coauthors - university of saskatchewans new/setac orlando...1900 2000 0.0 0.5 1.0 1.5 2.0 136-bcz...
TRANSCRIPT
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Polyhalogenated Carbazoles in Sediment of the Great Lakes: Natural or Anthropogenic?
An Li, PhD, Professor, University of Illinois at Chicago
[email protected], h@p://anli.people.uic.edu
SETAC 7th World Congress & North America 37th Annual MeeNng
Orlando, FL. Nov. 7, 2016
Coauthors An Li*, Jiehong Guo, Zhuona Li, Prabha Ranasinghe
School of Public Health, University of Illinois at Chicago
Karl J. Rockne, Solidea Bonina, Soheil Hosseini
Department of Civil and Materials Engineering,
University of Illinois at Chicago
Neil C. Sturchio, Margaret B. Corcoran, Colin Smalley
Department of Earth and Environmental Sciences,
University of Illinois at Chicago, University of Delaware
John P. Giesy
Department of Veterinary Biomedical Sciences and Toxicology Centre, University of Saskatchewan
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PHCZ IntroducKon
§ Structurally similar to PXDFs. § 135 congeners of polychlorinated
(CCZs), polybrominated (BCZs), or polyiodinated (ICZs). Total???
§ Numbering of halogen posiNons differs from that for PXDFs and also among studies!
§ First reported in the environment in the 1980s, but received li@le a@enNon.
C12H9-xNXx (X = Cl, Br, I, and x = n + m = 1-8)
Wellington Laboratories
Sediment sampling
29 cores (671 segments) 115 Ponar grabs
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(X = Cl, Br, and/or I)
024681012141618202224262830
0 8 16 24 32 40 48
Dep
th (cm
)
Concentration (ng/g)
dx.doi.org/10.1021 | ES&T, 2014, 48, 12807−12815
26 PHCZs found in GL sediment Abbrev. Full name Formula MW
Carbazoleb Carbazole C12H9N 167.07
3-CCZb 3-monochloro carbazole C12H8NCl 201.03
3-BCZb 3-monobromo carbazole C12H8NBr 244.98
36-CCZb 3,6-dichloro carbazole C12H7NCl2 235.00
1368-CCZ 1,3,6,8-tetrachloro carbazole C12H5NCl4 302.92
UNC-1 unknown-1 C12H6NClBr2 356.86
1-B-36-CCZ 1-bromo-3,6-dichlorocarbazole C12H6NCl2Br 312.91
UNC-2 unknown-2 C12H6NBr3 400.81
UNC-3 unknown-3 C12H7NBr2 322.89
27-BCZ 2,7-dibromo carbazole C12H7NBr2 322.89
36-BCZ 3,6-dibromo carbazole C12H7NBr2 322.89
18-B-36-CCZ
1,8-dibromo-3,6-dichlorocarbazole
C12H4NCl2Br2
390.82
UNC-4 unknown-4 C12H6NBr3 400.81
UNC-5 unknown-5 C12H5NClBr3 434.77
Abbrev. Full name Formula MW
UNC-6 unknown-6 C12H6NBr3 400.81
UNC-7 unknown-7 C12H5NClBr3 434.77
136-BCZ 1,3,6-tribromo carbazole C12H6NBr3 400.81
UNC-9 unknown-9 C12H5NBr4 478.72
1368-BCZ 1,3,6,8-tetrabromo carbazole C12H5NBr4 478.72
2367-CCZ 2,3,6,7-tetrachloro carbazole C12H5NCl4 302.92
UNC-16 unknown-16 C12H4NClBrI 404.84
UNC-10 unknown-10 C12H6NBr3 400.81
UNC-11 unknown-11 C12H4NClBr4 512.68
UNC-12 unknown-12 C12H4NBr5 556.63
UNC-13 unknown-13 C12H4NClBr3I 560.66
UNC-14 unknown-14 C12H4NBr4I 604.61
UNC-15 unknown-15 C12H4NBr3I2 652.60
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ConcentraKons
0
20
40
60
80
100
120
0.001
0.01
0.1
1
10
100
1000
Car
bazo
le
3-C
CZ
36-C
CZ
1368
-CC
Z
2367
CC
Z
3-B
CZ
UN
C-3
36-B
CZ
UN
C-2
UN
C-4
UN
C-6
136-
BC
Z
UN
C-1
0
UN
C-9
1368
-BC
Z
UN
C-1
2
UN
C-1
1-B
-36-
CC
Z
