Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Removal of methyl parathion from water by electrochemically generated Fenton's reagent

The electro-Fenton process was used to assess the degradation of methyl parathion (MP) in aqueous solutions. This oxidation process allows the production of hydroxyls radicals which react on the organic compounds, leading to their mineralization. Degradation experiments were performed either in perchloric, sulphuric, hydrochloric and nitric acid media under current controlled electrolysis conditions at different pH. The pH effect as well as the nature of the medium (i.e., the nature of the ions present in medium) on the degradation and mineralization efficiency were studied. The mineralization of the initial pollutant was investigated by total organic carbon measurements which show a complete mineralization at pH 3 in perchloric medium. The absolute rate constant of MP hydroxylation reaction was determined as (4.20+/-0.11)x10(9)M(-1)s(-1). Complete degradation of MP and its metabolites occur in less than 45min. Degradation reaction intermediates such as aromatic compounds, carboxylic acids and inorganic ions were identified and a mineralization pathway is proposed.     

Decolourization and removal of some organic compounds from olive mill wastewater by advanced oxidation processes and lime treatment

Background Olive mill wastewater (OMW) generated by the olive oil extracting industry is a major pollutant, because of its high organic load and phytotoxic and antibacterial phenolic compounds which resist biological degradation. Mediterranean countries are mostly affected by this serious environmental problem since they are responsible for 95% of the worldwide oliveoil production. There are many methods used for OMW treatment, such as adsorption, electro coagulation, electro-oxidation, biological degradation, advanced oxidation processes (AOPs), chemical coagulation, flocculation, filtration, lagoons of evaporation and burning systems, etc. Currently, there is no such economical and easy solution. The aim of this study was to evaluate the feasibility of decolourization and removal of phenol, lignin, TOC and TIC in OMW by UV/H₂O₂ (AOPs). The operating parameters, such as hydrogen peroxide dosage, times, pH, effect of UV and natural sunlight were determined to find the suitable operating conditions for the best removal. Moreover, there is no study reported in the literature related to the use of UV/H₂O₂ and lime together in OMW treatment. Methods OMW was obtained from an olive-oil producing plant (Muğla area of Turkey) which uses a modern production process. No chemical additives are used during olive oil production. This study was realised by using two different UV sources, while taking the time and energy consumption into consideration. These two sources were mercury lamps and natural sunlight. Before starting AOPs experiments, one litre of OMW was treated by adding lime until a pH of 7.00. Then, 100 ml was taken from each sample, and 1 to 10 ml of a 30% H₂O₂ (Riedel-deHaen) solution was added. These solutions in closed vessels were laid in the natural sunlight for a week and their compositions and colour changes were analysed daily by UV-Vis spectrophotometer. At the end of the one-week period, they were treated with lime. In this study, the effect of changes in the initial pH, times and H₂O₂ concentrations on removal was investigated. At the end of all experiments, changes in colour, phenol, lignin, TOC and TIC concentrations were analysed according to standard methods. Results and Discussion In the samples exposed to natural sunlight and having an H₂O₂/OMW ratio of 3 ml/100 ml, a significant colour removal was achieved approximately 90% of the time at the end of 7 days. When the same samples were treated with lime (pH: up to 7), 99% efficiency was achieved. When phenol and lignin removals were examined in the same concentration, phenol and lignin removal were found 99.5%, 35%, respectively. However, for maximum lignin removal, more use of H₂O₂ (10 ml H₂O₂/100 ml OMW) was found to be necessary. Under these conditions, it was found that lignin can be removed by 70%, but to 90% with lime, at the end of a seven-day period. Rate constants obtained in the experiments performed with direct UV were found to be much higher than those of the samples exposed to natural sunlight (k^a _lignin = 0.3883 ≫ k^b _lignin = 0.0078; k^a _phenol = 0.5187 ≫ k^b _phenol = 0.0146). Moreover, it should be remembered in this process that energy consumption may induce extra financial burden for organisations. Conclusions It was found, in general, that colour, lignin, total organic carbon and phenol were removed more efficiently from OMW by using H₂O₂ UV and lime OMW. Moreover, in the study, lime was found to contribute, both initially and after radical reactions, to the efficiency to a great extent. Recommendations and Perspectives Another result obtained from the study is that pre-purification carried out with hydrogen peroxide and lime may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Impacts of the fish farms on the water column nutrient concentrations and accumulation of heavy metals in the sediments in the eastern Aegean Sea (Turkey)

