Sampling and analytical procedures for the determination of VOCs released into air from natural and anthropogenic sources: A comparison between SPME (Solid Phase Micro Extraction) and ST (Solid Trap) methods

In the present study, two sampling and analytical methods for VOC determination in fumarolic exhalations related to hydrothermal-magmatic reservoirs in volcanic and geothermal areas and biogas released from waste landfills were compared: (a) Solid Traps (STs), consisting of three phase (Carboxen B, Carboxen C and Carbosieve S111) absorbent stainless steel tubes and (b) Solid Phase Micro Extraction (SPME) fibers, composed of DiVinylBenzene (DVB), Carboxen and PolyDimethylSiloxane. These techniques were applied to pre-concentrate VOCs discharged from: (i) low-to-high temperature fumaroles collected at Vulcano Island, Phlegrean Fields (Italy), and Nisyros Island (Greece), (ii) recovery wells in a solid waste disposal site located near Florence (Italy). A glass condensing system cooled with water was used to collect the dry fraction of the fumarolic gases, in order to allow more efficient VOC absorption avoiding any interference by water vapor and acidic gases, such as SO₂, H₂S, HF and HCl, typically present at relatively high concentrations in these fluids. Up to 37 organic species, in the range of 40–400 m/z, were determined by coupling gas chromatography to mass spectrometry (GC–MS). This study shows that the VOC compositions of fumaroles and biogas determined via SPME and ST are largely consistent and can be applied to the analysis of VOCs in gases released from different natural and anthropogenic environments. The SPME method is rapid and simple and more appropriate for volcanic and geothermal emissions, where VOCs are present at relatively high concentrations and prolonged gas sampling may be hazardous for the operator. The ST method, allowing the collection of large quantities of sample, is to be preferred to analyze the VOC composition of fluids from diffuse emissions and air, where these compounds are present at relatively low concentrations.     

Carbon dioxide stripping from anaerobic digestate of food waste using two types of aerators

Anaerobic digestate of organic wastes often contains high concentrations of ammonia and carbon dioxide. Ammonia can be removed from digestate by air stripping at elevated pH. However, it is difficult to increase pH of the digestate because dissolved carbon dioxide transforms into bicarbonate and carbonate ions. Thus, carbon dioxide in digestate needs to be removed to reduce alkali consumption in ammonia stripping process. This study aimed to optimize and compare the performances of diffused and packed tower aerators for anaerobic digestate of food waste. The diffused aerator removed 82.1% of dissolved carbon dioxide and 13.7% of total inorganic carbon, and increased pH of digestate from pH 7.87 to pH 8.53, under the following optimized conditions; digestate temperature of 45 °C, air flow rate of three volumes of air added to a unit volume of liquid per minute, aspect ratio of 2, agitation speed of 500 rpm with a turbine impeller, and retention time of 10 min. Operating conditions of the packed tower aerator were also optimized, and it was found that the packed tower aerator removed 15% and 44% less dissolved carbon dioxide and total inorganic carbon, respectively, than the diffused aerator. It was also found that overall coefficients of carbon dioxide mass transfer from liquid to gas phase determined the final pH of digestate and removal efficiencies of carbon species.     

红土型铝土矿中三水铝石的分离方法研究

研究了非水溶剂体系作为分离红土型铝土矿中三水铝石的选择性溶剂的优越性及其具体应用条件。实验表明，１ｍｏｌ／ＬＫＯＨ－０．３％水杨酸－无水乙醇溶液于沸水浴上浸取分离，可使该矿中高含量的三水铝石完全溶解，其浸出率＞９９％；而共存的一水硬铝的溶解率＜０．６，高岭石的溶解反应受到了明显的抑制，其最大溶解率从３０．５５％降至５．８６％。方法用于实际样品分析，获得了比较满意的结果。     

TBP萃淋树脂微色谱柱分离富集钼的研究及应用

研究了ＴＢＰ萃淋树脂微色谱柱分离富集微量钼的柱性能,确定了分离钼的最佳条件。在减压条件下,运用零空床体积洗脱技术,以３ｍｏｌ／ＬＨＣｌ为上柱介质,０．５ｍｏｌ／ＬＨＣｌ洗脱,可使钼（ＶＩ）与钨（Ⅵ）、铁（Ⅲ）、锡（Ⅳ）等干扰离子快速分离,采用邻氯苯基荧光酮胶束增溶光度法,测定矿石中微量钼,结果满意。     

Accurate Determination of Cobalt in South African Primary and Secondary Geochemical Reference Materials by Cation Exchange Chromatography and Atomic Absorption Spectrometry

Cobalt in the six S.A. primary (NIMROCS) and fourteen secondary reference samples as well as in a phosphate rock has been determined accurately by means of atomic absorption spectrometry. A selective and quantitative ion exchange separation procedure, using a 20 g column of AG50W-X8 cation exchange resin and 0.4 M hydrochloric acid-86% acetone and 1 M hydrochloric acid-80% acetone as eluting agents, is employed for the separation of cobalt from all other elements. The accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of cobalt. Amounts of 1, 10 and 100 μg of cobalt can be determined with a coefficient of variation of 1%, 0.3% and 0.2%. respectively.     

