A multi-method approach for the study of lanthanum speciation in coastal and estuarine sediments

Two independent analytical methods (sequential extraction and kinetic extraction methods) were applied in order to understand the distribution and speciation of La in the coastal and estuarine sediments from the central east coast of India. Sequential extraction study revealed that La was primarily present as inert complexes (~ 50–60% of the total La) in all the sediments. Amounts of ~ 20–30% of the total La in all the sediments were found to associate with the total organic carbon (TOC) in the sediments. The dissociation rate constants of La–sediment complexes obtained from kinetic extraction studies revealed that the concentration of thermodynamically weak complexes of La gradually increased with the increasing La/TOC ratio in the sediments.     

Molecular weight and chemical reactivity of dissolved trace metals (Cd,Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.     

根际环境锌镉镍的形态变化与植物有效性

以抚顺西露天采场60平盘5种修复植物根际与非根际土为研究对象，运用顺序提取实验和数理统计分析方法研究了根际与非根际土中Zn、Cd、Ni的形态分布与植物有效性。结果表明，Zn、Ni在根际与非根际土中主要以硫化物态存在；而Cd在非根际土中以硫化物态为主，在根际土中以可交换态和松、紧有机态为主。与Ni相比，非根际土中Zn的紧有机态、氧化物态和Cd的紧有机态、氧化物态、可交换态比例明显偏大；与非根际土相比，根际土中Zn的铁锰氧化物态和硫化物态含量增加，碳酸盐态含量降低，松有机态、紧有机态和可交换态Zn在不同植物根际变化不同。Cd的硫化物态降低，可交换态、松有机态、碳酸盐态、氧化物态和紧有机态含量在不同植物根际变化不同。Ni的紧有机态显著增加，可交换态、碳酸盐态和硫化物态明显降低，松有机态在不同植物根际变化不同；根际Cd的碳酸盐态增加和氧化物态降低有利于植物Cd的吸收；碳酸盐态Zn的减少可促进植物Zn的增高。     

样品处理与保存方法对表层沉积物中金属形态分析的影响

利用改进的Tessier连续萃取法研究了冷藏、冷冻、冻干、烘干和风干等样品处理与保存方法对表层沉积物中金属形态的影响。结果表明：各样品处理与保存过程对沉积物中Fe、Mn、Cu、Zn及Pb的形态均具有不同程度的影响,其中Fe的形态受其影响最小（<3.3%）,Mn的形态受其影响最大（最高可达10.2%）;冻干对各金属形态的影响最小（<4.6%）;烘干和风干对重金属Cu、Zn和Pb的可交换态（Ⅰ+Ⅱ）和非残渣态（Ⅰ-Ⅴ）分布影响较大,而冷藏、冷冻和冻干的影响相对较小。因此,综合考虑重金属的形态分布及其生物可利用性,冻干是较理想的沉积物样品处理与保存方法。     

The role of iron and sulfur in the visual appearance of lake sediment varves

Easily discernible sediment varves (annual laminations) may be formed in temperate zone lakes, and reflect seasonal changes in the composition of the accumulating material derived from the lake and its catchment (minerogenic and organic material). The appearance of varves may also be influenced by chemical processes. We assessed the role of iron (Fe) and sulfur (S) in the appearance of varves in sediments from Lake Nylandssjön in northern Sweden. We surveyed Fe in the lake water and established whether there is internal transport of Fe within the sediment. We used a unique collection of seven stored freeze cores of varved sediment from the lake, collected from 1979 to 2004. This suite of cores made it possible to follow long-term changes in Fe and S in the sediment caused by processes that occur in the lake bottom when the sediment is ageing. We compared Fe and S concentrations using X-ray fluorescence spectroscopy (XRF) in specific years in the different cores. No diagenetic front was found in the sediment and the data do not suggest that there is substantial vertical transport of Fe and S in the sediment. We also modeled Fe and S based on thermodynamic, limnological, and sediment data from the lake. The model was limited to the five components H⁺, e^?, Fe³⁺, SO₄ ^2?, H₂CO₃ and included the formation of solid phases such as Fe(OH)₃ (amorphous), FeOOH (aged, microcrystalline), FeS and FeCO₃. Modeling showed that there are pe (redox) ranges within which either FeS or Fe(OH)₃/FeOOH is the only solid phase present and there are pe ranges within which the two solid phases co-exist, which supports the hypothesis that blackish and grey-brownish layers that occur in the varves were formed at the time of deposition. This creates new possibilities for deciphering high-temporal-resolution environmental information from varves.     

