investigation of sorption of environmental … · blank values (sorp. on glass etc.) • 2-3...
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INVESTIGATION OF SORPTION OF
ENVIRONMENTAL POLLUTANTS TO VIRGIN
AND AGED MICROPLASTIC
Caroline Goedecke, Ulrike Mülow-Stollin, Selina Hering, Janine Richter,
Christian Piechotta, Andrea Paul, Ulrike Braun
19.06.2017
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Motivation
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19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
• increasing plastic consumption, plastic products in our environment
worldwide
• plastic fragments < 5 mm = Microplastics (MP)
• unknown sorption effects of environmental pollutants on microplastics
choice of proper materials to simulate natural occuring MP
extensive characterization of the materials
Creation of realistic sorption scenarios with relevant parameters
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Identification of relevant polymer types
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19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
detection of polymers in a sewage effluent analytical method:
TED-GC-MS
screening for: PS, PP, PE, PET, PA
PP, PS, PE are of environmental relevance
Sampling by M. Ricking, C.G. Bannick, German Environment Agency
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TED-GC-MS
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19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
ThermalExtractionDesorption-GC-MS
• identification via decomposition products
• fast analysis
• little to no sample cleanup
• large amount of sample
sample
Dr. Erik Dümichen
Paul Eisentraut
E. Dümichen, Fast identification of microplastics in complex environmental samples by a thermal degradation method, 2017, Chemosphere, 174, 572–584.
SPE
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Selection of the sorption materials
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19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
source sampling analytics Identified polymer
species
Gregory 1978 Pacific Ocean (NZ) FTIR PE, PP
Thompson 2004
Atlantic Ocean (UK) FTIR-microscope
PE, PP, PA, PES, Acryl
Reddy 2006 Indian Ocean (Ind) FTIR PU, PA, PS, PES
Frias 2010 Atlantic Ocean (P) FTIR-microscope PS, PE, PP
Browne 2011 various FTIR PES, PP, PE, PA, Acryl
Claessens 2011
Atlantic Ocean/ North Sea (B)
FTIR PS, PP, PA, PE, PVAL
Hirai 2011 Pacific Ocean NIR PE, PP
Murray 2011 Atlantic Ocean (UK) RAMAN PE, PP
Imhof 2013 Lake Garda (I) RAMAN PE, PP, PS, PVC, PA
Nor 2014 Singapore FTIR PP, PVC, PA
Lusher 2014 North East Atlantic Ocean
RAMAN Viscose, PES, PA
literature confirmed foundings
density below water: PE, PP
close to water: PS
above water: PA, PET, PVC
PP, PS,
PA instead of PE
detected polymers in sewage
effluent: PP, PE, PS
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Selection of the analyte-triacole fungicides
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pKa 1.07 logP 4.36 water solubility 15 mg L-1 analysis GC-MS
19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
• one of the most used organic fungicides (market share 20 %)
• chiral
• non-polar
• percieved as persistent in soil
Difenoconazole Specification
Investigation of sorption of difenoconazole on PP, PS and PA
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Sorption experiments of difenoconazole
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pH salinity agitation
a 6 0.1 % 0 min-1
b 6 0.1 % 240 min-1
c 8 0.1 % 0 min-1
d 8 0.1 % 240 min-1
e 6 3.5 % 0 min-1
f 6 3.5 % 240 min-1
g 8 3.5 % 0 min-1
h 8 3.5 % 240 min-1
• full factorial design
• 1 g MP, V=50 mL, c=0.02 mg L-1
• adsorption time 24 h
• sorption has been corrected with
blank values (Sorp. on glass etc.)
• 2-3 replicates per point
• quantification of difenoconazole via
GC-MS
19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
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Adsorption of Difenoconazole on virgin MP
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PA PP PS
high effect of agitation
pH and salinity of minor importance
highest adsorption on PS
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Simulation of aging processes
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cryo-milling of PP
enlargement of the surface:
factor 5-14
particle size distribution
environmental relevance
of the sizes
1 10 100 1000 10000 1000000
5
10
15
20
25
30
cu
mu
lative d
istr
ibu
tio
n/
%
particle size/µm
0
10
20
30
40
50
60
70
80
90
100
de
nsity d
istr
ibu
tio
n/%
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Influence of particle size
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virgin PP milled PP
smaller particle size leads to higher sorption effects (factor of ~4)
minor effect of pH and salinity
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• high shape inhomogenity
after milling
• spheric & non-spheric particles)
• low Tglass of PP (0-20 °C)
Characterization of the particles
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200 µm
• both particle size and shape
affect sorption behaviour
Photomicrograph of milled PP
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Simulation of aging processes
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12 % HCl,
20 % acetone
virgin PA PA flakes after
treatment
• PA easy to age through breaking of polymer chains
• aging by UV-radiation time consuming
simulation via chemical treatment
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Results of sorption on aged PA
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virgin PA
aging leads to higher sorption effects (factor of ~3)
small effects of pH and salinity
acid treated PA
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Characterization of PA6
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103
104
105
106
0,0
0,2
0,4
0,6
0,8
1,0
1,2
acid treated PA6
virgin PA6
W(l
og
M)
molar mass/g mol-1
19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
comparison of virgin PA & acid treated PA6
reduction of molar mass melting peak changed crystal
morphology
more sorption, but effect less significant than particle size
150 200 250
-1,5
-1,0
-0,5
DS
C/m
W m
g-1
temperature/°C
acid treated PA6
virgin PA6
221 °C 218 °C
GPC-elugrams DSC
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Results of ANOVA
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design „treatment“ • milling of PP:
strongest effect
• acid treatment on PS and PA-acid: similar
results of ANOVA confirm results of graphic evaluation
19.06.2017 Investigation of sorption of environmental pollutants to virgin and aged microplastics
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Summary
• sorption of difenoconazole on all selected polymers
• effects of pH, salinity and agitation were evaluated by factorial design
• strongest effect of agitation, whereas pH and salinity are negligible
• relevant: choice of polymer type and characteristics:
• amorphous PS sorbs stronger than semi - crystalline PP and PA
• small PP particles sorb more difenoconazole than granulate - but difficult
to characterize in model experiments
• aged PA sorbs more than fresh, because of changed material
morphology and possible increased absorption
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Acknowledgement
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• Erik Dümichen
• Jana Falkenhagen
• Axel Müller
• Luba Korup
• Korinna Altmann
• Paul Eisentraut
• Heidi Marx
Thanks to BMBF-Project for finance
Parts of this presentation are already published:
Goedecke C, Mülow-Stollin U, Hering S, Richter J, Piechotta C, et al. (2017) A First Pilot Study on the
Sorption of Environmental Pollutants on Various Microplastic Materials. J Environ Anal Chem 4: 191.
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18
Thank you all for your attention!