作物种类对中国2种典型土壤中铜锌有效性的影响

为阐明不同作物对土壤铜锌有效性的影响,采集2种典型土壤--红壤和黄泥土,人工制成铜锌单一与复合污染的土壤(铜为50 mg/kg、锌为200 mg/kg),进行盆栽试验,观察了小麦、油菜、番茄和小白菜4种作物的生物量、铜锌浓度及土壤有效态铜锌浓度.结果表明:(1)在2种土壤上,4种作物的生物量均小于没有污染的对照,且铜锌复合污染的作物生物量总体上比铜锌单一污染的低;(2)4种作物在红壤和黄泥土上种植对土壤有效态铜、锌浓度影响的趋势一致,均为种植番茄后铜锌污染土壤的有效态铜、锌浓度最高,油菜和小白菜次之,小麦最低,即番茄>油菜和小白菜>小麦,与作物中铜、锌浓度以及富集系数的高低顺序完全相反;(3)对照、铜锌单一与复合污染土壤pH变化均不甚明显;(4)作物对土壤铜锌有效性的影响并不只是通过提高土壤pH来降低有效态铜、锌浓度,对铜锌的吸收富集作用是降低其有效性的主要机制之一.     

施加磷元素后对小麦抗重金属铜毒性的影响

将小麦幼苗放在含有不同浓度磷元素(1 mmol/L和10 mmol/L)和铜元素(0.16μmol/L、100μmol/L和1 mmol/L)的培养液中处理12 h后,观察植物体内铜元素的含量、叶绿素含量、抗坏血酸循环的变化.结果表明,当培养液中施加的铜元素浓度相同时,施加较高浓度的磷(10 mmol/L)能促进植物根部吸收和积累铜,并能促进铜元素从根部向地上部的运输.此外,实验结果还表明,当培养液中都含有较少量的铜(0.16μmol/L)元素时,比较磷浓度对植物体内生理反应的影响时,发现在含有高浓度磷的培养液中培养的小麦体内的受到较少的膜质过氧化损伤,光合色素的含量保持稳定.但是,当培养液中有较高浓度的铜元素(100μmol/L和1 mmol/L)时,施加高浓度的磷反而加剧了植物体内的膜质过氧化损伤和引起光合色素的分解,从而不利于植物正常的生长发育.     

施加磷元素后对小麦抗重金属铜毒性的影响

将小麦幼苗放在含有不同浓度磷元素（1 mmol/L和10 mmol/L）和铜元素（0.16μmol/L、100μmol/L和1 mmol/L）的培养液中处理12 h后,观察植物体内铜元素的含量、叶绿素含量、抗坏血酸循环的变化.结果表明,当培养液中施加的铜元素浓度相同时,施加较高浓度的磷（10 mmol/L）能促进植物根部吸收和积累铜,并能促进铜元素从根部向地上部的运输.此外,实验结果还表明,当培养液中都含有较少量的铜（0.16μmol/L）元素时,比较磷浓度对植物体内生理反应的影响时,发现在含有高浓度磷的培养液中培养的小麦体内的受到较少的膜质过氧化损伤,光合色素的含量保持稳定.但是,当培养液中有较高浓度的铜元素（100μmol/L和1 mmol/L）时,施加高浓度的磷反而加剧了植物体内的膜质过氧化损伤和引起光合色素的分解,从而不利于植物正常的生长发育.     

柠檬酸对褐土中DTPA提取态铜、镉含量及对紫花苜蓿吸收铜、镉的影响

为了阐述有机酸对土壤中重金属生物有效性的影响,通过盆栽实验,研究了Cu、Cd复合污染下柠檬酸对褐土中二乙基三胺五乙酸(DTPA)提取态铜和镉含量的影响,并探讨了柠檬酸对植物吸收铜、镉的影响。结果表明,土壤中DT-PA-Cu含量随柠檬酸添加量的增加而减小,添加高浓度铜(Cu 1 000)处理中,DTPA-Cu含量减小更明显。在添加低铜浓度(Cu600)处理下,柠檬酸添加量为2和12 mmol/kg时,土壤DTPA-Cu含量随土壤镉含量的增加而增加,而柠檬酸含量为5mmol/kg时,DTPA-Cu含量在低镉处理(Cd 1)时含量最低。紫花苜蓿中铜含量随柠檬酸添加量的增加明显降低。土壤中DTPA-Cd含量随柠檬酸添加量的增加而减小,且随铜添加量的增加而降低。紫花苜蓿中的镉含量随柠檬酸添加量的增加先增加后减小;在相同柠檬酸添加量处理时,紫花苜蓿中镉的含量随镉含量的增加而增加;在低镉处理下,铜的加入对较低柠檬酸浓度时紫花苜蓿镉含量影响不明显,但柠檬酸浓度为12 mmol/kg时,紫花苜蓿中镉含量随铜添加量的增加而明显增加。     

