Chemical speciation and bioavailability of Cd,Cu, Pb and Zn in Western Balkan soils

Abstract

Three thermal power plants in Serbia, Croatia and Bosnia of the Western Balkan region were expected to be metal polluting sources, and this study was performed to investigate the bioavailability and chemical speciation of trace metals in soils and soil water extracts, respectively. Surface (0–15 cm) soil samples along with maize and grass samples were collected at a gradient from the pollution source. The chemical speciation of metals was conducted using the Windereme Humic Aqueous Model (WHAM)/Model VI for water, whereas the Diffusion Gradient in Thin Films (DGT) technique was used to estimate plant availability. The chemical speciation indicated that more than 99% of all four metals in soil water extracts were complexed to fulvic acid. This is connected to relatively high soil pH (> 6.5) and high contents of soil organic matter in these soils. The accumulation of trace metals by DGT was not correlated to plant uptake. This is connected to the very low partitioning of free ions in solution, but also to the low variation in metal solubility and metal concentration in plant tissue between sites. In spite of active thermal power plants located in the areas, hardly any differences in concentration of soil metals between sites were seen and the partition of metals in soil waters was insignificant. The latter indicates that these soils have a large metal-retaining capacity. The only significant soil chemical variable affecting the variation in metal solubility was the soil pH. In a time with large infrastructure and industrial expansion in these areas, this investigation indicates the importance of protecting these high-quality soils from industrial use and degradation. High industrial activity has so far had insignificant effect on soil quality with respect to bioavailability of trace metals in these soils.     

Biogeochemical interfaces in soil: The interdisciplinary challenge for soil science

Soil, the “Earth's thin skin” serves as the delicate interface between the biosphere, hydrosphere, atmosphere, and lithosphere. It is a dynamic and hierarchically organized system of various organic and inorganic constituents and organisms, the spatial structure of which defines a large, complex, and heterogeneous interface. Biogeochemical processes at soil interfaces are fundamental for the overall soil development, and they are the primary driving force for key ecosystem functions such as plant productivity and water quality. Ultimately, these processes control the fate and transport of contaminants and nutrients into the vadose zone and as such their biogeochemical cycling. The definite objective in biogeochemical‐interface research is to gain a mechanistic understanding of the architecture of these biogeochemical interfaces in soils and of the complex interplay and interdependencies of the physical, chemical, and biological processes acting at and within these dynamic interfaces in soil. The major challenges are (1) to identify the factors controlling the architecture of biogeochemical interfaces, (2) to link the processes operative at the individual molecular and/or organism scale to the phenomena active at the aggregate scale in a mechanistic way, and (3) to explain the behavior of organic chemicals in soil within a general mechanistic framework. To put this in action, integration of soil physical, chemical, and biological disciplines is mandatory. Indispensably, it requires the adaption and development of characterization and probing techniques adapted from the neighboring fields of molecular biology, analytical and computational chemistry as well as materials and nano‐sciences. To shape this field of fundamental soil research, the German Research Foundation (DFG) has granted the Priority Program “Biogeochemical Interfaces in Soil”, in which 22 individual research projects are involved.     

Physical,Chemical, and Biological Changes in the Rhizosphere and Nutrient Availability

The rhizosphere is the soil zone adjacent to plant roots which is physically, chemically, and biologically different from bulk or non-rhizosphere soil. Adaptative mechanisms of plants influence physical (temperature, water availability, and structure), chemical [pH, redox potential, nutrient concentration, root exudates, aluminum (Al) detoxification and allelopathy], and biological properties (microbial association) in the rhizosphere. These changes affect nutrient solubility, transport, and uptake and ultimately plant growth. Major rhizosphere changes are synthesized and their influence on nutrient availability is discussed. In the last decade, significant progress has been made in understanding the rhizosphere environment and nutrient availability. However, the subject matter is very complex and more research is needed to understand the interaction between the plant, the rhizosphere environment, and nutrient availability.     

