Ecotoxicological effect of zinc oxide nanoparticles on soil microorganisms

The widespread production and use of zinc oxide nanoparticles (ZnO-NPs) in recent years have posed potential threat to the ecosystem. This study aimed to investigate the ecotoxicological effect of ZnO-NPs on soil microorganisms using laboratory microcosm test. Respiration, ammonification, dehydrogenase (DH) activity, and fluorescent diacetate hydrolase (FDAH) activity were used as ecotoxicological parameters. The results showed that in the neutral soil treated with 1 mg ZnO-NPs per g soil (fresh, neutral), ammonification was significantly inhibited during the study period of three months, but the inhibition rate decreased over increasing time. Inhibition in respiration was observed in the first month of the test. In various ZnO-NPs treatments (1 mg, 5 mg, and 10 mg ZnO-NPs per g soil), DH activity and FDAH activity were inhibited during the study period of one month. For both enzyme activities, there were positive dose–response relationships between the concentration of ZnO-NPs and the inhibition rates, but the curves changed over time due to changes of ZnO-NPs toxicity. Soil type affected the toxicity of ZnO-NPs in soil. The toxicity was highest in the acid soil, followed by the neutral soil. The toxicity was relatively low in the alkaline soil. The toxicity was not accounted for by the Zn²⁺ released from the ZnO-NPs. Direct interaction of ZnO-NPs with biologic targets might be one of the reasons. The adverse effect of ZnO-NPs on soil microorganisms in neutral and acid soils is worthy of attention.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

石灰性土壤环境中缺锌机理的探讨

作者认为石灰性土壤中锌活性较低的原因,是由于碳酸盐导致土壤pH上升,在较高pH条件下氧化铁对锌的强烈固定,造成了大量专性吸附状态的氧化铁结合态锌及部份碳酸盐结合态锌,使交换态的有效锌含量很低,同时还证明:自然的石灰性土壤中,松结有机态锌与碳酸盐结合态是活性锌的直接给源,外源加入的锌仅为松结右机态锌。此外,石灰性土壤中各主要土壤的化学组份对外源锌的固定量高伛顺序为:氧化铁>有机质>粘土矿物>碳酸盐>氧化锰:对土壤中原有锌的固定作用大小依次为:粘土矿物>氧化铁>有机质>氧化锰>碳酸盐。     

干旱区绿洲土壤中重金属的形态分布及生物有效性研究

测定了Cd、Pb、Zn和Ni等重金属在不同处理土壤中的全量和各赋存形态,以及它们在盆栽试验油菜（Brassica cole）中的质量分数,并利用Pearson相关系数分析了该区土壤-油菜体系的生物有效性。结果表明,供试绿洲土壤原状土中,Cd、Pb、Zn和Ni均以稳定的残渣态形式存在;而在处理土壤中,重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Pb、Zn和Ni则主要以铁锰氧化态为主。根据相关性分析,油菜根部和叶部的Ni质量分数均与土壤中Ni的各非残渣态分布系数有相关性,表明当土壤中Ni以非残渣态存在时,活动性Ni的质量分数较高,其被生物吸收利用的可能性也较大;油菜根部的Zn质量分数与土壤中Zn的碳酸盐结合态分布系数显著的正相关性;油菜各部位Cd和Pb的质量分数与土壤中Cd和Pb的各形态分布系数之间无显著相关关系。     

不同使用年限蔬菜大棚土壤重金属含量变化

调查了 1、5、8、1 1a棚龄蔬菜大棚土壤中重金属元素As、Cd、Co、Cr、Cu、Hg、Fe、Mn、Mo、Ni、Pb和Zn的含量。结果表明 :同一使用年限的蔬菜大棚 0～ 40cm土层内重金属元素含量差异很小 ;与棚外土壤相比 ,除 1a棚龄的土壤外 ,多数土壤重金属含量随大棚使用年限的延长而有所增加 ;研究地区的蔬菜大棚土壤尚未发生重金属污染超标现象 ;大量施肥 (复合肥 )可能是导致蔬菜大棚土壤中重金属含量升高的主要原因     

