GEOENVIRONMENTAL CHARACTERS OF YELLOW (HUANGHE) RIVER SUSPENDED LOAD

Three important characters of the suspended load of the Yellow (Huanghe) River are discussed, i.e. its temporal fluctuation as a function of solar activity, its uneven spatial distribution along the main course and the inevitability of these phenomena as a natural earth process rather than a result of disturbed ecological system caused by human activity. Implications of this understanding with regard to the control of the Yellow River are also discussed.     

Pyrite Genesis During Early Diagenesis in Yellow Sea and East China Sea

The content and isotopic compositions of different sulphur species in pore-water and solid phases have been examined on five sediment cores taken from muddy sediment region in the Yellow Sea and the East China Sea. Relationships among these data have been investigated with the combination of morphology of mineral pyrite and organic matter so as to role out the diagenetic behaviour of sulphur species at the early stage of diagenesis in modern marine sediment and the origin of pyrite formation.     

New NIST sediment SRM for inorganic analysis

NIST maintains a portfolio of more than 1300 standard reference materials (SRM), more than a third of these relating to measurements in the biological and environmental fields. As part of the continuous renewal and replacement efforts, a set of new marine sediments has been recently developed covering organic and inorganic determinations. This paper describes the steps taken in sample preparation, homogeneity assay, and analytical characterization and certification with specific emphasis on SRM 2702 inorganics in marine sediment. Neutron activation analysis showed the SRM to be highly homogeneous, opening the possibility for use with solid sampling techniques. The certificate provides certified mass fraction values for 25 elements, reference values for eight elements, and information values for 11 elements, covering most of the priority pollutants with small uncertainties of only several percent relative. The values were obtained by combining results from different laboratories and techniques using a Bayesian statistical model. An intercomparison carried out in field laboratories with the material before certification illustrates a high commutability of this SRM.Electronic Supplementary Material Supplementary material is available in the online version of this article at     

Determination of mercury in soils and sediments by graphite furnace atomic absorption spectrometry with slurry sampling

A graphite furnace atomic absorption spectrometric procedure for the determination of mercury is presented, in which the samples are suspended in a solution containing hydrofluoric and nitric acids. Silver nitrate (4% m/v) and potassium permanganate (3%) are incorporated, in the order specified, and aliquots are directly introduced into the graphite furnace. A fast heating programme with no conventional pyrolysis step is used. The detection limit for mercury in a 125 mg ml⁻¹ suspension is 0.1 μg g⁻¹. Calibration is performed by using aqueous standards. The reliability of the procedure is proved by analysing certified reference materials.     

The Employ of Multiple Voltammetric Pulses for the Study of the Adsorption of Bipyridilium Pesticides in River Sediment

The multiple square‐wave voltammetry (MSWV) allied to gold microelectrode (Au‐ME) was used to establish an electroanalytical procedure for the determination of the paraquat and diquat pesticides in river sediment samples. For both pesticides, two reduction peaks, at around ?0.70 V (peak 1) and around ?1.00 V vs. Ag/AgCl 3.00 mol L^?1 (peak 2), with profile of the totally reversible redox process, were observed. The experimental and voltammetric conditions showed that the best conditions to reduce paraquat and diquat were a pH of 6.0, a frequency of 250 s^?1, a scan increment 2 mV, a square‐wave amplitude of 50 mV and pulse number of 8 pulses of potential in each step of staircase of potential. Under such conditions, the detection limit of 0.044 μg L^?1 (0.044 ppb) and 0.360 μg L^?1 (0.360 ppb ) for peak 1 and peak 2 of paraquat and 0.159 μg L^?1 (0.159 ppb) and 0.533 μg L^?1 (0.533 ppb) for peak 1 and peak 2 of diquat, respectively, were obtained. These results are an order of magnitude of about two less than those obtained and published in the literature. Also, the electroanalytical procedure proposed was applied for the determination of adsorption isotherms of pesticides on river sediments samples collected from Mogi‐Guaçu River in Sao Paulo State, Brazil. The experimental data were fitted using the Langmuir and Freundlich isotherms models; and the results indicated low intensities of adsorption process of the pesticides in the samples employed with distribution coefficients (K_d) lower 5.0, and paraquat showed slightly higher affinity than diquat in the sediments. The increase in organic matter and organic carbon leads to an increase in the K_d values, and consequently an increase in the organic matter constant (K_OM) organic carbon constant (K_OC) values. All results demonstrated that isotherms “L” type in the Giles classification were obtained, indicating that sediments have a medium affinity for the pesticides, and no strong competition from the solvent used (in this case Na₂SO₄) for adsorption sites occurs.     

