United States Prevention, Pesticides EPA 738-R-06-020
Environmental Protection and Toxic Substances July 2006
Agency (7508P)
Reregistration
Eligibility Decision
(RED) for Coppers
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REREGISTRATION ELIGIBILITY DECISION
FOR COPPERS
Case Nos. 0636, 0649, 4025, 4026
Approved by:
Debra Edwards, Ph.D.
Director, Special Review and
Reregistration Division
Date
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TABLE OF CONTENTS
Glossary of Terms and Abbreviations 3
EXECUTIVE SUMMARY 5
I. Introduction 10
II. Chemical Overview 12
A. Regulatory History 12
B. Chemical Identification 12
C. Use Profile 15
D. Estimated Usage of Copper Pesticides 18
III. Summary of Coppers Risk Assessments 22
A. Human Health Risk Assessment 22
1. Background on Copper 23
2. Exposure Sources of Copper 23
3. Human Metabolism of Copper 23
4. Toxicity Summary for Copper 24
5. FQPA Safety Factor Considerations 28
6. Aggregate Risk from Coppers (Dietary and Residential) 29
7. Occupational Exposure 29
8. Incidence Data on Copper Exposure 29
B. Ecological Risk Assessment 30
1. Environmental Fate 31
2. Ecological Exposure and Risk 32
3. Ecological Incidents 56
A. Determination of Reregistration Eligibility 58
B. Public Comments and Responses 58
C. Regulatory Position 59
1. FQPA Findings 59
2. Endocrine Disrupter Effects 60
3. Cumulative Risks 60
D. Tolerance Reassessment Summary 61
1. Tolerances Proposed to be Revoked 61
2. Tolerances Listed Under 40 CFR §180.1021 62
E. Regulatory Rationale 63
1. Human Health Risk Management 63
2. Ecological Risk Management for Non-target Organisms 65
3. Urban Uses 75
4. Advisory Language 77
5. 303(d) - Designated Impaired Water Bodies 78
V. What Registrants Need to Do 82
A. Manufacturing-Use Products 82
1. Generic Data Requirements 82
2. Labeling for Manufacturing-Use Products 82
B. End-Use Products 82
1. Additional Product-Specific Data Requirements 82
2. Labeling for End-Use Products 83
C. Labeling Changes Summary Table 83
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Coppers Reregistration Eligibility Decision Team
Office of Pesticide Programs
Biological and Economic Analysis Division
Andrew Lee
Jenna Carter
Richard Michell
William Phillips, II, Ph.D.
Environmental Fate and Effects Division
James Hetrick, Ph.D.
Paige Doelling Brown, Ph.D.
Health Effects Division
Alan Nielsen
Christina Jarvis
Elissa Reaves
Registration Division
Tony Kish
Risk Management
Rosanna Louie
Kevin Costello
Neil Anderson
Office of General Counsel
Andrew Simons
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Glossary of Terms and Abbreviations
ai Active Ingredient
aPAD Acute Population Adjusted Dose
APHIS Animal and Plant Health Inspection Service
ARTF Agricultural Re-entry Task Force
BCF Bioconcentration Factor
CDC Centers for Disease Control
CDPR California Department of Pesticide Regulation
CFR Code of Federal Regulations
ChEI Cholinesterase Inhibition
CMBS Carbamate Market Basket Survey
cPAD Chronic Population Adjusted Dose
CSFII USDA Continuing Surveys for Food Intake by Individuals
CWS Community Water System
DCI Data Call-in
DEEM Dietary Exposure Evaluation Model
DL Double layer clothing {i.e., coveralls over SL}
EC Emulsifiable Concentrate Formulation
EDSP Endocrine Disrupter Screening Program
EDSTAC Endocrine Disrupter Screening and Testing Advisory Committee
EEC Estimated Environmental Concentration. The estimated pesticide concentration in an environment,
such as a terrestrial ecosystem.
EP End-Use Product
EPA U.S. Environmental Protection Agency
EXAMS Tier II Surface Water Computer Model
FDA Food and Drug Administration
FFDCA Federal Food, Drug, and Cosmetic Act
FIFRA Federal Insecticide, Fungicide, and Rodenticide Act
FOB Functional Observation Battery
FQPA Food Quality Protection Act
FR Federal Register
GL With gloves
IDFS Incident Data System
IPM Integrated Pest Management
RED Reregistration Eligibility Decision
LADD Lifetime Average Daily Dose
LC50 Median Lethal Concentration. Statistically derived concentration of a substance expected to cause
death in 50% of test animals, usually expressed as the weight of substance per weight or volume of
water, air or feed, e.g., mg/1, mg/kg or ppm.
LD50 Median Lethal Dose. Statistically derived single dose causing death in 50% of the test animals
when administered by the route indicated (oral, dermal, inhalation), expressed as a weight of
substance per unit weight of animal, e.g., mg/kg.
LOAEC Lowest Observed Adverse Effect Concentration
LOAEL Lowest Observed Adverse Effect Level
LOG Level of Concern
LOEC Lowest Observed Effect Concentration
mg/kg/day Milligram Per Kilogram Per Day
MOE Margin of Exposure
MP Manufacturing-Use Product
MRID Master Record Identification (number). EPA's system of recording and tracking studies submitted.
MRL Maximum Residue Level
N/A Not Applicable
NASS National Agricultural Statistical Service
NAWQA USGS National Water Quality Assessment
NG No Gloves
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NMFS National Marine Fisheries Service
NOAEC No Observed Adverse Effect Concentration
NOAEL No Observed Adverse Effect Level
NPIC National Pesticide Information Center
NR No respirator
OPP EPA Office of Pesticide Programs
ORETF Outdoor Residential Exposure Task Force
PAD Population Adjusted Dose
PCA Percent Crop Area
PDCI Product Specific Data Call-In
POP USDA Pesticide Data Program
PF10 Protections factor 10 respirator
PF5 Protection factor 5 respirator
PHED Pesticide Handler's Exposure Data
PHI Preharvest Interval
ppb Parts Per Billion
PPE Personal Protective Equipment
PRZM Pesticide Root Zone Model
RBC Red Blood Cell
RED Reregistration Eligibility Decision
REI Restricted Entry Interval
RfD Reference Dose
RPA Reasonable and Prudent Alternatives
RQ Risk Quotient
RTU (Ready-to-use)
RUP Restricted Use Pesticide
SCI-GROW Tier I Ground Water Computer Model
SF Safety Factor
SL Single layer clothing
SLN Special Local Need (Registrations Under Section 24(c) of FIFRA)
TEP Typical End-Use Product
TGAI Technical Grade Active Ingredient
TTRS Transferable Turf Residues
UF Uncertainty Factor
USDA United States Department of Agriculture
USFWS United States Fish and Wildlife Service
USGS United States Geological Survey
WPS Worker Protection Standard
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EXECUTIVE SUMMARY
EPA has completed its review of public comments on the revised copper risk assessments
and is issuing its risk management decision for conventional (agricultural) uses of copper
pesticides. There are currently three tolerances being reassessed for coppers. The revised risk
assessments are based on review of the required target data base supporting the use patterns of
currently registered products and additional information received. After considering the risks
identified in the revised risk assessments, comments, and mitigation suggestions from interested
parties, EPA developed its risk management decision for uses of copper that pose risks of
concern. As a result, the Agency has determined that the agricultural uses of copper-containing
products are eligible for reregi strati on provided that data needs are addressed, risk mitigation
measures outlined in this document are adopted, and labels are amended accordingly. The
decision is discussed fully in this document.
Copper pesticides (copper or cupric ion) are extensively used in various agricultural
settings. Tens of millions of pounds are applied annually, predominantly in crop and algaecide
applications. Major crops and/or crops with high application rates include citrus, tree nuts,
tomato, pepper, grape, berries and peach. Included in the scope of the ecological risk
assessments are its use as a broad-spectrum fungicide on many food and ornamental crops, and
direct water applications as an algaecide, aquatic herbicide, bactericide and molluscicide.
Coppers also have residential uses as a garden and lawn fungicide and as a root-killer in sewer
systems. Coppers are also registered for antimicrobial applications, including uses as an anti-
foulant and preservative in wood and other materials. Although there are several forms of
copper-containing active ingredients under review, the active component of toxicological interest
is the cupric ion. Within the scope of this Reregi strati on Eligibility Decision (RED), the human
health assessment addressed cupric ion sources from both agricultural and antimicrobial
applications of copper-containing products, whereas the ecological assessment addresses
agricultural uses only. The Agency will complete its ecological assessment on antimicrobial
applications of copper products at a later date in a separate document.
Risk Summary
Copper is a naturally occurring metal that is efficiently regulated in the human system
and current available literature and studies do not indicate any systemic toxicity associated with
copper exposure. Thus, a qualitative human health assessment was conducted. Copper dietary
exposures do not pose any risks of concern. There are no residential or occupational risks of
concern resulting from exposure to copper products. Because several current agricultural
product labels do not specify typical application rates, minimum retreatment intervals or
frequency of treatments, the Agency made several assumptions on how coppers were applied to
assess potential exposure to non-target organisms. Based on these conservative assumptions, the
screening-level ecological assessment indicated that copper can pose acute risks to various
organisms, with the greatest risk to aquatic organisms resulting from direct water applications
and runoff from fields adjacent to water bodies.
Dietary Risk. Acute and chronic dietary (food and drinking water) risks from copper pesticides
are not of concern to the Agency. Copper is ubiquitous and naturally occurs in many food
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sources such as nuts, organ meats and grains. Humans have the capability to metabolize and
regulate copper levels in the body. Given the role copper plays as an essential element to the
human body, its ubiquitous nature in food and drinking water, and the lack of systemic toxicity
resulting from copper, acute and chronic dietary endpoints were not selected. Thus, a
quantitative toxicity assessment was not conducted for dietary, dermal, oral or inhalation
exposures.
Occupational and Residential Risk. Some copper species may cause acute dermal and eye
irritation in exposed individuals. Workers can be exposed to copper pesticides through mixing,
loading and/or applying the pesticide (handlers) or re-entering treated sites. Exposure may also
occur to residential handlers from home-use products. The irritating effects of individual
coppers are addressed through appropriate Personal Protective Equipment (PPE) or
precautionary labeling language for occupational or residential users, respectively. Since no
systemic toxicological endpoints of concern were identified for dermal exposures to coppers, no
dermal, oral or inhalation endpoints of toxicological concern were established. Occupational and
residential exposures to copper pesticides are not of concern to the Agency.
Aggregate Risk. Aggregate risk refers to the combined risk from dietary (food and drinking
water) and residential or other non-occupational exposures. Aggregate risk can result from one-
time (acute), short-term or chronic exposures. Because of the lack of systemic toxicity, copper
exposures from combined sources do not pose any health risks of concern.
Ecological Risk. The ecological risk assessment addresses only agricultural and direct aquatic
uses of copper-containing pesticides. The Biotic-Ligand Model was used to assess potential
exposures and risk to freshwater aquatic animals, whereas standard available models were used
to assess exposures to all other freshwater and marine/estuarine non-target organisms.
Terrestrial Organisms. The screening-level ecological risk assessment suggests potential risk to
terrestrial animals exposed to copper resulting from use as an agricultural pesticide. Risk
quotients (RQs) reflecting dietary exposure and toxicity to birds and mammals exceed both acute
and chronic levels-of-concern (LOCs). The ecological risk assessment presents both maximum
labeled rates and average typical application rates for terrestrial crops. Mitigation measures
which will reduce the maximum application rates for crop uses of coppers down to levels similar
to the typical rates evaluated result in significantly reduced acute and chronic RQs, but these
RQs still exceed acute and chronic LOCs for most feed items and weight classes of animals
considered.
There is some uncertainty in the finding of risk to birds and mammals because although
copper is toxic at high concentrations, it is also an important essential trace element for
organisms. Animals have the ability to cope with some amount of excess copper exposure by
storing it in the liver and bone marrow. As indicated by the laboratory toxicity studies, exposure
to high levels of copper in the diet can overwhelm the ability of birds and mammals to maintain
homeostasis. However, animals which are repeatedly exposed to levels of copper which do not
cause permanent harm may undergo enzymatic adaptation which allows them to cope with
greater levels of exposure.
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RQs based on limited toxicity data for terrestrial plants do not exceed the acute LOG
from exposure through spray drift. Available data from a honey bee acute toxicity study
indicated that copper is practically nontoxic to honey bees. However, because exposure
estimates for other insects cannot readily be determined, the potential risk of copper pesticides to
other insects is unknown.
Aquatic Organisms. Aquatic organisms also require some amount of copper as a nutrient, but
the main cause of copper toxicity to aquatic organisms is through rapid binding to the gill
membranes, which causes damage and interferes with osmoregulatory processes. Copper in the
water column occurs as dissolved ions and as a part of inorganic and organic complexes. The
toxic form of copper in water is the cupric ion. The amount of cupric ion in the environment,
and its toxicity to aquatic animals through gill damage, is dependent on a number of water
quality parameters including pH, alkalinity, and dissolved organic carbon.
The screening-level ecological risk assessment considered a wide range of water
chemistries, as represented by 811 water samples collected by the United States Geological
Survey nationwide. Risk to freshwater animals is presented as a percentage of the 811 resulting
RQs which exceed either acute or chronic levels of concern. Since the model used to perform
this analysis cannot currently be used for aquatic plants or estuarine/marine animals, these were
assessed using a single RQ per taxon.
Fewer than 1% of the 811 RQs for freshwater fish exceed the acute level of concern for
application rates up to 7.5 pounds of metallic copper per acre (Ibs Cu2+/A); the percentage
exceeding the chronic LOG ranges from 0% at 1 Ib Cu2+/A to 5.3% at 7.5 Ibs Cu2+/A. Almost all
revised maximum application rates for agricultural pesticidal uses of copper fall below 7.5 Ibs
Cu2+/A. There is a greater percentage of RQs which exceed LOCs for freshwater invertebrates.
At 1.0 Ib Cu2+/A, 3.2% and 4.2% of the 811 RQs exceed the acute and chronic LOCs,
respectively. At 7.5 Ibs Cu2+/A, these percentages increase to 25% and 32%, respectively. RQs
for freshwater non-vascular plants exceed the acute LOG for application rates of 1.5 Ibs Cu2+/A
or greater, and acute and chronic LOCs for estuarine/marine animals at rates of about 3.0 Ibs
Cu2+/A and above. The screening assessment does not indicate a risk to freshwater vascular
plants or estuarine/marine plants.
The percentage of freshwater animal RQs exceeding acute and chronic LOCs and the
magnitude of RQs for other aquatic organisms at revised application rates are significantly
reduced from those derived for maximum application rates on current copper pesticide labels.
Advisory language describing conditions which might result in greater spray drift of copper to
water bodies will help reduce that potential exposure. In addition, advisory language will be
added which describes the water quality conditions which would likely result in greater
concentrations and toxicity of copper in nearby water bodies.
The risk assessment concludes that direct water applications of copper would result in
greater than 95% of RQs exceeding acute and chronic LOCs for freshwater fish, invertebrates
and plants. The risk assessment assumes treatment of an entire water body to achieve the
maximum application rate, a water concentration of 1 ppm. Even with input from the user
community indicating that standard practice for most aquatic uses requires a lower application
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rate, and treatment of only a portion (up to 25-33%) of a water body at a time, direct aquatic
applications may result in risk to aquatic organisms. Treatment of only a portion of a water body
may allow fish and some invertebrates to leave the area being treated. Those that do not, or
cannot leave the treated area, may be at risk of adverse effects.
Benefits of Copper Use. Copper is significant as a cost-effective pesticide on crops and for
direct aquatic applications with no toxicity concerns to humans. The use of coppers on
agricultural crops as a fungicide and bactericide is significant to growers, as copper is generally
cost-effective, broad-spectrum, and in some cases the only available pesticide to manage the
target pest(s). Coppers are also among the few pesticides that are permitted for use on crops with
organic certifications. Copper products are used extensively for the management of nuisance
algae, aquatic weeds, mollusks, leeches. Algae and aquatic weeds may block and restrict water
quality and flow in irrigation and drinking water systems, which would require much costlier
management measures if these pests are not properly controlled. Algae may also produce
various toxic chemicals that may cause various problems for humans and animals, ranging from
dermal reactions to more severe toxicity problems, and in some cases, death for exposed animals.
Catfish aquaculture relies on copper sulfate to manage algae that may produce toxins that cause
off-flavors, rendering the entire fish crop unmarketable. Management of aquatic pests is
important for drinking water quality, as well as recreational waters to manage snail populations
that may host schistosomes that cause Swimmer's Itch, and leeches.
Endangered Species. At certain application rates, risk quotients in the screening-level risk
assessment for coppers exceed acute and chronic LOCs for various listed species of animals and
plants, should exposure actually occur. Acute and chronic LOCs are exceeded for birds,
mammals, and marine/estuarine fish and invertebrates. Freshwater non-vascular plants exceed
the acute LOCs. Screening-level modeling indicates that a number of sites exceed the
endangered species LOG for freshwater fish and invertebrates. Further, potential indirect effects
to any listed species dependent upon a species that experiences effects from use of copper can
not be precluded based on the screening level ecological risk assessment. These findings are
based solely on EPA's screening-level assessment and do not constitute "may affect" findings
under the Endangered Species Act for any listed species. If the Agency determines that the use
of copper "may affect" listed species or their designated critical habitat, EPA will employ
provisions in the Services regulations (50 CFRPart 402). Until species and site-specific
analyses are complete, the risk mitigation measures being implemented in this RED will reduce
the likelihood that endangered and threatened species may be exposed to copper at levels of
concern.
Regulatory Decision. The Agency has determined that all agricultural uses (terrestrial and
aquatic crops, bactericide on crops, urban fungicide, and sewer root-killer treatment) of copper
pesticides are eligible for reregi strati on provided that the risk mitigation measures and label
refinements outlined in this document are adopted, and label amendments are made to reflect
these measures.
Mitigation Summary. Because of the high number of registered crop sites, the Agency assessed
a subset of crops based on high application rates, high frequency of applications, and/or high
usage of copper products on that particular crop. EPA worked with the registrants and USD A to
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conduct extensive outreach efforts to the user community for additional refined information on
the actual use and needs of copper pesticides. Based on use information from the user
community, refined data indicated that most typical use rates are significantly lower than current
labeled maximum use rates. As a result, the registrants have agreed to refine their labels by
reducing application rates, defining application intervals, and determining seasonal maximum
application rates. Additional use pattern details for each crop are described in Appendix A.
Label language restricting spray applications of copper pesticides under certain weather
conditions, and advisory language describing steps users can take to minimize spray drift, will be
added to the agricultural use labels for copper pesticides. Registrants of copper-based pesticides
will be required to provide spray drift study data to fulfill guideline requirements. In addition,
advisory language will be added to copper pesticide product labels to inform users of surface
water quality conditions which can lead to greater bioavailability and toxicity of copper to non-
target aquatic organisms.
Next Steps. The Agency is issuing this RED document for public comment for agricultural uses
of copper pesticides as announced in a Notice of Availability in the Federal Register. In the
future, EPA intends to issue product-specific DCIs (PDCI) for data necessary to complete
product reregi strati on for agricultural end-use products containing copper.
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I. Introduction
The Federal Insecticide, Fungicide and Rodenticide Act (FIFRA) was amended in 1988
to accelerate the reregistration of products with active ingredients registered prior to November
1, 1984. The amended Act calls for the development and submission of data to support the
reregistration of an active ingredient, as well as a review of all submitted data by the U.S.
Environmental Protection Agency (EPA or the Agency). Reregistration involves a thorough
review of the scientific database underlying a pesticide's registration. The purpose of the
Agency's review is to reassess the potential risks arising from the currently registered uses of the
pesticide, to determine the need for additional data on health and environmental effects, and to
determine whether or not the pesticide meets the "no unreasonable adverse effects" criteria of
FIFRA.
On August 3, 1996, the Food Quality Protection Act of 1996 (FQPA) was signed into
law. This Act amends FIFRA and the Federal Food, Drug and Cosmetic Act (FFDCA) to require
reassessment of all existing tolerances for pesticides in food. FQPA also requires EPA to review
all tolerances in effect on August 2, 1996, by August 3, 2006. In reassessing these tolerances,
the Agency must consider, among other things, aggregate risks from non-occupational sources of
pesticide exposure, whether there is increased susceptibility to infants and children, and the
cumulative effects of pesticides with a common mechanism of toxicity. When a safety finding
has been made that aggregate risks are not of concern and the Agency concludes that there is a
reasonable certainty of no harm from aggregate exposure, the tolerances are considered
reassessed. EPA decided that, for those chemicals that have tolerances and are undergoing
reregistration, tolerance reassessment will be accomplished through the reregistration process.
As mentioned above, FQPA requires EPA to consider available information concerning
the cumulative effects of a particular pesticide's residues and "other substances that have a
common mechanism of toxicity" when considering whether to establish, modify, or revoke a
tolerance. The reason for consideration of other substances is due to the possibility that low-
level exposures to multiple chemical substances that cause a common toxic effect by a common
toxic mechanism could lead to the same adverse health effect as would a higher level of exposure
to any of the substances individually. Unlike other pesticides for which EPA has followed a
cumulative risk approach based on a common mechanism of toxicity, EPA has not made a
common mechanism of toxicity finding as to the copper ion and any other substances, and the
copper ion does not produce toxic metabolites produced by other substances. For the purposes of
this tolerance action; therefore, EPA has not assumed that the copper ion has a common
mechanism of toxicity with other substances.
This document presents EPA's revised human health and ecological risk assessments, its
progress toward tolerance reassessment, and the RED for agricultural uses of copper. The
ecological risk assessment addressing antimicrobial applications of copper will be assessed at a
later date. The Agency worked extensively with the registrants, USDA and the grower
community to reach the decisions as outlined in the RED. The document consists of six sections.
Section I contains the regulatory framework for reregistration tolerance reassessment. Section II
provides a profile of the use and usage of the chemical. Section III gives an overview of the
revised human health and ecological risk assessments based on submitted data, public comments,
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input and data received as a result of extensive communications with the grower community
through USD A, and other information received in response to the preliminary risk assessments.
Section IV presents the Agency's reregi strati on eligibility and risk management decisions.
Section V summarizes label changes necessary to implement the risk mitigation measures
outlined in Section IV. Section VI contains the Appendices, which list related information,
supporting documents, and studies evaluated for the reregi strati on decision. The revised risk
assessments for copper are available in the Federal Public Docket, under docket number EPA-
HQ-OPP-2005-0558, at www.regulations.gov.
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II. Chemical Overview
A. Regulatory History
The first recorded use of copper as a fungicide was in the mid-1700s, treating cereal
seeds with copper sulfate pentahydrate to control stinking smut or bunt. In the 1880s, the French
scientist Pierre Marie Alexis Millardet discovered the broad-spectrum fungicidal properties of
copper from the use of copper sulfate in the form of Bordeaux mixture (copper sulfate, hydrated
lime and water). The first registration for a copper-containing pesticide was issued in 1956.
Currently, 16 copper active ingredients (ai) have active food use registrations subject to tolerance
reassessment and reregi strati on review.
EPA issued Registration Standards for copper sulfate in March 1986, Guidance for the
Reregistration of Pesticide Products Containing Copper Sulfate as the Active Ingredient, and for
the Group II copper compounds, Guidance for the Reregistration of Pesticide Products
Containing Group II Copper Compounds as the Active Ingredient in April 1987. As a result,
Generic Data Call-In (GDCI) notices were issued in 1987 to the registrants for various copper
compounds to submit data in support of reregi strati on.
These comprehensive DCIs required various ecological fate and effects studies.
Additional DCIs were issued in 1993, which required various product chemistry studies, avian
toxicity studies and residue studies. These DCIs were issued so that data required by 40 CFR
Part 158 would be available to EPA before reregi strati on occurred.
B. Chemical Identification
Agricultural copper pesticides are formulated using various forms of copper, which
ultimately dissociates into the cupric ion, the active component of concern. Copper is a broad-
spectrum fungicide, bactericide, aquatic herbicide, algaecide and molluscicide for use on a
variety of agricultural crops, ornamentals and turf.
Common Name: Copper
Trade Names: Major trade names include Kocide, CuproFix, Basicop, K-Tea,
Cutrine Ultra, and Triangle Brand.
Technical Registrants:
In support of the agricultural uses of copper, the Copper Sulfate Task Force (CSTF) was
formed in 1986 to represent the interests of several registrants. The current members of the
CSTF are listed below.
Copper Sulfate Task Force Members (agricultural applications)
Albaugh, Inc. NuFarm Americas, Inc.
Cerexagri, Inc. Old Bridge Chemicals
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Chem One Ltd.
Chemical Specialties, Inc.
Drexel Chemical Company
Fabrica de Sulfato el Aguila S.A. de C.V.
Griffin L.L.C.
Isagro Copper S.p.A.
Micro-Flo Company
Nordox Industrier AS,
c/o Monterey Chemical Co.
Copper Reregi strati on Task Force (antimicrobial applications)
FBI/Gordon
Phelps Dodge Sales Co., Inc.
Phibro-Tech, Inc.
Quimetal Industrial S.A.
Spiess-Urania Chemicals GMBH
Teck Cominco American, Inc.
FULL MEMBERS:
American Chemet Corporation
Arch Wood Protection, Inc.
Bardyke Chemicals Ltd.
Chemical Specialties, Inc.
J.H. Baxter & Company
Nordox AS
Osmose, Inc.
Peninsula Copper Industries
Peninsula Copper Industries
Rohm and Haas Company
SCM Metal Products, Inc.
ASSOCIATE MEMBERS:
International Paint LLC (Akzo Nobel Chemicals Inc.)
ISP Minerals
Non-Task Force Members
Applied Biochemists
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Table 1 lists the copper pesticides and its respective cases that are addressed in the RED.
Table 1. Copper Compounds Subject to Reregistration.
