Biogeochemistry Of Trace Elements Research Articles

Effects of dams on As and Hg concentrations in three southeastern Brazil fluvial systems: Ocean inputs, sources and seasonal dynamics among environmental compartments

Damming rivers for hydropower generation interferes in the flow of water bodies and, consequently, in trace element biogeochemistry and transport. This study focused on the effects of dams on the seasonal dynamics of arsenic (As) and mercury (Hg) in three fluvial systems (Itabapoana River, Flechas Channel and Paraíba do Sul River) and on the input of these elements to the ocean. The elements were evaluated in suspended particulate matter (SPM), surface sediments, and the roots of the aquatic macrophyte Eichhornia crassipes. Our results showed that the proximity of the dams in the Flechas Channel and Rio Itabapoana in relation to their mouth (distances of 4 km and 58 km, respectively) changed As and Hg seasonal dynamics in the environmental compartments analyzed, with the Flechas Channel being the most impacted area. In contrast, the lower part of the Paraíba do Sul River that has more distant dams to its mouth (distance of 184 km) did not show such marked changes, suggesting that most of the inputs are coming from the long river reach. The isotopic and elemental composition of organic matter indicated the soils of native forests as the main source of trace elements to the water bodies. Flow rate was the main driver controlling As and Hg ocean inputs, with higher inputs observed in the Paraíba do Sul River (9.69 and 0.59 t∙year−1, respectively) compared to the other assessed fluvial systems. Also, this study demonstrated that, if a dam is closer to the mouth of a river, less contaminants will be input.

Particulate iron and other trace elements in near-surface waters of the high latitude North Atlantic following the 2010 Eyjafjallajökull eruption

In situ pumps were used to collect size-fractionated particles (>53 μm and 1–53 μm) from the upper ocean of the high latitude North Atlantic during spring and summer 2010, and samples were subsequently analysed for Al, P, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba and Pb. Two research cruises during May 2010 coincided with an eruption of the Eyjafjallajökull volcano in southern Iceland, which resulted in widespread dispersal of ash over the region. Ash deposition caused a noticeable perturbation of particulate trace element concentrations and content within marine particles in the Iceland Basin, relative to the Irminger Basin, most evident for lithogenic elements (Al, Ti, Fe), but also noticeable in elemental ratios for the other elements. The initial volcanic ash influence had largely disappeared by the third research cruise in July/August 2010, although there was evidence for a recent wind erosion event having transported remobilized volcanic ash from southern Iceland to the northern Iceland Basin in early July, further perturbing local trace element biogeochemistry. During summer 2010, concentrations of all measured elements except Ba were typically lower 10 m beneath the surface mixed layer relative to those within it, driven primarily by a rapid decrease in the concentrations of large (>53 μm) biogenic particles. Depth-dependent trends were more variable over the next hundred metres for all elements except the biogenic elements P and Cd, for which concentrations decreased further. The continued loss of biogenic material with depth due to remineralization (reflected by particulate P concentrations) led to an increase in content per mass of material for all other elements measured. The observed differences in upper ocean particulate P and Fe distributions highlight the mechanism driving seasonal Fe limitation in the high latitude North Atlantic: rapid loss of P by remineralization regenerates dissolved phosphate close to the base of the mixed layer, while most particulate Fe persists deeper in the water column, removing the potential for resupply of dissolved Fe to surface waters.

Comparing Trace Elements (As, Cu, Ni, Pb, and Zn) in Soils and Surface Waters among Montane, Upland Watersheds and Lowland, Urban Watersheds in New England, USA

Trace element biogeochemistry from soils to rivers is important for toxicity to aquatic ecosystems. The objective of this study was to determine whether trace element exports in contrasting watersheds are controlled by their abundance in soil, current land uses in the watershed, or geologic processes. Upland soils and river water samples were collected throughout the Deerfield watershed in southern Vermont and western Massachusetts and in the Quinebaug and Shetucket watersheds of eastern Connecticut. Soil concentrations were only an important predictor for dissolved Fe export, but no other trace element. Soil pH was not correlated with normalized dissolved exports of trace elements, but DOC was correlated with normalized dissolved Pb and Ni exports. The limited spatial and depth of soil sampling may have contributed to the poor correlation. Surprisingly, linear regressions and principal component analysis showed that human development was associated with higher soil trace metal concentrations but not significantly correlated with dissolved trace elements export. Instead, forest abundance was a strong predictor for lower Cu, Pb, and Zn soil concentrations and lower As, Fe, Ni and Pb dissolved exports across the watersheds. Dissolved exports of Al, K, and Si suggest that enhanced mineral dissolution in the montane watersheds was likely an important factor for matching or exceeding normalized pollutant trace element exports in more urbanized watersheds. Further studies are needed to evaluate subsurface/hyporheic controls as well as soil–surface water interface to quantify exchange and transport.

