Titration Curves: A Useful Instrument for Assessing the Buffer Systems of Acidic Mining Waters (10 pp)

Background, Aims and Scope The acidification of mine waters is generally caused by metal sulfide oxidation, related to mining activities. These waters are characterized by low pH and high acidity due to strong buffering systems. The standard acidity parameter, the Base Neutralization Capacity (BNC) is determined by endpoint titration, and reflects a cumulative parameter of both hydrogen ions and all buffering systems, but does not give information on the individual buffer systems. We demonstrate that a detailed interpretation of titration curves can provide information about the strength of the buffering systems. The buffering systems are of importance for environmental studies and treatment of acidic mining waters. Methods Titrations were carried out by means of an automatic titrator using acidic mining waters from Germany and Canada. The curves were interpreted, compared with each other, to endpoint titration results and to elemental concentrations contained therein. Results and Discussion The titration curves were highly reproducible, and contained information about the strength of the buffer systems present. Interpretations are given, and the classification and comparison of acidic mining waters, by the nature and strength of their buffering systems derived from titration curves are discussed. The BNC-values calculated from the curves were more precise than the ones determined by the standard endpoint titration method. Due to the complex buffer mechanisms in acidic mining waters, the calculation of major metal concentrations from the shape of the titration curve resulted in estimates, which should not be confused with precise elemental analysis results. Conclusion Titration curves provide an inexpensive, valuable and versatile tool, by which to obtain sophisticated information of the acidity in acidic water. The information about the strength of the present buffer systems can help to understand and document the complex nature of acidic mining water buffer systems. Finally, the interpretation of titration curves could help to improve treatment measurements and the ecological understanding of these acidic waters.     

Carbon isotope fractionation during abiotic reductive dehalogenation of trichloroethene (TCE)

Dehalogenation of trichloroethene (TCE) in the aqueous phase, either on palladium catalysts with hydrogen as the reductant or on metallic iron, was associated with strong changes in delta13C. In general, the delta13C of product phases were more negative than those of the parent compound and were enriched with time and fraction of TCE remaining. For dehalogenation with iron, the delta13C of TCE and products varied from -42/1000 to +5/1000. For the palladium experiments, the final product, ethane, reached the initial delta13C of TCE at completion of the dehalogenation reaction. During dehalogenation, the carbon isotope fractionation between TCE and product phases was not constant. The variation in delta13C of TCE and products offers a new monitoring tool that operates independently of the initial concentration of pollutants for abiotic degradation processes of TCE in the subsurface, and may be useful for evaluation of remediation efficiency.     

The distinctive isotopic signature of plant-derived chloromethane: possible application in constraining the atmospheric chloromethane budget

Chloromethane (CH(3)Cl) is the most abundant halocarbon in the atmosphere. Although largely of natural origin it is responsible for around 17% of chlorine-catalysed ozone destruction. Sources identified to date include biomass burning, oceanic emissions, wood-rotting fungi, higher plants and most recently tropical ferns. Current estimates reveal a shortfall of around 2 million ty(-1) in sources versus sinks for the halocarbon. It is possible that emissions from green plants have been substantially underestimated. A potentially valuable tool for validating emission flux estimates is comparison of the delta13C value of atmospheric CH(3)Cl with those of CH(3)Cl from the various sources. Here we report delta13C values for CH(3)Cl released by two species of tropical ferns and show that the isotopic signature of CH(3)Cl from pteridophytes like that of CH(3)Cl from higher plants is quite different from that of CH(3)Cl produced by biomass burning, fungi and industry. delta13C values for CH(3)Cl produced by Cyathea smithii and Angiopteris evecta were respectively -72.7 per thousand and -69.3 per thousand representing depletions relative to plant biomass of 42.3 per thousand and 43.4 per thousand. The characteristic isotopic signature of CH(3)Cl released by green plants should help constrain their contribution to the atmospheric burden when reliable delta13C values for all other major sources of CH(3)Cl are obtained and a globally averaged delta13C value for atmospheric CH(3)Cl is available.     

