Applicability of microwave-assisted extraction combined with LC-MS/MS in the evaluation of booster biocide levels in harbour sediments

A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g⁻¹. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).     

基于相对资源承载力的青岛市主体功能区区划

本文根据相对资源承载力研究方法,以全国作为参照区域计算了2005～2008年青岛市主要辖区相对自然资源承载力、相对经济资源承载力和综合承载力.分析结果表明:①对于相对自然资源承载力而言,平度市处于富余状态;莱西市处于临界状态;胶州市、即墨市、胶南市处于超载状态:青岛市市区则处于严重超载状态.相对自然资源承载力序列(由富余到超载):平度市>莱西市>胶州市>胶南市>即墨市>市区.②青岛市各辖区相对经济资源承载力全部处于富余状态,其中市区的相对经济资源承载能力最大.相对经济资源承载力序列(由富余到超载):市区>胶州市>胶南市>即墨市>藁西市>平度市.③青岛市各主要辖区综合承载力全部处于富余状态,且基本保持稳定.综合承载力序列(由大到小):市区>平度市>即墨市>胶州市>胶南市>莱西市.在此基础上.本文对青岛市2005-2008期间主要辖区的主体功能区进行了区划,结果显示青岛市所辖6市区均属于优化开发区,在"十二五"期间.产业调整与优化仍是区域可持续发展的重中之重.     

耕地集约利用影响因素的协整分析

耕地利用的集约度实质上是农户在其所面临的各种经济和制度环境约束条件下,所采取的不同耕种行为的直接结果和体现.本文试借助分析影响农户耕种行为的相关因素来探讨其对耕地集约利用的影响.利用Eviews 6.0统计软件,综合应用协整理论和误差修正模型,以湖北省为例,剖析耕地集约利用与其影响因素的长期均衡关系和短期波动效应.研究表明:在长期,户均农业劳动力人数、农业比较收入和耕地的产权保障对耕地利用的集约度存在正向影响,其增加1个百分点,将导致耕地利用的集约度分别提高0.166、0.430和0.035个百分点;农民家庭人均农业生产支出和农业生产资料价格指数对耕地利用的集约度存在负向影响,其增加1个百分点,将导致耕地利用的集约度分别下降0.004和0.008个百分点.而在短期,各影响因素对耕地利用集约度的作用方向相同而作用力大小不同.户均农业劳动力人数和农业比较收入对耕地集约利用的作用程度在短期与在长期是相似的;但耕地的产权保障和农业生产成本的变化对耕地集约利用的影响却更多体现在长期.因此,立足于稳定产权和降低农业生产成本的农业政策导向更有利于在长期保护耕地,提高耕地资源的配置和利用效率.     

Polychlorinated biphenyls and organochlorinated pesticides in birds from a contaminated region in South China: association with trophic level,tissue distribution and risk assessment

Purpose  

Birds have been used successfully for biomonitoring of the levels and effects of persistent organic pollutants (POPs) in the environments; however, there is exceedingly little data on organochlorinated pesticide (OCPs) and polychlorinated biphenyls (PCBs) residues in bird inhabiting in China. In the present study, we detected the concentrations of PCBs, dichlorodiphenyltrichloroethane and its metabolites (DDTs) and hexachlorocyclohexanes (HCHs) in muscle, liver and kidney of birds that inhabit in an e-waste recycling site. Associated with the stable isotope ratio (δ ¹⁵N), we investigated the effect of trophic level on the body burdens of persistent contaminants in birds. The tissue distributions of contaminants in these birds were examined, and a preliminary risk assessment was also conducted.     

Detection of human-induced environmental disturbances in a show cave

Purpose  

We investigated the effects of human-induced disruption in a subterranean stable environment containing valuable Palaeolithic paintings and engravings (Ardales Cave, Southern Spain) using a double analytical approach.     

Mn-CeOx/钛基层柱粘土(Ti-PILCs)低温选择性催化还原催化剂的钙中毒研究

以钛基层柱粘土(Ti-PILCs)为载体,制备了Mn-Ceox/Ti-PILCs低温选择性催化还原(SCR)催化剂,采用浸溃法模拟了催化剂钙中毒,研究了不同含钙量对催化剂活性的影响,并运用NH3-程序升温脱附(TPD)、H2-程序升温还原(TPR)及X射线光电子能谱(XPS)表征,分析了钙对催化剂的失活作用.结果表明:...     

Effect of lipids on sorption/desorption hysteresis in natural organic matter

The chemical composition and physical conformation of natural organic matter (NOM) play a major role in regulating its capacity to retain hydrophobic organic compounds. Naphthalene and phenanthrene were used to study the correlations between sorption/desorption isotherm nonlinearity and compositional data obtained from quantitative ¹³C solid-state DPMAS NMR spectroscopy for soil and peat organic matter with or without lipids. Sorption experiments were conducted using a batch equilibration method. Desorption experiments were carried out immediately following the sorption experiments by three successive decant-refill cycles. Hysteresis was observed in all samples. Nonlinear sorption behavior was increased by removal of lipids from the NOM. The hysteresis index, obtained from the ratio of the Freundlich exponents (N values) for the desorption and sorption isotherms, was lower in the lipid-extracted NOM samples than in the same samples without lipid extraction. The relationship between the extent of hysteresis and the characteristics of the ¹³C DPMAS NMR spectra indicates that altering NOM composition through lipid extraction not only increased the proportion of aromatic-C content, but also increased sorption/desorption hysteresis. Our data also suggest that the hysteresis index is negatively related to aromaticity.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Bromination of selected pharmaceuticals in water matrices

The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin > naproxen ? hydrochlorothiazide ≈ phenacetin ≈ metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK_a value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism.In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.