Groundwater temperature and degassing in the Mad River subwatershed of Lake Huron

Groundwater was measured 70 times in two years at 10 sites as it flowed 50 m over an accumulation of travertine (CaCO₃) before reaching the Mad River. At source, the groundwater was relatively cool (6.77 ± 2.89 °C), slightly acidic ( pH 6.86 ± 0.22), and had a moderately high specific conductivity (606 ± 51 μS). Degassing was assessed from increases in pH, and CaCO₃ deposition was assessed from decreasing conductivity. After flowing over the experimental site, degassing had increased pH to 8.04 ± 0.16 (P < 0.001), which was similar to river water (pH 8.07 ± 0.30). Concurrently, CaCO₃ deposition decreased conductivity to 577 ± 43 μS (P < 0.001) but this was still higher (P < 0.001) than river water (494 ± 72). Seasonal changes in air temperature affected the rate of degassing. The pH was correlated with air temperature (r = 0.15, P < 0.001) while conductivity was correlated with pH (r = − 0.27, P < 0.001), but no direct relationship of air temperature with conductivity was detected. Groundwater entering the river after atmospheric exposure had a fairly constant temperature (7.05 ± 1.22 °C) despite seasonal changes in air temperature, thus warming the river in winter (up to day 100 and after day 300) and cooling it in summer (from days 140 to 260). Degassing and CaCO₃ deposition in springs without travertine was similar to that observed in the study stream over travertine. These groundwater inflows provide favorable pH and temperature conditions for brook trout.     

CATALYTIC CRACKING OF RESIDUAL PETROLEUM FRACTIONS

ABSTRACT

Arabian Light crude oil vacuum bottoms has been fractionated into five high-boiling fractions by wiped film evaporation, and the fractions subjected to catalytic cracking in a fixed-fluidized bed using a commercial equilibrium cracking catalyst. Density, aromaticity, and heteroatom content generally increased with boiling point, as did metals content except for vanadium and iron which demonstrated possible bimodal distributions. The cracking response of these fractions showed increasing yields of dry gas and coke, with decreasing gasoline yields, as a function of increasing apparent boiling point as would normally be expected. Surprisingly, however, local maxima were observed for wet gas yield and total conversion, with local minima for cycle oil and slurry yields, in the region of the 1200–1263°F (650–680°C) middle fraction. All fractions showed significant response to cracking, with coke yields generally being the only negative factor observed.     

Effects of physical-chemical characteristics on the sorption of selected endocrine disruptors by dissolved organic matter surrogates

Sorption coefficients (K(oc) values) of selected endocrine disruptors for a wide variety of dissolved organic matter (DOM) were measured using fluorescence quenching and solubility enhancement. 17beta-Estradiol, estriol, 17alpha-ethynylestradiol, p-nonylphenol, p-tert-octylphenol, and dibutylphthalate were selected as endocrine disruptors. Aldrich humic acid, Suwannee River humic and fulvic acids, Nordic fulvic acid, alginic acid, dextran, and tannic acid were selected as DOM surrogates. The resulting sorption coefficients (log K(oc)) were independent of octanol-water partitioning coefficients (log K(ow)) of the selected endocrine disruptors, indicating the hydrophobic interaction is not the predominant sorption mechanism. Moreover, the K(oc) values for the selected endocrine disruptors, especially the steroid estrogens, correlated much better with UV absorptivity at 272 nm (A272) and phenolic group concentration of the DOM than with either the H/O or the (O+N)/C atomic ratio of the DOM. This suggests that the sorption mechanism is closely related to the interaction between pi-electrons and the hydrogen bonds, i.e., the affinity between phenolic groups of the steroid estrogens and DOM is suggested to provide a relatively large contribution to the overall sorption and yield the K(oc) values of the steroid estrogens as high as those of the alkylphenols and dibutylphthalate, which are suggested to be dominated by nonspecific hydrophobic interaction.     