18-B
-36-
CC
Z
UN
C-5
UN
C-7
UN
C-1
1
UN
C-1
3
UN
C-1
6
UN
C-1
4
UN
C-1
5
∑27
PHC
s
∑PC
Bs
BD
E209
Lake Michigan
0
20
40
60
80
100
120
0.001
0.01
0.1
1
10
100
1000
Car
bazo
le
3-C
CZ
36-C
CZ
1368
-CC
Z
2367
CC
Z
3-B
CZ
UN
C-3
36-B
CZ
UN
C-2
UN
C-4
UN
C-6
136-
BC
Z
UN
C-1
0
UN
C-9
1368
-BC
Z
UN
C-1
2
UN
C-1
1-B
-36-
CC
Z
18-B
-36-
CC
Z
UN
C-5
UN
C-7
UN
C-1
1
UN
C-1
3
UN
C-1
6
UN
C-1
4
UN
C-1
5
∑27
PHC
s
∑PC
Bs
BD
E209
Lake Superior
0
20
40
60
80
100
120
0.001
0.01
0.1
1
10
100
1000
Car
bazo
le
3-C
CZ
36-C
CZ
1368
-CC
Z
2367
CC
Z
3-B
CZ
UN
C-3
36-B
CZ
UN
C-2
UN
C-4
UN
C-6
136-
BC
Z
UN
C-1
0
UN
C-9
1368
-BC
Z
UN
C-1
2
UN
C-1
1-B
-36-
CC
Z
18-B
-36-
CC
Z
UN
C-5
UN
C-7
UN
C-1
1
UN
C-1
3
UN
C-1
6
UN
C-1
4
UN
C-1
5
∑27
PHC
s
∑PC
Bs
BD
E209
Lake Huron
Con
cent
ratio
n (n
g/g
dw)
Detection R
ate (%)
Temporal trend comparison
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 1 2 3 4
Carbazole
M011 M018 M032 M041
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0.0 0.2 0.4 0.6
3-CCZ 1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0.0 0.5 1.0 1.5 2.0
136-BCZ
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 5 10 15
BDE209
M011
M018
M032
M041
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 20 40 60
Cat-I 1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0.0 0.5 1.0 1.5 2.0
Cat-III 1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 10 20 30
Cat-II
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 2 4 6 8 10
1368-BCZ
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A lot more than PCBs and PBDEs!
§ The loads of PHCZs are much higher than any known anthropogenic pollutant groups.
§ The PHCZ loads could be under-‐esNmated, because many of them were found in the bo@om segments of the cores (30 cm for Lake Michigan), suggesNng the presence of unknown amount in deeper sediment.
1
10
100
1000
10000
Michigan Superior Huron
tonn
e
PHCZs BDE209 tPCBs
PCA analyses
§ PC1 explained 38% and PC2 32% of the total variance in the data § Based on PCA and spaNal-‐temporal analyses, we tentaNvely
grouped the 22 detected PHCZs into categories I, II, and III
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Where PHCZs come from? § Anthropogenic
• By-‐product of blue dye (indigo) producNon (Pare@e et al. 2015). • Carbazole has been produced for many decades. • Industrial halogenaNon of carbazole started before the 1910s. • Halogenated carbazoles are involved in the manufacturing of various industrial products such as dyes, pharmaceuNcals, organic semiconductor, and others.
• Many carbazole derivaNves are commercially available. § Natural
• Carbazole derivaNves are rich in crude oil and coal, suggesNng an origin in natural organic ma@er (NOM).
• Geological Michigan Basin and Illinois Basin have rich brine sources in deep rock, as evidenced by the salt springs in the region
§ Different PHCZs may have different predominant sources
Category I
§ 13 PHCZs • counNng for ~60% of total • Br only (1368-‐BCZ, and UNCs -‐2, -‐4, -‐9, -‐12)
• Br and Cl (UNCs -‐1, -‐5, -‐7, -‐11) • Iodine containing: UNCs -‐13 to -‐16
§ Lake Michigan > the other lakes; except UNC-‐12 for which Lake Superior had higher level.
