Far-Field Petahertz Sampling of Plasmonic Fields.

The response of metal nanostructures to optical excitation leads to localized surface plasmon (LSP) generation with nanoscale field confinement driving applications in, for example, quantum optics and nanophotonics. Field sampling in the terahertz domain has had a tremendous impact on the ability to trace such collective excitations. Here, we extend such capabilities and introduce direct sampling of LSPs in a more relevant petahertz domain. The method allows to measure the LSP field in arbitrary nanostructures with subcycle precision. We demonstrate the technique for colloidal nanoparticles and compare the results to finite-difference time-domain calculations, which show that the build-up and dephasing of the plasmonic excitation can be resolved. Furthermore, we observe a reshaping of the spectral phase of the few-cycle pulse, and we demonstrate ad-hoc pulse shaping by tailoring the plasmonic sample. The methodology can be extended to single nanosystems and applied in exploring subcycle, attosecond phenomena.

Rapid Freezing and Cryo-SEM-EDS Imaging of Foraminifera (Unicellular Eukaryotes) Using a Conductive Viscous Cryogenic Glue.

Spatial distribution of water-soluble molecules and ions in living organisms is still challenging to assess. Energy-dispersive X-ray spectroscopy (EDS) via cryogenic scanning electron microscopy (cryo-SEM) is one of the promising methods to study them without loss of dissolved contents. High-resolution cryo-SEM-EDS has challenges in sample preparation, including cross-section exposure and sample drift/charging due to insulative surrounding water. The former becomes problematic for large and inseparable organisms, such as benthic foraminifera, a unicellular eukaryote playing significant roles in marine ecosystems, which often exceed the size limit for the most reliable high-pressure freezing. Here we show graphite oxide dispersed in sucrose solution as a good glue to freeze, expose cross-section by cryo-ultramicrotome, and analyze elemental distribution owing to the glue's high viscosity, adhesion force, and electron conductivity. To demonstrate the effectiveness and applicability of the glue for cryo-SEM-EDS, deep-sea foraminifer Uvigerina akitaensis was sampled during a cruise and plunge frozen directly on the research vessel, where the liquid nitrogen supply is limited. The microstructures were preserved as faithfully in cryo-SEM images as those with the conventional resin-substituted transmission electron micrograph. We found elements colocalized within the cytoplasm originating from water-soluble compounds that can be lost with conventional dehydrative fixation.

Higher local intra- than interspecific variability in water- and carbon-related leaf traits among Neotropical tree species.

BACKGROUND AND AIMS: Intraspecific variability in leaf water-related traits remains little explored despite its potential importance in the context of increasing drought frequency and severity. Studies comparing intra- and interspecific variability of leaf traits often rely on inappropriate sampling designs that result in non-robust estimates, mainly owing to an excess of the species/individual ratio in community ecology or, on the contrary, to an excess of the individual/species ratio in population ecology. METHODS: We carried out virtual testing of three strategies to compare intra- and interspecific trait variability. Guided by the results of our simulations, we carried out field sampling. We measured nine traits related to leaf water and carbon acquisition in 100 individuals from ten Neotropical tree species. We also assessed trait variation among leaves within individuals and among measurements within leaves to control for sources of intraspecific trait variability. KEY RESULTS: The most robust sampling, based on the same number of species and individuals per species, revealed higher intraspecific variability than previously recognized, higher for carbon-related traits (47-92 and 4-33 % of relative and absolute variation, respectively) than for water-related traits (47-60 and 14-44 % of relative and absolute variation, respectively), which remained non-negligible. Nevertheless, part of the intraspecific trait variability was explained by variation of leaves within individuals (12-100 % of relative variation) or measurement variations within leaf (0-19 % of relative variation) and not only by individual ontogenetic stages and environmental conditions. CONCLUSIONS: We conclude that robust sampling, based on the same number of species and individuals per species, is needed to explore global or local variation in leaf water- and carbon-related traits within and among tree species, because our study revealed higher intraspecific variation than previously recognized.

Combining Passive Sampling with Suspect and Nontarget Screening to Characterize Organic Micropollutants in Streams Draining Mixed-Use Watersheds.

