A study of the geochemistry of suspended particulate matter in coastal waters

The concentrations of Si, Al, Ti, Fe, K, Ca, Mg, P and Mn, before and after chemical leaching, in particulate matter from waters off the west coast of Scotland have been measured in vertical profiles at two seasons. The distribution of Si and Ca are shown partly to reflect temporal changes in biological production in different waters. The distributions of Al, Ti, Fe, K and Mg have been used to distinguish different sources and types of suspended alumino-silicates, and to trace probable circulation patterns in the water mass.While Si and Ti contents of the particulate matter are unaffected by mild chemical leaching, large amounts of other elements, notably Mg, K and Al, can be removed by this treatment. Presumably, these losses indicate preferential release of these elements from octahedral and interlayer sites in clay mineral lattices.The distribution of particulate P covaries with non-silicate Fe in the surface waters, while in bottom waters, high concentrations of particulate Fe and Mn are associated. The relationship of Fe and P is considered to be due to the presence of particulate ferriphosphates derived from runoff. The particulate Mn and Fe in deep waters is produced by the precipitation of dissolved metals released from bottom sediments by diagenesis.     

Contrasting trace element geochemistry in two American and French salt marshes

Trace metals were analyzed in the bulk fine phase of two contrasting salt marsh cores on the North Atlantic east (Baie de l'Aiguillon, LaRochelle, France) and west (Lewes, DE, USA) coasts. The purpose is to gauge how the different clay mineral sources and surface sedimentary diagenetic conditions affect the respective trace element geochemistries. It has been established that there is considerably more clay mineral diagenesis at the zone of redox transition in the Delaware core than in the l'Aiguillon core. The Delaware core shows unweathered glacial sedimentary material directly deposited from the continental shelf whereas the l'Aiguillon core is formed from soil clays deposited after river and estuarine transport. Although there is strong Mn redox depletion in the Delaware salt marsh core, and enrichment in the French one at l'Aiguillon, transition elements seem to follow iron content in both cores. The trace pollutant elements Pb, Sn and Zn show pronounced depth profiles in both North Atlantic cores. The Pb, Sn and Zn appear to be carried by clay sources into the French marshes, while appearing to be largely deposited by atmospheric processes as well into the Delaware marsh.Upon deposition, the Zn appears to become decoupled from lead, which is probably more strongly fixed on clays. The Sn seems to be both air transported, and carried as well on non-clay phases contaminated by industrial organo-tins, including antifouling bottom paints. Copper while uniformly enriched in France, probably from use in regional vineyards, appears enriched only near the top at Delaware, suggesting diagenetic recycling in the more abundant peat in the surface. The Cs and Li appear to be tracers for specific soil-derived clay sources in the French core source materials. These observations suggest that clay is a very important carrier in fixing trace elements for historical records as salt marsh sediments.     

Factors influencing particulate matter geochemistry in the St. Lawrence estuary turbidity maximum

635 samples of suspended particulate matter (SPM), collected in the St. Lawrence river and estuary during periods of high and low river flow from a series of individual and anchor stations on a transect traversing the turbidity maximum zone, as well as two sediment box cores, were analyzed for Al, Si, Ca, Mg, Fe and Mn.An abrupt change in elemental composition occurs when traversing the front at the landward edge of the turbidity maximum. As the SPM concentration increases across the front from 20–200 mg l^?1, the Ca/Al and Mg/Al ratios of the SPM increase and the Si/Al, Fe/Al and Mn/Al ratios decrease. The almost 50% decrease of the Mn/Al ratio is not related to changes in salinity. Within the turbidity maximum the tidal-averaged Si/Al, Ca/Al, Mg/Al and Fe/Al ratios of the SPM do not differ significantly from the landward to the seaward end of the turbidity zone, but on one tidal station the ratios of Si, Ca and Fe to Al are significantly lower at high river flow than at low flow. The Mn/Al ratio is insensitive to the extreme variations of either salinity (0.6–30‰) or SPM concentrations (10–480 mg l^?1) within the turbidity zone. A tendency for higher Mn/Al ratios to be associated with near-bottom SPM, observed in the center of the turbidity zone during the low river flow period, is well developed in the lower reaches of the zone.Diagenetic mobilization within the rare fine-grained bottom sediments of the turbidity maximum is responsible for changes in Mn and Fe content of particulate matter, and early settling of coarse-grained components and size sorting within the zone are responsible for other compositional changes. Local sources, desorption and precipitation are apparently of secondary importance. The depletion of both Mn and Fe in the SPM and sediment of the upper estuary implies a net seaward escape of diagenetically mobilized metal.     

