Biochar application to hardrock mine tailings: Soil quality,microbial activity,and toxic element sorption

Waste rock piles from historic mining activities remain unvegetated as a result of metal toxicity and high acidity. Biochar has been proposed as a low-cost remediation strategy to increase soil pH and reduce leaching of toxic elements, and improve plant establishment. In this laboratory column study, biochar made from beetle-killed pine wood was assessed for utility as a soil amendment by mixing soil material from two mine sites collected near Silverton, Colorado, USA with four application rates of biochar (0%, 10%, 20%, 30% vol:vol). Columns were leached seven times over 65 days and leachate pH and concentration of toxic elements and base cations were measured at each leaching. Nutrient availability and soil physical and biological parameters were determined following the incubation period. We investigated the hypotheses that biochar incorporation into acidic mine materials will (1) reduce toxic element concentrations in leaching solution, (2) improve soil parameters (i.e. increase nutrient and water holding capacity and pH, and decrease compaction), and (3) increase microbial populations and activity. Biochar directly increased soil pH (from 3.33 to 3.63 and from 4.07 to 4.77 in the two materials) and organic matter content, and decreased bulk density and extractable salt content in both mine materials, and increased nitrate availability in one material. No changes in microbial population or activity were detected in either mine material upon biochar application. In leachate solution, biochar increased base cations from both materials and reduced the concentrations of Al, Cd, Cu, Pb, and Zn in leachate solution from one material. However, in the material with greater toxic element content, biochar did not reduce concentrations of any measured dissolved toxic elements in leachate and resulted in a potentially detrimental release of Cd and Zn into solution at concentrations above that of the pure mine material. The length of time of effectiveness and specific sorption by biochar is variable by element and the toxic element concentration and acidity of the initial mine material.     

Review of interactions between phosphorus and arsenic in soils from four case studies

Arsenic is a non-essential element that poses risks in many environments, including soil, groundwater, and surface water. Insights into the environmental biogeochemistry of As can be gained by comparing As and P reaction processes. Arsenic and P are chemical analogues, and it is proposed that they have similar chemical behaviors in environmental systems. However some chemical properties of As and P are distinct, such as redox reactions, causing the biogeochemical behavior of the two elements to differ. In the environment, As occurs as either As(V) or As(III) oxyanions (e.g., AsO₄^3? or AsO₃^3?). In contrast, P occurs predominantly as oxidation state five plus; most commonly as the orthophosphate ion (PO₄^3?). In this paper, data from four published case studies are presented with a focus on P and As distribution and speciation in soil. The goal is show how analyzing P chemistry in soils can provide greater insights into As reaction processes in soils. The case studies discussed include: (1) soil developed from shale parent material, (2) mine-waste impacted wetland soils, (3) phosphate-amended contaminated soil, and (4) plants grown in biochar-amended, mine-contaminated soil. Data show that while P and As have competitive reactions in soils, in most natural systems they have distinct biogeochemical processes that create differing mobility and bioavailability. These processes include redox reactions and rhizosphere processes that affect As bioavailability. Results from these case studies are used as examples to illustrate how studying P and As together allows for enhanced interpretation of As biogeochemical processes in soils.     

Bioavailability and toxicity of antimony

Antimony (Sb) is a toxic trace element widely distributed in the lithosphere and mainly associated with arsenic. Sb compounds are considered to be pollutants of high interest, however, the biogeochemical behaviour of Sb is still largely unknown, especially compared to other well-known toxic elements. In particular, questions remain about the availability of Sb to vascular plants. In this work, we focused on the following problems: (i) Sb uptake by plants; (ii) the availability of Sb to plants and (iii) variations in uptake and distribution of essential plant nutrients and trace elements resulting from bioaccumulation of Sb in Triticum aestivum (wheat) seedlings. The seedlings were either germinated or grown in media enriched with Sb. By the end of germination, concentrations of Sb in the seedlings germinated in Sb-amended media increased significantly. Sb content was highest in the roots and lowest in the leaves of the seedlings. After transfer of the seedlings germinated in an Sb-free medium to Sb-enriched media, Sb concentration in the seedlings increased with time, especially in the roots. Bioaccumulation of Sb influenced concentrations of different macro- and trace elements in all parts of the plants. The least variations were observed in the leaves, probably because the increase of Sb concentration in leaves was not as significant as in the seeds and roots.     

