1 Plant concentration data

1.1 Step 1: Results of reference materials

Reference materials were randomly incorporated into the routine samples to monitor analytical accuracy, precision, and any potential drift or offsets between batches. This approach also helped identify other types of analytical artifacts.

The reference materials used in this process were UPDEEP_SPRU_BARK_DRY, UPDEEP_SPRU_NEED_DRY, and UPDEEP_SPRU_TWIG_DRY. These materials were developed in-house as reference samples representing the three primary types of materials. While they do not adhere to international reference material standards, they have undergone multiple analyses by external laboratories to establish reliable reference values.

Additionally, the international reference material CLV-2 had been used.

1.1.1 Reference values of the reference materials

Below are the results for the reference values of these three reference materials:

Table 1.1: Number of above detection limit values for the preanalysed standard reference material (SRM) samples. The SRM samples are described and data is provided by Middleton et al. (2020). These preanalysed SRM analysis were made of dry-milled material with 2F method provided by Actlabs. The values were used as reference values in the x-charts.
Element UPDEEP_SPRU_BARK_DRY UPDEEP_SPRU_NEED_DRY UPDEEP_SPRU_TWIG_DRY
Ag 0 0 0
As 10 10 10
B 10 10 10
Ba 10 10 10
Be 0 0 0
Bi 10 0 1
Ca 10 10 10
Cd 10 10 10
Ce 10 10 10
Co 10 10 10
Cr 10 10 10
Cs 10 10 10
Cu 10 10 10
Dy 10 10 10
Er 10 10 10
Eu 10 10 10
Fe 10 10 10
Ga 10 10 10
Gd 10 10 10
Ge 10 1 9
Hf 8 0 5
Hg 10 0 0
Ho 10 10 10
In 0 0 0
K 10 10 10
La 10 10 10
Li 0 0 0
Lu 0 3 2
Mg 10 10 10
Mn 10 10 10
Mo 10 10 10
Na 10 10 10
Nb 10 10 10
Nd 10 10 10
Ni 10 10 10
Pb 10 7 10
Pd 0 0 0
Pr 10 10 10
Pt 0 0 0
Rb 10 10 10
Re 0 0 0
Sb 10 0 10
Sc 0 0 0
Se 8 4 7
Sm 10 10 10
Sn 1 0 0
Sr 10 10 10
Ta 10 10 10
Tb 10 6 10
Te 5 2 2
Th 10 10 10
Ti 10 10 10
Tl 10 10 10
Tm 0 0 0
U 10 10 10
V 10 10 10
W 1 1 1
Y 10 10 10
Yb 10 10 10
Zn 10 10 10
Zr 10 10 10

1.1.2 Measurement results of the reference materials

The aforementioned reference materials were randomly added to the sample set as supplementary samples within the larger batch of routine samples. Because of their random inclusion, both the sequence and order of the samples varied, as did the total number of measurements taken.

Table 1.2: Number of different SRM samples analysed with the routine samples. The UpDeep reference samples (Norway spruce needles, twigs and bark) are descibed by Middleton et al. (2020) and the CVL-2 (Black spruce) by Dalton and Dunn (1987).
ParentSampleID N
UPDEEP_SPRU_NEED_DRY 16
UPDEEP_SPRU_BARK_DRY 15
CLV-2 19
UPDEEP_SPRU_TWIG_DRY 16

The results of the measurements of the reference samples provide the following:

Table 1.3: Mean, madian, relative standard deviation (RSD) and relative mean absolute deviation (RMAD) of the four SRMs analysed with the routine samples.
Element CLV-2_Mean CLV-2_Median CLV-2_RSD CLV-2_RMAD UPDEEP_SPRU_BARK_DRY_Mean UPDEEP_SPRU_BARK_DRY_Median UPDEEP_SPRU_BARK_DRY_RSD UPDEEP_SPRU_BARK_DRY_RMAD UPDEEP_SPRU_NEED_DRY_Mean UPDEEP_SPRU_NEED_DRY_Median UPDEEP_SPRU_NEED_DRY_RSD UPDEEP_SPRU_NEED_DRY_RMAD UPDEEP_SPRU_TWIG_DRY_Mean UPDEEP_SPRU_TWIG_DRY_Median UPDEEP_SPRU_TWIG_DRY_RSD UPDEEP_SPRU_TWIG_DRY_RMAD
Ag 1.7e+01 1.7e+01 20 10 8.8e+00 8.6e+00 13 10 2.6e+00 2.9e+00 46 37 1.1e+01 1.2e+01 14 17
Al 1.1e+02 1.1e+02 13 11 9.3e+01 9.2e+01 6 6 7.6e+01 7.3e+01 15 6 9.4e+01 9.1e+01 14 11
As 3.4e+02 3.4e+02 15 17 3.0e+02 2.9e+02 11 13 1.0e+02 9.7e+01 18 17 5.2e+02 5.2e+02 8 6
Au 8.6e-01 5.2e-01 145 79 1.9e-01 1.5e-01 73 84 2.3e-01 2.5e-01 69 74 9.0e-01 2.1e-01 193 105
B 3.1e+01 4.2e+01 49 47 2.1e+00 1.9e+00 50 5 3.1e+00 2.8e+00 48 12 4.2e+00 2.6e+00 61 8
Ba 2.3e+04 2.3e+04 8 8 1.2e+05 1.2e+05 4 4 4.1e+04 4.1e+04 4 5 6.7e+04 6.6e+04 5 5
Be 4.7e+00 4.2e+00 50 33 1.5e+00 1.6e+00 46 52 4.6e+00 4.4e+00 27 28 1.3e+00 1.4e+00 36 30
Bi 9.8e+00 9.2e+00 21 19 8.9e+00 8.8e+00 16 18 3.3e+00 2.9e+00 77 38 4.1e+00 3.8e+00 52 56
Ca 7.5e+03 7.7e+03 8 5 1.0e+04 1.0e+04 8 10 5.4e+03 5.5e+03 7 7 4.0e+03 4.1e+03 6 4
Cd 1.3e+01 1.3e+01 23 15 1.3e+02 1.3e+02 7 6 1.4e+01 1.4e+01 14 11 4.2e+01 4.2e+01 8 10
Ce 2.3e+02 2.2e+02 10 9 7.6e+01 7.5e+01 10 6 1.7e+01 1.7e+01 8 11 7.7e+01 7.6e+01 12 12
Co 6.7e+01 7.0e+01 13 9 1.3e+02 1.3e+02 8 10 8.2e+01 8.1e+01 8 8 2.4e+02 2.3e+02 11 7
Cr 3.9e+02 3.8e+02 10 7 1.4e+02 1.4e+02 7 8 6.1e+01 4.9e+01 103 18 3.0e+02 3.0e+02 11 12
Cs 1.8e+01 1.7e+01 20 18 3.7e+01 3.7e+01 13 5 7.0e+01 6.9e+01 13 18 8.2e+01 8.2e+01 7 7
Cu 2.0e+03 1.9e+03 13 7 5.1e+03 5.1e+03 2 2 1.4e+03 1.4e+03 5 5 5.9e+03 5.8e+03 4 3
Dy 1.4e+01 1.4e+01 12 11 4.7e+00 4.8e+00 18 24 3.2e+00 3.2e+00 19 15 5.2e+00 5.3e+00 16 11
Er 6.4e+00 6.5e+00 15 17 2.5e+00 2.6e+00 21 23 1.7e+00 1.8e+00 27 13 2.8e+00 2.8e+00 22 22
Eu 4.2e+00 3.6e+00 37 44 1.7e+01 1.8e+01 23 4 6.0e+00 6.3e+00 25 10 8.1e+00 9.6e+00 48 33
Fe 2.6e+02 2.5e+02 9 7 9.2e+01 9.4e+01 6 7 4.0e+01 4.0e+01 6 8 1.2e+02 1.2e+02 4 5
Ga 5.3e+01 3.2e+01 53 37 6.6e+00 6.7e+00 61 75 6.7e+01 6.9e+01 26 14 1.6e+01 1.5e+01 31 16
Gd 1.0e+01 9.8e+00 12 12 5.4e+00 5.1e+00 24 25 2.5e+00 2.3e+00 25 17 5.3e+00 5.1e+00 20 21
