Total Metal Flux Research Articles

Attribution of sources to metal accumulation in an alpine tarn, the Snowy Mountains, Australia

This study analyses 1800 years of heavy metal accumulation in a remote alpine lake experiencing long-range atmospheric contamination and additional inputs of Ag from cloud seeding. In comparison to previous work undertaken on peats, lake sediments show limited post-industrial metal enrichment with enrichment factors of Ag: 1.3, Pb: 1.3, Zn: 1.1, Cu: 1.2 compared to Ag: 2.2, Pb: 3.3, Zn: 2.1, Cu: 4.1 for peat. We show this to be the result of substantial fluvial lithogenic flux of metals (92–97% of total metal flux) to the lake. Total annual metal flux to the lake ranges from: Ag: 4–12 ng/cm2/yr to Zn: 3 383–11 313 ng/cm2/yr. As a result, any contribution of cloud seeding to additional enrichment of Ag in lake sediments is considered negligible. Results show that metal enrichment is not necessarily ubiquitous through a landscape. This has implications for predicting the impacts of atmospheric metal pollution to complex environmental systems.

Near-Infrared Absorption in Lattice-Matched AlInN/GaN and Strained AlGaN/GaN Heterostructures Grown by MBE on Low-Defect GaN Substrates

We have investigated near-infrared absorption and photocurrent in lattice-matched AlInN/GaN and strained AlGaN/GaN heterostructures grown by molecular-beam epitaxy (MBE) on low-defect GaN substrates for infrared device applications. The AlGaN/GaN heterostructures were grown under Ga-rich conditions at 745°C. Material characterization via atomic force microscopy and high-resolution x-ray diffraction indicates that the AlGaN/GaN heterostructures have smooth and well-defined interfaces. A minimum full-width at half-maximum of 92 meV was obtained for the width of the intersubband absorption peak at 675 meV of a 13.7 A GaN/27.5 A Al0.47Ga0.53N superlattice. The variation of the intersubband absorption energy across a 1 cm × 1 cm wafer was ±1%. An AlGaN/GaN-based electromodulated absorption device and a quantum well infrared detector were also fabricated. Using electromodulated absorption spectroscopy, the full-width at half-maximum of the absorption peak was reduced by 33% compared with the direct absorption measurement. This demonstrates the suitability of the electromodulated absorption technique for determining the intrinsic width of intersubband transitions. The detector displayed a peak responsivity of 195 μA/W at 614 meV (2.02 μm) without bias. Optimal MBE growth conditions for lattice-matched AlInN on low-defect GaN substrates were also studied as a function of total metal flux and growth temperature. A maximum growth rate of 3.8 nm/min was achieved while maintaining a high level of material quality. Intersubband absorption in AlInN/GaN superlattices was observed at 430 meV with full-width at half-maximum of 142 meV. Theoretical calculations of the intersubband absorption energies were found to be in agreement with the experimental results for both AlGaN/GaN and AlInN/GaN heterostructures.

Metal flux through consuming interfaces in ligand mixtures: boundary conditions do not influence the lability and relative contributions of metal species

In a mixture of metal ions and complexes, it is difficult to predict ecological risk without understanding the contribution of each metal species to biouptake. For microorganisms, the rate of uptake (internalization flux) has not only a major influence on the total metal flux but also on the bioavailability of the various metal species and their relative contributions to the total flux. In this paper, the microorganism is considered as a consuming interface, which interacts with the metal ion, M, via the Michaelis-Menten boundary conditions. The contribution of each metal complex to the overall metal flux, in relation to its lability, is examined for a number of important boundary parameters (the equilibrium constant K(a) of metal with transport sites, internalization rate constant k(int) and total transport sites concentration {R}(t)). Computations were performed for Cu(II) complexes, in a multicomponent culture medium for microoganisms. For a one-ligand system, results were acquired using rigorous mathematical expressions, whereas approximate expressions, based on the reaction layer approximation (RLA) and rigorous numerical computations (computer codes MHEDYN and FLUXY), were employed for ligand mixtures. Under the condition of ligand excess, as often found in the natural environment, the relative contribution of each metal species to the total flux is shown to be independent of the boundary conditions. This finding has important implications, including an improved basis for relating the analytical signals of dynamic metal speciation sensors to metal bioavailability.

