Nitrogen

Exist in seven oxidation states NH3 (-III), N2 (O), N2O (I), NO

(II), N2O3 (III), NO2 (IV), N2O5 (V)
3 ionic species are important in environmental engineering
NH3 + H2O → NH4+ + OH-
N2O3 + H2O → 2H+ + 2NO2-
N2O5 + H2O → 2H+ + 2NO3-
Nitrogen is essential to life: the reduced form N(-III) is a
major element in amino acids, proteins, and nucleic acids
The oxidation state of nitrogen can be changed through
biological, chemical, and photochemical processes

From Chemistry for Environmental Engineering and Science Textbook

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 Entering of nitrogen from air to land and water: nitrogen
fixation
N2 (in air) → “fixed” forms of nitrogen
Need strong energy to break strong N ≡ N bond:
lightning, cosmic rays, manufacturing of urea (NH2)2CO)
Biological fixation: N2 + nitrogen fixing bacteria →
protein

Legumes such as
green peas, soya,
beans, etc.,
contain nitrogen-
fixing bacteria

(Rhizobium,
Azotobacter) in
their root nodules
Bacteria inside root nodule Detail at a higher
cells. Bar: 5 µm magnification. Bar: 1 µm

http://www.usu.edu/westcent/microstructure_food/n-fix-p.htm

Returning of nitrogen from land and water to the atmosphere

Biological denitrification
NO3- → NO2- → N2
NO3- → N2O
NO3- → NH4+ (NH4+ become NH3 at high pH)
Combustion: burning of fossil fuels and combustible
biomass contaning nitrogen → NOx
In water and land
Uptake (assimilation)
Conversion from NH4+ and NO3- to organic nitrogen
(proteins)
NH4+/NO3- + CO2 + green plants + sunlight → protein

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 Ammonification (decomposing of protein)
Bodies of dead animals and plants are converted to
NH3/NH4+ by bacteria
Protein (organic-N) + bacteria → NH3
Nitrification:
Oxidation of NH4+ in aerobic condition
2NH3 + 3O2 → 2NO2- + 2H+ + 2H2O (by
Nitrosomonas)
2NO2- + O2 → 2NO3- (by Nitrobacter)
Abiotic ion exchange and sorption
NH4+ is retented in clay, organic matter, and soil
materials (not applicable for NO3-)

Environmental significance
Atmospheric concerns: photochemical smog, global
warming, and stratospheric ozone depletion
Aquatic concerns
Indicator of water quality:
Recently polluted water: mostly organic and
ammonia nitrogen (great danger)

From Chemistry for

Environmental Engineering and
Science

6
 Nitrite caused methemoglobinemia in infant. EPA:
max nitrite-nitrogen = 1 mg/L and max nitrate-
nitrogen = 10 mg/L public water supplies
Nitrite + amines (protein) = nitrosamines (most are
carcinogenic)
Nutritional and related problems
Treatment plants: the waste must contains enough
nitrogen (food) for the organisms
Algae growth
Oxidation in rivers: nitrification requires oxygen → the
discharge of ammonia-nitrogen can seriously reduce
the dissolved oxygen level in rivers
Control of biological treatment process (organic carbon
removal, nitrification, denitrification)

Methods of analyis
Ammonia nitrogen:
Distillation to separate ammonia from other
impurities
Titration with H2SO4 to determine the amount of
ammonia
NO2- and NO3-: measure the absorption at appropriate
wavelength (with the addition of some chemical) -
spectrophotometry
Organic + ammonia nitrogen (Kjeldahl nitrogen)
Convert organic nitrogen to ammonia nitrogen
(digestion)
Total amount of nitrogen will then be determined
Total nitrogen: sum of all nitrogen species

