Pesticides and Related Toxicants in the Atmosphere.

Pesticides and other toxicants released into the environment can contaminate air, water, soil, and biota. This review focuses on sources, exposures, fate, analysis, and trends. The potential for exposures due to atmospheric transport and deposition of pesticides and related contaminants may pose risks to humans and wildlife. Emissions of chemicals to air are related to physicochemical properties (e.g., vapor pressure and chemical stability). Experimental design and computer-based modeling, as related to emissions and dispersion of pesticides along transects downwind from release sources, will be discussed using the example of pesticide volatilization and drift in California agriculture that results in the transport and deposition downwind to the Sierra Nevada mountains, where much work has been done to refine exposure data for use in risk assessment and management. Predictably, those chemicals found frequently in air are those used most extensively, have multiple emission sources, and resist degradation. Yet to be determined are definitive connections with adverse impacts to humans and wildlife, although the accumulating evidence suggests that endocrine disrupting chemicals, ChE inhibitors, and others warrant further attention. Steps that are being taken to limit emissions, such as in pest control and fuel combustion, offer promising opportunities for improving the quality of air and of the overall environment. Chemical degradation rates and products from trace organics in the air merit more attention, as do the potential for activation by photooxidation and bioaccumulation in food chains. The potential effect of climate change, on atmospheric processes affecting contaminant behavior, is an area ripe for further study.

California biomonitoring data: Comparison to NHANES and interpretation in a risk assessment context.

The California Environmental Biomonitoring Program (also known as Biomonitoring California) has been generating human biomonitoring data and releasing it via their website. The current Biomonitoring California program is a collection of smaller studies, targeting specific populations (e.g., fire fighters, breast cancer patients and controls, etc.). In this paper we compare the results from Biomonitoring California with those from the US National Health and Nutrition Examination Survey (NHANES). We also compare California's results with Biomonitoring Equivalents (BEs) for those compounds for which BEs exist. In general, the results from California are consistent with the biomonitoring levels found across the US via NHANES. A few notable exceptions are levels of flame retardants amongst fire fighters in California, which are higher than observed in NHANES and some persistent organic chemicals amongst a study of breast cancer patients and controls in California which are higher than in the overall adult population in NHANES. The higher levels amongst fire fighters may be a result of fire fighters being exposed to higher levels of flame retardants while fighting fires. The higher levels of the persistent organics amongst breast cancer patients is likely due to this population being older than the mean age in NHANES. Comparisons to BEs indicate that biomonitoring levels in California are all consistently below levels of concern as established by regulatory agencies.

Fumio Matsumura--accomplishments at the University of California, Davis, and in the Sierra Nevada Mountains.

Fumio Matsumura joined the University of California, Davis, faculty in 1987 where he served as founding director of the Center for Environmental Health Sciences, associate director of the U.C. Toxic Substances Research and Teaching Program, and chair of the Department of Environmental Toxicology. He was an active affiliate with the NIEHS-funded Superfund Basic Research Program and the NIH Comprehensive Cancer Center. He was in many instances a primary driver or otherwise involved in most activities related to environmental toxicology at Davis, including the education of students in environmental biochemistry and ecotoxicology. A significant part of his broad research program was focused on the long range transport of chemicals such as toxaphene, PCBs and related contaminants used or released in California to the Sierra Nevada mountains, downwind of the urban and agricultural regions of the state. He hypothesized that these chemical residues adversely affected fish and wildlife, and particularly the declining populations of amphibians in Sierra Nevada streams and lakes. Fumio and his students and colleagues found residues of toxaphene and PCBs at higher elevations, an apparent result of atmospheric drift and deposition in the mountains. Fumio and his wife Teruko had personal interests in, and a love of the mountains, as avid skiers, hikers, and outdoor enthusiasts.

Agricultural chemistry and bioenergy.

Renewed interest in converting biomass to biofuels such as ethanol, other forms of bioenergy, and bioenergy byproducts or coproducts of commercial value opens opportunities for chemists, including agricultural chemists and related disciplines. Applications include feedstock characterization and quantification of structural changes resulting from genetic modification and of the intermediates formed during enzymatic and chemical processing; development of improved processes for utilizing chemical coproducts such as lactic acid and glycerol; development of alternative biofuels such as methanol, butanol, and hydrogen; and ways to reduce greenhouse gas emission and/or use carbon dioxide beneficially. Chemists will also be heavily involved in detailing the phytochemical composition of alternative energy crops and genetically improved crops. A resurgence of demand for agricultural chemistry and related disciplines argues for increasing output through targeted programs and on-the-job training.

Acrylamide release resulting from sunlight irradiation of aqueous polyacrylamide/iron mixtures.

