Effects of Contaminants on Toxicity of the Lampricides TFM and Bayer 73 to Three Species of Fish

Waters in the Great Lakes basin contain more than 400 contaminant chemicals that potentially affect fishery resources, commerce, and human inhabitants. We determined in the laboratory the effects of selected contaminants on the toxicity of the widely used lampricides TFM (3-trifluoromethyl-4-nitrophenol) and Bayer 73 (2′,5-dichloro-4′-nitrosalicylanilide) to three species of fish—rainbow trout (Salmo gairdneri), white sucker (Catostomus commersoni), and fathead minnow (Pimephales promelas). The fish were exposed to paired mixtures of lampricides and selected contaminants in standardized, acute static toxicity tests to determine the resulting type of response—less than additive, additive, or greater than additive (synergistic). As expected, the toxicities of combinations of lampricides with organic pesticides, metal, industrial or municipal pollutants, and tannic acid were mostly additive. However, the toxicity of a combination of TFM, Delnav, and malathion was synergistic, and extremely small quantities of each chemical became lethal when mixed. The concentration that produced 50% mortality was 1.64 mg/L for TFM alone but only 0.041 mg/L for TFM with the pesticides. Toxicities of the pesticides in the combination also increased commensurately. The triple combination of chemicals produced extraordinary synergism and effectively demonstrated the hazards that may result if certain chemical combinations occur in the aquatic environment. However, synergism is not the only kind of toxic action that produces hazards to aquatic organisms. All three types of toxic action are of concern because toxic units produced by contaminant chemicals add to the toxic units of applied management chemicals. Since the toxicity of the majority of chemical combinations is simply additive, this cumulative toxic action contributes more total units to aquatic environments than the extreme actions of less than additive and synergism. The toxicity of the lampricide TFM, as well as other management chemicals, is reinforced by the presence of any contaminant that contributes additional units of toxicity. Therefore, all types of cumulative toxic action should be of concern to people and agencies involved with protecting the environment.     

Occurrence of Lawn Care and Agricultural Pesticides in the Don River and Humber River Watersheds (1998–2002)

Between 1998 and 2002, surface water samples were collected from several sites in the Don River and Humber River watersheds, both tributaries to Lake Ontario, and analyzed for a variety of pesticides, including those used for urban lawn care. Analyses included 152 pesticide active ingredients and eight metabolites. Samples were collected during base flow periods (i.e., dry events) and rainfall events (i.e., wet events). The objectives of the study were to determine which pesticides were detectable, whether there was a difference in the detection frequency between the two watersheds and between upstream and downstream in each river, and whether precipitation influenced the frequency of detection. Eleven pesticides and one metabolite were detected in surface waters of the Don and Humber rivers or their tributaries, with approximately 72% of samples containing at least one pesticide attributable to lawn care use. The pesticides and pesticide metabolite detected in this study included 2,4-D, atrazine, bromacil, carbofuran, chlorpyrifos, cypermethrin, diazinon, dicamba, MECOPROP, metolachlor, metribuzin, and an atrazine metabolite (des-ethyl atrazine). Four pesticides exceeded federal or provincial water quality guidelines/objectives. Diazinon exceeded the provincial water quality objective in 28% of the samples taken. For the three other pesticides (atrazine, carbofuran and chlorpyrifos) exceedance of a water quality criteria occurred in less than 1% of the samples.     

Combining feature spaces for classification

In this paper we offer a variational Bayes approximation to the multinomial probit model for basis expansion and kernel combination. Our model is well-founded within a hierarchical Bayesian framework and is able to instructively combine available sources of information for multinomial classification. The proposed framework enables informative integration of possibly heterogeneous sources in a multitude of ways, from the simple summation of feature expansions to weighted product of kernels, and it is shown to match and in certain cases outperform the well-known ensemble learning approaches of combining individual classifiers. At the same time the approximation reduces considerably the CPU time and resources required with respect to both the ensemble learning methods and the full Markov chain Monte Carlo, Metropolis-Hastings within Gibbs solution of our model. We present our proposed framework together with extensive experimental studies on synthetic and benchmark datasets and also for the first time report a comparison between summation and product of individual kernels as possible different methods for constructing the composite kernel matrix.     

