石墨炉原子吸收中的基体改进效应研究

本文回顾了石墨炉原子吸收基体改进效应的研究,包括无机和有机基体改进剂的应用,碳化物涂层技术和保护气体中引入氧和氢气。讨论了基体改进剂存在时的原子化机理和干扰机理。列表说明了基体改进效应在不同样品痕量元素测定中的应用及其方法概要。     

微波消解ICP-AES法测定土壤中的多种金属元素

采用微波消解法消解环境土壤标准物质NIST2710、NIST2711和ESS-4,使用ICP-AES双向观测法进行测定,采用了内标校正和元素间校正两种校正方法解决了土壤样品基体复杂、共存元素干扰大的难题,研究了土壤中多元素同时测定的分析方法.实验结果表明,土壤中的As、Cd、Co、Cr、Cu、Ni、Pb、V和Zn等多种元素的测定值与给定的标准值吻合,该方法线性相关系数大于0.99997,完全能满足土壤分析要求.     

巯基棉富集分离—氢化物原子吸收法分别测定水中痕量的碲(Ⅳ)和碲(Ⅵ)

随着碲在工业上的广泛应用和对环境的污染,人们对它的生物学效应、地球化学特征以及与存在状态、价态的关系日趋关心。因此,环境样品中痕量的不同价态碲的分别测定,已为分析化学工作者所重视。其中氢化法原子吸收和无焰原子吸收法报导较多[1—9]。 我们在用巯基棉纤维富集多种微量元素[10—12]、分离有机汞与无机汞[13]、砷(Ⅲ)与砷(Ⅴ)[14]、锑(Ⅲ)与锑(Ⅴ)[15]、硒(Ⅳ)与硒(Ⅵ)(16)的基础上,提出利用巯基棉对碲(Ⅳ)和碲(Ⅵ)截然不同的吸附性能加以分离富集,然后用氢化法原子吸收分别测定的新方法。 本法与文献报导的数种方法相比,富集倍数大、测定灵敏度高、分离简便、选择性强,且有效地消除了多种共存元素干扰,可直接准确测定环境水样中痕量的碲(Ⅳ)和碲(Ⅵ)。     

X射线荧光光谱测定土壤和水系沉积物中的主元素和痕量元素

采用X射线荧光法分析土壤和沉积物中22种元素含量,以水系沉积物标样(GSD)做为标准样品,回归方法求取各元素的工作曲线常数,元素间效应的影响系数和谱线重叠校正系数,散射内标法和经验系数法共同校正基体效应。用本方法分析了西藏土壤标准参考物(83401)和水系沉积物标准(81101)中的多种元素,结果与标准值或参考值一致。方法简便、快速、有较好的检出下限和准确度。     

电感耦合等离子体发射光谱法测定汽油中硅(Si)及多种元素直接分析检测

本方法采用最新技术的同步垂直火炬双向观测等离子体原子发射光谱仪(5100ICP-OES),利用直接稀释法、挥发性制冷雾化室、有机加氧去除积炭及内标校正等手段.分析了几种不同市售汽油中多种金属元素.实验分别进行了不同稀释比率、精密度、回收率检出限等方法验证.结果表明仪器的分析精密度良好,分析的各元素相关线性良好,相关系数≥0.999.该方法简便,样品处理简单,经济实用,稳定性与检出限好,适用于对汽油中多种元素的直接分析检测.     

微波消解—电感耦合等离子体质谱法测定植物中痕量稀土元素

研究了电感耦合等离子体质谱（ＩＣＰ－ＭＳ）测定植物中痕量稀土元素（ＲＥＥｓ）的方法。详细讨论了测定稀土元素的质谱干扰及基体的抑制效应,采用代数法可有效地校正质谱干扰,内标法可以补偿基体的抑制效应。根据植物标准参考物质（ＧＳＶ－２,ＧＳＶ－４）的分析结果评价方法的准确性。在微波条件下,ＨＦ／ＨＣｌＯ４／ＨＮＯ３混合体系能快速而有效地分解植物样品,直接稀释后用ＩＣＰ－ＭＳ测定其中的稀土元素。     

