The Getty Conservation Institute
University of Glasgow

Cecily Grzywacz
Amy Taketomo
Dusan Stulik
Norman Tennent
Period of Activity: 8/86 to 2/90

Project Description
For some decades, carbonyl compounds and organic acids have been recognized in the museum world as corrosive agents for lead objects, leaded bronzes, ethnographic objects, and a variety of other materials. These pollutants can be generated from materials used in storage areas and in the construction of display cases, such as particle board. Measurements have been sporadic and not quantitative. This was mainly due to the lack of an appropriate and accurate technique for the determination of low concentrations (parts per billion) of these pollutants. The technical development of High Performance Liquid Chromatography has provided a method for the measurement of these pollutants at the ppb level.

This research activity was designed to monitor the concentrations of carbonyl compounds and organic acids in a series of museums in Southern California, and in display cases, open galleries, and storage.

Major Findings
Expertise was transferred and a major museum survey undertaken. The following trends were determined. For [formic acid], the majority of sites (95%) had concentrations less than 5 parts per billion (ppb), 12 fell between 5-10 ppb, and only 6 had concentrations greater than 10 ppb. For [acetic acid], 80% of the samples taken were less than 10 ppb. For [formaldehyde], the spread was greater but still, 80% fell below 10 ppb. And lastly, for [acetaldehyde], 89% of the cases showed concentrations less than 10 ppb. For these values the trends were that concentrations appeared in the following order: display cases > storage > galleries.

Primary Publications
Druzik, C. M., and A. Taketomo, "Standard Operating Protocol: Analysis of Airborne Aldehydes, Ketones, and Carboxylic Acids with HPLC," Final Report to the Getty Conservation Institute, October 1988.

ABSTRACT-A standard operating protocol (SOP) has been developed for the measurement of low concentrations (ppb) of aldehydes and ketones in air. The method involves sampling with small C18 cartridges impregnated with a selective reagent, 2,4-dinitrophenylhydrazine. The carbonyl-2,4-dinitrophenylhydrazones thus formed are eluted from the cartridges with acetonitrile. They are separated and quantified by High Performance Liquid Chromatography (HPLC) using a photodiode array UV-Vis detector. Identification of components is based upon comparison of their retention times and ultraviolet-visible spectra with those of standards. Quantitation is obtained from peak area versus concentration calibration curves.

Grzywacz, C. M., "Indoor Air Quality in Museums," WAAC Annual Meeting, Tucson, Arizona, November 2-4, 1987.

ABSTRACT-Indoor-generated aldehydes, ketones, and carboxylic acids have long been recognized to be corrosive to metal and ethnographic objects. As the cost of natural wood products increases, so does the use of wood products in the construction of display cases, temporary exhibition supports, storage cases, and crating. The (Conservation at the Getty) Institute has an extensive environmental research program, part of which is a survey of the indoor air quality of eleven museums, two historical buildings, and several libraries. Air samples are taken from galleries, storage areas, and display cases; the concentration of airborne pollutants, (e.g., formaldehyde, acetone, and formic acid ) are determined. The results of the research to date are presented.

Druzik, C. M., D. Grosjean, A. Van Neste, and S. S. Parmar, "Sampling of Atmospheric Carbonyls with Small DNPH-Coated C18 Cartridges and Liquid Chromatography Analysis with Diode Array Detection," International Journal of Environmental Analytical Chemistry, Vol. 38, 1990, pp. 495-512.

ABSTRACT-Carbonyls in air are sampled using small DNPH-coated C18 cartridges and analyzed by liquid chromatography with diode array detection. Carbonyl structure confirmation is obtained by comparing diode array spectral scans of samples to the UV-vis spectra (190-600 nm) of some 20 carbonyl hydrazones recorded in the CH3CN-H2O eluent used for LC analysis. Analytical detection limits are 0.09-3.4 nanograms carbonyl and correspond to 0.14-1.24 ppb in 60 L air samples. Accuracy and precision are evaluated. Excellent agreement was obtained in an interlaboratory comparison that included hydrazone standards as well as museum air samples.

Cartridge collection efficiency has been tested over a range of conditions (sampling flow rate, volume of air sampled, presence of copollutants including photochemical oxidants) and is >0.95 for monofunctional carbonyls, unsaturated carbonyls, and alpha dicarbonyls. Carbonyl recovery by cartridge elution is >0.99 for all carbonyls tested. Examples of applications are given in the fields of atmospheric chemistry, indoor air pollution in museums, and outdoor air quality.

