Leaching potential of some phenylureas and their main metabolites through laboratory studies

BACKGROUND, AIMS AND SCOPE: Laboratory studies were conducted with the aim of defining the leaching potential of some phenylureas and their metabolites. A first study was performed for calculating their leaching index (as GUS) on the base of intrinsic properties: persistence (as DT50) and mobility (as Koc) in soil. Another study consisted of aged column leaching experiments whose meaning was to semi-quantify the occurrence of the tested compounds in the leachates, so simulating in field conditions. METHODS: The tested compounds were: diuron, linuron and monolinuron (parents); 3,4-dichloroaniline (DCA), 4-chloroaniline (CLA), 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU), 1-(3,4-dichlorophenyl)urea (DCPU), 1-(4-chlorophenyl)urea (CPU) and monuron, this latter considered both as a metabolite and parent compound. The Koc values of the examined substances were determined by the HPLC screening methods, according to the OECD TG 121. DT50 determinations and aged column leaching experiments were carried out according to SETAC procedures. RESULTS AND DISCUSSION: The examined compounds showed a rather wide range of persistence in soil, with DT50 values less than 2 days for DCA and CLA, close to 8 days for DCPU and CPU and from 16 (diuron) up to 24.8 (DCPMU) days for the others. Their mobility was generally high, based on their Koc values, which ranged from 33 (CPU) to 406 (linuron). The GUS indices indicated that monuron has a clear potential to contaminate groundwater (> 2.8); DCPMU, monolinuron, CPU and diuron are intermediate contaminants (1.8-2.8). Linuron, DCPU, CLA and DCA exhibited a non-leaching behaviour (< 1.8). The aged leaching column experiments showed that parents were found in the leachates at very high percentages respect to the doses applied. The metabolites reached much less percentages, the highest values were observed for monuron from diuron (5.7), CPU (7.2) and DCPMU (8.2%). CONCLUSION: Diuron, Monuron, CPU and DCPMU on the basis of their intrinsic properties, formation from their parents and occurrence in leachates from aged column leaching studies, seem to possess the characteristics of groundwater contaminants. The methodological approach of this study is relatively easy and rapid, hence it can represent a tool for a first screening of compounds such as pesticide metabolites (generally available only in small quantities and for which a field study is not conceivable) or other compounds for which not adequate environmental data are available.     

铜绿假单胞菌降解菲的产物鉴定及代谢过程

研究了1株能快速降解疏水性化合物的铜绿假单胞菌NY3对菲的降解机理。GC-MS分析表明,该菌代谢菲的各个阶段,能够被检测到的主要酸性产物有1-羟基-2-萘甲酸、α-萘酚、邻羟基苯基羰基乙酸、水杨酸、苯甲酸等。铜绿假单胞菌NY3经过一系列氧化代谢将菲转化为1-羟基-2-萘甲酸,进一步反应生成α-萘酚。由菲到1-羟基-2-萘甲酸,未检测到其他产物,说明该阶段产物被继续代谢的速度快,产物含量低不易积累。1-羟基-2-萘甲酸为体系中积累的唯一的主要代谢产物。尽管继续代谢速度慢,但它可以按照α-萘酚、邻羟基苯基羰基乙酸、水杨酸、苯甲酸途径被继续转化。NY3降解菲的代谢产物中未检测到二羟基萘、苯二酚等多羟基化合物,但羟基和羧基处于邻位的化合物,如1-羟基-2-萘甲酸和水杨酸有非常明显积累的趋势,α-萘酚和苯甲酸积累速度次之。     

Chemical studies on Indopacific Ceratosoma nudibranchs illuminate the protective role of their dorsal horn

Summary. Two Ceratosoma species, C. trilobatum and C. gracillimum (Mollusca: Gastropoda: Opistobranchia), collected along the South China Sea coast, have been studied in order to investigate their defensive strategies. Both species contain four typical sponge furanosesquiterpenoids, probably with a dietary origin. The tissue distribution of these compounds has been studied by ¹H-NMR analysis and preliminary bioassays have been carried out in order to evaluate the ecological role of the isolated metabolites. The main sesquiterpene component in both species was (–)-furodysinin (2), which showed significant feeding-deterrent and ichthyotoxic properties in bioassays with freshwater organisms. The work has been performed studying a very limited number of molluscs that prevented the realization of ecologically relevant experiments. However, the almost exclusive presence of compound 2 in the crude extract of the mantle glands concentrated in the dorsal horn of C. gracillimum strongly supports the defensive role of that dorsal protuberance, which probably acts as a defensive lure attracting potential predators to the part of the animal that contains the distasteful chemicals.     

