Low-temperature dry reforming of methane tuned by chemical speciations of active sites on the SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce catalysts

The cognition of active sites in the Ni-based catalysts plays a vital role and remains a huge challenge in improving catalytic performance of low temperature CO_(2) dry reforming of methane(LTDRM).In this work,typical catalysts of SiO_(2) and γ-Al_(2)O_(3) supported Ni and Ni-Ce were designed and prepared.Importantly,the difference in the chemical speciations of active sites on the Ni-based catalysts is revealed by advanced characterizations and further estimates respective catalytic performance for LTDRM.Results show that larger[Ni0-]particles mixed with[Ni-O-Sin])species on the Ni/SiO_(2)(R)make CH_(4) excessive decomposition,leading to poor activity and stability.Once the Ce species is doped,however,superior activity(59.0%CH_(4) and 59.8%CO_(2) conversions),stability and high H_(2)/CO ratio(0.96)at 600℃ can be achieved on the Ni-Ce/SiO_(2)(R),in comparison with other catalysts and even reported studies.The improved performance can be ascribed to the formation of integral([Ni0_(n))]-[CeⅢ-□-CeⅢ])species on the Ni-Ce/SiO_(2)(R)catalyst,containing highly dispersed[Ni]particles and rich oxygen vacancies,which can synergistically establish a new stable balance between gasification of carbon species and CO_(2) dissocia-tion.With respect to Ni-Ce/γ-Al_(2)O_(3)(R),the Ni and Ce precursors are easily captured by extra-framework Al_(n)-OH groups and further form stable isolated([Ni0_(n))]-[Ni-O-Al_(n)])and[CeⅢ-O-Al_(n)]species.In such a case,both of them preferentially accelerate CO_(2) adsorption and dissociation,causing more car-bon deposition due to the disproportionation of superfuous CO product.This deep distinguishment of chemical speciations of active sites can guide us to further develop new efficient Ni-based catalysts for LTDRM in the future.

Simultaneous Forecast for Three Speciations of Heavy Metal Elements Using Fuzzy Cluster-Artificial Neural Network

The three speciations（water extract, adsorption and organic speciations） of Cu, Zn, Fe and Mn in geo-chemical samples were determined by fuzzy cluster-artificial neural network（FC-ANN） method coupled with atomic absorption spectrometry. A back-propagation artificial neural network with one input node and three export nodes was constructed, which could forecaste three speciations of heavy metals simultaneously. In the learning sample set, the three speciations of each element were allowed to change in a wide concentration range and the accuracy of the analysis was apparently increased via the learning sample set optimized with the help of the fuzzy cluster analysis. The average relative errors of the three speciations of Cu, Zn, Fe or Mn from 100 geo-chemical samples were less than 5%. The relative standard deviations of the three speciations of each of four heavy metals were 0.008%―4.43%.

Thermodynamic simulation of stepwise precipitation of NH_(4)VO_(3)and NaHCO_(3)from carbonating Na_(3)VO_(4)solution

Thermodynamic simulation was conducted to design a new process of stepwise precipitating NH_(4)VO_(3)and NaHCO_(3)from regulating the CO_(2)carbonation of Na_(3)VO_(4)solution.Firstly,a new V(V)speciation model for the aqueous solution containing vanadate and carbonate is established by using the Bromley-Zemaitis activity coefficient model.Subsequently,thermodynamic equilibrium calculations are conducted to clarify the behavior of vanadium,carbon,sodium,and impurity species in atmospheric or high-pressure carbonation.To ensure the purity and recovery of vanadium products,Na_(3)VO_(4)solution is initially carbonated to the pH of 9.3-9.4,followed by precipitating NH_(4)VO_(3)by adding(NH_(4))_(2)CO_(3).After vanadium precipitation,the solution is deeply carbonated to the final pH of 7.3-7.5 to precipitate NaHCO_(3),and the remaining solution is recycled to dissolve Na_(3)VO_(4)crystals.Finally,verification experiments demonstrate that 99.1%of vanadium and 91.4%of sodium in the solution are recovered in the form of NH_(4)VO_(3)and NaHCO_(3),respectively.

