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    Environmental Chemistry: Cautions For A Finite World

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    Putri Imarotul Muttaqi
    The document discusses environmental chemistry and cautions for a finite world. It covers natural cycles like water, oxygen, carbon, and nitrogen, and how anthropogenic activities are burdening these cycles. The key points made are that all environmental sinks are finite, dilution is not a solution to pollution as it assumes infinite reservoirs, and that both thermodynamics and kinetics must be considered for evolving systems. It emphasizes the need for understanding and long-range planning to address issues like climate change, rather than assuming dilution will solve problems.

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    Environmental Chemistry: Cautions For A Finite World

    Uploaded by

    Putri Imarotul Muttaqi
    22 views26 pages
    The document discusses environmental chemistry and cautions for a finite world. It covers natural cycles like water, oxygen, carbon, and nitrogen, and how anthropogenic activities are burdening these cycles. The key points made are that all environmental sinks are finite, dilution is not a solution to pollution as it assumes infinite reservoirs, and that both thermodynamics and kinetics must be considered for evolving systems. It emphasizes the need for understanding and long-range planning to address issues like climate change, rather than assuming dilution will solve problems.

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    Environmental Chemistry

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    The document discusses environmental chemistry and cautions for a finite world. It covers natural cycles like water, oxygen, carbon, and nitrogen, and how anthropogenic activities are burdening these cycles. The key points made are that all environmental sinks are finite, dilution is not a solution to pollution as it assumes infinite reservoirs, and that both thermodynamics and kinetics must be considered for evolving systems. It emphasizes the need for understanding and long-range planning to address issues like climate change, rather than assuming dilution will solve problems.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    22 views26 pages

    Environmental Chemistry: Cautions For A Finite World

    Uploaded by

    Putri Imarotul Muttaqi
    The document discusses environmental chemistry and cautions for a finite world. It covers natural cycles like water, oxygen, carbon, and nitrogen, and how anthropogenic activities are burdening these cycles. The key points made are that all environmental sinks are finite, dilution is not a solution to pollution as it assumes infinite reservoirs, and that both thermodynamics and kinetics must be considered for evolving systems. It emphasizes the need for understanding and long-range planning to address issues like climate change, rather than assuming dilution will solve problems.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    of 26

