Chimia ecologică a apelor

reziduale
Lec 10
 Problemele de calitate a apei
• Dezvoltarea intensivă a civilizației umane presupune încărcare mare
de deșeuri solide și lichide asupra mediului, în particular asupra apei.
• Poluarea apei provine din surse naturale, industriale și
managere/casnice
• Problema poluării apei este de o importanță pentru toate țările,
deoarece fluxurile și obiectele acvaticede pe Pământ sunt
interconectate
• Poluarea apei este cea mai masivă și cea mai importantă deoarece
afectează poluarea solului și a aerului.
• Substanțele toxice din sistemele acvatice pătrund în sol și aer.
• Impactul transfrontalier al poluării
• Calitatea insuficientă a tratării apei
• Gestionarea ineficientă a apei
 Definiţie

Apele reziduale sau uzate sunt apele care au fost

folosite pentru necesităţile casnice sau industriale
şi care, datorită impurităţilor adăugate, şi-au
schimbat componenţa chimică iniţială sau
proprietăţile fizice.
 Principalele tipuri de ape uzate
• Ape uzate menajere/municipal, include ape de spălat,
excremente umane, lichide menajere
• Scurgerile urbane și apele meteorologice: ploi,
zăpadă, deoarece intră în contact cu poluanții solului
• Ape uzate agricole: irigații, creșterea animalelor,
cultura culturilor, acvacultura etc. Se foloseste
aproximativ 69% până la 90% din utilizarea globală a
apei dulci. Cea mai mare parte a acestuia se întoarce
în sol și în căile navigabile cu adaos de nutrienți și
contaminanți.
• Ape uzate industriale – de obicei, acestea sunt ape
puternic poluate cu metale grele, substanțe organice,
agenți tensioactivi, particule solide, uleiuri, etc.
 Categorii de ape uzate industriale
• Apele uzate din industria chimică, organică, şi de sinteză
• Apele uzate de la fabricarea coloranţilor şi a produşilor de sinteză fină
• Apele uzate de la fabricarea unor produşi petrochimici
• Apele uzate de la fabricarea substanţelor explozive
• Apele uzate de la industrializarea lemnului
• Apele uzate din industria petrolului
• Apele uzate din industria textilă
• Apele uzate din industria prelucrării pielii
• Apele uzate din industria alimentară
• Apele uzate de la fabricarea produselor de fermentaţie
• Apele uzate de la prelucrarea deşeurilor animale şi vegetale
• Apele uzate din industria minieră
• Apele uzate de la extracţia şi prepararea minereurilor
• Apele uzate din industria metalurgică şi siderurgică
• Apele uzate din industria materialelor de construcţii
• Apele uzate de la centralele termoelectrice
 Principalele tipuri de poluanți în apele uzate
Chemical pollutants
Biological pollutants

•• If the wastewater
Heavy contains
metals including hyman
lead, feces it mayetc.;
zinc, chromium, also contain pathogens of one of the four types:
•• Bacteria (for example
Organic particles Salmonella,
contained in the Shigella, Campylobacter,
feces, hairs, Vibrio plant
food, paper fibres, cholera),
material, humus as well as in those applied in industrial processes ;
•• Viruses
Soluble (for example
organic hepatitis
material such asA, urea,
rotavirus,
fruit enteroviruses),
sugars, soluble proteins, pharmaceuticals, drugs, etc.;
•• Protozoa
Inorganic (for example
particples Entamoeba
such histolytica,
as sand, grit, Giardia lamblia,
metal particles, Cryptosporidium parvum) and
ceramics;
•• Parasites such as helminths
Soluble inorganic andas
material such their eggs
acids and(e.g. ascarissalts
dissolved (roundworm),
(ammonia,ancylostoma (hookworm),
cyanides, hydrogen trichuris
sulfide, (whipworm);
thiosulfates);
•• It can also contain
Macro-solids non-pathogenic
(sanitary bacteria
napkins, needls, toys,and
deadanimals
animals such as insects,
or plants, etc.;arthropods, small fish.
• Gases such as hydrogen sulfide, carbon dioxide, methane, etc.;
• Emulsions including paints, anhesives, mayonnaise, hair colorants, oils, etc.;
Physical indicators
• Toxins such as pesticides, poisons, herbicides, etc.;
• Pharmaceuticals and hormones and other hazardous substances

