Characterizing kinetics of transport and transformation of selenium in water-sediment microcosm free from selenium contamination using a simple mathematical model

This study developed a seven-compartment model for predicting the fate of selenium (Se) in an aquatic environment containing a water-sediment boundary. Speciation of Se in water-sediment microcosms under microaerobic conditions was measured to evaluate first-order kinetics of Se transportation and transformation. The microcosm consisted of a 10-ml solution containing 1mM soluble Se as selenate (Se6+) or selenite (Se4+) and 8 g wet sediment that was free from Se contamination, sampled from the Senri, Yamato, or Yodo Rivers in Osaka, Japan. Stepwise reaction coefficients describing transportation and transformation were determined using an inverse method on this model which includes: selenate (Se(W)6+) and selenite (Se(W)4+) in ponded water; selenate (Se(S)6+) and selenite (Se(S)4+), elemental Se (Se0), organic Se (Se2-) in sediment; and gaseous Se (DMSe). During this 1-month experiment, soluble Se was transported from ponded water to the sediment and Se was transformed sequentially to other Se species through biochemical reactions. Experimental and kinetic analyses indicated quantitatively that the Yamato River microcosm, with its high organic matter content, had a high adsorption rate of soluble Se. The Yodo River microcosm had a low adsorption rate for Se6+ and a low Se reduction rate. The Senri River microcosm had an apparent high volatilization rate of DMSe. The model developed in this study is extremely useful for predicting fate of Se in aquatic environment in the field.     

Multiresidue screening methods for the determination of pesticides in tomatoes

The possibility of applying thin layer chromatography (TLC) detection for the analysis of pesticide residues in tomatoes was investigated. Samples of tomatoes that have never been treated with pesticide were fortified with atrazine, carbaryl, carbofuran, chloroxuron, diuron, dimethoate, imazalil, oxamyl and methamidophos. The samples were extracted, cleaned-up by gel permeation chromatography and then applied on silica gel plates. The pesticides were eluted with ethyl acetate and dichloromethane. Two eluting solvent systems were tested, one using the reagents o-toluidine + potassium iodite (o-TKI) and the other p- nitrobenzene fluoroborate (NBFB). After the development of the plates, the diameter of the spots was measured. The lowest minimum detection quantity (MDQ) for o-TKI system for atrazine was 12 ng. The highest was 125 ng for carbofuran. Using NBFB system, the lowest MDQ was 60 ng for carbaryl and the highest was 70 ng obtained for carbofuran. Considering the concentration of these pesticides in the spiked tomato samples, the minimum concentration was 1.1 ng/microL and 32.3 ng/microL for atrazine and carbofuran, respectively, by using o-TKI system. For NBFB system the minimum concentration reached was 3.5 ng/microL and 4.3 ng/microL for carbaryl and carbofuran, respectively. This study showed that TLC can be used for semi-quantitative analysis.     

Influence of oxalic acid formed on the degradation of phenol by Fenton reagent

The objective of this work is to examine the influence of oxalic acid formed on the degradation of phenol by Fenton reagent. Oxalic acid formed at initial stage within 30 min significantly suppresses the reduction of ferric ion, thus terminating degradation reaction. The yield of oxalic acid is dependent on the amount of ferrous ion dosed since the minimal amount of oxalic acid is formed after the degradation reaction terminates. Mineralization of phenol by Fenton reagent stagnates after 120 min under the conditions used in this study. The reason why the mineralization stagnated can be assumed to be following two mechanisms other than the depletion of H₂O₂. In the case where a small amount of ferrous ions is dosed, the reduction of ferric ions is minimal by oxalic acid formed. In the case where a large amount of ferrous ions is dosed, the amount of degradable organic compounds is insufficient owing to preferential conversion to oxalic acid. The mineralization can be enhanced by the intermittent dosing of ferrous ions, which facilitates the suppression of oxalic acid formation during the degradation by Fenton reagent.     

Residues of pharmaceutical products in recycled organic manure produced from sewage sludge and solid waste from livestock and relationship to their fermentation level

