Chaotic behaviour of acoustic emission induced in hard coal by gas sorption-desorption

This paper presents study of non-linear dynamics of acoustic emission (AE) generated in coal samples subjected to gas sorption-desorption. Carbon-dioxide and methane were used as sorbats. Experimental facilities used in high pressure sorption of CO₂ and/or CH₄ on coal comprised a pressure vessel and associated pressurisation and monitoring systems. Tests were conducted on medium-rank coal obtained from the Upper Silesia Basin. Several approaches to the treatment of experimental results are proposed in order to detect and characterize deterministic chaos: (1) analysis of fractal/multifractal character of AE energy rate, using fractal generalised dimensions D _q (q); (2) analysis of temporal changes of AE energy rate and its fractal correlation dimension D ₂; and (3) evaluation of attractor dimension within the reconstructed phase space from experimental time series. It was shown that AE generated during CO₂ sorption on medium-rank coal is a more heterogeneous and lower dimensional process in comparison with AE induced by CO₂ desorption. Yet, the AE associated with desorption of CO₂ exhibits higher heterogeneity than the AE generated during desorption of CH₄. There are certain similarities between changes of D₂ during desorption of CO₂ as well desorption of CH₄. However, dynamics of these changes and character of time distributions of D₂ differ, depending on a sorbate. We do not know the precise reason for observed differences, but we presume that the carbon-dioxide molecules dissimilarity to methane molecules can account for them.     

Acoustic emission and volumetric strain induced in coal by the displacement sorption of methane and carbone dioxide

The aim of this study was to assess whether acoustic emission (AE) could carry information on preferential sorption/desorption of CH₄ or CO₂ in coal. AE and expansion/contraction of two nearly identical cylindrical coal samples were continuously monitored during displacement sorption experiments. One sample was subjected to presorption of CH₄, followed by sorption of CH₄/CO₂ mixture. With the other one, presorption of CO₂ preceded sorption of the mixture. The results obtained are the following: first, AE and stain kinetics show that the affinity of the coal tested is higher for CO₂ than for CH₄; second, methane is preferentially desorbed after presorption of CH₄ — sorption of mixture of CH₄ and CO₂; third, during displacement sorption, kinetics of AE and sample swelling/shrinkage bring out the importance of presorption and the sorbate used. It matters whether the coal is first exposed to CH₄ or to CO₂. The present study has demonstrated that injection of CO₂ into the coal previously exposed to CH₄ causes considerable swelling of the coal. On desorption after CH₄/CO₂ exchange sorption, initial shrinkage is followed by swelling of the coal. These results could have implications for the sequestration of CO₂ in coal seams and CH₄ recovery from coalbeds (ECBM). Swelling/shrinkage of the coal matrix should be included in models used to predict coal permeability and gas flow rates. They also show that the AE technique can give more insights into coal matrix-gas interactions.     

Removal of Ni(II) Using Cation Exchange Resins in Packed Bed Column: Prediction of Breakthrough Curves

Sorptive removal of Ni(II) from electroplating rinse wastewaters by cation exchange resin Dueolite C 20 was investigated at the temperature of 30°C under dynamic conditions in a packed bed. The effects of sorbent bed length 0.1–0.2 m, fixed flow rate 6 dm³ min^?1, and the initial rinse water concentration (C₀) 53.1 mg L^?1 on the sorption characteristics of Dueolite C 20 were investigated at an influent pH of 6.5. More than 94.5% of Ni(II) was removed in the column experiments. The column performance was improved with increasing bed height and decreasing the flow rate. The Thomas, Yoon–Nelson, Clark, and Wolborska models were applied to the experimental data to represent the breakthrough curves and determine the characteristic design parameters of the column. The sorption performance of the Ni(II) ions through columns could be well described by the Thomas, Yoon–Nelson, and Wolborska models at effluent‐to‐influent concentration ratios (C/C₀) >0.03 and <0.99. Among the all models, the Clark model showed the least average percentage time deviation. The sorptive capacity of electroplating rinse water using Ni(II) was found to be 45.98 mg g^?1.     

