The potential for climatic factors as well as soil–plant–climate interactions to change as a result of rising levels of atmospheric CO₂ concentration is an issue of increasing international environmental concern. Agricultural and forest practices and managements may be important contributors to mitigating elevated atmospheric CO₂ concentrations. A computer model was developed using the Structural Thinking and Experiential Learning Laboratory with Animation (STELLA) software for soil CO₂ emissions from a short-rotation woody crop as affected by soil water and temperature regimes, root and microbial respiration, and surficial processes such as rainfall, irrigation, and evapotranspiration. The resulting model was validated with good agreement between the model predictions and the experimental measurements prior to its applications. Two scenarios were then chosen to estimate both diurnal and annual soil CO₂ emissions from a 1-ha mature cottonwood plantation as affected by soil temperature, soil (i.e., root and microbial) respiration, and irrigation. The simulation resulted in typical diurnal soil respiration and CO₂ emission patterns, with increases from morning to early afternoon and decreases from early afternoon to midnight. This pattern was driven by diurnal soil temperature variations, indicating that soil temperature was the main influence on soil respiration and CO₂ efflux into the atmosphere. Our simulations further revealed that the average seasonal soil respiration rate in summer was 1.6 times larger than in winter, whereas the average seasonal CO₂ emission rate in summer was 1.77 times larger than in winter. Characteristic annual variation patterns for soil respiration and CO₂ emission also were modeled, with both increasing from January 1 through June 30 followed by steady declines from September 1 through December 31. These results suggest that the STELLA model developed is a useful tool for estimating soil CO₂ emission from a short-rotation woody crop plantation.

In the present paper, undoped and Ni-doped TiO2 sol-gel nanopowders have been prepared in order to establish the effect of Ni dopant on both material structure and photocatalytic properties. Two dopant concentrations of the transition metal (0.5 and 2 wt%) have been tested. The influence of both Ni dopant concentration and temperature of thermal treatment on the prepared powders has been followed using X-ray diffraction (XRD) method. A proper program has been used in order to establish the complete XRD structural characterization (lattice parameters, crystrallite sizes, internal strains). X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM) coupled with surface area electron diffraction (SAED) techniques have completed the structural and morphological characterization of the prepared materials. Magnetic measurements and photocatalytic activity determinations have also been performed. The correlation between the results of the mentioned methods has been accomplished, and the detailed interpretation of the relation between structure and photocatalytic activity measurements has been done. The concentration of 0.5 wt% of Ni dopant ensures a better photocatalytic activity, compared to that of 2 wt%. © 2013 Springer Science+Business Media Dordrecht.

Understanding denitrification rates in groundwater ecosystems can help predict where agricultural reactive nitrogen (N) contributes to environmental degradation. In situ groundwater denitrification rates were determined in subsoil, at the bedrock interface and in bedrock at two sites, grassland and arable, using an in situ 'push-pull' method with 15N-labelled nitrate (NO3 --N). Measured groundwater denitrification rates ranged from 1.3 to 469.5 μg N kg-1 day-1. Exceptionally high denitrification rates observed at the bedrock interface at grassland site (470 ± 152 μg N kg-1 day-1; SE, standard error) suggest that deep groundwater can serve as substantial hotspots for NO 3 --N removal. However, denitrification rates at the other locations were low and may not substantially reduce NO3 --N delivery to surface waters. Denitrification rates were negatively correlated with ambient dissolved oxygen, redox potential, k s and NO3 - (all p values, p < 0.01) and positively correlated with SO4 2- (p < 0.05). Higher mean N 2O/(N2O + N2) ratios at an arable (0.28) site than the grassland (0.10) revealed that the arable site has higher potential to indirect N2O emissions. Identification of areas with high and low denitrification and related site parameters can be a tool to manage agricultural N to safeguard the environment. © 2013 Springer Science+Business Media Dordrecht.

