长春市大气颗粒汞及其干沉降通量

在1999-07～2000-01,监测了长春市5个功能区及一个对照点的大气颗粒汞浓度.非采暖期,市区颗粒汞浓度范围为0.022ng·m^-3～0.398ng·m^-3,平均为0.145 ng·m^-3,对照点平均为0.084ng·m^-3.采暖期,市区颗粒汞浓度范围为0.148ng·m^-3～1.984ng·m^-3,平均为0.461ng·m^-3,对照点平均为0.211ng·m^-3.采暖期颗粒汞浓度平均超出非采暖期2倍以上.燃煤与地面扬尘是大气颗粒汞的2个主要来源.地面扬尘对颗粒汞的贡献约占8%～30%.应用理论模型估算汞的干沉降通量,市区颗粒汞干沉降通量为43.06μg·(m2·a)^-1,对照点为21.28ng·(m²·a)^-1.     

Ce掺杂低钒V2O5-WO3/TiO2催化剂脱除烟气元素汞的研究

制备了Ce掺杂的低矾V₂O₅-WO₃/TiO₂催化剂,在模拟燃煤烟气条件下开展Hg⁰的脱除实验.结果表明该催化剂具有很好的Hg⁰脱除能力,在200～500℃的温度范围内能脱除烟气中95%的Hg⁰.催化剂表征结果表明,比表面积、 孔容和孔径与汞脱除能力没有显著相关性.XPS的结果表明,催化剂表面的Ce是以Ce⁴⁺的形式存在,有利于Hg⁰的脱除反应.抗硫抗水实验表明,H₂O会轻微抑制Hg⁰的脱除反应,主要原因是H₂O和Hg⁰在样品表面的竞争吸附;SO₂会促进Hg⁰的脱除反应,原因是SO₂能增加样品表面的酸吸附位且增加表面Hg⁰的吸附量.     

用TTC与INT-电子传递体系活性表征重金属对污泥活性的影响

研究了不同浓度的Cu²⁺、Zn²⁺、Cd²⁺、Hg²⁺、Ni²⁺、Pb²⁺和Ag⁺对污泥TTC和INT 电子传递体系活性产生的影响 ,比较了这 2个参数在表征污泥活性受重金属抑制时的灵敏性 .结果表明 ,各种重金属抑制污泥TTC 电子传递体系活性的IC₅₀小于抑制INT 电子传递体系活性的IC₅₀,TTC 电子传递体系活性反映重金属毒性作用的灵敏性大于INT 电子传递体系活性 .实验的重金属离子呈现出不同的毒性作用 ,以TTC 电子传递体系活性为评价参数 ,毒性顺序为 :Hg²⁺>Cd²⁺>Cu²⁺>Ag⁺>Zn²⁺>Ni²⁺>Pb²⁺,以INT 电子传递体系活性为评价参数 ,毒性顺序为 :Hg²⁺>Ag⁺>Cu²⁺>Cd²⁺>Zn²⁺>Ni²⁺>Pb²⁺.     

Coating zirconium oxide-nanocomposite with humic acid for recovery of mercury and chromium in hazardous waste of chemical oxygen demand test

Hazardous waste of chemical oxygen demand (COD) test (HW_COD) is one of the most common laboratory wastewaters, containing large amounts of H₂SO₄ and highly toxic Cr³⁺ and Hg²⁺. Current treatment methods suffered from incomplete removal of Cr³⁺ and high-cost. Herein, a humic acid-coated zirconium oxide-resin nanocomposite (HA-HZO-201) was fabricated for efficient recovery of Cr³⁺ and Hg²⁺ in HW_COD. The synthesized HA-HZO-201 shows excellent tolerance to wide pH range (1–5) and high salinity (3.5 mol/L NaCl), as well as adsorption capacity for Cr³⁺ (37.5 mg/g) and Hg²⁺ (121.3 mg/g). After treating with HA-HZO-201 by using a fixed-bed adsorption procedure, the final Cr³⁺ and Hg²⁺ concentrations in HW_COD decreased to 0.28 and 0.02 mg/L, respectively. In addition, the HA-HZO-201 can be regenerated by desorption and recovery of Cr³⁺ and Hg²⁺ using HNO₃ and thiourea as eluents, respectively. After 5 cycles of adsorption/desorption, the removal efficiencies still reach up to 86.0% for Cr³⁺ and 89.7% for Hg²⁺, indicating an excellent regeneration of HA-HZO-201. We hope this work open new opportunities for treatment of HW_COD with high-efficiency and low-cost.     