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Phosphorous and Phosphate
Phosphorous: chemical element (P)
Phosphorous compounds: mostly present in the water and
soil systems
Orthophosphate (H3PO4, H2PO4-, HPO42-, and PO43- )
Polyphosphate (Na3(PO3)6, Na5P3O10, Na4P2O7)
Organic phosphorous: formed primarily by biological
processes
Environmental significance
Major nutrients for plants and microorganisms
Common element limiting the eutrophication process

Sources of phosphorous in lakes and rivers

Point sources: well defined discharges from factories,
outlet of municipal sewer systems. In municipal
wastewater
Soap and detergent
Human waste
Diffuse source: run-off from rural and urban landscapes
Difficult to control

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 Environmental chemistry - a global perspective (vanLoon and Duffy)

11

Determination of phosphorous compounds in water

Orthophosphate: colorimetric method
Complexation with ammonium molybdate under
acidic condition to form a yellow molybdophosphate
complex
PO43- + 12(NH4)2MoO4 + 24H+ → (NH4)3PO4•12MoO3 +
21NH4+ + 12H2O
Polyphosphate: convert to orthophosphate at high
temperature in acidic condition
Organic phosphorus: digestion with persulfate in acidic
condition, organic phosphorus → orthophosphate

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Application of phosphorous data
Corrosion prevention
Assessing the potential biological productivity of
surface waters
Determine the amount of phosphorus can be discharged
into the receiving water bodies
Operation in wastewater treatment plants

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Particulate Matter
Suspended particles
Toxic metals and organic compounds
Chemically inert materials such as soil dust
Microorganisms: bacteria, algae, virus
Size range: nm (virus) to 𝜇m (sand grain)
In water, particles are classified by size
Easy to settle under the influence of gravity (settleable
solids): larger than 10 𝜇m diameter, can settle at a
velocity of several cm or more per hour
Suspended solid: easily removed by water filtration,
larger than 1 𝜇m diameter (2 𝜇m filter)

Colloidal solid: pass through a 2 𝜇m (or smaller) filter

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 From Environmental Engineering Science

15

From Environmental Engineering Science

16
 Environmental problems of suspended particles
Decreased visibility (turbidity): suspended particles
scatter light → reduce the transmission of light →
aesthetic problem for water and air
Disease transmission: host to bacteria and virus →
cause disease through inhalation or ingestion
Transport and delivery of toxic materials: heavy metals
(e.g., cadmium and lead), and toxic organics (e.g., PAHs
and PCBs) are found in particulate form → cause toxic
effects through inhalation and ingestion
Acute respiratory health effects

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Particulate Matter - Turbidity

The cloudiess of a fluid caused by the presence of
suspended matter (large size range)

A turbid fluid does not

permit light to be
transmitted directly from
an object to an observer

From Environmental Engineering Science

18
A wide variety of activities and materials (both inorganic
and organic) contributes to the turbidity of water in the
nature
Farming (disturb the soil), flooding (topsoil is washed),
raining (agriculture run-off), river passing through
urban areas (domestic and industrial wastewater)
Wide range of materials → impossible to have a general
guideline for removal of turbidity effectively
Important parameter used in public water supplies
Aesthetics: consumers want to have clear water
(perception: turbid water associates with wastewater
pollution)
Filterability: more difficult to filter higher turbid water.
Turbidity must be removed by chemical coagulation
before filtration

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Disinfection:
Effective disinfection: direct contact between
pathogenic organisms and disinfectant agent
(chlorine, ozone, UV, etc)
In turbid water: pathogenic organisms could
surrounded by particles → more difficult to kill
→ Have to remove turbidity using filtration before
disinfect the water
Unit and method of determination
Current unit (measured by a nephelometer): NTU
(nephelometric turbidity unit)
Use formazin polymer suspension standard
Measurement range: 0.02 - 40 NTU (need to do
dilution if the turbidity is higher than 40 NTU)

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From Environmental Engineering Science

21

Application of turbidity data

Determine the effectiveness of a treatment process
Estimate the amount of chemical needed
Check the operation of the filters
Conform with regulatory requirement

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 Particulate Matter - Solids

