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Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S1
1
Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
Andreas Ballota,b,
*, Morten Sandvikb, Thomas Rundberget
b, Christo J. Botha
c, Christopher O.
Milesb
*Corresponding author. Tel: +47 98215480; fax: +47 22185200; E-mail address:
aNorwegian Institute for Water Research, Gaustadalléen 21, N-0349 Oslo, Norway
bNorwegian Veterinary Institute, PO Box 750 Sentrum, N-0106 Oslo, Norway
cDepartment of Paraclinical Sciences, Faculty of Veterinary Science, University of Pretoria,
Private Bag X04, Onderstepoort, 0110, South Africa
Appendix A. Supplementary Data File (74 pp.)
Page S2 LC-MS Chromatograms of extracts of Hartebeespoort Dam and M. aeruginosa
AB2011/53
Page S4 MS2 spectra of microcystins. NB weaker peaks display some spurious peaks
due to reduced signal-to-noise, and for some very weak peaks, suitable MS2
spectra were not obtained.
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S2
2
Figure S1a. Chromatograms of Hartbeespoort Dam extract
LC-MS of Hartbeespoort Dam
(A) Underivatised extract
(B) Mercaptoethanol-derivatised extract
(C) Subtracted chromatogram (A minus B)
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Time (min)
20
40
60
80
100
20
40
60
80
100
Rela
tive
Ab
und
ance
20
40
60
80
100
3.92
996.0
3.83
987.9
3.75
1020.52.08
1038.8 4.15
1016.52.75
945.84.95
1048.55.37
1044.52.80
973.84.32
1068.97.50
926.45.48
1120.4
4.70
966.3
8.18
988.75.88
988.68.22
988.87.84
951.32.25
1038.9
8.69
920.1
7.09
904.0
6.26
1045.5
6.67
901.2
3.85
988.1
3.76
1020.64.17
1016.42.09
1116.92.77
945.93.50
1127.94.95
1048.55.37
1044.52.82
973.8 4.29
1146.97.50
926.65.50
1120.4
4.70
990.57.79
1066.65.90
988.58.05
1080.82.49
931.78.71
902.1
6.29
1023.3
7.19
981.4
6.75
1021.2
3.92
996.0
3.81
1045.8
2.08
1038.8 3.53
1049.84.18
1017.42.74
945.84.32
1068.92.78
973.98.18
988.75.35
1045.6
4.93
1048.58.22
988.87.47
1045.65.45
1043.9
7.89
1104.4
2.58
981.1
8.99
945.3
6.59
1047.7
5.92
893.8
7.16
962.3
LC-MS of Hartbeespoort Dam
(A) Underivatised extract
(B) Mercaptoethanol-derivatised extract
(C) Subtracted chromatogram (A minus B)
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Time (min)
20
40
60
80
100
20
40
60
80
100
Rela
tive
Ab
und
ance
20
40
60
80
100
3.92
996.0
3.83
987.9
3.75
1020.52.08
1038.8 4.15
1016.52.75
945.84.95
1048.55.37
1044.52.80
973.84.32
1068.97.50
926.45.48
1120.4
4.70
966.3
8.18
988.75.88
988.68.22
988.87.84
951.32.25
1038.9
8.69
920.1
7.09
904.0
6.26
1045.5
6.67
901.2
3.85
988.1
3.76
1020.64.17
1016.42.09
1116.92.77
945.93.50
1127.94.95
1048.55.37
1044.52.82
973.8 4.29
1146.97.50
926.65.50
1120.4
4.70
990.57.79
1066.65.90
988.58.05
1080.82.49
931.78.71
902.1
6.29
1023.3
7.19
981.4
6.75
1021.2
3.92
996.0
3.81
1045.8
2.08
1038.8 3.53
1049.84.18
1017.42.74
945.84.32
1068.92.78
973.98.18
988.75.35
1045.6
4.93
1048.58.22
988.87.47
1045.65.45
1043.9
7.89
1104.4
2.58
981.1
8.99
945.3
6.59
1047.7
5.92
893.8
7.16
962.3
(A) Underivatised extract
(B) Mercaptoethanol-derivatised extract
(C) Subtracted chromatogram (A minus B)
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0
Time (min)
20
40
60
80
100
20
40
60
80
100
Rela
tive
Ab
und
ance
20
40
60
80
100
3.92
996.0
3.83
987.9
3.75
1020.52.08
1038.8 4.15
1016.52.75
945.84.95
1048.55.37
1044.52.80
973.84.32
1068.97.50
926.45.48
1120.4
4.70
966.3
8.18
988.75.88
988.68.22
988.87.84
951.32.25
1038.9
8.69
920.1
7.09
904.0
6.26
1045.5
6.67
901.2
3.85
988.1
3.76
1020.64.17
1016.42.09
1116.92.77
945.93.50
1127.94.95
1048.55.37
1044.52.82
973.8 4.29
1146.97.50
926.65.50
1120.4
4.70
990.57.79
1066.65.90
988.58.05
1080.82.49
931.78.71
902.1
6.29
1023.3
7.19
981.4
6.75
1021.2
3.92
996.0
3.81
1045.8
2.08
1038.8 3.53
1049.84.18
1017.42.74
945.84.32
1068.92.78
973.98.18
988.75.35
1045.6
4.93
1048.58.22
988.87.47
1045.65.45
1043.9
7.89
1104.4
2.58
981.1
8.99
945.3
6.59
1047.7
5.92
893.8
7.16
962.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S3
3
Figure S1b. Chromatograms of Hartbeespoort Dam extract
LC-MS of AB2011/53 (1.8-5.5 min)
(A) Underivatised extract
(B) Mercaptoethanol-derivatised extract
(C) Subtracted chromatogram (A minus B)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4
Time (min)
20
40
60
80
100
20
40
60
80
100
Rela
tive
Ab
und
ance
20
40
60
80
100
3.89
995.9
1.97
906.03.77
1045.82.03
1038.8 4.11
1016.53.72
1020.55.34
1044.53.52
1049.84.92
1048.54.29
1068.83.30
988.55.03
1037.92.27
1052.1
2.98
992.5
2.59
999.64.56
1030.4
2.66
950.8
4.84
920.6
1.91
906.03.75
1073.8
3.70
1123.7 4.06
1016.4 5.30
1044.54.88
1048.5
3.40
1127.92.84
1225.74.21
1146.83.26
988.24.82
1115.82.92
1225.6
2.27
1132.04.54
1030.52.55
1180.7
5.00
1048.5
3.89
995.9
3.77
1045.82.03
1038.83.52
1049.85.32
1044.5
4.29
1068.84.18
1029.84.90
1048.5
5.03
1037.92.21
1003.6
4.40
1000.8
3.32
987.6
4.78
956.2
2.59
1090.5
2.83
969.7
3.23
1096.8
LC-MS of AB2011/53 (1.8-5.5 min)
(A) Underivatised extract
(B) Mercaptoethanol-derivatised extract
(C) Subtracted chromatogram (A minus B)
1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4
Time (min)
20
40
60
80
100
20
40
60
80
100
Rela
tive
Ab
und
ance
20
40
60
80
100
3.89
995.9
1.97
906.03.77
1045.82.03
1038.8 4.11
1016.53.72
1020.55.34
1044.53.52
1049.84.92
1048.54.29
1068.83.30
988.55.03
1037.92.27
1052.1
2.98
992.5
2.59
999.64.56
1030.4
2.66
950.8
4.84
920.6
1.91
906.03.75
1073.8
3.70
1123.7 4.06
1016.4 5.30
1044.54.88
1048.5
3.40
1127.92.84
1225.74.21
1146.83.26
988.24.82
1115.82.92
1225.6
2.27
1132.04.54
1030.52.55
1180.7
5.00
1048.5
3.89
995.9
3.77
1045.82.03
1038.83.52
1049.85.32
1044.5
4.29
1068.84.18
1029.84.90
1048.5
5.03
1037.92.21
1003.6
4.40
1000.8
3.32
987.6
4.78
956.2
2.59
1090.5
2.83
969.7
3.23
1096.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S4
4
Figure S2a. MS2 spectrum of tentative [DMAdda
5]MC-LA
Hartbeespoort Dam
m/z 896, Rt 6.18 min
[DMAdda5]MC-LA (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
878.5
877.6
879.5
860.4776.5
365.4
851.6833.4
663.3
758.6366.4 553.4 825.5
799.4662.4585.3 599.8 664.4 748.4523.5 693.5381.4 446.4 490.4 880.3402.3343.4321.4278.4
Hartbeespoort Dam
m/z 896, Rt 6.18 min
[DMAdda5]MC-LA (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
878.5
877.6
879.5
860.4776.5
365.4
851.6833.4
663.3
758.6366.4 553.4 825.5
799.4662.4585.3 599.8 664.4 748.4523.5 693.5381.4 446.4 490.4 880.3402.3343.4321.4278.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S5
5
Figure S2b. MS2 spectr um of tentative [Asp
3]MC-LA
Hartbeespoort Dam
m/z 896, Rt 7.50 min
[Asp3]MC-LA (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
762.4
745.4
744.6
559.3
375.3 693.4
509.3 860.5580.3454.3 661.4 829.5446.4 798.3
533.5 711.5673.5603.6388.3503.4 876.9481.4 642.5347.4 781.5439.5391.5334.3305.4282.3 896.7
Hartbeespoort Dam
m/z 896, Rt 7.50 min
[Asp3]MC-LA (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
