Chemical treatment of contaminated soils (in-situ or ex-situ) is the current most practical option for remediation. The degree of metal complexation by organic acids depends on the type, concentration, metal type, pH and temperature. The influence of pH, temperature on the extraction efficiency of lead, zinc and copper was evaluated using Sodium citrate and sodium acetate buffers. Sodium citrate buffer was selected for the soil treatment. The soil was characterized for its pH, total metal content and the distribution of target heavy metals in soil fractions. Optimal conditions for Pb extraction with 0.5M citrate buffer was used to treat soil in batches and in columns, to evaluate their extraction efficiency and possible use for in-situ remediation. / Chitosan, a derivative of chitin is a versatile biopolymer with metal uptake capabilities. Due to the large amounts of chitosan required to treat heavily contaminated leachates, magnesium (Mg) and iron (Fe) metals granules were evaluated for stripping the heavy metals from solution before the use of chitosan at optimized conditions to effectively polish the soil washing. (Abstract shortened by UMI.)

Persistent organic pollutants and heavy metals are released into the environment through different anthropogenic processes. They are of concern because they tend to bioaccumulate in the food chain and show adverse health effects ranging from acute to chronic toxicity. These pollutants need therefore to be monitored to conserve the environment. Conventionally, samples are sent to a laboratory for analysis by standard techniques such as chromatography and spectroscopy. Although these conventional techniques display high accuracy and low detection limits, they are expensive, require the use of highly trained personnel and tedious sample preparation. In comparison, electrochemical methods such as biosensors are sensitive, low cost and simple to operate. In this thesis, the determination of selected persistent organic pollutants (polybrominated diphenyl ethers, polybrominated biphenyls and polychlorinated biphenyls) and heavy metals (Cd, Pb and Cu) was achieved by the use of amperometric inhibition biosensor based on horseradish peroxidase (HRP) immobilized on the surface of platinum-polyaniline modified electrode. Polyaniline (PANI) film was electrochemically deposited on the platinum electrode surface. The film was characterized by cyclic voltammetry and spectrometric techniques. The CV results proved that the PANI was electroactive and exhibited a fast reversible electrochemistry. Characteristic Ultraviolet–Visible and Fourier Transform Infrared features of the polymer film were identified. They revealed that PANI film synthesized in this study is the conductive emeraldine salt. Horseradish peroxidase based biosensor was constructed by electrostatic attachment of the enzyme onto Pt-PANI electrode surface. Spectrometric and cyclic voltammetric results indicated that the immobilized HRP retained its bioelectrocatalytic activity towards the reduction of hydrogen peroxide. The Pt/PANI/HRP biosensor showed a linear response over a concentration range of 0.05 to 3.17 mM with a detection limit of 36.8 nM. Apparent Michaelis- Menten constant ( app M K ) was calculated as 1.04 mM. This implied that the HRP biosensor had a high affinity for H2O2. Furthermore, the fabricated biosensor showed high sensitivity, good reproducibility, repeatability and long-term stability. The Pt/PANI/HRP biosensor was applied to the determination of selected persistent organic pollutants and heavy metals. The latter was found to inhibit the HRP enzyme’s activity. The percentage inhibition of the investigated persistent organic pollutants decreases in the following order: 2,2´4,4´,6-pentabrominated diphenyl ether> 2-brominated biphenyl> 2-chlorinated biphenyl> 2,2´,4,5,5´-pentachlorinated biphenyl> 2,4,4´-trichlorinated biphenyl. In the case of heavy metals, the degree of inhibition of heavy metals was highest for Cd2+, followed by Cu2+ and then Pb2+. Kinetic study for the amperometric response to H2O2, recorded in the absence and presence of persistent organic pollutants and heavy metals revealed that for polybrominated diphenyl ethers, the inhibition process corresponded to a competitive type whereas for polybrominated biphenyls, polychlorinated biphenyls and heavy metals, it corresponded to the on-competitive type. The biosensor exhibited high sensitivity towards the determination of the metals and persistent organic pollutants as pollutants in real water samples, namely tap water and landfill leachate samples. / Thesis (M.Sc.)-University of KwaZulu-Natal, Durban, 2010.

