determination of halogenated volatile organic …10.1007/s11743... · web view1 university...

Determination of halogenated volatile organic hydrocarbons in water samples

Supporting Information

Analytical characterization and comparison of tristyrylphenol ethoxylates used in agrochemical formulation

Johannes Glaubitz1,2, Torsten C. Schmidt1,*

1 University Duisburg-Essen, Instrumental Analytical Chemistry, Universittsstr. 5, 45141 Essen, Germany

2 Bayer CropScience, Formulation Technology Analysis & Services, Alfred-Nobel-Strae 50, 40789 Monheim am Rhein, Germany

*Corresponding author:

Phone: +49 201 183-6774

Fax: +49 201 183-6773

E-mail: [email protected]

Table of Contents

1.Sample for testing on mass calibration of TOF-MS6

2.Mass spectra of the major compounds in TSP-168

3.Comparison of the ionization performance of APPI and ESI for the analysis of TSP-40-ethoxylates11

4.Determination of the limit of quantification13

5.Data bases and results files for the data mining17

6.Results of the principal components analysis according to the score of the single compounds17

7.Comparison of TSP-16 of different suppliers and qualities20

8.Statistical evaluation of the results on the content of the components in TSP-16 on their use for product identification23

9.Example for interference on analysis of TSP-16 in agrochemical formulations25

List of Figures

Figure S 1: The mass spectra of the major compounds are displayed in Figure S 1 (a) for PEG, in Figure S 1(b) for MSP ethoxylates, in Figure S 1 (c) for DSP ethoxylates, in Figure S 1(d) for TSP ethoxylates and in Figure S 1(e) for TeSP ethoxylates. These mass spectra were obtained using APCI as coupling to the TOF mass spectrometer7

Figure S 2: Ionization behavior of TSP-40 ionized by APPI (a) and ESI (b). In each case the mass spectrum over the peak of TSP-ethoxylates is displayed. For each experiment the same elution conditions with water and methanol as mobile phase, plus 5 mmol/L ammonium formiate, were chosen. The mass spectrometer used for this experiments was a Thermo Q-exactive.11

Figure S 3: Chromatograms for determination of the signal-to-noise ratio at the defined LOQ level for TSP with 16 EO units (a) and hexanophenone (b). The LOQ was defined as a signal-to-noise ratio of at least 20:1, which has been achieved for both analytes.13

Figure S 4: Linear ranges for TSP with 16 EO units (a) and hexanophenone (b) including the bands of prediction indicated green for the upper and red for the lower limit14

Figure S 5: Distribution of residues for the regression analysis of standards of TSP with 16 EO units a) and the internal standard hexanophenone b)15

Figure S 6: Principle component analysis of the data sets from supplier A (Cross), B1 (Arrow), B2 (Horizontal Bar) and C (Vertical bar) together with the data of the formulation samples containing TSP-16 of supplier A (Square), B1 (Diamond), B2 (Circle) and C (Triangle). For the PCA the whole data set was taken including the 3 repetition analysis each production batch and formulation sample.22

Figure S 7: Combined hierarchical clustering of the samples (x-axis) and the compounds (y-axis) detected in the samples of supplier A, B1, B2 and C together with sample of formulation containing TSP-16 of Supplier A, B1, B2 and C. Each sample is the average of 3repetition analyses. The content of a compound in the analyzed sample is coded via black-white rectangles in the column beneath the respective samples. The color ranges from black, compound not detected, over grey, compound as abundant as internal standard, to white, compound with the maximum content.23

Figure S 8: Extracted ion chromatograms obtained in the positive ionization mode of terminal phosphated (a) and sulfated (b) commercially available TSP-16. Indicated are the identified entities of DSP-, TSP and TeSP ethoxylates.25

Figure S 9: Principal component analysis of the data sets from supplier A (Cross), B1 (Arrow), B2 (Horizontal Bar) and C (Vertical bar) together with the data of the formulation samples containing TSP-16 of supplier A (Square), B2 (Circle) and C (Triangle). For the PCA the whole data set was taken including the 3 repetition analysis each production batch and formulation sample.26

List of Tables

Table S 1: Retention time and exact masses for compounds in the test sample for checking on mass calibration6