Development of low-cost passive sampler from cow bone char for sampling of volatile organic compounds

A simple and low-cost passive sampler for collection of volatile organic compounds, specifically benzene, toluene, ethylbenzene and xylene (BTEX), from the ambient air has been developed by using cow bone char (CBC) as an adsorbent with desorption by solvent extraction prior to analysis by gas chromatography–mass spectrometry (GC–MS). The laboratory-made CBC was prepared by calcination process in a partially oxidative atmosphere. The developed passive sampler was tested for a suitable amount of CBC used, diffusion tube type and size, and sampling duration, in a closed chamber saturated with each of the BTEX vapors. With the optimum amount of 250 mg CBC packed in a glass bottle (82.6 mm height × 11.1 mm i.d.) and the exposure time of 168 h, detection limits (µg/m³) for BTEX determination using this developed sampler together with GC–MS were 0.28 (benzene), 0.79 (toluene), 0.58 (ethylbenzene), 0.28 (p-xylene) and 0.54 (o-xylene). The proposed method was applied to sampling BTEX from selected petrol stations, traffic congestion areas and a rural area in Chiang Mai Province, Thailand. The BTEX concentrations detected were well correlated with their sources as they were the highest at the petrol station sites, lower at the traffic congestion area sites and the lowest at the rural area site. The laboratory-made passive sampler containing CBC has thus opened up a possibility of having a simple and effective device for sampling of BTEX in the ambient air.     

Human Health Risk Assessment of a landfill based on volatile organic compounds emission,immission and soil gas concentration measurements

A Human Health Risk Assessment (HHRA) was required for a closed landfill located in Cerdanyola del Vallès (Barcelona, Spain). The HHRA had two objectives, to evaluate the present risk of the identified receptors in the area and to safely develop the future urban planning of the area, therefore 3 scenarios for the current situation and 4 for the future situation were developed.After reviewing the existing data and exploring the needs of information, the assessment in this study was focused on the measurement of volatile organic compounds (VOCs) fluxes from the subsoil (emission from the landfill at 5 points), concentrations of VOCs in the air (immission in 4 urban sites) and concentration of VOCs in soil–gas (measurements at 5 m below ground surface outside the landfill at 8 sites). Around 70 VOCs were analyzed by using multi-sorbent tubes and Thermal Desorption Gas Chromatography (TD–GC–MS). The VOCs that were detected and quantified include alkanes, aromatic hydrocarbons, alcohols, ketones, halocarbons, aldehydes, esters, terpenoids, ethers and some nitrogenated and sulfur compounds, furans and carboxylic acids. Specific mercury flux measurements were performed in a hot spot by using carulite tubes, that were also analyzed by using Thermal Decomposition, Amalgamation, and Atomic Absorption Spectrophotometry.Results showed average values of volatile emission fluxes ranging from non-detected to 331 μg m⁻² day⁻¹ (dichlorodifluoromethane). In the case of immission, the concentration of VOCs measured in the air of populated area surrounding the landfill ranged values from non-detected to 42.0 μg m⁻³ (acetic acid). The soil–gas measurements in piezometers around the landfill showed individual VOC values with a maximum 830 μg m⁻³ for dichlorodifluoromethane.With the obtained fluxes and concentrations in air and soil–gas, USEPA methodology and modeling was used to evaluate equivalent concentration in the scenarios considered. Toxicity values from IRIS database were used to finally obtain chemical risk indicators. Admissible risk indicators were obtained in all scenarios. The VOCs that contributed more to risk indexes in RH2 were trichloroethylene, trimethylbenzene, chloroform, 1,2-dichloroethane and carbon tetrachloride. The carcinogenic risk in RH7 was linked to the presence of benzene and chloroform. The comparison of the measurements of the present work with other landfills evidence that HHRA in ambient air would be needed in order to perform a correct landfill management.     

