稻麦轮作下水稻土重金属形态特征及其生物有效性

在成都平原稻麦轮作下86个土样中重金属全量和各形态含量分析的基础上,采集分析相应点位上种植的主要粮食作物小麦和水稻籽粒的重金属含量,通过描述性统计分析、相关性分析及线性回归方程的模拟,研究了土壤中重金属的形态分布特征及其生物有效性。统计分析结果表明：土壤中Cr、Cu、Pb、Zn各形态含量的分配顺序为：残渣态〉有机物结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,而Cd各形态含量的分配顺序为：铁锰氧化物结合态〉残渣态〉碳酸盐结合态〉有机物结合态〉可交换态。若以活性态（非残渣态含量）而论,Cd的活性最高,Cr的活性最低。除Cr外,各元素全量与各活性形态之间的关系较为密切。土壤中全Cd含量与4种活性形态Cd含量间的相关性均达极显著水平;Cu、Zn全量分别与其铁锰氧化物和有机物结合态含量,Pb全量分别与其可交换态和铁锰氧化物含量间的相关系数达显著或极显著水平。用卫生部颁布的食品中重金属限量卫生标准评价稻麦籽粒重金属累积情况,其结果表明,小麦籽粒（旱作）中的Cd、Cr、Cu、Pb分别超标14.71%、8.70%、6.50%和17.40%,而水稻籽粒（水作）仅有Pb和Cd含量超标10.90%和8.70%。不同形态重金属对水稻和小麦籽粒中重金属累积的影响效应不同，从多元线性回归方程的回归系数来看：稻一麦籽粒中Cd含量受到土壤中各活性形态Cd含量的影响。除铁锰氧化态Cd和有机物结合态Cd含量分别对小麦和水稻籽粒中Cd的累积表现出负效应外，其余均为正效应。可交换态Cu含量对稻-麦籽粒Cu累积的效应最大，其次受碳酸盐结合态Cu含量的影响。稻一麦籽粒Pb含量的累积受土壤各活性态Pb含量影响效应的差异不甚明显。稻-麦籽粒Zn含量与土壤各活性态Zn含量间无显著线性关系。     

施硒对水稻土壤硒有效性的影响

硒在华南稻区酸性土壤中极易被固定使其有效性较低.本研究旨在通过盆栽试验,探明施用硒肥对水稻根际和非根际土壤硒有效性的影响.结果表明: 施硒能提高水稻产量,增加籽粒硒含量;水稻根际土壤中水溶态硒、交换态硒、铁锰氧化物结合态硒、有机物-硫化物结合态硒和残渣态硒含量均低于非根际土壤.各施硒处理之间,根际和非根际土壤中硒的迁移系数没有显著差异;施硒对根和叶片之间硒的迁移系数也没有显著影响,但是施硒提高了叶片和籽粒之间硒的迁移系数.施用0.5 mg·kg^-1硒增加了水稻根系有机酸的分泌,而施用1.0、5.0 mg·kg^-1硒则降低了有机酸的分泌.根系有机酸的分泌对根际土壤pH值影响不大,根际土壤pH值反而高于非根际土壤,但施硒显著降低了根际土壤pH值.随着施硒水平的提高,根际土壤黏土矿物(高岭石)的红外吸收光谱不断增强.施入土壤中的硒多转化为水稻难以吸收利用的形态,且不易向根际移动.根系分泌的有机酸也并不是通过影响土壤pH值来提高土壤硒的有效性.     

土壤和大气铅对玉米植株内铅积累的影响和贡献率

采用土壤添加Pb和叶面喷施Pb溶液的方式,分别研究了土壤Pb和大气Pb在玉米植株各器官中的积累规律和Pb污染浓度与籽粒Pb含量、叶片Pb含量与籽粒Pb含量的相关性,以及土壤Pb和大气Pb对玉米籽粒Pb的贡献率.结果表明:土壤添加Pb后,玉米各器官中Pb含量表现为根＞茎＞叶＞籽粒,且主要富集在根系中;叶面喷施Pb后,玉米各器官Pb含量大小顺序是叶片＞茎、根＞籽粒,且主要富集在叶片中;随着土壤和大气Pb浓度的增加,玉米各器官Pb含量均呈现不同程度的增加;玉米籽粒中的Pb含量与土壤和叶片Pb浓度呈显著正相关(P＜0.01);土壤施加Pb的毒性临界值为118.95 mg·kg-1;大气Pb对玉米籽粒的贡献率为53.7％,土壤Pb对玉米籽粒的贡献率为46.3％,说明大气Pb通过叶面传输是玉米籽粒吸收Pb的重要途径.     