• Wastewaters are characterized with specific color, odor, taste, pH value, temperature
• Thermal pollution comes from power stations and industrial manufacturers
Indicatori principali de calitate a apei
• Physical indicators: temperature, conductivity, suspended
sediments, transparence or turbidity, odor, color, taste

• Chemical indicators: dissolved gases, heavy metals, organic

substances (biochemical oxygen demand (BOD) and
chemical oxygen demand (COD), surfactants, pH (acids or
alkali contents), total hardness, hydrocarbons, total
dissolved solids, nutrients, industrial chemicals (furans,
dioxins, PCBs – polychlorinated byphenyls, etc.), nitrates,
pesticides, orthophosphates, .

• Biochemical indicators:

Microorganisms such as fecal coliform bacteris

(Escherichia coli), Cryptosporidium and Goardia Lamblia,
etc.

• Radiological indicators (total radioactitity, radon)

Forme de poluare a apelor
După felul acţiunii asupra bazinelor acvatice se pot distinge
următoarele forme de poluare:

1. Poluarea termică
2. Poluarea cu săruri minerale
3. Poluarea cu particule în suspensie
4. Poluarea apei cu metale grele
5. Poluarea apelor cu compuşi macromoleculari, în special
lignină
6. Poluarea apelor cu produse petroliere
7. Poluarea apelor cu substanţe organice
8. Poluarea apelor cu elemente biogene
Consumul zilnic a resurselor naturale

Consum pe zi: Evacuări pe zi:

Apă 625 mii m3
Ape reziduale
Produse alimentare 500 mii m3
2 mii tone
Oraş
Cărbune 4 mi tone 1 mln locuitori Deşeuri solide
2 mii tone

Petrol 2,8 mii tone

Gaze de evacuare (noxe)
SO2, NO2, CO2,
Gaz 2,7 mii m3 hidrocarburi, 0.8 mii m3
 Wastewater Treatment
Scopul:
Pentru a gestiona apa evacuată
din case, întreprinderi și industrii
pentru a reduce amenințarea
poluării apei.
 Water treatment issues
• La nivel global, doar 20% din apele
uzate produse sunt tratate
corespunzător. (UNESCO 2012).
• Capacitatea de epurare depinde
de obicei de nivelul veniturilor
țării, astfel încât capacitatea de
epurare reprezintă 70% din apa
uzată generată în țările cu venituri
mari, comparativ cu doar 8% în
țările cu venituri mici.
Simple Wastewater Treatment Technologies
• Tehnologiile de tratare a apelor uzate
relativ simple pot fi concepute pentru a
oferi servicii sanitare cu costuri reduse
și protecție a mediului, oferind în
același timp beneficii suplimentare din
reutilizarea apei.
• Aceste tehnologii folosesc sisteme
naturale acvatice și terestre.
• Cea mai simplă metodă de reducere a
încărcăturii de poluanți pe corpurile de
apă este dizolvarea apei poluate cu apă
dulce înainte de deversare.
 Diluarea apelor uzate cu apă
curată
• O metodă de bază pentru aprecierea calităţii apei este
biotestarea ei prin observarea acţiunii acesteia asupra
anumitor organisme-test

• Pe baza datelor de biotestare, în scopul atingerii valorii

biologice depline a apei în bazinele acvatice este necesară
diluarea apelor reziduale cu apă curată după curăţirea lor
biologică, în proporţia următoare:
- apele reziduale casnice şi gospodăreşti care conţin
detergenţi fără amestec de ape industriale - de 10 ori
- apele reziduale industriale, care conţin substanţe specifice
deosebit de toxice - de 25 ori
- industria de celuloză şi hârtie - până la 100 sau, după o
prelucrare specială, până la 50 ori
- unele ape din industria de producere a cauciucului - până
la 1000 ori
Main Stages of Wastewater Treatment

 Pre-treatment
 Preliminary treatment
 Primary treatment
 Secondary treatment
 Sludge (biosolids) disposal
Flow sheet for wastewater treatment and sludge management
process
Primary Treatment
Wastewater Treatment