762.4
745.4
744.6
559.3
375.3 693.4
509.3 860.5580.3454.3 661.4 829.5446.4 798.3
533.5 711.5673.5603.6388.3503.4 876.9481.4 642.5347.4 781.5439.5391.5334.3305.4282.3 896.7
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S6
6
Figure S2c. MS2 spectrum of tentative MC-LA
Hartbeespoort Dam
m/z 910, Rt 8.29 min
MC-LA
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
776.4
892.5
758.5
878.4 893.5693.4559.3375.3 509.4468.4402.3
580.3446.3 675.5860.4485.4 725.4 809.4597.4
661.3548.3331.2 777.5614.4314.3 821.6347.3 443.4 712.5282.4 909.9
Hartbeespoort Dam
m/z 910, Rt 8.29 min
MC-LA
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
776.4
892.5
758.5
878.4 893.5693.4559.3375.3 509.4468.4402.3
580.3446.3 675.5860.4485.4 725.4 809.4597.4
661.3548.3331.2 777.5614.4314.3 821.6347.3 443.4 712.5282.4 909.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S7
7
Figure S2d. MS2 spectrum of tentative MC-LAba
Hartbeespoort Dam
m/z 924, Rt 9.08 min
MC-LAba (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
790.4
906.4
772.4
888.5
794.5446.2 482.3 559.1 693.3
509.3375.3 862.6416.3 580.3 739.3 795.5
593.3 823.3755.5698.9689.4398.5 628.5477.2345.2 543.3
426.3314.4282.3 925.3
Hartbeespoort Dam
m/z 924, Rt 9.08 min
MC-LAba (tentative)
250 300 350 400 450 500 550 600 650 700 750 800 850 900
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
790.4
906.4
772.4
888.5
794.5446.2 482.3 559.1 693.3
509.3375.3 862.6416.3 580.3 739.3 795.5
593.3 823.3755.5698.9689.4398.5 628.5477.2345.2 543.3
426.3314.4282.3 925.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S8
8
Figure S2e. MS2 spectrum of tentative MC-YA from Hartbeespoort Dam
Hartbeespoort Dam
m/z 960, Rt 8.13 min
MC-YA (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
826.3
942.4
808.4
943.4623.3
928.4452.3518.3 743.3446.2 910.5375.3 509.3393.4 535.3 580.2
725.3 874.4624.4364.2 791.3711.4434.3 775.4 827.3477.3 548.2 650.3
347.3297.3 944.2
Hartbeespoort Dam
m/z 960, Rt 8.13 min
MC-YA (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
826.3
942.4
808.4
943.4623.3
928.4452.3518.3 743.3446.2 910.5375.3 509.3393.4 535.3 580.2
725.3 874.4624.4364.2 791.3711.4434.3 775.4 827.3477.3 548.2 650.3
347.3297.3 944.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S9
9
Figure S2f. MS2 spectrum of [Asp
3, DMAdda
5]MC-L R standard from Nostoc 152
Hydrolysed Nostoc culture 152
m/z 967, Rt 2.57 min
[Asp3, DMAdda5]MC-LR from hydrolysis
of confirmed [Asp3, ADMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
939.6
950.5
585.5
830.5
847.5539.4
557.5
895.7951.6
538.5
896.6586.5456.4
852.6
711.5375.3 700.5455.4 654.5521.4 802.6755.6739.6446.4383.3 511.4457.4368.4 611.5325.3 787.5650.6289.2
967.0
Hydrolysed Nostoc culture 152
m/z 967, Rt 2.57 min
[Asp3, DMAdda5]MC-LR from hydrolysis
of confirmed [Asp3, ADMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
939.6
950.5
585.5
830.5
847.5539.4
557.5
895.7951.6
538.5
896.6586.5456.4
852.6
711.5375.3 700.5455.4 654.5521.4 802.6755.6739.6446.4383.3 511.4457.4368.4 611.5325.3 787.5650.6289.2
967.0
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S10
10
Figure S2g. MS2 spectrum of confirmed [Asp
3, DMAdda
5]MC-LR stand ard from Hartbeespoort Dam
Hartbeespoort Dam
m/z 967, Rt 2.57 min
[Asp3, DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
949.6
948.6
583.3
950.6
922.6585.5
921.2
904.5605.4830.6 902.5539.5 557.5 951.5835.6
801.5538.5 784.5654.6637.4 669.4 755.6385.4 708.5496.4462.4 966.9407.4353.5342.5301.3
Hartbeespoort Dam
m/z 967, Rt 2.57 min
[Asp3, DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
949.6
948.6
583.3
950.6
922.6585.5
921.2
904.5605.4830.6 902.5539.5 557.5 951.5835.6
801.5538.5 784.5654.6637.4 669.4 755.6385.4 708.5496.4462.4 966.9407.4353.5342.5301.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S11
11
Figure S2h. MS2 spectrum of tentative [Asp
3, Dha
7]MC-LR standard from Hartbeespoort Dam
Hartbeespoort Dam
m/z 967, Rt 3.93 min
[Asp3, Dha7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
939.5
950.4
525.4
571.4524.3
542.4 838.5
600.4895.5837.5
951.5816.5
668.4918.4852.4696.4
508.4491.4469.5 714.4361.3
432.2 625.4 869.5414.4333.3 735.5653.4453.4 810.4753.4289.3958.0
Hartbeespoort Dam
m/z 967, Rt 3.93 min
[Asp3, Dha7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
939.5
950.4
525.4
571.4524.3
542.4 838.5
600.4895.5837.5
951.5816.5
668.4918.4852.4696.4
508.4491.4469.5 714.4361.3
432.2 625.4 869.5414.4333.3 735.5653.4453.4 810.4753.4289.3958.0
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S12
12
Figure S2i. MS2 spectrum of [DMAdda
5]MC-LR standard from Nostoc 152
Hydrolysed Nostoc culture 152
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR from hydrolysis of
confirmed [ADMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.6
964.5
585.4
553.4
844.5
852.6
557.5909.6
552.4965.6896.5
586.5 937.6
668.5 696.5 714.5862.6470.4 824.6
375.3 769.5535.4455.5 525.5 739.5611.4 816.5446.2285.3 397.3303.3 347.3 487.3 636.4966.1
Hydrolysed Nostoc culture 152
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR from hydrolysis of
confirmed [ADMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.6
964.5
585.4
553.4
844.5
852.6
557.5909.6
552.4965.6896.5
586.5 937.6
668.5 696.5 714.5862.6470.4 824.6
375.3 769.5535.4455.5 525.5 739.5611.4 816.5446.2285.3 397.3303.3 347.3 487.3 636.4966.1
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S13
13
Figure S2j. MS2 spectrum of confirmed [DMAdda
5]MC-LR standard from Hartbeespoort Dam
Hartbeespoort Dam
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.5
963.4
964.5585.3
553.4
844.5
557.5 861.5
965.5909.5
918.5
552.4 936.5896.5714.4
586.4 862.5668.4534.6
696.4375.3 816.2
588.3 769.5510.4455.4397.4 715.4654.3611.4 797.4303.3 474.6446.3347.3971.9
Hartbeespoort Dam
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.5
963.4
964.5585.3
553.4
844.5
557.5 861.5
965.5909.5
918.5
552.4 936.5896.5714.4
586.4 862.5668.4534.6
696.4375.3 816.2
588.3 769.5510.4455.4397.4 715.4654.3611.4 797.4303.3 474.6446.3347.3971.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S14
14
Figure S2k. MS2 spectrum of confirmed [DMAdda
5]MC-LR standard from M. aeruginosa AB2011/53
AB2011/53
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
953.6
963.6
585.5 964.6
583.3
553.5 844.6 861.6
909.6
552.6
557.5965.7
586.5 937.6714.5 896.6
696.6869.7
470.5 824.6668.5605.4375.3 637.4 769.6535.4 816.6715.6510.5399.4 455.5 611.5339.4 809.6285.3 654.4982.3
AB2011/53
m/z 981, Rt 2.59 min
[DMAdda5]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
953.6
963.6
585.5 964.6
583.3
553.5 844.6 861.6
909.6
552.6
557.5965.7
586.5 937.6714.5 896.6
696.6869.7
470.5 824.6668.5605.4375.3 637.4 769.6535.4 816.6715.6510.5399.4 455.5 611.5339.4 809.6285.3 654.4982.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S15
15
Figure S2l. MS2 spectrum of tentative [Asp