Distribution and speciation of arsenic around roots in a contaminated riparian floodplain soil: Micro-XRF element mapping and EXAFS spectroscopy

Riparian soils are periodically flooded, leading to temporarily reducing conditions. Diffusion of O₂ through plants into the rhizosphere maintains oxic conditions around roots, thereby promoting trace element fractionation along a redox gradient from the reduced soil matrix towards the oxic rhizosphere. The aim of this study was to determine the distribution and speciation of arsenic around plant roots in a contaminated (170-280 mg/kg As) riparian floodplain soil (gleyic Fluvisol). The analysis of soil thin sections by synchrotron micro-X-ray fluorescence (μ-XRF) spectrometry showed that As and Fe were enriched around roots and that As was closely correlated with Fe. Arsenic contents of three manually separated rhizosphere soil samples from the subsoil were 5-9 times higher than respective bulk As contents. This corresponds to the accumulation of about half of the total As in the subsoil in Fe-enrichments around roots. The speciation of As in the soil was assessed by oxalate extractions at pH 3.0 as well as by X-ray absorption near edge structure (XANES) and extended X-ray fine structure (EXAFS) spectroscopy. More than 77% of the total As was oxalate extractable in all samples. XANES and EXAFS spectra demonstrated that As was predominantly As(V). For the accurate analysis of the EXAFS data with respect to the bonding of As(V) to the Fe- or Al-octahedra of (hydr)oxides and clays, all 3-leg and 4-leg multiple scattering paths within the As^(V)O₄-tetrahedron were considered in a fully constrained fitting scheme. We found that As(V) was predominantly associated with Fe-(hydr)oxides, and that sorption to Al- and Mn-hydroxides was negligible. The accumulation of As in the rhizosphere may affect As uptake by plants. Regarding the mobility of As, our results suggest that by oxygenation of the rhizosphere, plants attenuate the leaching of As from riparian floodplain soils during periods of high groundwater levels or flooding.     

Ecotoxicological assessment of heavy metals in sewage sludge amended soils

Contamination of soils by potentially toxic elements (PTEs) (e.g. Zn, Cu, Ni, Cr, Pb, Cd) from amendments of sewage sludge is subject to strict controls within the European Community in relation to total permissible metal concentrations, soil properties and intended use. This paper highlights the need for ecotoxicological data for the assessment of PTE impacts in addition to geochemical data alone. The soil microflora plays an essential role in determining levels of soil fertility, being intimately associated with the biogeochemical cycling of essential plant nutrients and the turnover of organic carbon. The measurement of soil microbiological parameters can provide insight into the impact of PTEs upon soil fertility, where geochemical analysis alone can often be inadequate to assess contaminant effects on essential components of the soil ecosystem. Microbial investigations were conducted on soils sampled from a well-controlled field experiment previously amended with specific types and rates of sewage sludge. Key microbiological parameters measured included the activity of the dehydrogenase enzyme and the presence and number of effective nitrogen fixing cells of Rhizobium leguminosarum biovar trifolii capable of nodulating the host plant, white clover (Trifolium repens). Results were evaluated with respect to maximum permissible concentrations of PTEs in sludge amended soils, as stipulated under UK limit values and the European Directive 86/278/EEC. Important effects on the size of the Rhizobium population and dehydrogenase activity were apparent in soils samples in relation to the soil pH, sludge type, addition rates and the concentrations of PTE present.     

Use of molecular ratios to identify changes in fatty acid composition of Miscanthus × giganteus (Greef et Deu.) plant tissue,rhizosphere and root-free soil during a laboratory experiment

Fatty acids (FAs) are abundant lipids in plants, microorganisms and soil. Depending on chain length they provide potential for evaluating different sources of C in soil: shoots, roots and microorganisms. This, together with their fast turnover and transformation in living and decaying plant tissues, suggests the use of FA molecular ratios as source indicators in soil. To evaluate the applicability of FAs as source indicators, their dynamics in plant tissue and soil were traced during a laboratory experiment using the highly productive perennial C₄ energy grass Miscanthus x giganteus (Greef et Deu.). For the comprehensive use of FAs as source indicators various ratios were calculated: fatty acid ratio (originally defined as carboxylic acid ratio: CAR), carbon preference index (CPI), average chain length (ACL) and unsaturated vs. saturated C₁₈ acids. The FA composition was specific for individual plant tissues as indicated by the CAR, with high values in roots and lower ones in the above ground plant tissue. Based on ACL values of rhizosphere, soil and roots, an enrichment in root derived FAs vs. root-free soil could be estimated. The rhizosphere contained 35–70% more plant derived FAs than root-free soil. The ACL showed potential for estimating root derived carbon in the rhizosphere. The study documents for the first time very fast spatial processes in soil related to plant growth, thereby strongly influencing the FA composition of soil.     