Organic micropollutants (OMPs) represent an anthropogenic stressor on stream ecosystems. In this work, we combined passive sampling with suspect and nontarget screening enabled by liquid chromatography-high-resolution mass spectrometry to characterize complex mixtures of OMPs in streams draining mixed-use watersheds. Suspect screening identified 122 unique OMPs for target quantification in polar organic chemical integrative samplers (POCIS) and grab samples collected from 20 stream sites in upstate New York over two sampling seasons. Hierarchical clustering established the co-occurrence profiles of OMPs in connection with watershed attributes indicative of anthropogenic influences. Nontarget screening leveraging the time-integrative nature of POCIS and the cross-site variability in watershed attributes prioritized and confirmed 11 additional compounds that were ubiquitously present in monitored streams. Field sampling rates for 37 OMPs that simultaneously occurred in POCIS and grab samples spanned the range of 0.02 to 0.22 L/d with a median value of 0.07 L/d. Comparative analyses of the daily average loads, cumulative exposure-activity ratios, and multi-substance potentially affected fractions supported the feasibility of complementing grab sampling with POCIS for OMP load estimation and screening-level risk assessments. Overall, this work demonstrated a multi-watershed sampling and screening approach that can be adapted to assess OMP contamination in streams across landscapes.

An experimental simulation study of conventional waste burning practices in India for the assessment and inventorisation of PCDD/F/dl-PCB emissions.

The paper reports an update to the polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) annual emission inventory of India from open burning of municipal solid wastes (MSW) through the generation of nation-specific emission factors for air (EFair) and burned residue (EFland) vectors. The MSW characteristics and modes of disposal practiced in Indian cities exhibits subtle variations from that of developed nations due to differences in food habits, living standards and climatic conditions. The annual emission calculations based on EFs from hitherto studies simulating conditions prevailing in developed countries can lead to anomalous accounting of emission levels. It is the first experimental study reported from Indian subcontinent to determine EFs of dioxins and dl-PCBs from MSW open burning by simulated combustion experiments conducted in a custom fabricated Open Burning Test Facility (OBTF) - "Burn Hut", using real dumpsite waste samples. Iso-kinetic sampling and coning and quartering methods were employed for the sampling of air and land emissions from combustion experiments. The PCDD/F's EFair ranged from 3 to 675 µg toxicity equivalence (TEQ)/ton of waste with a geometric mean (GMair) of 67.0 µgTEQ/ton and EFland ranged from 10 to 2531 µgTEQ/ton waste (GMland - 100.0 µgTEQ/ton). The EFair and EFland of dl-PCBs ranged from 0.5 to 46 µgTEQ/ton (GMair 7.0 µgTEQ/ton) and 0.5 to 96 µgTEQ/ton of waste (GMland 6.0 µgTEQ/ton) respectively. A detailed assessment of correlations between emission and MSW composition/combustion practices were conducted along with a comparative evaluation of EFpresent vis-à-vis EFs reported elsewhere.

Recovery of RNA from avian nucleated whole blood stored under field conditions: an evaluation of commercial methods.

1. Whole blood can be used to gain insights on several molecular mechanisms involved in animal physiology. However, its use to extract RNA from organisms that carry nucleated red blood cells is limited due to its high nuclease content and instability under field conditions.2. Here, we evaluate three commercially available RNA preservation and extraction methods applied to avian whole-blood samples kept in different storage conditions to identify the most suitable ones for use in field studies.3. Whole-blood starting volume was the most important factor; only samples with a starting volume of 50 µl yielded RNA, whereas all 100 µl samples failed to provide any RNA regardless of the method used. RNA concentration decreased with storage time in every method employed. Samples stored at -20°C yielded higher RNA concentration than the ones stored at 4°C, although some possible effects of freeze-thaw cycles were observed.4. For two of the three methods, it is likely that DNA contamination and/or extensive degradation of RNA could have taken place. Only whole blood stored and extracted using the Quick RNA Whole Blood kit provided high-quality RNA in every condition tested.

Leaf shape and size variation in bur oaks: an empirical study and simulation of sampling strategies.

