SOIL POLLUTION WITH PETROLEUM HYDROCARBONS - BIOREMEDIATION: POTENTIALITY AND PRACTICE

Sažetak Sve više saznanja o ireverzibilnim i dugotrajnim utjecajima onečišćenja na pogoršanje kvalitete tla, sedimenata i zaliha pitke vode ima sve veći utjecaj na istraživanja i politiku upravljanja okolišem zadnjih dvadeset godina. Unos antropogenih, otrovnih i štetnih kemijskih spojeva u tlo ima ozbiljne posljedice na različita područja ljudskih aktivnosti, od poljoprivrede, opskrbe pitkom vodom, planiranja građenja do gospodarenja prirodnim resursima. Tlo je jednako ugrožen ekosustav kao zrak i voda pa su neke razvijene zemlje već pred dvadeset godina donijele zakone o očuvanju kvalitete tla a time i podzemnih voda. Uzroci onečišćenja tla i podzemnih voda jesu: nepropisno zakopan otpad, loše riješeni tokovi otpadnih voda, nepropisno korištenje kemikalija u poljoprivredi, slučajni izljevi izazvani nepažnjom, pretjerano crpljenje podzemnih voda, odlaganje sanitarnog otpada na zemlju, odlaganje otpadnih muljeva industrije, propuštanje iz industrijskih bazena za otpadne vode, propuštanje iz spremnika goriva na skladišnim prostorima, itd. Ugljikovodici su čest uzrok onečišćenja okoliša pa na naftnoj i petrokemijskoj industriji leži velika odgovornost za rješavanje problema onečišćenja okoliša. Industrije razvijenih zemalja su već šezdesetih godina prošlog stoljeća pokrenule istraživanja u suradnji sa znanstvenim institucijama u cilju rješavanja problema onečišćenja okoliša naftnim ugljikovodicima. Cilj je rada prikazati kako se biološke procese, kao temelj brojnih korisnih tehnologija, može upotrijebiti kao gospodarski opravdane i učinkovite postupke čišćenja tla i podzemnih voda u slučajevima njihova onečišćenja opasnim tvarima, napose naftnim ugljikovodicimaAbstract Increasing realizations on irreversible and long-term impacts of pollution on impairing soil and sediments quality and potable water reserves has had an increasing impact on research and policy of environmental management over the past twenty years. The introduction of anthropogenic, harmful and noxious chemical compounds into soil has had a serious impact on various areas of human activities, from agriculture, potable water supply, urban planning, to resource management. Soil is an equally endangered ecosystem as air and water, which is why some developed countries have already twenty years ago passed laws on the preservation of the quality of soil, and hence also of underground waters. Pollution causes of soil and underground waters are: improperly buried waste, bad solutions for wastewater flows, improper use of chemicals in agriculture, accidental spills caused by neglect, overuse of underground waters, disposal of sanitary waste into the ground, disposal of industrial waste sludge, leakage from industrial wastewater basins, leakage from fuel reservoirs in storage areas, etc. Hydrocarbons are a frequent cause of environmental pollution, which is why the oil and petrochemical industries have a great responsibility for resolving environmental protection problems. The industry of developed countries has already in the 60s started research in co-operation with scientific institutions for the purpose of resolving the issue of environmental pollution by oil hydrocarbons. The aim of the paper is to present how biological processes as base for many useful technologies could be used as economically justified and efficacious procedure for soil and groundwater decontamination in case of hazardous pollution, particularly with petroleum hydrocarbons