In recent years, sludge generated in sewage treatment plants (STPs) and solid waste from livestock being utilized is useful for circulation of nourishment in farmlands as recycled organic manure (ROM). In this study, we determined the residue levels and patterns of 12 pharmaceutical products generated by human activity in the ROMs produced from human waste sludge (HWS), sewage sludge (SS), cattle manure (CM), poultry manure (PM), swine manure (SM) and horse manure (HM).The kind and number of pharmaceutical products detected in ROMs were different. Fluoroquinolones (FQs) were detected at high levels in HWS and SS samples. In addition, the detection frequency and concentration levels of sulfonamides (SAs) in PM and SM were high. Moreover, high concentrations of chlortetracycline (CTC) were found in only SM. These differences reflect specific adherence adsorption of the pharmaceutical products to different livestock and humans. Moreover, it was found that the concentrations of pharmaceutical products and fermentation levels of ROMs had significant positive correlation (r = 0.41, p = 0.024).When the fermentation test of ROM was conducted in a rotary fermentor in a lab scale test, the residue levels of pharmaceutical products decreased effectively except carbamazepine (CBZ). The rates of decrease were in the case of tetracyclines (TCs): 85-92%, FQs: 81-100%, erythromycine: 67%, SAs: 79-95%, trimethoprim: 86% and CBZ: 37% by 30 d. Pharmaceutical products that can be decomposed by fermentation process at the lowest impact of residual antibiotic activities may therefore be considered as environmentally friendly medicines.     

Immunologic effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides in Japanese infants

Effects of perinatal exposure to dioxins, PCBs and organochlorine pesticides on lymphocyte subsets were investigated in the peripheral blood from 101 Japanese infants with approximately 10 months of age. Perinatal exposure to these organochlorine compounds were estimated by their contamination levels in the breast milk of the mothers. Lymphocyte subsets such as CD16+, HLA-DR+, CD4+, CD4+8+, CD8+, CD3+ and CD20+ cells in peripheral venous blood were assessed in a subgroup of 92 infants. Greater exposures to HCE, chlordane and dioxins were significantly associated with the increase in the percentages of CD8+ and CD3+ T lymphocytes and CD4+/CD8+ T cell ratios, respectively. In addition, higher HCH exposure was also associated with a decrease in the percentage of HLA-DR+ T lymphocytes. Furthermore effects of dioxins, DDT and PCBs on the percentage of CD16+ T lymphocyte were more pronounced by the combined exposure of dioxins and PCBs or by the combined exposure of DDT and PCBs. Effects of HCE on the percentages of CD8+ T lymphocyte were also more pronounced by the combined exposure of HCE and chlordane. In conclusion, our study suggests that greater exposures to dioxins, PCBs and organochlorine pesticides determined in this study (except dieldrin) influence the immune system of Japanese infant, although the clinical significance of these changes is uncertain.     

Lipid storage and composition in tropical surgeonfishes (Teleostei: Acanthuridae)

The lipid composition of tropical marine reef fishes is poorly known, despite their use as food by local human populations and recent interest in health-related benefits of fish lipids. We examined the composition of lipids from epaxial muscle, liver, and two storage sites [mesenteries surrounding the gut (intraperitoneal fat, IPFs) and retroperitoneal fat bodies (FBs) posterior to the peritoneal cavity] in three species of surgeonfishes from Ishigaki Island, Japan: Naso lituratus (Bloch and Schneider, 1801), Acanthurus lineatus (Linnaeus, 1758), and A. bariene (Lesson, 1830). Triacylglycerols dominated all samples of neutral lipid and constituted ≥ 99% of FBs and IPFs. Polar lipids generally contained large fractions of phosphatidylethanolamine and phosphatidylcholine. Quantified fatty acids ranged in length from C₁₄ to C₂₄. C₁₆ fatty acids prevailed (>35% of neutral fatty acids, >23% of polar fatty acids), although C₁₈ (>16 and >14%, respectively) and C₂₀ acids (>8 and >19%, respectively) were also common. Saturated fatty acids, dominated by palmitic acid (16:0), comprised 38.7 to 50.7% of acids from neutral lipids and 30.8 to 41.1% from polar lipids. The most common monounsaturated acids were 18:1n9 and 20:1n9. Polyunsaturated acids were prevalent in polar lipids (especially 20:4n6, 20:5n3, 22:2n3, 22:5n3, 22:5n6 and 22:6n3). Common polyunsaturated acids of neutral lipids were 18:2n6, 18:4n3, several n-3 and n-6 C₂₀ acids, 22:2n3 and 22:5n3. IPF and FB were almost identical across species, and lipids of fat bodies (IPFs, FBs) were more similar to those of muscle than those of liver for all three species. The FBs appear to constitute an accessory storage site, which overcomes constraints on lipid storage imposed by a small, inflexible abdominal cavity that contains both viscera and consistently voluminous gut contents. Fatty acid signatures indicate that largely overlooked epiphytic or epilithic diatoms contribute significantly to lipid acquisition. The combination of large quantities of both saturated and n-3 and other polyunsaturated fatty acids in surgeonfishes, in contrast to low saturates and high polyunsaturated acids in lipids of commercially important cool-water fishes, suggests that a study of dietary effects of fish lipids on human inhabitants of the tropics may be instructive insofar as human health and nutrition are concerned. Received: 16 March 1998 / Accepted: 6 August 1998     

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.     

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.     

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.