Co-exposure of sulfur nanoparticles and Cu alleviate Cu stress and toxicity to oilseed rape Brassica napus L.

Experiments were performed to explore the impact of sulfur nanoparticles (SNPs) on growth, Cu accumulation, and physiological and biochemical responses of oilseed rape (Brassica napus L.) inoculated with 5 mg/L Cu-amended MS medium supplemented with or without 300 mg/L SNPs exposure. Cu exerted severe phytotoxicity and inhibited plant growth. SNPs application enhanced the shoot height, root length, and dry weight of shoot and root by 34.6%, 282%, 41.7% and 37.1%, respectively, over Cu treatment alone, while the shoot and root Cu contents and Cu-induced lipid perodixation as the malondialdehyde (MDA) levels in shoots and roots were decreased by 37.6%, 35%, 28.4% and 26.8%. Further, the increases in superoxide dismutase (SOD), peroxidase (POD), catalase (CAT), ascorbate peroxidase (APX), glutathione reductase (GR) and glutathione S-transferase (GST) enzyme activities caused by Cu stress were mitigated in shoots (10.9%–37.1%) and roots (14.6%–35.3%) with SNPs addition. SNPs also positively counteracted the negative effects on shoot K, Ca, P, Mg, Mn, Zn and Fe contents and root K, Ca, Mg and Mn contents from Cu exposure alone, and significantly promoted the nutrients accumulation in plant. Additionally, in comparison with common bulk sulfur particles (BSPs) and sulfate, SNPs showed more positive effects on promoting growth in shoots (6.7% and 19.5%) and roots (10.9% and 15.1%), as well as lowering the shoot Cu content (40.1% and 43.3%) under Cu stress. Thus, SNPs application has potential to be a green and sustainable technology for increasing plant productivity and reducing accumulation of toxic metals in heavy metal polluted soils.     

Cu污染土壤-水稻系统中Cu的分布特征

对太湖流域某地误用硫酸铜废水灌溉导致的污染土壤和作物体铜（Ｃｕ）含量分析表明：Ｃｕ 主要富集于表层土壤,受Ｃｕ 污染的表层土壤Ｃｕ 含量是该地区非污染区的１．６～５．１倍． 受Ｃｕ 污染的农田种植水稻其糙米、稻壳和稻草中Ｃｕ 含量分别是非污染区的１１．１～４．６、１８．３～３．７ 和９．３～２．３ 倍． Ｃｕ 在水稻植株体分配是：稻草＞ 稻壳＞ 糙米． 土壤Ｃｕ 含量与稻草和稻壳Ｃｕ含量之间符合指数函数关系,与糙米Ｃｕ 含量之间符合线性函数关系． Ｃｕ 污染导致水稻减产１８％ ～２５％ ;主要是由于水稻Ｃｕ中毒影响水稻根系生长发育,抑制水稻分蘖和减少有效穗数． 如果不采取治理措施,使受Ｃｕ 污染土壤Ｃｕ 含量下降到该地区非污染区水平至少需要１５～９２ａ． 因此,对污染土地采取治理是必要的．     

Cu/Cu_2O材料的制备及形貌调控研究

目的一步制备和调控Cu/Cu_2O材料。方法采用水热法合成Cu/Cu_2O材料,通过改变反应时间、温度,原料投料量以及乙醇和水混合溶液中溶剂比等参数来调控Cu/Cu_2O复合材料的晶体形貌和Cu含量。结果增加氨水和甲酸使用量会明显提升Cu/Cu_2O复合材料中的Cu含量,硝酸铜和混合溶液(乙醇+水)中水量增加会使Cu/Cu_2O复合材料中Cu含量减少,而反应时间和反应温度均不会使复合材料中Cu量发生变化。氨水和甲酸使用量的增加,会使样品从菜花状、正八面体或十二面体向类球状转变。而硝酸铜和混合溶液(乙醇+水)中水量增加恰好使得样品形貌向相反方向变化。另外,反应温度过高会使得晶体向正八面体转变并且逐渐出现孔隙。结论通过改变样品合成参数可成功调控Cu/Cu_2O复合材料中Cu含量和形貌。     

