ATMOSPHERE
18
Mass
5.14 x 10 kg
20
Moles of air
1.8 x 10 mol
18
Mass of Troposphere
4.11 x 10 kg
18
Mass of stratosphere
0.5 x 10 kg
Height of Troposphere
12 km
Avg height for 0.5 atm
5.6 km
Molecular weight
28.96g / mol
3
Density of dry air @ STP 1.293kg / m
Density of atmosphere
Dry atmosphere by moles: N2 - 78%; O2
-21%; Ar 0.93%, CO2 380 ppmv, N2O
0.32ppm, CO 0.1ppm, O3 10ppb, NO2
0.2 ppb, NO 0.05 ppb, NH4 0.05 ppb
… by mass: N2 - 75%; O2 -23%; Ar
1.2%, CO2 ?
STP = 0 deg C, 1 atm. @ STP1 mol =
22.4L
OCEANS
14
2
Area
3.61 x 10 m
14
2
Ice-free Pacific
1.66 x 10 m
14
2
Ice-free Atlantic
0.83 x 10 m
14
2
Indian Ocean
0.65 x 10 m
14
2
Ice-free Arctic
0.14 x 10 m
14
2
Sea Ice
0.33 x 10 m
18
3
Total Volume
1.35 x 10 m
21
Total Mass
1.4 x 10 kg
16
Mixed Layer Volume
2.7 x 10 m
Mixed Layer Depth
75 m
Mean Depth
3,370 m
WATER
15
3
Stocks
x 10 m
Oceans
1,350
Ice
29
Groundwater
8.3
Freshwater Lakes
0.125
Salt Lakes / Big Seas
0.104
Soil Water
0.067
Atmosphere
0.013
Living Biomass
0.003
Stream Channels
0.001
12
3
Flows
x 10 m / yr
Precipitation on Land
108
Precipitation on Sea
410
Evaporation from Sea
456
ET from Land
62
World Runoff
46
US Precip
5.6
US ET
3.95
US Runoff
1.65
Average Precipitation ~1m /yr
Human impacts:
9
3
10 m / yr
World
US
Withdrawal
3300
480
Consumption
1200
160
EARTH AND LAND MASSES
24
Mass of Earth
5.98 x 10 kg
14
2
Total Surface Area
5.10 x 10 m
14
2
Area of Continents
1.48 x 10 m
Avg. Continental Elevation
840 m
6
Equator Radius
6.38 x 10 m
6
Polar Radius
6.36 x 10 m
11
Avg. Distance from Sun 1.495 x 10
ECOSYSTEMS
Ecosystem
Living
BM
12
10 kg
(C)
Dead
BM
12
10
kg
(C)
Continental
560
1500
Ocean
2
2000
Much lower residence time for C in
than on land!
Ecosystem
Area
Mass
12
10
kg(C)
2
m
/
2
m
Trop Forest
24.5
18.8
Temp Forest
12.0
14.6
Boreal Forest
12.0
9.0
Forest Totals
74.4
1013 kg & kg/yr
Wood/Shrubla
nd
Savanna
Grassland
Desert
Rock,Ice,Sand
Cultivated
Land
Swamp/Marsh
Lake/Stream
Open Ocean
Upwelling
Continental
Shelf
Algal Bed
Estuaries
NPP
12
10
kg
(C) /
yr
50
25
ocean
NPP
kg(C)
/
2
m -yr
0.83
0.56
0.36
3.14
8.0
2.7
0.27
15.0
9.0
18.0
24.0
14.0
15
0.7
0.3
0.01
0.5
1.8
0.23
0.032
0.015
0.29
2.0
2.5
332.0
1.13
0.23
0.057
0.4
26.6
6.8
0.01
0.001
4
0.01
0.005
0.6
1.4
0.9
0.45
0.90
0.81
0.23
0.16
SOIL
Soil Moisture
30%
Well-soaked Soil
~40%v H2O
Rough Approx depth
2m
3
Bulk Density
1.1 kg/m
≈
3
0.91 m /kg
3
3
Compacted
2.5 kg/m ≈ 0.40 m
/kg
12
Background Erosion
30 x 10 kg /
yr
12
Human Erosion
5 x 10 kg /
yr
ENERGY
Flows
26
Solar output
3.7 x 10 W
17
Incident on Earth’s
1.75 x 10 W
2
upper atmosphere (Ω)
1368 W/m
2
Ω over Earth Surf (Ω/4) 343 W/m
2
Reflected
103 W/m
2
Absorbed by Atm
86 W/m
2
Flux at ground level
154 W/m
2
Evapotranspiration
80 W/m
12
NPP
75-125 x 10 W
12
Geothermal
20-40 x 10 W
12
US Energy Consumption 3.34 x 10 W
12
World Energy Consump 14.9 x 10 W
Content Unless noted, J per Kg
7
3
Nat gas (STP)
3.9 x 10 J/m
6
Gasoline
48 x 10
6
Crude oil
43 x 10
6
Coal
29.3 x 10
6
Dry biomass
16 x 10
Heat Capacity
Water (at 15°C)
4184 J /ºC kg
Air (Cp)
1004.2 J /ºC kg
Vaporization Heat of H2O
17°C
2.46 E6 J/kg
100°C
2.26 E6 J/kg
CARBON
12
Stocks (in 10 kg(C) except as noted)
19
Rocks and sediment
10 kg (C)
Fossil fuels (9600), inorganic C in
seawater (40,000).
