Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Malic acid production from renewables: a review

Malic acid derived from fossil resources is currently applied in the food and beverage industries with a medium global production capacity. However, in the transition from a fossil-based to a bio-based economy, biotechnologically produced l -malic acid may become an important platform chemical with many new applications, especially in the field of biopolymers. In this review, currently used petrochemical production routes to dl -malic acid are outlined and insights into possible bio-based alternatives for microbial l -malic acid production are provided. Besides ecological reasons, the possibility to produce enantiopure l -malic acid by microbial fermentation is the biggest advantage over chemical synthesis. State-of-the-art and open challenges concerning production host engineering, substrate choice and downstream processing are addressed. With regard to production hosts, a literature overview is given covering the leading natural production strains of Aspergillus, Ustilago and Aureobasidium, as well as Escherichia coli as the most important engineered recombinant host. The utilization of renewable substrates as an alternative to glucose is emphasized in particular as a key aspect for a competitive bio-based production. Out of the alternative substrates discussed in this review, the industrial side-streams crude glycerol and molasses seem to be most promising for large-scale l -malic acid production. © 2019 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Ecophysiology and niche differentiation of Nitrospira-like bacteria, the key nitrite oxidizers in wastewater treatment plants.

Nitrite-oxidizing bacteria of the genus Nitrospira are key nitrifiers in wastewater treatment plants. Pure cultures of these organisms are unavailable, but cultivation-independent molecular methods make it possible to detect Nitrospira-like bacteria in environmental samples and to investigate their ecophysiology. Comprehensive screening of natural and engineered habitats and of public databases for 16S rRNA sequences of Nitrospira-like bacteria revealed a surprisingly high biodiversity in the genus Nitrospira, which comprises at least four phylogenetic sublineages. All Nitrospira-like bacteria detected in wastewater treatment plants belonged to the sublineages I and II. Subsequently, the population dynamics of different Nitrospira-like bacteria were monitored, by quantitative fluorescence in situ hybridization with rRNA-targeted probes, confocal laser scanning microscopy and digital image analysis, during incubation of nitrifying activated sludge in media containing different nitrite concentrations. These experiments showed that Nitrospira-like bacteria, which were affiliated with the phylogenetic sublineages I or II of the genus Nitrospira, responded differently to nitrite concentration shifts. Previously unknown properties of Nitrospira-like bacteria were discovered in the course of an environmental genomics project. Implications of the obtained results for fundamental understanding of the microbial ecology of nitrite oxidizers as well as for future improvement of nutrient removal in wastewater treatment plants are discussed.     

Bench- and pilot-scale sludge electrodewatering in a diaphragm filter press.

Electrodewatering is a technique in which pressure dewatering is combined with electrokinetic effects to realize an improved solid/liquid separation and hence increased filter cake dry matter contents. In order to be energy efficient, it is shown that sludge should be dewatered by pressure dewatering to a high extent prior to electric field application, and a sufficient contact time for the electric field must be guaranteed. In order to realize these goals, a bench- and pilot-scale diaphragm filter press suited for electrodewatering were constructed for treatment of sewage and other types of sludges. It was shown that electrodewatering of sludge is a feasible technique, especially for biological sludge types. Other types of sludge are less suited for electrodewatering because of the restricted improvements that can be realized in cake dry matter content and the high electric energy consumption. Furthermore, it was shown in pilot-scale tests that the use of a diaphragm filter press with electrodewatering facilities was very well suited to deliver dry filter cakes of sewage sludge at a moderate energy consumption. Depending on local market prices for investment, operating and sludge disposal costs, this technology may therefore lead to important savings in the sludge management process.     

