Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

MINIMIZING THE IMPACT OF URBANIZATION ON LONG TERM RUNOFF1

Increasing concern about the problems caused by urban sprawl has encouraged development and implementation of smart growth approaches to land use management. One of the goals of smart growth is water resources protection, in particular minimizing the runoff impact of urbanization. To investigate the magnitude of the potential benefits of land use planning for water resources protection, possible runoff impacts of historical and projected urbanization were estimated for two watersheds in Indiana and Michigan using a long term hydrological impact analysis model. An optimization component allowed selection of land use change placements that minimize runoff increase. Optimizing land use change placement would have reduced runoff increase by as much as 4.9 percent from 1973 to 1997 in the Indiana study watershed. For nonsprawl and sprawl scenarios in the Michigan watershed for 1978 to 2040, optimizing land use change placement would have reduced runoff increase by 12.3 percent and 20.5 percent, respectively. The work presented here illustrates both an approach to assessing the magnitude of the impact of smart growth and the significant potential scale of smart growth in moderating runoff changes that result from urbanization. The results of this study have significant implications for urban planning.     

Environment drives financial performance: The Jury is in

In a single day, June 13, 1994, the total stock market capitalization of Exxon dropped by a full 5 percent, with news of the company's exposure to additional legal damages from the Exxon Valdez disaster. Despite what should have been a jarring wake-up call, however, Wall Street investors and company CEOs continue for the most part to conduct business as usual, unpersuaded that environmental considerations are anything more than a superficial and temporary blip on their Bloomberg screens. There is mounting evidence that they're dead wrong. In this article, the authors contend what they're currently sleeping through is nothing less than the beginnings of a profound, worldwide industrial restructuring.     

Evaluating Nonpoint Pollution Policy Using a Tightly Coupled Spatial Decision Support System

Policy makers often must rely on the cumulative impact of independent actions taken by local landowners to achieve environmental goals. The connection between policy, regulation, and local action, however, is often not well understood and, thus, the impact of proposed policies may be difficult to predict. In this study we evaluate the effectiveness of alternative policy scenarios for agricultural set aside programs (e.g., the conservation reserve program administered by the United States Department of Agriculture) in reducing nonpoint pollution. Two alternative policy scenarios are developed and analyzed; one based on the erodibility index (detachment), the other sediment yield (transport). An estimate of the cumulative impact of associated land use change on nonpoint pollution is made using the AGNPS distributed parameter watershed model. This work is completed within the Cypress Creek watershed in southern Illinois. An analysis of the resulting data suggests that the most efficacious regulatory strategy for achieving nonpoint water pollution goals depends, in part, on place-specific land use patterns. This conclusion provides a solid argument for place-based regulatory strategies.     

Assessment of metal availability in smelter soil using earthworms and chemical extractions

Chemical immobilization is a relatively inexpensive in situ remediation method that reduces soil contaminant solubility, but the ability of this remediation treatment to reduce heavy metal bioavailability and ecotoxicity to soil invertebrates has not been evaluated. Our objectives were to (i) assess the ability of chemical immobilization amendments (municipal sewage sludge biosolids and rock phosphate) to reduce metal bioavailability and toxicity in a toxic metal-contaminated smelter soil and (ii) evaluate soil extraction methods using Ca(NO3)2 solution or ion-exchange membranes coated with diethylenetriaminepentaacetic acid (DTPA) as surrogate measures of metal bioavailability and ecotoxicity. We treated a soil contaminated by Zn and Pb milling and smelting operations and an uncontaminated control soil with lime-stabilized municipal biosolids (LSB), rock phosphate (RP), or anaerobically digested municipal biosolids (SS) and evaluated lethality of the remediated soils to earthworm (Eisenia fetida Savigny). Lime-stabilized municipal biosolids was the only remediation amendment to successfully immobilize lethal levels of Zn in the smelter soil (14-d cumulative mortality < or = 15%). Calcium nitrate-extractable Zn in the lethal Zn smelter soil-amendment combinations was 11.5 to 18.2 mmol/kg, compared with the nonlethal LSB amended soil (0.62 mmol/kg). The Ca(NO3)2-extractable Zn-based median lethal concentration (LC50) of 6.33 mmol/kg previously developed in Zn-spiked artificial soils was applicable in the remediated smelter soils despite a 14-fold difference in total Zn concentration. Chelating ion-exchange membrane uptake among the soils was highly variable (mean CV = 39%) compared with the Ca(NO3)2-extraction (mean CV = 1.9%) and not well related to earthworm toxicity.     

Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains"

Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.     

Using Sediment Budgets to Investigate the Pathogen Flux Through Catchments

We demonstrate a materials budget approach to identify the main source areas and fluxes of pathogens through a landscape by using the flux of fine sediments as a proxy for pathogens. Sediment budgets were created for three subcatchment tributaries of the Googong Reservoir in southeastern New South Wales, Australia. Major inputs, sources, stores, and transport zones were estimated using sediment sampling, dam trap efficiency measures, and radionuclide tracing. Particle size analyses were used to quantify the fine-sediment component of the total sediment flux, from which the pathogen flux was inferred by considering the differences between the mobility and transportation of fine sediments and pathogens. Gullies were identified as important sources of fine sediment, and therefore of pathogens, with the pathogen risk compounded when cattle shelter in them during wet periods. The results also indicate that the degree of landscape modification influences both sediment and pathogen mobilization. Farm dams, swampy meadows and glades along drainage paths lower the flux of fine sediment, and therefore pathogens, in this landscape during low-flow periods. However, high-rainfall and high-flow events are likely to transport most of the fine sediment, and therefore pathogen, flux from the Googong landscape to the reservoir. Materials budgets are a repeatable and comparatively low-cost method for investigating the pathogen flux through a landscape.     

Concentration and chemical speciation for the determination of Cu,Zn, Ni,Pb and Cd from refuse dump soils using the optimized BCR sequential extraction procedure

The optimized BCR sequential extraction procedure (proposed by the Standards, Measurements and Testing Programme (SM&T) of the European Union) was applied to seven topsoil samples from refuse dump sites for the determination of Cu, Zn, Ni, Pb and Cd. The metals were partitioned into four operationally defined chemical fractions: acid extractable, reducible, oxidizable and residual, and analysed using flame atomic absorption spectrophotometry, FAAS. The results were compared with total metal concentrations obtained using HNO₃, HClO₄ and HF digestion procedures. Results for total metal analysis ranged from - 15.55 to 43.45 for Cu, 37.15 to 222.35 for Zn, 5.15 to 12.10 for Ni, 10.30 to 93.05 for Pb and 0.35 to 3.75 for Cd in μgg⁻¹ dry weight. The results of the partitioning study showed that zinc prevailed in the more soluble fractions and was distributed between the acid-extractable (32.4%) and the reducible (40.3%) fractions, whereas Pb was distributed mainly in the reducible fraction. Copper and nickel were predominantly associated with the reducible and residual fractions - 53.4, 33.3 and 51.1, 24.1% respectively. The ranking of the four fractions for the partitioning of cadmium was: reducible > residual > oxidizable > acid extractable. The percentage recovery for all metals when comparing total metal concentration with the fractional sum of the optimized BCR procedure, were of the order: Zn(93%) > Pb(83%) > Cu(78) > Cd > (68%) > Ni(63%).