mycotoxins in the environment: ii. occurrence and origin

SUPPORTING INFORMATION TO ARTICLE:

Mycotoxins in the environment: II. Occurrence and origin in Swiss river waters

Judith Schenzel 1,2

, Konrad Hungerbühler 2, Thomas D. Bucheli

1 *

1) Research Station Agroscope Reckenholz-Taenikon ART, CH-8046 Zurich, Switzerland

2) Institute for Chemical and Bioengineering; Swiss Federal Institute of Technology (ETH), CH-8093

Zurich, Switzerland

* Corresponding author.

Content:

SI-1 Geographical situation within the sampling area.

Figure S1: Map of Switzerland including the location of the river water sampling stations:

river Glatt catchment (A-E); river Töss catchment (F-I) all from the AWEL monitoring

program (▲). NADUF (■) river sampling stations J) Thur; K) Rhine; L) Aare. The

agricultural area cropped with winter wheat of the total municipal area is given in percentage.

Figure S2: Map of the Canton of Zurich and the Canton of Aargau, including the location of

the river water sampling stations in the river Glatt (A-E), Töss (F-I; all from the AWEL

monitoring program (▲)), Thur (J), Rhine (K), and Aare (L; all from the NADUF monitoring

program (■)) catchments. The agricultural area cropped with silage maize of the total

agricultural area is given in percentage. (Source: Swiss Federal Statistical Office; Statistic of

the agricultural area of Switzerland for the year 2010),

Figure S3: Map of the Canton of Zurich and the Canton of Aargau, including the location of

the river water sampling stations in the river Glatt (A-E), Töss (F-I; all from the AWEL

monitoring program (▲)), Thur (J), Rhine (K), and Aare (L; all from the NADUF monitoring

program (■)) catchments. The agricultural area cropped with seed corn of the total municipal

area is given in percentage. (Source: Swiss Federal Statistical Office; Statistic of the

agricultural area of Switzerland for the year 2010)

SI-2 Analytical procedures and figures of merit.

Table S1: Ion suppressions, absolute recoveries, relative recoveries, and precisions of

mycotoxins in river water.

Table S2: Ion suppressions, absolute recoveries, relative recoveries, and precisions of

mycotoxins in waste water treatment plant effluents (WWTP effluents).

Table S3: Method detection limits [ng/L] of mycotoxins in river, and waste water.

SI-3 Concentrations for all detected mycotoxins [ng/L] at all sampling sites during the

investigation period January 2010 till end of October 2011.

Table S4: Concentrations of nivalenol [ng/L] at all sampling sites during the investigation

period from January 2010 till end of October 2011.

Table S5: Concentrations of 3-acetyl-deoxynivalenol [ng/L] at all sampling sites during the

investigation period from January 2010 till end of October 2011.

Table S6: Concentrations of beauvericin [ng/L] at all sampling sites during the investigation

period from January 2010 till end of October 2011.

SI-4 Concentration versus discharge: dilution as concentration determinant.

Figure S4: Mycotoxin concentrations depicted versus the average weekly river discharge

[m3/s] in the rivers Glatt, Töss, and the three sampled NADUF rivers (Thur, Rhine and Aare)

showing the dilution as one of the main determinant. A) Deoxynivalenol, B) Nivalenol, C) 3-

Acetyl-deoxynivalenol, and D) Beauvericin. LOD = limit of detection; LOQ = limit of

quantification.

SI-5 Occurrence of mycotoxins in all sampled river water stations from January 2010 until

November 2011.

Figure S5: Occurrence of mycotoxins in river water samples from AWEL station Aa at

Niederuster (Station A).

Figure S6: Occurrence of mycotoxins in river water samples from AWEL station Aabach at

Mönchaltorf (Station B).

Figure S7: Occurrence of mycotoxins in river water samples from AWEL station Glatt at

Fällanden (Station C).


Rheinsfelden (Station E).

Figure S9: Occurrence of mycotoxins in river water samples from AWEL station Töss at

Rämismühle (Station F).