Phosphorus and aluminium solubility relationships in acidic lowbush blueberry barren soils in Maine

Lowbush blueberry (Vaccinium angustifolium) is a native plant that is not cultivated, but managed in areas of sufficient plant density to provide commercial yields. A cropping systems study was initiated to compare how organic and three levels of conventional (low, medium and high input) management practices affected soil properties at 12 grower fields in the lowbush blueberry barrens of Maine. The fields under organic and low‐conventional treatments did not receive any fertilizer inputs. The high and medium conventional treatment fields received optimal and reduced diammonium phosphate inputs, respectively. Three measurements of soil P (modified‐Morgan soil test, oxalate extractable and total P) showed no significant effect of management treatment on the phosphorus status of the soils. This suggests that soil P may be leaching below the 0–10 cm rooting zone which was investigated in this study. Equilibrium chemical speciation of soil/water extracts showed that gibbsite was controlling the solubility of Al in these barren soils and that P was undersaturated with respect to amorphous Al(OH)₂PO₄. A laboratory one‐point P sorption study showed that dissolved organic matter derived from the organic pad sampled from the study sites did not inhibit the adsorption of the added P. This suggests that addition of carbon‐rich soil amendments such as compost may not increase P bioavailability of these acidic soils with high Al (oxy)hydroxide (gibbsite) mineral content.     

Application of soil amendments to contaminated soils for heavy metal immobilization and improved soil quality—a critical review

ABSTRACT

Today, soil metal pollution has become a significant environmental issue of great public concern. This is because soil is both a major sink for heavy metal(loid)s (HMs) released into the environment, by both pedogenic and anthropogenic activities; and also a major source of food chain contamination mainly through plant uptake and animal transfer. In addition, HM contamination of soil leads to negative impacts on soil characteristics and function by disturbing both soil biological and physiochemical properties (e.g. extreme soil pH, poor soil structure and soil fertility and lack of soil microbial activity). This eventually leads to decreased crop production. Various soil remediation techniques have been successfully employed to reduce the risks associated with HMs efflux into soil. Among these, the use of low-cost and environmentally safe inorganic and organic amendments for the in-situ immobilization of HMs has become increasingly popular. Immobilization agents have successfully reduced the availability of metal ions through a variety of adsorption, complexation, precipitation, and redox reactions. Soil amendments can also be a source of nutrients and thus can also act as a soil conditioner, improving the soil’s physiochemical properties and fertility, resulting in enhanced plant establishment in metal contaminated soils. This article critically reviews the use of immobilizing agents in HM contaminated agricultural and mining soils paying particular attention to metal immobilization chemistry and the effects of soil amendments on common soil quality parameters.     

Short‐term transformations of lead and cadmium compounds in soil after contamination

The behaviour and fate of trace metals, in particular lead and cadmium, when they contaminate the soil as atmospheric fall‐out are not well understood. To improve our understanding, we incorporated pure compounds of lead and cadmium into samples taken from surface horizons of three chemically contrasting soils and monitored the changes in their speciation by analysing the soil solution. In most instances the concentrations of trace metals in solution were maximal during the first few days after mixing the contaminants with the soil, and depended strongly on soil type. The exception was when the contaminant was added as sulphide particles. The initial speciation of metals also influenced their solubility, following a decreasing order which did not depend on the soil type:
Lead sulphide was progressively oxidized, but cadmium sulphide was hardly dissolved. When lead was added as sulphate, between 10 and 20% of lead particles dissolved, regardless of the soil type. For the other species, dissolution was enhanced at lower soil pH. Thermodynamic calculations with the WinHumic V program indicated that the solution was not saturated with respect to lead sulphate. We conclude that dissolution must be limited by the adsorption of inhibitors on reactive surfaces. The calculations also showed that precipitation of chloropyromorphite probably controls lead concentration in leachate from the acid organic soil. Finally, both soil type and initial speciation of contaminants control the behaviour of trace metals in soils for a time greater than a cropping season and must be considered for understanding their environmental impact.     

