Oxygenated polycyclic aromatic hydrocarbons from ambient ...
Presentation Title: Sample Hold Time Evaluation for Polycyclic Aromatic Hydrocarbons … ·...
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ANALYTICAL CHEMISTRY & TESTING SERVICES
Presentation Title: Sample Hold Time Evaluation for Polycyclic Aromatic Hydrocarbons in Water Samples
by: D.A. Birkholz and Jarrod RobertsRight solutions….
….Right partner
Special Chemistries Division
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ANALYTICAL CHEMISTRY & TESTING SERVICES
Acknowledgements
• ALS Laboratory Group for funding this study• ALS Special Chemistries for doing the work (Dr. Ralitsch)• Chris Lange, ALS Edmonton, sample collection • Lori Cormier, Jackie Kunka and Heather Amyotte sample
extraction, concentration• Andrea Hage and Jarrod Roberts GC/MS analysis, data
interpretation, reporting• Michelle Breland review and statistics
Acknowledgements
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Renewed Interest in PAHs• Toxicological focus both in terms of environmental and human health
• Procedures for the Derivation of Equilibrium Partitioning Sediment Benchmarks (ESBs) for the Protection of Benthic Organisms (EPA-600-R-02-013. Requires the analysis for 34 PAHs including homologues
• Potency Equivalency Factors (PEFs) for Carcinogenic Polycyclic Aromatic Hydrocarbons (Health Canada, 2006). Requires the analysis for 44 PAHs including homologues
• PEFs included in Federal Contaminated Site Risk Assessment in Canada: Guidance on Human Health Preliminary Quantitative Risk Assessment (Health Canada, 2007).
• PAHs are prime candidates for source tracking (forensics)
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US – EPA Sample Holding Time Reevaluation
• “Sample hold time reevaluation” October 2005, EPA/600/R-05/124
• SW-846 prescribed upper bound for allowable variability between replicates for semi-volatile organic compound extraction is coefficient of variation (CV) ≤ 25%
• Holding time recommended for soils/sediments under SW-846 is 14-days and for waters 7-days.
• Following a reassessment, holding time for sediments held at -20oC is 138-days (9.8 * MHT)
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Objective of this work• Determine if the MHT (7-days) for water
(SW-846) was defensible• Determine if the use of preservatives could
extend such holding times • Determine if differing water sources,
namely: slough water, river water, groundwater and lake water had an impact on PAH stability
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Methods• Water samples were obtained from the
following sources:• Slough (Northern Bear golf course)• River (N. Saskatchewan river, Rossdale
Water Treatment Plant raw water intake)• Lake (Lake Wabamun) • Groundwater (acreage)
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Methods• Samples were fortified with PAHs at the 1 ug/L level• Some samples were preserved with ascorbic acid (0.4
g/L), copper sulfate (5 mL/L, 10% w/v) and sulfuric acid (5 mL/L, 6N)
• Samples were analyzed on day 0, day 7 and day 21• Non-spiked (control) samples were analyzed as well• Surrogates were added prior to extraction including:
nitrobenzene-d5; 2-fluorobiphenyl and p-terphenyl-d14• Water samples ( 1L) were processed using EPA SW-846
method 8270• Analyses performed using gas chromatography/mass
spectrometry – selected ion-monitoring
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PAHs soughtacenaphthene acenaphthylene anthracenebenzo(a)anthracene benzo(a)pyrene benzo(b)fluoranthene
benzo(k)fluoranthene benzo(g,h,i)perylene biphenyl
1,3-dimethyl-naphthalene
2,3,5-trimethyl-naphthalene
C4-phenanthrene
chrysene dibenzo(a,h)anthracene dibenzothiophene
fluoranthene fluorene indeno(1,2,3,-cd)pyrene
1 - methyl naphthalene 2-methyl naphthalene naphthalene
phenanthrene pyrene retenebenzo(j)fluoranthene 2-methyl anthracene
26-compounds
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Statistics• Mean, standard deviation, and coefficient
of variation (RSD%) were obtained for all analytes
