Simultaneous determination of seven anticoagulant rodenticides in agricultural products by gel permeation chromatography and liquid chromatography–tandem mass spectrometry

A sensitive and reliable method for the simultaneous determination of hydroxycoumarin-type (brodifacoum, bromadiolone, coumatetralyl, and warfarin) and indandione-type (chlorophacinone, diphacinone, and pindone) rodenticides in agricultural products by gel permeation chromatography (GPC) and liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed. The procedure involved extraction of the rodenticides from samples with acetone, followed by liquid–liquid partitioning with hexane/ethyl acetate (1:1, v/v) and 10% sodium chloride aqueous solution, then cleanup using GPC, and finally, analysis using LC–MS/MS. High recoveries from the GPC column were obtained for all rodenticides tested using a mobile phase of acetone/cyclohexane/triethylamine (400:1600:1, v/v/v). An ODS column, which contains low levels of metal impurities, gave satisfactory peak shapes for both hydroxycoumarin- and indandione-type rodenticides in the LC–MS/MS separation. The average recoveries of rodenticides from eight agricultural foods (apple, eggplant, cabbage, orange, potato, tomato, brown rice, and soybean) fortified at 0.0005–0.001 mg/kg ranged from 76 to 116%, except for bromadiolone in orange (53%) and diphacinone in soybean (54%), and the relative standard deviations ranged from 1 to 16%. The proposed method effectively removed interfering components, such as pigments and lipids, and showed high selectivity. In addition, the matrix effects were negligible for most of the rodenticide/food combinations. The results suggest that the proposed method is reliable and suitable for determining hydroxycoumarin- and indandione-type rodenticides in agricultural products.     

Distribution,life history,and production of three species of <Emphasis Type="Italic">Neomysis</Emphasis> in Akkeshi-ko estuary,northern Japan

Spatial and seasonal distribution pattern, life history and production of three species of Neomysis (Mysidacea) which commonly occur in northwestern subarctic Pacific coastal waters, were investigated throughout the year in the Akkeshi-ko estuary, northern Japan. The most abundant species Neomysis awatschensis (annual mean density: 179.8 inds. m⁻², biomass: 108.8 mg DW m⁻²) occurred at the inner part of the estuary including low salinity areas with no clear preference for the seagrass bed. The second most abundant Neomysis mirabilis (mean density: 95.8 inds. m⁻², biomass: 90.1 mg DW m⁻²) occurred at relatively saline seagrass site throughout the year. Occurrence of Neomysis czerniawskii in the estuary was limited to the seagrass bed during summer when their population mainly consisted of juveniles, suggesting that this species is a seasonal migrant between the estuary and the marine environment. Both N. awatschensis and N. mirabilis populations were composed of two generation types, a larger sized overwintering and smaller sized spring/summer generations; however, each species had a different reproductive strategy. N. awatschensis was characterized by fast growth to maturity at a smaller size than N. mirabilis with a relatively high fecundity during warm season, suggesting that this species is an r-strategist which can utilize opportunistically a wide variety of habitats. In contrast, the seagrass bed resident N. mirabilis was a K-strategist which matures at a larger size producing fewer but larger offspring. The annual production of N. awatschensis (0.57–0.70 g DW m⁻², mean of the whole estuary) and N. mirabilis (0.58–0.68 g DW m⁻², mean of the seagrass bed) at their respective habitats was comparable. Consequently, species-specific life history and distribution pattern are concluded to allow Neomysis spp. to coexist in the estuary and the high carrying capacity of seagrass bed is suggested to contribute to maintain their high biomass level.     

Recent survey and effects of cooking processes on levels of PCDDs,PCDFs and Co-PCBs in leafy vegetables in Japan

