Kinetics and mechanistic aspects of As(III) oxidation by aqueous chlorine, chloramines, and ozone: relevance to drinking water treatment

Kinetics and mechanisms of As(III) oxidation by free available chlorine (FAC-the sum of HOCl and OCl-), ozone (O3), and monochloramine (NH2Cl) were investigated in buffered reagent solutions. Each reaction was found to be first order in oxidant and in As(III), with 1:1 stoichiometry. FAC-As(III) and O3-As(III) reactions were extremely fast, with pH-dependent, apparent second-order rate constants, k'app, of 2.6 (+/- 0.1) x 10(5) M(-1) s(-1) and 1.5 (+/- 0.1) x 10(6) M(-1) s(-1) at pH 7, whereas the NH2Cl-As(III) reaction was relatively slow (k'app = 4.3 (+/- 1.7) x 10(-1) M(-1) s(-1) at pH 7). Experiments conducted in real water samples spiked with 50 microg/L As(III) (6.7 x 10(-7) M) showed that a 0.1 mg/L Cl2 (1.4 x 10-6 M) dose as FAC was sufficient to achieve depletion of As(III) to <1 microg/L As(III) within 10 s of oxidant addition to waters containing negligible NH3 concentrations and DOC concentrations <2 mg-C/L. Even in a water containing 1 mg-N/L (7.1 x 10(-5) M) as NH3, >75% As(III) oxidation could be achieved within 10 s of dosing 1-2 mg/L Cl2 (1.4-2.8 x 10(-5) M) as FAC. As(III) residuals remaining in NH3-containing waters 10 s after dosing FAC were slowly oxidized (t1/2 > or = 4 h) in the presence of NH2Cl formed by the FAC-NH3 reaction. Ozonation was sufficient to yield >99% depletion of 50 microg/L As(III) within 10 s of dosing 0.25 mg/L O3 (5.2 x 10(-6) M) to real waters containing <2 mg-C/L of DOC, while 0.8 mg/L O3 (1.7 x 10(-5) M) was sufficientfor a water containing 5.4 mg-C/L of DOC. NH3 had negligible effect on the efficiency of As(III) oxidation by O3, due to the slow kinetics of the O3-NH3 reaction at circumneutral pH. Time-resolved measurements of As(III) loss during chlorination and ozonation of real waters were accurately modeled using the rate constants determined in this investigation.     

Hexabromocyclododecanes (HBCDs) in the environment and humans: a review

Hexabromocyclododecanes (HBCDs) are brominated aliphatic cyclic hydrocarbons used as flame retardants in thermal insulation building materials, upholstery textiles, and electronics. As a result of their widespread use and their physical and chemical properties, HBCDs are now ubiquitous contaminants in the environment and humans. This review summarizes HBCD concentrations in several environmental compartments and analyzes these data in terms of point sources versus diffuse sources, biomagnification potential, stereoisomer profiles, time trends, and global distribution. Generally, higher concentrations were measured in samples (air, sediment, and fish) collected near point sources (plants producing or processing HBCDs), while lower concentrations were recorded in samples from locations with no obvious sources of HBCDs. High concentrations were measured in top predators, such as marine mammals and birds of prey (up to 9600 and 19 200 ng/g lipid weight, respectively), suggesting a biomagnification potential for HBCDs. Relatively low HBCD concentrations were reported in the few human studies conducted to date (median values varied between 0.35 and 1.1 ng/g lipid weight). HBCD levels in biota are increasing slowly and seem to reflect the local market demand. One important observation is the shiftfrom the high percentage of the gamma-HBCD stereoisomer in the technical products to a dominance of the alpha-HBCD stereoisomer in biological samples. A combination of factors such as variations in solubility, partitioning behavior, uptake, and, possibly, selective metabolism of individual isomers may explain the observed changes in stereoisomer patterns. Recommendations for further work include research on how HBCDs are transferred from products into the environment upon production, use, and disposal. Time trends need to be analyzed more in detail, including HBCD stereoisomers, and more data on terrestrial organisms are needed, especially for humans. Whenever possible, HBCDs should be analyzed as individual stereoisomers in order to address their fate and effects.     

