ELECTROCHEMICAL TECHNOLOGIES FOR WATER AND WASTE

TREATMENT.
This course aims at filling the students, educational gaps on technologies for water, air
and soil decontamination, with focus on the application of electrochemical methods to
pollution sensing and abatement. The following topics will be discussed:
electrochemical behavior of pollutants, electrochemical sensing of pollutants,
electrochemical technologies for pollution control, electrochemical disinfection,
commercial applications. Seminaries will be given by industry representatives, both in
the field of technologies manufacturing and water managing.
Examen escrito que consta de 3 PREGUNTAS
1 MUY GENERAL  Describe ozonización
1 ESPECÍFICA  Describe un equipo
1 MUY ESPECÍFICA  Describir los electrodos de referencia
HAY 4 SEMINARIOS DISTINTOS QUE LOS INCLUIRÉ AL FINAL DE LAS
NOTAS DE CLASE.

TITULO LUNES 25/02/2019 y MIÉRCOLES 27/02/2019

1. SOME DEFINITIONS.
We begin with the term POLLUTANT.
A reasonable DEFINITION OF POLLUTANT is a substance present in greater than
natural concentration as a result of human activity and that has a net detrimental
(prejudicial) effect upon its environment or upon something of value in that
environment. Time and place determine what may be called pollutant. A contaminant
causes a deviation from the normal composition of an environment. Contaminants are
not normally classified as pollutants unless they have a deleterious (prejudicial) effect
on the environment. Every pollutant has a source from which it originates. This source
can be either natural or anthropogenic (i.e., human-made).
A reasonable definition of WASTE is something released into the environment.
Hazardous wastes (RESIDUOS PELIGROSOS) have been classified according to their
source of their characteristics.
Thus, in the first category, there is a list of industrial SOURCES that generate
hazardous substances (mostly chemicals)
The second category comprises waste materials not listed but exhibit one or more of the
hazardous characteristics which are the following ones:
 Ignitability (inflamabilidad).
 TOXICITY
 Corrosivity
 Reactivity
  Biological activity
This bring us to another controversial issue; the DEFINITION OF TOXICITY. The
standard method for measuring toxicity of a chemical is to perform bioassays
(bioensayos) on genetically sensitive animals. Unfortunately, these laboratory tests
require relatively high chemical dosage (dosificación) to generate adverse effects in the
test animals. Predictive models (Estadística) are then used to extrapolate to the lower
doses to which people are usually exposed.
2. ENVIRONMENTAL MEDIA AND POLLUTANT TRANSPORT
Traditional control of environmental pollution has focused primarily on the immediate
vicinity of the pollution source. Multimedia environmental transport models are needed
to account for global distribution of pollutants. Therefore, pollutant regulation has
gradually shifted from local and national governments to international scale.
The environmental mediums are:
 Air
A good rule for understanding pollutant transport is the PARTITIONING
RULE; that is, chemicals, once they are released into the environment, seek out
the environmental medium in which they are most soluble.

 Water
On the total store of water on this planet earth, the fresh water (la que se puede
beber) is just 0.01%. Fortunately, this freshwater supply is continually
replenished (reabastecida) by the precipitation of water vapor from the
atmosphere as rain or snow. The global water cycle is formed by precipitation,
evaporation and vapor transport.
Some pollutants enter the water cycle by way of the atmosphere. Best-known
examples of this transport route include the acid generation from NOx and SOx
emissions. An indirect effect of acid deposition is positive ion leaching out of
the soil, that has been implicated in several cases of fish-kill in rivers and lakes.
Ammonia from the atmosphere can also enter the groundwater through the soil.
Microbial action converts it into soluble nitrates. Another deleterious effect of
human activity is the introduction of large amount of nutrients, especially
phosphates, into the surface water reservoirs. This leads to excessive growth of
algae. When algae die, their microbial degradation consumes most of the
dissolved dioxygen in the water, vastly reducing the water’s capacity to sustain
life. This process is called eutrophication.

