Supporting Information

Year-round behaviour of soil microarthropod communities under plant protection product application

Ecotoxicology

Claudia Vaj1a, Cornelis AM Van Gestel2, Marco Vighi1*

1) Department of Environmental Sciences

University of Milano Bicocca

Piazza della Scienza, 1

20126 Milano

Italy

2)  Department of Ecological Science
Faculty of Earth and Life Sciences
VU University
De Boelelaan, 1085
1081 HV Amsterdam
The Netherlands

a) Present address: Dow AgroSciences Italia s.r.l., Viale A. Masini 36, 40126, Bologna, Italy.

* corresponding author:

Phone: +39 02 6448 2741

Fax: +39 02 6448 2795

e-mail:


SI.1 Procedure for estimating soil moisture content at the sampling dates from June 2008 and September 2008

For the sampling dates from June 2008 and September 2008 soil moisture content was estimated using the empirical equation derived from the USDA texture triangle (Soil Survey Division Staff 1993). Eq. SI.1 calculates moisture equivalent, assumed nearly equal to field capacity, using sand, silt and clay percentages.

(SI.1)

where:

ME (%) is moisture equivalent (the value is converted in g/kg for further analysis);

Sa (%) is sand (2-0.05 mm) content;

Si (%) is silt (0.05-0.002 mm) content;

Cl (%) is clay (<0.002 mm) content.

ME values were calculated for the three sampling stations using eq. SI.1: 344 g/kg for point A, 268 g/kg for point B and 232 g/kg for point C.

Through direct observations in the field and expert judgment, for each sampling date the ratio with the field capacity was assessed (%). Then the soil moisture content (g/kg) was estimated from the ratio percentage.

For example, on the sampling date June 2008 the soil was fairly dry and the ratio with the moisture equivalent was estimated as 27% of the calculated moisture equivalent of the three sampling points. This calculation was made for JulyI (dry, 25%), July II (very dry, 23%) and September (moist, 60%).

The same procedure was followed for a reference field situation (December 2008 sampling, under rain, wet soil) and the result was compared with the laboratory analyses. The difference between estimated and measured values never exceeded 20%.


Table SI.1 Rainfall measured from April 2008 to June 2009 by the meteorological station located in San Biagio di Callalta (TV, Veneto region, North-East Italy), close to the study vineyard sampled for studying the behaviour of the soil microarthropod communities under plant protection product applications (See Fig. 1). Bold: two irrigation events occurred on Pinot Grigio plants.