We report here the latest levels of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs) and coplanar polychlorinated biphenyls (Co-PCBs) in leafy vegetables in Japan as well as the effect of cooking processes on the reduction of these contaminants. Three kinds of leafy vegetables (“komatsuna”, lettuce and spinach) from seven districts in Japan in 1998 were analyzed for the 2,3,7,8-chlorine substituted PCDD/Fs and three non-ortho-PCBs (#77, 126 and 169). The mean total TEQ levels (using the WHO-TEFs) in the komatsuna, lettuce and spinach were 0.094, 0.025 and 0.196 pg/g fresh weight, respectively. The TEQ levels are dominated by 2,3,7,8-TCDD, 1,2,3,7,8-PeCDD, 2,3,4,7,8-PeCDF and 3,3^′,4,4^′,5-PeCB in many of the samples. For one of these isomers, the 2,3,4,7,8-PeCDF TEQ levels showed good correlation with the total TEQ levels in the samples (r=0.957). This suggests that 2,3,4,7,8-PeCDF may be an indicator for dioxin contamination in the analysis of the leafy vegetables. Also, the effects of two cooking processes (washing and washing followed by boiling) on the dioxin levels in two types of spinach samples were investigated. On average, in both samples, the total concentrations of the PCDDs, PCDFs and Co-PCB were reduced to about 38%, 73% and 88% of the initial concentrations by washing, and to 21%, 35% and 61% of the initial concentrations by washing followed by boiling. The total TEQ levels were reduced to about 30% of the initial TEQ levels by washing followed by boiling. Significant reductions in the TEQ levels were observed in the cooked samples. Thus, the cooking processes may reduce the risk of dioxin intake from the leafy vegetables.     

Heart rate changes reveal that little blue penguin chicks (Eudyptula minor) can use vocal signatures to discriminate familiar from unfamiliar chicks

Researchers investigating social recognition typically measure only behavioural responses during discrimination tests - physiological changes have been largely ignored. We examined whether little blue penguin chicks (Eudyptula minor) could distinguish siblings from other chicks using auditory cues, by measuring behavioural and heart rate changes during playback experiments. Chicks were exposed to five treatments: the begging calls of siblings, neighbouring chicks and unfamiliar chicks, and two controls (heterospecific begging calls and music). We also determined if chicks developed distinctive begging calls, by using F-ratios to quantify inter- versus intra-individual variability in a range of acoustic parameters, and applying a discriminant-function analysis. Inter-individual variation was greater for pitch than for temporal or amplitude parameters, suggesting that call pitch may be important for individual recognition. The discriminant-function analysis showed each chick's calls were distinctive and could act as a vocal signature. Treatments did not instigate different behavioural responses. However, chick heart rates during playback of sibling calls were significantly higher than those recorded during stranger, but not neighbour, playback. A simple recognition system based on familiarity may allow this plesiomorphic and loosely colonial penguin to gain at least some of the benefits associated with more advanced sibling recognition systems (some highly colonial seabirds discriminate siblings from neighbouring chicks). Heart rate could be a useful measure of social recognition abilities, particularly in species where changes in behaviour are not always evident or are difficult to observe.     

Residual congener pattern of dioxins in human breast milk in southern Vietnam

This study evaluated residual congener patterns of dioxin/furan (=PCDD/DF) related to tactical herbicides aerially sprayed over the regions of southern Vietnam through Operation Ranch Hand. The study focused on Cam Chinh (CC) commune, Quang Tri province (an area sprayed with tactical herbicides), and the Cam Phuc (CP) commune, Ha Tinh province (a non-sprayed area). Breast milk samples for analysis were collected in September 2002 and July 2003 from lactating primiparous and multiparous mothers born after the war (<31 years old). We found the levels of each congener in the CC commune were higher than in the CP commune, and determined specificity in the PCDD/DF congener pattern in CC commune samples by cluster analysis. The congener pattern is characterized by higher (the hexa-, the hepta-, and the octa-) chlorinated PCDD/DFs; this appears to be the same profile as that presented by pentachlorophenol (PCP), rather than 2,4,5-trichlorophenoxy acid (2,4,5-T) contaminated with 2,3,7,8-TCDD. A GC/MS study in the 1970s detected the chlorophenols 2,4-di and 2,4,6-trichlorophenol in some Agent Orange samples, which contained, like PCP, a wide variety of PCDD/DF congeners. In this context, it may be expected that certain tactical herbicides contaminated with various chlorophenol impurities, have a unique congener pattern when compared with pure 2,4,5-T formulations.     

