重金属和有机污染物在修饰土中的吸附

Sorption characteristics of both an organic pollutant （phenol） and a heavy metal （cadmium ion） on the clay layer of a Lou soil （Eum-orthic Anthrosol in Chinese Soil Taxonomy） along with the sorption mechanism were investigated using three soil treatments： modification with a cationic surfactant cetyltrimethylammonium bromide added at an amount equivalent to 50% and 100% of the soil CEC （50? and 100?）, modification with an amphoteric surface-modifying agent dodecyldimethylbetaine （commercially known as BS-12） added at an amount equivalent to 50% and 100% of the soil CEC （50% BS and 100%BS）, and an unmodified control （CK）. Results showed that the BS soil treatments increased sorption of both the heavy metal Cd^2＋ and the organic pollutant phenol. The equilibrium sorption amount of Cd^2＋ decreased in the order： 50%BS 〉 100%BS 〉 CK 〉 50? 〉 100?, with the BS soil treatments being about 1.3 to 1.8 times higher and the CB soil treatments about 23% to 41% lower than CK. Both the single-site and two-site Langmuir models could be applied to describe the sorption of Cd^2＋ in each soil treatment. The equilibrium sorption amount of phenol on the soil samples decreased in the order： 100? 〉 50? 〉 100%BS 〉 50%BS 〉 CK, with the CB soil treatments being 41.0 to 79.6 times higher and the BS soil treatments 4.0 to 8.3 times higher than CK. The Freundlich equation could also be used to describe the sorption characteristics of phenol. In the BS soil treatments, both an organophobic long carbon chain and hydrophilic charged groups resulted in a relatively strong sorption ability for both heavy metals and organic pollutants. In addition, the sorption ratio K, the ratio of phenol sorption amount of the modified soil to that of CK, increased initially and decreased later with the amount of phenol added, and the critical sorption ratio Kc, the peak value of the sorption ratio curve plotted against the added phenol concentration, was a good index for evaluating the sorption ability of phenol in the soil.     

Soil Immobilization of Heavy Metal Using Soil Amendments in a Greenhouse Study

ABSTRACT

The application of soil amendments to immobilize heavy metals is a promising technology to meet the requirements for environmentally sound and cost-effective remediation. The present work was carried out to evaluate the effect of phosphogypsum (PG) used alone and in combination with compost (CP) at a mix ratio of 1:1 wet weight ratio (PG+CP) at 10 and 20 g dry weight kg^?1 dry soil, on heavy metal immobilization in contaminated soil, and on canola growth (Brassica napus). The results were then compared with untreated soil (control). The results revealed that the Pb, Cd, and Zn uptake of canola plants was reduced by the application of PG alone and when it was mixed with CP. At an application rate of 10 g dry weight kg^?1 dry soil of (PG+CP), the dry weight of canola plants increased by 66.8%, which was increased in comparison on its weight in the untreated soil (control). The addition of PG alone resulted in more pronounced immobilization of heavy metals as compared to PG mixed with CP. Plant growth was improved with CP addition but heavy metals immobilization was greatest in PG alone treatments. Results suggest that PG may be useful for the immobilization of heavy metals in contaminated soils.     

Heavy Metal Immobilization in Contaminated Soils using Phosphogypsum and Rice Straw Compost

The application of soil amendments to immobilize heavy metals is a promising technology to meet the requirements for environmentally sound and cost‐effective remediation. The present study was carried out to evaluate the result of phosphogypsum (PG) used alone and in combination with compost (CP) at a mix ratio of 1:1 wet weight ratio (PG + CP) at 10 and 20 g dry weight kg⁻¹ dry soil, on heavy metal immobilization in contaminated soil and on canola growth. The results revealed that the Pb, Cd and Zn uptake of canola plants was reduced by the application of PG alone and when it was mixed with CP as compared with untreated soil. At an application rate of 10 g dry weight kg⁻¹ dry soil of (PG + CP) the dry weight of canola plants increased by 66·8% was increased in comparison with its weight in the untreated soil. The addition of PG alone resulted in more pronounced immobilization of heavy metal as compared with PG mixed with CP. Plant growth was improved with CP addition, but heavy metals immobilization was the greatest in PG alone treatments. Results suggest that PG may be useful for the immobilization of heavy metals in contaminated soils. Copyright © 2014 John Wiley & Sons, Ltd.     

