Purification of Indoor Air Environments by Enhanced Photocatalysis

Purification of Indoor Air Environments by Enhanced Photocatalysis A White Paper, Puradigm, LLC (17 Sep 2013) In the aggregate, the existent knowledge on the chemical action of ultraviolet constitutes a very considerable mass of facts. These, however, are scattered over so wide a field that their coordination and correlation is by no means a simple task. Carleton Ellis and Alfred A. Wells, The Chemical Action of Ultraviolet Rays, 1925. Overview The goals of management of Indoor Environment Quality (IEQ) are multiple: improvement of productivity in the work environment, occupant and worker health, and quality of sensitive products; protection of furnishings and décor, building HVAC equipment components; and building security; and reduction of building maintenance, energy costs, and fire hazards. Improvements in the health of building occupants are associated with cost savings in building operations. An ordered hierarchy of management strategies includes: source control, exposure control, ventilation, and air purification. Purification of indoor air environments of bioaerosols (*) by enhanced photocatalytic processes is the focus of this paper. I. Indoor Environmental Quality (Statement of the Problem) Indoor Environmental Quality (IEQ) defines living and working conditions within building environments that directly affect the health, safety, and comfort of building occupants. Air must be safe to breathe, water safe to drink, food safe to consume, and wastes safe to dispose. Management of both airborne and surface constituents must be considered during all phases of building design, construction, operation, and demolition. Air is mixture of major, minor, and trace constituents in various physical, chemical, and biological forms. Major constituents include: nitrogen, oxygen, carbon dioxide, and water. Minor constituents include: ammonia, nitrogen oxides, carbon monoxide, and inert gases. Trace constituents include: Volatile Organic Compounds (VOCs); Particulate Matter (PM x ); and Bioaerosols (BAs). These constituents may become airborne as gases, vapors, or suspended particles; or become deposited and attached to building structures and building occupants.

The indoor air environment is dynamic and constantly changing. Individual constituents are continually being created, removed, and transformed. Sources of indoor air constituents are primarily emissions, i.e. releases of volatiles or resuspension of particulates from building surfaces and furnishings. They can be byproducts of building HVAC operation, manufacturing, and cleaning, operations; and bioeffluents from occupants. Constituents are also transported between indoor and outdoor sources by air-handling systems for heating and cooling, ventilating, conditioning, and for purification ( HVAC+ systems). Individual constituents can be created and/or destroyed by natural atmospheric reactions or by engineered purification processes. A given air constituent may be essential, nonessential, and/or hazardous to human health. It all depends on how much, where and when, does what, to whom. Risk assessment requires knowledge of both the degree of effect and the degree of exposure that both determine hazard. Effects depend upon chemical, physical, and biological properties of the constituent; exposures depend upon concentrations and durations, and how the constituent is transported. Routes of exposure include respiration of air, ingestion of food and water, and direct skin contact Risk management requires decisions on how to reduce or eliminate the hazard posed by an undesired air contaminant. Control technologies are selected based on cost and on the level of control that is dictated by both environmental health demands and by cost to implement. Conventional technologies may range from simple removal and disposal, to partial reduction or elimination of harmful effects, or to complete destruction and elimination. Advanced technologies involve application of specific process for oxidation of VOCs, agglomeration of PM x, and inactivation of BAs. Proactive (preventive) technologies restrict accumulation of volatiles, deposition of particles, and proliferation of microbes on surfaces. Reactive (mitigative) technologies destroy volatiles, agglomerate particulates, and inactivate airborne and surface-bound microbes. The combined approach to air purification is to practice both before and after the fact. (*) Bioaerosols (BAs) are airborne particles of biological origin ubiquitous to indoor and outdoor environments. Some viable (living) forms can cause infection or disease; other non-viable (dead) forms can cause allergies and toxic reactions. Bioaerosols include both prokaryotes (bacteria) and eukaryotes (fungii, protozoa, algae), and particulate fragments of higher plants and animals. Pollen, mold, and dander are common bioaerosols. Antibiotic-resistant microorganisms represent the other extreme. A short review is found at http://aerosol.ees.ufl.edu/bioaerosol/section01-3.html Learn more @ PURADIGM.COM 2

