1 Envir Chem at KMUTT-JGSEE – June –Sept 08 Time: Location: Rich Kamens; 087 089 1520...

1

Envir Chem at KMUTT-JGSEE – June –Sept 08

Time: Location:

http://www.unc.edu/courses/2008fall/enst/110/001/

Rich Kamens; 087 089 1520 [email protected] http://www.unc.edu/~kamens/

http://www.unc.edu/courses/2008fall/enst/110/001/

mailto:[email protected]





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Textbook Environmental Chemistry by

Colin Beard and Michael Cann, ISBN > 0-7167-4877-0, publishers W.H. Freeman and Company, New York, 652 pages, 2005

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 >17 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

C=OO

cis-pinonaldhyde

particleC=OO

Gas phase reactions

TSPC

CK

gasi

parti

p

10

[ [ iigasgas] + [part] ] + [part] [ [ iipartpart]]

K

R T

p M wpLo

7 5 0 1

1 0 9

. fom

Kp = kon/koff

kon

koff

particle

kon

koff

C=OO

11

CHOOO

CH3

OO

O

Criegee2

Criegee1OO O

-pinene

O3

COOHCOOH

pinic acid

+ otherproducts

O

pinonic acid

CHOO

COOH

+ CO, HO2, OH

COOHO

norpinonaldehyde

norpinonic acid

Mechanism

12

pinonaldehyde

OH

OO

O2

+

(a)(b)

(c)

(d)

(e)

pinonaldehyde

acetone

O

OO.

NO2NO

O

O.

pinald-oo

OH

pinonic acid

O

pinO2

OO.

NO2

NO

organic nitrate

+HO2

+NO2

pinald-PAN

=o

=o

=o

=o

=o

=o

=o

OO.

O2

=o

OO=C8=O

C8-oo.

O2

NO2NO

O

+ h

+

+CO+HO2=o

OO.

NO2NO

=o

=o+HO2

+ h

NO2NO

=o

OO.

C8-oo. (C8O2)

+CO+HO2

NO2

NO

(f)

(g)

CO2+

pinO2H2O+

+HO2

O2

OO

H3C-OO.

+oxygenated products

+NO2

+H3C-OONO2PAN

(stab-oxy)

+HO2

norpinonaldehyde

OOH

O=o+

pin-ooH

+OH

O

OO.

=o

NO2

NO

+CO2

norpinaldPAN

+NO2

+HO2

norpinonic acid+norpin-ooH

O

OONO2

=o

+O2

ONO2

=o

+

=o

ONO2

+

organic nitrate

13

Overall kinetic Mechanism

linked gas and particle phase rate expressions

14

15

Chemical System

-pinene

+ NOx+ sunlight + ozone----> aerosols

16

0.95 ppm -pinene + 0. 44ppm NOx

O3NO

NO2

NO2

model

data

Time in hours EST

pp

mV

17

Gas phase pinonaldehdye

OO

mg

/m3

Time in hours EST

18

Particle phase

model TSP

mg

/m3

Particle phase

model TSP

mg

/m3

Measured particle mass vs. model

data

Time in hours EST

19

UNC outdoor chamber group

20

The Thai-CEP Undergraduate/Graduate Exchange Program

• 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.

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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

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Feasibility of Ethanol Use and an Energy Analysis and Environmental Impact of Ethanol in Thailand:KMUTT 2001- 2002

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The Feasibility of Bio-diesel Production as Petroleum Substitute in Thailand : KMUTT 2004

Energy balance

Used vegetable oil

Production from Jatropha

25

Water Quality Report:Mae Kha Canal & Ping River: CMU, Chiang Mai, 2004

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Air Pollution in Northern

Thailand

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28

29

0

50

100

150

200

250

300 u

g/m

3

12-Ma20-Ma

28-Ma05-Ap

13-Ap21-Ap

29-Ap05/07

05/15

PM2.5 standard Nui

PM2.5 concentrations

30

31

32

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Long standing relationship with Peking Universityand CRAES

Since 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

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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.

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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

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Thermodynamics

ui = uo1 +RT ln pi/p*

iL

fi = i Xipi*pure liquid

RT ln fi hx /fio

pure liq = RT lnfi H2O /fi

opure liq

fi hx = fi H2O

ln Kp = a 1/T+b

38amb

ambmfusiL T

TT

R

Spp is

)()(lnln **

Vapor pressure

)]()( ln.*lnT

T

T

Tp bbiL 58119

How to calculate boiling points

39

Vapor pressure and Henry’s law

KPC

P Viawi

iwiw

satsat

satsat

iL*

iw

Solubility and activity coefficients

Octanol-water partitioning coefficients

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Homework, quizzes, exams To insure that most of us stay

reasonably current with the lectures and readings, an option is to have 8-10 unannounced quizzes throughout the semester.

They will take ~10 minutes. Quizzes will count 20% of your grade.

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Another option is a set of short questions to be answered and handed in before most lectures (20% of your grade)—your choice!

