DO modeling in surface waters

EnE 210 Water Quality Processes

F.C. Ballesteros, Jr., Ph.D.

DO in surface waters
DO content is one of the most widely used
indicators of overall ecological health of a body
of water
fish need 4 to 5 mg/L to survive
under anaerobic conditions, undesirable
(smelly) microbes can take over
many factors affect the DO level

When WW is discharged
At the outfall, BOD of the river/wastewater
mixture (L0) is given by:

The BOD is comparable to what we have in our

stoppered bottle at the beginning of a BOD test
As time passes (ie
(ie,, the water moves downstream) the oxygen
content of the river water is consumed in just the same way
oxygen is consumed in the test
BOD (Lt) in a test bottle at time t is given by:
Lt = L0e-kDt
This formula holds in the river too (k
(kD is the deoxygenation
constant that we previously just called k; it can be
adjusted for temperature using kT = k20q T-20)

Effect of Organic Wastes on

Stream Ecosystems

Streeter--Phelps Model DO sag curve

Streeter





Many equations and computer programs are available

today to describe the quality of water in streams, rivers
and lakes
The most prevalent is the Streeter Phelps equation.
Addition of wastewater (BOD) typically causes a slow
decrease in O2, followed by a gradual increase close to
the dissolved oxygen (D.O.) saturation concentration

Streeter-Phelps Model

Assumptions of the Model


stream is an ideal plug flow reactor

steady--state flow and BOD and DO reaction
steady
conditions

The only reactions of interest are BOD
exertion and transfer of oxygen from air to
water across airair-water interface

Streeter-Phelps Model

Mass Balance for the Model

rate of deficit increase = rate of deoxygenation - rate of reaeration



Both reoxygenation and deoxygenation are 1st order

rate of deoxygenation = -k1C

k1= deoxygenation constant, function of waste type and
temperature

Streeter-Phelps Model
rate of reoxygenation = k2D
D = deficit in D.O. or difference between saturation
and current D.O.
k2 = reoxygenation constant

k2 =

3.9v

1
2

1
2

([1.025] )
(T20)

Table 3-2 Reaeration constants

Water body

Ranges of kR at 20C,
base e

Small ponds and backwaters

0.1-0:23

Sluggish streams and large lakes

0.23-0.35

Large streams of low velocity

0.35-0.46

Large streams of normal velocity

0.46-0.69

Swift streams

0.69-1.15

Rapids and waterfalls

Greater than 1.15

Source: Peavy, Rowe and Tchobanoglous, 1985

Streeter-Phelps Model
Where
 T = temperature of water, C
 H= average depth of flow, m
 v = mean stream velocity, m/s

Oxygen Deficit
D = S C

D.O. deficit = saturation D.O. D.O. in the water

Streeter-Phelps Model

Streeter-Phelps Model
Deoxygenation rate is equivalent to BOD of
waste
 ro = k1 Lt
 Lt = Loe-Kt
Lo or L = ultimate BOD of the wastewater and
stream water mixture

Streeter-Phelps Model

In terms of the deficit with time

dD
= k1C k 2 D
dt
k1t
C = Lo e

Streeter-Phelps Model

Substituting and integrating yields the following

equations
D=

k1 Lo
(e k1t e k2t ) + Do e k2t
k 2 k1

dD
= k 1 Lo e k1t k 2 D = 0
dt
k1
k1 t
Dc =
Lo e
k2

The above equation is the StreeterStreeter-Phelps oxygen

oxygen--sag curve
formula
Note that for a constant stream crosscross-section, t=x/u (with
u=stream velocity); therefore:

Streeter-Phelps Model
Since the BOD is decreasing as time goes on, at some point, the rate of
deoxygenation decreases to just the rate of reaearation
At this point (called the critical point) the DO reaches a minimum

dD
k1 t
= k 1 Lo e k 2 D = 0
dt
k1
Dc =
Lo e k1t
k2
Downstream of the critical point, reaeration occurs faster than
deoxygenation,, so the DO increases
deoxygenation

Time to reach critical DO

Streeter-Phelps Model

Example:
 Wastewater mixes with a river resulting in a

BOD = 10.9 mg/L, DO = 7.6 mg/L

The mixture has a temp. = 20 C
Deoxygenation const.= 0.2 day-1
Average flow = 0.3 m/s,
Average depth = 3.0 m
DO saturated = 9.1 mg/L

Find the time and distance downstream at which the
oxygen deficit is a maximum?

Find the minimum value of DO?

Streeter-Phelps Model
Initial Deficit
Do = 9.1 7.6 = 1.5 mg/L

Estimate the reaeration constant

(2020 )

3.9v
3.9(0.3m / s ) [1.025]
k2 =
=
3/ 2
H
(3.0m) 3 / 2
1/ 2

1/ 2

= 0.41 day 1

Streeter-Phelps Model

Calculate the time at which the maximum deficit

is reached, with tc:

k2 DOo (k2 k1 )
1
tc =
ln 1

k2 k1 k1
k1Lo

0.41 1.5(0.41 0.2)

1
ln
1
=

(0.41 0.2) 0.2

0.2 10.9
= 2.67days
xc = vtc = 0.3m / s 86,400s / day 2.67days = 69,300m

Streeter-Phelps Model

The maximum DO deficit is:

k1
k1t
Dc = Lo e
k2
0.2
(0.2day1 )(2.67days)
=
(10.9 mg/L)e
0.41
= 3.1 mg/L

Ion Exchange

Hardness and Nitrate Removal

Definition
Ion exchange is a reversible chemical
reaction wherein an ion (an atom or
molecule that has lost or gained an
electron and thus acquired an electrical
charge) from solution is exchanged for a
similarly charged ion attached to an
immobile solid particle.

