Action and Entropy in Heat Engines: An Action Revision of the Carnot Cycle.

Despite the remarkable success of Carnot's heat engine cycle in founding the discipline of thermodynamics two centuries ago, false viewpoints of his use of the caloric theory in the cycle linger, limiting his legacy. An action revision of the Carnot cycle can correct this, showing that the heat flow powering external mechanical work is compensated internally with configurational changes in the thermodynamic or Gibbs potential of the working fluid, differing in each stage of the cycle quantified by Carnot as caloric. Action (@) is a property of state having the same physical dimensions as angular momentum (mrv = mr2ω). However, this property is scalar rather than vectorial, including a dimensionless phase angle (@ = mr2ωδφ). We have recently confirmed with atmospheric gases that their entropy is a logarithmic function of the relative vibrational, rotational, and translational action ratios with Planck's quantum of action h. The Carnot principle shows that the maximum rate of work (puissance motrice) possible from the reversible cycle is controlled by the difference in temperature of the hot source and the cold sink: the colder the better. This temperature difference between the source and the sink also controls the isothermal variations of the Gibbs potential of the working fluid, which Carnot identified as reversible temperature-dependent but unequal caloric exchanges. Importantly, the engine's inertia ensures that heat from work performed adiabatically in the expansion phase is all restored to the working fluid during the adiabatic recompression, less the net work performed. This allows both the energy and the thermodynamic potential to return to the same values at the beginning of each cycle, which is a point strongly emphasized by Carnot. Our action revision equates Carnot's calorique, or the non-sensible heat later described by Clausius as 'work-heat', exclusively to negative Gibbs energy (-G) or quantum field energy. This action field complements the sensible energy or vis-viva heat as molecular kinetic motion, and its recognition should have significance for designing more efficient heat engines or better understanding of the heat engine powering the Earth's climates.

Partitioning Entropy with Action Mechanics: Predicting Chemical Reaction Rates and Gaseous Equilibria of Reactions of Hydrogen from Molecular Properties.

Our intention is to provide easy methods for estimating entropy and chemical potentials for gas phase reactions. Clausius' virial theorem set a basis for relating kinetic energy in a body of independent material particles to its potential energy, pointing to their complementary role with respect to the second law of maximum entropy. Based on this partitioning of thermal energy as sensible heat and also as a latent heat or field potential energy, in action mechanics we express the entropy of ideal gases as a capacity factor for enthalpy plus the configurational work to sustain the relative translational, rotational, and vibrational action. This yields algorithms for estimating chemical reaction rates and positions of equilibrium. All properties of state including entropy, work potential as Helmholtz and Gibbs energies, and activated transition state reaction rates can be estimated, using easily accessible molecular properties, such as atomic weights, bond lengths, moments of inertia, and vibrational frequencies. We conclude that the large molecular size of many enzymes may catalyze reaction rates because of their large radial inertia as colloidal particles, maximising action states by impulsive collisions. Understanding how Clausius' virial theorem justifies partitioning between thermal and statistical properties of entropy, yielding a more complete view of the second law's evolutionary nature and the principle of maximum entropy. The ease of performing these operations is illustrated with three important chemical gas phase reactions: the reversible dissociation of hydrogen molecules, lysis of water to hydrogen and oxygen, and the reversible formation of ammonia from nitrogen and hydrogen. Employing the ergal also introduced by Clausius to define the reversible internal work overcoming molecular interactions plus the configurational work of change in Gibbs energy, often neglected; this may provide a practical guide for managing industrial processes and risk in climate change at the global scale. The concepts developed should also have value as novel methods for the instruction of senior students.

17ß-Estradiol residues and estrogenic activities in the Hawkesbury River, Australia.

Two highly sensitive ELISAs for the specific detection of 17ß-estradiol (E2) residues were developed, showing the limits of detection (LOD, a concentration at 15% inhibition of color development) of 0.04 ±â€¯0.02 µg/L and 0.05 ±â€¯0.03 µg/L. The average recovery rate of the river water samples spiked with E2 at 1-50 ng/L range was 111.5% (68.6-252%) with the % relative standard deviation (RSD) of 0.5-86.3%. The ELISA demonstrated a good correlation with the GC-MS analyses of the spiked river water samples (r = 0.909). Applying the developed E2 ELISA assay to the monitoring of E2 residues in Hawkesbury River (New South Wales, Australia) found that all the tested creek samples contained E2 residues less than the biologically significant level of 10 ng/L. However, 25% of the water samples tested demonstrated the estrogen activity (determined by the yeast estrogen screening (YES) assay) above the levels that have been linked to the adverse effects in fish and other aquatic organisms (> 20 E2 Eq ng/L). It was apparent that the E2 residues together with the EE2 residues (reported in our previous study) contributed to most of the observed estrogenic activity in Hawkesbury River.

A survey of 17α-ethinylestradiol and mestranol residues in Hawkesbury River, Australia, using a highly specific enzyme-linked immunosorbent assay (ELISA) demonstrates the levels of potential biological significance.

