7 Dissolved Oxygen

Introduction Oxygen Saturation Biochemical Oxygen Demand Reaeration Streeter-Phelps Equation Nitrification Sediment Oxygen Demand Photosynthesis and Respiration Expanded Streeter-Phelps Equation Artificial Re-aeration

Dissolved Oxygen
Important for aquatic health

DO standards typically 5 to 6 mg/L Affects release of chemicals bound to sediments Anaerobic conditions => H2S

Redox chemistry

Oxygen Saturation
c s (T , S ) = exp{1.3934411x10 2 + 1.575701x10 5 /(T + 273.15) 6.642308 x10 7 /(T + 273.15) 2 + 1.243800 x1010 /(T + 273.15) 3 8.621949 x1011 /(T + 273.15) 4 S [1.7674 x10 2 10.754 /(T + 273.15) + 2.1407 x10 3 /(T + 273.15) 2 ]}

(1 p wv / p)(1 p) c s (T , S , p) = c s (T , S ) p ( 1 )( 1 ) wv
p wv = exp[11.8575 3.8407 x10 3 /(T + 273.15) 2.16961x10 5 /(T + 273.15) 2 ]

= 0.000975 1.426 x10 5 T + 6.436 x10 8 T 2

Standard Methods (1995)

Cs (T, S, p)
T=0o Effect of p (S=0)
p = 1 atm (z=0) p = 0.89 (1000m) p = 0.79 (2000m) 14.6 12.9 11.4 14.6 13.6 11.4 11.3 19.9 8.8 11.3 10.6 9.0 9.1 8.0 7.1 9.1 8.6 7.4 7.6 6.7 5.9 7.7 7.2 6.2

10

20

30

Effect of S (p=0)
S = 0 PSU S = 10 S = 35

Processes affecting DO
Re-aeration (+/-) BOD (-) P(+)/R(-)

Inflow (+/-)

SOD (-)

Biochemical Oxygen Demand

Organic wastes are food for microorganisms

Oxygen consumed in process Self-purification (bio-degradation) in natural waters Biological stage of WWT C2H6O2 NaHSO3

Other chemicals exert oxygen demand

Theoretical Oxygen Demand

C n H a Ob N c Pd + (n + + dH 3 PO4
3 NH 3 + O2 = NO2 + H + + H 2 O 2

a b 3c 5d a 3c 3d + )O2 = nCO2 + ( ) H 2 O + cNH 3 4 2 4 4 2 2 2

Carbonaceous BOD (CBOD) Nitrogenous BOD (NBOD)

NO2

1 + O2 = NO3 2

Issues

Different types of wastes Some not labile Rates vary (nitrification)

Practical Measures of Oxygen Demand

BOD

Traditional water quality measure Cumbersome and time-consuming Easy to measure State variable in WQ models

COD

TOC

Traditional BOD
Practical measure of O2 debt

How much DO would decrease due to respiration of organic wastes Observe the decline of DO over time (e.g. 5 days) Extrapolate to ultimate demand Used for wastewater and natural waters

BOD Jar Test

BOD Jar Test

Precautions

No photosynthesis Enough initial O2 Adequate dilution (WW) Enough microorganisms Non toxic sample Only carbonaceous BOD

[DO]

y(t) y5 = BOD5 yu = BODu

time
0 5 days

y = L(1 e K1t )
L5 L= 1 e 5 K1

In rivers
Kr = Kd + Ks

K 1 = K 1 (20) T 20

K 1 (20) ~ 0.1 0.5d 1 ; ~ 1.047

K s = ws / h

Other Measures of BOD

COD

Easy to measure Much quicker State variable in WQ models BOD5/COD ~ 0.4 to 0.8 BOD5/TOC ~1.0 to 1.6

TOC

Relationship to BOD (Metcalf & Eddy)

Stream Reaeration
z w h
H c cs

Water side control Flux F ~ DO deficit Piston velocity [LT-1]

F=kL(cs-c)

kL ~ kw Ka = K2 = kw/h Stagnant Film Surface Renewal

Reaeration rate [T-1]

= zw

Theories

Stream Reaeration
Stagnant Film
z w h
H c cs

kL = D/zw zw ~ (Dt)0.5 t ~ h2/Ez ~ h/u zw ~ (Dh/u)0.5 kL ~ (Du/h)0.5 Ka ~ (Du/h3)0.5

Surface Renewal
F=kL(cs-c)

Stream Reaeration Formulae

u in m/s, h in m,
3.93u 0.5 Ka = h1.5

T=20o

50 40 30 20

O'Connor

.05 0.1

Depth (ft.)

OConnorDobbins (1958) Churchill et al. (1962 Owens & Gibbs (1964)

5.0u K a = 1.67 h
5.3u 0.67 Ka = h1.85

10 8 6 5 4 3 2 1 0.8 0.6 0.5 0.4 0.3 0.1 5 10

0.5 1 Churchill 5 10

50

100

Owens 2 3 4 5 6

0.2 0.3 0.4 0.6 0.8 1 Velocity (ft./sec.)

Kovar, 1976
Figure by MIT OCW.

