Download as pdf or txt
Download as pdf or txt
You are on page 1of 16

This article was downloaded by: [National Sun Yat-Sen University]

On: 19 August 2014, At: 02:28


Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK

Analytical Letters
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lanl20

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

To link to this article: http://dx.doi.org/10.1080/00032710903137442

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.

This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014
Analytical Letters, 42: 2364–2377, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0003-2719 print=1532-236X online
DOI: 10.1080/00032710903137442

FLOW INJECTION ANALYSIS


Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

Determination of Ammonia in Water Using


Flow Injection Analysis with Automatic
Pervaporation Enrichment

Lingcheng Hong,1,2 Xiyan Sun,1 and Linqin Wang1


1
Institute of Environment and Engineering, Hohai University,
Nanjing, China
2
Delin Environmental Instrument Co. Ltd., Nanjing, China

Abstract: An automated ammonia monitoring system has been developed by put-


ting a pervaporation unit in an enrichment cycle used in flow injection analysis
mode. In the proposed system, an enrichment cycle was equipped to enable the
adjustment for the measuring range of ammonium by controlling the duration
of the enrichment circulation. Therefore, the system was capable to determine
ammonia in both the surface water with low ammonia concentration and the
ammonia-rich wastewater with the linear dynamic range of 0.05–15 mg l1 and
15–50 mg l1, respectively. The relative standard deviations were less than 1.9%
and the quantification limit is as low as 0.03 mg l1. The sampling frequency is
8–10 h1.

Keywords: Ammonia, automatic, enrichment cycle, flow injection analysis,


pervaporation unit

Received 14 February 2009; accepted 3 June 2009.


The authors are grateful to Delin Environmental Instrument Co. Ltd., for
financial and technological support.
Address correspondence to Xiyan Sun, Institute of Environment and
Engineering, Hohai University, Nanjing, China 210098. E-mail: xiyan-607@
163.com

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-
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

try, Berthelot reaction, distill-titration method, electrode method, etc. The


sensitivity of the Nessler reagent is too low for many applications (Mana
and Spohn 2000). Furthermore, there is a present tendency to disregard it
in view of the high concentration of mercury involved (Wen, Fan, and
Yuan 2005). As for the method of Berthelot reaction, the hypochlorite
is not a stable reagent, which must be prepared everyday, and is, therefore,
not suitable for an automatic on-line analysis system where reagents need
to last for a week or longer. In the distill-titration method, samples are first
distilled to vaporize the ammonia to meet with boric acid as the receiving
agent and methyl red-methylene blue as the indicator. This method is quite
complicated and time consuming. Surfactants and unstable electrodes can
affect the results when utilizing the electrode method based on direct
potentiometry (Wen et al. 2005). All these methods involved manual
collection and were time-consuming. With the seriousness of the pollution,
it is important to establish a rapid, simple, and reliable method for the
on-line analysis of ammonia. Industrial process and effluent streams are
increasingly being monitored using automatic on-line analyzers (Tryzell
and Karlberg 1995; Andrew, Worsfold, and Comber 1995).
Flow injection analysis (FIA) is a technique well suited to automated,
on-line industrial process analysis, because of it’s rapidity, robustness,
simplicity, versatility, and minimal capital=operating costs. The potential
and application of FIA for on-line process monitoring has been discussed
(Andrew et al. 1995; Aleksey et al. 2005; Wang et al. 2003; 2000; Van Son,
Schothorst, and den Boef 1983; Cerd a et al. 1995; Cling, Worsfold, and
Sweeting 1988).
Pervaporation technique was applied to flow injection systems and
was frequently used for the determination of volatile analytes in complex
samples (Tryzell and Karlberg 1995; Wang et al. 2003; 2000; Papaef-
stathiou and Luque de Castro 1997; Luque de Castro and Papaefstathiou
1998). No pretreatment of samples is needed, and continuous evapora-
tion is combined with the gas diffusion through a gas-permeable
membrane, which separates volatile composition from other materials
that could affect the analysis results. In addition, deterioration in the
permeability of the pervaporation membranes can be avoided, since the
donor stream does not contact the membrane (Wang et al. 2003; 2000;
2366 L. Hong et al.

