Gasmet EMISSIONS MONITORING HANDBOOK
Gasmet EMISSIONS MONITORING HANDBOOK
Emissions Monitoring
     Handbook
Foreword
This handbook aims to cover the topic of emissions monitoring holistically and
to provide you a comprehensive picture of emission monitoring in the context of
continuous and long-term monitoring for large industrial and combustion plants.
Each section is strongly linked to each other, which is why it is important they are
examined as one coherent handbook.
After reading this guide you are familiar with various emissions monitoring
technologies, available solutions and quality assurance of continuous emission
monitoring systems, and much more.
CONTENTS
3 WI BAT Conclusions                                                        16
Upcoming changes                                                             17
Key Findings for Emissions Monitoring                                        17
5 Monitoring solutions                                                     27
Continuous Emissions Monitoring Systems                                     28
     CEMS II e                                                              28
     FID (Flame Ionization Detector)                                        29
     Oxygen Analyzer                                                        29
Continuous Mercury Monitoring Systems                                       29
     CMM AutoQAL and CMM                                                    29
     New World Record                                                       31
Dioxin Sampling Systems                                                     31
     GT90 Dioxin+                                                           31
Gasmet Software                                                             33
     FTIR Analyzers: Calcmet software                                       33
     Mercury Analyzers: MAUI software                                       33
Customer Data                                                               33
1 Industrial Emissions
Monitoring & Suitable
Technologies
In the era of bustling industrial activity and growing number of industrial plants,
regulation and continuous monitoring of emissions have become increasingly
important.
In this section we will introduce you to various technologies, such as FTIR, CVAF and
dilution in emissions monitoring, and explain what needs to be taken into consideration
in an effective set-up for emissions monitoring. The guide is aimed at all emissions
monitoring professionals but is ideal for everyone interested in the field.
The measured components depend on various factors, such as the industry, the burned
fuel and the size of the plant. Environmental permit of a plant defines which gases and
components are required to monitor and what their set limits are. For example, both
small and large coal-fired power plants have their own regulations.
It is paramount that plants choose appropriate technologies and devices for the
emissions monitoring. It should be secured that the device is sensitive enough to
detect even the smallest levels of a component, as some industrial plants have very
low and strict emission limit values for certain gases.
Once the most suitable certified system for the continuous emissions monitoring
has been decided, purchased and commissioned, the operator needs to follow the
quality assurance procedure and verify the measurement results of each reported
component. This quality assurance procedure is explained in detail in the chapter 2 of
this Handbook.
•     Multicomponent capability
      FTIR is the only technology that measures such a wide range of gases
      simultaneously. All key emissions monitoring compounds such as NOx, SO2 and CO
      can be measured. In case of waste incineration, also HCl, HF and TOC are added to
      the measured gases, and NH3 if SCR or SNCR is used.
•     Proven technology
      Gasmet FTIR analyzers hold TÜV and MCERTS certificates (QAL1). All Gasmet’s
      FTIR emissions monitoring systems have been certified throughout their history.
•     Reliability
      FTIR is extremely sensitive, accurate and robust technology. It provides low
      maintenance cost for the user and long system lifetime combined with low
      uncertainty. Additionally, its high availability provides low downtime for the
      operators.
Mercury occurs naturally in the environment, in rocks and coal, in various forms, such
as metallic mercury and organic and inorganic mercury compounds.
Mercury can be harmful to the environment and is toxic to humans. Exposure to even
small doses can have serious health effects and exposure to large amounts can be
fatal. The largest sources of anthropogenic mercury emissions are:
•     Mining industry
•     Coal combustion
•     Cement production
•     Waste incineration
Many pollutants such as CO2, NOx and SO2 have been monitored continuously already
for decades. In the last years the awareness for the need to measure mercury has also
grown, and continuous mercury monitoring is becoming more and more relevant.
Especially industries burning coal, oil or waste, share the responsibility to monitor their
mercury emissions. All measuring techniques need to be able to tackle the challenges
mercury monitoring presents.
Mercury can occur in various forms and can even be bound to dust particles. Flue gas
includes elemental mercury Hg0 and oxidized mercury Hg2+ in the form of HgCl2. As
most measurement methods are based on measuring elemental mercury, it means that
the oxidized mercury compounds must be converted to elemental mercury.