PREMISE: Leaf shape and size figure strongly in plants' adaptation to their environments. Among trees, oaks are notoriously variable in leaf morphology. Our study examines the degree to which within-tree, among-tree, and among-site variation contribute to latitudinal variation in leaf shape and size of bur oak (Quercus macrocarpa: Fagaceae), one of North America's most geographically widespread oak species. METHODS: Samples were collected from four sites each at northern, central, and southern latitudes of the bur oak range. Ten leaf size traits were measured, and variance in these traits and eight ratios based on these traits was partitioned into tree and population components. Population means were regressed on latitude. We then parameterized a series of leaf collection simulations using empirical covariance among leaves on trees and trees at sites. We used the simulations to assess the efficiency of different collecting strategies for estimating among-population differences in leaf shape and size. RESULTS: Leaf size was highly responsive to latitude. Site contributed more than tree to total variation in leaf shape and size. Simulations suggest that power to detect among-site variance in leaf shape and size increases with either more leaves per tree (10-11 leaves from each of 5 trees) or more trees per site (5 leaves from each of 10+ trees). CONCLUSIONS: Our study demonstrates the utility of simulating sampling and controlling for variance in sampling for leaf morphology, whether the questions being addressed are ecological, evolutionary, or taxonomic. Simulation code is provided as an R package (traitsPopSim) to help researchers plan morphological sampling strategies.

Scattered Far-Field Sampling in Multi-Static Multi-Frequency Configuration.

This paper deals with an inverse scattering problem under a linearized scattering model for a multi-static/multi-frequency configuration. The focus is on the determination of a sampling strategy that allows the reduction of the number of measurement points and frequencies and at the same time keeping the same achievable performance in the reconstructions as for full data acquisition. For the sake of simplicity, a 2D scalar geometry is addressed, and the scattered far-field data are collected. The relevant scattering operator exhibits a singular value spectrum that abruptly decays (i.e., a step-like behavior) beyond a certain index, which identifies the so-called number of degrees of freedom (NDF) of the problem. Accordingly, the sampling strategy is derived by looking for a discrete finite set of data points for which the arising semi-discrete scattering operator approximation can reproduce the most significant part of the singular spectrum, i.e., the singular values preceding the abrupt decay. To this end, the observation variables are suitably transformed so that Fourier-based arguments can be used. The arising sampling grid returns several data that is close to the NDF. Unfortunately, the resulting data points (in the angle-frequency domain) leading to a complicated measurement configuration which requires collecting the data at different spatial positions for each different frequency. To simplify the measurement configuration, a suboptimal sampling strategy is then proposed which, by an iterative procedure, enforces the sampling points to belong to a rectangular grid in the angle-frequency domain. As a result of this procedure, the overall data points (i.e., the couples angle-frequency) actually increase but the number of different angles and frequencies reduce and lead to a measurement configuration that is more practical to implement. A few numerical examples are included to check the proposed sampling scheme.

Evaluation of a hybrid in-field sampling method for the detection of pathogenic bacteria through consideration of a priori knowledge of factors related to non-random contamination.

Pre-harvest testing is increasingly used to enhance the microbial safety of fresh produce. Traditional sampling assumes that sample collectors have no information on potential contamination sources. Knowledge of such factors could potentially increase the effectiveness of pre-harvest sampling programs. Simulation modeling and field validation trials were used to evaluate a hybrid "Samples of Opportunity" (SOO) sampling method that included a portion of the samples based on the sampler's knowledge of risk factors in pre-harvest produce fields. Relative effectiveness of SOO sampling was compared with three traditional sampling methods. These evaluations were based on three non-random contamination scenarios. The mean detection probability of SOO is 96% higher than traditional sampling methods (p < 0.001). However, if the site of actual contamination is offset from assumed area of contamination, the detection probability of SOO sampling drops, and becomes similar or even worse than that achieved by the other sampling methods. Preliminary field validation trials indicated indeed that SOO performed better than the other three sampling methods. This study provides a mathematical approach for evaluating the effectiveness of four pre-harvest sampling methods, and suggests that having a priori knowledge of the contamination source in the field would improve effectiveness of sampling, particularly if done using a standardized protocol.

Field Verification of the Prediction Model on Desert Locust Adult Phase Status From Density and Vegetation.

Previous studies investigated the effect of vegetation on density thresholds of adult Desert Locust gregarization from historical data in Mauritania. We examine here the prediction of locust phase based on adult density and vegetation conditions using the statistical model from Cisse et al. compared with actual behavior of Desert Locust adults observed in the field in Mauritania. From the 130 sites where adult locusts were found, the model predicted the phase of Desert Locust adults with a relatively small error of prediction of 6.1%. Preventive locust control should be rational, based on a risk assessment. The staff involved in implementation of the preventive control strategy needs specific indicators for when or where chemical treatment should be done. In this respect, we show here that the statistical model of Cisse et al. may be appropriate.

Impacts, causes and biofortification strategy of rice selenium deficiency based on publication collection.

