The purposes of this study were to establish the reference values of element concentrations and to estimate the food safety and the nutrient values of essential elements in the aquaculture fish products in Taiwan. 31 species of fishes, 4 species of crustaceans and 3 species of molluscs were collected from 11 aquaculture areas in Taiwan from September to November in 2004 to 2006. Concentrations of Ag, As, Cd, Co, Cu, Fe, Hg, Mn, Se, Sr and Zn in the muscles were analyzed. The results showed that the concentrations of those elements had significant difference among teleosteans, crustaceans and molluscs, excepted Hg and Se. Essential element concentrations in Cu, Sr and Zn were higher in invertebrates (shellfishes) than in vertebrates (teleosteans) but Co, Fe and Mn were higher in molluscs than others. All concentrations of non-essential elements excepted Hg were higher in molluscs. Significant species-differences were also found in our results, but not in the concentrations of Ag and Co in teleosteans. Among teleosteans, Trachinotus blochii (As and Se), Anguilla japonica (Cd and Zn), Lates calcarifer (Cu), Carassius auratus auratus (Fe), Epinephelus coioides (Hg), Rachycentron canadum (Hg) and Chanos chanos (Mn and Sr) contained the highest concentrations, showed in parenthesis. Whereas among shellfishes, Haliotis diversicolor (Ag), Meretrix lusoria (As, Cd, Co, Fe, Mn, Se and Sr), Corbicula fluminea (Co and Se), Scylla serrata (Hg and Zn) revealed the highest concentrations of those elements. The results were seminar to previous literatures reported for uncontaminated aquatic environment area worldwide, so they could be the reference values of element concentrations in the aquaculture fish products in Taiwan. The element concentrations in this study were all below the worldwide food safety standards of inorganic As = 1.0, Cd (for fish and crustaceans) = 0.2, Cd (for mollusks) = 2.0, Cu = 10, total Hg = 0.5, Se = 1.0 and Zn = 50 £gg / g wet wt. Based on the normal dietary habit of Taiwanese by consume 400g fishes and 200g shellfishes every week, the element concentrations of weekly intake were bellowed the standards of inorganic As = 15, Cd = 7 and organic Hg = 1.6 £gg / kg of body / week by PTWI, and could obtain more than 100% to Co and 58% to Se of RDA standards at the same time.

<p>Land use histories affect the rate and pattern of soil nutrients at regional and global scale. However, former studies have rarely focused on soil trace elements (B, Mn, Zn, Cu and Fe). In this study, we aimed at the long-term biogeochemical cycling pattern and spatial heterogeneity of soil trace elements in response to land use changes. We conducted experiment at Calhoun experiment forest in SC and surrounded relic hardwood forest, cultivated land and secondary pine forests with contrasting land use histories in a statistically rigorous and spatially explicit design. Our first study indicated that spatial heterogeneity is greatly reduced in many soil properties by agricultural practices, but that successional forest growth on previously cultivated soils re-structures heterogeneity of soil properties within a few decades. We document cases in which land use alters both the soil property's central tendencies and their heterogeneity (C, N, CN, Ca, K), and cases in which changes are apparent in central tendency but much less so in their heterogeneity (Db). In our second study, samples of the upper 0.6-m mineral soil archived in 1962 and 1997 revealed three cycling patterns: 1) Extractable B and Mn were significantly depleted because 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 about 10-fold more than accumulations in tree biomass. This study indicated that forest Fe cycling is qualitatively different from that of other macro- and micro-nutrients. Thirdly, our results revealed that long-term cultivation substantially diminished the activity of soil iron oxides relative to forest growth. Forest Fe cycling is derived from mineral soil weathering, which suggests a need to explore the underlying mechanisms by which bioturbation (e.g.earthworms) mediates transformations of iron bioavailability and oxidation of organic matter in soils. Overall, the wide range of responses to land use changes among the ecosystem's trace elements and other biogeochemical features illustrates the great dynamics of the soil system over time scales of decades to centuries.</p> / Dissertation

