Linking ground-water age and chemistry data along flow paths: implications for trends and transformations of nitrate and pesticides

Tracer-based ground-water ages, along with the concentrations of pesticides, nitrogen species, and other redox-active constituents, were used to evaluate the trends and transformations of agricultural chemicals along flow paths in diverse hydrogeologic settings. A range of conditions affecting the transformation of nitrate and pesticides (e.g., thickness of unsaturated zone, redox conditions) was examined at study sites in Georgia, North Carolina, Wisconsin, and California. Deethylatrazine (DEA), a transformation product of atrazine, was typically present at concentrations higher than those of atrazine at study sites with thick unsaturated zones but not at sites with thin unsaturated zones. Furthermore, the fraction of atrazine plus DEA that was present as DEA did not increase as a function of ground-water age. These findings suggest that atrazine degradation occurs primarily in the unsaturated zone with little or no degradation in the saturated zone. Similar observations were also made for metolachlor and alachlor. The fraction of the initial nitrate concentration found as excess N2 (N2 derived from denitrification) increased with ground-water age only at the North Carolina site, where oxic conditions were generally limited to the top 5 m of saturated thickness. Historical trends in fluxes to ground water were evaluated by relating the times of recharge of ground-water samples, estimated using chlorofluorocarbon concentrations, with concentrations of the parent compound at the time of recharge, estimated by summing the molar concentrations of the parent compound and its transformation products in the age-dated sample. Using this approach, nitrate concentrations were estimated to have increased markedly from 1960 to the present at all study sites. Trends in concentrations of atrazine, metolachlor, alachlor, and their degradates were related to the timing of introduction and use of these compounds. Degradates, and to a lesser extent parent compounds, were detected in ground water dating back to the time these compounds were introduced.     

Gas chromatographic methods for monitoring of wastewater chlorophenol degradation in anaerobic reactors

Wastewater samples from an anaerobic reactor were extracted with hexane and derivatized with diazomethane (method 1) and with acetic anidride (method 2). Gas chromatography with electron-capture detection (ECD) was employed for separating the parent compound and intermediates trichlorophenols (TCP) and dichlorophenols (DCP) which originated from the penta chlorophenol (PCP) degradation process. The relations between concentrations of PCP, TCP and DCP areas were linear in the range of concentrations of 0.2 to 8 mg/L and 0.025 mg/L to 5 mg/L for methods 1 and 2, respectively. The repeatability of the extraction methods was satisfactory, with variation coefficients lower than 11%. For method 1, at the fortification level of 0.2 mg/L, recovery of PCP, TCP, and DCP was 112%, 74% and 45%, respectively. For method 2, the corresponding recovery values at the fortification level of 0.1 mg/L were 91%, 93% and 103%, respectively. Storage of the frozen samples did not alter their PCP determination properties. The chromatographic methods adapted for chlorophenol determination in wastewater were suitable with relatively simple manipulation techniques. The obtained results were reproducible and allowed identification of intermediates formed during the PCP degradation process.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.     

Effects of repeated exposure to malathion on growth, food consumption, and locomotor performance of the western fence lizard (Sceloporus occidentalis)

Effects of repeated pollutant exposure on growth, locomotor performance, and behavior have rarely been evaluated in reptiles. We administered three doses of malathion (2.0, 20, or 100mg/kg body weight) to western fence lizards (Sceloporus occidentalis) over an 81day period. Eight and 23% mortality occurred at 20 and 100mg/kg (p=0.079) and 85% of lizards in the 100mg/kg group exhibited clinical symptoms of poisoning. Growth, food consumption, body condition index, and terrestrial locomotor performance were not significantly influenced by malathion. However, arboreal sprint velocity was significantly reduced in lizards receiving 100mg/kg. Fifty percent of lizards in the 100mg/kg group also refused to sprint in the arboreal setting (p=0.085). Based on these results, arboreal locomotor performance was the most sensitive metric of exposure we evaluated. Further study of compounds such as malathion is warranted due to highly variable application rates and exposure scenarios.     

Validation of evacuated canisters for sampling volatile organic compounds in healthcare settings

Healthcare settings present a challenging environment for assessing low-level concentrations of specific volatile organic compounds (VOCs) in the presence of high background concentrations of alcohol from the use of hand sanitizers and surface disinfectants. The purposes of this laboratory-based project were to develop and validate a sampling and analysis methodology for quantifying low-level VOC concentrations as well as high-level alcohol concentrations found together in healthcare settings. Sampling was conducted using evacuated canisters lined with fused silica. Gas chromatography/mass spectrometry analysis was performed using preconcentration (for ppb levels) and loop injection (for ppm levels). For a select list of 14 VOCs, bias, precision, and accuracy of both the preconcentration and loop injection methods were evaluated, as was analyte stability in evacuated canisters over 30 days. Using the preconcentration (ppb-level) method, all validation criteria were met for 13 of the 14 target analytes-ethanol, acetone, methylene chloride, hexane, chloroform, benzene, methyl methacrylate, toluene, ethylbenzene, m,p-xylene, o-xylene, alpha-pinene, and limonene. Using the loop injection (ppm-level) method, all validation criteria were met for each analyte. At ppm levels, alpha-pinene and limonene remained stable over 21 days, while the rest of the analytes were stable for 30 days. All analytes remained stable over 30 days at ppb levels. This sampling and analysis approach is a viable (i.e., accurate and stable) methodology that will enable development of VOC profiles for mixed exposures experienced by healthcare workers.     

