STANDARDNI POLUTANTI U VODAMA

Water is life and thus the quality of water is an essential measure of the quality of life or rather the existence of life. Consequently water quality management is (or should be) one of the most important activities of mankind, so as to protect and save human life and the life of other living things, which latter is a precondition of human life as well. Voda je ivot, a time je i kvaliteta vode kljucna mjera kvalitete ivota ili bolje kazano postojanja ivota. Upravljanje kvalitetom vode je (ili bi trebala biti) jedan od najvanijih aktivnosti ovjeanstva u cilju zatite i spasavanja ljudskog ivota i ivota drugih ivih bida, koja su preduvjet za opstojanost ljudskog ivota. The management of water quality, or the protection of the aquatic ecosystem in a broader sense, means the control of pollution. Water pollution originates from point and non-point (diffuse) sources and it is always due to human action (the author strongly believes that no such thing as natural pollution exists, as sometimes advocated by other people). Upravljanje kvalitetom vode, ili zatita vodenih ekosistema u irem smislu, znai kontrolu zagaenja. Zagaenje vode potjee iz takastog i netakastog (difuznog) izvora i uzrok je uvijek zbog ljudskog djelovanja . The control of water pollution, the protection of aquatic systems, is thus the control of human activities that result in pollution. Kontrola oneidenja voda i zatita vodenih sistema su stoga kontrola ljudskih aktivnosti koje rezultiraju oneidenjem voda.

A crucial element in the series of complex activities of planning and implementing water pollution control actions is the quantitative determination and description of the cause-andeflect relationships between human activities and the state (the response) of the aquatic system, its quantity and quality. These activities together can be termed the modelling of aquatic systems (hydrological, hydraulic and water quality modelling). These activities are aimed at calculating the joint effect (the impact) of natural and anthropogenic processes on the state of water systems. Kljuni element u seriji sloenih aktivnosti planiranja i provedbi kontrole zagaenja vode je kvantitativno odreivanje i opis uzrocno-posljedicnih odnosa izmeu ljudskih aktivnosti i drave vodenog sistema . Ove aktivnosti zajedno moemo nazvati modeliranje vodenih sistema (hidroloko, hidrauliko i modeliranje kvaliteta vode). Ove aktivnosti su usmjerene na izraunavanje zajednikih uinak a(utjecaja) prirodnih i antropogenih procesa na stanje vodovodnih sistema. The subject of this teaching aid is to introduce the basics of water quality modelling to the user. Although the qualitative and quantitative modelling of water systems (rivers, lakes and reservoirs) should be done simultaneously we will have to separate them for the purpose of this programme, always assuming that the quantitative state (the hydrological and hydraulic parameters) of the water system is known and sufficiently well described. With this we can focus on the quantitative, mathematical, description of processes that affect water quality. Cilj ovog seminarskog rada je upoznati osnove modeliranja kvaliteta vode sa eventualnim korisnicima. Iako bi kvalitativno i kvantitativno modeliranje vodovodnih sistema (rijeke, jezera i akumulacije) trebalo biti sprovedeno istodobno, u cilju jednostavnijeg boljeg razumijevanja morat cemo ih odvojiti jedno od drugog u seminarskom radu, uz pretpostavku da je kvantitativno stanje (hidroloki i hidrauliki parametri) vodenog sistema dobro opisano. Na taj nacin se moemo usredotoiti na kvantitativni, matematiki, opis procesa koji utjee na kvalitetu vode.

Consequently in the following sections of this programme all ,hydraulic and hydrological river parameters (e.g rate of flow, flow velocity, stream depth and width, etc) will be considered as given input data. Thus we will start with the introduction of the basic mass transport and transformation processes, relying on continuity and conservation of mass considerations. U nastavku ce se svi hidraulini i hidroloki paramatri rijeke (npr. stopa protoka, brzina protoka, dubina i irina protoka, itd) smatrati ulaznim podacima. Polazna osnova modeliranja ce biti transport mase i procesi transformacije, oslanjajudi se na zakon kontinuitet i ouvanja mase. Let us consider an elementary water body, a cube of dx, dy and dz dimensions as shown in Figure 1. The quality of water within this elementary water body depends on the mass of a polluting substance present there. Water quality models then should describe the change of the mass of a polluting substance within this water body. The change of the mass of this substance is calculated as the difference between mass-flows (mass fluxes) entering and leaving this water body, considering also the effects of internal sources and sinks of the substance, if any. The mechanism of mass transfer into and out of this water body includes the following processes: Posmatrajmo elementarni dio vodenog tijela, kocku elementarnih dimenzija dx, dy i dz kao to je prikazano na slici 1.Kvaliteta vode unutar ovog elementarnog dijela vode ovisi o masi oneidujudih tvari koje su prisutne. Modeli kvaliteta vode bi zatim trebali opisati promjenu mase zagaujucih tvari unutar ovog elementarnog vodenog tijela. Promjena mase ove tvari se racuna kao razlika izmeu masenih flukseva (masovni tokova) koji ulaze i napustaju tijelo, pri cemu se uzimaju u obzir i uinci unutarnjih izvora i ponora materije, ako istih ima .Mehanizam prenosa mase iz ovog vodnog tijela ukljuuje sljededi procesa:

