Knudsen cell and smog chamber study of the heterogeneous uptake of sulfur dioxide on Chinese mineral dust

The heterogeneous uptake processes of sulfur dioxide on two types of Chinese mineral dust（Inner Mongolia desert dust and Xinjiang sierozem） were investigated using both Knudsen cell and smog chamber system. The temperature dependence of the uptake coefficients was studied over a range from 253 to 313 K using the Knudsen cell reactor, the initial uptake coefficients decreased with the increasing of temperature for these two mineral dust samples, whereas the steady state uptake coefficients of the Xinjiang sierozem increased with the temperature increasing, and these temperature dependence functions were obtained for the first time. In the smog chamber experiments at room temperature, the steady state uptake coefficients of SO2 decreased evidently with the increasing of sulfur dioxide initial concentration from 1.72 × 1012 to 6.15 × 1012mol/cm3. Humid air had effect on the steady state uptake coefficients of SO2 onto Inner Mongolia desert dust.Consequences about the understanding of the uptake processes onto mineral dust samples and the environmental implication were also discussed.     

Heterogeneous uptake of nitrogen dioxide on Chinese mineral dust

Mineral dust is one of the major aerosols in the atmosphere. To assess its impact on trace atmospheric gases, in this work we present a laboratory study of the effect of temperature on the heterogeneous reaction of NO₂ on the surface of ambient Chinese dust over the temperature range from 258 to 313 K. The results suggest that nitrogen dioxide could mainly be adsorbed on these types of Chinese mineral dust reversibly with little temperature dependence. Similar to a previous study on NO₂ uptake on mineral aerosols, the uptake coefficients are mainly on the order of 10^− 6 for the Chinese dust, when BET areas are taken into account. HONO was observed as a product, and its formation and decomposition on Chinese mineral dust during the uptake processes were also studied. The complete dataset from this study was compiled with previous literature determinations. Atmospheric implications of the heterogeneous reaction between NO₂ and mineral dust are also discussed, in an effort to understand this important heterogeneous process.     

Dry deposition of PM10 over the Yellow Sea during Asian dust events from 2001 to 2007

Dry deposition velocities and fluxes of PM10during Asian dust events over the Yellow Sea from 2001 to 2007 were investigated using observation data in Qingdao, China and Jeju, Korea. The dry deposition velocities of PM10 during dust events over the Yellow Sea ranged from 0.19 to 8.17 cm/sec, with an average of 3.38 cm/sec. Dry deposition fluxes of PM10during dust events over the Yellow Sea were in the range of 68.5–2647.1 mg/(m2·day), with an average of 545.4 mg/(m2·day), which is 2–10 times higher than those reported by other studies for both dust and non-dust periods. It was estimated that 2.6 × 1011–48.7 × 1011g dust particles deposit to the Yellow Sea during dust events through dry deposition every year. Compared with the results in previous studies, it was found that the dry deposition of PM10over the Yellow Sea during dust events in the years with high frequency of dust could account for a large or overwhelming fraction of the annual total dry deposition. Backward air mass trajectory analysis showed that dust events influenced Jeju mainly originated from the desert regions located in Mongolia and Inner Mongolia, China. There were 119 backward trajectories influenced both Qingdao and Jeju during 15 dust events from 2001 to 2007, accounting for 61.3% of the total trajectories of 194, indicating that Qingdao and Jeju were usually on the same pathway of dust transport downwind from source areas.     

Reuse of Fenton sludge as an iron source for NiFe2O4 synthesis and its application in the Fenton-based process

The potentially hazardous iron-containing sludge from the Fenton process requires proper treatment and disposal, which often results in high treatment cost. In this study, a novel method for the reuse of Fenton sludge as an iron source for the synthesis of nickel ferrite particles(NiFe_2O_4) is proposed. Through a co-precipitation method followed by sintering at 800°C, magnetic NiFe_2O_4 particles were successfully synthesized, which was confirmed by powder X-ray diffraction(XRD), scanning electronic microscopy(SEM), energy dispersive spectroscopy(EDS), Fourier transform infrared spectroscopy(FT-IR) and Raman spectroscopy. The synthesized NiFe_2O_4 could be used as an efficient catalyst in the heterogeneous Fenton process. In phenol degradation with H_2O_2 or NiFe_2O_4 alone, the phenol removal efficiencies within the reaction time of 330 min were as low as 5.9% ± 0.1% and 13.5% ±0.4%, respectively. However, in the presence of both NiFe_2O_4 and H_2O_2, phenol removal efficiency as high as 95% ± 3.4% could be achieved, indicating the excellent catalytic performance of NiFe_2O_4 in the heterogeneous Fenton process. Notably, a rapid electron exchange between_Ni II and_Fe III ions in the NiFe_2O_4 structure could be beneficial for the Fenton reaction. In addition, the magnetic catalyst was relatively stable, highly active and recoverable, and has potential applications in the Fenton process for organic pollutant removal.     

