Our reference: ARABJC 320 P-authorquery-v8

AUTHOR QUERY FORM

Journal: ARABJC Please e-mail or fax your responses and any corrections to:

E-mail: corrections.esch@elsevier.sps.co.in

Article Number: 320 Fax: +31 2048 52799

Dear Author,
Please check your proof carefully and mark all corrections at the appropriate place in the proof (e.g., by using on-screen annotation in the PDF file) or
compile them in a separate list. To ensure fast publication of your paper please return your corrections within 48 hours.
For correction or revision of any artwork, please consult http://www.elsevier.com/artworkinstructions.

Any queries or remarks that have arisen during the processing of your manuscript are listed below and highlighted by flags in the proof. Click on the ‘Q’
link to go to the location in the proof.

Location in Query / Remark: click on the Q link to go

article Please insert your reply or correction at the corresponding line in the proof

Q1 The article title has been modified. Please check, and correct if necessary.
Q2 Please check the telecommunication data.
Q3 Please check the edit(s) made in the sentence ‘‘Moreover ....health ‘‘, and correct if necessary.
Q4 Please check the edit(s) made in the sentence ‘‘The analyzed...’’, and correct if necessary.

Q5 Please check the edit(s) made in the sentence ‘‘To 80C...’’, and correct if necessary.
Q6 Please check the edit(s) made in the sentence ‘‘Despite ....H2SO4 .’’, and correct if necessary.
Q7 This section comprises references that occur in the reference list but not in the body of the text. Please position each reference in the
text or, alternatively, delete it. Any reference not dealt with will be retained in this section.
 ARABJC 320 No. of Pages 9
17 February 2011
Arabian Journal of Chemistry (2011) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

3 Q1 Spectrophotometric determination of formaldehyde

4 based on the telomerization reaction of tryptamine
5 Nael G. Yasri *, Hasan Seddik, Maha A. Mosallb

6 Q2 Department of Chemistry, Faculty of Science, University of Aleppo, Aleppo, Syria

Received 8 December 2010; accepted 2 February 2011

KEYWORDS Abstract A simple and sensitive spectrophotometric method for the determination of formalde-
Formaldehyde; hyde FA in different samples using tryptamine TA in a sulfuric acid medium was developed. A trace
Tryptamine; amount of sodium nitrite was added to enhance the production of a red violet colored product
Spectrophotometery; exhibiting an absorbance maximum at 558 nm. Beer’s Law is obeyed for 0.80–23.00 lg mL 1 FA
Environmental samples (r = 0.999), the recoveries are within the range of 96.25–100.66%, with percent relative standard
deviations ranging from 1.02% to 2.73%. No interference was detected from commonly existing
contaminates in the liquid samples e.g. phenol, aminoacids, sugars and related compounds. The
method was applied successfully for the determination of formaldehyde in various environmental
samples, such as rain water, wood products, and total cigarette smoke.
11 ª 2011 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.

12 1. Introduction building materials and consumer products (Wakefield, 2008; 18

Priority Existing Chemical Assessment, 2006). 19
13 Formaldehyde (FA), HCHO, is the most commonly found Due to the high solubility (Heimlich, 2008), formaldehyde 20
14 aldehyde in the environment (Liteplo et al., 2002). In general, is found in natural rain, clouds, fog and steam, which paves 21
15 formaldehyde enters the environment from natural sources, its way as a pollutant. Moreover, the broad biological proper- Q3 22
16 forest fires and from direct human pollution sources, such as ties place formaldehyde among the significant industrial haz- 23
17 fuel combustion, industrial on-site uses and off gassing from ardous substances, with high impact on human health 24
(Heimlich, 2008; Liteplo et al., 2002; Programme on Chemical 25
* Corresponding author. Tel.: +963 933 685834. Safety Formaldehyde Health and Guide, 1991). In air, formal- 26
E-mail address: naelyasri@hotmail.com (N.G. Yasri). dehyde is considered as immediately dangerous to life and 27
health at a concentration level of 24 mg m 3, and exposure 28
1878-5352 ª 2011 King Saud University. Production and hosting by limit of 90 g m 3 (Institute for Occupational Safety and 29
Elsevier B.V. All rights reserved. Health, 1994). 30
Recently, there has been a tendency to determine the con- 31
Peer review under responsibility of King Saud University. centration of formaldehyde in the environmental samples for 32
doi:10.1016/j.arabjc.2011.02.005 pollution control purposes and to provide strict regulatory 33
restriction on the usage of consumer products. Therefore, a 34
Production and hosting by Elsevier simple, rapid and highly sensitive determination method is ur- 35
gently required (Heimlich, 2008). 36

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
2 N.G. Yasri et al.