Accurate Determination of Zinc and Lead in Silicate Rocks by Means of Cation Exchange Chromatography and Atomic Absorption Spectrometry

Zinc and lead in the six S.A. NIMROC Standards and in DTS-1 and PCC-1 have been determined accurately by means of atomic absorption spectrometry. A selective ion exchange separation procedure, using AG5OW-X8 cation exchange resin and 0.5 M HCl - 60% acetone as eluent, has been employed to separate zinc and lead from the matrix elements. To increase the sensitivity of lead, a slotted stainless steel tube, which is positioned on top of the air-acetylene burner head, has been used during atomic absorption measurements. The accuracy and precision of the described method is demonstrated by the analysis of synthetic mixtures containing various amounts of zinc and lead as well as major rock-forming elements.     

Accurate Determination of Copper in South African Primary and Secondary Reference Samples by Cation Exchange Chromatography and Atomic Absorption Spectrometry

Copper in S.A. primary (NIMROCS) and in six secondary reference samples has accurately been determined by means of atomic absorption spectrometry. A selective ion exchange separation procedure, using a 20 g column of AG50W-X8 cation exchange resin and 0.2 M hydrochloric acid and 0.5 M hydrobromic acid, both containing 85% acetone, is employed for the separation of copper from all other elements, except vanadium. Vanadium which can partially accompany copper, however, is separated at the start of the sorption step with 0.01 M nitric acid-0.15% hydrogen peroxide. Accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of copper. Amounts of 10 and 100 μg of copper can be determined with a coefficient of variation of 0.3% and 0.2%, respectively.     

基于多相流数值模拟的某石油污染场地地下水中VOCs自然衰减过程识别及能力评估

监测自然衰减(monitoring natural attenuation,MNA)技术是目前普遍认可的去除地下水中挥发性有机污染物(volatile organic compounds,VOCs)的技术。但受其修复周期长、监测费用昂贵等因素的影响,实地开展MNA技术修复污染场地具有一定的局限性。基于此,本研究运用多相流数值模拟手段识别了某石油污染场地内典型VOCs污染物(苯、甲苯、萘)在地下水中的自然衰减过程并评估了其自然衰减能力。结果表明:采用TMVOC所建立的多相流数值模拟模型能较好地预测和识别VOCs在地下水中的衰减规律;在研究区中,苯、甲苯和萘由于理化性质差异,在地下水中的污染羽分布特征不同,其自然衰减过程受挥发、吸附和生物降解作用的影响程度也不同;挥发和生物降解作用对VOCs自然衰减的影响程度均为苯>甲苯>萘,而吸附作用对VOCs自然衰减的影响程度为萘>甲苯>苯;在污染源被阻断的前提下,苯、甲苯和萘分别在泄漏发生7.0、6.5和6.0年后通过自然衰减达到理想去除效果。本文研究成果可以为水文地质条件类似的VOCs污染场地MNA修复方案的制定和修复效果评估提供理论支撑。     

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (K _d values).     

TECHNICAL NOTE An experimental investigation of air flow patterns in saturated soils during air sparging

Air sparging is an emerging method used to remediate saturated soils and groundwater that have been contaminated with volatile organic compounds (VOCs). During air sparging, air is injected into the subsurface below the lowest known depth of contamination. Due to buoyancy, the injected air will rise through the zone of contamination. Through a variety of mechanisms, including volatilization and biodegradation, the air will serve to remove or help degrade the contaminants. The contaminant-laden air will continue to rise towards the ground surface, eventually reaching the vadose zone, where the vapours are collected and treated using a soil vapour extraction (SVE) system.Air sparging performance and ultimately contaminant removal efficiency is highly dependent on the pattern and type of subsurface air flow. This paper presents the results of a laboratory experimental study which investigated the injected air flow pattern development within an aquifer simulation apparatus. The test apparatus consisted of a tank measuring 61 cm long by 25.4 cm wide by 38.1 cm high. The apparatus was equipped with one air injection well and two vapour extracton wells. Three different soils were used to simulate different aquifer conditions, including a sand, a fine gravel and a medium gravel. Experiments were performed with different injected air pressures combined with different vacuum and groundwater flow conditions. Experiments were also conducted by injecting air into simulated shallow aquifers with different thicknesses. The air flow patterns observed were found to depend significantly on the soil type, groundwater flow conditions and system controls, including injected air pressure, flow rate and applied vacuum. © Rapid Science Ltd. 1998     

Determination of Platinum and Palladium in Geological Samples by Inductively Coupled Plasma-Atomic Emission Spectrometry after Preconcentration with Immobilised Nanometric Titanium Dioxide