Mass transported by the flow, by the vX, vZ, and v, components of the flow velocity vector. This process is termed the advective mass transfer. The transfer of mass, that is the mass flux (in mass per time, M T-l, dimension) can be calculated in the direction x as C*v,*dy*dz, where C is the concentration of the substance in the water (in mass per volume dimension, M L), see also Equation 1.1. The other means of mass transfer is termed the dispersion or dispersive transport. Here one has to explain this term because there is usually considerable confusion with the terms diffusion and dispersion; -in short: dispersion is a term used for the combined effect of molecular diffusion and turbulent diffusion, and both of these latter processes is caused by pulsating motion, that is Prenos mase protokom preko VX, VZ, i V, komponentih strujnog vektora. Ovaj proces je nazvan advektivnim masenim prenosom. Prenos mase, odnosno fluks mase (jedinica mase u jedinici vremena, M TL, dimenzija) se moe izraunati u x-smjeru kao C * v, * dy * dz, gdje je C koncentracija tvari u vodi (jedinica mase po jedinici volumena ML "). Drugi aspekti prenosa mase nazivaju se disperzija ili disperzivni transport. Ovdje treba detaljnije objasniti taj pojam jer obino dolazi do mijesanja pojma difuzije i disperzije;-u k ratko: disperzija je termin koji se koristi za kombinovani uinak molekularne difuzije i turbulentne difuzije , a oba ova spomenuta procesa su uzrokovana pulsirajucim kretanjem , odnosno

- Brownovom toplotno induced motion of the molecule (molecular diffusion), and -- by the pulsation of the flow velocity around its mean value, caused by turbulence (called the turbulent diffusion). The dispersive mass transfer (E,, E,, E,) has the dimension of mass per time per area (M T- Le2) and it is usually expressed by the law of Fick which states that the transport of the

substance in a space direction is proportional to the gradient of the concentration of this substance in that direction the proportionality factor being the coefficient of dispersion, as shown in equation 1.1. -"Brownim" toplinsko induciranim kretanjem molekula (molekularna difuzija), i - Po pulzaciji brzine strujanja oko svoje srednje vrijednosti, uzrokovane turbulencijom (tzv. turbulentna difuzija). Disperzivni prenos mase (E, E, E,) ima dimenziju mase po jedinici vremenu po podruju (M T-' Le2) i obino se izraava po Fick-ovom zakonu po kojem je prenos materije u prostornom smjeru proporcionalan gradijentu koncentracije materije u tom smjeru. Faktor proporcionalnosti se zove koeficijent disperzije, kao prikazano u sljedecoj jednacini

Mass transport terms for deriving the basic model These equations describe the dispersive and advective transport of a polluting substance from the x direction into an elementary water body. The first term is actually the law of Fick which states that the diffusive (dispersive) transport of the substance in a space direction is proportional to the gradient of the concentration of this substance in that direction the proportionality factor being the coefficient of dispersion. The user finds more information on dispersion in the general part of this basic theory chapter and on the programme part on dispersion river models. The second term is the advective transport term, which states that the specific (per unit area) transfer of mass to a spatial direction is the product of the concentration of a substance and the velocity of flow in that spatial direction. These are the terms used in writing the overall mass balance (that is Eq. 1.2) of an elementary water body as shown in Figure 1.

Uslovi za izvoenje osnovnog modela prenosa mase Ove jednacine opisuju disperzivni i advektivni prenos zagaujuce tvare iz x-smjera u elementarno vodeno tijelo . Prvi izraz predstavlja zapravo prvi Fick-ov zakon u kojem se navodi da je difuzni (disperzivi) prenos materije u prostornom smjeru proporcionalan gradijentu koncentracije ove materije u istom smjeru Faktor proporcionalnosti se koeficijent disperzije. Drugi clan predstavlja advektivni prenos, u kojem se navodi da je specifini (po jedinici povrine) prenos mase u prostornom smjeru proizvod koncentracija tvari i brzine protoka u tom prostornom smjeru.

Legend c - is the concentration, the mass of the quality constituent in a unit volume of water (mass per volume, M Le3); LE,,E, - are the dispersive mass fluxes in the spatial directions x, y, and z (in M L-2 T-l dimension), with the assumption that the law of Fick holds for the joint effect of molecular diffusion and turbulent diffusion, that is for dispersion; v,,vy,vz - are the components of the flow velocity in spatial directions x, y , and z, (length per time, L T-l); dx,dy,dz - are the side lengths of an elementary cube, an elementary water body. egenda c - je koncentracija, masa zagadjujuce tvari po jedinici volumena vode (masa po volumenu, M Le3); LE,, E, - su disperzivni maseni fluksevi u prostornim smjerovima x, y, z (u M L-2 Tl dimenzija), sa pretpostavkom da Fick-ov zakon zajednicki obuhvata molekularnu difuziju i turbulentnu difuziju, odnosno za disperziju;

