UV-C-activated persulfate oxidation of a commercially important fungicide: case study with iprodione in pure water and simulated tertiary treated urban wastewater

Recently, the European Food Safety Authority (EFSA) has banned the use of iprodione (IPR), a common hydantoin fungicide and nematicide that was frequently used for the protective treatment of crops and vegetables. In the present study, the treatment of 2 mg/L (6.06 μM) aqueous IPR solution through ultraviolet-C (UV-C)-activated persulfate (PS) advanced oxidation process (UV-C/PS) was investigated. Baseline experiments conducted in distilled water (DW) indicated that complete IPR removal was achieved in 20 min with UV-C/PS treatment at an initial PS concentration of 0.03 mM at pH?=?6.2. IPR degradation was accompanied with rapid dechlorination (followed as Cl^? release) and PS consumption. UV-C/PS treatment was also effective in IPR mineralization; 78% dissolved organic carbon (DOC) was removed after 120-min UV-C/PS treatment (PS?=?0.30 mM) compared with UV-C at 0.5 W/L photolysis where no DOC removal occurred. LC analysis confirmed the formation of dichloroaniline, hydroquinone, and acetic and formic acids as the major aromatic and aliphatic degradation products of IPR during UV-C/PS treatment whereas only dichloroaniline was observed for UV-C photolysis under the same reaction conditions. IPR was also subjected to UV-C/PS treatment in simulated tertiary treated urban wastewater (SWW) to examine its oxidation performance and ecotoxicological behavior in a more complex aquatic environment. In SWW, IPR and DOC removal rates were inhibited and PS consumption rates decreased. The originally low acute toxicity (9% relative inhibition towards the photobacterium Vibrio fischeri) decreased to practically non-detectable levels (4%) during UV-C/PS treatment of IPR in SWW.

     

Effect of Fenton treatment on the aquatic toxicity of bisphenol A in different water matrices

Battery tests serve as integral tools to decide whether a treatment process is ecotoxicologically safe or not. In the present study, a battery of toxicity tests was employed to elucidate the toxicity of the potential endocrine-disrupting pollutant bisphenol A (BPA) and its advanced oxidation products. For this purpose, BPA was subjected to Fenton treatment in the growth medium of the test organisms employed as well as in real lake water. Treatment results indicated that BPA removals were fast and complete within less than a minute, whereas total organic carbon (TOC) removals were rather incomplete, speaking for the accumulation of refractory degradation products. The presence of chloride and/or natural organic matter influenced H₂O₂ consumption rates and the treatment performance of the Fenton’s reagent as well. The sensitivity of the selected test organisms for BPA and its Fenton treatment products in different water matrices was found in the following decreasing order: the freshwater microalgae (Pseudokirchneriella subcapitata) > the freshwater cladoceran (Daphnia magna) > marine photobacteria (Vibrio fischeri).     

Monitoring of heavy metal and organic compound levels along the Eastern Aegean coast with transplanted mussels

Within the framework of the MYTITURK project, heavy metals and organic compounds contaminations were assessed in transplanted mussels in eight different bays from the Eastern Aegean coast. Izmir Bay, Canakkale Strait entrance, Saros and Candarli Bay were defined low pollution extent according to Principal Component Analysis taking into metal accumulation. PAHs (Polycyclic Aromatic Hydrocarbons) levels in the range of 29.4–64.2 ng g⁻¹ (dry weight) indicated that PAH contamination level classified as low along the Aegean coast. Concentrations of Aroclor1254 and 1260 were higher in transplanted mussels from Canakkale Strait Outlet due to industrial activities was originated from Marmara Sea. The organochlorinated pesticides such as heptachlor (<0.4 ng g⁻¹), aldrin (<0.30 ng g⁻¹), dieldrin (<0.75 ng g⁻¹), endrin (<2.3 ng g⁻¹) concentrations were homogeneous however, HCB (Hexachlorobenzene) and lindane concentrations were found undetectable level along the coast. DDE/DDT ratio in the caged mussels form Gulluk and Gokova Bay indicated recent DDT (Dikloro difenil trikloroethan) usage in these areas. The residues of organochlorinated compounds in transplanted mussels confirm the long persistence of DDTs. According to world health authorities, the concentration of heavy metals in mussels for the study area can generally be considered not to be at levels posing a health risk except Zn. The levels of POPs indicated that transplanted mussels have a lack of risk for the human health.     