第13回微量元素の生物地球化学に関する国際会議（ICOBTE）の開催概要報告

第13回微量元素の生物地球化学に関する国際会議（ICOBTE）の開催概要報告

Relationship of the mobile forms of calcium and strontium in soils with their accumulation in meadow plants in the area of Kashin-Beck endemia.

This study was aimed at assessment of strontium and calcium mobility in soils and their accumulation with plants in the areas endemic for Kashin-Beck disease in Eastern Transbaikalia. The strontium and calcium mobility levels were determined using the method of sequential chemical extraction for 7 samples of meadow soils collected from the endemic region and 7 soil samples taken from conditionally control sites. To measure the Ca and Sr levels in the soil and plant samples, XRF analysis and AAS were used. The increased strontium level in the meadow soils of the endemic areas is accompanied by the element's higher mobility. The highest strontium yield was observed in the course of soil extraction using 1 M ammonium acetate, while the soils taken from the control sites gave lower amounts of the trace element. Furthermore, there is a positive correlation between the amount of the strontium extracted and its content in plants (r = + 0.86 - 0.98). At the sequential chemical extraction of calcium from the soils using the above method, the calcium yield was maximal in the ammonium acetate fraction (background sites) and in ammonium acetate and 6M HCl fractions (endemic areas). The correlation between the amount of the calcium extracted in 1M ammonium acetate and the macroelement levels found in plants was + 0.968. In addition, a peculiarly high accumulation of strontium in various willow species as compared to other meadow plants was revealed for the first time ever. Thus, the work introduces new data into the trace element biogeochemistry and environmental monitoring.

Welcome to the New L&O: Methods Associate Editors!

Welcome to the New <i>L&amp;O</i>: <i>Methods</i> Associate Editors!

Report on 15th International Conference on the Biogeochemistry of Trace Elements

Report on 15th International Conference on the Biogeochemistry of Trace Elements

ADM1 based mathematical model of trace element precipitation/dissolution in anaerobic digestion processes

Due to the complex biogeochemistry of trace elements (TEs, e.g. Fe, Ni and Co) in anaerobic digestion processes, their role and fate is poorly understood. Challenging, time consuming and low detection limits of analytical procedures necessitate recruitment of mathematical models. A dynamic mathematical model based on anaerobic digestion model no.1 (ADM1) has been proposed to simulate the effect of TEs. New chemical equilibrium association/dissociation and precipitation/dissolution reactions have been implemented to determine TE bioavailability and their effect on anaerobic digestion. The model considers interactions with inorganic carbonate (HCO3− and CO32−), phosphate (PO43−, HPO42−, H2PO4−) and sulfide (HS− and S2−). The effect of deficiency, activation, inhibition and toxicity of TEs on the biochemical processes has been modelled based on a dose-response type inhibition function. The new model can predict: the dynamics of TEs (among carbonate, sulfide and phosphate); the starvation of TEs; and the effect of initial sulfur-phosphorus ratio in an in-silico batch anaerobic system.

Intertidal geothermal hot springs as a source of trace elements to the coastal zone: A case study from Bahía Concepción, Gulf of California

We investigated the influence of the intertidal geothermal hot spring (GHS) on the biogeochemistry of trace elements in Santispac Bight, Bahía Concepción (Gulf of California). The geothermal fluids were enriched in As and Hg mainly in ionic form. The suspended particulate matter of the GHS had elevated enrichment factor (EF) >1 of As, Bi, Cd, Co, Cu, Mn, Mo, Sb, Sn, Sr, Ti, U and Zn. The sediment core from GHS1 had high concentration of As, Hg, Corg, S, V, Mo, and U and the extremely high EF of these elements at 8cm of the core. The maximum bioaccumulation of As and Hg was in seaweeds Sargassum sinicola collected near the GHS2. The results confirm the input of trace elements to the coastal zone in Bahía Concepción from geothermal fluids and the evident modification of the chemical composition of the adjacent marine environment.

