Más contenido relacionado La actualidad más candente (7) Similar a Future of environmental_forensics_inef2016 (20) Más de Chemistry Matters Inc. (20) Future of environmental_forensics_inef201620. © 2016
Chemistry Ma2ers Inc.
Toxicology Takes Over
• In 1973, AhR iden8fied as
mediator of dioxin toxicity
• Extensively studied to iden8fy
structural requirements for
binding to AhR
• TCDD and 2378 subs8tuted
PCDDs/PCDFs fit nicely in
binding site
– mid-1980s – binding site
defined
• Toxic equivalents and toxicity
equivalency factors born
20 INEF 2016 – Örebro, Sweden
Okey A, Toxicological Sciences, 2007, 98, 5–38.
Pandini A. et al, Biochemistry,
2009, 48, 5972–5983
25. © 2016
Chemistry Ma2ers Inc.
Production of 245-TCP – Process 1
0
20
40
60
80
100
0 50 100 150 200 250 300
CompositionofReactionMass:
PercentofmolesofComponentsIndicated
Reaction Time:
Minutes
Caustic added to Tetrachlorobenzene
25 INEF 2016 – Örebro, Sweden
27. © 2016
Chemistry Ma2ers Inc.
Reaction Vessel - 5 minutes
Mostly Tetrachlorobenzene
and few molecules of
245TCP
0
20
40
60
80
100
0 50 100 150 200 250 300
+
+
= 2378-TCDF
= 2378-TCDD
245-TCP forms in reactor
27 INEF 2016 – Örebro, Sweden
HEAT
30. © 2016
Chemistry Ma2ers Inc. 30
Formation of Other PCDD/Fs During
245-TCP Production
Any chlorinated
benzene
Any chlorinated
phenol formed
Multiple PCDD/F
Congeners
Add Base
• Chlorinated benzenes not 100% pure
• Any other chlorinated benzenes present would form
uninten8onal chlorinated phenols which would form mul8ple
PCDDs/PCDFs (other than 2347-TCDD)
INEF 2016 – Örebro, Sweden
35. © 2016
Chemistry Ma2ers Inc. www.chemistry-matters.com 35
US EPA 16 Priority Pollutants
PAH CompoundsWhen were the 16 PAHs selected?
acenaphthene
1,2-dihydroacenaphthylene
1,8-ethylnaphthalene
Naphthyleneethylene
peri-ethylenenaphthalene
acenaphthylenenaphthalene anthracene
paranaphthalene
phenanthrene
3-Helicene
ravatite
9H-fluorene
Fluorene
2,2’-methylenebiphenyl
o-biphenylenemethane
diphenylenemethane
chrysene
1,2-benzophenanthrene
benzo(a)phenanthrene fluoranthene
Pyrene
benzo(def)phenanthrene
tetraphene
benz(a)anthracene
benzo(a)anthracene
1,2-benzanthracene
2,3-benzophenanthrene
benzo(b)phenanthrene
benzo(e)acephenanthrylene
benzo(b)fluoranthene
2,3-benzfluoranthene
3,4-benz(e)acephenanthrylene
benzo[k]fluoranthene
11,12-benzofluoranthene
2,3,1’,8’binaphthylene
dibenzo(b,jk)fluorene
8,9-benzofluoranthene
benzo(k)tetraphene
1,2:5,6-dibenzanthracene
dibenzo(a,h)anthracene
benzo(pqr)tetraphene
benzo(a)pyrene
3,4-benzpyrene
1,2-benzpyrene
benzo(def)chrysene
benzo(ghi)perylene
1,12-benzoperylene
indeno[1,2,3-cd]pyrene
1,1-(1,2-phenylene)pyrene
1,10-(o-phenylene)pyrene
2,3-o-phenylenepyrene
35INEF 2016 – Örebro, Sweden
*Established in 1976
38. © 2016
Chemistry Ma2ers Inc.
Expanding the List of PAHs
Alkylated-PAHs and Other PAHs
C1-Phenanthrenes
1
2
3456
7
8
9 10
CH3
C2-Phenanthrenes
Phenanthrene
CH3
CH3
CH3
H3C
CH2 CH3
C3-Phenanthrenes
C4-Phenanthrenes… (?)
CH3
CH3
CH3
CH2
H2C
CH3
(5)
(30) (?)
38 INEF 2016 – Örebro, Sweden
43. © 2016
Chemistry Ma2ers Inc. 43
Muskeg is a very rich organic environment > 50% TOC
PHC Fractions analysis cannot differentiate natural
hydrocarbons (phytogenic) from petroleum hydrocarbons
(petrogenic).
INEF 2016 – Örebro, Sweden
58. © 2016
Chemistry Ma2ers Inc.
Extreme Sensitivity
(2,3,7,8-TCDD)
Weight Moles Molecules
Microgram (10-6) 3 Nanomoles (10-9) 2,000,000,000,000,000
Nanogram (10-9) 3 Picomoles (10-12) 2,000,000,000,000
Picogram (10-12) 3 Femtomoles (10-15) 2,000,000,000
Femtogram (10-15) 3 A2omoles (10-18) 2,000,000
A2ogram (10-18) 3 Zeptomoles (10-21) 2,000
Zeptogram (10-21) 3 Yaktomoles (10-24) 2
Yaktogram (10-24) 3 Fantomoles (10-27) 0.002
Currently at the attogram level with cryofocusing coupled
with high resolution mass spectrometry
Dr. Donald G. Patterson, Jr.
58 INEF 2016 – Örebro, Sweden
61. © 2016
Chemistry Ma2ers Inc.
Environmental Forensics in the
Gulf Oil Spill
• Reddy et al. sampled oil directly above well to conduct
comprehensive characterization
– Gas isotopes, GOR, fluid characteristics, API etc.
– Fingerprinted with 2D-GC-TOF
– Could distinguish between crudes
Reddy et al. 2011, PNAS Early Edition, p.1-6
61 INEF 2016 – Örebro, Sweden
62. © 2016
Chemistry Ma2ers Inc.
Environmental Forensics in the
Gulf Oil Spill
• Hall et al. took 41 samples (slicks, scrapings off rocks,
grasses and debris, sand patties etc)
• Oxidized hydrocarbons comprised of more than 50% of
extractable hydrocarbons
• Used 2D-GC-TOF of samples compared to oil to assess
weathering of oil spill using chemometric techniques
Hall et al. 2013, Marine
Pollution Bulletin, 75 (1–2), 140
62 INEF 2016 – Örebro, Sweden
74. © 2016
Chemistry Ma2ers Inc.
Thank you for your attention
Contact Info:
Chemistry Matters Inc.
Court Sandau
Cell: 403.669.8566
Email: csandau@chemistry-matters.com
URL: chemistry-matters.com
Visit my website and sign up for email for automatic
receipt of my blogs!
Twitter: @Chem_Matters
Slideshare: www.slideshare.net/csandau
74 www.chemistry-maoers.com