A Simple Method to Estimate Entropy and Free Energy of Atmospheric Gases from Their Action.

A convenient practical model for accurately estimating the total entropy (ΣSi) of atmospheric gases based on physical action is proposed. This realistic approach is fully consistent with statistical mechanics, but reinterprets its partition functions as measures of translational, rotational, and vibrational action or quantum states, to estimate the entropy. With all kinds of molecular action expressed as logarithmic functions, the total heat required for warming a chemical system from 0 K (ΣSiT) to a given temperature and pressure can be computed, yielding results identical with published experimental third law values of entropy. All thermodynamic properties of gases including entropy, enthalpy, Gibbs energy, and Helmholtz energy are directly estimated using simple algorithms based on simple molecular and physical properties, without resource to tables of standard values; both free energies are measures of quantum field states and of minimal statistical degeneracy, decreasing with temperature and declining density. We propose that this more realistic approach has heuristic value for thermodynamic computation of atmospheric profiles, based on steady state heat flows equilibrating with gravity. Potentially, this application of an action principle can provide better understanding of emergent properties of many natural or evolving complex systems, including modelling of predictions for global warming.

Growth Recovery of Lemna gibba and Lemna minor Following a 7-Day Exposure to the Herbicide Diuron.

In agricultural catchments, aquatic ecosystems can experience a pulse exposure to pesticides. Following such exposure, non-target organisms that are not extirpated may recover. This paper investigates the potential of two duckweed species (Lemna minor and Lemna gibba) to recover from a 7-day exposure to different concentrations (0.4-208 µg L(-1)) of the herbicide diuron. There was significant inhibition in the growth and biomass after the initial 7-day exposure (e.g. frond number EC50=59.2 and 52.2 µg L(-1) for L. minor and L. gibba, respectively). Following transfer to clean media, recovery (the highest concentration yielding no significant difference in the effect endpoint from the control) was observed for all effects endpoints at concentrations ranging 60-111 µg L(-1) for L. minor and 60-208 µg L(-1) for L. gibba. These results suggest that recovery is possible for primary producers at environmentally relevant concentrations considered significant in ecological risk assessment.

Probabilistic risk assessment of diuron and prometryn in the Gwydir River catchment, Australia, with the input of a novel bioassay based on algal growth.

A probabilistic risk assessment of the selected herbicides (diuron and prometryn) in the Gwydir River catchment was conducted, with the input of the EC50 values derived from both literature and a novel bioassay. Laboratory test based on growth of algae exposed to herbicides assayed with a microplate reader was used to examine the toxicity of diuron and prometryn on the growth of Chlorella vulgaris. Both herbicides showed concentration dependent toxicity in inhibiting the growth of Chlorella during the exposure period of 18-72 h. Diuron caused more toxicity as judged by growth rates than prometryn. Thalaba Creek at Merrywinebone was identified as the 'hotspot' for diuron and prometryn risk in the Gwydir catchment. The use of microplate assays coupled with probabilistic risk assessment is recommended for rapid assessment of ecotoxicity of indigenous species, allowing identification of locations in river catchments requiring environmental management.

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.

Computer-aided molecular modeling study on antibody recognition of small molecules: an immunoassay for triazine herbicides.

Most immunoassays for determination of small molecules are still designed on the basis of the "trial and error" method, due to the lack of understanding of antibody recognition. In the present study, we developed a heterologous indirect competitive enzyme-linked immunosorbent assay for determination of triazine herbicides, with limits of detection for 11 triazines ranging from 0.05 to 29.4 µg/L. Mechanisms of the antigen-antibody interaction were studied by computer-aided molecular modeling (CAMM)-based quantitative structure-activity relationship analyses. Co-effects of the analytes' substructural hydrophobic, electrostatic, and steric fields on antibody recognition were further revealed. Hydrophobicity of the antigens was demonstrated to have the most important impact. Even less exposed substituents provided hydrophobic force to the antigen-antibody interaction. Dislocated orientation of analyte functional groups could lead to steric hindrance and hydrophobic misleading of antibody recognition. This may happen even when the antigens contained the same substituent as the hapten. Frontier orbital energies also affect the reaction significantly. This study highlights of the power of CAMM-based analyses, providing insights into antibody recognition of small molecules.

Capitalizing on deliberate, accidental, and GM-driven environmental change caused by crop modification.

The transgenic traits associated with the majority of commercial genetically modified crops are focused on improving herbicide and insecticide management practices. The use of the transgenic technology in these crops and the associated chemistry has been the basis of studies that provide evidence for occasional improvement in environmental benefits due to the use of less residual herbicides, more targeted pesticides, and reduced field traffic. This is nicely exemplified through studies using Environmental Impact Quotient (EIQ) assessments. Whilst EIQ evaluations may sometimes illustrate environmental benefits they have their limitations. EIQ evaluations are not a surrogate for Environmental Risk Assessments and may not reflect real environmental interactions between crops and the environment. Addressing the impact cultivated plants have on the environment generally attracts little public attention and research funding, but the introduction of GM has facilitated an expansion of research to address potential environmental concerns from government, NGOs, industry, consumers, and growers. In this commentary, some evidence from our own research and several key papers that highlight EIQ assessments of the impact crops are having on the environment are presented. This information may be useful as an education tool on the potential benefits of GM and conventional farming. In addition, other deliberate, accidental, and GM-driven benefits derived from the examination of GM cropping systems is briefly discussed.

