Performance of poly(vinyl alcohol) gel columns on the ion chromatographic determination of perchlorate in fertilizers

Interest in possible sources of perchlorate (ClO4) that could lead to environmental release has been heightened since the Environmental Protection Agency placed this anion on its Contaminant Candidate List for drinking water. Although recent investigations have suggested that fertilizers are minor contributors to environmental perchlorate contamination overall, there is still interest in screening commercial products for possible contamination and quantitating perchlorate when it is found. Ion chromatography (IC) has been used for this application owing to its speed, low detection limits, widespread availability, and moderate ruggedness relative to other techniques. However, fertilizer matrixes complicate the IC analysis relative to potable water matrixes. In this study, the performance of poly(vinyl alcohol) gel resin IC columns (100 mm and 150 mm) was evaluated for fertilizer matrixes using method EPA/600/R-01/026. The NaOH eluent included an organic salt, sodium 4-cyanophenoxide. Detection was by suppressed conductivity. A set of 55 different field samples representing 48 products and previously used by the EPA to assess occurrence of perchlorate in fertilizers (EPA/600/R-01/049) was reanalyzed on the 150 mm column. The 100 mm column was used to further investigate the positive hits. Both columns gave satisfactory performance in fertilizer matrixes, with spike recoveries (+/- 15%), assured reporting levels (0.5-225 microg g(-1) except for one at 1,000 microg g(-1)), accuracy (relative error < 30% always and most < 15%), and precision [injection-to-injection reproducibility < 3% relative standard deviation (RSD)] comparable to those reported in other studies. Performance did not vary substantially between column lengths. Lastly, the results of this investigation provided further evidence in support of the conclusions that had been reached previously by the EPA on the occurrence of perchlorate in fertilizers.     

Inferring chemical effects on carbon flows in aquatic food webs: Methodology and case study

The majority of ecotoxicological enclosure experiments monitor species abundances at different chemical concentrations. Here, we present a new modelling approach that estimates changes in food web flows from such data and show that population- and food web level effects are revealed that are not apparent from abundance data alone. For the case of cypermethrin in freshwater enclosures, photosynthesis and excretion (d⁻¹) of phytoplankton at 3.643 μg L⁻¹ cypermethrin were 30% lower and 100% higher than in the control, respectively. The ingestion rate of mesozooplankton (d⁻¹) was 6 times higher in the treated enclosures than in the control as food concentration increased with insecticide exposure. With increasing cypermethrin concentrations, nanoflagellates progressively relied on phytoplankton as their main food source, which rendered the food web less stable. We conclude that this tool has excellent potential to analyse the wealth of enclosure data as it only needs species abundance and general constraints.     

The relation between Acid Volatile Sulfides (AVS) and metal accumulation in aquatic invertebrates: Implications of feeding behavior and ecology

The present study evaluates the relationship between Acid Volatile Sulfides (AVS) and metal accumulation in invertebrates with different feeding behavior and ecological preferences. Natural sediments, pore water and surface water, together with benthic and epibenthic invertebrates were sampled at 28 Flemish lowland rivers. Different metals as well as metal binding sediment characteristics including AVS were measured and multiple regression was used to study their relationship with accumulated metals in the invertebrates taxa.Bioaccumulation in the benthic taxa was primarily influenced by total metal concentrations in the sediment. Regarding the epibenthic taxa metal accumulation was mostly explained by the more bioavailable metal fractions in both the sediment and the water. AVS concentrations were generally better correlated with metal accumulation in the epibenthic invertebrates, rather than with the benthic taxa. Our results indicated that the relation between AVS and metal accumulation in aquatic invertebrates is highly dependent on feeding behavior and ecology.     

Influence of uncertain reaction rates on ozone sensitivity to emissions

Air quality models rely upon simplified photochemical mechanisms to efficiently represent the thousands of chemical species that interact to form air pollution. Uncertainties in the chemical reaction rate constants and photolysis frequencies that comprise those mechanisms can generate uncertainty in the estimation of pollutant concentrations and their responsiveness to emission controls. A high-order sensitivity analysis technique is applied to quantify the extent to which reaction rate uncertainties influence estimates of ozone concentrations and their sensitivities to precursor emissions during an air pollution episode in Houston, Texas. Several reactions were found to have much larger proportional effects on ozone’s sensitivities to emissions than on its concentrations. In particular, uncertainties in photolysis frequencies and in the rate of reaction between NO₂ and OH to form nitric acid can significantly influence the magnitude and sign of peak ozone sensitivity to nitrogen oxide (NO_x) emissions. Ozone sensitivity to VOCs exhibits a much more muted response to uncertainties in the reaction rate constants and photolysis frequencies considered here. The results indicate the importance of accurate reaction rate constants to predicting the ozone impacts resulting from NO_x emission controls.     

