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International Journal of Energy Science

IJES

Measurement Techniques for GHG Emission from Hydropower Reservoirs


Swati Kawade1 , M. P. Sharma2 , Arun Kuma3
Alternate Hydro Energy Centre Indian Institute of Technology, Roorkee, India
1

Swati.kawade786@g mail.co m; 2 mpshafah@iitr.ernet.in; 3 aheciitr.ak@g mail.co m The paper compares different methods used to measure gross GHG flu xes fro m hydroelectric reservoirs and natural water bodies considering only the diffusive emission in boreal water bodies as the majo r fo rm of emission. The contribution of ebullitive emission is very small but is more important in tropical water bodies [5, 10, 11]. The GHG flu xes measuring gears and different analy zers with different models used to analyze the GHG flu xes is co mpared based on the analysis of literature data. The results have indicated that floating chamber coupled to an automated instrument may be the best method for the measured of both diffusive and ebullit ive emissions. II. METHOD FOR MEASURING FLUXES ACROSS AIR WATER
INTERFACE

Ab stractIn order to improve the repeatability, reliability and


reproducibility of Green House Gas fluxes measurement from reservoirs and natural water bodies, a number of methods have been developed over the years. These methods are: thin boundary layer (TBL), floating chambers with in-situ or ex-situ laboratory analysis and floating chambers coupled to an automated instrument Non-Dis persive Infrared (NDIR) or Fourier Transform Infrared (FTIR). No significant difference in the results obtained from in-situ or ex-situ laboratory analysis is found. Number of results rejected for CO 2 fluxes are similar for both NDIR an d laboratory analysis. For CH4 fluxes, numbers of results rejected by floating chamber with in-situ labortary analysis are 3 times lower than other methods. Out of the above, floating chamber coupled to an automated instrument is found as the method of choice for GHG flux measurement due to its ability to sample large number of sites in relatively short period of time with the fairly good precision and yield higher flux values than other method. Keywords- Hydropower and Climate Change, GHG Emission from Reservoir

A. Floating Chamber with in-situ laboratory Analysis


1) Field Sampling:

I. INT RODUCTION Hydropower reservoirs are identified as potential sources of greenhouse gases emissions (GHGs) like carbon dio xide (CO2 ), methane (CH4 ) and n itrous o xide (N2 O). These are considered as anthropogenic aquatic system with substantial impacts on global water cycle [1][2][3]. These reservoirs are widely distributed and steadily increasing in numbers due to growing energy needs of the world [4]. In itially, they were considered GHG free clean energy sources but there is increasing awareness that hydropower reservoirs are not carbon neutral due to their significant contribution of GHG emission to the atmosphere and therefore, has generated scientific debate on the role of reservoirs in the global climate change. There are various pathways that lead to the emissions of GHG gases from hydropower reservoirs, lakes, etc. CH4 is produced at the bottom of lakes and in sediments through anaerobic biodegradation. The dissolved gas diffuses towards O2 rich surface layers where it is oxidized by microorganisms and partially released into atmosphere at water air interface depending on the surface concentration and wind speed [5][6][7]. Assuming the surface concentration relatively uniform, these emissions can be quantified quite accurately. In another pathway, CH4 is released fro m water as it passes the turbines downstream of the reservoirs [8]. The turbine discharge is usually well documented and CH4 concentration near intake can also be easily quantified. Thirdly, when CH4 production is high, the gas bubbles are formed and rise to the surface at a fast rate (ebullition). Since the ebullit ion process is extremely hydrogenous in space and time, the estimate using conventional floating chamber method has large measurement errors [9].

The method as detailed by Canuel et al. 1997 [5] makes use of rectangular floating chambers of 30*30*50 cm made of acrylic material with its outer surface covered with Mylar paper to prevent overheating of inner side of the chamber. About 10 cm of the chamber is kept under water and the level is positioned by Styrofoam collars (Fig 1). The intake fo r air sample prov ided on the top center of the chamber is connected to teflon or tygon tubing of 4 m long with internal d ia of 3.2 mm. At each site, four floating chambers are placed at a distance of about 2 m fro m the boat. A 60 ml polypropylene syringe connected to the tubing of the floating chamber is first pumped several times in order to ho mogenize the air in the tube and chamber. The first samp le is collected (t 0 ) after an hour. Four samp les are collected at 15 minutes intervals for a total of one hour at 15, 30, 45 and 60 minutes. Five CO2 concentrations are measured using Gas chro matograph (GC) having Flame ionization detector (FID) and Thermal conductivity detector (TCD) to calculate the flu x by linear regression using Equation 1 as shown in Fig. 2. Only sites with correlation coefficient higher than 0.85 for CO2 and 0.90 for CH4 are selected for further measurement .