灰化苔草叶片铜污染的高光谱响应研究

为了鄱阳湖湿地的生态安全,通过土壤盆栽实验,研究了不同Cu浓度(0、50、100、150、200和300 mg/kg)下灰化苔草(Carex cinerascens)在整个生长发育期内叶片光谱参数和叶绿素的变化过程。结果表明,灰化苔草对Cu的耐性上限浓度不超过300 mg/kg;随着添加Cu浓度的升高,叶片Cu含量和土壤有效态Cu含量均逐渐升高,叶片SPAD值渐次降低;叶片Cu含量与红谷深度、红边峰值、红边斜率、R750~1250 nm等光谱特征值之间均呈现显著的负相关关系;灰化苔草最佳监测生育期为生长期。由此,为鄱阳湖湿地生态健康变化进行快速诊断提供了科学依据。     

典型磺胺类抗生素对油菜叶片叶绿素、可溶性蛋白及抗氧化酶的影响

通过盆栽实验研究了典型磺胺类抗生素磺胺甲恶唑(SMZ)、磺胺甲基嘧啶(SM1)和磺胺噻唑(ST)对油菜叶片内抗氧化酶(POD)活性、叶绿素(CHL)含量和可溶性蛋白(SP)含量的影响。结果表明:在低浓度染毒处理(15.0mg/kg)和高浓度染毒处理(45.0mg/kg)下,SM1、ST对油菜叶片中的CHL含量均有显著抑制作用(P0.05),SMZ对油菜叶片中的CHL含量有极显著抑制作用(P0.01)。3种磺胺类抗生素对油菜叶片SP含量的抑制作用随着染毒浓度的增加逐渐增强,其中SMZ对SP含量的抑制作用最大。两种浓度的染毒处理下,3种磺胺类抗生素对油菜叶片的POD活性均产生极显著诱导(P0.01)作用,并且SMZ对POD活性的诱导作用最为显著。综上,SMZ、SM1和ST均显著影响了油菜体内的生化过程,并且3种抗生素中SMZ的毒性效应最强。     

碳酸钙和粉煤灰对铅胁迫下小麦毒害的缓解效应

采用室内盆栽和网室盆栽的方法,研究了碳酸钙和粉煤灰对铅污染土壤的小麦幼苗生物效应、成熟期籽粒含铅量和蛋白质含量及生物产量的影响,探讨了碳酸钙和粉煤灰缓解铅毒害小麦的生理机制.结果表明,在轻度铅污染(铅为350 mg/kg)的小麦农田,1.0 g/kg碳酸钙或50 g/kg粉煤灰对小麦生长有明显的促进作用.能有效缓解铅对小麦的毒害;在重度铅污染(铅为600mg/kg)的小麦农田,1.0～2.0 g/kg碳酸钙或50～100 g/kg粉煤灰对小麦铅毒害缓解效果较好.     

类芦对铅的耐性及富集能力探讨

通过野外调查和盆栽试验,研究了类芦(Neyraudia reynaudiana)对Pb的耐性和富集能力.研究结果表明,类芦对Pb耐受的临界浓度为800 mg/kg,在此浓度以下Pb对类芦的生长基本无抑制作用.随着处理浓度的增加,类芦生长变缓慢、出现中毒症状,但仍能存活.从富集能力来看,土壤Pb为中低浓度时,类芦的富集能力较强,但Pb浓度超过1 000 mg/kg后地上部富集量增加缓慢,而根部的含量则降低.在各种Pb处理浓度下,类芦地上部Pb含量均大于根部,说明这种植物对Pb有较好的迁移能力.研究发现,类芦具有较高的生物量,因此其地上部Pb迁移总量较高,在土壤Pb浓度为800 mg/kg时类芦地上部的迁移总量可达到221.77 mg/m2.综合分析可知,类芦对中度Pb污染土壤的植物修复具有较大的潜力.     

