HCL CEMS 

 Edul Chikhliwala \Chikli\ 

 to: 

 Keith Barnett 

 05/28/2010 10:24 AM 

 Show Details 

Dear Keith: 

 

Here is a "brain dump" regarding our existing HCL CEMS and issues related 

to the low levels associated with the Cement application. I provide a 

short discussion on the important aspects and have attached numerous 

supporting documents. I have intentionally kept this discussion informal 

but if need be, it can be converted into an appropriate technical 

document. Please review and give feedback. 

 

Thank you 

 

Edul Chikhliwala ("Chikli") 

EcoChem Analytics 

202 Reynolds, League City, TX 77573, USA 

281-338-9888 chikli@ecochem.biz 

 

=========================================================================

== 

=============================================== 

 

---- TYPE OF SYSTEM 

The EcoChem CEMS is based on HOT-WET MULTICOMPONENT TECHNOLOGY. The basic 

premise is to keep ALL surfaces that contact the flue gas to be above the 

dew point of the flue gas. Specifically, the probe, the sample line, the 

pump and the sample cell within the analyzer are maintained at 185 degC 

(365 degF) or higher. This ensures that there is no condensation of the 
reactive vapors leading to a reliable system and minimal downtime. In 

addition, we use a MULTICOMPONENT GAS ANALYZER -- a single analyzer 

measures up to 8 components. It is infra-red technology based instrument 

with an optional in-built Zirconium Oxide oxygen sensor. 

 

Specifically we use GAS FILTER CORRELATION (GFC) for measuring HCl. This 

technique uses an HCl gas filled cell along with an appropriate 

interference filter (centered around 3.6 micron and 4% band width). This 

allows us to be very specific to HCL and possible interference from other 

components is eliminated. The technique is simple and yet specific to 

HCL. 

This technique is described in detail in the book "Continuous Emission 

Monitoring" by James A. Jahnke and we have attached an relevant pages 

(note, in this book the emphasis of GFC is for CO detection but it can be 

equally applied towards HCl detection). In addition we have attached 

Proposed Test Method 322 which describes also the use of the Hot-Wet GFC 

technique for HCl monitoring at a Cement Kiln. This document also 

summarizes very well the EcoChem approach described in this email. 

 

--- CALIBRATION RELATED ISSUES 

HCl calibration gas can be difficult to obtain at higher accuracy levels. 

Typically +- 5% is the normal accuracy associated with HCl calibration 

gas. For lower concentrations, it is proposed that the HOVACAL (Hot Vapor 

Calibrator) be used for generating HCL vapors of known concentration. The 

HovaCAL has been certified and a paper describing the HovaCAL has been 

attached. The HovaCAL is widely used by EPA scientists and engineers for 

oxidized mercury calibration. In addition the HovaCAL has also been used 

for calibrating FTIR analyzers. 

 

--- BUDGETARY SYSTEM COST 

Attached please find an EcoChem quote for a HCL monitoring system which 

was purchased recently. This system will go online in two or three 

months. 

This system has dual range HCl (0-20 PPM and 0-200 PPM). 

 

---- MANPOWER REQUIRED TO RUN THE SYSTEM 

Our systems are designed for running 24 hours 365 days with minimal human 

intervention. More frequently, once a day a technician will check the 

calibration and make a visual check of the system. Every quarter 

maintenance is performed. The labor needs for our HCL system is no more 

than what is needed for a standard CEMS. 

 

--- SYSTEM INSTALLATIONS 

Attached please find a document which provides a list of installations 

using the EcoChem MC3 analyzer and measuring HCl as one of the 

components. 

 

--- CERTIFICATION BY REGULATORY AUTHORITIES 

The MC3 analyzer has been tested and approved by regulatory bodies in 

Europe. Attached please find the review reports of these evaluations (TUV 

in Germany and MCERTS in UK). Note, these studies were done several years 

ago and subsequently developments/optimization of the analyzer has 

occurred. For example, the TUV evaluation found cross-interference of >4% 

between the HCL signal and high SO2 levels. Subsequently by fine-tuning 
the optics and better choice of the interference filters this 

cross-interference has been eliminated. 

 

--- RELEVANCE TO EPA TEST METHODS AND DOCUMENTS 

As mentioned previously, EPA Proposed Test Method 321 (attached) is 

identical to the technology used by EcoChem. In addition, Eli Lilly has 

developed Performance Specification and QA/QC procedures for HCl CEMS 

which are posted on the EPA's website. These were developed for the Lilly 

incinerator T149 which uses an EcoChem MC3 analyzer. 

 

---- FUTURE ENHANCEMENTS 

The present MC3 analyzer has been certified for 0-9 PPM HCl by the TUV. 

The present MC3 analyzer has a 5.6 meter path length. So far customers 

have never requested lower ranges since there was no regulation. However 

for the cement application, we propose a MC3 analyzer with a range of 0 

to 

5 PPM HCL. This will be achieved by doing the following: 

--- Increasing the path length to 11.2 meter to increase the sensitivity 
A Portable Calibration Gas Generator for H2O, HCl, NH3 and Mercury 

Peter Wilbring1, Martin Schmaeh2

1

 TÜV Immissionsschutz und Energiesysteme GmbH, Am Grauen Stein, D-51105 Köln 

2

 IAS GmbH, Heddernheimer Landstraße 13A, D-60439 Frankfurt am Main 

presented at 

CEM 2001 

International Conference on Emissions Monitoring

25 – 27 April 2001 in Arnheim, Netherlands 

Abstract 

The calibration of emission measurement systems for water vapor, hydrogen chloride, ammonia and mercury is

difficult and span gas is not available for every component. On the principle of the dynamic evaporation of

liquids and the continuous addition of carries gas, a portable calibration gas generator was developed. Linearity, 

accuracy and the reproducibility is comparable with the quality of certified cylinder span gas or even better.

Besides a number of advantages over existing calibration methods, the system provides a calibration gas with

similar constitution as flue gas especially for water content. Mercury chloride has been investigated up to a 

concentration of 150 μg/m3. Besides carrier gas flow variation, also time constant and the speciation of mercury

under the influence of evaporator temperature has been examined. 

Introduction

The calibration of emission measuring systems for H2O, HCl, NH3 and mercury shows a few difficulties: H2O 

is not available as test gas up to the required concentrations and the handling of HCl needs appropriate 

experience [1]. The wall adsorption effects of HCl, NH3 and also HF even on heated surfaces of gas feeding 

components result in time lag, a dragging running behaviour and deviations of the reading, especially at low 

concentrations. Mercury as Hg° is available as test gas. But it is known, that the behaviour of HgCl2 is

completely different in terms of adsorption [2]. Moreover Hg° test gas is only suitable to check the photometer 

of the Hg-emission measuring system, but not the sample conditioning system. This demand has led to the 

development of the calibration gas generator HOVACAL. 

Principle of operation 

The device works on the principle of the dynamic evaporation of liquids and the constant addition of carrier gas.

A continuous flow of liquid is injected in an evaporator and mixed with a continuous carrier gas flow. Both

liquid and gas flow are monitored as mass flows and therefore independent of temperature and pressure. The

resulting concentrations can be calculated with the mixing equations given below. 

The basic equation for water vapour concentration is: 





 





• +

=

liquid

gas

H O

f v

v

c

1

100

2 ( 1) 

where cH2O is the water vapour concentration in % V/V, vliquid the liquid flow in g/min, vgas the carrier gas flow 

in ml/min based on standard conditions and f the volume factor from liquid to gas; the numerical value for water

is 1244,53.

1/7 
The use of aqueous solutions of hydrogen chloride, ammonia or mercury chloride in place of purified water 

result in gas vapour mixtures. The concentration of the gas components in the aqueous solution is an additional

parameter to the mix ratios of liquid and gas flows. This liquid concentration is usually given in mol/liter. 

The basic equation for aqueous solutions of components like HCl, NH3 and HgCl2 up to concentrations of 

approximate 1 mol/l , based on wet gas is:

6 •10

















+

• =

liquid

gas

K K

K

v

v

f

M n

c (2) 

where cK is the concentration of gaseous component in mg/m3

, MK the molecular mass of this component, nK is 

the liquid concentration in mol/liter and f is the volume factor for water. 

Is the concentration based on dry gas, the volume factor in equation (2) have to be omitted: 

6 •10

















• =

liquid

gas

K K

K

v

v

M n

c (3)

Principle of the device 

The calibration gas generator consists of a portable supply unit, an evaporator and an electronic balance. Supply 

unit and evaporator are connected via electrical power cables, temperature signal, carrier gas and liquid supply

lines. The construction is shown in diagrammatic form in Fig. 1.

Electronic balance

Carrier gas

Temperature controller

Liquid

Vaporizer

Supply unit

Gas-Vapor 

Mixture

Carrier gas

Pump

MFC

Fig. 1: Schematic representation of the calibration gas generator 

A peristaltic pump is used to pump the liquid into the evaporator from a liquid reservoir. The liquid is passed

through a fine filter to keep the evaporator and gas vapour mixture free of contamination. 

The mass of liquid pumped is dosed using a precision balance. The liquid flow is determined primarily by the 

speed of rotation and tube diameter of the pump. 

The carrier gas is fed to the supply unit at an overpressure and a mass flow controller injects a continuous and 

constant flow into the evaporator. 

2/7 
The evaporator can be set up some meters away from the supply unit. It has a carrier gas connection and a liquid 

supply port. The temperature of the evaporator can be controlled on the temperature controller integrated into

the supply unit. 

The gas vapour mixture must be extracted while still hot to prevent condensation and associated losses of gas 

components or water vapour. This is done by either connecting a heated pipe to the evaporator or

accommodating the entire evaporator in a larger heated unit, e.g. a measuring gas supply unit. 

Due to the liquid metering with an electronic balance and the gas metering with a mass flow controller, both

fluid flows are mass flows and the resulting concentration is independent of temperature and pressure. 

The evaporator can operated up to temperatures of 240 °C. Typical a temperature of 180 °C is used. At this 

temperature most of the sampling lines are operated. The temperature of the vaporisation is not critical, but the 

only criterion is that the temperature is well above the temperature of dew point. With 180 °C this condition is

fulfilled for water in any case and also for components like HCl, HF and NH3 in conjunction with water vapour. 

The working range for generating water vapour is defined in terms of three parameters and limited by the 

maximum power of the evaporator (800 W) . The presented device has characteristic, shown in Table 1.

Table 1: Characteristic of HOVACAL evaporator 

Parameter Minimum Maximum Optimum

Liquid flow rate in g/min 0,05 6 0,1 – 4 

Carrier gas flow in l/min 3 10 4 - 7 

Vaporisation temperature in °C 150 240 180 - 200 

Water vapour concentration % V/V 0,6 70 1,7 - 55 

Thus water vapour concentrations between 0 and 40 % V/V are generated in the optimum working range. 

For demand of higher water vapour content or higher carrier gas flow, the power of the evaporator can be

enhanced. 

Results and analysis

A laboratory test and a field trial have been made to examine the accuracy and linearity for the components H2O,

HCl, NH3 and HgCl2 [3, 4]. For verification of the concentration in laboratory, conventional methods have been

used. In the field trial, calibrated continuous emission measuring systems have been used. 

Accuracy

In Table 2, the accuracy of the calibration gas generator for the different components is shown. The carrier gas 

flow was set at 300 l/h, the temperature of the evaporator at 180 °C. The nominal value, calculated with above 

mixing equations, was set at the calibration gas generator, the analytical result was achieved by the specific 

conventional method. 

Table 2: Accuracy of HOVACAL in terms of mean deviation 

Component Measuring Range Number of

measurements 

Standard 

deviation 

% 

Slope 

Water vapour 0 – 40 % V/V 27 1,62 1,002 

Hydrogen chloride 0 –500 mg/m3 27 0,88 0,998 

Ammonia 0 – 500 mg/m3 27 0,97 0,999 

Mercury chloride 0 – 150 μg/m3 11 1,79 0,941 

The standard deviation as a result of a linear regression, shows high statistical security and a slope of nearly one 

for each component. The error of the conventional method has not been compensated. 

Linearity 

In Fig.2, 3 and 4 the linearity check for the different components are shown. A calibrated, continuous FTIRanalyser (CEMAS FTIR, ABB Automation Products) was used to monitor the test gas, generated by

3/7 
HOVACAL. The sampling system and measuring cell of the analyser was heated to 180 °C also temperature of 

evaporator and test gas. The evaporator was placed in the heated measuring gas supply unit of the analyser. The

carrier gas flow was set at 360 l/min. As carrier gas purified air or nitrogen was used. 

0

5

10

15

20

25

30

35

40

45

50

0 5 10 15 20 25 30 35 40 45 50

CEMAS Analyser Signal [Vol.-%]

Nominal Value HOVACAL [Vol.-%]

Water Vapour

Regression Curve

Confidence Area

Tolerance Area

Fig. 2: Linearity check of water vapour 

At 8 measuring points, 33 measurements were made. By linear regression a slope of 1,002 and a standard

deviation of 0,544 % V/V was found. 

0

20

40

60

80

100

120

140

160

180

0 20 40 60 80 100 120 140 160 180

CEMAS Analyser Signal [mg/m3]

Nominal Value HOVACAL [mg/m3]

Hydrogen Chloride

Regression Curve

Confidence Area

Tolerance Area

Fig. 3: Linearity check of hydrogen chloride 

At 6 measuring points, 24 measurements were made. By linear regression a slope of 0,982 and a standard

deviation of 4,436 mg/m3

 was found. 

4/7 
0

5

10

15

20

25

30

0 5 10 15 20 25 30

CEMAS Analyser Signal [mg/m3]

Nominal Value HOVACAL [mg/m3]

Ammonia

Regression Curve

Confidence Area

Tolerance Area

 Fig. 4: Linearity check of ammonia 

At 6 measuring points, 23 measurements were made. By linear regression a slope of 0,997 and a standard

deviation of 4,4.833 mg/m3

was found. 

Due to the low vapour pressure of water and aqueous hydrogen chloride solution, the handling of this solutions

is very simple. Aqueous ammonia solutions, especially at higher concentrations, cannot handled in an open 

bottle. A flexible bag system was designed for storage and handling them. 

In Fig. 5, the linearity check for mercury is shown over a range of 100 μg/m3

. The HOVACAL evaporator outlet 

was connected to a MERCEM analyser (Sick UPA). The gas tube between the evaporator and the analyser inlet 

was thoroughly heated up to 180 °C to prevent cold bridges and wall adsorption. 

0

20

40

60

80

100

120

140

0 20 40 60 80 100 120 140

MERCEM Analyser Signal [μg/m3]

Nominal Value HOVACAL [μg/m3]

Mercury

Regression Curve

Confidence Area

Tolerance Area

Fig. 5: Linearity check of mercury 

At 11 measuring points, 11 measurements were made. By linear regression a slope of 0,995 and a standard

deviation of 0,709 μg/m3was found. 

5/7 
Fig. 6 shows the speciation analysis. The ratio between elementary Hg and HgCl2 is between 20 and 30 %,

depending on the temperature of the evaporator [5].

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

230 °C 230 °C 220 °C 220 °C 200 °C 200 °C

Temperature of Evaporator

Hg-Concentration (μg/m3)

Hg(Cl2)-Concentration

Hg(0)-Concentration

Nominal Value HOVACAL

Fig. 6: Speciation analysis of HOVACAL mercury test gas 

At lower temperatures, the ratio Hg°/HgCl2 decreases. A hint, that thermal decomposition of HgCl2 

may occur at higher temperatures. The lower limit of temperature investigations is 180 °C, due to strong wall 

adsorption effects of mercury chloride. 

Conclusions 

The HCl- and NH3-test gas, produced with the calibration gas generator HOVACAL is comparable with

cylinder test gas. The humidity of the HOVACAL test gas can be adapted to the water content of the measuring

gas. Therefore, calibration and measuring conditions can be made very similar, especially in the case, when

instead of nitrogen or air, a span gas mixture of typical flue gas components is used. An additional advantage of 

the hot and wet span gas, is the reduced adsorption wall effect. 

The range of water vapour covers the typical applications in continuous emission monitoring for calibration and 

cross sensitivities check. 

The humidity of the generated mercury span gas can also adapted to the humidity of flue gas and allows besides

the calibration of Hg-analysers also the check of the sampling system. Further investigations will be made in 

defined change of the ratio between Hg° and HgCl2 . 

6/7 
7/7 

References 

[1] W. Jockel, C. Gökcek, H. Bollmacher: Stabilitätsuntersuchungen an HCl- und HF-Prüfgasen in 

Druckgasflaschen . Staub 47 (1987) 280 – 282 

[2] H. Braun, A. Gerig: Einfluß von Materialien bei der Beprobung quecksilberchlorid-haltiger Abgase. 

Staub 54 (1994) 167 – 170 

[3] P. Wilbring, Bericht über die Prüfung des Kalibriergasgenerators HOVACAL des Ing.-Büro Dr. 

Schmäh, Frankfurt, (1997), TÜV-Bericht 936/970001A 

[4] P. Wilbring, C. Röllig, Bericht über die Prüfung des Kalibriergasgenerators HOVACAL des Ing.-Büro 

Dr. Schmäh Frankfurt, für die Komponente Quecksilber, (1998) TÜV-Bericht 936/980001A 

[5] P. Wilbring, C. Röllig, Bericht über die Prüfung des Kalibriergasgenerators HOVACAL des Ing.-Büro 

Dr. Schmäh Frankfurt, für die Komponente Quecksilber, (2000) TÜV-Bericht 936/000001A 

Biographical detail of the authors 

Dr. Martin Schmäh, Physicist, IAS GmbH, Manufacturer of the calibration gas generator HOVACAL located in 

Frankfurt am Main, Germany . He works since 1987 in the area of gas analysis and since 1997 Manager of IAS. 

Dr. Peter Wilbring, Chemist, TÜV Immissionsschutz und Energiesysteme GmbH, D-51101 Köln, Germany. He 

works since 1990 in the field of environmental protection especially in the area testing of continuous emission 

measurement and ambient air measurement systems. 
EcoChem References and Installations

EcoChem Installations 

Third Generation Multicomponent Systems (since 2002) 

Beginning late 2001 and early 2002 EcoChem Analytics began installation of the updated, 3rd Generation 

multicomponent Infrared Analyzer Systems. These systems utilize the MC3 multicomponent analyzer. 

Aside from the process monitoring applications identified as such, the CEMS installed in the US have all 

been certified to US EPA Part 60, Part 75 and many state regulations including seven systems under 

PADEP (Pennsylvania Department of Environmental Protection) performance specifications. The following 

listing provides details of MC3 systems which have been placed into service. 

# Name Location Application Components 

EA-239 US EPA Research Triangle 

Park, NC 

Combustion Research HBr, HCl, NH3, SO2, NO, CO2, 

H2O, O2 

EA 229-238 CF Industries / 

Tyco 

Donaldsonville, 

LA 

Nitric Acid Plant NO, NO2, N2O, NH3, CO, H2O, 

O2 

EA 228 Schuylkill Energy 

Resources 

Shenandoah, PA Coal-Fired Power Plant NOx, SO2, CO2, H2O, O2 

EA 227 Wheelabrator 

Chambers 

Anahuac, TX Medical Waste Incinerator NOx, SO2, CO, H2O, O2 

EA 226 Wheelabrator 

Westchester 

Peekskill, NY Waste-to-Energy NOx, SO2, CO, H2O, O2 

EA 221-225 Ocean State 

Power 

Harrisville, RI Gas Turbine with SCR NO, NO2, CO, CO2, SO2, O2, 

H20 

EA 219 Rentech Midwest 

Energy 

East Dubuque, IL Nitric Acid / Ammonium 

Nitrate 

NO, NO2, N2O, SO2, CO, H2O 

EA 218 Wheelabrator 

Westchester 

Peekskill, NY Waste-to-Energy NOx, SO2, CO, H2O, O2 

EA 217-218 PCS Geismar, LA Nitric Acid NO, NO2, N2O, SO2, CO, H2O 

EA 216 Albemarle Pasadena, TX Chemical Facility NOx, NH3, CO, H2O 

EA 214-215 Wheelabrator 

Lisbon 

Lisbon, CT Waste-to-Energy NOx, SO2, CO, H2O, O2 

EA 213 Rentech Midwest 

Energy 

East Dubuque, IL Nitric Acid / Ammonium 

Nitrate 

NO, NO2, N2O, SO2, CO, H2O 

EA 212 Covanta 

Philippines 

Quezon, 

Philippines 

Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, O2 

EA 211 PCS Lima, OH Nitric Acid NO, NO2, N2O, SO2, CO, H2O 

EA 187 -210 Xcel Power Texas facilities Coal and natural Gas Fired 

Facilities 

NOx, SO2, CO, CO2, H2O, O2 

EA 186 Rosebud Power 

Plant 

Colstrip, MT Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, O2 

EA 185 Eli Lilly Shadeland, IN Waste Incinerator SO2, NOx, CO, CO2, H2O, O2 

EA 184 Ash Grove 

Cement 

Clancy, MT Cement Kiln SO2, NOx, CO, CO2, H2O, O2 

EA 182-183 Wasatch 

Integrated Waste 

Management 

District 

Layton, UT Waste-to-Energy NOx, SO2, CO, CO2, H2O, O2 

...Table continues on next page 
EcoChem References and Installations

Third Generation Systems (continued) 

# Name Location Application Components 

EA 181 Sunnyside 

Cogeneration 

Sunnyside, UT Coal-Fired Power Plant NOx, SO2, CO2, H2O, O2 

EA 180 Panther Creek 

Energy Facility 

Nesquehoning, PA Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, 

O2 

EA 179 Panther Creek 

Energy Facility 

Nesquehoning, PA Coal-Fired Power Plant NOx, SO2, CO, CO2, H2O, 

O2 

EA 178 Onyx 

Environmental 

Sauget, IL Waste Incinerator HCl, CO, O2 

EA 177 Onyx 

Environmental 

Port Arthur, TX Process Monitor CO, CO2, H2O, O2 

EA 176 Onyx 

Environmental 

Port Arthur, TX Process Monitor CO, CO2, H2O, O2 

EA 175 Pollution Control 

Department 

Bangkok, 

Thailand 

Mobile Van NOx, CO, CO2, SO2, H2O, 

O2, HCl, NH3, H2S, TRS 

EA 174 GCC Dacotah Rapid City, SD Cement Kiln SO2, O2, H2O 

EA 173 Eli Lilly Shadeland, IN Waste Incinerator NOx, CO, SO2, HCl, O2, 

H2O 

EA 172 Gilberton Power Frackville, PA Coal-Fired Power Plant NOx, SO2, CO2, H2O, O2 

EA 171-170 Onyx 

Environmental 

Sauget, IL Waste Incinerator NOx, CO, CO2, H2O, O2 

EA 169-167 Atlas Equipment Taipei, Taiwan Waste Incinerator NOx, CO, SO2, H2O, O2, 

HCl 

EA 166-163 Wheelabrator 

Falls Township 

Morrisville, PA Waste-to-Energy NOx, SO2, CO, HCl, H2O, 

O2 

EA 162 SE Analytics Kazakhstan Waste Incinerator NOx, CO, SO2, HCl, O2, 

H2O 

EA 161 SE Analytics Mozambique Waste Incinerator NOx, CO, SO2, HCl, O2, 

H2O 

EA 160 Eli Lilly Shadeland, IN Waste Incinerator NOx, CO, SO2, O2, H2O 

...Table continues on next page 
EcoChem References and Installations

Third Generation Systems (continued) 

# Name Location Application Components 

EA 158-

157 

Atlas Equipment Taipei, Taiwan Waste Incinerator NOx, CO, SO2, H2O, O2, HCl 

EA 156 Fodisch Korea Process HCl, NO, NO2, CO, NH3, H2O 

EA 155-

154 

GCC Dacotah Rapid City, SD Cement Kiln NOx, CO, O2, H2O 

EA 153-

152 

Atlas Equipment Taipei, Taiwan Waste Incinerator NOx, CO, SO2, H2O, O2, HCl 

EA 151-

50 

Sartec, Italy Sardinia, Italy Waste Incinerator NOx, CO, SO2, HCL, O2, H2O 

EA 149-

148 

Eli Lilly Shadeland, IN Regenerative Thermal Oxidizer NOx, CO, SO2, HCL, O2, H2O, 

THC 

EA 147 Measurementation Coldspring, TX Process Unit HCl 

EA 146 Graymont (QC) Inc Bedford, Quebec Lime Kiln NO, NO2, SO2, CO2, O2, H20 

EA 139-

136 

Ocean State Power Harrisville, RI Gas Turbine with SCR NO, NO2, CO, CO2, NH3, O2, 

H20 

EA 135 Onyx 

Environmental 

Sauget, IL Waste Incinerator SO2, CO, CO2, H2O, O2, HCl 

End of Table 
EcoChem References and Installations

First and Second Generation Multicomponent Systems 

The following is a summary of First and Second Generation multicomponent IR analyzer based CEMS that 

were designed, installed, and supported by the staff of EcoChem Analytics. The list goes back to 1989, 

covering the complete gamut of applications...from Gas Turbines to Cement Plants. The industries are 

broken out for clarity. A total of 52 second generation and 390 first generation systems were installed. 

