Bacterial stimulation of copper phytoaccumulation by bioaugmentation with rhizosphere bacteria

Copper contaminated areas pose environmental health risk to living organisms. Remediation processes are thus required for both crop production and industrial activities. This study employed bioaugmentation with copper resistant bacteria to improve phytoremediation of vineyard soils and copper mining waste contaminated with high copper concentrations. Oatmeal plant (Avena sativa L.) was used for copper phytoextraction. Three copper resistant bacterial isolates from oatmeal rhizosphere (Pseudomonas putida A1; Stenotrophomonas maltophilia A2 and Acinetobacter calcoaceticus A6) were used for the stimulation of copper phytoextraction. Two long-term copper contaminated vineyard soils (Mollisol and Inceptisol) and copper mining waste from Southern Brazil were evaluated. Oatmeal plants substantially extracted copper from vineyard soils and copper mining waste. As much as 1549 mg of Cu kg?1 dry mass was extracted from plants grown in Inceptisol soil. The vineyard Mollisol copper uptake (55 mg Cu kg?1 of dry mass) in the shoots was significantly improved upon inoculation of oatmeal plants with isolate A2 (128 mg of Cu kg?1 of shoot dry mass). Overall oatmeal plant biomass displayed higher potential of copper phytoextraction with inoculation of rhizosphere bacteria in vineyard soil to the extent that 404 and 327 g ha?1 of copper removal were respectively observed in vineyard Mollisol bioaugmented with isolate A2 (S. maltophilia) and isolate A6 (A. calcoaceticus). Results suggest potential application of bacterial stimulation of phytoaccumulation of copper for biological removal of copper from contaminated areas.     

Desorption of copper and cadmium from soils enhanced by organic acids

The adsorption/desorption behavior of copper and cadmium on soils was investigated in this study. The adsorption isotherm of copper and cadmium conformed to Langmuir equation better than Freundlich equation. The effect of ionic strength, pH, and organic acid, including ethylenediamine tetraacetic disodium acid salt (EDTA), citric acid, oxalic acid and tartaric acid, on the desorption of copper and cadmium was studied. The desorption of copper and cadmium increased with the increase of ionic strength, while the desorption decreased with the rise of pH. The desorption of copper and cadmium enhanced by organic acids was influenced by pH. EDTA showed excellent enhancement on the desorption of both copper and cadmium; citric acid demonstrated great enhancement on the desorption of copper but negligible enhancement on the desorption of cadmium; oxalic acid enhanced the desorption of copper only at pH around 6.4 and enhanced the desorption of cadmium in the pH range from 6.4 to 10.7; tartaric acid slightly enhanced the desorption of copper but negligibly enhanced the desorption of cadmium. The desorption mechanism in the presence of organic acids were explained as the competition of complexation, adsorption and precipitation. The net effect determined the desorption efficiency. This study provided guidance for the selection of organic acids to enhance the electrokinetic (EK) remediation of copper and cadmium from contaminated soils.     

Influence of growth form on the accumulation of airborne copper by lichens

Lichens are known to accumulate airborne elements. This characteristic makes them useful as biomonitors of air quality. However, direct correlations of element concentrations in the air with element concentrations in lichen thalli are generally unavailable. The purpose of this study was to quantitatively examine the relationship between concentrations of copper in ambient air samples and thalli of foliose and fruticose lichens. Lichen samples from four sites along an air copper gradient were collected and analyzed. Foliose specimens consistently accumulated more than twice as much copper as fruticose specimens at all four sites. The relationship between copper concentrations in foliose and fruticose lichens and ambient air samples along an airborne copper gradient was examined using a stepwise regression model. An R² value of (0.84) and an F-statistic of (182.5, p<0.001) for the model indicate that variability in lichen copper concentrations between sites is explained by airborne copper concentrations. Based on the regression analysis both foliose and fruticose growth forms appear to accurately predict airborne copper concentrations. A significant interaction between the airborne copper and growth form variables and large differences in the calculated slopes suggests that foliose lichens more efficiently accumulate airborne copper than fruticose lichens.     