海洋沉积物/颗粒物在生源要素循环中的作用及生态学功能

海洋沉积物/颗粒物是生源要素循环过程中的关键源与汇,沉积物/颗粒物一方面是海水生源要素的主要归宿,生源要素从溶解态经复杂的生物-化学过程转变为颗粒态,颗粒物质再沉降形成沉积物,另一方面,海洋沉积物/颗粒物经过微生物-浮游动物-底栖生物作用分解形成溶解态的生源要素,并释放到海水中再次被浮游植物利用,进入下一轮循环,所以,海洋沉积物/颗粒物具有异常重要的生态学功能。浮游植物是海水溶解态生源要素的利用者和海源颗粒态生源要素的初始形成者,浮游动物通过摄食浮游植物或其他有机颗粒物可释放出溶解态生源要素或形成更大的颗粒物,颗粒物沉降后形成的沉积物又通过底栖生物摄食-扰动-破碎等过程将颗粒生源要素释放进入水体参与再循环。生态系统不同类群的生物在颗粒生源要素的释放-沉降中所起的作用不同而又相互关联,其中浮游动物-底栖生物的摄食与代谢、微生物参与的分解过程起着非常重要的作用。所以,海洋沉积物/颗粒物生态学功能研究作为支撑海洋环境和资源的持续利用的科学基础,已成为海洋科学的前沿领域,必将获得跨越发展。     

Reduction of particulate matter and gaseous emission from marine diesel engines using a catalyzed particulate filter

Diesel engines are used widely as the power sources of coastal ships and international vessels primarily due to their high thermal efficiency, high fuel economy and durable performance. However, the gaseous and solid substances exhausted from diesel engines during the combustion process cause air pollution, in particular around harbor regions. In order to effectively reduce particulate matter and gaseous pollution emissions, a catalyzed particulate filter was equipped in the tail pipe of a marine diesel engine. The engine's performance and emission characteristics under various engine speeds and torques were measured using a computerized engine data control and acquisition system accompanied with an engine dynamometer. The effectiveness of installing a catalyzed particulate filter on the reduction of pollutant emissions was examined. The experimental results show that the exhaust gas temperature, carbon monoxide and smoke opacity were reduced significantly upon installation of the particulate filter. In particular, larger conversion of carbon monoxide to carbon dioxide — and thus larger CO₂ and lower CO emissions — were observed for the marine diesel engine equipped with a catalyzed particulate filter and operated at higher engine speeds. This is presumably due to enhancement of the catalytic oxidation reaction that results from an exhaust gas with stronger stirring motion passing through the filter. The absorption of partial heating energy from the exhaust gas by the physical structure of the particulate filter resulted in a reduction in the exhaust gas temperature. The particulate matter could be burnt to a greater extent due to the effect of the catalyst coated on the surface of the particulate filter. Moreover, the fuel consumption rate was increased slightly while the excess oxygen emission was somewhat decreased with the particulate filter.     

海洋悬浮颗粒物中氮同位素的 EA-IRMS法测定

本测定方法利用元素分析 同位素质谱 (EA IRMS)分析系统 ,设计改装了一套适用于大气氮标定钢瓶氮同位素的封闭分析系统 ,并建立了测定悬浮颗粒物中氮同位素的分析方法 .将海水样品经 45 0℃预燃烧过的玻璃纤维滤膜过滤 ,获得悬浮颗粒物 .设定大气δ1 5N值为零 ,连续进样 12次 ,测定大气氮的δ1 5Nair 值为 ( 0 .0 2±0 .0 3)‰ ;并对参考气高纯钢瓶氮进行了标定 ,其δ1 5Nair值为 ( -0 .0 9± 0 .0 2 )‰ ;其离子强度在 0 .5 0～ 6 .0V之间具有良好的线性 ,样品分析精度优于 0 .15‰ .采用该方法实测 5 8份海水悬浮颗粒物 ,获得1 5N天然丰度平均值为 0 .36 7% .     

Concentration of particulate trace metals and particulate organic carbon in marine surface waters by a bubble flotation mechanism

The transport of particulate organic carbon (POC) and particulate trace metals (PTM) to the sea surface by rising bubbles in samples of surface water collected in Narragansett Bay was examined using an adsorptive bubble separation technique. Recoveries of POC ranged from 30 to 59% while those of the particulate form of the trace metals, Al, Mn, Fe, V, Cu, Zn, Ni, Pb, Cr and Cd were generally greater than 50%. The recovery data were used to arrive at a rough order of magnitude estimate of the bubble transport of POC and PTM under open-ocean conditions. While transport rates of the trace metals to the sea surface by both bubble transport and atmospheric deposition varied over approximately 3 orders of magnitude, the ratio of bubble transport to atmospheric deposition for most metals varied over approximately one order of magnitude, perhaps suggesting some degree of coupling between atmospheric PTM and bubble-transported PTM.     

