同步辐射光谱技术在有机固废污染控制与资源化研究中的应用

有机固废中碳、磷、硫及重金属等元素赋存形态是决定其环境行为、反应活性及资源化再利用的关键因素.同步辐射光谱技术可以在分子水平、微纳米尺度原位表征有机固废中碳、磷、硫、重金属等元素赋存形态、结合位点、微观结构,为深入阐明有机固废环境行为、反应机制提供直接的证据.概述了X射线吸收光谱、微束X射线荧光光谱等同步辐射光谱技术在有机固废污染控制与资源化研究的中应用进展,并对同步辐射光谱技术在该领域应用前景和发展趋势进行了展望,以期为有机固废资源化再利用及其污染控制等研究提供参考.     

大气飘尘中若干元素的X射线荧光分析

大气飘尘主要来自人类生产活动和由风扬起的灰尘,它对人体健康和环境的质量有很大影响。研究飘尘组成,有助于了解它的来源、性质、迁移转化规律等。在飘尘元素组成分析中,广泛使用原子吸收、中子活化、发射光谱和X射线荧光光谱,这些方法各有优、缺点。X射线荧光光谱的主要优点:(1)对收集到滤膜上的颗粒物不经化学预处理就可分析多种元素;(2)非破坏性分析,样品可反复测定和适当保存;(3)对每个样品分析成本低,适于大量样品的例行分析。因此,X射线荧光光谱是飘尘分析的一种有效工具。本文以X射线荧光光谱研究和分析了北京地区收集的飘尘样品中的Fe、Ti、Ca、K、Si和S,并对Fe和S的分析     

国外环境样品的x—射线荧光分析近况

X—射线荧光光谱分析由于具有不破坏试样,能够直接分析固体,粉末,液体及大气试样中的大量元素和痕量元素,分析速度快,准确度较高等优点,很早就引起了科学工作者的注意。1962年,Z. H. Kalman等人开始应用粉末压片法测定了岩石和土壤中的痕量元素。1968年,N. B. Price等人将岩石粉末制成薄膜样品测定了其中的Sr、Ni,Cr等元素.此后,R. H.Barnhisel等也应用粉末压片法测定了土壤和团聚体中的铁和锰。但是总的来看,在     

浙东沿海城市大气颗粒物污染特征及来源解析研究

对2009年夏季浙东沿海地区环境空气质量进行监测,监测大气颗粒物(TSP、PM10、PM2.5、PM1.0)浓度,分析颗粒物污染特征、水溶性离子及无机元素组成,运用化学质量平衡受体模型(CMB模型)对浙东沿海地区大气TSP来源进行解析.结果表明,浙东沿海地区的大气颗粒物主要以细颗粒物为主,颗粒物中主要的水溶性离子为SO2-4、NH+4、Ca2+,土壤尘是该地区大气TSP的主要来源,北仑、乐清和奉化TSP中土壤尘的分担率分别达到55.49%、42.52%、40.70%,各监测点TSP来源具有一定的地域特征.     

某尾矿库附近各土壤层对U(Ⅵ)的吸附特性

针对南方某铀尾矿库附近棕红壤剖面中的淋溶层、淀积层和母质层等土层对铀的吸附机理和空间分布规律进行了探讨。采用比表面测定、X射线荧光、扫描电镜、傅里叶变换和X射线衍射等方法对各土层样的理化性质、结构和形貌进行了表征分析;采用静态吸附法考查了时间、U(Ⅵ)初始浓度、pH、温度、粒径等因素对各土层吸附U(Ⅵ)的影响;并使用热力学和动力学方程对吸附过程进行了模拟分析。结果表明,25℃下淋溶层和淀积层pH均为6.2、母质层pH为4.1时,其对U(Ⅵ)最大吸附量分别可达23.60、22.82和13.05 mg·g~(-1)。热力学和动力学拟合结果分别表明,各土层对U(Ⅵ)更符合Langmuir方程(R~20.999)和准二级动力学模型(R~20.98)。风化程度,Fe、Mn、Al、Ca等元素及有机质含量,pH和土壤粒径等因素是各土层对U(Ⅵ)吸附能力不同的主要原因;同时,外源铀进入土壤剖面后,大部分聚集在土壤表层,随着深度的下降的铀含量也逐渐降低。研究结果可为土壤剖面中的铀和其他重金属的污染防治提供参考。     