Copper-binding efficacy of water-soluble chitosans: characterization by aqueous binding isotherms

The major objective of the study is to measure directly the isotherms of copper binding onto soluble chitosan preparations, using ion-selective electrode technique. Copper uptake is found to decrease strongly when chitosan acetylation degree or chitosan concentration increased. When relating the bound copper concentrations to content of non-acetylated amine groups in a chitosan, differences between copper uptake on different chitosan preparations become reduced but not disappear. Other effects, in addition to the contents of non-acetylated amine groups, can involve differences in the copper binding by different chitosans. Due to isotherm non-linearity, the distribution coefficient K(d) of copper between a water-soluble chitosan and an aqueous solution may vary by two orders of magnitude as the free copper concentration C(free) varied. Linear relation between logK(d) normalized by free amine group content of chitosans and logC(free) may help in preliminary estimating of the copper binding by water-soluble chitosans at a certain pH.     

Relationship between copper speciation in sediments and bioaccumulation by marine bivalves of Taiwan

This paper evaluates the relationships between copper species in sediments and accumulation by the purple clam (Hiatula diphos) and venus clam (Gomphina aeguilatera) collected from the field and culture (aquaculture) ponds in the polluted coastal area of Lukang, Taiwan. Sediment was sampled along with the molluscs, including oysters (Crassostrea gigas), purple clams (Hiatula diphos), rock-shells (Thais clavigera), venus clams (Gomphina aeguilatera), and hard clams (Meretrix lusoria), from two unique environments of Lukang during the period from August 1993 to July 1994. The data indicate that the total copper concentrations in sediments from culture ponds (185 microg g(-1)) was higher than those of the field (44.0 microg g(-1)). Copper species in sediments were analyzed by a sequential leaching technique. Results show that concentrations of various copper species in the sediments are in the range of 1.14 +/- 0.59 to 13.2 +/- 22.4 microg g(-1) and 0.36 +/- 0.24 to 133 +/- 36.7 microg g(-1) for the two environments, respectively. Also the exchangeable copper in sediment from culture ponds was 15 times higher than that from the field. In addition, the sum of exchangeable and copper carbonates had the highest percentages of copper in both the pond sediment (86.6 %) and the field sediment (50.7 %). Maximum copper concentrations (309 +/- 35.1 microg g(-1)) in oysters were much higher than those in the other benthic organisms by about 4-127 times. Similarly, the data also showed that copper concentrations in Thais clavigera were 12-32 times higher than those in other benthic organisms. Copper concentrations in various benthic organisms differed significantly (p < 0.05) from that in Thais clavigera. This capacity makes Thais clavigera a potential candidate for monitoring copper in marine sediments. In terms of copper species, the best correlation was generally obtained between copper carbonates in sediments and copper concentrations in Hiatula diphos (r = 0.886*). A strong multiple regression correlation (p < 0.05, r2 = 0.7894) also indicates that the copper carbonates may dominate as the available form of copper to Hiatula diphos from various environments in the Lukang coastal area under natural physicochemical conditions.     

Depuration of copper and zinc by green oysters and blue mussels of Taiwan

This paper describes depuration processes of copper and zinc in green oysters (Crassostrea gigas) and in blue mussels (Mytilus smarangdium) collected from an environment with heavy copper contamination, and then transferred to natural clean seawater. Results show that the total loss of copper content per oyster is an exponential function of exposure time for the first 6 days with a depuration rate of 351 microg g(-1) day(-1) and then levels off. During this exponential decrease period approximately 67% of the copper accumulated in green oysters was depurated. However, when the copper contents in the oysters decreased from 2225 +/- 111 microg g(-1) to 344 +/- 18.7 microg g(-1) the depuration rates decreased from 245 microg g(-1) day(-1) to 0.08 microg g(-1) day(-1). This means that green oysters had a 16-fold higher copper depuration rate (351 microg g(-1) day(-1)) than normal oysters (21.5 microg g(-1) day(-1)) for the first 6 days. However, the depuration of accumulated copper and zinc by the mussels was a fast process in natural clean seawater. About 91% of the accumulated copper was lost during the first 6-day period; copper contents declined from 20.2 +/- 3.41 microg g(-1) to 1.80 +/- 0.21 microg g(-1). Only 36% of the accumulated zinc was lost during a depuration period of 6 days. Calculations show that the biological half-lives of copper in green and normal oysters were 11.6 and 25.1 days, respectively. The biological half-lives of zinc in green and normal oysters were 16.7 and 30.1 days, respectively. In spite of the relatively low initial copper content in blue mussels being 20.2 +/- 3.41 microg g(-1), the biological half-life is only 6.40 days. From these results it is important to emphasise that the fastest turnover rate is for copper in blue mussels. However, zinc is more retentive in blue mussels than copper.     

