Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Migration of dissolved trace elements in the mixing zone between Volga River water and Caspian seawater: Results of observations over many years

Based on natural observations over many years, the distribution of dissolved nutrients and trace elements was analyzed in the mixing zone between the freshwater of the Volga River and Caspian seawater. Most of the trace elements (Li, Rb, Cs, B, F, Br, I, Ga, Sc, Y, Co, Ni, Cu, Cd, Ag, V, As, Sb, Bi, Mo, W, and U) show a conservative behavior. During the period of the highest bioproductivity, dissolved phosphates and silica are intensely removed from solution (up to 60–90 and 46–82% of their supply by river runoff, respectively) mostly owing to uptake by aquatic organisms. The distribution of dissolved strontium was assigned to the weakly nonconservative type, because a minor excess of its content above the lines of conservative mixing (8–18%) was observed in some years; perhaps, this is related to different water transformation at the areas of moving and stagnant water in the delta and offshore mouth zone. Barium is characterized by additional input into the solution (up to 52%) in the regions of medium salinity owing to ion exchange reactions in the absorbed complex of river suspended material. The migration of dissolved species of aluminum, manganese, and iron in the mixing zone of Volga and Caspian waters is probably controlled by the coagulation and flocculation of organic and organo-mineral colloids, which is indicated by a sharp decrease in the content of these elements during the initial stage of salinization (59, 91, and 74%, respectively) followed by a plateau. The most complicated distribution was observed for titanium, lead, and rare earth elements (REE), the concentrations of which showed intense removal from the solution (up to 64–88% Ti, 52–87% Pb, and 66–83% REE) followed by a gradual increase, which is probably related to the elevated contents of these elements in the water of the northern Caspian above a local minimum in the zone of active flocculation of colloids.     

Adsorption characteristics of natural organic matter on activated carbons with different pore size distribution

The adsorption characteristics of natural organic matter (NOM) were investigated on the basis of fluorescence excitation emission matrix (EEM) by using four different coal-based activated carbons (ACs). For each AC, batch adsorption isotherms were analyzed using a modified Freundlich isotherm model on the basis of the fluorescence intensity of three major fluorescence peaks appeared in the fluorescence EEM reported to be reflective of the humic acid-like (P1), fulvic acid-like (P2) and aromatic protein-like (P3) substances, respectively, together with the well-used overall quality indices of dissolved organic carbon (DOC) and ultraviolet absorbance at the wavelength of 260 nm (UV260). It was found that, for all five quality indices, the adsorption capacity differed with the ACs used, and the modified Freundlich isotherm constant K estimated for P1, P2 and P3 was in close correlation with that of the total organic matter evaluated by DOC. Moreover, no matter which AC was concerned, the magnitude of the estimated K and the removal rate over a broader range of AC dose for P3 were apparently smaller than those for P1 and P2, suggesting the adsorbability of aromatic protein-like substances was lower than that of the humic acid-like and fulvic acid-like substances. The dependency of the adsorption capacity of NOM on the volume of pores in some specific size ranges of the ACs was also revealed.     

Temporal variations of colloidal carrier phases and associated trace elements in a boreal river

Elemental size distributions, from truly dissolved through colloidal to particulate, have been studied in a subarctic boreal river. The measurements, carried out during 2002, ranged from winter to summer conditions, including an intense spring flood event. Results are reported for a total of 42 elements. Size distributions were characterised using a combination of cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin-films (DGT). The three techniques showed similar trends, but quantitative comparisons reveal some important differences that warrant further investigation.Previous work has identified two colloidal carrier phases in fresh waters, dominated by iron and carbon, respectively. The majority of the elements studied are associated with one or both of these colloidal carrier phases. The exceptions are the alkali metals and several anions that are only very weakly associated with colloidal material, and which therefore occur mainly as truly dissolved material (<1 kDa in molecular weight). We discuss the likely origin for the two colloidal carrier phases and consider how associated trace elements fit into the geochemical framework. The relative affinities of the elements for iron and carbon colloidal carrier phases are related to their chemistries, and are compared with earlier data from the Delsjö Creek in southern Sweden.Elemental colloidal concentrations show strong seasonal variations related to changes in the colloidal carrier phase(s) with which they associate. In particular, many elements show a strong spring maximum in colloidal concentrations associated with the strong maximum in colloidal carbon concentration during the spring flood.     

