再生水灌溉对4类土壤Cd生物有效性的影响

根据国家土壤环境质量标准,选取重金属Cd含量为二级水平的4类土壤（红壤、 潮土、 土、 黑土）进行土培试验,研究再生水灌溉与小白菜生物量及Cd含量、 土壤有效态Cd含量、 pH、 微生物群落的关系,以及不同类型土壤间的差异性。结果表明, 再生水灌溉在不同类型土壤上对小白菜生物量及Cd含量、 土壤有效态Cd含量、 土壤pH和微生物数量的影响不同: 1）红壤、 潮土、 土上小白菜生物量增加显著,分别增加9.09%、 16.08%、 9.92%,黑土上增加不显著; 2）小白菜Cd含量在红壤上显著降低,由对照的0.29 mg/kg降低到0.22 mg/kg,在黑土上比对照增加了18.75%,在潮土和土上影响不大; 3）有效态Cd含量在红壤没有变化,但在潮土、 土、 黑土上增加显著; 4） 4类土壤微生物数量增加显著; 5）潮土、 土、 黑土的pH值有所降低。     

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.     

环境材料对Pb、Cd污染土壤玉米生长及土壤改良效果的影响

为探索环境材料对种植于Pb、Cd污染土壤中的玉米生长、品质的影响, 以及对Pb、Cd重金属污染土壤的改良效应, 本文采用温室盆栽方法, 研究了不同环境材料[腐殖质类材料(HA)、高分子材料(SAP)、煤基复合材料(FM)及粉质矿物材料(FS)]及其复合处理对Pb-Cd复合污染土壤中玉米(Zea mays L.)生长、品质及根系土壤环境的影响。结果表明, 添加环境材料组合F22(FM+SAP)、F23(FS+SAP)及F32(HA+SAP+FS)能促进苗期玉米生长, 长势好于对照; 所有环境材料处理中玉米地上部粗灰分含量都低于对照, 添加单一环境材料对玉米地上部粗淀粉含量的提高效果高于对照、优于组合; 处理FM、F33(SAP+FM+FS)及F4(HA+SAP+FM+FS)对土壤中Pb固定效果显著, 抑制土壤中Pb向玉米体内迁移; 单一处理FM、FS及组合F33(SAP+FM+FS)对土壤重金属Cd固化效果明显, 抑制土壤中Cd向玉米体内迁移。环境材料的添加在一定程度上有助于土壤基本理化性质的改善, 促进土壤改良, 同时环境材料对阻止土壤重金属向植物体迁移有一定作用。     

施污泥土壤中铜的形态分布及其生物有效性

利用蔬菜盆栽试验研究了黄棕壤(pH 6.2)和红壤(pH 4.3)中施用污泥对土壤中Cu转化和蔬菜吸收的影响.施用污泥初期提高了土壤溶液的pH,但种植蔬菜后,降低了土壤溶液的pH,其中黄棕壤溶液pH的下降更大;施用污泥和种植蔬菜提高了土壤溶液的NO3--N含量,黄棕壤溶液中NO3--N含量的增幅高于红壤.施用污泥增加了土壤溶液中Cu的含量,特别是在酸性更强的红壤中影响更大;施用污泥的红壤中主要增加了冰醋酸溶解态Cu的比例,而黄棕壤中主要增加了铁锰氧化物结合态Cu的比例;施用污泥促进了蔬菜的生长,但对蔬菜植株中Cu含量的影响较小.土壤pH是影响污泥重金属在土壤中转化和植物吸收的主要因素,在酸性更强的红壤中施用污泥导致污泥中Cu更多地转化为植物有效性Cu,具有更高的环境风险.     

生物炭对水稻-再生稻体系吸收土壤中Cd和Pb的影响

以矿区周边Cd—Pb复合污染的农田土壤为供试材料,设置0,2.5%和5%(w/w)3个生物炭添加处理,通过盆栽试验探讨生物炭对再生稻吸收土壤中Cd和Pb的影响。结果表明,生物炭施加提高土壤pH和有机质含量,使Cd和Pb从移动性较强的弱酸提取态转化为较稳定的可还原态,且土壤CaCl2提取的有效态Cd和Pb含量分别降低33.23%~53.23%和66.52%~91.45%。同时,生物炭抑制Cd在头季和再生季水稻叶到糙米中的迁移,降低Pb从茎到叶和糙米的迁移,从而减少Cd和Pb在糙米中的累积;在5%生物炭处理下,再生季糙米Cd含量为0.15mg/kg,低于食品安全国家标准限量值(0.2mg/kg);Pb含量比对照处理降低68.18%。此外,再生季糙米中Cd和Pb含量低于头季稻糙米中相应的含量。因此,生物炭可以抑制Cd和Pb在再生稻体内的累积,降低糙米的重金属污染风险。     

