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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr.

2/2011

SURSELE DE AZOT I BAZELE


PROCESULUI DE
NITRIFICARE - DENITRIFICARE

THE NITROGEN SOURCES AND


THE BASIS OF THE
NITRIFICATIONDENITRIFICATION PROCESS

Belingher Mihaela-Liliana, Drd.ing.


Chimerel Mircea-Eleodor, Drd.ing.
Universitatea din Petroani, Centru de
Doctorat i Formare Continu

Belingher Mihaela-Liliana, Drd.eng.


Chimerel Mircea-Eleodor, Drd.eng.
University of Petrosani, Centre of
Doctorate and Continous Education,

Rezumat: Ionul nitrat (sau azotat) are formula


chimic NO3-. Nitratul reprezint cea mai oxidat
form chimic a azotului ntalnit n sistemele
naturale. Nitratul este un ion negativ (anion) i se
cupleaz cu ioni pozitivi (cationi) formnd sruri
precum azotat de potasiu KNO3, sau azotat de sodiu,
NaNO3. Ionul nitrat este unul dintre cei mai solubili
anioni n ap cunoscui. Nitraii sunt cea mai
accesibil forma a azotului pentru microorganisme i
plante.
Poluarea cu nitrai reprezint ncrcarea
factorilor de mediu ap (subteran i de suprafa) i
sol cu compui ai azotului, ale crei urmari pot fi:
periclitarea
sntii
oamenilor,
afectarea
organismelor vii i a ecosistemelor terestre i acvatice,
stnjenirea folosinelor apei i deteriorarea ambianei
naturale.

Abstract: Nitrate ion (azotate) has the chemical


formula NO3-. Nitrate is the most oxidized chemical
form of nitrogen found in natural systems. The nitrate
is a negative ion ( anion) and is coupled with positive
ions (cations) forming salts such as KNO3 potassium
nitrate or sodium nitrate NaNO3. Nitrate ion is one of
the most known water soluble anions. The nitrates are
the most accessible form of nitrogen for plants and
microorganisms.
The nitrates pollution represent the loading of
the environmental factors, water (surface water and
underground water) and soil with nitrogen
compounds, whose consequences can be : endangering
the human health, damaging the living organisms and
the terrestrial and aquatic ecosystems, impairing the
water utilization and damaging the natural ambiance.
Keywords: nitrogen, nitrification, dentrification

Cuvinte cheie: azot, nitrificare, dentrificare

1.THE NITROGEN SOURCES


1.PROVENIENA AZOTULUI DIN
FROM THE WASTE WATERS
APELE UZATE
The nitrogen is one of the most
Azotul este unul dintre componentele
cele mai prezente n cadrul celor patru
elemente principale care formeaz biosfera:
atmosfera, hidrosfera, scoara terestr i
esuturile organismelor vii sau moarte.
Fiecare element conine azot sub diferite
forme. Cantitatea total de azot rmne
neschimbat, ns stocurile diverselor forme
sub care azotul exist se afl ntr-o continu
modificare.
Activitatea uman reprezint una din
sursele de azot cea mai frecvent ntlnit,
fiind n acelai timp unul din fluxurile
nentrerupte care modific continuu stocurile
de azot din biosfer. Punctul final, n care
azotul rezultat att din activitatea uman ct

present components in the four main elements


that form the biosphere: the atmosphere, the
hydrosphere, the earths crust and the living
or dead organisms tissues. Each element
contains nitrogen in various forms. The total
quantity of nitrogen remains unchanged, but
the stocks of the various forms in which the
nitrogen exists is in continuously change.
The human activity represents one of
the most common nitrogen sources, being in
the same time one of the continuously flows
that are modifying continuously the nitrogen
stocks in the biosphere. The final point in
which the resulted nitrogen both from the
human activity and from the other activities,
is reflected in hydrosphere which is a
collector for the nitrogen quantities resulted

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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011

i din celelalte activiti se regsete este


hidrosfera care constituie un colector pentru
cantitile de azot rezultate n exces.
Principalele efecte ale acumulrii azotului n
ap sunt: epuizarea cantitilor de oxigen
dizolvat din apele receptoare, stimularea
eutrofizrii, creterea toxicitii vieii
acvatice, periclitarea sntii publice i
diminuarea probabilitii ca apele s mai fie
reutilizabile.

