Определяне на неопределеността при анализ на...

:

- ( . : 00270) ( . : 00272)

:

.

22.01.2008.

.

:

1. .......................................................................................2

2. ...................................................2

3. ..........................................................2

4. ....................3

5. ........................................................................4

6. . .............................................................4

4.1. .................................................................4

4.2. 1: ............................................5

4.3. 2: ...................................................7

4.4. 3: .............................................8

4.5. 4: ........................................................................15

4.6. : ................................................................................17

:

:

o, () ().

:

, , . 4.1.

. 4.1:

:

:

: [mg kg-1];

: (max) ;

: () [g ml-1];: [ml];

: [g g-1] [mg kg-1];

: () (max) ;

: ;

: [g];

: ;

() :

- . 4.2.

. 4.2:

Repeatability

I(op)

c(ref)

V(op)

Calibration

I(op)

Linearity Purity(ref)

I(ref)

m(ref)

m(ref)

Temperature Calibration Temperature

V(ref)

dilution

V(ref)

Calibration

Calibration

Calibration

V(op)

m(sample)

dilution

P(op)

m(gross)

Linearity

m(tare)

Linearity

Calibration

Calibration

Calibration

F(hom) Recovery I(ref)

m(sample)

:

, , . 4.1 . 4.3 ( . 4.5).. 4.1:

DescriptionValue xStandard uncertainty u(x)Relative standard uncertainty u(x)/xComments

Repeatability(1)1.00.270.27Based on duplicate test of different types of samples

Bias (Rec) (2)0.90.0430.048Spiked samples

Other sourses (3)

(Homogeneity)1.00.20.2Estimation based on model assumptions

u(Pop) Pop----0.34Relative standard uncertainty

. 4.3:

. :

4.1

, . . . , , .

4.2 1: ()

- , .

:

. 4.4. :

I). : , 15 , . - , .

II). , .

III). (): , - , , Kuderna-Danish .

IV). - ().

V). / , , - .

VI). .

VII). ( 2 ml) 10 ml .

VIII). : ( ) 5 l , .

IX). 5 g ml-1 ( ).X). (-) , , , 5 l , . 4.4:

:

:

[g ml-1]

- ( mg kg-1) :

, cop:

: [mg kg-1];

: (max) ;

: () [g ml-1];

: [ml];

: [g g-1] [mg kg-1];

: () (max) ;

: ;

: [g];

:

0.01 2 mg kg-1, .

4.3 2:

-, - . . - , , .

, . , F(hom), - (. 4.5).

, , , . , , :

, . , . .

. 4.5: -

I(op)

c(ref)

V(op)

Calibration Precision

Linearity

Purity(ref)

m(ref)

Precision

TemperatureCalibration PrecisionTemperature

V(ref)

Calibration

Calibration

CalibrationPrecision

dilution

Precision

P(op)

m(gross)

Precision

Linearity

m(tare)

Sensitivity

Linearity

Precision

Calibration

Precision

Calibration

Sensitivity

Calibration

F(hom)Recovery I(ref)

m(sample)

:

: a a . , . , , , . , , .

4.4 3: :

7.7., , .

- .

- .

, .

- , - (. 4.6).

. 4.6: - Repeatability

I(op)

c(ref)

V(op)

Calibration

I(op)


I(ref)

m(ref)

m(ref)

Temperature Calibration Temperature

V(ref)

dilution

V(ref)

Calibration

Calibration

Calibration

V(op)

m(sample)

dilution

P(op)

m(gross)

Linearity

m(tare)

Linearity

Calibration

Calibration

Calibration

F(hom) Recovery I(ref)

m(sample)

:

, , . , . , . ( ) .

- , :

, . , -. -.

. 4.2:

ResidueD1

[mg kg-1]D2

[mg kg-1]Mean

[mg kg-1]Difference

D1-D2Difference/mean

Malathion1.301.301.300.000.000

Malathion1.300.901.100.400.364

Malathion0.570.530.550.040.073

Malathion0.160.260.21-0.10-0.476

Malathion0.650.580.620.070.114

Pirimiphos Methyl0.040.040.040.000.000

Chlorpyrifos Methyl0.080.090.085-0.01-0.118




Chlorpyrifos Methyl0.030.020.0250.010.400


Pirimiphos Methyl0.070.080.75-0.10-0.133

Chlorpyrifos Methyl0.010.010.100.000.000


1. / :

( , , ) , . . 4.2.

. , , . , , , , 0.382/ = 0.27.

:

, , . . - , . - , ( ) .

/ :

( ) () , ( ). . 4.3. .

( ) , 42 90%, (s) 28%. . 4.3:

SubstrateResidue

TypeConc

[mg kg-1] N 1)Mean 2)%S 2)[%]

Waste oilPCB10.08849

ButterOC0.653310912

Compound Animal Feed IOC0.325100909

Animal & Vegetable Fats IOC0.333410224

Brassicas 1987OC0.323210418

BreadOP0.13429028

RusksOP0.13308427

Meet & Bone FeedsOC0.32589512

Maize Gluten FeedsOC0.3259929

Rape Feed IOC0.325118913

Wheat Feed IOC0.32525889

Soya Feed IOC0.325138519

Barley Feed IOC0.32598422

(1). .