改性褐煤半焦的表面性质及对气态Hg0的吸附特性

以廉价的褐煤为原料制备褐煤原料半焦,通过化学改性研制脱除烟气中气态Hg⁰的改性半焦(MnO_x/褐煤半焦)吸附剂,运用N₂吸附-脱附、SEM(扫描电镜)、XRD(X射线衍射仪)及XPS(X射线光电子能谱)等对吸附剂的表面特性进行表征与分析,利用固定床吸附试验考察2种吸附剂对气态Hg⁰的吸附特性. 结果表明:原料半焦与改性半焦均具有较发达的孔隙结构,并且以2~5 nm的介孔结构为主;经化学改性后,半焦表面石墨化程度有所提高,石墨碳C─C所占比例由51.37%增至76.17%;MnO_x主要以高度分散的无定形状态均匀分布于改性半焦表面. 固定床吸附试验结果表明,温度为140 ℃时,原料半焦对气态Hg⁰的吸附性能较差,而改性半焦则表现良好,其最高吸附效率可达85.6%;初始ρ(Hg⁰)分别为10.1、20.3、30.0、40.6 μg/m³时,改性半焦的吸附性能随初始ρ(Hg⁰)升高而增强;当吸附温度由30 ℃升至140 ℃时,改性半焦的吸附性能也随着吸附温度的升高而增强. 改性半焦对气态Hg⁰的吸附作用应主要为化学吸附,被吸附后的汞主要以氧化态(Hg²⁺)形式存在.     

Elemental mercury (Hg0) removal from coal syngas using magnetic tea-biochar: Experimental and theoretical insights

Mercury is ranked 3^rd as a global pollutant because of its long persistence in the environment. Approximately 65% of its anthropogenic emission (Hg⁰) to the atmosphere is from coal-thermal power plants. Thus, the Hg⁰ emission control from coal-thermal power plants is inevitable. Therefore, multiple sorbent materials were synthesized using a one-step pyrolysis method to capture the Hg⁰ from simulated coal syngas. Results showed, the Hg⁰ removal performance of the sorbents increased by the citric acid/ultrasonic application. T5CUF_0.3 demonstrated the highest Hg⁰ capturing performance with an adsorption capacity of 106.81 µg/g within 60 min at 200 °C under complex simulated syngas mixture (20% CO, 20% H₂, 10 ppmV HCl, 6% H₂O, and 400 ppmV H₂S). The Hg⁰ removal mechanism was proposed, revealing that the chemisorption governs the Hg⁰ removal process. Besides, the active Hg⁰ removal performance is attributed to the high dispersion of valence Fe₃O₄ and lattice oxygen (α) contents over the T5CUF_0.3 surface. In addition, the temperature programmed desorption (TPD) and XPS analysis confirmed that H₂S/HCl gases generate active sites over the sorbent surface, facilitating high Hg⁰ adsorption from syngas. This work represented a facile and practical pathway for utilizing cheap and eco-friendly tea waste to control the Hg⁰ emission.     

左氧氟沙星对土壤中汞形态微生物转化的影响

为阐明左氧氟沙星（Levofloxacin）对土壤中汞形态转化的影响效应,探究了左氧氟沙星对2种能够影响汞形态转化的细菌—枯草芽孢杆菌（Bacillus subtilis subsp.spizizenii）和洋葱假单胞菌（Pseudomonas cepacian）的抑菌效果;并通过室内土培试验阐明了添加左氧氟沙星对土壤汞赋存形态的作用机制.结果表明,左氧氟沙星对2种细菌都有较好的抑菌效果,在添加0.1 mg·mL^-1左氧氟沙星时,枯草芽孢杆菌和洋葱假单胞菌的菌群数量都有显著降低.土壤培养实验中,接种枯草芽孢杆菌处理土壤中的Hg²⁺含量显著高于对照组（p<0.05）,而洋葱假单胞菌则导致土壤中Hg⁰生成量明显升高（p<0.05）.左氧氟沙星的添加减弱了土壤细菌对Hg²⁺和Hg⁰的转化作用;这主要归因于左氧氟沙星可以有效抑制土壤中菌群的数量及过氧化氢酶和汞还原酶的活性,从而导致2种菌对Hg的氧化和还原能力下降,降低了土壤中Hg²⁺和Hg⁰的含量.本研究对探究汞与抗生素复合污染土壤中汞的形态变化及其环境归趋具有一定的借鉴意义.     