Hydroacoustics as a tool for assessing fish biomass and size distribution associated with discrete shallow water estuarine habitats in Louisiana

We developed a relative index of fish biomass and size distribution in ultra-shallow waters (< 2 m) of Barataria Bay, Louisiana, based on the comparison of horizontal hydroacoustic data with gill net and push trawl catches in an effort to understand the role that habitat plays in both fish biomass and distribution. Exclosure net experiments indicated that the contribution of acoustic backscattering from sources other than fishes were negligible. Split-beam transducer, gill net, and push trawl sampling were conducted concurrently in Barataria Bay to provide information on fish composition and length distributions and for comparisons among gear types. Results suggest that acoustic fish biomass was generally higher in the low salinity stations and lower at the high salinity stations, at least in March 2004. We observed a greater mean length of fishes associated with oyster shell habitats when compared to adjacent sand-mud habitats. This paper demonstrates the utility of hydroacoustics as a tool to quantify relative acoustic fish biomass and size distribution associated with common estuarine habitats in ultra-shallow waters. This study also illustrates the potential of using acoustics for augmenting traditional sampling procedures.     

富钴结壳关键元素赋存状态与富集机理

富钴结壳是大洋低温海水中的溶解元素在海山边坡沉淀形成的壳状铁锰矿产,广泛分布于全球海山、海底高原斜坡之上,储量巨大。铁锰结壳高度富集Co、Ni、Pt、REE、Te等元素,达到海水丰度的105~1010倍,是未来新能源、高新技术元素的重要来源,具有极大的潜在经济价值。前人通过淋滤实验、吸附实验、现代海洋观测方法、海水化学分析、高分辨率精细矿物学研究等方法对富钴结壳中元素的赋存状态和富集机理进行了广泛而深入的研究。研究结果表明,富钴结壳主要由含铁水羟锰矿和铁氢氧化物组成,在海山附近的海洋化学过程中,含铁水羟锰矿和铁氢氧化物胶体分别优先吸附Co、Ni、Pt、REE和Cu、Pb、Te、REE等元素,表面氧化/置换作用造成了含铁水羟锰矿中Co、Pt、Ni、Ce及铁氢氧化物中Te、Ce的持续积累。富钴结壳极其缓慢的生长速率（1~10 mm/Ma）、超高孔隙度（60%）、极大的体表面积（300 m2/g）都促进了结壳中关键元素的超常富集。对富钴结壳关键元素富集机理的理解是富钴结壳古海洋反演研究的基础,海域富钴结壳地球化学差异的控制因素需要进一步研究,这些关键科学问题的理解有助于富钴结壳资源的勘探工作。     

Use of major and selected trace elements to describe mixing processes in a water reservoir

Data on temperature, major constituents and some trace elements, measured in the dissolved and particulate phases, were used to identify the hydrodynamics of a reservoir (the Bicaz reservoir, Romania). Results revealed that the reservoir experiences two thermal stratifications per year (summer and winter). However, the summer stratification is delayed by the high river inflow of June–July. Two layers were identified, a surface and a deep layer, whose location and impact vary with time. The surface layer originates from the river inflow (intrusion layer) and the deep current is produced by the outflow (velocity current). According to season, the river inflow either supplies the deep current or remains recordable up to the dam. Consequently, the structure of the water column, and thus the biogeochemical processes within it, are governed both by thermal stratification and by these layers.     

