published_or_final_version / Zoology / Master / Master of Philosophy

by Amber L. Garr. / Thesis (Ph.D.)--Florida Atlantic University, 2012. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2012. Mode of access: World Wide Web. / The presence of heavy metals and other pollutants is detrimental to marine ecosystems. The queen conch, once an important fisheries species in the Florida Keys, has not sufficiently recovered after a 25-year fishery closure. Research has shown high levels of copper and zinc in the gonads and digestive glands of adult conch found in the nearshore waters. Four sites relevant to queen conch larval recruitment were tested in 2010 for the presence of copper and zinc in the water, phytoplankton, sediment, and seagrass epiphytes over seven months. Both metals were detected in all sample types and no seasonal or geographical differences were detected. Surface water concentrations from the field were used to conduct acute and chronic toxicity tests on various ages of queen conch larvae and their phytoplankton food source. When zinc concentrations (0-40 (So(Bg/L) similar to those measured in situ were used, there was no significant impact on conch larval survival although some velar lobe de velopment was impaired. However, field concentrations of copper (0-15 (So(Bg/L), which often surpassed water quality standards, negatively impacted growth, survival, and development of the larvae. Chronic exposure to copper, through the water and food, disrupted the metamorphic success of competent larvae and decreased post-metamorphosis survival. Exposure to copper at later life stages increased mortality, suggesting that heavy metals have a negative effect on larval recruitment in localized areas of the Florida Keys. Structural equation modeling revealed that copper and zinc are moving through the systems differently and are best represented by two different models.

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An important task of research on trace metals in soils is to evaluate how much metals are potentially bioavailable and may cause toxic effects. In this thesis, the chemical speciation and complexation of cadmium (Cd), copper (Cu), mercury (Hg) and lead (Pb) were examined in eastern Canadian soils collected from different locations around smelters. Our goal is to be able to predict metal binding in the soil solution and on the solid phase under a wide range of field conditions. / In Chapter 2, speciation of Cd, Cu and Pb in the lysimeter soil solutions was determined using an ion exchange technique (IET) involving a resin column. The IET-speciation data were used to estimate the metal-dissolved organic carbon (DOC) binding constants using the non-ideal competitive adsorption (MICA)-Donnan model, which assumed a continuous distribution of binding affinities on the DOC molecule. The published Cd and Pb speciation data in a variety of soils (Chapter 3) were also used to test the effectiveness of two speciation models, the MICA-Donnan model and WinHumicV. Both models satisfactorily predicted the concentrations of Cd2+ and Pb2+. The two chapters of metal speciation demonstrated that the NICA-Donnan model could estimate the binding strength of organic matter in soil solutions. / Proton and metal complexation to the surface of soil particles (Chapters 4 and 5) was investigated using back-titration and batch adsorption procedures. It was shown that the surface binding of H+, Cd2+, Hg2+ and Pb2+ was significantly related to soil organic matter (SOM). Though the soil particle surface was covered by a mixture of organic and mineral components, a two-site distribution could be identified from the titration curves. With the parameters derived from the back-titration and adsorption data, the MICA-Donnan model reasonably predicted the surface complexation of proton and metals. Furthermore, the statistically significant relationships between the model parameters and soil organic matter supported the assumptions in this thesis: (1) Organic matter was the most important sorbent on the particle surface; (2) The MICA-Donnan model may be used to interpret the surface binding data in these soils.

There are two main components to the research: the theoretical and the experimental. Chapter 2 contains an analysis of the state of soil quality guidelines and the scientific methods used to determine them. A number of recommendations to improve soil quality criteria for trace metals are offered including the importance of considering bioavailability and the need to use realistic conditions, trace metal sources and organisms. / A critical review of the literature dealing with predicting the availability of trace metals to plants is presented in Chapter 3. We found little agreement among hundreds of similar studies which relate plant metal uptake to the amount of metal extracted by selective chemical dissolution procedures. An extensive summary of the data shows clearly that the extraction methods are not widely applicable. Differences between individual soils, their metal retention capacities, as well as plant factors and environmental conditions contribute to the variability of the results. Alternative ways of assessing bioavailability are suggested. / The experimental component of the thesis focuses on the availability of trace metals to plants. In Chapter 4 the uptake of Cu from different soil pools was examined and the free metal ion (Cu2+) was found to be the best predictor of uptake by lettuce (Latuca sativa cv. Buttercrunch), ryegrass (Lolium perenne cv. Barmultra) and radish (Raphanus sativus cv. Cherry Belle). / In Chapters 5 and 6 we examined the effect of low-cost in-situ treatments on the availability of metals to plants in greenhouse and field experiments. Synthetic zeolites, P amendments, organic matter and clean soil were used and their effect on the bioavailability of Cd, Cu, Pb, Ni and Zn evaluated. The plants for the experimental work were lettuce and perennial ryegrass. Only the clean soil treatment was consistently effective in reducing the concentration of metals in the plant. We also wanted to determine whether the trace metals in the plant tissue came from the soil or from direct deposition of pollutants on the leaf surfaces. We found little evidence that metals in plants were a result of atmospheric fallout. / A method for the accurate analysis of total metal concentrations in a range of contaminated soils including those containing oil and grease was developed (Chapter 7). For this research the trace metals of concern are Cd, Cu, Ni, Pb and Zn---all commonly found in urban/industrial soils. The proposed method using HNO3/HClO4 has several advantages over the common HNO3/H2O2 procedure. We were able to digest larger soil samples and hence the final concentration of trace metals was usually in the range for analysis by inductively coupled plasma atomic absorption spectrometry or flame atomic absorption spectrometry.

Bioavailability of trace metals in urban contaminated soils was investigated to relate chemical extraction efficiencies with biological effects. / Results from a Collembola reproduction bioassay showed minimal toxicity suggesting limited bioavailability. Chemical extractions were carried out on these urban soils. The sodium acetate extraction was the best predictor of the biological effects of Cd while the biological effects of Zn were best explained by a water extraction. / An earthworm uptake bioassay was done to quantify the bioavailable fractions. Cadmium, Cu, Pb and Zn accumulated in Lumbricus terrestris L. The sodium acetate extraction was the best predictor of Cd uptake while calcium chloride extraction best predicted Zn uptake by earthworms. / Treatments were made to urban soils to immobilize the metals and reduce their bioavailability. The metal concentrations were so low in the soils that the effects of the treatments could not be measured. / Collembola and earthworms are good indicators of trace metal bioavailability and should be included in the evaluation of contaminated soils.

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.

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