characterization of airborne ozone concentrations …
TRANSCRIPT
The Pennsylvania State University
The Graduate School
College of Earth and Mineral Sciences
CHARACTERIZATION OF AIRBORNE OZONE CONCENTRATIONS IN
A BOTTLED WATER MANUFACTURING FACILITY
A Thesis in
Industrial Health and Safety
By
James Gazza
© 2013 James Gazza
Submitted in Partial Fulfillment
of the Requirements
for the Degree of
Master of Science
May 2013
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The thesis of James Gazza was reviewed and approved* by the following:
William A. Groves
Associate Professor, Industrial Health and Safety
Graduate Program Chair
Thesis Adviser
Robert Larry Grayson
Professor, Energy & Mineral Engineering
Dennis Murphy
Professor, Agricultural Safety & Health and Extension Safety Specialist
*Signatures are on file in the Graduate School.
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ABSTRACT
Ozone is a material that has several diverse associations. One of these is ozone’s presence high
in the earth’s atmosphere that forms a barrier around the earth that protects human health, plant
life and aquatic ecosystems from the harmful rays of the sun. Another is ozone’s infamous
connection to smog and the detrimental impact smog has on public health. Still another is the
use of ozone as a disinfecting agent against water-borne microorganisms in drinking water. It is
this association that forms the basis for this research.
Over the past several decades, the use of ozone has emerged in the bottled water manufacturing
industry as the method of choice for disinfecting the bottle rinse water, product water, the bottle
and the associated bottling equipment. It does this efficiently and effectively then quickly
decomposes to oxygen without leaving an after taste or odor.
However, while ozone is working as a disinfectant, it is also off-gassing from the ozonated rinse
water and product water into the workplace atmosphere. It is at this point in the production of
bottled water that the workers operating the bottle filling equipment may be exposed to ozone
gas at potentially harmful airborne concentrations.
This research paper summarizes the air sampling methodology that was employed to measure
airborne ozone in an active bottled water manufacturing plant for the purpose of characterizing
the airborne ozone concentrations. The statistical analysis performed for this research identified
several variables that have the ability to influence the airborne ozone concentrations:
1) The level of ozone in the rinse water used to clean bottles prior to filling,
2) Production of ozonated water products versus spring water products,
3) Size of the bottles being filled, especially when filled with ozonated product water, and
4) The number of air handling units operating in the work area.
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Statistical analysis also revealed that there are specific production scenarios, including filling
larger bottles with ozonated product, for which the mean airborne ozone concentration can
temporarily exceed relevant occupational exposure limits such as the Occupational Safety and
Health Administration (OSHA) 8-hour PEL-TWA of 0.1 ppm, the American Conference of
Governmental Industrial Hygienists (ACGIH) 8-hour TLV-TWA (moderate work) of 0.05 ppm,
and the OSHA 15-minute short term exposure limit (STEL) of 0.3 ppm. Although short-term
concentrations for these scenarios ranged from 0.0516 - 0.1486 ppm, personal air sampling
results for equipment operators in this work setting indicate concentrations were below the
OSHA 12-hour adjusted TWA exposure limit of 0.067 ppm.
Examination of the ozone concentrations measured at the two sampling points where operators
spend most of their time, and for the time period over which three AHUs were operating,
showed that data were distributed normally with a mean of 0.052 ppm and standard deviation of
0.020 ppm. Further, the distribution indicates that approximately 80% of the measured
concentrations were below the OSHA 12-hour adjusted TWA exposure limit of 0.067 ppm.
Understanding how production variables influence airborne ozone concentration and the
measures such as room ventilation that can be taken to control exposures in the workplace
atmosphere to below established exposure limits will help ensure a safe and healthy work
environment for the operators of the bottle filling equipment.
It is important to note that the results of this research are site-specific and may not be reflective
of the bottled water industry (or other industries utilizing ozone as a disinfectant in their
processes) in general. However, the knowledge and understanding gained from this research,
with regard to how ozone behaves in an industrial setting, should be potentially useful to other
bottled water manufacturing facilities or industries dependent on ozone in its processes when it
comes to controlling this airborne contaminant.
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TABLE OF CONTENTS
List of Tables vi
List of Figures vii
Glossary ix
Acknowledgements xii
Chapter 1. Introduction 1
1.1. Background 1
1.2. Research Objectives 3
Chapter 2. Literature Review 5
2.1. Ozone Discovery 5
2.2. Generation of Ozone – Natural and Mechanical 5
2.3. The Dichotomy that is Ozone 7
2.4. Physical and Chemical Properties of Ozone 11
2.5. Ozone Decomposition / Half-Life in Air and Water 12
2.6. Bottled Water Manufacturing Industry and the U. S. Food and
Drug Administration 13
2.7. Use of Ozone as a Disinfectant in the Bottled Water Manufacturing
Industry 14
2.8. Advantages / Disadvantages of Using Ozone as a Disinfectant 15
2.9. Common Health Effects of Ozone Exposure 16
2.10. Who is Most at Risk From Ozone Exposure? 19
2.11. Ozone – Dose and Effect 21
2.12. Exposure Limits 22
2.12.1. Occupational Exposure Limits 22
2.12.1.1 Adjusted Occupational Exposure Limits 24
2.12.2. Public Health Exposure Limits 25
Chapter 3. Methods 27
3.1. Bottled Water Manufacturing – Process Overview 27
3.2. Product Water Treatment – Filtration 33
3.3. Product Water Treatment – Ozonation 35
3.4. Filler Room 39
3.5. Bottle Filling Process 46
3.6. Sources of Ozone in the Filler Room 48
3.7. Factors Affecting Airborne Ozone Concentrations 48
3.8. Ozone Sampling Methodology 48
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Chapter 4. Results and Discussion 55
4.1. Statistical Analysis 55
4.2. Study Design 56
4.2.1. Data Set Input Commands 59
4.3. Exploratory Data Analysis (EDA) 60
4.3.1. Effect of Line 4 Status 60
4.3.2. Effect of Purified Water Production 62
4.3.3. Effect of AHU 63
4.3.4. Effect of Sampling Points 65
4.3.5. Effect of Production Status on the Filler Being Sampled 67
4.3.6. Effect of Production Status with Size of Bottle 69
4.3.7. Correlation Between Ozone Concentrations in Air,
Rinse Water and Product Water 71
4.3.8. Interactions Between Predictor Variables 72
4.3.8.1. Interactions Between Ozone_RinseWater and
Categorical Predictor Variables 73
4.3.8.2. Interactions between Ozone_Product and Categorical
Predictor Variables 76
4.4. Model Construction and Analysis of Variance 78
4.5 Trends / Observations Identified During Research 84
4.6. Comparison of Airborne Ozone Concentrations to Occupational
Exposure Limits 86
Chapter 5. Conclusions and Recommendations for Future Research 94
5.1. Conclusions 94
5.2. Recommendations for Future Research 95
5.2.1. Other Factors Influencing the Level of Airborne Ozone 96
5.2.2. Potential Methods of Ozone Destruction 97
5.2.3. Air Flow Patterns and How They May Influence the
Level of Airborne Ozone 98
5.2.4. Detrimental or Therapeutic Effects of Ozone 99
Appendix A: Summary of Ozone Related Health Effects 102
Appendix B: National Ambient Air Quality Standards Values 106
Appendix C: Understanding the Air Quality Index 107
Appendix D: Air Quality Index Colors 108
Appendix E: Air Quality Guide for Ozone 109
Appendix F: Health Effects and Protective Actions for Specific Ozone Ranges 110
Appendix G: Ozone Monitoring Data Set 111
Appendix H: Ozone Monitoring Data Collection Sheet 123
References 124
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LIST OF TABLES
Table 2.1 Physical and Chemical Properties of Ozone Gas 12
Table 2.2 Typical Ozone Half-Life versus Temperature 13
Table 2.3 Toxic Effects of Ozone 21
Table 2.4 Selected Occupational Exposure Limits for Ozone 23
Table 2.5 12-Hour Adjusted Occupational Exposure Limits for Ozone 24
Table 4.1 List of the Categorical Variables 57
Table 4.2 Comparison of Production Scenarios with Selected Occupational
Exposure Limits 87
Table 4.3 History of Personal Sampling for Ozone Exposure 92
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LIST OF FIGURES
Figure 2.1 Formation of Ground-Level Ozone 9
Figure 3.1 Natural Spring Product Water – Manufacturing Process Flowchart 29
Figure 3.2 Purified Product Water – Manufacturing Process Flowchart 30
Figure 3.3 Ozone Generation from Corona Discharge 36
Figure 3.4 Filler Room Diagram 40
Figure 3.5 Aeroqual Ozone Series 500 Monitor – Exterior View 49
Figure 3.6 Aeroqual Ozone Series 500 Monitor – Interior View 50
Figure 3.7 Filler Room Schematic Illustrating Location of Sampling Points 52
Figure 3.8 Air Sampling Timeline 53
Figure 4.1 Timeline of the Events 58
Figure 4.2 Partial Data Set Arranged in Excel Format 58
Figure 4.3 SAS Window and the Run Icon 59
Figure 4.4 SAS Output of t-test of Airborne Ozone Concentration on
Variable Line4 61
Figure 4.5 SAS Output of t-test of Airborne Ozone Concentration on Purified 62
Figure 4.6 SAS Output for the Mean Airborne Ozone Concentration at
Different AHU 63
Figure 4.7 SAS Output for ANOVA of Airborne Ozone Concentration
on AHU 65
Figure 4.8 SAS Output for the Mean Airborne Ozone Concentration at
Different Sampling Points 66
Figure 4.9 SAS Output for ANOVA of Airborne Ozone Concentration on Point 67
Figure 4.10 SAS Output for the Mean Airborne Ozone Concentration at
Different Production Status 67
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Figure 4.11 SAS Output for ANOVA of Airborne Ozone Concentration on
Production 68
Figure 4.12 SAS Output for the Mean Airborne Ozone Concentration at Different
Production Status with Size 69
Figure 4.13 SAS Output for ANOVA of Airborne Ozone Concentration on
Production_Size 70
Figure 4.14 SAS Output for Correlation 71
Figure 4.15 Plot of Ozone_Air vs. Ozone_RinseWater for Purified and No Purified 73
Figure 4.16 Plot of Ozone_Air vs. Ozone_RinseWater with Different AHUs 74
Figure 4.17 Plot of Ozone_Air vs. Ozone_RinseWater with Different
Production_Size 75
Figure 4.18 Plot of Ozone_Air vs. Ozone_Product for Purified and No Purified 76
Figure 4.19 Plot of Ozone_Air vs. Ozone_Product with Different AHU 77
Figure 4.20 Plot of Ozone_Air vs. Ozone_Product with Different Production_Size 78
Figure 4.21 Studentized Residual Plots 80
Figure 4.22 SAS Output for Model Construction and Analysis of Variance 81
Figure 4.23 Studentized Residual Plots for Reduced Model 82
Figure 4.24 SAS Output of Testing the Significance of the Factors in the Reduced
Model 82
Figure 4.25 SAS Output of Least Squares Means 84
Figure 4.26 SAS Output of Multiple Comparisons with Tukey Adjustment 84
Figure 4.27 Probability Plot for Sampling Point 1 Ozone_Air 90
Figure 4.28 Probability Plot for Sampling Point 2 Ozone_Air 91
Figure 4.29 Probability Plot for Sampling Points 1 and 2 with AHU 93
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GLOSSARY
Air Changes - Defined as the number of times per hour that filtered outside or “fresh” air
replaces the existing volume in a building or room.
Categorical Variables - Any variable that is not quantitative is categorical. Categorical
variables take a value that is one of several possible categories. As measured, categorical
variables have no numerical meaning. Examples: Hair color, gender, field of study, college
attended, political affiliation, status of disease infection.
Ceiling Limit (C) - An exposure concentration that should not be exceeded, even
instantaneously, during any part of the workday.
Clean-In-Place (CIP) – method of cleaning using elevated water temperature and chemical
detergents to clean the interior surfaces of pipes, vessels, process equipment, filters and
associated fittings, without disassembly.
Continuous Variables - A continuous variable is one for which a subject or observation takes a
value from an interval of real numbers. For example, if age can be measured precisely enough it
takes any value from zero upwards.
Filler Room – Portion of the bottled water manufacturing facility where the bottles are rinsed,
filled with product water and capped. This is also the room where the air sampling for the
research project took place.
Forced Expiratory Volume in 1 Second (FEV1) - The amount of air which can be forcibly
exhaled from the lungs in the first second of a forced exhalation. Measuring FEV1 is done
through spirometry testing which helps a doctor determine a person’s lung function.
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Forced Vital Capacity (FVC) - The maximal volume of air that can be exhaled from full
inhalation by exhaling as forcefully and rapidly as possible.
Generally Recognized as Safe (GRAS) – Is a food ingredient regulatory classification of US
Food and Drug Administration (FDA). The scientific data and information about the use of a
substance, intentionally added to food, must be widely known and there must be a consensus
among qualified experts that those data and information establish that the substance is safe under
the conditions of its intended use.
High Efficiency Particulate Air (HEPA) Filter – A filter that is capable of trapping and
retaining 99.97% of all mono-dispersed particles 0.3 microns or greater in size from the air
stream flowing through it.
Immediately Dangerous to Life or Health (IDLH) - An atmospheric concentration of any
toxic, corrosive or asphyxiant substance that poses an immediate threat to life or would cause
irreversible or delayed adverse health effects or would interfere with an individual's ability to
escape from a dangerous atmosphere.
Odor Threshold - Lowest airborne concentration that can be detected by a population of
individuals. While odor thresholds can serve as useful warning properties, they must be used
cautiously because olfactory perception varies among individuals.
Purified Water - Is water that has been produced by distillation, deionization, reverse osmosis,
or other suitable processes.
Short-Term Exposure Limit (STEL) – A worker's 15 minute time-weighted average (TWA)
exposure that must not be exceeded in a work day.
Spring Water – Water derived from an underground formation from which water flows
naturally to the surface of the earth. Spring water must be collected only at the spring or through
a borehole tapping the underground formation feeding the spring.
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Time-Weighted Average (TWA) - The average airborne exposure that shall not be exceeded in
any 8-hour period during a 40-hour workweek.
Total Lung Capacity (TLC) - Maximum volume of air in the lungs that can be exhaled
following a maximal inhalation.
Trihalomethanes (THMs) - THMs are the by-products of chlorine disinfection of water that
contains natural organic matter. THMs may pose an increased risk of cancer.
xii
ACKNOWLEDGEMENTS
I would like to express my gratitude to my employer for allowing me time during my normal
work day to collect the air samples that comprised the data set for the research and to several of
my co-workers for providing insight into the water filtration and ozonation processes and the
operation of the bottle filling equipment and the air handling systems in the Filler Room.
I wish to extend my gratitude towards Dr. William Groves for his valuable suggestions and
guidance in directing my research efforts and organizing the content of my thesis.
I would also like to thank my wife for being patient with me while I isolated myself in our
basement over the past several years working on this thesis.
I would also like to congratulate myself for persevering through life’s trials and tribulations that
sprung up during the past years making it difficult at times to concentrate on completing my
thesis.
Finally, I would like to express my gratitude to PSU for being patient during my extended
attempt to complete the research and the drafting of this Thesis.
1
Chapter 1
INTRODUCTION
1.1. Background
Over the years, ozone has been routinely linked to its association with either the ozone layer in
the earth’s upper atmosphere that protects human beings and plant life from the sun’s harmful
ultraviolet (UV) rays or as a key component in smog. The former is viewed as being
significantly beneficial to the human race while the latter is viewed as a leading public health
concern.
There is one other use of ozone that helps provide a stable and safe source of water for the
beverage manufacturing industry. This use is as a disinfectant for purifying the water used in the
manufacture of beverage products without the use of any harmful chemicals. This benefit of
ozone has allowed one particular beverage industry to flourish over the recent decades – bottled
water. However, while ozone is working as a disinfectant it is also being liberated to the work
area atmosphere in concentrations that may pose a variety of health hazards to the workers
present in the room where the bottles are being filled. With this premise in mind, the research
for this project is centered on examining those factors that may play a significant role in
influencing the airborne concentrations of ozone in such a work environment.
A review of the literature identified hundreds of peer-reviewed articles involving controlled
human exposure, toxicological, animal and epidemiologic studies conducted over the past
several decades. These studies focused on both the short-term (acute) and long-term (chronic)
health effects of ozone exposure. The majority of these studies involved public health research
associated with human exposure to ground-level ozone as a component in smog and its effect on
the respiratory system at varying airborne concentrations. Many of these studies are cited and
summarized in compilation documents such as:
1) Policy Assessment for the Review of the Ozone National Ambient Air Quality Standards
(First External Review Draft), U.S. EPA. [1]
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2) Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third
External Review Draft), U.S. EPA. [2]
3) Review of the National Ambient Air Quality Standards for Ozone: Policy Assessment of
Scientific and Technical Information Office of Air Quality Planning and Standards Staff
Paper, U.S. EPA. [3]
4) Air Quality Criteria for Ozone and Related Photochemical Oxidants, U.S. EPA. [4]
What was found lacking in the literature search were articles involving scientific studies that
focused on three factors:
1) The use of ozone in an industrial setting;
2) The characteristics of a dynamic work environment (e.g., where product bottles are filled
with ozonated or spring water while workers operate and monitor the production
equipment) and the wide range of potential sources that contribute to or influence the
airborne concentrations of ozone gas that workers are potentially exposed to; and
3) How ozone concentrations encountered over the duration of a typical work shift (e.g., 8-,
10- or 12-hour shift) and workweek compare to the concentrations and health effects
identified in controlled human studies.
There were several documents identified during the literature search that somewhat reflected
ozone exposures in an industrial environment. These were:
1) Emergency and Continuous Exposure Guidance Levels for Selected Submarine
Contaminants Volume 2, National Research Council of The National Academies. [5]
2) OSHA Method ID-214 - Ozone in Workplace Atmospheres (Impregnated Glass Fiber Filter)
- February 2008. [6]
3) The Airliner Cabin Environment and the Health of Passengers and Crew, National
Research Council of The National Academies. [7]
4) ACGIH Threshold Limit Value (TLV) Documentation for Ozone. [8]
However, the majority of the studies cited in these documents were more reflective of controlled
human studies rather than worker exposure in a true industrial environment.
3
1.2 Research Objectives
The objective of this research is to begin to bridge the gap between existing studies focused on
ground-level ozone as a component in smog and its impact on public health or controlled human
exposure studies conducted under laboratory-type conditions, and the characterization of
airborne concentrations of ozone in an industrial setting.
This task was undertaken through the collection of multiple samples of airborne ozone in the
work area during the step of the bottled water production cycle in which bottles are rinsed with
ozonated water, filled with product water (either spring or spring water purified with ozone) and
then capped. The results of the samples along with information recorded for several other related
production variables were compiled to form the data set for this research. The variables in the
data set were statistically analyzed to identify significant contributors to the airborne ozone
concentrations present in the bottled water filling area of the facility.
This research also began the process of identifying and evaluating various features present in a
bottled water production area that can influence the airborne concentrations of ozone and should
be strongly considered when designing and constructing such a work area to help maintain the
airborne ozone concentrations at or below the established occupational exposure limits. These
design features should help to safeguard the health and safety of individuals working in this type
of manufacturing environment.
The remaining chapters of this thesis are organized as follows:
Chapter 2 – Literature Review:
1) History behind the discovery of ozone
2) Ozone and its link to smog
3) Characteristics of ozone
4) Ozone’s use in the bottled water manufacturing industry
5) Adverse health effects and vulnerable populations
6) Occupational and public health exposure limits for ozone
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Chapter 3 – Methodology:
1) The bottled water manufacturing process
2) Sources of ozone in the bottled water filling work area
3) Methodology used to collect the samples of airborne ozone
Chapter 4 – Results and Discussion:
1) Statistical analysis of the research variables
2) Trends and observation identified during the course of the research
3) Results of the analysis and the comparison of the airborne ozone concentrations to
occupational exposure limits for various production scenarios
Chapter 5 – Conclusion and Recommendations for Future Experiments:
1) Other factors that can influence the level of airborne ozone
2) Potential methods of ozone destruction
3) Air flow patterns and how they may influence the level of airborne ozone in the work
environment
4) Detrimental or therapeutic effects of ozone
It is important to note that this study is observational in nature. The data was not gathered under
controlled laboratory and experimental conditions; rather it was collected in an active bottle
water manufacturing facility and is reflective of real-time conditions experienced at the time of
sampling. Therefore it was not possible to control numerous parameters in the work area such as
room temperature and humidity; production activity; the quantity of airborne ozone off-gassing
from product water or bottle rinse water; naturally occurring ozone brought into the work area
where bottles were being filled with product water through its air handling system; effectiveness
of the work area’s air handling system to exhaust and return “fresh” air to the room; equipment
location/placement and its impact on air flow patterns within the work area; variation of ozone
level present in the product water or bottle rinse water; and efficiency of bottle filling equipment.
5
Chapter 2
LITERATURE REVIEW
2.1. Ozone Discovery
Industrially, ozone was first observed by Dutch chemist Martinus van Marum (1750-1837) in
1785 when he noticed a peculiar fresh smelling odor in the air while subjecting oxygen to
electrical discharges. However, he failed to identify it as a unique form of oxygen.
The compound remained unnamed for 55 years, until 1840 when German scientist Christian F.
Schönbein (1799-1868) detected the same peculiar odor in the oxygen liberated while conducting
experiments on the electrolysis of water at the University of Basel. He named the gas ozone
after the Greek word ozein, meaning, "to smell.” Schönbein believed that ozone was a new
element, and he went on to study its properties extensively.
The development of ozone generation remained in the laboratory until 1857 when German
inventor Werner Von Siemens (1816-1892) designed an ozone generator that has since evolved
into the present day, cylindrical dielectric type that makes up most of the commercially available
ozone generators in use, and which has sometimes been called the "Siemens Type" ozone
generator [9]. This was an important step forward in the use of ozone gas because it recognized
the fact that because the gas is unstable, cannot be stored in a container and is highly reactive, it
needs to be generated immediately before its use. The molecular formula of ozone was
determined in 1865 by Swiss chemist Jacques-Louis Soret (1827-1890) and confirmed by
Christian F. Schönbein in 1867 [10].
2.2. Generation of Ozone - Natural and Mechanical
Ozone is a highly unstable and reactive allotropic form of gaseous oxygen. It has a molecular
formula of O3. Ozone is constantly being created naturally in the earth's upper atmosphere, or
stratosphere, by the action of UV radiation generated by the sun and molecular oxygen (O2).
When high-energy UV rays at wavelengths shorter than 240 nanometers (nm) strike ordinary
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oxygen molecules (O2), they break the chemical bond and split the molecule into two single
oxygen atoms (O+O), known as atomic oxygen (O). This breaking of the chemical bond by UV
rays is called photolysis (Photo = light and lysis = cutting or breaking). A highly reactive free
oxygen atom then combines with another oxygen molecule to form a molecule of ozone (O3) (or
trivalent oxygen, O3.). Because ozone is so unstable, the UV rays quickly break it up, and the
“ozone-oxygen cycle” begins again [11]. Atmospheric ozone is also created naturally by
lightning strikes that occur during a thunderstorm. In fact the fresh smell that is so noticeable in
the air after a thunderstorm is actually the smell of ozone.
Ozone can also be mechanically generated by either corona discharge or UV light. Briefly,
corona discharge involves passing an oxygen-containing gas through two electrodes separated by
a dielectric and a discharge gap. Voltage is applied to the electrodes, causing electrons to flow
across the discharge gap. These electrons provide the energy to disassociate the oxygen
molecules, leading to the formation of ozone [12]. Since this method of ozone generation is used
at the bottled water manufacturing facility where the research took place, it will be discussed in
more detail in Chapter 3.
As an alternative to generating ozone via corona discharge, UV lamps can also be used to
generate ozone. Ozone is produced when air is passed over a UV lamp that is designed to allow
UV light at a wavelength of 185 nm to transmit through the lamp’s special quartz envelope.
This particular wavelength of UV light splits oxygen molecules (O2) in the air into single oxygen
atoms (O+O). These atoms, seeking stability, combine with other oxygen molecules (O2) to form
ozone (O3). The UV production of ozone, however, is at a lower rate as compared to a corona
discharge generator. Therefore, UV light is typically not used as a means of generating ozone
for use in bottle water production.
Conversely, UV light can also be used to destroy ozone in water very quickly. The mechanism
for destroying ozone is dissociation, which occurs when UV energy at a wavelength of 254 nm
“breaks” one of the oxygen bonds in the ozone molecule. Because of this reaction, each ozone
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molecule is converted into one oxygen atom and one oxygen molecule. Free oxygen atoms will
combine with each other to form oxygen molecules [13].
2.3. The Dichotomy That is Ozone
From a public health standpoint, naturally occurring ozone can be “good” or “bad” depending on
where it is located in the earth’s atmosphere. Ozone in the earth’s stratosphere is an essential gas
that helps to protect the earth from the sun’s harmful UV rays. This is the “good” ozone. By
contrast, the ozone found closer to the earth’s surface in the troposphere harms both human
health and the environment. This is the “bad” ozone that is found in smog. For this reason,
ozone is often described as being “good up high and bad nearby” [14].
This naturally occurring ozone gas is the substance that concentrates and forms a protective
circle around the entire earth’s surface in the upper part of the stratosphere, commonly known as
the ozone layer. Approximately 90% of the ozone in the earth's atmosphere is present in this
region. Ozone concentrations in the ozone layer are scarce and range from 1 to 10 parts per 1
million parts of air depending on geographic location, compared with about 210,000 parts of
oxygen per 1 million parts of air. This ozone is “good” because it provides a critical and
beneficial barrier or shield where 93 to 99% of the sun’s biologically damaging UV radiation is
absorbed by ozone thereby protecting humans, animals and vegetation. The remaining 10% of
ozone is in the troposphere of the earth. Ozone in this region is found at concentrations ranging
from 0.02 to 0.3 parts per million (ppm) [15].
The troposphere is where the “bad” ozone (also known as ground-level ozone) is found.
Ground-level ozone is a primary component of smog. Unlike other air pollutants, ground-level
ozone is not emitted directly from industrial operations into the atmosphere. Rather ground-level
ozone is a secondary pollutant produced through the same photochemical reaction in the
atmosphere involving strong sunlight (especially UV light), high daytime temperatures (>64oF),
oxygen and airborne emissions of additional compounds called precursors that ultimately results
in the formation of smog. The precursors typically involved in the generation of ground-level
ozone and smog consist of:
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1) Nitrogen oxides {NOx, which is the sum of nitric oxide (NO) and nitrogen dioxide (NO2)}
formed as a by-product when fossil fuels such as gasoline, kerosene, oil, natural gas or coal
is burned to generate electricity or used as a fuel in automobiles, trucks, buses, aircrafts,
lawn and garden equipment and locomotives. Nitrogen oxides are also naturally emitted
from soils, as a consequence of microbial processes occurring in the soil, and may also be
produced by lightning and by forest fires (many of which are started by lightning strikes).
[16].
2) Vapors from anthropogenic (man-made) volatile organic compounds (VOCs) (to include,
alkanes, alkenes, aromatic hydrocarbons, aldehydes, ketones, alcohols, organic peroxides,
etc.) emitted to the atmosphere from sources such as oil refineries, industrial use of
solvents and degreasers, chemical manufacturing plants, the gas pump nozzles from filling
stations, dry cleaning operations, evaporating paint, etc. Natural or biogenic VOCs,
mainly pinenes and terpenes, emitted from certain trees and other vegetation as well as
wildfires contributes to the overall volume of VOCs, although at a much smaller portion.