2.SURSE DE AZOT

in excess. The main effects of the nitrogen


accumulation in the water are: the depletion
of the oxygen dissolved in the receiving
waters, the eutrophication stimulation, the
increase of the aquatic life toxicity, the public
health endangering and the probability
diminution that water could be reusable.

2. NITROGEN SOURCES
Understanding the nitrogen sources
and their variability, it can provide a picture
of the contribution that the treatment plants
have on the cumulative effects of nitrogen in
nature. This thing may influence the
decisions regarding the level and type of
purification, which is usually specific to each
case. In analyzing the nitrogen pollution
problem a particular attention should be give
to the all nitrogen possible sources
determination such that the total evaluated
quantity to be as accurately estimated.
The matter with nitrogen content can
infiltrate in the aquatic environment, from
natural sources or from sources caused by
human peoples. The delimitation of the two
sources can be often confused, because the
apparent quantities from natural sources may
include nitrogen caused by human activity.
Some direct sources through which
nitrogen infiltrates in the aquatic environment
are shown in table no1, together with the
main transport mechanisms responsible for
the nitrogen existence in the receiving water
systems.

nelegerea surselor de azot precum i a


variabilitii acestora poate oferi o imagine a
contribuiei pe care staiile de epurare o au
asupra efectelor cumulative ale azotului n
natur. Aceasta poate influena deciziile
privind nivelul i tipul epurrii, care de regul
este specific fiecrui caz n parte. n
analizarea problemei polurii cu azot o
atenie
deosebit
trebuie
acordat
determinrii tuturor surselor de azot posibile
astfel nct cantitatea total evaluat s fie ct
mai exact estimat.
Materia cu coninut de azot poate
ptrunde n mediul acvatic fie din surse
naturale, fie din surse cauzate de oameni.
Delimitarea celor dou surse poate fi adesea
confundat deoarece cantiti aparente din
sursele naturale pot include azotul generat de
activitatea uman.
Cteva surse directe prin care azotul
ptrunde n mediul acvatic sunt evideniate n
tabelul nr. 1, mpreun cu principalele
mecanisme de transport responsabile pentru
existena azotului n sistemele de ap
receptoare.
Tabel 1 - Surse directe de azot
Surs
Ap uzat neepurat
Efluent epurat al staiilor de epurare
Reziduurile solide ale depozitelor controlate
Surse industriale
Emisii vulcanice sau alte emisii terestre
Ferme fertilizate
Reziduuri animaliere
Descompunerea plantelor i a esutului animal
Bazine septice
Vapoare/alte nave
Suprafee urbane

Tipul de transport la sistemele de ap naturale


Descrcare direct
Descrcare direct, utilizarea pmntului
Descrcare direct, utilizarea pmntului
Descrcare direct, deplasarea acviferului, precipitaii
Precipitaii, vnt i decantri gravitaionale
Scurgeri de suprafa, deplasarea acviferului
Volatilizare/precipitaii, curgere de suprafa, deplasarea
acviferului
Scurgeri de suprafa, deplasarea acviferului
Micarea acviferului
Descrcarea direct
Descrcri directe, scurgeri de suprafa

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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011
Combustibili minerali
Organisme care fixeaz azotul
Pmnt afnat
Levigatul depozitelor controlate de gunoi

Precipitaii, vnt i decantare gravitaional


In situ
Vnt i decantare gravitaional
Deplasri ale acviferului

Table 1 Direct sources of nitrogen


Source
Untreated waste water
Purified effluent of the treatment plants
Solide wastes of controlled deposits
Industrial sources
Vulcanic emissions or other terrestrial emissions
Fertilized farms
Animal residues
The plants and animal tissues decomposing
Septic basin
Boating/other vessels
Urban surfaces
Mineral fuels
Organisms that fixed the nitrogen
Dispersed soil
Deposits leaching controlled by nitrogen