Characterization of phosphorus engineered biochar and its impact on immobilization of Cd and Pb from smelting contaminated soils

Journal of Soils and Sediments - Biochar has been used as an amendment to immobilize toxic metals (TMs) and increase nutrient content in the contaminated soil. In this study, Ca(H2PO4)2-engineered...     

Chemical transformation of copper in some sludge-amended soils

In a laboratory incubation study, the periodic changes in different chemical fractions of copper (Cu) in three sludge-amended soil types (acidic sandy clay loam, neutral clay loam and alkaline clay loam) of varying soil reaction were monitored under field capacity and flooding moisture regime over 16 months. The water soluble and exchangeable fraction of Cu was very low (≤1% of total Cu) in all three soil types. At the end of incubation (16 months), the sodium acetate extractable (carbonate sorbed)- and residual-Cu fractions transformed into Fe-Mn oxide fraction, irrespective of moisture regime in all three soil types. However, the extent of transformation varied among soils.     

镉污染水稻秸秆生物炭对土壤中镉稳定性的影响

中国农田土壤镉等重金属污染问题突出,对其生产过程中产生的镉污染水稻秸秆进行无害化和资源化利用研究具有重要意义。该研究通过连续提取试验、风险评价指数法、吸附动力学/热力学、土柱试验,以及X射线衍射分析、傅里叶变换红外光谱分析等手段,探究了不同热解温度下制备的镉污染水稻秸秆生物炭对土壤中Cd的稳定特性。研究结果表明,镉污染水稻秸秆热解制备的生物炭可有效吸附土壤镉。热解温度显著影响生物炭对Cd的吸附能力（P<0.05）,高温生物炭对Cd吸附容量大,700 ℃下制备的生物炭对Cd的吸附容量可达72.57 mg/g。生物炭对Cd的吸附主要通过含氧官能团表面络合和碳酸盐共沉淀吸附,其吸附过程符合Langmuir方程和准二级动力学模型,吸附过程受化学速率控制。土柱试验表明,镉污染水稻秸秆生物炭能有效降低土壤Cd的下渗迁移能力,其作用机制主要是将土壤Cd从酸可提取态转化为残渣态,施入高温生物炭的土壤中Cd的残渣态比例最高。上述结果表明,热解可有效处理镉污染水稻秸秆,制备的生物炭可用于Cd等重金属污染土壤的稳定修复,有效解决镉污染水稻秸秆的潜在二次污染问题并实现其安全利用。     

低分子有机酸对土壤中重金属的解吸及影响因素

研究了柠檬酸、草酸、酒石酸和苹果酸对矿区土壤中重金属Pb、Cd、Cu和Zn的解吸行为,并探讨了介质pH值对其解吸土中重金属的影响。振荡解吸试验结果表明四种低分子有机酸对供试污染土壤中Pb、Cd、Cu和Zn都具有一定的解吸能力。由于土壤中重金属有效态含量较低,各重金属的解吸率都不高。在对Pb和Cd的解吸中,各低分子有机酸能力大小顺序为柠檬酸>酒石酸≈苹果酸>草酸;Cu的解吸顺序为柠檬酸>草酸>酒石酸≈苹果酸;Zn的解吸顺序为酒石酸>柠檬酸≈苹果酸>草酸。低分子有机酸随浓度的增加,其解吸能力提高。低分子有机酸对重金属的解吸量随pH值的降低而增加。     

Effects of natural zeolites on ryegrass growth and bioavailability of Cd,Ni, Pb,and Zn in an Albanian contaminated soil

Purpose

The use of eco-friendly and cost-effective adsorbent materials in the remediation of soils contaminated by potentially toxic elements (PTE) is a sustainable way of reducing the transfer of these elements into the food chain. However, an evaluation of the potential of natural zeolites to immobilize toxic elements in contaminated soils was required to enable their efficient use.

