Characterization of the Stabilization of Arsenic in Mine Tailings

Ferrous chloride has been evaluated as a novel approach to stabilize arsenic in mine tailings. The influence of iron/arsenic molar ratio, pH, stabilization time, granularity, and temperature on the concentration of released arsenic was evaluated. Arsenic speciation before and after stabilization was characterized. When the iron/arsenic molar ratio was 1 and the pH was between 6.5 and 7.5 below 50°C using a stabilization time of 1?h, the concentration of released arsenic was below 2.5?mg/L which meets national Chinese standards. Hence, this approach enhanced the stability of arsenic and reduced the toxicity of mining by-products.     

环境水中化学需氧量的FI分光光度法自动在线检测

本文将流动注射分光光度法用于环境废水中化学需氧量（ＣＯＤ）的自动在线检测，方法线性范围在０－１００ｍｇ／Ｌ之间，相对标准偏差＜２％以葡萄糖和苯二甲酸氢钾混合液制备标准溶液，对标准参考水样ＣＯＤ含量（Ｃｒ值）的测定结果表明两者有良好的相关性（Ｒ＝０．９８８０）对环境水样中ＣＯＤ含量的动态变化连续１０ｈ模拟试验，自制的在线过滤装置稳定，未发生堵塞现象；该系统可以较好地跟踪水样中ＣＯＤ浓度的实际变化     

Proximity‐Triggered Covalent Stabilization of Low‐Affinity Protein Complexes In Vitro and In Vivo

The characterization of low‐affinity protein complexes is challenging due to their dynamic nature. Here, we present a method to stabilize transient protein complexes in vivo by generating a covalent and conformationally flexible bridge between the interaction partners. A highly active pyrrolysyl tRNA synthetase mutant directs the incorporation of unnatural amino acids bearing bromoalkyl moieties (BrCnK) into proteins. We demonstrate for the first time that low‐affinity protein complexes between BrCnK‐containing proteins and their binding partners can be stabilized in vivo in bacterial and mammalian cells. Using this approach, we determined the crystal structure of a transient GDP‐bound complex between a small G‐protein and its nucleotide exchange factor. We envision that this approach will prove valuable as a general tool for validating and characterizing protein–protein interactions in vitro and in vivo.     

Experimental Study on COD Composition and Electrochemical Degradation of Wastewater in Offshore Oilfields

Chemical oxygen demand (COD ) of standard discharge wastewater in offshore oilfields is an important part of oilfield wastewater treatment. Polymer‐containing oily wastewater from oilfields in Bohai Sea was taken as the subject of this study. Combined with wastewater treatment experiments, the major composition of COD such as oils, polymer, and chemical agents is studied. Under certain conditions, the two‐dimensional plug‐flow electrochemical reactor was used to treat wastewater, and a linear relation between COD and concentration was established in the low concentration range. A preliminary study was carried out on the main factors of COD removal, and the results show that, compared to the polymer, oils are more easily electrolyzed whereas the chemical agents are more difficult to be electrolyzed. The highest COD removal by electrochemical treatment of wastewater was 75.34%, and the residual COD in wastewater was mainly contributed by the chemical agents and polymer that were not degraded completely.     

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O₂), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O₂^?, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO₂ in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO₂ can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O₂/CO₂ battery is developed. The CO₂ not only facilitates the in situ formation of a passivated protective Li₂CO₃ film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O₂^?. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li₂CO₃. The Li–O₂/CO₂ battery achieves a full discharge capacity of 6628 mAh g^?1 and a long life of 715 cycles, which is even better than those of pure Li–O₂ batteries.     

氢化物发生-原子荧光光谱法测定水系沉积物中铋和汞

水系沉积物试样用盐酸-硝酸-水(3+1+4)混合溶液溶解,氢化物发生-原子荧光光谱法测定铋和汞的含量。对介质酸度、硼氢化钾浓度、负高压和灯电流等影响铋和汞测定因素进行了试验并予以优化。铋和汞的检出限(3S/N)分别为0.02,0.01μg.L-1,相对标准偏差(n=11)均小于0.5%。应用此法分析了水系沉积物标准样品,测定值与推荐值相符。     

Characterization of Anthocyanins and Anthocyanin-Derivatives in Red Wines during Ageing in Custom Oxygenation Oak Wood Barrels

The ageing of wines in oak barrels is a key stage in the production of high-quality red wines, with the type of oak chosen and the amount of oxygen received by the wine being the determining factors of the process. This work analyses the effect of ageing the same red wine in barrels with different oxygenation rates for one year (OTR), specifically the effect on the evolution of anthocyanins, their derivatives and the appearance of new pigments according to the oxygen dosage in barrels. Results show that wines aged in High-Wood-OTR barrels have a large quantity of monomeric anthocyanins and wine aged in Low-Wood-OTR barrels presents a major intensity of colour. Moreover, using LC-MS analysis, it was possible to detect and identify different families of anthocyanin derivatives, including the tentative identification of two new aldehyde-flavanol-methylpyranoanthocyanin pigments.     