The type of transport to the natural water systems


Direct discharge
Direct discharge, soil utilization
Direct discharge, soil utilization
Direct discharge, aquifer movement, rainfalls
Rainfalls, wind and gravitational settling
Surface drains, the aquifer movement
Volatilization/rainfalls, surface flow, the aquifer movement
The surface flow, the aquifer movement
The aquifer movement
Direct discharge
Direct discharges, the aquifer movement
Rainfalls, wind and gravity settling
In situ
Wind and gravity settling
The aquifer movement

3. SURSE DE AZOT PRODUSE DE 3. NITROGEN SOURCES


PRODUCED BY THE HUMAN
OAMENI
Sursele de azot provenite din activitatea PEOPLE

uman includ apele uzate menajere epurate i


neepurate, reziduurile urbane, reziduurile
industriale, depuneri atmosferice i scurgeri
de suprafa.
a. Apele uzate menajere
b. Apele uzate industriale
c. Levigatul produs la depozitele
controlate de deeuri menajere
d. Depozitarea atmosferic
e. Scurgerea de suprafa a apelor de
ploaie

The nitrogen sources produced by the


human people include the treated and
untreated domestic sewages, industrial
wastes, atmospheric depositions and the
surface drains.
a. Sewages
b. Industrial waste waters
c. The soil leaching on the controlled
household waste deposits.
d. Atmospheric depositions
e. Surface drains of the rainwater.

4. TRANSFORMRILE
SUFERITE DE AZOT

4. THE NITROGEN
TRANSFORMATIONS

Nitrificarea este procesul prin care se


realizeaz oxidarea biologic a amoniului.
Aceasta se realizeaz n dou etape, prima la
forma de azotii i apoi la forma de azotai.
Responsabile pentru aceste dou etape sunt
dou bacterii chemoautotrofe (obin energie
din reacii chimice, prin oxidarea compuilor
anorganici asemenea amoniacului, azotiilor
i sulfidelor), respectiv nitrosomonas i
nitrobacter.

The nitrification is the process


through which the biological oxidation of
ammonium is realized. This is realized in two
stages, first to the form of nitrites and then to
the form of nitrates. Responsible for this two
stages are two bacteria chemoautrofe ( that
obtain energy from chemical reactions,
through the inorganioc compounds oxidation,
such as nitrites and sulphides) respectively
nitrosomonas and nitrobacter.

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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011

Reaciile de transformare sunt n


general cuplate i au loc rapid la forma de
azotat; nivelul de azotii la un moment dat
este relativ sczut. Azotaii pot fi folosii n
sintez pentru a sprijini creterea plantelor
sau pot fi substanial redui prin denitrificare.
Denitrificarea este reducerea biologic
a azotailor la azot gazos. Ea poate fi realizat
n mai multe etape pe cale biochimic, cu
producere final de azot gazos. O gam larg
de bacterii heterotrofe iau parte la proces,
necesitnd carbon organic ca surs de
energie.

Pentru ca procesul de epurare biologic


s se desfoare n condiii optime, raportul
optim C:N:P este ntre 100: 10:1 i 100: 5 : 1.
Principalele transformri pe care
azotul le sufer n cadrul mediului
nconjurtor sunt:
a.Reducere (fixare)
b.Amonificare
c.Sintez
d.Nitrificare
e.Denitrificare
Reaciile de amonificare, sintez,
nitrificare i denitrificare sunt mecanismele
primare angajate n epurarea apelor uzate
pentru controlul i/sau eliminarea azotului.
Condiiile de mediu care influeneaz
reaciile includ temperatura, pH-ul, procesele
microbiologice, potenialul de oxidare
reducere i disponibilitatea substratului,
nutrienilor i a oxigenului.
n cadrul procesului de epurare
biologic transformrile suferite de azot sunt
nitrificarea i denitrificarea.

