污泥中重金属的稳定化研究进展与去除方法简述

通过"十一五"污水处理厂的建设,我国污泥产量也随之大幅增长,污泥的处理处置已经成为制约社会经济发展的重要问题。国际上的经验表明土地利用是污泥最终处置的主要发展方向,然而污泥中的重金属成为其土地利用的主要障碍。越来越多的研究者意识到,重金属的环境危害不仅仅取决于其总量,更取决于重金属存在形态。目前,Tessier分步提取法作为主流的污泥重金属划分方法,取得了广泛应用,该法将污泥中的重金属分成5种形态,分别为可交换态、碳酸盐结合态、铁锰氧化物结合态、有机结合态和残渣态。本文以此为基础综述了目前国内外主要的污泥重金属稳定和去除方法的原理及研究进展,比较了不同重金属稳定及去除方法的优点与不足,并提出了新的展望。     

典型铅冶炼鼓风炉周边土壤重金属含量及化学形态研究

铅冶炼鼓风炉周边区域土壤中重金属含量及化学形态是研究揭示鼓风炉炼铅生产对周边影响的重要方式。本文以典型铅冶炼鼓风炉周边区域污染土壤为对象,研究了其重金属含量和As、Cd的化学形态。结果表明,土壤中存在一定的As、Pb、Cd、Cu、Zn等累积污染现象,特别是As、Cd污染较为突出,其平均污染程度远高于国家土壤污染风险筛选值;As、Cd的化学形态提取结果表明,土壤中Cd的活性态含量较高,特别是可交换态含量较高,具有一定的释放潜力和生物有效性,应当予以重点防控,而As的形态相对比较稳定,以残渣态为主,潜在危害相对较小。     

宁夏灌区不同类型农田土壤氮素累积与迁移特征

在宁夏灌区选择设施菜田（n=4）和水旱轮作大田（n=4）,通过田间多点取样观测和室内分析的方法,研究了2种类型农田土壤氮素累积与分布特点,以及其迁移对浅层地下水的影响。结果表明,设施菜田0~150 cm土壤剖面溶解性总氮（TSN）、硝态氮（NO3--N）和溶解性有机氮（SON）含量都显著高于大田,前者分别是后者的1.5~5.6、1.5~3.4倍和1.6~9.8倍。设施菜田土壤氮素主要累积在0~5 cm和5~20 cm土层,而大田主要在40~100 cm土体。设施菜田和大田土壤溶解性总氮占全氮比例分别在5.4%~11.5%和2.2%~4.9%之间,前者的淋失风险较高。设施菜田各形态氮素累积量表现为SON＆gt;NO3--N＆gt;NH4＋-N,大田为NO3--N＆gt;SON＆gt;NH4＋-N。设施菜田浅层地下水中TSN、NO3--N和SON含量也都显著高于大田,前者平均含量分别是后者的9.5、13.8倍和7.0倍。因此,硝态氮和溶解性有机氮都是2种类型农田氮素累积的主要形态,也是浅层地下水污染的重要来源。     

纳米羟基磷灰石修复镉锌复合污染紫色土效果初探

选取安宁河谷平原矿区周边受Cd和Zn复合污染紫色土为研究对象,采用老化试验,探索添加羟基磷灰石对土壤中重金属生物有效性以及形态分布的影响,羟基磷灰石添加比例(w/w)设置为0%(CK)、1%(P1)、3%(P3)和5%(P5)。结果表明:①添加羟基磷灰石能够显著提高土壤p H值,P1、P3和P5的p H值分别比CK升高了0. 13、0. 18、0. 21个p H单位;②添加羟基磷灰石能够显著降低土壤有效态Cd和Zn (0. 025 M HCl提取),相较于CK,P1、P3和P5的有效态Cd含量可分别降低36. 0%、78. 8%、90. 2%,有效态Zn含量可分别降低25. 4%、67. 4%、84. 5%;③添加羟基磷灰石能够明显降低土壤中活性较高的可交换态和碳酸盐结合态Cd和Zn的比例(P 0. 05),明显升高了活性较低的铁锰结合态、有机结合态以及残渣态Cd和Zn的比例(P 0. 05),从而促进Cd和Zn向非活性态转化。本研究证明了羟基磷灰石在安宁河谷平原土壤重金属污染修复中有较大的应用潜力。     

