RDX loss in a surface soil under saturated and well drained conditions

On military training ranges, low-order, incomplete detonations deposit RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) into surface soils. In this study, we evaluated RDX biodegradation in surface soils obtained from a military training range in Alaska. Two factors were compared: (i) soil water potential during the incubations; and (ii) the use of acetonitrile (ACN) as an RDX carrier to spike samples. Organic solvents have been used in laboratory studies to dissolve slightly water-soluble contaminants before addition to soil. We added ACN to obtain final soil ACN concentrations of 0 mg kg(-1) (0%), 1000 mg kg(-1) (0.1%) and 10 000 mg kg(-1) (1%). We then compared RDX attenuation in the soil under saturated and unsaturated conditions. RDX fell below the limit of detection within 3 wk of study initiation under the saturated condition. A maximum degradation rate of 0.15 mg RDX L(-1) d(-1) was measured. Under the unsaturated condition, 42% of the original RDX was still present at study termination (5 wk). The addition of acetonitrile at 0.1 or 1.0% had no affect on RDX loss in the saturated soil. In the unsaturated soil, however, ACN at 1.0% inhibited RDX loss by as much as 25%. These findings indicate that soil water potential and carrier solvent concentrations can impact the rate and extent to which RDX is attenuated in a surface soil.     

Chemistry and long-term decomposition of roots of Douglas-fir grown under elevated atmospheric carbon dioxide and warming conditions

Elevated atmospheric CO(2) concentrations and warming may affect the quality of litters of forest plants and their subsequent decomposition in ecosystems, thereby potentially affecting the global carbon cycle. However, few data on root tissues are available to test this feedback to the atmosphere. In this study, we used fine (diameter < or = 2 mm) and small (2-10 mm) roots of Douglas-fir (Pseudotsuga menziesii (Mirb.) Franco) seedlings that were grown for 4 yr in a 2 x 2 factorial experiment: ambient or elevated (+ 180 ppm) atmospheric CO(2) concentrations, and ambient or elevated (+3.8 degrees C) atmospheric temperature. Exposure to elevated CO(2) significantly increased water-soluble extractives concentration (%WSE), but had little effect on the concentration of N, cellulose, and lignin of roots. Elevated temperature had no effect on substrate quality except for increasing %WSE and decreasing the %lignin content of fine roots. No significant interaction was found between CO(2) and temperature treatments on substrate quality, except for %WSE of the fine roots. Short-term (< or = 9 mo) root decomposition in the field indicated that the roots from the ambient CO(2) and ambient temperature treatment had the slowest rate. However, over a longer period of incubation (9-36 mo) the influence of initial substrate quality on root decomposition diminished. Instead, the location of the field incubation sites exhibited significant control on decomposition. Roots at the warmer, low elevation site decomposed significantly faster than the ones at the cooler, high elevation site. This study indicates that short-term decomposition and long-term responses are not similar. It also suggests that increasing atmospheric CO(2) had little effect on the carbon storage of Douglas-fir old-growth forests of the Pacific Northwest.     

Dynamics of atmospheric nitrogen deposition in a temperate calcareous forest soil

In temperate forest ecosystems, soil acts as a major sink for atmospheric N deposition. A (15)N labeling experiment in a hardwood forest on calcareous fluvisol was performed to study the processes involved. Low amounts of ammonium ((15)NH(4)(+)) or nitrate ((15)NO(3)(-)) were added to small plots. Soil samples were taken after periods ranging from 1 h to 1 yr. After 1 d, the litter layer retained approximately 28% of the (15)NH(4)(+) tracer and 19% of (15)NO(3)(-). The major fraction of deposited N went through the litter layer to reach the soil within the first hours following the tracer application. During the first day, a decrease in extractable (15)N in the soil was observed ((15)NH(4)(+): 50 to 5%; (15)NO(3)(-): 60 to 12%). During the same time, the amount of microbial (15)N remained almost constant and the (15)N immobilized in the soil (i.e., total (15)N recovered in the bulk soil minus extractable (15)N minus microbial (15)N) also decreased. Such results can therefore be understood as a net loss of (15)N from the soil. Such N loss is probably explained by NO(3)(-) leaching, which is enhanced by the well-developed soil structure. We presume that the N immobilization mainly occurs as an incorporation of deposited N into the soil organic matter. One year after the (15)N addition, recovery rates were similar and approximately three-quarters of the deposited N was recovered in the soil. We conclude that the processes relevant for the fate of atmospherically deposited N take place rapidly and that N recycling within the microbes-plants-soil organic matter (SOM) system prevents further losses in the long term.     