5. BAZELE TEORETICE ALE


NITRIFICRII

The transformation reactions are


generally coupled and held fast to the form of
nitrogen, the level of nitrates at one time is
relatively low. Nitrates can be used in
synthesis to support the plant growth or it can
be substantially reduced by denitrification.
Denitrification is the biological
reduction of nitrates to gaseous nitrogen. It
can be done in several stages in a biological
way, with a final production of gaseous
nitrogen. A wide range of heterotrophic
bacteria take part in the process, requiring
organic carbon as an energy source.
Because the biological treatment must
to take place under optimum conditions, the
optimum ratio C:N:P is between 100: 10:1
and 100: 5 : 1
The main transformation that the
nitrogen undergoes in the environment are:
a.reduction(fixation)
b. ammonation
c. nitrification
d. denitrification
The
ammonification
reactions,
synthesis, nitrification, denitrification, are the
primary mechanisms involved in the waste
water treatment, for the nitrogen control
and/or removal.
The environmental conditions that
influence reactions, include the temperature,
pH, microbiological processes, the oxidation
potential, the sublayer,nutrients and oxygen
reduction and avalilability.
During the biological treatment
process, the transformations sustained by
nitrogen are the nitrification and the
denitrification.

5. THE THEORETICAL BASIS OF


NITRIFICATION

The process in which the nitrogen (as


ammonium ions) from the untreated or
Procesul n care azotul (sub forma de
decanted waste water is substantially
ioni de amoniu) din apa uzat neepurat sau
transformed in nitrites, is known as
decantat este substanial transformat n
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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011

nitrai este cunoscut sub denumirea de biological nitrification.


"nitrificare biologic".
In the nitrification process occurs two
important processes : the reduction of organic
n procesul de nitrificare au loc dou
substance that is produced with the help of
procese importante: reducerea substanei
some aerobic heterotrophic bacteria (see
organice, care se realizeaz cu ajutorul unor
figure 1 a), respectively the ammonia
bacterii aerobe heterotrofe (vezi figura 1a) i
nitrogen reduction (the nitrification itself)
respectiv reducerea azotului amoniacal
that is realized with the help of some
(nitrificarea propriu-zis) care se realizeaz
autotrophic aerobic bacteria populations (see
cu ajutorul unor populaii de bacterii aerobe
figure 1 b) which oxidizes ammonia to nitrate
autotrofe (vezi figura 1b), care oxideaz
with the intermediate formation of nitrite.
amoniul la nitrat cu formarea intermediar a
nitritului.

(a) aerobe heterotrofe


(a) heterotrophic aerobic
Fig. 1. - Reprezentarea schematic a
metabolismului bacteriilor implicate n
procesul de nitrificare

(b) aerobe autotrofe


(b)autotrophic aerobic
Fig. 1 Schematic representation of the
metabolism of bacteria involved
in the nitrification process.

Prin nitrificare nelegem oxidarea


azotului amoniacal (NH4-N) n nitrit (NO2-) i
a nitritului n nitrat (NO3-). Principalele dou
specii de bacterii care realizeaz procesul de
nitrificare sunt Nitrosomonas i Nitrobacter.
Sarcina oxidrii este aici preluat de
ctre bacteriile autotrofe (nitrosomonas,
nitrobacter):

By nitrification we understood the


ammoniacal nitrogen oxidation (NH4-N) to
nitrite (NO2-) and the nitrite into nitrate (NO3). The two main species of bacteria that
realize the nitrification process are
Nitrosomonas and Nitrobacter.
The oxidation load is here taken by
the autotrophic bacteria (nitrosomonas,
nitrobacter):

Treapta I: Nitrosomonas
NH4 + 3/2 O2 NO2-+ H2O + 2H+ + Energie
Treapta a II-a: Nitrobacter
NO2-+ 1/2 O2 NO3-+ 2 H+ + H2O + Energie
Reacia totala:
NH4+ 2O2 NO3-+ 2 H+ + H2O + Energie

Este caracterizat printr-un consum


mare de oxigen (1 g NH4-N necesit 4,6 g O2)
i printr-o producie mare de acizi (1 mol de
NH4-N formeaza 2 moli de H+).
Pentru
descompunerea
substanei
organice pe baz de carbon sunt
necesare:
- condiii aerobe
- microorganisme heterotrofe aerobe

It is characterized by a high
consuption of oxygen (1 g NH4-N requires
4,6 g O2) and through a large production of
acids (1 mole of NH4-N forms two moles of
H+).
For the organic on carbon base
substance decomposition are needed :
- aerobic conditions
aerobic
heterotrophic