Comparison of summer and winter California central valley aerosol distributions from lidar and MODIS measurements

Aerosol distributions from two aircraft lidar campaigns conducted in the California Central Valley are compared in order to identify seasonal variations. Aircraft lidar flights were conducted in June 2003 and February 2007. While the ground PM_2.5 (particulate matter with diameter ≤ 2.5 μm) concentration was highest in the winter, the aerosol optical depth (AOD) measured from the MODIS and lidar instruments was highest in the summer. A multiyear seasonal comparison shows that PM_2.5 in the winter can exceed summer PM_2.5 by 68%, while summer AOD from MODIS exceeds winter AOD by 29%. Warmer temperatures and wildfires in the summer produce elevated aerosol layers that are detected by satellite measurements, but not necessarily by surface particulate matter monitors. Temperature inversions, especially during the winter, contribute to higher PM_2.5 measurements at the surface. Measurements of the mixing layer height from lidar instruments provide valuable information needed to understand the correlation between satellite measurements of AOD and in situ measurements of PM_2.5. Lidar measurements also reflect the ammonium nitrate chemistry observed in the San Joaquin Valley, which may explain the discrepancy between the MODIS AOD and PM_2.5 measurements.     

Nitro-PAH formation studied by interacting artificially PAH-coated soot aerosol with NO2 in the temperature range of 295–523 K

Diesel particulate matter poses a threat to human health, and in particular nitrated polycyclic aromatic hydrocarbons (NPAHs) found within and on the surface of these particles. Although diesel particulate filters (DPFs) have been designed and implemented to reduce these and other harmful diesel emissions, the particle loaded filters may act as a reaction chamber for the enhanced production of NPAHs from the nitration of PAHs with NO₂.Focus is on the investigation of the heterogeneous reactions that occur on soot particles by exposing laboratory produced pyrene- or benzo(a)pyrene-coated spark discharge soot particles to varying concentrations of NO₂ and temperatures while following the formation of products over time. The sole nitration product that was observed throughout the experiments with pyrene-coated soot was 1-nitropyrene (1-NPYR), which increased linearly with reaction time for all NO₂ concentrations chosen (0.11, 1.0, 2.0, 4.0 ppm, m m^?1). Resulting 1-NPYR formation rate increased exponentially with [NO₂]. Throughout the 3-h experiments less than 10% of pyrene has been converted to 1-NPYR and the partial reaction order with regard to [NO₂] was estimated to 1.52. Benzo(a)pyrene (BaP) was more reactive than pyrene. After 3 h reaction time almost 80% of the BaP has been converted to 6-NBaP.Highest 1-NPYR concentrations on particles were detected at 373 K, and at higher temperatures a considerable decrease in particulate 1-NPYR was observed. A similar trend was observed in a DPF simulation system (PM-Kat^®-like) with BaP-coated soot. In this case, highest 6-NBaP concentration on particles was detected at 423 K. Backed by corroborating results from separate gas/solid-phase partition experiments with 1-NPYR and 6-NBaP, it is likely that the newly formed 1-NPYR and 6-NBaP became transferred from particle to gas phase at higher temperatures. Results from this study confirm the presence of 1-NPYR and 6-NBaP in particulate and gas phase under conditions encountered in DPFs, especially when operated at low temperature situations of the aftertreatment system.     

Enhancing corporate compliance with worksite safety and health legislation

Introduction: A 2-year prospective study evaluated the effectiveness of a managerial training program to enhance corporate compliance with statewide worksite safety and health regulations. The program offered participants information about regulatory requirements and emphasized organizational and environmental strategies for reducing occupational injuries and illnesses. Objectives: To assess the effects of a train-the-trainer program on business managers' knowledge of statewide occupational safety and health legislation and on levels of corporate compliance with regulatory requirements. Methods: Forty-eight small- and medium-sized companies participated in the training sessions during the first year of the study. These firms were compared with 46 control companies that did not receive the training until the conclusion of the study. Results: Participation in the program was associated with higher levels of corporate regulatory compliance 12 months after the training sessions were held (controlling for baseline levels of corporate compliance with the regulations). Program effects on compliance levels were mediated by posttraining changes in managers' knowledge of regulatory requirements. Conclusions: The REACH OUT training program raised managers' awareness of and corporate compliance with statewide worksite safety and health regulations. Impact on Industry: Smaller companies face greater challenges than larger ones in developing and maintaining worksite safety and health programs. Barriers to regulatory compliance, especially in small- and medium-size companies, should be identified and removed to enhance the efficacy of these programs.     

