Environmental fate of pesticides used in Australian viticulture IV. Aqueous stability of dithianon

Dithianon formulations are unstable in slightly basic aqueous solutions (pH 9, 20°C, t _½ = 5.6 h) but relatively stable in neutral or acidic solution (pH 4,20°C, t _½ = 6443 h). To ensure the efficacy of this fungicide it is important to prepare the spray mix fresh with neutral or slightly acidic water. Dithianon is unstable towards natural sunlight in the solid and aqueous phase, with half‐lives of approximately 68 and 42 days, respectively. Thermal hydrolysis does not seem to be the preferred degradation pathway when aqueous solutions are heated by the South Australian summer sun. The major aqueous phase photodegradation product has been identified as 2,3‐dihydro‐1,4‐dithiaanthraquinone. These results strongly suggest that should dithianon be accidentally released into basic Australian waters then it is likely to be rapidly chemically hydrolysed and pose little long term environmental threat. However, dithianon is only slowly chemically and photo‐lytically hydrolysed in neutral and acidic waters, and in this case accidentally release may pose a significant short term environmental threat.     

Determination of pesticides in apples,grapes and apple juice from a Kosovo market by gradient liquid chromatography with tandem mass spectrometry

Apple, grape, and apple juice were analyzed for pesticides using a multireaction mode (MRM) method in samples taken from a Kosovo market. With this method it was possible to analyze about 100 pesticides in the ESI mode. In these samples some types of pesticides were found, but most of them did not exceed the maximum tolerance levels. In apple samples, six pesticides were detected but only three of them were in sufficient quantitites. Dimethoat was below the limit, while acephate and imazalil exceeded the limit. In grape and apple juice samples, all of pesticides which were found did not exceed the maximum tolerable limits.     

Field dissipation and health hazard assessment of Fenhexamid on Egyptian grapes

Dissipation behavior and hazard assessment of the fungicide fenhexamid applied to grapes were investigated under climatic conditions in Egypt. Fenhexamid residues were extracted from grape samples with ethyl acetate. The extract was cleaned up by QuEChERS (quick, easy, cheap, effective, rugged, and safe) method, and determined by gas chromatographic method (GC-μECD). The average recoveries ranged between 94.2% and 99.4% with associated relative standard deviation not exceeding 12%. The estimated limit of quantification for fenhexamid was 0.1 mg/kg. The field results showed that fenhexamid dissipated rapidly from grapes and had a half-life of approximately 4.21 days. Hazard assessment was evaluated by using the hazard quotient (HQ). Data showed that the HQ value was significantly less than HQ = 1. Results indicate that hazard of fenhexamid use in grape even at 1.5-fold higher than recommended dosage was negligible to humans. This study could provide guidance for safe and reasonable use of fenhexamid in grapes and prevent health problems to consumers. However, further hazard assessment studies are needed to ascertain the hazard of fenhexamid residues on grape to vulnerable groups, including children, pregnant women, and elderly consumers.     

Determination of fluopicolide in grapes and soil using an easy sample preparation method and gas chromatography-mass spectrometry

A simple analytical method was developed and validated to determine fluopicolide residues in grapes and soil using the “Quick, Easy, Cheap, Effective, Rugged and Safe” approach followed by gas chromatography-mass spectrometry in the selected ion monitoring mode. Fluopicolide residues were extracted from grape and soil samples with acetonitrile, and the extracts were cleaned up by dispersive solid-phase extraction with primary secondary amine sorbent. The limit of quantification was 0.02 mg kg^?1 with grape and soil samples spiked at three levels, and recoveries were from 95% to 101% and 94% to 101% with relative standard deviations from 0.2% to 4.4%. The method is less expensive and safer than existing analytical methods for grapes and soil.     

