Evaluation of a combined fractionation and speciation approach for study of size-based distribution of organotin species on environmental colloids

Results relating to the first original application of an analytical approach combining asymmetric flow field-flow fractionation (As-Fl-FFF) with multi-detection and chemical speciation for determination of organotins in a landfill leachate sample are presented. The speciation analysis involved off-line head-space solid-phase microextraction (HS-SPME)–gas chromatography with pulsed-flame photometric detection (GC–PFPD) performed after three consecutive collections of five different fractions of interest from the As-Fl-FFF system and cross-flow part (assumed to be representative of the <10 kDa phase). After 0.45 μm filtration and without preconcentration before fractionation and speciation analysis, limits of detection (LOD) were 4–45 ng (Sn) L⁻¹ in the sample, with relative standard deviations (RSD) of 3–23%. The As-Fl-FFF fractionation of this sample enables characterization of two distinct populations—organic-rich and inorganic colloids with gyration radius up to 120 nm. Total Sn and mono and dibutyltins (MBT and DBT) appear to be distributed over the whole colloidal phase. Tributyl, monomethyl, monooctyl, and diphenyltins (TBT, MMT, MOcT, and DPhT) were also detected. Quantitative speciation analysis performed on the two colloidal populations and in the <10 kDa phase revealed concentrations from 130 ± 10 (MMT) to 560 ± 50 ng (Sn) L⁻¹ (DPhT).     

Development and complete validation of a method for the determination of dimethyl mercury in air and other media

The rigorous validation of a previously developed research method for the determination of dimethyl mercury ((CH₃)₂Hg) in environmental samples is presented. During atmospheric analysis, (CH₃)₂Hg was trapped on Carbotrap™ and analyzed by thermal desorption, isothermal GC separation, and cold vapor atomic fluorescence spectrometry (CVAFS). Water samples were analyzed after direct purging of 100 mL aliquots onto Carbotrap™, while sediment and tissue samples were digested with 10 mL of 25% KOH in methanol at 60 °C and diluted to 40 mL with methanol. An ambient air-spiking manifold, which allowed simultaneous replicate sampling, was constructed in a room controlled for temperature and humidity. (CH₃)₂Hg was introduced into the feed airflow (0.4 m³ min⁻¹) from a well-calibrated diffusion cell, to obtain a concentration of approximately 5.5 ng m⁻³ as Hg. Samples were collected onto Carbotrap™ columns, and the total volumes quantified by integrating mass flow meters. Trapping efficiency was investigated over a range of sampler flow rates (0.05-0.25 L min⁻¹), volumes (2-200 L), collection temperatures (15-42 °C) and relative humidity levels (10-70%). Method detection limits (MDLs), analytical precision and accuracy were quantified for all media. Carbotrap™ was found to be the best choice as a sampling media, whereas Tenax™ was found to be inadequate due to high breakthrough (>70%). This study verified that the method is sufficiently precise, accurate and robust for field sampling at mercury contaminated sites. No interferences were observed from elevated levels of potential co-contaminants, Hg⁰ (125 ng m⁻³) and H₂S (1.27 ppmv).     

Static headspace versus head space solid-phase microextraction (HS-SPME) for the determination of volatile organochlorine compounds in landfill leachates by gas chromatography

The determination of five volatile organochlorine compounds, VOX (chloroform, 1,1,1-trichloroethane, carbon tetrachloride, trichloroethene and tetrachloroethene) in raw landfill leachates and biologically cleansed leachates by GC-MS is investigated. Two extraction and preconcentration procedures were evaluated for recovery of such analies from the samples, including static headspace (HS) and solid phase microextraction by sampling the headspace above the sample (HS-SPME). Optimisation of operating parameters for the best performance of both, sampling and preconcentration techniques was described. Detection limits, time of analysis, precision and linear ranges of both introduction techniques have been established. Application of proposed methods to the determination of the five VOX under study in the above referred samples revealed the absence of such analytes in both leachates. Then both methods were applied to the determination to the five organochlorine compounds under study on spiked leachates samples. While HS-GC-MS offered better analytical precision than HS-SPME-GC-MS, this last technique gave a faster analytical response because no dilution must be done for a reliable VOX determination in landfill leachates. In any case, both sample introduction techniques tested provides excellent recoveries and good analytical precision (ranged from 1 to 3%).     

填埋垃圾稳定化进程的光谱学特性表征

采用光谱分析技术,对4个不同填埋年限垃圾提取出的水溶性有机物(DOM)进行了研究,探讨DOM的荧光和紫外光谱变化特征在填埋场稳定度表征中应用的可能性。荧光光谱显示：填埋0年垃圾DOM以类蛋白物质为主,而填埋1,5,10年垃圾DOM以类腐殖质物质为主,并且随着填埋龄的延伸其紫外区和可见光区荧光峰强度的比值r_(A,C)及荧光指数f_450/500呈下降趋势;DOM的紫外吸收光谱也表明,随着填埋年限的延伸填埋垃圾DOM的分子量增大,腐殖化程度加强,单位水溶性有机物浓度DOM的254 nm紫外吸收值SUVA随着填埋龄呈上升趋势,但DOM在465及665 nm吸光度值的比E₄/E₆随填埋龄的变化规律不明显。因此,填埋垃圾DOM的r_(A,C),f_450/500及SUVA值可以有效地表征填埋场和填埋垃圾的稳定化进程。     

