Regression models for octanol‐water partition coefficients,and for bioconcentration in fish

Octanol‐water partition coefficients (P) of a number of organochlorine insecticides (OCs) are presented. The merits of log‐log regressions between experimental ? values and calculated estimates of P, solute activity coefficients in water, solute molecular surface area data, and reversed‐phase liquid‐chromatographic net retention data, are critically evaluated for several classes of pollutants: polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes, chlorinated biphenyls and OCs. Special attention is paid to the predictive accuracy of such semi‐empirical regressions in connection with possible effects of solute molecular shape and polarity.

Finally, bioconcentration and ‐accumulation of hydrophobic pollutants in fish are briefly discussed.     

Sorption‐desorption kinetics of some organochlorine insecticides in silt‐water suspensions

Kinetic (batch) sorption and desorption experiments for some organochlorine insecticides in silt‐water suspensions are described. The effect of possible experimental artifacts on the results is examined. The influence of the silt/water ratio on the linear sorption coefficient and on the “nonextractable”; solute fraction is determined. The sorption process is described in terms of some kinetic models.     

Cleanup by solid‐phase extraction and HPLC of organochlorine insecticides and PCBS in various nonfatty and fatty samples

An accurate, simple and cheap extraction and cleanup procedure for capillary GC analysis of organo‐chlorine insecticides (OCs) in vegetables (cabbage and carrots) at the ng/g level, and for soil at the μg/g level is presented. The cleanup is carried out on solid‐phase extraction (SPE) cartridges, filled with 500 mg silica, 1 g of deactivated Florisil (10% w/w water), and 100 mg of anhydrous sodium sulphate. Recoveries >90% are obtained. The cleanup of OCs in fatty samples on an HPLC LiChrosorb Si 100 column is evaluated for subsequent capillary GC analysis. Fractionation of OCs and Aroclor 1254 and 1260 on an HPLC Nucleosil 100 column appears to be satisfactory.     

Diazinon leaching through a sandy soil amended with different humic materials

The water leaching of diazinon (O,O‐diethyl‐O‐2‐isopropyl‐6‐methylpyrirnidin‐4‐yl phosphoroth‐ioate) through soil columns, was studied after column amendments with two well characterized humic acids (HA), in both liquid and solid state, and with the original raw organic materials, an oxidized coal and a leonardite, from which the HA were extracted. The percolation curves and the pesticide distribution over the soil columns showed that the addition of the raw organic materials and the solid HAs reduced significantly the mobility of the pesticide along the soil column. The oxidized coal was more effective than the leonardite original material; the different origin of the two carbon‐rich materials had an influence on the diazinon movement along the soil columns and such difference was enhanced with increasing addition rates. Moreover, incubation at field capacity for two months of the soil columns treated with raw oxidized coal and leonardite, largely enhanced the described effects on pesticide behaviour. A complete adsorption of diazinon on columns and a practical absence of leaching was observed when the HA from both materials were added in dissolved form. These results were explained with the swelling of the humic micelles in water and the enhanced availability of inner hydrophobic surfaces for the strong adsorption of diazinon. The water diffusion into the solid humic materials after two months incubation, also explains their high pesticide retention capacity. This work indicates the usefulness of either solid o dissolved humic substances, with the proper hydrophobic character, in preventing the vertical leaching of non‐polar organic pesticides in soils.     

Ground water pollution by pesticides at the watershed‐soil catena scale: Lindane at the lower Colorado river basin (Argentina)

The movement of Lindane from application points at the surface soil towards the underground water and further transport within this compartment at the watershed‐soil catena scale, was inspected by measurements of the pesticide concentration in soil water at a controlled experiment where it was applied at a usual label dose. The concentrations of Lindane in soil water and the upper phreatic level were also measured at successive dates in samples obtained from a net of phreatimeter probes distributed over the area (1,500 km²) of the lower Colorado River basin (Bs. Aires, Argentina). The location of cultivated‐irrigated areas within the watershed was inferred from NDVI (Normalized Difference Vegetation Index)‐1 km‐10 day AVHRR images obtained at successive dates during the irrigation season. Feasible paths of underground gravitational water flows were computed by means of a GIS‐simulation model on the basis of local terrain slopes and aspects. The pattern of Lindane distribution over the basin was explained on the basis of the distribution of diffuse sources, the patterns of percolation and groundwater flows and the thermodynamic characteristics of the pesticide.     