• Percent reduction of analytes from day 0 was determined
• Average percent reduction along with coefficient of variation was determined
• Successful treatment was viewed if mean reduction was less than 25% from D0
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D0 River Water (n = 8)
0
5
10
15
20
25
Acena
phthe
ne
Acena
phthy
lene
Anthrac
ene
Benzo
(a)an
thrac
ene
Benzo
(a)py
rene
Benzo
(b)flu
oranth
ene
Benzo
(k)flu
oranth
ene
Benzo
(g,h,i
)perylen
eBiph
enyl
C2 nap
hthale
ne
C3 nap
hthale
ne
C4 phe
nanth
rene/a
nthrac
ene
Chryse
ne
Dibenzo
(a,h)a
nthrac
ene
Dibenzo
th iophe
ne
Fluoran
thene
Fluoren
e
Inden
o(c,d-
1,2,3)
pyren
e
Methyl
naph
thalen
e
Methyl
phen
anthr
ene/an
thrac
ene
Naphth
alene
Phena
nthren
ePyre
neRete
ne
Benzo
(j)fluo
ranthen
eC
oeff
icie
nt o
f Var
iatio
n
CI (CV) = x ± 2α = 11 ± 12%
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D0 Lake Water n = 8
0
2
4
6
8
10
12
14
16
Acena
phthen
e
Acena
phthyle
neAnth
racen
e
Benzo
(a)anthr
acen
e
Benzo
(a)pyren
e
Benzo
(b)fluora
nthene
Benzo
(k)flu
oranthe
ne
Benzo
(g,h,i)p
erylene
Biphenyl
C2 nap
hthalen
e
C3 nap
hthalen
e
C4 phe
nanthren
e/anthr
acen
eChry
sene
Dibenz
o(a,h)an
thrac
ene
Dibenz
othiop
hene
Fluoran
thene
Fluoren
e
Indeno
(c,d-1,
2,3)py
rene
Methyl
naphtha
lene
Methyl
phenan
threne/an
thrac
ene
Naphtha
lene
Phena
nthren
ePyre
neRete
ne
Benzo
(j)fluora
nthene
Coe
ffici
ent o
f Var
iatio
n
CI = 8 ± 6%
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D0 Slough Water n = 8
0
2
4
6
8
10
12
Acena
phthen
e
Acena
phthyle
neAnth
racen
e
Benzo
(a)anthr
acen
e
Benzo
(a)pyren
e
Benzo
(b)fluora
nthene
Benzo
(k)flu
oranthe
ne
Benzo
(g,h,i)p
erylene
Biphenyl
C2 nap
hthalen
e
C3 nap
hthalen
e
C4 phe
nanthren
e/anthr
acen
eChry
sene
Dibenz
o(a,h)an
thrac
ene
Dibenz
othiop
hene
Fluoran
thene
Fluoren
e
Indeno
(c,d-1,
2,3)py
rene
Methyl
naphtha
lene
Methyl
phenan
threne/an
thrac
ene
Naphtha
lene
Phena
nthren
ePyre
neRete
ne
Benzo
(j)fluora
nthene
Coe
ffici
ent o
f Var
iatio
n
CI = 7 ± 2%
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D0 Groundwater n = 8
0
2
4
6
8
10
12
14
16
Acena
phthen
e
Acena
phthyle
neAnth
racen
e
Benzo
(a)anthr
acen
e
Benzo
(a)pyren
e
Benzo
(b)fluora
nthene
Benzo
(k)flu
oranthe
ne
Benzo
(g,h,i)p
erylene
Biphenyl
C2 nap
hthalen
e
C3 nap
hthalen
e
C4 phe
nanthren
e/anthr
acen
eChry
sene
Dibenz
o(a,h)an
thrac
ene
Dibenz
othiop
hene
Fluoran
thene
Fluoren
e
Indeno
(c,d-1,
2,3)py
rene
Methyl
naphtha
lene
Methyl
phenan
threne/an
thrac
ene
Naphtha
lene
Phena
nthren
ePyre
neRete
ne
Benzo
(j)fluora
nthene
Coe
ffici
ent o
f Var
iatio
n
CI = 10 ± 6%
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River Water D21: % PAH Reduction from D0
-10
0
10
20
30
40
50
60
70
River Water D21 River Water D21 AA River Water D21 CS River Water D21 SA
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% PAH Reduction River Water 7 - Days
0
5
10
15
20
25
30
% R
educ
tion
from
D0
Unpreserved Preserved
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Lake Water D21: % PAH Reduction from D0
0
10
20
30
40
50
60
70
80
90
Lake Water D21 Lake Water D21 AA Lake Water D21 CS Lake Water D21 SA
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PAH % Reduction Lake Water 7-days
0
5
10
15
20
25
30
35
1
% R
educ
tion
from
D0
Lake Water Unpreserved Lake Water Preserved
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Groundw ater D21: % PAH Reduction from D0
0
5
10
15
20
25
30
35
40
45
50
Groundw ater D21 Groundw ater D21 AA Groundw ater D21 CS Groundw ater D21 SA
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Groundw ater Day 7
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
1
% R
educ
tion
from
D0
Groundw ater D7 Unpreserved Groundw aterDay 7 Preserved
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Slough Water D21: % PAH Reduction from D0
0
10
20
30
40
50
60
70
80
90
Slough Water D21 Slough Water D21 AA Slough Water D21 CS Slough Water D21 SA
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Slough Day 7
-15.00
-10.00
-5.00
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
1
% R
educ
