PCB 101
Spokane River Forum
May 25, 2011
Dave Hope,
Pacific Rim Laboratories Inc
Outline
• Pacific Rim Laboratories Inc.
• PCB – what is it and why are we still interested
•
•
•
•
•
in it
Toxicity
How do we analyze it – Analytical Methods
What does Not Detected mean?
Limitations to PCB analysis
Closing thoughts
Who Am I?
• Analytical Chemist
– PChem – ACPBC
– President, Canadian Council of Independent
Laboratories
– Owner, Lab Director Pacific Rim Laboratories
• I am not
– Toxicologist
– Consultant
Pacific Rim Laboratories Inc.
• Small ultra-trace organic laboratory specializing
•
•
•
in the analysis of Persistent Organic Pollutants
by High Resolution Mass Spectrometry
Located in Surrey, BC (suburb of Vancouver)
Accredited by WDOE, NELAC and SCC for the
analysis of PCB, PCDD/F and PBDE.
Work in the ppt, ppq and sub-ppq range
How small is small?
• $1 bill is approx. 100 cm2
• Area of Canada is 10M km2
• Finding a given dollar bill anywhere in
Canada is 1 ppq (10-15)
Polychlorinated Biphenyls (PCB)
• Manufactured until early 1970’s (1980’s in
Eastern Europe)
– Total production 1.3-1.5M Tonnes
– Aroclor 1016, 1242, 1254, 1260
– Kanaclor
• Byproduct in the manufacture of other chemicals
– Copper sulphate from China contaminated with
PCB126, 169 and 77.
Chemical Structure
• 209 possible congeners –
•
mono thru
decachlorobiphenyl
Twelve are considered
dioxin like and have been
assigned Toxic
Equivalency Factors (TEF)
•
•
•
•
•
•
•
•
•
•
MonoCB
DiCB
TriCB
TetraCB
PentaCB
HexaCB
HeptaCB
OctaCB
NonaCB
DecaCB
3 congeners
12 congeners
24 congeners
42 (2) congeners
46 (5) congeners
42 (4) congeners
24 (1) congeners
12 congeners
3 congeners
1 congeners
PCBs on ECD – Mix of Aroclor 1242,
1254, 1260
Global Production
• 48% produced
•
•
in USA
50% of
remaining
prduction
imported to
USA
97% in
Northern Hemi
Applications of PCB
• Closed systems
• Insulation and/or cooling fluid in
•
•
•
•
•
•
•
•
•
transformers (48%)
Dielectric fluid in capacitors (21%)
Switches
Partially open systems
Heat transfer fluids
Hydraulic fluid in lifting equipment,
trucks and high pressure pumps
Vacuum Pumps
Voltage Regulators
Liquid Filled Electrical Cables
Liquid Filled Circuit Breakers
•
•
•
•
•
•
•
•
•
•
•
Open systems (21%)
Paints
Lubricating fluid in oils and grease
Water-repellent impregnating agent
and fire retardant for wood, paper,
fabric and leather
Laminating agent in paper production
Additive in glues, sealants and
corrosion protection coatings
Carrier for insecticides
Polymerisation catalyst support for
petrochemicals
Immersion oils for microscopy
Pesticide Formulation
Cable coatings/casings
Stockholm Convention
• In 2001 the Stockholm convention was adopted,
restricting the manufacturing and use of twelve
Persistent Organic Pollutants – POPs
– PCDD/F, PCB
