Studies in seawater and lake water on interactions of trace metals with humic substances isolated from marine and estuarine sediments: II. Voltammetric investigations on trace metal complex formation in the dissolved phase

In seawater and lake water the complexation of several heavy metals, present in the dissolved state at relevant trace levels, with humic substances isolated from two marine and an estuarine sediment has been studied by differential pulse anodic stripping voltammetry (DPASV) at a hanging mercury drop electrode (HMDE). Taking Zn(II) as an example, the aim of this study was to gain direct information on the general level of importance of humic substances for the speciation of certain heavy metals in fresh and saline waters.In seawater humic acids originating from different sediments have very similar complexing properties for Zn(II), decreasing slightly in the order HAN > HAL > HAM. In lake water HAL is most efficient for complexing Zn(II), followed by HAN and HAM.In both types of natural waters, the sedimentary fulvic acid is less efficient in complexing Zn(II) than the respective humic acid from the same site. In general, the complexing efficiency decreases in the order EDTA > NTA > humic acids > fulvic acid.The problem of humic acid adsorption at the electrode, which somewhat limits the investigation of Pb(II) and Cd(II), and the impact of pH on the amount of complexed Zn(II) are also discussed.The findings provide further direct evidence for the conclusion previously drawn from existing complexation data that because of the rather low levels of dissolved humics in large parts of the oceans, the complexation efficiency of humics for Cd, Pb and Zn is too low to affect the speciation pattern of these three heavy metals.     

Partitioning of trace metals released from polluted marine aerosols in coastal seawater

Mobilization and transfer of atmospherically transported metals to major suspended particulate matter components in seawater have been studied in a multichamber leaching experiment. Data on the meteorological air mass history, enrichment factors and sequential extraction analysis indicate that the highly polluted marine aerosol samples collected on Helgoland are of anthropogenic origin. A significant fraction of the total cadmium (81%), zinc (58%), copper (41%), and lead (40%) was released in seawater within 1 h. When exposed to the aerosol and artificial suspended particulate matter components for another 100 h, a portion of the released metals ranging from 10 to 60% was readsorbed. Zinc and lead were scavenged by iron/manganese oxides or readsorbed by the aerosol particulates. Of the total scavenged copper portion 67% was bound to phytoplankton cell walls which evidences an ecological impact of the polluted marine aerosols even in the coastal environment.     

Chemical speciation of trace metals in seawater: Implication of particulate trace metals

Chemical speciation of particulate metals in seawater was examined theoretically. Mass balance considerations showed that the apparent conditional stability constant, defined for organically binding metals in suspended particles, coincides with the conditional stability constant determined for the corresponding metal-organic complexes dissolved in seawater. This hypothesis suggests that some metals, which are present as organic complexes (e.g. copper), are directly associated with particulate organic matter. Metals, whose free ion is buffered by organic and/or inorganic ligands, may be used as indicators of the presence of particulate organic matter in the marine environment.     

Influence of sedimentological features on the distribution of trace metals in marine sediments

The most important parameters influencing trace metal distribution in sediments are reviewed. The accent is put on sedimentation rate, grain size distribution and the knowledge of past events through sedimentological and mineralogical parameters. It is concluded that chemical data must be compared to sedimentological data before being interpreted.     

Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.     

Molecular weight and trace metal distributions in fulvic and humic acid fractions of coastal marine sediments

Molecular weight and trace metal distributions of fulvic and humic acid fractions of marine sediments from the Seto Inland Sea were investigated by using a gel filtration technique in combination with atomic absorption and emission spectrometries. A binary molecular weight distribution was found both in the fulvic acid fraction and in the humic acid fraction. The fulvic acid fractions with molecular weights of less than 1.5×10³ and of 5×10³?10⁴ accounted for 38–57 % and 25–41 % of the total fulvic acids, respectively, and the humic acid fractions with molecular weights of 10²?10⁴ and of over 2×10⁵ accounted for 58–73 % and 16–27 % of the total humic acids, respectively. The components with molecular weights of over 1.5×10³ contained 54 %, on average, of the Fe, Zn and Cu in the fulvic acid fraction, and the components with molecular weights of over 10⁴ contained 58 %, on average, of these metals in the humic acid fraction.     

