The provisions of §§ 1065.1103 through 1065.1111 specify procedures for measuring semi-volatile organic compounds (SVOC) along with PM. These sections specify how to collect a sample of the SVOCs during exhaust emission testing, as well as how to use wet chemistry techniques to extract SVOCs from the sample media for analysis. Note that the precise method you use will depend on the category of SVOCs being measured. For example, the method used to measure polynuclear aromatic hydrocarbons (PAHs) will differ slightly from the method used to measure dioxins. Follow standard analytic chemistry methods for any aspects of the analysis that are not specified.

(a) Laboratory cleanliness is especially important throughout SVOC testing. Thoroughly clean all sampling system components and glassware before testing to avoid sample contamination. For the purposes of this subpart, the sampling system is defined as sample pathway from the sample probe inlet to the downstream most point where the sample is captured (in this case the condensate trap).

(b) We recommend that media blanks be analyzed for each batch of sample media (sorbent, filters, etc.) prepared for testing. Blank sorbent modules (i.e., field blanks) should be stored in a sealed environment and should periodically accompany the test sampling system throughout the course of a test, including sampling system and sorbent module disassembly, sample packaging, and storage. Use good engineering judgment to determine the frequency with which you should generate field blanks. The field blank sample should be close to the sampler during testing.

(c) We recommend the use of isotope dilution techniques, including the use of isotopically labeled surrogate, internal, alternate, and injection standards.

(d) If your target analytes degrade when exposed to ultraviolet radiation, such as nitropolynuclear aromatic hydrocarbons (nPAHs), perform these procedures in the dark or with ultraviolet filters installed over the lights.

(e) The following definitions and abbreviations apply for SVOC measurements:

(1) Soxhlet extraction means the extraction method invented by Franz von Soxhlet, in which the sample is placed in a thimble and rinsed repeatedly with a recycle of the extraction solvent.

(2) XAD-2 means a hydrophobic crosslinked polystyrene copolymer resin adsorbent known commercially as Amberlite® XAD®-2, or an equivalent adsorbent like XAD-4.

(3) Semi-volatile organic compound (SVOC) means an organic compound that is sufficiently volatile to exist in vapor form in engine exhaust, but that readily condenses to liquid or solid form under atmospheric conditions. Most SVOCs have at least 14 carbon atoms per molecule or they have a boiling point between (240 and 400) °C. SVOCs include dioxin, quinone, and nitro-PAH compounds. They may be a natural byproduct of combustion or they may be created post-combustion. Note that SVOCs may be included in measured values of hydrocarbons and/or PM using the procedures specified in this part.

(4) Kuderna-Danish concentrator means laboratory glassware known by this name that consists of an air-cooled condenser on top of an extraction bulb.

(5) Dean-Stark trap means laboratory glassware known by this name that uses a reflux condenser to collect water from samples extracted under reflux.

(6) PUF means polyurethane foam.

(7) Isotopically labeled means relating to a compound in which either all the hydrogen atoms are replaced with the atomic isotope hydrogen-2 (deuterium) or one of the carbon atoms at a defined position in the molecule is replaced with the atomic isotope carbon-13.

(a) General. We recommend that you design your SVOC batch sampler to extract sample from undiluted emissions to maximize the sampled SVOC quantity. If you dilute your sample, we recommend using annular dilution. If you dilute your sample, but do not use annular dilution, you must precondition your sampling system to reach equilibrium with respect to loss and re-entrainment of SVOCs to the walls of the sampling system. To the extent practical, adjust sampling times based on the emission rate of target analytes from the engine to obtain analyte concentrations above the detection limit. In some instances you may need to run repeat test cycles without replacing the sample media or disassembling the batch sampler.

(b) Sample probe, transfer lines, and sample media holder design and construction. The sampling system should consist of a sample probe, transfer line, PM filter holder, cooling coil, sorbent module, and condensate trap. Construct sample probes, transfer lines, and sample media holders that have inside surfaces of nickel, titanium or another nonreactive material capable of withstanding raw exhaust gas temperatures. Seal all joints in the hot zone of the system with gaskets made of nonreactive material similar to that of the sampling system components. You may use teflon gaskets in the cold zone. We recommend locating all components as close to probes as practical to shorten sampling system length and minimize the surface exposed to engine exhaust.

(c) Sample system configuration. This paragraph (c) specifies the components necessary to collect SVOC samples, along with our recommended design parameters. Where you do not follow our recommendations, use good engineering judgment to design your sampling system so it does not result in loss of SVOC during sampling. The sampling system should contain the following components in series in the order listed:

(1) Use a sample probe similar to the PM sample probe specified in subpart B of this part.

(2) Use a PM filter holder similar to the holder specified in subpart B of this part, although you will likely need to use a larger size to accommodate the high sample flow rates. We recommend using a 110 mm filter for testing spark ignition engines or engines that utilize exhaust aftertreatment for PM removal and a 293 mm filter for other engines. If you are not analyzing separately for SVOCs in gas and particle phases, you do not have to control the temperature of the filter holder. Note that this differs from normal PM sampling procedures, which maintain the filter at a much lower temperature to capture a significant fraction of exhaust SVOC on the filter. In this method, SVOCs that pass through the filter will be collected on the downstream sorbent module. If you are collecting SVOCs in gas and particle phases, control your filter face temperature according to § 1065.140(e)(4).

(3) Use good engineering judgment to design a cooling coil that will drop the sample temperature to approximately 5 °C. Note that downstream of the cooling coil, the sample will be a mixture of vapor phase hydrocarbons in CO2, air, and a primarily aqueous liquid phase.

(4) Use a hydrophobic sorbent in a sealed sorbent module. Note that this sorbent module is intended to be the final stage for collecting the SVOC sample and should be sized accordingly. We recommend sizing the module to hold 40 g of XAD-2 along with PUF plugs at either end of the module, noting that you may vary the mass of XAD used for testing based on the anticipated SVOC emission concentration and sample flow rate.

(5) Include a condensate trap to separate the aqueous liquid phase from the gas stream. We recommend using a peristaltic pump to remove water from the condensate trap over the course of the test to prevent build-up of the condensate. Note that for some tests it may be appropriate to collect this water for analysis.

(d) Sampler flow control. For testing using the recommended filter and sorbent module sizes, we recommend targeting an average sample flow rate of 70 liters per minute to maximize SVOC collection. The sampler must be designed to maintain proportional sampling throughout the test. Verify proportional sampling after an emission test as described in § 1065.545.

(e) Water bath. Design the sample system with a water bath in which the cooling coil, sorbent module, and condensate trap will be submerged. Use a heat exchanger or ice to maintain the bath temperature at (3 to 7) °C.

This section describes the appropriate types of sample media and the cleaning procedure required to prepare the media and wetted sample surfaces for sampling.

(a) Sample media. The sampling system uses two types of sample media in series: The first to simultaneously capture the PM and associated particle phase SVOCs, and a second to capture SVOCs that remain in the gas phase, as follows:

(1) For capturing PM, we recommend using pure quartz filters with no binder if you are not analyzing separately for SVOCs in gas and particle phases. If you are analyzing separately, you must use polytetrafluoroethylene (PTFE) filters with PTFE support. Select the filter diameter to minimize filter change intervals, accounting for the expected PM emission rate, sample flow rate. Note that when repeating test cycles to increase sample mass, you may replace the filter without replacing the sorbent or otherwise disassembling the batch sampler. In those cases, include all filters in the extraction.

(2) For capturing gaseous SVOCs, utilize XAD-2 resin with or without PUF plugs. Note that two PUF plugs are typically used to contain the XAD-2 resin in the sorbent module.

(b) Sample media and sampler preparation. Prepare pre-cleaned PM filters and pre-cleaned PUF plugs/XAD-2 as needed. Store sample media in containers protected from light and ambient air if you do not use them immediately after cleaning. Use the following preparation procedure, or an analogous procedure with different solvents and extraction times:

(1) Pre-clean the filters via Soxhlet extraction with methylene chloride for 24 hours and dry over dry nitrogen in a low-temperature vacuum oven.

(2) Pre-clean PUF and XAD-2 with a series of Soxhlet extractions: 8 hours with water, 22 hours with methanol, 22 hours with methylene chloride, and 22 hours with toluene, followed by drying with nitrogen.

(3) Clean sampler components, including the probe, filter holder, condenser, sorbent module, and condensate collection vessel by rinsing three times with methylene chloride and then three times with toluene. Prepare pre-cleaned aluminum foil for capping the probe inlet of the sampler after the sampling system has been assembled.

(c) Sorbent spiking. Use good engineering judgment to verify the extent to which your extraction methods recover SVOCs absorbed on the sample media. We recommend spiking the XAD-2 resin with a surrogate standard before testing with a carbon-13 or hydrogen-2 isotopically labeled standard for each of the class of analytes targeted for analysis. Perform this spiking as follows:

(1) Insert the lower PUF plug into the bottom of the sorbent module.

(2) Add half of one portion of XAD-2 resin to the module and spike the XAD-2 in the module with the standard.

(3) Wait 1 hour for the solvent from the standard(s) to evaporate, add the remaining 20 g of the XAD-2 resin to the module, and then insert a PUF plug in the top of the sorbent module.

(4) Cover the inlet and outlet of the sorbent module with pre-cleaned aluminum foil.

(d) Sampling system assembly. After preparing the sample media and the sampler, assemble the condensate trap, cooling coil, filter holder with filter, sample probe, and sorbent module, then lower the assembly into the reservoir. Cover the probe inlet with pre-cleaned aluminum foil.

This section describes the process for disassembling and rinsing the sampling system and extracting and cleaning up the sample.

(a) Sampling system disassembly. Disassemble the sampling system in a clean environment as follows after the test:

(1) Remove the PM filter, PUF plugs, and all the XAD-2 from the sampling system and store them at or below 5 °C until analysis.

(2) Rinse sampling system wetted surfaces upstream of the condensate trap with acetone followed by toluene (or a comparable solvent system), ensuring that all the solvent remaining in liquid phase is collected (note that a fraction of the acetone and toluene will likely be lost to evaporation during mixing). Rinse with solvent volumes that are sufficient to cover all the surfaces exposed to the sample during testing. We recommend three fresh solvent rinses with acetone and two with toluene. We recommend rinse volumes of 60 ml per rinse for all sampling system components except the condenser coil, of which you should use 200 ml per rinse. Keep the acetone rinsate separate from the toluene rinsate to the extent practicable. Rinsate fractions should be stored separately in glass bottles that have been pre-rinsed with acetone, hexane, and toluene (or purchase pre-cleaned bottles).

(3) Use good engineering judgment to determine if you should analyze the aqueous condensate phase for SVOCs. If you determine that analysis is necessary, use toluene to perform a liquid-liquid extraction of the SVOCs from the collected aqueous condensate using a separatory funnel or an equivalent method. Add the toluene from this aqueous extraction to the toluene rinsate fraction described in paragraph (a)(2) of this section.

(4) Reduce rinsate solvent volumes as needed using a Kuderna-Danish concentrator or rotary evaporator and retain these rinse solvents for reuse during sample media extraction for the same test. Be careful to avoid loss of low molecular weight analytes when concentrating with rotary evaporation.

(b) Sample extraction. Extract the SVOCs from the sorbent using Soxhlet extraction as described in this paragraph (b). Two 16 hour extractions are necessary to accommodate the Soxhlet extractions of all SVOCs from a single sample. This reduces the possibility of losing low molecular weight SVOCs and promotes water removal. We recommend performing the first extraction with acetone/hexane and the second using toluene (or an equivalent solvent system). You may alternatively use an equivalent method such as an automated solvent extractor.

