Microdistribution of Am in structures of submerged macrophyte Elodea canadensis growing in the Yenisei River

A submerged macrophyte of the Yenisei River, Elodea canadensis, was used to study the microdistribution of the artificial radionuclide ²⁴¹Am among different components of the plant. The total amount of ²⁴¹Am added to the experimental system was 1850 ± 31 Bq/L. The total amount of ²⁴¹Am accumulated by the plants was 182 Bq per sample, or 758,333 ± 385 Bq/kg dry mass. It has been found that the major portion of ²⁴¹Am accumulated by E. canadensis, up to 85%, was bound to solid components of the cells. It is observed that the microdistribution of ²⁴¹Am within different components of the submerged plant E. canadensis was not uniform. ²⁴¹Am distribution vary depending on the age of the leaf blades, the state of the cells and morphological features of the plant stem.     

Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC-MS/MS

Simple high-throughput procedures were developed for the direct analysis of glyphosate [N-(phosphonomethyl)glycine] and aminomethylphosphonic acid (AMPA) in human and bovine milk and human urine matrices. Samples were extracted with an acidified aqueous solution on a high-speed shaker. Stable isotope labeled internal standards were added with the extraction solvent to ensure accurate tracking and quantitation. An additional cleanup procedure using partitioning with methylene chloride was required for milk matrices to minimize the presence of matrix components that can impact the longevity of the analytical column. Both analytes were analyzed directly, without derivatization, by liquid chromatography tandem mass spectrometry using two separate precursor-to-product transitions that ensure and confirm the accuracy of the measured results. Method performance was evaluated during validation through a series of assessments that included linearity, accuracy, precision, selectivity, ionization effects and carryover. Limits of quantitation (LOQ) were determined to be 0.1 and 10 µg/L (ppb) for urine and milk, respectively, for both glyphosate and AMPA. Mean recoveries for all matrices were within 89–107% at three separate fortification levels including the LOQ. Precision for replicates was ≤7.4% relative standard deviation (RSD) for milk and ≤11.4% RSD for urine across all fortification levels. All human and bovine milk samples used for selectivity and ionization effects assessments were free of any detectable levels of glyphosate and AMPA. Some of the human urine samples contained trace levels of glyphosate and AMPA, which were background subtracted for accuracy assessments. Ionization effects testing showed no significant biases from the matrix. A successful independent external validation was conducted using the more complicated milk matrices to demonstrate method transferability.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

Application of indoxacarb for managing shoot and fruit borer of eggplant (Solanum melongena L.) and its decontamination

Indoxacarb was applied at 75 and 150 g a.i. ha^{? 1} for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg^{? 1} and 3.64–3.68 mg kg^{? 1} from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg^{? 1}) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg^{? 1} thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO₄) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g^{? 1} spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.     

Rain‐washing of mimic®, RH‐5992, from balsam fir foliage following application of two formulations

Abstract

Two formulation concentrates of the insecticide, RH‐5992 [N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyI) hydrazine], an aqueous flowable (2F) and an emulsion‐suspension (ES), were diluted with water to provide spray mixes containing dosage rates ranging from 35 to 150 g of the active ingredient (AI)/ha. The mixes were sprayed in a laboratory chamber, onto balsam fir branch tips collected from field trees and greenhouse‐grown seedlings. Droplet spectra and spray mass recovery were determined on artificial samplers. Simulated rainfall of two different intensities was applied at different rain‐free periods, and rain droplet sizes were determined. Foliar washoff of RH‐5992 was assessed after application of different amounts of rain, and the increase in soil residues was evaluated.

A direct relationship was indicated between the amount of rainfall and RH‐5992 washoff. The larger the rain droplet size, the greater the amount washed off. Longer rain‐free periods made the deposits more resistant to rain. Regardless of the amount of rainfall, rain droplet size and rain‐free period, foliar deposits of the 2F formulation were washed off to a greater extent than the ES formulation. The increase in soil residues due to foliar washoff was greater for the 2F than for the ES formulation. The deposits of the emulsion‐suspension were consistently more resistant to rain‐washing than those of the aqueous flowable formulation.     