3) Carbon monoxide, carbon dioxide, sulfur oxides and methane are also involved in the
reaction that forms smog, although at a much lesser extent.
Figure 2.1 below provides an illustration that depicts how ground-level ozone is created.
9
Figure 2.1 Formation of Ground-Level Ozone
Source: AIRNow website (http://airnow.gov/index.cfm?action=aqibasics.ozone).
The reaction of these materials not only creates ground-level ozone but also creates
“photochemical smog”. This is one of the reasons why ground-level ozone and smog are often
mistakenly used interchangeably by the general public. Ground-level ozone is but one of several
constituents that make up smog. The other constituents that make up the majority of smog
include VOCs, nitrogen oxides (NO and NO2 – NO2 is the substance that gives smog its
characteristic brownish-yellow hazy appearance), sulfur oxides (SO2 and SO3), fine airborne
particulates (PM2.5 and PM10) and peroxyacytyl nitrates (PAN).
Another reason that the terms ground-level ozone and smog are often mistakenly used
interchangeably is the fact that collectively VOCs are substances with complicated chemical
structures. They are difficult to measure whereas ozone is very easy to measure and measure
accurately. Consequently, ozone has commonly been used as a yardstick for indicating the
10
severity or presence of smog because not only is it easy to measure but also it has a direct
relationship to levels of chemical pollutants found in smog. This despite the fact that in smog,
ozone occurs at a lesser concentration than the VOCs, or even the NOx [17].
The complex chemistry associated with the formation of ground-level ozone is also affected by
factors such as weather, temperature, wind speed, landforms, and altitude. Taking these factors
into consideration, meteorological conditions that are most favorable for ground-level ozone
formation consist of: an area where an ample supply of NOx and VOCs are present – typically an
urban area; during the months of May through September where long warm sunny days, higher
temperatures and high humidity are typically present; daytime hours; stagnant or slow wind
speeds; and during temperature inversions (atmospheric layer in which the upper portion is
warmer than the lower).
Conversely, ground-level ozone concentrations tend to be lowest when weather conditions are
cloudy, cool, rainy, windy, during the night time hours and throughout the winter months.
Because ground-level ozone concentrations are dependent on high temperature and sunlight, the
highest concentrations during the year occur in the summer months. Alternatively, the lowest
concentrations occur during the winter months.
Ground-level ozone concentrations also vary over different scales of time. In urban areas where
ground-level ozone is typically generated, ozone concentrations tend to peak in the middle of the
day and dip to their lowest concentrations during the middle of the night. After the suns sets, the
production of ozone stops. The ozone that remains in the atmosphere is consumed by a
multitude of reactions and therefore does not accumulate from one day to the next [18].
In addition to high ground-level ozone concentrations in urban and suburban areas, increasingly
high ground-level ozone concentrations are also being found in rural areas. This is due to
prevailing winds preventing the local build-up of the ground-level ozone precursor materials near
their sources and transporting them miles away from their original urban sources. While the
ozone precursors are blowing through the air, they continue to react to form additional ground-
level ozone. These factors can make it extremely difficult to predict ground-level ozone
11
concentrations based solely on the locations where emissions of NOx and VOC emission sources
are at their peak.
2.4. Physical and Chemical Properties of Ozone
From a worker health standpoint, one of the most relevant physical properties of a chemical is
the airborne concentration at which it can be detected by the sense of smell. Ozone has a variety
of characteristic odors at varying concentrations. Some describe ozone as having a pungent odor
that is detectable at 0.01 ppm [19]. Others describe it as having a “pleasant, characteristic” odor
at concentrations below 0.2 ppm but as “irritating” at concentrations above 0.2 ppm [20]. Still
others describe ozone as having an odor similar to high voltage discharges / electrical sparks or
the distinctive clean fresh smell in the air following a thunderstorm.
Ozone has an odor threshold ranging from 0.005 to 0.02 ppm, dependent upon the individual’s
sensitivity and health. Therefore, based on the concentrations of ozone routinely evaluated in
many of the scientific studies in the literature, the majority of individuals should be able to smell
ozone before it becomes a concern to their health. One other characteristic of ozone is that it is
known to cause olfactory fatigue; meaning a person’s ability to smell ozone is lost quickly as the
exposure to the substance continues.
Two of the more notable physical hazards associated with ozone are it is not flammable but can
enhance combustion of other substances. However, at high concentrations ozone can pose a
serious fire and explosion risk by reacting with combustible, flammable or other oxidizable
materials. This is due to ozone’s very strong oxidizing ability. It is dangerously reactive and
unstable at room temperature. It may decompose violently, under conditions of shock or elevated
temperatures and can react violently or explosively with many chemicals.
Other physical and chemical properties of ozone gas are summarized in Table 2.1.
12
Table 2.1 Physical and Chemical Properties of Ozone Gas
CAS Number 10028-15-6
Color Colorless to light /pale blue
Chemical Formula O3
Molecular Weight 48
Boiling / Condensation Point, oC (
oF) -112 (-170)
Freezing Point, oC (
oF) -192.5 (-314.5)
Vapor Density (air = 1) 1.65
Flash Point Not Applicable
Gas Density, g/l @ 0oC 2.144
2.5. Ozone Decomposition / Half-Life in Air and Water
In air, ozone decomposes much slower than in water. For example, at a temperature of 68
oF
(20oC), the half-life of ozone is 3 days. In water, ozone decays rapidly and must be produced on-
demand at the site of application. Theoretically, the half-life of ozone in water is approximately
30 minutes at 59oF (15
oC), which means that every half hour the ozone concentration will be
reduced to half its initial concentration. For example, if the starting concentration of ozone in
solution is 1 part per million (ppm), the concentration reduces by one-half every 30 minutes as
follows: 0.5 ppm, 0.25 ppm, 0.13 ppm, 0.06 ppm, etc. In practice, many factors can influence the
half-life and result in shorter half-life in use. For example, temperature, pH, agitation, and the
concentration of oxidizable substances in the water affect ozone stability and concentration [21].
Table 2.2 provides half-life information for both gaseous ozone and ozone dissolved in water.
13
Table 2.2 Typical Ozone Half Life Versus Temperature
Gaseous Ozone Ozone Dissolved in Water (pH 7)
Temp (oC/
oF) Half-Life Temp (
oC/
oF) Half-Life
-50/-58 3 months 15/59 30 minutes
-35/-31 18 days 20/68 20 minutes
-25/-13 8 days 25/77 15 minutes
20/68 3 days 30/86 12 minutes
120/248 1.5 hours 35/95 8 minutes
250/482 1.5 seconds
* These values are based on thermal decomposition, no wall effects or other catalytic (reaction) effects are
considered.
Source: McClain Ozone website (http://www.mcclainozone.com/research.html#top).
2.6. Bottled Water Manufacturing Industry and the U. S. Food and Drug Administration
The U.S. Food and Drug Administration (FDA) have responsibility over the bottled water
industry in the U.S. Bottled water is considered and regulated as a packaged food product by the
FDA. The FDA is also the government agency that monitors and inspects bottled water products
and processing plants under its general food safety program. There is no specific FDA bottled
water program [22].
In March of 1975, FDA recognized ozone treatment as a Good Manufacturing Practice (GMP)
within the bottled water industry as a means of sanitizing product water-contact surfaces and any
other critical area. The minimum ozone treatment for GMP is 0.1 parts per million (ppm) or 0.1
mg/L in an enclosed system for five minutes [23]. In 1982, the FDA declared ozone as
Generally Recognized as Safe (GRAS) for use as a disinfectant in the production of bottled water
up to a residual dissolved ozone concentration of 0.4 mg/l. The FDA reaffirmed the GRAS in
1995 [24].
Other GMPs require bottled water producers to:
1) Process, bottle, hold and transport bottled water under sanitary conditions;
14
2) Protect water sources from bacteria, chemicals and other contaminants;
3) Use quality control processes to ensure the bacteriological and chemical safety of the
water; and
4) Sample and test both source water and the final product for contaminants. [25]
Further proof of FDA’s endorsement of ozone’s use in food products is identified in 21 CFR
Food and Drugs, section 173 Secondary Direct Food Additives Permitted in Food for Human
Consumption, part 368 which states “ozone may be safely used in the treatment, storage, and
processing of foods, including meat and poultry when it is used as an antimicrobial agent in the
gaseous or aqueous phase in accordance with current industry standards of good manufacturing
practice” [26].
2.7. Use of Ozone as a Disinfectant in the Bottled Water Manufacturing Industry
Ozone is the second most powerful oxidizing agent, second only to fluorine. Ozone is 1.5 times
more powerful than gaseous chlorine, the most common water disinfection chemical, in terms of
its oxidizing potential and works at killing bacteria more than 3,000 times faster than chlorine
[27].
Ozone, when present in water, is a broad spectrum germicidal disinfectant that can destroy up to
99% of a wide range of pathogenic organisms that carry and spread disease including viruses,
bacteria, protozoan cysts, fungus, yeast, mold and organic materials that cause poor taste or odor.
Ozone accomplishes this disinfecting action due to the short time it takes to break apart and
return to its natural form of oxygen. As this process occurs, the free atom of oxygen oxidizes any
foreign particles in the water. This action virtually disintegrates most microorganisms / bacteria
or other organic matter, protecting the water from waterborne contamination [28]. Ozone
exhibits this disinfecting ability in both air and water and does it without the use of harsh
chemicals like chlorine and without having undesirable by-products associated with its use.
It is this unique ability to safely and effectively disinfect a wide variety of microorganisms that
made ozone the disinfectant of choice with the bottled water industry and greatly contributed to
15
the rapid growth experienced by the industry in the 1980’s and 1990’s. Ozone provided the
industry with the capability to disinfect all aspects of the bottling process – the water, the water
processing and bottling equipment, the bottle, the cap or closure and even the air – without using
chlorine. By using ozone, the bottlers could ensure that a great tasting, odor free, shelf-stable,
safe and healthy product was delivered to the market and ultimately the consumer [29].
2.8. Advantages / Disadvantages of Using Ozone as a Disinfectant
Ozone possesses other inherent advantages that are attractive to the bottled water industry, which
includes:
1) Ozone can disinfect at relatively low concentrations;
2) Ozone requires only a short contact time in water, which enables the microorganisms to be
killed within a few seconds;
3) Ozone decomposes rapidly into oxygen after disinfecting, and therefore, leaves no adverse
after taste or odor, harmful / undesirable by-products or residual effects that would need to
be removed from the water after treatment;
4) Ozone requires no other chemicals to disinfect – it is 100% natural and biodegradable;
5) Ozone oxidizes and precipitates iron, manganese and sulfides, thereby removing these
contaminants from the water and conditioning the water naturally without chemical
additives;
6) Unlike chlorine, ozone does not lead to the formation of harmful trihalomethanes;
7) Ozone destroys and removes algae;
8) Ozone reacts with virtually all organic matter in water;
9) Ozone can be used to control color, taste and odors in water;
10) Ozone is recognized as safe by the U.S. FDA for use as an antimicrobial agent in bottled
water; and
11) Ozone is easily and economically produced at the point of use and, consequently there are
no safety problems typically associated with shipping and handling a hazardous material.
16
2.9. Common Health Effects of Ozone Exposure
As mentioned in Chapter 1, the literature review revealed numerous scientific studies that
identified several common adverse health effects attributed to inhalation of ozone. The majority
of these studies typically involved human test subjects with varying characteristics such as young
or old, male or female, individuals with or without pre-existing lung conditions such as asthma
or chronic obstructive pulmonary disease (COPD), smokers/non-smokers, etc. The subjects were
exposed to a specific range/concentration (e.g., 0.05 to 0.75 ppm range) of ozone gas alone or
combined with a co-pollutant such as particulate matter. The tests were performed while the
subject was at rest or performing some type of moderate to vigorous steady or intermittent
exercise (usually riding a stationary bike or running on a treadmill) that caused the test subject to
progress from nasal to oral breathing coupled with increases in respiratory flow. Many of the
studies were conducted in a controlled inhalation chamber or while the test subject was wearing
a facemask. The studies were typically held over a set time period (e.g., 30 minutes to 8 hours).
The findings from the studies almost always identified adverse health effects involving mild to
severe lung inflammation or damage to bronchial and alveolar tissue as the ozone penetrated
deep into the lungs. The results of the majority of the studies also indicated a decrease in lung
function performance in the subject’s forced vital capacity (FVC), total lung capacity (TLC) or
forced expiratory volume in 1 second (FEV1).
Also mentioned in Chapter 1, the literature review identified very few studies involving the
quantitative assessment of an industrial environment to evaluate worker exposure to ozone and
the potential adverse health effects. Therefore, for the purpose of this research paper it is
assumed that workers employed in an industry where ozone is used in its processes would
experience health effects similar to those described in the multitude of controlled human
exposure, toxicological, animal and epidemiologic studies – particularly those involving
exposure to ground-level ozone.
The US EPA publication “Ozone and Your Health” [30] and the AIRNow website “Smog - Who
does it hurt?” [31], summarizes several of the common adverse health effects found in these
studies:
17
1) Irritates the respiratory system. When this happens, the exposed person may cough, feel
irritation or soreness in the throat, or experience chest tightness or pain when taking a deep
breath. These symptoms can last for a few hours after ozone exposure and may even
become painful.
2) Reduces lung function. When scientists refer to "lung function," they mean the volume of
air that a person draws in when they take a full breath and the speed at which the person is
able to blow the air out of the lungs. Ozone can make it more difficult for a person to
breathe as deeply and vigorously as normal. When this happens, the person may notice that
breathing starts to feel uncomfortable. If the person is exercising or working outdoors, they
may notice that they are taking more rapid and shallow breaths than normal. Reduced lung
function can be a particular problem for outdoor workers, competitive athletes, and other
people who exercise outdoors.
3) Inflames and damages cells that line the lungs. Some scientists have compared ozone's
effect on the lining of the lung to the effect of sunburn on the skin. Ozone damages the
cells that line the air spaces in the lung. Within a few days, the damaged cells are replaced
and the old cells are shed-much in the way that skin peels after sunburn.
Animal studies suggest that if this type of inflammation happens repeatedly over a long
time period (months, years, a lifetime), lung tissue may become permanently scarred,
resulting in less lung elasticity, permanent loss of lung function and a lower quality of life
[32].
4) Makes the lungs more susceptible to infection. Ozone reduces the lung’s defenses by
damaging the cells that move particles and bacteria out of the airways and by reducing the
number and effectiveness of white blood cells in the lungs. In addition, studies in animals
suggest that ozone may reduce the immune system's ability to fight off bacterial infections
in the respiratory system.
18
According to a study by Duke University Medical Center pulmonary researchers and study
lead author pulmonologist Dr. John Hollingsworth “it appears that ozone causes the innate
immune system to overreact, killing key immune cells, and possibly making the lung more
susceptible to subsequent invaders, such as bacteria.” [33].
5) Aggravates asthma. When airborne ozone concentrations are unhealthy, more people with
asthma have symptoms that require a doctor’s attention or the use of additional medication.
One reason this happens is that ozone makes people more sensitive to allergens, which are
the most common triggers for asthma attacks. In addition, asthmatics are more severely
affected by the reduced lung function and irritation that ozone causes in the respiratory
system.
6) Aggravates other chronic lung diseases such as emphysema and chronic bronchitis.
As concentrations of ground-level ozone increase, more people with lung disease visit
doctors or emergency rooms and are admitted to the hospital.
7) Can cause permanent lung damage. Repeated short-term ozone damage to children’s
developing lungs may lead to reduced lung function in adulthood. In adults, ozone
exposure may accelerate the natural decline in lung function that occurs with age.
Several of the above effects are considered to be transient and reversible in nature because they
eventually cease once the individual is no longer exposed to elevated concentrations of ozone.
Other effects, however, can lead to increased school or work absences, visits to doctors and
emergency rooms, hospital admissions and medication use among asthmatics.
Several studies identified during the literature review indicated the acute adverse effects from
repetitive exposure to low concentrations (0.2 ppm to 0.5 ppm) of ozone accumulate over many
hours. However, after several days of repeated exposures there appears to be resistance or
adaptation and noticeable diminishing of any further ozone-induced injury to the lungs
suggesting that tolerance may develop over time [34], [35], [36].
19
These and other health effects are discussed in the recently published US EPA document,
Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External
Review Draft) [2]. This document is a comprehensive compilation and review of the most recent
scientific studies associated with ozone exposure. These studies formed the foundation for the
most recent review of the primary (health-based) and secondary (welfare-based) National
Ambient Air Quality Standards (NAAQS) (See 2.10.2) for ozone and related photochemical
oxidants. The studies cited in this document are summarized in Appendix A.
2.10. Who is Most at Risk From Ozone Exposure?
There are several groups of people, described below, who are at especially high risk for health
problems associated with ground-level ozone exposure. These groups are particularly vulnerable
to unhealthy concentrations of ozone and become sensitive to ozone especially when they are
active outdoors. This is due in part to physical activity (such as jogging or outdoor work) causes
people to breathe faster and more deeply, drawing more ozone into the body. During activity,
ozone penetrates deeper into the parts of the lungs that are more vulnerable to injury. The US
EPA document Air Quality Index - A Guide to Air Quality and Your Health [37], identifies five
groups who are most vulnerable to ozone exposure. These groups consist of:
1) Children. Children often spend a large part of their summer vacation outdoors engaged in
vigorous activities making them the group that is at highest risk from ozone exposure.
Another reason is their lungs are still developing which makes them more susceptible to
ozone or other environmental threats than adults. Children are also more likely to have
asthma or other respiratory illnesses. Asthma is the most common chronic disease for
children and may be aggravated by ozone exposure.
Additionally, children breathe more rapidly than adults breathe and inhale more pollution per
pound of their body weight than adults inhale. In addition, children are less likely than adults
to notice their own symptoms and avoid harmful exposures [38].
20
2) Adults who are active outdoors. Healthy adults of all ages who exercise or work outdoors
(e.g., construction workers or road maintenance crews) are considered a "sensitive group"
because this activity in most cases takes place during the summer months, where ozone
production is at its peak. Additionally the activity level for those that exercise or work
outdoors can be vigorous leading to an increased respiratory rate and the inhalation of ozone
deep into the lungs.
3) Older adults (65 and older). These individuals may be at higher risk from ozone exposure
if they suffer from pre-existing respiratory disease, are active outdoors, or are unusually
susceptible to ozone.
4) People with respiratory diseases. Individuals who are afflicted with asthma, chronic
bronchitis, chronic obstructive pulmonary disease (COPD) and emphysema can be
particularly sensitive to ozone. There is no evidence that ozone causes asthma or other
chronic respiratory disease, but these diseases do make the lungs more vulnerable to the more
serious health effects at lower concentrations of ozone. Thus, individuals with these
conditions will generally experience the effects of ozone earlier and at lower concentrations
than individuals who are less sensitive to ozone.
5) People with unusual susceptibility to ozone. Scientists do not yet know why, but there is a
portion of the population that is otherwise healthy is simply more sensitive (or
hypersensitive) to the health effects of ozone gas than others. These individuals may
experience more health effects at lower ozone concentrations than the average person even
though they have none of the risk factors listed above. As is the case in other hypersensitivity
cases, there may be a genetic basis for this increased sensitivity.
The existence of populations especially vulnerable to the effects of ozone exposure can be
explained in part due to a wide variation in personal susceptibility. Certain individuals may
experience discomfort from hazardous substances at concentrations at or below the exposure
limit while others may not experience any effects at these or even slightly higher levels. Still
others may be affected more seriously by aggravation of a pre-existing condition, or by
21
development of an occupational disease. Furthermore, other workplace contaminants may affect
an individual's response. Finally, the effects of many combined chemical exposures are often
unknown or poorly defined [39].
2.11. Ozone – Dose and Effect
The following table provides a summary of airborne concentrations of ozone and the typical
heath effect(s) corresponding to the level.
Table 2.3 Toxic Effects of Ozone
Toxic Effects of Ozone
Concentration
(ppm) Duration of Exposure Effect
0.01 - 0.04 ppm - Odor Threshold
0.1 ppm - Minor eye, nose and throat
irritation.
0.1 ppm OSHA PEL - 8 hour average exposure limit
0.10 - 0.25 ppm 2-5 hours Headache, dry cough and some
reduction in lung function
0.3 ppm 2 hours
Reduction in lung function
during moderate work for all
persons.
0.3 ppm OSHA STEL - 15 minute exposure limit
>0.6 ppm 2 hours Chest pain, dry cough.
1 ppm 1 - 2 hours Lung irritation (coughing),
severe fatigue.
>1.5 ppm 2 hours
Reduced ability to think clearly.
Continuing cough and extreme
tiredness maybe lasting for 2
weeks. Severe lung irritation with
fluid build-up.
9 ppm Intermittent Severe pneumonia (arc welders).
10 ppm Immediately Dangerous to Life and Health
11 ppm 15 minutes Rapid unconsciousness.
50 ppm 30 minutes Expected to be fatal.
Source: Ozone Safe Work Practices, Work Safe BC, 2006 ed.
22
2.12. Exposure Limits
As previously mentioned, there is a multitude of scientific studies indicating the harmful effects
of breathing unhealthy concentrations of ozone. It is with this scientific knowledge that various
regulatory agencies, whether governing occupational settings or public health and the
environment, have established exposure limits designed to protect the industrial worker or the
individual exercising outdoors on a sunny summer day.
2.12.1 Occupational Exposure Limits
From a workplace standpoint, the industrial uses of ozone are extensive and varied and
encompass industries such as:
1) Aquaculture / Fish Farms (disinfecting)
2) Beverage and Brewery Industry (equipment and container cleaning and sanitation)
3) Drinking Water and Wastewater Treatment (COD/BOD reduction, disinfection, pesticide
removal and odor removal)
4) Food Processing (sterilization and fruit washing)
5) Medical Applications (equipment sterilization)
6) Pharmaceutical Industry (process and ultra-purity)
7) Paper and Pulp Industry (bleaching)
8) Textile Processes (dye removal)
9) Wineries (barrel and tank cleaning and sanitation and general surface sanitation)
10) Zoos and Public Aquariums (disinfection and sanitation)
Although not used directly as a gas in various welding operations, ozone is created as a by-
product when UV radiation from the electric arcs produced during metal inert gas (MIG) and
tungsten inert gas (TIG) welding splits oxygen molecules in the work area atmosphere into two
separate oxygen atoms that readily combine with other oxygen molecules.
To help protect workers from experiencing these acute and chronic adverse health effects of
ozone, several U.S. regulatory agencies and consensus standards organizations including OSHA,
ACGIH, NIOSH and The American National Standards Institute/American Society for Testing
23
Materials (ANSI/ASTM) have established occupational exposure limits which are summarized in
Table 2.4 below.
Table 2.4 Selected Occupational Exposure Limits for Ozone
Organization Type of Limit Exposure Limit
Occupational (Limits are for an 8-hour shift unless otherwise identified)
ACGIH TLV-TWA (heavy work)
TLV-TWA (moderate work)
TLV-TWA (light work)
TLV-TWA (2-h, all work types)
0.05 ppm
0.08 ppm
0.1 ppm
0.2 ppm
OSHA PEL-TWA
15-minute STEL
0.1 ppm
0.3 ppm
NIOSH REL-Ceiling
IDLH
0.1 ppm
5.0 ppm
ANSI/ASTM TWA
Ceiling
0.1 ppm
0.3 ppm
United Kingdom Health & Safety
Executive
15-minute STEL 0.2 ppm
British Columbia, Canada
TLV-TWA (heavy work)
TLV-TWA (moderate work)
TLV-TWA (light work)
TLV-TWA (2-h, all work types)
0.05 ppm
0.08 ppm
0.1 ppm
0.2 ppm
Germany Maximum Allowable Concentration
(MAK)
TWA
0.1 ppm
Submarine
NRC EEGL
1-hour
24-hour
1 ppm
0.1 ppm
CEGL
90-day
0.02 ppm
Aircraft
FAA >32,000 feet flight
4-hours or more flight segment cruising
between 27,000 feet and 32,000 feet
0.25 ppm
0.1 ppm
24
2.12.1.1 Adjusted Occupational Exposure Limits
The OSHA 8-hour PEL-TWA of 0.1 ppm and the ACGIH 8-hour TLV-TWAs were used as the
exposure limits of comparison for this research. However, these limits need to be adjusted to
reflect the 12-hour shifts worked by the equipment operators working in the Filler Room.
ACGIH recommends the use of the Brief and Scala model for adjusting TLVs to work shifts that
are greater in length than 8-hours/day. This model (see Equation 2-1) reduces the TLV
proportionately for both increased exposure time and reduced recovery time and is generally
used to adjust for shifts longer than 8-hours/day [40].
2-1
8 Hr {24 - Shift Length (Hr)}
Reduction Factor = x
Shift Length (Hr) 16
For a 12-hour shift, the reduction factor would be 0.5. OSHA does not provide specific guidance
for adjusting the ozone PEL for extended work shifts. However, in other OSHA standards the
PELs are adjusted in a simple proportionate manner. For example, the PEL is reduced by a
factor equal to the ratio of an 8-hour shift to the actual work shift: Adjusted PEL = 8-hour PEL x
{8-hour / Shift Length (Hr)}. In each case, the resulting adjusted exposure limit is lower than the
8-hour limit. See Table 2.5 for the adjusted exposure limits.
Table 2.5 12-Hour Adjusted Occupational Exposure Limits for Ozone
Organization Type of Limit Adjusted
Exposure Limit
ACGIH
TLV-TWA (moderate work) 0.04 ppm
OSHA
PEL-TWA 0.067 ppm
Part of the discussion included in Chapter 4 is a comparison of these 12-hour adjusted exposure
limits and the NIOSH REL-Ceiling Limit of 0.1 ppm with the mean airborne ozone
concentrations calculated as part of the analysis of the data set.
25
2.12.2 Public Health Exposure Limits
Similarly, in response to ground-level ozone’s presence in smog, the US EPA has also
established exposure limits to protect public health and the environment. Ozone has been
designated by the US EPA as one of the six principal pollutants under the Clean Air Act (law
enacted in 1970 that defines EPA's responsibilities for protecting and improving the nation's air
quality and the stratospheric ozone layer).
These six principal pollutants (also known as "criteria pollutants") are considered harmful to
public health and the environment. In addition to ozone, the other five pollutants are:
1) Carbon monoxide
2) Lead
3) Nitrogen dioxide
4) Particulate matter (PM2.5 and PM10)
5) Sulfur dioxide
Of the six pollutants, particulate matter and ground-level ozone are the most widespread health
threats [41].
The Clean Air Act also requires EPA to establish two types of national air quality standards for
each of the six principal pollutants. These are:
Primary standards that set limits to protect public health, including the health of "sensitive" or
at-risk populations such as asthmatics, children and the elderly.
Secondary standards that set limits to protect public welfare, including protection against
decreased visibility, damage to wildlife, crops, vegetation, national monuments, ecosystems,
buildings and visibility.
The Clean Air Act requires EPA to set these air quality standards, at levels sufficient but not
more than necessary, to protect the public health with an adequate margin of safety, and to
protect the public welfare, without considering the economic costs of implementing the standards
26
[42]. The values for the NAAQS are listed in Appendix B – the current standard for ozone is
0.075 ppm based on an 8-hour average. Also in response to the public health concerns posed by
these six principal pollutants, EPA created the Air Quality Index (AQI). The AQI provides a
uniform system of measuring pollution levels for five of the six major air pollutants regulated
under the Clean Air Act. Ozone is one of these five.