v,, VY, vz. - su komponente strujanja u prostornim smjerovima x, y i z, (duina po vremenu, L T-l); dx, dy, dz - su bone duzine elementarne kocke, elementarnog tijela vode. Derivation of simple practical models from the basic model equation The most simple water quality model (1) The basic three dimensional water quality model is seldom used in its original complex way (Eq. 1.3), mostly because three dimensional problems occur rarely. For example river problems can be frequently reduced to one-dimensional (linear) or two dimensional (longitudinal-transversal) problems, as it will be demonstrated in the programme. Another reason of using simplified models is that transversal or vertical velocity measurement data are seldom available. The internal source-sink terms, that were only denoted in Eq. 1.3 should be specified for each problem explicitly and they vary with the components considered. Here it will be briefly demonstrated how can one derive the most simple (river) models version of Eq. 1.3, which can be used in the practice. In order to arrive to the possible most simple water quality model we have to make first series of assumptions and approximations: Derivacija jednostavnih praktinih modela iz osnovnog modela jednacine Najjednostavniji model kvaliteta vode (1) Osnovni trodimenzionalni model kvaliteta vode se rijetko koristi u svom izvornom kompleksnom obliku(Eq. 1,3), uglavnom zato sto se trodimenzionalni problemi javljaju rijetko. Na primjer problemi rijeka se esto mogu svesti na jednodimenzionalne (linearne) ili dvodimenzionalne (uzduno-poprene) probleme . Drugi Razlog koritenja pojednostavljenih modela je sto su mjerni podaci poprene ili vertikalne brzine rijetko dostupni. Pojmovi unutrasnjeg izvora-ponora, koji su naznaeni u jed. 1,3 treba navesti za svaki problem eksplicitno i oni se razlikuju od prijasnjih komponenti.

Ovdje de se ukratko pokazati kako se moze derivirati najednostavniji (rijecni) oblik modela jednacine. 1.3, koji se moe koristiti u praksi. U cilju pronalazenja najednostavnijeg modela kvaliteta vode mora se napraviti niz pretpostavkih i aproksimacija: a, Neglect, for the time being, all terms accounting for dispersion. With this we assume that the system is fully mixed, which means that any external material input (load) to the river will be instantaneously and fully mixed with the water. This is a very rough approximation and its consequences will be discussed in a subsequent sections dealing with dispersion and mixing problems. However, this approximation holds with long linear systems, e.g in the case of smaller rivers with continuous steady input loads (waste water discharges). b, Considering a river and a sewage discharge of steady state conditions (with flow not varying in time) the initial concentration Co downstream of an effluent outfall can be described by the general dilution equation (see Equation 1.4). a)za nemarivanje svih uslova koji se ticu disperzije. Uz to moemo pretpostaviti da se sistem u potpunosti mijea, to znai da ce se bilo koji vanjski materijalni ulaz (opteredenje) u rijeku odmah i potpuno mijea sa vodom. Ova pretpostavka vai za sve duge linearne sisteme, npr. manje rijeke sa kontinuiranim ulazom opteredenja (otpadne vode). B Posmatrajuci rijeku i kanalizaciju otpadnih voda pri stacionarnim uslovima (sa tokom koji se ne mijenja u vremenu) poetna koncentracije Co nekog rukavca rijeke koji tece nizvodno moe biti opisana opdom jednacinom razrjedjivanja (vidi jednacinu 1,4).

The general dilution equation Considering a river and an effluent discharge of steady state conditions (with flows and concentrations not varying in time) and assuming instantaneous full cross-sectional mixing of the sewage water with the river water the initial concentration Co downstream of an effluent outfall can be calculated by the dilution equation (Eq. 1.4), which stems from the balance equation of in- and outflowing fluxes written for the section of the discharge point (e.g. background river mass flux plus pollutant discharge mass flux equals the combined mass flow downstream of the point of discharge). This equation is used very frequently in simple analytical water quality models for calculating the initial concentration of pollutants. OPCA JEDNACINA RAZRJEDJIVANJA Posmatrajuci rijeku i odvod otpadne vode pri stacionarnim uvjetima I pod pretpostavkom instantnog mijeanja otpadne vode po punom prjesjeku sa vodom rijeke poetna koncentracije Co odvoda otpadnih voda koji tece nizvodno se mogu izraunati preko jednacine za razrjedivanje (Eq. 1.4), koja proizlazi iz jednacine ravnotee za flukseve dotoka I odvoda napisanog za podrucje tacke ispustanja (npr. osnovni maseni fluks rijeke plus maseni fluks zagadjujucih tvari koji se ispustaju u rijeku su jednaki kombiniranom maseni protoku nizvodno od toke isputanja). Ova jednacina se koristi vrlo esto u jednostavnim analitikim modelima kvaliteta vode za izraunavanje poetne koncentracije oneidujudih tvari. Legend CtJ - background concentration of the polluting substance in concern in the river, (MLe3); cs - concentration of the pollutant in the waste water, (MLe3); Q- discharge (rate of flow) of the river upstream of the effluent outfall, (L3 T-l); qthe effluent discharge, (L3 T-l); The most simple water quality model (2)

