Abandoned metal mines in the Tamar catchment, south west England, represent a significant threat to surface water quality via generation of acid mine waters. Currently the River Tamar fails environmental quality standards (EQS) established under the Water Framework Directive (2000/60/EC) for dissolved Cu (x ̅ = 0.19 ± 0.05 μmol L-1) and Zn (x ̅ = 0.19 ± 0.06 μmol L-1, both 1997-2007) downstream of historic mining area of Gunnislake. The aim of this study was to quantify the risk to surface water quality by diffuse drainage generated by mine waste tips. For the first time, a GIS model was compiled and used to generate a priority list of known areas of mine waste, based on physical and environmental factors. The methodology was consistent with European guidance documentation published to meet the requirements of the Mining Waste Directive (2001/21/EC) and has since been applied, in a modified form, to other catchments in south west England. Two study sites, with contrasting mineralogy and hydrology, scored highly in the model and were the subject of field investigations from 2007-2009. These were Devon Great Consols (DGC), an abandoned Cu-As mine near Gunnislake and Wheal Betsy (WB), an abandoned Pb-Ag mine, near Mary Tavy. At each site, surface waters and shallow groundwaters were sampled and analysed for dissolved metals (including Al, Cu, Zn, Mn, Pb, Ni, and Cd), metalloids (As, Sb), major ions and anions. Samples of four selected mine waste tips were also gathered and subjected to a range of laboratory leaching experiments including the novel application of a dynamic upflow percolation test, based on an existing European method (CEN TS 14405). Leachates generated by the waste tips in the field were highly variable and elevated with respect to EQS for Al (up to 1850 μmol L-1), Cu (570 μmol L-1), Zn (34 μmol L-1), Ni (3.8 μmol L-1), Cd (0.17 μmol L-1), Mn (216 μmol L-1), Fe(537 μmol L-1) , As (380 μmol L-1) and Sb (5.4 μmol L-1). Estimated annual fluxes of dissolved metals were predicted using average rainfall data and catchment areas calculated in ArcHydro9 to estimate the annual discharge of waters from the tip. These calculations showed annual contaminant flux from the tips to exceed, or be of the same order of magnitude to, major adit discharges in the catchment (e.g. Cu 50900-66900 mol y-1 at DGC and 470 mol y-1 Cd at WB) and represented a significant contributor to metal flux in the Tamar catchment. Primary sulphide minerals in the waste were generally highly altered and metals (Pb, Cu, Zn, and Mn) and As were found to be strongly associated with secondary iron minerals, precipitated under oxic conditions. In finer wastes, sorption to clay minerals was also found to be very important for the retention of dissolved metals, particularly Pb. Concentrations of contaminants in column field leachates were similar for most metals (Cu, Zn, Mn, Ni and Cd) and may provide a useful tool for prediction of leachate composition. However, sorption and release of metals and As to the secondary phases and clays were highly sensitive to pH change and where laboratory experiments did not replicate field pH, discrepancies between in situ and laboratory results were observed up to two orders of magnitude in scale (particularly for As and Pb).

Agricultural nonpoint source pollution is recognised as a major cause of water pollution. The characteristics of nonpoint source pollution suggest that an efficient approach should focus on a source control and hence land-use management. Recently, the concept of Payments for Ecosystem Services (PES) has been advanced as an efficient market-based approach to protect in-stream water quality, while simultaneously supporting agriculture. Farmers can be rewarded for the adoption of certain ‘Best Management Practices’ (BMPs) in farming systems. But little is known about the adoption of BMPs in the context of Thai agriculture. This thesis examines the adoption of twelve BMPs on citrus farms in the Ping river basin in northern Thailand. In the context of potential PES development, three studies were undertaken using frameworks from economics and psychology. The first study used a bottom-up engineering approach to estimate economic costs of twelve BMPs at the farm-scale. The total annualised costs, including installation, maintenance, and land opportunity costs of each BMP were compared. The results indicated that land opportunity cost was the largest proportion of total costs. These estimates provided a basis for discussion on how the farmers’ perception of cost may influence their stated adoption intention. The second study used the Theory of Planned Behaviour (TPB), to investigate farmers’ intentions on adoption of twelve BMPs. A survey of 218 citrus farmers was undertaken in the application. Descriptive statistics and frequency of BMP selection were presented. The results showed that soil analysis was the most preferred BMP. A graphical analysis of other preferred measures suggested that these were not always consistent with the known cost information derived (above) and thus farmers’ perceived costs might not be the most important factor influencing adoption decisions. Further analysis based on TPB investigated other factors thought to be significant in farmers’ decision-making. Other potential external and psychological factors influencing adoption were investigated using a multinomial logistic model. The results indicated that the probability of adopting BMPs was associated with other psychological factors and external factors, rather than perceived costs. The significant psychological factors were farmers’ attitudes towards consumers and perception about farm returns, while the significant external factors were, for example, access to information and contribution of family labour to farm workload. The third study was based on the application of Q-Methodology, and aimed to obtain a deeper understanding of farmers’ perception towards BMPs. Seventy two participants were purposively selected from the 218 TPB observations. The results revealed four distinctive farmer groups holding different perceptions towards BMPs. The four groups were conservationist, traditionalist, disinterested, and risk-averse. These provided a specific segmentation to guide policy towards influencing attitudes and behaviours. The results suggested that farmers were not motivated solely by a profit maximisation goal. Overall, key findings from these three studies revealed some fundamental requirements for developing a water-related PES programme. These were: i) factors affecting eligibility to participate; ii) factors affecting desire to participate; and iii) factors affecting ability to participate. This information provided the basis for a set of recommendations addressing the development of the water-related PES programme in the Ping river basin.