铜与毒死蜱复合污染对淡水绿藻的毒性效应

重金属及农药残留在水环境中被频繁检测出,其复合污染对环境生物的联合毒性有别于单因子的生物效应.以淡水绿藻为受试生物,比较分析了有机磷农药毒死蜱（Chlorpyrifos）和重金属铜的单一及复合暴露对蛋白核小球藻急性毒性、细胞通透性及抗氧化应激的影响.铜、毒死蜱72小时单一暴露对小球藻的EC₅₀分别为0.68和12.71μmol/L,藻细胞叶绿素含量随污染物浓度的增大而降低,细胞通透性随污染物浓度的增大而增强,藻细胞活性氧和抗氧化酶被显著诱导.利用相加指数法（Additive Index,AI）确定铜、毒死蜱联合暴露对小球藻急性毒性的联合作用类型为拮抗作用,这与小球藻ROS产生量及抗氧化酶等指标的显著性水平分析结果一致.     

不同EPS组成生物膜对Cu2+吸附的研究

采用自行设计的反应器,通过调节培养液的配比对载体进行挂膜,得到蛋白质和多糖含量比分别为7:1、5:1和10:1的3种生物膜作为吸附剂,用其对Cu2+进行吸附试验,同时对吸附机理进行探讨.结果表明,培养8d后,生物膜可挂膜成熟,在C/N=12时,生物膜上的菌落数较C/N=4和C/N=37条件下多.PN/PS值越小,生物膜对铜的吸附量越高,EPS3对Cu2+的吸附量分别高出EPS1 7.37 %, EPS2 7.62%.在生物膜吸附Cu2+后,溶液中Ca2+、Mg2+、K+含量明显升高,表明离子交换对生物膜吸附Cu2+起主要作用,且Cu2+更易与Ca2+和Mg2+产生离子交换作用.当KNO3浓度在0.1~0.6mol/L之间,随着离子强度的增加,生物膜吸附Cu2+的量迅速减少,当KNO3浓度大于0.6mol/L时,生物膜对Cu2+吸附量的变化趋于平缓,说明生物膜对Cu2+的吸附同时包括离子交换吸附和化学吸附.     

土壤吸铜特性对铜毒性临界值的影响

本文选用四川紫色土共8个样品,进行了莴苣、辣椒的土培试验和Cu吸附试验,结果表明,土壤吸Cu能力因土壤不同而异,吸Cu特征指数按红棕紫泥>紫泥土>夹砂泥>豆办泥>大土泥>红砂土>红紫泥>砂土递减,高量Cu处理对莴苣、辣椒均有毒害,导致减产,不同土壤上Cu毒性大小的顺序正好与吸Cu特征指数相反,但是对于特定的作物都统一于平衡溶液浓度:莴苣0.5μg/mL,辣椒2.5μg/mL,初步认为,使用等温吸附方法估测作物Cu毒性临界值是可行的。     

Cu暴露条件下翡翠贻贝(Perna viridis)消化腺内金属和类金属硫蛋白的变化

通过室内急性暴露实验研究了翡翠贻贝(Perna viridis)消化腺富集Cu及其MTLP(metallothionein like protein)水平随时间的变化规律.结果表明,2种Cu浓度暴露条件下(12.7μg/L和63.5 μg/L),贻贝消化腺内Cu的平均吸收速率分别为2.045和7.028μg/·(g·d)-1,富集系数分别为2 074和1 619.实验测定了所有样本的溶解态Cu与总Cu含量,2个暴露组二者的比值随时间呈现出不同的变化趋势,低浓度组先降低随后上升到与对照样本几乎相同的水平,而高浓度组一直呈下降趋势,表明不同污染程度生物体内金属消化机制进程存在差异.利用Brdicka极谱法测定了贻贝消化腺内MTLP的含量,对照组贻贝消化腺的MTLP平均含量为(0.551±0.037)mg/g;12.7 μg/L Cu暴露组MTLP含量随时间的变化范围是0.407～0.699 mg/g,而63.5 μg/L Cu暴露组在暴露初始MTLP水平就显著增加(p＜0.001),变化范围由初始0.942 mg/g降至0.826 mg/g.分析结果表明贻贝消化腺内的MTLP水平随着水体及生物体内的金属含量升高而增加,并与体内Cu浓度成明显的负指数增长关系(p＜0.0001).     