Chemical characterization of humic substances isolated from mangrove swamp sediments: The Qinglan area of Hainan Island,China

In order to improve the understanding of structural and reactive features of sediment organic matter from mangrove swamp as well as evaluate the relationship between such features and the impact from different sources (marine and terrestrial), humic and fulvic acids were isolated from two mangrove swamp sediments located in the Qinglan harbors on Hainan Island, China. One is a forest surface sediment site (WWM2), and the other is an estuary subaqueous sediment site (BMW). The humic and fulvic acids were characterized and compared using chemical and spectroscopic methods, including elemental analysis, thermogravimetric analysis (TGA), Fourier Transformed Infrared Spectroscopy (FTIR), ¹³C nuclear magnetic resonance (¹³C NMR) and potentiometric titrations. The results indicated that there were less aliphatic compounds but more aromatic compounds and oxygen-containing functional groups in fulvic acids. Humic acids contained more long-chain hydrocarbons and nitrogen compounds. Comparison of the C/N ratios and δ¹³C values for the humic substances at both sites indicated a larger marine and/or microbial contribution to the BMW site. Humic substances at the WWM2 site have more acidic functional groups than those of the BMW site. Compared to the literature, more phenolic groups existed in the samples of both sites, which may be due to the autochthonous contribution of mangrove plants.     

Influence of salinity and humic substances on the uptake of trace metals by the marine macroalga, Ulva lactuca: Experimental observations and modelling using WHAM

Uptake of the trace metals, Pd, Cd, Hg and Pb, by the marine macroalga, Ulva lactuca, has been studied along a salinity gradient (S = 15–35; pH ~ 8.3) created by batch mixing of synthetic sea water and pure water, both in the absence and presence of humic substances. Factors defining the concentration ratio of metal taken up (w/w) to metal remaining in solution ranged from about 10² mL g^− 1 for Cd to 10³ mL g^− 1 for Pd and Hg. Within experimental error, only the biouptake of Cd appeared to exhibit a dependence on salinity, while the addition of 3 mg L^− 1 of humics resulted in a small suppression of Pd and Hg uptake and a moderate enhancement of Pb uptake compared with the humic-free system. Metal internalisation, evaluated from an EDTA wash of the alga, followed the sequence: Hg > Pd > Cd > Pb; and was notably inhibited in the presence of humics for Pb. Metal uptake (as adsorption and internalisation) was modelled using the Windermere Humic Aqueous Model (WHAM, v6) by encoding the macroalga as a polyelectrolytic binding phase whose properties were defaulted to those of aqueous humics in the software database. By setting the “activity” of the binding phase to about 0.1 and systematically reducing the default constants for metal binding, the magnitude of metal uptake by U. lactuca was reproduced. However, for all metals the model predicted a reduction in algal uptake as a function of salinity that was not always observed experimentally. Moreover, calculations performed in the presence of aqueous humic substances and using the earlier fitted constants significantly underestimated metal uptake by U. lactuca. Discrepancies between experimental observations and model calculations, which are attributed to the formation of ternary complexes at the algal surface, suggest that conventional equilibrium speciation considerations alone are not applicable for modelling metal interactions with marine macroalgae.     

13C NMR spectra and Cu(II) formation constants for humic acids from fluvial,estuarine and marine sediments

Humic acids extracted from fluvial, estuarine and marine sediments from the eastern coast of Florida were studied by CP/MAS ¹³C nuclear magnetic resonance. The freshwater humic acid contained a large percentage of lignin-derived aromatic carbon whereas the offshore marine samples contained large amounts of aliphatic carbon. The aliphatic carbon of the marine humic acids was more highly branched than that found for freshwater and estuarine sediments. Despite significant differences in the relative amounts and types of carbon present, conditional formation constants for Cu(II)-humic acid were very similar.     

海水和海洋沉积物中有机磷酸酯的研究进展

有机磷酸酯(OPEs)已广泛应用于阻燃剂和增塑剂,但由于其具有较高毒性、难降解和远距离迁移等特点,从而引发的一系列海洋环境问题也逐渐受到关注。本文基于国内外海水和沉积物中OPEs的最新研究数据,分析了海水和海洋沉积物中OPEs的分析检测技术、迁移转化、分布特征和影响因素等,并针对当前研究的不足进行了讨论和展望。通过本文总结发现,海水中OPEs主要来自河流输入和大气沉降的输送,且浓度分布特征表现为表层高于底层,三种氯代有机磷酸酯[磷酸三(2-氯乙基)酯(TCEP)、磷酸三氯丙酯(TCPP)和磷酸三(1, 3-二氯-2-丙基)酯(TDCPP)]是海水中OPEs的主要组分;海洋沉积物中OPEs的含量分布表现出港湾、近岸海域和沿岸城市经济发达区域较高的趋势,其主要组分存在差异,受辛醇-水分配系数(lg Kow)和总有机碳(TOC)两个因素的影响较大。     