Figure S10: Occurrence of mycotoxins in river water samples from AWEL station Kempt at

Winterthur (Station G).

Figure S11: Occurrence of mycotoxins in river water samples from AWEL station Eulach at

Wülfingen (Station H).

Figure S12: Occurrence of mycotoxins in river water samples from AWEL station Töss at

Freienstein (Station I).

SI-6 Seasonal load fractions of mycotoxins.

Figure S13: Seasonal load fraction (SLF) of each mycotoxin versus the ratio of total cropped

wheat area and number of inhabitants. A) Deoxynivalenol, B) Nivalenol, C) 3-Acetyl-

deoxynivalenol, and D) Beauvericin.

Table S7: Robust linear regression analysis of cumulative mycotoxin loads over the period of

nearly two years of investigation and during summertime 2010 vs. total cropped wheat area

and population equivalents in the corresponding river catchment. The cumulative mycotoxin

loads are at log scale.

SI-7 Mycotoxin fractions emitted from agricultural areas cropped with winter wheat and

from human excretion via WWTP effluents over an investigation period from January

2010 until November 2011 in the river Glatt and Töss catchment. The width of green and

blue boxes represent winter wheat area per catchment [km2] and average water flow Q

[m3/s] as observed during the period of investigation, respectively.

Table S8: Predicted loads [g] for the whole investigation period of mycotoxins coming from

human emission via WWTP and from agricultural areas cropped with small grain cereals.

Figure S14: Surface waters of the Canton of Zurich with the river Glatt and Töss highlighted

in dark blue. Inserted bar charts show the estimated amounts from WWTP effluents (blue),

and from agricultural areas cropped with winter wheat (green). They are compared to the total

nivalenol load [g] observed (red) at each sampling station over an investigation period from

January 2010 until November 2011.




3-acetyl-deoxynivalenol load [g] observed (red) at each sampling station over an investigation

period from January 2010 until November 2011.




beauvericin load [g] observed (red) at each sampling station over an investigation period from


SI-1 Geographical situation within the sampling area.

Figure S1: Map of Switzerland including the location of the river water sampling stations: river Glatt

catchment (A-E); river Töss catchment (F-I) all from the AWEL monitoring program (▲). NADUF

(■) river sampling stations J) Thur; K) Rhine; L) Aare. The agricultural area cropped with winter

wheat of the total municipal area is given in percentage (Source: Swiss Federal Statistical Office;

Statistic of the agricultural area of Switzerland for the year 2010).

Figure S2: Map of the Canton of Zurich and the Canton of Aargau including the location of the river

water sampling stations: river Glatt catchment (A-E); river Töss catchment (F-I) all from the AWEL

monitoring program (▲). NADUF (■) river sampling stations J) Thur; K) Rhine; L) Aare. The

agricultural area cropped with silage maize of the total municipal area is given in percentage (Source:

Swiss Federal Statistical Office; Statistic of the agricultural area of Switzerland for the year 2010).

Percentage of the total agricultural area cropped with silage maize

Percentage of the total agricultural area cropped with winter wheat

Figure S3: Map of the Canton of Zurich and the Canton of Aargau including the location of the river

water sampling stations: river Glatt catchment (A-E); river Töss catchment (F-I) all from the AWEL

monitoring program (▲). NADUF (■) river sampling stations J) Thur; K) Rhine; L) Aare. The

agricultural area cropped with seed corn of the total municipal area is given in percentage (Source:

Swiss Federal Statistical Office; Statistic of the agricultural area of Switzerland for the year 2010).

Percentage of the total agricultural area cropped with seed corn

SI-2 Analytical procedures and figures of merit.