A comprehensive list or specific references can be supplied for any of these industries. 

First Generation Multicomponent Systems (1989 – 1997) 

Industry Installations 

Cement Industry 64 

Coal Fired Utility 48 

Diesel Fired Utility Boiler 4 

Gas & Oil Utility Boiler 67 

Industrial 82 

Process Monitoring 6 

Waste Incineration 119 

Second Generation Multicomponent Systems (1998 - 2001) 

Industry Installations 

Cement Industry 2 

Utility (Coal, Gas, Oil, Wood) 12 

Industrial 6 

Waste Incineration 32 
EcoChem References and Installations

Installations in Europe 

EcoChem Messtechnik has an exclusive arrangement with Dr Fodisch Umweltmesstechnik AG for 

supplying systems in Germany. Additionally, some of these systems have also been provided to several 

international locations. The MCA-04 Emission analyzer provided by Dr Fodisch is identical to the standard 

EcoChem MC3 analyzer but is a private label brand name. Attached please find a list of the installations 

done by Dr Fodisch. 

 
EcoChem References and Installations
EcoChem References and Installations
EcoChem References and Installations
EcoChem References and Installations

Installations in Korea 

Deung Ju Instrument Co., Ltd of Korea provides CEMS based on the MC3 multicomponent analyzer to customers in 

Korea. Attached please find a list of installations
EcoChem References and Installations

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PERFORMANCE SPECIFICATION Z: 

SPECIFICATIONS AND TEST PROCEDURES FOR 

HCl CONTINUOUS EMISSION MONITORING 

SYSTEMS AT STATIONARY SOURCES 

 Revision 2.0 

 October, 2006 

 
i 

EXECUTIVE SUMMARY 

This performance specification describes the criteria that a hydrochloric acid (HCl) continuous 

emission monitoring system (CEMS) must meet to be considered valid for EPA compliance and/or 

other regulatory applications. Each HCl CEMS must meet the criteria for accuracy, stability, and 

instrumental response laid out in this document. In addition, each HCl CEMS must meet the 

installation requirements in PS-Z. 

 
ii 

REVISION HISTORY 

1.1 REVISION 1.0 

This document was part of the T149 Alternative Monitoring Petition, and was approved by the Office 

of Air Quality and Standards in January of 2006 

1.2 REVISION 2.0 

This revision is an update of the original Procedure Z document, October 2006. The following are key 

updates in revision 2.0: 

1. Recommendation that all HCL QA gases be certified with a minimum tolerance of 5% 

2. Recommendation that a site specific dynamic spiking protocol be used and, the dynamic 

spiking protocol would contain the detailed test procedure(s). 

3. Discussion for the use of quantitative introduction of the HCL calibration gas and subsequent 

total flow measurement as method for determining the reference HCL concentration during 

each test run. 

4. Updated the dynamic spiking overview section for easier flow of information 

5. Updated the equations to include percent relative standard deviation and the calculation for 

the reference HCL concentration when using quantitative introduction of the HCL calibration 

gas with subsequent total flow measurement. 
iii 

TABLE OF CONTENTS 

1.1 REVISION 1.0..................................................................................................................II

1.2 REVISION 2.0..................................................................................................................II

2.0 USING PERFORMANCE SPECIFICATION Z.......................................................................4

2.1 WHAT IS THE PURPOSE AND APPLICABILITY OF PERFORMANCE 

SPECIFICATION Z?........................................................................................................4

2.2 WHAT WILL BE DISCUSSED IN PS-Z?.........................................................................4

2.3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE 

SPECIFICATION TEST REQUIREMENTS?...................................................................5

2.4 WHAT SPECIAL DEFINITIONS APPLY TO PS-Z?........................................................6

3.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQUIREMENTS ..................................9

3.1 WHAT DO I NEED TO KNOW TO ENSURE THE SAFETY OF PERSONS 

USING PS-Z? ..................................................................................................................9

3.2 WHAT EQUIPMENT AND SUPPLIES DO I NEED?.......................................................9

3.3 WHAT REGENTS AND STANDARDS DO I NEED? ....................................................10

4.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING................................11

4.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPECIFICATION 

TESTS AND WHAT IS REQUIRED TO PERFORM THE TESTS? ..............................11

4.2 HOW DO I REPORT THE RESULTS OF THE INITIAL PERFORMANCE 

SPECIFICATION TEST?...............................................................................................15

5.0 PERFORMANCE CRITERIA AND CALCULATIONS..........................................................16

5.1 WHAT ARE THE PERFORMANCE CRITERIA FOR MY HCL CEMS?........................16

5.2 WHAT CALCULATIONS, EQUATIONS, AND DATA ANALYSES ARE 

NEEDED?......................................................................................................................17

5.3 CRITERIA FOR ACCEPTANCE....................................................................................25

5.4 BIAS CORRECTION .....................................................................................................25

6.0 OTHER REQUIREMENTS AND INFORMATION................................................................27

6.1 WHAT QUALITY CONTROL MEASURES ARE REQUIRED? .....................................27

6.2 WHAT CALIBRATION AND STANDARDIZATION PROCEDURES MUST I 

PERFORM?...................................................................................................................27

6.3 WHAT POLLUTION PREVENTION PROCEDURES MUST I FOLLOW? 

[RESERVED].................................................................................................................27

7.0 RELEVANT REFERENCES.................................................................................................30

 

Table 1. Performance Specification Test Calibration Gas Ranges 

Figure 1. Dynamic Spiking Overview
4 

2.0 USING PERFORMANCE SPECIFICATION Z 

2.1 WHAT IS THE PURPOSE AND APPLICABILITY OF PERFORMANCE SPECIFICATION Z? 

The purpose of Performance Specification Z (PS-Z) is to establish the initial performance requirements for 

evaluating the acceptability of a HCl CEMS. Such applications may include, (1) instrument, method or 

procedure calibration, and (2) evaluation or certification for initial acceptance. 

2.1.1 Application 

This specification is for evaluating the acceptability of a HCl CEMS at the time of installation and during 

periodic quality assurance checks. PS-Z applies to you if you will be using a HCl CEMS to demonstrate 

compliance with a regulatory HCl or HCl/Cl2 emission standard. 

2.1.2 Measurement Capabilities 

The HCl CEMS must be capable of measuring HCl concentrations in the units of the applicable standard 

or in units that can be converted to units of the applicable standard.

2.1.3 Other Monitoring

If your HCl CEMS is capable of reporting the HCl concentration in the units of the existing regulation, no 

additional monitoring is necessary. If your HCl CEMS does not report concentrations, in the units of the 

existing standard, then other monitoring (e.g., oxygen, temperature, and pressure) are necessary to 

convert the units reported by your CEMS to the units of the standard.

2.2 WHAT WILL BE DISCUSSED IN PS-Z? 

PS-Z covers two basic topics: (1) the instrument requirements for an HCl CEMS and (2) the requirements 

that each HCl CEMS must meet during the performance specification test. 

2.2.1 Instrument Requirements 

The HCl CEMS must be able to accurately report concentrations of HCl in stack effluent. It may do so by 

extracting a representative sample (path or point sampling may be used if the sample is representative) of 

stack effluent and analyzing the effluent to provide an output proportional to the HCl concentration. The 

CEMS operating range (zero to span) should encompass the response of the HCl CEMS for all expected 

HCl concentrations, including the applicable emission limit. The CEMS must have a system response 

time that is less than or equal to two minutes. Finally, the instrument or operator must be able to perform 

daily calibration drift tests, quarterly calibration error tests, and annual accuracy tests. 
5 

2.2.2 Performance Specification Test 

The purpose of the performance specification test is to establish the accuracy, precision, bias, and 

system response time of the HCl CEMS. Specifically, the following will be either tested or documented as 

part of the performance specification test requirements listed in Sections 3.0 and 4.0 of this document: (1) 

data recorder scale, (2) daily calibration drift, (3) installation and measurement location, (4) calibration 

drift test, (5) calibration error test, (6) system response time, (7) stratification test, (8) accuracy 

determination. 

2.3 WHAT ARE THE INSTALLATION AND PRE-PERFORMANCE SPECIFICATION TEST 

REQUIREMENTS? 

2.3.1 Installation Requirements 

The sampling location of the HCl CEMS should be downstream of all pollution control equipment at a 

position where the HCl concentration is directly representative or can be corrected so as to be 

representative of total emissions from the stationary source. It is recommended that the sampling 

location be at least two equivalent diameters downstream of the nearest control devices, point of pollution 

generation, bend, or other point at which a change in pollutant concentration or flow disturbance may 

occur. The sampling location is also recommended to be at least a half equivalent diameter upstream 

from the exhaust or control device. The equivalent diameter is calculated according 40 CFR Part 60, 

Appendix A, Method 1, Section 2.1I

. 

Either point or path sampling may be used. For point sampling the measurement point should be no less 

than 1.0 meter from the stack or duct wall or located over the centroidal area of the stack or duct cross 

section. For a path sampling CEMS the effective measurement path should be (1) totally within the inner 

area bounded by a line 1.0 meter from the stack or duct wall, or (2) have at least 70 percent of the path 

within the inner 50 percent of the stack diameter or duct cross section, or (3) be centrally located over any 

part of the centroidal area. 

The sample collection and instrumental analyzer portions of your HCl CEMS may be located any distance 

from the sampling point provided the transmission efficiency from the sampling point to the sample 

collection point can be determined and meets the criteria outlined later in this performance specification. 

It is also recommended that the sampling probe for the HCl CEMS be located at point without 

stratification (section 3.1.5).
6 

2.3.2 Reference Method Measurement Location 

You must select, as appropriate, an accessible reference method (RM) measurement point at least two 

equivalent diameters downstream from the nearest control device, the point of pollutant generation, or 

other point at which a change in the pollutant concentration or emission rate may occur, and at least a 

half equivalent diameter upstream from the effluent exhaust or control device. When pollutant 

concentration changes are due solely to diluent leakage (e.g., air heater leakages) and pollutants and 

diluents are simultaneously measured at the same location, a half diameter may be used in lieu of two 

equivalent diameters. The CEMS and RM locations need not be the same. If dynamic spiking is 

employed to determine the system accuracy, bias, and precision, the spiking of the calibration gas must 

encompass the sampling system of the HCL CEMS. 

2.3.2.1 Reference Method Traverse Points 

Select traverse points that assure acquisition of representative samples over the stack or duct crosssection. The minimum requirements are as follows: Establish a "measurement line" that passes through 

the centroidal area and in the direction of any expected stratification. If this line interferes with the CEMS 

measurements, displace the line up to 30 cm (12 in.) (or 5 percent of the equivalent diameter of the cross 

section, whichever is less) from the centroidal area. Locate three traverse points at 16.7, 50.0, and 83.3 

percent of the measurement line. If the measurement line is longer than 2.4 meters (7.8 ft) and pollutant 

stratification is not expected, the three traverse points may be located on the line at 0.4, 1.2, and 2.0 

meters from the stack or duct wall. This option must not be used after wet scrubbers or at points where 

two streams with different pollutant concentrations are combined. 

Other traverse points may be selected, provided that they can be shown to the satisfaction of the 

Administrator to provide a representative sample over the stack or duct cross section. Conduct all 

necessary RM tests within 3 cm (1.2 in.) of the traverse points, but no closer than 3 cm (1.2 in.) to the 

stack or duct wall. 

2.4 WHAT SPECIAL DEFINITIONS APPLY TO PS-Z? 

Calibration Drift: The difference in the CEMS output readings from the established reference value after 

a stated period of operation during which no unscheduled maintenance or adjustment took place. 

Calibration Error: The mean difference between the concentration indicated by the CEMS and the 

known concentration generated by a calibration source at three levels when the entire CEMS, including 

the sampling interface is challenged. A CE test is performed to document the accuracy and linearity of 

the CEMS over the entire measurement range.
7 

Centroidal Area: means a concentric area that is geometrically similar to the stack or duct cross section 

and is no greater than 1 percent of the stack or duct cross-sectional area. 

Continuous Emission Monitoring System: means the total equipment required for the determination of 

a gas concentration or emission rate. The sample interface, pollutant analyzer, diluent analyzer, and data 

recorder are the major subsystems of the CEMS. 

Correlation Coefficient: determines the extent of a linear relationship between two fields over a given 

period of time.

Data Recorder: The portion of the CEMS that provides a record of analyzer output, flags which indicate 

normal operation, and flags indicating abnormal operation. The data recorder may record other pertinent 

data such as effluent flow rates, and various instrument temperatures. 

Diluent Analyzer: means that portion of the CEMS that senses the diluent gas (i.e. O2) and generates an 

output proportional to the gas concentration. 

Dynamic Spiking: a procedure used to document the accuracy, precision, and bias of the monitoring 

system by quantitatively spiking a certified gas into the pollutant gas stream. 

High-level drift: means the absolute difference between a high-level calibration gas and the monitor 

response, in units of the applicable standard. 

Instrument Measurement Range: The range of HCl concentrations the instrument can reliably measure 

from the lowest concentration to the highest. 

Intercept: value of the Y variable when the X variable is equal to zero. 

Linear Regression: a methodology used to find a formula that can be used to relate two variables that 

are linearly related. 

Path Sampling CEMS: A CEMS that samples the source effluent along a path greater than 10 percent of 

the equivalent diameter of the stack or duct cross section. 

Point Sampling CEMS: A CEMS that samples the source effluent at a single point. 
8 

Pollutant Analyzer: means that portion of the CEMS that senses the pollutant gas and generates an 

output proportional to the gas concentration. 

Relative Accuracy (RA): means the absolute mean difference between the gas concentration or 

emission rate determined by the CEMS and the value determined by the Reference Method (RM), plus 

the 2.5 percent error confidence coefficient of a series of tests, divided by the mean of the RM tests or the 

applicable emission limit. 

Response Time: The time interval between the start of a step change in the system input and when the 

pollutant analyzer output reached 95% of the final value. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample acquisition, 

sample transport, sample conditioning, or protection of the monitor from the effects of stack gas. 

Slope: The rate of change of Y relative to the change in X. 

Stratification: means the change in effluent concentration in a duct, over time when comparing a 

reference measurement (centroid of duct) to traversed sampling concentrations. 

Zero drift: means the absolute difference between a high-level calibration gas and the monitor response, 

in units of the applicable standard. 
9 

3.0 INTERFERENCES, SAFETY, AND EQUIPMENT REQUIREMENTS 

3.1 WHAT DO I NEED TO KNOW TO ENSURE THE SAFETY OF PERSONS USING PS-Z? 

People using PS-Z may be exposed to hazardous material, operational hazards, and hazardous site 

conditions. PS-Z does not address all the safety issues associated with its use. It is your responsibility to 

ensure the safety of persons using PS-Z. Some helpful references may include the CEMS manual, the 

CEMS manufacturer, other reference methods, and on-site safety regulations. 

3.2 WHAT EQUIPMENT AND SUPPLIES DO I NEED? 

3.2.1 Equipment for the CEMS 

1. Sample Extraction System: This portion of the CEMS must present a sample of source 

effluent to the sampling module that is directly representative or can be corrected so as to be 

representative of source. The sample extraction system typically consists of a sample probe 

and a heated umbilical line. 

2. Pressure Regulation Module: The pressure regulation module is designed to remove both 

free particulates and water-soluble aerosols from the gas stream prior to analysis by the 

sampling module. This module also provides a sample gas to the analyzer at a constant 

pressure (optional). 

3. Analysis module: The portion of the CEMS that quantitates stack gas concentrations of HCl. 

4. Diluent Module: This portion of the CEMS quantifies stack gas concentrations of oxygen or 

CO2. For systems with a multi-component analyzer, the same analyzer quantifies the 

concentration of all measured analytes.

5. System Controller: This portion of the CEMS provides control of the analyzer, sample 

probe, pressure regulation module and the sample interface. 

6. Data recorder: Your HCl CEMS must be able to record HCl concentrations and instrument 

status signals (flags). 

3.2.2 Equipment Specifications 

The CEMS data recorder output range must include zero and a high-level value. The range of the data 

recorder and the measurement range of the HCl CEMS will be documented. The high-level value is 

chosen by the source owner or operator and is defined as follows: 
10 

For an HCl CEMS installed to measure controlled emissions or emissions that are in compliance with an 

applicable regulation, the high-level value should be at least 1.5 times the emission standard level and 

encompass the HCl concentration levels expected by the process. 

 The CEMS design should also allow the determination of calibration drift at the zero and high-level 

values. In special cases, the Administrator may approve a single-point calibration-drift determination. 

3.3 WHAT REGENTS AND STANDARDS DO I NEED? 

3.3.1 Reference Gases, Gas Cells, or Optical Filters 

See Table 1 for reference gas concentration ranges. 

 
11 

4.0 PERFORMANCE EVALUATION PROCEDURES AND REPORTING 

4.1 WHAT IS THE PURPOSE OF THE PERFORMANCE SPECIFICATION TESTS AND WHAT IS 

REQUIRED TO PERFORM THE TESTS? 

The purpose of the performance specification tests is to determine the accuracy, precision, bias, and 

system response time of the HCl CEMS. 

4.1.1 Pretest Preparation 

Prior to the start of your initial performance specification tests, you must be sure that the HCl CEMS is 

installed according to the specifications laid out in this document. After installing the HCl CEMS, it is 

recommended you use the CEMS for a period of time to familiarize yourself with its operation. It is also 

recommend that you conduct daily checks of the zero and high-level drift, conduct a calibration error test, 

and conduct a calibration drift check to verify that the instrument is functioning properly. When you are 

confident that the instrument is performing satisfactorily it is time to prepare for the performance 

specification tests. 

4.1.2 Data Recorder Scale Check 

The range of the data recorder and the measurement range of the HCl CEMS will be documented. The 

CEMS operating range (zero to span) and the range of the data recorder should encompass both the 

response of the HCl CEMS for all expected HCl concentrations and the applicable emission limit. 

4.1.3 Calibration Drift Check 

The HCL CEMS must perform a calibration check at least once per day. Certified gases must be used to 

perform the zero and high-level drift checks. All data will be recorded. 

4.1.4 Installation and Measurement Location Check 

The installation location of the HCL CEMS must adhere to section 1.3.1 of this document. In addition, the 

location of any reference method testing must adhere to section 1.3.2 of this document. 

4.1.5 Stratification Test 

 The stratification test must be conducted when the facility is operating during normal operation. The 

purpose of this test is to verify that excess stratification of the target pollutant does not exist at the 

sampling point of the monitoring system. 

 To determine whether effluent stratification exists, a dual probe system should be used to determine the 

average effluent concentration while measurements at each traverse point are being made. One probe, 
12 

located at the stack or duct centroid, is used as a stationary reference point to indicate change in the 

effluent concentration over time. The second probe is used for sampling at the traverse points specified 

in Method 1. The traverse points are sampled for five minutes at each point. You may test for 

stratification at the HCl CEMS sampling point by using either velocity tests as described in Method 2II, HCl 

concentrations using Methods 26 or 26A, or an acceptable alternative (i.e. CO or Nox) A minimum of 12 

sampling points will be used, with 6 sampling points along each of the two traverses. 

4.1.6 Seven-day Calibration Drift Test 

The seven-day calibration drift test must be conducted when the facility is operating during normal 

operation. The purpose of this test is to verify that the instrument operation is stable. During the 

calibration drift test period you must determine the magnitude of the zero calibration drift and the highlevel calibration drift at least once each day. During the stability tests no adjustments or calibrations may 

be made to the CEMS. If periodic automatic or manual adjustments are made to the CEMS zero and 

high-level calibration settings, conduct the CD test immediately before these adjustments, or conduct it in 

such a way that the CD may also be determined. 

The calibration drift will be determined at the zero and high-level value of the HCl CEMS. Introduce to the 

CEMS the reference gases, gas cells, or optical filters (these need not be certified) for the zero and high 

level values. Record the CEMS response and subtract this value from the reference value. The 

calibration gas concentrations are provided in Table 1. 

4.1.7 Calibration Error 

 The HCL CEMS will be challenged three non-consecutive times with zero, mid-level, and high-level 

certified HCL gases (Table 1). The cylinder gases need not be EPA Protocol 1 gases. The calibration 

gases will be injected into the sample system as close to the sampling probe outlet as practical and will 

pass through all CEMS components used during normal monitoring. The difference between the 

instrument response and the reference value (certified gas) will be calculated after each injection and the 

resulting three differences will be averaged to determine the CE at each measurement point. 

4.1.8 System Response Time 

Introduce zero gas into the analyzer. When the system output has stabilized (no change greater than 1 

percent of full scale for 30 sec), introduce an upscale calibration gas and wait for a stable value. Record 

the time (upscale response time) required to reach 95 percent of the final stable value. Next, reintroduce 

the zero gas and wait for a stable reading before recording the response time (downscale response time). 

Repeat the entire procedure three times and determine the mean upscale and downscale response 

times. The slower or longer of the two means is the system response time. 
13 

Calibration gas ranges for the response time test are provided in Table 1. If using a multi-component 

analyzer, the response time can be based on any analyte measured by the CEMS. 

4.1.9 CEMS Accuracy 

The accuracy of the HCl CEMS shall be determined by performing either a relative accuracy 

determination or by dynamic spiking. 

4.1.9.1 Relative Accuracy (RA) 

Conduct the RA test while the affected facility is operating during normal operation, or as specified in an 

applicable subpart. The RA test may be conducted during the CD test period. 

Reference Methods (RM). Unless otherwise specified in an applicable subpart of the regulations, 

Methods 26 or 26A, or their approved alternatives, are the reference methods for HCl. Other reference 

methods for moisture, oxygen, etc. may be necessary. 

Sampling Strategy for RM Tests. Conduct the RM tests in such a way that they will yield results 

representative of the emissions from the source and can be correlated to the CEMS data. It is preferable 

to conduct the diluent (if applicable), moisture (if needed), and pollutant measurements simultaneously. 

However, diluent and moisture measurements that are taken within an hour of the pollutant 

measurements may be used to calculate dry pollutant concentration and emission rates. In order to 

correlate the CEMS and RM data properly, note the beginning and end of each RM test period of each 

run (including the exact time of day) on the CEMS chart recordings or other permanent record of output. 

For integrated samples make a sample traverse of at least 21 minutes, sampling for an equal time at 

each traverse point. 

Number of RM Tests. Conduct a minimum of nine sets of all necessary RM test runs. 

NOTE: More than nine sets of RM tests may be performed. If this option is chosen, a maximum of three 

sets of the test results may be rejected so long as the total number of test results used to determine the 

RA is greater than or equal to nine. However, all data must be reported, including the rejected data. 

Correlation of RM and CEMS Data. Correlate the CEMS and the RM test data as to the time and 

duration by first determining from the CEMS final output (the one used for reporting) the integrated 

average pollutant concentration or emission rate for each pollutant RM test period. Consider system 

response time, if important, and confirm that the pair of results are on a consistent moisture, temperature, 

and diluent concentration basis. Then, compare each integrated CEMS value against the corresponding 

average RM value. If the RM has an integrated sampling technique, make a direct comparison of the RM 

results and CEMS integrated average value. 
14 

Calculate the mean difference between the RM and CEMS values in the units of the emission standard, 

the standard deviation, the confidence coefficient, and the relative accuracy according to the procedures 

in Section 4.0. 