Selenium (Se) deficiency in rice will result in a Se hidden hunger threat to the general public's human health, particularly in areas where rice consumption is high. Nevertheless, the impact scope and coping strategies have not been given sufficient focus on a worldwide scale. In order to evaluate the impacts, causes and biofortification strategies of Se-deficient rice, this study collected data from the publications on three themes: market survey, field sampling and controlled experiments. According to the market survey, global rice Se concentrations were 0.079 mg/kg on mean and 0.062 mg/kg on median. East Asia has a human Se intake gap due to the region's high rice consumption and the lowest rice Se concentration in markets globally. Total Se concentrations in East Asian paddy soils were found to be adequate based on the field sampling. However, over 70 % of East Asian paddy fields were inadequate to yield rice that met the global mean for rice Se concentration. The Se-deficient rice was probably caused by widespread low Se bioavailability in East Asian paddy fields. There were two important factors influencing rice Se enrichment including root Se uptake and iron oxide in soils. Concentrating on these processes is beneficial to rice Se biofortification. Since Se is adequate in the paddy soils of East Asia. Rather of adding Se exogenously, activating the native Se in paddy soil is probably a more appropriate strategy for rice Se biofortification in East Asia. Meta-analysis revealed water management had the greatest impact on rice Se biofortification. The risks and solutions for rice Se deficiency were discussed in our farmland-to-table survey, which will be a valuable information in addressing the global challenge of Se hidden hunger. This study also provided new perspectives and their justifications, critically analyzing both present and future strategies to address Se hidden hunger.

Effective Field Sampling of Rectoanal Mucosa-Associated Lymphoid Tissue for Antemortem Chronic Wasting Disease Testing in White-tailed Deer (Odocoileus virginianus).

Chronic wasting disease (CWD) is a fatal prion disease of cervids that has spread across much of North America. Although gold standard CWD diagnostics involve postmortem testing of medial retropharyngeal lymph nodes or obex (brain stem), a key tissue sample for antemortem testing is rectoanal mucosa-associated lymphoid tissue (RAMALT). However, collection of an adequate sample (i.e., enough lymphoid follicles) may be affected by factors such as deer age, repeated sampling, skill of the sampler, and adverse conditions during collection. Here, we document the protocol used to train personnel for RAMALT collection in a large study of free-ranging white-tailed deer (Odocoileus virginianus) in Wisconsin, USA, and determine factors that contributed to the occurrence of inadequate RAMALT samples. Our training protocol included hands-on experience with postmortem tissues, as well as a mentored collection process in the field. Collection of RAMALT under field conditions was highly successful, with 763/806 (94.7%) samples deemed adequate for subsequent testing. Although inadequate samples were rare, they were more likely to occur with older deer and when samples were collected at dusk (i.e., limited ambient lighting). We conclude that RAMALT collection can be highly successful under adverse field conditions, including with technicians with limited prior veterinary experience, and we provide details of our training program to facilitate repeatability in other antemortem CWD testing efforts.

A straightforward protocol to sample morphological traits of dragonflies and damselflies in the field.

Scarcity of morphological data limits the potential of functional ecology approaches, which rely on traits to elucidate ecological processes. Dragonflies and damselflies (Odonata) are a frequently used ecological model for which, however, only limited morphological data is available. Here, it is presented a field sampling protocol to collect ecologically relevant yet largely unavailable morphological traits of Odonata. The protocol enables the straightforward collection of traits from living individuals directly in the field. Those traits include body mass, wing area and wing loading as well as thorax width, hindwing length and body length. Furthermore, the protocol allows for posterior wing morphometric analyses. The protocol proved to be robust and universally applicable based on testing on roughly half (76) of all European odonate species. The use of this protocol can increase our understanding of odonatan morphology at interspecific and intraspecific levels and assist in developing mechanistic understanding of their ecology.

Spatial Distribution Pattern and Sampling Plans for Two Sympatric Tomicus Species Infesting Pinus yunnanensis during the Shoot-Feeding Phase.