The effect of pre-ozonation on the biocompatibility of reactive dye hydrolysates

Pre-ozonation of 14 different reactive dyestuff hydrolysates at alkaline pH was investigated to assess possible relationships between ozone transfer efficiency, first order decolourization kinetics, release of initially complexed heavy metals and relative changes in the biodegradability of the partially oxidized dye waste samples. Biocompatibility of the raw (untreated) and ozonated dye hydrolysates was comparatively tracked through specific oxygen uptake rate measurements from which the respirometric inhibition of biological activated sludge imparted by raw and ozonated reactive dye wastewater with respect to synthetic domestic wastewater was determined. It could be demonstrated that preliminary ozonation of reactive azo dyes increases their biological compatibility more significantly than formazan copper complex, copper complex azo and phythalocyanine dyes as a consequence of heavy metal release associated with the cleavage of associated chromophoric groupings right at the initial stages of pre-ozonation.     

Evaluation of the relationship of picoplankton and viruses to environmental variables in a lagoon system (Çakalburnu Lagoon,Turkey)

Lagoons are defined as wetlands separated from the sea coasts on which they are located and sit between continental and marine aquatic ecosystems. Çakalburnu Lagoon is a coastal wetland on the southern side of the Bay of ?zmir. Microorganisms, which are quite sensitive to changes occurring in environmental factors, are commonly used to determine the impact of environmental effects on the functioning of the ecosystem. In this study, variations in the abundance and biomass of picoplankton (Synechococcus spp. and bacteria) and the abundance of viruses, which identify the ecological productivity of the food chain, were seasonally examined by epifluorescence microscopy. Moreover, the microbial abundance and biomass relation over time between the physical and chemical parameters was evaluated. According to our results, the maximum abundance of Synechococcus spp. and viruses was 6.7?×?10⁴ cell/ml and 9.9?×?10⁸?cell/ml in the summer, respectively. Otherwise, the highest level of bacteria was measured at 3.6?×?10⁷ cell/ml in the spring. Based on the principal component analysis and Pearson correlation analysis results, we concluded that total suspended solids, Chl-a, particulate organic carbon and particulate organic nitrogen were the major parameters influencing the observed variability of the lagoon system. Overall, to protect and improve the ecological and microbiological quality of aquatic systems such as lagoons, the necessary monitoring and measurement studies should be conducted in these sensitive areas.     

Effect of inorganic and organic solutes on zero-valent aluminum-activated hydrogen peroxide and persulfate oxidation of bisphenol A

The effect of varying inorganic (chloride, nitrate, sulfate, and phosphate) and organic (represented by humic acid) solutes on the removal of aqueous micropollutant bisphenol A (BPA; 8.8 μM; 2 mg/L) with the oxidizing agents hydrogen peroxide (HP; 0.25 mM) and persulfate (PS; 0.25 mM) activated using zero-valent aluminum (ZVA) nanoparticles (1 g/L) was investigated at a pH of 3. In the absence of the solutes, the PS/ZVA treatment system was superior to the HP/ZVA system in terms of BPA removal rates and kinetics. Further, the HP/ZVA process was not affected by nitrate (50 mg/L) addition, whereas chloride (250 mg/L) exhibited no effect on the PS/ZVA process. The negative effect of inorganic anions on BPA removal generally speaking increased with increasing charge in the following order: NO₃^? (no inhibition)?<?Cl^? (250 mg/L)?=?SO₄^2??<?PO₄^3? for HP/ZVA and Cl^? (250 mg/L; no inhibition)?<?NO₃^??<?SO₄^2??<?PO₄^3? for PS/ZVA. Upon addition of 20 mg/L humic acid representing natural organic matter, BPA removals decreased from 72 and 100% in the absence of solutes to 24 and 57% for HP/ZVA and PS/ZVA treatments, respectively. The solute mixture containing all inorganic and organic solutes together partly suppressed the inhibitory effects of phosphate and humic acid on BPA removals decreasing to 46 and 43% after HP/ZVA and PS/ZVA treatments, respectively. Dissolved organic carbon removals were obtained in the range of 30 and 47% (the HP/ZVA process), as well as 47 and 57% (the PS/ZVA process) for the experiments in the presence of 20 mg/L humic acid and solute mixture, respectively. The relative Vibrio fischeri photoluminescence inhibition decreased particularly for the PS/ZVA treatment system, which exhibited a higher treatment performance than the HP/ZVA treatment system.     

