Enantioselective degradation and chiral stability of malathion in environmental samples

The dissipation behaviors of the two enantiomers of the organophosphorus pesticide malathion (MA) in environment samples were elucidated using a normal-phase high-performance liquid chromatography with a cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) chiral column. A validated chiral residue analysis method in soil and water was established; the average recoveries for the two enantiomers were 88-102% in soil and 81-99% in water. Racemic and enantiopure R-(+)- and S-(-)-MA were incubated in five soil and water systems. The results of the degradation of racemate in all of the environment samples showed the inactive S-(-)-enantiomer degraded more rapidly than the active R-(+)-enantiomer, resulting in a relative enrichment of the R-form. Moreover, when the enantiopure S-(-)- and R-(+)-MA were incubated in three well-chosen soil and water samples, respectively, inversion from one enantiomer to another was found, indicating that using the optically pure enantiomer will not help to increase the bioactivity and reduce the environmental pollution.     

Enantioselective environmental behavior of the chiral herbicide fenoxaprop-ethyl and its chiral metabolite fenoxaprop in soil

The enantioselective degradation behavior of fenoxaprop-ethyl (FE) and its chiral metabolite fenoxaprop (FA) in three soils under native conditions was investigated. Two pairs of enantiomers were analyzed by high-performance liquid chromatography (HPLC) with an amylose tri-(3,5-dimethylphenylcarbamate) (ADMPC) chiral column. The degradation of racemic FE in three soils showed the herbicidally inactive S-(-)-enantiomer degraded faster than the active R-(+)-enantiomer. FE was configurationally stable in soils because no interconversion to the respective antipodes was observed during incubation of the enantiopure S-(-)- or R-(+)-FE. The main metabolites of FE were confirmed as FA and 6-chloro-2,3-dihydrobenzoxazol-2-one (CDHB), and the formation of the chiral metabolite FA showed enantioselectivity in soils. The degradation of rac-FA was also enantioselective with the S-(-)-FA preferentially degraded: the half-life (t(1/2)) of the S-form in the three soils ranged from 2.03 to 5.17 days, and that of R-form ranged from 2.42 to 20.39 days. The inversion of the S-(-)-enantiomer into the R-(+)-enantiomer occurred in two of the three soils when the enantiopure S-(-)- and R-(+)-FA were incubated. The data from sterilized control experiments indicated that the enantioselectivity of FE and FA was attributed to microbially mediated processes.     

Application of capillary electrophoresis to study the enantioselective transformation of five chiral pesticides in aerobic soil slurries

The enantiomers of five chiral pesticides of environmental interest, metalaxyl, imazaquin, fonofos (dyfonate), ruelene (cruformate), and dichlorprop, were separated analytically using capillary electrophoresis (CE) with cyclodextrin chiral selectors. For metalaxyl, imazaquin, and fonofos, aqueous slurries of soil samples from two sites in Georgia and one in Ohio were spiked with the racemate of each pesticide at 50-60 mg/L of aqueous phase of the slurry, and CE analyses were performed at various time intervals to determine enantiomer fractions (EF). Metalaxyl underwent enantioselective transformation; in one soil, the half-life of the target active R-(+)-enantiomer was 17 days while that for the S-(-)-enantiomer was 69 days. Transformation occurred more slowly in the other two soils but was still selective for the R-(+)-enantiomer. Imazaquin and fonofos exhibited nonselective enantiomer loss over their 3 months of incubation time; this could have been due to abiotic or nonselective microbial reactions. Ruelene and dichlorprop were transformed selectively in a variety of soils in a previously reported study (7) that showed the influence of environmental changes on the transformation of chiral pollutants in soils; analytical methods used in that study are reported here to further illustrate the application of CE. CE is shown to be a simple, efficient, and inexpensive way to follow the transformation of chiral pesticides in laboratory microcosms where concentrations can be made high enough (25-50 mg/L initial racemate concentration) for detection of residual parent enantiomers during most of the process.     

