Analytical procedures to assay environmental samples for PCDD/PCDF, PHA, PCB, chlorobenzenes (CB) and chlorophenols (CP)

Sample extracts from each section of a blank stack sampling train are portioned into two fractions, one to be used for PCDD/PCDF and PCB/CB analysis and the other for PAH/CP. The results of recovery studies for spiked compounds are presented. Developed protocols will be applied to future stack sampling programs and other environmental monitorings.     

Comparison of variability in dioxin and furan data acquired using single train and simultaneous multiple train stack sampling methods

The variance of polychlorinated dibenzo-p-dioxin (PCDD; dioxin) and polychlorinated dibenzofuran (PCDF; furan) data obtained from single- and simultaneous multiple train methods was compared. Single train triplicate data were used from 4 stack tests obtained from a long dry kiln cement plant and 18 stack tests from a municipal solid waste (MSW) incinerator. Data from the American Society of Mechanical Engineers (ASME) report Reference Method Accuracy and Precision (ReMAP) (Lanier and Hendrix, 2001) were used for the simultaneous multiple samples, which accounted for 27 data points. Nineteen data points were acquired from an ASME research facility, 5 from a MSW incinerator unrelated to the single train MSW incinerator, and 3 from a lightweight aggregate kiln (LWAK). The ReMAP procedure was used to determine the relationship between the standard deviation and the concentration of the single train and simultaneous multiple train data. Results indicated that there was benefit from the use of simultaneous multiple train sampling for concentrations above 129 pg toxic equivalency (TEQ)/m³. There was no indication of benefit from the use of simultaneous multiple train sampling at concentrations below 129 pg TEQ/m³.

Implications:Precision of stack sampling data can be the difference between meeting and failing compliance limits. Generally, three dioxin/furan samples are acquired when stack sampling to meet compliance regulations. A reliable estimation of the data’s true concentration is not possible with this small amount of data. Increasing the precision decreases the chance that the acquired concentration deviates greatly from the true concentration. Facilities that use the appropriate stack sampling method will benefit by either improved data precision or minimal stack sampling expenses. The observations made suggest that facilities that are expected to have dioxin/furan concentrations above 129 pg TEQ/m³ would increase the precision of samples by using simultaneous multiple train sampling.     

Comparison of various sampling methods for PCDDs and PCDFs in stack gas

There have been discussions about how complete PCDDs and PCDFs are sampled from stack gas of waste combustion plants by various sampling methods. In Germany, at present, a sampling method is used, which was first proposed by Nottrodt et al.¹, consisting of a filter device, condenser, and an absorption train. Since this sampling procedure complicates sampling and analysis, we compared this “standard procedure” with a “dilution method”, where only a filter, impregnated with paraffin, is used as trapping device, and also tested the effectiveness of XAD-2 as an adsorption trap.

As standard procedure the standard train was always used in parallel to other sampling methods. The results of four parallel sampling periods confirmed, that comparable results are obtained, when parallel sampling is carried out with the standard train.

The result of our investigation can be summarized as follows: The total emission of PCDDs and PCDFs determined by different sampling procedures varies only insignificantly. This means that sampling and analysis for PCDDs and PCDFs in stack gas could be simplified considerably.     

Studies on sampling methods for PCDDs and PCDFs in stack emission

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in stack emission exist both as vapor and sorbed onto the surface of particles. The partition between the two phases is of a dynamic nature and changes rapidly with temperature. When monitoring stack emissions, a sampling method must be used that efficiently collects both phases as well as any condensation aerosol formed in the sampling train. In this study, the two sampling methods used in Sweden, the cooled probe polyurethane foam plug (PUFP) sampling train and the sampling train recommended by the Swedish Environmental Protection Board has been tested for particle collection ability. The results show that an aerosol filter has to be introduced after the condensor in order to collect particle bound PCDDs and PCDFs efficiently.     

