E PA-600/R-98-080
July 1998
INDOOR AIR EMISSIONS FROM OFFICE EQUIPMENT:
TEST METHOD DEVELOPMENT AND POLLUTION
PREVENTION OPPORTUNITIES
By
Coleen Northeim, Linda Sheldon, Don Whitaker,
Bob Hetes, and Jennifer Calcagni
Research Triangle Institute
3040 Cornwallis Road
P. O. Box 12194
Research Triangle Park, North Carolina 27709
EPA Cooperative Agreement No.: CR-822025
EPA Project Officer: Kelly W. Leovic
National Risk Management Research Laboratory
Research Triangle Park, North Carolina 27711
Prepared for
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
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NOTICE'
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
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FOREWORD
The U. S. Environmental Protection Agency is charged by Congress with pro-
tecting the Nation's land, air, and water resources. Under a mandate of national
environmental laws, the Agency strives to formulate and implement actions lead-
ing to a compatible balance between human activities and the ability of natural
systems to support and nurture life. To meet this mandate, EPA's research
program is providing data and technical support for solving environmental pro-
blems today and building a science knowledge base necessary to manage our eco-
logical resources wisely, understand how pollutants affect our health, and pre-
vent or reduce environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for
investigation of technological and management approaches for reducing risks
from threats to human health and the environment. The focus of the Laboratory's
research program is on methods for the prevention and control of pollution to air,
land, water, and subsurface resources; protection of water quality in public water
systems; remediation of contaminated sites and groundwater; and prevention and
control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental
technologies; develop scientific and engineering information needed by EPA to
support regulatory and policy decisions; and provide technical support and infor-
mation transfer to ensure effective implementation of environmental regulations
and strategies.
This publication has been produced as part of the Laboratory's strategic long-
term research plan. It is published and made available by EPA's Office of Re-
search and Development to assist the user community and to link researchers
with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
EPA REVIEW NOTICE
This report has been peer and administratively reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
This document is available to the public through the National Technical Information
Service, Springfield, Virginia 22161.
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Abstract
EPA's Air Pollution Prevention and Control Division (APPCD) and Research Triangle
Institute (RTI) began a cooperative agreement in October 1993 to research pollution prevention
approaches for reducing indoor air emissions from office equipment. The project included: (1)
forming a group of technical advisors from industry and academia; (2) preparing a literature
review and background report on the operation of, and emissions from, office equipment as well
as pollution prevention opportunities; (3) developing and evaluating an Emissions Testing
Guidance Document for Dry-Process Photocopy Machines', (4) identifying and evaluating
pollution prevention options; and (5) preparing technical papers, presentations, and reports.
Because no standard test method exists to measure emissions from office equipment (e.g.,
ozone, volatile organic compounds, aldehydes/ketones, inorganic gases, and particles), it is
difficult to compare data from different studies. Thus, the focus of this cooperative agreement
was the development and evaluation of a large chamber test method for measuring emissions
from dry-process photocopiers. The ultimate goal is to apply the method to better understand
emissions from office equipment and to develop lower emitting machines. Challenges and
complications encountered in developing and implementing the method include: heat generation
which can cause large increases in chamber temperature; finite paper supplies for photocopiers
which limit test duration; toner off-gassing between tests or toner carryover if different types of
toner are tested; varying power requirements that may require changes in chamber electrical
supply; and remote starting of the machines which is necessary to maintain chamber integrity.
The test method was evaluated in two phases. Phase I was a single laboratory evaluation
of the method at RTI using four mid-range dry-process photocopiers. Phase I results indicated
that the test method provided acceptable performance for characterizing emissions, adequately
identified differences in emissions between machines both in compounds emitted and their
emission rates, and was capable of measuring both intra- and inter-machine variability in
emissions. For Phase I, the compounds with the highest emission rates from the four different
machines tested were: ethylbenzene (28,000 |ig/hour), w,/?-xylenes (29,000 |!g/hour), o-xylene
(17,000 (ig/hour), 2-ethyl-l-hexanol (14,000 (ig/hour), and styrene (12,000 |ag/hour). Although
many of the same compounds were detected in emissions from each of the four photocopiers, the
relative contribution of individual compounds varied considerably between machines, with
differences greater than an order of magnitude for some compounds. The toners appear to be the
primary source of organic emissions from the photocopiers.
Because all chambers may not produce similar results, Phase II was a four-laboratory
round-robin evaluation of the method. A single dry-process photocopier was shipped to each of
the four laboratories along with supplies (i.e., toner and paper). Phase II results demonstrate that
the method was used successfully in the different chambers to measure emissions and that
differences in chamber design and construction appeared to have had minimal effect.
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TABLE OF CONTENTS
Abstract iii
List of Tables vi
List of Figures vii
Acknowledgments viii
1.0 INTRODUCTION 1-1
1.1 Background 1-1
1.2 Approach 1-2
1.2.1 Establishment of Technical Advisory Group 1-2
1.2.2 Literature Review 1-2
1.2.3 Development and Evaluation of Emissions Testing Guidance 1-3
1.2.4 Pollution Prevention Opportunities 1-3
1.2.5 Reporting 1-3
2.0 BACKGROUND 2-1
2.1 Introduction 2-1
2.2 Photoimaging Machines 2-4
2.2.1 Equipment Design and Operation 2-4
2.2.2 Published Indoor Air Emissions Data for Dry-Process Photoimaging
Machines 2-9
2.2.2.1 Ozone 2-9
2.2.2.2 Volatile Organic Compounds (VOCs) 2-10
2.2.2.3 Particulates 2-11
2.3 Summary 2-13
3.0 PHASE I: TEST METHOD DEVELOPMENT, EVALUATION, AND RESULTS .. 3-1
3.1 Discussion of Method 3-1
3.2 Validation and Use of the Method 3-4
3.3 Chamber Evaluation 3-8
3.3.1 Procedure 3-8
3.3.2 Results 3-10
3.4 Photocopier Test Results 3-14
3.4.1 Sample Collection and Emission Rate Calculations 3-14
3.4.2 Precision of Emission Rate Measurements 3-22
3.4.3 Between Copier Variability of Emission Rate Measurements 3-22
3.4.4 Within Copier Variability of Emission Rate Measurements 3-33
3.4.5 Emission Rates as a Function of Copier Operation Time 3-36
3.4.6 Practical Aspects of Test Implementation 3-50
3.4.6.1 Toner Aging/Headspace Analysis 3-50
3.4.6.2 Toner Carryover 3-52
3.4.6.3 Vent Gas Sampling 3-52
4.0 PHASE II: ROUND-ROBIN EVALUATION AND RESULTS 4-1
4.1 Materials and Methods 4-1
4.1.1 Chamber Dosing and Recovery Experiments 4-2
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TABLE OF CONTENTS (Continued)
4.1.2 Chamber Air Samples During Emissions Tests 4-3
4.1.3 Toner Samples for Headspace Analysis 4-4
4.2 Results 4-4
4.2.1 Chamber Dosing and Recovery Experiments 4-4
4.2.2 Emission Rates 4-6
4.2.3 Headspace Samples 4-10
4.2.4 Particle Samples 4-10
5.0 ADDITIONAL ISSUES RELATED TO OFFICE EQUIPMENT EMISSIONS 5-1
5.1 Paper Type 5-1
5.2 Recycled Toner Cartridges 5-3
5.3 Color Photoimaging Machines 5-4
6.0 POLLUTION PREVENTION OPPORTUNITIES 6-1
6.1 Literature 6-1
6.1.1 Pollution Prevention for Reducing Ozone Emissions 6-1
6.1.2 Pollution Prevention Opportunities for Toner 6-2
6.1.3 Pollution Prevention Related to Equipment Maintenance 6-3
6.2 Pollution Prevention Opportunities Resulting from Laboratory Testing 6-3
6.2.1 Reduced Emissions from Toners Used in Dry-Process Photocopiers ... 6-3
6.2.2 Reduced Ozone Emissions from Copiers 6-5
7.0 CONCLUSIONS AND RECOMMENDATIONS 7-1
7.1 Literature Review 7-1
7.2 Phase I Testing 7-1
7.3 Phase II Testing 7-3
7.4 Potential Pollution Prevention Opportunities 7-4
8.0 DATA QUALITY
8.1 Quality Assurance Project Plans 8-1
8.2 Data Quality Indicator Goals 8-1
8.2.1 Precision 8-5
8.2.2 Accuracy 8-5
8.2.3 Completeness 8-7
8.3 Quality Control 8-7
8.4 Inspections, Audits, and Data Reviews 8-7
9.0 References 9-1
Appendix A Participants and Recommendations from Technical Advisors Meeting A-l
Appendix B Standard Emissions Testing Guidance for Dry-Process Photocopy Machines .. B-l
Appendix C Other Sources of Information on Indoor Air Emissions from Office Equipment C-l
Appendix D EPA QA Audit of the RTI and EPA Large Chambers D-l
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LIST OF TABLES
2-1 Summary of Office Equipment Literature Review 2-3
2-2 Ozone Produced by Photocopiers Before and After Maintenance 2-10
2-3 Laser Printer Emission Rates of Various VOCs and TVOCs Reported
as Toluene Equivalents (mg/page), Source: Gressel, 1996 2-11
2-4 VOC Emitted from Processed Paper (Listed According to GC Retention Time) .... 2-12
2-5 TVOC Emissions from Fresh Copies (ng/copy sheet), Source: Wolkoff et al. 1993 . 2-13
3-1 Conditions for Chamber Testing 3-2
3-2 Organic Chemicals Targeted for Emissions Testing 3-3
3-3 Methods for Measuring Chamber Air Concentrations of Target Analytes 3-3
3-4 Experimental Design for Phase 1 Testing 3-6
3-5 Description of RTl's Large Environmental Test Chamber 3-7
3-6 Copiers Tested 3-8
3-7 Methods for Generating Standards with Known Emissioons 3-9
3-8 Chamber Recovery Test Results - VOCs 3-11
3-9 Chamber Recovery Test Results - Formaldehyde and Ozone 3-14
3-10 Copier Testing Procedure for Phase I (refer to Appendix B for details) 3-16
3-11 Conditions for Copier Testing 3-17
3-12 VOC Emission Rate Precision Data for Triplicate Large Chamber Tests of Copier 1 3-23
3-13 Aldehyde/Ketone and Ozone Emission Rate Precision Data for Triplicate Large
Chamber Tests of Copier 1 3-24
3-14 Estimated VOC Emission Rates (ng/h • copier) Dry-Process Photocopiers—Idle . . . 3-25
3-15 Estimated VOC Emission Rates (^g/h • copier) Dry-Process Photocopiers—During
Operation 3-26
3-16 Estimated VOC Emission Rates (ng/page) Dry-Process Photocopiers—During
Operation 3-27
3-17 Estimated Aldehyde/Ketone Emission Rates (|ig/h • copier) Dry-Process
Photocopiers—Idle 3-28
3-18 Estimated Aldehyde/Ketone Emission Rates (ng/h • copier) Dry-Process
Photocopiers—During Operation 3-29
3-19 Estimated Aldehyde/Ketone Emission Rates (ng/page) Dry-Process Photocopiers—
During Operation 3-30
3-20 Estimated Ozone Emission Rates (jig/h • copier) Dry-Process Photocopiers—During
Operation 3-30
3-21 Comparison of Intra-Machine (Copier 1) Variability in Emissions (|ig/h • copier)
During Replicate Runs—During Operation 3-34
3-22 Comparison of Intra-Machine (Copier 1) Variability in Emissions (ng/h • copier)
During Replicate Runs—Idle 3-35
3-23 Estimated Emission Rates as a Function of Time - Copier 1 3-46
3-24 Estimated Emission Rates as a Function of Time - Copier 4 3-47
3-25 Practical Considerations for Copier Testing Issues and Resolutions 3-51
3-26 Results of Toner Headspace Experiments 3-53
4-1 Descriptions of Test Chambers Used in Round-Robin Testing 4-2
4-2 Chamber Recoveries Based on Standard Emission Sources (//g/hour • copier) 4-5
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LIST OF TABLES (Continued)
4-3 Emission Rates Measured During Copier Operation — Selected VOCs
(|ig/hour • copier) 4-7
4-4 Copier Emission Rates During Operation Based on RTI Sample Analysis of
Duplicate Samples Collected at Each Laboratory (ng/hour • copier) 4-8
4-5 Emission Rates Measured During Copier Operation Selected Aldehydes/Ketones
and Ozone (jig/hour • copier) 4-9
4-6 Toner Headspace Results from Round-Robin Study (ng/mL headspace) 4-11
5-1 Approximate Cost Percentages over the Life-time of Laser Printers 5-4
6-1 Headspace Analysis of Toner Samples (ng/mL) 6-5
8-1 Summary of Data Quality Indicator Goals 8-2
8-2 Summary of Emission Rate Accuracy and Precision for Standard Emission Sources . . 8-3
8-3 Summary of Emission Rate Accuracy and Precision 8-4
8-4 Summary of Round-Robin Toner Headspace Analysis Precision 8-6
LIST OF FIGURES
2-1 Six steps in the photoimaging process 2-5
2-2 How photoimaging transfers the image to paper 2-6
2-3 Schematic of toner transfer to and from photoconductive drum 2-7
3-1 Recovery from chamber: chloroform 3-12
3-2 Recovery from chamber: toluene 3-13
3-3 Chamber recovery: ozone-recovery test 3 3-15
3-4 Copier 1, particle concentration during test run 3-18
3-5 Copier 1, particle size distribution during test run 3-19
3-6 Ozone results, copiers 1, 2, 3, and 4 3-31
3-7 Copier 1: styrene concentrations 3-37
3-8 Copier 1: m-, /^-xylene concentrations 3-38
3-9 Copier 1: o-xylene concentrations 3-39
3-10 Copier 1: ethylbenzene concentrations 3-40
3-11 Copier 4: styrene concentrations 3-41
3-12 Copier 4: benzaldehyde concentrations 3-42
3-13 Copier 4: 2-ethyl-l-hexanol concentrations 3-43
3-14 Copier 4: o-xylene concentrations 3-44
3-15 Plots of emission rate vs. time for styrene 3-48
3-16 Plots of emission rate vs. time for ethylbenzene 3-49
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ACKNOWLEDGMENTS
The authors would like to thank the manufacturers and technical advisors who offered assistance
throughout this project (see Appendix A) and the laboratories that participated in the round-robin
evaluation. Participating laboratories in the round-robin evaluation, in addition to RTI, included
Air Quality Sciences, Inc. in Atlanta, EPA's National Risk Management Research Laboratory in
Research Triangle Park, and an office equipment manufacturer. We would also like to
acknowledge EPA's Environmental Technology Verification Program which provided financial
support for the round-robin evaluation.
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1.0
INTRODUCTION
1.1 Background
Several studies by the U.S. Environmental Protection Agency (EPA) have identified
indoor air quality (IAQ) as one of the most important environmental risks to the Nation's health
(U.S. EPA, 1987a and U.S. EPA, 1990). Major findings from long-term EPA studies of indoor
air are (U.S. EPA's TEAM Studies):
• for many pollutants, indoor levels are 2 to 5 times higher than outdoors;
• in both rural and heavily industrialized areas, personal exposures and indoor
concentrations exceed outdoor air concentrations for essentially all of the prevalent
volatile organic compounds;
• after some activities, indoor air pollutant levels can be up to 1,000 times higher
than outdoors; and
• in new nonresidential buildings, levels of volatile organic compounds can be as
much as 100 times higher than outdoors.
People spend approximately 90 percent of their time in indoor environments, such as
residences, public buildings, and offices. In the case of offices, the advent of electronic
technologies has caused rapid changes. Photocopiers, printers, and fax machines have become
prevalent in office settings, from home offices to large commercial or institutional settings, and
can vary dramatically in size and numbers in use. Along with the technical and efficiency
opportunities offered by these technologies comes the potential for increased pollution in the
indoor environment. Researchers such as Wolkoff et al. (1992), National Institute for
Occupational Safety and Health (NIOSH 1991), and Gallardo et al. (1994) have reported that the
operation of office equipment can contribute to increased indoor air pollutant concentrations and
has, in some cases, been associated with health complaints from exposed workers.
Traditionally, approaches for improving IAQ have generally focused on mitigation
technologies, such as ventilation and air cleaning. These approaches do not prevent pollution—the
pollution is simply transferred to another medium or outdoors. Depending on the source of
indoor air pollution, another approach is to focus on source reduction, ensuring that pollutants do
not enter the indoor environment in the first place. In the Pollution Prevention Act of 1990,
Congress declared that pollution should be prevented or reduced at the source whenever feasible
(EPA 1990). Source reduction may be accomplished by modifications to equipment, processes,
and procedures; reformulations or redesign of products; substitution of raw materials; and
improvements in use procedures.
The EPA's Air Pollution Prevention and Control Division (APPCD) of the National Risk
Management Research Laboratory (NRMRL) is responsible for EPA's indoor environment
engineering research. APPCD's Indoor Environment Management Branch (IEMB) applies
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IEMB's expertise in IAQ (i.e., source characterization, ventilation, and microbials) to work
cooperatively with EPA Program Offices, industry, consumers, and other researchers to identify
and prevent pollutants from indoor sources (e.g., develop low emitting materials and products).
1.2 Approach
During a 1993 IAQ/Pollution Prevention workshop, office equipment was identified by
IEMB researchers and workshop participants as a source of indoor air emissions and as a
technology that merited further research (Sarsony, 1993). In October 1993, Research Triangle
Institute (RTI) and EPA's IEMB initiated a cooperative agreement to research pollution
prevention approaches for reducing indoor air emissions from selected types of office equipment.
The approach consisted of: (1) establishment of a group of technical advisors from industry and
academia; (2) preparation of a literature review and a background report on the operation of,
and emissions from, office equipment as well as pollution prevention opportunities;
(3) development and extensive evaluation an Emissions Testing Guidance Document for Dry-
Process Photocopy Machines; (4) identification and evaluation of selected pollution prevention
options; and (5) preparation of technical papers, presentations, and reports. These activities are
summarized in subsections below.
1.2. 1 Establishment of Technical Advisory Group
In March 1994, a technical advisors planning meeting was convened to discuss the
objectives and approach for this research and to get input on technical priorities. The technical
advisors strongly recommended that a standard test method - that could be used to evaluate
emissions from office equipment - be developed. It was felt that such a method was needed to
evaluate different equipment types and to establish comparable baseline emission data that could
then be used as a starting point for the development of specific pollution prevention approaches.
The recommendations from the technical advisors meeting along with a list of attendees are
included as Appendix A of this report.
1.2.2 Literature Review
Concurrently with the technical advisors meeting, a literature search was conducted to
identify and review published information on office equipment design; indoor air emissions of
ozone, particulates, and organics; and potential pollution prevention approaches for reducing
these emissions (Hetes et al., 1995). A summary of the literature review is presented in Section 2
and serves as background for the remainder of the report.
As was conjectured by the small amount of data identified during the literature review, and
confirmed by the technical advisors, much of the existing data on emissions from office equipment
are proprietary. Additionally, the methods used for emissions testing are highly variable, and
therefore, published data from different laboratories may not be comparable. These findings
supported the need for an Emissions Testing Guidance Document both for the purposes of this
cooperative agreement and for others conducting research on emissions from office equipment.
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1.2.3 Development and Evaluation of Emissions Testing Guidance
The large chamber emissions testing development activities were conducted in two phases
and comprised the majority of this project. Phase I activities required approximately 2 years and
consisted of method development and evaluation at RTI. A subset of the technical advisors
provided input and direction to this process. A summary of the Phase I testing methods and
results are presented in Section 3. Phase II was a 1 -year effort and consisted of a round-robin
evaluation of the draft method (contained in Appendix B) at four laboratories. Section 4 presents
the Phase II activities and results.
1.2.4 Pollution Prevention Opportunities
One of the primary goals of this research was to identify and evaluate pollution prevention
opportunities for reducing emissions from office equipment. This was accomplished through
literature reviews; discussions with the technical advisors; and laboratory testing of dry-process
photocopiers, copy machine toner powder, and different types of printed circuit board laminate
materials. Section 5 of this report includes discussions of some of the issues that were identified,
but not tested, during this research and that have potential pollution prevention implications.
Section 6 describes pollution prevention opportunities that were identified through the literature
review and laboratory testing.
1.2.5 Reporting
The objectives of this report are to summarize the major activities that took place as part
of this cooperative agreement and to present the results from the large chamber emissions test
method development activities. Conclusions and recommendations from this research are
presented in Section 7. Quality assurance activities were conducted throughout this research
effort and are summarized in Section 8 and Appendix D. Readers interested in obtaining
additional information on indoor air emissions from office equipment should refer to the sources
contained in Appendix C.
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2.0 BACKGROUND
One of the first activities of this project was a literature review (Hetes et al., 1995). The
review covered published information on the following types of office equipment:
• dry- and wet-process photoimaging machines (copiers, printers, and faxes);
• computers and computer terminals;
• spirit duplicators;
• mimeograph machines;
• digital duplicators;
• diazo (blueprint) machines; and
• impact (dot matrix) printers.
A summary of the report follows and provides background information useful for
understanding the technical issues associated with test method development presented in Sections
3 and 4.
2.1 Introduction
The office environment contains many types of equipment that emit indoor air pollutants.
Emissions may occur as a result of equipment operation, offgassing from components, or episodic
releases related to catastrophic failure of a unit. For equipment that does not use supplies (e.g.,
video display terminals), emissions are primarily from offgassing of residual organics. The source
of these organics can either be construction materials (e.g., plastic casings) or components (e.g.,
cards used in manufacturing integrated circuit boards). Emissions resulting from offgassing
decrease with time until they reach a point where they are negligible. It has been reported that
over 300 hours of "on time" are required before a video display terminal's emissions reach a
negligible level (Brooks et al., 1993).
Emissions from equipment that use supplies such as toner, ink, and paper (e.g.,
photocopiers, printers) result from both offgassing and operation. Emissions from offgassing will
decrease with time as noted above; however, emissions from operation will remain fairly constant
or may even increase between routine maintenance or as the equipment ages. For example,
Selway et al. (1980) reported that ozone emissions from five tested photocopiers ranged from 16
to 131 [ig/copy before routine maintenance and were reduced to less than 1 to 4 ^g/copy after
maintenance.
In general, published data on the emissions from office equipment are limited. However,
increased levels of ozone, total volatile organic compounds (TVOC), and particulates have been
observed in the presence of operating equipment (Etkin, 1992; Tsuchiya et al., 1988; Wolkoff et
al., 1993). Furthermore, it has been reported that there is a significantly increased perception of
headache; mucous irritation and dryness in the eyes, nose, and throat; and dry and tight facial skin
among subjects exposed to office equipment (Wolkoff et al., 1992). Other researchers have also
reported that emissions associated with normal operation of office equipment can contribute to
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increased indoor air pollutant concentrations and have been associated with complaints from
exposed workers.
Table 2-1 summarizes the published emission rates, IAQ impacts, and potential pollution
prevention solutions associated with the equipment types that were evaluated as part of the
literature review. The equipment is listed in priority order (highest priority at top) for evaluation
as part of this RTI/EPA cooperative agreement. The criteria used to prioritize the equipment
types include relatively high emissions (either as a unit or in total emissions), minimal design
differences among manufacturers, easily understood processes, and the feasibility (both technical
and economic) for pollution prevention measures. Certain types of equipment with limited
applications can have high emission rates but may only affect IAQ in a limited area or in a few
locations. Others may have much lower emission rates on a per unit basis but may be found
throughout a building and therefore have a greater overall impact on IAQ. Therefore, the number
of units in operation was considered when prioritizing equipment for test in this project.
As can be seen in Table 2-1, dry-process photocopiers were identified as a high priority
for testing and investigation of pollution prevention options. Dry-process photocopiers are
prevalent in most office environments and are a known source of ozone, volatile organic
compounds (VOC), and particulate emissions. The size of photocopiers can range from small
personal models to fairly large machines that can have relatively high emission rates.
Laser printers, which utilize a technology similar to that of dry-process photocopiers and
have been shown to have similar emissions, were identified as a secondary priority for emission
testing given that they are much smaller in terms of throughput and concomitant emission rates
than photocopiers. Furthermore, NIOSH has recently completed an emissions test on four
different models of laser printers. The report discussing the testing program and detailed results,
"Methods for Characterizing Emissions From Laser Printers" (Gressel, 1996), can be obtained
directly from NIOSH using the contact information in Appendix C of this report.
Wet-process photocopiers have been shown to be the major contributor to indoor air
VOC levels in several studies and have significantly greater emissions than dry-process machines
on a per unit basis (Hodgson and Daisey, 1989; Tsuchiya et al., 1988). However, wet-process
machines constitute a small part of the photocopier market. Therefore, although wet-process
machines have higher individual emission rates, dry-process photocopiers were considered to be a
higher priority for this project based on the greater number of units in operation.
Computers, fax machines, and dot matrix printers have emissions generally related to
outgassing from electronic components and basic construction materials. These emissions are
highest for new machines and are thought to diminish rapidly with time. Therefore, although they
may impact localized IAQ and are found in most office settings, their total combined impact on
IAQ is likely to be less than dry-process photocopiers. However, based on the recommendations
of the technical advisors on the project, a study was conducted as part of this project to evaluate
off gassing emissions from printed circuit board laminates. The results of this study are
summarized in Cornstubble and Whitaker (1998).
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Table 2-1. Summary of Office Equipment Literature Review
*
Type of
Equipment
Emissions
Emissions Rate/IAQ
Potential Options
for Reduced
Emissions
Summary of Prioritization
Dry-process
photocopy
machines
Hydrocarbons, respirablc
suspended particles, and
ozone
Particulate: 1 ng/m3 room
concentrat."
03: peak production 131 |ig/sheetb
0-1350 ng/min, avg. = 259 |ig/minc
48-158 |ig/copyd
TVOC: 0.5-16.4 |ig/sheet from
paper'
Lower voltage, toner
reformulation,
transfer efficiency
Common product found in most
office settings. Smaller units
lower emission rates but more
common, large production units
often with dedicated ITVAC
systems
Laser
printers
Hydrocarbons, respirable
particulates, and ozone
Particulate: 0.0007-0.002 (ig/page1;
0.1 -4 mg/m3 room concentration";
0.0009-0.06 mg/min.' TVOC: 2.0-
6.5 pg/sheet from paper" ;0.08-0.26
mg/page'
Charged rollers
Common technology found in
most office settings
Computer
terminals
Ozone, electromagnetic
fields (EMF), and
offgassing VOCs
Little published data on EMFs,
none on VOCs or ozone
Low-emitting
materials and/or
lower voltage
Thought to have relatively low
emissions when compared to other
sources that have operating
emissions as well
Wet-process
photocopy
machines
Aliphatic hydrocarbons,
VOCs and ozone
TVOC: 25 g/h, 0.241 g/copy
observed high room concentration
of 35 mg/m3 r
Solvent
reformulation, filters,
decrease voltage
Obsolete technology, shrinking
market share
Ink/bubble
jet printers
Hydrocarbons, ozone
No published emissions rate data
Solvent
reformulation
Used primarily for personal
printers, home use
Spirit
duplicators
Methanol
No published emissions rate data
Mineral spirits or
photocopiers
Limited market, schools and
institutions
Mimeograph
printers
Hydrotreated heavy and
light naphthenic
distillates
No published emissions rate data
Replacement -
photocopiers
Limited market, schools and
institutions
Fax
machines
Ozone and VOCs
No published emissions rate data
Charged rollers
Found in most office settings,
rapidly changing technology may
be integrated with copier/ printers
Blueprint
machines
(dyeline)
Ammonia, carbon
monoxide, methanol,
ethanol, trinitrofluorene,
trichloroethane
1-40 ppm NII3 in breathing zone of
operator, average = 8.2 ppm8
CAD/altemative
technologies
Older technology, losing market
share to CAD/altemative
technologies
Matrix
printers
VOCs
TVOC: 0.7-1.0 |ig/sheet from
paper" No data on emissions from
operation
Low-emitting
materials
Used generally for personal
printers, home use. Relatively low
emission rates.
Plotters
VOCs, hazardous waste
residuals
No published emissions rate data
Limited market share, sales
around 250,000 a year worldwide11
" Schnell ct al 1992 *Tuskes ct al., 1988.
Greenfield, 1987. h DeNucci; , 992
d»>. . ' Gressel, 1996.
Hannsen and Anderson, 1986.
