Zebra mussels were first reported in U.S. waters in the mid to late 1980's. The mussels live in fresh water and are not native to North America. Initially they were identified in Lake Erie and there was much discussion of the possibility that they would not live in the other Great Lakes, nor would they survive in inland rivers, lakes, ponds, or streams. Viable populations of the mussels have since been found throughout the Great Lakes, as far north as the upper reaches of the St. Lawrence Seaway and the Mississippi River past Minneapolis, Minn. They are present in the Illinois River, the Hudson River, and the St. Croix River. They have been found as far south in the Mississippi River as Vicksburg, Miss. and are present in the Atchafalaya River Basin. They have been found in the Arkansas River, the Tennessee River, the Ohio River from Cairo, Ill. to its confluence with the Monongahela at Pittsburgh, Pa. and in the Monongahela near Monesson, Pa. They have also been found in 45 inland lakes in Michigan, 15 lakes each in Indiana and New York, 8 inland lakes in Ohio and 7 inland lakes in Wisconsin. They have also been found in Lake Champlain in Vermont and Lakes Saratoga and George in New York.
The spread of zebra mussels may be due, in part, to its reproductive cycle. It is reported that a fully mature female mussel may produce several hundred thousand eggs per reproductive season. The eggs are fertilized outside the mussels body and within a few days develop into free swimming larvae called veligers. The veligers grow into the typical double shelled mussel shape. Within a year, a zebra mussel can grow up to an inch and become sexually mature. The mussels can become established regardless of depth, light intensity or winter temperature. Colonies of the mussels seem to grow rapidly wherever oxygen and particulate food is available and where the water currents are generally less than 6 feet per second. The mussels have also been found to colonize soft, sandy or muddy bottoms. Extensive mats of mussels several inches thick have been found on lake bottoms and on the inside and outside of pipes.
The attachment and growth of zebra mussels on water intake screens, intake structures, intake pipelines, boat bottoms, fisherman's nets, fish barrier nets, and virtually any other surface in the infested waters is a significant problem in the fresh waters of the United States.
Similarly, biofouling, the attachment and growth of aquatic organisms on submerged surfaces in fresh water, sea water, and all the intermediate water mixtures can interfere with the water supply, increase energy and fuel use requirements, increase corrosion rates, and generally cause problems and increase maintenance requirements.
For years it has been recognized that, at many locations, when pure copper or alloys high in copper content were used in sea water or mixtures of sea water and fresh water, the attachment and growth of aquatic organisms on the material was much less severe than on other materials. At a minimum, the strength of the attachment bond of the organisms to the material was not as strong to the copper based materials as it was to other materials--making cleaning and removal of the organisms easier. In general, biofouling in fresh waters was not a major concern because the fresh water organisms didn't create major problems.
The mechanism by which these alloys afford resistance to the attachment and growth of organisms in the water has generally been believed to be as a result of the release of copper or copper ions into the water source. It is commonly suggested that the biofouling resistance of copper and copper alloys is the result of copper dissolving into the water and "poisoning" the organisms. It has been observed that when some corrosion products form on the surface or debris accumulates on the surface, organisms attach to the debris or to the portion of the surface with corrosion products.
Zebra mussel attachment resistance and resistance to biofouling organism attachment without dependence on copper leaching is the unique combination of characteristics of copper nickel materials. Copper and nickel form a solid solution throughout all combinations of concentrations from 100% copper and 0% nickel to 0% copper and 100% nickel. The characteristic resistance to corrosion in fresh and sea water of the individual elements seems to be enhanced when the two elements are combined in solid solution. When the copper concentration in the solid solution equals or exceeds 65% resistance to the attachment of marine organisms has been observed. When the concentration of copper in the solid solution is in the range of 90% resistance to the attachment of zebra mussels is observed. The precise mechanisms for this resistance to attachment is not known. It may be as a result of increases in the thermal or electrical conductivity of the material which increases with increasing copper concentration. It may be as a result of the surface energy of the material. It may be as a result of the formation of oxides of copper and nickel which form on the material surface. The great resistance to corrosion of the copper nickel solid solutions in fresh and sea waters is a strong indicator that the mechanism of resistance to organism attachment is not a result of copper or copper ion leaching into the water.
The arrival of zebra mussels in U.S. waters created a new and significant biofouling problem in our fresh waters. The mussels' behavior of growing rapidly, attaching and growing on virtually any object, and growing on other mussel shells has resulted in clogging of water intake pipes and trash racks; interference with the operation of locks and dams; fouling of boat bottoms, fish nets, and barrier nets; and build ups that weigh down bouys, reducing their visibility and effectiveness.
An array of control and management techniques have been applied to biofouling and zebra mussel control.
One technique is chemical control. This is particularly common on intake systems and intake pipelines. Chlorine, chlorine dioxide, potassium permanganate or other disinfection chemicals are introduced into the water to kill the zebra mussels and their larvae. Chemical control can be effective. Chemical control also has problems. It can be expensive to install and operate a chemical control system. Great care must be used in handling the chemicals as they can be toxic to humans, as well as desirable aquatic organisms such as fish. Care must be exercised in the dispersal of the chemicals. Release of the chemicals into the open water source could result in death to fish and other desirable creatures in the water. Management and control of the chemicals can also be a hazard to people using the water that has been treated. The natural action of the chemicals produces disinfectant by-products which can be dangerous, particularly in drinking water supplies.