商业SCR烟气脱硝催化剂钙中毒研究

使用2种不同浓度的前驱体溶液(Ca(NO3)2和Ca(CH3COO)2溶液)浸渍新鲜商业SCR(selective catalytic reduction)烟气脱硝催化剂,并对浸渍中毒后催化剂的性能进行了研究。实验结果表明,物理中毒在本研究中占主导位置,化学中毒并不明显。采用离子色谱、氮气吸附-脱附分析、红外光谱分析、X射线衍射分析、扫面电镜分析等多种表征技术对中毒后催化剂进行了表征。结果表明,中毒后催化剂孔结构性质发生了变化,特别是Ca(CH3COO)2溶液浸渍催化剂,内部孔道堵塞较为严重。X射线衍射分析和扫描电镜分析也从另一方面说明了CaCO3的出现及积累导致催化剂脱硝效率降低。此外,催化剂红外光谱分析从表面活性位的角度说明了本研究催化剂化学中毒现象并不明显。     

北京市春季大气颗粒物污染特性研究

为研究北京市春季大气颗粒物污染特性,2008年3月至2008年5月,对北京市西三环大气颗粒物进行采样分析.测定了总悬浮颗粒物(TSP)与可吸入颗粒物(PM10)的日平均质量浓度,使用扫描电子显微镜(SEM)观察大气颗粒物的微观形貌,并通过X射线能谱仪(EDX)对样品中的元素组成进行分析.结果表明,TSP和PM10日平均质量浓度以初春最高,春天次之,春夏交际最低;PM10/TSP以春夏交际最高,初春次之,春天最低;大气颗粒物形态有规则和不规则2类,以不规则形态居多,同时发现花粉颗粒存在.EDX分析表明,大气颗粒物所附着的重金属中Pb所占的质量分散最高,并且集中吸附在细粒子颗粒物上.     

长沙市夏季大气颗粒物中重金属的形态及其源解析

对长沙市高开区、经开区、开福区以及马坡岭4个采样点夏季的大气颗粒物(TSP)浓度以及颗粒物中的重金属元素Cu、Zn、Mn、Pb和Cd的浓度和形态分布进行了研究分析,利用污染因子(Cf)对重金属元素的可保持能力进行了评价,并利用因子分析方法(PCA)分析TSP中重金属元素的主要来源。结果显示长沙市夏季TSP平均浓度为220.7μg/m3,表明长沙市颗粒物污染较严重。TSP中重金属元素浓度大小顺序为:ZnPbCuMnCd。从形态分布来看,大约63.3%~89.0%的Cu主要存在于可氧化态(F3),而Mn在这一态中分布最少。元素Zn、Cd则主要分布在弱酸提取态,分别占了70%和35%。Pb主要分布在残渣态,大约为24%~43%。由污染因子计算可知Cu、Cd和Zn比Mn、Pb有更高的迁移性。     

ZnCo2O4活化过一硫酸氢钾体系氧化降解水中吡虫啉

吡虫啉(IMI)作为第1代新烟碱类农药,在环境中残余量大、残留时间长,降低其在环境中的含量十分必要.采用凝胶法制备ZnCo2O4双金属氧化物催化剂,利用扫描电镜(SEM)、X射线衍射(XRD)、傅里叶红外光谱(FTIR)及X射线光电子能谱分析(XPS)等手段对催化剂进行了表征.通过ZnCo2O4活化过一硫酸氢钾(PMS...     