Kinetics,Mechanistic and Thermodynamics of Zn(II) Ion Sorption: A Modeling Approach

Biosorption potential of Cedrus deodara sawdust (CDS) in terms of sorption of Zn(II) ion across liquid phase has been evaluated in the present investigation. The surface of the CDS biomass before the sorption of Zn(II) ions seemed to be more porous, non‐crystalline and heterogeneous. The maximum uptake capacity of CDS was 97.39 mg g^?1. Sorption of Zn(II) ion on the surface of CDS sawdust was maximum at pH 5, temperature 45°C, initial concentration of Zn(II) ion 100 mg L^?1, biomass dose 1 g L^?1, contact time 150 min, and agitation rate 160 rpm. Pseudo second‐order kinetics with the highest linear regression coefficient (R² = 0.99), and lowest values of error functions, i.e., chi (χ²) and sum of square errors (SSE) against pseudo first‐order rate kinetics showed that the sorption of Zn(II) ion on the surface of CDS was mediated by chemosoprtive forces of attraction rather than physical adsorption. Mechanistically, relatively higher proportion of sorption of Zn(II) ion in early phase of contact time was profoundly explained by Bangham's equation and film diffusivity (D^f). Intraparticle or pore diffusion (D_p) of Zn(II) ion inside the pores of CDS was rate limiting step at the later stage of contact time. Furthermore, the thermodynamic study on sorption of metal ion delineated the fact that the Zn(II) sorption on the surface of CDS was spontaneous, endothermic together with increased entropy at solid liquid interface.     

Effect of Complexing Agents on the Acute Toxicity of Copper to Common Guppy Lebistes reticulatus (PETERS)

The acute toxicity of copper and copper plus complexing agents to common guppy Lebistes reticulatus was studied for 96 h by a static bioassay technique. The addition of complexing agents viz. disodium salt of EDTA, citric acid, sodium thiosulphate and glycine in Cu²⁺ solutions caused a great decrease in the per-cent mortality as compared to that of Cu²⁺ test solutions alone. 10 mg/l of complexing agent was added in each copper concentration in all the test series. The 96 h LC₅₀ values and 95% confidence limits in mg/l of Cu²⁺ plus were 1.23 (0.95…1.65) for Cu²⁺ alone; 4.30 (4.04 … 4.55) for Cu²⁺ plus EDTA; 1.94 (1.69 … 2.18) for Cu²⁺ plus citric acid; 3.44 (2.96 … 3.74) for Cu²⁺ sodium thiosulphate and 2.29 (2.22 … 3.02) for Cu²⁺ plus glycine.     

Der Einfluß der Komplexierung auf die Kupfertoxizität bei Blaualgen

Some aspects of the influence of copper speciation on toxicity for blue-green algae are reviewed. The experimental part concentrates on Oscillatoria redekei and Aphanizomenon gracile. The two investigated species produce strong extracellular copper complexing ligands: Oscillatoria redekei in the exponential and stationary growth phase, and Aphanizomenon gracile has a distinct detoxification capacity. The detoxification of copper by synthetic agents was investigated using ethylene-diamine-tetraacetic acid. Simultaneous addition of Cu²⁺ and Na₂EDTA gives evidence for a slow complexation reaction. Hence an excess of Na₂EDTA is necessary for a fast and complete detoxification of copper. Model calculations are reported to show that the precipitation of copper compounds is not probable under the conditions used.     

Variations in dissolved CO2 and CH4 in a first‐order stream and catchment: an investigation of soil–stream linkages

Spatial and seasonal variations in CO₂ and CH₄ concentrations in streamwater and adjacent soils were studied at three sites on Brocky Burn, a headwater stream draining a peatland catchment in upland Britain. Concentrations of both gases in the soil atmosphere were significantly higher in peat and riparian soils than in mineral soils. Peat and riparian soil CO₂ concentrations varied seasonally, showing a positive correlation with air and soil temperature. Streamwater CO₂ concentrations at the upper sampling site, which mostly drained deep peats, varied from 2·8 to 9·8 mg l^?1 (2·5 to 11·9 times atmospheric saturation) and decreased markedly downstream. Temperature‐related seasonal variations in peat and riparian soil CO₂ were reflected in the stream at the upper site, where 77% of biweekly variation was explained by an autoregressive model based on: (i) a negative log‐linear relationship with stream flow; (ii) a positive linear relationship with soil CO₂ concentrations in the shallow riparian wells; and (iii) a negative linear relationship with soil CO₂ concentrations in the shallow peat wells, with a significant 2‐week lag term. These relationships changed markedly downstream, with an apparent decrease in the soil–stream linkage and a switch to a positive relationship between stream flow and stream CO₂. Streamwater CH₄ concentrations also declined sharply downstream, but were much lower (<0·01 to 0·12 mg l^?1) than those of CO₂ and showed no seasonal variation, nor any relationship with soil atmospheric CH₄ concentrations. However, stream CH₄ was significantly correlated with stream flow at the upper site, which explained 57% of biweekly variations in dissolved concentrations. We conclude that stream CO₂ can be a useful integrative measure of whole catchment respiration, but only at sites where the soil–stream linkage is strong. Copyright © 2004 John Wiley & Sons, Ltd.     

Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

Regeneration and Reuse of a Seaweed‐Based Biosorbent in Single and Multi‐Metal Systems

A seaweed‐waste material resulting from the processing of Ascophyllum nodosum was previously shown to be very efficient at removing Zn(II), Ni(II) and Al(III) both in single and multi‐metal waste streams. In this study, the regeneration of the biosorbent using an acid wash resulted in the release of high metal concentrations during multiple desorption cycles. Maximum desorption efficiencies (DE) of 183, 122 and 91% were achieved for Zn(II), Ni(II) and Al(III), respectively, for subsequent metal loading cycles, significantly exceeding the desorption rates observed for conventional sorbents. The regeneration of the sorbent was accomplished with very little loss in metal removal efficiency (RE) for both single and multi‐metal systems. Values of 92, 96 and 94% RE were achieved for Zn(II), Ni(II) and Al(III), respectively, for the 5^th sorption cycle in single metal aqueous solutions. A slight decrease was observed for the same metals in multi‐metal systems with maximum REs of 85, 82 and 82% for Zn(II), Ni(II) and Al(III), respectively. This study showed that the novel sorbent derived from a seaweed industrial waste would be suitable for multiple metal sorption cycles without any significant loss in RE.     

Fourier transform infrared microspectroscopic characterization of Neoproterozoic organic microfossils from the Fifteenmile Group in Yukon,Canada

Conventional and synchrotron radiation‐based (SR) Fourier transform infrared microspectroscopies (micro‐FTIR) were applied to four types of ~ 810 Ma organic‐walled microfossils together with diffuse organic matter (OM) and one irregularly shaped structure from the Fifteenmile Group, in Yukon, Canada, for their chemical characterization. The microfossils comprised one filamentous type and three coccoidal types. Micro‐FTIR mapping analysis revealed the micrometer‐scale, spatial distribution of organic components (aliphatic C‐H bonds) and carbonate in the microfossils. Based on comparisons of CH₃/CH₂ peak height ratios (R_3/2) and morphologies of the microfossils (without the diffuse OM) to those of previously described Proterozoic microfossils, possible affinities of the microfossils are suggested, as follows. Palaeolyngbya? and Glenobotrydion belong to bacteria. Myxococcoides is not clearly characterized due to the significant mixing with diffuse OM containing abundant aliphatic C‐H groups. The irregularly shaped structure may represent a eukaryote. The diffuse OM may represent a mixture of decomposed microbial cells and extracellular polymeric substances (EPS). SR micro‐FTIR measurements of two coccoid types (Glenobotrydion and Unnamed Coccoid Form D) revealed that the R_3/2 values of the internal spots with wall structures are similar to those without wall structures in Glenobotrydion: those values from Unnamed Coccoid Form D were different. The results suggest that these two coccoids are different chemically as well as morphologically. Micro‐FTIR characterization of the organic‐walled microfossils together with morphological analysis provides new insight into their biological affinities.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Biosorption of Cd(II) and Zn(II) by Nostoc commune: Isotherm and Kinetics Studies

In this study, Nostoc commune (cyanobacterium) was used as an inexpensive and efficient biosorbent for Cd(II) and Zn(II) removal from aqueous solutions. The effect of various physicochemical factors on Cd(II) and Zn(II) biosorption such as pH 2.0–7.0, initial metal concentration 0.0–300 mg/L and contact time 0–120 min were studied. Optimum pH for removal of Cd(II) and Zn(II) was 6.0, while the contact time was 30 min at room temperature. The nature of biosorbent and metal ion interaction was evaluated by infrared (IR) technique. IR analysis of bacterial biomass revealed the presence of amino, carboxyl, hydroxyl, and carbonyl groups, which are responsible for biosorption of Cd(II) and Zn (II). The maximum biosorption capacities for Cd(II) and Zn(II) biosorption by N. commune calculated from Langmuir biosorption isotherm were 126.32 and 115.41 mg/g, respectively. The biosorption isotherm for two biosorbents fitted well with Freundlich isotherm than Langmuir model with correlation coefficient (r² < 0.99). The biosorption kinetic data were fitted well with the pseudo‐second‐order kinetic model. Thus, this study indicated that the N. commune is an efficient biosorbent for the removal of Cd(II) and Zn(II) from aqueous solutions.     