a)

b)

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International Journal of Energy Science


Figure 1 Floating chamber (a) laboratory analysis (b) automated system
700
CO2 concentration (ppm)

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underwater. The air is samp led fro m the top of the floating chamber and returned at the opposite end of the chamber. The air in the chamber is passed through a desiccant to prevent water condensation of water in the tubing. Another column of desiccant is placed just before the input to the instrument. Air is analyzed with an automated NDIR instrument or FTIR. Table 1 co mpares the important features of these two instruments.
TableI
COMPARISON OF THE NDIR AND FTIR INSTRUMENT
[12]

600 500 400 300 200 100 0 0 15 30 45 60


Cumulative time (min)

y = 35x + 431 R = 0.978

Equipment Models Figure 2 CO2 concentration vs .cumulative time with laboratory analysis Paramete rs Model No LI-6251 LI-CORa 0-3000 1-3 (at 350 ppm) 2-6 (at 1000 ppm) Type of Analyzer

The gas flu x can be calcu lated using Equation 1. Flu x (mg .m d )=
-2 -1

12 3

(1)

Manufacture r Rang (ppm) CO 2 CH4 N2O Accuracy(ppm) CO 2 CH4 N2O

NDIR LI7000 LICOR 0-3000 <1 % range -

CIRAS2SC PP system 0-2000 0.2 (at 300 ppm) 0.5 (at 1750 ppm) -

FT IR Gasmet DX4010 Temet Instrument 0-2000 0-100 0-10 <1 % range <1 % range <1 % range

Where, slope: slope co mputed fro m the graph of concentration versus time in ppm/ min; F1: conversion factor fro m pp m to g m-3 (1798.45 for CO2 and 655.47 for CH4 ); F2: conversion factor fro m minutes to day (1440); volu me: volume of air trapped in the chamber (m3 ); surface: surface of the floating chamber over the water (m2 ); F3: conversion factor fro m g to mg (1000).
2) Laboratory Analysis:

At the beginning of each sampling, the analysis is carried out at on-site laboratory set up for testing the instrument prior to analysis. Air samples are analy zed by GC using TCD for CO2 and FID for CH4 . 10000 pp m of high purity standard CO2 is used to calibrate the instrument. Standards are injected at the beginning of each set of analysis after every 10 samples. The detection limit for CO2 is 25 pp m and 0.375 pp m for CH4 . The reproducibility of analysis is + 5%. B. Floating Chambers with ex-situ Laboratory Analysis Field sampling is very similar to that described above. A Tygon tube of 2.5 m and 3.2mm internal dia is used for the air sampling. The sampling end of the tube is connected to a twoway valve. The volu me of the tube is 30 ml. The same equation and correlation coefficient can be used to calculate the flu xes. As reported by Dumas 2002, the air samples can also be analyzed by employing gas chromatograph (GC) equipped with a mass spectrometer detector (MS) in selective ion mode. The detection and quantificat ion limits are 0.2-0.6 ppm respectively for CO2 and 0.1-0.3 ppm for CH4 . The accuracy of method is + 5% for CO2 and +4% for CH4 . The repeatability is +4% fo r CO2 and +3% for CH4 . Standards of 100 and 1000 pp m are used for CO2 and standard of 100 ppm used for CH4 . A ll the standards are injected after 10 samples and 100 pp m CO2 standard is also injected after 5 samples. C. Floating Chambers Coupled to an NDIR or FTIR The floating chambers coupled to an automated instrument were used in 2001 and since 2002 these have been replaced by the floating chambers using syringes. Its design is slightly different fro m the laboratory analysis as discussed above. It is thermoplastic container with a surface area of 0.2 m2 and a height of 15 cm, of which 1 or 2 cm remains below the water surface. The volume of air trapped over the water is about 20 l. A floating chamber without sides creates more disturbances to the air-water interface than the chamber with 2 cm sides

