The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O₂H₂S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH₂S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe²⁺) and manganese (Mn²⁺) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO₃). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin.     

Processes controlling Fe,Mn and Zn in sediments of northern Chesapeake Bay

The dominant physical and chemical processes that control Fe, Mn and Zn are explored by comparing the compositions of sediments and their sources. The $\text{Mn}\text{Fe}$ and $\text{Zn}\text{Fe}$ ratios in sediment are found to be largely unaffected by local hydraulic sorting (unlike the actual concentrations of Fe, Mn and Zn) and thus are useful indicators of origin. The sediments in northern Chesapeake Bay have markedly lower $\text{Mn}\text{Fe}$ and $\text{Zn}\text{Fe}$ ratios than those found in the Susquehanna River (dissolved plus suspended) under ordinary flow, but not under high flow conditions. Since high flow conditions dominate sediment transport, seaward loss of a major fraction of the river-derived Mn and Zn need not be invoked to reconcile sediment and river compositions. Sediments in the seaward end of the northern bay have higher $\text{Mn}\text{Fe}$ and $\text{Zn}\text{Fe}$ ratios than their principal external source, the eroding shore deposits. The excess Zn appears to be derived from the atmosphere; the required depositional flux of Zn is consistent with measurements of the total atmospheric flux. The excess Mn can be explained by remobilization of roughly 5% of the river-borne Mn from sediments in the landward part of the northern bay. Because rare floods influence sediment composition markedly, comparing suspended particles in the river at ordinary stages with resuspended sediment in the estuary would lead to the false interpretation that Mn and Zn were being desorbed in the saltwater.     

Distribution and stoichiometry of Al,Mn, Fe,Co, Ni,Cu, Zn,Cd, and Pb in seawater around the Juan de Fuca Ridge

A central theme of the ongoing GEOTRACES program is to improve the understanding of processes occurring at ocean interfaces with continents, sediments, and ocean crust. In this context, we studied the distributions of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb around the Juan de Fuca Ridge (JdFR) in total dissolvable (td), dissolved (d), and labile particulate (lp) fractions, which represent a fraction in unfiltered samples, filtered samples through an AcroPak capsule filter, and the difference between td and d, respectively. Al and Fe were dominated by lp-species, while Ni, Zn, and Cd were dominated by d-species with undetectable amounts of lp-species. Major findings in this study are as follows: (1) The continental margin (CM) provided large sources of Al, Mn, Fe, and Co from the surface to ~2000 m in depth. The supply from CM caused high surface concentrations of dMn and dCo, a subsurface (100–300 m depth) maximum of dCo, and intermediate (500–2000 m depth) maxima of lpAl and lpFe. The supply of dFe from CM was ~10 times that from the high-temperature hydrothermal activity at station BD21, which is located at ~3 km from the Middle Valley venting site and ~ 200 km from Vancouver Island. (2) DPb was maximum at the top layer of North Pacific Intermediate Water, probably owing to isopycnal transport of anthropogenic Pb via advection of subducted surface waters. Although dCo and dPb had different sources in the upper water, they showed a strong linearity below 300 m (r ² = 0.95, n = 38), indicating concurrent scavenging. (3) A high-temperature hydrothermal plume occurred at a depth of 2300 m at BD21, accounting for maxima of dAl, dMn, dFe, lpCu, and lpPb and a minimum of dCu. (4) Strong bottom maxima of lpAl, lpMn, lpFe, lpCo, and lpPb occurred above the abyssal plain at the western foot of the JdFR, indicating resuspension of sediments. However, bottom maxima of d-species were apparent only for dAl and dCu.     

Regional variations in Mn,Ni, Cu,and Co of ferromanganese nodules from a basin in the Southeast Pacific

Deep-sea nodules from the Southeast Pacific (northern sector of the Nazca Plate) have been studied regarding their metal content, shapes, and sedimentary environment. The area investigated lies in the southern boundary region of the equatorial zone of high biological productivity. The nodules accumulate by two different growth processes: (1) early diagenetic growth by supply from pore water and (2) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules. Considering the $\text{Mn}\text{Fe}$ ratio, the examined basin can clearly be divided in three ferromanganese facies. The $\text{Mn}\text{Fe}$ quotient increases generally from south to north, whereas Ni and Cu concentrations show a distinct maximum in the mid facies at a $\text{Mn}\text{Fe}$ ratio of about 5. Computing the correlation of $\text{Mn}\text{Fe}$ quotient versus (Ni+Cu), hyperbolic regressions show the best coefficients of correlation and separate the quantity of nodules in two groups. The ascending and the descending hyperbola represent two geochemical ranges which are controlled by different accumulation mechanisms.     

The determination of Mn,Fe, Ni,Cu and Zn in seawater by atomic absorption spectrometry after coprecipitation with lanthanum hydroxide

A simple and rapid coprecipitation method for the determination of several trace metals in seawater is presented. These metals are coprecipitated with lanthanum hydroxide, the precipitate is dissolved, and then the metals are determined by atomic absorption spectrometry. Lanthanum hydroxide was chosen as a coprecipitant for the following reasons, (a) lanthanum hydroxide has a sufficiently low solubility and forms an easily filterable flocculate at about 80C, and (b) lanthanum has an absorption wavelength that is sufficiently separated from those of the other elements to be analysed, i.e., Mn, Fe, Ni, Cu and Zn. Experimental results show that these metals are coprecipitated by the present method with excellent recoveries.     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O₂/H₂S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O₂/H₂S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.     