(1) We recommend equipping the Soxhlet extractor with a Dean-Stark trap to facilitate removal of residual water from the sampling system rinse. The Soxhlet apparatus must be large enough to allow extraction of the PUF, XAD-2, and filter in a single batch. Include in the extractor setup a glass thimble with a coarse or extra coarse sintered glass bottom. Pre-clean the extractor using proper glass-cleaning procedures. We recommend that the Soxhlet apparatus be cleaned with a (4 to 8) hour Soxhlet extraction with methylene chloride at a cycling rate of three cycles per hour. Discard the solvent used for pre-cleaning (no analysis is necessary).

(2) Load the extractor thimble before placing it in the extractor by first rolling the PM filter around the inner circumference of the thimble, with the sampled side facing in. Push one PUF plug down into the bottom of the thimble, add approximately half of the XAD-2, and then spike the XAD-2 in the thimble with the isotopically labeled extraction standards of known mass. Target the center of the XAD-2 bed for delivering the extraction standard. We recommend using multiple isotopically labeled extraction standards that cover the range of target analytes. This generally means that you should use isotopically labeled standards at least for the lowest and highest molecular weight analytes for each category of compounds (such as PAHs and dioxins). These extraction standards monitor the efficiency of the extraction and are also used to determine analyte concentrations after analysis. Upon completion of spiking, add the remaining XAD-2 to the thimble, insert the remaining PUF plug, and place the thimble into the extractor. Note that if you are collecting and analyzing for SVOCs in gas and particle phases, perform separate extractions for the filter and XAD-2.

(3) For the initial extraction, combine the concentrated acetone rinses (from the sampling system in paragraph (a) of this section) with enough hexane to bring the solvent volume up to the target level of 700 ml. Assemble the extractor and turn on the heating controls and cooling water. Allow the sample to reflux for 16 hours with the rheostat adjusted to cycle the extraction at a rate of (3.0 ±0.5) cycles per hour. Drain the water from the Dean-Stark trap as it accumulates by opening the stopcock on the trap. Set aside the water for analysis or discard it. In most cases, any water present will be removed within approximately 2 hours after starting the extraction.

(4) After completing the initial extraction, remove the solvent and concentrate it to (4.0 ±0.5) ml using a Kuderna-Danish concentrator that includes a condenser such as a three-ball Snyder column with venting dimples and a graduated collection tube. Hold the water bath temperature at (75 to 80) °C. Using this concentrator will minimize evaporative loss of analytes with lower molecular weight.

(i) Rinse the round bottom flask of the extractor with (60 to 100) ml of hexane and add the rinsate to this concentrated extract.

(ii) Concentrate the mixture to (4 ±0.5) ml using a Kuderna-Danish concentrator or similar apparatus.

(iii) Repeat the steps in paragraphs (b)(4)(i) and (ii) of this section three times, or as necessary to remove all the residual solvent from the round bottom flask of the extractor, concentrating the final rinsate to (4 ±0.5) ml.

(5) For the second extraction, combine the toluene rinses (from the sampling system in paragraph (a) of this section) with any additional toluene needed to bring the solvent volume up to the target level of 700 ml. As noted in paragraph (a) of this section, you may need to concentrate the rinsate before adding it to the extraction apparatus if the rinsate solvent volume is too large. Allow the sample to reflux for 16 hours with the rheostat adjusted to cycle the extraction at a rate of (3.0 ±0.5) cycles per hour. Check the Dean-Stark trap for water during the first 2 hours of the extraction (though little or no water should be present during this stage).

(6) Upon completion of the second extraction, remove the solvent and concentrate it to (4 ±0.5) ml as described in paragraph (b)(4) of this section. Using hexane from paragraph (b)(4) of this section as the rinse solvent effectively performs a solvent exchange of toluene with hexane.

(7) Combine the concentrated extract from paragraph (b)(4) of this section with the concentrated extract from paragraph (b)(6) of this section. Divide the extract into a number of fractions based on the number of analyses you need to perform. Perform the separate sample clean-up described in paragraph (c) of this section as needed for each fraction.

(c) Sample clean-up. This paragraph (c) describes how to perform sample cleaning to remove from the sample extract any solids and any SVOCs that will not be analyzed. This process, known as “sample clean-up”, reduces the potential for interference or co-elution of peaks during analytical analysis. Before performing the sample clean-up, spike the extract with an alternate standard that contains a known mass of isotopically labeled compounds that are identical to the target analytes (except for the labeling). The category of the target analyte compounds (such as PAHs or dioxin) will determine the number of compounds that make up the standard. For example, PAHs require the use of four compounds in the alternate standard to cover the four basic ring structures of PAHs (2-ring, 3-ring, 4-ring, and 5-ring structures). These alternate standards are used to monitor the efficiency of the clean-up procedure. Before sample clean-up, concentrate the fractionated sample to about 2 ml with a Kuderna-Danish concentrator or rotary evaporator, and then transfer the extract to an 8 ml test tube with hexane rinse. Concentrate it to a volume of about 1 ml using a Kuderna-Danish concentrator. Use good engineering judgment to select an appropriate column chromatographic clean-up option for your target analytes. Note that these clean-up techniques generally remove compounds based on their polarity. The following procedures are examples of clean-up techniques for PAHs and nPAHs.

(1) PAH clean-up. The following method is appropriate for clean-up of extracts intended for analysis of PAHs:

(i) Pack a glass gravity column (250 mm × 10 mm recommended) by inserting a clean glass wool plug into the bottom of the column and add 10 g of activated silica gel in methylene chloride. Tap the column to settle the silica gel and then add a 1 cm layer of anhydrous sodium sulfate. Verify the volume of solvent required to completely elute all the PAHs and adjust the weight of the silica gel accordingly to account for variations among batches of silica gel that may affect the elution volume of the various PAHs.

(ii) Elute the column with 40 ml of hexane. The rate for all elutions should be about 2 ml/min. You may increase the elution rate by using dry air or nitrogen to maintain the headspace slightly above atmospheric pressure. Discard the eluate just before exposing the sodium sulfate layer to the air or nitrogen and transfer the 1 ml sample extract onto the column using two additional 2 ml rinses of hexane. Just before exposing the sodium sulfate layer to the air or nitrogen, begin elution of the column with 25 ml of hexane followed by 25 ml of 40 volume % methylene chloride in hexane. Collect the entire eluate and concentrate it to about 5 ml using the Kuderna-Danish concentrator or a rotary evaporator. Make sure not to evaporate all the solvent from the extract during the concentration process. Transfer the eluate to a small sample vial using a hexane rinse and concentrate it to 100 µl using a stream of nitrogen without violently disturbing the solvent. Store the extracts in a refrigerator at or below 4 °C, and away from light.

(2) nPAH clean up. The following procedure, adapted from “Determination and Comparison of Nitrated-Polycyclic Aromatic Hydrocarbons Measured in Air and Diesel Particulate Reference Materials” (Bamford, H.A., et al, Chemosphere, Vol. 50, Issue 5, pages 575-587), is an appropriate method to clean up extracts intended for analysis of nPAHs:

(i) Condition an aminopropyl solid phase extraction (SPE) cartridge by eluting it with 20 ml of 20 volume % methylene chloride in hexane. Transfer the extract quantitatively to the SPE cartridge with at least two methylene chloride rinses. Elute the extract through the SPE cartridge by using 40 ml of 20 volume % methylene chloride in hexane to minimize potential interference of polar constituents, and then reduce the extract to 0.5 ml in hexane and subject it to normal-phase liquid chromatography using a pre-prepared 9.6 mm × 25 cm semi-preparative Chromegabond® amino/cyano column (5 µm particle size) to isolate the nPAH fraction. The mobile phase is 20 volume % methylene chloride in hexane at a constant flow rate of 5 ml per minute. Back-flash the column with 60 ml of methylene chloride and then condition it with 200 ml of 20 volume % methylene chloride in hexane before each injection. Collect the effluent and concentrate it to about 2 ml using the Kuderna-Danish concentrator or a rotary evaporator. Transfer it to a minivial using a hexane rinse and concentrate it to 100 µl using a gentle stream of nitrogen. Store the extracts at or below 4 °C, and away from light.

(ii) [Reserved]

This subpart does not specify chromatographic or analytical methods to analyze extracts, because the appropriateness of such methods is highly dependent on the nature of the target analytes. However, we recommend that you spike the extract with an injection standard that contains a known mass of an isotopically labeled compound that is identical to one of the target analytes (except for labeling). This injection standard allows you to monitor the efficiency of the analytical process by verifying the volume of sample injected for analysis.

This subpart specifies procedures that may be used to measure emission constituents that are not measured (or not separately measured) by the test procedures in the other subparts of this part. These procedures are included to facilitate consistent measurement of unregulated pollutants for purposes other than compliance with emission standards. Unless otherwise specified in the standard-setting part, use of these procedures is optional and does not replace any requirements in the rest of this part.

Sections 1065.1113 through 1065.1121 specify procedures for determining vanadium emissions from a catalyst based on catalyst temperature. Vanadium can be emitted from the surface of SCR catalysts at temperatures above 550 °C, dependent on the catalyst formulation. These procedures are appropriate for measuring the vanadium sublimation product from a reactor by sampling onto an equivalent mass of alumina and performing analysis by Inductively Coupled Plasma—Optical Emission Spectroscopy (ICP-OES). Follow standard analytic chemistry methods for any aspects of the analysis that are not specified.

(a) The procedure is adapted from “Behavior of Titania-supported Vanadia and Tungsta SCR Catalysts at High Temperatures in Reactant Streams: Tungsten and Vanadium Oxide and Hydroxide Vapor Pressure Reduction by Surficial Stabilization” (Chapman, D.M., Applied Catalysis A: General, 2011, 392, 143-150) with modifications to the acid digestion method from “Measuring the trace elemental composition of size-resolved airborne particles” (Herner, J.D. et al, Environmental Science and Technology, 2006, 40, 1925-1933).

(b) Laboratory cleanliness is especially important throughout vanadium testing. Thoroughly clean all sampling system components and glassware before testing to avoid sample contamination.

Vanadium measurements rely on a reactor that adsorbs sublimation vapors of vanadium onto an alumina capture bed with high surface area.

(a) Configure the reactor with the alumina capture bed downstream of the catalyst in the reactor's hot zone to adsorb vanadium vapors at high temperature. You may use quartz beads upstream of the catalyst to help stabilize reactor gas temperatures. Select an alumina material and design the reactor to minimize sintering of the alumina. For a 1-inch diameter reactor, use 4 to 5 g of 1/8 inch extrudates or -14/+24 mesh (approximately 0.7 to 1.4 mm) gamma alumina (such as Alfa Aesar, aluminum oxide, gamma, catalyst support, high surface area, bimodal). Position the alumina downstream from either an equivalent amount of -14/+24 mesh catalyst sample or an approximately 1-inch diameter by 1 to 3-inch long catalyst-coated monolith sample cored from the production-intent vanadium catalyst substrate. Separate the alumina from the catalyst with a 0.2 to 0.4 g plug of quartz wool. Place a short 4 g plug of quartz wool downstream of the alumina to maintain the position of that bed. Use good engineering judgment to adjust as appropriate for reactors of different sizes.

(b) Include the quartz wool with the capture bed to measure vanadium content. We recommend analyzing the downstream quartz wool separately from the alumina to see if the alumina fails to capture some residual vanadium.

(c) Configure the reactor such that both the sample and capture beds are in the reactor's hot zone. Design the reactor to maintain similar temperatures in the capture bed and catalyst. Monitor the catalyst and alumina temperatures with Type K thermocouples inserted into a thermocouple well that is in contact with the catalyst sample bed.

(d) If there is a risk that the quartz wool and capture bed are not able to collect all the vanadium, configure the reactor with an additional capture bed and quartz wool plug just outside the hot zone and analyze the additional capture bed and quartz wool separately.

(e) An example of a catalyst-coated monolith and capture bed arrangement in the reactor tube are shown in the following figure:

(f) You may need to account for vanadium-loaded particles contaminating catalyst-coated monoliths as a result of physical abrasion. To do this, determine how much titanium is in the capture bed and compare to an alumina blank. Using these values and available information about the ratio of vanadium to titanium in the catalyst, subtract the mass of vanadium catalyst material associated with the catalyst particles from the total measured vanadium on the capture bed to determine the vanadium recovered due to sublimation.

