Removal behavior and mechanisms of cadmium and lead by coupled ethylenediaminetetraacetic acid washing and electrochemical reduction: influence of current conditions.

Ethylenediaminetetraacetic acid (EDTA) washing has been used extensively to remediate heavy metal-contaminated soils. Electrochemical reduction treatment of spent washing solution is an effective method of EDTA regeneration. However, at present, these two technologies are usually regarded as two independent treatment processes. This research raised a new heavy metal-contaminated soil treatment strategy-a combination technique of coupled EDTA washing and electrochemical reduction. We speculated that the combination of EDTA washing and electroreduction treatment could improve the efficiency of Cd and Pb removal from contaminated soil. In this study, the removal performance and mechanisms of Cd and Pb under different current conditions were investigated based on a coupling of EDTA washing and electrochemical reduction. The combination technique can increase Cd and Pb removal efficiencies by 13.37-15.24% and 14.91-27.05%, respectively, compared with EDTA washing alone. Sequential extraction analysis showed that the reducible fraction improved metal removal efficiency. The percentage of metal removed increased with an increased current value and EDTA concentration. In addition, pulse current mode removed more Cd and Pb than continuous current, although the difference was not significant (p > 0.05). However, pulse current could effectively eliminate the cathodic hydrogen evolution reaction, resulting in a further heavy metal deposition at the cathode. The combination technique exhibited enhanced removal efficiency due to EDTA regeneration in the suspension and the cathodic reduction reaction. The most cost-effective treatment in 48 h was a pulse current mode of 32 min on/16 min off-32 mA-EDTA-10 mM, where 47.56% of Cd and 77.00% of Pb were removed from the soil with an electric energy consumption of 8.24 Wh.

Two-compartment membrane electrochemical remediation of heavy metals from an aged electroplating-contaminated soil: A comparative study of anodic and cathodic processes.

In this study, two-compartment membrane electrochemical remediation (MER) based on the anode process and the cathode process strategies were compared for treating a multi metal -contaminated soil. Remediation effect, as well as energy consumption and risk evaluation of the two strategies under different current density conditions of electroplating-contaminated soil suspension were performed, the following conclusions were drawn. MERs based on both the anode and cathode processes exhibited a synergetic effect because the DC electric field and extractants dissolved more metals from the soil phase into the liquid phase of the suspension compared to a usual soil washing treatment. The maximum Cr, Cu, and Ni removal efficiencies of MERs based on the anode process were 79.5%, 86.2%, and 85.0%, respectively, compared to 27.5%, 72.5%, and 65.9% based on the cathode process. Risk assessment results showed lower soil environmental risk after MER based on the cathode process than after MER based on the anode process. In this study, MER based on the cathode process as an evolving soil remediation strategy was found to present high simultaneous remediation ability for soil heavy metals and leaching materials, showing its advantages of environmental friendliness and economic effectiveness.

The Forms, Distribution, and Risk Assessment of Sulfonamide Antibiotics in the Manure-Soil-Vegetable System of Feedlot Livestock.

Manure, soil, and vegetable samples were collected from different-sized livestock farms in Xinxiang, China. The residues of sulfadiazine, sulfamonomethoxine, and sulfamethoxazole were analyzed by high-performance liquid chromatography. The results indicated that the concentration ranges of the three total sulfonamides in manure, soil, and vegetables were 10.13-566.23 µg kg-1, 7.60-176.26 µg kg-1, and 0-32.70 µg kg-1, respectively. The mean concentrations were 219.71 µg kg-1, 70.73 µg kg-1, and 7.08 µg kg-1 for manure, soil, and vegetables, respectively. The mean concentrations in soil were lower than the ecotoxic effect trigger value (100 µg kg-1), indicating a low risk for organisms in soil. The concentrations of the three sulfonamides varied significantly in different types of vegetables and all were lower than the acceptable daily intake value (50 µg (kg day)-1). However, the potential ecotoxicity and danger to human and animal health via accumulation of the antibiotic in the food chain cannot be ignored.

Isotope-based water-use efficiency of major greening plants in a sponge city in northern China.