Primary Treatment Plant

 Primary treatment: bar screens

Bar Screen

catches large objects that

have gotten into sewer
system such as bricks,
bottles, pieces of wood,
etc.
Primary treatment: Mechanical screening
Primary Treatment Process

Primary treatment reduces the suspended solids

and the B.O.D. of the wastewater.
From the primary treatment tanks water is
pumped to the trickling filter for secondary
treatment.
Secondary treatment will further reduce the
suspended solids and B.O.D. of the wastewater.
 Secondary Treatment

Secondary treatment is a biological process

Utilizes bacteria and algae to metabolize
organic matter in the wastewater
In some treatment plants secondary
treatment occurs on the trickling filter
Secondary Treatment
Wastewater Treatment Stages
From secondary treatment on the trickling filter
water flows to the final clarifiers for further
removal of sludge.
The final clarifiers are another set of primary
sedimentation tanks.
From the final clarifiers the water is discharged to
the natural water bodies.
 Clarifying equipment
The final clarifiers
remove additional
sludge and further
reduce suspended
solids and BOD
(biological oxygen
demand – contents in
organic matter).
Membrane separation: used to remove very fine
particles or organics from water, to desalinate water
Filtration of treated water
Sedimentation is used for separation of solid particles that
are heavier than water
Sludge from wastewater treatment
 Disposal of sludge or biosolids

- the sludge undergoes lime stabilization (pH is

raised by addition of lime) to kill potential
pathogens
- the stabilized sludge is land applied by injection
into agricultural fields
- the sludge can be disposed by landfill or
incineration
 Wastewater issues in the Republic of Moldova
• Total amount of surface waters in the Republic of Moldova accounts for 1,32 bln
m 3. Water from Nistru river in geographical network makes 67%, river Prut -
24% and other rivers - 9%.
• In total, in the country there are 3621 rivers with total length of 16 000 km.
There are more then 3 500 natural water reservoirs and lakes.
• However, direct water consumption is often impossible because of high
pollution level.
• There are series of wastewater treatment plants (WWTP) in Moldova, but many
of them are out of operation and others are treating water unsatisfactory.
• There are 1534 settlements in Moldova, in 80% of them during 1960-1990ies
the WWTP were constructed
• In the last 20 years many WWTP were destroyed
• In 2006, from 131 WWTP in Moldova only 78 were functioning
• Many localities for many years do not have treatment plants at all (Soroca,
Rezina, Criuleni, Calarasi),
• In Moldova the operating WWTP have the capacity between 40 and 400
m3/day.
• In the last years (2014-2016) a series of new biological WWTS were constructed:
in the regions of Falesti, Rascani, Falesti, Orhei.
• In the wastewaters from agricultural sector (especially, wineries) COD values
may reach up to 15000-23000mg O2/l.
 Water treatment in
Moldova

At many enterprises and in rural areas there are no waste-water

treatment facilities or they are in an unsatisfactory condition

Water
treatment
facilities

1990 Present

Approx. 600 Approx. 154

Wastewater treatment levels applied in Moldova
• Primary treatment including screens, sedimentation and grit removal.
• Treatment includes:
filtering wastewater through fine screens to remove items such as paper,
cotton tips and plastic;
removing sand and grit that has fallen to the bottom of aerated grit tanks;
removing solids that have settled to the bottom of sedimentation tanks;
removing oil and grease that floats to the top of tanks using scrapers.
 
Wastewater treatment levels applied in Moldova
• Secondary treatment which removes nutrients and other
impurities dissolved in water.
Five Key stages:
• Fermentation tank
• Anaerobic zone
• Anoxic zone
• Aeration zone
• Secondary clarifiers
Wastewater treatment levels
applied in Moldova
• Tertiary treatment, as a rule, only
consists in disinfection of treated water
most often with chlorine (Cl2), or less
often, with sodium chloride (NaOCl) or
calcium chloride (CaCl2).
• Then, in the small towns, rayonal
(county) centers, water flows to the
biologic ponds before discharging into
the water bodies.
NATURAL WASTEWATER TREATMENT SYSTEMS IN THE
COUNTRY