Dissolved low-molecular weight thiol concentrations from the U.S. GEOTRACES North Atlantic Ocean zonal transect

Low-molecular weight thiols, including cysteine and glutathione, are biomolecules involved in a variety of metabolic pathways and act as important antioxidant and metal buffering agents. In this last capacity, they represent a potential mechanism for modulating the bioavailability and biogeochemistry of many trace elements in the ocean, particularly for chalcophilic elements (e.g., Cu, Zn, Cd, Ag and Hg). For this reason, and in the context of the international GEOTRACES program that seeks to understand the biogeochemistry of trace elements in the ocean, we measured the concentration of individual dissolved low-molecular weight thiols during the U.S. GEOTRACES North Atlantic Zonal Transect (USGNAZT). Only two thiols were identified, cysteine and glutathione, in contrast to results from the northeast subarctic Pacific Ocean, where the dipeptides glycine-cysteine and arginine-cysteine were also present and γ-glutamylcysteine was dominant. Concentrations of cysteine and glutathione in the North Atlantic Ocean were lower than in the Pacific and ranged from below detection (~0.01nM) to 0.61nM of cysteine and up to 1.0nM of glutathione, with cysteine generally more abundant than glutathione. Vertical profiles of cysteine and glutathione were broadly consistent with their biological production, being more abundant in surface water and usually below detection at depths greater than about 200m. Subsurface concentration maxima, often co-incident with the deep chlorophyll maximum, were frequently observed but not universal. We conclude that cysteine and glutathione do not make up significant portions of complexation capacity for Cu and Zn in the upper open ocean but could be important for Cd, Hg, and potentially other chalcophiles. Extremely low concentrations of cysteine and glutathione in deep water suggest that higher molecular-weight thiols are a more important ligand class for chalcophiles in that portion of the ocean.

Urban biogeochemistry of trace elements: What can the sediments of stormwater ponds tell us?

Humans are greatly modifying biogeochemical cycles, in part, by increasing the abundance of many trace elements in heavily developed environments. As a means to study the biogeochemical cycling of trace elements in the urban landscape, we examined their accumulation in the sediments of ponds located in residential developments. To do so, we measured the content of trace elements (Ti, V, Cr, Co, Ni, Cu, Zn, Mo, Ag, Cd, Ba, Tl, Pb) and minerals (Na, Mg, Al, K, Ca, Mn, Fe) in the sediments of stormwater management ponds located in residential catchments of southern Ontario, Canada. Trace elements and associated mineral composition of the sediments primarily clustered in three groups. In one group, several trace elements (e.g., Co and V) were correlated to soil-related minerals (Al and Fe), which indicate a predominant role of soil erosion in their movement across the urban landscape. Elements in the second group (Cd, Pb, Cu, Zn, and Mo) were positively correlated with sediment organic carbon content suggesting an importance of internal pond processing such as adsorption to organic matter. In the third group, Ca and Ag negatively correlated with most other elements likely because, at least for Ca, importation of carbonates in coarse particulate material (i.e., sand) dilutes the concentration of other trace elements. Variability in trace elements among ponds and between municipalities suggests that these elements are deposited and move differently among catchments in a relatively homogenous urban landscape. Our results demonstrate a trace element biogeochemistry in urban environments that is connected to human sources, physical disturbance of the landscape, biological processing, and underlying geological composition of the catchment.

Trace element biogeochemistry in the soil-water-plant system of a temperate agricultural soil amended with different biochars.

Various biochar (BC) types have been investigated as soil amendment; however, information on their effects on trace element (TE) biogeochemistry in the soil-water-plant system is still scarce. In the present study, we determined aqua-regia (AR) and water-extractable TEs of four BC types (woodchips (WC), wheat straw (WS), vineyard pruning (VP), pyrolyzed at 525 °C, of which VP was also pyrolyzed at 400 °C) and studied their effects on TE concentrations in leachates and mustard (Sinapis alba L.) tissue in a greenhouse pot experiment. We used an acidic, sandy agricultural soil and a BC application rate of 3% (w/w). Our results show that contents and extractability of TEs in the BCs and effectuated changes of TE biogeochemistry in the soil-water-plant system strongly varied among the different BC types. High AR-digestable Cu was found in VP and high B contents in WC. WS had the highest impact on TEs in leachates showing increased concentrations of As, Cd, Mo, and Se, whereas WC application resulted in enhanced leaching of B. All BC types increased Mo and decreased Cu concentrations in the plant tissue; however, they showed diverging effects on Cu in the leachates with decreased concentrations for WC and WS, but increased concentrations for both VPs. Our results demonstrate that BCs may release TEs into the soil-water-plant system. A BC-induced liming effect in acidic soils may lead to decreased plant uptake of cationic TEs, including Pb and Cd, but may enhance the mobility of anionic TEs like Mo and As. We also found that BCs with high salt contents (e.g., straw-based BCs) may lead to increased mobility of both anionic and cationic TEs in the short term.

