Cation-pi bonding: a new perspective on the sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Recent molecular modeling and spectroscopic studies have suggested that relatively strong interactions can occur between aromatic pi donors and metal cations in aqueous solutions. The objective of this study was to characterize potential cation-pi interactions between pi donors and exchangeable cations accumulated at mineral surfaces via both spectroscopic and batch sorption methods. Quadrupolar splitting in deuterium nuclear magnetic resonance ((2)H NMR) spectroscopy for d(2)-dichloromethane, d(6)-benzene, and d(8)-toluene (C(6)D(5)- moiety) in aqueous suspensions of a Na-saturated reference montmorillonite unambiguously indicated the ordering of solute molecules with respect to the clay surface. The half line broadening (Delta nu(1/2)) of (2)H NMR of d(6)-benzene in montmorillonite suspensions showed that soft exchangeable cations generally resulted in more benzene sorption compared with harder cations (e.g., Ag(+) > Cs(+) > Na(+) > Mg(2+), Ba(2+)). In batch sorption experiments, saturating minerals (e.g., porous silica gels, kaolinite, vermiculite, montmorillonite) with a soft transition metal or softer base cations generally increased the polycyclic aromatic hydrocarbon (PAH) sorption relative to harder cations (e.g., Ag(+) > Cs(+) > K(+) > Na(+); Ba(2+) > Mg(2+)). Sorption of phenanthrene to Ag(+)-saturated montmorillonite was much stronger compared with 1,2,4,5-tetrachlorobenzene, a coplanar non-pi donor having slightly higher hydrophobicity. In addition, a strong positive correlation was found between the cation-dependent sorption and surface charge density of the minerals (e.g., vermiculite, montmorillonite > silica gels, kaolinite). These results, coupled with the observations in (2)H NMR experiments with montmorillonite, strongly suggest that cation-pi bonding forms between PAHs and exchangeable cations at mineral surfaces and affects PAH sorption to hydrated mineral surfaces.     

Application of a hurdle negative binomial count data model to demand for bass fishing in the southeastern United States

This paper identifies factors that influence the demand for a bass fishing trip taken in the southeastern United States using a hurdle negative binomial count data model. The probability of fishing for a bass is estimated in the first stage and the fishing trip frequency is estimated in the second stage for individuals reporting bass fishing trips in the Southeast. The applied approach allows the decomposition of the effects of factors responsible for the decision to take a trip and the trip number. Calculated partial and total elasticities indicate a highly inelastic demand for the number of fishing trips as trip costs increase. However, the demand can be expected to increase if anglers experience a success measured by the number of caught fish or their size. Benefit estimates based on alternative estimation methods differ substantially, suggesting the need for testing each modeling approach applied in empirical studies.     

Using surfactant-modified clays to determine sorption mechanisms for a representative organic base, quinoline

Sorption of a representative ionizable nitrogen heterocycle, quinoline (pKa = 4.92), was investigated to determine the relative contributions of the neutral and protonated species to the overall process. Batch sorption experiments were conducted on surfactant-modified clays that were synthesized from the exchange of hexadecyltrimethylammonium cations for resident sodium cations on a specimen smectite (Swy-2) at 0, 60, 80, and 100% of the clay's cation exchange capacity (CEC). Hexadecyltrimethylammonium exchange creates highly effective organic partitioning domains within the clay interlayers in proportion to their coverage on the exchange complex. The fractionally exchanged clays, therefore, provided discrete exchange and organic partitioning domains for the protonated and neutral species of quinoline. Data were described by a combined Langmuir-linear isotherm that permitted independent characterization of both sorption components. Results indicated that cationic sorption dominated but that the neutral species can contribute substantially given sufficient organic carbon content relative to the CEC and at pH above the pKa of quinoline. The data obtained in this study for quinoline demonstrated that the combined isotherm (including cation exchange and hydrophobic partitioning terms) describes sorption data and compares favorably with the purely empirical Freundlish isotherm.     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Threshold estimation from the linear dose-response model: Method and radiation data

The linear dose-response model is considered a conservative, nonthreshold relationship. This is based on a confusion between the sufficient condition (that is, zero slope at zero dose) and the necessary condition (that is, response distinguishable from zero). Once the threshold is properly defined, it is shown that the linear model predicts thresholds for radiation data in good agreement with experimental results.     

