is accessed by the Tri-Service system for pollution prevention guidance.
23
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