Optimization and Validation of Thermal Desorption Gas Chromatography-Mass Spectrometry for the Determination of Polycyclic Aromatic Hydrocarbons in Ambient Air

Thermal desorption (TD) coupled with gas chromatography/mass spectrometry (TD-GC/MS) is a simple alternative that overcomes the main drawbacks of the solvent extraction-based method: long extraction times, high sample manipulation, and large amounts of solvent waste. This work describes the optimization of TD-GC/MS for the measurement of airborne polycyclic aromatic hydrocarbons (PAlls) in particulate phase. The performance of the method was tested by Standard Reference Material (SRM) 1649b urban dust and compared with the conventional method (Soxhlet extraction-GC/MS), showing a better recovery (mean of 97%), precision (mean of 12%), and accuracy (+/- 25%) for the determination of 14 EPA PAHs. Furthermore, other 15 nonpriority PAHs were identified and quantified using their relative response factors (RRFs). Finally, the proposed method was successfully applied for the quantification of PAI Is in real 8 h-samples (PM10), demonstrating its capability for determination of these compounds in short-term monitoring.The authors gratefully thank the University of the Basque Country UPV/EHU (Ref.: GIU 13/25, GIU 16/03, and UFI 11/47) and the Spanish Ministry of Science and Innovation (MICINN) for financing the project PROMESHAP (Ref.: CTM 2010-20607). Inaki Elorduy wants to thank the MICINN for his doctoral grant Ministerio de Ciencia e Innovacio

Development of a portable leaf photosynthesis and volatile organic compounds emission system.

Understanding how plant carbon metabolism responds to environmental variables such as light is central to understanding ecosystem carbon cycling and the production of food, biofuels, and biomaterials. Here, we couple a portable leaf photosynthesis system to an autosampler for volatile organic compounds (VOCs) to enable field observations of net photosynthesis simultaneously with emissions of VOCs as a function of light. Following sample collection, VOCs are analyzed using automated thermal desorption-gas chromatograph-mass spectrometry (TD-GC-MS). An example is presented from a banana plant in the central Amazon with a focus on the response of photosynthesis and the emissions of eight individual monoterpenes to light intensity. Our observations reveal that banana leaf emissions represent a 1.1 +/- 0.1% loss of photosynthesis by carbon. Monoterpene emissions from banana are dominated by trans-β-ocimene, which accounts for up to 57% of total monoterpene emissions at high light. We conclude that the developed system is ideal for the identification and quantification of VOC emissions from leaves in parallel with CO2 and water fluxes.The system therefore permits the analysis of biological and environmental sensitivities of carbon metabolism in leaves in remote field locations, resulting in the emission of hydrocarbons to the atmosphere.•A field-portable system is developed for the identification and quantification of VOCs from leaves in parallel with leaf physiological measurements including photosynthesis and transpiration.•The system will enable the characterization of carbon and energy allocation to the biosynthesis and emission of VOCs linked with photosynthesis (e.g. isoprene and monoterpenes) and their biological and environmental sensitivities (e.g. light, temperature, CO2).•Allow the development of more accurate mechanistic global VOC emission models linked with photosynthesis, improving our ability to predict how forests will respond to climate change. It is our hope that the presented system will contribute with critical data towards these goals across Earth's diverse tropical forests

Non-destructive measurement of volatile organic compounds in modified atmosphere packaged poultry using SPME-SIFT-MS in tandem with Headspace TD-GC-MS

A methodology was developed to measure volatile organic compounds (VOCs) in a non-destructive way inside modified atmosphere packaged (MAP) poultry (chicken fillets) samples stored at 4 degrees C. To achieve this, a solid-phase microextraction (SPME) fiber was inserted in the headspace of the package and was later desorbed within a heated injector coupled with a selected ion flow tube mass spectrometer (SIFT-MS). As this technique is not stand-alone, it was calibrated on the same matrix using online SIFT-MS measurements and headspace thermal desorption gas chromatography (HS-TD-GC-MS) with internal standard calibration. A total of eight compounds were successfully monitored within the same samples over a storage period of 15 days. Ethanol and dimethyl sulfide presented the highest overall increase with large variations between the samples, while a clear increase was observed for 2-propanol, 2-butanone, and 3-methylbutanal by the end of shelf life. Our method provides a fast (analysis time < 5 min) non-destructive alternative for VOC measurements within modified atmosphere packaged products at refrigerated conditions. This approach can be useful to determine potential biomarkers at real storage conditions of packaged food prior to the moment of consumption