Table S 2: Results for the test on heteroscedasticity against a level of significance of 0.05 on the data set used for linear regression of TSP-with 16 EO units and the internal standard hexanophenone according to Breusch-Pagan16

Table S 3: Given are the scores each compound for component 1 and 2 of the principle component analysis performed on the data set of the different suppliers of TSP-16, as it is graphically displayed in Figure 6 in the manuscript.17

Table S 4: Compounds used for the combined hierarchical clustering listed together with the corresponding arrays as defined in Figure 7 (see manuscript). The compounds are sorted according to the order obtained by the hierarchical clustering of the compounds.20

Table S 5: Table of composition of the model agrochemical formulation containing terminal sulfated TSP-16 alongside with TSP-1626

1. Sample for testing on mass calibration of TOF-MS

The retention times and exact masses for the compounds in the test sample for checking mass calibration of the used TOF-MS are given in Table S 1.

Table S 1: Retention time and exact masses for compounds in the test sample for checking on mass calibration

Compound

tN [min]

Exact mass [m/z]

Imidacloprid

2.0

254.0450

Thiacloprid

2.5

252.0236

Tebuconazole (1.Isomer)

4.3

307.1451

Triadimenol

4.6

295.1088

Tebuconazole (2.Isomer)

4.9

307.1451

Distyrylethoxylate-5-EO

5.8

522.2981


5.8

566.3244


5.8

610.3506


5.8

654.3768


5.8

698.4030


5.8

742.4292


5.8

786.4554


5.8

830.4816


5.8

874.5079


5.8

918.5341


5.8

962.5603


5.8

1006.5865


5.9

1050.6127


5.9

1094.6389


5.9

1138.6651


5.9

1182.6914


5.9

1226.7176


5.9

1270.7438


5.9

1314.7700


5.9

1358.7962


5.9

1402.8224


5.9

1446.8486


5.9

1490.8749


5.9

1534.9011


5.9

1578.9273


5.9

1622.9535

Nonylphenolethoxylate-5-EO

6.6

440.3138


6.3

484.3400


6.2

528.3662


6.2

572.3924


6.2

616.4186


6.2

660.4449


6.2

704.4711


6.2

748.4973


6.2

792.5235


6.2

836.5497


6.2

880.5759


6.2

924.6022


6.2

968.6284


6.2

1012.6546


6.2

1056.6808


6.2

1100.7070


6.2

1144.7332


6.2

1188.7594


6.2

1232.7857


6.2

1276.8119


6.2

1320.8381


5.9

1364.8643


5.9

1408.8905


5.9

1452.9167


5.9

1496.9429


5.9

1540.9692

Tristyrylethoxylate-5-EO

5.9

626.3607


5.9

670.38695


5.9

714.4132


6.5

758.4394


5.9

802.4656


5.9

846.4918


6.0

890.5180


6.0

934.5442


6.0

978.5705


6.0

1022.5967


6.0

1066.6229


6.0

1110.6491


6.0

1154.6753


6.0

1198.7015


6.0

1242.7278


6.0

1286.7540


5.9

1330.7802


5.9

1374.8064


5.9

1418.8326


5.9

1462.8588


5.9

1506.8850


5.8

1550.9113


5.8

1594.9375


5.8

1638.9637


5.8

1682.9899


5.8

1727.0161

2. Mass spectra of the major compounds in TSP-16

In the following Figure S 1 the mass spectra of the major compounds in TSP-16 are shown. In Figure S 1 (a) the mass spectrum of PEG, in Figure S 1 (b) the mass spectrum of MSP ethoxylates, in Figure S 1 (c) the mass spectrum of DSP ethoxylates, in Figure S 1 (d) the mass spectrum of TSP ethoxylates and in Figure S 1 (e) the mass spectrum of TeSP (4) ethoxylates are given.

