A Tool for Automated Load Duration Curve Creation1

Abstract: A recent study by the Texas Bacteria Total Maximum Daily Load (TMDL) Task Force has recommended the use of load duration curves as a primary tool in calculating bacterial TMDLs. This method is attractive because it effectively integrates flow regimes into TMDL analyses, clearly communicates data through a method that is understandable to the general public, and has been successfully applied in TMDL studies in other states. To ease the creation of load duration curves, an automated load duration curve creation tool called LDCurve has been created within a Microsoft Excel framework. Web services and a webscraper are used to retrieve U.S. Geological Survey streamflow data and Texas Commission on Environmental Quality water quality data. Data are imported to the spreadsheet, combined to create flow and load duration curves, and plotted. Final steps result in a preliminary estimate of the overall load reductions needed to meet water quality standards in the modeled segment. LDCurve is currently only applicable in the state of Texas, but may be updated to model water quality throughout the nation using analogous web services from the EPA STORET database. By using automated data retrievals and computations, the LDCurve tool reduces the amount of time required to create curves and calculate load reductions to a matter of minutes. LDCurve and all supporting materials are available online for free download at: http://tools.crwr.utexas.edu/LDCurve/ .     

Chemical and Microbiological Characteristics of Mineral Spoils and Drainage Waters at Abandoned Coal and Metal Mines

Mining is a long-established human activity. Abandonedmines, tailings, and mine spoils may have considerable impacton neighboring environments long after the sites are abandoned. Of greatest concern are derelict mines and wastes that generateacidic discharge waters that are enriched with iron and othermetals and metalloids. The chemistry and microbiology of thesesites are intricately intertwined. Whilst some indigenousmicroorganisms are responsible for accelerating sulfide mineraloxidation, thereby generating acidity and mobilizing metals,others catalyze reductive processes that essentially reversethese reactions and thereby ameliorate polluted mine waters.This article reviews current knowledge on the chemistry and microbiology of abandoned coal and metal mines, mine spoils and tailings.     

Effects of isolation by distance and geographical discontinuity on genetic subdivision of Littoraria cingulata

Littoraria cingulata (Philippi, 1846) is a Western Australian, mangrove littorine snail, represented by two morphologically distinct subspecies, whose distributions are separated by >300 km. The southern subspecies, L. cingulata pristissini, is distinguished from the northern subspecies, L. cingulata cingulata, by having a thinner, keelless shell with more primary grooves, and lower and much more numerous ribs. In contrast with these striking differences, L. cingulata cingulata is morphologically very similar to another species, L. sulculosa, with which it also shares a nearly coincident geographic range. Allozyme comparisons at 22 presumptive loci confirmed a large genetic distance between L. cingulata and L. sulculosa, and the apparent conspecificity of the morphologically divergent subspecies of L. cingulata. Based on geological evidence, the geographical separation of the morphologically divergent forms of L. cingulata has developed within the past 5000 to 10 000 yr. The extensive continuous distribution of the northern subspecies, L. cingulatacingulata, and the large geographic disjunction between the northern and Shark Bay subspecies, L. cingulata pristissini, allowed a test of the genetic importance of this relatively recent disjunction. Within the continuous distribution of the two subspecies, a pattern of isolation by distance was visible up to distances of 300 km. Beyond 300 km, genetic subdivision, measured by pairwise G _ST (the proportion of genetic diversity due to differences between populations), averaged 0.028, whereas subdivision between Shark Bay and northern populations averaged 0.055 over the same range of distances. Although the relative paucity of barriers to gene flow tends to limit genetic subdivision in marine species with planktotrophic larvae, the results for L. cingulata suggest that subdivision can occur within a continuous distribution, but that special events leading to major disjunctions can substantially increase divergence, even over a relatively short period of time. Received: 16 February 1998 / Accepted: 23 April 1998     

Effects of organic matter on the distribution of uranium in soil and plant matrices

This work studied interactions of uranium with pure organic compounds, such as glutathione, and more complex mixtures, such as humic acid and aqueous plant extracts. High performance liquid chromatography with UV absorption interfaced to inductively coupled plasma mass spectrometry sequential detection was used to detect organouranium complexes in a variety of soils and plant materials, indicating that nearly 100% of the uranium extracted from certain plant tissues was bound to organic ligands. In addition, soil sorption experiments indicated that humic acid generally decreased uranium sorption to soils and promoted subsequent desorption of uranium because of uranium partitioning to the organic phase. These experiments demonstrate that organic compounds influence the mobility and chemistry of uranium in the environment.     

