Fate of heavy metals in a strongly acidic shooting‐range soil: small‐scale metal distribution and its relation to preferential water flow

To assess the mobility of Pb and associated metals in a highly contaminated shooting range soil (Losone, Ticino, Switzerland), we investigated the spatial distribution of the metals and their relation to preferential water flow paths. A 2.2 m² plot located 40 m behind the stop butt was irrigated with a solution containing bromide and Brilliant Blue, a slightly sorbing dye. A soil profile 50 cm in width was sampled down to 80 cm with a spatial resolution of 2.5 cm, resulting in 626 samples. Concentrations of elements (12 ≤ Z ≤ 92) were determined by energy‐dispersive Xray fluorescence spectrometry, and Brilliant Blue concentrations were determined with a chromameter. In the acidic (pH 3), organic matter‐rich, well drained Dystric Cambisol, maximum concentrations of 80.9 g kg^‐1 Pb, 4.0 g kg^‐1 Sb, and 0.55 g kg^‐1 Cu were measured in the topsoil. Within 40 cm soil depth, however, Pb, Sb, and Cu approached background concentrations of 23 mg kg^‐1, 0.4 mg kg^‐1, and 9.4 mg kg^‐1, respectively. The even horizontal distribution and the steep gradient along soil depth indicate tight metal binding in the topsoil, and a fairly homogeneous transport front. In contrast, water flow through the profile was highly heterogeneous. In the uppermost 20 cm, preferential flow was initiated by heterogeneous infiltration at the soil surface, but had no influence on metal distribution. Below 20 cm, however, preferential flow originated from larger tree roots, and metal concentrations were significantly elevated along these macropores. Spatial distributions of Pb, Sb, and Cu were similar, suggesting that all three metals are strongly retained in the topsoil and transported along preferential water flow paths in the subsoil.     

引入分维理论评价土壤对优势流的敏感性

Food dye Brilliant Blue was introduced as the tracer in a dye-tracing experiment to obtain dye profile patterns of sandy loam soil,aeolian sandy soil,percolating paddy soil and permeable paddy soil.The dyed soil profiles were then photographed and the photos were scanned into a computer.Edited with certain software,only the dyed areas were left on the profile photos,which indicted the preferential flow paths for water and solute transport.Fractal dimensions of the dye patterns were calculated according to Arnold‘s function.Soil particle size distribution was analyzed by pipette method.The regression analysis showed that there was significant relationship between soil clay content and fractal dimension D of the dye pattern of soil profile.Based on the experiment results,the possibility of introducing fractal dimension to estimation of soil sensitivity to preferential flow is discussed.     

Field study on colloid transport using fluorescent microspheres

Understanding colloid movement through the vadose zone is important, because colloids may facilitate transport of some less mobile contaminants. Experimental evidence of colloid transport in the vadose zone, especially at the field scale, is rare. We developed and tested a method to detect and quantify local concentrations of fluorescent microspheres (MS) with a diameter of 1 μm in unsaturated soil based on fluorescent microscopy. The detection limit was 400 × 10⁶ MS kg^?1 field‐moist soil for an automated counting method, and 20 × 10³ MS kg^?1 for manual counting. To test the method in the field, we applied a 40‐mm pulse with an input concentration of 14.6 × 10⁹ MS litre^?1 on two plots during 6 hours, together with bromide (Br^?) and the food dye Brilliant Blue (BB). The concentrations of MS were determined on horizontal cross‐sections by a randomly distributed sampling scheme, either directly after application or 90 days after application and a rainfall of 100 mm. Mass recoveries for the MS of 85 and 65% were acceptable in view of the field conditions. Even after infiltration of particle‐free water, the largest MS concentrations were measured at the soil’s surface, which pointed at physical retention mechanisms. An additional selective sampling of hydrologically active preferential flow pathways, guided by the dye infiltration patterns, revealed that the MS were transported to similar depths as BB, that is 0.80 m directly after irrigation and 1.7 m after 90 days. This implies that also a small fraction of the particulate tracers was rapidly transported to larger depths, regardless of their physico‐chemical properties.     