Building a model of commitment to the natural environment to predict ecological behavior and willingness to sacrifice

We examined the connection between individuals’ relationships with the natural environment and their environmental behaviors with a focus on commitment to the environment, defined as psychological attachment and long-term orientation to the natural world. Commitment is theorized to emerge from structural interdependence with the environment and to lead to pro-environmental behaviors. Close relationships research has identified three key antecedents to commitment (satisfaction, alternatives, and investments). We developed environment-specific measures of these constructs, and factor analysis verified three distinct factors. A path analysis revealed that satisfaction with the environment and investments in the environment, but not alternatives to the environment, predicted commitment to the environment. Moreover, commitment mediated the effects of satisfaction and investments on general ecological behavior and willingness to sacrifice for the environment. In regression analyses, commitment predicted general ecological behavior and willingness to sacrifice for the environment, even when controlling for ecological worldview, inclusion of nature in the self, connectedness to nature, and environmental identity. Individuals who are satisfied with and invested in the natural world are likely to be committed to the environment and act with the well-being of the environment in mind.     

Field-scale variation in microbial activity and soil properties in relation to mineralization and sorption of pesticides in a sandy soil

Pesticides applied to agricultural soils are subject to environmental concerns because leaching to groundwater reservoirs and aquatic habitats may occur. Knowledge of field variation of pesticide-related parameters is required to evaluate the vulnerability of pesticide leaching. The mineralization and sorption of the pesticides glyphosate and metribuzin and the pesticide degradation product triazinamin in a field were measured and compared with the field-scale variation of geochemical and microbiological parameters. We focused on the soil parameters clay and organic carbon (C) content and on soil respiratory and enzymatic processes and microbial biomass. These parameters were measured in soil samples taken at two depths (Ap and Bs horizon) in 51 sampling points from a 4-ha agricultural fine sandy soil field. The results indicated that the spatial variation of the soil parameters, and in particular the content of organic C, had a major influence on the variability of the microbial parameters and on sorption and pesticide mineralization in the soil. For glyphosate, with a co-metabolic pathway for degradation, the mineralization was increased in soils with high microbial activity. The spatial variability, expressed as the CV, was about five times higher in the Bs horizon than in the Ap horizon, and the local-scale variation within 100 m(2) areas were two to three times lower than the field-scale variation within the entire field of about 4 ha.     

Broadening the statistical search for metal price super cycles to steel and related metals

During the past five years, industry analysts have proclaimed that metal prices are in the early phase of a ‘super cycle,’ driven primarily by Chinese industrial expansion. Academic economists have generally been very skeptical about the presence of long cycles. A time-series econometric analysis by Cuddington and Jerrett [2008. Super cycles in real metals prices? IMF Staff Pap. 55(4), in press], however, has used band-pass filtering techniques to isolate super cycles in the prices of six metals traded on the London Metal Exchange (the ‘LME6’). This paper extends the search for super-cycle behavior to three additional metal products that are critical in the early phases of industrial development and urbanization: steel, pig iron, and molybdenum (a key ingredient in many steel alloys). There is strong evidence of super cycles in these three metals, although their timing differs to some extent from the super cycles found for the LME6.     

A new way to use solid-state carbon-13 nuclear magnetic resonance spectroscopy to study the sorption of organic compounds to soil organic matter

Several solid-state 13C nuclear magnetic resonance (NMR) techniques were used to characterize soil organic matter spiked with 13C-labeled organic compounds spanning a range of hydrophobicities (benzoic acid, benzophenone, naphthalene, phenanthrene, and palmitic acid). The chemical shifts of NMR resonances of the sorbed species were shifted by up to 3 ppm relative to those of the neat compounds. Sorption also resulted in increased resonance linewidth for the compounds containing a single 13C label, indicating the presence of a range of different chemical environments at the sites of sorption. On the other hand, sorption decreased the linewidth of the resonance of naphthalene, which was uniformly 13C-labeled. This was attributed to the removal of intermolecular 13C-13C dipolar coupling. Heterogeneity of the organic matter was demonstrated using the spectral editing technique proton spin relaxation editing (PSRE), which enabled the identification and quantification of charcoal-rich domains characterized by rapid rates of proton spin-lattice relaxation in the static frame (T1H), and humic domains characterized by slow rates of T1H relaxation. Furthermore it was demonstrated that the sorbed 13C-labeled molecules "inherit" the T1H "signature" of the organic matrix in their immediate vicinity. Thus PSRE on the spiked soils enabled evaluation of the relative affinity of the two domain types for the sorbate molecules. The charcoal-rich domains were shown to have a twofold to tenfold greater affinity for the organic compounds, with greater differences found for the more hydrophobic compounds.     

