John R. Sodeau

Energy-dispersive X-ray analysis of the extracellular cadmium sulfide crystallites of Klebsiella aerogenes.

Klebsiella aerogenes forms electron-dense partieles on the cell surface in response to the presence of cadmium ions in the growth medium. These particles ranged from 20 to 200 nm in size, and quantitative energy dispersive X-ray analysis established that they comprise cadmium and sulfur in a 1:1 ratio. This observation leads to the conclusion that the particles are cadmium sulfide crystallites. A combination of atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, and acid-labile sulfide analysis revealed that the total intracellular and bound extracellular cadmium:sulfur ratio is also 1:1, which suggests that the bulk of the cadmium is fixed as extracellular cadmium sulfide. The tolerance of K. acrogenes to cadmium ions and the formation of the cadmium sulfide crystallites were dependent on the buffer composition of the growth medium. The addition of cadmium ions to phosphate-buffered media resulted in cadmium phosphate precipitates that remove the potentially toxic cadmium ions from the growth medium. Electrondense particles formed on the surfaces of bacteria grown under these conditions were a combination of cadmium sulfide and cadmium phosphates. The specific bacterial growth rate in the exponential phase of batch cultures was not affected by up to 2mM cadmium in Tricine-buffered medium, but formation of cadmium sulfide crystallites was maximal during the stationary phase of batch culture. Cadmium tolerance was much lower (10 to 150 μM) in growth media buffered with Tris, Bistris propane, Bes, Tes, or Hepes. These results illustrate the importance of considering medium composition when comparing levels of bacterial cadmium tolerance.

Adsorption of stratospherically important molecules on thin D2O ice films using reflection absorption infrared spectroscopy

The adsorption of DCl, CCl4, CFCl3, CF2Cl2 and CF3Cl on thin D2O ice films at 110 K has been studied using reflection–absorption infrared spectroscopy (RAIRS). These compounds interact to varying degrees with the ice surface via the OD bonds dangling into the vacuum. DCI was found to dissociate ionically, evidenced by a strong band attributable to D3O+ and the absence of any absorption band for molecular DCl.

Large pore bi-functionalised mesoporous silica for metal ion pollution treatment

Here we demonstrate aminopropyl and mercatopropyl functionalised and bi-functionalised large pore mesoporous silica spheres to extract various metal ions from aqueous solutions towards providing active sorbents for mitigation of metal ion pollution. Elemental analysis (EA) and FTIR techniques were used to quantify the attachment of the aminopropyl and mercatopropyl functional groups to the mesoporous silica pore wall. Functionalisation was achieved by post-synthesis reflux procedures. For all functionalised silicas the functionalisation refluxing does not alter particle morphology/agglomeration of the particles. It was found that sorptive capacities of the mesoporous silica towards the functional groups were unaffected by co-functionalisation. Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameters, packing of the pores and specific surface areas of the modified mesoporous silica spheres. Atomic absorption (AA) spectroscopy and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques were used to measure the extraction efficiencies of each metal ion species from solution at varying pHs. Maximum sorptive capacities (as metal ions) were determined to be 384micromolg(-1) for Cr, 340micromol g(-1) for Ni, 358micromol g(-1) for Fe, 364micromol g(-1) for Mn and 188micromol g(-1) for Pd.

The use of polar organic compounds to estimate the contribution of domestic solid fuel combustion and biogenic sources to ambient levels of organic carbon and PM2.5 in Cork Harbour, Ireland

PM(2.5) samples collected at Cork Harbour, Ireland during summer, autumn, late autumn and winter, 2008-2009 were analyzed for polar organic compounds that are useful markers for aerosol source characterization. The determined compounds include tracers for biomass burning primary particles, fungal spores, markers for secondary organic aerosol (SOA) from isoprene, α-/β-pinene, and d-limonene. Seasonal and temporal variations and other characteristic features of the detected tracers are discussed in terms of aerosol sources and processes. The biogenic species were detected only during the summer period where the contributions of isoprene SOA and fungal spores to the PM(2.5) organic carbon (OC) were estimated to be 1.6% and 1% respectively. The biomass burning markers, and in particular levoglucosan, were present in all samples and attributed to the combustion of cellulose-containing fuels including wood, peat, bituminous and smokeless coal. The contribution of domestic solid fuel (DSF) burning to the measured OC mass concentration was estimated at 10.8, 50, 66.4 and 74.9% for summer, autumn, late autumn and winter periods, respectively, based on factors derived from a series of burning experiments on locally available fuels. Application of an alternative approach, namely principal component analysis-multiple linear regression (PCA-MLR), to the measured concentrations of the polar organic marker compounds used in conjunction with real-time air quality data provided similar trends and estimates for DSF combustion during all seasons except summer. This study clearly demonstrates that, despite the ban on the sale of bituminous coal in Cork and other large urban areas in Ireland, DSF combustion is still the major source of OC during autumn and winter periods and also makes a significant contribution to PM(2.5) levels. The developed marker approach for estimating the contribution of DSF combustion to ambient OC concentrations can, in principle, also be applied to other locations.

Photophysical and photochemical characterisation of bacterial semiconductor cadmium sulfide particles

Klebsiella pneumoniae forms electron-dense cadmium sulfide particles (ca. 5–200 nm in diameter) on the cell surface in response to the presence of cadmium ions in the growth medium. In the current study, these ‘bio-semiconductor’ particles have been spectroscopically characterised using UV–VIS absorption and luminescence analysis. The spectroscopic properties observed suggest that they are similar in size and possess photoactive traits analogous to CdS systems prepared by conventional chemical methods. The optical nature of the bacterial semiconductor particles means that, in principle, they are capable of performing a variety of photoredox reactions. The reactions involving photoelectrochemical indicators such as methyl viologen (MV2+) and methyl orange (MO−) are considered and, by comparing initial rates of reaction and altering reaction variables, a general mechanism of photoactivity for the cadmium sulfide ‘bio-semiconductor’ is proposed.