ECOTOXIC COMPOUND AS BIOLOGICAL PARAMETER FOR ESTIMATION QUALITY OF THE REFINERY WASTEWATER

Sažetak Kompletnim tretmanom obrade procesnih otpadnih voda i provedbom sveobuhvatnog programa ispitivanja kakvoće izlaznog efluenta ostvaruje se u Rafineriji nafte Rijeka (RNR) vrlo učinkovita zaštita recipijenta i očuvanje prirodne biološke ravnoteže morskog ekosustava. Temeljem zakonske regulative potrebno je provoditi ispitivanje ekotoksičnosti izlaznih otpadnih voda prije ispuštanja u more radi ocjene utjecaja na ekosustav mora. U program praćenja kakvoće rafinerijskog efluenta, te podzemnih voda, ekotoksikološka ispitivanja uključena su od 1997. godine, te se raspolaže petogodišnjim rezultatima što sa stajališta znanstveno stručne obrade podataka predstavlja potrebni minimum praćenja za definiranje značajnosti utjecaja bioloških čimbenika. Za određivanje toksičnosti otpadnih i podzemnih voda korištena je njemačka standardna metoda po DIN-u (DIN 38 412-L-34). To je bioluminiscentna metoda koja spada među testove kratkog trajanja, a kao test organizmi korištene su fluoroscentne bakterije. Metoda je prilagođena mjerenju toksičnosti industrijskih otpadnih voda koje u pravilu sadrže povišene koncentracije soli. Ispitivanja ekotoksičnosti provode se već šestu godinu i sakupljeni podaci predstavljaju relevantne rezultate na osnovi kojih se mogu definirati zaključci o mogućem djelovanju intoksikacije prisutnih organskih ili anorganskih otrova, bilo s lokalnim ili resorptivnim učincima na test organizam. Osim toga, pri ocjeni stanja mora u koji se ispušta pročišćena rafinerijska otpadna voda, treba voditi računa o pratećim interakcijskim procesima, odnosno pokušati utvrditi opseg uzajamnog djelovanja svih kemijsko-fizikalnih i bioloških pratećih parametara na test organizme, uz prepoznavanje korelacijskih odnosa. Jedino na taj način mogu se razgraničiti i vrednovati biodepresivni ili biostimulativni učinci ispitivane otpadne vode na ekosustav recipijenta u koji se ispuštaju. Cilj rada i obrade rezultata ekotoksičnosti efluenta je utvrđivanje vrste i opsega mogućih utjecaja RNR na onečišćenja mora kao recipijenta, sa svrhom poboljšanja kakvoće izlazne vode i bolje ekološke zaštite morskih biocenoza.Abstract With the complete treatment of processing the wastewater and application of overall quality effluent research, the Petroleum Refinery Rijeka is practicing a very effective recipient protection and sustaining natural biological sea ecosystem balance. According to legislative regulations, the research of ecotoxicity of the discharged wastewater is needed before releasing it in the sea because of the evaluation of its affliction on the sea ecosystem. Ecotoxical research is included in the programme of monitoring quality of the refinery effluent and ground waters since 1997. Consequently, the 5 year results are available, which is, according to scientific data processing minimum, obligatory for defining the significance of biological parameter affliction. Standard German Method DIN is used in order to determine toxicity of the discharge and ground waters. The bio-illuminating method is one among the short term tests, where fluorescent bacteria is used as the test organism. This method is adjusted to measurement of toxicity of the industrial discharge waters that contain high levels of salinity in most cases. Information gathered in toxicity research for 6th year now, are relevant foundation to draw conclusions on possible intoxication of organic and inorganic poisons, both local and resorptive effects on test organisms. Furthermore, when evaluating state of the sea receiving recycled refinery wastewater, the side-effect interaction processes should be taken into the account, i.e. an effort should be taken to determine the measure of interactive influence of all chemical, physical and biological parameters on test organisms, with the recognition of collating relations. This is a unique way to separate and evaluate bio-depressive and bio-stimulative effects of the examined wastewater on recipient ecosystem. The aim of the paper and data processing on ecotoxicity of the effluent is to determine the sort and the amount of Petroleum Refinery Rijeka influence on the sea pollution with a purpose of improving quality of the discharged wastewater and ecological protection of biocenosis