The AQI provides the EPA and the public with accurate, timely, and easily understandable
information about daily air quality for these air pollutants, their associated health concerns at
various levels and the precautionary steps the public can take to protect their health when these
pollutants reach unhealthy levels. The AQI combines numerical ratings and a color-coding
scheme to represent the potential health effects of various airborne concentrations of the five
pollutants.
For additional information on the color-coding scheme used by the AQI to alert people to the
various levels of health concerns refer to the US EPA publications “Understanding the Air
Quality Index” (Appendix C) and “Air Quality Index Colors” (Appendix D). For additional
information, specifically on the health effects of ozone and what measures the public can take to
protect itself from these effects, refer to two other the US EPA publications “Air Quality Guide
for Ozone” (Appendix E) and “Health Effects and Protective Actions for Specific Ozone
Ranges” (Appendix F).
One other agency that has established air quality guidelines for ozone is the World Health
Organization (WHO). This organization has established air quality guidelines for Europe and
has set the guideline value for ozone levels at 100 μg/m3 (0.05 ppm) for an 8-hour daily average.
27
Chapter 3
METHODS
The sections that follow in this chapter provide background information on the bottled water
manufacturing process to include:
1) Treatment of product water,
2) Description of the Filler Room,
3) The bottle filling cycle which incorporates bottle rinsing, filling and capping,
4) Sources of ozone gas generation in the Filler Room, and
5) Features in the Filler Room that may affect the concentration of airborne ozone.
The information presented in these sections should provide the reader with a better
understanding of how each of the above could influence the concentrations of airborne ozone
present in the Filler Room. Finally, the methodology that was employed to collect the air
samples that identified the airborne ozone concentrations in the Filler Room is discussed in great
detail in section 3.8 of this chapter. It was the results of this air sampling along with several
other variables that provided the input for the ozone monitoring data set (Appendix G) that will
be used as the basis for the statistical analysis summarized in Chapter 4.
3.1. Bottled Water Manufacturing - Process Overview
The bottled water manufacturing facility consists of four production lines – commonly referred
to in the plant and in this research paper as Line #1, Line #2, Line #3 and Line #4. Each
production line consists of the following equipment:
1) Blowmolders (equipment where a pre-form is blown into the shape of a bottle) – there are
two blowmolders per production line.
2) Filler (equipment where bottles are rinsed, filled and capped) – there is one Filler per
production line.
3) Labeler (equipment where a label is applied to the bottle) - there is one Labeler per
production line with the exception of Line #4 which has two.
28
4) Case Packer (equipment where individual bottles are put together and packaged to form a
case) - there are two Case Packers per production line with the exception of Line #4 which
has one.
5) Palletizer (equipment where individual cases are put together to form a pallet of product) -
there is one Palletizer per production line.
The flowcharts depicted in Figures 3.1 and 3.2 that follow provide a visual overview of the
sequence of steps associated with the manufacturing process for the spring and purified lines of
bottled water products. Steps included are:
1) Water processing
2) Ozone generation
3) Bottle manufacturing
4) Bottle filling and packaging
29
Figure 3.1 Natural Spring Product Water – Manufacturing Process Flowchart
Ozone GenerationWater Processing Manufaccturing
and Packaging
Bottle
Bottle Filling
Pipeline to Plant - 1
Bag Filters - 2
1 Micron Filters - 3
Storage Silos - 4 UV Light - 4a
0.2 Micron Filters - 5
Ozone Contact Tank - 8
Blowmolder - 10
Air Veyor - 11
Rinser - 12
Filler - 13
Capper - 14
Labeler - 15
Case Packer - 16
Palletizer - 17
Warehouse - 18
Shipping - 19
Consumer - 20
UV Light - 9
Rinsewater Tank - 7
Air Compressor - 6a
Oxygen Separator - 6b
Ozone Generator - 6c
30
Figure 3.2 Purified Product Water – Manufacturing Process Flowchart
Purified Products
Water Processing Manufaccturing
and Packaging
Minerals for
Ozone Generation
Bottle
Bottle Filling
Pipeline to Plant - 1
Bag Filters - 2
1 Micron Filters - 3
Storage Silos - 4 UV Light - 4a
UV Light - 5
5 Micron Filters - 6
Reverse Osmosis - 7
Blowmolder - 13
Air Veyor - 14
Storage Tanks - 8
Rinser - 15
Filler - 16
Capper - 17
Labeler - 18
Case Packer - 19
Palletizer - 20
Warehouse - 21
Shipping - 22
Ozone Contact Tank -
Consumer - 23
Air Compressor - 9a
Oxygen Separator - 9b
Ozone Generator - 9c
Rinsewater Tank - 10
From Step 5 - Spring
Water Flowchart
Mineral Solution
Preparation - 12a
Mineral Injection -
12b
31
Additionally, the following paragraphs provide a descriptive overview of the four major bottled
water manufacturing process steps.
1) Water Processing
Filtration of natural spring water - Product water is initially passed through a series of
filtration steps prior to being stored in silos waiting further processing.
Ozonation of natural spring water used for purified water products - While the bottles are
being blown, ozone is being generated and transferred to the plant’s ozone contact tanks
(OCTs) where the disinfection of the plant’s purified line of water products takes place. The
ozonated product water is transferred through pipelines from the OCTs to the Fillers in the
Filler room.
UV treatment of natural spring water used for the spring water products - UV light at a
wavelength of 254 nanometers is used to disinfect natural spring water while it is being held
in storage silos and as it flows from the OCTs through the transfer pipeline to one of the
Fillers in the Filler Room.
Mineral injection for the purified water products - A solution of water and minerals is
prepared in batch tanks located in the Mineral Injection Skid (MIS) room. When needed, the
mineral solution is transferred to the OCTs where the water for the purified water products is
being prepared.
2) Ozone Generation
The ozone gas used at the plant is generated on-site by three ozone generators using the
corona discharge method. Ozone is used in the plant to ozonate product water, bottle rinse
water and water used in hose stations. The ozone generation equipment is located in the
plant’s water processing room. The ozonation process is discussed in more detail in section
3.3.
32
3) Bottle Manufacturing
A pre-form (appearance and size is similar to a test tube with a threaded neck) made of
polyethylene terephthalate (PET) is pre-heated at temperatures between 220oF to 230
oF in an
oven-like structure containing quartz lamps. The pre-form is then conveyed to a two-section
mold where it is blown into the configuration of a bottle using high-pressure compressed air.
This transformation from pre-form to finished bottle is accomplished in a machine called a
Blowmolder. The blown bottle is then transported to the Filler Room via an air conveyor
that moves the blown bottles with forced air.
4) Bottle Filling and Packaging
Rinsing/Filling/Capping - In the piece of equipment called the Filler, the empty bottle is first
rinsed with ozonated water, filled with product water and finally a closure or cap is applied to
the bottle. Cap handling equipment provides a supply of caps to the Filler. Once capped the
bottle is carried out of the Filler room on a belt conveyor with its next stop being the Labeler.
Labeling - Just as is name implies, the Labeler applies a label to the bottle that is typically
applied with a food grade adhesive. Once labeled, the bottle is transported on a belt
conveyor to the case packer.
Case formation - In the case packer, the bottles are aligned and formed into cases of 12, 24 or
32 bottles. The bottles are set on a cardboard tray and a plastic shrink wrap is draped around
the case. The case then travels through a heat tunnel where the wrap is “heat shrunk” around
the case. Once a case is packaged, it is transported on a belt conveyor to the palletizer.
Pallet formation - Individuals cases are formed into rows which are placed on a pallet. A
pallet is generally comprised of 5 to 6 rows of cases with 45 to 72 individual cases. The
pallet then has several layers of stretch wrap spun around to stabilize the pallet. The pallet is
then moved to the plant’s warehouse via forklift and is stored in racks where it awaits its
final destination – the consumer.
33
3.2. Product Water Treatment - Filtration
The plant’s portfolio of bottled water products is comprised of natural spring water and purified
water that has a blend of minerals added for flavor and taste. The water source used for all of
the plant’s products is natural spring water from an artesian spring located in Centre County, PA.
This spring water is gravity fed approximately 5 miles to the plant through a 16-inch diameter,
ductile iron pipeline. As the spring water enters the plant it initially passes through a series of
bag filters with a pore size of 15 microns and two banks of cartridge filters with a pore size of 1
micron. The purpose of the bag filters is to remove large materials. The 1 micron filters fall into
the class of microfiltration. Microfiltration has the following characteristics.
1) Very high effectiveness in removing protozoa (for example, Cryptosporidium, Giardia);
2) Moderate effectiveness in removing bacteria (for example, Campylobacter, Salmonella,
Shigella, E. coli);
3) Not effective in removing viruses (for example, Enteric, Hepatitis A, Norovirus, Rotavirus);
and
4) Not effective in removing chemicals [43].
After the spring water passes through these filters, the filtered water is stored in two of the
plant’s four water storage silos until it is needed to produce a batch of product water. The other
two storage silos are used to store water that has passed through the plant’s Reverse Osmosis
(RO) system. These silos are constructed of stainless steel, are approximately 80’ in height,
vertical in orientation and have a capacity of 60,000 gallons. These tanks are typically filled to a
level of 50,000 gallons.
All four of the storage silos are under the constant treatment of two UV lights with a wavelength
of 254 nanometers. The purpose of the first UV light is to disinfect the air in the headspace of
the silo to prevent growth of bacteria and other airborne contaminants. The second UV light is
placed in the silo’s recirculation pipeline to help disinfect the water in the storage silos when the
tanks are placed in the recirculation mode.
34
The natural spring water undergoes one more filtration step prior to being bottled. The water is
passed through two banks of cartridge filters with a pore size of 0.2 micron for final removal of
potential contaminants.
In addition to the initial microfiltration, the water for the purified line of products also undergoes
RO treatment. Water from either of the two spring water storage silos is transferred to the
plant’s RO system where it passes through a UV light and three banks of 5 micron cartridge
filters before it receives the RO treatment. RO is a high pressure water purification system using
semipermeable membranes with a tight pore structure of approximately 0.0001 micron by which
the solvent (spring water) is filtered of solutes (large organic molecules, viruses, ions and other
dissolved impurities) by being forced through the membranes through which the solvent, but not
the solute, passes through.
RO filtration can remove 90 to 99+ % of certain contaminants. RO systems have the following
characteristics:
1) Very high effectiveness in removing protozoa (for example, Cryptosporidium, Giardia);
2) Very high effectiveness in removing bacteria (for example, Campylobacter, Salmonella,
Shigella, E. coli);
3) Very high effectiveness in removing viruses (for example, Enteric, Hepatitis A, Norovirus,
Rotavirus); and
4) Will remove common chemical contaminants (metal ions, aqueous salts), including sodium,
chloride, copper, chromium, and lead; may reduce arsenic, fluoride, radium, sulfate, calcium,
magnesium, potassium, nitrate, and phosphorous [43].
After the water passes through the RO system, it is essentially pure water. The RO water is
stored in the plant’s other two water storage silos until it is needed to produce a batch of mineral-
enhanced product water.
35
3.3. Product Water Treatment - Ozonation
The plant has three ozone generators that are used to produce the ozone that is used on-site for
ozonating the water used:
1) For the plant’s purified water line of products,
2) For the bottle rinsing cycle prior to filling,
3) To provide lubricating water for the Filler rinser wheel and bottle pedestals,
4) For ozone flushes (type of equipment sanitation), and
5) In the hose stations in the Filler Room and MIS room
The three generators consist of two Brand A ozone generators and one Brand B ozone generator.
All three ozone generators use the corona discharge method to produce ozone.
Corona discharge is the condition created when a power supply is used to produce a high-energy
electrical discharge of 3,000 or more volts across two electrodes that are separated by an air gap.
Ozone is created when oxygen molecules in a gas such as oxygen-enriched air are passed
through the air gap and exposed to the high-energy electrical discharge. The oxygen molecules
(O2) are split by the electrical discharge resulting in two individual oxygen atoms (O+O). The
individual unstable oxygen atoms have a negative charge and will bond quickly with another
oxygen molecule to produce a three-atom molecule of ozone (O3) gas. This is similar to the
process that takes place when ozone is created naturally in the earth’s stratosphere by UV light.
A great deal of heat is generated from this process, which is removed from the ozone generating
equipment by a water jacket around the equipment. Figure 3.3 below illustrates a typical corona
discharge system.
36
Figure 3.3 Ozone Generation from Corona Discharge
Source: Ozone Solutions website (http://www.ozonesolutions.com/journal/2011/how-is-ozone-made-2nd-
installment/).
The process used by the Brand A equipment to generate ozone is as follows:
1) A supply of compressed air is generated by the plant’s low pressure air compressors located
in the plant’s Compressor Room.
2) This supply of air is initially sent to a dryer where humidity and moisture is removed from
the air stream. Dry air greatly increases ozone production (two to three times) compared to
atmospheric conditions [44].
3) The air is then held in a receiver until it is needed in the plant’s water processing room to
generate oxygen.
4) Once needed, the air in the receiver is fed to an oxygen generating unit located in the plant’s
water processing room. This piece of equipment conditions the compressed air (removes any
residual moisture, oil, particulate matter and other impurities from the air stream) and
produces pure oxygen which is held in an interconnected receiver. This oxygen stream will
serve as the feeder gas for the plant’s two Brand A ozone generating units.
5) When the Brand A ozone generators are called upon to produce ozone, the oxygen in the
receiver is fed to the Brand A equipment where they convert oxygen to ozone using the
corona discharge technology.
The plant’s Brand B generator also uses the corona discharge technology to generate ozone.
Unlike the Brand A equipment, however, the Brand B generator does not have a supplied stream
37
of oxygen as a feeder gas. This generator is somewhat self-sustaining in the fact that it
conditions a stream of ambient air and uses the oxygen from this air stream for its ozone
generating cycle.
Due to ozone’s rapid decomposition rate and its inability to be stored for any extended or
significant length of time, ozone gas must be dissolved in water immediately after it is generated
[45]. This is the point in the production process where the plant’s four OCTs enter the ozonation
cycle. The ozonation of the product water actually takes place within the OCTs. The function of
the OCTs is to maintain the ozone in contact with the product water for a set period of time to
ensure complete disinfection. This time is referred to as the “contact time. The International
Bottled Water Association (IBWA) recommends that ozone be applied in the 1.0 to 2.0
milligram per liter (mg/L) range for a period of four to ten minutes contact time to safely ensure
disinfection. Application at this level helps maintain 0.1 to 0.4 ppm residual ozone in the water at
the time of bottling. This provides an additional safety factor because the bottles can be
disinfected and sanitized while they are being filled with product water [46].
The OCTs are constructed of stainless steel, approximately 16 feet in height with a diameter of 3
feet, vertical in orientation and have a capacity of 750 gallons. The OCTs are filled to 80% of
capacity when supplying product water to one of the Fillers. Three of the OCTs supply ozonated
water to the plant’s Line #2, #3 and #4 Fillers.
NOTE - The Line #1 OCT is dedicated to natural spring water products only and therefore does
not produce any of the purified water products. However, it does have an ozone transfer line
from the Brand A equipment connected to it for the purpose of ozonating water for ozone flushes
(method of sanitization) in the Line #1 Filler.
RO water is used to produce the plant’s purified water products that are treated with ozone via
the following process:
1) In the MIS Room, a batch of the proprietary mineral solution for the mineral added products
is prepared in 150-gallon batch tanks using water from one of the RO storage silos. When
needed, these minerals are dosed into the Line #2, #3 or #4 OCTs.
38
2) At the same time, RO water is fed from one of the two RO storage silos to the Line #2, #3 or
#4 OCTs.
3) Ozone produced in the Brand A equipment is fed through a stainless steel distribution
pipeline to the plant’s Lines #2 and #3 OCTs where a gas bubbling system, located in the
bottom of the OCT, diffuses or “bubbles” the ozone into the water.
NOTE - With the diffusion or “bubbling” process, ozone is bubbled through the water in the
OCT. The disinfection of the product water occurs when the bubbles of ozone gas come in
contact with impurities in the water as the bubbles rise slowly through the OCT and escape into
the tank’s head space as ozone gas. The amount of ozone diffused into water depends on the
surface area of the gas/water interaction. Therefore, the smaller the bubbles, the more surface
area is available for the gas/water interaction the more efficient the bubbles will be at ozonating
the water [46]. As the bubbles of ozone pass through the water in the OCT, the third unstable
oxygen atom of the ozone molecule detaches, attacks, and destroys impurities in the water. The
residue in the water is pure oxygen, which quickly off-gasses in a few minutes. Any excess
dissolved ozone which is not needed for treatment, reverts to simple oxygen in approximately 20
to 30 minutes.
4) The Brand B generator supplies the ozone for the product water produced in the OCT for the
Line #4 Filler. The Brand B generator also uses a stainless steel distribution pipe line to
transfer the ozone to Line #4 OCT. Ozone for this OCT is not bubbled into the water;
instead ozone is diffused into this tank via a venturi injection system that is located on the
OCT recirculation pipeline.
5) The water in the OCTs is ozonated to a concentration between 0.1 ppm and 0.6 ppm.
6) When the ozone specification in the water present inside the OCT is reached, the computer
logic controlling the operation calls for the mineral solution from the batch tank to be dosed
into a pipeline that is located in the MIS Room. This pipeline then feeds the mineral solution
to the Line #2, #3 or #4 OCTs.
7) As the bottled water production cycle continues, the mineral solution continues to be dosed
into the pipeline while ozone is continuously supplied to the OCTs.
39
Ozone produced from the Brand A equipment is also the source of the ozone for the plant’s 300-
gallon Rinsewater Tank. This is the ozonated water that is piped to the Filler and used for
rinsing empty bottles prior to them being filled. This tank also supplies the ozonated water for
the bottle pedestals around the Filler bowl and the hose stations located in the Filler Room. The
water in this tank is also ozonated to a concentration between 0.1 to 0.6 ppm.
3.4. Filler Room
As previously mentioned, the Filler Room is the work area where the bottle rinsing, filling and
capping activities take place. It houses all four of the plant’s Fillers. This is also the work
environment where the air sampling for worker exposure to airborne ozone was performed for
this research project.
Figure 3.4 is a diagram of the Filler Room that provides a visual reference that illustrates the
following:
1) Spatial layout of the four Fillers,
2) Footprint of the original Filler Room that housed the Fillers for Lines #1, #2 and #3 as well
as the Fillers for retired production Lines #4 and #5,
3) Footprint of the addition to the Filler Room that was constructed to house Line #4 Filler,
4) Location of a temporary wall erected to allow for the construction of the Filler Room
addition while production continued on Lines #1, #2 and #3, and
5) Location of the Filler Room’s three air handling units (AHUs).
40
Figure 3.4 Filler Room Diagram
81'
AHU #3
AHU#1
Line #4 Filler
Original section of Filler Room 48'that included Lines #4 and #5 Fillers Filled
Bottles
Line #4 Expansion
51'
150'
Filled
Bottles
Filled
Bottles Key to Shapes
Capper
AHU#2 Filler
Rinser
Filled
BottlesAir Handling Unit
30'
Diagram is not to scale. For illustration purposes only - spacing of equipment is approximate.
Original section of Filler Room that
contained Lines #1, #2 and #3 Fillers
Line #1 Filler
Line #2 Filler
Line #3 Filler
Temporary Wall
41
The original footprint of the Filler Room was a 4,500 ft2 rectangular-shaped room 30 feet wide x
150 feet long with a ceiling height of 15 feet. This calculates to a volume of 67,500 ft3. The
Filler Room has walls erected from either concrete block or glass supported by an aluminum
framework. The floor of the Filler Room is constructed of concrete with an epoxy covering with
non-skid imbedded grit. Ceiling tiles fabricated for wet environments serve as the finish for the
ceiling.
The original Filler Room housed the Fillers for Lines #1, #2 and #3. It also housed the Fillers for
Lines #4 and #5. However, these two Fillers were removed to make room for the new Line #4
production line and Filler.
While the research for this project was taking place, a major addition to the Filler Room occurred
which involved the installation of a new high-speed bottling production line. This addition
housed the Line #4 Filler and cap handling equipment. This expansion involved the construction
of a 2,448 ft2 room 48 feet wide x 51 feet long with a ceiling height of 15 feet. The addition
changed the shape of the Filler Room from rectangular to “L” shaped. The total volume of the
addition was 36,720 ft3. The addition has the same wall, floor and ceiling tile construction. The
addition also added a third air handling device, AHU #3.
To allow for the bottling operations to continue on Lines #1, #2 and #3 while the construction of
the Line #4 addition took place, a temporary wall formed by 2 inches x 4 inches boards and
polyethylene plastic sheeting was erected to close off the active portion of the Filler Room. This
wall reduced the length of the original footprint of the Filler Room by approximately 48 feet to a
dimension of 30 feet wide x 102 feet long or 3,060 ft2. This new configuration housed Lines #1,
#2 and #3 and totaled 45,900 ft3. The new configuration also left AHU #2 as the only air
handling device in this area.
The Filler Room is designed with the principles of a classical clean room in mind. Federal
Standard 209E defines a clean room as a room in which the concentration of airborne particles is
controlled to specified limits. British Standard 5295 defines a clean room as a room with control
of particulate contamination, constructed and used in such a way as to minimize the introduction,
42
generation and retention of particles inside the room and in which the temperature, humidity, air
flow patterns, air motion and pressure are controlled [21].
A clean room differs from an ordinary ventilated/conditioned room mainly in three ways.
1) Room positive pressurization,
2) Increased air supply, and
3) The use of high efficiency air filters [21].
The first of these features to be discussed is the Filler Room having positive pressure with
respect to the remainder of the plant. The reason for this is to help prevent infiltration of
airborne contaminants that could taint product water. Positive pressure is produced by extracting
less air from the room than is supplied to it.
The positive pressure in the Filler Room is produced by three AHUs mounted above the Filler
Room. The housing and ductwork for the three AHUs is located on a mezzanine located directly
above the ceiling of the Filler Room, essentially on the roof of the room. These AHUs also have
the capability of heating or cooling the air they supply to the Filler Room. The original foot print
of the Filler Room contained two AHUs, AHU #1 and AHU #2 with each designed to supply
11,500 cfm of air (or 23,000 cfm total) to the Filler Room. A third AHU, AHU #3, was added to
the Filler Room during the addition of Line #4. This AHU was designed to supply 7,500 cfm to
the Filler Room.
These AHUs circulate the air within the Filler Room by exhausting air out of the Filler Room
through their main exhaust ducts and returning a supply of “fresh” air to the Filler Room through
thirty-four (34) 2 feet x 2 feet diffusers spaced throughout the ceiling of the Filler Room on 8
foot centers. The supplied volume of air to the Filler Room is closer to 25,000 cfm instead of the
theoretical design of 30,500 cfm. This volume of air was determined through air balancing
studies conducted in the Filler Room by a third-party consultant. This reduction in airflow
volume is attributed in part to friction and shock losses in the ductwork of the AHUs caused by
straight runs, bends, branches, tees and elbows. The air returned to the Filler Room is a
combination of ambient air exhausted from the Filler Room and “fresh” air drawn from either
43
outside of the building through fresh air intakes or inside the plant through louvers in the
ductwork of the AHUs.
AHU #1 has its exhaust duct work located in the Filler Room ceiling between the cap handling
equipment and the work platform for Line #4 Filler. AHU #2 has its exhaust duct opening
located in the glass wall of the Filler Room between Line #1 and #2 Fillers. AHU #3 has its
exhaust duct opening located in the Filler Room ceiling above the point where bottles exit the
Line #4 Filler. The location of each exhaust duct is depicted on the Filler Room diagram (refer to
Figure 3.4).
The AHUs are typically set at an 80-90% recirculation level meaning 80-90% of make-up air
returning to the Filler Room initially comes from the Filler Room while the remaining 10-20%
comes from a fresh air source. The purpose of re-circulating the Filler Room air is to conserve
energy by not having to heat or cool such a large volume of air. With this recirculation of Filler
Room air, obviously comes a recirculation of the residual ozone present in the atmosphere of the
Filler Room. This re-circulated ozone contributes to the background concentration of ozone
present in the Filler Room to which the workers in the Filler Room are exposed. There may also
be a very small fraction of naturally occurring ozone that infiltrates from the outdoors and enters
the plant through its roof air intake fans. This ozone enters the atmosphere of the plant and is
drawn into the Filler Room through the AHUs. Unfortunately, neither of these sources of ozone
were evaluated and quantified as part of the research.
In addition to the Filler Room having positive pressure, each of the four Fillers maintains
positive pressure in relation to the Filler Room. The positive pressure present in each of the
Fillers is produced by multiple blowers mounted on the top of the Fillers. These blowers draw
air through stainless steel mesh screens that house high efficiency particulate air (HEPA) filters.
The HEPA filters are used to help maintain a particulate free environment inside the Fillers.
The second clean room feature to discuss is the increased air supply in the Filler Room as a
means of contamination control, primarily the removal of particulates. Normal air-conditioning
systems are designed to provide 0.5 to 2 air changes per hour essentially based on the occupancy
44
level or as determined from the building exhaust levels. A clean room would have at least 10 air
changes per hour (indicative of a Class 100,000 clean room) and could be as high as 600 air
changes per hour (indicative of a Class 1 clean room) for absolute cleanliness. The purpose of
the increased air supply and subsequent numerous air changes in a clean room type environment
is to ensure an optimum removal of any contamination to an acceptable level for the workers or
the product. Further, the increased ventilation in a clean room also helps to maintain an
acceptable working climate for the workers in regards to humidity and temperature [21] (Bhatia
2012).
The equation for calculating air changes is as follows:
n = 60 q / V 3-1
where
n = air changes per hour (ACH)
q = air supplied to the room {Cubic Feet per Minute (cfm)}
V = volume of the room (Cubic Feet)
To calculate the air changes per hour in the original Filler Room foot print (Lines #1, #2, #3, #4
and #5) the following information is used:
q = 23,000 cfm (combined AHU #1 and AHU #2 supplied air volume)
V = 67,500 ft3 (original footprint of Filler Room 30 feet width x 15 feet height x 150 feet length)
n = 60 (23,000) / 67,500
n = 20.44 ACH
To calculate the air changes per hour in the modified Filler Room during the construction of Line
#4, the following information is used:
45
q = 11,500 cfm (supply of air from AHU #2 only; AHU #1 was isolated from modified Filler
Room by polyethylene sheeting wall)
V = 45,900 ft3
(30 feet width x 15 feet height x 102 feet length with the polyethylene sheeting
wall isolating Lines #1, #2 and #3 from the Line #4 addition)
n = 60 (11,500) / 45,900
n = 15.03 ACH
Once the Line #4 construction was completed, the polyethylene sheeting wall was removed
joining Lines #1, #2 and #3 with Line #4. This addition added a room with the dimensions of 48
feet wide x 15 feet height x 51 feet length for a total of 36,720 ft3. This brought the total area of
the new Filler Room to 6,948 ft2 with a volume of 104,220 ft
3. With the addition of Line #4, a
third AHU was brought on line to help maintain the positive pressure in the Filler Room as well
as provide comfort heating and cooling for the workers. This AHU provided 7,500 cfm of
supplied air to the Filler Room.