• Biological ponds with artificial aeration

• Biological ponds with natural aeration
• Constructed Wetlands (CWs) (Zone umede construite)
• Other types of Natural Treatment Systems (filtration fields, septic
tanks, anaerobic accumulation ponds) - in some localities, functioning
as a single treatment step.
Best practices of Constructed Wetlands operation
in Moldova
• Treatment plant in Rusca involves a septic tank (as a first
treatment stage) constructed in 2007.
• The second stage is a CW with 4 horizontal beds 300 m² each,
filled with gravel, which surface is planted with reed. Treatment
capacity is 40 m³/day.
• In this particular case, a 700-m canalization system was
additionally constructed, which allowed to connect 50 private
houses in Rusca village to the treatment plant.
Constructed Wetland in Moldova
(Photo Apasan Agency)

• 
• 
Biological water treatment technology: aerobic and anaerobic
treatment
Economy of Moldova is based mainly on agricultural production, which annually
produces a lots of vegetable and other replicable wastes – a feedstock for biogas
technology;
Aerobic treatment technologies – energy consuming, do not allow to reach
required treatment level because of high organic load;
Anaerobic technology – economically beneficial, producing biogas, treated water
for irrigation, stabilized sludge to be used as organic fertilizers;
Preferable approach – to combine aerobic treatment with anaerobic one.
Biochemical Treatment of Agro-industrial
Waste Waters

• Another water treatment technology

that has been essentially modified and
improved, was a well-known biogas
technology.
• The biogas formation process was
intensified and a high yield of a series of
useful products was obtained.
Main features of biogas technology
• Methane digestion, or biomethanogenesis is a process of
biomass transformation in energy, known long ago.

• It was discovered in year 1776 by Volta who proved the

presence of methane in the swamp gas.

• Biogas formation (a mixture of

65% СH4, 30% CO2, 1% Н2S and insignificant amounts of
N2,
O2, H2, CO) – a complex
microbiological process realized
with microbial consortium.

• Energy of 28 m3 biogas is
equivalent to energy of 16.8 m3 of
natural gas, 20.8 l of oil or 18.4 l of
diesel fuel. From 1 m3 biogas up
to 2 Kwt electric power can be generated.
The most simple biogas reactors
MECHANISM OF BIOGAS BIOCHEMICAL FORMATION
DURING THE ANAEROBIC TREATMENT OF WASTEWATERS

• Live activity of methane producing microorganisms is connected with the

intermediate stage of carbon dioxide formation and emission, which is a nutrition
medium for their development. The methane is thus formed according to the
following general type reactions:
• 4Н2А + СО2  4А + СН4 + 2Н2О
• 2Н2 + СО2 = СН4 + 2Н2О
• 2С2Н5ОН + СО2 = СН4 + 2СН3СООН
• 3С4Н9ОН + СО2 = СН4 + 2С3Н7СООН
• 4СН3СНОНСН3 + СО2 = СН4 + 4СН2СОСН3 + 3Н2О
• where Н2А – any compound for which given organism has an enzyme
 SPECIFICS OF METHANOGENESIS PROCESSES
1. At the first, methanogenic stage of biochemical reactions,
the protons reduction occurs with the concortium of
microorganisms. Therefore, the excessive reducer is
eliminated. As a result, hydrogen and carbon dioxide
emission occurs:
Pyruvite → Acetyl-CoF + СО2 + Н2
Formiate → СО2 + Н2
Acetaldehyde → Аcetate + Н2

2. Hydrogen emission is catalysed with two enzymes:

hydrogenase and specific СО-hydrogenase acting in common.
In the absence of final acceptor of electrons (oxygen, nitrates
and nitrites, etc.), carbon monoxide (CO) starts emitting