含泥钾矿浮选分离技术研究

从钾矿性质和浮选技术2个方面对盐湖含泥钾矿进行资源化利用研究,首先运用X射线荧光光谱、X射线衍射和扫描电镜对含泥钾矿的矿泥化学组成及其结构特征进行了分析,其次选用盐酸十八胺和煤油为浮选药剂,对浮选法脱除钾矿中泥进行了研究.结果表明,盐湖矿泥中70%以上为以长石、粘土和粉砂等为主的硅铝酸盐;矿泥多充填包裹于盐类矿物粒晶间...     

Emission inventory of eight elements,Fe, Al,K, Mg,Mn, Na,Ca and Ti,in dust source region of East Asia

Based on calculation of the emission rate of the atmospheric mineral dust and the data of elemental contents in surface soils, this paper calculates the emission inventory of eight main elements of the atmospheric dust, Fe, Al, K, Mg, Mn, Na, Ca and Ti, in the dust source region of East Asia. As the dust sources in both Northern China and the Southern Mongolia are of three types and, in each of the six source type areas, surface soils are relatively uniform in soil types and soil texture, a simple method to calculate the emission of an element in one source type area is proposed by multiplying the total emission of the dust PM₁₀ and PM₅₀ in the source type area with the mean percentage content of the element in surface soils of the area. Comparison of our calculation of the total Fe emission in the source region of East Asia with the total Fe deposition to the North Pacific Ocean, measured and calculated by previous authors, shows very good agreement. This general method can also be used for the emission calculation of any other element.     

Effects of Ni, Cr, Hg, Cu, Zn, Al on the dissolved oxygen balance of streams

Inorganic metals besides their direct toxic effects, carry the potential of causing serious variations on existing ecosystems in receiving waters. Self purification mechanism is vital for the continuity of the existing micro and macro living organisms in the streams. This mechanism is effected from the existence of metals. In this study, interferences of HgCl2, HgSO4, Ni(NO3)2, CrCl3, CuSO4.5H2O, K2Cr2O7, ZnSO4.7H2O and Al2(SO4)3.18H2O metal compounds on respirometric BOD and related effects on the self purification, are investigated with the representative formations of DO deficit curves. In the presence of these metals, streamwater BOD parameters and related DO deficit curve formations are significantly effected.     

Levels of polychlorinated biphenyls, organochlorine pesticides, mercury, cadmium, copper, selenium, arsenic, and zinc in the harbour seal, Phoca vitulina, in Norwegian waters

Residue levels of the chlorinated hydrocarbons polychlorinated biphenyls (PCBs), total DDT, alpha-, beta- and gamma-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), and oxychlordane in blubber, and the elements mercury, cadmium, copper, selenium, arsenic, and zinc in liver, of 82 harbour seals, Phoca vitulina, were determined. The seals were found dead or dying in Norwegian waters during the disease outbreak caused by a morbilli virus in 1988. Of the chlorinated hydrocarbons, the highest concentrations were found of PCBs, which were 2-4 times higher than the total DDT concentrations. P,p'-DDE was the main contributor to the total DDT, and constituted about 80%. The PCB and total DDT concentrations ranged from 0.4-38 and 0.1-8.8 mg kg(-1), respectively. The mercury concentrations ranged from 0.1-89 mg kg(-1). Significantly higher mean levels of PCBs (13 mg kg(-1) and mercury (16 mg kg(-1)) were found in blubber and liver, respectively, of seals from the Southern coast of Norway, as compared to the corresponding mean levels in seals from the Oslofjord (8.8 and 4.1 mg kg(-1)), and at the Northwestern coast (5.8 and 7.9 mg kg(-1)), respectively. A significant positive correlation was found between the concentrations of selenium and mercury. When the seals were grouped according to sex and age, females of ageclass > 1 and pups of both sexes had significantly lower PCB and total DDT levels than males ageclass > 1. Significantly higher hepatic mercury levels were found in seals ageclass > 1 as compared to pups. Only low levels of the other organochlorines, cadmium and arsenic, were found. Copper and zinc were considered to be present at normal physiological levels. The present organochlorine and heavy metal concentrations gave no support to suggestions that organochlorines and heavy metal pollution may be directly involved in the observed seal deaths.     

