Envir Chem at KMUTT-JGSEE

1
Envir Chem at KMUTT-JGSEE Jun. Sept., 09

• Time
• Location
•               
• http//www.unc.edu/courses/2009fall/enst/430/001/
  
• Rich Kamens
• kamens_at_unc.edu
• http//www.unc.edu/kamens/

2

• Textbook
• Environmental Chemistry by Colin Beard and
  Michael Cann, ISBN gt ISBN-13 978-1-4292-0146-0 ,
  publishers W.H. Freeman and Company, New York,
  773 pages, 2008

3
Who is Richard Kamens

• Professor of Atmospheric chemistry and teach
  graduate classes in Environmental chemistry
• Direct a smog chamber research group
• Focus on aerosol formation in the atmosphere
• Direct a student exchange program between UNC and
  Thai Universities

4
UNC outdoor chamber
5
Gas/Particle partitioning of toxics organics on
different aerosols
6
New UNC Aerosol Smog Chamber
7
Dual 270m3 chamber fine particle t 1/2 gt17 h
8
We generate models to predict organic aerosol
formation in the atmosphere from smog chamber
experiments

• Numerical fitting
• Semi-explicit

9
Link gas and particle phases
10

• igas part ipart

Kp kon/koff
11

Mechanism
12

pinonaldehyde
13
Overall kinetic Mechanism

• linked gas and particle phase rate expressions

14


15
Chemical System

NOx sunlight ozone----gt aerosols
a-pinene
16

0.95 ppm a-pinene 0. 44ppm NOx
17

Gas phase pinonaldehdye
Time in hours EST
18

Measured particle mass vs. model
Particle phase
Particle phase
data
3
mg/m
model TSP
model TSP
Time in hours EST
19
UNC outdoor chamber group
20
The Thai-CEP Undergraduate/Graduate Exchange
Program
The UNC-Thailand Field site

• Pollution does not understand boarders.
• We must begin to address these problems from both
  inside and outside ones culture.

21
General Approach

• Since 2001, UNC-CEP undergraduates participated
  in a 6 month experience in Thailand that begins
  at the end of May 2001
• Small groups of UNC students come together with
  Thai students to study and work on a research
  project at various Thai universities.
• Thai students will go back with UNC students for
  a semester at UNC.

22
Classes

• UNC students take 3 direct contact/web-based
  environmental classes
• Atmospheric and ecotoxicology
• LCA
• Energy and the Environment
• Climate Change and Eco
• Biomass and Energy
• Energy and the Environ

23
Feasibility of Ethanol Use and an Energy
Analysis and Environmental Impact of Ethanol in
ThailandKMUTT 2001- 2002
24
The Feasibility of Bio-diesel Production as
Petroleum Substitute in Thailand KMUTT 2004
Energy balance Used vegetable oil Production
from Jatropha
25
Water Quality ReportMae Kha Canal Ping River
CMU, Chiang Mai, 2004
26
(No Transcript)
27
(No Transcript)
28
(No Transcript)
29
(No Transcript)
30
(No Transcript)
31
(No Transcript)
32
(No Transcript)
33
Long standing relationship with Peking
Universityand CRAESSince 1983 there were 13
visiting Chinese scholars in our research group
at UNC
34
Introduction to Environmental Physical Organic
Chemistry

• Environmental chemistry may be defined as "the
  study of sources, reactions, transport, effects,
  and fates of chemical species in water, soil, and
  air environments, and the effects of technology
  thereon. Manahan, 1994

35
Class objectives

• Highlight some important areas in environmental
  chemistry
• present some of the common techniques that
  environmental chemists use to quantify process
  that occur in the environment
• It is assumed that everyone has courses in
  organic and physical chemistry.

36
Class objectives

• We will cover general topics Global warming,
  Strat. O3, aerosols, photochemical smog, acid
  rain, etc.
• Develop relationships will be used to help
  quantify equilibrium and kinetic processes

37
Thermodynamics

• ui uo1 RT ln pi/piL
• fi ?i Xipipure liquid
• RT ln fi hx /fiopure liq RT lnfi H2O /fiopure
  liqfi hx fi H2O
• ln Kp a 1/Tb

38
Vapor pressure
How to calculate boiling points
39
Vapor pressure and Henrys law
sat
P
sat
sat

?
?
?
i
K
P
V
iL
iw
sat
iaw
iw
C
iw
Solubility and activity coefficients Octanol-wate
r partitioning coefficients
40
Homework, quizzes, exams

• There will be example homework exercises These
  types of questions will appear on exams.

