Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Studying soil organic matter using 13C CP-MAS NMR: the effect of soil chemical pre-treatments on spectra quality and representativity

¹³C CP-MAS NMR spectroscopy is a technique that has proved to be useful in studying soil organic matter (SOM). Nevertheless, NMR spectra exhibit a weak signal and have very low resolution due to: the low natural abundance of ¹³C (1.1 % of C) in SOM, the generally low SOM content of soils, and the presence of paramagnetic impurities. This paper studies the effects of soil chemical pre-treatments on ¹³CP-MAS NMR spectra quality and spectra representativity i.e. soil C mass balance.

After chemical pre-treatment to increase total organic carbon (TOC) content and C/Fe ratio, eight soils characterized by different levels of organic carbon content and C/Fe ratios were studied using ¹³CP-MAS NMR. Moreover, where chemical treatments were not applicable due to high carbon losses, the number of ¹³CP-MAS NMR scans was increased in order to obtain satisfactory spectra.

Results show that chemical pre-treatment of soils with C/Fe > 1 caused high C losses. Bulk soils were therefore studied by increasing the number of ¹³CP-MAS NMR scans. Acceptable spectra were obtained from 8K scans (1K = 1024 transient). On the other hand, even when a large number of scan (32K) are used, soil with C/Fe < 1 cannot be studied. As these soils are characterized by low C losses after HCl treatments (range of 2.9–25.4%), a pre-treatment of at least 1.39 mol l⁻¹ HCl removes excess Fe and at the same time increases C/Fe ratio resulting in 32K scans providing good spectra.     

Physico-chemical versus microbial release of c-atrazine bound residues from a loamy clay soil incubated in laboratory microcosms

A loamy clay soil containing unextractable ¹⁴C-ring labeled atrazine residues was incubated in microcosms under abiotic and biotic conditions. The mineralization activity of the soil microflora was evaluated by the release of total CO₂ and ¹⁴C0₂. After 63 days of sample incubation the total organic carbon mineralization was of 1.71%, that of ¹⁴C-residues was of 0.72% of the initial radioactivity. No direct relationship was established between the mineralization of atrazine residues and the global mineralization. The contribution of soil microorganisms in the release of ¹⁴C-residues was weak. The availability of non-extractable residues was mainly controlled by physico-chemical factors. The low value of the reextractability rate and the distribution of bound residues during the soil sample incubation shown the active role of organic matter in detoxification procedure. Ninety percent of the residues remained bound after 63 days of incubation and were thus, potentially available without biocide activity.

The fractionation of soil organic matter allowed to specify the distribution of bound residues within the organic compartments. After a long-stay of pesticides in soils, approximately 65% of bound residues were associated with humin.     

Transformation products distribution of atrazine in corn plants treated with radiolabelled herbicide

Roots of whole plants at four leaf stage grown in specialized soil treatment vessels were treated with ¹⁴C-atrazine. Plant tissues were exhaustively extracted with methanol and extracts were separated by preparative thin layer chromatography (TLC). The extracted material was separated in two TLC bands at Rf0.00 and Rf0.18 containing 33% and 67% of plant ¹⁴C-residues, respectively. Methanol extracts of these bands subjected to derivatization, hydrolysis and analysis by TLC, revealed the presence of a number of transformation products consisting of hydroxy analogues of atrazine and their dealkylated metabolites. The transformation products had variable distribution patterns amongst leaf, stalk and root tissues. Diaminohydroxyatrazine, hydroxyatrazine, and deethylhydroxyatrazine were the main ¹⁴C-residues. Stalk tissue contained more ¹⁴C-residues which were largely located at and just below the ligule. The significance of ¹⁴C-residue accumulation at the ligule and the transformation product compartmentalization are discussed.     

