CA2290205A1 - Biocidal bait composition - Google Patents

Biocidal bait composition Download PDF

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Publication number
CA2290205A1
CA2290205A1 CA 2290205 CA2290205A CA2290205A1 CA 2290205 A1 CA2290205 A1 CA 2290205A1 CA 2290205 CA2290205 CA 2290205 CA 2290205 A CA2290205 A CA 2290205A CA 2290205 A1 CA2290205 A1 CA 2290205A1
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Canada
Prior art keywords
composition
copper
bait
protein
meal
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Abandoned
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CA 2290205
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French (fr)
Inventor
Harold Lindaberry
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Individual
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Individual
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Abstract

A selective particulate protein based copper Biocidal Bait Composition and method for the control of zebra mussel, sea lamprey, molluscs and other filter feeders

Description

BIOC',IDAL BAIT COMPOSITIONS
BACKGROUND OF THE INVENTION
I. FIELD OF THE INVENTION
The introduction of the exotic filter feeding pest species zebra mussels Dreissena polymorpha and related qua~;ga mussel Dreissena bu_ensis along with the sea lamprey Petromyson marinus have introduced serious biological and economic impact on native species. These species feed on microscopic organisms such as algae, bacteria and other small particulate plant and animal matter that are the very base of the food chain and impact species all the way up the food chain. In addition the mussels foul and plug water systems necessary for public water arnd power supply. They are extremely prolific and have caused serious economic impact.
Zebra mussels attach themselves to boats, trailers, and are easily dispersed.
In addition the microscopic veli,~er stage may be dispersed on swim equipment, on fish, in water and by other wildlife.
The present invention relates to the control of these filter feeders by introducing a toxic copper moiety material in particulate microscopic bait form requiring raising only the target organism to toxic levels rather than by raising the total water volume to a toxic concentration as is required vrith other control methods currently in use.
This reduces the total amount of material required for control and having less impact on non target species such as fish and other non fillter feeders introducing less material into the environment.
This invention is different from the current slow release technology currently in use with biocides in that the~~ release the material over an extended time whereas with this technology the aim is to retain the toxic moiety within the bait until ingested and thereby released in the target organi~;m. Anti fouling paints and coatings using various copper, tin and other compounds rely maintainin;~ a toxic level in the coating preventing establishment of mollusk colonies.
Sea lamprey return to streams to spawn lay their eggs which hatch and the larval ammocetes burrow into the bottom and feed on microscopic matter for 3 to S
years. They then go through a metamorphosis and return to the lake or ocean where they are parasitic feeding on fish until they reach maturity and return to spawn thus completing the cycle.
Control of these pests currentlly involves treating them in the streams before they go through this metamorphosis into the parasitic stage by raising the toxic level of the water to a toxic level. Data suggest that utilizing the method described in this invention that only the organisms themselves need to be brought to a toxic level.
2. PRIOR ART
Chlorine and various other toxicants have been utilized to control these species all involves the concept of raising the level of toxicant in water to toxic levels or by maintaining toxic levels in coating to prevent their establishment. I find no prior art involving the preparation of copper or~other toxicant containing bait materials which allows for control of these or other aquatic species.
SUMMARY OF THE INVENTION
In accordance with this invention the biocidal copper containing composition particulate bait materials may be produced utilizing any suitable plant or animal based materials that are acceptable to the target species. IDrieC or fresh material may be utilized as the bait food base. Materials that are in the proper particle size range such as single celled algae, yeast, blood may be utiilized without further particle size reduction.
Materials having a higher protein content specially those having a high chlorophyll content are specially attractive to the target specie; and appear to prevent the release of the fish toxic copper moiety in the water when pH of formulation is adjusted on the alkaline side of the isoelectric point of the proteins in the bait material where fish toxicity is not a problem such as intake pipes pH adjustment may not be necessary.
There are four factors that govern the success of a suitable bait material, 1.-It must be able to retain thf~, toxicant: in the bait material until ingested, 2.-The bait must be acceptable to the target species in order that they feed on it,
3.-The particle size must be in the range that the target species can feed on it,
4.-It must be able to release the toxic moiety rapidly enough to kill the organism before it is excreted.
Copper is an ideal toxic moiety from the human safety standpoint in that it is an essential mineral nutrient in human nutrition with a minimum daily requirement of 4 milligrams per day and acceptable wai:er tolerances of 2 parts per million have been established. Applications of these bait materials which would result in residue levels well below approved tolerance levels. Sohable copper compounds and soluble chelates do not exhibit selectivity between species that is demonstrated compounds of this invention.
The copper moiety may be introduced to the bait either by being absorbed into dry bait material or added directl~r to the fresh bait material. The bait material may be ground to the proper particle size either prior to or after the addition of the toxic copper moiety. The particle size of the bait should preferably be between 5 and I 000 microns in order to be ingested by zebra mussels and lampre~~, the smaller sizes are essential for control of the free swimming veliger stages whereas particle size between 20 and 150 microns appear optimum for the settled stages.
Virtually all particulate organic. food materials have been shown to reduce the fish toxicity, and increase selectivity to some degree, however some materials appear far superior to others. The toxic moiety farms ligands with the proteinacious material or is absorbed into the starch grains where it remains until it is ingested and released. Materials that have been shown to be suitable substrate including but not limited to algae, alfalfa meal, blood meal, fishmeal, oatmeal., yeast, starch, egg, casein, leafy plant tissue, bacteria, and sewage sludge.
The level of copper in the bait material may be varied from 0.25 to 50.0 percent depending on the composition of the bait.
For treatment of flowing water or swimming or suspended stages the addition of oils, fats, waxes or other buoyant materials with a low specific gravity may be used to adjust the specific gravity of the formulation near 1 in order to allow the material to flow with the stream enabling treatment of large areas from a single site, conversely for treatment of areas where the infestation is on the bottom as is usually the case with zebra mussels in deep water away from obstacles increasing the specific gravity of the formulation quick sinking formulations or larger particlE: size may be desirable to get the material to the target area as soon as possible.
Other agents such as algae flavoring agents agar, alginates gelatin, various gums fats, waxes oils may be incor~~orated to obtain a formulation having the suitable characteristics desired for the situation involved in obtaining the proper particle size, release rate, specific gravity and attractiveness of the formulation to the particular target species.
I~ETAIIJED DESCRIPTION
a.nd test methods Zebra mussel tests were conducted in 1.5 liter aquaria exposing 4 individuals of zebra mussels Dreissena polymorpha and fathead minnow Hybornhynchus notatus to varying concentrations of the test materials and the mortality was recorded periodically usually at 24, 48 and 96 hours and the results were compared with the standard copper sulfate CuS04 and copper carbonate C'u C03 for comparative purposes as follows all concentrations are expressed on the actual copper present.

