Professional Documents
Culture Documents
4: 123128
Abstract
J R., K. (2003): Analysis of cow milk by near-infrared spectroscopy. Czech J. Food Sci., 21:
123128.
In this work, the major components (total solids, fat, protein, casein, urea nitrogen, lactose, and somatic cells) were
determined in cow milk by near-infrared spectroscopy. Fifty calibration samples of milk were analysed by reference
methods and by FT NIR spectroscopy in reflectance mode at wavelengths ranging from 4000 to 10 000 cm1 with
100 scan. Each sample was analysed three times and the average spectrum was used for calibration. Partial least
squares (PLS) regression was used to develop calibration models for the milk components examined. Determined
were the highest correlation coefficients for total solids (0.928), fat (0.961), protein (0.985), casein (0.932), urea
nitrogen (0.906), lactose (0.931), and somatic cells (0.872). The constructed calibration models were validated by
full cross validation. The results of this study indicated that NIR spectroscopy is applicable for a rapid analysis
of milk composition.
Supported by Ministry of Education, Youth and Sports of the Czech Republic, Project No. MSM 432100001.
123
Vol. 21, No. 4: 123128 Czech J. Food Sci.
using the apparatus PRO-MILK from Foss Electric, diagnostic implement. It can calculate the optimal
Denmark. Urea nitrogen was determined spectro- number of factors.
photometrically at the wavelength of 420 nm after In an optimal course, PRESS shows a sharp fall
the reaction with p-dimethylaminobenzaldehyde and the next fall is gradual. The optimal number
(G et al. 1996). Lactose was determined of PLS factors will be found if the value of PRESS
polarimetrically (C et al. 1992). Somatic cell is minimal. A high number of PLS factors indicates
count was determined on Fossomatic apparatus a decreasing ability of prediction because PRESS
from Foss Electric. includes spectral interference. The numbers of
PLS factors for urea nitrogen, fat, total solids, and
RESULTS AND DISCUSSION somatic cells were low which demonstrated the
robustness of these models (Table 1). T et
The results are recapitulated in Table 1. All al. (1999, 2000) reported PLS factors for fat, total
results were evaluated using the variation sta- protein, and lactose to be from 8 to 10 which cor-
tistics (ANOVA) of the statistic package Unistat responds to our results on PLS factors for protein
(Table 2). (14), casein (10) and lactose (11).
The calibration model was created by PLS Dependable calibration takes place in the case
algorithm (Partial least squares). PLS factors of the value of the calibration coefficient of vari-
include spectral interference and information on ation CCV being lower than 5%, and the value of
concentration. PRESS dependence on factors used the prediction coefficient of variation being lower
on calibration with PLS method is an important than 10%. For all components (with the exception
Table 1. The calibration and validation of the results obtained in the determination of the components in raw
cow milk
Urea nitrogen (mg/100 ml) 0.9058 1.63 14.57 0.8251 2.18 19.48
R correlation coefficient; SEC standard error of calibration; SEP standard error of prediction; CCV calibration
coefficient of variation; PCV prediction coefficient of variation; n number of samples
124
Czech J. Food Sci. Vol. 21, No. 4: 123128
n number of samples; xNIR average of NIR values; xREF average of reference values; d difference between
average NIR and reference values
sd standard error of difference; P statistics values ; Fcrit significance factor
of urea nitrogen and somatic cells) the values of The determined correlation coefficients for cali-
the coefficients of variation were smaller than 5%. bration were for total solids 0.928, fat 0.961, protein
With urea nitrogen and somatic cells, the value of 0.985, casein 0.932, urea nitrogen 0.906, lactose 0.931
the prediction coefficient of variation was higher and somatic cells 0.872, and the correlation coef-
than 10%. ficients for validation found were for total solids
16
calibration validation linear calibration linear validation
NIR predictions (%)
14
y = 0.861x + 1.756
R = 0.928
12
y = 0.859x + 1.784
R = 0.896
10
8
9 11 13 15 Figure 1. Calibration and vali-
Laboratory values (%) dation results of solids
5.5
y = 0.923x + 0.319
R = 0.961
4.0
y = 0.919x + 0.336
R = 0.954
2.5
1.0
1.0 2.5 4.0 5.5 7.0
Figure 2. Calibration and vali-
Laboratory values (%) dation results of fat
125
Vol. 21, No. 4: 123128 Czech J. Food Sci.
4.4 calibration validation linear validation linear calibration Figure 3. Calibration and vali-
dation results of protein
3.8
NIR predictions (%)
y = 0.971x + 0.095
R = 0.985
3.2
y = 0.964x + 0.122
R = 0.951
2.6
2.0
2.4 2.8 3.2 3.6 4.0
Laboratory values (%)
2.9
y = 0.769x + 0.601
R = 0.932
2.6
y = 0.869x + 0.344
R = 0.851
2.3
2.0
2.0 2.4 2.8 3.2 Figure 4. Calibration and vali-
Laboratory values (%) dation results of casein
0.896, fat 0.953, protein 0.950, casein 0.851, urea the prediction of total solids 0.975, fat 0.967, and
nitrogen 0.825, lactose 0.750, and somatic cells protein 0.965.
