Prediction of polychlorinated dibenzofuran congener distribution from gas-phase phenol condensation pathways

A model for predicting the distribution of dibenzofuran and polychlorinated dibenzofuran (PCDF) congeners from a distribution of phenols was developed. The model is based on a simplified chemical mechanism. Relative rate constants and reaction order with respect to phenol precursors were derived from experimental results using single phenols and equal molar mixtures of up to four phenols. For validation, experiments were performed at three temperatures using a distribution of phenol and 19 chlorinated phenols as measured in municipal waste incinerator exhaust gas. Comparison of experimental measurements and model predictions for PCDF isomer distributions and homologue pattern shows agreement within measurement uncertainty. The R-squared correlation coefficient exceeds 0.9 for all PCDF isomer distributions and the distribution of PCDF homologues. These results demonstrate that the distribution of dibenzofuran and the 135 PCDF congeners from gas-phase condensation of phenol and chlorinated phenols can be predicted from measurement of the distribution of phenol and the 19 chlorinated phenol congeners.     

Investigation of adsorption characteristics of four toxic gases (nitric oxide,nitrogen dioxide,sulfur dioxide,and hydrogen chloride) on the inner surface of nickel-coated manganese steel cylinders and aluminum cylinders

To develop standard toxic gas mixtures, it is essential to identify adsorption characteristics of each toxic gas on the inner surface of a gas cylinder. Thus, this study quantified adsorbed amounts of the four toxic gases (nitric oxide [NO], nitrogen dioxide [NO₂], sulfur dioxide [SO₂], and hydrogen chloride [HCl]) on the inner surface of aluminum cylinders and nickel-coated manganese steel cylinders. After eluting adsorbed gases on the inside of cylinders with ultrapure water, a quantitative analysis was performed on an ion chromatograph. To evaluate the reaction characteristics of the toxic gases with cylinder materials, quantitative analyses of nickel (Ni), iron (Fe), and aluminum (Al) were also performed by inductively coupled plasma optical emission spectrometry (ICP-OES). It was found that the amounts of NO, NO₂, and SO₂ adsorbed on the inner surface of aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio, whereas the signal for most heavy metal elements were below their respective detection limits. This study found that the amounts of HCl adsorbed on the inner surface of nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas Ni (86 μmol) and Fe (28 μmol) were detected in the same cylinders. It was revealed that the adsorption mainly took place via the reaction of HCl with inner surface material of nickel-coated manganese steel cylinders. On the other hand, in the case of aluminum cylinders, the amounts of the adsorption were determined to be less than 1% at the level of HCl 100 μmol/mol mixing ratio, whereas most of Ni, Fe, and Al were detected at levels similar to their limits of detection. As a result, this study found that aluminum cylinders are more suitable for preparing HCl gas mixtures than nickel-coated manganese steel cylinders.

Implications: To develop a standard toxic gas mixture, it is essential to understand the adsorption characteristics of each toxic gas inside a gas cylinder. It was found that the amounts of NO, NO₂, and SO₂ adsorbed inside aluminum cylinders were less than 1.0% at the level of 100 μmol/mol mixing ratio. The amounts of HCl adsorbed inside nickel-coated manganese steel cylinders were less than 5% at the level of 100 μmol/mol mixing ratio, whereas those inside aluminum cylinders were less than 1%, indicating that aluminum cylinders are more suitable for preparing HCl gas mixtures.     

Accumulation of butyl- and phenyltin compounds in starfish and bivalves from the coastal environment of Korea

Triphenyltin (TPT) and tributyltin (TBT) concentrations were determined in two starfish species (Asteria pectinifera and Asterias amurensis), bivalves (Crassostrea gigas or Mytilus edulis), and seawater samples from sites around the coasts of Korea. Both TPT and TBT concentrations in starfish ranged from 8 to 1560 ng/g and from <2 to 797 ng/g as Sn on a dry weight basis, respectively. TPT concentration accounted for 75.4% and 86.4% of total phenyltin concentration in A. pectinifera and A. amurensis, respectively, while monobutyltin, a degradation product of TBT, accounted for 86.3% and 57.2% of total butyltin, respectively. Triphenyltin concentrations in A. pectinifera were significantly correlated to water and bivalve TPT concentrations, which implies that dietary uptake of TPT from contaminated prey as well as direct uptake from surrounding water contribute to TPT body residues in the starfish. Starfish could be target organisms for monitoring TPT compound in the marine environment, due to their high accumulation and low degradation capacity towards TPT.     