3. During the methane formation processes, bacteria use

the limited amounts of substrates, among them the most
important being acetate (up to 75 %), as well as carbon
dioxide, formiat, methanol, methylamines, carbon
monoxide:
СO2 + 4 H2 → CH4 + 2 H2O
4 HCOO- + 4 H+ → CH4 + 2 H2O + 3 CO2
4 CO + 2 H2O → CH4 + 3 CO2
CH3COO- + H+ → CH4 + CO2
4 CH3OH → 3 CH4 + CO2 + 2 H2O
Biogas technology possibilities in
Moldova
Out of 150 wineries, 32 have the
distilleries, forming high concentrated
waste waters, toxic for environment
(summary amount 5,0 mln m3/year,
average COD up to 25000 mgО2/l).
• Biogas yield from 1 kg COD - 0,5 м3
with 70% methane contents; total
biogas yield/year is 62,5 mln
m3/year
• Potential methane contents in biogas
apprx.
43,0 mln m3/year, which makes it
possible to cogenerate
82 mln kWt electric energy and 150
mln kWt heat energy
• Biogas reactor cost is 400 $/м3;
with average wineries operation
during 200 days/year, there is a need
in about 50 reactors 1000 м3 each,
with summary expenses 10 mln $, or
– 1 $/m3 generated methane.
• Payback of expenses – 3 years.
PILOT BIOGAS REACTOR AT THE
«BARDAR» WINERY, R.MOLDOVA

Biochemical formation of biogas as a result of methanogenic

digestion involves the following reactions:
4Н2А + СО2  4А + СН4 + 2Н2О
2Н2 + СО2 = СН4 + 2Н2О
2С2Н5ОН + СО2 = СН4 + 2СН3СООН
3С4Н9ОН + СО2 = СН4 + 2С3Н7СООН
4СН3СНОНСН3 + СО2 = СН4 + 4СН2СОСН3 + 3Н2,
where Н2А – any organic component subjected to
hydrolysis.
BIOGAS REACTOR AT THE FARLADENI AGRICULTURAL FARM
(R.MOLDOVA, HANCESTI REGION)
Intensive Water Treatment Technologies
• To provide the intensive waste water treatment, i.e. to reduce essentially the
treatment time or to reach much higher purification level in the time unit, it was
proposed to apply the combined treatment methods:
- A combination of physical-chemical and microbiological treatment;
- Combination of several physical-chemical methods: electrocolagulation, chemical
treatment and oxidation;
- Combination of electroflotation and electrocoagulation
- Other comnbined processes.
Photo-catalytic treatment of wastewaters polluted with the the persistent
organics
(hard biologically degradable substances)
Photocatalytical Treatment of Waste Waters Containing the Persistent
Organic Pollutants

• A comprehensive studies have been carried out in order to elaborate the intensified
and efficient methods and reactors for decomposition of refractory toxic pollutants in
water compartments and waste waters
 Combined photo- and biodegradation of
benzothyazols in the waste waters

• Benzothiazoles are manufactured and used

in large amounts throughout the world;
• They are refractory pollutants
• They are chemically stable and hard
biologically degradable substances
• They possess carcinogenic properties

Chromatograms of OBT water solutions prior to treatment (А)

(Conditions: Сinit. OBT = 5,18 mMol. рН = 7,0, t = 25 оС),
And after Fenton/UV-irradiation (B) within 0,5 h
PHOTOCATALYTIC REACTORS FOR THE DEGRADATION OF PERSISTENT
XENOBIOTICS (Benzothiazoles, etc.)

69
 Kinetics of Aminobenzothiazole photocatalytic
degradation

Conditions:
Iron cytrate-ammonia complex (CitrFe)
With direct UV-irradiation (λ = 253 nm):
1 – direct photolysis;
2 – in presence of 0,5 мМ Н2О2;
3 - CitrFe purified;
4 – CitrFe commercial;
5 – CitrFe + Н2О2 (0,5 мМ)
Scheme of the combined reactor for photo- and biodegradation of
the refractory organics during the treatment of wastewaters
COMBINED TREATMENT OF
THE INDUSTRIAL
WASTEWATERS
 PURIFICATION OF THE
WASTEWATER FROM TEXTILE
INDUSTRY, CONTAINING THE
COLORANTS

Direct colorant group: Active colorant group: Acid colorant group:

Active Orange (max = 490 nm; M=605 g/mol) Green – acid (VA): M = 706
Direct Blue K( max = 610 nm; M =683 g/mol)
OH
H 2N OH

NaO 3S N N N N

OCH3 OCH3 Active Red (max = 510 nm; M= 1381 g/mol)

SO3Na

Direct Brown (max= 490 nm; M =595 g/mol)