电絮凝-离子交换-生化法处理化学镀铜废液

采用电絮凝-离子交换-厌氧-好氧膜生物反应器(MBR)法处理印刷线路板化学镀铜废液。结果表明,电絮凝在pH为6.0,电流密度为50 m A/cm2、电解时间2 h的条件下,COD去除率约为71.5%,Cu去除率为86%左右,可生化指数从0.11提高到0.30。采用大孔苯乙烯系螯合型阳离子树脂吸附回收铜,在pH为5时,树脂对铜去除率最大,饱和吸附量为31.28 g/kg。流速为6 BV/h时,穿透时间为298 min,处理水量884 m L。选用质量分数为15%的盐酸作为解吸剂,解吸率可达96.4%。离子交换出水进行厌氧-好氧MBR法处理。电絮凝-离子交换法-厌氧-好氧MBR工艺能有效处理化学镀铜废液,生化出水COD浓度低于250 mg/L,铜浓度低于0.5 mg/L,达到广东省《水污染物排放限值(DB44/6-2001)》中COD和总铜的三级排放标准。     

镉胁迫对向日葵幼苗生长和生理特性的影响

采用溶液培养方法,研究了不同浓度镉(0、0.05、0.1、0.5和1 mg/L)处理7 d对向日葵幼苗生长和生理特性的影响。结果表明：随着镉处理浓度的增加，向日葵幼苗对镉的吸收显著增加。1 mg/L镉浓度处理时，叶、茎和根中镉浓度分别为0.05 mg/L镉处理时的16.3、19.2和581倍；根中积累的镉含量明显高于叶和茎, 各浓度根部积累的镉分别为叶和茎的37.8～63倍和29.4～41倍。镉胁迫显著抑制向日葵幼苗生长和叶绿素合成，当镉浓度达1 mg/L时，整株植物生物量和总叶绿素含量分别为对照的55.9%和52.6%。镉胁迫下向日葵幼苗游离脯氨酸和丙二醛（MDA）含量显著增加，1 mg/L镉浓度时，根中含量分别为对照的4和5.8倍。向日葵幼苗可溶性蛋白含量和过氧化物酶(POD)活性变化与镉胁迫浓度呈明显的倒U字型关系，可溶性蛋白含量在0.05 mg/L镉浓度时达到最大值，叶、茎、根中的POD活性分别在0.1、0.1和0.05 mg/L镉浓度时达到最大值。     

Effects of copper(II) and copper oxides on THMs formation in copper pipe

Little is known about how the growth of trihalomethanes (THMs) in drinking water is affected in copper pipe. The formation of THMs and chlorine consumption in copper pipe under stagnant flow conditions were investigated. Experiments for the same water held in glass bottles were performed for comparison. Results showed that although THMs levels firstly increased in the presence of chlorine in copper pipe, faster decay of chlorine as compared to the glass bottle affected the rate of THMs formation. The analysis of water phase was supplemented by surface analysis of corrosion scales using X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDX). The results showed the scales on the pipe surface mainly consisted of Cu₂O, CuO and Cu(OH)₂ or CuCO₃. Designed experiments confirmed that the fast depletion of chlorine in copper pipe was mainly due to effect of Cu₂O, CuO in corrosion scales on copper pipe. Although copper(II) and copper oxides showed effect on THMs formation, the rapid consumption of chlorine due to copper oxide made THM levels lower than that in glass bottles after 4 h. The transformations of CF, DCBM and CDBM to BF were accelerated in the presence of copper(II), cupric oxide and cuprous oxide. The effect of pH on THMs formation was influenced by effect of pH on corrosion of copper pipe. When pH was below 7, THMs levels in copper pipe was higher as compared to glass bottle, but lower when pH was above 7.     