Pulp and paper mill effluents may cause harmful effects to the aquatic environment due to the combined influence of physical factors, toxic compounds, and nutrient enrichment. In the present study, the effectiveness of secondary treatment in reducing the toxicity of an elemental chlorine-free bleached-kraft pulp mill effluent was evaluated. To characterize the toxicity of the effluent, before and after the implementation of secondary treatment, a battery of tests with organisms bearing different functions at the ecosystem level was used, namely Vibrio fischeri (5-min luminescence), Pseudokirchneriella subcapitata (72-h growth), Lemna minor (7-day growth), Daphnia magna (21-day reproduction and 24-h postexposure feeding), Chironomus riparius (9-day growth), and Danio rerio (28-day growth). For the effluent sample collected before the implementation of secondary treatment, P. subcapitata was the most sensitive organism followed by V. fischeri and D. magna, and no toxic effects were observed toward the other organisms. For the effluent sample collected after the implementation of secondary treatment, the effluent caused no toxic effects on any of the tested species. The present results demonstrated not only that secondary treatment efficaciously reduced effluent toxicity toward the selected test organisms but also the usefulness of a battery of tests to characterize the toxicity of pulp mill effluents.     

Monitoring and assessment of heavy metal/metalloid concentration by inductively coupled plasma mass spectroscopy (ICP-MS) method in Gonyeli Lake,Cyprus

The presence of heavy metals/metalloids in the ecosystem has been an increasing ecological and global public health concern due to their potential to cause adverse health effects. For this reason, the accumulation of some heavy metals such as Cr, Mn, Ni, Cu, As, Cd, Pb was assessed by way of ICP-MS in water, sediment and fish (Cyprinus carpio) sampled from Gonyeli Lake, North Cyprus. The results showed that these metals/metalloids are found widespread throughout the study area. In water, most concentrated element was manganese with 92.1 ppb and least concentrated was lead with 0.914 ppb. In sediment, copper had the highest concentration with 613 ppm, and cadmium the lowest with 1.57 ppm. In fish tissues (muscle and gills), the most concentrated element was manganese with 12.5 ppm and the least concentrated cadmium with 0.017 ppm. These results indicate that future remediation efforts are indispensable for the rehabilitation of the lake.     

Measuring the spatial impacts of urbanization on the surface water resource basins in Istanbul via remote sensing

Istanbul is one of the largest metropolitan cities in the World. The city has experienced rapid industrialization and urbanization in the second half of the twentieth century. Between 1950 and 2000, the city has grown by an average of 4.5% annually. Given the scale of the growth, neither local nor the central governments have shown capability of controlling the influx of migration, most of which settled illegally on public lands. Most of the settlements lack the basic sewerage facilities, and a significant portion of which are on the major water resource basins. As of today, Istanbul Metropolitan Municipality (IMM) not only has to cope with the infrastructure problems, but also has to find ways of solving the problem of illegal occupations of public lands and water resource basins. This paper presents the land use changes in the water resource basins providing water to the Istanbul Metropolitan Area. Using four consecutive Landsat images between 1990 and 2005, the changes in 12 different land use categories are obtained via overlay operations by GIS for water resource basins surrounding the City of Istanbul. It has been observed that the most critical land use changes are in the nearest basins to the city. The capability of Landsat and IKONOS images in determining the alterations in the macro form of the city are also discussed. Finally, possibility of utilization of new technologies in policy making regarding environmental management in Istanbul is discussed.     