4.1.9.2 Dynamic Spiking 

Dynamic spiking can be used in lieu of the Relative Accuracy Determination as an alternative method for 

documenting the accuracy, precision, and bias of the HCl CEMS. This section provides an overview of a 

typical dynamic spiking procedure. A site specific dynamic spiking protocol, which provides detailed 

steps of the actual procedure, is required. Figure 1 provides an overview of a typical dynamic spiking 

arrangement. 

While the HCl CEMS is sampling flue gas, HCl reference gas is introduced into the CEMS sample 

interface by using a mass flow controller (or equivalent). The target ratio of actual flue gas to the HCl 

reference gas is 9:1, but must be kept at a minimum ratio of 1:1. The HCl concentration is quantitated by 

the HCl CEMS. 

Certified HCL calibration gas is spiked at a minimum of three levels (low, mid, high) through the HCL 

CEMS measurement range. For each test level, a minimum of 30, one minute averaged HCL values are 

collected. The percent relative standard deviation, for each data set, should not exceed 20%. Table 1 

provides guidance on the HCL concentrations for the low, mid, and high test runs. 

Several methods exist to calculate the dynamically spiked HCL concentration (represents the reference 

HCL concentration). Two common methods are: (1) Use of an element of opportunity and (2) 

Quantitative introduction of the HCL calibration gas with total flow measurement. Other methods may be 

used; however, a site specific protocol should document the procedure(s) used. 

An element of opportunity can be used to calculate the dynamically spiked HCl concentration (represents 

the reference HCl concentration). The element of opportunity can either be be an analyte, which would 

normally be present in the flue gas at steady concentrations, or total flow through the system. Examples 

of prospective analytes which could be used as elements of opportunity are O2, NOx, SO2, CO2, or 

moisture. The analyte(s) is measured using a certified reference CEMS, separate from the HCL CEMS. 

Total flow through the system may also be used as an element of opportunity to calculate the dynamically 

spiked HCL concentration. Examples the total flow measurement are the use of a calibrated laminar flow 

element, or use of a tracer gas with subsequent downstream measurement (for example: hydrocarbon 

tracer gas with subsequent calibrated GC measurement downstream). 

Regardless of the element of opportunity, It is recommended that the element of opportunity data set, for 

each test level (low, mid, high) have a relative percent standard deviation less than or equal to 20%. 
15 

Quantitatively introducing the HCL calibration gas, and, measuring the total flow is another method for 

documenting the dilution, and subsequent theoretical value of the HCL concentration spiked for each test 

run. Use of this method requires documenting the quantitative introduction of HCL gas into the system; 

such as a method 205 procedure or similar protocol. 

It is important to compensate the HCl reference concentration(s) for any background HCL present in the 

flue gas. The HCl concentration of the flue gas (baseline HCL) shall be determined prior to each spiking 

trial. The baseline HCl concentration is based upon a series of at least 10, one-minute averaged data 

points. Baseline data must be collected immediately prior to each test run. The data points must include 

the HCl concentration, element of opportunity concentration(s) and/or the total flow. A site-specific 

standard operating procedure for the HCL dynamic spiking is required. 

Linear regression is used to establish the accuracy, precision, and bias of the HCl CEMS. The criteria for 

the HCl dynamic spiking are: 

1. The correlation coefficient (r) must be greater than or equal to 0.90 

2. The slope must be 1.0, +/- 0.15 

3. The Intercept must be equal to or less than 15% of the instrument span 

4.2 HOW DO I REPORT THE RESULTS OF THE INITIAL PERFORMANCE SPECIFICATION TEST? 

Summarize the results of the calibration drift, calibration error, response time, stratification, and accuracy 

tests in tabular form. Include all data sheets, calculations, and records of CEMS measurements 

necessary to substantiate the performance of the CEMS and any other devices or methods (e.g., method 

26A). The CEMS measurements shall be reported to the agency in units of ppmv, on a dry basis. 
16 

5.0 PERFORMANCE CRITERIA AND CALCULATIONS 

5.1 WHAT ARE THE PERFORMANCE CRITERIA FOR MY HCL CEMS? 

You must demonstrate that your HCl CEMS has adequate precision, accuracy, system response time and 

data reporting capabilities to determine if your facility is in compliance with HCl emission standards or 

operating permit limits as specified in applicable regulations or permits. You will demonstrate this 

capacity by showing that your HCl CEMS meets the following performance criteria. 

5.1.1 Data Recorder Scale 

The measurement range of the HCL CEMS, and the data recorder scale, must encompass the expected 

HCL concentrations as well as the applicable emission limit. 

5.1.2 Calibration Drift 

The daily zero and high-level calibration drift is 5% of the instrument span. Zero and high-level calibration 

drifts shall be adjusted, at a minimum, whenever the 24-hour zero drift exceeds the limits of the 

calibration drift specification. The amount of excess zero and high-level drift measured at the 24-hour 

interval checks will be recorded. Section 4.2 provides the equations for calculating the zero and highlevel calibration drifts. 

5.1.3 Installation and Measurement Location 

The installation requirements and measurement location of the HCL CEMS will meet the specifications 

outlined in section 3.1.1 and 3.1.2 of this document. 

5.1.4 Stratification Test 

The stratification in the stack or duct, at the measurement location, must be less than or equal to a 10 

percent between the average concentration in the duct or stack and the concentration at any point more 

than 1.0 meter form the duct or stack wall. Section 4.2.2 provides the equation for calculating the 

stratification of the stack or duct. 

5.1.5 Seven-day Calibration Drift Test Criteria 

The daily zero and high-level drift each must be less than 5% of the instrument span for seven 

consecutive days. See Section 4.2.2 for the equations used to determine the zero and high-level drift.
17 

5.1.6 Calibration Error Test 

The mean difference between the CEMS and the reference values, at all three test levels, must be no 

greater than 5% of span. See Section 4.2.3 for the equation used to determine the calibration error. 

5.1.7 Response Time Test 

The CEMS response time shall not exceed 2.0 min to achieve 95 percent of the final stable value. If 

using a multi-component analyzer, the response time can be based on any analyte measured by the 

CEMS. 

5.1.8 Relative Accuracy 

The RA of the CEMS must not be greater than 20% of the mean value of the reference method (RM) test 

data, or not greater than 10% in terms of the emission standard (ppmv, dry), or have an absolute 

difference of less than 5 ppmv between the mean reference value and the mean CEMS value. See 

Section 4.2.5 for the equations used to determine the relative accuracy of your CEMS. 

5.1.9 Dynamic Spiking 

Dynamically spiking may be used in lieu of a relative accuracy test as a means to document the accuracy, 

precision, and bias of the HCl CEMS. 

The criteria for the HCl dynamic spiking is: 

• The correlation coefficient, r, must be greater than or equal to 0.90 

• The slope must be 1.0, +/- 0.15 

• The Intercept must be equal to or less than 15% of the instrument span. 

See Section 4.2.8 for equations to determine the linear correlation coefficient, the slope and the intercept. 

At a minimum, the data set must meet the correlation coefficient. If this is not met, the dynamic spiking 

procedure must be repeated until the correlation coefficient criteria is met. If the HCl CEMS has met the 

correlation coefficient requirement, but does not meet either the slope, or intercept criteria, a bias exists 

and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine 

the corrected value are provided in Section 4.2.8.1. The correction factor must be applied to the HCl 

CEMS one-minute average data until a new dynamic spiking procedure indicates the specific bias no 

longer exists, or, a different correction factor (bias) is indicated. 

5.2 WHAT CALCULATIONS, EQUATIONS, AND DATA ANALYSES ARE NEEDED? 
18 

5.2.1 Daily Upscale and Zero Drift 

 CD =(⎪R - A⎪/ S ) * 100 (Equation 1) 

where: 

 CD = Percent calibration drift (%), 

 R = Reference value of zero or high level calibration gas introduced into the 

monitoring system (ppmv), 

 A = Actual monitor response to calibration gas (ppmv), 

 S = Span of the instrument (ppmv). 

5.2.2 Calibration Error 

 CE = ⎪davg / S⎪ * 100 (Equation 2) 

where: 

 CE = Percent calibration error (%), 

 davg = Mean difference between CEMS response and the known reference gas (ppmv), 

 S = Span of the monitor (ppmv). 

5.2.3 Mean Difference 

Calculate the arithmetic mean difference as follows: 

= ∑ i avg d

n

d 1 (Equation 3) 

where : 

davg = Arithmetic mean of differences 

n = Number of data sets 

di = difference of each data set 
19 

And 

di = xi − yi (Equation 4)

where: 

xi = Value at data set x 

yi = Value at data set y

5.2.4 Relative Accuracy 

The RA for the monitors will be calculated using the least restrictive of equation 6 or equation 7: 

RA = (⎪davg⎪ + ⎪CC⎪) (Equation 5)

 or 

RA = ((⎪davg⎪ + ⎪CC⎪) / TMavg ) * 100 (Equation 6)

where: 

RA = Relative accuracy, either percent or ppmv or % absolute, 

 davg = Arithmetic mean of differences between value measured by the installed CEMS and the 

reference method, 

 CC = Confidence coefficient, 

 TMavg = Average value measured by the reference test method monitors. 

5.2.5 Confidence Coefficient 

The confidence coefficient will be calculated using equation 8: 

 CC = t0.975 * (Sd / (n1⁄2)) (Equation 7)

where: 

 CC = Confidence coefficient, 

 t0.975 = t-value obtained from Table 2.1 in Performance Specification 2, 40 CFR Part 60 

Appendix B 
20 

5.2.6 Standard Deviation (of Differences) 

Sd = Standard deviation of differences measured between the installed CEMS and the 

reference methods calculated using equation 8: 

1 / 2 2

1

1

2

1

⎥

⎥

⎥

⎥

⎥

⎥

⎦

⎤

⎢

⎢

⎢

⎢

⎢

⎢

⎣

⎡

−

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

−

=

∑ ∑ =

=

n

n

d

S

n

i i n

i i

d

d (Equation 8)

where: n = Number of values in this data set. 

5.2.7 Stratification 

The value, at each traverse point, is compared to the average value for all sampling points to determine 

the percent stratification using the following equation: 

S = Ci −Cave *100% (Equation 9)

where: 

 S = percent stratification 

 Ci

 = concentration or velocity at sampling point i 

 Cave = average concentration or velocity at all sampling points 

5.2.8 Baseline data 

5.2.8.1 HCL CEMS data 

The baseline HCL concentration is measured prior to each dynamic spiking run. For each baseline HCL 

data set, calculate the average, in ppm, using equation 10. 

Calculate the arithmetic mean of a data set as follows: 

= ∑xi

n

x

1

(Equation 10) 

where : 
21 

x = Arithmetic mean 

n = Number of data points 

xi = Value of each data point 

5.2.8.2 Element of Opportunity Data 

The element of opportunity data set is acquired prior to each dynamic spiking test run, simultaneous to 

the baseline HCL concentration data set. For each element of opportunity, calculate the average value 

using equation 10. 

5.2.8.3 Flow via dilution 

When using dilution of a measured analyte (such as a hydrocarbon with subsequent GC measurement) 

as an indicator of total flow, calculate the total flow, in liters per minute using equation 11. 

Calculate the total flow as follows: 

 Tflow = 

( )

( ) *

Analyte measured

Analtye spike Tflow

−

− (Equation 11)

 Tflow = Total flow through the system in lpm 

 Analyte-Spike = Concentration of Spiked Analyte (ppm) 

 Analyte-measured = Measurement, downstream, of spiked Analyte (ppm) 

Calculate the average flow value, for the data set, using equation 10. 

5.2.9 Dynamic Spiking Test run data 

5.2.9.1 HCL CEMS data 

For each dynamic spiking test run, calculate the average and percent relative standard deviation of the 

data set using equations 10 and 12, respectively. 
22 

Calculate the percent standard deviation as follows: 

1 / 2 2

1

1

2

1

⎥

⎥

⎥

⎥

⎥

⎥

⎥

⎦

⎤

⎢

⎢

⎢

⎢

⎢

⎢

⎢

⎣

⎡

−

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

−

=

∑ ∑ =

=

n

n

d

PRS

n

i i n

i i

d

d (Equation 12)

 x

Where: 

PRSd = Percent Relative Standard Deviation of the data set 

 x = Arithmetic mean 

5.2.9.2 Element of Opportunity data 

For each dynamic spiking test run, calculate the average and percent relative standard deviation of the 

data set using equations 10 and 12, respectively. If using total flow as a means to determine the 

reference HCL calibration gas concentration, use equation 11 to calculate the total flow prior to 

determining the average and percent relative standard deviation of the data set. 

5.2.10 Reference HCL concentration calculations 

5.2.10.1 Element of opportunity to calculate reference HCL concentration 

Equation 13 is used to calculate the reference HCL concentration for a given dynamic spiking test run. 
23 

HCl ref = CalGas BaselineHCl

Opp pre

Opp post

avg

avg + −

− 1− * (Equation 13)

where: 

 

 Opp-post avg = average reference element of opportunity value during dynamic spiking test run 

 Opp-pre avg = average reference element of opportunity value during baseline test run 

 CalGas = HCl calibration gas concentration 

 Baseline HCl = CEMS HCl average baseline value 

5.2.10.2 Quantitative HCL calibration gas introduction and total flow to calculate reference HCL 

concentration 

When using the quantitative introduction of calibration gas and total system flow to calculation the 

reference HCL concentration for a given dynamic spiking test run, use equation 14. Equation 11 is used 

to calculate the total system flow. 

HCl ref = CalGas BaselineHCl

Tflow

Cflow

avg

avg * + (Equation 14)

Where: 

HCl ref = Reference HCl value for run “X” 

 Cflow = Average calibration HCL gas flow rate into system (lpm) 

 Tflow = Average Total System Flow during run (lpm) 

 CalGas = HCl calibration gas concentration 

 Baseline HCl = CEMS HCl average baseline value 
24 

5.2.11 Linear Regression 

Linear regression is used to calculate the accuracy, precision, and bias of the HCL CEMS. For each 

dynamic spiking test run, plot the HCL CEMS reference value, Xaxis, versus the HCL measured value, Y 

axis. Determine the correlation coefficient (r ), the slope, and the intercept using equations 15-18. 

y b b x o 1 ˆ = + (Equation 15)

where: 

bo = The y intercept 

b1 = The slope 

The intercept is calculated according to the following equation: 

b y b x o = − 1 (Equation 16)

where: 

∑=

=

n

i

i x

n

x

1

1 

∑=

=

n

i

i y

n

y

1

1 

The slope of the line is calculated according to equation below: 

∑

∑

=

=

−

− −

= n

i 1

2

i

n

i 1

i i

1

( x x )

( x x )( y y )

b (Equation 17) 

The linear correlation coefficient is calculated according to the following equation. 
25 

∑ ∑

∑

= =

=

− −

⎟

⎠

⎞ ⎜

⎝

⎛ − −

= n

i

i

n

i

i

n

i

i i

x x y y

x x y y

r

1

2

1

2

2

2 1

( ) ( )

( )( )

 (Equation 18) 

5.3 CRITERIA FOR ACCEPTANCE 

The criteria for the HCl dynamic spiking is: 

• The correlation coefficient, r, must be greater than or equal to 0.90 

• The slope must be 1.0, +/- 0.15 

• The Intercept must be equal to or less than 15% of the instrument span. 

At a minimum, the data set must meet the correlation coefficient. If this is not met, the dynamic spiking 

procedure must be repeated until the correlation coefficient criteria are met. If the HCl CEMS has met the 

correlation coefficient requirement, but does not meet either the slope, or intercept criteria, a bias exists 

and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine 

the corrected value are provided in Section 5.4. The correction factor must be applied to the HCl CEMS 

one-minute average data until a new dynamic spiking procedure indicates the specific bias no longer 

exists, or, a different correction factor (bias) is indicated. 

5.4 BIAS CORRECTION 

If the HCl CEMS fails to meet both the slope and intercept criteria, the following correction factor must be 

applied to the one-minute average HCl data: 

1

0

b

y b CC i − = (Equation 19) 

Where:

C C = corrected CEMS HCL concentration 
26 

yi

 = CEMS reported HCL concentration 

b0 = the intercept of the least squares linear regression line 

b1 = the slope of the least squares linear regression line 

b). If the HCl CEMS fails to meet the slope criteria, but meets the intercept criteria, the following 

correction factor must be applied to the one-minute average HCl data: 

1 b

y CC i = (Equation 20)

c). If the HCl CEMS fails to meet the intercept criteria, but meets the slope criteria, the following correction 

factor must be applied to the one-minute average HCl data: 

0 C y b i

C = − (Equation 21)
27 

6.0 OTHER REQUIREMENTS AND INFORMATION 

6.1 WHAT QUALITY CONTROL MEASURES ARE REQUIRED? 

Ongoing quality control will include daily calibration drift tests, quarterly calibration error audits (absolute 

calibration audit), and annual accuracy test audits. Specific procedures and performance criteria are 

included in Procedure DD: Quality Control and Quality Assurance Requirements for Hydrochloric Acid 

Continuous Emission Monitoring Systems at Stationary Sources. 

6.2 WHAT CALIBRATION AND STANDARDIZATION PROCEDURES MUST I PERFORM? 

Refer to your CEMS owner’s manual and manufacturer to determine what calibration and standardization 

procedures are required for your HCl CEMS. 

6.3 WHAT POLLUTION PREVENTION PROCEDURES MUST I FOLLOW? [RESERVED] 
28 

Table 1. Performance Specification Test Calibration Gas Ranges 

 HCl Calibration Gas Concentrations a

Test Units Zero Mid-Level High-Level 

Calibration Drift and 

Response Time Test b

% of Span 0-30 NA 50-100 

Calibration Error Test % of Span 0-30 30-50 50-100 

Dynamic Spiking % of Span 0-50 25-75 50-100 

a

A copy of the supplier’s certificate of analysis must be provided for each gas cylinder. Calibration gases 

do not need to be Protocol 1 gases. It is recommended that the calibration gases, for all QA, have a 

minimum tolerance of 5%. 

b

If conducting the response time using a multi-component analyzer, the response time test can be based 

on any measured analyte. 
29 

Figure 1. Typical Dynamic Spiking Apparatus 

Typical Dynamic Spiking Apparatus

HCL 

CEMS

900-1000 ppm HCL in N2

Calibration Manifold

(Mass flow meters)

Sample Probe

•Heated Filter 

• Pressure Control

•Laminar Flow 

Element

Heated sample line

Flue Gas

Gas

Conditioner

Reference

Measurement(s)

Heated line inside 

sample umbillical
30 

7.0 RELEVANT REFERENCES 

I. United States. Environmental Protection Agency [EPA]. Technology Transfer Network. Emission 

Measurement Center. Promulgated Methods. Method 1: Sample and Velocity Traverses for 

Stationary Sources. Washington, DC: EPA; 2004. Available: 

http://www.epa.gov/ttn/emc/promgate/m-01.pdf via the Internet. 

II. United States. Environmental Protection Agency [EPA}. Technology Transfer Network. 

Emission Measurement Center. Promulgated Methods. Method 2: Determination of Stack Gas 

Velocity and Volumetric Flow Rate. Washington, D.C: EPA; 2004. Available: 

http://www.epa.gov/ttn/emc/promgate/m-02.pdf via the Internet. 

III. United States. Environmental Protection Agency (EPA). Technology Transfer Network. Emission 

Measurement Center. Performance Specifications. Performance Specification 2- Specifications 

and Test Procedures for SO2 and NOx Continuous Emission Monitoring Systems in Stationary 

Sources, 40 CFR 60 Appendix B, February 2000. Available: 

http://www.epa.gov/ttn/emc/perfspec.html via the Internet. 

IV. United States. Environmental Protection Agency (EPA). Technology Transfer Network. Emission 

Measurement Center. Performance Specifications. Performance Specification 4A - 

Specifications and Test Procedures for Carbon Monoxide Continuous Emission Monitoring 

Systems in Stationary Sources, 40 CFR 60 Appendix B, February 2000. Available: 

http://www.epa.gov/ttn/emc/perfspec.html via the Internet. 

V. United States. Environmental Protection Agency (EPA). Technology Transfer Network. Emission 

Measurement Center. Performance Specifications. Performance Specification 4B - 

Specifications and Test Procedures for Carbon Monoxide and Oxygen Continuous Emission 

Monitoring Systems in Stationary Sources, 40 CFR 60 Appendix B, September 30, 1999. 

Available: http://www.epa.gov/ttn/emc/perfspec.html via the Internet. 
 

HCL Dynamic Spiking Protocol 

ELI LILLY AND COMPANY 

TIPPECANOE LABORATORIES 

LAFAYETTE, IN 

August, 2006 

Revision 2.0 
HCL Dynamic Spiking Protocol 

August, 2006 

 1

TABLE OF CONTENTS 

1 REVISION HISTORY............................................................................................................. 2

1.1 REVISION 1.0 ................................................................................................................. 2

1.2 REVISION 2.0 ................................................................................................................. 2

2 OVERVIEW ........................................................................................................................... 3

3 DEFINITIONS ........................................................................................................................ 5

4 EQUIPMENT ......................................................................................................................... 7

5 EQUIPMENT CALIBRATION AND STANDARDS ................................................................ 8

5.1 HCL CEMS...................................................................................................................... 8

5.2 ELEMENT OF OPPORTUNITY CEMS........................................................................... 8

5.3 FLOW MEASUREMENT SYSTEM................................................................................. 8

5.3.1 Laminar flow element ...................................................................................... 8

5.3.2 Flow by dilution................................................................................................ 9

5.4 GAS MANIFOLD ............................................................................................................. 9

5.5 HCL CALIBRATION GAS FOR DYNAMIC SPIKING ..................................................... 9

6 DYNAMIC SPIKING RANGE............................................................................................... 10

7 TYPICAL DYNAMIC SPIKING SET-UP .............................................................................. 10

8 DYNAMIC SPIKING PROCEDURE .................................................................................... 11

8.1 COLLECTION OF BASELINE DATA............................................................................ 11

8.2 COLLECTION OF TEST DATA .................................................................................... 11

8.3 DATA CALCULATIONS................................................................................................ 12

8.3.1 Baseline data................................................................................................. 12

8.3.2 Dynamic Spiking Test run data ..................................................................... 14

8.3.3 Reference HCL concentration calculations ................................................... 15

8.3.4 Linear Regression ......................................................................................... 16

8.4 CRITERIA FOR ACCEPTANCE ................................................................................... 17

8.5 BIAS CORRECTION..................................................................................................... 18

9 TABLES ............................................................................................................................... 19

10 REFERENCES .................................................................................................................... 20

11 APPENDIXES...................................................................................................................... 21
HCL Dynamic Spiking Protocol 

August, 2006 

 2

1 REVISION HISTORY 

1.1 REVISION 1.0 

Revision 1.0, Tippecanoe Laboratories NON-GMP Standard Operating Procedure, Eli Lilly and Company, 

December 18, 2005. 

1.2 REVISION 2.0 

This revision is an update of the original Dynamic Spiking protocol, December 2005. The following are 

key updates in revision 2.0: 

1. Recommendation that all HCL QA gases be certified with a minimum tolerance of 5% 

2. Discussion for the use of quantitative introduction of the HCL calibration gas and subsequent total 

flow measurement as method for determining the reference HCL concentration during each test 

run. 

3. Updated the dynamic spiking procedure description for easier flow of information 

4. Updated the equations to include percent relative standard deviation and the calculation for the 

reference HCL concentration when using quantitative introduction of the HCL calibration gas with 

subsequent total flow measurement. 
HCL Dynamic Spiking Protocol 

August, 2006 

 3

2 OVERVIEW 

Dynamic Spiking is procedure to establish the accuracy, precision, and bias of a monitoring system. 

During the dynamic spiking procedure, a certified calibration gas (+/- 5%) is spiked into the monitoring 

system while the system is sampling flue gas. It is important that the spiked calibration gas flow through 

the entire sampling system. The target ratio of flue gas to HCL calibration gas is 9:1, with a minimum 

requirement of 1:1. The HCL calibration gas is spiked in three ranges (low, mid, high) through the range 

of HCL detector. A minimum of 30, one minute averaged data points should be collected for each of the 

three test runs. It is recommended that the percent relative standard deviation of the data set, for each 

test level, be less than or equal to 20%. 