All the data of CO2 concentration with respect to time is plotted on a graph and the slope is calculated in ppm as shown in Fig 3. The flu x can be calculated using Eq. 2 or 3. The samples with correlation coefficient higher than those specified in Table 2 are only considered for flu xes calculat ion. The correlation coefficient accepted is d ifferent than the flu x measured. As the measured flu x approaches zero, the difference between consecutive readings becomes close to the precision of the instrument resulting in mo re fluctuations in the concentrations and a lower coefficient.
370 365 360 355 350 345 340 335 330 325

CO2 Concentration

y = 1.773x + 339.4 R = 0.986

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

Cumulative time Figure 3 Typical graph of the results with NDIR instrument

The flu x with NDIR instrument can be calcu lated using the following equation with slope: slope fro m g raph of concentration versus time in pp m/s; pressure: ambient pressure measured in kPa; F1: Molecular weight (44 for CO2 ); F2: conversion factor fro m seconds to day (86400); volu me: volume of air trapped in the chamber (m3 ); SP: standard pressure (101.33 kPa); R: gas constant (0.08207 Latm/ mole/ K); 273.15: conversion from C to K; T: ambient temperature (C); surface: surface of the floating chamber over the water (m2 ); Global conversion of atm to atm, L to m3 and g to mg is Equal to 1. Flu x (mg m-2 d -1 ) =
12 273.15+

(2)

The flu x with NDIR and FTIR instrument can be

IJES Vol.2 Iss.4 2012 PP.156-162 www.ijesci.org C World Academic Publishing ~ 157 ~

International Journal of Energy Science


calculated using the equation 1. The correlation coefficients are d ifferent fo r the NDIR and FTIR instrument (Tab le 2). Fo r a maximu m stability, the FTIR instrument needs a continuous purge of zero gas (nitrogen).
TableII Instrument
CORRELATION COEFFICIENT FOR ACCEP TING FLUXES

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emp irical equations [5, 7, 13]. The parameters required for the calculation are the concentration of the dissolved gas in the water, wind speed and temperature of the water. The wind speed is a majo r factor affect ing the flu x. The equations used for the calculations are not validated at low and high wind speeds (< 5 m/s and > 10 m/s, [7]). At each site, a samp le of water is taken at a depth of about 15 to 30 cm. The bottle is sealed underwater to avoid the presence of air bubbles in the sample. The samples were analyzed by in-situ as well as by the ex-situ laboratory method [12] . 2) Laboratory Analysis:

Gas

Flux (ppm) >200 >100 to <200 >100 (including all negatives) -50 to 50

R2 >0.85 >0.75 >0.50 All

NDIR CO2

CO2

>200 >100 to <200 >100 (including all negatives) -50 to 50 >2.0 >1.0 to <2.0 >1.0 (including all negatives) - 0.5 to 0.5

>0.85 >0.75 >0.50 All >0.70 >0.60 >0.35 all

FT IR CH4

After extraction of water, the gases are analyzed by the same method used for the floating chamber with in situ or ex situ laboratory analysis. The sample is first shaken to equilibriate with an equal volu me of inert gas like Nitrogen (N2 ) and argon (Ar) used for in-situ and ex-situ laboratory analysis respectively. For CO2 , there is no difference between extraction with N2 or Ar but for CH4 , Ar is a better choice as the nitrogen peak in the GC analysis could interfere in the analysis [14]. Table 3 co mpares the advantages and disadvantages of floating chamber when coupled to NDIR and FTIR for in-situ and ex-situ laboratory analysis. FTIR is shown as the best fit analyzer for GHG flu x measurement when it is coupled to floating chamber whereas TBL method is a also a best method for measuring diffusive flu xes but is less effective and important for ebbullit ive emission.

