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: Nickel Spike Sample Test Method/Procedure: EPA, Compendium Method IO-3.2, June 1999

Sample Name: Ambient Air Parameter Nickel as Ni

Sl. No. Verification Parameter Acceptance Criteria Verification Results Remarks

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

1 Intercept c≤2% -0.0005 ≤ 0.0021 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 0.658 ng/m3
(Annexure-1) acceptable

LOQ
3 -- 1.973 ng/m3 --
(Annexure-1)

DAY - 1 HorRAT = 0.3 < 0.43 > 1.3 Complies

Precision Repeatability
4 HORRAT = 0.3 to 1.3 DAY - 2 HorRAT = 0.3 < 0.4 > 1.3 Complies
(Annexure-2)

DAY - 3 HorRAT = 0.3 < 0.4 > 1.3 Complies

Intermediate Reproducibility
5 HORRAT = 0.3 to 1.3 DAY - 3 HorRAT = 0.3 < 0.41 > 1.3 Complies
(Annexure-2)

Accuracy
6 Recovery (RSD) = 10% Recover Mean RSD = 5.14% Complies
(Annexure-2)

Measurement Uncertainty
7 Expanded Uncertainty = 22 % 3.907 ± 0.502 mg/L" = 12.9% Complies
(Annexure-3)

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

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Verification Report
Annexure-1: LOD & LOQ Calculations
Doc No. : GCS/GF/LAB-520 Date(s) of Testing: 18.10.2022
Sample
Nickel Spike Sample Sample Name: Ambient Air Parameter Nickel as Ni
Code:

Concn % Difference for 90 to 110

Absorbance n 15
mg/L RF within 5 % % Recovery
0.1 0.0100 4.67 95.3 slope (m) 0.1049
0.1 0.0103 1.81 98.2 intercept (c) -0.0005 ≤ 0.0021
0.1 0.0101 3.72 96.3 r2 1.0000 ≥ 0.995
0.5 0.0515 1.81 98.2 residual standard deviation - SDxy 0.00054
0.5 0.0518 1.24 98.8 LOD 0.017 mg/L
0.5 0.0529 -0.86 100.9 LOQ 0.051 mg/L
1.0 0.1045 0.38 99.6 CHECKING (Is LOD < Cmin & 10 x LOD > Cmin)
1.0 0.1041 0.76 99.2 LOD is acceptable
1.0 0.1048 0.09 99.9
2.0 0.2085 0.62 99.4
2.0 0.2094 0.19 99.8
2.0 0.2084 0.67 99.3 (Ms-Mb)= Obsrved value from AAS, µg/L 16.8
5.0 0.5235 0.19 99.8 Vs = Extract Volume, mL 25
5.0 0.5244 0.02 100.0 Fa = Area of Paper, cm2 464.52

5.0 0.5246 -0.02 100.0 Ft = Used Area of Paper, cm2 206.44

RF = Response V=Air Volume, m3 1440

Factor

Method LOD, ng/m3 = 0.658

Method LOQ, ng/m3 = 1.97

0.6000
0.5000
0.4000
Absorbance

0.3000
0.2000
0.1000
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: Nickel Spike Sample Ambient Air Parameter Nickel as Ni
Name:

Vs = Extract Volume, mL 25
Fa = Area of Paper, cm2 464.52
Formula
Ft = Used Area of Paper, cm2 154.83
Precision V=Air Volume, m3 1440
Spike concentration (mg/L) +
Blank Absorbance mL Sample volume
Filter Paper
-0.0021 -0.0009 0.0007 25 25 25 2.50
Trial mg/L Ni in 25 ml final volume Observed value from AAS method
Sample Absorbance
Instrument Reading (ng/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 0.0105 0.0101 0.0102 0.100 0.096 0.097 5.214 5.000 5.052
2 0.0108 0.0096 0.0110 0.103 0.092 0.105 5.365 4.792 5.469
3 0.0094 0.0105 0.0108 0.090 0.100 0.103 4.688 5.209 5.365
4 0.0102 0.0108 0.0095 0.097 0.103 0.091 5.052 5.365 4.740
5 0.0110 0.0103 0.0105 0.105 0.098 0.100 5.469 5.104 5.209
6 0.0099 0.0101 0.0104 0.094 0.096 0.099 4.896 5.000 5.157
7 0.0107 0.0112 0.0099 0.102 0.107 0.094 5.313 5.573 4.896
Average, ng/m3 = 5.14 5.15 5.13
Standard Deviation, ng/m3 = 0.2786 0.2594 0.2549
RSDR, % = 5.42 5.04 4.97
(Based on Horwitz Eqn.) PRSDR,% = 12.5 12.5 12.51