河北农居环境颗粒态汞污染特征及健康评估研究

近年来,我国农村环境问题日渐加重,大气颗粒态汞对人体健康的危害逐渐凸现出来,而已有研究对我国农居环境中的汞污染状况关注较少. 以颗粒态汞为研究对象,于2009年7、8月及2010年10~12月,对河北省6个村庄中的34个典型农居环境进行PM₁₀和PM_2.5膜采样,采用冷原子荧光法测定颗粒态汞质量浓度. 结果表明,同一季节时,厨房PM₁₀中汞质量浓度约是庭院PM₁₀中汞质量浓度的2倍; 在同一空间内,PM₁₀中汞质量浓度大小依次是冬季(3.004 ng·m^-3)>秋季(1.550 ng·m^-3)>夏季(1.127 ng·m^-3); 同一季节时,PM_2.5中汞质量浓度大小依次是厨房(0.795 ng·m^-3±0.337 ng·m^-3)>客厅(0.398 ng·m^-3±0.159 ng·m^-3)>庭院(0.321 ng·m^-3±0.143 ng·m^-3); PM_2.5中的汞质量浓度占PM₁₀中汞质量浓度的百分比为(52.4±13.5)%. 对农居环境PM_2.5中汞的健康风险度水平进行评价,不同人群中儿童的暴露水平最高,其年均超额危险度<10^-8. 可知农居环境PM_2.5中汞对农户的健康风险在可以忽略的水平.     

Hg0 removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron (III) chloride were studied on alab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analy-ses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg²⁺). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃-HZSM-5 was mainly in the form of mercuric chloride(HgCl₂), while on FeCl₃-NaX and FeCl₃-NaA it was mainly mercuri coxide(HgO).     

Role of NO and SO2 in mercury oxidation over a La2O3/Fe2O3 catalyst with high thermal stability

In this study, the thermal stability of a ferric oxide catalyst for mercury oxidation was found to be considerably promoted by doping with La₂O₃. The catalysts doped with La₂O₃ maintained a higher surface area when subjected to high-temperature calcination, with lower average pore size and a narrower pore size distribution. X-ray diffraction (XRD) results revealed that La₂O₃ doping hinders the growth of catalyst particles and crystallization of the material at high temperatures. Both NO and SO₂ inhibited Hg⁰ oxidation over the La₂O₃/Fe₂O₃ catalyst. Fourier transform infrared (FTIR) spectra revealed that SO₂ reacts with O₂ over the catalysts to form several species that are inert for mercury oxidation, such as SO₄^2?, HSO₄^?, or other related species; these inert species cover the catalyst surface and consequently decrease Hg⁰ oxidation capacity. In addition, NO or SO₂ competed with Hg⁰ for active sites on the La₂O₃/Fe₂O₃ catalyst and hindered the adsorption of mercury, thereby inhibiting subsequent Hg⁰ oxidation. Hg⁰ oxidation on the La₂O₃/Fe₂O₃ catalyst mainly followed the Eley–Rideal mechanism. Moreover, the inhibition effects of NO and SO₂ were at least partially reversible, and the catalytic activity was temporarily restored after eliminating NO or SO₂.     

Absorption characteristics of elemental mercury in mercury chloride solutions

Elemental mercury （Hg^0） in flue gases can be efficiently captured by mercury chloride （HgCl2） solution. However, the absorption behaviors and the influencing effects are still poorly understood. The mechanism of Hg^0 absorption by HgCl2 and the factors that control the removal were studied in this paper. It was found that when the mole ratio of Cl^- to HgCl2 is 10：1, the Hg^0 removal efficiency is the highest. Among the main mercury chloride species, HgCl3^- is the most efficient ion for Hg^0 removal in the HgCl2 absorption system when moderate concentrations of chloride ions exist. The Hg^0 absorption reactions in the aqueous phase were investigated computationaIIy using Moller-Plesset perturbation theory. The calculated Gibbs free energies and energy barriers are in excellent agreement with the results obtained from experiments. In the presence of SO3^2- and SO2, Hg^2＋ reduction occurred and Hg^0 removal efficiency decreased. The reduced Hg^0 removal can be controlled through increased chloride concentration to some degree. Low pH value in HgCla solution enhanced the Hg^0 removal efficiency, and the effect was more significant in dilute HgCl2 solutions. The presence of SO4^2- and NO3^- did not affect Hg^0 removal by HgCl2.     