If the flue gas has significant amounts of HCL present, the data may be corrected for the baseline HCL 

concentration. This is performed by collecting at least 10, one minute average HCL data points prior to 

each test run. The average of the ten baseline HCL values will be used to compensate the subsequent 

test run data for background HCL concentrations. It is important that the control device be running at 

steady state; alleviating large fluctuations in the background HCL concentrations. 

The HCL CEMS will provide the measured HCL values. These values are compared, using linear 

regression, to the known or spiked HCL concentrations. There are two methods for calculating the known 

HCL concentrations: (1) Use of an element of opportunity and (2) Quantitative introduction of the HCL 

calibration gas with total flow through the system. 

An element of opportunity can be any element normally present, in steady concentrations, in the flue gas 

stream. Examples are O2, CO, NOx, SO2, CO2, and moisture. Total flow through the system is also an 

example of an element of opportunity. 

The element of opportunity is measured during the baseline data collection, prior to the test run. The 

average value during this baseline collection period is used to establish the baseline concentration, or 

flow value, without any spiking of the calibration gas. 

The element of opportunity is measured during each test run while the HCL calibration gas is being 

spiked. The elements of opportunity values, collected during each test run are averaged. Knowing the 

concentration of the HCL calibration gas, and the dilution of the element of opportunity due to the spiking, 

the known value of the HCL calibration gas in the measurement stream can be calculated. 

The known value of the spiked HCL calibration gas in the measurement stream can also be calculated by 

quantitatively introducing the HCL calibration gas, and, measuring the total flow through the system. In 

this case, the HCL calibration gas concentration, the flow rate of spiked HCL calibration gas into the 

measurement stream, and the total flow through the system are used to calculate the known value of the 

spiked calibration gas. 

As with the HCL CEMS data sets, it is recommended that the percent relative standard deviation for the 

element of opportunity data sets be less than or equal to 20%. 

Once the data is collected, linear regression is performed using the known HCL spike values and the 

correlating HCL CEMS measured values. Criteria for the HCL dynamic spiking are: 

1. The correlation coefficient ® must be greater than or equal to 0.90. 

2. the slope of the regression line must be 1.0 +/- 0.15. 
HCL Dynamic Spiking Protocol 

August, 2006 

 4

3. The intercept, of the regression line, must be less than or equal to 15% of the instrument span. 

The HCL CEMS must meet the correlation criteria. If either the slope and/or intercept criteria are not met, 

a bias may be applied to the HCL CEMS one minute value. Performance Specification Z: Specifications 

and Test Procedures for the HCL Continuous Emission Monitoring Systems at Stationary Sources should 

be as a reference document for dynamic spiking requirements and calculations. 
HCL Dynamic Spiking Protocol 

August, 2006 

 5

3 DEFINITIONS 

Bias: The difference between the reference value and the measured value. 

Calibration Drift: The difference in the CEMS output readings from the established reference value after 

a stated period of operation during which no unscheduled maintenance or adjustment took place. 

Continuous Emission Monitoring System: means the total equipment required for the determination of 

a gas concentration or emission rate. The sample interface, pollutant analyzer, diluent analyzer, and data 

recorder are the major subsystems of the CEMS. 

Correlation Coefficient: determines the extent of a linear relationship between two fields over a given 

period of time.

Data Recorder: The portion of the CEMS that provides a record of analyzer output, flags which indicate 

normal operation, and flags indicating abnormal operation. The data recorder may record other pertinent 

data such as effluent flow rates, and various instrument temperatures. 

Dynamic Spiking: a procedure used to document the accuracy, precision, and bias of the monitoring 

system by quantitatively spiking a certified gas into the pollutant gas stream. 

Element of Opportunity: Any element, present in the flue gas matrix (or total flow) that has little 

fluctuation and can be used to determine the reference HCL concentration during the dynamic spiking 

test runs. 

Gas Chromatograph: An analytical instrument which uses a carrier gas to transport gas/vapor phase 

samples to a solid matrix for separation, and subsequent detection by a analyte specific detector. 

Gas manifold: Individual, or series of flow controllers that allow controlled flow of a gas. Calibrated flow 

controllers can be used to quantitatively control the flow of gases. 
HCL Dynamic Spiking Protocol 

August, 2006 

 6

 Instrument Measurement Range: The range of HCl concentrations the instrument can reliably measure 

from the lowest concentration to the highest. 

Intercept: value of the Y variable when the X variable is equal to zero. 

Laminar Flow Element: A device used to measure the flow gas through a system by measuring the 

pressure drop of the gas over a restriction (forces parallel, or laminar flow). 

Linear Regression: a methodology used to find a formula that can be used to relate two variables that 

are linearly related. 

Response Time: The time interval between the start of a step change in the system input and when the 

pollutant analyzer output reached 95% of the final value. 

Sample Interface: The portion of the CEMS used for one or more of the following: sample acquisition, 

sample transport, sample conditioning, or protection of the monitor from the effects of stack gas. 

Slope: The rate of change of Y relative to the change in X. 

Upscale drift: means the absolute difference between a high-level calibration gas and the monitor 

response, in units of the applicable standard. 

Zero drift: means the absolute difference between a high-level calibration gas and the monitor response, 

in units of the applicable standard. 
HCL Dynamic Spiking Protocol 

August, 2006 

 7

4 EQUIPMENT 

The following list contains typical equipment required to perform the HCL dynamic spiking. 

1. HCL CEMS 

2. Reference Analyzer(s) for the element of opportunity (examples are NOx, SO2, CO, CO2, O2) 

3. Flow Measurement Systems 

a. Laminar flow element 

b. Gas chromatograph (for dilution flow with a hydrocarbon) 

4. Calibration Equipment 

a. Bubble Flow meter, manometer, or equivalent for primary flow calibration 

b. Certified HCL Calibration gas for spiking 

c. HCL calibration gases for zero and upscale drift check of the HCL CEMS 

d. Calibration gas for the element(s) of opportunity CEMS calibration 

e. Hydrocarbon gas for flow measurement via dilution sampling 

5. Quantitative gas manifold, or equivalent, for introduction of the HCL calibration gas 

6. Quantitative gas manifold, or equivalent, for the introduction of the hydrocarbon for dilution flow (if 

used) 

7. Various fittings and tubing 
HCL Dynamic Spiking Protocol 

August, 2006 

 8

5 EQUIPMENT CALIBRATION AND STANDARDS 

Prior to performing the HCL dynamic spiking, it is important that all equipment and/or analyzers are 

calibrated. This section provides guidance on the calibration requirements for all equipment used during 

the HCL dynamic spiking procedure. 

5.1 HCL CEMS 

Prior to performing the dynamic spiking procedure, the HCL CEMS must pass the QA requirements 

specified in performance specification Z: Specifications and Test Procedures For HCL Continuous 

Emission Monitoring Systems at Stationary Sources. Typically, this would include passing the daily zero 

and upscale calibration drift check, and for annual audits passing both the zero and upscale drift check as 

well as a seven day drift test. All calibration gases must be certified gases, with a recommended 

tolerance not to exceed +/- 5%. 

5.2 ELEMENT OF OPPORTUNITY CEMS 

The monitoring system used to measure the element(s) of opportunity, other than total flow, must pass a 

calibration directly prior to use. After dynamic spiking run, the zero and upscale calibration drift are 

checked. The drift requirement, for both zero and upscale, is 3% of the reference value, unless stated 

otherwise in the applicable reference method. If either the zero or upscale calibration check fails the drift 

limit after a dynamic spiking run, the run must be repeated. 

5.3 FLOW MEASUREMENT SYSTEM 

Total flow may be used as an element of opportunity, or, as part of measuring the quantitative 

introduction of the HCL calibration gas for the dynamic spiking tests. There are several methods that can 

be used to provide a total flow measurement. This protocol outlines two approaches, laminar flow 

element and flow by dilution. Other total flow measurement systems can be used; however, specific 

protocol describing the methodology must be used. 

5.3.1 Laminar flow element 

Prior to the dynamic spiking procedure, the laminar flow element is calibrated against a primary flow 

standard, such as a bubble flow meter. The calibration must include at least three points throughout the 

expected measurement range. After each dynamic spiking test run, the calibration drift is checked at 

each of the three points. The laminar flow element must be re-calibrated if any of the drift check points 

exceed 10% of the expected value (established during the pre-test calibration). 
HCL Dynamic Spiking Protocol 

August, 2006 

 9

5.3.2 Flow by dilution 

Flow by dilution is a method where a known concentration of gas is quantitatively introduced to the flue 

gas stream and measured downstream by a calibrated instrument. For example, a known concentration 

of propane can be quantitatively introduced to the flue gas stream and the diluted propane measured 

downstream. 

Prior to the dynamic spiking procedure, the gas chromatograph is calibrated, using at least four points 

through the expected measurement range. After the dynamic spiking procedure is complete, the gas 

chromatograph is checked for bias at each of the four calibration levels. The bias should be less than 5% 

of the expected value for each point. Method 18 provides guidance for the calibration procedure and 

requirements. 

Prior to the dynamic spiking procedure, the gas manifold (used to quantitatively introduce propane, or 

similar hydrocarbon), which is typically a mass flow controller, is calibrated to a primary standard. After 

each test run, the gas manifold is checked for drift, and adjusted if the drift exceeds 10% of the expected 

value (calibrated value prior to dynamic spiking procedure). Method 205 provides guidance for this 

procedure. 

5.4 GAS MANIFOLD 

HCL may be quantitatively introduced into the flue gas stream, and when used in conjunction with a total 

flow measurement, can provide the reference HCL spiking concentrations for each dynamic spiking run. 

Prior to the dynamic spiking procedure, the gas manifold (used to quantitatively introduce HCL), which is 

typically a mass flow controller, is calibrated to a primary standard. After each test run, the gas manifold 

is checked for drift, and adjusted if the drift exceeds 10% of the expected value (calibrated value prior to 

dynamic spiking procedure). Method 205 provides guidance for this procedure. 

5.5 HCL CALIBRATION GAS FOR DYNAMIC SPIKING 

The HCL calibration gas used for dynamic spiking must be a certified gas with a tolerance less than or 

equal to 5%. 
HCL Dynamic Spiking Protocol 

August, 2006 

 10

6 DYNAMIC SPIKING RANGE 

The flue gas stream must be spiked at a minimum of three separate levels (low, mid, high) throughout the 

range of the HCL CEMS. The low level should be between 0 – 50%, the mid range should be between 

25 – 75%, and the high range should be between 50 – 100% of the span of the instrument. The dynamic 

spiked HCL concentrations can only be used for one range (Table 1). 

7 TYPICAL DYNAMIC SPIKING SET-UP 

Figure 1. Typical Dynamic Spiking Apparatus 

Dynamic Spiking Apparatus

HCL 

CEMS

900-1200 ppm HCL in N2

Calibration Manifold

(Mass flow meters)

Sample Probe

•Heated Filter 

• Pressure Control

•Laminar Flow 

Element

Heated sample line

Flue Gas

Gas

Conditioner

Reference

Measurement(s)

Heated line inside 

sample umbillical
HCL Dynamic Spiking Protocol 

August, 2006 

 11

8 DYNAMIC SPIKING PROCEDURE 

This section describes the procedure used to perform HCL dynamic spiking. Prior to testing, it is 

important that all analyzers are calibrated according to section 6 of this document. In addition, the control 

device should be at a steady state (small fluctuations of HCL or elements of opportunity). 

8.1 COLLECTION OF BASELINE DATA 

The baseline data will be used to compensate the measured HCl, during the dynamic spiking run, for 

background concentrations of HCL which may be present during normal operations. It is important to 

collect all element of opportunity data as well as HCL background data during the baseline collection 

period. 

1. Collect a minimum of ten, 1 minute averaged HCL data points prior to each dynamic spiking 

test run. 

2. Collect ten, 1 minute averaged data points for the element(s) of opportunity to be used for 

calculating the reference HCL concentration. The element of opportunity data set is collected 

simultaneous to the HCL baseline data, and must be collected prior to each dynamic spiking 

test run. 

3. If using total flow, collect a minimum of one flow reading during the baseline data collection. 

4. Prior to beginning the dynamic spike, ensure that all baseline data (HCL, element of 

opportunity, flow) does not exhibit large fluctuations in concentration (steady state). If large 

fluctuations exist, the baseline data collection procedure must be repeated. 

8.2 COLLECTION OF TEST DATA 

The HCL CEMS must be tested at a minimum of three levels through the measurement range of the 

instrument (low, mid, high), Table 1. Prior to each dynamic spiking test run, it is important that the 

appropriate baseline data is collected (section 7.1) and that all equipment is calibrated and appropriate 

bias checks are performed (section 6). 

1. Introduce the HCL calibration gas to the measurement system and allow the HCL CEMS 

values to reach a steady state. This may take up to 15 minutes. 
HCL Dynamic Spiking Protocol 

August, 2006 

 12

2. Collect a minimum of 30, one minute average HCL data points. 

3. Collect a minimum of 30, one minute average element(s) of opportunity data points. 

4. If using total flow through the system, collect at least five data points during the dynamic 

spiking test run. 

5. If using quantitative introduction of the HCL calibration gas, collect at least five data points for 

the calibration gas flow rate into the system during the dynamic spiking test run. 

6. Before stopping the dynamic spiking test run, ensure that the data sets are complete. It is 

recommended that the percent standard deviation, for all data sets, be less than or equal to 

20%. 

7. Stop the HCL calibration gas dynamic spiking and allow the system to return to baseline 

conditions. 

8. Perform a bias check for the element of opportunity reference CEMS, the flow measurement 

system, and the gas manifold for the HCL calibration gas and hydrocarbon (if dilution flow is 

used to calculate the reference HCL concentration). Section 6 provides guidance for the bias 

checks. 

9. Repeat the baseline data collection, and the dynamic spiking data collection, for subsequent 

HCL test levels. 

10. If dilution flow is used to calculate the HCl reference values, after the HCL dynamic spiking 

test runs are complete, perform a bias check of the dilution analyzer. 

8.3 DATA CALCULATIONS 

This section provides the calculations required to determine the accuracy, precision, and bias of the HCL 

CEMS. 

8.3.1 Baseline data 

8.3.1.1 HCL CEMS data 

The baseline HCL concentration is measured prior to each dynamic spiking run. For each baseline HCL 

data set, calculate the average, in ppm, using equation 1. 
HCL Dynamic Spiking Protocol 

August, 2006 

 13

Calculate the arithmetic mean of a data set as follows: 

= ∑xi

n

x

1

(Equation 1) 

where : 

x = Arithmetic mean 

n = Number of data points 

xi = Value of each data point 

8.3.1.2 Element of Opportunity Data 

The element of opportunity data set is acquired prior to each dynamic spiking test run, simultaneous to 

the baseline HCL concentration data set. For each element of opportunity, calculate the average value 

using equation 1. 

8.3.1.3 Flow via dilution 

When using dilution of a measured analyte (such as a hydrocarbon with subsequent GC measurement) 

as an indicator of total flow, calculate the total flow, in liters per minute using equation 2. 

Calculate the total flow as follows: 

 Tflow = 

( )

( ) *

Analyte measured

Analtye spike Tflow

−

− (Equation 2)

 Tflow = Total flow through the system in lpm 

 Analyte-Spike = Concentration of Spiked Analyte (ppm) 

 Analyte-measured = Measurement, downstream, of spiked Analyte (ppm) 

Calculate the average flow value, for the data set, using equation 1. 
HCL Dynamic Spiking Protocol 

August, 2006 

 14

8.3.2 Dynamic Spiking Test run data 

8.3.2.1 HCL CEMS data 

For each dynamic spiking test run, calculate the average and percent relative standard deviation of the 

data set using equations 1 and 3, respectively. 

Calculate the percent standard deviation as follows: 

1 / 2 2

1

1

2

1

⎥

⎥

⎥

⎥

⎥

⎥

⎥

⎦

⎤

⎢

⎢

⎢

⎢

⎢

⎢

⎢

⎣

⎡

−

⎟

⎟

⎠

⎞

⎜

⎜

⎝

⎛

−

=

∑ ∑ =

=

n

n

d

PRS

n

i i n

i i

d

d (Equation 3)

 x

Where: 

PRSd = Percent Relative Standard Deviation of the data set 

 x = Arithmetic mean 

8.3.2.2 Element of Opportunity data 

For each dynamic spiking test run, calculate the average and percent relative standard deviation of the 

data set using equations 1 and 3, respectively. If using total flow as a means to determine the reference 

HCL calibration gas concentration, use equation 2 to calculate the total flow prior to determining the 

average and percent relative standard deviation of the data set. 
HCL Dynamic Spiking Protocol 

August, 2006 

 15

8.3.3 Reference HCL concentration calculations 

8.3.3.1 Element of opportunity to calculate reference HCL concentration 

Equation 4 is used to calculate the reference HCL concentration for a given dynamic spiking test run. 

HCl ref = CalGas BaselineHCl

Opp pre

Opp post

avg

avg + −

− 1− * (Equation 4)

where: 

 

 Opp-post avg = average reference element of opportunity value during dynamic spiking test run 

 Opp-pre avg = average reference element of opportunity value during baseline test run 

 CalGas = HCl calibration gas concentration 

 Baseline HCl = CEMS HCl average baseline value 

8.3.3.2 Quantitative HCL calibration gas introduction and total flow to calculate reference HCL 

concentration 

When using the quantitative introduction of calibration gas and total system flow to calculation the 

reference HCL concentration for a given dynamic spiking test run, use equation 5. Equation 2 is used to 

calculate the total system flow. 

HCl ref = CalGas BaselineHCl

Tflow

Cflow

avg

avg * + (Equation 5)

Where: 

HCl ref = Reference HCl value for run “X” 

 Cflow = Average calibration HCL gas flow rate into system (lpm) 
HCL Dynamic Spiking Protocol 

August, 2006 

 16

 Tflow = Average Total System Flow during run (lpm) 

 CalGas = HCl calibration gas concentration 

 Baseline HCl = CEMS HCl average baseline value 

8.3.4 Linear Regression 

Linear regression is used to calculate the accuracy, precision, and bias of the HCL CEMS. For each 

dynamic spiking test run, plot the HCL CEMS reference value, Xaxis, versus the HCL measured value, Y 

axis. Determine the correlation coefficient (r ), the slope, and the intercept using equations 6-9. 

y b b x o 1 ˆ = + (Equation 6)

where: 

bo = The y intercept 

b1 = The slope 

The intercept is calculated according to the following equation: 

b y b x o = − 1 (Equation 7)

where: 

∑=

=

n

i

i x

n

x

1

1 

∑=

=

n

i

i y

n

y

1

1 

The slope of the line is calculated according to equation below: 
HCL Dynamic Spiking Protocol 

August, 2006 

 17

∑

∑

=

=

−

− −

= n

i 1

2

i

n

i 1

i i

1

( x x )

( x x )( y y )

b (Equation 8) 

The linear correlation coefficient is calculated according to the following equation. 

∑ ∑

∑

= =

=

− −

⎟

⎠

⎞ ⎜

⎝

⎛ − −

= n

i

i

n

i

i

n

i

i i

x x y y

x x y y

r

1

2

1

2

2

2 1

( ) ( )

( )( )

 (Equation 9) 

8.4 CRITERIA FOR ACCEPTANCE 

The criteria for the HCl dynamic spiking is: 

• The correlation coefficient, r, must be greater than or equal to 0.90 

• The slope must be 1.0, +/- 0.15 

• The Intercept must be equal to or less than 15% of the instrument span. 

At a minimum, the data set must meet the correlation coefficient. If this is not met, the dynamic spiking 

procedure must be repeated until the correlation coefficient criteria are met. If the HCl CEMS has met the 

correlation coefficient requirement, but does not meet either the slope, or intercept criteria, a bias exists 

and a correction factor must be applied to the HCl CEMS for data collection. The equations to determine 

the corrected value are provided in Section 8.5. The correction factor must be applied to the HCl CEMS 

one-minute average data until a new dynamic spiking procedure indicates the specific bias no longer 

exists, or, a different correction factor (bias) is indicated. 
HCL Dynamic Spiking Protocol 

August, 2006 

 18

8.5 BIAS CORRECTION 

If the HCl CEMS fails to meet both the slope and intercept criteria, the following correction factor must be 

applied to the one-minute average HCl data: 

1

0

b

y b CC i − = (Equation 10) 

Where:

C C = corrected CEMS HCL concentration 

yi

 = CEMS reported HCL concentration 

b0 = the intercept of the least squares linear regression line 

b1 = the slope of the least squares linear regression line 

b). If the HCl CEMS fails to meet the slope criteria, but meets the intercept criteria, the following 

correction factor must be applied to the one-minute average HCl data: 

1 b

y CC i = (Equation 11)

c). If the HCl CEMS fails to meet the intercept criteria, but meets the slope criteria, the following correction 

factor must be applied to the one-minute average HCl data: 

0 C y b i

C = − (Equation 12)
HCL Dynamic Spiking Protocol 

August, 2006 

 19

9 TABLES 

Table 1. Ongoing Quality Assurance/Quality Control Calibration Gas Ranges 

 HCl Calibration Gas Concentrations a

Test Units Zero-level Mid-Level High-Level 

Daily Calibration Drift % of Span 0-30 NA 50-100 

Absolute Calibration 

Audit 

% of Span 0-29 30-49 50-100 

Dynamic Spiking % of Span 0-50 25-75 50-100 

a

A copy of the supplier’s certificate of analysis must be provided for each gas cylinder. Calibration gases 

do not need to be Protocol 1 gases. It is recommended that the calibration gases, for all QA, have a 

minimum tolerance of 5%. 
HCL Dynamic Spiking Protocol 

August, 2006 

 20

10 REFERENCES 

1. United States Environmental Protection Agency (EPA). Technology Transfer Network, Emission 

Measurement Center, Promulgated Methods, Test Method 205: Verification of Gas Dilution 

Systems for Field Instrument Calibrations. Available: http://www.epa.gov/ttn/emc/promgate/m205.pdf via the internet. 

2. United States Environmental Protection Agency (EPA). Technology Transfer Network, Emission 

Measurement Center, Promulgated Methods, Test Method 18: Measurement of Gaseous 

Organic Compound Emissions by Gas Chromatography. Available: 

http://www.epa.gov/ttn/emc/promgate/m-18.pdf via the internet. 

3. Performance Specification Z: Specifications and Test Procedures for Hydrochloric Acid 

Continuous Emission Monitoring Systems at Stationary Sources. Eli Lilly and Company, 2005. 

4. Procedure DD: Quality Control and Quality Assurance Requirements for Hydrochloric Acid 

Continuous Emission Monitoring Systems at Stationary Sources. Eli Lilly and Company, 2005. 

5. Dilution Flow Measurement Protocol: Measurement of Total flow using a tracer gas with 

subsequent down stream quantitation. Eli Lilly and Company, 2006. 
HCL Dynamic Spiking Protocol 

August, 2006 

 21

11 APPENDICES 
(PROPOSED) TEST METHOD 322 - MEASUREMENT OF HYDROGEN CHLORIDE

EMISSIONS FROM PORTLAND CEMENT KILNS BY GFCIR

1.0 Applicability and Principle

1.1 Applicability. This method is applicable to the

determination of hydrogen chloride (HCl) concentrations in

emissions from portland cement kilns. This is an instrumental

method for the measurement of HCl using an extractive sampling

system and an infrared (IR) gas-filter correlation (GFC)

analyzer. This method is intended to provide the cement industry

with a direct interface instrumental method. A procedure for

analyte spiking is included for quality assurance. This method

is considered to be self-validating provided that the

requirements in section 9 of this method are followed.

1.2 Principle. A gas sample is continuously extracted from

a stack or duct over the test period using either a source-level

hot/wet extractive subsystem or a dilution extractive subsystem. 

A nondispersive infrared gas filter correlation (NDIR-GFC)

analyzer is specified for the measurement of HCl in the sample. 

The total measurement system is comprised of the extractive

subsystem, the analyzer, and the data acquisition subsystem. 

