The potential of pesticides to contaminate the groundwater resources of the Axios river basin in Macedonia, Northern Greece. Part I. Monitoring study in the north part of the basin.

The Axios river basin is an area of high agricultural importance for Macedonia, Northern Greece. High priced crops such as cotton, corn, sugarbeets, vegetables and rice are rotated with cereals and alfalfa and thus a great variety of pesticides are used annually for the control of pests and diseases. Moreover, the groundwater resources of the specific area constitute the main source of potable water for the surrounding cities and villages. Therefore, a study was initiated to investigate the probable risks of groundwater contamination with pesticides. The leaching of pesticides from agricultural soils was monitored in the phreatic horizon as well as in soil water samples collected with suction lysimeters. In parallel studies, the presence of pesticides in the irrigation water and the water of Axios river was also monitored. Pesticides like carbofuran, atrazine, alachlor and prometryne, which were regularly applied in the northern part of the basin during 1992-1994 were detected at concentrations occasionally exceeding 1 microg/l in soil water from the deeper soil layers and in the phreatic horizon. Residues of pesticides others than the ones applied in the studied area like propanil, terbufos and paraoxon-methyl were also detected at the deeper soil layers and in the phreatic horizon. The latter pesticides were also detected at significant concentrations in the irrigation water which mainly consisted of riverine water. The lack of an independent soil draining system and the use of riverine water for irrigation purposes resulted in the redistribution of residual amounts of these pesticides in the phreatic horizon beneath the agricultural area.

The potential of pesticides to contaminate the groundwater resources of the Axios river basin. Part II. Monitoring study in the south part of the basin.

A monitoring study was conducted during 1992-1994 in the south part of the Axios river basin, which constitutes one of the main rice-cultivated basins of Greece. The potential of pesticides to contaminate groundwater resources was assessed under realistic agricultural conditions using suction lysimeters. Pesticide residues were also measured in local drainage canals, the phreatic horizon and Axios river. Carbofuran, atrazine, alachlor, prometryne and propanil were regularly detected at concentrations exceeding 1 microg/l in the soil water of deeper soil layers and in the phreatic horizon of the fields. Residues of those pesticides were measured in the soil water and the phreatic horizon of all the studied fields even though they had only been applied in certain fields. This almost uniform distribution of pesticide residues across the whole of the studied area was attributed to rice cultivation. Soil water and its pesticidal content was horizontally transported from saturated soil conditions beneath rice paddies to adjacent corn or cotton-cultivated fields with lower soil moisture contents. The presence of high pesticide concentrations in the water of the Axios river, which was used for the irrigation of the studied area, had probably contributed to the generalized pesticide contamination of the soil water in the studied area. These results suggest that there is a high risk for groundwater contamination in the basin.

Analysis of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil by microwave assisted solvent extraction and subsequent analysis of extracts by on-line solid-phase extraction-liquid chromatography.

A multiresidue method for the determination of phenoxyalkanoic acid herbicides and their phenolic conversion products in soil was developed. The method was based on microwave-assisted solvent extraction (MASE) of soil samples by an aqueous methanolic mixture and subsequent analysis of extracts by automated solid-phase extraction followed by on-line high-performance liquid chromatography and diode array detection. MASE parameters (extraction temperature and time, composition of the extraction mixture and extraction volume) were optimized with respect to analyte recoveries. The method was validated with two types of soils containing 1.5 and 3.5% organic matter, respectively, both types containing fresh and aged residues of sought analytes. Under the selected analytical conditions when soils with fresh residues were analyzed all target analytes were recovered above 80% from the soil containing 1.5% organic matter, while limits of identification at the level of 20-40 ng/g were achieved. From the soil containing 3.5% organic matter the least polar phenolic analytes exhibited slightly reduced recoveries, while identification limits of 30-50 ng/g were achieved. Samples with aged residues exhibited reduced recoveries for some analytes, the reduction amounting up to 6-12% within 1 month of aging period depending on soil organic matter.

Automated trace level determination of glyphosate and aminomethyl phosphonic acid in water by on-line anion-exchange solid-phase extraction followed by cation-exchange liquid chromatography and post-column derivatization.