Dissolved trace element biogeochemistry of a tropical river, Southwestern India

River Swarna, a small tropical river originating in Western Ghats (at an altitude of 1,160 m above mean sea level) and flowing in the southwest coast of India discharges an average of 54 m(3)s(-1) of water into the Arabian Sea, of which significant part is being discharged during the monsoon. No studies have been made yet on the water chemistry of the Swarna River basin, even as half a million people of Udupi district use it for domestic and irrigational purposes. As large community in this region depends on the freshwater of Swarna River, there is an urgent need to study the trace element geochemistry of this west flowing river for better water management and sustainable development. The paper presents the results on the biogeochemistry of dissolved trace elements in the Swarna River for a period of 1 year. The results obtained on the trace elements show seasonal effect on the concentrations as well as behavior and thus forming two groups, discharge driven (Li, Be, Al, V, Cr, Ni, Zr, In, Pb, Bi and U) and base flow driven (groundwater input; Mn, Fe, Co, Cu, Ga, Zn, As, Se, Rb, Sr, Ag, Cd, Cs, Ba and Tl) trace elements in Swarna River. The biogeochemical processes explained through Hierarchical Cluster Analysis show complexation of Fe, Ga and Ba with dissolved organic carbon, redox control over Mn and Tl and biological control over V and Ni. Also, the water quality of Swarna River remains within the permissible limits of drinking water standards.

GEOTRACES radium isotopes interlaboratory comparison experiment

In anticipation of the international GEOTRACES program, which will study the global marine biogeochemistry of trace elements and isotopes, we conducted a multi‐lab intercomparison for radium isotopes. The intercomparison was in two parts involving the distribution of: (1) samples collected from four marine environments (open ocean, continental slope, shelf, and estuary) and (2) a suite of four reference materials prepared with isotopic standards (circulated to participants as ‘unknowns’). Most labs performed well with 228Ra and 224Ra determination, however, there were a number of participants that reported 226Ra, 223Ra, and 228Th (supported 224Ra) well outside the 95% confidence interval. Many outliers were suspected to be a result of poorly calibrated detectors, though other method specific factors likely played a role (e.g., detector leakage, insufficient equilibration). Most methods for radium analysis in seawater involve a MnO2 fiber column preconcentration step; as such, we evaluated the extraction efficiency of this procedure and found that it ranged from an average of 87% to 94% for the four stations. Hence, nonquantitative radium recovery from seawater samples may also have played a role in lab‐to‐lab variability.

Zinc marine biogeochemistry in seawater: a review

The interest in trace element biogeochemistry has arisen from the well demonstrated iron hypothesis that revealed the central role that iron exerts on oceanic primary and associated biogeochemical cycles. The essentiality of zinc for key biological enzymes, coupled with a nutrient-like vertical distribution with low dissolved concentrations in many marine surface waters, provided motivation to study zinc in marine systems. Laboratory studies have confirmed the importance of zinc to sustain phytoplankton growth and its influence on the composition of the phytoplankton community. However, mixed results were obtained in the field, which suggest a more subtle effect of zinc on oceanic phytoplankton growth than iron. As a consequence, consensus on its biological role, mechanisms at play or regional versus global relevance is currently lacking and highlights the need for new conceptual models of zinc in marine systems. The recent GEOTRACES program is generating new data approaches to discuss and understand further zinc behaviour in the ocean.

Volatilization and Precipitation of Tellurium by Aerobic, Tellurite-Resistant Marine Microbes