Materials and methods

The effect of natural zeolite (Stilbite-Stellerite) from the Munella area (Northern Albania), added at rates ranging from 1.25 to 10 % w/w on a contaminated soil was investigated in a greenhouse pot experiment with ryegrass (Lolium multiflorum L.) and by selective extractions. PTE availability for plants was assessed either as their accumulation in plant tissue or by DTPA-extraction. Oral bio-accessibility was estimated by the in vitro PBET method and the mobility and consequent potential risk of leaching by the USEPA TLCP method. The effect of zeolites on soil properties (pH, electrical conductivity-EC, organic C, and total N) was also investigated. A five steps sequential extraction procedure (SEP) was applied to investigate the immobilization mechanism.

Results and discussion

The addition of 2.5% w/w of natural zeolites caused a significant decrease of PTE mobility, but to observe a significant reduction of DTPA-extractable metals, it was necessary to reach 10% addition rate. In contrast, plant growth showed a gradual increase with addition rate and a corresponding decrease of concentration of PTE in plant tissue. Correlation between DTPA-extractable PTE and their concentration in both root and shoot plant tissue was rather poor. Human hazard due to soil ingestion (PBET method) changed only for Cu and Zn in the gastric phase with 1.25 and 5% addition rate respectively, whereas decreased for Cu and Zn at 5% rate in the Intestinal phase. The results of SEP support the hypothesis that the main mechanism involved in metals fixation are as follows: (1) insolubilization by pH rise, (2) adsorption on Fe/Mn oxides (3) increase of cation exchange retention, (4) organic complexation.

Conclusions

The results of this work suggest that the addition of natural zeolites from the Munella area (AL) is a sustainable practice to reduce the environmental impact of PTE contaminated soils, but an assessment on the longevity of their immobilization need to be evaluated in the long-term perspectives.

     

影响土壤中镉的植物有效性的因素及镉污染土壤的植物修复

阐述了镉的来源及其对人类的危害,并对影响土壤中镉的植物有效性的土壤因素中的pH、氧化还原电位(Eh)、有机物质、营养物质浓度对镉的植物有效性的作用作了详细的阐述。此外对其它如EDTA、淤泥等对土壤中镉的植物有效性的影响和镉污染土壤的植物修复等方面也进行了综述,并对镉污染土壤的修复治理与趋势进行了展望。     

Solubility control of Cu, Zn, Cd and Pb in contaminated soils

We developed a semiempirical equation from metal complextion theory which relates the metal activity of soil solutions to the soil's pH, organic matter content (OM) and total metal content (MT). The equation has the general form: where pM is the negative logarithm (to base 10) of the metal activity, and a, b and c are constants. The equation successfully predicted free Cu²⁺ activity in soils with a wide range of properties, including soils previously treated with sewage sludge. The significant correlation of pCu to these measured soil properties in long-contaminated soils suggests that copper activity is controlled by adsorption on organic matter under steady state conditions. An attempt was made from separate published data to correlate total soluble Cu, Zn, Cd and Pb in soils to soil pH, organic matter content and total metal content. For Cu, the total Cu content of the soil was most highly correlated with total soluble Cu. Similarly, total soluble Zn and Cd were correlated with total metal content, but were more strongly related to soil pH than was soluble Cu. Smaller metal solubility in response to higher soil pH was most marked for Zn and Cd, metals that tend not to complex strongly with soluble organics. The organic matter content was often, but not always, a statistically significant variable in predicting metal solubility from soil properties. The solubility of Pb was less satisfactorily predicted from measured soil properties than solubility of the other metals. It seems that for Cu at least, solid organic matter limits free metal activity, whilst dissolved organic matter promotes metal solubility, in soils well-aged with respect to the metal pollutant. Although total metal content alone is not generally a good predictor of metal solubility or activity, it assumes great importance when comparing metal solubility in soils having similar pH and organic matter content.     

