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.     

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.     

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% .     

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.     

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.     

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.     

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.     

Surface reactivity of the Rhône suspended matter and relation with trace element sorption

The reactivity of the Rhône estuarine suspended matter is investigated through three operational parameters: the heat of immersion in water (HI), the ammonium saturation index (ASI) and the specific surface area (SSA). The two former parameters are highly correlated for samples collected both in surface river water and in its plume water and in a deeper nepheloid layer. Using both ASI and HI theoretical contributions of each main individual suspended matter component, it is shown that actual and calculated HI values are in agreement, whereas measured ASI values are significantly lower than those calculated. Surface normalization of these reactive properties is discussed on the basis of the SSA measured by the (BET) N2 adsorption. This evaluation, on freeze-dried suspended matter, appears to underestimate the actual particulate reactive surface area in the natural environment; indeed, it is shown that the ammonium ion surfacial density obtained from ASI and SSA data is unrealistically high.To verify that HI and ASI may be considered as criteria for the surface potential reactivity of particles, it has been attempted to relate these parameters and the extent of sorption of radioactive tracer, which is either discharged in the Rhone river or introduced in a batch experiment. Relationships between both ASI and HI and the content of ⁵⁴Mn, ⁶⁰Co, ⁶⁵Zn, ¹⁰⁹Cd and ¹³⁷Cs, which are established for some of them, suggest that HI and ASI are useful indicators of particulate affinity for certain metals.     

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.     

The distribution and geochemistry of some trace metals in the Bermuda coastal environment

Results of the analyses of the water column and sediments of the Bermuda Platform for Cd, Cu, Fe, Mn, Ni, Pb and Zn are presented. The major process controlling the water column concentrations is physical mixing of open ocean waters with inshore waters, which are polluted by a wide range of diffuse inputs. Sedimentation within the inshore waters plays a lesser, but significant, role as do fluxes from the sediments of Fe and Mn and possibly phytoplankton uptake of Zn. Concentrations within the sediments are controlled by the formation of trace metal enriched clay/organic particles in the inshore areas and their subsequent redistribution by sediment resuspension, except for Fe and Mn which are largely associated with clay lattices.     

Phosphorus distribution in sinking oceanic particulate matter

Despite the recognition of the importance of phosphorus (P) in regulating marine productivity in some modern oceanic systems and over long timescales, the nature of particulate P within the ocean is not well understood. We analyzed P concentration in particulate matter from sediment traps and selected core tops from a wide range of oceanic regimes: open ocean environments (Equatorial Pacific, North Central Pacific), polar environments (Ross Sea, Palmer Deep), and coastal environments (Northern California Coast, Monterey Bay, Point Conception). These sites represent a range of productivity levels, temporal (seasonal to annual) distributions, and trap depths (200–4400 m). P associations were identified using an operationally defined sequential extraction procedure. We found that P in the sediment traps is typically composed of reactive P components including acid-insoluble organic P ( 40%), authigenic P ( 25%), and oxide associated and/or labile P ( 21%), with lesser proportions of non-reactive detrital P depending on location ( 13%). The concentrations and fluxes of all particulate P components except detrital P decrease or remain constant with depth between the shallowest and the deepest sediment traps, indicating some regeneration of reactive P components. Transformation from more labile forms of P to authigenic P is evident between the deepest traps and core top sediments. Although for most sites the magnitudes of reactive P fluxes are seasonally variable and productivity dependent, the fractional associations of reactive P are independent of season. We conclude that P is transported from the upper water column to the sediments in various forms previously considered unimportant. Thus, acid-insoluble organic P measurements (typically reported as particulate organic P) likely underestimate biologically related particulate P, because they do not include the labile, oxide-associated, or authigenic P fractions that often are or recently were biologically related. Organic C to reactive P ratios are typically higher than Redfield Ratio and are relatively constant with depth below 300 m suggesting that preferential regeneration of P relative to C occurs predominantly at shallow depths in the water column, but not deeper in the water column (> 300 m). The view of P cycling in the oceans should be revised (1) to include P fractions other than acid-soluble organic P as important carriers of reactive P in rapidly sinking particles, (2) to include the efficient transformation of labile forms of P to authigenic P in the water column as well as in sediments, and (3) to consider the occurrence of preferential P regeneration at very shallow depths.     

Anthropogenic trace metals in sediment and settling particulate matter on a high-energy continental shelf (Sydney,Australia)

The anthropogenic contribution of trace metals to settling particulate matter (SPM) and surficial sediments was determined on the high-energy continental shelf adjacent to Sydney, Australia. Settling particulate matter and surficial sediment was collected in the vicinity of a major sewage outfall and at five control sites on the middle shelf (80-100 m water depth). Sediment traps were deployed on 10 occasions for up to 2 weeks during the summer and winter of 1995 and SPM was analyzed for Ag, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Cobalt, Fe, Mn and Ni act conservatively in SPM and in sediments regionally and are used as normalizing elements to determine anthropogenic enrichment. Surficial sediments and SPM are enriched in Ag, Cr, Cu, Pb and Zn near a major ocean outfall and at four of the five control sites, although sewage particles contribute < 5% of trace metals in the total sample. Silver is the most sensitive trace metal tracer for establishing the presence of sewage particulate matter. Sewage particulate matter flux near the outfall was estimated using a two end-member mixing model and is below 0.5 g m(-2) day(-1) during all deployment periods. The mean sewage particulate matter flux at sampling locations 30 km and 60 km north of the outfall are <0.13 g m(-2) day(-1) and <0.01 g m(-2) day(-1), respectively, indicating an efficient dispersal of anthropogenic material on this high energy continental shelf.     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