3]MC-LR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 981, Rt 3.87 min
[Asp3]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.5
964.5
599.4
539.4
909.5965.5
538.4571.4
910.5830.4 847.4600.4 932.4
866.5714.4696.4375.3668.4
456.4
724.4455.3 769.5521.4 625.4496.4368.3 397.4 439.3 812.5289.3 329.3 980.2
Hartbeespoort Dam
m/z 981, Rt 3.87 min
[Asp3]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
953.5
964.5
599.4
539.4
909.5965.5
538.4571.4
910.5830.4 847.4600.4 932.4
866.5714.4696.4375.3668.4
456.4
724.4455.3 769.5521.4 625.4496.4368.3 397.4 439.3 812.5289.3 329.3 980.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S16
16
Figure S2m. MS2 spectrum of tentative [Asp
3]MC-LR from M. aeruginosa AB2011/53
AB2011/53
m/z 981, Rt 3.87 min
[Asp3]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
953.6
964.6
599.5
539.5
909.6965.6
571.5538.5910.7
851.6830.6932.6600.5
852.7
883.6696.6714.5456.5375.4 668.5
469.6446.3 769.6511.4383.3 470.5 623.4 715.5368.3 796.6641.5439.4347.3289.3
966.7
AB2011/53
m/z 981, Rt 3.87 min
[Asp3]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
953.6
964.6
599.5
539.5
909.6965.6
571.5538.5910.7
851.6830.6932.6600.5
852.7
883.6696.6714.5456.5375.4 668.5
469.6446.3 769.6511.4383.3 470.5 623.4 715.5368.3 796.6641.5439.4347.3289.3
966.7
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S17
17
Figure S2n. MS2 spectrum of confirmed [Dha
7]MC-LR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 981, Rt 3.99 min
[Dha7]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
963.5953.5
964.5
539.4
538.4
852.5
571.4600.4 851.5
556.4965.5
710.4 909.5
830.4728.4682.4522.4 853.5
505.4 824.6470.4 668.4 869.5625.4361.3 729.5432.2285.3 333.3 414.3 797.5751.5
966.4
Hartbeespoort Dam
m/z 981, Rt 3.99 min
[Dha7]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
963.5953.5
964.5
539.4
538.4
852.5
571.4600.4 851.5
556.4965.5
710.4 909.5
830.4728.4682.4522.4 853.5
505.4 824.6470.4 668.4 869.5625.4361.3 729.5432.2285.3 333.3 414.3 797.5751.5
966.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S18
18
Figure S2o. MS2 spectrum of confirmed [Dha
7]MC-LR from M. aeruginosa AB2011/53
AB2011/53
m/z 981, Rt 3.99 min
[Dha7]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.5963.6
953.6 964.6
539.4
852.6538.4
556.5 600.5 851.6
965.6
909.6710.5830.6
728.5 932.6682.5 853.6522.5
505.4 824.6469.5668.5 869.7625.5487.4432.3361.3 729.6285.3 333.3 641.6397.4 797.5
966.3
AB2011/53
m/z 981, Rt 3.99 min
[Dha7]MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.5963.6
953.6 964.6
539.4
852.6538.4
556.5 600.5 851.6
965.6
909.6710.5830.6
728.5 932.6682.5 853.6522.5
505.4 824.6469.5668.5 869.7625.5487.4432.3361.3 729.6285.3 333.3 641.6397.4 797.5
966.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S19
19
Figure S2p. MS2 spectrum of confirmed [Asp
3]MC-LY from Hartbeespoort Dam
Hartbeespoort Dam
m/z 988, Rt 8.15 min
[Asp3]MC-LY (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
854.3
837.2
970.4
836.4
559.2971.4693.3
956.3546.3
375.3446.2 509.3480.3 580.2
939.3809.3
463.3 661.2753.4545.4435.3409.3 791.4 887.4 911.3713.2347.3 657.3629.3329.3296.2 776.4 972.2
Hartbeespoort Dam
m/z 988, Rt 8.15 min
[Asp3]MC-LY (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
854.3
837.2
970.4
836.4
559.2971.4693.3
956.3546.3
375.3446.2 509.3480.3 580.2
939.3809.3
463.3 661.2753.4545.4435.3409.3 791.4 887.4 911.3713.2347.3 657.3629.3329.3296.2 776.4 972.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S20
20
Figure S2q. MS2 spectrum of confirmed MC-LR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 995, Rt 3.89 min
MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
967.7978.7
599.5
553.5
866.7
571.5979.7923.7552.5
865.6
951.7600.5910.6
470.5 710.5682.6728.6 867.7375.3 838.6783.6
525.5397.4 453.5738.6285.3 625.5510.5 637.6 784.7303.4 347.4 428.4
980.3
Hartbeespoort Dam
m/z 995, Rt 3.89 min
MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
967.7978.7
599.5
553.5
866.7
571.5979.7923.7552.5
865.6
951.7600.5910.6
470.5 710.5682.6728.6 867.7375.3 838.6783.6
525.5397.4 453.5738.6285.3 625.5510.5 637.6 784.7303.4 347.4 428.4
980.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S21
21
Figure S2r. MS2 spectrum of confirmed MC-LR from M. aeruginosa AB2011/53
AB2011/53
m/z 995, Rt 3.89 min
MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
978.7967.7
599.5
553.5
866.7979.7571.6
552.5 923.7865.7
600.5844.6 951.7
910.6
710.5470.5682.6 867.7728.5 838.7469.5
883.7783.6375.4 397.4
453.5 525.5625.6510.5 729.6637.5285.4 347.4 784.6399.4303.4
980.3
AB2011/53
m/z 995, Rt 3.89 min
MC-LR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
978.7967.7
599.5
553.5
866.7979.7571.6
552.5 923.7865.7
600.5844.6 951.7
910.6
710.5470.5682.6 867.7728.5 838.7469.5
883.7783.6375.4 397.4
453.5 525.5625.6510.5 729.6637.5285.4 347.4 784.6399.4303.4
980.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S22
22
Figure S2s. MS2 spectrum of confirmed MC-LY from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1002, Rt 8.48 min
MC-LY
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
868.4
984.6
850.5
494.4 559.3
560.3970.4693.4
985.5446.3 580.3375.3 509.4
477.4 952.5817.4767.5476.4 901.5423.3 833.5699.5
661.3548.3397.3 706.4 772.4310.2 643.4 869.5596.4 939.5727.4347.3 1001.8
Hartbeespoort Dam
m/z 1002, Rt 8.48 min
MC-LY
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
868.4
984.6
850.5
494.4 559.3
560.3970.4693.4
985.5446.3 580.3375.3 509.4
477.4 952.5817.4767.5476.4 901.5423.3 833.5699.5
661.3548.3397.3 706.4 772.4310.2 643.4 869.5596.4 939.5727.4347.3 1001.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S23
23
Figure S2t. MS2 spectrum of tentative MC-HilR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1009, Rt 4.15 min
MC-HilR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
990.4981.5
992.5
599.4
567.4
880.5
566.4
937.6 993.5571.4 879.6
858.4 965.5600.4 924.5
728.4682.4 852.5881.5484.4
549.4375.3 897.6469.4 797.5739.4396.3 602.4539.4
446.3 625.3 798.5285.3 347.3995.4
Hartbeespoort Dam
m/z 1009, Rt 4.15 min
MC-HilR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
990.4981.5
992.5
599.4
567.4
880.5
566.4
937.6 993.5571.4 879.6
858.4 965.5600.4 924.5
728.4682.4 852.5881.5484.4
549.4375.3 897.6469.4 797.5739.4396.3 602.4539.4
446.3 625.3 798.5285.3 347.3995.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S24
24
Figure S2u. MS2 spectrum of tentative MC-HilR from M. aeruginosa AB2011/53
AB2011/53
m/z 1009, Rt 4.15 min
MC-HilR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
992.7
981.7
599.5
567.5
993.7880.7
566.5571.5 879.7 937.7
858.6 965.7924.7600.5
710.5881.7
728.5 852.7484.4 682.6375.3 882.7797.6539.4469.5 739.6602.5 752.5 840.5446.3 651.5396.5347.4 501.4285.3 428.3
AB2011/53
m/z 1009, Rt 4.15 min
MC-HilR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