Enantioselective separation and phytotoxicity on rice seedlings of paclobutrazol

The environmental significance of enantioselectivity in chiral insecticides and herbicides has been widely studied. However, little information is currently available on the enantioselective behavior of chiral plant growth regulators. In this study, paclobutrazol enantiomers were resolved and prepared by chiral high-performance liquid chromatography with a Sino-chiral OJ column. The relationship among absolute configuration, optical activity and circular dichroism of paclobutrazol enantiomers was established. The enantioselective behavior of paclobutrazol, including enantioselective effect of paclobutrazol on the growth of rice seedlings and cyanobacteria and enantioselective loss of paclobutrazol in rice seedling growth media, in rice culture system was studied. The (2S,3S)-(-)-enantiomer was almost 3.1 times more active than the (2R,3R)-(+)-enantiomer toward shoot growth as measured by 7 day EC50 values. Enantioselectivity could not be determined with respect to root growth of rice seedlings because a typical dosage response was not observed in the range of the concentrations studied. The dissipation of paclobutrazol in rice growth medium is not enantioselective. Enantiomers and diastereoisomer of paclobutrazol all facilitated the growth of cyanobacteria, which increase the effectiveness of rice biofertilizers. The (2S,3S)-(-)-enantiomer showed stronger stimulatory activity on Microcystis aeruginosa cyanobacteria than the (2R,3R)-(+)-enantiomer, whereas the latter was a more potent stimulator of Anabaena sp. growth. These observations indicate that application of the (2S,3S)-(-)-enantiomer of paclobutrazol and Microcystis aeruginosa in rice cultivation is a good strategy for improving rice seedling performance.     

Enantiomeric differences in permethrin degradation pathways in soil and sediment

Chirality occurs widely in synthetic pyrethroids. Studies have shown significant differences in both aquatic toxicity and degradation rates between enantiomers from the same diastereomer of selected pyrethroids. To better understand chiral selectivity in biodegradation of pyrethroids, 14C-labeled permethrin was used to characterize enantiomeric differences in the formation of transformation intermediates in two soils and a sediment. Individual enantiomers of permethrin were spiked into soil and sediment samples, and transformation products were identified with known standards. Enantioselectivity was observed in most treatments when the dissipation of the parent enantiomers, the amount of intermediates and bound residues formed, and mineralization rates were compared between the enantiomers. The results show that all enantiomers of permethrin hydrolyzed rapidly and that the hydrolysis products were quickly further transformed. The direct hydrolysis products, cyclopropanic acid (Cl2CA), 3-phenoxybenzyl alcohol (PBalc), and 3-phenoxybenzoic acid (PBacid), were recovered at small percentages, ranging from 1 to 14% for Cl2CA and from 0.2 to 6% for PBalc and PBacid. The R-enantiomer of both cis- and trans-permethrin was mineralized more quickly than the S-enantiomer after hydrolysis. The degradation products from cis-permethrin were more persistent than those from trans-permethrin. As some transformation intermediates of permethrin may have greater acute and chronic toxicity than the parent compound, enantioselectivity in the formation of degradation intermediates may lead to different overall toxicities and merit further investigation. This study suggests that for chiral compounds, enantioselectivity may be reflected not only in the dissipation of the parent enantiomers but also in the kinetics of formation of intermediate transformation products.     

Micronutrient Concentration in Horticultural Crops Grown on a Soil Amended with the Solid Phase of Pig Slurry