HIGHER PLANT BIOMARKERS IN PALEOGENE CRUDE OILS FROM THE YUFUTSU OIL-AND GASFIELD AND OFFSHORE WILDCATS, JAPAN

Geochemical investigation of Paleogene oils from the onshore Yufutsu oil- and gasfield, southern Hokkaido, and from two nearby offshore wells, revealed the presence of numerous biomarkers of higher plant origin. Biomarkers in the oils belong to different groups of both angiosperm and gymnosperm origin; they include bicyclic sesquiterpanes, diterpanes, and triterpanes and their aromatized counterparts, which suggests a terrestrial origin for the oils. The oils were characterized as having a high wax content, a low content of organosulphur compounds, a high pristane/phytane ratio, and a low C₂₇/(C₂₇+C₂₉) sterane ratio.
Although the oils from on- and offshore Southern Hokkaido are similar in their geochemical composition, notable differences were observed in the biomarker signature of both saturate and aromatic fractions. The oils from the offshore wells appeared to have a greater abundance of higher plant biomarkers compared to those from the Yufutsu field, suggesting an enrichment in higher plant components. Differences in biomarker fingerprint could not be linked to the maturity effect, since the oils appeared to be of similar maturity levels, corresponding to the late stage of the oil window (0.9–1.2%, Rc). The differences in the biomarker signatures between the oils from the Yufutsu field and the offshore wells are likely to be due to facies variations in source organic matter, resulting from differences in the quantity and quality of land plant input.     

PETROLEUM POTENTIAL, THERMAL MATURITY AND THE OIL WINDOW OF OIL SHALES AND COALS IN CENOZOIC RIFT BASINS, CENTRAL AND NORTHERN THAILAND

Oil shales and coals occur in Cenozoic rift basins in central and northern Thailand. Thermally immature outcrops of these rocks may constitute analogues for source rocks which have generated oil in several of these rift basins. A total of 56 oil shale and coal samples were collected from eight different basins and analysed in detail in this study. The samples were analysed for their content of total organic carbon (TOC) and elemental composition. Source rock quality was determined by Rock‐Eval pyrolysis. Reflected light microscopy was used to analyse the organic matter (maceral) composition of the rocks, and the thermal maturity was determined by vitrinite reflectance (VR) measurements. In addition to the 56 samples, VR measurements were carried out in three wells from two oil‐producing basins and VR gradients were constructed. Rock‐Eval screening data from one of the wells is also presented. The oil shales were deposited in freshwater (to brackish) lakes with a high preservation potential (TOC contents up to 44.18 wt%). They contain abundant lamalginite and principally algal‐derived fluorescing amorphous organic matter followed by liptodetrinite and telalginite (Botryococcus‐type). Huminite may be present in subordinate amounts. The coals are completely dominated by huminite and were formed in freshwater mires. VR values from 0.38 to 0.47%R_o show that the exposed coals are thermally immature. VR values from the associated oil shales are suppressed by 0.11 to 0.28%R_o. The oil shales have H/C ratios >1.43, and Hydrogen Index (HI) values are generally >400 mg HC/g TOC and may reach 704 mg HC/ gTOC. In general, the coals have H/C ratios between about 0.80 and 0.90, and the HI values vary considerably from approximately 50 to 300 mg HC/gTOC. The HI_max of the coals, which represent the true source rock potential, range from ～160 to 310 mg HC/g TOC indicating a potential for oil/gas and oil generation. The steep VR curves from the oil‐producing basins reflect high geothermal gradients of ～62°C/km and ～92°C/km. The depth to the top oil window for the oil shales at a VR of ～0.70%R_o is determined to be between ～1100 m and 1800 m depending on the geothermal gradient. The kerogen composition of the oil shales and the high geothermal gradients result in narrow oil windows, possibly spanning only ～300 to 400 m in the warmest basins. The effective oil window of the coals is estimated to start from ～0.82 to 0.98%R_o and burial depths of ～1300 to 1400 m (～92°C/km) and ～2100 to 2300 m (～62°C/km) are necessary for efficient oil expulsion to occur.     

