焦化废水生物出水溶解性有机物特性光谱表征

利用非离子型DAX-8树脂和离子型交换树脂对某焦化废水二级生物出水溶解性有机物(DOM)进行组分分离,从溶解性有机碳(DOC)、紫外-可见光谱、三维荧光光谱、傅立叶变换红外光谱(FT-IR)等4个方面对组分进行光谱学分析与特征识别.结果显示,疏水性酸性物质(Ho A)、亲水性酸性物质(Hi A)和亲水性中性物质(Hi N)为DOM的主要组分,其DOC含量占总DOC的39.88%、20.85%、25.38%;DOM主要含有单环芳香族化合物或共轭双键类化合物成分,类腐殖质物质和类富里酸物质是DOM的特征有机物;低分子量有机物在亲水性物质组分(HIS)中含量最高,E2 54/E3 65=3.89,E445/E665=1.91,SR=0.926均证明了这一点;亲水性碱性组分(Hi B)组分UV254占比为32%,SUVA值为49.94 L·mg-1·cm-1,不饱和物质和芳香性物质含量最高,芳香化程度最高;Ho A的E300/E400值为2.58,腐化程度最高,组分中含有类富里酸物质.DOM光谱分析能够提供组分中亲疏水性物质的比例、芳香性高低、分子量、发色团及有机基团等信息,可以作为判断废水特征的参考依据.     

厌氧环境雌黄溶解产物形态的XAS研究

雌黄是砷的环境地球化学过程中的重要的次生矿物.雌黄的溶解性研究对于研究砷在水环境中的形态转化和环境归趋具有重要意义.环境中p H和硫化程度对于雌黄中的砷的形态变化及其稳定性有重要影响.通过室内模拟实验,结合同步辐射X射线近边吸收光谱(XANES)和扩展X射线吸收光谱(EXAFS)表征手段研究了近中性厌氧条件下,有硫和无硫体系中雌黄溶解产物中稳定存在的砷形态.结果表明,在p H中性条件下,雌黄在两种体系中均形成硫代砷和亚砷酸盐的混合物,有硫体系中硫代砷是以全硫代为主,而无硫体系中硫代亚砷酸盐是部分硫代为主.线性拟合分析确定在有硫体系中硫代亚砷酸盐形态占总砷形态的88.2%,亚砷酸盐形态占总砷形态的11.8%,而在无硫体系中,硫代三价砷形态占总砷形态的43.7%,亚砷酸盐形态占总砷形态的56.3%.可见亚砷酸盐的形成与砷硫比有关,提高硫砷比可以提高亚砷酸盐中硫取代的比例以及全硫代亚砷酸盐的形成.     

三峡库区消落带土壤中溶解性有机质(DOM)吸收及荧光光谱特征

利用紫外-可见吸收光谱和三维荧光光谱技术,结合荧光区域积分法,分析了三峡库区消落带土壤DOM的地化特征.结果表明,各区县消落带土壤CDOM平均浓度大小顺序为:忠县丰都涪陵万州巫山云阳奉节开县,其中,忠县、丰都和涪陵土壤CDOM浓度[a(355)]、芳香性(SUVA254)和疏水组分(SUVA260)明显高于其它区县,而其腐殖化程度(HIX)均低于其它区县.三峡库区消落带土壤DOM中含有类腐殖质荧光团A、C、M和类色氨酸荧光团T,其中紫外区类腐殖质荧光团A的荧光区域积分比例最大.另外,类色氨酸荧光团T与a(355)呈极显著相关(r=0.674,P0.01),影响CDOM浓度变化的主要因素是类蛋白荧光峰T.3D-EEM总荧光强度(TOT)可作为表征三峡库区消落带土壤CDOM荧光团浓度的指标.消落带土壤DOM腐殖化程度较低,生物可利用性较高.另外,消落带干湿交替作用对不同高程土壤DOM地化特征影响的差异较小,这可能与当地农业活动、沿岸植物生长以及DOM矿化过程有关.     