Abstract

Previous studies carried out on metal fractionation have shown that more than 95% of metals are in the solid phase of pig slurries (SPPS), with copper (Cu), and zinc (Zn) being the commonly occurring micronutrients in animal slurries. The input of micronutrients associated with the application of SPPS could be an important pathway for the supply of these essential elements to arable crops in bioavailable forms, especially in calcareous soils, which induce the immobilization of these elements. The aim of this work was to study the effect of application of pig manures (fresh and composted) derived from the SPPS on the micronutrient—iron (Fe), Cu, Magnesium (Mn), and Zn—concentration on amended calcareous soils in horticultural plants (cucumber and Milan cabbage). In addition, the effect of composting and application rates were analyzed. The experiment was conducted in field conditions on a Xerofluvent soil with a clayey‐loam texture. The organic wastes used in this study were uncomposted and composted solid fractions of swine manure slurry (UC‐SPPS and C‐SPPS, respectively) at two different rates (supplying 300 kg N ha^?1 and 450 kg N ha^?1 respectively). A mineral fertilizer treatment equivalent to 300 kg N ha^?1 and a control treatment without fertilization were also included for comparison. The use of SPPS amendment induced a biomass production similar to the mineral fertilizer for cucumber, but higher in Milan cabbage plants, without any yield increment associated with the increased application rate of SPPS or composting. Micronutrient concentration in cucumber and cabbage plants was affected by the SPPS amendment, with an increase of Mn and Zn uptake and a decrease of Cu, compared to the control. The increasing application rate of SPPS did not induce a general increase in the plant uptake of micronutrients; the opposite was true for the crops grown in the C‐SPPS‐amended soils.     

Chemical composition of cabbage (Brassica oleracea L. var. capitata) grown on acid sulfate soils

The purpose of this study was to investigate the influence of soil geochemistry on the concentrations of Ca, K, Mg, P, Co, Ni, Zn, Mn, Cu, and Fe in cabbage (Brassica oleracea L. var. capitata) grown on acid sulfate (AS) soils in Western Finland. A total of 11 topsoil (0–20 cm) and corresponding cabbage samples and three whole‐soil profiles (≈ 0–260 cm) were collected on three agricultural fields. The concentrations of Co and Zn in cabbage were correlated with the NH₄Ac‐extractable (easily available) concentrations in the topsoil, indicating that the uptake of these elements in cabbage is largely governed by soil geochemistry. Yet, the concentrations of Co and Zn in cabbage were not in general elevated relative to that of Finnish average values, although some AS soils showed enriched concentrations of these metals in the soil and cabbage. Significant geochemical differences (e.g., oxidation depth, organic‐matter and S content, pH) were observed among the studied AS soils, while, on the other hand, the concentrations of Ca, K, Mg, P, Ni, Mn, Cu, and Fe in cabbage were relatively similar. The hydroxylamine‐extractable concentrations of these elements in the topsoil were not correlated to those in cabbage, suggesting that uptake is not governed by the oxide‐bound fraction of these elements in the soil. Similarly, the easily available concentrations of Ca, P, Ni, Mn, Cu, and Fe in the topsoil were not correlated to those in cabbage, indicating that uptake is independent of the easily available concentrations in the soil. Hence, it is suggested that cabbage can regulate and thus optimize its concentrations of Ca, P, Ni, Mn, Cu, and Fe. Oxidation depth affected neither the easily available concentrations of Co, Ni, Zn, and Mn in the topsoil nor the concentrations in cabbage. However, the subsoil with a lower oxidation depth, which is to a smaller extent affected by leaching, may partly be enriched in these metals. Nevertheless, these showed no increased concentrations in cabbage. Based on these findings, it is suggested that the large amounts of metals mobilized in AS soils are easily lost to drains, subsequently contaminating nearby waterways and estuaries whereas they are only partly enriched in cabbage and other previously studied crops (oat).     