Polycyclic aromatic hydrocarbon and particulate emissions from two-stage combustion of polystyrene: the effect of the primary furnace temperature

A study is presented on laboratory-scale combustion of polystyrene (PS) to identify staged-combustion conditions that minimize emissions. Batch combustion of shredded PS was conducted in fixed beds placed in a bench-scale electrically heated horizontal muffle furnace. In most cases, combustion of the samples occurred by forming gaseous diffusion flames in atmospheric pressure air. The combustion effluent was mixed with additional air, and it was channeled to a second muffle furnace (afterburner) placed in series. Further reactions took place in the secondary furnace at a residence time of 0.7 s. The gas temperature of the primary furnace was varied in the range of 500-1,000 degrees C, while that of the secondary furnace was kept fixed at 1,000 degrees C. Sampling for CO, CO2, O2, soot, and unburned hydrocarbon emissions (volatile and semivolatile, by GC-MS) was performed at the exits of the two furnaces. Results showed that the temperature of the primary furnace, where PS gasifies, is of paramount importance to the formation and subsequent emissions of organic species and soot. Atthe lowesttemperatures explored, mostly styrene oligomers were identified at the outlet of the primary furnace, but they did not survive the treatment in the secondary furnace. The formation and emission of polycyclic aromatic hydrocarbons (PAH) and soot were suppressed. As the temperature in the first furnace was raised, increasing amounts of a wide range of both unsubstituted and substituted PAH containing up to at least seven condensed aromatic rings were detected. A similar trend was observed for total particulate yields. The secondary furnace treatment reduced the yields of total PAH, but it had an ambiguous effect on individual species. While most low molecular mass PAH were reduced in the secondary furnace, concentrations of some larger PAH increased under certain conditions. Thus, care in the selection of operating conditions of both the primary furnace (gasifier/ burner) and the secondary furnace (afterburner) must be exercised to minimize the emission of hazardous pollutants. The emissions of soot were also reduced in the afterburner but not drastically. This indicates that soot is indeed resistant to oxidation; thus, it would be best to avoid its formation in the first place. An oxidative pyrolysis temperature of PS in the vicinity of 600 degrees C appears to accomplish exactly that. An additional afterburner treatment at a sufficiently high temperature (1,000 degrees C) may be a suitable setting for minimization of most pollutants. To obtain deeper understanding of chemical processes, the experimental results were qualitatively compared with preliminary predictions of a detailed kinetic model that describes formation and destruction pathways of chemical species including most PAH observed in the present work. The modeling was performed forthe secondary furnace assuming plug-flow conditions therein. The experimentally determined chemical composition at the outlet of the primary furnace was part of the input parameters of the model calculation.     

Exploring the influence of granular iron additives on 1,1,1-trichloroethane reduction

Bimetallic reductants are frequently more reactive toward organohalides than unamended iron and can also alter product distributions, yet a molecular-level explanation for these phenomena remains elusive. In this study, surface characterization of six iron-based bimetallic reductants (Au/Fe, Co/Fe, Cu/Fe, Ni/Fe, Pd/Fe, and Pt/Fe) revealed that displacement plating produced a non-uniform overlayer of metallic additive on iron. Batch studies demonstrated that not all additives enhanced rates of 1,1,1-trichloroethane (1,1,1-TCA) reduction nor was there any clear periodic trend in the observed reactivity (Ni/Fe approximately Pd/Fe > Cu/Fe > Co/ Fe > Au/Fe approximately Fe > Pt/Fe). Pseudo-first-order rate constants for 1,1,1-TCA reduction (kobs values) did, however, correlate closely with the solubility of atomic hydrogen within each additive. This suggests absorbed atomic hydrogen, rather than galvanic corrosion, is responsible for the enhanced reactivity of bimetallic reductants. In addition, all additives shifted product distributions to favor the combined yield of ethylene plus ethane over 1,1-dichloroethane. In rate-enhancing bimetallic systems, branching ratios between 1,1-dichloroethane and the combination of ethylene and ethane were uniquely dependent on kobs values, indicating an intimate link between rate-determining and product-determining steps. We propose that our results are best explained by an X-philic pathway involving atomic hydrogen with a hydride-like character.     

