Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

Fire‐induced changes in soil water repellency increased fingered flow and runoff rates following the 2004 Huelva wildfire

Water repellency (WR) from fire‐affected soils can affect infiltration processes and increase runoff rates. We investigated the effects of fire‐induced changes in soil WR and the related soil hydrological response after one of the largest wildfires in Spain in recent years. The vertical distribution of WR in soil profiles was studied under oak and pine forests and the wetting pattern was analysed after rainfall simulations (85 mm h^?1 during 60 min). After burning, the persistence of WR in soils under oaks increased in the upper 0–5 cm of soil in comparison with pre‐fire WR, but no significant changes were observed under pines. After a fire, WR was stronger and the thickness of the water‐repellent layer increased in soils under pines in the upper 0–16 cm of soil. The hydrophobic layer was thinner under oaks, where no strong to extremely water‐repellent samples were observed below 12 (in burnt soils) and 8 cm (in unburnt soils). Uniform wetting was observed through soil depth in burnt and unburnt soils under oaks, as a consequence of the prevailing matrix flux infiltration. Water was mostly stored in the upper few centimetres and soil became rapidly saturated, favouring a continuous rise in the runoff rate during the experiments. Moisture profiles under pines showed a heterogeneous wetting pattern, with highly irregular wetting fronts, as a result of wettable and water‐repellent three‐dimensional soil patches. In this case, runoff rates on burnt plots increased in relation to unburnt plots, but runoff generation reached a steady state after 25–30 min of simulated rainfall at an intensity of 85 mm h^?1. Rainfall water infiltrated over a small part of the ponded area, where the vertical pressure of the water column overcame the WR. Copyright © 2010 John Wiley & Sons, Ltd.     

A bimodal four‐parameter lognormal linear model of soil water repellency persistence

Soil water repellency may be characterized in terms of the delayed infiltration time of a water droplet resting on the soil surface, which is, water drop penetration time (WDPT), or repellency persistence. Such repellency persistence varies nonlinearly with soil water content (θ_g), although no models have been proposed to reproduce the variation of WDPT with θ_g in soils. Dynamic factor analysis (DFA) is used to identify two common patterns of unexplained variability in a scattered dataset of WDPT versus θ_g measurements. A four‐parameter lognormal distribution was fitted to both common patterns obtained by DFA, and these were combined additively in a weighted multiple linear bimodal model. We show how such an empirical model is capable of reproducing a large variety of WDPT versus θ_g curve shapes (N = 80) both within a wide range of measured WDPTs (0–17 000 s) and for samples with organic matter content ranging from 21·7 to 80·6 g (100 g)^?1. Copyright © 2009 John Wiley & Sons, Ltd.     

Fire severity and surface rock fragments cause patchy distribution of soil water repellency and infiltration rates after burning

Although fire‐induced soil water repellency (SWR) and its effects on soil hydrology and geomorphology have been studied in detail, very few studies have considered the effect of rock fragments resting on the soil surface or partly embedded in soil. In this research, we have studied the effect of rock fragments on the strength and spatial distribution of fire‐induced SWR at different fire severities. A fire‐affected area was selected for this experiment and classified into different zones according to fire severity (unburned, low, moderate and high) and rock fragment cover (low, <20% and high, >60%). During 7 days after fire, SWR and infiltration rates were assessed in the soil surface covered by individual rock fragments and in the midpoint between two adjacent rock fragments (with maximum spacing of 20 cm). SWR increased with fire severity. Rock fragments resting on the soil surface increased the heterogeneity of the spatial distribution of fire‐induced SWR. SWR increased significantly with rock fragment cover in bare areas under moderate and high fire severity, but quantitatively important changes were only observed under high fire severity. In areas with a low rock fragment cover, water repellency from soil surfaces covered by rock fragments increased relative to bare soil surfaces, with increasing SWR. In areas with a high rock fragment cover, SWR increased significantly from non‐covered to covered soil surfaces only after low‐severity burning. Rock fragment cover did not affect infiltration rates, although it decreased significantly in soil surfaces after high‐severity burning in areas under low and high rock fragment cover. Copyright © 2013 John Wiley & Sons, Ltd.     