992.7
981.7
599.5
567.5
993.7880.7
566.5571.5 879.7 937.7
858.6 965.7924.7600.5
710.5881.7
728.5 852.7484.4 682.6375.3 882.7797.6539.4469.5 739.6602.5 752.5 840.5446.3 651.5396.5347.4 501.4285.3 428.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S25
25
Figure S2v. MS2 spectrum of tentative [Mser
7]MC-LR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1013, Rt 3.65 min
[Mser7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.4
996.5
985.5599.4571.4
810.4969.5884.5570.4 997.5941.5393.3 600.5 862.4469.5 728.5710.4 753.5 844.4682.4 783.5528.4453.4375.2303.3 338.5 1000.5
Hartbeespoort Dam
m/z 1013, Rt 3.65 min
[Mser7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.4
996.5
985.5599.4571.4
810.4969.5884.5570.4 997.5941.5393.3 600.5 862.4469.5 728.5710.4 753.5 844.4682.4 783.5528.4453.4375.2303.3 338.5 1000.5
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S26
26
Figure S2w. MS2 spectrum of tentative [Mser
7]MC-LR from M. aeruginosa AB2011/53
AB2011/53
m/z 1013, Rt 3.65 min
[Mser7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.5
996.5
571.4
599.4 985.5
976.4
997.5884.5941.5553.5 630.6 728.6689.2 922.0393.4
809.9470.3 837.6743.5508.4 783.5453.3375.3365.2 416.4 693.4682.8300.1 999.6339.9
AB2011/53
m/z 1013, Rt 3.65 min
[Mser7]MC-LR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.5
996.5
571.4
599.4 985.5
976.4
997.5884.5941.5553.5 630.6 728.6689.2 922.0393.4
809.9470.3 837.6743.5508.4 783.5453.3375.3365.2 416.4 693.4682.8300.1 999.6339.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S27
27
Figure S2x. MS2 spectrum of unidentified MC-XR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1013, Rt 3.77 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
985.5
996.4
571.4 599.4
570.3984.6
941.5
884.5
600.5 997.5928.4 968.4
879.5
488.4469.4 569.3 682.5 885.5728.4543.3375.3 801.5 856.4 912.5606.4 729.4655.4509.4 756.1400.2 849.3446.2285.4 357.3339.3
998.6
Hartbeespoort Dam
m/z 1013, Rt 3.77 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
985.5
996.4
571.4 599.4
570.3984.6
941.5
884.5
600.5 997.5928.4 968.4
879.5
488.4469.4 569.3 682.5 885.5728.4543.3375.3 801.5 856.4 912.5606.4 729.4655.4509.4 756.1400.2 849.3446.2285.4 357.3339.3
998.6
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S28
28
Figure S2y. MS2 spectrum of unidentified MC-XR from M. aeruginosa AB2011/53
AB2011/53
m/z 1013, Rt 3.77 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.5
985.5996.5
571.3
599.4
884.5
997.5941.5570.4 883.5
964.5
600.5 879.4 928.4488.3 682.5 862.4 901.5
470.4375.3 728.5
554.3528.5 856.4683.4469.5 756.2625.3 834.5417.2 654.5347.4285.4
AB2011/53
m/z 1013, Rt 3.77 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
995.5
985.5996.5
571.3
599.4
884.5
997.5941.5570.4 883.5
964.5
600.5 879.4 928.4488.3 682.5 862.4 901.5
470.4375.3 728.5
554.3528.5 856.4683.4469.5 756.2625.3 834.5417.2 654.5347.4285.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S29
29
Figure S2z. MS2 spectrum of tentative [Asp
3]MC-RR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1024, Rt 2.12 min
[Asp3]MC-RR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
965.71006.6
966.7
895.6
1007.7
967.8
982.7962.7728.6599.5
892.5944.7896.7616.6 779.5581.5 710.7 875.6745.6 797.6426.6 675.5531.4340.4 521.6460.5 1008.7314.4 411.5
Hartbeespoort Dam
m/z 1024, Rt 2.12 min
[Asp3]MC-RR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
965.71006.6
966.7
895.6
1007.7
967.8
982.7962.7728.6599.5
892.5944.7896.7616.6 779.5581.5 710.7 875.6745.6 797.6426.6 675.5531.4340.4 521.6460.5 1008.7314.4 411.5
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S30
30
Figure S2aa. MS2 spectrum of unidentified possible MC-RR analogue from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1029, Rt 3.37 min
Unidentified MC-RR analogue?
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
965.5
966.5
1011.4599.4 947.5937.5836.4803.5 900.5523.4 759.5540.3 967.4710.4682.4504.4440.4416.3375.3 606.5352.2329.4
Hartbeespoort Dam
m/z 1029, Rt 3.37 min
Unidentified MC-RR analogue?
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
965.5
966.5
1011.4599.4 947.5937.5836.4803.5 900.5523.4 759.5540.3 967.4710.4682.4504.4440.4416.3375.3 606.5352.2329.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S31
31
Figure S2ab. MS2 spectrum of tentative MC-FR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1029, Rt 4.21 min
MC-FR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1001.6
1012.6
599.5
587.5
586.4 957.6900.7604.5
899.6571.5 944.6 980.6
878.5
710.5 872.6682.5504.4 901.6728.6375.3 559.4 817.6416.3 622.5469.5 759.4544.4431.3373.3 397.5 671.5 816.6 850.6303.4
Hartbeespoort Dam
m/z 1029, Rt 4.21 min
MC-FR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1001.6
1012.6
599.5
587.5
586.4 957.6900.7604.5
899.6571.5 944.6 980.6
878.5
710.5 872.6682.5504.4 901.6728.6375.3 559.4 817.6416.3 622.5469.5 759.4544.4431.3373.3 397.5 671.5 816.6 850.6303.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S32
32
Figure S2ac. MS2 spectrum of tentative MC-FR from M. aeruginosa AB2011/53
AB2011/53
m/z 1029, Rt 4.21 min
MC-FR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1001.6
1012.6
599.5
587.4
586.5 900.6957.7604.5 899.6
944.6878.6571.5 980.6
682.5 710.5504.4 872.6 901.7728.6 817.6
759.5416.3375.4 559.5469.5 622.4544.5397.4 671.5433.4 835.6373.3 799.5303.4
AB2011/53
m/z 1029, Rt 4.21 min
MC-FR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1001.6
1012.6
599.5
587.4
586.5 900.6957.7604.5 899.6
944.6878.6571.5 980.6
682.5 710.5504.4 872.6 901.7728.6 817.6
759.5416.3375.4 559.5469.5 622.4544.5397.4 671.5433.4 835.6373.3 799.5303.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S33
33
Figure S2ad. MS2 spectrum of tentative MC-RF from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1029, Rt 6.34 min
MC-RF (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1011.4
440.4 912.4
1001.5
865.5
957.5
950.4
753.5 913.4
984.6586.4 868.5
329.3754.3731.4
587.3441.3
780.5721.3 803.4 937.6605.4422.9 704.5 827.5552.3 667.2509.2461.3371.2 417.2327.2
Hartbeespoort Dam
m/z 1029, Rt 6.34 min
MC-RF (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1011.4
440.4 912.4
1001.5
865.5
957.5
950.4
753.5 913.4
984.6586.4 868.5
329.3754.3731.4
587.3441.3
780.5721.3 803.4 937.6605.4422.9 704.5 827.5552.3 667.2509.2461.3371.2 417.2327.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S34
34
Figure S2ae. MS2 spectrum of tentative [DMAdda
5]MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1031, Rt 2.40 min
[DMAdda5]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.5
1013.5
1014.5
585.4
603.4
894.4959.5911.4
557.4
620.41015.4987.5
946.4
912.5668.4 696.4520.3 714.4 874.5819.5432.3 920.5638.4455.4 788.4 866.4375.3 775.4519.3 537.3457.3431.2371.3303.3 1016.4
Hartbeespoort Dam
m/z 1031, Rt 2.40 min
[DMAdda5]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.5
