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Pur(tm) Packet Effectiveness in the Presence of Pesticides and Increased Organic Matter

Permanent Link: http://ufdc.ufl.edu/UFE0043050/00001

Material Information

Title: Pur(tm) Packet Effectiveness in the Presence of Pesticides and Increased Organic Matter
Physical Description: 1 online resource (56 p.)
Language: english
Creator: WILLIAMS,TACCARA N
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2011

Subjects

Subjects / Keywords: ATRAZINE -- CARBON -- DEVELOPING -- HUMIC -- ORGANICS -- PESTICIDES -- PUR -- TOC -- TOLUENE -- TREATMENT -- WATER
Environmental Engineering Sciences -- Dissertations, Academic -- UF
Genre: Environmental Engineering Sciences thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Point of use drinking water treatment has proven itself to be highly effective in regions where only primitive techniques, such as boiling water, were the only means of treating water. One product in particular, the PUR? packet, is widely known for treating water within the United States and abroad. Very little testing of this product, however, has been done outside of Procter & Gamble? to prove the overall effectiveness of this product. One particular area of interest was the PUR? packet?s ability to remove pesticides from water. With this product being advertised for use during hiking and camping trips, this is a serious concern especially in agriculture watersheds. Water from Lake Alice on the University of Florida Campus was selected for treatment. This source water was spiked with Humic Acid, Toluene, and Atrazine to create a more competitive environment for adsorption. This was also done to increase the Natural Organic Matter concentration. Atrazine was the primary pesticide focused on because it is widely used throughout America, particularly in the Midwestern Corn Belt. A series of tests were run to see if the PUR? packet alone was enough to combat this contaminant or if the addition of Activated Carbon was necessary for acceptable removal.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by TACCARA N WILLIAMS.
Thesis: Thesis (M.E.)--University of Florida, 2011.
Local: Adviser: Mazyck, David W.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2011
System ID: UFE0043050:00001

Permanent Link: http://ufdc.ufl.edu/UFE0043050/00001

Material Information

Title: Pur(tm) Packet Effectiveness in the Presence of Pesticides and Increased Organic Matter
Physical Description: 1 online resource (56 p.)
Language: english
Creator: WILLIAMS,TACCARA N
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 2011

Subjects

Subjects / Keywords: ATRAZINE -- CARBON -- DEVELOPING -- HUMIC -- ORGANICS -- PESTICIDES -- PUR -- TOC -- TOLUENE -- TREATMENT -- WATER
Environmental Engineering Sciences -- Dissertations, Academic -- UF
Genre: Environmental Engineering Sciences thesis, M.E.
bibliography   ( marcgt )
theses   ( marcgt )
government publication (state, provincial, terriorial, dependent)   ( marcgt )
born-digital   ( sobekcm )
Electronic Thesis or Dissertation

Notes

Abstract: Point of use drinking water treatment has proven itself to be highly effective in regions where only primitive techniques, such as boiling water, were the only means of treating water. One product in particular, the PUR? packet, is widely known for treating water within the United States and abroad. Very little testing of this product, however, has been done outside of Procter & Gamble? to prove the overall effectiveness of this product. One particular area of interest was the PUR? packet?s ability to remove pesticides from water. With this product being advertised for use during hiking and camping trips, this is a serious concern especially in agriculture watersheds. Water from Lake Alice on the University of Florida Campus was selected for treatment. This source water was spiked with Humic Acid, Toluene, and Atrazine to create a more competitive environment for adsorption. This was also done to increase the Natural Organic Matter concentration. Atrazine was the primary pesticide focused on because it is widely used throughout America, particularly in the Midwestern Corn Belt. A series of tests were run to see if the PUR? packet alone was enough to combat this contaminant or if the addition of Activated Carbon was necessary for acceptable removal.
General Note: In the series University of Florida Digital Collections.
General Note: Includes vita.
Bibliography: Includes bibliographical references.
Source of Description: Description based on online resource; title from PDF title page.
Source of Description: This bibliographic record is available under the Creative Commons CC0 public domain dedication. The University of Florida Libraries, as creator of this bibliographic record, has waived all rights to it worldwide under copyright law, including all related and neighboring rights, to the extent allowed by law.
Statement of Responsibility: by TACCARA N WILLIAMS.
Thesis: Thesis (M.E.)--University of Florida, 2011.
Local: Adviser: Mazyck, David W.

Record Information

Source Institution: UFRGP
Rights Management: Applicable rights reserved.
Classification: lcc - LD1780 2011
System ID: UFE0043050:00001


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1 PUR PACKET EFFECTIVENESS IN THE PRESENCE OF P ESTICIDES AND INCREASED ORGANIC MA TTER By TACCARA NAKIA WILLIAMS A THESIS PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF ENGINEERING UNIVERSITY OF FLORIDA 2011

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2 2011 Taccara Nakia Williams

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3 To my Nana

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4 ACKNOWLEDGMENTS First and foremost I have to thank my Lord and Savior, Jesus Christ, for bringing me to this point in my life. There were several days when I thought accomplishing this feat was impossible but he continued to hold my hand and see me through this experience and I am eternally grateful for His grace and mercy. To my advisor, Dr. David Mazyck, thank you for affording me the opportunity to work with you and to learn from you. I would also like to thank my committee members, Dr. Angela Lindner and Dr. Treavor Bo yer, for their time and consideration. There are several teachers that helped shaped my educational path and I am grateful for all of them. In particular I would like to thank Mr. John Reed for sending to me engineering camp and Dr. Stephanie Luster Teasl ey for introducing me to Environmental Engineering and encouraging me to attend graduate school. I would also like to thank my research group for all of their help and support. I would particularly like to thank Amy, Alec, and Emily for all their help in t he lab and in the classroom. To the Office of Graduate Minority Programs, thank you for all of your support. Whether it was financial or emotional you were instrumental in my success here. Lastly, I would be remi s sed if I neglected to thank my mother for b ringing me into this world and pushing me to be all I could be. Thank you also to my Grandma Pearl for setting the bar so high for her children so many years ago. Ojetta as well for being a second mother to me. I want to thank all of my family, but in particular Jessica, Jeanelle, Lance, Ashanti, Danielle, and Kevin just for being there. You all helped keep me grounded through this. Lastly, I would like to thank Eric for his unconditional love, support, and understanding through th is trying time. This journey is

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5 TABLE OF CONTENTS page ACKNOWLEDGMENTS ................................ ................................ ................................ .. 4 LIST OF TABLES ................................ ................................ ................................ ............ 7 LIST OF FIGURES ................................ ................................ ................................ .......... 8 ABSTRACT ................................ ................................ ................................ ..................... 9 CHAPTER 1 INTRODUCTI ON ................................ ................................ ................................ .... 10 2 LITERATURE REVIEW ................................ ................................ .......................... 13 2.1 PUR Packets ................................ ................................ ................................ ... 13 2.1.2 Coagulation and Flocculation ................................ ................................ .. 14 2.1.3 Current Application ................................ ................................ .................. 18 2.2 Activated Carbon ................................ ................................ .............................. 20 2.3 Atrazine ................................ ................................ ................................ ............. 22 3 MATERIALS AND METHODS ................................ ................................ ................ 25 3.1 PUR Packets ................................ ................................ ................................ ... 25 3.2 Humic Acid and Toluene Studies ................................ ................................ ...... 26 3.3 Atrazine Studies ................................ ................................ ................................ 27 3.4 Activated Carbon Production ................................ ................................ ............ 28 3.5 PUR and Activated Carbon Treatment ................................ ............................ 28 3.6 Total Organic Carbon ................................ ................................ ........................ 29 4 RE SULTS AND DISCUSSION ................................ ................................ ............... 30 4.1 Raw Water Tests ................................ ................................ .............................. 30 4.2 Humic Acid and Toluene Studies ................................ ................................ ...... 30 4.3 Atrazine Studies ................................ ................................ ................................ 32 4.4 Activated Carbon Creation ................................ ................................ ................ 33 4.5 PUR and Activated Carbon Treatment Results ................................ ............... 35 4.6 Total Organic Carbon Studies ................................ ................................ ........... 37 5 SUMMARY AND CONCLUSIONS ................................ ................................ .......... 43 APPENDIX A PUR PACKET TREATMENT PHOTOS ................................ ................................ 45 B CHEMICAL STRUCTURES ................................ ................................ .................... 48

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6 B.1. T oluene ................................ ................................ ................................ ........... 48 B.2. Humic Acid ................................ ................................ ................................ ...... 49 LIST OF REFERENCES ................................ ................................ ............................... 51 BIOGRAPHICAL SKETCH ................................ ................................ ............................ 56

