Evaluation of C18 solid‐phase extraction cartridges for the isolation of select pesticides and metabolites

Abstract

Nine different C₁₈ solid‐phase extraction (SPE) cartridges were evaluated for their efficiency at extracting nine pesticides and two s‐triazine metabolites from spiked deionized water samples. The SPE cartridges were found to contain nitrogen (N) and/or phosphorus (P) contaminants and varied in their extraction efficiency for certain pesticides and metabolites. Four of the nine SPE cartridges gave acceptable (70 to 120%) pesticide and metabolite recovery percentages, while five cartridges had marginal (50 to 70%) to poor (< 50%) recoveries. Statistical analyses showed that the poor to marginal recoveries found for three compounds could not be explained by considering several indigenous chemical and physical traits of the cartridge. It is suggested that proper SPE cartridge selection for pesticide recovery should be evaluated using several different cartridges.     

Metabolism of the Nonylphenol Isomer [Ring-U-14c]-4-(3′,5′-Dimethyl-3′-Heptyl)-Phenol by Cell Suspension Cultures of Agrostemma githago and Soybean

Abstract

The biotransformation of the nonylphenol isomer [ring-U-¹⁴C]-4-(3′,5′-dimethyl-3′-heptyl)-phenol (4-353-NP, consisting of two diastereomers) was studied in soybean and Agrostemma githago cell suspension cultures. With the A. githago cells, a batch two-liquid-phase system (medium/n-hexadecane 200:1, v/v) was used, in order to produce higher concentrations and amounts of 4-353-NP metabolites for their identification; 4-353-NP was applied via the n-hexadecane phase. Initial concentrations of [¹⁴C]-4-353-NP were 1 mg L^?1 (soybean), and 5 and 10 mg L^?1 (A. githago). After 2 (soybean) and 7 days (A. githago) of incubation, the applied 4-353-NP was transformed almost completely by both plant species to four types of products: glycosides of parent 4-353-NP, glycosides of primary 4-353-NP metabolites, nonextractable residues and unknown, possibly polymeric materials detected in the media. The latter two products emerged especially in soybean cultures. Portions of primary metabolites amounted to 19–22% (soybean) and 21–42% of applied ¹⁴C (A. githago). After liberation from their glycosides, the primary 4-353-NP metabolites formed by A. githago were isolated by HPLC and examined by GC-EIMS as trimethylsilyl derivatives. In the chromatograms, eight peaks were detected which due to their mass spectra, could be traced back to 4-353-NP. Seven of the compounds were side-chain monohydroxylated 4-353-NP metabolites, while the remaining was a (side-chain) carboxylic acid derivative. Unequivocal identification of the sites of hydroxylation/oxidation of all transformation products was not possible. The main primary metabolites produced by A. githago were supposed to be four diastereomers of 6′-hydroxy-4-353-NP (about 80% of all products identified). It was concluded that plants contribute to the environmental degradation of the xenoestrogen nonylphenol; the toxicological properties of side-chain hydroxylated nonylphenols remain to be examined.     

环境中苯并(a)芘监测技术及建议

环境中BaP是引起人们各类癌症的主要诱发物.叙述了环境中BaP的来源及其浓度状况,列举了国家制定的各项标准中的BaP含量的浓度限值,论述了环境水中和空气中BaP的样品采集、保存、前处理、分析测定及定量监测中应注意的几个问题,提出了监测BaP的4点建议.     

Mutagenicity of chloroaniline/lignin metabolites in the salmonella/microsome assay

Abstract

Chloroanilines are constituents of many agrochemicals and have been found to be metabolized to succinic acid conjugates, e.g., succinamides and succinimides. The mutagenic potential of five chloroanilines and their succinamides and succinimide derivatives have been tested with two strains of Salmonella typhimurium (TA98 and TA100) with and without rat hepatic micro‐somal fraction. None of the compounds produced a dose response effect with a two‐fold increase in revertants indicating that these compounds are not mutagens or promutagens in these assays.     

MODEL FOR PREDICTING TRANSPORT OF PESTICIDES AND THEIR METABOLITES IN THE UNSATURATED ZONE1

ABSTRACT: A finite element model based on Galerkin's upstream weighted residual technique was developed to predict the simultaneous convective-dispersion transport and transformations of pesticides and their metabolites in the unsaturated zone. Transformations of the parent compound and its metabolites were assumed to be first-order reactions for oxidation and hydrolysis, while adsorption of the pesticide species (parent compound and metabolites) to the soil components was assumed to be represented by a linear equilibrium (Freundlich type) isotherm. Volatilization and plant root uptake of pesticides in the solution phase were neglected in the analysis. The proposed model was used to simulate the transport and transformation of aldicarb and its metabolites, aldicarb sulfoxide and aldicarb sulfone, in the soil profile. Several examples are used to demonstrate the accuracy, validity, and applicability of the proposed model. Simulated results indicate that the proposed model can potentially be used to estimate the mass flux of water, and pesticide and pesticide metabolite concentrations in the subsurface environment. However, further verification of the model against actual field data is needed to fully demonstrate the model's potential.     