Test system performance specifications are included in this

method to provide for the collection of accurate, reproducible

data.

1.3 Test System Operating Range. The measurement range

(span) of the test system shall include the anticipated HCl

concentrations of the effluent and spiked samples. The range

should be selected so that the average of the effluent

measurements is between 25 and 75 percent of span. If at any

time during a test run, the effluent concentration exceeds the

span value of the test system, the run shall be considered

invalid.

2.0 Summary of Method

2.1 Sampling and Analysis. Kiln gas is continuously

extracted from the stack or duct using either a source level,

hot/wet extractive system, or an in-situ dilution probe or heated

out-of-stack dilution system. The sample is then directed by a

heated sample line maintained above 350EF to a GFC analyzer

having a range appropriate to the type of sampling system. The

gas filter correlation analyzer incorporates a gas cell filled

with HCl. This gas cell is periodically moved into the path of

an infrared measurement beam of the instrument to filter out

essentially all of the HCl absorption wavelengths. Spectral

filtering provides a reference from which the HCl concentration

of the sample can be determined. Interferences are minimized in

the analyzer by choosing a spectral band over which compounds

such as CO2 and H2O either do not absorb significantly or do not

match the spectral pattern of the HCl infrared absorption.
2.2 Operator Requirements. The analyst must be familiar

with the specifications and test procedures of this method and

follow them in order to obtain reproducible and accurate data.

3.0 Definitions

3.1 Measurement System. The total equipment required for

the determination of gas concentration. The measurement system

consists of the following major subsystems:

3.1.1 Sample Interface. That portion of a system used for

one or more of the following: sample acquisition, sample

transport, sample conditioning, or protection of the analyzers

from the effects of the stack gas.

3.1.2 Gas Analyzer. That portion of the system that senses

the gas to be measured and generates an output proportional to

its concentration.

3.1.3 Data Recorder. A strip chart recorder, analog

computer, or digital recorder for recording measurement data from

the analyzer output.

3.2 Span. The upper limit of the gas concentration

measurement range displayed on the data recorder.

3.3 Calibration Gas. A known concentration of a gas in an

appropriate diluent gas (i.e., N2).

3.4 Analyzer Calibration Error. The difference between the

gas concentration exhibited by the gas analyzer and the known

concentration of the calibration gas when the calibration gas is

introduced directly to the analyzer.

3.5 Sampling System Bias. The sampling system bias is the

difference between the gas concentrations exhibited by the

measurement system when a known concentration gas is introduced

at the outlet of the sampling probe and the known value of the

calibration gas.

3.6 Response Time. The amount of time required for the

measurement system to display 95 percent of a step change in gas

concentration on the data recorder.

3.7 Calibration Curve. A graph or other systematic method

of establishing the relationship between the analyzer response

and the actual gas concentration introduced to the analyzer.

3.8 Linearity. The linear response of the analyzer or test

system to known calibration inputs covering the concentration

range of the system.

3.9 Interference Rejection. The ability of the system to

reject the effect of interferences in the analytical measurement

processes of the test system.

4.0 Interferences

4.1 Sampling System Interferences. An important

consideration in measuring HCl using an extractive measurement

system is to ensure that a representative kiln gas sample is

delivered to the gas analyzer. A sampling system interferant is

a factor that inhibits an analyte from reaching the analytical

instrumentation. Condensed water vapor is a strong sampling

system interferant for HCl and other water soluble compounds. 
"Cold spots" in the sampling system can allow water vapor in the

sample to condense resulting in removal of HCl from the sample

stream. The extent of HCl sampling system bias depends on

concentrations of potential interferants, moisture content of the

gas stream, temperature of the gas stream, temperature of

sampling system components, sample flow rate, and reactivity of

HCl with other species in the gas stream. For measuring HCl in a

wet gas stream, the temperatures of the gas stream and sampling

system components and the sample flow rate are of primary

importance. In order to prevent problems with condensation in

the sampling system, these parameters must be closely monitored.

4.1.1 System Calibration Checks. Performing these

calibration checks where HCl calibration gas is injected through

the entire system both before and after each test run

demonstrates the integrity of the sampling system and capability

of the analyzer for measuring this water soluble and otherwise

unstable compound under ideal conditions (i.e., HCl in N2).

4.1.2 Analyte Spiking Checks. For analyte spiking checks,

HCl calibration gas is quantitatively added to the sample stream

at a point upstream of the particulate filter and all other

sample handling components both before and after each test run. 

The volume of HCl spike gas should not exceed 10 percent of the

total sample volume so that the sample matrix is relatively

unaffected. Successfully performing these checks demonstrates

the integrity of the sampling system for measuring this water

soluble and reactive compound under actual sample matrix

conditions. Successfully performing these checks also

demonstrates the adequacy of the interference rejection

capability of the analyzer. (See section 9.3 of this method.)

4.2 Analytical Interferences. Analytical interferences are

reduced by the GFC spectroscopic technique required by the

method. The accuracy of HCl measurements provided by some GFC

analyzers is known to be sensitive to the moisture content of the

sample. This must be taken into account in order to acquire

accurate results. These analyzers must be calibrated for the

specific moisture content of the samples. 

5.0 Safety

This method may involve sampling at locations having high

positive or negative pressures, or high concentrations of

hazardous or toxic pollutants, and cannot address all safety

problems encountered under these diverse sampling conditions. It

is the responsibility of the tester(s) to ensure proper safety

and health practices, and to determine the applicability of

regulatory limitations before performing this test method. 

Because HCl is a respiratory irritant, it is advisable to limit

exposure to this compound.

6.0 Equipment and Supplies

Note: Mention of company or product names does not

constitute endorsement by the U. S. Environmental Protection

Agency.
6.1 Measurement System. Use any GFC measurement system for

HCl that meets the specifications of this method. All sampling

system components must be maintained above the kiln gas

temperature, when possible, or at least 350EF. The length of

sample transport line should be minimized and sampling rate

should be as high as possible to minimize adsorption of HCl. The

essential components of the measurement system are described in

sections 6.1.1 through 6.1.12.

6.1.1 Sample Probe. Glass, stainless steel, HastalloyTM, or

equivalent, of sufficient length to traverse the sample points. 

The sampling probe shall be heated to a minimum of 350EF to

prevent condensation. Dilution extractive systems must use a

dilution ratio such that the average diluted concentrations are

between 25 to 75 percent of the selected measurement range of the

analyzer.

6.1.2 Calibration Valve Assembly. Use a heated, three-way

valve assembly, or equivalent, for selecting either sample gas or

introducing calibration gases to the measurement system or

introducing analyte spikes into the measurement system at the

outlet of the sampling probe before the primary particulate

filter.

6.1.3 Particulate Filter. A coarse filter or other device

may be placed at the inlet of the probe for removal of large

particulate (10 microns or greater). A heated (Balston® or

equivalent) filter rated at 1 micron is necessary for primary

particulate removal, and shall be placed immediately after the

heated probe. The filter/filter holder shall be maintained at

350EF or a higher temperature. Additional filters at the inlet

of the gas analyzer may be used to prevent accumulation of

particulate material in the measurement system and extend the

useful life of components. All filters shall be fabricated of

materials that are nonreactive with HCl. Some types of glass

filters are known to react with HCl. 

6.1.4 Sample Transport Lines. Stainless steel or

polytetrafluoroethylene (PTFE) tubing shall be heated to a

minimum temperature of 350EF (sufficient to prevent condensation

and to prevent HCl and NH3 from combining into ammonium chloride

in the sampling system) to transport the sample gas to the gas

analyzer.

6.1.5 Sample Pump. Use a leak-free pump to pull the sample

gas through the system at a flow rate sufficient to minimize the

response time of the measurement system. The pump components

that contact the sample must be heated to a temperature greater

than 350EF and must be constructed of a material that is

nonreactive to HCl. 

6.1.6 Sample Flow Rate Control. A sample flow rate control

valve and rotameter, or equivalent, must be used to maintain a

constant sampling rate within ±10 percent. These components must

be heated to a temperature greater than 350EF. (Note: The

tester may elect to install a back-pressure regulator to maintain
the sample gas manifold at a constant pressure in order to

protect the analyzer(s) from over-pressurization, and to minimize

the need for flow rate adjustments.)

6.1.7 Sample Gas Manifold. A sample gas manifold, heated

to a minimum of 350EF, is used to divert a portion of the sample

gas stream to the analyzer and the remainder to the by-pass

discharge vent. The sample gas manifold should also include

provisions for introducing calibration gases directly to the

analyzer. The manifold must be constructed of material that is

nonreactive to the gas being sampled.

6.1.8 Gas Analyzer. Use a nondispersive infrared analyzer

utilizing the gas filter correlation technique to determine HCl

concentrations. The analyzer shall meet the applicable

performance specifications of section 8.0 of this method. (Note: 

Housing the analyzer in a clean, thermally-stable, vibration free

environment will minimize drift in the analyzer calibration.) 

The analyzer (system) shall be designed so that the response of a

known calibration input shall not deviate by more than ±3 percent

from the expected value. The analyzer or measurement system

manufacturer may provide documentation that the instrument meets

this design requirement. Alternatively, a known concentration

gas standard and calibration dilution system meeting the

requirements of Method 205 of appendix M to part 51 of this

chapter, “Verification of Gas Dilution Systems for Field

Calibrations” (or equivalent procedure), may be used to develop a

multi-point calibration curve over the measurement range of the

analyzer.

6.1.9 Gas Regulators. Single stage regulator with cross

purge assembly that is used to purge the CGA fitting and

regulator before and after use. (This purge is necessary to

clear the calibration gas delivery system of ambient water vapor

after the initial connection is made, or after cylinder

changeover, and will extend the life of the regulator.) Wetted

parts are 316 stainless steel to handle corrosive gases.

6.1.10 Data Recorder. A strip chart recorder, analog

computer, or digital recorder, for recording measurement data. 

The data recorder resolution (i.e., readability) shall be 0.5

percent of span. Alternatively, a digital or analog meter having

a resolution of 0.5 percent of span may be used to obtain the

analyzer responses and the readings may be recorded manually. If

this alternative is used, the readings shall be obtained at

equally-spaced intervals over the duration of the sampling run. 

For sampling run durations of less than 1 hour, measurements at

1-minute intervals or a minimum of 30 measurements, whichever is

less restrictive, shall be obtained. For sampling run durations

greater than 1 hour, measurements at 2-minute intervals or a

minimum of 96 measurements, whichever is less restrictive, shall

be obtained.

6.1.11 Mass Flow Meters/Controllers. A mass flow meter

having the appropriate calibrated range and a stated accuracy of
±2 percent of the measurement range is used to measure the HCl

spike flow rate. This device must be calibrated with the major

component of the calibration spike gas (e.g., nitrogen) using an

NIST traceable bubble meter or equivalent. When spiking HCl, the

mass flow meter/controller should be thoroughly purged before and

after introduction of the gas to prevent corrosion of the

interior parts.

6.1.12 System Flow Measurement. A measurement device or

procedure to determine the total flow rate of sample gas within

the measurement system. A rotameter, or mass flow meter

calibrated relative to a laboratory standard to within ±2 percent

of the measurement value at the actual operating temperature,

moisture content, and sample composition (molecular weight) is

acceptable. A system which ensures that the total sample flow

rate is constant within ±2 percent and which relies on an

intermittent measurement of the actual flow rate

(e.g., calibrated gas meter) is also acceptable.

6.2 HCl Calibration Gases. The calibration gases for the

gas analyzer shall be HCl in N2. Use at least three calibration

gases as specified below:

6.2.1 High-Range Gas. Concentration equivalent to 80 to

100 percent of the span.

6.2.2 Mid-Range Gas. Concentration equivalent to 40 to 60

percent of the span.

6.2.3 Zero Gas. Concentration of less than 0.25 percent of

the span. Purified ambient air may be used for the zero gas by

passing air through a charcoal filter or through one or more

impingers containing a solution of 3 percent H2O2.

6.2.4 Spike Gas. A calibration gas of known concentration

(typically 100 to 200 ppm) used for analyte spikes in accordance

with the requirements of section 9.3 of this method.

7.0 Reagents and Standards

7.1 Hydrogen Chloride. Hydrogen Chloride is a reactive gas

and is available in steel cylinders from various commercial gas

vendors. The stability is such that it is not possible to

purchase a cylinder mixture whose HCl concentration can be

certified at better than ±5 percent. The stability of the

cylinder may be monitored over time by periodically analyzing

cylinder samples. The cylinder gas concentration must be

verified within 1 month prior to the use of the calibration gas. 

Due to the relatively high uncertainty of HCl calibration gas

values, difficulties may develop in meeting the performance

specifications if the mid-range and high-range calibration gases

are not consistent with each other. Where problems are

encountered, the consistency of the test gas standards may be

determined: (1) by comparing analyzer responses for the test

gases with the responses to additional certified calibration gas

standards, (2) by reanalysis of the calibration gases in

accordance with sections 7.2.1 or 7.2.2 of this method, or (3) by

other procedures subject to the approval of EPA.
7.2 Calibration Gas Concentration Verification. There are

two alternatives for establishing the concentrations of

calibration gases. Alternative No. 1 is preferred.

7.2.1 Alternative No. 1. The value of the calibration

gases may be obtained from the vendor's certified analysis within

1 month prior to the test. Obtain a certification from the gas

manufacturer that identifies the analytical procedures and date

of certification.

7.2.2 Alternative No. 2. Perform triplicate analyses of

the gases using Method 26 of appendix A to part 60 of this

chapter. Obtain gas mixtures with a manufacturer's tolerance not

to exceed ±5 percent of the tag value. Within 1 month of the

field test, analyze each of the calibration gases in triplicate

using Method 26 of appendix A to part 60 of this chapter. The

tester must follow all of the procedures in Method 26 (e.g., use

midget impingers, heated Pallflex TX40H175 filter (TFE-glass

mat), etc. if this analysis is performed. Citation 3 in section

13 of this method describes procedures and techniques that may be

used for this analysis. Record the results on a data sheet. 

Each of the individual HCl analytical results for each

calibration gas shall be within 5 percent (or 5 ppm, whichever is

greater) of the triplicate set average; otherwise, discard the

entire set and repeat the triplicate analyses. If the average of

the triplicate analyses is within 5 percent of the calibration

gas manufacturer's cylinder tag value, use the tag value;

otherwise, conduct at least three additional analyses until the

results of six consecutive runs agree within 5 percent (or 5 ppm,

whichever is greater) of the average. Then use this average for

the cylinder value.

7.3 Calibration Gas Dilution Systems. Sample flow rates of

approximately 15 L/min are typical for extractive HCl measurement

systems. These flow rates coupled with response times of 15 to

30 minutes will result in consumption of large quantities of

calibration gases. The number of cylinders and amount of

calibration gas can be reduced by the use of a calibration gas

dilution system in accordance with Method 205 of appendix M to

part 51 of this chapter, "Verification of Gas Dilution Systems

for Field Instrument Calibrations." If this option is used, the

tester shall also introduce an undiluted calibration gas

approximating the effluent HCl concentration during the initial

calibration error test of the measurement system as a quality

assurance check.

8.0 Test System Performance Specifications 

8.1 Analyzer Calibration Error. This error shall be less

than ±5 percent of the emission standard concentration or ±1

ppm,(whichever is greater) for zero, mid-, and high-range gases.

8.2 Sampling System Bias. This bias shall be less than

±7.5 percent of the emission standard concentration or ±1.5 ppm

(whichever is greater) for zero and mid-range gases.

8.3 Analyte Spike Recovery. This recovery shall be between
70 to 130 percent of the expected concentration of spiked samples

calculated with the average of the before and after run spikes. 

9.0 Sample Collection, Preservation, and Storage

9.1 Pretest. Perform the procedures of sections 9.1.1

through 9.1.3.3 of this method before measurement of emissions

(procedures in section 9.2 of this method). It is important to

note that after a regulator is placed on an HCl gas cylinder

valve, the regulator should be purged with dry N2 or dry

compressed air for approximately 10 minutes before initiating any

HCl gas flow through the system. This purge is necessary to

remove any ambient water vapor from within the regulator and

calibration gas transport lines; the HCl in the calibration gas

may react with this water vapor and increase system response

time. A purge of the system should also be performed at the

conclusion of a test day prior to removing the regulator from the

gas cylinder. Although the regulator wetted parts are corrosion

resistant, this will reduce the possibility of corrosion

developing within the regulator and extend the life of the

equipment.

9.1.1 Measurement System Preparation. Assemble the

measurement system by following the manufacturer's written

instructions for preparing and preconditioning the gas analyzer

and, as applicable, the other system components. Introduce the

calibration gases in any sequence, and make all necessary

adjustments to calibrate the analyzer and the data recorder. If

necessary, adjust the instrument for the specific moisture

content of the samples. Adjust system components to achieve

correct sampling rates.

9.1.2 Analyzer Calibration Error. Conduct the analyzer

calibration error check in the field by introducing calibration

gases to the measurement system at any point upstream of the gas

analyzer in accordance with sections 9.1.2.1 and 9.1.2.2 of this

method.

9.1.2.1 After the measurement system has been prepared for

use, introduce the zero, mid-range, and high-range gases to the

analyzer. During this check, make no adjustments to the system

except those necessary to achieve the correct calibration gas

flow rate at the analyzer. Record the analyzer responses to each

calibration gas. Note: A calibration curve established prior to

the analyzer calibration error check may be used to convert the

analyzer response to the equivalent gas concentration introduced

to the analyzer. However, the same correction procedure shall be

used for all effluent and calibration measurements obtained

during the test.

9.1.2.2 The analyzer calibration error check shall be

considered invalid if the difference in gas concentration

displayed by the analyzer and the concentration of the

calibration gas exceeds ±5 percent of the emission standard

concentration or ±1 ppm, (whichever is greater) for the zero,

mid-, or high-range calibration gases. If an invalid calibration
is exhibited, cross-check or recertify the calibration gases,

take corrective action, and repeat the analyzer calibration error

check until acceptable performance is achieved.

9.1.3 Sampling System Bias Check. For nondilution

extractive systems, perform the sampling system bias check by

introducing calibration gases either at the probe inlet or at a

calibration valve installed at the outlet of the sampling probe. 

For dilution systems, calibration gases for both the analyzer

calibration error check and the sampling system bias check must

be introduced prior to the point of sample dilution. For

dilution and nondilution systems, a zero gas and either a midrange or high-range gas (whichever more closely approximates the

effluent concentration) shall be used for the sampling system

bias check.

9.1.3.1 Introduce the upscale calibration gas, and record

the gas concentration displayed by the analyzer. Then introduce

zero gas, and record the gas concentration displayed by the

analyzer. During the sampling system bias check, operate the

system at the normal sampling rate, and make no adjustments to

the measurement system other than those necessary to achieve

proper calibration gas flow rates at the analyzer. Alternately

introduce the zero and upscale gases until a stable response is

achieved. The tester shall determine the measurement system

response time by observing the times required to achieve a stable

response for both the zero and upscale gases. Note the longer of

the two times and note the time required for the measurement

system to reach 95 percent of the step change in the effluent

concentration as the response time.

9.1.3.2 For nondilution systems, where the analyzer

calibration error test is performed by introducing gases directly

to the analyzer, the sampling system bias check shall be

considered invalid if the difference between the gas

concentrations displayed by the measurement system for the

sampling system bias check and the known gas concentration

standard exceeds ±7.5 percent of the emission standard or ±1.5

ppm, (whichever is greater) for either the zero or the upscale

calibration gases. If an invalid calibration is exhibited, take

corrective action, and repeat the sampling system bias check

until acceptable performance is achieved. If adjustment to the

analyzer is required, first repeat the analyzer calibration error

check, then repeat the sampling system bias check.

9.1.3.3 For dilution systems (and nondilution systems where

all calibration gases are introduced at the probe), the

comparison of the analyzer calibration error results and sampling

system bias check results is not meaningful. For these systems,

the sampling system bias check shall be considered invalid if the

difference between the gas concentrations displayed by the

analyzer and the actual gas concentrations exceed ±7.5 percent of

the emission standard or ±1.5 ppm, (whichever is greater) for

either the zero or the upscale calibration gases. If an invalid
calibration is exhibited, take corrective action, and repeat the

sampling system bias check until acceptable performance is

achieved. If adjustment to the analyzer is required, first

repeat the analyzer calibration error check.

9.2 Emission Test Procedures

9.2.1 Selection of Sampling Site and Sampling Points. 

Select a measurement site and sampling points using the same

criteria that are applicable to Method 26 of appendix A to part

60 of this chapter.

9.2.2 Sample Collection. Position the sampling probe at

the first measurement point, and begin sampling at the same rate

as used during the sampling system bias check. Maintain constant

rate sampling (i.e., ±10 percent) during the entire run. Field

test experience has shown that conditioning of the sample system

is necessary for approximately 1-hour prior to conducting the

first sample run. This conditioning period should be repeated

after particulate filters are replaced and at the beginning of

each new day or following any period when the sampling system is

inoperative. Experience has also shown that prior to adequate

conditioning of the system, the response to analyte spikes and/or

the change from an upscale calibration gas to a representative

effluent measurement may be delayed by more than twice the normal

measurement system response time. It is recommended that the

analyte spikes (see section 9.3 of this method) be performed to

determine if the system is adequately conditioned. The sampling

system is ready for use when the time required for the

measurement system to equilibrate after a change from a

representative effluent measurement to a representative spiked

sample measurement approximates the calibration gas response time

observed in section 9.1.3.1 of this method.

9.2.3 Sample Duration. After completing the sampling

system bias checks and analyte spikes prior to a test run,

constant rate sampling of the effluent should begin. For each

run, use only those measurements obtained after all residual

response to calibration standards or spikes are eliminated and

representative effluent measurements are displayed to determine

the average effluent concentration. At a minimum, this requires

that the response time of the measurement system has elapsed

before data are recorded for calculation of the average effluent

concentration. Sampling should be continuous for the duration of

the test run. The length of data collection should be at least

as long as required for sample collection by Method 26 of part 60

of this chapter. One hour sampling runs using this method have

provided reliable data for cement kilns.

9.2.4 Validation of Runs. Before and after each run, or if

adjustments are necessary for the measurement system during the

run, repeat the sampling system bias check procedure described in

section 9.1.3 of this method. (Make no adjustments to the

measurement system until after the drift checks are completed.) 
Record the analyzer's responses.

9.2.4.1 If the post-run sampling system bias for either the

zero or upscale calibration gas exceeds the sampling system bias

specification, then the run is considered invalid. Take

corrective action, and repeat both the analyzer calibration error

check procedure (section 9.1.2 of this method) and the sampling

system bias check procedure (section 9.1.3 of this method) before

repeating the run.

9.2.4.2 If the post-run sampling system bias for both the

zero and upscale calibration gas are within the sampling system

bias specification, then construct two 2-point straight lines,

one using the pre-run zero and upscale check values and the other

using the post-run zero and upscale check values. Use the slopes

and y-intercepts of the two lines to calculate the gas

concentration for the run in accordance with equation 1 of this

method. 