Assessment of bioavailable PAH, PCB and OCP concentrations in water, using semipermeable membrane devices (SPMDs), sediments and caged carp

Bioavailable water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed at several freshwater sites in and around the city of Amsterdam. Carp (Cyprinus carpio) were caged for 4 weeks at 10 sites, together with semipermeable membrane devices (SPMDs). In addition, sediment samples were taken at each site. SPMDs and sediments were analysed for PAHs, PCBs and OCPs. Carp muscle tissues were analysed for PCBs and OCP, while PAH metabolites were assessed in fish bile. Contaminant concentrations in the water phase were estimated using three different methods: 1. Using fish tissue concentrations and literature bioconcentration factors (BCFs), 2. Using SPMD levels and a kinetic SPMD uptake model, and 3. Using sediment levels and literature sorption coefficients (K_ocs). Since PAH accumulation in fish is not considered an accurate indicator of PAH exposure, calculated aqueous PAH concentrations from SPMD data were compared with semiquantitatively determined biliary PAH metabolite levels. Contaminant concentrations in the water phase estimated with fish data (Cw_fish) and SPMD data (Cw_spmd) were more in line for compounds with lower K_ow than for compounds with higher K_ow values. This indicates that the assumption of fish–water sorption equilibrium was not valid. At most sites, sediment-based water levels (Cw_sed) were comparable with the Cw_spmd, although large differences were observed at certain sites. A significant correlation was observed between biliary PAH metabolite levels in fish and aqueous PAH concentrations estimated with SPMD data, suggesting that both methods may be accurate indicators of PAH exposure in aquatic ecosystems.     

2, 4-二硝基甲苯在鲤鱼体内的代谢研究

应用水生生物体内实验方法，研究了２，４－二硝基甲苯在鲤鱼肝肠提取物中的生物浓缩及代谢转化过程。半静态条件下，采用３种不同的暴露浓度，测定肝，肠组织的生物浓缩曲线，并同步对肝提取物进行了ＨＰＬＣ检测。     

Identification of naphthalene metabolism by white rot fungus Armillaria sp. F022

Armillaria sp. F022, a white rot fungus isolated from tropical rain forest (Samarinda, Indonesia) was used to biodegrade naphthalene in cultured medium. Transformation of naphthalene by Armillaria sp. F022 which is able to use naphthalene, a two ring-polycyclic aromatic hydrocarbon (PAH) as a source of carbon and energy was investigated. The metabolic pathway was elucidated by identifying metabolites, biotransformation studies and monitoring enzyme activities in cell-free extracts. The identification of metabolites suggests that Armillaria sp. F022 initiates its attack on naphthalene by dioxygenation at its C-1 and C-4 positions to give 1,4-naphthoquinone. The intermediate 2-hydroxybenzaldehyde and salicylic acid, and the characteristic of the meta-cleavage of the resulting diol were identified in the long-term incubation. A part from typical metabolites of naphthalene degradation known from mesophiles, benzoic acid was identified as the next intermediate for the naphthalene pathway of this Armillaria sp. F022. Neither phthalic acid, catechol and cis,cis-muconic acid metabolites were detected in culture extracts. Several enzymes (manganese peroxidase, lignin peroxidase, laccase, 1,2-dioxygenase and 2,3-dioxygenase) produced by Armillaria sp. F022 were detected during the incubation.     