Seasonal and spatial distribution of nonylphenol in Shihwa Lake, Korea

Alkylphenols (APs) have been known as endocrine disruptors and consequently received much environmental concern. This study focused on seasonal variation and spatial distribution of nonylphenol (NP) in various matrixes including dissolved water, particulates, surface sediment, sediment trap and sediment core taken from Shihwa Lake and its adjacent areas. A total of 11 phenolic compounds including nonylphenol, t-octylphenol (t-OP) and bisphenol A (BPA) were measured in February, June and October 2002. NP is the most abundant chemical among the phenolic compounds and its concentrations in dissolved water, particulates and surface sediments from Shihwa Lake were measured as 17.4-1533.1 ng/l, 4.3-831.2 ng/l and 10.4-5054.1 ng/g dw, respectively. NP concentration in dissolved water varied with seasons and generally showed a decreasing order of June > October > February, while the seasonal trend was hardly found in sediment. High levels of NP were measured in surrounding industrial complexes, the concentrations was decreased gradually with distance from the industrial areas. NP in core samples showed an increasing trend toward the core depth. There exists a reasonable correlation between NP in dissolved water and in particulates, whereas the correlation between NP in dissolved water and in sediments is not significant. APs concentrations in Shihwa Lake were comparable to other highly polluted areas of the world and their possible effects on various organisms in the lake are discussed.     

Thermophilic-anaerobic digestion to produce class A biosolids: initial full-scale studies at Hyperion Treatment Plant.

The highest quality of biosolids is called exceptional quality. To qualify for this classification, biosolids must comply with three criteria: (1) metal concentrations, (2) vector-attraction reduction, and (3) the Class A pathogen-density requirements. The City of Los Angeles Bureau of Sanitation Hyperion Treatment Plant (HTP) (Playa del Rey, California) meets the first two requirements. Thus, the objective of this study was to ensure that HTP's biosolids production would meet the Class A pathogen-reduction requirements following the time-temperature regimen for batch processing (U.S. EPA, 1993; Subsection 32, Alternative 1). Because regulations require the pathogen limits to be met at the last point of plant control, biosolids sampling was not limited to immediately after the digesters, i.e., the digester outflows. The sampling extended to several locations in HTP's postdigestion train, in particular, the last points of plant control, i.e., the truck loading facility and the farm for land application. A two-stage, thermophilic-continuous-batch process, consisting of a battery of six egg-shaped digesters, was established in late 2001 for phase I of this study and modified in early 2002 for phase II. As the biosolids were discharged from the second-stage digesters, the Salmonella sp. (pathogen) and fecal-coliform (indicator) densities were well below the limits for Class A biosolids, even though the second-stage-digester temperatures were a few degrees below the temperature required by Alternative 1. Salmonella sp. densities remained below the Class A limit at all postdigestion sampling locations. Fecal-coliform densities were also below the Class A limit at postdigestion-sampling locations, except the truck-loading facility (phases I and II) and the farm for final use of the biosolids (phase II). Although federal regulations require one of the limits for either fecal coliforms or Salmonella sp. to be met, local regulations in Kern County, California, where the biosolids are land-applied, require compliance with both bacterial limits. Additional work identified dewatering, cooling of biosolids after the dewatering centrifuges, and contamination as possible factors in the rise in density of fecal coliforms. These results provided the basis for the full conversion of HTP to the Los Angeles continuous-batch, thermophilic-anaerobic-digestion process. During later phases of testing, this process was demonstrated to produce fully disinfected biosolids at the farm for land application.     

Evaluating safety management and culture interventions to improve safety: Effective intervention strategies

The Dutch Ministry of Social Affairs and Employment provided subsidy over the period 2004–2008 to a number of companies to introduce changes aimed at reducing accidents by changing their safety culture and aspects of their safety management. As part of the programme a scientific evaluation was set up to assess the effectiveness of the interventions in 17 of the projects, covering 29 companies. Before and after studies were made of the companies, documenting the state of their safety management and risk control efforts and their accident rates before the intervention, the changes made over the study period and the resulting changes in a range of measures aimed at assessing the success of the changes. The analysis led to a categorisation of the projects according to their degree of success.This paper describes the patterns of interventions distinguishing between successful and not successful projects and discusses the mechanisms lying behind them. Interventions bringing about constructive dialogue between shop-floor and line management, providing motivation to line managers and strengthening the monitoring and learning loops in the safety management system (SM) appeared more successful. The amount of energy and creativity injected by top managers and, above all, by the coordinator (safety professional) appeared also to be a distinguishing factor.     