Papaefstathiou and Luque de Castro 1997; Luque de Castro and


Papaefstathiou 1998). The pervaporation technique has been largely
applied in the analysis of ammonia (Wang et al. 2003; 2000; Olivereira
et al. 2007). However, like most FIA systems, this method presents some
limitations such as relatively high reagent consumption, larger waste
generation, and limited sensitivity due to the incomplete evaporation.
In this work, an enrichment cycle was employed. The injected sample
and NaOH donor solution were mixed and circulated repeatedly in the
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

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

2.1. Reagents and Solutions

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

2.2. The FIA Manifold

The FIA system (Fig. 1) consisted of an injector, two peristaltic pumps,


two specially designed rotary valves, a pervaporation unit, and a photo-
metric detector with a 30 mm flow-through cell. Delin Environmental
Instrument Co. Ltd. offered all components. As shown in Fig. 1, P1 is
an injector, which could give a persistent acceptor flow in the detecting
process. P2 and P3 are two peristaltic pumps. The function of P2 is to
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

drive the donor solution steadily to circulate in the enrichment cycle


and P3 draws the sample solution to the brim of the sample channel.
The pervaporation unit and the detector were put in a semiconductor
thermostatic device, which was incorporated into the flow injection
manifold whenever temperature control was needed.
All reactors and injection loops were made of polytetrafluoroethy-
lene (PTFE) tubing of 1.25 mm i.d. The enrichment coil consists of the
mixing coil (400 cm) and the sampling coil (82 cm).
In this FIA system, there was no commuted flow, so the unbalanced
distribution between the converging streams caused by pressure fluctuations
could be avoided. Thus, the results of the detection are more reproducible.

2.3. Procedures of the Operating System

In the flow injection system, a programmable logic controller (PLC,


Matsushita FP-X) was used to control all the components of the system,
to convert the analogue output signal from the photometric detector to

Figure 1. Scheme of the pervaporation enrichment flow-injection system.


2368 L. Hong et al.

digital, and to calculate and record all the data. The detailed flow
procedure was as follow:

1. Washing and injecting sample: V1 and V2 are adjusted to A status, P1


starts to inhaust BTB solution, and P2 starts to propel the NaOH
solution to wash the flow channel for 90 s. At the same time, start
P3 to propel the sample solution to wash and brim the sampling coil
for 30 s at the speed of 6.5 ml min1.
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

2. Enriching ammonia gas: V1 and V2 are adjusted to B status, thus the


sampling coil is switched into the enrichment cycle. First, start P1 to
pull out BTB solution and when the detected photo voltage is steady,
P1 is stopped and the photo voltage is recorded as baseline. Next, P2
starts to propel the solution in the enrichment cycle. The sample and
NaOH are mixed thoroughly in this cycle. The generated ammonia gas
is transferred through the semi-permeable membrane continuously
and is absorbed by the BTB acceptor flow, which is stopped during
this process.
3. Detecting: When P2 stops for 60 s, P1 starts to expel the BTB solution
steadily to the reaction coil and ultimately into the photometric
detector, PLC will read the peak height and calculate the absorbance
automatically. When the photo voltage returns to the level of baseline,
one detection process is finished and the system will return to the
status of step (1) to start the next determination.

2.4. The Pervaporation Unit

The homemade pervaporation unit is a gas diffuse device with two


separated rectangular perspex blocks (40  36  32 mm3), held together
by four stainless steel screws (Fig. 2). The upper block was carved with

Figure 2. Pervaporation unit.