Case
Copper Sulfates
#0636
Group II Copper
Compounds
#0649
Copper and
Oxides
#4025
Copper Salts
#4026
Other Copper
Compounds
Chemical Name
Basic Copper Sulfate
Copper Sulfate Pentahydrate
Copper sulfate monohydrate
Copper sulfate Anhydrous
Copper Chloride
Copper Ammonium Carbonate
Basic Copper Carbonate
Copper Hydroxide
Copper Oxychloride
Copper Oxychloride Sulfate
Copper Ammonia Complex
Chelates of Copper Copper
Gluconate
Copper chloride dihydrate
Copper Nitrate
Copper Oxalate
Chelates of copper citrate
Cuprous Oxide
EPA PC
Code
008101
024001
024402
024408
008001
022703
022901
023401
023501
023503
022702
023305
023701
076102
023305
044005
025601
C.A.S. Number
1344-73-6
7758-99-8
1332-14-5
7758-98-7
1332-40-7
33113-08-5
1184-64-1
20427-59-2
1332-65-6
8012-69-9
16828-95-8
814-91-5
10125-13-0
3251-23-8
814-91-5
10402-15-0
1317-39-1
Registrants
CSTF
Cancelled
CSTF
CSTF
CSTF
Cancelled
CRTF
Antimicrobial Uses Only
Copper (metal)
Cupric Oxide
Copper Salts of Fatty and Rosin
Acids
Copper Ethylenediamine
Copper Triethanolamine Complex
Copper 2-ethylhexanoate
(hexanoic acid)
Copper etidronic acid complex
Copper dehydroabietyl
ammonium 2-ethylhexanoate
Copper
ethylenediaminetetraacetate
(EDTA)
Copper linoleate
Copper oleate
Copper salts of the Acids of Tall
Oil
Cupric ferric subsulfate complex
022501
042401
023104
024407
024403
041201
024404
041202
039105
023303
023304
023103
042402
7440-50-8
1317-38-0
9007-39-0
13426-91-0
82027-59-6
22221-10-9
50376-91-5
53404-24-3
12276-01-6
7721-15-5
10402-16-1
61789-22-8
12168-20-6
CRTF
CSTF
Applied Biochemists
Cancelled
Unsupported
Cancelled
Antimicrobial Uses Only
Copper Naphthenate
Copper 8-quinolinolate
Copper Octanoate
Copper Ethanolamine Complex
023102
024002
023306
024409
1338-02-9
10380-28-6
20543-04-8
14215-52-2
CRTF
CSTF
Applied Biochemists
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Case Numbers:
Chemical Properties:
Reregi strati on cases included in the scope of this RED includes
#0636, #0649, #4025, #4026, and other food-use copper
compounds.
Table 2 describes the chemical properties for each of the copper
compounds that have registered food uses.
Table 2. Copper Chemical Properties
Common name
Copper sulfate pentahydrate
Basic copper sulfate
Copper hydroxide
Cuprous oxide
Copper carbonate
Copper ammonium complex
Copper ammonium carbonate
complex
Basic copper chloride
Copper oxychloride
Copper oxychloride sulfate
Copper salts of fatty and rosin acids
Copper ethylenediamine
Copper triethanolamine complex
Copper ethanolamine complex
Copper octanoate
Formula*
CuSO4-5H2O
3Cu(OH)2-CuSO4
Cu(OH)2
Cu20
Cu(OH)2CuCO3
Cu(NH3)42+
CuNH3(HCO3)2
3Cu(OH)2-CuCl2
Cu2Cl(OH)3
3Cu(OH)2-CuCl2 +
3Cu(OH)2-CuSO4
Mixture of compounds
C2H8N2Cu
C6H15O3NCu+2
C2H7ONCu+2
C8H1602Cu
Molecular weight*
249.65
468.29
81.56
143.08
221.12
131.58
190.54
427.133
213.57
879.43
NA
123.54
212.54
124.54
207.54
Percent Copper*
25.4
54.2
77.9
88.8
57.5
48.3
33.3
59.5
59.5
57.8
NA
51.43
29.89
51.01
30.61
Approximate formula, may vary slightly depending on manufacturing processes, molecular weight and percent
copper calculated based on formula
C.
Use Profile
Copper is a broad-spectrum fungicide, bactericide, aquatic herbicide, algaecide and
molluscicide for use on a variety of agricultural crops, ornamentals and turf. There are over two
hundred registered agricultural use sites, which include food, direct aquatic applications and
home-owner uses. The major crops that were assessed in this RED include citrus, strawberry,
tomato, pepper, rice, filbert, walnut, peach, apple, and grape. The following is information on
the currently registered agricultural and direct aquatic uses of coppers, including an overview of
use sites and application methods. A detailed description of uses of copper eligible for
reregi strati on is available in Appendix A.
15
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Type of Pesticide:
Target Pests:
Mode of Action:
Use Sites:
Coppers are registered for use as a fungicide, bactericide,
algaecide, herbicide, insecticide (leech), anti-fouling, wood
preservative.
Copper compounds control a broad spectrum of pests, including
fungi, bacteria, aquatic weeds, algae, mollusks, and leeches.
With fungal and algae organisms, the cupric ion binds to various
groups including sulfidal groups, imidazoles, carboxyls and
phosphate (thiol) groups that result in non-specific denaturing of
proteins, leading to cell leakage. In mollusks, copper disrupts
peroxidase enzymes and affects the functioning of the surface
epithelia.
Agricultural Crops. Copper is registered for use on virtually all
food/feed crops, including orchard, row, field, and aquatic crops.
Crops include, but are not limited to: root and tubers, leafy
vegetables (including brassica), bulb vegetables, fruiting
vegetables, citrus, stone fruit, pome fruit, legumes, cucurbits,
berries, cereals and tree nuts. Copper is also registered for several
ornamental crops, such as flowering/non-flowering plants and
trees.
Aquatic Applications of Copper Pesticides Copper is registered
for use on numerous aquatic use sites. Below is a description of
algaecide, herbicide, molluscicide, and macro-invertebrate use.
Algaecide Applications. Copper applications for algae control
include: aquaculture facilities, drainage systems (canal, ditch and
lateral), ponds (farm, industrial and recreational), fountains,
lakes, reservoirs (crop and non-crop irrigation, potable), sewage
lagoons, stocking (tank, water trough and ponds) and irrigation
canals.
Herbicide Applications. Copper applications for aquatic weed
control include: aquaculture facilities, drainage systems (canal,
ditch and lateral), ponds (farm, industrial and recreational), lakes,
reservoirs (crop and non-crop irrigation, potable), sewage lagoons,
stocking (tank, water trough and ponds) and irrigation canals.
Molluscicide and Macro-Invertebrate Applications. Copper is
registered for use to control freshwater snails that may be a vector
for harmful trematodes. Copper is also used to control leeches,
and tadpole shrimp in rice fields.
16
-------
Tolerances:
Use Classification:
Formulation Types:
Application Methods:
Application Rates:
Antimicrobial Applications. Copper is registered for use as a
wood preservative, mildewcide, water treatment, bactericide, and
as an anti-fouling in many products including paint, glue, building
materials and construction materials.
There are currently three tolerances established for coppers: 40
CFR§180.136, 40 CFR§180.538, and 40 CFR§180.1021.
Copper is a general use pesticide for agricultural, residential and
industrial applications.
Formulations of copper-containing pesticides include dust, liquid
concentrate, dry flowable, wettable powder (including water-
soluble packets), granule, water-dispersible granule, powder,
ready-to-use liquid, aerosol, and solid.
Agricultural copper application methods include aerial, airblast,
groundboom, rights-of-way equipment, mechanical duster, low-
and high-pressure handwand sprayer, handgun sprayer, push-type
spreader, dips, drip system, hose-end sprayer, and automatic-
metering system.
Application methods for direct aquatic applications of copper
include broadcast dry, broadcast spray, dragging, injection
(flowing water), slug or dump, or spot spray.
The ecological risk assessment addresses a range of application
rates up to the maximum labeled use rates. Copper application
rates vary depending on the use pattern and the severity of disease
or pest infestation. Additionally, input from user growers indicate
that actual use rates are lower than current maximum labeled rates.
From various efforts with outreach to the public through the CSTF
and USD A, refined use rates information was used to refine and
characterize the risk assessment. Below is a description of the use
rates assessed in the ecological assessment.
Maximum Labeled Rates. The highest maximum labeled rate
assessed was for filberts at 31.8 Ibs pounds of metallic copper per
acre (Ibs Cu2+/A), and for potatoes at 3.2 Ibs Cu2+/A. For both
uses, the Agency assumed four applications at weekly application
intervals.
Typical Use Rates. The highest typical application rate for food
crops is 6 Ibs Cu2+/A for filbert crops. However, the typical use
rate for all other crops ranges from 0.25 Ibs Cu2+/A up to
approximately 4.0 Ibs Cu2+/A. For control of tadpole shrimp in
rice fields, up to 2.5 parts per million (ppm) may be used. For
17
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direct water applications of copper for management of aquatic
weeds and algae control, the maximum concentration of metallic
copper is 1.0 ppm. For leech or snail control, up to 1.25 ppm of
metallic copper may be used. Because rates vary depending on
disease pressure or severity of pest infestation, determining a
maximum number of applications was not feasible. Thus, The
Agency assumed the same four applications at weekly application
intervals, as for the maximum labeled rates previously described.
The maximum residential application use rate is 0.5 Ib Cu2+/A for
root control in sewer systems.
Application Timings: Depending on the crop and stage of development, applications are
recommended during virtually all stages of crop/fruit development
including dormant applications; petal fall; bud break; early bloom;
post bloom; early spring; early summer; late summer; early fall;
late fall; after harvest. Treatment timings for direct aquatic uses
vary, depending on the proliferation of the target pest.
D. Estimated Usage of Copper Pesticides
Available usage data on the use of copper compounds on growing crops greatly varies.
The Agency's Screening Level Usage Analysis (SLUA) for the two major copper compounds is
described below. According to other available data sources, there is some uncertainty as to the
actual figures of copper used for agricultural crops, such as reporting errors of the copper
compound used on that site. The CSTF estimated that 9-11 million pounds of elemental copper
in the form of copper sulfate pentahydrate are applied each year solely for algae and weed
control. Applied Biochemists Company estimates that 300,000 pounds of elemental copper in
various forms of complexed copper compounds are applied annually for algae and weed control.
SLUA for Copper Hydroxide
Crop Lbs. A.I. Percent Crop Treated
Avg. Max.
1 Almonds 600,000 25 30
2 Apples 100,000 10 15
3 Apricots 40,000 30 45
4 Avocados 100,000 5 10
5 Beans, Green 70,000 25 50
6 Blackberries 4,000 30 35
7 Blueberries 4,000 20 55
8 Broccoli 1,000 <1 5
9 Cabbage 6,000 5 10
10 Cantaloupes 3,000 <1 5
11 Carrots 20,000 10 20
12 Cauliflower 1,000 5 5
13 Celery 30,000 35 45
18
-------
14 Cherries 100,000 15 25
15 Collards 1,000 5 5
16 Cucumber 40,000 10 15
17 Cucumbers 20,000 10 20
18 Dry Beans/Peas 80,000 5 5
19 Eggplant 3,000 35 60
20 Garlic 9,000 10 15
21 Grapefruit 700,000 55 70
22 Grapes 400,000 65 95
23 Greens, Mustard <500 5 5
24 Greens, Turnip 1,000 5 5
25 Hazelnuts (Filberts) 20,000 10 15
26 Lemons 50,000 20 30
27 Lettuce 3,000 <1 5
28 Limes 30,000 85 85
29 Nectarines 90,000 40 55
30 Olives 30,000 15 20
31 Onions 100,000 30 40
32 Oranges 1,800,000 40 50
33 Peaches 200,000 25 30
34 Peanuts 20,000 <1 5
35 Pears 30,000 10 25
36 Peas, Green 4,000 <1 <2.5
37 Pecans 20,000 <1 <2.5
38 Peppers 200,000 35 50
39 Pistachios 70,000 10 15
40 Potatoes 90,000 5 15
41 Prunes & Plums 100,000 15 15
42 Pumpkins 20,000 10 25
43 Raspberries 4,000 25 40
44 Rice 10,000 <1 <2.5
45 Spinach 6,000 10 25
46 Squash 10,000 10 15
47 Strawberries 5,000 5 10
48 Sugar Beets 4,000 <1 <2.5
49 Sweet Corn 1,000 <1 <2.5
50 Tangelos 20,000 60 65
51 Tangerines 60,000 45 65
52 Tomatoes 800,000 30 65
53 Walnuts 1,400,000 45 55
54 Watermelons 50,000 15 25
55 Wheat 5,000 <1 <2.5
19
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SLUA for Copper Sulfate Pentahydrate
Crop
Lbs. A.I.
1
2
O
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
Almonds
Apples
Apricots
Avocados
Beans, Green
Blackberries
Blueberries
Cabbage
Cantaloupes
Carrots
Cauliflower
Celery
Cherries
Cotton
Cucumber
Cucumbers
Dry Beans/Peas
Grapefruit
Grapes
Hazelnuts (Filberts)
Lemons
Lettuce
Limes
Onions
Oranges
Peaches
Peanuts
Pears
Pecans
Peppers
Pistachios
Potatoes
Prunes & Plums
Pumpkins
Raspberries
Rice
Spinach
Squash
Strawberries
Sugar Beets
Sweet Corn
Tangelos
100,000
60,000
9,000
40,000
10,000
1,000
2,000
1,000
1,000
10,000
<500
5,000
50,000
6,000
2,000
1,000
10,000
100,000
100,000
10,000
40,000
<500
<500
10,000
900,000
100,000
20,000
10,000
3,000
30,000
1,000
30,000
30,000
5,000
7,000
300,000
2,000
3,000
<500
20,000
1,000
1,000
Percent
Avg.
5
5
10
<1
5
10
5
<1
<1
<1
<1
5
5
<1
<1
<1
<1
15
15
10
15
<1
<1
<1
15
10
<1
5
<1
5
<1
<1
5
<1
30
<1
5
<1
<1
<1
<1
5
Crop Treated
Max.
5
5
15
5
10
10
20
<2.5
<2.5
5
<2.5
5
10
<2.5
<2.5
5
<2.5
25
30
10
20
<2.5
<2.5
5
35
20
<2.5
10
<2.5
10
<2.5
5
5
5
40
5
10
5
5
5
<2.5
10
20
-------
43 Tangerines 5,000 10 10
44 Tomatoes 40,000 <1 5
45 Walnuts 200,000 5 10
46 Watermelons 3,000 <1 <2.5
47 Wheat 3,000 <1 <2.5
21
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III. Summary of Coppers Risk Assessments
The following is a summary of EPA's human health and ecological risk assessments for
coppers, as presented fully in the documents, "Coppers: Revised Human Health Chapter of the
Reregistration Eligibility Decision Document (RED). Reregistration Case numbers 0636, 0649,
4025 and 4026, " dated June 29, 2006, and "Error Corrections for the Ecological Risk
Assessment for Re-Registration of copper sulfate (case #0636), group II copper compounds (case
#0649), and copper salts (case #0649) for use on crops and as direct water applications, " dated
April 20, 2006. The human health and ecological risk assessment documents and supporting
information listed in Appendix C were used to reach the safety finding and regulatory decision
for coppers. The revised risk assessments and related documents are available online at
www.resulations.sov under Public Docket EPA-OPP-HQ-2005-0558.
As part of the public participation process, the Agency solicited additional information
from the public, including grower groups, to further refine the risk assessments and to provide
input for risk mitigation suggestions. Because current agricultural-use labels for copper-
containing products contain inconsistent use rates and use application information, the Agency
made several assumptions in the ecological risk assessment. After conducting the preliminary
risk assessments, EPA determined that additional information on use rates and other application
information were necessary in order to refine the risk assessments.
In October 2005, the Agency requested that the registrants collect additional use
information from user groups, which was submitted shortly before the Phase 3 public comment
period. Although there was insufficient time to fully review the received data at that time, a
preliminary cursory review showed that this data was insufficient to fully refine the risk
assessments. Thus, the Agency solicited additional specific use information on major crops and
direct aquatic uses during the Phase 3 public comment period. As a result of response from the
public as well as outreach to the user community, several groups provided refined use
information that was considered and incorporated in the revised risk assessments, as well as in
the RED. This information was used to refine labels to further mitigate estimated risks.
As a result of comments received during the Phase 3 public comment period, the
following major revisions were made to the ecological risk assessment:
• Assessment of root-killer sewer treatment use with the E-F AST model
• Addition of screening spray drift assessment for agricultural uses
• Inclusion of available information on mammalian homeostatic capabilities, including
a 22% absorption factor to account for dietary metabolism effects
• Addition of screening risk assessment for marine/estuarine organisms
• Incorporation of typical use rates
A. Human Health Risk Assessment
This section of the document summarizes the human health risk estimates for exposures
to pesticide products containing copper as the active ingredient. In this qualitative assessment,
the EPA has considered aggregate or combined exposures from food, drinking water and non-
22
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occupational sources. The aggregate risk from all copper sources must be considered to reassess
the tolerance for residues of copper in food and water, in accordance with FQPA. EPA's reliance
on any study in the risk assessment is in accordance with the Agency's Final Rule promulgated
on January 26, 2006, related to Protections for Subjects in Human Research, which is codified in
40CFRPart26.
1. Background on Copper
Copper is a naturally-occurring, ubiquitous element in the environment. Copper is found
in water, air, and occurs naturally in various foods including organ meats, seafood, beans, nuts,
and whole grains. In most foods, copper is bound to macromolecules rather than as a free ion.
For many animals, copper is essential for the homeostasis of life. The role of copper in
maintaining normal health both in humans and animals has been recognized for many years.
Copper is an essential cofactor for approximately a dozen copper-binding proteins for the proper
regulation of copper homeostasis in humans. A deficiency of copper or a defect in copper-
carrying proteins may result in symptoms such as anemia, defective blood vessel development,
growth retardation, a compromised immune function or connective tissue symptoms.
2. Exposure Sources of Copper
Humans are exposed to copper primarily from food and drinking water sources, as well
as in the air. Copper is found naturally in various foods, including organ meats, seafood, beans,
nuts, and whole grains. It has been estimated that approximately 40% of dietary copper is
consumed from yeast breads, white potatoes, tomatoes, cereals, beef, dried beans and lentils.
The recommended dietary allowance (RDA) of copper, as established by the National Academy
of Science, ranges from 0.34 milligrams per day (mg/d) in young children to 1.3 mg/d for
pregnant and lactating females. The estimated total daily oral intake of copper (food plus
drinking water) is between 1 and 2 mg/d, although oral intake may sometimes exceed 5 mg/d.
Copper may also be found in drinking water, commonly due to the use of copper
plumbing fixtures and water pipes. Copper may also enter drinking water systems via
contamination from mining operations, incineration, industrial discharges, water treatments and
sewage treatment facilities. Other non-biological sources of copper include smelters, iron
foundries, power stations and combustion sources such as municipal incinerators. For water
quality management, a Maximum Contaminant Level Goal (MCLG) of 1.3 milligrams per liter
(mg/L, or 1.3 ppm) has been set by the EPA for copper in drinking water.
In addition to dietary sources, copper pesticide use may also result in oral, dermal and
inhalation exposures. There is potential for exposure to occupational mixers, loaders, and
applicators of copper pesticide products, as well as to residential homeowners who may apply
copper-containing pesticide products in and around their homes.
3. Human Metabolism of Copper
Although the metabolism pathways are not clearly known, the mechanisms for regulating
total copper in the body appear to be efficient in maintaining a generally consistent level of
23
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copper needed for homeostasis. The efficiency of copper absorption varies greatly, depending
on dietary intake. When dietary copper is high and more copper is absorbed, mainly through the
gastrointestinal tract, excretion of copper from the body increases, protecting against excess
accumulation of copper in the body. Depending on the copper status in the body at the time,
approximately 20 to 60% of dietary copper may be absorbed. Copper absorption is also affected
by other factors such as species, age, chemical form, and pregnancy. When copper intake is low,
little copper is excreted from the body, protecting against copper depletion. Generally, current
available data and literature studies indicate that there is a greater risk from the deficiency of
copper intake than from excess intake. A deficiency of copper or a defect in copper carrying
proteins may result in symptoms such as anemia, defective blood vessel development, or
connective tissue symptoms.
Some less common genetic conditions in humans may cause abnormal copper
metabolism, causing either excessive retention or incapable of absorbing copper. Some disorders
that result in copper toxicity include Wilson's Disease, Occipital Horn Syndrome, Tyrolean
Infantile Cirrhosis, Indian Childhood Cirrhosis, Idiopathic Copper Toxicosis, and
aceruloplasminanemia. For example, Wilson's disease is due to the inability for biliary excretion
of copper which leads to the gradual accumulation of copper predominately in the liver and
brain. In contrast, Menkes disease is an X-linked neurodegenerative disorder in infants
characterized by poor growth and unusual "kinky" hair texture. In Menkes disease, clinical
effects include low ceruloplasmin concentrations and decreased concentrations of copper in the
liver and brain. The major cause of this copper deficiency is minimal copper absorption by the
intestinal mucosa and transport of copper across the blood-brain-barrier, independent of copper
intake.
4. Toxicity Summary for Copper
Toxicity assessments are designed to predict whether a pesticide could cause adverse
health effects in humans (including short-term or acute effects such as skin or eye damage, and
lifetime or chronic effects such as cancer, development and reproduction deficiencies, etc.) and
the level or dose at which such effects might occur. The Agency has reviewed all toxicity
studies submitted for copper and has determined that the toxicological database is sufficient to
assess the hazard from pesticides containing copper.
The component of toxicological interest in copper pesticides is elemental copper (cupric
ion). Humans have homeostatic capabilities to regulate copper in the system. Effects such as
severe dermal, eye, and inhalation irritation seen in acute toxicity studies are a function of the
body's response mechanisms to reduce excessive copper exposure, rather than as a result of
systemic toxicity. Acute toxicity studies are available for several of the copper compounds.
These acute studies show that copper generally has low acute toxicity, with the exception of
cuprous oxide for acute inhalation. Based on available literature and studies submitted by the
registrant, there is no evidence of copper or its salts being carcinogenic or posing any other
systemic toxicity in animals having normal copper homeostasis. Thus, endpoints were not
established to quantify any potential risks from exposure to copper.
24
-------
Acute Toxicity. Acute toxicity studies are available for most copper species, with the exception
of copper ammonium carbonate, copper-ammonia complex, chelates of copper gluconate, copper
oxychloride sulfate, basic copper sulfate, and copper ethanolamine complex. Table 3 below
describes available acute toxicity studies on the respective copper compounds.
Table 3. Available Acute Toxicity Studies on Copper-Containing Compounds
Copper Type
Copper chloride
(57.7% Cu)
Chelates of
copper gluconate
Copper
ammonium
carbonate
Copper carbonate
(96%)
Copper
hydroxide (77%)
Copper-ammonia
complex
Copper
oxychloride
(94.1%)
Copper
oxychloride
sulfate
Basic copper
sulfate
Copper sulfate
anhydrous
Copper sulfate
pentahydrate
(99%)
PC
Code
008001
024405
022703
022901
023401
022702
023501
023503
008101
024408
024401
Acute Oral
LD50
(mg/kg)
M= 1796
F= 2006
Tox Cat. Ill
43769501
Acute
Dermal
LD50
(mg/kg)
> 2000 (M
&F)
Tox Cat III
43769502
Acute
Inhalation
(mg/L)
None
Available
Primary Eye
Irritation
Comeal opacity
cleared by 21
days
Tox Cat. II
43769503
Dermal
Irritation
Non-
irritating
Tox Cat. IV
43769504
Dermal
Sensitization
None Available
None Available
None Available
>2000
Tox Cat III
41889302
M = 2253
F=2160
Tox Cat. Ill
41421602
None
Available
>2000
Tox Cat III
00159371
00259424
None
Available
77%
M= 1.53
mg/L
F=1.04
mg/L
00160580
88% F = 0.5
mg/L
Tox Cat. Ill
Corrosive,
opacity at 21
days
Tox Cat I
41889301
Irritative
Comeal
opacity, iris
irritation,
chemosis,
invasion of
cornea by
blood vessels
Tox. Cat. I
Non-
irritating
Tox Cat IV
41889302
At 72 hrs,
very slight
erythema
Tox Cat. IV
None Available
Non-sensitizing
Guinea Pig
None Available
M= 1537
F=1370
Tox Cat. Ill
00155931
M&F=710
(281-1791)
Tox Cat II
> 1.7 mg/L
Tox Cat. Ill
00155932
Comeal opacity
redness and
vascularization
Tox Cat. I
00155934
Non-
irritating
Tox Cat IV
00155935
Nonsensitizing
00155936
None Available
None Available
None Available
M=790
F=450
Tox Cat II
43396201
>2000
Tox Cat IV
43452201
None
Available
Severe eye
irritation day 1
to day 21
Tox Cat. I
43396201
Non-
irritating
Tox Cat IV
43396201
25
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Copper Type
Copper metallic
Cupric oxide
(97.6%)
Cuprous oxide
(57%)
Copper from
triethanolamine
complex
[K-TEA]
Copper 8-
quinolinolate
Elemental copper
(ethyenediamine)
PC
Code
022501
042401
025601
024403
024002
024407
Acute Oral
LD50
(mg/kg)
50% copper
M= 1414
F= 1625
Tox Cat. Ill
00162424
>5050
(M&F)
Tox Cat IV
41502401
>5000
Tox Cat IV
00078971
99%
M=1170
F= 1312
Tox Cat. Ill
41759301
99.5%
>5000 M&F
Tox Cat. IV
KOMEEN
96%, K-Tea
99%
M=527
F=462
Tox Cat. II
41759201
Acute
Dermal
LD50
(mg/kg)
8.5%
elemental
>2000
Tox Cat. Ill
00150641
>2020
(M&F)
Tox Cat III
41502402
>2000
slight
erythema,
edema
Tox Cat III
00245650
99%
>2000
mg/kg
No deaths
Tox Cat. Ill
41759302
99.5%
>2000 M&F
Tox Cat. Ill
43558501
KOMEEN
& K-Tea
>2000
Tox Cat. Ill
41759202
Acute
Inhalation
(mg/L)
23% metallic
>0.1 but
0.59
Tox Cat III
00156396
>2.08 (M&F)
Tox Cat III
41502403
40.9% ai
0.1 to 0.59
Tox Cat I
42240303
None
Available
96%
0.09 M& 0.03
F
Tox Cat. II
43611901
KOMEEN &
K-Tea
M= 1.36
F= 0.56
Tox Cat. Ill
42130001
Primary Eye
Irritation
50% metallic
opacity,
irritation,
redness,
chemosis,
cleared by day
21
Tox Cat. II
00126194
Irritation
cleared in 7
days
Tox Cat III
41502404
Opacity, iris
irritation,
redness, and
chemosis
clearing by day
14
Tox Cat II
00078974
99%
moderate
irritation of
cornea, iris,
conjunctive
cleared by day
7.
