QUIZ 5 IS DUE 11 DECEMBER

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QUIZ 5 IS DUE 11 DECEMBER EXAM 3 WILL BE HELD ON
10 DECEMBER TERM PROJECT IS DUE 10 DECEMBER -
TURN IN IN CLASS (NOT LATER)
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A Plan to Power 100 Percent of the Planet with
Renewables ( Preview ) Wind, water and solar
technologies can provide 100 percent of the
world's energy, eliminating all fossil fuels.
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Environmental issues Will we mess up the
planet with all this bio stuff?
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Things we need to worry about

• Forest land (and other landscapes)
• Wildlife
• Water quality
• Biodiversity
• Climate change
• Toxic air and water emissions
• Toxic chemicals

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Environmental issues Toxic Chemicals
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• Environmental issues Toxic Chemicals
• Trace elements metals
• Persistent Organic Pollutants (POPs)

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Trace Elements

• 10 of 89 naturally occurring elements make up
  approximately 99 of the earths crust by weight
• The other 79 make up the rest and are referred to
  as trace elements.
• The trace elements are very important in many
  biological and industrial applications.

• Oxygen 49.2
• Silicon 25.7
• Aluminum 7.5
• Iron 4.7
• Calcium 3.4

• Sodium 2.6
• Potassium 2.4
• Magnesium 1.9
• Hydrogen 0.9
• Titanium 0.6

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Heavy Metals

• Most common trace element accumulations is in
  heavy metals.
• Lead
• Mercury
• Zinc
• Copper
• Arsenic
• Cadmium
• Some are essential for biological processes in
  trace quantities, but are toxic at higher
  concentrations.
• Metals never go away

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Sources, Reservoirs, and Pathways
Source TRACE ELEMENTS AND CONTAMINANTS,
Navratil and Minarik.
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Sources Of Trace Element Contamination

• Mining, smelting, and industrial processing of
  metals and ores.
• Coal combustion
• Vehicles
• Chemical industry

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Heavy Metal Production And Emissions
Source 1998. World Resources 1998-99
Environmental change and human health.
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Emissions of Trace Metals
Gg is a giga (109) gram which is 1000 metric tons
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Persistent Organic Pollutants (POPs)

• Compounds can remain in environment for months or
  years.
• Typically have low water solubility and high
  lipid (fats) solubility.
• Accumulations in fatty tissues in living
  organisms.
• Can lead to bioaccumulation.

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Persistent Organic Pollutants (POPs)

• Pesticides - DDT
• Polychlorinated Biphenyls - PCBs
• Poly Aromatic Hydrocarbons - PAHs
• Benzene, Toluene, and Xylene BTEX
• Dioxins TCDD
• Adsorbable Organic Halides - AOXs

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2001 STOCKHOLM CONVENTION ON PERSISTENT ORGANIC
POLLUTANTS (POPs)

• The Stockholm Convention is a global treaty to
  protect human health and the environment from
  persistent organic pollutants (POPs). 
• One goal is to eliminate production and use of

• Aldrin1
• Chlordane1
• DDT1
• Dieldrin1
• Endrin1
• Heptachlor1

• Hexachlorbenzene1,2,3
• Mirex1
• Toxaphene1
• PCBs2,3
• Chlorinated dioxins3
• Chlorinated furans3

1 Pesticide, 2 Industrial Chemical, 3 Byproduct
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PCB Production
Source Hellweger et al., 2003
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Dioxin

• Most Toxic Synthetic Chemical Known To Man
• ???

• Viktor Yushchenko
• President Ukraine
• Dioxin Poster Child

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Dioxin has impacted at least two major
industries Pulp and paper elimination of
chorine bleaching Municipal waste combustion
halted new construction
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Bleaching Chemicals
Oxygen Chlorine Dioxide Extraction Hydrogen Peroxide Ozone O D E P Z O2 NaOH ClO2 NaOH H2O2 O3
Prior to 1995 Chlorine (Cl2) would have been at
the top of the list Chlorine was effective and
cheap but it had one BIG problem
DIOXIN
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WHAT IS DIOXIN?
Furan
Dioxin
Dioxin Precursors
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CHLORINATED DIOXINS

• Any process that uses chlorine can change or
  generate chlorinated dioxins and furans
• Some chlorinated dioxin have been described as
  most toxic substance known
• In some laboratory animals, very small doses can
  cause death
• In human exposure, some studies have shown link
  with cancer, others were not able to link
  exposure to cancer

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Chlorinated Compounds

• Chlorinated Dioxin (2,3,7,8 TCDD)
• Chlorinated Furan (2,3,7,8 TCDF)

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Some Background

• 1950-1980
• Industrial accidents in W. Virginia and Seveso
  Italy exposed workers to significant levels of
  dioxin.
• Dow, Monsanto, and six other chemical firms
  settled with Vietnam War Vets exposed to agent
  orange for 180 million (dioxin implicated).
• Dioxin labeled most toxic synthetic chemical
  known to man
• Dioxin found in Times Beach and Love Canal.
• 1985 - Dioxin found in Androskoggin river - near
  a pulp mill

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How Bad Is Dioxin?Most Toxic Synthetic Chemical
Known To Man
Acute toxicity of TCDD in experimental animals is
ascertained on the basis of the LD50 the dose
(in micrograms per kilogram of body weight) that
kills half of a test group.
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• IF DIOXIN WAS AS TOXIC FOR HUMANS AS IT IS FOR
  GUINEA PIGS HOW MUCH OF THIS NASTY STUFF WOULD
  IT TAKE TO KILL YOU?