垃圾渗滤液水溶性有机物荧光谱特性研究

选取不同填埋年限的垃圾渗滤液样品,利用荧光检测技术,分析了渗滤液水溶性有机物(DOM)组成变化。DOM荧光同步扫描光谱表明,在填埋的0～5年,结构简单的化合物在较短波长(335,385 nm)的特征峰荧光强度急剧降低,而在5～10年的降低幅度较小。DOM三维荧光光谱显示,填埋0年,垃圾渗滤液DOM产生2个类蛋白荧光峰(Ex/Em = 270 nm/355.5 nm和Ex/Em=220 nm/350 nm);而填埋5年后,类蛋白荧光峰消失,形成2个分子结构复杂的类富里酸荧光峰(Ex/Em=330 nm/412.5 nm和Ex/Em=250 nm/416.5 nm),表明DOM分子中简单化合物减少,缩合度高的化合物增加。而后随着填埋时间的推移,DOM成分相对稳定,以富里酸类物质为主,但其数量及芳构化程度则呈增加的趋势。以上结果证实,随着填埋年限的增加,DOM分子呈复杂化趋势。     

A quartz crystal microbalance sensor for the determination of nitroaromatics in landfill gas

A new sensor based on oxidative combustion of nitroaromatics to NO₂ and its detection with a quartz crystal microbalance (QCM) coated with copper phthalocyanine (CuPc) was developed for determination of nitroaromatics in landfill gas. An alternative method based on gas chromatography–mass spectrometry (GC–MS) was also used in order to assess the performance of the proposed method. The results show that the analytical apparatus based on the QCM is less expensive than the GC–MS, and that the analytical error is 0.8% for both methods.     

RO处理早期垃圾渗滤液中DOM的荧光光谱分析

利用荧光检测技术对某垃圾填埋场渗滤液反渗透(RO)膜深度处理时的进水、出水、浓缩液、酸洗液以及酸洗后碱洗液中水溶性有机物(DOM)的组成变化进行了研究。同步荧光光谱显示,预处理后的渗滤液膜进水在波长280,340,370 nm出现三个较强的荧光峰,反渗透膜对此有效拦截,酸洗和碱洗的组合清洗方式有效去除了波长范围在300~420 nm的有机污染物。三维荧光光谱显示,进水含有2个类富里酸和3个类蛋白质荧光峰,RO膜出水仅含有2个类蛋白峰,浓缩液中出现其余3个高强度的荧光峰;酸洗和碱洗对膜上污染物质分子结构影响显著,存在着明显的荧光峰位移。结果表明,RO膜有效拦截了早期渗滤液中的类富里酸,而对膜的污染物除类富里酸外,还有类蛋白成分:主要为低激发类酪氨酸;为膜污染控制提供了理论支持。     

Multi-Element Analysis of Landfill Gas by ICP Emission and Mass Spectrometry

Methodology for the determination of trace elements in landfill gas by inductively coupled plasma emission and mass spectrometry is described. The approach is based on direct injection of landfill gas into the ICP using a simple gas sampling manifold. Chlorine and sulphur were quantified in landfill gas by ICP-OES while Sn, Mg, Cu and Zn were measured by ICP-MS. Due to the complex chemical composition of landfill gas, measurements in both emission and mass spectrometry were compromised by spectral interferences. The possibility for multi-element analysis of landfill gas samples based on the use of aqueous standard solutions was demonstrated.     

Development of a pre-concentrator-thermo-desorber/micro-gas chromatograph/mass spectrometer coupling for on-site analyses of emissions of volatile organic compounds from landfills

The development and use of a pre-concentrator-thermo-desorber/micro-gas chromatograph/mass spectrometer (μTD/μGC/MSD) coupling for the on-site analysis of VOCs in landfill gases are presented. The coupling has the advantage of analysing compounds with two detectors operated in series: the TCD (of the μGC) initially analyses the gas without destroying it, and then the MSD identifies the compounds. Due to the TCD response, the results were quantified with reference to toluene. The reliability of the analytical chain for quantitative analysis was validated by sampling two gaseous standards, including the EPA TO14 mixture, containing 39 compounds. With the OV1?μGC column, 24 compounds were identified and 16 correctly quantified. The repeatability of the measures estimated by their standard deviation was in the order of 1–2%. The detection limit was evaluated at 0.1?ppbv, for a 40?min pre-concentration on the Tenax of the μTD. The results of VOC analyses in the air of a landfill site obtained with the μTD/μGC/MSD coupling show its potential for on-site analyses: immediate results, high sensitivity, no storage for the samples, and measurements of pollution peaks.     

A bi-objective model for the location of landfills for municipal solid waste

This paper models the locations of landfills and transfer stations and simultaneously determines the sizes of the landfills that are to be established. The model is formulated as a bi-objective mixed integer optimization problem, in which one objective is the usual cost-minimization, while the other minimizes pollution. As a matter of fact, pollution is dealt with a two-pronged approach: on the one hand, the model includes constraints that enforce legislated limits on pollution, while one of the objective functions attempts to minimize pollution effects, even though solutions may formally satisfy the letter of the law. The model is formulated and solved for the data of a region in Chile. Computational results for a variety of parameter choices are provided. These results are expected to aid decision makers in the choice of excluding and choosing sites for solid waste facilities.