Water Applications

ƒ Irrigation
— largest withdrawal use , in areas with inadequate rain
ƒ Public water supply Department of Chemical and Petroleum Engineering
— Homes, schools, hospitals, workplaces, commercial, fire
fighting WASTEWATER ISSUES FOR THE
ƒ Industry OIL AND GAS INDUSTRY
— Direct use (beverage), indirect (oil and gas) ENCH 665 – ENEN 665
ƒ Transportation Session 3: Introduction (Cont’d)
— Boats, ships and tankers, since ancient times, most
economical Nasser Sallamie, Ph.D., P. Eng.
Fall 2022
ƒ Recreation
— Swimming, bathing and fishing
3 1

Water Quality Outline

ƒ Water, as rain dissolves chemical components in ƒ Basic definitions (cont’d)
surrounding atmosphere, runs over ground surfaces, and
percolates through the soil — Water application
ƒ Water often needs treatment to become suitable for use — Water quality
ƒ Application and initial quality defining treatments — Solids in water and wastewater treatment
ƒ Physical properties — Physical and chemical properties of water
— Taste and odour: volatile chemicals and decomposing organic
matter — Biochemical properties of water
— Colour: minerals such as iron and manganese, organic materials — Dissolved gases (physical and chemical)
and colored industrial wastes — Coal-bed methane
— Turbidity: Objectionable appearance, particles can harbour
pathogens
ƒ Chemical standards (natural or industrial origin)
— Hardness (temporary vs. permanent)
ƒ Biological standards
4 2
 Concentration Water Quality Standards

ƒ Different physical units International Comparison of

— mg/L or g/m3 Drinking Water Quality
Standards and Guidelines for
— Pg/L or ng/L for concentration of trace constituents
Chemicals (Maximum Allowable
— ppm (mass-to-mass ratio) Concentration). All standards
ƒ The relationship between mg/L and ppm is: and guidelines in mg/L
݉݃Ȁ‫ܮ‬
‫ ݉݌݌‬ൌ Courtesy of David Suzuki Foundation:
ܵ‫݀݅ݑ݈ܨ ݂݋ ݕݐ݅ݒܽݎܩ ݂ܿ݅݅ܿ݁݌‬ “Water We Drink, An International
ƒ For dilute systems Comparison of Drinking Water Quality
Standards and Guidelines”, by David
— mg/L or g/m3 same as ppm Boyd
— ppb and ppt same as Pg/L or ng/L, respectively
ƒ Dissolved gases Similar data could be
— Volumetric ppm, mg/m3 or Pg/L found from WHO, EPA and
ƒ Conversion of gas concentration between ppm, and Health Canada
mg/m3 is given by the Ideal Gas Law 7 5

Solids in W & W Water Quality Standards (Cont’d)

ƒ Total Suspended Solids (TSS) International Comparison of
— An arbitrary filter from 0.45 Pm to about 2.0 Pm to separate total Drinking Water Quality
suspended solids (TSS) from total dissolved solids (TDS) Standards and Guidelines for
— Comparison between two TDS meaningful with similar filter types Chemicals (Maximum Allowable
— TSS results used routinely to assess performance of conventional Concentration). All standards
treatment processes and need for effluent filtration in reuse and guidelines in mg/L
applications
ƒ TSS lacks a fundamental basis Courtesy of David Suzuki Foundation:
“Water We Drink, An International
— TSS values dependent on the type and size of the filter used Comparison of Drinking Water Quality
— Autofiltration depending on sample size used for TSS; suspended Standards and Guidelines”, by David
solids intercepted by the filters also serving as a filter Boyd
ƒ Autofiltration leads to an apparent increase in TSS value
— Depending on characteristics of particulate matter, small particles Similar data could be
may be removed by adsorption to materials already retained by
the filter found from WHO, EPA and
— TSS is a lumped parameter, number and size distribution of Health Canada
particles comprising the measured value is unknown.
8 6
 Solids in W & W Solids in W & W (Cont’d)
ƒ Total Solids (TS)
— Residue remaining after a wastewater sample being evaporated and
dried at a specified temperature (103 to 105oC)
ƒ Total Volatile Solids (TVS)
— Solids that can be volatilized and burned off when TS are ignited
(500 r 50oC)
ƒ Total Fixed Solids
— Residue remaining after TS being ignited (500 r 50oC)
ƒ Total Suspended Solids (TSS)
— Portion of TS retained on a filter with a specified pore size,
measured after being dried at a specified temperature (105oC).
— Most commonly for the determination of TSS is the Whatman glass
fiber filter with a nominal pore size of about 1.58 Pm
ƒ Volatile Suspended Solids (VSS)
— Solids that can be volatilized or burned off when the TSS is ignited
(500 r 50oC).
11 9

