Journal of Chromatography A, 1480 (2017) 62–69

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Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Validation of an analytical method for simultaneous high-precision

measurements of greenhouse gas emissions from wastewater
treatment plants using a gas chromatography-barrier discharge
detector system
Raffaella Pascale a , Marianna Caivano a , Alessandro Buchicchio a , Ignazio M. Mancini a ,
Giuliana Bianco b,∗ , Donatella Caniani a,∗
a
Scuola di Ingegneria, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano, 10, 85100 Potenza, Italy
b
Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano, 10, 85100 Potenza, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Wastewater treatment plants (WWTPs) emit CO2 and N2 O, which may lead to climate change and global
Received 1 August 2016 warming. Over the last few years, awareness of greenhouse gas (GHG) emissions from WWTPs has
Received in revised form increased. Moreover, the development of valid, reliable, and high-throughput analytical methods for
15 November 2016
simultaneous gas analysis is an essential requirement for environmental applications. In the present
Accepted 17 November 2016
study, an analytical method based on a gas chromatograph (GC) equipped with a barrier ionization dis-
Available online 18 November 2016
charge (BID) detector was developed for the first time. This new method simultaneously analyses CO2 and
N2 O and has a precision, measured in terms of relative standard of variation RSD%, equal to or less than
Keywords:
Barrier ionization discharge (BID)
6.6% and 5.1%, respectively. The method’s detection limits are 5.3 ppmv for CO2 and 62.0 ppbv for N2 O.
Carbon dioxide (CO2 ) The method’s selectivity, linearity, accuracy, repeatability, intermediate precision, limit of detection and
Gas chromatography (GC) limit of quantification were good at trace concentration levels. After validation, the method was applied
Greenhouse gas (GHG) to a real case of N2 O and CO2 emissions from a WWTP, confirming its suitability as a standard procedure
Method validation for simultaneous GHG analysis in environmental samples containing CO2 levels less than 12,000 mg/L.
Nitrous oxide (N2 O) © 2016 Elsevier B.V. All rights reserved.

1. Introduction environmental equilibria and its anthropogenic sources. Increas-

In recent years, it has been ascertained that wastewater treat-
ment plants (WWTPs) are potential sources of anthropogenic
greenhouse gases (GHGs), which contribute to climate change
and air pollution [1,2]. The United Nations Framework Conven-
tion on Climate Change (UNFCCC) calls for the stabilization of GHG
concentrations in the atmosphere at a level that would prevent
dangerous anthropogenic interference with the climate system.
The Kyoto Protocol provides binding targets based on a ‘basket’
of six GHGs: carbon dioxide (CO2 ), methane (CH4 ), nitrous oxide
(N2 O), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and
sulfur hexafluoride (SF6 ).
However, most studies dealing with climate change mainly
focus on CO2 because of its strong negative effects on
∗ Corresponding authors.
E-mail addresses: giuliana.bianco@unibas.it (G. Bianco),
donatella.caniani@unibas.it (D. Caniani).
ing attention is also given to the assessment of N2 O emissions due
to the high global warming potential (GWP) of N2 O, which is almost
300 times stronger than CO2 over an atmospheric residence time of
100–120 years [3]. In the last decade, N2 O emissions from WWTPs
have been evaluated, focusing on the biological nitrogen removal
(BNR) processes (e.g., nitrification, denitrification, and nitrifier den-
itrification) that are the major producers of N2 O [4,5]. Furthermore,
N2 O from WWTPs represents 3% of the global emissions from all
sources and represents the sixth most important contribution [6].
In addition to N2 O monitoring, it is useful to also measure
CO2 emissions produced by biomass growth through the oxida-
tion of biodegradable organic matter [2]. Although organic matter
degradation is considered a zero-emission process because the CO2
produced should be involved in the natural carbon cycle [7], result-
ing in negligible impact in terms of the greenhouse effect, recent
studies demonstrate that some of the incoming organic carbon is
not of biogenic origin. Indeed, a considerable part of the incoming
organic carbon is petroleum-derived (e.g., cosmetics, pharmaceu-
ticals, body care products, etc.) and is usually named fossil organic