Tox Cat. Ill
41759303
98%
comeal opacity,
redness to day
21
Tox Cat. I
KOMEEN &
K-Tea
moderate
irritation
Tox Cat. Ill
41759203
Dermal
Irritation
50%
metallic
erythema,
edema,
irritation,
cleared day
14
Tox Cat. IV
00126194
Irritation
cleared day
21
PI Index=
1.49
Tox Cat III
41502405
Severe
erythema,
edema
PIS=6.1/8
Tox Cat I
00078970
99%
mild
irritation
cleared by
day 3
Tox Cat. IV
41759304
99.7%
Non-
irritating
Tox Cat. IV
KOMEEN
& K-Tea
redness,
edema,
cleared by
day 3
41759204
Dermal
Sensitization
26% metallic
nonsensitizing
guinea pig
00144555
8.5% elemental
nonsensitizing
rabbit
00152166
Non-sensitizing
(guinea pig)
41502406
Non-sensitizing
(guinea pig)
00078970
None Available
99.7%
Non-sensitizing
guinea pig
KOMEEN &
K-Tea
non sensitizing
guinea pig
42130002
26
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Copper Type
Copper
naphthenate
Copper
octanoate, 10%
fatty acids
Copper salts of
fatty and rosin
acids
(Cu & zinc
neoisoate 35%)
Cuprous
thiocyanate
(99%)
Copper
ethanolamine
complex
PC
Code
023102
023306
023104
025602
024409
Acute Oral
LD50
(mg/kg)
8% Cu
M= >5050
F= >5050
Tox Cat. IV
43643701
>2000 M&F
Tox Cat. Ill
43947504
>7000
Tox Cat. IV
>5000
Tox Cat IV
40834601
Acute
Dermal
LD50
(mg/kg)
8% Cu
M= >2020
F= >2020
Tox Cat. Ill
43643702
>2000
M&F
Tox Cat. Ill
43947505
>2000
Tox Cat. Ill
>2000
Tox Cat III
40834601
Acute
Inhalation
(mg/L)
9.5% Cu
M&F=>2.96
Tox Cat. Ill
> 0.38 M&F
Tox Cat. Ill
43970201
None
Available
> 0.5 mg/L
Tox Cat. II
40834605
Primary Eye
Irritation
1. 8%Cu
irritation,
chemosis,
cleared by 48
hrs,
Tox Cat. Ill
43643703
2. 45% Cu
opacity,
redness,
chemosis &
discharge at 72
hrs
Tox Cat. I
00266172
irritation,
cleared by 48
hrs.
Tox Cat. IV
43937506
no irritation
Tox Cat. IV
non-irritant
40834605
Dermal
Irritation
8% Cu
erythema/es
char
slight edema
PIS=1.1
Tox Cat. Ill
43642704
2. 80% Cu
72 hrs
severe
erythema,
edema
Tox Cat. II
00260891
slight
erythema,
edema,
cleared by
72 hrs.
Tox Cat. IV
43947507
Edema,
erythema,
PIS=1.0
Tox Cat III
non-irritant
40834604
Dermal
Sensitization
9.5% Cu
sensitizer
Non-sensitizing
guinea pig
44116101
None Available
non-sensitizing
40834603
None Available
Copper generally has moderate to low toxicity (Toxicity Category II, III and IV) based on
acute oral, dermal and inhalation studies in animals. However, available studies indicate that
some copper species may cause severe irritation (Toxicity Category I), such as copper sulfate
pentahydrate, cuprous oxide, and copper 8-quinolinolate. Most dermal irritation studies indicate
Toxicity Category III or IV; however, cuprous oxide produced Toxicity Category I irritation.
Copper was generally non-sensitizing in animals, except for copper naphthenate which was a
skin sensitizer. When ingested, copper can be a gastric irritant and produce corrosion of the
gastric and intestinal epithelium. Open literature and data submitted by the registrants indicate
that acute responses to large copper concentrations are a result of acute irritation. Inhalation of
copper as dusts or mists is likely to be irritating to the respiratory system. Acute responses to
ingesting large amounts of copper may produce a metallic taste, abdominal pain, nausea and
vomiting, or diarrhea, especially if the stomach is empty and copper is taken with acidic foods,
beverages, or with other supplements.
All effects resulting from acute exposure to these copper-containing pesticides are due to
acute body responses to minimize excessive absorption or exposure to copper. Given the role
27
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copper plays as an essential element to the human body, its ubiquitous nature in food and
drinking water, the long-standing tolerance exemptions for the pesticidal use of copper on
growing crops, as well as on meat, milk, poultry, eggs, fish, shellfish, and irrigated crops, and the
lack of systemic toxicity resulting from copper, a quantitative acute toxicity assessment was not
conducted for acute dietary, dermal, oral or inhalation exposures. Current available data in
animals do not show any evidence of upper limit toxicity level that warrant determining acute
toxicity endpoints.
Sub-chronic and Chronic Toxicity. Based on available data, there is no evidence that warrants
determining any dietary, oral, dermal or inhalation endpoints to quantify sub-chronic and chronic
toxicity. Available short-term feeding studies with rats and mice indicate decreased food and
water intake with increasing oral concentrations of copper, with irritation of the stomach at
higher copper concentrations. High levels of excess copper administered in the drinking water of
mice suggested an altered immune response; however, the inhibition of immune responses is not
unusual since other trace elements have been linked with immuno-suppression. In addition,
cations like zinc, mercury, and lead have also been reported to alter immune responses. The
mechanism by which copper may be exerting a response in the immune system has not been
fully determined.
Longer feeding studies indicate decreased feed intake with reductions in body weight
gains, and increased copper concentration of the liver. Some available literature indicates that
chronic inhalations of copper may become cancerous, specifically seen in some professional
vineyard workers that were chronically exposed to Bordeaux mixture (copper sulfate and
hydrated lime mixture). However, this information is not definitive since no information is
available on the level of copper exposure to the workers, or any other substances with which they
might have come into contact. Available reproductive and developmental studies by the oral
route of exposure generally indicate that the main concern in animals for reproductive and
teratogenic effects of copper has usually been associated with the deficiency rather than the
excess of copper. Current available data in animals do not show any evidence of upper limit
toxicity level that warrant determining chronic toxicity endpoints for any potential routes of
exposure.
5. FQPA Safety Factor Considerations
FFDCA, as amended by FQPA, directs the Agency to use an additional 10X safety factor
(SF), to account for potential pre- and postnatal toxicity and completeness of the data with
respect to exposure and toxicity to infants and children. FQPA authorizes the Agency to modify
the 10X FQPA SF only if reliable data demonstrate that the resulting level of exposure would be
safe for infants and children. In humans, there does not appear to be any reports in the literature
of teratogenesis induced by exposure to excess copper. The only teratogenic effects observed in
available animal studies occurred after exposure with copper salts at high doses which were
likely maternally toxic. Moreover, there is no evidence to suggest susceptibility in infants and
children. Since copper is an essential trace element, with copper deficiency more common in
humans than toxicity from the excess, and since the dietary (food and drinking water)
contribution of copper to the total diet is low, endpoints to quantitatively assess dietary risk were
not selected. EPA has low concerns and no residual uncertainties with regard to pre- or postnatal
28
-------
toxicity from copper exposures. Since a qualitative assessment was conducted for potential
human health exposure to copper, the 10X FQPA SF was not retained.
6. Aggregate Risk from Coppers (Dietary and Residential)
The FQPA amendments to the Federal Food, Drug, and Cosmetic Act (FFDCA, Section
408(b)(2)(A)(ii)) require "that there is a reasonable certainty that no harm will result from
aggregate exposure to the pesticide chemical residue, including all anticipated dietary exposures
and other exposures for which there is reliable information." In accordance with the FQPA, the
Agency must consider and aggregate pesticide exposures and risks from three major sources or
pathways: food, drinking water, and if applicable, residential or other non-occupational
exposures.
Copper is a ubiquitous, naturally occurring metal that is essential to human health, found
naturally at low levels in a variety of food products as well as in drinking water from copper
plumbing pipes. Additionally, copper generally has low to moderate acute toxicity via the oral,
dermal, and inhalation routes of exposure. Available literature and studies do not indicate any
systemic toxicity associated with copper exposure. Effects seen in the existing data base are as a
result of response mechanisms that protect the body from excessive exposure to copper.
Considering all available information on copper and the relatively low toxicity via all exposure
routes from all sources, the cupric ion (regardless of the original form/species of copper) when
used in pesticide products is unlikely to pose a significant hazard to the general public or any
population subgroup. Based on available studies and literature, there are no human health
aggregate risks of concern resulting from aggregate dietary and residential exposures.
7. Occupational Exposure
Copper compounds are used on a variety of agricultural, commercial, and residential use
sites as fungicides, bactericides, algaecides, herbicides, wood preservatives, and anti-fouling
agents. There is potential for exposure to occupational mixers, loaders and applicators of
copper-containing pesticides. There is also the potential for post-application exposure.
However, adverse effects resulting from dermal, oral or inhalation exposures are due to the
irritating properties of copper, rather than a result of systemic toxicity. No dermal, oral or
inhalation endpoints were established to determine any potential systemic toxicity resulting from
occupational uses of copper products. Thus, there are no occupational risks of concern to the
Agency. Although there are no occupational risks of concern, the severe irritating properties of
some coppers warrant appropriate precautionary labeling to address any handler or post-
application exposures based on acute toxicity categories for individual copper compounds.
8. Incidence Data on Copper Exposure
The EPA's Incident Data System (IDS) has seven recorded pesticide incidents for copper;
five involve copper hydroxide and two involve copper sulfate pentahydrate. According to a
review of the scientific literature, copper compounds formulated as dusts and as powders are
irritating to the skin, respiratory tract, and the eyes. Most copper compounds have low systemic
toxicity, due mainly to their limited solubility and absorption. Occupational exposure to copper
29
-------
containing compounds frequently results in irritation effects. The majority of the noted effects
involved skin and eye irritation, nausea, vomiting, and headaches. These findings from the
scientific literature reflect the reported incidents from IDS.
The principle types of copper fungicides included in the Poison Control Center data
(1993-2003) are copper sulfate and copper hydroxide. Of the 82 copper exposures identified in
the Poison Control Center data, only 20 were seen in a health care facility, and three cases had a
moderate medical outcome. The leading symptoms included ocular irritation, vomiting, nausea,
and dermal irritation. Data from the California Department of Pesticide Regulation (1982-2003)
show that 156 cases (out of 494 reported) were due to copper compounds. The majority of these
cases show eye effects, skin effects, or other acute effects (i.e., respiratory effects). Of the top
200 chemicals for which the NPIC received calls from (1984-1991), copper hydroxide was
ranked 167th and copper sulfate was ranked 179th, with 15 and 13 reports of illness to humans,
respectively. National Institute for Occupational Safety and Health Sentinel Event Notification
Systems for Occupational Risks (NIOSH SENSOR) data reveal that out of 5899 reported cases
between 1998- 2003, only 34 cases were documented as involving copper (copper sulfate
pentahydrate, copper hydroxide, and copper-ammonia complex). Twenty-five of the 34
documented cases were from California, and most likely overlap the cases discussed above from
the California Department of Pesticide Regulation.
Given the long history of copper use over the past several centuries and the extensive use
of copper compounds in agricultural and direct aquatic applications, the number of reported
incidents related to copper is relatively low. Reported effects (i.e., eye and dermal irritation,
emesis, nausea, etc.) were consistent with acute irritation effects that may occur when exposed to
products containing copper. These reported incidents do not indicate systemic toxicity effects
resulting from copper exposure, but do support a conclusion that acute irritation effects are the
primary concern for exposures to copper compounds. The potential acute irritation effects of
some copper pesticides warrant appropriate precautionary labeling to address any handler or
post-application exposures. With these protective measures in place to reduce potential
exposures, there are no risks of concern to the Agency.
B. Ecological Risk Assessment
A summary of the Agency's environmental risk assessment for coppers is presented
below. As a bridging strategy to address the range of copper compounds included in this
assessment, the Agency has evaluated all copper active ingredients with registered agricultural
uses on the basis of the cupric ion (Cu2+) regardless of the original form of the copper compound.
Antimicrobial applications of copper will be assessed separately at a later date. The complete
revised environmental risk assessment for agricultural uses of coppers may be accessed online at
www.regulations.sov under Public Docket EPA-OPP-HQ-2005-0558. This risk assessment was
refined and updated to incorporate comments and additional data submitted by the registrants
and other stakeholders.
30
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1.
Environmental Fate
Copper naturally occurs in the environment, and continuously cycles through natural
geothermodynamic processes that binds or releases copper ions. Because copper is an element, it
cannot break down any further via hydrolysis, metabolism, or any other degradation processes.
The free cupric ion has a high sorption affinity for soil, sediments and organic matter, and copper
applied to the surface is not expected to readily move into groundwater.
The copper ion is highly reactive, especially in aquatic environments. Copper can exist
in various organic and inorganic forms, including the cupric ion (Cu2+), cuprous ion (Cu+),
inorganic complexes, organic complexes and minerals. In this assessment, the term "speciation"
refers to the relative proportion of total copper in these various forms. Figure 1 provides an
overview of the chemistry of copper in aqueous systems.
A
i —
i
r
Inorganic Cu
Complexes
Figure 1 - Environmental Fate Bridging Strategy for Cu Minerals and Complexes
Copper can exist in various oxidation states as inorganic complexes, organic complexes
and minerals; Figure 1 distinguishes these mineral states with Roman numerals (e.g., Cu(I) and
Cu(II)). The oxidation of Cu(0) to Cu(I) or Cu(II) depends on the redox conditions. Redox
potential is the tendency of the environment to deplete molecular oxygen from the system to
form oxygen-containing compounds. Redox potential can be measured as an electrical potential
in millivolts (mV). It also controls the chemical forms of other compounds in the environment.
The form in which Cu(I) or Cu(II) species is found depends on the pH of the medium and the
nature and concentration of other chemical species that can form copper-containing species.
-------
This ecological assessment addresses terrestrial crop and direct aquatic uses of Cu(II)
salts, oxides, hydroxides, and organic complexes. When used as a pesticide, the cupric ion is
released via dissolution of copper salts, oxides/hydroxides and/or by the breakdown of organic
complexes and/or degradation of the organic moiety. The extent of dissociation of copper
species is controlled by the solubility of the compound, which is dependent on the pH of the
environment. It also depends on redox potential, dissolved organic carbon (DOC) and
competing ligands. However, for the purposes of this assessment, copper compounds reaching
surface water (as simulated by PRZM/EXAMS) is assumed to completely and instantaneously
dissociate. As described below, speciation of this loading of dissolved copper is then simulated
using the Biotic-Ligand Model (BLM).
Since copper is a naturally occurring element, there are always background
concentrations of copper from which point and non-point sources cannot easily be distinguished.
Aside from natural environmental releases of copper, there are other sources, such as pesticides,
anti-foulants and wood preservatives, leaching from mining operations, industrial runoff,
architectural uses, and brake pads. Therefore, concentrations of copper measured in soil or water
can also reflect other point or non-point sources of copper besides pesticides.
2. Ecological Exposure and Risk
The Agency has used the existing environmental database and open literature for coppers
to characterize the environmental exposure associated with copper agricultural uses for this
screening-level assessment. The risk assessment is based on a subset of representative labels of
copper sulfate pentahydrate and copper hydroxide for agricultural uses, which represents a wide
range of application rates. Although there are several other registered active ingredients
containing copper, the risk assessment assumes instantaneous disassociation of the cupric ion
from its counter ion or ligand, which is a conservative estimate for the potential bioavailable
amount of copper to exposed organisms. The Agency assessed both maximum labeled rates and
typical average use rates. All copper concentrations are expressed in the risk assessments as the
copper or cupric ion, the toxic ion of concern.
The Agency's ecological risk assessment compares toxicity endpoints from ecological
toxicity data to estimated environmental concentrations (EECs) based on environmental fate
characteristics, soil and water chemistry, and pesticide use data. To evaluate the potential risks
to nontarget organisms from the use of copper pesticides, the Agency calculates a Risk Quotient
(RQ), which is the ratio of the EEC to the most sensitive toxicity endpoint values, such as the
median lethal dose (LD50) or the median lethal concentration (LCso).
RQ values are compared to the Agency's levels of concern (LOCs), which indicate
whether a pesticide, when used as labeled, has the potential to cause adverse effects on nontarget
organisms. When the RQ exceeds the LOG for a particular category, the Agency presumes a
potential risk of concern to that category. Table 4 describes the Agency's LOCs and its
respective risk presumptions. These RQ values may be further refined by characterization of the
risk assessment. Use, toxicity, fate and exposure are considered when characterizing the risk, as
well as the levels of certainty and uncertainty in the assessment.
32
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Table 4. Agency's LOCs and Risk Presumptions
Risk Presumption
Acute Risk - there is potential for acute risk;
regulatory action may be warranted.
Acute Endangered Species - there is potential for
endangered species risk; regulatory action may be
warranted.
Chronic Risk - there is potential for chronic risk;
regulatory action may be warranted.
LOC
Terrestrial Animals
0.5
0.1
1
LOC
Aquatic Animals
0.5
0.05
1
LOC
Plants
1
1
N/A
Copper is an essential nutrient required for proper homeostasis in all organisms. Most
organisms have homeostatic mechanisms to process excess copper or to manage the deficiency
of copper levels. However, aquatic animals are exposed to copper by more than just dietary
routes, and are more sensitive to copper than terrestrial animals. The mode of toxicity for
aquatic organisms is different than for terrestrial animals in that copper rapidly binds and causes
damage to the gill membranes, and interferes with osmoregulatory processes. Aquatic plants,
which are target organisms for most direct aquatic uses of copper, are also more sensitive to
copper than terrestrial plants.
The toxicity of copper to aquatic animals depends on the amount of bioavailable cupric
ion in the water. To address potential risk to freshwater organisms, the Agency used the Biotic-
Ligand Model (BLM) (Windows Version 2.0.0, 4/03) in addition to standard current methods to
assess exposure and toxicity to potentially exposed freshwater organisms. The BLM method is
discussed in greater detail below.
The BLM has not yet been parameterized for estuarine/marine organisms, as it has for
freshwater animals. This would require evaluating data for specific estuarine/marine species
under a sufficient range of water quality conditions to determine the effect of these conditions on
copper toxicity. Therefore, since the BLM could not be used, RQs for estuarine/marine animals
were calculated using estimates of total dissolved copper, and are therefore calculated using
conservative exposure values. For freshwater plants, saltwater organisms and terrestrial animals
and plants, standard Agency models and methods were used to assess potential copper
exposures.
For a more detailed explanation of the ecological risks posed by the agricultural use of
coppers, refer to Error Corrections for the Ecological Risk Assessment for Re-Registration of
copper sulfate (case #0636), group II copper compounds (case #0649), and copper salts (case
#0649) for use on crops and as direct water applications, dated April 20, 2006.
a. Aquatic Organisms
1. Freshwater Fish and Invertebrates
Agricultural Uses
The EECs of total dissolved copper (versus Cu2+ only) in surface water resulting from
agricultural uses of copper pesticides were simulated using the Agency's standard pesticide
33
-------
transport models PRZM and EXAMS (PRZM/EXAMS). However, the selection of input
parameters for these models was complicated by the elemental nature of copper.
PRZM/EXAMS require input for both persistence and mobility of the pesticide, and while the
various formulations of copper are assumed in the risk assessment to dissociate immediately in
water to release the cupric ion, the cupric ion itself does not degrade. All metabolism and
degradation parameters were set with half-lives long enough that copper would essentially not
degrade over the 30-year simulation. The one exception was the use of a 10-day aquatic
dissipation half-life in place of an aerobic aquatic metabolism half-life in EXAMS. This allowed
consideration of chronic exposure in the water column, imitating the preferential partitioning of
copper away from the dissolved phase and into a bound state in sediment. Soil partitioning
coefficients for sand and clay soils were used to allow consideration of scenarios in which
greater and lesser amounts of copper were bound to the soil.
Thirty-two separate PRZM/EXAMS modeling scenarios were selected to represent the
various crop groupings, which provided a range of geographic conditions and use rates. Use
rates for copper sulfate, copper sulfate pentahydrate, and copper hydroxide were derived from
representative labels. Because of the vast array of labels, a representative subset of labels was
chosen to assess the range of copper application rates. The screening-level risk assessment was
based on use sites with the highest application rates found for agricultural uses on crops that
account for the majority of agricultural use of copper hydroxide and copper sulfate. The number
of applications and application intervals were generally not specified on labels. Therefore, the
modeling was conducted assuming four applications at weekly intervals.
Because the PRZM/EXAMS model cannot account for chemical speciation of copper,
which affects its toxicity, the BLM was used to estimate the cupric ion concentration in surface
water. The BLM, essentially a combined speciation and toxicity model, allows calculation of
toxicity values based on site-specific water chemistry. Use of the BLM in this pesticide risk
assessment is consistent with the method used by the EPA's Office of Water (OW), which used
the BLM to revise the Aquatic Life Criteria (ALC) for copper in 2003. EPA OW is currently
preparing guidance on the use of the BLM to derive site-specific ALC for copper based on site-
specific water chemistry. Figure 2 describes the use of the BLM in the ecological risk
assessment.
34
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Exposure:
Developing Activity-based
Site Specific EECs
Effects:
Developing Activity-
based
Site Specific LC50s
PRZM/EXAMS
SIMULATIONS
(Site Specific
Scenarios)
EECs (ppb)
[Cu]
total dissolved
Site Specific
USGS Water Quality
Monitoring Data
Biotic Ligand Model
(Toxicity Mode)
Biotic Ligand Model
(Speciation Mode)
Site Specific
Daphnia magna LC50 (ppb)
Site Specific RQs
Daphnia magna
(unitless)
Figure 2. Site-specific aquatic assessment using the BLM
For the copper pesticides risk assessment, PRZM/EXAMS estimated total copper
concentrations (peak and 21-day average concentration) for low Kd (sandy soil) and high Kd
(clay soil) for each crop scenario to derive the copper input concentration in the BLM model. In
order to portion out speciated copper among its various forms in water, the BLM also requires
water quality input parameters which are mostly not input parameters for PRZM/EXAMS.
Water quality input parameters for the BLM model were populated using United States
Geological Service (USGS) water quality monitoring data for filtered water, from nationwide
monitoring programs such as NAWQA and NASQAN. The USGS water quality monitoring
data were censored to remove all samples with water input parameters outside the range of the
model. The samples that were removed were excluded predominantly for having water
temperature higher than the range handled by the BLM. However, the other water quality
parameters from these samples suggest that the copper exposure and toxicity that would result
would likely be within the range for the large number of USGS samples that were used in the
BLM.
35
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Eight-hundred eleven USGS sites representing median water quality conditions were
used in the BLM to assess a representative range of water column conditions in surface water
across the United States. Median conditions were selected rather than worst case conditions
because they represent the conditions most likely to occur. Table 5 describes the range of water
quality data inputs used in the BLM. Variability across sites is expected to be greater than
variability at a single site. BLM simulations provided an estimation of the cupric ion activity
(moles/liter) in water for each of the 811 sites.
Table 5. Summary of USGS Water Quality Data Used in the BLM1
Parameter
Temperature
pH
Cu
DOC
Humic Acid2
Ca2+
Mg2+
Na+
K+
SO42"
cr
Alkalinity
S2'
Units
°C
none
ug/L
mg/L
%
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
mg/L
Data Range for
BLM
10 to 25
4.9 to 9.2
ND
0.05 to 29.65
10 to 60
0.204 to 120.24
0.024 to 51. 9
0.16 to 236.9
0.039 to 278.4
0.096 to 278.4
0.32 to 279.72
1.99 to 360
ND
Missing
Data
0
0
363
0
0
0
0
0
0
0
0
0
811
Low Value
10
5.05
1.0
0.2
10
0.95
0.18
0.88
0.09
0.10
0.32
2.0
ND
High
Value
24.5
9.2
51.4
29.2
29.15
114
51.8
190
18
270
266
311
ND
Median
Value
17.4
8.0
1.2
3.00
14.90
37.6
10.6
10.3
2.2
26.1
11
116
ND
Average
Value
17.2
7.85
2.61
4.06
16.69
40.62
13.02
21.09
2.93
44.46
22.66
120.61
ND
1- Data represent median site water quality conditions within the range of data for development of BLM
2- Humic acid percentage was estimated from the DOC concentration
ND - No data available, oxic conditions assumed
Typically, the Agency would calculate RQs using the most sensitive LCso for a
taxonomic group and the 1-in-10-year acute and chronic EECs from PRZM/EXAMS. However,
potential copper toxicity in natural waters is largely a function of water chemistry, so the toxicity
to a particular organism will vary from site to site. Copper is most toxic in waters of low ionic
strength and/or low in dissolved organic carbon (DOC). The pH of the water also affects
toxicity.
Because the toxicity of copper varies greatly depending on water chemistry, the same
water chemistry data collected by USGS was input to the BLM to calculate LCsoS for Daphnia
magna (cladoceran, representing aquatic invertebrates), and Pimephalespromelas (fathead
minnow, representing fish). Daphnia were the most sensitive genera of aquatic invertebrates for
which data were available, and the most sensitive aquatic species overall. Salmonids (genus
Onchorynchus; genus mean acute value (GMAV) of 29.11 |ig/L) are the most sensitive fish
species, but at the time of this assessment, the BLM had not yet been implemented to calculate
the LCso for this genus, thus the fathead minnow LCsoS produced by the BLM was adjusted by
36
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the ratio of the Onchorynchus GMAV to the Pimephales GMAV (29.11 |ig/L:72.07 |ig/L;
adjustment factor 0.404).
The chronic toxicity of copper to aquatic animals was also calculated in a manner
consistent with that used by OW to derive ALC for copper. The minimum data requirements for
developing chronic ALC were not met, so OW elected to use the acute-to-chronic ratio (ACR)
approach to derive chronic criteria. OW determined an ACR of 3.23 for freshwater organisms,
which was a central value derived from a range of ACRs for freshwater species for which both
acute and chronic toxicity data were available. For the ecological risk assessment, the ACR was
applied to the acute toxicity value for each of the 811 sites to establish a chronic toxicity value
for RQ calculation.
At the time the ecological risk assessment for copper pesticides was conducted, many
product labels had inconsistent information on the maximum amount of copper that can be used
on many crops. The ecological risk assessment assumes four applications applied one week
apart at the maximum label rate in cases when the maximum rates and minimum intervals are not
described on the label. In order to allow an evaluation of potential risk at different application
rates that might be established on revised copper labels, the Agency performed a regression on
the peak cupric ion concentrations based on various application rates in the 32 PRZM/EXAMS
simulations run for copper. The data points used to calculate the regression and the resulting
regression equation are shown in Figure 3, below.