Farmyard runoff, i.e. the effluent generated by the rain falling over farmyards, tracks and roofs, is a significant and overlooked source of nutrients and pathogens which degrades aquatic ecosystems through eutrophication, siltation and wildlife poisoning, raises public health concerns, and incurs considerable costs for society. Among other Best Management Practices implemented to address agricultural water pollution and help achieve compliance with the Water Framework Directive, Constructed Farm Wetlands (CFWs), i.e. shallow surface flow wetlands comprising several vegetated cells in series, are being recommended for remediation of farmyard runoff, due to their capacity to remove or store pollutants. Investigation is therefore needed of their long-term water treatment efficiency and ecological value to optimize their design and cost-effectiveness and minimize their negative externalities. The main aims of this study were to: 1) evaluate the treatment performance of CFWs and the link between design, hydrology and efficiency; 2) assess their ecological value and the influence of water quality and design on wetland ecology; 3) identify their costs, benefits and the way they are perceived by farmers; and 4) inform guidelines for the design, construction and aftercare of sustainable CFWs. Research focused on two CFWs in south-east Scotland, one at a dairy farm and one at a mixed beef-arable farm, which receive runoff from yards and roofs, field drainage and septic tank overflow. From February 2006 to June 2008, rainfall, evaporation, water levels and flow at the CFWs were monitored, and their treatment efficiency was assessed from water samples collected manually regularly or with automatic samplers during storm events, and analysed using standard methods. In addition, their ecological value was assessed twice a year from vegetation and aquatic macroinvertebrate surveys. Finally, semi-structured interviews with eight farmers and a farm advisor and discussions with three CFW designers in Scotland and Ireland allowed collection of technical and economic data on farm practices, CFW construction and maintenance, and helped assess CFW cost-effectiveness and acceptance by farmers. Both CFWs reduced pollutant concentrations between inlet and outlet, with efficiencies at CFW1 and CFW2 respectively of 87% and < 0% for five-day biochemical oxygen demand, 86% and 83% for suspended solids, 68% and 26% for nitrate/nitrite, 42% and 34% for ammonium, and 12% and 31% for reactive phosphorus. Nevertheless, the concentration of all pollutants at the outlet of CFW1, and concentration of nitrate/nitrite at the outlet of CFW2 frequently exceeded river water quality standards. Water treatment efficiency varied seasonally, being significantly lower in winter, mainly due to lower temperatures, increased volume of inputs and reduced residence time. The ecological value of the two CFWs differed greatly. At CFW1 and CFW2 respectively, 14 and 22 wetland plant species and 24 and 46 aquatic macroinvertebrate species (belonging to 13 and 27 BMWP scoring families respectively) were recorded, illustrating the greater biodiversity conservation value of CFW2, which was one year older, larger, cleaner, comprised several ponds with a combination of open water and densely vegetated areas, and was subsequently more structurally diverse. The socio-economic study revealed that, despite significant costs associated with their construction (£20 000-£50 000 ha-1) and maintenance (£900-£1500 ha-1 yr-1), CFWs may still represent a more cost-effective alternative than conventional methods. However, their adoption, implementation and sustainable use by farmers were conditioned by land availability and suitability, existing farm infrastructure, detailed information on limitations and maintenance requirements, and adequate financial support for both construction and aftercare. To ensure a long-term, consistent and efficient water treatment, and to enhance biodiversity and landscape, well-maintained, large, vegetated, multi-cell CFWs with shallow overflows are recommended. Their size should be adapted to local precipitation patterns and catchment characteristics. Keywords: agriculture, best management practice (BMP), biodiversity, constructed farm wetland (CFW), costs, farmyard runoff, water pollution, water treatment.

