Toxicity and internalization of CuO nanoparticles to prokaryotic alga Microcystis aeruginosa as affected by dissolved organic matter

This is the first study investigating the toxicity of nanoparticles (NPs) to algae in the presence of dissolved organic matter (DOM). Suwannee river fulvic acid (SRFA), a type of DOM, could significantly increase the toxicity of CuO NPs to prokaryotic alga Microcystis aeruginosa. Internalization of CuO NPs was observed for the first time in the intact algal cells using high resolution transmission electron microscopy (HRTEM), and the cell uptake was enhanced by SRFA. A fast Fourier transformation (FFT)/inversed FFT (IFFT) process revealed that a main form of intracellular NPs was Cu(2)O, and an intracellular environment may reduce CuO into Cu(2)O. The internalization behavior alone did not seem to pose a hazard to membrane integrity as shown from the flow cytometry data. Elevated CuO nanotoxicity by SRFA was related to a combination of a lesser degree of aggregation, higher Cu(2+) release, and enhanced internalization of CuO NPs.     

Effects of copper nanoparticles exposure in the mussel Mytilus galloprovincialis

CuO NPs are widely used in various industrial and commercial applications. However, little is known about their potential toxicity or fate in the environment. In this study the effects of copper nanoparticles were investigated in the gills of mussels Mytilus galloprovincialis, comparative to Cu(2+). Mussels were exposed to 10 μg Cu·L(-1) of CuO NPs and Cu(2+) for 15 days, and biomarkers of oxidative stress, metal exposure and neurotoxicity evaluated. Results show that mussels accumulated copper in gills and responded differently to CuO NPs and Cu(2+), suggesting distinct modes of action. CuO NPs induced oxidative stress in mussels by overwhelming gills antioxidant defense system, while for Cu(2+) enzymatic activities remained unchanged or increased. CuO NPs and Cu(2+) originated lipid peroxidation in mussels despite different antioxidant efficiency. Moreover, an induction of MT was detected throughout the exposure in mussels exposed to nano and ionic Cu, more evident in CuO NPs exposure. Neurotoxic effects reflected as AChE inhibition were only detected at the end of the exposure period for both forms of copper. In overall, these findings show that filter-feeding organisms are significant targets for nanoparticle exposure and need to be included when evaluating the overall toxicological impact of nanoparticles in the aquatic environment.     

Magnesium nutrition on accumulation and transport of amino acids in tea plants

BACKGROUND: Free amino acids in young tea shoots are important chemical constituents, remarkably influencing the quality of green teas. Nutrient solution, soil pot and field experiments were conducted to investigate the effect of magnesium nutritional status on accumulation and transport of free amino acids in tea plants ( Camellia sinensis (L.) O. Kuntze). RESULTS: A sufficient supply of Mg in nutrient solution increased biomass production and concentrations of free amino acids, notably theanine in young shoots and roots, without affecting total N in the leaves, absorption rates of inorganic N and glutamine synthetase activity. Amino acids in xylem saps and phloem exudates or total sugars in phloem exudates of tea plants from pot and field experiments showed their highest levels in bud breaking and shoot extension in early spring (March and early April). Application of Mg increased the amounts of amino acids and total sugars in the xylem saps and phloem exudates. CONCLUSION: Adequate supply of Mg nutrient promoted the synthesis of theanine in roots and its accumulation in the young shoots of tea plants. Magnesium nutritional status was an important factor influencing the mobility of amino acids and sugars via xylem and phloem especially when N and C reserves remobilized to support spring growth of young shoots. Copyright © 2011 Society of Chemical Industry     

Sequestration of zinc from zinc oxide nanoparticles and life cycle effects in the sediment dweller amphipod Corophium volutator