MICROBIAL DEGRADATION OF EMULSIONS FOR COOLING AND LUBRICATION AT METALWORKING

Sažetak Kvarenje materijala je problem koji zaokuplja pozornost stručnjaka oduvijek, jer, prije svega, dovodi do velikih ekonomskih gubitaka. Zato su uzroci kvarenja različitih materijala predmet istraživanja već dugi niz godina. Organizirane grupe istraživača većinom u kemijskoj industriji podržane vladinim organizacijama bave se analizama i istraživanjima u tome području. Najveću ulogu u kvarenju ima biološko kvarenje koje je po definiciji svaka neželjena promjena svojstava materijala uzrokovana aktivnostima živih organizama. Biorazgradnja pod nazivom kvarenje, nepoželjan je proces kada je u pitanju proizvodnja i čuvanje materijala, ali je vrlo poželjan proces kada taj materijal postaje otpad, a u pitanju su obično često iste vrste mikroorganizama. Emulzije za hlađenje i podmazivanje pri obradbi metala s velikim udjelom vode do 98% upravo su zato vrlo podložne rastu mikroorganizama. Uljna faza je dobra hranjiva podloga za mikroorganizme kao izvor ugljika. Zbog raspršenih kapljica u vodi dodirna međufazna površina ulje/voda vrlo je velika pa je i površina za rast mikroorganizama dovoljna budući da je voda neophodni medij za razvoj. Pod utjecajem metabolizma mikroorganizama proizvod se mijenja kemijski i funkcionalno zbog čega nastaju sluzave mikrobne nakupine koje uzrokuju stalno čepljenje filtara i uređaja. Iako su koncentrati emulgirajućih tekućina od kojih se spravljaju radne emulzije obično sterilni, što je ispitano i u našem radu, mikroorganizmi se vrlo brzo nakon namješavanja s vodom razvijaju, jer niti okolina niti voda nisu sterilni. Budući da u spremnicima već postoje mikrorganizmi, nove emulzije se brzo inficiraju pa broj mikroorganizama vrlo brzo raste, ako nema antimikrobnog agensa i ako se uređaji i spremnici pravilno ne održavaju. Kako kvarenje napreduje, pjena i sluz postaju vidljivi. Suspendirane nakupine na površini upućuju na infekciju gljivama, a često se pojavljuje miris na amonijak, ali češće na sulfide. Emulzija promijeni boju, pH vrijednost progresivno pada, a isto tako i svojstvo zaštite od korozije. Naša ispitivanja su pokazala da su spremnici za emulzije u dva pogona bili znatno inficirani s više vrsta mikroorganizama, što je dokazano uzgojem na selektivnim hranjivim podlogama, kao i mikrobiološkom kontrolom u ovlaštenim laboratorijima. Ispitivanja su, nadalje, pokazala da se pravilnim postupanjem i održavanjem postrojenja i spremnika uvelike smanjuje kvarenje emulzija a time i zastoj u pogonu, čega je posljedica znatna financijska ušteda.Abstract Material degradation is a problem which has always been occupying the attention of experts, because, first of all, it leads to major economic losses. That is why the causes of deterioration of various materials have been the object of research for a number of years now. Organized groups of researchers, mostly in chemical industry, supported by governmental organizations, are engaged in analyses and research of this particular area. The biggest role in degradation is that of biodeterioration, defined as any unwanted change of the material properties caused by the activities of living organisms. Biodegradation in the form of deterioration constitutes an unwanted process when it comes to the production and storage of materials, but is in turn a most desirable process when the material in question becomes waste, both of these processes usually involving often the same kinds of microorganisms. Emulsions for cooling and lubrication at metalworking with a high water content of up to 98%, and are precisely for this reason most prone to microorganisms growth. The oil phase makes a good nutritional basis for microorganisms as a source of carbon. Because of the tiny drops dispersed in water, the contact interphase oil/water surface is very large, which is why the surface for microorganisms growth is sufficient as well, water being the essential medium for their development. Under the impact of the metabolism of microorganisms, the product changes both chemically and functionally, which is why the slimy microbial growths cause constant clogging of filters and devices. Although the concentrates of emulsifying fluids from which working emulsions are made are usually sterile according also to the results of this paper, microorganisms, after blending with water, develop very soon. That is because neither the environment nor the water are sterile. Since there already are microorganisms in the containers, new emulsions are soon infected and the number of microorganisms grows very fast unless there is an antimicrobial agent present, respectively unless the devices and containers are properly maintained. As deterioration progresses, the foam and the mucilage become visible. Suspended growths on the surface point to infection by fungi, while the smell of ammonia and even more frequently that of sulphides also frequently appears. Emulsion changes colour, while pH progressively decreases, along with the corrosion protection property. Our tests have shown that reservoirs for emulsions in two plants were quite infected with several kinds of microorganisms, which has been proven by cultivation on selective nutritive media, as well as through determination of species in authorized laboratories. The tests have furtherly shown that proper handling and maintenance of the plants and reservoirs considerably reduces emulsion deterioration, and hence also plant standstills, resulting in considerable financial savings