II. Air and Surface Purification (Solution to the Problem). The purification of (1) air circulating through rooms in buildings, and the purification of (2) extended surfaces that comprise the structure and furnishings of a building are often thought to be two separate applications to be treated by distinctly different technologies. One is directed at treating a gas while the other is directed at treating a solid. Conventional air purification involves the removal of particulates and bioaerosols by filtration; and the adsorption of gases and volatiles from the air. Traditionally, room air is (1) passed through disposable high-efficiency particulate air (HEPA) filters to remove particulate matter of prescribed sizes, or (2) passed through packed beds of activated carbon to scrub out unspecified odors and organic vapors ( gas-phase filtration ). The former requires the replacement of units; the latter requires the replacement or regeneration of units, and the disposal of wastes. Non-engineered controls of surface contaminants are passive, i.e. they are prescribed to control a perceived and preventable problem. Conventional processes for surface purification or the disinfection of bioaerosols attached to exposed surfaces include hand washing and scrubbing of building surfaces with topical disinfectants intended to reduce microbial contamination. These processes have historically required responsible storage and use of hazardous chemicals, such as water solutions of phenol, formaldehyde, hexachlorophene, isopropyl alcohol, quaternary ammonium salts, and sodium hypochlorite; or gases, such as ozone, hydrogen peroxide, and ethylene oxide. Conventional air purification technologies generally target high levels of broad classes of air contaminants. By comparison enhanced air purification technologies are designed to apply specific processes to target specific groups of contaminants, such as oxidation of VOCs, agglomeration of PMx, or inactivation of bioaerosols. Greater levels of control also can be achieved by applying multiple technologies in sequence. Technologies can also be applied according to anticipated greater demand during periods of high building occupancy or during the course of special building operations. Engineered controls of specific air contaminant classes, such as VOCs, PM x, and BAs, are more proactive and responsive to changing conditions. They were originally designed and operated to air flow, temperature, and humidity. Ventilation is the historic approach for control of airborne contaminants. It is essentially a dilution of contaminated dirty air with fresh clean air, and/or separation and venting of dirty air. Air cleaning, or purification, by contrast, involves the removal and/or conversion of individual classes of air contaminants into less noxious or hazardous forms. Evolution of technology (for air purification involving engineered systems) is a continual process. Electronic and photo-catalytic air cleaners comprise a diverse group of engineered devices that are significantly different in their functionalities, modes of operation, and targeted efficiencies. Bipolar air ionization is contrasted from both electrostatic precipitation and ozone generation. In air ionization, PM x is electrically neutralized by direct contact with cluster ions, as opposed to attraction to electrically-charged surfaces as in electrostatic precipitation. In air ionization, the primary active species are clusters of negative and/or positive air ions, and not ozone in the case of ozone generation. Enhanced photocatalytic technology has combined many of the features of early devices to greatly increase its utility in IEQ. III. Enhanced Photocatalytic Technology (Description of the Process). Explanation of photocatalytic technology requires a definition for plasma - the fourth state of matter - the others being gas, liquid, and solid. A plasma is formed by exposing electrically-neutral gas molecules, that make up most of normal air, to a high energy source, such as electricity or ultraviolet light. A very small number of the many oxygen molecules each gain an electron and are reduced to negatively-charged air ions. Likewise, a very small number of the many nitrogen molecules each lose an electron and are Learn more @ PURADIGM.COM 3