– Pesticides – Aldrin, Dieldrin, Endrin, DDT, Heptachlor,
Hexachlorobenzene, Mirex, Chlordane, Toxaphene
• Ratified in May 2004
• Currently 127 countries have ratified, excluding USA
• August 2010 – 9 additional chemicals included
– Hexachlorocyclohexane (α, β, γ (Lindane)), PBDE (commercial
Penta and Octa), hexabromobiphenyl, chlordecone,
pentachlorobenzene, PFOS/PFOA
– Endosulphan added last month
PCB Toxicity
• World Health Organization (WHO) defines twelve toxic
congeners
– Due to positioning of chlorines, the molecule is unable to rotate
and forms structure similar to dioxin
• 2,3,7,8-TCDD considered to have a toxicity of 1, all
•
others are relative to TCDD
Toxic Equivalency Factors (TEF)
– PCB126 (0.1), PCB169 (0.03), PCB077 (0.0001), PCB081
(0.0003)
– PCB105, 114, 118, 123, 156, 157, 167, 189 (0.00003)
• PCB TEQ = ∑Cx x TEFx for all PCB congeners
Toxicity of Aroclors
Congener
Chlorine
Number
Substitution
77
Pattern (IUPAC)
3,3',4,4'
81
3,4,4',5
105
2,3,3',4,4'
114
Aroclor Composition (Wt %)
A1016
A1242
Frame et al. (1996) Data
A1254a
A1254g
A1260
0.31
0.2
0.01
0.01
0.47
7.37
2.99
2,3,4,4',5
0.04
0.5
0.18
118
2,3',4,4',5
0.66
13.59
7.35
123
2,3',4,4',5'
0.03
0.32
0.15
126
3,3',4,4',5
0.02
0.01
156
2,3,3',4,4',5
1.13
0.82
0.52
157
2,3,3',4,4',5'
0.3
0.19
0.02
167
2,3',4,4',5,5'
0.35
0.27
0.19
169
3,3',4,4',5,5'
189
2,3,3',4,4',5,5'
0.01
0.01
0.1
Toxicity
trace
0.01
0.03
0.22
0.48
ppm
ppm
ppm
ppm
0.70
27
14
0.46
Regulatory Levels – Food
Max intake – 2 pg TEQ/kg bw/day
• European Food Regulations (pg
•
•
•
•
•
•
•
•
•
•
•
WHO-TEQ/g fat)
PCDD/F
Fish (fresh wt): 4
Pork:
1
Poultry
2
Beef / mutton: 3
Liver
6
Milk:
3
Eggs:
3
Vegetable oil: 0.75
Mix Animal fat: 2
Fish oil:
2
(&PCB)
(8)
(1.5)
(4)
(4.5)
(12)
(6)
(6)
(1.5)
(3)
(10)
•
•
•
•
•
•
•
•
European Feed Regulations
Feed*:
0.75 pg WHO-TEQ/g
Pet foods:
2.25 pg WHO-TEQ/g
Animal fat:
2 pg WHO-TEQ/g
Minerals:
1 pg WHO-TEQ/g
Fish oil:
6 pg WHO-TEQ/g
Fish meal:
1.25 pg WHO-TEQ/g
* - based on 12% moisture content
Food levels
• Eggs – 2.1-38 ug/kg fat
– 0.11 – 2.86 ng TEQ/kg fat
• Meat – 50 – 1960 ng/kg fat
– 0.001 – 0.182 ng TEQ/kg fat
• Fish 0.29 – 87 ug/kg
– 0.1 – 2.4 ng TEQ/kg
Fish sample – Cl4-Cl7
70
52
74 66
60
110
118
105
153
138
128
182/187
156
180 170
Fish sample – Cl7-Cl10
180
170
199 203
194
206 209
PCB Analysis in Blood
tetra-PCBs
• PCBs in blood
– 200-800 ug /kg lipid
– PCB153>138>180>18
7>118>170>99
penta-PCBs
hexa-PCBs
20
Analytical Methods
Good – Better - Best
• GC/ECD Methods
– EPA 8081, 8082, 608, 508
• GC/MS Methods
– EPA 8270
• GC/HRMS Methods
– EPA 1668
Analytes
Good – Better - Best
• Total PCB – Aroclor equivalents
• Homolog Totals
– 10 levels of chlorination
• Congener specific (209)
Sample Extraction & Clean-up
• Extraction
– Water – liquid/liquid
extraction
– Soil – soxhlet
– Tissue – acid digestion