一株假单胞菌MBR对亚碲酸盐的好氧还原特征

本实验室前期获得了一株假单胞菌MBR(Pseudomonas sp.MBR),能够在好氧环境以有机碳源为电子供体,将可溶性强、毒性高的亚碲酸盐还原为无毒的不溶性碲单质.本文主要报道对该菌好氧还原亚碲酸盐为碲单质的特性研究,结果表明,该菌对高浓度的亚碲酸钠具有抗性并还原为单质,由于碳源提供的电子供体不同,该菌对亚碲酸盐的最小抑制浓度(MIC)有较大差异,其中以丙酮酸为碳源的MIC最高,达到2 mmol/L.扫描电子显微镜和透射电子显微镜观察显示亚碲酸钠的毒性使细胞的形态发生了严重变形,细胞膜有裂解的迹象,还原的Te单质大量积累在细胞质内.     

季胺盐表面活性剂对微分脉冲阳极溶出伏安法的影响

本文介绍了不同条件下阳离子季胺盐表面活性剂用于微分脉冲阳极溶出伏安法,在分析微量金属时有增敏作用,且峰电流随金属离子所带电荷增加而增高。并对其机制进行初步探讨。     

疏水性有机物和有机酸碱溶解度的估算

本文从理论上建立了疏水性有机物和任意pH条件下有机酸碱溶解度的估算方法,并估算了不同类型有机物的溶解度,和实测值比较,结构和辛醇相近的有机物吻合较好;结构不同,则有一定的偏差,这是由于假设有机物在辛醇中的活度系物等于1所致。经校正后得到了较好的结果。     

ASD—ICP—MS联合快速测定土壤中部分金属元素

土壤环境质量例行监测正在全国展开,如何准确快速分析土壤中的金属含量成为当务之急。采用HNO3-HCl-HF—HClO4体系在全自动消解仪（ASD）上对土壤进行前处理,以50．0μg／L的铑作内标,电感耦合等离子体-质谱仪同时测定《土壤环境质量标准》的7种元素：Cd、As、Cu、Ph、Cr、Zn、Ni。各元素的方法检出限为0．003～0．40mg／kg,相对标准偏差小于6．0％,土壤标样的测定值与标准值吻合。该方法简便快捷、灵敏度高、重现性好,为大批量土壤重金属元素含量的快速测定提供了可靠地消解-分析方法。     

The Freshwater Mussel Parreysia Favidens (Benson) As A Biological Indicator of Polonium - 210 in A Riverine System

The concentration of ²¹⁰Po, an alpha emitter from the natural uranium series was measured in the soft tissues (total), shell, and different organs - digestive glands, gills, mantle and foot - of the freshwater mussel, Parreysia favidens (Benson), collected from the river Kaveri, at Tiruchirapalli in South India. the analyses were made in three size groups based on shell length (Group 1: 2-4 cm; Group 2: 4-5 cm; Group 3: 5-6 cm). the soft tissues of the mussel accumulated higher concentrations of ²¹⁰Po (74.0-125.5 Bq kg^-1 fresh) than the shell (2.9-3.9 Bq kg^-1 fresh). Further, younger mussels (1 group) showed higher concentrations (125.5+2.0 Bq kg^-1 fresh) in total soft tissues than older ones (III Group) (74.0+1.6 Bq kg^-1 fresh); concentration factors were 1.59x 10⁵ in I group and 9.37 × 10⁴ in III group. the ²¹⁰Po was observed to be non-uniformly distributed among the internal organs, which maintained the following descending order with reference to ²¹⁰Po accumulation: digestive glands, ranging from 286.2+3.5 Bq kg^-1 fresh to 43+1.3 Bq kg^-1 fresh. the concentration of ²¹⁰Po in the mussels was distinctly higher than that in the grass, Echinochloa colonum (J. Koenig), and carp, Cirrhinus cirrhosa (Bloch), from the same river. These data indicate that younger mussels could be used as an excellent biological indicator of ²¹⁰Po and among soft tissues, digestive glands are preferable to other tissues to monitor the distribution of ²¹⁰Po in the riverine system.     