http://dx.doi.org/10.1016/j.chroma.2016.11.024
0021-9673/© 2016 Elsevier B.V. All rights reserved.
 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69
carbon (FOC). This quantity of FOC in the influent wastewater is con-
sidered a CO2 emission source, thus contributing to the net carbon
footprint (CFP) of WWTPs [8]. These studies lead us to reconsider
the amount of CO2 produced during biological processes.
Therefore, N2 O and CO2 emissions must both be monitored dur-
ing BNR and organic carbon oxidation processes, respectively, along
the water treatment line. Estimation of the potential gas production
allows us to derive information about the effectiveness of the treat-
ment configuration and obtain better overview of the treatment
processes and the net wastewater cycle.
Gas chromatography (GC) has been commonly used to deter-
mine N2 O and CO2 concentrations in gaseous emissions produced
by biological processes employed for wastewater treatment [9].
Detectors measuring the concentrations of CO2 and N2 O in the
off-gas exiting the treatment units require different sensitivity,
because of different concentration ranges of the gases in the same
sample.
The most common detectors used for CO2 analyses are the
thermal conductivity detector (TCD) and the flame ionization
detector (FID), which are applied after catalytic transformation into
CH4 [10–12]. The most common detection system for N2 O is the
electron-capture detector (ECD), which, as reported in standard
methods [13–15], provided a detection limit of parts per billion by
volume (ppbv ). To our knowledge, even though a broad spectrum
of detectors, chromatographic columns and operating conditions
have been proposed for analyses of CO2 and N2 O, few studies deal-
ing with their simultaneous analysis are presently available in the
scientific literature [14–18].
Sitaula et al. [14] used a wide-bore capillary GC equipped with
three detectors, a TCD, a FID, and an ECD, for simultaneous analysis
of CO2 , CH4 , and N2 O with relative standard of variations of 0.7%,
0.6%, and 2.6%, respectively. Wang et al. [19] used two detectors, a
FID and an ECD, for simultaneous GC analysis of CH4 , CO2 , and N2 O.
Hedley et al. [20] implemented an automated GC procedure
to monitor gas exchanges at soil surfaces. After chromatographic
separation, the column effluent was switched to the FID, via a
methanizer or to the ECD for analysis of CH4 , CO2 , and N2 O with
precisions of 0.87%, 2.17%, and 0.74% and method detection limits
of 0.04 ppm, 25.5 ppm and 7.4 ppb, respectively.
Mondini et al. [17], by means of a TCD detector, used a micro-GC
designed for continuous gas analyses for measuring soil respira-
tion with detection limits for CO2 and N2 O equal to 2 and 1 ppmv ,
respectively. A Micro-GC coupled to a TCD detector was also used
by Cayuela et al. [18] for the evaluation of GHG emissions during
composting of lignocellulosic residues.
Field techniques have also been proposed [21–28] that have the
advantage of determining gas concentrations without the need to
capture, transport and store gaseous samples. However, most of
them do not allow simultaneous CO2 and N2 O detection and, com-
pared to GC analysis, are less sensitive and are characterized by a
narrow linear range, low precision and poor accuracy [21–28].
Although GC methods are more suitable for gas analyses, there
are still difficulties in using ECD and TCD or FID to estimate CO2 and
N2 O concentrations simultaneously. Indeed, N2 O concentrations
are commonly too low for TCD detection. ECDs areparticularly sen-
sitive to electronegative compounds, but CO2 cannot be detected.
The FID-methanizer combination can be used for CO2 analysis, but it
does not detect N2 O. Moreover, the use of three different detectors
(i.e., TCD, ECD and FID) is highly time-consuming and expensive.
Therefore, the need to identify a better methodology to estimate
GHG emissions from WWTPs led us to develop a simple and sen-
sitive method for simultaneous high-precision measurements of
N2 O and CO2 emissions using a GC equipped with a barrier ioniza-
tion discharge detector (BID). The GC-BID, to our knowledge, has
not been used before for measuring GHGs. BID is a sensitive detec-
tor in which the ionization process is obtained by a helium-based
63
dielectric barrier discharge plasma. The system offers highly sen-
sitive detection of all compounds (universal) except Helium (He)
and Neon (Ne). It has a sensitivity more than 2 times higher than
FIDs and over 100 times higher than TCDs, enabling stable analyses
over a long period [29,30].
In this study, a fully validated method for the simultane-
ous detection of N2 O and CO2 in gas environmental samples is
described, and its successful application on off-gas emissions from
WWTPs is presented.
2. Material and methods
2.1. Materials and reagents
Pure N2 O (99.998%) and CO2 (99.995%) were purchased from
Sigma Aldrich (Milano, Italy). He 6.0 (SIAD Corporation, Berg-
amo, Italy) was used as the carrier gas during chromatographic
separation. Gas standard mixtures (SIAD Corporation Bergamo,
Italy) containing mixed certified concentrations of CO2 (542 and
730 ppmv ) and N2 O (400 and 602 ppbv ) were used as reference
materials. A 10–100 cc/min scale RMA-150-BV rotamer (Rome-
tec, Roma, Italy) was used to keep the pressure drop in the loop
constant, for each injection. 10 ml, 1 ml, 250 ␮l and 100 ␮l gas-
tight syringes (Sigma Aldrich Milano, Italy) were used for preparing
calibration standards and quality control samples at different con-
centrations in 10 l Tedlar sampling bags equipped with PTFE fittings
(Zefon International, Ocala, USA). By means of the off-gas technique,
which is considered the main system for gas sampling [31], gas
samples were collected from the treatment units (i.e., oxidation
tank and secondary settler) of a WWTP located in Potenza (Basil-
icata, Southern Italy) that serves 160,000 equivalent inhabitants
(EI). To test the GC-BID method, gas collection was carried out with
1 l Tedlar bags (Zefon International, Ocala, USA) via a Gilian GilAir
Sampling Pump (Sensidyne, St. Petersburg, USA).
2.2. GC-BID analysis
A Shimadzu 2010 Plus Tracera GC (Shimadzu, Kyoto, Japan)
equipped with a Restek ShinCarbon ST micropacked column
(2 m × 1 mm i.d.) (Restek Corporation, Bellefonte, USA) and a BID
detector was used to analyse gas samples. The GC-BID system was
provided in a standard configuration, and a helium purifier (VICI,
Valco Instruments Co Inc., Schenkon, Switzerland) was used in
order to obtain the lowest background in the BID. The injection
temperature was set to 150 ◦ C. The oven temperature was 30 ◦ C
(the hold time was 5 min) and was increased to 120 ◦ C at a rate
of 10 ◦ C/min. All injections were made in the direct mode. Helium,
which was used as the carried gas, was supplied at a flow rate of
15.0 ml/min. The BID detector was operated at 250 ◦ C; 80 ml/min
discharge gas flow was used for analysis. A 1 ml sample loop was
employed for injection into the GC-BID system. Sample bags were
connected directly to the inlet loop and squeezed to generate a
pressure drop. When the pressure drop in the sample loop was con-
stant, measured in terms of flow rate, the sample valve was thrown
to initiate the run.
2.3. Validation study
During the evaluation process, the selectivity, response func-
tion (calibration curve), linearity, accuracy, precision (repeatability
and intermediate precision), limit of detection (LoD) and limit of
quantification (LoQ) were investigated [32]. A good linearity was