作物间作对油菜积累镉与铅的影响

采用盆栽试验,研究了与黑麦草(Lolium perenne)及紫云英(Astragalus siniucus)间作对芥菜型油菜(Bras-sica juncea)和甘蓝型油菜(B.napus)积累镉与铅的影响。结果表明:单种和混种紫云英显著增加土壤氮,单种和混种油菜及黑麦草显著降低土壤氮。栽培植物增加土壤的碱解氮、速效磷、速效钾和有机质,单种紫云英显著降低土壤pH值。间作时,两种油菜的生物量显著增加,其SOD活性显著降低,黑麦草和紫云英的SOD活性显著增加,两种油菜的镉和铅含量显著降低,黑麦草和紫云英的根部的镉和铅含量显著增加,两种油菜地上部和根部的镉与铅的生物富集系数显著下降,黑麦草和紫云英的根部的镉和铅的生物富集系数显著增加。因此,与黑麦草及紫云英间作可减少油菜积累镉与铅,降低重金属对人类危害。     

施用生物炭对红壤富硒区硒生物有效性的影响

研究生物炭调理措施对红壤区富硒土壤硒形态及硒生物有效性的影响,为富硒土壤硒活化及硒资源高效利用提供理论依据。通过盆栽试验,连续开展三批玉米苗期研究,设置3个生物炭添加水平：土壤质量0.5%(T1)、1.0%(T2)和1.5%(T3),以不添加生物炭处理为对照（CK）,分析生物炭添加对土壤硒形态及玉米硒素营养的影响。结果表明：施用生物炭后,T1、T2和T3的可溶态硒分别平均提高0.46、0.42和0.43个百分点;可交换态硒分别平均提高0.61、1.66和1.50个百分点;降低了铁锰氧化物结合态硒的比例;有机结合态硒比例先降低后逐渐提高,残渣态硒比例则先提高后逐渐降低。玉米根系硒含量与土壤可溶态、可交换态及有效硒含量均呈显著线性正相关,玉米茎叶硒含量与土壤各硒形态之间的相关性不显著。施用生物炭能提高玉米植株体内的硒累积量,T1、T2和T3处理玉米植株平均硒累积量分别比CK提高9.46%、31.00%和21.22%。可见,在红壤上施用生物炭能有效提高土壤硒的生物有效性并促进硒在植物体内的累积,其中以添加土壤质量1.0%的生物炭效果最好。     

The flux of Cd,Cu, Pb and Zn in mining polluted soils

The monitoring of heavy metal deposition onto soils surrounding old Pb-Zn mines in two locations in the UK has shown that relatively large amounts of Cd, Pb, Zn and, in one case, Cu are entering the soil annually. Small particles of ore minerals in windblown mine tailings were found to be contributing up to 1.46 g m^?2 yr^?1 of Pb, 1.41 g m^?2 yr^?1 of Zn and 0.027 g m^?2 yr^?1 of Cd. However, when these inputs from bulk deposition are compared with the concentrations of the same metals within the soil profiles it is apparent that relatively little long-term accumulation is occurring. Metals are being lost from the soil profiles, probably through leaching. A calculated relative retention parameter gave values that ranged from 0.01 to 0.17 for Cd, 0.11 to 0.19 for Zn, 0.32 to 0.63 for Cu and over 1 for Pb. These relative retention values were found to follow the order of electronegativity of the elements concerned: Pb>Cu>Zn>Cd. Distribution coefficient (Kd) values quantifying the adsorptive capacity of the mine soils for Cd and Pb showed marked differences for the two metals (12 to 69 cm³ g^?1 for Cd and 14 to 126 cm³ g^?1 for Pb) and may, in part, account for the two to one hundred-fold variation in the relative retention parameter for the different metals within these soils.     

修复剂调控铅镉污染棉田对土壤微生物多样性的影响

为探讨重金属铅(Pb)、镉(Cd)污染下棉粕腐植酸和聚丙烯酸钾修复剂对土壤微生物多样性的影响,采用田间桶栽试验,进行了棉粕腐植酸、聚丙烯酸钾以及两者复合施用修复污染棉田土壤的研究,通过高通量测序分析了土壤微生物多样性的变化,并利用傅里叶红外光谱进行了土壤化学结构的修复响应分析。结果表明:与未施用修复剂处理相比,施用棉粕腐植酸和聚丙烯酸钾减少了表层土壤Pb、Cd含量,其中两者复合处理可分别减少62.6%和52.3%;改变了土壤微环境进而影响了土壤微生物多样性,不同处理共发现土壤细菌25个门,69个纲,149个目,273个科,442个属,其中优势菌门主要为变形菌门、酸杆菌门、芽单胞菌门和放线菌门。聚丙烯酸钾处理增加了土壤中变形菌门的相对丰度,棉粕腐植酸和复合修复处理增加了酸杆菌门和芽单胞菌门的相对丰度。由此可见,铅镉复合污染土壤中微生物多样性丰富,优势菌群相对稳定,聚丙烯酸钾和棉粕腐植酸通过改变土壤微环境进而影响菌群丰度。     