 Soil
Soil receives large quantities of water products each year. Much of the Sox and
NOx emissions end up in the soil as sulfates and nitrates, respectively. Elevates
levels of heavy metals are found in the soil near industrial and mining facilities.
The soil receives enormous quantities of pesticides as an inevitable result of the
application to crops. The degradation and eventual fate of these chemicals in soil
largely determine their ultimate environmental impact.
 The three primary ways in which chemicals (including pesticides) are
decomposed in soil are: BIODEGRADATION, CHEMICAL DEGRADATION
and PHOTOCHEMICAL REACTIONS (in surface soil reactions). Microbial
degradations, however, remains the predominant decomposition pathway.
The soil constitutes an integral part of the human exposure pathway whereby the
pollutant ultimately enters the food chain. This is because most lipophilic
compounds reside mainly in the soil.

 Biota

3. CLASSES OF POLLUTANTS
ORGANICS
 Pesticides.
 Organic solvents
The BTEX family (benzene, toluene, ethylbenzene,xylene) are classified as
priority pollutants. These monocycle aromatics are concern in wastewater, and
particularly in sources of drinking water, because they are generally
nonbiodegradable. (They are highly water soluble and volatile compare to their
aliphatic counterparts). They are really stable and difficult to oxidize.
The partition rule tells us how much is of those is spread in the surrounding
ambient.

 Polycyclic Aromatic Hydrocarbons (PAHs)

They have attracted a good deal of attention because of the known
carcinogenicity of some of these compounds. These compounds are most likely
to be found in urban atmospheres and appear to be transported via adsorption on
particulate matter. As with the BTEX, inhalation is the primary exposure
pathway for PAHs.

 Surfactants
Mostly present in the water and soil.

 Industrial organics
PCBs behave as antioxidant which explains why are so persistent when released
into the environment.

Organic pollutants in general are classified as follows:

 Suspended solids
 Biodegradable organics
 High-priority pollutants (These are selected based on their known or suspected
behaviour as carcinogens, mutagens, or toxicity).
 Refractory organics: these compounds are not biodegradable.
  Volatile organic compounds (VOCs): These include organic compounds with
boiling points below that of water or vapor pressures greater than 1 mm Hg at
25ºC or both. When transferred to the vapor phase, their mobility increases
greatly and can lead to increased health risks or the formation of photochemical
oxidants.
 Malodorous compounds: some organic compounds, volatile or otherwise, may
lead to a foul smell (mal olor) so considered because of social impact.
We can group inorganic pollutants into several categories including the following:
INORGANICS

 Metals: the toxicity depends on the oxidation state and the coordination on the
metals.

Inorganic Pollutant Forms

Form Examples
Simple ions  In this example, Cd ( H 2 O )+2 6
because all the ions are hydrated in
water
Complex ions Cd Cl +¿¿
Differing oxidation states Ge (III) / Ge (VI)
Lipid soluble complexes CH3HgCl
Organometallic complexes CH3AsO(OH)2
Adsorbed species Cu2+ / humic acid / Fe2O3
Particulates [-]

The effects of metals and their compounds on humans, animals, and plans are
quite varied. Whereas some are essential nutrients, others are very toxic due to
their interactions with life processes (such as enzymatic activity). Especially
problematic are those capable of BIOACCUMULATION.

 Metalloids: for example, arsenic and selenium. Dissolved arsenic can occur in
natural waters in both inorganic and organic forms.

 Anions

 Microorganisms.

4. CURRENT METHODS FOR ENVIRONMENTAL ANALYSES

Instrumental techniques are used for sensing (and quantifying) organic and inorganic
pollutants. Automated procedures are generally used because the quality of the
analytical results is not severely compromised by human error.
We will look for a specific element, THE POLLUTANT, neglecting the others. This
element is tabulated and is settled the level of the social impact that those chemicals
cause.
The analytical protocol for pollutant analyses is specified by regulatory agencies such as
EPA. This protocol is formulated as “recipes” that describe everything the analyst needs
to know to complete a satisfactory analysis.
The EPA methods follow this PROTOCOL:
 Sample collection
 Sample preservation
 Sample shipment (organized in 24 hours without changing the temperature even
in summer where temperatures are very high) and storage
 Instrumentation and apparatus
 Reagents
 Analytical calibration
 Quality control
 Calculations and reporting results

In most cases, the methods are directed toward specific environmental matrices, for
example industrial wastewater. Clearly, each type of environmental medium discussed
previously – air, water, soil, and biota – requires its own set of sample acquisition,
storage, and pre-treatment procedures.