OH Blue – acid (A A) max = 626 nm, M = 678

NH 2
HO N N N N

COONa
Active Blue (max = 600 nm; M= 681 g/mol)
SO3Na
O NH2
Direct Bright Red (max = 540 nm; M =696 g/mol) SO3Na

NH 2 NH 2 N
O NH NH C C Cl
N N N N
SO3Na N N
C

SO3Na Cl
SO3Na Active Golden Yellow Red C (ARC) max = 540 nm, М = 360 g/mol
(max = 370 nm; M= 613 g/mol)
Direct Bright Blue (max = 626 nm; M = 968 g/mol) Cl
CH3
NH2 OH OH SO3Na
NH2 N
N N N NH N N
NaO3S N N SO3Na
N
OCH3 OCH3 Cl
NaO S SO3Na SO3 Na
3
Combination of coagulation and catalytic
oxidation of colorants
First stage:
Removal of textile colorants with aluminium coagulant, effect equals 75%
Optimum coagulation conditions:
•pH value = 5.5 – 6.5
•aluminum coagulant amount depends on the chemical nature of colorants
•maximum concentration of textile colorant in the solution is 250 mg /l.

Second stage:
Oxidative degradation of 22.5% of the initial concentration of colorants
Optimal conditions of oxidation and mineralization process:
•pH value = 2.0 – 2.5
•hydrogen peroxide concentration equals 2-3*10-3 mol/l and iron(II) is 3 to 5*10-4 mol/l;
•maximum concentration of colorant equals 50-75 mg/l.
Technological scheme of 
wastewater purification 
from textile industry
Wastewater issues in Europe
• Wastewater treatment in all parts of Europe has improved during
the last 15-20 years, with a growing proportion of the population
connected to waste water treatment facilities and with the waste
water being treated to more demanding standards.
• Pollution from agriculture and storm water overflows poses
problems in improving water quality.
• Nitrogen and phosphorus from waste water treatment plants and
industry, and emissions from agriculture — fertilisers and manure —
remain the main sources of nutrient and organic pollution. The other
pollutants emerge, which are chemicals present in low
concentrations but may have harmful effects on aquatic organisms
or those that feed on them.
• Micro-plastics, such as those found in personal care products, and
micro-organisms resistant to antibiotics, present risks to
environment.
• Expenses for WWT in EU countries for the last years reached more
than 14 bln Euros and are excpected to reach 22 bln Euros in the
next years.
 Procesele avansate de oxidare (PAO)
PAO sunt sisteme excelente pentru remedierea apelor uzate contaminate care conțin
poluanți organici greu oxidaili.
Cele mai studiate AOP sunt procesele pe baza de :
1. fotochimie (PAOF),
2. peroxid de hidrogen/UV,
3. fotocataliză eterogenă (FE),
4. foto-Fenton (FF),
5. UV&O3 și
6. combinația acestor tehnologii.
Toate PAO se bazează pe producerea de specii foarte reactive (în special radicali
hidroxilici, HO •) capabili să degradeze sau să transforme poluanții chimici, provocând în
cele din urmă mineralizarea totală.
Unul dintre dezavantajele majore ale PAO-urilor este că costurile operaționale sunt
relativ ridicate în comparație cu tehnologiile mai puțin costisitoare, cum ar fi
tratamentele biologice, utilizarea cărbunelui activ etc.
Cu toate acestea, aceste tehnologii pot fi utilizate combinate cu ele însele sau cu
tehnologiile convenționale. În ciuda unei cantități uriașe de publicații științifice, cererile
și metodele brevetate privind PAOF sunt rare.
Mai jos noi vom prezenta unde si cum pot fi utilizate PAO-urile.
 Istoria PAO

Din punct de vedere istoric, s-au folosit diferite metode

pentru tratarea apelor uzate industriale și menajere.
În majoritatea cazurilor, apa poluată antropogen poate fi
tratată eficient prin metode convenționale, cum ar fi:
1. procese biologice,
2. adsorbție pe cărbune activ sau alte materiale,
3. oxidare termică,
4. clorurare,
5. ozonare,
6. floculare-precipitare,
7. osmoză inversă (RO) etc.
Tipurile de PAO
1. UV/H2O2
Mulțumesc pentru atenție!