Druzik, C. M., D. C. Stulik, and F. Preusser, "Carbonyl and Carboxylic Acid Pollutants in the Museum Environment," Paper presented to the American Chemical Society Meeting, Division of Environmental Chemistry, Miami, Florida, September 10-15, 1989.

ABSTRACT-For many years volatile carbonyls and organic acids have been recognized in the museum world as corrosive pollutants damaging to cultural objects. These pollutants are often emitted from materials used to build protective and aesthetic environments of displayed or stored cultural objects. To study the presence of carbonyl and organic acid pollutants in the museum environment, an analytical protocol for measurement of ppb levels of pollutants has been developed. The method is based upon dynamic sampling with chemically modified solid-phase extraction cartridges and reverse-phase HPLC in combination with diode array detection. The protocol gives precise and accurate analytical data and the ability to qualitatively screen pollutant mixtures.

The analytical protocol was tested in the laboratory and applied to a field survey of airborne carbonyl and carboxylic acid pollutants in the museum environment. Statistical treatment of data collected during the survey has demonstrated the concentration dependence of these pollutants in the museum environment with respect to the materials used, the type of museum collection as well as the type of ventilation and environmental control in the museum.

Druzik, C. M., D. C. Stulik, and F. Preusser, "Carbonyl and Organic Aid Pollutants in the Museum Environment," Paper presented to the Objects Specialty Group, American Institute for Conservation Annual Meeting in Richmond, Virginia, 1990.

ABSTRACT-For several decades carbonyl compounds and organic acids have been recognized in the museum world as corrosive agents for lead objects and a variety of other materials. Prior to the present study, most measurements of concentration of carbonyl compounds and organic acids in the museum environment have been sporadic and not always quantitative. The development of high performance liquid chromatography and the development of techniques for simultaneous measurement of concentrations at the parts per billion (ppb) level of carbonyl compounds and low molecular weight carboxylic acids in air, has provided the tool for systematic study of these pollutants.

Sixteen institutions participated in the present study of carbonyl and organic acid pollutants. Participating institutions are located in Southern California, New York, Boston, and Honolulu. The selection of institutions included a broad range of different museum architecture types and museum collections. The museums' environments varied from open structures without environmental control to museums with highly sophisticated heat, ventilation, and air conditioning systems.

Over 500 samples from 183 sites at the sixteen institutions were collected. The concentrations detected ranged from 1 to 200 ppb. In the majority of the locations sampled, the concentrations were less than 10 ppb; however, there were a significant number of sites with high concentrations of carbonyl compounds. Samples were collected from four general areas or site types: galleries, storage areas, storage cabinets, and display cases. Concentration trends between pollutant pairs were detected acetic acid was higher than formic acid, acetaldehyde was higher than acetic acid, formaldehyde was higher than formic acid, and formaldehyde was higher than acetaldehyde.

Druzik, C. M., and D. C. Stulik, "Formaldehyde: Detection and Mitigation," WAAC Newsletter, Vol. 13, Nš 2, May 1991, pp. 13-16.

ABSTRACT-A detailed description is presented of the testing and validation studies employed in identifying a passive sampling device for the detection of indoor formaldehyde in museums. The best device capable of formaldehyde detection in the parts-per-billion range was found to be the GMD 570 series formaldehyde dosimeter. Mitigation of formaldehyde was also demonstrated using a small pump with an attached activated carbon cartridge.

Grzywacz, C., "Indoor Pollutants: Detection and Mitigation," Invited Speaker, Western Association of Law Librarians 1991 Annual Meeting, Salt Lake City, Utah, October 25, 1991.

ABSTRACT-None available.

Stulik, D. C., and C. M. G. Druzik, "Carbonyl Pollutants in the Museum Environment: Object Damage and Mitigation," ARAAFU 3rd International Symposium on Preventive Conservation, Paris, October 1992.

ABSTRACT-Indoor air pollutants identified in the (Conservation at the Getty) Institute's survey of carbonyl pollutants in the museum environment can create corrosive environments which may lead to the damage of objects. This study investigates the effects of low concentrations of formaldehyde on inorganic and organic materials. Furthermore, the survey of carbonyl compounds in the museum environment has shown that relatively high concentrations of these pollutants may be encountered in closed spaces such as storage cabinets and display cases. Use of pollutant outgassing materials or a breach of the proper technological regimes were identified as major sources of these pollutants. To mitigate a presence of carbonyl and carboxylic acid pollutants in places where the pollutant source cannot be removed we have developed and tested a so-called Pollutant Eliminator. Description of designing criteria, testing procedures, and use of the Pollutant Eliminator was discussed in detail.