To tackle urban water issues, the Chinese government has promoted the construction of sponge cities in recent years. Thirty cities have been designated as experimental sites to serve as models for future sponge city construction, as more than 80% of the built-up urban areas in China must reach the standards of sponge cities by 2030. Greening plants play an important role in sponge cities, and water-use efficiency (WUE) is a vital index to determine whether plants could adapt to and grow healthily in environments with water deficits. In this study, WUE of greening plants was quantified by measuring the stable carbon isotope fractionation. Suitable plants for the green spaces in Guyuan sponge city, in northern China, were selected based on their WUE, and the main factors affecting WUE were studied in four habitats within the city. Plant species identity had the greatest effect on WUE, while habitat and plant life form had lower effect, illustrating that WUE is a relatively stable and reliable index for the classification of plant species. We can improve the WUE and ecological function of green spaces in sponge cities by using isotope technology to select suitable plant species with high WUE. To our knowledge, this study is the first to select plant species for sponge city by using this method, providing a quick and scientific method for the selection of greening plants for future sponge cities.

Suppressing angiogenesis regulates the irradiation-induced stimulation on osteoclastogenesis in vitro.

Ionizing radiation-induced bone loss is a potential health concern in radiotherapy, occupational exposure, and astronauts. Although impaired bone vasculature and reduced proliferation of bone-forming osteoblasts has been implicated in this process, it has not been clearly characterized that whether radiation affects the growth of bone-resorbing osteoclasts. The molecular crosstalk between different cell populations in the skeletal system has not yet been elucidated in detail, especially between the increased bone resorption at early stage of post-irradiation and bone marrow-derived endothelial progenitor cells (BM-EPCs). In order to further understand the mechanisms involved in radiation-induced bone loss at the cellular level, we assessed the effects of irradiation on angiogenesis of BM-EPCs and osteoclastogenesis of receptor activator for nuclear factor-κB ligand (RANKL)-stimulated RAW 264.7 cells and crosstalk between these cell populations. We herein found significantly dysfunction of BM-EPCs in response to irradiation at a dose of 2 Gy, including inhibited proliferation, migration, tube-forming abilities, and downregulated expression of pro-angiogenesis vascular endothelial growth factors A (VEGF A). Meanwhile, we observed that irradiation promoted osteoclastogenesis of RANKL-stimulated RAW 264.7 cells directly or indirectly. These results provide quantitative evidences of irradiation induced osteoclastogenesis at a cellular level, and strongly suggest the involvement of osteoclastogenesis, angiogenesis and crosstalk between bone marrow cells in the radiation-induced bone loss. This study may provide new insights for the early diagnosis and intervention of bone loss post-irradiation.

Cadmium accumulation and main rhizosphere characteristics of seven French marigold (Tagetes patula L.) cultivars.

The study was conducted to determine Cd accumulation and Cd fraction in the rhizosphere soil of seven Tagetes patula cultivars (Little Hero Orange, Durango Yellow, Janie Yellow Bright, Lucifer Yellow, Hero Flame, Hongyun Red, Konghuang Yellow). T. patula cultivars showed strong tolerance and accumulation to Cd. The highest Cd concentration (273.77 mg kg-1) in shoots was observed in Little Hero Orange when treated with Cd100. For most cultivars, Cd treatments significantly affected rhizosphere pH values, but had a slight effect on dissolved organic carbon (DOC). pH were negatively correlated with Cd accumulation and Cd percentages in the exchangeable fraction in the rhizosphere soil of Little Hero Orange, Durango Yellow, and Konghuang Yellow. No significant correlation was observed between DOC, Cd accumulation and Cd percentage in the exchangeable fraction in the rhizosphere soil, except for Konghuang Yellow. The results suggested that pH might be related to Cd bioavailability and their uptake by T. patula. Among seven cultivars, Little Hero Orange showed the greatest pH decrease, highest shoot Cd accumulation and Cd percentage in the exchangeable fraction, suggesting the difference in pH responses to Cd levels among T. patula might be responsible for their different ability of Cd activation.

Indirect effects of X-irradiation on proliferation and osteogenic potential of bone marrow mesenchymal stem cells in a local irradiated rat model.