followed by liquid/liquid
extraction
• Clean-up
– Wash with conc. Sulfuric
acid
– Column on acidic silica gel
– Column on basic alumina
Quantitation Methods
Good – Better - Best
• External standard
– compare with calibration curve
– Requires known final volume and amount injected
• Internal Standard
– Add standard just before analysis
– Relative response factors determined from calibration curve
– With area of IS peak and RRF, can calculate concentration
• Isotope dilution
– Stable isotopes added before extraction used to quantify results
– Corrects for loses during work-up
EPA 8082
• Can be used to identify Aroclors or congeners
• 19 congeners – MonoCB – NonaCB
• PCB1, 15, 18, 31, 44, 52, 66, 87, 101, 110, 138, 141,
•
151, 153, 170, 180, 183, 187, 206
IS Method: One internal standard and one surrogate
standard
Pattern Recognition
• Must match the pattern
•
•
•
in the sample with one
of 7 Aroclor standards
Use 3-5 peaks in the
standard to quantify
sample (External Std)
Detection limits 0.05
ug/L
Problems with pattern
recognition in
weathered samples
GC/MS Methods
• EPA 8270
– Generic catch-all method
– Uses GC/MS for ultimate identification, but causes a greatly
reduced sensitivity (increased detection limit)
– Detection limits 10 ug/L (Aroclor equivalents)
• Homolog Total Methods
– Uses GC/MS in SIM for greater sensitivity and selectivity
– Internal Standard for each level of chlorination
– PCB defined as having peaks in QM and RM channels and being
within 15% of theoretical mass ratio
– Quantifies on congener basis but not identified
– Detection limits 0.001 ug/L on a congener basis
EPA Method 1668
• HRGC-HRMS congener specific method (first written
•
1999, revised in November 2008, June 2010)
Uses 27 internal standards (13C12-labeled congeners)
– All twelve dioxin-like PCBs
– First and last eluters in each level of chlorination (LOC)
– Three 13C12-clean-up standards and five 13C12-recovery standards
• Five (1-2000 ng/mL) or six point (0.2-2000 ng/mL)
•
•
calibration for dlPCBs and LOC PCBs
Single point calibration for all remaining PCBs
Two methods of quantification
– Isotope dilution (for 27 congeners with labeled standards)
– Internal standard – everything else
HRMS analysis - Issues
• Coelutions for TeCB, PeCB and HxCB
– M-Cl gives significant peak, therefore cannot have
coelutions with significant peaks of higher LOC
• Each LOC requires four ions
– PeCB, HxCB, HpCB and OcCB overlap
– Requires 16 ion channels
• Need to maximize sensitivity, therefore typical
collection rates of 1 hz (no 10-100 hz that can
be found with ECDs or MSDs)
GC Columns
• 1668 is based on SPB-octyl column, or dual column with
•
DB-1. Has been met with mixed reviews.
Resolves 159 peaks (180 with DB-1)
–
–
–
–
30/42 TeCB
29/46 PeCB
31/42 HxCB
PCB156 and 157 coelute