achieved, with a determination coefficient not lower than 0.998,
by a series of three injections (n = 3) of five standards (k = 5) within
concentration ranges of 50–1000 mg/l and 250–50000 ␮g/l for CO2
64 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69
and N2 O, respectively. The validation experiments (precision, cal-
ibration curve, LoD and LoQ) were performed with calibration
standards following the requirements established by the Interna-
tional Conference on Harmonization (ICH) [33]. The accuracy was
assessed by control repetitions (5 over non-consecutive days) using
certified reference materials. Moreover, the effect of CO2 concen-
tration on N2 O detection was established by measuring the N2 O
concentration in control samples with increasing CO2 levels which
could interfere with the N2 O peak.
3. Results and discussion
3.1. Chromatographic separation and selectivity of GC-BID
method
A thorough optimization was accomplished for the injector and
detector temperatures, BID discharge gas, injection volume and GC
parameters, such as oven temperature programming, flow rate, and
cleaning programme, in order to achieve the best possible separa-
tion of the test compounds. A typical chromatographic trace from
the GC-BID system is shown in Fig. 1; CO2 and N2 O are eluted with
good peak shapes at 11.1 min and at 12.5 min, respectively.
Selectivity refers to the extent to which the method can be used
to determine analytes of interest in mixtures or matrices without
interference from other components with similar behaviour [34].
To investigate the selectivity of the method, major air components
(oxygen, nitrogen and CH4 ) were evaluated (see Fig. 2). As environ-
mental gas samples are not complex matrices, O2 , N2 and CH4 are
well separated from the CO2 and N2 O peaks.
It should be considered that overlapping of the peaks of CO2
and N2 O, when both are present at relatively high concentrations,
could be detrimental to the quantitative analysis. Since CO2 usu-
ally occurs at concentrations (mg/L) higher than N2 O (␮g/L), CO2
can be considered the most important interfering species for N2 O
measurements when a GC-BID equipped with a ShinCarbon ST
micropacked column is used. To test the effect of CO2 concen-
tration on N2 O detection, different control samples with a fixed
N2 O concentration (approximately 400 ppbv ) and increasing CO2
concentrations (in the range of 500–25000 ppmv ) were analysed
(n = 3). In detail, for a 400 ppbv of N2 O, which can be considered
the global average atmospheric concentration [35], 12000 mg/l
(273 mM) of CO2 represents the maximum tolerable value for
simultaneous measurement of N2 O and CO2 (as illustrated in Fig. 3).
However, lower CO2 concentrations should be reached in sam-
ples for which N2 O has to be measured, and this can be obtained
by filtering gas samples through an absorption column (h = 5 cm,
d = 1 cm) filled with sodium hydroxide (NaOH) before injection into
the GC-BID system. As shown in Fig. 4, a CO2 concentration higher
than 12000 mg/l results in a broad chromatographic peak that does
not allow N2 O peak integration and therefore results in incorrect
quantification.
3.2. Calibration curve and linearity
Calibration curves were obtained via the external standard
method. Each point on the calibration curves was generated as the
area of CO2 and N2 O within a concentration range of 50–1000 mg/l
and 250–50000 ␮g/l, respectively. Calibration standards were pre-
pared at five (k = 5) concentration levels on three non-consecutive
days (p = 3) over three weeks: 50, 250, 500, 750, 1000 mg/l for CO2
and 250, 500, 5000, 25000, 50000 ␮g/l for N2 O. Each standard was
analysed in triplicate (n = 3). Linear regression equations and stan-
dard deviations were calculated by the least squares method (see
Table 1).
The Analytical Method Committee suggests the estimation of
the mean square error (R2 ) and the Fisher ratio (F) as a reliable
approach to check the linearity of calibration functions [36]. F val-
ues calculated for 3 and 12 ◦ of freedom were 3.20 and 2.66 for N2 O
and CO2 , respectively. The critical value at a significance level of 95%
is F0.05,3,12 = 3.49. Since the calculated values of F are less than the
tabulated values and the R2 values are greater than 0.998, indicat-
ing linearity, the proposed linear models are adequate to describe
the observed data, as shown in Table 1.
3.3. Accuracy
The accuracy of an analytical procedure is defined as the close-
ness of agreement between the conventional true value or an
accepted reference value and the obtained value [32]. The accuracy
of the GC-BID procedure can be assessed by analysing a certified ref-
erence material and comparing the measured value with the true
value supplied with the material, using a minimum of 9 determi-
nations [33]. We tested the accuracy with 2 concentrations and 5
replicates for each level. The acceptance criteria for accuracy allows
for a bias of not more than 15% from the accepted reference value
[37,38]. As shown in Table 1, accuracy values were in the range
of 9.8-13.7% for N2 O and 12.4-12.6% for CO2 , reflecting acceptable
accuracy of the proposed CO2 and N2 O analysis method.
3.4. Precision (repeatability and intermediate precision)
The precision of an analytical procedure expresses the closeness
of agreement (degree of scatter) between a series of measurements
obtained from multiple sampling of the same homogeneous sample
under prescribed conditions [33]. For the GC-BID method, the pre-
cision was assessed by calculating the relative standard deviation
(RSD%) of repeatability (intra-day precision) and the intermediate
precision (inter-day precision). The ICH [33] requires repeatability
to be tested from at least nine replications covering the entire speci-
fied ranges, which were 50–1000 mg/L for CO2 and 250–50000 ␮g/L
for N2 O, respectively. Intermediate precision was determined by
analysing 6 replicates (n = 6) of a calibration standard (k = 1) on
three non-consecutive days (p = 3) over three weeks. As shown in
Table 1, the relative standard deviation (RSD%) values for repeata-
bility were between 0.4% and 6.6%, and intermediate precision
values between 2.7% and 4.6%, in agreement with the acceptance
criteria for precision (15% RSD) [37–39].
3.5. LoD and LoQ
The limit of detection (LoD) of an individual analytical procedure
is the lowest amount of analyte in a sample that can be detected
but not necessarily quantified as an exact value, whereas the limit
of quantification (LoQ) is the lowest amount of analyte in a sample
which can be quantitatively determined [33]. The LoD and LoQ were
evaluated from the residual standard deviation of the regression as
LoD = 3.3 sb /a and LoQ = 10 sb /a, where (sb ) is the standard deviation
of the b-intercept and (a) is the slope of the calibration curve [40].
The LoD was 62.0 ␮g/l for N2 O and 5.3 mg/l for CO2 ; the LoQ was
188.0 ␮g/l for N2 O and 16.0 mg/l for CO2 (Table 1).
3.6. Analysis of CO2 and N2 O in environmental samples
The effectiveness of the validated GC-BID method was evaluated
by the analysis of several samples for the simultaneous presence of
CO2 and N2 O. These samples were collected using the off-gas sam-
pling method described in [31], from the treatment units (i.e., the
activated sludge tank and the secondary sedimentation tank) of
the full-scale WWTP in Potenza (Basilicata, Southern Italy), which
serves 160,000 EI. A gas collection polyethylene floating hood
 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69 65