Figure S 1: The mass spectra of the major compounds are displayed in Figure S 1 (a) for PEG, in Figure S 1(b) for MSP ethoxylates, in Figure S 1 (c) for DSP ethoxylates, in Figure S 1(d) for TSP ethoxylates and in Figure S 1(e) for TeSP ethoxylates. These mass spectra were obtained using APCI as coupling to the TOF mass spectrometer

(a)

PEG

PEG with 9 EO-units [M + NH4]+

Mass-to-Charge [m/z]

Signal intensity [counts]

(b)

(1) MSP-ethoxylates


MSP with 16 EO-units [M + NH4]+



(c)

(2) DSP-ethoxylates


DSP with 15 EO-units [M + NH4]+



(d)

(3) TSP-ethoxylates


TSP with 15 EO-units [M + NH4]+

(3) TSP-ethoxylates



(e)

(4) TeSP-ethoxylates


TeSP with 13 EO-units [M + NH4]+



As shown all compounds were identified as [M + NH4]-adducts, due to the addition 5mM of ammonium formate to the eluents. Furthermore, were identified entities of PEG for each of the styrenated phenol ethoxylates. This PEG is due to insource degradation of the respective styrenated phenol ethoxylates, as PEG originating from the sample of TSP-16 has been chromatographically separated and is eluting before the styrenated phenol ethoxylates between tR=1.0 min and tR=7.0 min.

3. Comparison of the ionization performance of APPI and ESI for the analysis of TSP-40-ethoxylates

The ionization performance of APPI and ESI was compared for the analysis of TSP-40-ethoxylates. For comparison the mass spectra of TSP-ethoxylates were taken for each ionization technique. Results for APPI are displayed in Figure S 2 (a) and for ESI in Figure S 2 (b).

(a)

TSP with 33 EO-units [M + Na]+

Relative abundance [%]


(b)

TSP with 35 EO-units [M + NH4]+

TSP with 43 EO-units [M + 4NH4]4+



Relative abundance [%]


Figure S 2: Ionization behavior of TSP-40 ionized by APPI (a) and ESI (b). In each case the mass spectrum over the peak of TSP-ethoxylates is displayed. For each experiment the same elution conditions with water and methanol as mobile phase, plus 5 mmol/L ammonium formiate, were chosen. The mass spectrometer used for this experiments was a Thermo Q-exactive.

For APPI a complex spectrum was obtained with a wide variety of signals, which can only partly be assigned to TSP-ethoxylates like the signal of TSP ethoxylate with 33 EO units. Given that the distribution of TSP-40 has its center on TSP with 33 EO units and not 40 EO units and taking into account the scatter of smaller peaks underlying the distribution it may be assumed that APPI is limited to ionization of entities with shorter EO chains. The ionization process, however, of entities with longer chain length leads to some sort of degradation shifting the center of distribution of ethoxylates and giving a wide variety of mass peaks, being fragments of this process. As the spectrum is very hard to interpret APPI is less favorable for characterization of TSP ethoxylates with longer EO chain lengths.

By comparison, the spectrum obtained by ESI shows only single to fourfold-charged mol peaks of TSP ethoxylates without apparent degradation products or fragments. Analogous to the spectrum obtained for TSP-16 in the manuscript in Figure 3 (b) the higher charged entities are dominant for longer EO chain lengths. The spectrum obtained by ESI was easier to interpret and without apparent degradation products and so ESI was taken as coupling to the mass spectrometer in this work.

4. Determination of the limit of quantification

The limits of quantification (LOQ) for both analytes hexanophenone and TSP with 16 EO units has been defined as a signal-to-noise ratio of at least 20:1 to ensure acceptable quantification results. In the following the respective chromatograms at LOQ level are given for TSP with 16 EO units (a) and hexanophenone (b) in Figure S 3, the linearity plots for TSP with 16 EO units (a) and hexanophenone (b) in Figure S 4 and the distribution of residues for TSP with 16 EO units (a) and hexanophenone (b) in Figure S 5. The data for the linear regression were found to be heteroscedastic according to the Breusch-Pagan with the results shown in Table S 2.

(a)


Acquisition time [min]

(b)



Figure S 3: Chromatograms for determination of the signal-to-noise ratio at the defined LOQ level for TSP with 16 EO units (a) and hexanophenone (b). The LOQ was defined as a signal-to-noise ratio of at least 20:1, which has been achieved for both analytes.