37 Sensitive methods for formaldehyde determination include chased from Merck and 5% (w/v) chromotropic acid from Mal- 93
38 GC (Bianchi et al., 2007; Del Barrio et al., 2006; Reche linckrodt Chemical was freshly prepared in bidistilled water. 94
39 et al., 2001; Velikonj et al., 1995; Davydova et al., 1986), vol-
40 tammetry (Zhao et al., 2006), fluorometry (Zhang and Tian, 3. Method 95
41 2004; Li et al., 2007), LC and HPLC (Possanzini and Di Palo,
42 2003; Witthauer et al., 1999; Isakau et al., 2009; Fu Liu et al., 3.1. Spectrophotometric calibration curve 96
43 2005; Huber and Fresenius, 1981; Chen et al., 2008). However,
44 spectrophotometric based methods (Teixeira et al., 2004; Feng Proper volumes of the FA working standard solution were 97
45 et al., 2004; Gigante et al., 2004; Tian et al., 2004; Cui et al., transferred to the stoppered test tubes to cover the concentra- 98
46 2007; Jagadeesan and Gupta, 1979; Li et al., 2008; Gibson tion range of 0.80–23.00 lg mL 1. The FA solution was di- 99
47 et al., 2008; Mohamed et al., 2008; Guo et al., 2006; Pinheiro luted with water to 4.0 mL, the test tubes were replaced in 100
48 et al., 2004) are among the relatively low-cost, simple and sen- the water bath at a constant temperature of 25 C, followed 101
49 sitive methods and are very popular. These methods are based by the addition of 4.0 mL concentrated H2SO4, the tempera- 102
50 on the reaction of formaldehyde with reagents, such as Schiff’s ture was allowed to stabilize then 1.0 mL of the working TA 103
51 reagent (Gibson et al., 2008), p-phenylenediamine (Mohamed solution was added followed by 1.0 mL sodium nitrite solu- 104
52 et al., 2008), chromotropic acid (Gigante et al., 2004), brilliant tion. All test tubes were then capped and left in the water bath 105
53 cresyl blue (Guo et al., 2006) and fluoral P (Pinheiro et al., for 35 min to ensure complete color development. A calibra- 106
54 2004). tion graph was prepared by recording the absorbance of the 107
55 The present work reports a simple, sensitive and accurate resulting solutions at 558 nm against a similarly prepared re- 108
56 spectrophotometric method for the determination of formalde- agent blank. All measured solutions were prepared in 109
57 hyde in aqueous samples. The method is based on the forma- triplicates. 110
58 tion of a colored telomere from the reaction of formaldehyde
59 with indol-3-ethylamine (knows as tryptamine; TA), in a sulfu- 3.2. Formaldehyde determination in rain water 111
60 ric acid medium. The method was optimized for the determina-
61 tion of unknown levels of formaldehyde in samples of Some portions of countryside rain water (Aleppo City, Syria) 112
62 rainwater, wooden products, and total cigarette smoke. were collected at two different time periods; each portion 113
was about 100 mL volume. The first collection was in the first 114
63 2. Material and methods autumn rainfall in the second week of September 2009 and the 115
second sample was collected from the same place after about 116
64 2.1. Apparatus one month. The collected rain water samples were immediately 117
filtered through a 0.45 lm membrane filter from which a vol- 118
65 A Jasco V-630 spectrophotometer with 1.0 cm quartz cell was ume of 100 mL was heated, with continuous stirring, in a water 119
66 used for spectrophotometric measurements. An HPLC system bath at 80 C for 10 min (Mohamed et al., 2008), in these con- 120
67 (Merck-Hitachi) equipped with a diode array detector L-2455, ditions, the volatile acetaldehyde was expelled, and at the same 121
68 quaternary pump L-2200 and column temperature regulator time they have a little effect on FA (recoveries of FA P97%), 122
69 L-2350 was used. The analytical column used was a RP8 HI- which begin to drift with water vapor at P90 C (Mohamed 123
70 BAR (250 · 4.6 mm ID 10 lm) from Merck. The chromato- et al., 2008). The solution was left for a few minutes to cool 124
71 graphic system was eluted by (45:55 v/v) acetonitrile:water after which bidistilled water was added to the volume to re- 125
72 solution as a mobile phase, with 20 lL injection volume at a place any evaporation. 126
73 flow rate of 1.0 mL min 1, and a detector set at 345 nm wave- In order to determine the low levels of FA a preconcentra- 127
74 length. A digital Orion Research Model 601 analyzer provided tion procedure was performed by subjecting the resulting solu- 128
75 with an Ingold U455 electrode was used for pH measurements. tion to a crystallization process with bisulfite. This was 129
proceeded as follows: 5 g sodium bisulfite was added to 130
76 2.2. Reagents and chemicals 100 mL of the rain water, then the mixture was kept in an 131
ice bath for one hour (ensuring a complete FA and bisulfite 132
77 Reagent-grade chemicals used were of the highest purity avail- reaction), after which an accurate volume of 50 mL ethanol 133
78 able from their sources. A stock FA solution of 1000 lg mL 1 (95%) was added without stirring (the aqueous: ethanol ratio 134
79 was prepared by diluting a volume of 2.5 mL (37%) formalde- was 2:1 (v/v)). The mixture was then refrigerated (at 4 C) 135
80 hyde solution FA (SCP, super chemical produces) to 1000 mL for 30 min which lead to the formation of crystals from bisul- 136
81 with bidistilled water and standardized using the sulfite method fite addition compound. The crystals were then filtered using 137
82 (Annual Book of American Society for Testing and (ASTM) 0.45 lm membrane filter, and the filtrate was discarded. The 138
83 Standards, 1979). FA working standard solutions of 100 and crystals were kept at room temperature for solvent evapora- 139
84 10 lg mL 1 were prepared daily from the stock standard solu- tion, followed by the dissolution of the dry crystals with suit- 140
85 tion by appropriate dilution. Tryptamine reagent TA able volume of 0.05 mol L 1 sulfuric acid, making the final 141
86 5 · 10 2 mol L 1 was prepared by dissolving 0.817 g (98% pur- FA concentration within the standard linear range of the sug- 142
87 ity, Merck chemicals) tryptamine in 1% H2SO4 and then com- gested method. A 3 mL volume of the resulting solution was 143
88 pleting the volume to 100 mL using the same solvent. Sodium used in the proposed method for FA determination. 144
89 nitrite solution 2 · 10 3 mol L 1 was prepared by dissolving A separate FA preconcentration study with bisulfite crys- 145
90 0.139 g of 99% sodium nitrite (BDH England), in bidistilled tals was performed to ensure higher recovery for trace FA le- 146
91 water and diluting to 1000 mL in a volumetric flask. Sulfuric vel. The study included ethanol to water ratio, bisulfite 147
92 acid (98%), 2,4-dinitrophenylhydrazine (DNPH) were pur- quantity, and FA concentration. 148