The transport of Cu and Zn from agricultural soils to surface water in a small catchment

Long-term manure-borne copper and zinc inputs (18-324 mg Cu m⁻² yr⁻¹ and 100-800 mg Zn m⁻² yr⁻¹) to grassland soils resulted in their catchment in water concentrations that often exceeded the surface water quality criteria (2 μg Cu l⁻¹ and 5 μg Zn l⁻¹). This paper compares retention and release of Cu and Zn by two types of soil, a mineral soil (MS) and a dark colored soil rich in organic matter (OS). On the basis of dry soil mass, the OS has a higher retention/affinity for Cu and Zn than the MS, but much less Zn accumulated in the MS when compared on an areal basis. This is largely because of the much smaller bulk OS density and larger dissolved metal concentrations in the OS drainage than that for the MS. However, because of the greater water retention capacity of the OS, elevated metal concentrations in the soil solution do not necessarily cause greater loss to water. It is concluded that artificially drained OS can contribute significantly to the observed elevated Cu and Zn concentrations of the river, especially during relatively dry weather conditions when the contribution of water seeping from OS to the total river water discharge becomes increasingly important.     

Photoelectrocatalytic reduction of CO_2 to methanol over a photosystem Ⅱ-enhanced Cu foam/Si-nanowire system

A solar-light double illumination photoelectrocatalytic cell(SLDIPEC) was fabricated for autonomous CO_2 reduction and O_2 evolution with the aid of photosystem II(PS-II, an efficient light-driven water-oxidized enzyme from nature) and utilized in a photoanode solution. The proposed SLPEC system was composed of Cu foam as the photoanode and p-Si nanowires(Si-NW) as the photocathode. Under solar irradiation, it exhibited a super-photoelectrocatalytic performance for CO_2 conversion to methanol, with a high evolution rate(41.94 mmol/hr), owing to fast electron transfer from PS-II to Cu foam.Electrons were subsequently trapped by Si-NW through an external circuit via bias voltage(0.5 V), and a suitable conduction band potential of Si(-0.6 e V) allowed CO_2 to be easily reduced to CH_3 OH at the photocathode. The constructed Z-scheme between Cu foam and Si-NW can allow the SLDIPEC system to reduce CO_2(8.03 mmol/hr) in the absence of bias voltage. This approach makes full use of the energy band mismatch of the photoanode and photocathode to design a highly efficient device for solving environmental issues and producing clean energy.     

The transport of Cu and Zn from agricultural soils to surface water in a small catchment

Long-term manure-borne copper and zinc inputs (18–324 mg Cu m⁻² yr⁻¹ and 100–800 mg Zn m⁻² yr⁻¹) to grassland soils resulted in their catchment in water concentrations that often exceeded the surface water quality criteria (2 μg Cu l⁻¹ and 5 μg Zn l⁻¹). This paper compares retention and release of Cu and Zn by two types of soil, a mineral soil (MS) and a dark colored soil rich in organic matter (OS). On the basis of dry soil mass, the OS has a higher retention/affinity for Cu and Zn than the MS, but much less Zn accumulated in the MS when compared on an areal basis. This is largely because of the much smaller bulk OS density and larger dissolved metal concentrations in the OS drainage than that for the MS. However, because of the greater water retention capacity of the OS, elevated metal concentrations in the soil solution do not necessarily cause greater loss to water. It is concluded that artificially drained OS can contribute significantly to the observed elevated Cu and Zn concentrations of the river, especially during relatively dry weather conditions when the contribution of water seeping from OS to the total river water discharge becomes increasingly important.     

鸭跖草(Commelina communis)对铜的耐性和积累研究

采用溶液培养法 ,研究了生长于铜矿山上的鸭跖草 (Commelinacommunis)和生长于正常土壤中的鸭跖草对Cu的耐性和吸收积累的差异 .实验显示 ,随着溶液中Cu浓度的增加 ,生长于矿山的鸭跖草的干重、生长速率均增加 ,而生长于非矿山的鸭跖草的干重、生长速率降低 ,2种鸭跖草体内含Cu总量和根、茎、叶Cu含量均随着培养液Cu浓度的增加而增加 ,两者呈明显正相关 .在相同Cu处理浓度下 ,矿山的鸭跖草体内Cu的含量高于非矿山的鸭跖草体内Cu含量 ;Cu在 2种鸭跖草体内各器官的分布一致 ,均为根 >茎 >叶 .在高Cu浓度处理下 ,矿山的鸭跖草地上部Cu含量 根Cu含量的比值不超过 1,但随着溶液中Cu浓度的增加而增加 ;而非矿山的鸭跖草除去对照处理 ( 0 2 5μmol L)外 ,地上部Cu 根Cu比值为 40— 2 40 μmol L ,随着溶液中Cu浓度的增加而增加 ,其比值超过了 1,但到了 3 2 0 μmol L时开始急剧下降 .结果表明矿山的鸭跖草已形成对Cu的耐性     