玉米根际土壤中铜形态的动态变化

采用根垫法研究玉米根际土壤形态动态变化。结果表明：玉米生长过程中根际土壤铜形态发生显著变化。植物生长前期交换态和碳酸盐结合态铜含量逐渐增加,随后增加量减少。植物生长后期根际交换态和碳酸盐结合态铜含量低于非根际土壤。这种变化主要由根际环境变化与植物吸收引起。与根限土壤中铜形态变化,特别是交换态铜含量变化关系密切的因素包括土壤溶解性有机碳、pH和土壤微生物。随着植物生物量的增加,对铜的吸收速率不断增加,导致根限土壤中有效态铜的先增后减。     

外源磷对苗期小麦和水稻根际砷形态及其生物有效性的影响

采用土(中度砷污染土)-土根袋培养的方法研究了两个浓度的外源磷(P)对苗期小麦和水稻根际砷(As)形态分布及其生物有效性的影响.结果表明:(1)两种作物生长的土壤中各砷形态的分配比例依次为:结晶铁锰或铁铝水化氧化物结合态(45%～52%)＞无定形和弱结晶铁铝或铁锰水化氧化物结合态(26%～34%)＞专性吸附态(12%～14%)＞残渣态(4%～7%)＞非专性吸附态(0.09%～0.25%).(2)添加外源磷浓度为100 mg·kg-1与不施磷处理相比显著提高了两种作物地上部的生物量(p＜0.01).(3)苗期小麦在添加100 mg·kg-1外源磷时,不仅促进了作物生长而且抑制根中砷向地上部的转运.(4)任何磷处理下,水稻对砷的吸收能力以及由根系向地上部转移能力均高于小麦.因此,在轻中度砷污染土壤上与水稻相比更适宜种植小麦(或其他旱作植物);而在水稻种植季,可以通过添加适量磷肥(100 mg·kg-1)来减弱砷在水稻体内的累积.     

绿洲土Cd、Pb、Zn、Ni复合污染下重金属的形态特征和生物有效性

通过模拟基于干旱区绿洲土壤Cd-Pb-Zn-Ni复合污染下的油菜盆栽试验,采用Tessier五步连续浸提法探究了重金属复合污染对油菜生长的影响及其各形态的转化归趋和生物有效性.结果显示,随着Cd-Pb-Zn-Ni复合胁迫水平的升高,油菜的干重先增加后减小,根系的生长由促进作用转变为抑制作用;对照土壤中4种重金属元素均以残渣态为主要赋存形态,可交换态的含量均很小;随着外源重金属的添加,油菜种植土壤中4种重金属元素的各形态含量随之增加,Cd、Pb、Zn的可交换态和Ni的碳酸盐结合态对外界胁迫响应强度最大,Cd、Pb、Zn、Ni的活性增加,且Cd、Pb的主要赋存形态迅速转变为碳酸盐结合态和铁锰氧化态,Zn的主要赋存形态由残渣态和碳酸盐结合态过渡到碳酸盐结合态和铁锰氧化态,Ni的主要赋存形态为碳酸盐结合态;Cd、Zn在茎叶中的含量大于根系,Pb、Ni反之,油菜能将Cd、Zn更多的运输至茎叶,Pb、Ni则主要积累在根系;油菜茎叶吸收Cd和油菜各部位吸收Zn的主要贡献形态为可交换态,根吸收Cd的主要贡献形态由可交换态转变为有机结合态,根吸收Pb和油菜各部位吸收Ni的主要贡献形态为碳酸盐结合态.     