Half-lives of tetra-, penta-, hexa-, hepta-, and octachlorodibenzo-p-dioxin in rats,monkeys, and humans--a critical review

The elimination half-lives (t1/2) in Sprague-Dawley rats for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), 1,2, 3,7,8-pentachlorodibenzo-p-dioxin (PeCDD), 1,2,3,4,7,8-hexachlorodibenzo-p-dioxin (HxCDD), 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) and 1,2,3,4,6,7,8,9-octachlorodibenzo-p-dioxin (OCDD) were estimated in long-term studies by Schlatter, Poiger and others. Furthermore, there are some published half-lives of TCDD in adult humans. The average half-life of TCDD in adult humans is approximately 2840 days, while in Sprague-Dawley rats the average t1/2 of TCDD is 19 days. The t1/2 of TCDD in humans is about 150 times that of rats. This factor was used to calculate the t1/2 values of the other polychlorinated dibenzo-p-dioxins (PCDDs) in humans from the rat data. Furthermore, the terminal t1/2 values of PCDDs in adult humans were calculated from the regression equation: logt1/2H = 1.34 logt1/2R + 1.25 which was recently established for 50 xenobiotics (t1/2H = terminal half-lives in days for humans, t1/2R = terminal half-lives in days for rats). The following terminal half-lives in adult humans were obtained: 12.6 years for 1,2,3,7,8-PeCDD, 26-45 years for 1,2,3,4,7,8-HxCDD, 80-102 years for 1,2,3,4,6,7,8-HpCDD and ca. 112-132 years for OCDD. These half-lives of PCDDs are critically compared with measured t1/2 values of PCDDs and other persistent organic pollutants in rats, monkeys and humans.     

Lead,mercury, cadmium,chromium, nickel,copper, zinc,calcium, iron,manganese and chromium (VI) levels in Nigeria and United States of America cement dust

This study was aimed at investigating the relative abundance of heavy metals in cement dust from different cement dust factories in order to predict their possible roles in the severity of cement dust toxicity. The concentrations of total mercury (Hg), copper (Cu), chromium (Cr), cadmium (Cd), nickel (Ni), manganese (Mn), lead (Pb), iron (Fe) and chromium (VI) (Cr (VI)) levels in cement dust and clinker samples from Nigeria and cement dust sample from the United States of America (USA) were determined using graphite furnace atomic absorption (GFAAS), while Zn and Ca were measured by flame atomic absorption spectrophotometry (FAAS), and Cr (VI) by colorimetric method. Total Cu, Ni and Mn were significantly higher in cement dust sample from USA (p < 0.05), also, both total Cr and Cr (VI) were 5.4–26 folds higher in USA cement dust compared with Nigeria cement dust or clinker (p < 0.001). Total Cd was higher in both Nigeria cement dust and clinker (p < 0.05 and p < 0.001), respectively. Mercury was more in both Nigeria cement dust and clinker (p < 0.05), while Pb was only significantly higher in clinker from Nigeria (p < 0.001). These results show that cement dust contain mixture of metals that are known human carcinogens and also have been implicated in other debilitating health conditions. Additionally, it revealed that metal content concentrations are factory dependent. This study appears to indicate the need for additional human studies relating the toxicity of these metals and their health impacts on cement factory workers.     