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
Spectrophotometric determination of formaldehyde based on the telomerization reaction of tryptamine 3

0.8
0.7
0.6
0.5

A 0.4
0.3
0.2
0.1
0.0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5
Volume of H 2SO4, mL

Figure 1 Effect of sulfuric acid volume on the absorbance values

Scheme 1 Home-made total cigarette smoke collection at 558 nm, Experimental conditions: 2.7 · 10 4 mol L 1 HCHO;
apparatus. 4 · 10 3 mol L 1 TA; 0.3 · 10 4 mol L 1 NaNO2, at 25 C and
wait for 45 min; 10 mL final testing mixture.
149 3.3. Formaldehyde determination in total cigarette smoke
acid concentration to volumes above this range shows good 186
150 A procedure for total cigarette smoke (TSS) collection, de- and nearly constant absorbance values. 187
151 scribed elsewhere (Mohamed et al., 2008), is applied for the For the same acidifying propose, various concentrated 188
152 FA determination in a local cigarette brand (Al Hamra long). acids, such as nitric acid (70%) hydrochloride acid (37%), ace- 189
153 The method in brief is as follows; a simple smoking apparatus tic acid (99%) and phosphoric acid (85%) were individually 190
154 was constructed as shown in Scheme 1, each trap (100 mL tested using a volume of 4 mL from each acid and using the 191
155 capacity) contained about 35 mL of chilled water. Just after same experimental conditions. The results show, no color 192
156 smoking three cigarettes, the two trap solutions were com- development in the solution by using the above mentioned 193
157 bined, filtered through a 0.45 lm membrane filter and heated, acids. An addition of 0.5 mL of 1.0 · 10 2 mol L 1 H2O2 to 194
158 with continuous stirring, in a water bath at 80 C for 10 min, the previously tested phosphoric acid gave a violet colored 195
159 Q4 to expel volatile acetaldehyde (Mohamed et al., 2008). The product with a broad peak at 566 nm (Fig. 2). The color devel- 196
160 remaining solution was then diluted to 250 mL in a volumetric opment using H3PO4 and H2O2 took approximately 3 h to 197
161 flask and sample aliquots of 3 mL were promptly analyzed. establish a stable colored product. Despite a low potential haz- Q6 198
ard of H3PO4 as compared with H2SO4, a longer period of 199
162 3.4. Formaldehyde determination in wood products time taken by the former to develop a colored product lead 200
to the preference of the cautious use of H2SO4. 201
163 FA in wood products, such as in medium density fiberboard
164 (MDF) and chipboard, was determined by applying the sug-
165 Q5 gested method. To each 1 g ground sample of MDF, chip-
166 board was added intermittently as very small pieces, 50 mL
167 of bidistilled water was added and the mixture was agitated
168 using an ultrasound bath for 10 min at 80 C. This ensured
169 the removal of acetaldehyde if present (Mohamed et al.,
170 2008), and the complete dissolution of free FA from the sam-
171 ple (British Standards Institution, 1995), total FA, however,
172 could be obtained by soaking the sample in a sulfuric acid
173 medium, (Chrastil and Reinhardt, 1986). The solution was
174 then left for a few minutes to cool, filtered then a 3 mL volume
175 of the filtrate was used in the proposed method for FA
176 determination.

177 4. Results and discussion

178 4.1. Effect of various concentrated acids

179 The addition of FA with TA, in the sulfuric acid medium,

180 developed a violet colored product with a clear absorbance
181 maximum at 558 nm. The effect of various volumes of concen-
182 trated sulfuric acid was studied using 3 mL of 8 lg mL 1 Figure 2 Absorption spectra show the effect of; (1) sulfuric acid
183 (2.7 · 10 4 mol L 1) FA concentration. The results, (Fig. 1), with sodium nitrite using 8 lg L 1 HCHO, (2) sulfuric acid using
184 show that the increases of acid volume, within the range 0.5– 8 lg L 1 HCHO, (3) phosphoric acid using 8 lg L 1 HCHO, (4)
185 4.0 mL, show an increase in the absorbance. Increasing the sulfuric acid with sodium nitrite using 1 lg L 1 HCHO.

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
4 N.G. Yasri et al.

