Ozone

Ozone has been seen as an environmentally friendly and more efficient replacement for chlorine, however high cost and volatility of the O3 molecule have made this treatment unpopular. Ozone produces OH- and HO2 as free radicals during decay; these radicals undergo an oxidation reaction with the tissue of target organisms destroying them.[1] ,[2] . In laboratory testing ozone was found to be as effective at killing mussels as chlorine and worked much quicker 5 hours compared to 18 for chlorine.[3] A second experiment found that this speed advantage decreased at higher temperatures (above 30°C) as chlorine and ozone became similar in time to 95% mortality.[4] O3 is created by exposing air to electricity; the electric charge provides energy which causes the O­2 molecules in the air to reform as O3[5] . Ozone has a fast rate of decay and must be made on site for the chemical to be used.[6] The fact that ozone decays rapidly means that it is safe to use in freshwater as it will not have long term toxic effects on the environment.[7] Ozone is currently very expensive compared to other treatment possibilities as it can cost ten times more than chlorine treatments[8] .While ozone could be an effective alternative to chlorine treatments high start up costs and the necessity for onsite production make ozone an undesirable alternative at this time.

Bromine

Bromine has been considered as a possible substitution for chlorine as it is also a halogen. Bromine is a liquid in its natural state making it easy to transport[9] . It is produced by treating seawater with chlorine gas and air[10] . Bromine can remain present much longer in an aquatic system than ozone as it degrades much more slowly[11] . It reacts much the same way as chlorine destroying organic matter through an oxidation reaction. Chlorine was found to be more effective at killing larval mussels than bromine in an intermittent exposure test with 85% mortality compared to 67%[12] . Bromine is potentially more effective than chlorine in high ph conditions (greater than 8.0)[13] Bromine has difficulty killing adult mussels as they will close when they sense the oxidant; this makes bromine more suitable as a preventative measure than as a solution[14] . Long term toxic effects for bromine are also a concern; bromine is slower to decay than chlorine and as such can remain in the water system and threaten no target species[15] . Bromine does not work as well as chlorine to kill mussels and as such has not become widely used[16] .

Potassium permanganate

Potassium permanganate is another oxidizing agent that we considered as a possible chlorine replacement. Potassium permanganate is a natural solid and is easy to move to different sites for possible deployment[17] . Field preparation creates no secondary waste products and has a relatively small environmental impact compared to other treatments[18] .It is worth noting that permanganate is also much more expensive to purchase than bulk chlorine 3500$/ton versus 233.75$/ton in 1997[19] [20] . The major drawback of permanganate is that it only kills muscles with high concentrations over a long period of time[21] . Permanganate also works through an oxidation reaction[22] . Potassium permanganate was found to be generally ineffective to kill mussels compared to chlorine being both slower and requiring higher chemical concentration[23] . While potassium permanganate is more environmentally friendly low toxicity against zebra mussels and high cost mean it has not been widely used as a treatment.

Hydrogen peroxide

Hydrogen peroxide has been considered as an alternative to chlorine treatment as it is more environmentally friendly. Unlike halogens which can produce toxic side products hydrogen peroxide breaks down into oxygen and water meaning treated areas are safe for human use[24] . Peroxide is mainly a preventative measure as it does not effectively kill adult mussels even at high concentrations[25] . While hydrogen peroxide does not kill zebra mussels it can be effective at preventing mussel larva from attaching to surfaces in treated areas[26] . Costing 4 to 500 dollars a ton hydrogen peroxide is more expensive than chlorine[27] . Like chlorine hydrogen peroxide combats mussels through an oxidation reaction. The necessity of using higher concentrations of hydrogen peroxide than of other solution has lead to this option being more expensive and as such it has not become a common treatment[28] .

Potassium Salts

Salts containing potassium are a viable treatment for killing zebra mussels, as they are relatively environmentally benign. Potassium salts are much more lethal to zebra mussels than they are to other species[29] , as they interfere with cellular respiration by reducing the activity of Na+/K+ ATP'ases. These enzymes catalyze the reaction to convert ATP (Adenosine Triphosphate) to ADP (Adenosine Diphosphate). This causes the cilia on the mussel's gills to stop beating, asphyxiating them. As salts such as KCl are already approved for use as additives to drinking water, the environmental impact of potassium salts is minimal.

Potential Bio-bullet applications

Killing mussels have a minimal impact on the physical body of the mussel as the shell is not affected by the chemical treatments[30]. Physical methods must be used to clear the mussels from their attachment once they have been killed. Chemical treatments have minimal impact on the shells of mussels due to a coating of protective proteins called Conchiolin. Conchiolin acts as a shield protecting the calcium carbonate of the shells from corrosion by acids and other chemical treatments[31]. This protective layer means the only way to kill a mussel with chemicals is to directly treat the mussel itself bypassing the shell. Bio-bullets are a new innovative way to deliver chemicals that would better get around the mussels natural defenses meaning the mussels can be killed much more easily.

Bio-bullets would be extremely difficult to use with Ozone. Ozone has a high rate of decomposition and would most likely decompose to water and oxygen before the bio-bullets could be deployed. Since Ozone must be produced onsite, bio-bullets would have to be produced on site as well meaning this option would be prohibitively expensive. Due to Ozone’s high rate of decomposition and the high cost of creating Ozone bio-bullets it would be ineffective to create bio-bullets with Ozone.

Bromine could be effectively be used in bio-bullets due to the long term stability of Bromine. Bromine’s natural state as a liquid means it has a high density so there would be a higher concentration of Bromine in each bio-bullet. This could allow Bromine to be delivered in higher amounts than Chlorine potentially making Bromine more effective than Chlorine in bio-bullet form. Bromine is also more stable than Chlorine over time meaning bio-bullets with Bromine centers could potentially be stored for more time than their Chlorine counterparts. Due to their similar nature and Bromine’s higher density Bromine could potentially be effectively used in bio-bullets.

As a stable solid potassium permanganate and could most likely be used in bio-bullets. Since potassium permanganate requires high concentrations to be effective bio-bullets would be extremely useful for getting as much chemical into the mussels as possible. The use of bio-bullets would also cut down on waste which is extremely important and potassium permanganate is expensive compared to other chemical treatments. Due to the stability of potassium permanganate as well as the likely cost benefits potassium permanganate could be an effective chemical for use in bio-bullets.

Hydrogen peroxide would be difficult to deliver in bio-bullet form as it decays relatively quickly. Low toxicity is also a deterrent for use as a higher volume of bio-bullets would have to be used with hydrogen peroxide than other more toxic chemicals. The preventative quality of hydrogen peroxide would also be cancelled with the use of bio-bullets making this option even less desirable. Since hydrogen peroxide is a preventative measure with a rapid decomposition it is likely bio-bullet use would decrease the effectiveness of the treatment.

The original active ingredient in the bio-bullets was Potassium Chloride, as it is especially toxic to zebra mussels, making it less likely to cause negative impact on other species. Although it is also toxic to other mussels, the speed at which the bio-bullets break down means that if the dosing is applied to a small area (such as the inlets and outlets of hydroelectric dams) the impact to other mussels would be minimized.
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