Experimental Study of Gold and Platinum Solubility in a Complex Fluid under Hydrothermal Conditions

Abstract: The solubility of gold was studied in water and aqueous NaCl (1– 5 m) solutions under oxygen and sulfur buffered conditions between 300–500C at a constant pressure 1 kb. Two buffer assemblages HMP and PPM were used. Analysis of the scatter in measured values in log m_Au–m_NaCl–T frame fixed linear dependence between log m_Au and T at any studied iso‐pleth (m_NaCl) in the form of log m_Au = a. T(C) + b. Coefficients of the equation were calculated for water and NaCl (1, 3, 5 m) solutions. The maximum solubility characterizes the NaCl‐free system in the presence of HMP. In the case, Au solubility increases from (log m_Au) –6. 72 to –5. 04 at 300 and 500C, respectively. In the presence of PPM, maximum of Au solubility was obtained for the 5 mNaCl solution. In a similar manner solubility rises from –6. 54 to –5. 77 at 300 and 500C, accordingly. In studied f_O2/f_S2 area the behavior of Au solubility testified that: (i) – a composite interaction between chloride and hydrosulfide speciation of gold affects its total solubility; (ii) – in addition of NaCl up to about 1. 5 m the solubility decreases, more pronounced in the presence of HMP; (iii) – the contribution of chloride in total Au solubility is more for PPM despite of lower f_O2value, than for HMP. The solubility of platinum was studied in the Pt–Cl–S–H₂O system between 300 and 500C, 1 kb. PPM solid buffer controlled oxidation state, pH and sulfur activity of solutions (H₂O, 1 mNaCl and 0. 1 mHCl). Under the conditions, PtS precipitated from the solutions with increasing temperature and acidity. The PtS solubility in the 0. 1 m_HCl solutions lowers slightly in the range of 300–500C from –5. 30 to –5. 60 (in log m_Pt) that is typical to the hydrosulfide species. It was deduced that reducing media, regulated by the PPM assemblage, suppress activity of chloride species of Pt. More oxidizing conditions were modeled in runs using mixtures of Mn(II), Mn(III) and Mn(IV) oxides to buffer the aqueous‐chloride solutions between 300 and 500C, 1 kb. It was found that MnO tends to oxidize at T below 400C forming intermediate Mn‐hydroxides (β–MnOOH, Mn (OH)₂ and Mn₂(OH)₃Cl). These phases are metastable and transfer to Mn₃O₄ with increasing duration. Generation of the Mn‐hydroxides leads to a change of physical‐chemical parameters of the solutions, such as water activity, pH and Eh. The last results in abrupt increase in the noble metals dissolution. At stable existence of only Mn₃O₄, the solubility of both Pt and Au lowers to equilibrium values. Essential catalysis effect of Pt on intensity and rate of Mn(II) oxidation was found. The dominant role of chloride of Pt and Au was defined under most oxidized conditions, specified by Mn₂O₃–MnO₂ buffer. So at 400C, dissolved Au (log m_Au) increases from –4. 40 in water to –1. 00 in 0. 1 m_HCl, and ones of Pt (log m_Pt) from –4. 80 to –2. 90 accordingly. Thus, mixing of hydrosulfide and chloride solutions, as well as transformation of the systems to the stable state act upon total solubility of the noble metals.     

湘西表生环境中的砷及其生态健康效应

湘西是金、砷、锑、汞等有色金属的重要成矿带,区域地层微量元素地球化学研究表明,湘西所出露的地层均显著富集砷,是砷的高区域地球化学异常区,元素存在相态的实验进一步表明,新元古界至寒武系中的砷以易迁移形式为主,母岩的这一性质决定了其风化土壤中的砷的含量较高,土壤砷的高背景特征受人为采矿活动的影响,局部地区呈现高异常,土壤、水体砷的高异常已影响到居民的身体健康。     

Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

江西省德兴铜矿矿区重金属元素的环境效应

本文系统研究了德兴铜矿排石场和尾砂库的环境问题,以环境介质（水土植物）中重金属元素含量为研究对象,论述矿区重金属的环境效应。研究结果表明祝家村低品位矿石堆浸场淋滤产生的酸性废水是造成大坞河流域重金属污染的主要来源。大坞河上游水体中Cu元素含量高达14506μg/L,是国家Ⅲ级水标准的14倍之多,Zn元素含量高达2938μg/L,是国家Ⅲ级水标准的2.9倍,同时pH值在3~4范围内;到中下游水体中Cu元素含量减小到几千到几百μg/L,水质有所改善。大坞河沿岸上游和中游土壤重金属含量受河水影响,随着与河岸距离的增加而减小。同时水稻中Pb元素含量是国家粮食标准的2倍。推测4#尾砂库尾砂表层氧化带深度大于80cm;而1#尾砂库库内尾砂中氧化带估计在0~25cm处。推测两个尾砂库产酸能力小于酸中和能力,故坝底水中pH值在7左右,对周围水体影响较小。与4#尾砂库距离近的石墩头村稻田表层土壤中Cu、Mo元素含量较高,远离尾砂库土壤中重金属含量降低。同时4#尾砂库周围土壤中Cd、Pb、Cu元素的吸附态、碳酸盐态比例在20%左右,因而在酸性环境下较容易被植物吸收。1#尾砂库矿建村种植的小白菜中Pb元素含量超过国家蔬菜标准的4倍,Cu、Pb、Zn元素含量严重超过背景值。