生物地球化学的概念与方法——DNDC模型的发展

生物地球化学作为一个学科包含4个概念,即生物地球化学量、流、群和场.这4个概念从不同角度描述了生命与其环境的关系.生物地球化学量探索生命及其无机环境在元素丰度上的相似性,这种相似性决定了生命体对环境化学状态的依赖性.生物地球化学流描写化学元素在生态系统中的迁移,此迁移导致了生命体与环境间的物质和能量交换.生物地球化学群描述化学元素在迁移转化时的复杂组合关系及其生物效应.生物地球化学场是生态系统中控制生物地球化学反应的各种环境营力的总和.生物地球化学模型即是这一综合力场及其对化学元素迁移转化影响的数学描述,DNDC模型即基于这些概念发展起来.DNDC模型可用来预测陆地生态系统中碳和氮的生物地球化学行为,该模型已被一些国家用来预测农业土壤的长期肥力和温室气体排放.     

区域生态地球化学评价数据的统计方法

如何根据一定数量有代表性样品的统计结果建立土壤元素各化学形态分量与全量或其他土壤参数的关系方程,是区域生态地球化学评价工作中急需解决的问题之一。提出了建立这类回归方程需要注意并坚持的主导性原则、简洁性原则、直接性原则、拟合优度和可识别性原则、理论一致性原则,回归方程还需要用抽取检验样品、划定预测区间等方法检验其合理性。对成都经济区土壤中有益元素和有害元素依据以上原则进行了统计分析,得到元素各形态,尤其是有效态含量与元素总量或其他重要土壤性质的回归方程,为利用面积性调查数据进行区域生态地球化学评价奠定了基础。     

The biogeochemical expression of deeply buried uranium mineralization in Saskatchewan, Canada

Ten kilometres from the eastern edge of the Athabasca Sandstone, near McClean Lake, uranium mineralization (locally up to 27% U₃O₈) lies 150 m beneath the surface at the unconformity between the Athabasca and crystalline basement.A biogeochemical survey of the area sampled A_H and B_F soil horizons, peat moss, and plant organs from the dominant species, viz. black spruce (Picea mariana), jack pine (Pinus banksiana), labrador tea (Ledum groenlandicum), and leather leaf (Chamaedaphne calyculata). Uranium concentrations in the ash of various media are surprisingly high: spruce twigs up to 154 ppm U; labrador tea and leather leaf stems around 100 ppm U. Conversely, labrador tea roots yield < 5 ppm U and spruce trunk wood usually < 1 ppm U. Soils give values of 1–3 ppm U. Contoured U values reveal that highest concentrations occur in plants growing above, but laterally displaced from the mineralization. Track-Etch data show a similar pattern. Upward migration of ions along steeply inclined fractures is invoked to explain the phenomenon. Other elements are present in varying concentrations, depending upon the plant species and the plant organ. High concentrations of several elements are recorded, most notably Cd and Ag in the conifers.     

Soil contamination by toxic metals in the cultivated region of Agia, Thessaly, Greece. Identification of sources of contamination

A soil geochemical survey was undertaken in the cultivated region of Agia in Thessaly area, Central Greece. The objectives of the study were to assess the levels of soil contamination in respect to average concentrations of toxic metals in the region, to determine the associations between the different toxic elements and their spatial distribution and to identify possible sources of contamination that can explain the spatial patterns of soil pollution in the area. One hundred seventy three soil samples were collected and analysed by ICP-AES after digestion with a mixture of HClO₄–HNO₃–H₂O. The study focused on eleven elements (Cu, Pb, Zn, Ni, Co, Mn, As, V, Cr, Fe and Mg) and all of them except Pb have mean concentrations above the average global soil composition. The elements Ni, Cr, Mn and V show concentrations that according to G.L.C guidelines the Agia soils are classified as slightly contaminated to contaminated. Factor analysis explained 84.02% of the total variance of the data through four factors. Combined with spatial interpretation of its output, the method successfully grouped the elements according to their sources and provided evidence about their natural or anthropogenic origin.     

