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 partitioning of trace metals (Cd,Cu, Ni,Pb, Zn) in Galveston Bay waters

The distribution of several trace metals has been studied in the surface waters of Galveston Bay, Texas, in order to assess the impact of complexation with organic and reduced sulfur species on the partitioning of trace metals between particulate and aqueous species. The distribution of trace metals in the filter-passing fraction (<0.45 μm) showed two apparent trends: (1) the carrier phase metals (i.e., Fe and Mn) were largely removed in the Anahuac Channel region, which was dominated by direct Trinity River inputs; (2) the other metals (Cd, Cu, Ni, Pb, and Zn) showed non-conservative mixing behaviour, with mid-salinity maxima, within the estuarine regions of Galveston Bay. The average percentage of metal in the filter-passing fraction, as compared to the total metal load, decreased in that region from 95% to 9% in the order Ni>Cu>Cd>Zn>Pb>Mn>Fe, while an increasing trend was found in the same sequence for the acid-leachable fractions. The average values of K_d1, the particle-water partition coefficient, expressed as the ratio of weak acid-leachable particulate fractions to the filter-passing fractions, increased in the order Ni<Cu<Cd<Zn<Mn<Pb<Fe. This sequence is consistent with the relative importance of particulate transport of these trace metals from estuaries to coastal oceans. The observed decrease of K_d1 of Cu with increasing concentrations of suspended particulate matter (SPM), also called the “particle concentration effect” (PCE), can be eliminated when the free ionic, rather than the total concentration of Cu in the filter-passing fraction is used for calculating this ratio. A particle concentration effect would be expected if the binding of these trace metals by particles is mediated by solution (i.e., filter-passing) phase ligands. Complexation of Cd, Cu, Ni, Pb, and Zn with reduced sulfur species could be one of the causes for the observed linear correlations between metals and reduced sulfur species in both the filter-passing and filter-retained fractions. Significant correlations between Cu in the weak acid-leachable fraction and chlorophyll a (Chl a) concentrations suggest biological mediation of Cu uptake into the particulate fraction.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

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.     

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.     

Seasonality in nutrient concentrations in Galveston Bay

In order to investigate factors controlling nutrient cycling in the shallow and turbid coastal ecosystem of Galveston Bay, data from: (1) the Texas Water Commission (TWC) database 1980–1989, and (2) salinity transects in 1989 and 1993 are presented and analyzed. Statistical regression and time-series analysis were carried out on data acquired by TWC between 1980 and 1989, in an attempt to establish seasonally of nutrient and chlorophyll-a (chl.-a.) concentrations in the bay and to determine factors which regulate these concentrations.A strong seasonality was found for phosphorus and chl.-a. in the upper and mid-bay stations. A recurring maximum for phosphate occurred in September and a chl.-a. maximum occurred regularly in March–April. It is hypothesized that benthic regeneration of phosphorus at the end of summer is responsible for the phosphate maximum. The inverse correlation of the partition coefficient (K_d) for phosphate with the concentration of suspended particulate matter (SPM), coupled to a strong enrichment of phosphate in suspended particles at low SPM concentrations, indicates additional control by geochemical and physical processes such as particle sorting and/or particle-colloid interactions. Nitrate is inversely correlated with salinity at the upper and mid-bay stations, indicating the Trinity River is a major source.Nutrient concentrations in the lower bay (East and West Bay stations) are considerably lower and less predictable, as they are not correlated with salinity or temperature. Data from the 1989 and 1993 transects confirm the yearly maximum in phosphate concentration in late summer months, with peak concentrations in the upper Trinity Bay. It is concluded that despite possible phosphate buffering by physical and geochemical mechanisms, relatively large concentration maxima recur regularly every year during the summer, possibly caused by a benthic source of phosphate.     

Distribution and Sources of Dissolved and Particulate Heavy Metals (Mn,Co, Ni,Cu, Zn,Cd, Pb) in Masan Bay,Korea

Ocean Science Journal - In this study, we investigated the spatial and temporal distribution and sources of dissolved and particulate heavy metals in Masan Bay, an area that for a long time has...     

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.     

海洋沉积物中铁、锰、锌、铬、铜、镍、钴、铅和镉的原子吸收测定

海洋环境及沉积地球化学的调查研究,常需同时了解多种元素在海洋底质中的含量及其分布规律.对于某些非金属及半金属元素,我们曾研究过应用碱性有机染料的萃取-光度测定法[1-3].原子吸收分光光度法则可以快速、准确地测定海洋沉积物中的许多种金属的含量[4-6],一般不需要大量的预处理.     