Biogeochemical and ecological considerations in designing wetland treatment systems in post-mining landscapes

Although wetlands have gained acceptance as important components of ecosystems in post-mining landscapes in the past decade, their roles in contaminant retention/removal have not been well integrated into the designing of restoration programs. This paper describes the integration of sediment microbial activities and natural precipitation processes, along with approaches to defining the contaminant load from the mine wastes. The contaminant removal rates, which can be expected by a wetland sediment, are summarized and how they need to be reflected in the wetland size required, and the carbon supply which is needed. Contaminant loading from mining wastes can be balanced by wetland ecological processes, including wetland primary production and microbial mineralization in the sediment. This ecological engineering approach is demonstrated using case studies on hard-rock mining waste in Canada.     

Mate quality,not aggressive spillover,explains sexual cannibalism in a size-dimorphic spider

Sexual cannibalism particularly before mating is costly for the male victim but also for the female aggressor if she risks remaining unmated. The aggressive spillover hypothesis explains the persistence of this behavior as a maladaptive side effect of positive selection on aggressiveness in a foraging context. The hypothesis predicts that the occurrence of sexual cannibalism is explained by female aggressiveness but is not related to male phenotype or behavioral type. An alternative hypothesis invokes sexual selection and makes the opposite prediction namely that sexual cannibalism is an expression of female choice and should hence mainly target males of low quality. We tested the above hypotheses on a sexually dimorphic nephilid spider Nephilengys livida, known for male monopolization of females via genital damage, female genital plugging, and mate guarding, by staging mating trials during which we recorded mating behaviors and occurrences of pre- and postcopulatory cannibalism. We did not restrict assessment of aggressiveness to the mating and foraging context but also included aggression against same sex conspecifics. To assess female personalities, i.e., consistent individual differences in behavior including aggressiveness, we repeatedly tested them for intra-sex aggression, voracity towards prey, locomotory activity, and boldness. Females exhibited consistent differences in intra-sex aggressiveness, latency to attack prey, and boldness. Aggressive females had shorter latencies to attack prey and were more active than non-aggressive ones. In contrast to the predictions of the aggressive spillover hypothesis, females that were aggressive towards prey and towards other females were not more likely to attack a male than non-aggressive females. In support of the mate choice hypothesis, less aggressive males were more likely attacked and cannibalized than more aggressive ones. This hints at sexual selection for aggressiveness in males and raises the question of mechanisms that maintain variation in male aggressiveness.     

Evaluating the Slope‐Area Method to Accurately Identify Stream Channel Heads in Three Physiographic Regions

Estimation of stream channel heads is an important task since ephemeral channels play a significant role in the transport of sediment and materials to perennial streams. The slope‐area method utilizes digital elevation model (DEM) and related information to develop slope‐area threshold relationships used to estimate the position of channel heads in the watershed. A total of 162 stream channel heads were mapped across the three physiographic regions of Alabama, including the Southwestern Appalachians (51), Piedmont/Ridge and Valley (61), and Coastal Plains (51). Using Geographic Information System and DEM, the local slope and drainage area for each mapped channel head was calculated and region‐specific models were developed and evaluated. Results demonstrated the local slope and drainage area had an inverse and strong correlation in the Piedmont/Ridge and Valley region (r² = 0.71) and the Southwestern Appalachian region (r² = 0.61). Among three physiographic regions, the weakest correlation was observed in the Coastal Plain region (r² = 0.45). By comparing the locations of modeled channel heads to those located in the field, calculated reliability and sensitivity indices indicated model accuracy and reliance were weak to moderate. However, the slope‐area method helped define the upstream boundaries of a more detailed channel network than that derived from the 1:24,000‐scale National Hydrography Dataset, which is commonly used for planning and regulatory purposes.     