Removal of pesticides from water samples by adsorption with fatty acids supported on barium sulphate

Oleic or linoleic acid supported on barium sulphate was used to remove atrazine and terbuthylazine in the range of 0.1–2.0 μg/L using spiked water samples. The sorption of atrazine depends on the stirring time and the best value is 150 min. Terbuthylazine is removed well with a stirring time of 60 min and its adsorption is about 90%. Detection of the residual pesticide in treated waters, after solid phase extraction (SPE), was carried out by GC‐MS operating in selected ion monitoring (SIM) using a calibration curve by direct injection of standard solutions of herbicide.     

Preliminary toxicity evaluation of water from rice fields using cost‐effective microbiotests

A study was performed in a Protected Area (Natural Reserve of Sado Estuary) in 1996, to evaluate the acute toxicity for aquatic life of surface water from rice fields treated with pesticides, particularly with molinate and quinclorac. As a preliminary assessment, the following rapid toxicity tests were used: “Rotoxkit F”;, “Thamnotoxkit F”; and the recently introduced “Daphtoxkit F magna”; and “Algaltoxkit F”;. Water samples were collected from: a water source for irrigating the rice fields, two rice plots, a drainage channel and from Sado river in which the water is discharged. The results showed that samples from the rice plot treated with molinate were more toxic than those obtained from rice plot treated with quinclorac. Water samples from the river were the most toxic, causing 100% of immobility in all organisms and a substantial inhibition in the algal growth. Water collected from the drainage channel in late July, was also found to be quite toxic. The results obtained until now indicate that some characteristics of these microbiotests, like their rapidity, simplicity and relatively low cost, make them a practical tool to evaluate acute effects of pesticides in freshwater ecosystems. They may also contribute to suggest some changes in pesticides use to promote agricultural practices with lower impact to aquatic life.     

Evaluation of linear alkylbenzenesulfonate (LAS) biodegradability in sediment by solid‐phase extraction and HPLC analysis

The linear alkylbenzenesulfonate (LAS) sorption on environmental sediments has been known long ago. Their high concentrations reflect the massive input of these chemicals from household and industrial uses. However few attempts were made to identify biodegradation metabolites of LAS in sediment. In this report, a method for the determination of these compounds in sediment samples by high‐performance liquid chromatography (HPLC) is described. The first step of our work was performed by solid‐phase extraction with octadecyl‐bonded silica (C18) mini‐columns and provided a suitable recovery of LAS (90 ± 5%) and most metabolites. Furthermore, laboratory investigations led to study the behaviour of LAS in sediment. The environmental samples used for this purpose were collected from a pond (named étang de Bolmon) located in the French Mediterranean coast. Our results were in agreement with an aerobic biodegradation process of LAS that occurred only with high values of sediment redox potential and needed the samples to be vigorously shaken to ensure adequate mixing and suspension of particulate material. In a stagnant sediment or under anaerobic conditions, LAS is not degraded. p‐Sulfophenylacetic acid and p‐sulfocinnamic acid were evidenced as predominant metabolites and were found not to be persistent.     

Determination and QSPR analysis of log Kow and log Koc for fluorine containing benzene derivatives

Octanol‐water partition coefficients (Kow) and soil organic carbon sorption coefficients (Koc) were determined for 14 fluorinated benzene derivatives. Quantitative structure‐property relationships were developed using molecular connectivity indices and quantum chemical parameters to analyze the most significant factors influencing these physico‐chemical properties of the compounds. The substitution by F in benzene derivatives has greater influence on Koc than on Kow.     

Recovery of seven kinds of cfc and cfc replacements on high‐surface area activated carbon

The adsorption isotherms, the constants of the Dubinin—Radushkevich plots, and the constants of the Langmuir plots of chlorofluorocarbon (CFC) and CFC replacements on high‐surface area activated carbon were investigated to estimate the recovery efficiency of CFC and CFC replacements. The adsorption and desorption of HFC134a on a high‐surface area activated carbon was much easier than that of CFC 113 and the CFC replacements. The recovery efficiency of CFC replacements depends on the hydrogen atoms in molecule. It is possible that the saturated amount adsorbed in the pores or on the surface of the activated carbon could be evaluated by the W_s constant of the the Langmuir equation and the W_o constant of the Dubinin‐Radushkevich equation. The a constant of the Langmuir equation and the BE_o constant of the Dubinin‐Radushkevich equation depend on the molecular composition.