PERC',ENT MORTALITY
Z=zebra mussel F=fathead Z F Z F Z F
CuS04 2.5 - 100 100 100 100 100 1.25 - 50 100 50 100 50 0.5 - 0.0 0.0 0.0 0.0 0.0 Z F Z F Z F
CuC03 2. S - 0.0 0.0 0.0 0.0 0.0 1.25 - 0.0 0.0 0.0 0.0 0.0 It is clear from these data that neither of these materials has any significant selectivity and or toxicity between the target species and fish. In all of the conducted tests none of the zebra mussel or tlhe fathead minnows showed any mortality and thus the untreated control data have been excluded even though untreated controls were included in each of the tests.
ZM 173 10 grams of CuS04 pentahydrate was dissolved in 40 ml of water and added to 40 grams of ground alfalfa meal and the product was dried at 200 F
overnight then 5 grams of Ca(OH)2 was added to 500 ml bring the pH over 7. The product was mixed in a blender and the product was tested and the results recorded. The 24 hour mortality figures for zebra mussels have been excluded due to the difficulty in assessing accurately mortality in that time frame.
'LEST RESULTS
WITH
BIOCIIJAL COMPOSITIONS
EXAMPLE I

Z F Z F Z F

ZM 173 3.75 - ~0.0 100 0.0 100 0.0 2.5 - 0.0 100 0.0 100 0.0 1.25 - 0.0 100 0.0 100 0.0 0.5 - 0.0 0.0 0.0 50 0.0 The above data show a 7.5 fold safety factor between levels that kill zebra mussels and fish.