To calculate the air changes per hour in the new Filler Room, the following information will be
used:
q = 30,500 cfm (the combined 23,000 cfm from AHU #1 and AHU #2 plus the 7,500 cfm
supplied by AHU #3)
V = 104,220 ft3
(original Filler Room 30 feet width x 15 feet height x 150 feet length plus the 48
feet width x 15 feet height x 51 feet length addition to house the Line #4 equipment)
n = 60 x 30,500 / 104,220
n = 17.56 ACH
The final clean room feature to discuss is the use of HEPA filters, which are used to filter the
supply of air into a clean room to ensure the removal of small particulates. The Filler Room
46
AHUs are equipped with a 3-staged filtering system consisting of bag, pleated and HEPA filters.
This series of filtration equipment prevents particulate contamination from entering the
cleanroom atmosphere. As previously mentioned, each of the four Fillers also has HEPA filters
that help to further cleanse the air inside the Fillers of particulate contamination.
3.5. Bottle Filling Process
Housed within the Filler Room are four Fillers with attached conveying and cap handling
equipment. As shown on Figure 3.4, each of the four Fillers is comprised of three interconnected
concentric chambers:
1) Bottle rinsing wheel,
2) Filler bowl, and
3) Capper wheel.
Before a bottle is filled with product water, it goes through a water rinse cycle to remove any
dust or other contaminants that may have accumulated on or in the bottle during its transport
from the Blowmolding equipment to the Filler Room via air conveyors. The actual rinsing takes
place in the bottle rinsing chamber of the Filler. Each individual bottle is conveyed to the Filler
and is inverted atop a rinser head that cycles compressed air, ozonated water spray then
compressed air again.
Once rinsed, the bottle moves to the Filler chamber where the bottle is filled with a prescribed
volume of product water from the Filler bowl. The bottle then moves to the Capper chamber of
the Filler where a closure or cap is applied to it before it exits the Filler on a conveyor heading to
the Labeler.
It is during this portion of the bottled water production cycle that the majority of the ozone is
liberated to the atmosphere of the Filler Room. For Lines #1, #2 and #3, this occurs through 78
positions that rinse bottles and 60 positions that fill bottles. For Line #4, this occurs through 120
positions that rinse bottles and 120 positions that fill bottles. The speed of a Filler is such that it
takes mere seconds to complete a cycle of rinsing a bottle, filling a bottle and capping a bottle.
47
Bottles manufactured and filled at the plant consisted of the following sizes:
Natural spring water:
1) 8.5 ounces (251 ml),
2) 11.2 ounces (330 ml) ,
3) 16.9 ounces (500 ml),
4) 20 ounces (591 ml),
5) 25 ounces (739 ml),
6) 33.5 ounces (1 liter), and
7) 50.7 ounces (1.5 liter)
Purified water:
1) 8.5 ounces (251 ml),
2) 16.9 ounces (500 ml)
Line #1 is used strictly for production of natural spring water products, while Lines #2, #3 and
#4 are used to produce either natural spring water or purified water products.
The Line #1, #2 and #3 Fillers fill bottles at a rate ranging from 250 to 560 bottles / min for the
larger size bottles (20 ounce and larger) and approximately 600 bottles / minute for the smaller
size (8.5, 11.2 and 16.9 ounce). The Line #4 Filler fills bottles at a rate of approximately 1,080
bottles / minute. Only the 16.9 ounce size bottle is run on Line #4.
The temperature of the water used to rinse the bottles is typically in the mid 50os F, while the
temperature of product water at time of bottling ranges from the mid to upper 50os F in the colder
months of the year to the mid 60os to low 70
os F in the warmer months. As previously
mentioned in section 2.2, the half-life in water is 30 minutes for 59oF, 20 minutes at 68
oF and 15
minutes for 77oF.
48
3.6. Sources of Ozone in Filler Room
With the bottle filling process, comes the introduction of ozone into the Filler Room and the
source of ozone exposure for the workers operating the equipment. The primary sources of
ozone gas liberation into the atmosphere of the Filler Room are:
1) Bottle rinse water,
2) Water for the purified products,
3) Constant trickle of water used to lubricate Rinser wheel and bottle bases/pedestals around
Filler bowl (water continues to flow regardless if a Filler is in operation or not),
4) Naturally occurring ozone in the earth’s atmosphere that is brought in as the “fresh” air
portion of the Filler Room air supply, and
5) Residual ozone present in the air recycled from the Filler Room.
3.7. Factors Affecting Airborne Ozone Concentrations
There are several factors that are suspected of having a potential effect on the airborne ozone
concentration that the workers in the Filler Room are exposed to while operating the bottle filling
equipment. These consist of:
1) Product mix – proportion of natural spring water versus purified water being produced,
2) Bottle size,
3) Bottles produced / minute,
4) Ozone level in the bottle rinse water or product water, and
5) Number of Fillers in operation at the same time.
The amount of ozone gas that each of these items contributes to the overall concentration will be
discussed in more detail in the statistical analysis section of Chapter 4.
3.8. Ozone Sampling Methodology
The sampling strategy that was followed for this research project consisted of measuring the
concentration of airborne ozone present in the work area atmosphere around each of the four
49
Fillers while bottles were being filled with product water. The instrument that was used to
measure the ozone was the Aeroqual Ozone Series 500 Monitor. The Aeroqual is a hand-held
direct reading monitor. The Aeroqual 500 User Guide describes the device as a single gas
monitor that is designed to measure the ambient concentration of ozone in real time employing
“active sampling.” The “active sampling” requires air to be drawn passed the instrument’s low
concentration sensor head by an internal fan in order to maximize the capture of ozone and
minimize ozone losses. The low concentration ozone sensor head is designed to measure ozone
concentrations from 0.000 to 0.500 ppm with an accuracy of +/-0.010 ppm from 0 to 0.100 ppm
and 10% from 0.100 to 0.500 ppm and has a resolution of 0.001 ppm. The instrument is
equipped with built-in data-logging capability and features minimum, maximum, average and
STEL reading functions. [47]
Refer to Figures 3.5 and 3.6 for illustrations of the Aeroqual Ozone Series 500 Monitor.
Figure 3.5 Aeroqual Ozone Series 500 Monitor – Exterior View
Source: Aeroqual 500 User Guide
50
Figure 3.6 Aeroqual Ozone Series 500 Monitor – Interior View
Source: Aeroqual 500 User Guide
The sampling protocol consisted of using the Aeroqual monitor to take real-time air samples of
airborne ozone at six positions around the perimeter of each of the four Fillers. These samples
were of the “area” type, which means the samples were taken at a specific point in the Filler
Room rather than on an individual worker. For the purpose of this paper, the six positions are
referred to as “sampling points.” The positions were selected because they correspond to areas
around the Filler that represent the three primary sections of the Filler (the bottle rinser wheel,
filler wheel and capper assembly) that are sources of ozone gas liberation into the atmosphere of
the Filler Room. The positions are:
1) Sampling Point #1 - Near cap hopper. Location serves as a control point due to its distance
from the Filler. This is also the location in the Filler Room where the Filler Operator spends
time loading caps into the cap hopper.
2) Sampling Point #2 - Near the Filler Operator work platform and Filler sash door. The Filler
Operator spends the majority of the work shift “stationed” at this location monitoring the
51
operation of the Filler, clearing jams, conducting quality control tests, recording data, etc.
This point best reflects the workplace exposure to ozone for the Filler Operator.
3) Sampling Points #3 and #4 - Two points around the rinser chamber of the Filler where
ozonated water is used to clean bottles prior to filling. These samples were taken at
plexiglass windows mounted in an exterior wall of the Filler.
4) Sampling Point #5 - Adjacent to the filler chamber where the bottles are filled with either
natural spring or ozonated product water, also at a plexiglass window.
5) Sampling Point #6 - At a plexiglass sash door near the capper chamber of the Filler and
adjacent to the section of the Filler deck where excess water tends to migrate to and drain out
of the Filler.
Figure 3.7 provides a schematic of the Filler Room that illustrates the positions of the Line #1,
#2, #3 and #4 Fillers along with the location of the sampling points where the airborne ozone
concentrations were measured for this research project. The positions are depicted on the
diagram as blue-colored circles with black-colored numbers.
52
Figure 3.7 Filler Room Schematic Illustrating Location of Sampling Points
This diagram displays the location
of the four Fillers that were
included in the air sampling
performed for this research project.
Sampling points are indicated on
the diagram by blue-colored circles
with a black numbers.
53
A sampling cycle consisted of measuring the airborne ozone concentrations at six positions
around each of the four Fillers. A complete series of samples taken at the six positions at each of
the four Fillers is referred to as a “sampling period.” During each sampling period, the airborne
ozone concentrations were measured three times at each sampling point using the Aeroqual
monitor. It took approximately 3-5 minutes to collect the three measurements for each sampling
point. The three measurements were recorded on the Ozone Monitoring Data Sheet (Appendix
H). The average of the three measurements was calculated with the result recorded on the data
set under the Ozone_Air column. This is the response variable for the statistical analysis which
will be discussed in more detail in Chapter 4.
Other information recorded on the Ozone Monitoring Data Sheet included the production status
of each of the four Fillers (meaning whether or not it was in operation at the time the samples
were being taken), the type of product being produced whether spring or purified, the size of the
bottles being produced and the temperature and humidity in the Filler Room at the time the
sampling period started.
The research reflects a total of 24 sampling periods performed between June 19, 2007 and
January 22, 2008. A timeline that displays the date when each sampling period was performed
follows as Figure 3.8. This timeline also shows when each of the AHUs was in operation, when
the temporary wall between Lines #3 and #4 was removed and when Line #4 came on line.
Figure 3.8 Air Sampling Timeline
While each sampling period was being performed, there were two other variables associated with
the filling of bottles that were documented in the data set. These were the ozone level in the
rinse water and the product water. The source of the data for the ozone level in the rinse water
came from samples, taken by QA lab personnel, of the water present in the rinse water tank. The
54
product water in filled bottles, pulled directly from the Fillers after the bottle was capped, served
as the source for the data for the level of ozone in the product water.
The impact that each of the factors previously mentioned in this chapter have on the
concentration of airborne ozone in the Filler Room will be discussed in more detail in Chapter 4.
55
Chapter 4
RESULTS AND DISCUSSION
4.1. Statistical Analysis
The goal of this research project is to characterize the airborne concentrations of ozone that
workers are exposed to in an active bottled water manufacturing facility.
The key research questions to be answered are:
Research Question 1:
1) Is there any significant difference between airborne ozone concentrations under the following
conditions?
a) Different air monitoring sampling points
b) Production status, to include:
Number of Fillers in operation (or the start-up of the Line #4 Filler),
Production of purified or spring products or no production, or
Size of bottles
c) Number of air handling units (AHUs) in operation
Research Question 2:
Is there a relationship between the airborne ozone concentration around the Fillers and the ozone
level in the rinse water or product water?
Research Question 3:
How do airborne ozone concentrations compare with applicable occupational exposure limits
such as the 8-hour and 12-hour adjusted exposure limits for the OSHA PEL and ACGIH TLV-
TWA, the OSHA 15-minute STEL and the NIOSH REL-Ceiling Limit?
56
Research Question 4:
What is the probability that mean airborne ozone concentrations for sampling points 1 and 2,
which are most reflective of the Filler Operator’s workstation, exceed applicable occupational
exposure limits?
A series of statistical analyses consisting of the following elements were conducted to examine
these research questions:
1) Construction of a model to identify significant factors affecting the response variable
(Ozone_Air), and the potential interactions among the various factors.
2) Testing of the correlation between the airborne ozone concentration and the ozone level in
the rinse water and product water.
4.2. Study Design
The data generated for this research project was organized in an Excel spreadsheet as a table with
each separate row documenting an observation and each separate column displaying one of the
variables under examination. For the purpose of this research, an observation is defined as one
of the six air samples taken at one of the Fillers. The data set was uploaded to the SAS software
version 9.3 for statistical analysis.
Table 4.1 below lists all the categorical variables (a variable that is not quantitative in nature)
involved in the study. The values for categorical variables are treated as labels to distinguish
between the different categories.
57
Table 4.1 List of the Categorical Variables
Variable Name Description Levels Level Values
Period Sampling Period 24 1 to 24
Line Production Line 4 1, 2, 3, 4
Point Sampling Points around Production
Lines 6 1, 2, 3, 4, 5, 6
Production Production Status 3
Spring
Purified
No Product
Production_Size
Production with Size
7
0.5 L Spring
0.33 L Spring
25 oz Spring
8.5 oz Spring
0.5 L Purified
8.5 oz Purified
No Product
AHU Number of Air Handling Units 3 1, 2, 3
Purified Any Purified Being Produced During
that Sampling Period 2
Yes
No
NOTE: The variables Production and Production_Size and process-related events of CIP,
Sanitizing and Down are combined into one category called “No Product.”
In addition to these seven categorical variables there are also three continuous variables (subject
or observation takes a value from an interval of real numbers) which have numerical values.
1) Ozone_Air is defined as the airborne ozone concentration in the Filler Room,
2) Ozone_RinseWater represents the ozone level in the rinse water contact tank, and
3) Ozone_Product is the ozone level in the product water.
Figure 4.1 below details the timeline showing when various events occurred over the time period
of June 19, 2007 through January 22, 2008 when the air sampling took place. The temporary
wall between Line #3 and Line #4 was removed at sampling period 16. Beginning with
sampling period 17, Line #4 came on line. The second AHU was put into operation beginning
with sampling period 4 and the third AHU was put into operation at sampling period 21.
58
Figure 4.1 Timeline of the Events
As identified in Figure 4.1 above, there was a total of 24 sampling periods performed for the
research project. As previously mentioned, the results of the sampling periods as well as other
related information comprise the data set for the project. An example of the information
contained in the data set is shown in Figure 4.2 below.
Figure 4.2 Partial Data Set Arranged in Excel Format
Among all the variables, Ozone_Air is the response variable, which is the variable whose values
can be explained or predicted by other variables. All the rest are the predictor variables, whose
values will be used to predict the values of the response variable.
59
A new variable called Line4 was also created to distinguish the airborne ozone concentrations
before and after bottles started to be filled on Line #4. As previously mentioned, this event
coincides with sampling period 17, which was the first sampling period involving Line #4.
4.2.1. Data Set Input Commands
Figure 4.3 below shows the SAS software input window. All the SAS commands are written in
the Editor screen with the results displayed in the Output screen. The results are displayed when
the command of interest is entered into the Editor screen and the running man icon (inside the
red circle) is clicked on to initiate the program.
Figure 4.3 SAS Window and the Run Icon
60
4.3. Exploratory Data Analysis (EDA)
There is a variety of factors that could potentially affect the response variable, Ozone_Air. In
order to identify the most important factors and exclude those that do not have a significant
impact on the response variable, an Exploratory Data Analysis (EDA) was performed before
model construction. EDA consists of calculating descriptive statistics and appropriate testing,
such as a t-test and ANOVA. A two-sample t-test is used to compare the means between two
groups. ANOVA partitions the observed variance into components due to different predictor
variables and is used to test whether the means of several groups are all equal. The type of
ANOVA that was used for this EDA section is the one-way ANOVA, where only one predictor
variable is involved. It is used to test for the differences among two or more groups of this
predictor variable, thus it is a generalization of two-sample t-tests. The tests here are only used
as a descriptive approach. For instance, a calculation can be performed to identify the means of
the airborne ozone concentrations with different numbers of AHUs at work. With some of the
ANOVA tests, a comparison of the means is made to see if there are significant differences
caused by the number of AHUs in operation. Exploratory ANOVA is important to simplify the
model and find the most appropriate statistical analysis.
4.3.1 Effect of Line 4 Status
The first effect examined involved a determination of whether the start-up of production on Line
#4 had a significant effect on the airborne ozone concentration in the Filler Room. This was
accomplished using a t-test.
For this analysis, a subset of the data where the variable Line is not equal to 4 (i.e., Line #1, #2
and #3) and where the variable Period is from 4 to 21 was used. The reason for this approach is
due to the fact that there were multiple factors changing in the Filler Room over the course of
data collection (refer to the timeline in Figure 4.1). For example, there was an additional AHU
functioning after Line #4 was put into operation. So if the airborne ozone concentrations in the
Filler Room before Line #4 began production were compared with the ozone concentrations after
Line #4 began production, it would be difficult to determine if the difference was caused by the
addition of Line #4 or the presence of an additional AHU. In addition, there was the need to
61
only compare the airborne ozone concentrations in Lines #1, #2 and #3, since there was no Line
#4 data for the simple fact it did not exist for the first 16 samples. Therefore, by using the subset
that only covers the sampling periods when two AHUs were in operation, the focus of this test
will be directed to the status of Line #4 only.
Figure 4.4 SAS Output of t-test of Airborne Ozone Concentration on Variable Line4
Figure 4.4 above displays the results from the t-test. The results indicate there is not much
difference in the mean airborne ozone concentrations between the two groups; before (indicated
on Figure 4.4 as BL4) (0.0905 ppm) and after Line #4 (indicated on Figure 4.4 as AL4) (0.0944
ppm) was put into operation. The Pr > | t | (p-value) is only used as a descriptive approach to
identify the importance of the grouping variable, which is Line4. A low p-value (< 0.05) would
indicate the significance of the variable and thus the variable should be included in the model,
while a high p-value (> 0.05) would indicate the insignificance of the variable and should be
excluded from the model. There are two p-values shown in the t-test, one for equal variance and
the other for unequal variance. Since the Pr > F (p-value for testing the equality of variance) is <
0.05 (0.0351), the equality of the variance is rejected and the p-value for unequal variance should
be considered.
62
Since the p-value (> 0.05) is quite high (0.5192), there is reason to believe, the Line #4 status
would not significantly impact the airborne ozone concentrations.
Further, since the removal of the temporary wall occurred almost at the same time as Line #4
began operation, it is reasonable to believe that there is not much difference in the mean airborne
ozone concentrations before and after the wall was removed.
4.3.2. Effect of Purified Water Production
The second variable screened using a t-test was an indicator of production status that denotes
when purified water products were being bottled to determine whether this had a significant
effect on the airborne ozone concentration in the Filler Room.
Figure 4.5 SAS Output of t-test of Airborne Ozone Concentration on Purified
63
Figure 4.5 above displays the results from the t-test. The mean airborne ozone concentration
when production included Purified products is 0.1062 ppm, which is much higher than the mean
ozone concentration of 0.0573 ppm when there was no Purified products being bottled at the
time the sample was taken. The low p-value (<0.0001) also confirms this. Based on these
results, it is obvious that the variable Purified will have a significant effect on the airborne ozone
concentration. This is expected since the Purified line of products provides an additional source
of ozone gas that is continually dissipating from the purified product water during the bottle
filling cycle.
4.3.3. Effect of AHU
The third variable evaluated was the number of AHUs in operation and whether this has a
significant effect on the airborne ozone concentration in the Filler Room. Since the variable
AHU has three levels (meaning throughout the period when the air sampling was conducted,
there was from one to three AHUs in operation at the same time), instead of a t-test, a one-way
analysis of variance (One-way ANOVA) was used. The primary purpose of the One-way
ANOVA is to test the differences in means for a variable with more than two levels.
Figure 4.6 SAS Output for the Mean Airborne Ozone Concentration at Different AHU
From Figure 4.6, a comparison can be made between the mean airborne ozone concentrations
and the different number of AHUs in operation. As one would expect, the mean ozone
concentrations decreased from 0.1486 ppm to 0.0516 ppm as more AHUs were put into
operation. Therefore, the variable AHU has a significant effect on airborne ozone concentrations
in the Filler Room and should be included in the model. This conclusion is further supported by
64
examining the number of room air changes per hour (ACH) for the Filler Room as it was
modified to include the Line #4 addition.
As discussed in section 3.4, when air sampling for the research started, there was a temporary
wall built in the Filler Room to isolate Line #1, Line #2 and Line #3 from the construction taking
place to install the Line #4 production equipment. This wall separated AHU #1 from this portion
of the Filler Room leaving only AHU #2 to provide air movement for the entire area housing
Line #1, Line #2 and Line #3, which resulted in an ACH of 15.03. During this time, sampling
periods 1 through 3 took place. As previously mentioned, this sampling interval had a mean
airborne ozone concentration of 0.1486 ppm. AHU #1 was put in operation when sampling
periods 4 through 15 took place. However, the temporary wall was still in place and once again
leaving AHU #1 theoretically cut-off from the area housing Line #1, Line #2 and Line #3. The
addition of this AHU resulted in a hypothetical ACH of 13.24, which encompassed the entire
footprint of the Filler Room. Interestingly enough, the mean airborne ozone concentration
during this sampling interval was reduced to 0.0859 ppm. Even with the temporary wall in
place, there apparently was a sufficient volume of air movement provided by AHU #1 to prevent
the ozone gas from accumulating in the work area, which enabled this reduction to occur. The
temporary wall was taken down during sampling periods 16 through 20, which resulted in a true
ACH of 13.24 for the Filler Room. During this sampling interval, Line #4 was put into
operation, which resulted in an increase in the mean airborne ozone concentration to 0.1106
ppm. This increase is expected since AHU #3 was still not in operation at this time. Finally,
when AHU #3 was put in operation the Filler Room’s ACH increased to 17.56. Sampling
periods 21 through 24 took place while all three AHUs were in operation, which reduced the
mean airborne ozone concentration to its lowest point of 0.0516 ppm.
65
Figure 4.7 SAS Output for ANOVA of Airborne Ozone Concentration on AHU
The results shown in Figure 4.7 confirm that the variable AHU is significant with a very low
(<0.0001) p-value.
4.3.4. Effect of Sampling Points
The potential effect of sampling location (Point) was evaluated using an ANOVA test to
determine if there were significant differences in ozone concentrations measured at the different
sampling positions in the Filler Room
66
Figure 4.8 SAS Output for the Mean Airborne Ozone Concentration at Different Sampling
Points
From Figure 4.8, the mean airborne ozone concentrations can be compared at different sampling
points. Results indicate that there is not a significant difference among the six sampling points
with 0.0140 ppm separating the highest (0.1005 ppm) mean concentration from the lowest
(0.0865 ppm) concentration. Therefore, the variable Point probably does not have a significant
effect on airborne ozone concentration in the Filler Room and should be excluded from the
model. This is confirmed by the results of the one-way ANOVA presented in Figure 4.9 which
show that the variable Point is very likely to be insignificant with a high (0.5883) p-value
(>0.05). Since the sampling points are not a source of ozone but simply a measuring location,
this result is reasonable.
Since the sampling points are not a source of ozone but simply a measuring location, this result is
reasonable.
67
Figure 4.9 SAS Output for ANOVA of Airborne Ozone Concentration on Point
4.3.5. Effect of Production Status on the Filler Being Sampled
A one-way ANOVA test was used to determine if production status (Spring, Purified or No
Product) has a significant effect on the airborne ozone concentration in the Filler Room.
Figure 4.10 SAS Output for the Mean Airborne Ozone Concentration at Different Production
Status
From Figure 4.10, the mean airborne ozone concentrations can be compared for the different
levels types of production status. The mean ozone concentration with the highest value of
0.1235 ppm is when purified products were being bottled on the particular Filler that was being
sampled. The second highest mean ozone concentration of 0.0843 ppm occurred when the Filler
68
being sampled was bottling spring products. The lowest mean ozone concentration of 0.0619
ppm is when the Filler had no production activity at the time of sampling, meaning the Filler was
not bottling product or a CIP or sanitation activity was taking place. The mean differs
substantially at the three levels. Therefore, is it likely that the variable Production does have a
significant effect on airborne ozone concentration in the Filler Room and should be included in
the model. This is confirmed by the results of the one-way ANOVA shown in Figure 4.11.
These values should be expected since purified products have the ozonated product water as an
extra source of ozone. Even though the water for the spring products is not ozonated, there is still
the ozonated rinse water being sprayed inside the bottles prior to being filled. Finally, it is no
surprise that the lowest mean ozone concentration occurs when there is no production activity
associated with a Filler. The only source of ozone encountered under this condition is the trickle
of ozonated water that is used as a lubricant on the bottle rinse wheel and filler bowl. Ozonated
water is not used during CIPs or sanitation activities.
Figure 4.11 SAS Output for ANOVA of Airborne Ozone Concentration on Production
69
4.3.6. Effect of Production Status with Size of Bottle
As previously noted, it was found that production status (Spring, Purified and No Product) has a
significant effect on the airborne ozone concentration. The next variable evaluated was the size
of the bottle being filled and the type of product. A one-way ANOVA test was used to
determine if this factor significantly influenced airborne ozone concentration.
Figure 4.12 SAS Output for the Mean Airborne Ozone Concentration at Different Production
Status with Size
From Figure 4.12, the mean airborne ozone concentrations can be compared at different types of
production status with size. The mean ozone concentrations are quite different with different
product and size. For example, Purified has two different sizes, and the larger size (0.5L) has the
higher mean ozone value (0.1270 ppm versus 0.0668 ppm for the 8.5 oz. size). Therefore, it is
believed that size also matters in this case, and the variable Production_Size should be
considered in the model instead of Production alone (without size). Once again, this is
reasonable due to the increased volume of ozonated water required to rinse the larger size bottles
as well as the larger size bottles providing a bigger reservoir for the ozone to off-gas into the air.
Among the product Spring, the smallest size (8.5oz) is associated with the highest (0.1675 ppm)
airborne ozone concentration, which upon first glance seems unreasonable. However when
reviewing the data set, it was found that 8.5oz Spring was only produced on Line #3 in sampling
periods 1, 2, 3 and 24. Comparing the ozone concentrations at these sampling periods, it has
70
much higher airborne ozone concentrations in sampling period 1, 2 and 3 than in period 24. This
is most likely a result of having only one AHU in operation during sampling periods 1, 2 and 3,
compared to three AHUs in operation for sampling period 24. In addition, the only AHU in
operation during sampling periods 1, 2 and 3 is located near Line #1 and is approximately 50 feet
away from Line #3, which further explains the high airborne ozone concentrations at Line #3
during those sampling periods. Therefore, it is believed that Production_Size should not be in
the model by itself, but rather Production_Size nested in AHU, denoted as
Production_Size(AHU). This means Spring 8.5oz at one AHU is different from Spring 8.5oz at
two AHUs, as well as Spring 8.5oz at three AHUs.
Figure 4.13 SAS Output for ANOVA of Airborne Ozone Concentration on Production_Size
The result from Figure 4.13 confirms that the bottle size does matter and the variable
Production_Size is significant with a very low p-value (<0.0001).
71
4.3.7. Correlation Between Ozone Concentrations in Air, Rinse Water and Product Water
This analysis involved determining the correlation between the Ozone_Air, Ozone_RinseWater
and Ozone_Product concentration variables. Correlation measures the strength of association
between two continuous variables.
Figure 4.14 SAS Output for Correlation
The results shown in Figure 4.14 show the correlations between the three variables. Based on
the output in Figure 4.14, the following hypothesis can be tested for correlation:
H0: There is no relationship between Ozone_Air and Ozone_RinseWater.
HA: There is a relationship between Ozone_Air and Ozone_RinseWater.
72
If Prob > | r | (p-value) is < 0.05, the H0 would be rejected, and it would be concluded that there
is a relationship between Ozone_Air and Ozone_RinseWater. If Prob > | r | (p-value) is > 0.05,
the H0 cannot be rejected leading to the conclusion that there is no relationship between
Ozone_Air and Ozone_RinseWater. The value for Prob > | r | (p-value) is the second number in
each cell of the 3 × 3 table in Figure 4.14. Since the p-value (< 0.05) for testing the relationship
between Ozone_Air and Ozone_RinseWater is low (< 0.0001), the H0 is rejected and we can
conclude that there is a relationship between Ozone_Air and Ozone_RinseWater. Therefore,
Ozone_RinseWater should also be in a model for predicting Ozone_Air.
