Evaluation of high-pressure microwave digestion methods for hydride generation atomic absorption spectrometric determination of total selenium and arsenic in sediment

Five closed-vessel microwave digestion methods were compared for the accurate determination of arsenic and selenium in NIST SRM 1645 River Sediment by flow-injection hydride-generation atomic absorption spectrometric methods. The digestion methods using five different acid mixtures (HNO₃/ H₂SO₄, HNO₃/HCl0₄, HNO₃/HCl, HNO₃/HCl/HF, HNO₃/H₂SO₄/HClO₄) were all found to be reliable for the determination of the analytes. Taking into consideration the safety and suitability for the analysis of other metals, the methods based on the use ofaqua regia are recommended for closed vessel microwave digestion with pressure control. Using the quick digestion program, the presence of up to 10% organic content in soil samples did not adversely affect the closed vessel digestion and did not cause the loss of volatile analytes. After digestion, opening the vessel under an inner pressure of below 345 kPa (50 psi) had no effect on the accuracy of the results. The recommended digestion methods (HNO₃/HCl and HNO₃/ HCl/HF) for the reliable determination of arsenic and selenium in different sediment samples were demonstrated. The calculated detection limits (3 _b ) were less than 0.030 g/g and 0.033 g/g for arsenic and selenium, respectively. All analytical results for arsenic and selenium in SRM 1645 River sediment, NRCC BCSS-1 Marine Sediment and NIES CRM Pond Sediment were within or near the certified and reported ranges, with the exception of selenium in NIES CRM No. 2 Pond Sediment.     

Fate of branched-chain fatty acids in anaerobic environment of river sediment

The fate of six different branched-chain fatty acids (BCFAs) in an anaerobic environment of a river sediment was studied in vitro by culturing enrichment consortia. The anaerobic consortium of BCFA-degrading genus degraded BCFAs with tertiary carbons through β-oxidation, followed by methanogenesis by methane-producing anaerobic bacteria. The consortium could not degrade BCFAs with quaternary carbon. Degree of branching at the alpha or beta position along the carbon chain interfered with the beta-oxidation mechanisms of the branched-chain fatty acid.     

Measurement of butyltin contamination of water and sediment in Osaka Bay,Japan

The concentration of tributyltin (TBT) in surface water from Osaka Bay ranged from 0.023 to 0.061 µg l⁻¹ in 1989 and from not detected (ND) to 0.059 µg l⁻¹ in 1990 while the proportion of TBT as a percentage of the total butyltins (BTs) was more than 40%. The concentration of TBT was also surveyed in the Port of Osaka and the Yodo River basin. TBT levels were highest in the estuary (the Port of Osaka), followed by sea areas (Osaka Bay) and rivers (Yodo River basin). A fairly high correlation coefficient between TBT concentration and salinity in water from the estuary and the sea areas was observed. This result shows that the TBT in the estuary water is diluted by seawater. Generally, the TBT concentrations in the water columns were distributed uniformly and the composition of the BTs was also constant. TBT was detected in sediment from Osaka Bay in the range from ND to 0.023 mg kg⁻¹ dry weight with a high ratio of monobutyltin (MBT) to the total BTs. TBT in sediment core was also measured; its concentration decreased with core depth. It was estimated from these measurements that the release of TBT into Osaka Bay began in the 1960s. Copyright © 1998 John Wiley & Sons, Ltd.     

Finite element analysis of axisymmetric elastic body problems

Linear form functions are commonly used in a long time for a toroidal volume element swept by a triangle revolved about the symmetrical axis for general axisymmetrical stress problems. It is difficult to obtain the rigidity matrix by exact integration, and instead, the method of approximate integration is used. As the locations of element close to the symmetrical axis, the accuracy of this approximation deteriorates very rapidly. The exact integration have been suggested by various authors for the calculation of rigidity matrix. However, it is shown in this paper that these exact integrations can only be used for those axisymmetric bodies with central hole. For solid axisymmetric body, it can be proved that the calculation fails due to the divergent property of rigidity matrix integration. In this paper a new form function is suggested. In this new form function, the radial displacementu vanishes as radial coordinatesr approach to zero. The calculated rigidity matrix is convergent everywhere, including these triangular toroidal element closed to the symmetrical axis. This kind of element is useful for the calculation of axisymmetric elastic solid body problems.     