Characterization of heavy metal-resistant endophytic bacteria from rape (Brassica napus) roots and their potential in promoting the growth and lead accumulation of rape

Two lead (Pb)-resistant endophytic bacteria were isolated from rape roots grown in heavy metal-contaminated soils and characterized. A pot experiment was conducted for investigating the capability of the two isolates to promote the growth and Pb uptake of rape from Pb-amended soil. The two isolates were identified as Pseudomonas fluorescens G10 and Microbacterium sp. G16 based on the 16S rDNA gene sequence analysis. Strains G10 and G16 exhibited different multiple heavy metal and antibiotic resistance characteristics and increased water-soluble Pb in solution and in Pb-added soil. Root elongation assays demonstrated increases in root elongation of inoculated rape seedlings compared to the control plants. Strain G16 produced indole acetic acid, siderophores and 1-aminocyclopropane-1-carboxylate deaminase. Increases in biomass production and total Pb uptake in the bacteria-inoculated plants were obtained compared to the control. The two strains could colonize the root interior and rhizosphere soil of rape after root inoculation.     

Toxicity of copper on rice growth and accumulation of copper in rice grain in copper contaminated soil

Pot soil experiments showed that copper (Cu) is highly toxic to rice. Rice grain yields decreased exponentially and significantly with the increase of soil Cu levels. Rice grain yield was reduced about 10% by soil Cu level of 100 mg kg(-1), about 50% by soil Cu level of 300-500 mg kg(-1) and about 90% by soil Cu concentration of 1,000 mg kg(-1). Root was more sensitive to soil Cu toxicity than other parts of rice plant at relatively lower soil Cu levels (less than 300-500 mg kg(-1)), but the growth of whole rice plant was severely inhibited at high soil Cu levels (300-500 mg kg(-1) or above). Cu concentrations in rice grain increased with soil Cu levels below 150-200 mg kg(-1), but decreased with soil Cu levels above 150-200 mg kg(-1), with peak Cu concentration at soil Cu level of 150-20 mg kg(-1). Cu was not distributed evenly in different parts of rice grain. Cu concentration in cortex (embryo) was more than 2-fold that in chaff and polished rice. More than 60% of the Cu in grain was accumulated in polished rice, about 24% in cortex (embryo), and about 12% in chaff. So, about 1/3 of the Cu in rice grain was eliminated after grain processing (chaff, cortex and embryo was removed).     

Dispersal and persistence of genetically modified oilseed rape around Japanese harbors

Background, aim, and scope

The possibility of gene transfer from genetically modified oilseed rape (OSR) to its cultivated or wild relatives is of concern since its commercial cultivation, because of its potential weediness and impact on the environment. Introgression of modified genes can affect conservation of agricultural crops, because there are many cultivars and wild Brassicaceae that may cross with genetically modified OSR (Brassica napus) in Japan. Japan imports more than 2 million tons of OSR a year from Canada and other countries. Since volunteers of GM OSR were found around harbors in 2004, a lot of feral GM OSR was discovered in Japan. To consider the way how to keep domestic Brassicaceae from GM contamination, we surveyed and analyzed the dispersal and persistence of GM OSR around Japanese harbors. We present the cause and abundance of GM OSR in Japan by this paper.

Materials and methods

Survey of the feral OSR was performed several times a year at different seasons when domestic OSR either grows or does not around port areas. Detection of herbicide tolerance in feral B. napus was done by test papers that cross react with the modified gene product. Two kinds of herbicide tolerance (glyphosate and glufosinate) were tested.

Results

The feral B. napus were discovered around all 13 harbors that import rapeseeds from foreign countries. Genetically modified, herbicide-tolerant OSR were frequently found in the surveyed populations. Two kinds of herbicide-tolerant OSR (glyphosate- and glufosinate-tolerant) were discovered in a natural condition 40 km from port to an oil factory where 60,000 tons of OSR seed are processed a year. The cause of voluntary growth of OSR is seed spillage during transportation by trucks from harbors to oil factories and other processing facilities. Some of the feral OSR growing along the roadsides of transport paths exhibited perennial growth spilling their seeds around the places. Alteration of the generation of feral GM OSR was discovered for the first time in Japan as a result of this study. We studied the yearly change of feral OSR abundances focusing on Yokkaichi port over the 4 years since 2004. The rate of GM OSR increases year to year, and reaches nearly 90% in 2008.

Discussion

The possibility and consequences of gene transfer from the genetically modified OSR to domestic species (B. rapa and B. juncea) were discussed in relation to impact on domestic agriculture and on environments. Evolutional meaning of the gene transfer was also discussed with respect to the gene construct of GM OSR. This study shows the importance of another pathway of modified gene transfer to non-GM relative species by seed transportation in addition to pollen transfer from commercial cultivation of genetically modified OSR.