Fig. 1. GC-BID trace of CO2 (800 ppmv ) and N2 O (500 ppmv ) peaks at retention times of 11.1 and 12.5 min, respectively.

(1 × 0.7 × 0.4 m, L × W × H) with a cross sectional area of 0.7 m2 was
used for off-gas sample collection [31]. The off-gas was pumped
through a PTFE tubing sampling line to 1 l Tedlar bags, which were
taken to the laboratory for off-site GC-BID analysis.
Qualitative comparison of chromatographic profiles of samples
collected from the activated sludge tank and the secondary sedi-
mentation tank and a standard mixture (602 ppbv N2 O, 730 ppmv
CO2 ) is reported in Fig. 5. Gas sampling plans depend on the
geometry of the tank and the presence/absence of the aera-
tion system. Therefore, the hood was positioned in 4 different
points along the main axis of the oxidation tank and another 8
positions over the secondary settler surface were chosen. N2 O
off-gas concentrations at several chosen points along the oxi-
dation tank were 813.8 (±1.4) ppbv , 965.8 (±1.4) ppbv , 1179.9
(±1.4) ppbv , and 1160.8 (±1.4) ppbv . The CO2 levels in the same
points were 10211.5 (±2.5) ppmv , 10243.5 (±2.5) ppmv , 10280.7
(±2.5) ppmv , and 10273.4 (±2.5) ppmv . In the off-gas from the sec-
ondary settler (Fig. 6), at a fixed hood position, concentrations of
452.5 (±1.4) ppbv , 454.6 (±1.4) ppbv , 460.3 (±1.4) ppbv , 466.7
(±1.4) ppbv , 470.6 (±1.4) ppbv , 475.7 (±1.4) ppbv , 485.0 (±1.4)