1 gram of CUS04 was dissolved in 20 ml of water and added to I 9 grams of dried chlorella algae the mixture ways dried at 200 F to the original weight and I
00 ml of water was added to the product and mixed in a blender and tested as described above.

MATERIAL PPM 24 HO1;IR 48 HOUR 96 HOUR

Z F Z F Z F
5.0 - 0.0 75 0.0 100 0.0 2.5 - 0.0 100 0.0 100 0.0 1.25 - 0.0 100 0.0 100 0.0 0.63 - 0.0 100 0.0 100 0.0 The above data demnstrate the' effectiveness of the bait biocidal composition increasing the safety level to 7.9 fold.

1.0 grams CuS04 pentahydrate was dissolved in 20 ml of water and added to 3 grams of oatmeal the product was then dried at 200 f. and added to 100 ml of water the product was blended and tested as described above Z h Z F Z F
ZM 143 1.25 - 0.0 75 0.0 100 0.0 0.63 - 0.0 25 0.0 100 0.0 The data clearly show at least a 2 fold safety factor with the above fomulation ZM 125 c I .0 gram of CuS04 pentahydrate was mixed with dry yeast 30 ml of heated water 10% agar 1 % chlorella solution was added and heated to allow it to be absorbed this was added to 100 ml of water to v~rhich 1.5 grams of sodium bicarbonate to bring the pH
over 7 and mixed in the blender prior to testing.

Z F Z F Z F
ZM 125 C 1.25 - 0.0 75 0.0 100 0.0 0.63 - 0.0 75 0.0 75 0.0 0.32 - 0.0 0.0 0.0 100 0.0 The above data clearly demonstrates at least a 4.7 fold safety factor between zebra mussel and fish toxicity.

5.0 grams blended whole egg was added to 45 grams copper sulfate pentahydrate the pH was adjusted to 6.~> with a 0.5% slurry of Ca{OH)2 and tested in accordance with the above test method.
r Z F Z F Z F
ZM 261 1.25 - 0.0 75 0.0 100 0.0 0.63 - 0.0 75 0.0 l00 0.0 0.32 - 0.0 0.0 0.0 75 0.0 This demonstrates about a threefold safety factor.

1.0 gram copper sulfate pentahydrate was dissolved in 10 ml of water and added to 3.0 grams of ground soybean meal and was evaporated at 200 F to dryness this was added to 100 ml of water mixed in a blender and tested in accordance with the above test method.

Z F Z F Z F

1.25 - 0.0 75 0.0 100 0.0 0.63 - 0.0 50 0.0 50 0.0 A test was initiated in 2 unaerated 6 gallon containers each containing 10 zebra mussels and 10 fathead minnows and the percent mortality recorded at various intervals over a 1 week period. ZM 1~!5 C described in example 4 was applied at the rate of 2 mg copper per square foot equivalent to 0.2 pounds per acre with the following results.
PER('.ENT MORTALITY
TREATMENT 1 DAY :? DAY 4 DAY 7 DAY
Z F Z F Z F Z F

This test demonstrate; these bait materials may be applied on a per acre basis rather than a ppm basis to obtain control of the target organisms as the calculated concentration was 0.09 ppm.

25 GRAMS of fish mc;al contaiining 45 percent protein was combined with 12.5 grams of copper sulfate pent~thydrate in 100 ml H20, liquefied and dried. 10 ml of a 2%
agar solution was added and dried and tested using the method described previously.
PER(:ENT MORTALITY
MATERIAL PPM 24 HOL:rR 48 HOUR 96 HOUR
Z F Z F Z F

