Major environmental and ecotoxicological processes of heavy metals in Lean River polluted by discharges from mining activities

１　ＩｎｔｒｏｄｕｃｔｉｏｎＣｈｉｎａｉｓｕｎｄｅｒｇｏｉｎｇｓｕｂｓｔａｎｔｉａｌａｎｄｒａｐｉｄｃｈａｎｇｅｓｉｎｉｔｓｓｏｃｉｅｔｙａｎｄｉｔｓｅｃｏｎｏｍｉｃｐｏｌｉｃｉｅｓ．Ａｍｏｎｇｖａｒｉｏｕｓｅｎｖｉｒｏｎｍｅｎｔａｌｐｒｏｂｌｅｍｓ，ｗａｔｅｒｐｏｌｌｕｔｉｏｎｉｓｏｎｅｏｆｔｈｅｍｏｓｔｃｒｉｔｉｃａｌｉｓｓｕｅｓｆａｃｉｎｇＣｈｉｎａｔｏｄａｙ．Ｔｈｅｓｅｐｏｌｌｕｔａｎｔｓｐｏｉｓｏｎａｑｕａｔｉｃｏｒｇａｎｉｓｍｓａｎｄａｃｃｕｍｕｌａｔｅｉｎｆｉｓｈａｎｄｏｔｈｅｒｅ…     

Performance, microbial community and inhibition kinetics of long-term Cu2+ stress on an air-lift nitritation reactor with self-recirculation

Biological nitrogen removal process could be affected due to the presence of heavy metals owing to their toxicity and accumulation in the sludge.In this study,the impact of Cu~(2+)shock on a long-term nitritation operation was investigated in an air-lift reactor with selfrecirculation.Both the dynamics of microbial community and inhibition kinetics under Cu~(2+) stress were ascertained.The results showed that Cu~(2+) exerted severe inhibition on nitritation performance of an air-lift reactor(ALR) at 25 mg/L.The corresponding NH_4~+-N removal efficiency decreased to below 50%,which was mainly due to the variation of microbial community structure,especially the inhibition of nitrifiers like Nitrosomonas(the relative abundance decreased from 30% to 1% after Cu~(2+)inhibition).Kinetic parameters were obtained and compared after fitting the Haldane model.The long-term Cu~(2+) stress on the ALR aggravated the ammonium affinity and the resistance to substrate self-inhibition of the nitritation sludge,but reduced the resistance to Cu~(2+) inhibition.Furthermore,Cu~(2+)acted as uncompetitive inhibitor on nitritation process.Our results provide new insights into the nitritation characteristics under long-term Cu~(2+) stress.     

生物炭对土壤有效态重金属的作用机制进展

为了深入探究生物炭对土壤有效态重金属变化的影响,研究重点从生物炭的直接和间接作用两个方面对重金属有效态的影响机制进行了归纳概述。直接作用是指生物炭利用自身较大比表面积、疏松孔隙、丰富官能团和矿物质来吸附固定重金属,进而影响重金属形态转化的过程,包括物理吸附、静电吸引、官能团络合、离子交换、阳离子-π、化学沉淀等多种机理;间接作用是指生物炭通过改变土壤理化性质或者微生物群落多样性来影响有效态重金属含量变化的过程,以化学和微生物机制为主。最后提出结论与展望,以期为土壤重金属污染生物炭修复技术的潜在应用提供理论基础。     