Particulate Emissions from Apartment House Boilers and Incinerators

The body of information presented in this paper is directed to researchers in stack testing methodology and to those concerned with reduction of emissions through equipment upgrading programs. Extensive testing was done using the U.S. Environmental Protection Agency’s Method 5 stack sampling train to obtain emission factors for existing apartment house boilers and incinerators in the City of New York. In addition to calculating emission factors, stack emission data were examined to compare results of simultaneous emission tests and to compare the dry particulate catch of the sampling train with the total particulate catch which included the impinger catch. Conclusions reached as a result of the testing were that published emission factors for boilers burning moderately high-sulfur residual oil are applicable to New York City boilers burning low-sulfur residual oil. In addition, it was found that the back half of the sampling train—the impinger section—collects a relatively constant amount of material when sampling oil-fired boilers. This may be due to absorption of S0₂ and S0₃ in the impingers and the subsequent formation of sulfuric acid. Comparison of simultaneous boiler tests indicated that the sampling train may be sensitive to variations in operating personnel, sampling conditions, and boiler operation. From tests of on-site incinerators, it was determined that previously published emission factors may be too high for well maintained and properly operated incinerators. The back half particulate catch was found to be relatively large which may have resulted from condensation of unburned organics from the burning waste material.     

Evaluation of the emission characteristics of PCDD/Fs from electric arc furnaces

Distribution of PCDD/F (polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran) congeners at two electric arc furnaces (EAFs) in Taiwan is evaluated via intensive stack sampling and analysis. Two kinds of exhaust system in EAFs including stack system and shutter system are selected for measuring dioxin emissions. In addition, dioxin emissions during oxidation and reduction stages at EAF-A were characterized. Results indicate that the PCDD/F concentration of stack gas in EAF-A was 4.39 ng/N m³ while total Toxic Equivalent Quantity (TEQ) concentration was 0.35 ng I-TEQ/N m³. The PCDD/F concentration of stack gas in EAF-B was 2.20 ng/N m³ and the TEQ concentration was 0.14 ng I-TEQ/N m³. 1,2,3,4,6,7,8-H_pCDF, OCDD and OCDF are the major contributors of the dioxin concentrations for two EAFs investigated and the percentage of PCDD/F in particulate phase increases as the chlorination level of the PCDD/F congener increases. The results obtained on gas/particulate partitioning of PCDD/Fs in flue gases prior to the APCD in EAFs indicate that more than 90% exists in particulate phase. In EAF-A, the PCDD/F concentration during oxidation stage is slightly higher than that measured during reduction stage, including the sampling points of CO converter outlet, prior to bag filter and stack. Majority of PCDD/Fs emitted from steel-making processes exists in particulate-phase (about 60–70%) at both EAFs investigated.     

Performance testing of a multimetals continuous emissions monitor

A prototype instrument, designed for continuous monitoring of hazardous air pollutant metal emissions in the stack gases of waste incinerators and industrial furnaces, has undergone a performance evaluation that included a relative accuracy test audit. The test results confirmed the instrument's ability to accurately measure stack gas metal concentrations and thus validate the applicability of the candidate technique for compliance assurance monitoring for the specific source involved. The analytical accuracy of this system, documented during the recent test exercise, represents a significant improvement in performance relative to that previously achieved, and can be attributed with certainty to the recent implementation of a shrouded nozzle sampling system. By reducing deposition losses of particulate matter in the extracted stack gas stream to acceptable levels, presentation of a more representative sample stream to the elemental analyzer has been accomplished. The present paper discusses the design and operation of the multimetals continuous emissions monitor (MMCEM), the shrouded nozzle sampling system, and the results of recent performance testing.     

Particle Size Distributions of Kraft Paper Mill Aerosols Obtained by Airborne Sampling

Size distributions of particles at several downwind points in a Kraft paper mill plume have been determined by means of airborne sampling. Size distributions from samples close to the stack were found to have a log normal frequency distribution, but significant deviations from the log normal were found farther downwind. Several possible physical mechanisms are postulated as causes for this behavior. Plume dilution with background particles appears to be the most likely mechanism. The airborne sampling system is described, and electron micrographs of sampled particles are presented.     

Performance Testing of a Multimetals Continuous Emissions Monitor

ABSTRACT

A prototype instrument, designed for continuous monitoring of hazardous air pollutant metal emissions in the stack gases of waste incinerators and industrial furnaces, has undergone a performance evaluation that included a relative accuracy test audit. The test results confirmed the instrument's ability to accurately measure stack gas metal concentrations and thus validate the applicability of the candidate technique for compliance assurance monitoring for the specific source involved. The analytical accuracy of this system, documented during the recent test exercise, represents a significant improvement in performance relative to that previously achieved, and can be attributed with certainty to the recent implementation of a shrouded nozzle sampling system. By reducing deposition losses of particulate matter in the extracted stack gas stream to acceptable levels, presentation of a more representative sample stream to the elemental analyzer has been accomplished. The present paper discusses the design and operation of the multimetals continuous emissions monitor (MMCEM), the shrouded nozzle sampling system, and the results of recent performance testing.     