A new method has been developed for the determination of platinum and palladium based on separation and preconcentration with a microcolumn packed with nanometric TiO₂ immobilised on silica gel (immobilised nanometric TiO₂) prior to their determination by inductively coupled plasma-atomic emission spectrometry. The optimum experimental parameters for the preconcentration of Pt and Pd, such as the pH of the sample solution, its flow rate and volume, the type and concentration of eluent and interfering ions, have been investigated. Platinum and Pd could be quantitatively retained by immobilised nanometric TiO₂ in the pH range 6–8, then eluted completely with 2.0 ml of 3% m/v thiourea in 1.0 mol l⁻¹ HNO₃. The detection limits of this method for Pt and Pd were 12 and 7. 6 ng l⁻¹ with an enrichment factor of 100, and the relative standard deviations were 4.7% and 3.3% at the 10 ng ml⁻¹ level. The method has been applied for the determination of Pt and Pd in geological samples with satisfactory results.     

重点行业企业用地地下水中60种挥发性有机物的测定分析方法研究

建立了吹扫捕集-气相色谱质谱法测定重点行业企业用地地下水中60种挥发性有机物的分析方法.采用屈臣氏双蒸水作为空白水,选择离子与全扫描模式交替方式进行定性定量,确定了保护剂的种类和用量,优化了吹扫捕集条件.方法检出限范围在0.3~1.2μg/L.该方法的线性范围为0~250μg/L,相关系数R²在0.9907~0.9999之间,3种不同浓度的加标平均回收率为87.2%~117%,相对标准偏差在1.7%~9.7%之间,优于《重点行业企业用地调查质量保证与质量控制技术规定(试行)》对地下水挥发性有机物的质控要求.本方法增加了VOCs的测试种类,线性范围宽,灵敏度高,适合于各类重点行业企业用地地下水中60种挥发性有机物的快速批量分析.     

Assessment of the impact of biogenic VOC emissions in a high ozone episode via integrated remote sensing and the CMAQ model

In many metropolitan regions, natural sources contribute a substantial fraction of volatile organic compound (VOC) emissions. These biogenic VOC emissions are precursors to tropospheric Ozone (O₃) formation. Because forests make up 59% of the land area in Taiwan Province, China, the biogenic VOC emissions from forests and farmland could play an important role in photochemical reactions. On the other hand, anthropogenic emissions might also be one of the major inputs for ground level O₃ concentrations. Hence, emission inventory data, grouped as point, area, mobile and biogenic VOC sources, are a composite of reported and estimated pollutant emission information and are used by many air quality models to simulate ground level O₃ concentrations. Before using relevant air quality models, the emission inventory data generally require huge amounts of processing for spatial, temporal, and species congruence with respect to the associated air quality modeling work. The fist part of this research applied satellite remote sensing and geographic information system (GIS) analyses to characterize land use/land cover (LULC) patterns, integrating various sources of anthropogenic emissions and biogenic emissions associated with a variety of plant species. To investigate the significance of biogenic VOC emissions on ozone formation, meteorological and air quality modeling were then employed to generate hourly ozone estimates for a case study of a high ozone episode in southern Taiwan, which is the leading industrial hub on the island. To enhance the modeling accuracy, a unique software module, SMOKE, was set up for emission processing to prepare emission inputs for the U.S. EPA’s Models-3/CMAQ. An emission inventory of Taiwan, TEDS 4.2, was used as the anthropogenic emission inventory. Biogenic emission modeling was accomplished by BEIS-2 in SMOKE, with improvement of local LULC data and revised emission factors. Research findings show that the majority of biogenic VOC emissions occur in the mountainous areas and farmlands. However, the modeling outputs show that downwind of the most heavily populated and industrialized areas, these biogenic VOC emissions have less impact on air quality than do anthropogenic emissions.     

不良溶剂对甲基丙烯酸丁酯ATRP反应的影响

以2-溴代异丁酸乙酯[2-（EiB）-Br]为引发剂,CuBr/2,2^1-bpy为催化体系,进行了甲基丙烯酸丁酯（BMA）在丙酮、丙酮/甲醇、丙酮/水中的原子转移自由基聚合,研究了溶剂、温度对聚合反应活性特征的影响.结果表明,水或甲醇的加入,使反应速率有所增加,水的影响最大;在其它反应条件相同时,水或甲醇对反应的影响在低温时更为明显.     

