丹江口水库表层沉积物不同形态氮的赋存特征及其生物有效性

为了揭示丹江口水库沉积物氮空间分布特征及其生物有效性,采用连续分级提取法研究了表层沉积物中可交换态氮(Exchangeable nitrogen,EN)、酸解态氮(Acid hydrolysable nitrogen,HN)及残渣态氮(Residue nitrogen,RN)的赋存特征,同时结合生物可利用态氮的含量,探讨了各形态氮对生物可利用态氮的贡献。结果表明,丹江口水库沉积物中总氮(Total nitrogen,TN)在425~5796 mg/kg之间,平均为1 319.32 mg/kg,其中EN、HN和RN的平均值相对比例为2.15∶1.95∶1,且各形态氮含量的空间分布呈入库河流大于库区开阔区域的特征,尤其在丹江、老灌河以及犟河-堵河入库口的含量较大。潜在矿化氮(Potential mineralized nitrogen,PMN)含量在40.20~1 468.95 mg/kg之间,平均为275.06 mg/kg,其中EN对丹江口水库沉积物PMN的贡献较大,比例在19.85%~90.80%之间,平均为63.47%。各形态氮在不同的水环境条件下发生迁移转化,保持着水-沉积物界面氮的动态平衡。     

A new direct thermal desorption-GC/MS method: Organic speciation of ambient particulate matter collected in Golden, BC

Particulate matter having an aerodynamic diameter less than 2.5 μm (PM2.5) is thought to be implicated in a number of medical conditions, including cancer, rheumatoid arthritis, heart attack, and aging. However, very little chemical speciation data is available for the organic fraction of ambient aerosols. A new direct thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed for the analysis of the organic fraction of PM2.5. Samples were collected in Golden, British Columbia, over a 15-month period. n-Alkanes constituted 33–98% by mass of the organic compounds identified. PAHs accounted for 1–65% and biomarkers (hopanes and steranes) 1–8% of the organic mass. Annual mean concentrations were: n-alkanes (0.07–1.55 ng m⁻³), 16 PAHs (0.02–1.83 ng m⁻³), and biomarkers (0.02–0.18 ng m⁻³). Daily levels of these organics were 4.89–74.38 ng m⁻³, 0.27–100.24 ng m⁻³, 0.14–4.39 ng m⁻³, respectively. Ratios of organic carbon to elemental carbon (OC/EC) and trends over time were similar to those observed for PM2.5. There was no clear seasonal variation in the distribution of petroleum biomarkers, but elevated levels of other organic species were observed during the winter. Strong correlations between PAHs and EC, and between petroleum biomarkers and EC, suggest a common emission source – most likely motor vehicles and space heating.     

Study on the hydrolysis/precipitation behavior of Keggin Al13 and Al30 polymers in polyaluminum solutions

The hydrolysis/precipitation behaviors of Al³⁺, Al₁₃ and Al₃₀ under conditions typical for flocculation in water treatment were investigated by studying the particulates' size development, charge characteristics, chemical species and speciation transformation of coagulant hydrolysis precipitates. The optimal pH conditions for hydrolysis precipitates formation for AlCl₃, PAC_Al13 and PAC_Al30 were 6.5–7.5, 8.5–9.5, and 7.5–9.5, respectively. The precipitates' formation rate increased with the increase in dosage, and the relative rates were AlCl₃ ? PAC_Al30 > PAC_Al13. The precipitates' size increased when the dosage increased from 50 μM to 200 μM, but it decreased when the dosage increased to 800 μM. The Zeta potential of coagulant hydrolysis precipitates decreased with the increase in pH for the three coagulants. The iso-electric points of the freshly formed precipitates for AlCl₃, PAC_Al13 and PAC_Al30 were 7.3, 9.6 and 9.2, respectively. The Zeta potentials of AlCl₃ hydrolysis precipitates were lower than those of PAC_Al13 and PAC_Al30 when pH > 5.0. The Zeta potential of PAC_Al30 hydrolysis precipitates was higher than that of PAC_Al13 at the acidic side, but lower at the alkaline side. The dosage had no obvious effect on the Zeta potential of hydrolysis precipitates under fixed pH conditions. The increase in Zeta potential with the increase in dosage under uncontrolled pH conditions was due to the pH depression caused by coagulant addition. Al–Ferron research indicated that the hydrolysis precipitates of AlCl₃ were composed of amorphous Al(OH)₃ precipitates, but those of PAC_Al13 and PAC_Al30 were composed of aggregates of Al₁₃ and Al₃₀, respectively. Al³⁺ was the most un-stable species in coagulants, and its hydrolysis was remarkably influenced by solution pH. Al₁₃ and Al₃₀ species were very stable, and solution pH and aging had little effect on the chemical species of their hydrolysis products. The research method involving coagulant hydrolysis precipitates based on Al–Ferron reaction kinetics was studied in detail. The Al species classification based on complex reaction kinetic of hydrolysis precipitates and Ferron reagent was different from that measured in a conventional coagulant assay using the Al–Ferron method. The chemical composition of Al_a, Al_b and Al_c depended on coagulant and solution pH. The Al_b measured in the current case was different from Keggin Al₁₃, and the high Al_b content in the AlCl₃ hydrolysis precipitates could not used as testimony that most of the Al³⁺ was converted to highly charged Al₁₃ species during AlCl₃ coagulation.     