Behavior of atrazine in soils of tropical zone

Abstract

Movement and degradation of ¹⁴C‐atrazine (2‐chloro 4‐(ethylamino)‐6‐(isopropylamino)‐s‐triazine, was studied in undisturbed soil columns (0.50m length × 0.10m diameter) of Gley Humic and Deep Red Latosol from a maize crop region of Sao Paulo state, Brazil. Atrazine residues were largely confined to the 0–20cm layers over a 12 month period Atrazine degraded to the dealkylated metabolites deisopropylatrazine and deethylatrazine, but the major metabolite was hydroxyatrazine, mainly in the Gley Humic soil. Activity detected in the leachate was equivalent to an atrazine concentration of 0.08 to 0.11μg/1.

The persistence of ¹⁴C‐atrazine in a maize‐bean crop rotation was evaluated in lysimeters, using Gley Humic and Deep Red Latosol soils. Uptake of the radiocarbon by maize plants after 14‐days growth was equivalent to a herbicide concentration of 3.9μg/g fresh tissue and was similar in both soils. High atrazine degradation to hydroxyatrazine was detected by tic of maize extracts. After maize harvest, when beans were sown the Gley Humic soil contained an atrazine concentration of 0.29 μg/g soil and the Deep Red Latosol, 0.13 μg/g soil in the 0–30 cm layer. Activity detected in bean plants corresponded to a herbicide concentration of 0.26 (Gley Humic soil) and 0.32μg/g fresh tissue (Deep Red Latossol) after 14 days growth and 0.43 (Gley Humic soil) and 0.50 μg/g fresh tissue (Deep Red Latossol) after 97 days growth. Traces of activity equivalent to 0.06 and 0.02μg/g fresh tissue were detected in bean seeds at harvest. Non‐extractable (bound) residues in the soils at 235 days accounted for 66.6 to 75% (Gley Humic soil and Deep Red Latossol) of the total residual activity.     

Do national levels of individualism and internal locus of control relate to well‐being: an ecological level international study

Data were collected from managers in 24 nations/territories on work locus of control (LOC), individualism–collectivism (I–C), and well‐being (job satisfaction, absence of psychological strain, and absence of physical strain). There were significant mean differences across samples on all five of these measures, and consistent with our hypothesis, at the ecological or sample mean level well‐being was associated with an internal locus of control. However, contrary to our hypothesis, well‐being was not associated with I–C, despite a strong correlation between I–C and LOC. Findings at the ecological level were consistent with the literature concerning the salutary effects of control on well‐being. Copyright © 2001 John Wiley & Sons, Ltd.     

Saltwater intrusion in coastal aquifer ??? comparison between the CIP and MOC simulation technique

Proper management and evaluation of environmental effects for coastal groundwater aquifers require accurate estimation of salt and fresh water movement. For this we compare two numerical methods to study saltwater intrusion. The two numerical methods are the CIP (constrained interpolation profile) and the MOC (method of characteristics). The two numerical methods are used to solve the salt transport equation. The two methods are applied and compared to saltwater intrusion experiments for confined and unconfined aquifer case studies. It is found that for both cases, the CIP-method is superior in terms of calculation time while keeping an acceptable numerical accuracy.     

Soil heterogeneity effects on acid flushing of lead-contaminated soil

A compact model for evaluation of acid flushing of heavy-metal-contaminated soil in a small-scale on-site treatment plant is proposed. The model assumes that the soil was re-packed in a container after excavation resulting in a soil structure with heterogeneous and random physical and chemical properties. To evaluate the effects of heterogeneity on the efficiency of contaminant removal by acid flushing, a numerical analysis of lead transport in the heterogeneous soil medium was performed. The model examines cation exchange and surface complexation reactions involving three cations (Ca, Pb, and H) and one anion (Cl) in both dissolved and exchangeable forms, two Pb surface complexes (SOPbCl and SOPbOH), and one Cl surface complex (SOH₂Cl). The transport of these species during flushing with acid in a synthetically generated two-dimensional heterogeneous soil was simulated in the model. Results indicated that the flushing fluid preferentially followed pathways with large permeability. The heterogeneous cation exchange capacity (CEC) distribution and surface complexation sites had a significant effect on the transport of dissolved species. Because the CEC was set to a relatively low value, Pb was adsorbed mainly as surface complexes (SOPbCl and SOPbOH). Simulation results suggest that blocks of low hydraulic conductivity located in the upper part of the model domain greatly impede solute transport. Ponding conditions did not significantly affect the efficiency of decontamination. The model and its results are useful in the design of small-scale treatment plants for acid flushing.