A rapid and simple method for the determination

of Formaldehyde in Fishery Products

Item Type article

Authors Rehbein, Hartmut; Schmidt, Thomas

Download date 28/08/2021 20:21:58

Link to Item http://hdl.handle.net/1834/21799

Inf. Fischwirtseh. 43(1), 1996 37

A rapid and simple method for the determination of

Formaldehyde in Fishery Products
Eine schnelle und einfache M~thode zur Bestimmung des Formaldehyd-Gehaltes
in Fischer.zeugnissen

H. Rehbein und T. Schmidt, Institut für Biochemie und Technologie

The content of free formaldehyde (FA) in minced fish musele was measured by the following procedure: A mix-
ture of minced fish musele and water was deproteinized by means of the Carrez reagent. The FA content of the
filtrate was determined reflectometrically using the Reflectoquant test strips and the RQflex. The results agreed
weIl with the colorimetrically (Nash test) measured FA content.

I ntroduction
Abstract:
The concentration of formaldehyde can be used as an Der· Gehalt an. ·freießlFormaldehyd (FA) in
indicator for the quality of frozen fishery products Fischerteugnissenwurde •. mitfolgender Methode
(Licciardello, et al. 1982). High amounts of FA result bestiIIllllt; Zerkleinertes Fischtleisch .wurde mit
in tough texture and low water binding capacity. Re- Wasser .homogenisiert . und mit. Carrez-Reagenz
cently the FA content of 271 fishery products from enteiweißt. Der Formaldehydgehaltdes Filtrates
retai! shops in Germany has been determined wurde reflektometrisch .unter .Verwendung· von
(Rehbein, et al. 1995). The mean values and ranges ReftectOquant..Teststät>chen> .llnd .•. des RQflex
ermittelt.Die>Ergebnissestimmtengutrnit kol-
(mg/kg wet weight) were 11.9 (0.2-60) for free (i.e.
orimetrisch. (Nash Test) gemessenen FA-
acid extractable) FA, and 47.4 (0-240) for the sum of Gehalten Überein.
free and bound (released by distillation of acidified
fish flesh) FA.
Chemical Analysis
A semiquantitative test for free FA and more sophisti-
Preparation of Extracts
cated methods for the determination of free and
bound FA in fishery products have been described Five grams of minced fish musele were homogenized
previously (Rehbein 1986). with 80 ml distilled water using the Krups 3 Mix 4000
equipped with the high speed cutting rod. After addi-
Here we present a method for the determination of
tion of 4 ml Carrez I (15 %, w/v, K4Fe(CN)6 x 3 HzO)
free formaldehyde, which is fast and easy to perform
and therefore useful for industrial quality control and 4 ml Carrez II (30 %, w/v, ZnS04 x 7 H20) the
laboratories and work on board of fishery research volume of the mixture was adjusted with distilled
vessels. water to 100 ml. Then the mixture was shaken
manually and precipitated material was removed by
filtration using a folded paper filter. The filtrate was
Materials and Methods stored at room temperature until being analysed for
FA on the same day.
Origin of Sampies
Fillets of hake (Merluccius merluccius), cod (Gadus Colorimetric Determination of Formaldehyde
morhua) and haddock (Melanogrammus aeglefinus) The Nash Test was used for colorimetric determina-
were taken from fish caught on cruises of the research tion of FA according to the procedure described pre-
vessel "Walther Herwig III". Onboard minced fillet viously (Rehbein 1986).
from cod and saithe (Pollachius virens), mixed with
blood or kidney of the respective species, were stored Reflectometric determination of Formaldehyde
in plastic bags for several days at 1 oe. Then the The method is based on the reaction of FA with 4-
minces were frozen and stored at about -25°C for 5 amino-3-hydrazino-5-mercapto-l,2,4-triazole to form
months to be analysed in the institute. a purple tetrazole derivative, the concentration of
which is measured by means of the RQflex (Merck,
Rainbow trout (Oncorhynchus mykiss) was obtained
Darmstadt). The Reflectoquant Formaldehyde Test
from the local fish market.
Strip (Merck 16989) was used according to the in-
structions given by Merck:
38 Inf. Fisch wirtsch. 43 (1), 1996

