Ketepatan (Accuracy)

Ketelitian (Precision)
Sensitifitas (Sensitivity)
Selektivitas (Selectivity)
Limit Deteksi (LOD)
Limit kuantifikasi (LOQ)
Accuracy (Ketepatan)
Dan
Precision (Ketelitian)
 Tepat & Teliti Tepat dan tidak teliti

Teliti dan tidak tepat Tidak teliti dan

tidak tepat
Accuracy and Precision
Exactnessof
Exactness ofan
an
Accuracy
Accuracy analyticalmethod
method
analytical

Degreeof
Degree of
repeatabilityof
repeatability ofan
an
Precision
Precision analyticalmethod
analytical method
Repeatability
Repeatability
Uncertainty
Uncertainty
Reproducibility
Reproducibility

Correctness//
Correctness Systematicerror
Systematic error// Recovery//
Recovery
Trueness Correctvalue
Correct value Bias
Bias
Trueness
4
Accuracy (Ketepatan)

Kedekatan antara data hasil pengukuran (HP) dengan

nilai yang sebenarnya (true value/ TV)

 
% Error x 100

% Accuracy = 100 - % error

 Misal: acceptable error +/- 5%
Nilai dari –5% s/d 5% dapat diterima
Nilai kurang dari –5% atau lebih dari 5% harus diuji ulang
Accuracy (Ketepatan)

Diuji ulang -5%

5% diuji ulang
Accuracy (Ketepatan)

Bagaimana cara mendapatkan TRUE VALUE (TV) ?

- Standard Reference Material (SRM)
- Certified Reference Material (CRM)
- Buku references, etc

Jika tidak ada SRM, CRM, atau reference lainnya?

- Proficiency (comparative) test
- Recovery test (spiked sample)
Accuracy (Ketepatan)

Proficiency (comparative) test:

Melibatkan beberapa laboratorium

dan analis yang berbeda untuk
melakukan analisa yang sama
terhadap sampel yang sama dan
membandingkan hasil yang
diperoleh.
Accuracy (Ketepatan)
Tujuan Proficiency (comparative) test:

• Memastikan analis memperoleh hasil

yang sama terhadap sampel yang sama

• Memastikan analis dalam satu

laboratorium mendapatkan hasil yang
sama untuk uji yang sama tehadap sampel
yang sama

• Memastikan hasil dari suatu laboratorium

mencerminkan hasil dari sebagian besar
laboratorium penguji (good agreement)
Accuracy (Ketepatan)
Recovery test (spiked sample)
Ke dalam sampel (S) ditambahkan analyte (A)
yang telah diketahui konsentrasinya
S+A
  % Recovery x 100

S Quantitative recovery : 80-110 %

Note: jumlah analyte yang ditambahkan (A) ke dalam sampel

TIDAK BOLEH berbeda jauh dengan analyte yang ada dalam
sampel (S)

• Dapat mengetahui pengaruh matriks terhadap

recovery analyte dalam sampel
Precision (Ketelitian)

Kedekatan antara data hasil pengukuran dengan

data hasil pengukuran lainnya

Mengukur ketelitian  Standard Deviasi (SD)

SD

Relative Standard Deviation (RSD)

Teliti
  x 100%
Precision (Ketelitian)
Repeatability
- Precision under similar conditions;
RSD within day (dlm hari yang sama) dari masing-masing analis pada
beberapa konsentrasi analyte

Reproducibility
- Precision under different conditions;
RSD between day (dlm hari yang beda) dari analis yang berbeda

3 konsentrasi berbeda analyte ,

3 analis berbeda,
3 hari berbeda
 Sensitivity

 The sensitivity of a measuring instrument is its ability to

detect quickly a small change in the value of a
measurement.
 Sensitivity

 A measuring instrument that has a scale with

smaller divisions is more sensitive.
 Sensitivity

 As an example, the length of a piece of wire is measured

with rulers A and B which have scales graduated in
intervals of 0.1 cm and 0.5 cm respectively, as shown in
Figure below. Which of the rulers is more sensitive?
 Sensitivity

 Results:
 Ruler A: Length = 4.8 cm
 Ruler B: Length = 4.5 cm
 Ruler A is more sensitive as it can measure to an accuracy
of 0.1 cm compared to 0.5 cm for ruler B
 Sensitivity

