8 Surface Processes

Mass Exchange

Volatilization Reaeration Oil spills Lake temperature models

Momentum Transfer

Surface Heat Transfer

Air water exchange

Equilibrium: Henrys Law

H=

c ge cle

c ge
cle

Typical units for [H]: atm-m3/mol (KH) or dimensionless (KH) For air KH ~ 42 KH

Two-film theory
zg

Ex: liquid side

J l = k l (cl cle )
(cl cle ) J l = Dl zl

cle=cge/H

cl

-zl

cg cge

k l (cl cle ) = k g (c ge c e ) = k (cl c g / H )

H= c ge cle
3 eqns, 3 unknows (cle, cge, k)

Two-film theory
1 1 1 = + k k l Hk g
1 2

c ge c g =
cl cle =

k l ( Hcl c g ) Hk g + k l
Hk g + k l

k g ( Hcl c g )

Resistances in series: kl << Hkg => 1 dominates (liquid side controlled) kl >> Hkg => 2 dominates (gas side controlled) Medium with lower equilibrium concentration controls

Typical values for air and water

Typical values for air (as gas) Dg ~ 0.1 cm2/s, 0.1 < zg < 1 cm => kg = Dg/zg = 0.1 to 1 cm/s Typical values for water (as liquid) Dl ~ 2x10-5 cm2/s, 0.002 < zl < 0.02 cm => kl = Dl/zl = 10-3 to 10-2 cm/s Kg ~ 100 kl so if H >> 0.01 then water side controlled (think DO); if H << 0.01 then air side controlled (think evaporation)

Example of liquid side control

H >> 0.01; assume H ~ 1 => cge = cle = ce
zg
ce cl

-zl

cg ce-cg cl-ce

ce c g =

k l ( Hcl c g ) Hk g + k l

(c l c g )

kl kg

cl c e =

k g ( Hcl c g ) Hk g + k l

(c l c g )

Liquid side control, contd

zg
ce cl

If we double kl (halve zl), (ce-cg) doubles, both gradients ~ double => twice the mass flux; red line
c

-zl

cg ce-cg cl-ce

If we double kg (halve zg), (ce-cg) is halved, both gradients ~ const => similar mass flux; green line Therefore mass flux controlled by liquid side

Surface Renewal Theory

Described previously for streamreaeration formulae (Chapter 7) zl (or zw or ) not stagnant, but timedependent ~ [Dt]1/2, where t is reciprocal of a renewal rate, depending on bottom generated turbulence. Thus kl (hence k) = Dl/zl ~ D1/2

Measurement of gas exchange

Gas-evasion experiment: introduce chemically conservative gas (e.g., CO2, propane, radon) at c > saturation, and watch c decline with distance due to volatilization In open water bodies (or rivers where you dont know flow rate) introduce a second, non-volatile tracer such as salt. Sometimes use tracer of opportunity

Application to rivers
x Qr
& nv cv m &v c nv m
1

&v m

(propane)

& nv (salt) m

e-1 0 0 hu/kl

& nv m c nv = Qr & v kl x / hu m cv = e Qr & v kl x / hu cv m = e & nv c nv m

x (stream reaeration coefficient Ka = kl/h)

Gasses other than oxygen

Ka ~ D (stagnant film), D1/2 (surface renewal), D2/3 (split the difference) From Chapter 1, Sc = /D ~ MWb (b ~ 0.35 to 0.4) Ka/K ~ (DO2/D)2/3 ~ (32/MW) -1/4 Example: Propane C3H8, MW = 44

Ka/K = (32/44) -1/4 = 1.08 Calibrations actually shows Ka/K ~1.39

How far downstream must one go?