Origin and Distribution of Suspended Organic Matter As Inferred From Carbon Isotope Composition in A Mediterranean Semi-Enclosed Marine System

The origin and distribution of suspended organic matter, the trophic features and the stable carbon isotopic composition of particulate organic carbon (POC) were studied monthly in a Western Mediterranean semi-enclosed basin. Sampling stations were selected as a function of wind-exposure and the degree of vegetation cover and then compared with an adjacent unvegetated site. the predominant vegetation was seagrass (Posidonia oceanica and Cymodocea nodosa) and Caulerpa prolifera. Water samples were analyzed for total suspended matter (inorganic and organic fractions), photosynthetic pigments (chlorophyll-a and phaeopigments), dissolved organic carbon, particulate organic carbon and their isotopic composition. Temperature and salinity were also measured at the same sampling sites within range of Mediterranean limits. the suspended organic matter concentration was 1.77 ± 1.55 mg l^-1; the chlorophyll-a concentration was low (0.35 ± 0.24 μg l^-1); the disolved organic carbon concentration was 2,140 ± 2,010 μg l^-1; the particulate organic carbon concentration was 212 ± 106 μg l^-1 and the isotopic composition was 18.77 ± 2.51%_°. There were significant temporal differences except for phaeopigments, POC and its POC isotopic composition, and there were no spatial differences other than for δ¹³C. This picture highlighted a general seasonal trend and trophical features similar to adjacent sea.

Spatial differences in δ¹³C showed that the source of suspended organic matter was different between stations as that between sources and wind-hydrodynamic constraints. In     

Retention of 137cesium in acid sulphate soils of South Central Thailand

Adsorption and desorption of ¹³⁷Cs by acid sulphate soils from the Nakhon Nayok province, South Central Plain of Thailand located near the Ongkarak Nuclear Research Center (ONRC) were investigated using a batch equilibration technique. The influence of added limestone (12 and 18 tons ha^-1) on ¹³⁷Cs adsorption-desorption was studied. Based on Freundlich isotherms, both adsorption and desorption of ¹³⁷Cs were nonlinear. A large portion (98.26-99.97%) of added ¹³⁷Cs (3.7 × 10³-7.03 × 10⁵ Bq l^-1) was sorbed by the soils with or without added lime. The higher lime treatments, however, favoured stronger adsorption of ¹³⁷Cs as compared with soil with no lime, which was supported by higher K_ads values. The addition of lime, the cation exchange capacity and pH of the soil increased and hence favoured the stronger adsorption of ¹³⁷Cs. Acid sulphate soils with a high clay content, medium to high organic matter, high CEC, and predominant clay types consisting of a mixture of illite, kaolinite, and montmorillonite were the main soil factors contributing to the high ¹³⁷Cs adsorption capacity. Competing cations such as NH₄⁺, K⁺, Na⁺, Ca²⁺, and Mg²⁺ had little influence on ¹³⁷Cs adsorption as compared with liming, where a significant positive correlation between K_ads and soil pH was observed. The ¹³⁷Cs adsorption-desorption characteristics of the acid sulphate soils studied exhibited a very strong irreversible sorption pattern. Only a small portion (0.09-0.58%) of ¹³⁷Cs adsorbed at the highest added initial ¹³⁷Cs concentration was desorbed by four successive soil extractions. Results clearly demonstrated that Nakhon Nayok province acid sulphate soils have a high ¹³⁷Cs adsorption capacity, which limits the ¹³⁷Cs bioavailability.     

Influence of pore structure on biologically activated carbon performance and biofilm microbial characteristics

• Pore structure affects biologically activated carbon performance. • Pore structure determines organic matter (OM) removal mechanism. • Microbial community structure is related to pore structure and OM removal. Optimizing the characteristics of granular activated carbon (GAC) can improve the performance of biologically activated carbon (BAC) filters, and iodine value has always been the principal index for GAC selection. However, in this study, among three types of GAC treating the same humic acid-contaminated water, one had an iodine value 35% lower than the other two, but the dissolved organic carbon removal efficiency of its BAC was less than 5% away from the others. Iodine value was found to influence the removal of different organic fractions instead of the total removal efficiency. Based on the removal and biological characteristics, two possible mechanisms of organic matter removal during steady-state were suggested. For GAC with poor micropore volume and iodine value, high molecular weight substances (3500–9000 Da) were removed mainly through degradation by microorganisms, and the biodegraded organics (soluble microbial by-products,<3500 Da) were released because of the low adsorption capacity of activated carbon. For GAC with higher micropore volume and iodine value, organics with low molecular weight (<3500 Da) were more easily removed, first being adsorbed by micropores and then biodegraded by the biofilm. The biomass was determined by the pore volume with pore diameters greater than 100 μm, but did not correspond to the removal efficiency. Nevertheless, the microbial community structure was coordinate with both the pore structure and the organic removal characteristics. The findings provide a theoretical basis for selecting GAC for the BAC process based on its pore structure.     