Heavy metal migration in soils and rocks at historical smelting sites

The vertical migration of metals through soils and rocks was investigated at five historical lead smelting sites ranging in age between 220 and 1900 years. Core samples were taken through metal-contaminated soils and the underlying strata. Concentration profiles of lead and zinc are presented from which values for the distances and rates of migration have been derived. Slag-rich soil horizons contain highly elevated metal concentrations and some contamination of underlying strata has occurred at all sites. However, the amounts of lead and zinc that have migrated from soils and been retained at greater depths are comparatively low. This low metal mobility in contaminated soils is partly attributed to the elevation of soil pH by the presence of calcium and carbonate originating from slag wastes and perhaps gangue minerals. Distances and rates of vertical migration were higher at those sites with soils underlain by sandstone than at those with soils underlain by clay. For sites with the same parent material, metal mobility appears to be increased at lower soil pH. The mean migration rates for lead and zinc reach maxima of 0.75 and 0.46 cm yr^–1 respectively in sandstone at Bole A where the elements have moved mean distances of 4.3 and 2.6 m respectively. There is some evidence that metal transport in the sandstone underlying Bole A and Cupola B occurs preferentially along rock fractures. The migration of lead and zinc is attenuated by subsurface clays leading to relatively low mean migration rates which range from 0.03 to 0.31 cm yr^–1 with many values typical of migration solely by diffusion. However, enhanced metal migration in clays at Cupola A suggest a preferential transport mechanism possibly in cracks or biopores.     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

Evaluation of heavy metal contamination in Phaeozem of northeast China

Surface and profile Phaeozem soil samples from 31 locations affected by various anthropogenic activities such as mining, chemical manufacturing, traffic emission and pesticide application were collected in Heilongjiang Province and Jilin Province, northeast China. The range of total concentrations of four heavy metals Cd, Pb, Cu and Zn in the soil was 0.011–3.137, 10.31–62.34, 9.74–51.21 and 39.54–247.59 mg kg⁻¹, respectively, determined using the acidic digestion procedure. Four methods including single contamination evaluation, background concentration comparison, surface/subsurface concentration comparison and exchangeable fraction evaluation were used to evaluate the extent of metal contamination in Phaeozem. The results indicated that different activities increased the concentrations of the heavy metals in surface soils, where high concentrations of cadmium and lead were found close to chemical plants and in the suburbs of the investigated cities. The four methods showed a general trend of increased soil contamination with heavy metals. Cadmium was of the most concern compared with the other contaminated elements in the study area, due to the long-term phosphatic fertilizer utilization and industrial activities. The proper evaluation method for cadmium contamination was the background concentration comparison, while for zinc and copper was the single contaminative index evaluation. Cadmium and lead could be the potential environmental risk in the Phaeozem area based on the different evaluations.     

Total and bioavailable metals in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo): relation to genetic variation in plant populations

Knowledge of total and bioavailable metal contents in soil is important for regional risk assessment and management. The main objective of the present study was to analyse the concentrations of metals in soils in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo). Genetic variation of plant populations was investigated to assess the potential impact of metal contamination on forest sustainability. The levels of copper, cobalt, zinc, arsenic, and lead were significantly higher (up to 200-fold) in mining sites in the Lubumbashi compared to the most highly contaminated Sudbury sites. The nickel content in soil samples from Lubumbashi was much lower compared to Sudbury region samples. Only 3.5% and 4 % of total copper and nickel, respectively, were phytoavailable, with values of 6%, 5.7%, 3.6%, and 5.4% for cobalt, magnesium, manganese, and zinc, respectively. There were significant positive correlations between total metal and phytoavailable metal concentrations for copper (r=0.99), nickel (r=0.86), cobalt (r=0.72), strontium (r=0.71), and zinc (r=0.66). Although genetic variation was high in Picea glauca populations from the Sudbury region, no association was found between metal contamination levels and genetic variation within and among the P. glauca populations.     

