Convenient dioxin measuring method using an efficient sampling train, an efficient HPLC system and a highly sensitive HRGC/LRMS with a PTV injector

An efficient sampling method for dioxins from flue gas, an efficient automatic purification and fractionation method by a new HPLC system using a sulfuric acid-silica/silica column, a Nitro column and a PGC column, and sensitive determination method by an economical HRGC/LRMS using a programmable temperature vaporization (PTV) injector were developed. It was confirmed that the dioxins could be easily collected by the proposed simple sampling train consisting of only two bottles, and the extracted sample could be purified sufficiently and separated as mono-ortho PCBs, non-ortho PCBs and PCDDs/PCDFs completely with the proposed HPLC system. The peak areas of GC/MS were increased linearly with the injection volume up to 40 microl by the PTV technique, and the sensitivity could be increased to 20 times higher than usual. This convenient measuring method can drastically reduce operation time, consumption of hazardous solvent and cost.     

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.     

Effects of atmospheric pollution on lichen biodiversity (LB) in a Mediterranean region (Liguria, northwest Italy)

The effects of air pollution on lichen biodiversity (LB) were monitored in Liguria (northwest Italy). A systematic sampling strategy was adopted in order to avoid the influence of spatial autocorrelation on the results. An eight LB class scale permitted to point out the levels of naturality/alteration in the region. The comparison of these results with the ones obtained by mean of physico-chemical methodologies shows a good accordance. The results of this study suggest the possibility of designing an integrated monitoring network, in which biological monitoring will allow to estimate the level of alteration in remote areas, which account for most of this region and which are currently not covered by measurements with automatic systems.     

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.     

Population Exposure to Toxic Substances: Use of 1970 Census Data

A particulate sampling train has been constructed which satisfies the conflicting requirements of isokinetic sample extraction and constant flow rate through an inertial sizing device. Its design allows a variable fraction of the filtered emission gas to be added to the sample upstream of the inertial sizing device in order to maintain a preselected flow rate through this device while the gas flow rate into the sampling nozzle is adjusted to remain isokinetic with the local duct velocity. The prototype emission gas recycle (EGR) train was constructed by relatively simple modifications of a commercially available Method 5 sampling system, and much of the sampling technique is identical with Method 5 protocol. The train was tested by comparison of parallel runs in the EPA/SRI wind tunnel using redispersed fly ash. In one series of runs performed without inertial sizing devices, the EGR train and a colocated non- EGR train sampled 3-point traverses. The differences of the average mass concentrations measured by the two trains was 3.3 percent, with a standard deviation of 4.7 percent. In the next series of runs, identical cyclone inertial sizing devices were added to each train. The difference of the average mass concentration for these runs was 1.2 percent, with a standard deviation of 5.7 percent.     

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.     

Woodstove smoke and CO emissions: comparison of reference methods with the VIP sampler

A new field sampler has been developed for measuring the particulate matter (PM) and carbon monoxide emissions of woodburning stoves. Particulate matter is determined by carbon balance and the workup of a sample train which is similar to a room-temperature EPA Method 5G train. A steel tank, initially evacuated, serves as the motive force for sampling and also accumulates a gas sample for post-test analysis of time-averaged stack CO and CO2 concentrations. Workup procedures can be completed within 72 hours of sampler retrieval. The system has been compared to reference methods in two laboratory test series involving six different woodburning appliances and two independent laboratories. The correlation of field sampler emission rates and reference method rates is strong.     

Woodstove Smoke and CO Emissions: Comparison of Reference Methods with the VPI Sampler

A new field sampler has been developed for measuring the particulate matter (PM) and carbon monoxide emissions of woodburning stoves. Particulate matter is determined by carbon balance and the workup of a sample train which is similar to a room-temperature EPA Method 5G train. A steel tank, initially evacuated, serves as the motive force for sampling and also accumulates a gas sample for post-test analysis of time-averaged stack CO and CO₂ concentrations. Workup procedures can be completed, within 72 hours of sampler retrieval. The system has been compared to reference methods in two laboratory test series involving six different woodburning appliances and two independent laboratories. The correlation of field sampler emission rates and reference method rates is strong.     