有机物料对滨海盐渍土重金属根际效应的影响 Ⅰ.土壤内源Zn形态分布

研究了排水条件下施用腐熟有机物料、种稻改良滨海盐渍土内源Zn形态分布。结果表明,单淹水使土中各形态Zn一定程度上向生物有效性较低的Zn形态转化,有效态Zn降低。土壤盐分量不同,明显影响无定形氧化铁结合态、紧结有机态以及硅酸盐矿物态Zn变化。种稻不施有机物料,根际交换态和硅酸盐矿物态Zn亏缺;碳酸盐结合态、氧化锰结合态和无定形氧化铁结合态Zn富集。根际Zn形态转化强度大于非根际,其有效态Zn量接近临界值并高于非根际。有机物料利于根际内外土壤中硅酸盐矿物态Zn的转化,低盐土壤根际更强烈。随有机物料用量增加,促使根际硅酸盐矿物态、碳酸盐结合态及氧化锰结合态Zn向交换态、紧结有机态和无定形氧化铁结合态Zn转化,低盐土壤较明显。     

有机物料对滨海盐渍土重金属根际效应的影响Ⅰ.土壤内源Zn形态分布

研究了排水条件下施用腐熟有机物料、种稻改良滨海盐渍土内源Ｚｎ形态分布．结果表明,单淹水使土中各形态Ｚｎ一定程度上向生物有效性较低的Ｚｎ形态转化,有效态Ｚｎ降低．土壤盐分量不同,明显影响无定形氧化铁结合态、紧结有机态以及硅酸盐矿物态Ｚｎ变化．种稻不施有机物料,根际交换态和硅酸盐矿物态Ｚｎ亏缺;碳酸盐结合态、氧化锰结合态和无定形氧化铁结合态Ｚｎ富集．根际Ｚｎ形态转化强度大于非根际,其有效态Ｚｎ量接近临界值并高于非根际．有机物料利于根际内外土壤中硅酸盐矿物态Ｚｎ的转化,低盐土壤根际更强烈．随有机物料用量增加,促使根际硅酸盐矿物态、碳酸盐结合态及氧化锰结合态Ｚｎ向交换态、紧结有机态和无定形氧化铁结合态Ｚｎ转化,低盐土壤较明显．     

硅对土壤-烟草系统中铅迁移及形态分布的影响

通过盆栽试验,以烟草为对象,研究了硅对土壤 烟草系统中铅的迁移以及土壤、烟草中铅形态分布的影响.结果表明： 施硅使非根际土壤可交换态铅向铁锰氧化物结合态转化,使根际土中交换态铅向铁锰氧化物结合态和残渣态转化,降低了土壤中铅的植物有效性与迁移性.施硅显著提高了烟草根部和叶部的生物量,显著降低了烟草铅的总吸收量和烟草各器官的铅含量,其中烟草铅的总吸收量降低了6.5%～44.0%,烟叶铅含量降低了3.1%～60.4%.施硅使烟草根、茎和叶中乙醇提取态、去离子水提取态和氯化钠提取态向盐酸提取态和残渣态转化,降低了烟草体内铅的毒性与迁移性.土壤-烟草系统中土壤向烟草根部的移动指数和根部向茎部的移动指数随施硅量的增加而降低,烟草茎部向叶部的移动指数随着施硅量的增加呈先增高后降低的趋势.硅通过降低土壤铅有效性、缓解铅对烟草的毒害、改变烟草体内铅的形态分布,进而抑制土壤中铅向烟草叶部的迁移,降低烟叶中的铅含量.施硅是降低土壤铅的迁移性及烟叶铅含量的有效措施.     

石灰性土壤上植物根际中Fe,Mn的形态分布及其与植物吸收的关系

研究了石灰性土壤上５种作物品种根际微生态环境中Ｆｅ、Ｍｎ的形态分布．结果表明,交换态Ｆｅ（ＥＸ－Ｆｅ）、碳酸盐结合态Ｆｅ（ＣＡＲＢ－Ｆｅ）、无定形氧化铁（ＡＯ－Ｆｅ）和交换态Ｍｎ（Ｅ－Ｍｎ）、碳酸盐结合态Ｍｎ（ＣＡＲＢ－Ｍｎ）在根际土壤中都呈现明显的累积．各品种根际中的累积量有较大差异．相关分析表明,黄潮土上植株含Ｆｅ量、吸Ｆｅ量与根际土壤ＡＯ－Ｆｅ含量呈显著正相关．根际有效态Ｆｅ累积不仅是根际ｐＨ作用的结果,与根系分泌物对难溶性Ｆｅ活化有关．根际有效态Ｍｎ累积则受到根际土壤Ｅｈ的影响．     

