Draft Internal Report 

Prepared for: 

Robert G. Fuerst 

Atmospheric Research and Exposure , . 

Assessment Laboratory 

Methods Research and Development Division I . 

Source Methods Research Branch . % 

U.S. Environmental Protection Agency 

Research Triangle Park, North Carolina 27711 

September 30, 1993 

RADIAN . 

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Prepared for: 

Robert G. Fuerst 

Atmospheric Research and Exposure Assessment Laboratory 

Methods Research and Development Division 

Source Methods Research Branch 

U.S. Environmental Protection Agency 

Research Triangle Park, North Carolina 27711 

Prepared by: 

Joette Steger 

P.O. Box 13000 

Research Triangle Park, North Carolina 27709 

September 30, 1993 
DISCLAIMER 

This document is intended for internal Agency use only. Mention of trade names or 

commercial products does not consititute endorsement or recommendation for use. 
Under all conditions tested, the presence of NH4C1 in the sampled gas introduced 

a positive bias into the HC1 measurement. This positive bias resulted from the NH4C1 

penetrating the filter and dissociating in the 0.1N H,S04 solution. A significant positive 

bias in the HCl measurement was observed even when the amount of NH4C1 spiked was 

as low as 2.44 ppmv. The positive bias in the HC1 measurement increased when the 

temperatures of the probe and filter increased. The positive bias in the HCl 

measurement may also be affected by the quantity of moisture in the sampled stream, 

increasing as the amount of moisture in the sampled stream decreases. The positive bias 

in the HCl measurement appears to be independent of the type of filter used in the 

sample train. When both HC1 and NH,CI are present in the sampled gas, a synergistic 

affect occurs, increasing the positive bias in the HC1 measurement. It may be possible to 

correct for the positive bias in the HC1 measurement by analyzing for ammonium ion 

and assuming the sole source of the ammonium ion is disassociated NH4C1. Finally, 

NH4Cl should be listed as an interferant in the method and the method should include a 
discussion of the trade off between filter and probe temperature and the negative and 

positive biases that will be introduced under various scenarios. 
3.0 RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1 

3.1 Baseline Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1 

3.2 High Temperature Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-6 

3.3 Moisture Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-6 

3.4 Hydrogen Chloride Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-7 

3.5 Filter Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-8 

3.6 Aerosol Spiking Solvent Experiment . . . . . . . . . . . . . . . . . . . . . . . . . 3-11 

4.0 CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1 

5.0 REFERENCES . . . . . . . . . . . . . . . . . . . . . . 

APPENDICES 

A TRAIN DATA OPERATING DATA SHEETS 

B TRAIN RECOVERY DATA SHEETS 

C ANALYSIS DATA SHEETS 
LIST OF TABLES 

Page 

Summary of Train Parameters and the Amount of Ammonium Chloride 

and HCl Spiked .............................................. 2-2 

Flow Rate. Purge Time. and Amount of HCl Spiked into each Reference 

Sample .................................................... 2-5 

Sample Train Reagent Type and Quantity by Impinger ................. 2-8 

Summary of Spiked Train Experiments Sampling at 0.76 CFM for Two 

Hours ..................................................... 3-2 

Distribution of Ammonium Chloride in Each Train Fraction ............ 3-3 

Summary of Measured HCl Bias for Each Test Condition .............. 3-4 

Summary of Analysis of Variance Results ........................... 3-5 

Spiked HCl Recoveries Corrected Based on Ammonium Ion Analysis ...... 3-9 

Summary of Reference Samples Prepared Using 262 ppmv HCl Gas ...... 3-10 

vii 
viii 

pyg

() 

halogens (X,) from stationary sources. The New Source Performance Standards (NSPS) 

sampling procedure for HX is 40 CFR Part 60, Method 26A. Method 26A is essentially 

the same as the sampling procedures in Method 0050. 

In Method 0050, gaseous and particulate pollutants are withdrawn isokinetically 

from the stationary source and are collected in a cyclone (optional), on a filter, and in 

absorbing solutions. The cyclone is used to collect liquid droplets and particulate matter. 