The influence of organic matter and atmospheric deposition on the particulate trace metal concentration of northwest Atlantic surface seawater

Particulate trace metals (PTM), organic carbon (POC), and organic nitrogen (PON) were measured in a series of surface bucket samples collected between the New England coast of the United States and Bermuda. PTM concentrations were lower or equivalent to the lowest PTM concentrations reported in the literature. Examination of the relative variations in PTM with respect to particulate aluminum and carbon led to the conclusion that organic matter was the probable regulator of PTM abundance in open-ocean surface waters and was important in this respect for continental shelf and slope waters as well.Enrichment factors of trace metals relative to their crustal abundances were found to be similar in the atmosphere sampled in Bermuda and in Sargasso Sea surface water particulate matter. A simplistic vertical flux model was constructed which showed atmospheric input of trace metals to the Sargasso Sea to be of the same approximate magnitude as the rate of removal of PTM from the mixed layer by sinking in association with POC. Essentially all of the particulate Al, Fe, and Mn in the Sargasso Sea mixed layer was attributed to aeolian sources. The fate of other atmospherically derived trace metals in the Sargasso Sea mixed layer was suggested to be a function of their solubility in seawater.     

The capacity of marine plankton, macrophytes and particulate matter to adsorb Cu in the presence of Mg

A complexometric titration technique was employed to measure the total capacity of a variety of marine organisms to adsorb Cu²⁺. Measured adsorption capacities were 0.22 meq g⁻¹ for phytoplankton, 0.3–1.0 meq g⁻¹ for macrophytes, 1.0–2.5 meq g⁻¹ for zooplankton and 0.3 meq g⁻¹ for suspended particulate matter. The capacity of these materials to adsorb Cu²⁺ was reduced significantly in the presence of Mg²⁺ at seawater concentrations. Competition between Mg^t2+ and Cu²⁺ for adsorption sites at pH 6 is described by an average conditional equilibrium constant of 10^3.7. This constant is such that very little Cu²⁺ may be adsorbed onto particulates and marine phytoplankton in the presence of Mg²⁺. Further, primary productivity data and estimates of the detrital carbon sedimentation in Long Island Sound suggest that the flux of particulate carbon is insufficient to remove significant amounts of Cu from the water column to sediments by adsorption mechanisms.     

Significance of oxides and particulate organic matter in controlling trace metal partitioning in a contaminated estuary

The sediment–water partitioning of radiolabelled Cd, Hg and Zn has been investigated along an estuarine salinity gradient using samples from the Mersey Estuary, UK. Partitioning was studied using untreated particles, and particles that had been extracted using either a reducing agent (NH₂OH.HCl–HOAc) or an oxidising agent (H₂O₂) in order to qualitatively evaluate the relative roles of Fe–Mn oxides and particulate organic matter (POM), respectively, on metal uptake. The extent of Cd partitioning between sediment and water, parameterised in terms of the distribution coefficient, K_D, exhibited a reduction with increasing salinity, regardless of whether or not particles had been digested. However, the magnitude of K_D decreased significantly following either chemical treatment, suggesting that both oxides and organic matter are important sorbents for Cd. The K_D for Hg in the presence of untreated particles increased with increasing salinity, and chemical reduction of the particles enhanced the uptake of Hg and reinforced this trend. Particle oxidation led to a significant reduction in the K_D for Hg, and uptake by the particles decreased with increasing salinity. These observations suggest that POM is considerably more important than Fe–Mn oxides in the removal of aqueous Hg, and that its presence is a prerequisite for enhanced sorption (or salting out) at elevated salinities. The salinity dependence of K_D for Zn displayed characteristics of both Cd (below salinities of about 5) and Hg (at greater salinities). However, the magnitude of K_D for Zn uptake was relatively insensitive to either chemical treatment, suggesting that oxides, POM, and residual phases contribute to the overall sorption of Zn by estuarine particles. Regression analyses of the metal partition data suggest that sorption to oxides and POM is nonadditive, and that the salinity dependence of metal partitioning results mainly from salinity-controlled interactions between metal and organic matter. Sequential extraction of metals bound to untreated and chemically treated particles in the partitioning experiments indicated that the exchangeability or lability of all metals increased on removal of either oxides or POM. This implies that sorption sites of relatively high energy are destroyed (or become less accessible), or sorption sites of relatively low energy are created (or become more accessible) on chemical treatment. These observations support a conceptual model for the particle surface whose integrity and binding properties are only maintained by the coexistence of and interaction between oxides and organic matter.     