Relationship of Cu Application Rate
and Peak Cu Concentration
100
O
o
O
80 -
60 -
O 40 -
CO
CD
Q_
20 -
Y=-0.3800+2.5358(X) I2=0.75
10
15
20
25
30
35
Cu Application Rate (Ib Cu/A)
Figure 3 - Correlation of Peak Cu2+ Concentrations in the Standard Small Water Body with
Application Rates
The peak cupric ion concentrations generated from PRZM/EXAMS were the inputs used
in the BLM. Using the BLM to estimate site-specific cupric ion concentrations and toxicity
37
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endpoints, individual RQs were calculated for each of the 811 USGS sample sites. The resulting
RQs were compared to the Agency's LOCs for aquatic animals. The potential for acute risk to
aquatic animals is described in terms of percentages of the 811 sites that exceed the Agency's
LOG for a range of potential application rates.
The screening-level risk assessment indicates that there are risks greater than the LOG to
freshwater invertebrates from terrestrial uses of copper at some portion of the 811 sites modeled,
regardless of the application rate. At the maximum label application rate considered in the risk
assessment, 31.8 pounds of metallic copper per acre (Ibs Cu2+/A) for filberts, RQs for nearly all
sites exceeded the acute and chronic LOCs. Over 99% of the sites exceeded the acute LOG for
invertebrates, and 80% exceeded for fish. Over 98% of the sites exceeded the chronic LOG for
invertebrates and 44.9% exceeded for fish.
The percentage of sites for which RQs exceed the acute LOG is significantly less for
typical rates more likely to be applied. The percentage of sites ranges from 3.2% at 1.0 Ib
Cu2+/A, and increases to about 25% of sites at an application rate of 7.5 Ibs Cu2+/A. The RQs
derived for freshwater fish with the BLM exceed the acute LOG for less than 1% of sites for
application rates of 1.0 Ib Cu2+/A and above.
The same exposure estimates translate into a greater number of sites exceeding the acute
endangered species LOG of 0.05. As shown in Table 6 below, even at a rate of 1.0 Ib Cu2+/A,
aquatic RQs exceed that LOG in 19% of the 811 sites for freshwater invertebrates, while only
exceeding the LOG for 1% of those sites for freshwater fish. The level of exceedence of the
acute endangered species LOG for freshwater invertebrates and fish increases to 84% and 17%,
respectively, based on an application rate of 7.5 Ibs Cu2+/A.
Table 6. Summary of Acute LOG Exceedences in Freshwater Environments from Agricultural Uses
Rate
Ibs Cu2+/A (ppb)
1.0 (2.2)
1.5 (3.4)
3.0 (7.2)
5.0(12.3)
7.5 (18.6)
Acute
Invertebrate1
3.2%
5.0%
10.3%
17.0%
24.6%
Fish1
<1%
<1%
<1%
<1%
<1%
Acute Endangered Species
Invertebrate1
19.0%
29.6%
53.4%
71.5%
84.0%
Fish1
1.0%
1.4%
6.0%
10.4%
17.1%
1 Presented in terms of the percentage of sites in the USGS data set exceeding the acute risk LOG or acute
endangered species LOG.
As part of the development of the ALC for copper, OW derived an acute-to-chronic ratio
(ACR) of 3.23 for freshwater organisms (USEPA 2003a). The BLM only estimates acute
toxicity, so the ACR was applied to site specific LCsos for both the daphnids and salmonids to
generate site specific chronic toxicity values. These were compared to the 21-day EECs
speciated by the BLM to derive chronic RQs. Table 7 shows the percentage of sites for which
freshwater animal RQs exceed the chronic LOG. RQs for fish are usually calculated using the
60-day EEC, but a suitable regression could not be fit to the 60-day EECs from the 32
PRZM/EXAMS scenarios. Therefore, although RQs for few sites exceed the chronic LOG for
fish at rates up to 7.5 Ib Cu2+/A, the assessment should be considered conservative because the
38
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21-day EECs are higher than 60-day EECs for any particular site.
Table 7. Summary of Chronic Risk LOG Exceedences in Aquatic Environments
Rate
Ibs Cu2+/A(Cu ppb)
1.0 (2.2)
1.5 (2.9)
3.0 (5.3)
5.0 (8.4)
7.5(12.3)
Freshwater
Invertebrate1
4.2%
6.3%
13.4%
22.2%
32.4%
Fish1
0.0%
0.1%
1.0%
2.5%
5.3%
Presented in terms of percentage of sites in the USGS data set exceeding the chronic risk LOCs
The distribution of the 811 RQ values reflects the distribution of the water quality
parameters from the 811 USGS sampling sites. Therefore, the shape of the distribution is the
same for each application rate. An example from the ecological risk assessment shows the range
of RQs for application to apples at an application rate of 3.8 Ibs Cu2+/A. Table 8 below shows
that the acute LOCs are exceeded for freshwater invertebrates, with a RQ range of 0.01 to 498.
The median value, however, is 0.47. Although nearly half of the RQs exceed the acute LOG of
0.5, the distribution of RQs is skewed toward the lower values in the distribution. The acute RQ
distribution for fish and the chronic RQ distribution for invertebrates and fish show this same
pattern.
Table 8. Aquatic RQ Summary: Orchard Average Application Rate (3.8 Ibs Cu2+/A)
Endpoint for RQ
Minimum RQ | Median RQ
Maximum RQ
Acute
Invertebrate
Fish
0.01
0.00
0.47
0.02
498
41
Chronic
Invertebrate
Fish
0.02
0.01
0.66
0.05
352
6.1
Acute LOG for invertebrates and fish = 0.5, Acute endangered species LOG for invertebrates and fish = 0.05, acute,
chronic LOG for invertebrates, fish =1.0
Exposure via Spray Drift
There is some uncertainty in the level of exceedances because spray drift was not
included as part of the potential total copper exposure in the BLM analysis. The assessment did
not include spray drift because the labels did not specify the method by which copper would be
applied. A screening-level spray drift analysis was conducted separately in the revised risk
assessment to evaluate the impact of copper spray drift from terrestrial crop uses on aquatic
environments. The analysis assumes drift loadings of 5% of the application rate for aerial spray
and 1% of application rate for ground spray into the standard farm pond used in EXAMS. Peak
concentrations of copper from spray drift were speciated using the BLM model to estimate the
concentration of cupric ion in the pond. Median USGS monitoring site water quality data for the
811 sites were used as input parameters for the BLM model.
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Site exceedences of the aquatic LOG and endangered species aquatic LOG were found
for both ground and aerial spray drift loadings. At the highest application rate proposed for
reregi strati on (6 Ibs Cu2+/A, for filberts), a single aerial application would result in 28% and 5%
of sites exceeding the acute LOG for freshwater invertebrates and fish, respectively. A
corresponding ground spray application would result in 7% and 4% exceedances, respectively.
The same simulated exposure suggests that the freshwater invertebrate endangered species LOG
would be exceeded at 89% and 32% of sites from aerial and ground spray, respectively. Lower
application rates associated with other crops would result in lower estimated exposure, and a
smaller percentage of sites at which the LOCs would be exceeded.
Uncertainties in Freshwater Animal Risk Assessment
There is some uncertainty in the level of exceedances of the acute and acute endangered
species LOCs from agricultural uses of copper, because the regression used to predict the
exposure input to the BLM was derived from 32 scenarios representing climatic and soil
conditions from around the country. In addition, the peak value from each of the 32 scenarios
was from a single year of modeling with PRZM/EXAMS. Standard exposure assessments with
PRZM/EXAMS simulate 30 years of applications with 30 years of daily rainfall and climate data
from a nearby weather station. Since elemental copper does not degrade, the effect of 30 years
of applications would be to accumulate copper in the static pond simulated by EXAMS. The
EEC simulated from the first of the 30 years of data would likely be less than the standard 1-in-
10-year exposure value calculated from a full 30-year simulation, although some of the 32 sites
would simulate heavier rainfall in that single year, and others would simulate light rainfall years.
The choice of the soil-partitioning coefficient (Kd) used as input to PRZM/EXAMS
served to make the estimated number of sites with RQs exceeding acute and chronic LOCs more
conservative. The environmental fate assessment reports a range of Kd values from 0.4 L/g (sand
soil) to 3.6 L/g(clay soil). PRZM-EXAMS models were used to estimate copper concentrations
for the low Kd and high Kd values for each crop scenario to derive the copper input concentration
for the BLM model. The regression used to estimate EECs for different application rates used
the output from the low Kd modeling runs, which causes the model to simulate more copper
transport from the field, and more copper in the dissolved phase in the pond (and less in the bed
sediment). This results in higher copper input to the BLM, and a conservative estimate of the
number of sites that would exceed an LOG for a particular application rate.
In addition, the number of applications and application interval was not the same for all
32 simulations, although the majority of them assumed four applications spaced a week apart.
The need to assume a number of applications and an application interval is a result of
inconsistent product labels for copper pesticides which do not specify the maximum number of
applications and minimum treatment interval. Imprecise product labels (unspecified application
intervals and application frequencies) represent the greatest source of uncertainty in the
ecological risk assessment for copper pesticides. Because the labels do not specify these limits,
the potential maximum loading of the chemical into the environment may grossly underestimate
or overestimate potential risk.
Finally, as mentioned earlier, the mean water quality characteristics from 811 USGS
40
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sampling sites result in a wide range of copper exposure and toxicity values, but may not
represent the full range of potential conditions. This data set of 811 sites represents 47 states (no
sites in Maine, South Carolina, or Virginia), but does not represent every region equally. For
instance, since the available data set was censored to remove any sites with temperature values
outside the range that can be assessed by the BLM, the southeastern United States is not as well
represented as other parts of the country.
Aquatic Uses
The aquatic risk assessment for direct application of copper pesticides to water uses the
EXAMS model in conjunction with the BLM to produce RQs over a range of water quality
conditions. EXAMS accounts for sediment-to-water partitioning, and the BLM incorporates the
effects of copper speciation. Use data indicate a target concentration for algae and aquatic weeds
control of 0.1-1 ppm. For snails, leeches, and other similar organisms, application rates may be
higher, ranging from 1-2.5 ppm. The risk assessment indicates that for an application rate of 1
ppm, peak concentrations of Cu2+ are predicted by EXAMS to be approximately 0.9 ppm if the
pesticide were to be applied to the entire water body. The estimated average 21-day
concentration at this rate is 522 ppb, and the estimated average 60-day concentration is 234 ppb.
For invertebrates, fish, and aquatic plants, >99% of sites exceed the endangered species
LOG and the acute risk LOG at this application rate. The chronic risk LOCs for aquatic
invertebrates, and fish are exceeded at >96% of the sites. The water body simulated by EXAMS
is a 1-hectare, 2-meter deep pond with no outlet. However, were an entire reservoir treated at the
same rate (which would require proportionally more copper), the level of predicted risk would be
the same.
The risk assessment also considers the potential for risk when only a portion of a water
body is treated. The EXAMS model was run in conjunction with the BLM to determine the
percentage of water bodies with characteristics of the 811 USGS samples would that exceed
LOCs for partial applications. A regression of these simulations suggests risk to freshwater fish
and invertebrates.
There is some uncertainty in this finding of risk for partial treatment of water bodies, due
to limitations of the exposure model itself. The EXAMS model simulates instantaneous mixing
of applied pesticide throughout the approximately 20,000,000-liter pond. Therefore, these
simulations of partial treatments are equivalent to full-pond treatments at a fraction of the
maximum application rate. Because of the great variance in water body chemistries across the
US, this will overestimate the potential risk to some aquatic organisms, and underestimate it for
others. The purpose of treating a portion of a water body can be to avoid killing enough plant
matter at one time to sharply increase oxygen-demand, and/or to give mobile aquatic animals the
opportunity to leave the treated area. When only a portion of the water body is treated,
organisms in the vicinity of the treatment can be exposed to the full concentration of copper
applied, while others farther from the treated area may not be exposed at all. This is especially
true for water bodies such as drinking water reservoirs, which are larger than the standard pond
simulated by EXAMS, both because of their size, and the amount of time it takes for total mixing
of water in those water bodies.
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However, for almost any direct water application of copper products, there are likely to
be effects on invertebrates and a reduction of primary production. Fish and larger, more mobile
invertebrates may be able to move out of the treated zone until the copper dissipates from the
water column, but smaller and more sedentary invertebrates will be affected. Recovery of the
affected organisms will vary on a site-to-site basis, and the specific effects on any given
ecosystem are impossible to predict given the scale of this assessment. Populations of
phytoplankton and zooplankton (the organisms most likely to be lethally affected by use of
copper) are dynamic. In aquatic systems where copper is applied frequently the community may
shift to more copper tolerant organisms, and/or some of the organisms present may develop
metabolic pathways for dealing with higher copper loading.
The potential risk to aquatic organisms must be considered in conjunction with the
environmental benefit intended for some uses of copper. Excessive algal growth in lakes or
ponds caused by high nutrient input can damage aquatic life by causing high oxygen demand, in
some cases leading to eutrophication. In other cases, copper is used to control invasive aquatic
plants which can out-compete and replace native plants, changing the ecosystem and reducing
food sources for aquatic and terrestrial animals in or near the water. The use of copper for
control of parasites (through snail control) benefits swimmers in recreational waters and fish that
can be infected.
Urban Uses
One of the risk assessment goals of the Office of Pesticide Programs (OPP) is to estimate
pesticide exposure through all significant routes of exposure from both agricultural and non-crop
uses. However, the ecological risk assessment for copper pesticides focuses on the agricultural
uses, because pesticide transport models are available to estimate potential aquatic exposure
from these uses. Based on laboratory toxicity tests with aquatic animals, aquatic exposure could
cause adverse effects in the environment.
Copper is used for a number of non-crop pesticidal uses, including use as a wood
treatment, lawn fungicide, pool and fountain algaecide, sanitary sewer root killer and ingredient
in anti-fouling paints. The wood treatment, anti-foulants, and other antimicrobial uses will be
addressed in a separate ecological risk assessment to be produced at a later date by the Agency's
Antimicrobials Division. This document addresses the root-killer and lawn uses to a limited
degree.
The root-killer use involves flushing two pounds of copper sulfate pentahydrate crystals
(0.5 Ib elemental copper) down a toilet as often as every six months to control tree root growth in
domestic sewer systems. Alternatively, label directions recommend one-half pound of product
each month as a "maintenance" treatment. The copper sulfate pentahydrate crystals cling to
roots and kill them over time.
The ecological risk assessment evaluates the sanitary sewer root-killer use with the
"down-the-drain" model E-FAST 2.0. In these simulations, wastewater containing copper
crystals flows from the building and passes through a sanitary sewer and publicly owned
treatment works (POTW) before being discharged to surface water. The E-FAST model uses the
42
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total national production of a pesticide and distributes it among all households in the nation.
However, since the amount of copper sulfate pentahydrate produced for this use could not be
distinguished from that manufactured for other uses, the ecological risk assessment made the
conservative assumption that each household in the United States applies 0.5 Ib of elemental
copper for root-control two times a year. This equates to approximately 2.2 million pounds of
metallic copper annually. The CSTF subsequently provided a preliminary estimate of potential
use of approximately 857,000 pounds of metallic copper annually. The assessment uses a copper
sulfate removal efficiency at the POTW of 1.8%, which was estimated using the model EPISuite.
The ecological risk assessment took the resulting concentrations of copper and used them
as input to the BLM. The resulting site-specific copper concentration estimates were compared
to the toxicity endpoints the BLM generated for each site. The assessment concluded that if all
households in the nation were to apply copper sulfate pentahydrate for root-control at maximum
recommended rates, then the acute LOG would be exceeded for 85% and 20% of model sites for
freshwater invertebrates and fish, respectively. The corresponding percentage of sites for which
the chronic level of concern could be exceeded would be 74% and 13%, respectively. However,
freshwater fish and invertebrates will not be directly exposed to the full amount of copper
applied for root control, since POTWs are required to first treat waste water received from
sanitary sewers.
The finding of risk described above should be considered an upper bound, since not every
household in the United States uses copper sulfate pentahydrate for root control. Since this
product label states that it is not for use in septic systems, even the total number of households
which could potentially use the product is lower than assumed in the risk assessment. However,
the use of copper sulfate pentahydrate in this manner does represent a direct introduction of
copper into the wastewater stream, which was a point of concern for commenters representing
POTWs. Tri-TAC, a technical advisory group for POTWs in California, commented that an
estimated 5 to 12% of copper received by POTWs in their state was a result of root-killer use.
The California Department of Pesticide Regulation has prohibited the use of copper sulfate
pentahydrate in nine counties in California out of concern that POTWs in the San Francisco Bay
area could not comply with water quality criteria for copper if this use continued.
The E-FAST model allowed a conservative, qualitative estimate of potential exposure
from the root-killer use, but no analogous exposure model has been developed to allow a similar
screening-level assessment for pesticides applied in an outdoor urban setting. As a result, the
Agency has had to take a qualitative approach to characterize the potential aquatic risk from
urban and suburban use of copper.
For outdoor urban uses, the Agency assumes that runoff water from rain and/or lawn
watering may transport pesticides to storm sewers and then directly to surface water. Copper
transported by runoff or erosion in an urban setting would take a path not only over lawns, but
also impervious surfaces such as walkways, driveways and streets. The Agency is unaware of
any model which can simulate the different application methods for urban use and the physical
representation of the urban landscape, storm sewer and receiving water configuration.
There are models available which can be calibrated to simulate sites and pesticides for
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which extensive flow and pollutant data have been collected in advance. The HSPF/NPSM
model, for instance, which is included in the EPA's BASINS shell, has been used to calibrate
stream flow and copper pesticide use data to simulate loading of these pesticides consistent with
concentrations measured in surface water monitoring. Risk assessors with the California
Department of Environmental Protection confirmed in conversations with the Agency that they
also have used watershed models to calibrate previously collected flow and pesticide monitoring
data, but that they did not know of any models capable of predicting concentrations of pesticides
that might occur because of outdoor urban uses.
Development of a screening model which could simulate the fate and transport of
pesticides applied in an urban setting would require a large body of data which is currently
unavailable. For instance, an urban landscape cannot be simulated as easily as an agricultural
field. The PRZM model simulates runoff from an agricultural field using readily available data
describing surface soil characteristics and laboratory data detailing the persistence and mobility
of pesticides in these soils. The agricultural field simulated is homogenously planted to a single
crop, and soil and water are transported from the field to a receiving water body with dimensions
consistent with USDA farm-pond construction guidelines.
By contrast, an urban landscape or suburban housing development consists of impervious
surfaces such as streets and sidewalks, and pervious surfaces such as lawns and parkland. One
could expect much greater mobility for pesticides applied to impervious surfaces, but laboratory
soil metabolism studies may not provide an accurate measure of the persistence of pesticides on
these surfaces. The path runoff water and eroded sediment might take is less obvious for an
urban setting than an agricultural field. First, an urban landscape cannot be considered
homogeneous, as the proportion of impervious and pervious surfaces varies for different
locations. In addition, the flow path of runoff water and sediment is not necessarily a direct path
over land, but can pass below ground through storm sewer networks, be directed, or slowed by
pumping stations or temporary holding ponds.
Finally, the timing and magnitude of urban uses is less well defined for urban uses than
agricultural uses. While agricultural uses would occur within a predictable window during the
growing season, the need for urban uses could occur at different times each year, and might
occur at different times within the same watershed. In addition, since records of how and to
what extent copper pesticides are applied by homeowners are not well defined, it is harder to
estimate the total load to model.
2. Freshwater Plants
Because the BLM has not been parameterized for freshwater plants, it could not be used
to assess potential copper exposure and toxicity from the cupric ion to freshwater plants. RQs
for freshwater plants were calculated using estimates of total dissolved copper using
PRZM/EXAMS, which overestimates the amount of copper that is potentially toxic to exposed
organisms. The RQs for aquatic plants are presented in Table 9 as individual RQs for each
application rate, because the actual toxicity posed by the cupric ion to these organisms cannot yet
be simulated by the BLM.
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The most sensitive aquatic plant species tested, the green alga, Selenastrum
capricormitum, (LCso = 3.1 ppb, NOEC = 0.2 ppb) was selected to represent non-vascular
aquatic plants. Duckweed, Lemna minor, (LCso = 2.3 ppm, NOEC = 0.1 ppm) was selected to
represent vascular aquatic plants. Since site-specific exposure and toxicity values for plants were
not generated using the BLM, risk is not described as a percentage of RQs above the LOG; rather
a single RQ is presented for each application rate, with EECs calculated using the regression
described above. Acute RQs based on the green alga, a target species for direct applications of
copper to water, exceed the acute and acute endangered species LOG of 1.0 for application rates
at or above 1 Ib Cu2+/A. RQs for vascular plants do not exceed the acute or acute endangered
species LOCs. Table 9 is a summary of the acute LOG exceedances for aquatic plants.
Table 9. Summary of Acute LOG Exceedences in Aquatic Environments from Agricultural Uses
Rate
Ibs Cu2+/A (ppb)
1.0 (2.2)
1.5 (3.4)
3.0 (7.2)
5.0(12.3)
7.5 (18.6)
Acute
Algae RQ
0.7
1.1
2.3
4.0
6.0
Vascular RQ
<0.01
<0.01
<0.01
0.01
0.01
Acute Endangered Species
Algae RQ
1.1
1.7
3.6
6.2
9.3
Vascular RQ
0.02
0.03
0.07
0.12
0.19
3.
Estuarine/Marine Fish and Invertebrates
Because the BLM has not been parameterized for estuarine/marine organisms, it could
not be used to assess potential copper exposure and toxicity from the cupric ion to
estuarine/marine animals. RQs for estuarine/marine animals and plants were calculated using
estimates of total dissolved copper using PRZM/EXAMS, which overestimates the amount of
copper that is potentially toxic to exposed organisms. In addition, the water body simulated by
PRZM/EXAMS, a static farm pond with no outflow, is smaller than estuarine and marine water
bodies, and does not take into account the dilutive effect of untreated seawater.
Acute toxicity values for saltwater fish and invertebrates were selected based on the most
sensitive assessed species. The most sensitive invertebrate is the mussel (Mytilus) with an LCso
of 6.49 ppb and the most sensitive fish is the summer flounder (Paralichthys dentatus), with an
LCso of 12.66 ppb. Chronic toxicity data were not available for estuarine/marine animals, so the
ACR of 3.23 used for freshwater animals was used to derive chronic RQs for marine/estuarine
animals.
As for the freshwater organism assessment, RQs for estuarine/marine organisms were
calculated using the same regression on the peak copper concentrations that resulted from
various application rates in the 32 PRZM/EXAMS simulations run for copper. At approximately
3 Ibs Cu2+/A, acute RQs exceedences occur for both fish and invertebrates. Table 10 lists the
acute RQs for marine/estuarine organisms for a range of copper application rates.
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Table 10. Risk Quotients for Estuarine/Marine Animals
Application Rate
Ibs Cu2+/A
1.0
1.5
3.0
5.0
7.5
Acute RQ
Fish
0.17
0.27
0.56
0.99
1.5
Invertebrate
0.35
0.55
1.2
2.0
3.0
Chronic RQ
Fish
1.1
1.5
2.8
4.4
6.4
Invertebrate
0.6
0.8
1.3
2.1
3.1
4.
Estuarine/Marine Plants
Because the BLM has not been parameterized for estuarine/marine plants, it could not be
used to assess potential copper exposure and toxicity from the cupric ion to estuarine/marine
plants. RQs for estuarine/marine plants were calculated using estimates of total dissolved copper
using PRZM/EXAMS, which overestimates the amount of copper that is potentially toxic to
exposed organisms. The single estuarine/marine plant species tested, the marine diatom,
Skeletonema costatum, (LCso = 0.25 ppm, NOEC = 0.124 ppm) was selected to represent
estuarine/marine plants.
Since site-specific exposure and toxicity values for plants were not generated using the
BLM, risk is not described as a percentage of RQs above the LOG; rather a single RQ is
presented for each application rate, with EECs calculated using the regression described above.
RQs for estuarine/marine plants do not exceed the acute or acute endangered species LOG of 1.0.
Table 11 summarizes potential acute risk for estuarine/marine plants.
Table 11. Acute Risk Quotients for Estuarine/Marine Plants
Application Rate
Ibs Cu2+/A (Cu ppb)
1.0 (2.2)
1.5 (3.4)
3.0 (7.2)
5.0(12.3)
7.5 (18.6)
Acute RQ
0.01
0.01
0.03
0.05
0.07
Acute Endangered Species RQ
0.02
0.03
0.06
0.1
0.13
b. Terrestrial Organisms
1. Birds and Mammals
Copper Exposure to Birds and Mammals
For birds and small mammals, dietary exposure to copper was estimated using the
Terrestrial Exposure (TREX, Version 1.1) model. Based on the Kenaga nomogram (Hoerger and
Kenaga 1972, Fletcher et al. 1994), TREX calculates estimated copper resides on food items
animals may consume. In this screening assessment, the Agency assumes that organisms forage
100% of the time in a treated area and that 100% of their diet is comprised of a particular food
item.
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A default foliar dissipation half-life for copper of 35 days was assumed, as no foliar
dissipation studies have been submitted for the copper compounds addressed in this RED.
Because copper is an element, it will not degrade by photolysis or hydrolysis into any other
metabolites or other byproducts. Thus, the primary means of removal is wash-off due to
precipitation or irrigation (e.g., drip) that governs how long copper remains on plant surfaces.
Because the amount of wash-off depends on the amount of precipitation, a plant dissipation
study would not capture the variability of wash-off rates across the country; thus, data from this
study would not provide any additional information to reduce any uncertainty or risk. Therefore,
the Agency is not requiring this study at this time.
The Agency modeled potential exposure to terrestrial animals from residues on forage
items based on the highest label application rates and the highest average application rates of
copper for orchard and row crops. Current copper labels indicate that the highest orchard label
application rate is 31.8 Ibs Cu2+/A for filberts and the highest row crop label application rate is
3.2 Ibs Cu2+/A for potatoes. Because intervals between applications and the maximum number
of applications were not specified on the product labels, the Agency assumed four applications
on a weekly basis per growing season. However, based on use data provided by the CSTF and
user groups, typical use is lower. These rates, 3.8 Ibs Cu2+/A for orchards (apples) and 0.8 Ib
Cu2+/A for row crops (potatoes), were also considered in the risk assessment.
Toxicity to Birds and Mammals
Copper is an essential micronutrient to many organisms, including birds and mammals.
Copper atoms are an important component of several enzymes, and reserve copper is stored in
the liver and bone marrow. Unlike aquatic animals, in which toxicity occurs when the cupric ion
binds to the gills, acute poisoning of terrestrial organisms requires dietary ingestion of toxic
levels of copper.