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7 LIST OF TABLES Table page 4 1 Raw water test results ................................ ................................ ........................ 30 4 2 Humic Acid and Toluene water test ................................ ................................ .... 31 4 3 Percent removal from Humic Acid and Toluene test ................................ ........... 32 4 4 Humic Acid, Toluene, and Atrazine test ................................ .............................. 32 4 5 Toluene and Atrazine percent removal ................................ ............................... 33 4 6 Nitrogen pyrolysis of sawdust ................................ ................................ ............. 33 4 7 Steam Activation of Pyrolyzed Sawdust ................................ ............................. 34 4 8 Activated Carbon particle analysis ................................ ................................ ...... 34 4 9 Carbon #1 treatment results ................................ ................................ ............... 35 4 11 Carbon #2 treatment results ................................ ................................ ............... 36 4 12 Percent removal Carbon #2 ................................ ................................ ................ 36 4 13 Carbon #4 treatment results ................................ ................................ ............... 36 4 14 Percent removal Carbon #4 ................................ ................................ ................ 37 4 15 Raw & DI water TOC concentration ................................ ................................ .... 40 4 16 Raw + Humic TOC concentration ................................ ................................ ....... 42

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8 LIST OF FIGURES Figure page 2 1 PUR Purifi er of Water Directions for Use ................................ .......................... 18 2 2 Chemical Composition of Atrazine ................................ ................................ ...... 23 4 1 TOC concentration for Carbon #1 ................................ ................................ ....... 38 4 2 TOC concentration for Carbon #2 ................................ ................................ ....... 39 4 3 TOC concentration for Carbon #4 ................................ ................................ ....... 39 4 4 Raw and DI water TOC concentration ................................ ................................ 40 4 5 Raw + Humic Acid TOC concentration ................................ ............................... 41 4 6 Raw vs. treated TOC concentration ................................ ................................ .... 42 A 1 Floc forming just after PUR mixing process ................................ ...................... 45 A 2 Settled floc after allowing mixture to settle for the recommended 5 minute period ................................ ................................ ................................ ................. 45 A 3 Front view of PUR treatment of Raw and DI water for the TOC concentration test ................................ ................................ ............................... 46 A 4 Top view of Raw and DI water after PUR treatment process ............................ 46 A 5 Filters after vacuum filtering the Raw and DI treated water ................................ 47 B 1 Basic Toluene chemical structure ................................ ................................ ....... 48 B 2 3 D Toluene structure created with Crystal Maker 8.1 and Accelrys DS Visualizer ................................ ................................ ................................ ............ 48 B 3 Humic Acid structure #1 ................................ ................................ ..................... 49 B 4 Humic Acid structure #2 ................................ ................................ ..................... 49 B 5 Humic Acid structure #3 ................................ ................................ ..................... 50

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9 Abstract of Thesis Presented to the Graduate School of the University of Florida in Partial Fulfillment of the Requirements for the Degree of Master of Engineering PUR PACKET EFFECTIVENESS IN THE PRESENCE OF P ESTICIDES AND INCREASED ORGANIC MA TTER By Taccara Nakia Williams May 2011 Chair: David Mazyck Major: Environmental Engineering Point of use drinking water treatment has proven itself to be highly effective in regions where only primitive techniques, such as boiling water, were the only means of treating water. One product in particular, the PUR packet, is widely known for treating water withi n the United States and abroad. Very little testing of this product, however, has been done outside of Procter & Gamble to prove the overall effectiveness of this product. One particular area of interest was the PUR pesticides from water. With this product being advertised for use during hiking and camping trips, this is a serious concern especially in agriculture watersheds. Water from Lake Alice on the University of Florida Campus was selected for treatment. This source water was spiked with Humic Acid, Toluene, and Atrazine to create a more competitive environment for adsorption. This was also done to increase the Natural Organic Matter concentration. Atrazine was the primary pesticide focused on because it is widely used thr oughout America, particularly in the Midwestern C orn B elt. A series of tests were run to see if the PUR packet alone was enough to combat this contaminant or if the addition of Activated Carbon was necessary for acceptable removal.

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10 CHAPTER 1 INTRODUCTION Water is one of the most basic necessities of every human being. For centuries, people have worked effortlessly to trea t and purify their drinking water to improve their health. In ancient times, it was assumed that clear, good tasting water was clean water 1 With advancements in technology and modern medicine, this truth was dispelled by the uncovering of several contamin ants, including bacteria and viruses, that impact drinking water quality and, in turn, impact human health. These findings prompted the need for safer drinking water treatment practices and fueled the creation of more advanced drinking water treatment syst ems. Today, a large amount of complex drinking water treatment plants that provide superior drinking water to their customers exist throughout the world ; however, this is not so in all regions. Underdeveloped nations that lack the resources and finances of their urbanized counterparts are deprived of this exceptional drinking water quality. This disparity has brought about the creation and application of a number p oint of use (POU) drinking water treatment devices in several third world countries. Even though these systems are not completely comparable to the types of water treatment available in urbanized nations, they are helping close the gap on the 1.1 billion p eople who do not have access to safe drinking water 2 throughout the world. Point of use treatment has proven itself to be highly effective in regions where only primitive techniques, such as boiling, were the only means of treating water. The initial succ ess of POU treatment has in turn sparked new developments in this area which are constantly being implemented in underdeveloped communities around the world. The impact of these efforts, however, is at times slighted by the lack of community

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11 acceptance or financial status of the target customers. With financial strain being one of the driving forces behind the lack of use, it has become more important now more than ever to find a more cost efficient way to treat water for people with limited resources. The use of activated carbon has proven to be very effective in previous years but, with the push for a more sustainable approach to water treatment, new tactics are on the rise. One of the most noteworthy projects carried out throughout the past decade has be en conducted by Dr. Greg Allgood. He, in collaboration wi th Procter & Gamble (P&G ), PUR and numerous other partners, helped to start a global initiative known 3 The CSDW is a program that strives to reduce sickness and death as a result of consuming contaminated drinking water. The program has provided aid to more than 40 developing countries to date. Although this organization is not the first to undertake such a great endeavor, they have a new and i nnovative approach to an ever present problem. The only purification system needed for their treatment process is the powdered contents of a packet similar to the packet used to make Kool Aid This invention is known as the PUR packet. The PUR through P&G The powdered mixture in these packets removes dirt, cysts, bacteria and viruses from contaminated water and turns it into safe, clean drinking water. Just one of these little packets can disinfect 10 liters of water which could potentially supply one person with 5 days worth of clean drinking water. The entire process takes only 30 minutes and requires fairly simple tools. To produce the clean water you need 2 containers that can hold 2.5 gallons of water, a PUR packet, a stirring spoon (or similar

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12 apparatus) and a 100% cotton cloth filter 4 One thing that makes the packet such a great resource is that it is so compact. Unlike sending cases of bottled water or building an ent ire treatment system, the packets are fairly inexpensive to ship and put in place. Their size makes it easy to send several at one time which is a great stride in helping cause has already donated over 2 billio n liters of clean water to several underdeveloped nations and has pledged to donate more than 4 billion liters by the year 2012. The PUR packet is also recommended for use during recreational activities such as camping, hiking, backpacking, fishing, and hunting. With the high use of pesticides such as Atrazine throughout the United States, there is always a growing concern of these pollutants leaching into water systems. This work focuses on the interaction of the PUR packet in the presence of increased organic matter and trace contaminants. As steps to analyze the effectiveness of the PUR packet in this environment, the following hypotheses and objective s were identified. Hypotheses: The PUR packet will create disinfection byproducts from the water pu rification procedure The PUR therefore, it was expected that the product would not remove Atrazine. Objectives: To test the PUR packet for color and turbidity removal To determine if d isinfection byproducts are formed To determine whether trace contaminants, such as Atrazine, are removed To determine if the addition of an easily produced activated carbon could aid in water purification

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13 CHAPTER 2 LITERATURE REVIEW 2.1 PUR Packets The PU R packet is the brain child of Dr. Greg Allgood and Procter & Gamble (P&G creation of this powder treatment source. Several undeveloped nations have to deal with waterbor ne illnesses that leave their people vulnerable to sickness and even death. Tainted water also makes life extremely difficult for individuals with compromised immune systems who may be suffering from diseases such as HIV/AIDS. Waterborne illnesses have bee n a problem for centuries, even in some of the most developed regions. The increased risk of such diseases was taking such a large toll on people worldwide that in the early 1900s people finally decided to figure out a way to disinfect their water. In 1908, chlorine was used to disinfect a U.S. municipal water supply in Jersey City, NJ 5 By the 1920s and 1930s, chlorine stopped most epidemics due to waterborne disease and chlorination seemed like the way to g o for appropriate disinfection. However, peo ple in developing nations that did not have access to such treatment facilities were still consuming unhealthy, contaminated drinking water. The cholera outbreak of 1991 in Peru is ultimately what led P&G to develop their own drinking water treatment proc ess To help combat cholera in Latin America, the Center for Disease Control (CDC) provided people with chlorine bleach solutions to treat contaminated drinking water throughout the region. This was administered in specially designed bottles that allowed p eople to effectively treat one jerry can of water using the