Cancer survivors after radiotherapy may suffer a variety of bone­related adverse side effects, including radioactive osteoporosis and fractures. Localized irradiation is a common treatment modality for malignancies. Recently, a series of reactions and injuries called indirect effects (remote changes in bone when other parts of the body are irradiated) have been reported on the indirect irradiated area of bone tissue after radiotherapy. To address this issue, we developed a rat localized irradiation model. Rats were irradiated with a single dose of X-rays to the left hind limbs, and bone marrow mesenchymal stem cells (BMMSCs) were isolated from bone marrow of the left (direct irradiated) and right (indirect irradiated) hind limbs 3, 7 and 14 days after irradiation, and assayed for the proliferation ability and osteogenic potential by alkaline phosphatase (ALP) activity, mineralization assay, RT­PCR and western blot analysis. The results showed that there were significant morphology changes in the BMMSCs from direct and indirect irradiated bone tissue with bigger cell bodies and increased granules. The proliferation of BMMSCs decreased both in the direct irradiated and non­irradiated bone tissue. The ALP expression and activities of BMMSCs from direct irradiated bone was consistently defected following a transient enhancement, the mRNA levels of RUNX2 and OCN, the protein expression of RUNX2, and the mineralization ability also showed the same trend. Simultaneously, in indirect irradiated group, the osteogenic potential indicators of BMMSCs decreased in the early stage of post­irradiation and were still impaired 14 days after irradiation. Our data demonstrate that localized irradiation may have both direct and indirect adverse effects on BMMSCs' proliferation and osteogenic potential into osteoblast, which may be the mechanism of radiation-induced abscopal impairment to the skeleton in the cancer radiotherapy-induced bone loss.

[Petroleum pollution and the microbial community structure in the soil of Shengli Oilfield].

Soils around a new oil well (2011- ) and an old oil well (1966-2003) were sampled to investigate the characteristics of petroleum pollution in the oilfield. The structure of soil microbial community was analyzed by PCR-DGGE and clone sequencing techniques. Results showed that the soils around the two oil wells were generally contaminated with petroleum, and the concentrations of total petroleum hydrocarbons mostly exceeded the threshold of the environmental quality standards of soil (500 mg x kg(-1)). The total petroleum hydrocarbons concentration of the polluted soil was significantly positively correlated with the contents of organic carbon, total nitrogen and available potassium, respectively. The microbial diversity index in the soil around the old oil well decreased with the increasing total petroleum hydrocarbons concentration, however, it was reversed for the soil around the new oil well. Sequence analysis of the prominent bands in DGGE profiles showed that some dominant species existed in the petroleum-contaminated soils around the oil wells and mostly were oil-associated and hydrocarbon degrading bacteria, including Microbacterium, Streptomyces, Dietzia, Flavobacterium, alpha-Proteobacteria, and gamma-Proteobacteria.

Mechanistic and kinetic study on the ozonolysis of n-butyl vinyl ether, i-butyl vinyl ether and t-butyl vinyl ether.

Density functional theory (DFT) and ab initio method are employed to elucidate the mechanisms for O(3)-initiated oxidation of n-butyl vinyl ether (n-BVE) and its isomers (i-BVE and t-BVE). For each BVE, the reactions proceed via O(3) cycloaddition resulting in the formation of primary ozonides (POZs) and then two self-decomposition pathways of POZs are followed. Major products are identified to be formaldehyde and butyl formates (CH(3)CH(2)CH(2)CH(2)OCHO for n-BVE, (CH(3))(2)CHCH(2)OCHO for i-BVE and (CH(3))(3)COCHO for t-BVE). The total and individual rate constants for main product channels have been calculated using the modified multichannel Rice-Ramsperger-Kassel-Marcus (RRKM) approach. At 298 K and 101 kPa, the calculated total rate constants are 2.50×10(-16), 3.41×10(-16) and 4.17×10(-16) cm(3) molecule(-1) s(-1) for n-BVE+O(3), i-BVE+O(3) and t-BVE+O(3), respectively, which are in perfect agreement with experimental results. The total rate coefficients are almost pressure independent in the range of 0.001-101 kPa but obviously positive temperature dependent over the whole study temperature range (200-400 K). Also, the favorable reaction pathways have been determined through the estimation of branching ratios. Moreover, the influence of alkoxy group structure on the reactivity of vinyl ethers was examined.