Degradation of organophosphorus pesticides in aqueous extracts of young green barley leaves (Hordeum vulgare L)

The degradation of the organophosphorus pesticides malathion, chlorpyrifos, guthion, diazinon, methidathion and parathion in an aqueous extract of young green barley leaves (Hordeum vulgare L) was monitored by gas chromatography. Aqueous solutions of various amounts of freeze‐dried young barley leaves containing 5.75 mg l⁻¹ of malathion were incubated at 37 °C and pH 7.4 over prolonged time periods. Over 95% of the malathion degraded in 4 h in a 3% (30 g l⁻¹) solution of young green barley leaves. When the barley solution was autoclaved at 120 °C for 25 min prior to the addition of malathion, no degradation of malathion was observed. When 10 mg l⁻¹ each of the above six pesticides was incubated in a 15% (150 g l⁻¹) solution of young green barley leaves for 3 h at 37 °C and pH 7.4, malathion and chlorpyrifos degraded 100%, whereas parathion (75%), diazinon (54%), guthion (41%) and methidathion (23%) showed lesser degrees of degradation. © 1999 Society of Chemical Industry     

Assessment of PCDD/F,PCB, OCP and BPA dietary exposure of non-breast-fed European infants

The aim of this study is to obtain data on the exposure of non-breast-fed infants to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), polychlorinated biphenyls (PCB), organochlorine pesticides (OCP), and bisphenol A (BPA) and its chlorinated derivatives through consumption of commercial infant foods with largest shares of the market in 22 European Union countries. The E-Screen bioassay was employed to assess the oestrogenicity of the baby foods and the ethoxyresorufin-O-deethylase (EROD) induction was measured to determine the levels of PCDD/F and PCB. Consequently, the highest total effective xenoestrogen burden (TEXB) of 73.60?pM?Eeq?g^?1 was found in the soy-based formula and the EROD bioassay was always below the limit of quantification (LOQ) (3.5?pg?g^?1). Overall, the estimated dietary exposure to BPA via commercial baby foods was lower than the tolerable daily intake (TDI) of 50?µg?kg^?1 body weight (bw). Furthermore, the findings indicated that the dietary exposure of 0–9-month-old infants through the products investigated here does not exceed the maximum TDI of 4?pg WHO-TEQ (toxic equivalents)?kg^?1 bw. However, exposure to more than 2?pg WHO-TEQ?kg^?1?bw?day^?1 might occur for 0–4-month-old infants consuming ‘starting’ hypoallergenic formula. Moreover, analysis of OCP indicated that the dietary exposure of non-breast-fed infants was not harmful. Considering the importance of early development and the vulnerability of infants and children, it is essential to determine their dietary exposure to contaminants in order to decide which efforts of risk reduction should receive highest priority.     

Multi-residue method for the analysis of pesticides in Arabica coffee using liquid chromatography/tandem mass spectrometry

Coffee is a major tropical agricultural commodity and represents a significant fraction of the economy of many countries. However, certain plant and animal species can damage coffee crops, affecting trade. A solution to this issue is the use of pesticides, some of which are harmful to human health and the environment. This work consisted of the development of a multi-residue method for the analysis of pesticides in coffee by using LC-MS/MS. The QuEChERS extraction procedure was used. The following analytical parameters were optimised: selectivity, analytical range, linearity, LOD, LOQ, precision (RSD%) and recovery of the method. The results showed that the method is selective, as they were linear in the range of 10.0–100.0 µg kg^?1. The sensitivity, recovery and precision were adequate for the multi-residue analysis of pesticides in coffee. The method was applied to the analyses of 15 Brazilian coffee samples.     