Erratum: Chemical composition of cabbage (Brassica oleracea L. var. capitata) grown on acid sulfate soils

The purpose of this study was to investigate the influence of soil geochemistry on the concentrations of Ca, K, Mg, P, Co, Ni, Zn, Mn, Cu, and Fe in cabbage (Brassica oleracea L. var. capitata) grown on acid sulfate (AS) soils in Western Finland. A total of 11 topsoil (0–20 cm) and corresponding cabbage samples and three whole‐soil profiles (≈ 0–260 cm) were collected on three agricultural fields. The concentrations of Co and Zn in cabbage were correlated with the NH₄Ac‐extractable (easily available) concentrations in the topsoil, indicating that the uptake of these elements in cabbage is largely governed by soil geochemistry. Yet, the concentrations of Co and Zn in cabbage were not in general elevated relative to that of Finnish average values, although some AS soils showed enriched concentrations of these metals in the soil and cabbage. Significant geochemical differences (e.g., oxidation depth, organic‐matter and S content, pH) were observed among the studied AS soils, while, on the other hand, the concentrations of Ca, K, Mg, P, Ni, Mn, Cu, and Fe in cabbage were relatively similar. The hydroxylamine‐extractable concentrations of these elements in the topsoil were not correlated to those in cabbage, suggesting that uptake is not governed by the oxide‐bound fraction of these elements in the soil. Similarly, the easily available concentrations of Ca, P, Ni, Mn, Cu, and Fe in the topsoil were not correlated to those in cabbage, indicating that uptake is independent of the easily available concentrations in the soil. Hence, it is suggested that cabbage can regulate and thus optimize its concentrations of Ca, P, Ni, Mn, Cu, and Fe. Oxidation depth affected neither the easily available concentrations of Co, Ni, Zn, and Mn in the topsoil nor the concentrations in cabbage. However, the subsoil with a lower oxidation depth, which is to a smaller extent affected by leaching, may partly be enriched in these metals. Nevertheless, these showed no increased concentrations in cabbage. Based on these findings, it is suggested that the large amounts of metals mobilized in AS soils are easily lost to drains, subsequently contaminating nearby waterways and estuaries whereas they are only partly enriched in cabbage and other previously studied crops (oat).     

Effects of soil pH and soil water content on prosulfuron dissipation

The sulfonylurea herbicide prosulfuron, 1-(4-methoxy-6-methyltriazin-2-yl)-3-[2-(3,3,3-trifluoropropyl)phenylsulfonyl]urea, is used for the selective control of broadleaf weeds in corn, sorghum, and cereal grains. To investigate its fate in soils, this study examined the effects of soil pH and water content on the rates of dissipation processes and the products formed under aerobic conditions. Radiometry and chromatography analyses were used to quantify the degradation products and bound residues formed in incubations of 10 different soils. The pH-dependent hydrolysis of the sulfonylurea bridge to form phenyl sulfonamide was the primary transformation process. Significant microbial degradation of prosulfuron occurred in 2 of the 10 soils, yielding (14)CO(2) and desmethyl prosulfuron among the major products. The time required for 50% dissipation of the herbicide (DT(50)) was determined for each soil and water content treatment. At equivalent water contents, prosulfuron DT(50) values were positively correlated with soil pH (P < 0.0001), varying from 6.5 days at pH 5.4 to 122.9 days at pH 7.9. Soil pH and water content strongly influence the fate of sulfonylurea herbicides in agricultural fields. Differences in the effect of soil water content on dissipation kinetics in a comparison of two soils were attributed to differences in soil pH, texture, and the ability of indigenous microorganisms to transform the herbicide.     

不同种类蔬菜幼苗对铅的敏感性研究

采用水培方法,探讨了小白菜（叶菜类）、黄瓜、豇豆（瓜果类）和萝卜（根茎类）幼苗对重金属Pb的吸收累积量大小及Pb对其幼苗生长发育的影响。结果表明,蔬菜幼苗根和茎叶累积Pb量均随Pb处理浓度的增加而显著增加（P〈0.05）,且同一处理浓度下根中Pb含量远高于茎叶中Pb含量。蔬菜苗期根对Pb的敏感性排序为黄瓜〉小白菜〉萝卜〉豇豆,茎叶为小白菜〉萝卜〉黄瓜〉豇豆。低浓度的Pb对叶绿素的合成有一定程度的刺激作用,随Pb浓度增加,叶片中叶绿素含量降低。小白菜过氧化氢酶（CAT）含量随着Pb浓度的增大先增大后缓慢降低,其他3种蔬菜则表现为先减小后增大的趋势。此外,黄瓜和豇豆出芽率显著降低,4种蔬菜幼苗根长均明显受到抑制。     