Residues,half-life times,dissipation, and safety evaluation of the acaricide fenpyroximate applied on grapes

A validated high-performance liquid chromatography–diode array detector method for simultaneous determination of the acaricide fenpyroximate on grape was developed. Estimated limit of detection and limit of quantification for fenpyroximate were 0.01 and 0.05 mg kg^?1, respectively. The intra- and inter-day precisions performed with relative standard deviation were better than 9.3% and 8%, respectively, while recoveries were in the range of 88.5%–100.4%. Residue levels of fenpyroximate in grape samples collected 10 days after field application were below the established maximum residue level values. The dissipation rates of fenpyroximate were described using first-order kinetics and its half-life, were approximately 3.5 days in grape. This study provides basic information for developing regulations to safeguard the use of fenpyroximate in grapes and prevent any potential health concerns for consumers.     

Application of an inclusion complex for determination of dithianon residues in water and fruits

A 3,3′-benzidine/β-cyclodextrin fluorescence derivative (BCDFD) was prepared and characterized by means of elemental analysis and ¹H NMR. An inclusion complex was formed between BCDFD and the pesticide dithianon based on the internal cavity of β-cyclodextrin (β-CD), and the binding constant (K_S ) of the inclusion complex was investigated. The inclusion complex could be applied for the determination of dithianon residues. Based on this, a sensitive method for the determination of dithianon was established. The linear dynamic range was from 0.63 to 12.5?mg?L^?1 with a correlation coefficient of 0.9927. The limit of detection for an aqueous solution of standard and the relative standard deviation (RSD) were 10.6?µg?L^?1 and 0.76%, respectively. The proposed method has been successfully applied for the determination of dithianon residues in water and fruit samples with satisfactory results, and recoveries in the range of 96.0–108% were obtained. The method is rapid, direct, economical, and sensitive for dithianon analysis.     

Effects of introducing threatened falcons into vineyards on abundance of passeriformes and bird damage to grapes

Agricultural landscapes are becoming an important focus of animal conservation, although initiatives to conserve predators to date have rarely provided economic benefits to agricultural producers. We examined whether introduction to vineyards of the New Zealand Falcon (Falco novaeseelandiae), a species listed as threatened by the New Zealand Department of Conservation, affected the abundance of 4 species of Passeriformes that are considered vineyard pests or affected the amount of economic loss due to grape (Vitis vinifera) damage. Three of the species were introduced and remove whole grapes from bunches (Blackbird [Turdus merula], Song Thrush [Turdus philomelos], and Starling [Sturnus vulgaris]), whereas the one native species (Silvereye [Zosterops lateralis]) pecks holes in grapes. The introduction of falcons to vineyards was associated with a significant decrease in the abundance of introduced passerines and with a 95% reduction in the number of grapes removed relative to vineyards without falcons. Falcon presence was not associated with a change in the number of Silvereyes, but there was a 55% reduction in the number of grapes pecked in vineyards with falcons. Our results indicate that, relative to damage in vineyards without falcons, the presence of a falcon could potentially result in savings of US$234/ha for the Sauvignon Blanc variety of grapes and $326/ha for Pinot Noir variety of grapes.     

Salmon, wildlife, and wine: marine-derived nutrients in human-dominated ecosystems of central California.

Pacific salmon transfer large quantities of marine-derived nutrients to adjacent forest ecosystems with profound effects on plant and wildlife production. We investigated this process for two highly modified California wine country rivers, one with consistent salmon runs (Mokelumne River) and one without (Calaveras River). Mokelumne River Chinook salmon transported biomass and N comparable to Pacific Northwest salmon streams. Calaveras River levels were much less. Scavenger numbers correlated with salmon carcass counts over time on the Mokelumne River but not the Calaveras River. Likewise, salmon carcasses were consumed significantly faster on the Mokelumne River. Native riparian vegetation as well as cultivated wine grapes adjacent to Mokelumne River spawning sites received 18-25% of foliar N from marine sources, significantly higher than vegetation along the Calaveras River. These data suggest that robust salmon runs continue to provide important ecological services with high economic value, even in impaired watersheds. Loss of Pacific salmon can not only negatively affect stream and riparian ecosystem function, but can also affect local economies where agriculture and salmon streams coexist.     

