A robust HS-SPME and GC/MS method was developed for analyzing the composition of volatiles in raw and dry-roasted almonds. Almonds were analyzed directly as ground almonds extracted at room temperature. In total, 58 volatiles were identified in raw and roasted almonds. Straight chain aldehydes and alcohols demonstrated significant but minimal increases, while the levels of branch-chain aldehydes, alcohols, heterocyclic and sulfur containing compounds increased significantly (500-fold) in response to roasting (p<0.05). Benzaldehyde decreased from 2934.6±272.5 ng/g (raw almonds) to 315.8±70.0 ng/g (averaged across the roasting treatments evaluated i.e. 28, 33 and 38 min at 138 °C) after roasting. Pyrazines were detected in only the roasted almonds, with the exception of 2,5-dimethylpyrazine, which was also found in raw almonds. The concentration of most alcohols increased in the roasted samples with the exception of 2-methyl-1-propanol, 3-methyl-1-butanol and 2-phenylethyl alcohol, which decreased 68%, 80%, and 86%, respectively.

Biological systems are exceedingly complex. The unraveling of the genome in plants and humans revealed fewer than the anticipated number of genes. Therefore, other processes such as the regulation of gene expression, the action of gene products, and the metabolic networks resulting from catalytic proteins must make fundamental contributions to the remarkable diversity inherent in living systems. Metabolomics is a relatively new approach aimed at improved understanding of these metabolic networks and the subsequent biochemical composition of plants and other biological organisms. Analytical tools within metabolomics including mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy can profile the impact of time, stress, nutritional status, and environmental perturbation on hundreds of metabolites simultaneously resulting in massive, complex data sets. This information, in combination with transcriptomics and proteomics, has the potential to generate a more complete picture of the composition of food and feed products, to optimize crop trait development, and to enhance diet and health. Selected presentations from an American Chemical Society symposium held in March 2005 have been assembled to highlight the emerging application of metabolomics in agriculture.

Abstract-Agricultural activity in California's Central Valley may be an important source of pesticides that are transported in the air to the Sierra Nevada Mountain Range, USA. Pesticides applied to this intensive crop production area may volatilize under warm temperatures typical of the valley and be transported through the atmosphere to be deposited in the cooler, higher elevation regions of the Sierra Nevada Mountains. To determine the extent of summertime atmospheric transport of pesticides to this region, highvolume air, dry deposition, and surface water samples were collected in the Central Valley and at different elevations in California's Sequoia National Park. Results revealed that the highest residue concentrations were those of compounds with heavy summertime agricultural use. A significant drop in pesticide concentrations in both air and water samples was observed within a few 100-m elevation from the valley; however, levels remained relatively constant between ϳ500 and 2,000 m. Water concentrations from two areas above 3,000 m contained levels less than a tenth as high as those at lower elevations. Possible effects of the pesticides were estimated using measured water concentrations to calculate total exposure of three aquatic species to organophosphate insecticides. Aggregate exposure calculations showed concentrations were well below 96-h LC50 values for rainbow trout and stonefly but concentrations may be harmful to amphipods.

Abstract-Atmospheric inputs of pesticides transported from California's Central Valley to the Sierra Nevada mountains (California, USA) were investigated by collecting winter-spring precipitation (rain and snow) from Sequoia National Park and from the Lake Tahoe basin. Pesticides currently used in California's Central Valley were detected in snow and rain samples from two elevations in Sequoia National Park (SNP) in the southern Sierras. At the lower elevation site (533 m), chlorothalonil was present at the highest levels (Ͻ0.4-85 ng/L), followed by malathion (Ͻ0.046-24 ng/L), diazinon (Ͻ0.21-19 ng/L), and chlorpyrifos (1.3-4.4 ng/ L). At 1,920 m elevation, chlorothalonil was also present at the highest levels (Ͻ0.57-13 ng/L) followed by diazinon (Ͻ0.057-14 ng/L), chlorpyrifos (1.1-13 ng/L), and malathion (Ͻ0.045-6 ng/L). Trifluralin, ␣-and ␥-hexachlorocyclohexane (HCH), and ␣-and ␤-endosulfan were also detected at both locations and at lower concentrations, generally ranging from 0.5 to 2 ng/L. In the Lake Tahoe basin, elevation 2,200 m, malathion was also found in snow at concentrations ranging from Ͻ0.046 to 18 ng/L, as was diazinon (Ͻ0.057-7 ng/L), chlorpyrifos (0.30-3.4 ng/L), and chlorothalonil (0.66-1.7 ng/L). Chlorothalonil, chlorpryifos, ␣-and ␥-HCH, and ␣-endosulfan were found in surface and deep water samples at two locations in Lake Tahoe and at concentrations similar to those found in snow within the lake basin. Lake Tahoe basin snow samples in general had lower concentrations than those from SNP. This difference in concentration levels reflects the closer proximity of downwind pesticide usage to SNP than the Lake Tahoe basin. An estimated annual loading of one chemical, chlorpyrifos, of 24 to 31 kg/year was made for the SNP land area. Comparisons of observed concentrations were made with reported aquatic toxicity and water criteria levels.