Raw water samples were filtered (glass fibre filters, pore size 1.2 µm, Millipore, Volketswil,

Switzerland) by vacuum filtration (Supelco, Bellfonte PA, USA), transferred to 1 L glass bottles and

stored in the dark at +4 °C until analysis within 2 weeks (storage tests showed that mycotoxins were

stable over this period of time). Before SPE, the pH was adjusted to between 6.6 and 7.0 by adding

either ammonium acetate or acetic acid. In routine analysis the exact volume of 1 L was spiked with

50 µL of the ILIS mixture before the storage or processing of the sample. The samples were shaken

vigorously before further treatment. Filtered water samples (1 L) were concentrated and purified by

performing reversed-phase SPE (Oasis HLB cartridges, 6 mL, 200 mg; Waters Corporation, Milford

MA, USA) on a 12-fold vacuum extraction box (Supelco, Bellfonte PA, USA). The SPE cartridges

were consecutively conditioned with 5 mL of MeOH, 5 mL of Milli-Q water and MeOH (1/1, v/v),

and 5 mL of Milli-Q water. One Liter water samples were passed through the cartridges with a

maximum flow rate of 10 mL/min. Subsequently, the cartridges were washed with 5 mL of Milli-Q

water. Without any additional column drying step the analytes were eluted with 5 mL MeOH and the

aliquots were collected in conical reaction vial vessels (Supelco, Bellfonte PA, USA). The 5 mL

MeOH aliquots were reduced to 100 µL under a gentle nitrogen gas stream at 50°C. The extracts were

reconstituted in 900 µL of Milli-Q water/MeOH (90/10, v/v) and transferred into 1.5 mL amber glass

vials. The samples were stored at +4°C and analyzed within 48 h.

Chromatographic separation and mass spectrometric detection: LC-MS/MS was performed on a

Varian 1200L LC-MS instrument (VarianInc, Walnut Creek CA, USA). The mycotoxins were

separated using a 125 mm × 2.0 mm i.d., 3 µm, Pyramid C18 column, with a 2.1 mm x 20 mm i.d. 3

µm guard column of the same material (Macherey-Nagel GmbH & Co. KG, Düren, Germany) at room

temperature. Two different chromatographic runs were used for the separation of all compounds, on in

the positive and one in the negative ionization mode, respectively. The optimized LC mobile phase

gradient for the analysis of the analytes measured in negative ionization mode was as follows: 0.0 min:

0% B (100% A), 2.0 min: 0% B, 15.0 min: 100% B, 18.0 min: 100% B, 19.0 min: 0% B, 24.0 min: 0%

B. The analytes measured in the positive ionization mode were separated with the following gradient:

0.0 min: 27% B (73% A), 1.0 min: 27% B, 1.3 min: 45% B, 5.0 min: 45% B, 5.3 min: 63% B, 9.0 min:

63% B, 9.3 min: 81% B, 13.0 min: 81% B, 13.3 min: 100% B, 20.0 min: 100% B, 21.0 min: 27% B,

24.0 min: 27% B. In both cases eluent A consisted of Milli-Q water/MeOH/acetic acid (89/10/1, v/v/v)

and eluent B of Milli-Q water/MeOH/acetic acid (2/97/1, v/v/v). Both eluents were buffered with 5

mM ammonium acetate. The injection volume was 40 µL and the mobile phase flow was 0.2 mL/min.

LC-MS interface conditions for the ionization of the acidic mycotoxins in the –ESI mode were: needle

voltage - 4000 V, nebulizing gas (compressed air) 3.01 bar, drying gas (N2, 99.5%) 275°C and 1.24

bar, shield voltage -600 V. The neutral mycotoxins were ionized in the +ESI mode: needle voltage +

4500 V, nebulizing gas (compressed air) 3.01 bar, drying gas (N2, 99.5%) 275°C and 1.24 bar, shield

voltage + 600 V.

Table S1: Ion suppressions, relative recoveriesª, absolute recoveries a, and precision of mycotoxins in

river water.

Compound Ion suppression

[%]

Concentration

level [ng/L]

Relative Recoveries

[%]

Absolute Recoveries

[%] Precision [%]

5 n.a. n.a.

3-Acetyl-DON -10 25 76 (7) 75 (7) 7

100 87 (7) 77 (6)

5 100 (6) 71 (7)

Deoxynivalenol -8 25 109 (2) 91 (4) 6

100 106 (3) 104 (3)

5 n.a.

