Sanja Fingler

Analysis of polychlorinated biphenyls, organochlorine pesticides and chlorophenols in rain and snow

Polychlorinated biphenyls (PCBs), organochlorine pesticides and chlorophenols were measured in samples of rain and snow collected at urban and suburban/semi-rural locations in the Zagreb City area, Croatia. PCBs and organochlorine pesticides were extracted with hexane from filtered aqueous samples and from particulate matter isolated by filtration. Chlorophenols were accumulated from rain and snow water by C18 reversed-phase adsorption. All samples were analysed by capillary gas chromatography using an electron-capture detector. Polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs) in rain and snow water were checked by gas chromatographic–mass spectrometric analysis of combined hexane extracts. PCBs were detected in all water (<1–203 ng l–1) and particle (40–4155 ng g–1) samples. The only organochlorine pesticide present in all rain and snow water (1–36 ng l–1) and in particle (7–512 ng g–1) samples was γ-hexachlorocyclohexane as a consequence of the regular local usage of lindane. A positive correlation was found between its concentration in the water phase and the average air temperature during the sampling period. Compounds of the DDT-type, trace amounts of which were detected in only two rain water samples, were determined in most particle samples. The DDE : DDT median concentration ratio in particles was lower than unity and indicated a recent input of DDT into the atmosphere. The incidence and concentrations of di-, tri-, tetra- and pentachlorophenols were higher in snow (single compound concentration 11–527 ng l–1) than in rain (single compound concentration 2–171 ng l–1). A quadratic decrease in chlorophenol concentrations in snow and rain with increasing air temperature was observed. Trace amounts of PCDDs and PCDFs were detected in both rain and snow water samples and the highest concentrations were measured for octa-CDD (2 pg l–1 in snow and 6 pg l–1 in rain).

Levels of atrazine and simazine in waters in the rural and urban areas of North-West Croatia

The triazine herbicides atrazine and simazine were measured in samples of surface, ground, drinking and rain/snow waters collected in the 1992–2001 period in rural areas north-west of Zagreb city and in the city area. Atrazine was detected in 367 and simazine in 40 out of the 477 water samples analysed. The highest atrazine concentrations (up to 8.28 µg L−1) were measured in surface waters from the rural area in the 1992–1995 period. In the later sampling period (2001) a decreasing trend in atrazine concentrations was observed in surface and ground waters collected from privately owned wells. However, there were no great variations in levels of atrazine in drinking waters in either the rural or the urban area. The atrazine concentration exceeded 0.1 µg L−1 in 29% of drinking water samples, reflecting the contamination of ground waters serving as drinking water supplies. The sorption intensity of atrazine and simazine was tested in soil and aquifer sediments collected close to the wells used for the public water supply systems. The values of Freundlich K f sorption coefficients indicated more efficient retention of compounds in the surface soil and in the aquitard layer than within the three aquifer porous ground water layers of more or less balanced gravel, sand, and silt content and with 0.99–1.5% of organic matter. The incidence and concentrations (<0.01–0.18 µg L−1) in rain/snow samples collected in the Zagreb city and at a rural site about 20 km north-west of the city centre indicated that atmospheric transport was also involved in atrazine environmental distribution.

Sorption behaviour of some chlorophenols in natural sorbents. 1. Validity of the partition model for sorption of phenolates

Abstract In order to verify the validity of the partition model for describing the sorption behaviour of hydrophobic but ionizable polar compounds in natural sorbents, a series of experiments was carried out in which three chlorophenols: 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol, were sorbed in 14 different soil and sediment samples. Freundlich isotherm coefficients K f and 1 n were calculated for all three compounds in all sorbents and compared with those favouring phenolate forms. The sorption coefficients K f were closely related to the total sorbent organic matter content with a high correlation coefficient. However, isotherm non-linearities were observed in almost all experiments. The removal of the sorbent organic matter from the three tested sorbents drastically decreased the sorption intensity in two of them, but considerably increased it in the third, indicating that interaction with the mineral surface could be much stronger than sorption in the organic phase. These results indicate that the simplified partition concept used for the sorption of non-polar compounds might not offer an adequate description of the sorption behaviour of chlorophenolates in natural sorbents.

