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Updated: 23 January 2016
Lecture #1
Introduction: Course Administration and
Chemistry Review
(Stumm & Morgan, Chapt. 1)
(pp.1-4)
(Benjamin, 1.1 & 1.4)
David Reckhow
CEE 680 #1
1
Course Administration
 Course Syllabus
 Textbook: Benjamin, Water Chemistry,
Waveland Press, 2010
 must read, not all topics may be covered
 Detailed Course Outline
 Homework policy
 most graded;
 Projects
 MINEQL, review of literature
 Web site
David Reckhow
CEE 680 #1
2
Other References
 1. Pankow, Aquatic Chemistry Concepts. Lewis Publ., Chelsea, MI,
1991
 2. Stumm & Morgan, Aquatic Chemistry. 3rd Ed., John Wiley &
Sons., 1995


Extra copy on shelf in 3rd floor Elab II office
UM Science GB855 .S78 1996
 3. Jensen, A problem Solving Approach to Aquatic Chemistry,
Wiley, 2003.

UM Science GB855 .J46 2003
 4. Sawyer, McCarty & Parkin, Chemistry for Environmental
Engineering, McGraw Hill, 2003.

Extra copy of 3rd edition on shelf in 3rd floor Elab II office
 5. Snoeyink & Jenkins, Water Chemistry, John Wiley & Sons., 1980.

David Reckhow
UM Science QD169.W3 S66
CEE 680 #1
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General Questions for Aquatic Chemists
 What is the chemical composition of natural
waters?
 Will it change with time, location?
 What happens to chemical species when they
enter new aquatic or non-aquatic environments?
 How does transport affect the chemistry?
 What types of reactions occur in treatment
systems?
 What do we need to do to make it work better?
David Reckhow
CEE 680 #1
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Examples from Water Treatment
 How can we use chemistry to stop corrosion and
dissolution of lead?
 What with the pH, alkalinity and hardness be after
mixing two different types of water
 e.g., groundwater and surface water
 How do we get the best performance from chemical
precipitation processes
 e.g., coagulation, softening
 What can we do to optimize oxidation treatments
 e.g., removal of Mn, trace organic constituents
David Reckhow
CEE 680 #1
5
Example 1: Lead and Water
 Lead is a neural toxin
 Especially serious in children
 EPA: Pb & Cur Rule Published in 1991
 The treatment technique for the rule requires systems to
monitor drinking water at customer taps. If lead
concentrations exceed an action level of 15 ppb or
copper concentrations exceed an action level of 1.3 ppm
in more than 10% of customer taps sampled (i.e.,
90%ile), the system must undertake a number of
additional actions to control corrosion.
David Reckhow
CEE 680 #1
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Flint Michigan Crisis
 Timeline
 April 2014: the city stopped getting its water from
Detroit as a cost-saving measure and began instead
drawing water from the Flint River.
 High blood lead levels noted in children
 Water led levels were above standard
 Oct 16, 2015: Flint switches back to Detroit Water
 Sources
 VPI website: http://flintwaterstudy.org/
 12/22/2015 Rachel Maddow video:
David Reckhow
CEE 680 #1
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Flint Water Quality - Edwards
Parameter
Before
4/2014
After
4/2014
units
pH
7.38
7.61
Hardness
101
183
mg-CaCO3/L
Alkalinity
78
77
mg-CaCO3/L
Chloride
11.4
92
mg/L
Sulfate
25.2
41
mg/L
CSMR
0.45
1.6
Inhibitor
0.35
None
Larson Ratio
0.5
2.3
mg-P/L
WQ data From MOR and 2014 WQR
CSMR = chloride to sulfate mass ratio
Larson Ratio = ([Cl-] + 2[SO4-2])/[HCO3-]
David Reckhow
CEE 680 #1
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 Edwards slide
David Reckhow
CEE 680 #1
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Daily Hampshire Gazette: 22 Jan 2013
 das
David Reckhow
CEE 680 #1
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Daily Hampshire
Gazette: 22 Jan
2013
 Environmental Justice
issue
David Reckhow
CEE 680 #1
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Example 2: differing water quality
 Many, perhaps most,
drinking water
utilities have
multiple sources
 Often those sources