孟加拉湾中部表层沉积物常微量元素地球化学:物源指示意义

通过对取自孟加拉湾中部的110个表层沉积物样品进行了常微量元素测试分析,探讨了其物质来源。在所有测试元素中,Si含量最高,其次为Al,且这两种元素的分布特征基本一致。化学蚀变指数（CIA^*）平均值为72.07,指示研究区沉积物风化程度位于喜马拉雅源区和印度源区沉积物之间。因子分析和判别函数计算分析表明研究区沉积物主要来自喜马拉雅源区和印度源区。使用Ti标准化后的元素比值反演模型估算的喜马拉雅源区和印度源区对研究区沉积物的相对贡献比例分别为83.5%和16.5%。其中,喜马拉雅源区对研究区东部沉积物贡献相对较大,而在研究区西部印度源区贡献比例相对东部为高。喜马拉雅源区物质向研究区输运的主要动力机制包括浊流及其溢流、表层季风环流携带的河流冲淡水,而印度源区物质主要通过表层季风环流特别是东印度沿岸流向研究区输运     

The nutrient and trace metal geochemistry of a dredge plume

Field sampling of the dissolved and particulate material field downstream of a large volume bucket dredge operating in the lower Thames River estuary near New London, Connecticut, was conducted in order to examine the magnitude and character of the dredge-induced resuspension. These data indicate that large amounts of dissolved phosphate, ammonia, silica, manganese, copper and particulate materials are released into the water column, whereas cadmium concentrations were unaffected. Concentrations in the vicinity of the dredge exceed background levels by two to nine times for the dissolved materials and by two orders of magnitude for particulates. During the ebb cycle, downstream material concentrations decrease rapidly to background within approximately 180 m for dissolved materials and 700 m for particulates.Two mechanisms were found to control the distribution of materials downstream of the dredge: (a) physical transport, including advection, turbulent mixing and diffusion, and (b) geochemical processes (i.e. adsorption, desorption, precipitation, dissolution, etc.). The concentration of dissolved materials downstream of the dredge decrease at a first order exponential rate. The downstream distribution of the dissolved ammonia and silica was found to be consistent with the reactivity experiments (Figure 8) which predicted that PO₄ would undergo a decay in concentration in the presence of suspended sediments. Absorption of phosphate onto suspended sediments and gravitational settling of the suspended particulates were the processes. Manganese and copper underwent a dual transformation which involved an initial dissolution, followed by flocculation and possible coprecipitation as MnO₂. Cadmium concentrations in the water column were unaffected by the dredging process due to low pore water concentrations.The observed spatial distribution indicates that dredge-induced injection of dissolved and particulate materials is primarily a near field phenomenon producing relatively minor variations as compared to those caused by naturally occurring storm events. These latter systems have been shown (Tramontano, 1978; Bohlen et al., 1979) to produce estuary-wide variations in suspended materials, PO₄ and NH₄ concentrations increasing the mass of materials in suspension by at least a factor of two. This increase in total suspended load, PO₄ and NH₄, is nearly an order of magnitude larger than that produced by the dredge.     

The geochemistry of trace metals in the Brazos River estuary

A seasonal study of trace metal behavior and transport in the Brazos River estuary was conducted in the winter, spring and fall of 1981. Surface water was analyzed for total dissolved Pb, Cu, Mn and Fe, and particulate Cd, Pb, Cu, Mn and Fe. Ancillary data included river discharge, total suspended matter, pH, major ions, nutrients, dissolved and particulate organic carbon and humic acid.The major ions were generally conservative across the river water-seawater mixing zone; however, a significant input of alkalinity and Ca was measured in the spring, attributable to cation exchange on clays and sediment diagenetic processes. Distinct concentration maxima were found in the 3–10‰ chlorinity range for dissolved Pb (0·06–0·9 nm), Cu (6–42 nm), Mn (2–290 nm) and Fe (5–80 nm). Particulate metal concentrations showed significant seasonal and spatial variations: Cd, 0·09–0·57 ppm; Pb, 15–43 ppm; Cu, 12–32 ppm; Mn, 250–1990 ppm and Fe 0·5–5·4%. Reducing conditions leading to diagenetic remobilization in estuarine sediments are proposed to be an important source of dissolved metals for estuarine water. Calculations of dissolved riverine metal transport to the ocean that include estuarine metal input are as much as 40 times greater than when estuarine processes are ignored.     