Model for calculating balance components of the biogenic matter field

To identify bioproductive zones in the ocean and to assess the intensity of primary production of the organic matter there, a model for the balance analysis of biogenic fields is proposed, which implies the calculation of advective, diffusive, and biochemical components. The model has been validated for an IBM PC/AT-386 in the MS DOS medium (version 3.30). As an example, computed data are provided on the silicic acid balance components in the Antarctic Ocean's euphotic layer during the vegetation period of 1985. The acquired data are compaed with available estimates. Translated by Vladimir A. Puchkin.     

The use of molluscs for monitoring trace elements in the marine environment in New Zealand 1. The contribution of ingested sediment to the trace element concentrations in New Zealand molluscs

Reference elements, such as silicon, were used to calculate the effect of sediment in the gut contents of molluscs on the estimation of the total body burden of trace elements. A significant proportion of the aluminium, iron, manganese, and lead are contributed by the sediment in the gut of many New Zealand mollusc species. Local mineralisation is likely to produce an important contribution for elements such as chromium, vanadium, and nickel in some areas of New Zealand and the ingested sediment in molluscs from “clean” environments will result in the real body burden of some elements such as lead being naturally lower than the available data suggests.     

Decomposition characteristics of particulate organic matter in hiroshima bay

The decomposition characteristics of particulate organic matter (POM) sampled with plankton nets in Hiroshima Bay were investigated under aerobic conditions in a laboratory experiment.The POM derived from plankton consisted of both a labile fraction (70–80 % of the whole) and a refractory fraction (20–30%). The labile fraction was completely decomposed within 40 days at 20°C. Although the concentrations of particulate organic carbon (POC) decreased gradually with time, an apparent lag phase was recognized in the decomposition of particulate phosphorus (PP) at an early stage, which might result from a specific uptake of dissolved inorganic phosphorus (DIP) by bacteria. A comparison of the metabolic activity between dissolved organic matter (DOM) and POM by measuring ATP contents showed that the former was one order of magnitude larger than the latter.On the other hand, there was no significant difference among the decomposition rates of POM collected at various depths. The change of the first-order rate constant (k) for the POM decomposition by temperature was expressed ask=0.0329 exp(0.0644T), and the Q₁₀ value was 1.94. There were fairly large variances ink values obtained from the various plankton species. Thek values averaged 0.144 day^–1 and ranged from 0.078 to 0.20 day^–1 at 20°C.     

The distributions of particulate atmospheric trace metals and mineral aerosols over the Indian Ocean

Data are presented for the concentrations of Al, Fe, Mn, Ni, Co, Cr, V, Cu, Zn, Pb and Cd in aerosols collected over two contrasting regions of the Indian Ocean. These are: (1) the northern Arabian Sea (AS), from which samples were collected in the northeast monsoon, during which the region receives an input of crustal material from the surrounding arid land masses; and (2) the Tropical Southern Indian Ocean (TSIO), a remote region from which samples were collected from air masses for which there were no large-scale up-wind continental aerosol sources. The TSIO samples can be divided into two populations: Population I aerosols, collected from air masses which have probably impinged on Madagascar, and Population II aerosols, which have been confined to open-ocean regions to the south of the area.The data indicate that there are strong latitudinal variations in the chemical signatures of aerosols over the Indian Ocean. The input of crustal material to the Arabian Sea gives rise to an average Al concentration of about 1000 ng m⁻³ of air in the northeast monsoon regime. As a result, the concentrations of all trace metals are relatively high, and the values of crustal enrichment factors are less than 10 for most metals, in the AS aerosols. In contrast, TSIO Population II ‘open-ocean southern air’ sampled during the southwest monsoon season, has an average Al concentration of only about 10 ng m⁻³ of air. Trace metal concentrations in the TSIO ‘open-ocean southern air’ during the southwest monsoon season are representative of ‘clean’ remote marine air and are generally similar to those reported over the central North Pacific.Mineral dust concentrations over the Indian Ocean decrease in a north to south direction, from about 15–20 μg m⁻³ of air in the extreme north to about 0.01–0.25 μg m⁻³ of air in the far south. The deposition of mineral dust over the northern Arabian Sea can account for approximately 75% of the non-carbonate material incorporated into the underlying sediments.In the Arabian Sea the dissolved atmospheric inputs of all the trace metals, with the exception of Cu and Co, exceed those from fluvial run-off by factors which range from 9.6 for Pb to 1.6 for Cr.