微生物诱导碳酸盐沉淀及其在固定重金属领域的应用进展

生物矿化已受到化学、物理、生物、材料、医学、生命及环境等多学科的广泛关注,其中,以尿素为底物的MICP（微生物诱导碳酸盐沉淀）技术是生物矿化领域的研究热点之一.在分析MICP过程中的酶解机理和生物大分子在微生物矿化过程中的作用基础上,通过对重金属离子的矿化产物和碳酸盐矿化菌的成矿因素分析,揭示MICP矿化产物的特征及形成条件.碳酸盐矿化菌主要产生脲酶分解尿素,增加土壤CO₃2-饱和度,其代谢产生的胞外聚合物具有多种功能团组合和键能连接,起着调控生物矿化的作用.MICP技术可用于固定土壤和水体中的Cu、Pb、Zn、Cd、Cr、As等重金属,重金属主要以共沉淀的形式被固定,阴阳离子型重金属以类质同象置换方式分别占据方解石中的CO₃2-位和Ca2+位,从而促使污染土壤中的可交换态重金属向碳酸盐结合态转移.但是,MICP技术主要针对减少重金属的生物可利用性,不能满足以全量来计算的现行土壤环境质量标准,且MICP技术在长期有效性、生物安全性和土壤理化性质等方面存在诸多隐患.因此,由试验条件转向实际应用具有一定挑战.建议寻找更稳定的方法以阻止碳酸盐矿物中的重金属溶出,且有必要将开发高效的土著微生物复合菌剂作为未来MICP研究的方向之一.      

污泥屏障氧化缓冲容量与重金属再溶出关系研究

借助微生物厌氧活动特别是硫酸盐还原反应,污泥屏障可用来固定尾矿堆场重金属.针对尾矿风化淋滤形成的酸性采矿废水(AMD)与污泥之间发生的氧化还原反应导致的重金属溶出问题,通过氧化滴定实验研究了不同污泥悬液的氧化缓冲容量及其与重金属浓度的关系.结果表明,污泥悬液的氧化缓冲容量随着悬液固液比的增大略有减小,但随着悬液厌氧培养时间的延长而增加.污泥的氧化缓冲容量主要来自Eh≤-150mV的强烈还原区间,可达氧化缓冲容量的50%以上.氧化滴定过程中发现,当Eh≥-150mV时,Zn首先明显溶出;当Eh≥150mV时,Cu和Pb明显溶出.基于实验结果,建立了污泥屏障在AMD渗流条件下氧化缓冲容量消耗的数学模型.模拟计算结果表明,当AMD水头高度为10m时,厚度2m的污泥屏障经历AMD溶液38787a的渗透氧化,仍可保持原有的强烈还原状态,具备对重金属的固定效果.     

浒苔生物炭促进土壤Pb固定并缓解植物Pb毒性

本文利用浒苔在不同温度下制备的生物炭（400℃和600℃,记为BC400与BC600）,以30g/kg生物炭添加量对1200mg/kg的Pb污染土壤进行香根草盆栽实验,研究浒苔生物炭对土壤中Pb固定和植物中Pb毒性的影响.结果表明,浒苔生物炭与香根草能协同促进土壤中Pb固定,较生物炭组提高了16.89%和14.82%,比植物组提高17.40%和15.02%.生物炭理化性质影响Pb固定,BC400的pH值（8.97）低于BC600（10.59）,但BC400固定Pb的效果优于BC600,因为羟基（—OH）、羰基（C═O）等基团较BC600丰富,且微孔结构完整.浒苔生物炭可抑制香根草对Pb的吸收,促进香根草生长,其中BC400有助于植物地上部分及根部Pb浓度降低（分别降低23.50%和22.92%）,同时降低富集系数,提高香根草的生物量、叶绿素含量及根系活力,提高抗氧化酶SOD、CAT和POD活性,丙二醛含量可降低13.40%.总之,浒苔生物炭通过高pH值和微孔结构吸附Pb,并通过官能团增加与金属的结合位点固定Pb,以降低Pb的毒性,提高香根草生存能力.鉴于滨海地区浒苔生物质资源丰富,生物炭与植物联合作用可作为Pb污染土壤修复的技术措施之一.     