The objects of this study were to investigate the differences of total mercury(THg), organic mercury(OHg) concentrations in the muscles of albacore and bigeye tuna from the Pacific Ocean, and the THg and OHg concentration in the livers , and the trace elements (Cu, Fe, Mn and Zn) in the muscles and livers of albacore, in order to evaluate the bioaccumulative status of the oceanic migratory fishes. Meanwhile, The relationships between mercury concentration and size (length and weight) and age were established, and the differences of mercury concentrations in the tuna between species and geography were examined. And that the safety consumption level was also discussed. One hundred eighty-five albacore and 134 bigeye tuna were sampled from the period October 2001 to April 2006 and from September 2005 to November 2006, respectively, in the Western and Central Pacific Ocean. The results showed that the average THg (mg/kg flesh wt.) and OHg (mg/kg flesh wt.) of muscles were 0.435¡Ó0.145 and 0.279¡Ó0.087, respectively, for albacore, and 0.935¡Ó0.655 and 0.544¡Ó0.396, respectively, for bigeye tuna. The THg and OHg of livers of albacore were 0.426¡Ó0.363 and 0.193¡Ó0.121, respectively. The average OHg percentages of the THg in albacore and bigeye tuna were 67¡Ó19 % and 62¡Ó20 %, respectively. Except there was no significant correlation between OHg and age in the liver of albacore, the THg and OHg in the muscles, and THg in the livers of albacore, and THg in the muscles of bigeye tuna showed a positive correlation with size and age. The THg and OHg levels in the muscles of albacore were lower than those of bigeye tuna, and the accumulative rates of THg and OHg in albacore were lower than those in bigeye tuna. No significant different of muscles-THg and -OHg concentrations of albacore from the four samplind areas. However, the THg and OHg levels in muscle of bigeye tuna showed that north group higher than those in equator. The concentrations of THg were similar in muscle and liver of albacore, but those OHg, Cu, Fe, Mn and Zn concentrations in liver were significantly higher than those in muscle. A detoxificated mechanism may be commenced when the concentration of THg in liver of albacore exceed 0.8 mg/kg, to maintain the muscle concentration of THg at a level about 0.7 mg/kg. The OHg concentrations of all albacore and 88% of bigeye tuna were below WHO food safety standard for migratory fishes(1.0 mg/kg). The consumption amount of albacore and bigeye tuna were no more than 300 and 150g, respectively, will not exceesed the PTWI(provisional tolerable weekly intake) set by WHO, that will not cause any health threat for consumer.

Elemental analysis of pottery sherds provided insights on the ceramic production in the Huancabamba Valley (northern highland-Peru) and the way in which the Incas administrate the provinces. The pottery sherds from six archaeological sites selected for elemental analysis indicated the use of similar clay sources in the manufacture of pottery. The production of ceramic vessels took place at the local level without the strict control of the Inca state. The Incas built administrative structures in the Huancabamba Valley in order to maintain control of their road system, which connected the north area of Peru to Ecuador. The ceramic assemblage recovered from Inca sites does not illustrate typical Inca pottery style or decoration from the heartland. The administrative centers built by the Incas throughout the Empire provided the means to support state activities such as pottery production of local wares. In addition, ethno-historic evidence suggests that during the Inca period coastal communities were relocated to highland settlements in order to serve as officers in state facilities, or to maintain the Inca road system. These coastal communities continue producing pottery following the traditional techniques from their homeland.

The research used dendro-chemical analysis of ash tree rings and current year leaf litter to track Cd, Pb, Zn, Cu, Mn, Cr, and Sn spread and cycling from a closed garbage dump-toxic waste site. This technique allowed for determination of areal extent, contaminant levels and time period of initial contaminant contact. Only Zn, Sn, and Cu were found in elevated quantities in the xylem wood and Pb in the leaf litter. Elemental concentrations of Pb, Sn and Cd in xylem wood and leaves of ash were positively correlated. Tin was the only element to demonstrate a clear initial contact period and elemental accumulation with age. Significant levels of Cu accumulated in the heartwood while Zn revealed significant but inconsistent accumulated patterns. Expected attenuation zones associated with municipal solid waste landfill leachate dispersion were not found; thus the pathway for contaminant dispersion was likely through groundwater flow. / An elemental index was developed to facilitate the use of dendro-chemical analysis in periods of suppressed tree growth resulting from environmental pollution.

