United States Environmental Protection Agency National Risk Management Research Laboratory Cincinnati, OH 45268 Research and Development EPA/600/SR-98/080 August 1998 Project Summary Indoor Air Emissions from Office Equipment: Test Method Development and Pollution Prevention Opportunities Coleen Northeim, Linda Sheldon, Don Whitaker, Bob Hetes, and Jennifer Calcagni The report describes development and evaluation of a large chamber test method for measuring emissions from dry-process photocopiers. Application of the test method will lead to a better understanding of emissions from of- fice equipment and to the development of lower emitting machines. Challenges and complications encountered in de- veloping and implementing the test 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 require- ments that may require changes in chamber electrical supply; and remote starting of the machines, which is nec- essary to maintain chamber integrity. The test method was evaluated in two phases. Phase I was a single labo- ratory evaluation at Research Triangle Institute (RTI) using four, mid-range, dry-process photocopiers. Phase I re- sults indicate that the test method pro- vides acceptable performance for characterizing emissions, adequately identifies differences in emissions be- tween machines both in compounds emitted and their emission rates, and is 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 are: ethylbenzene (28,000 ug/hour), m,p-xy- lenes (29,000 ug/hour), o-xylene (17,000 |jg/hour), 2-ethyl-1-hexanol (14,000 ug/ hour), and styrene (12,000 uxj/hour). Al- though 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 photo- copiers. To investigate whether all chambers produce similar results, a four-labora- tory, round-robin evaluation of the test method was performed in Phase II. A single, dry-process photocopier was shipped in turn to each of four labora- tories along with supplies (i.e., toner and paper). Phase II results demon- strate that the test method was used successfully in the different chambers to measure emissions and that differ- ences in chamber design and construc- tion appear to have minimal effect. This Project Summary was developed by the National Risk Management Re- search Laboratory's Air Pollution Pre- vention and Control Division, Research Triangle Park, NC, to announce key find- ings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction Emissions from office equipment include: volatile organic compounds (VOCs), alde- hydes/ketones, ozone, and particles. Ex- posure to these chemicals can contribute to health effects such as eye, nose, and respiratory system irritation, and several are listed as hazardous air pollutants un- ------- der the Clean Air Act (e.g., styrene, ethylbenzene, m,p-xylene, o-xylene, tolu- ene, and formaldehyde). In March 1994, a group of technical advisors met to discuss research on pol- lution prevention approaches for reducing indoor air emissions from office equip- ment and to solicit input on technical pri- orities for the research. The technical advisors strongly recommended that a test method be developed that could be used to evaluate emissions from office equip- ment. It was felt that such a method is needed to evaluate different equipment types and to establish comparable baseline emission data that could be used as a starting point for the development of spe- cific pollution prevention approaches. Con- currently with the technical advisors meeting, a literature search was conducted to identify and review published informa- tion on office equipment design; indoor air emissions of ozone, particulates, and or- ganics; and potential pollution prevention approaches for reducing these emissions. Based on the literature review and on input provided by the technical advisors, this research focused on development and evaluation of a large chamber test method for measuring emissions from dry-process photocopiers. EPA's objective in develop- ing the test method is to promote emis- sion testing of office equipment by manufacturers and others in order to in- crease understanding of emissions and encourage the development and manu- facture of lower emitting equipment. Overview of Test Method Research Triangle Institute (RTI) and EPA's Air Pollution Prevention and Con- trol Division collaborated with several of- fice equipment manufacturers to develop the large chamber test method. It is based on the experience of RTI and EPA in product testing, a published American So- ciety of Testing and Materials (ASTM) test method, and existing test methods used by the participating manufacturers of of- fice equipment. The test method utilizes large, flow-through dynamic chambers be- cause they are generally applicable to all types of equipment and can be used to mimic typical use conditions found in an office. Listed below are some unique con- siderations that are incorporated into the test method. 1. Chamber Size: The test chamber's linear dimensions must be a mini- mum of 1.4 times the dimensions of the equipment tested in accordance with typical industry testing proce- dures. 2. Heat Generation: To account for heat generation, a temperature range of 28.5 + 2.5° C and an air exchange rate of 2 air changes per hour (ACH) are specified. Relative humidity (RH) within the chamber is to be main- tained at 30-35%. (A RH of 35% at 31° C represents a mass of water equivalent to 50% RH at 23° C.) 3. Limited Paper Supply: A finite paper supply for copy machines limits test duration. For this study, a paper sup- ply of 2000 sheets was used for each test. 4. Remote Starting: Remote starting of the machines from outside of the chamber is necessary to maintain chamber integrity. 