have contrasting
water quality
 Especially common
for regional supplies,
like Tampa Bay
David Reckhow
CEE 680 #1
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Groundwater
and surface
water
 Tampa Bay area and
regional supply
 Groundwater
 River water
 Ocean water: desal
David Reckhow
CEE 680 #1
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Pinellas County Water
 Standard WQ Analyte List (103 total)
1,1-Dichloro-2propanone
Bromochloroacetonitrile
Total Haloacetic
Acids (HAA5)
sec-Butylbenzene
Chloropicrin
Trichloroacetic acid
Dichlorodifluoromethane
Styrene
Decafluorobiphenyl
Alkalinity as CaCO3
1,1-Dichloroethylene 4-Isopropyltoluene
Ethylbenzene
tert-Butylbenzene
Dibromoacetonitrile
Total Hardness
1,1-Dichloropropene Benzene
Fluorobenzene
Tetrachloroethylene Dichloroacetonitrile
Total Dissolved
Solids
cis-1,3Dichloropropene
Dibromochloro2,2-Dichloropropane
methane
Calcium
1,1,1-Trichloroethane 1,4-Dichlorobenzene
n-Propylbenzene
Iron
1,1,2,2Tetrachloroethane
ortho-Xylene
Magnesium
1,1,2-Trichloroethane 2-Chlorotoluene
Dibromomethane
Arsenic
1,1-Dichloroethane
Copper
Lead
Bromide
Chloride
Nitrate as N
Nitrite as N
1,2,3Trichlorobenzene
1,2,4Trichlorobenzene
1,2,4Trimethylbenzene
4-Chlorotoluene
Bromobenzene
Bromochloromethane Isopropylbenzene
Bromodichloromethane
1,2-Dichlorobenzene Bromoform
Orthophosphate as P 1,2-Dichloroethane
Hexachlorobutadiene Toluene
meta/para-Xylene
Methyl bromide
Carbon tetrachloride Methyl chloride
Total
Trihalomethanes
trans-1,2Dichloroethylene
trans-1,3Dichloropropylene
Total
Haloacetonitriles
Ammonia as N
Trichloroacetonitrile
Free Ammonia as N
Chloral hydrate
Total Organic Carbon
Decafluorobiphenyl
UV 254
1,2,3Trichloropropane
Trichlorofluorometha 2-Bromopropionic
ne
Acid
Heterotrophic Plate
Count
Total Coliforms
Trichloroethene
Orthophosphate as
PO4, calculated
1,2-Dichloropropane Chlorobenzene
Methylene chloride
Sulfate
1,3,5Trimethylbenzene
Methyl tert-butyl
ether
Vinyl chloride
Bromoacetic acid
Phosphorus, Total
(as P)
1,3-Dichlorobenzene Chloroform
Naphthalene
Xylene (total)
Chloroacetic acid
n-Butylbenzene
CEE
680 #1
1,1,1-Trichloro-2propanone
Dibromoacetic acid
Chloroethane
1,1,1,2cis-1,2David Reckhow 1,3-Dichloropropane Dichloroethylene
Tetrachloroethane
Dichloroacetic acid
E. coli
14
Keller 2
 Groundwater source: Eldridge Wilde Wellfield
 40 MGD
 WQ Challenge
 1-1.5 ppm H2S,
VOCs
 Water Treatment
 Air Stripping with
CO2
 Chlorination
 Ammoniation
 Polyphosphate
 Air treatment
 Water scrubbing
with caustic &
chlorine
David Reckhow
CEE 680 #1
15
Majors – mostly inorganics
 Keller Plant 2 Sample Station: Aug 9, 2010
Parameter
Calcium
Value Units
Parameter
77.7
mg/L
Sulfate
0.018
mg/L
Phosphorus, Total (as P)
5.08
mg/L
Arsenic
0.0002
Copper
Lead
Value
Units
4
mg/L
0.23
mg/L
Alkalinity as CaCO3
209
mg/L
mg/L
Total Hardness
215
mg/L
0.0013
mg/L
Total Dissolved Solids
316
mg/L
0.0001
mg/L
Ammonia as N
0.84
mg/L
Bromide
0.05
mg/L
Free Ammonia as N
0.16
mg/L
Chloride
22
mg/L
Total Organic Carbon
3.7
mg/L
0.04
mg/L
UV 254
0.117
cm - 1
Nitrite as N
0.02
mg/L
Heterotrophic Plate
Count
3
CFU/ml
Orthophosphate as P
0.12
mg/L
E. coli
1
MPN/100ml
Orthophosphate as PO4
0.37
mg/L
Total Coliforms
1
MPN/100ml
Iron
Magnesium
Nitrate as N
David Reckhow
CEE 680 #1
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Trace Organics above MDL
 Keller Plant 2 Sample Station: Aug 9, 2010
Parameter
Bromodichloromethane
Value
Units
Parameter
Value
Units
8.3
ug/L
Dibromoacetonitrile
0.77
ug/L
45
ug/L
Dichloroacetonitrile
10.7
ug/L
0.9
ug/L
Total Haloacetonitriles
13.3
ug/L
Total Trihalomethanes
54.2
ug/L
Trichloroacetonitrile
0.12
ug/L
1,1,1-Trichloro-2-propanone
3.47
ug/L
Chloral hydrate
5.45
ug/L
1,1-Dichloro-2-propanone
1.36
ug/L
Dichloroacetic acid
12.6
ug/L
Bromochloroacetonitrile
1.73
ug/L
Total Haloacetic Acids (HAA5)
31.8
ug/L
Chloropicrin
0.21
ug/L
Trichloroacetic acid
19
ug/L
Chloroform
Dibromochloromethane
David Reckhow
CEE 680 #1
17
Pinellas Questions
 What does the detailed analysis tell you?