There are systematic errors. When this happens, we must obtain the values that are true.
OBJECTIVE: Find the value that is more similar to the real one.

In our studies we can have two types of errors: SYSTEMATIC and RANDOM errors.
Random errors are produced randomly. No nos podemos librar de él.
El segundo error que mencionamos es el SYSTEMATIC error, también llamado sesgo.
Este se debe a un error en el diseño o en el análisis del estudio, que produce una
estimación incorrecta o no válida del efecto que estamos estudiando.

Systematic errors are consistently in the same direction. In contrast, random errors
produce different values in random directions.

RANDOM ERROR has high accuracy and low precision. Instead systematic errors are
characterized by a high precision and low accuracy (Compromete la validez de los
resultados).

Standards: control of concentration. We can evaluate the precision of the instruments

we are using. As precision in the instruments is higher, as result we can improve the
accuracy.

DETECTION LIMITS DONE IN DIFFERENT WAYS

The detection limit is the minimum concentration that we can analyse with the specific
degree of confident. The lowest concentration that can be measured of the noise level.

There are different detection limits that are commonly used:

 Instrument detection limits (IDL): the value which corresponds to 3 times the
standard value of the noise.
 Lower level of detection (LLD): quantitative of analyse that will produce a
measurable signal of 99% of the time. LLD ≈ 2·IDL
 Method detection limit (MDL): not specific of the step, it’s general. MDL ≈
4·IDL
 Practical Quantitation limit (PQL): it’s twenty times the first one. The lowest
limit for routine analysis. PQL ≈ 20·IDL
4.1 CLASSICAL ANALYTICAL METHODS FOR ENVIRONMENTAL
ANAYLYS.

Considering chemical methods, the most important are volumetric and gravimetric
analysis. Those analyses allow us to determine the amount of a constituent present in a
mixture of constituents. These methods can be used to determine a pollutant in a given
sample.
The following parameters will allow us to analyse our sample:

 Acidity of water:
pH=4.5 (Methyl orange: is a pH indicator frequently used in titration because of
its clear and distinct colour variance at different pH values. It shows red colour
in acidic medium and yellow colour in basic medium.

Variation of concentration. Chlorines and sulphates.

pH=8.3 (Phenolphthalein is often used as an indicator in acid-basic titrations.

For this application, it turns colourless in acidic solutions and pink in basic
solutions). We know the global acidity of our mixture.

 Alkalinity: capacity of water to resist changes in pH that would make the water
more acidic.

 Hardness: in water is due to the presence of dissolved salts of calcium and

magnesium.
Hardness of water is determined by titrating with a standard solution of EDTA
which a complexing agent is. Since EDTA is insoluble in water, the
corresponding salt of EDTA is taken for this experiment. EDTA can form four
or six coordination bonds with a metal ion.
−2 2−¿ (aq ) +2 H +¿ ¿ ¿

Ca2+¿ (aq) +H 2 Y ( aq ) → CaY ¿

 At pH 10, Ca2+ (aq) is first complexes with the indicator which is wine red. As
the stronger ligand EDTA is added, the indicator complex is replaced by the
EDTA complex which is transparent.
The indicator changes the colour, and with this we can determine how much Mg
or Ca is present in the water.

 Dissolved Oxygen (DO): The Winkler Method is a technique used to measure

dissolved oxygen in freshwater systems. Dissolved oxygen is used as an
indicator of the health of a water body, where higher dissolved oxygen
concentrations are correlated with high productivity and little pollution. This test
is performed on-site, as delays between sample collection and testing may result
in an alteration in oxygen content.
El Método de Winkler es un método que sirve para determinar la concentración
de oxígeno disuelto en muestras de agua. Usándolo, la concentración se
determina a través de una serie de reacciones de oxidación-reducción.