长江河口盐沼湿地酸挥发性硫化物的时空分布特征及影响因素

以长江河口典型潮间带(崇明东滩湿地)不同地貌单元植被根际柱样沉积物(0~33 cm)为研究对象,探讨了长江河口潮间带表层沉积环境中酸挥发性硫化物(AVS)的时空间变化特征及其与环境因子的关系.结果表明,不同植被根际沉积物中 AVS 含量存在显著季节变化,表现为:互花米草大于海三棱藨草和芦苇.各采样点根际沉积物中 AVS 含量垂向变化为:高潮滩芦苇,随深度的增加而降低;中潮滩互花米草与海三棱藨草,随深度的增加先增大后减小,且在地面下约20 cm 处显著增大. Pearson 相关分析表明,沉积物中 AVS含量与<16μm 的颗粒物、有机碳含量及含水率之间不存在简单的正相关关系.根际沉积物中 AVS 含量的时空变化可能受潮汐、植被生长等因素的综合影响,其时空变化特征反映了长江河口潮滩复杂多变的氧化还原条件.与芦苇和海三棱藨草相比,入侵物种互花米草对沉积物中硫酸盐异化还原有显著影响,其可能改变了潮滩湿地生态系统原有的氧化-还原生物地球化学循环过程     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

Estimating long-term soil respiration rates from carbon isotopes occluded in gibbsite

Carbon occluded in the soil gibbsite crystal structure at the Panola Mountain Research Watershed, Georgia, U.S. is presumed to be in isotopic equilibrium with the CO₂ respired from soil organics by microbes and plant roots. Fitting of the stable carbon isotopic data to a Fickian diffusion-based depth function results in an estimate of 47 gC m⁻² y⁻¹ for the long-term soil respiration rate. A numerical model that includes depth-dependent production and diffusion terms results in estimates of 28-12 gC m⁻² y⁻¹. These values range from 15 to 50 times less than the average of modern values for mixed deciduous forests in wet temperate climates. This disparity has several implications for our understanding of the geologic record of climate change, which include: (1) evidence for a cooler and seasonally drier climate during the mid-Holocene in the southeastern U.S., or (2) fluxes of carbon from the soil pool as recorded by soil mineral proxies (i.e., long-term soil respiration rates) under estimate atmosphere annual carbon flux measurements (i.e., short-term measures), and (3) the need to refine soil respiration models used to relate paleosol stable carbon isotopic measurements to paleo-atmospheric estimates.     

Performance Analysis of Piezo-Ceramic Elements in Soils

The application of piezo-ceramic elements for measuring shear and compression wave velocities in the soil mass is increasing day-by-day. Depending upon the configuration and polarity, these elements can either be used as benders or extenders, which can transmit and receive shear and compression waves, respectively. Though, several researchers have successfully employed these elements for characterizing the soil mass based on the shear and compression wave velocities, determination of the “time lag” between the input and output waves remains debatable. Even, the existing literature does not clearly present the response of these elements with respect to the frequency of excitation and the type of the material to be characterized. With this in view, extensive investigations were made to capture the performance of piezo-ceramic elements by changing their (a) wiring configuration (i.e., series or parallel) and (b) polarization (i.e., same or opposite) in the compacted soils of different characteristics (i.e., moisture content, dry density and type of the soil). Details of the methodology are presented in this paper and special attention has been paid to address various problems (i.e., wave attenuation, crosstalk phenomena, near field effect and overshooting of transmitting waves) that are associated with signal interpretation and may yield misleading results.     

Mobility of major-, minor- and trace elements in solutions of a planosolic soil: Distribution and controlling factors