A porous biochar supported nanoscale zero-valent iron material highly efficient for the simultaneous remediation of cadmium and lead contaminated soil

Risk associated with heavy metals in soil has been received widespread attention.In this study,a porous biochar supported nanoscale zero-valent iron（BC-nZVI） was applied to immobilize cadmium（Cd） and lead（Pb） in clayey soil.Experiment results indicated that the immobilization of Cd or Pb by BC-nZVI process was better than that of BC or nZVI process,and about 80% of heavy metals immobilization was obtained in BC-nZVI process.Addition of BC-nZVI could increase soil pH and organic matter（SOM）.Cd or...     

污泥预植重金属Cu炭化及炭中重金属的稳定性研究

提出一种污泥预植重金属炭化后固定的概念,并以重金属Cu为代表,以CuCl2的形式植入;研究了在不同Cu预植浓度、不同温度下炭化后污泥本身以及额外添加的重金属在炭中的保留率以及稳定特性,同时采用不同的浸出方法,确定与污泥炭最终处置目标相关的最大可预植量.结果表明,在污泥中Cu的预植量为0.5%(质量分数,以Cu元素计)时,经过热解炭化,90%以上的Cu都保留在污泥炭中,其固定效果与温度有关,400℃以上时,炭化温度越高,Cu越容易浸出.在污泥中预植重金属Cu存在最大容量限制,最大可预植量与污泥炭最终处置目标有关,若选择在卫生填埋场进行填埋,则Cu的预植量不宜超过0.5%.本研究提供了一种污泥包裹其他含重金属的废料共炭化实现无害化的新思路,从而达到用污泥治废的效果.     

河水-地下水交互带内砷及金属的自然衰减过程

在简单介绍污染物自然衰减作用定义的基础上,重点分析了河水-地下水交互带内As和以矿山废水为来源的金属污染物的自然衰减行为:主要包括吸附作用,氧化还原作用,生物转化作用等。其中详细介绍了金属Fe、Al的氢氧化物/氧化物对As化合物和其他金属如Cd、Cu和Zn等的吸附作用;Ca2+、Fe2+、磷酸盐、重碳酸盐等阴阳离子和天然有机质对吸附作用的影响;金属微生物氧化还原作用以及微生物作用下As(V)与As(III)的相互转化过程。研究发现,阳离子可以增强金属的吸附作用,阴离子主要是参与竞争吸附;天然有机质对金属吸附过程的抑制作用阻碍金属的固定;交互带内氧化还原条件的变化可以引起一系列的氧化还原反应;微生物催化还原不利于As的自然衰减。最后指出目前河水-地下水交互带内金属污染物衰减过程研究存在的问题以及今后的发展方向。     

Release of Pb adsorbed on graphene oxide surfaces under conditions of Shewanella putrefaciens metabolism

In this study, Pb(II) was used as a target heavy metal pollutant, and the metabolism of Shewanella putrefaciens (S. putrefaciens) was applied to achieve reducing conditions to study the effect of microbial reduction on lead that was preadsorbed on graphene oxide (GO) surfaces. The results showed that GO was transformed to its reduced form (r-GO) by bacteria, and this process induced the release of Pb(II) adsorbed on the GO surfaces. After 72 hr of exposure in an S. putrefaciens system, 5.76% of the total adsorbed Pb(II) was stably dispersed in solution in the form of a Pb(II)-extracellular polymer substance (EPS) complex, while another portion of Pb(II) released from GO-Pb(II) was observed as lead phosphate hydroxide (Pb₁₀(PO₄)₆(OH)₂) precipitates or adsorbed species on the surface of the cell. Additionally, increasing pH induced the stripping of oxidative debris (OD) and elevated the content of dispersible Pb(II) in aqueous solution under the conditions of S. putrefaciens metabolism. These research results provide valuable information regarding the migration of heavy metals adsorbed on GO under reducing conditions due to microbial metabolism.     