铜在拔节期小麦中的亚细胞分布

为了解小麦对Cu的解毒及耐性机制,通过盆栽试验并采用差速离心法研究了Cu在拔节期小麦根和叶片中的亚细胞分布。研究表明,在Cu胁迫下根和叶亚细胞组分中Cu含量随胁迫浓度的升高呈上升趋势,Cu主要富集在小麦根部,向地上叶片中输送较少,小麦根部Cu含量是叶片中的1.7~4.1倍。细胞质可溶性部分和细胞壁是Cu在小麦细胞内分布的主要位点,分别占总量的36%~81%和14%~48%,细胞器中分布较少,提高Cu胁迫浓度增强了细胞质可溶性部分对Cu的区隔化作用,减弱了细胞壁对Cu的固持作用,同时减少了Cu在细胞器中的分布;叶片细胞壁对Cu的固定作用较强,根部细胞质可溶性部分对Cu的区隔化作用较强。分析表明,细胞壁的沉淀和细胞质的区隔化作用对小麦对Cu的耐性起着重要的作用。     

Mn-Cu-O负载型催化剂上CO氧化性能的研究

研究了ＺｒＯ２或Ａｌ２Ｏ３负载Ｍｎ－Ｃｕ－Ｏ体系催化剂ＣＯ催化氧化活性，以及物相结构，表面氧性能与活性的关系。结果表明，锆基催化剂的氧化活性明显优于铝基催化剂，起燃温度Ｔ５０低达５０℃，ＺｒＯ２载 利于活性组份形成高活性物相，并促进表面吸附氧的脱附，表现出催化剂表面吸附氧的脱附温度高低次序与其氧化活性有一致的对应关系。     

Cu暴露条件下翡翠贻贝（Perna viridis）消化腺内金属和类金属硫蛋白的变化

通过室内急性暴露实验研究了翡翠贻贝（Perna viridis）消化腺富集Cu及其MTLP （metallothionein like protein）水平随时间的变化规律.结果表明,2种Cu浓度暴露条件下（12.7 μg/L和63.5 μg/L）,贻贝消化腺内Cu的平均吸收速率分别为2.045和7.028 μg·（g·d）^-1,富集系数分别为2 074和1 619.实验测定了所有样本的溶解态Cu与总Cu含量,2个暴露组二者的比值随时间呈现出不同的变化趋势,低浓度组先降低随后上升到与对照样本几乎相同的水平,而高浓度组一直呈下降趋势,表明不同污染程度生物体内金属消化机制进程存在差异.利用Brdicka极谱法测定了贻贝消化腺内MTLP的含量,对照组贻贝消化腺的MTLP平均含量为（0.551±0.037）mg/g;12.7 μg/L Cu暴露组MTLP含量随时间的变化范围是0.407～0.699 mg/g,而63.5 μg/L Cu暴露组在暴露初始MTLP水平就显著增加（p<0.001）,变化范围由初始0.942 mg/g降至0.826 mg/g.分析结果表明贻贝消化腺内的MTLP水平随着水体及生物体内的金属含量升高而增加,并与体内Cu浓度成明显的负指数增长关系（p<0.000 1）.     

Responses of Sesbania rostrata and S. cannabina to Pb, Zn, Cu and Cd toxicities

Responses of Sesbania rostrata and S. cannabina to Pb, Zn, Cu and Cd toxicities were assessed by a seed-suspending seedbed(SSS) approach. The results showed that the SSS approach was suitable for testing the tolerance of a plant to the stress of toxic metals. The endpoints include seed germination success, straightened radicle and hypocotyl of the seedlings from the seeds. The measurements could be done easily and accurately. It was found that the elongation of radicle was the most sensitive indicator to the stress of heavy metals among the endpoints. When exposure to lower or medium concentrations of Pb, Zn, and Cd, the development of the lateral roots were favorable. Species of S. rostrata was more tolerant than S. cannabina to the heavy metals, especially to Zn and Cd. The ED50 of Pb, Zn, Cu and Cd were 32.90, .5.32, 4.40 and 12.00 μg/ml for S. rostrata,respectively, and they were 30.11, 2.87, 4.0.5 and 4.94 μg/ml respectively for S. cannabina.     

