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Tony Venelinov
University of Architecture, Civil Engineering and Geodesy
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Tony I. Venelinov
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1. INTRODUCTION
T. I. Venelinov is with the University of Architecture, Civil Engineering and Geodesy, 1, Hristo
Smirnensky Boulevard, 1046-Sofia, Bulgaria (e-mail: tvenelinov_fhe@uacg.bg).
231 Conference Proceedings WATER 2016 23-25 June Constanţa
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2. EXPERIMENT DESCRIPTION
Apparatus
DR 3900 - portable spectrophotometer (Hach Lange GmbH) with 320 to
1100 nm wave length range (tungsten halogen lamp) and referent ray to compensate
lamp wear and power fluctuation was used. The devise has integrated system for
barcodes reading of the prepared tests, with ten measurements for rotation and
elimination of wrong reading caused by prepared cuvettes wasting.
LT 200 - thermo-reactor (Hach Lange GmbH) with thermo block was used
for heating up the cuvettes up to 1500C and TenSette plus - Electronic pipette 0.2 to 5
mL (Hach-Lange GmbH) was used for dilusions.
Materials
CRM (RTC COD 500-500) with certified value for COD of 500.00 ± 7.65
mgO2/L -(LOT No. 016203), CRM (CertiPrep) with certified value for NO3--N of
1005 ± 3 mg/L (LOT No. 2-78NO3N-2), CRM (RTC TPO 1000 to 500 ML) with
certified value for РО43--Р of 1000.0 ± 15.5 mg/L (LOT No. 017605), CRM (SPEX
Ammonium Standard) with certified value for NH4+-N of 1002 ± 3 mg/L (LOT No. 2-
95NH4N-2), CRM (RTC QC3130-500ML) with certified value for TOC of 38,0 ± 0,9
mg/L and TOC1K-XXX with certified value for TOC of 1000 ± 5 mg/L, CRM (Fluka
BCBC2167 with certified value for Cl- of 1000 ± 4 mg/L. (LOT No. 39883), were
used for the validation studies.
Cuvette tests (Hach-Lange GmbH) LCK 114 and LCK 314 were used for the
determination of COD in range 150-1000 mgO2/L and 15-150 mgO2/L, respectively.
LCK 339 was used for the determination of NO3--N in the range of 0.123-13.5 mg/L..
LCK 303 and LCK 305 were used for the determination of NH4+-N in the range of
2.0-47 mg/L and 1.0-12 mg/L, respectively. LCK 350 was used for the determination
of РО43--Р in the range of 2.0-20 mg/L. LCK 380 and LCK 381 were used for the
determination of TOC in the range of 2-65 mg/L and 65-730 mg/L. LCK 311 was
used for the determination of Cl- in the range of 1-1000 mg/L.
Sample preparations for all the parameters are described elsewhere [4].
Conference Proceedings WATER 2016 23-25 June Constanţa 232
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Experimental design
Uncertainty is best estimated during method validation. The experimental
design according to ISO/IEC 21748:2010 was set up in a way so that the repeatability,
reproducibility and trueness estimates are used for measurement uncertainty
estimation [2].
Trueness was proven by measurement of three independent samples of a
certified reference material on two different days. From these data the uncertainty of
trueness and method bias were calculated:
st2 ∑ u mat
2
st
ut = = + 2 (1)
nt nt n mat
sr MS within
ur = = −
(2)
n y
MS betweengroup − MS withingroup
sd n pergroup
u ip = = −
(3)
d y
2
s
ub = b + b2 + u Cref
2
(6)
n
M
2
u c ,rel = u Rw + u b2 (7)
ISO/IEC 21748:2010
Data for the measurement uncertainty estimation according to ISO/IEC
21748:2010 is presented in Table 1. The mean of the 15 measurements over a five-
days spread of a respective CRM for all the parameters was used to calculate method
bias and repeatability. The uncertainties of trueness, repeatability and due to
intermediate precision are based on ANOVA-single factor calculation. They are
expressed as relative uncertainties and summarized below.
ISO/IEC 11352:2012
If stable quality control (QC) samples that cover the whole analytical
process, including all sample preparation steps, are analysed regularly and if these QC
samples are similar in matrix and analyte concentration levels to test samples, then the
uncertainty component for the within-laboratory reproducibility, uRw , at this
concentration and for this matrix, can be estimated from the standard deviation of
235 Conference Proceedings WATER 2016 23-25 June Constanţa
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these QC results (5). A minimum number of eight measurements is required for the
estimation of each uncertainty component.
To evaluate the uncertainty associated with method and laboratory bias, the
difference from the certified value and the uncertainty of the certified value are
estimated. If only one reference material is available, the results of analyses of this
reference material are treated as the best available estimate for the measurement
uncertainty component associated with method and laboratory bias. A minimum
number of six measurements is required for the estimation of each uncertainty
component.
The estimation of measurement uncertainty is based on analytical quality
control results and validation data which represent the within-laboratory
reproducibility, and the method and laboratory bias. Measurements were combined,
so only eight measurements in a one-day run were used for the calculations. The
measurement uncertainty components, expressed as relative uncertainties are
summarized in Table 2.
4. CONCLUSIONS
6. REFERENCES