D. Thin Boundary Layer Method It consists of the following steps: 1) Field Sampling: This method is different fro m previous method as it does not involve a floating chamber and hence does not directly measure the flu x over water. It calculates the flu x using semi-

TableIII ADVANTAGE AND DISADVANTAGE OF DIFFERENT METHODS A) Advantages Floating Chambe rs Coupled to an NDIR or FTIR Instrument Disadvantages The instrument is expensive. Needs couple of weeks for repair The NDIR can measure only CO2 fluxes. The absorber columns for zero air needs frequent change/replacement. FT IR is less stable without N2 so the zero of the FTIR is set with nitrogen as zero gas. If N2 gas is exhausted, ambient air passed through solid absorbents may be used to make zero air. This results in less precision. Gives higher fluxes values than those measured by floating chambers with laboratory analysis.

Can measure real time concentration and change of concentration Problems in measurement can be detected rapidly. Contamination can be easily detected. The results can be obtained rapidly The FTIR can measure CO2 , CH4 and N2 O fluxes. Air trapped is mixed under the chamber during sampling. Flux measurement is fairly quick i.e. 10 to 15 min is taken for one measurement. 10-20 sites can be sampled each day. B) Advantages

Floating Chambe rs with in-situ Laboratory Analysis Disadvantages Difficult to set up the laboratory in remote areas. If the instrument breaks down, it may take some time to repair. Can be calibrated with only standards of 10000 ppm which does not correspond to the range of actual measurements (usually <1000 ppm). The measurement at site is costlier. Not possible to ensure adequacy of aeration of the chamber and tubing. No real mixing of the air trapped under the chamber during sampling. Takes long time (1 to 2 hrs) to measure the fluxes. Only 2-4 sites can be sampled per day.

The air samples can be analyzed in <24 hrs and there is no loss of stability of the samples. The results are known rapidly and it is possible to measure the flux couple of days after sampling

C) Advantages

Floating chambe rs with ex-situ laboratory analysis Disadvantages Loss of stability occurs when time lag between sampling and analysis is increasing for CO2 Difficult to transport the samples to the laboratory by plane or by bus from

GC analysis is more precise than other detectors. Standards used are closer to the range of actual measurements. No need to install a laboratory on site.

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Useful for a remote site where setting up of a laboratory is difficult.

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remote areas. No real mixing of the air trapped occurs under the chamber during sampling. Not possible to know the adequacy of aeration of the chamber and the tubing between sites. The results can be obtained within a week or more after sampling and is not possible to return on site if flux measurement is needed again. It time consuming as it takes about 1-1/2 hrs to measure a flux. Only 2-4 sites per day. TBL Method Disadvantages In remote areas, the transport of samples to the laboratory is difficult. The result obtained by the laboratory is low compared to theoretical concentrations of dissolved CO2. The fluxes measured are based on theoretical equations which are not validated at low and high wind speeds. On a day with calm winds, the fluxes become automatically zero. The error in the wind speed measurement is a serious error. The fluxes measured are usually lower than those measured with floating chambers with laboratory analysis.

Advantages

Very quick; as a site can be sampled in < 5 minutes. 20-40 sites/day can be easily sampled.

III. ST ABILITY OF AIR AND WATER SAMPLES IN SYRINGES AND


BOTTLES

For getting comparab le result, the syringes and bottles are important accessories for the transport of air and water samples to ensure their stability and to reduce the error in flu xes measurement. For in-situ laboratory method, the stability of the air samples in the syringes can be tested with a CO2 standard of 10000 pp m. Samp les are found stable for about 48 hours with losses of < 5% (Table 4). No stability test was done at concentrations near those measured. In ex-situ laboratory method, the stability of the air samples was tested at 10 concentrations ranging from 0 to 1200 ppm CO2 [14]. Samples near the ambient air concentration (350-530 ppm) are stable for 21 days. For other concentrations, there seems to be some diffusion of CO2 fro m o r into the syringe with t ime. An equation was used to correct the concentration of the sample according to the delay in sampling and analysis of samples with concentration higher than 530 pp m. In 2000 and 2001, 7% and 32% of the samples had a concentration higher than 530 pp m. The stability was also tested for the CH4 in the air around 4 and 8000 ppm [14]. Samples are stable fo r about 7 days, beyond which slight loss in concentration may occur. On average, samples were analyzed within 12 days of sampling in 2000 and 8 days in 2001 [12].
TableIV STABILITY OF AIR AND WATER SAMPLES IN SYRINGES AND BOTTLES In-Situ analysis 1. Air samples were tested with a CO2 standard of 10000 ppm Ex-Situ analysis The stability of the air samples can be tested at concentrations ranging from 0 to 1200 ppm CO2 CO2 samples are stable for 21 days near ambient air concentration (350530 ppm) and 7 days for CH4 around 4 and 8000 ppm. Stability test was done according to the delay between sampling and analysis for samples with concentration higher than 530 ppm for CO2 .