9.3 Analyte Spiking—Self-Validating Procedure. Use analyte

spiking to verify the effectiveness of the sampling system for

the target compounds in the actual kiln gas matrix. Quality

assurance (QA) spiking should be performed before and after each

sample run. The spikes may be performed following the sampling

system bias checks (zero and mid-range system calibrations)

before each run in a series and also after the last run. The HCl

spike recovery should be within ±30 percent as calculated using

equations 1 and 2 of this method. Two general approaches are

applicable for the use of analyte spiking to validate a GFC HCl

measurement system: (1) two independent measurement systems can

be operated concurrently with analyte spikes introduced to one of

the systems, or (2) a single measurement system can be used to

analyze consecutively, spiked and unspiked samples in an

alternating fashion. The two-system approach is similar to

Method 301 of this appendix and the measurement bias is

determined from the difference in the paired concurrent

measurements relative to the amount of HCl spike added to the

spiked system. The two-system approach must employ identical

sampling systems and analyzers and both measurement systems

should be calibrated using the same mid- and high-range

calibration standards. The two-system approach should be largely

unaffected by temporal variations in the effluent concentrations

if both measurement systems achieve the same calibration

responses and both systems have the same response times. (See

Method 301 of this appendix for appropriate calculation

procedures.) The single measurement system approach is

applicable when the concentration of HCl in the source does not

vary substantially during the period of the test. Since the

approach depends on the comparison of consecutive spiked and

unspiked samples, temporal variations in the effluent HCl

concentrations will introduce errors in determining the expected

concentration of the spiked samples. If the effluent HCl

concentrations vary by more than ±10 percent (or ±5 ppm,
whichever is greater) during the time required to obtain and

equilibrate a new sample (system response time), it may be

necessary to: (1) use a dual sampling system approach,

(2) postpone testing until stable emission concentrations are

achieved, (3) switch to the two-system approach [if possible] or,

(4) rely on alternative QA/QC procedures. The dual-sampling

system alternative uses two sampling lines to convey sample to

the gas distribution manifold. One of the sample lines is used

to continuously extract unspiked kiln gas from the source. The

other sample line serves as the analyte spike line. One GFC

analyzer can be used to alternately measure the HCl concentration

from the two sampling systems with the need to purge only the

components between the common manifold and the analyzer. This

minimizes the time required to acquire an equilibrated sample of

spiked or unspiked kiln gas. If the source varies by more than

±10 percent or ±5 ppm, (whichever is greater) during the time it

takes to switch from the unspiked sample line to the spiked

sample line, then the dual-sampling system alternative approach

is not applicable. As a last option, (where no other

alternatives can be used) a humidified nitrogen stream may be

generated in the field which approximates the moisture content of

the kiln gas. Analyte spiking into this humidified stream can be

employed to assure that the sampling system is adequate for

transporting the HCl to the GFC analyzer and that the analyzer's

water interference rejection is adequate.

9.3.1 Spike Gas Concentration and Spike Ratio. The volume

of HCl spike gas should not exceed 10 percent of the total sample

volume (i.e., spike to total sample ratio of 1:10) to ensure that

the sample matrix is relatively unaffected. An ideal spike

concentration should approximate the native effluent

concentration, thus the spiked sample concentrations would

represent approximately twice the native effluent concentrations. 

The ideal spike concentration may not be achieved because the

native HCl concentration cannot be accurately predicted prior to

the field test, and limited calibration gas standards will be

available during the field test. Some flexibility is available

by varying the spike ratio over the range from 1:10 to 1:20. 

Practical constraints must be applied to allow the tester to

spike at an anticipated concentration. Thus, the tester may use

a 100 ppm calibration gas and a spike ratio of 1:10 as default

values where information regarding the expected HCl effluent

concentration is not available prior to the tests. 

Alternatively, the tester may select another calibration gas

standard and/or lower spike ratio (e.g., 1:20) to more closely

approximate the effluent HCl concentration.

9.3.2 Spike Procedure. Introduce the HCl spike gas mixture

at a constant flow rate (±2 percent) at less than 10 percent of

the total sample flow rate. (For example, introduce the HCl

spike gas at 1 L/min (±20 cc/min) into a total sample flow rate

of 10 L/min). The spike gas must be preheated before
introduction into the sample matrix to prevent a localized

condensation of the gas stream at the spike introduction point. 

A heated sample transport line(s) containing multiple transport

tubes within the heated bundle may be used to spike gas up

through the sampling system to the spike introduction point. Use

a calibrated flow device (e.g., mass flow meter/controller) to

monitor the spike flow rate. Use a calibrated flow device (e.g.,

rotameter, mass flow meter, orifice meter, or other method) to

monitor the total sample flow rate. Calculate the spike ratio

from the measurements of spike flow and total flow. (See

equation 2 and 3 in section 10.2 of this method.)

9.3.3 Analyte Spiking. Determine the approximate effluent

HCl concentrations by examination of preliminary samples. For

single-system approaches, determine whether the HCl concentration

varies significantly with time by comparing consecutive samples

for the period of time corresponding to at least twice the system

response time. (For analyzers without sample averaging, estimate

average values for two to five minute periods by observing the

instrument display or data recorder output.) If the concentration

of the individual samples varies by more than ±10 percent

relative to the mean value or ±5 ppm, (whichever is greater), an

alternate approach may be needed.

9.3.3.1 Adjust the spike flow rate to the appropriate level

relative to the total flow by metering spike gas through a

calibrated mass flow meter or controller. Allow spike flow to

equilibrate within the sampling system for at least the

measurement system response time and a steady response to the

spike gas is observed before recording response to the spiked gas

sample. Next, terminate the spike gas flow and allow the

measurement system to sample only the effluent. After the

measurement system response time has elapsed and representative

effluent measurements are obtained, record the effluent unspiked

concentration. Immediately calculate the spike recovery.

9.3.3.2 If the spike recovery is not within acceptable

limits and a change in the effluent concentration is suspected as

the cause for exceeding the recovery limit, repeat the analyte

spike procedure without making any adjustments to the analyzer or

sampling system. If the second spike recovery falls within the

recovery limits, disregard the first attempt and record the

results of the second spike. 

9.3.3.3 Analyte spikes must be performed before and after

each test run. Sampling system bias checks must also be

performed before and after each test run. Depending on the

particular sampling strategy and other constraints, it may be

necessary to compare effluent data either immediately before or

immediately after the spike sample to determine the spike

recovery. Either method is acceptable provided a consistent

approach is used for the test program. The average spike

recovery for the pre- and post-run spikes shall be used to

determine if spike recovery is between 70 and 130 percent. 
C

gas

'

(mi% mf)

(C

avg

& bc)

mc

%(bi% bf)

2

10.0 Data Analysis and Emission Calculations

The average gas effluent concentration is determined from

the average gas concentration displayed by the gas analyzer and

is adjusted for the zero and upscale sampling system bias checks,

as determined in accordance with section 9.2.3 of this method. 

The average gas concentration displayed by the analyzer may be

determined by integration of the area under the curve for chart

recorders, or by averaging all of the effluent measurements. 

Alternatively, the average may be calculated from measurements

recorded at equally spaced intervals over the entire duration of

the run. For sampling run durations of less than 1-hour, average

measurements at 2-minute intervals or less, shall be used. For

sampling run durations greater than 1-hour, measurements at 2-

minute intervals or a minimum of 96 measurements, whichever is

less restrictive, shall be used. Calculate the effluent gas

concentration using equation 1.

(Eq. 1)

where:

bc = Yintercept of

the

calibration

leastsquares 

line.

bf = Y-intercept of the final bias check 2-point line.

bi = Y-intercept of the initial bias check 2-point 

line.

Cgas = Effluent gas concentration, as measured, ppm.

Cavg = Average gas concentration indicated by gas 

analyzer, as measured, ppm.

mc = Slope of the calibration least-squares line.

mf = Slope of the final bias check 2-point line.

mi = Slope of the initial bias check 2-point line.

The following equations are used to determine the percent

recovery (%R) for analyte spiking:

 %R = (SM/CE) x 100 (Eq. 2)

where:

SM = Mean concentration of duplicate analyte spiked 

samples (observed).

CE = Expected concentration of analyte spiked samples 

(theoretical).

 CE = CS(QS/QT) + SU(1-QS/QT) (Eq. 3)

where:

CS = Concentration of HCl spike gas (cylinder tag 

value).

QS = Spike gas flow rate.
QT = Total sample flow rate (effluent sample flow plus

spike flow).

SU = Native concentration of HCl in unspiked effluent

samples.

Acceptable recoveries for analyte spiking are ±30 percent.

11.0 Pollution Prevention

Gas extracted from the source and analyzed or vented from

the system manifold shall be either scrubbed, exhausted back into

the stack, or discharged into the atmosphere where suitable

dilution can occur to prevent harm to personnel health and

welfare or plant or personal property.

12.0 Waste Management

Gas standards of HCl are handled as according to the

instructions enclosed with the materials safety data sheets.

13.0 References

1. Peeler, J.W., Summary Letter Report to Ann Dougherty,

Portland Cement Association, June 20, 1996.

2. Test Protocol, Determination of Hydrogen Chloride

Emissions from Cement Kilns (Instrumental Analyzer Procedure)

Revision 4; June 20, 1996.

3. Westlin, Peter R. and John W. Brown. Methods for

Collecting and Analyzing Gas Cylinder Samples. Source Evaluation

Society Newsletter. 3(3):5-15. September 1978.
EcoChem 

Meßtechnik GmbH 

_____________________________________________ 

Geschäftsführer: Dr. Wolfgang Berkhahn 

Sitz der Gesellschaft: Überlingen/Bodensee 

Amtsgericht Überlingen HRB 1144 VAT-No. DE177730533 

Sparkasse Bodensee Überlingen 1009182 (BLZ 690 500 01) IBAN DE83 6905 0001 0001 0091 82

EcoChem Meßtechnik Alte Nußdorfer Str. 27 88662 Überlingen

To whom it may concern 

Überlingen, 24.04.2007 

Telefon : 07551 915 838 

Fax : 07551 915 839 

MC3-Stack Monitoring System 

Dear Sir or Madam, 

The MC3 has been approved by the German TÜV (TÜV Rheinland). 

The TÜV approval has been made in cooperation with the company Dr. Födisch Umweltmesstechnik AG and 

was financed 50% by EcoChem Meßtechnik GmbH. The system is sold in Germany under the Födisch label 

MCA04. The analyzer in the system is the EcoChem MC3. 

The report has passed the responsible committee in Germany August 17th. The “Umweltbundesamt” (UBA) 

has released the system for publication mid of September. The system is published and recommmended 

now in the “Bundesanzeiger”. 

Best regards 

- Wolfgang Berkhahn - 

2005_936_328560_21203173A.doc 

The duplicating of the report in an abridged way requires a written approval 

. 

TÜV Immissionsschutz und Energiesysteme GmbH 

TÜV Rheinland Group 

D–51105 Köln, Am Grauen Stein, Phone: +49-221/806-2756, Fax: +49-221/806-1349 

TÜV IMMISSIONSSCHUTZ 

UND ENERGIESYSTEME GmbH 

Report about the performance test of the 

measuring equipment MCA 04 for the 

components CO, NO, SO2, HCl, NH3, H2O, CO2

and O2 of the Company Dr. Födisch 

Umweltmesstechnik AG 

TÜV (MOT) report: 936/21203173/A 

Köln, 13.07.2005 

The TÜV Immissionsschutz und Energiesysteme GmbH is the Department Pollution Protection 

for the field of works: 

- Determination of the emissions and airborne substances of air pollution and odor nuisance; 

- Check of the regular installation and the function and calibration of continuously working emission measuring devices 

including systems for the data evaluation and emission remote monitoring; 

- Performance test of measuring equipment for the continuous monitoring of the emissions and airborne substances 

and of electronic systems for the data evaluation and emission remote monitoring 

accredited according to DIN EN ISO/IEC 17025 and DIN EN ISO 9002. 

The accreditation will be valid up to 04-12-2005. 

DAR Registration Number: DAP-PL-3856.99. 
2 

ABSTRACT 

On behalf of the Company Dr. Foedisch Umweltmesstechnik AG the TÜV 

Immissionsschutz und Energiesysteme GmbH carried out the performance test of the 

emission equipment MCA 04 for the components CO, NO, SO2, HCl, NH3, CO2, H2O 

and O2 according to the guidelines for continuous emission measurings [1]. 

The measuring equipment is operating according to the principles of the gas filter 

correlation and of the bi-frequency measurement process for infrared-active gas 

molecules. The oxygen measurement is carried out according to the circonium 

dioxide measurement process. 

The test was carried out within a laboratory test and a five-month field test with two 

measuring equipments in the waste gas of an industrial residual incineration. The 

smallest measurement ranges being tested were: 

Carbon monoxide: 0 up to 75 mg/m3

 Hydrogen chloride: 0 up to 15 mg/m3

Nitrogen monoxide: 0 up to 200 mg/m3 Ammonia: 0 up to 30 mg/m3

Sulphur dioxide: 0 up to 75 mg/m3

 Waste gas humidity: 0 up to 40 Vol.-% 

Carbon dioxide: 0 up to 20 Vol.-% Oxygen: 0 up to 25 Vol.-% 

The conditions of the minimum requirements were met with the performance test. 

The TÜV Immissionsschutz und Energiesysteme GmbH will therefore suggest a 

publication as a performance-tested measuring equipment for the continuous 

recording of the emissions of CO, NO, SO2, HCl, NH3 and CO2 and of the reference 

measurands H2O and O2 for systems according to TA Luft (Technical Instruction on 

Air), 13. BlmSchV and 17. BlmSchV and 30. BlmSchV.
3 

Accredited Test Institute 

DAP-PL-3856.99 

Report about the performance test of the measuring equipment MCA 04 

for the components CO, NO, SO2, HCl, NH3, H2O, CO2 and O2 of the 

Company Dr. Födisch Umweltmesstechnik AG 

Measuring equipment to be checked: MCA 04 

Equipment manufacturer: Dr. Födisch Umweltmesstechnik AG 

Zwenkauer Straße 22 

D-04420 Markranstädt 

Check period: Oktober 2004 bis Juli 2005 

Date of report: 13.07.2005 

Number of report: 936/21203173/A 

Size of report: 369 pages altogether 

Appendix as of page 186 

Manual as of page 237 with 132 pages 
4 

1 Summary and Suggestion of Announcement 

1.1 Summarized representation of the test results 

Minimum 

Requirement 

Requirement Test Result Assessment Page 

2.1 Common requirements for measuring and evaluation equipment for the determination of dusty 

and gaseous emissions 

2.1.1 General requirements 

2.1.1.1 Normative 

conditions 

Compliance with the valid 

performance criteria 

The performance test has been carried 

out in compliance with the mentioned 

guidelines. 

fulfilled 39 

2.1.1.2 Complete 

measuring 

equipment 

The test must cover the 

complete measuring 

equipment incl. operating 

instructions in German 

language. 

The performance-tested type covers the 

complete measuring equipment including 

sampling system, analyser cabinet and 

operating instructions in German 

language. 

fulfilled 40 

2.1.1.3 Compliance 

with the 

minimum 

requirements 

Two pieces of measuring 

equipment identically 

constructed. Laboratory 

and three-month field test. 

The laboratory tests have been 

completed successfully. The endurance 

test has been carried out from 27.01. 

2005 up to 06.07. 2005 with a single 

system. 

fulfilled 41 

2.1.1.4 Analysis 

function 

Statistically proved 

connection between the 

display of the equipment 

and the reference method 

of measurement. 

A statistically proved connection 

between the standard reference method 

of measurement and the display of the 

equipment could be proved for each 

individual measuring component. 

fulfilled 44 

2.1.1.5 Linearity Deviation of the actual 

values from the target 

values of the characteristic 

curve of the equipment ≤ 2 

% of the measuring range. 

The linearity has been tested with all 

measuring components. No deviations 

could be found being larger than ± 2 % 

each in relation to the measuring range 

respectively. 

fulfilled 105 

2.1.1.6 Adjustment of 

the settings 

Protection against unauthorized or unintentional 

misadjustment of the 

measuring equipment. 

The adjustment of the measuring 

equipment is only possible with the 

knowledge of the appropriate 

passwords. 

fulfilled 111 

2.1.1.7 Position of 

the zero point 

(living zero 

point) 

Position of the zero point at 

10 % or 20 %, position of 

the reference point at 70 % 

of the full deflection. 

The position of the zero point had been 

set to 4 mA. The position of the reference point may be adapted to the 

measuring range by the selection of the 

concentration of the test gas. 

fulfilled 112 
5 

Minimum 

requirement 

Requirement Test result Assessment Page 

2.1.1.8 

2.1.1.9 

Zero point 

drift in the 

maintenance 

interval 

Reference 

point drift in 

the 

maintenance 

interval 

Zero point drift in relation 

to the measuring range 

≤ 3 %. Reference point 

drift in relation to the 

measuring range ≤ 3 %. 

The pieces of measuring equipment 

have been set for all measuring 

channels to be tested until 28.01.2005. 

From 28.01.2005 to 16.06.2005 no 

deviations of the measuring channels 

could be found larger than 2.9 % in 

relation to the final value of the 

measuring range. Therefore the maximum drift of the reference point display 

for all measuring channels has been 

below 3 % within the complete test 

period in relation to the final value of 

the measuring range. 

fulfilled 113 

2.1.1.10 Display range Display range 1.5 times of 

the limiting value. 

As part of the performance test the 

measuring equipment has been set to 

the measuring ranges of the 17th

BlmSchV. Other measuring ranges 

may be set at the measuring 

equipment. 

fulfilled 119 

2.1.1.11 Measured 

value output 

Connection options for 

recording unit. 

The connection of additional measuring 

instruments and peripheral devices is 

possible with appropriate connections. 

fulfilled 120 

2.1.1.12 Status 

signals 

Message of the operating 

condition with the status 

signals operational 

readiness, maintenance, 

troubles. 

The measuring equipment is provided 

with the required status signals. 

fulfilled 121 

2.1.1.13 Availability Availability during the 

performance test ≥ 95 %. 

The equipment has an availability of 

98.1 or 98.7 %. Thus, as part of the 

performance test, they exceeded the 

required value of 95 % or 98 % for the 

oxygen measurement. The number of 

the invalid half-hour average values 

achieved at most due to the control and 

adjustment work required during 

normal operation is below the number 

of invalid half-hour average values 

permitted at most when dividing up the 

activities in two days according to the 

requirements for systems of the 13th

BlmSchV and also of the 17th

BlmSchV. 

fulfilled 122 

2.1.1.14 Maintenance 

interval 

Maintenance interval must 

be determined and it must 

be > 8 days. 

The zero point alignment is done 

automatically every 24 hours. The 

results of the drift examinations can be 

found in this report under item 6 

[2.1.1.8 Zero point drift in the 

maintenance interval] or 6 [2.1.1.9 

Reference point drift in the 

maintenance interval]. Therefore there 

was a maintenance interval of 2 

months. 

fulfilled 124 
6 

Minimum 

requirement 

Requirement Test result Assessment Page 

2.1.1.15 Repeatability The repeatability from 

double-specifications 

must be determined. 

The repeatability has been 

determined during the field test and 

it is fulfilled for all components. 

fulfilled 125 

2.1.1.16 Nominal utility 

conditions 

Requirements must be 

met with the nominal 

utility conditions 

according to DIN 43745 

for 

a) Power supply voltage 

b) Relative atmospheric 

 humidity 

c) Content of the air of 

 liquid water 

d) Oscillation. 

To a) 

No influence to the measurement 

signal could be found from 190 to 

250 V. 

To b) 

The influence of the atmospheric 

humidity has not been examined 

separately. But it has to be 

assumed due to the construction of 

the device that it is insensitive 

against atmospheric humidity, as 

long as the dewpoint is not 

reached. 

To c) 

The analyser is splash-proof, it 

should not be used unprotectedly 

at places with liquid water in the 

air. 

To d) 

During the endurance test the 

devices were exposed to the 

oscillations and vibrations occuring 

at the measuring position. No 

recognizable influences on the 

function of the devices could be 

found. For reason of precaution the 

site of installation or mounting 

place of the analyser should be 

possibly safe from vibrations. 

The manufacturer does not 

mention the operating position of 

the analyser separately; it is 

predefined by the design. 

fulfilled 126 

2.1.1.17 Automatic 

readjustment 

The corrective range 

permitted at most has to 

be determined. 

The measuring equipment carries 

out an automatic zero point 

alignment. If the control range of 6 

or 10 % is exceede, the measuring 

equipment issues a status signal. 

fulfilled 127 
7 

Minimum 

requirement 

Requirement Test result Assessment Page

2.1.1.18 Ambient 

temperature 

range 

With installation in the 

open: -20 to 50 °C, 

with installation at 

temperature-controlled 

places: 5 to 40 °C. 

Two devices of the type MCA 04 

have been exposed to temperature 

variations between +5 °C and +40 

°C. Doing this, maximum 

deviations on the zero point of 3.7 

% and of –4.1 % on the reference 

point have been determined in 

relation to the display range 

respectively, or 0.34 vol.-% with 

O2. 

fulfilled 128 

2.1.1.19 Influence test 

gas flow 

Influence on the 

measurement signal < 1 

% of the display range. 

It could be seen with the tested 

measurement equipment, that with 

a flow between 280 and 400 l/min 

the influence on the measurement 

signals is < 1 % in relation to the 

measurement range. If this range 

is exceeded, the measurement 

equipment issues a status signal. 

fulfilled 132 

2.1.1.20 Drift of the 

measuring ray 

With optical methods, 

maximum influence of 2 

% of the measurement 

range final value to the 

measurement signal at 

the angular range 0.3°. 

Not applicable, since the 

measurement equipment is 

operated extractively. 

Not applicable 134 

2.1.1.21 Contamination 

monotoring 

Contamination 

monotoring during the 

operation with optical 

methods 

Not applicable, since the 

measurement equipment is 

operated extractively. 

Not applicable 135 

2.1.1.22 Automatic 

recording of 

zero and 

reference 

point 

Measurement equipment 

must have a mechanism 

for the automatic 

recording of zero and 

reference point. 

Not applicable, since the 

measurement equipment has no 

possibility for the automatic 

recording of zero and reference 

points. 

Not applicable 136 

2.1.1.23 Setting time The t90 time must be 

≤ 200 s. 

According to the measuring 

components there are t90 times 

between 131 and 181 (O2 80 s) for 

the tested measurement 

equipment. Therefore the required 

t90 time has been met with all 

components. 

fulfiled 137 

2.1.1.24 Multi component 

measurement 

equipment 

The requirements must 

be met for each 

individual component. 

The measurement results for all 

channels have been provided 

simultaneously with the 

assessment of the minimum 

requirements. 

fulfilled 140 

2.1.1.25 Digital 

interface 

The digital interface 

must be completely 

described in the 

approriate standards and 

guidelines. 

Not applicable, since there is no 

authorized digital interface 

available. However, the 

measurement equipment MCA 04 

is able to issue its measurement 

signals and its status of equipment. 

Not applicable 141 
8 

Minimum 

requirement 

Requirement Test result Assessment Page 

2.1.1.26 Uncertainty of 

measurement 

Determination of 

extended uncertainty of 

measurement according 

to DIN EN ISO 14956, 

comparison with defined 

requirements. 

The uncertainties determined for 

all components are below the 

predefined values and therefore 

meet the requirements. 

fulfilled 142 

2.2 Additional requirements of measurement equipment for the determination of gaseous emissions 

 Not applicable here 

2.3 Additional requirements of measurement equipment for the determination of gaseous emissions 

2.3.1 General requirements 

2.3.1.1 Detection limit Less than or equal to 5 

% of the limit value of the 

daily average value. 

Detection limits between 0.49 and 

4.85 % of the respective limit value 

of the daily average value have 

been found for the measuring 

components according to 17th

BlmSCHV, for NH3 there has been 

a detection limit of 1.90 or 1.66 % 

of the measurement range. 

fulfilled 144 

2.3.1.2 Temperature 

drift 

Change of zero point 

and reference point 

display 

≤ 5 % of the 

measurement range 

starting out from 20 °C 

over the complete 

temperature range. 

For all tested devices the 

maximum temperature drift has 

been –3.7 % on the zero point and 

–3.5 % on the reference point for 

the components CO, NO, SO2, 

HCl, NH3 and CO2 of the 

measurement range respectively. 

fulfilled 147 

2.3.1.3 Transverse 

sensitivity 

The sum of the 

transverse sensitivities 

shall be ≤ 5 % of the 

measurement range. 

The transverse sensitivities 

determined at most with both 

devices were 4.0 % on the zero 

point and on the reference point in 

relation to the appropriate 

measurement range. 

fulfilled 148 

2.3.1.4 Sampling and 

preliminary 

processing 

Proper solid filtering, 

avoid crosscontamination effects as 

far as possible. 

The sampling systems used with 

the enduring prooftesting have 

been working properly in the more 

than tree-month field test even at 

higher waste gas humidities. 

