Photoelectrocatalytic degradation of 4-chlorophenol and oxalic acid on titanium dioxide electrodes

Photocatalytically active thin TiO(2) films were produced by spin-coating or dip-coating an alkoxy precursor onto a transparent conducting electrode substrate and by thermal oxidation of titanium metal. The thin films were used to study the photoelectrocatalytic or photoelectrochemical degradation of oxalic acid and 4-chlorophenol (4-CP) under near UV (monochromatic, 365 nm) light irradiation. Degradation was monitored by a variety of methods. In the course of oxalic acid degradation, CO(2) formation accounted for up to 100% of the total organic carbon degradation for medium starting concentrations; for the degradation of 4-CP, less CO(2) was detected due to the higher number of oxidation steps, i.e. intermediates. Incident-photon-to-current conversion efficiency, educt degradation and product formation as well as Faradaic efficiencies were calculated for the degradation experiments. Quantum yields and Faradaic efficiencies were found to be strongly dependent on concentration, with maximum values (quantum yield) around 1 for the highest concentrations of oxalic acid.     

Methane oxidation in two Swedish landfill covers measured with carbon-13 to carbon-12 isotope ratios

The release of methane (CH4) from landfills to the atmosphere and the oxidation of CH4 in the cover soils were quantified with static chambers and a 13C-isotope technique on two landfills in Sweden. One of the landfills had been closed and covered 17 years before this investigation while the other was recently covered. On both landfills, the tops of the landfills were compared with the sloping parts in the summer and winter. Emitted CH4, captured in chambers, was significantly enriched in 13C during summer compared with winter (P < 0.0001), and was enriched relative to anaerobic-zone methane. The difference between emitted and anaerobic zone delta 13C-CH4 was used to estimate soil methane oxidation. In summer, these differences ranged from 9 to 26@1000, and CH4 oxidation was estimated to be between 41 and 50% of the produced CH4 in the new landfill, and between 60 and 94% in the old landfill. In winter, when soil temperature was below 0 degree C, no difference in delta 13C was observed between emitted and anaerobic-zone CH4, suggesting that there was no soil oxidation. The temperature effect shown in this experiment suggests that there may be both seasonal and latitudinal differences in the importance of landfill CH4 oxidation. Finally the isotopic fractionation factor (alpha) varied from 1.023 to 1.038 and was temperature dependent, increasing at colder temperatures. Methanotrophic bacteria appeared to have high growth efficiencies and the majority of the methane consumed in incubations did not result in immediate CO2 production.     

Bioavailability of biosolids molybdenum to soybean grain

Legumes grown in biosolids-amended soils and then fed to ruminants can represent problematic sources of molybdenum (Mo), but few field data are available to quantify the risk. We used a set of fields amended to high cumulative biosolids Mo loads (>18 kg ha(-1)) over 27 yr to generate additional data. Soybean [Glycine max (L.) Merr.] was grown on 29 fields (pH values>6.8) amended to a wide range of soil Mo loads. Soybean grain harvested from each field was analyzed for Mo and the concentrations regressed against soil Mo loads estimated from actual soil Mo concentrations in the 0- to 15-cm depth. Slopes of such linear regressions represent uptake coefficients (UC values) used by the USEPA to assess risk of biosolids Mo to ruminants fed forage grown on biosolids-amended land. The UC value for all 29 fields was estimated as 1.66, which agrees with the few soybean grain data in the literature. The UC value, however, is well below a conservative UC value of 4, recently recommended for all fresh legume materials fed to cattle. Soybean grain can contain high concentrations of Mo (>10 mg kg(-1)) and have low (<2:1) Cu to Mo ratios, which can exacerbate molybdenosis problems in cattle. However, soybean grain normally constitutes only -10% of dairy cattle diet, and other constituents (e.g., corn grain, stover, mineral supplements) are sufficient, or can be manipulated, to control molybdenosis.     

Environmental indices in irrigation management

Irrigation management calls for objective criteria capable of representing the economy, reliability, and productivity of irrigation systems. These criteria must be compatible with long-term sustainability and conservation goals. The criteria representing the above goals are the economic effect of management on yield reduction, economic effect, and reliability referring to plant growth and operation of the network. In this study environmental indices are introduced to express the above criteria in quantitative terms. The inclusion of these indices at the farm and network level create a multicriteria framework for decision-making based on composite programming. An experimental study was conducted during the irrigation periods of 1989 and 1990 in Chania, Greece, concerning water delivered to 40 experimental plots, soil moisture content at the rootzone, and irrigation system operational failures. The data collected in real time were used for the calculation of the corresponding environmental indices. The variation in time and space is high and resulted in up to 62% of yield loss and low system performance (up to 7% of system temporal reliability). The study indicated that environmental indices could be incorporated to select alternatives and also to develop policies on water delivery. The final decision involves a trade-off analysis between cost of application and desired system performance. Measures of both primary objectives can be obtained using environmental indices that represent system operation aggregation at its basic levels (on farm and network).     