several stability tests were conducted. Contrary to air samples, standards were not available to confirm the actual concentration measured. For CO2 , the results were inconclusive due to variation in different types of water. For CH4 , samp les with dissolved CH4 concentration <10 pp m are stable for about 4 days [15]. IV. QUALITY CONTROL FOR ALL METHODS A. Precision Analysis of Duplicates Precision is obtained by comparing two result of the same sample taken in duplicate. This can be done by duplicate sampling of air or water sample, analysis in the laboratory , flu x measurement by laboratory analysis if all air sample were taken in duplicate and two or mo re chambers were installed side by side, flu x measurement by automated instrument if flu x is measured by two different instruments simultaneously with one or two chambers and if two flu xes are measured one immediately after the other. The precision can be calculated using Eq. 4. Lower % precision means a better precision. Two identical results have a 0% precision as there is no difference between the results. The precision is different for each method and varies fro m year to year (Table 5). Fo r in-situ laboratory analysis, no recorded informat ion was obtained to ascertain the precision. The precision for duplicates can be calculated by Precision coefficient =
2 ( )

di = difference between two duplicates; n = number of pair o f duplicates The precision is finally converted in % with the following equation: Precision (%) =

(3)

2.

Samples are stable for about 48 hrs with losses of 5%.

* 100

(4)

3.

No stability test was done at air or water

For in-situ laboratory method, no stability tests of the water samples were made wh ile for the ex-situ laboratory method,

As seen from Table 5, the precision of the ex-situ laboratory analysis is fairly good but lower than 7%. The precision of analysis of field duplicate samp les is lower than for laboratory duplicate samp les between 8 to 26% for air samples and between 7 to 35% fo r water samp les. One of the possible causes of this lower precision is the lack of real mixing of the air in the chamber and therefore the consecutive samples taken may have some difference in concentration. For water samples, sometimes the duplicates were taken at the

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beginning and at the end of a flu x measurement and one hour may have elapsed between the sampling of each duplicate. The precision for the flu xes measured with the in-situ laboratory
TableV

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method is lo wer than those measured by ex-situ laboratory method. For the last three years the same precision was found (30 % for CO2 ) for both the method.

P RECISION BY DIFFERENT METHODS AND TYPE OF DUPLICATES

Method Laboratory in situ Laboratory ex situ NDIR FT IR

Ye ar 1993 to 1999 2000 and 2001 2001 to 2003 2002 and 2003 2000 and 2001 1999 to 2001 2000 to 2002 1999 to 2001

Type of Duplicate n Flux from different chambers Flux from duplicate samples of the same chamber Laboratory analysis of the same water sample Laboratory analysis of the same air sample Laboratory analysis of duplicate water samples taken at the same time Laboratory analysis of duplicate water samples taken at the same time 414 77 1025 228 13 32 142 20 133

CO 2 % 52 31 34 24 36 5.9 3.1 6.6 7.7 n 430 39 131 3 31 142 20 133

CH4 % 62 30 52 15 6.2 6.7 35 26

Laboratory ex situ 2000 to 2001

For the automated method, the duplicates used for the calculation of the precision are not real duplicates. They are flu xes measured one after the other, usually in a short period of time (often <15 minutes and not more than one hour). Globally, the precision of the automated instruments (24 to 34%) is similar to the laboratory analysis for CO2 flu xes [16]. The precision of the CH4 flu xes measured with laboratory analysis method is 30% better for the last three years. The precision obtained with FTIR is lower (52%) due to the greater ability to measure very low flu xes with this instrument. It may be concluded that lower precision for NDIR and FTIR in so me sampling campaigns (with very low flu xes) affect the overall precision of the method [16]. The precision is not the same for each instrument used (Table 6). The LI-COR instruments obtained the lowest precision. These instruments are least user friendly in the field and therefore, most of the measurements were made with PP Systems and the Gasmet instruments.
TableVI P RECISION FOR NDIR INSTRUMENT USED FOR CO 2 MEASUREMENT [16] Company Instrument Model 206 208 LI-COR 209 All LI-COR 528 528 PP systems 527 577 578 All PP system 2002 2002 2002 2003 2003 2003 2003 2002 and 2003 5 63 193 116 235 275 74 893 64 43 32 40 28 25 31 31 Ye ar 2002 2002 n 8 50 Pre cision (%) 27 45