Insights into the use of time-lapse GPR data as observations for inverse multiphase flow simulations of DNAPL migration

Perchloroethylene (PCE) saturations determined from GPR surveys were used as observations for inversion of multiphase flow simulations of a PCE injection experiment (Borden 9 m cell), allowing for the estimation of optimal bulk intrinsic permeability values. The resulting fit statistics and analysis of residuals (observed minus simulated PCE saturations) were used to improve the conceptual model. These improvements included adjustment of the elevation of a permeability contrast, use of the van Genuchten versus Brooks-Corey capillary pressure-saturation curve, and a weighting scheme to account for greater measurement error with larger saturation values. A limitation in determining PCE saturations through one-dimensional GPR modeling is non-uniqueness when multiple GPR parameters are unknown (i.e., permittivity, depth, and gain function). Site knowledge, fixing the gain function, and multiphase flow simulations assisted in evaluating non-unique conceptual models of PCE saturation, where depth and layering were reinterpreted to provide alternate conceptual models. Remaining bias in the residuals is attributed to the violation of assumptions in the one-dimensional GPR interpretation (which assumes flat, infinite, horizontal layering) resulting from multidimensional influences that were not included in the conceptual model. While the limitations and errors in using GPR data as observations for inverse multiphase flow simulations are frustrating and difficult to quantify, simulation results indicate that the error and bias in the PCE saturation values are small enough to still provide reasonable optimal permeability values. The effort to improve model fit and reduce residual bias decreases simulation error even for an inversion based on biased observations and provides insight into alternate GPR data interpretations. Thus, this effort is warranted and provides information on bias in the observation data when this bias is otherwise difficult to assess.     

Toxicity of cobalt-complexed cyanide to <Emphasis Type="Italic">Oncorhynchus mykiss,Daphnia magna</Emphasis>, and <Emphasis Type="Italic">Ceriodaphnia dubia</Emphasis>

Background Cobalt cyanide complexes often result when ore is treated with cyanide solutions to extract gold and other metals. These have recently been discovered in low but significant concentrations in effluents from gold leach operations. This study was conducted to determine the potential toxicity of cobalt-cyanide complexes to freshwater organisms and the extent to which ultraviolet radiation (UV) potentiates this toxicity. Tests were also conducted to determine if humic acids or if adaptation to UV influenced sensitivity to the cyanide complexes. Methods Rainbow trout (Oncorhynchus mykiss), Daphnia magna, and Ceriodaphnia dubia were exposed to potassium hexacyanocobaltate in the presence and absence of UV radiation, in the presence and absence of humic acids. Cyano-cobalt exposures were also conducted with C. dubia from cultures adapted to elevated UV. Results With an LC50 concentration of 0.38 mg/L, cyanocobalt was over a 1000 times more toxic to rainbow trout in the presence of UV at a low, environmentally relevant irradiance level (4 μW/cm² as UVB) than exposure to this compound in the absence of UV with an LC50 of 112.9 mg/L. Toxicity was immediately apparent, with mortality occurring within an hour of the onset of exposure at the highest concentration. Fish were unaffected by exposure to UV alone. Weak-acid dissociable cyanide concentrations were observed in irradiated aqueous solutions of cyanocobaltate within hours of UV exposure and persisted in the presence of UV for at least 96 hours, whereas negligible concentrations were observed in the absence of UV. The presence of humic acids significantly diminished cyanocobalt toxicity to D. magna and reduced mortality from UV exposure. Humic acids did not significantly influence survival among C. dubia. C. dubia from UV-adapted populations were less sensitive to metallocyanide compounds than organisms from unadapted populations. Conclusions The results indicate that metallocyanide complexes may pose a hazard to aquatic life through photochemically induced processes. Factors that decrease UV exposure such as dissolved organic carbon or increased pigmentation would diminish toxicity.     