Sampling Airborne Solids in a Duct Following a 90° Bend

Present standardized methods (ASME Power Test Code 27, Western Precipitation Bulletin 50, etc.) of stack sampling usually stress sampling under conditions of steady flow (no variation with time) in order to obtain data representative of the source emissions. On many occasions these standardized methods are applied when the velocity and/or the mass flow rate of pollutants do vary with time, thus impairing the accuracy of the sampling results. In addition, it is difficult to evaluate any inaccuracy of the sampling data. This paper classifies these two source variables into four categories and suggests basic sampling approaches for each type of source condition. Several standardized procedures are evaluated and classified according to the source conditions to which the procedure is applicable. The intent of this paper is to show the most accurate sampling approach for each source condition and thus serve as a guide when planning source sampling programs.     

Interlaboratory sampling and analysis of PCDDS and PCDFS in emissions from urban incinerators

Three laboratories participated in a PCDD and PCDF sampling experiment on the stack of a municipal waste incinerator and six laboratories examined a fly ash sample for PCDD_S and PCDF_S in order to assess analytical precision.

The flue gas sampling results are in agreement for the three laboratories and show that the PCDD_S and PCDF_S are predominantly in the gas phase, whereas emitted particulate account for 20% of the total PCDD/PCDF concentration.     

Polycyclic aromatic hydrocarbon emissions from clinical waste incineration

Since the introduction of the Environmental Protection Act in the UK, there are few reports of PAH emissions from clinical waste incinerators (CWIs) operating to improved performance standards. The main aim of this study is to determine PAH emissions from a state-of-the-art CWI focusing on the effects of reactive gases and operating variables on emissions. This was carried out by collection of stack samples over three phases of operation.

At stack conditions, most PAHs are predicted to be in the vapour phase. Reactive losses of PAHs were closely correlated by rank with expected reactivities from laboratory studies. Estimates of emissions incorporating sampling losses were derived, although no correlation was found between PAH losses and the modest levels of reactive stack gases. PAH concentrations were one to two orders of magnitude lower than earlier reports from incinerators without effective air pollution control equipment (APCE). The low levels of carbon monoxide recorded were not correlated with any PAHs.

This study demonstrates the impact of efficient combustion conditions and APCE on PAH emissions from a CWI.     

Development of a Practical Source Sampling Slide Rule

Historically, use of the nomograph to calculate isokinetic sampling rates for an EPA train has been cumbersome and awkward. In sampling situations where nomograph assumptions are not applicable, e.g., pitot tube coefficient not 0.85, dry molecular weight not 29, or where the ranges available are inadequate, e.g., stack moisture content greater than 50%, orifice meter constant less than one, the sampler cannot use the nomograph and must resort to other means for isokinetic determinations. The recent introductions of slide rule type calculators have offered some relief, but they still have inadequate capabilities and in addition, are difficult to learn and time consuming to use. The only sure alternative has been the equations. However, the equations for nozzle selection and sampling rate are not readily available in useable form in the literature. They are therefore presented in this paper with explanations.     

Nomograph for Field Checking Meter Calibrations on EPA-Type Stack Sampling Trains

In a typical "EPA train" for stack sampling, there are two meters, the dry gas meter and the orifice meter, which require periodic calibration. The controversy which presently exists over the required frequency of calibration is the result of using meters which rarely need calibration, but which have the potential of changing calibration at any time.     

Memory effect on the dioxin emissions from municipal waste incinerator in Taiwan

Evaluation of the dioxin removal efficiency of the air pollution control device (APCD) at an existing municipal waste incinerator (MWI) located in Taiwan is conducted via stack sampling and analysis. The MWI investigated is equipped with cyclones, dry lime scrubbing systems and fabric filters as APCDs. Results indicate that the patterns of dioxin isomers at APCDs' inlet and stack are similar. During the first year of carbon injection, the concentrations of emitted dioxin decreased greatly. The dioxin removal efficiency increased from 26.9% to 96.6% after injecting 115 kg/day activated carbon (AC). At the second year, the dioxin removal efficiency reaches 98.7% after injecting the same rate of AC continuously. The lower efficiency achieved with activated carbon injection (ACI) during the first year can be attributed to the memory effect, i.e. the dioxin or precursor desorbs slowly to the flue gas and increases the dioxin concentration at stack, resulting in a lower dioxin removal efficiency than expected.     