    Environmental Chemistry

    Cautions for a Finite World


    Topics
    Natural Cycles Enviromental
    Water Divisions
    Oxygen Atmosphere
    Carbon Hydrosphere
    Nitrogen Biosphere
    Energy Lithosphere
    Anthropogenic “Better Living
    Burdens through Chemistry”
    “Solution to Pollution is Dilution”
    Mantra presumes infinite reservoirs.
    Treats pollution as a local concentration to
    be reduced by an  of natural purity.
    Need for reduction well below LD50.
    Diffusion and mass transport aid the myth.
    Unrelenting contamination overwhelms.
    All sinks are finite sinks.
    Equilibrium and kinetics are unforgiving.
    Kinetics and Thermodynamics
    In evolving systems, current states are
    a function of both.
    Thermodynamics says where equilibrium
    would lie if it ever arrived.
    Kinetics declares the rate at which species
    are evolving in time.
    • Via the rates of chemical reactions
    • Via diffusion and mass transport
    Degradation in Dilution Model
    As equilibrium (pollution homogeneity)
    approaches, sink rates slow.
    Product “pressures” dictate that reverse
    reactions (return of contaminants) rise
    to counter the cleansing protocols.
     dilution is not the answer.
    Understanding & long-range planning are.
    Global Water Cycle
    Despite drought and its famine …
    Water’s global cycle is little altered by us.
    Solar evaporation  humid atmosphere
    Cresting waves  microscopic salt crystals
    Rising air currents  lower air Tadiabatic
    Salt crystals seed condensation.
    Rainfall snares soluble gases, feeds Life,
    erodes mountains, and returns to the sea.
    But, as everything is connected…
    Anthropogenic particulates influence
    where it rains, and downwind it doesn’t.
    Anthropogenic combustion influences
    what the rain dissolves and bombards.
    H2O, the universal solvent, brings acid rain.
    Global Warming shifts precip. patterns.
    Redistributes coastlines and grain belts.
    Feast & famine migrates on the globe.
    Acid Rain
    Natural Acidity, CO2(aq)
    PCO2 = 370 ppmv, KH, Ka1 yield pH 5.6
    SO3 & N2O5 are strong acid anhydrides.
    Vulcanism, sour crude, and ore smelting
    produce S3; Nature is a minority polluter.
    CaS4 & H2S4 recovery are economical.
    pH 4 recorded in (now dead) lakes.
    O2 Cycle Secure
    Atmospheric O2 now at 1.21015 ton
    Holding there for over 500 million years!
    Biosphere holds only 1013 ton, but seas are
    a 1.41018 ton reserve (as H2O).
    Photosynthesis/Decay are the major
    source/sink at 109 ton each annually.
    1015 ton/109 ton yr–1  106 yr O2 lifetime
    Unless we clearcut & poison seas, O2 is OK.
    Carbon Cycle
    Natural
    • 2.51012 ton in atmosphere vs. 1.31014 in sea.
    – 1011 ton yr–1 exchange gives ~25 yr residency.
    – So oceans are the perfect sink for excess CO2.
    • 1013 ton in biosphere exchange 61010 ton yr–1.
    Anthropogenic
    • Fuel burn at ~10% of photosynthesis/decay
    exchange increases atmospheric CO2. Seas can
    absorb but only eventually. Le Châtlier wins.
    Growing CO2 Warms the Earth
    Greenhouse Effect is essential for Life!
    Earth’s radiative balance (solar input vs. IR
    output) leaves <TEarth> ~ – 20°C
    • Almost all water would be ice everywhere.
    • But Life requires ℓiquid water!
    H2O(g) and CO2 absorb outbound IR and
    reradiate it omnidirectionally.
    • So Earth intercepts ~½ that absorbed IR and
    gains <T> to +15°C.  H2O(ℓ) & we exist.
    Venus, the Runaway Greenhouse
    Being closer to Sol, Venus intercepts
    twice the solar flux of Earth.
    But it is twice as reflective (albedo), so
    its <Tradiative> is about the same, –29°C.
    But it’s surface T averages +435°C!
    90 atm CO2 gives an IR thickness of 68.
    Earth’s optical thickness is only 0.68
    Earthly Implications
    We won’t become Venus, but …
    PCO2 up 30% since Industrial Revolution.
    Fossil fuel combustion. PCO2 now 370 ppmv
    Growth in 2000 is +0.4% per year
    2 the average growth rate of last 150 yrs.
    ~600 ppmv in next 75 yrs, over 2 natural.
    Earth’s <T> is rising. T~2-3°C now.
    • 5-6°C triggers climate changes.
    Greenhouse Fixes
    Negative population growth.
    • Guarantees standard of living but impractical.
    Reduce burning of fossil fuels & forests.
    • H2/O2 fuel cells work in developed countries.
    • Nuclear power grid practical but unpopular.
    • But developing countries cannot afford either
    and have the highest population growths!
    Plan for and resign to the changes.
    Nitrogen Cycle
    Natural
    • 3.81015 ton in atmosphere resident 107 yrs.
    • Only 2.21013 ton in sea; 3.51010 in biomass
    • Life requires fixation (to NH3) by bacteria.
    – 2.3108 ton/yr fixation and (reverse) denitrification

    Anthropogenic
    • Crops, fertilizer & engines fix 0.8108 ton/yr
    • Combustion denitrifies 0.3108 ton/yr
    • Only a 13 ppb annual change; N sweat.
    Nitrogen Caveats
    NOX (generic nitrogen oxides)
    Fixation in engines generates NOX
    • Terrestrial contaminant of acid rain (HNO3)
    • Stratospheric contaminant of ozone destruction
    – NO + O3  NO2 + O2
    – NO2 + O  NO + O2
    Runoff from fertilized fields
    • Supports algal growth in waterways.
    • Algae consume O2 and suffocate water fauna.
    The Chemistry
    Fixation (Rhizobia, Azotobacter, etc.)
    N2 + 6e– + 12ATP + 12H20  2NH4+ + 12ADP + 4H+
    N2 + 3H2  2NH3 (Haber Process, 450°C, 200 atm, cat.)