1013.5
1014.5
585.4
603.4
894.4959.5911.4
557.4
620.41015.4987.5
946.4
912.5668.4 696.4520.3 714.4 874.5819.5432.3 920.5638.4455.4 788.4 866.4375.3 775.4519.3 537.3457.3431.2371.3303.3 1016.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S35
35
Figure S2af. MS2 spectrum of tentative [DMAdda
5]MC-YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1031, Rt 2.40 min
[DMAdda5]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.6
1013.6
585.5
603.4
894.5
911.6
959.7620.5 1015.7
557.5
946.6986.7
520.5 668.5 696.6 912.6714.6 874.6638.5
919.7375.4 455.5 788.5769.6519.5 819.6537.4431.5845.7347.4 456.5 758.8309.9 422.3 1026.4
AB2011/53
m/z 1031, Rt 2.40 min
[DMAdda5]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.6
1013.6
585.5
603.4
894.5
911.6
959.7620.5 1015.7
557.5
946.6986.7
520.5 668.5 696.6 912.6714.6 874.6638.5
919.7375.4 455.5 788.5769.6519.5 819.6537.4431.5845.7347.4 456.5 758.8309.9 422.3 1026.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S36
36
Figure S2ag. MS2 spectrum of tentative [Asp
3]MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1031, Rt 3.47 min
[Asp3]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1003.5
1014.5
599.4
589.4
959.5
588.4
571.4 606.4
1015.5982.4901.5880.4
916.5375.3
934.5696.4 761.4 819.5668.5 714.4469.4 488.4 624.3546.3 774.4744.3 868.4433.2 655.4397.4357.3289.3 320.2 1017.6
Hartbeespoort Dam
m/z 1031, Rt 3.47 min
[Asp3]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1003.5
1014.5
599.4
589.4
959.5
588.4
571.4 606.4
1015.5982.4901.5880.4
916.5375.3
934.5696.4 761.4 819.5668.5 714.4469.4 488.4 624.3546.3 774.4744.3 868.4433.2 655.4397.4357.3289.3 320.2 1017.6
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S37
37
Figure S2ah. MS2 spectrum of tentative [Asp
3]MC-YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1031, Rt 3.47 min
[Asp3]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1013.5
771.6
420.3
1003.6 1014.6
599.5787.4 846.3
589.5 769.4 789.5 959.7571.5 1015.7606.5 901.7880.5 982.6537.1 916.7696.6375.4 527.4469.6 625.5 744.6668.6 805.4459.4 879.7310.3 348.4 1031.9
AB2011/53
m/z 1031, Rt 3.47 min
[Asp3]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1013.5
771.6
420.3
1003.6 1014.6
599.5787.4 846.3
589.5 769.4 789.5 959.7571.5 1015.7606.5 901.7880.5 982.6537.1 916.7696.6375.4 527.4469.6 625.5 744.6668.6 805.4459.4 879.7310.3 348.4 1031.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S38
38
Figure S2ai. MS2 spectrum of tentative [Dha
7]MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1031, Rt 3.75 min
[Dha7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
1003.5
589.4
1014.5
588.3 902.5
571.4
901.5606.4
880.4 1015.5710.4
959.5
728.5903.5
554.5 625.5 682.4
668.5 913.5546.4432.3 469.6 875.5333.3 774.5361.1 520.4 846.5387.4 492.2 632.4444.4303.4 1016.4
Hartbeespoort Dam
m/z 1031, Rt 3.75 min
[Dha7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
599.4
1003.5
589.4
1014.5
588.3 902.5
571.4
901.5606.4
880.4 1015.5710.4
959.5
728.5903.5
554.5 625.5 682.4
668.5 913.5546.4432.3 469.6 875.5333.3 774.5361.1 520.4 846.5387.4 492.2 632.4444.4303.4 1016.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S39
39
Figure S2aj. MS2 spectrum of tentative [Dha
7]MC-YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1031, Rt 3.75 min
[Dha7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.7
599.5
1013.6
1014.6
589.5
588.5
902.7
571.5600.5
917.7901.7 946.7 959.7 1015.6897.6
710.7555.2
711.6700.4668.5470.5361.5 433.3 797.9746.3628.7539.4502.2414.6 869.7319.5
1030.8
AB2011/53
m/z 1031, Rt 3.75 min
[Dha7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.7
599.5
1013.6
1014.6
589.5
588.5
902.7
571.5600.5
917.7901.7 946.7 959.7 1015.6897.6
710.7555.2
711.6700.4668.5470.5361.5 433.3 797.9746.3628.7539.4502.2414.6 869.7319.5
1030.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S40
40
Figure S2ak. MS2 spectrum of tentative [Asp
3]MC-RY from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1031, Rt 5.12 min
[Asp3]MC-RY (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.6426.4
959.6
851.5
1013.6588.4
1014.6916.6
960.7606.5
897.6754.5717.5
986.6736.5 852.6581.4
329.4 427.4354.4917.7
873.6624.5311.3 934.7846.6555.4 761.5505.5 704.5 819.6375.4 1015.6492.5409.3 673.5537.4
645.61031.4
Hartbeespoort Dam
m/z 1031, Rt 5.12 min
[Asp3]MC-RY (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.6426.4
959.6
851.5
1013.6588.4
1014.6916.6
960.7606.5
897.6754.5717.5
986.6736.5 852.6581.4
329.4 427.4354.4917.7
873.6624.5311.3 934.7846.6555.4 761.5505.5 704.5 819.6375.4 1015.6492.5409.3 673.5537.4
645.61031.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S41
41
Figure S2al. MS2 spectrum of tentative trace [Asp
3]MC-RY from M. aeruginosa AB2011/53
AB2011/53
m/z 1031, Rt 5.12 min
[Asp3]MC-RY (tentative trace?)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.5
968.4
1013.9
984.8
898.5
851.2 963.5588.4
930.7426.3
581.6609.9 783.7
933.5427.2862.5
735.6
743.2
338.1 893.9829.8717.5 808.8537.1694.5384.1 486.7462.3 647.1 871.1
565.4506.4374.3436.6385.5305.2 350.3 1015.5
308.2 1017.9
AB2011/53
m/z 1031, Rt 5.12 min
[Asp3]MC-RY (tentative trace?)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1003.5
968.4
1013.9
984.8
898.5
851.2 963.5588.4
930.7426.3
581.6609.9 783.7
933.5427.2862.5
735.6
743.2
338.1 893.9829.8717.5 808.8537.1694.5384.1 486.7462.3 647.1 871.1
565.4506.4374.3436.6385.5305.2 350.3 1015.5
308.2 1017.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S42
42
Figure S2am. MS2 spectrum of tentative [DMAdda
5]C-(H4)YR from Hartbeespoort Dam
AB2011/53
m/z 1035, Rt 2.06 min
[DMAdda5]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.7
585.5
973.8915.7 963.8
999.3589.4 624.5869.7 906.6558.5
1019.6950.6853.7418.3 721.9435.5 668.5 771.7 792.4506.6 529.4401.6333.3303.2
AB2011/53
m/z 1035, Rt 2.06 min
[DMAdda5]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.7
585.5
973.8915.7 963.8
999.3589.4 624.5869.7 906.6558.5
1019.6950.6853.7418.3 721.9435.5 668.5 771.7 792.4506.6 529.4401.6333.3303.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S43
43
Figure S2an. MS2 spectrum of tentative [Asp
3]MC-(H4)YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1035, Rt 3.25 min
[Asp3]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.6
599.5
963.6
593.5 905.6610.5575.5 1019.6920.6884.6866.6714.5696.5375.3 823.6765.5668.6492.4 509.4421.4 469.5 558.4347.3326.3
Hartbeespoort Dam
m/z 1035, Rt 3.25 min
[Asp3]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.6
599.5
963.6
593.5 905.6610.5575.5 1019.6920.6884.6866.6714.5696.5375.3 823.6765.5668.6492.4 509.4421.4 469.5 558.4347.3326.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S44
44
Figure S2ao. MS2 spectrum of tentative [Asp
3]MC-(H4)YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1035, Rt 3.25 min