(a)

(b)

Figure S 4: Linear ranges for TSP with 16 EO units (a) and hexanophenone (b) including the bands of prediction indicated green for the upper and red for the lower limit

a)

b)

Figure S 5: Distribution of residues for the regression analysis of standards of TSP with 16 EO units a) and the internal standard hexanophenone b)

Table S 2: Results for the test on heteroscedasticity against a level of significance of 0.05 on the data set used for linear regression of TSP-with 16 EO units and the internal standard hexanophenone according to Breusch-Pagan

TSP with 16 EO units

Hexanophenone (ISTD)

p-Value

0.004

0.004

Hypothesis

H0 (Residues are homoscedastic) rejected

H0 (Residues are homoscedastic) rejected

Although the residues for the linear regressions were heteroscedastic, this was not considered for the calculation of the linear regression. As the aim of this work is the relative comparison of different suppliers of TSP-16 and not an absolute quantification of the single components this limitation is acceptable.

5. Data bases and results files for data mining

The compound search applied in this work, is a targeted on known compounds. The corresponding database is added as .csv file to the Supporting Information (TSP exact mass data base.csv). The resulting data set for the 2-step data mining approach on the nonionic surfactants in all the analyzed samples is added as a .txt file (TSP-16-ethoxylates_final.txt) to the Supporting Information together with the intermediate data sets obtained during data mining (TSP-16-ethoxylates molecular feature extractor.txt), normalization and reduction (TSP-16-ethoxylates Find-by-Formular.txt) to the defined linear range. The resulting data set on TSP 16 and TSP-16 in formulation samples is also added here (TSP-16-ethoxylates plus formulation samples.txt).

6. Results of the principal components analysis according to the score of the single compounds

In the following Table S 3 are shown the single scores each compound for component 1 and 2 of the principle component analysis as shown graphically in Figure 6 in the manuscript.

Table S 3: Given are the scores each compound for component 1 and 2 of the principle component analysis performed on the data set of the different suppliers of TSP-16, as it is graphically displayed in Figure 6 in the manuscript.