Terrestrial animals have varying degrees of homeostatic capability to metabolize copper
when ingested. Two studies (Johnson and Lee 1988, Yu et al., 1993) estimated copper
absorption in rats from dietary sources. Dependent on dose and method of estimation, absorption
efficiencies for rats with no known metabolic deficiencies ranged from 22-63%. Absorption
efficiency was consistently lower at high doses. Dietary copper concentrations ranged from 0.4-
100 ppm. In a study evaluating bioaccumulation models for mice (Torres and Johnson 2001),
the authors calculated a "GI absorption-elimination factor" of 28% based on data in the ASTDR1
Toxicological Profile for Copper. Thus, it appears that at least up to dietary concentrations
measured in these studies, small mammals have compensatory mechanisms to increase
absorption of copper at low concentrations, and reduce absorption of copper at high
concentrations, at least from dietary sources. No data were located to indicate at what copper
concentration these compensatory mechanisms might be overwhelmed, nor were similar data
available for birds.
The TREX model assumes that 100% of the ingested chemical is bioavailable, and uses
that estimate as an effective dose (adjusted by allometric equations). Based on the existing data,
Agency for Toxic Substances and Disease Registry
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this does not appear to be the case for copper. Dietary-based endpoints likely incorporate these
uptake effects, but dose-based endpoints will not. In order to account for these mechanisms, an
absorption efficiency correction of 22% (a high copper availability situation) was applied to the
mammal dose-based risk quotient calculations. Bird dose-based calculations were not corrected,
as it is uncertain to what extent the actual percentages may be valid across taxa, and dietary-
based data were available for acute effects.
Coppers are categorized as moderately toxic to birds on an acute oral and dietary basis.
The Agency assessed toxicity to avian species based on the acute oral LD50 of 98 mg/kg-bw, the
acute dietary LCso of 991 ppm of copper in feed and the chronic NOAEL of 58 mg/kg-bw.
Available avian guideline data are described in Table 12 below.
Table 12. Avian Guideline Data
Species
Compound
LD50/LC50
(mg/kg)
LOAEL (mg/kg)
NOAEL (mg/kg)
Acute oral
Bob white
Copper sulfate pentahydrate
as metallic copper
384
98a
ND
ND
Acute dietary
Bob white
Tri-basic copper sulfate
as metallic copper
1829
991a
NR
NR
Reproductive
Bob white
Copper oxychloride sulfate
as metallic copper
NR
500
289
100
58a
toxicity endpoint used in assessment
ND - not determined, NR - not reported
Available oral data on mammals indicate that copper is moderately toxic on an acute
basis. The Agency assessed toxicity to mammals based on the acute oral LD50 of 114 mg/kg-bw.
Because no reproductive or two-generation copper studies conducted with small mammals were
available, the Agency opted to use the chronic NOAEL study conducted on the mink from the
Superfund site-screening guideline studies. The NOAEL in this study was 85.5 mg/kg diet (11.7
mg/kg-bw on a dose basis). Available acute oral rat toxicity data and chronic mammalian
screening values are described below in Tables 13 and 14, respectively.
Table 13. Acute Oral Toxicity in Rats
Compound
Copper sulfate
pentahydrate
As Copper Compound
LD50
(mg/kg-bw)
790 (male)
450 (female)
As Metallic Copper
LD50
(mg/kg-bw)
200 (male)
114 (female)3
a toxicity endpoint used in assessment
48
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Table 14. Chronic Mammalian Screening Values
Category
Mammals
Test species: mink
Benchmark
NOAEL
11.7mg/kg-bwa
85.5mg/kgdieta
LOAEL
15.1 mg/kg-bw
1 10.5 mg/kg diet
Effects
Chronic dietary exposure during reproduction. Effects were
reduced survivorship of kits. Copper dose represented a base in
food (60.5 ppm) plus a supplement (25, 50, 100, and 200 ppm).
At 25 ppm in diet, kit survivorship was greater than in controls.
Reduced survivorship of kits was noted in the 50 ppm treatment
group.
a toxicity endpoint used in assessment
Risk to Birds and Mammals
The terrestrial animal risk assessment for copper pesticides assessed the potential for risk
at the highest application rate on any copper label for use on orchards and on row crops. These
application rates are 31.8 Ibs Cu2+/A for orchards (filberts) and 3.2 Ibs Cu2+/A for row crops
(potatoes). RQs were also calculated for the highest average application rate for orchards and for
row crops, as determined by the best data available to the Agency at the time the risk assessment
was completed. These rates were 3.8 Ibs Cu2+/A for orchards (apples) and 0.8 Ib Cu2+/A for row
crops (potatoes). Because the maximum number of applications and minimum application
interval were not specified on the product labels for these rates, the assessment assumed four
applications spaced seven days apart.
The RQs for the maximum application rates exceeded nearly all acute and chronic LOCs
for all weight classes of birds and mammals. However, as part of the stakeholder process in
formulating risk management decisions, the Agency has worked with copper pesticide registrants
and the user community to revise the labels to require lower application rates and more clearly
defined seasonal maximum use rates. Therefore, the RQs based on average application rates
shown below better reflect the lower rates to be established on revised copper product labels.
The RQs calculated using typical application rates indicate the potential for acute and
chronic risk to birds and mammals from dietary exposure. Dietary toxicity studies, in which
animals are exposed through ingestion of treated feed, would be expected to reflect the ability of
the animals to cope with exposure to a certain amount of copper beyond their dietary need
through homeostasis. However, this coping mechanism was clearly overwhelmed in the animals
which died in the laboratory toxicity tests.
The design of the laboratory studies leaves some uncertainty in how these effects would
translate to effects in the wild. Birds and mammals in the laboratory studies are only fed treated
feed, and the RQs in the risk assessment also assume that animals will derive 100% of their diet
from treated feed. Although animals in the wild need to eat more than their counterparts in the
laboratory (since lab feed is more nutritious, generally), most birds and mammals will spend only
a fraction of the time in or at the edge of a treated field. Animals which eat untreated feed as a
portion of their diet may have more of an opportunity to cope with ingested copper when the
exposure is not continuous. In addition, animals which are repeatedly exposed to levels of
copper which do not cause permanent harm may undergo enzymatic adaptation which allows
them to cope with greater levels of exposure. The sensitivity to copper toxicity, and the ability to
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adapt to repeated exposures, should be expected to vary within species, and between species of
birds and mammals.
Birds
Dose-based and dietary-based endpoints from available avian studies were used to
calculate acute RQs. Chronic endpoints for birds were based on data from reproductive studies
conducted on the bobwhite quail. The EECs are adjusted to reflect potential dietary exposure
based on the size of the animal and the respective amount of feed consumed.
Orchard Applications
The highest label rate for orchard applications was for filberts (31.8 Ibs Cu2+/A). At this
application rate, all size classes of birds exceed the acute, acute endangered species, and chronic
levels of concern for all food items. Table 15 describes the avian RQs for acute dose-based and
dietary-based RQs, and chronic RQs based on orchard labeled rates.
Table 15. Avian RQ Summary - Orchard Maximum Label Rate (31.8 Ibs Cuz/A)
Feed Item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Acute dose-based RQs
20g bird
220
101
124
13.8
lOOg bird
98.7
45.3
55.5
6.2
1000 g bird
31.2
14.3
17.5
2.0
Acute
dietary-based RQs
All birds
13.5
6.2
7.6
0.9
Chronic
RQs
All birds
231
106
130
14.5
The highest average rate for orchard applications was for apples (3.8 Ibs Cu2+/A). At this
application rate, all size classes of birds exceed the endangered species acute risk LOG and the
chronic risk LOG for all food items. Birds consuming the short grass, tall grass, and broadleaf
plants food categories all exceed the acute risk and chronic risk LOCs, whereas with the fruit
food item, larger birds and birds assessed with dietary-based endpoints are below the acute risk
LOG. Table 16 describes the avian RQs for acute dose-based and dietary-based RQs, and
chronic RQs based on orchard average application rate of 3.8 Ibs Cu2+/A.
Table 16. Avian RQ Summary - Orchard Average Rate (3.8 Ibs Cu2+/A)
Feed item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Acute dose-based RQs
20g bird
49.3
22.6
27.7
3.1
lOOg bird
22.1
10.1
12.4
1.4
1000 g bird
7.0
3.2
4.0
0.4
Acute
dietary-based RQs
All birds
3.0
1.4
1.7
0.2
Chronic
RQs
All birds
51.7
23.7
29.1
3.2
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Row Crop Applications
The highest label rate for row crop applications was for potatoes (3.2 Ibs Cu2+/A). At this
application rate, all size classes of birds consuming the short grass, tall grass, and broadleaf plant
food categories exceed the acute risk levels of concern. The small (20g) and medium (lOOg)
birds consuming a diet of fruits, pods, seeds, or large insects exceed the acute risk LOG, using
the dose-based calculation. All size classes of birds consuming all food types exceed the
endangered species acute risk LOG and the chronic risk LOG. Table 17 describes the avian RQs
for acute dose-based and dietary-based RQs, and chronic RQs based on row crop maximum
application rate of 3.2 Ibs Cu2+/A.
Table 17. Avian RQ Summary - Row Crop Maximum Label Rate (3.2 Ibs Cu2+/A)
Feed Item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Acute dose-based RQs
20g bird
41.5
19.0
23.3
2.6
lOOg bird
18.6
8.5
10.5
1.2
lOOOg bird
5.9
2.7
3.3
0.4
Acute
dietary-based RQs
All birds
2.6
1.2
1.4
0.2
Chronic RQs
All birds
43.5
20.0
24.5
2.7
The highest average rate for row crop applications was for potatoes (0.8 Ib Cu2+/A). At
this application rate, birds consuming the short grass, tall grass, and broadleaf plant categories
exceed the endangered species acute risk LOG and the chronic risk LOG. Using dose-based
RQs, all bird consuming these food categories also exceed the acute risk LOG. Only birds
consuming short grass exceed the acute risk LOG using the dietary-based RQs. Birds consuming
the fruits and pods food category exceed the endangered species acute risk LOG using dose-
based RQs, but not dietary-based RQs. Only the small bird (20g) in this category exceeds the
acute risk LOG using the dose-based RQ. Table 18 describes the avian RQs for acute dose-based
and dietary-based RQs, and chronic RQs based on row crop average application rate of 0.8 Ib
Cu2+/A.
Table 18. Avian RQ Summary - Row Crop Average Rate (0.8 Ib Cu /A)
Feed Item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Acute dose-based RQs
20g bird
10.4
4.8
5.8
0.7
lOOg bird
4.7
2.1
2.6
0.3
1000 g bird
1.47
0.67
0.83
0.1
Acute
dietary-based RQs
All birds
0.6
0.3
0.4
0.1
Chronic
RQs
All birds
10.9
5.0
6.1
0.7
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Mammals
Acute RQs from dose-based acute mammalian studies have been adjusted to include a
22% absorption factor to account for dietary effects described above. Because dietary-based
chronic data were available, the chronic dose-based values were not adjusted.
Orchard Applications
The highest labeled application rate for orchard use was for filberts at 31.8 Ibs Cu2+/A,
assuming four applications at weekly intervals. At this application rate, RQs for all size classes
of mammals consuming plants or small insects exceed the acute risk, endangered species acute
risk, and chronic risk LOCs. Except for l,000g granivores, all size classes and food groups
evaluated exceed the endangered species acute risk LOG. Table 19 summarizes acute and
chronic risks to mammals.
Table 19. Mammal RQ Summary - Orchard Maximum Label Rates (31.8 Ibs Cu2+/A)
Feed Items
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Seeds (granivores)
Acute dose-based RQs
(adjusted for 22%
absorption efficiency)
15g
11.2
5.1
6.3
0.7
0.15
35g
9.6
4.4
5.4
0.6
0.14
lOOOg
5.1
2.3
2.8
0.3
0.06
Chronic dose-based RQs
15g
381
175
214
23.8
5.3
35g
327
150
184
20.5
4.7
lOOOg
172
78.8
96.8
10.8
2.2
Chronic
dietary-based RQs
All mammals
157
71.9
88.3
9.8
Not determined
The highest average application rate for orchard use was apples at 3.8 Ibs Cu +/A (4
applications, 7-day interval). RQs for all size classes of organisms consuming the short grass,
tall grass, broadleaf plants, and small insects exceed both the acute risk LOG and the endangered
species LOG. Endangered species acute risk LOCs are also exceeded for the 15g and 35g
mammals consuming fruits and large insects. RQs for all diet classes exceed the chronic risk
LOG. RQs presented below are based on upper-bound EECs from the Kenaga nomogram
(Hoerger and Kenaga 1972, Fletcher et al. 1994). Table 20 describes the mammalian RQs for
acute dose-based and dietary-based RQs, and chronic RQs based on orchard average application
rateof3.81bsCu2+/A.
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Table 20. Mammal RQ Summary - Orchard Average Rate (3.8 Ibs Cu /A)
Feed item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Seeds (granivores)
Acute dose-based RQs
(adjusted for 22%
absorption efficiency)
15g
2.5
1.2
1.4
0.16
0.03
35g
2.2
0.98
1.21
0.13
0.03
lOOOg
1.13
0.52
0.63
0.07
0.01
Chronic dose-based RQs
15g
85.2
39.1
47.9
5.3
1.2
35g
73.2
33.5
41.2
4.6
1.0
lOOOg
38.5
17.6
21.6
2.4
0.5
Chronic
dietary-based RQs
All mammals
35.1
16.1
19.7
2.2
Not determined
Row Crop Applications
The highest average application rate for row crop use was potatoes at 0.8 Ib Cu2+/A (4
applications, 7-day interval). Only the RQs for the small mammals consuming short grass
exceed the acute risk LOG, although RQs for all size classes of mammals consuming grass,
broadleaf plants, and small insects exceed the endangered species acute risk LOG. Dietary-based
RQs for the mammals consuming grass, broadleaf plants, and small insects exceed the chronic
LOG. RQs presented below are based on upper-bound EECs from the Kenaga nomogram
(Hoerger and Kenaga 1972, Fletcher et al. 1994). Table 21 describes the mammalian RQs for
acute dose-based and dietary-based RQs, and chronic RQs based on row crop average
application rate of 0.8 Ib Cu2+/A.
Table 21. Mammal RQ Summary - Row Crop Average Rates (0.8 Ib Cu2+/A)
Feed item
Short grass
Tall grass
Broadleaf plants/small insects
Fruits/pods/seeds/large insects
Seeds (granivores)
Acute dose-based RQs
(adjusted for 22%
absorption efficiency)
15g
0.53
0.24
0.30
0.03
0.01
35g
0.45
0.21
0.25
0.03
0.01
lOOOg
0.24
0.11
0.13
0.01
0.01
Chronic dose-based RQs
15g
17.9
8.2
10.1
1.1
0.3
35g
15.4
7.1
8.7
1.0
0.2
lOOOg
8.1
3.8
4.6
0.5
0.1
Chronic
dietary-based RQs
All mammals
7.4
3.4
4.2
0.5
Not Determined
2. Nontarget Insects
Available data from a honey bee acute toxicity study indicated that copper is practically
nontoxic to honey bees, with an acute LD50 > 100 jig/bee. However, because exposure estimates
for other insects cannot readily be determined, the potential risk of copper pesticides to other
insects is unknown.
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3.
Terrestrial Plants
The Agency assessed potential indirect exposure and risk to plants adjacent to treated
areas. The Agency used the TerrPlant model, which calculates EECs for upland and wetland
areas adjacent to the application site based on a combination of the potential runoff from the field
and spray drift from the method of application. This type of exposure is then compared to
seedling emergence endpoints to derive acute RQs. To assess effects from spray drift, estimated
EECs are compared against a vegetative vigor endpoint to derive "drift only" RQs.
The Agency could not conduct a complete terrestrial plant risk assessment, since the
toxicity dataset for copper is incomplete. Vegetative vigor data for both monocots and dicots
were available from the public literature, but no suitable data from the registrant or open
literature were found to evaluate the effects of copper on seedling emergence. Therefore, it was
only possible to assess the potential risk from drift of copper pesticides alone. Copper is not
expected to pose a risk to plants through its fungistatic mode of action. As described above, data
available through the ECOTOX database were used to determine that copper pesticides does not
appear to pose a risk to terrestrial plants via adverse effects to vegetative vigor. Furthermore,
copper did not exceed the acute or endangered species levels-of-concern for vascular aquatic
plants. Hence, no additional data is required at this time, as it appears unlikely that copper would
pose a risk to terrestrial plants.
Consideration of terrestrial plant exposure from drift from the highest label application
rates for copper are sufficient to evaluate the potential risk from vegetative vigor effects. The
highest orchard application rate on copper labels at the time the risk assessment was developed
was 31.8 Ibs Cu2+/A for filberts. Because the Terr-Plant model assumes a default spray drift
exposure of 1% of applied pesticide for ground-spray applications, and 5% for aerial
applications, the drift exposure from that maximum application rate is 0.03 Ib Cu2+/A and 0.16 Ib
Cu2+/A, respectively.
Raw data to calculate the EC25 (used to determine the acute RQ) were not available. The
more sensitive NOAEC, which is used to evaluate potential effects on endangered plants, was
available for both monocots and dicots. Hence, RQs were calculated for endangered species
vegetative vigor endpoints for both monocots and dicots, also using the maximum label rates for
orchards of 31.8 Ibs Cu2+/A. As with other effects endpoints, the data were corrected to express
the toxicity value in terms of elemental copper. No RQs exceeded the acute endangered species
LOG at this rate, which is substantially higher than the maximum application rate on filberts will
be after mitigation measures detailed in Section IV take effect. Therefore, there appears to be no
acute risk to non-endangered or listed terrestrial plants from spray drift. Toxicity endpoints and
RQs for terrestrial plants are summarized below in Table 22.
Table 22. Coppers RQs for Terrestrial Plants for Spray Drift
Plant Type
Monocot
Dicot
Type of Endpoint
Vegetative vigor
NOAEC
(Ibs Cu2+/Acre)
6.8
36.7
Acute Endangered Species RQ
Ground Spray
0.05
0.01
Aerial, airblast, spray
chem illation
0.24
0.04
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c. Endangered Species
The risk assessment for copper pesticides indicates a potential for direct effects on listed
species as noted below, should exposure actually occur at modeled levels:
Terrestrial organisms
o
o
Mammals
Acute RQs exceed the endangered species LOG for all mammals feeding
on short grass, tall grass, broadleaf forage and small insects for all
application rates modeled.
Chronic RQs exceed the LOG for all mammals feeding on short grass, tall
grass, broadleaf forage and small insects, and fruits/pods/seeds/large
insects for all rates modeled (except lOOOg mammals feeding on
fruits/pods/seeds/large insects for application rate of 0.8 Ib Cu2+/A). The
chronic RQ for granivores exceeds for smaller mammals at higher
application rates (such as the 3.8 Ibs Cu2+/A representing an average
orchard application rate).
Birds
o
o
Acute RQs exceed the endangered species LOG for birds feeding on short
grass, tall grass, broadleaf forage and small insects, and
fruits/pods/seeds/large insects for all application rates modeled.
Chronic RQs exceed the LOG for all birds feeding on short grass, tall
grass, broadleaf forage and small insects, and fruits/pods/seeds/large
insects for all rates modeled (except for birds feeding on
fruits/pods/seeds/large insects for application rate of 0.8 Ib Cu2+/A). The
chronic RQ for birds feeding on fruits/pods/seeds/large insects exceeds the
LOG at higher application rates (such as the 3.8 Ibs Cu2+/A representing
an average orchard application rate).
Aquatic Organisms
Freshwater animals
o The percentage of acute RQs for freshwater fish modeled with
PRZM/EXAMS and the BLM that exceed the endangered species LOG
ranges from 1.0% at 1.0 Ib Cu2+/A to 17.1% at 7.5 Ibs Cu2+/A for
agricultural uses of copper.
o The percentage of acute RQs for freshwater invertebrates modeled with
PRZM/EXAMS and the BLM that exceed the endangered species LOG
ranges from 19.0% at 1.0 Ib Cu2+/A to 84.0% at 7.5 Ibs Cu2+/A for
agricultural uses of copper .
o The percentage of chronic RQs for freshwater fish modeled with
PRZM/EXAMS and the BLM that exceed the endangered species LOG
ranges from 0.0% at 1.0 Ib Cu2+/A to 5.3% at 7.5 Ibs Cu2+/A for
agricultural uses of copper.
55
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o The percentage of chronic RQs for freshwater invertebrates modeled with
PRZM/EXAMS and the BLM that exceed the endangered species LOG
ranges from 4.2% at 1.0 Ib Cu2+/A to 32.4% at 7.5 Ibs Cu2+/A for
agricultural uses of copper.
o For freshwater invertebrates and fish, >99% of sites modeled with
PRZM/EXAMS and the BLM exceed the acute endangered species LOG
at an application rate of 1 ppm.
• Estuarine/Marine
o The acute endangered species LOG is exceeded for estuarine/marine fish
and invertebrates for agricultural uses at application rates of 1.0 Ib Cu2+/A
and above.
o The chronic endangered species LOG is exceeded for estuarine/marine
fish for agricultural uses at application rates of 1.0 Ib Cu2+/A and above.
o The chronic endangered species LOG is exceeded for estuarine/marine
invertebrates for agricultural uses at application rates of around 3.0 Ibs
Cu2+/A and higher.
• Plants
o The acute endangered species LOG is exceeded for non-vascular
freshwater plants for agricultural uses at application rates of 1.0 Ib Cu2+/A
and higher.
Further, potential indirect effects to any listed species dependent upon a species that
experiences effects from use of copper can not be precluded based on the screening level
ecological risk assessment. These conclusions are based solely on EPA's screening-level
assessment and do not constitute "may effect" findings under the Endangered Species Act for
any listed species.
3. Ecological Incidents
Although copper pesticides have been used for over one hundred years and several
million pounds of copper are applied each year, there are relatively few reported incidents
associated with copper compounds. For the active ingredients addressed in this RED, the
Agency's Ecological Incident Information System (EIIS) reports 24 incidents related to copper
pesticide applications. Of the 24 incidents, seven were associated with terrestrial plants with
certainty rated as possible or probable. One reported case of damage to tomatoes in Washington
state occurred when copper applications were made according to labeled use instructions. The
other six incidents affecting corn and peanuts in Indiana, Minnesota and Oklahoma, reported
effects including plant damage, incapacitation and pinched corn ears. None of these six incidents
reported the legality of the use. Seventeen of the incidents were associated with kills of aquatic
organisms, primarily consisting offish. Of these incidents, ten were classified as possible,
probable or highly probable, with the assumption that coppers were used in accordance with the
registered label. Reported incidents were generally fish kills, with deaths ranging from 100 to
1,000, with the exception of one case in New York, where the report states that over one million
fish were killed. In all cases, mortalities effects were reported, but the mechanisms of toxicity
were not specified (direct toxicity or secondary effects such as low dissolved oxygen). The
56
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remaining aquatic incidents were cases of misuse or described effects which are unlikely to be
related to copper pesticide applications.
57
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IV. Risk Management, Reregistration, and Tolerance Reassessment Decision
A. Determination of Reregistration Eligibility
Section 4(g)(2)(A) of FIFRA calls for the Agency to determine, after submission of
relevant data concerning an active ingredient, whether or not products containing the active
ingredients are eligible for reregi strati on. The Agency has previously identified and required the
submission of the generic data required to support reregistration of products containing copper as
an active ingredient. The Agency has completed its review of these generic data and has
determined that the data are sufficient to support reregistration of all products containing copper
that have registered agricultural uses.
The Agency has completed its assessment of the dietary, occupational, residential, and
ecological risk (agricultural uses only) associated with the use of pesticide products containing
the active ingredient copper. Based on a review of these data and on public comments on the
Agency's assessments for copper, the Agency has sufficient information on the human health
and ecological effects of copper to make decisions as part of the tolerance reassessment process
under FFDCA and reregistration process under FIFRA, as amended by FQPA. The Agency has
determined that copper-containing products registered for agricultural uses are eligible for
reregistration provided that the risk mitigation measures outlined in this document are adopted
and label amendments are made to reflect these measures. Label changes are described in
Section V. The antimicrobial ecological assessment of copper compounds will be conducted at a
later date. Appendix A summarizes the uses of copper that are eligible for reregistration.
Appendix B identifies the generic data requirements that the Agency reviewed as part of its
determination of reregistration eligibility of copper, and lists the submitted studies that the
Agency found acceptable. Data gaps are identified as generic data requirements that have not
been satisfied with acceptable data.
Based on its evaluation of copper, the Agency has determined that agricultural uses
(terrestrial and aquatic crops, direct aquatic uses, urban uses) of copper products, unless labeled
and used as specified in this document, would present risks inconsistent with FIFRA.
Accordingly, should a registrant fail to implement any of the risk mitigation measures identified
in this document, the Agency may take regulatory action to address the risk concerns from the
use of copper. If all changes outlined in this document are incorporated into the product labels,
then all current risks for copper will be adequately mitigated for the purposes of this
determination under FIFRA. Once an Endangered Species assessment is completed, further
changes to these registrations may be necessary.
B. Public Comments and Responses
Through the Agency's public participation process, EPA worked extensively with
registrants, stakeholders and the public to reach the regulatory decisions for copper. Because the
June 2005 preliminary ecological risk assessment indicated significant risk exceedances for
virtually all non-target organisms, the Agency requested refined use information from the
registrants. The Agency initiated outreach efforts with the CSTF and USDA to contact the
grower community to provide additional information reflective of actual use rates and other use
58
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information on copper agricultural products. However, these data were still inadequate to fully
revise the ecological risk assessment. Thus, EPA requested additional refined use information
during the Phase 3 Public Comment period for the grower community and other user groups to
provide use information and other input on the use of copper products labeled for agricultural
uses. During the public comment period on the risk assessments, which closed on March 27,
2006, the Agency received extensive comments from registrants, commodity/grower groups,
cooperative extension specialists, and university/research facilities. The refined use information
provided by user groups was used to refine the ecological risk assessment. User groups also
provided information on the significance of coppers in agricultural and aquatic applications.
These comments in their entirety and the Agency's response are available in the public docket
(EPA-HQ-OPP-2005-0558) at http://www.regulations.gov.
C. Regulatory Position
1. FQPA Findings
a. Risk Determination
As part of the FQPA tolerance reassessment process, EPA assessed the risks associated
with exposure to copper pesticides. EPA has determined that individual and aggregate risk from
all sources of exposure (food, drinking water and residential uses) to copper, including
agricultural, direct aquatic, and antimicrobial uses, will not exceed EPA's LOCs. The EPA has
concluded that the tolerances for copper meet FQPA safety standards. In reaching this
determination, EPA has considered the available information on the special sensitivity of infants
and children, as well as aggregate exposure from copper.
b. Determination of Safety to U.S. Population
The Agency has determined that the established tolerances for copper, with amendments
and changes as specified in this document, meet the safety standards under the FQPA
amendments to section 408(b)(2)(D) of the FFDCA, and that there is a reasonable certainty no
harm will result to the general population or any subgroup from the use of copper pesticides. In
reaching this conclusion, the Agency has considered all available information on the toxicity, use
practices and exposure scenarios, and the environmental behavior of copper.
