A method of assessing air toxics concentrations in urban areas using mobile platform measurements.

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.

In situ chemical modification of peptide microarrays: application to the study of the antibody responses to methylated antigens.

Peptide microarrays are useful tools for characterizing the humoral response against methylated antigens. They are usually prepared by printing unmodified and methylated peptides on substrates such as functionalized microscope glass slides. The preferential capture of antibodies by methylated peptides suggests the specific recognition of methylated epitopes. However, unmodified peptide epitopes can be masked due to their interaction with the substrate. The accessibility of unmodified peptides and thus the specificity of the recognition of methylated peptide epitopes can be probed using the in situ methylation procedure described here. Alternately, the in situ methylation of peptide microarrays allows probing the presence of antibodies directed toward methylated epitopes starting from easy-to-make and cost-effective unmodified peptide libraries. In situ methylation was performed using formaldehyde in the presence of sodium cyanoborohydride and nickel chloride. This chemical procedure converts lysine residues into mono- or dimethyl lysines.

Effects Of Preservation On Wet Weight Dry-Weight Nitrogen And Carbon Contents Of Calanus-Helgolandicus (Crustacea Copepoda)

The lengths, wet and dry weights, nitrogen and carbon contents of fresh, frozen and formaldehyde-fixed specimens of Calanus helgolandicus (Claus) were determined. Samples were collected during May 1980 in the Celtic Sea. Individual Copepodite Stages 3, 4, 5, and Adult Male and Female Stage 6 were measured and analysed, and 36 linear regression equations derived for these variables together with mean values, standard deviations and 95% confidence limits. The range of nitrogen values in the fresh material, expressed as a percentage of dry weight, ranged from 8.08%±0.80 (Copepodite Stage 3) to 10.89%±0.27 (adult female); carbon values changed from 41.6%±3.05 (mean ±95% confidence limits) for Copepodite Stage 3 to 50.97%±2.63 in Copepodite Stage 5. The adult females had a high nitrogen and relatively low carbon content, while the converse was true for Stage 5 copepodites. There was a loss of dry weight from the frozen samples (57%) and the fixed samples (38%) compared with the mean of the fresh dry weight of all stages. The material lost from the copepods was rich in nitrogen, thus, artificially high percentage carbon values were determined from the frozen and fixed samples (52.0 to 60.3% and 44.7 to 58.5%, respectively).

XoxF encoding an alternative methanol dehydrogenase is widespread in coastal marine environments

The xoxF gene, encoding a pyrroloquinoline quinone-dependent methanol dehydrogenase, is found in all known proteobacterial methylotrophs. In several newly discovered methylotrophs, XoxF is the active methanol dehydrogenase, catalysing the oxidation of methanol to formaldehyde. Apart from that, its potential role in methylotrophy and carbon cycling is unknown. So far, the diversity of xoxF in the environment has received little attention. We designed PCR primer sets targeting clades of the xoxF gene, and used 454 pyrosequencing of PCR amplicons obtained from DNA of four coastal marine environments for a unique assessment of the diversity of xoxF in these habitats. Phylogenetic analysis of the data obtained revealed a high diversity of xoxF genes from two of the investigated clades, and substantial differences in sequence composition between environments. Sequences were classified as being related to a wide range of both methylotrophs and non-methylotrophs from Alpha-, Beta- and Gammaproteobacteria. The most prominent sequences detected were related to the family Rhodobacteraceae, the genus Methylotenera and the OM43 clade of Methylophilales, and are thus related to organisms that employ XoxF for methanol oxidation. Furthermore, our analyses revealed a high degree of so far undescribed sequences, suggesting a high number of unknown species in these habitats.

Enhanced Deuterium Fractionation in Dense Interstellar Cores Resulting from Multiply Deuterated H3+

In this Letter, we present the first results from updated models of interstellar deuterium chemistry that now include all possible deuterated isotopomers of H3+. We find that in regions of high density and heavy depletion, such as prestellar cores, the inclusion of HD2+ and D3+ enhances the fractionation of ionic and neutral species significantly. Our models are the first to predict the very high atomic D/H ratios (>=0.3) necessary for grain-surface chemistry models to reproduce the high formaldehyde and methanol fractionation seen in star-forming regions.

A survey of [ D2CO] /[ H2CO] and [ N2D^+] /[ N2H^+] ratios towards protostellar cores

Aims.We use observations and models of molecular D/H ratios to probe the physical conditions and chemical history of the gas and to differentiate between gas-phase and grain-surface chemical processing in star forming regions. Methods: As a follow up to previous observations of HDCO/H2CO and DCN/HCN ratios in a selection of low-mass protostellar cores, we have measured D2CO/H2CO and N2D^+/N2H+ ratios in these same sources. For comparison, we have also measured N2D^+/N2H+ ratios towards several starless cores and have searched for N2D+ and deuterated formaldehyde towards hot molecular cores (HMCs) associated with high mass star formation. We compare our results with predictions from detailed chemical models, and to other observations made in these sources. Results: Towards the starless cores and low-mass protostellar sources we have found very high N2D+ fractionation, which suggests that the bulk of the gas in these regions is cold and heavily depleted. The non-detections of N2D+ in the HMCs indicate higher temperatures. We did detect HDCO towards two of the HMCs, with abundances 1-3% of H2CO. These are the first detections of deuterated formaldehyde in high mass sources since Turner (1990) measured HDCO/H2CO and D2CO/H2CO towards the Orion Compact Ridge. Figures 1-5 are only available in electronic form at http://www.aanda.org