Chemical and biological characterization of non-extractable sulfonamide residues in soil

For sulfonamides, the formation of non-extractable residues has been identified by laboratory testing as the most relevant concentration determining process in manured soil. Therefore, the present study has been focused on the chemical and biological characterization of non-extractable residues of ¹⁴C-labeled sulfadiazine or sulfamethoxazole. In laboratory batch experiments, the test substances were spiked via standard solution or test slurry to microbially active soil samples. After incubation periods of up to 102 d, a sequential extraction technique was applied. Despite the exhaustive extraction procedure, sulfadiazine residues mainly remained non-extractable, indicating the high affinity to the soil matrix. The remobilization of non-extractable ¹⁴C-sulfadiazine residues was monitored in the activated sludge test and the Brassica rapa test. Only small amounts (<3%) were transferred into the extractable fractions and 0.1% was taken up by the plants. In the Lumbricus terrestris test A, the release of non-extractable ¹⁴C-sulfamethoxazole residues by the burrowing activity of the earthworms was investigated. The residues mainly remained non-extractable (96%). The L. terrestris test B was designed to study the immobilization of ¹⁴C-sulfamethoxazole in soil directly after the test slurry application. The mean uptake by earthworms was 1%. Extractable and non-extractable residues amounted to 5% and 93%, respectively. Consequently, the results of all tests confirmed the high affinity of the non-extractable sulfonamide residues to the soil matrix.     

Pharmacok inetics and metabolism of 1,2,3,7,8-pentachlorodibenzo-p-dioxin in the rat

¹⁴C-1,2,3,7,8-Pentachloroaibenzodioxin (P₅CDD), administered to rats as single oral dose (1.69–1.75 μg/animal, 8.42–10.06 μg/kg) was eliminated with a half life of 29.5±2.7 days from the body of the animals. Residual P₅CDD was located mainly in the liver and the adipose tissue. In the bile, polar metabolites of P₅CDD were detected but no unmetabolized P₅CDD.     

Stimulation of reductive dechlorination of hexachlorobenzene in soil by inducing the native microbial activity

The reductive dechlorination and behaviour of ¹⁴C-hexachlorobenzene (HCB) was investigated in an arable soil. The activity of the native anaerobic microbial communities could be induced by saturating the soil with water. Under these conditions high rates of dechlorination were observed. After 20 weeks of incubation only 1% of the applied ¹⁴C-HCB could be detected in the fraction of extractable residues. Additional organic substances, like wheat straw and lucerne straw, however considerably delayed and reduced the dechlorination process in the soil. The decline of HCB was not only caused by dechlorination but also by the formation of non-extractable residues, whereby their amounts varied with time depending on the experimental conditions. Several dechlorination products were detected, indicating the following main HCB transformation pathway: HCB → PCB → 1,2,3,5-TeCB → 1,3,5-TCB → 1,3-DCB, with 1,3,5-TCB as main intermediate dechlorination product. The other TeCB-, TCB- and DCB-isomers were also detected in low amounts, showing the presence of more than one dechlorination pathway. Since the methane production rates were lowest when the dechlorination rates were highest, it can be assumed that methanogenic bacteria were not involved in the dechlorination process of HCB. The established ¹⁴C-mass balances show, that with increasing dechlorination and incubation times, the ¹⁴C-recoveries decreased.     

Micro-scale bromination procedure for synthesis of “2,3,7,8-substituted” brominated dibenzo-p-dioxins and dibenzofurans from [C]-labeled precursors

Brominated dibenzo-p-dioxin and dibenzofuran (BDD/BDF) isomers, specifically having from one to three halogens located in the 2,3,7,8-substituent positions, that are [¹³C]-labeled for use as analytical internal standards in mass spectrometric methods are not yet commercially available. Based upon the current availability of [¹³C]-labeled dibenzo-p-dioxin and dibenzofuran (DD/DF) precursors, we have developed a simple and efficient synthetic procedure which produces brominated congeners that are predominantly substituted in the 2,3,7, and 8-positions. The gas/solid reaction of vaporized precursor and surface-supported iron (III) bromide occurs rapidly (seconds) at temperatures ≥ 240°C and can provide total product yields in the range of 30 to 50 mole % for initial precursor amounts between 1 μg and 10 mg. In this paper we shall describe the utility of this approach to produce 5 μg quantities of [¹³C₁₂]-2,7-dibromodibenzo-p-dioxin (27-DBDD) and [¹³C₁₂]-2,8-dibromodibenzo-p-dioxin (28-DBDD).     

Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

Physicochemical soil parameters affecting sequestration and mycobacterial biodegradation of polycyclic aromatic hydrocarbons in soil

Six soils, obtained from grasslands and wooded areas in Northeastern Illinois, were physicochemically characterized. Measured parameters included total organic carbon (TOC) content, contents of humic acid, fulvic acid and humin, pore volume and pore size distribution, and chemical makeup of soil organic matter (determined using solid-state ¹³C-NMR). Moistened, gamma-sterilized soils were spiked with 200 ppm of either phenanthrene or pyrene (including ¹⁴C label); following 0, 40, or 120 days of aging, the contaminant-spiked soils were then inoculated with Mycobacterium austroafricanum strain GTI-23, and evolution of ¹⁴CO₂ was assessed over a 28-day period. Results for both phenanthrene and pyrene indicated that increased contact time led to increased sequestration and reduced biodegradation, and that TOC content was the most important parameter governing these processes. One soil, although only tested with phenanthrene, showed significantly lower-than-expected sequestration (higher-than-expected mineralization) after 40 days of aging, despite a very high TOC value (>24%). Because the level of sequestration in this soil was proportional to the others after 120 days of aging, this implies some difference in the temporal progression of sequestration in this soil, although not in its final result. The primary distinguishing feature of this soil was its considerably elevated fulvic acid content. Further experiments showed that addition of exogenous fulvic acid to a soil with very low endogenous humic acids/fulvic acids content greatly enhanced pyrene mineralization by M. austroafricanum. Extractabilities of 13 three- to six-ring coal tar PAHs in n-butanol from the six soils after 120 days of sequestration were strongly TOC-dependent; however, there was no discernible correlation between n-butanol extractability and mycobacterial PAH mineralization.     

The enhancement of photodegradation efficiency using Pt-TiO2 catalyst

The residues from the extraction of lead/zinc (Pb/Zn) ores of most Pb/Zn mines are permanently stored in tailings ponds, which require revegetation to reduce their environmental impact. This can only be done if the main constraints on plant establishment are evaluated. This can readily be done by field and greenhouse studies.

To test this, the properties of different tailings from Lechang Pb/Zn mine located at the north of Guangdong Province in southern China have been studied. Physical and chemical properties including concentrations of metals (Pb, Zn, Cd and Cu) in the tailings and soils collected from different sites have been measured. The results showed that tailings contain low nitrogen (0.016–0.075%), low-organic matter (0.58–1.78%), high salt (3.55–13.85 dS/m), and high total and diethylene–tetramine–pentaacetic acid (DTPA)-extractable metal concentrations (total: 1019–1642 μg g⁻¹ Pb, 3078–6773 μg g⁻¹ Zn, 8–23 μg g⁻¹ Cd, and 85–192 μg g⁻¹ Cu; DTPA-extractable: 59–178 μg g⁻¹ Pb, 21–200 μg g⁻¹ Zn, 0.30–1.5 μg g⁻¹ Cd, and 4.3–12 μg g⁻¹ Cu). Aqueous extracts of tailings/soils (10%, 20% and 30%, w/v) from different sites were prepared for testing their effects on seed germination and root elongation of a vegetable crop Brassica chinensis and a grass species Cynodon dactylon. It was found that root elongation provided a better evaluation of toxicity than seed germination. The ranking of toxicity using root elongation was: high-sulfur tailings>tailingdam>sparsely vegetated tailings>densely vegetated tailings>mountain soil for both plants. This order was consistent with DTPA-extractable Pb contents in the tailings and soils. B. chinensis seedlings were then grown in the mixtures of different proportions of tailings and farm soil for 4 weeks, and the results (dry weights of seedlings) were in line with the root elongation test. All these demonstrated that heavy metal toxicity, especially available Pb, low content of nutrient, and poor physical structure were major constraints on plant establishment and colonization on the Pb/Zn mine tailings.     

