TEMA 1.

CURRENT METHODS FOR WATER/POLLUTANT TREATMENT

(SIGUE DENTRO DEL APARTADO 2).
INDICE:
1. Application of treatment processes
a) Important contaminants
b) Current methods for pollutant treatment
o Physical processes
o Chemical processes
o Biological processes

2. Advanced oxidation processes (AOPs)

1a. Important contaminants
a) Suspended solids
b) Biodegradable organics
Those are measured most commonly in terms of BOD (Biochemical Oxygen
Demand) and COD (Chemical Oxygen Demand)
If discharged untreated to environment, their biological stabilization can lead to
the depletion (REDUCCIÓN) of natural oxygen resources and to the development
of septic (QUE PRODUCE PUTREFACCIÓN) conditions.
c) Pathogenic organisms
Communicable diseases can be transmitted by the pathogenic organisms in
wastewater.
d) Priority pollutants
e) Refractory organics
These organics tend to resist conventional methods of wastewater treatment.
Typical examples include surfactants, phenols and agricultural pesticides.
f) Heavy metals
g) Dissolved inorganic constituents
Calcium, sodium, sulphates

These methods succeed in removing many pollutants, but this is not enough either for the
pollutants that remain in the water or for the law that foresees (que prevé) a greater
putrification.

d,e,f → These are the categories in which more can be done as a removal of more diffuse
methods (Current methods).

1b Current methods for pollutant treatment

Wastewater treatment is a multi-stage water treatment, in which wastewater is cleaned

before it is:

• Discharged to a body of water.

• Used for irrigation
• Recycled for other purposes.
• Wastewater plants remove organic matter, nutrients, pathogens and industrial
waste.

Wastewater treatment usually consists of four sequential processes:

• Preliminary treatment – removal of floating materials, grit and oily substances.

• Primary treatment – removal of suspended organic solids.
• Secondary treatment – removal of dissolved and colloidal organic matter.
• Tertiary treatment – additional purification to achieve certain water quality
criteria.
The unit operations commonly used in wastewater treatment include physical, chemical
and biological treatments.

Common physical treatments – screening, comminution, flow equalization,

sedimentation, flotation, flocculation, media filtration etc.

Screening:
Wastewater screening retains solids found in the wastewater. These solids must be
removed at the very beginning of the water treatment process, as these solids could make
the whole system less efficient, damage expensive and essential water treatment
equipment or contaminate water, causing small to large scale natural upsets for a region’s
entire ecosystem.
Chemical processes – chemical precipitation, coagulation, adsorption, chlorination etc.

Comminution: to reduce the size of the solids contained in the water.

Flow equalization: the process of controlling hydraulic velocity, or flow rate, through a
wastewater treatment system. The equalization of flow prevents short term, high volumes
of incoming flow, called surges, from forcing solids and organic material out of the
treatment process.

Sedimentation: gravitational settling of heavy particles.

Flotation: Dissolved air flotation (DAF) is a water treatment process that clarifies
wastewaters (or other waters) by the removal of suspended matter such as oil or solids.
The removal is achieved by dissolving air in the water or wastewater under pressure and
then releasing the air at atmospheric pressure in a flotation tank basin. The released air
forms tiny bubbles which adhere to the suspended matter causing the suspended matter
to float to the surface of the water where it may then be removed by a skimming device.

Granular medium filtration: process for removing suspended or colloidal particles; for
example removing suspended solids remaining after sedimentation clarification. It
reduces turbidity and improves clarity by removing various sized particles, from coarse
sediment down to 10.0 μm [10,12].

Chemical processes – chemical precipitation, coagulation, adsorption, chlorination

etc.
Chemical precipitation: Precipitation is a chemical unit process in which undesirable
soluble metallic ions and certain anions are removed from water or wastewater by
conversion to an insoluble form. It is a commonly used treatment technique for removal
of heavy metals, phosphorus, and hardness. The procedure involves alteration of the ionic
equilibrium to produce insoluble precipitates that can be easily removed by
sedimentation. Chemical precipitation is always followed by a solids separation operation
that may include coagulation and/or sedimentation, or filtration to remove the
precipitates. The process can be preceded by chemical reduction in order to change the
characteristics of the metal ions to a form that can be precipitated.

Adsorption with activated carbon: Activated carbon filtration is a commonly used

technology based on the adsorption of contaminants onto the surface of a filter. This
method is effective in removing certain organics (such as unwanted taste and odours,
micropollutants), chlorine, fluorine or radon from drinking water or wastewater.
However, it is not effective for microbial contaminants, metals, nitrates and other
inorganic contaminants. The adsorption efficiency depends on the nature of activated
carbon used, the water composition, and operating parameters. There are many types of
activated carbon filters that can be designed for household, community and industry
requirements. Activated carbon filters are relatively easy to install but require energy and
skilled labour and can have high costs due to regular replacement of the filter material.

Disinfection: Water disinfection means the removal, deactivation or killing of pathogenic

microorganisms. Microorganisms are destroyed or deactivated, resulting in termination
of growth and reproduction. When microorganisms are not removed from drinking water,
drinking water usage will cause people to fall ill.
Sterilization is a process related to disinfection. However, during the sterilization process
all present microorganisms are killed, both harmful and harmless microorganisms.