The cyclone is usually included in the sampling train to protect the filter when high 

levels of moisture and high levels of particulate matter are present. However, the 

cyclone may be removed from the train when the source emissions do not contain liquid 

droplets. It is important to protect the filter from high moisture because a wet filter will 

create a larger pressure drop in the train. The filter prevents halide salts from entering 

the impingers and biasing the results. The absorbing solutions consist of two impingers 

containing 0.1 N sulfuric acid (H,S04) and two impingers containing 0.1 N sodium 

hydroxide (NaOH). 
During HC1/C12 sampling, it is critical to maintain all surfaces between the 

stationary source wall and the filter at or above stack temperatures. Unheated sampling 

lines or cold spots in the sampling system can result in the deposition of water as 

condensate and possibly other materials on these cooled surfaces which may result in 

anomalous results. 

In a previous study,' the overall recommendations for collecting and analyzing 

HCl under either dry or humid conditions were: 

Operate the collection system at high (170°C [33g°F]) temperatures; and 

Use care to avoid the presence of moisture droplets in delivering HC1 

gases to impingers. 

No clear preference for glass or Teflon@ probe composition could be discerned 

from experimental data, so no recommendation can be made for choosing one over the 

other. Glass probes were used in this study. 

SW-846 Method 0050 is particularly well-suited for sampling at stationary sources 

that emit acid particulate matter and acidic vapor and that are controlled by wet 

scrubbers because the method collects acid aerosols, particulate matter, and gas phase 

HX. The acid particulate matter usually consists of HX dissolved in water droplets 

present as an aerosol. Other particulate matter, including halide salts, is collected on the 

filter. Acidic (0.1 N H,SO,) and alkaline (0.1 N NaOH) absorbing solutions are used to 

collect HX and X2, respectively. In the acidic absorbing solution, HX is solubilized to 

form halide ions (X-). Halogen gases, which have very low solubility in the acidic 

absorbing solution, pass through the acidic solution to the alkaline solution, where they 

are hydrolyzed to form a proton (H'), a X-, and a hypohalous acid (HXO). Ion 

chromatography (IC) is used to perform the analysis for X' in the absorbing solutions. 

The acidic and alkaline solutions are analyzed separately. The method is applicable to 
Ammonium chloride can exist in saturated pure mixtures as a molecular gas in 

equilibrium with its components (ammonia and chloride). However, NH4C1 has a strong 

tendency to dissociate at temperatures from 554°F to 626"~.' Because of this strong 

tendency to dissociate, NH4Cl is not thought to exist as a molecule in the gas phase, 

especially in unsaturated mixt~res.~ 

Though stack temperatures in many cement kilns and municipal waste combustors 

are lower (approximately 300°F), the concentration of ammonium and chloride in the 

stack is much lower (< 10 ppm HC1 and < 10 ppm ammonia), so the conditions favor 

dissociation2. The implication is that NH,C1 is not found in the stack gas in the gas 

phase. At ambient atmospheric conditions (6g°F), gaseous NH,C1 and particulate matter 

associated with NH,C1 have been detected at concentrations up to 5 micrograms per 

cubic meter.4 
Gaseous NH4Cl has not been found to be an interferant with continuous emission 

monitoring systems (CEMS). Solid NH4Cl collected on filters during Method 0050 or 

Method 26A sampling procedures should not skew chloride measurements since solid 

NH4C1 sublimes at 664°F while the filter holder temperature in Method 0050 and 

Method 26A is maintained at stack conditions (300°F [149"C] or higher). EPA 

Laboratory studies have shown that NH4Cl condensed onto particulate matter which is 

caught by the filter will have a high vapor pressure at stack temperatures. Pulling stack 

gas through the filter can allow NH4C1 to evaporate and pass through the filter to collect 

in the impinger solutions. However, an attempt to correlate ammonium ion 

concentrations in impinger solutions with chloride ions has not demonstrated a consistent 

relationship between the two ions. Ammonium chloride is therefore not the only source 

of chloride ions. Considering the physical data for NH,Cl which indicate complete 

disassociation into ammonia and HC1, it is not likely that a significant percentage of the 

chloride which is detected at cement kilns with Method 0050 or Method 26A originates 

from gaseous NH4Cl in the stack. 

A key issue with methods used to measure HC1 is a positive bias on sources 

containing ammonium chloride. Both Method 0050 and Method 26A show the positive 

bias and therefore may provide accurate results on sources emitting ammonium chloride. 

1.2 Obiectives 

This report of HCl and chloride sampling and analysis methods presents 

experimental results that address questions raised about the effect of ammonium 

chloride. The questions include: 

Does ammonium chloride penetrate the filter? 

How can interference from ammonium chloride be mitigated? 


total amount of ammonium chloride and HC1 spiked for each run are provided in 

Table 2-1. 