Metal Flux in Ligand Mixtures. 2. Flux Enhancement Due to Kinetic Interplay: Comparison of the Reaction Layer Approximation with a Rigorous Approach

The revisited reaction layer approximation (RLA) of metal flux at consuming interfaces in ligand mixtures, discussed in the previous paper (part 1 of this series) is systematically validated by comparison with the results of rigorous numerical simulations. The current paper focuses on conditions under which the total metal flux is enhanced in the ligand (and complex) mixture compared to the case where the individual fluxes of metal complexes are independent of each other. Such an effect is exhibited only in ligand mixtures and results from the kinetic interplay between the various complexes with different labilities. It is exemplified by the Cu/NTA/N-(2-carboxyphenyl)glycine system (see part 1 paper), in which we show that the flux due to the less labile complex (CuNTA) is increased in the presence of a ligand (2-carboxyphenyl)glycine) that forms labile Cu complexes, even when the latter is in negligible proportion in the bulk solution. This paper first explains how the so-called composite and equivalent reaction layer thicknesses computed by RLA can be determined graphically from the concentration profiles of free metal and its complexes, as obtained by rigorous calculations. This approach allows comparison between the latter and RLA predictions. Comparison between these reaction layer thicknesses is then done using the chemical system mentioned above. The mechanism of flux enhancement with this system is studied in detail by following the change of the concentration profiles and reaction layer thicknesses with the increase of concentration of the ligand forming labile complexes. The mechanism of flux enhancement is well explained by the RLA and is validated by the concentration profiles obtained by rigorous numerical simulations. Based on this validation, the RLA is used to predict the conditions of the individual complex labilities and degree of complexation required to get flux enhancement in a two-ligand system. Due to compensation effects between kinetic and thermodynamic factors, a maximum flux enhancement is observed in a specific range of ratios of the lability indices of the two complexes. Flux enhancement might play a significant role in metal uptake in environmental or biological systems and should be considered in data interpretation.

Interfacial Metal Flux in Ligand Mixtures. 1. The Revisited Reaction Layer Approximation: Theory and Examples of Applications

Understanding the physical chemical behaviors of each metal species in a solution containing a mixture of ligands is a prerequisite, e.g., for studying metal bioavailability or making predictions on dynamic risk assessment in ecotoxicology. For many years, the reaction layer concept has been used fruitfully due to its simplicity for understanding and making predictions on diffusion/reaction processes. Until now, it has been applied mainly to solutions containing one ligand. Here, we reconsider the fundamentals of this approach and extend it to multiligand systems. It is shown that each metal complex has its own reaction layer (so-called composite reaction layer), which results from the interplay of this particular complex with all the other complexes. Moreover, it is shown that the overall metal flux can be computed by assuming the existence of one single fictitious equivalent reaction layer thickness for the whole of the complexes. This equivalent reaction layer is a mathematical combination of all the composite reaction layers. Simple analytical equations are obtained, which make it possible to readily interpret the role of the various types of metal species in a mixture. The revisited reaction layer approach, denoted as the reaction layer approximation (RLA), is validated by comparing the total metal flux, the individual fluxes of each metal species, and their concentration profiles computed by the RLA with those obtained by a rigorous mathematical approach. The examples of Pb(II) in a modified Aquil medium and of Cu(II) in solutions of nitrilotriacetic acid and N-(2-carboxyphenyl)glycine are treated in detail. In particular, an original result is obtained with the Cu/NTA/N-(2-carboxyphenyl)glycine system, namely an unexpected flux enhancement is observed, which is specific to solutions with ligand mixtures. The corresponding physicochemical mechanism is not readily understood by the rigorous mathematical (either numerical or analytical) solutions due to their involved combination of parameters. On the other hand, we show that, due to the simplicity of the RLA concept, the RLA facilitates elucidation of the physicochemical mechanism underlying complicated processes.

Mn incorporation in GaN thin layers grown by molecular-beam epitaxy

GaMnN layers have been grown by MBE on Si(111) in a wide range of growth conditions. For different substrate temperatures the structural and composition dependence of the grown layers has been studied as a function of the Mn supply. We find that at regular substrate temperature the incorporation of Mn into the layer is low and difficult to control. Only at a reduced substrate temperature of 650 °C and under N-rich growth conditions it is possible to grow homogeneous GaMnN layers if the Mn supply is below 15% of the total metal flux. The incorporation efficiency in this range is about 30%, which corresponds to a maximum Mn content in the diluted layers of about 5%. Above a critical Mn supply, GaMn3N precipitates are formed, which often extend out of the surface with a typical pyramidal structure.

Plasma and process characterization of high power magnetron physical vapor deposition with integrated plasma equipment—feature profile model