Primero se añade Mn2+ (en forma de sulfato de manganeso) a una muestra de

agua. Después se añade un reactivo KI en NaOH. Bajo estas condiciones
causticas, el oxígeno presente en la muestra oxidará el Mn2+ a Mn4+, que
precipita como un óxido hidratado de color marrón:
1
−¿+ O2 → MnO2 (s )+ H 2 O ¿
2
2 +¿+2OH ¿
Mn

Después que el precipitado de MnO 2 se asiente en el fondo del frasco, se añade

ácido sulfúrico para acidificar la solución. Bajo condiciones de pH bajo el MnO 2
oxida el I- a I2 como se muestra en la siguiente reacción:
2+¿ +I + 2H O ¿
2 2

−¿+2 H + ¿→Mn ¿
¿
MnO 2 ( s )+ 2 I

Ahora la muestra de agua está lista para ser titulada con tiosulfato de sodio. En
esta reacción el ion tiosulfato se añade cuantitativamente para convertir el I2
nuevamente en I-. Recuerde que la cantidad de I2 presente en esta etapa del
procedimiento está directamente relacionada a la cantidad de oxígeno O 2
presente en la muestra original. Esta reacción se representa con la expresión:

−¿ ¿
2−¿+2 I ¿

I 2+ 2 S2 O2−¿→ S O 4 6 ¿
3

La titulación se completa cuando todo el I2 se ha convertido en I-. El punto final

de esta titulación se determina por un indicador colorimétrico. El indicador más
común es el almidón que cambia de color azul a transparente.
 Biochemical Oxygen Demand (BOD): is the amount
It’s the amount of dissolved oxygen needed by aerobic biological organisms to
break down organic material present in a given water sample at certain
temperature over a specific time period.
Addition of water by microbial seed (semillas). For example, air incubation of 5
days and determine the O2 that remains saturated in H2O.

4.2 SPECTROSCOPIC METHODS

 Adsorption Spectrophotometry

Many compounds absorb ultraviolet (UV) or visible (Vis) light. The amount of
radiation absorbed may be measured in the following way:
The absorbance can be easily calculated from percentage transmittance data:

A=log ( 100
%T )

So, if all the light passes through a solution without any absorption, then
absorbance is zero, and percent transmittance is 100%. If all the light is
absorbed, then percent transmittance is zero, and absorptions is infinite.
Beer’s Law  A=a·b·c
Where:
a= is the absorptivity which depends on the wavelength of the substance.
 b is the path length of the sample
c is the concentration of the compound in solution

For example, compounds that can be detected: ammonia, arsenic, boron,

chlorine, fluoride, nitrates, nitrogen, phenols…
Surfactants are compounds that lower the surface tension of a liquid in which is
dissolved:
NiH3 - As - B - Br2 - Cl2- CN- …
… F--NO3--NO2--N2-Phenols-PO43--Se-SiO2-S2-

 Atomic adsorption
It’s commonly used to analyse metals.

Used in toxicology research.

When we talk about plasma (gas) we are referring to the fourth state of matter.
The properties of this gas depend on the ionize state. It can be accelerated by
electricity.
There are positive ions in the plasma. The cathodes when are heated will release
atoms which will be excited. (Copper atoms will collide with the atoms in the
plasma).
Excited atoms colliding with the plasma will emit photons (2). Very small
wavelengths.
 The processes in a flame include the stages of:
o Desolvation (drying) in which the solvent is evaporated and the dry
sample nano-particles remain.
o Vaporization (transfer to the gaseous phase) in which the solid particles
are converted into gaseous molecule.
o Atomization in which the molecules are dissociated into free atoms
o Ionization where (depending on the ionization potential of the analyte
atoms and the energy available in a particular flame) atoms may be in
part converted to gaseous ions.
The metals which will be analysed in the atomizer must be the same that in the
Hollow cathode. There is a very small number of atoms that will react with a specific
wavelength.

