Zum Einfluß des pH-Wertes und des Calciumgehaltes auf Metall-Fulvinsäure-Bindungen — Inversvoltammetrische und chemometrische Untersuchungen     

W. v. Tümpling  S. Geiß  J. Einax 《洁净——土壤、空气、水》1992,20(6):320-325

The Influence of pH and Calcium Concentration on Metal-Fulvic Acid Bonds – Stripping Voltammetric and Chemometric Investigations. Electrochemically available metal concentrations of Cd, Cu and Zn were analyzed in dependence of different concentrations of calcium, fulvic acids and pH by Differential Pulse Anodic Stripping Voltammetry (DPASV). A statistical experimental design was the base to minimize the number of experiments and to include the multifarious interactions between the independent variables (Ca concentration, concentration of fulvic acids and the pH value) and otherwise the electrochemically available metal concentrations of Cd, Cu and Zn. At first analysis of experimental data was carried out by multiple linear regression. The main influence on available metal concentrations is the pH value especially for Cu. The Ca ion influence has not competitive effect and is only significant for Cd and Cu. It has an effect on the metal-fulvic acid-bonds. Two factor interactions exist for pH/fulvic acids and for Ca/fulvic acids too. The partial least squares regression (PLS) model was used to include the interactions between the metals Cd, Cu and Zn. For proving these two models the three parameters pH, Ca and fulvic acid were varied within the calibration range of the models and predicted values were compared with the experimental values. The approach with the PLS model is better than the approach with the multiple linear regression (normally used mathematical method of analysis of a factorial plan) with a relative error of 9.7% for modelling of Cd, 6.0% for Zn and 58% for Cu in relation to multiple linear regression with errors of 12% for Cd, 8.6% for Zn and 65% for Cu. The PLS modelling is a suited tool for modelling chemical interactions also in simulated natural matrices.  相似文献   

Selenium fractionation and speciation in rocks, soils, waters and plants in polluted surface mine environment   总被引：1，自引：0，他引：1  

M. Bujdoš  A. Muľová  J. Kubová  J. Medveď 《Environmental Geology》2005,47(3):353-360

A fractionation and speciation was performed to determine the distribution of selenium (Se) species in major components of quartzite surface mine environment (rocks, mine tailings, soils, stream sediments, surface waters and plants) in obov, Slovakia. A three-step sequential extraction procedure was utilised for the fractionation of Se in mine tailings and soils. The first extractant in order to evaluate the soluble and ligand exchangeable fraction of Se (0.1 mol/l K₂HPO₄ + KH₂PO₄ at pH 7.0) solubilized up to 15% of total Se content. The second step (0.1 mol/l K₂S₂O₈ at 90°C) which extracted Se associated or occluded with organic matter released 13 – 45% of total selenium. The decomposition of the residue (HNO₃ + H₂SO₄ 1+1) was used to solubilize the remaining 35–88% of total Se as the final step. The recovery of the procedure was between 97 and 106%. Selenate predominated in natural river and lake waters about pH 7.0 (>95%) but in acid mine leakings up to 40% of selenite was found. In the plants (birch leaves, grass leaves and roots) collected from the area acidified by mine leakings no significant accumulation of selenium was observed. The correlation between total Se and S in the rocks from the mine gives an evidence of the common origin of these elements in the studied area.  相似文献   

Mobility of some potentially toxic trace elements in the coal of Guizhou, China   总被引：5，自引：0，他引：5  

X. Feng  Y. Hong  B. Hong  J. Ni 《Environmental Geology》2000,39(3-4):372-377

 The mobility of 10 potentially toxic trace elements (PTTE), As, Cd, Cr, Cu, Hg, Ni, Pb, Se, Tl, and Zn from 32 coals of the Longtan Group formed in Permian Period in Guizhou Province, China was investigated using sequential extraction procedures. The results demonstrate that PTTEs such as Hg, As, Se, Cd, Cu, and Pb have the highest mobility at surface conditions, and the average extractable fractions of them are 86%, 95%, 79%, 76%, 69%, and 69% of the total amount in coal, respectively. The elements in coal with the lowest leachability include Tl, Cr, and Ni, and the average extractable fractions of them are 30%, 20%, and 29% of the total amount in coal respectively. Zinc has an intermediate behavior, and the average leachable fraction of it accounts for 46% of the total amount in coal. The results demonstrate that mobility of PTTE in coal depends on the speciation of these elements. The elements associated with sulfates, carbonates, sulfides and some organic matter in coal show the highest extraction rates during the weathering process, while elements with silicate affinities are inert at surface conditions. Received: 29 December 1998 · Accepted: 10 November 1998  相似文献   

