The efficiency of wastewater treatment systems is commonly measured by the reductions of parameters such as biological oxygen demand (BOD), chemical oxygen demand (COD) and total suspended solids (TSS) and/or reductions in levels of selected macro compounds (e.g. long-chained hydrocarbons and inorganic compounds). Less attention has generally been paid to micropollutants with high potential toxic effects, such as polycyclic aromatic compounds (PACs), including unsubstituted and alkylated polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes, polychlorinated biphenyls (PCBs), human pharmaceuticals and by-products formed during the treatment process. These organic micropollutants occur in wastewaters at trace and ultra-trace levels, therefore their detection requires advanced, costly analyses and large sample volumes. Furthermore, concentrations of micropollutants can fluctuate widely both diurnally and between days. Thus, in order to understand the fate of micropollutants in wastewaters there is a need to develop sampling techniques that allow representative samples to be readily collected. In the work underlying this thesis two types of diffusive passive samplers, semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs), were used to monitor non-polar and polar organic micropollutants in wastewaters subjected to various treatment processes. The pollutants sequestered in these samplers represent micropollutants in the dissolved phase that are available for aquatic organisms. Further, since they collect pollutants in an integrative manner, i.e. they sample continuously during the selected exposure time (usually approx. one to ca. three weeks), the results provide time-weighted average (TWA) concentrations. In addition, the effects of various environmental factors on the uptake of analyzed micropollutants in POCISs and SPMDs were investigated using laboratory calibration and in situ calibration with performance reference compounds (PRCs). The results confirm that SPMDs are good sampling tools for investigating the efficacy of wastewater treatment processes for removing non-polar PACs and PCBs, and the effects of varying the process settings. In addition, analyses of process streams in municipal sewage treatment plants demonstrated that conventional sewage treatment processes are not optimized for removing dissolved four-ringed PAHs, some of the five-ringed PAHs, and tri- to hexa-chlorinated biphenyls. The removal of bioavailable PACs was enhanced by adding sorbents with high sorption capacities to the sludge used in the activated sludge treatment step, and a biologically activated carbon system was designed that robustly removed bioavailable PACs, with removal efficiencies of 96.9-99.7 percent across the tested ranges of five varied process parameters. In situ SPMD calibration data acquired show that uptake of PACs, described by SPMD sampling rates (Rs), were four to eight times higher than published laboratory calibrated Rs values, mainly due to strong (bio)fouling and turbulence effects. In addition, the laboratory calibration study demonstrated that temperature affects the POCIS uptake of pharmaceuticals. The uptake of four pharmaceuticals was higher, by 10-56 percent, at 18 °C compared to 5 °C. For two of the pharmaceuticals our data indicate that the uptake was lower by 18-25 percent at 18 °C. Our results also indicate that uptake of the studied pharmaceuticals was in the linear phase throughout the 35 day exposure period at both temperatures. Finally, calibration studies enabled aqueous concentrations of micropollutants to be more accurately estimated from amounts collected in the passive samplers.

Pavement markings are vital for safely navigating roadways. The nighttime visibility of pavement markings is enhanced by addition of retroreflective glass beads, most of which are made from recycled glass. Concern has been raised over the presence of heavy metals in glass beads used in pavement markings and their effect on human and environmental health. Based upon the potential risk associated with the presence of arsenic and lead in the glass beads, two Bills are currently being considered before the 112th Congress of the United States of America seeking to set a maximum permissible limit for the amount of arsenic and lead in glass beads used within pavement marking systems on domestic roadways. This study was designed to support legislative decision making by providing data necessary for risk assessment. The experiments carried out provide: an analysis of glass bead metal content and extractability; an evaluation of the relationship between arsenic content of the glass beads and their retroreflective performance; an evaluation of analytical methods used to measure the total bead metal content; and an analysis of samples of glass bead and soil mixture from a glass bead storage site used to determine site-specific metal concentrations in the soil media. Mean arsenic content, measured using the Pacific Northwest National Laboratory's KOH fusion digestion, in all the glass beads examined ranged from 11 ppm to 82 ppm, while mean lead content, measured using KOH fusion digestion, ranged from below quantification limit to 199 ppm. Total metal content measurements indicated a high amount of variability in the glass bead samples; most likely associated with the use of recycled glass feed during manufacturing. The relationship between the retroreflective performance and the arsenic content of the glass beads was analyzed and a weak but positive correlation was observed between the two factors. However, a more detailed study is required to evaluate the relationship between arsenic content and retroreflectivity. Different methods to evaluate the total metal content in glass beads were compared; it is recommended that any analytical method may be used, as long as the standard reference material is reproduced within the range of concentration expected in the glass beads. In the analysis of the field site samples of soil containing glass beads obtained from a glass bead storage and transfer facility, the mass content of beads in the soil varied from a mean of 19% to 78% depending on the location within the facility. However, a detailed analysis with larger number of samples must be performed to evaluate the effect of glass beads on the total arsenic content of the soil.

The continuity of the menace of mercury (Hg) is due to the continuous production and use of Hg and Hg containing products. Toxicity is just an outfall of use and exposure. Anthropogenic activities such as coal combustion and artisanal and small-scale gold mining have led to increasing Hg contamination and is the major source of Hg pollution into the environment that needs to be remediated. This study aimed to assess the phytoextraction capability of sweet sorghum (Sorghum bicolor) under different fertiliser treatments in Hg-contaminated soil. The potted experiment in a controlled environment included control S. bicolor and three phytoremediation treatments, i.e., Hg only; the addition of 4:1 green compost and; the addition of 0.2% NPK fertiliser. There were conspicuous signs of Hg phytotoxicity in plants with Hg only, namely wilting, senescent, inhibition of growth, and photosynthesis. There was stunted growth, but healthy plants observed in the treatment with the addition of green compost towards the end (day 60) of exposure. However, S. bicolor grew well until the last day of exposure in the treatment with the addition of 0.2% NPK fertiliser. Thus, this treatment showed the most effective phytoextraction potential of S. bicolor in Hg-contaminated soil. The effectiveness of S. bicolor in reducing the level of mercury was best assessed in the Hg bioavailable concentration in the spiked soil in which the Hg + NPK treatment has the lowest (0.77 mg kg−1). That resulted in the highest uptake (84.31%) percentage of Hg concentration recorded in the treatment with the addition of 0.2% NPK fertiliser compared to the other two treatments. The results suggest that the proportion of phosphate in the NPK fertiliser used, plays a huge role in the phytoextraction of Hg in the contaminated soil by S. bicolor. The Translocation Factor (TF) and Bioconcentration Factor (BCF), although higher within Days 20 and 40, was greater than 1 at the end of the exposure period suggesting a high probability that Hg was significantly transferred to the aerial parts of the plants. This is regarded as typical hyperaccumulator plant species. While S. bicolor was able to reduce the level of Hg in all three treatments, Hg + NPK treatment gave overall best results in physiological growth, the uptake, and reducing the level of Hg bioavailable in the spiked soil in terms of the effectiveness of phytoremediation method. / Environmental Sciences / M. Sc. (Environmental Science)