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14 powerful disinfectant and it effectively eliminates viruses and bacteria, it still left the water looking dirt y due to the presence of suspended particles. With P&G being the main manufacturer of chlorine bleach, the company decided to take on the challenge of improving this treatment process. This new process would remove suspended solids in addition to disinfec ting the water. Thus, the PUR packet was born. 2.1.2 Coagulation and Flocculation The main additions P&G made to the already effective process of chlorine disinfection were coagulation, flocculation and filtration. The coagulant of choice for their proce ss is iron sulfate (ferric iron), of which the packet contains 352 mg. The total list of packet ingredients includes ferric sulfate, bentonite, sodium carbonate, chitosan, polyacrylamide, potassium permanganate, and calcium hypochlorite 6 One study by Rell er et al ( 2003 ) showed that the use of these ingredients was favored over the use of chlorine bleach alone for disinfection. The study showed a 29% decrease in the incidence of diarrhea of a few rural households in Guatemala. This study also showed that pa rticipants preferred this type of treatment over traditional chlorine disinfection alone because it removed some of the sediments that disinfection left behind. Coagulation and flocculation is one of the most effective and widely used treatment processes used today and its use dates back several centuries. The Ancient Egyptians are credited with the first use of these two methods. They developed their own techniques which are considered to be the first clarifying devices known to man The ir system was pict ured in the tombs of both Amenophis II and Rameses II, inscribed in the 15 th and 13 th century BC, respectively 7 Through this process the Egyptians are noted as the first to discover coagulation. They added alum to water in order to remove suspended solids a method still in use today.

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15 After the Renaissance period brought an end to scientific discovery, the world entered what is known as the Dark Ages. Water treatment was fairly stagnant and the same methods were being used until the brilliant discoveries o f three Dutchmen. In 1590, Hans Janssen and his sons, Zacharias and Hans, saw that objects could be magnified by putting a piece of concave glass in a tube 8 This became known as a compound microscope. The microscope brought light to a dimension of life t hat had never been seen before. Their invention was used for almost a century until it was perfected by a Dutch naturalist. In the late 16 th Century, Antony van Leeuwenhoek created what is known as the first microscope 9 Surprisingly, one of the main objec ts he chose to study was water. He was the first to see organisms living in water and brought these invisible impurities to the attention of others. He was able to achieve magnifications up to 270 times greater than the original object. After reporting his findings to the Royal Society, they were published throughout Europe and sparked the next evolution of drinking water treatmen t. After the discovery of microorganisms, a widespread implementation of filtration systems took place. During the 1700s, filtrat ion was recognized as an effective way of removing microscopic impurities. In 1703, Parisian scientist Phillipe La Hire brought forth the first idea of point of use drinking water treatment for all 10 He proposed a plan that would provide sand filters and rain water cisterns in every household. Later in 1749, a Frenchmen, Joseph Amy, was issued the first patent for a water filter 11 His device, comprised of both sponges and sand filters, became the first standard for filtration systems. During this period t he first patent was also issued for a household filter designed by a potter, Johanna Hempel. Although filtration became known as the most

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16 effective way of removing particles from water, the degree of its effectiveness was still not understood. It would tak e more scientific exploration to shed light on how clean drinking water was becoming. All of these advancements are what helped fuel a need for better contaminant removal practices. The microscope led scientists to physically examine the pathogens in the w ater that were making people sick and thus helped them find a way to tackle these impurities. After years of testing and technological growth, it was determined that the combined processes of coagulation, flocculation and filtration were some of the best w ays to combat these microscopic threats. Coagulation is the process of adding a chemical to water to stabilize the charges of suspended solids and particulate matter present in the source. With most particles in contaminated water being negatively charged, ferric iron, which has a 3+ charge, is a good coagulant. One reason an iron based coagulant may have been selected over an aluminum one is because the ferric flocs are a lot heavier than alum flocs causing them sink. For the PUR a mount of contaminants that are actually being removed from the water. Coagulation immediately promotes the formation of microflocs which in turn grow throughout the mixing process. The rapid mixing during coagulation is what stimulates particle collision t hus helping them to stick together and grow. Flocculation is what allows these microflocs to agglomerate into large flocs which makes it easier to remove contaminants. Flocculation is what occurs during the settling phase after rapid mixing. There is still a certain amount of gentle mixing that takes place during the settling phase which helps entrap any remaining contaminants left in solution. After creating the floc, it

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17 is necessary to separate it from the solution. The PUR packet process accomplishes th is through a method that was used quite some time ago. In ancient times, the methods of coagulation and flocculation were the only ones upheld until a well k nown Greek physician linked water attributes to human health. Around 400 BC, Hippocrates emphasized the importance of filtering water and its direct 12 filtration device that would remove solids such as sediment, something that was not focused on during that period of t ime. This invention later became known as the through to remove particles. This was used in addition to boiling to provide advanced contaminant removal. With coagulation, flocculation and cloth filtration having such a long history in drinking water treatment, it is no surprise that they are the main components of the PUR First the powder substance is added to 10 liters of contaminated wat er. The mix is then stirred for five minutes and allowed to settle for five minutes. Small flocs will immediately begin to form during the mixing process resulting in a large floc at the end of the settling process. A 100% cotton cloth is then placed over a second container which can also hold 10 liters of water and the newly treated water is filtered into an empty container that can also hold 10 liters of water. The floc is trapped on top of the cloth and is then disposed of in a latrine or on the ground. This process can be seen in Figure 1. The combination of these processes has effectively provided the removal of dirt, cysts, and pollutants and effectively kills viruses and bacteria.

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18 Figure 2 1. PUR Purifier of Water Directions for Use (Source: http:/ /www.purpurifierofwater.com/downloads/pur_packet_instructions.pdf ) 2.1.3 Current Application The PUR packets use throughout developed nations has been very well documented. Since its first distribution in 2004, Dr. Allgood has traveled all over the world helping combat issues such as diarrhea, cholera, and other waterborne illness through use of the PUR over 2 billion liters of clean water to people in underdeveloped nations and the group is see mingly on track to fulfill their goal of providing 4 billion liters of water to these regions by the year 2012. A six month pilot project in Northeastern Uganda 13 put the PUR packets to work with highly favorable results. This project selected 1500 people to participate in the implementation of household water purification and sanitation systems. The coupled sanitation system was necessary because poor drinking water quality is often the result of improper sanitation conditions in these regions. Similar pl ans have been used in others parts of the third world including Pakistan 14 In several incidences good hygiene practices often predict the ultimate success of a drinking water treatment plan. The end

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19 result of this study was the significant removal of E co li in several sample water sources. With 2 million deaths of children being attributed to waterborne illnesses or diseases, it only makes sense to try and educate the children. This is exactly what P&G did in a study conducted in the Democratic Republic o f Congo 15 This is a region where nearly 80% of the population does not have potable drinking water. Delivering the information directly to the children was extremely beneficial because they are often times the water carriers of the family. After educating the children about the PUR packets, t hey brought that knowledge home By the end of the study 95% of households knew how to sanitize their water and 91% were washing their hands before and after meals. This caused a drastic decrease in the incidence of diarrhea in households Similar studies have been conducted in Liberia 16 Kenya 17 and Guatemala (Reller et al 2003) In the wake of the devastation that hit Haiti in 2010 the PUR packets have also shown one of their alternative purposes. In addition to providing clean water to developing nations, the packets are also used for relief efforts after natural disasters. As seen with the earthquake in Haiti, the few clean sources of water that the nation did possess were completely obliterated. P&G and PUR immediately sprung into action delivering 6 million packets to the country which provide d a 3 mon th supply of clean water for 34 0 ,000 people 18 The device was used for a similar situation in Honduras back in 2008 19 With the help of Catholic Relief Services, PUR packets were distributed to families without access to safe drinking water after a Tropic al Depression struck the region in October of that year.

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20 Furthermore, the supplier recommends that this product also be used for recreational purposes such as camping, hiking, hunting, and backpacking. However, there has been very little research done to t est the effectiveness of the product in these environments. 2.2 Activated Carbon The use of Activated Carbon (AC) for drinking water treatment dates all the way back to ancient civilizations. One of the earliest known recordings of drinking water treatment dates back to 4000 BC 20 This was the first document ation of taste and odor control, two things that AC is often used to treat today. These ancient Greek and Sanskrit writings suggested filtering water through charcoal, exposing it to sunlight, boiling, a nd straining 21 Samhita sited impure water as the source of several medical concerns 22 This document also suggested two new treatment methods: dipping a heated rod into the water or filtering it thro ugh coarse sand or gravel. The activated carbon has also made a name for itself in the medical industry. Patients who are victims of chemical poisoning from household products are treated with AC because of its ability to absorb toxins. It has also been no ted that AC was used in 1500 BC to combat odors from gangrene wounds. Activated Carbon has also made strides in the air purification industry and has been in use there for quite some time as well. The exposure of soldiers to poisonous gases during World Wa r 1 led to the mass production of respirators with AC filters. Carbon filters are also found in several home and office air purifiers. 2.2.1 Manufacture Carbon can be activated through physical or chemical processes. Physical reactivation can occur in one of two ways. The first involves