Conclusions and recommendations

We identified unintended dispersal and persistence of GM OSR around Japanese harbors that import OSR from Canada and other countries. Both glyphosate- and glufosinate-tolerant feral B. napus were discovered. The cause of volunteer OSR is spillage of the seeds during transportation by truck to oil factory. The feral GM OSR sometimes showed perennial growth in Japanese phonological conditions which are not observed for domestic Brassicaceae. In addition, we confirmed an alteration of generations by feral GM OSR in Japan. The possibility of cross pollination and GM gene introgression to domestic varieties can occur in these environments. To improve the situation, each responsible organization, company, administration, or government should establish measures how to stop the dispersal and persistence of GM OSR in nature. Also, the GM plant developers are responsible for revising this situation.     

油菜秸秆直接液化为液体油工艺探讨

为了实现油菜秸秆的综合利用,将其在高温高压下催化液化制备液体油。结果表明:(1)油菜秸秆中的纤维素、半纤维素、木质素质量分数分别为25.45%、11.57%、28.73%,木质素最高,其次是纤维素。(2)油菜秸秆和残渣元素分析可知,液化反应前后油菜秸秆各元素含量无明显变化,热值(HHV)分别为10.58、10.47MJ/kg。(3)硫酸盐催化作用优于氯化物催化剂,硫酸铁和硫酸亚铁在中性反应溶剂条件下催化效果较佳,特别是在酮类反应溶剂中。在实验条件为固液比1.0∶19.3(油菜秸秆与混合溶剂的质量比)、反应时间4h、催化剂用量1%(质量分数)、丙酮作反应溶剂、硫酸铁作催化剂时,转化率可达47.106%。(4)预先将油菜秸秆浸泡在1%(质量分数)KOH溶液中12h,对生物质中纤维素、半纤维素和木质素有溶胀作用,能提高转化率。(5)通过热重(TG)/差热(DTG)曲线分析,残渣的燃烧反应性更好,活化能略低于油菜秸秆。     

Runoff rates,chemical speciation and bioavailability of copper released from naturally patinated copper

The release of copper, induced by atmospheric corrosion, from naturally patinated copper of varying age (0 and 30 years) has been investigated together with its potential ecotoxic effect. Results were generated in an interdisciplinary research effort in which corrosion science and ecotoxicology aspects were combined. The aim of the investigation was to elucidate the situation when copper-containing rainwater leaves a roof in terms of runoff rate, chemical speciation, bioavailability and ecotoxicity effects. Data have been collected during a three-year field exposure conducted in the urban environment of Stockholm, Sweden. The potential environmental effects have been evaluated using a combination of a copper specific biosensor test with the bacterium Alcaligenes eutrophus and the conventional 72-h growth inhibition test with the green alga Raphidocelis subcapitata. The results show annual runoff rates between 1.0 and 1.5 g/m2 year for naturally patinated copper of varying age. The runoff rate increased slightly with patina age, which mainly is attributed to the enhanced first flush effect observed on thicker patina layers. The total copper concentration in investigated runoff samplings ranged from 0.9 to 9.7 mg/l. Both computer modeling and experimental studies revealed that the majority (60-100%) of released copper was present as the free hydrated cupric ion, Cu(H2O)6(2+), the most bioavailable copper species. However, other copper species in the runoff water, such as, e.g. Cu(OH)+ and Cu2(OH)2(2+), were also bioavailable. The copper-containing runoff water, sampled directly after release from the roof, caused significant reduction in growth rate of the green alga. It should be emphasized that the results describe the runoff situation immediately after release from the copper roof and not the real environmental ecotoxicity. Therefore the data should only be used as an initial assessment of the potential environmental effect of copper runoff from building applications. Future risk assessments should also consider dilution effects of copper, changes in its chemical speciation and bioavailability during environmental entry, and type and sensitivity of the receiving ecosystem.     

