Trace Element Fluxes Research Articles

Seasonality of particle-associated trace element fluxes in the deep northeast Atlantic Ocean

In the framework of the German contribution to the Joint Global Ocean Flux Study (JGOFS), deep-water fluxes of particle-associated trace elements were measured in the northeast Atlantic Ocean. The sinking particles were collected almost continuously from 1992 to 1996 at three time-series stations, L1 (33°N/22°W), L2 (47°N/20°W), and L3 (54°N/21°W), using sediment traps. The focus of the present study is the temporal variability of the particle-associated elemental fluxes of Al, Ca, Cd, Co, Cu, Fe, Mn, Ni, P, Pb, Ti, V, and Zn at a depth of 2000 m. A clear seasonality of the fluxes that persisted for several years was documented for the southernmost station (L1) at stable oligotrophic conditions in the area of the North Atlantic Subtropical Gyre East (NASTE). At L2 and L3, an episodic nature of the elemental fluxes was determined. Mesoscale eddies are known to frequently cause temporal and spatial variability in the flux of biogenic components in that area. These events modified the simple seasonal pattern controlled by the annual cycle at L2, in the North Atlantic Drift Region (NADR), and at L3, which was influenced by the Atlantic Arctic province (ARCT). All stations were characterized by an additional episodic lithogenic atmospheric supply reaching the deep sea. The integrated annual fluxes during the multi-year study revealed similar flux magnitudes for lithogenic elements (Al, Co, Fe, Ti, and V) at L2 and L3 and roughly twofold fluxes at L1. Biogenic elements (Cd, P, and Zn) showed the opposite trend, i.e., two to fourfold higher values at L2 and L3 than at L1. For Mn, Ni, and Cu, the spatial differences were smaller, perhaps because of the intermediate behavior, between lithogenic and biogenic, of these elements. Similarly, among the three study sites, there were no noticeable differences in the total annual flux of Pb. The respective lithogenic fractions of the deep-sea fluxes of Cd, Co, Cu, Mn, Ni, V, and Zn were subtracted based on the amount of Al, with the average composition of the continental crust as reference. This procedure allowed estimation of the labile trace element fraction (TE exc) of the particles, i.e., TE taken up or scavenged during particle production and sedimentation. The ratios of TE exc/P clearly demonstrated an enrichment of TE over labile P from biogenic surface material to the deep sea for Zn (factor 4–6), Mn (12–27), Ni (3–5), and Cu (9–25); an intermediate status for Co (0.5–2.2); and depletion for Cd vs. P (0.2–0.4). Surprisingly, the recycling behavior of excess Co was found to be similar to that of P. Hence, Co exc behaved like a biogenic element; this is in contrast to total Co, which is dominated by the refractory lithogenic fraction. Moreover, it is argued that these excess elemental fluxes caused a loss of the dissolved elements in upper waters, since their transport reaches the deep-sea waters at 2000 m, a depth far below of deep-winter mixing and upwelling. The annual amount of excess TE exported from surface waters was estimated to be 1.3×10 9 mol Zn y −1, 4.4×10 9 mol Mn y −1, 4.9×10 8 mol Ni y −1, 2.2×10 7 mol Cd y −1, 7.4×10 8 mol Cu y −1, and 2.7×10 7 mol Co y −1 for the whole North Atlantic Ocean. Important primary sources that could replenish these losses are the aeolian and fluvial supply processes.

Dissolved, suspended, and colloidal fluxes of organic carbon, major and trace elements in the Severnaya Dvina River and its tributary