• DB-5ms is another popular column
• Performance specs similar to Octyl (165 peaks) however
separates 156 & 157
New column – SGE HT8 PCB
• 8% Phenyl (equiv.)
Polycarborane-siloxane
• 60 m column, 0.25 mm i.d,
–
–
–
–
–
Initial Temp 90 C for 1 min.
Ramp
20 C/min -> 190 C
Ramp2
1.5 C/min. -> 250 C
Ramp3
4.0 C/min. -> 300 C
Final Temp 300 C for 4.2 min.
• Thermo DFS HRMS with dual
Thermo Trace GCs,
split/splitless injection
Results
• 209 resolvable by ECD @ 100 hz
• 189 resolvable peak tops by HRMS
• 37/42 TeCB
• 37/46 PeCB
• 40/42 HxCB
C o ng en
N umb er
9 Pt
St d
C S2 0 9
PCB-001
PCB-002
PCB-003
10.44
13.02
13.30
10.29
12.94
13.23
PCB-010
PCB-004
PCB-009
PCB-007
PCB-006
PCB-008
PCB-005
PCB-014
PCB-011
PCB-013
PCB-012
PCB-015
14.18
14.29
16.35
16.60
17.78
18.31
18.39
19.95
22.45
23.17
23.19
46.47
14.04
14.22
16.31
16.49
17.76
PCB-019
PCB-030
PCB-018
PCB-017
PCB-024
PCB-027
PCB-032
PCB-016
PCB-023
PCB-034
PCB-029
PCB-026
PCB-025
PCB-031
PCB-028
PCB-021
PCB-020
PCB-033
PCB-022
PCB-036
PCB-039
PCB-038
PCB-035
PCB-037
19.56
20.41
22.27
22.67
23.24
23.75
24.66
24.90
25.95
26.41
26.61
27.56
27.99
28.50
29.03
29.98
30.55
30.59
31.49
32.70
33.78
35.41
37.36
38.64
18.30
19.88
22.47
23.16
23.96
19.50
20.38
22.25
22.61
23.21
23.73
24.62
24.88
25.95
26.39
26.59
27.54
27.98
28.49
29.03
29.99
30.56
31.51
32.73
33.85
35.43
37.43
38.72
C o ng en
N umb er
9 Pt
St d
C S2 0 9
PCB-054
PCB-050
PCB-053
PCB-051
PCB-045
PCB-046
PCB-069
PCB-052
PCB-073
PCB-043
PCB-049
PCB-065
PCB-075
PCB-062
PCB-048
PCB-047
PCB-044
PCB-059
PCB-042
PCB-064
PCB-072
PCB-071
PCB-041
PCB-068
PCB-040
PCB-057
PCB-067
PCB-063
PCB-058
PCB-061
PCB-074
PCB-070
PCB-055
PCB-066
PCB-080
PCB-076
PCB-060
PCB-056
PCB-079
PCB-078
PCB-081
PCB-077
25.37
27.37
28.95
29.71
30.56
32.09
32.90
33.01
33.27
33.45
33.68
33.95
34.23
34.39
34.35
34.40
36.33
36.56
36.98
37.85
38.27
38.28
38.37
39.08
39.81
40.37
41.32
41.69
41.92
42.18
42.73
43.54
43.78
44.36
44.37
45.58
46.94
47.22
49.75
51.27
52.51
54.16
25.37
27.35
28.98
29.73
30.56
32.09
33.01
33.31
33.68
33.94
34.27
34.38
36.35
36.59
36.99
37.86
38.18
38.33
39.11
39.83
40.40
41.35
41.73
41.93
42.20
42.78
43.59
43.78
44.39
44.49
45.61
47.00
47.26
49.84
51.36
52.59
54.20
C o ng en
N umb er
9 Pt
St d
C S2 0 9
PCB-104
PCB-096
PCB-103
PCB-100
PCB-094
PCB-093
PCB-102
PCB-098
PCB-095
PCB-088
PCB-091
PCB-121
PCB-084
PCB-092
PCB-089
PCB-090
PCB-101
PCB-113
PCB-099
PCB-112
PCB-119
PCB-083
PCB-109
PCB-086
PCB-125
PCB-117
PCB-097
PCB-116
PCB-115
PCB-087
PCB-111
PCB-085
PCB-110
PCB-120
PCB-082
PCB-124
PCB-108
PCB-107
PCB-123
PCB-106
PCB-118
PCB-114
PCB-122
PCB-105
PCB-127
PCB-126
33.92
37.12
38.48
39.55
40.55
41.75
41.89
41.96
42.11
42.55
43.15
43.69
45.76
45.98
46.18
46.84
47.17
47.65
48.10
49.10
49.34
49.59
49.73
50.31
50.43
50.48
50.63
50.87
51.11
51.19
51.78
51.91
52.60
52.68