Hg~(2+)-碘化物-番红花红T缔合体系褪色光度法测定微量汞

在0.01 mol/L硫酸介质中,Hg2+与过量I-和番红花红T(ST)反应生成稳定的离子缔合物[ST]2[HgI4],使ST褪色,据此建立了褪色光度法测定微量汞的方法。最大褪色波长为519 nm,体系的褪色程度与Hg2+浓度在0~1.35μg/mL内呈线性关系,表观摩尔吸光系数为1.24×105L/(mol.cm),检出限为2.26μg/L。采用巯基棉富集分离,测定河水中的微量汞,方法相对标准偏差(RSD,n=5)为1.2%~1.7%,回收率为98.3%~102.6%。     

Comparison of volatile organic compounds in stormwater and groundwater in Seoul metropolitan city,South Korea

Volatile organic compounds (VOCs) detected in stormwater were compared with VOCs present in emission sources, air, groundwater, and influent to sewage treatment plants in Seoul to understand their fate and transport in the urban hydrological system. Stormwater is a carrier of non-point source pollutants and contains VOCs from land surfaces and air. Samples of stormwater and influent to sewage treatment plants were collected and analyzed for 61 VOCs, while the VOCs in emission sources, air and groundwater were investigated through literature reviews for comparison. The results showed that the most frequently detected VOCs in stormwater were similar to those in air. However, the atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX), and methyl tertiary-butyl ether (MTBE) were too low to explain their frequent detection and high concentrations in stormwater. As a result, land surfaces seem to be a primary source of these VOCs in stormwater. Comparison of the VOCs in stormwater and groundwater showed that toluene and MTBE were frequently detected in both media, but more often and at higher concentrations in stormwater. This finding indicates that stormwater recharge is a source of toluene and MTBE in groundwater. Regarding groundwater, land surfaces seem to be a primary source of toluene, while urban air is the primary source in the case of MTBE. Specifically, the MTBE values in air were sufficiently high to explain its levels in groundwater, which had continually increased and remained low afterward. Furthermore, the high ratios of TEX (toluene, ethylbenzene, and xylenes) to benzene and MTBE in stormwater indicated that TEX had additional sources other than vehicles, most likely hydrocarbon solvents. These solvents seem to be a primary source of TEX and other frequently detected VOCs in stormwater. However, trichloroethylene (TCE), tetrachloroethylene (PCE) and their dechlorination intermediates were far more frequently detected and at higher concentrations in groundwater than in stormwater. Additionally, their concentrations frequently exceeded the water-quality criteria. It seems that halogenated solvents had produced contamination plumes of these chlorinated VOCs in the Seoul aquifer. Based on VOCs detected in Seoul, stormwater was mixed with groundwater in combined sewers and flowed into sewage treatment plants. The results imply that organic solvents should be handled with extreme care to protect groundwater quality.     

Mechanical trapping of fine particles in a medium of mono‐sized randomly packed spheres

Mechanical trapping (or straining) of fine particles is a key mechanism in many filtration systems. For example, the performance of rapid sand filters depends in part on mechanical trapping of larger fine particles, while relying on adsorptive processes to trap very small fine particles and microbes. The ability to trap these particles is directly related to the construction of the packed bed used for filtration in this system. Thus, the ability to model the effect of the inner structure of the packed bed can lead to more efficient design for improved filtration. Because of its significant efficiency, gravitational sphere packing is employed in this work to simulate a bed of mono‐sized randomly packed spheres. The simulated bed provides a way to visualize the pore network and estimate the pore size distribution associated with the void space between particles. Furthermore, by subsequently introducing fine particles into the bed, we evaluate the mass‐rate of fine particles passing through and possibly saturating the packed bed. Results show that fine particles between 15% and 25% of the coarse particle size can be physically strained within the randomly packed bed. These results differ significantly from the results obtained assuming a periodically spaced bed. The technique therefore provides an efficient yet accurate alternative for understanding how fine particles pass through a coarse particulate medium. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of grain packing tightness on strain estimation from the Fry method

How tightly should a sample be packed for strain estimation by the Fry method? We address this issue using synthetic simulations of 900 images such that each image contains 200 randomly distributed grains, but differs from other images with respect to the packing tightness and the degree of sorting. Each image is coaxially distorted by various known strain ratios and the strain estimates from distorted images are obtained by the Fry method. The statistical errors in the strain estimates are found to grow larger with the decrease in the packing tightness irrespective of the level of distortion. We demonstrate that a progressive decrease in the packing tightness results in an increasingly clustered nature of grain center distribution and hence the larger errors. These results, obtained from the synthetic images, are corroborated by two natural examples of sandstone, one loosely packed and the other tightly packed. Based on the results of tests on synthetic and natural examples, we recommend that the Fry method should be used only on those samples that have \({>}30\%\) packing density.