 Does it make sense?
 Expressions of concentration?
 Principle of electroneutrality?
 TDS, TH, Alk, TOC, UV – what do these mean
David Reckhow
CEE 680 #1
18
Pinellas calculations 1
Calcium
Iron
Magnesium
Arsenic
Copper
Lead
Bromide
Chloride
Nitrate as N
Nitrite as N
Orthophosphate as P
Orthophosphate as PO4,
calculated
Sulfate
Phosphorus, Total (as P)
Alkalinity as CaCO3
Total Hardness
Total Dissolved Solids
Ammonia as N
Free Ammonia as N
Total Organic Carbon
UV 254
Heterotrophic Plate
Count
E. coli
Total Coliforms
conc (mg/L)
77.70
0.02
5.08
0.00
0.00
0.00
0.05
22.00
0.04
0.02
0.12
77.7 mg/L
0.018 mg/L
5.08 mg/L
0.0002 mg/L
0.0013 mg/L
0.0001 mg/L
0.05 mg/L
22 mg/L
0.04 mg/L
0.02 mg/L
0.12 mg/L
0.37 mg/L
4 mg/L
0.23 mg/L
209 mg/L
215 mg/L
316 mg/L
0.84 mg/L
0.16 mg/L
3.7 mg/L
0.117 cm - 1
0.37
4.00
0.23
209.00
215.00
316.00
0.84
0.16
3.70
GFW
mM
charge/M meq/L
pos
neg
40.078
1.9387
2 3.87744 3.87744
55.845
0.0003
3 0.00097 0.00097
24.305
0.2090
2
0.41802
0.41802
74.922
0.0000
-1 0.00000 0.00000
63.546
0.0000
2 0.00004 0.00004
207.2
0.0000
2 0.00000 0.00000
79.904
0.0006
-1 -0.00063
-0.00063
35.453
0.6205
-1 -0.62054
-0.62054
14.007
0.0029
-1 -0.00286
-0.00286
14.007
0.0014
-1 -0.00143
-0.00143
30.974
0.0039
-3 -0.01162
-0.01162
94.97
96.061
30.974
50.037
100.074
0.0039
0.0416
0.0074
4.1769
2.1484
14.007
14.007
12.011
0.0600 .
0.0114
0.3081
-3
-2
-0.01169
-0.08328
0.00000
-4.17691
4.29682 .
-1
2
-0.08328
-4.17691
.
1
0.01142
0.00000
0.01142
0.00000
3 CFU/ml
1 MPN/100ml
1 MPN/100ml
Total =
854.33 add
323.33 exclude TDS, TH
sum
diff
%
David Reckhow
.
CEE 680 #1
4.30789 -4.89726
-0.58937
12.0%
19
Pinellas calcs 2
mass of E. coli
0.5 um
2 um
cylinder
volume =
density =
0.3927 um3 =
3.927E-10 mm3 =
3.93E-13 g =
1 in
3.93E-10 mg
100 mL
mass
concentra
tion = 3.93E-09 mg/L =
HPC example
conc =
3 in
mass
concentra
tion =
David Reckhow
3.927E-13 cm3
1 g/cm3
mass/cell
=
E.coli example
conc =
diameter
long
3.93E-06 ug/L =
3.93E-03 ng/L
1.18E-03 ug/L =
1.18E+00 ng/L
1 mL
1.18E-06 mg/L =
CEE 680 #1
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Pinellas Discussion
 Missing Na, K
 13.5 mg/L Na would close the balance
David Reckhow
CEE 680 #1
21
Relation with Environmental Engineering
Math
Environmental
Engineering
Biology
Physics
Chemistry
David Reckhow
CEE 680 #1
22
Relation with other Chemistry Disciplines
Physical
Chemistry
Analytical
Chemistry
Inorganic
Organic
Chemistry
Chemistry
Chemistry
680
Thermodynamics
684
Kinetics
 A cornerstone of the good grad programs in our field
David Reckhow
CEE 680 #1
23
Review
 Units
 Mass based
 Molarity
 Molality
 Normality
 Mole fraction
 Atmospheres
David Reckhow
CEE 680 #1
 Chemical Stoichiometry
 mass balance
 balancing equations
 Thermodynamics
 law of mass action
 types of equilibria
24
SI Unit prefixes
Factor
Prefix
Symbol
10-1
deci
d
10-2
centi
c
10-3
milli
m
10-6
micro
µ
10-9
nano
n
10-12
pico
p
10-15
femto
f
10-18
atto
a
David Reckhow
CEE 680 #1
Factor
101
102
103
106
109
1012
1015
1018
Prefix
deka
hecto
kilo
mega
giga
tera
peta
exa
Symbol
da
d
k
M
G
T
P
E
25
Mass Based Concentration Units