41
Why the interest?

• There are more than 100,000 synthetic chemicals
  that are in daily use
• solvents
• components of detergents
• dyes and varnishes
• additives in plastics and textiles
• chemicals used for construction
• antifouling agents
• herbicides, insecticides,fungicides

42
Some examples of environmental chemicals

• Polynuclear Aromatic HC (PAHs)
• Dioxins
• Ketones
• PCBs
• CFCs
• DDT
• O3, NO2, aerosols, SO2

43
PAHs

• Formed from small ethylene radicals building
  blocks produced when carbon based fuels are
  burned
• Sources are all types of burning
• in ChiangMai, Thailand a) 2-stroke
  motorcycle engines b) cars- light
  diesels c) open burning d) barbecued
  meat??

44
Combustion Formation of PAH
Badger and Spotswood 1960
45
PAHs

• Metabolized to epoxides which are carcinogenic O
  PAH
• are indirect acting mutagens in bacterial
  mutagenicity tests (Ames-TA98s9)
• methyl PAHs are often more biologically active
  than PAHs

46
Carcinogenic tests with PAHs

• Professor Gernot Grimmer extracted different
  types of smoke particles
• He then took the extract and applied it to mouse
  skin
• and implanted it into rat lungs
• How did he obtain extracts?
• How did he fractionate his extracts??

47

• Extraction by soxhlet extraction starts with
  solvent (MeCl2) in a flask

48

• Extraction by soxhlet extraction starts with
  solvent (MeCl2) in a flask

MeCl2
49

• The solvent is heated and starts to evaporate

Heat
50

• Evaporated solvent goes into a water cooled
  condenser where hot solvent drips out

Heat
51

• The hot solvent drips into another glass chamber
  that contains the filter.

sample
Heat
52

• Hot solvent fills this chamber and bathes the
  filter

Heat
53

• The solvent in the filter chamber then drains
  back into the heated flask withchemicalsfrom
  the particleson the filter

Heat
54

• The organic liquid in the soxhlet flask can be
  concentrated by evaporation by a dry nitrogen
  stream or rotary evaporation
• the extract can then be fractionated into
  different polarity compound groups

55
Professor Grimmer fractionated the exhaust
extracts
56
Professor Grimmer fractionated the exhaust
extracts
HPLC
column (silica gel)
57
Professor Grimmer fractionated the exhaust
extracts
HPLC
hexane
MeCl2
58
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
hexane
MeCl2
59
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
Totalextract
hexane
MeCl2
60
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
Total
hexane
PAH 23 rings
61
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
Total
hexane
MeCl2
PAHsgt3 rings
62
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
Total
ACN
Total-PAHs
63
Professor Grimmer fractionated the exhaust
extracts
HPLC
uv orfluorescencedetector
Total
Total
PAH 23 rings
PAHsgt3 rings
Total-PAHs
64
What did Grimmer see when exposed rats and mice
to the different fractions?

• skin painted mice
• implanted rat lungs

65
(No Transcript)
66
Total minus the PAH fraction
67
(No Transcript)
68
(No Transcript)
69
Chlorinated dibenzo dioxins and Furans

• These are some of the most toxic organics in the
  environment - LD50
• Created by burning organics which have chlorine
  incineration is a big source of atmospheric
  dioxins and furans
• bleaching in making paper is another source

70
Combustion Formation of Dioxins from
Polychlorinated phenol
O
H
Clx
.
OH
Clx
Flame
.
O
O
H

Polychlorinated
Phenol
C
l
y
O
OH
O
Cly
Cly
Clx
O
Clx
O
H
Chlorinated dibenzo dioxin
Shaub Tsang, EST 1983.
71
They have the following general structures
O
Cl
x
O
Cl
y
chlorinated dioxin
72
They have the following general structures
O
Cl
x
O
Cl
y
chlorinated dioxin
O
chlorinated furan
73
More than 200 different structures are possible