Allen et al197& VOCs = volatile organic compounds
Wo ko et a ., 1 3. TVOCs = total volatile organic compounds
Tsuchiya et al., 1988. CAD = computer-aided design
2-3
-------
As part of the literature review, other equipment that may have high individual emission
rates was identified. This equipment include spirit duplicators, mimeograph machines, plotters
digital duplicators and diazo (blueprint) machines. These types of equipment were not considered
for further investigation in this project because they are rather specialized with a smaller number
of units in operation. Furthermore, some of this equipment is no longer manufactured or is being
replaced by alternative technologies. Therefore, this equipment, although significant in a limited
number of settings, is believed to have lower total emissions and impact a smaller population than
dry-process photocopiers. Section 2.2 summarizes the information in the literature review on
photoimaging machines (Hetes et al., 1995).
2.2 Photoimaging Machines
Dry-process photocopiers, one type of photoimaging machine, make up a majority of the
photocopier market. The measurement of emissions from dry-process photocopiers was the focus
of the test method development activities of this cooperative agreement. Therefore, summary
information on photoimaging process design and operation, as well as selected emissions data, is
presented here for background purposes.
2.2.1 Equipment Design and Operation
Electrophotography is used in copiers, laser printers, and fax machines and is based on the
electrostatic transfer of toner to and from a charged photoconductive surface. The basic steps in
image processing are shown in Figure 2-1. They are: (1) charge, (2) expose, (3) develop, (4)
transfer, (5) fuse, and (6) clean. This six-step process is repeated for each copy. The imaging
process is depicted in Figure 2-2. The toner transfer process is depicted in Figure 2-3. The
critical element of any photoimaging process is the photoconductive drum, which typically has a
photoconductive coating such as selenium, cadmium sulfide, or zinc oxide. These materials have
the unique property of holding an electrostatic charge in the dark and losing the charge when
exposed to light, such as that reflected from the white areas of an original. Whether the drum is
positively or negatively charged during this process depends on the type of photoconductive
materials used. For the purposes of illustration, a positively charged selenium-based
photoconductive material is described.
Charge: Charging the photoconductive drum is the first step in the process. In the
charging step a uniform charge is imparted on the entire surface of the drum. In
conventional laser print and photocopier designs, electrically charged corona wires are
used to add a uniform primary charge across the surface of the photosensitive drum.
Canon, Inc., has developed an alternative dry-process photoimaging system in which the
corona wires are replaced with "charging" rollers. Unlike the corona wires, which are
separated from the drum by a small distance, the charging rollers are pressed directly
against the drum, requiring far lower voltages to generate the needed charge. This
technology is now available in laser printers as well and has been shown by Canon, Inc.
(1990) and Gressel (1996) to significantly reduce ozone emissions.
2-4
-------
5. Fix
Clean clean
Corotron Lamp
6. Clean
Cleaning
System
Light Imaging
4. Transfer
~
Transfer
Corotron
Photoconductive
Charge
Corotron
•* '*.i
1. Charge
>x Paper Path
Mirror
Mirror,'
l~-'' 2. Expose
Magnetic
Development System
3. Develop
Source: Adapted from Maren, T., Dry Toner Fundamentals, Xerox Research Center, 8th Annual Toner and Developer
Conference and Tutorial. September 1991, Diamond Research Company.
Figure 2-1. Six steps in the photoimaging process.
-------
Photoconductive
(e.g., Selenium-Coated
Drum is Positively Charged
Drum is Exposed to Light
(Positive Charge
Remains on Image)
Latent Image is D.eveloped
(Negative Toner Adheres
to Positive Image)
Develop
Charge
<(©
Transfer
Fix
\ \ \ V \ \ \
/ f
9 t t $ i i i
*******
Image is Transferred to Paper
(Positive Charge Behind
Paper Attracts Toner)
Image is Fused to Paper
by Heat and/or Pressure
Creating Exact Copy
of Original
Source: Adapted from Maren, T., Dry Toner Fundamentals, Xerox Research Center, 8th Annual Toner and Developer
Conference and Tutorial, September 1991, Diamond Research Company.
Figure 2-2. How photoircaging transfers ths image to paper.
-------
L2J
Transfer Corona
Pnotoconductive Drum
f Magnetic Drum
W
3a: Two component
development system
Toner
Carrier
Photoconductive Drum
Toner
Paper
l°J
Transfer Corona
3b: One component
development system
Figure 2-3. Schematic of toner transfer to and from photoconductive drum.
2-7
-------
Expose: During the exposure step the image is reflected onto the surface of the drum.
The original image (dark area) remains charged on the surface of the drum as the reflected
white areas of the original lose their charge when exposed to the reflected light.
Develop: The image is developed when the negatively charged toner particles or aerosols
are attracted to the positively charged areas of the image (see Figure 2-3). Developer
makes the latent electrostatic image on the drum visible. Developers are broadly divided
into dry and wet types. In general, the developer can consist of either one (toner alone) or
two components (toner and carrier). There are several physical processes by which the
toner is transferred to the charged image. The two-component developer (Figure 2-3a)
consists of a carrier and a toner that are oppositely charged. A magnetic field is used to
align the carrier (with attached toner) on a developing cylinder to form a "brush" that
carries the toner closer to the photoconductive drum. The charged surface (image) on the
drum then attracts the toner. A one-component system (Figure 2-3b) consists of toner
alone, made up of a resin (color) and magnetic material. Again, a magnetic cylinder is
used to align and uniformly collect the toner particles, which then are brought close to the
drum and attracted to the charged image. A blade is sometimes used to ensure uniform
coverage of toner on the magnetic drum.
Transfer: Once the image has been developed on the drum it must be transferred to the
paper (see Figure 2-3). To transfer the image to the paper, a transfer corona wire applies
a positive charge through the paper, which electrostatically attracts the negatively charged
toner particles off the photo drum and onto the surface of the charged paper. In the
Canon, Inc. process, a charged roller system is used to apply the positive charge to the
paper. One charging roller sits on top of the photosensitive drum within the toner
cartridge; the other charging roller (the transfer roller) is contained within the printer
housing and sits under the photosensitive drum. The paper travels between the transfer
roller and the photosensitive drum. The contact between the charging rollers and the
photosensitive drum prevents the formation of electrical arcs. About 75 percent of the
toner is transferred to the copy paper. The exact transfer efficiency depends on the
environment during transfer and the kind of paper used (Canon, 1990).
Fixing (Fusing^: Fusing refers to the process in which the toner that was transferred to the
copy paper is permanently bound to the paper. There are essentially two kinds of fixing
methods: heat fixing and pressure fixing (see Figure 2-2). In the heat fixing process, the
paper passes through two drums, one of which is heated to a temperature of about 160 to
200 °C, which heats the other drum upon contact. The paper passes between the heated
rollers and the toner is melted and pressed into the fibers of the paper, thus fixing the toner
to the paper. In a wet-process system, the heat results in the volatilization of the carrier
leaving the nonvolatile portion of the toner behind. In the pressure fixing method, the two
rollers are in very firm contact with each other. The paper passes between these rollers
and the toner is pressed firmly onto and into the paper, thus fixing the image. Some
machines use a combination of heat and pressure.
2-8
-------
Clean: Cleaning refers to the process in which any toner remaining on the surface of the
photoconductive drum after transfer is cleaned off so that the next copy image will be
clear and distinct. Cleaning is primarily a physical process in which a blade, brush, or web
is wiped across the drum surface to remove residual toner particles and collect the waste
toner. In some machines, a cleaning lamp may be used to remove the electrical charge
from the drum prior to the application of the web, blade, or brush.
All photoimaging processes contain the six basic steps outlined above; however, features
may differ with different equipment. For example, photocopiers use a high-intensity light source
to reflect the image onto the surface of a photoconductive drum while laser printers and fax
machines use a laser to impart the same charge on to the drum.
For dry-process photocopiers, the two-component developer described above consists of
toner (mainly carbon, resin, and adhesive) and carrier (iron powder). The size of the toner
particles typically range from 5 to 10 urn, and the carrier particles range from 50 to 200 ^m. The
one-component developer consists of toner alone, which is mainly resin and some magnetic
material. The sizes of these particles are similar to the toner particles in the two-component
system (about 10 jim). Toners are made primarily of styrene-based polyester resins with other
ingredients added as stabilizers (e.g., salicylic acid chromium (III) chelate) and pigments (for
color toner). Upon transfer of the toner to the charged paper, heat and pressure from the fuser
rollers fuse the toner to the paper and set the copied or printed image. In general, higher fuser
roller temperatures and smaller toner powder particle sizes are used in larger and faster photocopy
machines to hasten the fusing process, though the chemical makeup of the toner powders may
also be different. The temperature of the fuser rollers can be up to about 250 °C in the faster
machines, as compared to 160 to 200 °C found in most machines.
2.2.2 Published Indoor Air Emissions Data for Dry-process Photoimaging Machines
Photoimaging machines and related supplies contribute to indoor air emissions. Emissions
may result from operation and maintenance, equipment offgassing, or from processed paper.
Types of emissions include organics, ozone, and particulates. The following sections summarize
data in the literature on each of these emission types.
2.2.2.1 Ozone
Ozone is generated from the interaction of ultraviolet radiation with oxygen during
electrostatic discharges and from reactions with nitrogen dioxide and hydrocarbons. The nitrogen
dioxide and hydrocarbons may be produced in limited amounts from the source, may be found in
the indoor air as a result of other indoor sources, or may result from infiltration of outdoor air.
Ozone does not persist in the indoor environment because it quickly reacts and binds with
materials in the surrounding environment. As a result, the indoor air concentration of ozone
would be expected to decrease with distance from the source and with time. The electrically
charged corona wires used to add a uniform primary charge across the surface of the
photosensitive drum, and also to attract the toner from the drum to the paper surface, can
2-9
-------
contribute to ozone production and emissions. High voltages are applied to the corona wires to
attain the needed charge, and the associated electrical arcing results in the production of ozone.
Actual measurements of ozone emissions from photocopiers, typically using direct reading
instruments sampling the outlet air, are variable. According to some studies, advanced dry-
process photocopiers, even when recently serviced, can emit ozone at about 4 ^g per copy (Etkin,
1992). Greenfield (1987) found that ozone production with extended use can peak at 131 ^g per
copy, with an average of around 40 ^g/copy. By comparison, Allen et al. (1978) found that
emissions ranged from 48 to 158 ng per copy and that photocopier emissions have been found to
be dependent on copying rates, light intensity, and the maintenance status of the equipment.
Hannsen and Anderson (1986) surveyed 69 types of photocopying machines, which were found to
emit ozone at rates ranging from 0 to 1,350 |ig/min, with a mean of 259 pg/min. Gressel (1996)
evaluated ozone emissions from four different models of laser printers. Overall, their results
indicated that ozone emissions from older printers with corona wires were high enough (0.005-
0.06 mg/min) to cause concern in an indoor environment. On the other hand, newer printers with
a charged roller system produced very little ozone (0.0008 mg/min).
Many copiers are equipped with ozone filters that allow the ozone to react with the filter
media, thus reducing ozone emissions. These filters must be cleaned periodically to ensure proper
removal of ozone because the filter
media can be exhausted with time,
reducing the effectiveness of ozone
removal. Claridge (1983) presented data
to indicate the effectiveness of servicing
on reducing ozone production from
photocopiers. As shown in Table 2-2,
the amount of ozone produced per copy
was greatly reduced following routine
maintenance. Machines were serviced
after about 64,000 copies had been
made. Following servicing, the quantity
of ozone gradually returned to
preservicing levels after only 3,000
copies (Claridge, 1983).
Etkin (1992) also reports that some researchers have downplayed the significance of
indoor sources of ozone, demonstrating that in areas with high outdoor ozone levels, most indoor
ozone actually originates from outdoors. Etkin's report notes that, in most office buildings,
computer equipment, laser printers, and photocopying machines do not add significantly to indoor
ozone levels. However, high densities of this equipment and/or inadequate fresh air supplies can
lead to elevated ozone levels that may cause adverse health effects.
2.2.2.2 Volatile Organic Compounds (VOCs)
Table 2-2. Ozone Produced by Photocopiers
Before and After Maintenance
Emissions
(jig/copy)
Machines
Before Service
After Service
IBM 6800
22
4
Xerox 3400
47
1
Kodak 100
16
1
Source: Claridge, 1983.
2- 10
-------
NIOSH measured emissions of volatile organics from four different models of laser
printers (Gressel, 1996). The generation rates (per page) of various volatile organics are reported
in Table 2-3.
WolkofF et al. (1993) have conducted one of the most comprehensive studies on emissions
from finished products of selected office equipment. The study used both headspace analysis and
chamber studies to quantify emissions from copied paper from office copiers and printers.
Results from Wolkoff et al. (1993) indicate that the VOCs in toner powders include
solvent residues (e.g., benzene, toluene, xylene), monomers (styrene and acrylate esters),
monomer impurities (ethyl, propyl, and isopropyl benzenes, and diphenyl butane isomers),
coalescent agents (Texanol), monomer or polymer oxidation products (e.g., benzaldehyde), and
polymer toner additive decomposition products. The more volatile components from toner
powders dominate the emissions from paper. Xylenes and styrene were dominant in samples from
processed paper from all machines tested, and acrylates were found to be minor components.
Table 2-4 summarizes the major VOCs emitted from processed paper. Table 2-5 summarizes the
TVOC emission rates from fresh copies from all machines evaluated. In general, emissions rates
for matrix printers were lowest (0.7 to 1.0 (ag/sheet) while there was wide variation in the rates
from photocopied paper (0.5 to 16.4 (ig/sheet). The authors estimated a styrene concentration of
12 jig/m3 for 200 freshly processed copies in a 17-m3 office. The air exchange rate used in this
calculation was 0.25 air change per hour (ACH), and the emission rate used was 6 ng/m2/h.
2.2.2.3 Particulates
Gressel (1996) used a TSI aerodynamic particle sizer to measure particulate emissions
from four different models of laser printers. Particulate generation rates from the four printers
were reported as being "well below 0.1 |ag/min." However, particle generation from toner
cartridge replacement or the effect of paper and/or paper type on particle generation were not
considered.
Table 2-3. Laser Printer Emission Rates of Various VOCs and TVOCs Reported as
Toluene Equivalents (mg/page), Source: Gressel, 1996
Printer
Printing Rate
(pg/min)
Butanol
Toluene
Xylenes
Benzene"
Total VOCs
A
6.5
0.024
±0.0471
ND
0.050
±0.0688
ND
0.238
±0.318
B
6.5
0.042
±0.0183
ND
0.070
±0.0813
ND
0.257
±0.163
C
12.5
0.003
±0.00911
0.006
±0.0107
0.002
±0.00395
0.002
±0.00532
0.083
±0.131
D
6.5
0.022
±0.0276
0.003
±0.00666
0.020
±0.0232
ND
0.158
±0.158
ND = Nondetccted.
'Benzene was quantified for printer C only; not identified as a major peak on the gas chromatograph for other printers.
2-11
-------
Table 2-4. VOC Emitted from Processed Paper (Listed According to GC Retention Time)
Photocopied
Laser Printed
Matrix
Printed
A*
B
c
D
E
F
G
H
I
J K
Benzene
x
x+
x+
x+
*+
*+
X
x+
X
X X
1 -Butanol
x+
x+
X
x+
x+
X+
X
x+
X
Toluene
x+
*+
x+
*+
x+
*+
x+
x+
* X
Pyridine
x+
1 -Methyl-2-pentanone
x+
x+
Hexanal
*
X
X
X
X
X
X
X
x
* *
C4-Cyclohexane isomers
+
x+
+
+
1 -Butyl-ether
x+
+
X
+
x+
x+
x+
X X
Ethyl benzene
*+
*+
*+
*+
*+
*+
*+
*+
*+
X *
m- and p-Xylene
*+
x+
*+
*+
*+
*+
*+
*+
*+
X *
o-Xylene
x+
x+
*+
x+
x+
x+
x+
x+
*+
X X
Styrene
*+
*+
*+
*+
*+
*+
*+
*+
*+
* *
1 -Butyl acrylate
x+
*+
x+
2-Phenylpropane
X
x+
X
x+
x+
x+
x+
x+
x+
X X
3-Heptanol
x+
1 -Phenylpropane
X
x+
x+
x+
x+
x+
x+
x+
x+
X X
Ethyl toluene isomers
X
x+
x+
x+
x+
x
x+
x+
x+
X
3-Ethyoxy-3-ethyl-4,4-
dimethylpentane
*+
*
1 -Butyl methacrylate
x+
+
Benzaldehyde
+
x+
x+
x+
x+
x+
X X
Diethylbenzene isomers
X
X
x+
*+
X
X
2-Ethyl-1 -hexanol
x+
+
+
x+
x+
X
2-Ethylhexylacetate
+
+
x+
+
2,2-Azo-bis-
isobutyronitrile
+
x+
x+
x+
2-Ethylhexyl acrylate
x+
x+
x+
x+
X X
x = detected in processed paper emissions, * = four largest peaks, + = detected in toner powder.
' Hexane, 1,1 -dichloro-1 -nitroethane, octene, pentanal, and trichloroethene were all observed in paper emissions.
Source: Wolkoffet al., 1993.
2- 12
-------
Table 2-5. TVOC Emissions from Fresh Copies (fig/copy sheet)3, Source: WolkofT et alM 1993.
Photocopying Machines
Laser Printers
Matrix Printers
A
1.6
G
6.5
J 0.7
B
16.4
H
2.6
K 1.0
C
0.5
I
2.0
D
2.4
E
6.1
F
7.5
* Emitted from fresh black copies during 16 hours.
Schnell et al. (1992) used a continuous tape-feed Aethalometer to measure the black
carbon (BC) particulate emissions in an interior photocopier room in a six-story office/research
building. The room's interior measurements were 20ftxl5ftxl0ft (6x4.5x3 m). The
photocopier was a recent model (at the time of the study), designed for medium-volume office
use. At the end of the copying run, which was 200 to 800 copies, the photocopier was turned off
and an aethalometer continued to measure for 24 hours thereafter. The concentration of BC
aerosol produced by the photocopier occasionally raised room levels to the l-|ig/m3 level. This is
equivalent to BC levels observed in urban areas under moderate vehicle traffic (Schnell et al.,
1992). The concentration of finely dispersed, charged BC aerosol is reduced upon cessation of
photocopying. In the room (under no-air-ventilation conditions), BC concentrations fell to
background levels within 30 to 60 minutes.
The potential for particulate indoor air emissions is expected to increase over time
between maintenance cycles. Typically, about 75 percent of the toner is transferred to the
photoconductive drum. Toner particles that do not adhere to the drum become available for
emission to the indoor air. As the photoconductive surface of the drum deteriorates, the toner
transfer efficiency decreases. Although this decrease in efficiency increases the potential for
indoor air emissions, there were no published data on the extent to which these unbound toner
particles are emitted to the indoor environment.
2.3 Summary
This literature review suggested that there is a general lack of published emissions data.
Discussions with industry representatives indicated that much of the existing data on emissions
from office equipment are proprietary. Furthermore, the methods currently being used for
emissions testing both by researchers and by industry are variable. As a result, data from one
study are not comparable to those from another using a different method. In addition, the test
methods currently used often focus on measuring levels from equipment to determine if these
levels exceed occupational limits as opposed to measuring pollutants present in the indoor air of a
2- 13
-------
typical office environment. Given these limitations, a high priority of this research was the
development of a standard test method capable of providing emission rates for office equipment.
2- 14
-------
3.0 PHASE I: TEST METHOD DEVELOPMENT, EVALUATION, AND RESULTS
The procedure that was used to develop the emission testing guidance consisted of:
(1) forming an RTI/EPA/industry subcommittee; (2) obtaining and reviewing existing testing
methodologies; (3) developing an outline of the major testing issues and objectives; (4) preparing
a draft test method; and (5) reviewing and revising the method based on subcommittee member
comments. The revised test method was then submitted to the entire group of technical advisors
participating in this cooperative agreement for their input. The test methodology that resulted
from this collaborative process was based on many discussions about balancing the desire for a
specific and sophisticated method designed to establish minimum performance standards while
still providing flexibility to accommodate different equipment types and emission test facilities.
3.1 Discussion of Method
The test method is detailed in Appendix B (Emissions Testing Guidance Document for
Dry-Process Photocopy Machines), and a brief overview of the recommended chamber test
conditions is presented here and summarized in Table 3-1.
The test method presented in the Emissions Testing Guidance Document uses flow-
through dynamic chambers because they are generally applicable to all types of equipment and
generally mimic typical use conditions found in an office. The chamber's linear dimensions should
be a minimum of 1.4 times the dimensions of the equipment tested; e.g., the minimum size
chamber for a machine measuring 1.5 by 1 by 0.5 m is 2.1 by 1.4 by 0.7 m. The value of 1.4 was
selected based on the prior experience of manufacturers in chamber testing. Its primary basis is to
allow for adequate space for servicing of equipment in the chamber, while also allowing for air
movement.
Chamber temperature is maintained at 26-31°C by conditioning the inlet air. This
temperature range is a practical compromise between typical office conditions (e.g., 23 °C) and
temperatures that can be achieved when equipment that has a high thermal load is tested.
Because photocopiers can produce large amounts of heat, up to 24,000 Btu/hr (25,322 kJ/hr), it
may be difficult to maintain chamber temperatures below 26°C. An air exchange rate of 2.0 + 15%
air changes per hour (ACH) on a once-through basis (i.e., non-recirculating) was specified for this
method because it is a reasonable approximation of normal indoor conditions (approximately 1
ACH of outdoor air) and also addresses the need to dissipate heat that may be generated by
equipment operation while still maintaining a temperature between 26 and 31°C. [Note that the
American Society of Heating, Refrigerating and Air Conditioning Engineers (ASHRAE, 1989)
has a standard which specifies an outdoor air requirement of 2.50 L/s/s-m2 in duplicating and
printing areas. The standard also specifies that the installed equipment must incorporate positive
exhaust and control (as required) of undesirable contaminants.]
Relative humidity (RH) within the chamber is maintained between 30 and 35%. Initial
experiments targeted 50% RH; however, at the high end of the temperature range (31°C), it was
not possible to meet 50% RH. It was also anticipated that the amount of water needed to maintain
3 - 1
-------
50% RH in the chamber might cause problems with water collection on the sorbent tubes during
VOC analysis. A RH of 35% at 31°C represents a mass of water equivalent to 50% RH at 23°C.
Table 3-1. Conditions for Chamber Testing
Condition
Components Testing
Chamber Size
Temperature
% RH
Air Exchange Rate (ACH)
Copier Operation Time
Sample Collection Time (integrated)
Loading (L)
22.7 m3
26 to 3 PC
30 to 35
2.0 ± 0.2 h"1
20 to 40 min
140 to 160 min
1 Copier
The VOCs and aldehydes/ketones targeted for testing are shown in Table 3-2. VOCs
were selected based on screening analysis of chamber air samples collected during copier emission
tests. Replicate chamber air samples collected on a multisorbent tubes during each copier test
were analyzed by full-scan Gas Chromatograph/Mass Spectrometer (GC/MS) followed by an
electronic search of the National Institute of Health (NIH)/EPA Mass Spectral Data Base
(MSDB), National Bureau of Standards (NBS) library, and the Registry of Mass Spectral Library
(Wiley library) to identify the chemicals present. Manual verification was performed on each
peak to confirm computer identifications and to identify compounds not found using the computer
library search. Emission rates for these screening samples were estimated by comparison to a
calibration standard for the chemical or to toluene. Compounds with estimated emission rates of
about 400 /ag/h and greater (> 2.5 Mg/m3) were included in the target list. The target list for
aldehydes/ketones reflects the individual compounds found in a commercially available calibration
standard mix commonly used dinitrophenylhydrazine (DNPH) analysis. Methods for measuring
chamber air concentrations of VOCs, aldehydes/ketones, ozone, and particles are summarized in
The duration of the test was selected to ensure that chamber equilibrium is reached or that
total emissions are measured. In general, 4 air changes are required to replace 99% of the air in
the chamber used for this project since it is a single-pass system. Based on an ACH of 2.0, a 2
hour test is required for the chamber used in this study. Three alternative approaches could be
used:
1. Operate the equipment for 2 hours continuously, at which time sampling could occur and,
with the absence of wall effects, the chamber air concentration is assumed to be in
Table 3-3.
equilibrium.
3-2
-------
Table 3-2. Organic Chemicals Targeted for Emissions Testing
Chemical Class
VOCs
Aldehydes/ketones
Toluene
Benzaldehyde
/7-Butyl acetate
Ethylbenzene
/w,/?-Xylene
2-Heptanone
Styrene
o-Xylene
2-Butoxyethanol
Isopropyl benzene
n-Propyl benzene
Formaldehyde
Acetaldehyde
Acetone
Acrolein
Propionaldehyde
Crotonaldehyde
2-Butanone
Compounds
a-Methyl styrene
/7-Decane
2-Ethyl-1 -hexanol
a-Pinene
Limonene
/?-Nonanal
2,5-Dimethyl styrene
ft-Undecane
^-Decanal
wDodecane
BHT
Methacrolein
Butyraldehyde
Benzaldehyde
Valeraldehyde
/w-Tolualdehyde
w-Hexanal
Table 3-3. Methods for Measuring Chamber Air Concentrations of Target Analytes
Analytes Method
VOCs VOCs in air samples (1 to 8 L) collected on multisorbent tubes.
(Tenax/Ambrasorb/Charcoal tubes were used for Phase I. For Phase
II, RTI used Tenax/Carboxen 1000 tubes.) Tubes analyzed by gas
chromatography/mass spectrometry. Screening and quantitation
samples collected and analyzed. Screening samples used to identify
target VOCs. Quantitation samples used to measure air
concentrations of target VOCs using a multipoint calibration.
Aldehydes/ketones Aldehydes/ketones in air samples (36 L) collected on DNPH-coated
silica gel cartridges. Cartridges solvent desorbed with acetonitrile.
Extract analyzed by high performance liquid chromatography
(HPLC). Concentrations in sample extracts measured using a
multipoint calibration.
Continuous monitoring of chamber air concentrations using a
DASIBI model 1003-AH ozone monitor.
Continuous monitoring of chamber air concentrations using a particle
measuring systems LAS-X optical particle counter.
Ozone
Particles
3-3
-------
2. Operate the equipment for a defined period of time, collecting an integrated sample from
the start of operation until 2 hours (i.e., 4 air changes) after the equipment is turned off.
In the absence of wall effects, this sample should represent about 99% of total emissions
during operation for the chamber used in this study.
3. Take short-term periodic samples throughout the period of operation. This approach
should be used when information on the time course of emissions is required. This option
is useful to determine how emissions change with time of operation.
Note that some types of office equipment, such as photocopy machines and printers, can
operate unattended only for a limited period of time due to a finite paper supply. If the equipment
cannot operate continuously for the 2 hours required for the chamber to reach equilibrium plus the
time required to collect a sample, then one of the following approaches must be used:
• Multiple machines must operate sequentially so that operation is continuous for the time
period required (6 hours), or
• An integrated sample must be taken from the start of operation until 2 hours (4 air
changes) after the cessation of operation.
For the machines evaluated in this study, 2000 copies were printed for each test, and an
integrated sample was collected from the start of operation until 2 hours (i.e., 4 air changes) after
the paper supply was exhausted. The paper supply of 2000 sheets was exhausted after 20 to 40
minutes, depending on the machine, resulting in a total sample collection time of 140 to 160
minutes.
3.2 Validation and Use of the Method
After the test methodology was defined, it was evaluated using a two-phase process.
Phase I was a single laboratory evaluation of the method in the RTI large chamber, and Phase II
was a multilaboratory, or round-robin, evaluation. The following sections describe the Phase I
activities and results. A similar discussion for Phase II is in Section 4.
The primary goal of the Phase I testing was to conduct a single laboratory evaluation of
the test method for measuring emissions from dry-process photocopiers. Also, since the literature
review indicated that little emission data for photocopiers were currently available in the published
literature, a secondary goal of the effort was to develop emission rate data for dry-process
photocopiers. It was also expected that results from the Phase I testing would be used to guide
refinements in the test method prior to implementing the Phase II round-robin evaluation of the
test method. Testing was to include measurements for VOCs, aldehydes and ketones, ozone, and
particles. However, while the issue of particle emissions from photocopiers is important, it
became apparent early in the project that a thorough evaluation of the particles would be beyond
the scope of this study and, for this reason, particle measurements were not an emphasis of this
project.
3-4
-------
To meet the goals of the Phase I testing, four experimental objectives were defined.
1. Conduct a single laboratory evaluation of the large chamber test method
using standard materials as sources for generating emissions inside the
chamber. Precision and accuracy data for emission rate measurements
were to be determined for the large chamber method based on these
results. VOCs, aldehydes/ketones, and ozone were selected for evaluation
in the large chamber at RTI since standard emitting sources for these
chemical groups were easily available and could be shown to be reliable.