 Solid samples
17.5mg Pb 17.5 x10 −3 g Pb 17.5 g Pb
=
=
6
3
g soil
10
1kg soil
1x10 g soil
= 17.5 ppm m Pb in soil
1mg / kg = 1 ppmm
1µg / kg = 1 ppbm
David Reckhow
CEE 680 #1
26
 Liquid samples
Density of
Water at 5ºC
0.35mg Fe 1L water
x 3
1L water 10 g water
0.35mg Fe 0.35 x10 −3 g Fe 0.35 g Fe
= 3
=
=
6
3
10
g water
10 g water
10 g water
= 0.35 ppm m Fe in water
David Reckhow
CEE 680 #1
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Mass/Volume Units
Mass/Mass Units
Typical Applications
g/L (grams/liter)
mg/L (milligrams/liter)
10-3g/L
µg/L (micrograms/liter)
10-6g/L
ng/L (nanograms/liter)
10-9g/L
pg/L (picograms/liter)
10-12g/L
(parts per thousand)
ppm (parts per million)
ppb (parts per billion)
Stock solutions
Conventional pollutants
(DO, nitrate, chloride)
Trihalomethanes, Phenols.
ppt (parts per trillion)
PCBs, Dioxins
David Reckhow
CEE 680 #1
Pheromones
28
 Gas samples (compressible)
0.056mg Ozone
1m 3 air
 Could be converted to a ppmm basis
 But this would change as we compress the air
sample
 Could also be converted to a ppmv basis
 Independent of degree of compression
 But now we need to convert mass of ozone to
volume of ozone
David Reckhow
CEE 680 #1
29
Ideal Gas Law
By definition:
mass ( g )
n=
GFW
 An ideal gas
 Will occupy a certain fixed volume as determined by:
PV = nRT
RT mass ( g ) RT
V =n
=
P
GFW P
regardless of the nature of the gas
 Where:






David Reckhow
P=pressure
=22.4 L
V=volume
at 1 atm, 273.15ºK
n=number of moles
T=temp
R=universal gas constant=0.08205 L-atm/mole-ºK
GFW=gram formula weight
CEE 680 #1
30
Convert mass to moles
 Now we know that ozone’s formula is O3
 Which means it contains 3 oxygen atoms
 Therefore the GFW = 3x atomic weight of oxygen in
grams or 48 g/mole
0.056mg Ozone
3
1m air



David Reckhow
n=mass(g)/GFW
n=0.056x10-3g/(48g/mole)
n=0.00117x10-3 moles
CEE 680 #1
0.00117 x10 −3 moles Ozone
1m 3 air
31
Now determine ppmv
volumeozone
ppmv =
volumeair
0.00117 x10 −3 moles x 22.4 L / mole
=
1m 3 air
0.026 x10 −3 L Ozone
=
1x103 L air
= 0.026 ppm v O 3 in air
= 26 ppb v O 3 in air
David Reckhow
CEE 680 #1
32
Mole & volume fractions
 Based on the ideal gas law:
RT
Vi = ni
P
RT
Vtotal = ntotal
P
 The volume fraction (ratio of a component gas volume to
the total volume) is the same as the mole fraction of that
component
Vi
ni
=
 Therefore:
V
n
total
total
Defined as:
Volume fraction
Defined as:
mole fraction
 And since the fraction of the total is one-millionth of the
number of ppm:
David Reckhow
CEE 680 #1
Vi
ni
10 ppmv ≡
=
Vtotal ntotal
−6
33
PV = nRT
n
P = RT
V
Partial pressures
 Based on the ideal gas law:
 And defining the partial pressure (Pi) as the pressure a
component gas (i) would exert if all of the other
component gases were removed.
 We can write:
ni
Pi =
RT
Vtotal
 Which leads to:
Pi
ni
=
Ptotal ntotal
ni
= Ptotal 10 −6 ppmv
ntotal
 And:
David Reckhow
Pi = Ptotal
CEE 680 #1
and
Ptotal
ntotal
RT
=
Vtotal
34
Earth’s Atmosphere
David Reckhow
CEE 680 #1
Divide by 100 and
you get the partial
pressure for a total
pressure of 1 atm.
35
 To next lecture
David Reckhow
CEE 680 #1
36