土壤中钙、镁的形态分析及提取序列的研究

本文采用改进的BCR三步连续提取法对河北某食道癌高发地土壤中钙、镁进行了形态分析及提取序列的研究。实验表明：该地区土壤中镁主要以残渣态形式存在（占总量的83.66％-88.36％）,钙则受提取序列的影响很大,在第一提取序列中,以酸溶态为主（74.11％-83.38％）;第二提取序列中,以有机物结合态为主（78.12％-97.17％）;第三、四提取序列中,以氧化物结合态为主（87.49％-103％）。提取剂的加入顺序明显影响到钙的各个形态的真实含量。     

Americium,plutonium and uranium contamination and speciation in well waters,streams and atomic lakes in the Sarzhal region of the Semipalatinsk Nuclear Test Site,Kazakhstan

New data are reported on the concentrations, isotopic composition and speciation of americium, plutonium and uranium in surface and ground waters in the Sarzhal region of the Semipalatinsk Test Site, and an adjacent area including the settlement of Sarzhal. The data relate to filtered water and suspended particulate from (a) streams originating in the Degelen Mountains, (b) the Tel′kem 1 and Tel′kem 2 atomic craters, and (c) wells on farms located within the study area and at Sarzhal. The measurements show that ²⁴¹Am, ^239,240Pu and ²³⁸U concentrations in well waters within the study area are in the range 0.04–87 mBq dm⁻³, 0.7–99 mBq dm⁻³, and 74–213 mBq dm⁻³, respectively, and for ²⁴¹Am and ^239,240Pu are elevated above the levels expected solely on the basis of global fallout. Concentrations in streams sourced in the Degelen Mountains are similar, while concentrations in the two water-filled atomic craters are somewhat higher. Suspended particulate concentrations in well waters vary considerably, though median values are very low, at 0.01 mBq dm⁻³, 0.08 mBq dm⁻³ and 0.32 mBq dm⁻³ for ²⁴¹Am, ^239,240Pu and ²³⁸U, respectively. The ²³⁵U/²³⁸U isotopic ratio in almost all well and stream waters is slightly elevated above the ‘best estimate’ value for natural uranium worldwide, suggesting that some of the uranium in these waters is of test-site provenance. Redox analysis shows that on average most of the plutonium present in the microfiltered fraction of these waters is in a chemically reduced form (mean 69%; 95% confidence interval 53–85%). In the case of the atomic craters, the proportion is even higher. As expected, all of the americium present appears to be in a reduced form. Calculations suggest that annual committed effective doses to individual adults arising from the daily ingestion of these well waters are in the range 11–42 μSv (mean 21 μSv). Presently, the ground water feeding these wells would not appear to be contaminated with radioactivity from past underground testing in the Degelen Mountains or from the Tel′kem explosions.     

渗滤液污染包气带中铁的形态变化

从渗滤液场龄和包气带岩性两方面出发,研究了新、老渗滤液对亚粘土和细砂包气带环境中Fe的含量及存在形态的影响。结果表明：新、老渗滤液分别能使细砂包气带介质中除残渣态以外Fe的含量增加16.68%或降低13.82%。亚粘土比细砂作为包气带介质更能缓冲渗滤液对介质中Fe的影响程度,其受影响范围在包气带0～20 cm深度处。当亚粘土为介质的包气带被新渗滤液污染后,其表层介质中碳酸盐结合态Fe的含量会增加15倍之多,为缓冲渗滤液Fe的污染做出了巨大贡献,但这部分Fe的存在也是潜在的二次污染源,在环境pH急剧变化的情况下,它可能会引起地下水高铁污染。     