Settleable Solids (Imhoff Cone) Solids in W & W (Cont’d)

Suspended solids (ml/lit) settling out of a suspension within a ƒ Fixed Suspended Solids (FSS)
specified period of time — Residue remaining after TSS being ignited (500 r 50oC)
ƒ Total Dissolved Solids (TDS)
— Solids passing through the filter, and then evaporated and dried
at a specified temperature
— TDS is comprised of colloidal and dissolved solids
— Colloids typically in the size range of 1 nm to 1 Pm
ƒ Total Volatile Dissolved Solids (VDS)
— Solids that can be volatilized and burned off when TDS being
ignited (500 r 50oC)
ƒ Fixed Dissolved Solids (FDS)
— Residue remaining after TDS being ignited (500 r 50oC)
ƒ Settleable Solids
— Suspended solids (in milliliters per liter) settling out of a
suspension within a specified period of time
12 10
 Turbidity Sludge Volumetric Index (SVI)

ƒ A measure of the light transmitting properties of ƒ volume in milliliters occupied by 1 g of a suspension

water after 30 minutes settling
— Another test used to indicate the quality of waste — Typically used to monitor settling characteristics of activated
discharges and natural waters with respect to colloidal sludge and other biological suspensions
and residual suspended matter. — SVI not supported theoretically but useful in routine process
control
ƒ Measurement based on comparison of the intensity — Determine suspended solids concentration of a well-mixed
of light scattered by a reference suspension under sample; then determine the 30 min settled sludge volume:
same conditions (Standard Methods, 1998) ୗୣ୲୲୪ୣୢ ୗ୪୳ୢ୥ୣ ୚୭୪୳୫ୣ ሺ୫୐Τ୐ሻൈଵ଴଴଴
 ൌ
ƒ Formazine suspensions used as primary reference ୗ୳ୱ୮ୣ୬ୢୣୢ ୗ୭୪୧ୢୱ ሺ୫୥Τ୐ሻ
standard — Most common use of SVI in monitoring waste treatment plant
operation and in comparing the settling characteristics of
— Results reported in nephelometric turbidity units (NTU) various sludges
— Presence of air bubbles in the fluid will cause erroneous — For primary/secondary clarifiers, an SVI of 180 shows poor
turbidity reading settling; while 60 is excellent
15 13

Turbidity (Cont’d) Silt Density Index (SDI)

ƒ SDI: a measure for fouling capacity of water in

reverse osmosis (nanofiltration) systems
— Test measures the rate at which a 0.45-micrometre filter is
plugged when subjected to a constant water pressure of
206.8 kPa (30 psi)
— SDI gives the percent drop per minute in the flow rate of
water through filter, averaged over a period of time such
as 15 minutes, usually based on 5, 10 and 15 minute rates

