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Analele Universit ii Constantin Brncu i 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.eng. Chimerel Mircea-Eleodor, Drd.eng. University of Petrosani, Centre of Doctorate and Continous Education,
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

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

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.

2.SURSE DE AZOT

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 Universit ii Constantin Brncu i 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

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

3. SURSE DE AZOT PRODUSE DE 3. NITROGEN SOURCES PRODUCED BY THE HUMAN OAMENI Sursele de azot provenite din activitatea PEOPLE
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


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.

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.

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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.

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.

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

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 199

Analele Universit ii Constantin Brncu i 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 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):
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

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

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 201

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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

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. 202

7. CONCLUSIONS

Analele Universit ii Constantin Brncu i din Trgu Jiu, Seria Inginerie, Nr. 2/2011

BIBLIOGRAFIE

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

[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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