Mechanistic studies on the advanced oxidation and photochemical transformation of cyanotoxins (microcystins)

The increased occurrence of cyanobacteria (blue-green algae) blooms and the production of associated cyanotoxins have presented a threat to drinking water sources. Among the most common types of cyanotoxins found in potable water are microcystins (MCs), a family of cyclic heptapeptides containing substrates. MCs are strongly hepatotoxic and known to initiate tumor promoting activity. The presence of sub-lethal doses of MCs in drinking water is implicated as one of the key risk factors for an unusually high occurrence of primary liver cancer. ^ A variety of traditional water treatment methods have been attempted for the removal of cyanotoxins, but with limited success. Advanced Oxidation Technologies (AOTs) are attractive alternatives to traditional water treatments. We have demonstrated ultrasonic irradiation and UV/H2O2 lead to the degradation of cyanotoxins in drinking water. These studies demonstrate AOTs can effectively degrade MCs and their associated toxicity is dramatically reduced. We have conducted detailed studies of different degradation pathways of MCs and conclude that the hydroxyl radical is responsible for a significant fraction of the observed degradation. Results indicate preliminary products of the sonolysis of MCs are due to the hydroxyl radical attack on the benzene ring and substitution and cleavage of the diene of the Adda peptide residue. AOTs are attractive methods for treatment of cyanotoxins in potable water supplies. ^ The photochemical transformation of MCs is important in the environmental degradation of MCs. Previous studies implicated singlet oxygen as a primary oxidant in the photochemical transformation of MCs. Our results indicate that singlet oxygen predominantly leads to degradation of the phycocyanin, pigments of blue green algae, hence reducing the degradation of MCs. The predominant process involves isomerization of the diene (6E to 6Z) in the Adda side chain via photosensitized isomerization involving the photoexcited phycocyanin. Our results indicate that photosensitized processes play a key role in the environmental fate and elimination of MCs in the natural waters. ^

A state of war: Florida from 1939 to 1945

World War II profoundly impacted Florida. The military geography of the State is essential to an understanding the war. The geostrategic concerns of place and space determined that Florida would become a statewide military base. Florida's attributes of place such as climate and topography determined its use as a military academy hosting over two million soldiers, nearly 15 percent of the GI Army, the largest force the US ever raised. One-in-eight Floridians went into uniform. Equally, Florida's space on the planet made it central for both defensive and offensive strategies. The Second World War was a war of movement, and Florida was a major jump off point for US force projection world-wide, especially of air power. Florida's demography facilitated its use as a base camp for the assembly and engagement of this military power. In 1940, less than two percent of the US population lived in Florida, a quiet, barely populated backwater of the United States. But owing to its critical place and space, over the next few years it became a 65,000 square mile training ground, supply dump, and embarkation site vital to the US war effort. Because of its place astride some of the most important sea lanes in the Atlantic World, Florida was the scene of one of the few Western Hemisphere battles of the war. The militarization of Florida began long before Pearl Harbor. The pre-war buildup conformed to the US strategy of the war. The strategy of theUS was then (and remains today) one of forward defense: harden the frontier, then take the battle to the enemy, rather than fight them in North America. The policy of "Europe First," focused the main US war effort on the defeat of Hitler's Germany, evaluated to be the most dangerous enemy. In Florida were established the military forces requiring the longest time to develop, and most needed to defeat the Axis. Those were a naval aviation force for sea-borne hostilities, a heavy bombing force for reducing enemy industrial states, and an aerial logistics train for overseas supply of expeditionary campaigns. The unique Florida coastline made possible the seaborne invasion training demanded for US victory. The civilian population was employed assembling mass-produced first-generation container ships, while Floridahosted casualties, Prisoners-of-War, and transient personnel moving between the Atlantic and Pacific. By the end of hostilities and the lifting of Unlimited Emergency, officially on December 31, 1946, Floridahad become a transportation nexus. Florida accommodated a return of demobilized soldiers, a migration of displaced persons, and evolved into a modern veterans' colonia. It was instrumental in fashioning the modern US military, while remaining a center of the active National Defense establishment. Those are the themes of this work.

A State of War: Florida from 1939 to 1945

World War II profoundly impacted Florida. The military geography of the State is essential to an understanding the war. The geostrategic concerns of place and space determined that Florida would become a statewide military base. Florida’s attributes of place such as climate and topography determined its use as a military academy hosting over two million soldiers, nearly 15 percent of the GI Army, the largest force theUS ever raised. One-in-eight Floridians went into uniform. Equally,Florida’s space on the planet made it central for both defensive and offensive strategies. The Second World War was a war of movement, and Florida was a major jump off point forUSforce projection world-wide, especially of air power. Florida’s demography facilitated its use as a base camp for the assembly and engagement of this military power. In 1940, less than two percent of the US population lived in Florida, a quiet, barely populated backwater of the United States.[1] But owing to its critical place and space, over the next few years it became a 65,000 square mile training ground, supply dump, and embarkation site vital to the US war effort. Because of its place astride some of the most important sea lanes in the Atlantic World,Florida was the scene of one of the few Western Hemisphere battles of the war. The militarization ofFloridabegan long before Pearl Harbor. The pre-war buildup conformed to theUSstrategy of the war. The strategy of theUS was then (and remains today) one of forward defense: harden the frontier, then take the battle to the enemy, rather than fight them inNorth America. The policy of “Europe First,” focused the main US war effort on the defeat of Hitler’sGermany, evaluated to be the most dangerous enemy. In Florida were established the military forces requiring the longest time to develop, and most needed to defeat the Axis. Those were a naval aviation force for sea-borne hostilities, a heavy bombing force for reducing enemy industrial states, and an aerial logistics train for overseas supply of expeditionary campaigns. The unique Florida coastline made possible the seaborne invasion training demanded for USvictory. The civilian population was employed assembling mass-produced first-generation container ships, while Floridahosted casualties, Prisoners-of-War, and transient personnel moving between the Atlantic and Pacific. By the end of hostilities and the lifting of Unlimited Emergency, officially on December 31, 1946, Floridahad become a transportation nexus. Florida accommodated a return of demobilized soldiers, a migration of displaced persons, and evolved into a modern veterans’ colonia. It was instrumental in fashioning the modern US military, while remaining a center of the active National Defense establishment. Those are the themes of this work. [1] US Census of Florida 1940. Table 4 – Race, By Nativity and Sex, For the State. 14.