Spatiotemporal variability of wet atmospheric nitrogen deposition to the Neuse River Estuary, North Carolina

Excessive nitrogen (N) loading to N-sensitive waters such as the Neuse River estuary (North Carolina) has been shown to promote changes in microbial and algal community composition and function (harmful algal blooms), hypoxia and anoxia, and fish kills. Previous studies have estimated that wet atmospheric deposition of nitrogen (WAD-N), as deposition of dissolved inorganic nitrogen (DIN: NO3-, NH3/NH4+) and dissolved organic nitrogen, may contribute at least 15% of the total externally supplied or "new" N flux to the coastal waters of North Carolina. In a 3-yr study from June 1996 to June 1999, we calculated the weekly wet deposition of inorganic and organic N at eleven sites on a northwest-southeast transect in the watershed. The annual mean total (wet DIN + wet organics) WAD-N flux for the Neuse River watershed was calculated to be 956 mg N/m2/yr (15026 Mg N/yr). Seasonally, the spring (March-May) and summer (June-August) months contain the highest total weekly N deposition; this pattern appears to be driven by N concentration in precipitation. There is also spatial variability in WAD-N deposition; in general, the upper portion of the watershed receives the lowest annual deposition and the middle portion of the watershed receives the highest deposition. Based on a range of watershed N retention and in-stream riverine processing values, we estimate that this flux contributes approximately 24% of the total "new" N flux to the estuary.     

Index models to evaluate the risk of phosphorus and nitrogen loss at catchment scales

This paper investigates index models as a tool to estimate the risk of N and P source strengths and loss at the catchment scale. The index models assist managers in improving the focus of remediation actions that reduce nutrient delivery to waterbodies. N and P source risk factors (e.g. soil nutrient concentrations) and transport risk factors (e.g. distance-to-streams) are used to determine the overall risk of nutrient loss for a case study in the Tuross River catchment of coastal southeast Australia. In the development of the N index model for Tuross, particulate N was considered important based on the observed event water quality data. In contrast to previous N index models, erosion and contributing distance were therefore included in the Tuross River catchment N index. Event-based water quality monitoring, and soil information, or in data-poor catchments conceptual understanding, are essential to represent catchment-scale processes. The techniques have high applicability in other catchments, and are complementary to other modelling techniques such as process-based semi-distributed modelling. Index models generally provide much more detailed spatial resolution than fully- or semi-distributed conceptual modelling approaches. Semi-distributed models can be used to quantify nutrient loads and provide overall direction to set the broad focus of management. Index models can then be used to refine on-the-ground investigations and investment priorities. In this way semi-distributed models can be combined with index models to provide a set of powerful tools to influence management decisions and outcomes.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

Modelling deposition and air concentration of reduced nitrogen in Poland and sensitivity to variability in annual meteorology