Influence of soluble copper on the electrokinetic properties and transport of copper oxychloride-based fungicide particles

This article describes the influence of dissolved copper on the electrokinetic properties and transport of a copper oxychloride-based fungicide (COF) in porous media. The Zeta potential (ζ) of COF particles increases (viz. becomes less negative) with increasing concentration of Cu(2+) in the bulk solution. ζ decreases for COF when the electrolyte (NaNO(3)) concentration is raised from 1 to 10mM. This can be ascribed to ion correlation of Cu(2+) in the electrical double layer (EDL). COF transport tests in quartz sand columns showed the addition of Cu(2+) to the bulk solution to result in increased retention of the metal. Modelling particle deposition dynamics provided results consistent with kinetic attachment. Based on the effect of soluble Cu on colloid mobility, the transport of particulate and soluble forms of copper is coupled via the chemistry of pore water and colloid interactions. Mutual effects between cations and colloids should thus be considered when determining the environmental fate of particulate and soluble forms of copper in soil and groundwater (especially at copper-contaminated sites).     

Speciation and leachability of copper in mine tailings from porphyry copper mining: influence of particle size

Mine tailing from the El Teniente-Codelco copper mine situated in VI Region of Chile was analysed in order to evaluate the mobility and speciation of copper in the solid material. Mine tailing was sampled after the rougher flotation circuits, and the copper content was measured to 1150 mg kg (-1) dry matter. This tailing was segmented into fractions of different size intervals: 0-38, 38-45, 45-53, 53-75, 75-106, 106-150, 150-212, and >212 microm, respectively. Copper content determination, sequential chemical extraction, and desorption experiments were carried out for each size interval in order to evaluate the speciation of copper. It was found that the particles of smallest size contained 50-60% weak acid leachable copper, whereas only 32% of the copper found in largest particles could be leached in weak acid. Copper oxides and carbonates were the dominating species in the smaller particles, and the larger particles contained considerable amounts of sulphides.     

Interactions of copper and pyrene on phytoremediation potential of Brassica juncea in copper–pyrene co-contaminated soil

Phytoremediation which is a plant based remediation process is an emerging technology for treating inorganic (heavy metals) as well as organic pollutants. It may also be suitable for remediation of sites co-contaminated with heavy metals and organics which have become more prevalent. A glasshouse experiment was carried out to investigate the effect of 50 and 100 mg kg^?1 of copper or 250 and 500 mg kg^?1 of pyrene and the combined effect of copper and pyrene on the growth of Brassica juncea together with the uptake and accumulation of copper as well as dissipation of pyrene. Results showed a negative effect of copper–pyrene co-contamination on shoot and root dry matter and an inhibition of copper phytoextraction. Pyrene was significantly decreased in planted and non-planted soils accounting for 90–94% of initial extractable concentration in soil planted with B. juncea and 79–84% in non-planted soil which shows that the dissipation of pyrene was enhanced with planting. The occurrence of copper tended to increase the residual pyrene in planted soil, however in the presence of high concentration of Cu (100 mg kg^?1), the residual pyrene concentration in soil were similar to those in unplanted soil. This may suggest that changes in the root physiology or rhizospheric microbial activity resulting from Cu stress could be an impediment to pyrene dissipation. The inhibition of Cu phytoextraction and degradation of pyrene by B. juncea under co-contamination may reduce the viability of phytoremediation in sites containing multiple pollutants.     

The effects of copper ions and copper nanomaterials on the output of amino acids from marine microalgae

In this study, the marine microalgae Skeletonema costatum and Nitzschia closterium were exposed to different forms of copper, such as a metal salt (Cu²⁺), a nano-metal (nano-Cu), and nano-metal oxide (nano-CuO). During a 96-h exposure to nanoparticles (NPs) and salt, the cell number, Cu²⁺ concentration in the culture medium, morphology, and intracellular amino acids were measured to assess the toxicity of the copper materials and the toxicity mechanism of the NPs. As results, the toxicity of Cu²⁺, nano-Cu, and nano-CuO to marine phytoplankton decreased in order. The EC₅₀ values of Cu²⁺ and nano-Cu for S. costatum and N. closterium ranged from 0.356 to 0.991 mg/L and 0.663 to 2.455 mg/L, respectively. Nano-Cu inhibits the growth of marine phytoplankton by releasing Cu²⁺; however, nano-CuO is harmful to microalgae because of the effect of NPs. The secretion of extracellular polymeric substances by microalgae could also affect the toxicity of nano-Cu and nano-CuO to microalgae. S. costatum was more sensitive to copper than N. closterium. Cu²⁺, nano-Cu, and nano-CuO all reduced per-cell amino acids and the total output of algae-derived amino acids by affecting the growth of the phytoplankton. This study helps to understand the risk assessment of nano-Cu and nano-CuO to marine microalgae.