Compound

Component 1

Component 2

Mass

Retention Time

Hexanophenon

0

0

176.1201

4.58

Monostyryphenolethoxylate-11-EO

-21.518444

18.958761

682.392

4.92


-17.013428

17.149254

726.4198

4.94


-20.885107

20.679117

770.4452

4.96


-25.291218

23.80306

814.4709

4.99


-32.93415

28.694887

858.4977

5.01


-25.511671

39.14467

902.5234

5.03


-24.716763

39.249256

946.5495

5.05


-24.73755

38.80539

990.5766

5.07


-26.527723

40.04413

1034.602

5.08


-15.867841

32.809223

1078.629

5.10


-19.358452

27.466583

1122.653

5.11


-18.085913

16.839708

1166.68

5.13


-15.225504

13.234964

1210.703

5.14


-10.874819

8.432772

1254.729

5.16

Distyryphenolethoxylate-5-EO

-2.6254199

5.172396

522.3015

5.53


-4.185789

2.4134681

566.3277

5.55


-0.9710141

2.3733385

610.3523

5.56


-1.0998861

3.294223

654.3778

5.58


-2.7358875

1.6297657

698.4035

5.59


-1.941136

1.4260204

742.4296

5.60


-1.9511255

1.3822399

786.4559

5.60


-1.9803915

1.2908698

830.4822

5.61


-1.9467528

1.2308027

874.5083

5.62


-1.8844413

1.1279616

918.5346

5.63


-1.8335105

1.0220265

962.5605

5.64


-1.718206

0.90500146

1006.587

5.64


-1.6626208

0.81457263

1050.613

5.65


-1.5110463

0.68221706

1094.639

5.66


-1.4079044

0.5977382

1138.665

5.66


-1.2562836

0.45425314

1182.692

5.67


-1.150982

0.40137506

1226.718

5.67


-0.9551027

0.27022606

1270.744

5.68


0.3792616

-3.9362864

1314.77

5.68


-0.6929657

0.028805576

1358.796

5.68


-4.2088923

7.1047454

1402.823

5.68


-1.7542683

-0.26916566

1446.849

5.69


0.5838643

4.580197

1490.875

5.69


-6.2823634

-3.9688544

1534.901

5.69


25.656946

-21.225237

1578.929

5.65

Tristyryphenolethoxylate-5-EO

-3.4106627

1.4796438

626.361

6.00


-1.2727805

1.1529844

670.3875

6.01


-1.2660158

1.2475859

714.4137

6.01


-0.28587636

0.8669842

758.4396

6.01


-0.3896259

0.77770567

802.4657

6.02


-0.43556568

0.61594385

846.492

6.02


-0.47407123

0.57370925

890.5182

6.02


-0.4584877

0.45355675

934.5444

6.02


-0.41510287

0.36597556

978.5708

6.02


-0.36435264

0.29770425

1022.597

6.03


-0.27751935

0.1869533

1066.623

6.03


-0.193165

0.05831029

1110.649

6.03


-0.10277939

-0.066116735

1154.675

6.03


0.025035297

-0.1622553

1198.702

6.03


0.14945453

-0.3214445

1242.728

6.03


0.26133797

-0.3555113

1286.754

6.03


0.42371926

-0.5586756

1330.78

6.03


0.46660414

-0.41179907

1374.807

6.03


0.70624554

-0.7611214

1418.833

6.03


0.3835046

-0.1521237

1462.859

6.02


-0.5297137

-1.205153

1506.885

6.03


-0.9155471

0.63756394

1550.911

6.02


-4.92467

-0.46643406

1594.937

6.03


-2.411118

1.9084175

1638.963

6.02


-7.3978014

-11.465272

1682.99

6.02


40.23051

-31.489828

1727.015

6.00


13.274889

0.54010266

1771.045

6.06

Tetrastyryphenolethoxylate-5-EO

-3.7890558

-8.516457

730.4228

6.31


-12.51962

-19.076212

774.4505

6.33


-4.578877

-27.566341

818.4767

6.36


-19.086279

-12.592126

862.5024

6.37


-6.1373577

-26.144741

906.5262

6.35


-13.65941

-10.564696

950.5555

6.38


-6.8554664

-3.5307236

994.5801

6.38


-7.446675

-6.3279986

1038.607

6.38


-3.7851732

-4.298947

1082.633

6.38


-1.3549933

-0.73320895

1126.66

6.38


-1.3206834

-0.87198585

1170.686

6.38


-2.1694055

-0.7420312

1214.712

6.38


-6.312905

-8.372017

1258.738

6.37


-4.6640363

-1.1875252

1302.764

6.37


-15.150156

-6.937315

1346.79

6.37


-7.81072

-5.7653356

1390.817

6.37


-14.134495

-24.12576

1434.843

6.35


-14.034096

-10.08268

1478.87

6.36


-17.998505

-12.262659

1522.895

6.34


13.857056

-18.175201

1566.919

6.35


0.31084424

-0.30325606

1610.946

6.39

Monostyrylphenolprop-ethoxylate-5-EO-8-PO

26.74786

13.669259

882.5688

6.09


17.234734

8.269603

926.5933

6.12


29.101526

14.494107

970.6096

6.08


33.514618

16.18774

1014.637

6.06


35.42035

15.915241

1058.659

6.05


25.031956

16.850344

1102.685

6.06


17.60985

13.992486

1146.71

6.06


31.77927

15.785249

1190.735

6.05


5.6304994

0.3463299

1234.761

6.04

Distyrylphenolprop-ethoxylate-5-EO-8-PO

57.404755

7.765355

986.6327

6.39


57.82702

7.887388

1030.66

6.38


58.48031

7.788493

1074.686

6.38


58.59349

7.7376966

1118.711

6.38


58.646797

7.669096

1162.738

6.38


58.14472

7.6415954

1206.764

6.38


57.51143

7.6519156

1250.789

6.37


1.0730832

0.5492888

1062.638

6.05


56.77911

7.385921

1294.816

6.37


54.253757

9.28449

1338.839

6.37


54.626804

7.914997

1382.868

6.37


37.83858

4.5463367

1426.891

6.35


49.122604

8.906896

1470.919

6.37


6.9875383

-1.7860774

1514.936

6.29


37.346233

2.8904805

1558.969

6.35


3.4635794

0.73942816

1602.998

6.34

7. Comparison of TSP-16 of different suppliers and qualities

In Table S 4 the compounds in the different arrays determined by the hierarchical clustering (HCA) performed on the combined supplier data set are given.

