Studies on ice core records of dicarboxylic acids, ω-oxocarboxylic acids, pyruvic acid, α

246 Pages·2017·3.01 MB·English

by  Pokhrel, Ambarish

Studies on ice core records of dicarboxylic acids, ω-oxocarboxylic acids, pyruvic acid, α-dicarbonyls and fatty acids
Title
from southern Alaska since 1665 AD : A link to climate change in the Northern Hemisphere
Author(s) Pokhrel, Ambarish
Citation 北海道大学. 博士(環境科学) 甲第11786号
Issue Date 2015-03-25
DOI 10.14943/doctoral.k11786
Doc URL http://hdl.handle.net/2115/59331
Type theses (doctoral)
File Information Ambarish_Pokhrel.pdf

Instructions for use
Hokkaido University Collection of Scholarly and Academic Papers : HUSCAP
Studies on ice core records of dicarboxylic acids, ωωωω−−−−oxocarboxylic
acids, pyruvic acid, αααα-dicarbonyls and fatty acids from southern
Alaska since 1665AD: A link to climate change in the Northern
Hemispehre

By
Ambarish Pokhrel
ID:76125006

Doctorate Dissertation
Division of Earth System Sciences
Graduate School of Environmental Sciences
Hokkaido University, Japan
2015
A dissertation submitted for the partial fulfillment of the degree in
Environmental Science

Acknowledgement
This PhD thesis “Studies on ice core records of dicarboxylic acids,
ω−oxocarboxylic acids, pyruvic acid, α-dicarbonyls and fatty acids from southern
Alaska since 1665AD: A link to climate change in the Northern Hemispehre” was
done in Kawamura’s Lab, at Institute of Low Temperature Science, Hokkaido
University. This work was supported by ice core program of the Institute of Low
Temperature Science (ILTs), Hokkaido University (Shiraiwa’s ice core group), Japan
Society for the Promotion of Science through Grant-in-Aid No. 19340137 and
24221001, and Japan Student Service Organization (JASSO).
I would like to express my sincere gratefulness to my supervisor Prof. Kimitaka
Kawamura, ILTs for providing me opportunity to work on this topic and his critical
comments and suggestions during preparation this thesis and research articles. Again,
I am indebted to Professor Kawamura for providing tons of knowledge, answering my
queries during my study. It is my pleasure to thank Associate Prof. O. Seki and Asst.
Prof. Y. Miyazaki for their invaluable guidance and suggestions about my study
during group seminars.
In addition, my sincere thanks goes to scientist Dr. Chandra Mauli Pavuluri,
colleagues and technical staff Eri Tachibbana and K. Ono for their constant supports.
I especially thank my grandmother Karna Kumaree Pokhrel, grandfather Chandra
Kant Pokhrel, father Ram Chandra Pokhrel, mother Chitrakala Pokhrel and my other
family members for their continuous supports in my education. I am also very grateful
to my wife, Dr. Bhagawati Kunwar, ILTs and my small son Abhinav Bhusan Pokhrel
for their great courage and energy in the past few years; they always supported my
thoughts and released the pressure of work off me. All this made me enjoy my
research very much. There are many others that I didn’t manage to mention in this
short acknowledgement. I thank to all.
The work of this Ph. D. thesis belongs to all human beings!

