Passive & High-Volume Atmospheric Samplers:A Comparison of Sampling Rates for Currently-Used Pesticides
Jason Slobodian, Don Waite & Tom HarnerEnvironment Canada, Science & Technology BranchAir Quality Research Division
Allan CessnaAgriculture and Agri-Food Canada, Research Branch Environmental Health
Ludo TuduriUniversité Bordeaux ILaboratoire de Physico-toxicochimie des systèmes naturels
Jim Sproull & Diana ChauEnvironment Canada, Science & Technology BranchPrairie and Northern Laboratory
Agriculture on the PrairiesArea Seeded to Major Crops 2005(Grains, Oilseed and Pulse Crops)
Saskatchewan14.30 Mha
52.5%
Manitoba 3.26 Mha
12.0%Other
Provinces 3.08 Mha
11.3%
Alberta 6.59 Mha
24.2%Sources:
Alberta Agriculture, Food and Rural Development
Saskatchewan Agriculture and Food
Manitoba Agriculture, Food and Rural Initiatives
Pesticide Use on the PrairiesEstimated Annual Usage
Pesticide RankQuantity Used
in Canada(kg)
% Used inAlberta &Manitoba
Glyphosate 1 4.61×106 69%
MCPA 3 1.54×106 87%
2,4-D 4 1.49×106 92%
Saskatchewan, the largest pesticide user is Canada with 36% of sales, is not included
Source: Brimble et al. 2005, Pesticide utilization in Canada: A compilation of current sales and use data
PrairiePrairie & Northern Canada Atmospheric Network (PANCAN)
Current-Use PesticidesPre-emergent Herbicides
EthalfluralinTrifluralin
Triallate
Current-Use PesticidesPost-emergent Herbicides
BromoxynilDicamba
2,4-DMCPA
Current-Use PesticidesAmerican Herbicides
Alachlor AtrazineMetolachlor
Lindane(γ-HCH)
Insecticide
High-Volume Sampling
High-Volume SamplingTriallate 2005
0.00
1.00
2.00
3.00
4.00
5.00
6.00
18-M
ay-05
25-M
ay-05
1-Jun
-058-J
un-05
15-Ju
n-05
22-Ju
n-05
29-Ju
n-05
6-Jul-
0513
-Jul-0
520
-Jul-0
527
-Jul-0
53-A
ug-05
Con
cent
ratio
n (n
g/m
3 )
Bratt's Lake 1 mBratt's Lake 10 mBratt's Lake 30 mHaffordWaskesiu
High-Volume SamplingBromoxynil 2005
0.00
1.00
2.00
3.00
4.00
5.00
6.00
18-M
ay-05
25-M
ay-05
1-Jun
-058-J
un-05
15-Ju
n-05
22-Ju
n-05
29-Ju
n-05
6-Jul-
0513
-Jul-0
520
-Jul-0
527
-Jul-0
53-A
ug-05
Con
cent
ratio
n (n
g/m
3 )
Bratt's Lake 1 mBratt's Lake 10 mBratt's Lake 30 mHaffordWaskesiu
Passive Sampling?
Passive Sampling
Passive SamplingAdsorption Curve
Time
Qua
ntity
on
PUF
Linear
Curvilinear Equilibrium Partitioning
Laboratory Analysis of Samples
• Analysis was conducted by Environment Canada’s Prairie and Northern Laboratory in Edmonton
• Samples were:– Treated with 2,4-D d5– Soxhlet extracted– Concentrated– Methylated with diazomethane– Analyzed by GC/MS/MS
• For high-volume samples, the glass fibre-filter and PUF/XAD2 cartridge were simultaneously analyzed
% Detection of Pesticides in Passive SamplesRelative to High-Volume Samples
where the atmospheric concentration > 0.05 ng/m3
ND ND ND
• Sampling Rates are required to determine atmospheric concentrations
Quantity on PUF (ng)
Time Deployed (d)
Sampling Rates for Passive Samplers
÷ Sampling Rate (m3/d) = Atmospheric Conc. (ng/m3)
2,4-D Sampling Rate - Calculated by Linear Regression
y = 16.97x - 0.087R2 = 0.9223
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80
Hi-Vol Concentration (ng/m3)
Mas
s Sa
mpl
ing
Rat
e (n
g/d)
10 m30 m
Sampling Rate = 17 ± 2 m3/d
2,4-D Sampling RateBratt’s Lake Data 2003 - 2005
Triallate Sampling Rate - Calculated by Linear Regression
y = 12.646x + 0.4196R2 = 0.8627
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
0.00 1.00 2.00 3.00 4.00 5.00 6.00 7.00
Hi-Vol Concentration (ng/m3)
Mas
s Sa
mpl
ing
Rat
e (n
g/d)
10 m30 m
Sampling Rate = 13 ± 2 m3/d
Triallate Sampling RateBratt’s Lake Data 2003 - 2005
Trifluralin Sampling Rate - Calculated by Linear Regression
y = 1.2813x + 1.9684R2 = 0.0033
y = 8.1929xR2 =0.7345
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
0.00 0.10 0.20 0.30 0.40 0.50 0.60
Hi-Vol Concentration (ng/m3)
Mas
s Sa
mpl
ing
Rat
e (n
g/d)
10 m30 m
Trifluralin Sampling RateBratt’s Lake Data 2003 - 2005
Sampling Rates
Pesticide
Sampling Rate (ng/m3)
(±95% confidence interval)
Correlation Coefficient,
r
Ethalfluralin 10 ± 1 0.8395Trifluralin 8 ± 2 0.8570Triallate 13 ± 2 0.9288Bromoxynil 12 ± 1 0.8908Dicamba 18 ± 1 0.8725MCPA 14 ± 2 0.94482,4-D 17 ± 2 0.9604Lindane 10 ± 1 0.7608
Based on Data from 2003 - 2005
Determining Sampling Rates using Depuration Compounds
Time
Qua
ntity
on
PUF
Adsorption Curve
Depuration Curve
Depuration Compound Study 2005Comparison of passive sampling rates (m3/d) for lindane determined by: (1) deuterated depuration compound and
(2) hi-vol/passive calculation
(1) γ-HCH d6 (2) Hi-Vol/Passive13 1011 76 69 67 77 77 89 8
Average (S.D.) 9 ± 3 Average (S.D.) 8 ± 1
Minimum Detection Levels90 Day Deployment
PesticideLaboratory
Detection Limit(ng)
PassiveSampling Rate
(m3/d)
AtmosphericDetection Limit
(ng/m3)Ethalfluralin 50 10 0.06
Trifluralin 50 8 0.07
Triallate 50 13 0.04
Bromoxynil 50 12 0.05
Dicamba 50 18 0.03
MCPA 50 14 0.04
2,4-D 50 17 0.03
Lindane 10 10 0.01
Conclusions
• Passive samplers are a simple, cost-effective method for determining pesticides in the atmosphere.
• Further research is required to determine sampling rates for passive samplers.
Further Research
• Investigate whether physical-chemical properties of pesticides can be correlated with sampling rates (e.g. octanol/air partition coefficient).
• Conduct more extensive depuration study using 11 deuterated current-use pesticides.
• Perform a time series depuration study to determine the desorption curve.
Financial Support•Toxic Substances Research Initiative
•Pesticide Science Fund
Acknowledgements
Summer Students:• Kyle Galloway• Nathan Droneck• Mackenzie King
Bratt’s Lake Staff:• David Halliwell• Ormanda Niebergall
Technicians:• Dwight Quiring• Jon Bailey
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