Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Separation of Organic Materials and Metallic Elements from Marine Waters by the Operation of Gas-Bubble Extraction

A laboratory experimental investigation was conducted to define the action of rising bubbles with respect to heavy-metal enrichment at the sea surface. Analytical data (HMDE-differential pulse anodic stripping voltammetry technique) show possible enrichments of organic-bound Zn, Cu, Cd and Pb at the top of a laboratory bubble-extraction column filled with water samples collected in the Southern Tyrrhenian Sea. In consideration of analogy between natural and laboratory bubble-extraction processes, laboratory results, i.e., enriched-over-original concentration ratios, make it possible to assess the intrinsic heavy-metal flotation capability in marine waters.     

Application of decision tools to ethical analysis in biodiversity conservation

Achieving ethically responsible decisions is crucial for the success of biodiversity conservation projects. We adapted the ethical matrix, decision tree, and Bateson's cube to assist in the ethical analysis of complex conservation scenarios by structuring these tools so that they can implement the different value dimensions (environmental, social, and animal welfare) involved in conservation ethics. We then applied them to a case study relative to the decision-making process regarding whether or not to continue collecting biomaterial on the oldest of the two remaining northern white rhinoceroses (Ceratotherium simum cottoni), a functionally extinct subspecies of the white rhinoceros. We used the ethical matrix to gather ethical pros and cons and as a starting point for a participatory approach to ethical decision-making. We used decision trees to compare the different options at stake on the basis of a set of ethical desiderata. We used Bateson's cube to establish a threshold of ethical acceptability and model the results of a simple survey. The application of these tools proved to be pivotal in structuring the decision-making process and in helping reach a shared, reasoned, and transparent decision on the best option from an ethical point of view among those available.     

Effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in Japan

Journal of Material Cycles and Waste Management - This paper estimates the effects of a composition change of ordinary Portland cement on waste utilization and CO2 emissions in the Japanese cement...     

In vitro evaluation of atmospheric particulate matter and sedimentation particles using yeast bioassay system.

Little information on the evaluation of airborne particulate matter (APM) and sedimentation particles from subway stations is available. The thermal metamorphism of train wheels generating toxic particles in subway stations is a possibility. In this study, the toxicity and physiological effects of particles from subway stations were evaluated using a yeast bioassay system. Estrogenic and antiestrogenic activities of APM in APM extracts from subway stations were determined. No estrogenic activity was found in the APM fractions and their S9-activated APM samples. Sedimentation dust samples also showed no estrogen activity. In contrast, extracts from sedimentation dust samples showed antiestrogen activity. Marked yeast toxicity was observed in the samples extracted from sedimentation dust. Potent yeast toxicity was also found in the S9-activated extracts from sedimentation dust. The results suggest that sedimentation dust from a semiclosed area of a subway system has antiestrogen activity, although both the origin and generation system of this activity are uncertain. These pollutants in sedimentation dust may change to a more toxic form in vivo by S9 activation.     

Recycling process for yttria-stabilized tetragonal zirconia ceramics using a hydrothermal treatment

The recycling process for 3 mol% yttria-stabilized tetragonal zirconia polycrystals (3Y-TZP) sintered at 1450°–1550°C was examined by applying low-temperature degradation of zirconia ceramics under hydrothermal conditions. Hydrothermal treatment at a temperature from 200° to 240°C can lead to the spontaneous disintegration of 3Y-TZP sintered bodies into powdery particles. The hydrothermally obtained zirconia powder was found to consist of primary particles and aggregated particles. Detailed X-ray diffraction measurement revealed the formation of a cubic zirconia phase in the 3Y-TZP sintered bodies, which seemed to inhibit the disintegration of aggregated particles toward the primary particle level. The reclaimed 3Y-TZP powder was sintered again through a conventional powder processing route. The mechanical properties and microstructure of recycled 3Y-TZP sintered specimens were examined by comparison with those of the original 3Y-TZP sintered bodies. Dense recycled 3Y-TZP sintered at a higher temperature exhibited higher fracture toughness to some degree than the original 3Y-TZP.     

Chirality determines pheromone activity for flour beetles

Olfactory perception and orientation behaviour of female and male flour beetles (Tribolium castaneum, T. confusum) to single stereoisomers of their aggregation pheromone revealed maximal receptor potentials and optimal attraction in response to 4R,8R-(?)-dimethyldecanal, whereas its optical antipode 4S,8S-(+)-dimethyldecanal was found to be inactive in this respect. Female flour beetles of both species were ≈ 10³ times less attracted to 4R,8S-(+)- and 4S,8R-(?)-dimethyldecanal than to 4R,8R-(?)-dimethyldecanal, while male flour beetles failed to respond to the R,S-(+)- and S,R-(?)-stereoisomers. Pheromone extracts of prothoracic femora from unmated male flour beetles elicited higher receptor potentials in the antennae of females than in those of males. The results suggest that the aggregation pheromone emitted by maleT. castaneum as well as maleT. confusum has the stereochemical structure of 4R,8R-(?)-dimethyl-decanal, which acts as sex attractant for the females and as aggregant for the males of both species.     

Adsorption removal of pollutants by active cokes produced from sludge in the energy recycle process of wastes

This study proposes a recycling system of sludge into active cokes and the fundamental examinations for the application were carried out. In the system, active cokes were produced by carbonizing pellets of sludge in a steam stream. Pyrolysis gas yielded by carbonization can be available to a fuel for a steam generation boiler. The exhaust heat from the boiler is used sequentially for drying of sludge. The active cokes are applied to the adsorbent for dioxin removal in exhaust gas from incinerators of wastes, or for purification of gas obtained in a gasification process of wastes, particularly removal of H2S. The used adsorbent is not recycled, but incinerated in the furnace without a desorption process to decompose adsorbed dioxin or to oxidize H2S for a sequential desulfurization process of SO2. Dry pellets of sludge were carbonized in a quartz tube reactor under various atmospheres. The micro pore structure and the adsorption performance of the cokes produced without activation process were examined. The micro pore structure was influenced by the temperature, the sort of flow gas (N2, CO2 and steam) and carbonization time, and the active cokes produced under the condition of the temperature 823 K for 60 min in the steam atmosphere had a largest specific surface area in the diameter less than 5 nm. The amount of benzene adsorption as an alternative substance of dioxin into the active cokes had a similar quality to a commercial active char produced from coal if it was evaluated by adsorption per a unit specific surface area. This fundamental knowledge must be reflected to an optimum design for development of a simple continuous process to produce the active cokes by a fluidized bed type of the carbonization furnace.