Other formulations
Rate of Energy Dissipation (Tsivoglou LS H = & Wallace, 1972) T L / u = uS
Pool and Riffle Q < 0.56 Q > 0.56 Channel Control Q < 0.56 Q > 0.56 88(uS)0.313H-0.353 142(uS)0.333H-0.66W0.243

Melching and Flores (1999)

Reaeration Coefficient Ka 517(uS)0.524Q-0.242 596(uS)0.528Q-0.136 CV 0.61 0.44

0.59 0.60

(Streeter-Phelps, 1925)
Continuity
A + ( Au ) = q l t x

1-D Analysis

Mass Transport
c ( Ac ) + ( Auc ) = ( E L A ) + A(ri + re ) x x t x

BOD (c = L)
ri = K r L

re = ql Ll / A
q ( L L) dL u = K r L + l l A dx
dL = K r L + ( Ll L) d

dx = u ( x) 0

L( ) = Lo exp[ ( K r + ) ] +

(K r + )

Ll

{1 exp[( K r + ) ]}

DO (c = c)
ri = K d L
re = ql cl / A + K a (cs c)
u q (c c ) dc = K d L + K a (c s c ) + l l A dx

dc = K r L + K a (c s c ) + (c l c ) d
( ) = o exp[( K a + ) ] + +

= cs c

K dLl {1 exp[( K a + v) ]} ( K r + v)( K a + v)

Kd Ll L o {exp[( K r + v) ] exp[( K a + ) ]} (K a K r ) (K r + )

Streeter-Phelps-additional comments
cmin and xmin can be calculated analytically Multiple sources handled by superposition or re-initialization at stream confluences Procedures for anoxic conditions Neglect of longitudinal dispersion? Additional terms

Nitrification
C n H a Ob N c Pd + (n + + dH 3 PO4 a b 3c 5d a 3c 3d + )O2 = nCO2 + ( ) H 2 O + cNH 3 4 2 4 4 2 2 2

3 NH 3 + O2 = NO2 + H + + H 2 O 2
1 NO2 + O2 = NO3 2

(2)(32/14) = 4.57 (0.5)(32/14) = 1.14

Theoretical (upper bound) NBOD

NBOD = 4.57(Org N + NH 3 N ) + 1.14 NO2 N

NBOD 4.57TKN

TKN = total Kjeldalh nitrogen

[DO]

CBOD

NBOD 0 0

time Time scale for NBOD ~ 10 days => often insignificant in rivers If important, separate CBOD & NBOD analyses required May be better to include nitrogen species as state variables

Sediment Oxygen Demand (SOD)

BOD in sediments Significant downstream from outfalls or following algal blooms SB = 0.1 to 1 g/m2-d re = SB/h

Oth order process 0.1 to 1 mg/L-d (h = 1 m)

SOD (contd)
Measured

in situ with benthic flux chambers

in lab with core

Calculated from organic carbon content of settled solids Calibrated from oxygen model Complication: extraneous sources

Benthic Flux Chambers

Zebra Mussels

Algal Photosynthesis and Respiration

Photosynthesis (primary production) => fixation of CO2 by autotrophic bacteria Reverse is respiration 6CO2 + 6H2O C6H12O6 + 6O2

P/R (contd)
Limitations on primary production:

Light Temperature Nutrients Diurnal variation Depth variation

Time and space dependent

P(t)

Pm Pa 0
2f Pm 24

24 h

Pa =

f = photoperiod (hrs)

13

12

Curve A

Wyman Creek, Calif August 6, 1962 Average 10.1 MG/L

11

Dissolved Oxygen MG/L

10

9 Curve B 8 River Ivel, England May 31, 1959 Average 10.4 MG/L

7 0600

0900

1200N

1500

1800

2100

2400

0300

0600

Hours
Figure by MIT OCW.

EPA (1985)

Estimation of P/R
In situ measurements w/ Light & Dark Bottles
c o ct R= Kd L t dark

mg/L-d; L = ultimate BOD of filtered sample

ct c o ct c o P (t ) = t t light dark
P(t) is averaged over time t. t = 24 hrs => Pa; t< 24 h => fit to diurnal variation using f

Pm Pa 0 f 24 h t

Estimation of P/R (contd)

Calibrate to observed diurnal variation in P(t) using estimated Ka

Delta Method (Chapra and DiToro, 1979)

Correlate with chlorophyll-a

P = 0.25Chl a

R = 0.025Chl a

Expanded Streeter-Phelps Eqs*

S B ( P R) dc u = K r L K N L N + K a ( c s c ) + (c l c ) + d h h
CBOD NBOD* Reaeration Lat Inflow SOD P/R

L( ) = Lo exp[ ( K r + ) ] +

(K r + )

Ll

{1 exp[( K r + ) ]}

L N ( ) = L No exp[( K N + v) ]

Expanded S-P (contd)

= o exp[( K a + ) ] + Kd Ll Lo {exp[( K r + ) ] exp[( K a + ) ]} (K a K r ) Kr + K dLl {1 exp[( K a + ) ]} + ( K r + )( K a + ) K N L No {exp[( K N + ) ] exp[( K a + ) ]} + (K a K N ) (P R S B / H ) {1 exp[( K a + ) )]} (K a + )

Expanded S-P (contd)

Lateral BOD sources w/o significant inflow

q l Ll Lrd = A

=0

= x/u

K L = o exp( K a x / u ) + d o [exp( K r x / u ) exp( K a x / u )] Ka Kr K N L No {exp( K N x / u ) exp( K a x / u )} + (K a K N ) + K d Lrd [1 exp( K a x / u )] K d Lrd [exp( K r x / u ) exp( K a x / u )] Kr Ka (K a K r )K r

P R SB H [1 exp( K a x / u )] K a

Artificial Reaeration
Open water bodies (direct transfer, turnover, fountains) Hydropower stations (inject to turbine intake, downstream aeration)