GC × GC--A New Analytical Tool For Environmental Forensics

Comprehensive two-dimensional gas chromatography, GC 2 GC, is a new analytical tool with a tremendous capability to separate and identify organic compounds in complex environmental samples. GC 2 GC uses two different chromatography columns coupled serially by a modulator to produce a volatility by polarity separation and distribute compound peaks across a two-dimensional retention time plane. The two-dimensional separation produces an order of magnitude more resolved peaks than traditional GC methods. The grouping or ordering of the peaks in the GC 2 GC chromatogram facilitates the identification of unknown compounds and the comparison of complex environmental samples. When a mass spectrometer detector is used, each resolved GC 2 GC peak yields a single-component, interference-free mass spectrum that leads to accurate matching with mass spectral libraries. GC 2 GC examination of marine sediment extracts identified a wide variety of chemical contaminants including polychlorinated biphenyls, p -nonylphenol isomers, polycyclic aromatic hydrocarbons, benzotriazoles, and the alkane, cycloalkane, alkylbenzene, alkylnaphthalene, and biomarker fractions of petroleum. The two-dimensional GC 2 GC chromatogram image permits rapid screening of the sediment extracts for these and other unknown contaminants.     

A New Phosphorus Paradigm for the Baltic Proper

The external phosphorus (P) loading has been halved, but the P content in the water column and the area of anoxic bottoms in Baltic proper has increased during the last 30 years. This can be explained by a temporary internal source of dissolved inorganic phosphorus (DIP) that is turned on when the water above the bottom sediment becomes anoxic. A load-response model, explaining the evolution from 1980 to 2005, suggests that the average specific DIP flux from anoxic bottoms in the Baltic proper is about 2.3 g P m⁻² year⁻¹. This is commensurable with fluxes estimated in situ from anoxic bottoms in the open Baltic proper and from hydrographic data in the deep part of Bornholm Basin. Oxygenation of anoxic bottoms, natural or manmade, may quickly turn off the internal P source from anoxic bottoms. This new P-paradigm should have far-reaching implications for abatement of eutrophication in the Baltic proper.

Electronic supplementary material

The online version of this article (doi:10.1007/s13280-013-0441-3) contains supplementary material, which is available to authorized users.     

Biomass explosion testing: Accounting for the post-test residue and implications on the results

This work uses the ISO 1 m³ dust explosion equipment to study the explosion properties and combustion characteristics of pulverized biomass dust clouds. An unreported feature of this apparatus is that in rich concentrations only about half the dust injected is burned in the explosion, while the overpressures remain high. This work was undertaken to try to understand the mechanisms of these phenomena, through the accounting of the debris at the end of the explosion, some of which was found in the form of impacted “cake” against the vessel wall. One possible explanation is that the residue material was biomass dust blown ahead of the flame by the explosion induced wind, impacted on the walls where then the flame side underwent flame impingement pyrolysis and the metal (wall) side material was compacted but largely chemically unchanged. The results also show that the heat transfer insulation provided by the powder wall layer contributes to the higher observed pressures. The risk of explosion with significant overpressures remains at 100% in very rich environments (equivalence ratios of up to 6) although these environments are leaner than thought due to material sequestration within the “cake”. There was little indication that a rich combustion limit was approached, this was determined in standard testing equipment that has been modified and calibrated to handle larger quantities of powder than normal.     

Dehydration of ethanol with different salts in a packed distillation column

This work aimed the evaluation of a saline extractive distillation for the ethanol production. A thermodynamic model was used to predict the influence of the salts in the liquid–vapor equilibrium of the system water–ethanol and inside the packed column. The experiments were done in a distillation unit, with an internal diameter of 5.9 cm and a packing section with 37 cm of height, packed with raschig rings with 0.73 cm of characteristic inner made of glass. All the bottom and top samples were analyzed by refractive index. Two synthetic charges with the same composition of ethanol that are produced in the refinery (0.02 and 0.25 mol.L^-1) were distilled under atmospheric pressure. Sodium chloride, calcium chloride, potassium acetate, calcium nitrate and a mixture of sodium and potassium acetates were added to the synthetic charges and the results were compared to the experiments already done without the presence of the salts, revealing the ethanol enrichment in the top product of the distillation unit, for all the systems analyzed. Another charge from the refinery, known as load of wine without yeast, was evaluated and the results indicated the same behavior, enriching the ethanol with the application of the saline extractive distillation.     