Repeatability (HorRAT= 0.3 to 1.3) RSDR / PRSDr = 0.43 0.40 0.40

Intermediate Reproducibility, ng/m3 = 5.139
Standard Deviation, ng/m3 = 0.2643
RSDR, % = 5.14
(Based on Horwitz Eqn.) PRSDR,% = 12.51
Intermediate Reproducibility (HorRAT= 0.3 to 1.3) RSDr / PRSDr = 0.41

Precision (range) Chart:

Range , ng/m = 3
0.214 0.677 0.677 0.625 0.365 0.260 0.677
Range Standdeviation, s ng/m3 = 0.21

Mean Range d2 × s , ng/m = 3

Ṝ 0.357 0.357 0.357 0.357 0.357 0.357 0.357

CL 0.921 0.921 0.921 0.921 0.921 0.921 0.921

WL 0.733 0.733 0.733 0.733 0.733 0.733 0.733

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 the
D4 = factor to convert mean range to 3s(R) (3.267 for duplicates, as given in Table 1020:I) chart is zero. Therefore for precision charts, only upper warning limits
and upper control limits are meaningful.

Table 1020:I 1.000

0.900
0.800
0.700
0.600
R 0.500
a
n 0.400
g 0.300
e
0.200
0.100
0.000
1 2 3 4 5 6 7
PART
Ṝ CL WL Range
0.200
0.100
0.000
1 2 3 4 5 6 7
PART
Ṝ CL WL Range
Accuracy
Spike concentration (ng/m3) Accuracy (mean) Chart:
5.14 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
1 101.4 97.3 98.3 100.0 115.4 84.6 110.3 89.7
2 104.4 93.2 106.4 100.0 115.4 84.6 110.3 89.7
3 91.2 101.3 104.4 100.0 115.4 84.6 110.3 89.7
4 98.3 104.4 92.2 100.0 115.4 84.6 110.3 89.7
5 106.4 99.3 101.3 100.0 115.4 84.6 110.3 89.7
6 95.3 97.3 100.3 100.0 115.4 84.6 110.3 89.7
7 103.4 108.4 95.3 100.0 115.4 84.6 110.3 89.7
Average (90 to 110% Recovery) = 100.1 100.2 99.8
Standard Deviation = 5.421 5.048 4.960
Average Standard Deviation, S = 5.143
RSD, % = 5.42 5.04 4.97
Mean (10 RSD %) = 5.14

117.0

112.0

107.0

102.0

97.0 1 2 3 4 5 6 7

92.0

87.0

82.0
PART
Day - 1; Chemist-1 Day - 2; Chemist-2 Day - 3; Chemist-1 % Recovery Mean
UCL LCL UWL LWL

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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 Nickel
A.Step 1 : Specification of the Measurand
A.1 Scope
This method covers the Uncertainty in the estimation of Nickel in Ambient Air as per EPA, Compendium Method IO-3.2, June 1999

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 Nickel 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
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
4. Dilution Factor

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 1.09 0.025070 2 0.01150 u1
Time, min 480 0.35 2 0.00036 u2

Standard Uncertainty due to Air Volume, UAM = 16.5682

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

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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 Nickel
Uncertainty due to Area of Paper Used:
Uncertainty in Measuring Tape , UMT , cm= 0.001253 Area of Paper used, cm2 = 464.52
k= 2 (2 Times)
Standard Uncertainty due to Area of Paper Used, UAPU = SQRT(2 x (UMT/k)2) = 0.000886