Dead organic C: Continental (1500),
Marine-deep (2000), Mixed Layer (40)
Atmosphere @ 380 ppbv (820)
Living Organisms: Cont (560), Marine
(2)
12
Flows (in 10 kg (C)/yr where not noted)
Terrestrial: NPP -50; resp+decomp 50
Marine NPP -25; resp+decomp 25 (80%
in mixed layer)
Fossil fuel flux, Cement (~6.5 (Cow:
5.3))
Anthrop Land Use Change ~1
River Organic C->Oceans 0.2
Inorganic C from Weather 0.1
Human Total:
7.5 GtC/yr
Natural Total:
7.5 GtC/yr
SULFUR
12
Stocks (in 10 kg (S) where not noted)
2Dissolved as SO4 in seawater
18
1.4x10 kg
In dead OM (50), Living (3), Atmo.
(0.004)
2Atmospheric mostly as H2 S, SO2 , SO4
12
Flows (in 10 kg (S)/yr where not noted)
Plant Uptake: Land(0.15), Sea (0.6)
2SO2 /SO4 atmosphere->surface (0.24)
Flow to S from bio/seaspray/volcanos to
atmosphere (0.15)
Human emissions (0.085), River flow to
sea (0.1), Fertilizer/industrial fixing
(0.03).
Human total:
85 Mt (S)/yr
Natural Total:
150 Mt (S)/yr
NITROGEN
12
Stocks (in 10 kg (N) where not noted)
18
N2 in atmosphere
3.9x10 kg
Inorganic fixed N in soil (1-10), seawater
(350), atmosphere (1.4)
Organic (dead) on land (150), sea (300)
Organic (living) on land (7.5), sea (0.3)
12
Flows (in 10 kg (N) /yr where not noted)
Ammonification 5 (Org-N -> NH4)
Assimilation 5 (NH4 / NO3 (1:1) -> Org
N)
NH3 and NOx to atmosphere 0.5
NH4 / NOX precipitation 0.1
Denitrification 0.1 (NO3 -> NO / N2 1:1)
Bio-N fixation 0.2 (2/3 Terr, 1/3 marine)
Anthrop N-Fix 0.1 (2/3 fert, 1/3 combust)
Human total:
150 Mt (N)/yr
Natural Total:
150 Mt (N)/yr
!
3. Substitute back in and solve. Often
+
best to get [H ] terms all on one side.
Step (1) DOESN’T work with ≈ infinite
sources, eg. atmosphere.
TIME CONSTANTS
Transit time
E-folding Time
Residence time
(Initial Concentrations)
Trop. res time >20µm
Trop(SO2 ,H2 S, NO,HO2) –
pH of Pristine Atmosphere
Reactive or very soluble
"
"2
"
[H + ] = [HCO"3 ] + 2[CO"2
gases
3 ] + [HSO 3 ] + [SO 3 ] + [OH ]
Assume 0.2 ppbv SO2 ; 380 ppm CO2 :
Vertical mixing in
10"11.24 10"21.57 10"11.37 10"18.26 10"14 troposphere
+
[H ] =
+
+
+
+
[H + ]
[H + ]2
[H + ]
[H + ]2 [H + ] Troposphere particles < 1µm
+
!