• The most toxic is either the 2,3,7,8
  tetrachlorodibeno dioxin and furans

74

• These types of compounds produce toxic enzymes
  arylhydrocarbon hydroxylase and 7-ethoxyresorufin
  deethylase
• At low concentrations they may behave as
  environmental estrogens

75

• Environmentally, they are unreactive and can be
  transported long distances
• They did not start to show up in the environment
  until the 1920s when there was a big increase in
  the production of chloro-organics (Professor Ron
  Hites, and students)

76
Environmental Fate of Chlorinated Dioxins and
Furans(Czuczwa and Hites, 1984)

• Collected core sediment samples from southern
  Lake Huron in the USA
• Based on sedimentation rates they established age
  vs. concentration profiles for chlorinated
  dioxins and furans

77
US coal consumption vs chlorinated aromatic
production
78
Chlorinated aromatic production vs dioxinand
furan conc. in lake core samples
79
Polychlorinated biphenyls (PCBs)

• used as coolants - insulation fluids in
  transformers, capacitors , plastercisers,
  additives to epoxy paints
• are thermally stable and biologically stable
• can exist in the gas and particle phases

80
PCB structures

• Environmentally, they used to be considered
  unreactive, but there is evidence for some
  bio-degradation they can be transported long
  distances

81
What do we do now, when new compounds are
introduced into the environment...??

• toxicity??
• low concentration health effects?
• damage to the ecosystem ?
• where will it show up in the environment?
• how is it transported in the environment and what
  is its life-time?

82
Some examples of environmental exposures
83
1. There is a general concern that if we observe
abnormalities in wildlife, similar kinds of
mechanisms may exist in humans.
84
Mercury poisoning off the coast of Minamata,
Japan is an example

• Fishermen in the 1950s noticed sea birds were
  dying and feral cats that scavenged fish from the
  docks were stiff legged(see page 675 Baird and
  Cann,2008)
• Cerebral palsy and mental retardation started
  showing up in children.

85
2. Toxic loads

• Scientists have hypothesized that the fetus is
  sharing the mothers toxic load, and may actually
  provide some protection to the mother by reducing
  her internal exposure.

86
2. Toxic loads

• Children get 12 of their lifetime exposure to
  dioxins during the 1st year.
• Their exposure is 50 times greater than an adult
  during a very critical developmental period.

87
2. Toxic loads

• Firstborns from dolphins off the coast of Florida
  usually die before they separate from their
  mothers

88
2. Toxic loads

• It is speculated that mother dolphins unload 80
  of their accumulated pollutants into their
  calves, probably during nursing.
• The greatest exposures occurs with the 1st born
• Does this have any implications for humans?

89
3. Pesticide exposures

• Children of farm families in the western
  Minnesota area of the US have significantly
  higher rates of birth defects than the general
  population.
• The highest rates are among children conceived
  in the spring when spraying of pesticides is most
  intense male babies had far more birth defects
  than females

90
4. The end points may not only be cancer, but
compromised immune systems and generally poorer
health.
91
4. Immune systems Mothers milk

• In the Netherlands researchers have found that
  children with higher levels of dioxins and PCBs
  in their bodies have more health problems (immune
  system and hormonal changes) than children with
  lower levels.
• This was linked to levels of PCBs in Mothers
  milk.

92
4. Mothers milk

• Mothers milk from Inuit Indians in the Canadian
  Arctic has 7 times the PCBs as mothers milk from
  women in the urban industrialized areas of
  southern Quebec.

93
4. Mothers milk

• During the first year, Inuit babies suffer
  through 20 times more colds than babies in
  southern Quebec.
• Acute ear infections are rampant.

94
4. Mothers milk

• Babies nursed by mothers with the highest
  contamination levels in their milk are afflicted
  with more acute ear infections than bottle fed
  Inuit babies.
• Many of these children dont seem to produce
  enough antibodies for childhood vaccinations to
  take.

95
5. PCBs and lower intelligence

• There is evidence of lower intelligence in
  babies exposed to PCBs.
• In adults, a blood-brain barrier insulates the
  brain from many potentially harmful chemicals
  circulating through the body
• In a human child this barrier is not fully
  developed until 6 months after birth.