Innovative means and methods were tested to develop an economical, pragmatic and environmentally sustainable soil remediation process for heavy metal contaminated soils. An unsaturated-flow soil washing procedure was devised to dissolve the soil-bound toxic heavy metals; the latter were extracted by a chemical washing solution that percolated through the soil matrix. Subsequently, the leached toxic heavy metals were selectively concentrated, by a chemical precipitation process, into a solid waste. Thereby, a fraction of the spent ethylenediaminetetraacetic acid (EDTA), within the washing and rinsing leachate, was theoretically regenerated and recycle-ready. / The unsaturated-flow washing procedure was perfected by applying different treatments to a soil from a secure landfill. This soil was contaminated with Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, S and Zn. The major contaminants were Fe, Pb, Zn, S, Cu and Mn, making up 25, 1.9, 1.0, 0.4, 0.4 and 0.2%wt of the soil. The extraction responses of the contaminants and those of Al, Ca, Mg and P were established for citric acid (0.5 M) and different molarities of diammonium EDTA ((NH4)2EDTA). The DOW Chemical Company supplied the (NH4)2EDTA (i.e. VERSENE), a 1.37M industrial cleaner, which roughly costs $1.85kg-1 in bulk. The affordability of VERSENE was a pre-condition for hoping to satisfy the economical feasibility of remediating trace metal contaminated soils. / Ultimately, the developed unsaturated-flow washing procedure was tested in a pilot-scale experiment, for its ability to remediate a soil from an abandoned car battery recycling facility. The latter soil was severely contaminated with Pb (3.9%wt). Drip irrigation was used to apply (NH4) 2EDTA and water-rinsing solutions to the surface of soil heaps that rested atop an impermeable barrier, which permitted the retrieval of the leachate. A cumulative EDTA input to the soil of 10.6% wt extracted 49.4% of the total Pb content of the soil. Alternatively, readily biodegradable citric acid barely extracted 2.2% of the total Pb content of the soil, for a cumulative input of 18.1% weight of soil. Different treatments were tested for their effectiveness in concentrating the leached toxic heavy metals into a solid waste. The Pb was best precipitated with Na2S alone, as it provided the most concentrated solid toxic waste. / The environmental sustainability of remediating trace metal contaminated soils was thoroughly examined, as per the amounts of chemical entrants and toxic waste by-products, and per the post-treatment leaching of toxic levels of the remaining and potentially toxic trace metals. (Abstract shortened by UMI.)

The adsorption behaviour of trace metals in soil may provide us with a way to more accurately predict and assess the toxicity of metals in the environment. This thesis reports efforts to apply surface complexation modeling to agricultural and forest soil and to relate model parameters to common soil properties. This study considered Ca, Cd, Cu, Pb and Zn but the methods here could be applied to other metals. In Chapter 2, the surface charge and adsorption behaviour of a set of Ap horizons was characterised using back-titration and batch adsorption techniques. With the objective of simplifying the application of the NICCA model to surface charge and cation adsorption in whole soils the parameters of the NICCA model were related to soil properties (Chapter 3). Four of the six surface charge parameters could be predicted from soil properties and this enabled me to reasonably predict the surface charge of a second group of soils from soil properties. These results suggest that it is possible to make reasonable predictions about the surface charge and adsorption behaviour of a given type of soil using some easily measurable soil properties and a set of generic NICCA adsorption parameters for that soil type. In Chapter 4 this idea is applied to the determination of lime requirement for the agricultural soils.