The relative contribution of reduced nitrogen to acid and eutrophic deposition in Europe has increased recently as a result of European policies which have been successful in reducing SO(2) and NO(x) emissions but have had smaller impacts on ammonia (NH(3)) emissions. In this paper the Fine Resolution Atmospheric Multi-pollutant Exchange (FRAME) model was used to calculate the spatial patterns of annual average ammonia and ammonium (NH(4)(+)) air concentrations and reduced nitrogen (NH(x)) dry and wet deposition with a 5 km × 5 km grid for years 2002-2005. The modelled air concentrations of NH(3) and dry deposition of NH(x) show similar spatial patterns for all years considered. The largest year to year changes were found for wet deposition, which vary considerably with precipitation amount. The FRAME modelled air concentrations and wet deposition are in reasonable agreement with available measurements (Pearson's correlation coefficients above 0.6 for years 2002-2005), and with spatial patterns of concentrations and deposition of NH(x) reported with the EMEP results, but show larger spatial gradients. The error statistics show that the FRAME model results are in better agreement with measurements if compared with EMEP estimates. The differences in deposition budgets calculated with FRAME and EMEP do not exceed 17% for wet and 6% for dry deposition, with FRAME estimates higher than for EMEP wet deposition for modelled period and lower or equal for dry deposition. The FRAME estimates of wet deposition budget are lower than the measurement-based values reported by the Chief Inspectorate of Environmental Protection of Poland, with the differences by approximately 3%. Up to 93% of dry and 53% of wet deposition of NH(x) in Poland originates from national sources. Over the western part of Poland and mountainous areas in the south, transboundary transport can contribute over 80% of total (dry + wet) NH(x) deposition. The spatial pattern of the relative contribution of national sources to total deposition of NH(x) may change significantly due to the general circulation of air.     

Phosphorus sorption characteristics of estuarine sediments under different redox conditions

Phosphorus (P) plays a major role in eutrophication of aquatic systems. Estuarine sediments could function as sources or sinks for P to the overlying water column depending upon their physico-chemical characteristics. Understanding of P sorption phenomena in estuarine sediments is important in regulating the P availability in estuaries. Phosphorus sorption characteristics of sediments from the Indian River Lagoon, Florida, USA, were determined to examine the role of selected physico-chemical properties of the sediments on soluble reactive P status in estuary water. Mean equilibrium P concentrations (EPCo) of 0.75 mg L(-1) and mean P sorption maxima (Smax) of 32.2 mg kg(-1) were obtained under anaerobic conditions, compared with EPCo of 0.05 mg L(-1) and Smax of 132.7 mg kg(-1) under aerobic conditions. The higher EPCo values under anaerobic conditions and the greater Smax values under aerobic conditions were associated with amorphous and poorly crystalline iron. These results suggest that sediments enriched with amorphous and poorly crystalline forms of iron act as an excellent reservoir for P by adsorbing excessive P in aerobic sediment zones and releasing it upon burial under anaerobic conditions. This study also indicates that P compounds in sediments independently maintain equilibrium with P in solutions. Thus, heterogeneous systems like soil and sediment simply behave as a mixture of homogeneous surfaces as far as their P sorption characteristics are concerned, and hence can be successfully described by the Langmuir and Freundlich models.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.     

Soil organic carbon and nitrogen accumulation in plots of rhizoma perennial peanut and bahiagrass grown in elevated carbon dioxide and temperature

Carbon sequestration in soils might mitigate the increase of carbon dioxide (CO2) in the atmosphere. Two contrasting subtropical perennial forage species, bahiagrass (BG; Paspalum notatum Flügge; C4), and rhizoma perennial peanut (PP; Arachis glabrata Benth.; C3 legume), were grown at Gainesville, Florida, in field soil plots in four temperature zones of four temperature-gradient greenhouses, two each at CO2 concentrations of 360 and 700 micromol mol(-1). The site had been cultivated with annual crops for more than 20 yr. Herbage was harvested three to four times each year. Soil samples from the top 20 cm were collected in February 1995, before plant establishment, and in December 2000 at the end of the project. Overall mean soil organic carbon (SOC) gains across 6 yr were 1.396 and 0.746 g kg(-1) in BG and PP, respectively, indicating that BG plots accumulated more SOC than PP. Mean SOC gains in BG plots at 700 and 360 micromol mol(-1) CO2 were 1.450 and 1.343 g kg(-1), respectively (not statistically different). Mean SOC gains in PP plots at 700 and 360 micromol mol(-1) CO2 were 0.949 and 0.544 g kg(-1), respectively, an increase caused by elevated CO2. Relative SON accumulations were similar to SOC increases. Overall mean annual SOC accumulation, pooled for forages and CO2 treatments, was 540 kg ha(-1) yr(-1). Eliminating elevated CO2 effects, overall mean SOC accumulation was 475 kg ha(-1) yr(-1). Conversion from cropland to forages was a greater factor in SOC accumulation than the CO2 fertilization effect.     