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microorganisms
- mediu bogat in oxigen (min. 1
- environment rich in oxygen (
mgO2/l)
minimum 1 mgO2/l)
Pentru procesul de nitrificare sunt
necesare:
For the nitrification process is needed
- condiii aerobe
:
- aerobic conditions
- microorganisme autotrofe aerobe
- aerobic autotrophic microorganisms
- mediu bogat in oxigen (min. 2
- environment rich in oxygen (
mgO2/l)
minimum 2 mgO2/l)
Factorii care influeneaz procesul The factors that influence the denitrification
denitrificare
sunt:temperatura,concentraia process are : temperature, pH, the dissolved
oxigenului dizolvat, pH-ul, alcalinitatea, oxygen concentration, alkalinity, inhibitors,
inhibitorii, raportul carbon organic influent/ the report influential organic carbon/nitrogen,
oxidative reductive environment.
azot, mediile oxidativ reductive.

6. PROCESE DE DENITRIFICARE 6.THE DENITRIFICATION


PROCESSES
Transformarea - N la o form mai
uor de eliminat, este realizat de mai multe
tipuri de bacterii dintre care se pot meniona:
achromobacter,
aerobacter,
alcaligenes,
bacillus, brevibacterium, flavobacterium,
lactobacillus,
micrococcus,
proteus,
pseudomonas si spirillum [2]. Aceste bacterii
anoxice heterotrofe, ce i obin energia
necesar dezvoltrii din oxidarea carbonului
organic, sunt capabile de reducere a azotailor
n dou etape. Prima etapa o constituie
transformarea azotailor la azotii. Aceast
etap este urmat de producerea oxidului
nitric (NO), oxidului nitros (N2O) i apoi a
azotului gazos.

N conversion to a form more easily to


remove, is realised by a several type of
bacteria that may be mentioned :
achromobacter,
aerobacter,
alcaligenes,
bacillus, brevibacterium, flavobacterium,
lactobacillus,
micrococcus,
proteus,
pseudomonas and spirillum [1]. These anoxic
heterotrophic bacteria that obtain their energy
needed for development of organic carbon
oxidation, are able to reduce the nitrates in
two stages. The first stage is the conversion
of nitrates to nitrites. This step is followed by
the nitric oxide production (NO), nitrous
oxide (N2O), and then the gaseous nitrogen.

The last three compounds are of


Ultimii trei compui sunt de natur gaseous nature and they can be released into
gazoas i pot fi eliberai n atmosfer.
the atmosphere.
For the denitrification process is
Pentru procesul de denitrificare sunt needed :
necesare:
-anoxic conditions (environment poo
- condiii anoxice (mediu lipsit de in oxygen at most 2 mgO2/l)
oxigen cel mult 0,1 mgO2/l)
-anoxic heterotrophic microorganisms
- microorganisme heterotrofe anoxice
The conversion of nitrates to gaseous
Transformarea azotailor la azot gazos nitrogen occurs in the production of
are loc cu producere de alcalinitate, ceea ce alkalinity, leading to an increase of pH. The
va conduce la o cretere a pH-ului. Valorile optimum values of pH are in 7-8 domain with
optime pentru pH se gsesc n domeniu 7-8 different optimal values for different bacterial
cu diferite valori optime pentru diferite populations.
populaii bacteriene.
In case that for the denitrification
n cazul n care pentru procesul de process is not enough organic substrate for
denitrificare nu este destul substrat organic his ensuring it can be used different organic
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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011

pentru asigurarea lui se pot utiliza diveri


compui organici ca: metanol, etanol, acid
acetic, reziduuri materiale de natur organic.
Sursele cele mai utilizate ca donatori de
electroni sunt materia organic din apa uzat
i metanolul. Alegerea lor se face avnd n
vedere partea economic i disponibilitatea
local.

compounds as: methanol, ethanol, acetic acid,


residues of organic materials. Most used
sources as electron donors are the organic
matter from waste water and methanol. Their
choosing is made having regard the economic
part and the local availability.