Identification of sources of lead in the atmosphere by chemical speciation using X-ray absorption near-edge structure (XANES) spectroscopy

Sources of Pb pollution in the local atmosphere together with Pb species, major ions, and heavy metal concentrations in a size-fractionated aerosol sample from Higashi-Hiroshima(Japan) have been determined by X-ray absorption near-edge structure(XANES) spectroscopy, ion chromatography, and ICP-MS/AES, respectively. About 80% of total Pb was concentrated in fine aerosol particles. Lead species in the coarse aerosol particles were PbC2O4, 2PbCO3·Pb(OH)2, and Pb(NO3)2, whereas Pb species in the fine aerosol particles were PbC2O4, PbSO4, and Pb(NO3)2. Chemical speciation and abundance data suggested that the source of Pb in the fine aerosol particles was different from that of the coarse ones. The dominant sources of Pb in the fine aerosol particles were judged to be fly ash from a municipal solid waste incinerator and heavy oil combustion. For the coarse aerosol particles, road dust was considered to be the main Pb source. In addition to Pb species, elemental concentrations in the aerosols were also determined. The results suggested that Pb species in size-fractionated aerosols can be used to identify the origin of aerosol particles in the atmosphere as an alternative to Pb isotope ratio measurement.     

环氧富锌涂层对AZ91D镁合金的腐蚀防护能力研究

目的研究环氧富锌涂层对AZ91D镁合金的腐蚀防护能力。方法采用机械喷涂法在AZ91D镁合金表面制备一种保护性的环氧富锌涂层。采用电化学阻抗谱(EIS)研究环氧富锌涂层在0.5 mol/L的Na2SO4腐蚀溶液中的电化学腐蚀行为及其对镁合金的腐蚀防护能力。结果浸泡初期,环氧富锌涂层的阻抗谱中只出现一个时间常数,暗示着环氧富锌涂层优异的阻挡层作用;浸泡48 h后,环氧富锌涂层阻抗谱中出现两个时间常数,高频和低频时间常数分别对应环氧富锌涂层中高聚合的介电性质和锌粉的活性溶解;浸泡336 h后,环氧富锌涂层仍具有很高的阻抗模值,表明此时环氧富锌涂层对镁合金仍能提供良好的腐蚀防护。结论环氧富锌涂层在0.5 mol/L Na2SO4腐蚀溶液中能对AZ91D镁合金提供很好的腐蚀防护。     

黄渤海海域秋季营养盐及有色溶解有机物分布特征

本文利用2013年11月黄渤海海域航次采集的海水样品,对该海域有色溶解有机物(CDOM)、营养盐等的组成、来源、分布特征和主要环境影响因子进行了分析研究.通过三维荧光光谱-平行因子分析法(EEMs-PARAFAC)对CDOM进行分析,共鉴别出2类4种荧光组分:类腐殖质组分C1(325/410 nm)、C2(275,370/435 nm)、C3(270,395/495 nm)和类蛋白质组分C4(290/340 nm).3种类腐殖质组分在黄渤海海域各层的平面分布均为由近岸向远岸逐渐递减.黄海表层和渤海中层类蛋白质组分荧光强度在近岸和远岸海域均出现极大值,而其在渤海表底层及黄海中底层的分布呈现由近岸到远岸逐渐降低的趋势.各层CDOM高值区主要分布在近岸海域.渤海表层溶解无机氮(DIN)和溶解有机氮(DON)浓度高于底层浓度,底层溶解无机磷(DIP)浓度高于表层浓度.渤海DIN呈现由近岸到远岸逐渐降低的趋势,DIP由曹妃甸近岸海域及中部海域的高值区向北部、东部和南部海域逐渐降低的趋势,DON则呈现由渤海中部偏南海域的高值区向四周逐渐递减的趋势.黄海底层DIN和DIP浓度高于表层,而表层DON浓度最高.黄海表中层DIN和DIP呈现由近岸到远岸逐渐降低的趋势,底层DIN和DIP则呈现由近岸到远岸逐渐增加的趋势,DON呈现由近岸到远岸逐渐降低的趋势.渤海DIN、DON和DIP的总体浓度均高于黄海.将4种荧光组分(C1~C4)、吸收系数(a_(355))、溶解有机碳(DOC)与叶绿素a(Chl-a)、盐度(S)、溶解氧(DO)、DIN、DON、DIP进行冗余分析,结果表明黄渤海各荧光组分(C1~C4)主要受陆源输入的影响,DOC受陆源与海源的共同影响,但陆源影响较大.渤海DIN受陆源输入的影响较大,而DON受海源影响较大;黄海DIN受陆源和海源共同影响,而DON主要受陆源输入影响.黄渤海DIP均受陆源和海源共同影响.     