紫外催化湿式双氧水氧化处理化学镀铜废液

利用化学镀铜废液自身含有的铜作为催化剂,应用紫外催化湿式双氧水氧化工艺处理化学镀铜废液取得了良好效果。通过单因素实验确定的推荐工艺条件为：pH=2.0（保持原始值不变）;不额外投加铜催化剂;H₂O₂用量为2倍理论量。在此条件下处理化学镀铜废液180 min,COD去除率可达到96.6%;之后采用沉淀法回收铜,调节处理后废水pH到9.5,铜的回收率可达到99.8%。     

铜氰溶液的电子束辐照降解

研究了铜氰溶液中总氰初始浓度、pH、铜浓度等对总氰降解效率的影响,比较了KCN溶液和铜氰溶液的总氰降解率,初步推断了铜氰溶液在辐照过程中的降解机制.实验结果表明,在同样的辐照剂量下,随着总氰初始浓度的增加,总氰降解率降低,相应的总氰降解G值增大;铜浓度越低,总氰降解率越高;pH越小的铜氰溶液总氰降解率越高.电子束辐照KCN溶液和铜氰溶液的总氰降解反应属于表观一级反应.在相同的辐照剂量下,KCN溶液的总氰降解率比铜氰溶液要高得多.铜氰溶液的电子束辐照降解过程非常复杂,主要是铜氰络合离子逐步离解出的CN-与·OH的反应.     

Monitoring heavy metal pollution by aquatic plants

Introduction

The copper bioaccumulation by the floating Lemna minor and by the completely submerged Ranunculus tricophyllus as a function of exposure time and copper concentration was studied, with the aim of proposing these species as environmental biosensors of the water pollution.

Results

The results show that both these aquatic angiosperms are good indicators of copper pollution because the copper uptake is the only function of metal concentration (water pollution).

Conclusion

Uptake behavior is reported as a function of the time and concentration, based on the results of a 3-year study. Kinetic evaluations are proposed.     

高岭土模拟铜污染土壤电动力学修复

采用电动力学方法修复重金属污染土壤。研究中采用高岭土模拟铜污染土壤,结合电动力学修复理论,考察了不同电压、添加络合剂条件下铜的修复效果。结果表明,当电压强度为0．5V／cm时,最靠近阴极部分的土壤中Cu^2＋的C／C。为1．596,当电压强度为1V／cm时,C／C0为2．245,说明适当提高电压强度能够有效的增加Cu^2＋的迁移效果;土壤中未加入络合剂时,Cu^2＋大部分集中在第5段土壤中,C／C0为1．339,在土壤中加入络合剂以后Cu^2＋大部分集中在靠近阴极部分的土壤中,C／C。为1．716,说明在污染土壤中加入一定量的络合剂可以与Cu^2＋结合生成螯合物,提高Cu^2＋的迁移效果。     

化学修饰碳糊电极测定废水中痕量铜

研制了732型阳离子交换树脂碳糊修饰电极,在盐酸－乙二胺体系中,对Cu（Ⅱ）显示出良好的离子交换和选择性,电极具有很好的重现性和较长的使用寿命,可用于废水中痕量铜的测定。     

Green oysters caused by copper pollution on the Taiwan coast

The first case of green oysters (Crassostrea gigas) broke out along the Charting mariculture area of south-western Taiwan in January 1986. The green color was found to be due to high copper content in the oyster tissue. Since then, a long-term survey around this area shows that total dissolved copper ranges from 4.99 to 23.6 microg/liter and particulate copper ranges from 1.09 to 5.51 microg/liter in sea-water. The green oysters collected from the Erhjin Chi estuary on 26 January, 1989 gave the highest copper content, 4401+/-79 ppm dry wt. Other green oyster cases were occasionally observed in the Hsiangsan and Anpin mariculture areas. Meanwhile, an experiment of copper accumulation in oysters was conducted at three stations (south-western Taiwan) for up to 90 days. Multiple regression analysis indicates that the food pathway may predominate in copper accumulation by green oysters. This bioaccumulation experiment shows that the total uptake of copper per oyster is an exponential function of exposure time for the first 2 weeks with an accumulation rate of 214 ppm Cu/day and then levels off. The average values of concentration factors for oysters (about 5 x 10(5)) were very close to steady-state values under the natural conditions at each station.     

