View
225
Download
0
Category
Preview:
Citation preview
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Analysis of Biomixtures to Determine the Fate of Pesticides
29 th Sept 2015
1Institute of Bio- and Geosciences (IBG-3), Agrosphere Institute, Forschungszentrum Jülich
GmbH, 52425 Jülich, Germany2BASF SE, 67117, Limburgerhof, Germany
3Sustainable Campus, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany
Santanu Mukherjee*1, Lutz Weihermüller1, Wolfgang Tappe1, Diana Hofmann1, Stephan Köppchen1, Volker
Laabs2, Tom Schroeder2, Harry Vereecken1 and Peter Burauel3
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
� Motivation
� Objectives
� Materials and Methods
� Biochar
� Digestate
�14C labelled Pesticides
� Experimental Setup
� Results from Incubation Study
� Results from Degradation Experiment
� Results from Sorption Experiment
� Take Away message
Overview
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Pesticides in water:sources of contamination
Diffuse Point Source
DriftDrain flowSurface flowSeepage Leaching
Tank filling Waste disposal Washings Faulty equipmentSpillages
Motivation
IBG-3 : Agrosphere
• 40,000 t of pesticides applied in Germany between 2006 and 2011(www.umweltbundesamt.de)
• Approx. > 50% of the water pollution due to leaching and mixing of pesticides from the
agriculture practices (Agrawal et al., 2010)
• Point pollution contributes approx. 40-90 % of surface and ground-water contamination
(De Wilde et. al., 2009)
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Pesticides in water:sources of contamination
Diffuse Point Source
DriftDrain flowSurface flowSeepage Leaching
Tank filling Waste disposal Washings Faulty equipmentSpillages
Motivation
IBG-3 : Agrosphere
• 40,000 t pesticides applied in Germany between 2006 and 2011 (www.umweltbundesamt.de)
• Approx. > 50% of the water pollution due to leaching and mixing of pesticides from the
agriculture practices (Agrawal et al., 2010)
• Point pollution contributes approx. 40-90% of surface and ground-water contamination
(De Wilde et al., 2009)
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
• Study the fate of test compounds (Bentazone, Boscalid & Pyrimethanil)
on soils mixed with organic amendments (biochar and digestate)
Objectives
� Results should lead to improved Biofilter systems
1. Analyze the long-term stability of organic mixtures (Chapter 1)
2. Analyze the pesticide degradation behavior (Chapter 2)
3. Analyze the sorption-desorption behavior of pesticide (Chapter 3)
Biobac FranceBiomassbed Italy Biofilter Belgium Biobeds UK
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
• Study the fate of test compounds (Bentazone, Boscalid & Pyrimethanil)
on soils mixed with organic amendments (biochar and digestate)
Objectives
� Results should lead to improved Biofilter systems
Biobac FranceBiomassbed Italy Biofilter Belgium Biobeds UK
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Materials
Soils
Kaldenkirchen Merzenhausen(Silt loam)(Loamy sand)
Amendments
Biochar Digestate
Pesticides
Bentazone BoscalidPyrimethanil(Herbicide) (Fungicide) (Fungicide)
Degradation potential
Leaching potential
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Pesticide Degradation Experiment
� 10 x field application of Bentazone ,
Boscalid and Pyrimethanil.