Tronchuda cabbage (Brassica oleracea L. var. costata DC): scavenger of reactive nitrogen species

The ability of tronchuda cabbage ( Brassica oleracea L. var. costata DC) to act as a scavenger of the reactive nitrogen species nitric oxide and peroxynitrite was investigated. The aqueous extracts obtained from tronchuda cabbage seeds and from its external and internal leaves exhibited a concentration dependent scavenging capacity. The antioxidant potential observed against the two reactive species was as follows: seeds > external leaves > internal leaves. In order to establish a possible correlation with the chemical composition of the extracts, the activity of ascorbic and sinapic acids and kaempferol 3- O-rutinoside was also studied. Among the compounds tested, sinapic acid showed the strongest antioxidant activity against both species.     

Occurrence of (+)- and (-)-gossypol in wild species of cotton and in Gossypium hirsutum Var. marie-galante (Watt) Hutchinson

Gossypol occurs as a mixture of enantiomers in cottonseed. These enantiomers exhibit different biological activities. The (-)-enantiomer is toxic to animals, but it has potential medicinal uses. Therefore, cottonseed with >95% (-)-gossypol could have biopharmaceutical applications. The (+)-enantiomer shows little, if any, toxicity to nonruminant animals. Thus, cottonseed with >95% (+)-gossypol could be more readily utilized as a feed for nonruminants. The (+)- to (-)-gossypol ratio in commercial Upland (Gossypium hirsutum) cottonseed is usually about 3:2, whereas that in commercial Pima cottonseed (Gossypium barbadense) is approximately 2:3. Herein are reported the (+)- to (-)-gossypol ratios in the seed from 28 wild species of cotton (194 accessions), 94 accessions of G. hirsutum var. marie-galante, and 3 domesticated species (11 accessions). It was found that some or all of the accessions of Gossypium darwinii, Gossypium sturtianum, Gossypium areysianum, Gossypium longicalyx, Gossypium harknessii, and Gossypium costulatum produce an excess of (-)-gossypol but none >65%. At least one accession of Gossypium anomalum, Gossypium mustelinum, Gossypium gossypioides, and Gossypium capitis-viridis contained >94% (+)-gossypol. One of the 94 accessions of G. hirsutum var. marie-galante (i.e., no. 2469) contained 97% (+)-gossypol.     

Sorption behavior of triazole fungicides in Indian soils and its correlation with soil properties

Adsorption-desorption of triazole fungicides, hexaconazole [2-(2,4-dichlorophenyl)-1-(1H-1,2,4,-triazol-1-yl) hexan-2-ol], triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl) butan-2-one], and penconazole[1-(2,4-dichloro-beta-propyl phenethyl)-1H-1,2,4-triazole] was studied in five Indian soils using batch method. The adsorption isotherms fitted very well to the Freundlich equation. Adsorption of various triazole fungicides increased in this order: triadimefon > hexaconazole > penconazole. The product of the Freundlich adsorption constants, K(f)(1/n), showed good correlation with the soil organic carbon (OC) content, suggesting that soil OC is the main controlling factor for triazoles adsorption. Clay and silt content of the soil also affected the adsorption constants. Adsorption of hexaconazole and triadimefon was nearly reversible in two low OC soils (soil 3, soil 5) where 90-100% of the sorbed fungicides was released in a single washing step. Otherwise, desorption of triazole fungicides showed hysteresis, and 30-60% of the triazole fungicides were retained by the soil after single washing. IR spectra showed that H-bonds and charge-transfer bonds between humic acid and fungicides probably operated as mechanisms of adsorption.     

