Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

Groundwater resources at risk in the glaciofluvial formation of Jokkavaara in Rovaniemi area, Northern Finland

The best groundwater resources in Finland are generally situated in glaciofluvial formations with thick sand and gravel deposits. The glaciofluvial formation of Jokkavaara, in northern Finland near the town of Rovaniemi, is important for both its groundwater reserves and its sand and gravel resources. The groundwater and mineral resources of Jokkavaara was studied to define their quantity and quality, and to develop a land-use plan which would help civil servants of the municipality to make the decisions necessary for exploiting sand and gravel. The land-use plan shows the areas where exploiting mineral resources is not allowed or recommended because of the risks of contamination of groundwater, or because of injurious effects on the environment caused by noise and dust from gravel pits, or by spoilt landscape. The size of Jokkavaara is 5 km2, and its mineral resources are about 53 million cubic metres. The sand and gravel deposits are at the most, 50 m thick. Risks of contamination by fallout are small, due to the thick sand and gravel deposits above groundwater level. Exploiting mineral resources have no effect on groundwater quality either. By the land-use plan and legislation, good groundwater can also be protected in the future. Legislation limits the exploitation of mineral resources especially in groundwater areas.     

Photolytic degradation of quinalphos in natural waters and on soil matrices under simulated solar irradiation

The photochemical persistence of quinalphos, one of the most widely used organophosphorous insecticides, was investigated in a variety of environmental matrices such as natural waters and soils of different composition. Simulated solar irradiation was obtained using a xenon arc lamp (Suntest CPS+ apparatus) giving an irradiation intensity of 750 W m(-2) equivalent to a light dose per hour of irradiation of 2,700 kJ m(-2). The phototransformation rates were determined using solid-phase microextraction (SPME) and ultrasonic extraction (USE) coupled to GC-FTD, while the identification of photoproducts was carried out by GC-MS. In water samples, the degradation kinetics followed a pseudo-first-order reaction and photolysis half-lives ranged between 11.6 and 19.0 h depending on the constitution of the irradiated media. Dissolved organic matter (DOM) has a predominant retarding effect, while nitrate ions accelerated the photodegradation kinetics. In soil samples, the degradation kinetics was monitored on 1mm soil layer prepared on glass TLC plates. The kinetic behaviour of quinalphos was complex and characterized by a double step photoreaction, fast in the first 4h of irradiation followed by a slow degradation rate up to 64 h. The photolysis half-life of quinalphos was shorter in sandy soil compared to the rest of the soil samples, varying between 16.9 and 47.5 h, and showing a strong dependence on the composition of the irradiated media. Among the transformation products formed mainly through photohydrolysis and photoisomerization processes, some photoproduct structures were proposed according to their mass spectral information.     

TiO2 photocatalyzed degradation of diazinon in an aqueous medium

The photocatalytic degradation of diazinon was studied over TiO₂ catalysts. The kinetics obtained demonstrated that powder titania (t_1/2 = 9.7 min) was more efficient compared to pure titania thin film catalysts (t_1/2 = 29.4 min). Mineralization of organic carbon to CO₂ after 360 min of irradiation was found to be 75% while heteroatoms (P, S, N) were mineralized into phosphate, sulfate and nitrate ions, respectively. A microtox test was performed to evaluate the toxicity of solutions treated by catalysts. Illumination of diazinon in the presence of TiO₂ gave rise to several intermediates that have been identified by means of solid phase extraction and gas chromatography-mass spectrometry, while a simple degradation pathway is proposed.     

Closed wastewater cycle in a meat producing and processing industry

Creta Farm Plc, owns the largest meat producing (pigs rearing), processing and packaging unit in the island of Crete, in Greece, placed outside the city of Rethymnon in the north coast of the island. From the farm, where more than 20 000 pigs of various ages and sizes live, 300–320 m³ of wastewater are collected in a daily basis. From the slaughterhouse and the processing unit another 100–125 m³/d are produced. The wastewater treatment system is a combination of settling and aeration tanks, with decanters operating in different phases of the process, mainly for the removal of the solids from the wastewater. The average biochemical oxygen demand and total suspend solids values of the treated effluent are 40 and 80 mg/l, respectively. From this almost secondary treated effluent about 100 m³ are used for cleaning the sewage pipes of the rearing unit (animals houses). The remaining 300 m³ are disinfected with a weak chlorine solution before used for irrigating trees, grass and various other plants. More than 2000 eucalyptus trees, 1500 tamarix trees and a large number of olive trees are growing in the site creating a pleasant view and at the same time help minimising the odour problem.     

Antifouling paint booster biocide contamination in Greek marine sediments

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin in 1987. In this study, the concentrations of three biocides commonly used as antifoulants, Irgarol 1051 (2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine), dichlofluanid (N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl sulphamide) and chlorothalonil (2,4,5,6-tetrachloro isophthalonitrile) were determined in sediments from ports and marinas of Greece. Piraeus (Central port, Mikrolimano and Pasalimani marinas), Thessaloniki (Central port and marina), Patras (Central port and marina), Elefsina, Igoumenitsa, Aktio and Chalkida marinas were chosen as representative study sites for comparison with previous monitoring surveys of biocides in coastal sediments from other European countries. Samples were collected at the end of one boating season (October 1999), as well before and during the 2000 boating season. All the compounds monitored were detected at most of sites and seasonal dependence of biocide concentrations were found, with maxima during the period June-September, while the winter period (December-February) lower values were encountered. The concentrations levels ranged from 3 to 690 ng/g dw (dry weight). Highest levels of the biocides were found in marinas (690, 195 and 165 ng/g dw, for Irgarol, dichlofluanid and chlorothalonil respectively) while in ports lower concentrations were observed. Antifouling paints are implicated as the likely sources of biocides since agricultural applications possibly contributed for chlorothalonil and dichlofluanid inputs in a few sampling sites.     

Survey for the occurrence of antifouling paint booster biocides in the aquatic environment of Greece

Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the 'small boat' market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.