As discussed in Section III, the total acute and chronic dietary risks from copper do not
exceed EPA's LOG. Also, aggregate risk from exposure to copper from all sources, including
agricultural, direct aquatic, and antimicrobial uses, is not of concern. Aggregate exposures
include dietary (food and drinking water) and residential uses of copper.
c. Determination of Safety to Infants and Children
EPA has determined that the established tolerances for copper meet the safety standards
under the FQPA amendments to section 408(b)(2)(C) of the FFDCA, that there is a reasonable
certainty of no harm for infants and children. The safety determination for infants and children
considers factors on the toxicity, use practices and environmental behavior noted above for the
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general population, but also takes into account the possibility of increased dietary exposure due
to the specific consumption patterns of infants and children, as well as the possibility of
increased susceptibility in this population subgroup.
In determining whether or not infants and children are particularly susceptible to toxic
effects from exposure to residues of copper, the Agency considered the completeness of the
hazard database for developmental and reproductive effects, the nature of the effects observed,
and other information. Since copper is a natural essential trace element, with deficiency more
common in humans than toxicity from excess, and the low total dietary contribution of copper,
toxicity endpoints were not selected. As described in Section IV above, due to an absence of
systemic toxicity, risks were not quantified and application of an FQPA SF was unnecessary.
2. Endocrine Disrupter Effects
EPA is required under the FFDCA, as amended by FQPA, to develop a screening
program to determine whether certain substances (including all pesticide active and other
ingredients) "may have an effect in humans that is similar to an effect produced by a naturally-
occurring estrogen, or other endocrine effects as the Administrator may designate." Following
recommendations of its Endocrine Disrupter Screening and Testing Advisory Committee
(EDSTAC), EPA determined that there was a scientific basis for including, as part of the
program, the androgen and thyroid hormone systems, in addition to the estrogen hormone
system. EPA also adopted EDSTAC's recommendation that EPA include evaluations of
potential effects in wildlife. For pesticides, EPA will use FIFRA and, to the extent that effects in
wildlife may help determine whether a substance may have an effect in humans, FFDCA
authority to require the wildlife evaluations. As the science develops and resources allow,
screening of additional hormone systems may be added to the Endocrine Disrupter Screening
Program (EDSP).
The available human health and ecological effects data for copper currently do not
indicate any evidence of endocrine disruption. Based on current available data, the Agency does
not have any concerns for endocrine disruption from exposure to copper pesticides.
3. Cumulative Risks
The FFDCA, as amended by FQPA, requires that the Agency consider "available
information" concerning the cumulative effects of a particular pesticide's residues and "other
substances that have a common mechanism of toxicity." The reason for consideration of other
substances is due to the possibility that low-level exposures to multiple chemical substances that
cause a common toxic effect by a common toxic mechanism could lead to the same adverse
health effect as would a higher level of exposure to any of the substances individually. Unlike
other pesticides for which EPA has followed a cumulative risk approach based on a common
mechanism of toxicity, EPA has not made a common mechanism of toxicity finding as to the
copper ion and any other substances, and the copper ion does not produce toxic metabolites
produced by other substances. For the purposes of this RED, therefore, EPA has not assumed
that the copper ion has a common mechanism of toxicity with other substances. For information
regarding EPA's efforts to determine which chemicals have a common mechanism of toxicity
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and to evaluate the cumulative effects of such chemicals, see the policy statements released by
the Agency concerning common mechanism determinations and procedures for cumulating
effects from substances found to have a common mechanism on EPA's website at
http://www.epa.gov/pesticides/cumulative/.
4. Endangered Species
The Agency has developed the Endangered Species Protection Program to identify
pesticides whose use may cause adverse impacts on federally listed endangered and threatened
species, and to implement mitigation measures that address these impacts. The ESA requires
federal agencies to ensure that their actions are not likely to jeopardize listed species or adversely
modify designated critical habitat. To analyze the potential of registered pesticide uses that may
affect any particular species, EPA uses basic toxicity and exposure data developed for the REDs
and considers ecological parameters, pesticide use information, the geographic relationship
between specific pesticide uses and species locations and biological requirements and behavioral
aspects of the particular species. When conducted, this analysis will consider regulatory changes
recommended in this RED that are being implemented at that time. A determination that there is
a likelihood of potential effects to a listed species may result in limitations on the use of the
pesticide, other measures to mitigate any potential effects, or consultations with the Fish and
Wildlife Service or National Marine Fisheries Service as appropriate. If the Agency determines
that the use of copper "may affect" listed species or their designated critical habitat, EPA will
employ the provisions in the Services regulations (50 CFR Part 402). Until that species specific
analysis is completed, the risk mitigation measures being implemented through this RED will
reduce the likelihood that endangered and threatened species may be exposed to copper at levels
of concern.
D. Tolerance Reassessment Summary
Tolerance exemptions for residues of copper in/on plant, animal and processed
commodities are established under 40 CFR §180.1021. Additional tolerances for potable water
and post-harvest use on pears are established under 40 CFR §180.538 and 40 CFR §180.136,
respectively.
The Agency has determined that both the 3 ppm tolerance for residues of basic copper
carbonate in or on pears of combined copper from post-harvest use under 40 CFR §180.136, and
the 1 ppm tolerance for copper residues in potable water under 40 CFR §180.538 should be
revoked because these two tolerances are not necessary for human health protection. The
Agency has also determined that the copper tolerance expression under 40 CFR §180.1021
should be revised to include all current copper active ingredients with registered food uses.
1. Tolerances Proposed to be Revoked
40 CFR §180.136. The 3 ppm tolerance for residues of basic copper carbonate in or on pears of
combined copper from post-harvest use should be revoked. This 3 ppm tolerance is not
necessary for human health protection, as many food commodities not treated with copper
pesticides have naturally-occurring levels of copper that are higher than those found in or on
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pears as a result of residues from treated paper wrappers. In addition, toxicological studies
support that potential copper residue levels from the use of treated pear wrappers do not pose a
significant risk to human health. Thus, retaining this tolerance is not necessary.
40 CFR §180.538. The 1 ppm tolerance for copper residues in potable water should be revoked,
as this is an outdated tolerance and no longer applies to current regulations for managing copper
residues in drinking water. This 1 ppm tolerance is not necessary for human health protection.
2. Tolerances Listed Under 40 CFR §180.1021
The listed copper active ingredients are currently exempt from tolerance requirements on
all raw agricultural commodities under 40 CFR §180.1021. As part of the reregi strati on process
for copper, the Agency concludes that all food use copper formulations are still exempt from the
requirement of a tolerance. Should any additional copper active ingredients be registered for
new food uses in the future, the need for a tolerance for these formulations will be evaluated at
that time.
Copper linoleate and copper oleate should be removed from the list of copper compounds
described in 40 CFR § 180.102l(4)(b), because there are no current registrations that contain
either copper lineoleate or copper oleate. Both copper compounds are currently unsupported in
the United States. Bordeaux mixture and copper-lime mixture should also be removed from 40
CFR § 180.102l(4)(b), because copper sulfate is the active ingredient in these mixtures, which
has been assessed as part of this RED, and is already included as part of 40 CFR
§ 180.102l(4)(b). Cupric oxide should be removed from 40 CFR § 180.102l(4)(b) as well, as
there are no current products that contain cupric oxide that are registered for food use
applications.
There are some copper compounds that have registered agricultural uses on food crops
that are not currently described under 40 CFR §180.1021. The Agency has determined that even
with the inclusion of these copper compounds as part of tolerance reassessment, that the
tolerance exemption is still appropriate for all currently registered copper compounds when used
as labeled on growing crops, and the list described under 40 CFR § 180.102l(4)(b) should be
expanded to include the following copper compounds listed in Table 23.
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Table 23. List of Copper Compounds to Address under 40 CFR §180.1021(4)(b)
Chemical Name
Basic Copper Sulfate
Copper Sulfate Pentahydrate
Copper Chloride
Copper Ammonium Carbonate
Basic Copper Carbonate
(malachite)
Copper Hydroxide
Copper Oxychloride
Copper Oxychloride Sulfate
Copper Ammonia Complex
Copper in the form of chelates of
citrate and gluconate
Cuprous Oxide
Copper Salts of Fatty and Rosin
Acids
Copper Ethylenediamine
Complex
Copper Octanoate
EPA PC Code
008101
024001
008001
022703
022901
023401
023501
023503
022702
024405
025601
023104
024407
023306
C.A.S.
Number
1344.73-6
7758-99-8
1332-40-7
33113-08-5
1184-64-1
20427-59-2
1332-65-6
8012-69-9
16828-95-8
10402-15-0
1317-39-1
9007-39-0
13426-91-0
20543-04-8
Comments
No change
Needs to be added
No change
Needs to be added
No change
No change
Needs to be added
Needs to be added
Needs to be added
Needs to be added
No change
Needs to be added
No change
No change
Copper Compounds to Remove
Cupric Oxide
Copper oleate
Copper linoleate
Bordeaux Mixture
Copper Lime Mixtures
042401
023304
023303
None
None
1317-38-0
10402-16-1
7721-15-5
None
None
Remove; no currently registered food
uses.
Remove; this compound was cancelled
Remove; this compound was cancelled
Remove; active ingredient is copper
sulfate, which is already included.
Remove; active ingredient is copper
sulfate, which is already included.
E. Regulatory Rationale
The following is a summary of the rationale for mitigation measures necessary for
managing risks associated with the use of coppers and for agricultural copper products to be
eligible for reregi strati on. Where labeling revisions are warranted, specific language is set forth
in the summary table of Section V (Table 26 of this document).
1. Human Health Risk Management
All potential human health acute and chronic exposures (dietary, aggregate, residential,
and occupational) are below EPA's level of concern to the Agency for the U.S. general
population and all population subgroups, including infants and children. Copper is a ubiquitous
element that is essential for proper homeostasis in human health. Residues of copper on foods
resulting from agricultural pesticide use are not expected to significantly contribute to the overall
dietary intake of copper, as several foods already have naturally-occurring levels of copper.
Based on available literature and studies, there is no indication of systemic effects
resulting from copper exposures. Therefore, the minimum handler PPE (long-sleeved shirt and
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long pants, socks and shoes) for occupational workers will be required by the RED. However,
copper can be a severe irritant with effects resulting from dermal, oral, eye or inhalation
exposure that are solely due to the irritating properties of copper. These irritation effects are a
result of the body's mechanisms to reduce excessive exposure to copper. Each copper
compound and its product formulations can cause different degrees of acute oral, dermal, eye,
and inhalation irritation effects. To minimize irritation via these routes, commercial uses of
copper-based pesticides will be adequately protected through label-specified handler PPE (based
on the toxicity categories of the end-use product) and industrial workplace safety standards.
Depending on the acute toxicity of the active ingredient, the minimum re-entry interval (REI) is
12 hours, but may be up to 48 hours for copper compounds with greater acute toxicity categories.
To determine the appropriate specific PPE, registrants will need to submit product-specific data
as outlined in the product-specific DCIs (PDCI) subsequent to the issuance of this RED.
Post-application restrictions (REIs and early-entry PPE) will default to the measures as
required by the Worker Protection Standard (WPS) in 40 CFR §170. Depending on the acute
toxicity of the copper compound, the minimum REI is 12 hours, but may be up to 48 hours for
copper compounds with greater acute toxicity categories. The early-entry PPE will also be
determined by the acute toxicity of the active ingredient. Table 24 below describes the REI for
each copper compound. Appropriate REIs and early-entry PPE for each copper compound is
described in Table 26. For formulations with residential uses, dermal and eye irritation effects
will be addressed via end-use product labeling language.
Table 24. REIs for each Copper Compound
REI
48-hour
(Toxicity category I)
24-hour
(Toxicity Category II)
12-hour
(Toxicity Category
III or IV)
Copper Compound
Copper chloride
Chelates of copper gluconate
Copper ammonium carbonate
Copper carbonate
Copper hydroxide
Copper ammonia complex
Copper oxychloride
Copper oxychloride
Basic copper sulfate
Copper sulfate anhydrous
Copper sulfate pentahydrate
Cuprous oxide
Copper triethanolamine
complex
Copper 8-quinolinolate
Copper naphthenate
Copper salts of fatty and rosin
acids
Copper ethanolamine complex
Copper, metallic
Copper ethylenediamine
Cupric oxide
Copper octanoate
PC Code
008001
024405
022703
022901
023401
022702
023501
023503
008101
024408
024401
025601
024403
024002
023102
023104
024409
022501
024407
042401
023306
Study Reference
No studies available for dermal
sensitization
No studies available
No studies available
Primary eye irritation
Primary eye irritation
No studies available
Primary eye irritation
No studies available
No studies available
No studies available
Primary eye irritation
Acute dermal irritation
No studies available for acute dermal
sensitization
Primary eye irritation
Primary eye irritation
No studies available for acute dermal
sensitization
No studies available
Primary eye irritation
Acute oral irritation
Toxicity category III for acute dermal,
primary eye and dermal irritation
Toxicity category III for acute oral,
dermal and irritation studies
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Given the role copper plays as an essential element to the human body, its ubiquitous
nature in food and drinking water, low toxicity profile, and the lack of incidents showing any
effects resulting from systemic toxicity, there are no systemic human health risks of concern to
the Agency; thus, no mitigation is needed beyond that which is required to address the irritation
effects associated with copper compounds.
2. Ecological Risk Management for Non-target Organisms
Ecological risk mitigation measures may include lowering application rates, reducing the
number of applications in a given year, restricting the timing of applications, extending the
period between applications (application interval), and changing pesticide application methods to
reduce the potential for spray drift or runoff.
The screening-level ecological risk assessment for copper suggests acute and chronic risk
concerns for both freshwater and marine/estuarine organisms resulting from copper exposure at
maximum labeled rates. Additionally, the risk assessment suggests potential risk to terrestrial
animals exposed to high levels of copper resulting from pesticidal use. However, imprecise
product labels represent the greatest source of uncertainty in the ecological risk assessment for
copper pesticides. The ecological risk assessment assumed a number of applications and an
application interval for most uses because product labels for copper pesticides do not specify the
maximum number of applications and minimum treatment interval. Because the labels do not
specify these limits, the Agency made conservative assumptions with maximum application and
use information, which may underestimate or overestimate potential risk.
The registrants, grower groups, and other stakeholders have agreed to mitigation
measures to address potential risks to terrestrial and aquatic animals. Labels for agricultural uses
of copper will be revised to more accurately reflect use rates typically required to control specific
pests and diseases. This will result in lower maximum allowed application rates for most crops.
These labels will define maximum single application rate for each crop, minimum application
intervals for each use, and will specify the maximum amount of copper that can be applied each
year. The establishment of maximum individual and annual application rates and minimum
application intervals will reduce the potential loading of copper into ecosystems by preventing
unnecessarily high rates previously permitted and by limiting the frequency of exposure to non-
target organisms.
Additional advisory language will be required to minimize potential adverse ecological
effects. To reduce any adverse effects from potential spray drift, labels will be revised to include
advisory language on reducing the potential for spray drift. Labeling measures include aerial
applications only at or below certain wind speed and larger droplet size to reduce drift potential.
In addition, registrants will be required to submit spray drift data.For more details on additional
labeling requirements, refer to the Table 26. Because the chemistry of a water body greatly
influences potential copper toxicity, additional advisory language describing chemistry
conditions that likely would lead to increased copper toxicity potential (i.e., low pH and low
DOC) will be required on revised labels. Appendix A describes the refined single maximum
application rates, defined application intervals with a minimum number of days between
retreatments, and maximum seasonal rate that is permitted to be applied per year.
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a. Benefits of Copper Pesticides
Through extensive outreach to the public as well as additional comments and refined
information provided by the user community, the Agency has determined that there are many
benefits that support the significance and continued agricultural uses of copper pesticides. A
significant benefit is that copper exposure from all sources, including use as a pesticide in
agricultural settings, does not pose any human health concerns. Although there is still potential
for ecological effects to non-target organisms, there are many benefits to retain agricultural uses
of copper pesticides. For detailed discussions on the benefits of the continued use of copper
pesticides on the respective major crops/use sites, please refer to the Cursory Alternatives and
Assets Analysis of the Agricultural Uses of Copper Group II Pesticides, dated June 20, 2006, and
the Copper (Cu++) Alternatives Analysis for the Primary Aquatic Uses, dated June 20, 2006.
Below is a description of specific areas where the benefits of coppers are significant, and where
applicable, a discussion of general comparisons against available alternatives.
1. Terrestrial Uses
Coppers are significant for use as a broad-spectrum fungicide and bactericide on
agricultural crops. Based on its history of use for many centuries, there is little evidence to
indicate any significant pest-resistance problems. Copper pesticides are also used to remedy
copper-deficient soils. Coppers are used in some Integrated Pest Management (IPM) systems,
alternated with some systemic fungicides that have a high risk of developing resistance or have
shown early indications of some pesticide resistance. Comments provided by the University of
Georgia indicated that IPM programs using copper alternated with antibiotics is used in peach
productions. Copper use can reduce heavy reliance on the use of antibiotics for control of
bacterial diseases for some crops.
Copper use is significant in various market niches, including those in the US as well as
exported commodities. Although organically-grown crops represent a relatively small portion of
the agricultural market, organic growers rely heavily on copper pesticides. Several organic
growers reasserted that copper is one of the few pesticides available to growers to effectively and
efficiently manage target pests, namely bacterial diseases. Another specific niche is the use of
treating and preventing Septoria Spot on navel oranges from California for export to the
Republic of Korea. There is a current export agreement that requires a pesticide treatment
protocol that includes copper treatments on navel oranges for the treatment of Septoria Spot
caused by Septoria citri.
For many of the major crops, growers have indicated that there are few or sometimes no
suitable alternatives to copper pesticides for certain target pests. For example, the Florida Fruit
& Vegetable Association noted that copper products are the only registered and effective
pesticide available to manage citrus canker to avoid major crop losses. Although citrus canker
has only been found in Florida, other major citrus producers outside of Florida such as the Texas
Citrus Mutual group has expressed similar concerns and asserted the importance of retaining this
use. Copper is currently the only viable or available option to control some bacterial diseases for
which there are no registered antibiotics or where pests have developed resistance to some
available alternatives. Some growers have reported the lack of suitable alternatives for bacterial
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diseases in blueberries, apples, citrus, cherries, and strawberries. The Texas Vegetable
Association stated that there are no alternatives for controlling bacterial leaf spot on peppers and
tomatoes. In many cases, copper fungicides are the most cost-effective treatment that allows for
frequent retreatments and are effective in suppressing or managing bacterial diseases for which
there are no suitable alternatives.
2. Aquatic Weeds and Algae
Copper is extensively used in direct aquatic applications including the management of
algae, aquatic weeds, and mollusks that may host harmful parasites. Below is a description of
some major areas where the use of copper pesticides is significant for its respective target pests.
Aquaculture. A comment from the University of Mississippi noted that aquaculture ponds
containing certain cyanobacteria species can cause off-flavors in farm-raised catfish. Unlike
many other market animal or grain crop products, an off-flavor in farm-raised fish does not result
in a payment penalty; rather, it results in the rejection of all fish destined for market from that
particular farm until the algae is properly managed and the off-flavors are purged from the fish.
As a preventative measure, full-pond treatments are sometimes used for cyanobacteria control to
minimize potential algal blooms that may cause off-flavors. Copper is the only registered
chemical for which treatment of these off-flavor causing algae. In the past, special temporary
use permits (FIFRA Section 18s) allowed for the use of diuron to control cyanobacteria in catfish
and hybrid striped bass aquaculture ponds due to the rejection of off-flavor fish destined for
market, but is costlier than using copper.
Drinking Water. Algae can clog water filters, reducing filter run times and requiring frequent
backwashing, which all lead to greater coagulant demand and other treatments that impose
greater costs to treatment facilities. Some species of algae can cause various off-flavors in
drinking water, such as cyanobacteria, which can produce chemicals called cyanotoxins that lead
to earthy or musty flavors. Only rarely are taste and odor problems the result of algal toxins in
drinking water. Cyanobacterial blooms are not consistent and predictable, but often proliferate
quickly during a summer drought. Thus, this requires early detection and treatment of algae to
ensure effective treatment with the minimum amount of pesticide needed. These cyanotoxins
and other chemicals are often difficult and more expensive to remove during water treatment.
The use of copper for this application can be costly, but often times necessary for drinking water
quality. Current labels for copper compounds allow for up to 1 ppm of copper in drinking water,
which is in accordance with the Agency's 1.3 ppm MCLG for residues of copper in drinking
water.
Irrigation/Conveyance Systems. In the western part of the US, 68% of the crops produced rely
on irrigated water. Thus, regular maintenance of distribution canals in important for optimal
water flow to receiving fields. Dense mats of vegetation can be a mechanical hindrance to
valves and gate which divert and control the flow of water. Cyanobacteria and filamentous algae
can lead to clogging of water intake screens in lakes and aqueducts. This reduction in water flow
can result in millions of dollars lost due to failed crops as well as up-system flooding of areas
surrounding the canal. Aquatic weed control in irrigation systems is essential, since debris from
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weeds can decrease water flow. In addition, physical clogging by weeds can cause obstructions
to valves and gates needed to control or divert water flow to receiving fields.
Quiescent Water Bodies (Recreational Ornamental). Control of aquatic weeds in quiescent
water bodies, such as ponds and lakes, is needed to maintain the safety of recreants and
recreational activity operations that include fishing, water sports or swimming. In addition,
many of these water bodies are also used as drinking water supplies. On rare occasion,
cyanobacteria are known to produce hepatotoxins that may be harmful to humans and other
mammals. Excess algae and other vegetation in quiescent or near-quiescent water bodies can
impact overall water quality that may lead to decreased food availability and even fish kills.
Dense algal or weed mats can block sunlight from reaching submerged biota, potentially
affecting the entire ecological cycle, and even pose physical barriers for mobile animals. As the
plant debris die back, increased microbial decay would lead to the decrease of dissolved oxygen
available to fish and other organisms living in the same water body.
Alternatives. There are several limitations with the available alternatives to copper compounds.
For example, dyes and colorants cannot be used in moving waters with an outflow, and some
biocides may pose some human health exposure concerns. Multiple herbicides would be
required to replace the copper compounds in these systems. Some available alternatives only
control vegetation that has emerged above the water surface, while others may only control
certain types of weeds.
3. Aquatic Invertebrate Control
Leech. The macro-invertebrates that are controlled by copper sulfate pentahydrate are leeches
and tadpole shrimp. Leeches are often a problem in ponds and quiescent waters under drought
conditions. While leeches are usually a problem for fish, humans splashing in quiescent waters
may become an alternate host to leeches. Currently, copper sulfate pentahydrate is the only
registered compound for leech control in open water.
Tadpole Shrimp. Tadpole shrimp are often a problem in rice production, causing damage to
newly emerged/young rice plants. Carbaryl is available as an alternative to copper for tadpole
shrimp; however, copper sulfate pentahydrate has no human health risks of concern and is the
only available pesticide that would still allow for organic rice growers to retain certification for
organically-grown rice.
Freshwater Snails. Copper sulfate can be used to control freshwater snails to minimize potential
exposure to problematic trematodes. Freshwater snails may act as a vector to schistosomes and
other trematode cercariae that may affect exposed swimmers or farm-raised fish. Specific to
humans, these schistosomes may penetrate human skin, causing Swimmer's Itch. In catfish
production ponds, snails may be infected with a trematode from the Bolbophorus species. These
trematodes may also cause lesions in exposed catfish, rendering them unmarketable. There is no
treatment available for fish infected with this trematode.
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b. Terrestrial Organisms
1. Birds and Mammals
The Agency modeled potential exposure to terrestrial animals from residues on forage
items based on the highest label application rates and the highest average application rates of
copper for orchard and row crops. Current copper labels indicate that the highest orchard label
application rate is 31.8 Ibs Cu2+/A for filberts and the highest row crop label application rate is
3.2 Ibs Cu2+/A for potatoes. The highest average application rate for orchards and for row crops,
as determined by the best data available to the Agency at the time the risk assessment was
completed, were 3.8 Ibs Cu2+/A for orchards (apples) and 0.8 Ib Cu2+/A for row crops (potatoes).
Because intervals between applications and the maximum number of applications were not
specified on the product labels, the Agency assumed four applications on a weekly basis per
growing season.
The RQs for the maximum and highest average application rates exceeded nearly all
acute and chronic LOCs for all weight classes of birds and mammals. However, RQs for the
average application rates are much lower, reflecting the significantly reduced EECs. For
instance, the highest dose-based acute RQ for birds based on maximum orchard application rates
is 220 and the corresponding dietary-based acute RQ is 13.5. By contrast, the highest dose-based
acute RQ for birds based on average orchard application rates is 49 and the corresponding
dietary-based acute RQ is 3.0.
The RQs for the highest average application rates more closely reflect the application
rates that will be on copper product labels after the mitigation measures described above are put
into effect. An exception to this is the 6 Ibs Cu2+/A maximum application rate for filberts, the
highest maximum application rate for any crop. However, this high rate will only apply to a
small, defined area in the Pacific Northwest where copper is applied on filberts. According to
the USD A, approximately 2,000 acres of filberts in this region are treated with copper.
Application rates for other crops, which have been chosen based on input received after
extensive outreach to grower groups and the public, will range from less than one pound up to 4
Ibs Cu2+/A. Grower groups indicated that, depending on the crop, disease pressure, and timing,
many applications are made at longer than the weekly interval assumed for most crops in the risk
assessment. As described in Appendix A, longer minimum application intervals will be
established for copper application to many crops.
Because the RQs for the average application rates exceed acute and chronic LOCs,
application according to the revised labels can still potentially result in dietary risk to birds and
mammals. However, there are some uncertainties in this finding of risk associated with
assumptions used in the screening-level assessment itself, and with the response of birds and
mammals exposed to copper. For instance, RQs in this assessment were calculated using 95th
percentile residues from the Kenaga nomogram; mean residues from the Kenaga nomogram are
about 2/3 less per application. Therefore, a typical application of copper would be expected to
result in lower EECs than indicated in the assessment. In addition, a default foliar dissipation
half-life of 35 days was used in the terrestrial exposure model T-REX, because data were not
available to indicate how quickly copper might dissipate from leaf surfaces through wash-off. A
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shorter foliar dissipation half-life would result in lower RQs for every crop to which multiple
applications of copper are made.