This section describes the conditions and process required to operate the reactor described in § 1065.1115 for collection of the vanadium sublimation samples for determination of vanadium sublimation temperature. The reactor aging cycle constitutes the process of testing the catalyst sample over all the test conditions described in paragraph (b) of this section.

(a) Set up the reactor to flow gases with a space velocity of at least 35,000/hr with a pressure drop across the catalyst and capture beds less than 35 kPa. Use test gases meeting the following specifications, noting that not all gases will be used at the same time:

(1) 5 vol% O2, balance N2.

(2) NO, balance N2. Use an NO concentration of (200 to 500) ppm.

(3) NH3, balance N2. Use an NH3 concentration of (200 to 500) ppm.

(b) Perform testing as follows:

(1) Add a new catalyst sample and capture bed into the reactor as described in § 1065.1113. Heat the reactor to 550 °C while flowing the oxygen blend specified in paragraph (a)(1) of this section as a pretest gas mixture. Ensure that no H2O is added to the pretest gas mixture to reduce the risk of sintering and vanadium sublimation.

(2) Start testing at a temperature that is lower than the point at which vanadium starts to sublime. Start testing when the reactor reaches 550 °C unless testing supports a lower starting temperature. Once the reactor reaches the starting temperature and the catalyst has been equilibrated to the reactor temperature, flow NO and NH3 test gases for 18 hours with a nominal H2O content of 5 volume percent. If an initial starting temperature of 550 °C results in vanadium sublimation, you may retest using a new catalyst sample and a lower initial starting temperature.

(3) After 18 hours of exposure, flow the pretest oxygen blend as specified in paragraph (b)(1) of this section and allow the reactor to cool down to room temperature.

(4) Analyze the sample as described in § 1065.1121.

(5) Repeat the testing in paragraphs (b)(1) through (4) of this section by raising the reactor temperature in increments of 50 °C up to the temperature at which vanadium sublimation begins.

(6) Once sublimation has been detected, repeat the testing in paragraphs (b)(1) through (4) of this section by decreasing the reactor temperature in increments of 25 °C until the vanadium concentration falls below the sublimation threshold.

(7) Repeat the testing in paragraphs (b)(1) through (6) of this section with a nominal H2O concentration of 10 volume percent or the maximum water concentration expected at the standard.

(8) You may optionally test in a manner other than testing a single catalyst formulation in series across all test temperatures. For example, you may test additional samples at the same reactor temperature before moving on to the next temperature.

(c) The effective sublimation temperature for the tested catalyst is the lowest reactor temperature determined in paragraph (b) of this section below which vanadium emissions are less than the method detection limit.

This section describes the process for analyzing blanks. Use blanks to determine the background effects and the potential for contamination from the sampling process.

(a) Take blanks from the same batch of alumina used for the capture bed.

(b) Media blanks are used to determine if there is any contamination in the sample media. Analyze at least one media blank for each reactor aging cycle or round of testing performed under § 1065.1117. If your sample media is taken from the same lot, you may analyze media blanks less frequently consistent with good engineering judgment.

(c) Field blanks are used to determine if there is any contamination from environmental exposure of the sample media. Analyze at least one field blank for each reactor aging cycle or round of testing performed under § 1065.1117. Field blanks must be contained in a sealed environment and accompany the reactor sampling system throughout the course of a test, including reactor disassembly, sample packaging, and storage. Use good engineering judgment to determine how frequently to generate field blanks. Keep the field blank sample close to the reactor during testing.

(d) Reactor blanks are used to determine if there is any contamination from the sampling system. Analyze at least one reactor blank for each reactor aging cycle or round of testing performed under § 1065.1117.

(1) Test reactor blanks with the reactor on and operated identically to that of a catalyst test in § 1065.1117 with the exception that when loading the reactor, only the alumina capture bed will be loaded (no catalyst sample is loaded for the reactor blank). We recommend acquiring reactor blanks with the reactor operating at average test temperature you used when acquiring your test samples under § 1065.1117.

(2) You must run at least three reactor blanks if the result from the initial blank analysis is above the detection limit of the method, with additional blank runs based on the uncertainty of the reactor blank measurements, consistent with good engineering judgment.

This section describes the process for dissolution of vanadium from the vanadium sublimation samples collect in § 1065.1117 and any blanks collected in § 1065.1119 as well as the analysis of the digestates to determine the mass of vanadium emitted and the associated sublimation temperature threshold based on the results of all the samples taken during the reactor aging cycle.

(a) Digest the samples using the following procedure, or an equivalent procedure:

(1) Place the recovered alumina, a portion of the ground quartz tube from the reactor, and the quartz wool in a Teflon pressure vessel with a mixture made from 1.5 mL of 16 N HNO3, 0.5 mL of 28 N HF, and 0.2 mL of 12 N HCl. Note that the amount of ground quartz tube from the reactor included in the digestion can influence the vanadium concentration of both the volatilized vanadium from the sample and the method detection limit. You must be consistent with the amount ground quartz tube included in the sample analysis for your testing. You must limit the amount of quartz tube to include only portions of the tube that would be likely to encounter volatilized vanadium.

(2) Program a microwave oven to heat the sample to 180 °C over 9 minutes, followed by a 10-minute hold at that temperature, and 1 hour of ventilation/cooling.

(3) After cooling, dilute the digests to 30 mL with high purity 18MΩ water prior to ICP-MS (or ICP-OES) analysis. Note that this digestion technique requires adequate safety measures when working with HF at high temperature and pressure. To avoid “carry-over” contamination, rigorously clean the vessels between samples as described in “Microwave digestion procedures for environmental matrixes” (Lough, G.C. et al, Analyst. 1998, 123 (7), 103R-133R).

(b) Analyze the digestates for vanadium as follows:

(1) Perform the analysis using ICP-OES (or ICP-MS) using standard plasma conditions (1350 W forward power) and a desolvating microconcentric nebulizer, which will significantly reduce oxide- and chloride-based interferences.

(2) We recommend that you digest and analyze a minimum of three solid vanadium NIST Standard Reference Materials in duplicate with every batch of 25 vanadium alumina capture bed samples that you analyze in this section, as described in “Emissions of metals associated with motor vehicle roadways” (Herner, J.D. et al, Environmental Science and Technology. 2005, 39, 826-836). This will serve as a quality assurance check to help gauge the relative uncertainties in each measurement, specifically if the measurement errors are normally distributed and independent.

(3) Use the 3-sigma approach to determine the analytical method detection limits for vanadium and the 10-sigma approach if you determine the reporting limit. This process involves analyzing at least seven replicates of a reactor blank using the analytical method described in paragraphs (a) and (b)(1) of this section, converting the responses into concentration units, and calculating the standard deviation. Determine the detection limit by multiplying the standard deviation by 3 and adding it to the average. Determine the reporting limit by multiplying the standard deviation by 10 and adding it to the average. Determine the following analytical method detection limits:

(i) Determine the ICP-MS (or ICP-OES) instrumental detection limit (ng/L) by measuring at least seven blank samples made up of the reagents from paragraph (a) of this section.

(ii) Determine the method detection limit (µg/m 3 of flow) by measuring at least seven reactor blank samples taken as described in § 1065.1119(d).

(iii) We recommend that your method detection limit determined under paragraph (b)(3)(ii) of this section is at or below 15 µg/m 3. You must report your detection limits determined in this paragraph (b)(3) and reporting limits (if determined) with your test results.

(4) If you account for vanadium-loaded particles contaminating catalyst-coated monoliths as a result of physical abrasion as allowed in § 1065.1115(f), use the 3-sigma approach to determine the analytical method detection limits for titanium and the 10-sigma approach if you determine the reporting limit. This process involves analyzing at least seven replicates of a blank using the analytical method described in paragraphs (a) and (b)(1) of this section, converting the responses into concentration units, and calculating the standard deviation. Determine the detection limit by multiplying the standard deviation by 3 and subtracting it from the average. Determine the reporting limit by multiplying the standard deviation by 10 and subtracting it from the average.

(i) Determine the ICP-MS (or ICP-OES) instrumental detection limit (ng/L) by measuring at least seven blank samples made up of the reagents from paragraph (a) of this section.

(ii) Determine the method detection limit (µg/m 3 of flow) by measuring at least seven reactor blank samples taken as described in § 1065.1119(d).

The provisions of § 1065.1125 describe system specifications for measuring percent opacity of exhaust for all types of engines. The provisions of § 1065.1127 describe how to use such a system to determine percent opacity of engine exhaust for applications other than locomotives. See 40 CFR 1033.525 for measurement procedures for locomotives.

Smokemeters measure exhaust opacity using full-flow open-path light extinction with a built-in light beam across the exhaust stack or plume. Prepare and install a smokemeter system as follows:

(a) Except as specified in paragraph (d) of this section, use a smokemeter capable of providing continuous measurement that meets the following specifications:

(1) Use an incandescent lamp with a color temperature between (2800 and 3250) K or a different light source with a spectral peak between (550 and 570) nm.

(2) Collimate the light beam to a nominal diameter of 3 centimeters and maximum divergence angle of 6 degrees.

(3) Include a photocell or photodiode as a detector. The detector must have a maximum spectral response between (550 and 570) nm, with less than 4 percent of that maximum response below 430 nm and above 680 nm. These specifications correspond to visual perception with the human eye.

(4) Use a collimating tube with an aperture that matches the diameter of the light beam. Restrict the detector to viewing within a 16 degree included angle.

(5) Optionally use an air curtain across the light source and detector window to minimize deposition of smoke particles, as long as it does not measurably affect the opacity of the sample.

(6) The diagram in the following figure illustrates the smokemeter configuration:

(b) Smokemeters for locomotive applications must have a full-scale response time of 0.5 seconds or less. Smokemeters for locomotive applications may attenuate signal responses with frequencies higher than 10 Hz with a separate low-pass electronic filter that has the following performance characteristics:

(1) Three decibel point: 10 Hz.

(2) Insertion loss: (0.0 ±0.5) dB.

(3) Selectivity: 12 dB down at 40 Hz minimum.

(4) Attenuation: 27 dB down at 40 Hz minimum.

(c) Configure exhaust systems as follows for measuring exhaust opacity:

(1) For locomotive applications:

(i) Optionally add a stack extension to the locomotive muffler.

(ii) For in-line measurements, the smokemeter is integral to the stack extension.

(iii) For end-of-line measurements, mount the smokemeter directly at the end of the stack extension or muffler.

(iv) For all testing, minimize distance from the optical centerline to the muffler outlet; in no case may it be more than 300 cm. The maximum allowable distance of unducted space upstream of the optical centerline is 50 cm, whether the unducted portion is upstream or downstream of the stack extensions.

(2) Meet the following specifications for all other applications:

(i) For in-line measurements, install the smokemeter in an exhaust pipe segment downstream of all engine components. This will typically be part of a laboratory configuration to route the exhaust to an analyzer. The exhaust pipe diameter must be constant within 3 exhaust pipe diameters before and after the smokemeter's optical centerline. The exhaust pipe diameter may not change by more than a 12-degree half-angle within 6 exhaust pipe diameters upstream of the smokemeter's optical centerline.

(ii) For end-of-line measurements with systems that vent exhaust to the ambient, add a stack extension and position the smokemeter such that its optical centerline is (2.5 ±0.625) cm upstream of the stack extension's exit. Configure the exhaust stack and extension such that at least the last 60 cm is a straight pipe with a circular cross section with an approximate inside diameter as specified in the following table:

(iii) For both in-line and end-of-line measurements, install the smokemeter so its optical centerline is (3 to 10) meters further downstream than the point in the exhaust stream that is farthest downstream considering all the following components: exhaust manifolds, turbocharger outlets, exhaust aftertreatment devices, and junction points for combining exhaust flow from multiple exhaust manifolds.