 In addition to the size of the divisions on the scale of the

instrument, the design of the instrument has an effect on
the sensitivity of the instrument. For example, a
thermometer has a higher sensitivity if it can detect small
temperature variations. A thermometer with a narrow
capillary and a thin-walled bulb has a higher sensitivity.
 The slope of the calibration curve at the concentration
of interest is known as calibration sensitivity.
S = mc + Sbl Y = ax + b
S = measured signal; c= analyte concentration;
Sbl = blank signal; m = sensitivity (Slope of line)
Analytical sensitivity ()
 = m/ss
m = slope of the calibration curve
ss = standard deviation of the measurement
 Specificity/Selectivity
 Identity: Signal to be attributed to the analyte
 Selectivity: The ability of the method to determine accurately
the analyte of interest in the presence of other components
in a sample matrix under the stated conditions of the test.
 Specificity is a state of perfect selectivity

Baseline separation
 Selectivity: Verification of the identification criteria

 MS – criteria
• 3 or 4 identification points
• 1 precursor and 2 transition ions
• Relative ion intensities

 LC – criteria
• Relative retention time (RRT): +/-
2.5 % (LC)

 UV – criteria
• Spectrum match
• +/- 3 nm
 Linearity (Linearitas)
• Larutan Standard
• Signals: Peak Area, Intensitas,
• Kurva Kalibrasi
• Internal Standard (->instrumental drift)
• Pengaruh Matrik (Adisi standard ,
Matrix-Match Calibration).
 Linearity (Linearitas)
Signals: Peak Area, Intensitas

Peak Area
Intensitas

CONTOH !!

Konsentrasi

Mana yang lebih baik?

Konsentrasi vs Intensitas
Kosentrasi vs peak area
 Linearity (Linearitas)
Kurva Kalibrasi

• How well a calibration curve follows a straight

line (Konsentrasi proporsional terhadap
intensitas)
• R2 (Koefisien korelasi)  > 0.95 ?
 Linearity (Linearitas)
Pengaruh Matrik

• “Matrix effects” harus diperhitungkan !

• “Matrix effects”  compensating : “Adisi
standard / matrix-matched calibration”.
Sensitivitas
turun !!!!!!!!!
Matrix-Match Calibration
All calibration standard solutions and blanks should
contain similar components as the sample being analysed,
except for the analyte of interest
 Matrix Removal

Liquid-liquid extraction Solid-phase extraction (SPE)

Requirement of Less solvent consumption
organic solvents in and disposal
large amount
High recovery value
Low recovery value
Less laborious operation
Laborious operation
Fast extraction time
Time-consuming

Single equilibrium state  low extraction Multiple equilibrium state  high extraction
efficiency efficiency
 Limit of Detection (LOD)
Limit of Quantification (LOQ)
 Limit of Detection (LOD)
IUPAC:
LOD: the smallest concentration of analyte
that has a signal significantly larger than the
signal arising from a reagent blank
Calculation of LOD (1)
The analyte’s signal at the detection limit, (SA)LOD

(SA)LOD = Sreag + zsreag

Sreag : the signal for a reagent blank
sreag : the known standard deviation for the reagent blank’s signal
z : factor accounting for the desired confidence level
(typically, z is set to 3)

Limit of Quantification (LOQ) : The smallest concentration or

absolute amount of analyte that can be reliably determined (ACS)

(SA)LOQ = Sreag + 10sreag

 Calculation of LOD (1)
LOD is calculated based on (SA)LOD divided with slope of
calibration graph (a)

y = ax + b y
(SA)LOD = a * LOD + b a
b
x
 Limit of Quantification (LOQ)
LOQ: The smallest concentration or absolute amount of analyte
that can be reliably determined (American Chemical
Society)

(SA)LOQ = Sreag + 10sreag

y = ax + b
(SA)LOQ = a * LOQ + b
 Calculation of LOD (2)
Signal to Noise Ratio (S/N) method
Signal to Noise Ratio (S/N) is a dimensionless measure of the
relative strength of an analytical signal (S) to the average strength of
the background instrumental noise (N)

S/N = 3
LOQ
S/N = 10
Calculation of LOD (2)
Signal to Noise Ratio (S/N) method

y = ax + b
3N = a * LOD + b
Calculate LOD of Ga, Ge, and In
　 Ion Count (CPS)
　 Ga Ge In

blank 1 29.78 9.08 18.67

blank 2 30.53 9.50 23.34
blank 3 25.91 10.79 28.41
blank 4 27.73 10.16 20.025
blank 5 29.82 9.78 23.49
blank 6 29.11 10.09 31.93
blank 7 25.31 12.52 23.80
blank 8 28.63 11.188 24.72
blank 9 26.21 13.22 17.21
blank 10 30.04 12.56 23.86
Std 1 (1 ppb) 250.87 43.07 60.56
Std 2 (2 ppb ) 499.68 77.36 108.95
Std 3 (3 ppb ) 773.46 109.43 151.83