Table 7 lists the number and percentage of rejected flu xes for all methods [17, 16, 12]. The percentage of flu xes rejected is variable not only for each method but for each year of sampling. For CO2 flu xes, % of rejected flu xes are slightly better for NDIR (20%) co mpared to the laboratory methods (24 to 26%) while % of rejected flu xes is highest for the FTIR for CH4 flu xes. The method with less flu x rejection is with in-situ laboratory analysis. The other two methods (ex-situ laboratory analysis and FTIR) have the same % rejected flu xes between 51 and 58% on an average.
TableVII NUMBER AND % OF CO 2 AND CH 4 FLUXES REJECTED FOR EACH
METHOD
[16]

Numbe r of Fluxes Method Ye ar Measure d For CO 2 Floating Chamber with analysis in situ Floating Chamber with analysis ex situ Floating Chamber with NDIR Floating Chamber with FTIR 1993 to 1999 2000 and 2001 2001 to 2003 2002 and 2003 For CH 4 Floating Chamber with analysis in situ Floating Chamber with analysis ex situ Floating Chamber with FTIR 1993 to 1999 2000 and 2001 2002 to 2003 833 243 902 127 123 527 833 243 2702 916 201 64 547 399 Re jecte d

% of Fluxes Re jecte d

24 26 20 44

15 51 58

n presents the number of pairs of duplicates not the number of sites sampled.

B. Completeness Percentage of Rejected Fluxes As discuss earlier, each flu x is accepted or rejected according to the coefficient of correlation. The flu x can be rejected, if problem occurs during sampling. The nu mber o f samples accepted or rejected is different for each method.

For the NDIR and FTIR, the numbers of rejected flu xes are very different for each campaign. In some cases, there are no rejected flu xes. The % of rejected flu xes is very high in those sampling campaigns where most of the flu xes were very lo w or negative. For such flu xes, there is a lot o f variation between samples and as a consequence, the coefficient of correlation is lower and the number of flu xes rejected is higher. Without

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these campaigns, the number of rejected flu xes would be lower for the automated instrument. C. Comparison of the Two Methods with Syringe Due to logistical constraints, a direct comparison of the two different methods in the field cannot be made. The average flu xes measured in the same area at the same period of the year were used. For CO2 , the average flu x is similar for both methods except for the year 1994. For that year, there are so me sites with very high flu xes that result in a higher average and standard deviation. For CH4 , the flu xes measured in 2000 and 2001 with ex-situ laboratory analysis are lower than those measured with the in situ laboratory method between 1993 and 1997. This difference is due to the fact that most sites sampled between 1993 and 1997 were located near the shores or in small bays. Usually these sites have a higher flu x of CH4 than sites located in the middle of the reservoir. D. Comparison of Syringe and TBL Methods Duchemin et al. 1999 [7] co mpared both the methods with 1994 data. Fo r the studied sites, it was shown that the TBL method obtained slower flu xes co mpared to the floating chamber method with in-situ analysis. The same observation was made in 1999 (with in-situ laboratory analysis) and in 2001 (with ex-situ laboratory analysis) [16, 12]. Also, the correlation between the two methods is very low for 1999 and 2001 data (R2 of 0.05 fo r CO2 and 0.43 for CH4 ) as shown in Fig. 4 and 5 [18]. In calm conditions, the flu xes obtained with the floating chambers are higher than those obtained with the TBL method. The design of the floating chamber may affect the flu xes measured. Because of the logistical constraints related to the analysis of the water samples and the fact that the TBL method gives lower flu xes co mpared to the floating chamber method, the use of this method was not made.