Effect of Zinc Oxide nanoparticles on cellular oxidative stress and antioxidant defense mechanisms in mouse liver

Zinc oxide nanoparticles (ZnO₂), a common ingredient of cosmetics has a huge variety of applications. Previous studies reported oxidative stress mediated toxicity of ZnO₂ nanoparticles on various mammalian cell lines. Although zinc (Zn) is an essential mineral at higher concentrations this metal is toxic. The present study focused on size determination by monitoring changes in activities of antioxidant defense mechanism in response to oxidative stress induced by ZnO₂ nanoparticles using mouse liver tissue homogenates. The study also investigated effects of oxidative stress induced DNA damage by determining formation of 8-OHdG in mouse liver homogenate. A cytotoxicity assay was also carried out in L929 cells to determine cell viability. The results of the study indicated that 50μg/ml of ZnO₂ nanoparticles induced 50% cell death. Alterations in antioxidant parameters and 8-OHdG were also noted. Data showed that there was a concentration-dependent fall in cell viability, decrease antioxidant enzyme levels and increase formation of DNA adduct (8-OHdG) when mouse liver tissue homogenate were exposed to ZnO₂ nanoparticles.     

植物吸收修复对土壤镍及其主要化学性质的影响

采用室内盆栽试验方法,研究了外源镍污染土壤的植物吸收修复对土壤镍形态和土壤主要化学性质的影响。试验用水稻土添加NiSO4·6H2O(100～1600mgkg-1)经过12周的驯化培养后,种植了镍超累积植物Alyssu mmurale,110 d后收获植物并进行了试验土壤镍的形态和主要化学性质的分析,采用再分配系数和结合强度系数对植物修复效果进行了定量分析。结果表明,根区土壤中DTPA提取态镍的数量明显减少,根区土壤DTPA-Ni与非根区土壤DTPA-Ni之比的范围在0.33～0.61之间。每盆植物提取镍量为6.61～31.18mg,植物提取量随着添加镍量增加而增加,地上部分最大镍含量达到12454.1mgkg-1。根区的再分配系数在2.17～4.19之间,而非根区的再分配系数在6.87～15.91之间,再分配系数随着镍添加量的增加而增大;根区的结合强度系数为0.84～0.39,而非根区的则为0.88～0.26,随着土壤中镍添加量的增加,结合强度系数逐渐减小。植物吸收修复后,根区土壤镍的再分配系数降低、结合强度系数增大,表明土壤镍各形态之间的稳定性增加,因此植物修复可以加快外源镍在土壤中的稳定。试验结果也表明,根区土壤中pH随着镍添加量的增加呈下降趋势、但较非根区土壤的高;根区土壤有机碳亦较非根区的高。     

Reduction of availability of trace metals in urban soils using inorganic amendments

Urban soils in medium- and large-sized cities generally have shown elevated contents of environmentally important trace metals (e.g. lead, copper, zinc). Such high concentrations in soils of green areas, mainly recreational areas, can be a source of potentially toxic elements and pose a risk for human health. Thus the availability of these contaminants is an essential control parameter, as it indicates potential plant uptake and their transfer to humans via inhalation of suspended dust, or direct ingestion (i.e. hand to mouth pathway), or consumption of contaminated foodstuff. Young children are the most sensitive segment of the population. Addition of amendments to the soil is a feasible technique to reduce the availability of trace metals. Accordingly, four urban soils of green areas of Seville (Spain), with relatively high lead contents and moderate copper and zinc contents, were amended in the laboratory with four inorganic materials [acid zeolite (AZ), sodium zeolite (SZ), Slovakite (SL), apatite (AP)], at two rates (1%, 5% w/w) and incubated for 1 year. Significant decreases in EDTA-extractable metal contents were observed in some of the treatments after adding the amendments even before the incubation begun, mainly for SL treatments. The amendment that produced the longest lasting immobilisation effect, compared to control treatments, was AZ at the higher rate. The effects of SZ and SL tended to decrease with time, while the AP effect was almost negligible after 3 months of ageing. This study confirms the feasibility of using certain inexpensive soil amendments to at least temporarily immobilise metals in urban soils for the purpose of protecting human health, especially that of young children.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