会泽铅锌矿床中自然锑的发现及伴生元素的分布特征

文章对会泽铅锌矿床的主要矿体进行了系统观察、采样，对其矿石进行了岩矿鉴定、化学分析(包括部分单矿物)和电子探针分析，并对其成矿作用做了探讨。首次在矿石中发现了自然锑，初步查明整个矿床中Ag，Cd，Ge，Cu，Sb等伴生元素的平均含量(wB／10^-6)分别为121．77、660．99、62．10、203．78和169．87，认为它们是晚成矿阶段形成的。     

Changes in concentration and size distribution of aerosols during fog over the south Indian Ocean

Measurements of the concentration and size distribution of aerosol particles in the size-ranges of 0.5–20 μm and 16–700 nm diameters were made during six fog episodes over the south Indian Ocean. Observations show that concentrations of particles of all sizes start decreasing 1–2 hours before the occurrence of fog. This decrease is more prominent for coarse particles of >1 μm diameter and continues until 10–20 minutes before the onset of fog when particle concentrations in all size ranges rapidly increase by one/two orders of magnitude in ∼20 minutes. Thereafter, concentrations of particles of all sizes gradually decrease until the dissipation of fog. After the fog dissipation, concentrations of coarse mode particles rapidly increase and restore to their pre-fog levels but concentrations of the Aitken mode particles decrease slowly and reach their pre-fog levels only after 1–2 hours. The net effect of fog is to change the bimodal size distributions of aerosols with a coarse mode at 1.0 μm and an accumulation mode at 40–60 nm to a power law size distribution. It is proposed that the preferential growth and sedimentation of the coarse mode hygroscopic particles in the initial phase cause a large decrease in the aerosol surface area. As a result, the low vapour pressure gases which were initially being used for the growth of coarse mode particles, now accelerate the growth rates of the accumulation and Aitken mode particles.     

Spatial distribution of deuterium in atmospheric water vapor: Diagnosing sources and the mixing of atmospheric moisture

We measured the stable isotopic composition of hydrogen (δD) within atmospheric water vapor collected simultaneously at six sites in the vicinity of a lake (Lake Kasumigaura, Eastern Japan) to determine its spatial distribution characteristics and thereby diagnose sources and mixing of atmospheric moisture. The measured spatial distribution of δD showed no relation to distance from the lake, although it showed a correlation with the distribution of the water-vapor mixing ratio Q. For two of the three sampling days, we found a simple two-component (i.e., water vapor transpiring from local land surfaces and pre-existing vapor in the background atmosphere) mixing line in a Keeling plot (i.e., δ − 1/Q diagram). On a third day, however, contributions from lake evaporation were detected in addition to the above components. On this day, lake-derived vapor accounted for approximately 10-20% of atmospheric water vapor at the sites located leeward of the lake. The observed differences in mixing patterns among sampling days can be explained by a simple atmospheric moisture budget. Thus, it is likely that simultaneous isotopic measurements of atmospheric water vapor at multiple locations with aid of Keeling plot are capable of giving us useful information in diagnosing the sources and mixing pattern of the vapor.     

Factors controlling the solubility of aerosol trace metals in the atmosphere and on mixing into seawater