生物矿化在重金属污染治理领域的研究进展

生物矿化通过生物代谢影响金属及类金属物质的形态分布,进而改变金属及类金属物质的生物有效性及毒性,在环境污染治理领域成为研究热点.文献计量学结果显示,2007—2017年生物矿化研究以微生物为主要对象,在纳米颗粒物和矿区修复等方面形成热点,并在环境学、生物学、化学和工程学等领域形成交叉学科.结合典型矿化菌与重金属间的矿化关联规律和微界面反应对微生物矿化中重金属的钝化机制进行归纳:①依据矿化菌与矿化产物的关联性对矿化菌进行分类,从碳酸盐、铁锰氧化物、硫化物和磷酸盐4类矿化产物角度汇总了碳酸盐矿化菌、铁锰氧化菌、硫酸盐还原菌及磷酸盐溶解菌的代表微生物;②矿化菌通过诱导矿化的方式固定重金属离子,其中碳酸盐矿化菌、硫酸盐还原菌及磷酸盐溶解菌可以直接促进金属矿物的形成,铁锰氧化菌生成的矿物间接吸附金属离子;③微生物矿化是由外及内的过程,细胞壁及胞外多聚物具有丰富基团,在矿化初期提供吸附和成核位点,原生质体也可以提供矿化场所,在矿化中后期继续固定游离离子.但是,由于微生物复杂的细胞结构及独特的生理习性,矿化过程的微界面反应机制研究尚显不足,需要利用生物学、矿物学、环境科学等领域的先进技术进一步的探索;同时也应开展宏观生态水平的生物矿化研究,并结合实际问题完善生物矿化在环境污染治理中的理论,为重金属污染地区的治理提供新的思路和技术.      

Geochemical and microbial reactions affecting the long-term performance of in situ ‘iron barriers’

The in situ application of granular iron (Fe⁰) has become popular for the destruction of halogenated organic compounds and for the immobilization of specific metals in groundwater. However, a knowledge gap exists concerning the long-term performance of the Fe⁰-barriers. The corrosion of Fe⁰ may produce mineral precipitates that alter the system’s hydraulic integrity. For example, data from existing barriers show varying trends in pH, alkalinity, mineral precipitation, and microbial activity. Although the chemical behaviors are site-specific, this paper discusses the concepts involved in developing a generic approach for predicting the trend of aqueous and surface speciation, and the resulting effects on Fe⁰ treatment systems. Observations from existing Fe barriers are summarized, and the chemical and microbial processes that influence chemical speciation, both in water and on surfaces, are reviewed. A conceptual geochemical model is presented, which illustrates the factors that must be considered in developing a quantitative model that can be used to design monitoring plans for timely detection of clogging in Fe⁰ reactive barriers. In order to develop quantitative predictive models, field and laboratory research should: (1) assess the extent and rates of media deterioration by analyzing coupled chemical and microbial reactions; and (2) identify the controlling mechanisms for hydraulic alteration within and around Fe⁰ barriers.     

环境pH对微生物生物膜吸附重金属的影响研究进展

重金属污染以其强毒性、富集性和持久性成为全球性的环境难题.在现有的重金属污染治理技术中,基于微生物生物膜的修复技术因其高效、低成本、可持续等优势,在预防、控制和修复重金属污染等方面被广泛应用,成为了新兴研究热点技术.为了进一步揭示微生物生物膜与重金属之间的内在关系.本文通过对最近二十年微生物生物膜吸附重金属等方面的文献...     

Performance assessment and microbial diversity of two pilot scale multi-stage sub-surface flow constructed wetland systems

This study assessed the performance and diversity of microbial communities in multi-stage sub-surface flow constructed wetland systems(CWs). Our aim was to assess the impact of configuration on treatment performance and microbial diversity in the systems. Results indicate that at loading rates up to 100 g BOD5/(m2·day), similar treatment performances can be achieved using either a 3 or 4 stage configuration. In the case of phosphorus(P), the impact of configuration was less obvious and a minimum of 80% P removal can be expected for loadings up to 10 g P/(m2·day) based on the performance results obtained within the first16 months of operation. Microbial analysis showed an increased bacterial diversity in stage four compared to the first stage. These results indicate that the design and configuration of multi-stage constructed wetland systems may have an impact on the treatment performance and the composition of the microbial community in the systems, and such knowledge can be used to improve their design and performance.     