Four of the 14 trains with quartz filters were spiked with aqueous ammonium 

chloride and added moisture while being operated at 121°C (250°F). These experiments 

were designed to determine the effect of ammonium chloride on the chloride levels 

measured in the sulfuric acid collection solutions when the train was operated using the 

conditions recommended in the method. 

Triplicate trains with quartz filters were spiked with aqueous ammonium chloride 

and moisture while being operated at 200°C (400°F). These experiments were designed 

to determine the effect of train operating temperature on the amount of ammonium 

chloride that breaks through the filter. 
Table 2-1 

Summary of Train Parameters and the Amount of Ammonium Chloride and HCI Spiked 

" Capillary spiking nozzle plugged during run. 

Run ID and 

Date (1993) 

C-1 917 

C-2 917 

C-3 918 

C-4 9/10 

C-5 9/10 

C-6 9/10 

C-6W 9/13 

D-7 9/13 

D-8 9/14 

C-9 9/16 

C-10 9/16 

C-11 9/17 

D-15 9/23 

D-16 9/23 

M-17 9/23 

Probe 

Temp. 

("C) 

124 

126 

128 

121 

194 

207 

210 

125 

123 

123 

124 

121 

123 

121 

122 

Filter 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Teflon@ 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Quartz 

Moisture 

( O/O 

15.5 

16.2 

18.9 

22.0 

21.4 

22.4 

21.8 

4.18 

4.48 

17.9 

18.7 

19.2 

4.04 

4.03 

4.6 3 

Ammonium 

mL 

60 

70 

65 

60 

60 

60 

60 

60 

60 

62 

60 

50 

60 

8 5 

mL/min 

0 

0 

0 

0 

0 

0 

0 

0 

0 

1780 

1768 

1753 

0 

0 

0 

Chloride 

ppmv 

29.5 

2.44 

34.2 

31.8 

29.1 

29.1 

29.4 

29.1 

29.1 

29.1 

30.1 

29.1 

24.4 

29.1 

41.2 

Spiked 

Total mg 

180 

15.0 

210 

195 

180 

180 

180 

180 

180 

180 

186 

180 

150 

180 

255 

HCI Spiked 

ppmv 

0 

0 

0 

0 

0 

0 

0 

0 

0 I 

21.6 

2 1.5 

21.3 

0 

0 

0 

Total mg 

0 

0 

0 

0 

0 

0 

0 

0 

0 

91.0 

90.4 

89.6 

0 

0 

0 
One train with a quartz filter was spiked with ammonium chloride in methanol 

solution and no added moisture while being operated at 121°C (250°F). This experiment 

was designed to determine the effect of the aerosol spiking solution solvent on the 

amount of ammonium chloride that broke through the filter. 

Before the start of each run where HCl was spiked, a reference sample was 

generated, as shown in Figure 2-1, by purging the spike gas directly into a series of two 

impingers containing 100 mL of 0.1 N H,SO,. Flow rates and collection times for the 

reference samples are provided in Table 2-2. The reference samples were designed to 

confirm the concentration of HC1 in the supply cylinder and the amount of HCl 

dynamically spiked into the sample train. 
Uqukl NHdCI 

Splko In 

Teflon Glear GI-r Probo 

Too Tea Unor To 

I 1 1 S~~DIO 

I I \ Hoatod Probo 

Flow 

Controller 

I 

Ir I Sway 

Vahm 

sway 

Valvo 

Purge to Vent 

HCI 

Cyllndw 

Sbarn Ha Gsr & NH4CI 

In Injocbd at Sam. Point 

Mlnl Buck 

flow Cali brator 

To 

Vent 

f 

Figure 2-1. Mass Flow Controller and Impinger Set-up Used for Reference Samples H1 

to H-3. 

2.2 Method 0050 Samolin~ Train 

The Method 0050 sampling train was assembled as shown in Figure 2-2 from all 

glass components and charged with reagents as described in Table 2-3. All of the trains 

were spiked with ammonium chloride aerosol as described in Section 2.3. For Runs C-9 

through C-11, a tee connector was used between the nozzle and probe to introduce the 

gaseous 262 ppmv hydrogen chloride (HC1) in nitrogen. The flow rate of the HC1 gas 

was controlled with a Tylan@ mass flow controller for Runs C-9 through C-11. Gas flow 

rate was confirmed using a mini-Buck calibrator. 