土壤和沉积物中凝聚态有机质的表征

在375℃条件下用三氟醋酸(TFA)、通氧燃烧的方法,从珠江三角洲被污染的3个土壤和6个沉积物样品中提取非水解有机碳(NHC)和碳黑(BC),并进行了元素分析、傅里叶变换红外光谱(FTIR)、固态13C核磁共振(13CNMR)、放射性碳加速质谱等一系列定性、定量的研究。结果表明:用三氟醋酸(TFA)可以成功地提取凝聚态的非水解碳,消除了碳水化合物等可水解有机质对凝聚态有机质研究的干扰。样品中非水解碳和碳黑碳分别占总有机碳含量的25.6%～70.5%和4.14%～17.3%,其平均值分别为44.2%和11.2%。非水解碳和碳黑两者的O/C和H/C比值都比较低;13C核磁共振显示NHC中主要含有脂肪碳和芳香碳峰,其中含氧官能团几乎可以忽略。研究表明,非水解碳主要由不同成熟度的沥青或干酪根、古老的陆源有机质、碳黑、煤、木质素等组成。实验结果表明:用水解的方法可以从土壤和沉积物中分离出凝聚态的碳。     

氧化与还原条件下伊通河长春区段沉积物重金属形态特征的对比研究

利用改进的Tessier连续萃取法研究了伊通河长春市自由大桥处不同深度沉积物样品在氧化及还原条件下Cu,Pb,Zn和Ni的形态变化规律,同时分析了沉积物样品中酸可挥发性硫(Acid volatile sulfide,AVS)和同时提取重金属(Simultaneous extract metals,SEM)的含量. 实验结果表明，样品经干燥、研磨处理后,Cu有机/硫化物结合态比例减少40%,锰氧化物结合态的比例显著增加; Pb,Zn和Ni 3种元素有机/硫化物结合态比例均略有下降,变化幅度小于Cu,并重新分配到不同的化学相中. 通过SEM中各金属含量与有机/硫化物结合态中金属含量的对比可知,还原性沉积物中Cu除了与硫化物结合外,很大一部分是以有机物形态存在的,Pb,Zn,Ni,Fe和Mn则主要以硫化物形态存在,各元素形态分析均不同程度地受到萃取剂的影响.     

沱江流域Pb、Cd的环境污染化学行为研究

对沱江流域金堂、简阳、内江三地河流沉积物中重金属Pb和Cd含量及其时空分布特征进行了研究,并结合与沉积物中Fe、Mn和LOI等参数的相关性对河流沉积物中Pb和Cd地球化学性质进行了初步的分析和讨论。结果表明,沱江三地沉积物中Cd、Pb含量不高,平均含量按上、中、下游次序逐渐降低;从垂向分布行为看,Cd在上游金堂地区上部含量高于下部,而中、下游两地则相反,而Pb均随着深度的增加而减少,反映了近年来人类活动所产生Pb污染的加剧;TOC、沉积物性状和上覆水体中的物化性质对于其垂向分布有着较大影响。对于深入揭示水环境中重金属的环境地球化学循环有着重要的指导意义。     

龙门山地区水系沉积物中铀含量分布特征

铀元素是具有毒性和放射性的锕系元素之一,对区域环境和人体健康具有极大的危害,开展铀元素污染评价具有重要的现实意义。以龙门山地区主要水系为主要研究对象,采集了大量的水系沉积物样品,对该地区的铀元素分布特征进行了研究。研究表明,大渡河水系沉积物中铀平均质量分数为5.50 mg/kg,绵远河水系沉积物中的铀平均质量分数为3.07 mg/kg,其余河流水系沉积物中铀含量均较低。通过龙门山地区水系沉积物中铀元素分布特征与龙门山地区矿产分布对比发现,煤矿、磷矿开发区是水系主要铀元素来源。     

Stabilization and kinetics in the emulsion copolymerization of butyl acrylate and methyl methacrylate