Hydrochemical behaviour of dissolved nitrogen and carbon in a headwater stream of the Canadian Shield: relevance of antecedent soil moisture conditions

This paper examines the impact of contrasting antecedent soil moisture conditions on the hydrochemical response, here the changes in dissolved nitrogen (NO₃^?, NH₄⁺ and dissolved organic nitrogen (DON)) and dissolved organic carbon (DOC) concentrations, of a first‐order stream during hydrological events. The study was performed in the Hermine, a 5 ha forested watershed of the Canadian Shield. It focused on a series of eight precipitation events (spring, summer and fall) sampled every 2 or 3 h and showing contrasted antecedent moisture conditions. The partition of the eight events between two groups (dry or wet) of antecedent moisture conditions was conducted using a principal component analysis (PCA). The partition was controlled (first axis explained 86% of the variability) by the antecedent streamflow, the streamflow to precipitation ratio Q/P and by the antecedent groundwater depth. The mean H⁺, NO₃^?, NH₄⁺, total dissolved nitrogen and DOC concentrations and electrical conductivity values in the stream were significantly higher following dry antecedent conditions than after wetter conditions had prevailed in the Hermine, although the temporal variability was high (17 to 138%). At the event scale, a significantly higher proportion of the changes in DON, NO₃^?, and DOC concentrations in the stream was explained by temporal variations in discharge compared with the seasonal and annual scales. Two of the key hydrochemical features of the dry events were the synchronous changes in DOC and flow and the frequent negative relationships between discharge and NO₃^?. The DON concentrations were much less responsive than DOC to changes in discharge, whereas NH was not in phase with streamflow. During wet events, the synchronicity between streamflow and DON or NO₃^? was higher than during dry events and discharge and NO₃^? were generally positively linked. Based on these observations, the hydrological behaviour of the Hermine is conceptually compatible with a two‐component model of shallow (DON and DOC rich; variable NO₃^?) and deep (DON and DOC poor; variable NO₃^?) subsurface flow. The high NO₃^? and DOC levels measured at the early stages of dry events reflected the contribution from NO₃^?‐rich groundwaters. The contribution of rapid surface flow on water‐repellent soil materials located close to the stream channel is hypothesized to explain the DOC levels. An understanding of the complex interactions between antecedent soil moisture conditions, the presence of soil nutrients available for leaching and the dynamics of soil water flow paths during storms is essential to explain the fluxes of dissolved nitrogen and carbon in streams of forested watersheds. Copyright © 2007 John Wiley & Sons, Ltd.     

Spatial and temporal variability of surface water repellency in sandy loam soils of NW Spain under Pinus pinaster and Eucalyptus globulus plantations

This work was undertaken for two main purposes. One was to examine spatial and temporal variability in surface water repellency under field conditions in sandy loam forest soils of NW Spain, and its relationship to weather and soil moisture conditions. The other purpose was to get further inside in the dynamics of soil water repellency by studying a wetting–drying cycle under controlled laboratory conditions. Both for the field and laboratory study, water repellency was determined using the Water Drop Penetration Time test. Soil water repellency under field conditions was found to exhibit a seasonal pattern, i.e. it peaked during the summer and was absent between November and May. The time required for repellency to become re‐established during the spring was shorter under eucalyptus than under pine. Spatial variability peaked at an early stage of soil drying and was minimal during the wet period when soils were hydrophilic as well as at the end of the summer, when repellency was strongest. Spatial and temporal variability in water repellency was found to be negatively correlated with soil moisture and, to a lesser extent, with antecedent rainfall. The moisture range of the so‐called transition zone (below which the soil is hydrophobic and also above which it is hydrophobic) differed for the pine (21–50%) and eucalyptus plantations (17–36%). The lower and upper bounds of the transition zone agreed well with the soil moisture contents at the permanent wilting point and at field capacity, respectively. The laboratory results with samples in the wetting phase confirmed those of the field tests. Water repellency increased slightly during the drying phase, but not so much as in the field. Copyright © 2011 John Wiley & Sons, Ltd.     

On standardizing the ‘Water Drop Penetration Time’ and the ‘Molarity of an Ethanol Droplet’ techniques to classify soil hydrophobicity: A case study using medium textured soils

Two common methods to assess soil hydrophobicity are the ‘Water Drop Penetration Time’ and ‘Molarity of an Ethanol Droplet’ techniques. For these, uncertainty exists regarding the representativeness of laboratory tests reflecting field conditions, their replicability, and the comparability of results between the two techniques. Using air-dried soils with a broad particle size and hydrophobicity range, this study shows that a high representativeness and replicability of results can be achieved. A close relationship between the two tests was found for highly, but not for moderately hydrophobic soils. Guidelines are suggested to increase representativeness, replicability and comparability of results in future studies. © 1998 John Wiley & Sons, Ltd.     

