On-Site Gas Chromatography/Mass Spectrometry (GC/MS) Analysis to Streamline Vapor Intrusion Investigations

Distinguishing between vapor intrusion and indoor sources of volatile organic compounds (VOCs) is a significant challenge in conventional vapor intrusion assessments. For this research project, the authors developed a step-by-step protocol to streamline building-specific investigations by using on-site gas chromatography/mass spectrometry (GC/MS) analysis and building pressure manipulation to determine the source of VOCs in indoor air during a 1-day field investigation. Protocol validation included implementation in industrial buildings and testing alongside conventional methods. The new protocol compares favorably to conventional approaches, yielding more definitive results in less time. This article presents three case studies which illustrate application of the protocol.     

Photolytic and photocatalytic degradation of quinclorac in ultrapure and paddy field water: identification of transformation products and pathways

Quinclorac (QNC) is an effective but rather persistent herbicide commonly used in rice production. This herbicide presents a mean persistence in the environment so its residues are considered of environmental relevance. However, few studies have been conducted to investigate its environmental behavior and degradation. In the present work, direct photolysis and TiO₂ photocatalysis of the target compound in ultrapure and paddy field water were investigated. After 10 h photolysis in ultrapure water, the concentration of QNC declined 26% and 54% at 250 and 700 W m⁻², respectively. However, the amount of quinclorac in paddy field water remained almost constant under the same irradiation conditions. QNC dissipated completely after 40 min of TiO₂ photocatalysis in ultrapure water, whereas 130 min were necessary to degrade 98% of the initial concentration in paddy field water.Possible QNC photolytic and photocatalytic degradation pathways are proposed after structure elucidation of the main transformation products, through liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry and exact mass measurements. Pyridine ring hydroxylation at C-9 followed by ring opening and/or oxidative dechlorination were the key steps of QNC degradation.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L⁻¹. For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L⁻¹ of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L⁻¹, lakes up to 600 ng L⁻¹ and groundwater and tap water up to 70 ng L⁻¹. The metabolite DKP was only detected in wastewater up to 200 ng L⁻¹ and at low detection frequencies.     

臭氧预氧化处理葡萄酒废水

葡萄酒废水的季节性波动常造成生化处理系统不稳定,使传统的生化处理工艺难以满足新的污水排放标准的要求。研究了臭氧预处理工艺对葡萄酒废水的处理效果及主要控制参数,结果表明,单独的臭氧预氧化对COD几乎无去除效果,但对色度的去除可达到90%;采用O3/H2O2组合工艺可使COD的去除率提高4倍。经臭氧预处理的出水再采用SBR进行好氧处理时,出水COD能降至80 mg/L以下,COD的降解速度及程度都高于未经臭氧处理的稀释原水。高效液相色谱(HPLC)分析显示,经臭氧处理后,除麦芽糖成分被完全去除外,其他各种成分的数量变化不大;GC/MS对废水中多酚类有机物的分析显示,臭氧预处理可将大量难降解的多酚类有机物分解,从而有助于后续生化处理的出水达到更高的污水排放标准。     

植物-微生物联合修复石油污染土壤的实验研究

筛选高效石油降解菌并考察菌株的石油降解能力,通过植物-微生物联合修复石油污染土壤室内实验,在修复过程中测定了土壤中细菌和固氮菌,碱解氮、速效磷和速效钾的含量变化,同时采用傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)考察了植物-微生物联合修复效果。结果表明,菌株3#、4#的生长适应性较强,其混合菌的降解效果最好,将其混合菌液与植物进行植物-微生物联合修复不同浓度的石油污染土壤,经过150 d的温室降解,最高降解率达到73.47%。ESI FT-ICR MS分析结果表明,与空白组相比,植物组的O1、O2和N1类等化合物相对丰度都发生了显著变化,石油污染物得到一定程度的生物降解。     

Mass flows of endocrine disruptors in the Glatt River during varying weather conditions