Averaging flow and concentration over the cross section Equation 1.3 simplifies into Equation 1.5 where v is the average flow velocity along the stream. Introducing the time of travel t = x/v and assuming first order reaction kinetics for a single decay or decomposition process, as the only internal process (sink) one obtains the possible most simple river water quality model in the form of Equation 1.6 This equation (the principle of first order reaction kinetics) states that the decay/decomposition of a pollutant is proportional to the concentration of the pollutant and the factor of proportionality is K, the decay rate coefficient (T-l). Solving Eq. 1.6 for the initial conditions defined above (C = C, at x=x,, that is t = tJ the simple exponential decay equation (Equation 1.7) is obtained, which is at the same time the most simple water quality model used in the practice. Equation 1.7 will be subsequently referred to also as the Decay Equation. This equation can be used for a number of water quality modelling purposes (such as the decay of BOD, COD, etc, see also at the description of BOD-DO models), and forms an essential part in developing coupled reaction models (see under this heading for more details). legenda CtJ - koncentracija zagaujucih tvari koji postoje rijeci prije mijesanja sa otpadnim vodama, (MLe3); CS - koncentracija zagaujucih tvari u otpadnim vodama, (MLe3); Q- brzina toka rijeke uzvodno od tacke izlijevanja otpadnih voda, (L3 Tl); Q- brzina toka otpadnih voda, (L3 T-l); Najjednostavniji model kvaliteta vode (2) Usrednjavanje protoka koncentracije po poprecnom presjeku jednacina 1.3. se pojednostavljuje u Jednacinu 1.5. gdje je v je prosjena brzina toka rijeke duz cijele duzine. Uvodjenje pojma "vrijeme putovanja" t = x / v, a pod predpostavkom kinetike reakcije prvog reda za process propadanja ili raspadanja , kao jedini unutrasnji procesu (ponor) dobiva se

najjednostavnijiji oblik modela kvaliteta vode rijeke u obliku jednacine 1.6. Ova jednacina (pravilo kinetike reakcije prvog reda) pokazuje da je propadanje / raspadanje tetnih tvari proporcionalno koncentraciji oneidujudih tvari i faktor proporcionalnosti je K, koeficijent brzine propadanja (TL). Rjeavanje jednacine. 1.6 sa poetnim uslovima utvrdjenim iznad (C = C, u x = x,, da je t = TJ ) dobiva se jednostavna jednacina eksponencijalnog raspada (jednacina 1.7.), koji je istovremeno model kvaliteta vode koji senajvise koristi u praksi. Jednacina 1.7 se takodjer naziva Jednacina raspada . Ova jednacina se moe koristiti za razne svrhe modeliranja kvaliteta vode i ini bitnu osnovu za razvoj slozenijih modela kvaliteta vode. Legenda Legend C- is the concentration, the mass of the quality constituent in a unit volume of water (mass per volume, M Lm3); C, - is the initial concentration of the pollutant downstream of a point source of pollution (see also Eq. 1.4) V- is the mean flow velocity of a river reach investigated (L T-l) denotes the internal sources and sinks of the substance, (M Lm3 T-l); K- is the reaction rate coefficient for first order kinetics (T) t- is the time of travel interpreted as t =x/v X- the distance downstream (L) pri cemu je : C-je koncentracija, masa sastojka kvalitete koja se mjeri po jedinici volumena vode (masa po volumenu, M Lm3); C - je poetna koncentracija zagadujucih tvari nizvodno od toke izvora zagaenja (vidi takoer Jed. 1.4)

V-je srednja brzina protoka rijeke (L Tl) i oznaava unutarnje izvore i ponore tvari, (M Lm3 Tl); K-je koeficijent brzine promjene reakcije prvog reda kinetike (T ") t-je vrijeme putovanja te se tumai kao t = X / V X- udaljenost nizvodno (L) Derivation of coupled reaction models Chemical, biological or biochemical processes to which water quality constituents are subjected seldom occur alone but in a coupled way. If we consider such a coupled process situation, still in a generalizable way, assuming that the product of a decomposition/decay process of a water quality component (C,) is another water quality constituent (C,) which latter is subjected to further decay/decomposition then we can derive a simple set of coupled reaction models in the form of Equations 1.8 and 1.9, where K, and K, are the respective reaction rate coefficients of the not yet named water quality processes. With this we have actually derived the still most frequently used basic river model, the oxygen sag curve model (Streeter and Phelps, 1925). Assuming that the parameter C, is the biologically decomposable organic matter content of the water (expressed in Biochemical Oxygen Demand, BOD which is the amount of oxygen utilized by microorganisms from a unit volume of water for the decomposition of organic matter during a selected period of time) and assuming that the other parameter C, is the oxygen deficit compared to saturation level Eq 1.8 and 1.9 are the basic equations of the traditional oxygen sag curve model which states that the oxygen consumed by microorganisms adds to the oxygen deficit, while the process of aeration (or reaeration; the uptake of oxygen across the water surface due to turbulence and molecular diffusion) reduces this deficit.