oxidized to positively-charged air ions. In photocatalytic processes, these energized species interact in many chemical and physical reactions, both homogeneous and heterogeneous (*). These air ions are highly energized, but the bulk of the surrounding gas molecules remains un-ionized and the mixture remains at essentially room temperature. These simple air ions are relatively short-lived (fractions of a second) and prefer to revert to their original un-ionized forms, or alternatively, combine with water molecules to form larger hydrated cluster ions, which have multiple electrical charges, and which may exist for several hundred seconds. This enhanced technology involving cluster ions has intriguing properties. Those defined as reactive oxygen species (ROS) are very chemically active and can convert most VOCs into simpler products of complete oxidation like carbon dioxide and water. Those defined as reactive charged species (RCS) are very physically active and can agglomerate fine particulate matter PM x into larger clumps that are more easily removed from the surrounding air. The distinction between ROS and RCS is mainly semantics. ROS are assumed to be involved in chemical reactions; RCS are assumed to be involved in physical reactions. Both can and do occur simultaneously and sequentially. Air molecules become ionized when exposed to thermal, electrical, or light energies. Physico-chemical reactions (both physical and chemical) are accelerated on the surface of a photoactive solid exposed to light [typically titanium dioxide (TiO 2 ) exposed to ultraviolet (UV) light]. This reaction generates free hydroxyl radicals ( HO ) that react further to form various ROS and RCS. Photocatalysis is very efficient and does not require high energies or result in high temperatures and loss as heat Puradigm LLC currently applies enhanced photocatalytic technology (*) to improve IEQ, and is building on this foundation. The energy source is a broad-spectrum, high-efficiency dual-wavelength UV X lamp (253.7 & 185.4 nm). A unique honeycomb matrix is used to maximize surface exposure available to promote photocatalysis. Rates of the most desirable reactions are further increased by applying the UV light directly and reflecting it indirectly onto the photocatalyst matrix to greatly enhance the ionization efficiency of air passing across the cell. Any accumulation of undesirable films on the catalyst surface is also minimized. A proprietary six-metal hydrophobic coating of the lamp further enhances the production of preferable reactive oxygen species while eliminating the formation of undesirable ozone and nitrogen oxides. Free radical reactions with water vapor promote the formation of hydroxyl, superoxide, and hydroperoxy radicals that create an aggressive atmosphere of reactive oxygen species and reactive charged species. The ionized cloud of ROS and RCS are then directed into enclosed spaces or room where they have pronounced effects on bioaerosols. (*) Enhanced Photocatalysis of Biological, Chemical, and Physical Constituents is described in detail in the Appendix. IV. Microbial Inactivation (Description of the Mechanism). Microorganisms are small unicellular (single cells) organisms that are commonly found in aggregates in suspended bioaeorols or in biofilms attached to surfaces. There is a great diversity among microbial species. They are very opportunistic and are found in all types of normal and abnormal environments: hot to cold, dry to wet, aerobic to anaerobic, etc. Some have the ability to form spores that can be very longlived and are very resistant to extreme conditions. They are found in air, water, and soil environments, and associated with living and dead plants and animals. The aggregate of microorganisms living on or in humans is called the human microbiome. The average human is made up of trillions of cells. The total number of non-human microbial cells may outnumber human cells by a factor of ten The aggregate of human cells greatly outweigh the aggregate of microbial cells! There are thousands of diverse microbial species normally present in the human body. Some assist their hosts in food digestion or preventing disease by attacking pathogenic organisms. Most are along for the ride and the free lunch and their effects on the host are largely unknown. Learn more @ PURADIGM.COM 4