利用粘粒矿物修复重金属污染农业土壤研究进展

Heavy metal contamination of agricultural soils poses risks and hazards to humans.The remediation of heavy metal-polluted soils has become a hot topic in environmental science and engineering.In this review,the application of clay minerals for the remediation of heavy metal-polluted agricultural soils is summarized,in terms of their remediation effects and mechanisms,influencing factors,and future focus.Typical clay minerals,natural sepiolite,palygorskite,and bentonite,have been widely utilized for the in-situ immobilization of heavy metals in soils,especially Cd-polluted paddy soils and wastewater-irrigated farmland soils.Clay minerals are able to increase soil pH,decrease the chemical-extractable fractions and bioavailability of heavy metals in soils,and reduce the heavy metal contents in edible parts of plants.The immobilization effects have been confirmed in field-scale demonstrations and pot trials.Clay minerals can improve the environmental quality of soils and alleviate the hazards of heavy metals to plants.As main factors affecting the immobilization effects,the pH and water condition of soils have drawn academic attention.The remediation mechanisms mainly include liming,precipitation,and sorption effects.However,the molecular mechanisms of microscopic immobilization are unclear.Future studies should focus on the long-term stability and improvement of clay minerals in order to obtain a better remediation effect.     

菲在土壤/沉积物上的吸附-解吸过程及滞后现象的研究

实验研究了菲在土壤 /沉积物上的吸附 解吸过程。CHL土壤和HFH沉积物中有机质的固相13 CCPMASNMR谱图很相似 ,表明样品中有机质的组成差异不大 ;菲在土壤 /沉积物上的吸附过程表现出明显的非线性 ;线性模型不适合拟合菲的吸附等温线 ,Freundlich模型和双区位反应模型 (DRDM)较好地拟合了菲的吸附等温线 ,其中DRDM模型还清楚地反映菲在低浓度和高浓度下不同的吸附方式 ;另外 ,研究表明菲在土壤 /沉积物上的解吸过程中存在明显的滞后现象 ,这可能和土壤 /沉积物有机质的异质性和土壤胶团微小孔隙的存在有关。     

Microbial immobilization and mineralization of dissolved organic nitrogen from forest floors

Dissolved organic nitrogen (DON) plays a key role in the N cycle of many ecosystems, as DON availability and biodegradation are important for plant growth, microbial metabolism and N transport in soils. However, biodegradation of DON (defined as the sum of mineralization and microbial immobilization) is only poorly understood. In laboratory incubations, biodegradation of DON and dissolved organic carbon (DOC) from Oi and Oa horizons of spruce, beech and cypress forests ranged from 6 to 72%. Biodegradation of DON and DOC was similar in most samples, and mineralization of DON was more important than microbial immobilization. Nitrate additions (0-10 mg N L⁻¹) never influenced either DON immobilization by microorganisms or mineralization. We conclude that soil microorganisms do not necessarily prefer mineral N over DON for meeting their N demand, and that biodegradation of DON seems to be driven by the microbial demand for C rather than N. Quantifying the dynamics of DON in soils should include consideration of both C and N demands by microbes.     

Mitigating Negative Microbial Effects of <Emphasis Type="Italic">p</Emphasis>-Nitrophenol,Phenol, Copper and Cadmium in a Sandy Loam Soil Using Biochar