The Indo-Burma biodiversity hotspot for ferns:Updated phylogeny,hidden diversity,and biogeography of the java fern genus Leptochilus(Polypodiaceae)

The Indo-Burma Biodiversity Hotspot is renowned for its rich biodiversity,including that of vascular plants.However,the fern diversity and its endemism in this hotspot have not been well understood and so far,the diversity of very few groups of ferns in this region has been explored using combined molecular and morphological approaches.Here,we updated the plastid phylogeny of the Java fern genus Leptochilus with 226(115%increase of the latest sampling)samples across the distribution range,specifically those of three phylogenetically significant species,Leptochilus ovatus,L.pedunculatus,and L.pothifolius.We also reconstructed the first nuclear phylogeny of the genus based on pgiC gene data.Based on molecular and morphological evidence,we identified three new major clades and six new subclades,redefined three existing species,discovered a number of cryptic species of the genus,and elucidated the evolution of the three most variable characters.Our divergence time analyses and ancestral area reconstruction showed that Leptochilus originated in the Oligocene and diversified from early Miocene and 15 dispersal events from lower to higher latitudes are identified.The evolution of three most important morphological characters is analyzed in a context of the new phylogeny.Our analysis showed that 30(59%of total 51)species of Leptochilus occur in Indo-Burma hotspot,24(80%of the 30 species)of which are endemic to this hotspot.We argue that the Indo-Burma hotspot should be recognized as a diversity hotspot for ferns.

Quantitative Evaluation of Heavy Metal Pollution and Its Influencing Factors in Water Bodies of Karst Areas

At present, there is relatively little research on the synergistic effects of heavy metals in soil, sediment, and bedrock on heavy metal pollution in water bodies. In this paper, heavy metals in soil, sediment, bedrock, and water of a typical karst watershed in southwest China were investigated. The results indicated that the average values of heavy metals in soil and sediment were relatively higher than those in bedrock except for Ni and As. During the research period, As and Cd were the main heavy metal elements polluting the soil and sediment in the study area, while water bodies were mainly polluted by Ni, As, and Cd. The pollution assessment indicated that there were instances of poor or very poor water quality in the study area during the study period;the soil as a whole was slightly polluted by Cd and As;sediment was subject to moderate Cd pollution and mild As pollution. Analysis of geochemical form for heavy metals showed that heavy metals in soil and sediment were mainly in residual form, and the proportions of exchangeable As and Cd were relatively high. Multiple statistical analysis showed that heavy metals in sediment, soil, and bedrock explained 23.8%, 16.8%, and 16.2% of the changes in heavy metals of water, respectively. The research results can provide scientific basis for the prevention and control of heavy metal pollution in water bodies.

Investigation of Hexavalent Chromium Reduction in Strong Saline and Acidic Nitro-Phosphate Solutions

Phosphorus fertilizers from less pure sedimentary sources become increasingly important, due to depletion of phosphorus from igneous rock of high quality. Consequently, robust methods with potential to remove various types of hazardous elements are required. Among such impurities, hexavalent chromium (Cr(VI)) is very likely to become a future challenge. Different industrial ways to treat phosphate rock are currently being practised, and we have here studied how chromium behaves when using the nitro-phosphate process. The reduction mechanism of Cr (VI) in nitric acid and phosphoric acid solutions was investigated by measuring redox potential and UV-VIS spectra. The results show that Cr (VI) is not stable in strong nitric acid solutions. Reduction of Cr (VI) species decreased with decreasing temperature, NO2 concentration, ionic strength and absence of light. These findings support the proposed reduction reaction:The reduction rate was observed proportional to the nitric acid decomposition: .

Neural network approach to predicting mercury emission from utility boiler

The feasibility of using an ANN method to predict the mercury emission and speciation in the flue gas of a power station under un-tested combustion/operational conditions is evaluated. Based on existing field testing datasets for the emissions of three utility boilers, a 3-layer back-propagation network is applied to predict the mercury speciation at the stack. The whole prediction procedure includes： collection of data, structuring an artificial neural network （ANN） model, training process and error evaluation. A total of 59 parameters of coal and ash analyses and power plant operating conditions are treated as input variables, and the actual mercury emissions and their speciation data are used to supervise the training process and verify the performance of prediction modeling. The precision of model prediction （ root- mean-square error is 0. 8 μg/Nm3 for elemental mercury and 0. 9 μg/Nm3 for total mercury） is acceptable since the spikes of semi- mercury continuous emission monitor （SCEM） with wet conversion modules are taken into consideration.

