Problems and results of trace analysis of 2,3,7,8-tetrachlorodibenzo-p-dioxin in 2,4,5-trichlorophenoxyacetic acid and its esters

Quantitative analysis of tetrachlorodibenzo-p-dioxins (TCDDs) has gained increasing importance in the public domain. The analytical problem is complex because of the large number of interfering isomers and the extremely low limit of determination enforced by legislation. DAPA elaborated a procedure based on the latest published methods and on the existing experience of the collaborators. This procedure involves preseparation of the original sample on a silica column and cleanup by liquid chromatography (LC) on alumina. Alkaline saponification of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) esters seems to create artificial dioxins in the organic extract. Final determination is performed by capillary gas chromatography (GC)-low resolution mass spectrometry (MS). Final international collaborative work was carried out on 4 samples. Results were reported by 13 of 20 laboratories. Mean values ranged from 3.5 to 8.7 micrograms/kg. The interlaboratory reproducibilities ranged from 3.4 to 8.2 micrograms/kg (about 100% of the mean value).     

Effects of pentachlorophenol and 2,4,5-trichlorophenoxyacetic acid on the microflora of the soil in a beech wood

Summary Every second month for 2 years a beech forest floor was treated with pentachlorophenol and 2,4,5-trichorophenoxyacetic acid each in two concentrations. The microbial biomass and its respiration activity in the three litter horizons were measured during this time and during a recovery period of 2 years after the treatment was stopped. The microbial biomass, mainly fungi, was decreased dose-responsively, as was the respiration rate. The doubling time of the fungal biomass was estimated to be about 50–100 days in the F horizon, and considering the natural decreases and recovery times observed, it is suggested, following Domsch et al. (1983), that a biomass decrease of 75%–93.75% is tolerable, a decrease of less than 75% is negligible, and a decrease of over 93.75% is critical.     

Protection of tomato seed germination from the inhibitory effect of 2,4,5-trichlorophenoxyacetic acid by inoculation of soil with Burkholderia cepacia AC1100

The effect of 2,4,5-trichlorophenoxy acetic acid (2,4,5-T) on the germination and seedling vigor of different crop seeds was tested. Seeds of rice, maize, sorghum, finger millet, and horse gram were comparatively more tolerant to the chemical with no marked effect up to a concentration of 200 mg 2,4,5-T L(-)(1) as tested by the filter paper method. Tomato and brinjal (egg plant) were highly susceptible. Even at 5 and 10 mg 2,4,5-T L(-)(1), marked reduction in the germination and seedling vigor of tomato and egg plant, respectively, was observed. At 20 and 30 mg L(-)(1), the germination of tomato and egg plant seeds, respectively, were completely inhibited on filter paper, whereas the inhibitory concentrations in soil was 40 mg 2,4,5-T kg(-)(1) soil. Several abnormalities were observed in the chemically affected seedlings. Protease activity of the seeds germinating in the presence of the chemical was drastically reduced. Bioremediation of the chemically contaminated soil with Burkholderia cepacia AC1100, by inoculation of the soil 7 days before sowing the seeds, completely protected the seeds, resulting in normal germination and an improved seedling vigor.     

Estimating organic acid contributions to surface water acidity in Quebec (Canada)

Inorganic ion balances for lake waters lying on the Canadian Shield in the province of Quebec, Canada, consistently show significant anion deficits (mean deficit 70 to 90 μeq L^?1). Models taking into account organic anions have been tested for their ability to eliminate this anion deficit. The data set consisted of the chemical composition (pH, all major ions, major trace metals, dissolved organic and inorganic C, total alkalinity) of ≈1200 lakes from four hydrographic regions. The relative performances of three models (the 1983 Oliver et al. model and two derived models) were evaluated by comparing the capacity of each model to compensate fully for the anionic deficit of the waters. The study showed that without calibration all models systematically underestimated the anionic deficit. The two derived models were recalibrated and validated by regional discrimination of the data; charge balances calculated with the recalibrated models were markedly improved. Based on calculated anion deficits, the contribution of natural organic acids to Quebec surface water acidity increases from southwest to northeast and greatly exceeds that previously reported.     

Behavior of glyphosate and aminomethylphosphonic acid (AMPA) in soils and water of reservoir Radeburg II catchment (Saxony/Germany)

The behavior of the herbicide glyphosate and its main metabolite aminomethylphosphonic acid (AMPA) was investigated in soils and water in a well-defined catchment of the reservoir Radeburg II near Dresden (Saxony/Germany). The half-life of glyphosate in soil ranged from 11 to 17 days. Glyphosate and AMPA completely disappeared from soil after about 5 months following application of the products ”︁Roundup Ultra” and ”︁Touchdown”. The aquatic system in the test areas (surface water, soil solution, and groundwater) was not significantly affected by direct application of the compound. In general, there was a clear indication of strong sorption of the two substances by soil particles. Settlement areas were recognized as possible sources of glyphosate and AMPA intake in aquatic systems.     