Previous work has shown that the type and pH history of an aerosol governs trace metal solubility in rainwater. This study concentrates on the crustal elements Al, Fe and Mn and identifies additional processes which affect dissolution not only in the atmosphere but also on mixing into seawater. Aerosol dissolution experiments (at aerosol concentrations of about 30 mg 1^–1) show manganese exhibiting high solubility at the low pH values typical of clouds (54±2.5% at pH 2, with results expressed in mole percent units) with 85% of this increase occurring within 6 hours of acidification. The percentage dissolution decreases to 50% at pH values representative of rainwater (pH 5.5) and to 26±4% at pH 8, typical of seawater. No such dramatic solution phase removal occurs at pH 8 in the presence of inorganic anions (to a final solubility of 44±2%). Thus the extent of manganese dissolution depends strongly on whether aerosols are cycled through acidic environments and on subsequent inorganic complexation once rainwater mixes into sea. Aluminium shows highest dissolution (7.1±0.6%) at low pH with 78% of this increase occurring within 6 hours of acidification. Rapid solution phase removal occurs on increasing the pH to that representative of rainwater (to 0.9±0.4% with 87% of this decrease occurring within 15 min). As a consequence of acid cycling and aluminium's amphoteric nature, solubility is enhanced at seawater pH (2.3±0.3%) over that in rain. Iron shows a strong pH-solubility relationship with highest solubility at low pH (4.7±0.2%), 70% of this value being reached within 6 hours of acidification, and decreasing rapidly to 0.17% as pH is raised to 8. Addition of inorganic anions at pH 8 to simulate mixing into seawater causes a further decrease in solubility, perhaps due to anion induced colloid destabilisation. Photochemical reduction also effects solubility under low pH conditions with Fe(II) comprising 1% of the total iron in the Saharan Aerosol used and 8.4% in an Urban material at a pH of 2. This element shows rapid solution phase removal with increasing particulate load which is tentatively rationalised in terms of a simple Kd approach.     

Aggregation of montmorillonite and organic matter in aqueous media containing artificial seawater

Background  

The dispersion-aggregation behaviors of suspended colloids in rivers and estuaries are affected by the compositions of suspended materials (i.e., clay minerals vs. organic macromolecules) and salinity. Laboratory experiments were conducted to investigate the dispersion and aggregation mechanisms of suspended particles under simulated river and estuarine conditions. The average hydrodynamic diameters of suspended particles (representing degree of aggregation) and zeta potential (representing the electrokinetic properties of suspended colloids and aggregates) were determined for systems containing suspended montmorillonite, humic acid, and/or chitin at the circumneutral pH over a range of salinity (0 – 7.2 psu).     

Major and trace elements in German bottled water,their regional distribution,and accordance with national and international standards

The market for mineral water has been growing steadily over the last few years. Germany is the country with the highest number of bottled mineral water brands (908 bottled water samples from 502 wells/brands were analyzed). The per capita consumption of mineral water in Germany in 2003 was 129 L. A wide range of values of one to seven orders of magnitude was determined for 71 elements in the bottled water samples analyzed by ICP-QMS, ICP-AES, IC, titration, photometric, conductometric and potentiometric methods. A comparison of the element concentrations and the legal limits for both bottled and tap water (EU, Germany, US EPA, WHO) shows that only 70% of the 908 mineral water samples fulfill the German and EU drinking water (i.e., tap water) regulations for all parameters (not including pH) for which action levels are defined. Nearly 5% of the bottled water samples not fulfill the German and EU regulations for mineral and table water. Comparison of our results with the current German and European action levels for mineral and table water shows that only 42 of the bottled water samples exceed the limits for one or more of the following elements: arsenic, nitrate, nitrite, manganese, nickel and barium concentrations. Ten of the bottled water samples contain uranium concentrations above the 10 μg/L recommended limit.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