0.854 (Table 1, Figures 17). T et al. (1999, The results of the reference values of samples and
2000) and R and G (2000) obtained similar of the calculated values of NIR were statistically
results for non-homogenised milk. K et analysed by ANOVA test in UNISTAT. Statistically
al. (2000) found the best calibration results for significant differences were not found between the
17
y = 0.820x + 2.001
R = 0.906
14
11
y = 0.654x + 3.827
R = 0.825
8
126
Czech J. Food Sci. Vol. 21, No. 4: 123128
3.5
4 4.6 5.2
Laboratory values (%)
400
y = 0.760x + 58.68
300 R = 0.872
200
y = 0.757x + 59.16
100 R = 0.854
0
0 50 100 150 200 250 300 350 400 450 Figure 7. Calibration and vali-
Laboratory values (1000/ml) dation results of somatic cells
reference values and the calculated values of NIR protein 0.950, casein 0.851, urea nitrogen 0.825,
(Table 2). lactose 0.750, and somatic cells 0.854.
Statistically significant differences between the
Conclusions reference values and the calculated values of NIR
were not found.
Correlation coefficients obtained for the compo-
nents of calibration were higher than 0.90 (with
the exception of somatic cells). The correlation References
coefficients were determined as follows: for total
solids 0.928, fat 0.961, protein 0.985, casein 0.932, C Z., P L., E. (1992): Chemick a fy-
urea nitrogen 0.906, lactose 0.931, and somatic cells zikln-chemick metody v kontrole jakosti mlka
0.872. The coefficient of correlation for lactose is a mlkrenskch vrobk. VPP STI, Praha: 1213.
low, together with a high number of PLS factors it G S., J P., H A. (1996): Somatic cell
shows a small degree of robust method. The whole counts in goat milk and their relation to milk com-
calibration is influenced by three samples with a position and properties. ivo. Vr., 41: 2531.
very low concentration of lactose. It is necessary to K O., L., J J. (2000): Multivariate
make this calibration for lactose more accurate. calibration of raw cow milk using NIR spectroscopy.
Cross validation indicates the possibility of Czech J. Food Sci., 18: 14.
using NIR spectrometry to determine the basic M R.T. (1992): Standard methods for the exami-
ingredients of milk. The correlation coefficients nation of dairy products. 16th Ed. Am. Public Health
of validation were for total solids 0.896, fat 0.953, Assoc., Washington.
127
Vol. 21, No. 4: 123128 Czech J. Food Sci.
Souhrn
J R., K. (2003): Analza kravskho mlka NIR spektroskopi. Czech J. Food Sci., 21: 123128.
Pomoc NIR spektroskopie jsme stanovovali obsah jednotlivch sloek nehomogenizovanho kravskho mlka,
pedevm obsahu suiny, tuku, celkovch blkovin, kaseinu, laktosy, moovinovho dusku a somatickch bu-
nk. Men bylo provdno u 50 vzork mlka na pstroji FT NIR Nicolet Antaris v rozsahu vlnovch dlek
4 00010 000 cm1 se 100 scany a rozlienm 8. Vzorky mlka byly zahty na 40 C, protepny a ochlazeny na
20 C. IR spektra vzork byla mena na integran sfe v reimu reflektance (technika mc absorpci zen
po odrazu paprsku od povrchu vzorku, kter byl umstn v Petriho misce, a mc prostor vymezen zrctkem).
Kalibrace byla vyhotovena pomoc PLS metody. Kad vzorek byl promen tikrt a pro kalibraci bylo pouito
prmrn spektrum. Vytvoen kalibran modely pro jednotliv sloky mlka byly oveny kovou validac.
Pro vytvoen validanho modelu byla pouita stejn sada vzork jako pro kalibraci. Zhodnocen vsledk bylo
provedeno na zklad korelace mezi referennmi hodnotami a hodnotami vypotenmi z kalibranch rovnic
a na zklad smrodatnch odchylek kalibrace a validace (SEC a SEP). Zjitn korelan koeficienty pro kalibra-
ce: suina 0,928, tuk 0,961, ist blkoviny 0,985, kasein 0,932, moovinov dusk 0,906, laktosa 0,931 a somatick
buky 0,872. Korelan koeficienty pro validaci byly zjitny pro suinu 0,896, tuk 0,953, blkoviny 0,950, kasein
0,851, moovinov dusk 0,825, laktosu 0,750 a somatick buky 0,854. Hodnoty sledovanch ukazatel sloen
mlka namen NIR spektrofotometri byly metodou ANOVA statisticky porovnny s hodnotami namenmi
referennmi metodami. Mezi obma metodami stanoven nebyly zjitny statisticky prkazn rozdly.
Corresponding author:
128