SDI<5: Reasonable quality

SDI=6.7: Complete blockage in 15 minutes

16 14
 Hardness (Cont’d) Color

ƒ Scale-produced on heating or failure to form lather ƒ Caused by natural materials (iron, manganese,
ƒ Sum of concentration of multivalent ions vegetable origin humus and tannins) and industrial
color discharges (mining, refining, pulp and food
— Ca, Mg, Fe, Mn, Ba, Zn, and Al industry)
ƒ Generally expressed in terms of equivalent milligrams ƒ True color
per liter (mg/L) of CaCO3 or in milliequivalents per liter — Attributable to substances in solution after removal of
— Grain per gallon (used in the past), where 17.1 mg/L (as CaCO3) suspended materials by centrifuging or filtration)
is equal to 1 gr/gal ƒ Apparent color
ƒ Total hardness — due to suspended materials
— Sum of Ca and Mg hardness (mg/L) as CaCO3 ƒ Standard color
— Sum of carbonate and none-carbonate hardness — Made by chemicals (K2PtCl6, potassium hexachloroplatinate, solution
tinted with CoCl2) or lab colorimeter, The color produced by 1
ƒ Carbonate hardness: carbonates and bicarbonates of Ca mg/L of platinum in combination of with 1/2 mg/L metallic
and Mg cobalt is taken as 1 standard color unit.
ƒ Non-carbonate hardness: non-carbonate salts of Ca and ƒ Laboratories often employ a colorimeter for reading
Mg (such as sulfate and chloride) 19 17

Hardness (Cont’d) Hardness

Hardness mg/L as CaCO3
Soft 0-75
Moderate 75-150 ƒ Temporary (carbonate) hardness
Hard 150-300 — Precipitation of scale in boilers due to carbonates and
Very hard 300+ bicarbonates of calcium and magnesium (can be removed
ƒ EDTA titration to determine hardness and (Ca2+ Mg2+) by boiling)
ƒ Ca ion complexed with EDTA molecule as of CaEDTA-2, ƒ Permanent (non-carbonate) hardness
or C10H12O8N2Ca — Water-soluble salts (cannot be removed by boiling)
— Carbon atoms: black ƒ Calcium sulfates
— Hydrogen atoms: white, ƒ Calcium chlorides
— Oxygen atoms: red, ƒ Calcium nitrates
— Nitrogen atoms: blue
— Calcium ion: the green ball
20 18
 Alkalinity (Cont’d) Electroneutrality

ƒ Determined by titrating against a standard acid ƒ Sum of positive ions (cations) equals sum of negative
— Expressed in mg/L as CaCO3 ions (anions) in solution
— Alkalinity can be defined in terms of molar quantities σ ‫ =ݏ݊݋݅ݐܽܥ‬σ ‫ݏ݊݋݅݊ܣ‬
Alk. mol/L = [HCO3-] + 2 [CO32-] + [OH-] – [H+] ƒ cations and anions expressed in terms of equivalent
ƒ Corresponding expression in terms of equivalents is: weight per liter (eq/L) or milliequivalent per liter
Alk. eq/L = (HCO3-) + (CO32-) + (OH-) – (H+) (meq/L)
ƒ In practice, alkalinity is expressed in terms of CaCO3 ƒ Equivalent weight of a compound is defined as:
ƒ To convert from meq/L to mg/L as CaCO3 ெ௢௟௘௖௨௟௔௥ ௐ௘௜௚௛௧ǡ௚Ȁ௠௢௟
ଵ଴଴ ௠௚Ȁ௠௠௢௟௘ ƒ ‫ݐ݄ܹ݃݅݁ ݐ݈݊݁ܽݒ݅ݑݍܧ‬ǡ ݃Τ݁‫ ݍ‬ൌ
‹ŽŽ‹‡“—‹˜ƒŽ‡– ƒ•• ‘ˆ ƒଷ ൌ ௏௔௟௘௡௖௘ ஼௛௔௥௚௘ ǡ௘௤Ȁ௠௢௟
ଶ ௠௘௤Ȁ௠௠௢௟௘

— Thus 3 meq/L of alkalinity equals 150 mg/L as CaCO3

͵ǤͲ ݉݁‫ݍ‬ ͷͲ ݉݃ ‫ܱܥܽܥ‬ଷ
ŽƒŽ‹‹–› ƒ• ƒଷ ൌ ൈ ൌ ͳͷͲ ݉݃Τ‫ƒ ݏܽ ܮ‬ଷ
‫ܮ‬ ݉݁‫ܱܥܽܥ ݍ‬ଷ
23 21