Screening of endogenous antioxidants in some medicinal plants

The evaluation of antioxidant enzymes and antioxidant metabolites was done in leaf tissues of Azadirachta indica, Butea monosperma, Cassia fistula, Mangifera indica, and Syzygium cumini growing in the Thar Desert, Rajasthan, India. The plants are naturally exposed to drought stress and high temperatures during summer. Enzymatic reactive oxygen species (ROS) scavenging mechanisms in plants include superoxide dismutase (SOD), ascorbate peroxidase (APX), glutathione reductase, catalase, and guaiacol peroxidase, and non-enzymatic antioxidants including the carotenoids, proline, and vitamin C were studied. The strategies to cope up with ROS under these extreme conditions are plant-specific. The highest activity of APX was found in M. indica (13.6?±?2.4?units?g^?1 fresh wt.). A. indica exhibited maximum guaiacol peroxidase activity (0.024?±?0.006?units?min?g^?1 fresh wt.), while S. cumini showed maximum SOD (12.5?±?2.3?units?g^?1 fresh wt.) and catalase activities (6.9?±?2.2?units?g^?1 fresh wt.). M. indica and S. cumini have been found to be more potent antioxidant systems among the studied plants.     

Biodegradation of phenylurea herbicide diuron by microorganisms from long-term-treated sugarcane-cultivated soils in Kenya

The phenylurea herbicide diuron [N-(3,4-dichlorophenyl)-N,N-dimethylurea] is widely used alone or in a broad range of herbicide formulations. Its degradation in sugarcane-cultivated soils which have been impacted by the herbicide through repeated applications was studied. Liquid culture experiments with diuron as the only carbon source led to the isolation of different bacterial strains capable of degrading diuron. The bacterial species belonging to the genera Bacillus, Vagococcus, and Burkholderia, identified through biochemical and molecular characterization, degraded diuron to different extents. The isolated Bacillus cereus, Vagococcus fluvialis, Burkholderia ambifaria, and Bacillus spp1 degraded diuron by 21%, 25%, 22%, and 19% of the initially applied concentration of 40?mg?L^?1, respectively, after 35 days of incubation in liquid culture media. Small amounts of 3,4-dichloroaniline and the de-methylated metabolite N-(3,4-dichlorophenyl)-N-methylurea were detected in liquid culture media. The combination of V. fluvialis and B. ambifaria showed an enhanced degradation of up to 30% of the initially applied concentration of 40?mg?L^?1. Degradation by pure isolates was low (18–25%) compared to the capacities of diuron degradation shown by the bacterial communities (58–74%). This study showed the presence of diuron degraders in sugarcane-cultivated soils impacted by diuron due to repeated applications.     

新农药吡虫啉及其代谢产物对土壤呼吸的影响

为评价吡虫啉对土壤生态环境造成的影响,用直接吸收法测定土壤呼吸强度,比较了吡虫啉浓度为0、10、40和100μg/g及40μg/g水解、光解产物的影响.结果表明高浓度吡虫啉对土壤呼吸的抑制作用较强,水解产物对土壤呼吸的影响小于吡虫啉,10min光解产物对土壤呼吸的影响要略强于吡虫啉,但30min光解产物对土壤呼吸的影响大大降低.13d后各处理的土壤呼吸强度基本恢复.吡虫啉及其代谢产物均属于低毒或无实际危害的农药,对土壤微生物影响较小.     

Glucosinolates and other metabolites in the leaves of <Emphasis Type="Italic">Arabidopsis thaliana</Emphasis> from natural populations and their effects on a generalist and a specialist herbivore

Because many secondary metabolites in plants act as defense against herbivores it has been postulated that these compounds have evolved under selective pressure by insect herbivores. One explanation for the within-species variation in metabolite patterns in a particular species is that different populations are under selection by different herbivores. We tested this hypothesis, using Arabidopsis thaliana plants that originated from dune and inland areas. We analyzed Arabidopsis thaliana leaves using NMR spectroscopy and multivariate data analysis. Major differences in chemical composition were found in water-methanol fractions and were due to higher concentrations of sinigrin and fumaric acid in dune plants. Inland plants showed lower levels of glucose. Quantitative analysis of glucosinolates was performed with HPLC. Individual plants and populations demonstrated differences in glucosinolate composition and concentration. In growth chamber experiments, the generalist herbivore, Spodoptera exigua grew significantly better on the inland plants, while the specialist herbivore Plutella xylostella performed equally well on plants of both origins. Aliphatic glucosinolate as well as total glucosinolate concentrations negatively correlated with larval mass of Spodoptera exigua. No significant correlations, however, were found between larval mass of Plutella xylostella and glucosinolates in the leaves. A specialist and a generalist herbivore were responding differently to plant secondary chemistry, as was also found in several other studies. This is an important indication that differences in glucosinolate concentrations among populations may result from differential selection by different guilds of herbivores.