Table S 4: Compounds used for the combined hierarchical clustering listed together with the corresponding arrays as defined in Figure 7 (see manuscript). The compounds are sorted according to the order obtained by the hierarchical clustering of the compounds.

Array

Compound

Array

Compound

1

Distyrylphenolprop-ethoxylate-16-EO 8-PO

5

Distyrylphenolethoxylate-15-EO

1


5


1


5

Tristyrylphenolethoxylate-22-EO

1


5


1


5


1


5


1


5


1


5


1


5


1


5


1


5


1

Monostyrylphenolprop-ethoxylate-11-EO 8-PO

5


1


5


1


5

Hexanophenone (Internal Standard)

1


5


1


5


1


5


1


5


1


5


1


5


1


5


2


5


2


5


2


5


2

Tetrastyrylphenolethoxylate-25-EO

5


2


5


2

Tetratstyrylphenolethoxylate-5-EO

5


2


5


2

Monostyrylphenolethoxylate-24-EO

5


2


5


2


5


2


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


3


5


4


5


4


5


4


5


4


5


4


5


4


5


4


5


5


5


5


5


5


5


5


5


5


8. Statistical evaluation of the results on the content of the components in TSP-16 on their use for product identification

As described, there were substantial differences in the contents of the main components, MSP-, DSP-, TSP- and TeSP ethoxylates, and the by-products, copolymerized propoxylates-ethoxylates of MSP and DSP, in the commercial TSP-16. These differences could be used as signature for product identification. Therefore, model formulation samples were prepared containing TSP-16 of each supplier and quality (A, B1, B2, C). In order to validate the clustering on TSP-16 according to its suppliers, the samples used for the model formulation were not part of the original data set. These samples were then analyzed in order to test if they were assigned correctly to their suppliers using both PCA and hierarchical clustering. In the following, the results of the PCA (Figure S 6) and of the HCA (Figure S 7) are displayed. In case of the HCA the clustering according to the compounds (y-axis) is compressed as only the clustering according to the samples (x-axis) was of interest.

Component 2 (22.1 %)


Figure S 6: Principle component analysis of the data sets from supplier A (Cross), B1 (Arrow), B2 (Horizontal Bar) and C (Vertical bar) together with the data of the formulation samples containing TSP-16 of supplier A (Square), B1 (Diamond), B2 (Circle) and C (Triangle). For the PCA the whole data set was taken including the 3 repetition analysis each production batch and formulation sample.

Figure S 7: Combined hierarchical clustering of the samples (x-axis) and the compounds (y-axis) detected in the samples of supplier A, B1, B2 and C together with sample of formulation containing TSP-16 of Supplier A, B1, B2 and C. Each sample is the average of 3repetition analyses. The content of a compound in the analyzed sample is coded via black-white rectangles in the column beneath the respective samples. The color ranges from black, compound not detected, over grey, compound as abundant as internal standard, to white, compound with the maximum content.

As demonstrated, both data analysis techniques were correctly assigning the TSP-16 in the model formulation to their corresponding suppliers. Using the PCA all four formulation samples were identified in their corresponding supplier cluster. They were all group within the clusters of their suppliers, as shown in the top dendrogram. The linkage of the formulation samples to a sample of the corresponding supplier cluster in the HCA was formed for all four samples at least two levels lower than the linkage of the respective supplier cluster. The assignments to the corresponding suppliers displayed in Figure S 7 were thus reasonable. The developed method combining instrumental analysis and multivariate data mining enables the identification of a supplier of TSP-16, without apparent matrix interference even though another functionalized PEG, an ethoxylated alcohol, had been used as well in the chosen model formulation.

9. Example for interference on analysis of TSP-16 in agrochemical formulations

The identification of the different suppliers in an agrochemical formulation can be interfered by end group sulfated or phosphated TSP ethoxylates, if they are contained in the agrochemical formulation. The chromatograms of commercially available TSP-16 terminal phosphated (a) and sulfated (b) are shown in Figure S 8 obtained in the positive ionization mode with the identified entities of DSP-, TSP- and TeSP ethoxylates.

(a)



(b)



Figure S 8: Extracted ion chromatograms obtained in the positive ionization mode of terminal phosphated (a) and sulfated (b) commercially available TSP-16. Indicated are the identified entities of DSP-, TSP and TeSP ethoxylates.