Application of a health promotion model to community-based sustainability planning

The future of human health and that of all other species depends on the viability and sustainability of a host of environments and ecosystems. Human behaviours have profound effects (both positive and negative) on such ecosystems. Despite the obviousness of these statements, there remains a lack of clarity around the mechanisms for altering specific behaviours related to sustainability and their impact on environments. This paper offers a conceptual framework for identifying relations between human behaviour and ecosystem health and sustainability. We also discuss strategies for changing target behaviours in the context of a programme or policy planning. Finally, we draw on research that applies this adaptation to a small island community near Vancouver, Canada.     

Assessing the application of an additive model to estimate toxicity of a complex effluent

A number of industries monitor levels of chemicals in their effluent, but few have undertaken prolonged biological monitoring of this wastewater. The focus of the present study was to determine whether past chemical data for effluent from a lead smelter could be used to estimate its past toxicity. Since the interactive effects of metals in effluents are often assumed to be additive, it was hypothesized that an additive model, 100/[sigma(metal concentration in effluent/EC50 for individual metal)], could be used to generate an EC50 from chemical data (where EC50 is the concentration of test material that affects 50% of the test organisms). To test the approach, a larval development toxicity test with the marine polychaete, Galeolaria caespitosa, was used to test 26 separate samples of effluent from a lead smelter, generating empirical EC50 values. EC50 values for each individual metal in the effluent were also generated using the larval development toxicity test. The concentrations of trace metals in each effluent sample were determined and, using the additive model, EC50 values were calculated. For the majority of effluent samples tested, the additive model underestimated toxicity, suggesting the presence of additional unidentified contaminants in the effluent samples. Additionally, a nonlinear rather than linear regression curve was found to best describe the relationship between the model and empirically derived EC50 values. This relationship was then used to estimate past trends in toxicity of the smelter effluent. Forty-eight percent of the variability in measured toxicity was explained by the model, with the model underestimating toxicity in the majority of samples.     

Beyond water data: benefits to volunteers and to local water from a citizen science program

Survey results of citizen science water data collection volunteers are presented, indicating personal benefits (e.g., being in nature, helping local water quality), and suggesting potential long-term benefits of improved watershed health (e.g., behavior change). These results can inform citizen science program development and contribute to watershed planners’ understanding of the broad benefits of such programs. We suggest that respondents’ positive feelings toward the watershed's major river and desire to learn about science and nature are place-specific elements that watershed and citizen science program managers could utilize in program development. Moreover, we explore the potential of social diffusion and behavior change and suggest the need for further research in these areas. We conclude that citizen science has potential not just as a means to collect large amounts of data (cheaply), but as a means to engage citizens to make environmentally friendly decisions.     

The role of condensed organic matter in the nonlinear sorption of hydrophobic organic contaminants by a peat and sediments

This study examines the effect of soil organic matter heterogeneity on equilibrium sorption and desorption of phenanthrene, naphthalene, 1,3,5-trichlorobenzene (1,3,5-TCB), and 1,2-dichlorobenzene (1,2-DCB) by soils and sediments. Two estuary sediments, a Pahokee peat (PP; Euic, hyperthermic Lithic Haplosaprist), and two subsamples (base- and acid-treated peat [TP] and acid-treated peat [FP]) of the peat were used as the sorbents. The contents of black carbon particles were quantified with a chemical extraction method. Petrographical examinations revealed the presence of the condensed soil and sediment organic matter (SOM) in Pahokee peat. The Freundlich isotherm model in two different forms was used to fit both sorption and desorption data. The results show that the sorption and desorption isotherms are generally nonlinear and that the apparent sorption-desorption hysteresis is present for phenanthrene and TCB. Detailed analysis of sorption data for the tested sorbent-sorbate systems indicates that black carbon is probably responsible for sorption isotherm nonlinearity for the two sediments, whereas the humic substances and kerogen may play the dominant role in nonlinear sorption by the peat. This investigation suggests that the microporosity of SOM is important for the hydrophobic organic contaminant (HOC) sorption capacity on the peat.     