Sorption of copper and nickel by spent animal bones

Animal bone is able to adsorb copper and nickel ions from their single aqueous solutions. It was noted that a decrease in the sorbent concentration with constant copper or nickel concentration, or an increase in the copper or nickel concentration with a constant sorbent concentration resulted in a higher metal loading per unit weight of the sorbent. Increase in the initial pH of the metal solution resulted in an increase in the metals uptake per unit weight of the sorbent. Freundlich isotherm model was found to be applicable for the experimental data of Cu2+ and Ni2+. The results showed that animals bones can be used for the adsorption of the Cu2+ and Ni2+ with higher affinity toward Cu2+ ions. The new sorbent was able to decrease copper concentration to a limit lower than the limit permitted by the environmental regulations.     

Removal of metal ions and humic acid from water by iron-coated filter media

Iron oxide is an excellent, regenerable adsorbent, and often controls free metals through adsorption reaction. The utilization of heating process for coating iron oxide on sand surface allowed the media to be used in a packed column. Iron-coated sand was investigated for adsorbing metal ions and natural organic matter from water by batch and column experiments. Chemical analysis (energy dispersive analysis of X-ray, EDAX) was used for characterizing the copper and lead adsorption sites on iron-coated sand. From the batch experiment results, the copper and lead ions could be removed simultaneously by the iron-coated sand in the competition adsorption system. The interaction between copper, lead ions and iron oxide on sand surface was primarily the chemical bonds. The maximum adsorption capacities of iron-coated sand for copper and lead were 0.259 mg Cu/g-sand and 1.211 mg Pb/g-sand, respectively. The presence of humic acid led to increase the adsorption of copper and lead. Results from column experiments indicated that the copper ions, lead ions and humic acid could be removed completely before the breakpoint. Consequently, the iron-coated sand may be applied for the adsorption/filtration of metal ions and natural organic matters from water.     

Incorporating bioavailability into management limits for copper in sediments contaminated by antifouling paint used in aquaculture

Although now well embedded within many risk-based sediment quality guideline (SQG) frameworks, contaminant bioavailability is still often overlooked in assessment and management of contaminated sediments. To optimise management limits for metal contaminated sediments, we assess the appropriateness of a range methods for modifying SQGs based on bioavailability considerations. The impairment of reproduction of the amphipod, Melita plumulosa, and harpacticoid copepod, Nitocra spinipes, was assessed for sediments contaminated with copper from antifouling paint, located below aquaculture cages. The measurement of dilute acid-extractable copper (AE-Cu) was found to provide the most useful means for monitoring the risks posed by sediment copper and setting management limits. Acid-volatile sulfide was found to be ineffective as a SQG-modifying factor as these organisms live mostly at the more oxidised sediment water interface. SQGs normalised to %-silt/organic carbon were effective, but the benefits gained were too small to justify this approach. The effectiveness of SQGs based on AE-Cu was attributed to a small portion of the total copper being present in potentially bioavailable forms (typically <10% of the total). Much of the non-bioavailable form of copper was likely present as paint flakes in the form of copper (I) oxide, the active ingredient of the antifoulant formulation. While the concentrations of paint-associated copper are very high in some sediments, as the transformation of this form of copper to AE-Cu appears slow, monitoring and management limits should assess the more bioavailable AE-Cu forms, and further efforts be made to limit the release of paint particles into the environment.     

氧化亚铁硫杆菌浸出线路板中铜的研究

从煤堆积水中分离得到氧化亚铁硫杆菌，利用该菌种对线路板中的铜进行了浸出实验。研究了不同线路板粉末添加量对浸出效果的影响，观察了浸出过程中pH和氧化还原电位（Eh）的变化，结果表明添加量为10g／L和20g／L时，在15d内线路板Cu几乎全部浸出，而50g／L和100g／L在15d内亦有较高的浸出效率，并呈持续上升趋势。     

氧化亚铁硫杆菌浸出线路板中铜的研究

从煤堆积水中分离得到氧化亚铁硫杆菌,利用该菌种对线路板中的铜进行了浸出实验.研究了不同线路板粉末添加量对浸出效果的影响,观察了浸出过程中pH和氧化还原电位(Eh)的变化,结果表明添加量为10 g/L和20 g/L时,在15 d内线路板Cu几乎全部浸出,而50g/L和100g/L在15 d内亦有较高的浸出效率,并呈持续上升趋势.     