Date / Rain (mm) / Date / Rain (mm) / Date / Rain (mm) / Date / Rain (mm)
5-Apr-08 / 0.2 / 7-Jul-08 / 0.8 / 30-Nov-08 / 22 / 28-Mar-09 / 5.0
6-Apr-08 / 0.8 / 13-Jul-08 / 2.0 / 1-Dec-08 / 8.8 / 29-Mar-09 / 83
9-Apr-08 / 0.2 / 14-Jul-08 / 17.8 / 2-Dec-08 / 1.6 / 30-Mar-09 / 3.2
10-Apr-08 / 2.8 / 17-Jul-08 / 0.4 / 5-Dec-08 / 19.8 / 31-Mar-09 / 3.0
11-Apr-08 / 6.0 / 18-Jul-08 / 2.4 / 9-Dec-08 / 0.2 / 1-Apr-09 / 2.4
12-Apr-08 / 3.8 / 22-Jul-08 / 0.8 / 10-Dec-08 / 30.8 / 2-Apr-09 / 10.2
13-Apr-08 / 0.2 / 28-Jul-08 / 2.2 / 11-Dec-08 / 8.2 / 5-Apr-09 / 1.4
15-Apr-08 / 1.2 / 31-Jul-08 / 30.0 / 12-Dec-08 / 6.0 / 16-Apr-09 / 2.2
16-Apr-08 / 0.8 / 8-Aug-08 / 13.4 / 13-Dec-08 / 3.0 / 17-Apr-09 / 0.4
18-Apr-08 / 6.8 / 15-Aug-08 / 2.4 / 14-Dec-08 / 5.8 / 19-Apr-09 / 2.2
19-Apr-08 / 4.6 / 16-Aug-08 / 13.6 / 15-Dec-08 / 18.8 / 20-Apr-09 / 5.8
21-Apr-08 / 11.4 / 23-Aug-08 / 6.8 / 16-Dec-08 / 20.8 / 21-Apr-09 / 1.0
22-Apr-08 / 0.4 / 24-Aug-08 / 0.4 / 25-Dec-08 / 1.8 / 23-Apr-09 / 2.2
25-Apr-08 / 3.0 / 2-Sep-08 / 1.2 / 1-Jan-09 / 14.4 / 26-Apr-09 / 4.4
29-Apr-08 / 0.2 / 4-Sep-08 / 12.2 / 2-Jan-09 / 0.4 / 27-Apr-09 / 13.2
3-May-08 / 0.4 / 5-Sep-08 / 7.0 / 14-Jan-09 / 9.8 / 28-Apr-09 / 31
4-May-08 / 2.4 / 7-Sep-08 / 5.4 / 15-Jan-09 / 5.2 / 29-Apr-09 / 8.8
5-May-08 / 6.2 / 12-Sep-08 / 5.0 / 18-Jan-09 / 0.8 / 4-May-09 / 3.8
15-May-08 / 3.4 / 13-Sep-08 / 34.0 / 19-Jan-09 / 3.8 / 5-May-09 / 7.6
18-May-08 / 49.2 / 14-Sep-08 / 0.6 / 20-Jan-09 / 21.2 / 24-May-09 / 1.0
19-May-08 / 0.4 / 20-Sep-08 / 10.0 / 21-Jan-09 / 17.6 / 27-May-09 / 20.6
20-May-08 / 1.2 / 28-Oct-08 / 3.2 / 22-Jan-09 / 1.4 / 5-Jun-09 / 0.2
23-May-08 / 12.2 / 29-Oct-08 / 15.8 / 23-Jan-09 / 4.0 / 6-Jun-09 / 1.6
25-May-08 / 1.0 / 30-Oct-08 / 6.8 / 26-Jan-09 / 3.6 / 7-Jun-09 / 7.8
4-Jun-08 / 16.0 / 31-Oct-08 / 7.2 / 27-Jan-09 / 12.2 / 8-Jun-09 / 0.2
5-Jun-08 / 26.8 / 1-Nov-08 / 1.2 / 28-Jan-09 / 0.4 / 9-Jun-09 / 0.2
6-Jun-08 / 0.8 / 3-Nov-08 / 0.8 / 1-Feb-09 / 2.8 / 15-Jun-09 / 4.0
7-Jun-08 / 0.6 / 4-Nov-08 / 12.8 / 2-Feb-09 / 22.4 / 20-Jun-09 / 19.8
11-Jun-08 / 7.0 / 6-Nov-08 / 2.0 / 3-Feb-09 / 10.4 / 23-Jun-09 / 0.2
12-Jun-08 / 0.4 / 7-Nov-08 / 1.8 / 6-Feb-09 / 5.0 / 24-Jun-09 / 4.4
14-Jun-08 / 4.0 / 12-Nov-08 / 2.6 / 7-Feb-09 / 20 / 25-Jun-09 / 5.0
17-Jun-08 / 7.6 / 13-Nov-08 / 46.8 / 8-Feb-09 / 0.6 / 26-Jun-09 / 0.2
18-Jun-08 / 15.2 / 14-Nov-08 / 0.6 / 3-Mar-09 / 2.6 / 27-Jun-09 / 49.6
1-Jul-08 / 0.8 / 24-Nov-08 / 3.8 / 4-Mar-09 / 58 / 28-Jun-09 / 1.4
2-Jul-08 / 0.4 / 28-Nov-08 / 10.4 / 5-Mar-09 / 17.4 / 29-Jun-09 / 0.2
6-Jul-08 / 0.6 / 29-Nov-08 / 4.0 / 6-Mar-09 / 1.6


Table SI.2 Active ingredients applied in the vineyard in the Veneto region (North-East Italy) sampled for studying the behaviour of the soil microarthropod communities under plant protection product applications (in italics those applied only on the Pinot Grigio variety), see Fig. 1. Also given are application dates and rates. A: action; H: herbicide, F: fungicide, I: insecticide.