Using a GIS model to assess terrestrial salamander response to alternative forest management plans.

A GIS model predicting the spatial distribution of terrestrial salamander abundance based on topography and forest age was developed using parameters derived from the literature. The model was tested by sampling salamander abundance across the full range of site conditions used in the model. A regression of the predictions of our GIS model against these sample data showed that the model has a modest but significant ability to predict both salamander abundance and mass per unit area. The model was used to assess the impacts of alternative management plans for the Hoosier National Forest (Indiana, USA) on salamanders. These plans differed in the spatial delineation of management areas where timber harvest was permitted, and the intensity of timber harvest within those management areas. The spatial pattern of forest openings produced by alternative forest management scenarios based on these plans was projected over 150 years using a timber-harvest simulator (HARVEST). We generated a predictive map of salamander abundance for each scenario over time, and summarized each map by calculating mean salamander abundance and the mean colonization distance (average distance from map cells with low predicted abundance to those with relatively high abundance). Projected salamander abundance was affected more by harvest rate (area harvested each decade) than by the management area boundaries. The alternatives had a varying effect on the mean distance salamanders would have to travel to colonize regenerating stands. Our GIS modeling approach is an example of a spatial analytical tool that could help resource management planners to evaluate the potential ecological impact of management alternatives.     

Compromise solutions to the acid deposition control problem: a theoretical model and some simulation results

Acid deposition is a muitifaceted environmental phenomenon whose control represents one of the most controversial environmental policy areas. Because of the longrange transport of air pollutants contributing to acid deposition, its control is the responsibility of more than one region. Given the interdependence between the economic and environmental impacts of acid deposition as well as the interregional conflicts over its control, the present article proposes an interregional integrated economic-environmental model for the study of the impacts of acid deposition control policies. This model is solved with the use of a compromise programming procedure which facilitates the explicit treatment of conflicting regional goals. After the theoretical and operational forms and the solution procedure of the proposed model are described, the use of the model is illustrated with a simulation example using the 1963 MRIO accounts and hypothetical environmental data. The compromise programming procedure can form the basis for interactive decision processes when policy makers are exposed to the solutions yielded by the model. The model's usefulness and future research directions are discussed.     

Application of a GIS-based stream buffer generation model to environmental policy evaluation

In this article a GIS method is presented for riparian environmental buffer generation. It integrates a scientifically tested buffer width delineation model into a GIS framework. Using the generally available data sets, it determines buffer widths in terms of local physical conditions and expected effectiveness. Technical burdens of data management, computation, and result presentation are handled by the GIS. The case study in which the method was used to evaluate the stream buffer regulations in a North Carolina county demonstrates its capability as a decision support tool to facilitate environmental policy formulation and evaluation, and environmental dispute resolution.     

Use of a generalized linear model to evaluate range forage production estimates

Interdisciplinary teams have been used in federal land planning and in the private sector to reach consensus on the environmental impact of management. When a large data base is constructed, verifiability of the accuracy of the coded estimates and the underlying assumptions becomes a problem. A mechanism is provided by the use of a linear statistical model to evaluate production coefficients in terms of errors in coding and underlying assumptions. The technique can be used to evaluate other intuitive models depicting natural resource production in relation to prescribed variables, such as site factors or secondary succession.     

Modelling soil series data to facilitate targeted habitat restoration: a polytomous logistic regression approach

Habitat restoration at a landscape scale is becoming increasingly important in environmental management. In this context, geographical information systems are well suited as they can store and integrate many of the abiotic and biotic criteria used to assess the ecological worth of a site. However, this capacity can be limited by the availability or suitability of spatial data sets. A classic example of the latter case is the National Soil Map of England and Wales, which groups soils of a varied nature into associations. Consequently the national soil map has proved to be a poor predictor of habitat suitability. Using polytomous logistic regression we put forward a method for separating soil associations into their constituent soils within the Chilterns Natural Area. This approach used soil association, aspect, slope and relative height as variables for this analysis. Whilst the model's performance is likely to have been limited by the accuracy of the soil association data set, a predictive accuracy of between 47 and 65% is sufficient to facilitate better targeting of habitat restoration when combined with other abiotic factors such as climate and topography.