Fig. 2. GC-BID trace of major air components (oxygen, nitrogen and methane) at retention times of 1.4, 2.1 and 5.2 min.
66 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69

Fig. 3. Profile of detected N2 O concentration values in different control samples with increasing CO2 concentrations in the range of 500–25000 ppmv . CO2 levels, which are
less than 12000 ppmv , do not interfere with N2 O measurement.

ppbv , and 514.4 (±1.4) ppbv for N2 O and 600.45 (± 0.15) ppmv ,
601.62 (±0.15) ppmv , 612.34 (±0.15) ppmv , 615.13 (±0.15) ppmv ,
615.39 (±0.15) ppmv , 629.66 (±0.15) ppmv , 633.21 (±0.15) ppmv ,
and 653.46 (±0.15) ppmv for CO2 were observed. Average values
for N2 O were 1030.1 ppbv in the oxidation tank and 472.5 ppbv
in the off-gas exiting the secondary settler. CO2 average values of
10252.3 ppmv and 620.16 ppmv were observed in off-gas from the
oxidation tank and secondary settler, respectively. Even though
several studies have investigated the emission levels of N2 O and
CO2 from WWTPs [13,24,41–45], it is known that GHG emissions
depend on wastewater plant configuration; therefore, a compar-
ison with the literature is difficult [5]. However, many studies
[21,22,44,46,47] report higher levels of GHGs emitted from aerated
tanks due to the stripping effect from the liquid into the gas phase
through aeration submerged devices [48].