运用染色示踪方法研究土壤质地对土壤水非均匀流动特征的影响

为研究土壤质地对土壤水流运动非均匀特征的影响,在砂土、壤土和粉质粘土中采用亮蓝(砂土)和碘离子(壤土和粉质粘土)作为示踪剂分别开展了2个、5个和4个不同入渗条件(土壤初始含水率和入渗水量)的染色示踪试验,通过计算活动流场模型(Active Region Model,ARM)分形特征参数(γ)来定量描述和比较不同入渗条件下土壤水流运动的非均匀特征。研究结果表明,(1)活动流场模型较好的捕捉到了土壤水流运动整体的非均匀信息;(2)当其它入渗条件(土壤初始含水率和入渗水量)相同时,土壤水在细质地土壤中运动的非均匀程度要高于其在粗质地土壤中运动的非均匀程度。     

黄淮海平原三种土壤中优势流现象的试验研究

在黄淮海平原选择三种不同质地类型的土壤（砂壤土、淤土、风沙土）,各设１．５ｍ×１．５ｍ两个小区,其中一个小区在试验开始前两癸灌水约５６ｋｇ,以获得不同的初始含水量。将１００ｍｍ含有染色剂亮蓝的水灌入小区,一天之后,开挖１ｍ×１ｍ的剖面拍照,进行图像分析处理,计算剖面中染色百分比随深度的变异,研究所形成的优势流的状况与土壤类型、土壤初始含水量的关系。结果表明：不同土壤发生优势流的程度不同,结构发育好     

Dye tracer infiltration in the plough layer after straw incorporation

Straw residues may be accumulated in isolated zones in the plough layer after mouldboard ploughing. This may limit straw decomposition because of limited nitrogen availability depending on the prevalent water flow pathways induced by tillage. In this study, we used the food dye Brilliant Blue FCF (Color Index 42090) to make visible the flow pathways in the plough layer of a loamy soil after incorporation of 10 tonne of dry mass ha^− 1, and to get a qualitative and quantitative interpretation of the small-scale flow behaviour. Approximately 1.3 L of a 4 g L^− 1 Brilliant Blue solution was applied at a matric head of − 1 cm with an infiltrometer, equipped with a 25 cm-diameter disk. Horizontal cross-sections of 50 × 50 cm were photographed at 1.5 to 3.5 cm depth intervals. High-resolution spatial maps of Brilliant Blue concentration were derived from the scanned photographs, using separate calibration relationships between the measured Brilliant Blue concentrations and the color spectra and depth for the soil and the straw. Pronounced lateral dye movement was observed through the soil matrix owing to soil sorptivity. In cases of high sorptivity, the dye barely reached the depth of straw incorporation. Otherwise, enhanced preferential dye transport directed towards the incorporated straw was made visible and the stained water eventually ponded on the plough pan which induced lateral redistribution. Although the straw inclusions contributed to dye transport, they did not retain a substantial part of the applied dye mass, owing to the low density and surface area of straw. However, these inclusions may enhance the fast migration of potential pollutants such as nitrate or pesticides out of the tilled layer where much of the transformation occurs due to biological activity.     

Analysing flow patterns from dye tracer experiments in a forest soil using extreme value statistics

Preferential flow of water in soil is now recognized as a common phenomenon. It results in complex flow patterns that can be visualized by dye tracers and increases the risk of pollutants reaching greater depths. We analysed the behaviour of a risk index for vertical solute propagation based on extreme value theory. This risk index can be calculated from binary images of dye‐stained soil profiles and is defined as the form parameter of the generalized Pareto distribution. We did five tracer experiments with Brilliant Blue and iodide under changing initial (variable initial soil moisture) and experimental conditions (different irrigation rates). Our results indicate some persistence of the risk index against small changes of experimental conditions such as the irrigation rate. On the other hand, it seems to be affected by initial soil moisture. Comparisons of Brilliant Blue and iodide patterns show that the form parameter alone is not sufficient to estimate the risk of vertical solute propagation. Therefore we propose to combine the risk index with the scale parameter of the generalized Pareto distribution.     