Particles were omitted from this evaluation since methods for accurately
evaluating them in the chamber is complex and would be difficult without
potentially contaminating the chamber. A thorough evaluation of particles
in the chamber would also require more effort than resources for this study
could reasonably provide. Without particle recovery information, chamber
validation for particles would not be possible and overall data accuracy
would not be known. Because of these issues, evaluating particle
emissions was limited to making some unvalidated initial measurements so
some general conclusions might be possible, and the focus of the evaluation
was centered on VOC, aldehyde/ketone, and ozone emissions.
2. Conduct triplicate tests on a single dry-process photocopier to identify emissions
and quantify emission rates for VOCs. aldehydes/ketones. and ozone. During each
test, a single time-integrated sample was collected to measure average chamber air
concentrations over the test period. Results were used to determine precision of
emission-rate measurements for the chamber test method during equipment
operation.
3. Conduct tests on four dry-process photocopiers from different manufacturers to
identify emissions and quantify emission rates for VOCs. aldehvdes/ketones. and
ozone. Tests were conducted using time-integrated samples to measure average
chamber air concentrations over the test period. Results were used to identify the
important emissions and to evaluate variability in emission rates between copiers.
4. Conduct emissions time-course tests on two dry-process photocopiers. During
testing, samples were collected every 10 to 15 minutes to quantitate emission rates
as a function of time. Results were used to evaluate changes in emission rates over
time of copier operation and to determine if integrated samples were adequate.
Table 3-4 gives an overview of the experimental design that was used for Phase I testing.
All testing was conducted in a 22.7 m3 chamber at RTI designed for organic emissions testing. A
description of the chamber is given in Table 3-5. Conditions for chamber testing are given in
Table 3-1.
3 - 5
-------
Table 3-4. Experimental Design for Phase I Testing
Type of Testing
Replicates
Purpose
CHAMBER PERFORMANCE
Standard emitters for VOCs, aldehydes/ketones,
ozone. Single time-integrated chamber air sample
collected during chamber testing. Data generated
over a 1-week period.
Standard emitter for VOCs. Single time-integrated
chamber air sample collected during chamber
testing.
Standard emitter for VOCs. Chamber air samples
collected every 10 to 15 minutes during testing.
PHOTOCOPIERS
Photocopier 1. Single time-integrated chamber air
sample collected during testing.
Photocopier 1. Single time-integrated chamber air
sample collected during testing. Chamber air
samples also collected every 10 to 15 minutes
during test run.
Photocopier 1. Single time-integrated chamber air
sample collected during testing. All filters changed
in copier.
Photocopier 2. Single time-integrated chamber air
sample collected during testing.
Photocopier 3. Single time-integrated chamber air
sample collected during testing.
Photocopier 4. Single-time integrated chamber air
sample collected during testing. Chamber air
samples also collected every 10 to 15 minutes
during test run.
To generate precision and accuracy data for VOC,
aldehyde/ketone, ozone emission rates for large
chamber test method.
To demonstrate ongoing recovery of known VOC
emitters from the test chamber during the
emissions testing.
To demonstrate recovery of known VOC emitters
from the chamber over short time intervals; used to
judge method performance for time-course testing;
to compare results from integrated and time-course
samples.
To identify VOCs emitted; to measure emission
rates for VOCs, aldehydes/ketones, ozone, and
particles in the full power and the idle mode; to
evaluate precision of emission rate measurement
for copiers in the full operation mode.
To evaluate reproducibility of test method over an
extended time period; to evaluate changes in
emission rate over time of copier operation.
To evaluate change in emissions as a result of
changing operating conditions.
To identify VOCs emitted; to measure emission
rates for VOCs, aldehydes/ketones, and particles in
the full power and idle modes; to assess variability
between copiers operated in the full power and idle
modes.
To identify VOCs emitted; to measure emission
rates for VOCs, aldehydes/ketones, and particles in
the full power and idle modes; to assess variability
between copiers operated in the full power and idle
modes.
To identify VOCs emitted; to measure emission
rates for VOCs, aldehydes/ketones, and particles in
the full power and idle modes; to assess variability
between copiers operated in the full power and idle
modes; to evaluate changes in copier emissions
over operating time.
3-6
-------
Table 3-5. Description of RTI's Large Environmental Test Chamber
Parameter
Description
Size
3.05 x 3.05 x 2.5 m (22.7m3)
or 10 x 10 x 8 ft. (800ft3)
Construction Materials
Ducts: Aluminum
Ceiling/Walls: Aluminum
Floor: Stainless Steel
Gaskets: Viton
Air Supply System
Outside air passed through particulate filters then through
Carasorb 200 filters for organics removal, followed by HEPA
filtration and a final charcoal filter
Temperature Control
18 to 35°C ± 1 °C (64 to 95° ± 2°F)
Humidity Control
40 to 70% Relative Humidity (RH) ±5%
Air Exchange Rate
0.2 air changes/h to 2 air changes/min
Sampling Ports
0.635 cm (0.25 inch) stainless steel Swagelok Adaptable to meet
other requirements
Measurement Systems
Temperature/Humidity - General Eastman Model 850
Air Flow - Carrier Comfort Network Distributed Controller
Data Acquisition - 386 PC
During Phase I, testing was conducted on four mid-range copiers (30-150 copies per
minute). This type of copier was selected because the literature review (Hetes et al., 1995)
indicated that these types of copiers are prevalent in the office environment. The process used to
select the specific copier models for testing included a review of the Buyers Laboratory Copier
Specification Guide (BLI, 1995) to identify mid-range copiers using different toner types,
developing systems, fusing mechanisms, and photoconductive drum surface materials.
Characteristics of the four copiers selected for testing are given in Table 3-6.
3-7
-------
Table 3-6. Copiers Tested
Copier ID
1
2
3
4
Toner Type
dry, dual-
dry, dual-
dry, mono-
dry, dual-
component
component
component
component
Development
magnetic
magnetic
magnetic
magnetic
brush
brush
roller
brush
Fusing
heat/
heat/
hot roller
heat/
pressure
pressure
pressure
Photoconductor
organic
organic
amorphous
organic
drum
belt
silica drum
drum
Toner Condition
used
new
new
used
Condition
used-50,000
new
new <100
used -76,000
copies
copies
copies
Copies per Minute
50
85
50
50
3.3 Chamber Evaluation
3.3.1 Procedure
As a first step in evaluating the large chamber test method, a recovery study was
conducted to evaluate the accuracy and precision of the emission rate measurements. This was
accomplished by introducing selected VOCs, formaldehyde, and ozone into the chamber at known
rates. Procedures for generating and introducing these chemicals into the chamber air are
outlined in Table 3-7. Chamber air samples were then collected and analyzed for pollutant
concentrations using procedures identical to those used during the emission tests with
photocopiers. The measured amount of pollutant emitted during each test was calculated as
Em = Ccx Vcx AcxTs (1)
where
Em = the measured amount of target pollutant emitted during each test in (ig.
Cc = the measured chamber air concentration in ng/m3.
Vc = the chamber volume in m3.
A,. - the air exchange rate in h"1.
Ts = the sample collection time in h.
3 - 8
-------
Table 3-7. Methods for Generating Standards with Known Emissions
Chemical Class Method
VOCs Cylinder containing toluene and chloroform or n-decane prepared
• 10 L volume metered into chamber at a rate of 1.0 LPM.
Samples collected over 2 hr 10 min period to give an integrated
chamber air concentration of ~ lO^g/m3.
• 10 L volume metered into chamber at a rate of 0.25 LPM over 40
min. Time point samples collected for T = 0-10, 10-20, 20-30, 30-
45, 45-60, 60-75, 75-90, 90-105, 105-120, and 120-160 min.
Aldehydes/Ketones Aqueous solution of formaldehyde (-53 ng/mL) delivered to
chamber with HPLC pump, vaporized by passing through 350 °C
heated tubing at rate of 2.1 mL/min for 30 min, samples collected
over a 2 hr 30 min period.
Ozone Generator producing -75-90 ppm 03 at 1 LPM attached to
chamber for 2 hr period. Monitored increase and decrease of
chamber concentration.
Percent recovery of the emitted pollutant was used to evaluate accuracy of the emissions test
method. Percent recovery (%R) was calculated as
%R = Eam/Easxl00 (2)
where Eam is the amount measured during the recovery test in fig, and is the amount that was
introduced into the chamber during the test in (ig.
Recovery tests using integrated samples collected over the test period were conducted in
triplicate for the VOCs, formaldehyde, and ozone. For these recovery tests, precision of the
emission rate measurement was evaluated as percent relative standard deviation (%RSD) of the
replicate tests.
For the VOCs, the recovery test was repeated midway through the Phase 1 testing to
demonstrate ongoing performance of the large chamber. A time-course recovery study was also
conducted to evaluate the recovery of VOCs from the chamber over time. For this latter test,
both time-point samples and an integrated sample for the entire test period were collected to
allow a comparison of data generated by both collection schemes.
3-9
-------
3.3.2 Results
Results of the VOG recovery tests are summarized in Table 3-8. Data for the time-course
recovery study are given in Figures 3-1 and 3-2 which are plots of chamber air concentration vs.
time for chloroform and toluene, respectively. The figures show both the concentrations
measured during testing and the theoretical concentration given the known emission source under
the chamber test conditions.
In general, the results show good accuracy and precision for the chamber evaluation.
Observations from the results follow.
• For the triplicate recovery tests using time integrated samples (Test 1 to 3,
Table 3-8), both accuracy and precision of the test method was good for both
chloroform and toluene.
• The repeat test for the time-integrated recovery study (Test 4, Table 3-8) again
showed good recovery for both chloroform and toluene demonstrating that
acceptable performance of the emission test method continued throughout Phase 1
testing.
• Results for the time course study (Test 5, Table 3-8) showed good recovery for
toluene for both the time-point and the integrated sample. However, for
chloroform, calculated recovery using data from the time-point samples showed
good recovery, but the integrated sample showed poor recovery. Poor recovery
using the integrated sample was due to a problem during analysis, not poor
recovery from the chamber. Excess water collected on the time-integrated sample
suppressed the signal from the MS during analysis to give a low measured chamber
air concentration for chloroform.
• Plots of the data for the time-point samples (Figures 3-1 and 3-2) showed good
agreement between the measured and the theoretical concentrations for all time
points except the point at 37.5 minutes. Given the good agreement for the other
time points, it is likely that the lower measured concentration at this point may be
due to an inaccuracy for sample collection or analysis.
Results for the recovery test for formaldehyde and ozone are given in Table 3-9. Data
again showed reasonable accuracy and precision of the large chamber test method for these two
pollutants. A plot of the ozone concentration data over time compared to the theoretical values is
given in Figure 3-3. Recovery of ozone is on the low side possibly due to reactions with the
chamber surfaces or due to comparison to the relatively crude method of using Drager tubes for
determining generator concentrations.
3 - 10
-------
Table 3-8. Chamber Recovery Test Results - VOCs
Chemical
Date
Measured Theoretical
Mass (ng) Mass (ng) % Recovery
Chloroform
Test 1
Test 2
Test 3
Test 4
Test 5
Integrated sample
Time-point sample
5/22/95
5/23/95
5/25/95
9/1/95
9/14/95
2,700
2,900
2,600
3,100
1,500
2,200
3,000
3,000
3,000
Mean
3,000
2,600
2,600
90
97
87
91 (6.2)a
103
58b (52)b'c
85 (73)c
Toluene
Test 1
Test 2
Test 3
Test 4
Test 5
Integrated sample
Time-point sample
5/22/95
5/23/95
2,400
2,500
5/25/95 2,500 (2. l)a
9/1/95
9/14/95
2,400
2,000
2,100
2,100
2,100
2,100
Mean
2,100
1,800
1,800
114
119
119
118 (2. l)a
114
111 (95)c
117 (99)c
3 %RSD of replicate chamber air samples.
b Water in sample suppressed signal for chloroform to give low calculated emission.
c Release rate from cylinder changed slightly over 40-minute release period. Recovery given in
parentheses calculated using the higher release rate. Change in release rate at the start was
probably due to pressure buildup in the valve.
3 - 11
-------
Time (hours)
Figure 3-1. Recovery from chamber
chloroform.
-------
70 ,~
60
50
CO
E
=3
C
0
~CD
1
-+—»
c
0
o
c
o
o
40
30
20
10
0
a A
0
0.5
Measured
Theoretical
1 1.5
Time (hours)
Figure 3-2. Recovery from chamber
toluene.
2
2.5
-------
Table 3-9. Chamber Recovery Test Results - Formaldehyde and Ozone
Measured Emission Rate (ng/h)
Compound
Test 1
Test 2
Test 3
Mean % RSD
Theoretical
Emission
% Rec.
Rate(ng/h)
Formaldehyde
5800
5900
6100
6000 2.0
6400
93
Ozone (peak conc.)
6700
6600
5600
6300 9.4
8800a
72
a Based on Drager tube measurements.
3.4 Photocopier Test Results
3.4.1 Sample Collection and Emission Rate Calculations
Large chamber emission tests were performed on four dry-process photocopiers from
different manufacturers. As described in Table 3-4, five experimental objectives were defined:
1. Evaluate precision of the emission rate measurements for one copier in the idle and full
operation modes using a fixed set of operating conditions;
2. Evaluate the variability of emission rate measurements between copiers from different
manufacturers;
3. Evaluate the variability of emission rate measurements for one copier using different
operating conditions;
4. Evaluate the change in emission rates as a function of copier operating time; and
5. Evaluate the practical aspects of test method implementation.
To address these experimental objectives, a total of nine separate emissions tests were
conducted. For each test, the same basic sequence of operations was performed as outlined in
Table 3-10. The copiers tested and specific conditions for each test are given in Table 3-11. For
each test, concentrations of VOCs, aldehydes/ketones, and ozone were measured in the chamber
air. Particles were measured for a subset of the nine photocopier tests. However, since
experiments were not conducted to determine the recovery of particles from the chamber, little
emphasis was placed on these results. This was not to say that the results were not important,
just that a full evaluation of the particle measurements/validation was beyond the scope of this
study. Figure 3-4 shows a typical particle trace of photocopier 1 during an emissions test and
Figure 3-5 shows the particle size distribution during the same test.
3 - 14
-------
10
00
90
80
70
60
50
40
30
20
10
0
Measured ppb 03
Theoretical ppb 03
0 60 120 180 240
Time (min)
Figure 3-3. Chamber recovery
ozone - recovery test 3.
-------
Table 3-10. Copier Testing Procedure for Phase I (refer to Appendix B for details)
1. Background air samples collected from empty chamber.
2. Copier placed in chamber.
3. Service representative checked copier and assisted in setting up remote start capability.
4. Paper loaded in copier, copier powered up, equilibrated overnight.
5. Air samples collected during copier powered up but idle.
6. Air samples collected during full copier operation
- 2,000 copies/30-40 minute operation time
- For integrated sample, sample collection started when copier started printing; collection
continued for 2 hours (4 air changes after copying process ended)
- For time-point samples, sample collected for T = 0-10, 10-20, 20-30, 30-45, 45-60, 60-
75, 75-90, 90-105, 105-120, and 120-160 minutes after copier began printing.
7. Carbon monoxide release made during copier operation to accurately determine air
exchange rate.
3 - 16
-------
Table 3-11. Conditions for Copier Testing
Copier
1
1
1
1
1
1
2
3
4
Test
1
2
3
4
5
6
7
8
9
Date
5/1/95
5/4/95
5/5/95
5/8/95
9/19/95
9/21/95
4/25/95
8/30/95
8/28/95
Toner Type
dry, dual
dry, dual
dry, dual
dry, dual
dry, dual
dry, dual
dry, dual
dry, mono
dry, dual
Development
magnetic
brush
magnetic
brush
magnetic
brush
magnetic
brush
magnetic
brush
magnetic
brush
magnetic
brush
, magnetic
roller
magnetic brush
Fusing
heat/
heatJ
heat/
heat/
heat/
heat/
heat/
hot roller
heat/
pressure
pressure
pressure
pressure
pressure
pressure
pressure
pressure
Photoconductor
organic
drum
organic
drum
organic drum
organic drum
organic drum
organic drum
organic
belt
amorphous
silica drum
organic drum
Toner Lot
1-1
1-2
1-2
1-2
1-2
1-2
2-1
3-1
4-1
Toner Condition
used
new
new
new
used
used
new
new
used
Copier Condition
used
used
used
used
used
filters
new
new -
used -76,000
-50,000
-51,000
-53,000
-55,000
-57,000
replaced
<100
copies
<
copies
copies
copies
copies
copies
-59,000
copies
copies
Run Time (min)
19.17
37.85
37.78
37.72
37.55
37.58
22.98
39.90
37.12
# Pages
999
2,000
2,000
2,000
2,000
1,998
1,929
1,998
1,998
ACH
1.86
1.82
1.82
1.91
1.79
1.87
1.86
1.89
1.85
Chamber T (°C)
Idle (avg)
26.2
26.5
26.3
26.8
26.2
26.6
26.9
26.9
26.4
Max
27.8
29.0
28.7
29.5
28.3
29.4
31.1
29.1
28.1
Change
1.6
2.5
2.4
2.7
2.1
2.8
4.2
2.2
1.7
Chamber RH (%)
Idle (avg)
32.6
32.7
32.6
32.8
27.2
31.5
32.7
31.1
31.6
Max
39.1
45.3
44.0
42.3
47.9
40.6
36.6
46.4
51.7
Change
6.5
12.6
11.4
9.5
20.7
9.1
3.9
15.3
20.1
Sampling
Integrated
Integrated
Integrated
Integrated
Time-Course.
Integrated
Integrated
Integrated
Integrated
Time Course,
Integrated
ACH = air changes per hour
T = temperature
RH = relative humidity
-------
Copier 1
Figure 3-4. Copier 1, particle concentration during test run.
-------
Copier 1
Standard Size Distribution
1E5
1E4
1E3
1E2
is^Copier
^Background
Diameter (urn)
Figure 3-5. Copier 1, particle size distribution during test run.
-------
For VOCs and aldehydes/ketones, chamber air samples were collected then analyzed for
the target chemicals. As outlined in Table 3-10, a chamber air sample was collected prior to
placing the copier in the chamber. A second chamber air sample was collected after the copier
was placed in the chamber and was powered up but was not printing. This sample was collected
to provide data on the equilibrium chamber air concentration in the idle mode and was taken after
the copier had equilibrated in the chamber overnight. Finally, a third chamber air sample was
collected from the time the copier started printing until 2 hours (4 chamber air changes) after
printing was completed. This sample provided data on the average time-integrated chamber air
concentration over the test period. For the chamber used for this study, 4 air changes are
required to replace 99% of the air in since it is a single-pass system.
The emission rate (Er^ in the idle mode was calculated assuming steady-state conditions
after the copier had been idling in the chamber overnight.
ERi = [(Q - Cb) x Vc x AJ/n (3)
where,
ERj = emission rate in the idle mode in ng/h • copier
C; = chamber air concentration in the idle mode in ng/m3
Cb = background chamber air concentration in ng/m3
Vc = chamber volume in m3
Ac = chamber air exchange rate in h"1
n = number of copiers in chamber.
The emission rate of VOCs attributed to printing (ERJ was calculated using a simple mass
balance equation and applying the following assumptions:
1. There is no reversible or irreversible adsorption of the target organics in the chamber
during the testing period. This was demonstrated to be true through chamber recovery
tests.
2. The chamber air is well-mixed. This was demonstrated for each test through the release
and measurement of CO in the chamber air during testing.
3. The chemicals in the chamber are in the vapor phase and uniformly distributed in the
chamber air. This is a property of VOCs.
4. The steady state emissions measured in the idle mode remain constant during the copying
mode. Any changes are considered to result from copying, therefore by definition, a
change will be attributed to printing.
After 4 air changes, 99% of the chamber air was exhausted from the chamber. Since chamber air
samples were collected from the time the copier started until the time that 4 air changes had been
achieved after copying had stopped, 99% of the VOCs emitted during testing were exhausted
from the chamber during the sample collection period. Under these conditions:
ERc = M/ (Tp x n ) (4)
where,
ERC = emission rate attributed to printing in (ig/h • copier
M, = total net mass of VOC measured in the chamber air in [ig
T = time the copier was printing in h
3 -20
-------
Mt =(Cp -Q x Tw (5)
where
Cp = measures time-integrated chamber air concentration measured during the
chamber test in j^g/m3
C; = chamber air concentration measured during idle mode in fig/m3
Tav = total volume of air that passed through the chamber during testing in m3.
Here we have taken the approach that the concentration of VOCs in the chamber air attributed to
printing can be estimated by correcting the total concentration measured during the chamber
copying experiment by the concentration measured during the chamber idle experiment.
Tav = Vc x Ac x Tc (6)
where
Vc = chamber volume in m3
= chamber air exchange rate in h"1
Tc = time the sample was collected for in h.
Equations 4, 5, and 6 are then combined, resulting in the following equation:
ERc = [(Cp-Q x Vc x A, x Tc)] / (Tp x n) (7)
In two tests, chamber air samples for VOC analysis were also collected at shorter time
intervals (10 to 15 minutes) throughout the test period. Average emission rates for each time
interval were calculated using the chamber air concentration at that time interval as
ER, = (AQ /ATj + AcCt) x Vc / n (8)
where,
ER, = emission rate for time interval t in ng/h • copier
AC, = change in chamber air concentration for time interval t in (ag/m3
AT; = length of time interval T in hours
C, = average measured chamber air concentration for time interval t in ng/m3
For ozone, chamber air concentrations were measured over the test period using real time
instruments. Here, these chemicals emission rates were calculated as
ERq = [(Cc x \ x Vc)/(1 - e"AcTp)]/n (9)
where
ERj, = emission rate for ozone in [ig/h • copier
Cc = equilibrium chamber air concentration in ng/m3
3-21
-------
3.4.2 Precision of Emission Rate Measurements
Precision of the emission rate measurements in the idle and print modes was evaluated by
conducting triplicate large chamber tests on copier 1 using a single set of operating conditions.
Precision was evaluated as % RSD of the triplicate emission rate measurements. Precision data
for the replicate large chamber emissions tests are provided in Table 3-12 (VOCs) and Table 3-13
(aldehydes/ketones and ozone). Results are provided for the average emission rate measurements
and their %RSD for the triplicate tests in both the idle and the print modes. Results for the print
mode generally show excellent precision (RSD < 10% in many cases) for the emission rate
measurements. The exceptions were for those compounds where measured emission rates were
low (i.e., 2-butoxyethanol and H-decanal in the print mode, ethylbenzene and the xylenes in the
idle mode) or the background level for either the method blank or the chamber background
samples were relatively high (i.e., acetone and acetaldehyde) compared to the chamber air
concentrations measured during emission testing.
3.4.3 Between Copier Variability of Emission Rate Measurements
Large chamber emissions tests were conducted at RTI on four different dry-process
photocopiers. For each of these tests, estimated emission rates were calculated based on results
from integrated chamber air samples collected over the entire test period (as outlined in Table 3-
10). Results of these tests are given in Tables 3-14 to 3-20, and Figure 3-6 as follows.
Table 3-14 — VOCs during idle in |ig/h • copier,
Table 3-15 — VOCs during operation in jag/h • copier,
Table 3-16 — VOCs during operation in ng/page,
Table 3-17 — Aldehydes/ketones during idle in (ig/h • copier,
Table 3-18 -- Aldehydes/ketones during operation in jj.g/h • copier,
Table 3-19 — Aldehydes/ketones during operation in ng/page,
Table 3-20 -- Ozone during operation in ^g/h • copier., and
Figure 3-6 -- Continuous ozone concentrations in ppb.
Note that tables 3-16 and 3-19 report the results in ng/page, not ng/h-copier. Consequently,
emission rates that have low per copier values may have high per page values and vice versa,
depending on the copy feed rate or speed of the copier (see Table 3-11).
Overall results tend to show varied emission rates between the different copiers, although
most of the same chemicals were emitted from all four copiers. Tests were conducted over a 5-
month period, and the recovery tests during that period showed acceptable performance (Table 3-
8). Therefore, differences in measured emission rates should be considered to be a result of
differences between copiers and not a result of changing test performance.
3-22
-------
Table 3-12. VOC Emission Rate Precision Data for Triplicate Large Chamber Tests of
Copier l"1"
Idle Print
Chemical
Average
Emission Rate
(ng/h • copier)
% RSD
Average
Emission Rate
(|ig/h • copier)
% RSD
Toluene
C
—
760
14
n-Butyl Acetate
—
—
50
13
Ethylbenzene
180
38
27,000
6
m,p-Xy\ene
160
38
29,000
6
2-Heptanone
--
—
--
--
Styrene
44
23
9,900
4
o-Xylene
88
28
17,000
4
2-Butoxyethanol
--
—
67
141
Isopropyl benzene
—
—
400
3
Benzaldehyde
NTd
--
NT
—
a-Pinene
NT
--
NT
—
w-Propyl benzene
—
—
790
1
a-Methyl styrene
13
9
1,100
7
w-Decane
12
15
450
13
2-Ethyl-l-hexanol
33
15
230
11
Limonene
—
—
220
23
n-Nonanal
--
—
1,100
13
2,5-Dimethyl styrene
—
--
—
--
«-Undecane
36
10
2,000
8
«-Decanal
—
--
130
52
n-Dodecane
54
18
960
8
BHT
—
—
—
—
a Data generated for Copier 1, tests 2, 3, and 4. (See Table 3-11)
b Values are based on three runs
c Less than 10 (jg/h • copier
d NT = Not tested
3-23
-------
Table 3-13. Aldehyde/Ketone and Ozone Emission Rate Precision Data for Triplicate
Large Chamber Tests of Copier 1 a'b
Idle
Print
Chemical
Average
Emission Rate
(Hg/h • copier) % RSD
Average
Emission Rate
(|ig/h • copier)
% RSD
Formaldehyde
C
<500d
--
Acetaldehyde
140 36
710d
27
Acetone
—
2,000d
45
Acrolein
--
--
--
Propionaldehyde
--
~
--
Crotonaldehyde
--
—
—
2-Butanone
—
—
—
Methacrolein
--
—
—
Butyraldehyde
--
160
5.4
Benzaldehyde
--
1,800
11
Valeraldehyde
—
540
10
/w-Tolualdehyde
—
—
—
w-Hexanal
—
210
17
Ozone
NCC NC
3,000
7.1
a Data generated during Copier 1, Tests 2, 3, and 4 (see Table 3-11)
b Values are based on three runs
c Less than 10 jig/h • copier
d High background on cartridges or in chamber
e NC = Not calculated
3-24
-------
Table 3-14. Estimated VOC Emission Rates (fig/h • copier) Dry-Process Photocopiers—Idle
Chemical
Emission Rate (^g/hr
• copier)
Copier 1
Test 2-4
(average)
Copier 2
Test 7
Copier 3
Test 8
Copier 4
Test 9
Toluene
a
—
390
74
w-Butyl Acetate
—
140
--
—
Ethylbenzene
180
--
10
—
m,p-Xylene
160
48
--
23
2-Heptanone
—
460
--
—
Styrene
44
220
49
47
o-Xylene
88
--
—
14
2-Butoxyethanol
—
~
—
--
Isopropyl benzene
—
—
—
--
Benzaldehyde
NTb
NTb
—
--
a-Pinene
NTb
NTb
—
—
^-Propyl benzene
~
—
—
—
a-Methyl styrene
13
10
17
—
n-Decane
12
~
24
—
2-Ethyl-l-hexanol
33
150
82
—
Limonene
—
130
11
93
n-Nonanal
—
40
120
—
2,5-Dimethyl styrene
—
~
—
—
n-Undecane
36
~
49
—
w-Decanal
--
—
—
--
«-Dodecane
54
—
35
—
BHT
--
70
—
--
NT = Not tested
a Less than 10 ng/h • copier
3-25
-------
Table 3-15. Estimated VOC Emission Rates (jLig/h • copier) Dry-Process Photocopiers--
During Operation
Chemical
Emission Rate (ng/hr • copier)
Copier 1
Test 2-4
(average)
Copier 2
Test 7
Copier 3
Test 8
Copier 4
Test 9
Toluene
760
290
220
110
w-Butyl Acetate
50
110
a
--
Ethylbenzene
28,000
2,400
<50
360
w,/?-Xylene
29,000
6,100
100
510
2-Heptanone
—
—
—
--
Styrene
9,900
12,000
300
3,000
o-Xylene
17,000
4,500
—
850
2-Butoxyethanol
70
1,400
—
500
Isopropyl benzene
400
3,000
—
660
Benzaldehyde
NT
NT
—
6,200
a-Pinene
NT
NT
--
70
«-Propyl benzene
790
2,100
~
460
a-Methyl styrene
330
60
--
—
w-Decane
450
—
62
320
2-Ethyl-l-hexanol
230
14,000
130
5,600
Limonene
220
1,100
--
200
w-Nonanal
1,100
3,600
2,000
3,900
2,5-Dimethyl styrene
—
--
—
—
«-Undecane
2,000
70
103
62
w-Decanal
130
500
380
224
H-Dodecane
960
120
75
82
BHT
--
--
170
--
NT = Not tested
aLess than 50 (ag/h • copier.