Novel sampling methods for atmospheric semi-volatile organic compounds (SOCs) in a high altitude alpine environment

High- and low-volume active air samplers as well as bulk deposition samplers were developed to sample atmospheric SOCs under the adverse conditions of a mountain environment. Active sampling employed separate filters for different European source regions. Filters were switched depending on daily trajectory forecasts, whose accuracy was evaluated post hoc. The sampling continued on three alpine summits over five periods of four months. The prevailing trajectories varied stronger between sampling periods than between stations. The sampling equipment (active and bulk deposition) proved dependable for operation in a mountain environment, with idle times being mainly due to non-routine manipulations and connectivity.     

A High Volume Stack Sampler

This paper deals with the development design, and trial application of a sampling train to gather a relatively large amount of particulate sample in a short period of time. With air pollution sources installing control equipment to reduce emissions to the required low levels, it becomes necessary to use a sampling device which can collect a representative sample in a reasonable period of time. Some of the sampling trains currently being specified are expensive, awkward, and nearly impossible to use under field conditions. The high-volume train overcomes ail of these shortcomings and has some additional advantages. It uses the same glass fiber filter that is specified for ambient air particulate sampling so the emission test results are directly comparable to ambient air sampling data. The laboratories currently weighing and analyzing the glass filters need no additional equipment for the emission sampling analysis. The sample collected by the high-volume probe may be analyzed microscopically for size and characteristics of the particles. This is very important if control equipment is to be specified for the process or source. The high-volume sampler was evaluated on field tests of wood fired boilers, incinerators, wigwam burners, asphalt batching plants, seed cleaning plants, and wood fiber filtration systems. The results of several typical tests using the sampler on these sources are included in the paper.     

Stochastic model to forecast ground-level ozone concentration at urban and rural areas

Stochastic models that estimate the ground-level ozone concentrations in air at an urban and rural sampling points in South-eastern Spain have been developed. Studies of temporal series of data, spectral analyses of temporal series and ARIMA models have been used. The ARIMA model (1,0,0) x (1,0,1)24 satisfactorily predicts hourly ozone concentrations in the urban area. The ARIMA (2,1,1) x (0,1,1)24 has been developed for the rural area. In both sampling points, predictions of hourly ozone concentrations agree reasonably well with measured values. However, the prediction of hourly ozone concentrations in the rural point appears to be better than that of the urban point. The performance of ARIMA models suggests that this kind of modelling can be suitable for ozone concentrations forecasting.     

Arizona Hazardous Air Pollutants Monitoring Program

ABSTRACT

In order to evaluate the existing risk to public health in Arizona related to hazardous air pollution, ambient air monitoring for selected hazardous air pollutants (HAPs) was carried out in 1994-1996 in several representative urban and rural areas of Arizona. A wide range of organic HAPs was monitored, requiring a variety of sampling and analysis methods. Stainless steel SUMMA canisters were used for collection of volatile hydrocarbons and halocarbons, which were analyzed by capillary gas chromatography with flame ionization and electron capture detection (GC-FID/ECD). Carbonyl compounds were collected using 2,4-dinitrophenylhydrazine-impregnated cartridges and analyzed by high performance liquid chromatog-raphy with ultraviolet detection. Semi-volatile and non-volatile polycyclic aromatic compounds were collected using a sampling train consisting of a filter followed by a PUF/XAD-4/PUF sandwich cartridge. Following extraction, samples were analyzed by capillary GC with mass spectrometric detection (GC-MS). Database software was developed for data processing and reporting functions. This paper describes the sampling strategy and the sampling and analysis methods employed in the monitoring program and presents a summary of all the results obtained during the duration of the sampling program.     

A Method of Predicting Point and Path- Averaged Ambient Air VOC Concentrations,Using Meteorological Data

A method of predicting point and path-averaged ambient air VOC concentrations is described. This method was developed for the case of a plume generated from a single point source, and is based on the relationship between wind directional frequency and concentration. One-minute means of wind direction and wind speed were used as inputs to a Gaussian dispersion model to develop this relationship.

Both FTIR spectrometry and a whole-air sampling method were used to monitor VOC plumes during simulated field tests. One test set was also conducted using only whole-air samplers deployed in a closely-spaced network, thus providing an evaluation of the prediction technique free of any bias that might exist between the two analytical methods.