96
5. PCBs and lower intelligence

• In 1979 in Taiwan, more than 2000 people were
  exposed to PCB-contaminated cooking oil.
• In the 1st 3 months many babies died outright.
  As the surviving children grew up, many were
  slower intellectually than other kids their age,
  were hyperactive and had behavioral problems.

97
5. PCBs and lower intelligence

• Similar observations were made in "high-PCB
  kids" in the Lake Michigan area.
• This was associated with mothers eating salmon
  and trout from the Lake during the years before
  their children were born.

98
5. PCBs and lower intelligence

• At age 4 the high exposure group had poor short
  term memories. At age 11 the 30 most highly
  exposed kids had average IQ scores that were 6
  points lower than the lowest-exposed group.
• biomarker-metabolites???

99
7. Sexual impairment

• There is evidence for sexual impairment in both
  animals and humans from high PCB exposures and
  other environmental chemicals.
• Male beluga whales in the very polluted St.
  Lawrence River have exhibited female organs.

100
7. Sexual impairment

• Highly exposed humans, alligators and panthers
  exhibit smaller male sex organs and low sperm
  counts.
• Testicular cancers have nearly doubled among
  older teenagers in the US between 1973 and 1992.
• In previous lectures I have said these have been
  linked to toxic exposures....long way from
  finding proof.

101
7a. Sexual impairment

• In a new study (Hardwell et al, Environ Presp,
  2003) woman whove had substantial exposure to
  certain environmental pollutants are more likely
  to bear sons who develop testicular cancers (men
  30 years of age)
• From 1973-1999 testicular cancers up 67
• Men with test-cancers had high cis nona
  chloridane, not PCBs, etc
• Mothers, however, had high PCBs, HCB
  (hexa-chlorobenzenes) and cis nona chloridane

102
7b. Sexual impairment

• These same mothers probably had high exposures
  when environmental contaminates peaked in
  Scandinavia in the 1970s
• Richard Sharpe of Edinburogh and Niels Skakkebek
  (Denmark) proposed that exposure to endocrine
  disruptors before birth can alter testicular-cell
  development and some of these cells may be
  cancerous after puberty.
• This may also may explain rising rates of male
  infertility, and other sexual deformities

103
8. Endocrine disrupters

• These studies have led to the notion of
  environmental "endocrine disrupters".
• In the lock and key relationship between hormone
  and receptor molecules, these "hormone impostors"
  can

104
8. Endocrine disrupters

• bind with receptors and trigger biological
  processes
• or bind with receptors and tie up an active
  hormone site
• Some of these have been called environmental
  estrogens

105
9. Other chemicals

• From a historical perspective, everyone is now
  carrying at last 250 measurable chemicals that
  were not part of human chemistry before the 1920s
  (Peter Myers, 1996)
• The most basic toxicity testing results cannot be
  found in the public record for nearly 75 of the
  top volume chemicals in commercial use in the USA

106
9. Other chemicals

• In other words, the public cannot tell whether a
  large majority of the highest-use chemicals in
  the United States pose health hazards or not
  (Amicus Journal, p23, Spring 1998).
• An example are phthalates that go into many types
  of plastics which have been shown to reduce the
  sperm counts in mice.

107
9. Other chemicals

• Bisphenol-A (BPA) is an additive in polycarbonate
  plastics used in food liners, dental sealants,
  and dental fillings.
• BPA causes increased prostate size in mice
  exposed to tiny doses while in the womb. These
  doses were 25,000 times smaller than the EPA
  threshold.

108
9. Phthalates

• Exposure of female rates to 200 to 1000 mg/kg
  body weight results in much lower testosterone in
  male offspring( L. Earl Gray. Jr. EPA, RTP, J.
  Tox and Ind. Health, Mar, 1999).
• Exposures to the herbicide linuron made the
  epididymis (sperm-storing organ in rats) is much
  smaller in male rats.

109
epididymus
110
Recommendations

• During the insecticide spraying season, farmers
  should not try to have children.
• Limit exposures to pesticides around the home.
• When possible, buy foods that were grown without
  pesticides.
• Governments must try to limit PCB introduction
  into the environment.
• If incineration is used, chlorinated plastics
  should be removed, along with modern technology.