OConnor-Dobbins at 20oC: Ka = 3.9u 0.5/h1.5 u = 0.3 m/s, h = 1 m, Ka = 2.1 d-1 x~ u/Ka = (0.3 m/s)(86400s/d)/(2.1d-1) ~ 12 km

Application to open waters

x u h = water depth or thermocline depth

& v (propane) m
& nv (salt) m
& nv cv m 1 &v c nv m
e-1 0 0 hu/kl

c nv =

& nv m

2 uh &v m y 2 / 2 2 kl x / hu cv = e e 2 uh & v kl x / hu cv m = e & nv c nv m

x

y 2 / 2

Mass transfer in lakes and oceans

Most contaminants of concern are water side controlled (e.g., DO, VOC) In rivers, source of turbulence is bottom roughness In deep water bodies (lakes, oceans) it is wind stress => uw* (water-side friction velocity) which affects zl Contaminants that are air side controlled also affected by wind (through zg)

kl vs uw*
4 4 44 44 4

w (Sc = 600)

KL [cm/s]

5 5

4 2 3

2 3 1 33 3 3

333

10-3

(I) 10-3

10-1

100 u* w [cm/s]

101

10-1

100 Fraction vel. u* w [cm/s]

lab
Figure by MIT OCW.

field

uw* because transfer is water side controlled and uw* is indicator of turbulence; yet uw* not easily measured

w (Sc = 600) 101

10-2

41 2 4 22 2 41

[m/d] 10-2

Wind Stress
z ua(z)

= C10 a u10 2 = w u w* 2 u10 = 10 m wind

u w* = C10 a
speed;

u10

C10 = drag coef.

C10 = (0.8+0.065u10) x 10-3 uw(z) [u10 > 1 m/s; Wu, 1980] u10 -> C10 -> uw* -> kl

kl (or zl) vs u10

10-3
n=2

KL, Overall Liquid Film Coefficient at 20o C, m/sec.

n=1

1000 500
ELA Lakes

10-4

Konwisher (1963) Smooth surface Konwisher (1963) 3 cm waves 60/mm Hoover and Berkshire (1969) Thurber and Broecker (1970) Liss (1973)

n = 3/2

Zl
(microns) 100 50
Central, Atlantic (Broecker and Peng 1971)

10-5

n=1

n = 3/4

Downing and Truesdale Juliano Mattingly Yu et al

10 5

North Pacific (Peng et al. 1974)

10

12

14

10-6

10

50

100

U10, Wind

Velocity,(ms-1)

U10, Average Wind Speed, m/sec. at 10 m

Yu and Hamrick (1984)

Figures by MIT OCW.

Emerson (1075)

Example film coefficients

k l = 0.0004 + 0.00004u10
k g = 0.3 + 0.2u10
kl and kg in cm/s; u10 in m/s [Schwarzenbach et al, 1993] Note that both depend on u10
2

Examples
Above eqns: u10 = 5 m/s => kl = 1.4x10-3 cm/s (green dot); kg = 1.3 cm/s Figure 8.8: zl = = 120 m = 1.2x10-2 cm. For DO, D = 2x10-5 cm2/s kl = D/zl = 2x10-5/1.2x10-3 = 1.7x10-3 cm/s (red dot)

kl (or zl) vs u10

10-3
n=2

1000
n=1

KL, Overall Liquid Film Coefficient at 20o C, m/sec.

500

ELA Lakes

Konwisher (1963) Smooth surface Konwisher (1963) 3 cm waves 60/mm Hoover and Berkshire (1969) Thurber and Broecker (1970) Liss (1973)

10-4

Zl
n = 3/2

(microns)

100 50
Central, Atlantic (Broecker and Peng 1971)

10-5

n=1

n = 3/4

Downing and Truesdale Juliano Mattingly Yu et al

10 5

North Pacific (Peng et al. 1974)

10

12

14

U10, Wind 50 100

Velocity,(ms-1)

10-6

10

U10, Average Wind Speed, m/sec. at 10 m

Figure by MIT OCW.

Yu and Hamrick (1984)

Emerson (1075)

Volatile Halogenated Organic Compound (VHOC) Experiment

CH3Cl3 and other one carbon VOCs (THMs) and two carbon VOCs (solvents) discharged with waste water. Used to

compute volatilization (assuming known residence time) or compute residence time (with known volatilization)

TCE data in Boston Harbor

TCE loading from Deer & Nut Island TPs: 24 m3/s at 11 g/L Ave harbor TCE concentration 241 ng/L (all pts) 214 ng/L (excl. 840) Harbor volume = 6x108 m2 Kossik, Gschwend & Adams, 1987

