Maria N. Kostopoulou

Organochlorine pesticides in the surface waters of Northern Greece

A survey undertaken in Northern Greece has shown that organochlorine pesticides are present in the surface waters. Surface water samples have been collected seasonally from four rivers and five lakes for a period of two years. Solid-phase extraction followed by gas chromatographic techniques with electron capture detection was used for the determination of the compounds. The most commonly encountered organochlorine pesticides in surface waters were the isomers of hexachlorocyclohexane, aldrin, dieldrin and endosulfan sulfate. In some cases the concentrations detected were higher than the qualitative target levels set by the European Union, especially for hexachlorocyclohexane and aldrin. The occurrence of these compounds in Greek surface waters can be attributed to intense agricultural activity as well as to transboundary pollution.

Application of different analytical methods for determination of volatile chlorination by-products in drinking water.

Four analytical methods have been applied for the determination of volatile chlorination by-products in drinking water, based on the following techniques: liquid-liquid extraction-gas chromatography-electron capture detection (LLE-GC-ECD); liquid-liquid extraction-gas chromatography-mass spectrometry (LLE-GC-MS); purge and trap-gas chromatography-mass spectrometry (purge and trap-GC-MS); and headspace-gas chromatography-mass spectrometry (headspace-GC-MS). The compounds studied were trihalomethanes, haloacetonitriles, haloketones, chloral hydrate and chloropicrin. LLE-GC-ECD method proved to be the most sensitive for determination of all compounds studied, followed by LLE-GC-MS. Purge and trap-GC-MS method gave good results in the case of trihalomethanes, but had high detection limits for the other volatile chlorination by-products. Headspace-GC-MS method had acceptable recoveries for trihalomethanes, but the detection limits were higher.

Determination of volatile organic compounds in surface waters and treated wastewater in Greece

The occurrence of volatile organic compounds (VOCs) was studied in river water, lake water, seawater and treated wastewater in Greece from October 1998 to September 1999. The determination of 41 VOCs was performed with a Purge and Trap-Gas Chromatography-Mass Spectrometry method. Samples were collected seasonally from 10 rivers, seven lakes, three gulfs and four wastewater treatment plants. In surface water samples, 15 VOCs were detected. In wastewater samples, occurrence of 31 VOCs was observed. The results suggest that not only agricultural and industrial activity within the Greek territory, but also transboundary pollution deriving from neighbouring countries consist important sources of VOCs in surface waters of Greece. However, the measured concentrations did not in any case exceed the guideline values proposed by the EC.

DBP levels in chlorinated drinking water: effect of humic substances.

Chlorination is the most widely used technique for disinfection of drinking water. A consequence of chlorination is the formation of Disinfection By-Products (DBPs). The formation of DBPs in drinking water results from the reaction of chlorine with naturally occurring organic materials, principally humic and fulvic acids. This paper focuses on the effect of humic substances on the formation of twenty-four compounds belonging to different categories of DBPs. This investigation was conducted in two water treatment plants in Greece, Menidi and Galatsi, from July 1999 to April 2000. Humic substances were determined by the diethylaminoethyl (DEAE) method with subsequent UV measurement. The techniques used for the determination of DBPs were liquid-liquid extraction, gas chromatography and mass spectrometry. The concentrations of DBPs were generally low. Total trihalomethanes (TTHMs) ranged from 5.1 to 24.6 μg L-1, and total haloacetic acids (HAAs) concentration ranged from 8.6 to 28.4 μg L-1, while haloaketones (HKs) and chloral hydrate (CH) occurred below 1 μg L-1. The content of humic substances was found to influence the formation of DBPs and especially TTHMs, trichloroacetic acid (TCA), dibromoacetic acid (DBA), CH, 1,1-dichloropropanone (1,1-DCP) and 1,1,1-trichloropropanone (1,1,1-TCP). Seasonal variation of TTHMs and HAAs generally followed that of humic substances content with peaks occurring in autumn and spring. The trends of 1,1-DCP, 1,1,1-TCP and CH formation seemed to be in contrast to TTHMs and HAAs. Trends of formation of individual compounds varied in some cases, probably due to influence of parameters other than humic substances content. Statistical analysis of the results showed that the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DBA are strongly affected from humic substances content (at 0.01 confidence level). The opposite is true for dichloroacetic acid (DCA) concentration. Humic substances also vary to a statistically significant degree during different months, as well as the concentrations of TTHMs, CH, 1,1-DCP, 1,1,1-TCP, TCA and DCA. The variance of DBA was not statistically significant. Regarding the effect of sampling station, humic substances content showed no statistically significant difference between the two raw water sources studied.

