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Ammonia PDF
Ammonia PDF
Analytical Letters
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Determination of Ammonia
in Water Using Flow Injection
Analysis with Automatic
Pervaporation Enrichment
a b a a
Lingcheng Hong , Xiyan Sun & Linqin Wang
a
Institute of Environment and Engineering, Hohai
University , Nanjing, China
b
Delin Environmental Instrument Co. Ltd. , Nanjing,
China
Published online: 05 Oct 2009.
To cite this article: Lingcheng Hong , Xiyan Sun & Linqin Wang (2009) Determination
of Ammonia in Water Using Flow Injection Analysis with Automatic Pervaporation
Enrichment, Analytical Letters, 42:15, 2364-2377, DOI: 10.1080/00032710903137442
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Analytical Letters, 42: 2364–2377, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032710903137442
2364
Pervaporation Enrichment 2365
1. INTRODUCTION
Excessive ammonia in river and lake water would cause serious eutrophi-
cation and algal blooms, which jeopardize the survival of fish and affect
human health. There is an urgent need for timely monitoring of the
ammonia concentration in water to ensure that the ammonia in waste-
water stays within appropriate limitations.
The ammonia is often quantified by Nessler reagent spectrophotome-
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enrichment cycle. During the circulation, the acceptor flow was stopped
and the ammonia gas generated was absorbed continuously by the BTB
acceptor solution in the pervaporation unit which was set within the enrich-
ment cycle. In this way, the measuring range of ammonia could be adjusted
by controlling the duration of the enrichment circulation. Also, the con-
sumption of sample and donor flow was reduced and the sensitivity of the
method was improved greatly. When detecting wastewater with high ammo-
nia concentration, the duration of the enrichment cycle should be prolonged,
which could ensure adequate reaction to cause higher peak height and finally
improve the sensitivity. When detecting the surface water with low ammonia
concentration, the duration could be shortened appropriately, which could
ensure the same reaction efficiency and higher sampling frequency. Through
this way, the linear dynamic rang of the system was scaled-up.
2. EXPERIMENTAL
All solutions were prepared using analytical grade reagents and deionized
water. The stock donor solution (0.1 mol l1) was prepared by dissolving
4 g sodium hydroxide in 1000 ml deionized water. Different concentra-
tions (0.01–0.1 mol l1) of sodium hydroxide were prepared by diluting
the stock solution.
The pH and concentration of bromothymol blue (BTB) in the accep-
tor stream was also investigated. The BTB stock solution (100 mg l1)
was prepared by dissolving 0.100 g bromothymol blue in 16 ml ethanol,
and further diluted to 1000 ml. Acceptor solutions were prepared by
appropriately diluting the stock solution and adjusting to pH 6.5 with
a sodium hydroxide solution of 0.1 mol l1.
Ammonium stock standard solution (1000 mg l1) was prepared by
dissolving 3.819 g ammonium chloride and 1 ml concentrated hydrochlo-
ric acid to 1000 ml with deionized water. Working standard solutions
were prepared by appropriate dilution of this stock solution. The
standard stock solution can be used for a month.
Pervaporation Enrichment 2367
digital, and to calculate and record all the data. The detailed flow
procedure was as follow:
The flow system was optimized by varying the chemical and flow condi-
tions, targeting the best sensitivity for ammonia and better performance
of the FIA system.
The study for flow rate of the proposed system was mainly focused on
two parts: the donor enrichment cycle and the acceptor stream.
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The effect of flow rate for both the donor and acceptor solutions was
studied sequentially in the range of 1.0 to 8.0 ml min1. The results showed
that the flow rate affected the analytical signals significantly and the
optimum flow rate of the donor enrichment cycle is 6.0 ml min1. As for
the acceptor stream, the highest absorbance was achieved at a flow rate
of 1.6 ml min1.
Similar to the flow rate, the sample volume affected the sensitivity and
the analytical signal (Van Son, Schothorst, and den Boef 1983; Clinch,
Worsfold, and Sweeting 1988; Papaefstathiou, Luque de Castro, and
Valcarcel 1996) by affecting the sample throughput and the extent of
reaction. A larger sample volume usually resulted in a higher sensitivity
but produced an incomplete mixing of the analyte (ammonia) with the
reagent (the indicator mixture). As a result, a sample volume of 1 ml,
equivalent to a sampling coil length of 82 cm, was chosen as an acceptable
compromise between the sensitivity and sample throughput.