Subsurface waters circulating in an unpolluted soil of a planosolic horizon (Massif Central, France) were studied in order to determine their physico-chemical characteristics. Three water sampling sites were chosen along a toposequence. For each site, two piezometers were placed above and in the gravelly and concretion-rich horizon (Fe- and Mn- oxyhydroxides). Concentrations of major-, minor- (cations, anions, Fe, Mn, P and Si) and trace elements (Al, Ba, Cd, Co, Cr, Cu, Ni, Pb, Rb, Sr, Zn and U) were monitored on bulk and filtered water (0.45 μm) to study both the particulate and the dissolved components, from 2004 to 2006, during the soil saturation period (i.e., from November to May). Chemical characteristics of soil solutions provide evidence for various chemical water compositions and for temporal variations of water quality, revealing that the hydrodynamic and chemical reactivity in the solution is different for the three sites. Calculations of pe values indicate a range of redox state of the soil solutions. The pe ranges are different for each piezometer but correspond to anoxic solution. For all piezometers, distribution between the dissolved and the particulate fraction and correlations between the various elements in the soil solutions indicate that: (i) Al and Fe show similar behaviour, (ii) Al is mainly present as oxyhydroxides and (iii) some trace metals are mainly associated with particles which have a mixed nature. The impact of a concretion-rich horizon is noticed both on the nature of particles and on the speciation of trace metals and could be explained by the hydrodynamic and chemical reactivity of the circulating solution. Very few correlations exist between elements in the dissolved phase.     

酸活化坡缕石对土壤中Cd的钝化效果研究

为探究不同浓度H2SO4溶液活化的坡缕石对土壤中Cd的钝化效果,使用浓度分别为5％、7.5％、10％、12.5％、15％的H2SO4溶液对坡缕石进行活化,加入Cd污染土壤进行钝化实验和盆栽实验.结果表明:施加不同浓度H2SO4溶液活化的坡缕石均能显著降低土壤有效态Cd含量,10％的H2SO4活化的坡缕石钝化效果最显著,...     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

Toxic metal(loid) speciation during weathering of iron sulfide mine tailings under semi-arid climate

Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3–2.3).Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mmol kg⁻¹ (3080, 2200, and 2570 mg kg⁻¹), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2-fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25–54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0–35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO₄·nH₂O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.     

Accumulation behavior of toxic elements in the soil and plant from Xinzhuangzi reclaimed mining areas,China

The concentration and distribution characteristics of toxic elements in soil and plant were investigated in the coal refuse reclaimed areas of Huainan, China. Ninety soil samples from different depth (0–20, 20–40, 40–60 cm) and 120 plant samples were collected based on grid sampling method. The concentrations of the selected toxic elements (As, Cd, Cu, Ni, Pb and Zn) in the soil and plant samples were determined by using inductively coupled plasma mass spectrometry. The elevated concentrations of toxic elements in the soils at the depth of 20–40 and 40–60 cm suggested that the coal refuse reclamation may lead to potential environmental impacts. The toxic element tolerance could be observed in all the selected plant samples. The concentrations of toxic elements in the underground tissues were higher than that of aboveground tissues. Conclusively, the present study provided a comprehensive evaluation of soil and plant toxic element implications from coal refuse reclaimed areas in China and was also helpful for environmental protection and monitoring the safety of plant.     

Contribution of maize root derived C to soil organic carbon throughout an agricultural soil profile assessed by compound specific C analysis

Cutin and suberin structural units might be stabilized in subsoils and contribute to the aliphatic structures observed in stabilized soil organic matter (SOM). We studied their dynamics in subsoils by measuring the concentrations and ¹³C contents of cutin and suberin markers in soil profiles under wheat (C₃) and after 9 years of maize cropping (C₄ plant). Alkandioic acids were considered as markers for roots, mid-chain hydroxy acids were only present in shoots and ω-hydroxy acids were identified in both roots and shoots. The diacid concentrations greatly increased below the ploughed layer after 9 years of maize cropping, possibly due to a higher root density of maize compared to wheat or to a faster turnover of fine roots and increased exudation of maize compared to wheat. From 0-75 cm, 9 years of maize cropping did not affect the distribution of shoot biomarkers but increased their concentrations. By contrast, below 75 cm, the shoot marker concentrations drastically decreased from the wheat control to the 9 year maize soil. The difference of δ¹³C observed for shoot markers was always lower than that observed for ω-hydroxy acids, and below 15 cm, it was close to that observed for SOC. The difference in δ¹³C of diacids was much more variable along the profile. Since the concentrations of the different markers were not at equilibrium, it was not possible to estimate their turnover. This study suggests several caveats for the use of molecular markers of roots and shoots to study the dynamics of SOM in deep soils: the higher heterogeneity compared to the ploughed layer, the presence of long history record of past vegetation that may hinder the short time scale changes tracked with the ¹³C isotope technique, and the difficulty in evaluating root inputs in the soil systems.