A Review of the Usefulness of Various ASTM
and SW-846 Methods Which May Be Used by the Thermal Treatment Industry
A wide variety of existing and proposed ASTM and SW-846 methods for
waste analysis are reviewed. With a focus on those methods needed for
of waste prior to thermal treatment, a brief summary of various methods
along with a discussion of the advantages and disadvantages of selected
methods is included. Special emphasis is placed on methods used to
heat content, ash, halogens, metals and organic constituents. Selected
ASTM standards, currently undergoing development within ASTM, that may
prove useful to the thermal treatment industry are also reviewed.
David G. Gossman
President - Gossman Consulting, Inc.
Presented at the AWMA International Specialty Conference on Waste Combustion in Boilers and Industrial Furnaces March, 1995
In 1984, EPA released its first guidance document on Waste Analysis Plans (WAPs). In May of 1994, EPA released an updated guidance on waste analysis at Treatment Storage and Disposal Facilities (TSDFs). Neither of these guidance documents have dealt realistically with many WAP related issues at thermal treatment facilities. In addition, recent enforcement actions against thermal treatment facilities have frequently included issues involving Waste Analysis Plans, their adequacy and execution.
Furthermore, the Preamble to SW-846 3rd Edition for the Federal Register, February 8, 1990 states:
"This notice, or the subsequent final rule, should not be construed to require the use of SW-846, Third Edition methods except where specifically prescribed by regulation."
"Except for those situations where the RCRA regulations specify use of a particular method, it is appropriate for the chemist to use judgement, tempered by experience, in selecting an appropriate set of methods from SW-846 or the scientific literature for preparing and analyzing a given sample."
"Implicit in the proceeding argument is the fact the SW-846 was designed largely for use in showing that a waste does not contain certain hazardous constituents or characteristics. In that regard, many SW-846 sample preparation methods are designed around trace analysis rather than the percent level determinations often required for concentrated wastes. These methods, however, might be suitable for percent level determination analysis when appropriately modified by the analyst."
It was therefore of value to review a wide variety of existing and proposed ASTM and SW-846 methods for waste analysis. With a focus on those methods needed for analysis of waste prior to thermal treatment, a brief summary of various recommended methods along with a discussion of the advantages and disadvantages of selected methods is included. Special emphasis is placed on methods used to determine heat content, ash, halogens, metals and organic constituents. Selected ASTM standards, currently undergoing development within ASTM, that may prove useful to the thermal treatment industry are also identified.
Heat Content, Ash, Halogen and Sulfur
Heat content is perhaps the single most common determination made by thermal treatment facilities. The most common reference in thermal treatment facility WAPs is ASTM D240. A relatively new method is ASTM D5468, "Standard Test Method for Gross Calorific & Ash Value of Waste Materials" . This method was developed by ASTM Committee D-34 for use on wastes. It incorporates a procedure for ash as well as the option to use it for preparing samples for total sulfur and halogen analysis.
Although EPA has recommended the use of D808 for sample preparation for halogen and sulfur determinations, D5468 is better suited. D5468, for example includes an allowance for the use of the ion chromatography eluant as the absorption and wash medium. This eliminates the water dip in the chromatograph. This method also allows ash to be determined using the bomb residue thus eliminating the need for the more traditional muffle furnace. Although a wide variety of electrometric, colorimetric, and turbidimetric techniques have successfully been used for halogen and sulfur determinations, the most accurate and generally most efficient method is ion chromatography. SW-846 9056, "Anion Chromatography Method", used in conjunction with D5468 as mentioned above is highly recommended.
ASTM 5513 was specifically designed for BIF facilities and was presented at a previous A&WMA BIF Conference. ASTM E926 Method A was designed for refuse derived fuel and is the only method used to date on successful published mass balances for trace metals in cement kilns.
The preamble to the 3rd edition of SW-846 published in the Federal Register February 8, 1990 states:
"Sample preparation methods are not currently available in SW-846 to render nonaqueous liquids in a form that can be analyzed by the atomic absorption or inductively coupled plasma atomic emissions (ICP) type analytical methods for six important elements. These elements are: mercury, arsenic, selenium, lead, barium, and silver."
Indeed, it is generally recognized that matrices containing silicates including soils, ashes and rocks cannot be fully digested using nitric acid and HCl utilized in SW-846 methods. EPA is, in fact, developing a microwave digestion technique (SW-846 3052) using HF to fill this gap. Despite these facts, few thermal treatment facility WAPs reference methods to perform complete digestion. Both ASTM E926 Method A and the recently developed ASTM D5513, "Standard Practice for the Microwave Digestion of Industrial Furnace Feedstreams for Trace Element Analysis", have shown excellent results on a wide variety of matrices. In fact, the draft version of SW-846 3052 is very similar to ASTM D5513.