西湖和东苕溪沉积物重金属化学形态分析

不同赋存形态重金属的环境行为和生态效应不同,水体沉积物中重金属的迁移转化及其潜在环境危害更大程度上取决于其赋存形态。本研究在西湖和东苕溪设置12个采样点采集沉积物样品,采用改进BCR分步提取法,提取了重金属污染物的4种化学形态,分别为弱酸提取态、可还原态、可氧化态及残渣态。结果表明:沉积物中Cd以弱酸提取态为主,对外界环境的变化极其敏感,并易于发生迁移转化,生态风险较高。Cu离子对有机质表现出极强的亲和力导致Cu的可氧化态含量较高也有一定的生态风险。Pb会被Fe-Mn氧化物所吸附导致Pb的可还原态含量较高,存在较高的潜在生态危害。Mn的弱酸提取态、可还原态和残渣态含量都较高,在迁移的过程中变化地较快,能够逐渐降低Mn对自然环境的危害。其他各重金属(As、Cr、Zn)则都以残渣态为主,潜在危害较低。     

北方河流湿地土壤NO3-N和NH4+-N的空间变化特征研究

以辽河保护区七星湿地为研究对象,通过对湿地土壤NO3--N和NH4+-N空间分布及湿地土壤含水量与pH指标分析,研究流域湿地土壤无机氮空间变化特征.研究结果表明,湿地土壤含水量影响NO3--N和NH4+-N的空间分布,湿地土壤含水量高,土壤中NO3--N的含量相对较高;湿地土壤含水量低,土壤中NH4+-N的含量相对较高...     

宜宾兴文县僰王山镇水田土壤中硒形态分布特征及研究

为了客观分析土壤中硒形态分布特征及硒有效性影响因素,依据硒不同形态下的溶解度不同,采用四步五态连续浸提取技术,由弱到强的选择顺序提取僰王山镇水田土壤中硒的水溶态、可交换态、有机质结合态、硫化物/硒化物态、残渣态这5种形态,并用原子荧光光谱法分析和氢化物发生-原子荧光光谱法测定了土壤样品中5种形态硒和总硒的含量。初步总结了研究区水田土壤硒含量特征和硒形态分布特征。研究结果发现,僰王山镇水田土壤总硒含量变化范围为0.51~0.93 mg/kg,平均值0.714 mg/kg,远远超过全国土壤总硒平均值0.290 mg/kg,且超过了目前认为的富硒土壤的标准值0.4 mg/kg。从土壤中5种形态分析结果所占比例来看,有机质结合态和硫化物/硒化物态硒是硒元素的主要赋存形态,两者占土壤总硒含量的54.63%,反应了研究区土壤中硒富集与有机质结合态存在密切关系。     

攀枝花市攀钢工业区土壤重金属污染特征及评价

本文对攀枝花市攀钢工业区土壤中五种重金属元素（Cu、Pb、Zn、Cr、Cd）的空间的分布特征、形态分布特征进行了研究，并应用污染负荷指数法对各重金属的污染程度进行了评价。研究发现，Cu、Pb、Zn、Cr的最大值与最小值分别相差2．98、3．4、5．2、2．7倍，cd的最大值与最小值甚至相差15．7倍。重金属元素相关性特征可分为Cd—Pb—Zn和Cu—Cr两组。形态分布特征表现在Cu、Zn、Pb、Cr主要以稳定的残渣态存在，Cd主要以可利用性最强的可交换态和碳酸盐结合态存在。污染较严重的是攀钢机关、攀钢原料场。     