Soil hydrological response under simulated rainfall in the Dehesa land system (Extremadura,SW Spain) under drought conditions

Soil hydrology was investigated in the Guadelperalón experimental watershed in order to determine the influence of land use and vegetation cover on runoff and infiltration within the Dehesa land system. Five soil–vegetation units were selected: (1) tree cover, (2) sheep trials, (3) shrub cover, (4) hillslope grass and (5) bottom grass. The results of the simulated rainfall experiments performed at an intensity of 56·6 mm h⁻¹ during one hour on plots of 0·25 m², and the water drop penetration time test indicate the importance of water repellency in the Dehesa land system under drought conditions. Low infiltration rates (c. 9–44 mm h⁻¹) were found everywhere except at shrub sites and in areas with low grazing pressure. Soil water repellency greatly reduced infiltration, especially beneath Quercus ilex canopies, where fast ponding and greater runoff rates were observed. The low vegetation cover as a consequence of a prolonged drought and grazing pressure, in conjunction with the soil water repellency, induces high runoff rates (15–70 per cent). In spite of this, macropore fluxes were found in different locations, beneath trees, on shrub-covered surfaces, as well as at sites with a dominance of herbaceous cover. Discontinuity of the runoff fluxes due to variations in hydrophobicity causes preferential flows and as a consequence deeper infiltration, especially where macropores are developed. © 1998 John Wiley & Sons, Ltd.     

Synergistic effects of water repellency and macropore flow on the hydraulic conductivity of a burned forest soil,south‐east Australia

Research shows that water repellency is a key hydraulic property that results in reduced infiltration rates in burned soils. However, more work is required in order to link the hydrological behaviour of water repellent soils to observed runoff responses at the plot and hillslope scale. This study used 5 M ethanol and water in disc infiltrometers to quantify the role of macropore flow and water repellency on spatial and temporal infiltration patterns in a burned soil at plot (<10 m²) scale in a wet eucalypt forest in south‐east Australia. In the first summer and winter after wildfire, an average of 70% and 60%, respectively, of the plot area was water repellent and did not contribute to infiltration. Macropores (r > 0·5 mm), comprising just 5·5% of the soil volume, contributed to 70% and 95%, respectively, of the field‐saturated and ponded hydraulic conductivity (K_p). Because flow occurred almost entirely via macropores in non‐repellent areas, this meant that less than 2·5% of the soil surface effectively contributed to infiltration. The hydraulic conductivity increased by a factor of up to 2·5 as the hydraulic head increased from 0 to 5 mm. Due to the synergistic effect of macropore flow and water repellency, the coefficient of variation (CV) in K_p was three times higher in the water‐repellent soil (CV = 175%) than under the simulated non‐repellent conditions (CV = 66%). The high spatial variability in K_p would act to reduce the effective infiltration rate during runoff generation at plot scale. Ponding, which tend to increase with increasing scale, activates flow through macropores and would raise the effective infiltration rates at larger scales. Field experiments designed to provide representative measurements of infiltration after fire in these systems must therefore consider both the inherent variability in hydraulic conductivity and the variability in infiltration caused by interactions between surface runoff and hydraulic conductivity. Copyright © 2010 John Wiley & Sons, Ltd.     

矿物法组合处理垃圾填埋场渗滤液的研究

垃圾填埋场渗滤液水质复杂,危害性大,对其无害化处理尚未得到很好解决。研究发现,垃圾渗滤液中有机污染物可标识划分为亲水性和疏水性两大类物质。实验针对性采用亲水的天然膨润土处理亲水性有机物,疏水的有机膨润土处理疏水性有机物,再结合鸟粪石结晶法去除氨氮,从而获得一套处理中晚期垃圾渗滤液的经济高效的矿物法组合处理技术。采用GC-MS技术鉴定经矿物法处理后的垃圾渗滤液,亲水性和疏水性有机污染物的种类和含量都明显降低。检测进水与出水的COD、氨氮及重金属浓度这三项关键指标,垃圾渗滤液原液COD为2566 mg/L,氨氮3859 mg/L,重金属Hg为0.305 mg/L。矿物法组合处理后出水的COD为245mg/L,氨氮48 mg/L,重金属Hg未检出。矿物组合法为垃圾渗滤液的无害化处理提供了一条新的思路。