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How Bad Is Dioxin?Most Toxic Synthetic Chemical
Known To Man
Lipophilic Fat Loving. Concentrates in the
food chain
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How Bad Is Dioxin?Most Toxic Synthetic Chemical
Known To Man
Lipophilic Ends up in meat and especially fish
TEQ ppt Total equivalent (dioxin level) part
per trillion
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How Bad Is Dioxin?Most Toxic Synthetic Chemical
Known To Man
Ingestion of dioxin from typical American diet
pg picogram 0.000000000001 grams
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How Bad Is Dioxin?Most Toxic Synthetic Chemical
Known To Man

• Significant exposure of humans to dioxin have
  resulted in chloracne - a fairly serious skin
  condition

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How Did the Paper Industry Deal With The Crisis?
Billions
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Major Process Changes To Eliminate Dioxin In Pulp
Mill Effluent

• Add oxygen pulping
• After kraft digester and before bleaching
• Effluent from O2 goes back to pulp mill recovery
• Replace Chlorine (Cl2) with Chlorine Dioxide
  (ClO2) throughout the bleach sequence

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US Annual Release Of DioxinToday
Total Release 40, 134 grams (40 kg)
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DIOXIN IN PRODUCTS
Food contact paper has dioxin levels less than 2
ppt. Industry - FDA goal.
One In A Million Risk - 400 miles of air
travel 60 miles of travel by car
3/4 of a cigarette 1-1/2 minutes of rock
climbing 20 minutes of being a man aged
60
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What Is A Safe Limit?
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How Bad Is Dioxin?

• Cancer Maybe
• Herbicide exposure - yes
• Significant dioxin exposure - no (chloracne)
• Immune System
• Suppressor
• Stimulant
• 1994 EPA Report
• Human studies demonstrate that exposure to
  dioxin and related compounds is associated with
  subtle biochemical and biological effects whose
  clinical significance is yet unknown and with
  chloracne.

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Environmental Dioxin Levels
Source C3.org
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Human Dioxin Levels
Source C3.org
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The Seattle Time 28 September 2008
Dioxin in soil? South Park takes finding in stride
Paul Marshall stands Sunday in front of the home
that he has been renting for about a year in the
South Park area. The former asphalt plant nearby
and the neighborhood around it was found to
contain high levels of dioxin.
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Air Water Emissions
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Emissions

• Anything that goes into the environment we would
  rather not.
• Atmospheric
• Water

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Major atmospheric emissions from a that may come
from biorefineries

• Sulfur dioxide SO2
• Nitrogen oxides - NOx
• Particulates
• Reduced sulfur compounds
• CO2?????

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• 3 April 2007 Supreme Court Decision
• Justices Say E.P.A. Has Power to Act on Harmful
  Gases

The Environmental Protection Agency has the
authority to regulate heat-trapping gases in
automobile emissions. The court further ruled
that the agency could not sidestep its authority
to regulate the greenhouse gases that contribute
to global climate change unless it could provide
a scientific basis for its refusal.
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Sulfur dioxide SO2

• Where does it come from burning compounds that
  have sulfur in them.
• Recall we need to use sulfur in kraft pulping
• What is the hazard
• Respiratory illness
• Children and the elderly.
• Acid rain
• SO2 can be transported large distances by wind

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Nitrogen Oxides - NOx

• Where does it come from Any combustion process.
• Largest source is cars and trucks
• What is the hazard
• Catalyze formation of ozone
• Serious respiratory problems.
• Smog
• Acid rain
• Water quality
• NOx can be transported large distances

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Particulates

• Where does it come from Any combustion process.
• What is the hazard
• Serious respiratory problems.
• Haze
• Soil quality
• Erosion of buildings and monuments

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Global Warming
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Reduced Sulfur Compounds

• Where does it come from Incomplete combustion
  with sulfur present
• What are they
• Hydrogen Sulfide H2S (rotten egg smell)
• Methyl Mercaptan CH3SH
• Goes into natural gas to make it smell - safety
• What is the hazard
• Very toxic chemicals at higher concentrations.
• Very strong smell
• You can smell it at about 1 ppb (part per
  billion)
• Emission Target ?2-5 ppb