The removal of uranium from mining waste water using algal/microbial biomass

We describe a three step process for the removal of uranium (U) from dilute waste waters. Step one involves the sequestration of U on, in, and around aquatic plants such as algae. Cell wall ligands efficiently remove U(VI) from waste water. Growing algae continuously renew the cellular surface area. Step 2 is the removal of U-algal particulates from the water column to the sediments. Step 3 involves reducing U(VI) to U(IV) and transforming the ions into stable precipitates in the sediments. The algal cells provide organic carbon and other nutrients to heterotrophic microbial consortia to maintain the low E(H), within which the U is transformed. Among the microorganisms, algae are of predominant interest for the ecological engineer because of their ability to sequester U and because some algae can live under many extreme environments, often in abundance. Algae grow in a wide spectrum of water qualities, from alkaline environments (Chara, Nitella) to acidic mine drainage waste waters (Mougeotia, Ulothrix). If they could be induced to grow in waste waters, they would provide a simple, long-term means to remove U and other radionuclides from U mining effluents. This paper reviews the literature on algal and microbial adsorption, reduction, and transformation of U in waste streams, wetlands, lakes and oceans.     

Water resources and land use and cover in a humid region: the southeastern United States

It is widely recognized that forest and water resources are intricately linked. Globally, changes in forest cover to accommodate agriculture and urban development introduce additional challenges for water management. The U.S. Southeast typifies this global trend as predictions of land-use change and population growth suggest increased pressure on water resources in coming years. Close attention has long been paid to interactions between people and water in arid regions; however, based on information from regions such as the Southeast, it is evident that much greater focus is required to sustain a high-quality water supply in humid areas as well. To that end, we review hydrological, physicochemical, biological, and human and environmental health responses to conversion of forests to agriculture and urban land uses in the Southeast. Commonly, forest removal leads to increased stream sediment and nutrients, more variable flow, altered habitat and stream and riparian communities, and increased risk of human health effects. Although indicators such as the percentage of impervious cover signify overall watershed alteration, the threshold to disturbance, or the point at which effects can been observed in stream and riparian parameters, can be quite low and often varies with physiographic conditions. In addition to current land use, historical practices can greatly influence current water quality. General inferences of this study may extend to many humid regions concerning climate, environmental thresholds, and the causes and nature of effects.     

Carbon isotope fractionation during reductive dechlorination of TCE in batch experiments with iron samples from reactive barriers

Reductive dechlorination of trichloroethene (TCE) by zero-valent iron produces a systematic enrichment of 13C in the remaining substrate that can be described using a Rayleigh model. In this study, fractionation factors for TCE dechlorination with iron samples from two permeable reactive barriers (PRBs) were established in batch experiments. Samples included original unused iron as well as material from a barrier in Belfast after almost 4 years of operation. Despite the variety of samples, carbon isotope fractionations of TCE were remarkably similar and seemed to be independent of iron origin, reaction rate, and formation of precipitates on the iron surfaces. The average enrichment factor for all experiments was -10.1 per thousand (+/- 0.4 per thousand). These results indicate that the enrichment factor provides a powerful tool to monitor the reaction progress, and thus the performance, of an iron-reactive barrier over time. The strong fractionation observed may also serve as a tool to distinguish between insufficient residence time in the wall and a possible bypassing of the wall by the plume, which should result in an unchanged isotopic signature of the TCE. Although further work is necessary to apply this stable isotope method in the field, it has potential to serve as a unique monitoring tool for PRBs based on zero-valent iron.     

An Ecologically-Sustainable Surface Water Withdrawal Framework for Cropland Irrigation: A Case Study in Alabama

Agricultural production in the state of Alabama, USA, is mostly rain-fed, because of which it is vulnerable to drought during growing season. Since Alabama receives a significant portion of its annual precipitation during winter months, the goal of this study was to evaluate the feasibility of water withdrawal from streams during winter months for irrigation in the growing season. The Soil and Water Assessment Tool (SWAT) was used to estimate the quantity of water that can be sustainably withdrawn from streams during winter high flow periods. The model was successfully calibrated and validated for surface runoff, base flow, and total stream flow. The stream flows generated by the model at several locations within the watershed were then used to examine how much water can be sustainably withdrawn from streams of various orders (first, second and third). Although there was a considerable year-to-year variability in the amount of water that can be withdrawn, a 16-year average showed that first, second, and third order streams can irrigate about 11.6, 10.3, and 10.6% of their drainage areas, respectively. The percentage of drainage area that can be irrigated was not a function of stream order.