Sorption behaviour of chlorophenols and triazine herbicides in reference euro-soils

The influence of different soil sorption-controlling properties on sorption behaviour of chlorophenols (2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol and pentachlorophenol) and triazine herbicides (chlorotriazines atrazine and simazine, and methylthiotriazines ametryn and prometryn) in natural sorbents was studied. Experiments were carried out with six European reference soils differing in soil organic matter content (SOM), grain size distribution, cation exchange capacity, and acidity, as well as in silt, clay, sand, iron oxide and aluminium oxide content. Freundlich isotherm coefficients K f and 1/n as well as organic matter sorption coefficient and free energy change were calculated for all compounds in all sorbents. The sorption intensity for chlorophenols increased with increase of SOM, cation exchange capacity and sorbent sand content and decreased with increase of sorbent pH, silt and clay content. For chlorotriazines atrazine and simazine, statistically significant positive correlation between K f sorption coefficients and SOM was obtained and the sorption was also favoured by lower content of coarse- and medium-grainy fractions of silt.

A comparative study of trace enrichment of chlorophenols in water by extraction with C6 and C8 alkanes and by C18 reversed-phase adsorption

The efficiency, reproducibility and sensitivity ofn-hexane and iso-octane extraction and of C18 reversed-phase adsorption for accumulation of 4-chloro-, 2,4-dichloro-, 2,4,5- and 2,4,6-trichloro-, 2,3,4,6-tetrachloro- and pentachlorophenol from aqueous solutions were compared. In extraction procedures the acetyl and pentafluorobenzoyl derivatives of chlorophenols were extracted from water. In adsorption procedure chlorophenols adsorbed on a Sep-Pak C18 cartridge were eluted with acetone and after that derivatized analogously.All three procedures were found to be applicable for an efficient trace enrichment of chlorophenols in water, the proper choice being dependent on the required sensitivity of the analysis. Lower detection limits of single compounds at ≈10 ng·1−1 levels were achieved by adsorption procedure owing to the more uniform and for most chlorophenols higher adsorption than extraction recoveries as well as owing to the possibility of treating larger volumes of water samples. The extraction procedure could be successfully applied to the concentrations of chlorophenols in water ≥1μg·1−1.Owing to its higher efficiency and better sensitivity the C18 reversed-phase adsorption procedure was chosen as the more suitable one for the determination of chlorophenol levels in surface, ground and drinking waters. The conversion of chlorophenols accumulated from a water sample parallel to both acetyl and pentafluorobenzoyl derivatives and the analysis of both types of derivatives on two basically different gas Chromatographic columns were recommended for a more reliable identification and quantitation of the compounds analyzed.

Trace enrichment of chlorophenols in human urine by C18 reversed-phase adsorption and by n-hexane extraction

SummaryThe efficiency and sensitivity of C18 reversed-phase adsorption of free chlorophenols and of n-hexane extraction of either free or acetylated chlorophenols from human urine were compared. All procedures were found to be efficient for the trace enrichment of 2,4-dichlorophenol, 2,4,6- and 2,4,5-trichlorophenols, 2,3,4,6- and 2,3,4,5-tetrachlorophenols and pentachlorophenol. The recoveries of chlorophenols from non-hydrolysed and acid hydrolysed urine samples were comparable. By treatment of 1 ml urine sample detection limits of 1–2 ng/ml were achieved, while the treatment of 5 ml samples enhanced the detection sensitivity to less than 1 ng/ml. The n-hexane extraction of acetylated chlorophenols from 1 ml urine samples is the simplest and fastest procedure because the acetylation and extraction of chlorophenols are performed simultaneously in one step. The C18 adsorption seems to be more suitable than n-hexane extraction for accumulation of chlorophenols from a urine volume of 5 ml and higher because the elution is performed always with the same small volume of acetone. Both C18 adsorption and n-hexane extraction procedures were applied for analysis of chlorophenols in general population and in persons with possible occupational exposure to organochlorine compounds.