Complexation of Hg with phytochelatins is important for plant Hg tolerance

Three-week-old alfalfa (Medicago sativa), barley (Hordeum vulgare) and maize (Zea mays) were exposed for 7 d to 30 μm of mercury (HgCl(2) ) to characterize the Hg speciation in root, with no symptoms of being poisoned. The largest pool (99%) was associated with the particulate fraction, whereas the soluble fraction (SF) accounted for a minor proportion (<1%). Liquid chromatography coupled with electro-spray/time of flight mass spectrometry showed that Hg was bound to an array of phytochelatins (PCs) in root SF, which was particularly varied in alfalfa (eight ligands and five stoichiometries), a species that also accumulated homophytochelatins. Spatial localization of Hg in alfalfa roots by microprobe synchrotron X-ray fluorescence spectroscopy showed that most of the Hg co-localized with sulphur in the vascular cylinder. Extended X-ray Absorption Fine Structure (EXAFS) fingerprint fitting revealed that Hg was bound in vivo to organic-S compounds, i.e. biomolecules containing cysteine. Albeit a minor proportion of total Hg, Hg-PCs complexes in the SF might be important for tolerance to Hg, as was found with Arabidopsis thaliana mutants cad2-1 (with low glutathione content) and cad1-3 (unable to synthesize PCs) in comparison with wild type plants. Interestingly, high-performance liquid chromatography-electrospray ionization-time of flight analysis showed that none of these mutants accumulated Hg-biothiol complexes.     

南极生物粪对汞的生物放大作用

首次报道了南极地区金图企鹅、阿德利企鹅、黑背鸥和巨海燕 4种海鸟 ,以及象海豹、威德尔海豹、毛皮海狮等 3种海豹新鲜粪便中的全 Hg含量 ,并对比了该区风化土壤的 Hg含量 ,其中 Hg含量水平依次为 :土壤背景值 <黑背鸥粪 <金图企鹅粪 <阿德利企鹅粪 <威德尔海豹粪 <象海豹粪 <巨海燕粪 <毛皮海狮粪 ,可见 ,相对于背景土壤生物粪明显富集 Hg元素。此外 ,结合上述粪便样品的 δ15 N测定结果 ,讨论了南极生物粪对 Hg的生物放大作用。研究表明 ,随着 δ15 N升高 ,即生物营养级的升高 ,其粪便的全 Hg含量有逐步增高的趋势 ,这证实了生物粪和生物肌体一样存在对 Hg的生物放大作用。文中还对南极阿德雷岛一个经过企鹅粪污染的 Y2湖泥芯剖面上 15个样品的 2 6种元素进行了聚类分析 ,结果表明 ,沉积物中的汞和企鹅粪的标型元素具有同源性 ,即沉积物中的汞主要是由企鹅粪带入的 ,由于生物粪对汞的生物富集作用 ,生物粪的混入会造成湖泊沉积物中汞含量的增高     

G-quadruplex DNAzyme-based Hg2+ and cysteine sensors utilizing Hg2+-mediated oligonucleotide switching

A simple and sensitive colorimetric Hg(2+) detection method is reported, based on the Hg(2+)-mediated structural switch of an unlabeled oligonucleotide strand. In the absence of Hg(2+), the oligonucleotide strand forms a stem-loop. A G-rich sequence in the strand is partially caged in the stem-loop structure and cannot fold into a G-quadruplex. In the presence of Hg(2+), T-Hg(2+)-T coordination chemistry leads to the formation of another stem-loop structure and the release of the G-rich sequence. The released sequence folds into a G-quadruplex, which binds hemin to form catalytically active G-quadruplex DNAzymes. This is detected as an absorbance increase in a H(2)O(2)-2,2'-azinobis(3-ethylbenzothiozoline)-6-sulfonic acid (ABTS) reaction system using UV-vis absorption spectroscopy. This simple colorimetric sensor can detect aqueous Hg(2+) at concentrations as low as 9.2 nM with high selectivity. Based on the strong binding interaction between Hg(2+) and the sulfur-containing amino acid cysteine (Cys), and the competition between Cys and a oligonucleotide for Hg(2+), the proposed Hg(2+)-sensing system can be further exploited as a Cys-sensing method. The method has a detection limit for Cys of 19 nM.     