内蒙古草地生长季植被变化对气候因子的响应

基于MODIS NDVI数据,研究分析了2000-2010年内蒙古典型草原、草甸草原和荒漠草原生长季NDVI时空变化趋势,探讨不同类型草地生长季NDVI对温度、降水的响应。结果表明,内蒙古草地生长季NDVI整体年增长速率为0.735%,典型草原最为明显,年增长率达到1.063%;但是仍有31.807%的草地NDVI呈现下降趋势,其中典型草原、草甸草原和荒漠草原分别有8.664×10⁴、6.814×10⁴、2.841×10⁴ km²。除东北部草甸草原外,大部分草地生长季NDVI与降水量的相关性高于温度;草地生长季NDVI与温度和降水的相关系数均呈现出草甸草原>典型草原>荒漠草原的变化规律。内蒙古草地植被变化对温度和降水的响应具有滞后作用,且具有明显的经度地带性和纬度地带性特征,其滞后时间随着经度和纬度的增加逐渐减少。     

Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag

Basic oxygen furnace slag(BOFS) has the potential to remove hexavalent chromium(Cr(VI))from wastewater by a redox process due to the presence of minerals containing Fe2+. The effects of the solution p H, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope(SEM) equipped with an energy dispersive spectrometer(EDS)system and X-ray diffractometer(XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe2+released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe2+responsible for Cr(VI) removal was primarily derived from the dissolution of Fe O and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum(Ca SO4·2H2O)could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe2+and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps.     

Enhanced catalytic complete oxidation of 1,2-dichloroethane over mesoporous transition metal-doped γ-Al2O3

High-surface-area mesoprous powders of γ-Al₂O₃ doped with Cu^2 +, Cr^3 +, and V^3 + ions were prepared via a modified sol–gel method and were investigated as catalysts for the oxidation of chlorinated organic compounds. The composites retained high surface areas and pore volumes comparable with those of undoped γ-Al₂O₃ and the presence of the transition metal ions enhanced their surface acidic properties. The catalytic activity of the prepared catalysts in the oxidation of 1,2-dichloroethane (DCE) was studied in the temperature range of 250–400°C. The catalytic activity and product selectivity were strongly dependent on the presence and the type of dopant ion. While Cu^2 +- and Cr^3 +-containing catalysts showed 100% conversion at 300°C and 350°C, V^3 +-containing catalyst showed considerably lower conversion. Furthermore, while the major products of the reactions over γ-alumina were vinyl chloride (C₂H₃Cl) and hydrogen chloride (HCl) at all temperatures, Cu- and Cr-doped catalysts showed significantly stronger capability for deep oxidation to CO₂.     

1981—2010年内蒙古草地土壤有机碳时空变化及其气候敏感性

草地土壤有机碳储量巨大,其较小幅度的波动即可能显著反馈于气候变化. 基于1981—2010年内蒙古自治区境内及其周边共计92个气象台站气候要素插值数据,采用空间化的生物地球化学模型——CENTURY 4.5,模拟分析近30年来内蒙古草地表层(0~20 cm)土壤有机碳的空间格局与动态变化特征,并通过构建气候变化情景探讨其对主要气候要素的敏感性. 结果表明:近30年内蒙古草地表层土壤有机碳密度平均值约为1.99 kg/m2(以C计),在空间上呈由东北向西南逐渐减少的分布特征. 近30年来内蒙古草地表层土壤有机碳密度略有增加,年均增幅约0.22%,其中草甸草原的增速〔14.25 g/(m2·a)〕最大,荒漠草原的增速〔1.36 g/(m2·a)〕最小. 草地表层土壤有机碳密度年际变化差异明显,1980s至1990s的增加较为缓慢,1990s至2000s的增幅约为前者的2倍,其中草甸草原和典型草原土壤有机碳增幅较大. 气候敏感性分析结果显示,区域降水量变化可能是近30年内蒙古草地表层土壤有机碳密度变化的主要影响因素,但不同草地类型表层土壤有机碳密度对气候变化的敏感性存在较大差异;典型草原与草甸草原表层土壤有机碳变化主要受控于降水量变化,荒漠草原则主要受控于温度变化.      