The chemical status of major and trace elements (TE) and organic carbon (OC) has been studied in the Severnaya Dvina and Pinega rivers draining granitic moraine, carbonate and sedimentary deposits of the Arkhangelsk region (NW Russia, the White Sea basin of the Arctic Ocean). Sampling was performed during winter and summer baseflow seasons and during the spring flood (2007–2008). Size separation procedure included on-site filtration through 5 µm, 0.22 µm, 100, 10 and 1 kDa, and dialysis through 1 kDa and 10 kDa pore-size membranes. The organic carbon concentration in “truly” dissolved form (< 1 kDa) does not depend on rock lithology or season, being on average equal to 5.0 ± 1.4 mg/L. Our observations may suggest the presence of two types of organic matter pool: i) allochtonous large-size colloids formed by lixiviation from upper soil horizons and ii) autochthonous (aquatic) small molecular-size substances, probably linked to bacterial and phytoplankton exudates. The total dissolved concentration of colloidal TE correlates with OC and Fe contents, being highest during the spring flood and lowest in winter time. There are two different patterns of TE colloidal status during different periods of the year, depending on their association with the organic or organo-mineral constituents of the colloidal matter pool. Trace and major element concentrations in the suspended matter of the River Severnaya Dvina were measured during different seasons over three years of observation. Based on collected data, we evaluate here, for the first time, the seasonal fluxes of major and trace elements in the suspended (> 0.22 µm), total dissolved (< 0.22 µm) and colloidal (1 kDa–0.22 µm) forms. On an annual basis, there is a significant contribution (≥ 30%) of conventionally dissolved species (< 0.22 µm) to the overall flux of usually weakly mobile elements such as the divalent transition metals, Cd, Pb, V, Y, all REEs, Zr, Hf and Th. The transport of these insoluble elements occurs essentially in colloidal form. The spring flood occurring in May provides between 30 and 60% of the total annual dissolved and suspended flux of many insoluble trace elements (Fe, Co, Ni, Cr, Y, all REEs, Cd, Pb, Zr, Hf and Th). We argue that trace element fluxes in Arctic rivers are often characterized by a high proportion of total dissolved matter (< 0.22 µm) compared to suspended particulates, due mostly to the large contribution of organically-bound colloidal forms.

日本海側地点（長崎県松浦市）における微量元素の乾性沈着フラックスとその変動要因

日本海側地点（長崎県松浦市）における微量元素の乾性沈着フラックスとその変動要因

Deep mantle subduction flux

We assess the flux of incompatible trace elements into the deep mantle in the Aleutian, Central America, Izu‐Bonin, Kurile, Lesser Antilles, Mariana, Sunda, and Tonga subduction zones. We use a simple mass balance approach in which we assume that all of the material lost from the subducting crust and sediment (the “slab”) is incorporated into the magmas erupted above the subduction zone, and we use these assumptions to calculate a residual slab composition. The calculated residual slabs are enriched in incompatible elements compared to mid‐ocean ridge basalts and highly enriched compared to primitive or depleted mantle. Almost all of the subducted Nb, Ta, and intermediate and heavy rare earths survive into the deep mantle, as do most of the light rare earths. On average, 73% of Th and Pb, 74% of K, 79% of U, 80% of Rb, 80% of Sr, and 82% of Ba survive into the deep mantle. Pb/Ce ratios are systematically lower, and Nb/U ratios are systematically higher, in the deep mantle flux than they are in the flux of material into the trench. Nevertheless, most residual slabs have Pb/Ce and Nb/U ratios outside the typical mantle range. Changes to U/Pb and Th/U ratios tend to be small and are not systematic. Rb/Sr ratios significantly decrease in some subduction zones but increase in others. In contrast, Sm/Nd ratios increase by small but significant amounts in most arcs. Based on these results, we attempt to predict the Sr, Nd, and Pb composition of anciently recycled material now in the mantle. We find that such material would most resemble enriched mantle II–type oceanic island basalts (OIB). None of our calculated residual slabs would evolve to Sr‐Nd‐Pb isotopic compositions similar to either high 238U/204Pb or enriched mantle I. The range of Sr and Pb isotope ratios in anciently recycled material is similar to that seen in modern OIB, but Nd isotopic compositions do not range to ɛNd values as low as those in some modern OIB. Neither radiogenic nor unradiogenic Pb isotope compositions can be exclusively associated with recycled material.