Bioaerosols (BAs) differ from inanimate particulate matter (PM x ) in being living organisms that are capable of metabolizing, growing, and reproducing, and causing adverse effects upon higher organisms. It is desirable to control bacteria which are implicated as the cause of hospital-acquired illnesses (nosocomial infections) attributed to antibiotic-resistant species ( Superbugs ), and outbreaks of food poisoning in restaurants attributed to accidental contamination. The airborne transmissions of viruses, bacteria, fungal spores, and other bioaerosols are of major concern. Microorganisms in indoor environments can be present both as particulates (cells and/or spores) and can produce natural microbial VOCs (MVOCs). Mitigation, therefore, may require combinations of processes to effect the desirable level of destruction and removal. Airborne (and waterborne) microbes prefer to attach to almost any surface. Traditionally, attempts have been made to create and maintain sanitary, microbially-clean surfaces, e.g. painted and tiled surfaces, smooth ducts and piping, and antibacterial coatings. No surface is ever completely free of microbes, although special laboratories and biologically clean rooms for handling potent disease agents approach zero limits. Sterilization can be accomplished by thermal (heating, freezing), chemical (disinfectants, germicides), physicochemical (surface antimicrobials), irradiation, high pressure, filtration, or photochemical (UV germicidal irradiation) means. Traditional non-engineered controls of aerosols and surface contaminants are prescriptive and passive. Conventional processes for surface purification or the disinfection of bioaerosols attached to exposed surfaces include hand washing and scrubbing of exposed surfaces. Topical disinfectants is prescribed to reduce microbial contamination. These processes have historically required storage and handling of hazardous chemicals. Disinfection of building surfaces is broadly defined as the partial inactivation of microorganisms (or their toxins or vectors) and rendering them incapable of causing adverse effects upon human health. The process is not usually intended to kill all microorganisms, especially not bacterial spores, which are more resistant than whole cells. Rather, it results in a greatly reduced population of microorganisms that is much less likely to spread infection and disease. Sterilization is a much more extreme physical and/or chemical process to achieve essentially complete inactivation. It is intended to achieve asepsis, a sterile microbial environment, such as operating rooms, surgical instruments, medications, and biological culture media, where complete elimination of all types of life is required. Cell walls of bacteria provide structural support and protection of the cellular membrane and the cytoplasm. Depending upon the species, bacterial cell walls may contain peptidoglycan, a polymer of sugars and amino acids, and lipopolysaccharides, containing lipids and polysaccharrides. These and other chemical components make up one or more layers of the bacterial cell wall, which can have different configurations and thicknesses for different classes of bacteria.(*) The exteriors of non-bacterial cells and non-microbial bioaerosol particles have different structures. The mechanism usually invoked to explain nonspecific inactivation, i.e. disinfection and sterilization, of most microorganisms by commonly used technologies involves the complete destruction of the cell wall and/or the disruption of internal cellular structures. Dead and disintegrated cells appear in photomicrographs as shriveled prunes. The mechanism that might be invoked to explain specific inactivation of bioaerosols by cluster ions (ROS and RCS), however, may be quite different. The dead cells in photomicrographs appear as pincushions struck by tiny invisible arrows. The use of the word target seems apropos. Damage by ROS appears to be confined to the structures of the cell wall and no internal structures appear to be adversely affected. This has consequence in that RNA and DNA in the interiors of the cells do not appear to be affected. Selective neutralization of net surface charges by RCS on the outer cell wall is involved in the agglomeration of dead cells. (*) Bacteria can be differentiated as (G+ and G-) based on reactions to the differential Gram staining technique. G+: Bacillus, Clostridia, Staphylococcus, Enterococcus, Micrococcus, Sarcina, Listeria, Learn more @ PURADIGM.COM 5