Pervaporation Enrichment 2369

a zigzag flow channel configuration of 1.0 mm i.d. (Olivereira et al. 2007)


with an 80 ml of the total volume. The donor chamber (20  10  8 mm3)
was machined on the lower block. A quadrate semi-permeable PTFE
membrane (pore size of 0.45 mm, purchased from Far East Fluorine
Plastic Product Co. Ltd., China) was fixed between the two blocks.
The donor chamber was designed to the depth (8 mm deep) needed in
order to obtain a headspace above the donor solution, thus the
semi-permeable membrane, which will not be deteriorated or blocked
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

by the impurity of samples, would make the longevity a reality. All


perspex surfaces were polished to allow visual observation of the liquid
level in the donor chamber.

3. RESULT AND DISCUSSION

3.1. Optimization of Chemical Composition and Flow Parameters

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.

3.1.1. Chemical Composition of the Acceptor and the Donor Streams

The pH and concentration of BTB acceptor solution was studied first. A


standard solution containing 30 mg l1 NHþ 4 was used to test the response.
The concentration of BTB in the acceptor solution was studied in a range
of 20–100 mg l1. A 36% increase on sensitivity was observed up to
50 mg l1. For higher concentration, the sensitivity decreased, therefore,
an upper concentration of 50 mg l1 was selected. The pH of the indicator
solution was studied in a range of 6.0 to 7.6. The highest sensitivity was
obtained using a pH of 6.5–6.7. As the pH value increased, the color of
acceptor solution deepened. In order to avoid memory effect of color in
the loop, a pH 6.5 acceptor solution was selected for further experiments.
The concentration of NaOH donor solution was investigated within
the range of 0.01–0.1 mol l1. The results showed obvious increases in the
analytical signal from 0.01 to 0.02 mol l1 and a slight increase above
0.02 mol l1, so we chose 0.02 mol l1 as the donor concentration.

3.1.2. The Optical Path Length in Photometric Detector

To improve the sensitivity of the photometric detector, the flow-through


cells with the path length of 20 mm, 30 mm, 40 mm and 50 mm were
2370 L. Hong et al.

tested. The highest sensitivity was achieved using a flow-through cell of


30 mm path length.

3.1.3. Flow Rates for Donor and Acceptor Solutions

The study for flow rate of the proposed system was mainly focused on
two parts: the donor enrichment cycle and the acceptor stream.
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

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.

3.1.4. Sample Volume

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.

3.1.5. Mixing Coil Length

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).

3.2. The Temperature in the Pervaporation Unit

Temperature of the flow injection system considerably influences the


evaporation and diffusion of ammonia in the pervaporation system,
Pervaporation Enrichment 2371

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
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

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.

3.3. The Duration of Enrichment Cycle

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.

Table 1. Flow system parameters optimized in present study


Parameter Range studied Optimal value

NaOH concentration (mol l1) 0.01–0.1 0.02


BTB concentration (mg l1) 10–100 50
PH value 6.0–7.6 6.5
Sample volume (ml) 0.20–3.5 1.0
Mixing coil length (cm) 100–400 400
Temperature ( C) 10–80 25
2372 L. Hong et al.
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

Figure 3. Effect of the duration time of the circulation on the optimized linear
detection range and the best R2.

The repeatability of the method was evaluated by comparing the


slopes of the analytical curves obtained under the same working condi-
tions over a period of 2 weeks. In this period the slope did not change
by more than 5% thus showing that the repeatability of the proposed
enrichment method was excellent.

3.4. BTB Solution’s Stop Period

Previous literature (Cerd a et al. 1995; Olivereira et al. 2007) indicated


that the stopped flow approach would improve the diffusion efficiency,
and stop periods played a decisive role in the extent of absorption.
In our system, the stop periods of the BTB solution, which refer to
the time between the enrichment cycle finished and P1 started to push
again, can be controlled conveniently by modifying the state of the injec-
tor pump. In this study, it was observed that the peak height increased
with the increasing of the stop period, a maximum was reached at around
60 s, after which peak height leveled off. Therefore, a stop period of
60 s was selected as the complete absorption time.