Emissions of Chlorinated Organics from Two Municipal Incinerators in Ontario

In this paper the results of sampling for trace chlorinated organics at two municipal refuse incinerators in Ontario are presented. The information may be of Interest to individuals concerned with the assessment of PCDD/PCDF (polychlorinated dibenzo-p-dioxin/polychlorinated dibenzofuran) emissions from incineration of refuse and their impact on the energyfrom- waste program. PCDDs, PCDFs, PCBs (polychlorinated biphenyls), CBs (chlorobenzenes) and CPs (chlorophenols) were quantified in all process streams including refuse, ash and stack emissions. Manual sorting of refuse and collection of ash samples were carried out simultaneously with three 24-hour continuous stack sampling tests at each plant. The results suggested that the total output of PCDDs and PCDFs varied proportionately with their input at both incinerators. However, the input of PCDDs/PCDFs could not account for their total output. The chemistry of PCDDs/PCDFs in the input and output streams were different in that only heptachlorinated and octachlorinated species were present in significant quantities in the refuse while lower chlorinated species were predominant in stack emissions and ash streams. There was no correspondence between the Input of PCBs/CBs/CPs and the output of PCDDs/PCDFs. The output of PCDDs/PCDFs, however, varied Inversely with the total output of PCBs/CBs/CPs, suggesting that the latter compounds could have been partially responsible for the formation of PCDDs and PCDFs. The PCDF emissions were also affected by combustion conditions; they were higher in magnitude and consisted of predominantly tetrachlorinated and pentachlorinated species at the plant where the combustion temperatures were lower.     

Dilution-based emissions sampling from stationary sources: Part 1--Compact sampler methodology and performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.     

Analysis of heavy metals in foliage near a modern refuse incinerator

Heavy metals such as cadmium and lead are typically found at high levels in fly ash from refuse incinerators. In two earlier studies it was found that such heavy metals on grass or tree foliage in the vicinity of old refuse incinerators with relatively low stacks and limited or no emission control devices showed a high degree of correlation between diminishing foliar concentration and the logarithm of sampling distance from the incinerator. In the study reported here of the concentration of cadmium and lead on foliage near a modern refuse incinerator with a high stack and efficient emission controls, the foliar concentrations of the metals showed no significant diminution with sampling distance from the incinerator. Factors affecting heavy metal emissions from refuse incinerators and contamination of nearby areas are discussed.     

Design of a compact dilution sampler for stationary combustion sources

The dilution sampling method simulates the rapid cooling and dilution processes after hot flue gas have left the stack. This allows gases or vapors to nucleate both homogeneously and heterogeneously, and to condense on preexisting particles in processes analogous to those that occur in the ambient environment. Using this method the authors can collect filterable particulate matter (PM) and condensible PM, that is, primary PM, simultaneously. In order to make this method more suitable for field investigation, a compact dilution sampler was developed. The sampler enhances mixing of dilution air with the stack gas, and thus shortens the length of the mixing section. The design decreases the nominal flow rate through the aging section, and accordingly reduces the size of the residence chamber. The decreased size of the sampler is suitable for field test. Sampling gas is pressured into the residence chamber, and air pressure in the chamber is micro-positive. Uncollected redundant gas is automatically discharged through unused sampling ports, which keeps the unit stable. Performance evaluation tests demonstrate that the design is reasonable. The sampler has been applied to characterize PM emissions from various combustion sources in China.     

Measuring Inorganic and Alkyl Lead Emissions from Stationary Sources

Described are the results from studies done to provide test methods for state and local air pollution control agencies to measure accurately the lead emissions from stationary source stacks as required in the National Ambient Air Quality Standard for Lead. Separate test methods were developed for measuring inorganic lead and alkyl lead compounds. Inorganic lead is collected in a standard particulate sampling train, digested with 50% (V/V) nitric acid and 3% hydrogen peroxide and analyzed by atomic absorption spectrometry. Alkyl lead compounds are collected in iodine monochloride and analyzed by atomic absorption spectrometry without prior solvent extraction. Standard solutions of inorganic lead in dilute nitric acid are used to calibrate the spectrophotometer in both methods. The inorganic lead test method was evaluated using baghouse dust samples from a primary copper and a primary lead smelter and stack samples from a lead recovery furnace, a primary battery manufacturing plant, a gray iron foundry and a secondary lead smelter. The alkyl lead method was evaluated using alkyl lead motor mix fluids and samples from an alkyl lead manufacturing plant vent stack.