Eco-toxic effects of sulfadiazine sodium, sulfamonomethoxine sodium and enrofloxacin on wheat, Chinese cabbage and tomato.

Investigation of the toxic effects of three veterinary drugs [sulfadiazine sodium (SDS), sulfamonomethoxine sodium (SMMS), and enrofloxacin (EFLX)] on seed germination, root elongation and shoot elongation of wheat (Triticum aestivum L.), Chinese cabbage (Brassica campestris L.) and tomato (Cyphomandra betacea) was carried out. Significant linear relationships between the root and shoot elongation and the concentration of veterinary drugs addition were observed. The effects of the three veterinary drugs on seed germination of wheat, Chinese cabbages and tomato were not significant (P > 0.05), but on shoot and root elongation they were markedly significant (P < 0.05). The inhibitory rates of veterinary drugs on root and shoot elongation of crops were significantly stronger than that on seed germination. Based on IC(50) (drugs concentration when 50% plants show inhibition) of root elongation, wheat was the most sensitive plant to the toxicity of SDS with a IC(50) value as high as 28.1 mg/kg; Chinese cabbage was the most sensitive plant to the toxicity of SMMS with a IC(50) value as high as 27.1 mg/kg; tomato was the most sensitive plant to the toxicity of EFLX with a IC(50) value as high as 125.7 mg/kg. The toxic effects of sulfadiazine sodium and sulfamonometh-oxine sodium on the three crops were much higher than that of enrofloxacin.

[Degradation dynamics of POPs atrazine in soils under long-term located fertilization conditions].

To evaluate the difference of POPs atrazine degradation dynamics in soils under different fertilization conditions, we set up an analysis method of the atrazine residue in soils and studied residue dynamics of atrazine in soils under a long-term located fertilization conditions. After extracted by surging with acetone, liquid-liquid partition and eluted through florisil, the residue of atrazine in soils was detected by gas chromatogram with 63Ni-ECD. The minimum detectable quantity of atrazine is 6.4 x 10(-12) g and the minimum detectable concentration is 6.4 x 10(-9) g x kg(-1) in the soil. The spiked recoveries of atrazine with the three concentration of 0.11, 1.1, 11.0 mg x kg(-1) in soils are 91.41% +/- 4.36%, 93.58% +/- 4.54%, 90.35% +/- 3.59%, according with the request of pesticide residue analysis. The degradation of atrazine in soil under a long-term located fertilization conditions was studied. The results show the degradation of atrazine follows stair dynamic equation, and the degradation half-life of atrazine in soils fertilized with CK, NPK, NPK + M, NPK + S are 20.6, 23.0, 28.5, 33.2 d, respectively. Subjected to analysis of LSR, NPK and organic fertilizers are obviously propitious to the degradation of atrazine. The separate regression and stepwise regression analysis prove the degradation half-life of atrazine in soils is well related with the content of alkaline nitrogen, organic matter and total nitrogen, and the coefficients are 0.9983, 0.9826 and 0.9521, respectively. Maybe the reason is that these soil nutrient substance offers enough the element carbon and nitrogen for action of microbe, and the higher action of microbe quickens the degradation of atrazine in soils.

[Relationships between cadmium accumulation and organic acids in leaves of Solanum nigrum L. as a cadmium-hyperaccumulator].