Oxygen isotopes of phosphatic compounds—Application for marine particulate matter, sediments and soils

The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (δ¹⁸O_p) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO₄³⁻). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H₂¹⁸O (spiked) and unspiked acid and then converted the samples to silver phosphate for δ¹⁸O_p analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50 °C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the δ¹⁸O_p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for δ¹⁸O_p to demonstrate the utility of this approach for understanding sources and cycling of P.     

Optimization of the direct simultaneous atomic absorption determinations of several elements in marine or riverine particulate matter

A highly sensitive procedure is proposed for direct simultaneous atomic absorption determinations of three elements (Ag, Cd, and Pb or Cd, Pb, and Tl) in marine and riverine particulate matter. To decrease the influence of nonselective interference and matrix effects and to improve the detection limits of the elements, the course of the analysis included a preliminary stage of fractional evaporation of the sample (a graphite rod with a diaphragm as the evaporator) and condensation of the elements (a graphite rod as the collector). The condensate atomization proceeded in a rod-cell electrothermal graphite atomizer with independent heating of the zones of evaporation and atomization.     

The lipid geochemistry of antarctic marine sediments: Bransfield strait

Ten sections of a 10m long sediment core from Bransfield Strait, Antarctic region, have been examined for hydrocarbons, fatty acids, fatty alcohols, sterols, hopanoic acids, lignins and stable isotope ratios. The resolvable lipid compound classes generally occur in the following order of abundance: n-fatty acids > n-alkanes > n-alcohols > sterols > PAH with n-fatty acids comprising 50–80% of the lipids. The distribution of various lipid components indicate that they are principally from marine autochthonous sources, largely from diatoms and bacteria and to a lesser extent from dinoflagellates. There is no evidence from the lipid fraction of significant terrestrial plant input, which was also confirmed by the absence of methoxyphenols of the lignin degradation products. Aeolian transport from other continents appears to be minor or negligible. Minor amounts of epigenetic (mature) triterpenoids and polynuclear aromatic hydrocarbons found in all the samples are probably derived from submarine outcrops of weathered coaliferous shales. Stable carbon isotope ratios fall within a narrow range (−25 to −26‰), characteristic of Antarctic plankton. Coprostanol is the major stanol identified in the sediment core, most probably derived from the excreta of marine mammals, i.e. whales. Perylene, the dominant PAH, appears to be of marine origin in these Antarctic sediments. The presence of labile alkenes, unsaturated fatty acids and diploptene to a depth of 10m implies that little diagenetic alteration of the lipids has occurred. The sub-zero bottom water temperatures and the anoxic environmental conditions of this basin have preserved the total organic matter in the sediments, at least down to a depth of 10m.     

Techniques for determination of trace metals in small samples of size-fractionated particulate matter: phytoplankton metals off central California

The oceanic biogeochemical cycles of many trace elements are dominated by their association with the growth, death, consumption and sinking of phytoplankton. The trace element content of marine phytoplankton reflects nutritional status, species composition, surface area to volume ratios, and interactions with bioactive and toxic elements in the ambient seawater. Despite the ecological and environmental importance of trace element assimilation by autotrophs, there are few modern measurements of trace elements in phytoplankton assemblages from the natural environment. Here we introduce a new method for collection and analysis of size-fractionated particulate samples from practical seawater volumes. We pay particular attention to accurate determination of trace element filter blanks which are typically the limiting factor for analysis of such samples. Metals were determined at very low detection limits by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) for 11 elements (Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, U, Zn and P, which is used as a biomass normalizer) in three types of polymer filters (0.45, 5.0, and 53 μm pore size) and a quartz fiber filter (0.8 μm pore size). To place these new determinations in a practical context, results are presented for a vertical profile of samples filtered from 1–4 l of coastal seawater (0.3–1.0 mg total solid dry weight) at a station off central California. The results demonstrate that the blanks of the evaluated filter types, precleaned appropriately, are sufficiently low to allow accurate determination of the trace metal content of three size-classes of phytoplankton. At the Pacific station, measured phytoplankton Zn content (as Zn/P) agrees with values predicted from single-species culture studies growing at seawater Zn concentrations expected for coastal waters. The new method has utility as a generally applicable and simple size fractionation technique, and allows determination of natural and pollutant elements in small samples of phytoplankton and particles in coastal, estuarine and offshore marine regimes.     

Scavenging of particulate matter in coastal waters

The uptake of a suite of 19 metals from coastal seawaters upon both glass and Teflon surfaces reflected primarily the sorption of particulate matter derived from crustal rock weathering. Uptake for all elements was greater in the light than in the dark. Based upon these and earlier results, a new definition of scavenging for environmental systems is proposed.