THE DIESEL AND BIODIESEL FUEL BIODEGRADATION TESTING IN ORDER TO CONTROL SUPPLY CHAIN AND PRESERVE FUEL QUALITY

Najveći problem vezan uz područje mikrobiologije goriva jest što mikrobiološke infekcije uzrokuju gubitak kvalitete proizvoda, formiranje muljeva, naslage na filtrima, cijevima i ventilima, oštećenja cjevovoda i spremnika goriva u rafinerijama zbog procesa biokorozije i time visoke troškove popravaka ili zamjene dijelova opreme, promjene u radu motora i, na kraju, gubitak ugleda (korisnici govore o problemima). U radu su prikazani rezultati ispitivanja potencijala autohtone mikrobne populacije izolirane iz tla za biorazgradnju dizelskog goriva (eurodizel) i biodizela (metilnih estera masnih kiselina FAME). Testirane su mješavine dizelskog goriva s 10 % (v/v) FAME (B10), dizelsko gorivo i biodizel (B100). Također su iz dizelskog goriva i biodizela izolirane mješovite kulture mikroorganizama. Rezultati istraživanja pokazali su da mješovita mikrobna populacija koja nije prethodno bila izložena naftnim ugljikovodicima u laboratorijskim uvjetima razgrađuje FAME u potpunosti nakon šest dana, a čisto dizelsko gorivo također, ali u manjoj mjeri. Razlika je uočena i u brzini rasta ovisno o izvoru ugljika (FAME ili čisti eurodizel) kao i u uvjetima rasta ovisno o sastavu hranjive podloge za uzgoj. Iz rezultata se može zaključiti da će u cijelom lancu proizvodnje, skladištenja i opskrbe uz dodatak FAME biti pojačana mikrobna proliferacija što može, ukoliko se ne primjenjuju mjere održavanja čistoće u svim segmentima proizvodnje i distribucije, imati posljedicu smanjenja kvalitete goriva, pojavu biokorozije i, na kraju, pad ugleda distributera na tržištu. Cilj je bio upoznati upravu kompanije s kojom vrstom problema vezanih na kvalitetu goriva će se suočiti uvođenjem biodizela u proces proizvodnje kao i na vrijeme uvesti brze i točne metode za utvrđivanje mogućih mikrobnih infekcija. Također, na temelju rezultata istraživanja, stanja lanca opskrbe i distribucije te iskustava naftne industrije u svijetu, predložene su preventivne i zaštitne mjere.The mayor microbial problem in the petroleum refining industry in the world is that microbial contamination of stored products leads to loss of product quality, sludge formation, deterioration of pipework and storage tank in the refinery due to bio corrosion processes, huge costs of equipment reparation and replacement, deposition and blockage of filters, pipes, valves, engine failures and finally loss of reputation (customers are talking about). In this paper the results of biodegradability potential of autochthonous microbial culture isolated from hydrocarbon unpolluted soil are presented. Mixture of biodiesel/diesel B10 (10% biodiesel/diesel (v/v) and biodiesel B100 (FAME, fatty acid methyl ester) was tested. The results were compared to the results of reference fuel (euro diesel). From diesel and biodiesel fuel, mixed microbial cultures were isolated as well. The results showed that the mixed microbial population that has not previously been exposed to petroleum hydrocarbons in the laboratory degraded FAME completely after six days and pure diesel fuel but to a lower extent. The difference was observed in the growth rate depending on the source of carbon (FAME or pure eurodiesel) as well as in growth conditions, depending on the culture medium composition. From the study results, it can be concluded that in the entire fuel production, storage and supply chain after FAME addition there will be the enhanced microbial proliferation, which can, if "good housekeeping practice" will not be implemented, resulted with fuel quality reduction and biocorrosion. The aim was to meet company authorities what kind of problems the company will face after the introduction of biodiesel (fatty acid methyl ester FAME) in the production process and to introduce the new fast and precise methods for fuel microbial infection detection. In addition, based on laboratory research result, company’s fuel and distribution supply chain conditions and experience from petroleum industry in the world preventive and protective measures were proposed. fuels, biofuels, quality, biodegradatio