Fat, Oil and Grease (FOG) Alkalinity

ƒ Fats, oils, waxes, and similar compounds ƒ Acid absorbing capability of water samples
— Fat, oil and grease (FOG) used previously, replaced by oil and grease ƒ Results from the presence of OH-, CO3–2, and HCO3– of
ƒ Negative impact on wastewater cations of Ca+, Mg+, Na+, K+, and NH3+
— clogged lines, causing sewage spills, manhole overflows, or sewage — Of these, Ca(HCO3)2 and Mg(HCO3)2 the most common
backups in homes and businesses
— Borates, silicates, phosphates, and similar compounds can also
— Interference with biological life
contribute to the alkalinity
— unsightly films in surface water (oil thickness required to form a
translucent film on the surface of a water body is about 0.0003048 ƒ Alkalinity in wastewater helps to resist changes in pH
mm or 0.0000120 in) caused by the addition of acids
ƒ Two types of FOG pollutants common to wastewater systems — Wastewater is normally alkaline, receiving its alkalinity from
— Petroleum-based oil and grease (non-polar Concentration), water supply, groundwater and materials added during
businesses using oil and grease, and can usually be identified and domestic use
regulated by municipalities through local limits and associated
pretreatment permit conditions ƒ contamination of alkalinity in wastewater important in
— Animal and vegetable-based oil and grease (polar concentration) chemical and biological treatment, in biological nutrient
more difficult to regulate due to the large number of restaurants and removal, and in ammonia removal by air stripping
fast-food outlets in every community 24 22
 Biochemical Oxygen Demand (BOD) Oil and Grease Analysis
ƒ DO measurement is very important ƒ Hexane: The EPA Method 1664 using hexane as
— change in DO concentration is measured over a given period of
time in water samples at a specified temperature the extractant and a gravimetric procedure for
ƒ To be consistent, a very small amount of micro-organism analysis
seed is added to each sample being tested.
— Seed is typically generated by diluting organisms with buffered ƒ S-316: ASTM Method D 7066 – 04 (July 2004)
dilution water
— Sample being diluted with oxygen saturated dilution water,
dimer/trimer of chlorotrifluoroethylene (S-316)
inoculating it with a fixed aliquot of seed using Infrared Determination
— DO measured first, sample being sealed and kept in dark at 20°C in
to prevent photosynthesis for 5 days when DO being measured ƒ Perchloroethylene (Tetrachloroethylene):
again
Perchoroethylene (perc) is much like S-316. It also
ƒ Ultimate BOD, total amount of O2 consumed allowing
biochemical reaction to proceed to completion requires using the InfraCal TOG/TPH Analyzer,
ƒ Time-intensive Ultimate BOD, 5-day BOD being universally Model CVH, and reads down to 2 ppm
adopted as a measure of relative pollution effect

27 25

BOD vs. BOD5 Biochemical Oxygen Demand (BOD)

ƒ Two stages of decomposition in the BOD test: ƒ DO is the actual amount of oxygen available in dissolved
— Carbonaceous Stage: First stage representing portion of O2 form in the water. For DO below a certain level, normal
demand involved in conversion of organic carbon to CO2 life forms in that water not possible
— Nitrogenous Stage: Second stage representing a combined ƒ A chemical procedure for determining BOD
carbonaceous plus nitrogeneous demand (organic nitrogen, ƒ Amount of dissolved O2 (DO) needed by aerobic biological
ammonia, and nitrite are converted to nitrate) organisms in a body of water to break down organic
— Nitrogenous oxygen demand generally begins after about 6 material present (given water sample, temperature and
days time)
ƒ For some sewage with ammonia and nitrite present , — Commonly in mg of O2 consumed per lit of sample during 5 days
of incubation at 20°C
nitrification can occur in less than 5 days.
— Used as a robust surrogate of the degree of organic pollution of
— Add nitrification inhibitor to sample if the intent is to water, low BOD is an indicator of good quality water
measure only the carbonaceous demand. — Used as a gauge of effectiveness of wastewater treatment plants
— Results are reported as carbonaceous BOD (CBOD), or as ƒ Despite common application, not a precise quantitative
CBOD5 when using a nitrification inhibitor
test
28 26
 Other Quality Measures BOD vs. BOD5
ƒ Total Oxygen Demand (TOD): oxygen required for stable
contaminants (pyridine, benzene and ammonia) not digested
by COD chemical detection method
ƒ Total organic carbon (TOC): amount of carbon bound in an
organic compound (mg C/lit) often used as a non-specific
indicator of water quality or cleanliness of pharmaceutical
manufacturing equipment
— TOC highly sensitive, non-specific measurement of all organics present
in a sample
— TOC is obtained by subtracting the inorganic carbon from the total
carbon
— Another common variant of TOC involves removing IC portion first and
then measuring the leftover carbon - purging an acidified sample with
carbon-free air or nitrogen prior to measurement, non-purgeable
organic carbon (NPOC)
ƒ Inorganic carbon (IC): content of dissolved CO2 and carbonic
acid salts
ܶ‫ ܥ‬ൌ ܱܶ‫ ܥ‬൅ ‫ܥܫ‬
31 29