Linear anionic polyacrylamide (PAM) has been used in irrigation practices as a flocculating agent to minimize water losses through seepage in earthen canals. The stability of PAM is of concern because of the possibility of acrylamide (AMD) monomer release during environmental weathering. Aqueous solutions of commercial PAM mixed with ferric sulfate, subjected to simulated and natural sunlight irradiation, showed polymer chain scission and release of the AMD monomer. At acid/neutral pH, the amount of AMD released was directly related to the concentration of ferric ion and the irradiation time. At alkaline pH (approximately 8), PAM/Fe(3+) mixtures were stable under irradiation. PAM chain scission involved the hydroxyl radical, but specific AMD release appeared to require PAM-bound iron. Low iron concentrations and alkaline pH of irrigation water would limit AMD release. Residual monomer in PAM can contribute AMD to irrigation water, but concentrations would remain below the U.S. EPA drinking water standard of 0.5 ppb.

Applications of metabolomics in agriculture.

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.

13th IUPAC International Congress of Pesticide Chemistry: Crop, Environment, and Public Health Protection, Technologies for a Changing World.

This introductory paper provides an overview of Perspectives papers written by plenary speakers from the 13th IUPAC International Congress of Pesticide Chemistry held in San Francisco, CA, USA, in August 2014. This group of papers emphasizes some of the emerging issues and challenges at the forefront of agricultural research: sustainability; agriculture's response to climate change and population growth; pollinator health and risk assessment; and global food production and food security. In addition, as part of the Congress, a workshop on "Developing Global Leaders for Research, Regulation, and Stewardship of Crop Protection Chemistry in the 21st Century" identified specific recommendations to attract the best scientists to agricultural science, to provide opportunities to study and conduct research on crop protection chemistry topics, and to improve science communication skills.

Environmental behavior and analysis of agricultural sulfur.

Sulfur has been widely used for centuries as a staple for pest and disease management in agriculture. Presently, it is the largest-volume pesticide in use worldwide. This review describes the sources and recovery methods for sulfur, its allotropic forms and properties and its agricultural uses, including development and potential advantages of nanosulfur as a fungicide. Chemical and microbial reactivity, interactions in soil and water and analytical methods for determination in environmental samples and foodstuffs, including inexpensive analytical methods for sulfur residues in wine, beer and other food/beverage substrates, will be reviewed. The toxicology of sulfur towards humans and agriculturally important fungi is included, with some restrictions on use to promote safety. The review concludes with areas for which more research is warranted.

The nexus of food, energy, and water.

The Earth's population is expected to exceed 9 billion by 2050, posing significant challenges in meeting human needs while minimally affecting the environment. To support this population, we will need secure and safe sources of food, energy, and water. The nexus of food, energy, and water is one of the most complex, yet critical, issues that face society. There is no more land to exploit, and the supply of fresh water in some areas of the world limits the use of land for food. All solutions must also deal with the overlay of global climate change. Meeting current and future populations needs will require security in food, energy, and water supplies. A nexus approach is needed to improve food, energy, and water security integrating the management of the limited resources while transitioning to a more "green" economy, which provides adequate food, energy, and water for the expanding human population.

Biopesticides: state of the art and future opportunities.

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.

Determination of toxic α-dicarbonyl compounds, glyoxal, methylglyoxal, and diacetyl, released to the headspace of lipid commodities upon heat treatment.

Toxic α-dicarbonyl compounds, glyoxal, 2-methylglyoxal, and diacetyl, released from the headspace from butter, margarine, safflower oil, beef fat, and cheese heated at 100 and 200 °C were analyzed by gas chromatography as quinoxaline derivatives. Total amounts of α-dicarbonyl compounds ranged from 40.5 ng/g (butter) to 331.2 ng/g (beef fat) at 100 °C and from 302.4 ng/g (safflower oil) to 4521.5 ng/g (margarine) at 200 °C. The total amount of α-dicarbonyl compounds increased approximately 55- and 15-fold in the headspace of heated butter and margarine, respectively, when the temperature was increased from 100 to 200 °C. However, only slight differences associated with temperature variation were observed in the cases of safflower oil and beef fat (1.3- and 1.1-fold, respectively). Diacetyl was found in the highest amounts among all samples, ranging from 13.9 ± 0.3 ng/g (butter) to 2835.7 ng/g (cheese) at 100 °C and from 112.5 ± 102 ng/g (safflower oil) to 2274.5 ± 442.6 ng/g (margarine) at 200 °C, followed by methylglyoxal, ranging from 13.0 ± 0.5 to 112.7 ± 10.1 ng/g (cheese) at 100 °C and from 34.7 ± 5.0 ng/g (safflower oil) to 1790 ± 372.3 ng/g (margarine) at 200 °C. Much less glyoxal formed, in amounts ranging from 13.6 ± 0.7 ng/g (butter) to 53.4 ± 11.2 ng/g (beef fat) at both temperatures. The amounts of α-dicarbonyl compounds released into the vapor phase from lipid commodities during heating were satisfactorily analyzed.

Perspectives on communicating risks of chemicals.