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21 carbonization in which is the material is pyrolyzed or heated in the absence of oxygen. The second is exposing the carbonaceous material to an oxidizing atmosphere such as steam. These two methods ca n also be combined to im prove pore size and surface area. Chemical activation requires impregnating the material with a chemical and then carbonizing it at lower temperatures. Both processes have been proven to be effective s. The pore sizes of activated carbon are measured in angstroms ( ). One angstrom is equal to 1 x 10 10 m which is the e quivalent to a grain of sugar. AC pore structures are characterized with three size distinctions: Micropores (0 20 ) Mesopores (20 500 ), and Macropores (>500 ). AC surface areas are normally in excess of 500 m 2 for 1 gram of carbon. One technique for creating AC in ancient times was by using charcoal kilns. Such devices are still in use today throughout the developing world. A project in Indonesia studied the effective yield of carbon between six types of charcoal kilns used in the region 23 Similar devices are used throughout Asia, Africa, and South America. These kilns are normally made of soil, clay, brick, or stone and are construct ed by hand. The systems in urbanized nations are more advanced but achieve the same goal. The activation process normally takes place in either a rotary kiln, shaft kiln (multiple hearth furnace), or a fluidized bed 24 These devices allow for better contro l of temperature which directly effects pore structure development. Achieving a desired pore size and surface area can be accomplished through both of the physical an d chemical processes discussed. Activated carbon can be produced from a number of material s. A lot of these source materials come from the food and forestry industries. These are businesses that

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22 tend to produce a fair amount of waste and have now found an environmentally friendly way to dispose of it. There are several studies that show how wa ste from farming processes have been used to created activated carbon. Some of these studies include examining sawdust 25 rise husks 26, 27 nutshells 28, 29 pomegranate seeds 30 and sago waste 31 2.3 Atrazine Atrazine is a well known herbicide in the wor ld of agriculture and lawn care. This fact is proven by the 74 80 million pounds of Atrazine that are used each year in the United States 32 alone. Despite its ban for use in the European Union in 2003 33 it is still one of the most widely used herbicides i n the world. Atrazine is mainly used in agriculture and more specifically on corn crops. It is credited with being capable of eliminating or preventing the growth of both broadleaf and grassy weeds, plants thought to be a nuisance in this industry. This pr oduct is also used for the cultivation sorghum, guava, hay, macadamia nuts, pasture grasses, and winter wheat 34 On the non agricultural side, Atrazine is also used for golf courses, landscape maintenance, forests, and recreational areas normally in Florid a and other Southeastern states. The highest use of Atrazine, however, is in the Midweste rn region of the United States. Once Atrazine is applied for these purposes it is very slow to break down in the environment. This is largely due to its triazine struc ture which can be seen below in Figure 2. The large size of this compound is what prevents it from easily breaking down. The triazine structure is one that promotes Hydrogen doning and accepting because of the presence of several Hydrogen and Nitrogen mole cules. The duality of the compound is what makes it dissolve readily in water and have a low tendency to adhere to soil particles. This ultimately results in a large contamination of streams, rivers, lakes, and

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23 drinking water supplies as a whole. Contamina tion levels normally spike in the spring when large amounts of the herbicide are applied to agricultural crops. Two sources, rain runoff and ground infiltration, allow the product to enter waterways and groundwater supplies. Once Atrazine is in the environ ment it can persist for long per iods of time. Figure 2 2. Chemical Composition of Atrazine Although drinking water is one of the main sources of exposure to Atrazine, there are also a few others that are no t commonly recognized. Children playing on lawns or in soil that have recently been sprayed are at risk for direct exposure. It is also important to note that Atrazine can persist in soil for an extended period so a child playing on a lawn that was treated months ago is still at risk. During applic ation there is a certain amount of drift that may occur. The drift of Atrazine causes it to become airborne and it has been found in dust particles at low levels in homes throughout the Midwest 35, 36, 37 and in California 38 These studies also found that p eople residing in households with farmers or individuals who apply the pesticide are at an extremely high risk because the contaminant may be in the clothes or shoes of that person when they reenter the home. Atrazine residues have also been detected in fo od samples 39, 40 but these levels were aximum contaminant level (MCL).

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24 2.3.1 Health e ffects One of the things that makes Atrazine a contaminant of concern are the number of adverse health effects associated with it. One study by Ochoa Acu a et al in 2009 41 found that exposure to Atrazine during pregnancy produced a significant increase in the amount of babies born small for gestational age. This means that the birth weight, length, or head circumference of the child was below the 10 th p ercentile for a specific gestational age. In 2004, occupational exposure to Atrazine was linked to causing increased risk of infertility and adverse pregnancy outcomes such as miscarriages, preterm delivery and birth defects 42 Atrazine has also been foun d to effect infant mortality and morbidity rates. There are also several health risks for adults exposed to Atrazine. In 2004, Swan found that Atrazine exposure contributed to reduced sperm quality of men in Missouri. Another study also linked the pesticid e to diminished sperm motility 43 Atrazine has also been shown to potentially affect the heart, brain, and lungs 44, 45 There is still a large debate as to whether or not Atrazine can be linked to any forms of cancer. The EPA reports that there is no corr elation but several epidemiological studies are now exploring the possible link to the agricultural uses of Atrazine to various types of cancer. It has however been documented that the endocrine disrupting properties of Atrazine have shown to effect fish amphibians, and reptiles 46 It is in turn feared that this herbicide is a risk factor for reproductive cance rs in humans and other mammals.

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25 CHAPTER 3 MATERIALS AND METHODS 3.1 PUR Packets The PUR packets were obtained from an online retailer (Walmart ) which supplies the treatment kit. These packets were used to treat raw water from Lake Alice on the University of Florida campus. Lake Alice was chosen for the ease of access to the water source and the amount of natural organic matter (NOM) though to b e present in the water. To increase the quantity of experiments that could be performed using a single PUR packet, the powder was split into tenths, thus allowing for 10 experiments to be performed from each packet. Therefore, 0.4 g of PUR powder was use d to treat 1 liter of water in every experiment. Although there was no research found about the scalability of the PUR packet, the powder was thoroughly mixed to increase the potential of each component making it into the scaled treatment process. However, it will be helpful for future experiments to determine the concentrations of each component to ensure each is present in the modified treatment process. The water treated in these experiments was only used for analysis. None of it was consumed after treat ment. The directions for use of the PUR packet were modified for this reason. The edited directions for use are as follows: 1. Mix Measure out 0.4 grams of PUR powder. Add the powder to a clean beaker holding 1 liter of source water. 2. Stir Stir the powder vi gorously in the water for 5 minutes using a magnetic stir rod and stir plate Be sure a vortex is created when stirring. Then, let the water stand for 5 minutes or until it becomes clear. 3. Filter

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26 Once the water looks clear, and the floc is at the bottom of the beaker filter the water through a vacuum filter in to a clean storage container The filter must be a clean, 0.4 5 um membrane filter without holes, that prevents the floc from passing through. The floc will be left behind in the bottom o f the container and in the membrane filter. Discard the floc from the water treatment process in a trash receptacle All of the experiments were carried out in progression; meaning that duplicate experiments were not performed for this analysis. This was becau se after the PUR packet proved its effectiveness at one level, the packet was then tested at the next level. After the water was treated, samples were sent to Engineering Performance Solutions (EPS Gainesville, Florida) for water quality analysis. More detailed pictures of the treatment process can be seen in Appendix A: PUR Packet Treatment Photos. The first set of experiments was designed to test the PUR remove color and turbidity from the water and also examine whether or not th e packet produced disinfection byproducts (DBPs). This test was also designed to check for Atrazine in the source water from Lake Alice. The water was treated using the modified directions given above. The mixing was done on a magnetic stir plate at a medi um setting. After vacuum filtration, 200 mL samples of source water and treated water was sent to EPS for analysis. 3.2 Humic Acid and Toluene Studies The purpose of these tests was to see how the PUR packet would behave in the presence of in creased orga nic matter and another organic substance. Instead of adding viruses and bacteria to the raw water, Toluene was selected as the additional contaminant. Actual viruses and bacteria such as Hepatitis A and Coliform were not added because they are very dangero us to handle. Toluene was used to simulate the

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27 increased competitive adsorption environment that this packet is normally used to treat. Just like viruses and bacteria, Toluene is able to bind to organic material in aqeuos environments, increasing its longe vity in these systems. These experiments were also still testing the hypothesis of the PUR packet producing DBPs. The total organic carbon (TOC) level of Lake Alice was initially 8 mg/L. It was desired to increase this concentration to 10, 15, and 20 mg/ L in three different beakers. This was done by adding 2, 7, and 12 mg of Humic Acid to the beakers, respectively. The Humic Acid was obtained from the International Humic Substance Society (St. Paul, Minnesota). The type of Humic Acid used was Suwannee Riv er Humic Acid Standard II. Then, a 10 uL dose of Toluene was added to each beaker. The beakers were then thoroughly mixed by hand with a stirring apparatus and a 200 mL sample was extracted from each for water quality analysis. The substance in each beaker then underwent the modified treatment process. Three new sample mixtures were created using the same contaminants and dosages as listed above. These mixtures were allowed to undergo treatment for 60 minutes instead of the recommended 5 minutes. This was d one to see if extended exposure to the PUR powder would create more DBPs. They were then vacuum filtered and 200 mL samples from each were extracted. All nine samples collected from this process were then sent to EPS for water quality analysis. 3.3 Atraz ine Studies The experiments conducted with Atrazine followed a similar pattern to the Humic Acid and Toluene experiments. Just as before, there were three beakers with 1 liter of water, 10 uL of Toluene and 2,7, or 12 mg of Humic Acid Each beaker was then spiked with 20 uL of Atrazine. With no Atrazine being detected in the raw source water from the