Biochars are adsorptive solids potentially of benefit to soil microbes by providing improved nutrient retention, a carbon substrate and contaminant adsorption. A 28-day incubation experiment gauged the interactive effects of biochar application and contaminants on the microbial biomass and respiration of a sandy loam soil. Soil was amended with 250 mg/kg phenol or p-nitrophenol (two toxic but nevertheless biodegradable organic contaminants) or 50 mg/kg cadmium or copper. Biochar application generally caused increased microbial respiration and biomass relative to non-amended controls. Of the heavy metal-amended soils, Cu effected significant reductions in microbial biomass carbon and basal respiration, which were improved with concurrent biochar amendment. The biochar’s functional groups are likely to have mitigated the metals’ negative effects via complexation and sorption, while the soil’s proportion of negative pH-dependent sites was increased by the pH rise induced by biochar application, allowing more cationic retention. Organic contaminant-spiked soils had higher microbial biomass-specific respiration without biochar amendment, indicating that surviving microbes utilised the compounds and necromass as substrates. Paranitrophenol proved to be particularly toxic without biochar application, causing marked reductions in the microbial quotient and biomass carbon. Remarkably, concurrent biochar and pNP application led to hugely increased microbial biomass carbon and nitrogen, significantly higher than those in contaminant-free replicates. It is likely this arose from biochar sorbing the contaminant and allowing its microbial utilisation as a carbon and nitrogen source, stimulating growth. Biochar application is a highly promising strategy for reducing the soil microbial toxicity of heavy metals and aromatic organic contaminants, particularly p-nitrophenol.     

秸秆生物质炭吸附溶液中Cu2+ 的影响因素研究

生物质炭在吸附土壤中重金属和有机污染物方面发挥着重要作用,然而关于生物质炭吸附重金属的影响因素研究较少。以小麦和玉米秸秆为原料制备生物质炭,分析了生物质炭和溶液性质对水溶液中Cu2+吸附的影响。结果表明生物质炭可有效吸附Cu2+,且不易解吸。Cu2+吸附量随pH和Cu2+初始浓度的升高而增加;高温炭对Cu2+的吸附随离子强度增强而增大;柠檬酸抑制低温炭对Cu2+的吸附,而腐植酸促进Cu2+吸附;生物质炭灰分对Cu2+吸附无显著影响。     

中国东部太湖地区酸性水稻土团聚体上铜的专性和非专性吸附动力学研究

The Taihu Lake region in East China has become prone to soil acidification, which changes heavy metals such as copper(Cu) in soil into water-soluble species and increases the mobility and contamination risks of heavy metals in the biological environment. In this study, the kinetics of Cu2+sorption by the bulk soil and the aggregate size fractions of an acidic paddy soil collected from the Taihu Lake region, the effects of temperature on Cu2+sorption, and the p H changes of the solution were investigated by static sorption and magnetic stirring. The aggregate size fractions were prepared by low-energy ultrasonic dispersing and freeze-drying. The total sorption amounts of the bulk soil and the aggregate size fractions for Cu2+followed a descending order of clay > coarse sand > bulk soil > silt> sand, corresponding to those of organic matter content, free iron oxide content, free aluminum oxide content, and cation exchange capacity. The kinetic sorption curves of Cu2+by the bulk soil and the aggregates, which were divided into two stages(rapid and slow sequentially), were well fitted by the first-order equation, the diffusion equation, and the Elovich equation, showing significant correlations(P < 0.05). Specific and non-specific sorption dominated in the fast and slow stages, respectively, and the former was predominant throughout the sorption process. The specific sorption accelerated and the non-specific sorption decelerated with rising temperature. The p H of the solution decreased significantly during the specific sorption and remained unchanged or increased slightly during the non-specific sorption. When the specific sorption terminated, the p H of the solution was minimized nearly simultaneously.The sorption progress of Cu2+by the bulk soil significantly preceded that by the aggregates. Therefore, heavy metal contamination may be another factor reducing soil p H and metal sorption forms should be taken into consideration in studies of mitigating soil heavy metal pollution or determining environmental capacity of heavy metal in soil.     

Field-Scale Assessment of Phytotreatment of Soil Contaminated with Weathered Hydrocarbons and Heavy Metals (9 pp)