Nivalenol 39 25 22 (2) 7

100 21 (2)

5 56 (8)

Beauvericin -19 25 73 (11) 1

100 44 (8)

n.a. not available due to higher method detection limit; a Absolute standard deviation (five replicates) in parenthesis

Table S2: Ion suppressions, relative recoveriesª, absolute recoveries a, and precision of mycotoxins in

waste water treatment plant effluent.

Compound Ion suppression

[%]

Concentration

level [ng/L]

Relative Recoveries

[%]

Absolute Recoveries

[%] Precision [%]

5 n.a. n.a.

3-Acetyl-DON -42 25 104 (7) 79 (7) 9

100 94 (5) 85 (2)

5 106 (12) 33 (8)

Deoxynivalenol -61 25 105 (5) 69 (7) 10

100 96 (6) 72 (3)

5 n.a.

Nivalenol -28 25 20 (1) 6

100 11 (0)

5 76 (6)

Beauvericin 18 25 77 (4) 7

100 104 (8)

n.a. not available due to higher method detection limit; a Absolute standard deviation (five replicates) in parenthesis

Table S3: Method detection limit [ng/L]ª of mycotoxins in river water and waste

water treatment plant effluent (WWTP).

Compound MDL river water MDL WWTP effluent

3-Acetyl-Deoxynivalenol 6.1b 6.0b

Deoxynivalenol 1.3 1.2

Nivalenol 1.5b 1.6b

Beauvericin 1.3 3.4

a Three times the absolute standard deviation at 5 ng/L; b Three times the absolute standard

deviation at 25 ng/L.

SI-3 Concentrations for all detected mycotoxins [ng/L] at all sampling sites during the investigation period January 2010 till end of October 2011.

Table S4: Concentrations of nivalenol [ng/L] in the weekly and fortnightly collected flow-proportional surface water

samples from the AWEL and NADUF sampling sites from January 2010 to November 2011.

River location detected/#

samples

analyzed

min

concentration

[ng/L]c

max

concentration

[ng/L]c

median

concentration

[ng/L]c

cumulative NIV

load [kg]d

SLFe [%]

River Glatta

Aa at Niederuster (A) 41/95 1.5 f 15.8 5.6 0.4 74 ± 7

Aabach at Mönchaltorf (B) 51/95 1.5 f 20.1 6.4 0.2 74 ± 8

Glatt at Fällanden (C) 21/95 1.5 f 11.8 5.7 0.4 63 ± 4

Glatt at Oberglatt (D) 51/95 1.5 f 17.2 5.9 1.1 74 ± 7

Glatt at Rheinsfelden (E) 57/95 1.5 f 16.8 5.9 1.2 71 ± 7

River Tössa

Töss at Rämismühle (F) 14/95 1.5 f 8.8 1.5 0.1 80 ± 2

Kempt at Winterthur (G) 37/95 1.5 f 24.1 3.4 0.1 72 ± 4

Eulach at Wülflingen (H) 45/95 1.5 f 15.1 5.2 0.1 83 ± 5

Töss at Freienstein (I) 42/95 1.5 f 13.8 3.2 0.6 60 ± 4

Larger Rivers in the Swiss Midlandsb

Thur at Andelfingen (J) 23/78 1.5 f 16.0 6.4 4.7 91 ± 3

Rhine at Rekingen (K) 4/73 1.5 f 10.5 7.6 13.6 63 ± 1

Aare at Brugg (L) 4/48 1.5 f 8.0 2.8 2.5 85 ± 1

amonitoring network: AWEL (Office for waste, water, energy and air, Canton Zurich, Switzerland); bmonitoring network:

NADUF (National River Monitoring and Survey Program); Letter in parenthesis indicate abbreviations in Figure 1. cout of

detected samples. d cumulative loads were obtained by a simple addition of all quantified loads which were detected after 22

months. e SLF: seasonal load fraction, sum of the NIV loads detected in summer and autumn at each specific station ± uncertainty

obtained by an error propagation based on the analytical method precision.10

f above LOD of 1.5 ng/L, but below LOQ of 4.5

ng/L.