The Phytomanagement of Trace Elements in Soil

Trace elements (TEs) occur at low concentrations (<1000 mg kg −1) in organisms, yet they have a large biological effect, both as essential nutrients and environmental contaminants. Phytomanagement describes the manipulation of soil-plant systems to affect the fluxes of TEs in the environment with the goal of remediating contaminated soils, recovering valuable metals, or increasing micronutrient concentrations in crops. Phytomanagement includes all biological, chemical, and physical technologies employed on a vegetated site. Successful phytomanagement should either cost less than other remediation or fortification technologies, or be a profitable operation, by producing valuable plant biomass products. This may include bioenergy or timber production on contaminated land, a practice that does not reduce food production. We review the components of phytomanagement and the underlying biogeochemical processes, with a view to elucidating situations where this technology may be successfully applied and identifying future research needs. Many full-scale operations have proved the efficacy of plants to reduce contaminant mobility in soils (phytostabilization), particularly when used in combination with other technologies. As a stand-alone technology, the oft-touted use of plants to extract TEs from contaminated soils (phytoextraction) or low-grade ore bodies (phytomining) is unsuitable for most, if not all, sites due to low-extraction rates and problems caused by site heterogeneity, the limited rooting depth of plants and the presence of contaminant mixtures. Unsubstantiated claims about phytoextraction have tarnished the reputation of all “phyto” technologies. Nevertheless, phytoextraction, as part of a larger environmental toolkit, has a role in phytomanagement. The growth, or lack thereof, of profitable companies that provide phytomanagement will indicate its value. A critical knowledge gap in phytomanagement is the integration of the processes that affect plant–TE interactions and the biophysical processes affecting TE fluxes in the root zone, especially the effect of roots on contaminant fluxes.

Factors contributing to seasonal variations in wet deposition fluxes of trace elements at sites along Japan Sea coast

In this study, we measured the wet deposition fluxes of ten trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb, Sb, V and Zn) from December 2002 to March 2006 at three sites along the Japan Sea coast, which have been strongly affected by the long-range transport of air pollutants from the Asian continent. Also, factors, contributing to their seasonal variations were investigated. At the northern and central sites, the monthly wet deposition fluxes of all or most trace elements greatly increased during the cold season (typically, November–April), along with their monthly average (volume-weighted) concentrations in the precipitation. The cold/warm season ratios for the average concentrations of trace elements in precipitation were within the range of 2.7–5.1 at the northern site and 1.8–5.9 at the central site, which were similar to the average scavenging ratios (= concentration in precipitation/concentration in air) at each site. However, there were small differences (0.47–1.2 at the northern site and 0.73–1.7 at the central site) in the ratios of average concentrations in air between the two seasons. These suggest that the increase in the wet deposition fluxes of trace elements during the cold season is due to increases in their scavenging ratios. On the other hand, the result for the southern site was different from those at the other sites. The number of days when the daily maximum wind speed exceeded 10 m s −1 at the meteorological observatories near the study sites increased markedly during the cold season at the northern and central sites, showing that strong winds usually blow during the cold season at those sites, but not at the southern site. Higher wind speed transports larger amounts of constituents into the cloud system, which can result in their increased concentrations in precipitation. Thus, high scavenging ratios of trace elements during the cold season may be caused by the increase in their amounts of discharge into the cloud system owing to high wind speed, suggesting that wind speed is an important factor in the seasonal variations in the wet deposition fluxes.

Atmospheric fall-out of metals around the Murano glass-making district (Venice, Italy)

Murano's glass-makers have held a monopoly on quality glass-making for centuries known all over the world. Artistic glass manufacture entails exposure to complex mixtures of pollutants, including metals. A few studies have reported high levels of trace elements in marine waters, sediments and mussels around Murano and shown that emissions from Murano glass-making workshops significantly influence air quality in the Venice area. Nevertheless, to date, there is very little information on atmospheric concentrations and virtually none on atmospheric deposition fluxes of trace elements around the island. This study presents data on the distribution of trace elements in the air and atmospheric depositions around Murano, based on a 2-year sampling period. Airborne PM10 particulate matter was collected daily in the period December 2001-June 2003 (254 air samples), and atmospheric depositions were collected every 19 +/- 6 days, in the period August 2001-July 2003 (38 samples) on the roof of the Experimental Glass Laboratory on the island of Murano. All samples were analysed by ICP-MS for As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Se and Zn contents. Atmospheric concentrations of As, Cd, Cr, Ni, Pb, Se and Zn were 1-2 orders of magnitude greater on the island of Murano than in the nearest urban areas (Venice and Mestre), with values higher than those reported for European industrial sites. The atmospheric deposition fluxes of all elements were also higher in Murano than those detected by other studies in Venice and Mestre and in the Porto Marghera industrial zone, with As, Cd, Sb and Se 1-2 orders of magnitude higher. In order to study the spatial variability of the atmospheric fall-out, data from other sampling stations belonging to Venice atmospheric deposition monitoring networks were used. A decreasing gradient from Murano to the closer leeward stations was observed for As, Cd and Se. Pb and Zn deposition fluxes in Venice were also comparable to those observed in the Porto Marghera industrial zone, thus, indicating a similar or even higher level of contamination. Principal component analysis confirmed significant contamination from the glassworks. As shown by our study, atmospheric loadings of metals around Murano are significant. These observations confirm that emissions from Murano also significantly influence atmospheric deposition in the Venice area. Specifically, the mean daily Cd flux in the most affected area, which includes the whole of the historic city centre of Venice, is approximately 18 microg m(-2) day(-1), i.e. more than 65 times higher than the Dutch limit and more than three times higher than that of Germany. On the basis of our data, there is a clear-cut need for remedial action in the Lagoon of Venice. Monitoring is indispensable, so that the efficacy of remedial measures can be evaluated and appropriate information about risks for human health and well-being can be made available. The atmospheric compartment must also be considered by Italian and European law which, until now, has not yet established any standard for atmospheric deposition.