Quantifying dye tracers in soil profiles by image processing

Developing and testing models for solute transport in the field requires experimental data on the spreading of solutes in the soil. Obtaining such data is costly, and a substantial part of the total costs is in the preparation and chemical analysis of the tracing compounds in the gathered samples. We developed a cheap method to quantify the concentration of the mobile dye tracer Brilliant Blue FCF from digitized photographs of stained soil profiles, and we have tested it in the field. Soil sampling and chemical analyses were necessary only to establish a calibration relation between the dye content and the colour of the soil. The digital images were corrected for geometrical distortions, varying background brightness, and colour tinges, and then they were analysed to determine the soil colour at sampling points in the profiles. The resident concentration of the dye was modelled by polynomial regression with the primary colours red, green, blue and the soil depth as explanatory variables. Concentration maps of Brilliant Blue were then computed from the digitized images with a spatial resolution of 1 mm. Validation of the technique with independent data showed that the method predicted the concentration of the dye well, provided the corrected images contained only the colours included in the calibration.     

Water and bromide transport in a heterogeneous glacial sand

We investigated water flow and bromide transport under agricultural field conditions, using TDR and tensiometer measurements as well as a bromide tracer experiment. The soil, an Albic Luvisol consisting of sand covering glacial loam, is highly heterogeneous with polygon nets formed by sand‐filled frost wedges. Water flow and bromide transport are influenced by the thickness of the glacial sand horizon and the soil structure. Both cause a variation of the actual evapotranspiration up to ± 25 mm/yr. Water and bromide are preferentially transported on the inclined soil layer boundaries into the sand wedges. From there infiltrating water may be redistributed into the surrounding glacial till. Approximately, the depths of the bromide centers of mass can be deduced using the piston flow concept. Small‐scale mass balances of the tracer show that vertical sections with bromide deficits and bromide surpluses are well balanced within a horizontal range of 1.8 m to 2.8 m. This distance is interpreted as the lateral influence of the sand wedges.     

Spatial variation of tracer distribution in a structured clay field soil

Within the sensitive soils of the River Oder Basin (E Brandenburg, Germany), chloride‐tracer transport was studied with respect to soil‐surface conditions of the well structured clayey topsoil (disturbed vs. undisturbed) and irrigation mode (flooding vs. sprinkling). The spatial variation of chloride and dye distribution was sampled in a regular grid within different soil depths. Different methods were used for the analysis of spatial heterogeneity: a heterogeneity index HI derived from fitting parameters of the cumulative distribution function, semivariogram analyses to identify the spatial representativity of observations and to classify the spatial variation, and Spearman's rank correlations to examine the spatial similarity of tracer distribution across different soil depths. Soil aggregation was obvious throughout the soil profile, and macropores and fractures were preferred flow paths for the tracer. Flood irrigation resulted in more “uniform” distribution than sprinkling did. However, preferential flow was identified for all treatments, where, once established below the surface layer, flow paths led to heterogeneity indices manifesting nonuniform flow and reduced lateral mixing between macropores and soil matrix. Within the flooded plot, spatial structure of chloride concentration was moderate unlike the strongly structured variation within the sprinkled plots. For purposes to generalize and to assess regional risk of the water and solute transport within the topsoil of the River Oder Basin, spatial autocorrelation ranges of about 15 cm should be considered and included into concepts of soil protection and land‐use management, soil‐sampling strategies, or modeling approaches.     