Long-term monitoring of the impact of a capture-based bluefin tuna aquaculture on water column nutrient levels in the Eastern Aegean Sea, Turkey

Capture-based aquaculture of Atlantic bluefin tuna in the Mediterranean has been expanding rapidly but little is known about its environmental impact. In order to understand the consequences of this new sector, long-term monitoring is needed. For this purpose, we investigated the impact of a capture-based tuna farm located in the Gerence Bay (Aegean Sea) on the water column on a seasonal basis from 2005 to 2008, where in the water column, temperature, salinity, pH, dissolved oxygen, nutrients (nitrite, nitrate, ammonium, and phosphate), and chlorophyll a, in the sediment organic carbon variables were measured. Although highest nutrient concentrations were observed at the cage station as compared to the two controls in the production period, differences were not statistically significant between stations. Monitoring of physico-chemical parameters, nutrients, and chlorophyll a in water column together with organic carbon in sediment did not show detectable impact of fattening of Atlantic bluefin tuna. This was probably caused by strong currents present in the area, location of the cages away from the coast, hence high water depth, controlled feeding, and periodic presence of tuna farming activity in the study area.     

Environmental effects of maritime traffic on the İstanbul Strait

The Istanbul Strait, which separates the European and the Asian parts of Istanbul, is one of the narrowest straits in the world that is used for international shipping. The Strait has very special ecological conditions in terms of marine environment (atmospheric/oceanographic conditions, plant and animal diversity) and terrestrial environment. It also has roles as biological corridor and biological barrier between the Mediterranean Sea and the Black Sea and form an acclimatization zone for migrating species. Due to being the only maritime access for the neighboring Black Sea states and the Central Asian Turki Republics, the Istanbul Strait has been exposed to dense marine traffic for centuries and substantial increase has occurred in size and tonnage of the ships passing through the Strait with hazardous cargo varieties and amounts they carry. Increase in the number of vessels that navigates on the Strait and being on the transportation way of hazardous and dangerous materials pose serious environmental and safety hazards for the Istanbul Strait, Marmara Sea and the surrounding residential areas. Geographic and oceanographic features of the Istanbul Strait makes the navigation on the Strait rather difficult and consequently the Strait has faced many casualties that caused severe environmental problems due to thousands tons of oil spill occurring in recent decades.     

Mineral contents of the head, caudal, central fleshy part, and spinal columns of some fishes

In the experiment, mineral contents of the head, caudal, central fleshy part, and spinal columns of fishes were determined by inductively coupled plasma atomic emission spectrometry. The Ca content of base fleshy part ranged from 1,682 to 5,505 mg/kg. The Ca contents of central fleshy part were found between 104 and 428 mg/kg. This value was found between 5,582 and 7,368 in the spinal column parts. The K content in general ranged from 2,411 (Carassius gibellio) and 4,419 mg/kg (Scomber scombrus). The highest potassium was found on the central fleshy part and ranged between 3,214 and 4,419. The P content was found mostly on the bones and it range between 28,833 and 34,726. The least phosphor amount was found on the central fleshy part. While the Cd content ranges between 0.019 ppm and 0.104 mg/kg, Cr content changed between 1.32 and 4.20 ppm.     

Determination of heavy metal contents in some freshwater fishes

The concentrations of heavy metals in tench, pike-perch, and common carp fish caught in four different seasons from Damsa dam lake (Nev?ehir) were determined. Heavy metal contents of fishes changed depending on seasons. The highest Al (20.894 mg/kg) in tench was established in winter, and the lowest Al (1.605 mg/kg) was determined in summer. Fe content of tench fish changed between 112.906 mg/kg (autumn) and 31.207 mg/kg (spring). In addition, Zn contents of tench were found between 36.0323 mg/kg (summer) and 430.586 mg/kg (winter). The results indicate that concentrations of Cu of tench varied from 0.1934 mg/kg (winter) to 15.422 mg/kg (autumn). Results indicate that concentrations varied from 2.923 mg/kg (autumn) to 32.078 mg/kg (summer) with a mean of 11.1893 mg/kg for Al; 0.2483 mg/kg (spring) to 3.3088 mg/kg (autumn) with a mean of 1.6189 mg/kg for Ni; 0.5325 mg/kg (spring) to 0.845 mg/kg (autumn) with a mean of 0.7234 for Pb; and 7.0464 mg/kg (winter) to 253.686 mg/kg (summer) with a mean of 133.6348 for Zn. In common carp, Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn, Se, Ga, and Te contents were determined as 3.9623 mg/kg; 0.1293, 0.2336, 0.0526, 0.1543, 4.2406, 0.726, 1.797, 0.6216, 6.8536, 0.1783, 0.7876, and 0.371 mg/kg in autumn, respectively.