As shown there are entities of DSP-, TSP- and TeSP ethoxylates detectable in commercially available terminal sulfated and phosphated TSP-16 in the chosen ionization mode. These entities of DSP-, TSP- and TeSP ethoxylates can be explained by incomplete phosphating or sulfating of the educt TSP-16 which was not removed after the reaction from the final commercially product. Possible interferences of these entities on the identification of the different suppliers of TSP-16 in the matrix of the model agrochemical formulations were investigated next. TSP-16 of supplier A, B2 and C and terminal sulfated TSP-16 were mixed in the model agrochemical as shown in Table S 5.

Table S 5: Table of composition of the model agrochemical formulation containing terminal sulfated TSP-16 alongside with TSP-16

Raw material

Content [%] (w/w)

Active ingredient

23.0

TSP-16

2.5

TSP-16, sulfated

2.5

Dispersing agent (non-ionic)

10.0

Emulsifier 1 (non-ionic, functionalized PEG)

15.0

Emulsifier 2 (non-ionic, functionalized PPG-PEG-co-polymer)

9.0

Hydrophbically modified Clay

0.1

Acid

0.4

Solvent

37.5

These formulation samples were subjected to the analysis and multivariate data analysis techniques developed and used in this work, with the results of the principal component analysis (PCA) shown in Figure S 9.



Figure S 9: Principal component analysis of the data sets from supplier A (Cross), B1 (Arrow), B2 (Horizontal Bar) and C (Vertical bar) together with the data of the formulation samples containing TSP-16 of supplier A (Square), B2 (Circle) and C (Triangle). For the PCA the whole data set was taken including the 3 repetition analysis each production batch and formulation sample.

As shown the entities of DSP-, TSP- and TeSP ethoxylates contained in end group sulfated TSP-16 interfere with the developed method. As formulations using a combination of TSP-16 and another TSP ethoxylates derivate are not widely spread this potential interference can be accepted. Nevertheless, further investigations should test the possibility for a correction of the observed interferences.

33.20000000000000324.90000000000000216.6000000000000016.64000000000000154.97999999999999953.32000000000000071.66000000000000040.664000000000000030.332000000000000020.1328103282137848166535936321759221646147112024256685623083015571784418Intervall of confidence neg33.85989571657380325.55989571031982917.2598957040437787.29989569601604775.63989569468010383.97989569335392272.31989569195844061.32389569111107890.991895690921665190.79269569074186952103282137848166535936321759221646147112024256685623083015571784418Intervall of confidence pos32.54010428342620324.24010428968017515.9401042959562255.98010430398395524.32010430531989532.66010430664607881.00010430804155994.1043088889213264E-3-0.32789569092166521-0.52709569074186946103282137848166535936321759221646147112024256685623083015571784418

c [mg/L]

counts

121.9999999999999997.673.19999999999998948.824.412.26.12.441.2227802032206059163586210492045103902453731195065022921583Intervall of confidence pos125.31938061340226100.9193805119662776.51938041122758752.11938030758070527.71938021238656815.5193801655650989.41938014332773755.75938013108832974.539380126027341927802032206059163586210492045103902453731195065022921583Intervall of confidence neg118.6806193865977194.28061948803372269.8806195887723945.48061969241928921.0806197876134298.8806198344349012.7806198566722613-0.87938013108833024-2.099380126027342427802032206059163586210492045103902453731195065022921583

c [mg/L]

counts

Active33.20000000000000324.90000000000000216.6000000000000016.64000000000000154.97999999999999953.32000000000000071.66000000000000040.664000000000000030.332000000000000020.1328-1.42733632036734240.361945623210172982.00127043876130010.596695772778707110.376275276833674180.22213322829178342-0.40265430166777577-0.84593576804330584-0.36181318123530065-0.52058076856184898

Content TSP with 16-EO units [mg/L]

Standardisierte Residuen

Active121.9999999999999997.673.19999999999998948.824.412.26.12.441.220.960326617972534490.18747841979465302-0.40568916291110613-1.7482164140449588-0.91272507722714635-0.295131954568851220.316007856736906010.966903047932612170.93104666631530619

Content ISTD [mg/L]

Standardisierte Residuen

1

6

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