Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

LOW-HEAD HYDROPOWER IMPACTS ON STREAM DISSOLVED OXYGEN1

ABSTRACT: A method to evaluate the effect of hydropower development on downstream dissolved oxygen (DO) is presented for a low head dam. Water, previously aerated during release over spillways and under gates, is diverted through the hydropower facility without further aeration. The oxygen transfer that occurs as a result of air entrainment at the various release points of a dam is measured. Oxygen transfer efficiencies are calculated and incorporated into an oxygen transfer model to predict average release DO concentrations. This model is used to systematically determine the effect of hydropower operation on downstream DO. Operational alternatives are investigated and a simple operational guide is developed to mitigate the effects of hydropower operation. Combinations of reduced generation and optimal releases from the dam allow the hydropower facility to operate within DO standards.     

CONCEPTUAL DESIGN PROCEDURE FOR HYDRAULIC DESTRATIFICATION SYSTEMS IN SMALL PONDS,LAKES, OR RESERVOIRS FOR WATER QUALITY IMPROVEMENT1

ABSTRACT: Forced artificial mixing of temperature-stratified ponds, or small lakes or reservoirs, by liquid jets can enhance water quality and can also be energy efficient. Based on previous studies of jet mixing mechanics of stratified water bodies, a conceptual design approach is presented. The main “operational” and “system” design parameters are considered in the proposed method. Using minimization of a total cost estimate as a criterion, an iterative method for the selection of the number and size of the jets is developed and illustrated.     

ANALYSIS OF WIND- AND SHIP-INDUCED SEDIMENT RESUSPENSION IN DULUTH-SUPERIOR HARBOR1

ABSTRACT: Suspended solids and ammonium concentration profiles measured at five locations in Duluth-Superior Harbor during July-October 1985 were analyzed to quantify wind and ship effects on sediment resuspension and resulting harbor water quality. Wind components from the SE quadrant correlated strongly with depth-averaged suspended solids concentrations that were unaffected by ship passage or thermal stratification. Winds from that quadrant have the largest fetch in the harbor. The highest correlation (r²= 0.93) was with the 6-hour average of the ESE wind velocity component. Multiple linear regression analysis of data from post-ship passage concentration profiles yielded numerical estimates of settling velocities of 0.08 to 0.25 cm s^?1, typical of ship-resuspended sediments, and vertical eddy diffusivities of 4 to 13 cm² s¹. The results suggest that ambient vertical eddy diffusivities in the harbor are less than 4 cm² s^?1 in the absence of ship passages and with winds less than 5 m s^?1 (10 knots).     

Model simulations of dissolved oxygen characteristics of Minnesota lakes: Past and future

A deterministic, one-dimensional, unsteady numerical model has been developed, tested, and applied to simulate mean daily dissolved oxygen (DO) characteristics in 27 lake classes in the state of Minnesota. Reaeration and photosynthesis are the oxygen sources, while respiration, sedimentary, and biochemical water column oxygen demand are the sinks of oxygen in the model. The lake classes are differentiated by surface area (A _s), maximum depth (H _max), and trophic status expressed as Secchi depth (Z _s). Because lake stratification is most important to lake oxygen dynamics, simulated DO characteristics are plotted in terms of a stratification parameterA _s/H _max ^0.25 and Secchi depthZ _s. Simulations provide DO profiles on a daily time scale. Specific DO characteristics of ecological and environmental interest are epilimnetic DO, hypolimnetic DO, DO gradient from surface to bottom, and DO minima and maxima. Specific results are as follows: Simulated mean daily and weekly DO values in the epilimnion of all lakes for both past and future climate scenarios are near saturation over the summer season. Hypolimnetic DO values depend strongly on lake morphometry, trophic status, and time throughout the summer season. Future climate conditions are specified as the historical records from 1955 to 1979, adjusted (monthly) by the 2 × CO₂ GISS model output to account for doubling of atmospheric CO₂. With this climate change, weekly averaged epilimnetic DO is projected to drop by less than 2 mg/liter, and will remain above 7 mg/liter throughout the open water season. The hypolimnetic DO reductions after climate change are on the order of 2–8 mg/liter. Periods of anoxia are longer by as much as 80 days. Those changes would alter water quality dynamics in lakes and have a profound effect on lake ecosystems including indigenous fishes. The results presented are useful for evaluating environmental management options.     

STREAM TEMPERATURE ESTIMATION FROM AIR TEMPERATURE1

ABSTRACT: Air temperatures are sometimes used as substitutes for stream temperatures. To examine the errors associated with this procedure, linear relationships between stream temperatures, T, and air temperatures, T_a, recorded for 11 streams in the central U.S. (Mississippi River basin) were analyzed. Weather stations were an average 42 miles (range 0 to 144 miles) from the rivers. The general equations, T_w= 5.0 + 0.75 T_a and T_w= 2.9 + 0.86 T_a with temperatures in °C, were derived for daily and weekly water temperatures, respectively, for the 11 streams studied. The simulations had a standard deviation between measurements and predictions of 2.7°C (daily) and 2.1°C (weekly). Equations derived for each specific stream individually gave lower standard deviations, i.e., 2.1°C and 1.4°C, respectively. Small, shallow streams had smaller deviations than large, deep rivers. The measured water temperatures follow the air temperatures closely with some time lag. time lags ranged from hours to days, increasing with stream depth. Taking into account these time lags improved the daily temperature predictions slightly. Periods of ice cover were excluded from the analysis.     

Sulfur nutrition of deciduous trees

Sulfur in its reduced form (-II) is an essential nutrient for growth and development, but is mainly available to plants in its oxidised form as sulfate. Deciduous trees take up sulfate by the roots from the soil solution and reduce sulfate to sulfide via assimilatory sulfate reduction in both roots and leaves. For reduction in the leaves, sulfate is loaded into the xylem and transported to the shoot. The surplus of sulfate not reduced in the chloroplast or stored in the vacuole and the surplus of reduced S not used for protein synthesis in the leaves is loaded into the phloem and transported back to the roots. Along the transport path, sulfate and glutathione (GSH) is unloaded from the phloem for storage in xylem and phloem parenchyma as well as in pit and ray cells. Re-mobilised S from storage tissues is loaded into the xylem during spring, but a phloem to xylem exchange does not appear to exist later in the season. As a consequence, a cycling pool of S was only found during the change of the seasons. The sulfate:glutathione ratio in the phloem seems to be involved in the regulation of S nutrition. This picture of S nutrition is discussed in relation to the different growth patterns of deciduous trees from the temperate climate zone, i.e. (1) terminated, (2) periodic and (3) indeterminate growth patterns, and in relation to environmental changes.