CVAA, CVAF and DOAS are all measurement technologies used in certified systems.
Selecting the right technique depends on your analytical needs. The choice of analyzing
method may also be determined by regulatory compliance. Therefore, it’s vital to check
which regulatory methods you need to comply with when choosing a mercury analyzer.
Principle of CVAF
CVAF measurement principle is explained below via the main parts of the mercury
analyzer:
1. Mercury vapor lamp: Lamp acts as a UV light source. Lamp emits UV light at a
   wavelength specific for mercury. The light is directed to the sample cell.
2. Sample cell: Mercury atoms in sample gas are excited by UV light. The excited
   atoms then start to re-radiate the absorbed energy (fluorescence).
                                                       2
                                SCEN
                            ORE
                         FLU LIGH
                                                                  UV
                                                                   LI
               3
                                                                       GH
                                                                        T
           PHOTON
           COUNTING                                                             1
           DETECTOR
                                                                            UV LIGHT
                                                                              SOURCE
The photon counting detector is usually placed at a 90 ° angle to the light source, to
reduce stray light entering the detector, since fluorescence is omnidirectional, meaning
the light is emitted in all directions. This way, only the photons derived from the
mercury atoms can be detected.
For more information and answers to frequently asked question, navigate to our blog:
TO CVAF BLOG
Thanks to the CVAF technology and Gasmet design, continuous and precise
measurement with no need for sample pre-concentration is achieved. The integrated
thermal converter converts all mercury compounds to elemental mercury to measure
total gaseous mercury. The converter is directly connected to the sample cell to prevent
recombination reactions, where atomic mercury converts back to oxidized forms.
2. Low detection limit: Secondly, the mercury concentrations are extremely low
   compared to other emission gas compounds. The concentrations are generally few
   μg/m3 in waste incineration and power plants. These extremely low concentrations
   naturally require that the measurement technique has low detection limits. It
   should be noted that depending on the plant or process, there can be relatively
   high concentrations of mercury from time to time. Because of occasionally varying
   concentrations of mercury, the measuring system needs to be able to withstand
   and detect the Hg peaks as reliably as the lower concentrations.
These requirements have been met through the development of CMM AutoQAL and
CMM systems. This paper will describe the main features of the systems employing
CVAF technology.
2 Quality Assurance of
Continuous Emissions
Monitoring Systems
EN 14181 sets the quality criteria for permanently installed measuring equipment at
the industrial plants.
QAL1
QAL1 requires that instruments are shown to be suitable for purpose based upon a set
of laboratory and field tests, as set out in the EU Standard EN 15267. Testing must be
carried out by an approved laboratory accredited to EN ISO/IEC 17025 by a national
body.
QAL1 aims to find out whether the selected measuring equipment for a plant is
effective enough and meets not only the required legal criteria, but also the needs of an
industry operator. This includes the analyzer system itself (such as an FTIR), as well as
the sample delivery and sample conditioning system (sample probe, sample lines etc.),
so it is an assessment of a complete measuring system.
QAL2
The requirements of QAL2 cover the calibration of the CEMS / AMS against nationally
approved analytical methods applied by a test organization typically accredited to EN
ISO/IEC 17025 (and MCERTS in the UK) by a national body.
This stage of quality assurance specifies the procedures to ensure that the continuous
emissions monitoring system has been correctly installed, calibrated by comparison
measurement and independently verified.
Typically, QAL2 tests are carried out every 5 years (as defined in the site’s environmental
permit). It is, however, important to point out that if there are any major changes made
to the plant or process being measured that might affect the emissions (both positively
and negatively) or the ability of the CEMS to measure a parameter, an operator must have
the AMS evaluated and conduct another QAL2 assessment. A major change could mean,
for example, a change in the fuel types, an alteration to combustion or incarceration
processes, or anything that might radically change the emissions.
QAL3
QAL3 refers to the ongoing monitoring of a CEMS between the QAL2 tests. Operators are
required to keep an eye on the stability and performance of their monitoring systems.
