To augment the removal of pharmaceuticals different conventional and alternative wastewater treatment processes and their combinations were investigated. We tested the efficiency of (1) two distinct laboratory scale biological processes: suspended activated sludge and attached-growth biomass, (2) a combined hydrodynamic cavitation-hydrogen peroxide process and (3) UV treatment. Five pharmaceuticals were chosen including ibuprofen, naproxen, ketoprofen, carbamazepine and diclofenac, and an active metabolite of the lipid regulating agent clofibric acid. Biological treatment efficiency was evaluated using lab-scale suspended activated sludge and moving bed biofilm flow-through reactors, which were operated under identical conditions in respect to hydraulic retention time, working volume, concentration of added pharmaceuticals and synthetic wastewater composition. The suspended activated sludge process showed poor and inconsistent removal of clofibric acid, carbamazepine and diclofenac, while ibuprofen, naproxen and ketoprofen yielded over 74% removal. Moving bed biofilm reactors were filled with two different types of carriers i.e. Kaldnes K1 and Mutag BioChip™ and resulted in higher removal efficiencies for ibuprofen and diclofenac. Augmentation and consistency in the removal of diclofenac were observed in reactors using Mutag BioChip™ carriers (85%±10%) compared to reactors using Kaldnes carriers and suspended activated sludge (74%±22% and 48%±19%, respectively). To enhance the removal of pharmaceuticals hydrodynamic cavitation with hydrogen peroxide process was evaluated and optimal conditions for removal were established regarding the duration of cavitation, amount of added hydrogen peroxide and initial pressure, all of which influence the efficiency of the process. Optimal parameters resulted in removal efficiencies between 3-70%. Coupling the attached-growth biomass biological treatment, hydrodynamic cavitation/hydrogen peroxide process and UV treatment resulted in removal efficiencies of >90% for clofibric acid and >98% for carbamazepine and diclofenac, while the remaining compounds were reduced to levels below the LOD. For ibuprofen, naproxen, ketoprofen and diclofenac the highest contribution to overall removal was attributed to biological treatment, for clofibric acid UV treatment was the most efficient, while for carbamazepine hydrodynamic cavitation/hydrogen peroxide process and UV treatment were equally efficient.

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The surface water geochemistry and carbon cycling studied here depend mainly on geological composition of the river catchment. The investigated surface waters in the river Pesnica catchment that are heavily hydromorphologicaly altered (reservoirs, channelization, land melioration systems) represent waters influenced by chemical weathering of carbonates and of mostly clastic rocks (claystone, sandstones, marlstones and siltstones). The objectives of our study were to analyze hydrogeochemical and isotopic composition of dissolved (δ 13 C DIC ) and particulate carbon (δ 13 C POC ) with characterization of suspended matter and evaluate biogeochemical processes in Pesnica River in Slovenia before and after the retention. Surface waters are generally close to saturation regarding calcite and dolomite, dissolved CO 2 is 49 to 1000 times oversaturated relative to atmosphere. δ 13 C DIC was in the range from -14.8 to -4.2 ‰ and shows following biogeochemical processes in river system: degradation of organic matter, dissolution of carbonates and biological activity, which was confirmed with SEM microscopy and EDXS microanalysis. Results of SEM/EDXS showed that suspended matter is composed of K, Mg and Ca from locations Pesnica 1 and Pesnica 2 (above retention Perniško lake). Sample from Pesnica 3 (below retention) shows higher biological activity, while sample from Pesnica 4 (tributary of Pesnica, drainage channel Biš) contains a lot of particles of microporous structure and fiber structure, which are probably of anthropogenic origin. δ 13 C POC is changing from -29.5 to-27.6‰ and showed different stages of degraded terrestrial material. More negative δ 13 C POC are shown at location at drainage channel Biš and show higher terrestrial input in river system as locations 1, 2 and 3 Pesnica, which have higher δ 13 C POC values. This first results about suspended matter in Pesnica watershed serve for evaluation of anthropogenic influences specially in relation with further influences and longer time planning of sustainable river water management. IzvlečekGeokemija površinskih voda in kroženje ogljika v naši študiji v glavnem zavisita od geološke podlage v porečju. Raziskane površinske vode v porečju Pesnice, ki je hidromorfološko močno preoblikovano (vodni zadrževalniki, urejanje struge, melioracije), predstavljajo vode, na katere vpliva kemijsko preperevanje karbonatov in v glavnem klastičnih kamnin (glinavcev, peščenjakov, laporovcev in meljevcev). Namen naše raziskave je bil analizirati hidrogeokemično in izotopsko sestavo raztopljenega in partikulatnega ogljika skupaj s karakterizacijo suspendirane snovi in oceno biogeokemijskih procesov v porečju Pesnice v Sloveniji pred zadrževalnikom in za njim. Površinske vode so večinoma blizu nasičenja glede na kalcit in dolomit, raztopljen CO 2 je od 49 do 1000 krat prenasičen relativno na atmosfero. δ 13 C DIC je bil v razponu od -14.8 do -4.2 ‰ in kaže na sledeče biogeokemijske procese v rečnem sistemu: razgradnja organske snovi, raztapljanje karbonatov in biološka aktivn...