We studied the effects of ZnO nanoparticles [ZnO NPs, primary particle size 35 ± 10 nm (circular diameter, TEM)], bulk [160 ± 81 nm (circular diameter, TEM)], and Zn ions (from ZnCl(2)) on mortality, growth, and reproductive endpoints in the sediment dwelling marine amphipod Corophium volutator over a complete lifecycle (100 days). ZnO NPs were characterized by size, aggregation, morphology, dissolution, and surface properties. ZnO NPs underwent aggregation and partial dissolution in the seawater exposure medium, resulting in a size distribution that ranged in size from discrete nanoparticles to the largest aggregate of several micrometers. Exposure via water to all forms of zinc in the range of 0.2-1.0 mg L(-1) delayed growth and affected the reproductive outcome of the exposed populations. STEM-EDX analysis was used to characterize insoluble zinc precipitates (sphaerites) of high sulfur content, which accumulated in the hepatopancreas following exposures. The elemental composition of the sphaerites did not differ for ZnO NP, Zn(2+), and bulk ZnO exposed organisms. These results provide an illustration of the comparable toxicity of Zn in bulk, soluble, and nanoscale forms on critical lifecycle parameters in a sediment dwelling organism.     

Synchrotron micro-XRF and micro-XANES confirmation of the uptake and translocation of TiO₂ nanoparticles in cucumber (Cucumis sativus) plants

Advances in nanotechnology have raised concerns about possible effects of engineered nanomaterials (ENMs) in the environment, especially in terrestrial plants. In this research, the impacts of TiO(2) nanoparticles (NPs) were evaluated in hydroponically grown cucumber (Cucumis sativus) plants. Seven day old seedlings were treated with TiO(2) NPs at concentrations varying from 0 to 4000 mg L(-1). At harvest, the size of roots and shoots were measured. In addition, micro X- ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS), respectively, were used to track the presence and chemical speciation of Ti within plant tissues. Results showed that at all concentrations, TiO(2) significantly increased root length (average >300%). By using micro-XRF it was found that Ti was transported from the roots to the leaf trichomes, suggesting that trichomes are possible sink or excretory system for the Ti. The micro-XANES spectra showed that the absorbed Ti was present as TiO(2) within the cucumber tissues, demonstrating that the TiO(2) NPs were not biotransformed.     

基于表面增强拉曼光谱快速检测苹果汁中亚胺硫磷

利用种子生长法合成出不同大小(35～91nm,金核19nm;66～127nm,金核43nm)的金核银壳纳米粒子(Au-Ag NPs),对其形貌和光学特性进行表征,并将其作为表面增强拉曼散射(SERS)基底,探究不同粒径和金银比例对亚胺硫磷检测的影响。试验结果显示:42nm Au-Ag NPs(金核19nm)和78nm Au-Ag NPs(金核43nm)对亚胺硫磷标准溶液具有最佳的SERS增强效果,最低检出浓度可低至0.05mg/L。但Au-Ag NPs基底应用于苹果汁中亚胺硫磷的SERS快速检测效果存在较大差异,以42,78nm Au-Ag NPs作为增强基底时,苹果汁中的亚胺硫磷最低检出浓度分别为5.0,0.5 mg/L。研究表明通过筛选出合适的粒径及金银比例的Au-Ag NPs有望实现对果汁中亚胺硫磷的现场快速检测。     

楠竹笋对土壤中铅和镉的吸收特征分析

为了研究楠竹笋生长时期对土壤中铅(Pb)和镉(Cd)的累积效应及在各器官中的分配特征,在竹笋生长期的楠竹林里,施加外源硝酸铅(Pb(NO₃)₂)和硝酸镉(Cd(NO₃)₂)模拟土壤不同污染程度:5 mg·m-2轻度污染、50 mg·m-2中度污染、500 mg·m-2重度污染以及0 mg·m-2(对照)4个浓度梯度的Pb、Cd,分析Pb和Cd在楠竹笋不同生长期及各器官中的富集、累积和分配特征。结果表明:笋中各部位Pb、Cd的富集与外施Pb、Cd浓度和时间呈正相关,竹笋体内Pb和Cd的累积量随时间推移、污染程度增强而明显增加。三种污染程度中,除重度污染笋底在第21 d Pb含量超标,楠竹笋可食部分Pb含量均低于国家食品卫生标准(1.0 mg·kg-1);轻度、中度污染的竹笋可食部分Cd含量在0.02~0.14 mg·kg-1,低于国家食品卫生标准(0.2 mg·kg-1),然而重度镉污染使可食部分竹笋在第14 d以后含量超过国家食品卫生标准。重度污染时,施药第21 d后Pb、Cd在竹笋各器官中的累积百分比分别表现为笋根(73.84%、72.79%),笋底(6.33%、6.97%),笋中(2.52%、1.95%),笋尖(2.68%、0.52%),笋皮(14.63%、17.77%)。生物富集系数(BCF)和转移系数(TF)呈"上升"趋势。综上认为,Pb和Cd在楠竹笋体内具有明显的累积效应,并可转移到竹笋地上部各器官或组织中,导致这些器官或组织被Pb和Cd污染。     

