Validation of transfer functions predicting Cd and Pb free metal ion activity in soil solution as a function of soil characteristics and reactive metal content.

According to recent insight, the toxicity of metals in soils is better related to the free metal ion (FMI) activity in the soil solution than to the total metal concentration in soil. However, the determination of FMI activities in soil solution is a difficult and time-consuming task. An alternative is to use empirical equations (so called transfer functions (TFs)) that relate FMI activity in solution to the reactive metal concentration in the solid phase and to soil properties (pH and organic matter content). Here we test the applicability of two sets of TF for Cd and Pb using independent data from a wide range of soil types and regions that are not represented in the datasets used to derive the TFs. From these soils, soil solution was extracted using four different methods. For all these extracts, FMI activities were calculated from total concentrations in solution using the speciation program WHAM VI. In some of the soils, Cd and Pb FMI activities were also measured using a Donnan membrane technique. Most of these FMI activities deviated from the TF predictions by less than one order of magnitude and were within the 95% confidence interval of the TFs, irrespective of the method used to extract soil solution. Predictability was higher for Pb than for Cd and differed also between the two TF sets

A necessary nomadism : rethinking a place in the sun

[v.1]. Sub-thesis -- [v.2]. Studio repor

Prediction of accumulation and leaching of fungicide copper in agricultural soils

Copper is applied extensively to protect a number of crops, including vines/grapes, citrus and other fruits, against fungal attack. In contrast to biodegradable organic chemicals, metals such as copper cannot be degraded in the environment and so can potentially remain as contaminants in the environment for extended periods of time. Metals can undergo processes such as ‘aging’ in certain environmental compartments, such as soils, that reduce their bioavailability and toxicity, but typically a significant proportion of the metal remains in a potentially bioavailable form for extended periods. There is thus a need to assess the potential ecological risks of the ongoing use of copper as a fungicide. This study has been commissioned by the European Copper Task Force (ECTF) to assess the potential risks of the current and future use of copper as a fungicide. Using a set of typical copper application rates, and a set of scenarios covering a representative range of soil types across Europe, we have simulated copper accumulation in soils, surface waters and sediments using an intermediate complexity dynamic model (the IDMM) designed specifically for the long term behaviour of metals. Predicted copper concentrations over time have been compared with Predicted No Effect Concentrations for soil, waters and sediments to assess the current potential risks, and the prospects for the future development of risk under a scenario of continued copper application have been assessed

Applications of metal oxides in the contact systems of organic electronic devices

Metal oxides are a group of materials that have shown great promise in improving the efficiency of devices based on organic materials through inclusion in the contact structures of such devices. In this work, the deposition technique of spray pyrolysis is developed for use for the deposition of doped zinc oxide films and molybdenum oxide films. Spray pyrolysis is of great interest as a technique for use in the organic electronics field due to its cost, scalability and compatibility with other solution processing techniques. This makes the technique particularly interesting for use in devices intended for large scale applications such as lighting The study of doped zinc oxide focuses on its application as an alternative transparent conducting layer to the standard indium tin oxide layer. The zinc oxide layer was doped with aluminium to increase its conductivity, and the effect of lithium doping was investigated with the intent of improving the conductivity of the layers further. Annealing of the layers in a nitrogen environment was found to produce layers of a similar conductivity to that of indium tin oxide and the lithium doping was found to result in higher conductivities in annealed layers. The study of molybdenum oxide focuses on its application as a hole injection layer included in the anode contact of organic light emitting diodes. The deposition temperature was found to have a large effect on the resulting device efficiencies. This effect was determined to be due to variation of the work function and ion ratios present in the molybdenum oxide layer with deposition temperature. This work resulted in the fabrication of devices with efficiencies double that of the standard solution processed hole injection layer.Open Acces

An analysis of the effectiveness and contribution to the needs of its graduates, in the worthy use of leisure time, of the boys physical education program in the Dedham, Massachusetts, High School.