This study reports on the potential status of 17α-ethinylestradiol (EE2) and mestranol (MeEE2) residues in aquatic environments in New South Wales (NSW), Australia, based on the analysis by a specific ELISA we developed. Polyclonal antibodies were raised against the EE2 hapten with a linker attached at the C3-position to direct the antibody binding towards the ring D of EE2/MeEE2. Using this approach, an ELISA highly specific to EE2 and MeEE2 was successfully developed, showing less than 3.1% cross-reactivity (% CR) with other major steroidal sex hormones and their derivatives. The assay performed with the limit of detection (LOD) of 0.04 ± 0.01µg/L for both EE2 and MeEE2, and the limit of quantitation (LOQ) of 0.05 ± 0.01ng/L when it was coupled with the SM2-Biobeads solid phase extraction. Prior to conducting the survey study, it was validated against the gas chromatography-mass spectrophotometry (GC-MS) method, which showed high correlation with R2 of 0.934. Fresh surface water samples collected at different sites along Hawkesbury River in New South Wales (NSW) were analyzed for the EE2/ MeEE2 residues using the developed ELISA. The EE2/MeEE2 levels were found to range between 4.1 and 8.3ng/L in Emigrant Creek, NSW, where the primary activity was macadamia plantation, and higher levels between 15 and 29ng/L in South Creek, NSW, Greater Western Sydney at sites upstream and downstream of the municipal sewage treatment plants.

Development of an ELISA to detect clenbuterol in swine products using a new approach for hapten design.

This research outlines the application of an enzyme-linked immunosorbent assay (ELISA) for the analysis of clenbuterol in animal products. Our assay showed good sensitivity for clenbuterol (0.4 ng/g or 0.4 ppb) and low detection limit (0.09 ng/g or 0.09 ppb). A low cross-reactivity for other ß2-agonist drugs such as salbutamol, terbutaline, and epinephrine led to formatting an ELISA kit considered to have a high specificity for clenbuterol. A survey of Ho Chi Minh City pork market was conducted as part of the validation of our ELISA. ELISA results showed a surprisingly high value of contamination. However, it will be necessary to conduct a more statistically valid replicated survey with evaluation by other instrumental methods to obtain a definite conclusion. This ELISA kit will be used to monitor growth promoter residues in Vietnam's animal products.

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.

Indigenous actinorhizal plants of Australia.

Indigenous species of actinorhizal plants of Casuarinaceae, Elaeagnaceae and Rhamnaceae are found in specific regions of Australia. Most of these plants belong to Casuarinaceae, the dominant actinorhizal family in Australia. Many of them have significant environmental and economical value. The other two families with their indigenous actinorhizal plants have only a minor presence in Australia. Most Australian actinorhizal plants have their native range only in Australia, whereas two of these plants are also found indigenously elsewhere. The nitrogen-fixing ability of these plants varies between species. This ability needs to be investigated in some of these plants. Casuarinas form a distinctive but declining part of the Australian landscape. Their potential has rarely been applied in forestry in Australia despite their well-known uses, which are being judiciously exploited elsewhere. To remedy this oversight, a programme has been proposed for increasing and improving casuarinas that would aid in greening more regions of Australia, increasing the soil fertility and the area of wild life habitat (including endangered species). Whether these improved clones would be productive with local strains of Frankia or they need an external inoculum of Frankia should be determined and the influence of mycorrhizal fungi on these clones also should be investigated.

Field monitoring of plant-growth-promoting rhizobacteria by colony immunoblotting.

Inoculant plant-growth-promoting bacteria are emerging as an important component of sustainable agriculture. There is a need to develop inexpensive methods for enumerating these organisms after their application in the field, to better understand their survival and impacts on yields. Immunoblotting is one potential method to measure viable cells, but the high cost of the conventionally used nylon membranes makes this method prohibitive. In this study, less expensive alternative materials such as filter papers, glossy photo papers, and transparencies for the purpose of colony immunoblotting were evaluated and the best substance was chosen for further studies. Whatman filter paper No. 541 combined with a 0.01 mol·L(-1) H(2)SO(4) rinsing step gave similar results to nylon membranes but <20% of the overall cost of the original colony immunoblotting assay. The application of the modified immunoblot method was tested on nonsterile clay soil samples that were spiked with high numbers (>10(7) CFU·g(-1)) of the plant-growth-promoting bacteria Pseudomonas fluorescens , Azospirillum brasilense , or Rhizobium leguminosarum . The modified protocol allowed the identification and recovery of over 50% of the inoculated cells of all three strains, amidst a background of the native soil microflora. Subsequently, the survival of P. fluorescens was successfully monitored for several months after application to field-grown rice at Jerilderie, New South Wales, Australia, thus validating the procedure.

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.

Rapid determination of fumonisin B1 in food samples by enzyme-linked immunosorbent assay and colloidal gold immunoassay.