    Nitrification (Nitrobacter)
    NH3 + (3/2)O2  NO2– + H2O + H+

    Denitrification (Pseudomonas)
    2NO3+ + 12H+ + 10e–  N2 + 6H2O
    • Only runs under anaerobic conditions: wetlands & swamps
    • Those are disappearing with development.
    The Energy Cycle
    1/3 of available solar energy absorbed.
    2/3 (planetary albedo) reflected into space.
    Most insolation warms oceans.
    Oceanic gyres (currents) transport solar
    heat to the poles to disperse it (where
    insolation is oblique) returning cold water.
    Earth’s energy departs as infrared light.
    Man’s heat budget no threat to Nature.
    But climate change & desertification change albedo!
    The Atmosphere
    A heated ideal gas w condensible (H2O)
     turbulent in the majority of its moles.
    Mesosphere interacts w solar “wind.”
    • O2 + hUVC  2 O  < 2000Å
    Stratosphere, home to the O3 blanket.
    O + O2 + M  O3 + M*
    O3 + hUVB  O + O2 + heat  < 3000Å
    • O + O3  2 O2
    Stratospheric Contamination
    CFC, chlorofluorocarbons (CnClxFy)
    • CFyClx + hUV  CFyClx–1 + Cl
    Cl + O3  ClO + O2
    ClO + O  Cl + O2
    • ~50 year ClOX lifetime & still migrating up.
    • Ozone hole at both poles migrating down.
    • NOX also destroys odd oxygen catalytically.
    Fix: international agreement to end CFC
    Troposphere
    Up to 8-12 km above sea level.
    Turbulent!
    Tropopause (boundary with stratosphere)
    stops weather because it’s warmer above.
    Air pollution in troposphere (photochemistry)
    • NO2+ O2 + h  NO + O3
    • O3 + h  O + O2
    • O + H2O  2 OH [OH] ~ 106 molecules/cc
    • OH radical is dominant oxidizer in troposphere!
    Smog: health hazard
    “Smoke and fog,” a term from London.
    Engine exhaust components
    CO, NO, unburnt hydrocarbons
    Lean mix minimizes CO, hc, maximizes NO
    Rich mix minimizes NO, maximizes CO, hc
    • Run a little rich and catalytically kill CO to CO2
    OH + CO + O2  CO2 + HO2
    Peroxides like PeroxyAcetylNitrate result
    Hydrosphere
    All the waterways on Earth
    Civilization created on rivers (Euphrates)
    Population pressure
    Irrigation consumes rivers, lakes, aquifers
    Salts concentrated in what little is left
    Industrial and Agricultural pollution
    Both chemical and thermal (remediable)
    Biosphere
    The zone of Life
    Wherever it’s found: thermal vents?
    Ocean: Life’s Nursery and O2 Factory
    Phytoplankton make ~90% of photo-
    synthetic O2 on Earth. Sensitive to UV!
    So bigger ozone holes adversely effect O2
    production.
    PhytoplanktonZooplanktonFishUs.
    Frankenfixes
    Altering the environment chemically
    alters the kind and number of lifeforms.
    Cleaning the environment can rest, in
    part, on genetic engineering.
    Giving wheat Rhizobia, reduces fertilizer.
    Giving bacteria a taste for oil, cleans spills.
    But it’s not nice to fool Mother Nature
    unless you are as smart as She.
    Environmental Awareness
    As scientists, we are morally obliged to
    consider the consequences of our acts.
    We create a molecule for profit but
    must consider its fate when discarded.
    E.g., plastic bottles now biodegrade and
    are no longer immortal.
    E.g., non-chlorinated refrigerants now cool
    beer without sacrificing the Ozone Layer.

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