Studies on the functional role of tintinnids in the Southern California Bight. II. Grazing rates of field populations

The feeding behavior of relatively undisturbed natural populations of tintinnids was studied in a series of experiments which utilized water samples collected in Southern California coastal waters. Dilute suspensions of corn starch were presented to the tintinnids and the rates of ingestion of this visual tracer determined after short (5 to 20 min) incubations followed by fixation in Lugol's iodine fixative. Tintinnids were observed to ingest particles of diameters up to approximately 43% of their lorica oral diameter and at rates proportional to their oral diameters. Grazing rates observed in these experiments ranged up to approximately 10 l tintinnid^-1 h^-1, and generally agreed well with the rates observed in experiments utilizing laboratory cultures of tintinnids. No significant diel periodicity in feeding rates was observed in the one study extending over a 24 h period.     

Acetaldehyde contamination of water,alcoholic, and non-alcoholic beverages stored in glass or plastic bottles

Acetaldehyde is a naturally found chemical in food substances characterized by a fruity aroma at low levels. However, high levels of acetaldehyde can add to or change the taste of foods and beverages. More importantly, acetaldehyde has recently been found to be possibly carcinogenic to humans (Group 2B). In this investigation, the amounts of acetaldehyde in several alcoholic and non-alcoholic beverages consumed in Greece, including red or white wine, retsina, tsipouro, grappa, fruit-based liqueurs, beers with different alcohol content as well as mineral water, soft drinks, and fruit juices were measured. The analytical method used is based on derivatization of acetaldehyde with 2,4-dinitrophenylhydrazine and its subsequent measurement using high performance liquid chromatography. High concentrations (median, min–max) were detected in grappa (29.4, 29.2–52.7 mg L^?1) and tsipouro (17.1, 0.8–55.6 mg L^?1), followed by beer (6.8, 6.7–6.9 mg L^?1) and red wine (3.7, 1.6–29.4 mg L^?1); the lowest levels were detected in soft drinks (0.067, 0.033–0.075 mg L^?1) and mineral water (0.04, 0.002--0.096 mg L^?1). Levels of acetaldehyde in retsina were very high (68.1, 63.9--68.3 mg L^?1) when after opening, the wine remained in plastic bottles for a long time, much higher than in samples taken from just opened bottles (7.2, 7.1–7.4 mg L^?1). The amount of acetaldehyde shows some positive correlation to the alcoholic content. These results suggest that regulatory measures and consumer guidance may be necessary for acetaldehyde in beverages.     

Testicular cellular toxicity of cadmium : transmission electron microscopy examination

It is clear that environmental heavy metals influence life systems and reproductive system. In the present study histological investigation revealed that cadmium was testicular toxicant in mice. Here we compared the fine-structure of spermatogenesis in two groups of mice (SWR), experimental and control. The experimental group underwent cadmium ingestion at 1 mg/kg daily for 4 weeks. The control group underwent ingestion of distilled water with equal dosages, using the same type of injectors, for 4-weeks. After cadmium exposure period both control and experimental groups were killed and samples of the testes were processed for microscopic examination. Ultra sections were examined and photographed by Transmission Electron Microscope (JEOL- 100SX) at 80KV. Ultrastructure examination revealed, vascular endothelial, interstitial, and sertoli cells damages. Early impairments of germinal cellular differentiation resulted in deformations in all parts of late spermatid. There were dislocation of accrosomal granules, nuclear damage associated with chromatin heterogeneity, detached spermatid from the apical process of sertoli cell, disarrangement of the mitochondria, abnormal oriented tail piece, and abnormal microtubules complex. These ultra morphological abnormalities relate to cell injury and to the resulting physiological abnormality, necrobiosis. Based on the results of this investigation it can be concluded that cadmium ingestion at 1000 microg/kg caused testicular toxicity and abnormalities in early sperm development.     