Determining annual suspended sediment and sediment-associated trace element and nutrient fluxes

Suspended sediment is a major factor in the biological and geochemical cycling of trace elements and nutrients in aquatic systems. The design of effective studies involving the collection, processing, and subsequent chemical analysis of suspended sediment requires a clear understanding of the problems associated with using this sample medium. This review summarizes the current state of knowledge relative to the various issues/problems associated with the collection of representative suspended sediment samples in fluvial systems. It also addresses issues associated with accurately determining the concentrations and fluxes of sediment-associated trace elements and nutrients.

Sinking fluxes of minor and trace elements in the North Pacific Ocean measured during the VERTIGO program

As part of the Vertical Transport in the Global Ocean (VERTIGO) program, we collected and analyzed sinking particles using sediment traps at three depths in the oceanic mesopelagic zone and at two biogeochemically contrasting sites (N. Central Pacific at ALOHA; N. Pacific Western Subarctic Gyre at K2). In this paper, we present the results of minor and trace element determinations made on these samples. Minor and trace elements in the sinking material showed 2 trends in flux with depth: increasing and constant. The sinking particulate phase of some elements (Al, Fe, Mn) was dominated by material of lithogenic origin and exhibited flux that was constant with depth and consistent with eolian dust inputs (ALOHA), or increasing in flux with depth as a result of lateral inputs from a shelf (K2). This shelf-derived material also appears to have been confined to very small particles, whose inherent sinking rates are slow, and residence time within the mesopelagic ‘‘twilight zone’’ would be consequently long. Furthermore, the flux of this material did not change with substantial changes in the rain of biogenic material from the surface (K2), suggesting mechanistic decoupling from the flux of organic carbon and macronutrients. Micronutrient (Fe, Co, Zn and Cu) fluxes examined in a 1-D mass balance suggest widely differing sources and sinks in the water column as well as impacts from biological uptake and regeneration. For example, total Fe fluxes into and out of the euphotic zone appeared to be dominated by lithogenic material and far exceed biological requirements. The export flux of Fe, however, appeared to be balanced by the eolian input of soluble Fe. For Zn and Cu, the situation is reversed, with atmospheric inputs insufficient to support fluxes, and the cycling therefore dominated by the draw down of an internal pool. For Co, the situation lies in between, with important, but ultimately insufficient atmospheric inputs.

Wet and dry deposition fluxes of trace elements in Tokyo Bay

The annual wet and dry deposition fluxes of As, Cd, Cr, Cu, Hg, Mn, Ni, Pb and V were measured on the basis of data obtained from 2 years of observation (December 2003–November 2005) at three sites in the Tokyo Bay area, which is highly affected by anthropogenic sources. Moreover, the concentrations of these trace elements in the air and bay sediments were determined concurrently. Using these data, we evaluated the factors affecting wet and dry deposition fluxes and the contribution of the atmospheric input of each element to the supply of trace elements to the bay. The order of the average ratios of dry/wet deposition fluxes at three sites was Cr, 6.9>As, 5.9>Mn, 4.7>V, 4.5>Cu, 4.4>Ni, 3.7>Cd, 2.9>Pb, 2.0>Hg, 1.0. Thus, the atmospheric deposition of the trace elements except Hg in Tokyo Bay is predominantly dry deposition. For such trace elements, the wet and dry deposition fluxes within the bay were higher than those inland. Except in the case of some elements, the differences in wet and dry deposition fluxes between these sites were primarily due to the differences in scavenging ratio (=concentration in precipitation/concentration in air) and dry deposition velocity (=deposition flux/concentration in air), respectively, rather than in atmospheric concentration. Also, a significant correlation ( r 2=0.76, P<0.001) was observed between the scavenging ratios and dry deposition velocities of the trace elements. These suggest that large particles from sources in the coastal regions contribute largely to the wet and dry depositions of trace elements to the bay. The contributions of the atmospheric input of the trace elements to the bay ranged from 5% to 26%. Atmospheric deposition seems to have no significant role in the supply of trace elements to Tokyo Bay, suggesting the importance of river and effluent discharges.