42

There will be a homework problem set associated with each assigned chapter of the book.

These problem sets should take between 1 and 3 hrs.

43

Some of these could appear on exams

There will be two exams

There are more than 70,000 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

Why the interest?

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

Some examples of environmental chemicals

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??

PAHs

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Combustion Formation of PAH

Badger and Spotswood 1960

(I) (II) (III) (IV)

C

C

C

C

C

C

CC

CC

CC

(VII) (VI) (V)

Benzo a Pyrene

Metabolized to epoxides which are carcinogenic; O PAH

are indirect acting mutagens in bacterial mutagenicity tests (Ames-TA98+s9)

methyl PAHs are often more biologically active than PAHs

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??

Carcinogenic tests with PAHs

50

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

51

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

MeCl2

52

The solvent is heated and starts to evaporate

Heat

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

Heat

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

Heat

sample

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Hot solvent fills this chamber and bathes the filter

Heat

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

Heat

57

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

58

Professor Grimmer fractionated the exhaust extracts

59


HPLC

column (silica gel)

60


HPLC

hexane MeCl2

61


HPLC

hexane MeCl2

uv orfluorescencedetector

62


HPLCTotalextract

hexane MeCl2


63


HPLC

PAH 2&3 rings

Total

hexane


64


HPLCTotal

PAHs>3 rings

hexane MeCl2


65


HPLCTotal

Total-PAHs


ACN

66


HPLC

PAH 2&3 rings

Total

PAHs>3 rings

Total

Total-PAHs


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skin painted mice implanted rat lungs

What did Grimmer see when exposed rats and mice to the different fractions?

0

10

20

30

40 %

can

cers

TotalTotal-PAHs

PAHs 2&3 ringsPAHs > 3 rings

rat lungs Mouse-skin

0

10

20

30

40 %

can

cers

TotalTotal-PAHs



Total minus the PAH fraction

0

10

20

30

40 %

can

cers

TotalTotal-PAHs



0

10

20

30

40 %

can

cers

TotalTotal-PAHs



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

Chlorinated dibenzo dioxins and Furans

73

Combustion Formation of Dioxins from Polychlorinated phenol

O H

PolychlorinatedPhenol

Flame

OH .

.OO H

C ly

+

O

O H

+ OH

Chlorinated dibenzo dioxin

ClxO

O

Shaub & Tsang, ES&T 1983.

Cly

Clx

ClxCly

Clx

They have the following general structures

O

O Clx

Cly chlorinated dioxin

They have the following general structures

O

O Clx

Cly chlorinated dioxin

O Clx

Cly chlorinated furan

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

More than 200 different structures are possible

O

O

Cl

Cl

Cl

Cl

These types of compounds produce toxic enzymes: arylhydrocarbon hydroxylase and 7-ethoxyresorufin deethylase

At low concentrations they may behave as environmental estrogens

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)

79

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

80

US coal consumption vs chlorinated aromatic production

0

100

200

300

400

500

600

700 U

S c

oal

in 1

0^6

shor

t-to

ns

0

200

400

600

800

10^6

lbs

Cl-a

rom

atic

s

1860 1880 1900 1920 1940 1960 1980

Year

Coal

chloro-aromatics

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Chlorinated aromatic production vs dioxinand furan conc. in lake core samples

0

200

400

600

800

1000

1200 To

tal d

ioxi

ns a

nd fu

rans

in p

pt

0

200

400

600

800

10^6

lbs

Cl-a

rom

atic

s

1900 1920 1940 1960 1980

Year

chlorinateddioxins andfurans

chloro-aromatics

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

Polychlorinated biphenyls (PCBs)

83

Cl y

Cl x

PCB structures

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

84

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?

Some examples of environmental exposures

86

1. There is a general concern that if we observe abnormalities in wildlife, similar kinds of mechanisms may exist in humans.

87

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”

Cerebral palsy and mental retardation started showing up in children.

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2. Toxic loads

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

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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.

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2. Toxic loads

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

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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?

92

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

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4. The end points may not only be cancer, but compromised immune systems and generally poorer health.

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4. Immune systems & Mother’s 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 Mother’s milk.

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4. Mother’s milk

Mother’s milk from Inuit Indians in the Canadian Arctic has 7 times the PCBs as mother’s milk from women in the urban industrialized areas of southern Quebec.

96

4. Mother’s milk

During the first year, Inuit babies suffer through 20 times more colds than babies in southern Quebec.

Acute ear infections are rampant.

97

4. Mother’s 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 don’t seem to produce enough antibodies for childhood vaccinations to take.

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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.

99


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.

100


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.

101


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???

102

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.

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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.

104

7a. Sexual impairment

In a new study (Hardwell et al, Environ Presp, 2003) woman who’ve 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

105

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

106

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:

107

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

108

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

109

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.

110

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.

111

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.

112

epididymus

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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.

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1 Envir Chem at KMUTT-JGSEE – June –Sept 08 Time: Location: Rich Kamens; 087 089 1520...

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