Derivacija modela kombinovanih reakcija Hemijski, bioloki ili biokemijski procesi kojima su sastojci kvalitete vode podvrgnuti se rijetko odvijaju odvojeni, vec u kombinaciji jedan sa drugim. Ako razmatramo takvu situaciju kombinacije procesa ,jo uvijek po poopdenim pravilima, uz pretpostavku da je proizvod procesa razgradnje / propadanja komponente kvalitete vode (C,) je neki drugi kvalitete vode (C,) koji je kasnije isto podvrgnut daljnjim procesima propadanja / razgradnje onda moemo izvudi jednostavan niz kombinovanih modela reakcije u obliku jednacina 1.8 i 1.9, gdje su K i K, odgovarajudi koeficijenti brzine reakcije procesa kvalitete vode koji jos nisu imenovani. Na ovaj nacin je zapravo izvrseno izvodjenje najede uportrebljenog osnovnog modela rijeke tzv. Model krivulje pada kisika (Streeter i Phelps, 1925). Uz pretpostavku da je parametar C, bioloki rastvorljiva organska tvar iz vode (izraen u Biohemijskoj Potronja Kisika, gdje BPO koliina kisika koju koriste mikroorganizami u jedinici volumena vode za razgradnju organske tvari u toku nekog odredenog vremena) i uz pretpostavku da je drugi parametar C, je nedostatak kisika u odnosu na razinu zasidenosti Jednacine 1.8 i 1.9 su osnovne jednacine tradicionalne modela krivulje pada kisika SAG po kojoj se kisik koji konzumiraju mikroorganizami nadoknaduje nedostatak (manjak) kisika, dok se proces aeracije (ili rearacije; unos kisika po cijeloj povrini vode uslijed turbulencije i molekularne difuzije) smanjuje taj nedostatak. Here the reaction rate coefficients gain specific meaning, that is K1is the rate coefficient of biochemical decomposition of organic matter (T-l) K, - is the reaeration rate coefficient (T-l) t- is the time, that is the time of travel in the river interpreted as t=x/v, where x is the distance downstream of the point of effluent discharge The set of differential equations (Eqs 1.8, and 1.9) can be solved for initial conditions C, =C1,O and C2=C2,0 at x=0; (t=t& (to be calculated with the dilution equation (Eq 1.4) in

a similar way as shown there), obtaining Equations 1.10 and 1.11. Ovdje koeficijenti brzine reakcije dobivaju specifina znaenja, a to je K1-je koeficijent biohemijske razgradnje organske materije (TL) K - je koeficijent brzine promjene rearacije (TL) t-je vrijeme, odnosno vrijeme putovanja tumaeno kao t = X / V, gdje je x je udaljenost nizvodno od toke ispusta otpadnih voda. Skup diferencijalnih jednadbi (1.8 i 1.9) moe se rijeiti za poetne uvjete C, = C1, O i C2 = C2, 0 na x = 0, (t = t & se racuna pomocu jednacina za razrjeivanje (Eq 1.4) ) za dobivanje jednacina 1.10 i 1.11. Cl, c2 - Are concentrations of interacting water quality constituents (the product of the decomposition process of C1 is C,, which latter is also a decaying od decomposing constituent (MLe3) G&20 - are initial concentrations of the above two water quality constituents (see also Eq. 1.4) (ML-3) K,& - are the reaction rate coefficients of the above processes, (T-l) t- is the time of travel interpreted as t =x/v, (T) X- the distance downstream (L) Cl, c2 - su koncentracije interativnih sastojaka kvalitete vode (proizvod procesa dekompozicije C1 je C, pri cemu je potonji takoer proizvod procesa propadanja (MLe3) G & 20 - su poetne koncentracije navedena dva sastojka kvaliteta vode (vidi takoer Jed. 1.4) (ML-3) K & - su koeficijenti brzine reakcije navedenih procesa, (TL) t-je vrijeme putovanja tumaeno kao t = X / V, (T) X-je udaljenost nizvodno (L)

The main process that affect (deplete) the oxygen content of water is the oxygen consumption of microorganisms, living in the water, while they decompose biodegradable organic matter. This means that the presence of biodegradable organic matter is the one that mostly affect the fate of oxygen in the water. There are internal and external.sources of such biodegradable organic matter. Internal sources include organic matter that stem from the decay (death) of living organisms, aquatic plants and animals (also termed detritus, or dead organic matter). Among external sources anthropogenic ones are of major concern and this includes waste water (sewage) discharges and runoff induced non-point source or diffuse loads of organic matter. Glavni proces koji utjee na promjenu kolicine kisika u vodi je potronja kisika od strane mikroorganizama, koji ive u vodi, dok razgrauju biorazgradive organske tvari. To znai da prisutnost biorazgradive organske materije najvie utjee na sadrzaj kisika u vodi. Postoje unutrasnji i vanjski izvori biorazgradive organska materije. Unutrasnji izvori ukljuuju organske tvari koje potjeu od propadanja (smrti) ivih organizama, vodenih biljaka i ivotinja (tzv. mrtva organska materija). Meu vanjskim izvorima od velike vaznosti su antropogeni izvori, a to ukljuuje otpadnu vodu (kanalizacija) i isputanje i otjecanje vode izazvano nestacionarnim izvorima ili nagomilanom difuznom organskom materijom.

In the models biodegradable organic matter is taken into consideration by a parameter termed Biochemical oxygen demand, BOD. BOD is defined as the quantity (mass) of oxygen consumed from a unit volume of water by microorganisms, while they decompose organic matter, during a specified period of time. Thus BOD, is the five day biochemical oxygen demand, that is the amount of oxygen that was used up by micro-organisms in a unit volume of water during five days incubation time in the respective laboratory experiment. Thus the

unit of BOD is mass per volume (e.g g0,/m3, which equals mgO,/l). Pri modeliranju biorazgradive organske materije, uzima se u obzir parametar nazvan "Biohemijska potronja kisika, BPK". BPK se definira kao koliina (masa) kisika potrosena od jedinice volumena vode od strane mikroorganizama, dok razgrauju organsku materiju , tijekom odreenog vremenskog intervala. Tako BPK, je petodnevna biohemijska potrosnja kisika, odnosno ona koliina kisika koja se konzumira od strane mikroorganizama u jedinici volumena vode tijekom pet dana "inkubacije" u odgovarajudem laboratorijskom eksperimentu. Tako je jedinica BPK masa po jedinici volumena (npr. G0, / m3, to iznosi MgO, / l).