Development and validation by accuracy profile of a method for the analysis of monoterpenes in indoor air by active sampling and thermal desorption-gas chromatography-mass spectrometry

peer reviewedThe technique of thermal desorption (TD)-GC/MS was evaluated for the measurement of monoterpenes in indoor air. The validation strategy was intentionally oriented towards routine use and the reliability of the method rather than extreme performance. For this reason, validation by accuracy profile was chosen. The accuracy profile procedure, which is based on the concept of total error (bias + standard deviation), guarantees that a known proportion of future results obtained with the method will be within acceptance limits. For all the compounds tested in the present study, α-pinene, α-terpineol, β-pinene, d-limonene, Δ3-carene, camphene, 1,8-cineole, p-cymene, linalool, but not in the case of carvone, the accuracy profile procedure established that at least 95% of the future results obtained would be within the ±15% acceptance limits of the validated method over the whole defined concentration range. Other parameters, such as selectivity, recovery, repeatability, stability of the molecules of interest and the effect of temperature, were also determined. The performance of the described method was finally evaluated by the analysis of indoor air from new timber frame constructions

Organic Contamination Baseline Study: In NASA JSC Astromaterials Curation Laboratories. Summary Report

In preparation for OSIRIS-REx and other future sample return missions concerned with analyzing organics, we conducted an Organic Contamination Baseline Study for JSC Curation Labsoratories in FY12. For FY12 testing, organic baseline study focused only on molecular organic contamination in JSC curation gloveboxes: presumably future collections (i.e. Lunar, Mars, asteroid missions) would use isolation containment systems over only cleanrooms for primary sample storage. This decision was made due to limit historical data on curation gloveboxes, limited IR&D funds and Genesis routinely monitors organics in their ISO class 4 cleanrooms

Laboratory and field evaluation of acetic acid-based lures for male Asian citrus psyllid, Diaphorina citri.

The Asian citrus psyllid (ACP) is a vector of a pathogen associated with greening and thus a major problem in citriculture worldwide. Lures are much needed for improving ACP trapping systems for monitoring populations and surveillance. Previously, we have identified acetic acid as a putative sex pheromone and measured formic acid- and propionic acid-elicited robust electroantennographic responses. We have now thoroughly examined in indoor behavioral assays (4-way olfactometer) and field tests the feasibility of these three semiochemicals as potential lures for trapping ACP. Formic acid, acetic acid, and propionic acid at appropriate doses are male-specific attractants and suitable lures for ACP traps, but they do not act synergistically. An acetic acid-based homemade lure, prepared by impregnating the attractant in a polymer, was active for a day. A newly developed slow-release formulation had equal performance but lasted longer, thus leading to an important improvement in ACP trap capture at low population densities

Volatile methyl siloxanes (VMS) concentrations in outdoor air of several Catalan urban areas