3 -26
-------
Table 3-16. Estimated VOC Emission Rates (ng/page) Dry-Process Photocopiers—During
Operation
Emission Rate (ng/page)
Copier 1
Test 2-4
Copier 2
Copier 3
Copier 4
Chemical
(average)
Test 7
Test 8
Test 9
Toluene
240
58
73
34
tt-Butyl Acetate
a
20
--
—
Ethylbenzene
8,800
480
—
110
m,p-X ylene
9,100
1,200
30
158
2-Heptanone
--
--
--
~
Styrene
3,100
2,400
100
930
o-Xylene
5,300
890
—
260
2-Butoxyethanol
20
280
—
150
Isopropyl benzene
130
600
—
200
Benzaldehyde
NT
NT
"
1,900
a-Pinene
NT
NT
"
20
w-Propyl benzene
250
420
—
140
a-Methyl styrene
100
10
—
—
«-Decane
140
—
"
100
2-Ethyl-l-hexanol
70
2,800
43
1,700
Limonene
70
220
—
60
H-Nonanal
340
700
670
1,200
2,5-Dimethyl styrene
—
—
—
—
«-Undecane
630
15
34
20
n-Decanal
40
100
130
70
A?-Dodecane
300
25
25
25
BHT
—
—
57
—
NT = Not tested
a Less than 17 ng/page
3-27
-------
Table 3-17. Estimated Aldehyde/Ketone Emission Rates (jig/h • copier) Dry-Process
Photocopiers—Idle
Emission Rate (|ig/hr • copier)
Copier 1
Test 2-4
Copier 2 Copier 3
Copier 4
Chemical
(average)
Test 7 Test 8
Test 9
Formaldehyde
a
1,100
—
Acetaldehyde
140
—
—
Acetone
—
220 2,200
—
Acrolein
—
—
—
Propionaldehyde
—
—
--
Crotonaldehyde
—
—
—
2-Butanone
—
—
—
Methacrolein
—
—
--
Butyraldehyde
~
—
—
Benzaldehyde
--
—
—
Valeraldehyde
—
—
—
/w-Tolualdehyde
—
—
—
«-Hexanal
—
—
--
aLess than 100 ng/h • copier
3-28
-------
Table 3-18. Estimated Aldehyde/Ketone Emission Rates (jig/h • copier) Dry-Process
Photocopiers—During Operation
Chemical
Emission Rate (ng/h • copier)
Copier 1
Test 2-4
Copier 2
Test 7
Copier 3
Test 8
Copier 4
Test 9
Formaldehyde3
<500a
2600
2200
<500a
Acetaldehyde"
710
960
1200
<500a
Acetone
2000
<500
2800
b
Acrolein
--
~
—
—
Propionaldehyde
—
160
260
150
Crotonaldehyde
~
--
100
—
2-Butanone
—
380
190
210
Methacrolein
—
—
—
—
Butyraldehyde
160
840
--
--
Benzaldehyde
1800
2600
—
3800
Valeraldehyde
540
—
250
270
/w-Tolualdehyde
—
--
—
—
«-Hexanal
210
1200
440
100
a background contamination on cartridge and in chamber increased detection limit.
b less than 100 fig/hr • copier
3-29
-------
Table 3-19. Estimated Aldehyde/Ketone Emission Rates (ng/page) Dry-Process
Photocopiers—During Operation
Emission Rate (ng/page)
Copier 1
Copier 2
Copier 3
Copier 4
Chemical
Test 2-4
Test 7
Test 8
Test 9
Formaldehyde3
<150a
520
740
<150
Acetaldehyde3
220
700
390
<150
Acetone"
630
<500
940
b
Acrolein
--
—
--
—
Propionaldehyde
—
33
88
48
Crotonaldehyde
—
—
34
—
2-Butanone
—
76
63
66
Methacrolein
—
—
—
--
Butyraldehyde
54
170
—
—
Benzaldehyde
570
530
—
1,200
Valeraldehyde
170
—
82
83
w-Tolualdehyde
—
—
—
—
«-Hexanal
69
240
150
39
background contamination on cartridge and in chamber increased detection limit
bLess than 30 ng/page
Table 3-20. Estimated Ozone Emission Rates (ng/h • copier) Dry-Process Photocopiers—
During Operation
Emission Rate
Copier (Mg/hr • copier)
1 3,000
2 4,700
3 7,900
4 1,300
3-30
-------
00
90
80
70
60
50
40
30
20
10
0
3
.J
0 30 60 90 120 150 180
TiME (MIN)
Figure 3-6. Ozone results
copiers 1, 2, 3, and 4.
-------
The following observations can be made from the results:
• In most cases, emission rates of individual compounds in the idle mode were low
(<500 ng/h) as shown in Tables 3-14 and 3-17. Two exceptions were relatively high
measured emission rates for formaldehyde and acetone from copier 3 (Table 3-17).
Copier 3 was the only copier with a monocomponent toner. It is possible that
differences in toner type could be responsible for elevated emission rates for these two
chemicals in the idle mode.
• In almost all cases, higher emission rates of individual compounds were measured in
the print mode compared to the idle mode. This result suggests that the most
important impacts on IAQ will occur during printing; as a corollary, pollution
prevention strategies should focus on the print operation. Exceptions to this general
observation were measured emission rates for toluene from copier 3 (Tables 3-14, 3-
15); butyl acetate, 2-heptanone, and BHT from copier 2 (Tables 3-14, 3-15); and
acetone from copier 2 (Tables 3-17, 3-18). In all of these cases, the emission rates in
both the print and idle modes were relatively low. Two additional exceptions were
emission rates for formaldehyde and acetone from copier 3 as discussed above.
• As indicated by Table 3-15, three of the four copiers (1,2, and 4) showed relatively
high emission rates for styrene (3,000 to 12,000 (ag/h • copier). All three of these
copiers used dual-component toners, which contain styrene polymers as a base. On
the other hand, copier 3, which uses a monocomponent toner, showed a much lower
emission rate for styrene (300 ^g/h • copier).
• For the VOCs, Table 3-15 shows lowest emission rates were measured for copier 3
(the copier with the monocomponent toner). Copier 1 had the highest emission rates
for the aromatic hydrocarbons. Copier 2 also had high emission rates for several of
the aromatic hydrocarbons and for several polar VOCs, including 2-ethyl-l-hexanol
and H-nonanal. Copier 4 showed high emission rates for several polar VOCs,
including benzaldehyde, 2-ethyl-l-hexanol, and w-nonanal. It is hypothesized that
differences in emission rates for VOCs from different copiers may be due to
differences in the chemical composition of the toners.
• Generally, emission rates for the individual aldehydes/ketones in the print mode were
lower than for the individual VOCs (comparing Tables 3-15 and 3-18). However,
relatively high emission rates (>1000 jag/h • copier) were measured for formaldehyde
from copiers 2 and 3; acetaldehyde from copier 3; acetone from copiers 1 and 3;
benzaldehyde from copiers 1, 2, and 4; and «-hexanal from copier 2. Although the
paper supply could be considered a source for aldehydes/ketones, the same lot of
paper was used throughout testing; consequently, differences in emission rates
between copiers are probably not due to the paper supply. As for the VOCs,
differences in emission rates may be due to differences in toners.
3 - 32
-------
• Tables 3-16 and 3-19 show the emission rates per page for VOCs and
aldehydes/ketones, respectively. Generally, the trends for the emission rate per page
were similar to the emission rates per copier per hour for the individual compounds.
Exceptions to this trend include styrene (copier 1 had highest per page emissions;
copier 2 had highest per hour emission rates), formaldehyde (copier 3 had highest per
page emissions; copier 2 had highest per hour emission rates), and acetaldehyde
(copier 2 had highest per page emissions; copier 3 had highest per hour emission
rates).
• For ozone, as indicated in Table 3-20, substantial differences in emission rates were
seen between the four copiers, ranging from a low of 1,300 |ig/h • copier for copier 4
to 7,900 ng/h • copier for copier 3. It should be noted that copier 4 is advertised as a
low ozone emitting copier. Results confirm that this machine resulted in lower ozone
emissions during copier operation than the other three copiers.
• As indicated previously, limited particulate data were collected for two of the four
machines tested. Preliminary results showed that operation of Copier 1 increased
particle levels to approximately 30 times chamber background levels for particles
smaller than 0.2 //m in diameter.
3.4.4 Within Copier Variability of Emission Rate Measurements
Multiple large chamber emission tests (Tests 1 through 6, Table 3-11) were conducted on
copier 1 in order to determine within-copier variability over a number of runs. VOC emission
rates for these tests are presented in Tables 3-21 and 3-22 for the print and idle modes,
respectively. As shown in Table 3-11, the tests were conducted at two different times and used
several different toner lots. Tests 1, 2, 3, and 4 were conducted during an initial 8-day period.
Tests 5 and 6 were conducted approximately 4 months later. Test 1 utilized a toner cartridge that
was shipped with the copier and had only enough toner to complete 999 copies before it was
empty. A new toner cartridge was installed for Tests 2, 3, and 4. Tests 5 and 6 used the same
toner cartridge as Tests 2, 3, and 4; however Tests 5 and 6 were conducted 4 months after
installing the toner cartridge. No special storage precautions were taken during this time period -
the toner was left in the copier and the copier stored at room temperature during the 4-month
period. Since the tests were conducted and samples analyzed during two time periods
approximately 4 months apart, a duplicate multisobent cartridge that had been collected during
Test 4 and stored in a freezer was analyzed with the second set of samples to verify that the
analytical system was performing consistently. These results are also shown in Table 3-21. (Note
that previous experience at RTI has shown that control samples on multisorbent tubes yield
consistent results after as much as 1 year in the freezer.) Just prior to performing Test 6, all
photocopier particle and charcoal filters were replaced by the manufacturer's service technician.
3-33
-------
Table 3-21. Comparison of Intra-Machine (Copier 1) Variability in Emissions
(jLig/h • copier) During Replicate Runs—During Operation
Emission Rate (|ig/h • copier)
New Toner
Old Toner
Chemical
Test 2-4
Mean
Test 2-4
% RSD
Test 4
Test 1
Test 5
Test 6
Test Date
Analysis Date
4/95
4/95
4/95
9/95
4/95
9/95
9/95
9/95
9/95
9/95
Toluene
760
14
560
600
760
26,000
Butyl Acetate
50
13
-
-
-
Ethylbenzene
27,000
6
31,000
18,000
18,000
21,000
m,p-X ylene
29,000
6
33,000
20,000
19,000
21,000
2-Heptanone
-
-
-
-
-
-
Styrene
9,000
4
9,900
6,600
5,500
6,300
o-Xylene
17,000
4
18,000
13,000
10,000
12,000
2-Butoxyethanol
67
141
-
-
-
-
Isoproply benzene
400
3
410
270
220
240
Benzaldehyde
NTb
-
2,500
1,500
1,200
1,400
a-Pinene
NT
-
81
91
-
-
Propyl benzene
790
1
740
590
400
440
a-Methyl styrene
1,100
7
1,100
1,300
600
650
«-Decane
450
1
300
480
94
-
2-Ethyl-1 -hexanol
230
11
90
98
110
52
Limonene
220
23
250
280
74
-
w-Nonanal
1,100
13
3,000
1,300
770
1,400
2,5-Dimethly
styrene
-
-
-
-
-
-
n-Undecane
2,000
8
1,900
1,900
530
-
/j-Decanal
130
52
100
-
-
-
rt-Dodecane
960
8
870
950
260
77
BHT
-
-
-
-
-
-
" Less than 50 (ig/h • copier
b Not Tested
Test 1: toner had run out (old toner) during test run.
Test 2-4: toner cartridge replaced and triplicate runs made, average of these three runs and %RSD presented.
Test 4: original test 4 run in 4/95, duplicate sample was analyzed in 9/95 to evaluate analytical differences between runs.
Test 5: same toner cartridge used in test 2-4 (timc-scries test also run).
Test 6: same toner cartridge used in test 2-4 all filters replaced.
3-34
-------
Table 3-22. Comparison of Intra Machine (Copier 1) Variability in Emissions
(jig/h • copier) During Replicate Runs—Idle
Emission Rate (ng/h • copier)
New Toner
Old Toner
Chemical
Test 2-4
Test 2-4
Test 5
Test 6
Mean
% RSD
Old filters
New Filters
Test Date 4/95
Toluene
a
-
-
180
Butyl Acetate
-
-
-
-
Ethylbenzene
180
38
34
120
7M,/>-Xylene
160
38
30
120
2-Heptanone
-
-
-
-
Styrenc
44
23
13
-
o-Xylene
88
28
18
-
2-Butoxyethanol
-
-
12
-
Isoproply benzene
-
-
-
Benzaldehyde
NTb
-
-
-
a-Pinene
NT
-
-
-
Propyl benzene
-
-
-
-
a-Methyl styrene
13
9
-
-
M-Decane
12
15
-
-
2-Ethyl-l-hexanol
33
15
-
-
Limonene
-
-
-
12
w-Nonanal
-
-
-
39
2,5-Dimethly styrene
-
-
-
-
M-Undecane
36
10
-
13
w-Dccanal
-
-
-
-
n-Dodccane
54
18
-
-
BHT
-
-
-
-
"Less than 50 ng/h • copier
bNot tested
Test 1: toner had run out (old toner) during test run.
Test 2-4: toner cartridge replaced and triplicate runs made, average of these three runs and RSI).
Test 5: same toner cartridge used in test 2-4 (time-series test run).
Test 6: same toner cartridge used in test 2-4 all filters replaced.
3-35
-------
As seen in Table 3-21, a comparison of results for the tests conducted when the toner
cartridge was "new" (Tests 2-4) compared to tests conducted with the "old toner" 4 months
later (Tests 5 and 6) showed consistently higher emission rates associated with the "new" toner.
For the aromatic hydrocarbons such as ethylbenzene, m-,p~, and o-xylenes, and styrene, the
emission rates with "new" toner were approximately 50% higher than the emission rates with the
"old toner." The same trend was also seen with benzaldehyde. For the other VOCs (most of
which had low emission rates), no noticeable trend was observed. The multisobent cartridge
collected and frozen during Test 4 and later analyzed during the second round showed results
comparable to those measured during the first analysis. This indicates that the differences
between the tests are real and not due to analytical response. For Tests 2, 3, and 4, conducted
during the same time period and with the same "new" toner, the results are very consistent, as
shown by the generally low %RSD values. This indicates that the photocopier test results are
reproducible if the proper variables are controlled. These results indicate that offgassing of the
toner during storage can impact the emissions.
Replacement of the filters (Test 6 compared to Test 5) seemed to have little effect on the
emissions with the exception of toluene. Toluene substantially increased after the change out of
the filters. This may be due to adhesives used to hold the filters in place. Most of the filters have
a peel and apply backing to attach the filters to the copier. This may also be the reason for the
presence of toluene during the idle period for Test 6 (Table 3-22).
3.4.5 Emission Rates as a Function of Copier Operation Time
During the chamber emissions tests with copiers 1 and 4 (Test 5 and 9, Table 3-11),
chamber air samples for VOC determinations were collected at short-time intervals throughout
the test period to evaluate the change in emission rate over time. For these tests, samples were
collected at T = 0-10, 10-20, 20-30, 30-45, 45-60, 60-75, 75-90, 90-105, 105-120, and 120-160
minutes after the copier started printing. A time-integrated sample over the entire test period (T =
0-160 minutes) was also collected for comparison.
Chamber air concentration measured during these tests are shown in Figures 3-7 to 3-14
as follows for selected compounds:
Figure 3-7 -
Figure 3-8 -
Figure 3-9 --
Figure 3-10 •
Figure 3-11
Figure 3-12 -
Figure 3-13
Figure 3-14 •
Copier 1
Copier 1
Copier 1
- Copier 1
- Copier 4
- Copier 4
- Copier 4
- Copier 4
Styrene
m,p-X ylene
o-Xylene
Ethylbenzene
Styrene
Benzaldehyde
2-Ethyl-l-hexanol
o-Xylene.
3 - 36
-------
120
110
100
90
80
70
60
50
40
30
20
10
0
¦—©- -
Measured
Calculated, R(i)=5456
Calculated, R(a)=6195
N'
2.5
Time (hours)
Figure 3-7. Copier 1
styrene concentrations.
-------
400
V
0 s&
0
0.5
Measured
~
Calculated, R(i)=18794
Calculated, R(a)=22038
o
1 1.5
Time (hours)
2
2.5
Figure 3-8. Copier 1
,p-xylene concentrations.
-------
250
200
VO
CO
£
15)
ZJ
c
o
-»—»
03
150
c
0
o
c
o
O
100
50
0
—e-~
Measured
Calculated, R(i)=10210
Calculated, R(a)=11963
1 1.5
Time (hours)
2.5
Figure 3-9. Copier 1
o-xylene concentrations.
-------
/
—©—
Measured
—E3-—
Calculated, R(i)=18093
Calculated, R(a)=21930
0.5
1 1.5
Time (hours)
Copier 3-10. Copier 1
ethylbenzene concentrations.
-------
60
50
-------
120
100 -
NJ
£ 80
13)
ZJ
I 60
ro
c
0
o
c
o
O
40
20
. /
. /
0 d ;-
0
0.5
—e—
Measured
Calculated, R(i)=6223
Calculated, R(a)=4864
1 1.5
Time (hours)
2.5
Figure 3-12. Copier 4
benzaldehyde concentrations.
-------
100
Measured
Calculated, R(i)=5600
Calculated, R(a)=4995
0
0
0.5
1 1.5
Time (hours)
Figure 3-13. Copier 4
2-ethyl-l-hexanol concentrations.
i
i
m 1
2.5
-------
14
12
CO
10
CD
=5
C
o
03
-4—'
c
d)
o
c
o
O
8
0
Measured
—5=3
Calculated, R(i)=845
Calculated, R(a)=786
1 1.5 2
Time (hours)
Figure 3-14. Copier 4
-xylene concentrations.
-------
In each figure, the average measured chamber air concentration is plotted for each time
period at the midpoint for that time period, e.g., the concentration for T=10-20 minutes (0.17-
0.33 hours) is plotted at the T=15 minutes (0.25 hours) point. For comparison, the theoretical
concentrations at the same time point calculated using the emission rate generated for the time-
integrated sample (R(I)) and the average emission rate generated for the time-point samples
(R(a)) are also given. The area under the curve for the measured concentrations and the
concentrations calculated using R(a) should be equal.
For copier 4, plots for all four VOCs (Figures 3-11 to 3-14) show good agreement between
the measured concentrations and the theoretical concentrations. Differences between the
measured and the theoretical concentrations are usually less than 10 percent, well within the
expected precision of the analytical methods. These results suggest that emission rates are
constant over time while the copier is printing and that emissions drop to zero or close to zero
once printing is stopped. Results for copier 1 show a different trend, although the data are
consistent for the four VOCs shown. Data for copier 1 shows lower measured concentrations
compared to the theoretical concentration during the first two time periods. Higher
concentrations than theoretical are measured during the later time periods. The lower-than-
expected concentration at the start of the test suggests that emission rates are not constant over
time; essentially the emission rates at the start of printing are lower and then increase with time.
The higher than expected concentrations after printing has stopped suggest that the copier is
still emitting VOCs after the printing has stopped. The same trend of higher-than-expected
chamber air concentrations after copying stops would be seen if VOCs were reversibly absorbed
to the chamber surfaces; however, plots of VOC concentration over time for the recovery tests
(Figures 3-1 and 3-2) indicate that this is not occurring.
To further evaluate the data, emission rates were calculated for selected VOCs for each time
period. These data are given in Table 3-23 for copier 1 and in Table 3-24 for copier 4. These
data are displayed graphically for styrene in Figure 3-15 and for ethylbenzene in
Figure 3-16. These data for emission rates show the same trends as described above for chamber
air concentrations. For copier 4, the emission rates are fairly constant during the period when
copies are being made, then drop substantially when copying stops.
For copier 1, on the other hand, the emission rates at the first time point (0-10 min) were
substantially lower than for the other time points when the copier is operating. It should be noted
that only a single sample was collected and analyzed at this time point; thus, this difference could
be due to analytical variability. However, the differences in emission rates for this time point
compared to the other time points is greater than what would be considered normal analytical
variability. These results suggest that, for copier 1, emission rates are not constant over time but
increase with time after copying starts. Data for copier 1 also show that VOCs are still emitting
after copying stops. This is most apparent for the first time point (T = 52.5 min) after the copier
is turned off.
3-45
-------
Table 3-23. Estimated Emission Rates as a Function of Time - Copier 1
Emission Rate (ng/h • copier)
Copier on
Copier off
Chemical
Time (min)
Integrated 90- 105- 120-
0-10 10-20 20-30 30-45 Sample 40-60 60-75 75-90 105 120 160
Toluene
Ethylbenzene
w,/7-Xylene
o-Xylene
Styrene
2-Ethyl-l-hcxanol
Isopropyl benczene
Benzaldehyde
a-Pinene
Limonene
Propylbenzene
480 350 370 260
440
56
18 30
11
31
-10
9000 18000 22000 19000 22000 4900 730 1600 1100 1600 480
9000 18000 22000 20000 22000 4900 730 1600 1100 1600 480
5200 10000 13000 11000 12000 2300 120 720 390 720 230
2500 5100 6200 5500 6200 1400 240 460 330 480 180
42
27
100 120
43
75
48
110 220 280 240
600 1500 1600
16
16
120 46
210 400 500 430
100
240
780
53
48
450
53
44
13
12
12
20 340 190 68
16
74
16
0.2
11
16
18
25
16
15
10
12
32
9
0
27
3
I
120
II
0
3-46
-------
120-
160
22
10
4.0
11
43
10
12
170
34
30
5
Table 3-24. Estimated Emission Rates as a Function of Time - Copier 4
Emission Rate (ng/h • copier)
Copier on Copier off
90- 105-
0-10 10-20 20-30 Integrated 45-60 60-75 75-90 105 120
150 36 46 130 60 42 24 38 34
240 280 290 340 26 33 35 23 27
360 430 430 470 22 39 24 22 39
680 770 700 790 17 42 33 33 46
2500 2900 2600 2900 18 77 99 100 160
5500 5700 5100 5000 620 170 5 46 150
540 600 530 610 4 28 23 30 43
4500 6600 5800 4900 960 400 320 230 8
170 5 18 66 75 25 16 12 11
47 56 140 139 40 28 14 2 15
400 440 410 430 9 14 12 14 23
3-47
-------
Emission Rates
Copier '1' - Styrene
7000
£ 5000 i
V 4000 +-
2 3000 --
Time (h)
Emission Rates
Copier '4' - Styrene
3000
2500 --
E 1500 --
1000 --
500 --
-Br
0 0.2 0.4 O.C 0.8 1 1.2 1.4 1.8 1.8 2 2.2 2.4
Tim« (h)
Figure 3-15. Plots of emission rate vs. time for styrene.
(Verticle line indicates copying stopped)
3-48
-------
Emission Rates
Copier '1' - Ethylbenzene
25000
20000 -
15000 -t-
s 10000 -
5000 -L
0 0.2 0.4 0.6 0.8 1 12 1 4 1.6 1 8 2 22 24
Tim« (h)
Emission Rates
Copier '4' - Ethylbenzene
300
250
S 150
100 -l-
50 --
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 12 2.4
Time (h)
Figure 16. Plots of emission rate vs. time for ethylbenzene.
(Verticle line indicates copying stopped)
3 -49
-------
3.4.6
Practical Aspects of Test Implementation
Throughout the course of Phase I, several issues arose concerning the practical aspects for
conducting the large chamber emissions tests for photocopiers. A listing of these issues and their
resolution during this study are given in Table 3-25.
3.4.6.1 Toner Aging/Head space Analysis
In addition to the issues listed on Table 3-25, another issue related to toner lot and age and
the effect on emissions was identified. Specifically, variability of data was observed for a single
copier tested multiple times under the same chamber conditions during Phase I. This occurred
both during a changeover to a new toner lot and when extended periods of time (1-3 months) had
elapsed between tests using the same toner lot. It was necessary to resolve this issue before any
round-robin testing could be conducted for Phase II. To do this, different toner lots were
evaluated both by chamber testing and by a headspace analysis method. Headspace tests were
conducted on samples from six different toner lots, but all manufactured by the same company for
use with Copier 1, defined as follows:
Toner 1— old toner from previous copier 1 runs (Lot 1-2),
Toner 2— new toner cartridge for copier 1 (Lot 1-4),
Toner 3— new toner cartridge for copier 1 (Lot 1-3),
Toner 4— new toner cartridge for copier 1 (Lot 1-5, A & B),
Toner 5— new toner cartridge for copier 1 (Lot 1-7, A), and
Toner 6— old toner sampled from existing RTI copier; age unknown, (Lot 1-8).
For each test, 50 mg of toner was placed in a 28.3 mL container and allowed to equilibrate for 1.5
hours at which time a 1 mL headspace gas sample was withdrawn using a gas-tight syringe. An
injection was made into a flash evaporation system and purged onto a multisorbent cartridge.
The multisorbent cartridge was analyzed by GC-Flame Ionization Detector (FID). Tests were
conducted at 100 °C for all toner samples (the bottom of the fusing temperature range for all the
copiers tested) and at 35 °C and 200 °C for some of the samples. In all tests, the four major
peaks from the chamber tests (ethylbenzene; m-,p-\ylene; oxylene; and styrene) were quantified.
As a check on the analysis, duplicate samples were taken from one toner cartridge (toner 5, Lot 1-
7A) and single samples were taken from two separate cartridges from the same lot (toner 4, Lot
1-5A and 1-5B). The results from these tests are presented in Table 3-26. As can be seen from
the data:
• increased temperature resulted in increased equilibrium headspace concentrations;
3-50
-------
Table 3-25. Practical Considerations for Copier Testing Issues and Resolutions
Issue
Resolution
Maintaining Chamber Temperature
• Increased Acceptable Test Range
with Added Head Load
Increased Allowed Air Exchange Rate
• Decreased Supply Air Temperature
Remote Operation of Copier
- Hardware Issues (start/Stop,
Removed Keyboard or Jumpered Start Switch and
Reset Switches)
extended cables to allow operation outside Chamber
- Software Issues
• Reprogrammed Features
• Paper Capacity
- Infeed
• Required High Capacity Paper Tray
- Outfeed
Outfeed Trays were Inadequate so a "Catch
Basket" was used
Power Requirements
Capability of 110V and 220V necessary
• Humidity
• Supplied Humidity at Mass Equivalent
to 23 °C, 50%RH
3-51
-------
• large differences were observed between the headspace concentrations of different toner
lots having the same manufacturer's specifications;
• the ratio of the headspace concentration results of toner 1 (old toner) to toner 2 (new
toner) is similar to the ratio of copier emissions data for runs (using old toner) to runs
using new toner (See Table 3-21).
3.4.6.2 Toner Carryover
Following the headspace tests, additional chamber tests were run sequentially using the same
copier but different lots of toner. It became apparent that the residual toner in the toner delivery
system of the copier needed to be depleted and replenished with fresh toner when changing
cartridges or when a period of a week or so elapsed between tests using the same lot. Without
the depletion/replenishment, toner from a new cartridge would be diluted by the residual toner in
the delivery system. A procedure for performing this depletion/replenishment was developed for
the round-robin testing and was included in the Emission Testing Guidance Document for Dry-
process Photocopiers (Appendix B). It should be noted that the specific method for toner
depletion/replenishment is dependent on the particular copier being tested, and therefore each
copier must be evaluated individually.
3.4.6.3 Vent Gas Sampling
Because the large chamber emissions measurement method developed during this cooperative
agreement requires specialized facilities and is relatively expensive to perform, preliminary
investigations were conducted to evaluate an option for rapid-screening of copier organic
emissions: copier vent gas analysis. Preliminary results from the vent gas sampling and analysis
appeared to indicate that a correlation existed between the vent gas concentrations and the
chamber data for the one copier that was evaluated. However, because each copier is designed
differently, with a different number of vents and different vent flow rates, a single screening
method that could be used for all copiers is highly unlikely.