 Atomic emission techniques: very commonly for practical use.

Inductively coupled plasma atomic emission spectroscopy (ICP-AES):
analytical technique used for detection of chemical elements.
Type of emission spectroscopy that uses the inductively coupled plasma to
produce excited atoms and ions that emit electromagnetic radiation at
wavelengths of a particular element.
It’s a flame technique. The intensity of the emission is indicative of the
concentration of the element within the sample.

 CHROMATOGRAPHY

 Gas chromatography (GC)

It’s a common type o chromatography for separating and analysing

compounds that can be vaporized without decomposition.
The gaseous compounds being analysed are a mixture of volatile materials.
The mixture passes through a column (usually made of metal or glass) which
is packed with an inert solid of high surface area, and this solid can be
covered by a liquid phase. (STATIONARY PHASE). As an alternative, we
an have an active solid without the liquid phase.
The gaseous compounds being analysed interact with the walls of the
column, which is coated with the stationary phase. This causes each
compound to elute at a different time, known as the retention time of each
compound. The comparison of retention times is what gives GC its
usefulness.
Initially there is a mixture of components. The different components will
emerge out of the column in different times depending on the strength of
interaction between each single component and the active phase.

Representación de una GC:

 A gas chromatograph is a chemical analysis instrument for separating
chemicals in a complex example. A gas chromatograph uses a flow-
through narrow tube known as the COLUMN, through which different
chemical constituents of a sample passs in a gas stream (carrier inert gas,
mobile phase) at different rates depending on their various chemical and
physical properties and their interaction with a specific column filing,
called the stationary phase. As the chemicals exit the column, they are
detected and identified electronically. The function of the stationary
phase in the column is to separate the different components, causing each
one to exit the column a different time (retention time). Other parameters
that can be used to alter the order or time of retention are the carrier gas
flow rate, column length and TEMPERATURE.
The process of separating the compounds in a mixture is carried out
between a liquid stationary phase and a gas mobile phase. The column
through which the gas passes though is located in an oven where the
temperature of the gas can be controlled. The concentration of a
compound in the gas phase is solely a function of the vapor pressure of
the gas.

BEST POSSIBLE ANALYSIS (COMBINATION):

GC + MASS SPECTROMETRY

 High- Performance Liquid Chromatography (HPLC).

In HPLC the stationary phase is a solid and the mobile phase is a liquid. It
has no temperature control (We don’t need to heat the sample in order to
have the phase transition.)

The sample (the mixture of components) goes in a liquid phase (solvent).

We have a solvent which is pumped (high pressure pump) through the
column which is filled with a solid adsorbent material. Each component in
the sample interacts slightly differently with the adsorbent material, causing
different flow rates for the different components and leading to the
separation of the components as they flow out of the column.

USUALLY MASS SPECTROMETRY AS

DETECTOR.

 Ion Chromatography

It’s a specific case of liquid chromatography. Here you can distinguish ions.
(Phosphates from phosphites … Arsenates from arsenites).
Example:

ASO43- ASO33-

PO43- PO33- P2O74-

 MASS SPECTOMETRY (MS)

MS is an analytical technique that measures the mass-to- charge ratio of ions.

Application: Identification of organic pollutants.

The results are typically presented as a MASS SPECTRUM, a plot of intensity

as a function of the mass-to-charge ratio.

A mass spectrum is a plot of the ion signal as a function of the mass-to-charge

ratio. These spectra are used to determine the masses of particles and of
molecules.

In a typical MS procedure, a sample is ionized, for example by bombarding it

with electrons. The pollutants molecules are broken by the electrons into
charged fragments having specific mass-to-charge ratio. These ions are then
separating according to their mass-to-charge ratio, for example by accelerating
them and subjecting them to an electric or magnetic field: ions of the same mass-
to-charge ratio will-undergo the same amount of deflection. Results are
displayed as spectra of the signal intensity of detected ions as a function of the
mass-to-charge ratio. The atoms or molecules in the sample can be identified by
correlating known masses (an entire molecule) to the identified mases or through
a characteristic fragmentation pattern.