Ecological risk assessment of heavy metals in sediments of Xiawan Port based on modified potential ecological risk index

Modified potential ecological risk index （MRI） was proposed based on the potential ecological risk index （RI） and risk assessment code （RAC） by modifying an index. The modified index was relevant to the chemical speciation of heavy metals. Xiawan Port, a typical region contaminated by industrial production, was selected as a case study area. The total concentrations and chemical speciation of heavy metals in sediments of Xiawan Port were analyzed. The experimental data indicate that Xiawan Port is seriously polluted by heavy metals, especially by Cd. The risks of heavy metals are evaluated by RI, RAC and MRI, respectively. The resluts of MRI show that the risks of heavy metals are in the decreasing order of Cd〉Pb〉Cu〉Zn. Comparison of results by different methods reveals that MRI integrates the characters of RI and RAC. MRI is recognized to be useful for risk managemnt of heavy metals in sediments.

Differential utilization and speciation transformation of orthorhombic α-S_8 and amorphous μ-S by substrate-acclimated mesophilic Acidithiobacillus ferrooxidans

The utilization and speciation transformation of α-S8 and μ-S by the typical mesophilic acidophilic strain Acidithiobacillus ferrooxidans ATCC 23270 were investigated.A.ferrooxidans cells first acclimated to the energy source α-S8 or μ-S,respectively.The results of cell growth and sulfur oxidation behavior showed that the strain grown on α-S8 entered slowly（about 1 d later） into the exponential phase,while grew faster in the exponential phase and attained higher maximal cell density and lower p H value than that on μ-S.After bio-corrosion,both of the two sulfur samples were evidently eroded and modified by A.ferrooxidans cells.After growth of A.ferrooxidans,the surface composition of amorphous μ-S became 63.1% μ-S and 36.9% α-S8,and that of orthorhombic α-S8 became 68.3% α-S8 and 31.7% μ-S,while the surface compositions of α-S8 and μ-S in sterile experiment were not changed,indicating that these two elemental sulfur species can be interconverted by A.ferrooxidans.

Fractional distribution and risk assessment of heavy metal contaminated soil in vicinity of a lead/zinc mine

The pollution characteristics of Pb, Cd, Zn, Cu and Ni in soil of lead-zinc mining area were studied. The results indicate that the contamination degree followed the sequence of Cd〉Pb〉Zn〉Ni〉Cu and concentrations of Pb, Cd and Zn exceeded corresponding limits of the Chinese National Soil Environmental Quality Standard III. The soil was extremely polluted by Cd（Iego=5.26）, moderately to heavily polluted by Zn（Iego=2.38）, heavily to extremely polluted by Pb（Iego=4.13）. The results of BCR three-step sequential extraction procedure show that the active Cd, Pb and Zn were relatively high and might exert adverse effects on the plants grown in the soil, while Cu and Ni existed in soil with a relatively stable form. Potential ecological risk results indicate that soils were engaging in a high potential ecological risk by pollution of Cd and should be given rise to concern.

Primary Speciation Analysis on 6 Kinds of Microelements in Glycyrrhiza uralensis Fisch.

[Objective]The aim was to analyze the primary speciation of 6 microelements in Glycyrrhiza uralensis Fisch. and provide theoretical basis for explaining pharmacodynamic principle of liquorice and discussing quality control of liquorice planting. [Method]The 6 elements Cu,Zn,Ca,Fe,Mg and Mn in roots of G.uralensis were extracted based on traditional decoction method and were separated into water-soluble state and suspension state by micro porous filtering film. The elements in water-soluble state were detected by flame atomic adsorption spectrophotometry （FAAS）. [Result]The results showed that extractive rates of the elements were in the range of 1.71%-60.06%,and immerse-residue ratio in 0.018 3-1.682 0; the results also indicated that the immerse-residue ratio of Zn was biggest （1.68）,Zn played an important medical role and might be considered as the best characteristic element in G.uralensis; the recoveries of the elements were ranged from 95.72% to 103.15% and relative standard deviations （RSD） were less than 2.38%. [Conclusion]Because of its high accuracy,FAAS method is feasible for analyzing primary speciation of microelements in G.uralensis.