Enantiomeric resolution and growth-retardant activity in rice seedlings of uniconazole

The increasing application of chiral pesticides has enhanced interest in their enantioselectivity. However, little relevant information is currently available for enantioselective activity of chiral plant growth regulators. In an attempt to screen active enantiomers of uniconazole, this work investigated enantiomeric separation and the enantioselective effect of uniconazole on the growth of rice seedlings and cyanobacteria. Baseline resolution of uniconazole enantiomers was achieved on a Chiralpak AD column by chiral high-performance liquid chromatography (HPLC). The relationship among circular dichroism (CD), optical rotation (OR), and absolute configuration was successfully established by coupling of CD and OR detection. The t test at the 95% level of confidence indicated significant differences between the enantiomers in their retardant activity toward growth of rice seedlings and stimulation effect on growth of cyanobacteria, the natural biofertilizers in rice paddy fields. The S-(+)-enantiomer was more active than the R-(-)-enantiomer in retarding growth of rice seedlings and stimulating growth of Microcystis aeruginosa . This special enantiomeric selectivity was further elucidated by probing the binding mode of enantiomers to gibberellin (GA) 20-oxidase by molecular docking. The S-(+)-enantiomer was found to bind tightly with GA 20-oxidase. The results suggested that the S-(+)-enantiomer instead of a racemate of uniconazole should be used to improve rice seedling quality.     

不同啶虫脒剂型对烟粉虱的毒力差异及原因分析

为探讨农药剂型对烟粉虱的毒力差异,分别以甘蓝和黄瓜叶片作为生物测定载体,比较了啶虫脒乳油(EC)、微乳剂(ME)、可溶性液剂(SL)、可溶性粉剂(SP)及可湿性粉剂(WP)等5种剂型对烟粉虱成虫的毒力,并通过对植物叶片临界表面张力、啶虫脒药液表面张力、动态接触角及叶片持液量的测定,分析了不同啶虫脒剂型间毒力差异形成的原因。结果表明:以甘蓝叶片为生物测定载体,不同啶虫脒剂型间对烟粉虱的毒力差异明显;以黄瓜叶片为生物测定载体,不同剂型间毒力差异不明显。啶虫脒SL、SP、WP在两种生物测定载体间的毒力差异大于EC和ME。甘蓝和黄瓜叶片的临界表面张力值分别为30.73 mN.m 1和57.91~63.30 mN.m 1。啶虫脒有效成分浓度大于7.81 mg.L 1时,啶虫脒EC和ME溶液表面张力即小于甘蓝和黄瓜叶片的临界表面张力;啶虫脒有效成分浓度大于500 mg.L 1时,啶虫脒SL、SP、WP溶液的表面张力才小于甘蓝叶片的临界表面张力。啶虫脒ME溶液液滴接触两种植物叶片的瞬间(0 s),液滴与叶片间的接触角就明显小于90°。甘蓝叶片对低浓度的啶虫脒ME和EC溶液的持液量高于其他3种剂型,黄瓜叶片对啶虫脒各剂型溶液的持液量无明显差异。植物叶片表面性质和不同剂型溶液表面张力的差异是导致剂型间产生毒力变化的重要原因。     

基于小白菜Cd吸收推算土壤Cd安全阈值

Cadmium(Cd), a common toxic heavy metal in soil, has relatively high bioavailability, which seriously threatens agricultural products. In this study, 8 different soils with contrasting soil properties were collected from different regions in China to investigate the Cd transfer coefficient from soil to Chinese cabbage(Brassica chinensis L.) and the threshold levels of Cd in soils for production of Chinese cabbage according to the food safety standard for Cd. Exogenous Cd(0–4 mg kg~(-1)) was added to the soils and equilibrated for 2 weeks before Chinese cabbage was grown under greenhouse conditions. The influence of soil properties on the relationship between soil and cabbage Cd concentrations was investigated. The results showed that Cd concentration in the edible part of Chinese cabbage increased linearly with soil Cd concentration in 5 soils, but showed a curvilinear pattern with a plateau at the highest dose of exogenous Cd in the other 3 soils. The Cd transfer coefficient from soil to plant varied significantly among the different soils and decreased with increasing soil p H from 4.7 to 7.5. However, further increase in soil pH to 8.0 resulted in a significant decrease in the Cd transfer coefficient. According to the measured Cd transfer coefficient and by reference to the National Food Safety Standards of China, the safety threshold of Cd concentration in soil was predicted to be between 0.12 and 1.7 mg kg~(-1) for the tested soils. The predicted threshold values were higher than the current soil quality standard for Cd in 5 soils, but lower than the standard in the other 3 soils. Regression analysis showed a significant positive relationship between the predicted soil Cd safety threshold value and soil p H in combination with soil organic matter or clay content.     

