Regulating Copper in San Francisco Bay: Importance of Appropriate Use of Aquatic Chemistry and Toxicology

G. Fred Lee, PhD, PE, DEE and Anne Jones-Lee, PhD
G. Fred Lee & Associates
El Macero, CA

Regulation of Copper and Other Heavy Metals in Urban Area Street and Highway Stormwater Runoff

Need for Biogeochemistry and Aquatic Toxicology to Develop Technically Valid, Cost-Effective Regulation of Heavy Metals

Presented at Fourth International Conference on the Biogeochemistry of Trace Elements, Berkeley, CA, June (1997).

RMP 1995 Annual Report

copper concentrations in water, 1995

Near-Total Coppe in Estuary reach

Water Quality Criteria for Copper in Marine Waters

National Toxics Rule - December 1992

National Cu Criteria For:

Salt water

1 Hour Average 2.9 g/L
4 Day Average 2.9 g/L

SFRWQCB Site-Specific Objective 1995

Total Copper Objective 4.9 g/L/hr average

Based on Water Effect Ratio

US EPA 1995 National Toxics Rule

Convert Salt Water 1 Hr Average Total Copper to Dissolved Copper Multiplied by 0.83

San Francisco Bay Dissolved Copper Site-Specific Objective is 4.1 g/L

San Francisco Bay Waters in 1995 Showed Exceedances of the Total and Dissolved Copper Site-Specific Objectives

1995 aquatic bioassays

1994 water bioassays

Clean Water Act Requirements

Exceedance of Water Quality Standard for More than Once in Three Years


Water Quality Limited


Waste Load Allocation


Total Maximum Daily Loads


Phased Approach


If the Phase 1 Load Reductions Do Not Result in Achieving Site-Specific Water Quality Objective So There Is No More than One Exceedance of Any Magnitude Every Three Years, Establish New TMDLs for Phase 2

Mass Loading Limits for Copper by 2003

Stormwater Runoff
Riverine Inputs to Bay
Municipal and Industrial Wastewaters



(SFRWQCB, 1993)

Not Based on Copper Load Bay Concentration Response Relationship

Sacramento River Watershed

Copper Regulatory Issues

Copper of Concern Because of Potential Toxicity to Aquatic Life

National Criterion Based Principally on Copper Toxicity to Mytilus edulis Larvae

San Francisco Bay Water with "Excessive" Copper Non-Toxic to Mytilus edulis Larvae

Where Is the Water Quality Problem?

"Administrative" Exceedance - Not Related to Water Quality Use Impairment


Copper in San Francisco Bay Water in Non-Toxic, Non-Available Form

Copper in Sediment, 1995

copper concentrations

San Francisco Bay Sediment Copper Issues

San Francisco Bay Sediments, In General, Do Not Contain Elevated Concentrations of Copper

Average Copper in California Soils - 50 mg/kg

San Francisco Bay Shallow Sediments Stirred into the Water Column with Each Storm

Will Not Achieve Water Quality Standards with Only One Exceedance Every Three Years, Even if All Copper Inputs to the Bay Terminated

Phased Approach for Copper Control for San Francisco Bay Technically Invalid and Could Result in Expenditures in Excess of $1 Billion to Try to Meet Regulatory Requirements, Ultimately Failing to Achieve Them

- - - - - - - - - -

Toxicity of San Francisco Bay Sediments Not Related to Copper Content

Brake Pad Partnership

Common Ground Brake Pad Partnership

Moran report on Brake Pad Partnership

stormwater runoff copper concentrations

urban stormwater copper sources

South Bay copper sources

Auto Brake Pad Copper Substitution Issues

Based on Current Information, Auto Brake Pad Copper Substitution is a Mis-Directed Effort

Where is the Real Water Quality Use Impairment Due to Copper Exceedance of Water Quality Objectives?