2.5 - - - - 100 25 1.25 - - - - 100 0.0 0.5 - - - - 75 0.0 Test results indicate a safety factor of about 2 to 2 I /2 fold 25 grams of dried blo~~d was added to 100 grams of water and liquefied in a blender and 12.5 grams of copper sulfate pent~ahydrate was added the pH was adjusted to 6.8 with NaOH and dried and tested in accordance with the previously described method.
PERCENT MORTALITY
MATERIAL PPM 24 HOtTR 48 HOUR 96 HOUR
Z lF Z F Z F
ZM 260 1.25 - 0.0 75 0.0 100 0.0 0.5 - 0.0 50 0.0 100 0.0 0.32 - 0.0 0.0 0.0 50 0.0 The above data demonstrate a better than 2 fold safety factor.
TOXICITY ~;M 173 TO SEA LAMPREY
The following tests ware conducted in 10 liter aerated aquaria 4 larvae were placed in each container and exposed to test .concentrations and observations made at various time intervals and the date recorded SEA LAMPREY LARVAE Petromyson marinus ( test 3 ) PPM SICK DEAD

0.25 100 % 12 hrs~ 50 % 24 hrs SO % 24 hrs, 100 % 30 hr 0.5 50 % 12 hrs 50 % 24 hrs 75 % 28 hrs 100 % 34 hrs ( test 2 ) SICK DEAD
1.0 50 % 17 hrs 50% 12 hrs 100% 24 hours SEA LAMPREY LARVAE Petromyson marinus ( test I ) I .0 75 % 12 hrs :~ 5 % 17 hrs 50 % 15 hrs 100 % 24 hrs 5.0 100 % S hrs 25 % 8 hrs 100 % 24 hrs water temperature SS to 57 F
It is obvious from these data and the fish data previously described in the zebra mussel tests that there is a wide margin between the dose that kills fish and the levels required to kill sea lamprey without significant fish kill.

Claims (8)

I Claim:
1. A particulate copper containing protein based biocidal bait composition and method for the control of zebra mussel, sea lamprey, mollusks, and other filter feeders wherein the copper concentration is from about 0.005 to about 0.50, the particulate particle size ranging from about 1 to about 1000 microns with the preferred range being 5 to 100 microns, the protein containing portion of the composition being derived from either plant or animal sources.
2. A composition and method according to claim 1 where the pH is adjusted above the isoelectric point of the protein utilized preferably in the range of 6.0 to 11.0
3. A composition and method according to claim 1 where the plant protein containing portion is taken from a group consisting of algae, alfalfa, yeast, bacteria, soybean meal, soy protein, soy flour, peanut meal, oatmeal, wheat, corn, chlorophyll containing plant tissue.
4. A composition and method according to claim 1 where the animal protein portion of the bait is taken from a group consisting of fish meal, blood meal, gelatin, egg, milk solids, or other animal derived protein containing material.
5. A composition and method according to claim 1 where moisture resistance and specific gravity modifying agents are incorporated selected from a group consisting of a gel, starch.
agar, algin, gums, fats and oils.
6. A composition and method according to claim 1 where the water soluble portion of the copper in the bait is less than 10 percent.
7. A composition and method according to claim 1 where the active copper application rate is greater than 0.01 pounds per acre.
8. A composition and method according to claim 1. where the copper application rate is from 0.01 to 10.0 ppm.
CA 2290205 1999-02-17 1999-11-16 Biocidal bait composition Abandoned CA2290205A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11700499P 1999-02-17 1999-02-17
US60/117004 1999-02-17

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001052634A3 (en) * 2000-01-21 2001-12-27 Biobullets Ltd Delivering substances to invertebrate organisms
CN111280104A (en) * 2020-01-21 2020-06-16 浙江省海洋水产研究所 Compound shellfish and algae reef fish gathering device
US20220279783A1 (en) * 2021-03-04 2022-09-08 Clyde Morgan Compositions, methods, and systems for controlling invasive mussel species

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001052634A3 (en) * 2000-01-21 2001-12-27 Biobullets Ltd Delivering substances to invertebrate organisms
US7378104B2 (en) 2000-01-21 2008-05-27 Biobullets Limited Delivering substances to invertebrate organisms
CN111280104A (en) * 2020-01-21 2020-06-16 浙江省海洋水产研究所 Compound shellfish and algae reef fish gathering device
US20220279783A1 (en) * 2021-03-04 2022-09-08 Clyde Morgan Compositions, methods, and systems for controlling invasive mussel species

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