The influence of different cadmium concentrations on the organic acid level in leaves of the Cd hyperaccumulator, Solanum nigrum L., in particular, the relationship of organic acids with Cd accumulation in S. nigrum was investigated based on the pot-culture experiment. The results showed that the Cd concentration in S. nigrum leaves exceeded 100 microg x g(-1), the threshold value used to define Cd-hyperaccumulators, and the bioaccumulation coefficient of cadmium in shoots of S. nigrum was higher than 1 when Cd concentration in soil was 25 microg x g(-1). The level of organic acids in leaves of S. nigrum had significant differences between the seedling stage and the mature stage. At the seedling stage, the sequence of organic acids in leaves of S. nigrum was acetic acid> tartaric acid> malic acid> citric acid. On the contrary, the accumulation of organic acids in S. nigrum at the mature stage was approximately in the following sequence malic acid> tartaric acid, acetic acid> citric acid. The significant positive correlation between Cd accumulation in leaves of S. nigrum and the concentration of tartaric acid in leaves of S. nigrum was observed at the seedling stage, whereas there was a significant positive correlation between Cd accumulation in leaves of S. nigrum and both acetic and citric acid concentrations at the mature stage. These results indicated that tartaric, acetic and citric acids in leaves of S. nigrum might act as the indication of Cd hyperaccumulation.

[Research advances on eco-chemical behaviors and toxicological effects of cadmium in root-soil interface].

Many active substances such as organic acids and enzymes excreted by living plant roots could induce a great difference of Eh and pH values between root-soil interface and non-rhizosphere soil, forming a special root-soil interface miniature environment. As a mini-type ecological area with most frequent exchanges of substances, root-soil interface plays a crucial role in their absorption, transformation, migration and eco-toxicological effects. In this paper, the eco-chemical behaviors of Cd in root-soil interface affected by the change of pH, Eh and root secretion, and its eco-toxicological effects on microorganisms and enzymes in root-soil interface were reviewed, based on the related research advances in recent decade. The shortages in relevant fields were pointed out, and the scientific problems to be researched in the future were suggested.

[Effects of long-term fertilization on soil microorganism and its role in adjusting and controlling soil fertility].

To clarify the relationships between soil microorganisms and soil fertility under the condition of long-term fertilization, a 12-year fertilization experiment was installed on a fluvo-aquic soil, and the amount of soil microorganisms and the content of soil nutrients were determined and analyzed. The results showed that chemical fertilizers combined with organic manure could significantly improve soil fertility and increase the amount of soil microorganisms. Organic manure was obviously superior to corn straw in improving soil fertility. The correlation between soil microorganisms and soil fertility was significant. A positive correlation was found between the amount of bacteria and azotobacteria and the contents of organic matter, total N, alkalified N, total P and available P. The relationship between the amount of fungi and actinomycetes and the content of soil nutrients was not obvious.

[Biodegradation of herbicide pendimethalin by fungi and its characteristics].

Fungi, which can grow on and degrade pendimethalin, were isolated from activated sludge and soil. The biodegradation characterization in vitro was studied. The results showed that pendimethalin could be degraded by fungi, 16 fungi were isolated by enrichment culture, among which, 10 fungi could degrade more than 60% pendimethalin in 5 days in culture fluid. According to the physiological resistance and the capacity to degrade pendimethalin, three fungi were considered as efficiently degrading strains identified as Aspergillus terreus, Monilochaetes and Aspergillus furnigatus. The efficiency of degradation was affected by culture conditions such as pH, temperature, and concentration of cane sugar and pendimethanlin. The results showed that when the additional carbon source was 0.5%-1.0%, pH value was 6-8, and cultivated temperature was 20-30 degrees C, the growth amount of fungi and the degradation rate were enhanced. The fungi grew quickly, and the biodegradation rate was high under pendimethalin concentration being 100 mg.L-1. The removed amount of pendimethalin increased with increasing pendimethalin concentration. The optimal conditions were proposed, which could provide theoretic basis for prevention and control of pesticides pollution.

[Effect of atrazine on urease activity in soils with different fertility].

Four soils with different fertility were treated with different concentrations of atrazine. The results showed that the urease activity was stimulated in the soils treated with low concentration of atrazine at the first day, while inhibited after treated with high concentration of atrazine during the whole period of the experiment. There was a significant difference in urease activity in soils with different fertility after treated with high concentration atrazine. The urease activity in CK and in NPK was significantly inhibited, the inhibition rate reached 30.35% and 28.89%, respectively, but in NPK + S and NPK + M, the inhibition rate was only 21.35% and 16.86%, respectively. The maximum inhibition rate appeared later in soils with high than with low fertility, showing that soils with high fertility could endure the effect of atrazine.