Sources and fluxes of atmospheric trace elements to the Gulf of Aqaba, Red Sea

We present the first comprehensive investigation of the concentrations, fluxes and sources of aerosol trace elements over the Gulf of Aqaba. We found that the mean atmospheric concentrations of crustally derived elements such as Al, Fe and Mn (1081, 683, and 16.7 ng m−3) are about 2–3 times higher than those reported for the neighboring Mediterranean area. This is indicative of the dominance of the mineral dust component in aerosols over the Gulf. Anthropogenic impact was lower in comparison to the more heavily populated areas of the Mediterranean. During the majority of time (69%) the air masses over the Gulf originated from Europe or Mediterranean Sea areas delivering anthropogenic components such as Cu, Cd, Ni, Zn, and P. Airflows derived from North Africa in contrast contained the highest concentrations of Al, Fe, and Sr but generally lower Cu, Cd, Ni, Zn, and P. Relatively high Pb, Ni, and V were found in the local and Arabian airflows suggesting a greater influence of local emission of fuel burning. We used the data and the measured trace metal seawater concentrations to calculate residence times of dissolved trace elements in the upper 50 m surface water of the Gulf (with respect to atmospheric input) and found that the residence times for most elements are in the range of 5–37 years while Cd and V residence times are longer.

Monitoring urban impacts on suspended sediment, trace element, and nutrient fluxes within the City of Atlanta, Georgia, USA: program design, methodological considerations, and initial results

AbstractAtlanta, Georgia (City of Atlanta, COA), is one of the most rapidly growing urban areas in the US. Beginning in 2003, the US Geological Survey established a long‐term water‐quantity/quality monitoring network for the COA. The results obtained during the first 2 years have provided insights into the requirements needed to determine the extent of urban impacts on water quality, especially in terms of estimating the annual fluxes of suspended sediment, trace/major elements, and nutrients.During 2004/2005, suspended sediment fluxes from the City of Atlanta (COA) amounted to about 150 000 t year−1; ≥ 94% of the transport occurred in conjunction with storm‐flow, which also accounted for ≥ 65% of the annual discharge. Typically, storm‐flow averaged ≤20% of the year. Normally, annual suspended sediment fluxes are determined by summing daily loads based on a single calculation step using mean‐daily discharge and a single rating curve‐derived suspended sediment concentration. Due to the small and ‘flashy’ nature of the COAs streams, this approach could produce underestimates ranging from 25% to 64%. Accurate estimates ( ± 15%) require calculation time‐steps as short as every 2–3 h.Based on annual median base‐flow/storm‐flow chemical concentrations, the annual fluxes of ≥ 75% of trace elements (e.g. Cu, Pb, Zn), major elements (e.g. Fe, Al), and total P occur in association with suspended sediment; in turn, ≥ 90% of the transport of these constituents occur in conjunction with storm‐flow. As such, base‐flow sediment‐associated and dissolved contributions represent relatively insignificant portions of the total annual load. An exception is total N, whose sediment‐associated fluxes range from 50% to 60%; even so, storm‐related transport typically exceeds 80%. Hence, in urban environments, non‐point‐sources appear to be the dominant contributors to the fluxes of these constituents. Published in 2007by John Wiley &amp; Sons, Ltd.