We carried out emulsion homopolymerizations and copolymerizations of butyl acrylate (BuA) and methyl methacrylate (MMA) with different types and concentrations of surfactants to determine the influence of these parameters on the particle size and particle size distribution and to elucidate the mechanism of particle formation. As expected, the mechanisms of nucleation above and below the critical micelle concentration were very different; however, it was also found that the presence of partially soluble monomers such as MMA in the water phase had a significant influence on the critical micelle concentration of Triton X‐405 (>50%). In addition, the nucleation mechanism during copolymerization seemed to be dominated by BuA, with the number of particles per liter being very similar to the number nucleated during its homopolymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2832–2846, 2001     

Identification of Phototoxic Polycyclic Aromatic Hydrocarbons in Sediments Through Sample Fractionation and QSAR Analysis

Abstract

The toxicity of certain polycyclic aromatic hydrocarbons (PAHs) can be greatly increased by simultaneous exposure of test organisms to ultraviolet (UV) wavelengths present in sunlight. This phenomenon, commonly termed photoinduced toxicity, had been evaluated extensively in laboratory settings where only one chemical of concern was present. However, more recent studies have demonstrated that complex mixtures of PAHs present, for example in sediments, also can cause phototoxicity to a variety of aquatic species when the samples are tested in simulated sunlight. Unfortunately, because these types of samples can contain thousands of substituted and unsubstituted PAHs it is difficult, if not impossible, to use conventional analytical techniques to identify those responsible for photoinduced toxicity. The objective of the present study was to link two powerful ecotoxicology tools, toxicity-based fractionation techniques and QSAR models, to identify phototoxic chemicals in a sediment contaminated with PAHs emanating from an oil refinery. Extensive chromatographic fractionation of pore water from the sediment, in conjunction with toxicity testing, yielded a simplified set of sample fractions containing 12 PAHs that were identified via mass spectroscopy. Evaluation of these compounds using a recently developed QSAR model revealed that, based upon their HOMO-LUMO gap energies, about half were capable of producing photoinduced toxicity. We further evaluated the phototoxic potential of the reduced set of PAHs by determining their propensity to bioaccumulate in test organisms, through calculation of octanol-water partition coefficients for the chemicals. These studies represent a novel linkage of sample fractionation methods with QSAR models for conducting an ecological risk assessment.     

Determination of Lead,Cadmium and Mercury in Surface Marine Sediments and Mussels

Abstract

Lead, cadmium and mercury were determined in sediments and mussels, and the ability of these indicators to record metal variations in coastal marine environment is described in this work. The results of an extended investigation of the status of three gulfs at Northern Greece are given, regarding the content of these metals in surface sediments and Mytilus galloprovincialis. The samples were collected during a four-year period. The total concentration of the above heavy metals was determined after digestion of the samples by suitable mixtures of acids, including nitric, perchloric and hydrofluoric acid. The digestion was carried out in a steel pressurised bomb with closed teflon vessels. Lead and cadmium were determined by means of electrothermal atomic absorption spectrometry (ETAAS), and mercury by cold vapour atomic absorption spectrometry (CVAAS). The results were statistically evaluated by analysis of variance, and emphasis was given to annual, seasonal and spatial sources of variation. The annual changes during the last four years and the spatial distribution of heavy metals load is also discussed.     

Characterization of a Stable Adaptive Calibration Model Using Near-Infrared Spectroscopy and Partial Least Squares with a Kalman Filter

The calibration model of near-infrared (NIR) spectra established using the Kalman filter-partial least square (partial least squares combined with a Kalman filter) method can be adapted to outdated equipment, environmental changes, external samples, and other applications. However, the variance of the measurement noise estimation for NIR spectrum measurements cannot be easily obtained using Kalman filter-partial least squares; therefore, the variance in the measurement noise is often assumed to be zero for the Kalman filter-partial least square calibration model, which affects the stability of the model. In this study, the measured input and output data were used effectively, and the gamma test method for estimating the measurement noise variance was used to improve the stability of the Kalman filter-partial least square calibration model. First, an accurate estimation of the measurement noise variance was obtained, and accurate modeling was then performed using Kalman filter-partial least squares. Finally, 600 abandoned drilling fluid samples were used to confirm the validity of the proposed method. The Kalman filter-partial least square and gamma test-Kalman filter-partial least square methods are compared. Testing of external samples 401–600 demonstrated that the stability of the Kalman filter-partial least square model decreased. The root mean square error of the prediction of the Kalman filter-partial least square model was 27.135, which was worse than that of the gamma test-Kalman filter-partial least square model (20.307). The validation results show that the proposed method has better stability in tracking the evolution of the NIR spectrometer’s measurement state.     

