State of the Art Report on Multivariate Chemometric Methods in Environmental Forensics☆

Environmental forensic analysis has evolved significantly from the early days of qualitative chemical fingerprint evaluations. The need for quantitative rigor has made the use of numerical methods critical in identifying and mapping contaminant sources in complex environmental systems. Given multiple contaminant sources, the environmental scientist is faced with the challenge of unraveling the contributions of multiple plumes with overlapping spatial and temporal distributions. The problem may be addressed through a multivariate statistical approach, but there is a mind-boggling array of the available "chemometric" methods. This paper provides an overview of these methods, along with a review of their advantages, disadvantages, and pitfalls. Methods discussed include principal component analysis and several receptor-modeling techniques.     

不同垃圾渗滤液组合处理工艺中DOM的变化特征

为了快速表征垃圾渗滤液处理过程中有机物的特性变化,分别采用紫外光谱和三维荧光光谱对2种垃圾渗滤液处理工艺不同单元溶解性有机物(DOM)的变化进行了系统分析。结果表明,二级RO和厌氧+好氧+MBR+NF+RO工艺对渗滤液COD和NH3-N的去除率分别为98.7%、99.0%和98.8%、98.6%。随着处理过程的进行,2个处理工艺中DOM的SUVA254、E253/E203分别由0.74、0.33和0.46、0.12下降至0.015、0.014和0.010、0.012,有机物的芳香性和不饱和性下降,脂肪链芳香烃化合物开始增加。不同处理阶段渗透液DOM三维荧光光谱表明,随着处理过程的进行,类富里酸和类蛋白物质的含量逐渐下降,芳构化程度开始降低。其中二级RO系统对渗滤液中类富里酸物质的去除效果较好,而厌氧-好氧-MBR-NF-RO工艺中,类酪氨酸物质主要通过微生物降解去除,NF和RO膜对类富里酸和类腐殖酸物质的截留效果较好。     

张家口市沙尘天气过程气溶胶单颗粒特征研究

利用单颗粒气溶胶质谱仪对张家口市2015年春季的一次典型沙尘过程进行了监测,分析了沙尘过程对当地大气颗粒物成分的影响。结果表明,监测期间的颗粒物类型主要分为8种:矿物质(MD)、左旋葡聚糖(LEV)、元素碳(EC)、有机碳(OC)、混合碳(ECOC)、重金属(HM)、富钾(K)、其他(Other)。对比沙尘天气来临前、中、后3个时段,随着沙尘天气的来临,本地大气颗粒物成分发生较大变化,矿物质、左旋葡聚糖等成分含量升高,而有机碳、重金属等成分含量下降,其中矿物质在PM10峰值时段小时比例高达27.8%;沙尘天气期间,由于矿物质颗粒占比增加,使得总颗粒物的粒径分布向0.9μm以上的粗粒径段偏移;此外,沙尘天气期间的颗粒物各成分与二次组分的混合程度相较非沙尘天气时段的低,说明其老化程度相对较低。     

Identification and Classification of Key Variables and their Role in Environmental Impact Assessment: Methodology and Software Package Intra

There is, as yet, no proven methodology to enable, objectively,the identification of key parameters out of a large number one normally encounters during any EIA. As EIA is a costly and time-consuming exercise, it is necessary to separate the man from the boys – so to speak – in order to optimize costs andefforts.In this paper a methodology for distinguishing the moreimportant parameters from the less important ones, developed byus, is described. The methodology aims at identifying andshortlisting the key parameters which ought to be studied in agiven EIA situation, thereby helping in reducing time, effort,and cost of EIA. With this methodology a system structure is developed whichgives hierarchical pattern of inter-parameter interaction, andreveals several distinguishing features of each parameter. Asoftware package INTRA (INTer-parameter Relationship Analysis)based on this methodology, has been developed. The paper alsodescribes a case study in which INTRA has been used to study theenvironmental impacts of urbanization of a typical third worldtown (Roorkee).     

Atmospheric Aerosol over a Southeastern Region of Texas: Chemical Composition and Possible Sources

Speciated samples of PM_2.5 were collected at a site in Jefferson County, Texas by US EPA (Environmental Protection Agency) from July of 2003 to August of 2005. A total of 269 samples with 52 species were measured; however, 22 species were excluded in this study because of too many below-detection-limit data. The data set was analyzed by positive matrix factorization (PMF) to infer the sources of PM observed at the site. The analysis identified ten sources: sulfate-rich secondary aerosol I (35.9%), sulfate-rich secondary aerosol II (21.0%), cement/carbon-rich (11.7%), wood smoke (8.8%), metal processing (6.3%), motor vehicle/road dust (5.7%), nitrate-rich secondary aerosol (3.3%), soil (3.2%), sea salt (2.6%), and chloride depleted marine aerosol (1.6%). Sulfate and nitrate mainly exist as salts. The two sulfate-rich secondary aerosols account for almost 57% of the PM_2.5 mass concentration. The factor containing highest concentrations of Cl and Na was attributed to sea salt due to the proximity of the monitoring site to the Gulf of Mexico. The chloride depleted marine aerosol was related to the sea salt aerosol. Cement/carbon-rich, wood smoke, metal processing, and motor vehicle/road dust factor were likely to be the local sources.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