Irradiance and the elemental stoichiometry of marine phytoplankton

We analyzed the elemental composition (C, N, P, S, K, Mg, Ca, Sr, Fe, Mn, Zn, Cu, Co, Mo, and Ni) of five marine phytoplankton species representing the four major marine phyla grown over a range of growth irradiances. We found substantial variability in the elemental composition between different species, which is consistent with previously reported differences associated with evolutionary history. We found that many elements (Fe, Mn, Zn, Cu, Co, and Mo) are enriched relative to phosphorus by about two to three orders of magnitude under irradiances that are limiting for growth, and net steady‐state uptake of element : P is often elevated under lower irradiances. For most elements, the variability in element : P due to irradiance is comparable to the variability due to phylogenetic differences at any irradiance, but often the interaction between genetic differences and the phenotypic response to irradiance amplifies the differences in elemental composition between species. The fractionation of trace elements relative to phosphorus into phytoplankton biomass under low light is consistent with depleted levels of Cu2+ and Mn2+ in deep chlorophyll maxima, suggesting that the export of lowlight‐ acclimated phytoplankton is a major source of trace element flux to the deep ocean and an important factor in the biogeochemical cycles of many of the biologically limiting elements in the oceans.

Diurnal hydrological – physicochemical controls and sampling methods for minor and trace elements in an Alpine glacial hydrological system

Summary We present diurnal (i) 0.45 and 0.1 μm pore-size filtered and (ii) operationally defined labile particulate-associated major, minor and trace element concentrations and fluxes in glacial outflow waters draining Haut Glacier d’Arolla, Switzerland. We use speciation modelling (PHREEQCi) and water-suspended sediment interaction experiments are utilised under conditions analogous to the subglacial channellised hydrological system, in order to assess controls on, and the most suitable sampling methods to investigate short-term variations in the mode of major, minor and trace element species export from a glacierised headwater catchment. 0.45 μm pore-size filtered major ions, Sr and U are exported in glacial outflow waters predominately as mobile monovalent or divalent ions or as carbonate complexes, and are controlled by hydrological variations over diurnal cycles, exhibiting an inverse concentration with increasing meltwater discharge. Conversely, 0.45 μm pore-size filtered concentrations of most minor and trace elements (e.g. Fe, Mn, Co, Ba and Pb) exhibit variations that are not strongly inter-correlated with meltwater discharge or suspended sediment concentrations (SSC) over diurnal periods. The use of 0.45 and 0.1 μm pore-size filter membranes indicates that significant colloidal material is not passing through the 0.45 μm pore-size filters, and these unsystematic variations are not a result of colloid measurement. Speciation modelling applied to meltwaters and observations during water–rock interaction experiments suggest that these unsystematic temporal variations reflect physicochemical controls. This includes sorption, and the oversaturation and precipitation of Fe and Al (oxi)hydroxides, and the co-precipitation of other species. Diurnal pH variations appear important in controlling such short-term physicochemical controls, which limits such species use for hydrological investigations. The percentage of total elemental fluxes exported as the labile particulate-associated flux (%PAF) for each minor and trace element changes dramatically between and during the diurnal cycles, reflecting species-specific sensitivity to hydrological and physicochemical controls. Hydrological interpretations of hydrochemical data must be made carefully when using chemical determinations by ICP-MS, since we demonstrate that measurements will comprise of any material that passes through the filter. This can lead to higher concentration measurements than if determined by ion chromatography, which measures truly ionic dissolved species.

Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

The chemical status of ∼40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2–5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03–0.4 mg/L), aluminum (0.03–0.4 mg/L), OC (10–20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20–30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1–10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1–100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ⩾30%) of conventionally dissolved (<0.22 μm) forms for usually “immobile” elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10–100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.

Paleo-ocean chemistry records in marine opal: Implications for fluxes of trace elements, cosmogenic nuclides ( 10Be and 26Al), and biological productivity