The response of finely textured and organic soils to lime and phosphorus application: Results from an incubation experiment

A soil's responses to phosphorus (P) input differs based on its chemical composition. Soil acidity and the presence of metallic cations dictate a soil's chemical composition. Currently, soil P application recommendations are universal and do not account for differing soil composition. A targeted soil-specific approach is required to optimize P efficiency and availability. A pot incubation experiment was established to explore the effects of contrasting lime and P application rates across a range of soils (25), characterized by fine particle size and high levels of soil organic matter. Three contrasting rates of P were applied (0, 50, and 150 kg P ha⁻¹) both with and without ground lime (CaCO₃) at 5 tonne ha⁻¹ over a 140-day incubation period. The addition of lime buffered the soil, increasing nutrient availability and reducing P fixation. The 50 kg P ha⁻¹ treatment rate was required to achieve sufficient plant available P in both mineral soil textural classes. Current legislative recommendations however do not allow the application of such rates, which has an impact on agronomic performance. Loam soils experienced a greater increase in M3 soil P in comparison to clay and organic soils. Organic soils posed a major threat to water quality due to poor P retention. A re-evaluation of P recommendations is required to account for soil variability as current P allowances are insufficient on these particular soils.     

硫在稻根微域中化学行为及其对水稻吸收重金属的影响机理

我国水稻种植面积和产量分别占世界23%和40%.人类活动,如农药和除草剂施用、采矿、污水灌溉,已经导致了一些地区水稻土污染.开发能够控制、减少水稻对重金属吸收和经食物链传递的技术与方法,对确保食物安全具有重要意义.硫(S)有6个化合态,土壤硫化合物种类多,其在土壤中转化相当复杂,在土壤环境化学研究中具有重要地位.本文收集了国内外有关文献,评述了S在水稻土中的含量、形态及转化,重点阐述了S在根际微域化学行为及其与水稻吸收重金属之间的关联,并提出了未来应开展的主要研究方向.     

Soil carbon dynamics in saline and sodic soils: a review

Soil salinity (high levels of water-soluble salt) and sodicity (high levels of exchangeable sodium), called collectively salt-affected soils, affect approximately 932 million ha of land globally. Saline and sodic landscapes are subjected to modified hydrologic processes which can impact upon soil chemistry, carbon and nutrient cycling, and organic matter decomposition. The soil organic carbon (SOC) pool is the largest terrestrial carbon pool, with the level of SOC an important measure of a soil's health. Because the SOC pool is dependent on inputs from vegetation, the effects of salinity and sodicity on plant health adversely impacts upon SOC stocks in salt-affected areas, generally leading to less SOC. Saline and sodic soils are subjected to a number of opposing processes which affect the soil microbial biomass and microbial activity, changing CO₂ fluxes and the nature and delivery of nutrients to vegetation. Sodic soils compound SOC loss by increasing dispersion of aggregates, which increases SOC mineralisation, and increasing bulk density which restricts access to substrate for mineralisation. Saline conditions can increase the decomposability of soil organic matter but also restrict access to substrates due to flocculation of aggregates as a result of high concentrations of soluble salts. Saline and sodic soils usually contain carbonates, which complicates the carbon (C) dynamics. This paper reviews soil processes that commonly occur in saline and sodic soils, and their effect on C stocks and fluxes to identify the key issues involved in the decomposition of soil organic matter and soil aggregation processes which need to be addressed to fully understand C dynamics in salt-affected soils.     

Innovative methods in soil phosphorus research: A review

Phosphorus (P) is an indispensable element for all life on Earth and, during the past decade, concerns about the future of its global supply have stimulated much research on soil P and method development. This review provides an overview of advanced state‐of‐the‐art methods currently used in soil P research. These involve bulk and spatially resolved spectroscopic and spectrometric P speciation methods (1 and 2D NMR, IR, Raman, Q‐TOF MS/MS, high resolution‐MS, NanoSIMS, XRF, XPS, (µ)XAS) as well as methods for assessing soil P reactions (sorption isotherms, quantum‐chemical modeling, microbial biomass P, enzymes activity, DGT, ³³P isotopic exchange, ¹⁸O isotope ratios). Required experimental set‐ups and the potentials and limitations of individual methods present a guide for the selection of most suitable methods or combinations.     