不同波长和强度光照对水体汞还原的影响

采用室内模拟实验,探讨不同光波长、强度对HgCl2还原反应的影响,根据载气中Hg0的实时浓度跟踪HgCl2还原反应的过程,计算Hg0释放通量来进行汞光还原程度定性分析、动力学定量分析,并运用积分法和微分法确定反应级数.结果表明,Hg2+的还原量与光波长呈负相关、与光强度呈正相关,说明光子提供的能量对汞的光还原反应起关键性作用,汞还原率由光波长和强度共同决定,并且受溶液体积和载气流速影响;在各组实验中,载气中的Hg0浓度均表现为先上升再下降后趋于平稳的规律,Hg0浓度上升阶段的主要反应是Hg2+的还原反应和Hg0的释放,而下降阶段的主要反应是Hg0的释放;本研究中可见光下的汞还原反应为一级反应,UVA、UVB光照下的汞还原反应为二级反应,这与汞的配合物具有特定的光谱吸收带和实验用灯提供的光波范围有关.     

Some aqueous reactions of potential importance in the atmospheric chemistry of mercury

Reactions of Hg(I) and Hg(II) with oxidizing and reducing agents have been investigated using stopped-flow and spectroscopic techniques. Hg₂²⁺ was found to be oxidized by HClO and radicals produced by Fentons reagent (Fe²⁺ + H₂O₂). The rate determining step in the reaction of Hg₂²⁺ and HClO is probably a relatively rapid reaction of Hg⁰ and HClO. A photochemically induced reduction of Hg(OH)₂(aq) to Hg⁰ was observed when irradiating with simulated sunlight (λ>290 nm), which may be a process of environmental importance. Aqueous Hg(CN)₂ and HgCl₂ were found to be stable. The rate of reduction of Hg(SO₃)₂²⁻ is not affected by irradiation. No oxidation of Hg₂²⁺ was found when mixing solutions containing H₂O₂ or Fe³⁺ or a mixture of the two which suggests that H₂O₂ is not an important oxidant for mercury under environmental conditions.     

Hg removal from flue gas over different zeolites modified by FeCl3

The elemental mercury removal abilities of three different zeolites (NaA, NaX, HZSM-5) impregnated with iron(III) chloride were studied on a lab-scale fixed-bed reactor. X-ray diffraction, nitrogen adsorption porosimetry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and temperature programmed desorption (TPD) analyses were used to investigate the physicochemical properties. Results indicated that the pore structure and active chloride species on the surface of the samples are the key factors for physisorption and oxidation of Hg⁰, respectively. Relatively high surface area and micropore volume are beneficial to efficient mercury adsorption. The active Cl species generated on the surface of the samples were effective oxidants able to convert elemental mercury (Hg⁰) into oxidized mercury (Hg^2 +). The crystallization of NaCl due to the ion exchange effect during the impregnation of NaA and NaX reduced the number of active Cl species on the surface, and restricted the physisorption of Hg⁰. Therefore, the Hg⁰ removal efficiencies of the samples were inhibited. The TPD analysis revealed that the species of mercury on the surface of FeCl₃–HZSM-5 was mainly in the form of mercuric chloride (HgCl₂), while on FeCl₃–NaX and FeCl₃–NaA it was mainly mercuric oxide (HgO).     

低分子有机酸对汞氧化还原反应的影响

为探究植被根系分泌物的主要成分低分子有机酸对汞氧化还原反应的影响,采用室内模拟试验,探讨了酒石酸、柠檬酸及琥珀酸对汞的还原、氧化反应的影响,并分析了其相应的作用机制.结果表明,酒石酸对汞还原反应有明显的促进作用,柠檬酸有抑制作用.低浓度琥珀酸对汞还原反应有促进作用,高浓度为抑制作用.酒石酸还原Hg2+的反应为二级动力学反应,速率常数为0.0014~0.0056 L·(ng·min)-1.3种有机酸在反应初期对Hg0表现出一定的氧化作用,但随后被氧化的Hg0又被重新还原.3种有机酸对Hg0的氧化能力顺序为:柠檬酸>酒石酸>琥珀酸.     