土壤优先流运动的活动流场模型模拟和敏感性分析

在壤土和砂土条件下分别采用碘-淀粉染色示踪方法和亮蓝染色示踪方法各开展了2个染色示踪试验,分别采用活动流场模型和二域模型模拟计算了各试验入渗后染色区内的土壤含水率和溶质浓度分布,通过相对均方根误差分析评价了两个模型模拟预测优先流发展的有效性;此外,通过敏感性分析研究了不同入渗条件（土壤质地、入渗水量和土壤初始含水率）下活动流场模型模拟预测结果（入渗深度）对活动流场模型分形特征参数变化的敏感度。模型检验分析结果显示活动流场模型对土壤水入渗深度、入渗后染色区内土壤含水率和溶质浓度分布的预测精度要明显高于二域模型的模拟预测精度;活动流场模型较好的捕捉到了优先流运动整体的非均匀特征。敏感性分析结果显示,当降雨入渗水量和土壤初始含水率相同时,入渗深度对活动流场模型分形特征参数（γ）的敏感度随着γ的增大而增大;相同活动流场模型分形特征参数（γ）值条件下（即流动非均匀程度相同）,入渗深度对活动流场模型分形特征参数（γ）的敏感度随着入渗水量的增大和土壤初始含水率的升高而减小。     

鹤大高速（G11）低路基边坡土壤优先流特征研究

为了探明盐分在低路基公路边坡土壤中的运移方式,以鹤大高速公路(G11)低路基段边坡土壤为研究对象,引入优先流,来探讨盐分随土壤水分运动的过程。采用亮蓝染色示踪和图像解析方法,分析土壤剖面优先路径水平和垂直分布特征。结果显示:染色区和非染色区的土壤性质存在显著差异,染色区土壤存在较多的大孔隙。在水平剖面上,相同影响半径优先路径数量随着土层深度的增加而减少,同一土层中1.0~10.0mm影响半径的优先路径数量要远远多于10.0mm影响半径的优先路径数量。在垂直剖面上,优先流特征指标染色覆盖率(DC)、均匀入渗深度(UF)、优先流分数(PF-fr)、长度指数(LI)和峰值(PI)分别为40.10%,4.10cm,801.96cm2,74.44%,543.6cm和5。低路基边坡土壤这种重塑的土体中存在较为明显的优先流现象,且优先流对氯盐在土壤中的运移起着重要的作用。优先流指标的提出,为今后量化土壤优先流发生程度提供了一个很好的研究方法。     

Macropore flow estimations under no-till and till systems

The processes associated with water movement through silt loam soils involve both the flow through macropores as preferential flow or macropore flow and flow through the micropore as matrix flow. Macropore and matrix flow components were separated from total flow by a hydrograph-separation technique which used the assumption of dual porosity and a tracer mass balance. A mixture of potassium bromide was applied through a rain simulator to four plots in northern Mississippi in two rain events at 12.7 mm/h lasting 5 and 3 h separated by 6 h. The plots were either tilled or no-tilled with drains installed by two methods at the surface of the fragipan. The magnitude of water and bromide (Br⁻) transported by macropore flow to a drain line were estimated and the resulting hydrographs provided an indication of the potential significance of macropore flow in transporting water and non-reactive chemicals through macropores to the shallow groundwater system. Matrix flow appears to contribute the majority of the water moving to the drains even during the early stages of the drain flow hydrographs. The no-till plots produced more macropore flow than the tilled plots, independent of how the drains were installed. Macropore flow in the drainage at any time was small as compared to the matrix flow; however it contributed a disproportionate amount of Br⁻ tracer. These data support the concept that models used to predict mass balances using only the matrix (Darcian) flow will underestimate those chemicals that move like bromide into the soil profile.     

Percolation characteristics of a water-repellent sandy forest soil

In a tracer experiment TDR transect measurements were made to study percolation behaviour in a 120‐year‐old pine stand (Pinus sylvestris) on a water‐repellent sandy soil (Haplic Arenosol). The experiment (with potassium iodide) showed an 80% labelling of the total flow in organic layers, whereas the area of transport in the mineral soil was sharply reduced to 12–30%. The average diameters of these preferential flow paths were about 8–15 cm. The TDR measurements indicate a homogeneous flow only for a short period from February until April. At this time of the year preferential flow is insignificant, because the soil is at approximately field capacity and not repellent to water. During summer (May to September) the soil dries out, and most precipitation results in preferential flow during this period. For any daily rainfall exceeding 10 mm, water infiltrates down to 1 m depth in the soil, which nevertheless, is still within the root zone. This kind of deep percolation results in the subsoil’s wetting to field capacity (pF 1.8) earlier than the topsoil. A one‐dimensional numerical model (SWAP) was used to simulate mean water balance with hydraulic functions with and without a water‐repellency term. From the results of our tracer experiment we showed that the de‐watering process in spring could be simulated well using the traditional piston flow concept, while the rewetting behaviour could be described more realistically using the mobile–immobile concept for water repellency.     