� ~ 60 % WHCmax
� CO2 trapped by NaOH
� Residue extraction using H2O /
Methanol
Incubator for Degradation Experiment (~ 25 °C)
Methods (Chapter 1)Respiration Experiment
� 2 soils and 13 different biomixtures
� Biomixtures = soil + Biochar + digestate
� Variation in % amendents
� Weekly measurements
Respirometer system
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Respiration Merzenhausen (silt loam)
� Not proportional degradation of C with increasing amount of digestate
� Large reduction after biochar addition
� Larger reduction for LB compared to HB
IBG-3 : Agrosphere
0 10 20 30 40 50 60 70 80 900.0
1.0
2.0
3.0
4.0
5.0
day of incubation
ca
rbo
nd
eg
rad
ed
[%C
]
control
1.0% HTB
2.5% HTB
5.0% HTB
1.0% LTB
2.5% LTB
5.0% LTB
5.0% DG
15.0% DG
30.0% DG
5% DG 1% HTB
5% DG 5% HTB
5% DG 1% LTB
5% DG 5% LTB
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Respiration Kaldenkirchen (loamy sand)
� Not proportional degradation of C with increasing amount of digestate
� Large reduction after biochar addition
� Higher relative degradation compared to MRZ
IBG-3 : Agrosphere
0 10 20 30 40 50 60 70 80 900.0
1.0
2.0
3.0
4.0
5.0
day of incubation
ca
rbo
nd
eg
rad
ed
[%C
]
control
1.0% HTB
2.5% HTB
5.0% HTB
1.0% LTB
2.5% LTB
5.0% LTB
5.0% DG
15.0% DG
30.0% DG
5% DG 1% HTB
5% DG 5% HTB
5% DG 1% LTB
5% DG 5% LTB
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Measurement of Dissolved Organic Carbon (DOC) and Calculation of SUVA
Sample ID Mean DOC (mg L-1) Mean UVA254 nm
(m-1) Mean SUVA
(L mg-1 m-1)
Soil (KK) 12.00 ± 2.40 21.93 ± 2.42 1.85 ± 0.16
Soil (KK) + 30% DG 50.10 ± 6.63 332.00 ± 101. 23 6.80 ± 2.88
Soil (KK) + 30% DG+ 5% Biochar 4.06 ± 0.29 5.65 ± 0.38 1.40 ± 0.08
5.89 ± 3.88 14.80 ± 11. 75 1.52 ± 1.12
Soil (KK) + 5% DG 12.20 ± 1.22 38.24 ± 12.84 3.12 ± 0.90
Soil (KK) + 5% Biochar+ 5% DG 4.13 ± 0.72 9.30 ± 1.78 2.26 ± 0.40
Soil (KK) + 5% Biochar
� 5 g of each and every following biomixtures was extracted with 10 ml 10 mM CaCl2 in horizontal shaker
for 15 min, centrifugation was done at 3210 g for 15 min
� Filtration of the supernatant was done with 0.45 µm polycarbonate filter
� SUVA (L mg-1 m-1) = UVA (cm-1) / DOC (mg L-1) * 100
IBG-3 : Agrosphere
Principle findings :
�Adsorption of DOC from digestate onto biochar surface
� Soil and Digestate mixture released max. amount of DOC
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Large reduction of C degradation when biochar added to soil / digestate mixtures
Principle Finding
Proposed Hypotheses
�Adsorption of DOC onto the biochar surface
�Chances of ammonia toxicity at higher concentration of nitrogen enriched substances
�Chemisorption of CO2 to biochar surface
�Precipitation of CO2 as mineral carbonates
�At a certain threshold, compounds from biochar could potentiallybecome microbiologically toxic
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Pesticide Degradation Experiment
� 10 x field application of Bentazone ,
Boscalid and Pyrimethanil.