(3) Orient the light beam perpendicular to the direction of exhaust flow. Install the smokemeter so it does not influence exhaust flow distribution or the shape of the exhaust plume. Set up the smokemeter's optical path length as follows:

(i) For locomotive applications, the optical path length must be at least as wide as the exhaust plume.

(ii) For all other applications, the optical path length must be the same as the diameter of the exhaust flow. For noncircular exhaust configurations, set up the smokemeter such that the light beam's path length is across the longest axis with an optical path length equal to the hydraulic diameter of the exhaust flow.

(4) The smokemeter must not interfere with the engine's ability to meet the exhaust backpressure requirements in § 1065.130(h).

(5) For engines with multiple exhaust outlets, measure opacity using one of the following methods:

(i) Join the exhaust outlets together to form a single flow path and install the smokemeter (3 to 10) m downstream of the point where the exhaust streams converge or the last exhaust aftertreatment device, whichever is farthest downstream.

(ii) Install a smokemeter in each of the exhaust flow paths. Report all measured values. All measured values must comply with standards.

(6) The smokemeter may use purge air or a different method to prevent carbon or other exhaust deposits on the light source and detector. Such a method used with end-of-line measurements may not cause the smoke plume to change by more than 0.5 cm at the smokemeter. If such a method affects the smokemeter's optical path length, follow the smokemeter manufacturer's instructions to properly account for that effect.

(d) You may use smokemeters meeting alternative specifications as follows:

(1) You may use smokemeters that use other electronic or optical techniques if they employ substantially identical measurement principles and produce substantially equivalent results.

(2) You may ask us to approve the use of a smokemeter that relies on partial flow sampling. Follow the instrument manufacturer's installation, calibration, operation, and maintenance procedures if we approve your request. These procedures must include correcting for any change in the path length of the exhaust plume relative to the diameter of the engine's exhaust outlet.

The test procedure described in this section applies for everything other than locomotives. The test consists of a sequence of engine operating points on an engine dynamometer to measure exhaust opacity during specific engine operating modes to represent in-use operation. Measure opacity using the following procedure:

(a) Use the equipment and procedures specified in this part 1065.

(b) Calibrate the smokemeter as follows:

(1) Calibrate using neutral density filters with approximately 10, 20, and 40 percent opacity. Confirm that the opacity values for each of these reference filters are NIST-traceable within 185 days of testing, or within 370 days of testing if you consistently protect the reference filters from light exposure between tests.

(2) Before each test and optionally during engine idle modes, remove the smokemeter from the exhaust stream, if applicable, and calibrate as follows:

(i) Zero. Adjust the smokemeter to give a zero response when there is no detectable smoke.

(ii) Linearity. Insert each of the qualified reference filters in the light path perpendicular to the axis of the light beam and adjust the smokemeter to give a result within 1 percentage point of the named value for each reference filter.

(c) Prepare the engine, dynamometer, and smokemeter for testing as follows:

(1) Set up the engine to run in a configuration that represents in-use operation.

(2) Determine the smokemeter's optical path length to the nearest mm.

(3) If the smokemeter uses purge air or another method to prevent deposits on the light source and detector, adjust the system according to the system manufacturer's instructions and activate the system before starting the engine.

(4) Program the dynamometer to operate in torque-control mode throughout testing. Determine the dynamometer load needed to meet the cycle requirements in paragraphs (d)(4)(ii) and (iv) of this section.

(5) You may program the dynamometer to apply motoring assist with negative flywheel torque, but only during the first 0.5 seconds of the acceleration events in paragraphs (d)(4)(i) and (ii) of this section. Negative flywheel torque may not exceed 13.6 N·m.

(d) Operate the engine and dynamometer over repeated test runs of the duty cycle illustrated in Figure 1 of this appendix. As noted in the figure, the test run includes an acceleration mode from points A through F in the figure, followed by a lugging mode from points I to J. Detailed specifications for testing apply as follows:

(1) Continuously record opacity, engine speed, engine torque, and operator demand over the course of the entire test at 10 Hz; however, you may interrupt measurements to recalibrate during each idle mode.

(2) Precondition the engine by operating it for 10 minutes at maximum mapped power.

(3) Operate the engine for (5.0 to 5.5) minutes at warm idle speed, ƒnidle, with load set to Curb Idle Transmission Torque.

(4) Operate the engine and dynamometer as follows during the acceleration mode:

(i) First acceleration event—AB. Partially increase and hold operator demand to stabilize engine speed briefly at (200 ±50) r/min above ƒnidle. The start of this acceleration is the start of the test (t = 0 s).

(ii) Second acceleration event—CD. As soon as measured engine speed is within the range specified in paragraph (d)(4)(i) of this section, but not more than 3 seconds after the start of the test, rapidly set and hold operator demand at maximum. Operate the dynamometer using a preselected load to accelerate engine speed to 85 percent of maximum test speed, ƒntest, in (5 ±1.5) seconds. The engine speed throughout the acceleration must be within ±100 r/min of a target represented by a linear transition between the low and high engine speed targets.

(iii) Transition—DEF. As soon as measured engine speed reaches 85 percent of ƒntest, rapidly set and hold operator demand at minimum and simultaneously apply a load to decelerate to intermediate speed in (0.5 to 3.5) seconds. Use the same load identified for the acceleration event in paragraph (d)(4)(iv) of this section.

(iv) Third acceleration event—FGH. Rapidly set and hold operator demand at maximum when the engine is within ±50 r/min of intermediate speed. Operate the dynamometer using a preselected load to accelerate engine speed to at least 95 percent of ƒntest in (10 ±2) seconds.

(5) Operate the engine and dynamometer as follows during the lugging mode:

(i) Transition—HI. When the engine reaches 95 percent of ƒntest, keep operator demand at maximum and immediately set dynamometer load to control the engine at maximum mapped power. Continue the transition segment for (50 to 60) seconds. For at least the last 10 seconds of the transition segment, hold engine speed within ±50 r/min of ƒntest and power at or above 95 percent of maximum mapped power. Conclude the transition by increasing dynamometer load to reduce engine speed as specified in paragraph (d)(4)(iii) of this section, keeping operator demand at maximum.

(ii) Lugging—IJ. Apply dynamometer loading as needed to decrease engine speed from 50 r/min below fntest to intermediate speed in (35 ±5) seconds. The engine speed must remain within ±100 r/min of a target represented by a linear transition between the low and high engine speed targets.

(6) Return the dynamometer and engine controls to the idle position described in paragraph (d)(3) of this section within 60 seconds of completing the lugging mode.

(7) Repeat the procedures in paragraphs (d)(3) through (6) of this section as needed to complete three valid test runs. If you fail to meet the specifications during a test run, continue to follow the specified duty cycle before starting the next test run.

(8) Shut down the engine or remove the smokemeter from the exhaust stream to verify zero and linearity. Void the test if the smokemeter reports more than 2 percent opacity for the zero verification, or if the smokemeter's error for any of the linearity checks specified in paragraph (b)(2) of this section is more than 2 percent.

(e) Analyze and validate the test data as follows:

(1) Divide each test run into test segments. Each successive test segment starts when the preceding segment ends. Identify the test segments based on the following criteria:

(i) The idle mode specified in paragraph (d)(3) of this section for the first test run starts immediately after engine preconditioning is complete. The idle mode for later test runs must start within 60 seconds after the end of the previous test run as specified in paragraph (d)(6) of this section. The idle mode ends when operator demand increases for the first acceleration event (Points A and B).

(ii) The first acceleration event in paragraph (d)(4)(i) of this section ends when operator demand is set to maximum for the second acceleration event (Point C).

(iii) The second acceleration event in paragraph (d)(4)(ii) of this section ends when the engine reaches 85 percent of maximum test speed, ƒntest, (Point D) and operator demand is set to minimum (Point E).

(iv) The transition period in paragraph (d)(4)(iii) of this section ends when operator demand is set to maximum (Point F).

(v) The third acceleration event in paragraph (d)(4)(iv) of this section ends when engine speed reaches 95 percent of ƒntest (Point H).

(vi) The transition period in paragraph (d)(5)(i) of this section ends when engine speed first decreases to a point more than 50 r/min below ƒntest (Point I).

(vii) The lugging mode in paragraph (d)(5)(ii) of this section ends when the engine reaches intermediate speed (Point J).

(2) Convert measured instantaneous values to standard opacity values, κstd, based on the appropriate optical path length specified in Table 1 of § 1065.1125 using the following equation:

(3) Select opacity results from corrected measurements collected across test segments as follows:

(i) Divide measurements from acceleration and lugging modes into half-second intervals. Determine average opacity values during each half-second interval.

(ii) Identify the 15 highest half-second values during the acceleration mode of each test run.

(iii) Identify the five highest half-second values during the lugging mode of each test run.

(iv) Identify the three overall highest values from paragraphs (e)(3)(ii) and (iii) of this section for each test run.

(f) Determine percent opacity as follows:

(1) Acceleration. Determine the percent opacity for the acceleration mode by calculating the average of the 45 readings from paragraph (e)(3)(ii) of this section.

(2) Lugging. Determine the percent opacity for the lugging mode by calculating the average of the 15 readings from paragraph (e)(3)(iii) of this section.

(3) Peak. Determine the percent opacity for the peaks in either acceleration or lugging mode by calculating the average of the 9 readings from paragraph (e)(3)(iv) of this section.

(g) Submit the following information in addition to what is required by § 1065.695:

(1) Exhaust pipe diameter(s).

(2) Measured maximum exhaust system backpressure over the entire test.

(3) Most recent date for establishing that each of the reference filters from paragraph (b) of this section are NIST-traceable.

(4) Measured smokemeter zero and linearity values after testing.

(5) 10 Hz data from all valid test runs.

(h) The following figure illustrates the dynamometer controls and engine speeds for exhaust opacity testing:

Sections 1065.1131 through 1065.1145 specify procedures for aging compression-ignition engine aftertreatment systems in an accelerated fashion to produce an aged aftertreatment system for durability demonstration. Determine the target number of hours that represents useful life for an engine family as described in the standard setting part. The method described is a procedure for translating field data that represents a given application into an accelerated aging cycle for that specific application, as well as methods for carrying out aging using that cycle. The procedure is intended to be representative of field aging, includes exposure to elements of both thermal and chemical aging, and is designed to achieve an acceleration of aging that is ten times a dynamometer or field test (1,000 hours of accelerated aging is equivalent to 10,000 hours of standard aging).

(a) Development of an application-specific accelerated aging cycle generally consists of the following steps:

(1) Gathering and analysis of input field data.

(2) Determination of key components for aging.

(3) Determination of a thermal deactivation coefficient for each key component.

(4) Determination of potential aging modes using clustering analysis.

(5) Down-selection of final aging modes.

(6) Incorporation of regeneration modes (if necessary).

(7) Cycle generation.

(8) Calculation of thermal deactivation.

(9) Cycle scaling to reach thermal deactivation.

(10) Determination of oil exposure rates.

(11) Determination of sulfur exposure rates.

(b) There are two methods for using field data to develop aging cycles, as described in § 1065.1139(b)(1) and (2). Method selection depends on the type of field data available. Method 1 directly uses field data to generate aging modes, while Method 2 uses field data to weight appropriate regulatory duty cycles that are used for emissions certification.

(c) Carry out accelerated aging on either a modified engine platform or a reactor-based burner platform. The requirements for these platforms are described in § 1065.1141 for engine bench aging and § 1065.1143 for burner-based bench aging.

This section describes the gathering and analysis of the field generated data that is required for generation of the data cycle. Gather data for the determination of aftertreatment exposure to thermal, lubricating oil, and sulfur related aging factors. You are not required to submit this data as part of your application, but you must make this data available if we request it.