Influence of dissolved organic matter character on mercury incorporation by planktonic organisms：An experimental study using oligotrophic water from Patagonian lakes

Ligands present in dissolved organic matter （DOM） form complexes with inorganic divalent mercury （Hg^2＋） affecting its bioavailability in pelagic food webs. This investigation addresses the influence of a natural gradient of DOM present in Patagonian lakes on the bioaccumulation of Hg^2＋ （the prevailing mercury species in the water column of these lakes） by the algae Cryptomonas erosa and the zooplankters Brachionus calyciflorus and Boeckella antiqua. Hg^2＋ accumulation was studied through laboratory experiments using natural water of four oligotrophic Patagonian lakes amended with^197Hg^2＋. The bioavailability of Hg^2＋ was affected by the concentration and character of DOM. The entrance of Hg^2＋ into pelagic food webs occurs mostly through passive and active accumulation. The incorporation of Hg^2＋ by Cryptomonas, up to 27% of the Hg^2＋ amended, was found to be rapid and dominated by passive adsorption, and was greatest when low molecular weight compounds with protein-like or small phenolic signatures prevailed in the DOM. Conversely, high molecular weight compounds with a humic or fulvic signature kept Hg^2＋ in the dissolved phase, resulting in the lowest Hg^2＋ accumulation in this algae. In Brachionus and Boeckella the direct incorporation of Hg from the aqueous phase was up to 3% of the Hg^2＋ amended. The dietary incorporation of Hg^2＋ by Boeckella exceeded the direct absorption of this metal in natural water, and was remarkably similar to the Hg^2＋ adsorbed in their prey. Overall, DOM concentration and character affected the adsorption of Hg^2＋ by algae through competitive binding, while the incorporation of Hg^2＋ into the zooplankton was dominated by trophic or dietary transfer.     

Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke

The adsorption characteristics of virgin and potassium permanganate modified lignite semi-coke (SC) for gaseous Hg⁰ were investigated in an attempt to produce more effective and lower price adsorbents for the control of elemental mercury emission. Brunauer-Emmett-Teller (BET) measurements, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface physical and chemical properties of SC, Mn-SC and Mn-H-SC before and after mercury adsorption. The results indicated that potassium permanganate modification had significant influence on the properties of semi-coke, such as the specific surface area, pore structure and surface chemical functional groups. The mercury adsorption efficiency of modified semi-coke was lower than that of SC at low temperature, but much higher at high temperature. Amorphous Mn⁷⁺, Mn⁶⁺ and Mn⁴⁺ on the surface of Mn-SC and Mn-H-SC were the active sites for oxidation and adsorption of gaseous Hg⁰, which oxidized the elemental mercury into Hg²⁺ and captured it. Thermal treatment reduced the average oxidation degree of Mn^x+ on the surface of Mn-SC from 3.80 to 3.46. However, due to the formation of amorphous MnO_x, the surface oxidation active sites for gaseous Hg⁰ increased, which gave Mn-H-SC higher mercury adsorption efficiency than that of Mn-SC at high temperature.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

耐汞好氧反硝化菌的鉴定及适应汞离子的特性研究

从实验室保存的高效好氧反硝化菌种中筛选得到一株抗汞细菌并命名为X1,经生理生化特性和16SrRNA基因序列分析,初步鉴定该菌为恶臭假单胞菌(Pseudomonasputida).对菌株X1进行Hg2适应特性研究,结果表明,对于Hg2浓度为2、67++4、、mg·L-1的实验组,菌体分别需要被延滞12、284018、、h后进入对数期,而8mg·L-1实验组则不能进入对数期;在好氧反硝化过程中,Hg2浓度在7mg·L+-1范围内各实验组的好氧反硝化过程中NO3-N浓度变化速率、NO2-N累积峰值、pH特征点出现时刻随着Hg2浓度的增大而增大(延迟),而Hg2浓度呈现出同硝氮一致的下降趋势,并且在对数期内除汞率能达到100%.研究表明,菌株X1对Hg2最大适宜耐受浓度为7mg·L+-1,相应适应时间约为40h.在最大耐受浓度范围内,菌株X1的生长和好氧反硝化过程呈现出"被抑制-适应-受刺激"的变化规律,其中,被抑制的时间和受刺激的程度都随着Hg2浓度的增大而增大,主要表现为延滞期的延长和对数期的缩短.此外,在对数期,菌株X1的生长速率、达到稳定期的浓度和好+氧反硝化速率也都随着Hg2浓度的增大而增大,且大于无Hg2菌组.++