Fig. 4. GC-BID trace where high CO2 levels, corresponding to the very broad peak, interfere with N2 O measurement (ppbv ) (trace a). This kind of interference can be overcome
filtering gas samples through an adsorption column filled with NaOH before injection into the GC-BID system (trace b).
 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69 67

Table 1
Validation parameters of analytical method for N2 O and CO2 measurements by GC-BID.

Calibration curve (k = 5, n = 3, p = 3)
Analyte Linear equation, y = ax + b R2 LoDa LoQb
CO2 y = (1.634 ± 0.042)104 x − (1.096 ± 0.260) 105 0.999 5.3 mg/L 16.0 mg/L
N2 O y = (2.112 ± 0.016)104 x − (1.428 ± 0.397) 103 0.998 62.0 ␮g/L 188.0 ␮g/L
Linearity (␣= 0.05; k = 5; n = 3)
Analyte F calculated F tabulated F test Relationship
CO2 2.66 3.49 H-null accepted Linear
N2 O 3.20 3.49 H-null accepted Linear
Accuracy (relative bias%) (k = 2, n = 5, p = 3)
Analyte Levels Relative Bias (%)
542 ppmv − 12.6
CO2
730 ppmv + 12.4
400 ppbv +13.7
N2 O
602 ppbv − 9.8
Precision
Analyte Levels Repeatibility (RSD%) Intermediate precision (RSD%)
(k = 3, n = 3) (k = 1, n = 6, p = 3)
50 ppmv 5.8
CO2 500 ppmv 6.6 4.6
1000 ppmv 0.4
250 ppbv 5.1
N2 O 5 ppmv 1.0 2.7
50 ppmv 1.1
a
LoD was calculated as 3.3 sb /a with sb standard deviation of the b-intercept and a the slope of the calibration curve.
b
LoQ was calculated as 10 sb /a with sb standard deviation of the b-intercept and a the slope of the calibration curve.

Fig. 5. Comparison of chromatographic profiles of gas samples collected from the activated sludge tank (black line), the secondary sedimentation tank (pink line) and a
standard mixture containing 602 ppbv N2 O and 730 ppmv CO2 (blue line). (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

4. Conclusion the simultaneous, sensitive and selective determination of N2 O and

CO2 emissions from WWTPs, and it is promising for other environ-
In this study, a new GC-BID method is described. The developed mental applications, provided that CO2 concentrations are equal to
method has been validated and demonstrated to be suitable for or less than 12000 mg/l. The GC-BID method allows us to measure
68 R. Pascale et al. / J. Chromatogr. A 1480 (2017) 62–69
Fig. 6. Comparison of chromatographic profiles of gas samples collected from different points along the secondary sedimentation surface.
gas concentrations accurately and reliably (15%) within concentra-
tion ranges of 0.25–50 ppbv for N2 O and 50–1000 ppmv for CO2 . In
the same concentration ranges, the analytical precision (RSD% less
than 6.6) for both analytes is greater than or equal to that of conven-
tional methods of analysis for these trace gases. Our study proposes
an analytical method for the simultaneous measurement of N2 O
and CO2 concentrations in WWTPs. The results could contribute to
the development of a standard methodology for gas sampling and
measurement, which is not presently available. Indeed, monitoring
of GHG emissions from WWTPs using this validated GC-BID method
allows us to improve our knowledge of the biological processes and
operational conditions in WWTPs and is useful for developing new
modelling approaches for lowering the environmental impact of
water utilities and the CFP of WWTPs.
Acknowledgements
Part of this study was funded by the Italian Ministry of Educa-
tion, University and Research (MIUR) through the Research project
of national interest PRIN2012 (D.M. 28 dicembre 2012 n. 957/Ric
− Prot. 2012PTZAMC) entitled “Energy consumption and Green-
House Gas (GHG) emissions in the wastewater treatment plants:
a decision support system for planning and management” (http://
ghgfromwwtp.unipa.it) in which Donatella Caniani is responsible
as the principal investigator for the Unibas Research Unit.
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