3-52
-------
Table 3-26. Results of Toner Headspace Experiments
Concentration in Headspace (ng/mL)
ethyl-benzene
m, p-xylene
o-xylene
styrene
Tests at 100°C
Toner 1 (Lot 1-2)
490
510
250
64
Toner 2 (Lot 1-4)
710
770
350
79
Toner 3 (Lot 1-3)
960
960
450
110
Toner 4A (Lot 1-5 A)
150
430
140
23
Toner 4B (Lot 1-5B)
130
410
140
21
Toner 5A (Lot 1-7A)
120
380
120
18
Toner 5B, duplicate
(Lot 1-7 A)
120
400
120
18
Toner 6 (Lot 1-8)
450
510
230
120
Tests at 200 °C
Toner 1 (Lot 1-2)
720
950
460
190
Toner 2 (Lot 1-4)
1100
1300
670
240
Tests at 35°C
Toner 2 (Lot 1-4)
94
110
60
N/A
Toner 2, duplicate
(Lot 1-4)
110
130
60
N/A
NA = not available
3 - 53
-------
4.0
PHASE II: ROUND-ROBIN EVALUATION AND RESULTS
The primary goal of Phase II testing was to evaluate the method outlined in the guidance
document (Appendix B) for measuring emissions of VOCs, aldehydes/ketones, and ozone from
dry-process photocopiers. The usefulness of the method was determined by comparing the results
from four laboratories in a round-robin test. The following major activities were part of the
Phase II testing:
• conducted round-robin testing using the same photocopier (copier 1) under
identical conditions at four test laboratories using procedures developed and
revised in Phase I;
• reviewed data from the round-robin testing to determine if the data were
comparable between laboratories and if the method is useful for accomplishing the
objectives; and
• summarized and reported on emissions results from all laboratories.
The following sections summarize the materials and procedures followed for the round-
robin testing.
4.1 Materials and Methods
Four U.S. laboratories participated in the round-robin tests. To minimize the variability
due to the copier, a single photocopier, whose emissions had already been measured at RTI, was
sent to the other three laboratories for the round-robin testing program and returned to RTI for a
final test. The copier was transported via a commercial office products shipping firm to all
locations. Upon arrival at each location, a field technician representing the manufacturer
inspected, set up, and tested the copier to ensure that it was performing properly.
A representative from RTI traveled to each of the test facilities to perform a release of
standard emissions sources in the participating test chambers to evaluate performance. A single
lot of toner and a single lot of copier paper were used by all participating laboratories in the
round-robin copier test. The same standard test pattern image (representing 15% coverage) was
used for all tests (Appendix B, pages B-17 and B-18). The RTI representative also helped with
the toner depletion/replenishment and remote start aspects of the copier tests as discussed in
Section 3.3.6.2 and Appendix B. Personnel at each chamber facility were responsible for the
chamber operation and sample collection. Each laboratory was responsible for providing sample
cartridges for samples to be analyzed at the laboratory; however, RTI provided sample cartridges
for replicate samples to be analyzed at RTI. Specific instructions were provided to participating
laboratories when necessary to explain collection of toner samples and VOC and
aldehydes/ketones sampling. The RTI representative observed at least one copier test at each
facility to promote consistency between laboratories. Descriptions of the participating laboratories'
test chambers are provided in Table 4-1. Particle measurements were attempted by three of the labs
using gravimetric and/or particle counters; however, results were inconclusive.
4- 1
-------
A total of seven separate emission tests were conducted at the four participating facilities.
(At one facility, the copier was tested three times to evaluate the precision at a facility other than
RTI.) For each test, concentrations of VOCs, aldehydes/ketones, and ozone were measured in
the chamber air. For each test, the same sequence of operations was performed:
Step 1. Service representative checked copier and assisted in setting up remote start
capability;
Step 2. Toner depletion/replenishment was conducted on copier;
Step 3. Background air samples collected from empty chamber;
Step 4. Copier placed in chamber;
Step 5. Copier powered up, paper loaded in copier, remote start tested, and
equilibrated overnight;
Step 6. Chamber air samples collected during copier idle period;
Step 7. Chamber air samples collected during full copier operation
(1,998 copies, -38 minute operation time, total sample collection time of- 158
minutes) and
samples collected for 4 air changes after copy process ends; and
Step 8. Air exchange rate accurately determined through CO or other method during test.
Table 4-1. Descriptions of Test Chambers Used in Round-robin Testing
Lab
Chamber Dim.
(m x m x m)
Chamber Vol.
(m3)
Construction
Materials
Air System
Air Exchange
Rate (h"')
Lab 1
3 x 3 x 2.5
22.7
aluminum walls, stainless
steel floor, viton door seals
single pass
1.88
Lab 2
5.1x2.15x2.34
25.7
aluminum walls, stainless and
galvanized steel floor
single pass
1.75
Lab 3
4.7x3x2.3
35.4
Marlite walls, ceiling, and
vinyl floors
recirc.
0.904
Lab 4
4 x 2.8 x 2.6
29.1
stainless steel
single pass
1.62
4.1.1 Chamber Dosing and Recovery Experiments
Chamber dosing and recoveries were determined by introducing selected VOCs,
formaldehyde, and ozone into the chamber at known rates (See Table 3-7). Chamber air samples
were collected and analyzed for pollutant concentrations using procedures identical to those used
during the Phase I emission tests with photocopiers. Percent recovery of the emitted pollutant
was used to evaluate the accuracy of the emission test method and to ensure consistency between
the different test chambers.
4-2
-------
4.1.2 Chamber Air Samples During Emissions Tests
The chamber designs allowed for continuous operation of the copier being tested and
sampling of chamber air without opening the chamber during the test. Sampling points for the
chamber air had to be representative of the chamber concentrations. A duplicate set of VOC and
aldehyde samples were collected for analysis at RTI by the participating laboratory using
cartridges and pumps supplied by RTI.
Methods used for collection and analysis of VOCs included various multisorbent tubes and
Tenax cartridges. Each participating laboratory was allowed to use either type method as long as
adequate performance could be demonstrated. For each method, the sample volumes collected
for analysis and sampling time were determined by the flow rate and analytical sensitivity required.
Although other methods could have been used, all laboratories used the silica gel/2,4-
DNPH method for monitoring formaldehyde and other low molecular weight aldehydes/ketones
(Winberry, 1988). Using this method, aldehydes/ketones were collected by passing chamber air
through cartridges containing silica gel impregnated with DNPH. Formaldehyde, as well as other
aldehydes and ketones, react with the DNPH and are collected on the cartridge material. With the
DNPH method, care had to be taken to address the potential interference of ozone. Potassium
iodide-coated denuders or commercially available potassium iodide scrubbers were placed
upstream of the DNPH cartridge to remove ozone.
For VOCs and aldehydes/ketones, chamber air samples were collected and analyzed for
the target chemicals. As outlined in the steps listed above, a chamber air sample was collected
prior to placing the copier in the chamber. A second chamber air sample was collected after the
copier was placed in the chamber, powered up (but not printing), and equilibrated overnight in the
chamber. This sample provided data on the equilibrium chamber air concentration in the idle
mode. Finally, a third chamber air sample was collected from the time the copier started printing
until 4 chamber air changes after printing was completed (approximately 2 hours). This sample
provided data on the average time-integrated chamber air concentration over the test period.
Each laboratory stored collected samples in a manner consistent with their usual handling
practices. For RTI, this consisted of storing the VOC cartridges in sealed glass tubes inside
friction-sealed steel cans in a freezer maintained at -10 °C. The DNPH cartridges were stored in
sealed polypropylene jars supplied by the manufacturer in a refrigerator maintained at 4 °C.
These storage methods were recommended to the other participating laboratories.
For the two laboratories performing particle mass measurements (Laboratories 2 and 3),
chamber air was passed through a particle size selective device (impactor) at a constant and
specified flow rate. Particles less than 10 were collected on a preweighed filter. The mass of
the collected particles was determined gravimetrically using an analytical balance. At the third lab
(Laboratory 4), measurements using a real time particle counter were attempted.
4-3
-------
4.1.3 Toner Samples for Headspace Analysis
Toner samples of 50 mg from each toner cartridge used were collected by the testing
laboratory and sent to RTI for headspace analysis. These samples were collected so that the
chemical consistency of the different toner cartridges from the same lot could be compared. The
toner samples were collected by the participating laboratory immediately following each copier
emission test. RTI provided a sampling kit complete with detailed sampling instructions to each
laboratory prior to testing. Headspace analysis procedures were the same as those used during
Phase I testing (see Section 3.4.6.1) except that the temperature during Phase II testing was
150°C.
4.2 Results
In general, the results (calculated using the equations presented in Section 3) show good
accuracy and precision for the round-robin chamber tests. The results demonstrate that the
method can be used successfully by other laboratories to measure VOCs, ozone, and
aldehydes/ketones from dry-process photocopiers. Particle measurements provided poor data for
these purposes and results are inconclusive.
4.2.1 Chamber Dosing and Recovery Experiments
Results of the VOC, aldehyde, and ozone recovery tests are summarized in Table 4-2.
These emission rate values are the result of the release of the standard emission sources. The
emission rates measured during the release at each laboratory, the theoretical emission rates, and
the calculated percent recoveries of the sources are presented. These recovery tests were
conducted using the same chamber conditions as when the copier was tested. General recoveries
for toluene and n-decane are very good for Laboratories 1, 2, and 4. Likewise, recoveries for
formaldehyde for Laboratories 1 and 4 are also greater than 90%. Results from the recovery tests
confirmed the bias observed at Lab 3 and are discussed in Section 4.2.2. The reason for the low
recovery of formaldehyde at laboratory 2 is unknown. However, it may be due to the
complicated system required for formaldehyde delivery at this location or, there could have been
an unobserved (due to the fact that one could not see into this chamber) malfunction of the
system. Ozone recoveries vary from 25 to 86%.
Due to the limited time schedule at each test facility, time was not allotted for each
laboratory to analyze recovery data and optimize recovery conditions or take corrective action
before testing the copier. Each laboratory was expected to have already performed basic recovery
evaluations prior to this study. Also, part of this study was to evaluate the effects of different
chambers relative to the test method. The recovery data were used to evaluate the copier results
after each laboratory's data were reported. Once reported to RTI, data were reviewed at RTI for
calculation errors and analytical bias. Participating labs were notified of problems and allowed
to make justified corrections before the data were included in this report.
4-4
-------
Table 4-2. Chamber Recoveries Based on Standard Emission Sources (fig/hour • copier)
Lab 1
Lab 2
Lab 3
Lab 4
Chemical
Theoretical
Measured
1 % Recovery
Measured
% Recovery
Measured
% Recovery
Measured
% Recovery
Samples Analyzed
at Each Laboratory
Toluene
12000
13000
108
14000
117
17000
142
10000
83
Decane
14000
14000
100
a
-
20000
143
13000
93
Formaldehyde
6400
6000
94
3700
58
23000
359
6900
108
Ozone
8800
5500
62
4800
55
2200
25
7600
86
Samples Analyzed
atRTI
Toluene
12000
13000
108
15000
125
_ b
-
15000
125
Dccane
14000
14000
100
a
-
_ b
-
15000
107
Formaldehyde
6400
6000
94
2600
41
5400
84
7000
109
a Decanc not included in standard released at laboratory 2.
b Data not reported due to low internal standard area counts in sample.
-------
4.2.2 Emission Rates
The results of the VOC emission rate measurements generated by each round-robin
laboratory during copier operation are shown in Table 4-3. Samples collected during copier idle
period were only reported by two of the four laboratories. RTI's idle data were similar to those
obtained during Phase I testing (see Table 3-12). For all of the tests while the copier was
operating, the compounds with the highest emission rates were ethylbenzene, m, /^-xylene, o-
xylene, and styrene. Results show very good general agreement between laboratories for most
compounds. The precision between laboratories 1, 2, and 4 (tests 1 and 3 only since test 2 was
incomplete) was excellent with relative standard deviations (RSDs) of 5.0% for ethylbenzene,
4.0% for m, p-xylene, 14.6% for o-xylene, 7.6% for total xylenes, and 3.7% for styrene. (RSD
was calculated only for the four chemicals with emissions greater than 1000 ng/h.) These results
compare favorably with a previous 20-laboratory round-robin study done with small chambers
where RSDs of interlaboratory comparisons ranged from 26 to 42% for a polyvinyl chloride
(PVC) flooring material (Colombo et al., 1993).
As discussed below, results of the duplicate analysis suggest that the higher emission rates
observed for laboratory 3 are due to a laboratory measurement bias. If the results from laboratory
3 are included in the calculation of precision, RSDs increase to 17.5 % for ethylbenzene, 16.9%
for total xylenes, and 20.6% for styrene. However, if the RSDs are calculated instead, using the
duplicate samples for laboratory 3 that were analyzed at RTI, the RSDs are considerably better:
6.9% for ethylbenzene, 8.2% for total xylenes, and 4.1% for styrene.
The results for the Phase I testing at RTI are also shown in Table 4-3 for a general
comparison between Phases I and II. The results obtained from Phase II are comparable with the
Phase I results; however, note that different toner lots were used and some changes were made to
the test method for the Phase II testing (e.g., toner depletion and replenishment) so a rigorous
comparison between the two Phases is not appropriate.
Results of the duplicate samples collected in the individual laboratories and analyzed by
RTI are shown in Table 4-4. When laboratory 3 conducted its own analysis (Table 4-3), the
emission rates tended to be at least 30% higher than those reported by the other laboratories.
However, when RTI conducted the analysis for duplicate chamber air samples (Table 4-4),
emission rate data for laboratory 3 were in agreement with results from the other laboratories
(with the exception of toluene which was higher). The results of this duplicate analysis suggest
that higher emission rates observed for laboratory 3 in Table 4-3 are due to measurement bias in
the analysis at laboratory 3 rather than chamber performance.
Aldehyde/ketone and ozone results for the samples collected and analyzed at each facility
are shown in Table 4-5. Laboratory 3 had a high positive bias for formaldehyde as was seen in
the VOC analysis. For the data reported, measurements among the four laboratories were
generally more variable for the aldehydes/ketones than for the VOCs. For formaldehyde, the
precision among laboratories 1, 2, and 4 was fairly good with an RSD of 20.0%. Ozone emission
4-6
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Table 4-3. Emission Rates Measured During Copier Operation — Selected VOCs (fig/hour • copier)
Phase II Phase I
Lab 1 Lab 2 Lab 3 Lab 4a RTI
Chemical Test 1 Test 2b Test 3
Toluene
440
1100
NRd
370
BDL'
350
760
Ethylbenzene
23000
24000
32000
22000
18000
21000
28000
m,p - Xylene
21000
23000
46000c
21000
17000
21000
29000
Styrene
6100
6600
9600
NR
6200
5200
6000
9900
o - Xylene
11000
14000
10000
8700
10000
17000
Isopropvlbenzene
140
220
NR
BDL
BDL
BDL
NR
n - Propvlbezene
340
480
NR
390
350
0.4
790
a-Methvlstvrene
500
790
NR
660
610
600
330
a Three copier tests performed at Lab 4, values in most cases represent average of two measurements
b Test 2, copier paper feed jammed, only 1020 copies produced instead of 1998
c Value represents the sum of the ortho, meta, and para-xylene isomers
d NR = not reported
c BDL = below detection limit
-------
Table 4-4. Copier Emission Rates During Operation Based on RTI Sample Analysis of Duplicate Samples
Collected at Each Laboratory * (fig/hour • copier)
Chemical
Lab 1
Lab 2
Lab 3
Test 1
Lab 4 b
Test 2c
Test 3
Toluene
590
1000
2000
540
24000
(c)
Ethylbenzene
23000
29000
25000
27000
23000
-
m,p - Xylene
22000
29000
24000
25000
21000
-
Styrene
6300
8400
6600
6700
6000
-
o - Xylene
12000
15000
12000
NDe
11000
-
Isopropvlbenzene
160
160
160
ND
160
-
n - Propylbezene
360
450
390
ND
330
-
a-Methylstyrene
500
730
550
25
530
-
Formaldehyde
1900
2400
3200
2400
2700
2200
Acetaldehyde
1100
1300
1300
510
610
800
Propionaldehyde
_ d
-
-
-
-
-
2-Butanone
600
-
570
-
-
-
Butraldehyde
300
280
410
-
-
-
Benzaldehvde
1500
1200
980
1000
1200
630
Hexanal
590
690
950
-
-
730
a Values not corrected for idle concentration - idle samples not collected for analysis by RTI
b Three copier tests performed at Lab 4
c Test 2, copier paper feed jemmed, only 1020 copies produced instead of 1998
e ND = not detected
d Represents data not listed due to one of the following reasons - not reported by lab, below calibration rate,
or not detected.
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Table 4-5. Emission Rates Measured During Copier Operation Selected Aldehydes/Ketones and Ozone
(jig/hour • copier)
Phase II Phase I
Chemical
Lab 1
Lab 2
Lab 3
Test 1
Lab 4 a
Test 2 b
Test 3
RTI
Formaldehyde
1300
2200
4700
1500
BCR
1700
<500
Acetaldehyde
386
1635
NRC
BDLd
BDL
BDL
710
Propionaldehvde
192
ND"
NR
NR
NR
NR
<100
2-Butanone
307
ND
NR
NR
NR
NR
<100
Butraldehyde
300
ND
NR
NR
NR
NR
160
Bcnzaldehyde
1139
1834
NR
BCRf
BDL
BCR
1800
Hexanal
300
ND
NR
BDL
BDL
BDL
210
Ozone
1700
7500
1700
2000
2900
2400
3000
a Three copier tests performed at Lab 4, values in most cases represent average of two measurements
b Test 2, copier paper feed jammed, only 1020 copies produced instead of 1998
c NR = not reported
d BDL = below detection limit
c ND = not detected
f BCR = below calibration range
-------
rates measured during copier operation were relatively consistent except for the emission rate
measured for laboratory 2.
4.2.3 Headspace Samples
Results of the headspace samples for Phase II are shown in Table 4-6. All round-robin
tests were performed with the same lot of toner although a fresh cartridge was used at each test
lab. These results are not comparable with Phase I since this lot was not tested during Phase I,
and the analysis temperature was different. These results are reported in ng/mL of headspace and
show that for laboratories 1, 3, and 4 no major differences were seen in the concentrations of the
various containers of the lot of toner used for the round-robin testing. The toner sample from
laboratory 2 was held for approximately 3 months prior to being analyzed. Volatile loses may
have occurred during this time as indicated by the lower headspace results.
4.2.4 Particle Samples
As stated previously (Section 3.2), accurately measuring chamber recovery for particulates
is complex. While an attempt was made to measure particle emissions, results are not reported
since the tests were not conducted at all facilities, and the results obtained from those that did are
inconclusive. In general, no weight gain was measured on the filters by gravimetric analysis.
4- 10
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Table 4-6. Toner Headspace Results from Round-Robin Study' (ng/mL headspace)
Chemical
Lab 1
Lab2b
Lab 3
Lab 4
Toluene
4
0.8
2.1
3
Ethylbenzene
620
260
460
580
m,p - Xylene
620
270
440
570
Styrene
200
100
140
180
o - Xylene
410
210
300
380
Isopropylbenzene
7
4
5
6
n - Propylbenzene
14
9
21
14
a-Methylstyrene
28
23
22
33
a All headspace analyses were performed at RTI.
b Sample held for ~ 3 months; volatile losses may have occurred during this time.
4- 11
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5.0 ADDITIONAL ISSUES RELATED TO OFFICE EQUIPMENT EMISSIONS
Throughout this project, several issues were raised as either having potential pollution
prevention implications or areas requiring additional research:
• paper type and its effect on emissions from photocopy machines;
• recycled toner cartridges and the effect of their use on photocopier emissions; and
• emissions from color versus monochromatic copiers.
While each of these issues could constitute a significant research effort on their own, they were
investigated to a varying degree throughout this cooperative agreement and are summarized in the
following sections.
5.1 Paper Type
The technical advisors for this research effort indicated that emissions from copy machines
and printers would be different depending on the paper type being used. Specifically they were
referring to paper such as preprinted forms, labels, coated paper, transparencies, and both
recycled and virgin office paper. The literature review that was conducted as the first step in this
cooperative agreement identified several references discussing the effect of carbonless copy paper
on worker health complaints (Morgan and Camp, 1986; Marks et al., 1984; Marks, 1981; and
LaMarte et al., 1988). Carbonless copy paper was considered an "office product" and therefore
outside the scope of this research. In addition, it was decided that evaluation of the other types of
paper with respect to their emissions and their effect on overall copier emissions, while it may
have an impact, was not the highest priority. The primary goals were to develop a method that
could be used for evaluating emissions from office equipment and to use that method to identify
pollution prevention opportunities. Because of the complexity of developing the method and the
number of variables that are introduced by using several different types of copy machines, it was
decided that the paper supply should be kept constant throughout the research effort. This
allowed the number of experimental variables to be reduced and the data analysis to be simplified.
Paper from the same manufacturer and lot (with a recycled content of 25 %) was used
throughout all Phase II testing. In the beginning stages of Phase I, a different type of paper was
used (recycled content of 20 %) but experienced some paper jamming. The 25 %-recycled paper
performed well in all subsequent testing. Questions have been raised concerning the use of
recycled paper and its effect on copy quality, runnability, and emissions. The issue of varying
emissions from both recycled and virgin copy paper, even from the same manufacturer, is very
complex. Emissions not only are dependent on the specific manufacturing and recycling
technologies but also can be affected by variables such as the tree species and recycled material
that was used to derive the pulp.
5 - 1
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Buyers Laboratory, Inc. (BLI) conducted a survey of its subscribers to obtain information
on use and problems associated with recycled copy paper (BLI, 1995). They received 210
responses, of which 91 % indicated overall satisfaction with recycled paper. One of the greatest
concerns that was expressed by recycled paper users was runnability. Of the respondents, 82%
rated the runnability of the recycled paper that they use as good or excellent. In general, "it is the
physical characteristics of the paper, such as surface smoothness, thickness and porosity—not
recycled paper content—that determines whether the paper will run well (BLI, 1995)." It should
be noted that these important physical characteristics are easier to control when the source of
fiber used to manufacture the paper is consistent. A consistent source of fiber cannot always be
obtained from recycling operations because of the nature of the supply of waste paper. For the
photocopier testing that was done as part of the RTI/EPA cooperative agreement, better machine
runnability was obtained when using a paper with 25 % post-consumer recycled content as
opposed to a paper with 20 % recycled content. Researchers also found that some machines were
better able to run various types of paper without experiencing paper jams. In general, the BLI
report suggests that buyers purchase paper that falls within their machine's specifications and stay
with the type(s) that work well.
Runnability can also be affected by humidity and/or the moisture content of the paper
used. The BLI report states that moisture has a greater effect (and hence greater potential for
paper jams) on recycled paper than on virgin paper because it is more attracted to the recycled
fiber. Some high-speed copy machines are equipped with dehumidifiers to maintain the optimum
conditions for paper. Storage of paper in a climate-controlled environment can help to reduce the
impact of humidity on recycled paper runnability.
Another significant concern that is often expressed regarding the use of recycled paper is
its effect on equipment service (requiring a technician) and/or user maintenance. Of the
respondents to BLI's survey, 84% indicated that they saw no change in the need for equipment
servicing by a technician after switching to recycled paper. Also, 70% said that the need for user
maintenance, such as cleaning, was the same with both virgin and recycled paper. The most
significant factors that contribute to the need for service/maintenance include contaminants, such
as glue, that may be contained in the recycled pulp and paper dust. Contaminants in the recycled
paper fiber, resulting from inconsistent raw materials or glue remaining after the de-inking
process, may leave a residue on the internal components of copy machines. This residue may
build up over time and increase the need for equipment servicing.
BLI's survey results indicated that "in general, users of recycled paper with the higher
post-consumer materials complained more about paper dust than users whose recycled paper
contained lesser amounts." Excess paper dust in copy machines was linked to spots on copies and
resulted in the need for more frequent cleaning of the machine parts. BLI's report noted that a
survey respondent using recycled paper with 25 % post-consumer waste had no more dust than
when using virgin paper. It is interesting to note that this paper was the same brand that was used
during the round-robin evaluation that was part of this research. Dust generation was reported as
being less of a concern for printer and fax operation—likely due to less throughput, slower
operating speeds, and shorter paper paths.
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5.2 Recycled Toner Cartridges
Several manufacturers have initiated recycling consumable materials, including toner
cartridges and photoconductive drums. It has been reported that 30 million laser toner cartridges
were sold and discarded in 1993 and that, industry-wide, refilling would reach 22 % in the year
1998 (Global Recycling Network—Recycle Talk Answers from Fred Friedman 11-27-96; Internet
source). Another source estimated that in 1996, over 40,000 tons of unrecycled cartridges, which
are generally made from non biodegradable plastic, went into landfills in the United States
(Internet source: http://www.laserlux.com). This same source reports that one pint of oil is
required to produce each new cartridge and therefore remanufacturing would save over 2.5
million gallons of oil in 1997.
Laser printer toner cartridges are the most frequently recycled element, both by the
original manufacturer and by small businesses dedicated to that purpose, although cartridges from
photocopiers, fax machines, and inkjets are also remanufactured. A 1994 survey in Recharger
Magazine (Vernon, 1994) showed that approximately 5,000 companies remanufactured
cartridges. Nearly one-third of all remanufacturers represented by the survey had been in business
for less than 2 years, and only 5 % of the industry had been in business for more than 7 years.
The performance of a recycled toner cartridge can vary based on the condition of the
cartridge and the process used to remanufacture it (U.S. EPA, 1994). When the industry began
remanufacturing cartridges, "drill and fill" cartridges gave remanufactured toner cartridges a poor
reputation. A hole was drilled in the bottom of a cartridge and sealed with tape, and the cartridge
was sold to consumers along with two bottles of toner and two tape seals. When the cartridge
ran out of toner, the customer removed the tape and poured the toner from one of the bottles into
the cartridge and resealed the hole. This process was repeated when the toner ran out again. The
drill-and-fill cartridges caused quality problems because the toner debris cavity was not emptied
each time; if this cavity overfills, excess toner leaks into the machine.
There is currently no standard remanufacturing process in the cartridge recharging
industry. Each company remanufactures its product to its own standard; however, BLI performs
certification of remanufactured cartridges. The certification procedure includes on-site inspection
and analysis of a remanufacturer's procedure and facilities and testing of the remanufactured
cartridges. BLI certifies that a company uses sound remanufacturing procedures and that the
remanufactured cartridges perform as well as or better than new cartridges.
Although no standard process exists, the remanufacturing process is similar for each type
of cartridge: the cartridge is tested for any deficiencies that would prohibit it from being
remanufactured and is taken apart, cleaned and inspected for worn parts that need to be replaced,
and refilled. If there is no replacement part available for a cartridge, the cartridge may only be
used for one cycle or may not be used at all.
The waste toner cannot be reused for its original purpose and is generally disposed of in a
landfill. In some circumstances, waste toner can be mixed with asphalt for highway construction.
Most toner cartridges, including wet- and dry-toner cartridges, generate approximately 20-30
5-3
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grams of waste per cartridge. There is generally 150 to 700 grams of toner in a newly
manufactured cartridge.)
In addition to environmental benefits, using remanufactured toner cartridges has financial
benefits as well. It was reported in 1994 that the average price of a new laser printer cartridge
was $100, while a remanufactured cartridge for the same machine cost $45 (Clayton, July 1994).
One cartridge remanufacturer advertises that its remanufactured cartridges cost 30 to 75 % less
than new ones (Internet source: http://www.laserlux.com). These cost differences can be
significant because the toner accounts for approximately 75 % of the total cost over the life of a
printer (Table 5-1).
Table 5-1. Approximate Cost Percentages over the Lifetime of Laser Printers
Parts
% of Total Costs
Laser printer—original equipment cost
10%
Paper
15%
Toner cartridges (original equipment manuf.)
75%
Source: Clayton, 1994.
5.3 Color Photoimaging Machines
One of the recommendations from the March 1994 technical advisors planning meeting for
this project was to evaluate the emissions from color dry-process photocopiers and/or printers.
The technical advisors as well as the scientific literature indicated that the emissions from both
dry- and wet-process color photoimaging are not well characterized and therefore should be
evaluated further. They suggested that an evaluation should include an investigation to determine
the relative toxicity of color toners with respect to the traditional black toners and the potential
need for reformulation. Color image processing requires the use of lower fuser temperatures,
requires multiple passes within the machine, and uses characteristically different toners. Each of
these requirements may affect IAQ and subsequent pollution prevention strategies. The lower the
fuser temperature, the lower the anticipated rate of emissions of VOCs; however, the need for
multiple passes increases the time that the image may be subjected to heat and therefore may also
affect emissions. Therefore, an investigation of the balance between the fuser temperature and
time in contact with the fuser rollers is needed.
The initial research plans for this project included color copiers. Due to the high demand
and low supply of these copiers at the time of the early testing, a color copier was unavailable.
