烯唑醇免疫亲和色谱柱的制备及其在样品前处理中的应用

将四甲氧基硅烷(TMOS)水解后与烯唑醇抗体聚合,采用溶胶-凝胶法合成了烯唑醇免疫亲和色谱(IAC)柱固定相,并用其制备了对烯唑醇具有特异性亲和力的IAC柱。对IAC柱条件进行了优化,选择超纯水作为吸附与平衡介质,30%～50%(体积分数)甲醇水溶液作为洗脱剂。结果表明: 在优化条件下,IAC柱对烯唑醇的动态柱容量达125.4 μg/g。在河水样品和水果样品中添加烯唑醇,经IAC柱净化富集,洗脱液采用高效液相色谱检测,河水中烯唑醇的平均回收率为90.36%～100.14%,相对标准偏差(RSD)为2.03%～6.08%;水果中烯唑醇的平均回收率为85.55%～94.02%, RSD为3.38%～6.78%。本研究为烯唑醇在河水、水果等样品中的残留分析提供了一种新的高效前处理手段。     

Quantitative Determination and Environmental Risk Assessment of 102 Chemicals of Emerging Concern in Wastewater-Impacted Rivers Using Rapid Direct-Injection Liquid Chromatography—Tandem Mass Spectrometry

The rapid source identification and environmental risk assessment (ERA) of hundreds of chemicals of emerging concern (CECs) in river water represent a significant analytical challenge. Herein, a potential solution involving a rapid direct-injection liquid chromatography–tandem mass spectrometry method for the quantitative determination of 102 CECs (151 qualitatively) in river water is presented and applied across six rivers in Germany and Switzerland at high spatial resolution. The method required an injection volume of only 10 µL of filtered sample, with a runtime of 5.5 min including re-equilibration with >10 datapoints per peak per transition (mostly 2 per compound), and 36 stable isotope-labelled standards. Performance was excellent from the low ng/L to µg/L concentration level, with 260 injections possible in any 24 h period. The method was applied in three separate campaigns focusing on the ERA of rivers impacted by wastewater effluent discharges (1 urban area in the Basel city region with 4 rivers, as well as 1 semi-rural and 1 rural area, each focusing on 1 river). Between 25 and 40 compounds were quantified directly in each campaign, and in all cases small tributary rivers showed higher CEC concentrations (e.g., up to ~4000 ng/L in total in the R. Schwarzach, Bavaria, Germany). The source of selected CECs could also be identified and differentiated from other sources at pre- and post- wastewater treatment plant effluent discharge points, as well as the effect of dilution downstream, which occurred over very short distances in all cases. Lastly, ERA for 41 CECs was performed at specific impacted sites, with risk quotients (RQs) at 1 or more sites estimated as high risk (RQ > 10) for 1 pharmaceutical (diclofenac), medium risk (RQ of 1–10) for 3 CECs (carbamazepine, venlafaxine, and sulfamethoxazole), and low risk (RQ = 0.1–1.0) for 7 CECs (i.e., RQ > 0.1 for 11 CECs in total). The application of high-throughput methods like this could enable a better understanding of the risks of CECs, especially in low flow/volume tributary rivers at scale and with high resolution.     

Method Development for the Speciation of Chromium in River and Industrial Wastewater Using GFAAS

A simple, sensitive and inexpensive method for the speciation of Cr(VI) and Cr(III) in river and industrial wastewater was developed, optimized and validated. Samples were collected, filtered and then chromium species were determined in the filtrate. In the filtrate, total Cr was determined directly by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). A portion of the filtered sample was buffered to pH 6.4, extracted with Amberlite LA-2/MIBK and finally Cr(VI) was determined in the organic extract and Cr(III) in the aqueous phase using GFAAS. The method was evaluated by analysis of the certified reference material, CRM 544, and good accuracy was obtained. The limit of detection for Cr(VI) and Cr(tot)/Cr(III) was found to be 0.30 and 0.08 µg L⁻¹, respectively, and a precision expressed as relative standard deviation of better than 11% was achieved for nine replicates. A number of water samples from the Tinishu Akaki River, Ethiopia, and wastewater samples from a chemical plant in Germany, were analysed. In addition to the GFAAS method, Cr(tot) was also determined using ICP-MS (in CRM 544, lyophilized water, and Tinishu Akaki River water samples) and Cr(tot) and Cr(VI) using UV-VIS spectrophotometry (in CRM 544 and industrial wastewater samples). Good agreement between the different methods was found.     

