Passive breath monitoring of livestock: using factor analysis to deconvolve the cattle shed.

Respiratory and metabolic diseases in livestock cost the agriculture sector billions each year, with delayed diagnosis a key exacerbating factor. Previous studies have shown the potential for breath analysis to successfully identify incidence of disease in a range of livestock. However, these techniques typically involve animal handling, the use of nasal swabs or fixing a mask to individual animals to obtain a sample of breath. Using a cohort of 26 cattle as an example, we show how the breath of individual animals within a herd can be monitored using a passive sampling system, where no such handling is required. These benefits come at the cost of the desired breath samples unavoidably mixed with the complex cocktail of odours that are present within the cattle shed. Data were analysed using positive matrix factorisation (PMF) to identify and remove non-breath related sources of volatile organic compounds. In total three breath factors were identified (endogenous-, non-endogenous breath and rumen) and seven factors related to other sources within and around the cattle shed (e.g. cattle feed, traffic, urine and faeces). Simulation of a respiratory disease within the herd showed that the abnormal change in breath composition was captured in the residuals of the ten factor PMF solution, highlighting the importance of their inclusion as part of the breath fraction. Increasing the number of PMF factors to 17 saw the identification of a 'diseased' factor, which coincided with the visits of the three 'diseased' cattle to the breath monitor platform. This work highlights the important role that factor analysis techniques can play in analysing passive breath monitoring data.

Monoterpenes from tropical forest and oil palm plantation floor in Malaysian Borneo/Sabah: emission and composition.

Regional estimates of VOC fluxes focus largely on emissions from the canopy and omit potential contributions from the forest floor including soil, litter and understorey vegetation. Here, we measured monoterpene emissions every 2 months over 2 years from logged tropical forest and oil palm plantation floor in Malaysian Borneo using static flux chambers. The main emitted monoterpenes were α-pinene, ß-pinene and d-limonene. The amount of litter present was the strongest indicator for higher monoterpene fluxes. Mean α-pinene fluxes were around 2.5-3.5 µg C m-2 h-1 from the forest floor with occasional fluxes exceeding 100 µg C m-2 h-1. Fluxes from the oil palm plantation, where hardly any litter was present, were lower (on average 0.5-2.9 µg C m-2 h-1) and only higher when litter was present. All other measured monoterpenes were emitted at lower rates. No seasonal trends could be identified for all monoterpenes and mean fluxes from both forest and plantation floor were ~ 100 times smaller than canopy emission rates reported in the literature. Occasional spikes of higher emissions from the forest floor, however, warrant further investigation in terms of underlying processes and their contribution to regional scale atmospheric fluxes.

A review of stereochemical implications in the generation of secondary organic aerosol from isoprene oxidation.

The atmospheric reactions leading to the generation of secondary organic aerosol (SOA) from the oxidation of isoprene are generally assumed to produce only racemic mixtures, but aspects of the chemical reactions suggest this may not be the case. In this review, the stereochemical outcomes of published isoprene-degradation mechanisms contributing to high amounts of SOA are evaluated. Despite evidence suggesting isoprene first-generation oxidation products do not contribute to SOA directly, this review suggests the stereochemistry of first-generation products may be important because their stereochemical configurations may be retained through to the second-generation products which form SOA. Specifically, due to the stereochemistry of epoxide ring-opening mechanisms, the outcome of the reactions involving epoxydiols of isoprene (IEPOX), methacrylic acid epoxide (MAE) and hydroxymethylmethyl-α-lactone (HMML) are, in principle, stereospecific which indicates the stereochemistry is predefined from first-generation precursors. The products from these three epoxide intermediates oligomerise to form macromolecules which are proposed to form chiral structures within the aerosol and are considered to be the largest contributors to SOA. If conditions in the atmosphere such as pH, aerosol water content, relative humidity, pre-existing aerosol, aerosol coatings and aerosol cation/anion content (and other) variables acting on the reactions leading to SOA affect the tacticity (arrangement of chiral centres) in the SOA then they may influence its physical properties, for example its hygroscopicity. Chamber studies of SOA formation from isoprene encompass particular sets of controlled conditions of these variables. It may therefore be important to consider stereochemistry when upscaling from chamber study data to predictions of SOA yields across the range of ambient atmospheric conditions. Experiments analysing the stereochemistry of the reactions under varying conditions of the above variables would help elucidate whether there is stereoselectivity in SOA formation from isoprene and if the rates of SOA formation are affected.