-
PHOSPHORUS
12
Stocks
(in 10 kg (P) )
Organic: Living (5); Dead (25)
Inorganic: Soil (200)
Dissolved/susp. MixLyr (3), Deep Ocean
!
(300)
12
Flows
(in 10 Kg (P)/yr)
Bio-Uptake=Decay (0.2 sea / 1.0 marine)
Human mining (0.2); Riverflow (0.2);
Guano deposition and fishing each
(0.0004)
ALKALINITY
Acid-Base Reactions
-1.47
[H2CO3] = p(CO2) x 10
+
-14
H2O < > H + HO
10
+
-6.35
H2CO3 < > H + HCO3
10
+
-2
-10.33
HCO3 < > H + CO3
10
+
3
H2SO4 < > H + HSO4
10
+
-2
-1.9
HSO4 < > H + SO4
10
0.096
[H2SO3] = p(SO2) x 10
+
-1.77
H2SO3 < > H + HSO3
10
+
-2
-7.21
HSO3 < > H + SO3
10
-1.6
[HNO3] = p(NO2) x 10
+
1
HNO3 < > H + NO3
10
+2
-2
-8.42
[Ca ][CO3 ] = 10
(calcite)
Henry’s constant for: H2 CO3 -1.47, H2 SO3
0.096, HNO3 -1.6, NH3 1.76, CO -3.0,
N2O -1.59, H2 S -0.97
moles of pH
!
!
!
Some tricks:
1. Complete dissociation when you have
fixed amt of acid with -log [acid] > pK.
2. Look for negligible terms.
!
!
-
Solve for H assuming HCO3 & HSO3
only spp.
@380 pH = -5.50 ; @275 ppm; pH= 5.54
"
+
[Alk] = [HCO"3 ] + 2[CO"2
3 ] + [OH ] - [H ]
+2
+
+
-
+
moles of H ions added
Draw and understand Alkalinity – pH
curves.
Acidity<-> damage relationships.
CLIMATE CHANGE
-8
2
4
Sigma = 5.67x10 W/m /ºK
Simple model: Energy balance between
outermost of atmosphere and inflow:
!
To =
(1# a)1/4 = This energy is supplied
4"
through radiation from bottom up.
Earth’s Surface gets all inflow.
Ts = (n + 1)1/4 To =
!(n + 1)1/4
(1# a)1/4
4"
n≈2 for earth. This overpredicts T≈303
ºK
Actual Surface temp = 288ºK
EQUATIONS
Donor Controlled Model
dM
= a " bM and
dt
b=
1
t res
;b tot = b1 + b 2 + ...+ b n
>100
days
1 year
10 years
-2
alkalinity
E = "T 4
10 days
Probability
=2[Ca ]+2[Mg ]+[Na ]+[K ]–[NO 3 ]– [SO 4 ]
Can also solve in terms of other ions by
using net charge balance = 0. Also,
remember that this is in
EQUIVALENTS/L. And, if [Alk]=0, then
pH is 5.6 from natural sources like
dissolved CO2 .
Pre-industrial pH was 5.51 in rainwater
and 8.3 in oceans.
+2
Interhemispheric mixing
Mixing time of stratosphere,
trop restime for CO2. ,non
reactive gases trop>stratosphere
<1 day
1 day
BIOMASS
Tree makeup 30% H2O of total weight,
70% Rough formula CH2O. Remember
CH2O ≠ C
Deevey Formula C150 H 300 O 150 N10 P 2S1
C:N Ratios : Leaves (10), Trees (300400)
GPP ~2x NPP, or roughly half of NPP>resp.
2
3
6
9
12
15
18
PREFIXES
h-hecto
k-kilo
M-mega
G-giga
T-tera
P-peta
E-exa
-2
-3
-6
-9
-12
-15
-18
c-centi
m-milli
µ-micro
n-nano
p-pico
f-femto
a-atto
ELEMENTS
H-1 ; C-12; N-14; O-16; P-31, S-32; Ca40
2
1ha = (100m) , 1J = 0.2390cal,
3
2
Vsphere = 4/3 x pi x r , Asphere = 4 x pi x r
2
Vcone = h/3 x pi x r