54.02
55.49
55.81
55.84
56.14
56.28
56.59
57.27
57.87
59.08
59.26
61.33
33.90
37.15
38.50
39.55
40.59
41.81
42.59
43.15
43.73
45.80
45.99
46.22
46.88
47.19
47.68
48.12
49.12
49.72
49.72
50.48
50.91
51.16
51.89
51.99
52.65
52.73
54.05
55.51
55.86
56.15
56.30
56.61
57.29
57.91
59.09
59.28
61.36
C o ng en
N umb er
PCB-155
PCB-150
PCB-152
PCB-145
PCB-136
PCB-148
PCB-154
PCB-151
PCB-135
PCB-144
PCB-147
PCB-149
PCB-139
PCB-140
PCB-143
PCB-134
PCB-142
PCB-131
PCB-133
PCB-165
PCB-132
PCB-146
PCB-161
PCB-153
PCB-168
PCB-141
PCB-137
PCB-130
PCB-163
PCB-164
PCB-138
PCB-160
PCB-158
PCB-129
PCB-166
PCB-159
PCB-128
PCB-162
PCB-167
PCB-156
PCB-157
PCB-169
9 Pt
St d
C S2 0 9
43.35
46.70
47.77
50.01
50.05
50.58
51.88
52.99
53.51
53.73
53.80
54.56
54.59
55.08
55.41
55.61
56.03
56.25
56.70
57.25
57.45
57.50
57.78
58.29
58.39
59.06
59.51
59.70
60.06
60.07
60.19
60.21
60.37
60.53
60.79
61.47
61.59
61.74
62.09
62.98
63.17
64.43
43.37
46.70
47.77
48.99
50.06
50.58
51.89
52.99
53.52
53.87
53.81
54.59
55.10
55.43
55.63
56.02
56.27
56.70
57.25
57.50
57.50
57.78
58.32
58.39
59.08
59.52
59.70
60.08
60.21
60.31
60.39
60.53
60.79
61.49
61.61
61.76
62.09
62.97
63.17
64.46
C o ng en
N umb er
9 Pt
St d
C S2 0 9
PCB-188
PCB-184
PCB-179
PCB-176
PCB-186
PCB-178
PCB-175
PCB-182
PCB-187
PCB-183
PCB-185
PCB-174
PCB-181
PCB-177
PCB-171
PCB-173
PCB-172
PCB-192
PCB-180
PCB-193
PCB-191
PCB-170
PCB-190
PCB-189
55.30
56.25
57.48
58.31
58.91
59.98
60.39
60.54
60.56
60.94
61.38
61.66
61.74
61.90
62.19
62.40
62.99
63.13
63.32
63.35
63.55
64.24
64.35
65.67
55.31
56.27
57.50
58.31
58.93
60.00
60.41
PCB-202
PCB-200
PCB-204
PCB-197
PCB-201
PCB-198
PCB-199
PCB-196
PCB-203
PCB-195
PCB-194
PCB-205
61.42
61.85
61.97
62.26
62.79
64.05
64.10
64.37
64.41
65.37
66.60
66.96
61.45
61.87
61.97
62.27
62.81
64.08
64.13
64.39
64.43
65.36
66.60
66.95
PCB-208
PCB-207
PCB-206
64.69
65.04
67.59
64.72
65.05
67.59
PCB-209
68.05
68.05
60.56
60.95
61.38
61.66
61.74
61.89
62.20
62.40
62.99
63.14
63.35
63.45
63.57
64.24
64.38
65.68
What is the Detection Limit?
• Standard methods for MDL determination
–
–
–
–
7-10 blank samples spiked at low level with analytes of interest
MDL = 3 * SD (approximately)
Better precision leads to low MDLs
Our MDLs are 1-13 pg/L
• Isotope dilution allows for lower theoretical MDLs due to
•
•
lower SD
Many isotope dilution methods call for the reporting of
Instrument Detection Limits based on 2.5 x SN
Can give IDLs <1 pg/L
Analyte
PCB #
Blank
n
t
pg/L
Average
Stdev (s)
pg/L
pg/L
RSD
Recovery
MDL (ts)
pg/L
2-MoCB
1
3.80
9
2.896
12.06
2.00
17%
165%
6.0
2,4'-DiCB
8
7.89
9
2.896
21.15
2.40
11%
265%
7.5
2,2',6-TriCB
19
9
2.896
8.10
0.62
8%
162%
1.8
2,2',5-TriCB
18
9
2.896
9.86
3.00
30%
197%
9
2,4,4'-TriCB
28
9
2.896
17.63
4.13
23%
142%
12
2,2',5,5'-TeCB
52
9
2.896
4.93
1.94
39%
99%
5.8
3,4,4',5-TeCB