Estimation of Similarity in the Qualitative Composition of Humic Substance in Marine Sediments By Means of an Uv-Spectroscopic Library

In this paper a method for the study of the qualitative similarity of extractable humic substance (EHS) in marine sediments based on the realisation of UV spectral library of EHS is described. the spectral library was built including the digitised spectra of humic substance extracted from several marine sediments (46 samples) and two samples of standard materials (lignin sulphonate and humic substance) in a Statistica data file. the data matrix was elaborated by means of different multivariate statistic techniques such as Cluster Analysis (CA), Principal Components Analysis (PCA) and the univariate technique Spectral Correlation Analysis (SCA). This approach allows us to show the contribution of different organic compounds (aromatic, lipid and acid) to the composition of EHS and moreover it evidences also the structural characteristics of EHS in terms of similarities in the qualitative composition of samples such as presence of terrestrial and/or vegetal contributions. the UV library is an objective tool to study the qualitative composition of EHS and it represents a complementary approach to the most common methods based on the application of spectroscopic (IR, ¹³CNMR), potentiometric and chromatographic techniques.     

Whole pictures of halogenated disinfection byproducts in tap water from China’s cities

When bromide/iodide is present in source water, hypobromous acid/hypoiodous acid will be formed with addition of chlorine, chloramine, or other disinfectants. Hypobromous acid/hypoiodous acid undergoes reactions with natural organic matter in source water to form numerous brominated/iodinated disinfection byproducts (DBPs). In this study, tap water samples were collected from eight cities in China. With the aid of electrospray ionization-triple quadrupole mass spectrometry by setting precursor ion scans of m/z 35, m/z 81, and m/z 126.9, whole pictures of polar chlorinated, brominated, and iodinated DBPs in the tap water samples were revealed for the first time. Numerous polar halogenated DBPs were detected, including haloacetic acids, newly identified halogenated phenols, and many new/unknown halogenated compounds. Total organic chlorine, total organic bromine, and total organic iodine were also measured to indicate the total levels of all chlorinated, brominated, and iodinated DBPs in the tap water samples. The total organic chlorine concentrations ranged from 26.8 to 194.0 μg·L^–1 as Cl, with an average of 109.2 μg·L^–1 as Cl; the total organic bromine concentrations ranged from below detection limit to 113.3 μg·L^–1 as Br, with an average of 34.7 μg·L^–1 as Br; the total organic iodine concentrations ranged from below detection limit to 16.4 μg·L^–1 as I, with an average of 9.1 μg·L^–1 as I; the total organic halogen concentrations ranged from 31.3 to 220.4 μg·L^–1 as Cl, with an average of 127.2 μg·L^–1 as Cl.     

Decoding and quantitative detection of antibiotics by a luminescent mixed-lanthanide-organic framework

● A series of mixed-LOFs and portable LOF-fibers were synthesized. ● LOF-S3 was selected as a luminescent sensor for antibiotics. ● Mixed-LOF was capable of decoding antibiotics by emission intensity ratios. ● Linear relationship between antibiotic concentration and I545nm/I618nm was observed. Due to the potential risk of antibiotics to the environment, the development of inexpensive, simple, and reliable antibiotic detection methods is significant but also faces challenges. In this work, several lanthanide-organic frameworks (LOFs), constructed from lanthanide ions (Eu³⁺ and/or Tb³⁺) and 1,3,5-benzene-tricarboxylic acid (BTC), were synthesized by solvothermal method. LOF-S3 with comparable emission peaks of ⁵D₄ → ⁷F₅ (Tb³⁺, 545 nm) and ⁵D₀ → ⁷F₂ (Eu³⁺, 618 nm) was selected as a luminescent sensor. In this system, the highly efficient energy transferred from the organic linker to lanthanide ions and from Tb³⁺ to Eu³⁺ occurs. LOF-S3 sensor was capable of decoding antibiotics by distinguishable emission intensity ratios. Therefore, a two-dimensional decoded map of antibiotics was established. The linear relationship between antibiotic concentration and emission intensity ratio indicated the quantitative determination of antibiotics was feasible. As a typical analyte, the response mechanism of nalidixic acid (NA) was investigated in detail. The competition of NA and BTC for UV light absorption, as well as the binding propensity of NA and Tb, affected the organic linkers-to-lanthanide ions and Tb-to-Eu energy transfer, resulting in the change of fluorescence intensity ratio. The self-calibrating mixed-LOF sensor overcame the uncontrollable errors of the traditional absolute emission intensity method and generated stable luminescent signals in multiple cycles. Furthermore, the integration of LOF-S3 with polymer fibers enabled the formation of a LOF-polymer fibrous composite with fluorescence detection capability, which is a promising portable sensor for practical applications.     