区域地震应急能力优先建设矩阵构建方法的初步研究——以四川省为例

借鉴新一代的时间管理理论——"时间管理优先矩阵",提出并分析了区域地震应急能力优先建设矩阵的概念。分别以区域绝对和相对地震应急能力作为优先建设矩阵中"紧迫与否"和"重要与否"的定量化评价指标,构建了区域地震应急能力优先建设矩阵,划分了能力建设的四种类型,即需重点建设且紧迫性较强的区域类型(第Ⅰ类)、需重点建设但紧迫性较弱的区域类型(第Ⅱ类)、次重要建设但具一定紧迫性的区域类型(第Ⅲ类)和次重要建设且紧迫性较弱的区域类型(第Ⅳ类),在区域能力建设过程中应当遵循从第Ⅰ类到第Ⅳ类建设力度由重到轻、时间由急到缓,逐步开展的原则。最后,以四川省为例,以县(市)为基本评价单元,给出了四川省未来地震应急能力建设的优先等级类型。     

Assessment of GC–MS response of selected pesticides in apple matrices related to matrix concentration

A uniform analyte response is required for GC–MS analysis in order to obtain acceptable quantitative results. The response of pesticides in complex matrices is susceptible to variation due to the interactions of co-extractives, both with pesticides or with GC–MS system. This study was conducted to determine the magnitude of the interactions, called matrix effect, and their behavior with the matrix dilution. The response of pyrimethanil (4,6-dimethyl-N-phenylpyrimidin-2-amine), cyprodinil (4-cyclopropyl-6-methyl-N-phenylpyrimidin-2-amine), trifloxystrobin (methyl-(2Z)-2-methoxyimino-2-[2-[[(E)-1-[3(trifluoromethyl)phenyl]ethylidene amino]oxymethyl]phenyl]acetate) and bifenthrin(2-methyl-3-phenylphenyl)methyl-3-[(Z)-2-chloro-3,3,3-trifluoroprop-1-enyl]-2,2-dimethylcyclopropane-1-carboxylate), used in apple crops protection, was evaluated in different concentrations of peel and flesh extracts of Granny Smith, Golden Delicious and Demi Rouge, selected as representatives of different matrix types. The matrix effect ranged from ?0.05 to 146.14%, depending on matrix type and pesticide. The highest response variation was observed in extracts of Granny Smith—an enhancement in flesh and suppression in peel extract. With the dilution, the matrix effect decreased with different magnitudes, but for Granny Smith peel extract an inverted effect was observed. The presence of the matrix effect in GC–MS pesticides analysis was obvious, requiring the application of matrix-matched calibration in quantification procedures for each variety, with calibration standards matched by the matrix concentration.     

Variation of short-lived beta radionuclide (radon progeny) concentrations and the mixing processes in the atmospheric boundary layer

Radon is emitted to the atmosphere with quasi constant emission rates depending on the radium concentration in the earth's crust and soil physical properties. In this way, the ²²²Rn and ²²⁰Rn concentration in air reflects significantly the thickness of the atmospheric boundary layer (ABL). The aerosol-associated, beta-emitting progeny nuclides of ²²²Rn were measured daily in the framework of the atmospheric radioactivity monitoring program of NIMH at Sofia. The ²¹⁴Pb concentration was estimated from the measured short-lived beta activity of 24-h filter samples, changed daily at 6:00 GMT. The impact of some meteorological factors such as wind direction, wind velocity, humidity, and temperature on short-lived beta radionuclides is estimated, and the results show no simple statistical relationship. A seasonal pattern was observed with winter minima and late summer-early autumn maxima. High variability in daily morning concentrations and mean monthly values was observed. There were well pronounced differences between years. The height of the convective ABL was estimated from daily radio-soundings at 12:00 GMT for the period 2001-2006 and from seven soundings per day during the experimental campaign in Sofia in October 2003. In general, concentrations of short-lived ²²²Rn progeny nuclides decreased with increased convective ABL height.     

Phenol degradation using combined effects of hydrodynamic cavitation and oxidant: Doehlert matrix

Hydrodynamic cavitation (HC)-based treatments have been proposed for the degradation of phenol as a toxic pollutant. The present work aimed to optimize the degradation of phenol using HC by means of Doehlert experimental design, which has not been previously addressed. Initially, operational parameters of hydraulic characteristics of the pump, inlet pressure, solution pH, and initial concentration were optimized; later, the effects of pH solution and H₂O₂ loading or initial pollutant concentration on phenol degradation were explored using the Doehlert experimental design. It was observed that phenol degradation is strongly dependent on the pH of the solution. Also, the acidic condition favors the formation of hydroxyl radicals and thus, the degradation of phenol. Based on the Doehlert matrix, the 94.1% phenol degradation and 68.60% total organic carbon (TOC) were obtained in 180 min at 304.5 mg/L of hydrogen peroxide at an initial concentration of 20 mg/L, 2.0 pH, and 90 psi inlet pressure, providing a cavitational yield of 6.33 × 10⁻⁶ mg/J and minimum treatment cost of US$/L 0.13. Overall, it has been observed that HC can be a promising route for the removal of pollutants (phenol) effectively using hydrogen peroxide as an additive.