Biological processes – activated sludge, aerated lagoons, trickling filters, pond

stabilization, anaerobic digestion, biological nutrient removal etc.

Explicados en los apuntes

2 Advanced oxidation processes (AOPs)

They are getting diffused so they can be considered conventional. (Due to the more
restricted regulations of the past years).

General properties:
a) All of them are CHEMICAL OXIDATION PROCESSES of the POLLUTANTS.
b) They operate at ROOM TEMPERATURE AND PRESSURE.
c) In order to OXIDIZE POLLUTANTS, you use RADICALS (Pretty strong
oxidizing species, highly reactivity, non-selective reactivity, short lifetime).
d) Radicals will not travel a long distance far from their source because they have a
SHORT LIFETIME: 10-9 s.
e) Non-selective, so they can attack both ORGANIC and NON-ORGANIC
POLLUTANTS.

Ideal Process starting from POLLUTANT MIXTURE. (Not always this result, usually
we have by-products).

−
𝑷𝒐𝒍𝒍𝒖𝒕𝒂𝒏𝒕 𝒎𝒊𝒙𝒕𝒖𝒓𝒆 + (𝑨𝑶𝑷) → 𝑪𝑶𝟐 + 𝑯𝟐 𝑶 + 𝑺𝑶𝟐− −
𝟒 , 𝑪𝒍 , 𝑵𝑶𝟑

OBJECTIVE OF USING AOPS:

They are used to oxidize complex organic contaminants that are found in wastewater and
that are difficult to degrade into simpler end products through biological processes.

THEORY OF AOP:
The basic principle of AOPs entails the generation of hydroxyl free radical HO∙, non-
selective chemical oxidant, as a strong oxidant for destroying organic compounds which
cannot be oxidized by conventional oxidants such as ozone, oxygen and chlorine.
Hydroxyl radicals are effective in the destruction of organic chemicals due to the fact they
are reactive electrophiles which not only react rapidly, but also non-selectivity with
almost all organic compounds that electron-rich. Their oxidation potential is quantified
as 2.80 V, and this makes them to exhibit faster rates of oxidation reactions compared to
conventional oxidations.
Table 1. Oxidation potential of various oxidants

Oxidant Oxidation Potential (V)

Hydroxyl radical (OH∙) 2.7/2.8
Ozone (O3) 2.08
Hydrogen peroxide (H2O2) 1.78
Chlorine (Cl2) 1.36
Molecular oxygen (O2) 1.23

Classification of AOPs:
There are several methods that are classified under the broad definition of advanced
oxidation processes. Most of these methods combine a strong oxidizing agent such as
H2O2 or O3 with a catalyst such as transition metal ions and irradiation such UV. Evidence
shows titanium dioxide (TiO2)/UV light processes, Fenton’s reactions and hydrogen
peroxide (H2O2)/UV light as the most popular AOP producing hydroxyl radicals.

1. Processes using chemicals → Homogeneous process without using energy

2. Photolytic processes → Homogeneous process using ultraviolet energy
3. Photocatalytic processes → Heterogeneous process
4. Electrochemical processes → Homogeneous process using electrical energy

AOPS
Los que tienen asterisco (*) tienen INDUSTRIAL APPLICATIONS.
Using chemicals (1) Photolytic (2) Photocatalytic (3) Electrochemical (4)
O3* O3/UV* TiO2/UV Anodic hydrolysis
O3/H2O2* H2O2/UV* TiO2/H2O2/UV Electro-Fenton
Fenton* PAA/UV TiO2/UV/Bias
Photo-Fenton* TiO2/UV/H2O/Bias

Fenton Process:
The Fenton reagent is a mixture of iron (II) salt and hydrogen peroxide. Fenton described
the oxidation power of hydrogen peroxide on various organic molecules in which OH∙
radicals are produced from H2O2 through addition of Fe (II) as the catalyst.
Fe2+ + H2O2 → Fe3+ + OH- + OH·
Fe3+ + H2O2 → Fe2+ + HOO· + H+

2H2O2 → OH· + HOO· + H2O (OVERALL REACTION)

Applications of AOPs:

AOPs are usually applied to wastewaters with low COD due to the low cost of H2O2
and/or ozone required for the generation of hydroxyl radicals.

a) Industrial wastewaters (Petrochemical, Agroindustrial wastewaters, Metallurgic

industrial wastewater…).
b) Dangerous effluents (Hospitals).
c) Refractory organic compounds (Chlorinated solvents, pesticides, DAES).
d) Endocrine disrupting chemicals (EDC) and Pharmaceutical and Personal Care
Products (PPCPS).
e) Disinfection.
f) Removal of heavy metals.
g) Sludge conditioning and stabilization.

Overview:
The reasoning behind using AOPs for disinfection is that free radicals that are generated
from ozone are more powerful oxidants that ozone alone and this makes them effective
for oxidation of microorganisms and refractory organic materials in wastewater.
However, the fact that the half-life of the hydroxyl free radical is short and as a result it
is impossible to achieve high concentrations. Extremely low concentrations imply that
the required detention times for disinfection if microorganisms are much higher and are
determined on the basis of CT concept.

· End of first topic ·