81
9
2.896
5.68
0.45
8%
114%
1.3
3,3',4,4'-TeCB
77
9
2.896
6.54
0.25
4%
131%
0.75
2,2',4,5,5'-PeCB
101
2.19
9
2.896
9.03
1.81
20%
137%
5.4
2,2',4,4',5-PeCB
99
1.38
9
2.896
6.22
1.22
20%
97%
3.7
2,3,3',4',6-PeCB
110
6.17
9
2.896
11.01
2.07
19%
97%
6.2
2,3',4,4',5'-PeCB
123
9
2.896
5.48
0.47
9%
110%
1.4
2,3',4,4',5-PeCB
118
9
2.896
9.36
0.99
11%
121%
3.0
2,3,4,4',5-PeCB
114
9
2.896
5.61
0.37
7%
112%
1.1
2,3,3',4,4'-PeCB
105
9
2.896
7.17
0.50
7%
81%
1.5
3,3',4,4',5-PeCB
126
9
2.896
4.99
0.47
9%
100%
1.4
2,2',3,4',5',6-HxCB
149
9
2.896
20.08
4.11
20%
206%
13
2,2',3,4,5,5'-HxCB
141
9
2.896
4.71
0.47
10%
94%
1.4
2,2',3,3',4,5-HxCB
138
9
2.896
10.00
1.38
14%
180%
4.1
2,3',4,4',5,5'-HxCB
167
9
2.896
5.28
0.56
11%
106%
1.7
2,3,3',4,4',5-HxCB
156
9
2.896
5.59
0.42
7%
112%
1.3
2,3,3',4,4',5'-HxCB
157
9
2.896
5.47
0.46
8%
109%
1.4
3,3',4,4',5,5'-HxCB
169
9
2.896
4.35
0.46
10%
87%
1.4
2,2',3,3',4,4',6-HpCB
171
9
2.896
9.60
1.30
13%
192%
3.9
2,3,3',4,4',5,5'-HpCB
189
9
2.896
5.54
0.41
7%
111%
1.2
2,2',3,3',5,5',6,6'-OcCB
202
9
2.896
5.54
0.60
11%
111%
1.8
2,2',3,3',4,5',6,6'-OcCB
201
9
2.896
3.66
0.34
9%
73%
1.0
2,2',3,3',4,4',5,5',6-NoCB
206
9
2.896
5.63
0.64
11%
113%
1.9
2,2',3,3',4,4',5,5',6,6'-DeCB
209
9
2.896
6.66
1.14
17%
133%
3.4
10.54
3.33
3.10
9.76
1.02
IUPAC Name
PCB #
CAS #
Conc.
IDL
2-MoCB
PCB-001
2051-60-7
3-MoCB
PCB-002
4-MoCB
PCB-003
2,6-DiCB
pg/L
pg/L
9.9
0.8
J
2051-61-8
5.6
0.8
J
2051-62-9
3.2
0.8
J
PCB-010
33146-45-1
3.7
3.7
UJ
2,2'-DiCB
PCB-004
13029-08-8
30.2
3.7
2,5-DiCB
PCB-009
34883-39-1
3.7
3.7
UJ
2,4-DiCB
PCB-007
33284-50-3
3.7
3.7
UJ
2,3'-DiCB
PCB-006
25569-80-6
3.7
3.7
UJ
2,3/2,4'-DiCB
PCB-005/008
7.2
3.7
J
3,5-DiCB
PCB-014
34883-41-5
3.7
3.7
UJ
3,3'-DiCB
PCB-011
2050-67-1
44.4
3.7
3,4/3,4'-DiCB
PCB-012/013
3.7
3.7
4,4'-DiCB
PCB-015
2050-68-2
4.3
3.7
J
2,2',6-TrCB
PCB-019
38444-73-4
0.9
0.9
UJ
2,4,6-TrCB
PCB-030
35693-92-6
0.9
0.9
UJ
2,2',5-TrCB
PCB-018
37680-65-2
12.6
0.9
2,2',4-TrCB
PCB-017
37680-66-3
5.4
0.9
J
2,3,6-TrCB
PCB-024
55702-45-9
0.9
0.9
UJ
2,3',6-TrCB
PCB-027
38444-76-7
0.9
0.9
UJ
2,4',6-TrCB
PCB-032
38444-77-8
0.9
0.9
UJ
2,2',3-TrCB
PCB-016
38444-78-9
4.4
0.9
J
2,3,5-TrCB
PCB-023
55720-44-0
0.9
0.9
UJ
2,3',5'-TrCB
PCB-034
37680-68-5
0.9
0.9
UJ
2,4,5-TrCB
PCB-029
15862-07-4
0.9
0.9
UJ
2,3',5-TrCB
PCB-026
38444-81-4
0.9
0.9
UJ
2,3',4-TrCB
PCB-025
55712-37-3
0.9
0.9
UJ
2,4',5-TrCB
PCB-031
16606-02-3
8.6
0.9
J
2,4,4'-TrCB
PCB-028
7012-37-5
6.8
0.9
J
2,3,4-TrCB
PCB-021
55702-46-0
0.9
0.9
UJ
4.7
0.9
J
PCB-020/033
Flag
UJ
2,3,4'-TrCB
PCB-022
38444-85-8
0.9
0.9
UJ
3,3',5-TrCB
PCB-036
38444-87-0
0.9
0.9
UJ
3,4',5-TrCB
PCB-039
38444-88-1
0.9
0.9
UJ
3,4,5-TrCB
PCB-038
53555-66-1
0.9
0.9
UJ
3,3',4-TrCB
PCB-035
37680-69-6
0.9
0.9
UJ
3,4,4'-TrCB
PCB-037
38444-90-5
0.9
0.9
UJ
• Values >IDL are
real
• Values between
IDL and MDL???