Determination of organochlorine pesticides in river water using dispersive liquid–liquid microextraction and gas chromatography–electron capture detection

Dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–electron capture detection (GC–ECD), has been developed for the extraction and determination of 14 organochlorine pesticides (hexachlorocyclohexanes (α-HCH, β-HCH and δ-HCH), Lindane (γ-HCH), Aldrin, Dieldrin, Endrin, Heptachlor, Heptachlor epoxide, α-Chlordane, β-Chlordane and p,p′-DDT, p,p′-DDD, p,p′-DDE) in river water samples. Factors relevant to the microextraction efficiency, such as the kind of extraction and disperser solvent, their volume and the salt effect was investigated and optimised. In this method the appropriate mixture of extraction solvent (13.5 µL carbon disulphide) and disperser solvent (0.50 mL acetone) were rapidly injected into the aqueous sample by syringe. The values of the detection limit of the method were in the range of 0.05–0.001 µg L^?1, while the relative standard deviations for five replicates varied from 2.7 to 9.3%. A good linearity (0.9894 ≤ r ² ≤ 0.9998) and a broad linear range (0.01–200 µg L^?1) were obtained. The method exhibited enrichment factors ranging from 647 to 923, at room temperature. The relative standard deviations varied from 2.7 to 9.3% (n = 5). The relative recoveries of each pesticide from water samples at spiking levels of 2.00 and 10.0 µg L^?1 were 88.0–111.0% and 95.8–104.1%, respectively. Finally, the proposed method was successfully utilised for the preconcentration and determination of the organochlorine pesticides in the Jajrood River water samples.     

冬季平原河网水体溶存甲烷和氧化亚氮浓度特征及排放通量

以长江三角洲上海地区和海河流域天津地区水网为研究对象,对冬季河网表层水体溶存甲烷（CH4）和氧化亚氮（N2O）浓度、饱和度及水-气界面排放通量进行了研究.结果表明,冬季我国平原河网水体溶存CH4和N2O的浓度值都很高,呈高度过饱和状态：CH4浓度均值为0.86mol/L（饱和度：758%）,范围在（0.043±0.001）～（25.3±9.32）μmol/L之间;N2O浓度均值为86.8nmol/L（饱和度：488%）,范围在（9.71±0.41）～（691±35.2）nmol/L之间变化.天津排污河水体CH4和N2O浓度显著高于其他河流（均值分别为38.4mol/L和88.9nmol/L）.水体溶存CH4和N2O浓度、饱和度存在很大的地区差异,上海河网的CH4和N2O浓度和饱和度均值高于天津河网.河网水体水-气界面CH4和N2O排放通量变化范围很广,CH4通量在（1.35±0.22）～（665±246）mol/m2h之间,平均值为24.1mol/m2h,N2O通量在（0.19±0.02）～（22.6±5.05）mol/m2h之间,平均值为2.28mol/m2h.相关分析发现,河网水体溶存CH4浓度与DO显著负相关,与NH4＋显著正相关;N2O浓度则与NH4＋和NO3＋NO2显著正相关.河网水-气界面CH4和N2O排放通量均呈现出市区高郊区和农村低的空间分布规律,污染严重的河流已显然成为大气CH4和N2O的潜在排放源.     