A beaker of water on a hot plate was used to generate steam for Runs C-1 

through C-6W and Runs C-9 through C-11. The nozzle was placed directly over the 

beaker. Room air conditioned, by adding steam, was pulled through the train at 

approximately 0.75 ft3/minute for two hours. For all of the runs, the probe and filter hot 

box were heated to 121°C (250°F) or 200°C (400°F) before starting the purge gas through 

the train. 

2.3 Aerosol Soiking System 

The ammonium chloride was spiked into the train as an aerosol using a high 

pressure aerosol injection system developed under Work Assignment 32 of EPA Contract 

No. 68-Dl-0010 for dynamically spiking aryl amines into a Modified Method 5 sample 

train. The high pressure aerosol injection system was further evaluated and refined for 

spiking an aqueous ammonium chloride solution. The final design is shown in 

Figure 2-3. 

The aerosol spiking system consisted of a nitrogen cylinder equipped with a high 

pressure regulator. The regulator was connected to a 114-inch stainless steel tee with a 

3-foot long piece of 114-inch outer diameter (O.D.) stainless steel tubing. One end of 
Figure 2-2. Method 0050 Train Used for Ammonium Chloride Studies 
Table 2-3 

Sample Train Reagent Type and Quantity by Impinger 

5 I 200 I Silica Gel I Straight Stem 

Impinger Type 

Greenburg-Smith Tip 

w/plate 

Straight Stem 

Greenburg-Smith Tip 

w/plate 

4 Straight Stem 

Reagent Type 

0.1N H2S0, 

0.1N H,SO, 

0.1N NaOH 

Impinger 

Number 

1 

2 

3 

Reagent Quantity 

(s) 

100 

100 

100 

100 0.1N NaOH 
2-3. High pressure ~~rosol spiking system - - --* into a 

Method 0050 Train* 

- -. " --.-"- 

Used to spike 
the tee was connected to a pressure release valve so that the spiking system could be 

vented after use and before disassembling. The other end of the tee was connected to a 

107-mL stainless steel high pressure vessel with 1116-inch O.D. stainless steel tubing. 

The high pressure vessel made from an empty high performance liquid 

chromatography columnwas modified by drilling a port in the side so that the vessel 

could be refilled without disassembling the spiking system. An on/off valve was 

connected to the port using an 118-inch NPT to 114-inch Swageloke stainless steel fitting. 

The other end of the onloff valve was connected using 114-inch O.D. Teflon@ tubing to 

a 1-Liter polyethylene bottle with a 25-mL bottle top dispenser. 

The outlet end of the high pressure vessel was connected to an on/off valve. The 

onloff valve was connected through 1116-inch stainless steel tubing to a piece of 

capillary fused silica tubing (1 pm inner diameter). The fused silica tubing was placed 

inside a sheath of 114-inch Teflon@ tubing and inserted into a 518-inch glass tee with 

screw cap ends. The middle leg of the glass tee terminated in a female socket that was 

placed 114 inches above an erlenmeyer flask of boiling water. 

The performance of the dynamic aerosol high pressure spiking system was 

evaluated at several operating pressures between 850 and 1500 psig to determine the 

operating limits of the system. The injection system operated best at higher pressures 

with 1000 psig as a minimum operating pressure. At 1250 psig the system operated 

satisfactorily; however, an operating pressure of 1500 psig provided the most reliable and 

constant delivery rate of approximately 0.5 mL/min. 

For one train the aqueous ammonium chloride solution was substituted with a 

solution of ammonium chloride in methanol. The methanol solution made a finer 

aerosol than the aqueous solution and sprayed into the train at a faster rate using the 

same capillary restrictor and cylinder pressure. 
the 0.1N NaOH impingers. All of the impingers were weighed before being recovered 

into the appropriate tared bottles. The impingers and other train components were 

rinsed three times with deionized water and the rinses were added to the appropriate 

recovery bottles. 

2.6 Ion Chromatomaahic Analysis 

The samples were analyzed on a completely inert, metal-free Dionex DX-300 

gradient chromatography system for ion chromatography. For chloride determination, an 

AG4A guard column and an AS4A-SC anion separator column were used. Chloride was 

eluted using a buffer solution consisting of 17-mmoiar sodium carbonate and 18-mmolar 

sodium bicarbonate. For ammonium determination, a CGlO guard column and a CSlO 

cation separator column were used. Ammonium was eluted using a buffer solution 

consisting of 40-mmolar HC1 and 4-mmolar D,L-2,3-diaminopropionic acid 
monohydrochloride. Data from the Dionex-300 were processed through a Perkin-Elmer 

Nelson 2600 chromatography data system. 

