Source characterization of ambient fine particles at multiple sites in the Seattle area

To identify major PM_2.5 (particulate matter ≤2.5 μm in aerodynamic diameter) sources with a particular emphasis on the ship engine emissions from a major port, integrated 24 h PM_2.5 speciation data collected between 2000 and 2005 at five United State Environmental Protection Agency's Speciation Trends Network monitoring sites in Seattle, WA were analyzed. Seven to ten PM_2.5 sources were identified through the application of positive matrix factorization (PMF). Secondary particles (12–26% for secondary nitrate; 17–20% for secondary sulfate) and gasoline vehicle emissions (13–31%) made the largest contributions to the PM_2.5 mass concentrations at all of the monitoring sites except for the residential Lake Forest site, where wood smoke contributed the most PM_2.5 mass (31%). Other identified sources include diesel vehicle emissions, airborne soil, residual oil combustion, sea salt, aged sea salt, metal processing, and cement kiln. Residual oil combustion sources identified at multiple monitoring sites point clearly to the Port of Seattle suggesting ship emissions as the source of oil combustion particles. In addition, the relationship between sulfate concentrations and the oil combustion emissions indicated contributions of ship emissions to the local sulfate concentrations. The analysis of spatial variability of PM_2.5 sources shows that the spatial distributions of several PM_2.5 sources were heterogeneous within a given air shed.     

人工神经网络用于铅的化学形态模拟计算

用前馈线性网络法求解水体系中Ｐｂ（２＋）与ＯＨ－之间的反应常数，不同训练算法对求解结果的精度、收敛速度及权值均有影响．结果表明，批处理算法的精度最好，权值不出现负值，但运算时间最长；在线算法的精度虽不如批处理算法，而比数据变换－在线算法好，权值有时会出现负值．运算时间较长；数据变换－在线算法的优点是运算时间短，但相对误差较大，权值出现负值的机会多。采用反馈网络模拟计算铅的各种化学形态的浓度．用物料核算的方法对反馈网络模型进行检验表明，此种模型用于平衡计算是可行的，详细分析了理论模拟和实验曲线的差异的原因，温度的影响最小，在４＜ｐＨ＜９时，ＣＯ有重要的影响．在国代检验时，ｎ值取整所引入的误差的影响亦不可忽视。从本文的结果可以看到，采用前馈网络和反馈网络相结合的方法考察水体中的化学形态是可行的．从而为解决这一类问题提供了一种可能的途径．     

水环境中重金属的生物毒性预测模型

简要介绍了近年来发展的几种金属生物毒性预测模型，如FIAM、GSIM和BLM等模型。金属与生物有效性和毒性之间的关系，是制定金属的水质标准的依据，随着对金属形态及其生物有效性和毒性关系研究的深入，产生了很多的机理描述模型。描述金属与生物作用的现存模型有多种，分别从多种角度解释了环境因素对金属形态分布及其生物毒性的影响，各模型在一定程度上可给出重金属的生物毒性信息，但都存在缺陷，不能完全替代毒性实验。建立合理的金属毒性预测模型，为建新的水质标准提供依据，正是国际环境界研究的热点。     

煤飞灰中铬铁元素的形态分析研究

用连续提取法将煤飞灰中的铬、铁元素依结合态区分为水溶态,交换态,表面氧化物和碳酸结合态,铁锰氧化物结合态,金属有机物和硫化物结合态,磁性四氧化三铁结合态和硅铝酸盐矿物态,用原子吸收法及X-衍射分析进行测定。并对煤飞灰化学形态分布进行了讨论。     

Hazard property classification of waste according to the recent propositions of the EC using different methods

Hazard classification of waste is a necessity, but the hazard properties (named “H” and soon “HP”) are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors.In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>1 0 0).Data for 45 wastes – documented with extensive chemical analysis and flammability test – were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values.This data set showed HP 14 ‘Ecotoxic chronic’ is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 ‘Carcinogenic’. The third most frequent hazard is HP 10 ‘Toxic for reproduction’ and the fourth most frequent hazard is HP 4 “Irritant – skin irritation and eye damage”. In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties.The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.     