In the previous studies (Wang et al. 2003; 2000), the length of mixing coil
had a certain influence on the analytical signal. In our study, the length of
mixing coil in the range of 100 to 400 cm did not obviously affect the
analytical signal as the chemical reaction time could be adjusted by the
time of the enrichment. A 400 cm coil length was selected to conveniently
connect with the whole pipeline and achieve a complete mixing of the
sample with the reagent (NaOH).
and higher temperature increases the vapor pressure of the analyte in the
headspace and speeds up the diffusion (Wang et al. 2000; Papaefstathiou
et al. 1996; G
amiz-Gracia and Luque de Castro 1999).
For the study on the impact of temperature on the system, a home-
made thermostatic device was used to control the temperature of the per-
vaporation unit and the detector by immersing them in a thermostatic
bath. It was observed that after the initial linear increase of the analytical
signal with temperature, a maximum was reached at around 25 C and
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fluctuated slightly from 25 C to 40 C, after that the signal started to
become unstable. So a semiconductor thermostatic device was assembled
to control the temperature at 25 C.
Due to the fact that the acceptor flow is stopped during the enrichment
cycle, the duration of the enrichment cycle is directly related to the
throughput-rate of ammonia in the gas diffusion unit; thus, the duration
time is an important factor for the linear range.
A different duration time of the cycle was tested under the optimum
working condition listed in Table 1.
In the study, the sample concentration was tested from 0 to 100 mg l1.
However, only the appropriate linear range (R2 0.9985) was included in
Fig. 3 and Table 2. The data indicated that short duration time was ben-
eficial to low concentrations of ammonium sample while a longer duration
time of the enrichment cycle allowed a larger dynamic linear range. When
the duration time was too long, both sensitivity and the sampling rate were
decreased. For the on-line analysis of water samples, the duration time of
ammonia-rich water was fixed at 120 s, and the duration time for water
with low ammonia concentration was 60 s. In this condition, the system
could meet the needs of measurement accuracy in the shortest possible
time.
Figure 3. Effect of the duration time of the circulation on the optimized linear
detection range and the best R2.
3.5. Interferences
The coexisting gases (CO2, H2S, SO2) were converted into CO2 – 2
3 , HS , SO3
when reacting with alkali liquor (NaOH) and these anions cannot penetrate
through the semi-permeable PTFE membrane, therefore, their interferences
were not taken into account. Benzene, phenol, pyridine, quinoline do not
interfere in the proposed system because they are not volatile.
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Table 2. Analytical features of the proposed FIA system with different duration time of the circulation
The line corresponding Duration time of the Linear detection Linear
to that in Fig. 3 enrichment cycle (s) range (mg l1) equations R2
2373
Line 3 120 15–50 absorbance ¼ 0.0273 þ 0.0033X 0.9991
Line 4 150 20–50 absorbance ¼ 0.0723 þ 0.038X 0.9986
Line 5 180 20–50 absorbance ¼ 0.05 þ 0.0039X 0.9985
A water sample was injected into the flow system with the enrichment
cycle, and the ammonia concentration was calculated using a previously
established analytical curve based on absorbency. Various water samples
such as surface water, urban sewage, and industrial effluent were
analyzed with suitable circulation time.
4. CONCLUSIONS
The proposed flow system offers a better alternative for ammonia deter-
mination because it consumes a very limited amount of the toxic BTB
reagent, produces low effluent volumes, and makes use of simple and
low cost instrumentation. The combination of enrichment cycle and per-
vaporation unit was used successfully for the determination in industrial
effluent samples and natural waters.
Additionally, the system possesses simple principle and better accu-
racy. The system was compared with other FIA systems using BTB as
2376 L. Hong et al.
Table 5. Comparison of the proposed system to other systems using BTB as the
acceptor solution
Flow Linear range Detection limit Determination R.S.D
system (mg l1 NHþ4) (mg l1 NHþ 4) frequency (h1) (%) Ref.
the acceptor solution based on the same reaction and detection system
(Table 5). The method described herein reveals sufficient sensitivity and
detection limit to be applicable to natural waters with low levels of
ammonia and the ammonia-rich wastewater.
REFERENCES
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