Date / A / Active ingredient / Application rate (kg/ha) / Date / A / Active ingredient / Application rate (kg/ha)
28-Apr-08 / F / mancozeb / 2.25 / 15-Jul-08 / F / Cu oxychloride / 1.4
28-Apr-08 / F / sulfur / 3.2 / 15-Jul-08 / I / chlorpyrifos / 0.45
5-May-08 / F / sulfur / 3.2 / 22-Jul-08 / F / Cu sulphate / 0.65
5-May-08 / F / mancozeb / 2.25 / 22-Jul-08 / F / sulfur / 6.0
14-May-08 / F / mancozeb / 2.25 / 30-Jul-08 / F / Cu sulphate / 0.65
14-May-08 / F / sulfur / 3.2 / 30-Jul-08 / F / sulfur / 6.0
19-May-08 / F / sulfur / 3.2 / 5-Aug-08 / F / mepanipyrim / 0.5
19-May-08 / F / mancozeb / 2.25 / 5-Aug-08 / H / glyphosate / 0.889
19-May-08 / F / dimethomorph / 0.25 / 5-Aug-08 / F / Cu oxychloride / 1.125
20-May-08 / H / glyphosate / 0.72 / 5-Aug-08 / F / sulfur / 4.8
20-May-08 / H / oxadiazon / 0.74 / 11-Aug-08 / F / Cu sulphate / 0.488
24-May-08 / F / dimethomorph / 0.25 / 11-Aug-08 / F / sulfur / 4.0
24-May-08 / F / folpet / 1.6 / 15-Apr-09 / F / folpet / 1.2
24-May-08 / F / mancozeb / 1.5 / 15-Apr-09 / F / sulfur / 2.4
24-May-08 / F / sulfur / 4.0 / 20-Apr-09 / H / glyphosate / 0.72
27-May-08 / F / sulfur / 4.0 / 25-Apr-09 / F / folpet / 1.0
27-May-08 / F / folpet / 2.0 / 25-Apr-09 / F / sulfur / 2.4
2-Jun-08 / F / folpet / 4.0 / 2-May-09 / F / sulfur / 2.4
2-Jun-08 / F / dimethomorph / 0.25 / 2-May-09 / F / folpet / 1.0
2-Jun-08 / F / sulfur / 4.8 / 10-May-09 / F / folpet / 1.0
8-Jun-08 / F / mancozeb / 2.25 / 10-May-09 / F / sulfur / 3.2
8-Jun-08 / F / folpet / 1.6 / 16-May-09 / F / sulfur / 3.2
8-Jun-08 / F / sulfur / 4.0 / 16-May-09 / F / folpet / 0.8
14-Jun-08 / F / sulfur / 4.0 / 22-May-09 / F / folpet / 0.8
14-Jun-08 / F / folpet / 1.6 / 22-May-09 / F / sulfur / 3.2
14-Jun-08 / F / mancozeb / 1.5 / 29-May-09 / F / sulfur / 4.0
14-Jun-08 / F / iprovalicarb / 0.15 / 29-May-09 / F / folpet / 0.96
17-Jun-08 / F / cyprodinil / 0.375 / 7-Jun-09 / F / folpet / 1.2
17-Jun-08 / F / fludioxonil / 0.25 / 7-Jun-09 / F / sulfur / 4.4
20-Jun-08 / F / mancozeb / 2.25 / 7-Jun-09 / F / thiophanate-metyla / 0.45
20-Jun-08 / F / sulfur / 4.0 / 12-Jun-09 / F / cyprodinil / 0.375
23-Jun-08 / H / glyphosate / 0.72 / 12-Jun-09 / F / fludioxonil / 0.25
27-Jun-08 / F / sulfur / 4.8 / 12-Jun-09 / F / folpet / 1.029
27-Jun-08 / F / dimethomorph / 0.25 / 12-Jun-09 / F / Cu oxychloride / 0.6125
27-Jun-08 / I / thiamethoxam / 0.05 / 12-Jun-09 / F / sulfur / 4.4
27-Jun-08 / F / Cu oxychloride / 1.05 / 14-Jun-09 / H / glyphosate / 0.72
5-Jul-08 / F / Cu oxychloride / 1.225 / 22-Jun-09 / I / thiamethoxam / 0.05
5-Jul-08 / F / sulfur / 4.8 / 22-Jun-09 / F / Cu oxychloride / 1.125
15-Jul-08 / F / sulfur / 4.8 / 22-Jun-09 / F / sulfur / 4.8