Preferential sorption of some natural organic matter fractions to titanium dioxide nanoparticles: influence of pH and ionic strength

Natural organic matter (NOM) sorption to nanoparticles (NPs) can influence their transport and bioavailability in the aquatic environment. The sorption affinity of NOM to surfaces including NPs is size dependent, and depending on environmental conditions, NOM may enhance or mitigate NPs toxicity. The aim of this study was to investigate the preferential sorption of different-sized fractions of NOM to titanium dioxide (TiO₂) NPs. We specifically investigated the influence of pH, ionic strength, and NOM concentration on the extent of this preferential sorption using a constant sorbent concentration (400 mg/L TiO₂ NPs). Additionally, sorption of NOM to TiO₂ NPs at varying pH was investigated. The nonsorbed NOM was separated from the sorbed, by 50 nm polycarbonate membrane filters and ultracentrifugation. High-performance size exclusion chromatography (HPSEC) was used to determine the average molecular weights of NOM (MWw). Corroborative evidence of preferential sorption of different-sized molecular weight fractions of NOM was obtained from optical techniques such as absorbance and fluorescence spectrophotometry. The total organic carbon was measured by the Total Organic Carbon Analyzer—Shimadzu (TOC-VCPH). The results indicated that there is preferential sorption of larger sized fractions of NOM to TiO₂ NPs irrespective of NOM concentration. It was observed that the sorption of larger sized fractions of NOM was much enhanced at lower pH and at higher ionic strength. Both absorbance and fluorescence spectrophotometric techniques gave credible corroborative evidence on the extent of preferential sorption of lager sized fractions of NOM with respect to pH and ionic strength. The sorption results demonstrated higher sorption at lower pH than at higher pH. Overall, the results of this study suggest that the environmental conditions are key factors that can contribute to NOM’s fractional preferential sorption to NPs in the aquatic environment.     

Simulating and delineating future land change trajectories across Europe

Explorations of future land use change are important to understand potential conflicts between competing land uses, trade-offs associated with particular land change trajectories, and the effectiveness of policies to steer land systems into desirable states. Most model-based explorations and scenario studies focused on conversions in broad land use classes, but disregarded changes in land management or focused on individual sectors only. Using the European Union (EU) as a case study, we developed an approach to identifying typical combinations of land cover and management changes by combining the results of multimodel simulations in the agriculture and forest sectors for four scenarios from 2000 to 2040. We visualized land change trajectories by mapping regional hotspots of change. Land change trajectories differed in extent and spatial pattern across the EU and among scenarios, indicating trajectory-specific option spaces for alternative land system outcomes. In spite of the large variation in the area of change, similar hotspots of land change were observed among the scenarios. All scenarios indicate a stronger polarization of land use in Europe, with a loss of multifunctional landscapes. We analyzed locations subject to change by comparing location characteristics associated with certain land change trajectories. Results indicate differences in the location conditions of different land change trajectories, with diverging impacts on ecosystem service provisioning. Policy and planning for future land use needs to account for the spatial variation of land change trajectories to achieve both overarching and location-specific targets.

     

Social-ecological system resonance: a theoretical framework for brokering sustainable solutions

Sustainability science is a solution-oriented discipline. Yet, there are few theory-rich discussions about how this orientation structures the efforts of sustainability science. We argue that Niklas Luhmann’s social system theory, which explains how societies communicate problems, conceptualize solutions, and identify pathways towards implementation of solutions, is valuable in explaining the general structure of sustainability science. From Luhmann, we focus on two key concepts. First, his notion of resonance offers us a way to account for how sustainability science has attended and responded to environmental risks. As a product of resonance, we reveal solution-oriented research as the strategic coordination of capacities, resources, and information. Second, Luhmann’s interests in self-organizing processes explain how sustainability science can simultaneously advance multiple innovations. The value logic that supports this multiplicity of self-organizing activities as a recognition that human and natural systems are complex coupled and mutually influencing. To give form to this theoretical framework, we offer case evidence of renewable energy policy formation in Texas. Although the state’s wealth is rooted in a fossil-fuel heritage, Texas generates more electricity from wind than any US state. It is politically antagonistic towards climate-change policy, yet the state’s reception of wind energy technology illustrates how social and environmental systems can be strategically aligned to generate solutions that address diverse needs simultaneously. This case demonstrates that isolating climate change—as politicians do as a separate and discrete problem—is incapable of achieving sustainable solutions, and resonance offers researchers a framework for conceptualizing, designing, and communicating meaningfully integrated actions.