Uptake of arsenic species by turnip (Brassica rapa L.) and lettuce (Lactuca sativa L.) treated with roxarsone and its metabolites in chicken manure

Roxarsone is an organoarsenic feed additive that can be metabolised to other higher toxic arsenic (As) species in animal manure such as arsenate, arsenite, monomethylarsonic acid, dimethylarsinic acid, 3-amino-4-hydroxyphenylarsonic acid and other unknown As species. The accumulation, transport and distribution of As species in turnip (Brassica rapa L.) and lettuce (Lactuca sativa L.) amended with roxarsone and its metabolites in chicken manure were investigated. Results showed arsenite was the predominant As form, followed by arsenate in turnip and lettuce plants, and a low content of dimethylarsinic acid was detected only in lettuce roots. Compared with the control plants treated with chicken manure without roxarsone and its metabolites, the treatments containing roxarsone and its metabolites increased arsenite content by 2.0–3.2% in turnip shoots, by 6.6–6.7% in lettuce shoots, by 11–44% in turnip tubers and by 18–20% in lettuce roots at two growth stages. The enhanced proportion of arsenate content in turnip shoots, turnip tubers and lettuce roots was 4.3–14%, 20–35% and 70%, respectively, while dimethylarsinic acid content in lettuce roots increased 2.4 times. Results showed that the occurrence of dimethylarsinic acid in lettuce roots might be converted from the inorganic As species and the uptake of both inorganic and organic As compounds in turnip and lettuce plants would be enhanced by roxarsone and its metabolites in chicken manure. The pathway of roxarsone metabolites introduced into the human body via roxarsone → animal → manure → soil → crop was indicated.     

Environmental implications of nanoparticle aging in the processing and fate of copper-based nanomaterials

Copper nanomaterials are being used in a large number of commercial products because these materials exhibit unique optical, magnetic, and electronic properties. Metallic copper nanoparticles, which often have a thin surface oxide layer, can age in the ambient environment and become even more oxidized over time. These aged nanoparticles will then have different properties compared to the original nanoparticles. In this study, we have characterized three different types of copper-based nanoparticle (NP) samples designated as Cu(new) NPs, Cu(aged) NPs, and CuO NPs that differ in the level of oxidation. The solution phase behavior of these three copper-based nanoparticle samples is investigated as a function of pH and in the presence and absence of two common, complexing organic acids, citric and oxalic acid. The behavior of these three copper-based NP types shows interesting differences. In particular, Cu(aged) NPs exhibit unique chemistry including oxide phases that form and surface adsorption properties. Overall, the current study provides some insights into the impacts of nanoparticle aging and how the physicochemical characteristics and reactivity of nanomaterials can change upon aging.     

Heavy metals (Pb,Cu, Zn and Cd) in the system soil – grapevine – grape

An Erratum has been published for this article in Journal of the Science of Food and Agriculture 79(15)1999, 2122. The investigation was carried out in the period 1991–1995 in a region with a major industrial pollutant, the Non‐Ferrous‐Metal Works, and a region with no industrial pollutants (as a control). The heavy metal content in soil, roots, annual shoots and perennial parts of grapevine, leaves, grapes and wine, was determined. Soil samples and roots of the rootstock Kober 5BB were taken at 10 cm intervals from depths of 0–100 cm. Roots were divided by thickness in fractions at 1 mm intervals. The shoots, bark, vascular tissue, wood, core and diaphragm were investigated. The leaf analyses included leaf blade and leaf petioles, and those of grapes, berry‐free raceme (washed in a lot of water and unwashed). Berries were analysed (the berry skin, the pulp and the seeds). The results obtained for the Pb, Cu, Zn and Cd contents in the grapevine roots show that they depend significantly both on their amounts in the soil and the age of the roots. The main parts of the heavy metal amounts taken by the roots of the grapevine from the soil are fixed and accumulated in the young feed rootlets (with diameters of 1 mm), and small amounts of them move through the conducting system to the older, larger diameter root system. The experimental data obtained for the presence of Pb, Cu, Zn and Cd in the separate tissues and organs of grapevines grown in an industrially polluted region showed that their amounts were mainly due to the heavy‐metal‐containing aerosols falling from the atmosphere. Part of them, however, got into the soil, and from there, even if in minimal amounts, penetrated via the root system into the grapevine plants and accumulated into their different overground parts. © 1999 Society of Chemical Industry     