Evidence that piezometers vent gas from peat soils and implications for pore‐water pressure and hydraulic conductivity measurements

Entrapped gas bubbles in peat can alter the buoyancy, storativity, void ratio and expansion/contraction properties of the peat. Moreover, when gas bubbles block water‐conducting pores they can significantly reduce saturated hydraulic conductivity and create zones of over‐pressuring, perhaps leading to an alteration in the magnitude and direction of groundwater flow and solute transport. Some previous researches have demonstrated that these zones of over‐pressuring are not observed by the measurements of pore‐water pressures using open‐pipe piezometers in peat; rather, they are only observed with pressure transducers sealed in the peat. In has been hypothesized that open‐pipe piezometers vent entrapped CH₄ to the atmosphere and thereby do not permit the natural development of zones of entrapped gas. Here we present findings of the study to investigate whether piezometers vent subsurface CH₄ to the atmosphere and whether the presence of piezometers alters the subsurface concentration of dissolved CH₄. We measured the flux of methane venting from the piezometers and also determined changes in pore‐water CH₄ concentration at a rich fen in southern Ontario and a poor fen in southern Quebec, in the summer of 2004. Seasonally averaged CH₄ flux from piezometers was 1450 and 37·8‐mg CH₄ m^?2 d^?1 at the southern Ontario site and Quebec site, respectively. The flux at the Ontario site was two orders of magnitude greater than the diffusive flux at the site. CH₄ pore‐water concentrations were significantly lower in open piezometers than in water taken from sealed samplers at both the Ontario and Quebec sites. The flux of CH₄ from piezometers decreased throughout the season suggesting that CH₄ venting through the piezometer exceeded the rate of methanogenesis in the peat. Consequently we conclude that piezometers may alter the gas dynamics of some peatlands. We suggest that less‐invasive techniques (e.g. buried pressure transducers, tracer experiments) are needed for the accurate measurement of pore‐water pressures and hydraulic conductivity in peatlands with a large entrapped gas component. Furthermore, we argue that caution must be made in interpreting results from previous peatland hydrology studies that use these traditional methods. Copyright © 2009 John Wiley & Sons, Ltd.     

Dynamic,Mechanistic, and Thermodynamic Modeling of Zn(II) Ion Biosorption onto Zinc Sequestering Bacterium VMSDCM

The surface of the bacterial cells before the biosorption of Zn(II) ion has been found rough, heterogeneous, and non‐crystalline together with tremendous protrusions and negatively charged functional groups. The bacterium was characterized as rod shaped with Gram‐negative type of cell wall structure. In reaction dynamics, pseudo‐second‐order kinetics with higher linear correlation coefficient (R²) ranging between 0.97 and 0.99, lower sum of square errors (SSE) (0.035–0.081) and chi (χ²) (0.0013–0.009) provided a better explanation of sorption of Zn(II) ion on bacterium surface as compared to pseudo‐first‐order model. The removal of Zn(II) was governed by both film and intra‐particle diffusion at onset and later stage of sorption of metal ion on the surface of bacterial cells. The R² (0.92–0.94) for intra‐particle diffusion model was quite higher with lower values of SSE (9.56–16.33) and chi (χ²) (11.26–19.65) against the Bangham's model. The positive value of ΔH (16.628 × 10^?6 kJ/mol) and ΔS (5320.90 kJ/mol/K) showed that the biosorption of Zn(II) ion across liquid phase on bacterial surface was endothermic with increased randomness at solid–liquid interface. The negative values of ΔG demarcated the whole process as spontaneous in nature. In the present work, the distribution coefficient was found to be > 0.5 at various temperature ranges. At the attainment of equilibrium, the residual concentration of Zn(II) ion in liquid phase was around 0.6 mg/L, which was much below the limit described by United States Environmental Protection Agency (USEPA), i.e. 5 mg/L.     