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28 first set of experiments, it was necessary to analyze whether or not the PUR packet could actually remove this substance. The Atrazine w as obtained from SPEX CentriPrep (Metuchen, NJ) through Fisher Scientific Company. A 200 mL aliquot was removed from each beaker and all beakers were then treated according to the modified directions. A 200 mL sample was then obtained from each of the trea ted beakers and all 6 samples were sent to EPS for water quality analysis. 3.4 Activated Carbon Production The activated carbon used in these experiments was created from sawdust The first step of this process was nitrogen pyrolysis. The sawdust was char red in batches of 1.5 grams per sample. This process took place in a furnace set to a temperature of 450 o C with a Nitrogen flowrate of 30 mL/min for 15 minutes. These pyrolyzed samples were then compiled into one large batch. The furnace temperature was th en increased to 700 o C for steam activation. The newly pyrolyzed sawdust was activated in four batches each containing 1.5 g of material. Two samples were activated at a steam flowrate of 0.2 mL/min for 15 and 30 minutes. A second set of samples was activat ed at a steam flowrate of 0.5 mL/min for 15 and 30 minutes. A small portion of each sample (0.2 g) was analyzed using the Quantachrome Instruments NOVA 2200e surface area analyzer. Three of these activated carbons were selected for use in the next set of e xperiments. 3.5 PUR and Activated Carbon Treatment For this process, 1 liter of water was added to three 1500 mL beakers. There were then 3 mg of Humic Acid added to each beaker. They were all spiked with 10 uL of Toluene and 20 uL of Atrazine. The first beaker was treated with activated carbon first and then the PUR powder. The second beaker was treated with activated carbon and

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29 the PUR powder at the same time. The third beaker was treated with the PUR powder first and then activated carbon. In every c ase the activated carbon was used in accordance with the modified directions used for the PUR packet. This process was completed a total of six times using 20 mg and 100 mg doses of each carbon. Each mixture was vacuum filtered in the final stage and eigh teen 200 mL samples were sent to EPS for analysis. 3.6 Total Organic Carbon There were several needs for this type of testing. It was thought that TOC played a fairly vital role in the effectiveness of the PUR packet. Therefore, several TOC tests were co nducted at various stages in the experimentation process. It was first necessary to determine the amount of TOC reduction the PUR packet and the activated carbon were capable of. This was done by testing the TOC of the water during the PUR and activated carbon treatment experiments. Testing was also necessary to determine if any of the treatment agents in the PUR packet were creating organic carbon. All TOC analysis was carried out on a Tekmar Dohrmann Apollo 9000 Combustion TOC/TN analyzer. This machine required a 40 mL vial from each treated sample which was extracted after the vacuum filtration.

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30 CHAPTER 4 RESULTS AND DISCUSSI ON 4.1 Raw Water Tests The first set of experiments was used to determine the quality of raw water obtained from Lake Alice and the ability of the PUR packet to treat this water. The water quality parameters examined were color, turbidity, Atrazine, and disinfection byproducts (expressed as TTHMs). The results for this test can be seen below in Table 4 represents the water sample taken after treating Lake Alice water with the PUR powder. Table 4 1. Raw water test r esults Specification Raw Clean Color (Pt Co) 22 3 Turbidity (FAU) 70 24 Atrazine ( ug/L) ND ND TTHM (ug/L) ND 2.09 *5 minutes of contact time ND = Below detection limit of 0.5 ug/L for Atrazine ND = Below detection limit of 0.5 ug/L for TTHMs From the table it can be seen that the PUR packet had removal in both color and turbidity. W ith no Atrazine being detected in the source water it is reasonable for there to be none detected in the treated water. Although some disinfection byproducts were created during the cleaning process, the detected amount of 2.09 ug/L is still approximately ug/L. 4.2 Humic Acid and Toluene Studies After seeing the PUR effectiveness in the presence of increased organic matter and another contaminant.

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31 Each beaker was spiked with Humic Acid to increase the TOC concentration and Toluene to introduce an additional pol lutant. Once again the PUR packet combated color and turbidity well, even with the excess organic matter present. The packet was also effective in removing Toluene. Again, a small amount of DBPs were formed in the process but they still were not significa nt. The results of this are displayed in Table 4 2. The parameters examined in these tests were color, turbidity, Toluene, and TTHMs. Tab le 4 2. Humic Acid and Toluene water t est Sample ID Color (Pt Co) Turbidity (FAU) Toluene (ug/L) TTHM (ug/L) Raw 10 mg/L 146 87 2830 ND Raw 15 mg/L 143 46 525 0.9 Raw 20 mg/L 231 22 513 0.9 Clean 10 mg/L 5 min 7 0 1329 1.4 Clean 10 mg/L 60 min 25 0 61 1.2 Clean 15 mg/L 5 min 14 0 289 2.1 Clean 15 mg/L 60 min 30 1 15 1.5 Clean 20 mg/L 5 min 24 0 64 1.6 Clean 20 mg/L 60 min 21 0 2 ND ND = Below detection limit of 0.5 ug/L for Toluene and TTHMs The Raw 10, 15 and 20 mg/L represent the three different beakers that were spiked with 2, 7, and 12 mg of Humic Acid, respectively. Each of these samples was e Raw 10 mg/L beaker with the PUR powder. The endings notations of 5 and 60 minutes denote how long each beaker was allowed to mix with the PUR powder. The removal of color, turbidity, and Toluene can be seen in Table 4 3. The percent removal of Toluene was almost 100% after 60 minutes of treatment for all three

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32 samples (i.e., when starting with 10, 15, and 20 mg/L of TOC). Turbidity removal was 100% for all samples except for one which was relatively close at 97% removal. Table 4 3. Percent r emov al from Humic Acid and Toluene t est Sample ID Color (%) Turbidity (%) Toluene (%) Clean 10 mg/L 5 min 95 100 53 Clean 10 mg/L 60 min 83 100 98 Clean 15 mg/L 5 min 90 100 45 Clean 15 mg/L 60 min 79 97 97 Clean 20 mg/L 5 min 90 100 88 Clean 20 mg/L 60 min 91 100 100 4.3 Atrazine Studies During the Atrazine tests, color and turbidity were still removed but an interesting phenomenon occurred when Toluene and Atrazine were both present in the water. In the presence of Atrazine the removal efficiency of Tol uene was greatly diminished. The removal of Atrazine itself was almost nonexistent (Table 4 4). The percent removal (Table 4 5) shows how little of both substances were removed in comparison to Table 4 3. Table 4 4. Hum ic Acid, Toluene, and Atrazine t est Sample ID Color (Pt Co) Turbidity (FAU) Toluene (ug/L) Atrazine (ug/L) Raw 10 mg/L 56 4 2145 40 Raw 15 mg/L 134 6 494 22 Raw 20 mg/L 180 5 476 14 Clean 10 mg/L, 5 min 16 2 2020 34 Clean 15 mg/L, 5 min 8 0 322 24 Clean 20 mg/L, 5 min 7 0 307 14 The sample IDs of Raw 10, 15, and 20 mg/L still represent the three different beakers that were spiked with 2, 7, and 12 mg of Humic Acid, respectively. Each beaker was also spiked with 10 uL of Toluene and 20 uL of Atrazine. The samples labeled

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33 clean ar e samples of treated water from that corresponding beaker (i.e. Clean 15 mg/L was treated from Raw 15 mg/L). T able 4 5. Toluene and Atrazine percent r emoval Sample ID Color (%) Turbidity (%) Toluene (%) Atrazine (%) Clean 10 mg/L, 5 min 71 50 5.9 14 Clean 15 mg/L, 5 min 94 100 35 8.8 Clean 20 mg/L, 5 min 96 100 36 2.1 Diminished removal of all four parameters was seen in this set of experiments. This could possibly be related to the number of contaminants present in the water. Toluene, color, and turbidity were all removed quite well before Atrazine was added to the sys tem. The large chemical structure of Atrazine could have al so contributed to its lack of adsorption and also the lack of ad sorption of the other two contaminants. A more in depth depiction of the Humic Acid and Toluene structures can be seen in Appendix B: Chemical Structures. After discovering this lack of removal, it was necessary to examine the possible effect activated carbon might have on the mixture. 4.4 Activated Carbon Creation Only 1.5 g of saw dust was used during Nitrogen pyrolysis and steam act ivation to ensure all of the material had the ability to fully react. During pyrolysis there was at least 40% mass loss in every sample (Table 4 6). This value of mass loss is typical when using this process because non carbonaceous material is burned off. Table 4 6. Nitrogen p yrolysis of s awdust Sample ID Mass Before (g) Mass After (g) Mass Loss (%) 1 1.5 0.889 40.7 2 1.5 0.846 43.6 3 1.5 0.856 42.9 4 1.5 0.864 42.4 5 1.5 0.848 43.5 6 1.5 0.877 41.6 7 1.5 0.886 41.0 8 1.5 0.896 40.2 9 1.5 0.875 41.7