Correlations between observed point concentrations and wind directional frequencies were significant at the 0.05 level in most cases. Predicted path-integrated concentrations, based on observed point concentrations and meteorological data, were strongly correlated with observed values. Predicted point concentrations, based on observed path-integrated concentrations and meteorological data, accurately reflected the location and magnitude of the highest concentrations from each test, as well as the shape of the concentration-versus-crosswind distance curve.     

A high efficiency all glass sampling and concentration device for adsorptive semivolatile organics

A low-volume, inert sampling and enrichment device for semivolatile organic vapors is described. The device consists of two concentric fused silica capillaries. A small portion of the inter-capillary volume, cooled with a burst of compressed carbon dioxide, serves as a trap for the semivolatile organics. The low mass of the trap permits rapid sampling and desorption cycles suitable for applications requiring fast monitoring of semivolatile chemicals. The device is devoid of switching valves in the sampling train and consequently does not suffer from analyte loss due to irreversible adsorption or interference resulting from cross contamination. The device was successfully used for sampling low concentrations of highly adsorptive nitroaromatic compounds and is applicable for polychlorinated dibenzo-p-dioxins (PCDDs) and polyaromatic hydrocarbons (PAHs).     

Trace Metal Samples Collected in the Front and Back Halves of the E.P.A. Stack Sampling Train

A Purdue University industrial source sampling team has been involved since 1972 with a number of industrial and municipal collaborators, in order to characterize the flow of trace metals into the atmosphere. The plants involved in this cooperative research effort include the East Chicago municipal incinerator, rated at 450 ton/day of residential and commercial solid waste; a multiple furnace open hearth shop at a Northwest Indiana steel mill producing approximately 8 million ton/yr of steel; a coker arid sinter plant serving a 100,000 ton/yr vertical retort zinc production facility; and the Purdue University coal fired power plant equipped with 250,000 lb/hr steam boilers. At each of these facilities a number of stack samples have been obtained using the standard E.P.A. train. Analysis of the probe, filter, and impinger catch showed that in each case the front half of the E.P.A. Method 5¹ sampling train was highly efficient for collection of trace metal particulate.     

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.     

Experimental design strategy for the Weibull dose response model

The objective of this research was to determine optimum design point allocation for estimation of relative yield losses from ozone pollution when the true and fitted yield-ozone dose response relationship follows the Weibull. The optimum design is dependent on the values of the Weibull model parameters. A transformation was developed which allowed the optimum design (by the determinant criterion) for one parametric situation to be translated to any other, and permitted the search for optimum designs to be restricted to one set of Weibull parameters. Optimum designs were determined for the case where the Weibull parameters are assumed known, and effects of deviating from the optimum designs were investigated. Several alternative design strategies were considered for protecting against incorrectly guessing the Weibull model parameters when their true values are not known.     

Influence of temporally variable groundwater flow conditions on point measurements and contaminant mass flux estimations

Monitoring of contaminant concentrations, e.g., for the estimation of mass discharge or contaminant degradation rates, often is based on point measurements at observation wells. In addition to the problem, that point measurements may not be spatially representative, a further complication may arise due to the temporal dynamics of groundwater flow, which may cause a concentration measurement to be not temporally representative. This paper presents results from a numerical modeling study focusing on temporal variations of the groundwater flow direction. “Measurements” are obtained from point information representing observation wells installed along control planes using different well frequencies and configurations. Results of the scenario simulations show that temporally variable flow conditions can lead to significant temporal fluctuations of the concentration and thus are a substantial source of uncertainty for point measurements. Temporal variation of point concentration measurements may be as high as the average concentration determined, especially near the plume fringe, even when assuming a homogeneous distribution of the hydraulic conductivity. If a heterogeneous hydraulic conductivity field is present, the concentration variability due to a fluctuating groundwater flow direction varies significantly within the control plane and between the different realizations. Determination of contaminant mass fluxes is also influenced by the temporal variability of the concentration measurement, especially for large spacings of the observation wells. Passive dosimeter sampling is found to be appropriate for evaluating the stationarity of contaminant plumes as well as for estimating average concentrations over time when the plume has fully developed. Representative sampling has to be performed over several periods of groundwater flow fluctuation. For the determination of mass fluxes at heterogeneous sites, however, local fluxes, which may vary considerably along a control plane, have to be accounted for. Here, dosimeter sampling in combination with time integrated local water flux measurements can improve mass flux estimates under dynamic flow conditions.