Another main process in the oxygen household of streams is the process of reaeration, the uptake of oxygen across the water surface due to the turbulent motion of water and to molecular diffusion. This process reduces the oxygen deficit (D) of water, which is defined as the difference between saturation oxygen content and the actual dissolved oxygen level. Drugi glavni proces kisika toku rijeke je proces rearacije, unos kisika preko povrine vode zbog turbulentnog strujanja vode i molekularne difuzije. Ovaj proces smanjuje "deficit kisika" (D) vode, to je definirano kao razlika izmeu zasidenog sadrzaja kisika i stvarne otopljene kolicine kisike. General description of the traditional oxygen sag curve In this model the decomposition of biodegradable organic matter is expressed as the first order decay of BOD (termed here L) in function of the time The oxygen line, the oxygen sag curve, is written for the oxygen deficit D is such a way that oxygen consumed by microorganisms adds to the oxygen deficit, while the process of aeration (or reaeration; the uptake of oxygen across the water surface due to turbulence and molecular diffusion) reduces this deficit (Equations 2.3 and 2.4). In these equations the initial conditions, e.g L = I+ and D = D, at x =0 (t =t,,) should be

calculated using the Dilution equation (Eq 1.4). The substitution of waste water and river parameter values is relatively straight forward in the case of calculating L, (Eq. 2.5), while for calculating D, first the initial oxygen concentration should be calculated (Eq. 2.6) and the result of this should be subtracted from the saturation DO concentration to achieve D, (Eq. 2.7). The saturation dissolved oxygen concentration of the water is temperature dependent, and the respective values can be obtained either from tables published in the relevant literature or from experimental expressions. In this teaching aid we will use the latter method in the form of Equation 2.8 (Wang et. al, ref. Gromiec, 1983): Opdi opis tradicionalnog modela krivulje pada kisika U ovom modelu raspadanje biorazgradive organske materije se izraava kao raspad prvog stepena BPK u funkciji vremena Linija kisika, odnosna krivulja pada kisika, je nacrtana za deficit D kisika na takav nain da se kisik konzumiran od strane mikroorganizama dodaje deficitu (manjku) kisika, dok proces aeracije (ili rearacije; upijanje kisika preko povrine vode uslijed turbulencije i molekularne difuzija) smanjuje taj deficit (Jednadbe 2,3 i 2,4). U spomenutim jednacinama poetni uvjeti, npr. L = I + i D = D, pri x = 0 (t = t,,) se racunaju pomocu "jednacine razrijedjivanja (dilution equation)" (EQ 1.4).Zamjenom vrijednosti parametara otpadnih voda i rijeke se dobiva vrijednost parametara L, (Eq. 2.5), dok se za izraunavanje D, prvo treba izraunati pocetna kolicina kisika(J. 2,6) i rezultat toga treba oduzeti od koncentracije zasidenja DO kako bi se izracunala vrijednost D, (J. 2.7). Koncentracija zasidenog otopljenog kisika u vodi zavisi od temperature i odgovarajudih vrijednosti mogu se dobiti iz tablica objavljenih u literaturi ili

iz eksperimentalnih izraza. U ovom nastavku demo koristiti metodu pomocu jednacine u obliku2,8 (Wang i sur, ref Gromiec, 1983.). The oxygen sag curve (which the user can see in the Graph window when in the respective menu item) has a critical point where the dissolved oxygen content of water is the lowest, that is when the oxygen deficit is the highest. The time of travel (or the corresponding downstream distance) can be expressed by finding the minimum of the sag curve. It is obtained in the form of Eq. 2.9 for tcrit,, Eq. 2.10 for x Crit, and Eq. 2.11 for Dcrit. Thus the critical dissolved oxygen concentration is obtained as the difference between saturation oxygen concentration and the critical oxygen deficit (Eq. 2.12). For the practical use of the above simple model equations one should find, estimate, the values of the two model parameters K, and K,. There are two basic ways of estimating values of the reaction rate parameters: 1. If one has in-stream measurement data of DO and BOD then one can calibrate the model, by fitting the calculated curves to the measured ones. This can be easily done for BOD (for K,), expressing K, from Eq. 2.2; but the value of reaeration coefficient K, can be found only by trial-error model 2. If you do not have access to measurement data then you can estimate model parameters using formulae and tables published in the relevant literature. Krivulja pada kisika ima kritinu taku na mjestu gdje kolicina otopljenog kisika u void najnia, odnosno kada je kisik deficit najvii. Vrijeme putovanja (ili odgovarajuda udaljenost nizvodno) moe se izraziti pronalaeci minimalnu vrijednost krivulje. To je dobiveno u obliku jed. 2,9 za t krit, J. 2,10 x za krit, I J. 2,11 za Dcrit. Tako se kritina vrijednost koncentracije otopljenog kisika dobiva kao razlika izmeu zasidene koncentracije kisika i kritinog deficita kisika(J. 2,12). Za praktinu primjenu navedenih jednostavnih modela jednacina treba pronadi o procijeniti,