Effects of wastewater irrigation on soil and cabbage‐plant (brassica olerecea var. capitate cv. yalova‐1) chemical properties

The use of wastewater for irrigation is increasingly being considered as a technical solution to minimize soil degradation and to restore nutrient contents of soils. The aim of this study is to increase fertility and minimize degradation of soils irrigated with wastewater exposed to different purification treatments. A field experiment was conducted to investigate the effects of control and irrigation with wastewater, which had undergone different purification treatments, on macro‐ and micronutrient distribution within the soil profile and nutrient contents of cabbage (Brassica olerecea var. Capitate cv. Yalova‐1) in Erzurum, Turkey. Wastewater irrigation and preliminary treatment–wastewater irrigation significantly affected soil chemical properties especially at 0–30 cm soil depth and plant nutrient contents after one year. Application of wastewater increased soil salinity, organic matter, exchangeable Na, K, Ca, Mg, plant‐available P, and micro‐elements and decreased soil pH. Wastewater increased also yield and N, P, K, Fe, Mn, Zn, Cu, B, and Mo contents of cabbage plants. Undesirable side effects were not observed in plant heavy‐metal contents, due to salinity and toxic concentrations of metals from the application of wastewater to soil.     

An applied bioassay with tropical soil analyses for clayey oxisol fertility improvement

Abstract

There is a need for improved methodology providing reliable yield response data for tropical soils that correlate with soil testing results. However, both root development and desirable soil microbial activities are usually repressed with the heavy clayey oxisols in small pot greenhouse experiments. Fertility of the ultisols and oxisols is governed by soil organic matter content and soil microbial transformations. These are not determined with soil test extraction procedures and must be established with actual measurement of the complex biological permutations involved. The objective of these studies was to develop bioassay procedures suitable for boil fertility investigations with a heavy, clayey oxisol (56% clay) of Jaiba, a tropical region of central Brazil.

Soil dilution to 5.6% clay content with sterile, coarse quartz sand resulted in an optimum rhizosphere for plant nutrient studies using 500 g bioassay cultures. Phosphorus was the first limiting plant nutrient. Both N and K produced yield increases when applied singly although the largest increases in corn dry matter resulted with NPK combinations. Available N, P and S were related to organic matter transformations with response to S attained after exhaustive cropping. Significant responses to Zn, B and Mo were not obtained in these studies. Practical value of this procedure results from attaining reliable plant growth response to levels and combinations of fertilizer treatments with small quantities of soil. These data are fundamental for interpretation of soil test results that are utilized for highly diverse ultisols and oxisols. Sound recommendations for improved soil management practices are essential for the small, provincial subsistence type farms having very limited resources within the extensive, underutilized neotropics of the world.     

Bioavailability of hydrophobic organic contaminants in soils: fundamental concepts and techniques for analysis

Soils represent a major sink for organic xenobiotic contaminants in the environment. The degree to which organic chemicals are retained within the soil is controlled by soil properties, such as organic matter, and the physico‐chemical properties of the contaminant. Chemicals which display hydrophobic and lipophilic characteristics, as well as a recalcitrant chemical structure, will be retained within the soil, and depending on the ‘strength’ of the association may persist for long periods of time. This review describes the behaviour of hydrophobic organic contaminants in soils, focusing on the mechanisms controlling interactions between soil and contaminants. The bioavailability of contaminants in soil is also discussed, particularly in relation to contact time with the soil. It considers the degradation of organic contaminants in soil and the mechanisms microbes use to access contaminants. Finally, the review discusses the ‘pros’ and ‘cons’ of chemical and biological techniques available for assessing bioavailability of hydrophobic organic chemicals in soils, highlighting the need to quantify bioavailability by chemical techniques. It concludes by highlighting the need for understanding the interactions between the soil, contaminants and biota which is crucial to understanding the bioavailability of contaminants in soils.     

