黄棕壤中不同粒径组分的提取分级与表征

以去离子水为分散剂,采用连续分级法,结合使用筛分、沉降、离心及错流超滤(CFF)等技术,将60目黄棕壤提取分级为细砂粒(50~250μm)、粉粒(5~50μm)、粗黏粒(1~5μm)、细黏粒(0.1~1μm)、纳米微粒(<0.1μm)5个组分;采用激光粒度仪、透射电镜(TEM)、X射线衍射(XRD)等方法对分级结果进行了表征.激光衍射粒度分析所测得各组分实际粒径分布结果与划定的粒径分级范围均很好吻合,表明按上述方法对土壤颗粒进行分级是有效、可行的.TEM观察到的纳米粒级成分呈规则球形,绝大部分颗粒粒径在20~40nm之间,有少部分大颗粒团聚体存在.     

重金属及养分元素在城市污泥主要组分中的分配及其化学形态

通过沉降／离心法将城市污泥区分为生物絮凝体、颗粒态、胶体及水溶态四种组分，并研究了重金属与养分元素在其中的分配及其各组分中重金属的化学形态，生物絮凝体组分占污泥干物质６８％，其次为颗粒态组分（占２３％），胶体及水溶态组分所占比例最少，有机Ｃ，总Ｎ，Ｐ，Ｋ及Ｃｕ，Ｐｂ，Ｚｎ，Ｃｄ，Ｈｇ，Ａｓ也主要分配在生物絮凝体组分中，从重金属在各组分中的形态分布看，重金属的化学活性依次为，污泥水溶性＋胶体组分〉生     

大气甲醛稳定碳同位素分析方法研究

利用气相色谱/燃烧/同位素比值质谱(GC/C/IRMS)技术,采用2,4-二硝基苯肼(DNPH)衍生化,初步研究了单体化合物稳定碳同位素方法研究大气甲醛来源问题.根据不同同位素组成的甲醛与DNPH反应,模拟大气采样,具体讨论了甲醛与DNPH衍生化过程的同位素效应及分析方法的重现性与精确度.结果表明,每个甲醛2,4-二硝基苯腙样品分析的最大标准偏差为0.3‰;不同同位素组成的甲醛衍生化产物甲醛2,4-二硝基苯腙与理论值的平均偏差为0.24‰±0.14‰(从0.03‰到0.35‰),小于仪器分析误差0.5‰,该衍生化过程不存在同位素分馏.采用该方法对酒店大厅内外大气甲醛碳同位素组成进行了初步研究,结果表明不同来源的甲醛同位素组成具有显著差异,可以为大气甲醛的来源分析提供非常有效的信息.     

Risk assessment of heavy metal contaminated soil in the vicinity of a lead/zinc mine

Heavy metal contamination of soils through anthropogenic activities is a widespread and serious problem confronting scientists and regulators throughout the world. In this study we investigated the distribution, chemical species and availability of lead, zinc, cadmium and copper in nine surface（0 to 20 cm） soils from near an abandoned lead/zinc mine tailings located in Shaoxing, Zhejiang, China. Total heavy metal contents ranged from 5271 to 16369 mg/kg for Pb, 387 to 1221 mg/kg for Zn, 3.0 to 9.3 mg/kg for Cd and 65 to 206 mg/kg for Cu. In general, all heavy metals exceeded China National Standards for Soil Environmental Quality of Heavy Metals by a factor of 3-65 times. Comparison of the heavy metal concentrations（Pb, Zn, Cd and Cu） with clay content revealed a strongly significant relationship while significant relationship（ P 〈 0.001 ） was also obtained between Cd ＋ Zn and Pb ＋ Cu. Solid phase speciation of the soils using Tessier procedure showed that the heavy metals were distributed in the order： residual 〉〉 organically complexed-Fe-Mn oxides occluded 〉 carbonate bound 〉 exchangeable 〉 water soluble. In the organic matter fraction, the ratio of Pb（29.1% ） to its total concentration in the soils was higher than those of Zn（4.70% ）, Cd（3.16% ） and Cu（9.50% ）. The percentages of the water soluble and the exchangeable fractions of Pb（1.80% ） and Cd（2.74% ） were markedly greater than those of Zn（0.10% ） and Cu（0.15% ）, suggesting that Pb and Cd are relatively more mobile and hence more toxic in the contaminated soils. Strongly significant relationships between H20-Pb, H20-Zn and H20-Cu, strong positive correlations between H20-Pb, H20-Zn, H20-Cu and organic matter in soil were found. The content of H20-Pb, H20-Zn, H20-Cu was negatively correlated with pH values. The similar negative relationships between pH values and exchangeable heavy metals were also recorded. It is suggested that increasing soil pH or liming the soil could decrease bioavailability of heavy metals in the soil.     