Dietary exposure of Hong Kong adults to pesticide residues: results of the first Hong Kong total diet study

The use of pesticides and other chemicals has become a common practice in modern agriculture to enhance and stabilise crop yield, protect the nutritional integrity of food, facilitate food storage to assure year-round supplies, and provide attractive and appealing food products. With the adoption of strict good agricultural practice (GAP), only minimal amounts of pesticide residues should remain on the crops or in connected foods of animal origin up the food chain. To assess their associated health risk to local people, the dietary exposure of Hong Kong adults to residues of four groups of pesticides or their metabolites – organophosphorus pesticides (OPPs), carbamates, pyrethrins and pyrethroids, and dithiocarbamate (DTC) metabolites – is estimated in the first Hong Kong Total Diet Study (TDS). A total of 150 commonly consumed food items were collected and prepared “as consumed”. A total of 600 composite food samples were analysed for 85 pesticides or their metabolites by liquid chromatography-tandem mass spectrometry (LC-MS/MS). These pesticides were primarily found at low levels (highest mean = 350 μg kg^?1) in food samples of plant origin such as vegetables and fruits. Dietary exposures to pesticide residues were estimated based on the analytical results and the food consumption data of the local residents. The estimated dietary exposures of Hong Kong adults to all individual pesticides were well below their respective acceptable daily intakes (ADIs). The percentage contributions of the estimated mean and 95th percentile dietary exposures to the ADIs of individual pesticides were <6% and <24% for the OPPs, <1% for the carbamates and pyrethrins and pyrethroids, and <1% and <4% for the DTC metabolites, respectively. The findings indicate that dietary exposures to all the pesticide residues analysed in this study were unlikely to pose unacceptable health risks to the Hong Kong population.     

Determination of multi-class pesticide residue in dietary supplements from grape seed extracts by ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry

A new method was developed and validated for the determination of multi-class pesticide residues in nutraceutical products obtained from grape seed extracts. The extraction procedure was based on QuEChERS methodology using ethyl acetate as solvent and a dispersive solid-phase extraction (dSPE) clean-up stage with C₁₈ was included to minimise matrix effects. Pesticides determination was achieved using ultra-high-performance liquid chromatography coupled to triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS); total running time was 11 min. Pesticides were quantified using matrix-matched calibration. The developed method was validated in terms of matrix effect, linearity, selectivity, limits of detection and quantification, trueness, repeatability and inter-day precision at three concentration levels (10, 50, 100 µg kg^?1). Suitable recovery values were obtained for 76% of analysed pesticides at the lowest concentration (10 µg kg^?1). For most of the compounds, relative standard deviation values were lower than 20% and 25% for intra- and inter-day precision, respectively. Finally, 106 pesticides were determined, and the method was applied to seven dietary supplements from grape seed extract, obtaining various positive results for piperonyl butoxide, cyromazine and diniconazole at concentrations ranging from 2.0 to 13.4 µg kg^?1.     

食品中有机磷农药残留分析研究进展

有机磷农药在生物链中的积累较低,被广泛应用于农作物病虫害防治领域,但它对生物机体机能有着较为严重的毒害作用.建立有效、快速、灵敏的有机磷农药痕量残留的检测技术,成为当前研究者关注的课题.本文重点对农药残留的检测方法进行综述,内容涵盖了近年来国内外食品中有机磷农药残留的提取与分离新技术方法和现代分析方法.     

QuEChERS-HPLC-Q-TOF/MS快速筛查蔬菜中32种农药残留

建立了QuEChERS-高效液相色谱-四极杆-飞行时间质谱法用于蔬菜中32种农药残留的快速筛查与确证分析方法。乙睛为提取剂,氯化钠盐析,C18和PSA为净化剂,电喷雾正离子扫描。通过TOF MS-IDA-MS/MS扫描模式,一次采集即可同时获得农药分子的一级精确质量数和二级质谱图信息。在线性范围内32种化合物线性关系良好,相关系数均大于0.9990,在三个加标水平(1,4和20 LOQ)下的平均回收率为70.41%~103.1%,相对标准偏差为1.2%~11.2%,方法检出限LOD为0.3~1.3μg/kg,定量限LOQ为1.0~4.0μg/kg。与国标相比,大大缩短前处理时间;此外,该方法中吡虫啉、虫酰肼等9种农药的方法检出限得到了有效降低;除乙霉威和嘧菌酯回收率略低,其它30种农药回收率均无明显差别。该方法简单快速、高效准确、灵敏度高,能够快速筛查和分析蔬菜中残留农药。