A rapid enzyme-linked immunosorbent assay (ELISA) test (microwell plate) and a membrane-based colloidal gold immunoassay in flow-through and lateral-flow formats for the rapid detection of fumonisin B1 (FB1) were developed. The rapid microwell assay can be completed within 20 min with the detection limit of 0.5 +/- 0.2 microg/L. Membrane-based colloidal gold immunoassays had a visual detection limit of 1.0 microg/L for FB1 with the detection time of <10 min. Matrix interference was eliminated by 15-fold dilutions of methanol extracts with buffer. These immunoassays can be used as quantitative or qualitative tools for the rapid detection of FB1 residues in 10-20 min on-site.

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.

A rapid and sensitive chemiluminescence enzyme-linked immunosorbent assay for the determination of fumonisin B1 in food samples.

An enzyme-linked immunosorbent assay (ELISA) based on polyclonal antibody with enhanced chemiluminescent (ECL) detection of fumonisin B1 (FB1) in food samples has been developed. Assay conditions, including concentrations of antibody and enzyme conjugate, competition time and so on, were optimized. The effects of pH and two different organic solvents were investigated. The optimized ECL-ELISA system allowed FB1 determination in a linear working range of 0.14-0.9 microg L(-1) with IC50 value of 0.32 microg L(-1) and a limit of detection of 0.09 microg L(-1). The ECL-ELISA was about 10 times more sensitive and about 30% time less than that of colorimetric ELISA using the same antibody and HRP-conjugate. Good recoveries with spiked food samples were obtained, and the results correlated well with those obtained using conventional direct competition ELISA assay and HPLC method, which indicated that ECL-ELISA was capable of being applied for the specific detection and routine monitoring of FB1 in food samples.

Wheat root colonization and nitrogenase activity by Azospirillum isolates from crop plants in Korea.

Nitrogen-fixing bacteria were isolated from the rhizosphere of different crops of Korea. A total of 16 isolates were selected and characterized. Thirteen of the isolates produced characteristics similar to those of the reference strains of Azospirillum, and the remaining 3 isolates were found to be Enterobacter spp. The isolates could be categorized into 3 groups based on their ARDRA patterns, and the first 2 groups comprised Azospirillum brasilense and Azospirillum lipoferum. The acetylene reduction activity (ARA) of these isolates was determined for free cultures and in association with wheat roots. There was no correlation between pure culture and plant-associated nitrogenase activity of the different strains. The isolates that showed higher nitrogenase activities in association with wheat roots in each group were selected and sequenced. Isolates of Azospirillum brasilense CW301, Azospirillum brasilense CW903, and Azospirillum lipoferum CW1503 were selected to study colonization in association with wheat roots. We observed higher expression of beta-galactosidase activity in A. brasilense strains than in A. lipoferum strains, which could be attributed to their higher population in association with wheat roots. All strains tested colonized and exhibited the strongest beta-galactosidase activity at the sites of lateral roots emergence.

A rapid aflatoxin B1 ELISA: development and validation with reduced matrix effects for peanuts, corn, pistachio, and Soybeans.

Among the competitive ELISAs for aflatoxins that have been described, few have been adequately validated for reduced matrix effects. Using an aflatoxin B(1) (AFB(1))-specific polyclonal antibody (produced from AFB(1)-oxime conjugated to bovine serum albumin (BSA)) and AFB(1)- and AFB(2)-enzyme conjugates, four direct competitive ELISAs based on 96-microwell plates (two standard assays and two rapid assays) were developed, paying special attention to producing a robust assay relatively free of interferences for a range of agricultural products. The antibody was AFB(1)-specific, detecting only AFB(1) in a mixture of four aflatoxins (AFB(1), AFB(2), AFG(1), and AFG(2)), but showed significant cross-reaction with AFG(1) (57-61%) when an individual compound was tested. Standard assays (long assays) exhibited higher sensitivities than rapid assays (short assays) with IC(50) values of 12 +/- 1.5 and 9 +/- 1.5 microg/kg in sample (with 1 in 5 dilution of sample extract) for AFB(1) and AFB(2)-enzyme conjugates, respectively. These assays have narrower detection ranges (7.1-55.5 microg/kg in sample) and required dilution of sample extracts to overcome solvent and matrix interferences, making these assays less ideal as analytical methods. Rapid assays exhibited IC(50) values of 21.6 +/- 2.7 and 12 microg/kg in sample for AFB(1)- and AFB(2)-enzyme conjugates, respectively. These assays have ideally broader detection ranges (4.2-99.9 microg/kg in sample) and showed no methanol effects up to 80% with significantly reduced matrix interferences as a result of the shorter incubation times and increasing the amounts of enzyme conjugate used. Therefore, the rapid assays were formatted to perform without a need for extract dilution. The rapid assays can be completed within 15 min, potentially suitable for receival bays where quick decision-making to segregate low and high contamination is critical. Further validation using the rapid assay with AFB(1)-enzyme conjugate indicated relatively good recoveries of AFB(1) spiked in corn, peanuts, pistachio, and soybeans, which were free from significant matrix effects. It can be concluded that this rapid assay would be suitable for monitoring aflatoxin AFB(1) at current legal maximum residue limits of 10 microg/kg in food such as corn, peanuts, pistachio, and soybeans.