Oxidation of diesel soot on binary oxide CuCr(Co)-based monoliths

Binary oxide systems (CuCr₂O₄, CuCo₂O₄), deposited onto cordierite monoliths of honeycomb structure with a second support (finely dispersed Al₂O₃), were prepared as filters for catalytic combustion of diesel soot using internal combustion engine's gas exhausts (O₂, NO_x, H₂O, CO₂) and O₃ as oxidizing agents. It is shown that the second support increases soot capacity of aforementioned filters, and causes dispersion of the particles of spinel phases as active components enhancing thereby catalyst activity and selectivity of soot combustion to CO₂. Oxidants used can be arranged with reference to decreasing their activity in a following series: O₃ ? NO₂ > H₂O > NO > O₂ > CO₂. Ozone proved to be the most efficient oxidizing agent: the diesel soot combustion by O₃ occurs intensively (in the presence of copper chromite based catalyst) even at closing to ambient temperatures. Results obtained give a basis for the conclusion that using a catalytic coating on soot filters in the form of aforementioned binary oxide systems and ozone as the initiator of the oxidation processes is a promising approach in solving the problem of comprehensive purification of automotive exhaust gases at relatively low temperatures, known as the “cold start” problem.     

Effect of organic matter on phosphorus recovery from sewage sludge subjected to microwave hybrid pretreatment

Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H₂O₂, and MW-H₂O₂-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca^2 +, and Mg^2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H₂O₂ is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg^2 +:NH₄⁺-N:PO₄^3 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH₄⁺-N and PO₄³-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.     

Modeling of acute cadmium toxicity in solution to barley root elongation using biotic ligand model theory

Protons（H⁺）as well as different major and trace elements may inhibit cadmium（Cd）uptake in aquatic organisms and thus alleviate Cd toxicity.However,little is known about such interactions in soil organisms.In this study,the independent effects of the cations calcium(Ca²⁺),magnesium(Mg²⁺),potassium（K⁺）,H+and zinc(Zn²⁺)on Cd toxicity were investigated with 5-day long barley root elongation tests in nutrient solutions.The tested concentrations of selected cations and trace metal ions were based on the ranges that occur naturally in soil pore water.The toxicity of Cd decreased with increasing activity of Ca²⁺,Mg²⁺,H⁺and Zn²⁺,but not K⁺.Accordingly,conditional binding constants were obtained for the binding of Cd²⁺,Ca²⁺,Mg²⁺,H⁺,and Zn²⁺ with the binding ligand:log K_CdBL5.19,logK_CaBL2.87,logK_MgBL2.98,logK_HBL5.13 and logK_ZnBL5.42,respectively.Furthermore,it was calculated that on average 29% of the biotic ligand sites needed to be occupied by Cd to induce a 50% decrease in root elongation.Using the estimated constants,a biotic ligand model was successfully developed to predict the Cd toxicity to barley root elongation as a function of solution characteristics.The feasibility and accuracy of its application for predicting Cd toxicity in soils were discussed.     

基于IOCS的内蒙古潜在植被NPP空间分布特征研究

以综合顺序分类系统(IOCS)为基础,利用1985-2009年内蒙古及周边常规气象站的观测资料,采用NPP分类指数模型模拟内蒙古各潜在植被类型NPP,分析其空间分布特征及NPP与气候因子之间的关系。研究表明:①内蒙古地区植被NPP在空间分布上表现出一定的经向分布特征,多年均值介于0~366.5 gC·m^-2·a^-1之间,高值区中心分布在大兴安岭东北部;②各潜在植被类型中,碳汇潜力贡献率最大的潜在植被类型为微温微干温带典型草原类(ⅢC),其值为23.6%;最小的为寒温微干山地草原类(ⅡC),接近于0;③内蒙古潜在植被类型NPP表现出明显的干湿地带性和纬度地带性,且随寒温→微温→暖温、微干→微润→湿润→潮湿的变化其NPP值逐渐增大;但暖温极干暖温带荒漠类(ⅣA)和暖温干旱暖温带半荒漠类(ⅣB)并不符合这一规律,主要原因是较高的温度和较少的降水,达不到植被物质生长的需求。     

Kinetic and products study of the gas-phase reaction of Lewisite with ozone under atmospheric conditions

The rate constant for the gas-phase reaction of O_3 and Lewisite was studied in air using the smog chamber technique. The experiments were carried out under pseudo-first-order reaction conditions with [O_3] [Lewisite]. The observed rate constant of O_3 with Lewisite was(7.83 ± 0.38) × 10~(-19)cm~3/(molecule·sec) at 298 ± 2 K. Lewisite was discussed in terms of reactivity with O_3 and its relationship with the ionization potential. Our results show that the rate constant for the gas-phase reaction of O_3 with Lewisite is in line with the trend of the rate constants of O_3 with haloalkenes.     