Sustainability indicators for environmental performance and sustainability assessment of the productions of four fine Italian wines

Increased awareness of the importance of environmental protection and the introduction of international standards like ISO 14001 stimulated development of environmental sustainability indicators as a means to measure systems environmental performance. Here, a thermodynamic approach, emergy analysis (Odum, 1988) was used to obtain sustainability indicators able to analyse and quantify the productive and ecological performance of four famous Italian wine productions: Chianti, Brunello di Montalcino, Nobile di Montepulciano, and Barbera d'hti. The application to agricultural production was motivated by the growing need for productive and environmentally sound development in modern agriculture, in which the resource base, the environment, is preserved. The choice of wines, more precisely, grape production, is due to their importance for Italian agriculture and the economy. All the wines demonstrated a good long-term environmental sustainability, especially in view of their high quality and in comparison with the average Italian wine production. Emergy analysis proved a powerful tool for assessing environmental performance of these systems, and its use could easily be extended to other wine productions to obtain a form of environmental performance classification of this product. Systematic use of emergy analysis to assess environmental performance of different processes and products, not necessarily in agriculture, could be useful for environmental certification.     

Seed trait changes in dispersers' guts and consequences for germination and seedling growth

The effectiveness of a frugivore as a disperser of a plant is greatly determined by how fruits and seeds are handled in its mouth and its digestive tract. Although a number of studies have investigated the effect of avian ingestion on germination, we still know very little about the modifications to seeds during ingestion and the specific consequences on plant fitness. Here we investigate for the first time the different mechanisms by which germination patterns of seeds are modified following ingestion by frugivores. Specifically, we examine changes in seed mass, water content, permeability, seed coat thickness, texture, and resistance in two common Mediterranean fleshy-fruited plants, Phillyrea angustifolia and Myrtus communis, after ingestion by Eurasian Blackbirds, Turdus merula. We found a number of differences between the plant species: Phillyrea seeds lost mass, mainly due to water loss, and had thinner coats after gut passage, but Myrtus seeds did not. Seeds of both species showed increased permeability, while Myrtus seeds in particular became less resistant to breakage. No quantifiable changes in seed coat texture were detected in either species, although this trait was partly associated with differences in germination rate in Phillyrea. High intraspecific plant variation was found for most seed traits measured. Seed passage through birds' guts sped up germination in both species, especially in Myrtus. Increased permeability in seeds of both species following ingestion resulted in a higher germination rate. Moreover, seeds with thick coats (and in the case of Phillyrea, harder coats) germinated at a slower rate and produced seedlings that also grew more slowly, indicating a cost of coat thickness and/or hardness for seedling emergence. Results obtained here contribute to explaining the great heterogeneity in germination responses among and within plant species and the large variety of factors, both intrinsic and extrinsic to the plants, that influence such responses.     

Short-term changes in feeding and digestion by the copepodCalanus pacificus

The planktonic marine copepodCalanus pacificus exhibits an enhanced feeding rate, or hunger response, when exposed to food following short periods of starvation. In a scries of laboratory experiments with copepods collected from the main basin of Puget Sound, Washington, during 1982 and 1984, we measured maximum ingestion rate, assimilation efficiency, and digestive enzyme activity to determine the time scales over which the feeding behavior ofC. pacificus responds to increases in food. These laboratory results were then compared to field studies of diel fluctuations in digestive enzymes and gut fluorescence ofC. pacificus in Dabod Bay, a fjord of Puget Sound, during September, 1980, and the closely relatedC. marshallae off the Washington coast, in August, 1981. Laboratory experiments demonstrated that the hunger response ofC. pacificus lasts approximately 6 h before ingestion rate returns to a steady state level of about one-half maximum. On the order of 12h of starvation were required to induce the maximum ingestion rate of the hunger response. Digestive enzyme activities did not change over these time scales. Assimilation efficiency peaked within a few hours of the onset of feeding, with low initial rates possibly related to the period of starvation prior to feeding. These results were consistent with diel patterns observed in the field. The hunger response ofC. pacificus appears to be controlled by processes within the gut, and our results are discussed in relation to recent studies of the digestive processes of calanoid copepods.Contribution No. 1772 from the School of Oceanography, University of Washington, Seattle, Washington 98195, USA     

