GREEN CHEM SOLUTIONS PVT LTD

Verification Report
Doc No. : GCS/GF/LAB-520 Date(s) of Testing: 18.10.2022 to 28.10.2022

Sample Code: Lead Spike Sample Test Method/Procedure: IS 5182 Part 22 : 2004 (Reaff.2009)

Sample Name: Ambient Air Parameter Lead as Pb

Sl. No. Verification Parameter Acceptance Criteria Verification Results Remarks

Linearity
0.995 ≤ r2 0.995≤ 0.9994 Complies
(Annexure-1)

1 Intercept c≤2% 0.0006 ≤ 0.0008 Complies

Calibration verification : % All Response Factor values Difference

Within 2.5 % Complies
Difference for RF within 2.5 %

LOD LOD is
2 LOD < Cmin & 10 x LOD > Cmin 25 mg/L
(Annexure-1) acceptable

LOQ
3 -- 464.52 mg/L --
(Annexure-1)

Working Range (Annexure-

4 -- 0.01 to mg/L --
1)

DAY - 1 HorRAT = 0.3 < 0.32 > 1.3 Complies

Precision Repeatability
5 HORRAT = 0.3 to 1.3 DAY - 2 HorRAT = 0.3 < 0.33 > 1.3 Complies
(Annexure-2)

DAY - 3 HorRAT = 0.3 < 0.32 > 1.3 Complies

Intermediate
6 Reproducibility HORRAT = 0.3 to 1.3 HorRAT = 0.3 < 0.32 > 1.3 Complies
(Annexure-2)
Accuracy
7 Recovery (RSD) = 10% Recover Mean RSD = 9.28% Complies
(Annexure-2)

Measurement Uncertainty
8 Expanded Uncertainty = 44 % 0.085 ± 0.026 mg/L" = 31% Complies
(Annexure-3)

Conclusion:
The verification data show that the method is precise, accurate and hence the method is fit for determining
Lead as Pb in Ambient Air.

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Prepared on: 10.10.2022

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GREEN CHEM SOLUTIONS PVT LTD
Verification Report
Annexure-1: LOD & LOQ Calculations
ID No. : GCS/GF/LAB-520 Date(s) of Testing: 18.10.2022
Sample
Lead Spike Sample Sample Name: Ambient Air Parameter Lead as Pb
Code:

Concn % Difference for 90 to 110

Absorbance n 15
mg/L RF within 5 % % Recovery
0.5 0.0201 -1.66 101.7 slope (m) 0.0395
0.5 0.0198 -0.14 100.1 intercept (c) 0.0006 ≤ 0.0008
0.5 0.0195 1.38 98.6 r 2
0.9994 ≥ 0.995
1.0 0.0405 -2.41 102.4 residual standard deviation - SDxy 0.00162
1.0 0.0394 0.37 99.6 LOD 0.135 µg/ml
1.0 0.0399 -0.90 100.9 LOQ 0.406 µg/ml
2.0 0.0804 -1.66 101.7 CHECKING (Is LOD < Cmin & 10 x LOD > Cmin)
2.0 0.0797 -0.77 100.8 LOD is acceptable
2.0 0.0802 -1.40 101.4
3.0 0.1201 -1.23 101.2
3.0 0.1205 -1.57 101.6
3.0 0.1212 -2.16 102.2 (Ms-Mb)= Obsrved value from AAS, µg/ml 0.135
5.0 0.1998 -1.05 101.0 Vs = Extract Volume, mL 25
5.0 0.1992 -0.75 100.7 Fa = Area of Paper, cm2 464.52