Improved thermodynamic calculations for concentrated mixed electrolyte systems including ion pairing (or the absence of it)     

Peter M. May   《Marine Chemistry》2006,99(1-4):62

Knowledge of the activity coefficients of solutes under temperature and pressure ranges of interest is generally required for calculations of the physicochemical properties of aqueous multicomponent electrolyte solutions such as seawater. Whilst these activity coefficients are well characterized for the predominant salts individually, fewer data are available for minor components under a sufficiently wide range of conditions and there are significant interactions between some of the chemical species involved which can substantially alter the required activity coefficients in mixtures.For these reasons, accurate thermodynamic predictions for seawater and other multi-electrolyte solutions in moderate or high concentration are more difficult than is often supposed. In particular, progress in this area has been slowed by uncertainty regarding the nature and extent of ion pairing in concentrated strong electrolyte solutions, a problem that has been debated for decades. Zdanovskii's rule, described originally almost a century ago but widely neglected, provides a fundamentally sound method for calculating the properties of mixed electrolyte solutions. Modelling developments are described, which accord with various types of experiment, from our laboratory and from the chemical literature. It has become clear that, when treated in an appropriate way based on solvent activity, linear mixing behaviour of strong electrolyte solutions can be considered the norm. This is an inevitable consequence, first recognized by Guggenheim, of the cancellation of ion pairing and other interactions as, conceptually, one ion replaces another. Stronger solute–solute interactions, described by equilibrium constants, can then easily be coupled in a thermodynamically consistent manner.  相似文献   

Mercury speciation in sediments at a municipal sewage sludge marine disposal site   总被引：3，自引：0，他引：3  

Shoham-Frider E  Shelef G  Kress N 《Marine environmental research》2007,64(5):601-615

Mercury speciation was performed in excess activated sewage sludge (ASS) and in marine sediments collected at the AAS disposal site off the Mediterranean coast of Israel in order to characterize the spatial and vertical distribution of different mercury species and assess their environmental impact. Total Hg (HgT) concentrations ranged between 0.19 and 1003ng/g at the polluted stations and 5.7 and 72.8ng/g at the background station, while the average concentration in ASS was 1181+/-273ng/g. Only at the polluted stations did HgT concentrations decrease exponentially with sediment depth, reaching background values at 16-20cm, the vertical distribution resulting from mixing of natural sediment with ASS solids and bioturbation by large populations of polycheates. Average Methyl Hg (MeHg) concentration in ASS was 39.7+/-7.1ng/g, ca. 3% of the HgT concentration, while the background concentrations ranged between 0.1 and 0.61ng/g. MeHg concentrations in surficial polluted sediments were 0.7-5.9ng/g (ca. 0.5% of the HgT) and decreased vertically, similar to HgT. A positive correlation between MeHg and Hg only at the polluted stations, higher MeHg concentrations at the surface of the sediment and not below the redoxline, and no seasonality in the concentrations suggest that the MeHg originated from the ASS and not from in situ methylation. By doing selective extractions, we found that ca. 80% of the total Hg in ASS and polluted sediments was strongly bound to amorphous organo-sulfur and to inorganic sulfide species that are not bioavailable. The fractions with potential bioaccessible Hg had maximal concentrations in the range in which biotic effects should be expected. Therefore, although no bioaccumulation was found in the biota in the area, the concentration in the polluted sediments are not negligible and should be carefully monitored.  相似文献   

Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans   总被引：1，自引：0，他引：1  

Qiu JW  Tang X  Zheng C  Li Y  Huang Y 《Marine environmental research》2007,64(5):563-573

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19micromol site mg(-1) C, and a logK' of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu-FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC(50) of 58.9microgl(-1). However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC(50) ranging from 55.6microgl(-1) in the no-FA control to 137.4microgl(-1) in the 20mgl(-1) FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu-FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.  相似文献   

The variability of δ34S and sulfur speciation in sediments of the Sulejów dam reservoir (Central Poland)     