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E. Comparison of Syringe and Automated Instrument Methods To co mpare the results of syringes and automated instruments, the fluxes measured by both methods at the same site were co mpared. Total sites were 24 in 2001 and 2002 [16, 12] . The two chambers were installed at the same site. Du ring the sampling o f the chamber with syringes, one or more flu xes were measured with the automated instrument and it is found that there is a good correlat ion between the two series (R2 of 0.92 for CO2 and 0.81 for CH4 ) as shown in Fig. 6 and 7. Fo r CH4 , the flu xes measured with the syringes are usually slightly higher than those measured with the FTIR instrument. On average, the flu xes are 19% higher if all the sites were considered.

Figure 6 Comparison of CO2 fluxes (mgm -2 d-1) measured by floating chamber with syringes and with NDIR/FTIR instrument

The above result indicated that the CO2 flu xes measured by automated instrument are usually higher than those measured with the syringes. The difference is more impo rtant for flu xes higher than 1000 mgm-2 d -1 (average 96% difference) than for smaller flu xes (average 19% difference). The differences between the two methods are attributed to the different designs of the floating chambers. F. Comparison of NDIR and FTIR Instruments Observations obtained from NDIR and FTIR were compared with the certified gas cylinder of CO2 (concentration in the range of 400-450 ppm). A slight difference between the instrument and the gas cylinder, usually around 10 pp m and less than 30 ppm is always found which does not significantly affect the results as the increase in concentration (ppm/s) and not the absolute concentration was used to calculate the flu x.

Figure 4 Comparison of CO2 fluxes (mgm d ) measured by T BL and with floating chamber method with syringes

-2

-1

In 2002 and 2003, instruments of three different models (LI-COR, PP Systems and Gasmet) were used to ensure to produce similar results.

Figure 5 Comparison of CH4 fluxes (mgm -2 d-1) measured with T BL and with floating chambers with syringes (The dotted line represents the 1:1 line. Fluxes on the upper portion of the line mean that fluxes measured with the T BL method are lower than those measured with floating chamber with syringes.)

Figure 7 Comparison of CH4 fluxes (mgm -2 d-1) measured with syringes and with FTIR instrument (The dotted line represents the 1:1 line. Fluxes on the upper portion of the line mean that fluxes measured with the FTIR instrument are higher than those measured with syringes.)

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Flu x measurement was carried out in the field at the same time with two or more instruments. The comparison was made in three different ways:

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the method of choice that can enable sampling at large nu mber of sites in a relatively short time with fairly good precision giving higher flu x values co mpared to the laboratory analysis and thin boundary layer. Acknowledgement: One of the authors acknowledges the support of Ministry of Human Resources in the form of research assistance to carry out this work.
REFERENCES [1] [2] Rudd JWM, Harris R, Kelly CA, Hecky RE (1993) Are hydroelectric reservoirs signifiant sources of greenhouse gases? Ambio 22:246-248G. Rosa LP, Dos Santos MA (1998) Dams and Climate Change. Proceedings of International Workshop on Hydrodams, Lakes and Greenhouse Gas Emissions (December 4-5), Rio de Janeiro. Duchemin E, Lucotte M (1995) Production of the greenhouse gases CH4 and CO2 by hydroelectric reservoirs of the boreal region, Glob Biochem Cycles 9(4):529-540. Pircher, W. 1993. 36 000 dams and still more needed. International Water Power & Dam Construction 45:51518. Canuel R, Duchemin E, Lucotte M (1997) Handbook on greenhouse gases sampling and analytical techniques. International Workshop on Greenhouse Gases, Santarm, Brazil. Carignan R, Blais AM, Vis C (1998) Measurement of primary production and community respiration in oligotrophic lakes using the Winkler method. Can J Fish Aquat Sci 55:1078-1084. Duchemin E, Lucotte M, Canuel R (1999) Comparison of static chamber and thin boundary layer equation methods for measuring greenhouse gas emissions from large water bodies. Environ Sci Tech 33:350-357. Rosa LP, Matvienko B, Santos MA, Sikar E (2002) Carbon dioxide and methane emissions from brazilian power dams. Project BRA/95/G31, PNUD/ELETROBRS/MCT , Background Reports. Grelle A, Lindroth A (1996) Eddy-correlation system for long-term monitoring of fluxes of heat, water vapour and CO2 . Glob Change Biol 2:297-307. UNESCO/IHA. 2008. Assessment of the GHG Status of Freshwater Reservoirs Scoping Paper. April 2008. Therrien J (2003) Revue des connaissances sur les gaz a effet de serre des milieux aquatiques Le gaz carbonique, loxide nitreux et le methane. Rapport du Groupe conseil GENIVAR inc. presente a Hydro Quebec, Direction Barrages et Environnement, Montreal. Lambert M, Frchette JL (2002) Campagne dchantillonnage sur les missions de gaz effet de serre des rservoirs et des lacs environnants, rapport de terrain 2001. Direction Environnement, Hydro-Qubec, Montral. Liss PS, Slater PG (1974) Flux of gases across the sea-air interface. Nature 247:181-184. Dumas P (2002) Analyse des gaz effet de serre: mthane et dioxyde de carbone. t 2001. Direction de toxicologie humaine, Institut national de sant publique du Qubec. Dumas P (2001) Rapport mthodologique. Amlioration et validation de la mthode danalyse des gaz effet de serre dans leau et lair. tude des contenants utiliss pour lchantillonnage. Centre dexpertise en toxicology humaine, Institut national de sant publique du Qubec. Lambert M, Frechette JL, Dumas P, Tremblay A, Varfalvy L (2001) Development of ex-situ GC/MS analysis technique for greenhouse gas samples collected by floating chambers and a hydroplane. Proceedings of the 28th Congress of the Societas Internationalis Limnologiae (SIL), February 4-10th, Melbourne, Australia. Bourassa J (2001) Banque de donnes UQAM sur les missions de gaz effet de serre. Bilan statistique. Direction Environnement, HydroQubec, Montral. Matthews CJD, St.Louis VL, Hesslein RH (2003) Comparison of three techniques used to measure diffusive gas exchange from sheltered aquatic surfaces. Environ Sci Tech 37:772-780.