海湾河口表层沉积物中重金属形态连续萃取方法的优化研究

采用单一萃取程序对建立的重金属形态连续萃取方法的萃取条件进行优化.分别以Ca和Mg、Fe、有机质(OM)和酸可挥发性硫(AVS)作为萃取剂释放酸溶态、还原态、有机质结合态和硫化物结合态等重金属目标形态的表征参量,考察萃取剂对相应目标形态的萃取能力和选择性.分别根据表征参量和重金属在萃取溶液中的含量变化确定最优萃取时间和萃取样液比.结果表明,优化萃取条件后,萃取剂对目标形态重金属均有很强的释放能力.酸溶态萃取剂对其它非残留态影响很小;还原态萃取剂除对酸溶态有少量提取外,对其它形态影响较小;有机质结合态萃取剂对硫化物结合态有少量萃取,对其它形态影响较小.硫化物结合态在酸溶态、还原态和有机质结合态之后萃取,避免了对这三种形态的影响.优化后的连续萃取方法对重金属形态有较好的选择性,可对海湾和河口表层沉积物中重金属的目标形态进行较为合理地分离和评价.     

determination of Carbon,Nitrogen and Sulfur in Soils,Sediments and Wastes: A Comparative Study

Abstract

The determination of low levels (< 1 %) of total carbon and nitrogen in soils, sediments and solid wastes is made fast using an automated elemental NCS analyzer (Carlo Erba NA-1500). The recoveries of total N obtained were similar with either the elemental analyzer or the Kjeldahl digestion method used. The recoveries and precision of the TC, TOC data were better and more predictable using the elemental analyzer than the wet digestion procedure used in this study. Acid pre-treatment prior TOC determinations using the NCS analyzer resulted in lower total N recoveries. The determination of S in the same materials using this analyzer is not recommended due to low recoveries and poor precision.     

微波辅助提取-液相色谱-氢化物发生-原子荧光光谱法分析沉积物中砷的形态

采用微波辅助提取-液相色谱-氢化物发生-原子荧光光谱法(LC-HG-AFS)联用技术分析了太湖沉积物中砷的形态[亚砷酸(As(III))、二甲基砷酸钠(DMA)、一甲基砷酸二钠(MMA)和砷酸As(V)]。测得沉积物中以无机砷为主,且以As(V)居多。选定以1mol/L的磷酸和0.1mol/L抗坏血酸为提取液,在微波辅助萃取(功率为60W,时间12min)下,萃取率达79.84%～91.57%,回收率在94.78%～107.6%之间。4种砷的形态在0～160μg/L之间时线性良好,检测限为0.6～2.3μg/L,相对标准偏差RSD为1.62%～2.20%。方法具有简便、快速、灵敏的特点。     

Stabilization of the Pentazolate Anion in a Zeolitic Architecture with Na20N60 and Na24N60 Nanocages

The experimental detection and synthesis of pentazole (HN₅) and its anion (cyclo‐N₅^?) have been actively pursued for the past hundred years. The synthesis of an aesthetic three‐dimensional metal–pentazolate framework (denoted as MPF‐1) is presented. It consists of sodium ions and cyclo‐N₅^? anions in which the isolated cyclo‐N₅^? anions are preternaturally stabilized in this inorganic open framework featuring two types of nanocages (Na₂₀N₆₀ and Na₂₄N₆₀) through strong metal coordination bonds. The compound MPF‐1 is indefinitely stable at room temperature and exhibits high thermal stability relative to the reported cyclo‐N₅^? salts. This finding offers a new approach to create metal–pentazolate frameworks (MPFs) and enables the future exploration of interesting pentazole chemistry and also related functional materials.     

Stabilization, injection and control of quantum cascade lasers, and their application to chemical sensing in the infrared

Quantum cascade lasers (QCLs) are a relatively new type of semiconductor laser operating in the mid- to long-wave infrared. These monopolar multilayered quantum well structures can be fabricated to operate anywhere between 3.5 and 20 microm, which includes the molecular fingerprint region of the infrared. This makes them an ideal choice for infrared chemical sensing, a topic of great interest at present. Frequency stabilization and injection locking increase the utility of QCLs. We present results of locking QCLs to optical cavities, achieving relative linewidths down to 5.6 Hz. We report injection locking of one distributed feedback grating QCL with light from a similar QCL, demonstrating capture ranges of up to +/-500 MHz, and suppression of amplitude modulation by up to 49 dB. We also present various cavity-enhanced chemical sensors employing the frequency stabilization techniques developed, including the resonant sideband technique known as NICE-OHMS. Sensitivities of 9.7 x 10(-11) cm(-1) Hz(-1/2) have been achieved in pure nitrous oxide.