Background, Aim and Scope   Phytoremediation is a remediation method which uses plants to remove, contain or detoxify environmental contaminants. Phytoremediation has successfully been applied for the removal of fresh hydrocarbon contamination, but removal of aged hydrocarbons has proven more difficult. Biodegradation of hydrocarbons in the subsurface can be enhanced by the presence of plant roots, i.e. the rhizosphere effect. Phytostabilization reduces heavy metal availability via immobilization in the rhizosphere. Soils contaminated by both hydrocarbons and heavy metals are abundant and may be difficult to treat. Heavy metal toxicity can inhibit the activity of hydrocarbon-degrading microorganisms and decrease the metabolic diversity of soil bacteria. In this experiment, weathered hydrocarbon- and heavy metal- contaminated soil was treated using phytoremediation in a 39- month field study in attempts to achieve both hydrocarbon removal and heavy metal stabilization. Materials and Methods: A combination of hydrocarbon degradation and heavy metal stabilization was evaluated in a field-scale phytoremediation study of weathered contaminants. Soil had been contaminated over several years with hydrocarbons (11400±4300 mg kg dry soil)-1 and heavy metals from bus maintenance activities and was geologically characterized as till. Concentrations of soil copper, lead and zinc were 170±50 mgkg-1, 1100±1500 mg kg-1 and 390±340 mg kg-1, respectively. The effect of contaminants, plant species and soil amendment (NPK fertilizer or biowaste compost) on metabolic activity of soil microbiota was determined. Phytostabilization performance was investigated by analyses of metal concentrations in plants, soil and site leachate as well as acute toxicity to Vibrio fischeri and Enchtraeus albidus. Results: Over 39 months hydrocarbon concentrations did not decrease significantly (P=0.05) in non-amended soil, although 30% of initial hydrocarbon concentrations were removed by the last four months of study. In soil amended with NPK fertilizer and municipal biowaste compost, 65 % and 60 % of hydrocarbons were removed, respectively. The soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Compost addition resulted in a slight increase in enzymatic activities. Diesel fuel utilization potential in Biolog MT2 plates inoculated with a soil suspension was enhanced by both compost and NPK compared to non-amended soil. Soil toxicity to V. fischeri and E. albidus was low. The leachate was not toxic to V. fischeri. Pine (Pinus sylvestris), poplar (Populus deltoides x Wettsteinii), grasses and clover (Trifolium repens) survived to varying degrees in the contaminated soil. All plants suffered from phytotoxicity symptoms and some trees died during the study period. Plants formed a dense cover over the compost-amended soil, whereas non-amended soil had areas devoid of vegetation throughout the study. Vegetation coverage in the NPK-amended quarter was about 50 % after the first four months of study, but increased gradually to 100 %. Heavy metals did not accumulate in plant tissue. Discussion: Removal of hydrocarbons from weathered unfertilized hydrocarbon-contaminated soil was not statistically significant despite the presence of a viable hydrocarbon-degrading microbial community. This effect is attributed to soil heterogeneity and low bioavailability of hydrocarbons. Hydrocarbon concentrations were not reduced to the desired level, i.e., 1500 mg hydrocarbons (kg of dry soil)-1, in any treatment. . The presence of clay minerals and organic matter within the compost may have limited heavy metal transfer to leachate and plant tissue. Conclusions: Weathered hydrocarbons were partly decomposed in soil fertilized with NPK fertilizer or biowaste compost, but not from unfertilized soil. The active hydrocarbon-degrading microbiota and low toxicity of soil to V. fischeri and E. albidus indicates low availability of contaminants to microorganisms. Despite high heavy metal concentrations, the soil contained metabolically diverse bacteria, measured as carbon source utilization and extracellular enzymatic activities. Heavy metals did not accumulate in test plants. Pine and poplar suffered from phytotoxicity symptoms in the soil and could not enhance hydrocarbon removal in compost-amended soil. Compost addition combined with a grass and legume crop is suggested for stabilization of combined hydrocarbon- and metal-contaminated soil. Recommendations and Perspectives: Both compost and NPK fertilizers can be used to enhance phytoremediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals; however, compost addition is recommended since it enables greater vegetative coverage. This in turn may decrease heavy metal mobility. Phytoremediation can be used for remediation of soil contaminated with weathered hydrocarbons in the presence of heavy metals. However, phytoremediation of weathered contaminants requires extended periods of time; thus, other remediation methods should be considered in the event of soil contamination posing an immediate public health and/or environmental threat.     