High power magnetron physical vapor deposition (HPM-PVD) has recently emerged for metal deposition into deep submicron features in state of the art integrated circuit fabrication. However, the plasma characteristics and process mechanism are not well known. An integrated plasma equipment-feature profile modeling infrastructure has therefore been developed for HPM-PVD deposition, and it has been applied to simulating copper seed deposition with an Ar background gas for damascene metalization. The equipment scale model is based on the hybrid plasma equipment model [M. Grapperhaus et al., J. Appl. Phys. 83, 35 (1998); J. Lu and M. J. Kushner, ibid., 89, 878 (2001)], which couples a three-dimensional Monte Carlo sputtering module within a two-dimensional fluid model. The plasma kinetics of thermalized, athermal, and ionized metals and the contributions of these species in feature deposition are resolved. A Monte Carlo technique is used to derive the angular distribution of athermal metals. Simulations show that in typical HPM-PVD processing, Ar+ is the dominant ionized species driving sputtering. Athermal metal neutrals are the dominant deposition precursors due to the operation at high target power and low pressure. The angular distribution of athermals is off axis and more focused than thermal neutrals. The athermal characteristics favor sufficient and uniform deposition on the sidewall of the feature, which is the critical area in small feature filling. In addition, athermals lead to a thick bottom coverage. An appreciable fraction (∼10%) of the metals incident to the wafer are ionized. The ionized metals also contribute to bottom deposition in the absence of sputtering. We have studied the impact of process and equipment parameters on HPM-PVD. Simulations show that target power impacts both plasma ionization and target sputtering. The Ar+ ion density increases nearly linearly with target power, different from the behavior of typical ionized PVD processing. The total metal flux to the wafer increases with target power due to enhanced target sputtering. However, the ionization fraction of the total flux decreases due in part to the increased diffusion loss of charged species. Wafer bias power controls ion energy, and it has a negligible impact on plasma ionization and deposition flux composition. Feature simulations show the redistribution of deposited metals within a feature when wafer resputtering is promoted at sufficient bias power. Target-wafer spacing (TWS) impacts the total ionization and metal flux to the wafer. The Ar+ density and deposition rate decrease with increasing TWS due to increased surface loss. Simulations suggest that reducing the TWS results in more efficient usage of target source.

A statistical analysis of copper bottom coverage of high-aspect-ratio features using ionized physical vapor deposition

Ionized physical vapor deposition (IPVD) is a new method for depositing metal into high-aspect-ratio features used as interconnects in microelectronic fabrication. It is similar to sputtering except that a portion of the metal flux to the substrate is ionized. We show how a high ionized-metal-flux fraction (IMFF) at the deposition location improves the bottom coverage of deposited metal films. To measure IMFF, a tool was developed, that biased the front surface of a microbalance crystal directly so as to repel ions. Cu IMFFs to the substrate of greater than 90 % along with deposition rates of 1000 /spl Aring//min can be achieved. A statistical model for both IMFF and total metal flux as a function of four control variables, chamber height, Ar pressure, ionizer power, and sputter power, was developed.

Environmental risk increase due to heavy metal contamination caused by a copper mining activity in Southern Brazil.

The Camaquã Copper Mines (CCM) were the main sulphide deposit in Southern Brazil and have been in operation from last century to 1996. To evaluate water contamination and environmental risk increase by heavy metals from mining operations, two points on the João Dias Creek were sampled (Station 1, background area and Station 2, contaminated area). Mining activity increased the natural weakly heavy metal fluxes by approximately 5424 kg. (approximately 60%) of the total metal flux, 1542 kg. (approximately 49%) of dissolved and 3881 kg (approximately 66%) of particulate metal flux. Total metal flux of anthropic origin was mostly due to Fe followed by Cu > Zn > Mn whereas Cd, As and Pb fluxes were negligible. The potential human health hazards and risk assessment related to daily intake of water from João Dias Creek are mostly due to Mn and should be of concern for the contaminated area. The ingestion of water from station 2 represents incremental risks of 130% and 59% respectively, considering the non-carcinogenic and the carcinogenic effects. The real increase of human health hazards may be greater than those related to the total concentrations since Mn and As dissolved concentrations were 5.5 and 2.0 higher than acceptable, respectively.

Role of ozone in reactive coevaporation of lead zirconate titanate thin films

The role of ozone in the reactive coevaporation of the lead zirconate titanate thin film was investigated by depositing films at various growth rates with various ozone fluxes or molecular oxygen fluxes on unheated substrates and then crystallizing them using rapid thermal annealing. The oxidation state of lead in the as-deposited film was determined from the ratio of the ozone to the total metal fluxes. The amount of atomic oxygen supplied to the surface of the film was at least 103 times larger when the deposition was done using ozone rather than molecular oxygen. When the ozone flux was more than one-third of the total metal flux, well-oxidized films were obtained. To ensure obtaining well-oxidized film, the ozone flax should be more than twice as much.

What fraction of the total metal flux into lakes is retained in the sediments?

What fraction of the total metal flux into lakes is retained in the sediments?

The Estuarine Surface Microlayer and Trace Metal Cycling in a Salt Marsh

The aqueous surface microlayer in a Delaware salt marsh carries an average of 10 percent of the copper, 19 percent of the zinc, and 23 percent of the iron relative to the total metal flux including the dissolved and seston components. Such trace metals cycle in the salt marsh by net import on the surface microlayer and net export in the dissolved and seston components during maximum monthly tides.