Adsorption and desorption effects 

could not be observed during the 

test. 

fulfilled 155 

2.3.1.5 Repeatability Repeatability ≥ 30. For the repeatability of the 

individual measuring components 

within the tested measurement 

ranges values between 30 and 183 

have been determined. 

fulfilled 156 
9 

Minimum 

requirement 

Requirement Test result Assessment Page 

2.3.2 Additional requirements of measurement equipment for the determination of organic compounds 

 (total carbon) 

 Not applicable here 

2.4 Additional requirements of measurement equipment for the determination of reference values 

2.4.1 Measurement equipment for the determination of the oxygen content 

2.4.1.1 Availability Availability during the 

performance test ≥ 98 % 

The devices have an availability of 

98.1 % or 98.7 %. With that as part 

of the performance test they 

exceeded the required value of 

98 % for oxygen. 

fulfilled 163 

2.4.1.2 Detection limit ≤ 0.2 vol.-% O2 Detection limits of 0.14 and 0.15 

vol.-% O2 have been determined 

for the measurement equipment. 

fulfilled 164 

2.4.1.3 Repeatability Repeatability ≥ 70 The repeatability has been 

determined for the measurement 

range 0 to 25 vol.-% O2. The result 

was a value of 172. 

fulfilled 165 

2.4.1.4 Temperature 

drift 

Change of zero point 

and reference point 

display 

≤ 0.5 vol.-% O2, starting 

out from 20 °C over the 

complete temperature 

range. 

Two devices of the type MCA 04 

have been exposed to 

temperatures between +5 °C and 

+40 °C in a climatic chamber. No 

deviations 

> 0.34 vol.-% O2 have been 

determined. 

fulfilled 167 

2.4.1.5 Transverse 

sensivity 

The sum of the 

transverse sensivities 

should be ≤ 0.2 vol.-% 

O2. 

For the measurement equipment 

MCA 04 no relevant transverse 

sensivities could be determined 

with the component O2. 

fulfilled 168 

2.4.1.6 Sampling Proper solid filtering, 

avoid crosscontamination effects as 

far as possible. 

The sampling systems used with 

the enduring prooftesting have 

been working properly in the field 

test. Adsorption and desorption 

effects could not be observed 

during the test. Pay attention to a 

sufficient and complete heating of 

all components. The sampling 

systems may be adapted to the 

systems to be monitored according 

to the formulation. 

fulfilled 170 

2.4.1.7 Drift in the 

maintenance 

intervall 

≤ 0.2 vol.-% O2 There were no drifts < 0.2 vol.-% 

O2 to be determined during the field 

test. The maintenance interval for 

the test gas task correspondingly 

results according to item 6 

[2.1.1.14 maintenance interval] of 2 

months. 

fulfilled 171 
10 

Minimum 

requirement 

Requirement Test result Assessment Page 

2.4.1.8 Linearity Deviation of the actual 

values from the target 

values of the 

characteristic curve of 

the equipment 

≤ 0.3 vol.-% O2

The linearity has been tested for 

the measurement range 0 to 25 

vol.-%. There has been no larger 

deviation determined than 0.17 

vol.-%. 

fulfilled 172 

2.4.2 Measurement equipment for the determination of the waste gas volumetric flow 

 Not applicable here 

2.4.3 Measurement equipment for the determination of the moisture content 

2.4.3.1 Display range Measured values shall 

be in the upper third of 

the display range during 

normal operation. 

The important application cases 

may be covered with the 

measurement range 0 to 40 vol.-%. 

A reduction of the measurement 

range to smaller values is possible. 

fulfilled 173 

2.4.3.2 Detection limit Smaller than 5 % of the 

measurement range. 

With values of < 0.4 % in relation to 

the measurement range the 

conditions of the minimum 

requirement were clearly reached. 

The measurement range 0 to 40 

vol.-% meets the measuring range 

0 to 321.4 g/m3

 as mass 

concentration. 

fulfilled 174 

2.4.3.3 Repeatability Repeatability ≥ 30 The repeatability for water in the 

tested measurement ranges is 253. 

fulfilled 175 

2.4.3.4 Temperature 

drift 

Change of zero point 

and reference point 

display 

≤ 0.5 % of the 

measurement range, 

starting out from 20 °C 

over the complete 

temperature range. 

When testing the devices in a 

climatic chamber with a 

temperature range of +5 °C to 

+40 °C there was a maximum 

deviation at the zero point of 

–0.1 %, and at the reference point 

of –2.7 % in relation to the 

measurement range. 

fulfilled 177 

2.4.3.5 Transverse 

sensitivities 

The sum of the 

transverse sensitivities 

shall be ≤ 4% of the 

measurement range. 

The maximum transverse 

sensitivity was 1 % and it is 

therefore < 4% of the display range 

with both devices. 

fulfilled 178 

2.4.3.6 Calibration Gravimetric calibration The measurement equipment has 

been adjusted, performance-tested 

and calibrated with gravimetric 

methods. 

fulfilled 180 

Appendix E Requirements of measurement and evaluation equipment in the sense of the 17th BlmSchV 

E1 Requirements to measurement equipment of systems in the sense of the 17th BlmSchV 

E 1.1 Measurement 

range 

requirements 

for the daily 

average value 

Proof of the minimum 

requirements in the 

range of the one and a 

half times limit value 

TMW. 

The display range of the tested 

measurement equipment had been 

set for the measuring component 

NO to 1.53 times of the limit value 

for the daily average value. 

fulfilled 181 

E 1.2 Measurement 

range 

requirements 

for the halfhour average 

value 

Measurement range up 

to the one and a half 

times of the limit value 

HMW shall be covered. 

The display range of the tested 

measurement equipment may be 

adapted to the appropriate 

measurement task. 

fulfilled 182 
11 

1.2 Suggestion of Announcement 

Due to the achieved positive results the following recommendation is given for the announcement as a 

performance-tested measurement equipment: 

1.2.1 Measurement task : Continuous monitoring of the emissions 

1.2.2 Name of device : MCA 04 

1.2.3 Measuring 

components 

: H2O, HCl, CO, NO, SO2, NH3, CO2, O2 

1.2.4 Manufacturer : Dr. Foedisch Umweltmesstechnik AG, D-04420 Markranstädt 

1.2.5 Suitability : For systems requiring official approval and systems of the 27th BlmSchV 

1.2.6 Measurement ranges 

with the performance 

test 

: 

Component Measurement ranges 

 Waste gas humidity H2O 0 - 40 vol.-% 

 Hydrogen chloride HCl 0 – 15 

0 - 90 

mg/m3 

mg/m3

 Carbon monoxide CO 0 – 75 

0 - 300 

mg/m3 

mg/m3

 Nitrous oxide NO 0 – 200 

0 - 395 

mg/m3 

mg/m3

 Sulphur dioxide SO2 0 – 75 

0 - 300 

mg/m3 

mg/m3

 Ammonia NH3 0 – 30 

0 - 75 

mg/m3 

mg/m3

 Carbon dioxide CO2 0 – 20 mg/m3

 Oxygen O2 0 - 25 mg/m3

1.2.7 Software version : MC3 Firmware V 1.83 

1.2.8 Restrictions • For the component SO2 in the measurement range 0 to 75 

mg/m3 the minimum requirements for the transverse sensitivity at 

concentrations of HCl > 50 mg/m3

 and N2O > 20 mg/m3 are not 

met. 

• For the component HCl in the measurement range 0 to 15 mg/m3 

the minimum requirements for the transverse sensitivity at 

concentrations of SO2 > 200 mg/m3 and N2O > 20 mg/m3 are not 

met. 

1.2.9 Notes : • The measurement equipment is operated with humid waste gas. 

• The maintenance interval for the test gas task for the 

measurment equipment MCA 04 is two months. 

 

1.2.10 Test institute : TÜV Immissionsschutz und Energiesysteme GmbH, Köln 

TÜV Rheinland Group 

1.2.11 Test report : 936/21203173/A of 13.07. 2005 
 

This certificate may only be reproduced in its entirety and without change 

Page 1 of 7 

PRODUCT CONFORMITY CERTIFICATE 

This is to certify that the 

MCA 04 Multi Component Analyser 

manufactured by: 

Dr. Födisch Umweltmesstechnik AG 

Zwenkauer Straße 159

D-04420 Markranstädt / OT Kulwitz

Germany 

has been assessed by Sira Certification Service 

and for the conditions stated on this certificate complies with: 

MCERTS Performance Standards for Continuous Emission 

Monitoring Systems, Version 2, Revision 1 (April 2003) 

Certification Ranges : 

SO2 0 to 75 mg/m30 to 300 mg/m3

NO 0 to 200 mg/m30 to 395 mg/m3

CO 0 to 75 mg/m30 to 300 mg/m3

HCl 0 to 15 mg/m30 to 90 mg/m3

NH3 0 to 20 mg/m30 to 75 mg/m3

 O2 0 to 25 %vol 

CO2 0 to 20 %vol 

 H2O 0 to 40 %vol 

Project No: 674/0258 

Certificate No: Sira MC 070115/00 

Initial Certification: 02 July 2007 

This Certificate Issued 02 July 2007 

Renewal Date: 01 July 2012

Technical Director 

MCERTS is operated on behalf of the Environment Agency by 

Sira Certification Service 

12 Acorn Industrial Park, Crayford Road, Crayford 

Dartford, Kent, UK, DA1 4AL 

Tel: 01322 520500 Fax: 01322 520501 
 

This certificate may only be reproduced in its entirety and without change 

Page 2 of 7 

Approved Site Application 

Any potential user should ensure, in consultation with the manufacturer, that the emission 

monitoring system is suitable for the process on which it will be installed. For general 

guidance on stack emission monitoring techniques refer to Environment Agency Technical 

Guidance Note M2: Monitoring of stack emissions to air. This is available on the Agency’s 

website at www.mcerts.net 

On the basis of the assessment and the ranges required for compliance with EU Directives this 

instrument is considered suitable for use on waste incineration and large coal-fired 

combustion plant applications. 

Basis of Certification 

This certification is based on the following Test Report(s) and on Sira’s assessment and 

ongoing surveillance of the product and the manufacturing process: 

TÜV Rheinland Report No: 936/21203173/A dated 13/07/05 

TÜV Rheinland Report No: 936/21203173/B dated 23/12/05 

TÜV Rheinland Report No: 936/21204231/C dated 22/06/07 

TÜV reports are accepted on the basis of the Environment Agency’s document ‘MCERTS – 

Guidance on the acceptance of German type approval test reports for CEMS’ Version 2 

(October 2003) 

 

Product Certified 

The MCA04 measuring system consists of the following parts: 

• Heated sampling probe Type SP 2000 H 

• Heated line (length during QAL1 10m) 

• Analyser unit MCA04 

This certificate applies to all instruments fitted with software version MC3 V1.83 onwards 

(serial number 05002 onwards). 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007
 

This certificate may only be reproduced in its entirety and without change 

Page 3 of 7 

Certified Performance

The instrument was evaluated for use under the following conditions: 

Ambient Temperature Range: +50C to +400C 

Unless otherwise stated the evaluation was carried out on the certification ranges SO2 0 to 75 mg/m3, NO 0 to 200 mg/m3, CO 0 

to 75 mg/m3, HCl 0 to 15 mg/m3, NH3 0 to 20 mg/m3, O2 0 to 25%vol, CO2 0 to 20%vol & H2O 0 to 40%vol. 

Test Results expressed as % of the 

certification range 

Other results MCERTS 

specification 

<0.5 <1 <2 <4 

Linearity CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2 0.17 

-0.7 

-0.9 

-0.9 

-0.8 

-0.7 

2.0 

2.0 

<2% 

<2% 

<2% 

<2% 

<2% 

<2% 

<0.3% 

Cross-sensitivity (O2, H20, CO2, CH4, 

N2O, NO, NO2, NH3, SO2, HCl) 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2 <0.02 

-2.7 

-3.9 

-4.0 

-4.0 

3.6 

1.0 

-2.5 

Note 1 

<4% 

<4% 

<4% 

<4% 

<4% 

<4% 

<4% 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007
 

This certificate may only be reproduced in its entirety and without change 

Page 4 of 7 

Test Results expressed as % of the 

certification range 

Other results MCERTS 

specification 

<0.5 <1 <2 <4 

Temperature dependent zero shift 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

0.12 

0.15 

0.09 

0.25 

0.08 

0.01 

0.01 

<0.01 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.5%/oC 

Temperature dependent upper 

reference point shift 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

0.13 

0.10 

0.21 

0.25 

0.11 

0.18 

0.15 

0.03 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.3%/oC 

<0.5%/oC 

Response time 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

144 

151 

162 

181 

176 

151 

131 

85 

<200s 

<200s 

<200s 

<600s 

<200s 

<200s 

<200s 

<200s 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007
 

This certificate may only be reproduced in its entirety and without change 

Page 5 of 7 

Test Results expressed as % of the 

certification range 

Other results MCERTS 

specification 

<0.5 <1 <2 <4 

Detection Limit 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

0.21 

0.36 

0.28 

0.15 

0.77 

0.61 

1.97 

1.90 

<2% 

<2% 

<2% 

<2% 

<2% 

<2% 

<2% 

<0.2% 

Interference of test gas flow on the 

measurement signal 

O2

-0.7 Note 2 <1% 

Vibration test 

(10 to 60Hz (±0.3mm), 60 to 150Hz at 

19.6m/s2)

Note 3 To be reported 

Mains voltage (190V to 250V) No effect Not specified 

Sample gas pressure Note 3 To be reported 

Sample gas temperature Note 3 To be reported 

Analysis function Note 4

CO 

NO 

SO2

H2O 

CO2

O2

99.5% 

96.2% 

98.9% 

99.8% 

99.8% 

99.9% 

>95% 

>95% 

>95% 

>95% 

>95% 

>95% 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007 
 

This certificate may only be reproduced in its entirety and without change 

Page 6 of 7 

Test Results expressed as % of the 

certification range 

Other results MCERTS 

specification 

<0.5 <1 <2 <4 

Integral performance Note 4

NH3 

HCl 

5.0 

9.6 

<10% 

<10% 

Availability Note 4 98.1% >95% 

Zero drift during field trial Note 4 

CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

0.20 

0.15 

0.43 

<0.1 

0.0 

<0.1 

<0.01 

1.0 

<2%/week 

<2%/week 

<2%/week 

<2%/week 

<2%/week 

<2%/week 

<0.2%/week 

Upper reference point drift during field 

trial Note 4 CO 

NO 

SO2

HCl 

NH3

H2O 

CO2

O2

0.30 

0.35 

0.06 

0.52 

1.10 

0.60 

1.00 

-0.8 

<4%/week 

<4%/week 

<4%/week 

<4%/week 

<4%/week 

<4%/week 

<0.2%/week 

Maintenance Interval Note 4 3 months To be reported 

Note 1: For the component SO2 the requirement for cross-sensitivity were not met with concentrations of HCl 

40mg/m3and N2O >20mg/m3. For the component HCl the requirement for cross-sensitivity were 

not met with concentrations of SO2 > 200mg/m3and N2O >20mg/m3. 

Note 2: The instrument met the requirements with a flow rate between 280-400L/h. If the flow is outside this 

range the instrument alarms. 

Note 3: MCA04 is an extractive analyser. Test not applicable. 

Note 4: Field test: The MCA04 analyser was assessed on the basis of a six month field trial mounted on a 

waste incinerator. 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007 
 

This certificate may only be reproduced in its entirety and without change 

Page 7 of 7 

Description: 

The multi-component MCA 04 system is an absorption-spectrometric multi-gas sensor for flue 

gas measurement and can measure up to 8 components. 

 

The MCA04 analyser extracts sample gas from the stack via a heated probe and heated line 

to the analyser which is a heated IR analyser. All components of the MCA04 system are 

heated to a temperature above the acid dew point to allow monitoring on various applications. 

The MCA04 analyser uses gas filter correlation and a bi-frequency measuring principle 

depending on the components being measured. For the oxygen measurement a zirconia 

sensor is used. 

General Notes 

1. This certificate is based upon the equipment tested. The Manufacturer is responsible for 

ensuring that on-going production complies with the standard(s) and performance 

criteria defined in this Certificate. The Manufacturer is required to maintain an approved 

quality management system controlling the manufacture of the certified product. Both 

the product and the quality management system shall be subject to regular surveillance 

according to ‘Regulations Applicable to the Holders of Sira Certificates’. The design of 

the product certified is defined in the Sira Design Schedule for certificate No. Sira MC 

070115/00. 

2. If certified product is found not to comply, Sira Certification Service should be notified 

immediately at the address shown on this certificate. 

3. The Certification Marks that can be applied to the product or used in publicity material 

are defined in ‘Regulations Applicable to the Holders of Sira Certificates’. 

4. This document remains the property of Sira and shall be returned when requested by 

the company. 

Certificate No: Sira MC 070115/00 

This Certificate Issued: 02 July 2007 
EcoChem 

Analytics 

Headquarters: 202 Reynolds, League City, TX 77573 Tel: 281-338-9888 Fax: 332-6152 

Eastern USA: 8 Paret Lane, Hartsdale, NY 10530 Tel: 914-683-5920 Fax: 683-1029 

Germany Alte Nussdorfer Str 27, D-88662 Uberlingen Tel:+49(7551)915838 Fax: 915-839 

Email: sales@ecochem.biz Website: www.ecochem.biz 

BUDGETARY PROPOSAL 

Continuous Emissions Monitoring System (CEMS)

Quotation Number: XXXXXX 

Quotation Date: XXXXX 

Customer: 

XXXXXXXXXX 

XXXXXXXXXX 

XXXXXXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 1 

Table of Contents 

1.0 BUDGETARY PRICING & SCHEDULE .........................................................................2

1.1 Budgetary Pricing ...........................................................................................................2 

1.2 Project Schedule and Milestone Payments................................................................4 

2.0 CEMS DESCRIPTION .......................................................................................................5

2.1 MC3 Analyzer..................................................................................................................5 

2.2 MC3 System Cabinet .....................................................................................................7 

2.3 MC3 System Controller................................................................................................10 

2.4 Sample Probe................................................................................................................12 

2.5 Sample Line...................................................................................................................12 

2.6 Data Acquisition System..............................................................................................12 

2.7 Building Shelter.............................................................................................................16 

2.8 System Documentation................................................................................................19 

2.9 CEMS Drawings............................................................................................................19 

3.0 PROJECT ADMINISTRATION, TERMS AND CONDITIONS...................................23

3.1 Warranty.........................................................................................................................23 

3.2 Additional Insurance Coverage ..................................................................................23 

3.3 Order Cancellation Policy............................................................................................23 

3.4 Terms and Conditions..................................................................................................24 

3.5 Payment Schedule .......................................................................................................24 
Budgetary Proposal No: XXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 2 

1.0 BUDGETARY PRICING & SCHEDULE 

1.1 Budgetary Pricing 

# Item Description Qty Unit Cost Ext Cost 

1a Multicomponent Gas CEMS 

Each MC3 based system will include the capability to 

simultaneously measure HCl, CO2, and H2O on a HOTWET basis. Each entire system is mounted inside a 

standalone cabinet, includes Operator Interface Color 

Touch Screen and sample system components (cell and 

pump filters, flow indication, sample pump) designed to 

operate in conjunction with a heated probe and sample 

line. 

1 $51,500 $51,500

1b OPTION – O2 Measurement 

The MC3 analyzer described in item 1a enhanced 

to include an oxygen measurement.

1 $1,890 $1,890

2 Heated Probe 

The probe will have initial filtration, probe isolation and 

injection ports for calibration gas (for sample system 

calibrations) and probe blowback. The probe will be 

controlled from temperature controllers in the analyzer 

cabinet. Probe length is one meter from flange to tip. 

Probe tube heaters are also provided. 

1 $12,090 $12,090

3 Heated Sample Lines 

The heated sample line contains five tubes and 10 wires. 

The lines include a full redundant heaters and RTD. 

The umbilical typically operates at 185°C or higher and 

is controlled by the system. 

--- $69/ft $69/ft

4 Factory Acceptance Test 

The FAT will be conducted in League City (Houston), 

TX and customer’s engineers will be able to test and 

verify system performance and functionality before it is 

shipped to customer’s plant site. Limited training is also 

conducted 

1 $6,400 $6,400

5 QA/QC Manual 

EcoChem will assist in creating a custom QA/QC Plan 

for customer to ensure high system reliability, maximum 

online availability and meeting regulatory requirements. 

Weekly, monthly, quarterly and annual checklists are 

provided detailing proper maintenance intervals. 

1 $3,400 $3,400
Budgetary Proposal No: XXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 3 

6 Spare Parts -- Consumable (2 YEARS) 

Consumable parts like filters, sample pump rebuild kits 

for TWO-year operation 

2 $1,440 $2,880

7 Spare Parts NON-Consumable Inventory 

Typical MC3 CEMS non-consumable spare parts kit 

1 $7,800 $7,800

8 Calibration Gas Regulators 

Dual stage regulators for the gases to be measured – 

one Brass and one 316-Stainless Steel dual stage 

regulators will be provided. Provisions for use of 

instrument air as cal gas will be incorporated.

Set of 2 $2,800 $2,800

9 Data Acquisition System 

PART 60 Data acquisition system (software and 

hardware) configured for collecting data from MC3 

analyzer and producing EXCEL reports. 

1 $12,400 $12,400

10 Building Enclosure 

8’ x 8’ x 9’ (internal height) building enclosure housing 

one CEMS. Dual 18,000 BTU A/C unit with 125 amp 

power panel. 

1 $28,450 $28,450

11 Sensors for Building Enclosure 

MSA Ultima X Series Gas Monitors for O2 and HCl 

detection within the Building Enclosure 

1 $5,600 $5,600

12 Expedited Delivery Charge 

System to be delivered in 60 days. An expedited fee of 

10% on specific items from the original quote: items 

1(CEMS), item 3 (sample line) and item 10 (Building 

Enclosure) is proposed.

1 $8,650 $8,650
Budgetary Proposal No: XXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 4 

1.2 Project Schedule and Milestone Payments 

Normal delivery schedule is 45 to 60 days delivery time after receipt of order (Without 

Building Enclosure) 

Normal delivery schedule is 60 to 90 days delivery time after receipt of order (With 

Building Enclosure) 

Milestone Payments (net 30 days) 

Receipt of order 30% 

Factory Acceptance Test or System shipped from EcoChem 60% 

Final Acceptance or before system leaves US 10% 

For international sales, complete payment before system leaves US 
Budgetary Proposal No: XXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 5 

2.0 CEMS DESCRIPTION 

2.1 MC3 Analyzer 

The MC3 is a multicomponent IR gas analyzer that is specifically designed for continuous 

monitoring of a flue gas stream. The infrared optical bench, sample cell and control components 

are all integrated into one convenient, and easily serviced ventilated enclosure. Each enclosure 

cabinet is self-standing and weighs less than 500 lbs. 

The MC3 has the following measurement range intervals: 

Gas Range Interval** Measurement 

Technique*** 

Suggested Range**** 

CO2 0-10% to 0-50% SBDW To be decided 

HCl 0-20 PPM to 0-200 PPM GFC To be decided 

H2O 0-10% to 0-50% SBDW To be decided 

* All components at 185°C or above; standard sample cell path 6 meters 

** User can select appropriate range within the interval; two ranges (i.e.: dual ranging) are available but 

must be specified at time of order. 

*** GFC = Gas Filter Correlation, SBDW=Single Beam Dual Wavelength, ZRO=Zirconium Oxide 

**** Suggested range can be modified – final choice of range to be decided when system is ordered. For 

certain components, inlet and outlet ranges will be different. 

Weight 56 lb (25 kg) 

Dimensions Standard 19in rack mount (Height x Depth x Width): 

8.75in x 23in x 19in (22cm x 58 cm x 48cm) 

Flow Rate 2-7 liter per minute with 1⁄4” Swagelok connectors 

Display Menu-driven LCD Panel can be field-customized 

Power 115 volts AC / 60 Hz and 220 volts AC / 50 Hz 

Accuracy ± 2 % of full-scale value 

Lower Threshold 1 % of lowest range 

Response Time 10 sec 

Output Signals Analog: 8 signals of 0/4 – 20 mA; Digital: 2 ports RS 232-C, 1 port RS 

422-A; Relays: Failure Indicator, Service and Maintenance 

Operating Temperature 0 – 105°F (0 – 40°C) 

Sample cell 185 oC or above with 6m path length 

Update Frequency Every 10 seconds 

The infrared optical bench consists primarily of an infrared source with chopper, a sample cell that 

the infrared light pulses travel through, a motor driven filter disk with different optical filters or gas 

filled cells in the infrared light beam, and a solid state detector to measure energy of the infrared 

light pulses. 
Budgetary Proposal No: XXXXXX 

Quote valid for 60 days from date of issue Budgetary Project Proposal Page 6 

In order to understand the operation of the multi-component analyzer, we have summarized some 

of the important aspects of its functioning: 

Analysis Techniques 

The multi-component IR gas analyzer can measure different gases using the Gas Filter 

Correlation (GFC) or the Single Beam Dual Wavelength (SBDW) techniques. 