Constructed wetlands are considered an inefficient technology for long-term phosphorus (P) removal. The P retention effectiveness of subsurface wetlands can be improved by using appropriate substrates. The objectives of this study were to: (i) use sorption isotherms to estimate the P sorption capacity of the two materials, masonry sand and light weight expanded shale; (ii) describe dissolved P removal in small (2.7 m3) subsurface flow wetlands; (iii) quantify the forms of P retained by the substrates in the pilot cells; and (iv) use resulting data to assess the technical and economic feasibility of the most promising system to remove P. The P sorption capacity of masonry sand and expanded shale, as determined with Langmuir isotherms, was 60 mg/kg and 971 mg/kg respectively. In the pilot cells receiving secondarily treated wastewater, cells containing expanded shale retained a greater proportion of the incoming P (50.8 percent) than cells containing masonry sand (14.5 percent). After a year of operation, samples were analyzed for total P (TP) and total inorganic P (TIP). Subsamples were fractionated into labile-P, Fe+Al-bound P, humic-P, Ca+Mg-bound P, and residual-P. Means and standard deviations of TP retained by the expanded shale and masonry sand were 349 + 169 and 11.9 + 18.6 mg/kg respectively. The largest forms of P retained by the expanded shale pilot cells were Fe+Al- bound P (108 mg/kg), followed by labile-P (46.7 mg/kg) and humic-P (39.8). Increases in the P forms of masonry sand were greatest in labile-P (7.5 mg/kg). The cost of an expanded shale wetland is within the range of costs conventional technologies for P removal. Accurate cost comparisons are dependent upon expansion capacity of the system under consideration. Materials with a high P sorption capacity also have potential for enhancing P removal in other constructed wetland applications such as stormwater wetlands and wetlands for treating agricultural runoff.

No description available.

Submitted in fulfillment of the academic requirements for the Degree of Master of Technology: Biotechnology, Durban Institute of Technology, 2005. / The cumulative effects of pollution have led to increased public concern, which is resulting in strict legislation on the discharge of wastes in whatever state they are present, i.e. solid, liquid or gas. Currently, in South Africa, effluents with a high organic load are sent to landfills or marine outfall because the cost of discharge to sewer is prohibitive. In regions where there is a net surplus of rainfall, landfill sites have the potential to pollute the groundwater due to saturated soil conditions. Therefore, many landfill sites should not receive liquid effluents. If liquid wastes are disposed onto landfills, then an alternate sink is required for the treatment of the high volumes of leachate that are generated. These concentrated effluents could then be treated by biological, chemical or physical methods to reduce the pollution load in the natural water resources. In this study, anaerobic digestion has been identified as one of the biological processes that can be applied to treat high-strength or toxic organic liquid effluents, since a survey conducted by Sacks (1997) indicated that many anaerobic digesters in the KwaZulu-Natal region have spare capacity. However before high strength industrial wastes can be treated in existing anaerobic digesters, their impact on the digestion process, i.e. their toxicity and biodegradability under anaerobic conditions, needs to be determined. During this project, several high-strength or toxic industrial effluents were tested to assess their toxicity and biodegradability under anaerobic conditions. These include three synthetic textile size effluents from the textile industry (Textile effluent 1, 2, and 3) and three hazardous landfillieachates (Holfontein, Shongweni and Aloes). In addition, the components of a textile effluent, i.e., starch and wax, were tested to determine which / M

Ph.D. / Except for agriculture, the mining industry is considered as not only the oldest but also the most important industry. Mining involves the removal of minerals from the earth's crust for usage by mankind. The disturbance during mining activities such as mining effluent has an effect on the natural aquatic environment. In any freshwater environment, the macroinvertebrates form a vital link between the abiotic envinronment and the organisms in higher trophic levels. It is thus true that specific environmental contaminants, such as mining effluent, may directly affect the survival of macorinvertebrates. The density and diversity of macroinvertebrates is in a direct relation with the water quality. For the purpose of this study, attention was given to the effects of gold and coal mine effluent on the macroinvertebrate fauna, as well as to the determination of metal accumulation from the water through the macroinvertabrates to fish. At Case Study Mine One, with an open water system, acidic conditions of the water caused a reduction in the number and diversity of macroinvertebrates. A closed water system, characteristic of Case Study Mine Two, presented a slightly more abudandant macroinvertebrate population than with the previous mine. The results lead one to conclude that the surface water in this study area is of a better quality. Case Study Mine Three had a complex water circuit and presented a greater number and diversity of macroinvertebrates, with the best water quality of the three mines investigated.

