Multiresidue analysis of organophosphate and pyrethroid pesticides in duplicate-diet solid food by pressurized liquid extraction

An analytical method was developed for determining organophosphate pesticides (OPP) and pyrethroid pesticides (PYR) in duplicate-diet solid food. The method consisted of pressurized liquid extraction (PLE) with dichloromethane followed by cleanup with gel permeation and solid phase extraction columns and gas chromatography/mass spectrometry (GC/MS) analysis. Quantitative recoveries (73-117 %) of the target pesticides were obtained for spiked duplicate-diet food samples. The percent standard deviation (% RSD) of replicate food samples was within ± 20 %. Another method was developed for determining a common OPP metabolite, 3, 5, 6-trichloro-2-pyridinol (TCP) in duplicate-diet food. The method consisted of a PLE with methanol followed by liquid-liquid partitioning, derivatization, and GC/MS analysis. Recoveries of TCP ranged from 83 to 101 % for spiked duplicate-diet food samples. The % RSD of replicate food samples was within ± 15 %. The results confirmed that these methods are reliable and robust, and that they can be used in routine analysis. In addition, a storage stability study for a common OPP, chlorpyrifos (CPF), in solid food samples was performed. The fortified (15)N-(13)C-labeled CPF was stable over 16 mo storage at -20° C in the dark. The developed analytical methods were successfully applied to 278 duplicate-diet food samples from preschool children, demonstrating that these methods are robust and suitable for routine analysis in future exposure monitoring studies.     

Improvements to TCE Microcosm Protocols for Biostimulation in Bedrock Aquifers

In this study, a factorial‐designed experiment of biostimulated trichloroethene (TCE) dechlorination in fractured bedrock aquifers using microcosms evaluated several potential biostimulants (i.e., nutrients, vitamins, and sterile groundwater). Substantial cost savings and resource efficiency can be provided by this approach because: factorial designs require relatively few microcosms per factor; the interpretation of the observations can proceed largely by common sense, simple arithmetic, and computer graphics; the observations can indicate promising directions for further experimentation and causative relationships; and designs can be suitably augmented when a more in‐depth exploration is needed. TCE degradation was evaluated using three methods of data analysis: (1) analysis of covariance (ANCOVA) between biotic and abiotic treatment trend‐line slopes; (2) calculation of biodegradation half‐life; and (3) effects screening by model fitting. Microcosm preparation with crushed rock in groundwater was found to more closely match the previously observed field rates than the preparation with only groundwater. Injection of nutrient and vitamin mixtures was made into microcosms that were previously aged to obtain consistent conditions, and the TCE concentration measured after incubating for 45 days. Comparison of results indicated that the nutrient mixture slows or inhibits the degradation of TCE compared to the sterile groundwater; however, the vitamin mixture offsets and nearly compensates for the inhibitory effect of the nutrient mixture. It is recommended that this factorial experiment be augmented with additional studies of individual or groups of compounds from the vitamin mixture using this methodology to isolate and identify the specific factor or interaction responsible for the inhibitory compensation. © 2013 Wiley Periodicals, Inc.     

Diplomacy for science: strategies to promote international collaboration

Technology innovation is an increasingly globalized exercise with dramatic consequences for scientific and diplomatic goals alike, and requires enhanced participation and integration of scientists and science-minded diplomats within diplomatic missions to advance shared policy goals. This more general problem is addressed in the present article by focusing on recent collaborations between U.S. and German scientists, including several of the coauthors.     

Is an assessment factor of 10 appropriate to account for the variation in chemical toxicity to freshwater ectotherms under different thermal conditions?