Photodecomposition of an acaricide,fenazaquin, in aqueous alcoholic solution

Fenazaquin (I) is a new acaricide of the quinazoline class. The photodecomposition of I was studied in aqueous methanolic and 2-propanolic solution under UV light (30 h) and sunlight (70 h) separately. The photolytic half-lives in aqueous methanolic solution were found to be 17.1 h (UV) and 38.1 h (sunlight), whereas these were 12.9 h (UV) and 29.2 h (sunlight) for aqueous 2-propanolic solution; all followed a first-order reaction kinetics. Six photoproducts were obtained: beta-phenyl (p-tert-butyl) ethyl alcohol (II), 4-hydroxyquinazoline (III), p-tert-butyl vinyl benzene (IV), 2,4-dihydroxyquinazoline (V), phenyl (p-tert-butyl) acetic acid (VI), and 2-methyl-2-[4'-(2' '-hydroxyethyl)phenyl]propanoic acid (VII). Compounds VI and VII could be isolated only from aqueous 2-propanolic solution under sunlight irradiation. The major degradation products are formed as a result of cleavage of the ether bridge linking the quinazoline and phenyl ring systems of the molecule, oxidation of the tert-butyl substituent, and oxidation of the heterocyclic portion of the quinazoline ring. A probable mechanism of formation of the photoproducts is also suggested.     

Thermal stability of texture in Chinese water chestnut may be dependent on 8,8'-diferulic acid (aryltetralyn form)

Ferulic acid (FA) cross-links have been implicated in the thermal stability of texture in Chinese water chestnut (CWC) tissues. The aim of the current study has been to investigate this concept further. CWC tissue strips were measured for their mechanical properties before and after extraction in increasing strengths of alkali. The mechanical properties were related to the associated mode of fracture (cell separation or breakage) at the fracture surfaces and the phenolic composition of the cell walls. CWC tissue softened after prolonged extraction in cold alkali due to an increase in the ease of cell separation. Analysis of wall-bound phenolics demonstrated that most FA moieties, including five of the six dehydrodimers, were released before tissue strength was reduced. Loss of strength was, however, coincident with the loss of 8,8'-diferulic acid, aryltetralin (AT) form. It has been suggested that this dehydrodimer may be particularly concentrated at the edge of the cell faces. These results provide further evidence for the involvement of this dehydrodimer in conferring thermal stability of cell-cell adhesion and hence texture in CWC. However, they do not exclude the other diferulates from involvement in cell adhesion.     

Theoretical speciation of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) in agronomic conditions

The presence of ethylenediamine-N-(o-hydroxyphenylacetic)-N'-(p-hydroxyphenylacetic) acid (o,p-EDDHA) as the second largest component in commercial EDDHA iron chelates has recently been demonstrated. Here is reported the speciation of o,p-EDDHA by the application of a novel methodology through the determination of the complexing capacity, protonation, and Ca(2+), Mg(2+), Cu(2+), and Fe(3+) stability constants. The pM values and species distribution in solution, hydroponic, and soil conditions were obtained. Due to the para position of one phenol group in o,p-EDDHA, the protonation constants and Ca and Mg stability constants have different values from those of o,o-EDDHA and p,p-EDDHA regioisomers. o,p-EDDHA/Fe(3+) stability constants are higher than those of EDTA/Fe(3+) but lower than those of o,o-EDDHA/Fe(3+). The sequence obtained for pFe is o,o-EDDHA/Fe(3+) >/= o,p-EDDHA/Fe(3+) > EDTA/Fe(3+). o,p-EDDHA/Fe(3+) can be used as an iron chelate in hydroponic conditions. Also, it can be used in soils with limited Cu availability.     

Isolation of Cd-binding protein of water hyacinth (Eichhornia crassipes) grown in Nile river water

Many investigators have reported that water hyacinth plants can accumulate toxic heavy metal ions and may be useful for elutriation of polluted water. The purpose of our study was to search for the mechanism by which these plants tolerate and accumulate toxic metal ions. Cadmium was accumulated in the plants against the concentration gradient, mostly as a soluble form in the cytoplasm. Isolation and Purification of Cd-binding protein with sephadex A-25 and fractionation on sephadex G-100 showed that the accumulated Cd was associated with two major protein fractions.The first with molecular weight 25 - 20 kD contained about 35% of bound Cd. The second fraction with molecular weight 12 - 8 kD contained about 40% of bound Cd. The two forms were found also in water hyacinth cultivated in Nile water as a control, although the amount of Cd accumulated was less than those exposed to excess Cd.