Soil quality guidelines are currently based on total trace metal loads. There is a need to define indices of bioavailability to allow reasonable predictions for plant metal uptake and toxicity in soils. Trace metal toxicities to plants often correlate best with free metal ion activities. The first objective was to develop a plant bioassay that is sensitive to trace metals at concentrations realistic for soils. The root elongation of lettuce Lactuca sativa 'Buttercrunch' was used as toxicological endpoint. This endpoint was sensitive and reproducible to environmentally relevant concentrations of Cd, Cu, Ni, Pb and Zn. The second objective was to test whether free metal ion activities are constant predictors of metal toxicities in synthetic solutions and in soil extracts that differ in their concentrations of cations and ligands. The root elongation assay was used to test this hypothesis. In synthetic solutions, the rhizotoxicity of Cd, Cu, Ni, Pb and Zn decreased with increasing Ca and H concentrations. This could not be explained with the effect of higher cationic concentrations on root growth or on solution speciation. It was concluded that Ca and H inhibited the rhizotoxicity of all metals tested. The rhizotoxicity of Cu and Cd was further examined in soil extracts. Both metals became less rhizotoxic at higher H and dissolved organic matter concentrations. The rhizotoxicity endpoints from the experiments in synthetic solution were used to develop parameters for a Biotic Ligand Model (BLM) for Cd, Cu, Ni, Pb and Zn. The BLM accounts for solution speciation and interprets cationic inhibition of rhizotoxicity as competition of metals with Ca and H for potential sites of rhizotoxicity. The BLM predicted metal rhizotoxicity better than the free metal ion activity in synthetic solutions and in soil extracts. Different models were tested against literature rhizotoxicity data for metals at different Ca and H concentrations. Predictions for metal rhizotoxicity given by BLM, Gouy-Chapman-Stern model and Freundlich equation model were compared with predictions based on free metal ion activities in solution. The BLM predicted rhizotoxicity most accurately. The BLM seems promising for predictions of metal toxicity and metal bioavailability in soils to support site-specific environmental risk assessments.

Trace elements added to the soil by human activities could contaminate it and occasionally cause a threat to environmental and human health. The toxicity and mobility of a trace element are affected by the element's solubility, which in turn is influenced by the soil properties. When mobile, trace elements can be leached out of the soil. If leaching occurs at a faster rate than atmospheric deposition, element concentrations in the soil will decrease by natural attenuation. / We analyzed soil properties in 40 soils and their soil solutions to obtain a set of equations with the most significant predictors of As, Cd, Co, Cu, Mo, Ni, Pb and Zn in solution. The total element concentration and the pH were the best predicting variables of the amount of element in solution for all trace elements analyzed, while organic carbon and Al or Mn oxides also influenced the solubility of some trace elements. Using the equations predicting elemental solubility, we wrote a model for natural attenuation in the computer program Stella that considers atmospheric deposition as the input for trace elements and leaching as the output. Simulations were carried out for the 40 soils during 1,000 years with steady deposition inputs. / At current atmospheric deposition rates and the neutral to alkaline pH of these soils, attenuation occurred in most soils for Mo. For As, Cd, Co, Cu and Ni it occurred only in soils with abundant total element concentrations or an acidic pH. Minor retention occurred with Pb and Zn. Only Cd and Cu were of concern in leaching waters. The developed model can serve as a decision making tool in the selection of natural attenuation as a remediation strategy.

The goal of this research was to devise a new analytical technique, using Accelerator Mass Spectrometry (AMS), to measure Platinum Group Element (PGE) concentrations to the sup-ppb levels in natural, insulating, samples. The challenges were threefold. First, a method of sputtering an insulating sample to successfully produce a stable beam of anions needed to be devised. Second, a suitable standard of known PGE concentrations had to be found and third, spectral analysis of the beam had to verify any claims of PGE abundance. The first challenge was met by employing a modified high intensity negative ion source flooded with neutral caesium that successfully sputtered insulators to produce a beam of negative ions. The second challenge, that of finding a suitable standard, was fraught with difficulties, as no synthesized standards available were found to be appropriate for this work. As a result, direction is provided for future production of standards by ion implantation. The third challenge, successful spectral analysis, was accomplished using a newly designed gas ionization detector which allowed for resolution of the interfering molecular fragment from the PGE ions. Coupled with the use of the SRIM computer programme, positive identification of all peaks in the spectra of the analyzed samples was accomplished. The success of the first and third challenges lead to the qualitative analyses of geological samples for sub-ppb levels of PGE by AMS. Quantitative analyses await only for the appropriate standards and with those will come a whole new range of research possibilities for measuring sub-ppb levels of PGE in insulating samples by AMS.