Simultaneous electrochemical determination of hydrazine and nitrite based on Au nanoparticles decorated on the poly(Nile Blue) modified carbon nanotube

In this study, simultaneous determination of toxic hydrazine and nitrite was performed on composite electrodes of poly(Nile blue)(NB), carbon nanotube(CNT) and gold nanoparticles(AuNPs). The prepared AuNPs/CNT/poly(NB)/GCE was used for as a sensor platform for individual and simultaneous determination of hydrazine and nitrite. Electrodes were characterized by HRTEM, SEM, XPS, EIS. The LOD for nitrite and hydrazine was 5.0 μM and 3.1 μM at AuNP/CNT/poly(NB)/GCE, respectively. Also, sensitive amperometric determinations of hydrazine and nitrite were performed and LOD were calculated as 0.33 μM and 0.68 μM, respectively. The method was applied to sausage and river water samples and recovery results were obtained in the range 85–115 %.     

The influence of inert solids on ethanol production by Saccharomyces cerevisiae

The catalytic role of various inert solid supports on acceleration of alcohol fermentation by Saccharomyces cerevisiae was investigated. The enhanced rate of alcohol production was dependent on the nature of the support as well as on the amount used. Among all the tested supports, chitosan flakes showed the maximum yield of alcohol (93% of theoretical yield). This higher rate of alcohol production was associated with the twofold increase in the activity of alcohol dehydrogenase over control. Our results suggest that the addition of a small fraction of solids in submerged fermentations to facilitate cell anchorage for enhanced metabolic activity is easier and more economical compared to cell immobilization processes. IICT Communication No. 4266. Some of the results in this article are covered under a patent.     

Evaluation of a synergetic effect between Rh as permanent chemical modifier and acetylacetone as complexing agent in Sc determination in sediment slurry samples by ETAAS

In the present work, scandium was determined in sediment slurry samples (from three different rivers) by electrothermal atomic absorption spectrometry (ETAAS). Slurries were prepared by weighting 100 mg of dry sediment samples (≤53 μm particle sizes) and adding 6 ml of HCl:HNO₃:HF (3:1:2, v/v). Accurate results were only possible due to the synergetic effect between Rh as permanent chemical modifier and acetylacetone (Acac) as complexing agent. The same platform was used for 400 heating cycles. The performance of the chemical modification was evaluated by using scanning electron microscopy (SEM), synchrotron radiation X-ray fluorescence (SRXRF) and some figures of merit (precision and detectability). The best analytical conditions were attained using 1500 and 2550 °C as pyrolysis and atomization temperatures. The scandium content in the liquid phase of the slurries ranged from 61 to 73%, thus indicating, in this study, that both liquid and solid phases play an important role in slurry analyses. An amount of 5.0–20.0 μg l⁻¹ Sc linear range as well as LOD and LOQ of 0.19 and 0.62 μg l⁻¹, respectively, were obtained under these conditions. The accuracy was checked by using microwave-assisted decomposition, and the results compared to those obtained with the proposed methodology (slurry analysis). By checking both sets of the results, there is no statistical difference at the 95% confidence levels.     

长三角地区房地产市场是如何实现"去库存"的?

长三角地区在全国房地产"库存"的背景下,实现了房地产市场的不断向好.对长三角地区有关面板数据进行实证研究,实证结果表明房地产开发投资、医院床位数、工业生产总值与人均房地产成交面积呈正相关.城镇人口数,中、长期贷款利率与人均房地产成交面积呈负相关,高收入城市比低收入城市人均房地产成交面积低14.%,教育支出和城镇居民总的可支配收入对人均房地产成交面积影响不显著.     

有Logistic增长的媒介传播模型分析

建立了贮存宿主鸟类与传染宿主蚊子都具有Logistic增长的西尼罗河病毒传播模型,获得了基本再生数R_0.当R_0<1时,通过构造Lyapunov函数,证明了无病平衡点的全局渐近稳定性.当R_0>1,且满足不同条件时,得到了正平衡点的存在性,数值模拟验证了理论结果的正确性.