vrijednosti dva parametra modela K i K,. Postoje dva osnovna naina procjene vrijednosti parametara brzine reakcije: 1. Ako netko ima umetnute mjerne podatke DO i BOD u rijeci, onda se moe kalibrirati model, uporedujuci izraunate krivulje izmjerenim. To moe lako biti uinjeno za BPK (za K,), izraavajudi K, u jed. 2,2, ali vrijednost koeficijenta reaeracije K, moe se nadi samo na osnovu gresaka pri pokusaju simulacije modela 2. Ako se nema pristup podacima mjerenja onda se moe procijenit modela pomodu parametara koristeci formule i tablice objavljene u literaturi. The value of the reaeration coefficient K, depends, eventually, on the hydraulic parameters of the stream and a large number of experimental formulae have been presented in the literature along with reviews of these literature equations (Gromiec, 1983, Jolankai 1979, 1992). These expressions deviate from each other, sometimes substantially. For the purpose of this CAL programme we have developed a special equation on the basis of a number of literature published equations that give, the value of K2 in function of flow velocity v and stream depth H, by simply averaging the coefficient values of different authors (when they were relatively close to each other). The thus obtained formula is Equation 2.13. Vrijednost koeficijenta K rearacije zavisi od hidraulikih parametara toka rijeke i od velikog broja eksperimentalnih formula prikazanih u literaturi zajedno sa recenzijama tih literatura (Gromiec, 1983, Jolankai 1979, 1992). Ovi izrazi odstupaju jedan od drugih, ponekad bitno te je stoga razvijena posebna jednacina na temelju velikog broja jednacina objavljenih u literaturi koje daju, vrijednost K2 u funkciji brzine strujanja v i dubine toka H, tako sto se uzimala prosjecna vrijednost koeficijenata razliitih autora Tako dobivena formula je jednacina 2.13.

Both the reaeration coefficient K, and especially the decomposition rate coefficient K, depend on the ambient (water) temperature. For this latter the most widely accepted formula is Eq. 2.14 One should note that reported literature values of K, and K2 vary over wide ranges of which, for this teaching aid programme, we will consider the following domain: K, - 0.1 - 1.7 day- Kz - 0.2 - 1.2 day- If we discretize this domain at 0.1 day- steps we can obtain the Table 2 for the variation of the f =K,/K, ratio. The table is not shown but is included in the programme. From this table one should not adopt values of f lower than 0.5 or higher than 5 .O Oba koeficijenta rearacije, a posebno koeficijent brzine raspadanj K, ovisi o sobnoj (voda) temperaturi. Obicno se za raspon vrijednosti koeficijenata koriste sljededi domeni: K - 0,1 do 1,7 dana-' K - 0,2 do 1,2 dana-' The BOD decay model The BOD decay model describes the decomposition of biodegradable organic matter is expressed as the first order decay of BOD (termed here L) in function of the time (which is the time of travel along the stream t =x/v). In Equation 2.2 the initial conditions, e. g L = L, at x = 0 (t = t& should be calculated using the Dilution equation (Equation 1.4 and 2.5). For more details see the Basic theory, the General description of BOD-DO river models and the General description of the traditional oxygen sag curve. t

Legend L- BOD in the water (M, usually g0,/m3) Loinitial BOD in the stream (below waste water discharge), see also Eq. 2.5 (M, usually g Q/m31 K*is the rate coefficient of biochemical decomposition of organic matter (T-l, usually day-) t- is the time, that is the time of travel in the river interpreted as t =x/v, where x is the distance downstream of the point of effluent discharge (T, usually days) Model propadanja BPK Model propadanja BPK koji opisuje razgradnju biorazgradivog organske materije je izraena kao propadanje "prvog reda" BPK u funkciji vremena (koje je vrijeme putovanja uz tok rijeke t = x / v). U jednacini 2,2 poetni uvjeti, e. g L = L, u x = 0 (t = t & treba izraunati pomodu " jednacine razrijedjivanja" (jednacine 1.4 i 2.5). t legenda L-BPK u vodi (M, obino G0, / m3) LoPoetne vrijednosti BPK u potoku, vidi takoer Jed. 2,5 (M, obino g Q/m31 K*je brzina promjene koeficijenta biokemijske razgradnje organske materije (Tl, obino dan-')

t-je vrijeme, odnosno vrijeme putovanja uz tok rijeke, te se tumai kao t = X / V, gdje je x udaljenost nizvodno od toke ispusta (T, obino dana) The dissolved oxygen model The traditional dissolved oxygen model describes the fate, the sag, of the dissolved oxygen in the river as influenced by the decay of biodegradable organic matter and the reaeration process (across the water surface). In Equation 2.4 the initial conditions, e.g D=D,, L=L, at x=0 (t=tJ should be calculated using the Dilution equation (Equation 1.4, 2.5 and 2.6). For more details see the Basic theory, the General description of BOD-DO river models and the General description of the traditional oxygen sag curve.