EN 14181 recommends that plant operators start collecting data for QAL3 immediately
after the CEMS has been installed and commissioned. This ensures that there is
enough reported information of the performance and functionality of the monitoring
system and helps reduce the chances of the measurement system not meeting the
requirements as set out in QAL2. This bedding-in period is typically around 3 months,
though on very stable processes with good performing systems, this period is often
reduced. Minimum interval for QAL3 is defined in the QAL1 field test.
With QAL3 monitoring, industrial plants are able to spot any drifts in the zero/span
levels and point out if the system has any needs for maintenance.
AST
Annual Surveillance Tests are very similar to QAL2 test but are carried out in a smaller
scale. These mini-QAL2 tests are functional laboratory spot tests that map out the
performance of a CEMS.
Their purpose is to verify the continuing validity of the calibration function, and the
requirements and responsibilities for carrying out the AST tests are the same as for QAL2.
Test Laboratories:
Note: Functional tests can be carried out by the manufacturer / supplier / System
integrator. It is the responsibility of the Test Laboratory to ensure that such tests are
carried out correctly.
3 WI BAT Conclusions
This section introduces the key findings of conclusions for Best Available Technology
Reference document for Waste Incineration (WI BREF). It was accepted by European
Integrated Pollution Prevention and Control Bureau (EIPPCB) in summer 2019 and the WI
BAT conclusions published on 3rd December 2019, under the IED Directive 2010/75/EU.
In the following chapters we will introduce the upcoming changes and the ranges for
daily average limits for new plants and existing plants.
Abbreviations:
BAT-AEL:		             BAT-associated emission levels
Upcoming changes
The revised BREF defines the technical basis and BAT-associated emission levels (BAT-
AELs) for national authorities in the EU to set operating permits for installations. The
BAT-AELs work as a framework for authorities to set plant-specific ELVs (Emissions
Limit Values).
  Regardless of whether the BAT-AELs change or not, all environmental permits of
existing waste incineration installations in Europe need to be reviewed during the
implementation period of four years. This may cause changes in the plant-specific
ELVs (within the limits defined by the BAT-AELs).
  New installations must comply with the new requirements immediately without any
implementation period. Even though in different countries and plants, the specific ELVs
may differ, they need to be set according to the BAT-AEL requirements.
                                2006                                           2019
                       Daily                           Daily average for Daily average for
   Component                           IED limit                                             Unit
                      average                              New plant      Existing plant
 The BAT-AELs set for mercury (Hg) emissions for incineration and co-incinerations of
 waste happens for the first time at the EU level. Continuous monitoring is required if it
 cannot be proven that the waste incinerated has low and stable mercury content.
    The mercury content of different waste feeds can vary significantly, which can be
 clearly spotted with continuous mercury monitoring. During the day, the new feed is
 introduced approximately every four hours, resulting in mercury peaks as the waste is
 incinerated, as seen in the graph below:
                                       700
 Total mercury concentration (μg/m3)
600
500
400
300
200
100
                                        0
                                         12.00 AM       6.00 AM                 12.00 PM     6.00 PM    12.00 AM
                                                                                   Time
In addition, the BAT Conclusions for Waste Incineration sets new BAT-AELs for the
following compounds: TVOC/PCDD/F and dioxin-like PCBs (see table below):
                                                      BAT-AEL
     Parameter            Unit                                                          Averaging period
                                          New Plant          Existing Plant
(1) Either the BAT-AEL for PCDD/F or the BAT-AEL for PCDD/F + dioxin-like PCBs applies.
(2) The BAT-AEL does not apply if the emission levels are proven to be sufficiently stable.
1. For the first time in history, BAT-AELs for Mercury were introduced for incineration
   and co-incinerations of waste.
2. Continuous Mercury Monitoring will become obligatory, unless it can be proven that
   the waste incinerated has low and stable mercury content.
3. All environmental permits will be reviewed by 2023, which might cause changes to
   plant specific ELVs.
The LCP BAT Conclusions explain new emission limits values (ELVs) for sulfur dioxide,
nitrogen oxides, mercury, and particulate matter, and require large combustion plants in
Europe to comply with those limits by 2021.
BAT-AELs (best available technology associated emission levels) are set as a range
and based on evidence from plants that are in operation all over the world. The concept
of BAT covers not only the environmental performance of the technique but also that it
is currently used and economically viable. The BAT AEL-ranges shall be the reference
for setting these emission limit values, taking into account fuel type, combustion
technology and other relevant conditions.