5. Toner Carryover: When testing equipment that uses toner, a toner depletion and replenishment proce- dure is to be followed to avoid carryover of the previous toner be- tween tests. Without the toner deple- tion/replenishment, toner from a new cartridge may be diluted by the toner still retained in the delivery system or the "old" toner may off-gas be- tween tests, affecting emission re- sults. The sequence of operations below was performed for the testing. Appendix B of the report presents a complete descrip- tion of the test method. 1. Check out copier (by service repre- sentative); 2. Perform toner depletion/replenish- ment; 3. Collect background air samples from empty chamber; 4. Place copier in chamber; 5. Power up copier, load paper, and test remote start; 6. Equilibrate copier in chamber over- night in idle mode (i.e., powered but not copying); 7. Collect integrated chamber air sample for the copier in the idle mode for a total of the estimated copying time plus a time period equal to 4 air changes (i.e., for a chamber oper- ating at 2 ACH, the total idle period sample collection time is the copy- ing time plus 120 minutes); 8. Collect integrated chamber air sample during full copier operation and continue for a post-copying time period equal to 4 air changes (i.e., for a chamber operating at 2 ACH, the total sample collection time is the copying time plus 120 minutes); and 9. Determine air exchange rate using pulse injection of a tracer gas (e.g., carbon monoxide) during the test. In this study, toner recommended by the manufacturer and the same type of paper (containing 25% recycled materi- als) were used. A standard image, repre- senting about 15% coverage of the paper, was used to represent a typical maximum image for copying. For the copiers evalu- ated in this study, 2000 copies were pro- duced for each test. Copying time for the 2000 sheets ranged, depending on the machine, from 20 to 40 minutes, for a total sample collection time of 140 to 160 minutes. Chamber air concentrations of VOCs were determined using multisorbent tubes analyzed by a gas chromatograph/ mass spectrometer (GC/MS). Aldehyde/ ketone samples were collected on 2,4- dinitrophenylhydrazine (DNPH)-coated silica gel cartridges and analyzed by high performance liquid chromatography. At RTI, ozone was monitored continuously using a DASIBI monitor. Limited particle measurements were made using a LAS-X optical particle counter. Evaluation of the Test Method The test method was evaluated in two phases: I) four, dry-process photocopiers were evaluated in RTI's chamber; and II) a round-robin evaluation of one dry-pro- cess photocopier was done in four differ- ent laboratories (including RTI). Results of triplicate measurements made in Phase I show that the test method provides ac- ceptable performance for characterizing emissions from copiers. Percent recovery for calculated emission rates for standard materials released into the chamber at known rates was greater than 85%. Preci- sion of replicate tests using both standard emitters and copiers was good, with less than 10% Relative Standard Deviation (RSD). The data were also analyzed to deter- mine differences in emissions between the four copiers (Table 1). Emissions of VOCs were consistently lower for Copier 3, which used a mono-component toner, than for the three machines that used dual-com- ponent toners (Copiers 1, 2, and 4). How- ever, emission rates for many of the aldehydes and ketones were higher for Copier 3. Also, ozone levels for Copier 3 were higher than for the other three ma- chines. The data show that, although the same compounds were emitted from all four machines, the emission rates of these compounds varied considerably between machines. For example, the emission rate for ethylbenzene was 28,000 |ig/h for Copier 1 and <50 |ig/h for Copier 3. Lim- ited particulate data were collected for two of the four machines tested. Results show that operation of one of the machines increased particulate levels to 30 times chamber background levels for particles smaller than 0.2 :m in diameter. ------- Table 1. Estimated VOC, Aldehyde/Ketone, and Ozone Emission Rates from Four Copiers. (|ig/h • copier) Chemical Copier 1 Copier 2 CopierS Copier 4 ethylbenzene m,p-xylene styrene o-xylene propylbenzene 2-ethyl-1-hexanol n-nonanal formaldehyde acetaldehyde acetone benzaldehyde ozone 28,000 29,000 9,900 17,000 790 230 1,100 <500 710 2,000 1,800 3,000 2,400 6,100 12,000 4,500 2,100 14,000 3,600 2,600 960 <500 2,600 4,700 <50 100 300 <50 <50 130 2,000 2,200 1,200 2,800 <100 7,900 360 510 3,000 850 460 5,600 3,900 <500 <500 <100 3,800 1,300 To investigate whether all chambers pro- duce similar results (results may vary due to differences in sink effects, for example), a round-robin evaluation of the test method was performed in four U.S. laboratories during Phase II. To establish a common basis for comparison, a single, dry-pro- cess photocopier was shipped to each laboratory in turn along with supplies (i.e., toner and paper). The tests followed the same methodology used in Phase I with one exception: a procedure for toner deple- tion/replenishment was developed for the copier in the round-robin testing. As dis- cussed above, without the depletion/re- plenishment process, off-gassing from a toner cartridge left in the copier for an extended time period prior to testing (at least 1 month for these tests) would affect emissions during subsequent testing. The round-robin evaluation demon- strated that differences in chamber design and construction had minimal effect on results. Excluding problems with suspected analytical bias observed from one of the laboratories, measurement agreement be- tween laboratories is excellent for VOCs, with RSDs of less than 10% in most cases. More variability was observed between laboratories for aldehydes/ketones (RSD of 20% for formaldehyde). Ozone emis- sion rates between three of the laborato- ries were consistent (RSD of 15%), but emission rates measured at the fourth laboratory were much higher. Particle mea- surements were not a focus of the study because of the complexity of generating known masses of particles (which would be required for method evaluation). Conclusions and Recommendations Conclusions and recommendations are included for both Phase I and Phase II. Phase I Results of Phase I testing provided valu- able information on the performance of the test method and the emissions char- acteristics of dry-process photocopiers. The large chamber test method devel- oped as part of this project provides ac- ceptable performance for characterizing emissions from dry-process photocopy machines. 