Druzik, C. M. G., and D. C. Stulik, "Carbonyl Pollutants in the Museum Environment: Detection and Museum Survey," ARAAFU 3rd International Symposium on Preventive Conservation, Paris, October 1992.

ABSTRACT-See abstract of citation above.

Metro, B., and C. M. G. Druzik, "A Showcase for Preventive Conservation," ARAAFU 3rd International Symposium on Preventive Conservation, Paris, October 1992.

ABSTRACT-The paper will present a variation of the typical museum showcase, wooden base with acrylic vitrine, developed at the J. Paul Getty Museum. The case design is simple in construction and modest in cost, appropriate for the small or medium-sized museum or museum with an active changing exhibition program. The case is constructed using commercially available materials. However, unlike the typical museum showcase of this style, this design variation provides a display area devoid of harmful materials, includes RH control capabilities, and a passive system to remove interior pollutants. Performance results will also be presented, including RH control (one case has maintained an RH 25% lower than its surroundings for more than nine months) and a series of internal air quality measurements conducted by the Getty Conservation Institute, quantitating carbonyl pollutants and other volatile organic compounds.

Grzywacz, C., "Detection and Mitigation of Museum Pollutants: An Update," Objects Specialty Group, 20th Annual Meeting, American Institute for Conservation, Buffalo, New York, June 2-7, 1992.

ABSTRACT (abridged)-The conservation community has been aware of effects of the environment on cultural property for the last several years. This recognition was precipitated by the number of reported incidents of object damage while on display or in storage. Based on these concerns research has developed in the areas of environmental testing, evaluation of building materials, and pollutant mitigation. This paper discusses current research in these areas.

In the 1980s, the Getty Conservation Institute (GCI) developed a research program targeting indoor-generated carbonyl pollutants found in museum environments. The goal of this research program was to provide an integrated problem solving approach to the study of carbonyl pollutants in museum environments. From this research base, other related programs were developed, including analysis of volatile organic compounds released from display and storage case materials and physical and chemical mitigation of pollutants. The GCI sampled the indoor environment at sixteen collecting institutions from four general areas or site types: galleries, storage areas, storage cabinets, and display cases. The survey demonstrated that problem areas were specific to building materials used and air circulation patterns. An advanced technical survey of carbonyl concentrations is not necessarily accessible to all institutions. For this reason, economical passive sampling devices were identified that would provide reliable pollutant concentration data. The GCI evaluated a number of commercially available passive monitors and identified the Series 570 Formaldehyde Badge (GMD Systems, Inc.) for detection of low levels of formaldehyde. A direct reading (no analysis required) passive dosimeter was also evaluated. Still the question remained: "Where do these pollutants originate?" To determine the source of pollutants, a systematic study of volatile organic compounds (VOCs) emitted from materials used in the construction of display and storage cases was conducted. A list of the most frequently used materials for display, storage, and transportation of objects was compiled from a survey of over 1600 preparators and objects conservators. Based on this list, the testing of materials began. The VOCs were determined by gas chromatography-mass spectrometry (GC-MS). The type and concentrations of VOCs from various materials were determined with this highly sophisticated technique.

Grzywacz, C. M., and D. C. Stulik, "Carbonyl Pollutants in the Museum Environment," Paper presented at the Problems in Store Symposium at the Burrell Collection, Glasgow, Scotland, October 1992; Paper printed in the Scottish Society for Conservation and Restoration Journal, Vol. 4, Nš 1, January 1993, pp. 16-19.

ABSTRACT-In the 1980s the Getty Conservation Institute developed a research program targeting indoor-generated carbonyl pollutants found in museum environments. Several interlocking research areas such as analytical method development, museum pollution surveys, passive monitors, material damage studies, and mitigation methods allowed for the development of a well-rounded, integrated approach to museum pollutant problem solving.

Grzywacz, C. M., "Indoor Air Pollution: Identifying the Problem," IIC-CG Conference, Halifax, Nova Scotia, May 28-30, 1993.

ABSTRACT-The Getty Conservation Institute has implemented an integrated research program to address the concerns of detrimental museum environments. Three parts of the program will be discussed: museum environmental surveys, qualification and quantification of volatile organic compounds (VOCs) released from materials used in proximity to museum objects, and the evaluation and use of simple, economical passive sampling devices (PSDs).