The absorption and translocation of polychlorinated biphenyl congeners by Cucurbita pepo ssp pepo

The mobility of polychlorinated biphenyl (PCB) congeners within Cucurbita pepo ssp pepo cv. Howden (pumpkin), a PCB phytoextracting plant, was investigated through a comparison of field-weathered soil, root, shoot, and xylem sap congener profiles. This is the first study to show the presence of PCBs in xylem sap (range: 0.03-0.18 μg·mL(-1)), confirming that PCB translocation throughout the plant occurs via this medium. A comparison of soil (5.2 ± 2.5 μg·g(-1)), root (27.1 ± 2.1 μg·g(-1)), shoot (range: 1.9 ± 0.5 μg·g(-1) - 8.2 ± 1.4 μg·g(-1)), and xylem sap (0.09 ± 0.04 μg·g(-1)) samples showed significant differences in congener profiles, with lower chlorinated congeners (predominately trichlorinated ones) found within xylem sap in higher amounts than higher chlorinated congeners. The total PCB concentrations of xylem sap samples collected at various lengths along the primary plant shoot were not significantly different from each other, while those of primary shoot tissue samples significantly decreased (two-sample t test, p = 0.01) as the distance from the plant base increased. PCA analysis of individual congeners in the roots, shoots and xylem sap indicated that movement of the PCB congeners in the plant was affected by the number of chlorines in the molecule, and hence possibly log K(ow) and molecular weight, but not by planarity.     

一株广域pH耐受性微小噬菌体αα的分离、纯化及生理学特性分析

本研究采用双层平板法从污水中分离纯化出一株烈性沙门氏菌噬菌体αα。利用电镜观察其形态特征,通过琼脂糖凝胶电泳分析其核酸组成,并对其生理学特性进行分析,包括一步生长曲线、温度耐受性、pH耐受性、裂解谱、最佳离子浓度和最佳感染复数。结果表明,该烈性噬菌体αα有一个直径为20 nm的头部,无尾部结构,其核酸类型为单链DNA。由此推断,噬菌体αα属于微小噬菌体科。该噬菌体无明显潜伏期,裂解期为60 min,在pH2.10~11.45内和温度40~50 ℃内效价分别保持在106~108和108 pfu/mL左右,最佳感染复数值为10-4,钙镁离子均能促进该噬菌体的液体增殖,其中培养基中含10 mmol/L MgCl₂时促进效果最佳,与未添加离子的对照组相比提高了1.5个log。研究结果为噬菌体的多样性及其应用等方面的研究奠定了基础。     

不同芥菜型油菜基因型砷毒耐性研究

采用溶液培养法筛选196个芥菜型油菜基因型的砷（Na3AsO4）毒耐性。结果表明,2mg/L As（以砷酸钠水溶液中的砷离子浓度计）处理条件下,不同基因型油菜的生长和砷累积表现出明显的差异性。调查地上部干重的As/CK（砷处理与对照的比值）和根部的As/CK,发现各基因型变化范围分别为0.48～1.51和0.5～2.06,其变异系数分别为18.5%和30.2%。地上部或根部砷含量的变化范围分别是5.2～168.0mg/kg和117.1～1 544.3mg/kg,其变异系数分别为73.2%和37.5%。依据砷胁迫下油菜的相对干重（As/CK）及砷的含量,筛选出砷排异基因型（生长不受影响,且砷主要累积在根部,茎叶中砷含量较低）15个,砷低吸收基因型（生长不受影响,且茎和叶中砷含量较少）2个,以及砷敏感基因型（生长受严重抑制）5个。     