Abbreviations:
LCP BREF: Best Available Techniques Conclusions for Large Combustion Plants
reference document.
LCP BATC / LCP BAT Conclusions: A document containing the parts of a BAT reference
document (LCP BREF) laying down the conclusions on best available techniques.
Different variations of conventional power plants used for mechanical power and
heat generation are covered in the BREF. Industrial combustion installations are
covered if they use conventional fuel. The conventional fuels considered in these BAT
conclusions are any solid, liquid and/or gaseous combustible material including:
*BAT-AELs for mercury emissions to air are specified for coal and lignite burning power
plants. E.g. A new coal-fired power plant with ≥ 300 MWth has a BAT-AEL of <1-2 μg/Nm3
mercury (yearly average), and an existing lignite-fired power station with a thermal input
under 300 MW has a BAT-AEL of <1-10 μg/Nm3 mercury. Permits will have to be updated.
Table 2. BAT-associated emission levels for mercury emissions to air from the
combustion of coal and lignite.
                                                                               BAT-AELs (μg/Nm3)
             Combustion plant total rated
                 thermal input (MWth)                              Yearly average or average of samples
                                                                         obtained during one year
Table 3. BAT-associated emission levels for HCl emissions to air from the combustion
of solid biomass and/or peat.
                                                                               BAT-AELs (μg/Nm3)
    Combustion plant total rated thermal input
                      (MWth)                                       Yearly average or average of samples
                                                                         obtained during one year
Table 4. BAT-associated emission levels for NOx emissions to air from the combustion
of coal and/or lignite
                                                                                           BAT-AELs (μg/Nm3)
           Combustion plant total rated thermal input (MWth)
                                                                                            Yearly average
                                                                                       New Plant     Existing Plant
                                      <100                                              100–150         100–270
                                     100–300                                            50–100          100–180
                      ≥300, FBC boiler combusting coal and/
                      or lignite and lignite-fired PC boiler                             50–85          <85–150
Table 5. BAT-associated emission levels for SO2 emissions to air from the combustion
of coal and/or lignite.
                                                                                           BAT-AELs (μg/Nm3)
           Combustion plant total rated thermal input (MWth)
                                                                                            Yearly average
                                                                                       New Plant     Existing Plant
                                      <100                                              150–200         150–360
                                     100–300                                            80–150          95–200
                                  ≥300, boiler                                           10–75          10–130
                           ≥300, Fluidized bed boiler                                    20–75          20–180
Table 5. BAT-associated emission levels for SO2 emissions to air from the combustion
of coal and/or lignite.
NB: BAT conclusions are the technical basis for national authorities in the EU
countries to set permit conditions for LCPs. If the authorities use the BAT conclusions
to set permit conditions at the lowest end of the indicated emission level ranges,
this can drive a sizeable reduction of emissions from the plants subject to the new
environmental standards.
Checklist:
•     Each EU country will set their own emission limit values (ELVs) based on BAT-AELs.
      Find out the ELVs You need to comply with.
•     Invest in emission monitoring technology that is up to date with the LCP BREF and
      meet the new requirements.
•     Pay special attention to lower emission limits and new continuous monitoring
      requirements
• Please note that if SCR or SNCR is used, NH3 needs to be measured continuously.
Gasmet CEMS II e is EN 15267 certified for measurement of CO, NO, NO2, N2O, SO2,
HCl, HF, NH3, CO2, H2O, O2, CH4 and CH2O in extended ranges.
The certification ranges can be found here: Certificate of Product Conformity (QAL 1) -
Gasmet CEMS II e
Also see: The MCERTS Product Conformity Certificate for CMM system.
Gasmet’s CMM has the lowest certified Hg measuring range in the world, from 0 to 5
μg/m3.
Gasmet offers both stationary and portable monitoring systems and technology for
continuous gas measurements. Gasmet is up to date with the changes in emissions
measuring legislations and makes sure that its systems meet the requirements of the
future.