土壤pH对东南景天修复镉污染土壤的影响研究

东南景天是一种镉和锌的超积累植物,改变土壤p H能否有效提高其吸收镉的效率,需要进一步验证。采用盆栽实验研究不同土壤p H下东南景天吸收和积累Cd的差异以及对Ca Cl2提取有效态镉的影响。结果表明,降低土壤p H值显著提高了土壤镉的有效态含量。弱酸性土壤即p H接近5.5时东南景天生物量及累积镉的量最大,土壤镉去除率也最高,达6.6%。强酸性即当p H接近4时,虽然植物地上与地下镉含量均最高,但生物量最小,植物去除率较其他处理低。研究证实降低土壤p H是提高植物提取效率的有效办法,这为进一步利用东南景天修复镉污染土壤,提高修复效率提供了科学依据。     

四川马边某磷矿区土壤重金属特征及形态分析

为研究四川马边某磷矿区土壤重金属分布状况及特征,采集矿区土壤样品,用ICP-MS测定了重金属As、Cu、Zn、Cd、Pb、Cr的含量及其形态,并用潜在生态危害指数法对土壤重金属污染程度进行评价。结果表明,研究区土壤重金属中的Cd和Pb含量高于四川土壤背景值的10. 00、7. 14倍,高于全国土壤背景值8. 14、8. 48倍,其余元素均略高于各背景值,经相关性分析,As、Zn、Cd 3种重金属具有同源性。形态分析显示,Cd的形态分布以可还原态为主,易迁移释放,其余元素均以残渣态为主,Pb除残渣态外,可还原态与可氧化态占一定比例,具有一定的潜在风险。潜在生态危害指数法分析表明,重金属的单一潜在生态危害程度E_r~i顺序为Cd Pb As Cu Cr Zn,各样点重金属潜在生态危害指数RI平均值为378. 87,属于强生态危害,其中又以Cd贡献率最大,为78%。     

Trace element changes in soil after long-term cattle manure applications

Manure application supplies plant nutrients, but also leads to trace element accumulation in soil. This study investigated total and EDTA-extractable B, Cd, Co, Cu and Zn in soil after 25 annual manure applications. The residual effect of 14 annual manure applications followed by 11 yr with no applications was also investigated. Manure was applied at 0, 30, 60 and 90 Mg ha(-1) yr(-1) (wet weight) under rainfed (treatments Mr0, Mr30, Mr60, and Mr90) and at 0, 60, 120 and 180 Mg ha(-1) yr(-1) under irrigated conditions (Mi0, Mi60, Mi120, and Mi180). The manure applications had no significant effect on soil B, Cd and Co content under both rainfed and irrigated conditions, but significantly increased total Cu and Zn content under irrigated conditions with Zn in Mi120 and Mi180 reaching the lower maximum concentration (MAC) level set by the European Community. Manure application also significantly increased EDTA-extractable Cd and Zn content in soil. Up to 27% of the total Cd (0.156 mg kg(-1)) and 21% of total Zn (38 mg kg(-1)) are found in EDTA-extractable form (Mi180 at 0-15 cm). EDTA-extractable Cd and Zn content was also significantly elevated in the irrigated residual plots due to the higher manure rates used. Thus, the impacts of cattle manure application on trace elements in soil are long lasting. Elevated Cd and Zn are a concern as other studies have linked them with certain types of cancers and human illnesses.     