The research provides data of pH and conductivity, some anions (e. g. fluoride, chloride, bromide, nitrate, phosphate and sulphate), monovalent cations (e. g sodium, ammonium and potassium), divalent cations (e. g calcium and magnesium) heavy metals (e. g. iron, copper, zinc, nickel, cobalt, cadmium and manganese) and organic compounds – from water samples of rivers of Brunei Darussalam, namely, Brunei River, Belait River, Tutong River and Temburong River. The higher values of certain parameters with respect to the acceptable standard limits for river water indicate the pollution in river water samples of the study area, make the waters unsuitable for various applications and do pose a human health hazard. The pH levels in Brunei Darussalam is quite reassuring and mostly safe. Although there are some stretches of rivers that show slightly lower levels of pH, there is no cause for any alarm as these waterways are not sources of drinking water. As for anions and cations, the only anion of significant levels detected in Brunei Rivers is chloride whereas only monovalent cation detected in significant levels, is sodium. The concentrations of chloride and sodium ions are below the standard concentrations. Brunei Rivers are still free from chloride and sodium pollution. For heavy metals, only iron is detected in Brunei Rivers. Brunei being a oil based country experiments were done to identify levels of a numbers of significant toxic organic compounds, including, toluene and benzene which have been detected in the waters of the oil mining district of Belait District but are within normal limits. The use of a photolytic cell system to achieve the photodegradation of benzene, toluene, ethylenediaminetetra-acetic acid (EDTA) and the surfactant – hexadecyltrimethyl-ammonium bromide (C19H42NBr) is reported. The system has been optimised by investigating the effects of the addition of hydrogen peroxide (H202) as an oxidant and the addition of titanium dioxide (TiO2) as a catalyst. The results show that the photolytic system can be used to achieve >99% degradation of organic contaminants. The research also includes a final chapter on management system which covers water protection, pollution control and solid waste management in Brunei. In addition to investigating various factors of the solid waste management in Brunei, the researcher has also exposed some of the weaknesses that need immediate addressing. Various measures have been suggested to make Brunei's water more efficient. Moreover, ways of preserving the high quality of Brunei's water figures in this chapter.

This thesis reviews literature relating both to the treatment of metal rich wastewaters by the use of constructed wetlands and the use of slurry analytical procedures for the determination of heavy metals in environmental micro-samples. A survey of metal contaminated wetland sites showed that aquatic plants maintain low levels of metals in aerial parts despite some very elevated sediment metal concentrations and extreme acidity. A series of greenhouse trials investigated the uptake of metals into aerial sections of Typha, Phragmites and Equisetum in long term hydroponic experiments. Phragmites was shown to accumulate zinc to a higher level than Typha. The toxicity of zinc supplied in the nutrient solution at 5 mg.dm-3 over long periods was found to limit the viability of such non-sediment based systems. A reliable routine analytical procedure was developed along with a program of quality control for the study of metal uptake into aquatic plants. A micro sampling technique, eminently suited for the analysis of small plant sections was developed. This technique uses ozone to ash the plant samples at a low temperature and following suspension in a liquid medium provides a sample ready for slurry determinations by a variety of analytical instrumentation. It is proposed that this method may also be suitable for the determination of metals in individual invertebrates and other zoological micro-samples as well as potential applications in the medical field.

In 1995, the Environment Agency for England and Wales developed urban runoff treatment wetlands at two selected locations in Outer London. The systems have been monitored for a wide range of parameters including heavy metals, suspended solids and BOD over a period of two years. Seven storm events were also monitored. The ability of micro-organisms, isolated from the rhizosphere of wetland plants collected at both systems, to tolerate and accumulate heavy metals has also been investigated. This study has demonstrated that constructed wetland treatment systems are capable of reducing the pollutant loadings associated with urban runoff, and that such systems can be successfully established within urban areas. During dry weather, pollutant concentrations and loadings were typically low and associated removal efficiencies highly variable. However, during storm events, pollutant loadings increased and removal efficiencies improved, with mean removal efficiencies of 71% for Pb and 81% for Cr at the Dagenham wetland. An exception to this was for suspended solids which showed an overall increase of 99% during storm events. Several design and operational issues have been identified and addressed during the course of the monitoring programme, and recommendations for the improved design and operation of urban runoff treatment wetland systems have been made. A range of micro-organisms, isolated from both wetland systems, were able to tolerate elevated Zn and Pb concentrations. Two strains (Beauveria bassiana and Rhodotorula mucilaginosa) were selected for further work. Both strains could accumulate Zn and Pb, with B. bassiana showing a high capacity to bind Pb (maximum concentration of 136mgPb/g cells dry weight). Comparison of the growth of B. bassiana at 4°C and 30°C suggested that processes of microbial metal accumulation may occur throughout the year in treatment wetlands. The presence of Pb inside hyphae of B. bassiana, associated with hyphae walls and in the surrounding medium was confirmed. This study has found that micro-organisms isolated from urban runoff treatment wetlands can tolerate and accumulate Zn and Pb, and the application of these results to wetland treatment processes is discussed.