The same hypothesis testing can be performed between Ozone_Air and Ozone_Product. The
results indicate that this correlation is also significant.
4.3.8. Interactions Between Predictor Variables
From the preceding series of exploratory ANOVA and t-tests, it was determined that several
variables can be excluded from the model since they do not have much effect on the airborne
ozone concentration. From the correlation test, it was determined that Ozone_Air has a linear
relationship with both Ozone_RinseWater and Ozone_Product. The next step in the analysis is
to determine whether there are any interactions between these variables. Interaction means the
failure of a response to one factor to be the same at different levels of another factor.
In order for an interaction to be examined, the data set must include at least one observation for
every combination of the factor levels for the two factors under consideration. However, looking
first at the three categorical variables identified as possibly having significant effects on airborne
ozone concentration (Production_Size(AHU), AHU, and Purified), a complete set of
combinations between any two factor levels does not exist in the data set.
For example, with 1 AHU, all the observations are recorded when Spring and Purified are being
produced - there is no combination of 1 AHU with No Purified. Therefore, the interaction
between AHU and Purified cannot be tested. The same logic applies to Purified and
Production_Size(AHU). In addition, AHU is nested in Production_Size(AHU), so no interaction
73
can be considered between these two variables. In the following subsections, interactions will be
considered for those combinations of factors having adequate representation in the data set.
4.3.8.1. Interactions Between Ozone_RinseWater and Categorical Predictor Variables
The next step in this analysis is to determine if there is any interaction between
Ozone_RinseWater and any of the three categorical variables. A plot showing ozone air
concentration versus ozone rinse water concentration for the two levels of the Purified variable
(Yes, No) is shown in Figure 4.15.
Figure 4.15 Plot of Ozone_Air vs. Ozone_RinseWater for Purified and No Purified
Purified is the red-colored line (symbol red x) and No Purified is the blue line (symbol blue o).
Both lines have a positive slope, which means as the level of Ozone_RinseWater increases,
Ozone_Air increases in both groups. In addition, the two lines appear to be parallel. This
indicates no interactions between Ozone_RinseWater and Purified, which means for every unit
increase in Ozone_RinseWater, Ozone_Air will increase by approximately the same amount for
Purified and No Purified. Therefore, Purified and Ozone_RinseWater should be included in the
model as additive terms rather than interactive terms.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_RinseWater
0.18 0.20 0.22 0.24 0.26 0.28 0.30 0.32 0.34 0.36 0.38 0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56 0.58 0.60 0.62 0.64 0.66 0.68
Ozone in Air versus Ozone in Rinse Water for Purified and No Purified
Purified No Yes
74
The next step in the analysis is to plot similar lines to determine if there is any interaction
between Ozone_Air vs. Ozone_RinseWater for the three different levels of the AHU variable (1
AHU, 2 AHUs and 3 AHUs).
Figure 4.16 Plot of Ozone_Air vs. Ozone_RinseWater with Different AHUs
Figure 4.16 shows three fitted lines for Ozone_Air versus Ozone_RinseWater: 1 AHU is the
blue-colored line (symbol o), 2 AHUs the red line (symbol x) and 3 AHUs the green line
(symbol +). Not all three lines appear to be to be parallel. This indicates there might be an
interaction between Ozone_RinseWater and AHU, which means for every unit increase in
Ozone_RinseWater, Ozone_Air will increase differently for three groups with different numbers
of AHUs. Therefore, an interaction between Ozone_RinseWater and AHU (denoted as
Ozone_RinseWater*AHU) should be included in the model for further investigation.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_RinseWater
0.18 0.20 0.22 0.24 0.26 0.28 0.30 0.32 0.34 0.36 0.38 0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56 0.58 0.60 0.62 0.64 0.66 0.68
Ozone in Air versus Ozone in Rinse Water for Different AHUs
AHU 1 2 3O O O
O
O
OO
O
O
O
O
O
OO
O
O
O
O
O
OO
O
OO
OOO
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
75
The next step in the analysis is to plot the lines to determine if there is any interaction between
Ozone_Air vs. Ozone_RinseWater for different Production_Size.
Figure 4.17 Plot of Ozone_Air vs. Ozone_RinseWater with Different Production_Size
Figure 4.17 shows seven fitted lines for Ozone_Air versus Ozone_RinseWater, with each
indicating a different level of Production_Size. Six of the seven lines appear to be approximately
parallel, while the line for the 8.5 oz. Spring shown in orange is different. The orange-colored
line (symbol *) has a much larger slope, compared to the others. This is due to some
observations with high ozone levels in the air for 8.5 oz. Spring, which are shown in the upper
part of this figure. When Figure 4.17 is compared with Figure 4.16, it is evident that these
possible outliers correspond to the 1 AHU. Therefore, this can be explained by the previous
discussion presented in the exploratory one-way ANOVA for Production_Size. Given these
potentially outlying data points, it is believed there is likely no interaction between
Ozone_RinseWater and Production_Size. However, this interaction will still be included in the
model to test its significance.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_RinseWater
0.18 0.20 0.22 0.24 0.26 0.28 0.30 0.32 0.34 0.36 0.38 0.40 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56 0.58 0.60 0.62 0.64 0.66 0.68
Ozone in Air versus Ozone in Rinse Water for Different Production_Size
Production_Size .33L Spring .5L Purified .5L Spring 25oz Spring 8.5oz Purified 8.5oz Spring No ProductO O O M M M
O
OOO
O
O
O
OOO
O
O
O
O
O
O
O
O
M
M
M
M
M
M
MM
M
M
M
M
M
MM
M
M
M
MM
M
MM
M
M
M
M
M
M
M
MMM
M
MM
M
M
M
MM
MMMMM
MM
M
MM
MM
M
M
MMM
M
M
M
MM
M
MM
M
MM
M
76
4.3.8.2. Interactions between Ozone_Product and Categorical Predictor Variables
The next step in the study is to determine if there are any interactions between Ozone_ Product
and any of the three categorical variables by plotting the lines between Ozone_Air vs.
Ozone_Product for two different groups, Purified and No Purified.
Figure 4.18 Plot of Ozone_Air vs. Ozone_Product for Purified and No Purified
Figure 4.18 shows the two fitted lines for Ozone_Air and Ozone_Product, with Purified in red
(symbol x) and No Purified in blue (symbol o). The red-colored line appears to have a
decreasing trend, while the blue-colored line is almost horizontal. The two lines do not appear to
be parallel. This indicates there might be an interaction between Ozone_Product and Purified.
Therefore, the interaction between Ozone_Product and Purified (Ozone_Product*Purified) is to
be included in the model for further investigation.
The next interaction examined was for Ozone_Air vs. Ozone_Product for three different groups,
1 AHU, 2 AHUs and 3 AHUs.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_Product
0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.20 0.21 0.22 0.23 0.24 0.25 0.26 0.27 0.28 0.29 0.30 0.31 0.32 0.33 0.34
Ozone in Air versus Ozone in Product Water for Purified and No Purified
Purified No YesO O O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OOO
O
O
O
O
O
O
O
O
OO
O
O
OOO
O
O
OO
O
O
O
O
O
OO
O
O
O
O
O
O
O
O
OO
O
OO
O
OO
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OOO
O
OO
O
OOO
O
OO
O
OO
O
O
OOO
O
O
77
Figure 4.19 Plot of Ozone_Air vs. Ozone_Product with Different AHU
Figure 4.19 shows three fitted lines for Ozone_Air and Ozone_Product: 1 AHU in blue (symbol
o), 2 AHUs in red (symbol x) and 3 AHUs in green (symbol +). All three lines appear to be
approximately parallel. This indicates there might not be an interaction between Ozone_Product
and AHU. Therefore, an interaction between Ozone_Product and AHU will not be included in
the model.
The last potential interaction considered was for Ozone_Air vs. Ozone_Product for different
Production_Size. Figure 4.20 shows the seven fitted lines for Ozone_Air and Ozone_Product.
Each line indicates a different level of Production_Size. The lines do not appear to be parallel.
This indicates that there might be an interaction between Ozone_Product and Production_Size
and therefore the interaction (Ozone_Product*Production_Size) is to be included in the model
for further investigation.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_Product
0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.20 0.21 0.22 0.23 0.24 0.25 0.26 0.27 0.28 0.29 0.30 0.31 0.32 0.33 0.34
Ozone in Air versus Ozone in Product Water for Different AHUs
AHU 1 2 3O O O
O
O
OO
O
O
O
O
O
OO
O
O
O
O
O
OO
O
OO
OOO
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
OO
O
O
O
O
O
78
Figure 4.20 Plot of Ozone_Air vs. Ozone_Product with Different Production_Size
4.4. Model Construction and Analysis of Variance
From the previous sections, it was determined that several of the variables and interactions that
do not have a significant effect on airborne ozone concentrations can be excluded from further
examination. The next step is to construct a model with variables that have significant effects on
airborne ozone concentrations. Those interactions that were identified as potentially being
significant will also be included in the model for testing.
In this study, all the factors of interest are fixed. A factor is viewed as a fixed effect when all
levels of interest from the factor are included in the study. Alternatively, a factor can be a
random effect, which is the case for those factors where there is only a sample of the possible
levels, but inferences about the whole population need to be made. A mixed model will include
both fixed and random factors.
Ozone_Air
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0.11
0.12
0.13
0.14
0.15
0.16
0.17
0.18
0.19
0.20
0.21
0.22
0.23
0.24
0.25
0.26
0.27
0.28
0.29
0.30
0.31
0.32
0.33
Ozone_Product
0.13 0.14 0.15 0.16 0.17 0.18 0.19 0.20 0.21 0.22 0.23 0.24 0.25 0.26 0.27 0.28 0.29 0.30 0.31 0.32 0.33 0.34
Ozone in Air versus Ozone in Product Water for Different Production_SIze
Production_Size .33L Spring .5L Purified .5L Spring 25oz Spring 8.5oz Purified 8.5oz Spring No ProductO O O M M M
O
OOO
O
O
O
OOO
O
O
O
O
O
O
O
O
M
M
M
M
M
M
MM
M
M
M
M
M
MM
M
M
M
MM
M
MM
M
M
M
M
M
M
M
MMM
M
MM
M
MM
MM
M
M
MMM
M
M
M
MM
M
MM
M
MM
M
79
The experimental unit is the subject exposed to the treatment. In this study, the production line
is considered as the experimental unit since during different sampling periods, one production
line may have a different status. Thus, production line nested in sampling period should be
considered as the experimental unit, denoted as Line(Period). This means Line 1 in Period 1 is
different from the Line 1 in Period 2.
Air sampling was performed on each production line six times within each sampling period, at
points 1 through 6. Since there could be correlation between the observations at different
sampling points of the same production line, they are not independent with each other. This is
called repeated measures.
Since it is likely there could be correlation between the observations at different sampling points
of the same production line, it is also necessary to specify the covariance structure for the
correlated data. Here we consider it as the repeated measures through time, and assume that 6
measurements at 6 points are taken in order.
Using these assumptions, a mixed model containing the following eight terms was fit to the
experimental data set: Production_Size(AHU), AHU, Purified, Ozone_RinseWater,
Ozone_Product, Ozone_RinseWater*AHU, Ozone_Product*Purified and
Ozone_Product*Production.
Residual plots for the resulting model are presented in Figure 4.21. The basic assumption for an
ANOVA model is that errors are normally distributed with zero mean and constant variance.
Statisticians have shown that residuals have different variances, thus studentized residuals are
used, which can be achieved by dividing residuals by their standard errors, to verify whether the
assumptions of ANOVA model are satisfied. The plot in the upper-left corner in Figure 4.21 is
the plot of studentized residuals versus predicted means. Since no sharply increasing or
decreasing trends are identified, the assumption that the variance is constant can be accepted.
The plot in the upper-right corner is the histogram, while the plot in the lower-left corner is the
Q-Q plot. Both can be used to check the normality assumption. If the shape of the histogram is
80
bell-shaped, and the Q-Q plot is almost a straight line, the normal assumption can be accepted.
Results indicate that no large violations of assumptions occurred.
Figure 4.21 Studentized Residual Plots
The output from the model construction shown in Figure 4.22 can be used to test the following
hypothesis for the interaction Ozone_RinseWater*AHU:
H0: There is no interaction between Ozone_RinseWater and AHU.
HA: There is interaction between Ozone_RinseWater and AHU.
If Pr > F (p-value) is < 0.05, the H0 would be rejected, and we would conclude that there is a
significant interaction between Ozone_RinseWater and AHU. If Pr > F (p-value) is > 0.05, the
H0 cannot be rejected, leading to the conclusion that there is no significant interaction between
Ozone_RinseWater and AHU.
81
Figure 4.22 SAS Output for Model Construction and Analysis of Variance
Since the p-value (>0.05) here for Ozone_RinseWater*AHU is high (0.3602), the H0 is not
rejected and the conclusion can be made that there is no significant interaction between
Ozone_RinseWater and AHU. The same hypothesis testing can be performed on the other two
interactions, Ozone_Product*Purified and Ozone_Product*Production_Size. It was found that
these interactions are not significant, therefore, these terms were removed and a reduced model
was fit.
The resulting residual plots and ANOVA output are shown for the reduced model in Figures 4.23
and 4.24, respectively. Again, the studentized residual plots are checked - the residuals are
approximately normally distributed with zero mean and constant variance. No obvious
violations of assumptions are detected.
82
Figure 4.23 Studentized Residual Plots for Reduced Model
Figure 4.24 SAS Output of Testing the Significance of the Factors in the Reduced Model
83
Based on the output in Figure 4.24, the following hypothesis for AHU can be tested:
H0: There is no significant effect due to AHU or μ1AHU = μ2AHU = μ3AHU.
HA: There is significant effect due to AHU or at least one of the means is different.
If Pr > F (p-value) is < 0.05, the H0 would be rejected, and we conclude that there is a significant
effect of AHU. If Pr > F (p-value) is > 0.05, the H0 cannot be rejected, and we conclude that
there is no significant effect of AHU.
Since the p-value (< 0.05) here for AHU is small (< 0.0001), H0 is rejected and we can conclude
that AHU is highly significant.
The same hypothesis testing can be performed on Production_Size(AHU), Purified,
Ozone_RinseWater, and Ozone_Product. It was determined that all are significant.
It has been shown that there are significant differences in the ozone levels at different levels of a
variable (e.g. AHU). That is to say, μ1AHU, μ2AHU and μ3AHU are not all equal to each other. At
least one of them is different. For the next step in this analysis, the goal is to identify which one
or ones are different. This is accomplished by performing a comparison of the least squares
means, which are the means from the model that fits the data so that the sum of squared residuals
(observation minus estimates) is minimized.
One test that needed to be performed was to examine the differences among all different levels of
AHU simultaneously. In the hypothesis inference, if there is only one test, then the probability
that the null hypothesis would be rejected when it is true is at most 0.05 (the significance level).
However, with multiple comparisons (in this case, the data includes three simultaneous tests), it
is more likely to reject the null hypothesis incorrectly. There are several types of adjustments
which have been developed to control this error, such as Tukey, Dunnett and Bonfferoni.
Tukey’s adjustment is used for all pairwise comparisons. Dunnett’s adjustment is for comparing
one mean with all others. Bonfferoni’s adjustment is usually used when you want to compare a
certain number of pairs of the means. Since it is necessary to compare all the possible pairs
84
(μ1AHU vs. μ2AHU, μ1AHU vs. μ3AHU, μ2AHU vs. μ3AHU), the Tukey’s multiple comparisons procedure
will be used.
Figure 4.25 SAS Output of Least Squares Means
Figure 4.25 shows the least squares means estimates at all the three levels of AHU. This is a
little different from the means in Figure 4.6. This difference is due to the fact that all the
significant factors are being taken into consideration in the model.
Figure 4.26 SAS Output of Multiple Comparisons with Tukey Adjustment
From the results shown above in Figure 4.26, it is evident that the difference between 1 AHU
and 2 AHUs is significant (adjusted p-value < 0.0001), as well as the difference between 1 AHU
and 3 AHUs. However, the difference between 2 AHUs and 3 AHUs is not significant (adjusted
p-value = 0.8551 > 0.05).
4.5. Trends / Observations Identified During Research
In addition to the factors that were initially recognized in section 3.6 as being potential sources
of ozone in the Filler Room, there were several additional sources identified while the air
sampling was being conducted for this research project. These included:
85
1) Filler equipment malfunctions (e.g., conductivity probe), especially affecting filler tubes, that
can lead to “flood filling” bottles that result in the overfilling of bottles with excess ozonated
water flowing onto the deck of the Filler and discharging to the floor trenches in the Filler
Room.
2) Ozone flushes, which are a form of equipment sanitization lasting approximately 15-minutes
in duration, can introduce ozone. Process involves transferring ozonated water from an OCT
through the filler bowl, out of the filler bowl and onto the deck of the Filler where it
discharges out of the Filler and into the floor trenches.
3) Samples of filled bottles used for various quality tests such as cap torque testing and bottle
weight verification {3 sampling cycles per 12-hour shift of 15 bottles (Lines #1, #2 and #3)
and 30 bottles (Line #4)}. Task takes approximately 10 minutes with the product water from
the bottles dumped into one of the Filler room floor trenches.
4) Ozonated water delivered from the water hose stations in the Filler Room used to rinse
stainless steel cleaner from the exterior of a Filler or a sanitizing chemical from the interior
of a Filler. The hose stations also provide the water to rinse a chemical cleaner off the floor
of the Filler Room.
5) Ozonated product water splashing out of bottles and onto the deck of the Filler as bottles are
being filled and passed through a series of flywheels prior to capping.
6) Ozone off-gassing from the ozonated water that collects in the floor trenches in the Filler
Room – the flow pattern in the floor trenches varies where in certain trenches the flow is
towards a Filler Operator’s normal work position while in others its away from this position.
These flow patterns can influence the concentration of airborne ozone that the workers
attending the equipment in the Filler Room are exposed to.
7) Workers periodically opening sash doors on the Filler to clear bottle or cap jams or to clear
the Filler deck of caps/bottles resulting in ozone being blown out of the Filler with the
equipment’s positive pressure air stream.
It is believed that each of these sources contributes to a portion of the overall airborne ozone
concentration in the Filler Room.
86
4.6. Comparison of Airborne Ozone Concentrations to Occupational Exposure Limits
Table 4.2 includes various production scenarios for which mean airborne ozone concentrations
were calculated as part of the analysis of the data set. This table lists the scenario and its
calculated concentration along with relevant exposure limits from OSHA, ACGIH and NIOSH.
An “X” in the box under one of the occupational exposure limit columns indicates the calculated
mean airborne ozone concentration exceeded that specific exposure limit. Results show that
many of the short-term concentrations exceeded one or more of the following exposure limits:
the OSHA PEL of 0.1 ppm and the ACGIH TLV-TWA (moderate work) of 0.05 ppm for an 8-
hour work shift, the OSHA 15-minute STEL of 0.3 ppm, and the NIOSH REL-Ceiling limit of
0.1 ppm. However, it should be noted that a true determination of compliance with an 8-hour
TWA exposure limit would require sampling for the full shift.
With this in mind, the production scenarios where five of the six exposure limits of interest were
potentially exceeded (none exceeded the OSHA 15-minute STEL) include the following:
1) When only one AHU was in operation, which covered sampling periods 1 through 3
(0.1486),
2) When the 0.5L purified product was being bottled (0.1270 ppm),
3) When a sampling cycle was conducted on a Filler where purified products were being bottled
(0.1235 ppm),
4) When all four Fillers were in operation but only two of the three AHUS were operating,
which covered sampling periods 16 through 20 (0.1106 ppm),
5) Whenever purified products were being bottled on one of the four Fillers (0.1062 ppm), and
6) Measurements taken at sample point #4 (point reflects location where the Filler rinser wheel
and filler wheel are adjacent to each other; primary sources of ozonated water in the Filler)
(0.1005 ppm).
Conversely, the Production scenarios where only one of the six exposure limits (the 12-hour
adjusted ACGIH TLV-TWA) was exceeded include the following:
1) When all three AHUs were in operation (0.0516 ppm),
2) When natural spring water products were being produced (0.573 ppm), and
87
3) When a sampling cycle was conducted on a Filler where no production was taking place
(0.0619 ppm).
Table 4.2 Comparison of Production Scenarios with Selected Occupational Exposure Limits
Scenario with
Mean Airborne
Ozone
Concentration
OSHA
8-hour
PEL-TWA
(0.1 ppm)
OSHA
12-hour
Adjusted
PEL-TWA
(0.067 ppm)
ACGIH
8-hour
TLV-TWA
(moderate
work)
(0.08 ppm)
ACGIH
12-hour
Adjusted
TLV-TWA
(moderate
work)
(0.04 ppm)
OSHA
15-minute
STEL
(0.3 ppm)
NIOSH
REL
Ceiling
(0.1 ppm)
Before Line #4 in
operation
(0.0905 ppm)
X X X
After Line #4 in
operation
(0.0944 ppm)
X X X
Production during
the sampling
period included
Purified products
on one or more
Fillers
(0.1062 ppm)
X X X X
X
Production during
the sampling
period included
Spring products
on one or more
Fillers
(0.0573 ppm)
X
Purified product
was being bottled
on the Filler being
sampled
(0.1235 ppm)
X X X X
X
Spring product
was being bottled
on the Filler being
sampled
(0.0843 ppm)
X X X
88
Scenario with
Mean Airborne
Ozone
Concentration
OSHA
8-hour
PEL-TWA
(0.1 ppm)
OSHA
12-hour
Adjusted
PEL-TWA
(0.067 ppm)
ACGIH
8-hour
TLV-TWA
(moderate
work)
(0.08 ppm)
ACGIH
12-hour
Adjusted
TLV-TWA
(moderate
work)
(0.04 ppm)
OSHA
15-minute
STEL
(0.3 ppm)
NIOSH
REL
Ceiling
(0.1 ppm)
No production
activity on the
Filler being
sampled (meaning
the Filler being
sampled was not
bottling water or a
CIP or sanitation
activity was taking
place)
(0.0619 ppm)
X
Sampling periods
1 through 3 with
Lines #1, #2 and
#3 in operation,
temporary wall in
place and only
AHU #1 in
operation
(0.1486 ppm)
X X X X
X
Sampling periods
4 through 15 with
Lines #1, #2 and
#3 in operation,
temporary wall in
place and AHU #2
and AHU #1 in
operation
(0.0859 ppm)
X X X
Sampling periods
16 through 20
with Lines #1, #2,
#3 and #4 in
operation,
temporary wall
taken down and
AHU #2 and AHU
#1 in operation
(0.1106 ppm)
X X X X
X
Sampling periods
21 through 24
with Lines #1, #2,
#3 and #4 in
operation, and
AHU #2, AHU #1
and AHU #3 in
operation
(0.0516 ppm)
X
89
Scenario with
Mean Airborne
Ozone
Concentration
OSHA
8-hour
PEL-TWA
(0.1 ppm)
OSHA
12-hour
Adjusted
PEL-TWA
(0.067 ppm)
ACGIH
8-hour
TLV-TWA
(moderate
work)
(0.08 ppm)
ACGIH
12-hour
Adjusted
TLV-TWA
(moderate
work)
(0.04 ppm)
OSHA
15-minute
STEL
(0.3 ppm)
NIOSH
REL
Ceiling
(0.1 ppm)
Sampling point #1
(0.0899 ppm) X X X
Sampling point #2
(0.0952 ppm) X X X
Sampling point #3
(0.0865 ppm) X X X
Sampling point #4
(0.1005 ppm) X X X X
X
Sampling point #5
(0.0933 ppm) X X X
Sampling point #6
(0.0903 ppm) X X X
Bottle size 0.5L
Spring
(0.0783 ppm)
X X
Bottle size 25 oz
Spring
(0.0743 ppm)
X X
Bottle size
8.5 oz Spring
(0.1675 ppm)**
X X X X
X
Bottle size 0.5L
Purified
(0.1270 ppm)
X X X X
X
Bottle size 8.5 oz
Purified
(0.0668 ppm)
X X
No product
produced
(0.0619)
X
** Elevated airborne ozone concentration is a result of the 8.5 oz spring product being produced during sampling
periods 1 through 3 when only one of the three AHUs was in operation.
The last analysis undertaken was an examination of the distribution of ozone exposure
concentrations at sampling points 1 and 2. Of the six sampling points around each Filler, these
two points would be most representative of the Filler Operator’s normal workstation. Therefore,
the individual measurements taken at these two points should best reflect the Filler Operator’s
exposure to airborne ozone on both a short-term and full-shift basis. Probability plots were
prepared for each sampling point and are presented in Figures 4.27 (sampling point 1) and 4.28
(sampling point 2). Results indicate that the concentrations measured at both sampling points
90
were consistent with a normal distribution as indicated by a goodness of fit test (p-value > 0.05).
The mean ozone concentration was 0.0898 ppm (sd = 0.048), and 0.0952 ppm (sd = 0.052) for
sampling points 1 and 2, respectively.
Figure 4.27 Probability Plot for Sampling Point 1 Ozone_Air
The probability plots are useful in estimating the likelihood of exposure exceeding applicable
occupational exposure limits. Referring to Figure 4.27, 100% of the 80 measurements were
below the OSHA 15-minute STEL of 0.3 ppm while approximately 60% of the measurements
were below the OSHA 8-hour PEL-TWA of 0.1 ppm. Likewise, Figure 4.28 for sampling point
2 shows that 100% of the 78 measurements were below the OSHA 15-minute STEL while
approximately 55% of the measurements were below the OSHA 8-hour PEL-TWA of 0.1 ppm.
The mean airborne ozone concentration for both sampling points is also below both the OSHA
STEL and 8-hour PEL-TWA exposure limits.
91
Figure 4.28 Probability Plot for Sampling Point 2 Ozone_Air
The comparison between the exposure limits and calculated mean ozone concentrations for the
various production scenarios identified in Table 4.2, and the data presented in Figures 4.27 and
4.28 come with a qualifying statement. As previously mentioned, all of the air samples collected
for this research project were of the area type. These samples were essentially instantaneous
readings that reflected the measured airborne ozone concentration at a specific location in the
Filler Room over a very short time period, roughly 3-5 minutes. These short-term samples are
important when comparing the measured concentrations to ceiling limits or 15-minute STELs.
Equally important is an individual’s exposure to a contaminant measured over an entire work
shift and that is reflective of the work activities and airborne concentrations encountered
throughout the day. This is where the personal sampling method of evaluating an individual’s
exposure to an airborne contaminant is preferred.
Though not part of the research project, the bottling facility has a history of personal ozone
exposure samples available that covers the 12-hour extended work shift. These sampling results
represent a different exposure profile than the short-term area samples. Referring to these results
(Table 4.3), only two of thirteen personal samples exceed one of the exposure limits, the 12-hour
adjusted ACGIH TLV-TWA (an “X” in the exposure limit column indicates the limit may have
92
been exceeded). Even these two samples have extenuating circumstances as neither covered the
complete 12-hour work shift.