Internal short circuit in Li-ion cells

Effects of internal short circuit (ISCr) on thermal stability of Li-ion cells of various sizes (130-1100 mAh) are investigated using a combination of experimental methods and thermal modeling. Three experimental methods were evaluated: small nail penetration, small indentation, and cell pinch test. The small nail penetration and indentation tests created significant heat sinking to the cell-can or to the nail. Only the cell pinch test provided a reasonable approximation of a high risk ISCr event. ISCr location plays a critical role in the consequences of an ISCr event. ISCr at the edge of the electrode is the worst case because of its limited heat conduction to the cell-can. The effects of cell capacity and state of charge on ISCr are also evaluated through tests and thermal modeling.     

Impact of Inspected Buffers on Production Parameters of Construction Processes

This paper examines the production implications of quality control inspections conducted on the buffer between processes in a construction project by modeling the linkage between these processes. Inspection of partially completed work at the end of one activity but before the beginning of work by the next activity is fairly common. Work that is deemed to be of sufficient quality is then made available for the next activity. Work that is deemed insufficient requires rework, typically by the trade appropriate to the activity that fed into the buffer, to bring the work into compliance. This has implications for workload management for that trade, of course, as well as for the reliability of work flow to the successor or downstream processes. While such situations are common in all construction sectors, an example from the residential construction sector was examined via a simulation model augmented by field data collected from residential construction projects. The impacts of the work flow into the predecessor process, the inspection pass rate, and resource availability were examined. The inspection pass rate was found to dramatically affect the reliability of work flow, unless resources are unlimited. Furthermore, the inspection pass rate was found to be functionally related to the production parameters of the process.     

A fast compact algorithm for cubic spline smoothing

An efficient algorithm is presented for computing discrete or continuous cubic smoothing splines with uniformly spaced and uniformly weighted measurements. The algorithm computes both the spline values and the generalized cross-validation score. Execution time and memory use are reduced by carefully exploiting the problem’s rich structure. The frequency domain properties of the steady-state cubic spline smoother are also examined.     

Fabrication of switchable liquid crystal devices using surface relief gratings in photopolymer

Holographically recorded surface relief gratings in dry, self-developing acrylamide based photopolymer were used to fabricate two types of switchable liquid crystal (LC) device. One is an electrically switchable LC diffraction grating and the other is an electrically switchable polarization rotator. The electrically switchable diffraction grating was characterized by measuring the dependence of the intensity in the first diffracted order on the applied electric field. The polarization rotator was characterized by studying the influence of the applied electric field on the twist angle and the variation of intensity in the zero and the first orders of diffraction.     

Characterisation of inhomogeneous inclusions in Darwin glass using ion beam analysis

Darwin glass is an impact glass resulting from the melting of local rocks during the meteorite impact that formed the 1.2 km diameter Darwin Crater in western Tasmania. These glass samples have small spheroidal inclusions, typically a few tens of microns in diameter, that are of great interest to the geologists. We have analysed one such inclusion in detail with proton microbeam ion beam analysis (IBA). A highly heterogeneous composition is observed, both laterally and in depth, by using self-consistent fitting of photon emission and particle backscattering spectra. With various proton energies near 2 MeV we excite the ¹²C(p,p)¹²C resonance at 1734 keV at various depths, and thus we can probe both the C concentration, and also the energy straggling of the proton beam as a function of depth which gives information on the sample structure. This inclusion has an average composition of (C, O, Si) = (28, 56, 16) mol% with S, K, Ca, Ti and Fe as minor elements and Cr, Mn, Ni, Cu, Zn and Br as trace elements. This composition includes, at specific points, an elemental depth profile and a density variation with depth consistent with discrete quartz crystals a few microns in size.