Thesis (Ed.M.)--Boston Universit

Ecological indicators for abandoned mines, Phase 1: Review of the literature

Mine waters have been identified as a significant issue in the majority of Environment Agency draft River Basin Management Plans. They are one of the largest drivers for chemical pollution in the draft Impact Assessment for the Water Framework Directive (WFD), with significant failures of environmental quality standards (EQS) for metals (particularly Cd, Pb, Zn, Cu, Fe) in many rivers linked to abandoned mines. Existing EQS may be overprotective of aquatic life which may have adapted over centuries of exposure. This study forms part of a larger project to investigate the ecological impact of metals in rivers, to develop water quality targets (alternative objectives for the WFD) for aquatic ecosystems impacted by long-term mining pollution. The report reviews literature on EQS failures, metal effects on aquatic biota and effects of water chemistry, and uses this information to consider further work. A preliminary assessment of water quality and biology data for 87 sites across Gwynedd and Ceredigion (Wales) shows that existing Environment Agency water quality and biology data could be used to establish statistical relations between chemical variables and metrics of ecological quality. Visual representation and preliminary statistical analyses show that invertebrate diversity declines with increasing zinc concentration. However, the situation is more complex because the effects of other metals are not readily apparent. Furthermore, pH and aluminium also affect streamwater invertebrates, making it difficult to tease out toxicity due to individual mine-derived metals. The most characteristic feature of the plant communities of metal-impacted systems is a reduction in diversity, compared to that found in comparable unimpacted streams. Some species thrive in the presence of heavy metals, presumably because they are able to develop metal tolerance, whilst others consistently disappear. Effects are, however, confounded by water chemistry, particularly pH. Tolerant species are spread across a number of divisions of photosynthetic organisms, though green algae, diatoms and blue-green algae are usually most abundant, often thriving in the absence of competition and/or grazing. Current UK monitoring techniques focus on community composition and, whilst these provide a sampling and analytical framework for studies of metal impacts, the metrics are not sensitive to these impacts. There is scope for developing new metrics, based on community-level analyses and for looking at morphological variations common in some taxa at elevated metal concentrations. On the whole, community-based metrics are recommended, as these are easier to relate to ecological status definitions. With respect to invertebrates and fish, metals affect individuals, population and communities but sensitivity varies among species, life stages, sexes, trophic groups and with body condition. Acclimation or adaptation may cause varying sensitivity even within species. Ecosystem-scale effects, for example on ecological function, are poorly understood. Effects vary between metals such as cadmium, copper, lead, chromium, zinc and nickel in order of decreasing toxicity. Aluminium is important in acidified headwaters. Biological effects depend on speciation, toxicity, availability, mixtures, complexation and exposure conditions, for example discharge (flow). Current water quality monitoring is unlikely to detect short-term episodic increases in metal concentrations or evaluate the bioavailability of elevated metal concentrations in sediments. These factors create uncertainty in detecting ecological impairment in metal-impacted ecosystems. Moreover, most widely used biological indicators for UK freshwaters were developed for other pressures and none distinguishes metal impacts from other causes of impairment. Key ecological needs for better regulation and management of metals in rivers include: i) models relating metal data to ecological data that better represent influences on metal toxicity; ii) biodiagnostic indices to reflect metal effects; iii) better methods to identify metal acclimation or adaptation among sensitive taxa; iv) better investigative procedures to isolate metal effects from other pressures. Laboratory data on the effects of water chemistry on cationic metal toxicity and bioaccumulation show that a number of chemical parameters, particularly pH, dissolved organic carbon (DOC) and major cations (Na, Mg, K, Ca) exert a major influence on the toxicity and/or bioaccumulation of cationic metals. The biotic ligand model (BLM) provides a conceptual framework for understanding these water chemistry effects as a combination of the influence of chemical speciation, and metal uptake by organisms in competition with H+ and other cations. In some cases where the BLM cannot describe effects, empirical bioavailable models have been successfully used. Laboratory data on the effects of metal mixtures across different water chemistries are sparse, with implications for transferring understanding to mining-impacted sites in the field where mixture effects are likely. The available field data, although relatively sparse, indicate that water chemistry influences metal effects on aquatic ecosystems. This occurs through complexation reactions, notably involving dissolved organic matter and metals such as Al, Cu and Pb. Secondly, because bioaccumulation and toxicity are partly governed by complexation reactions, competition effects among metals, and between metals and H+, give rise to dependences upon water chemistry. There is evidence that combinations of metals are active in the field; the main study conducted so far demonstrated the combined effects of Al and Zn, and suggested, less certainly, that Cu and H+ can also contribute. Chemical speciation is essential to interpret and predict observed effects in the field. Speciation results need to be combined with a model that relates free ion concentrations to toxic effect. Understanding the toxic effects of heavy metals derived from abandoned mines requires the simultaneous consideration of the acidity-related components Al and H+. There are a number of reasons why organisms in waters affected by abandoned mines may experience different levels of metal toxicity than in the laboratory. This could lead to discrepancies between actual field behaviour and that predicted by EQS derived from laboratory experiments, as would be applied within the WFD. The main factors to consider are adaptation/acclimation, water chemistry, and the effects of combinations of metals. Secondary effects are metals in food, metals supplied by sediments, and variability in stream flows. Two of the most prominent factors, namely adaptation/ acclimation and bioavailability, could justify changes in EQS or the adoption of an alternative measure of toxic effects in the field. Given that abandoned mines are widespread in England and Wales, and the high cost of their remediation to meet proposed WFD EQS criteria, further research into the question is clearly justified. Although ecological communities of mine-affected streamwaters might be over-protected by proposed WFD EQS, there are some conditions under which metals emanating from abandoned mines definitely exert toxic effects on biota. The main issue is therefore the reliable identification of chemical conditions that are unacceptable and comparison of those conditions with those predicted by WFD EQS. If significant differences can convincingly be demonstrated, the argument could be made for alternative standards for waters affected by abandoned mines. Therefore in our view, the immediate research priority is to improve the quantification of metal effects under field circumstances. Demonstration of dose-response relationships, based on metal mixtures and their chemical speciation, and the use of better biological tools to detect and diagnose community-level impairment, would provide the necessary scientific information