Romanian River Basins Lag Time Analysis. The SCS-CN Versus RNS Comparative Approach Developed for Small Watersheds

Romanian policy makers have to perceive that human intervention on river basins land cover is influencing rainfall-runoff relation and the used methodology cannot accurately estimate watershed surface flow transformations. Global water cycles and energy fluxes understanding is leading to better predictions of land atmosphere interaction and local hydro-climates evolution. The water transfer time determination from rainfall to runoff needs accurate measurements of river basins hydrological parameters. Here, we analyzed and compared the lag time value results of two different methodologies (curve number and rational methodology) used for 54 Romanian small catchment areas study. The focus of this paper is the lag time evaluation and interpretation for an effective implementation of the best methodology approach in the Romanian geographical space. Our research in small river basins was developed using remote sensing technology maps, GIS and environmental datasets in combination with field work on every drainage basin in order to assess the specific morphological features and validate the land cover typology. We found that Soil Conservation Service - Curve Number (SCS-CN) method is widely used according to USA landscape features classification, but not necessarily applicable to Romanian river basins characteristics. Our results show how the official Romanian rational methodology national standard (RNS) can be improved and the limits of SCS-CN method.

     

Numerical modelling of production from the Poihipi dry steam zone: Wairakei geothermal system,New Zealand

The Poihipi power station utilizes dry steam from a shallow zone near the margin of the Wairakei geothermal reservoir. The station has been in operation for several years, with daily variations in the fluid production rate following variations in time-of-day pricing of electricity. The corresponding varying pressure history provides a good database for testing models of the geothermal reservoir.     

Real-time three-dimensional wind simulation for windmill rig tests

This paper deals with the methods of three-dimensional fixed-point wind speed real-time simulation modelled in large band, in order to use them in test rigs for experimental investigation of the wind energy conversion systems. The medium- and long-term components of the non-stationary wind speed are considered as known, being issued from measured data or by adopting a generic model. The spectral characteristics of three-dimensional turbulence are described either by the Kaimal or the von Karman models. The turbulence intensity and the length scale that take part in these models are calculated by the site parameters, using current standards. The basic idea of the methods for large-band three-dimensional wind simulation is to use rational shaping filters that approximate non-integer orders shaping filters issued from the Kaimal and the von Karman models. All the synthesized rational shaping filters use one time constant, automatically adapted to the medium- and long-term components that pilot the other time constants of the shaping filters by a set of parameters practically constant. Some numerical results concerning time series that simulate the non-stationary wind speed with three-dimensional turbulence components based on Kaimal and von Karman models are presented.     

La CLAve to increase psychosis literacy of Spanish-speaking community residents and family caregivers.

The authors developed and tested a 35-min psychoeducational program with the goal of increasing Spanish-speaking persons’ literacy of psychosis. The program uses popular cultural icons derived from music, art, and videos, as well as a mnemonic device—La CLAve (The Clue)—to increase (a) knowledge of psychosis, (b) efficacy beliefs that one can identify psychosis in others, (c) attributions to mental illness, and (d) professional help-seeking. Assessments were conducted before and after administering the program to both community residents (n = 57) and family caregivers of persons with schizophrenia (n = 38). For community residents, the authors observed increases across the 4 domains of symptom knowledge, efficacy beliefs, illness attributions, and recommended help-seeking. For caregivers, increases were observed in symptom knowledge and efficacy beliefs. La CLAve is a conceptually informed psychoeducational tool with a developing empirical base aimed at helping Spanish-speaking Latinos with serious mental illness obtain care in a timely manner. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Onset of convection in a horizontal porous layer driven by catalytic surface reaction on the lower wall

The onset of convection in a horizontal layer filled with a fluid-saturated porous medium is studied in this paper. On the lower wall there is an exothermic surface reaction, described by the Arrhenius kinetics, while the upper wall is subjected to uniform temperature and concentration. The problem, cast in dimensionless form, is governed by three dimensionless parameters pertaining to the exothermic reaction and the Lewis number. Once the basic state is solved, a linearized stability analysis is then performed and the resulting eigenvalue problem is solved using a conventional shooting method. One determines numerically the critical Rayleigh and wave numbers at the onset of convection, for various values of the problem parameters.     