Dispersal mode and assessments of recovery on the shores of Gruinard, the 'anthrax island'

Formaldehyde run-off was an unintended impact of the anthrax decontamination procedure on the island of Gruinard. The death of intertidal organisms was observed where formaldehyde reached the shore during 1986. The extent to which shores on Gruinard have recovered was assessed with survey work in 2000. Recovery estimates were based on the hypothesis that the process of recolonization is partly dependent on species' dispersal capability. Underdevelopment of the assemblage of species lacking planktonic dispersal stages (direct developers) is therefore evidence that the process of recolonization is ongoing, rather than complete. A novel multivariate test showed that, when comparing quadrats from Gruinard and nearby mainland shores, assemblages of direct developing molluscs were significantly more distinct than assemblages of molluscs with planktonic dispersal stages. The average densities of species with direct development were generally lower on Gruinard than on mainland shores. While some species with direct development have similar densities on Gruinard and on the surrounding shores, the recovery of the overall assemblage was still incomplete after 14 years. In contrast, the harvested species, Littorina littorea, appeared to benefit from the absence of humans visiting Gruinard's shores. Populations of L. littorea on Gruinard contained significantly higher proportions of large individuals. Depending on the dispersal capabilities of different species, Gruinard is either still in recovery or acts as a reserve.

First-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis

Extensive density function theory calculations are performed to study the mechanism of the formation of aldehyde and alcohol on Co surfaces in Fischer-Tropsch synthesis, a challenging issue in heterogeneous catalysis. Three possible pathways for the production of formaldehyde and methanol on flat and stepped Co(0001) surfaces are investigated: (i) CO + 4H -> CHO + 3H -> CH2O + 2H -> CH3O + H -> CH3OH; (ii) CO + 4H -> COH + 3H -> CHOH + 2H -> CH2OH + H -> CH3OH; and (iii) the coupling reactions of CH2 + O -> CH2O and CH3 + OH -> CH3OH. It is found that these pathways are generally favored at step sites, and the preferred mechanism is pathway (i) via CHO. Furthermore, the three traditional chain growth mechanisms in Fischer-Tropsch synthesis are semi quantitatively compared and discussed. Our results suggest that the two mechanisms involving oxygenate intermediates (the CO-insertion and hydroxycarbene mechanisms) are less important than the carbene mechanism in the production of long chain hydrocarbons. However, the CO-insertion mechanism may be responsible for the production of long-chain oxygenates.

Activation of waste MDF sawdust charcoal and its reactive dye adsorption characteristics

This paper reports an experimental investigation of converting waste medium density fibreboard (MDF) sawdust into chars and activated carbon using chemical activation and thermal carbonisation processes. The MDF sawdust generated during the production of architectural mouldings was characterised and found to have unique properties in terms of fine particle size and high particle density. It also has a high content of urea formaldehyde resin used as a binder in the manufacturing of MDF board. Direct thermal carbonisation and chemical activation of the sawdust by metal impregnation and acid (phosphoric acid) treatment prior to pyrolysis treatment were carried out. The surface morphology of the raw dust, its chars and activated carbon were examined using scanning electron microscopy (SEM). Adsorptive properties and total pore volume of the materials were also analysed using the BET nitrogen adsorption method. Liquid adsorption of a reactive dye (Levafix Brilliant red E-4BA) by the derived sawdust carbon was investigated in batch isothermal adsorption process and the results compared to adsorption on to a commercial activated carbon (Filtrasorb F400). The MDF sawdust carbon exhibited in general a very low adsorption capacity towards the reactive dye, and physical characterisation of the carbon revealed that the conventional chemical activation and thermal carbonisation process were ineffective in developing a microporous structure in the dust particles. The small size of the powdery dust, the high particle density, and the presence of the urea formaldehyde resin all contributed to the difficulty of developing a proper porous structure during the thermal and chemical activation process. Finally, activation of the dust material in a consolidated form (cylindrical pellet) only achieved very limited improvement in the dye adsorption capacity. This original study, reporting some unexpected outcomes, may serve as a stepping-stone for future investigations of recycle and reuse of the waste MDF sawdust which is becoming an increasing environmental and cost liability. (C) 2004 Elsevier Ltd. All rights reserved.