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34 During steam activation each sample experienced a mass loss greater than 50%, which is also typical for this process (Table 4 7). It was expected that the mass loss would be greater from 15 minute to 30 minute activation times but it was discovered t hat the increase in mass loss was very small. Using 0.2 mL/min of steam the mass loss increased from 53.7% to 54.2% (a minor difference of 0.5%). Using 0.5 mL/min of steam the mass loss increased from 55.0% to 55.9% (a difference of 0.9%). Table 4 7. Steam Activation of Pyrolyzed Sawdust Sample ID Mass Before (g) Mass After (g) Mass Loss (%) Steam Flowrate (mL/min) Time (min) # 1 1.5 0.687 53.7 0.2 30 # 2 1.5 0.694 54.2 0.2 15 # 3 1.5 0.661 55.9 0.5 30 # 4 1.5 0.675 55.0 0.5 15 Analyzing each sample on the NOVA 2200e gave a more in depth look at the carbon capacity and pore size (Table 4 8). The maximum surface area achieved was 416 m 2 /g and the minimum was 168 m 2 /g. The pore volume followed a similar trend with the largest pore volume residing in the 416 m 2 /g sample and the smallest pore volume residing in the 168 m 2 /g sample. The average pore size however had a different result. The pore size for Carbon #1, #3, and #4 were all around 9 while the pore size for Carbon #2 (which had the smallest surface area) was 12.8 Table 4 8. Activated Carbon particle a nalysis Sample ID Sample Mass (g) Surface Area (m 2 /g) Pore Size () Pore Volume (cm 3 /g) #1* 0.183 327 9.2 0.15 #2* 0.194 168 12.8 0.11 #3 0.181 398 9.0 0.18 #4 0.167 416 9.1 0.19 Carbon was selected for final treatment process

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35 4.5 PUR and Activated Carbon Treatment Results Color and turbidity were still effectively taken care of in these experiments. With the addition of activated carbon, it was expected that there would be increased removal of both Atrazine and Toluene. Its presence, however, was almost unrecognizable in th e results. The two contaminants added to the water were still removed in relatively small percentages (Tables 4 9 through 4 14). Though these percentages were small, it was apparent that use of activated carbon in conjunction with the PUR packet would be a possible solution to combating these contaminants. sample was first treated with activated carbon and then the PUR powder. Sample IDs powder at the same time. powder and then AC. The endings of 20 mg and 100 mg represent the dose of carbon used to treat that sample. Table 4 9. Carbon #1 treatment r esults Sample ID Color (Pt Co) Turbidity (FAU) Toluene (ug/L) Atrazine (ug/L) Raw Spiked 109 32 308 37 AC Before 20 mg 6 0 256 26 AC During 20 mg 8 0 261 33 AC After 20 mg 8 0 88 28 AC Before 100 mg 10 2 19 16 AC During 100 mg 10 0 285 24 AC After 100 mg 15 1 171 27

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36 Table 4 10. Percent r emoval Carbon #1 Sample ID Toluene (%) Atrazine (%) AC Before 20 mg 17 30 AC During 20 mg 15 10 AC After 20 mg 72 25 AC Before 100 mg 94 57 AC During 100 mg 8 34 AC After 100 mg 44 28 Table 4 11. Carbon #2 treatment r esults Sample ID Color (Pt Co) Turbidity (FAU) Toluene (ug/L) Atrazine (ug/L) Raw Spiked 109 32 308 37 AC Before 20 mg 10 0 256 26 AC During 20 mg 12 0 278 32 AC After 20 mg 11 0 228 21 AC Before 100 mg 10 0 171 29 AC During 100 mg 25 2 274 32 AC After 100 mg 15 0 244 34 Table 4 12. Percent r emoval Carbon #2 Sample ID Toluene (%) Atrazine (%) AC Before 20 mg 17 30 AC During 20 mg 10 15 AC After 20 mg 26 43 AC Before 100 mg 44 22 AC During 100 mg 11 14 AC After 100 mg 21 8 Table 4 13. Carbon #4 treatment r esults Sample ID Color (Pt Co) Turbidity (FAU) Toluene (ug/L) Atrazine (ug/L) Raw Spiked 109 32 308 37 AC Before 20 mg 11 0 260 33 AC During 20 mg 10 9 101 28 AC After 20 mg 12 1 308 30 AC Before 100 mg 13 1 177 33 AC During 100 mg 13 1 278 29 AC After 100 mg 13 2 184 31

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37 Table 4 14. Percent r emoval Carbon #4 Sample ID Toluene (%) Atrazine (%) AC Before 20 mg 16 15 AC During 20 mg 67 25 AC After 20 mg 0 18 AC Before 100 mg 43 12 AC During 100 mg 10 23 AC After 100 mg 40 18 completely removed from solution before using the second method (i.e. activated carbon was completely filtered out before using PUR PUR samples). From these results it was observed that the best removal of Toluene when using a 100 mg dose was found by using AC before the PUR packet. With the 20 mg dose Carbon #1 and #2 performed better by using carbons after the PUR packet while Carbon #4 performed well in conjunction with the PUR packet. The best removal of Atrazine using either a 20 m g or 100 mg dose was using AC before the PUR packet in Carbon #1 and #2. The best removal of this contaminant using Carbon #4 was found using it during the PUR treatment process. It is duly noted that none of these carbons were able to provide adequate r emoval to meet EPA standard for Atrazine of 3 ug/L but it is a good indicator that a larger surface area, more porous carbon may be able to eliminate it from the system. 4.6 Total Organic Carbon Studies The lack of removal of Toluene and Atrazine after add ing activated carbon to the experiment prompted a desire to investigate TOC levels in the water. The observed

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38 concentrat ion could explain the lack of ad sorption which could possibly be linked to a potentially more competitive environment due to the increas ed amount of contaminants. High TOC values would also indicate a possible lack of removal of Humic Acid as well. TOC was first examined from the PUR and AC tests. The three carbons presented varied results. Carbon #1 (Figure 4 1) exhibited better TOC remo val with the 100 mg dose. The removal before, during, and after with this carbon was consistently lower than the 20 mg dose. This was expected to be the trend in all three carbons but the other two had different outcomes. Carbon #2 (Figure 4 2) showed bett er removal with the 20 mg dose. This may be attributed to the small surface area of 168 m 2 /g of the material. The carbon may have been dealing with too many competing particles, preventing it from effectively absorbing organic matter as it did in Carbon #1 Figure 4 1. TOC c oncentration for Carbon #1 Carbon #4 (Figure 4 3) had very little difference in TOC concentration before, during, or after the PUR treatment process. This was the most surprising result because this carbon possessed the largest surface area (416 m 2 /g) and the highest pore volume (0.19 cm 3 /g) of all three ACs. 0.0 5.0 10.0 15.0 20.0 During Before After Concentration (mg/L) Sample ID Carbon #1, 20 mg Carbon #1, 100 mg

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39 Figure 4 2. TOC c oncentration for Carbon #2 Figure 4 3. TOC c oncentration for Carbon #4 With most of the TOC values being above the assumed starting concentration of 8 mg/L, it was necessary to investigate the possible effect the PUR packet might have had on the water. In Figure 4 4 and Table 4 15, the effect of t he PUR packet on TOC concentration was examined. 0.0 5.0 10.0 15.0 20.0 25.0 During Before After Concentration (mg/L) Sample ID Carbon #2, 20 mg Carbon #2, 100 mg 0.0 5.0 10.0 15.0 20.0 25.0 During Before After Concentration (mg/L) Sample ID Carbon #4, 20 mg Carbon #4, 100 mg

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40 Figure 4 4. Raw and DI water TOC c oncentration Table 4 15. Raw & DI water TOC c oncentration Sample ID Concentration (mg/L) RAW 1 13 RAW 2 14 RAW 3 7.7 RAW 4 7.7 DI 1 0.37 DI 2 0.40 DI 3 0.64 DI 4 0.60 Raw 1 and 2 were samples from the Lake Alice source water without any additional chemicals. DI 1 and 2 were samples of deionized water. There is an evident decrease in TOC concentration observed in Raw 3 and 4 at 7.70 mg/L and 7.71 mg/L, respectiv ely. There is a slight increase in TOC concentration for DI 3 and 4 but this difference is negligible. The increase can possibly be credited to the coagulant aids present in the PUR concen tration of the Lake Alice source water was around 13 mg/L. This could be due to 0 2 4 6 8 10 12 14 16 RAW 1 RAW 2 RAW 3 RAW 4 DI 1 DI 2 DI 3 DI 4 TOC Conentration (mg/L) Sample ID