In-situ measurement and distribution of flue gas mercury for a utility PC boiler system

The in-situ instrumentation technique for measuring mercury and itsspeciation downstream a utility 100 MW pulverized coal (PC) fired boiler system was developed andconducted by the use of the Ontario hydro method (OHM) consistent with American standard test methodtogether with the semi-continuous emissions monitoring (SCEM) system as well as a mobile laboratoryfor mercury monitoring. The mercury and its speciation concentrations including participate mercuryat three locations of before air preheater, before electrostatic precipitator (ESP) and after ESPwere measured using the OHM and SCEM methods under normal operation conditions of the boiler systemas a result of firing a bituminous coal. The vapor-phase total mercury Hg(VT) concentration declinedwith the decrease of flue gas temperature because of mercury species transformation from oxidizedmercury to particulate mercury as the flue gas moved downstream from the air preheater to the ESPand after the ESP. A good agreement for Hg°, Hg^(2+) and Hg( VT) was obtained between the twomethods in the ash-free area. But in the dense particle-laden flue gas area, there appeared to be abig bias for mercury speciation owing to dust cake formed in the filter of OHM sampling probe. Theparticulateaffinity to the flue gas mercury and the impacts of sampling condition to accuracy ofmeasure were discussed.

Iron L-edge and sulfur K-edge XANES spectroscopy analysis of pyrite leached by Acidianus manzaensis

Iron L-edge and sulfur K-edge X-ray absorption near edge structure（XANES） spectroscopy analysis of pyrite leached by extreme thermophilic Archaea strain Acidianus manzaensis（A.manzaensis） was carried out.Leaching experiments show that the oxidation of pyrite can be accelerated by A.manzaensis.Leaching results show that with the increase of leaching time,pH value in the leaching solution gradually decreases,redox potential increases rapidly from day 0 to day 3,and then increases slowly.The SEM results show that the pyrite surfaces are corroded gradually by A.manzaensis,and the XRD results show that the leaching residues contain new compositions of jarosite and elemental sulfur（S0）.The iron L-edge XANES spectroscopy analysis of pyrite during biooxidation indicates that pyrite is gradually converted to Fe（III）-containing species.The sulfur K-edge XANES spectroscopy analysis indicates that elemental sulfur is produced during bioleaching and maintains mass fractions of 3.2%-5.9%.Sodium thiosulfate was also detected from day 2 to day 4,indicating the existence of thiosulfate during biooxidation of pyrite.

涂料行业重点挥发性有机物的筛选与建议

挥发性有机物(VOCs)是当前核心大气污染物,而涂料的生产和使用过程中VOCs的排放一直得到关注。文中基于美国EPA的SPECIATE数据库和实际企业调研,研究了涂料行业重点VOCs的筛选原则与方法,确定VOCs的评分标准和量化处理方法;选取15个类型的涂料涂装工序,以质量分数、嗅阈值、饱和蒸气压、空气环境目标值和最大增量反应活性为评估参数,采用分级赋值和多参数综合评分筛选出7种(类)涂料行业重点VOCs。对重点VOCs的执行标准现状进行了调研比较,提出了修订的建议。

Soil Heavy Metal Pollution Around the Dabaoshan Mine,Guangdong Province,China

Soil contamination in the vicinity of the Dabaoshan Mine, Guangdong Province, China, was studied through determi- nation of total concentrations and chemical speciation of the toxic metals, Cu, Zn, Cd, and Pb, using inductively coupled plasma mass spectrometry. The results showed that over the past decades, the environmental pollution was caused by a combination of Cu, Zn, Cd, and Pb, with tailings and acid mine drainage being the main pollution sources affecting soils. Significantly higher levels （P ≤ 0.05） of Cu, Zn, Cd, and Pb were found in the tailings as compared with paddy, garden, and control soils, with averages of 1486, 2516, 6.42, and 429 mg kg^-1, respectively. These metals were continuously dispersed downstream from the tallings and waste waters, and therefore their concentrations in the paddy soils were as high as 567, 1 140, 2.48, and 191 mg kg^-1, respectively, being significantly higher （P ≤ 0.05） as compared with those in the garden soils. The results of sequential extraction of the above metals from all the soil types showed that the residual fraction was the dominant form. However, the amounts of metals that were bound to Fe-Mn oxides and organic matter were relatively higher than those bound to carbonates or those that existed in exchangeable forms. As metals could be transformed from an inert state to an active state, the potential environmental risk due to these metals would increase with time.