苯并芘对稀有鮈鲫的内分泌干扰效应研究

为评价典型有机污染物对长江三峡库区上游特有珍稀鱼类的环境风险,本实验以稀有鮈鲫为对象,研究了低剂量多环芳烃(PAHs)暴露而引起的内分泌干扰效应.将成年稀有鮈鲫暴露于不同浓度(0、0.1、0.3、1.0和3.0μg·L-1)的苯并芘(Ba P)中28 d,测定了体质系数、性激素含量、下丘脑-垂体-性腺(HPG)轴和肝脏中与繁殖相关基因的表达.结果显示:在雌鱼中,Ba P暴露后,睾酮(T)的含量显著升高,雌二醇(E2)的水平显著下降并改变了T/E2的比值;在雄鱼中,T和E2的含量都显著下降.雌雄鱼性激素的改变可能与类固醇合成相关基因(Cyp17、Cyp19a)表达量的改变有关.Ba P暴露显著抑制了雌雄鱼肝脏中卵黄蛋白原(VTG)基因的表达.以上检测到的激素或者基因表达的改变主要发生在高剂量(3.0μg·L-1)Ba P暴露下,而长江上游库区水体中多环芳烃含量较低(100 ng·L-1),因此推测,库区存在的多环芳烃不会对三峡库区上游水体中的鱼类产生内分泌干扰效应.     

Bacterial colonization of the phyllosphere of nineteen plant species and antimicrobial activity of their leaf secondary metabolites against leaf associated bacteria

Summary. The scope of this work was to examine whether leaf constitutive secondary metabolites play a role in determining bacterial colonization of the phyllosphere. To this aim, we surveyed nineteen native or cultivated plant species that share a common bacterial pool in a North Mediterranean area, and estimated the size of total and ice nucleation active (INA) bacterial populations on their leaves. Large differences in the colonization of their phyllosphere were found; the population size of epiphytic bacteria ranged from 7.5 × 10² to 1 × 10⁶ CFU/g fresh weight, in eucalypt and celery, respectively. Species native in Mediterranean-type climate areas, particularly those belonging to the group of aromatic plants, are characterized by scarce presence of INA bacteria. The antibacterial activity of essential oils, surface phenolics and leaf tissue extracts was also estimated against the INA strains P. syringae and E. herbicola, isolated from two of these plant species. E. herbicola proved more sensitive than P. syringae. Of the species examined, oregano [Origanum vulgare L. subsp. hirtum (Link.) Ietswaart], an aromatic plant, had the highest antimicrobial activity, whereas six species showed no activity at all. Further experiments were performed with oregano and bean (Phaseolus vulgaris L.) that represent two extremes in their secondary metabolite content. Both plants were inoculated with P. syringae. By the end of incubation, the bacterial population on bean plants was about 100 times higher than that on oregano leaves. Scanning electron micrographs showed that bacterial growth on oregano leaves was confined to sites away from glandular hairs. Results from the bacterial colonization survey together with those from the toxicity tests showed that all species rich in antibacterial secondary metabolites harbored low leaf bacterial populations. These results provide substantial evidence that leaf secondary metabolites function as constitutive defense chemicals against microbial invasions. However, the fact that species with non- or moderately active leaf secondary metabolites are not always highly colonized suggests mediation of other unknown factors, the contribution of which requires further investigation.     

Secondary metabolism — evolution and function: Products or processes?

Summary The distinguishing characteristics of secondary metabolism and its associated metabolites are outlined. Current theories relating to the function of secondary metabolism in plants and micro-organisms are enumerated and the view that consideration of the processes rather than the products may best explain the origins of secondary metabolism is discussed.     

How do slugs cope with toxic alkaloids?

Summary. Arion lusitanicus and other slugs are able to feed on a variety of plants, even those containing toxic secondary metabolites, such as alkaloids. Alkaloids, like sparteine, lupanine, quinidine and atropine are avoided in no-choice feeding experiments only when they are present in concentrations above 1 mg/g food pellet. Alkaloids (sparteine, lupanine, cytisine, quinidine, atropine, senecionine, eserine, and harmaline) are toxic to Arion lusitanicus when injected. LD₅₀ values are 10 to 20 fold higher than in vertebrates indicating that slugs have a high tolerance towards food toxins. The tolerance is higher in young animals than in adult slugs. Injected alkaloids are rapidly detoxified within 72 h. Tolerance and detoxification can be induced by feeding slugs on non-lethal doses of lupin alkaloids. Using isolated microsomal preparations from the digestive gland, active detoxification was observed in vitro. Evidence is presented that cytochrome p450 plays an important role in detoxification of the applied alkaloids. A powerful and inducible detoxification systems appears to be the main mechanism that allows slugs to feed on plants rich in secondary metabolites (when no other food is available), that are usually avoided by other herbivores.     

Volatile metabolites from indoor molds grown on media containing wood constituents

Since volatile mold metabolites are used for the detection of mold growth in buildings, it was interesting to determine whether different indoor mold species show different affinity for the major components of wood, a common building material. Growth and volatile metabolites were studied when Aspergillus versicolor, Penicillium chrysogenum, and P. palitans were grown on laboratory substrates containing the major wood constituents cellulose, xylan and lignin. Microbial volatile organic compounds (MVOCs) were characterized by thermal desorption/gas chromatography/mass spectroscopy. Growth and volatile metabolites varied considerably and there appeared to be complementary substrate specificities for P. chrysogenum, and P. palitans grown on cellulose and xylan. The failure of A. versicolor to produce characteristic MVOCs when grown on media containing wood constituents suggests that systems using volatile metabolites to detect microbial growth in buildings may be fundamentally unreliable for the detection of this species.