Distribution of oxygen-containing functional groups and elements in humic acids from marine sediments

The elemental composition and oxygen-containing functional groups contents in the marine humic acids from the five sediment samples from Sagami Bay and Suruga Bay were determined. Kumada's method of classification of soil humic acids was applied to the marine humic acids. The carbon, nitrogen, hydrogen, oxygen and sulfur contents of the marine humic acids were, on average, 52.96, 5.12, 5.79, 34.99 and 1.13%, respectively, without wide variation. In comparison with terrestrial humic acids, the marine ones had relatively lower carbon content and higher hydrogen and nitrogen contents. It is suggested that the marine humic acids have more aliphatic and less aromatic character, as expected from their possible origins, e.g., phytoplankton. The total acidity, carboxyl, phenolic and alcoholic hydroxyl, carbonyl and methoxyl group contents in the marine humic acids were, on average, 5.80, 3.27, 2.53, 2.53, 3.09 and 0.41 milliequivalents per gram of dry ash-free humic acid (me g^–1), respectively. From quantitative data on the elemental composition and functional groups of the average marine humic acid, its empirical formula was calculated to be C₁₀₇H₁₃₈O₂₀(COOH)₉(OH)₇ ^phenolic (OH)₇ ^alcoholic (CO)₉(OCH)₃N₁₀S. The marine humic acids were similar to the so-called B type of soil humic acids with regard to the distribution of functional groups and spectroscopic properties.     

Characterization of humic and fulvic acids isolated from marine sediments of Sagami and Suruga Bays with C-13 and proton nuclear magnetic resonance

The C-13 and proton NMR spectra of marine humic and fulvic acids isolated from sediments of Sagami and Suruga Bays and Aldrich humic acid were obtained using pulse Fourier transform mode. The C-13 and proton NMR spectra, which clarified the differences in chemical characteristics among the various humic substances, showed that the marine humic acids had more aliphatic and less aromatic character than the Aldrich humic acid, and the marine fulvic acids had polysaccharide-like character. The C-13 NMR spectra of the marine humic substances, in particular, had many relatively well-resolved peaks with significant intensities, indicating the presence of variously bonded carbon atoms in them.     

Heavy metals in Changjiang estuarine and offshore sediments: responding to human activities

The Changjiang (Yangtze) estuarine and offshore sediments were analyzed for total heavy metals concentrations and chemical fractions.Distributions of heavy metals show typical banded diffusion pattern,with high concentrations near the river mouth and following a decreasing trend in the offshore direction.According to chemical fractions,Fe/Mn oxide fraction is the major non-residual fraction in the Changjiang estuarine and offshore sediments.Higher percentage of non-residual fraction of Pb implies that,the industrial contaminations transported via the atmosphere and river input,may affect the non-residual fraction of heavy metals.Over past fifteen years,the concentration of Pb normalizing to Al presents significant increasing trend,corresponding to the effect of human activities.By comparison of heavy metals fractions in 2003 to 2006,it has been realized that increasing water and sediment may cause a higher percentage non-residual fraction of Cu in the southern part of offshore muddy sediments.     

Release and uptake of dissolved silica in seawater by marine sediments

Natural marine sediments can release dissolved silica to silica-poor seawater and can remove silica from seawater enriched with dissolved silica. These are fast reactions, with sufficient reaction occurring within the first 48 hours to indicate clearly the direction of the reaction. The relative importance of these two processes varies with the ratio of clays to biogenic silica in the sediment. Both the release and the uptake reactions approach the interstitial water concentration of dissolved silica as an end point, which suggests that these reactions may influence this concentration. No change in sediment reactivity with respect to silica uptake or release reactions was observed with increasing depth in core for the three sediment cores investigated; this indicates that uptake sites are not saturated, and silica is available for dissolution for a long time after deposition.     

ICP-MS测定海水中溶解态痕量重金属——直接稀释法

海水水质监测是环境监测中的重要一环[1]。海水中痕量重金属元素地球化学研究现今仍面临两大挑战:一是痕量重金属元素有机和无机形态分析,二是海水中痕量重金属元素的含量测定[2]。海水的含盐量为35 g/dm3左右,基体中除了大量的NaCl外,还含有相当量的SO₄2-,Ca2+,Mg2+等离子及有机质。由于海水中溶解态重金属元素的含量基本上都在微克每立方分米量级或更低,在传统的分析方法中这部分元素含量的测定或受到严重的光谱干扰、或低于仪器检测限,定量分析相当困难。