Immobilization and species of heavy metals in soils in the absence and presence of rhizobia

Abstract

The effect of bacterial inoculation of Rhizobium fredii HN01 on the immobilization and speciation of Cu, Zn, and Cd was studied in Red and Cinnamon soil which are typical Chinese soils. The soil was mixed with bacterial suspension for one week followed by an immobilization of each heavy metal for another week. The total binding and fractionation of heavy metals in soils were analyzed. As compared with the control, the retention of total Cu, Zn, and Cd in Red soil increased by 28, 16, and 28%, respectively, in the presence of rhizobia. The amount of exchangeable, NH₄OAc-extractable, Mn oxides-bound and organic matter-bound Cu increased by 23–123%. There were significant decrease of exchangeable Cu and marked increases of NH₄OAc-extractable and Mn oxide-bound Cu in Cinnamon soil with the presence of rhizobial cells, although no changes for the total retention of Cu were observed. The amount of exchangeable Zn in Red soil-rhizobia composite was 20% greater than that of the no-rhizobia soil. Addition of rhizobia also increased exchangeable Cd and specifically-adsorbed Cd by 25 and 93%, respectively, in Red soil. No considerable differences were found for the total immobilization of Zn and Cd as well as their distribution in various solid fractions of Cinnamon soil in the absence and presence of rhizobial cells. In terms of soil components, it is assumed that bacterial biomass had a relatively less impact on the species of heavy metals bound with Fe oxides. Results suggested that the retention and speciation of heavy metals in soil are governed largely by the interactions of bacteria with various inorganic and organic soil constituents. The data are useful in understanding the impact of microorganisms on the behavior, mobility and transformation of heavy metals in soil environments.     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.     

Elucidating the fundamental chemistry of soils: past and recent achievements and future frontiers

Contributions in the field of soil chemistry have immensely benefited humankind, including enhanced agricultural production and the quality of our environment. This review focuses on research breakthroughs since the mid-1970s and delineates frontiers in soil chemistry for the upcoming decade. However, early contributions in ion exchange, sorption phenomena, and soil acidity are highlighted. Beginning in the 1970s, soil chemistry paradigms shifted from the chemistry of plant nutrient reactions/processes in soils to studies on environmental soil chemistry. The latter included research on: acid rain effects on soils and waters; trace metal/metalloid, environmentally important plant nutrient, radionuclide, and organic chemical reaction mechanisms and retention; speciation of soil contaminants using chemical extraction and molecular scale analytical techniques; facilitated colloid transport of metals and organic chemicals; humic substance structure; kinetics of soil chemical processes; redox transformations of contaminants in soils; modeling of soil chemical reactions; and soil remediation. Frontiers in soil chemistry over the next decade will undoubtedly involve the use of advanced in situ technologies in combination with interdisciplinary research efforts to unlock important information on: speciation of contaminants in soils; cycling of trace elements and nutrients and impacts on global climate change; development of models to accurately predict the rate, fate, and transport of contaminants in the subsurface environment; elucidation of mechanisms for microbial transformations of contaminants; unraveling the precise structure of soil organic matter; and enhanced understanding of rhizosphere chemistry. In summary, the future of soil chemistry is bright for the 21st century.     

Biodegradation of pyrene and catabolic genes in contaminated soils cultivated with Lolium multiflorum L

Background, aim, and scope  

In the soil environment, polycyclic aromatic hydrocarbons (PAHs) and heavy metals (HMs) are of great environmental and human health concerns due to their widespread occurrence, persistence, and carcinogenic properties. Bioremediation of contaminated soil is a cost-effective, environmentally friendly, and publicly acceptable approach to address the removal of environmental contaminants. However, bioremediation of contaminants depends on plant–microbe interactions in the rhizosphere. The microorganisms that can mineralize various PAHs have PAH dioxygenase genes like nahAc, phnAc, and pdo1. To understand the fate of pyrene in rhizospheric and non-rhizospheric soils in the presence or absence of Pb, pyrene biodegradation, bacterial community structure, and dioxygenase genes were investigated in a pot experiment.     