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.
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

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

Line 1 60 0.05–15 absorbance ¼ 0.0132 þ 0.003X 0.9999


Line 2 90 0.05–20 absorbance ¼ 0.0205 þ 0.003X 0.9987

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

X: the concentration of NHþ


4.
2374 L. Hong et al.

Possible interfering species include metal ions and volatile amines


(International Organization for Standardization 2005). Interference from
metal ions were tested using 10 mg l1 NHþ 4 solution where metal ions
(Kþ, Ca2þ, Naþ, Mg2þ, Fe2þ, Fe3þ, Al3þ, Cu2þ) were added. None of
the studied species (100 mg l1) appeared to interfere since the obtained
relative deviations were less than 5%. The interferences of volatile amines
were studied as they may pass the gas-permeable membrane and change
the pH of the acceptor solution (Oms et al. 1996). Each amine was
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

studied separately by adding a concentration of 2 mg l1 to a standard


solution containing 10 mg l1 of NHþ 4 . The results were as follows: for
ethylamine, methylamine, dimethylamine and trimethylamine, the
relative error is 16.2%, 21.4%, 15.2%, and 14.5%, respectively.

3.6. Analysis of Environmental Samples

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.

Table 3. Sample concentrations and recovery tests


Duration of the Added Founda Recoverya
Sample circulation (s) (mg l1) (mg l1) (%)

Surface water 60 0.0 0.56 –


0.3 0.88 107.0
0.5 1.12 112.0
0.7 1.22 94.3
0.9 1.43 96.7
Industrial effluent 60 0.0 4.18 –
(yellow phosphorus 2.0 6.05 96.6
factory) 4.0 8.21 100.8
6.0 10.28 101.7
8.0 12.35 102.1
Urban sewage 120 0.0 25.64 –
5.0 30.66 100.4
10.0 36.54 109.0
15.0 40.17 96.9
20.0 44.82 95.9
a
n ¼ 9.
Pervaporation Enrichment 2375

Table 4. Results for ammonium determination (n ¼ 6)


Proposed Nessler Difference
Sample method (mg l1) method (mg l1) (mg l1)

SW-1 0.74 0.80 0.06


SW-2 4.30 4.23 þ0.07
SW-3 5.17 6.04 0.87
SW-4 5.41 5.91 0.50
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

WW-1 6.81 7.03 0.22


WW-2 7.11 6.80 þ0.31
WW-3 22.1 21.5 þ0.60
WW-4 15.9 14.3 þ1.60

Difference ¼ observed value (proposed)—expected value (conventional).


SW ¼ surface water; WW ¼ waste water.

The pretreatment of the turbid environmental samples was needed to


achieve the optimal measurements and eliminate the possibility of flow
path jam. Wastewater samples with granular impurity should be filtered
through qualitative filter paper or 0.45 mm filter membrane (Wang 2007).
No treatment is necessary for clean tap water and rain water samples.
To assess the accuracy of the methodology, recovery experiments
were conducted by multiple point standard addition with a known
concentration of ammonia. Recoveries close to 100% were achieved in
the four concentration levels (Olivereira et al. 2007) for all the samples
listed in Table 3.
Manual laboratory experiments were carried out to confirm the
reliability of the enrichment flow-injection method applied to environ-
mental samples. Details of the monitoring performance compared with
the Nessler method are listed in Table 4. The results are in good
agreement to each other (t0.05,7 ¼ 1.90, t ¼ 0.436  t0.05,7).

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.

FIA 0.05–50 30 10=8 1.9 –


FIA 1.3–128 770 12 3.4 4
FIA 0.2–20 100 11 3.0 7
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

FIA 0.018–1.8a 18 100 3.0 8


FIA 0.50–60 300 NA 2.0 9
FIA 0–6.4 17 NA 2.1 10
MCFIA 0.05–1.0 42 20 1.5 13

NA: not available.


a
Based on a theoretical model.