Tomicus minor (Hartig) and Tomicus yunnanensis Kirkendall and Faccoli are two sympatric species that infest Pinus yunnanensis (Franchet) in southwest China, contributing to growth losses. Accurate sampling plans are needed to make informed control decisions for these species. We investigated three pine forests within experimental sites in Yuxi, Yunnan province, China from 2016 to 2018. The spatial distribution patterns of two pine shoot beetles during the shoot-feeding phase were determined using Taylor's power law. The optimum sample sizes and stop lines for precision levels of 0.25 and 0.10 were calculated. The model was validated using an additional 15 and 17 independent field datasets ranging in density from 0.06 to 1.90 beetles per tree. T. minor and T. yunnanensis adults showed aggregated spatial distributions. For T. minor, sample sizes of 41 and 259 trees were adequate for a D of 0.25 and 0.10, respectively, while for T. yunnanensis, a mean density of one individual per tree required sample sizes of 33 plants (D = 0.25) and 208 plants (D = 0.10). The software simulations of this sampling plan showed precision levels close to the desired levels. At a fixed-precision level of 0.25, sampling is easily achievable. This sampling program is useful for the integrated pest management (IPM) of two sympatric Tomicus species.

Efficacy of Soft-Rot Disease Biocontrol Agents in the Inhibition of Production Field Pathogen Isolates.

The Dickeya and Pectobacterium bacterial species cause blackleg and soft-rot diseases on potato plants and tubers. Prophylactic actions are essential to conserve a high quality of seed potato tubers. Biocontrol approaches are emerging, but we need to know how efficient biocontrol agents are when facing the natural diversity of pathogens. In this work, we sampled 16 production fields, which were excluded from the seed tuber certification scheme, as well as seven experimental parcels, which were planted with seed tubers from those production fields. We collected and characterized 669 Dickeya and Pectobacterium isolates, all characterized using nucleotide sequence of the gapA gene. This deep sampling effort highlighted eleven Dickeya and Pectobacterium species, including four dominant species namely D. solani, D. dianthicola, P. atrosepticum and P. parmentieri. Variations in the relative abundance of pathogens revealed different diversity patterns at a field or parcel level. The Dickeya-enriched patterns were maintained in parcels planted with rejected seed tubers, suggesting a vertical transmission of the pathogen consortium. Then, we retained 41 isolates representing the observed species diversity of pathogens and we tested each of them against six biocontrol agents. From this work, we confirmed the importance of prophylactic actions to discard contaminated seed tubers. We also identified a couple of biocontrol agents of the Pseudomonas genus that were efficient against a wide range of pathogen species.

Metabolomics for in situ monitoring of attached Crassostrea gigas and Mytilus edulis: Effects of offshore wind farms on aquatic organisms.

While offshore wind power has support from countries around the world, studies show that offshore wind farms (OWFs) may affect marine organisms. Environmental metabolomics is a high-throughput method that provides a snapshot of an organism's metabolic state. To elucidate the effects of OWFs on aquatic organisms, we studied, in situ, Crassostrea gigas and Mytilus edulis attached within and outside of OWFs and their reef areas. Our results show that epinephrine, sulphaniline, and inosine 5'-monophosphate were significantly increased and L-carnitine was significantly reduced in both Crassostrea and Mytilus species from the OWFs. This may be related to immune response, oxidative stress, energy metabolism and osmotic pressure regulation of aquatic organisms. Our study shows that active selection of biological monitoring methods for risk assessment is necessary and that metabolomics of attached shellfish is useful in elucidating the metabolic pathways of aquatic organisms in OWFs.

The performance of field sampling for parasite detection in a wild passerine.

Parasites can impact the behavior of animals and alter the interplay with ecological factors in their environment. Studying the effects that parasites have on animals thus requires accurate estimates of infections in individuals. However, quantifying parasites can be challenging due to several factors. Laboratory techniques, physiological fluctuations, methodological constraints, and environmental influences can introduce measurement errors, in particular when screening individuals in the wild. These issues are pervasive in ecological studies where it is common to sample study subjects only once. Such factors should be carefully considered when choosing a sampling strategy, yet presently there is little guidance covering the major sources of error. In this study, we estimate the reliability and sensitivity of different sampling practices at detecting two internal parasites-Serratospiculoides amaculata and Isospora sp.-in a model organism, the great tit Parus major. We combine field and captive sampling to assess whether individual parasite infection status and load can be estimated from single field samples, using different laboratory techniques-McMaster and mini-FLOTAC. We test whether they vary in their performance, and quantify how sample processing affects parasite detection rates. We found that single field samples had elevated rates of false negatives. By contrast, samples collected from captivity over 24 h were highly reliable (few false negatives) and accurate (repeatable in the intensity of infection). In terms of methods, we found that the McMaster technique provided more repeatable estimates than the mini-FLOTAC for S. amaculata eggs, and both techniques were largely equally suitable for Isospora oocysts. Our study shows that field samples are likely to be unreliable in accurately detecting the presence of parasites and, in particular, for estimating parasite loads in songbirds. We highlight important considerations for those designing host-parasite studies in captive or wild systems giving guidance that can help select suitable methods, minimize biases, and acknowledge possible limitations.