Growth management of vetiver (Vetiveria zizanioides) under Mediterranean conditions

In spite of the advantages of Vetiver grass in light of environmental aspects, this plant is not used in the Mediterranean region. The objectives of the present study were: (i) to elucidate growth parameters and establishment of Vetiver under Mediterranean conditions suitable for its various environmental applications; and (ii) to develop management practices for growing vetiver under Mediterranean conditions. In greenhouse experiments conducted under controlled conditions it was found that, in general, increasing the minimum/maximum temperatures to 21-29 degrees C significantly increased plant height. In the Mediterranean region, this range of air temperatures is obtained mainly during the summer, from June to September. For air temperatures up to 15-23 degrees C the effect of day length on plant height was insignificant, whereas in air temperature >15-23 degrees C, the plant heights under long day conditions were significantly higher than under short day. The number of sprouts per plant increased exponentially with increasing air temperature, and was not significantly affected by the day length at any air temperature range. In open fields, the heights of irrigated vetiver plants were significantly higher than those of rain-fed plants. It was concluded that, once they were established, vetiver plants could survive the dry summer of the Mediterranean region under rain-fed conditions, but they would be shorter than under irrigation. Cutting or burning of the plant foliage during the spring did not improve the survival of vetiver during the dry summer. In order to obtain fast growth of vetiver and to increase the possibility of its using the rainwater, the plants should be planted in the winter, during February and March. However, under this regime, the vetiver plant cannot be used as a soil stabilizer during the first winter, because the plant is still small. In contrast, under irrigation it is advantageous to plant vetiver at the beginning of the summer; the plant then has sufficient time to grow and develop before the beginning of the winter, so that its effect as a soil stabilizer in the following wet winter could be maximal. It was found that vetiver could grow in a wide range of substrates, such as: sandy soil, loamy sand, clay soil, crushed limestone, sandy clay loam, and tuff/peat mixture.     

Effect of surfactants on solubilization and degradation of phenanthrene under thermophilic conditions

The bioavailability and biodegradation of polycyclic aromatic hydrocarbons (PAHs) can be increased through the addition of surfactants. Previous studies of this nature have been conducted under mesophilic conditions. Hence, the aim of the present study was to investigate the effects of synthetic surfactants and biosurfactants on solubilization and degradation of phenanthrene (PHE) in a series of batch solution experiments under thermophilic conditions. Tween 80, Triton X-100, and biosurfactants produced from Pseudomonas aeruginosa strain P-CG3 (P-CG3) and Pseudomonas aeruginosa ATCC 9027 (P. 9027) were used in this study. Surfactants effectively enhanced the solubility of PHE at 50 degrees C and the biosurfactant from P-CG3 was most effective with a 28-fold increase in apparent solubility of PHE at a concentration of 10 x critical micelle concentration (CMC) compared with the controls. However, addition of synthetic surfactants or biosurfactants inhibited the biodegradation of PHE in mineral salts medium by an isolate Bacillus sp. B-UM. Degradation of PHE diminished with increasing surfactant concentrations, and PHE degradation was completely inhibited for all the surfactants tested when the concentrations were greater than their respective CMC. The growth test suggested that Tween 80 and biosurfactants were degradable, but preferential utilization of these surfactants as substrates was not the mechanism for explaining the inhibition of PHE biodegradation. Because of the hydrophobic property of B-UM, degradation inhibition of PHE by surfactants was probably due to the reduction of direct contact between bacterial cells and PHE.     