Table S5: Concentrations of 3-Acetyl-deoxynivalenol [ng/L] in the weekly and fortnightly collected flow-

proportional surface water samples from the AWEL and NADUF sampling sites from January 2010 to November

2011.


samples

analyzed

min

concentration

[ng/L]c

max

concentration

[ng/L]c

median

concentration

[ng/L]c

cumulative

3-AcDON

load [kg]e

SLFe [%]

River Glatta

Aa at Niederuster (A) 41/95 6.1f 6.1f 6.1f 0.06 41 ± 1

Aabach at Mönchaltorf (B) 51/95 6.1f 6.1f 6.1f 0.04 76 ± 2

Glatt at Fällanden (C) 21/95 6.1f 6.1f 6.1f 0.09 42 ± 1

Glatt at Oberglatt (D) 51/95 6.1f 19.2 6.1f 0.44 49 ± 3

Glatt at Rheinsfelden (E) 57/95 6.1f 6.1f 6.1f 0.86 77 ± 3

River Tössa

Töss at Rämismühle (F) 14/95 6.1f 6.1f 6.1f 0.03 0

Kempt at Winterthur (G) 37/95 6.1f 6.1f 6.1f 0.10 52 ± 2

Eulach at Wülflingen (H) 45/95 6.1f 6.1f 6.1f 0.03 50 ± 1

Töss at Freienstein (I) 42/95 6.1f 6.1f 6.1f 0.40 46 ± 2


Thur at Andelfingen (J) 23/78 6.1f 6.1f 6.1f 0.66 33 ± 1

Rhine at Rekingen (K) 4/73 nd. nd. nd. nd. -

Aare at Brugg (L) 4/48 6.1f 6.1f 6.1f 0.95 100 ± 1

amonitoring network: AWEL (Office for waste, water, energy and air, Canton Zurich, Switzerland); bmonitoring network:

NADUF (National River Monitoring and Survey Program); Letter in parenthesis indicate abbreviations in Figure 1. cout of

detected samples. d cumulative loads were obtained by a simple addition of all quantified loads which were detected after 22

months. nd.: not detected. e SLF: seasonal load fraction, sum of the 3-AcDON loads detected in summer and autumn at each

specific station ± uncertainty obtained by an error propagation based on the analytical method precision.10

f above LOD of

6.1 ng/L, but below LOQ of 18.3 ng/L.

Table S6: Concentrations of beauvericin [ng/L] in the weekly and fortnightly collected flow-proportional surface water

samples from the AWEL and NADUF sampling sites from January 2010 to November 2011.


samples

analyzed

min

concentration

[ng/L]c

max

concentration

[ng/L]c

median

concentration

[ng/L]c

cumulative

BEA load [kg]e

SLFe [%]

River Glatta

Aa at Niederuster (A) 41/95 1.3f 10.5 1.3f 0.03 33 ± 1

Aabach at Mönchaltorf (B) 51/95 1.3f 22.0 1.3f 0.03 23 ± 2

Glatt at Fällanden (C) 21/95 1.3f 1.3f 1.3f 0.03 51 ± 2

Glatt at Oberglatt (D) 51/95 1.3f 20.7 1.3f 0.13 10 ± 2

Glatt at Rheinsfelden (E) 57/95 1.3f 17.3 1.3f 0.24 12 ± 2

River Tössa

Töss at Rämismühle (F) 14/95 1.3f 18.0 1.3f 0.07 17 ± 2

Kempt at Winterthur (G) 37/95 1.3f 7.0 1.3f 0.03 25 ± 2

Eulach at Wülflingen (H) 45/95 1.3f 5.3 1.3f 0.01 8 ± 1

Töss at Freienstein (I) 42/95 1.3f 4.8 1.3f 0.09 16 ± 2


Thur at Andelfingen (J) 23/78 1.3f 5.5 1.3f 0.22 90 ± 1

Rhine at Rekingen (K) 4/73 nd. nd. nd. nd. -

Aare at Brugg (L) 4/48 1.3f 12.4 4.6 4.39 24 ± 1

amonitoring network: AWEL (Office for waste, water, energy and air, Canton Zurich, Switzerland); bmonitoring network: NADUF

(National River Monitoring and Survey Program); Letter in parenthesis indicate abbreviations in Figure 1. cout of detected samples. d cumulative loads were obtained by a simple addition of all quantified loads which were detected after 22 months. nd.: not detected. e SLF: seasonal load fraction, sum of the BEA loads detected in summer and autumn at each specific station ± uncertainty obtained

by an error propagation based on the analytical method precision.10

f above LOD of 1.3 ng/L, but below LOQ of 3.9 ng/L.