5.0 0.1936 2.09 97.9 Ft = Used Area of Paper, cm2 206.44

RF = Response V=Air Volume, m3 1440

Factor

Method LOD, µg/m3 = 0.005

Method LOQ, µg/m3 = 0.02

0.2500

0.2000

0.1500
Absorbance

0.1000

0.0500

0.0000
0.0 1.0 2.0 3.0 4.0 5.0 6.0
Concentration, mg/L
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 GREEN CHEM SOLUTIONS PVT LTD
Verification Report
Annexure-2: Accuracy & Precision
Doc No. : GCS/GF/LAB-520 Date(s) of Testing: 18.10.2022 to 21.10.2022
Sample
Sample Code: Lead Spike Sample Ambient Air Parameter Lead as Pb
Name:

Vs = Extract Volume, mL 25
Fa = Area of Paper, cm2 464.52 Pb µg/m3
Formula
Ft = Used Area of Paper, cm2 206.44
Precision V=Air Volume, m3 1440

Blank Absorbance mL Sample volume Spike concentration (mg/L)

-0.0010 0.0007 0.0003 25 25 25 0.50

Trial mg/L Pb in 100 ml final volume Observed value from AAS method
Sample Absorbance
instrument Reading (µg/m3)
Day - 1; Day - 2; Day - 3; Day - 1; Day - 2; Day - 3; Day - 1; Day - 2; Day - 3;
Chemist-1 Chemist-2 Chemist-1 Chemist-1 Chemist-2 Chemist-1 Chemist-1 Chemist-2 Chemist-1
1 0.0186 0.0197 0.0203 0.471 0.499 0.513 0.018 0.019 0.020
2 0.0174 0.0193 0.0186 0.441 0.489 0.471 0.017 0.019 0.018
3 0.022 0.0169 0.0192 0.557 0.428 0.486 0.022 0.017 0.019
4 0.0198 0.0206 0.0189 0.501 0.522 0.478 0.020 0.020 0.019
5 0.0204 0.0168 0.0213 0.516 0.425 0.539 0.020 0.017 0.021
6 0.0193 0.0217 0.0178 0.489 0.549 0.451 0.019 0.021 0.018
7 0.0169 0.0185 0.0231 0.427 0.468 0.584 0.017 0.018 0.023
Average, µg/m3 = 0.019 0.019 0.020
Standard Deviation, µg/m3 = 0.0017 0.0018 0.0018
RSDR, % = 9.17 9.56 9.11
(Based on Horwitz Eqn.) PRSDR,% = 29.06 29.08 28.91

Repetability (HorRAT= 0.3 to 1.3) RSDR / PRSDr = 0.32 0.33 0.32

Intermediate Reproducibility, µg/m3 = 0.019
Standard Deviation, µg/m3 = 0.0018
RSDR, % = 9.27
(Based on Horwitz Eqn.) PRSDR,% = 29.01
Intermediate Reproducibility (HorRAT= 0.3 to 1.3) RSDr / PRSDr = 0.32

Precision (range) Chart:

Range , µg/m3 = 0.0016 0.0019 0.0050 0.0017 0.0045 0.0038 0.0061

Range Standdeviation, s µg/m = 3
0.00

Mean Range d2 × s , µg/m3 = Ṝ 0.0031 0.0031 0.0031 0.0031 0.0031 0.0031 0.0031

CL 0.0079 0.0079 0.0079 0.0079 0.0079 0.0079 0.0079

WL 0.0063 0.0063 0.0063 0.0063 0.0063 0.0063 0.0063

D2 = factor to convert s to the range (1.128 for duplicates, as given in Table 1020:I), Perfect agreement between replicates or duplicates results in a
s(R) = standard deviation of the range, and difference of zero when the values are subtracted, so the baseline on
D4 = factor to convert mean range to 3s(R) (3.267 for duplicates, as given in Table 1020:I) the chart is zero. Therefore for precision charts, only upper warning
limits and upper control limits are meaningful.