[Asp3]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.7
1007.6
599.5
973.7585.5
571.6 906.6 963.6610.6 884.6
510.4 1019.6937.4624.5 792.6489.3 689.7 775.6714.7379.4 550.5 824.8431.4357.6 862.4338.8
AB2011/53
m/z 1035, Rt 3.25 min
[Asp3]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.7
1007.6
599.5
973.7585.5
571.6 906.6 963.6610.6 884.6
510.4 1019.6937.4624.5 792.6489.3 689.7 775.6714.7379.4 550.5 824.8431.4357.6 862.4338.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S45
45
Figure S2ap. MS2 spectrum of tentative [Dha
7]MC-(H4)YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1035, Rt 3.52 min
[Dha7]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6599.5
1007.7
592.6906.6
971.6610.5571.5
963.7905.6682.5 710.5 878.7 907.6418.5 1019.6469.7 866.6668.4547.5531.5 728.6 765.6626.5 805.6400.4325.4 369.1
Hartbeespoort Dam
m/z 1035, Rt 3.52 min
[Dha7]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6599.5
1007.7
592.6906.6
971.6610.5571.5
963.7905.6682.5 710.5 878.7 907.6418.5 1019.6469.7 866.6668.4547.5531.5 728.6 765.6626.5 805.6400.4325.4 369.1
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S46
46
Figure S2aq. MS2 spectrum of tentative [Dha
7]MC-(H4)YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1035, Rt 3.52 min
[Dha7]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.8599.5
999.8
906.8950.1
992.6610.5592.4
905.9 935.5 1019.6575.6435.3722.4 806.9 839.5523.4 780.8565.5 611.5421.3 646.4470.6 868.8686.3309.7 358.2 390.2
AB2011/53
m/z 1035, Rt 3.52 min
[Dha7]MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1017.6
1018.6
1007.8599.5
999.8
906.8950.1
992.6610.5592.4
905.9 935.5 1019.6575.6435.3722.4 806.9 839.5523.4 780.8565.5 611.5421.3 646.4470.6 868.8686.3309.7 358.2 390.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S47
47
Figure S2ar. MS2 spectrum of tentative MC-AnaR from M. aeruginosa AB2011/53
AB2011/53
m/z 1037, Rt 5.05 min
MC-AnaR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1009.7
1019.7
599.5
595.5
965.8
594.5908.7
571.5 612.5 886.6975.8952.7
880.7710.5682.6 728.6512.5 925.8375.3 767.6 825.7469.5 567.5 630.5 780.6750.6424.4397.4 679.5 868.6529.5347.4303.3
AB2011/53
m/z 1037, Rt 5.05 min
MC-AnaR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1009.7
1019.7
599.5
595.5
965.8
594.5908.7
571.5 612.5 886.6975.8952.7
880.7710.5682.6 728.6512.5 925.8375.3 767.6 825.7469.5 567.5 630.5 780.6750.6424.4397.4 679.5 868.6529.5347.4303.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S48
48
Figure S2as. MS2 spectrum of confirmed MC-RR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1038, Rt 2.13 min
MC-RR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1020.7
996.7
909.7 978.7867.7728.6 958.7926.7599.6 753.6 822.6710.5 770.6440.4 682.6571.6535.5 625.5375.4 488.5303.4 328.5 424.6
Hartbeespoort Dam
m/z 1038, Rt 2.13 min
MC-RR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1020.7
996.7
909.7 978.7867.7728.6 958.7926.7599.6 753.6 822.6710.5 770.6440.4 682.6571.6535.5 625.5375.4 488.5303.4 328.5 424.6
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S49
49
Figure S2at. MS2 spectrum of confirmed MC-RR from M. aeruginosa AB2011/53
AB2011/53
m/z 1038, Rt 2.13 min
MC-RR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1020.5
996.5
909.5867.5 978.5728.4 976.5910.5599.4 753.5 866.6822.5710.4 770.5440.3303.2 625.4569.4375.3 681.5457.5 535.4488.0347.3 397.6
AB2011/53
m/z 1038, Rt 2.13 min
MC-RR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1020.5
996.5
909.5867.5 978.5728.4 976.5910.5599.4 753.5 866.6822.5710.4 770.5440.3303.2 625.4569.4375.3 681.5457.5 535.4488.0347.3 397.6
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S50
50
Figure S2au. MS2 spectrum of confirmed MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1045, Rt 3.84 min
MC-YR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.5
1028.4
599.4
603.3
916.5
973.5620.4915.5571.4
960.4894.3 996.4
682.4 710.4 917.5520.3 888.5728.4 833.5375.3 638.4 933.5775.3519.4432.3 469.4 560.4 788.3 882.5397.4639.4347.3303.3
Hartbeespoort Dam
m/z 1045, Rt 3.84 min
MC-YR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.5
1028.4
599.4
603.3
916.5
973.5620.4915.5571.4
960.4894.3 996.4
682.4 710.4 917.5520.3 888.5728.4 833.5375.3 638.4 933.5775.3519.4432.3 469.4 560.4 788.3 882.5397.4639.4347.3303.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S51
51
Figure S2av. MS2 spectrum of confirmed MC-YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1045, Rt 3.84 min
MC-YR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.6
1028.6
599.5
603.4
973.6620.5 916.6
571.5 894.6 960.6983.6
682.5 710.5917.6888.7520.4 728.5
833.6375.3 638.4432.3 519.5 775.5469.5 560.4 788.5 882.7397.4 639.5488.5347.4303.3
AB2011/53
m/z 1045, Rt 3.84 min
MC-YR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.6
1028.6
599.5
603.4
973.6620.5 916.6
571.5 894.6 960.6983.6
682.5 710.5917.6888.7520.4 728.5
833.6375.3 638.4432.3 519.5 775.5469.5 560.4 788.5 882.7397.4 639.5488.5347.4303.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S52
52
Figure S2aw. MS2 spectrum of confirmed MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1045, Rt 5.31 min
MC-RY
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.5
440.3
973.5
602.3 865.4
1018.5
620.4 1027.4
916.5 974.5
1028.5
754.4 983.5911.5368.3
866.5595.3 917.5731.4441.3329.3 960.5
621.4519.4 775.3 860.4833.5357.3 431.4311.3 569.3 934.4520.3 888.5476.3375.3 687.3 816.4639.3
Hartbeespoort Dam
m/z 1045, Rt 5.31 min
MC-RY
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1017.5
440.3
973.5
602.3 865.4
1018.5
620.4 1027.4
916.5 974.5
1028.5
754.4 983.5911.5368.3
866.5595.3 917.5731.4441.3329.3 960.5
621.4519.4 775.3 860.4833.5357.3 431.4311.3 569.3 934.4520.3 888.5476.3375.3 687.3 816.4639.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S53
53
Figure S2ax. MS2 spectrum of probable MC-RY from M. aeruginosa AB2011/53
AB2011/53
m/z 1045, Rt 5.31 min
MC-RY (tentative trace)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
998.9
973.4
440.41017.4
943.9
620.5691.8
927.4
914.2
873.5802.0590.9368.2
844.3509.0 742.8666.0457.1 765.6708.3533.3 553.9 629.7423.2 506.6329.4 405.2
AB2011/53
m/z 1045, Rt 5.31 min
MC-RY (tentative trace)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
998.9
973.4
440.41017.4
943.9
620.5691.8
927.4
914.2
873.5802.0590.9368.2
844.3509.0 742.8666.0457.1 765.6708.3533.3 553.9 629.7423.2 506.6329.4 405.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S54
54
Figure S2ay. MS2 spectrum of tentative MC-(H4)YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1049, Rt 3.56 min
MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1031.5
1021.5
599.4
987.5
606.4 977.5920.5571.4 624.4 964.5915.5710.4682.4 728.4 880.4375.3 506.4 625.4418.3 837.5435.4 959.5779.4523.4347.3303.3
Hartbeespoort Dam
m/z 1049, Rt 3.56 min
MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1031.5
1021.5
599.4
987.5
606.4 977.5920.5571.4 624.4 964.5915.5710.4682.4 728.4 880.4375.3 506.4 625.4418.3 837.5435.4 959.5779.4523.4347.3303.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S55
55
Figure S2az. MS2 spectrum of tentativee MC-(H4)YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1049, Rt 3.56 min
MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1031.4
1021.5
599.4
987.5607.4
920.5 977.5571.4 624.4915.5710.4682.5 921.5892.5375.3 625.4418.3 837.4506.3 728.5435.3 779.4523.4303.3 347.3
AB2011/53
m/z 1049, Rt 3.56 min
MC-(H4)YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1031.4
1021.5
599.4
987.5607.4
920.5 977.5571.4 624.4915.5710.4682.5 921.5892.5375.3 625.4418.3 837.4506.3 728.5435.3 779.4523.4303.3 347.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S56
56
Figure S2ba. MS2 spectrum of tentative [DMAdda
5]MC-WR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1054, Rt 3.11 min
[DMAdda5]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1036.6
1026.6
991.7 1037.6
585.5
626.5
391.4
925.7643.5 934.6
982.6625.4
969.7586.4557.5
455.3894.6714.6
696.5543.4 935.6598.2393.3 779.6 890.5525.4 788.6472.4439.4 761.5 852.5347.2310.41055.0
Hartbeespoort Dam
m/z 1054, Rt 3.11 min
[DMAdda5]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1036.6
1026.6
991.7 1037.6
585.5
626.5
391.4
925.7643.5 934.6
982.6625.4
969.7586.4557.5
455.3894.6714.6
696.5543.4 935.6598.2393.3 779.6 890.5525.4 788.6472.4439.4 761.5 852.5347.2310.41055.0
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S57
57
Figure S2bb. MS2 spectrum of tentative [DMAdda
5]MC-WR from M. aeruginosa AB2011/53
AB2011/53
m/z 1054, Rt 3.11 min
[DMAdda5]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1026.6
1037.6
585.4
391.3 626.5
925.6581.4
917.5625.5
1009.7934.6 982.6
455.4
557.5 586.5668.5
943.6714.5897.6392.4 541.4 842.7
375.3 519.4 696.6472.2 811.6453.4 737.5 754.6608.4 868.7357.4312.31044.8
AB2011/53
m/z 1054, Rt 3.11 min
[DMAdda5]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1026.6
1037.6
585.4
391.3 626.5
925.6581.4
917.5625.5
1009.7934.6 982.6
455.4
557.5 586.5668.5
943.6714.5897.6392.4 541.4 842.7
375.3 519.4 696.6472.2 811.6453.4 737.5 754.6608.4 868.7357.4312.31044.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S58
58
Figure S2bc. MS2 spectrum of tentative [Asp
3]MC-WR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1054, Rt 4.13 min
[Asp3]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1036.4
1026.5
1037.4
599.4
1018.3
611.4982.5 1038.5
571.4
629.4 925.5696.4 903.5939.5
630.3 714.4491.4 760.4375.2 458.3 668.5414.4 529.3 797.4 868.5838.4310.3 323.4 1040.2
Hartbeespoort Dam
m/z 1054, Rt 4.13 min
[Asp3]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1036.4
1026.5
1037.4
599.4
1018.3
611.4982.5 1038.5
571.4
629.4 925.5696.4 903.5939.5
630.3 714.4491.4 760.4375.2 458.3 668.5414.4 529.3 797.4 868.5838.4310.3 323.4 1040.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S59
59
Figure S2bd. MS2 spectrum of tentative [Asp
3]MC-WR from M. aeruginosa AB2011/53
AB2011/53
m/z 1054, Rt 4.13 min
[Asp3]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1035.6
1036.6
1037.6
1026.6
599.5941.7
612.4 1018.5982.6924.6571.5 629.5 714.6 903.5469.5 647.5 784.5528.5375.3 441.3 725.6 842.7397.4310.3 331.3
AB2011/53
m/z 1054, Rt 4.13 min
[Asp3]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1035.6
1036.6
1037.6
1026.6
599.5941.7
612.4 1018.5982.6924.6571.5 629.5 714.6 903.5469.5 647.5 784.5528.5375.3 441.3 725.6 842.7397.4310.3 331.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S60
60
Figure S2be. MS2 spectrum of tentative [Dha
7]MC-WR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1054, Rt 4.35 min
[Dha7]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
599.5
1026.6
612.51036.6
1037.6
629.5
924.6
1010.7571.5 969.5
920.5682.5 760.6967.6728.5 898.9860.5
779.5547.5469.6 668.7 809.7310.3 844.5 893.6490.3332.9 453.4420.4398.6 1054.9
Hartbeespoort Dam
m/z 1054, Rt 4.35 min
[Dha7]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
599.5
1026.6
612.51036.6
1037.6
629.5
924.6
1010.7571.5 969.5
920.5682.5 760.6967.6728.5 898.9860.5
779.5547.5469.6 668.7 809.7310.3 844.5 893.6490.3332.9 453.4420.4398.6 1054.9
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S61
61
Figure S2bf. MS2 spectrum of tentative [Dha
7]MC-WR from M. aeruginosa AB2011/53
AB2011/53
m/z 1054, Rt 4.35 min
[Dha7]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1026.6
599.5
1037.6
924.6612.5
629.5
1010.7925.5
584.5571.5 728.4710.4630.5 903.6
741.5968.2898.0700.6 778.5682.4395.2 560.3 885.9361.3310.2 802.7 838.6473.4 535.5430.5
377.2
AB2011/53
m/z 1054, Rt 4.35 min
[Dha7]MC-WR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1026.6
599.5
1037.6
924.6612.5
629.5
1010.7925.5
584.5571.5 728.4710.4630.5 903.6
741.5968.2898.0700.6 778.5682.4395.2 560.3 885.9361.3310.2 802.7 838.6473.4 535.5430.5
377.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S62
62
Figure S2bg. MS2 spectrum of tentative [DMAdda
5]MC-Y(OMe)R from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1061, Rt 2.40 min
[DMAdda5]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1018.4
915.5
585.5
633.4
999.4
1033.5
924.4 989.5
926.4 1044.4
1045.5943.5635.4 871.5
876.4573.3
911.5976.4594.3 811.3
650.4618.5849.5693.5557.5 794.5749.3 893.5
481.5 817.3499.3456.5330.3 389.4320.1
Hartbeespoort Dam
m/z 1061, Rt 2.40 min
[DMAdda5]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1018.4
915.5
585.5
633.4
999.4
1033.5
924.4 989.5
926.4 1044.4
1045.5943.5635.4 871.5
876.4573.3
911.5976.4594.3 811.3
650.4618.5849.5693.5557.5 794.5749.3 893.5
481.5 817.3499.3456.5330.3 389.4320.1
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S63
63
Figure S2bh. MS2 spectrum of tentative [DMAdda
5]MC-Y(OMe)R from M. aeruginosa AB2011/53
AB2011/53
m/z 1061, Rt 2.40 min
[DMAdda5]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1043.7
1042.7
1044.6
1033.7
1025.4585.5
633.5 924.5
1017.7941.7
1016.6626.4
989.6 1045.8904.5557.5 634.4625.5 668.6 887.5 945.5696.5 860.5759.4549.5383.4 833.4801.6479.4401.2348.3 455.4317.1
1053.1
AB2011/53
m/z 1061, Rt 2.40 min
[DMAdda5]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1043.7
1042.7
1044.6
1033.7
1025.4585.5
633.5 924.5
1017.7941.7
1016.6626.4
989.6 1045.8904.5557.5 634.4625.5 668.6 887.5 945.5696.5 860.5759.4549.5383.4 833.4801.6479.4401.2348.3 455.4317.1
1053.1
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S64
64
Figure S2bi. MS2 spectrum of tentative [Asp
3]MC-Y(OMe)R from M. aeruginosa AB2011/53
AB2011/53
m/z 1061, Rt 3.60 min
[Asp3]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1043.6
1044.6
1033.6
599.5
932.6
1017.6619.4
989.6933.6571.5910.6
1045.6976.5636.4
728.6817.5682.5 951.6375.3
729.5637.4 882.6536.5 831.6469.5 791.5448.3 518.4347.3 397.3329.3 1052.3