Plant-based remediation techniques that can address mixtures of heavy metals and organic contaminants in soil warrant investigation due to their cost effectiveness and public acceptability. The potential of phytoremediation to remediate mixtures of heavy metals and hydrocarbons in soil is presented in two papers. A hydropic screening of twenty-seven forage grasses, grown in a solution containing 100 muM Zn, 5 muM Cu and 1 muM Cd, provided six species that were exceptionally metal tolerant. These six species were examined for their growth response and root phenolic secretion at five levels of hydroponic heavy metal contamination. Phenolic secretion, an indicator of a plant's capacity to promote polycyclic aromatic hydrocarbon (PAH) degradation, increased with heavy metal contamination, however, the values were low (<30 mug/g root). Two high biomass producing, metal-tolerant grasses, Bromus riparius and Arrhenatherum elatius, were combined with M2Rhizo4, a strain of plant growth-promoting rhizobacteria. The plant-bacterial combinations were established in artificial and genuine soils contaminated with heavy metals and PAHs at a range of concentrations. In contaminant-free artificial soil, inoculation promoted B. riparius growth by 25% compared to non-inoculated plants. In artificial soil, contaminated with 495 mg/kg Zn, 263 mg/kg Cu and 23 mg/kg Cd, M2Rhizo4 promoted B. riparius growth by 22%. In chromated-copper-arsenate (CCA) and creosote contaminated soil, M2Rhizo4 inoculated A. elatius had 15% more biomass and greater survival rates than non-inoculated A. elatius. A phytoremediation system composed of metal-tolerant plants inoculated with hydrocarbon-degrading or plant growth promoting bacteria may be suitable for sites contaminated with a mixtures of hydrocarbons and heavy metals.

Thesis (Ph. D.)--University of Hawaii at Manoa, 1995. / Includes bibliographical references (leaves 171-187). / Microfiche. / xix, 187 leaves, bound ill. 29 cm

University of Technology, Sydney. Faculty of Science. / The suitability of the Sydney rock oyster (Saccostrea commercialis) as a monitor of heavy metal contamination in estuarine and coastal waters was assessed. Case study I examined the influence of body size (ie: soft tissue dry weight) on the tissue concentrations of Cu, Zn, and Fe. Sampling was replicated both spatially and temporally in order to determine whether the size-metal relationship for these elements varied with geographical location (ie: differing levels of environmental contamination) or season. All oysters were collected from 'wild' populations in the HawkesburyfNepean estuary. Least-squares regression analysis indicated that Cu concentrations were independent of body size at all times. Analysis of covariance (ANCOVA) showed that this relationship did not change with either geographical location or season. Size-metal relalionships for Zn indicated that concentrations for this element varied from being independent of size to being size-dependent with proportionally greater concentrations present in the larger individuals. Yet lests for homogeneily of slopes (ANCOVA) showed that no differences in regression coefficients occurred with geographical location or season. Iron concentrations were size-dependent with proportionally greater concentrations in the smaller individuals. ANCOVA revealed that homogeneity of slopes with geographical location occurred only on two of the four sampling occasions. Further examination of data revealed that the size·range of the individuals sampled may be important in determining size-metal relationship for iron. Case Study II examined the concentrations of Cu and Zn in S. commercialis deployed into the Georges River/Botany Bay and the Port Stephens estuaries. The influence of tissue assimilation/loss on metal concenlralions was also examined. Organisms of a homogenous genetic stock, of a similar size and age, and transplanted to a similar lidal height were utilized. As all organisms were of a similar size and age at the time of their deployment any differences in size during sampling were attributed to growth. Results indicated that tissue loss (ie: 'degrowth') not accompanied by a similar loss of metal resulted in an increase in metal concentrations. The assimilation of new tissue at a greater rate than metal accumulation (ie: 'dilution') resulted in decreased metal concentrations. From these relationships it was apparent that measures must be taken to reduce, account for, or eliminate the effects of growth in bivalve monitoring programs. Unless this problem is addressed, metal concentration values in S. commercialis are likely to give an inaccurate estimation of the level of environmenlal contamination and confound attempts to isolate pollution point sources.