Relationship between electron donor and microorganism on the dechlorination of carbon tetrachloride by an anaerobic enrichment culture

An investigation involving the supplement of different concentrations of substrates and microorganisms was carried out under anaerobic condition to assess the feasibility of bioremediation of carbon tetrachloride (CCl₄) with the amendment of low concentrations of auxiliary substrate and microorganisms. The concentrations of substrate and microorganisms ranged from 10 to 100 mg/l and from 3.7 × 10⁴ to 3.7 × 10⁶ cell/ml, respectively. The biotransformation rate of CCl₄ increased progressively with the increase in the concentrations of the substrate and microorganisms. In the low biomass-amended system (3.7 × 10⁴cells/ml), 28–71% and 57–96% of CCl₄ removals were exhibited when 10–100 mg/l of acetate or glucose was supplemented, respectively, whereas nearly complete degradation of CCl₄ was observed in the heavily inoculated systems (3.7 × 10⁶ cells/ml). An addition of electron donor in the low microbial activity batches enhanced greater efficiency in dechlorination than in the high microbial activity batches. The second-order rate constants ranged from 0.0059 to 0.0092 l/mg/day in high biomass input system, while a two- to four-fold increase in rate constant was obtained in the low microbial activity system. This study indicates that biomass was the more important environmental parameter than substrate affecting the fate of CCl₄. The addition of auxiliary substrates was effective only in low biomass-amended batches (0.56 mg-VSS/l) and diminished inversely with the increase of microbial concentration.     

Role of dissolved humic acids in the biodegradation of a single isomer of nonylphenol by Sphingomonas sp

This study shows the important role of humic acids in the degradation of ¹⁴C and ¹³C labeled isomer of NP by Sphingomonas sp. strain TTNP3 and the detoxification of the resulting metabolites. Due to the association of NP with humic acids, its solubility in the medium was enhanced and the extent of mineralization of nonylphenol increased from 20% to above 35%. This was accompanied by the formation of significant amounts of NP residues bound to the humic acids, which also occurred via abiotic reactions of the major NP metabolite hydroquinone with the humic acids. Gel permeation chromatography showed a non-homogenous distribution of NP residues with humic acids molecules, with preference towards molecules with high-molecular-weight. Solid state ¹³C nuclear magnetic resonance spectroscopy indicated that the nonextractable residues resulted exclusively from the metabolites. The chemical shifts of the labeled carbon indicated the possible covalent binding of hydroquinone to the humic acids via ester and possibly ether bonds, and the incorporation of degradation products of hydroquinone into the humic acids. This study provided evidences for the mediatory role of humic acids in the fate of NP as a sink for bacterial degradation intermediates of this compound.     

Equilibrium sorption of phenanthrene by soil humic acids

This study investigated the effect of chemical heterogeneity of humic acids (HAs) on the equilibrium sorption of phenanthrene by HA extracts. Six HA samples were extracted from three different soils with 0.5 M NaOH and 0.1 M Na₄P₂O₇ and were characterized with elemental analysis, infrared spectrometry, and solid-state ¹³C nuclear magnetic resonance (NMR) spectrometry. The equilibrium sorption measurements were carried out with a batch technique and using the six HA solids as the sorbents and phenanthrene as the sorbate. The measured sorption isotherm data were fitted to the Freundlich equation. The results showed that, for the same soil, (i) the total HA mass extracted with Na₄P₂O₇ was 13.7–22.6% less than that extracted with NaOH, (ii) the Na₄P₂O₇-extracted HA had higher O/C atomic ratio, greater content of polar organic carbons (POC), and lower aliphatic carbon content than the NaOH-extracted HA, and (iii) the Na₄P₂O₇-extracted HA exhibited greater sorption isotherm linearity and but not dramatic difference in sorption capacities than the NaOH extracted HA. The differences in the HA properties resulting from the two different extraction methods may be because NaOH can hydrolyze insoluble HA fractions such as fatty acid like macromolecules bound on soils whereas Na₄P₂O₇ could not. As a result, the HAs extracted with the two different methods had different polarity and functionality which affected their sorption property for phenanthrene.     