tion
from
D0
Slough Day 7 Unpreserved Slough Day 7 Preserved
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Effect of Preservation on Select PAHs
0
10
20
30
40
50
60
70
80
90
100
Acena
phthe
neAce
naph
thylen
eAnth
racen
e
Biphen
ylC2-N
aphth
alene
C3-Nap
hthale
neDiben
zoth iop
hene
Fluoren
eMeth
yl na
phtha
lene
Methyl
anthr
acen
eNap
hthale
nePhe
nanth
rene
Perc
ent R
educ
tion
from
D0
% Reduction f rom D0 Unpres River Water D21 % Reduction f rom D0 River Water SA Preserved
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% Reduction of PAHs from Lake Water
-20
-10
0
10
20
30
40
50
60
70
80
Acena
phthe
neAce
naph
thylen
eAnth
racen
e
Biphen
ylC2-N
aphth
alene
C3-Nap
hthale
neDiben
zoth iop
hene
Fluoren
eMeth
yl na
phtha
lene
Methyl
anthr
acen
eNap
hthale
nePhe
nanth
rene
% R
educ
tion
from
D0
% Reduction f rom D0 Unpreserved Lake Water D21 %Reduction f rom D0 Preserved Lake Water D21
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% PAH Reduction Slough Water
-20
0
20
40
60
80
100
120
Acena
phthe
neAce
naph
thylen
eAnth
racen
e
Biphen
ylC2-N
aphth
alene
C3-Nap
hthale
neDiben
zoth iop
hene
Fluoren
eMeth
yl na
phtha
lene
Methyl
anthr
acen
eNap
hthale
nePhe
nanth
rene
% R
educ
tion
from
D0
% Reduction f rom D0 Unpreserved Slough Water D21 % Reduction f rom D0 Slough Water Preseved D21
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% Reduction of PAHs
0
5
10
15
20
25
30
35
40
45
Anthracene Methyl anthracene Naphthalene
% R
educ
tion
from
D0
% Reduction f rom D0 Unpreserved River Water D7 % Reduction f rom D0 Preserved River Water D21
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Problem PAHs• Anthracene and methyl anthracene are not stable even
after preservation, 39% reduction from D0 for both• The potency equivalency factor (PEF) for anthracene and
methyl anthracene is 0 so they are of no consequence in human health risk assessments
• Anthracene and methyl anthracene are near the CV limit of 25% after seven day storage, 21 and 24% reduction, respectively
• The CCME ambient water criteria for anthracene is 4 ug/L chronic and 0.1 ug/L in the presence of light (phototoxic).
• Our preservation method would underestimate toxicity by a factor of two for these two analytes only.
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Conclusions• SW-846 coefficient of variation of 25% for semi-
volatile compounds (such as PAHs) was proven valid
• Upper bound confidence intervals for the CVs were: river water (23%); lake water (14%); slough water (9%); and groundwater (16%)
• % PAH reduction from day 0 in river water was 33 ± 31% after 21-days storage at 4oC, and 20 ±4% after 7-days storage
• % PAH reduction from day 0 in river water was 11 ± 13% after 21-days storage when preserved with sulfuric acid.
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Conclusions• %PAH reduction from day 0 in lake water was 46
± 14% after 21-days storage and 23 ± 7% after 7-days storage
• %PAH reduction from day 0 in lake water was 14 ± 11% after 21-days storage when preserved with sulfuric acid
• %PAH reduction from day 0 in slough water was 46 ± 38% after 21-days storage and 4 ± 9% after 7-days storage
• %PAH reduction from day 0 in slough water was 31 ± 16% after 21-days storage when preserved with sulfuric acid
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Conclusions• %PAH reduction from day 0 in
groundwater was 21 ± 15% after 21-days storage and 22 ± 17% after 7-days storage
• %PAH reduction from day 0 in groundwater was 15 ± 9% after 21-days storage when preserved with sulfuric acid
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Conclusions• Anthracene and methyl anthracene degrade
even after preservation.• From a human health perspective this is of no
consequence because the PEF is 0• Anthracene is important with respect to ambient
water criteria.• Our preservation method would underestimate
anthracene by a factor of 2.• Other that this we feel our preservation method
has merit in extending the holding of PAHs, including the alkylated homologues from 7 to 21 days.