垃圾焚烧飞灰H3PO4稳定化技术及机理研究

分析了焚烧飞灰的全组分和浸出毒性,表明飞灰中含有多种重金属,其中Pb的浸出浓度为67.03mg/L,超过危险废物鉴别标准.研究了H₃PO₄投加量对飞灰稳定化效果及其环境长期稳定性的影响,结果表明:投加相当于飞灰质量8%～14%的H₃PO₄就能够有效地使焚烧飞灰无害化;8%和12%H₃PO₄稳定化飞灰都具有良好的环境稳定性;过多的H₃PO₄投加量会降低处理后飞灰对酸性环境的缓冲能力.对于12%H₃PO₄稳定化飞灰,XRD检测出Cr₂P₂O₇、ZnP₂、Pb₃P₄O₁₃、Pb₃P₂O₇、NaZnPO₄、NaPbP₃O₉、Ca₂ZnSi₂O₇等少量重金属的结晶相;SEM发现了大量独立存在的飞灰颗粒、直径约0.3～0.5μm的Pb₅(PO₄)₃Cl棒状物;CHBr₃浮选没有得到浓缩的重金属.综合分析得到:H₃PO₄是通过与强碱性飞灰之间的中和反应,激活飞灰中的重金属,改善稳定化进行的环境,并产生稳定化所需的PO₄^3-.被激活的重金属与产生的PO₄^3-在飞灰颗粒表面结合.所产生的重金属磷酸盐与SiO₂、CaCO₃、CaSO₄、KCl和NaCl等飞灰主要构成固溶相,几乎不独立存在.     

Effects of heavy metal pollution on soil microbial biomass

１Ｉｎｔｒｏｄｕｃｔｉｏｎ１．１ＢａｓｉｃｃｏｎｃｅｐｔｏｆｍｉｃｒｏｂｉａｌｂｉｏｍａｓＳｏｉｌｍｉｃｒｏｂｉａｌｂｉｏｍａｓｉｓｄｅｆｉｎｅｄａｓｔｈｅｌｉｖｉｎｇｐａｒｔｏｆｓｏｉｌｏｒｇａｎｉｃｍａｔｅｒ，ｅｘｃｌｕｄｉｎｇｐｌａｎｔｒｏｏｔ...     

Microbial diversity accumulates in a downstream direction in the Three Gorges Reservoir

Organic and inorganic materials migrate downstream and have important roles in regulating environmental health in the river networks. However, it remains unclear whether and how a mixture of materials (i.e., microbial species) from various upstream habitats contribute to microbial community coalescence upstream of a dam. Here we track the spatial variation in microbial abundance and diversity in the Three Gorges Reservoir based on quantitative PCR and 16S rRNA gene high-throughput sequencing data. We further quantitatively assess the relative contributions of microbial species from mainstem, its tributaries, and the surrounding riverbank soils to the area immediately upstream of the Three Gorges Dam (TGD). We found an increase of microbial diversity and the convergent microbial distribution pattern in areas immediately upstream of TGD, suggesting this area become a new confluence for microbial diversity immigrating from upstream. Indeed, the number of shared species increased from upstream to TGD but unique species decreased, indicating immigration of various sources of microbial species overwhelms local environmental conditions in structuring microbial community close to TGD. By quantifying the sources of microbial species close to TGD, we found little contribution from soils as compared to tributaries, especially for sites closer to TGD, suggesting tributary microbes have greater influence on microbial diversity and environmental health in the Three Gorges Reservoir. Collectively, our results suggest that tracking microbial geographic origin and evaluating accumulating effects of microbial diversity shed light on the ecological processes in microbial communities and provide information for regulating aquatic ecological health.     