Streptococcus spp. G-: Pseudomonas, Escherichia, Serratia, Shigella, Legionella, Salmonella, Enterobacter, Helicobacter, Neisseria spp. http://en.wikipedia.org/wiki/gram-negative_bacteria http://en.wikipedia.org/wiki/gram-positive_bacteria Learn more @ PURADIGM.COM 6

V. Environmental Evaluation (Operation and Safety). Proper operation of enhanced air purification systems to improve IEQ requires optimization of process variables describing both the air handling system and the air quality demand. The process control unit should be centrally located. Inputs are set manually, based on fixed design parameters, or set automatically, based on monitored demand parameters. Manual inputs include: power capacity, and airflow area, and desired levels of air ions. The latter may be monitored indirectly through applied power levels. Electronic inputs might include: airflow, humidity, outside air quality, return air quality, and detection of specific VOCs. Sensors measure volumetric airflow and humidity. Air quality sensors placed in the return air duct and in the outside air intake can be used to measure VOCs and PMx. Another air quality sensor can be used to monitor ozone, to ensure that any ozone present in the outside air is below the recommended ASHRAE limit (50 ppb). A third type of air quality sensor can be used to measure relative levels of certain size fractions of particulate matter (PMx). Signals from the sensors can be logged by a personal computer or transmitted by modem to an internet data center. Performance of the system then can be visually displayed in real-time plots and stored for archival retrieval or real-time viewing using a standard web browser. Collectively, the population of all charged species in the air environment contributes to a net negative, or positive, space charge that can be monitored Safety of any new technology applied for the purification of indoor air constituents must insure safe operation within the occupied spaces of a living/working building environment. Acceptance of photocatalytic technology, therefore, involves gaining a basic understanding of underlying chemistry and physics, and then learning how to best apply its features to the control of bioaerosols, especially in industries like food processing and healthcare that are sensitive to public opinion. Puradigm Technology (*) ROS and ROS generated by the Puradigm Technology are not considered to pose significant hazards to human health. Any risks attributable to ROS or RCS are considered much less than those associated with the trace air contaminants. The ROS and RCS generated by the Puradigm Technology mimics natural formation of similar species in the atmosphere. There is a considerable body of literature that describes the beneficial effects of negative air ions. A natural low-level background of air ions is present in the atmosphere that is increased during periods of electric storms. There is a growing literature on the beneficial effects of air ions to enhance the IEQ of living and working environments. The Puradigm Technology is applied for the purification of both room air and building surfaces. It involves the generation of hydrated cluster ions using photocatalytic devices installed directly in rooms or air-handling systems. The cluster ions are generated in situ and immediately react with the targeted air contaminants. Any unreacted cluster ions revert back to their original state within a short time. Concerns over the incidental generation of ozone by other types of air cleaners are not applicable. The Puradigm Technology was intentionally designed to essentially eliminate the formation of ozone. Byproducts of incomplete oxidation are considered to be below detectable limits. There is no direct exposure to UV radiation with the Puradigm technology. The alternate use of chemical disinfectants applied in the extreme may require vacating a building until any residues are neutralized or purged to eliminate residues. There are no unused reactants to dispose of using photocatalytic processes. The only residues upon the application of the Puradigm Technology are considered to be the terminal products of oxidation like water and carbon dioxide. Agglomerated particulates are removed by conventional filters in HVAC units. Learn more @ PURADIGM.COM 7