Winter methane dynamics beneath ice and in snow in a temperate poor fen

The influence of winter on methane (CH₄) stored in pore water and emitted through snow was investigated in a temperate poor fen in New Hampshire over two winters. Methane accumulated beneath ice layers (1 cm) deposited by freezing rain, resulting in snow-pore air mixing ratios as high as 140 ppmv during the first winter and 600 ppmv during the second. An early winter snow crust of 300 kg m^?3 caused no discontinuity in a linear mixing ratio profile and therefore was not observed to retard snowpack emissions. Methane concentration-depth profiles in pore water steepened and concentrations increased by as much as 400 μM at the 10 and 20 cm depths as the ice cover formed. This suggests that the peat-ice cover plays an important part in CH₄ build-up in pore water by limiting the transport of gases between the peat and the atmosphere. Pore water concentrations gradually declined through late winter. The seasonality of dissolved CH₄ in pore water over two winters and one summer showed an average annual amplitude of 1.3 gCH₄m^?2 (25–75cm depth range), with a winter maximum of 4.7gCH₄m^?2. Emissions during the winter with average snowfall accounted for a larger percentage (9.2% in 1993–1994) of total annual emission than the winter with below-average snowfall and warmer air temperature (2% in 1994–1995). Emissions averaged 56 and 26mg m^?2 day^?1 during the first and second winter (December, January and February), respectively.     

Removal of Copper,Nickel, and Zinc Ions from Electroplating Rinse Water

Removal of copper, nickel, and zinc ions from synthetic electroplating rinse water was investigated using cationic exchange resin (Ceralite IR 120). Batch ion exchange studies were carried out to optimize the various experimental parameters (such as contact time, pH, and dosage). Influence of co‐existing cations, chelating agent EDTA on the removal of metal ion of interest was also studied. Sorption isotherm data obtained at different experimental conditions were fitted with Langmuir, Freundlich, Redlich–Peterson, and Toth models. A maximum adsorption capacity of 164 mg g^?1 for Cu(II), 109 mg g^?1 for Ni(II), and 105 mg g^?1 for Zn(II) was observed at optimum experimental conditions according to Langmuir model. The kinetic data for metal ions adsorption process follows pseudo second‐order. Presence of EDTA and co‐ions markedly alters the metal ion removal. Continuous column ion exchange experiments were also conducted. The breakeven point of the column was obtained after recovering effectively several liters of rinse water. The treated rinse water could be recycled in rinsing operations. The Thomas and Adams–Bohart models were applied to column studies and the constants were evaluated. Desorption of the adsorbed metal ions from the resin column was studied by conducting a model experiments with Cu(II) ions loaded ion exchange resin column using sulfuric acid as eluant. A novel lead oxide coated Ti substrate dimensionally stable (DSA) anode was prepared for recovery of copper ions as metal foil from regenerated liquor by electro winning at different current densities (50–300 A cm^?2).     

Adsorption of Zinc using Tea Factory Waste: Kinetics,Equilibrium and Thermodynamics

In India, the annual production of tea is ca. 857,000 tonnes, which is 27.4% of the total world production. The amount of tea factory waste (TFW) produced per annum after processing is ca. 190,400 tonnes. TFW can be used as a low cost adsorbent for the removal of toxic metals from the aqueous phase. An investigation was carried out to study the feasibility of the use of TFW as an adsorbent for the removal of the heavy metal, zinc. Equilibrium, kinetic and thermodynamic studies were reported. The straight line plot of log (q_e–q) versus time t for the adsorption of zinc shows the validity of the Lagergren equation. The various steps involved in adsorbate transport from the solution to the surface of the adsorbent particles were dealt with by using a Weber‐Morris plot, q_e versus t^0.5 for the TFW. The rate controlling parameters, k_id,1 and k_id,2, were determined and it was found that the macro‐pore diffusion rate was much larger than micro‐pore diffusion rate. A batch sorption model, which assumes the pseudo‐second‐order mechanism, was used to predict the rate constant of sorption, the equilibrium sorption capacity and the initial sorption rate with the effect of initial zinc (II) ion concentration. Equilibrium data obtained from the experiments were analyzed with various isotherms, i. e., Freundlich, Langmuir, Redlich‐Peterson and Tempkin. The adsorption equilibrium was reached in 30 min and the adsorption data fitted well to all models. The maximum adsorption capacity of TFW for zinc (II) ions was determined to be 14.2 mg/g. The capacity of adsorption on Zn(II) increased with increasing temperatures and pH. The maximum uptake level of zinc was observed at pH of 4.2. The various thermodynamic parameters, i. e., ΔG°, ΔH° and ΔS°, were estimated. The thermodynamics of the zinc ion/TFW system indicated a spontaneous, endothermic and random nature of the process. The results showed that the TFW, which has low economical value, is a suitable adsorbent for the removal of zinc (II) ions from aqueous solutions.     