Persistent organochlorine compounds in water and soil environments

Reviews compound physico‐chemical properties and water and soil properties influencing the transport and distribution of organochlorine pesticides, polychlorinated biphenyls (PCBs) and chlorophenols in a water and soil environment. As highly hydrophobic compounds of low water solubility, organochlorine pesticides and PCBs are rapidly and strongly sorbed by most soils and sediments. The sorption of weakly acidic chlorophenols comprises both molecular and ionic forms and depends not only on the soil/sediment organic matter content but also on the pH and ionic strength of the aqueous phase. Briefly describes the analytical methods for trace analysis of organocholorine pesticides, PCBs and chlorophenols in water and soil/sediment samples. Presents some results of those micropollutants’ analysis in surface, ground and drinking waters, soils, river sediments and wet depositions in Croatia.

The impact of multiple anthropogenic contaminants on the terrestrial environment of the Plitvice Lakes National Park, Croatia

The anthropogenic impact on the terrestrial environment of the Plitvice Lakes National Park (PLNP) was investigated through the analysis of three groups of major contaminants (persistent organochlorine pollutants including 15 organochlorine pesticides (OCPs) and 17 polychlorinated biphenyls (PCBs), trace elements/heavy metals (6 major and 23 trace constituents), and anthropogenic radionuclides (90Sr, 134Cs, and 137Cs)) in three terrestrial compartments (soil, air, and bioindicators of air contamination) during 2011–2013. The correlation coefficients of element mass fractions with soil properties indicated that total Fe and Al minerals, soil organic matter (OM), and organic carbon (OC) content affected the mass fractions of most trace elements in the topsoils. The annual and spatial distributions of heavy metals in total deposited matter (TDM) indicated that the metals came from natural sources and long-range transfer of particulate matter. The PCB and OCP levels found in soil and conifer needles corresponded to global environmental pollution levels by persistent organic pollutants and represented the lower end of the mass fraction ranges reported in the relevant literature. Analyses of anthropogenic radionuclides in bioindicators (conifer needles, lichens, and mosses) showed low but measurable activity concentrations of 134Cs (for the first time after the Chernobyl accident), which indicated origin from the March 2011 Fukushima Nuclear Power Plant accident. Our overall results indicated that human activity inside or near the PLNP had no significant impact either on contaminant spread by air or on their content in topsoils.

Dissipation dynamics of terbuthylazine in soil during the maize growing season

Abstract Ever since terbuthylazine (TBA) replaced atrazine in herbicide crop treatment, its much greater persistence has raised considerable environmental concern. The aim of our field experiment was to establish the dissipation dynamics of TBA and its degradation product desethylterbuthylazine (DET) in soil over five months of maize growth. We applied TBA as part of pre-emergent treatment in the regular and double-the-regular amounts. Soil samples were collected periodically at the following depths: 0-10 cm, 10-20 cm, 20-30 cm, and 30-50 cm. For TBA and DET soil residue analysis we used microwave-assisted extraction with methanol, followed by HPLC-UV/DAD. Regardless of the application rate, more than 80 % of the applied TBA dissipated from the first 50 cm of soil in the two months after herbicide application and 120 mm of rainfall. Three months later (at maize harvest), less than 4 % of total TBA remained in the soil, mostly in the top 20 cm rich with organic carbon on which TBA is likelier to adsorb. The loss of TBA from soil coincided with the rise in DET, especially the top soil layers, during the periods of low rainfall and highest soil temperatures. This points to biodegradation as the main route of TBA dissipation in humic soils. The applied amount had no significant effect on TBA dissipation in the top (humic) layers, but in the layers with less than 1 % of organic carbon, it was higher when the doublethe- regular dose was applied.