� ~ 60 % WHCmax
� CO2 trapped by NaOH
� Residue extraction using H2O /
Methanol
Incubator for Degradation Experiment (~ 25 °C)
Methods (Chapter 2)Respiration Experiment
� 2 soils and 13 different biomixtures
� Biomixtures = soil + biochar + digestate
� Variation in % amendents
� Weekly measurements
Respirometer system
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
� Highest mineralization in case of 30% DG followed by 30% DG and 5% biochar
� Lowest mineralization in case of soil and 5% biochar
� Mineralization not proportional to DG concentration
� Addition of digestate enhanced bentazone mineralization (~20%) compared to blank soil
Bentazone Mineralization (Kaldenkirchen)
Application Rate :12.80 mg kg-1 mixture
IBG-3 : Agrosphere
day of incubation
% M
ine
rali
zati
on
%
Min
era
liza
tio
n
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Pyrimethanil Mineralization (Kaldenkirchen)
Application Rate :10.67 mg kg-1 mixture
� Highest mineralization in case of 30% DG followed by 30% DG and 5% biochar
� Lowest mineralization in case of soil and 5% biochar� Mineralization not proportional to DG concentration
� Digestate enhanced pyrimethanil mineralization (~400%) compared to bare soil
IBG-3 : Agrosphere
day of incubation
% M
ine
rali
zati
on
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Boscalid Mineralization (Kaldenkirchen)
Application Rate :1.33 mg kg-1 mixture
� Highest mineralization in case of 30% DG followed by 30 % DG and 5 % biochar
� Lowest mineralization in case of soil and 5% biochar
� Mineralization not proportional to DG concentration
� Addition of digestate enhanced mineralization (~32%) compared to blank soil
IBG-3 : Agrosphere
% M
ine
rali
zati
on
day of incubation
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
% of applied radioactivity after 120 days of incubation
IBG-3 : Agrosphere
13%
49%
38%
reference soil
18%9%
73%
5% DG + 5% BC
4%
50%
46%
6% 2%
92%
2%
59%
39%
Bentazone
Boscalid
Pyrimethanil
2% 3%
95%
Mineralized
Extracted
Non-extracted
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
�Digestate blending with char exerted a positive effect on the mineralization rates for all pesticides
�Pesticide mineralization was not proportional to the amount of added digestate
�A 40 days of lag phase observed for pyrimethanil
Principle Findings
Proposed Hypotheses�Biochar can act as a good habitat for soil microbes
�Water extractable DOC quantity is not proportional to the digestate content
�Adaptation time needed for the microbial community
�Biochar acts as a sorbent to pesticides
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
IBG-3 : Agrosphere
96 hrs 168 hrs
Soil : Solution ratios and Equilibrium time (hr) : Soil (KK)
Bentazone Bentazone
Boscalid Boscalid
Pyrimethanil
Methods (Chapter 3)
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
IBG-3 : Agrosphere
Soil : Solution ratios and Equilibrium time (hr) : Soil (KK) + 30% DG+ 5% Char
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Soil Soil + 5% DG
Soil + 30% DG Soil + 5% DG + 5 % BC
Soil + 30% DG + 5% BC
Bentazone sorption-desorption
(Kaldenkirchen)
IBG-3 : Agrosphere
� Higher KOC and Kd values for biochar
and digestate based mixtures
� 1/nf <1
� 30% DG showed higher sorption
affinity than reference soil and 5%
DG mixture (higher KL and Smax
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Soil + 5% DG
Soil + 5% DG + 5 % BC
Soil + 30% DG + 5% BC
Boscalid sorption-desorption
(Kaldenkirchen)
Soil
Soil + 30 % DG
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Soil Soil + 5% DG
Soil + 5% DG + 5 % BC
Soil + 30% DG + 5% BC
Pyrimethanil sorption-desorption
(Kaldenkirchen)
Soil + 30% DG
IBG-3 : Agrosphere
� Higher KOC and Kd, Kf and KL values for
biochar and digestate based mixtures.
� 1/nf <1
� Kfdes < Kfads
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
�Kd and KOC values were higher for hydrophobic pesticides
�L-type sorption isotherms observed mostly for all soil and digestate based mixtures (1/nf <1) and C-type (1/nf ~1) for biochar and digestate based mixtuIn general, 1/nfdes << 1/nfads observed.