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 PUCAL 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 °C
-4 -1

volume variation ± 25 × 3 × 0.00021 0.01575

The assumption of a rectangular distribution for the temperature Standard Uncertainty, ml PUTEM
1.732 0.00909
variation (√3 ) (Ur)
Three contributions are combined Standard Uncertainty due to make up volume, ml UMV = SQRT ((PUREP) 2+ (PUCAL)2 + (PUTEM)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 = 1.720
mg/L RF within 2.5 %
1 0.1 0.0100 2.6244 4.6696 Residual Std Devn - SDxy = 0.00054
2 0.1 0.0103 2.6244 1.8097 n= 15
3 0.1 0.0101 2.6244 3.7163 Slope (b) = 0.1049
4 0.5 0.0515 1.4884 1.8097 Sxx =(∑Xi - X)^2 46.4
5 0.5 0.0518 1.4884 1.2377 Intercept (a) = -0.0005 ≤ 0.0021
6 0.5 0.0529 1.4884 -0.8595 Sample Results Direct Instrument Reading, mg/L = 0.100
7 1.0 0.1045 0.5184 0.3798 Sample Trial, k = 3
8 1.0 0.1041 0.5184 0.7611
9 1.0 0.1048 0.5184 0.0938
10 2.0 0.2085 0.0784 0.6181
11 2.0 0.2094 0.0784 0.1891
12 2.0 0.2084 0.0784 0.6658
13 5.0 0.5235 10.7584 0.1891
14 5.0 0.5244 10.7584 0.0175
15 5.0 0.5246 10.7584 -0.0206
Sample 0.103 0.0108 -
Trial - 1
Sample 0.095 0.0100 -
Trial - 2
Sample 0.102 0.0107 -
Trial - 3

Uncertainty due to calibration graph, Ucal_graph mg/L =

0.0034

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) = 0.10 mg/L ± = 0.0073
k= 2
Standard Uncertainty due to calibration graph, Ucal_graph = Ucal.graph / k = mg/L 0.0037

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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 Nickel
C.5 Uncertainty in Nickel in Ambient Air:
Repeatability - Method (Precision)

The method verfication shows a repeatability for the determination of 5.143% 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 5.14 ng/m3
Spike concentration 2.50 mg/L
Relative Standard Deviation URep = 5.143 %
No. of Repeatability 21
1 = %RSD / 100% of Uncertainty 0.0514
UMRep, 1 0.0514
D.Step 4 : Calculate the combined standard and Expanded uncertainty
D.1 Combined Standard Uncertainty and Expanded Uncertainty in Nickel in Ambient air:

Using the values given below

(Ms-Mb)= Obsrved value from AAS, µg/L 100.00
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, ng/m3 = 3.907

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

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

A UMRep, 1.000 0.0514 0.05143 Ux1

A Ucal-graph mg/L 0.10 0.0037 0.03674 Ux2
B UAM m3 1440 16.5682 0.01151 Ux4
B UAP cm2 464.5 0.000886 0.0000019 Ux5
B UAPU cm2 464.5 0.000886 0.0000019 Ux6
B SMFUMV mL 25 0.0436 0.00174 Ux7

Combined Uncertainty, = 3.9 ng/m3 0.2511

Expanded Uncertainty @ 95% confident level (k=2), UE = 2 * UC = 0.5021

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

SMFUMV 0.00174

UAPU 0.0000019

UAP 0.0000019

UAM 0.01151

Ucal-graph 0.03674

UMRep, 0.05143

0 0.01 0.02 0.03 0.04 0.05 0.06

E.Step 5 : Reporting uncertainty

Nickel in Ambient Air = 3.91 ± 0.5 mg/L

The acceptance criterion is up to 22%.

% of Uncertainty = 12.85

F.Step 6 : Examine the uncertainty budget

Nickel 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 0.100 1440 464.5 464.5 25.0
3 Uncertainty 0.0514 0.0037 16.5682 0.001 0.0009 0.04356
4
5 Ux1 1.0 1.051 1.0 1.0 1.0 1.0 1.0
6 Ux2 0.100 0.100 0.1037 0.100 0.100 0.100 0.104
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 464.5 464.5 464.5 464.5 464.5 464.521 464.5
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 4 ng/m3 4.10741378647 4.05004665142196 3.9514491908 3.90651 3.9065097 3.91330859
14 u(y,xi) 0.2009 0.1435 0.0449 0.0000 0.0000 0.0068
u(y)2,u(y,
15 0.063037 0.04036542827 0.02060498288148 0.0020202236 5.56E-11 5.5554E-11 4.6326E-05
xi)2
16
17 U(Ni) 0.2511

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