Solute recycling by crops and leaching in a drained arable soil

Preferential flow, as it bypasses the soil matrix, can greatly enhance the leaching of chemicals. When a soil is drained there is the risk that such short‐circuiting results in more or less direct passage of polluting chemicals from the soil to the groundwater. If the groundwater table is shallow the chemicals could be transferred back into the surface soil by hydraulic lift through roots and subsequent release by exudation or from decaying plant residues and again become exposed to leaching by preferential flow, thus strongly enhancing the chance of export via the drains. We investigated the leaching of bromide in a tile‐drained arable field over 2 years of crop rotation. The site was a former wetland, artificially drained a century ago for agriculture. Bromide was applied over 1.6 ha at a dosage of 10 g Br per m² in August 1995 after the harvest of wheat. During the 2 years 18% of the applied bromide was exported via the drainage system, most of it in preferential flow events and more than half of it in a single winter storm 5 months after the application. Within 7 months 56% of the applied tracer was leached out of the main root zone into the groundwater. Subsequently the tracer re‐emerged in water taken up by sugar beet in the following season. The beet accumulated 50% of the initially applied bromide in their leaves and released it again after harvest when the leaves were left as green manure on the field. Our results show that this recycling of solutes to the topsoil can have an important influence on their leaching as the solutes are thus again exposed to preferential transport into drains in the course of preferential flow events.     

A morphological approach to understanding preferential flow using image analysis with dye tracers and X-ray Computed Tomography

A key problem facing soil physics and hydropedology at present is some of the standard theories of water flow in soils do not fully reflect the processes at the pore scale, and thus, cannot be adequately used for prediction. As such, examination of soil structure is vital for hydropedologists. Realisation that solutes move preferentially through soil into groundwaters has meant research in this area has increased in importance. This paper describes a multi-scale approach to analyse transport mechanisms using visualisation techniques. Chloride and Brilliant Blue tracers were applied to undisturbed soil cores to examine the physical and morphological properties associated with preferential flow in a range of soil types. Following collection of serial digital images, it was possible to examine and quantify the nature of active water flow mechanisms in terms of both dye-stained pathways and spatial distribution of dye concentration, using image analysis. Preferential flow linked to water potential and soil structural discontinuity was observed in all but the coarsest textured soil which conformed to uniform flow theory. A high level of variability in flow patterns was noted between the soil types. Such information as to how a soil dynamically re-wets is key for hydropedologists involved in applications such as pollution modelling. This is especially significant when considering a wetting mechanism, such as preferential flow, that cannot be adequately described by conventional soil physics.     

Estimation of nitrate retention in a Ferralsol by a transient-flow method

Anion retention is important in highly weathered soils that contain large amounts of iron and aluminium oxides with surfaces of variable charge. Sorption mechanisms retard anionic solute transfer through these soils. We determined the retardation factor for nitrate in highly weathered Ferralsols from New Caledonia from dynamic experiments using a transient‐flow method, and we evaluated the effect of soil solution concentration and organic matter content. A simple method with sectionable tubes was used to determine the nitrate isotherm during non‐steady‐state water flow under unsaturated conditions. The topsoil retarded the movement of nitrate, and the sorption followed a linear isotherm. In subsoils, retardation factors were larger and increased from 1.15 to 2.05 at soil pH as the NO₃^–‐N concentration of the input solution decreased from 71.43 to 0.35 mm , indicative of a non‐linear isotherm. Positive surface charge sites were considered to be of two types: one with strong affinity for nitrate at small concentrations and one with weak affinity for adsorption of nitrate at larger concentrations. This type of isotherm with high‐ and low‐energy sites is similar to those found for oxyanions and heavy metals. The related anion exchange capacity was larger than that usually observed in soils of variable charge. Not all exchange sites were detected with our method, and some sites were obviously not available for nitrate retention.     