An overview on biochar production, its implications, and mechanisms of biochar-induced amelioration of soil and plant characteristics

The degradation of soil fertility and quality due to rapid industrialization and human activities has stimulated interest in the rehabilitation of low-fertility soils to sustainably improve crop yield. In this regard, biochar has emerged as an effective multi-beneficial additive that can be used as a medium for the amelioration of soil properties and plant growth. The current review highlights the methods and conditions for biochar production and the effects of pyrolysis temperature, feedstock type, and retention time on the physicochemical properties of biochar. We also discuss the impact of biochar as a soil amendment with respect to enhancing soil physical (e.g., surface area, porosity, ion exchange, and water-holding capacity) and chemical (e.g., pH, nutrient exchange,functional groups, and carbon sequestration) properties, improving the soil microbiome for increased plant nutrient uptake and growth, reducing greenhouse gas emissions, minimizing infectious diseases in plants, and facilitating the remediation of heavy metal-contaminated soils. The possible mechanisms for biochar-induced amelioration of soil and plant characteristics are also described, and we consider the challenges associated with biochar utilization. The findings discussed in this review support the feasibility of expending the application of biochar to improve degraded soils in industrial and saline-alkali regions, thereby increasing the usable amount of cultivated soil. Future research should include long-term field experiments and studies on biochar production and environmental risk management to optimize biochar performance for specific soil remediation purposes.     

Speciation of phosphorus in temperate zone forest soils as assessed by combined wet‐chemical fractionation and XANES spectroscopy

Phosphorus availability in terrestrial ecosystems is strongly dependent on soil P speciation. Here we present information on the P speciation of 10 forest soils in Germany developed from different parent materials as assessed by combined wet‐chemical P fractionation and synchrotron‐based X‐ray absorption near‐edge structure (XANES) spectroscopy. Soil P speciation showed clear differences among different parent materials and changed systematically with soil depth. In soils formed from silicate bedrock or loess, Fe‐bound P species (FePO₄, organic and inorganic phosphate adsorbed to Fe oxyhydroxides) and Al‐bound P species (AlPO₄, organic and inorganic phosphate adsorbed to Al oxyhydroxides, Al‐saturated clay minerals and Al‐saturated soil organic matter) were most dominant. In contrast, the P speciation of soils formed from calcareous bedrock was dominated (40–70% of total P) by Ca‐bound organic P, which most likely primarily is inositol hexakisphosphate (IHP) precipitated as Ca₃‐IHP. The second largest portion of total P in all calcareous soils was organic P not bound to Ca, Al, or Fe. The relevance of this P form decreased with soil depth. Additionally, apatite (relevance increasing with depth) and Al‐bound P were present. The most relevant soil properties governing the P speciation of the investigated soils were soil stocks of Fe oxyhydroxides, organic matter, and carbonate. Different types of P speciation in soils on silicate and calcareous parent material suggest different ecosystem P nutrition strategies and biogeochemical P cycling patterns in the respective ecosystems. Our study demonstrates that combined wet‐chemical soil P fractionation and synchrotron‐based XANES spectroscopy provides substantial novel information on the P speciation of forest soils.     

Overcoming the Confounding Effects of Salinity on Sodic Soil Research

The adverse effects of sodicity on plant growth are difficult to quantify using naturally occurring soils because of the confounding variation in other soil properties, particularly salinity, pH, organic matter, soil nutrients, mineralogy, and texture. We applied a method involving the equilibration of large soil volumes with solutions varying in sodium adsorption ratio (SAR), followed by excess salt removal with solutions of similar SAR but lower ionic strength. Application of this method to a calcareous nonsodic, nonsaline Vertosol from Narrabri, New South Wales, resulted in soils with exchangeable sodium percentage (ESP) values between 2% and 25% but with similar magnesium and potassium concentrations and constant electrical conductivity (～2.7 dS/m). Soil pH and solution phosphorus concentrations automatically increased as the ESP of the soil rose, which is important to consider when addressing plant growth results. This method can successfully minimize the confounding of sodicity with other soil properties that so often plagues sodic soil research.     

