Effects of pH and Ca competition on complexation of cadmium by fulvic acids and by natural organic ligands from a river and a lake

The technique of competitive ligand-exchange/anodic stripping voltammetry (CLE-SV) was used to investigate effects of pH and Ca concentration on cadmium complexation by fulvic acid (FA), as well as Cd speciation in two different freshwaters, a hardwater Lake Greifen and a softwater River Wyre. Binding of Cd to Suwannee river FA (10 mg/l) was determined at different pH (7–8.5) and in the presence of various concentration of Ca²⁺ (0–2 mmol/l). The results from one-ligand discrete models were compared to simulations by the WHAM VI model. In Lake Greifen, the determined dissolved [Cd²⁺] ranged from 10⁻¹³ to 10⁻¹² mol/l, and the conditional stability constant with natural ligands was log K _CdL about 9.5–10.5 (pH 8.6–8.8) with ligand concentrations of 1.2–7.8 × 10⁻⁶ mol/g C. In the softwater River Wyre, dissolved [Cd²⁺] ranged from 4 × 10⁻¹² to 1 × 10⁻¹¹ mol/l, and the ligands were weaker (log K _CdL 8.9–9.8, pH 8.0) with lower ligand concentrations (0.9–2.3 × 10⁻⁶ mol/g C). The titration curves of FA samples were close to the simulated curves by the WHAM VI model at pH 8.0–8.5, but deviated more from the model at lower pH, indicating that the results determined with CLE-SV for Cd-FA complexation are relevant to the data base in the model. Calculation of the Ca competition for Cd binding by FA showed a competition effect of similar strength as the measured one, but indicated a systematic difference between measured and modeled data at pH 7.5. Using the WHAM model for comparison with FA, the complexation of Cd by the River Wyre ligands was close to that of FA, whereas stronger complexation was observed in the Lake Greifen water. These differences may originate from different ligand composition in the lake and the river.     

Distribution of protons and Cd between bacterial surfaces and dissolved humic substances determined through chemical equilibrium modeling

Bacteria and dissolved humic substances are capable of binding significant concentrations of metals in natural environments. Recent advances in understanding bacteria-metal and humic-metal complexation have provided a framework for directly comparing the binding capacities of these components. In this study, we use chemical equilibrium modeling to construct an internally consistent set of thermodynamic equilibrium constants for proton and Cd binding onto dissolved humic substances, using a variety of published data sets. Our modeling approach allows for the direct comparison of humic substance binding constants and site densities to those previously published for proton and Cd binding onto natural consortia of bacteria. We then combine these constants into a unified model that accounts for the competition between bacterial surfaces and humic and fulvic acids in order to determine the relative importance of each component on the total Cd budget. The combined model is used to examine the relative contributions of bacteria and dissolved humic substances to Cd complexation in natural settings. Calculations are performed for three representative systems: (1) one with a maximum realistic concentration of bacteria and a minimum realistic concentration of humic substance, (2) one with a maximum realistic concentration of humic substance and a minimum concentration of bacteria, and (3) one with an intermediate concentration of both components.Our modeling results indicate that dissolved humic substances have 2 orders of magnitude more available binding sites than bacterial surfaces (per gram). Humic substances also have a greater affinity than bacterial surfaces for binding Cd over circumneutral pH ranges. The combined model results demonstrate that, depending upon their relative concentrations, both Cd-humic and Cd-bacteria complexes are capable of dominating Cd-speciation in specific natural environments. This modeling approach is useful in that it can easily be extended to include other metals and binding ligands; however, thermodynamic data must be gathered on additional components to facilitate the modeling of more realistic systems.     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

Metal Complexation with Different types of Soluble and Adsorbed Freshwater Ligands Followed by DPASV

In order to understand metal speciation in a polluted river (Este River, Northern Portugal) filtrate, freeze dried particles and organics desorbed from surfaces were titrated with Cd(II) and Zn(II), followed by differential pulse anodic stripping voltammetry (DPASV). The obtained results are compared with those previously published for Pb(II) and Cu(II). Due to the heterogeneity of the system, a continuous and a discrete ligand model were used to interpret the titration data. Two types of ligands could be detected and quantified by the discrete ligand model: small molecules with high affinities for cations such as Cd(II), Cu(I), and Zn(II) and macromolecules with higher affinities for Pb(II) and Cu(II). Small ligands were strongly adsorbed onto the particles, as inferred from the desorption of Zn(II) during titration with Pb(II) and Cd(II). The total concentrations of the different ligands and the complex formation constants with the different metals are reported.     