Growth inhibition of bloom forming cyanobacterium Microcystis aeruginosa by green route fabricated copper oxide nanoparticles

The cyanobacterium Microcystis aeruginosa can potentially proliferate in a wide range of freshwater bionetworks and create extensive secondary metabolites which are harmful to human and animal health. The M. aeruginosa release toxic microcystins that can create a wide range of health-related issues to aquatic animals and humans. It is essential to eliminate them from the ecosystem with convenient method. It has been reported that engineered metal nanoparticles are potentially toxic to pathogenic organisms. In the present study, we examined the growth inhibition effect of green synthesized copper oxide nanoparticles against M. aeruginosa. The green synthesized copper oxide nanoparticles exhibit an excitation of surface plasmon resonance (SPR) at 270 nm confirmed using UV–visible spectrophotometer. The dynamic light scattering (DLS) analysis revealed that synthesized nanoparticles are colloidal in nature and having a particle size of 551 nm with high stability at ?26.6 mV. The scanning electron microscopy (SEM) analysis shows that copper oxide nanoparticles are spherical, rod and irregular in shape, and consistently distributed throughout the solution. The elemental copper and oxide peak were confirmed using energy dispersive x-ray analysis (EDAX). Fourier-transform infrared (FT-IR) spectroscopy indicates the presence of functional groups which is mandatory for the reduction of copper ions. Besides, green synthesized copper oxide nanoparticles shows growth inhibition against M. aeruginosa. The inhibition efficiency was 31.8 % at lower concentration and 89.7 % at higher concentration of copper oxide nanoparticles, respectively. The chlorophyll (a and b) and carotenoid content of M. aeruginosa declined in dose-dependent manner with respect to induction of copper oxide nanoparticles. Furthermore, we analyzed the mechanism behind the cytotoxicity of M. aeruginosa induced by copper oxide nanoparticles through evaluating membrane integrity, reactive oxygen species (ROS), and mitochondrial membrane potential (Δψm) level. The results expose that there is a loss in membrane integrity with ROS formation that leads to alteration in the Δψm, which ends up with severe mitochondrial injury in copper oxide nanoparticles treated cells. Hence, green way synthesized copper oxide nanoparticles may be a useful selective biological agent for the control of M. aeruginosa.     

Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin

Nanoscale zerovalent copper supported on a cation resin was successfully synthesized to enhance the removal of carbon tetrachloride (CCl(4)) from contaminated water. The use of the cation resin as a support prevents the reduction of surface area due to agglomeration of nanoscale zerovalent copper particles. Moreover, the cation resin recycles the copper ions resulting from the reaction between CCl(4) and Cu(0) by simultaneous ion exchange. The decline in the amount of CCl(4) in aqueous solution results from the combined effects of degradation by nanoscale zerovalent copper and sorption by the cation resin; thus the amount of CCl(4) both in aqueous solution and sorbed onto the resin were measured. The pseudo-first-order rate constant normalized by the surface-area and the mass concentration of nanoscale zerovalent copper (k(SA)) was 2.1+/-0.1 x 10(-2)lh(-1)m(-2), approximately twenty times that of commercial powdered zerovalent copper (0.04 mm). Due to the exchange between Cu(2+) and the strongly acidic ions (H(+) or Na(+)), the pH was between 3 and 4 in unbuffered solution and Cu(2+) at the concentration of less than 0.1 mg l(-1) was measured after the dechlorination reaction. In the above-ground application, resin as a support would facilitate the development of a process that could be designed for convenient emplacement and regeneration of porous reductive medium.     

Biodegradable chelate enhances the phytoextraction of copper by Oenothera picensis grown in copper-contaminated acid soils

Oenothera picensis plants (Fragrant Evening Primrose) grow in the acid soils contaminated by copper smelting in the coastal region of central Chile. We evaluated the effects of the biodegradable chelate MGDA (methylglycinediacetic acid) on copper extraction by O. picensis and on leaching of copper through the soil profile, using an ex situ experiment with soil columns of varying heights. MGDA was applied in four rates: 0 (control), 2, 6 and 10 mmol plant⁻¹. MGDA application significantly increased biomass production and foliar concentration, permitting an effective increase in copper extraction, from 0.09 mg plant⁻¹ in the control, to 1.3 mg plant⁻¹ in the 6 and 10 mmol plant⁻¹ treatments. With 10 mmol plant⁻¹ rate of MGDA, the copper concentration in the leachate from the 30 cm columns was 20 times higher than in the control. For the 60 cm columns, copper concentration was 2 times higher than the control. It can be concluded that at increased soil depths, copper leaching would be minimal and that MGDA applications at the studied rates would not pose a high risk for leaching into groundwater. It can thus be stated that applications of MGDA are an effective and environmentally safe way to improve copper extraction by O. picensis in these soils.