�Lower DOC content of biochar and digestate mixture enhanced sorption
Principle Findings
Proposed Hypotheses�Higher organic C content attributed to the enhanced sorption
�Water extractable DOC competes for the sorption sites
�Highest lignin content of 30% DG mixture enhanced bentazone and pyrimethanil sorption
�Stronger retention lead to difficulties in desorption of hydrophobic pesticide
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
�C degradation is not proportional to the input of the digestate
(in respiration study)
�Biochar reduces C degradation from soil/digestate mixture (in
respiration study)
�Mixture of biochar & digestate = highest pesticide
mineralization
�Biochar adddition reduces pesticide mineralization
�Biochar showed largest NE residues followed by mixture of
char & digestate
�Stronger retention of the hydrophobic pesticides observed in
the biomixtures
Take away message
� Mixture of char & digestate most appropriate (5% DG and 5% BC) IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
IBG-3 : Agrosphere
Publications�Mukherjee, S., Weihermueller, L., Tappe, W., Vereecken, H., Burauel, P., 2015. Microbial respiration of biochar and digestate based mixtures. Biology and Fertility of Soils (Published)- Chapter 1
�Mukherjee, S., Tappe, W., Weihermueller, L., Hofmann, D., Köppchen, S., Laabs, V., Schroeder, T., Vereecken, H., Burauel, P., 2015. Dissipation of contrasting pesticides in biochar and digestate based soil mixtures for biopurification systems. Science of the total Environment (Submitted)-Chapter 2
�Mukherjee, S., Weihermueller, L., Tappe, W., Hofmann, D., Köppchen, S., Laabs, V., Schroeder, T., Vereecken, H., Burauel, P., 2015. Sorption-desorption behaviour of Pesticides in biochar and digestate based soil mixtures for biopurification systems (under preparation) - Chapter 3
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Acknowledgements
Ulrich Disko
Sirgit Kummer
Martina Krause
Andrea Kubica
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Degradation Experiment Set up :
Field rate of application of Bentazone : 960 g/ha
Rate of application in Experiment : 12.80 µg/g soil mixtures
(B.D = 1.5 g/cm3 , Soil layer = top 1 cm )
Thermostat Incubator for Degradation Set up ( Temp. ~ 25 °C)
Water content of biomixture ~ 60 % of WHC max.
Total Applied Radioactivity/3.15 kg biomixture : 1.52 MBq ± 0.04
Evolution of 14 CO2 as a product of mineralization is measured by 1.5 ml 2 M NaOH
solution .
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Some features of Test Substances proposed for Degradation Study :
Characters Bentazone Boscalid Pyrimethanil
Type Herbicide Fungicide Fungicide
Chemical Group Benzothiazone Carboxamide Anilopyrimidine
Water Solubility
(mg/L)
570 4.6 121
Principle metabolite n-methyl bentazone NA 2-amino-4,6-methyl
pyrimidine
Proposed
pesticide/soil
mixture (mg/100g
dry mass basis )
1.28 0.133 1.067
Proposed
radioactivity (kBq)
46.85 6.66 224.7
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Some useful informations about Sorbents:
Materials Soil 1 Soil 2 BC400 BC 800 Digestate
Source /place and texture Kaldenkirchen (loamy sand)
Merzenhausen (silty loam)
Woodchips§ Woodchips§§ Maize-silage, Chicken manure and Beef waste
pH 5.7* 7.0* n.d n.d n.d
CEC(cmolc kg-1) 7.8* 11.4* n.d n.d n.d
COC (%) 1.07* 1.24* 75.9§ 74.4§§ 40
H
_ _
1.64§ 0.5§§
_
O
_ _
5.05§ 10.6§§
_
H/C Atomic Ratio
_ _
0.26 0.08
_
O/C Atomic Ratio
_ _
0.05 0.11
_
Surface Area (N2) (m2/g) n.d n.d 231 225 3.09
Surface Area (CO2) (m2/g) n.d n.d 634 625 37.90
Micropore volume (cc/g)
_ _
0.22 0.21 0.01
*(Kasteel et. al. , 2010), §(Carbon Terra, 2011) and §§(Pyreg, 2011)
IBG-3 : Agrosphere
Mitglie
d d
er
Helm
holtz-G
em
ein
schaft
Digestate : Solid material remaining after the anaerobic digestion of a biodegradable
feedstock.
Fiber: Solid fraction of digestate with low nutrients
- used as soil conditioner
(http://en.planet-biogas.de)
Approx. Elemental Composition On Dry Matter Basis
(g/kg )
* Wheat Straw *Solid Digestate
Organic C 429 404
Total N 5.6 93
Lignin 177 200
C/N 76.6 4.34
Selected characteristics of the Straw and Digestate:
*(Tambone et. al., 2009)
IBG-3 : Agrosphere
Recommended