Immunoassay for phenylurea herbicides: application of molecular modeling and quantitative structure-activity relationship analysis on an antigen-antibody interaction study.

An indirect competitive enzyme-linked immunosorbent assay (icELISA) for 12 phenylurea herbicides (PUHs) was established with the half-maximum inhibition concentration (IC(50)) of 1.7-920.7 µg L(-1). A method of computer-aided molecular modeling was established in quantitative structure-activity relationship (QSAR) studies to obtain a deeper insight into the PUHs' antibody interactions on how and which molecular properties of the analytes quantitatively affect the antibody recognition. A two-dimensional (2D)-QSAR model based on the Hansch equation and a hologram QSAR (HQSAR) model were constructed, and both showed highly predictive abilities with cross-validation q(2) values of 0.820 and 0.752, respectively. It was revealed that the most important impact factor of the antibody recognition was the PUHs' hydrophobicity (log P), which provided a quadratic correlation to the antibody recognition. Hapten-carrier linking groups were less exposed to antibodies during immunization; thus, groups of the analytes in the same position were generally considered to be less contributive to antibody recognition during immunoassay. But the results of substructure-level analysis showed that these groups played an important role in the antigen-antibody interaction. In addition, the frontier-orbital energy parameter E(LUMO) was also demonstrated as a related determinant for this reaction. In short, the result demonstrated that the hydrophobicity and the lowest unoccupied molecular orbital energy (E(LUMO)) of PUH molecules were mainly responsible for antibody recognition.

Calculation of pesticide degradation in decaying cotton gin trash.

Pesticide residues were measured in stockpiled cotton gin trash (CGT) over a 2-year period. Samples were analysed by GC/MS/MS and interpretation of the results was aided by the presence of DDE residues, remnant from prior DDT use. Fourteen pesticide residues from current agricultural practice were detected in CGT. Several of these, including indoxacarb, profenofos, chlorpyrifos, propargite, bifenthrin, ethion and cyhalothrin, were more persistent than expected on the basis of published data for soil dissipation. The results showed a complex pattern of pesticide residue decay over time because of the simultaneous decomposition of the CGT matrix.

Sorption and desorption of endosulfan sulfate and diuron to composted cotton gin trash.

This paper investigates the potential use of composted cotton gin trash (CCGT) as a pesticide sorption medium in remediation of contaminated tailwater. CCGT was found to contain a large organic matter fraction (25.22%). Sorption of endosulfan sulfate and diuron, using the batch equilibrium method, was rapid but not limited for the range of applied concentrations, with diuron failing to reach equilibrium after two days. The partition K d and organic carbon partition K(OC) coefficients determined diuron ( Kd = 78; K(OC) = 526) and endosulfan sulfate ( Kd = 1500; K(OC) = 10,111) to reside in the solid phase. Limited desorption of diuron and higher range concentrations of endosulfan sulfate (50-100 microg L(-1)) were quantified. Sorption and desorption resulted from hydrophobic and hydrophilic interactions with the humic components of the compost. CCGT was concluded to have a superior sorption capacity to other sorbents reported in the literature, an assessment that requires field substantiation.

The effect of vegetation on pesticide dissipation from ponded treatment wetlands: quantification using a simple model.

Field data shows that plants accelerate pesticide dissipation from aquatic systems by increasing sedimentation, biofilm contact and photolysis. In this study, a graphical model was constructed and calibrated with site-specific and supplementary data to describe the loss of two pesticides, endosulfan and fluometuron, from a vegetated and a non-vegetated pond. In the model, the major processes responsible for endosulfan dissipation were alkaline hydrolysis and sedimentation, with the former process being reduced by vegetation and the latter enhanced. Fluometuron dissipation resulted primarily from biofilm reaction and photolysis, both of which were increased by vegetation. Here, greater photolysis under vegetation arose from faster sedimentation and increased light penetration, despite shading. Management options for employing constructed wetlands to polish pesticide-contaminated agricultural runoff are discussed. The lack of easily fulfilled sub-models and data describing the effect of aquatic vegetation on water chemistry and sedimentation is also highlighted.

Pesticide removal from cotton farm tailwater by a pilot-scale ponded wetland.

A pilot-scale, ponded wetland consisting of an open pond and a vegetated pond in series was constructed on a cotton farm in northern New South Wales, Australia, and assessed for its potential to remove pesticides from irrigation tailwater. Ten incubation periods ranging from 7 to 13 days each were conducted over two cotton growing seasons to monitor removal of residues of four pesticides applied to the crop. Residue reductions ranging 22-53% and 32-90% were observed in the first and second seasons respectively. Average half-lives during this first season were calculated as 21.3 days for diuron, 25.4 days for fluometuron and 26.4 days for aldicarb over the entire wetland. During the second season of monitoring, pesticide half-lives were significantly reduced, with fluometuron exhibiting a half-life of 13.8 days, aldicarb 6.2 days and endosulfan 7.5 days in the open pond. Further significant reductions were observed in the vegetated pond and also following an algal bloom in the open pond, as a result of which aldicarb and endosulfan were no longer quantifiable. Partitioning onto sediment was found to be a considerable sink for the insecticide endosulfan. These results demonstrate that macrophytes and algae can reduce the persistence of pesticides in on-farm water and provide some data for modelling.