instruments connected to the same chamber in a closed loop; instruments connected to different chambers at the same time and flu x measured by different instrument one after the other with the same chamber.

As the fluxes measured by different instruments at the same site and at the same t ime can be considered as duplicates and the precision was calculated. Table 8 shows that the instruments with the more co mparable results are the Gas met and the PP Systems (model No. 528) with a precision of 14%. The PP Systems are co mparable between themselves with a precision around 10%. The LI-COR has lo wer precision compared to Gas met and the PP Systems (precision range fro m 23 to 74%). As discussed elsewhere there are also instruments with the lowest precision for duplicates from the same instru ment.
TableVIII COMPARISON OF FLUXES MEASURED WITH DIFFERENT NDIR/FTIR [12] INSTRUMENTS AT THE SAME SITE , AT THE SAME TIME Instrument Compare d Year 2002 Gasmet PP System 528 Gasmet-LI-COR 206 Gasmet-LI-COR 208 Gasmet-LI-COR 209 PP System 528-LI-COR 206 PP System 528-LI-COR 208 PP System 528-LI-COR 209 Year 2003 PP System 527-528 PP System 577-528 PP System 577-528 Numbe r of Duplicates 76 17 23 7 15 30 8 44 46 46 Pre cision (%) 14 27 74 68 23 45 61 10 9 10

[3]

[4] [5]

[6]

[7]

[8]

[9]

[10] [11]

In view of above, it is conclude that the Gas met has flu xes slightly lower than those of the PP Systems and the LI-COR have flu xes h igher than those obtained with both the Gas met and PP Systems. Since the LI-COR is less user friendly in the field and has the lowest precision, these instruments were used only in the first month of field measurements in 2002. For all other field measurements, only the Gas met and the PP Systems were used. V. CONCLUSIONS The review o f methods discussed above reveals that it is almost impossible to find a perfect method to accurately measure GHG d iffusive flu xes in water bodies. As such, when gross emissions of GHG are measured with floating chambers, the air-water interface is d isturbed, thereby affecting the measured flu x. Each method has its pros and cons. To obtain an adequate representation of the mean flu x for a reservoir o r a natural water body, it is important to have a large nu mber of data fro m different locations. Based on the results the floating chamber with an automated instrument (NDIR or FTIR) has been found

[12]

[13] [14]

[15]

[16]

[17]

[18]

IJES Vol.2 Iss.4 2012 PP.156-162 www.ijesci.org C World Academic Publishing ~ 162 ~

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