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. A standard test method for measuring indoor air emissions from office equip- ment can present numerous challenges and complications. Specific considerations identified and addressed during this study are: heat generation, limited paper sup- ply, power requirements, remote starting, and toner depletion and replenishment. Although many of the same compounds tended to be detected in emissions from each of the four photocopiers, the relative contribution of individual compounds var- ied considerably between machines, with differences greater than an order of mag- nitude for some compounds. The varia- tion in compounds is most likely due to different toner formulations and/or toner manufacturing processes. Many of the compounds detected in this study (benzaldehyde, ethylbenzene, nonanal, ozone, styrene, and xylenes) are consistent with compounds identified in the literature from photoimaging equip- ment. Again, any variation in compounds is most likely due to the different toner formulations used for different machines. The integrated sampling approach for generating emission rate data was deter- mined to be acceptable. Time-point samples were evaluated for two machines. However, it is more labor-intensive and costly; thus, the need for collecting time- point samples should be evaluated on a case-by-case basis. Toner headspace testing indicates that increased temperatures result in increased organic concentrations in the headspace gas. Results from the toner headspace analysis also indicate 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. Toner lot, manufacturing process, and age (as measured by the amount of time that a cartridge has been opened) have 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. Phase II Results obtained from different cham- ber facilities are comparable. The VOCs reported to have the highest emission rates by all of the participating laboratories are ethylbenzene, o-, m-, p-xylenes, and sty- rene. These are also the compounds with the highest emission rates reported from Phase I testing. Excluding problems with analytical bias as seen from one laboratory, agreement between laboratories for VOC measure- ments is excellent (RSD of less than 10% in many cases). Aldehyde/ketone and ozone emission rates are more variable. Differences in chamber design and con- struction at the different laboratories seemed to have little effect on test re- sults. However, an analytical bias was identified at one of the laboratories based on the analysis of duplicates at RTI. Potential Pollution Prevention Opportunities Potential opportunities for reduced emis- sions from office equipment, specifically, dry-process photocopiers, were identified from the literature, discussions with manu- facturers, and tests conducted as part of this research. The use of charged roller systems de- creases ozone emissions; however, the charged roller system presently has copy rate limitations. Therefore, it is recom- mended that future research focus on in- vestigating the application of this design change to higher throughput machines. Both the literature and laboratory test- ing indicate that the greatest level of or- ganic emissions from dry-process photocopiers comes from the toner during the operating mode. As a corollary, higher temperatures were shown to result in higher organic emissions during toner headspace tests. Therefore, additional pol- lution prevention research should focus on the relationship between toner formu- lation and the fusing process. Specifically, this could include: ------- investigating the relationship between fusing temperature and time in con- tact with the fusing rollers; testing of designs that use only pres- sure fusing; evaluating specific differences be- tween 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 reformu- lation and the use of high purity raw materials; and • evaluating other toner/fuser combi- nations, such as ultraviolet (UV)-cur- ing technologies, that are being used by other sectors of the printing in- dustry. This research indicates that emissions can vary depending on the specific toner manufacturing process. The extrusion pro- cess for manufacturing toner should be investigated further. As one measure for ensuring that multimedia pollution preven- tion is being achieved, specifications should be refined to ensure consistent and "clean" raw materials for the toner manufacturing process. Photocopier emissions have been shown to increase between routine main- tenance 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. C. Northeim, L Sheldon, D. Whitaker, B. Hetes, and J. Calcagni are with Research Triangle Institute, P.O. Box 12194, Research Triangle Park, NC 27709. Kelly W. Leovic is the EPA Project Officer (see below). The complete report, entitled "Indoor Air Emissions from Office Equipment: Test Method Development and Pollution Prevention Opportunities," (Order No. PB98-165137; Cost: $36.00, subject to change) will be available only from National Technical Information Service 5285 Port Royal Road Springfield, VA22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at Air Pollution Prevention and Control Division National Risk Management Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 Official Business Penalty for Private Use $300 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 EPA/600/SR-98/080 ------- |