Effects of elevated CO2, nitrogen supply and tropospheric ozone on spring wheat-II. Nutrients (N, P, K, S, Ca, Mg, Fe, Mn, Zn)

CO(2) enrichment is expected to alter leaf demand for nitrogen and phosphorus in plant species with C(3) carbon dioxide fixation pathway, thus possibly causing nutrient imbalances in the tissues and disturbance of distribution and redistribution patterns within the plants. To test the influence of CO(2) enrichment and elevated tropospheric ozone in combination with different nitrogen supply, spring wheat (Tritium aestivum L. cv. Minaret) was exposed to three levels of CO(2) (361, 523, and 639 microl litre(-1), 24 h mean from sowing to final harvest), two levels of ozone (28.4 and 51.3 nl litre(-1)) and two levels of nitrogen supply (150 and 270 kg ha(-1)) in a full-factorial design in open-top field chambers. Additional fertilization experiments (120, 210, and 330 kg N ha(-1)) were carried out at low and high CO(2) levels. Macronutrients (N, P, K, S, Ca, Mg) and three micronutrients (Mn, Fe, Zn) were analysed in samples obtained at three different developmental stages: beginning of shoot elongation, anthesis, and ripening. At each harvest, plant samples were separated into different organs (green and senescent leaves, stem sections, ears, grains). According to analyses of tissue concentrations at the beginning of shoot elongation, the plants were sufficiently equipped with nutrients. Elevated ozone levels neither affected tissue concentrations nor shoot uptake of the nutrients. CO(2) and nitrogen treatments affected nutrient uptake, distribution and redistribution in a complex manner. CO(2) enrichment increased nitrogen-use efficiency and caused a lower demand for nitrogen in green tissues which was reflected in a decrease of critical nitrogen concentrations, lower leaf nitrogen concentrations and lower nitrogen pools in the leaves. Since grain nitrogen uptake during grain filling depended completely on redistribution from vegetative pools in green tissues, grain nitrogen concentrations fell considerably with severe implications for grain quality. Ca, S, Mg and Zn in green tissues were influenced by CO(2) enrichment in a similar manner to nitrogen. Phosphorus concentrations in green tissues, on the other hand, were not, or only slightly, affected by elevated CO(2). In stems, 'dilution' of all nutrients except manganese was observed, caused by the huge accumulation of water soluble carbohydrates, mainly fructans, in these tissues under CO(2) enrichment. Whole shoot uptake was either remarkably increased (K, Mn, P, Mg), nearly unaffected (N, S, Fe, Zn) or decreased (Ca) under CO(2) enrichment. Thus, nutrient cycling in plant-soil systems is expected to be altered under CO(2) enrichment.     

Urinary arsenic,cadmium, manganese,nickel, and vanadium levels of schoolchildren in the vicinity of the industrialised area of Asaluyeh,Iran

Asaluyeh is one of the most heavily industrialised areas in the world where gas, petrochemical, and many downstream industries are located. This study aims to survey the biomonitoring of four metals and one metalloid in children living in the vicinity of Asaluyeh area. To do this, we analysed the creatinine-adjusted urinary levels of arsenic (As), cadmium (Cd), vanadium (V), manganese (Mn), and nickel (Ni) in 184 elementary schoolchildren (99 boys and 85 girls) living in Asaluyeh and compared them with a reference population. The comparisons were done for two seasons (spring and fall). The results showed that in the case area (Asaluyeh), the levels of As, V, Mn, and Ni were significantly higher and that of Cd was not significantly higher than the reference city for both seasons. The mean concentration of metal(loid)s in Asaluyeh (case) and Sadabad (reference) area as μg g^?1 creatinine was As 2.90 and 2.24, V 0.06 and 0.03, Mn 0.28 and 0.25, Ni 0.54 and 0.29, and Cd 0.31 and 0.28 in spring and As 3.08 and 2.28, V 0.07 and 0.03, Mn 0.30 and 0.26, Ni 0.91 and 0.30, and Cd 0.36 and 0.31 in the fall. Seasonal variations played a key role in determining urinary metal(loid) concentration, as we saw the significant level of As, Cd, V, and Ni in fall than in spring. With regard to the impact of gender on the absorption and accumulation of urinary metal(loid)s, boys showed higher levels of the studied elements, especially for As, than girls as outdoor activities are more popular among boys. Due to the values being lower than those reported in literature, more research is needed on various population groups and other exposure sources in order to judge whether living in the vicinity of the gas and petrochemical industries in Asaluyeh is a threat to nearby residents.     