An automated method based on the on-line coupling of anion-exchange solid-phase extraction (SPE) and cation-exchange liquid chromatography followed by post-column derivatization and fluorescence detection has been developed for the trace level determination of glyphosate and its primary conversion product aminomethyl phosphonic acid (AMPA) in water. PRP-X100 poly(styrene-divinylbenzene)-trimethylammonium anion-exchange cartridges (20 x 2 mm, 10 microm) were selected for the SPE of glyphosate and AMPA. The ionic compounds present in the samples strongly influenced the extraction of both analytes; however, when an on-line ion-exchange clean-up step was introduced before sample SPE, the problem was largely solved. By processing 100-ml samples detection limits better than 0.02 microg/l for glyphosate and 0.1 microg/l for AMPA were achieved in river water. Both analytes were unstable in solution and the approach of storing samples on the PRP-X100 SPE cartridges was evaluated for a period of 1 month under three different storage conditions (deep freeze, refrigeration and 20 degrees C).

Use of an automated on-line SPE-HPLC method to monitor caffeine and selected aniline and phenol compounds in aquatic systems of Macedonia-Thrace, Greece.

Caffeine and selected aniline and phenol compounds have been monitored in the river, lake, and ground water of Northern Greece (Macedonia-Thrace) from September 1999 to December 2000 by means of a fully automated on-line SPE-HPLC method. Among the target aniline and phenol compounds the most abundant was 2,6-di-tert-butyl-4-methylphenol, which was found to be present in both surface and ground water samples. Caffeine was also very frequently present in river and ground water, although its presence in lake water was rare. Caffeine and 2,6-di-tert-butyl-4-methylphenol were also monitored by off-line SPE of water samples and GC-ion-trap MS analysis of extracts.

Development of an automated on-line solid-phase extraction-high-performance liquid chromatographic method for the analysis of aniline, phenol, caffeine and various selected substituted aniline and phenol compounds in aqueous matrices.

A fully automated solid-phase extraction (SPE)-high-performance liquid chromatographic method has been developed for the simultaneous analysis of substituted anilines and phenols in aqueous matrices at the low- to sub-microg/l level. Diode array and electrochemical detection operated in tandem mode were used for analyte detection. Two new polymeric sorbent materials (Hysphere-GP and Hysphere-SH) were evaluated for the on-line SPE of substituted anilines and phenols from aqueous matrices and their performance was compared with the PRP-1 and PLRP-S sorbents. Hysphere-GP sorbent packed in 10 x 2 mm cartridges was found to give better results in terms of sensitivity and selectivity of the overall analytical method. The proposed analytical method was validated for the analysis of these compounds in Axios river water that receives industrial, communal and agricultural wastes. The detection limits for all the compounds range between 0.05 and 0.2 microg/l, except for aniline and phenol which have detection limits of 0.5 and 1 microg/l, respectively (aniline detected by electrochemical detection). The recoveries for all the compounds are higher than 75% except for aniline (6%), phenol (50%) and 3-chlorophenol (67%). Finally, in order to evaluate the efficiency of the Hysphere-GP (10 x 2 mm) cartridges for sample stabilization and storage, the stability of the compounds of interest at the sorbed state onto these cartridges has been evaluated under three different temperature regimes (deep freeze, refrigeration, 20 degrees C).

A fully automated system for analysis of pesticides in water: on-line extraction followed by liquid chromatography-tandem photodiode array/postcolumn derivatization/fluorescence detection.

A fully automated system for on-line solid phase extraction (SPE) followed by high-performance liquid chromatography (HPLC) with tandem detection with a photodiode array detector and a fluorescence detector (after postcolumn derivatization) was developed for analysis of many chemical classes of pesticides and their major conversion products in aquatic systems. An automated on-line-SPE system (Prospekt) operated with reversed-phase cartridges (PRP-1) extracts analytes from 100 mL acidified (pH = 3) filtered water sample. On-line HPLC analysis is performed with a 15 cm C18 analytical column eluted with a mobile phase of phosphate (pH = 3)-acetonitrile in 25 min linear gradient mode. Solutes are detected by tandem diode array/derivatization/fluorescence detection. The system is controlled and monitored by a single computer operated with Millenium software. Recoveries of most analytes in samples fortified at 1 microgram/L are > 90%, with relative standard deviation values of < 5%. For a few very polar analytes, mostly N-methylcarbamoyloximes (i.e., aldicarb sulfone, methomyl, and oxamyl), recoveries are < 20%. However, for these compounds, as well as for the rest of the N-methylcarbamates except for aldicarb sulfoxide and butoxycarboxim, the limits of detection (LODs) are 0.005-0.05 microgram/L. LODs for aldicarb sulfoxide and butoxycarboxim are 0.2 and 0.1 microgram, respectively. LODs for the rest of the analytes except 4-nitrophenol, bentazone, captan, decamethrin, and MCPA are 0.05-0.1 microgram/L. LODs for the latter compounds are 0.2-1.0 microgram/L. The system can be operated unattended.