Pretreatment of cyanided tailings by catalytic ozonation with Mn/O

The increasing amount of cyanided tailings produced as a by-product has gained significant attention in recent years because of the rapid development of the gold industry and extensive exploitation of gold mineral resources. The effective use of these secondary resources is becoming an important and urgent problem for all environmental protection staff. Manganese-catalyzed ozonation for the pre-oxidation of cyanided tailings was studied and the effects of Mn^2 + dosage, initial sulfuric acid concentration, ozone volume flow, temperature and agitation speed on pretreatment were examined. The optimum reaction conditions were observed to be: ore pulp density 2.5%, agitation speed 700 r/min, temperature 60°C, Mn^2 + dosage 40 g/L, ozone volume flow 80 L/hr, initial sulfuric acid concentration 1 mol/L, and reaction time 6 hr. Under these conditions, the leaching rate of Fe and weight loss could reach 94.85% and 48.89% respectively. The leaching process of cyanided tailings by Mn^2 +/O³ was analyzed, and it was found that the leaching of pyrite depends on synergetic oxidation by high-valent manganese and O³, in which the former played an important part.     

2011年春季辽宁一次沙尘天气过程及其对不同粒径颗粒物和空气质量的影响

利用2011年5月11—12日辽宁沙尘天气过程的相关资料,分析了沙尘天气对不同粒径颗粒物及空气质量的影响及此次沙尘过程的天气成因.结果表明:沙尘天气发生前后可吸入颗粒物PM₁₀、PM_2.5和PM₁的浓度变化很大,沈阳、鞍山、本溪和丹东4城市PM₁₀、PM_2.5的小时浓度最大值都增大了1.5~20倍;粗粒子PM_(2.5~10)的数量浓度分别增加了30~41倍,质量浓度分别增加了27~30倍;细粒子PM_(1~2.5)的质量浓度分别增加了30~35倍,数量浓度分别增加了15~30倍;微粒子的数量浓度和质量浓度各城市表现不同,沈阳微粒子的数量浓度和质量浓度最大值增大了3倍和5倍,而鞍山PM₁的数量浓度和质量浓度分别减少了50%和10%.受蒙古气旋的影响内蒙古地区产生大风降温天气,大风将内蒙古地区的沙尘带到高空并随西风带向东移动进入辽宁,由于辽宁地区风速比较小,造成了辽宁大部分地区的浮尘天气,并对辽宁各地空气质量造成了严重影响,除丹东外辽宁其他13个城市空气质量都达到了轻微污染到重度污染的级别,铁岭、阜新、沈阳和抚顺的污染指数分别超过了300,达到了重度污染的级别.     

New insight into adsorption characteristics and mechanisms of the biosorbent from waste activated sludge for heavy metals

The adsorption characteristics and mechanisms of the biosorbent from waste activated sludge were investigated by adsorbing Pb2+and Zn2+in aqueous single-metal solutions. A p H value of the metal solutions at 6.0 was beneficial to the high adsorption quantity of the biosorbent. The optimal mass ratio of the biosorbent to metal ions was found to be 2. A higher adsorption quantity of the biosorbent was achieved by keeping the reaction temperature below 55°C. Response surface methodology was applied to optimize the biosorption processes, and the developed mathematical equations showed high determination coefficients(above 0.99 for both metal ions) and insignificant lack of fit(p = 0.0838 and 0.0782 for Pb2+and Zn2+, respectively). Atomic force microscopy analyses suggested that the metal elements were adsorbed onto the biosorbent surface via electrostatic interaction. X-ray photoelectron spectroscopy analyses indicated the presence of complexation(between –NH2,-CN and metal ions) and ion-exchange(between –COOH and metal ions). The adsorption mechanisms could be the combined action of electrostatic interaction, complexation and ion-exchange between functional groups and metal ions.     