Color copying has increased substantially in the past 3 years, and that trend is likely to continue as
the technology matures and prices become lower. Therefore, emissions from color dry- and wet-
5-4
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process photoimagining machines is still an important issue that should be considered for future
research efforts.
5-5
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6.0 POLLUTION PREVENTION OPPORTUNITIES
An initial objective of this research was to identify and evaluate potential pollution
prevention technologies that could be used to reduce indoor air emissions from office equipment.
As stated in Section 2, the initial literature search revealed a lack of data on emissions as well as
the lack of a standard method that could be used to evaluate throughly both VOC and ozone
emissions from office equipment. Without a standard test method, the impact of pollution
prevention in the form of design, technology, or raw material changes could not be measured.
Therefore, research priorities were broadened to include the development of an emissions testing
guidance document that could be used both by manufacturers and by other researchers to evaluate
emissions in order to identify and evaluate pollution prevention opportunities.
Throughout the literature review, test method development, and emission measurement
activities, pollution prevention options have been identified that may result in reduced emissions
from office equipment. In some cases, testing has confirmed literature data and/or identified areas
where more research is needed. The following sections are organized according to pollution
prevention options identified through the published literature and through laboratory testing
conducted as part of this project.
6.1 Literature
6.1.1 Pollution Prevention for Reducing Ozone Emissions
Ozone is one of the most significant pollutants generated in dry-process photoimaging. As
described in Section 2.2.2.1, some equipment manufacturers have modified their printers and
photocopiers to reduce ozone emissions. In previous and some current designs, electrically
charged corona wires are used to add a uniform primary charge across the surface of the
photosensitive drum and the paper surface. The corona wires are separated from the drum by a
small distance and, therefore, high voltages are applied to the corona wires to attain the needed
charge. Electrical arcing results from the corona wire, which produces ozone. In newer designs,
the two corona wires are replaced with "charging" rollers. Unlike the corona wires, the charging
rollers are in direct contact with the photosensitive drum, which eliminates the need for high
voltage and prevents the formation of electrical arcs and ozone. A recent NIOSH study (Gressel,
1996) of printer emissions indicates that ozone emissions from printers with corona wires were
high enough (0.005-0.06 mg/min) to cause concern in an indoor environment. While the ozone
emissions from a printer with the newer charged roller design produced very little ozone (0.0008
mg/min). During Phase I evaluation of different dry-process photocopiers in this project, a wide
range of ozone emission rates were observed (1,300 to 7,900 ng/hr • copier). The copier with the
lowest emission rate was advertised as a low-ozone-emitter. The charged roller system presently
has copy rate limitations, so future research investigating the application of this system to higher
throughput machines could yield pollution prevention benefits.
6- 1
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6.1.2 Pollution Prevention Opportunities for Toner
One manufacturer has developed a technology for improving toner transfer efficiency
through the use of a replaceable cartridge system. The cartridge system houses the toner as well
as the photosensitive drum and other consumables. As the photoconductive surface of the drum
deteriorates, the toner transfer efficiency decreases, increasing the potential for indoor air
emissions. The photosensitive drum is automatically replaced at regular intervals (whenever the
toner is changed), thereby restoring the transfer efficiency to its original state and preventing
increasing particulate pollution. Printers in which the photoconductive drum are not replaced as
part of regular maintenance will suffer a gradual decrease in toner transfer efficiency as the drum
ages, leaving more toner particles within the printer chassis or in the indoor air. Therefore,
expanding the use of this technology to other manufacturers or other types of equipment could
result in pollution prevention by minimizing particulate emissions.
For dry-process systems, reducing the temperature of the fusing operation to reduce the
volatilization of VOCs from the toner may be a pollution prevention option for consideration.
Elevated temperatures used in the fusing process can increase the volatilization of VOCs present
in the toner as confirmed by the toner headspace tests conducted as part of this cooperative
agreement (see Section 3.4.6.1). Reducing the fusing temperature (by changes in pressure or in
toner formulation) may result in lower VOC emissions. Therefore, an investigation of the balance
between the fusing temperature and time in contact with the fuser rollers may result in pollution
prevention benefits. Indoor air emissions may be reduced through a greater reliance on pressure
fusing than on heat fusing.
Changes in toner particle size may have an impact on toner transfer efficiency, the fusing
process, print quality, and overall emissions. The size of the particles emitted also influences the
degree to which they are inhaled and the potential for adverse health effects. Therefore, research
focused on toner chemistry and reformulation could also consider the potential pollution
prevention benefits of various toner particle sizes. It should be emphasized that the different
aspects of the fusing process—temperature, pressure, and toner formulation—are interrelated;
therefore, any changes in one aspect may require changes in the others for proper equipment
operation.
In wet-process systems, toners (and developers, where applicable) are the major source of
indoor air emissions. These emissions occur from the volatilization and/or aerosolization of toner
and toner solvents. Reformulation of toners using lower-volatility solvents can result in lower
emissions. However, changing solvents may impact the quality of the printed images and may
lead to mechanical problems such as clogging of the ink or bubble jets. Pollution prevention
research taking place within the printing and publication industry could also be considered for
other toner options. For example, water-based toners and ultraviolet (UV)-cured solid toners
used in the printing industry may prove useful for some printers and photocopiers.
The toner cartridge is the most common element being recycled, or remanufactured, both
by the original manufacturer and by small businesses dedicated to that purpose. In 1993,
approximately 30 million toner cartridges were sold in the U.S. and after use, most discarded in
6-2
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landfills (Global Recycling Network—Recycle Talk Answers from Fred Friedman 11-27-96;
Internet source). Toner cartridge recycling is projected to reach 22 percent in 1998 and not only
diverts plastic from landfills, but it also saves oil. It is reported that one pint of oil is required to
produce each new cartridge and therefore remanufacturing will save over 2.5 million gallons of oil
in 1997 (Internet source: http://www.laserlux.com). This topic is discussed in Section 5.2.
6.1.3 Pollution Prevention Related to Equipment Maintenance
Pollution prevention may also be achieved through modified equipment maintenance
procedures or by redesigning machines so that less maintenance is needed. Organic solvent-based
products are typically used to clean glass, mirrors, and rollers; the use of water-based products
should be investigated. Reformulation of solvents for cleaning glass and mirrors may be easily
accomplished but may be more difficult for other cleaning products that not only clean but also
replenish the rubber parts (rollers) within the machine. In addition, because emissions have been
shown to increase with time since the previous maintenance cycle (Claridge, 1983), reduced
indoor air emissions can be expected from proper and timely equipment maintenance. In one
study of five different photocopy machines, ozone emissions before maintenance ranged from 16
to 131 |ag/copy. Emissions after maintenance were 4 ng/copy or lower in all five machines
(Selway et al., 1980).
6.2 Pollution Prevention Opportunities Resulting from Laboratory Testing
Laboratory testing efforts were focused in these areas: (1) measurement of emissions
from dry-process photocopiers, (2) evaluation of ozone emissions, and (3) evaluation of emissions
circuit board laminates used in electronic equipment such as computer monitors.
6.2.1 Reduced Emissions from Toners Used in Dry-process Photocopiers
Initial research conducted as part of this cooperative agreement identified toners as a
primary contributor to indoor air emissions from dry-process photocopiers. Toners supply the
image to the page and generally consist of a polymeric resin carrier (e.g., styrene-based
copolymers) between 5 and 10 |im in diameter. There are two types of toner used in dry-process
photocopiers depending on the machine: monocomponent toners and dual-component toners.
Machines that use monocomponent toners use toner only; the toner may also include a magnetic
material to aid in toner transfer. Machines that use dual-component toners include a carrier
(sometimes referred to as developer) in the toner. These particles generally consist of iron
particles between 50 and 200 |jm in size and serve to deliver the toner particles to the
photoconductive drum during the photocopy process.
Toners are commonly manufactured by melt-mixing pigment and polymers together,
followed by high-impact fracture. Toner processing is most commonly carried out in an extruder,
Banbury® mixer, or continuous mixer. As a general rule, extruded toners are "cleaner" than
toners produced in a Banbury® mixer. The extrusion process is more modern and, in addition,
the toner can be manufactured under a vacuum, which may decrease the amount of volatile
compounds in the toner (Bever, 1986).
6-3
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To better understand the relative contribution of toner emissions, two methods were used
to collect the data presented in this section: (1) the large chamber test method developed
specifically for this project and (2) headspace analysis. The data collected from the large chamber
test are from the Phase I testing of four different dry-process photocopy machines (see Section 3
for details). Three of the machines use dual-component toners, and the fourth machine uses
monocomponent toners. The data presented from the headspace analysis were obtained using the
procedure described in Section 3.4,6.1 (although the testing described in this section was
conducted at 150 °C) and are from three dual-component toners. The toner evaluated in the
headspace analysis is manufactured by the same manufacturer as one of the machines tested in the
large chamber.
Calculated VOC emission rates resulting from the Phase I large chamber tests are
summarized in Section 3. These results show that the lowest VOC emission rates were measured
for copier 3 (the only copier with monocomponent toner). It is hypothesized that differences in
emission rates for VOCs from different copiers may be due to differences in the chemical
composition of the toners. Such variations in emissions indicate a potential opportunity for
pollution prevention through copier redesign, toner reformulation, and/or specification of
"cleaner" raw materials for the toner to reduce emissions of concern (e.g., sensory irritants and/or
HAPs).
As presented in Section 3, in most cases, emission rates from the four copiers tested
during Phase I were low in the idle mode (<500 |ig/h) when compared with emissions in the print
mode. Where this was the case, the impact on indoor air quality should also be low. Two
exceptions were relatively high measured emission rates for formaldehyde and acetone from
copier 3. It is possible that differences in toner type could be responsible for elevated emission
rates for these two chemicals in the idle mode. This result suggests that the most important
impacts on IAQ will occur during printing; as a corollary, pollution prevention strategies should
focus on the print operation.
To determine the effect of toner age on emission rates, two large chamber tests were
conducted during Phase I using an existing toner cartridge and compared with results from three
tests conducted immediately after a new toner cartridge had been installed. A comparison of
results for the tests conducted with new vs. old toner cartridges showed substantially elevated
emission rates for the tests with the new toner. For the aromatic hydrocarbons, such as
ethylbenzene, the xylenes, and styrene, the emission rates with new toner were approximately 50
percent higher than the emission rates with old toner. These results show the substantial impact
that toner age may have on emission rates and support the conclusion that pollution prevention
research specifically focused on toner manufacturing and formulation be pursued.
6-4
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The results from the toner headspace analysis are shown in Table 6-1 and compare three
different toners that are manufactured for use with copier 1. Please note that these results are not
comparable to those shown in Table 3-26 although the same lots were analyzed. These results are
from headspace samples heated to 150 °C, not 35, 100, or 200 °C. According to the Material
Safety Data Sheets, all three toners are comprised of: 80-90 weight percent styrene/acrylate
copolymer; 5-10 weight % carbon black; 5-10 % polypropylene wax; 1-3 % titanium dioxide; and
less than 1 % quarternary ammonium salt. The three toners are each manufactured at different
plants using the same raw materials, but the manufacturing process for toner C is different than
the process for toners A and B. Toner C is manufactured using the extrusion process, while
toners A and B are manufactured using the Banbury® process. The data shown in Table 6-1
indicate that headspace concentrations resulting from toners A and B are typically 2 to 5 times
higher than concentrations from toner C. As previously stated, the extrusion process (toner C) is
more modern; additionally, the toner can be manufactured under vacuum, which may decrease the
amount of VOCs in the toner (Bever, 1986). Based on these limited results, it is recommended
that the extrusion process be further explored as a potential option for producing lower-emitting
toners.
Table 6-1. Headspace Analysis of Toner Samples (ng/mL)a
Chemical Emitted
Toner A (Lot 1-3)
Toner B (I^ot 1-4)
Toner C (Lot 1-5A)
Ethyl benzene
1100
950
220
m,p-X ylene
1100
930
470
Styrene
290
260
130
o-Xylene
740
660
290
a Tests at 150 °C.
6.2.2 Reduced Ozone Emissions from Copiers
As presented in Section 3 (Table 3-20), substantial differences in ozone emission rates
were seen between the four copiers tested during Phase I, ranging from 1,300 jag/h • copier for
copier 4 to 7,900 ng/h • copier for copier 3. Copier 4 was advertised as a low ozone emitting
copier. Results show that the techniques applied to this copier for reducing ozone emissions have
been successful and should be further explored.
6-5
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7.0 CONCLUSIONS AND RECOMMENDATIONS
The research that was conducted as part of this cooperative agreement is separated into
four major activities:
• literature review;
• Phase I method development and testing;
Phase II round-robin evaluation; and
• identification of pollution prevention opportunities.
The conclusions and recommendations resulting from each of these four activities follow.
7.1 Literature Review
At the beginning of this cooperative agreement, a literature review was conducted to
obtain information on office equipment technologies, emissions, and measurement methods. A
separate report (Hetes et al., 1995) resulted from this review. General conclusions that can be
made from the report are:
1. Sources of emissions from office equipment include materials of construction (e.g., plastic
casings, printed circuit board laminates), supplies used (e.g., toner), and generation of
emissions during operation (e.g., ozone).
2. No standard method for measuring emissions from office equipment was available.
Therefore, development and validation of an emissions testing guidance document was a
top priority for this research.
3. Office Equipment technologies (see Table 2-1) showing rapid growth in market share
(e.g., color coping, printing) should be considered a priority for any future research.
7.2 Phase I Testing
Results of Phase I testing provided valuable information on the performance of the test
method and the emissions characteristics of dry-process photocopiers. Conclusions and
recommendations resulting from the Phase 1 testing are:
1. The large chamber test method developed as part of this project provided acceptable
performance for characterizing emissions from dry-process photocopy machines. Percent
recovery for calculated emission rates for standard materials emitted into the chamber at
known rates was generally greater than 85%. Ozone was the exception with only 72%
recovery. Precision of replicate tests using both standard emitters and photocopiers was
good (% RSD<20 in most cases). In general, precision was much better for the emission
rate measurements in the print mode than in the idle mode where measured emission rates
had much lower values.
7-1
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2. Measuring emissions from office equipment can present numerous challenges and
complications. Specific considerations identified and addressed during this study follow.
• Heat Generation: Depending on the machine, heat generation in the chamber may
be a problem. As a result, the test method developed as part of this project
specifies a temperature range of 28.5 ± 2.5 °C and 2 ACH.
• Limited Paper Supply: A finite paper supply for copy machines limits the duration
of the test. For this study, a paper supply of 2,000 sheets was used for each test.
This supply was exhausted after 20 to 40 minutes for the mid-range dry-process
machines evaluated. Collection of integrated chamber air samples continued for an
additional 4 air changes (i.e., 2 hours for this study).
• Power Requirements: The type of outlet required varies among copiers. Therefore,
installation of new outlets, changing outlets, or multiple outlet formats may be
required.
• Remote Starting: Remote starting of the machines is necessary to maintain the
integrity of the chamber. Complications from remote starting can result from either
the software (automatic reset) and/or hardware (lack of electronic overdrive
capability). These problems can be minimized if an experienced service technician
installs, sets up, and checks out the equipment.
• Toner Depletion and Replenishment: Testing indicated that toner age can have a
significant impact on photocopier emissions, as can a variation between different
lots of toner. To control for this variable it was determined that residual toner in
the toner delivery system needed to be depleted and replenished with fresh toner
when changing cartridges or when a period of more than two weeks elapsed
between tests using the same toner lot. A procedure for this was developed and
included in the standard test guidance.
3. During Phase I testing, chamber air concentrations of styrene in the range of 40-60 ng/m3
(7,000-10,000 ng/hour • copier) were observed (Tables 3-12, 3-15). Emissions testing
was conducted using chamber conditions that approximate conditions found in office
buildings; therefore, it is possible that indoor air concentrations of this magnitude could
also be found in offices. For comparison, median indoor air concentrations for styrene
measured in the Total Exposure Assessment Methodology (U.S. EPA, 1987b) study were
about 1.0 ng/m3.
4. Although many of the same compounds tended to be detected in emissions from each of
the four photocopiers, the relative contribution of individual compounds varied
considerably between machines, with differences greater than an order of magnitude for
some compounds. The variation in compounds is most likely due to different toner
formulations used for the different machines.
7-2
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5. Many of the compounds detected in this study—benzaldehyde, ethylbenzene, nonanal,
ozone, styrene, and xylenes—were consistent with compounds identified in the literature
from photoimaging equipment. Again, any variation in compounds is most likely due to
the different toner formulations used for different machines.
6. The integrated sampling approach for generating emission rate data was determined to be
acceptable. Although the use of time-point samples provides some additional information,
it is more labor-intensive and costly.
7. Toner headspace testing indicated that increased temperatures resulted in increased
organic concentrations in the headspace gas. Results from the toner headspace analysis
also indicated that there may be some correlation between toner headspace analysis and
copier emissions; however, more testing of this relationship is required before any
conclusions can be drawn.
8. Toner lot, manufacturing process, and age (as measured by the amount of time that a
cartridge has been opened) has a significant impact on organic emissions during both
headspace tests and copier operation. Therefore, any organization planning to conduct
photocopier emission tests or analyze emissions data needs to consider and control for this
variable. In addition, it is recommended that further investigation be conducted to
evaluate the effect of toner manufacturing process and purity of raw materials on
photocopier emissions.
9. Because the large chamber emissions measurement method developed during this
cooperative agreement requires specialized facilities and is relatively expensive to perform,
preliminary investigations were conducted of an option for rapid-screening of copier
organic emissions: copier vent gas analysis. Results from the very preliminary vent gas
sampling and analysis appeared to indicate that a correlation exists between the vent gas
concentrations and the chamber data for the one copier that was evaluated. However,
because each copier is designed differently, with a different number of vents and different
vent flow rates, a single screening method that could be used for all copiers is highly
unlikely.
7.3 Phase II Testing
In general, the results show fairly good accuracy and precision for the round-robin
chamber test results. The results demonstrate that the emissions testing guidance document can
be used successfully by other laboratories to measure VOCs and aldehydes/ketones from dry-
process photocopiers. Conclusions and recommendations from the results are:
1. Results obtained from different chamber facilities are comparable. The VOCs reported to
have the highest emission rates by all of the participating laboratories were ethylbenzene,
o-, m-, p-xylenes, and styrene. These were also the compounds with the highest emission
rates reported from the Phase I testing.
7-3
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2. Excluding problems with analytical bias as seen from one laboratory, the precision
between laboratories for VOC measurements was excellent (RSD of less than 10% in
many cases). This can be compared to other round-robin studies for small chamber tests
where agreement between laboratories was not as good (RSD 25-46 %).
Aldehyde/Ketone and ozone emission rates were more variable.
3. Differences in chamber design and construction at the different laboratories seemed to
have little effect on the test results. Perhaps more important than the chamber
construction is the analytical methodology used to analyze the sample cartridges.
4. The methods of introducing standard emission sources to the chambers seemed to work
well with the exception of formaldehyde at laboratory 2.
5. Sufficient test parameters seem to have been addressed to provide consistent results with
this photocopier during this phase of testing. However, some photocopiers or other types
of office equipment may not allow depletion/ replenishment of toners as easily as the
copier that was used during the round-robin testing. This is an issue that should be
addressed with further investigation.
6. Based on the results from Phase I and Phase II, the emissions testing guidance document
can be used as written for generating emission rate data from dry-process photocopiers.
Laboratories that are planning to conduct these tests must first demonstrate proficiency in
the method using the same evaluation procedures that were used for the round-robin
study.
7. Throughout the method development and testing, a single paper supply and lot of toner
supplied by the copier manufacturers was used. The reason for this was to limit the
number of copier-related variables. It is recommended that future testing evaluate the
effect of different paper types (including pre-printed forms, labels, transparencies, etc.),
remanufactured toner, and color technologies on emissions.
7.4 Potential Pollution Prevention Opportunities
Potential opportunities for reduced emissions from photocopiers were identified from the
literature, discussions with manufacturers, and from the tests conducted as part of this research.
They are:
1. The use of charged roller systems decreases ozone emissions; however, the charged roller
system presently has copy rate limitations. Therefore, it is recommended that future
research focus on investigating the application of this design change to higher throughput
machines.
2. Both the literature and laboratory testing indicate that the greatest level of organic
emissions from dry-process photocopiers results from the toner during the operating
mode. Additionally, higher temperatures were shown to result in higher organic emissions
7-4
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during toner headspace tests. Therefore, pollution prevention research should focus on
the relationship between toner formulation and the fusing process. Specifically this could
include:
• investigating the relationship between fusing temperature and time in contact with
the fusing rollers;
• testing of designs that use only pressure fusing;
• evaluating specific differences between mono- versus dual-component toners and
the resulting differences in emissions;
• evaluating the effect of toner particle size on toner transfer efficiency and
particulate emissions;
• investigating methods for increasing the life of the photosensitive drum that would
result in better transfer efficiency;
• identifying options for toner reformulation and the use of high purity raw
materials; and
• evaluating other toner/fiiser combinations, such as ultraviolet (UV)-curing
technologies, that are being used by other sectors of the printing industry.
3. The research indicated that emissions can vary depending on the specific toner
manufacturing process. The extrusion process for manufacturing toner should be
investigated further. It should be noted that while this process may result in lower-
emitting toner to an indoor air environment, the multimedia pollution prevention
implications of the extrusion process should also be investigated. As one measure for
ensuring that multimedia pollution prevention is being achieved, specifications should be
refined to ensure consistent and "clean" raw materials for the toner manufacturing
process.
4. Photocopier emissions have been shown to increase between routine maintenance cycles.
Therefore, development of new equipment designs that require less (or even no)
maintenance but are still able to operate with the lowest possible emission rates could
result in pollution prevention benefits over the life of a copier.
7-5
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8.0 DATA QUALITY
Quality assurance (QA) activities were an integral part of this research program. QA
activities that were conducted in support of this study included:
• Preparing quality assurance project plans (QAPPs),
• Developing data quality indicator goals for data collected,
Monitoring quality control procedures and results, and
• Conducting inspections, audits, and data reviews.
8.1 Quality Assurance Project Plans
RTI prepared two, Category III QAPPs addressing all of the aspects of each phase of the
research. Each QAPP was approved by EPA prior to testing.
8.2 Data Quality Indicator Goals
Chamber air concentrations and emission rates were the critical measurements in this
study. The data quality indicator goals proposed in the QAPP are shown in Table 8-1. This table
was prepared to insure that each participating laboratory was aware of the level of accuracy,
precision, and completeness desired for the round-robin testing. Each laboratory was responsible
internally for assuring compliance of the details such as relative humidity, temperature, sample
collection, air flow measurements, and chamber air concentrations. Since this was a performance
based evaluation (results evaluated based on each laboratories' recovery of the standard emitters),
not all of this information was provided to RTI by each participating laboratory. Only the final
calculated emission rates of the standard emitters and copier tests were required to be reported.
From these reported data, Tables 8-2 and 8-3 have been constructed to show the within (intra)
and between (inter) laboratory summaries of the precision and accuracy. These tables are based
on reported emission rates provided by each laboratory.
In general the data quality goals were met. There were some specific cases in which the
goals were not met; however, these cases usually indicated a specific problem associated with a
laboratory or variation in the analytical methods and/or chambers at the different laboratories.
Refer to Section 4 for technical evaluations of the observed differences. (Example:
aldehyde/ketone interlaboratory precision goal for emission rates during copying, <35% RSD
goal vs. 62 %RSD measured for all labs and 21%RSD measured for samples collected at other
labs but analyzed at RTI. This indicates an analytical problem at a lab, not a problem with the test
method.)
8- 1
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Table 8-1. Summary of Data Quality Indicator Goals
Precision (% RSD)
Parameter
Accuracy Completeness
Intralaboratory Interlaboratory (% Recovery) (%)
VOCs
Air Flow Measurements
Chamber Air
Concentrations
Emission Rates
Headspace Equilibrium
Concentrations
Aldehydes/ketones
Ozone
Sample Collection Air
Flow
Chamber Air
Concentrations
Emission Rates
Air Flow Measurements
Chamber Air
Concentrations
*10
^20
^25
<25
<10
<15
<;20
<10
NT"
NAC
<30
^35
<25
NA
^30
<35
NA
NTb
>90
s75
>70
>75
>90
2: 80
2:70
>90
z80
95
80
80
100
95
80
80
95
80
Emission Rates
<15
<25
: 70
80
Not tested - duplicate ozone monitors not available.
Not tested - materials for assessing accuracy not available.
NA-Not applicable
8-2
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Table 8-2. Summary of Emission Rate Accuracy and Precision for Standard
Emission Sources
Accuracy (% Recovery)
Precision (%RSD)
Parameter
Intralab
(RTI)
Interlab
Analysis at
RTIa
Interlab
Analysis at
each labb
Intralab
(RTI)
Interlab
Analysis at
RTIa
Interlab
Analysis at
each labb
Chamber Evaluation
(Standard Emitters)
Toluene
115 0
119
112
2.9
8.2
22
Chloroform
94d
NTf
NT
7.6
NT
NT
Decane
NT
104
112
NT
4.8
24
Formaldehyde
93 e
82
155
2.2
36
89
Ozone
72e
NT
57
9.3
NT
44
a Releases made at each participating lab; duplicate samples collected at each lab and analyzed at RTI.
b Releases, collection, and analysis performed at each participating lab.
c Calculations based on five standard emitter releases.
d Calculations based on four standard emitter releases; five releases actually made; however, internal standard
in one sample was low indicating desorption problem during analysis.
e Calculations based on three standard emitter releases
f NT = not tested
8-3
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Table 8-3. Summary of Emission Rate Accuracy and Precision
Accuracy (% Recovery)
Precision (%RSD)
Parameter
Intralab
(RTI)
Interlab
Analysis at
RTIa
Interlab
Analysis at
each labb
Intralab
(RTI)
Interlab
Analysis at
RTIa
Interlab
Analysis at
each labb
Analytical Methods
(Spikes, Replicate
Samples)
VOC
NT0
NT
NT
NT
NT
NT
Formaldehyde
93
NT
NT
2.7
NT
NT
Ozone
NT
NT
NT
NT
NT
NT
Emission Rate
Determination
(Same Copier
VOCd
NT
NT
NT
5.5
12
20
VOCe
NT
NT
NT
5.7
21
60
Aldehydes/ketonesf
NT
NT
NT
11
19
62
Aldehydes/ketonesg
NT
NT
NT
15
21
62
Ozone
NT
NT
NT
7.1
NT
88
' Releases made at each participating lab; duplicate samples collected at each lab and analyzed at RTI.
b Releases, collection, and analysis performed at each participating lab.
c NT = not tested
d Average %RSD of target VOC compounds with emission rates >1000 |ig/hr»copier.
e Average %RSD of all target VOC compounds.
f Average %RSD of target aldehydes/kctones with emission rates >1000 |ig/hr*copier.
8 Average %RSD of all target aldehyde/ketone compounds.
8-4
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8.2.1 Precision
Precision is expressed as the percent relative standard deviation (%RSD) between
replicate samples or tests. The %RSD is calculated as
%RSD = - x 100
Y
where: %RSD = relative standard deviation
S = standard deviation
Y = mean of replicate samples
Intralaboratory precision of the quantitative analytical methods for measuring chamber air
concentration was evaluated by collecting and analyzing duplicate chamber air samples.
Intralaboratory precision of the emission rates in Phase I was evaluated by conducting triplicate
emission tests on a single dry-process photocopier (see Tables 3-12 and 3-13).
In Phase II, interlaboratory precision for the measurements were based on chamber air
measurements for the standard emitter. In addition, replicate samples were collected by each
laboratory and shipped to RTI for analysis. Interlaboratory precision of emission rate
measurements was evaluated by comparing emission rates for known emission standards and for
the same copier tested at the four laboratories. A summary of the precision and accuracy for the
standard emission sources is shown in Table 8-2. A summary for the emission rate precision and
accuracy is in Table 8-3.
Toner headspace results were evaluated for precision only. These analyses were
performed to verify that the toner cartridges from the "same lot" of cartridges used for the round-
robin testing were uniform in initial composition. These analyses were used for comparison
purposes only with no intent to directly link the concentrations found from the toner headspace to
the resulting emission rates during operation. No recovery experiments were performed to
demonstrate the accuracy of the headspace analyses. All toner headspace samples were prepared
and analyzed in duplicate with the exception of the toner collected at Lab 4 in which case four
samples were analyzed. Results of these analyses are shown in Table 8-4.
8.2.2 Accuracy
Accuracy of chamber air concentrations was evaluated by determining the percent
recovery of VOCs, aldehydes, and ketones from spiked sample cartridges:
%REC = (Am/AJ x 100%
where A,,, is the amount of VOC measured during chemical analysis and \ is the amount of VOC
spiked onto a sampling cartridge. For ozone, measurement accuracy for chamber air
concentrations was evaluated by determining the ozone concentration at the generator source
using Drager tubes.