Fate of hexachlorobenzene-14C in wheat plants and soil under outdoor conditions

Residues of hexachlorobenzene-¹⁴C were found in all parts of wheat plants grown from treated seeds or in contaminated soil. Besides the parent compound and bound residues in plants and soil, very small amounts of soluble acidic metabolites were present in plants, which were characterized and determined quantitatively.     

Interactions of tillage and rainfall on atrazine leaching under field and laboratory conditions

Laboratory studies were conducted to evaluate effects of tillage reversal and rainfall on ¹⁴C-atrazine (2-chloro4-ethylamino-6-isopropylamino- -triazine) leaching patterns. Twelve intact soil cores (16 cm dia x 20 cm deep) were collected from 8-yr no-till (NT) fields. Half the cores were tilled (5 cm deep) prior to ¹⁴C-atrazine treatment (2.7 mg core⁻¹) to all cores. All cores received two rains (27 mm rain in 1.5 h, one day after application followed, two days later, by a 17 mm rain in 2.5 h) and leachate was collected and analyzed for atrazine. These rains simulated the timing, amount and duration of natural rainfall events from a tillage reversal field study. During the first high inte ity rainfall event, a pulse (2.1 μg L-1) of atrazine leached through tilled cores while leaching rate was linear and decreased (1.25 to 0.9 μg L-1) through un-tilled cores. Leaching rate was linear for both the tilled and un-tilled cores during the second rain. Less atrazine was left in the surface 5 cm of tilled soil than un-tilled after the two rains. Results confirmed field observations and suggested that when tillage is reversed on well structured soils, pesticide leaching may increase relative to un-tilled soil but these effects are probably confined to the first rain events after application only.     

Determination of 99Tc deposited on the ground within the 30-km zone around the Chernobyl reactor and estimation of 99Tc released into atmosphere by the accident

Technetium-99 was determined in samples from the 30-km zone around the Chernobyl reactor. Concentrations of ⁹⁹Tc in soil samples taken from three forest sites ranged from 1.1 to 14.1 Bq kg⁻¹ dry weight for the organic soil layers, and from 0.13 to 0.83 Bq kg⁻¹ dry weight for the mineral soil layers. In particular, for the organic layers, the measured ⁹⁹Tc concentrations were one or two orders of magnitude higher than those due to global fallout ⁹⁹Tc. The ⁹⁹Tc depositions (Bq m⁻²), based on the sum of the depositions measured in organic and mineral layers, ranged from 130 Bq m⁻² within the 10-km zone to about 20 Bq m⁻² close to the border of the 30-km zone. Taking the corresponding measured ¹³⁷Cs depositions into account, it was found that the activity ratio of ⁹⁹TW/¹³⁷Cs ranged from 6 × 10⁻⁵ to 1.2 × 10⁻⁴. It was estimated that about 970 GBq of ⁹⁹Tc had been released by the Chernobyl accident. This figure corresponded to 2%–3% of the total ⁹⁹Tc inventory in the core.     

Preliminary study on persistence in soil and residues in maize of imidacloprid

The aim of this work was to study the distribution of imidacloprid in soil and its translocation to roots and aerial parts of maize plant. The main objective was to assess imidacloprid residues in field environment, in order to provide data on honeybees exposure level to such an active substance. Imidacloprid has been detected and quantified by Triple Quadrupole HPLC-MS-MS. Pesticide persistence in the soil and its residues in pollen and in maize plants have been evaluated during the growing of maize plants developed from seeds dressed with Gaucho 350 FS (imidacloprid: 1.0 mg/seed). The sowing has been performed by means of a pneumatic precision drill. Samples have been collected at 30, 45, 60, 80, 130 days after the sowing, as pollen samples have been collected at the tasseling. Imidacloprid presence in aerial part of maize plant declined to 2-3 μg/kg 80 days after the sowing, while concentration in kernel at harvest was <1 μg/kg. Maize pollen represents an important part of protein supply of beehives, and it is of critical importance to bee foraging. The values detected (imidacloprid residues <1 μg/kg) showed that maize pollen source should not be relevant for acute toxicity impact on honey bees.     