Assessment of heavy metal contamination in Candarli Gulf sediment, Eastern Aegean Sea

Concentrations of selected heavy metals (Fe, Mn, Ni, Cu, Zn, Pb, Hg, Cr, Al, and As) in surface sediments from 18 stations in the Candarli Gulf were studied in order to understand current metal contamination due to urbanization and economic development in Candarli region, Turkey. The sediment samples were collected by box corer in Candarli Gulf in 2009 to assess heavy metal pollution. Heavy metal concentrations in surface sediment varied from 1.62% to 3.60% for Fe, 0.38?C2.53% for Al, 173?C1,423 for Mn, 8?C100 for Ni, 3?C46 for Cu, 55?C119 for Zn, 16?C138 for Pb, 0.2?C6.3 for Hg, 16?C71 for Cr, and 11?C37 mg kg^???1 for As. This study showed that the concentrations of Mn, Ni, Zn, Pb, Hg, and Cr in the surface sediment layers were elevated when compared with the subsurface layers. Both metal enrichment and contamination factors show that Hg, Zn, and Pb contamination exists in the entire study area and contamination of other metals is also present in some locations depending on the sources.     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

Ozonation of Procaine Penicillin G formulation effluent Part I: Process optimization and kinetics

Ozonation characteristics of synthetic Procaine Penicillin G (PPG) formulation effluent were investigated in a semi-batch ozone reactor at different pH (3, 7 and 12), ozone feed rates (600-2600 mg h-1) and COD values (200-600 mg l-1). Ozonation of aqueous PPG effluent resulted in 37 (82)% COD removal after 60 (120) min ozonation when the reaction pH was kept constant at pH=7.900 mg l-1 (corresponding to 50% of the total introduced) ozone was absorbed during a reaction period of 1 h. The effects of increasing the applied ozone dose and the initial COD on the COD abatement rates of PPG effluent were also studied. Results have indicated that increasing the ozone dose and decreasing the COD content both have positive effects on COD removal rates. The significant contribution of the free radical (.OH) reaction pathway to PPG ozonation could be traced using tert-butyl alcohol as the .OH probe compound at varying concentrations. The bimolecular reaction rate constants for the direct reaction of PPG with ozone were found as 152 and 2404 M-1 h-1 at pH=3 and 7, respectively, using the gas phase ozone partial pressures determined from of the outlet gas stream analysis. It could be demonstrated that ozone decomposition to free radicals being triggered by increasing the pH from 3 to 7 is essential for the rate enhancement of PPG effluent ozonation.     

Effect of textile auxiliaries on the biodegradation of dyehouse effluent in activated sludge

The textile industry is confronted with serious environmental problems associated with its immense wastewater discharge, substantial pollution load, extremely high salinity, and alkaline, heavily coloured effluent. Particular sources of recalcitrance and toxicity in dyehouse effluent are two frequently used textile auxiliaries; i.e. dye carriers and biocidal finishing agents. The present experimental work reports the observation of scientific and practical significance related with the effect of two commercially important textile dye carriers and two biocidal finishing agents on biological activated sludge treatment at a textile preparation, dyeing and finishing plant in Istanbul. Respirometric measurements of the dyehouse effluent spiked with the selected textile chemicals were carried out for the assessment of the "readily biodegradable COD fraction" of the wastewater. The respirometric data obtained to visualize the effect of the selected textile auxiliaries on biomass activity was evaluated by an adopted activated sludge model. Results have indicated that the tested biocides did not exert any significant inhibitory effect on the treatment performance of the activated sludge reactor at the concentrations usually encountered in the final, total dyehouse effluent. The situation with the dye carriers was inherently different; one dye carrier appeared to be highly toxic and caused serious inhibition of the microbial respirometric activity, whereas the other dye carrier, also known as the more ecological alternative, i.e. the "Eco-Carrier", appeared to be biodegradable. Finally, the respirometric profile obtained for the Eco-Carrier was described by a simplified respirometric model.