202 4.2. Effect of sodium nitrite concentration and other oxidants reaction time and a maximum was reached after 6 h. Alterna- 224
203 material tively, the presence of 2 · 10 4 mol L 1 NaNO2 enhanced the 225
reaction rate with a nearly stable colored product formation 226
204 It has been noticed during preliminary testing experiments that after 35 min that remained for 6 h. 227
205 the addition of trace amount of oxidants, e.g. H2O2 and Fe3+ It has been known that NaNO2 in acidic solution gives ni- 228
206 [as Fe2(SO4)3], increases the reaction speed with no effect on trous acid which decomposed with the evolution of nitrogen 229
207 the total absorbance value. Adding a trace amount of sodium oxides, but at these reaction conditions of temperature and or- 230
208 nitrite to the sulfuric acid media containing FA and TA, how- der of material addition (FA, H2SO4, TA, and then NaNO2), 231
209 ever, caused an increase in both, the absorbance (Fig. 2) and in the absorption and the reaction speed were surprisingly in- 232
210 the reaction speed. creased, even at a temperature reaching 25 C. 233
211 The effect of NaNO2 concentration was studied within the It is suggested that the presence of NaNO2 could enhance 234
212 range of 0.5 · 10 5–1.4 · 10 3 mol L 1. The results (Fig. 3) the formation of a hydrated semi oxidized species of formalde- 235
213 show that the absorbance increased rapidly with increasing hyde that have more efficiency to condense with indole and its 236
214 NaNO2 concentration with a maximum at 2 · 10 4 mol L 1. derivatives. 237
215 Further increases in the NaNO2 concentration to a value more
216 than 9 · 10 4 mol L 1, may lead to a decrease in the absorp- 4.3. Constitution of the colored product 238
217 tion value. Thereafter, a concentration of 2 · 10 4 mol L 1
218 of NaNO2 was adopted for further experiments. The nature of the binary colored product (FA-TA) was deter- 239
219 Taking into consideration the color development period, mined by performing two studies, the first using continuous 240
220 the absorbance of the color was monitored for 8 h both in variation method (Likussar and Boltz, 1971). In this method, 241
221 the absence and in the presence of NaNO2. In the absence of a series of solutions were prepared, with that the concentration 242
222 sodium nitrite, the result (Fig. 4) shows that the colored prod- of FA plus TA were held constant at 1.0 · 10 3 mol L 1. A 243
223 uct formation increased gradually during the first 3 h of the graph was prepared by plotting absorbance against the ratio 244
[FA]/[FA] + [TA]. The result of applying this method, 245
(Fig. 5), indicated that the (TA:FA) ratio is 2:1. 246
1.1
The second study used a molar ratio method (Meyer and 247
1.0 Ayres, 1957), this was performed by increasing the TA concen- 248
0.9 tration within the range of (1.3 · 10 3–2.1 · 10 4) mol L 1, for 249
the formation of the colored product with constant FA con- 250
0.8
A centration of 2.7 · 10 4 mol L 1. 251
0.7

0.6

0.5 0.4

0.4
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 0.3
Concentration of NaNO 2 mol.L-1, ×10-4
A 0.2
Figure 3 The effect of sodium nitrite concentration on the
absorbance values at 558 nm. Experimental conditions: HCHO
2.7 · 10 4 mol L 1; TA 5 · 10 3 mol L 1; 4 mL H2SO4 (98%); at 0.1
25 C and wait for 30 min; 10 mL final testing mixture.
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
[FA]/[FA] + [TA]
1.2
Figure 5 Continuous variation method for FA-TA colored
1 production at 558 nm. Experimental conditions: 2 · 10 4 mol L 1
0.8
NaNO2; 4 mL H2SO4 (98%); at 25 C and wait for 30 min; 10 mL
final testing mixture.
A 0.6
0.4

0.2
NH 2 NH2 NH 2
0
0 1 2 3 4 5 6 7 8 9 CH 2 CH2 CH 2
CH 2 CH 2 CH 2
Time, hour O +
+ C H CH2
2
Figure 4 The absorbance variation at 558 nm during 8 h time in N H H - H2O N N
the absence and in 2.7 · 10 4 mol L 1 HCHO: the present of H H H
2 · 10 4 mol L 1 NaNO2. Experimental conditions:
5 · 10 3 mol L 1 TA; 4 mL H2SO4 (98%); at 25 C; 10 mL final Scheme 2 Possible telomerisation reaction of formaldehyde with
testing mixture. tryptamine.

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
Spectrophotometric determination of formaldehyde based on the telomerization reaction of tryptamine 5

252 The result shows rapid increases in the absorbance with

Table 1 Sensitivity and regression parameters.
253 increasing TA concentration (maxima at 5 · 10 3 mol L 1),
254 with an intersection point of 2 on the [TA]/[FA] axes versus Parameter Proposed method
255 absorption. Hence, according to these results and the Hop- kmax (nm) 553
256 kins-Cole biochemical reaction (Berg et al., 2006), which is Linear range (lg mL 1) 0.80–23.00
257 used for qualitative determination of tryptophan, the composi- Molar absorptivity (e) (L mol 1 cm 1) 2972.2
258 tion of the binary colored product formed TA-FA, may be ex- Sandell sensitivitya (lg cm 2) 0.1
259 pressed as 2:1 (Scheme 2). Limit of detection (LOD) (ng mL 1) 290
Limit of quantification (LOQ) (lg mL 1) 0.88
Intercept (a) 0.003
260 4.4. Effect of temperature
Slope (b) 0.109
Regression coefficient (r) 0.999
261 The effect of temperature was studied within the range 5– a
262 95 C. In these set of experiments the mixture was prepared Limit of determination as the weight in lg mL 1 of solution
which corresponds to an absorbance of A = 0.01 measured in a
263 in test tubes placed in a water bath at a defined temperature
cuvette of cross-sectional area 1 cm2 and l = 1 cm. Y = a + b X,
264 for a period of 30 min after which the ambient temperature where Y is the absorbance, X is the concentration in lg mL 1, a is
265 was maintained. the intercept, b is the slope.
266 The result (Fig. 6), demonstrated that the colored product
267 formed at a temperature in the range of 5–25 C exhibited
268 nearly stable absorbance, whereas increasing the temperature
minations and b is the slope of the calibration curve (Miller 289
269 within the range of 26–35 C showed a decrease in the absor-
and Miller, 1993). 290
270 bance (around 2%). Increasing the temperature within the
The precision and accuracy were assessed according to the 291
271 range of 40–90 C, caused the absorbance to decrease dramat-
IUPAC recommendations (Miller and Miller, 1993) by analyz- 292
272 ically with the dissociation of the colored product, resulting in
ing 0.08, 0.10, 0.30, 0.50, 0.80, 1.0, 5.0, 10.00, 15.00, 18.00, 293
273 uncontrollable conditions of the reaction. Thus, the method
20.00, and 23.00 lg mL 1 FA in aqueous solutions (Table 2). 294
274 should be performed at a temperature less than or equal to
The relative accuracy R% was within the range of 96.25– 295
275 25 C.
100.60%, with RSD% 62.73%, indicating a good accuracy 296
with high precision of the method. The reproducibility of the 297
276 4.5. Method validation
method also known as the inter precision was evaluated by 298
performing replicate analyses solution over a period of five 299
277 Beer’s Law is obeyed within FA concentration range of (0.80–
days. The inter day RSD values were less than or equal to 300
278 23.00) mg L 1 (r = 0.999). The calibration graph is described
3.90% reflecting the usefulness of the method in routine 301
279 by the equation: Y = bX + m, obtained by the method of least
analysis. 302
280 squares (where Y = absorbance, m = intercept, b = slope and
Method robustness was tested by making small incremental 303
281 X = concentration in lg mL 1). Correlation coefficient, inter-
changes in either TA concentration, H2SO4 concentration, 304
282 cept and slope for the calibration data, as well as, the sensitiv-
NaNO2 concentration or temperature. To check the rugged- 305
283 ity parameters such as apparent molar absorptivity and
ness, an analysis was performed by three different analysts 306
284 Sandell’s sensitivity values, the limits of detection and quanti-
and on three different spectrophotometers by the same analyst. 307
285 fication are calculated and summarized in (Table 1). The LOD
The robustness and the ruggedness were checked at three dif- 308
286 and LOQ were calculated according to the same guidelines
ferent concentrations of FA. The intermediate precision, ex- 309
287 using the formulae: LOD = 3.3 SD/b and LOQ = 10 SD/b,
pressed as RSD percent, which is a measure of robustness 310
288 where SD is the standard deviation of five reagent blank deter-
and ruggedness was within the acceptable limits as shown in 311
the Table 3. 312