Abstract
Alaskan ice core (180 m long, 343 years) has been analyzed for a homologous
series of normal (C - C ), branched chain (iC - iC ), unsaturated (maleic, fumaric,
2 11 4 6
methylmaleic and phthalic), multifunctional dicarboxylic (malic, oxomalonic and 4-
oxopimelic), ω-oxocarboxylic acids (ωC - ωC ), pyruvic acid, glyoxal and
2 9
methylglyoxal using gas chromatography (GC/FID) and GC/mass spectrometry
(GC/MS) to understand historical changes in water soluble organic aerosols.
Similarly, homologous series of straight chain fatty acids (C - C ) has been
12:0 30:0
detected by using GC/FID and GC/MS system.
Predominance of oxalic acid was found followed by adipic and succinic acid.
Molecular distributions of ω-oxocarboxylic acids are characterized by the
predominance of 9-oxononanoic, followed by 4-oxobutanoic and glyoxylic acids.
Historical concentrations of diacids, oxoacids and α-dicarbonyls are formed by the
oxidation of precursor compounds emitted from biogenic and biomass burning
activities and which are controlled under climate oscillations and similar
meteorological parameters. Historical trends of monoterpene and isoprene SOA
tracers showed significant concentrations since the 1660s, which are associated with
ambient atmospheric temperature and controlled by Aleutine Low.
Molecular distributions of fatty acids are characterized by even carbon number
predominance with a peak at palmitic (C ) followed by oleic (C ) and myristic
16:0 18:1
acid (C ). The historical trends of short-chain fatty acids, together with correlation
14:0
analysis with inorganic ions and organic tracers suggest that short-chain fatty acids
(except for C and C ) were mainly derived from sea surface micro layers. In
12:0 15:0
contrast, long-chain fatty acids (C - C ) are originated from terrestrial higher
20:0 30:0
plants, soil organic matter and dusts, which are also linked with Greenland
Temperature Anomaly (GTA). Hence, this study suggests that Alaskan fatty acids are
strongly influenced by Pacific Decadal Oscillation/North Pacific Gyre Oscillation
and/or extra tropical North Pacific surface climate and Arctic Oscillation.
Organic tracers in ice core were derivatized with N,O-bis-(trimethylsilyl)
trifluoroacetamide (BSTFA) with 1% trimethylsilyl chloride (TMCS) and pyridine
and the derivatives were analyzed using GC/MS system. Levoglucosan,
dehydroabietic and vanillic acid showed higher concentration with many sporadic
peaks since 1660s-1830s, 1913, and 2005. Moreover, there are a few discrepancies of
higher spikes among them after 1980s with sporadic peaks in 1994-2007 for
dehydroabietic acid. Historical trends of levoglucosan, dehydroabietic and vanillic
acid showed that biomass burning activities from resin and lignin phenols from boreal
conifer trees and other higher plants and grasses were significant before 1840s and
after 1980s in the source regions of southern Alaska.
Nitrite (NO -), nitrate (NO -), sulfate (SO 2-) and methanesulfonate (CH SO -)
2 3 4 3 3
were determined for an ice core of the Aurora Peak in southeast Alaska using ion
chromatograph. They have common periods for higher spike during the years 1665-
2008. They are attributed to the same source regions and similar pathways.
Interestingly, we found multi-decadal scale atmospheric transport from lower to
higher latitudes in the North Pacific, which is reflected in historical concentration
trends of anions. Moreover, correlation of levoglucosan with NH +, NO - , SO 2- and
4 3 4
NO - suggests that these anions and cations are poor tracer of biomass burning
2
activities in the source regions of southern Alaska. Hence, this study revels a new
dimension of anions periodic cycles in the North Paficic region, which may alter the
concept of other ice core studies in the Northern and Southern Hemisphere.
Table of Contents
Acknowledgement
Abstract

Chapter 1. Introduction 1
1.1. Ice Core Study 1
1.2. Importance of Paleoclimate 3
1.3. Atmospheric Aerosol for an Ice Core 4
1.4. Aging for an Ice Cores 8
1.5. Purpose of this Study 9
References

Chapter 2. Ice core records of dicarboxylic acids, ωωωω-oxocarboxylic acids, 17
pyruvic acid and αααα-dicarbonyls from south Alaska: Implications
for climate change in the Northern Hemisphere since 1660s
2.1. Introduction 17
2.2.1. Site Description 18
2.2.2. Chemical Analysis 18
2.2.3. Backward Air Mass Trajectories 19
2.3. Results and Discussion 20
2.3.1. Correlation Analysis: Possible Sources and Formation 20
Mechanism
2.3.2. Principal Component Analysis for Selected Organic 21
Compounds
2.3.3. Historical Changes in the Concentration of Dicarboxylic 22
Acids
2.3.3.1. Shorter-Chain Diacids: Possible Sources and Formation 22
Mechanism
2.3.3.2. Longer-Chain Diacids: Possible Sources and Formation 25
Mechanism
2.3.3.3. Branched Chain Saturated and Unsaturated 27
Dicarboxylic Acids
2.3.3.4. Aromatic and Multifunctional Diacids: Possible Sources 28
and Formation Mechanism
2.3.3.5. ω-Oxoacids and Pyruvic Acid: Possible Sources and 29
Formation Mechanism
2.3.3.6. α-Dicarbonyls: Possible Sources and Formation 32
Mechanism
2.3.4. Contributions of Diacids and Related Compounds to WSOC 33
2.3.5. Response of Ice Core Organic Tracers to Non Periodic 35
Events
2.3.6. Response of Ice Core Organic Tracers to Lower Tropospheric 36
Temperature
2.3.7. Response of Ice Core Organic Tracers to Climate Oscillations 38
2.4. Conclusions 40
References
Chapter 3. Ice core profiles of saturated fatty acids (C - C ) and oleic 70
12:0 30:0
acid (C ) from southern Alaska since 1660s: A link to climate
18:1
change in the Northern Hemisphere
3.1. Introduction 70
3.2. Ice Core Samples and Analytical Procedures 71
3.3. Results 72
3.4. Discussion 73
3.4.1. Molecular compositions of fatty acids and their historical 73
profile
3.4.2. Multiple Responses of Alaskan Ice Core to Climate Change 77
3.5. Conclusions 82
References