湛江湾表层沉积物重金属分布及污染评价

利用ICP-MS分析测定了湛江湾表层沉积物中Cr、Cu、Zn、Cd、Pb等重金属含量。各站位中Cr、Cu、Zn、Cd和Pb等元素全海湾平均含量分别为(84.84±3.86)×10-6、(29.51±1.44)×10-6、(110.02±10.14)×10-6、(0.205±0.003)×10-6、(56.49±1.31)×10-6。各站位表层沉积物中重金属含量较高及其富集系数较大的区域大多集中在人类活动较频繁的港口、码头等海域,体现了人类活动加速重金属沉积过程的痕迹。相关性分析结果表明,Cr与Cu、Pb、Zn等元素的沉积行为差异较大,可能与其在沉积物中主要赋存形态为氧化态和残渣态,而Zn、Cd和Pb等元素在各相中都有富集有关。与已有结果比较,湛江湾表层沉积物中Cr、Cu、Pb、Zn等引起的污染呈逐渐加重的演变趋势,须采取有效的预防措施。     

Effect of land management on soil microbial N supply to crop N uptake in a dry tropical cropland in Tanzania

In Sub-Saharan Africa, conservation of available soil N during early crop growth, when N loss by leaching generally occurs, is important to improve crop productivity. In a dry tropical cropland in Tanzania, we assessed the potential role of soil microbes as a temporal N sink-source to conserve the available soil N until later crop growth, which generally requires substantial crop N uptake. We evaluated the effect of land management [i.e., no input, plant residue application before planting (P plot) with or without fertilizer application, fertilizer application alone, and non-cultivated plots] on the relationship between soil N pool [microbial biomass N (MBN) and inorganic N] and crop N uptake throughout the ∼120-d crop growth period in two consecutive years. In the P plot, MBN clearly increased (∼14.6-29.6 kg N ha⁻¹) early in the crop growth period in both years because of immobilization of potentially leachable N, and it conserved a larger soil N pool (∼10.5-21.2 kg N ha⁻¹) than in the control plot. Especially in one year in which N leaching was critical, increased MBN maintained a larger soil N pool in the P plot throughout the experimental period, and a delay of increased MB C:N ratio and a substantial decrease in MBN was observed, indicating better soil microbial N supply for crop N uptake during later crop growth. Therefore, plant residue application before planting should enhance the role of soil microbes as a temporal N sink-source, leading to the conservation of potentially leachable N until later phase of crop growth, especially in years in which N leaching is relatively severe. Although further studies are necessary, our results suggest that plant residue application before planting is a promising option to achieve better N synchronization.     

再生水中的Pb对萝卜根际土壤微生物群落结构的影响研究

采用盆栽方法研究再生水、再生水+Pb、清水+Pb处理浇灌萝卜,以清水浇灌为对照对萝卜根际土壤微生物群落的影响进行研究。结果表明:(1)土壤总PLFA含量及各菌群生物量从大到小依次为:再生水再生水+Pb清水清水+Pb。再生水灌溉有利于萝卜根际微生物各类群数量的增加,丰富微生物多样性。用含铅的溶液(再生水+Pb、清水+Pb)浇灌萝卜,可抑制土壤微生物各类群的数量,G-受到的抑制尤为明显。(2)主成分分析表明,再生水灌溉与对照相比,土壤微生物群落结构差异最大。(3)土壤微生物各类群与土壤速效钾、硝酸盐氮含量呈极显著正相关(P0.01),真菌、放线菌与土壤有机质含量,G~+、G~-菌与p H均呈极显著正相关(P0.01)。G~+、G~-与萝卜地下鲜重均呈极显著负相关(P0.01),土壤微生物各类群与地上部分硝酸盐含量、与根冠比呈极显著正相关(P0.01)。