Actual determinant methods for metals cover a range of techniques including ICP, AA, GFAA, CVAA and XRF. Most facilities reference the SW-846 methods. All of these techniques have interferences that can be problematic in waste analyses given the variety of interfering factors that may be present and variable from one batch of waste to the next.
XRF is a technique apparently in disfavor by EPA yet widely accepted elsewhere in the world. It has the advantage of a fast sample preparation that does not require the use of hazardous acids. The disadvantage is the inability to determine berrylium. ASTM D-34 is developing an XRF method for hazardous wastes.
Volatile and semivolatile organic determinations are generally performed in order to provide information needed to protect worker health and safety. There appears an interesting pattern in the referenced methods. Those thermal treatment facilities that perform this determination, as a required part of the WAP, were generally cement plants which generally referenced ASTM methods. Those facilities that do not include this determination as a required step in the WAP were generally incinerators and generally referenced SW-846 methods. None of these methods truly represent the broad scan volatile/semivolatile analysis performed at many facilities. A representative method is under development within ASTM D-34.
PCB determinations are one of the most common at thermal treatment facilities because of regulatory controls on which facilities are permitted to burn PCBs. Nearly all cement plant and aggregate plants limit PCBs in receipts to <50 ppm. Even those incinerators that don't have limits in their WAPs frequently do testing. Most thermal treatment facilities provide SW-846 reference methods in their WAPs. Special care should be utilized in adapting PCB methods to waste matrices. False negatives have occurred, for example, when using florisil with some matrices because the PCBs stayed with the florisil. Internal standards or spiked samples should be a routine part of the PCB QA/QC program.
Cyanide is more commonly tested at incineration facilities than at BIF units because of the broader class of waste handled at incinerators. Nevertheless, the development of a convenient ASTM screening technique, ASTM D5049, "Standard Test Method for the Screening of Cyanides in Waste," has resulted in some BIFs now performing the screening.
Sulfide determinations generally go hand in hand with cyanide determinations. Like cyanide, the availability of an ASTM screening method, ASTM D 4978, "Standard Test Methods for Screening of Sulfides in Waste," should promote this parameter as part of WAPs throughout the industry.
Radioactivity, although screened for at many thermal treatment facilities, has no EPA or ASTM method. ASTM Committee D-34 is developing a screening technique that should prove quite useful.
SW-846 should not be considered the bible of analytical methods for
the hazardous waste management industry. EPA has itself acknowledged
significant shortcomings of this compendium. ASTM methods developed in
a consensus atmosphere with strict format and content guidelines often
fill the gaps left behind by EPA. The ASTM method development process
provides an excellent technical, nonconfrontational forum for all
of the interested community to work together toward common goals.
1. Gossman, D., Black, M., Ward, M., "The Fate of Trace Metals in the Wet Process Cement Kiln" in Proceedings on the 1990 A&WMA International Specialty Conference on Waste Combustion in Boilers and Industrial Furnaces" Air and Waste Management Association: Kansas City, MO, 1990; pp 70-93.
2. Pedersen, Bruce A.; "A Microwave Digestion Technique for Trace Element Analysis of Industrial Furnace Feedstreams" in Proceedings of the 1992 A&WMA conference on New RCRA Regulations for Industrial Boilers, Furnacs and Incinerators, Air & Waste Management Association, Pittsburgh, PA.
3. Test Methods for Evaluating Solid Waste, Vol 1A, 1B, 1C: Laboratory Manual Physical/Chemical Methods, and Vol 2: Field Manual Physical/Chemical Methods, EPA SW-846 Third Edition; U.S. Environmental Protection Agency, Office of Solid Waste and Emergency Response, Washington, DC, 1986.
4. Trial Burn and Compliance Test Report, Lone Star Industries, Greencastle, Indiana & Systech Environmental Corporation, Prepared by Gossman Consulting, Inc. and Team Environmental Services, Inc., Tracer Technologies Division, Vol. 1, August, 1992.
5. Trial Burn and Compliance Test Report, Holnam Inc. Holly Hill, South Carolina & Safety-Kleen Corporation, Prepared by Gossman Consulting, Inc., Vol. 1, August, 1992.
6. Trial Burn and Compliance Test Report, Continental Cement Company, Hannibal Missouri, Prepared by Gossman Consulting, Inc. & Clean Air Engineering, Vol. 1, July, 1992.
7. Trial Burn and Compliance Test Report, Holnam Inc., Clarksville, Missouri & Safetyy-Kleen Corporation, Prepared by Gossman Consulting, Inc., Vol.1, July, 1992.
8. ASTM Standards as Published by American Society for Testing and Materials, 100 Barr Harbor Dr., W Conshohocken, PA, various standards, and dates.