Biodegradation: The Reason for the Inefficiency of Small Organic Acids in Chelant-Assisted Phytoextraction

Natural low molecular weight organic acids (NLMWOA) have been shown to be useful in enhancing phytoextraction without a high leaching probability. Nevertheless, their efficiency has in many cases been unsatisfactory. The objective of this study was to investigate the reason for the inefficiency of three NLMWOAs (citric acid, oxalic acid and tartaric acid) in enhancing phytoextraction. In several experiments attention was directed not only to the biodegradation of the NLMWOAs, but also to the microorganisms involved, and their influence on the bioavailability of Cu. During a time period of 96 h the biodegradation of the NLMWOAs increased the natural pH-value of the soil by approximately 1 unit and decreased the bioavailability of Cu from 175 mg kg^?1 to approximately 140 mg kg^?1. As microorganisms were detected with polymerase chain reaction sequencing and with the aid of high performance liquid chromatography measurements, it can be deduced that the fungi, Cordyceps sp., Paecilomyces sp. and the bacteria Burkholderia sp. can degrade all three used NLMOWA. A successive application of the three NLMWOAs to increase the efficiency is therefore not feasible, because with each NLMWOA application the number of microorganisms which can degrade the NLMWOAs increases and thus the degradation is accelerated. These results combined with result from previous studies show that the NLMWOAs are unsuitable in enhancing phytoextraction of heavy metals from the soil.     

改良剂原位修复重金属污染土壤研究进展

改良剂原位修复重金属污染土壤因其成本低廉、易于实施,已经得到广泛应用。然而,改良剂对土壤重金属的修复仍然存在着一定的局限性和潜在风险。无机和有机改良剂的修复效果不仅与重金属离子的种类有关,而且还受作物、土壤类型及环境因子的制约。本文就目前常用改良剂的修复效果,存在的问题,改良剂原位修复重金属污染土壤的作用机制以及国内外研究进展作简要综述,并对此方面研究的未来趋势提出展望。     

制备条件对生物质炭特性及修复重金属污染农田土壤影响研究进展

生物质炭是生物质废弃物在限氧条件下热解产生的多孔、低密度的富碳材料。前体物质和热解条件在很大程度上决定了生物质炭的表面积和阳离子交换量,影响生物质炭将重金属污染物吸附到其表面的能力,从而影响重金属在农田土壤中的迁移。本文从生物质炭的前体物质种类及热解条件对生物质炭的特性、改良土壤以及修复重金属污染农田土壤的影响等方面进行综述,并提出生物质炭修复重金属污染农田土壤研究的未来发展趋势。     

Sorption of Cu by organic matter from the decomposition of rice straw

Purpose

Sorption of heavy metals on soil components plays an important role in reducing their mobility and bioavailability. Organic matter is an important sorbent of heavy metals in soil. Crop residues which are important sources of soil organic matter will undergo decomposition after addition to the soil. However, few studies reported the effect of organic matter decomposition on heavy metal sorption. This study aimed to investigate the effect of straw decomposition on the sorption of Cu.

Materials and methods

Rice straw was decomposed in aerobic conditions for 1, 3, 6, and 12 months, respectively. Solid organic matter in decomposed rice straw was collected and marked OM-1, OM-3, OM-6, and OM-12, respectively. Sorption isotherms and kinetics of Cu on solid organic matter were studied by batch experiments. The sorption of Cu was calculated by the difference between the amount of Cu added initially and that remained in the supernatant. Sorption thermodynamics of Cu were studied by isothermal titration calorimetry technique. Potential mechanisms of Cu sorption were analyzed by combining the information from sorption thermodynamics, desorption experiments, and Fourier transform infrared spectroscopy observations. All sorption experiments were carried out at pH 5.0.

Results and discussion

The maximum sorption of Cu was 165.8, 170.5, 186.6, and 226.9 mmol kg^?1, and the rate constant of Cu sorption was 0.80, 0.58, 0.50, and 0.32 kg mmol^?1 h^?1 on OM-1, OM-3, OM-6, and OM-12, respectively, indicating that the maximum sorption of Cu increased while sorption rate of Cu decreased with increasing the duration of straw decomposition from 1 to 12 months. The negative values of Gibbs free energy change and positive values of enthalpy change and entropy change revealed that Cu sorption was spontaneous, endothermic in nature, and the randomness was increased during sorption. Carboxyl and hydroxyl in solid organic matter were involved in Cu sorption. The percentage of Cu desorbed by NH₄Ac from OM-1, OM-3, OM-6, and OM-12 was 45.0, 43.5, 42.8, and 37.8 %, respectively.

Conclusions

In the current study, the decomposition of straw promoted the sorption capacity but reduced the sorption rate of Cu on solid organic matter. Copper sorption was an endothermic and spontaneous process. The formation of inner-sphere complexes was the main mechanism of Cu sorption, and its role in Cu sorption tended to increase with increasing the duration of straw decomposition. The information will facilitate the understanding of the contamination and remediation of heavy metal in cropland.