SI-5 Concentration versus discharge: dilution as concentration determinant.

Figure S4: Mycotoxin concentrations depicted versus the average weekly river discharge [m3/s] in the rivers Glatt ( ), Töss ( ), and the three sampled NADUF

( ) rivers (Thur, Rhine and Aare) showing the dilution as one of the main determinant. A) Deoxynivalenol, B) Nivalenol, C) 3-Acetyl-deoxynivalenol, and D)

Beauvericin. LOD = limit of detection; LOQ = limit of quantification.

Weekly discharge [m3/s]

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SI-6 Occurrence of mycotoxins in all sampled river water stations from January 2010 until

November 2011.

Figure S5: Occurrence of mycotoxins [ng/L] in river water samples from AWEL station Aa at

Niederuster (Station A). Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C)

deoxynivalenol [ng/L]; (D) beauvericin [ng/L]; (E) weekly river water discharge [m3/s]. The colored

stripes indicate the seasons: spring: green; summer: red; autumn: yellow; winter: white. LOD: limit of

detection; points under LOD-level: not detected. Note that on the right axis of the graph for panel B,

C, and D the corresponding loads [g] are given.

Aa at Niederuster (A)

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Figure S6: Occurrence of mycotoxins in river water samples from AWEL station Aabach at

Mönchaltorf (Station B). Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C)





Aabach at Mönchaltorf (B)

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Figure S7: Occurrence of mycotoxins in river water samples from AWEL station Glatt at Fällanden

(Station C). Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C) deoxynivalenol

[ng/L]; (D) beauvericin [ng/L]; (E) weekly river water discharge [m3/s]. The colored stripes indicate

the seasons: spring: green; summer: red; autumn: yellow; winter: white. LOD: limit of detection;

points under LOD-level: not detected. Note that on the right axis of the graph for panel B, C, and D

the corresponding loads [g] are given.

AWEL Station - Glatt at Fällanden (C)

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Rheinsfelden (Station E). Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C)





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Figure S9: Occurrence of mycotoxins in river water samples from AWEL station Töss at Rämismühle

(Station F): Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C) deoxynivalenol





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Figure S10: Occurrence of mycotoxins in river water samples from AWEL station Kempt at

Winterthur (Station G): Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C)





Kempt at Winterthur (G)

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Figure S11: Occurrence of mycotoxins in river water samples from AWEL station Eulach at

Wülfingen (Station H): Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C)





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Figure S12: Occurrence of mycotoxins in river water samples from AWEL station Töss at Freienstein

(Station I): Left axis (A) 3-acetyl-deoxynivalenol [ng/L]; (B) nivalenol [ng/L]; (C) deoxynivalenol





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SI-6 Seasonal load fractions of mycotoxins.

Figure S13: Seasonal load fraction (SLF) of each mycotoxin versus the ratio of total cropped wheat

area and number of inhabitants. A) Deoxynivalenol, B) Nivalenol, C) 3-Acetyl-deoxynivalenol, and

D) Beauvericin.

wheat area/inhabitant ratio0.0000 0.0020 0.0025

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TABLE S7: Linear regression analysis of cumulative mycotoxin loads from nine locations of the rivers Glatt and Töss over the period of nearly two

years of investigation and during summertime 2010 vs. total cropped wheat area and population equivalents in the corresponding catchments. The

cumulative mycotoxin loads are at log scale.a

vs. wheat area vs. inhabitants

compound R2 MSE p-value slope intercept R2 MSE p-value slope intercept

January 2010 - November 2011:

Deoxynivale

nol

0.46 0.000854 0.044 15.23 -0.75 0.89 4.19E-07 0.00014 215084.2 -0.85

Nivalenol 0.31 0.00171 0.119 13.72 -0.72 0.91 8.37E-07 0.00008 238745.6 -0.87

3-Acetyl-

DON

0.54 0.00589 0.025 13.3 -1.4 0.91 5.78E-07 0.00007 176301.9 -1.3

Beauvericin 0.17 0.000553 0.271 8.56 -1.56 0.65 2.71E-07 0.00897 170201.4 -1.74

June 2010 – October 2010:

Deoxynivale

nol

0.5 0.00293 0.033 18.03 -1.08 0.87 2.88E-07 0.00025 241809.2 -1.15

Nivalenol 0.19 0.00301 0.248 11.71 -1.08 0.82 2.95E-07 0.00076 251366.7 -1.24

3-Acetyl-

DON

0.31 0.00457 0.193 9.3 -1.8 0.83 4.49E-07 0.00443 158626.6 -2

Beauvericin 0.17 0.000217 0.271 8.56 -1.56 0.65 2.13E-08 0.00897 170201.4 -1.74 ato obtain normally distributed values. Note that there is no correlation between wheat area and population equivalent (R2=0.41; p-value=0.35204).

The Tukey-Anscombe plot showed normal distributed residuals. MSE = mean squared error.

SI-7 Estimated mycotoxin fractions emitted from agricultural areas cropped with winter wheat and from human excretion via WWTP effluents over

an investigation period from January 2010 until November 2011 in the river Glatt and Töss catchment. The width of green and blue boxes represent

winter wheat area per catchment [km2] and average water flow Q [m

3/s] as observed during the period of investigation, respectively.

Table S8: Predicted loads [g] over the whole investigation period of mycotoxins coming from human emission via WWTP and from agricultural areas

cropped with small grain cereals.

total loads [g] WWTP agriculture

DON NIV 3-Ac-DON BEA DON NIV 3-Ac-DON BEA

Glatt catchment

Aabach at Mönchaltorf

(A)

123 ± 47 32 ± 39 51 ± 27

250%

9 ± 1 177 ± 309 106 ± 164 30 ± 27 -

Aa at Niederuster (B) 587 ± 223 154 ± 188 242 ± 128 14 ± 6 282 ± 491 141 ± 217 21 ± 19 -

Glatt at Fällanden (C) 251 ± 96 66 ± 81 104 ± 55 18 ± 3 0.6 ± 0.9 0.4 ± 0.6 0.05 ± 0.04 - Glatt at Oberglatt (D) 839 ± 319 220 ± 268 346 ± 183 60 ± 8 567 ± 986 396 ± 611 84 ± 75 -

Glatt at Rheinsfelden (E) 1366 ± 519 358 ± 437 564 ± 299 98 ± 14 1735 ± 3020 720 ± 1108 154 ± 138 -

Töss catchment

Töss at Rämismühle (F) 79 ± 30 21 ± 26 33 ± 17 6 ± 1 84 ± 146 79 ± 122 9 ± 8 -

Kempt at Winterthur (G) 202 ± 77 53 ± 65 83 ± 44 14 ± 2 168 ± 293 144 ± 222 17 ± 15 -

Eulach at Wülfingen (H) 53 ± 20 14 ± 17 22 ± 12 4 ± 1 409 ± 711 170 ± 261 44 ± 39 -

Töss at Freienstein (I) 1505 ± 572 394 ± 481 621 ± 329 108 ± 15 1231 ± 2143 585 ± 900 231 ± 207 -

Figure S14: Surface waters of the Canton of Zurich with the river Glatt and Töss highlighted in

dark blue. Inserted bar charts show the estimated amounts from WWTP effluents (blue),

and from agricultural areas cropped with winter wheat (green). They are compared to the

total nivalenol load [g] observed (red) at each sampling station over an investigation period

from January 2010 until November 2011.

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mycotoxins in the environment: ii. occurrence and origin

Documents