(a) Field data target selection. Use good engineering judgment to select one or more target applications for gathering of input field data for the accelerated aging cycle generation that represent a greater than average exposure to potential field aging factors. It should be noted that the same application may not necessarily represent the worst case for all aging factors. If sufficient data is not available to make this determination with multiple applications, you may select the application that is expected to have the highest sales volume for a given engine family.

(1) Thermal exposure. We recommend that you select applications for a given engine family that represent the 90th percentile of exposure to thermal aging. For example, if a given engine family incorporates a periodic infrequent regeneration event that involves exposure to higher temperatures than are observed during normal (non-regeneration) operation, we recommend that you select an application wherein the total duration of the cumulative regeneration events is at the 90th percentile of expected applications for that family. For an engine that does not incorporate a distinct regeneration event, we recommend selecting an application that represents the 90th percentile in terms of the overall average temperature.

(2) Oil exposure. Use a combination of field and laboratory measurements to determine an average rate of oil consumption in grams per hour that reaches the exhaust. You may use the average total oil consumption rate of the engine if you are unable to determine what portion of the oil consumed reaches the exhaust aftertreatment.

(3) Sulfur exposure. The total sulfur exposure is the sum of fuel- and oil-related sulfur. Oil-related sulfur will be accounted for in the acceleration of oil exposure directly. We recommend that you determine fuel-related sulfur exposure by selecting an application that represents the 90th percentile of fuel consumption. Use good engineering judgment to determine that average rate of fuel consumption for the target application. You may use a combination of field and laboratory measurements to make this determination. Calculate the average rate of fuel-related sulfur exposure in grams per hour from the average rate of fuel consumption assuming a fuel sulfur level of 10 ppm by weight.

(b) Application data gathering. Use good engineering judgment to gather data from one or more field vehicles to support the accelerated aging cycle generation. We recommend that you gather data at a recording frequency of 1 Hz. The type of data that you gather will depend on the method you plan to use for cycle generation. Record both the data and the number of engine operating hours which that data represents regardless of method, as this information will be used to scale the cycle calculations. Use good engineering judgment to ensure that the amount of data recorded provides an accurate representation of field operation for the target application. If your application includes a periodic regeneration event, you must record multiple events to ensure that you have accurately captured the variation of those events. We recommend that you record at least 300 hours of field operation, and at least 3 different regeneration events if applicable.

(1) When using Method 1, direct field data use, as described in § 1065.1139(b)(1), record data for exhaust flow rate and at least one representative inlet temperature for each major aftertreatment system catalyst component, such as a diesel oxidation catalyst (DOC), diesel particulate filter (DPF), or selective catalytic reduction (SCR) catalyst. If a given catalyst component has multiple substrates installed directly in sequence, it is sufficient to record only the inlet temperature for the first catalyst substrate in the sequence. It is not necessary to record separate temperatures for substrates that are “zone-coated” with multiple catalyst functions. Record a representative outlet temperature for any major catalyst component that is used to elevate the temperature of downstream components. This could be the inlet of the next major component if that would be representative. We recommend that you record engine fuel rate to assist in the determination of sulfur exposure rates, but you may use other data for this purpose.

(2) When using Method 2, weighting of certification cycles, as described § 1065.1139(b)(2), record data for engine speed and engine load. Record sufficient ECM load parameters to determine a torque value that can be compared directly to engine torque as measured in the laboratory. You may optionally use ECM fuel rate measurements to determine load, but only if the same measurements can also be performed during laboratory testing on certification test cycles using sensors with comparable response characteristics. For example, you could use ECM fuel consumption rates for both field data and during laboratory tests.

(i) Optionally, as an alternative to the parameters required in this paragraph (b)(2), you may use a system exhaust temperature measurement to represent load. This requires one recorded temperature that represents the aftertreatment system. We recommend that you use a temperature recorded at the outlet of the first major catalyst component. If you choose to use this option, you must use the same temperature sensor for both field and laboratory measurements. Do not compare measurements between on-engine production temperature sensors with laboratory temperature sensors.

(ii) Optionally, as an alternative to the parameters required in this paragraph (b)(2), you may use exhaust flow and temperature measurements recorded in the field to support Method 2 calculations. Only one recorded temperature that represents the aftertreatment system is needed in this case. We recommend that you use a temperature recorded at the outlet of the first major catalyst component. Do not compare measurements between on-engine production temperature sensors with laboratory temperature sensors.

(3) If you have an aftertreatment system which involves periodic regeneration events where the temperature is raised above levels observed during normal operation, you must record data to characterize each such event. Data must be recorded at a frequency of at least 1 Hz, and you must record the exhaust flow rate and inlet temperature of each key catalyst component that will experience elevated temperatures during the regeneration. In addition, record a flag or variable that can be used to determine the beginning and end of a regeneration event. You must record at least three such events to allow determination of the average regeneration profile. If you have multiple types of regeneration events which influence different catalyst components in the system, you must record this data for each type of event separately. Use good engineering judgment to determine the average duration of each type of regeneration event, and the average interval of time between successive regeneration events of that type. You may use the data recorded for this cycle determination, or any other representative data to determine average regeneration duration or regeneration interval. These values may be determined from the analysis used to determine emission adjustments to account for infrequent regeneration of aftertreatment devices in § 1065.680.

Most compression-ignition engine aftertreatment systems contain multiple catalysts, each with their own aging characteristics. However, in the accelerated aging protocol the system will be aged as a whole. Therefore, it is necessary to determine which catalyst components are the key components that will be used for deriving and scaling the aging cycle.

(a) The primary aging catalyst in an aftertreatment system is the catalyst that is directly responsible for the majority of NOX reduction, such as a urea SCR catalyst in a compression ignition aftertreatment system. This catalyst will be used as the basis for cycle generation. If a system contains multiple SCR catalysts that are separated by other heat generating components that would result in a different rate of heat exposure, then each SCR catalyst must be tracked separately. Use good engineering judgment to determine when there are multiple primary catalyst components. An example of this would be a light-off SCR catalyst placed upstream of a DOC which is used to generate heat for regeneration and is followed by a DPF and a second downstream SCR catalyst. In this case, both the light-off SCR and the downstream SCR would have very different thermal history, and therefore must be tracked separately. In applications where there is no SCR catalyst in the aftertreatment system, the primary catalyst is the first oxidizing catalyst component in the system which is typically a DOC or catalyzed DPF.

(b) The secondary aging catalyst in an aftertreatment system is the catalyst that is intended to either alter exhaust characteristics or generate elevated temperature upstream of the primary catalyst. An example of a secondary component catalyst would be a DOC placed upstream of an SCR catalyst, with or without a DPF in between.

This section describes the method for determining the thermal reactivity coefficient(s) used for thermal heat load calculation in the accelerated aging protocol.

(a) The calculations for thermal degradation are based on the use of an Arrhenius rate law function to model cumulative thermal degradation due to heat exposure. Under this model, the thermal aging rate constant, k, is an exponential function of temperature which takes the form shown in the following equation:

(b) The process of determining Ea begins with determining what catalyst characteristic will be tracked as the basis for measuring thermal deactivation. This metric varies for each type of catalyst and may be determined from the experimental data using good engineering judgment. We recommend the following metrics; however, you may also use a different metric based on good engineering judgment:

(1) Copper-based zeolite SCR. Total ammonia storage capacity is a key aging metric for copper-zeolite SCR catalysts, and they typically contain multiple types of storage sites. It is typical to model these catalysts using two different storage sites, one of which is more active for NOX reduction, as this has been shown to be an effective metric for tracking thermal aging. In this case, the recommended aging metric is the ratio between the storage capacity of the two sites, with more active site being in the denominator.

(2) Iron-based zeolite SCR. Total ammonia storage capacity is a key aging metric for iron-zeolite SCR catalysts using a single storage site at 250 °C for tracking thermal aging.

(3) Vanadium SCR. Vanadium-based SCR catalysts do not feature a high level of ammonia storage like zeolites, therefore NOX reduction efficiency at lower temperatures in the range of 250 °C is the recommended metric for tracking thermal aging.

(4) Diesel oxidation catalysts. Conversion rate of NO to NO2 at 200 °C is the key aging metric for tracking thermal aging for DOCs which are used to optimize exhaust characteristics for a downstream SCR system. HC reduction efficiency (as measured using ethylene) at 200 °C is the key aging metric for DOCs which are part of a system that does not contain an SCR catalyst for NOX reduction. This same guidance applies to an oxidation catalyst coated onto the surface of a DPF, if there is no other DOC in the system.

(c)(1) Use good engineering judgment to select at least three different temperatures to run the degradation experiments at. We recommend selecting these temperatures to accelerated thermal deactivation such that measurable changes in the aging metric can be observed at multiple time points over the course of no more than 50 hours. Avoid temperatures that are too high to prevent rapid catalyst failure by a mechanism that does not represent normal aging. An example of temperatures to run the degradation experiment at for a small-pore copper zeolite SCR catalyst is 600 °C, 650 °C, and 725 °C.

(2) For each temperature selected, perform testing to assess the aging metric at different times. These time intervals do not need to be evenly spaced and it is typical to run these experiments using increasing time intervals (e.g., after 2, 4, 8, 16, and 32 hours). Use good engineering judgment to stop each temperature experiment after sufficient data has been generated to characterize the shape of the deactivation behavior at a given temperature.

(d) Generate a fit of the deactivation data generated in paragraph (b) of this section at each temperature using the generalized deactivation equation:

(e) Using the data pairs of temperature and thermal aging rate constant, k, from paragraph (c)(2) of this section, determine the thermal reactivity coefficient, Ea, by performing a regression analysis of the natural log of k versus the inverse of temperature, T, in Kelvin. Determine Ea from the slope of the resulting line using the following equation:

Generation of the accelerated aging cycle for a given application involves analysis of the field data to determine a set of aging modes that will represent that field operation. There are two methods of cycle generation, each of which is described separately below. Method 1 involves the direct application of field data and is used when the recorded data includes sufficient exhaust flow and temperature data to allow for determination of aging conditions directly from the field data set and must be available for all of the key components. Method 2 is meant to be used when insufficient flow and temperature data is available from the field data. In Method 2, the field data is used to weight a set of modes derived from the laboratory certification cycles for a given application. These weighted modes are then combined with laboratory recorded flow and temperatures on the certification cycles to derive aging modes. There are two different cases to consider for aging cycle generation, depending on whether or not a given aftertreatment system incorporates the use of a periodic regeneration event. For the purposes of this section, a “regeneration” is any event where the operating temperature of some part of the aftertreatment system is raised beyond levels that are observed during normal (non-regeneration) operation. The analysis of regeneration data is considered separately from normal operating data.

(a) Cycle generation process overview. The process of cycle generation begins with the determination of the number of bench aging hours. The input into this calculation is the number of real or field hours that represent the useful life for the target application. This could be given as a number of hours or miles, and for miles, the manufacturer must use field data and good engineering judgment to translate this to an equivalent number of operating hours for the target application. The target for the accelerated aging protocol is a 10-time acceleration of the aging process, therefore the total number of aging hours is always set at useful life hours divided by 10. For example, if an on-highway heavy duty engine has a full useful life of 750,000 miles and this is determined to be represented by 24,150 field hours, the target duration for the DAAAC protocol for this application would be 2,415 bench-aging hours. The 2,415 hours will then be divided among different operating modes that will be arranged to result in repetitive temperature cycling over that period. For systems that incorporate periodic regeneration, the total duration will be split between regeneration and normal (non-regeneration) operation. The analysis of normal operation data is given in paragraph (b) of this section. The analysis of regeneration data is given in paragraph (c) of this section.

(b) Analysis of normal (non-regeneration) operating data. This analysis develops a reduced set of aging modes that represent normal operation. As noted earlier, there are two methods for conducting this analysis, based on the data available.

