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Glenn P. Sullivan, CLM Allied Biological, Inc. NJCOLA Meeting, April 21, 2007

Early uses of copper sulfate. 4th millennium BC - dyeing, medical ointments400 BC Greece - pulmonary disease 18th Century AD - mental disorders and afflictions of the lungs. . Current uses of copper sulfate. Baby food additiveVitamin tonicsWood preservativesAgricultural fungicide. . . Printing and engravingAnti-fouling paintsSkin Care.

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Glenn P. Sullivan, CLM Allied Biological, Inc. NJCOLA Meeting, April 21, 2007

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    1. Glenn P. Sullivan, CLM Allied Biological, Inc. NJCOLA Meeting, April 21, 2007

    2. Early uses of copper sulfate 4th millennium BC - dyeing, medical ointments 400 BC Greece - pulmonary disease 18th Century AD - mental disorders and afflictions of the lungs

    3. Current uses of copper sulfate Baby food additive Vitamin tonics Wood preservatives Agricultural fungicide Printing and engraving Anti-fouling paints Skin Care

    4. Mat forming filament alga

    6. Pseudanabaena limnetica Cyanobacteria – “filamentous” (trichomes) Taste & Odor producer – MIB’s (Methyl Isoborneol) & Geosmin Significant problem in drinking water reservoirs.

    7. Pithophora sp.(Green Alga) Forms pads that comprise mats Thick branched filaments that have reproductive cells called “Akinetes”

    8. Hydrodictyon(Green Alga) Lite Green to Yellow appearing mats “Net like” cell linkage Fast growing Mid-summer

    9. Lyngbya sp. (Cyanobacteria)

    10. Oscillatoria sp. (Cyanobacteria) Forms green sometimes leather like mats Green to dark green in color

    11. Pre-1925 use of copper sulfate in lakes Dry crystals scattered over lake in RI Venturi application in San Francisco Flow through boxes in Pasadena Continuous feed at dam in NYC Continuous feed with chlorine in inlet streams at Wanaque Reservoir Crystals on reservoir wall in Albany, NY

    12. NJDEP Positions NJDEP Surface Water Quality Standard - 0.017 ppm copper Standard not applied to algae treatments Trout susceptibility - 0.035 ppm copper (0.56 ppm copper sulfate) In 1994, maximum dosage rate of copper limited to 0.035 when trout production or maintenance waters occur downstream

    13. Fish tolerances to copper Trout 0.14 ppm Carp 0.33 ppm Catfish 0.40 ppm Pickerel 0.40 ppm Perch 0.67 ppm Sunfish 1.35 ppm Black Bass 2.00 ppm

    14. “Copper does not bioaccumulate up to high levels in fish tissue and is a required metabolic micronutrient for most aquatic species”. NYSDEC Technical Report January 2001

    15. NYSDEC Technical Report on Impacts of Copper Sulfate Compared 9 lakes treated with CuSO4 with 5 untreated lakes in New York Lakes treated with CuSO4 had significantly higher sediment copper concentrations than untreated lakes. Lakes treated with CuSO4 had lower macro-invertebrate species richness. Hexagenia (a Mayfly)was not found in any lake treated with CuSO4.

    16. Skyrocketing cost of copper

    17. An alternative to CuSO4?

    18. Chelated coppers also have a variety of uses

    19. Advantages of Chelated Copper over Copper Sulfate Chelated Copper retains solubility, works better in “hard” water Low copper concentration and Increased margin of safety to beneficial organisms Will not cause fragmentation, which leads to faster re-growth Spray application gives even distribution of copper, better control Non-Corrosive to spray equipment No dust exposure to applicator

    20. Advantages of Chelated Copper over Copper Sulfate Chelated Copper retains solubility, works better in “hard” water Low copper concentration and Increased margin of safety to beneficial organisms Will not cause fragmentation, which leads to faster re-growth Spray application gives even distribution of copper, better control Non-Corrosive to spray equipment No dust exposure to applicator

    21. How is it used? Copper Sulfate is usually applied to 1/2 lake volume 40 acre lake X 4’ AD = 208 lbs. CuSO4 = 52.4 lbs. copper Chelated coppers are also applied to 1/2 lake volume 40 acre lake X 4’ AD = 48 gallons CC = 43.6 lbs. copper

    22. Slow release of chelated coppers means there is always less copper in the water Rapid dissolution of copper sulfate means majority of copper is present during first 24 hours

    23. Percent Copper Loss 65 ppm Alkalinity pH 7.4

    24. “Study of Anabaena Control with Copper Sulfate and Cutrine” Barry H. Rosen Division of Science and Math University of Tampa Anabaena circinalis collected from Hillsborough Reservoir in Tampa, FL

    25. “Study of Anabaena Control with Copper Sulfate and Cutrine” Short term results At 0.3-1.0ppm CuSO4, 40% of Anabaena fragmented within 1 hour, 97% within 4 hours At 0.3 - 1.0 ppm Cutrine, no fragmentation during 24 hours of exposure

    26. “Study of Anabaena Control with Copper Sulfate and Cutrine” Long Term Results At 0.01 - 0.3ppm CuSO4, only single cells were found by Day 4 At 0.01 - 0.3 ppm Cutrine only caused slight fragmentation during experiment

    27. “Study of Anabaena Control with Copper Sulfate and Cutrine” Copper sulfate treated cells recovered even after 24 hours of exposure to 1.0 ppm Cutrine exposed cells consistently did not recover with even a 1 hour exposure

    28. “Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish Ictalurus punctatus” David L. Straus and Craig S. Tucker Delta Research and Extension Center Stoneville, Mississippi

    29. “Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish Ictalurus punctatus” 96 hr LC50 (mg Cu/L) pH 7.3 Alkalinity 16 Hardness 16 CuSO4 0.054 - 0.055 Chelated copper 0.51- 0.65

    30. “Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish Ictalurus punctatus” 96 hr LC50 (mg Cu/L) pH 8.2 Alkalinity 76 Hardness 83 CuSO4 0.700 - 0.762 Chelated copper 1.362 - 1.657

    31. “Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish Ictalurus punctatus” 96 hr LC50 (mg Cu/L) pH 8.4 Alkalinity 127 Hardness 161 CuSO4 0.768 - 1.139 Chelated copper 1.503 - 2.436

    32. “Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish Ictalurus punctatus” 96 hr LC50 (mg Cu/L) pH 8.7 Alkalinity 239 Hardness 287 CuSO4 0.925 - 1.041 Chelated copper 1.603 - 1.878

    33. Why switch to chelated copper?

    34. For better balance…

    35. Acknowledgements Clemson University - Dr. John Rogers Bill Ratajczyk, Applied Biochemists NYSDEC Technical Report, E. Paul, 1/2001 Use of Copper Sulfate In Control of Microscopic Organisms, Dr. Frank E. Hale Copper.org Control of Anabaena with Copper Sulfate and Cutrine-Plus, Barry H. Rosen, Univ. of Tampa Acute Toxicity of Copper Sulfate and Chelated Copper to Channel Catfish, Straus & Tucker, Journel of the World Aquaculture Society, Sept. 1993 Ralph Smith, NJDEP, Alliance for Environmental Concern Update, July-October 2000

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