Things pass through 2𝛍m pore size filter

Things retain on 2𝛍m pore size filter

From Environmental Engineering Science

23

Water for domestic use: TS should be < 500 mg/L

High TDS water: stain glassware, bad impacts on irrigated
crops, plants, and grasses.
SS of treated wastewater is regulated
Application of solids data
Settleable solids: determine the need for and design of
primary settling tanks in plants employing biological
treatment process, determine the efficiency of
sedimentation unit
SS and VSS: evaluate the strength of domestic and
industrial waste, control the biological solids in the
activated sludge process (VSS = bacterial content)
TS and VS (apply to sludge): design and operation of
sludge digestion, vacuum filter, and incineration units

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 pH
Expresses the intensity of the acid or alkaline condition of
a solution
A way of expressing the hydrogen-ion concentration
pH = -log[H+]
Chemical speciation (logC-pH diagram) and particle
surface charges depends on pH (will be discussed later)
In water supply: affect on chemical coagulation,
disinfection, water softening, and corrosion control
In wastewater treatment: affect on biological treatment,
dewatering sludges, and oxidizing of pollutants

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pH = 0 - 7: acid range pH = 7 - 14: alkaline range

Kw depends on temperature → pH depends on
temperature (will be discussed later)
Measurement of pH
pH paper: quick and cheap but not accurate
pH meter: accurate but more expensive (than pH paper)
Note: calibration is needed for a proper pH
measurement

http://cdn.bernell.com/images/ http://www.capitolscientific.com/Thermo-Scientific-
uploads/PH9958.jpg Orion-STARA1115-Orion-Star-A111-Benchtop-pH-
Meter-Kit-Parameters-pH-ISE-mV-Tem

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 Color
Coloring material in water
Humic substances (produced by the degradation of
organic debris such as leaves and wood)
Negatively charged colloidal particles (nanoparticles)
Dissolved salt (e.g., CuSO4)
Pollution (dye from textile industry)

Gold nanoparticles CuSO4

http://www.tedpella.com/gold_html/goldsols.htm https://s-media-cache-ak0.pinimg.com/564x/86/
b6/29/86b62942be100f888b2a24df997a581f.jpg

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Sapphire Pool in Yellowstone National Park, USA

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 Definition
Apparent color: color of the whole water sample (from
both dissolved and suspended components (micron
sized))
True color: measured after all suspended material
(micron sized) were removed (filtered)
Significance In public health
Natural water (not harmful): yellow-brownish color
from the decay of natural substances = color of urine
→ people do not want to drink water having color
Disinfection using chloride in the presence of natural
organic matter → disinfection by products
(chloroform, trihalomethane (THM), etc) - possible
human carcinogen
WHO and EPA: < 15 color units for human use

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Determination
Compare the color of the sample with standard color
solutions: potassium choloroplantinate (K2PtCl6)
solution + with small amount of cobalt chloride (CoCl2)
Color produce by 1 mg/L of Pt (in the form of
K2PtCl6) = standard unit of color
In the lab: use a spectrophotometer
Application of color data
In natural water: indirect indicator of the formation of
THM → Need to find the optimal goal for treating color
(not harmful and not expensive to treat)
In raw and and treated water: chemical selection,
chemical dosage and storage

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 Hardness
The sum of the normalities of all multivalent cations (i.e.,
charge of + 2 or greater): Ca2+, Mg2+, Sr2+, Fe2+, Mn2+, Fe3+,
and Al3+)
Problems caused by hard water
Scaling on inner surface of pipes and fittings
Precipitates build upon bathroom and utensils
Soap does not lather well
GOOD: deposition of some scale: protect the pipes against
corrosion

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http://www.waterfilterevansville.com/hardness.php

water.me.vccs.edu/courses/ENV115/lesson9.htm

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 Hardness is from the
contact between water and
rock/soil formation
Bacterial action in soil
produce CO2 → Soil water
has H2CO3 → Low pH
condition → Dissolve
limestone formation