What is Total PCB?
• Sounds simple, add up individual results
for all 209 congeners
• How do you handle different detection
limits? Co-elutions? Low level
concentrations?
• Should data be reported below EQL?
PCB #
A
B
C
D
E
Blank
Homologs
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
Monochlorobiphenyls
10.8
10
12.3
10.7
11
0
Dichlorobiphenyls
19.6
74.6
50.5
52
14.4
0
Trichlorobiphenyls
63
12.6
0
11.3
0
0
Tetrachlorobiphenyls
101
0
10.4
0
0
0
Pentachlorobiphenyls
152
23.2
15.5
27.6
0
29.9
Hexachlorobiphenyls
69.2
0
0
0
0
0
Heptachlorobiphenyls
0
0
0
0
0
0
Octachlorobiphenyls
0
0
0
0
0
0
Nonachlorobiphenyls
0
0
0
0
0
0
Decachlorobiphenyl
0
0
0
0
0
0
415
110
88.7
102
25.4
Total PCB
29.9
PCB #
A
B
C
D
E
Blank
Homologs
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
Monochlorobiphenyls
14.5
18.7
18.5
20.1
17.6
9.3
Dichlorobiphenyls
19.6
86.1
50.5
52
14.4
0
Trichlorobiphenyls
88.2
42.5
31.5
36
34.7
0
Tetrachlorobiphenyls
132.8
29.5
33.6
37.7
24.4
0
Pentachlorobiphenyls
173.4
40.2
24
27.6
15.5
29.9
Hexachlorobiphenyls
119.3
9.2
14.5
4.6
5.6
1.8
Heptachlorobiphenyls
30.2
0
0
0
2.3
0
Octachlorobiphenyls
11.6
0
2.5
0
1.4
0
Nonachlorobiphenyls
0
0
0
0
0
0
Decachlorobiphenyl
4.4
0
0
0
0
0
Total PCB
594
226.2
175.1
178
115.9
41
A
B
C
D
E
Blank
Homologs
pg/L
pg/L
pg/L
pg/L
pg/L
pg/L
Monochlorobiphenyls
10.8
10
12.3
10.7
11
0
Dichlorobiphenyls
19.6
74.6
50.5
52
14.4
0
Trichlorobiphenyls
63
12.6
0
11.3
0
0
Tetrachlorobiphenyls
101
0
10.4
0
0
0
Pentachlorobiphenyls
152
23.2
15.5
27.6
0
29.9
Hexachlorobiphenyls
69.2
0
0
0
0
0
Heptachlorobiphenyls
0
0
0
0
0
0
Octachlorobiphenyls
0
0
0
0
0
0
Nonachlorobiphenyls
0
0
0
0
0
0
Decachlorobiphenyl
0
0
0
0
0
0
415
110
88.7
102
25.4
29.9
PCB #
Total PCB
What is Blank?
•
•
•
•
PCB is omnipresent
Almost impossible to achieve a complete blank in the lab
Every sample we analyze has detectable PCB levels.
In order to reduce blank levels in the lab
– Use carbon filtered water
– Disposable glassware (not always possible)
– Keep food samples away!
• <20 pg/L per congener is excellent
What is achievable?
• Less than 20 labs in North America can
run EPA 1668
• No analytical confidence at 3 pg/L for
Total PCB
• Reductions will be hard to measure
– Are they lab caused or real?
• Focus on Toxic PCBs rather than 209
congeners
Thank you!
dave@pacificrimlabs.com
www.pacificrimlabs.com