SPECIATE数据库及其在环境政策制定中的应用

介绍了SPECIATE数据库的主要内容及其在涂料行业排放标准制定中的相关作用,初步探究了SPECIATE数据库对筛选行业优先控制污染物的应用。

Heavy metal availability and impact on activity of soil microorganisms along a Cu/Zn contamination gradient

All the regulations that define a maximum concentration of metals in the receiving soil are based on total soil metal concentration. However, the potential toxicity of a heavy metal in the soil depends on its speciation and availability. We studied the effects of heavy metal speciation and availability on soil microorganism activities along a Cu/Zn contamination gradient. Microbial biomass and enzyme activity of soil contaminated with both Cu and Zn were investigated. The results showed that microbial biomass was negatively affected by the elevated metal levels. The microbial biomass-C （Cmic）/organic C （Corg） ratio was closely correlated to heavy metal stress. There were negative correlations between soil microbial biomass, phosphatase activity and NH4NO3 extractable heavy metals. The soil microorganism activity could be predicted using empirical models with the availability of Cu and Zn. We observed that 72% of the variation in phosphatase activity could be explained by the NH4NO3-extractable and total heavy metal concentration. By considering different monitoring approaches and different viewpoints, this set of methods applied in this study seemed sensitive to site differences and contributed to a better understanding of the effects of heavy metals on the size and activity of microorganisms in soils. The data presented demonstrate the relationship between heavy metals availability and heavy metal toxicity to soil microorganism along a contamination gradient.

Transformation of mercury speciation through the SCR system in power plants

Coal-fired utility boilers are now identified as the largest source of mercury in the United States. There is speculation that the installation of selective catalytic reduction （SCR） system for reduction of NOx can also prompt the oxidation and removal of mercury. In this paper, tests at six full-scale power plants with similar type of the SCR systems are conducted to investigate the effect of the SCR on the transformation of mercury speciation. The results show that the SCR system can achieve more than 70%-80% oxidation of elemental mercury and enhance the mercury removal ability in these units. The oxidation of elemental mercury in the SCR system strongly depends on the coal properties and the operation conditions of the SCR systems. The content of chloride in the coal is the key factor for the oxidization process and the maximum oxidation of elemental mercury is found when chloride content changes from 400 to 600 ppm. The sulfur content is no significant impact on oxidation of elemental mercury.

Changes of Cu, Zn, and Cd speciation in sewage sludge during composting

The potential toxicity risks from heavy metals depend on their chemical speciation. The four stages of the Tessier sequential extraction method were employed to investigate changes in heavy metal speciation （Cu, Zn, and Cd） of sewage sludge during forced aeration composting, and then to identify whether the composting process would reduce or enhance their toxicities. Throughout the composting process, the exchangeable, carbonate-bound, Fe-Mn oxide-bound, and organic matter-bound fractions of Cu were converted to the residual Cu fraction. The organic matter-bound Cu fraction greatly contributed to this transformation. Residual Zn fraction was transformed to the Fe-Mn oxide-bound and organic matter-bound fractions after composting. The residual Zn fraction was a major contributor to the organic matter-bound Zn fraction. The availability of Cu and Zn was reduced by composting such that the risk of heavy metal toxicity decreased with prolonged treatment times. Additionally, attention should be paid to the increased availability of Cd in sewage sludge after composting treatment.

Influences of phosphate nutritional level on the phytoavailability and speciation distribution of cadmium and lead in soil

A pot experiment was conducted to examine the influence of phosphate levels on the phytoavailability and speciation distribution of cadmium （Cd）, lead （Pb） in soil. Spring wheat （Triticum aestivum L.） was selected as the tested plant. There were 5 phosphate fertilizer（Ca（H2PO4）2） levels including 0, 50, 100, 200, and 400 mg P2O5/kg soil, marked by P0, P1, P2, P3, and P4, respectively. CdCl2·2.5H2o and Pb（NO3）2 were added to soil as the following levels： Cd ＋ Pb = 25＋0, 0＋1000, and 25＋1000 mg/kg, marked by T1, T2, and T3, respectively. The results showed that the P fertilizer promoted the dry weight of wheat in all treatments and alleviated the contamination induced by Cd and Pb. With increasing levels of the additional P fertilizer, Cd concentration in different parts （root, haulm, chaffand grain） of wheat decreased at the P1 level at first and then increased. The soluble plus exchangeable （SE） fraction of Cd in soil decreased at the P1 level and then increased from P2 to P4 levels. The moderate P fertilizer reduced the phytoavailability of Cd. The application of P could obviously restrain the uptake of Pb by wheat and there were significantly negative correlations between the levels of P and the uptake of Pb. Phosphorus supply resulted in a decrease in the SE fraction of Pb and there was a significantly negative correlation between the levels of P and the SE fraction of Pb in soil. All the levels of the P fertilizer in this experiment could reduce the phytoavailability of Pb. Thus, it is feasible to apply the P fertilizer （Ca（H2PO4）2） to Pb contaminated soils. However, the levels of P application should be restricted in case that redundant P may increase the phytoavailability of Cd.