Ge 2.8e+00 2.7e+00 41 36 2.9e+00 3.0e+00 29 26 5.3e+00 5.4e+00 30 15 1.3e+01 1.7e+01 64 15
Hf 3.4e+00 2.6e+00 86 31 9.0e-01 8.0e-01 41 45 3.1e-01 2.3e-01 90 68 1.2e+00 1.1e+00 29 24
Hg 2.8e+01 2.9e+01 14 14 1.7e+02 1.7e+02 5 5 2.8e+01 2.8e+01 10 6 2.5e+01 2.5e+01 8 9
Ho 2.6e+00 2.6e+00 8 5 1.1e+00 1.1e+00 19 20 7.9e-01 8.4e-01 22 16 1.0e+00 1.0e+00 19 19
In 4.7e-01 4.2e-01 45 56 3.8e-01 3.4e-01 65 101 1.7e-01 1.4e-01 80 69 2.4e-01 1.9e-01 97 80
K 3.7e+03 3.8e+03 9 4 9.0e+02 8.9e+02 7 7 4.0e+03 3.9e+03 7 8 3.8e+03 3.8e+03 4 2
La 1.2e+02 1.1e+02 12 8 6.4e+01 6.5e+01 8 5 2.3e+01 2.3e+01 7 6 6.4e+01 6.5e+01 7 7
Li 1.8e+02 1.7e+02 20 15 1.0e+01 1.0e+01 27 12 1.9e+01 1.9e+01 13 10 3.3e+01 3.4e+01 13 13
Lu 4.9e-01 4.4e-01 39 43 2.6e-01 1.9e-01 79 44 1.2e-01 1.1e-01 66 62 2.9e-01 1.9e-01 105 37
Mg 8.2e+02 8.6e+02 12 5 2.2e+02 2.3e+02 13 20 8.2e+02 8.2e+02 10 12 9.0e+02 9.0e+02 9 9
Mn 1.7e+06 1.8e+06 9 7 3.8e+05 3.8e+05 4 4 1.1e+06 1.1e+06 3 2 5.4e+05 5.4e+05 4 2
Mo 7.1e+01 7.1e+01 15 14 1.4e+01 1.3e+01 28 19 3.1e+01 3.1e+01 16 11 3.0e+01 2.9e+01 17 8
Na 7.4e+00 7.2e+00 33 38 7.6e+01 7.8e+01 7 8 3.0e+01 3.1e+01 8 8 4.9e+01 5.0e+01 8 4
Nb 9.7e+00 1.2e+01 54 76 3.6e+00 3.2e+00 40 19 8.6e-01 8.4e-01 39 11 6.2e+00 4.0e+00 62 18
Nd 9.7e+01 1.0e+02 13 11 3.7e+01 3.6e+01 12 15 1.4e+01 1.4e+01 16 14 4.4e+01 4.3e+01 16 19
Ni 5.2e+02 5.0e+02 25 11 7.5e+02 7.5e+02 9 8 6.6e+02 6.9e+02 11 9 2.3e+03 2.2e+03 18 3
P 8.8e+02 9.1e+02 9 6 1.8e+02 1.8e+02 10 10 1.4e+03 1.5e+03 8 7 1.1e+03 1.1e+03 7 4
Pb 1.1e+03 1.1e+03 10 7 1.2e+03 1.2e+03 6 7 6.9e+01 6.8e+01 17 9 4.6e+02 4.5e+02 12 7
Pd 2.3e+00 1.5e+00 94 138 6.4e+00 6.6e+00 29 18 4.5e+00 4.8e+00 29 12 3.5e+00 4.4e+00 66 37
Pr 2.5e+01 2.5e+01 12 11 9.8e+00 9.7e+00 11 16 3.6e+00 3.6e+00 10 12 1.1e+01 1.1e+01 16 17
Pt 1.2e-01 3.9e-02 146 136 1.7e-01 2.0e-01 74 99 2.0e-01 1.1e-01 80 116 1.8e-01 1.8e-01 65 75
Rb 2.9e+03 3.0e+03 7 4 4.2e+03 4.2e+03 3 4 1.0e+04 1.0e+04 5 3 1.2e+04 1.2e+04 3 3
Re 2.6e+01 2.6e+01 6 3 4.4e-02 3.5e-02 67 100 3.6e-02 2.1e-02 99 120 3.1e-02 2.3e-02 77 96
Sb 3.9e+01 3.4e+01 39 36 2.6e+01 2.4e+01 37 20 6.5e+00 5.5e+00 67 25 2.9e+01 2.1e+01 59 22
Se 3.5e+02 3.9e+02 50 37 3.7e+01 2.8e+01 99 117 3.3e+01 1.9e+01 100 131 6.1e+01 5.1e+01 86 130
Sm 1.8e+01 1.8e+01 17 9 7.0e+00 7.0e+00 14 13 2.9e+00 2.6e+00 33 36 8.0e+00 8.5e+00 23 16