烟草废弃物快速堆肥过程中重金属Cd形态变化特征

以烟草废弃物为原料,活性土壤为载体建立堆体,研究重金属镉的形态变化,及堆肥过程中的动态变化规律。结果表明,烟草废弃物与活性土壤混合能快速腐熟。堆肥总质量下降,重金属镉含量相对增加。重金属镉的铁锰氧化态比例增加19%,有机结合态比例在堆肥升温阶段增加,腐熟后有所下降。残渣态比例大幅度上升,增加达到5倍,且在腐熟阶段增幅最大。说明堆肥处理有利于降低重金属镉的活性。     

Association of plutonium with sediments from the Ob and Yenisey Rivers and Estuaries

The present study applied sequential extraction techniques to investigate the binding and mobility of plutonium (Pu) in sediments from the rivers and estuaries of the Ob and Yenisey. As a study site, the Ob and Yenisey are particularly interesting as both rivers have weapons-grade Pu sources in their catchment areas, including the Russian Pu production and reprocessing plants at Mayak, Tomsk-7 and Krashnoyarsk, and the Semipalantinsk nuclear weapons testing site in Kazakhstan. Plutonium activity and ²⁴⁰Pu/²³⁹Pu ratios were determined using accelerator mass spectrometry (AMS). Sequential extractions showed that between 47 and 80% of the Pu in Yenisey River sediments and 35–53% of the Pu in soils around the Techa River are mobilized with weak oxidising agents, which can indicate that Pu is bound to organic material. In contrast, Pu in Ob and Yenisey Estuarine sediments was more strongly bound, with 60–100% being found in the HNO₃-extractable fraction. This change in speciation could reflect either that Pu bound to organic material in the Techa and Yenisey River sediments becomes more fixed to the sediments with time, or that organic-bound Pu is mobilized and released to the water when the sediments encounter the more saline water of the Ob and Yenisey estuaries. In general, ²⁴⁰Pu/²³⁹Pu ratios were relatively consistent between different extraction fractions, although, in whole sediments, an increase in ratio was observed with distance from the source. This reflects the increased influence of weapon fallout from catchment runoff within the river systems, as compared to the weapons-grade sources close to the production and reprocessing plants. Knowledge of Pu speciation in the Ob and Yenisey Rivers, and the processes controlling its behaviour in estuarine systems, can improve predictions of its transfer and subsequent environmental impact to Arctic Seas.     

Inorganic and methyl-mercury speciation in sediments of the Swarzędzkie Lake

Sediment samples were analysed for mercury and methylmercury content in different parts of the bottom sediment of Swarz ?dzkie Lake, which were influenced by different external pollution sources. The results of determination with two methods of mineralization using two separate media (HNO₃/H₂O₂ and HF) were compared. The accuracy of the studied methods was analysed using certified reference material IAEA 405 of river sediment. The recovery of mercury was satisfactory and ranged from 97.5 to 98.8%. Methylmercury compounds in the studied sediments were found in limited concentrations. Their concentrations ranged from 0.26 to 58.1 μg kg^?1, i.e. 1.0–7.4% of the total mercury content. The depth profile displayed high values of both total and methylmercury content at a depth of 10–20 cm, related to the heavy pollution of the lake in the 1980s. Canonical analysis displayed the relationship of both total mercury and methylmercury concentrations with organic matter and phosphorus content in bottom sediments.     

Investigation of trace metal binding properties of lignin by diffusive gradients in thin films

The binding behavior of lignin for Pb, Cu, Co, Mn, Cd and Ni was studied using the diffusive gradients in thin films technique (DGT). Samplers with different structures of diffusive gel were used in the well-stirred systems containing known concentrations of metals along with (a) 10, 20 and 40 μM lignin and; (b) 0.64 and 6.47 μM Suwannee river fulvic acid + 40 μM lignin at an ionic strength of 0.01 M (NaNO₃) and pH = 7. Diffusion coefficients of lignin complexes in acrylamide gels were estimated and found to be less than 5% of the equivalent coefficients for the uncomplexed metal ions. These values were used to calculate concentrations of labile metals from DGT measurements in solutions, where lignin could discriminate metals in the order of Pb⁺² > Cu⁺² > Cd⁺² > Ni⁺² > Co⁺² > Mn⁺². Stability constants (Log K) were calculated using Visual MINTEQ II and WHAM V software. The K values were compared with the stability constants from titration of Pb and Cd with 10 μM lignin aqueous samples and with those of humic substances in natural waters. The constants obtained from measurement of complexing capacities might bias the real corresponding values unless two line regression analyses on titration data are considered. The DGT study of fractionation of metal species at varying ratios indicated that the proportion of organic complexes decreased with increasing ratios and gradually more metals were exchanged with inorganic phases. Speciation of Pb and Cd is affected by the concentrations of FA, Cd is dominantly bound with FA while Pb is evenly partitioned between the ligands. The comprehensive knowledge of metal-lignin complexes sheds some light on in situ operational speciation information that can be achieved by DGT.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).