Interrelation of Quality Measures COD

ƒ Measures indirectly amount of organic carbon in

ƒ TOC is a clear parameter (measureable online) water expressed as mass of O2 (mg) consumed per
ƒ TOC does not provide the necessary info, it is liter of solution
independent of the oxidation state of the organic — Determining amount of organic pollutants found in
compound. It does not reflect the type of matter surface water or wastewater making COD a useful
contributing to COD or BOD measure of water quality
ƒ BOD is harder to define, but more informative ƒ Assumption: nearly all organics be oxidized with
ƒ For specific case, a correlation may be given between strong oxidizing agents (such as K2Cr2O7) under
TOC and COD (or BOD) acidic conditions
ƒ Real oxidation about 95-100% of the theory

32 30
 Dissolved Gases (Chemical) Dissolved Gases (Physical)
ƒ Gases, like CO2, may also experience chemical ƒ Solubility of a gas in a solvent directly proportional to
dissociation: partial pressure of that gas above the solvent
CO2(g) ֖ CO2 (l)
CO2(l) + H2O ֖ H2CO3 ƒ Henry Law
H2CO3 ֖ H+ + HCO3– ‫ ݌‬ൌ ‫ܭ‬ு ‫ܥ‬
HCO3– ֖ H+ + CO3ଶ–
KH: a T-dependent constant
p: partial pressure (atm)
c: concentration of the
ƒ Solubility is a function of pH
dissolved gas in the liquid (mol/L)
ƒ At constant pH, solubility of CO2 reduces as
temperature increases
— With pH changes, chemical equilibrium defines
concentrations of different species 35 33

pH/CO2 Equilibria Dissolved Gases (Physical)

Similar influence of pH on solubility of species such as NH3 ƒ Plot defines saturation at given temperatures
and H2S ƒ CO2 has a solubility of 1.8 g/L at 20°C
pH/CO2 equilibra — 1.8 grams of CO2
1.0
will dissolve in 1 liter
0.9
of water to make a
0.8

0.7
saturated solution
[HCO3-]
0.6
at 20°C. No more than
c (mol/l)

[CO3 2-]
[H2CO3]=[CO2]l
0.5

0.4
1.8 grams of CO2
0.3 as long as T remains
0.2

0.1
constant at 20°C
0.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
36 34
 CBM (Cont’d) Coal-Bed Methane (CBM)

ƒ Methane released when coal seam depressurized ƒ Coal-bed methane (CBM) or Coal Bed Methane, coal-bed
gas or coal mine methane (CMM) form of natural gas
ƒ To economically retrieve reserves of methane, wells extracted from coal beds
drilled into the coal seam, seam being dewatered — A source of energy in United States, Canada, and other
— Goal is to decrease water pressure by pumping water from countries In recent decades
the well — Rich deposits in Australia known as coal seam gas "CSG”
— Decrease in pressure allows methane to desorb from coal ƒ Methane adsorbed into the solid matrix of the coal,
and flow as a gas up well to surface called 'sweet gas' because of its lack of H2S
ƒ Methane is extracted from seam, compressed and ƒ CBM distinct from sandstone or other conventional gas
reservoir, methane stored within coal by adsorption
piped to market
ƒ Methane in a near-liquid state, lining the inside of pores
ƒ Coal-bed wells typically produce more water with less within the coal (matrix). Open fractures in the coal
gas during their initial production period compared (cleats) can also contain free gas or be saturated with
to conventional gas wells water
39 37