Ecotoxicity tests are often conducted following standard methods, and thus carried out at a fixed water temperature under controlled laboratory conditions. Yet, toxicity of a chemical contaminant may vary in a temperature-dependent manner, depending on the physiology of the test organism and physicochemical properties of the chemical. Although an assessment factor of 10 (AF10) is commonly adopted to account for variability in toxicity data related to temperature in the development of water quality guidelines and/or ecological risk assessment, no one has ever rigorously assessed the appropriateness of AF10 to account for potential variation in temperature-dependent chemical toxicity to aquatic organisms. This study, therefore, aims to address this issue through a meta-analysis by comparing median lethal concentration data for nine chemicals (cadmium, copper, nickel, lead, silver, zinc, arsenic, selenium and DDT) on a range of freshwater ectothermic animal species at different temperatures, and to assess whether AF10 is under- or over-protective for tropical and temperate freshwater ecosystems. Our results reveal varying extents of interaction between temperature and different chemicals on organisms and the complexity of these interactions. Applying AF10 sufficiently protects 90 % of the animal species tested over a range of temperatures for cadmium, copper, nickel, silver, zinc and DDT in the tropics, but it is insufficient to adequately encompass a larger temperature variation for most studied chemicals in temperate regions. It is therefore important to set specific AFs for different climatic zones in order to achieve the desired level of ecosystem protection.     

Historical reconstruction of polychlorinated biphenyl (PCB) exposures for workers in a capacitor manufacturing plant

We developed a semiquantitative job exposure matrix (JEM) for workers exposed to polychlorinated biphenyls (PCBs) at a capacitor manufacturing plant from 1946 to 1977. In a recently updated mortality study, mortality of prostate and stomach cancer increased with increasing levels of cumulative exposure estimated with this JEM (trend p values?=?0.003 and 0.04, respectively). Capacitor manufacturing began with winding bales of foil and paper film, which were placed in a metal capacitor box (pre-assembly), and placed in a vacuum chamber for flood-filling (impregnation) with dielectric fluid (PCBs). Capacitors dripping with PCB residues were then transported to sealing stations where ports were soldered shut before degreasing, leak testing, and painting. Using a systematic approach, all 509 unique jobs identified in the work histories were rated by predetermined process- and plant-specific exposure determinants; then categorized based on the jobs’ similarities (combination of exposure determinants) into 35 job exposure categories. The job exposure categories were ranked followed by a qualitative PCB exposure rating (baseline, low, medium, and high) for inhalation and dermal intensity. Category differences in other chemical exposures (solvents, etc.) prevented further combining of categories. The mean of all available PCB concentrations (1975 and 1977) for jobs within each intensity rating was regarded as a representative value for that intensity level. Inhalation (in microgram per cubic milligram) and dermal (unitless) exposures were regarded as equally important. Intensity was frequency adjusted for jobs with continuous or intermittent PCB exposures. Era-modifying factors were applied to the earlier time periods (1946–1974) because exposures were considered to have been greater than in later eras (1975–1977). Such interpolations, extrapolations, and modifying factors may introduce non-differential misclassification; however, we do believe our rigorous method minimized misclassification, as shown by the significant exposure–response trends in the epidemiologic analysis.     

An assessment of the metabolic profile implied by agricultural change in two rural communities in the North of Argentina

The soy expansion model in Argentina generates structural changes in traditional lifestyles, which can be associated with different biophysical and socioeconomic impacts. To explore this issue, we apply an innovative method for integrated assessment—the multi-scale integrated analysis of societal and ecosystem metabolism framework—to characterize two communities in the Chaco Region, Province of Formosa, North of Argentina. These communities have recently experienced the expansion of soy production, altering their economic activity, energy consumption patterns, land use and human time allocation. The integrated characterization presented in the paper illustrates the differences (biophysical, socioeconomic and historical) between the two communities that can be associated with different responses. The analysis of the factors behind these differences has important policy implications for the sustainable development of local communities in the area.     