滇池沉积物磷形态的水平分布特征

本文以滇池33个表层沉积物样品为试验材料,采用分级提取的方法逐步提取沉积物中铁磷、铝磷和钙磷,分析沉积物中各磷形态的水平分布特征,结果表明:滇池沉积物总磷浓度的水平分布呈现南北高、中间低的状况,总磷的平均浓度为2 728 mg/kg,局部浓度超过13 000 mg/kg;铁磷、铝磷含量相对较低,不足30%,钙磷和有机磷含量较高,占70%以上;H+浓度影响活性磷的状态,与沉积物铁铝磷显著相关;铁铝磷作为总磷的重要组成部分与总磷显著相关(R=0.701,p0.01)。     

Heavy Metals Fractionation in Ganga River Sediments, India

The Ganga River is the largest river in India which, originates in the Himalayas and along with the Brahmaputra River, another Himalayan river, transports enormous amounts of sediments from the Indian sub-continent to the Bay of Bengal. Because of the important role of river sediments in the biogeochemical cycling of elements, the Ganga river sediments, collected from its origin to the down stretches, were studied in the present context, to assess the heavy metals associated with different chemical fractions of sediments. The fractionation of metals were studied in the sediments using SM&T protocol for the extraction of heavy metals and geo-accumulation index (GAI) (Muller, Schwermetalle in den sedimenten des rheins – Veranderungen seit. Umschau, 79, 778–783, 1979) and Metal Enrichment Factor (MEF) in different fractions were calculated. As with many river systems, residual fractions constitute more than 60% of total metals, except Zn, Cu and Cr. However, the reducible and organic and sulfide components also act as major sinks for metals in the down stretches of the river, which is supported by the high GAI and MEF values. The GAI values range between 4 and 5 and MEF exceed more than 20 for almost all the locations in the downstream locations indicating to the addition of metals through urban and industrial effluents, as compared to the low metals concentrations with less GAI and MEF in the pristine river sediments from the rivers in Himalayas.     

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ^66/64Zn_JMC ≈ + 0.30‰) and anthropogenic (δ^66/64Zn_JMC ≈ + 0.15‰) end members. The lighter δ^66/64Zn_JMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.     

Trace metals in the shells of blue mussels (Mytilus edulis) from the Poland coast of Baltic sea

The Odiel salt marshes (Marismas del Odiel) are an important nature area declared a Biosphere Reserve, but they are greatly affected by pollution from the Odiel River. Surface sediments from this area were analysed using the latest version of the BCR sequential extraction procedure to determine the fractionation of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn among four geochemical phases (acid-soluble, reducible, oxidisable and residual). The total content of each of the metals and As was also determined. The results showed high concentrations of As, Cd, Cu, Pb and Zn, with maximums of 791 mg kg⁻¹ of As, 8.5 mg kg⁻¹ of Cd, 2,740 mg kg⁻¹ of Cu, 1,580 mg kg⁻¹ of Pb and 3,920 mg kg⁻¹ of Zn. The concentrations of Cr, Mn and Ni were low since there are no sources of pollution by them in the area. A comparison of the metal and As levels with the sediment quality guidelines showed that the pollution is sufficient to produce noxious effects in aquatic organisms in most of the Odiel salt marshes. Based on the chemical distribution of the elements, it was found that Cd and Zn were the most mobile (i.e., elements that can pass easily into the water under changing environmental conditions). However, Cr, Fe, Ni and As were present in the greatest percentages in the residual fraction, which implies that these elements are strongly linked to the sediments.     

美国NIST元素汞发生器的基准溯源传递方法

综述了美国NIST元素汞发生器的基准溯源传递方法,通过在输出的汞标准气体中混合加入已知高纯度的201Hg0气体（201Hg2＋标准溶液还原雾化）,并采用同位素稀释电感耦合等离子体/质谱法（IDICP/MS）测量加标后201Hg/202Hg同位素丰度比例,计算出待溯源元素汞发生器输出的Hg0 质量浓度.该过程实现了从元素汞一级标准物质SRM 3133到201Hg2＋标准溶液,再到元素汞发生器输出标准气体的溯源传递,完成了从NIST元素汞基准到仪器供应商生产基准的一级溯源传递,为建立符合我国需求的元素汞溯源传递方法和形成元素汞发生器溯源传递能力提供借鉴.     

Investigation on the Chemical Structure of Nonextractable Residues of the Fungicide Cyprodinil in Spring Wheat Using 13C-C1-Phenyl-Cyprodinil on 13C-Depleted Plants—An Alternative Approach to Investigate Nonextractable Residues

Abstract

¹³C-labelled cyprodinil was applied on ¹³C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of ¹⁴C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The ¹³C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.