Tracing the geographic origin of traded leopard body parts in the indian subcontinent with DNA‐based assignment tests

Illicit trade in wildlife products is rapidly decimating many species across the globe. Such trade is often underestimated for wide‐ranging species until it is too late for the survival of their remaining populations. Policing this trade could be vastly improved if one could reliably determine geographic origins of illegal wildlife products and identify areas where greater enforcement is needed. Using DNA‐based assignment tests (i.e., samples are assigned to geographic locations), we addressed these factors for leopards (Panthera pardus) on the Indian subcontinent. We created geography‐specific allele frequencies from a genetic reference database of 173 leopards across India to infer geographic origins of DNA samples from 40 seized leopard skins. Sensitivity analyses of samples of known geographic origins and assignments of seized skins demonstrated robust assignments for Indian leopards. We found that confiscated pelts seized in small numbers were not necessarily from local leopards. The geographic footprint of large seizures appeared to be bigger than the cumulative footprint of several smaller seizures, indicating widespread leopard poaching across the subcontinent. Our seized samples had male‐biased sex ratios, especially the large seizures. From multiple seized sample assignments, we identified central India as a poaching hotspot for leopards. The techniques we applied can be used to identify origins of seized illegal wildlife products and trade routes at the subcontinent scale and beyond.     

超声辅助乳化液相微萃取分析绿茶饮料和番茄汁中有机磷农药残留

农药施用于田间,必然会残留于环境中。农药残留的分析方法多种多样。为探究灵敏度高、重现性好的样品前处理方法,建立了超声辅助乳化液相微萃取,结合气相色谱和火焰光度检测器测定绿茶饮料和番茄汁中5种有机磷农药的方法,对萃取条件进行了优化,如萃取溶剂种类和体积、超声频率和时间、盐效应。在优化后的萃取条件下,5种有机磷农药实现良好分离,空白添加实验结果表明在0.1~10μg·L-1之间,线性相关系数在0.9985~0.9994之间,检测限在0.005~0.020μg·L-1之间,相对标准偏差(n=5)在4.3%~9.4%之间。在绿茶饮料和番茄汁实际样本检测中,目标分析物含量均低于检出限。样本添加回收试验的回收率均大于88.5%,相对标准偏差(n=3)在2.2%~9.8%之间,结果表明该方法用于液体样本中农药残留检测真实可靠。     

Bestimmung der resorptionsverfügbaren PCDD/PCDF aus Kieselrot

For the estimation of intestinal absorption of polychlorianted dibenzodioxins/dibenzofurans (PCDD/F), ain-vitro model was developed in order to study PCDD/F mobilization by digestion of technogenic soils using ?Kieselrot” (red slag) as substrate and digestive juice model mixtures. Red slag samples were shaken successively with model mixtures of saliva, gastric juice, duodenal juice and bile. The solids were separated, the aqueous phase was extracted with hexane, the hexane extract analyzed for PCDD/F. Additionally, the PCDD/F-content of the red slag was determined. Extraction efficiency was tested with three different digestive juice model mixtures and also tap water for comparision. The percentage of PCDD/F transferred from the red slag sample into the digestive juice mixture was defined as absorption availability. In our experiments, a maximum absorption availability of 2 % was found.     