Will Disappear If Independent Applicability Policy Terminated

Substitute for Copper Could Cause Real Water Quality Problems

Alternatives Not Properly Evaluated for Public Health and Environmental Impacts

Should Focus Water Pollution Control Resources on Finding Real, Significant Water Quality Use Impairment--i.e. Organophosphorus Pesticides

Search for Problems Due to Copper in Auto Brake Pads

If Found, Implement Control After Proper Evaluation of Alternative Materials

Pollution Prevention

Removal of Copper from Auto Brake Pads Advocated As a "Pollution Prevention" Activity

Pollution Is an Impairment of the Designated Beneficial Uses of a Waterbody

No Pollution Found for Copper Currently Present in San Francisco Bay Water and Sediments

Pollution Prevention Should Be Based On Pollution Control and Not Chemical Constituent Control

Requires Comprehensive Investigation of Aquatic Chemistry and Toxicology of Potential Pollutants

Lee & Jones-Lee

Validity of US EPA Water Quality Criteria
to Estimate Toxic Concentrations of Chemical

Criteria Assume Worst-Case Conditions - 100% Toxic/Available Forms and Chronic - Extended Periods of Exposure

Only Small Part of the Total Copper Toxic

Aqueous Chemistry and Toxicology of Copper in Marine Waters Such That Worst-Case Assumptions Over-Estimate Actual Toxicity

aquatic chemistry of chemical contaminants

Water Effect Ratio Adjustment

Measure Toxicity of Copper in Standard Lab Water and in Bay Water, Use Ratio to Adjust Water Quality Objective

Water Effect Ratio = (Site Water LC50) / (Lab Water LC50)

Only Considers Short-Term Equilibration, Does Not Consider Total and Dissolved Slow Equilibration

Underestimates Water and Specific Chemical Form Impacts

Relationship Between Analytical Chemistry and Water Quality

Poor Relationship Between Analytically Measured Concentrations and Water Quality Impacts

Purpose of Water Pollution Control

Protect and Where Degraded, Enhance Designated Beneficial Uses of Waterbody for Aquatic Life-Related Beneficial Uses

Cannot Use Chemical Analysis to Predict Toxicity

Must Use Bioassays - Toxicity Test as Primary Regulatory Tool

Need Research on Chemical Species Toxicity Test Results

Reassessment of metals criteria for aquatic life protection

aquatic toxicology

Urban Stormwater Runoff Water Quality Impacts
New Regulatory Area

US EPA 1990 Stormwater Runoff Water Quality Management Program Requires Controlling Pollution of Receiving Waters for Stormwater Runoff to the Maximum Extent Practicable Using Best Management Practices (BMPs)

Urban Area Streets and Highway Stormwater Runoff Contains Several Heavy Metals Such as Cu, Pb, Cr, Zn, Hg and As at Excessive Concentrations Compared to US EPA Water Quality Criteria

If Urban Stormwater Runoff Regulated to the Same Degree as Domestic Wastewaters-No Exceedance of Water Quality Standard Outside of Mixing Zone, Will Cost Urban Dwellers $1 to $2 per Person per Day

Must More Reliably Evaluate Real Water Quality Impacts of Stormwater Runoff-Associated Constituents

Rarely Are the Heavy Metals In Stormwater Runoff from Urban Area Streets in a Toxic-Available Form

Independent Applicability Policy

US EPA Adopted Independent Applicability Policy in Early 1990s

No Public Review

Requires Attainment of Chemically-Based Water Quality Criteria/Standards Even If Biological Assessments - Toxicity and/or Organism Assemblages Show No Impacts Due to the Chemical Present in Excess of Criterion/Standard

Leads to Administrative Exceedances of Criterion/Standard Without Adverse Impacts on Beneficial Uses of Water

Technically Invalid and Wasteful of Public Funds

Focuses on Chemicals Rather than Chemical Impacts

Ignores Purpose of Water Quality Management

Protection of Beneficial Uses

US EPA Announced Proposed Rulemaking

Possible Change Independent Applicability Policy

Lee & Jones-Lee paper Independent Applicability

Lee & Jones-Lee Appropriate Use

Suggested Regulatory Approach

Do Not Regulate Based on Worst-Case Criteria/Standards Where Exceedances Require Establishing TMDLs

Use Exceedance of Criterion as an Indicator of Potential Water Quality Problems

If Exceedance of Water Quality Criteria Found for Potentially Toxic Chemicals, Allow Discharger/Source Option of Complying With the National Chemical Criteria or Demonstrating Lack of Biological Impact-Toxicity

Problems With Conventional Water Quality Monitoring
of Stormwater Runoff

Conventional Monitoring of Runoff/Discharge Water for Suite of Chemical Parameters Produces Little Useful Information on Water Quality Impacts

Focus on Exceedance of Water Quality Criteria

Urbonas & Torno, ASCE Stormwater NPDES Related Monitoring Needs (1994) Conference Summary,

"Very little meaningful monitoring is being directed toward measuring the actual effect of stormwater discharges on the short- or long-term health of the environment. Furthermore, there is no consensus on how this monitoring should be done."