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41 the different season in which the water was collected causing a slight change in water quality. Recognizing the PUR packet did not have a significant impact on the TOC levels, the effect of Humic Acid was then evaluated. Four samples were extracted from a beaker of raw water spiked with 3 mg of Humic Acid. The result showed a significant increase in TOC concentration ( Figure 4 5, Table 4 16). The error bars present in Figure 4 5 represent the standard deviation between the samples. The average concentration was observed to be 22.7 mg/L with a maximum of 23.7 mg/L and a minimum of 22.2 mg/L. This was a fairly notable inc rease of approximately 10 mg/L from the previously observed average raw water concentration of 13.5 mg/L. It was assumed that the adding 3 mg of Humic Acid to the system that the TOC concentration would increase by no more than 3 mg/L. Knowing that approxi mately half of the composition of organic matter is carbon, it was expected that only a 1.5 mg/L increase would be observed. Figure 4 5. Raw + Humic Acid TOC c oncentration 0 5 10 15 20 25 30 RAW 1 RAW 2 RAW 3 RAW 4 TOC Concentration (mg/L) Sample ID

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42 From all of these TOC tests it was determined that the PUR packet was in fact decreasing TOC instead of creating it as previously thought. This can be confirmed by comparing the average concentration in the raw water spiked with Humic Acid to the values obtained from treating the contaminated water with PUR and AC (Figure 4 6). All values obtained after treating water were below the spiked concentration of 23 mg/L. Figure 4 6. Raw vs. treated TOC c oncentration 0.0 5.0 10.0 15.0 20.0 25.0 Concentration (mg/L) Sample ID Carbon #1 Carbon #2 Carbon #4 Table 4 16. Raw + Humic TOC c oncentration Sample ID Concentration (mg/L) RAW 1 22.7 RAW 2 23.7 RAW 3 22.4 RAW 4 22.2 23 mg/L

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43 CHAPTER 5 S UMMARY AND CONCLUSIO NS The PUR packet was examined for its potential to create disinfection byproducts and its ability to remove Atrazine from drinking water. Humic Acid and Toluene were also added to the water to analyze the PUR contaminant loadin gs in the water. As suspected, the PUR packet aided in color and turbidity removal from the contaminated water. Testing the water at both its raw and saturated conditions did not yield a significant amount of disinfection byproducts. Although some DBPs we regulated limit. As hypothesized the PUR packet was not effective in removal of Atrazine in the presence of increased contaminants and organic matter. This is likely due to the increased competitio n for adsorption by the other compounds present. Although it is unclear how all of the components of the PUR packet work, it was assumed that with the presence of so many treatment chemicals within the powder it would potentially be more effective in comb ating Atrazine and Toluene. With these results proving that the packet does not perform well in this setting, it suggests a need for more work to be done to investigate the purpose of each component of the PUR powder. It may not be practical to list this product for use during recreational activity if it does not remove likely potential hazards from the water. It was also found that an easily produced activated carbon was not sufficient in aiding the removal of Toluene or Atrazine. This may be due to the short contact time or the very high level of TOC in the water. It is known that commercially ready activated carbons are effective in removing both Toluene and Atrazine from water. The purpose

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44 of this experiment, however, was to create a low cost activate d carbon from a natural resource which could be incorporated with the PUR in developing regions, as well as those in remote areas of developed countries, do not have access to these commercially prepared ACs. If activated carbon is not feasible to pair with PUR there are other alternatives such as ion exchange treatment that have down well with Atrazine removal in solution 47 Regardless, something needs to be done to improve the PUR recreational uses. For future work it would be interesting to examine the interactions between Humic Acid and Atrazine, Humic Acid and Toluene, and Atrazine and Toluene. Some research suggests that the presence of natural organic matter hinders the removal of Atrazine 48 and it would be interesting t o see if this is also true for the other interactions previously mentioned. There would also be examination of the molecular structures of Humic Acid Toluene, and Atrazine to determine what molecular forces occur within each and what exchanges occur betwe en them. Lastly, a deeper look will be taken at possibly creating a simple AC that would have a greater effect on removing contaminants from drinking water that the PUR packet is unable conquer.

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45 APPENDIX A PUR PACKET TREATMENT PHOTOS These are various shots taken throughout the PUR Packet water treatment process. Figure A 1 Floc forming just after PUR mixing process Figure A 2. Settled floc after allowing mixture to settle for the recommended 5 minute period

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46 Figure A 3. Front view of P UR treatment of Raw and DI water for the TOC concentration test (Raw water from Lake Alice on the left, Deionzied water on the right) Figure A 4. Top view of Raw and DI water after PUR treatment process (Raw Lake Alice water on the left, Deionized water on the right)

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47 Figure A 5. Filters after vacuum filtering the Raw and DI treated water (Raw water filter is on the left, DI water filter is on the right)

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48 APPENDIX B CHEMICAL STRUCTURES Toluene, Atrazine, Humic Acid (several types) B.1. Toluene MW: 92.14 g/mol Empirical Formula: C 7 H 8 or C 6 H 5 CH 3 Figure B 1. Basic Toluene chemical structure Figure B 2. 3 D Toluene structure created with Crystal Maker 8.1 and Accelrys DS Visualizer (Source: Ben Mills)

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49 B.2 Humic Acid Humic Acids come in several shapes and sizes. These are just a few examples of the various types of Humic Acid. There large size and differ ent compositions all create varying molecular weights and empirical formulas. Figure B 3. Humic Acid s tructure #1 Figure B 4. Humic Acid s tructure #2

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50 Figure B 5. Humic Acid s tructure #3

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51 LIST OF REFERENCES 1. Histo ry of Water Filters 2004 Retrieved November 23, 2009, from http://www.historyofwaterfilters.com/early water treatment.html. 2. U.S. Centers for D isease Control and Prevention. Safe Water System: A Low Cost Technology for Safe Drinking Water Fact Sheet, World Water Forum 4 Update, March 2006 Retrieved November 23, 2009 3. Procter & Gamble. Retrieved November 23, 2009 from http://www.csdw.org/csdw/dr_greg_allgoods_work.shtml 4. Procter & Gamble. A New Complementary Approach for Providing Safe Drinking Water ., Retrieved January 28, 2010 from http://www.pghsi.com/pghsi/safewater/pdf/International_PPOW_handout.pdf. 5. Wat er Quality and Health Council. A Public Health Giant Step: Chlorination of U.S. Drinking Water http://www.waterandhealth.org/dr inkingwater/chlorination_history.html, 2009 6. Reller, M.E.; Mendoza, C.E.; Lopez, M.B.; Alvarez, M.; Hoekstra, R.M.; Olson, C.A.; Baier, K.G.; Keswick, B.H.; and Luby S.P A Randomized Controlled Trial of Household Based Flocculant Disinfectant Drinking Water Treatment for Diarrhea Prevention in Rural Guatemala. The American Society of Tropical Medicine and Hygiene 2003 Vol. 69(4), 411 419. 7. Jesperson, K. Search for Clean Water Continues http://www.nesc.wvu.edu/old_website/ndwc/ndwc_DWH_1.html 8. Encyclop edia Britannica Microscope. Encyclopedia Britannica Online Retrieved December 5, 2009 from, . 9. Encyclopedia Britannica Antonie van Leeuwenhoek Encyclopedia Britannica Online Retrieved Decembe r 5, 2009 from . 10. City of Lewisville TX The History of Water Treatment Retrieved January 29, 2010 from, http://www.cityoflewisville.com/wcmsite/publishing.nsf/Content/Water+Facts 11. Wang, R.G.M. Water Contamination and Health: Integration of Exposure Assessment, Toxicology and Risk Assessment Page 4, 1994 12. Weise, J. Historic Milesto n e s in Drinking Water History Division of Environmental Health, Drinking Water Program.