湖相深水细粒物质的混合沉积作用探讨*

沉积物的混合是自然界的普遍现象,湖盆中广泛发育的深水细粒沉积岩本身就是一类混积岩。以东营凹陷古近系沙河街组三段下亚段—沙河街组四段上亚段细粒沉积岩为研究对象,通过厘米级岩心观察描述、小型沉积构造解剖、岩石薄片观察、X射线衍射全岩矿物分析及微量元素测试等方法,研究细粒物质的产出状态和混合方式;分析湖盆流体、气候及水体性质对细粒物质迁移、混合、沉积的控制作用,尝试探讨细粒物质的混合沉积机制。结果表明,湖相深水细粒沉积岩既有物质成分上的混合,也有结构的混合,且在宏观与微观的不同尺度均存在混合;混合沉积作用有均匀混合、纹层叠置混合、不均匀团块状混合等类型。纹层叠置混合沉积是最主要的混合沉积方式,依据纹层接触关系、所占比例及矿物产出状态可分为泥砂—灰纹层叠置混合型、泥—灰纹层叠置混合型、泥砂粒序—灰纹层叠置混合型、灰—泥—云纹层叠置混合型等。湖相深水细粒物质的混合沉积作用类型多且往往受多个因素同时控制,气候及水动力条件是控制细粒混合沉积岩发育的最主要因素,不同流体(浊流和底流)作用下的细粒沉积物混合作用存在差异。气候引起湖水性质变化及水体分层,从而控制不同类型细粒物质的絮凝沉降及化学沉积。不同构造部位、不同水体深度的混合作用不同;相同构造部位在垂向上也存在混合沉积方式的差异。     

Forms and bioavailability of phosphorus associated with natural organic matter

Natural organic matter （NOM） is an important ingredient in soil which can improve physical, chemical, and biological properties of soils and nutrient supplies. In this study, we investigated the spectral features and potential availability of phosphorus （P） in the IHSS Elliott Soil humic acid standard （EHa）, Elliott soil fulvic acid standard Ⅱ （EFa）, Waskish peat humic acid reference （WHa）, and Waskish peat fulvic acid reference （WFa） by fluorescence spectroscopy, FT-IR, solution 31P NMR, 3-phytase incubation and UV irradiation. We observed more similar spectral features between EHa and EFa as well as between WHa and WFa than between the two humic acids or two fulvic acids themselves. Phosphorus in WHa and WFa was mainly present in the orthophosphate form. However, only about 5% was water soluble. After treatment by both UV irradiation and enzymatic hydrolysis, soluble orthophosphate increased to 17% of WHa P, and 10%o of WFa P. Thus, it appears that a large portion of P in Waskish peat humic substances was not labile for plant uptake. On the other hand, both orthophosphate and organic phosphate were present in EHa and EFa. Treatment by both UV irradiation and enzymatic hydrolysis increased soluble orthophosphate to 67% of EHa P and 52% of EFa P, indicating that more P in Elliott soil humic substances was potentially bioavailable. Our results demonstrated that source （soil vs. peat） was a more important factor than organic matter fraction （humic acid vs. fulvic acid） with respect to the forms and lability of P in these humic substances.     

Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios

Assessments of inorganic elemental speciation in seawater span the past four decades. Experimentation, compilation and critical review of equilibrium data over the past forty years have, in particular, considerably improved our understanding of cation hydrolysis and the complexation of cations by carbonate ions in solution. Through experimental investigations and critical evaluation it is now known that more than forty elements have seawater speciation schemes that are strongly influenced by pH. In the present work, the speciation of the elements in seawater is summarized in a manner that highlights the significance of pH variations. For elements that have pH-dependent species concentration ratios, this work summarizes equilibrium data (S = 35, t = 25°C) that can be used to assess regions of dominance and relative species concentrations. Concentration ratios of complex species are expressed in the form log[A]/[B] = pH - C where brackets denote species concentrations in solution, A and B are species important at higher (A) and lower (B) solution pH, and C is a constant dependent on salinity, temperature and pressure. In the case of equilibria involving complex oxy-anions (MO _x (OH) _y ) or hydroxy complexes (M(OH) _n ), C is written as pK _n = -log K _n or pK _n * = -log K _n * respectively, where K _n and K _n * are equilibrium constants. For equilibria involving carbonate complexation, the constant C is written as pQ = -log(K ₂ ^l K _n [HCO₃ ^-]) where K ₂ ^l is the HCO₃ ^- dissociation constant, K _n is a cation complexation constant and [HCO₃ ^-] is approximated as 1.9 × 10^-3 molar. Equilibrium data expressed in this manner clearly show dominant species transitions, ranges of dominance, and relative concentrations at any pH.