我国主产区紫花苜蓿营养状况分析

为探究我国主产区紫花苜蓿营养现状以及生产中肥料使用的科学性, 2012年5-6月,对我国紫花苜蓿主产区21个大田样地苜蓿初花期时的土壤养分、 植物组织营养以及第一茬产草量和施肥管理情况进行测定和调研,对土壤和植物营养状况进行评价,对土壤和植物养分含量与产草量间的关系进行了分析。研究表明, 紫花苜蓿主产区土壤以砂性为主,有机质含量低。紫花苜蓿组织中氮素营养处于充足水平,磷素（P）和钾素（K）普遍缺乏, 微量元素中锌（Zn）、 硼（B）、 钼（Mo）元素缺乏。土壤中磷素和植物体内硼（B）、 钼（Mo）和铁（Fe）含量与第一茬产草量显著正相关。施用氮肥地块有12个,磷肥有5个, 钾肥有3个,没有有针对性施用微量元素肥料的地块。建议在紫花苜蓿大田生产上控制氮肥施用,注重P、 K肥的施用,有针对性地施用B、 Mo等微量元素。     

Role of Soil Organic Matter in Maintaining Sustainability of Cropping Systems

Soil organic matter (SOM) has long been recognized as an important indicator of soil productivity. The SOM refers to the organic fraction of the soil exclusive of undecayed plant and animal residues. It plays a crucial role in maintaining sustainability of cropping systems by improving soil physical (texture, structure, bulk density, and water-holding capacity), chemical (nutrient availability, cation exchange capacity, reduced aluminum toxicity, and allelopathy), and biological (nitrogen mineralization bacteria, dinitrogen fixation, mycorrhizae fungi, and microbial biomass) properties. The preservation of SOM is crucial to ensure long-term sustainability of agricultural ecosystems. Improvement/preservation of soil organic matter can be achieved by adopting appropriate soil and crop management practices. These practices include conservation tillage, crop rotation, use of organic manures, increasing cropping intensity, use of adequate rate of chemical fertilizers, incorporation of crop residues, liming acidic soils, and keeping land under pasture. Organic matter can adsorb heavy metals in the soils, which reduce toxicity of these metals to plants and reduce their escape to ground water. Similarly, SOM also adsorbs herbicides, which may inhibit contamination of surface and ground water. Furthermore, SOM also functions as a sink to organic carbon and mitigates carbon dioxide (CO₂) gas escape to the environment. Globally, soil organic matter contains about three times as much carbon as found in the world's vegetation. Hence, organic matter plays a critical role in the global carbon balance that is thought to be the major factor affecting global warming. Overall, adequate amounts of soil organic matter maintain soil quality, preserve sustainability of cropping systems, and reduce environmental pollution.     

基于废弃物的潞安煤矿废弃地改良土壤基质配比研究

为解决潞安矿区煤矸石山、塌陷地生态修复缺土少肥问题,本研究将粉煤灰、污泥与垃圾堆肥以5%、10%、20%体积比例正交混合配制改良土壤基质进行盆栽试验,观测不同配比土壤的理化性质、养分及重金属含量、高羊茅与紫叶小檗生长状况,并用主成分–聚类分析法筛选最优配比。结果表明:添加垃圾堆肥可以提高土壤有效养分与有机质含量,对土壤理化性质改良有明显效果;添加污泥仅提升土壤有效磷含量;添加粉煤灰在降低土壤容重、增大总孔隙度与非毛管孔隙度上效果明显,但对土壤p H、阳离子交换量(CEC)与碱解氮的改良具有显著负效应。各废弃物改良基质的碱解氮、有效磷、速效钾、有机质等含量均较高,土壤重金属含量也处在安全范围,而土壤容重、非毛管孔隙、pH、电导率(EC)与CEC等指标性质较优的处理组为粉煤灰∶污泥∶垃圾堆肥∶土=5%∶20%∶20%∶55%、10%∶10%∶20%∶60%、20%∶5%∶20%∶55%3个处理。经过综合筛选,本研究基质最优混合配比为粉煤灰∶污泥∶垃圾堆肥∶土=5%∶20%∶20%∶55%,可作为当地矿区废弃地生态修复客土材料推荐方案。     

低分子量有机酸对可变电荷土壤和矿物表面化学性质的影响

低分子量有机酸是土壤中广泛存在的,它们参与土壤中许多化学过程,在营养元素活化、解铝毒和矿物风化等方面发挥重要作用。本文综述了可变电荷土壤和矿物对低分子量有机酸的吸附及这类有机酸对土壤的表面电荷、动电性质和土壤吸附无机阴、阳离子的影响,为从事相关研究工作的同志提供参考。