4种典型纳米材料对小鼠胚胎成纤维细胞毒性的初步研究

为探讨不同种类纳米材料对原代培养小鼠胚胎成纤维细胞(Mouse embryo fibroblasts,MEF)的毒性效应及作用机制,选择4种典型的纳米材料(纳米碳、单壁碳纳米管、纳米氧化锌、纳米二氧化硅)制备颗粒悬液,设立5个剂量组(5、10、20、50、100μg·mL-1)对BALB/c小鼠MEF细胞进行24、48、72h染毒培养,利用细胞形态学观察和噻唑蓝实验(MTT比色法)检测上述4种纳米材料对MEF细胞活性的影响,同时,测定染毒24h后细胞培养液上清中乳酸脱氢酶(LDH)活性以探讨纳米颗粒对细胞膜完整性的影响.结果显示:1)4种纳米材料均能明显影响MEF细胞的生长形态.染毒24h后,MEF细胞发生不同程度的回缩变形,细胞间隙增大,排列稀疏,胞内颗粒物增多,细胞透明度下降.2)纳米碳、纳米氧化锌、纳米二氧化硅对MEF细胞增殖的抑制作用和对细胞膜完整性的损伤作用均随染毒剂量的升高而增强,具有明显的剂量-效应关系,其半数致死浓度(24h-IC50)分别为21.85、21.94、461.10μg·mL-1;碳纳米管组的剂量-效应之间不呈对数线性关系,未能得出其24h-IC50.3)在不同染毒剂量水平上,4种纳米材料的毒性对比差异显著:低剂量水平上纳米碳与碳纳米管的毒性强于纳米氧化锌和纳米二氧化硅,随着剂量的升高纳米氧化锌的细胞毒性升高最为显著.结果提示,纳米材料能够对MEF细胞造成毒性损伤,破坏细胞膜的完整性可能只是作用途径之一;纳米材料的毒性可能受粒径、形状、化学组成等许多因素的影响.     

Oral bioaccessibility of metals in an urban catchment,Newcastle upon Tyne

The metal content was determined in soils from a former, historic, contaminated land site and now a ‘green’ public open space in N.E. England. Using a systematic sampling grid approach, 32 soil samples were taken from locations across the site and analyzed for six potentially toxic elements (Cd, Cr, Cu, Ni, Pb, and Zn). Initially, the pseudo-total metal content of the soils was determined using acid digestion followed by inductively coupled plasma mass spectrometry analysis. This data was evaluated against published soil guideline value (SGV) and generic assessment criteria (GAC) values; it was found that 21% (i.e., 41 samples) exceeded the stated lower values. The data was then compared to the oral bioaccessibility of the soils, which was assessed by an in-vitro gastrointestinal extraction procedure. The results, determined as the % BAF, indicated that overall bioaccessibility was low (<10% BAF) for all the elements studied; the exception was Cd. Given that SGV/GAC values are based on generic land-use categories and not a public open space, as investigated in this work, further work is recommended on developing a qualitative risk assessment at the site to estimate the risks posed to human health via the direct and indirect soil ingestion pathway.     

紫花苜蓿改良盐渍土对土壤微生物活性和养分含量的影响

为探讨干旱地区种植紫花苜蓿改良盐渍土对土壤微生物生物量及其活性和土壤养分的影响,选择河西走廊黑河流域国有临泽农场的草甸盐土荒地作为对照,研究了种植紫花苜蓿2、3、4年后的改土效果。结果表明：与CK相比,连续种植4年后,所测定的土壤化学性质和微生物化学性质指标都发生了极显著（P〈0.01）的有利变化,电导率下降5.96 mS.cm-1,pH下降0.25,有机碳增加1.50 g.kg-1,微生物生物量碳增加48.93 mg.kg-1,微生物熵上升0.43%,荧光素二乙酸酯水解率提高10.87μg.g-1.h-1,碱解氮增加17.37 mg.kg-1,速效磷增加2.87 mg.kg-1,速效钾增加44.93 mg.kg-1。相关分析表明,微生物生物量碳、微生物熵、荧光素二乙酸酯水解率、碱解氮、速效磷、速效钾与土壤有机碳之间极显著（P〈0.01）正相关,相关系数分别为0.86、0.80、0.87、0.85、0.79、0.80,而与电导率之间极显著（P〈0.01）负相关,相关系数分别为-0.83、-0.79、-0.84、-0.86、-0.88、-0.78。研究认为,种植紫花苜蓿对草甸盐土有显著的改良效果,电导率下降,有机碳含量提高,微生物活性增强,速效养分含量增加。     