From Chemistry for Environmental Engineering and Science

33

Hardness: usually expressed as normality (meq/L) or

equivalent mass concentration of CaCO3 that would
produce the same hardness
A hardness of 1 meq/L = a hardness of 50 mg/L as CaCO3
Example: calculate the hardness of solution containing 5
mM MgCl2

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Classification Hardness (meq/L) Hardness (mg/L as CaCO3)

Soft < 1.5 < 75

Moderately hard 1.5 - 3 75 - 150

Hard 3-6 150 - 300

Very hard >6 > 300

From Environmental Engineering Science

35

Total hardness (TH) = carbonate hardness (CH) +

noncarbonate hardness (NCH)
CH is contributed by the dissolution of CaCO3, MgCO3,
Ca(HCO3)2
NCH is contributed by the dissolution of non-carbonate,
e.g., CaCl2, MgSO4, Ca(OH)2
To determine CH and NCH
Normality of carbonate species, NC=[HCO3-]+2[CO32-]
If NC<TH, then CH=NC, and NCH=TH-CH
If NC>TH, then CH=TH, and NCH=0

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 Exmaple: Calculate the total hardness, carbonate
hardness, and non carbonate hardness of water that
contains the following ion concentrations (pH = 7)

Species M (mol/L) N (eq/L)

Na+ 2.43 x 10-3 2.43 x 10-3 TH = sum of normality of Ca2+,
Ca2+ 1.00 x 10-3 2.00 x 10-3 Mg2+ and Al3+ = 7.8 meq/L
Mg2+ 1.25 x 10-3 2.50 x 10-3 NC = 3.1 meq/L

HCO3- 3.11 x 10-3 3.11 x 10-3 NC < TH, CH = NC = 3.1 meq/L

Cl- 4.65 x 10-3 4.65 x 10-3 NCH = TH - CH = 4.7 meq/L

Al3+ 1.11 x 10-3 3.33 x 10-3

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Determine hardness:
Calculation method: bassed on the concentrations of
each multivalent cations
EDTA titration method: EDTA can form stable complex
ions with divalent ions causing hardness (will be
discussed later)

blue wine red

M2+ + Eriochrome black T (blue) → (M-Eriochrome black T)complex
Titration with EDTA
M2+ + EDTA →[M-EDTA]complex

[M-EDTA]complex is more stable than (M-Eriochrome black T)complex

→ wine red change to blue color

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 blue wine red
M2+ + Eriochrome black T (blue) → (M-Eriochrome black T)complex

EBT is blue in a
buffered solution at
pH 10. It turns red
when Ca2+ ions are
added
https://en.wikipedia.org/wiki/
Eriochrome_Black_T

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Alkalinity
Alkalinity is the capacity of water to neutralize acid
In most uncontaminated water
Alkalinity = [OH-] + [HCO3-] + 2[CO32-] - [H+]
Alkalinity has little public health significance
Measured by calculation and titration
A strong acid (e.g., HCl) is slowly added to the water
sample until the pH decrease to ~ 4.5
The amount of acid added per L of water sample = the
measured alkalinity

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Application of alkalinity data
Chemical coagulation: coagulant (e.g., FeCl3 releases H+
→ reduce alkalinity, need to maintain optimal pH (~ 5.5 -
8.5) for an effective coagulation
Corrosion control
Evaluating the buffer capacity of wastewater and sludge
Regulation (industrial wastes)

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Solution Properties
Ionic strength: the total amount of ions in water
1
(Ci zi2 )
2∑
I=
i
Ci: molar concentration of the ith ionic species (M)
zi: number of net electrical charges associated with the
ith species
Electroneutrality: the sum of the normalities of all cations
in an aqueous solution must be equal the sum of the
normalities of all anion
zi: charge per molecule on the
∑
ziCi = 0 i the ion, (+) for cations and (-)
i,cations and ions for anions

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