A classification and regression tree model of controls on dissolved inorganic nitrogen leaching from European forests

Often, there is a non-linear relationship between atmospheric dissolved inorganic nitrogen (DIN) input and DIN leaching that is poorly captured by existing models. We present the first application of the non-parametric classification and regression tree approach to evaluate the key environmental drivers controlling DIN leaching from European forests. DIN leaching was classified as low (<3), medium (3-15) or high (>15 kg N ha⁻¹ year⁻¹) at 215 sites across Europe. The analysis identified throughfall NO₃⁻ deposition, acid deposition, hydrology, soil type, the carbon content of the soil, and the legacy of historic N deposition as the dominant drivers of DIN leaching for these forests. Ninety four percent of sites were successfully classified into the appropriate leaching category. This approach shows promise for understanding complex ecosystem responses to a wide range of anthropogenic stressors as well as an improved method for identifying risk and targeting pollution mitigation strategies in forest ecosystems.     

Models for the field-based toxicity of copper and zinc salts to wheat in 11 Australian soils and comparison to laboratory-based models

Laboratory-based relationships that model the phytotoxicity of metals using soil properties have been developed. This paper presents the first field-based phytotoxicity relationships. Wheat (Triticum aestivum L.) was grown at 11 Australian field sites at which soil was spiked with copper (Cu) and zinc (Zn) salts. Toxicity was measured as inhibition of plant growth at 8 weeks and grain yield at harvest. The added Cu and Zn EC10 values for both endpoints ranged from approximately 3 to 4760 mg/kg. There were no relationships between field-based 8-week biomass and grain yield toxicity values for either metal. Cu toxicity was best modelled using pH and organic carbon content while Zn toxicity was best modelled using pH and the cation exchange capacity. The best relationships estimated toxicity within a factor of two of measured values. Laboratory-based phytotoxicity relationships could not accurately predict field-based phytotoxicity responses.     

Mapping Conflicts Between Biodiversity and Human Needs in Langtang National Park, Nepal

We mapped areas of congruence and conflict between the objectives of protecting red pandas ( Ailurus fulgens ) and meeting the claims and needs of people who live in and around Langtang National Park, Nepal. Semi-structured interviews were used to solicit information on land-use practices, and spatial information technology (sketch maps, satellite images, geographical information systems) was used to place these practices in a spatial context and to model the effects of grazing. Spatial information technology was useful for delineating areas where conflicts occur between the objectives of preserving biodiversity and meeting the needs of local residents. Despite the fact that villagers recognize pasture boundaries, rules and regulations govern pasture management, and sanctions are imposed on violators, over 60% of the red panda's habitat is heavily grazed, and all available land within the study site suitable for grazing is already being used. The study suggests that common property management of natural resources to protect biodiversity (i.e., red pandas) and meet the needs of local people at the same time will be difficult.     

Agrobiodiversity with emphasis on plant genetic resources

The science of agrobiodiversity has emerged during the last 10 years. We review here the most important aspects of biodiversity for conservation. One of the aims of agrobiodiversity research is to introduce or to re-introduce into present-day agriculture and horticulture more diversity from gene banks, botanical or zoological gardens, and other secondary sources of diversity. To enlarge the basis of agricultural and horticultural resources for human and animal nutrition, a sustainable use of these native and cultivated resources is necessary, including animal and plant genetic resources. The total number of botanical plant species cultivated as agricultural or horticultural crops is estimated at almost 7,000. However, only 30 major crop species "feed the world". Comparable numbers of animal species have been lost. The reduction in crop species and variety diversity, in particular, has led to the establishment of germplasm collections, so called gene banks, or ex situ collections. Six million plant accessions are conserved in gene banks worldwide. All these accessions belong to a very limited number of species. About half of them are advanced cultivars or breeders' lines, and only a third are landraces or old cultivars. Approximately 15% are wild relatives of crop species and weeds. Among other obvious gaps, minor crops and underutilized species are underrepresented in these collections, particularly primitive cultivars and wild relatives from the centers of origin, diversity, and cultivation. To date, only a third of all gene bank accessions have been fully characterized.