An Ecoregional Context for Forest Management on National Wildlife Refuges of the Upper Midwest,USA

To facilitate forest planning and management on National Wildlife Refuges, we synthesized multiple data sources to describe land ownership patterns, land cover, landscape pattern, and changes in forest composition for four ecoregions and their associated refuges of the Upper Midwest. We related observed patterns to ecological processes important for forest conservation and restoration, with specific attention to refuge patterns of importance for forest landbirds of conservation priority. The large amount of public land within the ecoregions (31–80%) suggests that opportunities exist for coarse and meso-scale approaches to conserving and restoring ecological processes affecting the refuges, particularly historical fire regimes. Forests dominate both ecoregions and refuges, but refuge forest patches are generally larger and more aggregated than in associated ecoregions. Broadleaf taxa have increased in dominance in the ecoregions and displaced fire-dependent taxa such as pine (Pinus spp.) and other coniferous species; these changes in forest composition have likely also affected refuge forests. Despite compositional changes, larger forest patches on refuges suggests that they may provide better habitat for area-sensitive forest landbirds of mature, compositionally diverse forests than surrounding lands if management continues to promote increased patch size. We reason that although fine-scale research and monitoring for species of conservation priority is important, broad scale (ecoregional) assessments provide crucial context for effective forest and wildlife management in protected areas.     

An energy systems view of sustainability: emergy evaluation of the San Luis Basin, Colorado

Energy Systems Theory (EST) provides a framework for understanding and interpreting sustainability. EST implies that "what is sustainable" for a system at any given level of organization is determined by the cycles of change originating in the next larger system and within the system of concern. The pulsing paradigm explains the ubiquitous cycles of change that apparently govern ecosystems, rather than succession to a steady state that is then sustainable. Therefore, to make robust decisions among environmental policies and alternatives, decision-makers need to know where their system resides in the cycles of change that govern it. This theory was examined by performing an emergy evaluation of the sustainability of a regional system, the San Luis Basin (SLB), CO. By 1980, the SLB contained a climax stage agricultural system with well-developed crop and livestock production along with food and animal waste processing. The SLB is also a hinterland in that it exports raw materials and primary products (exploitation stage) to more developed areas. Emergy indices calculated for the SLB from 1995 to 2005 revealed changes in the relative sustainability of the system over this time. The sustainability of the region as indicated by the renewable emergy used as a percent of total use declined 4%, whereas, the renewable carrying capacity declined 6% over this time. The Emergy Sustainability Index (ESI) showed the largest decline (27%) in the sustainability of the region. The total emergy used by the SLB, a measure of system well-being, was fairly stable (CV?=?0.05). In 1997, using renewable emergy alone, the SLB could support 50.7% of its population at the current standard of living, while under similar conditions the U.S. could support only 4.8% of its population. In contrast to other indices of sustainability, a new index, the Emergy Sustainable Use Index (ESUI), which considers the benefits gained by the larger system compared to the potential for local environmental damage, increased 34% over the period.     

Diverging response patterns of terrestrial and aquatic species to hydromorphological restoration

Although experiences with ecological restoration continue to accumulate, the effectiveness of restoration for biota remains debated. We complemented a traditional taxonomic analysis approach with information on 56 species traits to uncover the responses of 3 aquatic (fish, macroinvertebrates, macrophytes) and 2 terrestrial (carabid beetles, floodplain vegetation) biotic groups to 43 hydromorphological river restoration projects in Germany. All taxonomic groups responded positively to restoration, as shown by increased taxonomic richness (10–164%) and trait diversity (habitat, dispersal and mobility, size, form, life history, and feeding groups) (15–120%). Responses, however, were stronger for terrestrial than aquatic biota, and, contrary to our expectation, taxonomic responses were stronger than those of traits. Nevertheless, trait analysis provided mechanistic insights into the drivers of community change following restoration. Trait analysis for terrestrial biota indicated restoration success was likely enhanced by lateral connectivity and reestablishment of dynamic processes in the floodplain. The weaker response of aquatic biota suggests recovery was hindered by the persistence of stressors in the aquatic environment, such as degraded water quality, dispersal constraints, and insufficient hydromorphological change. Therefore, river restoration requires combined local- and regional-scale approaches to maximize the response of both aquatic and terrestrial organisms. Due to the contrasting responses of aquatic and terrestrial biota, the planning and assessment of river restoration outcomes should consider effects on both components of riverine landscapes.