Table 4.3 History of Personal Sampling for Ozone Exposure
Filler Operator
Workstation
Date
Sampled
Result
(ppm)
OSHA
12-hour Adjusted
PEL-TWA
(0.067 ppm)
ACGIH
12-hour Adjusted
TLV-TWA
(moderate work)
(0.04 ppm)
Filler Line #1 8/23/2006 0.054 X1
Filler Line #4 8/23/2006 0.035
Filler Line #1 7/22/2008 <0.022
Filler Line #2 7/22/2008 <0.046 X2
Filler Lines #2 and #3 7/23/2008 <0.025
Filler Line #4 7/22/2008 0.023
Filler Line #1 12/7/2010 <0.04
Filler Lines #1, #2 and #4 12/7/2010 <0.04
Filler Line #1 12/8/2010 <0.04
Filler Line #2 12/8/2010 0.04
Filler Line #23 3/13/2013 0.046
Filler Line #33 3/13/2013 0.041
Filler Line #43 3/13/2013 0.059
1 - Pump faulted 156 minutes into sample, restarted and ran for remainder of shift.
2 - Employee only worked 1/2 day - sample time 378 minutes.
3 - Samples reflect an 8-hour sampling time instead of 12 hours.
Even though the personal air samples were not part of the research project, they were still taken
under similar production conditions. This means that there was some combination of spring
water and purified products being produced, that similar concentrations of ozone were present in
the product and rinse water, and that possibly one or more Fillers were down (no production)
during the sampling.
The primary difference that these personal samples have compared with the samples collected
for this research study involves the number of AHUs in operation. The samples from 2006 were
collected before the expansion of the Filler Room when two AHUs were in operation.
Additionally, the Filler Room configuration at that time had 2,448 fewer square feet than the
footprint encompassed by the new Line #4. The samples from 2008, 2010 and 2013 were taken
with all three AHUs in operation, which is the exact circumstance experienced during sampling
93
periods 21 through 24 for which the mean airborne ozone concentration of 0.0516 ppm was the
lowest calculated. An additional probability plot was prepared to examine the distribution of
ozone concentrations at sampling points 1 and 2 for this time period when three AHUs were in
operation (Figure 4.29). Results show that these data are consistent with a normal distribution
(goodness of fit test p-value >0.05) with a mean concentration of 0.053 ppm (sd = 0.020)
Figure 4.29 Probability Plot for Sampling Points 1 and 2 with AHU
Once again using the measurements of airborne ozone gas taken at sampling points 1 and 2 as
the basis for comparison, Figure 4.29 indicates 97% of the 30 measurements are below the
OSHA 8-hour PEL-TWA and NIOSH REL-Ceiling limit values of 0.1 ppm. Further,
approximately 80% of the concentrations are below the OSHA 12-hour Adjusted PEL-TWA
value of 0.067 ppm. Based on this knowledge as well as the fact that sampling periods 21
through 24 (time frame when there were 3 AHUs) had the lowest calculated mean airborne
ozone concentration of 0.0516 ppm out of all the production scenarios analyzed, the importance
of room ventilation as a primary and effective means of controlling the airborne ozone
concentration in a work area is apparent.
.
94
Chapter 5
CONCLUSIONS
AND
RECOMMENDATIONS FOR FUTURE RESEARCH
5.1. Conclusions
As mentioned in Chapter 1, the current literature is essentially void of research articles focusing
on ozone’s use as a disinfectant in any type of manufacturing environment and how its use my
affect workers. Therefore, the research conducted for this project initiated the evaluation and
characterization of the airborne ozone that workers are exposed to while working in a bottled
water manufacturing facility, specifically in the portion of the facility where bottles are actively
being filled with product water. Additionally, the research began the identification of certain
factors present in these work areas where ozone is present in its atmosphere and an evaluation of
how these factors influence the concentration of the airborne ozone. It was also mentioned in
Chapter 1, that the circumstances, under which the air sampling took place, were far from what is
typically encountered under controlled laboratory and experimental conditions.
Despite these limitations, there was valuable information compiled, organized and analyzed that
provided an enhanced level of insight into which factors have or do not have an impact on the
concentrations of airborne ozone in the Filler Room.
Some of the key findings identified during the statistical analysis of the data set indicated the
following:
1) The airborne ozone concentration is definitely influenced by the type of products being
produced with purified products accounting for the highest mean airborne ozone
concentrations, followed by natural spring water products and ending with no products being
produced having the lowest mean airborne ozone concentrations.
95
2) The mean airborne ozone concentration is considerably higher when the larger size bottles
(0.5L) of purified water are being filled when compared to the smaller size bottles (8.5 oz).
3) The number of AHUs in operation has a significant affect over the mean airborne ozone
concentrations. As the number of AHUs in operation increased from one to two and finally
to three, the mean airborne ozone concentrations decreased considerably.
4) As the ozone level in the ozonated rinse water increases, the airborne ozone concentration
increases proportionately regardless if purified products or spring water products are being
bottled or even when no bottles are being filled.
5) The status of Line #4 did not significantly affect the airborne ozone concentrations. The
analysis determined that there was not much difference in the mean airborne ozone
concentrations before or after the temporary wall was removed even though its removal
coincided very closely with the startup of Line #4.
6) There are many factors occurring simultaneously in an active Filler Room that have the
potential to either liberate ozone gas into the Filler Room or influence (increase, decrease or
have little or no effect) the airborne ozone concentration. The interactions between certain
combinations of these factors can make it rather difficult to quantitatively determine which
variables take precedence over the others when it comes to understanding which ones present
the most influence over the airborne ozone concentration in the Filler Room. However, the
production of purified water and the number of AHUs in operation seem to have a significant
influence on the airborne ozone concentrations.
5.2. Recommendations for Future Research
It is worth noting that the research triggered several ideas that warrant further experimentation,
data collection and study. These additional experiments should help to further advance the
understanding of how ozone gas behaves in a workplace atmosphere and how the airborne
concentrations can be managed to safe levels.
96
The first of these ideas recognizes the realization that there were several other factors that were
not considered in the initial research. Further research may provide a better understanding as to
how these factors can influence the level of airborne ozone present in a work area where bottles
are filled with water.
The second idea involves methods that can be used to destroy residual levels of ozone in the
incoming air from the outside of the building as well as the air recirculated from the Filler Room
that would help reduce the level of airborne ozone present in the room.
The third idea involves performing studies of the airflow patterns created by the AHUs and the
equipment layout in the Filler Room to gain a better understanding as to how ventilation
influences the airborne ozone concentrations.
Finally, the Filler Room offers a unique setting to further understand how the levels of airborne
ozone affects the health of the workers present in this type of work environment by conducting
additional air sampling but this time focusing on personal sampling of the workers.
Each of these ideas will be discussed in more detail in the paragraphs that follow.
5.2.1. Other Factors Influencing the Level of Airborne Ozone
In addition to the various factors that were studied and formed the basis of the research for this
paper, other factors that may influence the level of airborne ozone in the Filler Room were not
studied when the initial round of 24 sample periods took place. Many of these factors will need
to be monitored somewhat simultaneously with the results recorded over the course of an
individual sampling period involving each of the four fillers. These factors include:
1) Incremental production downtime that periodically occurs to a filler throughout a production
shift.
2) The relative humidity and temperature profile in the Filler Room.
3) The level of ozone present in the air stream exhausted from the Filler Room by each AHU
and recirculated back into the Filler Room through the diffusers.
97
4) The level of naturally occurring ozone in the intake air of each AHU brought into the
building from the outside prior to mixing with the recirculated air from the Filler Room.
Research indicates that the daytime summer seasonal background ozone concentration in the
United States is estimated to range from 0.025 to 0.045 ppm [48].
5) The concentration of background ozone in the vicinity of the plant recorded over a year’s
span so that the seasonal changes in the naturally occurring ozone that is brought into the
plant through the AHUs can be documented and evaluated. These measurements should be
taken on the roof of the facility near the Filler Room air intakes. This information will help
test the theory that airborne ozone concentrations are higher in summer months and lower in
winter months.
6) The concentration of background ozone that occurs during the night in the vicinity of the
plant. This information will help test the theory that ozone concentrations tend to peak in
early- to mid-afternoon in areas where there is strong photochemical activity such as in urban
areas and later in the day in rural areas (such as where the plant for this research took place)
where wind drift transports higher ozone concentrations at night.
7) The local ambient weather conditions (e.g., temperature, relative humidity, wind direction
and speed and percentage of cloud cover / sun shine).
5.2.2. Potential Methods of Ozone Destruction
Understanding which factors and how a specific factor can influence the level of airborne ozone
in a Filler Room are important when it comes to controlling worker exposure. What is equally
important is to identify methods that can be implemented to destroy the residual ozone in the air
recirculated from the Filler Room as well as the naturally occurring ozone in the fresh air that is
brought into the plant from the exterior of the building through the AHUs’ outside air intake
ductwork. There are two theories that the literature review identified as being effective at
destroying residual ozone. However, each of them must be proven to be effective through
experimentation in the AHUs of an active bottled water manufacturing facility.
The first of these methods is to use air filters positioned inside the AHUs for the Filler Room that
have been impregnated or embedded with a catalyst (e.g., precious metals to include platinum,
gold or palladium on a support surface or metallic oxides such as manganese, copper or nickel
98
oxide) that has been specifically engineered for the exothermic decomposition of ozone to
molecular oxygen. The theory behind this experiment is as the ozone-containing air passes
through the filters, the ozone will be destroyed by the exothermal catalytic reaction of the
catalyst. This setup is similar to the ozone destruct systems that are commonly installed on
OCTs for the purpose of destroying the excess ozone in the headspace of OCTs as it is exhausted
from an OCT. Parameters that may be of benefit to help facilitate the ozone destruction are the
airstream temperature and the speed at which the airstream passes through the filters. As is the
case with most catalyst, it will eventually become ineffective over time and will need to be
regenerated. This ozone destruct idea is based on research conducted by Zhao et al [49].
The second method is to simply install a UV light in the plenum of the Filler Room AHUs. As
discussed in section 2.2, a UV light set at the appropriate wavelength of 254 nm is designed to
destroy ozone and reduce it to one oxygen atom and one oxygen molecule. The same principle
of operation that was mentioned for the air filter / catalyst could also be used for the UV light.
The idea is to pass the air stream in the AHU plenum through the UV light at a rate that would be
conducive to the destruction of the residual ozone.
Either of these methods should prove effective for eliminating the residual fraction of ozone
circulated through the Filler Room’s AHUs, which should help maintain the ozone
concentrations below established occupational exposure limits.
5.2.3. Air Flow Patterns and Their Influence on the Level of Airborne Ozone
As with most cases of successfully controlling hazardous contaminants in the workplace
atmosphere, the effectiveness of the ventilation in the particular work area plays a key role.
There are several factors associated with the ventilation within the Filler Room that warrant
further study. These include:
1) Using smoke tubes to visualize the air flow patterns within the Filler Room to identify any
“dead spots,” cross-drafts or other interferences created by competing air moving devices
(e.g., air conveyor blowers), layout / spatial configuration of production and conveying
equipment or other obstructions that can adversely impact the air flow patterns in the Filler
Room and hinder the effective removal of airborne ozone.
99
2) Identifying the optimal locations (e.g., at the floor level, 6 feet above floor level or near
ceiling height) where the intakes for the AHU exhaust ducts and supply diffusers in the Filler
Room should be positioned to minimize “dead spots,” cross-drafts and other unfavorable air
currents and optimize the efficient removal of airborne ozone.
3) Determining what impact, if any, an increase or decrease in the number of air changes per
hour has on the airborne ozone concentrations in the Filler Room.
5.2.4. Detrimental or Therapeutic Effects of Ozone
The final idea warranting further study involves two topics: conducting additional personal air
sampling and correlating the results with health effects experienced by the Filler Room workers.
The additional sampling would involve following the OSHA method Ozone in Workplace
Atmospheres (Impregnated Glass Fiber Filter) (ID-214) that utilizes either a cassette and an air
sampling pump or a personal monitoring badge to perform the sampling. This equipment would
be affixed to each worker, who is operating one of the plant’s four Fillers, to monitor his or her
daily shift exposure to airborne ozone. As previously discussed in Chapter 3, the initial research
relied solely on area samples. This additional personal sampling is necessary to provide a better
representation and quantification of the actual airborne ozone workers are exposed to in their
breathing zone as they complete their daily work activities over an entire shift.
From a worker health standpoint, the Filler Room environment provides a group of potential test
subjects, who are members of a unique population, that are routinely exposed to ever changing
concentrations of airborne ozone while working at a relatively light metabolic work rate. What
makes this group unique is the fact that the workers in the Filler Room are present in this work
environment for up to 12 hours in an atmosphere where low concentrations of ozone are
constantly present. This is because the workers follow an annual work cycle of three consecutive
days of 12-hour shifts with four consecutive days off followed by four consecutive days of 12-
hour shifts followed by three consecutive days off. This work cycle is similar to the research
cited in Chapter 2 that indicates individuals repeatedly exposed to low concentrations of airborne
ozone may actually build up a tolerance to ozone’s ability to induce injury to the lungs [34], [35],
[36]. Additionally, the level of exposure and work rate experienced by this group is quite
different from many of the controlled human studies that challenge the test subject with a known
100
and fixed concentration of ozone while the subject is exercising at a relatively brisk rate, leading
the person to inhale deeply which deposits ozone deep into the lungs.
Using the above scenarios as the basis for future worker health studies, it would be instructive to
determine if these individuals experience similar ozone induced short- and long-term adverse
health effects at the same severity and frequency to what the general public experiences when
exposed to ground-level ozone in smog or test subjects when exposed to ozone under controlled
laboratory conditions. One variable that would need to be calculated and recorded for this study
is the work rate of the equipment operators.
Conversely, the health of the workers could also be monitored to determine if ozone, at these low
concentrations, provides a therapeutic effect on the worker’s health. This is similar to the effect
that is achieved by using the small-scale medical ozone generators designed for a home
environment. As mentioned in Chapter 2, ozone is one of the most effective disinfectants against
viruses and bacteria. Based on this property of ozone, the health study could be expanded to
determine if these workers experience a lower incidence of ailments such as the common cold;
headaches; eye, nose and throat irritation; sinus infections; bronchitis; persistent cough;
influenza; nasal and lung congestion; pneumonia; etc. Additionally, the individuals could be
evaluated against the same lung function performance tests {such as forced vital capacity (FVC),
total lung capacity (TLC) or forced expiratory volume in 1 second (FEV1)} identified in section
2.9 to determine if their lungs have experienced any level of impairment.
It is understood that the experiments will require significant resources from a monetary and
manpower standpoint as well as considerable time spent to setup and oversee the experiments
and to analyze the collected data. Additionally, multiple analytical instruments will be required
to collect the data for the experiments. This is due in part for the need to simultaneously monitor
the various factors so they can be collectively evaluated for their impact on the overall airborne
ozone concentration in the Filler Room. However, the knowledge acquired from understanding
the impact the above factors have on the airborne ozone concentration can help engineers and
architects include the appropriate features in the design of the prototypical layout for a bottled
101
water filler room, which should help create and maintain a safe and healthy work environment
for the equipment operators to work in.
102
APPENDIX A: Summary of Ozone Related Health Effects
Table provides a summary of evidence from epidemiologic, controlled human exposure,
and animal toxicological studies on the health effects associated with short- and long-term
exposure to ozone.
Health Outcome Conclusions from 2006
Ozone AQCD
Conclusions from 2012 3rd Draft
Integrated Science Assessment
Short-Term Exposure to Ozone
Respiratory Effects The overall evidence supports a causal
relationship between acute ambient ozone
(O3) exposures and increased respiratory
morbidity outcomes.
Evidence integrated across controlled human
exposure, epidemiologic, and toxicological
studies and across the spectrum of respiratory
health endpoints continues to demonstrate that
there is a causal relationship between short-
term O3 exposure and respiratory health
effects.
Lung Function Results from controlled human exposure
studies and animal toxicological studies
provide clear evidence of causality for the
associations observed between acute (≤ 24
h) O3 exposure and relatively small, but
statistically significant declines in lung
function observed in numerous recent
epidemiologic studies. Declines in lung
function are particularly noted in children,
asthmatics, and adults who work or exercise
outdoors.
Recent controlled human exposure studies
demonstrate group mean decreases in FEV1 in
the range of 2 to 3% with 6.6 hour exposures
to as low as 60 ppb O3. The collective body of
epidemiologic evidence demonstrates
associations between short-term ambient O3
exposure and decrements in lung function,
particularly in children with asthma, children,
and adults who work or exercise outdoors.
Airway hyperresponsiveness Evidence from human clinical and animal
toxicological studies clearly indicate that
acute exposure to O3 can induce airway
hyperreactivity, thus likely placing atopic
asthmatics at greater risk for more
prolonged bouts of breathing difficulties
due to airway constriction in response to
various airborne allergens or other
triggering stimuli.
A limited number of studies have observed
airway hyperresponsiveness in rodents and
guinea pigs after exposure to less than 300
ppb O3. As previously reported in the 2006
O3 AQCD, increased airway responsiveness
has been demonstrated at 80 ppb in young,
healthy adults, and at 50 ppb in certain strains
of rats.
Pulmonary inflammation,
injury and oxidative stress
The extensive human clinical and animal
toxicological evidence, together with the
limited available epidemiologic evidence, is
clearly indicative of a causal role for O3 in
inflammatory responses in the airways.
Epidemiologic studies provided new evidence
for associations of ambient O3 with mediators
of airway inflammation and oxidative stress
and indicate that higher antioxidant levels may
reduce pulmonary inflammation associated
with O3 exposure. Generally, these studies had
mean 8-h max O3 concentrations less than 73
ppb. Recent controlled human exposure
studies show O3-induced inflammatory
responses at 60 ppb, the lowest concentration
evaluated.
Respiratory symptoms and
medication use
Young healthy adult subjects exposed in
clinical studies to O3 concentrations ≥ 80
ppb for 6 to 8 h during moderate exercise
exhibit symptoms of cough and pain on
deep inspiration. The epidemiologic
evidence shows significant associations
between acute exposure to ambient O3 and
increases in a wide variety of respiratory
symptoms (e.g., cough, wheeze, production
of phlegm, and shortness of breath) and
medication use in asthmatic children.
The collective body of epidemiologic evidence
demonstrates positive associations between
short-term exposure to ambient O3 and
respiratory symptoms (e.g., cough, wheeze,
and shortness of breath) in children with
asthma. Generally, these studies had mean 8-h
max O3 concentrations less than 69 ppb.
103
Health Outcome Conclusions from 2006
Ozone AQCD
Conclusions from 2012 3rd Draft
Integrated Science Assessment
Lung host defenses Toxicological studies provided extensive
evidence that acute O3 exposures as low as
80 to 500 ppb can cause increases in
susceptibility to infectious diseases due to
modulation of lung host defenses. A single
controlled human exposure study found
decrements in the ability of alveolar
macrophages to phagocytize
microorganisms upon exposure to 80 to 100
ppb O3.
Recent controlled human exposure studies
demonstrate the increased expression of cell
surface markers and alterations in sputum
leukocyte markers related to innate adaptive
immunity with short-term O3 exposures of 80-
400 ppb. Recent studies demonstrating altered
immune responses and natural killer cell
function build on prior evidence that O3 can
affect multiple aspects of innate and acquired
immunity with short-term O3 exposures as low
as 80 ppb.
Allergic and asthma related
responses
Previous toxicological evidence indicated
that O3 exposure skews immune responses
toward an allergic phenotype, and enhances
the development and severity of asthma-
related responses such as AHR.
Recent controlled human exposure studies
demonstrate enhanced allergic cytokine
production in atopic individuals and
asthmatics, increased IgE receptors in atopic
asthmatics, and enhanced markers of innate
immunity and antigen presentation in health
subjects or atopic asthmatics with short-term
exposure to 80-400 ppb O3, all of which may
enhance allergy and/or asthma. Further
evidence for O3-induced allergic skewing is
provided by a few recent studies in rodents
using exposure concentrations as low as 200
ppb.
Respiratory Hospital
admissions, ED visits, and
physician visits
Aggregate population time-series studies
observed that ambient O3 concentrations
are positively and robustly associated with
respiratory-related hospitalizations and
asthma ED visits during the warm season.
Consistent, positive associations of ambient
O3 with respiratory hospital admissions and
ED visits in the U.S., Europe, and Canada with
supporting evidence from single city studies.
Generally, these studies had mean 8-h max O3
concentrations less than 60 ppb.
Respiratory Mortality Aggregate population time-series studies
specifically examining mortality from
respiratory causes were limited in number
and showed inconsistent associations
between acute exposure to ambient O3
exposure and respiratory mortality.
Recent multicity time-series studies and a
multicontinent study consistently
demonstrated associations between ambient
O3 and respiratory-related mortality visits
across the U.S., Europe, and Canada with
supporting evidence from single city studies.
Generally, these studies had mean 8-h max O3
concentrations less than 63 ppb.
Cardiovascular Effects The limited evidence is highly suggestive that O3
directly and/or indirectly contributes to
cardiovascular-related morbidity, but much remains to be done to more fully substantiate the
association.
The overall body of evidence across disciplines is
suggestive of a causal relationship for relevant
short-term exposures to O3 and cardiovascular
effects.
Central Nervous System
Effects
Toxicological studies report that acute
exposures to O3 are associated with
alterations in neurotransmitters, motor
activity, short- and long-term memory,
sleep patterns, and histological signs of
neurodegeneration.
Together the evidence from studies of short-
term exposure to O3 is suggestive of a causal
relationship between O3 exposure and CNS
effects.
Total Mortality The evidence is highly suggestive that O3
directly or indirectly contributes to non-
accidental and cardiopulmonary-related
mortality.
Taken together, the body of evidence indicates
that there is likely to be a causal relationship
between short-term exposures to O3 and
all-cause total mortality.
104
Health Outcome Conclusions from 2006
Ozone AQCD
Conclusions from 2012 3rd Draft
Integrated Science Assessment
Long-term Exposure to Ozone
Respiratory Effects The current evidence is suggestive but
inconclusive for respiratory health effects
from long-term O3 exposure.
Recent epidemiologic evidence, combined
with toxicological studies in rodents and non-
human primates, provides biologically
plausible evidence that there is likely to be a
causal relationship between long-term
exposure to O3 and respiratory health
effects.
New onset asthma No studies examining this outcome were
evaluated in the 2006 O3 AQCD.
Evidence that different genetic variants
(HMOX, GST, ARG), in combination with O3
exposure, are related to new onset asthma.
These associations were observed when
subjects living in areas where the mean annual
8-h max O3 concentration was 55.2 ppb,
compared to those who lived where it was 38.4
ppb.
Asthma hospital admissions No studies examining this outcome were
evaluated in the 2006 O3 AQCD.
Chronic O3 exposure was related to first
childhood asthma hospital admissions in a
positive concentration-response relationship.
Generally, these studies had mean annual 8-h
max O3 concentrations less than 41 ppb.
Pulmonary structure and
function
Epidemiologic studies observed that
reduced lung function growth in children
was associated with seasonal exposure to
O3; however, cohort studies of annual or
multiyear O3 exposure observed little clear
evidence for impacts of longer-term,
relatively low-level O3 exposure on lung
function development in children. Animal
toxicological studies reported chronic O3-
induced structural alterations, some of
which were irreversible, in several regions
of the respiratory tract including the
centriacinar region. Morphologic evidence
from studies using exposure regimens that
mimic seasonal exposure patterns report
increased lung injury compared to
conventional chronic stable exposures.
Evidence for pulmonary function effects is
inconclusive, with some new epidemiologic
studies observing positive associations (mean
annual 8-h max O3 concentrations less than 65
ppb). Information from toxicological studies
indicates that long-term maternal exposure
during gestation (100 ppb) or development
(500 ppb) can result in irreversible
morphological changes in the lung, which in
turn can influence pulmonary function.
Pulmonary inflammation,
injury and oxidative stress
Extensive human clinical and animal
toxicological evidence, together with
limited epidemiologic evidence available,
suggests a causal role for O3 in
inflammatory responses in the airways.
Several epidemiologic studies (mean 8-h max
O3 concentrations less than 69 ppb) and
toxicology studies (as low as 500 ppb) add to
observations of O3-induced inflammation and
injury.
Lung host defenses Toxicological studies provided evidence
that chronic O3 exposure as low as 100 ppb
can cause increases in susceptibility to
infectious diseases due to modulation of
lung host defenses, but do not cause greater
effects on infectivity than short exposures.
Consistent with decrements in host defenses
observed in rodents exposed to 100 ppb O3,
recent evidence demonstrates a decreased
ability to respond to pathogenic signals in
infant monkeys exposed to 500 ppb O3.
Allergic responses Limited epidemiologic evidence supported
an association between ambient O3 and
allergic symptoms. Little if any information
was available from toxicological studies.
Evidence relates positive outcomes of allergic
response and O3 exposure but with variable
strength for the effect estimates; exposure to
O3 may increase total IgE in adult asthmatics.
Allergic indicators in monkeys were increased
by exposure to O3 concentrations of 500 ppb.
105
Health Outcome Conclusions from 2006
Ozone AQCD
Conclusions from 2012 3rd Draft
Integrated Science Assessment Respiratory mortality Studies of cardio-pulmonary mortality were
insufficient to suggest a causal relationship
between chronic O3 exposure and increased
risk for mortality in humans.
A single study demonstrated that exposure to
O3 (long-term mean O3 less than 104 ppb)
elevated the risk of death from respiratory
causes and this effect was robust to the
inclusion of PM2.5.
Cardiovascular Effects No studies examining this outcome were
evaluated in the 2006 O3 AQCD.
The overall body of evidence across
disciplines is suggestive of a causal
relationship for relevant long-term
exposures to O3 and cardiovascular effects.
Reproductive and
Developmental effects
Limited evidence for a relationship between
air pollution and birth-related health
outcomes, including mortality, premature
births, low birth weights, and birth defects,
with little evidence being found for O3
effects.
Overall, the evidence is suggestive of a causal
relationship between long-term exposures to
O3 and reproductive and developmental
effects.
Central Nervous System
Effects
Toxicological studies reported that acute
exposures to O3 are associated with
alterations in neurotransmitters, motor
activity, short and long term memory, sleep
patterns, and histological signs of
neurodegeneration. Evidence regarding
chronic exposure and neurobehavioral
effects was not available.
Together the evidence from studies of long-
term exposure to O3 is suggestive of a causal
relationship between O3 exposure and CNS
effects.
Cancer Little evidence for a relationship between
chronic O3 exposure and increased risk of
lung cancer.
Overall, the evidence is inadequate to
determine if a causal relationship exists
between ambient O3 exposures and cancer.
Total Mortality There is little evidence to suggest a causal
relationship between chronic O3 exposure
and increased risk for mortality in humans.
Collectively, the evidence is suggestive of a
causal relationship between long-term O3
exposures and total mortality.
Source: Integrated Science Assessment of Ozone and Related Photochemical Oxidants (Third External Review
Draft), U.S. EPA
106
APPENDIX B: National Ambient Air Quality Standards
EPA has set National Ambient Air Quality Standards for six principal pollutants, which are
called "criteria" pollutants. They are listed below. Units of measure for the standards are parts
per million (ppm) by volume, parts per billion (ppb) by volume, and micrograms per cubic meter
of air (µg/m3).