《Chemie der Erde / Geochemistry》2017,77(1):147-157

The study was carried out on the Sulejów dam reservoir (Central Poland). Water and sediment samples were collected between February and October 2006. Sulfur compounds in the sediment were chemically extracted and subjected to isotopic analysis.Large variability of SO₄²⁻ concentration in the water column (from 10.3 to 36.2 mg/dm³) and the isotopic composition of sulfur (δ³⁴S from 2.1 to 5.4‰) was observed. The main identified sources of SO₄²⁻ were watercourses, surface runoff, and phosphorus fertilizers.Both oxidized sulfur species (SO₄²⁻) and its reduced forms were found in sediments. Particular sulfur forms were characterized by large variations in both, concentrations and the isotopic composition of sulfur. SO₄²⁻ in the sediment and in the water column had different genesis. Bacterial oxidation of organic sulfur and its binding in SO₄²⁻ were observed in the sediment. Under reducing conditions, oxidized and organic sulfur is converted to H₂S which reacted with Fe or other metallic ions leading to metal sulfide precipitation. Monosulfides were shown to have a very low concentration, ranging up to 0.07 mg/g of sediment. The transformation of elemental sulfur from sulfides through their chemical oxidation occurred in the sediment.  相似文献   

Total,methyl and organic mercury in sediments of the Southern Baltic Sea     

《Marine pollution bulletin》2014,88(1-2):388-395

Distribution of sedimentary mercury in the Southern Baltic was investigated. Sediment samples were collected from the Southern Baltic in the period from 2009 to 2011, and concentrations of sedimentary total mercury (average 102 ng/g, range 5.8–225 ng/g) and methyl mercury (average 261 pg/g, range 61–940 pg/g) were measured in the manner that the influence of both patchiness and seasonal changes were assessed. Moreover, sedimentary mercury extracted with organic solvent- the so-called organic mercury was also analyzed (average 425 pg/g, range 100–1440 pg/g). There is a statistically significant dependence between organic mercury and both methyl mercury and total mercury concentrations in the sediments. Methyl mercury contribution to total mercury varied from 0.12% to 1.05%, while organic mercury contributed to 2% of total concentration on average. The area studied, although mercury concentrations exceed threefold the geochemical background, can be regarded as moderately contaminated with mercury, and methylmercury.  相似文献   

Thorium speciation in seawater   总被引：1，自引：4，他引：1  

P.H. Santschi  J.W. Murray  M. Baskaran  C.R. Benitez-Nelson  L.D. Guo  C.-C. Hung  C. Lamborg  S.B. Moran  U. Passow  M. Roy-Barman   《Marine Chemistry》2006,100(3-4):250

Since the 1960s, thorium isotopes occupy a special place in the oceanographer's toolbox as tracers for determining rates and mechanisms of oceanic scavenging, particle dynamics, and carbon fluxes. Due to their unique and constant production rates from soluble parent nuclides of uranium and radium, their disequilibrium can be used to calculate rates and time scales of sinking particles. In addition, by ratio-ing particulate ²³⁴Th (as well, in principle, other Th-nuclides) to carbon (and other elements), and linking this ratio to the parent–daughter disequilibrium in the water column, it is possible to calculate fluxes of carbon and other elements. Most of these applications are possible with little knowledge of the dissolved chemical properties of thorium, other than its oxidation state (IV) and tendency to strongly sorb to surfaces, i.e., its “particle- or surface-activity”. However, the use of any tracer is hindered by a lack of knowledge of its chemical properties. Recent observations in the variability of carbon to ²³⁴Th ratios in different particle types, as well as of associations of Th(IV) with various marine organic biomolecules has led to the need for a review of current knowledge and what future endeavors should be taken to understand the marine chemistry of thorium.  相似文献   

图们江口水中Zn,Cd,Pb,Cu的形式分析   总被引：1，自引：0，他引：1  

张首临  李泽林 《海洋科学》1992,16(5):47-50

本文用防吸附物理涂汞电极反问极谱对图们江口、东海及日本海水中Zn,Cd,Pb,Cu进行了形式分析,其不稳定态的平均浓度分别为5.9,0.071,0.039,0.69ug/L(占总量的15～27％),分布较为均匀,证实了痕量金属离子(自由离子及不稳定络离子的均匀分布规律。有机结合态Zn,Cd及Pb(10～30％)和颗粒态Zn,Cu和Cu(15～40％)的较高含量位于长江口、东海及图们江口。  相似文献