Submitted in fulfillment of the requirements for the degree of Doctorate of Technology: Biotechnology, Durban University of Technology, Durban, South Africa, 2014. / All over the world concerns have been raised over the possible adverse effects that may occur when exposed to chemicals that have the potential to interfere and affect the endocrine system. The concern is directed at both humans and wildlife. There is still a lack of public awareness regarding Endocrine Disrupting Chemicals (EDCs) and the harmful effects on humans and wildlife. It has only been within the last decade that South Africa began the actual task for proper management and control for water and wastewater quality. There are many ways to detect these EDCs all of which are very laborious and most of the cases these EDCs are either in the pico or nano gram per litre range, too minute for many methods to detect effectively; so therefore the research project aimed to use rapid and sensitive techniques to determine the quickest means to detect the very low concentrations of theses EDCs. Two techniques were researched, i.e., Enzyme Linked immunoassays (ELISAs) and Radio-immunoassays (RIAs). The research study thus assessed the solid phase extraction (SPE) technique for total recovery of hormones; the ELISA and RIA techniques for rapid detection of natural (estrone (E1), estradiol (E2) and estriol (E3) and synthetic ethinylestradiol (EE2) by validating the precision and reproducibility . These techniques were then applied to determine hormone EDC removal first at laboratory scale investigations and then applied to full scale wastewater treatment plants (WWTP) with different configurations in order to deduce removal efficiency of each type of plant. The next phase assessed the toxicity of individual and combined estrogen standards as well as the toxicity in the WWTPs and classify and to determine if there was a correlation between hormone concentration and toxicity in final effluents. The assessment of the SPE and the immunoassay procedures (ELISA AND RIA) using standards and controls found that both these assays can be utilised to quantify hormone estrogens in wastewater. The small sample volume required reduced the labour time and application of the procedure made it cost effective and reliable techniques. The intra-assay and inter-assay validation procedures as well as the standard recoveries confirmed reproducibility and precision of the immunoassays. The % CV were <10% for both the intra-assay and inter-assay validations. The laboratory scale investigations included the operation of a modified Ludzak-Ettinger (MLE) process which enabled control and manipulation over the operational parameters in order to establish how certain parameters influenced the removal of hormone EDCs. One such parameter that was manipulated was the sludge retention time (SRT). The MLE tests showed that the SRTs definitely have an effect on the removal of hormones from the influent as well as the overall performance of sewage treatment. The 10 day SRT proved that longer SRTs will definitely aid in the removal of hormones and possibly other EDCs in raw sewage. During the 10 day SRT the influent hormone concentrations (E1: 59.11 ng/L, E2: 61.40 ng/L) were almost double than the influent hormone concentrations (E1: 26.46 ng/L, E2: 27.60 ng/L) during the 5 day SRT, which impacted on the removal efficiency. The 5 day SRT had an overall average E2 and E1 removal of 78.11% and 81.71% respectively while the 10 day SRT had average E2 and E1 removal of 91.24 % and 80.56% respectively. The 24 hour batch test provided evidence of the reversible metabolism of the E2 hormone. This was seen by the rapid decrease of E2 and the rapid increase of E1 in less than 3 hours, which proved that E2 can be metabolized in to E1. An average reduction of 94.44% of E2 was seen after 5 hours and after 10 hours was no longer detected. After 13 hours E1 could no longer be detected. This finding also provided clarity as to the lower percentage removal of E1 during the 10 day SRT of the MLE process. The Vibrio fischeri biotox method implemented was the most economic and easiest way to conduct the toxicity tests. The validation of the test used a 52.9 mg/L K2Cr2O7 standard which provided a Cr (VI) concentration of 18.7 mg/L in the final test suspension which is the theoretical effective concentration causing 50% inhibition (EC50). This specific concentration of the Cr (VI) exhibited an EC50 at 20.08 mg/L. The toxicity investigations of the individual and mixed hormone standards revealed that at the 10 ng/L concentration the individual E2 standard had the highest percentage inhibition (%INH) of 45.99% after the 30 minute contact time (T30), and when this standard was further diluted to 5 and 1 ng/L also showed higher % INH (26.04 and 23.66 %INH, respectively) than the individual EE2 standard (21.92 %INH) at 10 ng/L. . According to the toxicity classification system and after interpretation of the data, all the hormone standards were classified as Class II as they all exhibited slight acute toxicity. The 10 ng/L E2 standard had Toxicity Units (TU) of 0.8 which was close to the Class III level; however when it was in a mixture with E1 and E3, the TU was much lower (0.6 TU). The synthetic EE2 hormone also showed slight acute toxicity and had the lowest TU of 0.4. The application of the above mentioned techniques to full scale WWTPs with different configurations showed different removal efficiencies. The WWTPs ranged from the most primary consisting of just oxidation ponds to biological trickling filters, to biological nutrient removal (BNR) to conventional activated sludge (AS) plants. Removal rates ranged from 29% to 96% for E2, 0% to 89% for E1 and 0% to 100% for EE2. The overall ranking of the WWTPs from the most efficient to least efficient in terms of hormone removal were as follows: Plant E (91%) = Plant D (before UF) (91%) > Plant B (east side) (88%) > Plant B (west side) (77%) > Plant C (east side) (71%) > Plant D (after UF) (57%) > Plant A (56%) > Plant C (west side) (12%). Using the Vibrio fischeri method to evaluate the reduction of toxicity in WWTPs C, D and E proved effective. It was seen immediately after secondary biological treatment in the clarifier effluent the toxicity was reduced. Plants C, D and E had reduced the toxicities by 100, 80 and 97 % immediately after secondary biological treatment, while after the addition of the Chlorine disinfectant in the final stage of treatment the toxicity increased having %INH of 99.9, 15.7 and 99.9 respectively. In conclusion the SPE can be used as an extraction procedure for hormones in wastewater and the immunoassays can be used as rapid techniques for quantification of hormone EDCs in wastewater. The ELISA technique proved to be the slightly superior to the RIA in terms of facilities required. The laboratory scale procedures proved that some hormones can be oxidised to other hormones and therefore longer sludge retention times may be required to improve the removal. The study of the different WWTPs configuration showed that plant configuration and operational parameters impact the removal of hormone EDCs. The composition of the influent received by the plant also has an effect on the removal, i.e., whether it’s industrial, domestic or a mixture of both. Results concluded that plants which have either mixing and/or aeration with activated sludge and longer SRTs of more than 10 days have a higher rate of hormone removal than those plants with shorter SRTs and that the activated sludge processes were capable of reducing the toxicity of the influent. Overall results indicated that hormone EDCs are indeed being discharged with the effluents from WWTPs in South Africa. However whether the concentrations left in the final effluents will still have an adverse effect on the aquatic life is a question that still remains unanswered. The aquatic ecosystems are inevitably being polluted with these EDCs and their breakdown products. / D