Legend D- is the oxygen deficit of water (g0,/m3), see also equations 2.7 and 2.8. L- BOD in the water (g0,/m3) PJis the initial oxygen deficit in the water (downstream of effluent outfall) (g0,/m3), see also equations 2.6 and 2.7 Lois the initial BOD concentration in the water (g0,/m3), (downstream of effluent discharge), see also Eq 2.5 Kis the rate coefficient of biochemical decomposition of organic matter (T-l, usually day-) K, - is the reaeration rate coefficient (T-l, usually day-) t- is the time, that is the time of travel in the river interpreted as t=x/v, where x is the

distance downstream of the point of effluent discharge; and v - is the mean flow velocity of the river reach in concern. (T) Model otopljenog kisika Tradicionalni model otopljenog kisika opisuje pad otopljenog kisika u rijeci kao posljedicu utjecaja propadanja biorazgradive organske materije i procesa reaeracije. U jednacini 2,4 poetne uvjete,. D = D, L = L, u x = 0 (t = TJ treba izraunati pomodu " jedacine za razrjeivanje " (jednacina 1.4, 2.5 i 2.6). legenda D- deficit kisika u vodi (G0, / m3), vidi takoer jednacine 2,7 i 2,8. L-BPK u vodi (G0, / m3) PJje poetni deficit kisika u vodi (nizvodno od ispusta otpadnih voda) (G0, / m3), vidi takoer jednadbe 2,6 i 2,7 Loje poetna BPK koncentracija u vodi (G0, / m3), (nizvodno od tacke ispustanja otpadne vode ), vidi takoer Eq 2,5 Kje brzina promjene koeficijent biohemijske razgradnje organske materije (Tl, obino dan-') K - je brzina promjene koeficijenta rearacije (Tl, obino dan-') t-je vrijeme, odnosno vrijeme putovanja uz tok rijeke, te se tumai kao t = X / V, gdje je x udaljenost nizvodno od toke ispusta (T, obino dana)

TThe dilution equations for BOD and DO Considering a river and an effluent discharge of steady state conditions (with flows and concentrations not varying in time) and assuming instantaneous full cross-sectional mixing of the sewage water with the river water the initial concentration C, downstream of an effluent outfall can be calculated by the dilution equation (Eq. 1.4), which stems from the balance equation of in- and outflowing fluxes written for the section of the discharge point (e.g. back-ground river mass flux plus pollutant discharge mass flux equals the combined mass flow downstream of the point of discharge). This equation is used very frequently in simple analytical water quality models for calculating the initial concentration of pollutants. This two dilution equations compute the initial concentration of BOD and DO in the river downstream of a point source sewage discharge, with the assumption of instantaneous mixing. For more details see the Basic theory, the General description of BOD-DO river models and the General description of the traditional oxygen sag curve. Legend L, - is the initial concentration of BOD in the river, downstream of the effluent discharge point (MLm3, e.g. mgO,/l); Lbis the background concentration of BOD in the river, (ML3, e.g. mgO,/l); L, - is the BOD content of the waste water, (MLm3, e.g. mgO,/l); DO0 - is the initial concentration of dissolved oxygen in the river, downstream of the effluent discharge point (MLm3, e.g. mgO,/l); DO, - is the background concentration of dissolved oxygen in the river, (MLe3, e.g. mgO,/l); DO, - is the dissolved oxygen content of the waste water, (MLe3, e.g. mgO,/l); Qb - discharge (rate of flow) of the river upstream of the effluent outfall, (L3 T-l, e.g. m3/s);

9s the effluent discharge, (L3 T-l, e.g. m3/s); Jednacine razrjeivanje za BPK i DO Posmatrajuci rijeku i odlijevanje vode u stacionarnim uvjetima (tok i koncentracija ne variraju u vremenu), i pod pretpostavkom da se otpadna voda trenutna puna presjeka mijea sa vodom rijeke preko citavog presjeka spoetna koncentracija C, nizvodno od ispusta otpadnih voda se moze izraunati jednacine za razrjedjivanje (J. 1.4), koja proizlazi iz jednacine ravnotee za ulijevanje i izlijevanje masenih tokova rijeke pisane za dionicu ispusta (npr. maseni tok nadolazece rijeke plus maseni tok otpadnih voda jednak je kombiniranom masenom toku nizvodno od toke isputanja otpadnih voda). Ova jednacina se koristi vrlo esto u jednostavnim analitikim obradama modela kvaliteta voda za izraunavanje poetne koncentracije oneidujudih tvari. Ove dvije jednacine za razrjeivanje racunaju poetnu koncentraciju BPK i DO u rijeci nizvodno od kanalizacijske take izvora isputanja, s pretpostavkom trenutnog mijeanja. Legenda L, - je poetna koncentracija BPK u rijeci, nizvodno od tacke ispusta (MLm3, npr. MgO, / l); Lbje koncentracija BPK nadolazece rijeke, (ML3, npr. MgO, / l); L, - je BPK sadraj otpadnih voda, (MLm3, npr. MgO, / l); DO0 - je poetna koncentracija otopljenog kisika u rijeci, nizvodno od tacke isputanja otpadnih voda(MLm3, npr. MgO, / l); DO, - je koncentracija otopljenog kisika nadolazece rijeke, (MLe3, npr. MgO, / l); DO, - je koliina otopljenog kisika otpadnih voda, (MLe3, npr. MgO, / l); QB - protok rijeke uzvodno od ispusta otpadnih voda, (L3 Tl, npr. m3 / s);/

qs- kolicina ispusta