The consequences of tourism for sustainable water use on a tropical island: Zanzibar, Tanzania

Many developing countries in the tropics have focused on tourism to generate additional income sources and to diversity the economy. Coastlines in particular have been on the forefront of tourist infrastructure development. Here, the presence of a large number of tourists has often had negative consequences for the sustainable use of the available resources, which in turn has had an effect on the integrity of the ecosystems. In this paper, the situation is described for the use of freshwater resources on the east coast of Zanzibar, Tanzania. This region is water poor, relying on freshwater derived from seasonal rains and stored in less efficient aquifers, which consist of freshwater lenses floating on the underlying seawater. Tourism in the area has grown rapidly in recent years and is expected to further increase in the future. This development is expected to put additional pressure on the freshwater resources of the east coast, which show already signs of over-use. The consequences of overexploitation can include the lowering of the groundwater table, land subsidence, deteriorating groundwater quality, and saltwater intrusion. These, in turn, determine the living conditions in coastal areas and the effects will be felt both by the local populations and the tourist industry. An investigation is made into the causes and consequences of water abstraction by the tourist industry. The results show that present levels of withdrawal are not sustainable, and parts of the local populations are already experiencing water deficits on a daily basis. In the future, if the expected increase in tourist numbers occurs, the pressure on the aquifers will correspondingly increase. The results could be that the tourism in the area becomes unsustainable, which could have an adverse effect on the national economy and also on the local population and environment. Therefore, a precautionary water-management approach is suggested.     

Testing hypotheses about management to enhance habitat for feeding birds in a freshwater wetland

The level of water was manipulated in a freshwater wetland, with the aim of enhancing abundances of benthic animals and, ultimately, improving habitat for feeding birds (Japanese Snipe, Gallinago hardwickii). We tested whether these actions had the predicted and desired effects on benthic animals, by contrasting changes in two managed locations to one control location which was left unmanipulated. The number of taxa and abundances of chironomids decreased strongly and significantly in the manipulated locations, while the abundance of oligochaetes appeared to vary in a seasonal manner. Temporal variability of the structure and composition of assemblages was also increased in manipulated locations. Such effects have previously been suggested to indicate stress in benthic assemblages. Therefore, in contrast to what was predicted, managerial actions made benthic fauna less abundant and thus, less suitable as habitat for feeding birds. Several general lessons can be learned from these results. (1) Effects of managerial actions like these are difficult to predict a priori and can only be reliably evaluated with an experimental framework. (2) Because abundances of animals vary naturally, evaluations of managerial actions must include appropriate spatial replication. (3) Sampling at hierarchical temporal scales is important, because abundances of animals may vary in an unpredictable manner at short temporal scales and because changes in temporal variability may be a symptom of stress. (4) Combined use of uni- and multivariate techniques provides a comprehensive set of tools to assess the effects of restoration and creation of new habitats. Finally, these results emphasise the need for clear predictions about desired outcomes and specific experimental plans about how to test whether the desired results were achieved, before managerial actions are taken. Although this is often very difficult to achieve in real situations, it is necessary for practices of management to evolve on the basis of sound empirical experience.     

Nitrate and chloride loading to groundwater from an irrigated north-central U.S. sand-plain vegatable field

Groundwater pollution and associated effects on drinking water have increased with the expansion of irrigated agriculture in north-central U.S. sand plains. Controlling this pollution requires an ability to measure and predict pollutant loading by specific agricultural systems. We measured NO3 and Cl loading to groundwater beneath a Wisconsin central sand plain irrigated vegetable field using both a budget method and a new monitoring-based method. By relying on frequent monitoring of shallow groundwater, the new method overcomes some limitations of other methods. Monitoring-based and budget methods agreed well, and indicated that loading to groundwater was 165 kg ha(-1) NO3-N and 111 kg ha(-1) Cl for sweet corn (Zea mays L.) in 1992, and 228 kg ha(-1) NO3-N and 366 kg ha(-1) Cl for potato (Solanum tuberosum L.) in 1993. Nitrate N loading was 56 to 60% of available N, or 66 to 70% of fertilizer N. Sweet corn NO3 loading was about typical for this region, but potato NO3 loading was probably 50% greater than typical because heavy rains provoked extra fertilizer application. Our results imply that typical NO3-N loading would be 119 kg ha(-1) for sweet corn and 203 kg ha(-1) for potato, even with strict adherence to University Extension fertilizer recommendations. To keep average groundwater NO3-N within the 10 mg L(-1) U.S. drinking water standard, each irrigated vegetable field would need to be offset by five to eight times as much land supplying NO3-free groundwater recharge.     

Ecological impacts of arable intensification in Europe

Although arable landscapes have a long history, environmental problems have accelerated in recent decades. The effects of these changes are usually externalized, being greater for society as a whole than for the farms on which they operate, and incentives to correct them are therefore largely lacking. Arable landscapes are valued by society beyond the farming community, but increased mechanization and farm size, simplification of crop rotations, and loss of non-crop features, have led to a reduction in landscape diversity. Low intensity arable systems have evolved a characteristic and diverse fauna and flora, but development of high input, simplified arable systems has been associated with a decline in biodiversity. Arable intensification has resulted in loss of non-crop habitats and simplification of plant and animal communities within crops, with consequent disruption to food chains and declines in many farmland species. Abandonment of arable management has also led to the replacement of such wildlife with more common and widespread species. Soils have deteriorated as a result of erosion, compaction, loss of organic matter and contamination with pesticides, and in some areas, heavy metals. Impacts on water are closely related to those on soils as nutrient and pesticide pollution of water results from surface runoff and subsurface flow, often associated with soil particles, which themselves have economic and ecological impacts. Nitrates and some pesticides also enter groundwater following leaching from arable land. Greatest impacts are associated with simplified, high input arable systems. Intensification of arable farming has been associated with pollution of air by pesticides, NO2 and CO2, while the loss of soil organic matter has reduced the system's capacity for carbon sequestration. International trade contributes to global climate change through long distance transport of arable inputs and products. The EU Rural Development Regulation (1257/99) provides an opportunity to implement measures for alleviating ecological impacts of arable management through a combination of cross-compliance and agri-environment schemes. To alleviate the problems described in this paper, such measures should take account of opportunities for public/private partnerships and should integrate social, cultural, economic and ecological objectives for multifunctional land use.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.