This study focused on the occurrence and behaviour in wastewater and surface waters of several phenolic endocrine disrupting compounds (EDCs) including parabens, alkylphenolic compounds, phenylphenol (PhP) and bisphenol A (BPA). Analytical procedures using solid-phase-extraction and LC-MS/MS techniques were applied to samples of influents and effluents of wastewater treatment plants (WWTPs) discharging into the Glatt River (Switzerland) as well as to river water samples. A mass flow analysis provided insight into the main sources and the fate of these contaminants during different weather conditions. Concentrations in influents were in the low μg/L range for most analytes. Removal of parabens in the WWTPs was mostly above 99%. Nonylphenol polyethoxylates (A₉PEO) removal amounted to 98%, but in some cases nonylphenoxy acetic acid (A₉PEC) or nonylphenols (NP) were formed. In effluents, concentrations were highest for the A₉PEC, A₉PEO and NP. Concentrations in river water were in the high ng/L range for alkylphenolic compounds and in the low ng/L range for BPA, PhP and the parabens. During the sampling period, in which several rain events occurred, both water flows and mass flows varied strongly. Mass flows in WWTP effluents and in the river increased with increasing water flows for most compounds indicating that higher water flows do not lead necessarily to a proportional dilution of the pollutants. Throughout the low water flow period, mass flows predicted from the known inputs were similar to the actual mass flows at the end of the river for most analytes. For none of the EDCs, significant in-stream removal could be observed. In the periods with high water flows, mass flows in the river were much higher than can be explained by the initially defined sources. Discharge of untreated wastewater influent into the river was assessed as an additional source. Adding this source improved the mass balance for some, but not all of the analytes.     

Structural characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2,5,6-tetrabromocyclooctane (TBCO)

1,2,5,6-Tetrabromocyclooctane (TBCO) is a commercial brominated flame retardant that is employed mainly as an additive in textiles, paints and plastics. Very little is known about its presence or behavior in the environment or its analysis. TBCO can exist as two diastereomers, the stereochemistries of which have not been previously reported. We have named the first eluting isomer, under HPLC conditions, as alpha-TBCO (α-TBCO) and the later eluting isomer as beta-TBCO (β-TBCO) when using an Acquity UPLC BEH C₁₈ column with methanol/acetonitrile/water as the mobile phase. The structural elucidation of these two isomers was accomplished by ¹H NMR spectroscopy, GC/MS, LC/MS and X-ray structure determinations. α-TBCO is (1R,2R,5S,6S)-1,2,5,6-tetrabromocyclooctane and β-TBCO is rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane. As with some other brominated cycloaliphatic compounds, TBCO is thermally labile and the isomers easily interconvert. A thermal equilibrium mixture of α- and β-TBCO consists of approximately 15% and 85% of these isomers, respectively. Separation of the two diastereomers, with minimal thermal interconversion between them, is achievable by careful selection of GC-capillary column length and injector temperature. LC/MS analyses of TBCO also presents an analytical challenge due to poor resolution of the isomers on chromatographic stationary phases, and weak intensity of molecular ions (or major fragment ions) when using LC-ESI/MS. Only bromide ions were seen in the mass spectra. APCI and APPI also failed to produce the molecular ion with sufficient intensity for identification.     

Comparison of atmosphere/aquatic environment concentration ratio of volatile chlorinated hydrocarbons between temperate regions and Antarctica

For the purpose of understanding the transport and deposition mechanisms and the air–water distribution of some volatile chlorinated hydrocarbons (VCHCs), their atmosphere/aquatic environment concentration ratio was evaluated. In addition, for the purpose of differentiating VCHC behaviour in a temperate climate from its behaviour in a polar climate, the atmosphere/aquatic environment concentration ratio evaluated in matrices from temperate zones was compared with the concentration ratio evaluated in Antarctic matrices.In order to perform air samplings also at rigid Antarctic temperatures, the sampling apparatus, consisting of a diaphragm pump and canisters, was suitably modified.Chloroform, 1,1,1-trichloroethane, tetrachloromethane, 1,1,2-trichloroethylene and tetrachloroethylene were measured in air, water and snow using specific techniques composed of a purpose-made cryofocusing-trap-injector (for air samples) and a modified purge-and-trap injector (for aqueous samples) coupled to a gas chromatograph with mass spectrometric detection operating in selected ion monitoring mode. The VCHCs were retrieved in all the investigated matrices, both Italian and Antarctic, with concentrations varying from tens to thousands of ng m⁻³ in air and from digits to hundreds of ng kg⁻¹ in water and snow.The atmosphere/aquatic environment concentration ratios were always found to be lower than 1. In particular, the Italian air/water concentration ratios were smaller than the Antarctic ones, by reason of the higher atmospheric photochemical activity in temperate zones. On the other hand, the Antarctic air/snow concentration ratios proved to be largely in favour of snow with respect to the Italian ratios, thus corroborating the hypothesis of a more efficient VCHC deposition mechanism and accumulation on Antarctic snow.     

气质联机法分析水中N,N-二甲基苯胺方法的研究

随着社会经济的发展,人们环境意识的提高,水中有机污染越来越受人们关注,目前国家尚没有N,N-二甲基苯胺的标准分析方法,但在工作中时常能遇到N,N-二甲基苯胺的监测分析.通过对采用气质联机法分析水中N,N-二甲基苯胺的方法的研究,希望能为国内环保监测工作提供一定的经验与技术.