AB2011/53
m/z 1061, Rt 3.60 min
[Asp3]MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1043.6
1044.6
1033.6
599.5
932.6
1017.6619.4
989.6933.6571.5910.6
1045.6976.5636.4
728.6817.5682.5 951.6375.3
729.5637.4 882.6536.5 831.6469.5 791.5448.3 518.4347.3 397.3329.3 1052.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S65
65
Figure S2bj. MS2 spectrum of tentative [Mser
7]MC-YR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1063, Rt 3.68 min
[Mser7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1045.5
1046.5
1035.5
599.4
621.4 991.5934.5
638.4
933.6571.4 1047.5710.4393.3 978.6894.5738.4 793.4552.4535.4375.3 493.4 877.3833.5 974.6683.4401.3 470.4359.4323.3
Hartbeespoort Dam
m/z 1063, Rt 3.68 min
[Mser7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1045.5
1046.5
1035.5
599.4
621.4 991.5934.5
638.4
933.6571.4 1047.5710.4393.3 978.6894.5738.4 793.4552.4535.4375.3 493.4 877.3833.5 974.6683.4401.3 470.4359.4323.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S66
66
Figure S2bk. MS2 spectrum of tentative [Mser
7]MC-YR from M. aeruginosa AB2011/53
AB2011/53
m/z 1063, Rt 3.68 min
[Mser7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1045.4
1046.5
1035.5
978.7599.4 1019.5
934.5621.4
1018.5962.4638.3 929.4 1047.5979.6537.4711.4520.4 894.6876.1561.1393.4 803.5738.5 983.6659.7446.5
352.3 476.0316.8
AB2011/53
m/z 1063, Rt 3.68 min
[Mser7]MC-YR (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1045.4
1046.5
1035.5
978.7599.4 1019.5
934.5621.4
1018.5962.4638.3 929.4 1047.5979.6537.4711.4520.4 894.6876.1561.1393.4 803.5738.5 983.6659.7446.5
352.3 476.0316.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S67
67
Figure S2bl. MS2 spectrum of confirmed MC-WR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1068, Rt 4.32 min
MC-WR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1040.6
1051.6
599.5
626.4
939.6
643.5 996.6938.6
571.5 1006.6983.6917.5
710.4940.6543.5 728.5 911.6
682.5798.5 856.5455.4 542.4 882.5438.3375.3 469.6
753.5437.4 838.5347.3310.3
Hartbeespoort Dam
m/z 1068, Rt 4.32 min
MC-WR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1040.6
1051.6
599.5
626.4
939.6
643.5 996.6938.6
571.5 1006.6983.6917.5
710.4940.6543.5 728.5 911.6
682.5798.5 856.5455.4 542.4 882.5438.3375.3 469.6
753.5437.4 838.5347.3310.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S68
68
Figure S2bm. MS2 spectrum of confirmed MC-WR from M. aeruginosa AB2011/53
AB2011/53
m/z 1068, Rt 4.32 min
MC-WR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1040.6
1051.6
599.5
626.5
939.6
643.5 996.7571.5 938.6
1006.7983.6917.6
710.4728.5543.4 940.7682.5469.5 856.6 956.6911.6542.6438.3375.3 661.4 798.5
472.4 781.5 811.5347.3 395.3310.3
AB2011/53
m/z 1068, Rt 4.32 min
MC-WR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1040.6
1051.6
599.5
626.5
939.6
643.5 996.7571.5 938.6
1006.7983.6917.6
710.4728.5543.4 940.7682.5469.5 856.6 956.6911.6542.6438.3375.3 661.4 798.5
472.4 781.5 811.5347.3 395.3310.3
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S69
69
Figure S2bn. MS2 spectrum of tentative MC-Y(OMe)R from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1075, Rt 3.87 min
MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1047.5
599.4
633.3
946.5
632.31003.5650.4
945.51013.5571.4 924.4
990.4
947.5918.5710.4682.4550.3
462.3 728.4 805.4 964.5549.4375.3 863.5 882.4469.5397.4 788.3533.3453.3 735.4 883.5845.5347.3317.2
Hartbeespoort Dam
m/z 1075, Rt 3.87 min
MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Re
lative
Ab
und
ance
1047.5
599.4
633.3
946.5
632.31003.5650.4
945.51013.5571.4 924.4
990.4
947.5918.5710.4682.4550.3
462.3 728.4 805.4 964.5549.4375.3 863.5 882.4469.5397.4 788.3533.3453.3 735.4 883.5845.5347.3317.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S70
70
Figure S2bo. MS2 spectrum of tentative MC-Y(OMe)R from M. aeruginosa AB2011/53
AB2011/53
m/z 1075, Rt 3.87 min
MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1047.7
1058.7
599.5
633.5
1003.8946.7650.5
632.5
945.7
1013.7
990.7571.5 941.6
924.7600.5 947.7710.6682.6 918.7
550.4 728.6 805.5 963.9375.4 479.5462.4 729.6533.4397.5347.4 788.6 806.6 882.7
303.4
AB2011/53
m/z 1075, Rt 3.87 min
MC-Y(OMe)R (tentative)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1047.7
1058.7
599.5
633.5
1003.8946.7650.5
632.5
945.7
1013.7
990.7571.5 941.6
924.7600.5 947.7710.6682.6 918.7
550.4 728.6 805.5 963.9375.4 479.5462.4 729.6533.4397.5347.4 788.6 806.6 882.7
303.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S71
71
Figure S2bp. MS2 spectrum of unidentified MC-XR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1085, Rt 4.01 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1067.5
1066.6
1056.5599.4 1068.5
642.4
955.5
600.41041.6
659.4 1012.6954.6
933.5571.5 956.5
471.3 682.4 999.5710.4 872.4625.3 728.5558.4453.3 488.4 542.4 927.4827.4796.9410.3375.4313.4
Hartbeespoort Dam
m/z 1085, Rt 4.01 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1067.5
1066.6
1056.5599.4 1068.5
642.4
955.5
600.41041.6
659.4 1012.6954.6
933.5571.5 956.5
471.3 682.4 999.5710.4 872.4625.3 728.5558.4453.3 488.4 542.4 927.4827.4796.9410.3375.4313.4
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S72
72
Figure S2bq. MS2 spectrum of unidentified MC-XR from M. aeruginosa AB2011/53
AB2011/53
m/z 1085, Rt 4.01 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1056.6
599.5
1068.6
642.4
955.6641.5
1012.7659.5
1039.6954.6571.6 999.7600.5
625.5 661.5 950.5559.4 728.6 957.6872.5453.4 471.4 710.5 814.6753.6910.6332.3 771.6558.5357.3 854.6428.2393.3 526.3329.2
AB2011/53
m/z 1085, Rt 4.01 min
Unidentified MC-XR
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
und
ance
1056.6
599.5
1068.6
642.4
955.6641.5
1012.7659.5
1039.6954.6571.6 999.7600.5
625.5 661.5 950.5559.4 728.6 957.6872.5453.4 471.4 710.5 814.6753.6910.6332.3 771.6558.5357.3 854.6428.2393.3 526.3329.2
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S73
73
Figure S2br. MS2 spectrum of confirmed MC-NfkR from Hartbeespoort Dam
Hartbeespoort Dam
m/z 1100, Rt 3.99 min
MC-NfkR (confirmed)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
un
da
nce
1072.5
1083.5
599.4
658.3
1028.5971.5
770.5657.3
1084.51015.5
675.3 1055.5970.5571.4
949.4600.4929.4
771.5487.3 682.4 972.5710.4
641.3469.4 830.3504.3 888.4753.5375.2558.3 813.5426.3347.3
1099.8
Supplementary Data File
Ballot et al., Diversity of cyanobacteria and cyanotoxins in Hartbeespoort Dam, South Africa
S74
74
Figure S2bs. MS2 spectrum of confirmed MC-NfkR from M. aeruginosa AB2011/53
AB2011/53
m/z 1100, Rt 3.99 min
MC-NfkR (confirmed)
300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
Rela
tive
Ab
un
da
nce
1072.6
1083.7
599.5
658.5
1015.6657.5 971.51028.7770.6 1084.6
1056.6970.7675.5
571.5 929.6682.6 710.6
600.5487.2989.6
771.7641.4 830.6 888.5470.4375.4 502.4 558.3 728.5452.3 796.5
324.1 365.3 1099.1