Cadmium solubility and sorption in a long-term sludge-amended arable soil

Cadmium solubility and sorption in an arable clay loam soil that had received sewage sludge for 41 years were compared to an unsludged control in batch studies. Soil pH dominated Cd sorption, explaining >92% of the variation in Kd values in both treatments. At any pH, Cd sorption was apparently slightly but significantly (p < 0.05) smaller in the sludge-amended soil compared to the control, even though the organic carbon content was 70% larger and the ammonium oxalate-extractable iron content was roughly doubled. Correction for dissolved organic carbon (DOC) complexation with the speciation model WHAM reduced the difference in sorption between treatments, but the sludged soil still had significantly smaller Kd values (p < 0.01). Batch equilibrations without addition of Cd showed that there was no significant difference in the solubility of "native" cadmium (defined as EDTA-extractable Cd) in sludged and control soils. The reason for the lack of increase in Cd sorption in the sludge-amended soil has not been established, but it may be due to competition for sorption sites on humic compounds with sludge-derived Fe and trace metals such as zinc. The fact that the pyrophosphate-extractable (i.e., organically associated) iron content was seven times larger in the sludged soil provides some supporting evidence for this hypothesis.     

Modeling organic carbon dynamics and cadmium fate in long-term sludge-amended soil

A model is described that may help to resolve uncertainty and controversy over the long-term consequences of sludge applications to arable land, especially with regard to the effects of sludge adsorption characteristics on trace metal solubility and bioavailability (e.g., the sludge "time bomb" or sludge "protection" hypotheses). Mass balances of organic and inorganic material derived from sludge and crop residues are simulated. Each pool has a potentially different adsorption affinity for trace metals, and this leads to changes in the adsorption capacity of sludge-amended soil that influence leaching and crop uptake. Model simulations were compared with measured changes in organic carbon and ethylenediaminetetraacetic acid (EDTA)-extractable cadmium contents in a clay loam soil following 41 years of sludge applications. The model adequately reproduced the data, although discrepancies in the vertical distribution of Cd were attributed to the effects of macropore transport and root-uptake driven recirculation. A Monte Carlo sensitivity analysis demonstrated that the most important parameters affecting leaching and crop uptake were the Cd loading and parameters controlling adsorption, especially the partition coefficient for sludge-derived inorganic material and the exponent regulating the effect of pH on sorption. Scenario simulations show that no general conclusions can be drawn with respect to the validity of the sludge "time bomb" and sludge "protection" hypotheses. Either may occur, or neither, depending on three key system parameters: the ratio of sludge adsorption capacity to the initial adsorption capacity of the soil, the proportion of the sludge adsorption capacity contributed by the inorganic fraction, and the sludge Cd loading.     

Changes in the rhizosphere of metal-accumulating plants evidenced by chemical extractants

The plants Salix viminalis L. (common osier) and Thlaspi caerulescens J. Presl & C. Presl have been studied often because of their high potential to extract heavy metals from soils. The soil properties favoring this phytoextraction are not yet fully known. In this study we compared three frequently used single-extracting agents (NaNO3, diethylenetriaminepentaacetic acid [DTPA], and ethylenediaminetetra-acetic acid [EDTA]) with a sequential extraction procedure to describe changes in the different Cd, Cu, and Zn pools in the rhizosphere of S. viminalis and T. caerulescens grown on calcareous and acidic Swiss soils in a pot experiment. The sequential extraction was used to assess the chemical affinities of these heavy metals (HM) in the soil whereas the single extractants were used for estimating the bioavailable HM pools in the soils. Cadmium depletion in several pools was most apparent in the acidic soil, with a significant decrease observed in the NaNO3-, DTPA-, and EDTA-extractable fractions following T. caerulescens growth compared with control pots. The sequential extraction showed that most Cd extracted by the plant from the acidic soil originated from the organic pool, which implies that heavy metals bound to organic matter may constitute a significant part of the bioavailable Cd pool in soils. In the calcareous soil only a small amount of Cd was taken up by T. caerulescens, and this came mainly from the carbonate-bound fraction. This study shows that T. caerulescens, and to a lesser extent S. viminalis, can alter the heavy metal distribution in different soil pools within 90 d.     