中国多金属结核开辟区间隙水中铜、锰、镍的分布规律

通过对东北太平洋海域中国多金属结核开辟区沉积物间隙水中铜、锰、镍等微量元素的详细研究表明,锰主要受沉积环境的影响,其含量的变化范围在0.16～8.61μg/dm3之间;铜和镍则主要与表层海水的初级生产力有关,研究区内间隙水中铜和镍含量的变化范围分别为0.16～20.8和0.80～3.12μg/dm3,且这些元素在沉积物—水界面处均存在最大浓度梯度.利用“Fick扩散定律”计算表明,锰在研究区主要是从上覆海水向沉积物扩散,是沉积物中锰的主要来源之一;而铜和镍则是从沉积物向上覆海水扩散,是底层海水中铜和镍的主要来源。与表层海水中铜和镍向底层海水的输送通量计算结果相比,底层海水中铜和镍的含量主要受沉积物的控制.     

福建主要港湾悬浮物、悬浮有机质等环境因子的分布与变化

依据2001年福建主要港湾水体中悬浮物质的调查资料,讨论了悬浮物(TPM)、悬浮有机质(POM)的分布和动态变化特征。TPM季平均质量浓度为20.86~22.68 mg.dm-3,年平均为21.50 mg.dm-3;其季节变化为11月最高,8月次高,5月最低。11月最高主要受风浪和潮流的影响。POM季平均质量浓度为3.14~3.36 mg.dm-3,年平均为3.27 mg.dm-3;其季节变化为8月最高,5月次高,11月最低。夏季POM的含量分布主要受生物活动影响。叶绿素a季平均质量浓度为6.01~9.02 mg.m-3,初级生产力季平均为54.9~412.8 mgC.m-2.d-1,都是8月最高,11月最低。浮游植物细胞数季平均为3 563.4×103~24 862.4×103个.m-3,5月最高,11月最低。     

The distribution of Mn,Fe, Cu,Ni, Co,Ga, Cr,V, Ba,Sr, Sn,Zn, and Pb,in some soil-sized particulates from the lower troposphere over the world ocean

Soil-sized particulates have been collected on board ship by a mesh technique from the lower troposphere of the North, Equatorial and South Atlantic Ocean, northern and southern Indian Ocean, South and East China Sea and various coastal localities.Spectrographic analysis reveals that, on average, the particulates have concentrations of Mn, Ni, Co, Ga, Cr, V, Ba, and Sr which are of the same order of magnitude as those in average crustal material. In contrast, the average concentrations of Pb, Sn, and Zn are one order of magnitude higher than those in average crustal material.Within this “world-wide” average there are significant geographical variations in the distributions of Pb, Sn, and Zn which may be related to anthropogenic sources.On the basis of trace-element distributions lower tropospheric soil-sized marine particulates have been divided into four genetic components; local, zonal, inter-zonal, and global. The proportions of these components vary geographically, and each component may have both a natural and an anthropogenic fraction.     

Phosphorus and metals bound to organic matter in coastal sediments - An investigation of complexes of P,Cu, Zn,Fe, Mn,Ni, Co and Ti by inductively coupled plasma-atomic emission spectrometry with sephadex gel chromatography

Phosphorus and metals bound to organic matter were separated from coastal sediments of Harima Sound in Seto Inland Sea, Japan by extraction with NaOH and fractionated by Sephadex G-25 chromatography. Phosphorus and metals were determined in the eluates by a multi-channel, inductively coupled plasma-atomic emission spectrometer. Phosphorus and Cu, Zn, Fe, Mn, Ni, Cr, Co and Ti bound to organic matter with high molecular weights (OMHMW) (MW ? 5000) were found to be present in the sediments, but no Mo or V were found. The technique provides minimum estimates of the amounts of P and metals bound to organic matter. These organic complexes show surface enrichment in a sediment core (0–20 cm) and their contents decrease with depth. Also, the amounts of eighteen elements, namely: P, Fe, Mn, Zn, Cu, Si, Al, Ti, Pb, Co, Ni, Cr, Mo, V, Na, K, Ca and Mg, in H₂O, ammonium acetate at pH 7 and 5, hydrogen peroxide, hydroxylamine hydrochloride and hydrogen fluoric acid soluble fractions have been determined with a selective chemical leaching technique for the ²¹⁰Pb-dated sediment core sample. Considerable amounts of P (6–19%) and Cu (5–21%) were associated with organic matter, in contrast to other metals such as Fe, Mn, Zn, Ni, Cr, Co and Ti which were associated with sulfide and silicate.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

白令海底栖生物体内的Cd、Cu、Cr、Zn含量及其生物富集作用

The Bering Sea is an area of high biological productivity, with large populations of sea-birds, demersal and pelagic fishes, so it seemed desirable to assess the bioaccumulation of trace metals in the ...     

Distribution of total Al,Cd, Co,Cu, Ni and Zn in the tongue of the ocean and the northwestern Atlantic Ocean

The elements Al, Cd, Co, Cu, Ni and Zn were concentrated from seawater using tetraethylenepentamine resin and analysed by atomic absorption spectrophotometry. The spatial distribution of these elements in the northwest Atlantic Ocean is discussed with respect to possible riverine inputs to the area from Puerto Rico.     

大气颗粒物中微量营养元素Fe、 Mn和Cu的来源与沉降

测定了义乌市大气颗粒物中总悬浮颗粒物(TSP)及微量营养元素Fe、Mn和Cu的浓度,并对颗粒物粒径分布和外形进行了扫描电镜分析,同时分析了这3种金属的来源和沉降量。结果表明,微量营养元素Fe和Mn主要来源于地壳,而Cu来源于人为污染;Fe与Mn之间的相关性极显著;绝大部分颗粒物的粒径小于9μm;Fe和Mn湿沉降量大于干沉降量,而Cu以干沉降为主。     

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.