Biodegradation of indole by a newly isolated Cupriavidus sp. SHE

Indole, a typical nitrogen heterocyclic aromatic pollutant, is extensively spread in industrial wastewater. Microbial degradation has been proven to be a feasible approach to remove indole, whereas the microbial resources are fairly limited. A bacterial strain designated as SHE was isolated and found to be an efficient indole degrader. It was identified as Cupriavidus sp. according to 16S rRNA gene analysis. Strain SHE could utilize indole as the sole carbon source and almost completely degrade 100 mg/L of indole within 24 hr. It still harbored relatively high indole degradation capacity within pH 4–9 and temperature 25°C–35°C. Experiments also showed that some heavy metals such as Mn^2 +, Pb^2 + and Co^2 + did not pose severe inhibition on indole degradation. Based on high performance liquid chromatography–mass spectrum analysis, isatin was identified as a minor intermediate during the process of indole biodegradation. A major yellow product with m/z 265.0605 (C₁₅H₈N₂O₃) was generated and accumulated, suggesting a novel indole conversion pathway existed. Genome analysis of strain SHE indicated that there existed a rich set of oxidoreductases, which might be the key reason for the efficient degradation of indole. The robust degradation ability of strain SHE makes it a promising candidate for the treatment of indole containing wastewater.     

Phosphate recovery from anaerobic digester effluents using CaMg(OH)4

Dolomite lime(DL)(CaMg(OH)_4) was used as an economical source of Mg~(2+)for the removal and recovery of phosphate from an anaerobic digester effluent of a municipal wastewater treatment plant(MWWTP) wastewater. Batch precipitation results determined that phosphate was effectively reduced from 87 to less than 4 mg-P/L when the effluent water was mixed with 0.3 g/L of DL. The competitive precipitation mechanisms of different solids in the treatment system consisting of Ca~(2+)–Mg~(2+)–NH_4~+–PO_4~(3-)CO_3~(2-)were determined by comparing model predictions with experimental results. Thermodynamic model calculations indicated that hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2), Ca_4H(PO_4)_3?3H_2O, Ca_3(PO_4)_2(beta), and Ca_3(PO_4)_2(am2)were more stable than struvite(MgNH_4PO_3?6H_2O) and calcite(CaCO_3). However, X-ray diffraction(XRD) analysis determined the formation of struvite and calcite minerals in the treated effluent. Kinetic experimental results showed that most of the phosphate was removed from synthetic effluent containing NH_4~+within 2 hr, while only 20% of the PO_4~(3-)was removed in the absence of NH_4~+after 24 hr of treatment. The formation of struvite in the DL-treated effluent was due to the rapid precipitation rate of the mineral. The final pH of the DL-treated effluent significantly influenced the mass ratio of struvite to calcite in the precipitates. Because more calcite was formed when the p H increased from 8.4 to 9.6, a p H range of 8.0–8.5 should be used to produce solid with high PO_4~(3-)content. This study demonstrated that DL could be used for effective removal of phosphate from the effluent and that resultant precipitates contained high content of phosphate and ammonium.     

农垦与放牧对内蒙古草原N2O、CO2排放和CH4吸收的影响

利用优选静态箱/气相色谱法(GC),首次对我国内蒙古草原典型地区进行了人类活动对N₂O、CO₂和CH₄交换通量影响的实验观测结果表明,农垦麦田N₂O平均排放通量比原始草原高出3倍,并改变了草甸草原为CO₂汇的性质,使其季节排放净通量以C计增加14.3 mg·(m²·h).随放牧强度的增加CO₂排放通量呈线性增长,轻牧会引起草原对CH₄吸收的大幅增加,而随着放牧压力的增大,增加值迅速回落.农垦麦田与草甸草原相比地-气间CH₄交换无显著变化,放牧强度对N₂O排放影响无显著规律.土壤湿度和温度是影响草原排放N₂O和CO₂、吸收CH4季节变化形式的关键因子,而人类活动仅影响排放强度.排放和吸收量年际间差异很大,但主要受降水的影响.N₂O和CO₂排放与CH₄吸收峰值相反现象普遍存在.     

Insights into properties of activated carbons prepared from different raw precursors by pyrophosphoric acid activation

Low-cost activated carbons (ACs) were prepared from four kinds of solid wastes: petroleum coke, Enteromorpha prolifera, lignin from papermaking black liquid and hair, by pyrophosphoric acid (H₄P₂O₇) activation. Thermo-gravimetric analysis of the pyrolysis of H₄P₂O₇-precursor mixtures implied that H₄P₂O₇ had different influences on the pyrolysis behavior of the four raw materials. N₂ adsorption/desorption isotherms, scanning electron microscopy, Fourier transform infrared spectroscopy and adsorption capacities for dyes were used to characterize the prepared activated carbons. AC derived from E. prolifera exhibited the highest surface area (1094 m²/g) and maximum monolayer adsorption capacity for malachite green (1250 mg/g). Kinetic studies showed that the experimental data were in agreement with the pseudo-second-order model. The adsorption isotherms were well described by the Langmuir isotherm model, indicating the adsorption of dye onto the ACs proceeded by monolayers.