汞对土壤酶活性的影响

利用室内模拟方法,研究了重金属Hg对不同土样脲酶、转化酶和中性磷酸酶活性的影响.结果表明,Hg可显著地抑制土壤脲酶和转化酶的活性,但不同土样Hg对两种酶活性的抑制程度有很大差别.HgCl₂浓度与两种酶活性之间的关系均可用对数方程很好地描述(P<0.05).4个土样的脲酶ED₅₀(生态剂量)分别为87.99、5.47、24.05和19.88 mg·kg^-1;转化酶的ED₅₀分别为76.68、727.49、236.52和316.59 mg·kg^-1.脲酶对Hg污染比转化酶敏感;有机质对土壤酶活性有一定的保护作用.除连续2年施用大量有机肥的草甸棕壤土样中Hg对中性磷酸酶有显著的激活作用外(P<0.05),其它土样无显著变化,表明中性磷酸酶活性对Hg污染反应不敏感.     

Reduction of Hg(II) to Hg(0) by Biogenic Magnetite from two Magnetotactic Bacteria

Understanding the biogeochemical cycle of the highly toxic element mercury (Hg) is necessary to predict its fate and transport. In this study, we determined that biogenic magnetite isolated from Magnetospirillum gryphiswaldense MSR-1 and Magnetospirillum magnetotacticum MS-1 was capable of reducing inorganic mercury [Hg(II)] to elemental mercury [Hg(0)]. These two magnetotactic bacteria (MTB) lacked mercuric resistance operons in the genomes. However, they revealed high resistance to Hg(II) under atmospheric conditions and an even higher resistance under microaerobic conditions (1% O₂ and 99% N₂). Neither strain reduced Hg(II) to Hg(0) under atmospheric conditions. However, a slow rate (0.05–0.21 µM·d^?1) of Hg(II) loss occurred from late log phase to stationary phase in two MTBs' culture media under microaerobic conditions. Increased Hg(II) entered both cells under microaerobic conditions relative to atmospheric conditions. The majority of Hg(II) was still blocked by the cell membrane. Hg(II) reduction was more effective when biogenic magnetite was extracted out, with or without the magnetosome membrane envelope. When magnetosome membrane was present, 8.55–13.53% of 250 nM Hg(II) was reduced to Hg(0) by 250 mg/L biogenic magnetite suspension within 2 hours. This ratio increased to 55.07–64.70% while magnetosome membrane was removed. We concluded that two MTBs contributed to the reduction of Hg(II) to Hg(0) at a slow rate in vivo. Such reduction was more favorable to occur when biogenic magnetite is released from dead cells. It proposed a new biotic pathway for the formation of Hg(0) in aquatic systems.     

Acclimation of aquatic microbial communities to Hg(II) and CH3Hg+ in polluted freshwater ponds

The relationship of mercury resistance to the concentration and chemical speciation of mercurial compounds was evaluated for microbial communities of mercury-polluted and control waters. Methodologies based on the direct viable counting (DVC) method were adapted to enumerate mercury-resistant communities. Elevated tolerance to Hg(II) was observed for the microbial community of one mercury-polluted pond as compared to the community of control waters. These results suggest an in situ acclimation to Hg(II). The results of the methylmercury resistance-DVC assay suggested that minimal acclimation to CH₃Hg⁺ occurred since similar concentrations of CH₃HgCl inhibited growth of 50% of organisms in both the control and polluted communities. Analyses of different mercury species in pond waters suggested that total mercury, but not CH₃Hg⁺ concentrations, approached toxic levels in the polluted ponds. Thus, microbial acclimation was specific to the chemical species of mercury present in the water at concentrations high enough to cause toxic effects to nonacclimated bacterial communities.