Distribution and movement of sludge-derived trace metals in selected Nigerian soils

Use of metal-rich sewage sludge as soil fertilizer may result in trace- metal contamination of soils. This study was conducted to evaluate the effects of long-term sludge application on trace-metal (Zn, Cu, Pb, and Ni) distribution and potential bioavailability in Nigerian soils under a tropical wet-dry climate. Total metal analyses, sequential chemical fractionation, and DTPA extractions were carried out on samples of control and sludge-amended pedons in Nigeria (a Rhodic Kandiustult and two Rhodic Kandiustalfs from Nigeria, respectively). The sewage sludge applied to the soils contained higher levels of Zn and Cu than Pb and Ni. The control pedon contained low levels of all four metals. Soil enrichment factors (EF) were calculated for each metal in the sludge-amended pedons. Compared with the control soil, the sludge-amended pedons showed elevated levels of Zn and Cu, reflecting the trace-metal composition of the sewage sludge. Zinc and Cu in the sludge-amended soils were strongly enriched at all depths in the profile, indicating that they had moved below the zone of sludge application. The sequential extraction and DTPA analyses indicated that the sludge-amended soils contained more readily extractable and bioavailable metal ions than the unamended soil.     

Chicken manure biochar as liming and nutrient source for acid Appalachian soil

Acid weathered soils often require lime and fertilizer application to overcome nutrient deficiencies and metal toxicity to increase soil productivity. Slow-pyrolysis chicken manure biochars, produced at 350 and 700°C with and without subsequent steam activation, were evaluated in an incubation study as soil amendments for a representative acid and highly weathered soil from Appalachia. Biochars were mixed at 5, 10, 20, and 40 g kg into a Gilpin soil (fine-loamy, mixed, active, mesic Typic Hapludult) and incubated in a climate-controlled chamber for 8 wk, along with a nonamended control and soil amended with agronomic dolomitic lime (AgLime). At the end of the incubation, soil pH, nutrient availability (by Mehlich-3 and ammonium bicarbonate diethylene triamine pentaacetic acid [AB-DTPA] extractions), and soil leachate composition were evaluated. Biochar effect on soil pH was process- and rate-dependent. Biochar increased soil pH from 4.8 to 6.6 at the high application rate (40 g kg), but was less effective than AgLime. Biochar produced at 350°C without activation had the least effect on soil pH. Biochar increased soil Mehlich-3 extractable micro- and macronutrients. On the basis of unit element applied, increase in pyrolysis temperature and biochar activation decreased availability of K, P, and S compared to nonactivated biochar produced at 350°C. Activated biochars reduced AB-DTPA extractable Al and Cd more than AgLime. Biochar did not increase NO in leachate, but increased dissolved organic carbon, total N and P, PO, SO, and K at high application rate (40 g kg). Risks of elevated levels of dissolved P may limit chicken manure biochar application rate. Applied at low rates, these biochars provide added nutritional value with low adverse impact on leachate composition.     

Response of soil microbiological activities to cadmium,lead, and zinc salt amendments

Heavy metal pollution of soil has been recognized as a major factor impeding soil microbial processes. From this perspective, we studied responses of the soil biological activities to metal stress simulated by soil amendment with Zn, Pb, and Cd chlorides. The amounts of heavy metal salts added to five metal-polluted soils and four nonpolluted soils were selected to match the total metal concentrations typically found in polluted soils of the Silesia region of Poland. From the perspective of soil quality, metal mobility in amended soils could not be described by simple functions of pH or organic matter. Reaction of Pb with the soil caused strong immobilization with less than 1% of the Pb amendment recovered by 0.01 M CaCl2 extractions. Immobilization of Cd was also significant, whereas immobilization of the Zn amendment was much weaker than that of Cd or Pb. The Zn amendment had substantial inhibitory effect on soil dehydrogenase, acid and alkaline phosphatase, arylsulfatase, urease, and nitrification potential. Generally, Cd and Pb had limited or stimulatory effect on most of these biological activities, with an exception of Pb strongly inhibiting soil urease. The effect of the metal amendments on biological activities could not be satisfactorily accounted for by metal toxicity because no strong relationship was observed between extractable metal content and the degree of inhibition. The Zn amendment had a significant effect on soil pH, resulting in confounding effects of pH and Zn toxicity on activities. Metal amendment experiments seem to be of limited utility for meaningful assessment of metal contamination effects on soil quality.     