The use of biopesticides and related alternative management products is increasing. New tools, including semiochemicals and plant-incorporated protectants (PIPs), as well as botanical and microbially derived chemicals, are playing an increasing role in pest management, along with plant and animal genetics, biological control, cultural methods, and newer synthetics. The goal of this Perspective is to highlight promising new biopesticide research and development (R&D), based upon recently published work and that presented in the American Chemical Society (ACS) symposium "Biopesticides: State of the Art and Future Opportunities," as well as the authors' own perspectives. Although the focus is on biopesticides, included in this Perspective is progress with products exhibiting similar characteristics, namely those naturally occurring or derived from natural products. These are target specific, of low toxicity to nontarget organisms, reduced in persistence in the environment, and potentially usable in organic agriculture. Progress is being made, illustrated by the number of biopesticides and related products in the registration pipeline, yet major commercial opportunities exist for new bioherbicides and bionematicides, in part occasioned by the emergence of weeds resistant to glyphosate and the phase-out of methyl bromide. The emergence of entrepreneurial start-up companies, the U.S. Environmental Protection Agency (EPA) fast track for biopesticides, and the availability of funding for registration-related R&D for biorational pesticides through the U.S. IR-4 program provide incentives for biopesticide development, but an expanded effort is warranted both in the United States and worldwide to support this relatively nascent industry. ABSTRACT: The use of biopesticides and related alternative management products is increasing. New tools, including semiochemicals and plant-incorporated protectants (PIPs), as well as botanical and microbially derived chemicals, are playing an increasing role in pest management, along with plant and animal genetics, biological control, cultural methods, and newer synthetics. The goal of this Perspective is to highlight promising new biopesticide research and development (R&D), based upon recently published work and that presented in the American Chemical Society (ACS) symposium "Biopesticides: State of the Art and Future Opportunities," as well as the authors' own perspectives. Although the focus is on biopesticides, included in this Perspective is progress with products exhibiting similar characteristics, namely those naturally occurring or derived from natural products. These are target specific, of low toxicity to nontarget organisms, reduced in persistence in the environment, and potentially usable in organic agriculture. Progress is being made, illustrated by the number of biopesticides and related products in the registration pipeline, yet major commercial opportunities exist for new bioherbicides and bionematicides, in part occasioned by the emergence of weeds resistant to ...

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The discovery of the very acidic nature of fog and clouds has created much interest in sampling, analysing, and elucidating the chemistry of fog, principally because an understanding of the chemical transformations leading to acid fog may provide important clues to the origin of acid rain. Recently, the knowledge of the chemistry of fog has expanded to include carbonyl compounds, volatile organic acids, and alkyl sulphonates. We have discovered that a variety of pesticides and their toxic alteration products are present in fog, and that they occasionally reach high concentrations relative to reported rainwater concentrations. In our experiments, we were able to measure the air-water distribution coefficients of pesticides between the liquid fog and the interstitial gas phase. These measurements reveal that some chemicals are enriched several thousandfold in the suspended liquid fog droplets compared to equilibrium distributions expected from Henry's Law coefficients for pure aqueous solutions.

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