TCE Experiment, contd

Nominal residence time (w/o volatilization; excluding presumed outlier)

cV (214 x10 9 kg / m 3 )(6 x10 8 m 3 ) * = = = 5.6d 3 6 3 Qo co (24m / s )(86400 s / d )(11x10 kg / m )

TCE Experiment, contd

With volatilization
dc V = kAc Q f dt k A Q dc c = + dt V V

k = piston velocity ~ kl (water side control) * = bulk removal rate (t-1) V/Q = = hydraulic res time kA/V = k/h

=1/* D = 1.0x10-5 cm2/s

For CH3Cl3 H = 1.13 (dimensionless) >> 1 => ws control

TCE Experiment, contd

From Figure 8.8 and u10 = 5 m/s, = 1.2x10-2 cm k = D/ =(1.0x10-5)/(1.2x10-2)= 0.00083 cm/s = 3 cm/hr = 0.72 m/d 1/t* = 1/t + k/h 1/t = 1/t* - k/h = (1/5.6d) (0.72 m/d)/6m =0.18 0.12 = 0.06d-1 => = 17 d Estimated is too high; reason is likely extraneous or under-accounted sources of CH3Cl3

Momentum Exchange
Chapters 2, 3 discussed surface shear stress for eddy diffusivity and hydrodynamic modeling Previous section discussed stress as source of turbulence governing mass exchange Also of interest in transporting floating material, specifically spilled hydrocarbons

Oil Spills

Composition Fate Transport (spreading, advection) Clean-up

Marine Sources (103 MT/yr)

N. America Natural Seeps Petroleum Extraction Petroleum Transport Petroleum Consumption Total
About half is anthropogenic

Global 600 38 150 480 1300

160 3 9 84 260

(Oil in the Sea III, NRC, 2003)

Composition
Crude and Refined Oils Always multiple constituents Characterized by Boiling Point (or distillation cut)

Fate
Volatilization (lighter fractions) Emulsification (depending on oil) Natural dispersion (if enough energy) Biodegradation Dissolution Photo-oxidation Sediment particle interaction Output from NOAAs ADIOIS model; independent of transport

Transport Models
Spreading and Advection Pre-planning (evaluate risk) Real-time (assist clean-up; needs to be quick and dirty) Hind-cast (who is responsible, damage assessment)

Simple advection model

z ua(z)
a =
fa f f a u a 2 = w w (u s u w ) 2 = w w (u s ) 2 2 2 2 a u s fw fa = 0.03 ua w

us uw(z)

Surface current speed ~ 3% of wind speed. (Also explained by Stokes Drift due to surface waves) In which direction?

Ekman Model
Linearized equations of motion; constant viscosity

u 2u v = E 2 t z

= 2 sin Coriolis parameter

v 2v + u = E 2 t z

w = u + iv

Complex velocity

w=0
w sx + i sy = E z w

At depth (z = - oo) At surface (z = 0)

Ekman Model, contd

w=

sy w

i exp (1 + i ) z + 4 E 2E

y s z=0 x z

Surface drift 45o to right; Depth average drift 90o to right Field experiments show surface drift ~ 10o to right. Explained by variable vertical viscosity E ~ z (Madsen, 1977)

Other effects of wind: Coastal Upwelling/Downwelling

Other effects of wind: Langmuir Circulation

Oil Streaks

Wind

Figure by MIT OCW.

Idealized Spreading (Fay, 1969)

D h

dD ~ dt

1 g'h ~ g 'V D

Gravity-Inertia Gravity-Viscous Surface Tension-Viscous

dD g 'V 2 t ~ dt D5 w

fr dD t ~ dt w D w

Idealized spreading, contd

Regime Gravity-Inertia D = 2k1[gVt2]1/4 K1=1.14

Gravity-Viscous D = 2k2[gV2t3/2/w 1/2]1/6 K2=0.98 to 1.45 D=2k3[frt3/w2w]1/4 Surface Tension-Viscous K3=1.6

Comments
Theory applies down to slick thickness of about 0.1 mm Additional spreading due to

Time-varying spillage Wind, waves and non-uniform currents Dispersion of submerged (slower moving) oil droplets