Sorption of Cd and Pb by selected temperate and semi-arid soils: effects of sludge application and ageing of sludged soils

Five soils from semi-arid regions of India and 5 soils from England were compared with regard to their ability to sorb Cd and Pb when mixed with sewage sludge and as unsludged controls. The application of sewage sludge at 150t ha^?1 significantly increased the amount of Cd retained by the soils. The sorption data were statistically best-fit to the linearized Freundlich equation and the slopes of the isotherms were steeper with sludge application, indicating an increased affinity for Cd in the soil-sludge mixtures. A similar trend in Pb sorption was also observed for the English soils following the sludge treatment. In contrast, most of the Indian soils showed a decline in Pb sorption following the sludge application. Liming an acidic English soil to pH 7.0 was shown to increase its metal sorption capacity. The longer-term persistence of these observed effects of sewage sludge addition on metal sorption by soils was investigated in two sludge-soil mixtures maintained under experimental conditions for up to 450 days. Samples of these soils taken 1,60 and 450 days after the mixing with the sludge were batch equilibrated with Cd and Pb and it was found that the metal retention in both soils decreased significantly over this time period.     

黑土中镉、铅的化学形态分布及其植物效应研究

采用盆栽试验和连续形态分析方法研究了黑土中Cd、Pb的化学形态特征及其与油菜生长及吸收Cd、Pb量的关系。结果表明,随土壤Cd、Pb含量的增加,Cd交换态含量增幅较大,而Pb碳酸盐结合态、铁锰氧化物结合态含量增幅较大,交换态Pb含量相对较低。随土壤Cd、Pb含量的增加,油菜地上、地下部分的Cd、Pb含量呈递增趋势,但增加速度随土壤Cd、Pb含量的升高而递减。地下部分Cd、Pb含量远高于地上部分的含量。与Pb相比,Cd向地上部分的迁移率较大,其毒害作用更强。土壤中Cd、Pb各形态含量与油菜地下、地上部分吸收的Cd、Pb量均显著相关,碳酸盐结合态对油菜吸收Cd、Pb的贡献最大。     

温度对土壤吸附有机肥中可溶性有机碳、氮的影响

可溶性有机碳、氮(Soluble organic carbon or nitrogen,SOC和SON)可被土壤吸附.土壤可溶性有机碳、氮组分复杂,土壤对可溶性有机物吸附的不均一性会导致可溶性有机物组分的变化,大部分疏水性化合物被吸附,而亲水性化合物被释放进入溶液中[1].因此,可溶性有机碳、氮在土壤中的吸附,直接影响其在土壤-水系统中的迁移和行为[2-3].林地土壤中含有相当数量的可溶性有机养分,因此,关于林地土壤对可溶性有机养分的吸附特性,国外研究者已开展了不少研究.研究表明,可溶性有机碳吸附特性与土壤性质如pH、表面积、有机碳、铁铝氧化物和黏粒含量等因素有关[4-5].关于农业土壤对可溶性有机碳的吸附特性的影响,国内也开展了一些研究,主要集中在pH、铁铝氧化物含量等对吸附影响方面[6-9].     

施用污泥后石灰性土壤中铜、锌、镉的植物有效性

The toxicity of trace elements (TEs), such as copper (Cu), zinc (Zn), and cadmium (Cd), often restrict land application of sewage sludge (SS) and there was little information about soil-plant transfer of TEs in SS from field experiments in China. In this study pot and field experiments were carried out for 2 years to investigate the phytoavailability of TEs in calcareous soils amended with SS. The results of the pot experiment showed that the phytoavailability of Zn and Cu in the SS was equal to 53.4%-80.9% and 54.8%-91.1% of corresponding water-soluble metal salts, respectively. The results from the field experiment showed that the contents of total Zn, Cu, and Cd in the soils increased linearly with SS application rates. With increasing SS application rates, the contents of Zn and Cu in the wheat grains initially increased and then reached a plateau, while there was no significant change of Cd content in the maize grains. The bioconcentration factors of the metals in the grains of wheat and maize were found to be in the order of Zn > Cu > Cd, but for the straw the order was Cd > Cu > Zn. It was also found that wheat grains could accumulate more metals compared with maize grains. The results will be helpful in developing the critical loads of sewage sludge applied to calcareous soils.