Chapter 4. Ice core records of biomass burning organic tracers in the 96
Aurora Peak of Alaska since 1660s: Implications for forest fire
activities in the Northern Hemisphere
4.1. Introduction 96
4.2. Samples and Analytical Procedures 97
4.3. Result and Discussion 98
4.3.1. Levoglucosan 99
4.3.2. Dehydroabietic acid 104
4.3.3. Vanillic acid 107
4.4. Comparision with Ammonium, Nitrite, Nitrate and Sulfate 108
4.5. Conclusions 109
References

Chapter 5. The pristine atmospheric signal recorded in NO -, NO -, SO 2- 119
2 3 4
and methanesulfonate (CH SO -) from Aurora Peak of Alaskan
3 3
ice core records (1665-2008): Implications for climate change in
the Northern Hemisphere
5.1. Introduction 119
5.2. Samples and Analytical Procedures 120
5.3. Results and Discussion 121
5.3.1. Historical Concentration Changes of NO - 121
3
5.3.2. Historical Concentration Changes of NO - 128
2
5.3.3. Historical Concentration Changes of SO 2- 130
4
5.3.4. Comparison to Open Ocean Water and Ice Core Records of 133
Nitrogen Species
5.3.5. Comparison to biomass burning tracer of ice core records 135
5.3.6. Historical Concentration Changes of MSA- 137
5.4. Responses of Alaskan ice core to climate change 139
5.5. Conclusions 139
References
Chapter 6. Ice core records of biogenic secondary organic tracers from
isoprene and monoterpenes from Aurora Peak in Alaska since 156
1660s
6.1. Introduction 156
6.2. Samples and Analytical Procedures 157
6.2.1. Site Description 157
6.2.2. Chemical Analysis 158
6.3. Results and Discussion 159
6.3.1. Historical Concentrations of Monoterpene Tracers 159
6.3.2. Historical concentrations of isoprene SOA tracers 162
6.4. Response of Ice Core Monoterpene and isoprene SOA Tracers and 164
Lower Tropospheric Temperature
6.5. Conclusions 169
References

Chapter 7. Climate signal recorded in dicarboxylic acids, 179
ketocarboxylic acids and α-dicarbonyls from the Kamchatka-
Peninsula (300 yrs) for an ice core: Climate change implications in
the Northern Hemisphere

7.1. Introduction 179
7.2. Samples and Analytical Procedures 180
7.3. Results 182
7.3.1. Molecular Composition and Concentration of Organic 182
Compounds
7.3.2. Historical Concentration Changes of Organic Compounds 183
7.4. Discussion 184
7.4.1. Correlation Analyses: Possible Sources and Formation 184
Mechanism
7.4.2. Principal Component Analyses 185
7.4.3. Origin of Dicarboxylic Acids, Ketocarboxylic Acids and 185
α−Dicarbonyls
7.4.3.1. Shorter-Chain Diacids (C -C ) 186
2 4
7.4.3.2. Longer-Chain Diacids (C -C ) and Related Compounds 189
5 12
7.4.3.3. ω-oxocarboxylic (ωC -ωC ) and Pyruvic acid 193
2 9
7.4.3.4. Glyoxal and Methylglyoxal 195
7.4.4. Climatic Window and Response of Organic Compounds 196
7.4.4.1. Response of Ambient Atmospheric Temperature 197
7.4.4.2. Response of Solar Irradiance 198
7.4.4.3. Response of Greenland Temperature Anomaly 200
7.5. Conclusions 204
References

Chapter 8. Summary and Conclusions 231