§ Higher concentraNons in deposiNonal zones than in near shore areas.
– Unlikely to relate to modern industries
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 20 40 60
Cat-I
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Category I
1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0 2 4 6 8 10
1368-BCZ
§ High and constant level before ~1900; aner that a conNnuous decline.
§ This chronological trend may reflect the impact of human se@lement.
§ Land cover changed drasNcally This could have altered the sources and the characterisNcs of NOM in Lake Michigan
The virgin northern mesic forests was largely replaced by non-‐forest land; rises of ragweeds
Dependence on water depth
§ ConcentraNon of category I PHCZs depends strongly on the water depth at sampling locaNons.
§ Recent fluxes to sediment of Category I is inversely correlated with sediment TOC.
§ These are in contrast to the cases for PCBs and BDE209.
y = -0.066x + 3.327 R² = 0.671
-2
-1
0
1
2
3
4
0 20 40 60 80
Ln R
ecen
t Flu
x, u
g/cm
2-yr
TOC, mg/g
Category-I
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Category II
§ Includes 36-‐BCZ, 136-‐BCZ, UNC-‐3, UNC-‐6, UNC-‐10, and 1-‐B-‐36-‐CCZ. • No more than 3 halogens • CounNng 36% of total Σ26PHCZ
1550 1600 1650 1700 1750 1800 1850 1900 1950 2000 2050
0.0 0.5 1.0 1.5 2.0
136-BCZ
§ More even spaNal distribuNon than Cat-‐I, some are high in southern Lake Huron.
§ Temporal trend is similar to Cat-‐I, except the recent increase.
§ Weaker correlaNon with water depth than Cat-‐I
§ Recent input flux decreases from south to north, similar to anthropogenic pollutants such as PCBs, PBDEs, etc.
– Emerging Concerns!
Dependence on LaKtude
§ The recent fluxes (but not inventory) depend log-‐linearly on the laNtude of the sampling locaNons over the three lakes: • Cat-‐II: R2 = 0.85, p = 10-‐6 • In sharp contrast with Cat-‐I (R2 = 0.06, p = 0.42). • Similar to industrial pollutants such as BDE209 (r = -‐0.89, p < 10-‐8) and PCBs (r = -‐0.76, p < 10-‐4).
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1550
1600
1650
1700
1750
1800
1850
1900
1950
2000
2050 0.0 0.1 0.2 0.3 0.4 0.5
3-CCZ
§ 3-‐CCZ, 3-‐BCZ, and 36-‐CCZ • contribuNng <5% of Σ26.
§ ConcentraNons tend to be higher in deeper sediment.
§ DehalogenaNon is known to have occurred in sediment where anaerobic condiNons prevail. For example, PCBs show a clear sign of dechlorinaNon, as the fracNons of less chlorinated homologs increase with depth of sediments
Category III – formed from dehalogenaNon?
Summary § 26 PHCZs were detected, and
their total accumulaNon of in the upper Great Lakes is around 3,000 tonnes.
§ The dominant sources are likely to differ among individual PHCZs, and they are also locaNon-‐ and Nme-‐ dependent.
1
10
100
1000
10000
Cab
azol
e
Cat
-I
Cat
-II
Cat
-III
ΣPH
CZs
BD
E209
t-PC
Bs
tonn
e
Lake Michigan
§ Category I – unlikely to relate to modern industries § Category II – have natural origin but should be of emerging
concerns and be invesNgated for industrial emissions § Category III – both natural and industrial sources are likely
§ This work shows the complexity of the sources and illustrates the intertwinement of natural and human impacts.
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Acknowledgment to my teammates
Acknowledgement § We thank the Captain and
crew of R/V Lake Guardian for their assistance in sediment sampling.
§ This work has been supported by the U.S. Environmental ProtecNon Agency (No. GL-‐00E00538), the University of Illinois at Chicago, and the University of Saskatchewan.
§ … and thank you for listening!