CBM Production CBM

ƒ Unlike conventional reservoirs, CBM contain very little

heavier HC’s such as propane or butane, and no natural
gas condensate and contains up to a few percent CO2
— Some coal seams, such as those in certain areas of the Illawarra
Coal Measures in NSW, Australia, contain little methane, with
the predominant coal seam gas being CO2
ƒ Methane, accounting for 95% of the gas contained in
coal, is retained within coal in one of three states:
— As adsorbed molecules on the internal surfaces and within the
structure of the coal into the solid coal matrix (coal macerals)
— As gas trapped within the pores or fractures of the coal
— In solution within the groundwater that may exist within the
fracture system
40 38
 CBM Global Resources Water Production in CBM

Country trillion m3
Low High
Canada 17 92
Russia 17 80
China 30 35
Australia 8 14
USA 4 11
Total 76 232
Source: IEA CCC 2005

Location Reserves (trillion m3)

Horseshoe Canyon 1.04
Pembina (including Ardley) 0.84
Mannville 4.76
Alberta/BC Foothills 3.70
(Gates/Mist Mtn)
Source: AAPL (2005) 43 41

National CBM Resources CBM Resources

ƒ Coal-bed methane reserve estimates vary; a 1997
estimate from U.S. Geological Survey predicted over
700 trillion ft3 (20 trillion m3) of methane within the US.
At a natural gas price of US$6.05 per million Btu
(US$5.73/GJ), worth US$4.37 trillion. At least 100 trillion
ft3(2.8 trillion m3) used to be economical to produce
— (Current price of natural gas ~US$ 7.50 per million Btu)
ƒ British Columbia estimated to have about 90 trillion ft3
(2.5 trillion m3) of coal-bed gas
ƒ Alberta, to date the only province with commercial CBM
Probable Economically Recoverable CBM wells, estimated to have about 170 trillion ft3(4.8 trillion
Reserves in Canada (trillion ft3) Primary CBM Potential Areas in Alberta
m3) of economically recoverable CBM
(Source: Alberta Energy and Utility Board – 2004) (Source: Alberta Energy and Utility Board – 2004) ƒ Recent depressed natural gas prices have made CBM less
economically viable compared to the past few years
44 42
 Natural Gas Price Produced Water in CBM

ƒ Amount of water produced, as well as the ratio of

Henry Hub Front-Month Natural Gas Future Prices
January 2017 – July 2022
water to gas, varies widely among basins with
CBM production.
ƒ Causes of variations include the duration of CBM
production in the basin, original depositional
environment, depth of burial, and type of coal.
ƒ Relatively recent regulations concerning disposal
and withdrawal of produced water have led to
more accurate reporting of water data

Courtesy of CME Group, Bloomberg , L.P.

47 45

Produced Water in CBM (Cont’d)

Source: Management and Effects of Coal-bed Methane Produced

Water in the United States, National Academy of Science, 2010

Basin State Start Depth Estimated Estimated Approx. Estimated

Date (feet) Water Gas No. of Water-to-
to Coalbeds Production Production CBM Gas Ratio
for (million (million Wells (barrels/MCF)
Methane barrels) MCF)
Production
Powder WY, 1989, 450-4,500 718 435.2 18,000 1.65
River MT 1998
San Juan CO, 1985 Up to 4,000 46 1,210.5 7,500 0.038
NM
Raton CO Early Up to 2,400 131 147.2 3,400 0.89
1980s
Piceance CO 1989 Up to 6,000 0.30 0.25 110 1.2
Uinta UT Early 4,200-4,400 31 73.8 1,255 0.42
1990s

46