Bioavailability of bound residue derived from ^(14)C-labeled chlorsulfuron in soil and its mechanism of phytotoxicity

The bioavailability of bound residue(BR) derived from 14 C-labeled chlorsulfuron in soil and effect of the main components of the BR on growth of rape(brassica napus) and rice(Oryza sativa L.) were investigated. The results showed that the BR with the concentration of 0 28 and 0 56 nmol/g air-dried soil, which was calculated by special radioactivity of 14 C-labeled chlorsulfuron parent compound, resulted in significant depression effect on growth of rape seedling. It was assured that the main components(2-amino-4-methoxyl-6-methyl-1,3,5-triazine, 2-amino-4-hydroxyl-6-methyl-1,3,5-triazine, and 2-chloro-benzenesul-f onamide) of the BR did not inhibit the growth of rape and rice. LC-MS analysis demonstrated that the parent compound previously bound to the soil matrix could be again released and transformed into methanol-extractable residue during the course of rape growth. It was concluded that the molecular leading to the phytotoxicity to rape and rice in the BR is still the parent compound.

Identification of the bound residue composition derived from ^(14)C-labeled chlorsulfuron in soil by using LC-MS and isotope tracing method

A new method for extracting the bound residue(BR) derived from 14 C-labeled chlorsulfuron in soils was developed, and the technique of combining LC-MS with isotope tracing method was subsequently applied to identify the composition of the 14 C-BR in a loamy Fluvent derived from marine deposit. The results showed that the 14 C-[2-amino-4-methoxyl-6-methyl-1,3,5]-triazine, 14 C-[2-amino-4-hydroxyl-6-methyl-1,3,5]-triazine and 14 C-chlorsulfuron parent compound constituted the main composition of the 14 C-BR derived from 14 C-labeled chlorsulfuron in the soil. The radioactive ratio of three compounds accounted for 39.8%, 35.4% and 17.9% of total recovered radioactivity, respectively. However, a small amount(3.6% of total recovered radioactivity) of the complex of 14 C-[2-amino-4-hydroxyl-6-methyl-1,3,5]-triazine might have existed in the 14 C-BR in association with an unknown soil substrate. 2-chlorobenzenesulfonamide was also detected to be one of the components of the BR. The results could well explain the mechanism of phytotoxicity caused by the BR derived from chlorsulfuron in soil. In addition, the mechanism of BR formation in soil was also discussed in details.

Response of Rice Varieties to Bound Residues of Metsulfuron-Methyl in a Paddy Soil

Metsulfuron-methyl is one of the widely used sulfonylurea herbicides. However, approximately half of the applied metsulfuron-methyl may remain as bound residues in soil. To characterize the response of rice plants to residual metsulfuron-methyl in soil, the activities of acetolactate synthase （ALS）, superoxide dismutase （SOD）, peroxidase （POD）, and catalase （CAT） were investigated in two rice varieties that differed in susceptibility to the herbicide. Changes in the activity of these enzymes in leaves and roots of Xiushui 63, a sensitive rice variety, were greater than those in a resistant variety Zhenong 952. Irrespective of variety, changes in the enzyme activity were greater in the roots than in the leaves. The activities of ALS and CAT decreased, while the SOD activity increased with the increase in the amounts of bound residues of metsulfuron-methyl （BRM） in soil. The POD activity increased at the BRM level of 0.025 mg kg^-1, but decreased at the BRM level of 0.05 mg kg^-1. The results showed that the bound residues of sulfonylurea herbicides may affect metabolism of rice plants.

Bound ^(14)C-metsulfuron-methyl residue in soils

Bound residue(BR) of 14 C-metsulfuron-methyl ( 14 C-BR) in seven kinds of soil was significantly negative-related to soil pH and positive-related to the clay content during the initial 20 d of incubation, but only was significantly negative-related to soil pH after 30 d incubation. Again, the soil pH was found to be the dominant factor affecting BR formation from 14 C-metsulfuron-methyl among the basic properties(soil pH, clay, OM and CEC etc.) of soil. The maximum content of 14 C-BR in the 7 soils accounted for 19.3%-52.6% of applied amount. In addition, the composition of the 14 C-BR in fluvio marine yellow loamy(S 7) at the 90 d of incubation was identified using the coupling technique of LC-MS and isotope tracing method. The results showed that the 14 C-[2-amino-4-hydroxyl-6-methyl-1, 3, 5]-triazine, 14 C-[2-amino-4-methoxy-6-methyl-1, 3, 5]-triazine and 14 C-metsulfuron-methyl parent compound constituted the main components of the BR derived from 14 C-metsulfuron-methyl in the S 7. The relative percentage of the three compounds accounted for 41.4%, 35.8% and 19.3% of total recovery radioactivity, respectively. The results also indicated that a non-radioactive component, 2-methylformate-benzenesulfonyl-isocyanate, one of the degraded products of metsulfuron-methyl in soil, was also found to be one of the components of the BR. The parent compound in BR can well explain the phytotoxic effect on substitution crops caused by the BR derived from metsulfuron-methyl in soil.

Toxic Effects of Bound Malathion Residues in Rats

The level of bound malathion residues in treated wheat grain and its toxic effects on rats were investigated. Wheat grain was treated with [14C] malathion (specific activity: 2.76 MBq/mg) to determine the bioavailability of bound residues in rats. At the same time, grain was treated with nonlabeled malathion to test for possible toxic effects of bound residues in a subchronic (90 days) feeding study in rats at two dose levels. 10 and 100 ppm.It was observed that the level of malathion-bound residues amounted to 11.28% of the applied dose (for six months). Also, it was noted that the main route of [14C]-malathion excretion was through the urine. This signifies that grain-bound malathion was bioavailable. In subchronic test on rats bound malathion residues (both dose levels) induced effects to some extent in organ weight (spleen and adrenals), and blood ChE activity. In both, males and females, there was an increase in SGPT activity (lower dose), and in alkaline phosphatase in females (higher dose). Hematological data showed changes only in hemoglobin concentration in males (both dose levels).