Cu2+对两种生态型鸭跖草Cu积累和抗氧化酶的影响

在Hoagland培养基中加入CuSO4模拟Cu2 污染环境,比较了不同Cu2 浓度([Cu2 ])对鸭跖草(Commelina communis L.)耐性生态型和敏感生态型的耐性、Cu积累和抗氧化酶[过氧化氢酶(CAT)、超氧化物歧化酶(SOD)和过氧化物酶(POD)]的影响.结果表明,两种生态型鸭跖草的Cu2 中毒临界浓度和中毒症状有明显的差异,[Cu2 ]≥40祄ol/L时,耐性生态型鸭跖草的耐性明显高于敏感生态型.耐性生态型鸭跖草叶和根中的Cu2 含量都明显高于敏感生态型,根中更为明显.不同生态型甚至同一生态型不同器官的POD、CAT、SOD活性对Cu2 的敏感性不同.一般来说,根对Cu2 的敏感性高于叶;POD活性对Cu2 的敏感性高于CAT和SOD.根比叶在清除丙二醛(MDA)的过程中起更重要作用.耐性生态型鸭跖草叶和根中CAT、POD和SOD活性、叶中MDA的变化并没有与根中MDA含量的变化趋势(大幅增加)保持一致,表明除了抗氧化酶外,可能还存在其他机制影响耐性生态型与敏感生态型鸭跖草在Cu2 耐性上的差异.     

两个海州香薷种群根对Cu的吸收及Cu诱导的ATP酶活性差异

通过水培实验,比较分析了分别来自湖北省铜绿山矿区和红安非矿区的海洲香薷种群根对铜的抗性和对Cu的吸收累积差异,同时应用微囊膜技术进行了ATPase的诱导和活性测定.结果发现,来自铜绿山种群植物的铜耐受性明显高于红安种群,在20μmol·L-1 Cu处理时红安种群根尖开始变黑,生长明显受到抑制;而铜绿山种群在80μmol·L-1 Cu处理时仍然能正常生长;在所有Cu处理中,铜绿山种群植物根的Cu含量明显低于红安种群.Cu诱导的ATPase活性在铜绿山种群根质膜有明显的变化,在1μmol·L-1 Cu处理时,其活性显著增加,5μmol·L-1 Cu处理时,其活性先到达高峰而后降低;而红安种群则没有出现Cu诱导的ATPase活性的升高,除了100μmol·L-1 Cu明显降低了ATPase活性外,其它处理则没有显著的变化.在还原型谷光苷肤(GSH)存在的条件下,Cu诱导的ATPase活性在铜绿山种群中显著提高,且有明显的Cu浓度效应,而红安种群虽有提高但没有浓度效应.这些结果表明,矿区种群根细胞中可能存在Cu-ATPase,该酶在根的Cu吸收运输方面可能起重要的调节作用,从而使其具有较高的Cu抗性.     

无定形氧化铁-胡敏酸复合胶体对Cu2+的吸附特征

采用Cu2 选择电极研究了不同pH值条件下胡敏酸(HA)、无定形Fe2O3、HA-Fe2O3复合胶体对Cu2 的等温吸附规律.结果表明,随着pH值的升高,3种胶体饱和吸附量和吸附平衡常数均增大,有利于吸附的进行.HA和无定形Fe2O3等温吸附Cu2 的4种拟合方程中,Langmuir方程整体拟合效果最佳,其次为对数方程和Freundlich方程,Linear方程较差.HA-Fe2O3复合胶体等温吸附Cu2 的4种拟合方程均达到显著相关.在相同pH值条件下,无定形Fe2O3对Cu2 吸附量最小,复合胶体次之,HA胶体最大;而且,无定形Fe2O3和复合胶体的饱和吸附量之和小于HA胶体.