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52 13. Mufute, R P&G Safe Drinking Water for Uganda (SDWU) Final Report 2008 Retrieved January 27, 2010, fr om. http://www.pghsi.com/pghsi/safewater/pdf/africare_PG_final_report_dec2008.pdf 14. Luby, S.P.; Agboatwalla, M.; Paint er, J.; Altaf, A; Billhimer, W.; K eswick, B.; Hoekstra, R.M Combining drinking water treatment and hand washing for diarrhoea prevention, a cluster randomised controlled trial. Tropical Medicine and Health 2006 11(4), 479 486. 15. In ternational Medical Corps Final report on The Gateway Initiative: S ensitizing Children to Promote Healthy Behaviors and Families. Water Program 2008 Retrieved November 30 2009, from http://www.pghsi.com/pghsi/safewater/pdf/IMC PG_DRC_Final_report_11_25_08.pdf 16. Doocy, S.; Burnham, G Point of use water treatment and diarrhea reduction in the emergency context: an effectiveness trial in Liberia. Tropical Medicine and Health 2006 11(10 ), 1542 1552. 17. BMJ Publishing Group Ltd Household based treatment of drinking water with flocculant disinfectant for preventing diarrhea in areas with turbid surface water in rural Kenya 2005 Retrieved November 30, 2009, from http://www.pghsi.com/pghsi/safewater/pdf/bmjCrump.pdf 18. Procter and Gamble Procter & Gamble Exceed $2 Million to Haiti Relief. PRNewswire 2010 Retrieved February 5, 2010, from http://www.pginvestor.com/phoenix.zhtml?c=104574&p=irol newsArticle&ID=1383211&highlight =. 19. Catholic Relief Services Honduras final report on Use of PUR 2009 Retrieved March 2, 2010, from http://www.pghsi.com/pghsi/safewater/pdf/CRS_Honduras PUR_water%20treatment_final.pdf 20. The History of Drinking Wate r Treatment ; EPA 816 F 00 006; United States Environmental Protection Agency Office of Water. Retrieved November 30, 2009 from http://www.epa.gov/ogwdw000/consumer/pdf/hist.pdf 21. Marples, G The History of Water Filters The Pure Source of Life Thehistoryof.net. Retrieved September 11, 2008 from http://www.thehistoryof.net/history of water filters.html 22. HM Digital History of Water Quality, Purification and Filtration Retrieved November 30, 2009 from http://www.tdsmeter.com/education?id=0002 2008.

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53 23. Ando, K.; Ishibashi, N.; Pari, G.; Miyakuni, K Trials on Some of Charcoal Production Methods for Carbon Sequestra tion in Indonesia 2001 Retrieved January 9, 2011, from http://www.biorefinery.uga.edu/char%20sypm%2004%20%20PDF%20Files/present ations/AndoPresentation.pdf 24. Wigmans, T Industrial Aspects of Production and Use of Activated Carbons. Carbon 1989 2(1), 13 22. 25. Krishnan, K. ; Sreejaleksh mi, K. G.; Varghese, S Adsorptive retention of citric acid onto activated carbon prepared from Havea braziliansis sawdust: Kinetic and isotherm overview. Desalination 2010 257(1 3), 46 52. 26. Awwad, N. S.; Gad, H. H.; A hmad, M. I.; Aly, H. F Sorption of lanthanum and erbium from aqueous solution by activated carbon prepared from rice husk. Colloids & Surfaces B: Biointerfaces 2010 81(2), 593 599. 27. Imyim, A., & Prapalimrungsi, E. (2010). Humic acids removal from water by aminop ropyl functionalized rice husk ash. Journal of Hazardous Materials 2010 184(1 3), 775 781. 28. Hayash i, J.; Horikawa, T.; Takeda, I.; Muro yama, K.; Nasir Ani, F Preparing activated carbon from various nutshells by chemical activation with K 2 CO 3 Carbon 2002 40(13), 2381. 29. Wang, K .; Li, C.; San, H.; Do, D The importance of finite adsorption kinetics in the sorption of hydrocarbon gases onto a nutshell derived activated carbon. Chemical Engineering Science 2007 62(23), 6836 6842. 30. Uar, S.; Erdem, M .; T ay, T.; Karagz, S Preparation and characterization of activated carbon produced from pomegranate seeds by ZnCl 2 activation. Applied Surface Science 2009 255(21), 8890 8896. 31. Kadirvelu, K.; Kavipriya, M.; Karthika, C.; Vennil amani, N.; Pattabhi, S Mercu ry (II) adsorption by activated carbon made from sago waste. Carbon 2004 42(4), 745. 32. Pesticide Industry Sales and Usage: 2000 2001 Market Estimates U.S. Environmental Protection Agency Office of Prevention, Pesticides and Toxic Substances. Retrieved Apr il 29, 2010 from http://www.epa.gov/pesticides/pestsales/01pestsales/market_estimates2001.pdf. 33. Australian Government Chemicals in the News: Atrazine Australian Pesticides and Veterinary Medicines Authority Retrieved June 30, 2010 from http://www.apvma.gov.au/news_media/chemicals/atrazine.php#what_is. 34. Weitz & Luxenberg. Atrazine Uses Retrieved February 28, 2011 from http://www.weitzlux.com/atrazineuses_403127 .html.

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54 35. Andrew Clayto n, C.; Pellizzari, E. ; Whitmore, R.; Quackenboss, J.; Adgate, J.; Sefton, K and polynuclear aromatic hydrocarbons in the Minnesota Children's Pesticide Exposu Journal of Exposure Analysis & Environmental Epidemiology 2003 13(2), 100. 36. Colt, Js. ; Camann, D.E.; Hartge, P #51 Pesticides in carpet dust and self reported pesticide use in four areas of the us. Annals of Epidemiology 2002 12(7) 508. 37. Curwin, B.D.; Hein, M.J. ; Sanderson, W.T.; Striley,C.; Heederik, D.; Kromh out,K.; Alavanja, M. C Urinary Pesticide Concentrations Among Children, Mothers and Fathers Living in Farm and Non Farm Households in Iowa. Annals of Occupational Hygiene 20 07 51(1), 53 65. 38. Bradman, A.; Whitaker, D.; Quir s, L.; Castorina, R.; Henn, B.; Nishiok a, M.; Eskenazi, B Pesticides and their Metabolites in the Homes and Urine of Farmworker Children Living in the Salinas Valley, CA. Journal of Exposure Science & Envi ronmental Epidemiology 2007 17(4), 331 349. 39. M aqbool, U.; Qureshi, M Comparison of in house developed ELISA with HPLC techniques for the analysis of atrazine residues. Journal of Environmental Science & Health Part B -Pesticides, Food Contaminants, & Agricultural Wastes 2008 43(3), 224 230. 40. Gabaldnt, J. A.; Cascales, J. M.; Morias, S. S.; Maquieira, A. A.; Puchades, R. R Determination of atrazine and carbaryl pesticide residues in vegetable samples using a multianalyte dipstick immunoassay format. Food Additives & Contaminants 2003 20(8), 707. 41. Ochoa Acua, H.; Frankenberger, J. ; Hahn, L.; Carbajo, C Drinking Water Herbicide Exposure in Indiana and Prevalence of Small for Gestational Age and Preterm Delivery. Environmental Health Perspectives 200 9 117(10), 1619 1624. 42. Greenlee, A. R.; Ellis, T. M.; Berg, R. L Low Dose Agrochemicals and Lawn Care Pesticides Induce Developmental Toxicity in Murine Preimplantation Embryos. Environmental Health Perspectives 2004 112(6), 703 709. 43. Betancourt, M.; R esndiz, A.; Fierro, E Effect of two insecticides and two herbicides on the porcine sperm motility patterns using computer assisted semen analysis (CASA) in vitro. Reproductive Toxicology 2006 22(3), 508 512. 44. Chan, Y.; Chang, S.; Hsuan S.; Chien, M.; Lee, W.; Kang, J.; Liao, J. Cardiovascular effects of herbicides and formulated adjuvants on isolated rat aorta and heart. Toxicology in Vitro 2007 21(4), 595 603. 45. Roberge, M. T .; Hakk, H.; Larsen, G Cytosolic and localized inhibition of phosphodiestera se by atrazine in swine tissue homogenates. Food & Chemical Toxicology 2006 44(6), 885 890.

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55 46. WuQiang, F.; Yanase, T.; Morinaga, H.; Gondo, S. ; Okabe, T.; Nomura, M.; Nawata, H Atrazine Induced Aromatase Expression Is SF 1 Dependent: Implications for Endocrine Disruption in Wildlife and Reproductive Cancers in Humans. Environmental Health Perspectives 2007 115(5), 720 727. 47. Humbert, H.; Gallard, H.; Suty, H.; Crou, J Natura l organic matter (NOM) and pesticides removal using a combination of ion exchange resin and powdered activated carbon (PAC). Water Research 2008, 42(6/7), 1635 1643. 48. Lazorko Conno n, S. S.; Achari, G. G Atrazine: its occurrence and treatment in water. Env ironmental Reviews 2009 17(1), 199 214.

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56 BIOGRAPHICAL SKETCH Taccara Nakia Williams was born in May of 1987 in Waterbury, CT. She graduated from Crosby High School in 2005 with honors and went on to pursue an engineering degree at Temple University in Philadelphia, PA. Craving a more challenging and intimate learnin g environment she transferred to North Carolina Agricultural and Technical State University in Greensboro, NC in the Fall of 2006. Here she earned her Bachelor of Science degree in civil engineering and graduated Magna cum Laude in May of 2009. She also re ceived a Waste Management Certificate during her matriculation. Her desire to get a more in depth understanding of water quality and quantity issues led her to pursue a graduate degree in environmental engineering at the University of Florida. In the futur e she hopes to use the knowledge she has acquired in her educational career to help improve the water quality and quantity issues of the world.