高效液相色谱-电感耦合等离子体质谱法测水中不同形态砷

采用高效液相色谱(HPLC)分离水中两种常见的砷形态As(III)、As(V),电感耦合等离子体质谱系统进行检测鉴定,利用C8色谱柱,探讨了甲醇含量、磷酸二氢钾浓度、四丁基氢氧化铵浓度、p H等测试条件,由此建立了水中砷形态的分析方法。结果表明,以1.5 mmol/L磷酸二氢钾、2 mmol/L四丁基氢氧化铵(TBAOH)、5%甲醇作为流动相,调节流动相为p H 5.5,流速为1.4 m L/min,上述两种不同形态的砷可在5.5 min内得以有效分离,As(III)、As(V)检出限分别为0.001、0.01μg/L,定量下限分别为0.005、0.03μg/L。该方法实现了对水中常见的不同形态砷(As(III)、As(V))的同时分析,具有灵敏度高、选择性好、检测速度快的特点,在水质分析领域具有重要意义与应用价值。     

The sorption of heavy metal species by sediments in soakaways receiving urban road runoff

Infiltration facilities are designed for both the retention of non-point pollutants and the replenishment of groundwater in urban areas. In this study, sorption tests were conducted to evaluate the speciation of heavy metals and their behaviour in infiltration facilities receiving urban road runoff containing high DOC concentrations and stable heavy metal organic complexes. Road dust and three soakaway sediments were collected from heavy traffic areas and a residential area with an infiltration-type sewerage system in Tokyo, Japan. Sequential multiple batch tests were conducted by adding prepared road dust leachate (artificial road runoff) or deionised water to soakaway sediment to obtain soakaway sediment leachate (artificial percolating water from soakaway sediment), which mimicked the sorption by sediments in soakaways receiving urban road runoff. Heavy metal speciation was assessed by means of a combination of anion-exchange resin measurements and MINTEQA2 model calculations, and further validated by chelating resin measurements. In road dust leachates and soakaway sediment leachates, Cu predominantly existed as organic complexes and carbonates, whereas most Mn, Zn and Cd were found to exist in the form of free ions and carbonate complexes. Stable organic complexes of Cu in road dust leachates were strongly adsorbed by soakaway sediments despite the limited adsorption of DOC. On the other hand, desorption of free Mn, Zn and Cd ions from the sediment receiving road dust leachates was observed, indicating that heavy metals such as Mn, Zn and Cd may ultimately reach groundwater as free ions.     

大宝山矿区水体中重金属的行为研究

广东大宝山矿区矿山废水的排放使周边生态环境遭受了严重的破坏。水体中重金属Cu、Zn、Cd和Pb的溶解态浓度分别达到13.82、50.83、0.103和2.91 mg.L-1。Cu、Zn、Cd和Pb的溶解态和悬浮态含量沿河流主干道断面呈相似的空间分布规律,上游都是沿水流方向降低,下游因吸附于悬浮物中的重金属重新释放略有增加。悬浮物中重金属元素的化学形态提取和扫描电镜能谱分析(SEM/EDAX)表明:4种重金属元素都以残渣态为主要存在形态,其次为可还原态,个别断面的Cd可还原态甚至超过了残渣态的含量,说明该水体这4种元素对环境都有一定的潜在威胁性。     

风浪扰动对太湖水体重金属形态的影响

对不同风浪条件下水体中的悬浮颗粒物,采用ICP-AES测定其中Co,Cr,Cu,Ni,Pb,Zn,Al,Fe和Mn不同形态的含量.研究表明,水体中Al,Fe,Co,Cr,Pb和Ni可提取态含量随风浪扰动程度的增强其含量均有不同程度的增大. Mn,Zn和Cu在7m·s-1风浪下含量最高,11m·s-1风浪次之,2m·s-1风浪最小.7m·s-1风浪与2m·s-1风浪相比,水体中Mn, Co, Cr, Zn, Cu和Ni的B1, B2, B3态含量增加3-20倍.11m·s-1风浪与7m·s-1风浪相比,Co, Cr和Ni的B1态含量分别增加31.1%-76.8%,Mn, Zn和Cu分别减少22.1%-38.6%; Cr,Zn和Ni的B2态含量增加12.1%-50.2%, Mn减少65.6%, Co和Cu的含量相当; Co和Ni的B3态含量增加15.4%-10.3%,Cr,Mn,Zn和Cu略微减少.水体中的金属主要以Fe-Mn氧化物结合态存在,且金属的三态比例随风浪的变化不明显. Mn的生物有效性最高,Zn,Cu和Ni次之,毒性较大的Pb和Cr的生物有效性较低.Al, Fe和Pb的Fe-Mn氧化物结合态比例非常高,约有74.56%-100%. Co,Cr和Ni的有机结合态比例较高,且Co和 Ni的三态比例比较均一,Cu的B3态较低.