Validation of a hydride generation atomic absorption spectrometry methodology for determination of mercury in fish designed for application in the Brazilian national residue control plan

In the present study, a method for the determination of mercury (Hg) in fish was validated according to ISO/IEC 17025, INMETRO (Brazil), and more recent European recommendations (Commission Decision 2007/333/EC and 2002/657/EC) for implementation in the Brazilian Residue Control Plan (NRCP) in routine applications. The parameters evaluated in the validation were investigated in detail. The results obtained for limit of detection and quantification were respectively, 2.36 and 7.88 μg kg^?1 of Hg. While the recovery varies between 90–96%. The coefficient of variation was of 4.06–8.94% for the repeatability. Furthermore, a comparison using an external proficiency testing scheme was realized. The results of method validated for the determination of the mercury in fish by Hydride generation atomic absorption spectrometry were considered suitable for implementation in routine analysis.     

Detailed analysis of polybrominated biphenyl congeners in bird eggs from Norway

Individual eggs of six species of birds from Norway representing different food chains were analysed for residues of polybrominated biphenyls (PBBs). In all species, the residue pattern was dominated by hexaBBs. The dominating congeners were PBB 153, PBB 154, and PBB 155. Whereas PBB 153 is present in technical hexabromobiphenyl, PBB 154 and PBB 155 are formed by the reductive debromination of decabromobiphenyl. This was evidenced by the detection of several heptaBBs and octaBBs all of which are typical degradation intermediates of PBB 209. Hepta- and octaBBs were more than one order of magnitude less abundant than the hexaBBs. The second most prevailing homologue group was pentaBBs. The most relevant pentabrominated isomers were PBB 99 and PBB 101. Concentrations of the three hexaBBs - PBB 153, PBB 154, and PBB 155 - amounted to 1.3-13 ng/g wet weight or 3-23% of the contamination with polybrominated diphenyl ethers.     

活性炭处理甲苯气体吸附再生实验研究

研究了活性炭对甲苯废气的吸附穿透过程及热空气解吸过程.穿透曲线实验结果表明,在常规空塔气速范围内,传质区高度基本在5.06～9.75 cm,传质区不饱和度在0.4～0.7.在动态运行情况下,活性炭对甲苯的饱和吸附容量在0.16～0.24 g/g.热空气吹脱实验表明,适宜的脱附工况条件为脱附温度180 ℃、脱附空气流速0.106 m/s、脱附时间40 min.     

Carbon source/sink function of a subtropical, eutrophic lake determined from an overall mass balance and a gas exchange and carbon burial balance

Although studies on carbon burial in lake sediments have shown that lakes are disproportionately important carbon sinks, many studies on gaseous carbon exchange across the water-air interface have demonstrated that lakes are supersaturated with CO(2) and CH(4) causing a net release of CO(2) and CH(4) to the atmosphere. In order to more accurately estimate the net carbon source/sink function of lake ecosystems, a more comprehensive carbon budget is needed, especially for gaseous carbon exchange across the water-air interface. Using two methods, overall mass balance and gas exchange and carbon burial balance, we assessed the carbon source/sink function of Lake Donghu, a subtropical, eutrophic lake, from April 2003 to March 2004. With the overall mass balance calculations, total carbon input was 14 905 t, total carbon output was 4950 t, and net carbon budget was +9955 t, suggesting that Lake Donghu was a great carbon sink. For the gas exchange and carbon burial balance, gaseous carbon (CO(2) and CH(4)) emission across the water-air interface totaled 752 t while carbon burial in the lake sediment was 9477 t. The ratio of carbon emission into the atmosphere to carbon burial into the sediment was only 0.08. This low ratio indicates that Lake Donghu is a great carbon sink. Results showed good agreement between the two methods with both showing Lake Donghu to be a great carbon sink. This results from the high primary production of Lake Donghu, substantive allochthonous carbon inputs and intensive anthropogenic activity. Gaseous carbon emission accounted for about 15% of the total carbon output, indicating that the total output would be underestimated without including gaseous carbon exchange.     

Preconcentration technique for the determination of trace elements in natural water samples by ICP-AES

A procedure was developed for the determination of Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES) after preconcentration on a morpholine dithiocarbamate (mor-DTC) supported by bagasse (Saccharam aphisinaram). The sorbed elements were subsequently eluted with 4,M HNO₃ and the acid eluates were analysed by ICP–AES. The influence of various parameters such as pH, flow rate of sample, eluent concentration, volume of the sample and volume of eluent were investigated to enhance the sensitivity of the present method. A 20,mL disposable syringe served as preconcentration column. Under the optimal conditions Cd, Cu, Zn, Co, Ni, Mn, Pb and Mo in aqueous sample was concentrated about 100-fold. The sorption recoveries of elements were higher than 99.6%. The method is also applied for the analysis of natural and spiked water samples.