Table 1020:I 0.0090

0.0080
0.0070
0.0060

R 0.0050
a 0.0040
n
g 0.0030
e 0.0020
0.0010
0.0000
1 2 3 4 5 6 7
PART
Ṝ CL WL Range
0.0020
0.0010
0.0000
1 2 3 4 5 6 7
PART
Ṝ CL WL Range
Accuracy
Spike concentration (µg/m3) Accuracy (mean) Chart:
0.02 Control Level Warning Level
%
Observed value from Recovery
Trial AAS method UCL LCL UWL LWL
Mean
(80 to 120 % Recovery)

Day - 1; Day - 2; Day - 3;

X + 3S X - 3S X + 2S X - 2S
Chemist-1 Chemist-2 Chemist-1 X
1 96.0 101.7 104.6 100.0 127.8 72.2 118.5 81.5
2 89.9 99.7 96.0 100.0 127.8 72.2 118.5 81.5
3 113.5 87.2 99.0 100.0 127.8 72.2 118.5 81.5
4 102.1 106.4 97.4 100.0 127.8 72.2 118.5 81.5
5 105.2 86.6 109.9 100.0 127.8 72.2 118.5 81.5
6 99.7 111.9 91.9 100.0 127.8 72.2 118.5 81.5
7 87.0 95.4 119.0 100.0 127.8 72.2 118.5 81.5
Average (90 to 110% Recovery) = 99.0 98.4 102.5
Standard Deviation = 9.079 9.407 9.339
Average Standard Deviation, S = 9.275
RSD, % = 9.17 9.56 9.11
Mean (10 RSD %) = 9.28

130.0
125.0
120.0
115.0
110.0
105.0
100.0
95.0 1 2 3 4 5 6 7
90.0
85.0
80.0
75.0
70.0
PAR
T
Day - 1; Chemist-1 Day - 2; Chemist-2 Day - 3; Chemist-1 % Recovery Mean
UCL LCL UWL LWL

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 LOGO
GREEN CHEM SOLUTIONS PVT LTD
Estimation of Measurement Uncertainty in Testing
Doc No.: GCS/QF/7.6 -1 Sample Code: 2246 AAQ1+Spike Date(s) of Testing: 21.10.2022
Sample Name: Ambient Air Test Parameter Lead
A.Step 1 : Specification of the Measurand
A.1 Scope
This method covers the Uncertainty in the estimation of Lead in Ambient Air as per IS 5182 Part 22 : 2004 (Reaff.2009)

A.2 Measurement Procedure

The Atomic Absorption Spectroscopy (AAS) technique makes use of absorption Spectrometry to assess the concentration of an analyte
in the sample. The method is based on active sampling using PM10 High Volume Sampler and then sample analysis is done by atomic absorption spectrophotometer.

Take aliquot Acid Digestion Make up sample Homogenise AAS

of sample leachate Determination

Results
Prepared AAS
Calibration Determination
Standard

A.3 Formula

Where
(Ms-Mb)= Obsrved value from AAS, µg/L Vs = Extract Volume, mL
Fa = Area of Paper, cm2 V=Air Volume, m3
Ft = Used Area of Paper, cm2

B.Step 2 : Identifying and analysing uncertainty source

B.1 Cause and Effect Diagram:

Repeatability Calibration CRM

Uncertainty in Lead in Ambient Air

Flow Rate Sampling Time

Extract Volume Area of Paper

Air Volume
Area of Paper used

B.2 Equipment Used

1. Hot plate 2. Glasswares
3. Atomic Absorption spectrometry 4.Air Volume Sampler
B.3 Sources of Uncertainty
Type - A Type - B
1. Repeatability ( Method Verfication Precision) 1. Air Volume sampler
2. Concentration ( Calibration Graph) 2. Paper area
3. Extract Volume

C.Step 3 : Quantifying uncertainty Component

C.1 Uncertainty in Air Volume

Air Volume, m3 = 1440
Description X U K U/(x*K)
Flow Rate, m3/min 1.05 0.024150 2 0.01150 u1
Time, min 1440 0.35 2 0.00012 u2