Secondary ozonides of substituted cyclohexenes: a new class of pollutants characterized by collision-induced dissociation mass spectrometry using negative chemical ionization

Recent studies indicate that secondary ozonides of cyclic alkenes are formed in atmospheric reactions and may be relatively stable. The secondary ozonides (SOZs) of cyclohexene (1), 1-methylcyclohexene (2), 4-isopropyl-1-methylcyclohexene (3) and 4-isopropenyl-1-methylcyclohexene (limonene) (4) have been characterized by rapid gas chromatography electron ionization (EI), negative and positive chemical ionization (CI: ammonia, isobutane and methane) and collision-induced dissociation (CID) mass spectrometry. Both EI and positive CI spectra were found unsuitable for reproducible analysis. However, negative CI showed stable (M−H)⁻ ions with minor fragmentation. CID of the (M−H)⁻ ions resulted in simple and reproducible fragmentation patterns for all four SOZs with loss of m/z 18, 44 and 60, tentatively assigned as H₂O, CO₂ and C₂H₄O₂ or CO₃, respectively. Thus, negative CI-MS–MS in combination with rapid gas chromatography is the preferred method for identification of secondary ozonides of cyclohexenes.     

刚果红-巯基棉分离富集光度法测定垃圾渗滤液中镉

基于在pH值为4.0～5.2的BR缓冲介质中，镉与刚果红发生显色反应并生成蓝色离子缔合物的原理，建立了测定垃圾渗滤液中镉的巯基棉分离富集光度法。其最大正吸收波长和最大负吸收波长分别为604nm和492nm，线性范围分别为0.10mg／L～2.80mg／L和0.10mg／L～3．40mg／L，采用双波长叠加测定灵敏度更高。探讨了渗滤液的处理方法及共存离子对测定的影响，优化了试验条件，实际样品的测定结果与原子吸收法对比无显著差异，加标回收率为98，6％～104％。     

Mass balance and long-term fate of PCDD/Fs in a lagoon sediment and paddy soil, Niigata, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in a sediment core and in samples of surface sediment and paddy soil collected from the Toyano lagoon and Kameda basin in Niigata, Japan, were analyzed to elucidate the temporal trends of their concentrations in the lagoon sediment and the relationship between the sediment and the paddy soil. The mass balance of these pollutants was also estimated to determine their long-term fate in surface waters. An analysis by chemical mass balance identified the agrochemicals pentachlorophenol and 2,4,6-trichlorophenyl 4-nitrophenyl ether as the major sources of PCDD/Fs. On the basis of the findings regarding the mass balance in the Kameda basin over the last 40 years, we estimate that more than half the input of PCDD/Fs to the Kameda basin has disappeared. We suggest that the PCDD/Fs that flowed out from the paddy fields have been transferred to the lower basin.     

质谱技术在环境突发性事故中的应用

介绍了质谱技术在环境突发性事故应急监测中的应用,通过分析化工仓库爆炸应急监测和水厂污染事故调查监测两个实际案例,指出质谱技术能提供准确的定性定量结果,是环境突发性事故应急监测强有力的手段和工具.     

Seasonal air-water exchange fluxes of polychlorinated biphenyls in the Hudson River Estuary

Polychlorinated biphenyls (PCBs) were measured in the air and water over the Hudson River Estuary during six intensive field campaigns from December 1999 to April 2001. Over-water gas-phase SigmaPCB concentrations averaged 1100 pg/m3 and varied with temperature. Dissolved-phase SigmaPCB concentrations averaged 1100 pg/L and displayed no seasonal trend. Uncertainty analysis of the results suggests that PCBs with 5 or fewer chlorines exhibited net volatilization. The direction of net air/water exchange could not be determined for PCBs with 6 or more chlorines. Instantaneous net fluxes of SigmaPCBs ranged from +0.2 to +630 ng m(-2) d(-1). Annual fluxes of SigmaPCBs were predicted from modeled gas-phase concentrations, measured dissolved-phase concentrations, daily surface water temperatures and wind speeds. The net volatilization flux was +62 microg m(-2) yr(-1), corresponding to an annual loss of +28 kg/yr of SigmaPCBs from the Hudson River Estuary for the year of 2000.     

Emission modelling and validation of VOCs' source strengths in air-conditioned office premises

An emission model for indoor volatile organic compounds (VOCs) based on mass balance considerations has been presented and validated under steady state conditions. Comparison were made for the measured and predicted concentrations of 37 selected VOCs and TVOC through a case intervention study on the filters of the ventilation system in a new commercial air-conditioned office building. The intervention involved replacing media filters with electronic and carbon filtration. TVOC and 37 compounds selected for their health and comfort impact, representation of major chemical classes that occur in indoor air and their utility as markers of pollution sources were studied. The concentration levels predicted by the model were compared with actual measurements. Twenty-five target compounds and the TVOC were adequately described by the model where the measured concentrations were in agreement with the predicted concentrations. Modeling of the remaining 12 compounds was found to be affected by the emission rates that were occupant related.