Before sample analysis, the instrument was calibrated using four standards over 

the range of 5.0 to 20.0 ppm for chloride and 5.0 to 20.0 ppm for ammonium. A least 

squares fit applied to the data points resulted in curves with correlations of 0.9950 or 

better. 

Quality control samples made from separate sources of chloride and ammonium 

were analyzed using the established curve before and after every 20 samples. For the 

sample analysis to be acceptable, the quality control sample analysis had to be within 

k 10% of the target concentration. A blank and duplicate sample were run for every 

sample set or for every 20 samples. A matrix spike and matrix spike duplicate were run 

for every sample set or for every 20 samples. For the data analysis to be acceptable, the 

matrix spike and matrix spike duplicate analysis recoveries had to be within +.20%aof 

target. Any samples with responses above the calibration curve were diluted and 

reanalyzed. 
experiment started with spiking a 2.7 g/L ammonium chloride solution into the train at 

approximately 0.5 mL/minute. The probe and quartz filter were heated to 125°C and 

moisture was added at 18 k 4 percent. 

For Run C-2 the capillary spiking nozzle plugged, reducing the amount of 

ammonium chloride spiked into the train. This data indicate that even small amounts of 

ammonium chloride in the sampled gas can cause measureable bias in the determined 

HCl concentration. Bias for all four runs at 125°C ranged from + 1.38 to +24.3 mg HC1. 

Between 34 and 87% of the ammonium chloride spiked was accounted for in the four 

train components analyzed. Approximately 10 to 80% of the ammonium chloride 

remained in the probe and an additional 0.06 to 8.7% was collected on the filter. An 

additional 5 to 20% was collected in the H,SO, impingers. Less than 1% was collected 

in the NaOH impingers. 
Run Date Filter/Probe Amount/Concentration 

Number (1993) Temp. ("C) NH4CI Spiked 

I C-1 1 9-7 1 124 ( 29.5 ppmv (180 mg) 

Table 3-1 

Summary of Spiked Train Experiments Sampling at 0.76 CFM for Two Hours 

c - 2" 9-7 126 2.44 ppmv (15.0 mg) 

C-3 1 9-8 1 128 1 . 34.2 ppmv (210 mg) 

C - 4 9-10 12 1 3 1.8 ppmv ( 195 mg) 

C-5 9- 10 194 29.1 ppmv (180 mg) 

C-6 9-10 207 29.1 ppmv (180 mg) 

I C-6W 1 9-13 1 2 10 1 29.4 ppmv (1 80 mg) 

D-7 9-13 125 29.1 ppmv (180 mg) 

ID-8' 19-14 1 123 1 29.1 ppmv (1 80 mg) - - 

C-9 9-16 123 29.1 ppmv ( 180 mg) 

C-10 9-16 124 30.1 ppmv (1 86 mg) 1 

C-11 9-17 121 29.1ppmv(180mg) ~ 

D-15 9-23 123 24.4 ppmv (150 mg) I 

D-16 9-23 121 29.1 ppmv (1 80 mg) 

M-17d 9-23 122 41.2 ppmv (255 mg) 

Si 

a Bias = Measured - Spiked 

Capillary spiking nozzle plugged during run 

Teflon. filter used instead of quartz 

Percent 

Moisture Spiked Measured (mg) 

NH4Cl in methanol solution used instead of aqueous NH4CI solution 
Run Numb


3.2 High Temperature Experiments 

Runs C-5, C-6, and C-6W were designed to determine the effect of train operating 

temperature on the positive bias that has been reported when ammonium chloride is 

present in the sampled gas. The high temperature experiments started with spiking a 

2.7272 g/L ammonium chloride solution into the train at approximately 0.5 mL/minute. 

The probe and quartz filter were heated to 204°C and moisture was added at 

21.9 r 0.5 percent. 

Bias for all three runs at 204°C ranged from + 112 to + 115 mg HCl. Between 91 

and 94% of the ammonium chloride spiked was accounted for in the four train 

components analyzed. Less than 1% of the ammonium chloride remained in the probe 

or was collected on the filter. Over 90% was collected in the H2S0, impingers. Less 

than 1% was collected in the NaOH impingers. Thus, the bias in the HCl measurement 

from the presence of ammonium chloride was significantly increased by raising the 

temperature of the probe and filter to 204°C. Thus, when ammonium chloride is present 

in the sampled gas, the operating temperature of the train should be kept as low as 

possible, preferably 121°C or below. 