Common Problems

Hardness

Nitrates

Uranium

Arsenic

Heavy Metals

Typical Skid Mounted Systems

Ion Exchange Process

Types of Ion Exchange Systems

+++++++ Cation exchangers, which
have positively charged mobile ions
available for exchange
------- Anion exchangers, whose
exchangeable ions are negatively
charged

Resins

Strong Acid Cation Resins

Strong acid resins are so named because their

chemical behavior is similar to that of a strong

acid.

The resins are highly ionized in both the acid
(R-SO3H) and salt (R-SO3Na) form. They can
convert a metal salt to the corresponding acid
by the reaction:
2(R-SO3H)+ NiCl2  (R-SO4),Ni+ 2HCI

Strong Base Anion Resins

Strong base resins are highly ionized and can

be used over the entire pH range.

These resins are used in the hydroxide (OH)
form for water deionization. They will react
with anions in solution and can convert an
acid solution to pure water:
R--NH3OH+ HCl  R-NH3Cl + HOH

Selectivity of ion Exchange Resins

Order of Decreasing Preference
Strong acid cation exchanger
1. Lead
2. Calcium
3. Nickel
4. Cadmium
5. Copper
6. Zinc
7. Magnesium
8. Potassium
9. Hydrogen
10. Ammonia
11. Sodium

Strong base anion exchanger

1. Iodide
2. Nitrate
3. Bisulfite
4. Chloride
5. Cyanide
6. Sulfate
7. Hydroxide
8. Fluoride
9. Bicarbonate

About Ion Exchange Media

These solid ion exchange particles are either naturally

occurring inorganic zeolites or synthetically produced

organic resins.

The synthetic organic resins are the predominant type
used today because their characteristics can be tailored
to specific applications.

An organic ion exchange resin is composed of highmolecular-weight polyelectrolytes that can exchange
their mobile ions for ions of similar charge from the
surrounding medium.

Each resin has a distinct number of mobile ion sites that
set the maximum quantity of exchanges per unit of
resin.

Regeneration Process
1.

2.

3.

4.

5.

The column is backwashed to remove suspended solids

collected by the bed during the service cycle and to
eliminate channels that may have formed during this cycle.
The back-wash flow fluidizes the bed, releases trapped
particles, and reorients the resin particles according to size.
The resin bed is brought in contact with the regenerant
solution. In the case of the cation resin, acid elutes the
collected ions and converts the bed to the hydrogen form.
A slow water rinse then removes any residual acid.
The bed is brought in contact with a sodium hydroxide
solution to convert the resin to the sodium form. Again, a
slow water rinse is used to remove residual caustic. The
slow rinse pushes the last of the regenerant through the
column.
The resin bed is subjected to a fast rinse that removes the
last traces of the regenerant solution and ensures good
flow characteristics.
The column is returned to service.

About Calculations

Resin capacity is usually expressed in terms of equivalents

per liter (eq/L) of resin.

An equivalent is the molecular weight in grams of the
compound divided by its electrical charge or valence. For
example a resin with an exchange capacity of 1 eq/L could
remove 37.5 g of divalent zinc (Zn+2, molecular weight of 65)
from solution.
Much of the experience with ion exchange has been in the
field of water softening: therefore, capacities will frequently be
expressed in terms of kg of calcium carbonate per cubic foot
of resin.
This unit can be converted to equivalents per liter by
multiplying by 0.0458.
The capacities are strongly influenced by the quantity of acid
or base used to regenerate the resin.
Weak acid and weak base systems are more efficiently
regenerated; their capacity increases almost linearly with
regenerate dose.

Quick 80% Accuracy Calculation

1.
2.
3.
4.

5.

Cation columns
Take your water TDS (total dissolved solids)
analysis.
Look at Calcium, Magnesium and Sodium
concentrations in ppm.
Add up the total ppm and divide by 17.1 (i.e., 250
ppm/17.1 = 14.6 grams/gal).
Assuming a conservative 16 kilogram/cu. ft.
capacity with an economical regeneration, now
divide 16,000 by 14.6 (16000/14.6 = 1095).
You will get over a thousand gallons of
decationized water per cubic foot of resin.

Quick 80% Accuracy Calculation

1.
2.
3.
4.
5.

Anion columns
Next add up the anions, they should be equal to
the cations plus silica (SiO2) and dissolved CO2 .
Add up the anions plus silica and carbon dioxide in
ppm. Lets say total carbonate and silica is 20 ppm.
Take the total anion ppm and divide by 17.1 (270
(250+20)ppm /17.1 = 15.8 g/gal..).
Divide 14 kilogram/ft3 by your answer (14,000/15.8
= 886 gallons per cubic foot).
A 5 gpm system would require about 2.5 cu.ft. of
cation resin and about 3 cubic feet of anion resin,
resulting in about 2500 gallons of DI water
between regenerations.

MIEX Ion Exchange Process- Magnetic Ion

Exchange

End of presentation