Degradation Pathway of the Photochemical Oxidation of Ethylenediaminetetraacetate (EDTA) in the UV/H2O2-process

The degradation pathway for the oxidation of EDTA in the UV/H₂O₂-process was investigated. In absence of iron ions, the mineralization of EDTA is dominated by the reaction of the HO-radicals generated by the photolysis of H₂O₂. The organic degradation products iminodiacetate (IMDA), glycinate, oxamate, glyoxylate, oxalate and formate, and the inorganic degradation products carbon dioxide, ammonia, nitrate, nitrite, and cyanate were found. In the presence of iron ions, photolytic decarboxylation processes inside the complex get an important role during degradation, and the organic degradation products ethylenediaminetriacetate (ED3A), ethylenediaminediacetate (EDDA), ethylenediaminemonoacetate (EDMA) were also found. By combining product studies with balances of carbon and nitrogen, the degradation pathway in the UV/H₂O₂-process could be elucidated. The degradation of EDTA was fast (k_deg = 0.012 s^–1), and no toxic degradation products were identified. Therefore, the process is well suited for the elimination of EDTA in water treatment.     

Carbon fluxes from eroding peatlands – the carbon benefit of revegetation following wildfire

Peatlands are among the largest long‐term soil carbon stores, but their degradation can lead to significant carbon losses. This study considers the carbon budget of peat‐covered sites after restoration, following degradation by past wildfires. The study measured the carbon budget of eight sites: four restored‐revegetated sites, two unrestored bare soil control sites, and two intact vegetated controls over two years (2006–2008). The study considered the following flux pathways: dissolved organic carbon (DOC); particulate organic carbon (POC); dissolved carbon dioxide (CO₂); primary productivity; net ecosystem respiration, and methane (CH₄). The study shows that unrestored, bare peat sites can have significant carbon losses as high as 522 ± 3 tonnes C/km²/yr. Most sites showed improved carbon budgets (decreased source and/or increased sink of carbon) after restoration; this improvement was mainly in the form of a reduction in the size of the net carbon source, but for one restored site the measured carbon budget after four years of restoration was greater than observed for vegetated controls. The carbon sequestration benefit of peatland restoration would range between 122 and 833 tonnes C/km²/yr. Copyright © 2011 John Wiley & Sons, Ltd.     

The impact of pipe flow in riparian peat deposits on nitrate transport and removal

The effect of preferential flow in soil pipes on nitrate retention in riparian zones is poorly understood. The characteristics of soil pipes and their influence on patterns of groundwater transport and nitrate dynamics were studied along four transects in a 1‐ to >3‐m deep layer of peat and marl overlying an oxic sand aquifer in a riparian zone in southern Ontario, Canada. The peat‐marl deposit, which consisted of several horizontal layers with large differences in bulk density, contained soil pipes that were generally 0.1 to 0.2 m in diameter and often extended vertically for 1 to >2 m. Springs that produced overland flow across the riparian area occurred at some sites where pipes extended to the peat surface. Concentrations of NO₃^?–N (20–30 mg L^?1) and dissolved oxygen (DO) (4–6 mg L^?1) observed in peat pipe systems and surface springs were similar to values in the underlying sand aquifer, indicating that preferential flow transported groundwater with limited nitrate depletion. Low NO₃^?–N concentrations of <5 mg L^?1 and enriched δ¹⁵N values indicated that denitrification was restricted to small areas of the peat where pipes were absent. Groundwater DO concentrations declined rapidly to <2 mg L^?1 in the peat matrix adjacent to pipes, whereas high NO₃^?–N concentrations of >15 mg L^?1 extended over a larger zone. Low dissolved organic carbon values at these locations suggest that supplies of organic carbon were not sufficient to support high rates of denitrification, despite low DO conditions. These data indicate that it is important to develop a greater understanding of pipes in peat deposits, which function as sites where the transport of large fluxes of water with low biogeochemical reaction rates can limit the nitrate removal capacity of riparian zones. Copyright © 2011 John Wiley & Sons, Ltd.