Microbial resistance to tellurite, an oxyanion of tellurium, is widespread in the biosphere, but the geochemical significance of this trait is poorly understood. As some tellurite resistance markers appear to mediate the formation of volatile tellurides, the potential contribution of tellurite-resistant microbial strains to trace element volatilization in salt marsh sediments was evaluated. Microbial strains were isolated aerobically on the basis of tellurite resistance and subsequently examined for their capacity to volatilize tellurium in pure cultures. The tellurite-resistant strains recovered were either yeasts related to marine isolates of Rhodotorula spp. or gram-positive bacteria related to marine strains within the family Bacillaceae based on rRNA gene sequence comparisons. Most strains produced volatile tellurides, primarily dimethyltelluride, though there was a wide range of the types and amounts of species produced. For example, the Rhodotorula spp. produced the greatest quantities and highest diversity of volatile tellurium compounds. All strains also produced methylated sulfur compounds, primarily dimethyldisulfide. Intracellular tellurium precipitates were a major product of tellurite metabolism in all strains tested, with nearly complete recovery of the tellurite initially provided to cultures as a precipitate. Different strains appeared to produce different shapes and sizes of tellurium containing nanostructures. These studies suggest that aerobic marine yeast and Bacillus spp. may play a greater role in trace element biogeochemistry than has been previously assumed, though additional work is needed to further define and quantify their specific contributions.

FOUR-DECADE RESPONSES OF SOIL TRACE ELEMENTS TO AN AGGRADING OLD-FIELD FOREST: B, MN, ZN, CU, AND FE

In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.

GEOTRACES – An international study of the global marine biogeochemical cycles of trace elements and their isotopes

Trace elements serve important roles as regulators of ocean processes including marine ecosystem dynamics and carbon cycling. The role of iron, for instance, is well known as a limiting micronutrient in the surface ocean. Several other trace elements also play crucial roles in ecosystem function and their supply therefore controls the structure, and possibly the productivity, of marine ecosystems. Understanding the biogeochemical cycling of these micronutrients requires knowledge of their diverse sources and sinks, as well as their transport and chemical form in the ocean. Much of what is known about past ocean conditions, and therefore about the processes driving global climate change, is derived from trace-element and isotope patterns recorded in marine deposits. Reading the geochemical information archived in marine sediments informs us about past changes in fundamental ocean conditions such as temperature, salinity, pH, carbon chemistry, ocean circulation and biological productivity. These records provide our principal source of information about the ocean's role in past climate change. Understanding this role offers unique insights into the future consequences of global change. The cycle of many trace elements and isotopes has been significantly impacted by human activity. Some of these are harmful to the natural and human environment due to their toxicity and/or radioactivity. Understanding the processes that control the transport and fate of these contaminants is an important aspect of protecting the ocean environment. Such understanding requires accurate knowledge of the natural biogeochemical cycling of these elements so that changes due to human activity can be put in context. Despite the recognised importance of understanding the geochemical cycles of trace elements and isotopes, limited knowledge of their sources and sinks in the ocean and the rates and mechanisms governing their internal cycling, constrains their application to illuminating the problems outlined above. Marine geochemists are poised to make significant progress in trace-element biogeochemistry. Advances in clean sampling protocols and analytical techniques provide unprecedented capability for high-density sampling and measurement of a wide range of trace elements and isotopes which can be combined with new modelling strategies that have evolved from the World Ocean Circulation Experiment (WOCE) and Joint Global Ocean Flux Study (JGOFS) programmes. A major new international research programme, GEOTRACES, has now been developed as a result of community input to study the global marine biogeochemical cycles of trace elements and their isotopes. Here, we describe this programme and its rationale.

Metal ion binding to iron oxides

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Assessment of the Geochemical Role of Colloids and Their Impact on Contaminant Toxicity in Freshwaters: An Example from the Lambro−Po System (Italy)

The role of colloids in regulating element transport, behavior, and bioavailability in aquatic systems is now well-established. It appears that further progress in this research field is being slowed by (i) a limited integration between the geochemical and the biological aspects of the research on colloids and (ii) a persistent gap between well-controlled laboratory studies and real field situations. This paper presents a simultaneous evaluation of the role of colloids in controlling element environmental fate and bioavailability at the confluence between a major river and a polluted tributary. Fractionation of trace elements among suspended particulate matter, colloids, and true solution suggests that colloids may play a role in the removal of trace elements from the water column to bed sediments during the mixing of the two rivers. Toxicity testing of water samples indicates that, in this specific system, contaminants associated with colloids can contribute to water toxicity for the rotifer Brachionus calyciflorus but not for the green alga Pseudokirchneriella subcapitata. To the best of our knowledge, the results for B. calyciflorus are the first ones pointing to the possible contribution of colloid-bound contaminants to water toxicity in environmental samples. Despite the uncertainties associated with field variability, the results of chemical analysis and toxicitytesting show several points of convergence. Following these observations, a few innovative research approaches are suggested to improve the understanding of trace element biogeochemistry in real field situations.