Roesner in Same Conference Discussion,

"....the course we are taking with the NPDES stormwater permitting program is going to cost municipalities a lot of money, but is not going to result in any significant improvement in the quality of our urban receiving water systems."

Factors That Must Be Considered in Translating Runoff
Concentrations to Potential Aquatic Life Water Quality Impacts

Stormwater runoff

Need Information:

  • measured concentration of constituent during runoff event - concentration time profile
  • discharge of the runoff waters during runoff event - hydrograph
  • analytical chemistry of the method used for analyses - what chemical species are measured

Receiving waters

Physical factors - Need Information:

  • Currents, tides - transport-advection
  • Mixing-dispersion
  • Biological factors - Need Information:

    • Duration of organism exposure to toxicant
    • Organism movement - locomotion
    Diel migration
    • Sensitivity to toxicants
    • Organism assemblages - resident populations relative to habitat characteristics

    Chemical factors - need information:

    • Aquatic chemistry

    Kinetics and thermodynamics of reactions

    Additive, synergistic and antagonistic reactions and impacts

    • Toxic and non-toxic, non-available forms
    • Background concentrations of constituents of concern

    Evaluation Monitoring As An Alternative to Conventional
    Water Quality Monitoring and Management

    Need Alternative Monitoring/Evaluation Approach to Determine if Real Water Quality Use Impairments Are Occurring in Receiving Waters for Urban Stormwater Runoff

    Metals and Many Other Constituents in Urban Area and Highway Stormwater Runoff in Particulate, Non-Toxic Forms

    Episodic, Short-Term Exposures Occur with Stormwater Runoff Events

    Rare that Real, Significant Water Quality Use Impairments Will Occur from Urban Area and Highway Stormwater Runoff-Associated Constituents

    Evaluation Monitoring

    Find a Real Water Quality Use Impairment in Receiving Waters for Stormwater Runoff that is Due to Stormwater Runoff-Associated Constituents

    Rather Than Measuring Suite of Potentially Toxic Chemicals, Measure Toxicity in Runoff Waters and Receiving Waters

    • If Significant Toxicity Found, Determine Its Cause through TIEs
    • Determine Sources of Toxic Constituents through Forensic Studies
    • Develop Control Programs for Toxic Constituents at Source

    Technically Valid, Cost-Effective Approach

    Lee & Jones-Lee Learned Discourses: Timely Scientific Opinions


    Possibility of Copper-Caused, Non-Detected, Subtle
    Water Quality Impacts

    While No Identified Water Quality Problems - Use Impairments Have Been Found - No One Can State With Certainty that No Subtle Problems Will Be Found in the Future

    Evaluation Monitoring Requires that Funds Be Made Available to Search for Subtle Water Quality Use Impairments

    Prioritize Water Quality Use Impairments - Focus on Most Important Problems

    With Limited Financial Resources Available for Water Pollution Control, Focus the Funds Available on the Most Significant, Readily Discernible Water Quality Use Impairments

    Search for More Subtle Problems


    • Traditional Regulatory Approaches for Heavy Metals Such as Copper Fail to Reliably Incorporate Aquatic Chemistry of Regulated Constituents into Regulatory Approach
    • Leads to Over-Regulation and Waste of Public and Private Funds in Unnecessary Waste Treatment Facilities/Control Programs
    • Need to Shift Regulatory Approach from Control of Chemicals to Managing Water Quality of Concern to the Public
    • Use Toxicity Tests to Determine if Toxicity Present. If Present, Determine Cause band Sources
    • Urban Stormwater Runoff New Regulatory Area Where There Is Need to Integrate Use of Aquatic Chemistry and Toxicology to Define Real Water Quality Problems

    References as:"Lee, G.F. and Jones-Lee, A., 'Regulating Copper in San Francisco Bay: Importance of Appropriate Use of Aquatic Chemistry and Toxicology,' Presented at Fourth International Conference on the Biogeochemistry of Trace Elements, Berkeley, CA, June (1997)."

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