Long-term effects of titanium dioxide nanoparticles on nitrogen and phosphorus removal from wastewater and bacterial community shift in activated sludge

The expanding use of titanium dioxide nanoparticles (TiO(2) NPs) in a wide range of fields raises concerns about their potential environmental impacts. However, investigations of the potential effects of TiO(2) NPs on biological nitrogen and phosphorus removal and bacterial community in activated sludge are sparse. This study evaluated the influences of TiO(2) NPs on biological nutrient removal in the anaerobic-low dissolved oxygen (0.15-0.50 mg/L) sequencing batch reactor. It was found that 1 and 50 mg/L TiO(2) NPs had no acute effects on wastewater nitrogen and phosphorus removal after short-term exposure (1 day). However, 50 mg/L TiO(2) NPs (higher than its environmentally relevant concentration) was observed to significantly decrease total nitrogen (TN) removal efficiency from 80.3% to 24.4% after long-term exposure (70 days), whereas biological phosphorus removal was unaffected. Denaturing gradient gel electrophoresis profiles showed that 50 mg/L TiO(2) NPs obviously reduced the diversity of microbial community in activated sludge, and fluorescence in situ hybridization analysis indicated that the abundance of nitrifying bacteria, especially ammonia-oxidizing bacteria, was highly decreased after long-term exposure to 50 mg/L TiO(2) NPs, which was the main reason for the serious deterioration of ammonia oxidation. Further study revealed that 50 mg/L TiO(2) NPs inhibited the activities of ammonia monooxygenase and nitrite oxidoreductase after long-term exposure, but had no significant impacts on the activities of exopolyphosphatase and polyphosphate kinase, and the transformations of intracellular polyhydroxyalkanoates and glycogen, which were consistent with the observed influences of TiO(2) NPs on biological nitrogen and phosphorus removal.     

Effects of copper sources and dietary cation-anion balance on copper availability and acid-base status in dairy calves.

Twenty-four Holstein and Jersey calves (14 Holstein), 4 to 11 d of age, were assigned randomly to six treatments in a 2 x 3 factorial arrangement to examine the effects of Cu sources and dietary cation-anion balance on Cu availability and acid-base balance. Treatments were cationic basal diet (20 meq of dietary cation-anion balance on a DM basis), cationic basal diet supplemented with CuO, cationic basal diet supplemented with CuSO4, anionic basal diet (-10 meq), anionic basal diet supplemented with CuO, and anionic basal diet supplemented with CuSO4. Copper sources did not show any effect on growth of calves. The cationic diet increased calf growth compared with the anionic diet at wk 12 of the experiment. Blood pH was increased by the cationic diet in comparison with the anionic diet at wk 8 and 12. Blood pH also was increased by CuSO4 compared with CuO treatment in the early period of the treatment. Blood bicarbonate concentration was decreased by CuO and the anionic diet. Interactions between Cu sources and cation-anion balance were found for blood pH and bicarbonate concentration. Liver Cu concentration was increased by CuSO4 but not by CuO supplementation compared with control. Therefore, CuSO4 was found to be highly available, whereas CuO was a very poorly available source of Cu for young calves.     

Evidence for internalization of Escherichia coli into the aerial parts of maize via the root system

Escherichia coli introduced into the hydroponic growing medium of maize plants was detected 48 h later in the shoot. Decapitation of root tips or severing of the plant root system at the root-shoot junction enhanced bacterial internalization. The density of the bacteria in shoots of plants with damaged roots or removed root systems was 27.8 and 23.9 times higher than that in plants with intact roots, respectively. The concentration of viable cells in the hydroponic solution decreased over time from 9.3 x 10(6) CFU/ml at the time of inoculation to 8.5 x 10(1) CFU/ml 4 days thereafter. The number of E. coli cells associated with the roots also decreased with time, but a significant decline appeared only at 4 days postinoculation. At the time of sampling for E. coli presence in the shoot, 10(2) CFU/ml was present in the nutrient solution and 8 x 10(3) CFU/g was associated with the roots. The present study is the first to demonstrate internalization of E. coli via the root in a monocotyledonous plant.     