The lines in the graph above are intensity lines.

Imagine: SEVERAL POLLUTANTS IN A SAMPLE  You break all of them,

but you don’t know which one corresponds to the first pollutant.

You have a 50 ratio  You can have possible fragments corresponding to this
ratio (NOT JUST ONE).
 For each line spectrum will give you different fragments.

 ASSAY (TEST=PRUEBA) OF MICROORGANISMS

A coliform count of water samples is performed by making appropriate dilutions

and incubating them at 35ºC for 48 hours in a nutrient broth. If the medium
becomes turbid, the presence of bacteria is indicated, and it can be spread over
an agar gel plate. After an additional 24 hours incubation, the number of bacteria
colonies on the plate is counted under a microscope and expressed in colony
forming units (CFUs).

Coliform bacteria, however, provide only a partial profile of the extent of

pollution of the water with pathogenic micro-organisms.

First, you take a sample of water (which MUST BE DILUTED). Then this
sample is in INCUBATION for 48 hours in a NUTRIENT BROTH at 35ºC. (It
looks like a cotton disk).
After some time, you see there are some spots which you can count one by one:

You counted 20 spots in 20 mm diluted water. Now you need to redo all the
calculations by the other way around.

Imagine they say it’s diluted 1/10  You take 2 mm and then you put then in
the oven for 48 hours at 35 ºC finding those spots. You can count them with
optical lenses:
 As a result: 20 cfu (colony-forming units) in 2 mm of water  You can go back
to the initial ratio since the ratio is 1/10.

 WATER SAMPLING AND PRESERVATION

FALTA AÑADIR ALGO

Some parameters must be analysed in the FIELD:
- Temperature
- Desorbed gases
- pH
(Microbial activity affects BOD).

WAYS of SAMPLING:
- Grab sampling: the analysis refers to water in that specific time in that
specific place. (Sample taken one time in one place).

- Composite sampling: you get samples periodically (Example: one sample

every day for a week). After, you mix everything, and you analyse the water.
You have an average of the conditions of the water.

 TOTAL ORGANIC CARBON (TOC).

TOC is the amount of carbon in an organic compound and is often used as a
non-specific indicator of water quality. Very general parameter to state the
pollution levels of water. Best parameter for indicating the total organic content
in samples.
How to determine it? Measurement:
Step 1: ACIDIFICATION of water
You want to get rid of all the inorganic carbons present in the water. So, by
bubbling an inert gas (like N2) into the water allows all bicarbonate and
carbonate ions to be converted to carbon dioxide.
2−¿
HCO−¿
3 /CO3 → CO2 ¿ ¿

Step 2: OXIDATION
This step includes the oxidation of all the carbon in the remaining carbon (which
now is organic) to CO2.
Modern TOC analyzers perform this oxidation in several processes:
Combustion, photo-oxidation and many different kinds of oxidation processes.

Step 3: DETECTION and QUANTIFICATION

 Accurate detection and quantification are the most vital components of the TOC
analysis process. Conductivity is one of the common detection methods.

5. METHODS FOR WATER TREATMENT. ALSO, FOR POLLUTANT

TREATMENT.

The table that is below, lists current methods for the treatment or organic,
inorganic, and microbiological pollutants in air, water, and soil.

TREATMENTS depending if the specie to analyse is…

ORGANICS INORGANICS MICROORGANISMS
Incineration and Precipitation/Coagulation Incineration
pyrolysis
Air stripping Membrane separation High-energy (γ)-
irradiation
Carbon adsorption Distillation Filtration
Microbial treatment Chemical treatment Carbon adsorption
Electrochemical Direct UV irradiation
treatment
Microbial treatment Ozonation
Chlorination

ME FALTA COMPLETAR AQUÍIII MIERCOLES 06/03 LUNES 04/NO

HUBO CLASE