References 1. Daniels, Stacy L., On The Ionization of Air for Removal of Noxious Effluvia (Air Ionization of Indoor Environments for Control of Volatile and Particulate Contaminants with Nonthermal Plasmas Generated by Dielectric Barrier Discharge, Special Issue on Nonthermal Medical/Biological Treatments Using Electromagnetic Fields and Ionized Gases, IEEE Trans. Plasma Sci. 30(4), 1471-81 (August 2002). 2. Daniels, Stacy L., On the Qualities of the Air as Affected by Radiant Energies (Photocatalytic Ionization Processes for Remediation of Indoor Environments), J. Env. Eng. Sci. 6(3), 329-42 (May 2007). 3. Tupman, David, Enhanced Photo-Catalytic Cells, U.S. Pat. Apps. 20120058006, 8 Mar 2012; 20120141320, 7 Jun 2012. (*) Puradigm and other marks are registered trademarks of Puradigm, LLC. Learn more @ PURADIGM.COM 8

Appendix: Enhanced Photocatalysis of Biological, Chemical, and Physical Constituents. Ordinary air contain mostly electrically neutral diatomic oxygen ( O 2 ) and nitrogen ( N 2 ) molecules. These diatomic (two atoms) molecules do not react well with most other molecules, but can be activated by energies supplied from electrical or light sources. Neutral diatomic oxygen gains an electron ( e - ) and is reduced to a negatively-charged air ion. Neutral diatomic nitrogen loses an electron and is oxidized to a positively-charged air ion. (Eqn. 1) O 2 + e - O 2 - ; N 2 - e - N 2 + (1) These simple air ions can revert back to their original forms, or alternatively, combine with water (H 2 O) molecules to form larger hydrated cluster ions having multiple electrical charges. Superoxide ( O 2 - ) is considered to be both a radical ( ), (central dot) and an anion (charge of 1 ). It reacts with itself to produce hydrogen peroxide and oxygen through a reaction known as dismutation. (Eqn. 2) 2 O 2 - + 2 H + H 2 O 2 + O 2 (2) Superoxide can be further reduced to peroxide ( O 2-2 ), another activated form of oxygen also represented as hydrogen peroxide ( H 2 O 2 ). This process can be catalyzed by metallic ions and energized by photons to produce the highly reactive hydroxyl radical ( HO ), not to be confused with hydroxyl anion ( OH - ), or hydrogen cation ( H + ). (Eqn. 3) O 2 - + H 2 O 2 O 2 + HO + HO - (3) Superoxide, while much more reactive than molecular oxygen, is the least reactive, the most stable, and the most likely oxygen radical species to be encountered at ambient temperatures on earth. The hydroxyl radical, one of the strongest oxidants, is also naturally produced in the troposphere, but is very short-lived. Superoxide also reacts with ozone ( O 3 ) to form hydroxyl anion and hydroxyl radical. (Eqn. 4) 2 O 2 - + O 3 + H 2 O 2 O 2 + HO - + HO (4) A series of reactions can be postulated in which superoxide, and other ROS generated by air ionization, simply depicted as O 2, initiate the oxidation of volatile organic hydrocarbons ( C a H b ), inorganic ammonia ( NH 3 ), hydrogen sulfide ( H 2 S ) and hydrogen chloride ( HCl ). The terminal products of oxidation are carbon dioxide ( CO 2 ), water ( H 2 O ), nitrate anion ( NO 3 - ), sulfate anion ( SO 4-2 ), and chloride anion ( Cl - ) (*). (Eqns. 5a, 5b, 5c, 5d) C a H b + (a + b/4) O 2 a CO 2 + (b/2) H 2 O (5a) NH 3 + 2 O 2 - NO 3 + H 2 O + H + (5b) H 2 S + 2 O 2-2 SO 4 + 2 H + + H 2 O (5c) HCl Cl - + H + (5d) The above reaction scheme is a very simplified explanation. Identification of the many other individual chemical species that might become involved in transient chemical reactions in air environments is not trivial. Modeling of the full reaction scheme may involve dozens of homogeneous and heterogeneous reactions amongst various reactive oxygen species (ROS) and reactive changed species (RCS). Enhanced photocatalysis can be expressed in three statements. (Eqns. 6, 7, 8) Volatile organic compounds ( VOCs ) are oxidized: VOCs + ROS CO 2 + H 2 O (6) Learn more @ PURADIGM.COM 9

Particulate matter ( PM x ) is agglomerated into larger particles (PM y ): PM x + RCS PM y, where y << x (7) Biological aerosols ( BAs ) are converted from active to inactive forms (sterilized, killed, destroyed): Active BAs + ROS, RCS Inactive BAs (8) (*) Ionizability is predicted for all compounds having ionization energies less than oxygen (12.0697 ev). The typical atmospheric molecule has an energy of ~ 0.03 ev corresponding to room temperature. [Subscripts (atom number); superscripts (charge number), and central scripts (free radicals) have specific meanings.] Learn more @ PURADIGM.COM 10