The use of 'exotic' framework structures in waste management

The use of porous framework materials in waste management applications has the potential to be a powerful tool in toxic metal remediation. The properties that these materials possess, including high surface area and ion-exchange capacity, are theoretically valuable. Furthermore, the flexibility of many of these frameworks allows the potential for immobilisation of waste materials with the framework of the material, in addition to the traditional capture in the pore structure. However, for either of these routes to be useful for waste management purposes, these structures must also be stable in any proposed storage media. This study examines the stability of a range of porous materials whose frameworks are made out of zinc and arsenic, both considered toxic minesite wastes, when exposed to aqueous media. The three frameworks examined (sodalite analogue Na(6)(H(2)O)(8)(ZnAsO(4))(6), open framework K(3)Zn(4)O(AsO(4))(3).3.5H(2)O, and an ABW type framework NH(4)ZnAsO(4)) all have similar hydrothermal synthetic routes and bulk framework compositions, but differ in counter ion used, pore size and complexity of structure. The phases were examined before and after storage in an aqueous environment, and their crystallinity and leaching were determined. All phases prepared were found to be extremely unstable outside their original synthetic environment, and very soluble when exposed to water, calling into question their practical use in any environment.     

Controls on Mercury and Methylmercury Deposition for Two Watersheds in Acadia National Park, Maine

Throughfall and bulk precipitation samples were collected for two watersheds at Acadia National Park, Maine, from 3 May to 16 November 2000, to determine which landscape factors affected mercury (Hg) deposition. One of these watersheds, Cadillac Brook, burned in 1947, providing a natural experimental design to study the effects of forest type on deposition to forested watersheds. Sites that face southwest received the highest Hg deposition, which may be due to the interception of cross-continental movement of contaminated air masses. Sites covered with softwood vegetation also received higher Hg deposition than other vegetation types because of the higher scavenging efficiency of the canopy structure. Methyl mercury (MeHg) deposition was not affected by these factors. Hg deposition, as bulk precipitation and throughfall was lower in Cadillac Brook watershed (burned) than in Hadlock Brook watershed (unburned) because of vegetation type and watershed aspect. Hg and MeHg inputs were weighted by season and vegetation type because these two factors had the most influence on deposition. Hg volatilization was not determined. The total Hg deposition via throughfall and bulk precipitation was 9.4 μg/m²/year in Cadillac Brook watershed and 10.2 μg/m²/year in Hadlock Brook watershed. The total MeHg deposition via throughfall and bulk precipitation was 0.05 μg/m²/year in Cadillac Brook watershed and 0.10 μg/m²/year in Hadlock Brook watershed.     

Landscape Controls on Mercury in Streamwater at Acadia National Park, USA

Fall and spring streamwater samples were analyzed for total mercury (Hg) and major ions from 47 locations on Mount Desert Island in Maine. Samples were collected in zones that were burned in a major wildfire in 1947 and in zones that were not burned. We hypothesized that Hg concentrations in streamwater would be higher from unburned sites than burned watersheds, because fire would volatilize stored Hg. The Hg concentrations, based on burn history, were not statistically distinct. However, significant statistical associations were noted between Hg and the amount of wetlands in the drainage systems and with streamwater dissolved organic carbon (DOC). An unexpected result was that wetlands mobilized more Hg by generating more DOC in total, but upland DOC was more efficient at transporting Hg because it transports more Hg per unit DOC. Mercury concentrations were higher in samples collected at lower elevations. Mercury was positively correlated with relative discharge, although this effect was not distinguished from the DOC association. In this research, sample site elevation and the presence of upstream wetlands and their associated DOC affected Hg concentrations more strongly than burn history.     

Mass Balances of Mercury and Nitrogen in Burned and Unburned Forested Watersheds at Acadia National Park, Maine, USA

Precipitation and streamwater samples were collected from 16 November 1999 to 17 November 2000 in two watersheds at Acadia National Park, Maine, and analyzed for mercury (Hg) and dissolved inorganic nitrogen (DIN, nitrate plus ammonium). Cadillac Brook watershed burned in a 1947 fire that destroyed vegetation and soil organic matter. We hypothesized that Hg deposition would be higher at Hadlock Brook (the reference watershed, 10.2 μg/m²/year) than Cadillac (9.4 μg/m²/year) because of the greater scavenging efficiency of the softwood vegetation in Hadlock. We also hypothesized the Hg and DIN export from Cadillac Brook would be lower than Hadlock Brook because of elemental volatilization during the fire, along with subsequently lower rates of atmospheric deposition in a watershed with abundant bare soil and bedrock, and regenerating vegetation. Consistent with these hypotheses, Hg export was lower from Cadillac Brook watershed (0.4 μg/m²/year) than from Hadlock Brook watershed (1.3 μg/m²/year). DIN export from Cadillac Brook (11.5 eq/ha/year) was lower than Hadlock Brook (92.5 eq/ha/year). These data show that ∼50 years following a wildfire there was lower atmospheric deposition due to changes in forest species composition, lower soil pools, and greater ecosystem retention for both Hg and DIN.