Acclimation temperature had a significant effect on the lethality of copper to fathead minnows in replicated 96-hour lethality tests. Lowest median lethal copper concentrations (LC50) were recorded at 12 and 22°C, with LC50s at 5 and 32°C at least 140 μg/1 higher. This research found LC50 copper concentrations in the 300 to 500 μg/1 range and a polynomial relationship between LC50s and acclimation temperature. Following a 24-hour exposure to three sublethal concentrations of copper, critical thermal maxima (CTMax) were tested in minnows acclimated to four temperatures. Sublethal exposure to copper significantly decreased the CTMaxs relative to controls at three of the four temperatures. Control CTMaxs ranged from 28.6 to 40.4°C and increased 0.46°C for each 1°C increase in acclimation temperature.

Three suspended solids types containing a range of physicochemical characteristics were used to determine the effect of suspended solids on the bioavailability of acenaphthene, 1,2,4,5-tetrachlorobenzene, zinc, and chlordane to Daphnia magna and Pimephales promelas. Generally, the bioavailability of zinc and chlordane decreased due to interactions with all suspended solids types while bioavailability of acenaphthene and 1,2,4,5-tetrachlorobenzene were not clearly reduced. Partition coefficients and slope of dose-response curves related chemical characteristics and organism sensitivity, respectively, to experimentally determined results. It is believed that the biologically available form of these chemicals to Daphnia magna and Pimephales promelas resides in the aqueous phase.