4.6. Interference study 313

1.2
The influence of various ions, some of organic and inorganic 314
1.0 compounds, commonly found with FA in the aqueous envi- 315
ronment was examined within the concentration range of 15– 316
0.8
1000 lg mL 1. A relative error of ±5% on the concentration 317
A 0.6 of FA was considered tolerable. No interference within the 318
testing range of concentration was observed from sugars, such 319
0.4 as glucose and fructose, ketones as acetone, aminoacids as leu- 320
cine, urea, phenol and the following ions Na+, K+, Ca2+, 321
0.2
Cu2+, Pb2+, Al3+, Fe2+, Zn2+ Cl , and NH4+. However, 322
0.0
1 11 21 31 41 51 61 71 81 91
Temperature,ºC O
C Stir together HO SO3 Na
in ice bath
Figure 6 Effect of temperature on the absorbance values at H H + NaHSO3 C
558 nm. Experimental conditions: 2.7 · 10 4 mol L 1 HCHO; Dilute acid H H
5 · 10 3 mol L 1 TA; 4 mL H2SO4 (98%);
2 · 10 4 mol L 1 NaNO2; 10 mL final testing mixture. Scheme 3 Reaction of bisulfite with formaldehyde.

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
6 N.G. Yasri et al.

Table 2 Evaluation of precision and accuracy for FA determination.a

FA taken (lg mL 1) Intra-day accuracy and precision Inter-day accuracy and precision
1 1
FA lg mL (n = 6) FA lg mL (n = 5)
Found ± SD R% RSD% Found ± SD R% RSD%
0.80 0.77 ± 0.021 96.25 2.73 0.76 ± 0.030 95.62 3.90
1.00 0.97 ± 0.024 97.00 2.47 0.96 ± 0.031 96.50 3.25
5.00 4.95 ± 0.109 99.00 2.20 4.87 ± 0.140 97.40 2.87
10.00 10.02 ± 0.160 100.20 1.60 10.00 ± 0.256 100.00 2.56
15.00 15.10 ± 0.172 100.60 1.14 14.98 ± 0.277 99.87 1.85
20.00 19.84 ± 0.202 99.20 1.02 19.82 ± 0.287 99.10 1.45
23.00 22.70 ± 0.232 98.69 1.02 22.64 ± 0.265 98.43 1.17
a 3 1
The experiments were performed using the optimum conditions of 5 · 10 mol L TA, 4 mL H2SO4 (98%) with final testing mixture
volume at 10 mL (or 39.2% (w/w)) and 2 · 10 4 mol L 1 NaNO2.

Table 3 Robustness and ruggedness expressed as intermediate precision.

FA taken (lg mL 1) Method robustness Method ruggedness
Parameter altered RSD% (n = 3) Inter-analysists RSD% (n = 3) Inter-instruments RSD% (n = 3)
1 a b
TA (mol L ) Acid (w/w%)
1.0 2.12 3.30 2.08 1.89
10.0 2.49 2.98 1.97 1.54
20.0 1.01 1.20 0.98 0.87
Temperature (C)c NaNO2 (mol L 1)d
1.0 2.26 2.71
10.0 2.15 2.51
20.0 1.07 0.97
a
TA concentrations used were (4, 5, 6) · 10 3 mol L 1.
B
Sulfuric acid used were 37.0, 39.2, and 41.0 w/w%.
c
Temperature used were 27, 25, and 23 C.
d
NaNO2 concentrations used were (1.5, 2.0, 2.5) · 10 4 mol L 1.