3.3 Moisture Experiments 

Runs D-7, D-15, and D-16 were designed to determine the effect of moisture on 

the positive bias that has been reported when ammonium chloride is present in the 

sampled gas. The moisture experiments started with spiking a 2.7272 g/L ammonium 

chloride solution into the train at approximately 0.5 mL/minute. The probe and quartz 

filter were heated to 123°C and moisture was added at 4.08 2 0.1 percent. 

Bias for all three runs at 4.08% moisture ranged from + 19.4 to +39.3 mg HCl. 

Between 86 and 100% of the ammonium chloride spiked was accounted for in the four 
ppy y pg ppg

standard into the train at 1.767 + 0.014 L/min. The probe and quartz filter were heated 

to 123°C and moisture was added at 18.6 a 0.7 percent. 

Bias for all three runs where the sampled stream contained 21.5 k 0.2 ppmv HCl 

and 29.4 a 0.7 ppmv ammonium chloride ranged from +52.0 to +69.4 mg HC1. Based 

on the ammonium ion analysis, between 107 and 112% of the ammonium chloride spiked 

was accounted for in the four train components analyzed. Between 19 and 52% of the 

ammonium chloride remained in the probe. Between 4 and 19% was collected on the 

filter. Between 31 and 48% was collected in the H,SO, impingers. Less than 25% was 

collected in the NaOH impingers. Thus, the bias in the HC1 measurement when both 

ammonium chloride and HC1 were present in the sampled gas approximately quadrupled. 

When ammonium chloride and HC1 are present in the sampled gas, the bias in the HCl 

measurement may be greater than when only ammonium chloride is present. 
The HC1 measurements were corrected for the ammonium ion measured in the 

0.1N H2S04 assuming that all of the ammonium ion collected was from ammonium 

chloride. The corrected HCl measurements are reported in Table 3-5 and ranged from 

110 to 132 percent. Thus, it may be possible to correct the HC1 results by also analyzing 

the samples for ammonium ion. 

Before the start of each run, a reference sample was generated by purging the 

spike gas directly into a series of three impingers. The first two impingers contained 

0.1N H2S04 and the last impinger contained 0.1N NaOH. Table 3-6 summarizes the 

reference results for Runs H-1 through H-3. The reference samples were generated by 

purging the gas at the flow rate used to spike the train for 10 minutes. The reference 

sample recoveries varied from 96.1 to 164 percent. 

3.5 Filter Experiment 

Run D-8 was designed to determine the affect of the filter material on the 

breakthrough of ammonium chloride into the impinger train. The filter experiment 

started with spiking a 2.7272 g/L ammonium chloride solution into the train at 

approximately 0.5 mL/rninute. The probe and Teflon@ filter were heated to 123°C and 

moisture was added at 4.48 percent. 

Bias for the run where the sample train used a Teflon@ filter was +27.3 mg HCl. 

Based on the ammonium ion analysis, 81% of the ammonium chloride spiked was 

accounted for in the four train components analyzed. Approximately 47% of the 

ammonium chloride remained in the probe. Another 5.94% was collected on the filter. 

The H2S04 impingers collected 22 percent. Less than 7% was collected in the NaOH 

impingers. Thus, the bias in the HCl measurement when a Teflon@ filter was used was 

similar to the bias obtained when quartz filters were used under the same sampling 

Table 3-6 

Summary of Reference Samples Prepared Using 261 ppmv HCl Gas 

Recovery 

132 

96.1 

164 

Reference 

Number 

H- 1 

H-2 

H-3 

Date 

9-16-93 

9-16-93 

9- 17-93 

Flow Rate 

(L/minute) 

1.780 

1.770 

1.75 1 

Collect ion 

Time 

(minutes) 

10 

10 

10 

Amount HCl 

Spiked (mg) 

7.58 

7.54 

7.46 

Table 3-6 

Summary of Reference Samples Prepared Using 261 ppmv HCl Gas 

Recovery 

(%) 

132 

96.1 

I H-3 1 9-17-93 1 1.751 1 10 1 7.46 1 164 I 

Reference 

Number 

H- 1 

H-2 

Date 

9- 16-93 

9- 16-93 

Amount HCl 

Spiked (mg) 

7.58 

7.54 

Flow Rate 

(L/minute) 

1.780 

1.770 

Collect ion 

Time 

(minutes) 

10 

10 
Approximately 54% of the ammonium chloride remained in the probe. Another 3.7% 

was collected on the filter. The H,SO, impingers collected 24.4 percent. Less than 5% 

was collected in the NaOH impingers. Thus, the bias in the HC1 measurement when the 

ammonium chloride was spiked as a methanol solution appeared to be slightly higher 

than the bias obtained when an aqueous ammonium chloride spiking solution was used. 