(1) Method 1—Direct clustering. Use Method 1 when sufficient exhaust flow and temperature data are available directly from the field data. The data requirements for Method 1 are described in § 1065.1133(b)(1). The method involves three steps: clustering analysis, mode consolidation, and cycle building.

(i) The primary method for determining modes from a field data set involves the use of k-means clustering. K-means clustering is a method where a series of observations is partitioned into set of clusters of “similar” data points, where every observation is a member of a cluster with the nearest mean, which is referred to as the centroid of that cluster. The number of clusters is a parameter of the analysis, and the k-means algorithm generally seeks an optimal number of clusters to minimize the least-squares distance of all points to their respective centroids. There are a number of different commercially available software programs to perform k-means clustering, as well as freely available algorithm codes. K-means clustering can arrive at many different solutions, and we are providing the following guidance to help select the optimal solution for use in accelerated aging cycle generation. The process involves analyzing the data multiple time using an increasing number of clusters for each analysis. Use at least 5 clusters, and we recommend developing solutions for the range between 5 and 8 clusters, although you may use more if desired. Each cluster is a potential aging mode with a temperature and flow rate defined by the centroid. More clusters result in more aging modes, although this number may be reduced later via model consolidation.

(ii) The cubic clustering criteria (CCC) is a metric calculated for each solution having a different number of clusters. The computation of CCC is complex and described in more detail in the following reference. The CCC computation is normally available as one of the metrics in commercially available software packages that can be used for k-means clustering. The optimal solution is typically the one with the number of clusters corresponding to the highest CCC.

(iii) Check each solution, starting with the one with the highest CCC to determine if it satisfies the following requirements:

(A) No more than one cluster contains fewer than 3% of the data points.

(B) The temperature ratio between the centroid with the maximum temperature and the centroid with the minimum temperature is at least 1.6 for clusters containing more than 3% of the data points.

(C) If that solution does not satisfy these requirements move to the solution with the next highest CCC.

(iv) The process described in paragraph (c)(1)(iii) of this section generally works well for most data sets, but if you have difficulty with the CCC metric in a particular data set, use good engineering judgment to leverage additional criteria to help the down-selection process. Examples of alternate clustering metrics include a Davies-Bouldin Index (optimizing on the minimum value) or a Calinski-Harabasz Index (optimize on the maximum value).

(v) The initial candidate mode conditions are temperature and flow rate combinations that are the centroids for each cluster from the analysis in paragraph (c)(1)(iii) of this section. As part of the analysis, you must also determine the 10th percentile and 90th percentile temperatures for each cluster. These additional values may be needed later for the cycle heat load tuning process described in § 1065.1143.

(vi) The mode weight factor for a given cluster is the fraction data points contained within that cluster.

(2) Method 2—Cluster-based weighting of certification cycle modes. Use Method 2 if there is insufficient exhaust flow and temperature data from the field at the time the cycle is being developed. The data requirements for Method 2 are described in § 1065.1133(b)(2). You also need laboratory data recorded in the form of 1 Hz data sets for the regulatory duty cycles you are certifying to for your application as described in the standard setting part. Include exhaust flow rate and the inlet temperature for each key catalyst component in the laboratory data sets, as described in paragraph (e) of this section. The laboratory data sets must also include parameters that match the field data as described in § 1065.1133(b)(2), which will be used to facilitate the clustering analysis.

(i) Perform k-means clustering is described in § 1065.1133(b)(1) but using data sets containing the two parameters recorded in the field data sets. For example, you might use speed and torque, as recorded both in the field and the laboratory for Method 2 clustering.

(ii) Determine the fraction of points from each of the regulatory laboratory duty-cycles that are within each cluster, in addition to the overall fraction of points from the entire data set.

(iii) For each cycle, calculate a square sum error, SSE, as follows:

(iv) For each cycle, calculate a dissimilarity index as follows:

(v) If you have more than one regulatory duty cycle, weight the regulatory cycles.

(A) Determine the weighting factors for a given regulatory cycle, wi, by solving a system of equations:

(B) For example, for three duty cycles, calculate w1 as follows:

(C) Calculate subsequent wi values after calculating w1 as follows:

(D) Calculate the sum of the weighting factors to verify that they are equal to one.

(vi) For each regulatory cycle determine the average exhaust flow and the average inlet temperature for each key catalyst. Determine the 25th and 90th percentile inlet temperatures for the primary catalyst and the respective associated exhaust flow rate for each data point.

(vii) Use the cycle weights from paragraph (b)(2)(v) of this section and the mode conditions from paragraph (b)(2)(vi) of this section to generate a set of candidate aging modes by multiplying the cycle weight factor, w[cycle] by 0.25 for the 25th percentile temperature mode, 0.65 for the 50th percentile temperature mode, and by 0.10 for the 90th percentile temperature mode. This will generate a weighted set of mode numbers three times the number of regulatory cycles for the target application. Each mode will have a target temperature and exhaust flow rate.

(viii) If you have only one regulatory cycle for your application, use the cycle modes and weighting factors as they are given in the standard setting part.

(3) Determination of mode total durations. The output for either method will be a set of mode exhaust conditions, with an associated weighting factor for each mode. Multiply the mode weight factors by the total number of normal operating (non-regenerating) hours, to get a target mode duration for each mode. This will be used in the heat load calculations.

(c) Mode consolidation. Sometimes the clustering analysis process will generate multiple modes that are very similar to each other in temperature, such that although they are distinct modes they will not have a significantly different impact on aftertreatment aging. To reduce the complexity of the aging cycle, you may consolidate modes that are similar into a single mode as described below.

(1) Consolidate any two or more modes which have a target temperature within 10 °C into a single mode. If you choose to do this, the target temperature of the single consolidated mode is the temperature associated with the highest weight factor mode before consolidation. If the modes being consolidated all have weighting factors within 0.05 of each other, use the highest temperature among the modes.

(2) Use the highest exhaust flow target among the modes being combined as the target exhaust flow for new consolidate mode.

(3) Use the combined sum of the weighting factors for all modes being consolidate as the weighting factor for the new consolidated mode. Similarly, the total duration of the new consolidated mode is the sum of the durations of the modes being consolidated.

(d) Analysis of regeneration data. Regeneration data is treated separately from the normal operating mode data. Generally, the target for accelerated aging cycle operation is to run all of the regenerations that would be expected over the course of useful life. If multiple types of regeneration are conducted on different system components, each type of regeneration must be analyzed separately using the steps in this paragraph (d). The data requirements for input into this process are described in § 1065.1133(b)(3). The process described below is meant to determine a representative regeneration profile that will be used during aging. You may also ask us to allow the use of other engineering data or analysis to determine a representative regeneration profile.

(1) The total number of regenerations that will be run during the accelerated aging process will be the same as the total number of regenerations over useful life. Calculate this number by dividing the total number of useful life hours by the interval between regenerations as determined in § 1065.1133(b)(3).

(2) Use the 1 Hz regeneration data to determine an appropriate regeneration profile. The recorded regeneration event begins when the engine indicates it has started regeneration using the recorded regeneration indicator and ends when the aftertreatment has returned back to the normal operating temperature after the flag indicates the regeneration is complete.

(3) For each recorded regeneration, calculate the cumulative deactivation, Dt, using the equations in paragraph (e) of this section.

(4) If you have a large number of recorded regenerations in your data set, select a regeneration event with a cumulative deactivation representing the 75th percentile of the distribution of heat loads in your recorded data set. If you have a smaller number of recorded regenerations, such that you cannot clearly identify the real distribution, select the recorded regeneration with the highest recorded cumulative deactivation.

(5) This regeneration event will be used as the regeneration profile for that type of event during aging. The profile should include the entire event, include the temperature ramp and cool-down period.

(6) The regeneration must be conducted in the same manner as it is run in the field. For instance, if the regeneration temperature is generated from an exothermic reaction by injecting fuel in front of a DOC, this methodology should also be used during bench aging.

(7) If part of the system is at a lower temperature during regeneration because it is upstream of the temperature generating component, the set the target temperature for the aftertreatment system inlet to be equivalent to the system inlet temperature used during the highest duration non-regeneration mode, or 350 °C, whichever is lower.

(e) Heat load calculation and tuning for systems that have regeneration events. Perform this procedure after the preliminary cycles are completed for both normal and regeneration operation. The target cumulative deactivation is determined from the input field data, and then a similar calculation is performed for the preliminary aging cycle. If the cumulative deactivation for the preliminary cycle does not match cumulative deactivation from the field data, then the cycle is tuned over a series of steps until the target is matched.

(1) The deactivation for a given catalyst is calculated for each time step as follows:

(2) Calculate the cumulative deactivation, Dt, for a given catalyst over a series of time steps, N, using the following equation:

(3) Calculate the cumulative deactivation, Dt, for the input field data set. The time step for the calculations should be 1 second for 1-Hz input data.

(i) First calculate Dt for the non-regeneration portion of the field data set. For Method 2 use the 1-Hz data from the regulatory cycles as the field data set.

(ii) Divide the calculate field Dt by the number of hours represented in the field data set.

(iii) Multiply the hourly Dt by the number of hours required to reach full useful life. This is the target Dt,field-normi.

(iv) Multiply the total number of regenerations for full useful life by the cumulative deactivation Dt for the target regeneration profile determined in paragraph (d)(4) of this section. This is the target Dt,field-regen.

(v) The total target cumulative deactivation for the field data, Dt,field, is the sum of Dt,field-normi and Dt,field-regen.

(4) Calculate the cumulative deactivation for the candidate aging cycle generated under paragraphs (c) and (d) of this section as follows:

(i) Using the modes and mode durations for normal operation generated in paragraph (c) of this section, calculate the cumulative deactivation, Dt,cycle-norm, using the method given in paragraph (e)(2) of this section.

(ii) The total cumulative deactivation for the candidate aging cycle, Dt, is the sum of Dt,cycle-norm and Dt,field-regen.

(5) If Dt,cycle is within ±1% of Dt,field, the candidate cycle is deemed representative and may be used for aging.

(6) If Dt,cycle is not within ±1% of Dt,field, the candidate cycle must be adjusted to meet this criterion using the following steps. It should be noted that if the Dt,cycle is outside of the criteria it will usually be lower than the Dt,field.

(i) Increase the duration of the stable portion of the regeneration profile, which is defined as the portion of the regeneration profile where the temperature has completed ramping and is being controlled to a stationary target temperature. Note that this will increase the number of hours of regeneration time. You must compensate for this by decreasing the total number of normal operation (non-regeneration) hours in the cycle. Recalculate the duration of all the normal operation modes. You may not increase the duration of the stable portion of the regeneration profile by more than a factor of 2. If you reach this limit and you still do not meet the criteria in paragraph (e)(5) of this section, proceed to the next step.

(ii) Increase the target temperature of the stable portion of the regeneration profile by the amount necessary to reach the target criteria. You may not increase this temperature higher than the temperature observed in the regeneration profile with the highest Dt observed in the field. If you reach this limit and you still do not meet the criteria in paragraph (e)(5) of this section, proceed to the next step.

(iii) Increase the target temperature of the highest temperature normal operation mode. You may not increase this temperature above the 90th percentile determined in paragraph (b)(1)(v) of this section for Method 1, or above the maximum temperature for the regulatory cycle from which the mode was derived for Method 2. If you reach this limit and you still do not meet the criteria in paragraph (e)(5) of this section, you may repeat this step using the next highest temperature mode, until you reach the target, or all modes have been adjusted.

(iv) If you are unable to reach the target deactivation by following paragraphs (e)(6)(i) through (iii) of this section, use good engineering judgment to increase the number of regenerations to meet the criteria in paragraph (e)(5) of this section. Note that this will increase the total regeneration hours, therefore you must decrease the number of normal operation hours and re-calculate mode durations for the normal operation modes.

(f) Heat load calculation and tuning for systems that do not have regeneration events. Follow the steps described for systems with regeneration events to calculate Dt,field and Dt,cycle, omitting the steps related to regeneration events. The Dt,cycle will be well below the Dt,field. Follow the steps given below to adjust the cycle until you meet the criteria in paragraph (e)(5) of this section.

