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.     

Response of Ceriodaphnia dubia to ionic silver: discrepancies among model predictions, measured concentrations and mortality

Silver thiosulfate, often a waste product of photoprocessing, is less bioavailable or toxic to aquatic organisms than is ionic silver. We conducted duplicate 48-h Ceriodaphnia dubia tests in reconstituted laboratory water using treatments of 92.7 nM Ag+ with various concentrations of thiosulfate. Expected Ag+ concentrations were generated for thiosulfate treatment levels using MINEQL + chemical equilibrium modeling. Ag+ concentrations in treatments were determined using a novel silicon-based sensor. Based on predicted Ag+ and published 48-h LC50 values for C. dubia, we did not expect to observe adverse effects. Yet, 100% mortality was observed at low thiosulfate treatments, whereas > 85% and > 95% survival was observed at higher thiosulfate treatment levels, respectively. Our results indicate that biotic responses match the sensor-based Ag+ concentrations. However, there is a discrepancy between these empirical results and responses expected to occur with Ag+ concentrations as predicted by MINEQL + chemical modeling. By correlating silicon sensor data with toxicity results obtained from our laboratory, our work clearly relates a specific chemical form (Ag+) to toxicity results.     

Investigations into the transport and pathways of scallop larvae--the use of numerical models for managing fish stocks

The scallop fisheries off the southeast coast of Ireland have historically been considered a valuable resource for coastal communities, and hence their management is important. The scallop fishing grounds consist of a number of scallop beds dispersed throughout the St George's Channel and the southern Irish Sea. The boundaries between stocks and the interconnection in populations of adult scallops, through larval transport, is generally unknown. Until the time of this research, the stocks of scallop in this region had not been assessed. A research project was undertaken to develop novel, spatially explicit and multi-disciplinary approaches to the assessment of the scallop fisheries in the region. The project supported research in three related areas under the broad objective of developing stock assessment protocols and methods in order to promote sustainable management of these fisheries. One of these areas was the development and application of numerical models. The objectives of this modelling research were: (a) to reconstruct the physical environment of the study area; (b) investigate how this environment affects the demographics and nature of scallop; and (c) determine migration-transport pathways of the scallop larvae. From these investigations, light is shed on how the spatial variability in certain parameters of the natural environment determine habitats and the scallop populations. Also, the investigations now enable determinations to be made on the interconnectivities of 'disparate' scallop beds and where larvae are, in general, likely to be found. Thus, through the use of complex computer models, important clues are deduced that enable us to now understand key behavioural components of scallop larvae and their transport pathways. The analysis of these clues is assisting the development of protocols for managing the fish stock in a sustainable manner.     

Tribute chromite mining and environmental management on the northern Great Dyke of Zimbabwe

A combination of poor mining methods, waste storage and disposal systems, as well as the day-to-day activities associated with tribute and contract chromite mining are primarily responsible for environmental problems on the Zimbabwe Great Dyke. For instance, the unsystematic dumping of waste rocks in rivers blocks channels and results in flooding, which further sterilizes agricultural land and mineral resources. Erosion of these haphazardly located dumps causes siltation of water bodies and results in the dispersion of heavy metals in soils and watercourses. Vegetation growth on waste dumps is limited and constrained by the high pH levels from phytotoxic metals in soils, the lack of nutrients, poor moisture retention qualities of the mining waste and critical cation imbalances within dumps. This article attributes poor environmental management on the Dyke to poverty, a direct result of the nature of tribute agreements and output prices. Prices based on output targets are exploitative and undervalue labour and thus perpetuate poverty. By absolving claim holders from environmental liability, tribute agreements contribute directly to environmental problems. Thus, the incorporation of enforceable dual environmental responsibility requirements in contract mining agreements is needed to overcome this problem. This article recommends that, to break the poverty cycle, the primary cause of environmental mismanagement in the sector, miners need to be empowered through claim ownership and the enhancement of their capacity to negotiate prices with buyers of chrome.     

New York State urban and rural measurements of continuous PM2.5 mass by FDMS, TEOM, and BAM

Field evaluations and comparisons of continuous fine particulate matter (PM2,5) mass measurement technologies at an urban and a rural site in New York state are performed. The continuous measurement technologies include the filter dynamics measurement system (FDMS) tapered element oscillating microbalance (TEOM) monitor, the stand-alone TEOM monitor (without the FDMS), and the beta attenuation monitor (BAM). These continuous measurement methods are also compared with 24-hr integrated filters collected and analyzed under the Federal Reference Method (FRM) protocol. The measurement sites are New York City (the borough of Queens) and Addison, a rural area of southwestern New York state. New York City data comparisons between the FDMS TEOM, BAM, and FRM are examined for bias and seasonality during a 2-yr period. Data comparisons for the FDMS TEOM and FRM from the Addison location are examined for the same 2-yr period. The BAM and FDMS measurements at Queens are highly correlated with each other and the FRM. The BAM and FDMS are very similar to each other in magnitude, and both are approximately 25% higher than the FRM filter measurements at this site. The FDMS at Addison measures approximately 9% more mass than the FRM. Mass reconstructions using the speciation trends network filter data are examined to provide insight as to the contribution of volatile species of PM2.5 in the FDMS mass measurement and the fraction that is likely lost in the FRM mass measurement. The reconstructed mass at Queens is systematically lower than the FDMS by approximately 10%.