Pollutant
[final rule cite]
Primary/
Secondary Averaging Time Level Form
Carbon Monoxide [76 FR 54294, Aug 31, 2011]
primary 8-hour 9 ppm Not to be exceeded more than once per
year 1-hour 35 ppm
Lead
[73 FR 66964, Nov 12, 2008]
primary and
secondary Rolling 3 month average 0.15 μg/m3 (1) Not to be exceeded
Nitrogen Dioxide
[75 FR 6474, Feb 9, 2010] [61 FR 52852, Oct 8, 1996]
primary 1-hour 100 ppb 98th percentile, averaged over 3 years
primary and
secondary Annual 53 ppb (2) Annual Mean
Ozone
[73 FR 16436, Mar 27, 2008]
primary and
secondary 8-hour 0.075 ppm (3)
Annual fourth-highest daily maximum 8-
hr concentration, averaged over 3 years
Particle Pollution [71 FR 61144,
Oct 17, 2006]
PM2.5 primary and
secondary
Annual 15 μg/m3 annual mean, averaged over 3 years
24-hour 35 μg/m3 98th percentile, averaged over 3 years
PM10 primary and
secondary 24-hour 150 μg/m3
Not to be exceeded more than once per
year on average over 3 years
Sulfur Dioxide
[75 FR 35520, Jun 22, 2010]
[38 FR 25678, Sept 14, 1973]
primary 1-hour 75 ppb (4) 99th percentile of 1-hour daily maximum
concentrations, averaged over 3 years
secondary 3-hour 0.5 ppm Not to be exceeded more than once per year
as of October 2011
(1) Final rule signed October 15, 2008. The 1978 lead standard (1.5 µg/m3 as a quarterly average) remains in effect
until one year after an area is designated for the 2008 standard, except that in areas designated nonattainment for the
1978, the 1978 standard remains in effect until implementation plans to attain or maintain the 2008 standard are
approved.
(2) The official level of the annual NO2 standard is 0.053 ppm, equal to 53 ppb, which is shown here for the purpose
of clearer comparison to the 1-hour standard.
(3) Final rule signed March 12, 2008. The 1997 ozone standard (0.08 ppm, annual fourth-highest daily maximum 8-
hour concentration, averaged over 3 years) and related implementation rules remain in place. In 1997, EPA revoked
the 1-hour ozone standard (0.12 ppm, not to be exceeded more than once per year) in all areas, although some areas
have continued obligations under that standard (“anti-backsliding”). The 1-hour ozone standard is attained when the
expected number of days per calendar year with maximum hourly average concentrations above 0.12 ppm is less than
or equal to 1.
(4) Final rule signed June 2, 2010. The 1971 annual and 24-hour SO2 standards were revoked in that same
rulemaking. However, these standards remain in effect until one year after an area is designated for the 2010
standard, except in areas designated nonattainment for the 1971 standards, where the 1971 standards remain in effect
until implementation plans to attain or maintain the 2010 standard are approved.
Source: US EPA Air and Radiation website (http://www.epa.gov/air/criteria.html)
107
APPENDIX C: Understanding the Air Quality Index The purpose of the Air Quality Index (AQI) is to help the public understand what local air
quality means to their health for five of the six pollutants (excludes lead). To make it easier to
understand, the AQI is divided into six numerical categories:
Air Quality Index (AQI) Values
Levels of Health Concern Colors
When the AQI is in this range: ..air quality conditions are: ...as symbolized by this color:
0-50 Good Green
51-100 Moderate Yellow
101-150 Unhealthy for Sensitive Groups Orange
151 to 200 Unhealthy Red
201 to 300 Very Unhealthy Purple
301 to 500 Hazardous Maroon
This page was last updated on Friday, December 09, 2011.
Each category corresponds to a different level of health concern. The six levels of health concern and what they
mean are:
"Good" AQI is 0 - 50. Air quality is considered satisfactory, and air pollution poses little or no risk.
"Moderate" AQI is 51 - 100. Air quality is acceptable; however, for some pollutants there may be a
moderate health concern for a very small number of people. For example, people who are unusually
sensitive to ozone may experience respiratory symptoms.
"Unhealthy for Sensitive Groups" AQI is 101 - 150. Although general public is not likely to be affected at
this AQI range, people with lung disease, older adults and children are at a greater risk from exposure to
ozone, whereas persons with heart and lung disease, older adults and children are at greater risk from the
presence of particles in the air. .
"Unhealthy" AQI is 151 - 200. Everyone may begin to experience some adverse health effects, and
members of the sensitive groups may experience effects that are more serious.
"Very Unhealthy" AQI is 201 - 300. This would trigger a health alert signifying that everyone may
experience more serious health effects.
"Hazardous" AQI greater than 300. This would trigger a health warning of emergency conditions. The
entire population is more likely to be affected.
Source: AIRNow website Air Quality Index (AQI) - A Guide to Air Quality and Your Health
(http://airnow.gov/index.cfm?action=aqibasics.aqi)
108
APPENDIX D: Air Quality Index Colors
EPA has assigned a specific color to each AQI category to make it easier for the public to
understand quickly whether air pollution is reaching unhealthy levels in their communities. For
example, the color orange means that conditions are "unhealthy for sensitive groups," while red
means that conditions may be "unhealthy for everyone," and so on.
Air Quality Index Levels of Health
Concern
Numerical Value
Meaning
Good 0 to 50 Air quality is considered satisfactory, and air pollution poses little or no risk
Moderate 51 to 100 Air quality is acceptable; however, for some pollutants there may be a moderate health concern for a very small number of people who are unusually sensitive to air pollution.
Unhealthy for Sensitive Groups
101 to 150 Members of sensitive groups may experience health effects. The general public is not likely to be affected.
Unhealthy 151 to 200 Everyone may begin to experience health effects; members of sensitive groups may experience more serious health effects.
Very Unhealthy 201 to 300 Health warnings of emergency conditions. The entire population is more likely to be affected.
Hazardous 301 to 500 Health alert: everyone may experience more serious health effects
This page was last updated on Friday, December 09, 2011.
Source: AIRNow website Air Quality Index (AQI) - A Guide to Air Quality and Your Health
(http://airnow.gov/index.cfm?action=aqibasics.aqi)
109
APPENDIX E: Air Quality Guide for Ozone
This Table identifies health effects associated with different levels of ground-level ozone, along
with the cautionary statements that would be appropriate if the ground-level ozone in a
community were to fall into one of the "unhealthful" categories on the AQI scale.
Ozone Concentration (ppm) (8-hour average, unless noted)
Air Quality Index
Protect Your Health
0.0 to 0.064 Good (0-50)
No health impacts are expected when air quality is in this range.
0.065 to 0.084 Moderate (51-100)
Unusually sensitive people should consider limiting prolonged outdoor exertion.
0.085 to 0.104 Unhealthy for
Sensitive Groups (101-150)
The following groups should limit prolonged outdoor exertion:
People with lung disease, such as asthma
Children and older adults
People who are active outdoors
0.105 to 0.124 Unhealthy (151-200)
The following groups should avoid prolonged outdoor exertion:
People with lung disease, such as asthma
Children and older adults
People who are active outdoors
Everyone else should limit prolonged outdoor exertion.
0.125 (8-hr) to 0.404 (1-hr) Very Unhealthy
(201-300)
The following groups should avoid all outdoor exertion:
People with lung disease, such as asthma
Children and older adults
People who are active outdoors
Everyone else should limit outdoor exertion.
Source: AirNow website Smog – Who Does It Hurt? (http://airnow.gov/index.cfm?action=smog.page1#1)
110
APPENDIX F: Health Effects and Protective Actions for Specific Ozone Ranges
Ozone Level Health Effects and Protective Actions
Good What are the possible health effects?
No health effects are expected.
Moderate What are the possible health effects?
Unusually sensitive individuals may experience respiratory effects from prolonged exposure to ozone during outdoor exertion.
What can I do to protect my health?
When ozone levels are in the "moderate" range, consider limiting prolonged outdoor exertion if you are unusually sensitive to ozone.
Unhealthy for Sensitive Groups
What are the possible health effects?
If you are a member of a sensitive group,(1)
you may experience respiratory symptoms (such as coughing or pain when taking a deep breath) and reduced lung function, which can cause some breathing discomfort.
What can I do to protect my health?
If you are a member of a sensitive group,(1)
limit prolonged outdoor exertion. In general, you can protect your health by reducing how long or how strenuously you exert yourself outdoors and by planning outdoor activities when ozone levels are lower (usually in the early morning or evening).
You can check with your State air agency to find out about current or predicted ozone levels in your location. This information on ozone levels is available on the Internet at http://www.epa.gov/airnow
Unhealthy What are the possible health effects?
If you are a member of a sensitive group,(1)
you have a higher chance of experiencing respiratory symptoms (such as aggravated cough or pain when taking a deep breath), and reduced lung function, which can cause some breathing difficulty.
At this level, anyone could experience respiratory effects. What can I do to protect my health?
If you are a member of a sensitive group,(1)
avoid prolonged outdoor exertion. Everyone else-especially children-should limit prolonged outdoor exertion.
Plan outdoor activities when ozone levels are lower (usually in the early morning or evening).
You can check with your State air agency to find out about current or predicted ozone levels in your location. This information on ozone levels is available on the Internet at http://www.epa.gov/airnow.
Very Unhealthy What are the possible health effects?
Members of sensitive groups(1)
will likely experience increasingly severe respiratory symptoms and impaired breathing.
Many healthy people in the general population engaged in moderate exertion will experience some kind of effect. According to EPA estimates, approximately: - Half will experience moderately reduced lung function. - One-fifth will experience severely reduced lung function. - 10 to 15 percent will experience moderate to severe respiratory symptoms (such as aggravated cough and pain when taking a deep breath).
People with asthma or other respiratory conditions will be more severely affected, leading some to increase medication usage and seek medical attention at an emergency room or clinic.
What can I do to protect my health?
If you are a member of a sensitive group,(1)
avoid outdoor activity altogether. Everyone else especially children should limit outdoor exertion and avoid heavy exertion altogether.
Check with your State air agency to find out about current or predicted ozone levels in your location. This information on ozone levels is available on the Internet at http://www.epa.gov/airnow.
1 Members of sensitive groups include children who are active outdoors; adults involved in moderate or strenuous outdoor activities; individuals with respiratory disease, such as asthma; and individuals with unusual susceptibility to ozone.
Source: Smog – Who Does It Hurt? (http://www.epa.gov/airnow/health/smog.pdf)
111
APPENDIX G: Ozone Monitoring Data Set
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
1 1 1 Spring 25oz Spring 1 Yes 0.111 0.36 0.19 BL4
1 1 2 Spring 25oz Spring 1 Yes 0.13 0.36 0.19 BL4
1 1 3 Spring 25oz Spring 1 Yes 0.125 0.36 0.19 BL4
1 1 4 Spring 25oz Spring 1 Yes 0.126 0.36 0.19 BL4
1 1 5 Spring 25oz Spring 1 Yes 0.116 0.36 0.19 BL4
1 1 6 Spring 25oz Spring 1 Yes 0.111 0.36 0.19 BL4
1 2 1 Purified .5L Purified 1 Yes 0.165 0.36 0.19 BL4
1 2 2 Purified .5L Purified 1 Yes 0.197 0.36 0.19 BL4
1 2 3 Purified .5L Purified 1 Yes 0.142 0.36 0.19 BL4
1 2 4 Purified .5L Purified 1 Yes 0.169 0.36 0.19 BL4
1 2 5 Purified .5L Purified 1 Yes 0.172 0.36 0.19 BL4
1 2 6 Purified .5L Purified 1 Yes 0.19 0.36 0.19 BL4
1 3 1 Spring 8.5oz Spring 1 Yes 0.151 0.36 0.19 BL4
1 3 2 Spring 8.5oz Spring 1 Yes 0.137 0.36 0.19 BL4
1 3 3 Spring 8.5oz Spring 1 Yes 0.171 0.36 0.19 BL4
1 3 4 Spring 8.5oz Spring 1 Yes 0.239 0.36 0.19 BL4
1 3 5 Spring 8.5oz Spring 1 Yes 0.209 0.36 0.19 BL4
1 3 6 Spring 8.5oz Spring 1 Yes 0.212 0.36 0.19 BL4
2 1 1 Spring 25oz Spring 1 Yes 0.06 0.39 0.19 BL4
2 1 2 Spring 25oz Spring 1 Yes 0.084 0.39 0.19 BL4
2 1 3 Spring 25oz Spring 1 Yes 0.084 0.39 0.19 BL4
2 1 4 Spring 25oz Spring 1 Yes 0.098 0.39 0.19 BL4
2 1 5 Spring 25oz Spring 1 Yes 0.098 0.39 0.19 BL4
2 1 6 Spring 25oz Spring 1 Yes 0.097 0.39 0.19 BL4
2 2 1 Purified .5L Purified 1 Yes 0.139 0.39 0.19 BL4
2 2 2 Purified .5L Purified 1 Yes 0.204 0.39 0.19 BL4
2 2 3 Purified .5L Purified 1 Yes 0.139 0.39 0.19 BL4
2 2 4 Purified .5L Purified 1 Yes 0.177 0.39 0.19 BL4
2 2 5 Purified .5L Purified 1 Yes 0.154 0.39 0.19 BL4
2 2 6 Purified .5L Purified 1 Yes 0.166 0.39 0.19 BL4
2 3 1 Spring 8.5oz Spring 1 Yes 0.157 0.39 0.19 BL4
2 3 2 Spring 8.5oz Spring 1 Yes 0.174 0.39 0.19 BL4
2 3 3 Spring 8.5oz Spring 1 Yes 0.186 0.39 0.19 BL4
2 3 4 Spring 8.5oz Spring 1 Yes 0.236 0.39 0.19 BL4
2 3 5 Spring 8.5oz Spring 1 Yes 0.169 0.39 0.19 BL4
2 3 6 Spring 8.5oz Spring 1 Yes 0.198 0.39 0.19 BL4
3 1 1 Spring 25oz Spring 1 Yes 0.022 0.41 0.19 BL4
3 1 2 Spring 25oz Spring 1 Yes 0 0.41 0.19 BL4
112
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
3 1 3 Spring 25oz Spring 1 Yes 0.044 0.41 0.19 BL4
3 1 4 Spring 25oz Spring 1 Yes 0.097 0.41 0.19 BL4
3 1 5 Spring 25oz Spring 1 Yes 0.09 0.41 0.19 BL4
3 1 6 Spring 25oz Spring 1 Yes 0.071 0.41 0.19 BL4
3 2 1 Purified .5L Purified 1 Yes 0.076 0.41 0.19 BL4
3 2 2 Purified .5L Purified 1 Yes 0.105 0.41 0.19 BL4
3 2 3 Purified .5L Purified 1 Yes 0.086 0.41 0.19 BL4
3 2 4 Purified .5L Purified 1 Yes 0.149 0.41 0.19 BL4
3 2 5 Purified .5L Purified 1 Yes 0.137 0.41 0.19 BL4
3 2 6 Purified .5L Purified 1 Yes 0.183 0.41 0.19 BL4
3 3 1 Spring 8.5oz Spring 1 Yes 0.186 0.41 0.19 BL4
3 3 2 Spring 8.5oz Spring 1 Yes 0.163 0.41 0.19 BL4
3 3 3 Spring 8.5oz Spring 1 Yes 0.222 0.41 0.19 BL4
3 3 4 Spring 8.5oz Spring 1 Yes 0.323 0.41 0.19 BL4
3 3 5 Spring 8.5oz Spring 1 Yes 0.311 0.41 0.19 BL4
3 3 6 Spring 8.5oz Spring 1 Yes 0.267 0.41 0.19 BL4
4 1 1 Spring .5L Spring 2 No 0.081 0.29 0.19 BL4
4 1 2 Spring .5L Spring 2 No 0.075 0.29 0.19 BL4
4 1 3 Spring .5L Spring 2 No 0.06 0.29 0.19 BL4
4 1 4 Spring .5L Spring 2 No 0.068 0.29 0.19 BL4
4 1 5 Spring .5L Spring 2 No 0.097 0.29 0.19 BL4
4 1 6 Spring .5L Spring 2 No 0.041 0.29 0.19 BL4
4 2 1 No Product No Product 2 No 0.058 0.29 0.19 BL4
4 2 2 No Product No Product 2 No 0.064 0.29 0.19 BL4
4 2 3 No Product No Product 2 No 0.058 0.29 0.19 BL4
4 2 4 No Product No Product 2 No 0.069 0.29 0.19 BL4
4 2 5 No Product No Product 2 No 0.045 0.29 0.19 BL4
4 2 6 No Product No Product 2 No 0.065 0.29 0.19 BL4
4 3 1 Spring .5L Spring 2 No 0.03 0.29 0.19 BL4
4 3 2 Spring .5L Spring 2 No 0 0.29 0.19 BL4
4 3 3 Spring .5L Spring 2 No 0.014 0.29 0.19 BL4
4 3 4 Spring .5L Spring 2 No 0.042 0.29 0.19 BL4
4 3 5 Spring .5L Spring 2 No 0.023 0.29 0.19 BL4
4 3 6 Spring .5L Spring 2 No 0.015 0.29 0.19 BL4
5 1 1 Spring .5L Spring 2 No 0.184 0.34 0.13 BL4
5 1 2 Spring .5L Spring 2 No 0.204 0.34 0.13 BL4
5 1 3 Spring .5L Spring 2 No 0.159 0.34 0.13 BL4
5 1 4 Spring .5L Spring 2 No 0.115 0.34 0.13 BL4
5 1 5 Spring .5L Spring 2 No 0.082 0.34 0.13 BL4
5 1 6 Spring .5L Spring 2 No 0.052 0.34 0.13 BL4
5 2 1 No Product No Product 2 No 0.057 0.34 0.13 BL4
5 2 2 No Product No Product 2 No 0.058 0.34 0.13 BL4
113
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
5 2 3 No Product No Product 2 No 0.065 0.34 0.13 BL4
5 2 4 No Product No Product 2 No 0.079 0.34 0.13 BL4
5 2 5 No Product No Product 2 No 0.069 0.34 0.13 BL4
5 2 6 No Product No Product 2 No 0.055 0.34 0.13 BL4
5 3 1 Spring .5L Spring 2 No 0.017 0.34 0.13 BL4
5 3 2 Spring .5L Spring 2 No 0.002 0.34 0.13 BL4
5 3 3 Spring .5L Spring 2 No 0.043 0.34 0.13 BL4
5 3 4 Spring .5L Spring 2 No 0.065 0.34 0.13 BL4
5 3 5 Spring .5L Spring 2 No 0.049 0.34 0.13 BL4
5 3 6 Spring .5L Spring 2 No 0.046 0.34 0.13 BL4
6 1 1 Spring .5L Spring 2 No 0.021 0.19 0.2 BL4
6 1 2 Spring .5L Spring 2 No 0.063 0.19 0.2 BL4
6 1 3 Spring .5L Spring 2 No 0.076 0.19 0.2 BL4
6 1 4 Spring .5L Spring 2 No 0.076 0.19 0.2 BL4
6 1 5 Spring .5L Spring 2 No 0.08 0.19 0.2 BL4
6 1 6 Spring .5L Spring 2 No 0.064 0.19 0.2 BL4
6 2 1 No Product No Product 2 No 0.101 0.19 0.2 BL4
6 2 2 No Product No Product 2 No 0.065 0.19 0.2 BL4
6 2 3 No Product No Product 2 No 0.064 0.19 0.2 BL4
6 2 4 No Product No Product 2 No 0.069 0.19 0.2 BL4
6 2 5 No Product No Product 2 No 0.061 0.19 0.2 BL4
6 2 6 No Product No Product 2 No 0.041 0.19 0.2 BL4
6 3 1 Spring .5L Spring 2 No 0.051 0.19 0.2 BL4
6 3 2 Spring .5L Spring 2 No 0.044 0.19 0.2 BL4
6 3 3 Spring .5L Spring 2 No 0.078 0.19 0.2 BL4
6 3 4 Spring .5L Spring 2 No 0.082 0.19 0.2 BL4
6 3 5 Spring .5L Spring 2 No 0.066 0.19 0.2 BL4
6 3 6 Spring .5L Spring 2 No 0.038 0.19 0.2 BL4
7 1 1 Spring .5L Spring 2 No 0.011 0.59 0.34 BL4
7 1 2 Spring .5L Spring 2 No 0.064 0.59 0.34 BL4
7 1 3 Spring .5L Spring 2 No 0.07 0.59 0.34 BL4
7 1 4 Spring .5L Spring 2 No 0.093 0.59 0.34 BL4
7 1 5 Spring .5L Spring 2 No 0.083 0.59 0.34 BL4
7 1 6 Spring .5L Spring 2 No 0.073 0.59 0.34 BL4
7 2 1 No Product No Product 2 No 0.08 0.59 0.34 BL4
7 2 2 No Product No Product 2 No 0.077 0.59 0.34 BL4
7 2 3 No Product No Product 2 No 0.062 0.59 0.34 BL4
7 2 4 No Product No Product 2 No 0.068 0.59 0.34 BL4
7 2 5 No Product No Product 2 No 0.064 0.59 0.34 BL4
7 2 6 No Product No Product 2 No 0.05 0.59 0.34 BL4
7 3 1 Spring .5L Spring 2 No 0.034 0.59 0.34 BL4
7 3 2 Spring .5L Spring 2 No 0.035 0.59 0.34 BL4
114
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
7 3 3 Spring .5L Spring 2 No 0.043 0.59 0.34 BL4
7 3 4 Spring .5L Spring 2 No 0.099 0.59 0.34 BL4
7 3 5 Spring .5L Spring 2 No 0.107 0.59 0.34 BL4
7 3 6 Spring .5L Spring 2 No 0.056 0.59 0.34 BL4
8 1 1 Spring .5L Spring 2 Yes 0.128 0.47 0.13 BL4
8 1 2 Spring .5L Spring 2 Yes 0.128 0.47 0.13 BL4
8 1 3 Spring .5L Spring 2 Yes 0.122 0.47 0.13 BL4
8 1 4 Spring .5L Spring 2 Yes 0.139 0.47 0.13 BL4
8 1 5 Spring .5L Spring 2 Yes 0.125 0.47 0.13 BL4
8 1 6 Spring .5L Spring 2 Yes 0.13 0.47 0.13 BL4
8 2 1 Purified .5L Purified 2 Yes 0.098 0.47 0.13 BL4
8 2 2 Purified .5L Purified 2 Yes 0.147 0.47 0.13 BL4
8 2 3 Purified .5L Purified 2 Yes 0.13 0.47 0.13 BL4
8 2 4 Purified .5L Purified 2 Yes 0.164 0.47 0.13 BL4
8 2 5 Purified .5L Purified 2 Yes 0.127 0.47 0.13 BL4
8 2 6 Purified .5L Purified 2 Yes 0.12 0.47 0.13 BL4
8 3 1 Spring .5L Spring 2 Yes 0.106 0.47 0.13 BL4
8 3 2 Spring .5L Spring 2 Yes 0.088 0.47 0.13 BL4
8 3 3 Spring .5L Spring 2 Yes 0.11 0.47 0.13 BL4
8 3 4 Spring .5L Spring 2 Yes 0.132 0.47 0.13 BL4
8 3 5 Spring .5L Spring 2 Yes 0.119 0.47 0.13 BL4
8 3 6 Spring .5L Spring 2 Yes 0.061 0.47 0.13 BL4
9 1 1 Spring .5L Spring 2 Yes 0.088 0.53 0.28 BL4
9 1 2 Spring .5L Spring 2 Yes 0.116 0.53 0.28 BL4
9 1 3 Spring .5L Spring 2 Yes 0.111 0.53 0.28 BL4
9 1 4 Spring .5L Spring 2 Yes 0.119 0.53 0.28 BL4
9 1 5 Spring .5L Spring 2 Yes 0.121 0.53 0.28 BL4