7.CONCLUZII

7. CONCLUSIONS

Compusii care pot duce, prin modificarea The compounds which may lead to the
lor, la producerea de nitrati sunt :
nitrates production are:
azotul molecular ce se regaseste in
The molecular nitrogen which is
mod normal in atmosfera (79%) N2 ;
found normally in the atmosphere
combinatii organice naturale cu azot
(79%) N2 ;
aflate in : humus, proteinele animale
Natural organic combinations with
sau vegetale, biomasa microbiana,
nitrogen founded in : mold, animal or
excrementele animale, urina;
vegetable proteins, microbial biomass,
nitritii (NO2-) ;
animal feces, urine;
compusi
ai
amoniului
NH4+,
Nitrites (NO2-)
amoniacul, oxizi ai azotului ;
Ammonium
compounds
NH4+,
compusi pentru fertilizarea solului ammonia, oxides of nitrogen
ingrasaminte chimice organice si
Compounds for soil fertility : organic
anorganice cu continut de azot :
and inorganic fertilizers containung
ingrminte cu azot sub form nitric
nitrogen: fertilizers with nitrogen as
(azotatul de calciu, azotatul de sodiu,
nitric( calcium nitrate, sodium nitrate,
azotatul de potasiu) , ingrminte cu
potassium nitrate), fertilizers with
azot sub form amoniacal (amoniac
nitrogen as ammonia( anhydrous
anhidru, ape amoniacale, sulfat de
ammonia,
ammoniacal
waters,
amoniu etc), ingrminte cu azot
ammonium sulphate) fertilizers with
nitric i amoniacal (Azotatul de
nitrate
and
ammonia
amoniu, nitrocalcarul), ngrminte
nitrogen(ammonium
nitrate,
cu azot amidic (Urea), ingrminte
nitrocalcar)
amide
nitrogen
cu azot sub form organic
fertilizers(urea), nitrogen fertilizers
(ngrmintele cunoscute sub numele
with organic form(known as organic
de organominerale care conin azot
minerals containing organic nitrogen,
organic i se obin din lignit i uree),
derived from coal and urea) fertilizers
ingrminte cu azot organic i
with organic and mineral nitrogen,
mineral (compuii de adiie ai ureei
organic compounds such as laystall,
ureosulfatul de amoniu, azotatul de
compost, garden soil, green fertilizers,
uree, ureoazotatul de calciu), compusi
etc.
organici precum gunoiul de grajd,
Industrial compounds released into
compost, mranita, ingrasaminte verzi
the atmosphere : nitrogen oxides,
etc ;
ammonia, special pollutants organic
compusi eliminati in atmosfera din
and inorganic, including with nitrogen
industrie : oxizi de azot, amoniac,
molecule
poluanti speciali - anorganici si
Removed compounds from soil or
organici, inclusiv cu azot in
water from industry: nitrogenous
molecula ;
substances(pharmaceuticals,
compusi eliminati pe sol sau in apa
colorants,etc) ammonia.
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Analele Universitii Constantin Brncui din Trgu Jiu, Seria Inginerie, Nr. 2/2011

din industrie : substante azotate BIBLIOGRAPHY


(industria farmaceutica, a colorantilor, [1] Bucur, Aurelia -Elements of water
etc.), amoniac .
chemistry, Publishing House *H*G*A*,
1999

BIBLIOGRAFIE

[1] Bucur, Aurelia - Elemente de chimia apei [2] Negulescu, M. Urban wastewaters
Editura *H*G*A*,1999
treatment, , Technical Publishing House
Bucuresti, 1978
[2] Negulescu, M. - Epurarea apelor uzate
oreneti. Editura Tehnic, Bucuresti, 1978
[3] Robescu, D; - Processes and mechanical
[3] Robescu, D; - Procedee i echipamente equipemnts for the water treatment and
mecanice pentru tratarea i Stoianovici purification, Publishing House Bucureti
1982
epurarea apei, Editura Bucureti 1982
[4] Robescu, Dverestoy,
simularea proceselor de
Tehnic, Bucuresti 2004

- Modelarea i [4] Robescu, DVerestoy, - The modellind


epurare, Editura and the treatment simulation, Technical
Publishing House , Bucuresti 2000.

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