Geochemical factors controlling free Cu ion concentrations in river water

Copper speciation was determined monthly at seven sites on four rivers in southern New England to understand which geochemical factors control free metal ion concentrations in river water. Samples were conventionally filtered (<0.45 μm) and then ultrafiltered (3.000 molecular weight cut-off) to determine Cu speciation in the truly dissolved size fraction. Differential pulse anodic stripping voltammetry (DPASV) was used to quantify natural organic complexation and cathodic stripping square wave voltammetry (CSSWV) to measure directly both Cu sulfide complexes and total EDTA concentrations. The results showed both dissolved organic matter (DOM) and sulfide complexation dominate Cu speciation and control the concentrations of free ion. Free Cu²⁺ was calculated to be in the subnanomolar range for the majority of the year. Only in the winter months, when concentrations of DOM and metal sulfides complexes were at a minimum were free metal ions directly measurable by DPASV at low nanomolar concentrations. The extent of sulfide complexation appears to be dominated by the size of headwater marshes (upstream sampling sites) and by the amount of sewage treatment plant effluent (downstream sites). DOM complexation was related to the organic matter composition and followed model organic ligands. Indirect evidence suggests variations in river water pH and Ca²⁺ (metal competition) has only a minor role in Cu complexation. Measured concentrations of total EDTA suggest this synthetic ligand can control Cu speciation in some highly developed watersheds; however, competition from Ni (and possibly Fe) limits the extent of this complexation.     

1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

¹H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -(CH₂)_n - CH₃ (n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.     

Phosphorus in marine and non-marine humic substances

The phosphorus content of marine humic acids (HA) is in the range of 0.1–0.2%. The C/P ratios of the HA are 300 to 400. Marine fulvic acids (FA) contain 0.4–0.8% P and have C/P ratios of 80 to 100. High molecular weight organic matter dissolved in pore waters (DOM) contains 0.5% P and has C/P of 90. The data suggest that during the formation sequence: Plankton → DOM → FA → HA → Kerogen, phosphorus is lost, mainly in the FA → HA (and possibly also in the HA → Kerogen) step. Diagenesis of sedimentary humic acids is accompanied by loss of phosphorus (as well as of nitrogen) to form HA with C/P ratios of 1000.Soil humic substances resemble marine humates in P content (0.3%) and soil FA's are about three to fivefold enriched in P relative to HA. C/P ratios are lower in soil HA (ca. 200) as compared with marine HA. Humic acids from diagenetic products such as peat and lignite are highly depleted in P. Rough calculations indicate that humate bound P may account for 20–50% of the organic phosphorus reservoir in sediments. The chemical speciation of this P is unknown, but lack of correlation with ash, Fe, Ca or Al content (in marine humates, at least) indicates that it is organically bound.     

Adsorption of Copper, Nickel, and Cadmium on Goethite in the Presence of Organic Ligands

Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).     

Characterization of sedimentary humic matter by alkaline hydrolysis

Humic matter fractions from modern sediments of Lake Huron and Lake Michigan have been compared. Large yields of saccharinic acids from alkaline hydrolysis suggest that these fractions contain large portions of carbohydrate materials. Evidence for contributions of aquatic lipid (C-16 fatty acids) and of liginin (phenolic acids) to these sediments is also present in the hydrolysis products. Qualitative differences among fulvic acid, humic acid and humin from the same lake are minor, suggesting common (or similar) organic sources for these fractions. The lability of sedimentary humic matter to alkaline hydrolysis is inversely related to its degree of exposure to oxidative weathering. Lability may also be related to diagenetic state as fulvic acids generally yield greater quantities of hydrolysis components than humic acids which in turn yield more than humin.     

Sedimentary humic acid and fulvic acid as fluorescent organic materials

Fluorescence and absorption spectra of sedimentary humic acid (HA) and fulvic acid (FA), with molecular weights ranging from < 10,000 to >300,000, were measured at 20°C and pH 8. The maximum excitation and emission wavelengths of HA were longer than those of FA, being independent of molecular weight. The excitation and emission maxima can be utilized to differentiate between sedimentary HA and FA. It is suggested that the fluorophors in HA are of a higher molecular weight aromatic groups than those in FA.Smaller molecules were found to have a greater fluorescence than larger ones for sedimentary humic substances and this phenomenon is similar to those obtained for humic substances of terrestrial origin. The absorption coefficient (1/g/cm) of HA decreased, while that of FA increased with the increase in molecular weight. It was shown that fluorescence intensity per weight concentration unit of HA increases and that of FA decreases with increasing absorption coefficient.     