(1) Increase the temperature of the highest temperature mode. Use good engineering judgment to ensure that this temperature does not exceed the limits of the catalyst in a way that might cause rapid deactivation or failure via a mechanism that is not considered normal degradation.

(2) Increase the duration of the highest temperature mode and decrease the duration of the other modes in proportion. You may not increase the duration highest temperature mode by more than a factor of 2.

(g) Final aging cycle assembly. The final step of aging cycle development is the assembly of the actual cycle based on the mode data from either paragraph (e) of this section for systems with infrequent regeneration, or paragraph (f) of this section for systems that do not incorporate infrequent regeneration. This cycle will repeat a number of times until the total target aging duration has been reached.

(1) Cycle assembly with infrequent regenerations. For systems that use infrequent regenerations, the number of cycle repeats is equal to the number of regeneration events that happen over full useful life. The infrequent regenerations are placed at the end of the cycle. The total cycle duration of the aging cycle is calculated as the total aging duration in hours divided by the number of infrequent regeneration events. In the case of systems with multiple types of infrequent regenerations, use the regeneration with the lowest frequency to calculate the cycle duration.

(i) If you have multiple types of infrequent regenerations, arrange the more frequent regenerations such that they are spaced evenly throughout the cycle.

(ii) Determine the length of the normal (non-regeneration) part of the cycle by subtracting the regeneration duration, including any regeneration extension determined as part of cycle tuning from paragraph (e) of this section, from the total cycle duration. If you have multiple types of regeneration, then the combined total duration of regeneration events performed in the cycle must be subtracted from the total. For example, if you have one type of regeneration that is performed for 30 minutes every 30 cycle hours, and a second type that is performed for 30 minutes every 10 cycle hours (such that 3 of these secondary events will happen during each cycle), then you would subtract a total of 2 hours of regeneration time from the total cycle duration considering all 4 of these events.

(iii) Divide the duration of the normal part of the cycle into modes based on the final weighting factors determined in paragraph (c) of this section following any mode consolidation.

(iv) Place the mode with the lowest temperature first, then move to the highest temperature mode, followed by the next lowest temperature mode, and then the next highest mode, continuing in this alternating pattern until all modes are included.

(v) Transition between normal modes within (60 to 300) seconds. The transition period is considered complete when you are within ±5 °C of the target temperature for the primary key component. Transitions may follow any pattern of flow and temperature to reach this target within the required 300 seconds.

(vi) For normal modes longer than 30 minutes, you may count the transition time as time in mode. Account for the transition time for modes shorter than 30 minutes by shortening the duration of the longest mode by an equivalent amount of time.

(vii) If the shortest normal operating mode is longer than 60 minutes, you must divide the normal cycle into shorter sub-cycles with the same pattern in paragraph (g)(1)(iii) of this section, but with shorter durations, so that the pattern repeats two or more times. You must divide the cycle into sub-cycles until the duration of the shortest mode in each sub-cycle is no longer than 30 minutes. No mode may have a duration shorter than 15 minutes, not including transition time.

(viii) If a regeneration event is scheduled to occur during a normal mode, shift the start of regeneration to the end of the nearest normal mode.

(2) Cycle assembly without infrequent regenerations. For systems that do not use infrequent regenerations, the cycle will be arranged to achieve as much thermal cycling as possible using the following steps.

(i) Assign a duration of 15 minutes to the mode with the lowest weight factor. Calculate the duration of the remaining modes in proportion to the final weight factors after mode durations have been adjusted during heat load tuning in paragraph (f) of this section.

(ii) Place the mode with the lowest temperature first, then move to the highest temperature mode, followed by the next lowest temperature mode, and then the next highest mode, continuing in this alternating pattern until all modes are included.

(iii) Transition between normal modes within (60 to 300) seconds. The transition period is considered complete when you are within ±5 °C of the target temperature for the primary key component. Transitions may follow any pattern of flow and temperature to reach this target within the required 300 seconds.

(iv) For normal modes longer than 30 minutes, you may count the transition time as time in mode. Account for the transition time for modes shorter than 30 minutes by shortening the duration of the longest mode by an equivalent amount of time.

(v) This cycle will be repeated the number of times necessary to reach the target aging duration.

(h) Determination of accelerated oil exposure targets. The target oil exposure rate during accelerated aging is 10 times the field average oil consumption rate determined in § 1065.1133(a)(2). You must achieve this target exposure rate on a cycle average basis during aging. Use good engineering judgment to determine the oil exposure rates for individual operating modes that will achieve this cycle average target. For engine-based aging stands you will likely have different oil consumption rates for different modes depending on the speed and load conditions you set. For burner-based aging stands, you may find that you have to limit oil exposure rates at low exhaust flow or low temperature modes to ensure good atomization of injected oil. On a cycle average basis, the portion of oil exposure from the volatile introduction pathway (i.e., oil doped in the burner or engine fuel) must be between (10 to 30)% of the total. The remainder of oil exposure must be introduced through bulk pathway.

(1) Determination of accelerated fuel sulfur exposure targets. The target sulfur exposure rate for fuel-related sulfur is determined by utilizing the field mean fuel rate data for the engine determined in § 1065.1133(a)(3). Calculate the total sulfur exposure mass using this mean fuel rate, the total number of non-accelerated hours to reach full useful life, and a fuel sulfur level of 10 ppmw.

(i) For an engine-based aging stand, if you perform accelerated sulfur exposure by additizing engine fuel to a higher sulfur level, determine the accelerated aging target additized fuel sulfur mass fraction, wS, as follows:

(ii) If you use gaseous SO2 to perform accelerated sulfur exposure, such as on a burner-based stand, calculate the target SO2 concentration to be introduced, xSO2,target, as follows:

(iii) You may choose to turn off gaseous sulfur injection during infrequent regeneration modes, but if you do you must increase the target SO2 concentration by the ratio of total aging time to total normal (non-regeneration) aging time.

(2) [Reserved]

An engine-based accelerated aging platform is built around the use of a compression-ignition engine for generation of heat and flow. You are not required to use the same engine as the target application that is being aged. You may use any compression-ignition engine as a bench aging engine, and the engine may be modified as needed to support meeting the aging procedure requirements. You may use the same bench aging engine for deterioration factor determination from multiple engine families. The engine must be capable of reaching the combination of temperature, flow, NOX, and oil consumption targets required. We recommend using an engine platform larger than the target application for a given aftertreatment system to provide more flexibility to achieve the target conditions and oil consumption rates. You may modify the bench aging engine controls in any manner necessary to help reach aging conditions. You may bypass some of the bench aging engine exhaust around the aftertreatment system being aged to reach targets, but you must account for this in all calculations and monitoring to ensure that the correct amount of oil and sulfur are reaching the aftertreatment system. If you bypass some of the engine exhaust around the aftertreatment system, you must directly measure exhaust flow rate through the aftertreatment system. You may dilute bench aging engine exhaust prior to introduction to the aftertreatment system, but you must account for this in all calculations and monitoring to ensure that the correct engine conditions and the correct amount of oil and sulfur are reaching the aftertreatment system. Your engine-based aging stand must incorporate the following capabilities:

(a) Use good engineering judgment to incorporate a means of controlling temperature independent of the engine. An example of such a temperature control would be an air-to-air heat exchanger. The temperature control system must be designed to prevent condensation in the exhaust upstream of the aftertreatment system. This independent temperature control is necessary to provide the flexibility required to reach temperature, flow, oil consumption targets, and NOX targets.

(b) Use good engineering judgment to modify the engine to increase oil consumption rates to levels required for accelerated aging. These increased oil consumption levels must be sufficient to reach the bulk pathway exposure targets determined in § 1065.1139(h). A combination of engine modifications and careful operating mode selection will be used to reach the final bulk pathway oil exposure target on a cycle average. You must modify the engine in a fashion that will increase oil consumption in a manner such that the oil consumption is still generally representative of oil passing the piston rings into the cylinder. Use good engineering judgment to break in the modified engine to stabilize oil consumption rates. We recommend the following methods of modification (in order of preference):

(1) Install the top compression rings inverted (upside down) on all the cylinders of the bench aging engine.

(2) If the approach in paragraph (b)(1) of the section is insufficient to reach the targets, modify the oil control rings in one or more cylinders to create small notches or gaps (usually no more than 2 per cylinder) in the top portion of the oil control rings that contact the cylinder liner (care must be taken to avoid compromising the structural integrity of the ring itself).

(c) We recommend that the engine-aging stand include a constant volume oil system with a sufficiently large oil reservoir to avoid oil “top-offs” between oil change intervals.

(d) If the engine-aging stand will be used for aging of systems that perform infrequent regenerations, the aging stand must incorporate a means of increasing temperature representative of the target application. For example, if the target application increases temperature for regeneration by introducing fuel into the exhaust upstream of an oxidation catalyst, the aging stand must incorporate a similar method of introducing fuel into the exhaust.

(e) If the engine-aging stand will be used for aging systems that incorporate SCR-based NOX reduction, the aging stand must incorporate a representative means of introducing DEF at the appropriate location(s).

(f) Use good engineering judgment to incorporate a means of monitoring oil consumption on at least a periodic basis. You may use a periodic drain and weigh approach to quantify oil consumption. You must validate that the aging stand reaches oil consumption targets prior to the start of aging. You must verify oil consumption during aging prior to each emission testing point, and at each oil change interval. Validate or verify oil consumption over a running period of at least 72 hours to obtain a valid measurement. If you do not include the constant volume oil system recommended in paragraph (c) of this section, you must account for all oil additions.

(g) Use good engineering judgment to establish an oil change interval that allows you to maintain relatively stable oil consumption rates over the aging process. Note that this interval may be shorter than the normal recommended interval for the engine due to the modifications that have been made.

(h) If the engine-aging stand will be used for aging of systems that incorporate a diesel particulate filter (DPF), we recommend you perform secondary tracking of oil exposure by using clean (soot free) DPF weights to track ash loading and compare this mass of ash to the amount predicted using the measured oil consumption mass and the oil ash concentration. The mass of ash found by DPF weight should fall within (55 to 70)% of the of mass predicted from oil consumption measurements.

(i) Incorporate a means of introducing lubricating oil into the engine fuel to enable the volatile pathway of oil exposure. You must introduce sufficient oil to reach the volatile pathway oil exposure targets determined in paragraph (h) of this section. You must measure the rate of volatile pathway oil introduction on a continuous basis.

(j) If you perform sulfur acceleration by increasing the sulfur level of the engine fuel, you must meet the target sulfur level within ±5 ppmw. Verify the sulfur level of the fuel prior to starting aging, or whenever a new batch of aging fuel is acquired.

(k) If you use gaseous SO2 for sulfur acceleration, you must incorporate a means to introduce the gaseous SO2 upstream of the aftertreatment system. Use good engineering judgment to ensure that gaseous SO2 is well mixed prior to entering the aftertreatment system. You must monitor the rate of gaseous SO2 introduction on a continuous basis.

A burner-based aging platform is built using a fuel-fired burner as the primary heat generation mechanism. The burner must utilize diesel fuel and it must produce a lean exhaust gas mixture. You must configure the burner system to be capable of controlling temperature, exhaust flow rate, NOX, oxygen, and water to produce a representative exhaust mixture that meets the accelerated aging cycle targets for the aftertreatment system to be aged. You may bypass some of the bench aging exhaust around the aftertreatment system being aged to reach targets, but you must account for this in all calculations and monitoring to ensure that the correct amount of oil and sulfur are reaching the aftertreatment system. The burner system must incorporate the following capabilities:

(a) Directly measure the exhaust flow through the aftertreatment system being aged.

(b) Ensure transient response of the system is sufficient to meet the cycle transition time targets for all parameters.