gested method, a procedure for FA collection from these sam- 331

Table 4 Tolerable concentration of foreign species in the
ples is needed. A modified FA crystallization collection 332
determination of 1.66 · 10 4 mol L 1 FA.
method with sodium bisulfite (NaHSO3) was performed in or- 333
Interference Tolerable limita Tolerable concentration A(I)/Ab der to determine FA. This crystallization method was used to 334
substances ([species]/[HCHO]) (mol L 1) collect formaldehyde from air samples (U.S. Department of 335
4
Acetaldehyde 4.2 6.9 · 10 1.050877 Health and Services, 1994). The method depends on the crys- 336
3
H2O2 24 4.0 · 10 0.948823 tallization of aldehydes and ketones with bisulfite in aqueous 337
Fe3+ 48 7.9 · 10 3
0.935002 media (Scheme 3) (Clayden et al., 2000). This method in brief 338
Ni2+ 54 8.9 · 10 3
0.949123 included the addition of excess of bisulfite to the collected rain- 339
Co2+ 54 8.9 · 10 3
0.940344 water, forming a dissolved compound with FA, and addition 340
a
Defined as ±5% relative error. of ethanol caused the compound to crystallize. 341
b
A(I): absorbance in the presence of interference substances; A: The optimum experimental conditions were determined for 342
absorbance without the interference. the concentrations of FA which are lower than the linearity 343
range of the suggested method (these concentrations were 344
not capable for the analysis by applying the suggested method. 345
323 interference was observed, (Table 4), from acetaldehyde (4.2- Varying the bisulfite quantity for the preconcentration of 346
324 fold) and oxidant material as hydrogen peroxide (24-fold) 0.1 lg mL 1 FA present in 100 mL of bidistilled water, after 347
325 which causes dissociation of the colored product. Interferences which the analysis procedure was performed, reveals higher 348
326 were also observed with ions, such as Fe(III) at 48 fold, Ni(II) recoveries of 95%, with a relative standard deviation RSD of 349
327 and Co(II) up to 54-fold. 2.8%, by using 5 g bisulfite. Increasing the bisulfite quantity 350
up to 8 g/100 mL shows no variation in the recovery value. 351
328 4.7. Preconcentration with bisulfite crystals On the other hand, using 1.0, 2.0, 3.0, 4.0 g/100 mL of bisulfite 352
gives a recovery of 50%, 61%, 79%, and 84%, respectively. 353
329 Considering that the concentration of FA found in samples, For the same preconcentration purpose, and for the same 354
330 such as in rain water, could be less than the limit of the sug- FA concentration, varying the ethanol (95%):water ratio as 355

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
Spectrophotometric determination of formaldehyde based on the telomerization reaction of tryptamine 7

Table 5 Determination of formaldehyde in different testing samples.

a
Sample Proposed method (n = 5) Reference method (n = 5)
No Type HCHO added (lg mL 1) HCHO (found ± S.D)b R%e Found ± S.D (lg mL 1)
1 Rainc – 1.58 ± 0.037 – 1.57 ± 0.050
0.5 2.06 ± 0.032 96.00 F = 1.82
1.5 3.06 ± 0.041 98.67 t = 0.60
d
2 Rain – 0.87 ± 0.024 – 0.85 ± 0.032
0.5 1.36 ± 0.028 98.00 F = 1.77
1.5 2.36 ± 0.039 99.33 t = 1.85
3 TSS – 18.31 ± 0.188 – 18.17 ± 0.202
1 19.31 ± 0.201 100.00 F = 1.15
3 21.28 ± 0.232 99.00 t = 1.66
4 Wood (MDF) – 5.10 ± 0.076 – 5.14 ± 0.103
0.5 5.58 ± 0.095 96.00 F = 1.84
1.5 6.58 ± 0.110 98.66 t = 1.17
5 Wood – 6.50 ± 0.116 – 6.48 ± 0.124
0.5 6.99 ± 0.104 98.00 F = 1.14
1.5 7.98 ± 0.111 98.67 t = 0.38
The value of t (tabulated) at 95% confidence level and for four degrees of freedom is 2.78.
The value of F (tabulated) at 95% confidence level and for four degrees of freedom is 6.39.
a
All of the analytical samples had unknown FA concentration.
b
Expressed for TSS in lg per cigarette, and lg mL 1 the for other samples.
c
Collected from the first rain (countryside, Aleppo city, Syria) and preconcentrated twice.
d
Collected after a period of one month (countryside, Aleppo, Syria) and preconcentrated 10 times.
e
The recovery values for added FA concentrations.