Interaction of Cr(III) with the humus acids of soil,water, and bottom sediments

The interaction of Cr(III) with humus acids [fulvic (FA) and humic (HA) acids] was studied in the systems Cr(III)-FA, Cr(III)-HA, and Cr(III)-FA-HA. Chromium(III) reacts with FA extracted from the headwaters of the Moscow River and from the Krapivenka River (a tributary of Lake Seliger) to form a highly soluble high-molecular-weight Cr(III)-hydroxofulvate complexes with \(\bar \beta _{11} \) = 1.93 × 10⁶ and 5.70 × 10⁶, respectively. Humic acids extracted from peat in the Tver area and the sapropel of Lake Seliger behave as complexing sorbents with conditional affinity constants logβ = 3.78 and 3.23 for Cr(III) sorption at HA sites in the peat and sapropel, respectively. In the three-component system Cr(III)-FA-HA, the Cr(III) distribution coefficient between solution and precipitate is controlled by the pH value and FA content in the solution and decreases by 1–1.5 orders of magnitude with increasing fulvic acid content.     

Study of exchangeable metal on colloidal humic acids and particulate matter by coupling ultrafiltration and isotopic tracers: Application to natural waters

A new method is proposed to characterize the complexation properties of colloids and metal–colloid interactions in natural waters. Based on the association of ultrafiltration with isotopic tracing, this method could quantify the pool of elements in an exchangeable position and also address the kinetic aspects of these exchanges. Basically, it consists of the comparison of isotopic compositions between the bulk sample and a succession of filtrates through time. Exchanges between colloidal humic acids (HA) and metals were first characterized, before applying such manipulations on natural waters. A few elements, representative of a wide range of complexation properties, were chosen: Cu, Zn, Cd, Pb, Sr, Nd, Ni, Th and U. In the case of humic acids, very small (less than 10% of isotopes), but significant isotopic shifts were observed compared to the isotopic equilibrium. It means that more than 90% of the isotopes were exchanged just after addition of isotopic tracers. Experiments on natural organic-rich waters (Mengong and Nyong streams) indicate isotopic composition variations close to those of humic acids. On the contrary, ultrafiltration performed on the total Sanaga River water (including suspended matter “SM”) shows an important isotopic shift between the filtered and unfiltered solutions. It means that in the case of the Sanaga River, a significant part of the chemical elements did not exchange.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

桂林毛村岩溶区自然植被土壤团聚体中腐殖质组成初步研究

探索土壤有机碳物理保护与化学保护的关系,有助于揭示土壤固碳和培肥机理,明确不同粒级团聚体和不同腐殖物质组分对土壤固碳和肥力的贡献。本研究对岩溶区自然植被土壤团聚体中腐殖质含量进行了研究,结果表明:(1)灌丛和林地土壤团聚体中有机碳含量总体上均表现为随着土层深度的增加逐渐下降,而在不同土层深度随着团聚体粒径范围的变化则有机碳含量的变化规律则不同,无明显一致的规律;(2)两种土地利用方式各粒径团聚体中胡敏酸和富里酸均比全土小。这可能是由于在湿筛分离团聚体的过程中溶于水的那部分胡敏酸和富里酸成分被损失掉;(3)各腐殖质组分随着团聚体粒径范围的减小在两种自然植被上均无明显一致的规律,但胡敏酸和富里酸总量则基本表现为随着团聚体粒径范围的减小而逐渐升高,即在0.25mm和0.5~0.25mm粒径范围团聚体中最大;(4)两种自然植被土壤各土层中和各团聚体中胡敏酸/富里酸(HA/FA)基本上表现为小于1,这主要是因为研究区温度相对较高,湿度较大,植被覆盖度大,微生物降解作用强所致。     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Kinetics and mechanisms of kaolinite dissolution: effects of organic ligands

The effect of protons, low molecular weight organic ligands, soil humic acid (HA), and stream water dissolved organic matter (DOM) on the rate of dissolution of kaolinite was examined. In acid solution (no ligands present) the rate of dissolution increased with increasing [H⁺] and the rate of Si dissolution was generally faster than Al. Low molecular weight organic ligands markedly increased the dissolution rates of both Al and Si in the following order: oxalate > malonate ≈ salicylate > o-phthalate. In the presence of organic ligands, the rate of Al dissolution was generally much greater than Si. Soil HA and stream water DOM did not promote the dissolution of kaolinite under the experimental conditions examined in this study.

The dissolution kinetics of Al were interpreted in terms of a surface complexation model and the rate equations described in terms of the concentrations of specific (i.e. inner sphere) surface complexes.     

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d’Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.