A second technique is the use of very warm water. Subjecting zebra mussels to very warm water has been found to kill the mussels or inhibit their growth or reproductive systems. The use of heat can be effective. The use of heat also has its problems. Among these problems are the need for a source of a significant quantity of very warm water. A thermal electric generating station may have a source for such water, a municipal treatment plant might find the production of a sufficient quantity of very warm water excessively expensive. If a sufficient quantity of very warm water is available then the next problem with this technique must be addressed--getting the water to the point where control is desired. This can often be very expensive and difficult to accomplish. The use of very warm water for control also presents challenges with regard to environmental protection. Introduction of very warm water into the source water body can distort the natural ecosystem in the vicinity of the heated water discharge. Sudden loss of supply of the very warm water can result in thermal shock that kills fish that have been attracted to the area. The need for control of the zebra mussels must be balanced against the possible damage to fish and other aquatic organisms in the water body and the cost of producing and delivering the water.
A third technique is the use of pure copper as the material of construction. It has been reported that a copper alloy with copper concentration of 70% produced no noticeable reduction in zebra mussel attachment when compared to stainless steel or acrylic material. There are reports of copper alloy materials producing successful resistance to zebra mussel attachment and growth. The composition of the materials is not identified in the reports. Construction with materials containing high concentrations of copper, 70% or more in sea water and higher for zebra mussel control, may be an effective control technique. Construction with materials containing 70% or more copper also has problems. In general, these alloys are soft and not very strong. As a result, more material is required to provide the structural integrity required by the application. The materials are heavy--about 10% heavier than steel or stainless steel. When weight and strength are both design factors, the copper and copper alloy materials may require 50% to 100% greater weight of material than a similar construction in stainless steel. The materials are expensive, costing 21/2 to 5 times as much as stainless steel. The materials, particularly the alloys, are not always readily available in the required shapes, sizes or thicknesses to allow their use in construction. Copper and some of the alloys corrode readily in fresh water, sea water, and mixtures. As a result, these materials also have a limited service life--they waste away. They release copper and copper ion into the water. There are also some indications that the presence of corrosion products on the material surface interferes with their biofouling and zebra mussel resistance. Corrosion of the material creates an additional problem for municipal water systems. These systems must meet a lead-copper concentration standard at the water taps of their customers. Corrosion of copper materials in these systems could make meeting the standard more difficult.
A fourth technique is mechanical cleaning. Zebra mussels and other biofouling organisms can be removed by scraping, chipping, plucking, or blasting the material off the surface to be cleaned. Divers may work under water to remove the unwanted organisms or the surface of interest can be removed from the water, the organisms removed, and then the surfaces returned to the water. This technique can be effective but it also has its problems. The principal problems are cost and accessibility. In some cases it is very difficult for divers to be able to reach and clean the surfaces that need to be cleaned.
The fifth technique is the use of coatings. The coatings are of generally two forms: One form is copper-containing paints and organotin paints that have been used to control fouling on boat bottoms for years. A variety of antifouling paints have been developed for sea water applications and are currently being employed for zebra mussel resistance. This form of coating is designed to inhibit the attachment and growth of organisms on the coated surface through the release of material toxic to the organisms of concern. The second form is coatings that depend on slipperiness to minimize the strength of attachment of zebra mussels and biofouling. These coatings don't resist attachment, instead they are intended to make removal of the attached growth easier or depend on high local velocities to remove accumulated materials. Some work has been done on cladding of surfaces for control of marine biofouling. Thin layers of copper or copper alloy sheet are secured to the structure to be protected. Coating with copper bearing paints, organotin paints, antifouling paints, and cladding can be effective. These coatings also have problems. Paints tend to lose their biofouling resistance over time as the toxic components are lost and the paints need to be reapplied on a regular basis. In fact, the preponderance of these paints that have been demonstrated to be effective are "ablative" by design. The paints are designed to wear away so that new biofouling or zebra mussel resistant material is exposed. There are also problems with the binders used in the paint and difficulties with wear and abrasion of the coatings when the materials are placed in natural waters. These coatings are designed to have a relatively short term service life and intended to be re-applied on a regular basis to maintain resistance to attachment and growth. For both the coatings intended to provide resistance and the coatings intended to enhance the slipperiness of the surface, there are problems with the carriers used in the paints. The carriers are often volatile organic compounds and the application process must be done in such a way as to minimize the release of these VOC's to the surrounding environment. An additional problem with all of the paints is application--particularly to structures such as water intake screens with smaller openings. The paint has a tendency to block the openings in the screen and preclude water from entering the system. A further problem with many forms of coatings and cladding is that they are frequently thick and not particularly flexible. As a result, application of the coating on items such as fish nets makes it impossible for them to be used for their intended purpose.
Claddings are generally expensive, difficult to install, and, in some cases, impossible to install in such a way as to provide the desired coverage and protection.
USPTO Backgrounds
USPTO Backgrounds