Determination of haloacetic acids in water by acidic methanol esterification–GC–ECD method

Acidic methanol esterification followed by gas chromatography (GC) with electron capture detection (ECD) was applied for the determination of the nine haloacetic acids in water. The main advantage of this method is the use of acidic methanol as the derivatization agent instead of the hazardous diazomethane. The recoveries, estimated at concentrations ranging from 0.5 to 30 microg/l, are high for eight of the nine haloacetic acids, with the only exception being monochloroacetic acid. However, problems with this compound have been reported with diazomethane derivatization methods as well. The detection limits of the method range from 0.01 to 0.2 microg/l.

Use of a multiple regression model for predicting trihalomethane formation

For many years the water supply system of Athens in Greece has been disinfected mainly by chlorination. A consequence of chlorination is the formation of trihalomethanes (THMs). A survey was conducted to determine their levels in the Athens water supply system over a period of time. A multiple regression model for THM formation was generated for predicting THMs in the finished water leaving the plant using the field sampling of the Galatsi Treatment Plant (GTP) of Athens with respect to temperature, pH, chlorine dose, bromide and chlorophyll a. In general, this model was found to give acceptable fits. Overall 82% of the predicted values were within ±20% of the measured values.

Decomposition of dihaloacetonitriles in water solutions and fortified drinking water samples

An investigation of the decomposition of dihaloacetonitriles (DHANs) in water solutions and fortified drinking water samples was conducted. The concentrations of dichloroacetonitrile (CHCl2CN, DCAN), bromochloroacetonitrile (CHBrClCN, BCAN) and dibromoacetonitrile (CHBr2CN, DBAN) were determined by a gas chromatography mass spectrometry (GC-MS) method at regular time intervals and different temperatures. The effect of sodium thiosulfate (Na2S2O3), which is used as a preservative in water samples, was also examined. The rates of decomposition were determined for each compound. The results show that the reactions are faster in fortified drinking water samples than in ultrapure water solutions. They are also favored at higher temperature, especially when sodium thiosulfate is present. The highest decomposition rate is shown by DCAN, followed by BCAN and DBAN, while at the presence of sodium thiosulfate the decomposition of DBAN is the fastest.

Volatile organic compounds in the surface waters of Northern Greece

An investigation into the occurrence of volatile organic compounds (VOCs) was conducted for a period of two years in the surface waters of Northern Greece. Samples from four rivers and five lakes were taken seasonally and analyzed for VOCs. The analysis has been performed by purge-and-trap (PAT) gas chromatographic-mass spectrometric (GC-MS) technique. The most commonly encountered VOCs in surface waters were chloroform, carbon tetrachloride, trichloroethylene, dichlorobromomethane, tetrachloroethylene, and chlorodibromomethane.

Investigation of the behaviour of haloketones in water samples

The behaviour of the haloketones (HKs) 1,1-Dichloropropanone (1,1-DCP), 1,1,1-Trichloropropanone (1,1,1-TCP) and 1,3-Dichloropropanone (1,3-DCP) in ultrapure water solutions and in fortified drinking water samples was investigated. Their concentrations were determined at regular time intervals by the use of a gas chromatography-electron capture detector (GC-ECD) method. Two different temperatures were studied. The results have shown that HKs decompose both in ultrapure water solutions and in drinking water samples. The decomposition rates are higher in the drinking water samples, especially at higher temperature. 1,1,1-TCP is the compound which decomposes fastest followed by 1,3-DCP and 1,1-DCP. Chloroform was formed both in the ultrapure water solutions and in the drinking water samples, probably due to the decomposition of 1,1,1-TCP. In the drinking water samples, formation of chloral hydrate was also observed.

Volatile halogenated organics in the water supply system in Athens, Greece

Abstract A survey undertaken in Athens has shown that Volatile Halogenated Organics (VHO) are present in chlorinated drinking water; analysis has been performed by purge-and-trap (PAT) gas chromatographic (GC) technique. Samples from different points of the Menidi Treatment Plant (MTP) and the distribution network of Athens were taken and analyzed for VHO. Surface water samples have been collected every month for a period of eight months, and have shown the occurrence of chloroform, dichlorobromomethane, chlorodibromomethane as a result of the chlorination of raw water and of tetrachloroethylene and 1,1,1,2-tetrachloroethane.