Food ingestion by the marine planktonic copepod Paracalanus in relation to abundance and size distribution of food

Juveniles and adult females were presented a food spectrum of three algae of different sizes (4.5, 12 and 20 m cell width). The increase in rate of ingestion of the medium-sized alga with an increase in copepod size was significantly greater than the increase in rate of ingestion of the small alga. It is hypothesized that the perception of chemical signals from the small alga by a copepod decreases as the copepod moults from stage to stage. The rate of ingestion of the large alga by copepod stage V (CV) and adult females was lower than the rate of ingestion of the medium-sized alga at mid- and high phytoplankton concentrations. The amount of nitrogen ingested when the medium-sized alga alone was offered was either higher than (stage C II) or not significantly different from that when the three algae were offered together (stage C IV). Ingestion rates are reduced when there is a multialgal food source. This implies that there is increased stability in the ocean because multiparticle food sources are more slowly depleted than unialgal foods. Weight-specific ingestion rates of copepods fed the three algae simultaneously increased from nauplius to stage C III and then decreased as adulthood approached. The contribution of the small alga to the total amount of nitrogen ingesied was greatest for naupliar stages while the contribution of the medium-sized cells was greater for later stages. The largest alga was readily ingested by stage C V and adult females but never contributed more than 25% of the nitrogen ingested. Eight to 12% of the nitrogen ingested by adult females was from the small alga. It is hypothesized that the algal cell size for maximum nitrogen ingestion in upwelled waters is relatively small, round or square and close to the size threshold below which adult females do not sense individual cells.     

Characteristics of feeding on dinoflagellates by newly hatched larval crabs

The zoeal larvae of brachyuran crabs must feed soon after hatching on a diet that includes large micro- and mesozooplankton in order to satisfy nutritional requirements. However, newly hatched larvae have been shown to ingest a variety of dinoflagellates, perhaps using microbial carbon sources to sustain them until they encounter more favored prey. Ingestion of dinoflagellates by larval crabs has been documented previously under conditions in which the larvae were exposed to algae provided in monoculture or in defined mixtures of cells. We report here on experiments conducted on the hatching stage of five crab species to determine if ingestion of dinoflagellates occurred when they were provided in combination with Artemia sp. nauplii or after a period of feeding on mesozooplankton. Quantitative measurements of chl a in the larval guts provided evidence of ingestion of algal cells. Active ingestion of the dinoflagellate Prorocentrum micans at specified intervals during an extended feeding period was determined on larvae of two crab species using fluorescently labeled cells provided for brief periods at prescribed time intervals. Stage 1 larvae of four of the five crab species ingested dinoflagellates when they were provided in combination with nauplii and larvae of all five species ingested cells after feeding solely on nauplii for 24 h. Ingestion of algal cells was first evident in the larval guts after 6 h of feeding at both low (200 cell ml⁻¹) and high (1,000 cells ml⁻¹) prey densities. Higher prey densities resulted in higher gut chl a. Larvae continuously exposed to dinoflagellates actively ingested cells at every 3 h interval tested over a 36 h period. Results confirm previous studies that larvae will ingest dinoflagellates even when they are encountered in a mixed prey field or when having previously fed. Ingestion of cells may occur on a continual basis over time.     

Phthalatkonzentrationen in Böden naturnaher Standorte des Sollings (Niedersachsen)

The phthalat concentrations in soil samples from the Solling (Ecological Research Project Solling) were measured. The samples were collected from a beech and a spruce forest and aTrisetum flavescens meadow. The distance from the tree trunks and the different horizons were taken into consideration as well. Dimethylphthalat, diethylphthalat, dibutylphthalat, butylbenzylphthalat, di-(2-ethylhexyl) phthalat and dioctylphthalat were determinated using GC/MS. From the six phthalates investigated, four were detected in the samples. Dimethyl and diethylphthalat were found at very low concentrations in only one sample. Dibutyl- and di-(2-ethylhexyl)phthalat were detected in eight of 21 samples. No phthalates were found in the samples from theTrisetum flavescens meadow. Two of the nine samples from the beech forest showed phthalates. In six of the nine samples from the spruce forest phthalates were detected. Phthalate concentrations in the spruce forest were always higher than those found in the beech forest.