Field experiments show oil often very nonuniform (90% of volume in 10% of area)

Oil Transport Models

Slick advected with underlying surface current plus 3% of wind speed (~10% deflection to right) (3-D) models simulate transport of subsurface dispersed oil. Currents can be observed or predicted (sophistication depends on application available time) Fate processes often computed independently from transport

Model Simulations

NOAAs 3D GNOME; ANS Crude off Coast of Florida

Mechanical Clean-up

Chemical Dispersion
Surfactants that reduce interfacial tension Create dispersed droplets Subsurface/bottom impacts vs surface/shoreline Air (large spills) or boat application Window of opportunity

Chemical Dispersion, contd

NRC, 1989

In situ Burning
Considered secondary option (like chemical dispersants) Most appropriate for offshore spills (reduced AQ impacts)

Surface Heat Transfer and Temperature Modeling

Surface heat fluxes Linearized surface heat transfer Cooling ponds Natural lakes and reservoirs

Importance of Temperature
Important WQ parameter

Thermal pollution Species preference (fish habitat) K=K20T-20 = (T)

Affects rate constants

Produces density stratification

Important tracer (e.g., Ez)

Surface Heat Transfer (W-m-2)

s sr a ar br e c

Net solar, sn Net atmospheric, an Back radiation, r Evaporation, e Conduction, c

60 to 300 200 to 450 250 to 500 0 to 350 -70 to 200

n = sn + an br e c

Solar Radiation
Short wave length (< 3m) Direct plus diffuse (scattered, reflected) Absorbed & re-radiated (> 3m) by clouds Measured by pyranometer Incident clear sky radiation calculated from latitude, date and time of day Corrections for cloud cover and reflection

Net Solar Radiation (contd)

sr/s (%) Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

10

sn = s sr 0.94 sc (1 0.65C
C = fractional cloud cover

Depth-variation of solar radiation

Measured with Secchi disk or in-situ pyranometer

z = (1 ) sn e

1.7 = dD
~ 0.5

Atmospheric Radiation
Long wave length (> 3m) Re-radiated from atmosphere Measured by pyrgeometer Incident clear sky radiation calculated from absolute air temperature, vapor pressure Corrections for cloud cover and reflection

Incident Radiation Formulae

ac = (Ta + 273)
4

= Stefan-Boltzman const (5.7x10-8 W/m2-oK4) = emissivity (dimensionless)

= 0.92 x10 5 (Ta + 273) 2

e = 1.24 (T + 273) a
1 7

Swinbank (1963) Itso-Jackson (1969)

={ 1.0 0.26 / exp[7.77 x10 5 (Ta ) 2 ]}

e = vapor pressure, mbar Brutsaert (1975

Net Atmospheric radiation

an = 0.97 (Ta + 273) (1.0 + 0.17C
4 2

C = fractional cloud cover ~3% reflection

Back Radiation
Water surface is nearly a black body

( ~ 0.97)
4 8 4

br = 0.97 (Ts + 273) = 5.5 x10 (Ts + 273)

Evaporative Heat Flux

Measured

eddy flux (short term) evaporation pans (long term)

E = f(Wz) (es-ez) Daltons Law

Computed from mass transfer formulae

es = vapor pressure at surface ez = vapor pressure at elevation z f(Wz) = wind speed function = a + bWz (kg)

Evaporative Heat Flux (contd)

Mass transfer => heat transfer using latent heat of vaporization
Lv = ( 2493. 2.26Ts ) 10 3
J/Kg

e = Lv E = f (W z )(e s ea )

e = 3.72W2 (es e2 )
e = 5.1A 0.05W2 (e s e2 )
(A in ha)

Lake Hefner, Marciano and Harbeck (1954) Fetch-dependence Harbeck, (1962)

(W/m2; W2 in m/s; es, e2 in mb)

ez

Wz es

ez and Wz vary vertically (height above water) and horizontally (above water or on-shore)

Evaporation from non-natural water bodies

es increases with temperature

Heated water bodies have increased evaporation (water vapor also lighter than air) Saline bodies have decreased evaporation

ez

es decreases with salinity

es e = f(Wz) (es-ez)

es decreases with pressure

Conductive Heat Flux

Computed from evaporative flux using Bowen Ratio

c = Rb e
(Ts Tz ) Rb = Cb (e s e z )
Cb =0.61 mb/oC;