(2). (s) %. , 1.0. t, :

, n-1 95% ( n , Rec). t - tcrit, Rec 1.0.

(1/Rec) Rec .

:- . 4.7. , (1) , (2) (3) .

. 4.7:

Repeatability(1)I(op)

c(ref)

V(op)

Calibration(2)

I(op)


I(ref)

m(ref)

m(ref)

Temperature(2) Calibration(2)Temperature(2)

V(ref)

dilution

V(ref)

Calibration(2)

Calibration(3)

Calibration(2)

V(op)

m(sample)

dilution

P(op)

m(gross)

Linearity

m(tare)

Linearity

Calibration(3)

Calibration(2)

Calibration(2)

F(hom)(3) Recovery(2) I(ref)

m(sample)(1) (FRep 4.1) .

(2) .

(3) .

. , . , , . , ( Iref Iop ), . 99.53% 0.0006%. 0.0006/ = 0.00035 ( ). ( ), . , , . . 4.2 . 4.3, . . , .

. , ( , , ). . . , . , ( 4.6.). :

() : 0.58.

() , - : 0.20

() , : 0.05-0.10 ( )

() . ( ) . () - . () - , (). 0.20.

4.5. 4: :

- , . 4.4.

. 4.4:

DescriptionValue xStandart

Uncertainty u(x)Relative standart

Uncertainty u(x)Remark

Repeatability (1)1.00.270.27Duplicate tests of different types of sample

Bias (Rec)(2)0.90.0430.048Spiked samples

Other sources (3) Homogenity1.00.20.2Estimations founded on model assumptions

u(Pop)/Pop----0.34Rellative standart uncertainty

, ( 4.1):

(. 4.5) . 4.5. , 1.1111 0.373/1.11=0.34.

. . 4.8 |u(y, xi)| . 4.5. - . , - . , .

u(pop) 2 :

4.8:

u(y, xi) (mg kg-1)

u(y, xi) = (y/xi). u(xi) 4.5.

4.5:

ABCDE

1RepeatabilityBiasHomogeneity

2Value1.00.91.0

3Uncertainty0.270.0430.2

4

5Repeatability1.01.271.01.0

6Bias0.90.90.9430.9

7Homogeneity1.01.01.01.2

8

9Pop1.11111.4111.06041.333

10u(y,xi)0.30-0.5070.222

11u(y)2, u(y,xi)20.14200.090.002570.04938

12

13u(Pop)0.377(0.377/1.111=0.34 as a relative standard uncertainty)

C2 E2. - (C3 E3). C2 E2 B5 B7. B9 (= B5 * B7/ B6, 4.1). C5 C2, C3. C9 C5 C7. D E . 10 (C10 E10) 9 (C9 E9) B9. B11 11 (C11 E11) 10 (C10 E10). B13 , B11.

A4.6 : :

, . , - , , , . - , . L1 L2, . . . , n , .

: =n*(p1l1 + p2l2)

=np1*(l1-l2) + nl2 [1]

=np1*(1-p1)*(l1-l2)2 [2]

l1 l2 , L1 L2, X, p1 p2 (n - , ). : , 2 12 24 cm, 2 2 2 cm ( 432 ), 15 .

(): ( ) . L2 l2; L1=1. , , l1 . , 1 6 (2/12) , p1 1/6 0.167, l1 X/72(.. 72 ).=15*0.167*l1 = 2.5 l1

2 =15*0.167*(1-0.17)*l12=2.08 l12

= =1.44 l1

RSD= /=0.58

: X , 432/15, X:

, . , , RSD.

(): . , , l1 , l2 , p1 , :

p1 2. , l1=X/272.

: (). :

=15*0.63* l1=9.5 l1

2=15*0.63*(1-0.63)* l12=3.5 l12

= =1.87 l1

RSD= /=0.2

(): 0 . - (), p1=0.37 l1 X/160. :=15*0.37* l1=5.6 l1

2=15*0.37*(1-0.37)* l12=3.5 l12

= =1.87 l1

RSD= /=0.33

, , l1 l2, . , 50% 50% , :

l1=2*l2 l1=X/296

=15*0.37*( l1- l2)+15*l2

=15*0.37*l2+15*l2=20.6 l2

2=15*0.37*(1-0.37)*(l1-l2)2=3.5 l22

RSD=1.87/20.6=0.09

1 ., . 1 -. , ( ). (), / 0.09.

: , , - . , , ( , ) , . , , , , .

:

1. , Quantifying Uncertanity, edition: 2002, Example A.4

Homogenise

Extraction

Clean-up

Prepare calibration standard

Bulk up

GC Calibration

GC Determination

RESULT

Homogenise

Extraction

Clean-up

Prepare calibration standard

Bulk up

GC Calibration

GC Determination

RESULT

3

_1262460997.unknown

Определяне на неопределеността при анализ на...

Documents

Transcript of Определяне на неопределеността при анализ на...