The uptake and distribution of copper in perennial ryegrass and white clover grown in flowing solution culture with a controlled supply of copper

The uptake and distribution of copper was examined in perennial ryegrass and white clover when these were grown in flowing solution culture with a controlled supply of copper at 0.025 mg litre^?1 (0.4 μM). Although the concentration of copper in the shoots of white clover was greater than that in those of ryegrass, there was no difference between the two species in (i) absorption per unit of root or (ii) the transport of copper from roots to shoots. Differences in the growth patterns of the two plants may be responsible for differences in copper concentration in their dry matter. The proportion of the shoot's copper that was associated with cell walls fell, during growth over 33 days, from 23 to 12% in ryegrass and from 35 to 7% in white clover. There was some indication that terminating the supply of phosphate to the plants (which did not affect absorption by roots or transport to shoots) may have increased the degree of association of copper with the cell walls of the shoots.     

盐胁迫对油菜幼苗离子吸收和分配的影响

以宝杂油1号和本课题组选育品系南盐油11号为材料,比较了100和200mmol·L-1NaCl胁迫10d对两个甘蓝型油菜（Brassica napus L.）品种（系）幼苗生长及其离子吸收和分配的效应。结果表明,盐胁迫明显抑制油菜幼苗的生长,其中南盐油11号的耐盐性明显高于宝杂油1号。盐胁迫导致植株盐分（Na＋、Cl-）含量上升,地上部Na＋、Cl-积累明显高于根系;植株体内K＋、Ca2＋含量明显降低。盐胁迫下,维持体内较高的K＋/Na＋、Ca2＋/Na＋比率,维持较高的SK,Na、SCa,Na（离子吸收和运输的K＋、Ca2＋、Na＋选择性比率）是南盐油11号耐盐性高于宝杂油1号的重要原因。     

Some observations on the effect of grassing-down,nitrogen fertilisation and irrigation on the growth,leaf nutrient content and fruit quality of young golden delicious apple trees

In a 3 year trial the growth and leaf nutrient content of newly planted Golden Delicious/MM 106 apple trees was compared under grassed-down and clean cultivated conditions. With no fertiliser applications grassing down, compared with cultivation, decreased shoot extension and trunk girth increment in all three seasons and total dry weight of both tops and roots of trees at the end of the 3 year period. Grassing-down generally decreased total N and increased concentrations of P, K and Ca in the leaves. Generally, in the third season, the mineral composition of the fruit paralleled that in the leaves. Application of fertiliser N to cultivated plots in the second and third seasons had no significant effect on tree growth; N fertilisation significantly increased tree growth and total leaf area per tree under grassed-down conditions, particularly in the third season. During the third season irrigation had only a small effect on the growth of trees from the grassed-down non-fertilised plots. However, there was a large positive interaction between N fertilisation and irrigation on tree growth, total dry weight of both shoots and roots of trees and on fruit size.     

In-situ synthesis of CuO nanoparticles on cotton fabrics using spark discharge method to fabricate antibacterial textile

In this research, the spark discharge method (SDM) was used for in-situ synthesis of copper and copper oxide nanoparticles (NPs) on cotton fabrics for producing antibacterial textile. Varieties of analytical techniques were applied for the characterization of both NPs and synthesized CuO NPs on cotton fabrics. The structural characterization of the particles was carried out by the X-ray powder diffraction method. Also, the morphological properties of treated cotton samples were investigated using scanning electron microscope. Particle size and size distribution were measured by dynamic light scattering apparatus. The results show that concentration of 100 ppm is enough for killing 10⁶ CFU/mL of bacteria. It is indicated that the synthesized CuO NPs are very strong against both Staphylococcus aureus and Escherichia coli. Also, the durability of antibacterial efficiency after 15 times of washing was tested. The results confirm that the antibacterial fastness properties are significant and no colonies spread over agar plate after 15 cycles of washing. It was concluded that SDM for in-situ synthesize of nano-CuO on cotton fabrics in batch systems is very promising method.