CEMS II e, CMM, CMM AutoQAL and GT90 Dioxin+ systems will be introduced in the
next chapters. Also see more information on our website:
5 Monitoring Solutions
This section introduces you to the emissions monitoring solutions that Gasmet offers
for continuous emission monitoring needs.
•     The Continuous Emission Monitoring System CEMS II e offers TÜV and MCERTS
      certified solution (QAL1) for a wide range of demanding emission monitoring
      applications. The system is generally used to simultaneously measure several
      gaseous components, such as CO and NO2.
•     The Continuous Mercury Monitoring systems CMM AutoQAL and CMM have the
      lowest certified range in the world (0-5 µg/m3). CMM AutoQAL has an automatic
      and integrated QAL3 validation tool. Systems are perfect for monitoring mercury
      continuously from hot, wet and corrosive flue gases.
The Dioxin Monitoring System GT90 Dioxin+ is a device designed for long-term
sampling of dioxin emissions in conformity to the European standard EN 1948-1 and
EN 15267. The system represents the cutting-edge technology for dioxin long-term
sampling and fulfills all the requirements of the dioxin measurement standard.
CEMS II e is a fully automatic system and it has a variety of I/O configuration options.
Gas component concentrations and alarm information can be transferred to other
automation or reporting systems in analog or digital format.The system has options for
TCP/IP and Profibus DP. CEMS II e system is also equipped with the possibility to use
analog and digital inputs for external data, for example from eternal analyzers like flow
and dust.
Oxygen Analyzer
Gasmet oxygen analyzer measures oxygen concentration continuously from wet or dry
flue gases. The analyzer is suitable for several industrial applications where accurate
and reliable oxygen measurement is required.
The measurement is made with a ZrO2 sensor. The analyzer can measure oxygen from
1 ppm to 25 vol-%.
CVAF technology and Gasmet design guarantee a continuous and precise measurement
without the need for sample pre-concentration. The integrated thermal converter converts
all mercury compounds to elemental mercury to measure total gaseous mercury.
CMM AutoQAL 15 000 € 200 € 1738 € 200 € 32 384 € 2 000 € 34 384 € Liquid only
The GT90 Dioxin+ was designed to sample even the lowest dioxin and dioxin-like
compound concentrations in harsh industrial environments. The system has been
performance tested and validated, allowing measurements down to 0.0003 – 0.252 ng
I-TEQ /m3. The system can withstand dust loads up to 150 mg/m3 and velocities up to
30 m/s without any effect to the performance.
Gasmet Software
FTIR analyzers: Calcmet software
All Gasmet FTIR analyzers come with the Calcmet software. The software collects,
stores and visualizes the FTIR spectra of the sample gas and analyzes the sample
spectra for the gas concentrations.
The Calcmet software analyzes the sample spectrum using a sophisticated algorithm.
It can simultaneously detect, identify and quantify up to 50 different gas components
from a single sample. Cross-interference effects are compensated, and analysis
accuracy is maintained even when analyzing complex gas mixtures where gases have
overlapping absorption spectra.
Sample spectra can be easily re-analyzed, since the sample spectra are stored as
separate files on an external computer.
Calcmet software can also identify previously unknown components – a feature that
has often shown its value in process control.
Customer Data
Real-life example data measured with Gasmet CEMS II e from Municipal waste
incineration plant on oil burner during commissioning. Online data is updated every 60
seconds (1 min measurement time).
80%
                                     70%
Concentration percent of range (%)
60%
50%
                                                                                                                                CO
                                     40%
                                                                                                                                H20
                                                                                                                                NO
                                     30%                                                                                        NH3
20%
10%
                                     0%
                                     12.00 AM   1.00 AM   2.00 AM   3.00 AM           4.00 AM   5.00 AM   6.00 AM   7.00 AM
Time
Real-life example data measured with Gasmet CMM system from coal-fired power
plant in Europe. Zero calibration of the system takes place at 4:50 am and span
calibration for 5 μg/m3 at 5:50 am
In the field of gas analysis, our company have established a global reputation for
high-tech, customer-driven and reliable solutions. As a global company, we place a
heavy emphasis on high levels of pre- and post-sale technical support.
Gasmet Technologies Oy
Mestarintie 6, 01730 Vantaa
email: contact@gasmet.fi
phone: +358 9 7590 0400
www.gasmet.com