Thus, the way the ammonium chloride is spiked into the train may affect the magnitude 

but not the direction of the bias in the HC1 measurement. 

When both HC1 and ammonium chloride are present in the sampled gas, a 

synergistic affect occurs, increasing the positive bias in the HCl 

measurement; 

It may be possible to correct for the positive bias in the HC1 measurement 

by analyzing for ammonium ion and assuming the ammonium ion is 

disassociated ammonium chloride; 

Ammonium chloride should be listed as an interferent in the method; and 

The method should include a discussion of the trade off between filter and 

probe temperature and the negative and positive biases that will be 

introduced under various scenarios. 

Based on the results from Task A of this work assignment, operating the train at 

higher temperatures increases the precision of the HCl measurement and reduces the 

loss of HC1 in the cyclone.' Additional data is also available to show that operating the 

train at 200°C (400°F) also eliminates the negative bias reported when sampling sources 

containing less than 20 ppmv HCL6 However, based on the results of the experiments 
reported here, operating at higher temperatures significantly increases the positive bias 

in the HCl measurement when ammonium chloride is present in the source sample. 

People using the method on sources where ammonium chloride is present may 

want to use continuous emission monitoring when possible. When ammonium chloride is 

present and the levels of HCl are above 20 ppmv and the source sample is not saturated 

with water, maintaining the probe and filter temperature at 120°C or lower and 

measuring the ammonium ion to allow the HCl measurement to be corrected may 

provide HCl measurements with minimal bias. For sources where no information is 

available on the presence of ammonium chloride, maintaining the probe and filter at 

200°C (400°F) and analyzing for ammonium ion in the 0.1N H,SO, impingers may 

provide the best results. 

There are three recommendations for additional work. First, the sample train, 

operated at 121 -c 14" (250 2 25"F), should be spiked with 25 ppmv HCl and ammonia 

with approximately 20% moisture to determine whether the presence of ammonia biases 

the HCl measurement. It is possible that HCl and ammonia could react to form 

ammonium chloride and precipitate in the probe. Second, the sample train, operated at 

121 5 14" (250 5 25"F), should be spiked with 25 ppmv HCl and ammonium salts other 

than ammonium chloride with approximately 20% moisture to determine whether the 

presence of other ammonium salts biases the HC1 measurement. Again it is possible 

that HCI and ammonium salts could react to form ammonium chloride and precipitate in 

the probe. Third, sampling should be conducted at an actual source where both HCI and 

ammonium chloride, ammonia, or other ammonium salts are present. 
No. 68-Dl-0010, Work Assignment 52, September, 30, 1993. 

APPENDIX A 

TRAIN DATA OPERATING DATA SHEETS 









I// 

iii 

Operator Ambient Tern~erahre rR 

I -- 

- 

Pbnt . AREAL 

Date 

- Sampling Locslian 

Sample Type  on ~~mber . 

t

1 Traverse I Time I 


4: 

PC: 


APPENDIX B 

TRAIN RECOVERY DATA SHEETS 

(g) (g) 1 (g) 

0-IM 

1 Haso, I 00 W\ 8qu.3 oabx an.1 

' 

I J 

Total Weight Gain (g) 37Y. 0 ! 

I 
Total Weight Gain 
Total Weight Gain (g) / q%a - 0 1 

1 

2 

3 

o4N 

hY+ 

0 IN 

(LSOu 

04 

N.l ot, 

(g) 

\ e 0 

100 

\ 00 

1 

4 YISC 

sL;#+ 

4s .I p\& 

w.7 

7.333 

Gll,s 

61a -5 an.% 

I 

577.6 /5+-3 

5%-o 23-4 I 
MOISTURE RECOVERY FORM FOR METHOD 4 

Plant 

Date 

Sampling Location 

Sample ~ype 

Run Number 

Impinger. Box Number 

Recovery Person. 