The determination of Cd,Cu, Fe,Ni, Pb and Zn in Baltic Sea water

Cd, Cu, Fe, Ni, Pb and Zn were determined in 123 samples from the Baltic Sea proper. The trace metals were extracted directly on board the vessel, using a dithiocarbamate-Freon procedure. Final analyses of the extracts are performed onshore by atomic absorption spectrometry.Similar trace-metal concentrations are found in different areas of the Baltic proper. Most values fall in the following ranges: Cd, 30–60 ng 1^?1; Cu, 0.6–1.0 μg 1^?1; Fe, 0.3–0.9 μg 1^?1; Ni, 0.6–0.9 μg 1^?1; Pb, 0.05–0.2 μg 1^?1; and Zn, 1.5–3.5 μg 1^?1. The metal-concentrations are generally independent of depth. However, copper exhibits a small but significent decrease in concentration below 80 m.Filtration did not affect trace-metal concentrations, with the exception of iron in waters from lower layers. Similarly, storage under acid conditions was shown to affect only the concentration of iron. An electro-chemical technique was also used to determine Cu in some samples.     

Distributions of carbohydrates, including uronic acids, in estuarine waters of Galveston Bay

The concentrations of carbohydrates, including uronic acids, in dissolved (≤0.45μm) and colloidal (1 kDa—0.45 μm) phases were measured in estuarine waters of Galveston Bay, TX, in order to study their role in heavy metal detoxification. The concentrations of dissolved monosaccharides (MCHO) in Galveston Bay ranged from 13 to 62 μM-C, and those of dissolved polysaccharides (PCHO) ranged from 10 to 42 μM-C. On average, MCHO and PCHO contributed about 11% and 7% to dissolved organic carbon (DOC), respectively. The colloidal carbohydrates (CCHO) in Galveston Bay varied from 7 to 54 μM-C, and accounted for 9% to 24% of the colloidal organic carbon (COC), with an average value of 17%, suggesting that CCHO is abundant in the high molecular weight (HMW) fraction of DOC. The concentration of CCHO is generally significantly higher than that of PCHO. This result is attributed to entrainment of low molecular weight (LMW) carbohydrates into the retentate fraction during ultrafiltration. The concentration of total dissolved uronic acids (DUA) in the same samples varied from 1.0 to 8.3 μM-C, with an average value of 6.1 μM-C, while the colloidal uronic acids (CUA) ranged from 0.8 to 6.4 μM-C, with an average value of 4.8 μM-C. The concentrations of DUA are higher than the previously reported values in coastal waters. Furthermore, CUA represent a dominant component of DUA in Galveston Bay waters. More importantly, significant correlations of PCHO and DUA to dissolved Cu concentrations (≤0.45 μm) were found, suggesting that acid polysaccharides were produced in response to trace metal stressors.     

The Role of Primary-Producer-Mediated Organic Complexation in Regional Variation in the Supply of Mn,Fe, Co,Cu, Ni and Zn to Oceanic,Non-Hydrothermal Ferromanganese Crusts and Nodules

Oceanic, non-hydrothermal ferromanganese crusts and nodules are variably enriched in Mn, Fe, Co, Cu, Ni and Zn. Comparison of the content of these elements in crusts and nodules with the level of primary productivity in the South Pacific Ocean suggests that primary-producer-mediated complexation of several of these elements by organic ligands in solution may contribute to explaining a pattern of distinctive associations observed between compositional variations for these elements in these deposits and variations in the level of primary productivity.     

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.     

Historical contamination of PAHs, PCBs, DDTs, and heavy metals in Mississippi River Delta, Galveston Bay and Tampa Bay sediment cores

Profiles of trace contaminant concentrations in sediment columns can be a natural archive from which pollutant inputs into coastal areas can be reconstructed. Reconstruction of historical inputs of anthropogenic chemicals is important for improving management strategies and evaluating the success of recent pollution controls measures. Here we report a reconstruction of historical contamination into three coastal sites along the US Gulf Coast: Mississippi River Delta, Galveston Bay and Tampa Bay. Within the watersheds of these areas are extensive agricultural lands as well as more than 50% of the chemical and refinery capacity of the USA. Despite this pollution potential, relatively low concentrations of trace metals and trace organic contaminants were found in one core from each of the three sites. Concentrations and fluxes of most trace metals found in surface sediments at these three sites, when normalized to Al, are typical for uncontaminated Gulf Coast sediments. Hydrophobic trace organic contaminants that are anthropogenic (polycyclic aromatic hydrocarbons, DDTs, and polychlorinated biphenyls) are found in sediments from all locations. The presence in surface sediments from the Mississippi River Delta of low level trace contaminants such as DDTs, which were banned in the early 1970's, indicate that they are still washed out from cultivated soils. It appears that the DDTs profile in that sediment core was produced by a combination of erosion processes of riverine and other sedimentary deposits during floods. Most of the pollutant profiles indicate that present-day conditions have improved from the more contaminated conditions in the 1950-1970's, before the advent of the Clean Water Act.     

