Pyrolysis behavior of tire-derived fuels at different temperatures and heating rates

Pyrolytic product distribution rates and pyrolysis behavior of tire-derived fuels (TDF) were investigated using thermogravimetric analyzer (TGA) techniques. A TGA was designed and built to investigate the behavior and products of pyrolysis of typical TDF specimens. The fundamental knowledge of TGA analysis and principal fuel analysis are applied in this study. Thermogravimetry of the degradation temperature of the TDF confirms the overall decomposition rate of the volatile products during the depolymerization reaction. The principal fuel analysis (proximate and ultimate analysis) of the pyrolytic char products show the correlation of volatilization into the gas and liquid phases and the existence of fixed carbon and other compounds that remain as a solid char. The kinetic parameters were calculated using least square with minimizing sum of error square technique. The results show that the average kinetic parameters of TDF are the activation energy, E = 1322 +/- 244 kJ/mol, a pre-exponential constant of A = 2.06 +/- 3.47 x 10(10) min(-1), and a reaction order n = 1.62 +/- 0.31. The model-predicted rate equations agree with the experimental data. The overall TDF weight conversion represents the carbon weight conversion in the sample.     

Source and persistence of pesticides in a semi-confined chalk aquifer of southeast England

Pesticide contamination in groundwater is an increasing problem that poses a significant long-term threat to water quality. Following the detection of elevated concentrations of diuron in boreholes in a semi-confined chalk aquifer from southeast England, a sampling programme was undertaken. Between 2003 and 2004 diuron was observed in 90% of groundwaters analysed. In 60% of groundwater samples metabolites of diuron were more prevalent than the parent compound. Longer-term (1989-2005) monitoring shows that pollution of the aquifer by atrazine, simazine, and more recently diuron, shows a positive correlation with periods of high groundwater levels. Results from groundwater residence time indicators suggest that the highest diuron concentrations are associated with waters containing the greatest proportion of recent recharge. There is some evidence to indicate that diuron occurrence can be spatially related to areas of urban and industrial development and is probably correlated with amenity usage.     

Probabilistic study of well capture zones distribution at the Lauswiesen field site

The delineation of well capture zones is of utmost environmental and engineering relevance as pumping wells are commonly used both for drinking water supply needs, where protection zones have to be defined, and for investigation and remediation of contaminated aquifers. We analyze the probabilistic nature of well capture zones within the well field located at the "Lauswiesen" experimental site. The test site is part of an alluvial heterogeneous aquifer located in the Neckar river valley, close to the city of Tübingen in South-West Germany. We explore the effect of different conceptual models of the structure of aquifer heterogeneities on the delineation of three-dimensional probabilistic well catchment and time-related capture zones, in the presence of migration of conservative solutes. The aquifer is modeled as a three-dimensional, doubly stochastic composite medium, where distributions of geo-materials and hydraulic properties are uncertain. We study the relative importance of uncertain facies geometry and uncertain hydraulic conductivity and porosity on predictions of catchment and solute time of travel to the pumping well by focusing on cases in which (1) the facies distribution is random, but the hydraulic properties of each material are fixed, and (2) both facies geometry and material properties vary stochastically. The problem is tackled within a conditional numerical Monte Carlo framework. Results are provided in terms of probabilistic demarcations of the three-dimensional well catchment and time-related capture zones. Our findings suggest that the uncertainty associated with the prediction of the location of the outer boundary of well catchment at the "Lauswiesen" site is significantly affected by the conceptual model adopted to incorporate the heterogeneous nature of the aquifer domain in a predictive framework. Taking into account randomness of both lithofacies distribution and materials hydraulic conductivity allows recognizing the existence of preferential flow paths that influence the extent of the well catchment and the solute travel time distribution at the site.     

Quality assured measurements of animal building emissions: gas concentrations

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH3), hydrogen sulfide (H2S), carbon dioxide (CO2), methane (CH4), nonmethane hydrocarbons (NMHC), particulate matter <10 microm in diameter, and total suspended particulate from swine and poultry production buildings in the United States. This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with > or =10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH3, H2S, CO2, CH4, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Evaluation of the persistence of micropollutants through pure-oxygen activated sludge nitrification and denitrification.