Development of aminopolycarboxylate chelants (APCs) having enhanced biodegradability is gaining increasing focus to replace the EDTA and its homologs with those used widely for the ex situ treatment of contaminated soils and are potential eco-threats. The paper reports the chelant-assisted extraction of the toxic metals (Cd, Cu, Pb, and Zn) from the metal-spiked European reference soils (Eurosoil 1 and Eurosoil 4) using biodegradable APCs, namely EDDS, GLDA, and HIDS. The effects of chelant-to-metal molar ratio, solution pH, and metal/chelant stability constants were evaluated, and compared with that of EDTA. The selectivity aptitude of the biodegradable chelants towards the toxic metals was assumed from the speciation calculations, and a proportionate correlation was observed at neutral pH. Pre- and post-extractive solid phase distributions of the target metals were defined using the sequential extraction procedure and dissolution of metals from the theoretically immobilized fraction was witnessed. The effect of competing species (Al, Ca, Fe, Mg, and Mn) concentrations was proven to be minimized with an excess of chelant in solution. The highlight of the outcomes is the superior decontamination ability of GLDA, a biodegradable APC, at minimum chelant concentration in solution and applicability at a wide range of pH environments.

Hydrogels based on p(4-VP) of different dimensions were prepared and, after chemical modification, were used in the removal of one of the most potent toxic materials, cyanide. Macro and micron p(4-VP) hydrogel swelling behavior was evaluated in various aquatic environments. HCl, bromoethane, 1-bromobutane, 1-bromohexane, and 2-bromoethylamine were used as quaternizing agents to generate positive charges on both p(4-VP) macrogels and microgels. The modified p(4-VP) macrogels and microgels were used in cyanide ion removal for the first time from aqueous environments. The p(4-VP)-HCl at macro and micro sizes removed almost 49 and 61 mg cyanide ions per gram hydrogel in deionized water after modification, respectively. Moreover, the absorption capacity of the modified p(4-VP) hydrogel did not change significantly in tap, drinking, and creek waters. Parameters that affect the absorption process, such as cyanide concentration, contact time, hydrogel amount, and contaminated water source, were investigated. Additionally, magnetic field responsive macro and micro p(4-VP) hydrogel composites provided many advantages, such as easy handling after cyanide absorption, e.g., ready removal of cyanide-loaded p(4-VP) composites with an externally applied magnetic field. Langmuir and Freundlich adsorption isotherms were applied to the data obtained for cyanide uptake from aqueous environments.

Many studies have shown the relationship between fire clearing and mercury contamination of aquatic ecosystems in the Brazilian Amazon. This study aimed at quantifying mercury content in long-time cultivated soils and at assessing the potential of a fire-free alternative clearing technique on mercury retention for long-time cultivated soils compared to traditional slash-and-burn. This case study included five land uses: one crop plot and one pasture plot cleared using slash-and-burn, one crop plot and one pasture plot cleared using chop-and-mulch, and one 40-year-old forest as a control. Low mercury concentrations were recorded in the surface horizon (24.83 to 49.48 ng g⁻¹, 0–5 cm depth). The long-time cultivation (repeated burnings) of these soils triggered large mercury losses in the surface horizon, highlighted by high enrichment factors from surface to deeper horizons. The predominant effect of repeated burnings before the experimental implementation did not let us to distinguish a positive effect of the chop-and-mulch clearing method on soil mercury retention for crops and pastures. Moreover, some processes related to the presence of the mulch may favor mercury retention (Hg volatilization decrease, cationic sites increase), while others may contribute to mercury losses (cationic competition and dislocation, mobilization by the dissolved organic matter).