Soil humic acids may favour the persistence of hexavalent chromium in soil

The interaction between hexavalent chromium Cr(VI), as K₂CrO₄, and standard humic acids (HAs) in bulk solution was studied using three complementary analytical methods: UV-Visible spectroscopy, X-ray absorption spectroscopy and differential pulse stripping voltammetry. The observed UV-Vis and X-ray absorption spectra showed that, under our experimental conditions, HAs did not induce reduction of Cr(VI) to its trivalent chemical form. The interaction between Cr(VI) and HAs has rather led to the formation of Cr(VI)-HAs micelles via supramolecular chemical processes. The reported results could contribute towards explaining the relative persistence of ecotoxic hexavalent chromium in soils.     

An alternative method to measure carbonate in soils by FT-IR spectroscopy

Measurements of calcium carbonate contents in soils were performed with FT-IR (Fourier transform infrared) spectroscopy and with the gas volumetric Scheibler method. To the authors’ knowledge it is the first time that carbonate was quantified in soil samples by FT-IR spectroscopy. The carbonate contents of the test soils ranged from 11.3 to 13.1%. Both methods gave similar results, however, results obtained from FT-IR spectra depend on the spectral band used for the carbonate determination. In our investigation we used the bands at 875 and 2506 cm⁻¹. In case of the band at 2506 cm⁻¹ the difference between FT-IR and Scheibler method was a factor of 1.56, in case of 875 cm⁻¹ the respective factor was 1.16. It can be concluded that FT-IR with both bands has a potential to be used in practice as substitution of the Scheibler method. The advantages of the FT-IR method are better reproducibility and the simultaneous characterization of soil organic matter in bulk samples. The disadvantage is its higher cost.     

Upward movement of plutonium to surface sediments during an 11-year field study

An 11-year lysimeter study was established to monitor the movement of Pu through vadose zone sediments. Sediment Pu concentrations as a function of depth indicated that some Pu moved upward from the buried source material. Subsequent numerical modeling suggested that the upward movement was largely the result of invading grasses taking up the Pu and translocating it upward. The objective of this study was to determine if the Pu of surface sediments originated from atmosphere fallout or from the buried lysimeter source material (weapons-grade Pu), providing additional evidence that plants were involved in the upward migration of Pu. The ²⁴⁰Pu/²³⁹Pu and ²⁴²Pu/²³⁹Pu atomic fraction ratios of the lysimeter surface sediments, as determined by Thermal Ionization Mass Spectroscopy (TIMS), were 0.063 and 0.00045, respectively; consistent with the signatures of the weapons-grade Pu. Our numerical simulations indicate that because plants create a large water flux, small concentrations over multiple years may result in a measurable accumulation of Pu on the ground surface. These results may have implications on the conceptual model for calculating risk associated with long-term stewardship and monitored natural attenuation management of Pu contaminated subsurface and surface sediments.     

活性炭氯乙烷防护时间测定方法的改进

活性炭氯乙烷防护时间是用于表征活性炭对难吸附有机物的物理吸附性能。本文对活性炭吸附法测定氯乙烷浓度进行了试验,试验表明,测浓管使用的最佳时间是20-40min。针对活性炭吸附法的不足．本文提出了使用红外光谱技术检测氯乙烷浓度,研究表明,红外光谱仪检测氯乙烷浓度是现实可行的。