GFC is a well-established method to reduce cross sensitivities to gases that cause interference 

in infrared measurements. In the technique an optical band pass filter is used to select an 

infrared band and then a cell filled with 100% concentration of the gas of interest is placed in 

the beam, effectively blocking the spectral lines that the gas absorbs at. It is important to note 

that variations in optical clarity like dirt on cell windows, source strength, and other causes not 

related to the spectral lines selected, will have no effect on the ratio of two pulses, making 

GFC an extremely sensitive and selective analytical technique. Typically CO, NO, NH3 and 

HCl are measured using the GFC technique. 

In the SBDW technique ultra narrow band optical filters are used to select infrared 

wavelengths. One wavelength is at a spectral line that the gas of interest absorbs (measuring) 

at, and the other is one at which it does not (reference). Typically SO2, NO2, CO2, H2O are 

measured using the SBDW technique. 

Folded Path Sample Cell 

The MC3 analyzer uses a folded path sample cell that is achieved by a specialized mirror 

configuration. These simple and robust sample cells have allowed IR photometers to routinely 

have extremely long path lengths (up to 20 meters) yet occupy small volumes. The sample 

cell path length is fully adjustable for optimization of each application and has reduced 

volume to save on maintenance and calibration gases. 

Construction 

The gas analyzer is specifically designed for Continuous Emission Monitoring service and the 

optical bench, sample cell and control components are all integrated into one convenient, and 

easily serviced enclosure. In particular, the integrated design allows the photometer source 

and detector to be housed in the same temperature controlled housing which significantly 

improves stability. A stepper motor controls the filter disk. The geometry and size of the filters 
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is such that alignment of the filters is not critical. The solid-state detector is located on its own 

subassembly but in the temperature controlled housing. 

User Interface 

The MC3 analyzer has a very simple user interface with a digital alphanumeric keypad 

incorporated on the front panel. 

The User Interface also allows complete access to system functionality and diagnostic 

information. 

Inputs and Outputs 

The IR analyzer communicates with the external devices (for example, PLC and/or plant 

control system) using a serial link and Modbus communications protocol. The analyzer 

also can be configured to provide 8 analog output signals (4-20 mamp). 

2.2 MC3 System Cabinet 

The system cabinet houses the MC3 analyzer along with other necessary components. Interaction 

with the system is through a color touch screen display on the front panel. Components placement 

is optimized for easy access and there is ample space available to house other equipment such as a 

datalogger, flow meter controller and/or other analyzers. On the following pages we show the 

system cabinet internals along with an overall system configuration. 

Digital keypad 

Escape (ESC) key

Enter key 

Navigation keys (Up, Down, Left, Right) Online Help 

Measure Mode 

Display screen 
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MC3 System Cabinet 
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MC3 System Configuration 
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2.3 MC3 System Controller 

A Programmable Logic Controller (PLC) controls the entire system (sampling system and MC3 

analyzer). A commonly used industry standard PLC is deployed. The PLC is flexible and has the 

capability to accommodate various configurations. Depending upon the customers needs separate 

modules can be added for input/output purposes, temperature controllers, Ethernet or serial 

communication etc. The PLC can be easily programmed in the field using a touch-screen display. 

Graphical illustrations (e.g. strip charts, bar charts etc) of gaseous concentration levels and various 

system conditions are also shown on the display screen. The touch-screen system provides over a 

dozen interactive screens. The MC3 analyzer communicates with the PLC using a serial link and 

Modbus protocol. The PLC unit can be connected to the plant’s network and standard Ethernet 

TCP/IP can be used for communications. The PLC will include all hardware necessary to run the 

sample system along with analog inputs and outputs of measured parameters and digital signals. 

The MC3 System Controller and Touch Screen capabilities are summarized below: 

PLC/MC3 Interface 

Capabilities & Displays 

System Capabilities & 

 Typical Base System Hardware 

Database Capabilities 

 Concentration Values 

 Absorbance Values 

 Energies – IR Optics 

 Span Factors - Range 1 

 Span Factors - Range 2 

 Cal Factors for Absorbance 

 Pre-amp Gains 

 RAMF Factors 

 Signal Filtering times 

 System Temperatures 

 O2 mV and Offset 

 Start Cal (Auto/Manual) 

 Start single blend (Manual) 

 Probe Purge (Auto/Manual) 

 System into Maintenance 

 System into Standby 

 Run 9-15 point CGA (option) 

 Reset Zero Point 

 Reset Span Point 

 Reset O2 Low 

 Reset O2 20.9

 Temperature Controllers (8) 

 Control Sample System (16 

Outputs) 

 Analyzer Auto Correction 

 Display Last Calibration 

 2 Hours of Strip Chart Data 

 O2 Wet & Dry Calculations 

 Customer Analog Inputs (8) 

 Customer Analog Outputs (8) 

 Customer Digital Inputs (8) 

 Customer Digital Outputs (8) 

 Timeshare Capability 

 Linearized O2 Capability 

 O2 Slope and Intercept Capability 

 Monitor Sample Flow from 

analyzer O2 sensor 

 Direct PLC Access 

 Modbus Port Available

 All 1-minute averages for 16 

channels (8 MC3 parameters 

and 8 analog inputs) written 

to SQL or to Excel CSV file 

(Daily File) 

 System Status is written to 

database every minute 

 Energies, Absorbance and Cal 

Factors written to DB once 

per day for long term 

diagnostics 

 10-second values for MC3 

values written to Database 

during calibration 

 Graphical interface to 10-

second calibration data 

 Graphical interface to 1-

minute data 

 Graphical interface to digital 

status data.

 Historical calibrations – 30 

days
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19. Passwords for 

different levels of user 

access

20. Display of system flow 

rates and related 

variables

21. Advanced system settings

22. Settings related to 

time-sharing of analyzer 

between two sources

23. Access PLC internal 

settings

24. Analyzer setup 

connected to PLC

13. Graphical display of 

Calibration sequence

14. Defining the zero, 

span, calibration factor, 

range for calibration 

sequence

15. Tabular display results 

for all components during 

last calibration sequence

16. Calibration Gas Audit 

setup and sequencing

17. Flow monitor 

calibration setup

18. Initiating Flow Monitor 

and Opacity calibration 

sequences

6. Name, unit and fullscale of components

7. PLC address locations 

for various tasks

8. Defining temperature 

settings for MC3 cell, 

detector, O2 sensor, 

sample line, sample 

pump, probe filter and 

probe tube

9. Analog input name, 

unit, full scale

12. Analog output 

reading, status and logic

10. Digital input name 

and status

11. Digital output status 

and logic

12 12

11

11

10

10

9

9

8 8

7 7

6

6

5 5

4 4

3

3

18 18

17

17

16

16

15

15

14

14

13

13

24

24

23

23

22

22

21

21

20

20

19

19

2 2

1

1

3. Operation mode 

(Normal, Standby, 

Maintenance) and Initiate 

Calibration Sequence

4. Status (Bad, 

Maintenance, Calibration 

and Online) for all 

components

5. Monitor energy levels 

for components and O2 

sensor performance

1. Online screen-specific 

help and guidance

2. Real-Time stripchart for 

components being 

measured

19. Passwords for 

different levels of user 

access

20. Display of system flow 

rates and related 

variables

21. Advanced system settings

22. Settings related to 

time-sharing of analyzer 

between two sources

23. Access PLC internal 

settings

24. Analyzer setup 

connected to PLC

19. Passwords for 

different levels of user 

access

20. Display of system flow 

rates and related 

variables

21. Advanced system settings

22. Settings related to 

time-sharing of analyzer 

between two sources

23. Access PLC internal 

settings

24. Analyzer setup 

connected to PLC

13. Graphical display of 

Calibration sequence

14. Defining the zero, 

span, calibration factor, 

range for calibration 

sequence

15. Tabular display results 

for all components during 

last calibration sequence

16. Calibration Gas Audit 

setup and sequencing

17. Flow monitor 

calibration setup

18. Initiating Flow Monitor 

and Opacity calibration 

sequences

13. Graphical display of 

Calibration sequence

14. Defining the zero, 

span, calibration factor, 

range for calibration 

sequence

15. Tabular display results 

for all components during 

last calibration sequence

16. Calibration Gas Audit 

setup and sequencing

17. Flow monitor 

calibration setup

18. Initiating Flow Monitor 

and Opacity calibration 

sequences

6. Name, unit and fullscale of components

7. PLC address locations 

for various tasks

8. Defining temperature 

settings for MC3 cell, 

detector, O2 sensor, 

sample line, sample 

pump, probe filter and 

probe tube

9. Analog input name, 

unit, full scale

12. Analog output 

reading, status and logic

10. Digital input name 

and status

11. Digital output status 

and logic

6. Name, unit and fullscale of components

7. PLC address locations 

for various tasks

8. Defining temperature 

settings for MC3 cell, 

detector, O2 sensor, 

sample line, sample 

pump, probe filter and 

probe tube

9. Analog input name, 

unit, full scale

12. Analog output 

reading, status and logic

10. Digital input name 

and status

11. Digital output status 

and logic

12 12

11

11

10

10

9

9

8 8

7 7

6

6

5 5

4 4

3

3

18 18

17

17

16

16

15

15

14

14

13

13

24

24

23

23

22

22

21

21

20

20

19

19

2 2

1

1

3. Operation mode 

(Normal, Standby, 

Maintenance) and Initiate 

Calibration Sequence

4. Status (Bad, 

Maintenance, Calibration 

and Online) for all 

components

5. Monitor energy levels 

for components and O2 

sensor performance

1. Online screen-specific 

help and guidance

2. Real-Time stripchart for 

components being 

measured

3. Operation mode 

(Normal, Standby, 

Maintenance) and Initiate 

Calibration Sequence

4. Status (Bad, 

Maintenance, Calibration 

and Online) for all 

components

5. Monitor energy levels 

for components and O2 

sensor performance

1. Online screen-specific 

help and guidance

2. Real-Time stripchart for 

components being 

measured

MC3 System Controller Capabilities 
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2.4 Sample Probe 

The probe for the project is a one-meter heated probe with filter heater. This probe will include a 

stainless filter and a probe tip 316 stainless steel filter. The probe will have probe isolation and 

injection ports for calibration gas and probe blowback. The probe will be controlled and powered 

from centralized temperature controllers in the CEMS enclosure. Probe tube heaters are also 

provided. 

2.5 Sample Line 

The heated sample line contains five tubes and 10 wires. The lines include a fully redundant heater 

and RTD. The composition of the tubing and wiring is as follows: 

2 – 3/8” Heated PFA tubes for sample gas (one is spare) 

1 – 3/8” Non-heated Line for Blowback Air 

1 – 1⁄4” Non-heated PFA line for Calibration Gas 

1 – 1⁄4” Non-heated line for Probe Isolation 

10 wires for heating the probe and probe tube 

1 set heat trace 

2 RTDs 

2.6 Data Acquisition System 

CEMTRAC II is a data acquisition and handling system developed by EcoChem for facilities that 

need data logging for Process Performance Monitoring or Regulatory requirements like 40CFR 

Part 60. The system interfaces to the CEMS and Plant Parameters through Programmable Logic 

Controllers (PLC) using the industry standard MODBUS communications protocol. Utilizing the 

power of a PLC it is possible to control the analyzers and also have a local repository of data. This 

eliminates the use of proprietary dataloggers leading to very cost-effective, reliable and flexible 

system architecture. 
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Proposed system configuration for Agrifos facility

The CEMTRAC II user interface can be integrated within a plant network or connected to the 

Internet. The system runs as an application in Windows XP / Vista thus making it simple to 

integrate into existing operations. CEMTRAC II supports multiple concurrent users and offers 

unlimited flexibility for future development. The database incorporates the power and reliability of 

Microsoft SQL Server 2005 (a widely-used industry standard program). It utilizes robust graphical 

database management tools native to SQL Server to automate backup and data integrity testing, 

schedule tasks and communicate events as they arise. CEMTRAC II incorporates powerful SQL 

transactions facilitating data import, export, transformation and analysis. It also provides easy 

access to program parameters (for customization) and the data itself (e.g. export of data to 

Microsoft EXCEL for analysis is easily accomplished.) 

 

CEMTRAC II also creates regulatory reports that are linked to the database. The reporting interface 

is based around Microsoft EXCEL. Standard reports include parameter values (one minute, 15-

minute, hourly and daily averages), daily summary, calibration, downtime, and alarm reports. In 

addition, custom reports can be easily created depending upon site-specific requirements. 
Budgetary Proposal No: XXXXXX 

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Data flow for Cemtrac Data Acquisition System 

Main Display Screen with Stripchart and System Status 

Realtime Display 

Database Reportin

PLC 

MC3 
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Quote valid for 60 days from date of issue Budgetary Project Proposal Page 15 

Microsoft EXCEL Reporting Interface 

Query Report 
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2.7 Building Shelter 

The CEMS building is a fiberglass constructed metal framed freestanding shelter with a rigid steel 

skid. The building is secure and is specifically designed to house one MC3-based CEMS along with 

necessary computer hardware (for combustion control, data acquisition and remote diagnostics). The 

housing shelter is assembled at the EcoChem facility in Houston and will be shipped to the customer 

plant site. The shelter is pre-wired to the lights, REDUNDANT air conditioners (18,000 BTU) with 

dual logic thermostat controller, room baseboard heaters (optional), wall outlets and CEMS. The 

overall dimensions of the shelter are approximately 8 feet long, 8 feet wide by 10 feet height. The 

shelter is insulated with 31⁄2" insulation in the walls and 6" in the ceiling. Also mounted is a panel 

containing the interface terminals for the customer's plant input and output signals. The shelter 

contains an entry plate for the sample line and dedicated vent line exhausts for the analyzers. The 

floor in the shelter will be a diamond plate floor. An external grounding lug to the building frame 

for building grounding is provided. The building will also contain an air dryer for the incoming 

plant instrument air together with the appropriate plumbing for air and calibration gas distribution 

to the two systems. A calibration gas cylinder rack is included within the building enclosure. A 

counter desk is provided inside the housing shelter where system documentation can be conveniently 

organized. 

Recently EcoChem provided an almost identical building shelter to a coal-fired power plant. Below 

please find a collection of relevant photographs. 

Shelter Side View – Dual Air Conditioners 
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Quote valid for 60 days from date of issue Budgetary Project Proposal Page 17 

Shelter Front View 

System cabinet within shelter MC3 analyzer within cabinet 
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Breaker Panel within Building HVAC Control within Building 

Electrical bundle and Calibration Gas 

Tubing Entering Cabinet 

Fire Alarm & Internal Lighting 

Desk within Building Crane loading Building shelter on Trailer 
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Quote valid for 60 days from date of issue Budgetary Project Proposal Page 19 

2.8 System Documentation 

The delivered system includes documentation consisting of the following master hard copy and 3 

CDs: 

1. System Drawings – layout, I/O, power distribution, interconnection 

2. Operations Guide to MC3 – operation, calibration, and preventive maintenance of MC3 

3. Systems Guide – analyzer & system interface, measuring principle, troubleshooting 

4. Parts List – detailed listing, recommended quantities, and description of consumable & 

spare parts 

5. Auxiliary equipment manuals and/or website information on specific components (i.e. 

HVAC, pump, etc.) 

2.9 CEMS Drawings 

In this section we provide representative drawings applicable for the installation. 

1. A sample flow diagram showing the calibration gas and flue gas flow paths 

2. A diagram showing the dimensions of a typical EcoChem CEMS cabinet 

3. A representative diagram showing the building shelter
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25 PSI25 PSI

HEATED PROBE

BACK PURGE

CONTROL AIR

CALIBRATION GAS

Y1

Y6Y7

HEATED

IN

DETECTOR

OPTICAL FILTERS

IR SOURCE

MC3 HEATED CELL

185°C

CO, NOX, SO2, O2, H2O, CO2

SPAN GAS 2SPAN GAS 1

SAMPLE

CEMS

ENCLOSURE

FTR1 - 10u

Y2

Y3

CONTROL AIRBACK PURGE

SAMPLE LINE

HEATED SAMPLE LINE

SPAN GAS 3

PETERS

ZrO2

OXYGEN

SENSOR

1/4"

3/8"

Y5

SAFETY AIR

VENT1/4" TUBE

FM

 PER PROBE/ EVERY FOUR HOURS

PURGE FREQUENCY: 1 MINUTE -

PROBE FILTER REQUIREMENTS:

PRESSURE: 80 - 120 PSIGFLOWRATE: 14 SCFM

DEWPOINT: -30°FDRY, CLEAN, OIL-FREE AIR

INSTRUMENT AIR REQUIREMENTS

ZERO GAS

Y4

SPAN GAS 4

Y10

CGA MIDCGA LOWNOX, SO2CO, CO212% O2, BALANCE N2

1-5 LPM

SPAN GAS 5

Y11

CGA HIGH

NO. REVISION APPR. DATE: DATE:

DATE:

DATE:

PROJECT: 

DWN.

CKD.

APPRD.

0

Sample Flow Diagram 

(Example schematic – final design dependent upon scope of project) 
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PETERS

2 4 VDC COIL

264 LP

M

AIR

8

1 0

TOP VIEW

BACK PANEL W/ RACK REMOVED SWING/SLIDE RACK 

ZERO GAS ENTRYSPAN 1 ENTRYSPAN 2 ENTRYSPAN 3 ENTRY

INSTRUMENT AIR

POWER ENTERY

SAMPLE LINE ENTRY

2 4 VDC COIL

LEFT SIDE DOOR

3/

24

1

12

43

26

5

978

10

11

18

1513

141617

21

19

20

2223

CABINET - 72" HIGH X 32" X 32"TOUCH SCREENMERCURY DISPLACEMENT RELAYSOLID STATE RELAYSOLENOID VALVES24 VDC POWER SUPPLY24 VAC POWER SUPPLYFILTER REGULATORCAL GAS FLOW METERSAMPLE PUMPMC3 ANALYZERPLUG STRIPPLC OUTPUT CARD - 8 RELAY OUTPUTSPLC OUTPUT CARD - TEMPERATURE CONTROLPLC WITH 450 CPUPLC ETHERNET CARD

25

NO. REVISION APPR. DATE: DATE:

DATE:DATE:

PROJECT: 

DWN.

CKD.

APPRD.

MC3 CEMS Cabinet 

(Example schematic – final design dependent upon scope of project)
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Quote valid for 60 days from date of issue Budgetary Project Proposal Page 22 

CEMS Shelter 

(Example schematic – final design dependent upon scope of project)
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3.0 Project Administration, Terms and 

Conditions 

3.1 Warranty 

Unless specified otherwise, all non-consumable parts and operations have a warranty of 12 months from startup or 

18 months from shipment whichever occurs earlier provided system is maintained and operated consistent with 

manufacturer’s guidelines. General conditions to be met by operator/owner for EcoChem Warranty and 

performance specifications to be valid: 

1. Electrical power to instrumentation – is required to be 120VAC +/- 10 VAC with proper surge protection 

and conditioning. 

2. Instrument Air – required quality is particulate and oil-free with a dew point of -20°F or better. 

3. Ambient room conditions – proper dust control with temperatures controlled between 50°F to 85°F. 

Humidity should be controlled and vibrations minimized. 

4. Calibration Gas – for certified systems, EPA Protocol #1 gas is required from a mutually approved 

supplier for certification testing. 

5. Probe Access – proper safety and reasonable access is required for probe to be properly maintained. 

For EcoChem to stand behind the CEMS of greater than 95%+ availability the following general guidelines are 

highly recommended: 

1. Proper modem access by High speed VPN or dedicated telephone line

2. Proper inventory of consumable parts as detailed in EcoChem’s pre-delivery package available onsite 

prior to certification testing. 

3. Proper inventory of Spare Parts (Level 1 and Level 2) as detailed in EcoChem’s pre-delivery package. 

4. Technician training – minimum of 3 days during warranty period. Factory Acceptance testing and 

training is strongly recommended. Additional training as staff turnover warrants or as or before 

maintenance contract expires. 

5. First 12 months minimal maintenance contract – visits every 6 months by EcoChem. 

6. Initial verification testing requires EcoChem’s onsite support to assist plant staff or third party with 

Drift, Response, Linearity (Cal error), and RATA testing. 

7. Timely notification to EcoChem of system problems related to warranty of CEM by competent project 

designee(s) with sufficient detail. Cell phone or land-line availability in the process monitoring or CEM 

building expedites troubleshooting and corrective action. 

3.2 Additional Insurance Coverage 

Should customer’s insurance requirements exceed existing coverage carried by EcoChem Analytics, costs of any 

additional coverage's mutually agreed to will be invoiced on a prorated basis for the duration of the project and 

maintenance contract. 

3.3 Order Cancellation Policy 

After receipt of Purchase Order (PO) the following cancellation fee will apply to the project total: 

• For orders cancelled after receipt of order the cancellation fee is 25% of PO 

• For orders cancelled 15-30 days after receipt of order the cancellation fee is 50% of PO 

• For orders cancelled greater than 30 days after receipt of order the cancellation fee will be 75% or more 

depending upon the amount of work performed on the project 
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3.4 Terms and Conditions 

1. LEGAL JURISDICTION: All questions concerning the validity and operation of this Agreement (Proposal, 

Contract, Quote, etc.) and the performance of the obligations imposed on both Parties under this Agreement 

(Proposal, Contract, Quote, etc.) will be governed and enforced by the laws of the State of Texas, U.S.A. 

2. REPRESENTATION: EcoChem will not be bound by any promise or representation, written or oral, not 

made a part of the order and signed by an authorized representative of EcoChem Analytics. 

3. END-USE: The determination as to the adaptability of any of EcoChem’s products to the specific needs of the 

purchaser is solely the purchaser’s prerogative and responsibility. EcoChem is glad to offer suggestions on the 

use of its various products. Nevertheless, there are no warranties or product guarantees given except such 

expressed warranties offered in connection with the sale of a particular product. 

4. ACCEPTANCE OF GOODS: All orders are subject to final acceptance at our corporate facilities, League 

City, Texas, U.S.A. 

5. FIRM PRICE PERIOD: Unless otherwise stated, all pricing is firm for (60 days) from date of quotation and 

is firm for goods released within (60 days) of order acceptance. Quoted price is valid only for the quantity 

indicated per item. 

6. FREIGHT CHARGES: Collect to Customer or Direct Bill to Representative unless otherwise specified. 

7. F.O.B. POINT: F.O.B. point is EcoChem’s factory in League City, Texas, USA. Our standard practice is to 

use F.O.B. SP PP & Add (Title of ownership passes at EcoChem’s factory. Shipping charges are prepaid by 

EcoChem and added to invoice. Insurance liability is that of the buyer.) In addition, if you have a specific 

freight forwarder, please communicate this information to us. Feel free to contact your EcoChem representative 

who will assist you in making arrangements regarding this item. 

8. DELAYS: EcoChem Analytics Inc shall not be held responsible for delays or nonperformance by causes 

beyond EcoChem’s immediate control, including but not limited to delays of vendors or carriers, acts of God, 

fires, governmental actions and material shortages. Any such delays will automatically and without penalty 

affect a corresponding extension of scheduled shipping dates. In all cases, scheduled shipping dates are 

understood to be approximate and in no event will EcoChem be liable for consequential or incidental damages 

due to delays or nonperformance. 

3.5 Payment Schedule 

Upon invoice net 30 days. Milestone payments specified in Section 1.2. 

Delay of written purchase order receipt or milestone payments may result in a day-for-day delay in project 

schedule. 

 Payments made to: 

EcoChem Analytics 

202 Reynolds Avenue 

League City, TX 77573, USA 

Attention: Accounting 

Tel: 281-338-9888 Fax: 281-332-6152