(c) Incorporate a means of oxygen and water control such that the burner system is able to generate oxygen and water levels representative of compression-ignition engine exhaust.

(d) Incorporate a means of oil introduction for the bulk pathway. You must implement a method that introduces lubricating oil in a region of the burner that does not result in complete combustion of the oil, but at the same time is hot enough to oxidize oil and oil additives in a manner similar to what occurs when oil enters the cylinder of an engine past the piston rings. Care must be taken to ensure the oil is properly atomized and mixed into the post-combustion burner gases before they have cooled to normal exhaust temperatures, to insure proper digestion and oxidation of the oil constituents. You must measure the bulk pathway oil injection rate on a continuous basis. You must validate that this method produces representative oil products using the secondary method in § 1065.1141(h) regardless of whether you will use the burner-based aging stand to age systems which include a DPF. Use good engineering judgment to select a DPF for the initial validation of the system. Perform this validation when the burner-based aging stand is first commissioned or if any system modifications are made that affect the oil consumption introduction method. We also recommend that you examine ash distribution on the validation DPF in comparison to a representative engine aged DPF.

(e) Incorporate a means of introducing lubricating oil into the burner fuel to enable the volatile pathway of oil exposure. You must introduce sufficient oil to reach the volatile pathway oil exposure targets determined in § 1065.1139(h). You must measure the rate of volatile pathway oil introduction on a continuous basis.

(f) If the burner-based aging stand will be used for aging of systems that perform infrequent regenerations, the aging stand must incorporate a means of increasing temperature representative of the target application. For example, if the target application increases temperature for regeneration by introducing fuel into the exhaust upstream of an oxidation catalyst, the aging stand must incorporate a similar method of introducing fuel into the exhaust.

(g) If the burner-based aging stand will be used for aging of systems that incorporate SCR-based NOX reduction, the aging stand must incorporate a representative means of introducing DEF at the appropriate location(s).

(h) If the burner-based aging stand will be used for aging of systems that incorporate a diesel particulate filter (DPF), we recommend you perform secondary tracking of oil exposure by using clean (soot free) DPF weights to track ash loading and compare this mass of ash to the amount predicted using the measured oil consumption mass and the oil ash concentration. The mass of ash found by DPF weight should fall within (55 to 70)% of the of mass predicted from oil consumption measurements.

(i) You must incorporate a means to introduce the gaseous SO2 upstream of the aftertreatment system. Use good engineering judgment to ensure that gaseous SO2 is well mixed prior to entering the aftertreatment system. You must monitor the rate of gaseous SO2 introduction on a continuous basis.

The aging cycle generally consists first of practice runs to validate and tune the final cycle, followed by the actual running of the repeat cycles needed to accumulate field equivalent hours to reach full useful life. During the course of the aging run, various aging parameters are tracked to allow verification of proper cycle execution, as well as to allow for correction of the aging parameters to stay within the target limits.

(a) Preliminary cycle validation runs. Prior to the start of aging, conduct a number of practice runs to tune the cycle parameters. It is recommended that initial practice runs be conducted without the aftertreatment installed, but with the backpressure of the aftertreatment simulated to help ensure that the tuned cycle is representative. For final cycle tuning, including regenerations, it is recommended to use a duplicate or spare aftertreatment system of similar design to the target system, to avoid damage or excessive initial aging during the tuning. However, it is permissible to conduct final tuning using the target system being aged, but you must limit the total duration to no more than 100 field equivalent hours (10 hours of accelerated aging), including both thermal and chemical components. The process followed for these initial runs will vary depending on whether you are using an engine-based platform or a burner-based platform.

(1) Engine-based platform. (i) Initial cycle development. It will be necessary to determine a set of engine modes that will generate the required combinations of temperature, exhaust flow, oil consumption, and NOX to meet the target aging requirements. The development of these modes will be an iterative process using the engine and independent temperature control features of the aging stand. This process assumes that you have already implemented the oil consumption increase modifications, and that these have already been stabilized and validated to reach the necessary levels of bulk oil exposure. In general, we recommend the use of higher engine speeds and loads to generate the desired oil consumption, leveraging the temperature controls as needed to lower temperature to the targets. Several iterations will likely be needed to reach all targets. Note that during transitions you may utilize any combination of conditions necessary to help primary component catalysts reach the target temperature and flow conditions within no more than 5 minutes. For example, you may use a higher exhaust flow rate and lower temperature to rapidly cool the aftertreatment system to the next temperature. NOX targets do not need to be met during transitions. It is permissible to deviate from engine-out NOX emission targets if needed to reach the temperature, exhaust flow, and oil consumption targets. We recommend that you maintain a NOX level that is at the target level or higher, but you may lower NOX by up to 25%, if necessary, on some modes. Note that validation of oil consumption requires at least 72 hours of operation. Tune the parameters for infrequent regeneration towards then end of this initial development process (such as hydrocarbon injection schedules and temperature ramp rates).

(ii) Final cycle validation. Once the cycle is tuned, conduct a final run using the target aftertreatment system to verify conditions and log temperatures for heat load calculation. Using the recorded cycle data, calculate Dt for all primary component catalysts to ensure that you are matching the desired Dt,cycle targets. If you are not within ±3% of the target Dt,cycle, adjust the cycle accordingly. Calculate Dt for any secondary catalyst components to verify that they are within ±3% of either the target Dt or the target aging metric. Note that the accelerated aging methodology assumes that the relationship between the temperature of the primary and secondary catalyst components will the be same as the field observations. If this relationship deviates in the lab by having more or less heat transfer through the system, it may be necessary to modify that relationship on the aging stand. You may need to take measures such as adding or removing insulation or utilize external cooling fans to help these parameters match more closely.

(2) Burner-based platform. (i) Cycle development. The burner-based platform will be able to meet the exhaust flow, temperature, NOX, and oil consumption targets directly without the need for additional cycle development. This process assumes that you have already implemented and validated your oil consumption exposure methods to reach the necessary levels of bulk oil exposure. In addition, you must meet the oxygen and water targets during aging modes within ±2% for oxygen and ±2% for water. Note that during transitions you may utilize any combination of conditions necessary to help primary component catalysts reach the target temperature and flow conditions within no more than 5 minutes. For example, you may use a higher exhaust flow rate and lower temperature to rapidly cool the aftertreatment system to the next temperature. NOX, oxygen, and water targets do not need to be met during transitions.

(ii) Final cycle validation. Once the cycle is tuned, conduct a final run using the target aftertreatment system to verify conditions and log temperatures for heat load calculation. Using the recorded cycle data, calculate Dt for all primary components catalysts to ensure that you are matching the desired Dt,cycle targets. If you are not within ±3% of the target Dt,cycle, adjust the cycle accordingly. Calculate Dt for any secondary catalyst components to check that they are within ±3% of either the target Dt or the target aging metric. Note that the accelerated aging methodology assumes that the relationship between the temperature of the primary and secondary catalyst components will the be same as that observed in the field. If this relationship deviates in the lab by having more or less heat transfer through the system, it may be necessary to modify that relationship on the aging stand. You may need to take measures such as adding or removing insulation or utilize external cooling fans to help these parameters match more closely.

(b) Aftertreatment break in. Break in the emission-data engine and aftertreatment prior to the initial zero-hour test by running both on an engine dynamometer as described in subpart E of this part. Use good engineering judgment to develop a representative cycle that represents the field data. You may use the same data used for accelerated aging cycle development or other data. If your system utilizes infrequent regeneration, include at least one complete regeneration event, but we recommend that you include at least two such events to stabilize emissions performance. Your break in process must include at least 125 hours of engine operation with the aftertreatment system. You may ask to use a longer break in duration based on good engineering judgment, to ensure that emission performance is stabilized prior to the zero-hour testing.

(c) Initial emission testing. Prior to the start of accelerated aging conduct the initial zero-hour emission test and any required engine dynamometer aging following the requirements of the standard setting part for your engine. Dynaometer aging hours count toward the total aging hours.

(d) Accelerated aging. Following zero-hour emission testing and any engine dynamometer aging, perform accelerated aging using the cycle validated in either paragraph (a)(1) or (2) of this section. Repeat the cycle the number of times required to reach full useful life equivalent aging. Interrupt the aging cycle as needed to conduct any scheduled intermediate emission tests, clean the DPF of accumulated ash, and for any facility releated reasons. We recommended you interrupt aging at the end of a given aging cycle, following the completion of any scheduled infrequent regeneration event.

(e) QA tracking and validation. During aging, track a number of aging parameters to ensure that fall within the required limits. Correct aging parameters as need to remain within the required control limits.

(1) Thermal load tracking. For each primary catalyst component, generate a target line which describes the relationship between aging hours on the cycle and cumulative deactivation, Dt. Generate control limit lines that are ±3% of the target line. You must remain within these control limits over the course of aging. Adjust aging parameters as needed to remain within these limits for the primary catalyst components. For each secondary catalyst component, generate both a target Dt line and a line describing the target behavior of the aging metric directly. You must remain within either ±10% of either the Dt line or ±3% of the aging metric target line for any secondary catalyst component. Adjust aging parameters as needed to remain within these limits noting that you must remain within limits for the primary components. Adjusting the secondary catalyst aging may require altering heat transfer through the system to make it more representative of the field aging.

(2) Oil consumption tracking. Generate a target oil consumption line for both the bulk and volatile pathway which describes the relationship between oil exposure and aging hours on the cycle. For the engine-based stand the control limits are ±10% for total oil consumption, noting that the volatile pathway must not exceed 30% of the total. For the burner-based stand, the controls limits are ±5% for both pathways, which are tracked separately.

(i) Changing engine oil. For an engine-based platform, periodically change engine oil to maintain stable oil consumption rates and maintain the health of the aging engine. Interrupt aging as needed to perform oil changes. Perform a drain-and-weigh measurement. Following an oil change you must run at least 4 hours with the exhaust bypassing the aftertreatment system to stabilize the new oil. If you see a sudden change in oil consumption it may be necessary to stop aging and either change oil or correct an issue with the accelerated oil consumption. If the aging engine requires repairs to correct an oil consumption issue in the middle of aging, you must re-validate the oil consumption rate for 72 hours before you continue aging. The engine exhaust should be left bypassing the aftertreatment system until the repaired engine has been validated.

(ii) Secondary oil consumption validation. If your aftertreatment includes a diesel particulate filter, we recommend that you perform secondary validation of oil consumption by using clean (soot free) DPF weights to track ash loading and compare this mass of ash to the amount predicted using the measured oil consumption mass and the oil ash concentration. The mass of ash found by DPF weight should fall within a range of (55 to 70)% of the of mass predicted from oil consumption measurements. Perform this validation at the end of aging, at any intermediate emission test points, and at any point where you need to clean the DPF of accumulated ash in according with recommended maintenance.

(iii) Sulfur tracking. Generate a fuel sulfur exposure line describing the relationship between aging hours and cumulative target sulfur exposure mass. The control limits for sulfur exposure are ±3%. Log actual fuel consumption and the measured fuel sulfur level of the current batch of fuel (if you are doping fuel to accelerate sulfur exposure) for engine stand aging. Use these measurements to ensure that sulfur exposure remains within the control limits. Adjust sulfur doping levels in the fuel from batch to batch as needed to stay within limits. If you use gaseous SO2 for sulfur acceleration, monitor the mass flow rate of the gaseous sulfur. Use these measurements to calculate total sulfur mass exposure, and correct SO2 gas flow rates as needed to stay within the control limits.

(f) Emission testing at intermediate and final test points. Conduct emission testing at the end of aging and at any intermediate emission test points as described in the standard setting part. Following installation of the aged aftertreatment system on the emission-data engine at intermediate or final test points, prior to the start of emission testing, use good engineering judgment to operate the engine and aftertreatment system for a number of hours to stabilize emission controls and to allow any adaptive controls to update. Declare the number of stabilization hours prior to the start of the accelerated aging program.