9 1 6 Spring .5L Spring 2 Yes 0.101 0.53 0.28 BL4
9 2 1 Purified .5L Purified 2 Yes 0.173 0.53 0.28 BL4
9 2 2 Purified .5L Purified 2 Yes 0.169 0.53 0.28 BL4
9 2 3 Purified .5L Purified 2 Yes 0.145 0.53 0.28 BL4
9 2 4 Purified .5L Purified 2 Yes 0.151 0.53 0.28 BL4
9 2 5 Purified .5L Purified 2 Yes 0.169 0.53 0.28 BL4
9 2 6 Purified .5L Purified 2 Yes 0.132 0.53 0.28 BL4
9 3 1 Spring .5L Spring 2 Yes 0.094 0.53 0.28 BL4
9 3 2 Spring .5L Spring 2 Yes 0.062 0.53 0.28 BL4
9 3 3 Spring .5L Spring 2 Yes 0.086 0.53 0.28 BL4
9 3 4 Spring .5L Spring 2 Yes 0.082 0.53 0.28 BL4
9 3 5 Spring .5L Spring 2 Yes 0.077 0.53 0.28 BL4
9 3 6 Spring .5L Spring 2 Yes 0.045 0.53 0.28 BL4
10 1 1 Spring .5L Spring 2 No 0.109 0.43 0.19 BL4
10 1 2 Spring .5L Spring 2 No 0.154 0.43 0.19 BL4
115
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
10 1 3 Spring .5L Spring 2 No 0.123 0.43 0.19 BL4
10 1 4 Spring .5L Spring 2 No 0.118 0.43 0.19 BL4
10 1 5 Spring .5L Spring 2 No 0.098 0.43 0.19 BL4
10 1 6 Spring .5L Spring 2 No 0.08 0.43 0.19 BL4
10 2 1 No Product No Product 2 No 0.073 0.43 0.19 BL4
10 2 2 No Product No Product 2 No 0.06 0.43 0.19 BL4
10 2 3 No Product No Product 2 No 0.048 0.43 0.19 BL4
10 2 4 No Product No Product 2 No 0.123 0.43 0.19 BL4
10 2 5 No Product No Product 2 No 0.08 0.43 0.19 BL4
10 2 6 No Product No Product 2 No 0.13 0.43 0.19 BL4
10 3 1 Spring .33L Spring 2 No 0.086 0.43 0.19 BL4
10 3 2 Spring .33L Spring 2 No 0.062 0.43 0.19 BL4
10 3 3 Spring .33L Spring 2 No 0.067 0.43 0.19 BL4
10 3 4 Spring .33L Spring 2 No 0.065 0.43 0.19 BL4
10 3 5 Spring .33L Spring 2 No 0.053 0.43 0.19 BL4
10 3 6 Spring .33L Spring 2 No 0.033 0.43 0.19 BL4
11 1 1 Spring .5L Spring 2 No 0.034 0.19 0.19 BL4
11 1 2 Spring .5L Spring 2 No 0.049 0.19 0.19 BL4
11 1 3 Spring .5L Spring 2 No 0.044 0.19 0.19 BL4
11 1 4 Spring .5L Spring 2 No 0.046 0.19 0.19 BL4
11 1 5 Spring .5L Spring 2 No 0.05 0.19 0.19 BL4
11 1 6 Spring .5L Spring 2 No 0.039 0.19 0.19 BL4
11 2 1 Spring .5L Spring 2 No 0.02 0.19 0.19 BL4
11 2 2 Spring .5L Spring 2 No 0.021 0.19 0.19 BL4
11 2 3 Spring .5L Spring 2 No 0.036 0.19 0.19 BL4
11 2 4 Spring .5L Spring 2 No 0.029 0.19 0.19 BL4
11 2 5 Spring .5L Spring 2 No 0.031 0.19 0.19 BL4
11 2 6 Spring .5L Spring 2 No 0.02 0.19 0.19 BL4
11 3 1 Spring .33L Spring 2 No 0.039 0.19 0.19 BL4
11 3 2 Spring .33L Spring 2 No 0.033 0.19 0.19 BL4
11 3 3 Spring .33L Spring 2 No 0.03 0.19 0.19 BL4
11 3 4 Spring .33L Spring 2 No 0.029 0.19 0.19 BL4
11 3 5 Spring .33L Spring 2 No 0.02 0.19 0.19 BL4
11 3 6 Spring .33L Spring 2 No 0.009 0.19 0.19 BL4
12 1 1 Spring .5L Spring 2 Yes 0.044 0.24 0.24 BL4
12 1 2 Spring .5L Spring 2 Yes 0.067 0.24 0.24 BL4
12 1 3 Spring .5L Spring 2 Yes 0.064 0.24 0.24 BL4
12 1 4 Spring .5L Spring 2 Yes 0.072 0.24 0.24 BL4
12 1 5 Spring .5L Spring 2 Yes 0.068 0.24 0.24 BL4
12 1 6 Spring .5L Spring 2 Yes 0.057 0.24 0.24 BL4
12 2 1 Purified .5L Purified 2 Yes 0.088 0.24 0.24 BL4
12 2 2 Purified .5L Purified 2 Yes 0.098 0.24 0.24 BL4
116
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
12 2 3 Purified .5L Purified 2 Yes 0.092 0.24 0.24 BL4
12 2 4 Purified .5L Purified 2 Yes 0.102 0.24 0.24 BL4
12 2 5 Purified .5L Purified 2 Yes 0.084 0.24 0.24 BL4
12 2 6 Purified .5L Purified 2 Yes 0.086 0.24 0.24 BL4
12 3 1 Spring .33L Spring 2 Yes 0.098 0.24 0.24 BL4
12 3 2 Spring .33L Spring 2 Yes 0.089 0.24 0.24 BL4
12 3 3 Spring .33L Spring 2 Yes 0.081 0.24 0.24 BL4
12 3 4 Spring .33L Spring 2 Yes 0.063 0.24 0.24 BL4
12 3 5 Spring .33L Spring 2 Yes 0.048 0.24 0.24 BL4
12 3 6 Spring .33L Spring 2 Yes 0.029 0.24 0.24 BL4
13 1 1 Spring .5L Spring 2 Yes 0.111 0.57 0.2 BL4
13 1 2 Spring .5L Spring 2 Yes 0.133 0.57 0.2 BL4
13 1 3 Spring .5L Spring 2 Yes 0.112 0.57 0.2 BL4
13 1 4 Spring .5L Spring 2 Yes 0.123 0.57 0.2 BL4
13 1 5 Spring .5L Spring 2 Yes 0.115 0.57 0.2 BL4
13 1 6 Spring .5L Spring 2 Yes 0.091 0.57 0.2 BL4
13 2 1 Purified .5L Purified 2 Yes 0.116 0.57 0.2 BL4
13 2 2 Purified .5L Purified 2 Yes 0.163 0.57 0.2 BL4
13 2 3 Purified .5L Purified 2 Yes 0.146 0.57 0.2 BL4
13 2 4 Purified .5L Purified 2 Yes 0.173 0.57 0.2 BL4
13 2 5 Purified .5L Purified 2 Yes 0.134 0.57 0.2 BL4
13 2 6 Purified .5L Purified 2 Yes 0.099 0.57 0.2 BL4
13 3 1 Purified 8.5oz Purified 2 Yes 0.095 0.57 0.2 BL4
13 3 2 Purified 8.5oz Purified 2 Yes 0.097 0.57 0.2 BL4
14 1 1 Spring .5L Spring 2 Yes 0.107 0.34 0.21 BL4
14 1 2 Spring .5L Spring 2 Yes 0.109 0.34 0.21 BL4
14 1 3 Spring .5L Spring 2 Yes 0.107 0.34 0.21 BL4
14 1 4 Spring .5L Spring 2 Yes 0.113 0.34 0.21 BL4
14 1 5 Spring .5L Spring 2 Yes 0.105 0.34 0.21 BL4
14 1 6 Spring .5L Spring 2 Yes 0.102 0.34 0.21 BL4
14 2 1 Purified .5L Purified 2 Yes 0.158 0.34 0.21 BL4
14 2 2 Purified .5L Purified 2 Yes 0.147 0.34 0.21 BL4
14 2 3 Purified .5L Purified 2 Yes 0.119 0.34 0.21 BL4
14 2 4 Purified .5L Purified 2 Yes 0.151 0.34 0.21 BL4
14 2 5 Purified .5L Purified 2 Yes 0.144 0.34 0.21 BL4
14 2 6 Purified .5L Purified 2 Yes 0.094 0.34 0.21 BL4
14 3 1 Purified .5L Purified 2 Yes 0.1 0.34 0.21 BL4
14 3 2 Purified .5L Purified 2 Yes 0.125 0.34 0.21 BL4
14 3 3 Purified .5L Purified 2 Yes 0.099 0.34 0.21 BL4
14 3 4 Purified .5L Purified 2 Yes 0.088 0.34 0.21 BL4
14 3 5 Purified .5L Purified 2 Yes 0.11 0.34 0.21 BL4
14 3 6 Purified .5L Purified 2 Yes 0.071 0.34 0.21 BL4
117
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
15 1 1 Spring .5L Spring 2 Yes 0.069 0.27 0.19 BL4
15 1 2 Spring .5L Spring 2 Yes 0.074 0.27 0.19 BL4
15 1 3 Spring .5L Spring 2 Yes 0.085 0.27 0.19 BL4
15 1 4 Spring .5L Spring 2 Yes 0.09 0.27 0.19 BL4
15 1 5 Spring .5L Spring 2 Yes 0.077 0.27 0.19 BL4
15 1 6 Spring .5L Spring 2 Yes 0.124 0.27 0.19 BL4
15 2 1 Purified .5L Purified 2 Yes 0.13 0.27 0.19 BL4
15 2 2 Purified .5L Purified 2 Yes 0.146 0.27 0.19 BL4
15 2 3 Purified .5L Purified 2 Yes 0.1 0.27 0.19 BL4
15 2 4 Purified .5L Purified 2 Yes 0.154 0.27 0.19 BL4
15 2 5 Purified .5L Purified 2 Yes 0.179 0.27 0.19 BL4
15 2 6 Purified .5L Purified 2 Yes 0.179 0.27 0.19 BL4
15 3 1 Purified .5L Purified 2 Yes 0.133 0.27 0.19 BL4
15 3 2 Purified .5L Purified 2 Yes 0.147 0.27 0.19 BL4
15 3 3 Purified .5L Purified 2 Yes 0.138 0.27 0.19 BL4
15 3 4 Purified .5L Purified 2 Yes 0.13 0.27 0.19 BL4
15 3 5 Purified .5L Purified 2 Yes 0.113 0.27 0.19 BL4
15 3 6 Purified .5L Purified 2 Yes 0.151 0.27 0.19 BL4
16 1 1 Spring .5L Spring 2 Yes 0.107 0.35 0.18 BL4
16 1 2 Spring .5L Spring 2 Yes 0.126 0.35 0.18 BL4
16 1 3 Spring .5L Spring 2 Yes 0.109 0.35 0.18 BL4
16 1 4 Spring .5L Spring 2 Yes 0.122 0.35 0.18 BL4
16 1 5 Spring .5L Spring 2 Yes 0.112 0.35 0.18 BL4
16 1 6 Spring .5L Spring 2 Yes 0.118 0.35 0.18 BL4
16 2 1 Purified .5L Purified 2 Yes 0.167 0.35 0.18 BL4
16 2 2 Purified .5L Purified 2 Yes 0.127 0.35 0.18 BL4
16 2 3 Purified .5L Purified 2 Yes 0.105 0.35 0.18 BL4
16 2 4 Purified .5L Purified 2 Yes 0.143 0.35 0.18 BL4
16 2 5 Purified .5L Purified 2 Yes 0.14 0.35 0.18 BL4
16 2 6 Purified .5L Purified 2 Yes 0.154 0.35 0.18 BL4
16 3 1 Purified .5L Purified 2 Yes 0.169 0.35 0.18 BL4
16 3 2 Purified .5L Purified 2 Yes 0.236 0.35 0.18 BL4
16 3 3 Purified .5L Purified 2 Yes 0.153 0.35 0.18 BL4
16 3 4 Purified .5L Purified 2 Yes 0.165 0.35 0.18 BL4
16 3 5 Purified .5L Purified 2 Yes 0.118 0.35 0.18 BL4
16 3 6 Purified .5L Purified 2 Yes 0.156 0.35 0.18 BL4
17 1 1 Spring .5L Spring 2 Yes 0.059 0.31 0.2 AL4
17 1 2 Spring .5L Spring 2 Yes 0.073 0.31 0.2 AL4
17 1 3 Spring .5L Spring 2 Yes 0.065 0.31 0.2 AL4
17 1 4 Spring .5L Spring 2 Yes 0.068 0.31 0.2 AL4
17 1 5 Spring .5L Spring 2 Yes 0.073 0.31 0.2 AL4
17 1 6 Spring .5L Spring 2 Yes 0.078 0.31 0.2 AL4
118
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
17 2 1 Purified .5L Purified 2 Yes 0.116 0.31 0.2 AL4
17 2 2 Purified .5L Purified 2 Yes 0.123 0.31 0.2 AL4
17 2 3 Purified .5L Purified 2 Yes 0.083 0.31 0.2 AL4
17 2 4 Purified .5L Purified 2 Yes 0.134 0.31 0.2 AL4
17 2 5 Purified .5L Purified 2 Yes 0.079 0.31 0.2 AL4
17 2 6 Purified .5L Purified 2 Yes 0.051 0.31 0.2 AL4
17 3 1 Spring .5L Spring 2 Yes 0.126 0.31 0.2 AL4
17 3 2 Spring .5L Spring 2 Yes 0.121 0.31 0.2 AL4
17 3 3 Spring .5L Spring 2 Yes 0.108 0.31 0.2 AL4
17 3 4 Spring .5L Spring 2 Yes 0.111 0.31 0.2 AL4
17 3 5 Spring .5L Spring 2 Yes 0.089 0.31 0.2 AL4
17 3 6 Spring .5L Spring 2 Yes 0.087 0.31 0.2 AL4
17 4 1 Purified .5L Purified 2 Yes 0.111 0.31 0.2 AL4
17 4 2 Purified .5L Purified 2 Yes 0.115 0.31 0.2 AL4
17 4 3 Purified .5L Purified 2 Yes 0.102 0.31 0.2 AL4
17 4 4 Purified .5L Purified 2 Yes 0.102 0.31 0.2 AL4
17 4 5 Purified .5L Purified 2 Yes 0.112 0.31 0.2 AL4
17 4 6 Purified .5L Purified 2 Yes 0.11 0.31 0.2 AL4
18 1 1 Spring .5L Spring 2 Yes 0.064 0.32 0.21 AL4
18 1 2 Spring .5L Spring 2 Yes 0.078 0.32 0.21 AL4
18 1 3 Spring .5L Spring 2 Yes 0.079 0.32 0.21 AL4
18 1 4 Spring .5L Spring 2 Yes 0.092 0.32 0.21 AL4
18 1 5 Spring .5L Spring 2 Yes 0.045 0.32 0.21 AL4
18 1 6 Spring .5L Spring 2 Yes 0.077 0.32 0.21 AL4
18 2 1 Purified .5L Purified 2 Yes 0.129 0.32 0.21 AL4
18 2 2 Purified .5L Purified 2 Yes 0.119 0.32 0.21 AL4
18 2 3 Purified .5L Purified 2 Yes 0.098 0.32 0.21 AL4
18 2 4 Purified .5L Purified 2 Yes 0.11 0.32 0.21 AL4
18 2 5 Purified .5L Purified 2 Yes 0.125 0.32 0.21 AL4
18 2 6 Purified .5L Purified 2 Yes 0.125 0.32 0.21 AL4
18 3 1 Spring .5L Spring 2 Yes 0.114 0.32 0.21 AL4
18 3 2 Spring .5L Spring 2 Yes 0.104 0.32 0.21 AL4
18 3 3 Spring .5L Spring 2 Yes 0.1 0.32 0.21 AL4
18 3 4 Spring .5L Spring 2 Yes 0.1 0.32 0.21 AL4
18 3 5 Spring .5L Spring 2 Yes 0.076 0.32 0.21 AL4
18 3 6 Spring .5L Spring 2 Yes 0.081 0.32 0.21 AL4
18 4 1 Purified .5L Purified 2 Yes 0.105 0.32 0.21 AL4
18 4 2 Purified .5L Purified 2 Yes 0.103 0.32 0.21 AL4
18 4 3 Purified .5L Purified 2 Yes 0.083 0.32 0.21 AL4
18 4 4 Purified .5L Purified 2 Yes 0.067 0.32 0.21 AL4
18 4 5 Purified .5L Purified 2 Yes 0.084 0.32 0.21 AL4
18 4 6 Purified .5L Purified 2 Yes 0.089 0.32 0.21 AL4
119
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
19 1 1 Spring .5L Spring 2 Yes 0.071 0.43 0.2 AL4
19 1 2 Spring .5L Spring 2 Yes 0.085 0.43 0.2 AL4
19 1 3 Spring .5L Spring 2 Yes 0.067 0.43 0.2 AL4
19 1 4 Spring .5L Spring 2 Yes 0.076 0.43 0.2 AL4
19 1 5 Spring .5L Spring 2 Yes 0.067 0.43 0.2 AL4
19 1 6 Spring .5L Spring 2 Yes 0.073 0.43 0.2 AL4
19 2 1 Purified .5L Purified 2 Yes 0.134 0.43 0.2 AL4
19 2 2 Purified .5L Purified 2 Yes 0.178 0.43 0.2 AL4
19 2 3 Purified .5L Purified 2 Yes 0.118 0.43 0.2 AL4
19 2 4 Purified .5L Purified 2 Yes 0.104 0.43 0.2 AL4
19 2 5 Purified .5L Purified 2 Yes 0.233 0.43 0.2 AL4
19 2 6 Purified .5L Purified 2 Yes 0.19 0.43 0.2 AL4
19 3 1 Spring .5L Spring 2 Yes 0.089 0.43 0.2 AL4
19 3 2 Spring .5L Spring 2 Yes 0.088 0.43 0.2 AL4
19 3 3 Spring .5L Spring 2 Yes 0.102 0.43 0.2 AL4
19 3 4 Spring .5L Spring 2 Yes 0.065 0.43 0.2 AL4
19 3 5 Spring .5L Spring 2 Yes 0.058 0.43 0.2 AL4
19 3 6 Spring .5L Spring 2 Yes 0.09 0.43 0.2 AL4
19 4 1 Purified .5L Purified 2 Yes 0.058 0.43 0.2 AL4
19 4 2 Purified .5L Purified 2 Yes 0.061 0.43 0.2 AL4
19 4 3 Purified .5L Purified 2 Yes 0.047 0.43 0.2 AL4
19 4 4 Purified .5L Purified 2 Yes 0.059 0.43 0.2 AL4
19 4 5 Purified .5L Purified 2 Yes 0.059 0.43 0.2 AL4
19 4 6 Purified .5L Purified 2 Yes 0.075 0.43 0.2 AL4
20 1 1 Spring .5L Spring 2 Yes 0.074 0.68 0.17 AL4
20 1 2 Spring .5L Spring 2 Yes 0.119 0.68 0.17 AL4
20 1 3 Spring .5L Spring 2 Yes 0.098 0.68 0.17 AL4
20 1 4 Spring .5L Spring 2 Yes 0.145 0.68 0.17 AL4
20 1 5 Spring .5L Spring 2 Yes 0.124 0.68 0.17 AL4
20 1 6 Spring .5L Spring 2 Yes 0.127 0.68 0.17 AL4
20 2 1 Purified .5L Purified 2 Yes 0.237 0.68 0.17 AL4
20 2 2 Purified .5L Purified 2 Yes 0.19 0.68 0.17 AL4
20 2 3 Purified .5L Purified 2 Yes 0.137 0.68 0.17 AL4
20 2 4 Purified .5L Purified 2 Yes 0.168 0.68 0.17 AL4
20 2 5 Purified .5L Purified 2 Yes 0.185 0.68 0.17 AL4
20 2 6 Purified .5L Purified 2 Yes 0.233 0.68 0.17 AL4
20 3 1 Spring .5L Spring 2 Yes 0.186 0.68 0.17 AL4
20 3 2 Spring .5L Spring 2 Yes 0.127 0.68 0.17 AL4
20 3 3 Spring .5L Spring 2 Yes 0.153 0.68 0.17 AL4
20 3 4 Spring .5L Spring 2 Yes 0.148 0.68 0.17 AL4
20 3 5 Spring .5L Spring 2 Yes 0.116 0.68 0.17 AL4
20 3 6 Spring .5L Spring 2 Yes 0.188 0.68 0.17 AL4
120
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
20 4 1 No Product No Product 2 Yes 0.113 0.68 0.17 AL4
20 4 2 No Product No Product 2 Yes 0.11 0.68 0.17 AL4
20 4 3 No Product No Product 2 Yes 0.11 0.68 0.17 AL4
20 4 4 No Product No Product 2 Yes 0.117 0.68 0.17 AL4
20 4 5 No Product No Product 2 Yes 0.099 0.68 0.17 AL4
20 4 6 No Product No Product 2 Yes 0.099 0.68 0.17 AL4
21 1 1 Spring .5L Spring 3 No 0.027 0.23 No data AL4
21 1 2 Spring .5L Spring 3 No 0.018 0.23 No data AL4
21 1 3 Spring .5L Spring 3 No 0.007 0.23 No data AL4
21 1 4 Spring .5L Spring 3 No 0.023 0.23 No data AL4
21 1 5 Spring .5L Spring 3 No 0.042 0.23 No data AL4
21 1 6 Spring .5L Spring 3 No 0.005 0.23 No data AL4
21 2 1 No Product No Product 3 No 0.02 0.23 No data AL4
21 2 2 No Product No Product 3 No 0.029 0.23 No data AL4
21 2 3 No Product No Product 3 No 0.043 0.23 No data AL4
21 2 4 No Product No Product 3 No 0.024 0.23 No data AL4
21 2 5 No Product No Product 3 No 0.027 0.23 No data AL4
21 2 6 No Product No Product 3 No 0.032 0.23 No data AL4
21 3 1 No Product No Product 3 No 0.034 0.23 No data AL4
21 3 2 No Product No Product 3 No 0.032 0.23 No data AL4
21 3 3 No Product No Product 3 No 0.032 0.23 No data AL4
21 3 4 No Product No Product 3 No 0.03 0.23 No data AL4
21 3 5 No Product No Product 3 No 0.035 0.23 No data AL4
21 3 6 No Product No Product 3 No 0.037 0.23 No data AL4
21 4 1 Spring .5L Spring 3 No 0.06 0.23 No data AL4
21 4 2 Spring .5L Spring 3 No 0.045 0.23 No data AL4
21 4 3 Spring .5L Spring 3 No 0.037 0.23 No data AL4
21 4 4 Spring .5L Spring 3 No 0.057 0.23 No data AL4
21 4 5 Spring .5L Spring 3 No 0.055 0.23 No data AL4
21 4 6 Spring .5L Spring 3 No 0.053 0.23 No data AL4
22 1 1 Spring .5L Spring 3 Yes 0.058 0.26 0.31 AL4
22 1 2 Spring .5L Spring 3 Yes 0.057 0.26 0.31 AL4
22 1 3 Spring .5L Spring 3 Yes 0.044 0.26 0.31 AL4
22 1 4 Spring .5L Spring 3 Yes 0.047 0.26 0.31 AL4
22 1 5 Spring .5L Spring 3 Yes 0.049 0.26 0.31 AL4
22 1 6 Spring .5L Spring 3 Yes 0.055 0.26 0.31 AL4
22 2 1 No Product No Product 3 Yes 0.06 0.26 0.31 AL4
22 2 2 No Product No Product 3 Yes 0.053 0.26 0.31 AL4
22 2 3 No Product No Product 3 Yes 0.052 0.26 0.31 AL4
22 2 4 No Product No Product 3 Yes 0.063 0.26 0.31 AL4
22 2 5 No Product No Product 3 Yes 0.061 0.26 0.31 AL4
22 2 6 No Product No Product 3 Yes 0.072 0.26 0.31 AL4
121
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
22 3 1 Spring .5L Spring 3 Yes 0.066 0.26 0.31 AL4
22 3 2 Spring .5L Spring 3 Yes 0.065 0.26 0.31 AL4
22 3 3 Spring .5L Spring 3 Yes 0.058 0.26 0.31 AL4
22 3 4 Spring .5L Spring 3 Yes 0.048 0.26 0.31 AL4
22 3 5 Spring .5L Spring 3 Yes 0.018 0.26 0.31 AL4
22 3 6 Spring .5L Spring 3 Yes 0.043 0.26 0.31 AL4
22 4 1 Purified .5L Purified 3 Yes 0.083 0.26 0.31 AL4
22 4 2 Purified .5L Purified 3 Yes 0.069 0.26 0.31 AL4
22 4 3 Purified .5L Purified 3 Yes 0.061 0.26 0.31 AL4
22 4 4 Purified .5L Purified 3 Yes 0.097 0.26 0.31 AL4
22 4 5 Purified .5L Purified 3 Yes 0.106 0.26 0.31 AL4
22 4 6 Purified .5L Purified 3 Yes 0.103 0.26 0.31 AL4
23 1 1 No Product No Product 3 Yes 0.054 0.22 0.24 AL4
23 1 3 No Product No Product 3 Yes 0.045 0.22 0.24 AL4
23 1 4 No Product No Product 3 Yes 0.047 0.22 0.24 AL4
23 1 5 No Product No Product 3 Yes 0.049 0.22 0.24 AL4
23 1 6 No Product No Product 3 Yes 0.058 0.22 0.24 AL4
23 2 1 No Product No Product 3 Yes 0.063 0.22 0.24 AL4
23 2 3 No Product No Product 3 Yes 0.054 0.22 0.24 AL4
23 2 4 No Product No Product 3 Yes 0.07 0.22 0.24 AL4
23 2 5 No Product No Product 3 Yes 0.068 0.22 0.24 AL4
23 2 6 No Product No Product 3 Yes 0.051 0.22 0.24 AL4
23 3 1 Purified 8.5oz Purified 3 Yes 0.06 0.22 0.24 AL4
23 3 2 Purified 8.5oz Purified 3 Yes 0.082 0.22 0.24 AL4
23 3 3 Purified 8.5oz Purified 3 Yes 0.059 0.22 0.24 AL4
23 3 4 Purified 8.5oz Purified 3 Yes 0.053 0.22 0.24 AL4
23 3 5 Purified 8.5oz Purified 3 Yes 0.044 0.22 0.24 AL4
23 3 6 Purified 8.5oz Purified 3 Yes 0.044 0.22 0.24 AL4
23 4 1 Spring .5L Spring 3 Yes 0.056 0.22 0.24 AL4
23 4 2 Spring .5L Spring 3 Yes 0.044 0.22 0.24 AL4
23 4 3 Spring .5L Spring 3 Yes 0.039 0.22 0.24 AL4
23 4 4 Spring .5L Spring 3 Yes 0.053 0.22 0.24 AL4
23 4 5 Spring .5L Spring 3 Yes 0.055 0.22 0.24 AL4
23 4 6 Spring .5L Spring 3 Yes 0.05 0.22 0.24 AL4
24 1 1 Spring 25oz Spring 3 Yes 0.018 0.27 0.29 AL4
24 1 2 Spring 25oz Spring 3 Yes 0.033 0.27 0.29 AL4
24 1 3 Spring 25oz Spring 3 Yes 0.034 0.27 0.29 AL4
24 1 4 Spring 25oz Spring 3 Yes 0.041 0.27 0.29 AL4
24 1 5 Spring 25oz Spring 3 Yes 0.043 0.27 0.29 AL4
24 1 6 Spring 25oz Spring 3 Yes 0.051 0.27 0.29 AL4
24 2 1 No Product No Product 3 Yes 0.058 0.27 0.29 AL4
24 2 2 No Product No Product 3 Yes 0.06 0.27 0.29 AL4
122
Period Line Point Production Production_Size AHU Purified Ozone_Air Ozone_RinseWater Ozone_Product Line4
24 2 3 No Product No Product 3 Yes 0.051 0.27 0.29 AL4
24 2 4 No Product No Product 3 Yes 0.058 0.27 0.29 AL4
24 2 5 No Product No Product 3 Yes 0.055 0.27 0.29 AL4
24 2 6 No Product No Product 3 Yes 0.048 0.27 0.29 AL4
24 3 1 Spring 8.5oz Spring 3 Yes 0.053 0.27 0.29 AL4
24 3 2 Spring 8.5oz Spring 3 Yes 0.052 0.27 0.29 AL4
24 3 3 Spring 8.5oz Spring 3 Yes 0.052 0.27 0.29 AL4
24 3 4 Spring 8.5oz Spring 3 Yes 0.051 0.27 0.29 AL4
24 3 5 Spring 8.5oz Spring 3 Yes 0.052 0.27 0.29 AL4
24 3 6 Spring 8.5oz Spring 3 Yes 0.05 0.27 0.29 AL4
24 4 1 Purified .5L Purified 3 Yes 0.1 0.27 0.29 AL4
24 4 2 Purified .5L Purified 3 Yes 0.071 0.27 0.29 AL4
24 4 3 Purified .5L Purified 3 Yes 0.059 0.27 0.29 AL4
24 4 4 Purified .5L Purified 3 Yes 0.083 0.27 0.29 AL4
24 4 5 Purified .5L Purified 3 Yes 0.085 0.27 0.29 AL4
24 4 6 Purified .5L Purified 3 Yes 0.107 0.27 0.29 AL4
123
APPENDIX H: Ozone Monitoring Data Collection Sheet
Date of Sampling Event: _______________ Person Performing Sampling: ______________
Sampling Instrument: _________________ Date “ZERO CAL” Performed: _____________
Sampling Start Time: _________________ Sampling End Time: ______________________
Temperature: ____ o F Humidity: ___%
Production Status:
Line #1: __ Up __ Down __ CIP __ Other: ____ Line #2: __ Up __ Down __ CIP __ Other: ____
Line #3: __ Up __ Down __ CIP __ Other: ____ Line #4: __ Up __ Down __ CIP __ Other: ____
Products Being Run: Line #1: _______________________________
Line #2: _______________________________
Line #3: _______________________________
Line #4: _______________________________
Pt #1 Pt #2 Pt #3 Pt #4 Pt #5 Pt #6
Filler #1 ______ ______ ______ ______ ______ _____ Min: ____
______ ______ ______ ______ ______ ______ Max: ____
______ ______ ______ ______ ______ ______ Ave: ____
STEL: ____
Pt #1 Pt #2 Pt #3 Pt #4 Pt #5 Pt #6
Filler #2 ______ ______ ______ ______ ______ _____ Min: ____
______ ______ ______ ______ ______ ______ Max: ____
______ ______ ______ ______ ______ ______ Ave: ____
STEL: ____
Pt #1 Pt #2 Pt #3 Pt #4 Pt #5 Pt #6
Filler #3 ______ ______ ______ ______ ______ _____ Min: ____
______ ______ ______ ______ ______ ______ Max: ____
______ ______ ______ ______ ______ ______ Ave: ____
STEL: ____
Bottle Exit Oprt Pltf Rinser #6 Rinser #9 Filler #10 Filler #11
Filler #4 ______ ______ ______ ______ ______ _____ Min: ____
______ ______ ______ ______ ______ ______ Max: ____
______ ______ ______ ______ ______ ______ Ave: ____
STEL: ____
124
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