Adsorption of Pb,Cd, Cu,Zn, and Ni to titanium dioxide nanoparticles: effect of particle size,solid concentration,and exhaustion

Purpose  

Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO₂ nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion.     

A 40+ year record of Cd,Hg, Pb,and U deposition in sediments of Patroon Reservoir,Albany County,NY, USA

Sediments of the Patroon Creek watershed (33 km(2)) are known to contain significant concentrations of heavy metals derived from two industrial sites within the watershed. Mercury Refining, Inc (Mereco) has stored and recycled Hg from 1955 to the present day, and National Lead Industries (NLI) manufactured aircraft components containing Cd, Pb, and U from 1958 to 1984. Here we present the first record of heavy metal deposition as preserved in a 3-m long sediment core collected in 1999 from Patroon Reservoir, a small water body (1.3 ha) downstream of the industrial sites. Bulk sediment samples were collected from the core at 0.05-m intervals and analyzed for total Cd, Pb, and U by ICP-MS and total Hg by CVAAS. Total Hg increases from less than 1 mg kg(-1) (dw) below 1.68 m, to a maximum of 6.2 mg kg(-1) at 0.80 m, and then declines to the sediment-water interface. Total Cd, Pb, and U concentrations increase abruptly above 1.68 m to maximum values of 25, 320, and 3600 mg kg(-1) (dw), respectively, and then decline gradually upwards. By correlating metal profiles with industrial history, we conclude that the 1.68 m horizon was deposited no earlier than 1958, the beginning of aircraft component manufacturing at NLI. The average, apparent sedimentation rate within the reservoir has a minimum value of approximately 0.04 m year(-1) for the 41-year period from 1958 to 1999. In the interval 0--1.68 m, average concentrations of Cd, Hg, Pb, and U are 1.69, 1.50, 461, and 13 mg kg(-1), respectively. These levels are comparable with other lake, reservoir and stream sediments that have been moderately to severely impacted by industrial pollution and are above levels expected to be detrimental to aquatic organisms.     

Toxicity of mancozeb,chlorothalonil, captan,fluopyram, boscalid,and difenoconazole to Didymella applanata isolates from Serbia

Field isolates of Didymella applanata, the causal agent of spur blight of raspberry, were evaluated in vitro for their sensitivity to mancozeb, chlorothalonil, captan, fluopyram, boscalid and difenoconazole. A total of 10 isolates, collected during 2013 at five localities in the major raspberry growing region in Serbia, and characterized as copper hydroxide, dithianon, and tebuconazole (sensitive), pyraclostrobin (sensitive or highly resistant) and fluazinam (sensitive or moderately resistant), were used in this study. The EC₅₀ values for the isolates ranged from 1.33 to 2.88 mg L^?1 for mancozeb, from 3.18 to 6.65 mg L^?1 for chlorothalonil, from 15.75 to 24.69 mg L^?1 for captan and from 1.80 to 8.20 mg L^?1 for fluopyram. The narrowest range of EC₅₀ values was recorded for difenoconazole (0.23–0.49 mg L^?1), whereas the widest range was obtained for boscalid (4.49–49.25 mg L^?1). The calculated resistance factors showed that all D. applanata isolates were sensitive to mancozeb, chlorothalonil, captan, and difenoconazole. Four isolates were moderately resistant to boscalid, while three of them were also moderately resistant to fluopyram. This finding of moderately resistant isolates to these SDHI fungicides indicates a possible cross-resistance which should be clarified in further investigations.