Recovery Rinses 

Sample Identification 

Filter Number 

Xk&D Number 

Total Weight Gain 

~y b 

64 \L\ I 

- 

2 

LM 2.5.1.- 0.~53) 

/A 

Impinger 

Number 

Impinger 

Solution 

Amount of 

Solution ( Configuration1 Final i Initial 

Impinger Tip 

Impinger W 
Total Weight Gain (g) $$ I 
Total Weight Gain 

1 

2 

3 

0-iN 

o, 

0-1 N 

k5sf. 

O.IN 

n, GH 

1 o3 

1 OQ 

\Or3 

glb-S 

625-7 

G/IS 

w/ pl rf-c 

5Ls~\ 

&/ I s 

\-I pI+e 

s66- 

796. 

564. 
Total Weight Gain (g) 

(g) 

G.lN 

1 \OQ 63.3 

I I 1 I I 

75 -1 1 

j 
MOISTURE RECOVERY FORM FOR METHOD 4 

Plant 

Date 

Sampling Location 

Sample Type 

, Run Number 

Impinger Box Number 

Total Weight Gain ( 

ARhprC PA X3. 

743 -73 

LC& 

1 

Impinger 

Number 

1 

Recovery Person I KLPj 

Impinger 

Solution 

c-IN 

Recovery Rinses 

Sample Identification 

Filter Number 

,XAD Number 

1 I t-uo~t I I 4 ++e I 

X "1 '91 %O 

I \ 

(0 .SSW 

597.7 

Amount of 

Solution 

S6L.b 

Impinger Tip 

Configuration 

I 

Impinger W 

loo 

Final 

& [S 

Initial 

(g) 
(R) (g) 1 (g) 

c.iN 

\GQ G $ 1 kaSolt 6S%a 612 w.~ 
Total Weight Gain 
7 

Total Weight Gain (g) 
MOISTURE RECOVERY FORM FOR METHOD 4 

Impinger W 

Impinger Impinger Amount of Impinger Tip 

Number Solution Solution Configurationi Final t Initial 

Plant 

Date 

Total Weight Gain 

&RE LvHq? S 1 

9 - 17 -'I3 

Sampling Location 

Sample Type 

Run Number 

Impinger Box Number 

Recovery Person 

Recovery Rinses 

Sample Identification 

Filter Number . 

XAD Number 

I b w\ 1 C\> 

2 

'K.Lr\ 

7~ ~/m 
(g) (g) (g) I I/- 

Total Weight Gain (g) ( S7 .3 1 I I 
Total Weight Gain 

2 

3 

4 

0 -/)I 

1 

r 

0.1 N 

HxS 0, 

O-IN 

NQ OH. 

G-I tJ 

NaGh 

(g) 

lo@ 

l (Ic 

1 Qo 

\ QQ 

(37,Lf 

s&-c; $1~ 

E/ $ 

~r/ y\ hte 

S\unls~~ 

6( S.( 

(g) 

k, c 7 - 

%bLt 

$71.3 

553-3 .,; 

$'/I. 6 

565.' 
Total Weight Gain (grams) 4748- 

Number So1 ut i on (a) Conf iaurat i on Final Initial Gain , 

lo-IN I I i 

1 

I / S8.Mi IS.8. I Wo, I I 

2 I 0.N I 1 00 / 5G,3\t 1 6-33 2' 1 c;~~.l 76.7 %$Cq I I 

I 0.N I 

I I N4 I 100 I ..I !\(kt 

61 1 -SW.I~ $70.~; \a.y s 

C-\H I I I J 

1 Ns OV I \GO I +J : SXY-I 77q.3 73' 

I SIC I 

5 

I I 

I &EL I 100 I () I I ~~7.51 b7Y.9I 2A-6j I 

I I I I 
MOISTURE RECOVERY FORM FOR METHOD L 

i I I I Impinger u 

Impinger Amount of Impinger Tip 

Solution I Solution Configuration I Final 1 initial 

RFAL W A #53, 

7- & -73 

L& 

M\ d 

3 

Wl"r 

3~ yHn-h0 HC\ L% xh+qc3 

\ - 

N /A 

' 

Total Weight Gain 

Plant 

Datc 

Sampling Location 

Sample Type 

Run Number 

Impinger Box Number 

Recovery Person 

Recovery Rinses 

Sample Identlf lcation 

Filter ~umberXAD Number 
Total Weight Gain (g) 

(g) (g) 1 1 

I 

3, 1 

I 
(g) 1 

(2. IN 

1 WC, l@C s?-fyU 

Total Weight Gai: 
APPENDIX C 

ANALYSIS DATA SHEETS 







17.1 22.1 1