土壤性质对入渗再分布影响的显色示踪试验研究

同时使用染色剂和碘离子作为示踪剂,染色剂用于示踪大孔隙通道,根据碘-淀粉显色反应确定实际流动模式。开展了6组试验,研究了土壤大孔隙特征和非均匀流动特性,比较了粉土和粘土2种土壤,入渗水量分别为20、40、60和80 mm以及不同流动边界条件下的土壤水和溶质再分布特性。实验资料显示,入渗水再分布主要受到湿润模式的影响。入渗水量较小的情况下,水流运动主要发生在大孔隙中,随着入渗水量增大,入渗模式与孔隙发育表现出显著的区别,随着入渗水量的增加,水流运动非均匀性表现出先增加,随后减小的趋势。溶质迁移非均匀性取决于水流非均匀流动特性,然而表现出更多的不确定性。     

Interaction Between Plant Roots and Soil Water Flow in Response to Preferential Flow Paths in Northern China

Preferential flow is expected to provide preferential channels for plant root growth and variations in soil water flow, but few studies were conducted to imply the impacts of these changes, particularly for preferential flow in stony soils. This study aimed to characterize soil water flow and plant root distribution in response to preferential flow paths and quantitatively describe the relation between plant root distribution and soil water flow. Field dye‐tracing experiments centered on experimental plants were conducted to determine the root length density and soil water flow process. Laboratory analyses were performed to characterize changes in the relative concentration of the accumulated effluent and the degree of interaction between plant roots and soil water flow. The amount of fine plant roots with preferential flow paths decreased with increasing soil depth for all experimental plots. The largest plant roots were recorded in the upper soil layers to a depth of 20 cm. The relative concentration of the accumulated effluent increased with time and decreased with soil depth under saturated soil conditions, whereas a distinct early turning point for the relative concentration of the accumulated effluent was observed in the 0–20‐cm soil columns, and the relative concentration of the accumulated effluent initially decreased and then increased with time under unsaturated soil conditions. This study provides quantitative information with which to characterize the interaction between plant roots and soil water flow in response to preferential flow paths in soil–plant–water systems. Copyright © 2016 John Wiley & Sons, Ltd.     

Identification of efficient transport pathways from the soil surface to field drains by smoke injection

Surface‐applied agrochemicals have been measured soon after application in drainage water from agricultural fields in various studies. The bypass flow from the soil surface into drains may result from direct macropore connections. In order to identify such macropores, smoke was injected into three 1.15‐m deep tile drains in a sandy loam soil using ‘smoke oil’ and an air blower. Smoke‐emitting macropores (SEM) at the soil surface were characterized as having either strong or weak plumes when compared with reference plumes from 3‐ and 6‐mm wide tubes. A total drain length of 93 m, at three separate sub‐drain lines, was investigated after harvest of wheat in autumn 2010 and in spring 2011. Smoke only reached the soil surface layer via earthworm burrows, located in a 1‐m wide belt directly above the drain lines. The distributions of SEM across the drain line were similar in autumn and spring. The average number of SEM along the drain lines was 2.3 SEM m^?1 drain line. Ponded water in 6‐cm wide rings was applied above 52 burrows, including 17 reference burrows that did not emit smoke, and 13 pathways in the soil were examined with dye tracer. Strong SEM marked the entrance of efficient transport pathways conducting surface‐applied water and dye tracer into the drain. Water infiltration rates were significantly larger (P < 0.05) in strong SEM (geometric mean, 195 ml minute^?1; n = 19) than in weak SEM (geometric mean, 63 ml minute^?1; n = 16) and for the reference burrows (geometric mean, 39 ml minute^?1; n = 17). The results suggest that the smoke injection technique is a valuable means of identifying potentially efficient pathways for surface‐applied contaminants to enter drains, such pathways being associated primarily with strong SEM.