Here, we provide evidence suggesting that marine (diatom) opal contains not only a high fidelity record of dissolved oceanic concentrations of cosmic ray-produced radionuclides, 10Be and 26Al, but also a record of temporal variations in a large number of trace elements such as Ti, Fe, Zn and Mn. This finding is derived from measurements in purified biogenic opal that can be separated from detrital materials using a newly developed technique based on surface charge characteristics. Initial results from a sediment core taken near the present-day position of the Antarctic Polar Front (ODP Site 1093) show dramatic changes in the intrinsic concentrations of, Be, Al, Ti, Fe, Mn and Zn in the opal assemblages during the past ∼140 kyr BP. The results imply appreciable climatically controlled fluctuations in the level of bioreactive trace elements. The time series of total Be, Al, Ti, Fe and 10Be in the sediment core are all well correlated with each other and with dust records in the polar ice cores. The observations suggest that a significant flux of these trace metals to oceans is contributed by the aeolian dust, in this case, presumably from the Patagonia. This observation also allows determination of fluxes of dust-contributed 10Be to the Antarctica ice sheets. However, our data show that the relationships among the various metals are not perfectly linear. During periods of higher dissolved concentrations of trace elements (indicated by Fe and Ti) the relative concentrations of bioreactive elements, Be, Al, Mn and Zn are decreased. By contrast, the Fe/Zn and Fe/Mn ratios decrease significantly during each transition from cold to warm periods. The relative behavior could be consistent with any of the following processes: (i) enhanced biological productivity due to greater supply of the bioreactive elements (e.g. Zn) during cold periods (ii) increased biological and inorganic scavenging of particle active elements (e.g. Be and Al) during early interglacial periods (iii) differential uptake/removal of the metals by the various diatom taxa whose relative productivity or growth rate changes with large scale climate. In any case, with one sedimentary phase and in single sedimentary sections, we now have the potential to compare directly a proxy for aeolian input of micronutrients (e.g. Fe or Ti), with a proxy for production (e.g. 26Al/Al ratios). We expect that studies of the temporal records of trace elements and cosmogenic nuclides in contrasting regions of upwelling and productivity, which exhibit different sensitivities to global climate fluctuations and micronutrient inputs, would lead to a direct and comprehensive test of ideas such as the hypothesis of iron control of atmospheric carbon dioxide [Martin, J.H., 1990. Glacial–interglacial CO 2 change: the iron hypothesis. Paleoceanography 5, 1–13]. Our present data from a single site do not show that increases in dissolved Fe concentrations, per se, were responsible for increased biological productivity. However, a much clearer picture of the effect of increased dust fluxes should emerge when we have data for trace elements and the cosmogenic nuclides, 10Be and 26Al from various oceanic provinces.

Short-term variability of dissolved trace element concentrations in the Marne and Seine Rivers near Paris

The concentrations of dissolved trace elements (Li, B, Mn, Cu, As, Rb, Sr, Mo, Cd, Ba, Pb) in the Marne and Seine rivers in the Paris urban area were monitored over a 2-year period. The resulting data indicated moderate contamination of waters by the most toxic elements (Cu, As, Cd and Pb). The River Marne upstream and the River Seine downstream of the city of Paris displayed similar concentrations. However higher fluxes of trace elements were observed in the Seine than in the Marne due to their different discharges.Li, B, Rb, Sr and Ba concentrations were correlated with river discharge and concentrations were higher during high river flow. This was interpreted as a dilution by discharge from a major natural or anthropogenic source. Mn, Cu, Mo, Cd and Pb concentrations were not correlated with discharge. Dissolved Mn, Cu and Cd increased rapidly in summer, whereas the concentration of Mo decreased. These variations were attributed to redox processes. During summer when the dissolved oxygen concentrations decrease, Mn, Cu, Cd and Pb are released into solution whereas Mo is immobilised.Like metals, variations in arsenic contents were not linked with discharge. Its similarity with phosphate distribution suggests similar controls involving phytoplankton uptake and release from sediments through organic matter mineralization.

Regional variations in wet and dry deposition fluxes of trace elements in Japan

The annual wet and dry deposition fluxes of 12 trace elements (i.e., As, Cd, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se and V) were measured on the basis of 1 year of observations (December 2003–November 2004) at 10 sites in Japan. Precipitation and dry deposition (gases and particles) samples were collected every half month using an automatic sampler, which is composed of a precipitation sampler and a water surface sampler for dry deposition. The wet deposition fluxes of Hg, Pb and Se exceeded their dry deposition fluxes at most sites. In contrast, the dry deposition fluxes of Cr, Cu, Mn, Mo, Ni and V were significantly higher than their wet deposition fluxes. The annual wet deposition fluxes of trace elements except for Cu, Mo and Ni were correlated with the annual precipitation amount ( P < 0.05 ). In particular, about 70–80% of the variance of the wet deposition fluxes for Hg ( r 2 = 0.80 ), Sb ( r 2 = 0.68 ) and V ( r 2 = 0.80 ) was explained using the precipitation amount. The wet deposition fluxes of As, Cd, Pb and Se at sites on the Japan Sea coast tended to be higher than those expected from the precipitation amount. This suggests a large contribution of their long-range transport from the Asian continent. On the other hand, the regional variations in the dry deposition fluxes of the trace elements were different from those in the wet deposition fluxes. A markedly higher dry deposition fluxes were observed at sites in industrial and urban areas. The relatively high dry deposition fluxes of Cr, Cu, Mn, Ni and Pb suggest that these elements are mainly from electric steel furnaces near the sites, because they are abundant in furnace emission particles. The results of lead isotope analyses indicate that the lead isotope ratios in the dry deposition samples at industrial and urban sites are different from those at other sites. This implies that lead dry deposition at such sites is dominated by emissions from peculiar sources, although whether those sources are the electric steel furnaces is unknown.