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
Andrew, K. N., P. J. Worsfold, and M. Comber. 1995. On-line flow injection
monitoring of ammonia in industrial liquid effluents. Anal. Chim. Acta
314: 33–43.
Cerdà, A., M. T. Oms, R. Forteza, and V. Cerdà. 1995. Evaluation of flow
injection methods for ammonium determination in wastewater samples. Anal.
Chim. Acta 311: 165–173.
Clinch, J. R., P. J. Worsfold, and F. W. Sweeting. 1988. An automated spectro-
photometric field monitor for water quality parameters. Anal. Chim. Acta
214: 401–407.
Gamiz-Gracia, L., and M. D. Luque de Castro. 1999. Determination of formal-
dehyde in liquid, solid and semisolid pharmaceuticals and cosmetics by flow
injection-pervaporation. Analyst. 124: 1119–1121.
International Organization for Standardization, ISO 11732, 2005.
Luque de Castro, M. D., and I. Papaefstathiou. 1998. Analytical pervaporation:
A new separation technique. Trends. Anal. Chem. 17: 41–49.
Mana, H., and U. Spohn. 2000. Rapid and selective determination of ammonium
by fluorometric flow injection analysis. Fresenius J. Anal. Chem. 366: 825–829.
Moskvin, A. L., and L. N. Moskvin. 2005. Water and aqueous environments:
on-line chemical analysis, problems and solutions. Russ. Chem. Rev. 74: 145–152.
Oliveira, S. M., T. I. M. S. Lopes, I. V. Toth, and A. O. S. S. Rangel. 2007. A
multi-commuted flow injection system with a multi-channel propulsion unit
Pervaporation Enrichment 2377

placed before detection: Spectrophotometric determination of ammonium.


Anal. Chim.Acta 600: 29–34.
Oms, M. T., A. Cerdà, A. Cladera, V. Cerdà, and R. Forteza. 1996. Gas diffusion
techniques coupled sequential injection analysis for selective determination of
ammonium. Anal. Chim. Acta 318: 251–260.
Papaefstathiou, I., and M. D. Luque de Castro. 1997. Hyphenated pervaporation—
solid-phase preconcentration—gas chromatography for the determination of
volatile organic compounds in solid samples. J. Chromatogr. 779: 352–359.
Downloaded by [National Sun Yat-Sen University] at 02:28 19 August 2014

Papaefstathiou, I., M. D. Luque de castro, and M. Valc arcel. 1996.


Flow-injection=pervaporation coupling for the determination of sulphide in
Kraft liquors. Fresenius J. Anal. Chem. 354: 442–446.
Tryzell, R., and B. Karlberg. 1995. Efficiency and response studies on gas diffu-
sion manifolds in flow-injection systems. Anal. Chim. Acta 308: 206–213.
Van Son, M., R. C. Schothorst, and G. den Boef. 1983. Determination of total
ammoniacal nitrogen in water by flow injection analysis and a gas fusion
membrane. Anal. Chim. Acta 153: 271–275.
Wang, C. 2007. On some points for attention in the determination of ammonia.
J. Changchun Universit. 17: 97–99.
Wang, L., T. J. Cardwell, R. W. Cattrall, M. D. Luque de Castro, and S. D.
Kolev. 2000. Pervaporation-flow injection determination of ammonia in the
presence of surfactants. Anal. Chim. Acta 416: 177–184.
Wang, L., T. J. Cardwell, R. W. Cattrall, M. D. Luque de Castro, and S. D.
Kolev. 2003. determination of ammonia in beers by pervaporation flow injec-
tion analysis and spectrophotometric detection. Talanta 60: 1269–1275.
Wen, L., C. Fan, and Z. Yuan. 2005. Ammonia-nitrogen analysis method in
China environment monitoring. Environmental Monitoring in China 21: 28–32.

You might also like