Summary
n = sn + an br e c
functions of Ts

functions of external factors (met and astronomical conditions) Strategies for computation: table look up Self regulation: errors in calculations compensate

Linear Heat Transfer

e

Equilibrium Temp, Te

Ts for which n = 0 Function of met

Surface Heat Exchange Coefficient, K

Slope K

Slope of n vs Ts

n = -K(Ts-Te) K ~ 20-50 W/m2oC

Te

Ts

Example: Periodic Heat Loss

cV
dT dt

= As n
n k = K/cph

dT = k (T Te ) dt

As h= V/As

Te = Te + Te e

iwt

= 2/P

T = T + T * e it
T = Te + Te i e it

Periodic Heat Loss (contd)

T = T + T * e
it

T * = Te i

T = Te + Te i e it

T = Te + Te i (t t L )
k T * = = k + i Te k k2 +2 e

t L = ( 2 ) P
i tan 1 ( / k )

Phase lag

= tan 1 ( / k )
tL = P tan 1 ( / k ) 2

Amplitude

Te T

Examples
K/c = 1m/d*; h = 10m, k=K/ch = 0.1d-1

P =2/P T/Te =k/(k2+2)0.5 =tan-1(-/k) tL = P/2tan-1(/k)

* K ~ 48 W/m2oC

1 day 0.17d-1 0.016 -89o 0.247 d

365 6.28d-1 0.986 -10o 10 d

Cooling Lakes and Ponds

Used to cool electric power plants Shallow (vertically well-mixed)

Erected with dikes T = T(x,y) + T(t) Damming of reservoirs r=KAp/cQo

Deep reservoirs

Cooling capacity

Cooling Ponds
Deep Stratified

Shallow Dispersive

Shallow Recirculating Plan View Elevation

Example: shallow-longitudinal dispersive

2

d 2T dT cQo = cWHEL K (T TE )W 2 dx dx

T1 - TE T0

Single pass
Ti TE = To TE 4ae
1 2E * L a 2 E * L

(1 + a )2 e

a 2E * L

(1 a )2 e

Continuous operation
(To = Ti + To)
Ti TE = To 4ae
1 2E * L a 2E * L
0 0

Plug Flow

5 2 0 0.1 0.2

EL*
1 0.5

Completely mixed

3 r

Figure by MIT OCW.

(1 + a )2 e

a 2E * L

(1 a )2 e

4ae

1 2E * L

Jirka et al. (1978)

Stratification in Lakes & Reservoirs

Factors causing vertical stratification

Differential absorbtion Reduced vertical mixing Strong through flow Strong wind Differential absorbtion

Factors causing horizontal stratification

Reservoir classification based on horizontal through flow (Orlob, 1969)

Through flow velocity = L/(V/Q) Intl wave speed ~ (g/h)0.5 ~ Nh

N = buoyancy freq = [(g/)(d/dz)]0.5 L = length; Q = flow; h = depth; V = vol Fr << 1 vertically stratified Fr >> 1 vertically mixed

Fr = LQ/VNh

1-D Reservoir Modeling

z qout z Q 0 h T

qin

Q = qin q out z

T 1 1 T qin Tin q out T + (QT ) = AE z + t A z z A z A

Surface Layer
Well mixed layer

T WML

Convective mixing Wind mixing

Wind mixing algorithm for surface

Oceans (Kraus-Turner)

1-D

1-D model below

Surface Layer (contd)

PE h gh = (gh ) = u e t 2 2 A KE 2 3 = u* u s t ~ u* t A
PE = const KE 2 ue u* ~ = Ri 1 u * gh

=u*2 T h h

Many variants

Lake stability
Stability index (PE of water body with equivalent mass and heat content but uniform density PE of stratified body)

SI = [ ( z )][ z z c ]gA( z )dz

0

= ( z ) A( z )dz
0

A( z)dz
0

Average density Center of mass

z c = ( z ) A( z ) zdz
0

( z ) A( z )dz
0