不同种类蔬菜苗期对镉的敏感性研究

产地环境中镉（Cd）对蔬菜的影响主要表现为蔬菜可食部分超标,高浓度时影响其生长发育,基于评述蔬菜幼苗对Cd的敏感性是按其对Cd的吸收累积量来排序,累积Cd量越高定义为该蔬菜幼苗对Cd越敏感,采用水培方法,探讨了Cd对小白菜（叶菜）、黄瓜、豇豆（果菜）和萝卜（根菜）幼苗吸收累积量及生长发育的影响。结果表明,蔬菜幼苗根和茎叶中累积Cd量均随Cd处理浓度的增加而显著增加（P〈0．05）。同一处理浓度下根中Cd含量远高于茎叶中Cd含量,根和茎叶对Cd的累积强弱顺序也即蔬菜苗期对Cd的敏感性排序为小白菜〉萝卜〉黄瓜〉豇豆;随Cd浓度增加,叶片中叶绿素含量降低,过氧化氢酶（CAT）含量升高;蔬菜出苗率、幼苗根长、植株鲜重显著降低。     

Fate of (14)C-labeled soybean and corn pesticides in tropical soils of Brazil under laboratory conditions

The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.     

钼对小白菜抗坏血酸氧化还原的影响

采用盆栽试验研究了钼对小白菜抗坏血酸含量、氧化还原状态及相关酶活性的影响。结果表明,各施钼水平均提高了小白菜产量、抗坏血酸总量以及还原型抗坏血酸（ASC）含量。随着施钼水平的提高,抗坏血酸过氧化物酶（APX）、单脱氢抗坏血酸还原酶（MDHAR）、脱氢抗坏血酸还原酶（DHAR）活性均呈上升的趋势;抗坏血酸氧化酶（AAO）活性逐渐下降。表明施用钼肥能够促进小白菜抗坏血酸氧化还原及再生循环过程,从而提高了抗坏血酸的含量。     

Pyruvate kinase activity as an indicator of the level of K(+), Mg(2+), and Ca(2+) in leaves and fruits of the cucumber: the role of potassium fertilization.

Little is known about the effects of K(+) fertilization on pyruvate kinase (PK) activities in cucumber (Cucumis sativus L. cv. Brunex) grown in the greenhouse on calcareous soils. Here, the effect of K rates on the concentrations of K(+), Mg(2+), and Ca(2+) and on the PK activity as a possible indicator of the levels of these cations in the leaves and fruits of cucumber plants has been studied. The treatments consisted of applications of three rates of K in the form of K(2)SO(4) (K1 = 0.075 mg mL(-)(1), K2 = 0.15 mg mL(-)(1), and K3 = 0.30 mg mL(-)(1)). In general, K(+) application in calcareous soils proved beneficial. The highest application of K(+) (K3) to the culture medium reduced, in both the leaves and fruits, the foliar concentrations of Mg(2+) and Ca(2+). These results are reflected by the lowest basal PK activities and the highest differences between the basal PK activity and activities stimulated by these two cations. The opposite effect resulted with K2, with maximal basal PK activity and minimal differences between this activity and activities stimulated by the cations, indicating a better balance in this treatment between the different cations under the experimental conditions. Finally, this trend might partly account for the highest commercial yield in plants treated with K2.