356 0.5:2, 0.75:2, 1:2, 1.25:2, 1.5:2, and 2:2 gives recoveries of FA in the two rain water samples analyzed indicate high levels 387
357 50.2%, 94.5%, 95.3%, 94.7%, 30.7%, and 0.0%, respectively, of FA pollutant, which demand more attention and control of 388
358 with that, the excess of ethanol to a ratio more than 1:2 caused the pollutant’s emission in the region. 389
359 re-dissolution of the crystal.
360 Similar treatment of a solution containing trace formalde- 6. Conclusion 390
361 hyde levels of 0.08, 0.05, and 0.03 lg mL 1 gives (recov-
362 ery ± RSD)% of (95.25 ± 2.9)%, (94.80 ± 3.1)%, and A spectrophotometric method has been developed for the 391
363 (94.07 ± 3.7%) respectively. determination of low level formaldehyde. The developed meth- 392
od depends on the formation of a red violet colored product 393
364 5. Application from the telomerisation of FA with TA in the presence of con- 394
centrated sulfuric acid and trace NaNO2 amounts. The method 395
365 The analytical results of FA with the suggested method in rain is shown to be selective, sensitive, simple and easy to perform. 396
366 water were compared with the result obtained by HPLC mea- The colored product that has been formed is stable at a tem- 397
367 surement (Tsai et al., 2003), and are in good agreement. The perature less than or equal to 25 C, and does not interfere 398
368 HPLC measurement depended on the derivatization of FA with substances normally present as pollutants. The method 399
369 with 0.1% of 2,4-dinitrophenylhydrazine reagent (DNPH). validation proved the accuracy and precision for the routine 400
370 While the analytical results for the other samples of wood application of low level formaldehyde determination. 401
371 products, and TSS samples were compared with the standard
372 chromotropic acid method adopted by NIOSH (Institute for 7. Uncited reference 402
373 Occupational Safety and Health, 1994). The obtained analyti-
374 cal results, Table 5, gave quantitative recoveries in the range of Dean (1998). Q7 403
375 96.0–100.0%. The test of significance shows that Student’s t-
376 test values and F-values at 95% confidence level are less than References 404
377 the theoretical values, indicating that there is a good agree-
378 ment between the results obtained by the proposed method Annual Book of American Society for Testing and Material (ASTM) 405
379 and the reference method with respect to accuracy and preci- Standards, Part (29), D2194, 1979, pp. 65–71. 406
380 sion. These results prove the validity and reliability of the pro- Berg, J.M., Tymoczko J.L., Stryer, L., Biochemistry, 16th Ed., The 407
381 posed method to analyze different aqueous samples. Tripe Helix, 2006. 408
382 In rainwater, however, the concentration of FA is different Bianchi, F., Careri, M., Musci, M., Mangi, A., 2007. Fish and food 409
383 according to the area, gas emission and of pollutants present safety: determination of formaldehyde in 12 fish, species by SPME 410
extraction and GC–MS analysis. Food Chem. 100, 1049–1053. 411
384 (Reeve, 2002). The first autumn rain collection contained more
British Standards Institution, Formaldehyde in textiles. Part 2. 412
385 pollutants, due to the washing out of the dissolvable sub-
‘‘Method for determination of free formaldehyde’’, British Stan- 413
386 stances present in air, moreover, the concentration levels of dard, BS 6782, Part 7, 1995, p. 12. 414

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005
 ARABJC 320 No. of Pages 9
17 February 2011
8 N.G. Yasri et al.