A novel porous biomorph-genetic composite of α-Fe₂O₃/Fe₃O₄/C (PBGC-Fe/C) with eucalyptus wood template was prepared, characterized and tested for its sorption capacity of As(V) from aqueous solution. The result indicated that the PBGC-Fe/C material retained the hierarchical porous structure of eucalyptus wood with three different types of pores (widths 70∼120, 4.1∼6.4 and 0.1∼1.3 μm) originating from vessels, fibres and pits of the wood, respectively. Its surface area was measured to be 59.2 m²/g. With increasing initial As(V) concentration from 5 to 100 mg/L, the amounts of As(V) sorbed on the pulverized PBGC-Fe/C sorbent (<0.149 mm) increased from 0.50 to 4.01 mg/g at 25 °C, from 0.50 to 4.83 mg/g at 35 °C and from 0.50 to 4.19 mg/g at 45 °C, and the corresponding removal rates decreased from 99.97 to 40.10 % at 25 °C, 99.95 to 48.40 % at 35 °C and 99.92 to 42.05 % at 45 °C. At the initial concentrations of 5, 10 and 50 mg/L, the sorption capacities for the unpulverized PBGC-Fe/C sorbent (>3 mm) were determined to be 0.50, 0.99 and 2.49 mg/g, respectively, which exhibited a similar average value to those of fine particles or nanoparticles of iron oxides. The sorption could well be described by the pseudo-second-order kinetic equation. The equilibrium data were found to follow Freundlich as well as Langmuir isotherms.

Persistence and dissipation kinetics of clothianidin were studied in sandy loam soil of sugarcane ecosystem by adopting a rapid and sensitive analytical method. This single-step analytical method was observed to be superior to multi-step conventional method reported to quantify the residues of clothianidin in soil, in terms of recovery, sensitivity and rapidity besides cost-effectiveness. The recoveries of clothianidin were in the range of 93.19 ± 3.07-95.43 ± 2.09 % at 0.01-0.1 μg/g level of fortification in soil. The limit of quantification of the method was 0.01 μg/g. Dissipation pattern of clothianidin followed first-order kinetics with a good fit (R 2 > 0.96). Half-life of clothianidin was 17.2 and 17.4 days at the single (50 g a.i./ha) and double doses (100 g a.i./ha), respectively. Clothianidin was observed to be more persistent than imidacloprid and thiamethoxam in the soil of tropical sugarcane ecosystem. © 2013 Springer Science+Business Media Dordrecht.

The impacts of dissolved organic matter (DOM) on the removal of 17β-estradiol (E2) in horseradish peroxidase (HRP)-mediated oxidative coupling systems were investigated in this study. The results showed that the removal rate of E2 and the affinity of HRP to E2 had been significantly decreased in the presence of DOM. Compared with urban sludge DOM (USDOM), river sediment DOM (RSDOM), which features relatively low aromaticity and molecular weight and a large number of O-containing groups, more strongly inhibited the E2–HRP–H₂O₂ reactions than USDOM. The products were analyzed with electrospray ionization mass spectrometry. The results suggested that the self-coupling of E2 was suppressed in the presence of DOM, likely resulting from cross-coupling between DOM and E2 or self-coupling of DOM in the HRP system. The results are useful in understanding the fate of estrogens in natural systems.

The growth of white-rot fungus Pleurotus eryngii F032 in a suitable medium can degrade an azo dye Reactive Black 5 (RB5), because of its ability to produce ligninolytic enzymes such as lignin peroxidase (LiP), manganese peroxidase (MnP), and laccase that able to degrade and transform the complex structure of the dye into a less toxic compound. The effect of environmental factors such as initial concentration of Reactive Black 5, pH, temperature of growth medium, surfactant (Tween 80), and agitation were also investigated. The productions of ligninolytic enzymes were enhanced by increasing the white-rot fungi growth in optimum conditions. The decolorization of Reactive Black 5 were analyzed by using UV–vis spectrophotometer at the maximum absorbance of 596 nm. The white-rot fungus, P. eryngii F032 culture exhibited 93.56 % decolorization of 10 mg/L RB5 within 72 h of incubation in dark condition with agitation. The optimum pH and temperature for the decolorizing activity was recorded at pH 3 and 40 °C, respectively. The addition of surfactant (Tween 80) increased the decolorization to 93.57 % and agitation of growth medium at 120 rpm enhanced the distribution of nutrients to the fungus thus optimized the enzymatic reaction that resulted maximum decolorization of RB5 which was 93.57 %. The molecular docking studies were performed using Chimera visualization software as to analyze the decolorization mechanism of RB5 at molecular level.