RUNOFF OF METALS FROM ALUM-TREATED HORSE MANURE AND MUNICIPAL SLUDGE1

ABSTRACT: Land application of organic soil amendments can increase runoff concentrations of metals such as Fe and Zn, metalbids such as B and As, and non-metals such as P and S that have the potential for causing adverse environmental impacts. Aluminum sulfate, or alum (Al₂(SO₄)3*(14H₂O), can reduce concentrations of some materials in runoff from sites treated with organic amendments. The objectives of this study were to (a) quantify concentrations of selected constituents (Al, As, B, Ca, Cd, Co, Fe, K, Mg, Mn, Mo, Na, P, Pb, 5, Se, Ti, and Zn) in runoff from plots treated with horse manure (mixed with stall bedding) and municipal sludge, (b) assess runoff quality effects of alum addition to those treatments, and (c) determine time variations in concentrations of the constituents. Horse manure and municipal sludge were applied to twelve 2.4 by 6.1 m fescue plots (six each for the manure and sludge). Alum was added to three of the manure-treated and three of the sludge-treated plots. Simulated rainfall (64 mm/h) was applied to the 12 treated plots and to three control (no treatment) plots. The first 0.5 h runoff was sampled and analyzed for the constituents described above. Addition of manure or sludge had no effect on runoff concentrations of the majority of constituents. In some cases (e.g., Al, As, Fe, Zn), however, concentrations were near or in excess of threshold values recommended for marine wildlife protection. Alum addition increased runoff of Al, Ca, K, and 5, due likely to its composition and by the addition of lime to counteract the acidity of alum. Concentration decreases of more than 50 percent were noted for P for the horse manure treatment. No alum effect was detected for P in runoff from the sludge-treated plots, possibly due to relatively stable P forms in the sludge. Runoff concentrations of Al, As, Fe, K, Mn, and P followed an approximately first-order decline with respect to time. Runoff concentrations of Ca and 5, however, peaked during the second runoff sample (four minutes following initiation of runoff), suggesting that differences in mobility and/or transport mechanisms exist among the materials investigated.     

Adsorption of cadmium on biosolids-amended soils

Debate exists over the biosolid phase (organic or inorganic) responsible for the reduction in phytoavailable Cd in soils amended with biosolids as compared with soils amended with inorganic salts. To test the importance of these two phases, adsorption isotherms were developed for soil samples (nine biosolids-amended soils and their five companion controls) and two biosolids samples from five experimental sites with documented histories of biosolids application. Subsamples were treated with 0.7 M NaClO to remove organic carbon. Cadmium nitrate was added to both moist soil samples and their soil inorganic fractions (SIF) in a 0.01 M Ca(NO3)2 solution at three pH levels (6.5, 5.5, and 4.5), and equilibrated at 22 +/- 1 degrees C for at least 48 h. Isotherms of Cd adsorption for biosolids-amended soil were intermediate to the control soil and biosolids. Decreasing pH did not remove the difference between these isotherms, although adsorption of Cd decreased with decreasing pH level. Organic matter removal reduced Cd adsorption on all soils but had little influence on the observed difference between biosolids-amended and control soils. Thus, increased adsorption associated with biosolids application was not limited to the organic matter addition from biosolids; rather, the biosolids application also altered the adsorptive properties of the SIF. The greater affinity of the inorganic fraction of biosolids-amended soils to adsorb Cd suggests that the increased retention of Cd on biosolids-amended soils is independent of the added organic matter and of a persistent nature.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.