Volatile methyl siloxanes (VMS) were evaluated in ten Catalan urban areas with different industrial impacts, such as petrochemical industry, electrical and mechanical equipment, metallurgical and chemical industries, municipal solid waste treatment plant and cement and food industries, during 2013–2015. 24 h samples were taken with LCMA-UPC pump samplers specially designed in our laboratory, with a flow range of 70 ml min-1. A sorbent-based sampling method, successfully developed to collect a wide-range of VOC, was used. The analysis was performed by automatic thermal desorption coupled with capillary gas chromatography/mass spectrometry detector. The presented methodology allows the evaluation of VMS together with a wide range of other VOC, increasing the number of compounds that can be determined in outdoor air quality assessment of urban areas. This aspect is especially relevant as a restriction of several VMS (D4 and D5) in consumer products has been made by the European Chemicals Agency and US EPA is evaluating to include D4 in the Toxic Substances Control Act, regarding the concern of the possible effects of these compounds in human health and the environment. SVMS concentrations (L2-L5, D3-D6 and trimethylsilanol) varied between 0.3 ± 0.2 µg m-3 and 18 ± 12 µg m-3, determined in a hotspot area. Observed VMS concentrations were generally of the same order of magnitude than the previously determined in Barcelona, Chicago and Zurich urban areas, but higher than the published from suburban sites and Arctic locations. Cyclic siloxanes concentrations were up to two-three orders of magnitude higher than those of linear siloxanes, accounting for average contributions to the total concentrations of 97 ± 6% for all samples except for the hotspot area, where cyclic VMS accounted for 99.9 ± 0.1%. D5 was the most abundant siloxane in 5 sampling points; however, differing from the generally observed in previous studies, D3 was the most abundant compound in the other 5 sampling points.Peer ReviewedPostprint (author's final draft

Secondary Organic Aerosol Formation from Healthy and Aphid-Stressed Scots Pine Emissions.

One barrier to predicting biogenic secondary organic aerosol (SOA) formation in a changing climate can be attributed to the complex nature of plant volatile emissions. Plant volatile emissions are dynamic over space and time, and change in response to environmental stressors. This study investigated SOA production from emissions of healthy and aphid-stressed Scots pine saplings via dark ozonolysis and photooxidation chemistry. Laboratory experiments using a batch reaction chamber were used to investigate SOA production from different plant volatile mixtures. The volatile mixture from healthy plants included monoterpenes, aromatics, and a small amount of sesquiterpenes. The biggest change in the volatile mixture for aphid-stressed plants was a large increase (from 1.4 to 7.9 ppb) in sesquiterpenes-particularly acyclic sesquiterpenes, such as the farnesene isomers. Acyclic sesquiterpenes had different effects on SOA production depending on the chemical mechanism. Farnesenes suppressed SOA formation from ozonolysis with a 9.7-14.6% SOA mass yield from healthy plant emissions and a 6.9-10.4% SOA mass yield from aphid-stressed plant emissions. Ozonolysis of volatile mixtures containing more farnesenes promoted fragmentation reactions, which produced higher volatility oxidation products. In contrast, plant volatile mixtures containing more farnesenes did not appreciably change SOA production from photooxidation. SOA mass yields ranged from 10.8 to 23.2% from healthy plant emissions and 17.8-26.8% for aphid-stressed plant emissions. This study highlights the potential importance of acyclic terpene chemistry in a future climate regime with an increased presence of plant stress volatiles

Root-emitted volatile organic compounds: can they mediate belowground plant-plant interactions?

Background Aboveground, plants release volatile organic compounds (VOCs) that act as chemical signals between neighbouring plants. It is now well documented that VOCs emitted by the roots in the plant rhizosphere also play important ecological roles in the soil ecosystem, notably in plant defence because they are involved in interactions between plants, phytophagous pests and organisms of the third trophic level. The roles played by root-emitted VOCs in between- and within-plant signalling, however, are still poorly documented in the scientific literature. Scope Given that (1) plants release volatile cues mediating plant-plant interactions aboveground, (2) roots can detect the chemical signals originating from their neighbours, and (3) roots release VOCs involved in biotic interactions belowground, the aim of this paper is to discuss the roles of VOCs in between- and within-plant signalling belowground. We also highlight the technical challenges associated with the analysis of root-emitted VOCs and the design of experiments targeting volatile-mediated root-root interactions. Conclusions We conclude that root-root interactions mediated by volatile cues deserve more research attention and that both the analytical tools and methods developed to study the ecological roles played by VOCs in interplant signalling aboveground can be adapted to focus on the roles played by root-emitted VOCs in between- and within-plant signalling