超临界流体色谱法同时测定海洋水体及沉积物中的4种双酚

在超临界流体色谱分析条件下,建立了由液液萃取与超临界流体色谱（supercritical fluid chromatography,SFC）同时测定海洋水体中双酚A（BPAF）、双酚AF（BPA）、双酚C（BPC）、四溴双酚A（TBBPA）4种内分泌干扰物的方法。实验结果表明,当SFC流动相为超临界态二氧化碳和甲醇,检测波长为230 nm,柱温为36 ℃、流速为2.0 mL·min^-1、系统背压为12 MPa时,5 min内即可实现对双酚类化合物的分离。在线性浓度范围内,双酚类化合物的线性相关系数均高于0.998 9,检出限为0.03~0.06 mg·L^-1,4种双酚类化合物在实际样品中的加标回收率为85.7%~112.0%,相对标准偏差均小于10.3%。本文方法可简便快速地检测海洋水体中的双酚,灵敏度和选择性较高,对研究和追踪海洋环境中双酚类化合物的分布具有重要意义。     

松散沉积物的有效密度及其声压反射损失

本文将液型介质向松散的沙质沉积物中延拓,获得了松散沙质沉积物中的有效密度表达式,利用该表达式计算了松散的沙质沉积物表面上的平面声波的反射系数的模,并与实验数据进行比较,理论与实验相符合。     

Solubility of highly charged anionic polyelectrolytes in presence of multivalent cations: Specific interaction effect

Studies performed on strong polyelectrolytes and on a weak polyelectrolyte, sodium poly(acrylate), show that their stability in presence of multivalent cations depends on the chemical nature of the charged side groups of the polymer. For sulfonate groups (SO₃ ^-) or sulfate groups (OSO₃ ^-) phase separation generally occurs in presence of inorganic cations of valency 3 (as La³⁺) or larger and a resolubilization takes place at high salt concentration. The interactions of the polyelectrolyte with multivalent cations are of electrostatic origin and the phase diagrams are weakly dependent on the chemical nature of the polymer backbone and on the specificity of the counterions. For acrylate groups, (COO^-), the phase separation was observed with inorganic cations of valency 2 (as Ca²⁺) or larger without resolubilization at high salt concentration. The phase separation is due to a chemical association between cations and acrylate groups of two neighboring monomers of the same chain. This chemical association creates a hydrophobic complex by dehydrating both monomer and cation. With organic trivalent cation, as spermidine ⁺H₃N(CH₂)₄NH₂ ⁺(CH₂)₃NH₃ ⁺, where no chemical association occurs with the charged side groups COO^- or SO₃ ^- of the polyelectrolyte, similar phase diagrams were observed whatever was the polyelectrolyte with a resolubilization at high trivalent cation concentration. Received 3 March 1999 and Received in final form 2 September 1999     

Analytical method development for the determination of four biocides used in antifouling paints in estuarine waters and sediments by gas chromatography-mass spectrometry

Summary Irgarol 1051, chlorothalonil, dichlofluanid and diuron are biocides utilised in antifouling paints as alternatives to organotin compounds, after restrictions imposed in the use of tributyltin in 1987. Effective analytical methods for the simultaneous determination of these four biocides in waters and sediments have been developed and method performance data are presented. Quantification is by gas chromatography—electron ionisation mass spectrometry (GC-EI-MS). The method involves the simultaneous extraction of the biocides from water with dichloromethane or from sediments with dichloromethane and acetone. For the determination of diuron the extract was methylated prior to GC analysis to avoid thermal degradation in the instrument. The method was applied to water and sediment samples spiked with the biocides. The highest detection sensitivities were achieved in the selected-ion monitoring (SIM) mode. Recovery studies were performed at 20, 2 and 1 ppb for all biocides in water and 400, 40 and 20 ppb in sediments. The percentage recoveries ranged between 90 and 100% for waters and 80 and 90% for sediments. Seven determinations were made at each concentration level along with a procedural blank. The quantification limit of the method was around 0.2 ppb for water and 5 ppb for sediments depending on the individual compound.     

海河底泥中12种抗生素残留的液相色谱串联质谱同时检测

建立了同时检测河流底泥中12种抗生素(4种磺胺类、3种喹诺酮类、2种四环素类、2种大环内酯类、甲氧苄啶)残留的高效液相色谱串联质谱检测方法(HPLC-MS/MS)。样品提取过程中以NaF为离子交换剂,经2种提取液逐次提取,合并提取液,正己烷脱脂,萃取物经SAX-HLB固相萃取系统净化浓缩,氮吹,定容。以乙腈和0.3%甲酸为流动相,采用梯度洗脱进行液相色谱分离,以Simatone为内标物,用质谱检测器进行定性和定量分析。12种目标物的检出限为1.0~5.0 ng/g,回收率为65%~91%,相对标准偏差为0.6%~5.1%(n=4)。     

自动消解仪—ICP法测定水系沉积物中6种重金属元素

建立了自动消解仪-电感耦合等离子体发射光谱法(ICP-OES)同时测定水系沉积物中Cu、Zn、Ni、Cr、Pb、Co六种元素含量的方法。该方法的相关系数好、检出限低。方法经国家标准物质(GBW07361)验证,准确度和精密度均能达到环境监测分析的要求,为水系沉积物中重金属元素含量的测定提供了简单可靠的分析方法。