a Partly degrades in soil into carbendazim.


Table SI.3 Physical-chemical properties and half-lives (DT50) of plant production products (PPPs) used for soil exposure assessment in the vineyard in the Veneto region (North-East Italy) sampled for studying the behaviour of the soil microarthropod communities under PPP applications (- = no data available). Where more than one value was available in the literature, the most conservative field value was chosen. MW: molecular weight, S: solubility in water, VP: vapour pressure; H: herbicide, F: fungicide, I: insecticide.

Active Ingredient / Action / MW / S (g/m3) / VP (Pa) / Log KOW / DT50 soil (d) / DT50 photo-degradation (d)
carbendazim / F / 191.2a / 8a / 1.50E-04a / 1.51a / 10b / -
chlorpyrifos / I / 350.6a / 1.4a / 2.70E-03a / 5.261c / 70c / 5d
cyprodinil / F / 225.3a / 13a / 5.10E-04b / 4.00c / 40c / 0.24e
dimethomorph / F / 387.9a / 49.2a / 9.85E-07b / 2.63c / 44c / -
fludioxonil / F / 248.2a / 1.8a / 3.90E-07a / 4.12c / 18b / 0.125e
folpet / F / 296.6a / 0.8a / 2.10E-05a / 3.63c / 4.3c / -
glyphosate / H / 169.1a / 10500a / 1.31E-05a / -3.20b / 60c / -
iprovalicarb / F / 320.4a / 8.9a / 7.70E-08a / 3.20a / 15.5b / 62f
mancozeb / F / 271.3a / 6.2a / 1.30E-05b / 0.26a / 0.5c
mepanipyrim / F / 222.3a / 3.1a / 2.32E-05a / 3.28a / 57b / -
oxadiazon / H / 345.2a / 1a / 1.00E-04a / 4.91a / 151b / -
thiophanate-methyl / F / 342.4a / 20a / 9.50E-06a / 1.50a / 5b / -
thiamethoxam / I / 291.7a / 4100a / 6.60E-09a / -0.13a / 39b / 10000g
copper oxychloride / F / 427.1a / 1.19b / 1.00E-08b / - / 10000b* / -
copper sulphate / F / 249.7a / 230500a / 3.40E-13b / - / 1600b* / -
sulphur / F / 32.1a / 0.063b / 9.80E-05b / - / 30b / -

a Tomlin (2003); b FOOTPRINT (2006); c Verro et al. (2009); d Calliera et al. (2008); e Garau et al. 2002; f EC (2002), g EC (2006)

*Copper does not degrade; DT50 values for copper sulphate and copper oxychloride were only used to construct curves that mimic their environmental fate in soil in this case study.

16

Table SI.4 Time Weighted Average (TWA) soil concentrations of the plant protection products (PPPs) applied in the vineyard in the Veneto region (North-East Italy) sampled for studying the behaviour of the soil microarthropod communities under PPP applications. TWA concentrations were calculated for each point in the time period of 14 days before each sampling date (na: not applied before the sampling date; nd: not drifted; neg: negligible value, <0.0001 mg/kg soil).