Metal furnace heated by flame as a hydride atomizer for atomic absorption spectrometry: Sb determination in environmental and pharmaceutical samples

The present work describes a metallic hydride atomizer for atomic absorption spectrometry, by evaluating the performance of the Inconel 600^® tube. For this purpose, stibine was used as the model volatile compound and antimony determination in river and lake sediments and in pharmaceutical samples was carried out to assess the metal furnace performance. Some parameters are evaluated such as those referring to the generation and transport of the hydride (such as KBH₄ and acid concentrations, carrier gas flow rate, injected volume, etc.), as well as those referring to the metal furnace (such as tube hole area, flame composition, long-term stability, etc.). The method presents linear Sb concentration from 2 to 80 μg L⁻¹ range (r > 0.998; n = 3) and the analytical frequency of ca. 140 h⁻¹. The limit of detection (LOD) is 0.23 μg L⁻¹ and the precision, expressed as R.S.D., is less than 5% (40 μg L⁻¹; n = 10). The accuracy is evaluated through the reference materials, and the results are similar at 95% confidence level according to the t-test.     

Efficiency of tributyltin extraction from rhine river sediment

A Rhine river sediment sample was spiked with tributyltin (TBT), equilibrated for ten days and the tributyltin extraction efficiency was optimised using a simplex algorithm. Analysis was effected using hydride generation gas chromatography-atomic absorption spectroscopy (GC-AAS) apparatus. The results show that, in this sediment sample, different molarities of HCl in methanol extract different species with varying extraction efficiencies. The least polar extraction solution extracted TBT more efficiently, whilst DBT and MBT require molar solution of HCl in methanol for efficient extraction.     

Evaluation of a synergetic effect between Rh as permanent chemical modifier and acetylacetone as complexing agent in Sc determination in sediment slurry samples by ETAAS

In the present work, scandium was determined in sediment slurry samples (from three different rivers) by electrothermal atomic absorption spectrometry (ETAAS). Slurries were prepared by weighting 100 mg of dry sediment samples (≤53 μm particle sizes) and adding 6 ml of HCl:HNO₃:HF (3:1:2, v/v). Accurate results were only possible due to the synergetic effect between Rh as permanent chemical modifier and acetylacetone (Acac) as complexing agent. The same platform was used for 400 heating cycles. The performance of the chemical modification was evaluated by using scanning electron microscopy (SEM), synchrotron radiation X-ray fluorescence (SRXRF) and some figures of merit (precision and detectability). The best analytical conditions were attained using 1500 and 2550 °C as pyrolysis and atomization temperatures. The scandium content in the liquid phase of the slurries ranged from 61 to 73%, thus indicating, in this study, that both liquid and solid phases play an important role in slurry analyses. An amount of 5.0–20.0 μg l⁻¹ Sc linear range as well as LOD and LOQ of 0.19 and 0.62 μg l⁻¹, respectively, were obtained under these conditions. The accuracy was checked by using microwave-assisted decomposition, and the results compared to those obtained with the proposed methodology (slurry analysis). By checking both sets of the results, there is no statistical difference at the 95% confidence levels.     

Air-Segmented Continuous-Flow Analysis for Molybdenum in Various Geochemical Samples

 An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L⁻¹ and 17 pmol L⁻¹, and the reproducibilities at 10 nmol L⁻¹ were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our knowledge, and is also convenient for routine analysis of molybdenum in various natural samples. Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp Received October 23, 2002; accepted January 28, 2003 Published online May 19, 2003     

Dynamic release process of pollutants during suspended sediment transport in aquatic system

Pollutants release is highly consistent with suspended sediment concentration （SSC） in water column, especially during re-suspension and transport events. The present research focuses on pollutant dynamic release from re-suspended sediment, especially the vertical distribution relationship between them. The sediment erosion experiments on a series of uniform flow are conducted in a circulate flume. Reactive tracer （phosphorus） is used as the contaminant in fine-grained sediments to identify the release characteristic length and time. Experimental results show that the flow condition near-bed depends on the sediment surface roughness. The region with high turbulent intensities corresponds to a high concentration sediment layer. In addition, the SSC decreases with the distance, water depth, and particle grain size. The sediment in a smaller grain size takes much more time to reach equilibrium concentration. Total phosphorus （TP） concentration changes along the water depth as SSC in the initial re-suspension stage, appearing in two obvious concentration regimes： the upper low-concentration layer and the high-concentration near-bottom layer. This layered phenomenon remains for about 3 hours until SSC distri- bution tends to be uniform. Longitudinal desorption plays an important role in long-way transport to reduce the amount of suspended sediment in water column.