High capacity carbon based electrodes for lithium/oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol (R) and formaldehyde (F)catalyzed by sodium carbonate (C) followed by carbonization of the resultant aerogels at 800? in an inert atmosphere. The porous texture of the carbons has been adjusted by the change of the molar ratio of resorcinol to catalyst (R/C) in the gel precursors in the range of 100 to 500. The porous structure of the aerogels and carbon aerogels are characterized by N2 adsorption-desorption measurements at 77 K. It is found that total pore volume and average pore diameter of the carbons increase with increase in the R/C ratio of the gel precursors.The prepared carbon aerogels are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested by using them as cathodes in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that with an increase of R/C ratio, the specific capacity of the Li/O2 cell fabricated from the carbon aerogels increases from 716 to 2077 charge/discharge cycles indicate that the carbon samples possess excellent stability on cycling.

Preparation of controlled porosity carbon-aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO2 atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O2 cell using the carbon with the largest pore volume (2.195cm3/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290mAh g-1.

Characterizing capacity loss of lithium oxygen batteries by impedance spectroscopy

Polymer based carbon aerogels were prepared by synthesis of a resorcinol formaldehyde gel followed by pyrolysis at 1073K under Ar and activation of the resultant carbon under CO2 at different temperatures. The prepared carbon aerogels were used as active materials in the preparation of cathode electrodes for lithium oxygen cells and the electrochemical performance of the cells was evaluated by galvanostatic charge/discharge cycling and electrochemical impedance measurements. It was shown that the storage capacity and discharge voltage of a Li/O2 cell strongly depend on the porous structure of the carbon used in cathode. EIS results also showed that the shape and value of the resistance in the impedance spectrum of a Li/O2 cell are strongly affected by the porosity of carbon used in the cathode. Porosity changes due to the build up of discharge products hinder the oxygen and lithium ion transfer into the electrode, resulting in a gradual increase in the cell impedance with cycling. The discharge capacity and cycle life of the battery decrease significantly as its internal resistance increases with charge/discharge cycling.

COMPARISON OF THE GROWTH INHIBITORY AND BACTERIOCIDAL EFFECTS OF TAUROLIDINE AND TAURULTAM ON A CLINICAL ISOLATE OF ESCHERICHIA-COLI

To investigate the mode of action of Taurolin, an antimicrobial preparation, the growth inhibitory and bacteriocidal effects of taurolidine and taurultam solutions on Escherichia coli isolated from a diagnosed urinary tract infection were examined at 37-degrees-C. The inhibitory effects of taurolidine solutions were observed to be greater than those of taurultam solutions at comparative concentrations; however, the presence of sublethal concentrations of formaldehyde (methylene glycol) associated with taurolidine was sufficient to account for this. The bacteriocidal activity of taurolidine (2.0% w/v) was greater than that of taurultam (4.5% w/v). Both compounds produced biphasic death rates with dissimilar initial slopes, suggested to be due to the presence of formaldehyde in taurolidine solutions. These observations indicate that the growth inhibitory and bacteriocidal effects of Taurolin solutions are primarily due to taurultam, however, the presence of sublethal concentrations of formaldehyde is significant in the expression of this activity.

Characterising cement-superplasticiser interaction using zeta potential measurements

The zeta potential generated at the interface between cement particle surfaces adsorbed with superplasticisers have been studied using electroacoustic technique, which is capable of measuring zeta potential at high concentrated suspensions. The study has been undertaken to examine the differences in the magnitude of the zeta potential for ordinary Portland cement (OPC) and Portland pozzolanic (fly ash) cement (PPC) pastes along with the differential impacts of different types of superplasticisers on both the varieties of cement pastes. In the latter context, the effects of three different types of superplasticisers namely Ligno Sulphonate (LS), Sulphonated Melamine Formaldehyde (SMF) and Sulphonated Naphthalene Formaldehyde (SNF) have been specifically studied. The results show that the cement pastes with PPC shows better dispersion when compared with the OPC. The paper also endeavors to unfold the relationship and significance of cement interaction with three different superplasticisers.

On-line FTIR spectroscopic investigations of methanol oxidation in a direct methanol fuel cell

A real-time Fourier transform infrared spectroscopy (FTIRS) analysis of the products of methanol oxidation in a prototype direct-methanol fuel cell operating at high temperatures (150 to 185°C) is reported here. The methanol oxidation products on platinum black and platinum-ruthenium catalyst surfaces were determined as a function of the fuel cell operating temperature, current density, and methanol/water mole ratio. Neither formaldehyde nor formic acid was detected in anode exhaust gas at all cell operating conditions. The product distributions of methanol oxidation obtained by on-line FTIRS are consistent with our previous results obtained by on-line mass spectroscopy under similar conditions. With pure methanol in anode feed, methanaldimethylacetal was found to be the main product, methyl formate and CO were also found. However, when water was present in the anode feed, the main product was CO , and the formation of methanaldimethylacetal and methyl formate decreased significantly with increase of the water/methanol mole ratio. Increase of cell operating temperature enhanced the formation of CO and decreased the formation of methanaldimethylacetal and methyl formate. Pt/Ru catalyst is more active for methanol oxidation and has a higher selectivity toward CO formation than Pt-black. Nearly complete methanol oxidation, i.e., the product was almost exclusively CO , was achieved using a Pt/Ru catalyst and a water/methanol mole ratio of 2 or higher in the anode feed at a temperature of 185°C or above.