Determination of polybrominated diphenyl ethers and polychlorinated biphenyls in human adipose tissue by large-volume injection-narrow-bore capillary gas chromatography/electron impact low-resolution mass spectrometry

A new analytical method has been developed for the quantification of polybrominated diphenyl ethers (PBDEs) in human adipose tissue samples. After Soxhlet extraction and a cleanup procedure using two successive solid-phase extraction cartridges containing acid silica and acid silica: neutral silica:deactivated basic alumina (from top to bottom), detection can been achieved by narrow-bore (0.10-mm i.d.) capillary gas chromatography/electron impact low-resolution mass spectrometry using a large-volume injection technique. Using narrow-bore capillaries, it is possible to analyze complex mixtures in a short time (up to 10 min), saving 50% or more of the analysis time of conventional columns while maintaining a similar resolution power. The method allows the determination of five major PBDE congeners (BDE 28, 47, 99, 100, and 153) at concentrations below 1 ng/g lipid weight. Detection limits in the selected ion mode varied between 0.05 and 0.30 ng/g lipid weight, depending on the degree of bromination. The sensitivity of this method can compete with low-resolution mass spectrometry with electron capture ionization, while a much better selectivity is obtained. Levels of PBDEs in 20 Belgian human adipose tissue samples ranged between 2.18 and 11.70 ng/g lipid weight and were similar to previously reported values from Europe.     

Recursion Engineering for Reduction Incorporated Parsers

Reduction Incorporated (RI) recognisers and parsers deliver high performance by suppressing the stack activity except for those rules that generate fully embedded recursion. Automaton constructions for RI parsing have been presented by Aycock and Horspool [John Aycock and Nigel Horspool. Faster generalised LR parsing. In Compiler Construction, 8th Intnl. Conf, CC'99, volume 1575 of Lecture Notes in Computer Science, pages 32 – 46. Springer-Verlag, 1999] and by Scott and Johnstone [Adrian Johnstone and Elizabeth Scott. Generalised regular parsers. In Gorel Hedin, editor, Compiler Construction, 12th Intnl. Conf, CC'03, volume 2622 of Lecture Notes in Computer Science, pages 232–246. Springer-Verlag, Berlin, 2003] but both can yield very large tables. An unusual aspect of the RI automaton is that the degree of stack activity suppression can be varied in a fine-grained way, and this provides a large family of potential RI automata for real programming languages, some of which have manageable table size but still show high performance. We give examples drawn from ANSI-C, Cobol and Pascal; discuss some heuristics for guiding manual specification of stack activity suppression; and describe work in progress on the automatic construction of RI automata using profiling information gathered from running parsers: in this way we propose to optimise our parsers' table size against performance on actual parsing tasks.     

Seismic Site Response for Near-Fault Forward Directivity Ground Motions

Forward directivity effects in the near-fault region produce pulse-type motions that differ significantly from ordinary ground motions that occur at greater distances from the causative fault. Current code site factors are based on empirical observations and analyses involving less intense nonpulse ordinary ground motions. Nonlinear site response analyses with bidirectional shaking are performed using representative site profiles to quantify seismic site response effects for intense near-fault motions resulting from forward directivity. Input rock motions are represented with simplified velocity pulses that characterize the amplitude and period of forward directivity motions. Results indicate that site response affects both the amplitude and period of forward directivity pulses, and hence, local site conditions should be considered when evaluating seismic designs in the near-fault region. Stiff soil sites tend to amplify the peak ground velocity and increase the period of pulse-type motions, particularly, when the period of the rock motion coincides with the degraded period of the site. Amplification is limited at soft soil sites by the dynamic strength of the weak soil, so attenuation occurs for intense input motions. This nonlinearity is not reflected in the site factors in current building codes. Guidance is provided for estimating the amplitude and pulse period for velocity pulses at soil sites.