Standard Uncertainty due to Air Volume, UAM = 16.5609

C.2 Uncertainty in Paper Area

Uncertainty due to Area of Paper:
Uncertainty in Measuring Tape , UMT , cm= 0.001253 Area of Paper, cm2 = 464.52

k= 2 (2 Times)
Standard Uncertainty due to Area of Paper, UAP = SQRT(2 x (UMT/k)2) = 0.000886
Uncertainty due to Area of Paper Used:
Uncertainty in Measuring Tape , UMT , cm= 0.001253 Area of Paper used, cm2 = 206.44
k= 2 (2 Times)
Standard Uncertainty due to Area of Paper Used, UAPU = SQRT(2 x (UMT/k)2) = 0.000886

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 LOGO
GREEN CHEM SOLUTIONS PVT LTD
Estimation of Measurement Uncertainty in Testing
Doc No.: GCS/QF/7.6 -1 Sample Code: 2246 AAQ1+Spike Date(s) of Testing: 21.10.2022
Sample Name: Ambient Air Test Parameter Lead

C.3 Uncertainty due to make up volume of sample : ( Volumetric Flask ) GCS/LAB/VP-25ml

Repetability: Replicate weighing measurements of the volumes of Flask give astandard deviation of value, which will be used = PUREP 0.03800
directly in the final calculation of standard uncertainty

Calibration : Uncertainty in Flask , mL= 0.03850 ml sample Volume V, mL = 25

k= 2 Standard Uncertainty, ml PU CAL 0.019250

Temperature : According to the manufacturer the flask has been calibrated at a temperature of 20 °C, whereas the laboratory temperature aries between the
limits of ± 3 °C. The coefficient of volume expansion for water is 2.1 ×10 -4 °C-1

volume variation ± 25 × 3 × 0.00021 0.01575

The assumption of a rectangular distribution for the temperature Standard Uncertainty, ml PU TEM
1.732 0.00909
variation (√3 ) (Ur)
Three contributions are combined Standard Uncertainty due to make up volume, ml UMV = SQRT ((PUREP) + (PUCAL) + (PUTEM) )
2 2 2
0.0436

C.4 Uncertainty in Concentration Solution

Uncertainty due to Calibration Graph:
Con., Xi, % Difference for
S. No. Abs.Y (∑Xi - X)^2 X- Mean value of Calibrn Stds, Cm = 2.300
µg/ml RF within 2.5 %
1 0.5 0.0201 3.2400 -0.6973 Residual Std Devn - SDxy = 0.00062
2 0.5 0.0198 3.2400 0.8056 n= 15
3 0.5 0.0203 3.2400 -1.6993 Slope (b) = 0.0399
4 1.0 0.0405 1.6900 -1.4488 Sxx =(∑Xi - X)^2 38.4
5 1.0 0.0394 1.6900 1.3066 Intercept (a) = 0.0003 ≤ 0.0008
6 1.0 0.0399 1.6900 0.0541 Sample Results Direct Instrument Reading, µg/L = 2.17
7 2.0 0.0814 0.0900 -1.9498 Sample Trial, k = 3
8 2.0 0.0797 0.0900 0.1794
9 2.0 0.0802 0.0900 -0.4468
10 3.0 0.1201 0.4900 -0.2798
11 3.0 0.1205 0.4900 -0.6138
12 3.0 0.1212 0.4900 -1.1983
13 5.0 0.1998 7.2900 -0.0962
14 5.0 0.1992 7.2900 0.2044
15 5.0 0.1996 7.2900 0.0040
Sample 2.16 0.0862 -
Trial - 1
Sample 2.21 0.0885 -
Trial - 2
Sample 2.13 0.0851 -
Trial - 3

Uncertainty due to calibration graph, Ucal_graph mg/L =

0.0098

At the 95% confidence level, the 2-tailed Student t value for 15 degrees of freedom = 2.1314
Uncertainty in Calibration cure of Unknown Concentration (Ucal.graph) = 2.17 mg/L ± = 0.0209
k= 2
Standard Uncertainty due to calibration graph, Ucal_graph = Ucal.graph / k = µg/mL 0.0104