415 Chen, L., Jin, H., Wang, L., Sun, L., Xu, H., Ding, L., Yu, A., Zhang, extraction and formation constants. Anal. Chem. 43 (10), 1265– 483
416 H., 2008. Dynamic ultrasound-assisted extraction coupled on-line 1272. 484
417 with solid support derivatization and high-performance liquid Liteplo, R.G., Beauchamp, R., Meek, M.E., 2002. Report by 485
418 chromatography for the determination of formaldehyde in textiles. International Programme on Chemical Safety IPCS. Canadian 486
419 J. Chromatography 1192, 89–94. Centre for Occupational Health and Safety (CCOHS). 487
420 Chrastil, J., Reinhardt, R.M., 1986. Direct colorimetric determination Liteplo, R.G., Beauchamp, R., Meek, M.E., 2002. Health Canada, 488
421 of formaldehyde in textile fabrics and other materials. Anal. Chern. Ottawa, Canada, and R. Chénier, World Health Organization, 489
422 58, 2848–2850. Geneva 490
423 Clayden, J., Greeves, N., Warrer, S., Wothers, P., 2000. Organic Meyer, A.S.J., Ayres, G.H., 1957. The mole ratio method for 491
424 Chemistry. Oxford University. spectrophotometric determination of complexes in solution. J. 492
425 Cui, X., Fang, G., Jiang, L., Wang, S., 2007. Kinetic spectrophoto- Am. Chem. Soc. 79 (1), 49–53. 493
426 metric method for rapid determination of trace formaldehyde in Miller, J.C., Miller, J.N., 1993. Statistical in Analytical Chemistry, 3rd 494
427 foods. Anal. Chem. Acta 590, 253–259. ed. Ellis Horwood. 495
428 Davydova, E.A., Stolyanova, A.G., Ostrovskaya, E.G., 1986. Com- Mohamed, A.A., Mubarak, A.T., Marestani, Z.M.H., Fawy, K.F., 496
429 parative assessment of gas-chromatographic and photometric 2008. Highly sensitive and selective catalytic determination of 497
430 methods to determine formaldehyde in laboratory studies on formaldehyde and acetaldehyde. Talanta 74, 578–585. 498
431 construction polymers. Gig-Sanit. 3, 56. Pinheiro, H.C., Valéria de Andrade, M., Afonso de Paula Pereira, P., 499
432 Dean, J.R., 1998. Extraction Methods for Environmental Analysis, de Andrade, J.B., 2004. Spectrofluorimetric determination of 500
433 John Wiley & Sons Ltd, University of Northumbria at Newcastle, formaldehyde in air after collection onto silica cartridges coated 501
434 UK. with Fluoral P. Microchem. J. 78, 15–20. 502
435 Del Barrio, M.A., Hu, J., Zhou, P., Cauchon, N., 2006. Simultaneous Possanzini, M., Di Palo, V., 2003. Simultaneous determination of 503
436 determination of formic acid and formaldehyde in pharmaceutical HCHO, CH3 CHO and O(x) in ambient air by hydrazine reagent 504
437 excipients using headspace GC/MS. J. Pharm. Biomed. Anal. 41, and HPLC. Ann. Chim. 93 (1-2), 149–156. 505
438 738–743. Priority Existing Chemical Assessment, Report No. 28, Report by 506
439 Feng, S., Fan, J., Wang, A., Chen, X., Hu, Z., 2004. Kinetic National Industrial Chemicals Notification and Assessment 507
440 spectrophotometric determination of formaldehyde in fabrics and Scheme (NICNAS), Common wealth of Australia (2006). 508
441 air by sequential-injection analysis. Anal. Lett. 37, 2545–2555. International Programme on Chemical Safety; Formaldehyde Health 509
442 Fu Liu, J., Peng, J.F., Chi, Y.G., Jiang, G.B., 2005. Determination of and Safety Guide n. 57, World Health Organization, Geneva, 1991, 510
443 formaldehyde in shiitake mushroom by ionic liquid-based liquid- p. 48. 511
444 phase microextraction coupled with liquid chromatography. Talan- Reche, F., Garrigos, M., Sanchez, A., Jimenez, A., 2001. Determina- 512
445 ta 65, 705–709. tion of formaldehyde in finger-paints for children use by SFE 513
446 Gibson, L.T., Kerr, W.J., Nordon, A., Reglinski, J., Robertson, C., combined with spectrophotometric and chromatographic tech- 514
447 Turnbull, L., Watt, C.M., Cheung, A., Johnstone, W., 2008. On- niques. Anal. Lett. 34, 1311–1322. 515
448 site determination of formaldehyde: a low cost measurement device Reeve, N.R., 2002. Introduction to environmental analysis. John 516
449 for museum environments. Anal. Chem. Acta 623, 109–116. Wiley & Sons Ltd, University of Sunderland, UK. 517
450 Gigante, A., Gotardo, M., Tognolli, J., Pezza, L., Pezza, H., 2004. Teixeira, L., Leao, E., Dantas, A., Pinheiro, H., Costa, A., de- 518
451 Spectrophotometric determination of formaldehyde with chromo- Andrade, J., 2004. Determination of formaldehyde in Brazilian 519
452 tropic acid in phosphoric acid medium assisted by microwave oven. alcohol fuels by flow-injection solid phase spectrophotometry. 520
453 Microchem. J. 77, 47–51. Talanta 64, 711–715. 521
454 Guo, Y., Yan, H.T., Pei, R.H., Jia, S.Y., 2006. Kinetic spectropho- Tian, L., Zhang, A., Zhai, Y., 2004. Determination of trace formal- 522
455 tometric determination of formaldehyde by catalytic oxidation of dehyde in air by fast spectrophotometry with acetylacetone. Fenxi- 523
456 brilliant cresyl blue with sodium bromate. Fenxi-Shiyanshi 25, 92– Shiyanshi 23, 63–65. 524
457 94. Tsai, C., Shiau, H., Lee, S., Chou, S., 2003. Determination of low 525
458 Heimlich J.E., 2008. Formaldehyde; The Invisible Environment Fact, molecule weight aldehydes in packed drinking water by high 526
459 Sheet Series, The Ohio State University, CDFS-198-08. performance liquid chromatography. J. Food Drug Anal. 11, 46– 527
460 Huber, W., Fresenius, Z., 1981. Mechanization of photometric 52. 528
461 analysis with the component parts of liquid chromatography. II. U.S. Department of Health and Human Services, Public Health 529
462 Fast precise determination of formaldehyde. Anal. Chem. 309, Service, Centers for Disease Control, National Institute for 530
463 386–390. Occupational Safety and Health. NIOSH Manual of Analytical 531
464 National Institute for Occupational Safety and Health, NIOSH Methods. 4th ed. Methods A-Z & Supplements. Washington, DC: 532
465 Manual of Analytical Methods, 4th ed., Department of Health U.S. Government Printing Office, Aug 1994. 533
466 and Human Services, NIOSH, Cincinnati OH, USA, 1994. Velikonj, S., Jarc, I., Zupancic, L.K., Marsel, J., 1995. Comparison of 534
467 Isakau, H., Robert, M., Shingel, K.I., 2009. A novel derivatization-free gas-chromatographic and spectrophotometric techniques for the 535
468 method of formaldehyde and propylene glycol determination in determination of formaldehyde in water. J. Chromatography 704, 536
469 hydrogels by liquid chromatography with, refractometric detection. 449–454. 537
470 J. Pharm. Biomed. Anal. 49, 594–600. J.C. Wakefield, Formaldehyde-General information, Report by Health 538
471 Jagadeesan, N., Gupta, V., 1979. New spectrophotometric method for Protection Agency, CHAPD HQ, HPA Version 1, 2008. 539
472 determination of formaldehyde in air. Talanta 26, 962–963. Witthauer, J., Heilemann, K.J., Bischof, W., 1999. The applicability of 540
473 Li, Q., Oshima, M., Motomizu, S., 2007. Flow-injection spectrofluo- DNPH active collectors as passive collectors for the determination 541
474 rometric determination of trace amounts of formaldehyde in water of formaldehyde in indoor air. Gefahrstoffe-Reinhalt Luft. 59 (10), 542
475 after derivatization with acetoacetanilide. Talanta 72, 1675–1680. 369–373. 543
476 Li, Q., Sritharathikhum, P., Oshima, M., Motomizu, S., 2008. Zhang, A.M., Tian, L.Q., 2004. Kinetic spectrophotometric and 544
477 Development of novel detection reagent for simple and sensitive spectrofluorimetric determination of trace formaldehyde. Fenxi- 545
478 determination of trace amounts of formaldehyde and its applica- Kexue-Xuebao 20, 519–521. 546
479 tion to flow injection spectrophotometric analysis. Anal. Chem. Zhao, C., Li, M., Jiao, K., 2006. Determination of formaldehyde by 547
480 Acta. 612, 165–172. staircase voltammetry based on its electrocatalytic oxidation at a 548
481 Likussar, W., Boltz, D.F., 1971. Theory of continuous variations plots nickel electrode. J. Anal. Chem. 61, 1204–1208. 549
482 and a new method for spectrophotometric determination of 550

Please cite this article in press as: Yasri, N.G. et al., Spectrophotometric determination of formaldehyde based on the telomer-
ization reaction of tryptamine. Arabian Journal of Chemistry (2011), doi:10.1016/j.arabjc.2011.02.005