This thesis presents the results of an investigation into the uptake and distribution of cadmium (Cd) in two cultivars of potato (Solanum tuberosum L.) shown to contain different concentrations of Cd in the tuber at maturity. An initial glasshouse trial sought to determine whether differences in tuber Cd between these two cultivars resulted from differences in uptake from the soil, or were due to differences in the allocation of Cd to the various tissues within the plant. Total uptake of Cd from the soil did not differ between cultivars, nor did the yield of tubers. However, there were marked differences in Cd distribution within the plant. Most of the differences in tuber Cd concentration could be accounted for by a large (3-fold) retention of Cd in the roots of cultivar Wilwash. The concentration of Cd in the shoots of Wilwash was also higher than of Kennebec, although to a lesser extent than the roots. Further studies were conducted to trace the pathways of Cd uptake and movement within the plant. A split-pot trial, involving long-term growth of potatoes in 109Cd-labelled soil, was undertaken to determine the overall pattern of Cd distribution and the importance of the root system in supplying Cd to the tubers. The root system of the potato plant is different to many plants, in that the main root system (basal roots) is augmented after tuber initiation by roots extending from the stolon and from the tuber itself. The basal roots were found to be the dominant source of Cd to all tissues and accounted for approximately 85 % of tuber Cd. The remaining tuber Cd was sourced directly from the stolon and tuber roots. However, there was no evidence of a direct link between the main (basal) root system and the stolons. Although Cd was found to accumulate in the periderm of the tubers, there was no uptake into the tuber tissue itself. Isotopic studies were undertaken to investigate the short-term movement of newly absorbed Cd in the xylem and the phloem. Cadmium was found to be highly mobile in both the xylem and phloem, with added Cd being rapidly assimilated into all tissues following both root and foliar application. Newly absorbed Cd was rapidly sequestered by the stems when applied to either the soil or to a source leaf, suggesting that the stems may act as a transitional storage pool when rapid turnover of nutrients and other mineral elements is required during tuber bulking. Inhibition of Cd uptake by zinc (Zn), has been proposed as a method for reducing the concentration of Cd in various agricultural crops, including potatoes. The ability of Zn to reduce Cd uptake was found to be highly dependent upon cultivar and on the concentration of Cd in the external medium. Although competition between Zn and Cd was found for cultivar Wilwash when the external concentration of Cd was low, when the concentration of Cd in the external media was high, increasing Zn served to increase Cd uptake. Both synergistic and competitive responses were also noted for cultivar Kennebec. However, the patterns of response were opposite to those evident in Wilwash. The complexity of these interactions highlighted the possible shortcomings in using soil applied Zn to limit Cd uptake by potatoes. / Thesis (Ph.D.) -- University of Adelaide, School of Earth and Environmental Sciences, 2004.

This thesis presents the results of an investigation into the uptake and distribution of cadmium (Cd) in two cultivars of potato (Solanum tuberosum L.) shown to contain different concentrations of Cd in the tuber at maturity. An initial glasshouse trial sought to determine whether differences in tuber Cd between these two cultivars resulted from differences in uptake from the soil, or were due to differences in the allocation of Cd to the various tissues within the plant. Total uptake of Cd from the soil did not differ between cultivars, nor did the yield of tubers. However, there were marked differences in Cd distribution within the plant. Most of the differences in tuber Cd concentration could be accounted for by a large (3-fold) retention of Cd in the roots of cultivar Wilwash. The concentration of Cd in the shoots of Wilwash was also higher than of Kennebec, although to a lesser extent than the roots. Further studies were conducted to trace the pathways of Cd uptake and movement within the plant. A split-pot trial, involving long-term growth of potatoes in 109Cd-labelled soil, was undertaken to determine the overall pattern of Cd distribution and the importance of the root system in supplying Cd to the tubers. The root system of the potato plant is different to many plants, in that the main root system (basal roots) is augmented after tuber initiation by roots extending from the stolon and from the tuber itself. The basal roots were found to be the dominant source of Cd to all tissues and accounted for approximately 85 % of tuber Cd. The remaining tuber Cd was sourced directly from the stolon and tuber roots. However, there was no evidence of a direct link between the main (basal) root system and the stolons. Although Cd was found to accumulate in the periderm of the tubers, there was no uptake into the tuber tissue itself. Isotopic studies were undertaken to investigate the short-term movement of newly absorbed Cd in the xylem and the phloem. Cadmium was found to be highly mobile in both the xylem and phloem, with added Cd being rapidly assimilated into all tissues following both root and foliar application. Newly absorbed Cd was rapidly sequestered by the stems when applied to either the soil or to a source leaf, suggesting that the stems may act as a transitional storage pool when rapid turnover of nutrients and other mineral elements is required during tuber bulking. Inhibition of Cd uptake by zinc (Zn), has been proposed as a method for reducing the concentration of Cd in various agricultural crops, including potatoes. The ability of Zn to reduce Cd uptake was found to be highly dependent upon cultivar and on the concentration of Cd in the external medium. Although competition between Zn and Cd was found for cultivar Wilwash when the external concentration of Cd was low, when the concentration of Cd in the external media was high, increasing Zn served to increase Cd uptake. Both synergistic and competitive responses were also noted for cultivar Kennebec. However, the patterns of response were opposite to those evident in Wilwash. The complexity of these interactions highlighted the possible shortcomings in using soil applied Zn to limit Cd uptake by potatoes. / Thesis (Ph.D.) -- University of Adelaide, School of Earth and Environmental Sciences, 2004.