Sn 7.4e+01 5.1e+01 139 33 1.7e+01 1.6e+01 29 28 4.3e+00 2.9e+00 97 80 1.2e+01 1.3e+01 64 68
Sr 1.7e+04 1.7e+04 8 6 2.7e+04 2.7e+04 3 3 1.9e+04 1.9e+04 3 3 2.1e+04 2.1e+04 6 3
Ta 5.6e-01 4.8e-01 72 69 1.6e+00 1.6e+00 45 51 9.0e-01 4.9e-01 144 101 1.7e+00 1.4e+00 53 23
Tb 2.6e+00 2.6e+00 15 18 1.1e+00 1.0e+00 25 18 5.9e-01 5.8e-01 24 31 1.0e+00 9.8e-01 20 17
Te 1.1e+01 7.6e+00 91 101 8.2e+00 6.0e+00 61 30 5.8e+00 5.9e+00 16 22 4.5e+00 4.8e+00 37 32
Th 4.5e+01 4.4e+01 15 21 6.0e+00 5.7e+00 25 12 1.9e+00 1.5e+00 86 44 6.2e+00 5.8e+00 24 26
Ti 2.3e+03 2.3e+03 19 15 3.1e+03 3.0e+03 12 16 8.9e+02 8.2e+02 23 15 4.1e+03 4.1e+03 15 9
Tl 1.4e+01 1.5e+01 21 22 1.6e+01 1.6e+01 12 6 3.1e+01 3.0e+01 11 6 3.8e+01 3.7e+01 17 16
Tm 6.7e-01 8.0e-01 40 41 1.6e-01 1.6e-01 31 35 1.1e-01 9.7e-02 48 48 2.4e-01 1.8e-01 58 45
U 2.9e+03 3.1e+03 15 11 2.3e+00 2.4e+00 20 17 5.2e-01 4.1e-01 93 56 2.3e+00 2.3e+00 18 25
V 3.0e+02 3.1e+02 9 8 2.4e+02 2.4e+02 4 4 4.8e+01 4.7e+01 18 22 2.3e+02 2.3e+02 6 6
W 1.1e+02 7.8e+01 88 29 4.2e+00 3.6e+00 47 30 9.1e-01 9.0e-01 44 35 4.3e+00 4.2e+00 21 26
Y 6.1e+01 6.3e+01 13 11 3.1e+01 3.0e+01 16 12 3.2e+01 3.1e+01 20 28 3.3e+01 3.3e+01 14 12
Yb 4.9e+00 4.9e+00 18 19 2.1e+00 2.1e+00 28 25 1.2e+00 1.1e+00 41 46 2.2e+00 2.2e+00 34 33
Zn 6.3e+04 6.3e+04 7 3 1.0e+05 1.0e+05 3 3 5.6e+04 5.5e+04 2 2 8.6e+04 8.7e+04 3 3
Zr 8.4e+01 8.0e+01 16 18 3.8e+01 4.0e+01 15 16 7.4e+00 8.1e+00 70 81 4.4e+01 4.4e+01 23 16

1.1.3 Comparison of reference values with measurement values

The preanalysed values are provided from the measurements of the reference material powder at external labs, in this case ACTLAB.

X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.

Figure 1.1: X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.

X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.

Figure 1.2: X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.

X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.

Figure 1.3: X-charts of UPDEEP_SPRY_NEED_DRY/UPDEEP_SPRY_TWIG_DRY/UPDEEP_SPRY_BARK_DRY SRMs analysed with the routine samples (dots) vs. the preanalysed SRM values (mean as solid line, 1st standard deviation as dashed line.) The lines of the predefined values are missing if the SRM values were below detection limit. See Table 1.1 for the numbers of the preanalysed SRMs and their missing values. The two laboratory batches (A20-02249, A20-02250) are distinquised by colour.