Atmospheric dry deposition fluxes of trace elements measured in Bursa, Turkey

Trace element dry deposition fluxes were measured using a smooth, greased, knife-edge surrogate surface (KSS) holding greased Mylar strips in Bursa, Turkey. Sampling program was conducted between October 2002 and June 2003 and 46 dry deposition samples were collected. The average fluxes of crustal metals (Mg, Ca, and Fe) were one to four orders of magnitude higher than the fluxes of anthropogenic metals. Trace element fluxes ranged from 3 (Cd) to 24 230 (Ca) μg m −2 d −1. The average trace element dry deposition fluxes measured in this study were similar to those measured in other urban areas. In addition, ambient air samples were also collected simultaneously with flux samples and concentrations of trace elements, collected with a TSP sampler, were between 0.7 and 4900 ng m −3 for Cd and Ca, respectively. The overall trace element dry deposition velocities, calculated by dividing the fluxes to the particle phase concentrations ranged from 2.3±1.7 cm s −1 (Pb) to 11.1±6.4 cm s −1 (Ni). These values are in good agreement with the values calculated using similar techniques. The anthropogenic and crustal contributions were estimated by employing enrichment factors (EFs) calculated relative to the average crustal composition. Low EFs for dry deposition samples were calculated. This is probably due to contamination of local dust and its important contribution to the collected samples.

The influence of the Amazonian floodplain ecosystems on the trace element dynamics of the Amazon River mainstem (Brazil)

The purpose of this paper is to forecast the role of riverine wetlands in the transfer of trace elements. One of the largest riverine wetlands in the world is the floodplain (várzea) of the Amazon River and its tributaries ( Junk and Piedade, 1997). The central Amazon wetlands are constituted by a complex network of lakes and floodplains, named várzeas, that extend over more than 300,000 km 2 (Junk, W.J., The Amazon floodplain- a sink or source for organic carbon? In Transport of Carbon and Minerals in Major World Rivers,edited by E.T. Degens, S. Kempe, R. Herrera, SCOPE/UNEP; 267–283, 1985.) and are among the most productive ecosystems in the world due to the regular enrichment in nutrients by river waters In order to understand if the adjacent floodplain of Amazon River have a significant influence on the trace element concentrations and fluxes of the mainstem, the concentrations of selected elements (i.e., Al, Mn, Fe, Co, Cu, Mo, Rb, Sr, Ba, and U) have been measured in the Amazon River water (Manacapuru Station, Amazonas State, Brazil) and in lake waters and plants (leaves) from a várzea (Ilha de Marchantaria, Amazonas State, Brazil) during different periods of the hydrological cycle. Four plant species (two perennial species: Pseudobombax munguba and Salix humboldtiana, and two annual herbaceous plants: Echinochloa polystachya and Eichhornia crassipes) were selected to represent the ecological functioning of the site. Time series obtained for dissolved Mn and Cu (<0.20 μm) in Amazon River water could not be explained by tributary mixing or instream processes only. Therefore, the contribution of the waters transiting the floodplains should be considered. These results suggest that the chemical composition of the waters draining these floodplains is controlled by reactions occurring at sediment–water and plant–water interfaces. Trace elements concentrations in the plants (leaves) vary strongly with hydrological seasonality. Based on the concentration data and the biological productivity of floodplain ecosystems, a first order approximation of trace element storage (permanent or temporary) in the vegetation of these floodplains was made. It was found that floodplain-mainstem elemental fluxes make a significant contribution to the dissolved flux of the Amazon River. This study is part of the Brazilian_French joint research program Hybam (Hydrology and Geochemistry of the Amazonian Basin).