As described in the risk assessment, there is additional uncertainty in the risk finding
because terrestrial animals have varying degrees of homeostatic capability to metabolize ingested
copper. Copper is an essential micronutrient to many organisms, including birds and mammals.
The dietary-based RQs for birds likely incorporate these uptake effects to some extent, and an
absorption efficiency correction factor was applied to the mammal dose-based RQ calculations.
These RQs still exceed LOCs, but the design of the laboratory studies leaves some
uncertainty in how these effects would translate to effects in the wild. Birds and mammals in the
laboratory studies are only fed treated feed, and the RQs in the risk assessment also assume that
animals will derive 100% of their diet from treated feed. Although animals in the wild need to
eat more than their counterparts in the laboratory (since lab feed is more nutritious, generally),
most birds and mammals will spend only a fraction of the time in or at the edge of a treated field.
Animals which eat untreated feed as a portion of their diet may have more of an opportunity to
cope with ingested copper when the exposure is not continuous. In addition, animals which are
repeatedly exposed to levels of copper which do not cause permanent harm may undergo
enzymatic adaptation which allows them to cope with greater levels of exposure. The sensitivity
to copper toxicity, and the ability to adapt to repeated exposures, should be expected to vary
within species, and between species of birds and mammals.
Based on these factors, EPA has determined that the reduction in application rates and
defining minimum retreatment intervals will greatly reduce potential adverse exposures to non-
target terrestrial animals. In addition, this screening-level assessment includes conservative
assumptions, such as the animal feeding in a treated area 100% of the time. To date, there are no
reported bird or mammal incidents.
2. Terrestrial Plants
The Agency could not conduct a complete terrestrial plant risk assessment, since the
toxicity dataset for copper is incomplete. No suitable data from the registrant or open literature
were available for evaluating seedling emergence effects. Vegetative vigor data for both
monocots and dicots were available from the public literature.
No RQs exceeded the acute or acute endangered species LOG at the rate of 31.8 Ibs
Cu2+/A for filberts, which is substantially higher than all rates, that will be on copper pesticide
labels after mitigation measures detailed above take effect. Therefore, there appears to be no
acute risk to non-endangered or listed terrestrial plants from spray drift. In any case, the reduced
maximum application rates will reduce the maximum amount of copper to which terrestrial
plants will potentially be exposed, and no further mitigation is needed.
3. Insects
Available data from a honey bee acute toxicity study indicated that copper is practically
nontoxic to honey bees, with an acute LDso > 100 jig/bee. However, because exposure estimates
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for other insects cannot readily be determined, the potential risk of copper pesticides to other
insects is unknown. Based on available data, no additional mitigation to address exposure to
non-target insects is needed at this time.
c. Aquatic Organisms
1. Agricultural Uses
The Agency's screening-level ecological risk assessment for copper suggests acute and
chronic risk concerns for both freshwater and marine/estuarine organisms resulting from copper
exposure at maximum labeled rates, assuming four applications at weekly intervals. However,
exposure is expected to be significantly lower based on application rates, defined retreatment
intervals, seasonal maximum rates, and advisory spray drift language that will be on copper
product labels after the mitigation measures described above are put into effect.
Freshwater Animals
The screening-level risk assessment indicates that there are risks greater than the LOG to
freshwater invertebrates from terrestrial uses of copper at some portion of the 811 sites modeled,
both at the typical and at the maximum labeled application rate. At the maximum application
rate considered in the risk assessment, 31.8 Ibs Cu2+/A for filberts, RQs for nearly all sites
exceeded the acute and chronic LOCs. Over 99% of the sites exceeded the acute LOG for
invertebrates, and 80% exceeded for fish. Over 98% of the sites exceeded the chronic LOG for
invertebrates and 44.9% exceeded for fish.
The rate reductions that will be brought about through mitigation are expected to
significantly reduce the number of sites at which freshwater animals are at risk from exposure to
copper applied as an agricultural pesticide. The percentage of sites with acute exceedences for
invertebrates, for instance, ranges from 3.2% at 1.0 Ib Cu2+/A applied, and increases to about
25% of sites at an application rate of 7.5 Ibs Cu2+/A. The RQs derived for freshwater fish with
the BLM exceed the acute LOG for less than 1% of sites for application rates of 1 Ib Cu2+/A up
to7.51bsCu2+/A.
Table 25 shows some examples of the reductions in application rates for some of the high
application rates for the respective crops. The reduction in the maximum application rate for
citrus and grapes, with defined application interval and maximum seasonal rates, brings
maximum potential exposure down to a level at which 10% of the 811 RQs considered in the
assessment would exceed the acute LOG for freshwater invertebrates, and < 1% of RQs would
exceed the acute RQ for fish. Approximately 13% and 1% of the sites would exceed the chronic
LOG for freshwater invertebrates and fish, respectively.
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Table 25. Example Comparison of Rates Used in Risk Assessment and Revised Label Rates
Crop
Citrus
Filbert
Peach
Current Labeled Rate
or Revised Rate
Current
Revised (algal spot,
melanose, scab)
Current
Revised (eastern filbert
blight)
Current
Revised (dormant
application)
Application Rate
Ibs Cu2+/A
15.43
3.15
31.8
6
6.75
3.15
Application
Interval (days)
7 (assumed)
7
7 (assumed)
14
7 (assumed)
30
Seasonal Maximum
Application
(Ibs Cu2+/A)
61.72 (assumed)
12.6
63.6 (assumed)
24
13.5 (assumed)
6.3
Appendix A lists the revised maximum application rates, minimum retreatment intervals
and maximum seasonal rates for agricultural uses of copper. The refined maximum single
application rates for these crops are significantly less than the highest labeled rate considered in
the risk assessment, where most are 3.15 Ibs Cu2+/A or less. The majority of retreatment
intervals are 7 days or longer, with only a few exceptions such as tomatoes and peppers.
Although these crops have a 3-day application interval, single application rates were to 0.79 and
1.6 Ibs Cu2+/A for peppers and tomatoes, respectively. The crop with the highest seasonal
application rate is Easter lilies, but the registrant has indicated that this crop is grown in a very
small portion of the country, and will revise labels to include language limiting treatment to only
one season every four years.
Although the rate reductions are expected to result in fewer freshwater bodies having
aquatic animals potentially at risk, there is some uncertainty in the percentage of sites. As
detailed earlier, the risk estimates for each application rate were calculated using a regression of
the peak values from 32 PRZM/EXAMS scenarios. Because label instructions were inconsistent
for use of copper on many crops, many of the 32 scenarios were run based on the maximum
single application rate, assuming four applications a week apart. As indicated in Appendix A,
revised labels will include the maximum single application rate, maximum seasonal rates, and
defined minimum application intervals.
There is also some uncertainty in the peak values used in the regression. Screening
assessments were performed using PRZM/EXAMS use the 1-in-10-year peak value as the acute
EEC. Because of concerns that EXAMS could not properly simulate 30 years of successive
application of a stable pesticide, the peak value from the first year of application was used as the
EEC. The EEC simulated from the first of the 30 years of data would likely be less than the
standard 1-in-10-year exposure value calculated from a full 30-year simulation, although some of
the 32 sites would simulate heavier rainfall in that single year, and others would simulate light
rainfall years.
Therefore, EPA has determined that with the reduction of rates, establishing minimum
retreatment intervals and defining seasonal maximum rates, estimated exposures described in the
screening-level ecological assessment will be significantly lower. Adding advisory language to
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product labels to minimize potential spray drift and water chemistry criteria that may lead to
greater copper toxicity in water bodies will also reduce potential adverse effects.
Freshwater Plants
Because the BLM has not been parameterized to assess freshwater plants, it could not be
used to assess potential copper exposure and toxicity to freshwater plants. RQs for freshwater
plants were calculated using estimates of total dissolved copper using PRZM/EXAMS, which
overestimates the amount of copper that is potentially toxic to exposed organisms. The risk
assessment provides a single RQ for a range of application rates, based on a regression of results
from 32 PRZM/EXAMS scenarios. These RQs signal a potential risk to non-vascular plants
(based on algae data) for application rates of 1.5 Ibs Cu2+/A and above. However, RQs for
aquatic vascular plants and endangered species are below the Agency's level of concern.
In addition to the use of total dissolved copper EECs in the calculation of aquatic plant
RQs, the uncertainties described above for the regression of the peak values from 32
PRZM/EXAMS scenarios also apply to the aquatic plant assessment. Some potential for risk to
aquatic plants is not unexpected, since algae and aquatic plants are target species for direct water
applications of copper pesticides. However, the reductions in maximum application rates, and
the establishment of maximum seasonal rates and minimum application intervals will reduce the
potential for risk to aquatic plants from agricultural applications of copper.
Marine/Estuarine Organisms
As with freshwater aquatic plants, the RQs for estuarine/marine organisms used in the
assessment should be considered conservative because estimates of copper concentrations are for
total copper, not the cupric ion. The BLM has not been parameterized for estuarine/marine
organisms, so it could not be used to assess potential copper exposure and toxicity to
estuarine/marine animals. As for the freshwater organism assessment, RQs for estuarine/marine
organisms were calculated using the same regression on the peak copper concentrations that
resulted from various application rates in the 32 PRZM/EXAMS simulations run for copper. At
a rate of approximately 3 Ibs Cu2+/A, acute and chronic RQs exceedences occur for both
estuarine/marine fish and invertebrates, respectively. Acute RQs for invertebrates are exceeded
at 1.5 Ibs Cu2+/A, and chronic RQs for fish are exceeded at 1 Ib Cu2+/A. RQs for
estuarine/marine plants did not exceed the acute LOG.
In addition to the use of total dissolved copper EECs in the calculation of aquatic plant
RQs, and the uncertainties described for use of the peak EEC regression, there is also uncertainty
in the use of the PRZM/EXAMS static pond scenario to represent exposure in an estuary. Many
crops can be grown adjacent to estuaries, and transport to estuaries in parts of the copper use area
is likely. However, the static pond does not simulate the daily ebb and flow of freshwater and
saltwater in an estuary, and the resulting changing salinity and hardness of the water would also
affect the speciation of dissolved copper.
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In spite of these uncertainties, the reductions in maximum application rates, and the
establishment of maximum seasonal rates and minimum application intervals will reduce the
potential for risk to estuarine/marine animals from agricultural applications of copper.
2. Direct Aquatic Uses
Because of the inconsistent and incomplete use application information on current labels
for direct aquatic uses, the Agency made several assumptions in the aquatic risk assessment. The
risk assessment assumes treatment of an entire water body to achieve the maximum application
rate, a water concentration of 1 ppm. For invertebrates, fish, and aquatic plants, RQs for this rate
exceed the endangered species LOG and the acute risk LOG at >99% of sites simulated by the
BLM. The chronic risk LOCs for aquatic invertebrates, and fish are exceeded at >96% of the
sites
Input from major user groups indicates that typical rates are significantly lower than the
maximum rate allowed, ranging from 0.2 to 0.5 ppm for algae management, the greatest use of
copper products in direct aquatic applications. Use rates will greatly fluctuate, depending on pest
infestation in a given water body. In addition, users indicated that it is standard practice for most
aquatic uses to treat only a portion (up to 25-33%) of a water body at a time. The EXAMS
model is used in the risk assessment to evaluate the risk from application to a fraction of the
water body, but because of limitations in the model, this in essence is an assessment of a
fractional application to the entire water body.
As discussed in the risk assessment, even application of copper to only a portion of a
water body is likely to result in risk to aquatic organisms. When only a portion of the water body
is treated, organisms in the vicinity of the treatment can be exposed to the full concentration of
copper applied, while others further from the treated area may not be exposed at all. Fish and
larger, more mobile invertebrates may be able to move out of the treated zone until the copper
dissipates from the water column, but smaller and more sedentary invertebrates will be affected.
Recovery of the affected organisms will vary on a site-to-site basis, and the specific
effects on any given ecosystem are impossible to predict given the scale of this assessment.
Populations of phytoplankton and zooplankton (the organisms most likely to be lethally affected
by use of copper) are dynamic, as the recovery of these populations is difficult to predict to
determine its impact on the rest of the ecosystem. In aquatic systems where copper is applied
frequently the community may shift to more copper tolerant organisms, and/or some of the
organisms present may develop metabolic pathways for dealing with higher copper exposure.
Because of the great variance in water body chemistries across the US, this will
overestimate the potential risk to some aquatic organisms, and underestimate it for others.
However, based on refined use information provided by user groups, estimated exposures will be
significantly lower. Typical application rates are significantly lower than the maximum assessed
rate in the screening-level ecological assessment; thus, adverse effects to non-target organisms
are expected to be lower. Additionally, the benefits of properly managing the target pests are
significant in protecting human health and animals, including potential harmful toxins from algal
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blooms, and water body maintenance to reduce the development and decay of algal and plant
matter than can reduce DOC needed by organisms.
3. Urban Uses
One of the risk assessment goals of the Agency is to estimate pesticide exposure through
all significant routes of exposure from both agricultural and non-crop uses. However, the
ecological risk assessment for copper pesticides focuses on the agricultural and direct aquatic
uses, being the greatest usage of copper pesticides, and pesticide-transport models are available
to estimate potential aquatic exposure from these uses. Based on laboratory toxicity tests with
aquatic animals, adverse effects could occur to exposed organisms in aquatic environments.
Other potential sources of copper-treated products/sites that may result from a number of
non-crop pesticidal uses, including use as a wood treatment, lawn fungicide, pool and fountain
algaecide, sanitary sewer root killer and ingredient in anti-fouling paints. The wood treatment,
anti-foulants, and other antimicrobial uses will be addressed in a separate ecological risk
assessment to be produced at a later date by the Agency. The ecological risk assessment
addresses the root-killer and lawn uses to a limited degree.
Root Control in Sewer Lines
The national-scale risk assessment for use of copper sulfate as a sewer line root-killer
discussed in the previous chapter provides an upper bound estimate of potential risk. The E-
FAST model requires an estimate of total production of a pesticide to come up with a per capita
loading estimate, but the total production of copper sulfate pentahydrate for root control can not
be distinguished from other uses on the same label. Therefore, the risk assessment assumes that
every household in the United States applies a total of 0.5 Ib Cu2+ per application twice a year.
This equates to approximately 2.2 million pounds of metallic copper. The CSTF subsequently
provided a preliminary estimate of potential use of approximately 857,000 pounds of metallic
copper annually.
The ecological risk assessment indicates that if all households in the nation were to apply
copper sulfate pentahydrate for root-control at maximum recommended rates in a single year,
then the acute LOG would be exceeded for 85% and 20% of model sites for freshwater
invertebrates and fish, respectively. The corresponding percentage of sites for which the chronic
LOG could be exceeded would be 74% and 13%, respectively. This assessment assumes that all
of the copper applied to sanitary sewers will be transported to water bodies in which aquatic
animals and plants might be exposed. In fact, much of this copper must be removed by publicly
owned treatment works (POTWs), which must limit the amount of copper that pass through to
surface water according to the terms of waste-water discharge permits.
Although there are no available models or data to refine the screening-level assessment
on urban uses, as well as uncertainties with the available data, the Agency believes that actual
exposures are significantly lower. As stated earlier in Section III with respect to the root-killer
treatment, the "down-the-drain" model assumes that all households simultaneously used the
sewer treatment at the maximum labeled rate. Available information indicates that
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approximately 25% of all households have septic systems, for which treatments of copper in this
type of sewer system is not permitted. Alternatives to homeowner root-killer treatments include
mechanical removal of invasive roots such as high pressure water jet, mechanical snake, and a
steel cutter. Other available chemical alternatives include products that contain lye or sulfuric
acid.
At least one jurisdiction has considered the risks and benefits of the root control use of
copper sulfate pentahydrate on a more regional scale, and determined that mitigation was
warranted. For instance, the California Department of Pesticide Regulation has prohibited the
use of copper sulfate pentahydrate in nine counties in California out of concern that POTWs in
the San Francisco Bay area could not comply with water quality criteria for copper if this use
continued. Tri-TAC, a technical advisory group for POTWs in California, commented that an
estimated 5 to 12% of copper received by POTWs in their state was a result of root-killer use.
Similar load estimates to POTWs from use of copper as a root killer were not available
for other regions. The assessment of copper sources in the San Francisco Bay watershed
performed for the Clean Estuary watershed concentrated on urban runoff, not inputs from
sanitary sewers to POTWs. Their description of other studies in Maryland and Sweden of copper
loadings concentrated on runoff and storm water in a like manner. TMDLs may potentially
discuss discharge of copper from POTWs as a point source, but not detail the sources of copper
to the POTW itself.
Since this product label states that it is not for use in septic systems, approximately 25%
of households cannot use this product. In addition, while it is certain that not all of the remaining
households use copper sulfate for root control in the same year, it is not possible to estimate the
number that do in any particular year. Homeowners can choose to apply alternative chemicals
for root control; some options include sulfamic or sulfuric acid and sodium or potassium
hydroxide (Ohio Department of Agriculture, 2002). Even if the amount of root killer product
sold were estimated, there are no records of how much homeowners actually use. The
preliminary estimate provided by the CSTF is more than 1/3 of the Agency's highly conservative
estimate that was assessed. Even with the estimate that the CSTF provided, the Agency believes
that this estimate is a conservative value, as this figure is based on annual marketing data.
Professional root control services may use copper sulfate pentahydrate, but are more likely to
remove roots mechanically. Professionals may also use chemical alternatives such as metam
sodium and dichlobenil, diquat or others.
A risk-benefit decision for the root control use of copper sulfate pentahydrate would
therefore require consideration of the additional burden placed on POTWs to remove excess
copper from the waste stream in addition to the potential risk to aquatic animals and plants. Use
data is not available to allow such an evaluation on a nationwide scale. Therefore, no changes
will be made to the copper sulfate pentahydrate label for root control use at this time. The
Agency will solicit comments on the extent of copper use as a root killer, and the potential
burden placed on POTWs by this use, during the comment period which will follow publication
of the copper RED.
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Other Urban Uses
As described in Section III, above, the Agency does not currently have a model capable
of predicting concentrations of pesticides that might occur because of outdoor urban uses, such
as the use of copper as a lawn fungicide. Furthermore, the amount of copper used by
homeowners for this use cannot be precisely determined. The relative importance of lawn uses
of copper as a potential source of loading to surface water will vary between different
watersheds, as there are many other potential urban sources of copper, as described above. No
mitigation is proposed for other urban or suburban uses of copper at this time.
4. Advisory Language
To be eligible for reregi strati on, labeling changes are necessary to implement mitigation
measures outlined above. Specific language to incorporate these changes is specified in the
Table 26. Generally, conditions for the distribution and sale of products bearing old
labels/labeling will be established when the label changes are approved. However, specific
existing stocks time frames will be established case-by-case, depending on the number of
products involved, the number of label changes, and other factors.
For agricultural products containing copper to be eligible, revised labels need to include
the following advisory language to ensure that copper pesticides are used appropriately and to
minimize potential adverse exposure effects to humans and other non-target organisms in the
environment. To minimize effects to non-target aquatic organisms, aquatic hazard statements on
the labels must be revised to describe water chemistry conditions (e.g., low pH level and low
DOC) that would likely lead to greater copper toxicity to non-target organisms. Labels also need
to include advisory language on measures which users can adopt to reduce spray drift potential,
such as language recommending that:
• Application not occur during temperature inversions;
• Applications be made when wind velocity favors on-target deposition (approximately 3
to lOmph);
• Application not be made when wind speed exceeds 15 mph;
• Aerial spray should be released at the lowest height consistent with pest control and flight
safety;
• Ground boom and aerial applications use only medium or coarse spray nozzles; and
• For aerial applications, the spray boom should be mounted on the aircraft as to minimize
drift caused by wingtip or rotor vortices. The minimum practical boom length should be
used.
Specific label language including these recommendations is detailed in Table 26. With
the implementation of these additional advisory label language points, risk to non-target
organisms will be reduced.
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5. 303(d) - Designated Impaired Water Bodies
The California Regional Water Quality Control Board (CRWQCB) commented that
copper has been named as a cause for water quality impairments for some 626 water bodies in
the United States under section 303(d) of the Clean Water Act (CWA). When a water body is
listed as impaired by an identified pollutant, States may be required to devise a plan to regulate
the Total Maximum Daily Load (TMDL) of the pollutant entering the water body through point
and non-point sources. The development of a TMDL requires identification of the sources of the
pollutant in the watershed, and an estimate of the relative load from each source. TMDLs have
been approved for 246 of the 626 water bodies for which copper is listed as a cause of
impairment. A majority of these sites list other metals in addition to copper as pollutants, either
from mining or other non-agricultural sources.
Impairments Potentially Due to Agricultural Use of Copper
Eight of the 246 approved TMDLs for copper identify agricultural use of copper as the
most likely source causing the impairment. These eight are all in Kansas. Land use in the eight
watersheds is 95 to 99% combined cropland/pasture and rangeland, with no less than 68% of any
watershed characterized as cropland/pasture. The water quality criteria for copper in Kansas are
site-specific, based on an equation that takes the hardness of the water into account.
The eight TMDLs for copper in Kansas identify a number of possible agricultural sources
of copper. An important source identified is the use of copper sulfate to treat livestock for hoof
diseases. Copper sulfate is also used in these watersheds at 3 to 6 Ibs Cu2+/A to alleviate copper
deficiency in soybeans, and as a feed supplement for swine. Finally, the TMDLs mention that
copper can be applied to agricultural crops such as orchards.
The King County Department of Natural Resources and Parks (KCDNRP) in Washington
reported water body impairments that might be related to use of copper as an agricultural
pesticide. Washington State water quality criteria for copper are 0.0070 mg/L (acute) and 0.0075
mg/L (chronic) at median hardness. The compliance standard is that the 1-hour concentration
cannot be exceeded more than once every 3 years. The chronic criterion was reported to be
exceeded once at Mill creek (0.0056 mg/L, presumably at a lower hardness) during base flow
and the acute criterion once at a tributary of Newaukum Creek (0.0072 mg/L) during storm flow
(KCDNRP, 2004).
The Agency's TMDL web site indicates that a TMDL has not been submitted for the
Green-Duwamish watershed, in which these Washington water bodies are located. In addition,
the State of Washington has not reported the potential sources of the copper pollutant in these
waters. However, the report prepared for the KCDNRP identifies the sampling location for
Newaukum Creek as representing agricultural and pasture land uses. Land use in the Mill Creek
basin is reported to be forest, residential and agricultural.
Impairments from Aquatic Use of Copper
Two water bodies in California are listed as impaired due to the use of copper as an
algaecide applied directly to water. In 2002, the Tinemaha Reservoir in California, which had
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previously been listed under 303(d) of the CWA for generic "metals" contamination, was more
specifically listed for copper pollution caused by use of copper sulfate as an algaecide for taste
and odor control in drinking water. However, 10 months of surface water sampling undertaken
for the development of a TMDL for the reservoir showed the reservoir to be in compliance with
water quality standards for both total and dissolved copper. Therefore, the staff of the
CRWQCB recommended in a published report that the Tinemaha Reservoir be removed from the
list of impaired water bodies during the next listing cycle.
The Haiwee Reservoir in California was also listed as impaired due primarily to
application of copper as an algaecide. In addition to the discharge of copper sulfate to the
reservoir itself, copper sources include a percentage of "unspecified" copper, such as copper
coming in from the Los Angeles Aqueduct (LAA) with no readily identifiable source from the
available data and naturally occurring contributions of copper. Potential sources of this copper
are historic mining activities, elevated copper in ground or surface waters due to copper-bearing
minerals in soil or rock and undetermined water supply management practices in the watershed
The Washington Department of Ecology (WDOE) identifies Steilacoom Lake as a water
body impaired by copper with an approved TMDL
http://www.ecy.wa.gov/programs/wq/tmdl/approved_tmdls.html. In their report, "Copper in
Sediments from Steilacoom Lake, Pierce County, WA," the WDOE reports that copper levels in
sediment range to over 1000 mg/kg dry weight, and that the "primary source of the metal in the
sediments is many years of application of the algaecide, copper sulfate." Steilacoom Lake is a
320 acre man-made lake with a maximum depth of 20 feet. This urban lake is surrounded by
single family homes, and is classified as eutrophic.
The WDOE performed a series of bioassays with the sediment, and reports that aquatic
invertebrates Hyalella azteca and Hexagenia limbata showed significant adverse acute response
in bioassays (WDOE, 1992). Both of these invertebrates spend at least a portion of their life
span dwelling in bottom sediment. When exposed to Steilacoom Lake sediment, Hyalella azteca
suffered 30% mortality over 14 days, and Hexagenia limbata suffered 50% mortality. No
adverse effects were observed in acute or chronic bioassays using Daphnia magna,
Ceriodaphnia dubia, and Chironomus tentans.
Impairments Due to Antimicrobial Use of Copper
As described above, ecological exposures from antimicrobial uses of copper are not
considered in this RED. These uses will be evaluated in a subsequent risk assessment planned to
be completed at a later date.
TMDLs have been developed for two water bodies in California impaired by the use of
copper in anti-fouling paints applied to boat hulls. An analysis of the likely sources of copper in
the Shelter Island Yacht Basin in San Diego Bay concluded that as much as 98% of the copper
detected was from leaching of anti-fouling paints from boat hulls and the scrubbing of boat
bottoms treated with this paint. The Agency's Technical Support Document (TSD) for the San
Diego Creek and Newport Bay Toxics TMDL (U.S. EPA, 2002) used information from the
Shelter Island Yacht Basin TMDL to estimate sources of copper leading to impairment. The
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document estimates that 50,000 of 58,000 pounds of copper per year are attributable to copper
from anti-fouling paint, with the rest due to urban road runoff, contaminated sediments,
atmospheric deposition, and sea water.
A 2004 report titled "Copper Sources in Urban Runoff and Shoreline Activities,"
prepared for the Clean Estuary Partnership, summarized the sources of copper carried to the San
Francisco Bay via runoff, or introduced directly by shoreline activities. The report also
attempted to quantify the loading of copper from each of the sources. Although the uncertainty
in these loading estimates varied between sources, and for some sources may have been as high
as a 10-fold error in their judgment, it allowed the authors to rank the sources for the amount of
copper introduced to the bay. The San Francisco Bay is not currently listed as impaired by
copper, but the report details many sources of copper beyond those included in this RED which
can lead to impairment of water bodies.
The report lists the pesticidal use of copper in anti-fouling paints on boat hulls as the
greatest source of copper in San Francisco Bay (an estimated 20,000 pounds annually).
Additional copper contribution from direct application of pesticides to the Bay and its tributaries
as an algaecide was considered a smaller contribution, at an estimated 4,000 pounds annually.