THE ORIGIN OF DOLOMITE IN THE ASMARI FORMATION (OLIGOCENE-LOWER MIOCENE), DEZFUL EMBAYMENT, SW IRAN

Dolomitisation is an important factor controlling reservoir quality in the Asmari Formation in many producing fields in SW Iran. Dolostones have higher average porosities than limestones. Petrographic and geochemical studies have been used to determine the causes of Asmari dolomitisation at the Bibi Hakimeh and Marun fields and at the Khaviz anticline. The formation is generally characterized by a large‐scale trend of upward‐decreasing accommodation. Basal strata were deposited under relatively open‐marine, high‐energy conditions, whereas the Middle to Upper Asmari succession was deposited in relatively protected settings with more frequent evidence of exposure and evaporitic conditions. There is a general upward increase in the abundance of both anhydrite (occurring as nodules and cement) and dolomite. Two main types of dolomite fabric are recognised, reflecting the textures of the precursor limestones: (1) finely crystalline pervasive dolomite (commonly <20μ) replacing mud‐rich facies; and (2) combinations of finely crystalline replacive dolomite and surrounding areas of coarser dolomite cement (crystals up to 100μ) in grain‐supported facies. Fluid inclusion data indicate that finely crystalline dolomites formed at low temperatures (ca. <50°C), while the coarser dolomite formed at higher temperatures (50–;140°C). Whole rock‐carbonate oxygen and carbon isotope analyses of pure dolostone samples show no apparent correlation with either depositional or diagenetic textures: δ¹⁸O is generally 0 to 2.7‰ PDB, and δ¹³C is ?1 to 4‰ PDB. The importance of evaporated seawater to Asmari dolomitisation is indicated by the ubiquitous occurrence of felty‐textured anhydrite nodules in dolostone beds and the presence of high‐salinity fluid inclusions in dolomite. The derivation of dolomitising fluids from contemporaneous seawater is supported by the general correspondence between age estimates derived from the strontium isotope composition of anhydrites and dolomites and those derived from stratigraphic considerations. This suggested synsedimentary dolomitisation. Dolomitisation of the upper half of the Asmari Formation may have occurred as a result of two syn‐sedimentary mechanisms: (1) by the reflux of evaporative brines concentrated in shallow lagoons or sabkhas, through immediately underlying strata (mainly during highstands); and (2) by the flushing of platform‐top carbonates by basinal evaporated waters during lowstand/early transgression. Continued dolomitisation during deeper burial is supported by the presence of high‐temperature fluid inclusions and iron‐rich crystal rims. Dolomite within the lower part of the Asmari Formation probably mostly formed during burial as a result of compaction of, and fluid exclusion from, the underlying Pabdeh marls and shales.     

Control of reactive distillation production of high-purity isopropanol

The process characteristics and control strategy of a high-purity IPA reactive distillation column were investigated. A robust nominal operation was found by maintaining an excess of propylene feed to the column and recycling the unreacted propylene to the feed instead of the top stage. Stage temperature and propylene composition with one-to-one relationship with reboiler duty and propylene feed are selected as controlled variables for maintaining bottom purity and feed ratio in the presence of possible measurement bias respectively. High nonlinearity between selected input–output pair was reduced by using variable transformation. Dynamic simulations demonstrated that such a control scheme with nonlinear transformed variable was capable of providing much superior control performance than the one using natural variable.     

Time-resolved in-situ analysis of phase evolution for the directional solidification of carbon steel weld metal

Kinetic information about the phase transformation, during solidification process and solid-state transformation is essential to the material processing, such as welding. In our research group, in-situ phase identification system consisting of undulator beam and imaging plate have recently been used. The welding torch is driven by stepping-motor in the system. Those make possible that phase transformation can be identified in real-time under the condition of directional solidification and the spatial resolution of 100 × 500 μm. The time-resolution is 0.3125 seconds. In the present work, combination of analyzing method: the in-situ phase identification system, morphological observation by high-temperature laser scanning confocal microscopy and observation of microstructure at room temperature by OM, SEM and micro diffraction-system, is suggested to analyze the phase transformation during welding process. Phase transformation process of hypereutectoid carbon steel, during welding was analyzed as an example of combination observation.     

Theoretical and practical implications of creep curve shape analyses for 7010 and 7075

Over tensile stress ranges giving creep lives up to 2000 hours at 373 to 463 K, the creep and creep fracture properties of 7010 are compared with results recorded for 7075 and other precipitation-hardened aluminum alloys. Using the ϕ methodology to quantify the systematic variations in creep curve shape with changing test conditions, the behavior patterns displayed by the different alloys are shown to depend on the extent to which precipitate coarsening causes a progressive loss of creep strength with increasing test duration and temperature. The ϕ relationships also introduce new approaches for rationalization and interpretation of creep data sets, based on the activation energy for lattice diffusion in the alloy matrices and the yield stress or UTS at the creep temperatures.