Phytoextraction of heavy metals by willows growing in biosolids under field conditions

Biosolids produced by sewage treatment facilities can exceed guideline thresholds for contaminant elements. Phytoextraction is one technique with the potential to reduce these elements allowing reuse of the biosolids as a soil amendment. In this field trial, cuttings of seven species/cultivars of Salix(willows) were planted directly into soil and into biosolids to identify their suitability for decontaminating biosolids. Trees were irrigated and harvested each year for three consecutive years. Harvested biomass was weighed and analyzed for the contaminant elements: As, Cd, Cu, Cr, Hg, Pb, Ni, and Zn. All Salix cultivars, except S. chilensis, growing in soils produced 10 to 20 t ha(-1) of biomass, whereas most Salix cultivars growing in biosolids produced significantly less biomass (<6 t ha(-1)). Salix matsudana (30 t ha(-1)) and S. × reichardtii A. Kerner (18 t ha(-1)) had similar aboveground biomass production in both soil and biosolids. These were also the most successful cultivars in extracting metals from biosolids, driven by superior biomass increases and not high tissue concentrations. The willows were effectual in extracting the most soluble/exchangeable metals (Cd, 0.18; Ni, 0.40; and Zn, 11.66 kg ha(-1)), whereas Cr and Cu were extracted to a lesser degree (0.02 and 0.11 kg ha(-1)). Low bioavailable elements, As, Hg, and Pb, were not detectable in any of the aboveground biomass of the willows.     

White spruce response to co-composted hydrocarbon-contaminated drilling waste: effects of compost age and nitrogen fertilization

There are growing interests to use co-composted drilling wastes contaminated with hydrocarbons as growth media for planting in land reclamation. However, such use of the compost may have potential problems such as inherent toxicity of residual hydrocarbon and microbial N immobilization due to high compost C to N ratios. We investigated the growth, biomass production, N uptake, and foliar delta13C of white spruce (Picea glauca [Moench] Voss) seedlings in a pot experiment using 1-, 2-, 3-, and 4-yr-old composts (with different hydrocarbon concentrations and C to N ratios) and a local noncontaminated soil with (200 kg N ha(-1)) or without N fertilization. Growth and N content of seedlings (particularly N content in roots) were lower when grown in the compost media as compared with those grown in the soil. Within the compost treatments seedling growth was affected by compost age, but the magnitude of growth reduction was not linearly proportional to hydrocarbon concentrations. Plant N uptake increased with compost age, which corresponds with an increase in indigenous mineral N concentration. Effects of N fertilization on N uptake were curtailed by the presence of indigenous mineral N (e.g., in the 4-yr-old compost) and by fertilization-induced stimulation of microbial activities (e.g., in the 1-yr-old compost). The differences in foliar delta13C values between seedlings grown in compost and soil (P < 0.05) suggest that limitations on water uptake caused by the residual hydrocarbon might have been the predominant factor limiting seedling growth in the compost media. This study suggests that water stress caused by residual hydrocarbons may be a critical factor for the successful use of co-composted drilling wastes as a growth medium.     

Integrated BIosphere Simulator (IBIS) yield and nitrate loss predictions for Wisconsin maize receiving varied amounts of nitrogen fertilizer