The persistence of pharmaceuticals, hormones, and household and industrial chemicals through a pure-oxygen activated sludge, nitrification, denitrification wastewater treatment facility was evaluated. Of the 125 micropollutants that were tested in this study, 55 compounds were detected in the untreated wastewater, and 27 compounds were detected in the disinfected effluent. The persistent compounds included surfactants, fire-retardant chemicals, pesticides, fragrance compounds, hormones, and one pharmaceutical. Physical-chemical properties of micropollutants that affected partitioning onto wastewater solids included vapor pressure and octanol-water partition coefficients.     

Interaction effects of metals and salinity on biodegradation of a complex hydrocarbon waste

The presence of high levels of salts because of produced brine water disposal at flare pits and the presence of metals at sufficient concentrations to impact microbial activity are of concern to bioremediation of flare pit waste in the upstream oil and gas industry. Two slurry-phase biotreatment experiments based on three-level factorial statistical experimental design were conducted with a flare pit waste. The experiments separately studied the primary effect of cadmium [Cd(II)] and interaction effect between Cd(II) and salinity and the primary effect of zinc [Zn(II)] and interaction effect between Zn(II) and salinity on hydrocarbon biodegradation. The results showed 42-52.5% hydrocarbon removal in slurries spiked with Cd and 47-62.5% in the slurries spiked with Zn. The analysis of variance showed that the primary effects of Cd and Cd-salinity interaction were statistically significant on hydrocarbon degradation. The primary effects of Zn and the Zn-salinity interaction were statistically insignificant, whereas the quadratic effect of Zn was highly significant on hydrocarbon degradation. The study on effects of metallic chloro-complexes showed that the total aqueous concentration of Cd or Zn does not give a reliable indication of overall toxicity to the microbial activity in the presence of high salinity levels.     

HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2-5.5 ng g(-1) and averaged 3.5 ng g(-1) in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g(-1), with a mean of 34.5 ng g(-1). In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g(-1) and averaged 13.8 ng g(-1), whereas the concentrations of t-DDT were in the range of 1.5-24.8 ng g(-1) with a mean value of 5.9 ng g(-1). The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant "one high with two low" and "one low with two high" effect in the Yangtze Estuary.     

Evaluating the role of desorption in bioavailability of sediment-associated contaminants using oligochaetes, semipermeable membrane devices and Tenax extraction

The success of the rapidly desorbing fraction as an available fraction was challenged by using sediment ingesting and non-ingesting oligochaetes (Lumbriculus variegatus) together with passive samplers (semipermeable membrane devices, SPMDs) in accumulation and kinetic modelling exercises for carbon-14 labelled model compounds (pyrene, benzo[a]pyrene and 3,4,3',4'-tetrachlorobiphenyl). Passive samplers clearly produced lower uptake rate constants and steady state factors than either of the oligochaete treatments when residue concentrations were based on animal lipid or total SPMD weight. The rapidly desorbing chemical fractions in sediments did not show a significant relationship with the biota sediment accumulation factors or SPMD accumulation factors. A distinctly better relationship was observed between the accumulation factors and the desorption rate constants. The results support the assumption that desorption plays an important role in bioavailability, although animal behaviour and the diffusional limitations of hydrophobic contaminants in sediment together probably affect the actual available pool.     

Contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area, Portugal since the 19th century

The main purpose of this study was to evaluate the contribution of anthropogenic pollutants to the increase of tropospheric ozone levels in the Oporto Metropolitan Area (Portugal) since the 19th century. The study was based on pre-industrial and recent data series, the results being analyzed according to the atmospheric chemistry. The treatment of ozone and meteorological data was performed by classical statistics and by time-series analysis. It was concluded that in the 19th century the ozone present in the troposphere was not of photochemical origin, being possible to consider the respective concentrations as reference values. For recent data a cycle of 8h for ozone concentrations could be related to traffic. Compared to the 19th century, the current concentrations were 147% higher (252% higher in May) due to the increased photochemical production associated with the increased anthropogenic emissions.     

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.