Terrestrial ecosystem health under long-term metal inputs: modeling and risk assessment

Metal contamination of soils may pose long-term risks to ecosystem health if not properly managed. Future projection of contamination trends, coupled with ecological assessment, is needed to assess such risks. This can be achieved by coupling dynamic models of soil metal accumulation and loss with risk assessment on the basis of projected metal levels. In this study, we modeled the long-term dynamics of Cu, Zn, and Cd in agricultural topsoils of a northern Chinese catchment (Guanting reservoir) and related projected metal levels to 2060 to ecological risk. Past metal dynamics were simulated using historical metal inputs from atmospheric deposition, irrigation, fertilizers, and animal manures. Modeling future dynamics was done using scenarios of projected metal input rates. Ecological risk assessment was done using the Potentially Affected Fraction (PAF) approach to estimate the combined toxic pressure due to the three metals. Modeled labile soil metals agreed well with measurements from monitoring in 2009 following adjustment of the porewater dissolved organic concentration. Metals were predicted to be largely retained in the topsoil. Projections were sensitive to changes in imposed soil pH, organic matter, and porewater dissolved organic carbon. Modeling suggests that decreases in input rates to between 5% and 7.5% of 2009 levels are required to prevent further accumulation. Computed PAFs suggest zinc makes the greatest contribution to ecological risk. Under the most conservative estimate of PAF, the threshold of potential ecological risk was reached before 2060 in two of the three future input scenarios

WHAM-FTOXβ – An aquatic toxicity model based on intrinsic metal toxic potency and intrinsic species sensitivity

We developed a model that quantifies aquatic cationic toxicity by a combination of the intrinsic toxicities of metals and protons and the intrinsic sensitivities of the test species. It is based on the WHAM-FTOX model, which combines the calculated binding of cations by the organism with toxicity coefficients (αH, αM) to estimate the variable FTOX, a measure of toxic effect; the key parameter αM,max (applying at infinite time) depends upon both the metal and the test species. In our new model, WHAM-FTOXβ, values of αM,max are given by the product αM* × β, where αM* has a single value for each metal, and β a single value for each species. To parameterise WHAM-FTOXβ, we assembled a set of 2182 estimates of αM,max obtained by applying the basic model to laboratory toxicity data for 76 different test species, covering 15 different metals, and including results for metal mixtures. Then we fitted the log10 αM,max values with αM* and β values (a total of 91 parameters). The resulting model accounted for 72% of the variance in log10 αM,max. The values of αM* increased markedly as the chemical character of the metal changed from hard (average αM* = 4.4) to intermediate (average αM* = 25) to soft (average αM* = 560). The values of log10 β were normally distributed, with a 5–95 percentile range of -0.73 to +0.56, corresponding to β values of 0.18 to 3.62. The WHAM-FTOXβ model entails the assumption that test species exhibit common relative sensitivity, i.e. the ratio αM,max / αM* is constant across all metals. This was tested with data from studies in which the toxic responses of a single organism towards two or more metals had been measured (179 examples for the most-tested metals Ni, Cu, Zn, Ag, Cd, Pb), and statistically-significant (p < 0.003) results were obtained

Relating metal exposure and chemical speciation to trace metal accumulation in aquatic insects under natural field conditions

The present study investigated to what extent measured dissolved metal concentrations, WHAM-predicted free metal ion activity and modulating water chemistry factors can predict Ni, Cu, Zn, Cd and Pb accumulation in various aquatic insects under natural field conditions. Total dissolved concentrations and accumulated metal levels in four taxa (Leuctra sp., Simuliidae, Rhithrogena sp. and Perlodidae) were determined and free metal ion activities were calculated in 36 headwater streams located in the north-west part of England. Observed invertebrate body burdens were strongly related to free metal ion activities and competition among cations for uptake in the biota. Taking into account competitive effects generally provided better fits than considering uptake as a function of total dissolved metal levels or the free ion alone. Due to the critical importance and large range in pH (4.09 to 8.33), the H+ ion activity was the most dominant factor influencing metal accumulation. Adding the influence of Na+ on Cu2+ accumulation improved the model goodness of fit for both Rhithrogena sp. and Perlodidae. Effects of hardness ions on metal accumulation were limited, indicating the minor influence of Ca2+ and Mg2+ on metal accumulation in soft-water streams (0.01 to 0.94 mM Ca; 0.02 to 0.39 mM Mg). DOC levels (ranging from 0.6 to 8.9 mg L− 1) significantly affected Cu body burdens, however not the accumulation of the other metals. Our results suggest that 1) uptake and accumulation of free metal ions are most dominantly influenced by competition of free H+ ions in low-hardness headwaters and 2) invertebrate body burdens in natural waters can be predicted based on the free metal ion activity using speciation modelling and effects of H+ competition