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 LOGO
GREEN CHEM SOLUTIONS PVT LTD
Estimation of Measurement Uncertainty in Testing
Doc No.: GCS/QF/7.6 -1 Sample Code: 2246 AAQ1+Spike Date(s) of Testing: 21.10.2022
Sample Name: Ambient Air Test Parameter Lead
C.5 Uncertainty in Lead in Ambient Air:
Repeatability - Method (Precision)
The method verfication shows a repeatability for the determination of 9.277% as Relative standard Deviation. This value can be used directly for the
calculation of the combined standard uncertainty associated with the different repeatability terms.
Avg.Repeatability concentration 0.02
Spike concentration 0.5 mg/L
Relative Standard Deviation URep = 9.277 %
No. of Repeatability 21
1 = %RSD / 100% of Uncertainty 0.0928
UMRep, 1 0.0928
D.Step 4 : Calculate the combined standard and Expanded uncertainty
D.1 Combined Standard Uncertainty and Expanded Uncertainty in Lead in Ambient air:

Using the values given below

(Ms-Mb)= Obsrved value from AAS, µg/ml 2.17
Vs = Extract Volume, mL 25
Fa = Area of Paper, cm2 464.52
Ft = Used Area of Paper, cm2 206.44
V=Air Volume, m3 1440
Results, µg/m3 = 0.085

Table D.1. Combined Standard Uncertainty in Lead in Ambient Air

Type Description Value, X Std. Uncert. UX Relat. Std. Uncert. UX/X

A UMRep, 1.000 0.0928 0.09277 Ux1

A Ucal-graph µg/m3 0.085 0.0104 0.12330 Ux2
B UAM m3 1440 16.5609 0.01150 Ux3
B UAP cm2 464.5 0.000886 0.0000019 Ux4
B UAPU cm2 206.4 0.000886 0.0000043 Ux5
B SMFUMV mL 25 0.0436 0.00174 Ux6

Combined Uncertainty, = 0.08 µg/m3 0.0131

Expanded Uncertainty @ 95% confident level (k=2), UE = 2 * UC = 0.0262

Figure D.1. Uncertainty Contribution in Lead in Ambient Air

UAPU 0.00174

UAP 0.0000043

UAM 0.0000019

Ucal-graph 0.01150

UMRep, 0.12330

Description 0.09277

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14

E.Step 5 : Reporting uncertainty

Lead in Ambient Air = 0.08 ± 0.03 µg/m3

The acceptance criterion is up to 44%.

% of Uncertainty = 30.95

F.Step 6 : Examine the uncertainty budget

Lead in Ambient Air – spreadsheet calculation of uncertainty
A B C D E F G H I
1 Ux1 Ux2 Ux3 Ux4 Ux5 Ux6 Ux7
2 Value 1.0 0.085 1440 464.5 206.4 25.0
3 Uncertainty 0.0928 0.0104 16.5609 0.001 0.0009 0.04356
4
5 Ux1 1.0 1.093 1.0 1.0 1.0 1.0 1.0
6 Ux2 0.085 0.085 0.0951 0.085 0.085 0.085 0.095
7 Ux3 1440 1440 1440 1456.6 1440 1440 1440
8 Ux4 464.5 464.5 464.5 464.5 464.52 464.5 464.56
9 Ux5 206.4 206.4 206.4 206.4 206.4 206.441 206.4
10 Ux6 25.0 25.0 25.0 25.0 25.00 25.0 25.04
11 Ux7 0.0 0.0 0.0 0.0 0.0 0.000 0.0
12
13 Results 0 ng/m3 0.09249343012 0.09507722467109 0.0856143064 0.084641 0.0846412 0.08478835
14 u(y,xi) 0.0079 0.0104 0.0010 0.0000 0.0000 0.0001
u(y)2,u(y,
15 0.000172 6.1662496E-05 0.00010891722724 9.475532E-07 2.61E-14 1.3204E-13 2.1747E-08
xi)2
16
17 U(Pb) 0.0131

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