The Agrochemicals Division symposium "Perfecting Communication of Chemical Risk", held at the 244th National Meeting and Exposition of the American Chemical Society in Philadelphia, PA, August 19-23, 2012, is summarized. The symposium, organized by James Seiber, Kevin Armbrust, John Johnston, Ivan Kennedy, Thomas Potter, and Keith Solomon, included discussion of better techniques for communicating risks, lessons from past experiences, and case studies, together with proposals to improve these techniques and their communication to the public as effective information. The case studies included risks of agricultural biotechnology, an organoarsenical (Roxarsone) in animal feed, petroleum spill-derived contamination of seafood, role of biomonitoring and other exposure assessment techniques, soil fumigants, implications of listing endosulfan as a persistant organic pollutant (POP), and diuron herbicide in runoff, including use of catchment basins to limit runoff to coastal ecozones and the Great Barrier Reef. The symposium attracted chemical risk managers including ecotoxicologists, environmental chemists, agrochemists, ecosystem managers, and regulators needing better techniques that could feed into better communication of chemical risks. Policy issues related to regulation of chemical safety as well as the role of international conventions were also presented. The symposium was broadcast via webinar to an audience outside the ACS Meeting venue.

From detrimental to beneficial constituents in foods: tracking the publication trends in JAFC.

A large part of the research focus on food constituents in the 20th century was toward health-detrimental contaminants-pathogens, toxins, chemical residues, and some food additives. This is reflected in the publications in the Journal of Agricultural and Food Chemistry and other journals. This era witnessed the formation of the U.S. Food and Drug Administration (FDA) and Environmental Protection Agency (EPA) and the rise and fall of DDT and other synthetic chemicals, as well as a number of artificial sweeteners, preservatives, and coloring/flavoring agents that attracted consumer and government attention. During the past 25 years or so, the emphasis in food chemistry and biochemistry has trended more toward health-beneficial chemicals in foods, as their examination yields information on naturally occurring components-polyphenolic antioxidants, unsaturated fatty acids, soluble fibers, and many other classes of constituents that may ward off chronic diseases. This perspective addresses the changes in emphases in published research to the present and trends that indicate the directions that food chemistry/biochemistry and related sciences might follow in the future.

Contributions of pesticide residue chemistry to improving food and environmental safety: past and present accomplishments and future challenges.

The principles of modern pesticide residue chemistry were articulated in the 1950s. Early authors pointed out the advantages of systematizing and standardizing analytical methods for pesticides so that they could be widely practiced and the results could be reproduced from one laboratory to the next. The availability of improved methods has led to a much more complete understanding of pesticide behavior and fate in foods and the environment. Using methods based largely upon gas chromatography (GC) and high-performance liquid chromatography (HPLC) coupled increasingly with mass spectrometry (MS) and MS(n) as the detection tool, residues can be measured at parts per billion levels and below in a variety of food and environmental matrices. Development of efficient extraction and cleanup methods, techniques such as ELISA, efficient sample preparation techniques such as QuEChERS, and automated laboratory and field instrumentation has also contributed to the tools available for use in modern pesticide residue analysis. As a result, great strides have been made in improving food and worker safety and in understanding environmental behavior and fate of pesticides. There are many challenges remaining in the field of pesticide residue chemistry that will continue to stimulate analytical chemists. New chemistries are emerging, often patterned on complex natural products. Analyzing for the parent chemicals and potentially multiple breakdown products will require analytical ingenuity. The development of more sensitive bioassays and knowledge of unintended side effects will challenge residue chemistry as well, as in the case of following the fate of environmental endocrine disruptors associated with some pesticides as well as nonpesticide contaminants from packaging materials and other familiar articles. Continued funding and other resources to ensure better training, international cooperation, and accelerated research and development activities will be a constant need in pesticide residue chemistry as it is for all areas of science that aim to mitigate or eliminate contaminants that can affect human and environmental health and safety.

Correlation to estimate emission rates for soil-applied fumigants.

The emission rates [ER (µg m⁻² s⁻¹)] for subsurface injections and surface chemigations for 15 fumigant applications were combined with the physicochemical properties of the fumigants [vapor pressure, VP (Pa); water solubility, S(w) (mg L⁻¹); soil adsorption coefficient, K(oc) (mL g⁻¹)] and with application conditions [application rate, AR (kg ha⁻¹); depth of application, d (cm)]. This resulted in the regression Ln ER = 3.598 + 0.9400 Ln R [R = (VP × AR)/(S(w) × K(oc) × d)], which can be used to estimate emissions for new applications. Emission rates derived from the linear correlation were used as input to an atmospheric dispersion model to estimate concentrations of fumigants in air at various downwind distances, and the results were compared with concentration values measured in the field near sources. The fumigant correlation along with an atmospheric dispersion model can be used as a rapid screening method by regulatory and enforcement agencies for exposure and risk assessment.