     

Depth distribution and bioavailability of pollutants in long-term differently tilled soils

Pollutants can be introduced to soil through the application of organic and inorganic fertilizers and pesticides and through atmospheric depositions. The objective of this research was to evaluate the influence of long-term (9–17 years) tillage systems on the behavior of pollutants in soils. Bioavailability and enrichment of heavy metals, arsenic, and organics, i.e. polychlorinated biphenyls (PCB’s) and a chlorinated phenol (2,4-DCP) were measured in a Eutric Cambisol and a Luvisol under conventional tillage (CT), reduced tillage (RT), and no-tillage (NT). Soil samples were collected from 0 to 3, 3 to 10, and 10 to 25 cm depths.

The upper layer of NT soils was enriched in pollutants, but concentrations decreased with increasing soil depth. Atmospheric deposition of pollutants and input via organic fertilizers was noticeable in soils under long-term NT. Total amount of zinc (59 mg kg⁻¹) was significantly enriched in the 0–3 cm depth of the Luvisol under NT and this was attributed to higher sorption capacity for heavy metal input via liquid manure. In the Eutric Cambisol, NT resulted in significant increase of cadmium extracted by aqua regia in the arable layer of 0–25 cm. As a result of higher soil organic C, long-term accumulation of PCB’s in NT soils was more pronounced than in plowed soils. In plowed soils the mixing effect resulted in homogeneous distribution of pollutants within a soil depth of 0–25 cm.

The enrichment of organic C in RT and NT soils emphasizes the role of soils as a sink for pollutants, buffering the contaminants against leaching and transfer into crops.     

Interactions of simazine, metsulfuron-methyl, and tetracycline with biochars and soil as a function of molecular structure

Purpose

Biochars are increasingly recognized as effective, inexpensive, and environmentally friendly sorbents for abating organic contaminants. In this study, the sorption and competitive sorption characteristics of simazine (SZ), metsulfuron-methyl (ME), and tetracycline (TC) to corn straw biochars and soil were examined to understand the interactions of herbicides and antibiotics with biochars and the potential role of biochars as engineered sorbents.

Materials and methods

Biochars were obtained by pyrolyzing corn straw at 400, 500, and 600 °C for 6 h under oxygen-limited conditions and were characterized via elemental analysis, N₂-BET surface area determination, ¹³C nuclear magnetic resonance spectroscopy, and Fourier transform infrared spectroscopy. Soil was collected from North Tanggu Farm in Tianjin, and its organic carbon, cation exchange capacity, and particle size distribution were analyzed. The batch sorption experiments were performed to obtain the sorption isotherms of SZ, ME, and TC to biochars and soil.

Results and discussion

The biochars that were pyrolyzed at higher temperatures had higher sorption affinities for SZ, ME, and TC, which may be due to the enhancement of hydrophobic interactions, charge transfer (π–π*) interactions, and pore-filling mechanism. The sorption affinities for these compounds to all biochars decreased in the order SZ?>?TC?>?ME, indicating that the neutral molecule with a stronger hydrophobicity is more easily adsorbed by biochars. For soil, the decrease of the sorption affinities followed the order TC?>?SZ?>?ME due to the high sorption affinity of TC with clays in the soil. Moreover, the sorption affinities of TC by biochars were lower than by soil, indicating that corn straw biochars may be not an ideal sorbent for the immobilization of TC. Biochars were much more effective in sorbing SZ and ME than soil, indicating that corn straw biochars can potentially prevent transport of the herbicides to surface and ground water. Nevertheless, the presence of TC significantly hinders biochar adsorption of SZ and ME, implying that the coexisting contaminants should be considered when developing biochars as engineered sorbents.

Conclusions

The observations in this study demonstrated that the sorption of organic contaminants by biochars is dependent on the properties of the biochars and the molecular structures of the contaminants. Corn straw biochars effectively retain SZ and ME and hinder their transportation to surface and ground water; however, the coexisting contaminants should be considered. Our results will be helpful for designing biochars as engineered sorbents for environmental applications.