A Review of Non-Invasive Sampling in Wildlife Disease and Health Research: What's New?

In the last decades, wildlife diseases and the health status of animal populations have gained increasing attention from the scientific community as part of a One Health framework. Furthermore, the need for non-invasive sampling methods with a minimal impact on wildlife has become paramount in complying with modern ethical standards and regulations, and to collect high-quality and unbiased data. We analysed the publication trends on non-invasive sampling in wildlife health and disease research and offer a comprehensive review on the different samples that can be collected non-invasively. We retrieved 272 articles spanning from 1998 to 2021, with a rapid increase in number from 2010. Thirty-nine percent of the papers were focussed on diseases, 58% on other health-related topics, and 3% on both. Stress and other physiological parameters were the most addressed research topics, followed by viruses, helminths, and bacterial infections. Terrestrial mammals accounted for 75% of all publications, and faeces were the most widely used sample. Our review of the sampling materials and collection methods highlights that, although the use of some types of samples for specific applications is now consolidated, others are perhaps still underutilised and new technologies may offer future opportunities for an even wider use of non-invasively collected samples.

Femtosecond Thermal and Nonthermal Hot Electron Tunneling Inside a Photoexcited Tunnel Junction.

Efficient operation of electronic nanodevices at ultrafast speeds requires understanding and control of the currents generated by femtosecond bursts of light. Ultrafast laser-induced currents in metallic nanojunctions can originate from photoassisted hot electron tunneling or lightwave-induced tunneling. Both processes can drive localized photocurrents inside a scanning tunneling microscope (STM) on femto- to attosecond time scales, enabling ultrafast STM with atomic spatial resolution. Femtosecond laser excitation of a metallic nanojunction, however, also leads to the formation of a transient thermalized electron distribution, but the tunneling of thermalized hot electrons on time scales faster than electron-lattice equilibration is not well understood. Here, we investigate ultrafast electronic heating and transient thermionic tunneling inside a metallic photoexcited tunnel junction and its role in the generation of ultrafast photocurrents in STM. Phase-resolved sampling of broadband terahertz (THz) pulses via the THz-field-induced modulation of ultrafast photocurrents allows us to probe the electronic temperature evolution inside the STM tip and to observe the competition between instantaneous and delayed tunneling due to nonthermal and thermal hot electron distributions in real time. Our results reveal the pronounced nonthermal character of photoinduced hot electron tunneling and provide a detailed microscopic understanding of hot electron dynamics inside a laser-excited tunnel junction.

Preservation of vapor samples on adsorbent alumina capillaries and implications for field sampling.

Dynamic vapor microextraction (DVME) is a vapor preconcentration method that employs a capillary trap coated with an adsorbent, followed by solvent elution to recover the sample. DVME has been developed for applications in the laboratory, including highly precise vapor pressure measurements, and in the field. When vapor collection is conducted outside the laboratory, samples must almost always undergo some interval of storage representing the time between collection and analysis. This interval may be hours, days, or longer, depending on the situation. Regardless, in all situations there must be confidence that the integrity of the samples is maintained until processing and analysis. In this paper, we present results of two studies that tested the stability of a 50% weathered gasoline headspace sample on alumina PLOT (porous layer open tubular) capillaries stored at room temperature for periods from 24 h up to 20 wk. We used principal component analysis (PCA) to reduce the dimensionality of the chromatographic and mass spectral data and elucidate trends in stability with respect to the complex sample's range of hydrocarbon classes and molecular weights. Both analyses identified changes over storage periods of six weeks or more. The hydrocarbon class analysis, which used selected ion monitoring (SIM) data as input, proved more sensitive to changes over shorter storage periods. Sample integrity was preserved for at least 24 h, but losses, especially of high-volatility compounds, occurred by 168 h (7 d). Near total loss of sample occurred by 20 wk. These findings, which are specific to the sample, adsorbent, and storage conditions, will guide choices in experimental and instrumental design to ensure that data from future field studies is reliable.