8-5
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Table 8-4. Summary of Round-Robin Toner Headspace Analysis Precision "'b
Precision (%RSD)
Compound
Lab 1
Lab 2
Lab 3
Lab 4
Average
Toluene
1.8
18
20
26
17
Ethylbenzene
1.4
15
4
7.8
6.9
m,p-Xylene
1.5
14
8
8.3
8.0
Styrene
2.1
16
18
5.3
10
o-Xylene
1.0
13
10
7.2
8.1
Isopropylbenzene
1.1
13
16
6.8
9.1
n-Propylbenzene
0.5
14
18
6.0
9.8
a-Methylstyrene
12
37
42
22
28
a Based on duplicate samples collected at labs 1, 2, 3 and four samples at lab 4. All samples
analyzed at RTI
b Toner samples collected from toner cartridge immediately after copier chamber test.
8-6
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Accuracy of emissions factors was evaluated by determining the percent recovery of
VOCs, aldehydes/ketones, and ozone spiked into chamber air at measured concentrations:
%rec = (cycj x 100%
where CLl and C9 are the chamber air concentrations measured at the inlet and the sampling port of
the test chamber, respectively. Summaries of the accuracies for the standard emission sources and
for emission rates are presented in Tables 8-2 and 8-3, respectively.
8.2.3 Completeness
General goals for completeness were met for this project. All laboratories reported
emission rate measurements for the copier and standard emitters tested.
8.3 Quality Control
Chamber air samples collected from empty test chambers and blank cartridges were
analyzed to monitor background and accidental contamination. Calibration curves were prepared
prior to analysis of chamber air samples, and check standards were analyzed at regular intervals to
assure that the calibration remained valid. All data were generated when the analytical systems
were operating within the control criteria.
8.4 Inspections, Audits, and Data Reviews
Throughout the research, several inspections, audits, and data reviews were conducted by
QA officers at RTI to ascertain that standard operating procedures (SOPs) for instrumentation
were being implemented; procedures in the QAPPs were being followed; data were being
recorded properly; and that records and controls conformed to good laboratory practice. In
addition, QA audits of both the RTI large chamber and the EPA large chamber were conducted
by the EPA QA Officer. Copies of the reports resulting from these audits are in Appendix D.
8-7
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Bever, Michael B. 1986. Encyclopedia of Material Science and Engineering, Vol. II. MIT Press,
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Brooks, B.O., G.M. Utter, J.A. DeBroy, W.F. Davis, and R.D. Schimke. 1993. Chemical
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Canon, Inc. 1990. Fundamentals of Copier Technology. Japan.
Claridge, M. 1983. Photocopiers: An Office Hazard. Environmental Health. Vol. 91,
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Clayton, Bill. 1994. Laser Plus. Personnel Communication. June 16, June 22, July 20, and August
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Cornstubble, D.R. and D.A. Whitaker. 1998. Personal Computer Monitors: A Screening
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Gallardo, M., P. Romero, M.C. Sanchez-Quevedo, and J.J. Lopez-Caballero. 1994.
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APPENDIX A. Participants and Recommendations from Technical Advisors Meeting on
Application of Pollution Prevention Techniques to Reduce
Indoor Air Emissions from Office Equipment
March 9,1994
PARTICIPANTS
Jack C. Azar
Xerox Corporation
Bradford Brooks
IBM/ImmunoCompetence
Joel Farley
U.S. Environmental Protection Agency
Alan Hedge
Cornell University
Robert G. Hetes
Research Triangle Institute
Frankie Hutchings
Underwriters Laboratory
Gerald G. Leslie
Lexmark International, Inc.
Kelly Leovic
U.S. Environmental Protection Agency
Mary Moore
Research Triangle Institute
Dennis Naugle
Research Triangle Institute
Coleen Northeim
Research Triangle Institute
Philip Nowers
Association of Reproduction Materials
Joseph A. Palmeri
Canon USA, Inc.
Leon J. Przybyla
Underwriters Laboratories
Charles E Rodes
Research Triangle Institute
Michael Romano
Hewlett Packard Company
Betsy Howard
U.S. Environmental Protection Agency
Linda Sheldon
Research Triangle Institute
Dennis L. Stein
3M Company
John Thompson
The Gillette Company
Gene Tucker
U.S. Environmental Protection Agency
Charles Weschler
BellCore
James White
U.S. Environmental Protection Agency
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RECOMMENDATIONS
1. Paper phenol circuit board card. It was suggested that a low emitting substitute for paper
phenol circuit board cards could reduce emissions and would have a broad-based
application in numerous technologies. However, the replacement will need to be
economically feasible or industry will not accept it.
2. Supplies and paper types. In some cases, equipment can be poisoned by the operating
environment (e.g., filters) which should be considered when setting up the models and
testing protocol for this research. The issue of different paper types needs further
investigation (e.g., preprinted paper, carbonless paper, recycled paper). Competitive
supplies should also be considered in the design of any research program. The type of
supplies used can also have a dramatic effect on emissions. One approach for applying
pollution prevention to reduce indoor air emissions from office equipment could be
through modifications of the supplies (e.g., toner, paper).
3. Standard testing methodology. It was strongly recommended that a subcommittee be
formed to devel
4. op a representative test/screening method for evaluating emission from office equipment.
5. Effect on the indoor environment with proper maintenance. In general, emissions tend to
increase with equipment age and the time between maintenance. It was recommended to
look at the issue of maintaining equipment properly and how the lack of maintenance and
proper procedures effect the overall emission rate. A pollution prevention strategy may be
to focus on overall maintenance, changing the ease of maintenance, or changes in
technology which reduce maintenance needs.
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APPENDIX B. Emissions Testing Guidance Document
for Dry-Process Photocopiers
1.0 Scope/Objective
The overall objectives of this cooperative agreement between the Research Triangle
Institute (RTI) and the U.S. Environmental Protection Agency (EPA) are to identify pollution
prevention opportunities for manufacturers and/or users of office equipment and to measure the
effectiveness of proposed pollution prevention actions. This guidance document was developed to
measure emissions from dry-process photocopiers.
Based on triplicate measurements at RTI and on a four-laboratory comparison study with
one copier, it was found that the test method is analytically sensitive and generally applicable to all
types of dry-process photocopiers. This method is intended to characterize emissions and to
support identification of potential pollution prevention strategies. It is intended to promote
uniform testing and research into pollution prevention opportunities rather than to determine
regulatory compliance (i.e., if occupational exposure standards are met).
2.0 Facilities and Equipment
Flow-thorough dynamic test chambers are recommended because they are generally
applicable to all types of equipment, and they provide data that can be compared with other
emission sources and used as inputs for indoor air quality models The major components of a
dynamic environmental test chamber include the chamber, the clean air supply, operational and
control systems, sample collection and analysis equipment, and standards generation and
calibration systems. A schematic of a test chamber is shown in Figure 1 as an example.
Attachment A provides a specific description of the chamber facilities used for this study,
performance characteristics, and guidance on how to demonstrate chamber performance.
Minimum chamber performance requirements are presented in the guidance.
2.1 Chamber Construction - Chambers should be constructed so that the interior surfaces are
smooth, nonadsorbent, and chemically inert to minimize the potential for interior walls to act as
either sinks or sources. Inert surfaces such as electro or Summa polished stainless steel or
aluminum are recommended for this purpose. Other materials (e.g., Tedlar) may be used
provided inertness is demonstrated. Inertness can be demonstrated by conducting recovery
efficiency tests for target analytes. All joints should be permanently sealed (except required
openings) to minimize the potential for leakage. Seals and sealant must be nonadsorbent with
minimal use of caulks and adhesives that may emit or adsorb VOCs. An airtight access door, inlet
and outlet ports for air flow, and temperature and humidity probes are also required. The
chamber's linear dimensions should be a minimum of 1.4 times the dimensions of the product
tested to be consistent with typical industry practice. If multiple machines are used in the test
chamber, the minimum dimensions of the chamber should be 1.4 times the total dimensions of the
equipment tested. The chamber should be designed to operate under positive pressure to
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EXHAUST TO OUTDOORS
Q-N
(2) FAN
|\| DAMPER
INLET
AIR
PRE-
CONDITIONING
DEHUMID-
IFIER
~o
ADSORBER
v I MAIN
\ ^ CONDITIONING "
Figure 1. Schematic of a large test chamber.
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eliminate the infiltration of contaminants from the exterior of the chamber. The air-intake port
and exhaust port should be on different walls of the chamber and at different elevations;
alternative designs are allowed if it can be shown that the chamber is well-mixed (see Section
2.2 Mixing - Mixing is important to ensure that emissions resulting from equipment operation are
accurately measured. Low-speed mixing fans or multiport inlet and outlet diffusers should be
used. The completeness of mixing must be characterized within the chamber. There is currently
no definitive quantitative guidance on completeness of mixing. However, mixing should be
assessed according to the guidelines established in ASTM D5116-90, "Standard Guide for Small-
Scale Environmental Chamber Determinations of Organic Emissions from Indoor
Materials/Products." Mixing should be measured by introducing a tracer gas (e.g., SF6 or CO)
with the inlet air at known concentration, quantity, or flow, and measuring the concentration in
the chamber outlet over time. Examples of two methods for determining mixing both based on
the same equation are described as follows.
The first method is to introduce a constant source of tracer gas into the chamber and then
compare chamber air concentration to a theoretical curve for a completely mixed chamber based
on the equation:
where
C = chamber concentration
C0 = inlet concentration
t = time
N = air exchange rate, calculated as N=Q/V
Q = flow rate through the chamber
and
V = chamber volume
The second approach is to inject or introduce a "slug" of a known quantity of tracer gas
(e.g., CO) into the chamber and measure the decay in concentration. The measured
concentrations must then be compared to the following equation:
where the variables are the same as those defined above.
If the measured data closely approximate the curve (e.g., within 5 %), the chamber may be
considered well mixed. If the measured data lie above the theoretical concentration versus time
curve, the flow is being short circuited, perhaps because of poor placement of the air inlet and/or
outlet ports. If measured data fall below the curve, some of the tracer gas may be adsorbing or
2.2).
C = C0(l - e"Nt)
(1)
ln(C0/C) = Nt
(2)
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absorbing onto the chamber surfaces, the chamber may be leaking, or incomplete mixing may be
occurring. Tests should be conducted, not only on the empty chamber but also with equipment of
the types to be tested, to ensure that the placement of the samples in the chamber will not result in
inadequate mixing.
2.3 Environmental Control Systems - Controls required for air flow, temperature, and humidity,
can be either automated or manual. Specific systems that are required are described in the
following sub sections.
2.3.1 Temperature Control - Temperature within the chamber should be maintained at 26 - 31°C
by conditioning the inlet air. This range is a practical compromise between typical chamber
conditions, (i.e. 23°C) and what is achievable when equipment with a high thermal load is tested.
Temperature should be measured via thermocouples or thermistors and should characterize the
immediate operating environment of the device being tested. Temperature maintenance may be
improved by using a larger chamber (with respect to the equipment tested), if available, to better
dissipate the heat load. The temperature of both the inlet and chamber air should be continuously
monitored and recorded.
2.3.2 Clean Air Generation - The background chamber air concentration must be maintained at or
below detection limits for the target analytes (described in Section 2.5) by using clean inlet air.
The purity of the supply air should guarantee that inlet air is below the minimum detection limits
established for the samples and described in Section 2.5. In general, background air should be
maintained at or below 2.5 ng/m3 for individual volatile organics, 5 ppb for ozone, and 5 ng/m3
(gravmetric) for particulates. Organics and ozone can be removed using charcoal filters, oxidizing
filters, and catalytic oxidizers; high-efficiency particulate air (HEPA) filters can effectively remove
suspended aerosols.
2.3.3 Flow Control - Based on a single-pass system, the air flow rate through the chamber should
be maintained at 45±5.0 m3/h. For a 22m3 chamber that air flow rate is equivalent to
approximately 2 ACH. For some photocopiers, large amounts of heat (up to 24,000 BTU/h) can
be produced during testing. To offset this heat load, air flow rate through the chamber can be
increased from 22 m3/h (equal to 1 ACH for a 22 m3/h chamber) to 45 m3/h (equal to 2 ACH for a
22 m3 chamber).
2.3.4 Humidity Control - Test conditions have been set so that a constant water concentration,
not a constant relative humidity (RH) is maintained in the chamber. Given the target temperature
range of 26° to 31 °C, a RH maintained between 30 and 35 percent corresponds to typical test
conditions of 50% RH at 23 °C. Adjustments in water concentration can be achieved by adding
deionized water or HPLC-grade distilled water to the air stream as steam, injected directly into
the air stream (controlled by the pump setting), or saturated air can be mixed with dry air
(controlling the temperature of the water and flow of saturated air) to achieve the desired
concentration. Water concentration can be measured using several types of sensors, including
dewpoint detectors and thin-film capacitors.
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2.4 Sample Collection System - The chamber design and operation should allow for continuous
equipment operation and sampling of chamber air without violating chamber integrity. The
exhaust flow from the chamber (outlet air stream) may be used as the sampling point or,
alternatively, separate sampling ports in the chamber may be used. Particle collectors and
counters should be located as close as possible to the exhaust port of the copier. External particle
counters must be connected through sample lines designed to minimize losses of particles up to 10
|im. Multiport sampling manifolds can be used for duplicate sampling. All sampling systems that
come in contact with the chamber air prior to collection or measurement should be constructed of
inert materials. For example, ozone must contact only Teflon and glass surfaces. Chamber air
concentrations may be low for many contaminants, requiring larger sample volumes and the use of
integrating sample collection media (e.g., adsorbent).
There are a number of sorbent materials available for the collection of volatile organic
compounds (VOCs). Sorbents are available either singly or in combination (e.g., activated
carbon, glass beads, Ambersorb, Tenax, and XAD-2). Multisorbent sampling tubes are
recommended and the air sample volumes collected for analysis should be based on detection
limits and breakthrough volumes. Sampling flow rates will be determined by total sampled
volume over the desired test period.
Given the reactive nature of aldehydes/ketones, alternative sampling methods to those
used for VOCs are recommended. Aldehydes/ketones should be collected by passing chamber air
through cartridges containing silica gel impregnated with 2,4-dinitrophenylhydrazine (DNPH).
Formaldehyde, as well as other aldehydes and ketones, reacts with the DNPH and is collected on
the cartridge material. To account for the potential interference of ozone with the DNPH
method, it is recommended that a potassium iodide-coated tubular denuder or scrubber be placed
upstream of the DNPH cartridge to remove ozone.
The recovery efficiency must be determined for collection and analysis of each chemical
constituent. Background concentration recoveries must meet designated performance standards
or the analytical data are not acceptable.
2.5 Sample Analysis - The analytical systems used to analyze chamber air concentrations should
be selected based on the physical and chemical properties of the pollutants being analyzed and
must meet the minimum detection limits established in this guidance.
2.5.1 Volatile Organic Compounds - Collected chamber air samples should be analyzed for
organic chemicals to identify and quantitate individual volatile organic compounds (IVOC) and
total volatile organic compounds (TVOC). Gas chromatography/ mass spectrometry (GC/MS)
analysis is required for the identification of unknown IVOCs in chamber air samples. Due to its
selectivity, GC/MS analysis is strongly recommended for quantitative analysis. Detection limits
for both chamber air concentrations and emission rates should be as low as possible to effectively
measure the efficiency of pollution prevention efforts. Target detection limits for chamber air
concentrations are set at 2.5 (ig/m3 (general background for IVOCs in indoor air), levels of
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concern for specific health effects, odor thresholds, or 1% of the threshold limit value (TLV),
whichever is smaller. For TVOC, a target detection limit of 10 ng/m3 has been set. The relatively
low detection limits are necessary to identify the range of individual compounds emitted from
operating dry-process photocopiers.
When sorbent tubes are used for sample collection, the analysis usually is performed by
thermal desorption, focusing, and subsequent injection into a GC/MS system. For qualitative
analysis, components in the GC/MS chromatogram are identified by comparing the mass spectrum
of the sample component to a library reference spectrum (NIH/EPA/MSDC Mass Spectral Data
Base and the Registry of Mass Spectral Data). This is most effectively accomplished using an
electronic database search with manual verification of results. Qualitative results are then used to
select a list of target IVOCs for quantitative analysis. Relative abundance, adverse health effects,
or adverse sensory effects are criteria that are commonly used to select target VOCs.
For quantitative analysis, the GC/MS instrument must be calibrated prior to analysis. This
is done by analyzing sorbent cartridges spiked with known levels of target IVOCs at four to six
different concentrations. During analysis, identification of target IVOCs is based on
chromatographic retention times relative to the standard cartridges and on the relative abundances
for the extracted ion fragment selected for quantitation.
Quantitation of IVOCs is performed using chromatographic peak areas derived from extracted ion
profiles. Relative response factors (RRFs) for each target compound are generated from the
calibration standards as:
RRF =
(AT)(AmtQS)
(AqsKAmti.)
where
Ar = peak area of the quantitation ion for the target IVOC
AqS = peak area of the external standard
AmtT = mass of the target compound on the calibration cartridge
AmtQS = mass of the external standard in the calibration cartridge
These RRF values are then used to calculate the mass of the target IVOC on each cartridge.
TVOC is quantitated using the GC/MS reconstructed ion chromatogram (RIC). The total area of
the RIC is in the retention window from n-hexane to n-tetradecane. The RRF generated for
toluene is often used for quantitating TVOC. Performance requirements for this method are given
in Table 1. This method is the same as EPA Method TOl, except that multisorbent rather than
Tenax cartridges are used. Alternative methods may be used if performance similar to Method
TOl can be demonstrated.
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Table 1. QA/QC Requirements for VOC and Aldehyde Analysis
Pollutant
Measurement
Requirement
VOCs
(Tenax and
multisorbent
method)
Initial demonstration of laboratory capability
• Analysis of 3 laboratory blanks. Acceptance criteria = <5ng of any target VOC and
100 ng of T VOC on cartridges.
• Analysis of 3 laboratory controls spiked at 100 ng for selected VOCs. Acceptance
criteria = recovery of 100 + 25%.
Sample Analysis
• Multipoint calibration (25-500 ng). Acceptance criteria = %RSD of mean relative
response factor <25%.
• Lowest calibration standard within the linear range, signal-to-noise ratio for lowest
standard of 10 to 1.
• Calibration check sample - measured value - 75 to 125% of known value.
Analysis of QC samples per test
• One chamber blank - acceptance criteria = <2.5 |ig/m3 for each specific VOC; <10
Hg/m3 for TVOC.
• One field control - acceptance criteria = recovery of 75 to 125%.
• One duplicate sample collected and analyzed - acceptance criteria = RSD of duplicate
measurement <25%.
Formaldehyde
and other
aldehydes
Blank analysis of 10% of all cartridges before use, acceptance criteria = <50 ng
aldehyde/cartridge.
Initial demonstration of laboratory capability
• Analysis of 3 laboratory blanks. Acceptance criteria = <30 ng aldehyde/cartridge.
• Analysis of 3 laboratory controls spiked at 3 concentrations. Acceptance criteria =
recovery of 100 + 20%.
Sample Analysis
• Multipoint calibration (0.05-20 ng/nl, DNPH-aldehyde derivative). Acceptance
criteria = correlation coefficient >0.995.
• Lowest calibration standard within the linear range, signal-to-noise ratio for lowest
standard of 10 to 1.
• Calibration check sample - measured value - 80 to 120% of known value.
• Every 8 hours of analysis, midpoint check standard, acceptance criteria = measured
concentration within 15% of prepared value.
Analysis of QC samples per test
• One chamber blank - acceptance criteria = <2.5 ng/m3 for each target aldehyde.
• One field control - acceptance criteria = recovery of 80 to 120%.
• One duplicate sample collected and analyzed - acceptance criteria = <25% RSD.
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Aldehyde analysis must be conducted independently of the IVOC analysis. When
aldehydes are collected on DNPH cartridges, the aldehyde/DNPH derivatives are eluted from the
cartridge with 5 mL of acetonitrile. The extract is then analyzed by high performance liquid
chromatography (HPLC) with ultraviolet (UV) detection at 347 nm. Quantitation of target
aldehydes is accomplished by the external standard method using calibration standards prepared in
the range of 0.05 to 15 ng/|iL (ng/mL) of the DNPH/aldehyde derivatives. Target aldehydes will
be identified based on chromatographic retention time of the sample components relative to
calibration standards. Performance requirements for this method are also given in Table 1. This
method is essentially the same as EPA Method TOl 1 (Winberry, 1988). Alternative methods may
be used if similar performance can be demonstrated for the aldehydes of interest.
2.5.2 Ozone - Continuous monitoring of ozone should be conducted with an EPA-designated
equivalent monitor so that a minimum detection limit of 10 ppb is achieved. A monochromic, UV
spectrophotometer specific to ozone can be used for this purpose. Continuous measurements can
be made and the output connected to a data logger for data recording and storage. Particulates
have been shown to interfere with ozone measurement when these continuous monitors are used.
Where particulate levels are high, or where sampling occurs for long periods of time, a (Teflon)
particulate filter can be placed upstream of the ozone monitor. However, using a particulate filter
will typically slow the response of the instrument. Past testing on equipment in chambers has
shown that particulate levels are not expected to interfere with ozone measurements and are,
therefore, not recommended for initial testing. However, a particulate filter may be required if
initial results indicate levels sufficiently high to warrant it.
2.5.3 Particulate/Aerosol - Continuous sampling of aerosols should be conducted at the exhaust
outlet of the copier. Gravimetrically based sampling for PM10 is recommended with the desired
supplement of an optical particle counter to report the emission rate in particles/time for specified
particle size ranges. Particles less than 10 (aerodynamic mass median diameter) are
considered to be those of most concern.
3.0 Test Procedure
3.1 Chamber Preparation - The chamber should be thoroughly cleaned prior to testing.
Background levels of target pollutants in the chamber air should be measured before each test and
should be below the detection limits established for the individual pollutants analyzed. The
chamber should also be purged between runs until the air concentrations of targeted contaminants
are below analytical limits of detection.
3.2 Recovery Tests - A recovery efficiency test for gas-phase contaminants should be conducted in
the empty chamber to determine the potential for wall effects (where a chemical may adhere to
chamber walls, gaskets, or other chamber materials). This test should be conducted by spiking the
chamber with a known amount (e.g., minimum of 10 times the detection limit) of particular pollutants
in the inlet air and measuring the amount of contaminant recovered by the sample analysis.
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Chamber dosing and recoveries can be determined by introducing known amounts (E.J of
toluene, n-decane, formaldehyde, and ozone into the chambers at known rates. Chamber air
samples should be collected and analyzed using procedures identical to those used during the
photocopier emission tests (Section 3.3). The measured amount of pollutant emitted during each
test is calculated as,
En, = CcxVtxA,xT, (4)
where
Em =
the measured amount of target pollutant emitted during each test in ng.
Cc =
the measured chamber air concentration in |ig/m3.
Vc =
the chamber volume in m3.
Ac =
the air exchange rate in h"1.
Ts =
the sample collection time in h.
Percent recoveiy of the emitted pollutant is used to evaluate the accuracy of the emission
test method. Percent recovery, %R, is calculated as:
%R = E^/E^ x 100 (5)
where E^ is the amount measured during the recovery test in ^g, and E^ is the amount that is
introduced into the chamber during the test in ng.
3.3 Overvie»> of Test Procedures-The following steps should be performed for each test once
the chamber has been prepared and recovery tests performed. Detailed information on test
duration (Section 3.3.1) and photocopier preparation, handling, and operation follow (Section
3.3.2):
Step 1. Checkout of copier by service representative;
Step 2. Perform toner depletion/replenishment (Section 3.4);
Step 3. Collect background air samples from empty chamber;
Step 4. Place copier in chamber;
Step 5. Power up copier, load paper and standard test image, and test remote start;
Step 6. Equilibrate copier in chamber overnight in idle mode, i.e., powered but not
copying;
Step 7. Collect integrated chamber air samples for the copier in the idle mode for a
total of anticipated copying time plus a time period equal to 4 air changes;
Step 8. Collect integrated chamber air samples during full copier operation (i.e.,
until paper supply is gone) and continue air sample collection for a post-
copying time period equal to 4 air changes; and
Step 9. Determine air exchange rate during test using pulse injection of a tracer gas
(e.g., carbon monoxide, SF6).
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3.3.1 Test Duration - Steps 7 and 8 above describe the test duration used for this study. The
paragraphs below discuss other alternative approaches that could be used.
The chamber should operate for a sufficiently long initial period to ensure that chamber
equilibrium is reached prior to beginning sampling. In general, 4 air changes are required to
replace 99% of the air in the chamber. For example, based on an ACH of 2.0, about 2 hours is
required. Three alternative approaches can be used.
1. Operate the equipment for 2 hours continuously, at which time sampling could occur and,
with the absence of wall effects, the chamber air concentration is assumed to be in
equilibrium.
2. Operate the equipment for a defined period of time, collecting an integrated sample from
the start of operation until 2 hours (i.e., 4 air changes) after the equipment is turned off.
In the absence of wall effects, this sample should represent about 99% of total emissions
during operation for the chamber used in this study.
3. Take short-term periodic samples throughout the period of operation. This approach
should be used when information on the time course of emissions is required. This option
is useful to determine how emissions change with time of operation.1
Dry-process photocopiers are limited as to the length of time they can operate
continuously (due to paper supply limitations). If the equipment cannot operate continuously for
the 2 hours required for the chamber to reach equilibrium plus the 2 hours required to collect a
VOC sample, then one of the following approaches must be used:
• Multiple machines must operate sequentially so that operation is continuous for the time
period required (2 hours); or
• An integrated sample must be taken from the start of operation until 2 hours after the
cessation of operation.
The latter approach was followed for the testing and evaluation in this study.
3.3.1 Photocopier Preparation. Handling, and Operation - Before testing of the photocopier can
begin, several preparative steps must be addressed. Due to the various designs of photocopiers,
specific instructions for each cannot be described in this text; however, the following provides
general information regarding what issues to address.
The photocopier must be configured for remote start and operation from outside the test
chamber. This will vary depending on the specific model and must be customized for each. This
is best done through discussions with the manufacturer's engineers and field technicians.
Examples of possible approaches include the addition of contact switches that simply start the
'it should be noted that using multisorbent collection media requires a 2-hour sampling period that may not be
appropriate for this alternative. A grab sample using canisters may be more appropriate.
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copier when pressed or removal and extension of the keypads to allow more complete operations.
Also, any timed features such as automatic resets for number of copies must be disabled to allow
remote operation.
To control for toner offgassing and toner carryover, a process of depletion and
replenishment of the toner is required to insure consistent, representative results. This is
especially necessary if the toner cartridge has been changed or if the toner has been in the machine
for a prolonged period of time (greater than 1 month) prior to the test. The specific method for
toner depletion and replenishment is dependent on the particular copier model being tested. Each
copier model must be evaluated individually to determine the appropriate steps for toner depletion
and replenishment based on its toner delivery system. Methods should be developed through
discussions with the manufacturer's engineers and field technicians to prevent damage to the
copier. Toner depletion and replenishment probably is not necessary between tests if only a short
(several days) time passes between tests.
As an example, the following procedure for toner depletion/replenishment was developed
specifically for one of the photocopiers used in this study. To deplete the toner, the toner
cartridge was removed from the copier, and 3500 copies of the standard image were made. As the
toner in the delivery system was depleted, the image became very faint on the paper. To replenish
the toner in the delivery system, a new toner cartridge was inserted into the copier, and 500
copies of the standard image were made. At this point, the copy images appeared uniformly dark.
To verify that the toner had been properly restored, a copy of the manufacturer's test
pattern/image was made and compared against the original. This procedure appeared to be
effective in "flushing" the older toner from the machine, replacing it with toner from the "fresh"
cartridge.
Ideally, a study should yield emission factor estimates for all phases of product operation,
i.e., continuous monitoring of emissions. However, designing a study to accomplish that could be
resource intensive given the number of factors to be considered. Therefore, this method
recommends that the copier be tested while idling (powered up but not operating) and at full
maximum operation to define the maximum emissions. The standard operating conditions
described previously will allow for comparison among various manufacturers. For example, for
image processing machines (i.e., copiers and printers), a standard image (percent coverage) will
be processed that represents a typical maximum image to define worst-case emissions and
exposure. For monochromic machines, a standard image of about 15% coverage is used. The
standard image to be printed or copied on monochromic machines is described in Attachment B.
Manufacturer-recommended supplies should be used including toner and paper. Recycled paper
and toner cartridges can also be used to compare their effect on overall emission rates.