Other urban copper pesticide uses included landscaping fungicide uses, use as wood
preservatives, and use as an algaecide in pools, spas and fountains (<8,000 - < 10,000 pounds per
year total). The lower source contribution of these other copper pesticides uses is due in part to
efforts by municipalities in the San Francisco Bay watershed to reduce the use of copper-based
pesticides, both through public outreach and the prohibition of the sale and use of copper-based
root control products.
Other urban sources of copper were predicted to add an additional 27,000 pounds of
copper to the total load annually. These included wear of vehicle brake pads (>10,000 pounds
per year) and vehicle fluid leaks and dumping. Also included in the estimates were deposition of
copper air emissions, soil erosion, architectural use of copper, industrial effluent and copper in
domestic storm water.
Comparison of Ecological Risk Assessment and Watershed Loading Assessments
The screening-level ecological risk assessment indicates the potential for agricultural uses
to pose acute and chronic risk to aquatic animals (and acute risk to aquatic plants) under certain
water quality conditions. However, there are aspects of the scenario simulated by the combined
PRZM/EXAMS model which limit its utility as a tool for predicting which surface water bodies
might become impaired from the agricultural use of copper pesticides. PRZM/EXAMS is not a
watershed model; it simulates application to a 10-hectare field which is directly adjacent to a
pond that is one hectare and two meters deep. Applied pesticide is transported to the pond by
runoff and drift, and the pesticide load is instantaneously mixed throughout the 20,000,000-liter
pond.
In a typical screening-level ecological risk assessment, 30 years of applications and
weather data are used to calculate daily concentrations in the pond. These daily concentrations
represent the concentration from the previous day reduced by a day's worth of biotic and abiotic
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degradation, plus the instantaneous mixing of additional load added that day. Since the model
simulates a static pond, the concentration is not reduced by outflow from the pond.
The exercise of predicting if a specific water body or stream segment could become
impaired is more complex than the edge-of-field model represented by PRZM/EXAMS. The
loading of a pesticide within a watershed is likely to come from fields at varying distances from
a water body. The entire watershed is unlikely to be treated with the pesticide. In addition, the
different sizes of water bodies and the possibility of flow would result in slower mixing than
simulated by the model, or flashiness in the concentrations caused by flow of the contaminant
downstream.
The screening-level risk assessment is meant to represent a vulnerable scenario which
allows the Agency to be confident in a finding of no risk if no LOCs are exceeded. When an
LOG is exceeded, the Agency does not assume that specific water bodies will be at risk, but
those classes of organisms in some waters with certain characteristics and/or associated land use
may be at risk from particular pesticide uses. In the case of copper, the BLM allows further
refinement of the assessment in that certain water quality conditions in surface water may lead to
increased exposure, due to increased bioavailability and toxicity to aquatic organisms.
Although the assessment does not attempt to predict copper loading from agricultural
uses on a watershed scale, mitigation measures put in place in response to risks identified by the
screening assessment will serve to reduce potential loading from these uses. As indicated in the
ecological risk assessment, the percentage of sites (represented by 811 USGS sampling stations)
which have estimated RQs above the LOCs for freshwater animals would be significantly lower
at application rates lower than the maximum rates previously allowed on copper product labels.
The RQs for estuarine/marine animals and plants, although not calculated with the BLM for a
range of sites, are also significantly reduced at lower application rates.
As mentioned previously, the Agency's Office of Water (OW) has established a draft
ALC for copper, and is working on a revised ALC which will use the BLM to take site-specific
water chemistry into account. OPP has collaborated with OW during the development of the
copper RED on the use of BLM, sharing information gathered in the process to help in the
development of the revised ALC for copper. Once the revised ALC is completed, states will be
able to use the BLM to derive consistent, site-specific standards that meet local needs.
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V. What Registrants Need to Do
The Agency has determined that agricultural uses of coppers are eligible for reregi strati on
provided that the risk mitigation measures outlined in this document are adopted and label
amendments are made to reflect these measures. To implement the risk mitigation measures, the
registrants will be required to amend their product labeling to incorporate the label statements set
forth in the Label Summary Table (Table 26) below. In the near future, the Agency intends to
issue Data Call-In (DCI) Notices requiring label amendments, product-specific data and
additional generic (technical grade) data. Generally, registrants will have 90 days from receipt of
a DCI to complete and submit response forms or request time extension and/or waiver requests
with a full written justification. For product-specific data, the registrant will have eight months
to submit data and amended labels. For generic data, due dates can vary depending on the
specific studies being required. Below is a list of additional generic data and label amendments
that the Agency intends to require for coppers to be eligible for reregi strati on.
A. Manufacturing-Use Products
1. Generic Data Requirements
The generic data base supporting the reregi strati on of agricultural uses of copper has been
reviewed and determined to be substantially complete. However, the Agency has identified data
necessary to confirm the reregi strati on eligibility decision for coppers. These studies are listed
below and will be included in the generic DCI for this RED, which the Agency intends to issue
at a future date.
Environmental Toxicology
Old Guideline New Guideline Description
201-1 840.1100 Spray Droplet Size Spectrum
202-1 835.4200 Spray Drift Field Deposition
2. Labeling for Manufacturing-Use Products
To ensure compliance with FIFRA, manufacturing-use product (MP) labeling should be
revised to comply with all current EPA regulations, PR Notices, and applicable policies. The
MP labeling should bear the labeling contained in Table 26.
B. End-Use Products
1. Additional Product-Specific Data Requirements
Section 4(g)(2)(B) of FIFRA calls for the Agency to obtain any needed product-specific
data regarding the pesticide after a determination of eligibility has been made. Registrants must
review previous data submissions to ensure that they meet current EPA acceptance criteria and if
not, commit to conduct new studies. If a registrant believes that previously submitted data meet
current testing standards, then the study MRID numbers should be cited according to the
instructions in the Requirement Status and Registrants Response Form provided for each
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product. The Agency intends to issue a separate product-specific data call-in (PDCI), outlining
specific product-specific data requirements. These data requirements will also be included in the
PDCI.
2. Labeling for End-Use Products
To be eligible for reregi strati on, labeling changes are necessary to implement measures
outlined in Section IV above. Specific language to incorporate these changes is specified in
Table 26. Generally, conditions for the distribution and sale of products bearing old
labels/labeling will be established when the label changes are approved. However, specific
existing stocks time frames will be established case-by-case, depending on the number of
products involved, the number of label changes, and other factors.
C. Labeling Changes Summary Table
For coppers to be eligible for reregi strati on, all agricultural labels of copper-containing
products must be amended to incorporate the risk mitigation measures outlined in Section IV.
Table 26 describes specific label amendments.
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Copper Compounds Labeling Changes Summary Table 26
In order to be eligible for reregi strati on, all product labels must be amended to incorporate the risk mitigation measures outlined in
Section IV. The following table describes how language on the labels should be amended.
Description
Copper Compounds Required Labeling Language
Placement on Label
Manufacturing-Use Products
Required on all MUPs for
all Copper Compounds
containing directions for
any use
"Only for formulation into [fill blank with the appropriate pesticide type(s): fungicides,
bactericides, algaecides, herbicides, leech control, freshwater snail control, anti-foulants and wood
preservatives] for the following use(s) [fill blank only with those uses that are being supported by
MP registrants]."
Directions for Use
One of these statements
may be added to a label to
allow reformulation of the
product for a specific use or
all additional uses
supported by a formulator
or user group.
Note: Manufacturing Use Products can not have end use directions. Similarly, End Use Products
can not have formulation directions.
"This product may be used to formulate products for specific use(s) not listed on the MP label if the
formulator, user group, or grower has complied with U.S. EPA submission requirements regarding
support of such use(s)."
"This product may be used to formulate products for any additional use(s) not listed on the MP label
if the formulator, user group, or grower has complied with U.S. EPA submission requirements
regarding support of such use(s)."
Directions for Use
Environmental Hazards
Statements Required by the
RED and Agency Label
Policies
"This pesticide is toxic to fish and aquatic invertebrates. Do not discharge effluent containing this
product into lakes, streams, ponds, estuaries, oceans or other waters unless in accordance with the
requirements of a National Pollutant Discharge Elimination System (NPDES) permit and the
permitting authority has been notified in writing prior to discharge. Do not discharge effluent
containing this product to sewer systems without previously notifying the local sewage treatment
plant authority. For guidance contact your State Water Board or Regional Office of the EPA. Do
not contaminate water when disposing of equipment washwaters or rinsate."
Directions for Use
Required on all MUPs for
All Copper Compounds
For all copper compounds label, the Ingredient Statement panel must state and describe the
ingredient(s) in the following manner:
the original form/species (i.e., copper hydroxide, copper ethanolamine complex, copper
sulfate pentahydrate) as the active ingredient,
the percentage of active ingredient contained in the product,
the respective Chemical Abstracts Service (CAS) number must be listed,
and the amount of metallic copper equivalent must be expressed as the percentage by
weight directly below the Ingredient Statement.
Front Panel, Ingredient
Statement
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End-Use Products Intended for Occupational Use (WPS and non-WPS)
Required on all EUPs for
All Copper Compounds
For all copper compounds label, the Ingredient Statement panel must state and describe the
ingredient(s) in the following manner:
the original form/species (i.e., copper hydroxide, copper ethanolamine complex, copper
sulfate pentahydrate) as the active ingredient,
the percentage of active ingredient contained in the product,
the respective Chemical Abstracts Service (CAS) number must be listed,
and the amount of metallic copper equivalent must be expressed as the percentage by
weight directly below the Ingredient Statement.
Ingredient Statement
Environmental
Hazards Statements
For labels that include terrestrial uses (remove "drift" if a granular formulation), include the
following statement(s):
"For terrestrial uses: Do not apply directly to water, or to areas where surface water is present or to
intertidal areas below the mean high water mark. Do not contaminate water when disposing of
equipment washwater or rinsate."
"This product may contaminate water through runoff. Poorly draining soils and soils with shallow
water tables are more prone to produce runoff that contains this product. Drift and runoff may be
hazardous to aquatic organisms in water adjacent to treated areas."
For labels that include direct aquatic uses, include the following statement:
"Waters treated with this product may be hazardous to aquatic organisms. Treatment of aquatic
weeds and algae can result in oxygen loss from decomposition of dead algae and weeds. This
oxygen loss can cause fish and invertebrate suffocation. To minimize this hazard, do not treat more
than i/2 of the water body to avoid depletion of oxygen due to decaying vegetation. Wait at least 10
to 14 days between treatments. Begin treatment along the shore and proceed outwards in bands to
allow fish to move into untreated areas. Consult with the State or local agency with primary
responsibility for regulating pesticides before applying to public waters, to determine if a permit is
required."
Environmental Hazards
Statement
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Environmental
Hazards Statements
(All Copper Compounds)
For terrestrial and aquatic uses of copper-containing products, include the following statements:
"ENVIRONMENTAL HAZARDS"
"This pesticide is toxic to fish and aquatic invertebrates and may contaminate water through runoff.
This product has a potential for runoff for several months or more after application. Poorly draining
soils and soils with shallow water tables are more prone to produce runoff that contains this product.
For terrestrial uses, do not apply directly to water, to areas where surface water is present or to
intertidal areas below the mean high water mark. Do not contaminate water when disposing of
equipment wash-waters or rinsate."
"Certain water conditions including low pH (<6.5), low dissolved organic carbon (DOC) levels (3.0
mg/L or lower), and "soft" waters (i.e., alkalinity less than 50 mg/L), increases the potential acute
toxicity to non-target aquatic organisms."
For copper products with terrestrial uses (remove "drift" if a granular formulation), include the
following statements:
"Drift and runoff may be hazardous to aquatic organisms in waters adjacent to treated areas. "
Precautionary
Statements under
Environmental Hazards
For end-use products that include use of copper compounds to treat potable water sources, the
following statement must be included:
"Potable water sources treated with copper products may be used as drinking water only after
proper additional potable water treatments."
Precautionary
Statements: Hazards to
Humans and Domestic
Animals
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Minimum Handler PPE
Requirements
(All Copper Compounds)
NOTE:
PPE established on the basis
of Acute Toxicity of the
end-use product must be
compared to the active
ingredient PPE in this
document. In the case of
multiple active ingredients,
the more protective PPE
must be placed on the
product labeling. For
guidance on which PPE is
considered more protective,
see PR Notice 93-7.
"Personal Protective Equipment (PPE)"
"Mixers, loaders, applicators, and other handlers must wear the following:
- long-sleeve shirt,
- long pants,
- shoes plus socks."
Instruction to Registrant:
If chemical resistant gloves, apron or footwear are required by the product specific data, add the
following statement:
"Some materials that are chemical-resistant to this product are (registrant inserts correct chemical-
resistant material). If you want more options, follow the instructions for category [registrant
inserts A,B,C,D,E,F,G,or H] on an EPA chemical-resistance category selection chart."
Precautionary
Statements: Hazards to
Humans and Domestic
Animals
Signal Word
For products subject to the WPS that are classified as toxicity category I or II must also bear the
corresponding Spanish signal word and statement:
"Si usted no etiende la etiqueta, busque a alguien para que se la explique a usted en detalle. (If you
do not understand the label, find someone to explain it to you in detail.)"
Front Panel
User Safety Requirements
(All Copper Compounds)
"Follow manufacturer's instructions for cleaning/maintaining PPE. If no such instructions for
washables exist, use detergent and hot water. Keep and wash PPE separately from other laundry:
"Discard clothing and other absorbent material that have been drenched or heavily contaminated
with the product's concentrate. Do not reuse them."
Precautionary
Statements: Hazards to
Humans and Domestic
Animals immediately
following the PPE
requirements
User Safety
Recommendations
(All Copper Compounds)
"USER SAFETY RECOMMENDATIONS"
"Users should wash hands before eating, drinking, chewing gum, using tobacco, or using the toilet.'
"Users should remove clothing/PPE immediately if pesticide gets inside. Then wash thoroughly
and put on clean clothing."
"Users should remove PPE immediately after handling this product. As soon as possible, wash
thoroughly and change into clean clothing."
Precautionary
Statements under:
Hazards to Humans and
Domestic Animals
immediately following
Engineering Controls
(Must be placed in a
box.)
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Note to Registrant: If gloves are required on the label (either for handlers or early entry workers),
add the following in addition to the above:
"Wash the outside of gloves before removing."
Restricted-Entry Interval
for products with WPS uses
Note: REI's are determined
by the acute toxicity of each
copper compound which
can vary. For products
containing more than one
copper compound, the most
restrictive REI must appear
on the label.
"Do not enter or allow worker entry into treated areas during the restricted entry interval of (insert
the correct REI as specified below):
Products containing any of the following copper compounds require a 48 hour REI:
Basic copper chloride (008001)
Chelates of copper gluconate or copper citrate (023305)
Copper ammonium carbonate (022703)
Copper carbonate (022901)
Copper hydroxide (023401)
Copper ammonia complex (022702)
Copper oxychloride (023501)
Copper oxychloride sulfate (023503)
Basic copper sulfate (008101)
Copper sulfate pentahydrate (024401)
Cuprous oxide (025601)
Copper 8-quinolinolate (024002)
Copper napthenate (023102)
Copper ethanolamine complex (024409)
Products containing any of the following copper compounds require a 24 hour REI:
Copper, metallic (022501)
Products containing any of the following copper compounds require a 12 hour REI:
Copper ethylenediamine (024407)
Cupric oxide (042401)
Copper octanoate (023306)
Copper triethanolamine complex (024403)
Copper salts of fatty and rosin acids (023104)
Directions for Use,
Agricultural Use
Requirements Box
Early Entry Personal
Protective Equipment for
products with WPS uses
Note: Early Entry PPE is
determined by the acute
toxicity of each copper
PPE required for early entry to treated areas that is permitted under the Worker Protection Standard
and that involves contact with anything that has been treated, such as soil or water, is (insert correct
Early Entry PPE specified below)
Products containing any of the copper compounds listed directly below require the following
early entry PPE:
Directions for Use,
Agricultural Use
Requirements Box
-------
compound which can vary.
For products containing
more than one copper
compound, the most
restrictive REI must appear
on the label.
Coveralls over long-sleeved shirt and long pants,
chemical-resistant gloves made of any waterproof material,
chemical-resistant footwear plus socks^
chemical resistant headgear if overhead exposure,
protective eyewear, and
chemical-resistant apron when mixing, loading, cleaning equipment or spills, or otherwise exposed
to the concentrate:
Chelates of copper gluconate or copper citrate (024405)
Copper ammonium carbonate (022703)
Copper ammonia complex (022702)
Copper oxychloride (023501)
Copper oxychloride sulfate (023503)
Basic copper sulfate (008101)
Cuprous oxide (025601)
Copper napthenate (023102)
Copper ethanolamine complex (024409)
Products containing any of the copper compounds listed directly below require the following
early entry PPE:
Coveralls,
shoes plus socks,
chemical-resistant gloves made of any waterproof material, and
protective eyewear.
Basic copper chloride (008001)
Copper carbonate (022901)
Copper hydroxide (023401)
Copper sulfate pentahydrate (024401)
Copper 8-quinolinolate (024002)
Copper, metallic (022501)
Products containing any of the copper compounds listed directly below require the following
early entry PPE:
Coveralls,
shoes plus socks
chemical-resistant gloves such as or made out of any waterproof material
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Copper ethylenediamine (024407)
Cupric oxide (042401)
Copper octanoate (023306)
Copper triethanolamine complex
Copper salts of fatty and rosin acids
Double Notification
Statement
Products containing any of the copper compounds listed directly below require the following
statement:
"Notify workers of the application by warning them orally and by posting warning signs at
entrances to treated areas."
Chelates of copper gluconate (024405)
Copper ammonium carbonate (022703)
Copper ammonia complex (022702)
Copper oxychloride (023501)
Copper oxychloride sulfate (023503)
Basic copper sulfate (008101)
Cuprous oxide (025601)
Copper napthenate (023102)
Copper ethanolamine complex (024409)
Directions for Use,
Agricultural Use
Requirements Box
Entry Restrictions
for products with non-WPS
uses on the label
Entry Restriction for products applied as a spray:
"Do not enter or allow others to enter until sprays have dried."
Entry Restriction for products applied dry:
"Do not enter or allow others to enter until dusts have settled."
If no WPS uses on the
product label, place the
appropriate statement
in the Directions for
Use Under General
Precautions and
Restrictions. If the
product also contains
WPS uses, then create a
Non-Agricultural Use
Requirements box as
directed in PR Notice
93-7 and place the
appropriate statement
inside that box.
General Application
Restrictions for products
with WPS or non-WPS uses
on the label
"Do not apply this product in a way that will contact workers or other persons, either directly or
through drift. Only protected handlers may be in the area during application. For any requirements
specific to your State or Tribe, consult the State or Tribal agency responsible for pesticide
regulation."
Place in the Direction
for Use, following the
misuse statement.
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Other Application
Restrictions
Maximum Application Rates, Application Interval (days) and Seasonal Maximum Application
Rates must be specified on all product labels. See Appendix A for the correct application rates and
intervals for each site or crop.
Directions for Use
under General
Precautions and
Restrictions and/or
Application
Instructions
Entry Restrictions
General Application
Restrictions
Environmental Hazards
Products Primarily Used by Consumers/Homeowners
Entry Restriction for products applied as a spray:
"Do not allow adults, children, or pets to enter the treated area until sprays have dried."
Entry Restriction for products applied dry:
"Do not allow adults, children, or pets to enter the treated area until dusts have settled."
"Do not apply this product in a way that will contact adults, children, or pets, either directly or
through drift."
"This pesticide is toxic to fish and aquatic invertebrates and may contaminate water through runoff.
For terrestrial uses, do not apply directly to water. Do not contaminate water when disposing of
equipment washwaters or rinsate."
Directions for use
under General
Precautions and
Restrictions
Place in the Direction
for Use
Precautionary
Statements
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Appendix A
Crop
Maximum per
Application Rate
(Ibs Cu^/A)1
Maximum Annual
Rate (Ibs Cu2+/A)2
Minimum
Retreatment
Interval3
Notes
TREE FRUIT
Fall, late
Pome Fruit (apple, dormant
pear, quince)
Bloom, growing
season
Atemoya, Sugar Apple (Annona)
Avocado
Banana
Carambola
Citrus (grapefruit, kumquat, lemon,
orange, pummelo, tangelo, tangerine,
lime)
Guava
Mamey Sapote
Mango
Olive
Papaya
Passion Fruit
Persimmon
Stone Fruit (peach, Dormant, late
plum, nectarine, dormant
almond, apricot, cherry, Bloom/
prune) growing season
8.0
0.5
3.15
3.15
1.05
2.1
3.15
1.23
2.1
2.6
3.15
2.63
2.36
1.0
8.0
1.5
16.0
12.6
18.9
18.9
10.5
12.6
4.92
8.4
18.2
6.3
21.2
9.44
6.0
18.0
n/a (only 1
application
per season
permitted)
5 days
7 days
14 days
7 days
7 days
7 days
7 days
14 days
30 days
30 days
14 days
7 days
14 days
7 days
5 days
Quince use not permitted in
California
Not for use in California
Not for use in California
Not for use in California
Not for use in California
Not for use in California
Not for use in California
TREE NUTS
Betel Nut (Guam)
Cacao
0.75
2.25
8.25
15.75
7 days
14 days
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Crop
Coffee
Filbert
Litchi
Macadamia
Pecan, Pistachio
Walnut
Maximum per
Application Rate
(Ibs Cu^/A)1
2.1
6
1.23
2.36
2.1
3.15
Maximum Annual
Rate (Ibs Cu2+/A)2
12.6
24
4.92
9.44
8.4
25.2
Minimum
Retreatment
Interval3
14 days
14 days
7 days
7 days
14 days
7 days
Notes
Permitted only in
Washington State and
Oregon
Not for use in California
FIELD CROPS
Alfalfa
Corn (Field Corn, Popcorn, Sweet Corn)
Peanut
Potato
Soybean
Sugar Beet
Tobacco
Wheat, Barley, Oats
0.53
1.05
0.79
2.5
0.79
1.31
2.0
0.53
1.12
4.2
4.74
25
4.74
7.86
8.0
1.06
30 days
7 days
7 days
5 days
7days
10 days
10 days
10 days
Not permitted in California
SMALL FRUITS
Brambles (aurora, blackberry, boysen,
cascasde, chehalem, logan, marion,
raspberry, santiam, thornless evergreen)
Blueberry
Cranberry
Currant, Gooseberry
Strawberry
2.0
2.1
2.1
2.5
1.5 (severe disease)
1.0
10.0
8.4
6.3
10.0
8.19
7 days
7 days
7 days
10 days
7 days
Not for use in California
VEGETABLE
Bean (Dry, Green)
Beet (Table Beet, Beet Greens)
0.79
1.31
4.74
7.86
7 days
10 days
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Crop
Carrot
Celery, Celeriac
Crucifers (broccoli, brussel sprout,
cabbage, cauliflower, collard greens,
mustard greens,
turnip greens)
Cucurbits (cantaloupe, casaba, chayote,
cucumber, gourd, honeydew, muskmelon,
pumpkin, squash, watermelon)
Eggplant
Lettuce (endive, escarole)
Okra
Onion, Garlic
Pea
Pepper
Spinach
Tomato
Watercress
Maximum per
Application Rate
(Ibs Cu^/A)1
1.0
1.0
0.53
1.05
0.79
1.0
1.05
1.0
0.79
0.79
0.79
0.53
0.53
Maximum Annual
Rate (Ibs Cu2+/A)2
5.0
5.3
2.65
5.25
7.9
8.0
5.25
6.0
3.95
11.85
3.95
17.4
2.12
Minimum
Retreatment
Interval3
7 days
7 days
7 days
5 days
7 days
5 days
5 days
7 days
7 days
3 days
7 days
3 days
7 days
Notes
Not for use on celeriac in
California
Not for use in California
Not for use in California
VINES
Grape
Hops
Kiwi
3.0
0.53
2.1
20.0
2.65
6.3
3 days
10 days
30 days
MISCELLANEOUS
Chives
Dill
Ginseng
Parsley
Turfgrass
0.53
0.79
1.05
1.0
3.0
2.65
3.95
5.25
2.0
9.0
7 days
7 days
7 days
10 days
10 days
Not for use in California
Not for use in California
Not for use in California
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Crop
Maximum per
Application Rate
(Ibs Cu^/A)1
Maximum Annual
Rate (Ibs Cu2+/A)2
Minimum
Retreatment
Interval3
Notes
ORNAMENTALS
Lilies, Easter
All Other Ornamentals
2.5
2.0
75.0
20.0
7 days
7 days
Maximum pounds of
metallic copper which may
be applied in a 12 month
period. Do not apply any
additional copper pesticide
to this land for 36 months.
Application restrictions
apply for several
ornamentals in California
DIRECT AQUATIC RATES4
Sewer Line Treatment
Algae, cyanobacteria, aquatic weeds
(Elodea spp., hydrilla, Potamogeton spp.,
irrigation canal weed, annual naiads)
Schistosome-infected freshwater snail
control
Algae control in aquaculture
Tadpole shrimp in rice fields
0.5
1 part per million
(ppm)
1.5 ppm
0.4 ppm
2.5 ppm
2.0
n/a
n/a
n/a
n/a
6 months
14 days
n/a
n/a
n/a
No more than two
applications per calendar
year. Not permitted in the
State of Connecticut and
California counties
No more than !/> of the water
body may be treated at one
time. If the treated water is
to be used as a source of
potable water, the metallic
copper concentration must
not exceed 1 ppm.
No more than two
applications per calendar
year. In the State of New
York, this pesticide is a
restricted use pesticide.
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Crop
Leech control
Maximum per
Application Rate
(Ibs Cu^/A)1
1.5 ppm
Maximum Annual
Rate (Ibs Cu2+/A)2
n/a
Minimum
Retreatment
Interval3
n/a
Notes
1 - Maximum pounds of metallic copper which may be applied to an acre for each application. Product labels must also include application rates
described in liquid units or pounds of total product.
2 - Maximum amount of metallic copper which may be applied to an acre each growing season. Lower single application rates at higher
application frequencies may be used.
3 - Minimum number of days between each application.
4 - The use of this product in may pose a hazard to certain federally designated endangered species known to occur in specific areas of the
following counties and its respective states: Solano (CA); Lawrence, Wayne, Hancock (TN); Lauderdale, Limestone, Madison (AL); Grayson,
Smyth, Scott, Washington, Lee (VA). Before using this product, refer to the appropriate EPA Bulletin specific to your area. This Bulletin
identifies areas where the use of this pesticide is prohibited, unless specified otherwise.
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