Adsorption and ionization of HCl on an ice surface

In this article, we describe a series of experiments investigating the interaction of the important stratospheric reservoir species HCl with the surface of a thin ice film. Reflection absorption infrared spectroscopy and thermal desorption spectroscopy have been used to identify the nature of the ionic hydrates formed under a variety of pressure, temperature, and exposure regimes.

Ionisation and solvation of stratospherically relevant molecules on ice films

Heterogeneous reactions of stratospheric reservoir species such as HCl, N2O5 and ClONO2 on type I (nitric acid hydrates) and type II (water-ice) polar stratospheric cloud (PSC) particles are believed to play an important role in the extremely large losses of stratospheric ozone observed during the Antarctic spring. Laboratory studies of such processes, using thin ice films as PSC particle surface mimics, can provide mechanistic information about individual elementary steps and overall reaction schemes. IR and mass spectrometry have been used to identify reaction products and intermediates and it has been shown that the primary step in all the studied reaction schemes involves the formation of ionic surface species. Furthermore, the nature and stability of the ions are found to be inextricably linked with the amount of ‘free’ water available to solvate them. The following questions are also addressed: Are adsorbed ions (e.g. nitrate, chloride and oxonium) reactive on ice surfaces? If so, are the products formed the same as those suggested when their corresponding molecular parents are involved? The answers, which have important implications for understanding stratospheric heterogeneous chemistry, are discussed in terms of ionic reaction mechanisms and novel surface intermediates.

Using the WIBS-4 (Waveband Integrated Bioaerosol Sensor) Technique for the On-Line Detection of Pollen Grains

Primary biological aerosol particles (PBAP) such as pollen and fungal spores can induce allergenic responses and affect health in general. Conditions such as allergic rhinitis (hay fever) and asthma have been related to pollen concentrations. Likewise some pollen have been shown to induce ice nucleation and cloud condensation at higher temperatures than those associated with some chemical species, thereby affecting planet Earths albedo and overall radiative balance. Hence, the near real-time (on-line) monitoring of airborne pollen and other PBAP using a variety of spectroscopic and light scattering techniques represents an area of growing development and consequence. In this study, two separate field campaigns (one at a rural site in Ireland and the other at an urbanized location in Germany) were performed to detect and quantify pollen releases using a novel on-line fluorescence spectrometer (WIBS-4). The results were compared with results obtained using more traditional Hirst-type impactors. Size, “shape,” and fluorescence characteristics of ambient particles were used to determine the concentrations and identity of the PBAP likely to be pollen grains. The concentration results obtained for both methodologies at both the Irish and German sites correlated very well, with R 2 values >0.9 determined for both campaigns. Furthermore, the sizing data available from the WIBS-4 approach employed in Ireland indicated that pollen grains can be identified in appropriate conditions. WIBS-4 measurements of Yew pollen both in the laboratory and at the rural site indicated almost identical size ranges of 25 to 27 μm. Yew pollen is generally reported to be in this range, but the measurements reported here are the first of their type providing data on the size of in-flight Yew pollen. Copyright 2014 American Association for Aerosol Research

Mechanisms for the heterogeneous hydrolysis of hydrogen chloride, chlorine nitrate and dinitrogen pentoxide on water-rich atmospheric particle surfaces

The heterogeneous interaction of the stratospheric reservoir species HCl, ClONO 2 , and N 2 O 5 with water-rich polar stratospheric particle mimics is characterized by the formation of solvated ionic products. Simple semiempirical calculations have been used to explain the nature of the species observed in infrared spectroscopic measurements and to elucidate the mechanism by which they are formed. The initial stages of the interaction appear to involve an S N 2-type nucleophilic attack by the oxygen atom of the surface water molecule upon the most accessible electrophilic site of the adsorbing reactant. Mechanistic schemes involving protonated acid intermediates and their subsequent decomposition or hydrolysis can be used to accurately predict and explain the stable reaction products observed spectroscopically under stratospheric conditions.

Atmospheric Concentrations of Alternaria, Cladosporium, Ganoderma and Didymella Spores Monitored in Cork (Ireland) and Worcester (England) During the Summer of 2010

This study represents the first international intercomparison of fungal spore observations since 1990, focusing on atmospheric concentrations of Alternaria, Cladosporium, Ganoderma and Didymella spores. The campaigns were performed at sites located in Cork (Ireland) and Worcester (England) during summer 2010. Observations were made using Hirst-type volumetric spore traps and corresponding optical identification at the genus level by microscope. The measurements at both sites (including meteorological parameters) were compared and contrasted. The relationships between the fungal spore concentrations with selected meteorological parameters were investigated using statistical methods and multivariate regression trees (MRT). The results showed high correlations between the two sites with respect to daily variations. Statistically significant higher spore concentrations for Alternaria, Cladosporium and Ganoderma were monitored at the Worcester site. This result was most likely due to the differences in precipitation and local fungal spore sources at the two sites. Alternaria and Cladosporium reached their maxima a month earlier in Cork than in Worcester, and Didymella with Ganoderma peaked simultaneously with similar diurnal trends found for all the investigated spore types. MRT analysis helped to determine threshold values of the meteorological parameters that exerted most influence on the presence of spores: they were found to vary at the two sites. Our results suggest that the aeromycological profile is quite uniform over the British Isles, but a description of bioaerosols with respect to overall load and daily concentration can be quite diverse although the geographical difference between sites is relatively small. These variations in the concentrations therefore need to be explored at the national level.