4.0 Data Analysis
4.1 Environmental Data - Environmental data (i.e., temperature and RH) should be recorded
continuously. This can be done by a PC-based system. Summary statistics that describe the
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environmental condition "setpoints" and the actual values achieved (including variability) should
be computed and a data summary sheet prepared.
4.2 Chemical Analysis Data - The environmental information and the chemical analysis results
are combined to give chamber air concentrations for individual compounds. In calculating
concentrations the following factors are considered:
• Chemical analysis system background (including sorbent blanks for sampling cartridge)
• Chamber background
• Sampling time
• Sampling volume
• Mass observed for individual selected organic compounds, ozone , and particulates.
4.3 Chamber Air Concentration - Chamber air concentration for individual pollutants for each
sample are calculated by dividing the mass by the sample volume.
4.4 Emission Factor Calculation - The emission rate (Er^ in the idle mode is calculated
assuming steady-state conditions after the copier has been idling in the chamber overnight.
ERj - [(Cj - Cb) x Vc x AJ/n (6)
where,
ER; = emission rate in the idle mode in jag/h • copier
C; = chamber air concentration in the idle mode in ng/m3
Cb = background chamber air concentration in ng/m3
Vc = chamber volume in m3
= chamber air exchange rate in h"1
n = number of copiers in chamber.
The emission rate of VOCs attributed to printing (ER,.) is calculated using a simple mass
balance equation and applying the following assumptions:
1. There is no reversible or irreversible adsorption of the target organics in the chamber
during the testing period. This is demonstrated to be true through chamber recovery tests.
2. The chamber air is well-mixed. This is demonstrated for each test through the release and
measurement of CO in the chamber air during testing.
3. The chemicals in the chamber are in the vapor phase and uniformly distributed in the
chamber air. This is a property of VOCs.
4. The steady state emissions measured in the idle mode remain constant during the copying
mode. Any changes are considered to result from copying, therefore by definition, a
change will be attributed to printing.
After 4 air changes, 99% of the chamber air is exhausted from the chamber. Under these
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conditions:
where,
ERC
M,
ERc = M/(Tpxn)
emission rate attributed to printing in (j.g/h • copier
total net mass of VOC measured in the chamber air in jag
time the copier was printing in h
(7)
Mt =(CP -Q) x Ta,
(8)
where
Q
T
measures time-integrated chamber air concentration measured during the
chamber test in ^g/m3
chamber air concentration measured during idle mode in |ag/m3
total volume of air that passed through the chamber during testing in m3.
This assumes that the concentration of VOCs in the chamber air attributed to printing can be
estimated by correcting the total concentration measured during the chamber copying experiment
by the concentration measured during the chamber idle experiment.
where
Vc
A,
T,
Tav = Vc x A, x Tc
chamber volume in m3
chamber air exchange rate in h"1
time the sample was collected for in h.
(9)
Equations 4, 5, and 6 are then combined, resulting in the following equation:
ERc = [(CVQ xVcxAcx Tc)] / (Tp x n)
(10)
If time-course data are collected, average emission rates for each time interval are
calculated using the chamber air concentration at that time interval as
ERt = (AC; /AT; + A^,) x Vc / n
(11)
where,
ER,
AC,
AT;
a
emission rate for time interval T in jag/h • copier
change in chamber air concentration for time interval T in (ig/m3
length of time interval T in hours
average measured chamber air concentration for time interval T in ng/m3
For ozone, emission rates are calculated as
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ERo= [(Cc * A,. * Vc)/(1 - e'AcTp)]/n
(12)
where
ERo
Cc
emission rate for ozone in |ig/h • copier
equilibrium chamber air concentration in ng/m3
5.0 Quality Assurance/Quality Control
Standard analysis methods, such as EPA and the National Institute for Occupational
Safety and Health (NIOSH) methods, should be used when available and practical. In all cases,
testing should include meeting existing standards addressing analytical techniques and chamber
operation and calibration, including:
• ASTM D3195 Recommended Practice for Rotameter Calibration
• ASTM D1356 Definitions of Terms Related to Atmospheric Sampling and Analysis
• ASTM E355 Recommended Practice for Gas Chromatography Terms and Relationships
• ASTM D3609 Practices for Calibration Techniques using Permeation Tubes.
The QA/QC procedures described in the methods should be followed. Specific QA/QC activities
for consideration include sample logbook, standard operating procedures, standards preparation
log, calibration logs, instrument maintenance logs, materials testing logs, sorbent cartridge
cleanup/desorption logs, log of electronically stored data, routine maintenance, daily recording of
calibration, timely monitoring and percent recovery of internal and spiked standards, chamber
background determination, duplicate chamber runs and duplicate samples, blanks, methods
detection limit checks, and audit gas analysis.
6.0 Reporting Test Results
The report of the test results should contain the following sections :
• Facilities and Equipment: description of test chambers, clean air system, environmental
measurement and control, sample collection, analytical instrumentation, and standards
generation and calibration;
• Experimental Design: test conditions including temperature, RH, and air exchange rate;
• Sample Descriptions: complete description of product tested;
• Experimental Procedures: procedures used in testing including sampling and analysis;
• Data Analysis: show methods including appropriate models and equations (sample test
data sheet provided in Attachment C);
• Results: chamber air concentrations and emission factor for each type of sample and test
condition (including the detection limits for testing);
• Discussion and Conclusions: discuss relevance and conclusions (e.g., the effect of
equipment cycle or percent coverage on emission rate); and
• Quality Assurance/Quality Control: compare the test data to the data quality objectives.
B-14
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7.0 References
American Society for Testing and Materials. Small-Scale Environmental Chamber
Determinations of Organic Emissions from Indoor Materials and Products, ASTM
Standard Guide D5116-90, Philadelphia, PA, 1990.
American Society for Testing and Materials. Recommended Practice for Rotameter Calibration,
ASTM D3195-94, Philadelphia, PA, 1994.
American Society for Testing and Materials. Practices for Calibration Techniques using
Permeation Tubes, ASTM D3609-96, Philadelphia, PA, 1996.
American Society for Testing and Materials. Recommended Practice for Gas Chromatography
Terms and Relationships, ASTM E355-96, Philadelphia, PA, 1996.
American Society for Testing and Materials. Definitions of Terms Related to Atmospheric
Sampling and Analysis, ASTM D1356-97, Philadelphia, PA, 1997.
Gressel, Michael G. Final Report: Methods for Characterizing Emissions from Laser Printers.
Report No: 211-04. National Institute for Occupational Safety and Health, U.S.
Department of Health and Human Services, Cincinnati, OH, 1996.
Winberry, W.T.; Murphy, N.T., Riggan, R.M. "Compendium of Methods for the Determination
of Toxic Organic Compounds in Ambient Air," EPA/600-4-89/017 (NTIS PB90-127374);
U.S. Environmental Protection Agency, Research Triangle Park, NC, 1988.
B-15
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Attachment A:
Description of Environmental Test Chamber
Size
800 ft3 (22.7 m3), 10 x 10 x 8 ft (3.05 x 3.05 x 2.44 m)
Construction Materials
Ducts: Aluminum
Ceiling/Walls: Aluminum
Floor: Stainless steel
gaskets: Viton®
Air Supply Systems
Outside air passed through particulate filters then through Carasorb 200 filters for
organics removal, followed by HEPA filtration
Temperature Control
65 to 94 + 2 °F (18 to 35 ± 1 °C)
Humidity Control
35 to 70% RI-I, ±5%
Air Exchange Rate
0 air changes to 120 air changes/hour
Sampling Ports
1/4-inch stainless steel Swagelok, adaptable to meet other requirements
Measurement Systems
Temperature/Humidity - General Eastman Model 850
Air Flow - Carrier Comfort Network Distributed Controller
Data Acquisition - 386 PC
Experimental Work to Demonstrate Chamber Capabilities
Purpose
Approach
Acceptance Criteria
Demonstrate acceptable chamber
operation
Air exchange rate validation - air
exchange rate measured in chambers
at 0.2 and 0.5 ACM using SF6 or CO
Air mixing - SF6 measurements
compared to curve
Temperature and RI I - measured
constantly over 8-hour period
Air exchange rate must be within
±10% of specified
SF6 curve must be within 5% of
predicted values
Temperature must be within ±2 °C
Relative humidity must be within ±5%
Chamber background
Measurements taken from chamber air
using the proposed sampling and
analytical methods
Background must be less than 1 ng/m3.
Method quantitation limit estimated as
3xS.D of replicate measurements.
Recovery of constituents
Standards (VOC, formaldehyde) are
introduced into chamber air at 10 to
20 ng/m3 (-10 times estimated
method quantitation limit) over a
4-hour period
Recovery of constituents should be 80
to 120%
B-16
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Attachment B
Description of Test Page
To allow for comparison between machines, a standard test image is recommended. This image was also used
by the National Institute for Occupational Safety and Health* (NIOSI I) as part of their testing program. The page is
described below and a sample test page follows.
Font:
Prestige Elite
Size:
10 point
Lines/page:
54
Character/line:
78
Top Margin:
1 inch
Bottom Margin:
1 inch
Left Margin:
1 inch
Right Margin:
1 inch
Program:
WordPerfect 5.1
See sample on next page.
* Gressel, 1996.
B-17
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Attachment C
TESTING DATA FOR EMISSIONS FROM PHOTOCOPIERS
Test Run:
Determination of Zero
Value
1. Measurement
2. Measurement
Time of Measurement
Date:
From:
To:
Date:
From:
To:
Date:
From:
To:
Temperature (°C)
Average:
Max:
Min:
Average:
Max:
Min:
Average:
Max:
Min:
Humidity (%)
Beginning:
Max:
Beginning:
Max:
Beginning:
Max:
Copier Output/
Measurement Period
Copies
= % Max.
Output
Copies
= % Max.
Output
OZONE
Meter reading
Hg/m3
1. 1 /2 h ave
1. 1 /2 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
Avg (2,3,4)
Avg (2,3,4)
Calculation under
consideration of zero
value
1. 1/2 h avc
1. 1/2 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
Avg (2,3,4)
Avg (2,3,4)
PARTICULATE
Optical particle
counter
particles /min
1. 1 /2 h avg
1. 112 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
2. 1/2 h avg
3. 1/2 h avg
4. 1/2 h ave
Avg (2,3,4)
Avg (2,3,4):
Gravimetric method
Wt of filter + dust =
Wt of filter =
Dust collected=
Vol of air sample =
Dust concentration =
Wt of filter + dust =
Wt of filter =
Dust collected=
Vol of air sample =
Dust concentration =
TOTAL VOLATILE ORGANICS (TVOC)
B-19
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Test Run:
Determination of Zero
Value
1. Measurement
2. Measurement
INDIVIDUAL VOLATILE ORGANIC COMPOUNDS
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
Compound:
B-20
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APPENDIX C. Other Sources of Information
on Indoor Air Emissions from Office Equipment
The following is a list of sources or groups that may be contacted to obtain additional information
related to office equipment, indoor air emissions, and general environmental, health, and safety
issues in the work and home environment.
Blue Angel
(German Eco-labeling program started in 1977. Other counties have similar programs.)
http.V/www. ecomarkt. nt/europe/label/bengel. html
Consumer Product Safety Commission (CPSC)
Washington, DC 20207
Hotline: 800-638-2772
Health Sciences Directorate
301-504-0477
301-504-0051 (fax)
http://www.cpsc.gov
EnviroCenter
(Internet source of information on IAQ information, products and services)
http ://www. envirocenter. com/
EPA's Energy Star Program
(Specifically related to energy efficient office equipment)
U.S. EPA
Mail Code 6202J
401 M Street, SW
Washington, DC 20460
202-233-9114
http://www.epa.gov/docs/appdstar/esoe/index.html
EPA's Indoor Air Quality Home Page
http://www.epa.gov/docs/iedwebOO/index.html
EPA Indoor Air Quality Information Clearinghouse
P.O. Box 37133
Washington, DC 20013-7133
800-438-4318
301-585-9020
http ://www. epa.gov/iaq/iaqinfo. html
C-l
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Green Seal
(Independent non profit org dedicated to protecting the environment by promoting the
manufacture and sale of environmentally responsible consumer products.)
1730 Rhode Island Avenue
Suite 1050
Washington, DC 20036-3101
202-331-7337
http://vAvw.greenseal.org/index.htm
National Institute of Occupational Safety and Health (NIOSH)
(Work environment only)
Technical Information Branch
Mail Stop CI9
4676 Columbia Parkway
Cincinnati, OH 45226
800-356-4674
http://ftp.cdc.gov/niosh/homepage.html
Occupational Safety and Health Administration (OSHA)
Directorate of Technical Support
200 Constitution Ave. N.W.
Rm. N3653
Washington, DC 20210
202-219-7031
http://www.osha-slc.gov/
Technical Association of the Pulp and Paper Industry
(Paper manufacturing industry trade association)
http://www.tappi.org
The IAQ Insider: Home Page
envirovillage.com/newsletters/PureAir/Tdefault.htm
C-2
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APPENDIX D. EPA Quality Assurance Audit of the
RTI and EPA Large Chamber Laboratories
Quality Assurance No.
Audit Type
Audit Date
Research Project
Project Officer
Auditors
Audit Site
Audi tees
Date Issued
RTI AUDIT
Performed by
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
93029/III
Performance Evaluation
January 23, 1997
Application of Pollution Prevention to Reduce Indoor Air
Emissions from Office Equipment
Kelly Leovic
Indoor Environment Management Branch (MD-54)
Shirley J. Wasson,
Jeff Ryan
QA Staff, Technical Services Branch (MD-91)
Paul Groff
Acurex Environmental
RTI Large Chamber
Herbert Building
Research Triangle Institute
Research Triangle Park, NC 27711
Colleen Northeim, Project Leader
Linda Sheldon, Supervisor
Don Whitaker, Test Coordinator
Jeffrey Keever, Analyst
May 1997
D-l
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TABLE OF CONTENTS
Page
1.0 Introduction D-3
1.1 Purpose of Audit D-3
1.2 Audit Preparation D-3
1.3 Audit Activity D-3
2.0 Audit Summary D-4
3.0 Audit Findings D-4
4.0 Conclusions and Recommendations D-6
5.0 References D-6
D-2
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1.0 Introduction
1.1 Purpose of Audit
The U.S. EPA is participating in a research project to identify office equipment which
performs well in the prevention of polluting emissions. Research Triangle Institute (RTI) has
performed the preliminary work of measuring emissions from dry-process office photocopiers
using RTI's large chamber, and writing a generic protocol. The project has progressed to phase II
in which copier QC2 is being round-robin tested in several large chambers using the protocol. RTI
participated in the round-robin by testing copier QC2 in their large chamber in January, 1997.
The independent performance evaluation audit (PEA) tested the ability of project personnel to
measure some of the volatile organic compounds (VOCs) which were emission targets of the
study, using the protocol. A further audit objective was to compare the results of the independent
audits from dissimilar large chambers.
1.2 Audit Preparation
The auditors studied project materials including the phase II QA plan for the round robin
testing entitled Application of Pollution Prevention to Reduce Indoor Air Emissions from Office
Equipment, Phase II: Round-Robin Testing. Arrangements for the audit were made through pre-
audit contact with the project leader and test coordinator. The performance audit was partially
funded through QA WA 3/02 with EPA's on-site contractor, Acurex Environmental, who
identified a certified cylinder containing the specified target VOCs, arranged for recertification by
the commercial vendor, and participated in the audit. Funding for RTI to perform the analysis of
the multisorbent cartridges which were used to trap the audit target compounds was provided by
the QA contract with RTI. Plans for this audit closely followed the plans for the audit of the EPA
large chamber (LC). The equipment used for measurement and delivery of the audit gas included
a mass flow controller, a proper regulator for the cylinder, an electronic flowmeter, a 3-way
stainless steel valve, Teflon tubing, a thermometer, and a stopwatch.
1.3 Audit Activity
The audit was performed on January 23, 1997. To prepare for the audit, RTI provided
multisorbent cartridges containing Tenax and Carboxen 1000 sorbents. The test coordinator
operated the chamber in the same range of temperature, relative humidity, and air exchange rate
as was used for the copier test. Meanwhile the auditors conditioned the regulator and delivery
system with the audit gas (venting it outside the room) and determined the delivery flow rate
using the electronic bubble flow meter. The audit gas, from cylinder ALM057570, containing the
target VOCs, was then released into the chamber for 38 minutes by stopwatch to simulate the
amount of time that the copier operated. The gas was delivered through unheated Teflon tubing
by connection with a Swagelok fitting through a wall port which extended into the chamber 12
inches. During the release, RTI large chamber personnel collected duplicate multisorbent cartridge
samples from the chamber port. Sampling continued for 4 air changes after the release for a total
D-3
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of 158 minutes. After the sampling the cartridges were taken by the RTI test coordinator for
analysis by the RTI project analyst.
A letter report from RTI project personnel was delivered on March 13, 1997. It contained
chamber conditions (see Table 1) and a table containing concentrations and emission rates of the
duplicate samples taken during the chamber release.
Table 1. Process Conditions During the VOC Release as Reported by the Auditees
Condition
Permissible Range
Actual Range
Chamber Temperature
26°C
-------
Table 2. Total Mass VOCs Released into the Chamber
Compound
Reported by
Auditees—
Sample 1
fog)
Reported by
Auditees—
Sample 2
fog)
Calculated
by Auditors
fog)
Recovery-
Sample 1
(%)
Recovery-
Sample 2
(%)
Toluene
5200
5000
3770
138
133
Ethyl Benzene
5400
5300
4370
124
121
m,p-Xylene
10000
10000
8700
115
115
Styrene
3200
3200
4100
78
78
2. The reported values for chamber air concentrations (Table 3) met the
interlaboratory goal for precision, ^25%.
Table 3. Reported Values for Chamber Air Concentrations
Compound
Reported by
Auditees—Sample 1
fog)
Reported by
Auditees—Sample 2
fog)
Relative %
Difference
Toluene
5200
5000
2
Ethyl Benzene
5400
5300
2
m,p-Xylene
10000
10000
0
Styrene
3200
3200
0
3. Due to the lack of information in the report, nothing can be said about actual
conditions during the audit other than the information given in Table 1.
Although planning information was available in the QA plan, not enough was available for
the auditors to achieve on of their audit objectives. They wanted to be able to compare several
specific parameters for each of the chambers during the audit to show that chamber or audit
conditions dissimilarity is not a barrier to achieving comparable results. Nothing is known about
chamber background, blanks, chain-of-custody procedures, calibration procedures, holding time
or storage conditions until analysis, what instrument was used for the analysis, minimum detection
limits, quantitation limits for project samples, any QC samples run with the audit samples, or
actual conditions of sampling (actual rate of sampling and actual sample volume).
D-5
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4.0 Conclusions and Recommendations
The audit showed that RTI's large chamber is adequate to measure the volatile target
analytes of the project. Without calibration, blank, background, or surrogate recovery
information, the auditors cannot determine why toluene was recovered outside of accuracy goal
limits. We recommend that reports of results of performance evaluation audits contain at a
minimum the following information: results of blanks, baseline samples, calibration checks,
surrogate or QC check samples analyzed at the same time as the project samples, holding time and
storage conditions of samples, date of analysis, analysis instrument and conditions, name of
analyst, chain-of-custody information, and actual sampling conditions.
5.0 References
1. Quality Assurance Project Plan, Application of Pollution Prevention to Reduce Indoor
Air Emissions from Office Equipment, Phase IP. Round-Robin Testing, Research Triangle
Institute, October 10, 1996.
D-6
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EPA AUDIT
Performed by
Air Pollution Prevention and Control Division
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
Quality Assurance No. IA03/III
Audit Type Performance Evaluation
Audit Date December 26, 1996
Research Project Application of Pollution Prevention to Reduce Indoor Air
Emissions from Office Equipment
Project Officer Kelly Leovic
Indoor Environment Management Branch (MD-54)
Shirley J. Wasson
Jeff Ryan
QA Staff, Technical Services Branch (MD-91)
EPA Large Chamber
Indoor Emissions Management Branch
U.S. EPA Environmental Research Center
86 T.W. Alexander Drive
Research Triangle Park, NC 27711
Betsy Howard, Project Leader, U.S. EPA
Andy Kegl, SEE Employee
Ivan Dolgov, SEE Employee
U.S. EPA Environmental Research Center
86 T.W. Alexander Drive
Research Triangle Park, NC 27711
May 1997
Auditors
Audit Site
Auditees
Date Issued
D-7
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TABLE OF CONTENTS
Page
1.0 Introduction D-9
1.1 Purpose of Audit D-9
1.2 Audit Preparation D-9
1.3 Audit Activity D-9
2.0 Audit Summary D-10
3.0 Audit Findings D-ll
4.0 Discussion D-ll
5.0 Conclusions and Recommendations D-12
6.0 References D-12
D-8
-------
1.0
Introduction
1.1 Purpose of Audit
The U.S. EPA is participating in a research project to identify office equipment which
performs well in the prevention of polluting emissions. Research Triangle Institute has performed
the preliminary work measuring emissions of dry-process office photocopiers and writing a
generic protocol. The project has progressed to phase II where copier QC2 is being round-robin
tested in several large chambers using the protocol. The EPA large chamber (LC) laboratory
operated by the Indoor Emissions Measurement Branch (IEMB) of APPCD is participating.
Copier testing was performed in December, 1996. The performance evaluation audit (PEA)
independently tested the ability of project personnel to measure some of the volatile organic
compounds (VOCs) which were emission targets of the study using the protocol.
1.2 Audit Preparation
The auditors studied project materials including the phase II QA plan for the round robin
testing entitled Application of Pollution Prevention to Reduce Indoor Air Emissions from Office
Equipment, Phase II: Round-Robin Testing, and the draft and final Dry-Process Photocopier Test
Plan. The auditors were also familiar with the approved manual which details every operation of
the LC facility. One of the auditors met with IEMB and contractor personnel to determine
appropriate audit target compounds and expected concentration ranges. The performance audit
was funded through QA WA 3/02 with the on-site contractor, who identified a certified cylinder
containing the specified target VOCs, and arranged recertification by the commercial vendor. The
contractor also performed the analysis of the multisorbent cartridges which were used to trap the
audit target compounds. The other auditor designed and produced the setup for the performance
audit. The equipment included a mass flow controller, a proper regulator for the cylinder, an
electronic flowmeter, a 3-way stainless steel valve, Teflon tubing, a thermometer, and a
stopwatch. An audit plan was prepared.
1.3 Audit Activity
The first attempt to perform the audit occurred on 12/23/96. Due to a miscalculation by
one of the auditors, not enough VOC audit gas was released into the chamber to provide a
measurable concentration. The collected samples were scrapped, and the audit was rescheduled
for 12/26/96.
To prepare for the audit, LC personnel obtained properly quality-controlled multisorbent
cartridges from the contractor analytical personnel. They operated the chamber in the same range
of temperature, relative humidity, and air exchange rate as was used for the copier test. These
conditions are given in Table 1. Having flushed the chamber during the previous two days, they
performed background testing by taking duplicate background VOC samples from the chamber
D-9
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port and chamber exhaust for analysis. They also sampled the background with the Xontech
analyzer. They determined air exchange rate by injecting a known amount of sulfur hexafluoride
(SF6) into the chamber and analyzing it using a B & K analyzer. Meanwhile the auditor
conditioned the regulator and delivery system with the audit gas (venting it outside the building)
and determined the delivery flow rate using the electronic bubble flow meter. The audit gas from
cylinder ALM057570 containing the target VOCs was then released into the chamber for 38
minutes by stopwatch to simulate the amount of time that the copier operated. The gas was
delivered through unheated Teflon tubing by connection with a Swagelok fitting through a wall
port which extended into the chamber 15 inches. During the release, LC personnel collected
duplicate multisorbent cartridge samples from the chamber port, duplicate samples from the
exhaust, and continued the Xontech measurements. Sampling continued for 4 air changes after
the release for a total of 197 minutes. After the sampling the cartridges were stored in an IEMB
freezer until analysis. Process and sampling data were collected in bound laboratory notebooks
and on data sheets.
Table 1. Process Conditions During the VOC Release as Recorded by Auditor
Condition
Permissible Range
Actual
Chamber Temperature
25.5°C
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3.0 Audit Findings
1. LC project personnel recovered all of the target compounds except styrene within
the data quality goals of 75 to 125%.
The auditors compared the total mass injected as calculated by project personnel with the
total mass injected as calculated by audit personnel using the recertified audit cylinder
concentrations. The results are given in Table 2.
Table 2. Total Mass VOCs Releasee
into the Chamber
Compound
Reported by
Auditees—
Exhaust (mg)
Reported by
Auditees—
Chamber (mg)
Calculated
by Auditors
(mg)
Recovery-
Exhaust
(%)
Recovery-
Chamber
(%)
Toluene
3.845
3.972
3.74
104
106
Ethyl Benzene
4.657
4.765
4.33
108
110
m,p-Xylene
9.190
9.368
8.62
107
109
Styrene
2.91
2.97
4.06
72
73
2. The exhaust background sample was not analyzed. The blank sample was analyzed
and reported as the exhaust background.
Lack of chain-of-custody (COC) documentation may have contributed to the
miscommunication between LC personnel and contractor personnel regarding the identity of the
samples which were required to be analyzed. Chamber personnel usually provided COC
documentation, but COC sheets were temporarily not available on audit day. ID 2560 was
reported as chamber exhaust by analytical laboratory personnel, but in fact was the blank sample.
The exhaust background is not known for the audit.
4.0 Discussion
The results for styrene were slightly below QA goals. This loss may be the result of
sticking to delivery vehicles or LC surfaces, or failure to desorb from the multisorbent tubes.
There are some discrepancies among the data and summary sheets. For instance, the
sample volume of the chamber release sample is reported as 4035 mL on page 3 and 4038.5 mL in
the first Analytical Results table. Sample ID 2560 is listed as exhaust background in the first
Analytical Results table, as a blank in the sample identification table on page 3, as a blank in the
reproduced laboratory notebook page on page 4, and as exhaust background in "Table 1.
Analytical Results", on page 8. Fortunately the sample confusion did not materially alter the result
D-ll
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of the audit, but it may have been prevented by the LC's usual COC documentation procedures.
5.0 Conclusions and Recommendations
The audit shows that LC personnel are providing excellent measurement capability for
VOC emissions measurement. We recommend validating styrene measurement if it is considered
an important target compound for this project.
We recommend keeping a good supply of COC documents on hand to ensure clear
communication between project and analytical laboratory personnel.
6.0 References
1. Quality Assurance Project Plan, Application of Pollution Prevention to Reduce Indoor
Air Emissions from Office Equipment, Phase II: Round-Robin Testing, Research Triangle
Institute, October 10, 1996.
2. E.M.Howard, Dry-Process Photocopier Final Test Plan, December 6, 1996.
3. Facility Manual, Large Indoor Air Quality Environmental Test Chamber, Revision IV,
approved November 18, 1996.
D-12
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before comple
1. REPORT NO. 2.
EPA-600/R-98-080
3.
4. TITLE AND SUBTITLE
Indoor Air Emissions from Office Equipment: Test
Method Development and Pollution Prevention
Opportunities
5. REPORT DATE
July 1998
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
C.Northeim, L.Sheldon, D.Whitaker, B.Hetes, and
J. Calcagni
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. O. Box 12194
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
CR 822025
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Air Pollution Prevention and Control Division
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final: 10/93 - 12/97
14. SPONSORING AGENCY CODE
EPA/600/13
16.supplementary NOTES APPCD project 0fficer is Kelly W. Leovic, Mail Drop 54, 919/
541-7717.
i6. abstract rep0rf- describes the development and evaluation of a large chamber
test method for measuring emissions from dry-process photocopiers. The test
method was evaluated in two phases. Phase 1 was a single-laboratory evaluation at
Research Triangle Institute (RTI), using four mid-range dry-process photocopiers.
Phase 1 results indicate that the test method provides acceptable performance for
characterizing emissions, adequately identifies differences in emissions between
machines both in compounds emitted and their emission rates, and is capable of
measuring both intra- and inter-machine variability in emissions. Toners appear to
be the primary source of organic emissions from the photocopiers. To investigate
whether all chambers produce similar results, a four-laboratory round-robin evalua-
tion of the test method was performed in Phase 2. A single dry-process photocopier
was shipped in turn to each of four laboratories along with supplies (i.e., toner and
paper). Phase 2 results demonstrate that the test method was used successfully in
the different chambers to measure emissions and that differences in chamber design
and construction appear to have minimal effect.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Emission
Photocopying
Office Equipment
Organic Compounds
Pollution Prevention
Stationary Sources
Indoor Air
Toners
13 B
14 G
14E
15E
07C
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
193
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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