A novel ortho-dehalogenation reaction of 2-chlorocinnamic acid catalyzed by the pink yeast Rhodotorula rubra Y-1529

In the present study, a resting cells suspension of Rhodotorula rubra Y-1529 was shown to have the capacity to perform an ortho-dehalogenation reaction on 2-chlorocinnamic acid. The results from the biodegradation of U-[¹⁴C]benzoic acid, cinnamic acid, 3-chlorocinnamic acid and 4-chlorocinnamic acid suggest that the first step of the ortho-dehalogenation reaction occurred during the oxidation of the unsaturated C3 side chain of 2-chlorocinnamic acid to 2-chlorobenzoic acid. None of the 2-chlorobenzoic acid was found in the biodegradation system, suggesting that this step was a highly regulated step. After the side-chain oxidation reaction, the hydroxylation of the benzene ring was determined to be at the para-position first, followed by the meta-position. The occurrence of 3:4-position ring fission reactions and the production of the final product, CO₂, was proven by the biodegradation of U-[¹⁴C] benzoic acid. This oxidative dehalogenation reaction catalyzed by R. rubra was found to be regiospecific for 2-chlorocinnamic acid; the chloride ion was probably removed after the ring fission reaction. A pathway of the ortho-dehalogenation reaction of 2-chlorocinnamic acid catalyzed by R. rubra was proposed based on these data.     

Distribution of pesticides and heavy metals in trophic chain

Determination of triazines herbicides (atrazine and simazine) by high performance liquid chromatography (HPLC) in samples of trophic chain were worked out. Determination limits of 0.5 μg g⁻¹ for atrazine, 0.8 μg g⁻¹ for simazine with pesticides recovery of 70–77% in trophic chain samples were obtained. The content of simazine in soils was in range 1.72–57.89 μg g⁻¹, in grass 5–88 μg g⁻¹, in milk 2.32–15.29 μg g⁻¹, in cereals 10.98–387 μg g⁻¹, in eggs 30.14–59.48 μg g⁻¹, for fruits: 2.45–6.19 μg g⁻¹. The content of atrazine in soils was in range 0.69–19.59 μg g⁻¹, in grass 7.85–23.85 μg g⁻¹, in cereals 1.88–43.08 μg g⁻¹. Cadmium, lead and zinc were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) in the same samples as atrazine and simazine. Determination limits for cadmium 5 × 10⁻³ μg g⁻¹, for lead 1 × 10⁻² μg g⁻¹, and for zinc 0.2 × 10⁻³ μg g⁻¹, were obtained. The content of cadmium in soil was in range 0.13–5.89 μg g⁻¹, in grass 114–627.72 × 10⁻³ μg g⁻¹, in milk 8.88–61.88 × 10⁻³ μg g⁻¹, in cereals 0.20–0.31 μg g⁻¹, in eggs 0.11–0.15 μg g⁻¹, in fruits 0.23–0.59 μg g⁻¹. The content of lead in soils was in range 0.57–151.50 μg g⁻¹, in grass 0.16–136.57 μg g⁻¹, in milk 1.16–3.74 μg g⁻¹, in cereals 1.05–5.47 μg g⁻¹, in eggs 5.79–55.87 μg g⁻¹, in fruits 21.00–87.36 μg g⁻¹. Zinc content in soil was in range 9.15–424.5 μg g⁻¹, in grass 35.20–55.87 μg g⁻¹, in milk 20.00–34.38 μg g⁻¹, in cereals 14.94–28.78 μg g⁻¹, in eggs 15.67–32.01 μg g⁻¹, in fruits 14.94–18.88 μg g⁻¹.

Described below extraction and mineralization methods for particular trophic chains allowed to determine of atrazine, simazine, cadmium, lead and zinc with good repeatability and precision. Emphasis was focused on liquid–liquid extraction and solid-phase extraction of atrazine and simazine from analysed materials, as well as, on monitoring the content of herbicides and metals in soil and along trophic chain. Higher concentration of pesticides in samples from west region of Poland in comparison to that of east region is likely related to common applying them in Western Europe in relation to East Europe. The content of metals strongly depends on samples origin (industry area, vicinity of motorways).