FLOCCULATION OF DISSOLVED Fe, Al, Mn, Si, Cu, Pb AND Zn DURING ESTUARINE MIXING

This is the first study of the flocculation of dissolved Fe, Al, Mn, Si, Cu, Pb and Zn during mixing in Zhujiang Estuary, based on the experiment on a series of solutions of salinities ranging from 0 to 24 by mixing the Zhujiang water near Zhongshan University and the seawater in Wan-shan Archipelago area. The mechanism of flocculation of the 7 elements is explored, and the effects of time, acidity and temperature on flocculation are discussed. The results show that the flocculation rates of Fe and Pb in the Zhujiang water are almost a hundred per cent, while that forCu reaches 76%; for Mn, 51%; for Al, 48%; for Zn, 28%; and for Si, 1.2%, indicating that Si is conservative.     

Metal-organic complexes in seawater — An investigation of naturally occurring complexes of Cu,Zn, Fe,Mg, Ni,Cr, Mn and Cd using high-performance liquid chromatography with atomic fluorescence detection

Metal-organic complexes were isolated from coastal seawater by adsorption onto octadecyl-bonded silica (SEP-PAK cartridges) and injected into a high-performance liquid chromatograph. Trace metals were identified in the eluate by a four-channel non-dispersive atomic fluorescence detector. Organic complexes of copper, zinc, iron, magnesium, nickel and manganese were found to be present but no complexes of chromium or cadmium were detected. The complexes covered a wide range of polarities with no specific complexes being predominant. Interference from the stainless-steel chromatograph was negligible. The technique provides a minimum estimate of the amount of metal organics and it is suggested that a significant fraction of the metal organics present are too polar to be completely retained by the SEP-PAK cartridges. Typical values of the amounts of trace metal isolated by this technique corresponded to concentrations in the original seawater of >65 ngl^?1 (Cu), >27 ngl^?1 (Fe) and >41 ngl^?1 (Zn).     

离子交换—原子吸收光谱法测定海水中痕量铜、铅、锌、镉、铁、锰

本文介绍了用国产D401型螯合树脂分离富集海水中铜、铅、锌、镉、铁、锰等痕量元素,并用原子吸收光谱仪测定其含量的方法。讨论了各元素的分离条件选择及干扰元素的影响,并与溶剂萃取法的结果作了比较。各元素检测的定量下限为:铜0.5μg/L、铅0.1μg/L、锌1.0μg/L、镉0.01μg/L、铁2.0μg/L、锰2.0μg/L。方法精密度在4—8％之间,回收率为90—102％。     

Effect of food quantity and quality on egg production of Acartia tonsa Dana from East Lagoon,Galveston, Texas

The nutritional value of natural particle diets on egg production of Acartia tonsa from subtropical East Lagoon was studied from April to November 1981. During the summer, monospecific blooms of dinoflagelates and chloromonads dominated the natural particle assemblages. But during the spring and fall, the inorganic fraction was dominant and chlorophyll concentrations were lower. At ambient concentrations of natural particles from East Lagoon, specific egg production rates were correlated in stepwise multiple regressions with temperature, salinity, and C:N ratio but not phytoplankton pigment concentrations. For stepwise multiple regression including all natural particle concentrations, specific egg production rates were correlated with C:N ratio, average particle diameter, percent nanoparticles (5–20 μm), and percent phytoplankton picoparticles. A nonlinear regression developed for the entire data set revealed that above the critical chlorophyll concentration (∼ 5 μg 1⁻¹ at all temperatures), an increase in temperature of 4°C caused about the same increase in specific egg production rates as a decrease in salinity from 30 to 10‰, or a decrease in C:N ratio from 10 to 5. On a seasonal scale, temperature is the dominant influence on egg production of A. tonsa in East Lagoon where temperature ranges from 10 to 30°C but on shorter time scales food quality, food quantity or salinity may influence egg production rates as much as temperature.     

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.