- Rinse the test vessel several times with the

sampie solution (filtrate), then fill to 5-ml
12
mark.
- Add lO drops of reagent Fo-l and swirl.
10
- Remove one test strip and immediately reclose
the tube. .
-- Press start button of the reflectometer and at
the same time immerse both reaction zones of
the test strip in the meas urement solution for
approximately 2 sec.
- Vigorously shake off excess liquid from the
test strip.
- As soon as the beeper sounds (5 sec before end
of the reaction time), insert the test strip all
the way into the strip adapter of the RQflex
with the reaction zones facing the display. Concent,..tlon of Foraalde/l\jde <.g/.I>
- Read off the result from the display in mg/I
Fig.1: Calibration curve for Rqflex readings
FA.
The entire procedure takes about 2 minutes. the RQflex readings were enhanced about 15 %
(Table 2). There was a linear relationship between the
concentration of FA in Carrez filtrate and the RQflex
Results and Discussion readings (Figure 1):
At first the correlation between the RQflex readings
CFA (mg/I) = 0.90 x RQflex value (mg/I) - 0.13
and the FA concentration of the sampie solution was
established. FA solution (37 %, Merck 104003) was The coefficient of correiation (rcor) was 0.998.
diluted with distilled water or Carrez filtrate (which is
prepared Iike an extract, but omitting fish musc1e) to The suitability of the reflectometric FA determination
obtain FA concentrations between 2 and 12 mg/I. The for analysis of fishery products was investigated with
actual FA concentrations of the sampie solutions were a number of fish fillets and minces containing differ-
measured using the Nash test. ent amounts of formaldehyde. The resuIts, which are
Tab. 1: Influence of the Carrez reagent on FA determination
compiled in Table 3, show that this method can be
by means of the Nash test. A 37 % FA solution was diluted used for estimating the content of free FA in fishery
with distilled water or Carrez filtrate, and FA was measured products. The RQflex readings were consistently
using the Nash test.
higher than the FA values obtained by the Nash test,
FA concentration (mgll) in sam pie solutions made from
but they correiated satisfactory with the results of the
Distilied water Carrez filtrate Nash test (rcor = 0.993, Y = 0.86x - 6.57, y: Nash test
2.1 2.1 value).
4.2 4.1 Tab. 3: Comparison of colorimetric and reflectometric
6.2 5.9 determination of FA in fish fillets and minees.
8.2 7.8
10.1 10.1 Type of fishery FA content (mg/kg wet weight)
product Nash test RQflex values
Table 2: Influence of the Carrez reagent on FA determination hake fillet 36 54
using the RQflex. A 37 % FA solution was diluted with dis- hake fillet 14 36
tilled water or Carrez filtrate, and FA was measured reflec- cod fillet 24 40
tometrically. haddock fHlet 4 low
FA concentration (mg/mi) in sam pie solutions made from rainbow traut fillet 4 low
Distilled water Carrez filtrate minced cod fillet 34 44
minced cod fillet, stored for
2.4 2.6 10 d at 1 °C 22 40
3.9 4.5 cod fillet, mixed with blood 48 64
5.9 6.9
7.5 8.6 cod fillet, mixed with kidney 1050 1200
9.7 11.5 • stored at 1 °C for 3 d 580 610
- stored at 1 °C for 5 d 450 480
minced saithe fillet 14 20
saithe fillet, mixed with blood 42 58
Table 1 demonstrates that the N ash test was not dis-
saithe fillet, mixed with kidney 567 790
turbed by the Carrez reagent. The Reflectoquant test Extracts were diluted with Carrez filtrate if neccessary.
was influenced by the Carrez reagents in the way that
Inf. Fischwirtseh. 43(1), 1996 39

Recently, a method for the determination of formal- suited as a preliminary test for identification of those
dehyde in shrimps has been published, which used fishery products, which contain unacceptable high
ZnS04 to extract FA from alcalised shrimp muscle amounts of formaldehyde.
(Yamagata and Low 1995). FA was measured col-
orimetrically by means of the same chemical reaction References
as occurring in the Reflectoquant test strrp. The re- Licciardello, J.1., Ravesi, E.M., Lundstrom, R.C., Wil-
sults obtainecl with that method, being more time helm, KA., Correia, F.F., Allsup, M.G.: Time-
consuming than the procedure described here, cor- temperature tolerance and physical-chemical quality
roborate that the underlying chemistry is suited for tests for frozen red hake. J. Food Qual. 5, 215-234,
FA determination in fishery products. Extraction of 1982.
FA by Carrez reagent has several advantages com- Rehbein, H., Eichenauer, D., Feser, P., Friedrich, R.,
pared to perchloric acid extraction: (i) Perchloric acid Glück, B., Harz, A., Waming, W., Werkmeister, K,
is a corrosive reagent, prohibiting application of Winkler, F.: Formaldehyd und Dimethylamin in
tiefgekühlten Fischerzeugnissen aus dem Handel - eine
household mixers for homogenization of fish sampIes. Bestandsaufnahme. Archiv LebensmiUelhyg. 46, 122-
(ii) Perchloric acid extracts have to be neutralized 124, 1995.
before being used to reflectometric FA measurement. Rehbein, H.: Formaldehyd in Fischprodukten: Nach-
(iii) Carrez reagent is cheaper and less hazardous than weis- und Bestimmungsmöglichkeiten. Inf. Fisch-
perchloric acid. wirtsch. 33(3), 134-141, 1986.
Yamagata, M. and Low, L.K: Rapid determination of
formaldehyde in banana shrimp, Penaeus merguiensis.
Conclusions J. Food Sci. 60, 718-720,1995.
From the results described above the conclusion is
justified that the reflectometric test system is weIl

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