干旱区绿洲灌漠土Cu、Zn和Pb的吸附解吸特征

土壤重金属吸附解吸是影响土壤系统中重金属移动性和归宿的主要过程,影响重金属的生物有效性以及重金属在食物链中的传递等.配制一系列不同浓度的重金属,灌漠土对重金属溶液进行吸附实验24 h以达到平衡,再用硝酸铵和乙酸铵进行解吸实验24 h以达到平衡.利用热力学吸附平衡法,对西北干旱区绿洲灌漠土重金属Cu、Ni和Pb的吸附解吸行为进行序批实验研究.实验结果表明:(1)灰漠土在常温下对铜、锌和铅重金属离子的吸附等温线符合Freundlich型吸附模式,灰漠土对重金属铜、锌和铅的吸附能力由强到弱的顺序为:铅,铜,锌.(2)硝酸铵和乙酸铵解吸重金属的量与灰漠土吸附重金属量呈现出线性正相关,乙酸铵解吸重金属的量比硝酸铵解吸重金属的量大,两种解吸剂对铜、锌和铅重金属离子的解吸能力由大到小的顺序都为:铜,锌,铅,说明了一般外源的铜、锌和铅进入土壤以后,铜和锌可能比铅容易向四周转移.(3)硝酸铵和乙酸铵的解吸率呈谷形曲线,开始时硝酸铵和乙酸铵解吸重金属量的百分比随灰漠土吸附重金属量的增加而减小,在吸附量达到某一特定值时,解吸率随吸附量的增加而增加.灰漠土对铜、锌和铅的吸附作用以专性吸附为主,被灰漠土吸附的铜、锌和铅重金属离子较难解吸.     

Baseline zinc content of soils and plants in Poland

Topsoils from Poland were analysed for total and extractable zinc, and for a range of major elements and selected soil properties. Plant samples from the same locations were also analysed for zinc content. The geometric mean concentrations of zinc in samples were (mg/kg dry weight): soil total-Zn, 45.9; soil extractable-Zn 3.1; grass, 30.0; dandelion-tops, 45.9; dandelion-roots, 23.2; oat-leaves, 20.0; oat-grains, 29.7; lichens, 111.5. Significant relationships were found for zinc in grass and extractable-Zn in soils as well as for zinc in lichens and both total and extractable Zn in soils. Zinc in soils varied for soil kinds and regions.     

腐殖酸存在下镉和铅对土壤脱氢酶活性的影响

采用室内培养试验研究Cd和Pb污染红壤添加不同组分腐殖酸后,其脱氢酶活性的变化,结果表明,红壤遭受镉和铅污染后,脱氢酶活性显著降低,然而腐殖酸特别是胡敏酸的存在能够使脱氢酶活性得到显著回升,说明腐殖酸与重金属的相互作用对重金属污染土壤微生物活性的改善和修复功能,对土壤有一定的去污降毒作用.不同腐殖酸组分的效应大小为:灰色胡敏酸(GHA)>棕色胡敏酸(BHA)>富里酸(FA),表明分子量愈大、芳构化程度愈高的腐殖酸组分,其对重金属的钝化愈强,从而解除土壤重金属对生物毒害的能力愈强.     

中国东部花岗岩、玄武岩及石灰岩上土壤微量元素含量的纬向分异

在中国东部花岗岩、玄武岩和石灰岩地区布设91个采样点,采集土壤剖面和母岩样品,测试13种微量元素的含量,研究其纬向分异规律及影响因素。结果表时：（1）土壤微量元素含量顺序为：玄武岩土壤＞石灰岩土壤＞花岗岩土壤;（2）花岗岩和玄武岩上土壤微量元素含量与母岩接近,石灰岩上土壤微量元素含量远高于母岩;（3）花岗岩上土壤微量元素的含量由北向南呈降低趋势,而玄武岩和石灰岩上土壤微量元素含量由北向南均呈增高趋势,且与游离氧化铁含量的增高同步;（4）微量元素含量与氧化铁含量在玄武岩土壤中的相关性大于这两者在花岗岩土壤中的相关性。