Community Experiments Using Benthic Chambers: Microbial Significance in Highly Organic Enriched Sediments

The structure of the benthic microbial loop was studied in order to understand heterotrophic pathways in the suboxic sediments of the Rapallo Harbour in autumn, 1996. Sediments were characterized by the large accumulation of organic detritus (17.2 - 21.4 μg chloroplastic pigment equivalents (CPE)g^-1; carbohydrates and proteins: 7.8-16.7 and 6.7-7.5 mg g^-1). Due to the high organic load, benthic bacteria and protozoa displayed extremely high densities (1.4 × 10⁹ cells g^-1 and 26.9 × 10⁵ cells g^-1). Meiofauna, protozoa and bacteria showed an approximate biomass ratio of 1:2:20. the presence of large amounts of organic matter appeared to determine a shift of the benthic size structure toward the increasing dominance of the smaller components of the benthic food webs. These data indicate that the sediments of the Rapallo Harbour were dominated by microbial biomasses to a larger extent than in non-food limited environments, characterized by a lower organic contamination. On the results presented in this study, the microbial dominance in highly organic enriched sediments can be explained with: (1) a reduction of the top-down control and grazing pressure of meio- and macrofauna on the microbial components; (2) the opportunistic composition and high metabolic activity of the microbial components.     

Chemical reclamation of crude-oil-inundated soils from Niger Delta, Nigeria

Crude-oil-inundated soils were collected from the Agbada oil field in the Niger Delta region of Nigeria 2 months after the recorded incidence of oil spillage. The soils were taken on the second day of reconnaissance from three replicate quadrats, at surface (0-15 cm) and subsurface (15-30 cm) depths, using the grid sampling technique. The total extractable hydrocarbon content (THC) of the polluted soils ranged from 1.24 × 10² to 3.86 × 10⁴ mg/kg at surface and subsurface depths (no overlap in standard errors at a 95% confidence level). Greenhouse trials for possible reclamation were later carried out using 10-100 g of (NH₄)₂SO₄, KH₂PO₄ and KCl (NPK) fertilizer as nutrient supplements. Nitrogen as NO₃-N and potassium were optimally enhanced at 2% (w/w) and 3% (w/w) of the NPK supplementation, respectively. Phosphorus, which was inherently more enhanced in the soils than the other nutrients, maintained the same level of impact after treatment with 20 g of NPK fertilizer. Total organic carbon (%TOC), total organic matter (%TOM), pH, and percentage moisture content all provided evidence of enhanced mineralization in the fertilizer-treated soils. If reclamation of the crude-oil-inundated soils is construed as the return to normal levels of metabolic activities of the soils, then the application of the inorganic fertilizers at such prescribed levels would duly accelerate the remediation process. However, this would be limited to levels of pollution empirically defined by such THC values obtained in this study.     

Radioactivity Monitored From Moored Oceanographic Buoys

The principles and operation of a gamma radiation sensor mounted on oceanographic buoys are described. the sensor has proved rugged in severe weather conditions and has satisfactory detection limits and accuracy. Continuous monitoring of artificially produced γ-emitters such as ¹³⁷Cs, ¹³⁴Cs, ¹³¹I, ¹³³I, ¹³²Te, naturally occuring emitters such as ⁴⁰k and ²¹⁴Bi in open sea conditions can provide important information in critical situations.