TWA 14 d 10 cm (mg/kg soil) / JUNE08 / JULYI
A / B / C / A / B / C
mancozeb / 0.22 / 0.0094 / 0.0042 / 0.17 / neg / Neg
sulfur / 17 / 0.96 / 0.43 / 18 / 1.1 / 0.48
dimethomorph / 0.75 / 0.025 / 0.011 / 0.69 / 0.028 / 0.012
glyphosate / 1.2 / nd / nd / 1.3 / nd / Nd
oxadiazon / 0.86 / nd / nd / 0.78 / nd / Nd
folpet / 2.1 / 0.076 / 0.034 / 0.23 / 0.0032 / 0.0014
iprovalicarb / 0.080 / 0.0029 / 0.0013 / 0.057 / 0.0024 / 0.0011
cyprodinil / 0.16 / 0.0084 / na / 0.18 / 0.012 / Na
fludioxonil / 0.10 / 0.0052 / na / 0.073 / 0.0052 / Na
thiamethoxam / na / na / na / 0.046 / 0.0019 / 0.00086
copper oxychloride / na / na / na / 1.7 / 0.11 / 0.049
chlorpyrifos / na / na / na / na / na / Na
copper sulphate / na / na / na / na / na / Na
mepanipyrim / na / na / na / na / na / na
thiophanate-methyl / na / na / na / na / na / na
carbendazim / na / na / na / na / na / na
TWA 14 d 10 cm (mg/kg soil) / JULYII / SEPT
A / B / C / A / B / C
mancozeb / 0.0029 / neg / neg / neg / neg / neg
sulfur / 19 / 1.1 / 0.50 / 15 / 0.72 / 0.32
dimethomorph / 0.65 / 0.022 / 0.099 / 0.31 / 0.010 / 0.0046
glyphosate / 1.1 / nd / nd / 1.4 / nd / nd
oxadiazon / 0.73 / nd / nd / 0.58 / nd / nd
folpet / 0.24 / 0.00034 / 0.00015 / 0.062 / neg / neg
iprovalicarb / 0.043 / 0.0013 / 0.00057 / 0.0068 / 0.00014 / neg
cyprodinil / 0.14 / 0.0096 / na / 0.059 / 0.0041 / na
fludioxonil / 0.042 / 0.0031 / na / 0.0064 / 0.00046 / na
thiamethoxam / 0.046 / 0.0015 / 0.00067 / 0.019 / 0.00063 / 0.00028
copper oxychloride / 3.0 / 0.17 / 0.077 / 5.7 / 0.23 / 0.10
chlorpyrifos / 0.28 / 0.020 / 0.0088 / 0.18 / 0.012 / 0.0054
copper sulphate / 0.51 / 0.015 / 0.0068 / 2.3 / 0.083 / 0.037
mepanipyrim / na / na / na / 0.39 / 0.015 / na
thiophanate-methyl / na / na / na / na / na / na
carbendazim / na / na / na / na / na / na

Table SI.4. Continued

TWA 14 d 10 cm (mg/kg soil) / DEC / APR
A / B / C / A / B / C
mancozeb / neg / neg / neg / neg / neg / neg
sulfur / 2.7 / 0.12 / 0.054 / 0.15 / 0.0064 / 0.0029
dimethomorph / neg / neg / neg / neg / neg / neg
glyphosate / 0.58 / nd / nd / 0.13 / nd / nd
oxadiazon / neg / nd / nd / neg / nd / nd
folpet / neg / neg / neg / neg / neg / neg
iprovalicarb / neg / neg / neg / neg / neg / neg
cyprodinil / neg / neg / na / neg / neg / na
fludioxonil / neg / neg / na / neg / neg / na
thiamethoxam / neg / neg / neg / neg / neg / neg
copper oxychloride / 5.98 / 0.23 / 0.10 / 5.9 / 0.22 / 0.099
chlorpyrifos / 0.021 / 0.0014 / 0.00064 / neg / neg / neg