Agriculture in the U.S. Midwest faces the formidable challenge of improving crop productivity while simultaneously mitigating the environmental consequences of intense management. This study examined the simultaneous response of nitrate nitrogen (NO3-N) leaching losses and maize (Zea mays L.) yield to varied fertilizer N management using field observations and the Integrated BIosphere Simulator (IBIS) model. The model was validated against six years of field observations in chisel-plowed maize plots receiving an optimal (180 kg N ha(-1)) fertilizer N application and in N-unfertilized plots on a silt loam soil near Arlington, Wisconsin. Predicted values of grain yield, harvest index, plant N uptake, residue C to N ratio, leaf area index (LAI), grain N, and drainage were within 20% of observations. However, simulated NO3-N leaching losses, NO3-N concentrations, and net N mineralization exhibited less interannual variability than observations, and had higher levels of error (20-65%). Potential effects of 30% higher (234 kg N ha(-1)) and 30% lower (126 kg N ha(-1)) fertilizer N use (from optimal) on NO3-N leaching loss and maize yield were simulated. A 30% increase in fertilizer N use increased annual NO3-N leaching by 56%, while yield increased by only 1%. The NO3-N concentration in the leachate solution at 1.4 m below the soil surface was 30.7 mg L(-1). When fertilizer N use was reduced by 30% (from optimal), annual NO3-N leaching losses declined by 42% after seven years, and annual average yield only decreased by 8%. However, NO3-N concentration in the leachate solution remained above 10 mg L(-1) (11.3 mg L(-1)). Clearly, nonlinear relationships existed between changes in fertilizer use and NO3-N leaching losses over time. Simulated changes in NO3-N leaching were greater in magnitude than fertilizer N use changes.     

Photodegradation of selected herbicides in various natural waters and soils under environmental conditions

The photochemical degradation of herbicides belonging to different chemical groups has been investigated in different types of natural waters (ground, river, lake, marine) and distilled water as well as in soils with different texture and composition. Studied herbicides and chemical groups included atrazine, propazine, and prometryne (s-triazines); propachlor and propanil (acetanilides); and molinate (thiocarbamate). The degradation kinetics were monitored under natural conditions of sunlight and temperature. Photodegradation experiments were performed in May through July 1998 at low concentrations in water samples (2-10 mg/L) and soil samples (5-20 mg/kg), which are close to usual field dosage. The photodegradation rates of all studied herbicides in different natural waters followed a pseudo-first order kinetics. The half-lives of the selected herbicides varied from 26 to 73 calendar days in waters and from 12 to 40 d in soil surfaces, showing that the degradation process depends on the constitution of the irradiated media. The presence of humic substances in the lake, river, and marine water samples reduces degradation rates in comparison with the distilled and ground water. On the contrary, the degradation in soil is accelerated as the percentage of organic matter increases. Generally, the photodegradation process in soil is faster than in water. The major photodegradation products identified by using gas chromatography-mass spectrometry (GC-MS) techniques were the hydroxy and dealkylated derivatives for s-triazines, the dechlorinated and hydroxy derivative for the anilides, and the keto-derivative for the thiocarbamate, indicating a similar mode of degradation for each chemical category.     

Entropy maximizing evolutionary design optimization of water distribution networks under multiple operating conditions

Environment Systems and Decisions - The informational entropy model for flow networks was formulated over 30&nbsp;years ago by Tanyimboh and Templeman (University of Liverpool, UK) for a single...     

Steam reforming of glycerol for syngas generation under cold plasma conditions: A DFT study

Density functional theory (DFT) has been used to investigate the reaction pathways with steam reforming of glycerol under cold plasma conditions. Total energies, energy barriers, and reaction enthalpies at 298.15 K have been calculated at the GGA/PW91/DNP level. The calculation shows that, with the presence of steam, the energy barrier of glycerol conversion is reduced and the conversion from glycerol to H₂ and CO is promoted under cold plasma conditions. The formation of syngas was through a multi-step pathway via the conversion of OHCH₂CHOH, CH₂OH, CH₂O, HCO,·and CH₃, while the recombination of H generated extra H₂. The synthesis of hydrocarbons are from the recombination of·CH₃,·CH₂, and·CH, which could be primarily generated through glycerol dissociation. The structure of glycerol anion was also studied in this work, and it was less stable than the neutral molecule. The route for the formation of OHCH₂CHOH·and CH₂OH·from glycerol anion is thermodynamically favorable.