A drop in the bucket: when is a pay raise a pay raise?

Although merit pay continues to receive much theoretical and practical attention, little systematic effort is devoted to determining how large a pay raise must be before employees see it as a pay raise. This study uses psychophysical reasoning and techniques in a sample of 192 student ‘employees’ to establish the size of pay raise thresholds in a relatively controlled setting. Results indicate that, below about the 7 per cent level, increases in pay amounts are unlikely to evoke positive perceptual and attitudinal reactions among employees. Theoretical, methodological, and practical implications of these results are highlighted. © 1997 by John Wiley & Sons, Ltd.     

The role of black carbon as a catalyst for environmental redox transformation

Black carbon (BC) is an important class of geosorbents that control the fate and transport of organic pollutants in soil and sediment. We previously demonstrated a new role of BC as an electron transfer mediator in the abiotic reduction of nitroaromatic and nitramine compounds by Oh and Chiu (Environ Sci Technol 43:6983–6988, 2009). We proposed that BC can catalyze the reduction of nitro compounds because it contains microscopic graphitic (graphene) domains, which facilitate both sorption and electron transfer. In this study, we assessed the ability of different types of BC—graphite, activated carbon, and diesel soot—to mediate the reduction of 2,4-dinitrotoluene (DNT) and 2,4-dibromophenol (DBP) by H₂S. All three types of BC enhanced DNT and DBP reduction. H₂S supported BC-mediated reduction, as was observed previously with a thiol reductant. The results suggest that BC may influence the fate of organic pollutants in reducing subsurface environments through redox transformation in addition to sorption.     

Overview of GHS (Globally Harmonized System) in Korea and the direction of further development

Many chemicals are being developed with the growth of science technology. Such chemicals bring many advantages to humans but also cause many social problems because of the hazards of the materials. Therefore, it is necessary to have a system which identifies the hazards of chemicals. Some acts or regulations about information on warning labels or MSDS (Material Safety Data Sheet) information for chemicals are similar in each country but there are differences in definitions of degree of hazard, standard classification of harmful level, and indication methods. GHS is the indication method of worldwide integrated classification standard in order to prevent damage caused by disease or risks of accidents resulting from confusion by the users. In keeping pace with the world trend, Korea has conducted translation of the GHS manual from UN and selected it as the official GHS manual of the Korean government. The official Korean GHS translated version was published in July 2005. After that, the Korea Ministry of Employment and Korea Labor and the Ministry of Environment have implemented GHS MSDS for chemical substances since July 1, 2010 so that manufacturers and importers are required to apply it. The full implementation for compound materials will start on July 1, 2013. In Korea, database information for chemicals is provided by four organizations including The Korea Occupational Safety and Health Agency. However, domestic information on chemicals provided by domestic information providers has problems including differences in basic content and incorrect recording because of trade secrets. Efforts for improvement including reinforcing training for manufacturers and importers on recording consistent information for different organizations are urgently needed.     

Analysis of underlying causes of investigated loss of containment incidents in Dutch Seveso plants using the Storybuilder method

In the Netherlands there are around 400 “Seveso” sites that fall under the Dutch Major Hazards Decree (BRZO) 1999. Between 2006 and 2010 the Dutch Labour Inspectorate's Directorate for Major Hazard Control completed investigations of 118 loss of containment incidents involving hazardous substances from this group. On the basis of investigation reports the incidents were entered in a tailor-made tool called Storybuilder developed for the Dutch Ministry of Social Affairs and Employment for identifying the dominant patterns of technical safety barrier failures, barrier task failures and underlying management causes associated with the resulting loss of control events. The model is a bow-tie structure with six lines of defence, three on either side of the central loss of containment event. In the first line of defence, failures in the safety barriers leading to loss of control events were primarily equipment condition failures, pre start-up and safeguarding failures and process deviations such as pressure and flow failures. These deviations, which should have been recovered while still within the safe envelope of operation, were missed primarily because of inadequate indication signals that the deviations have occurred. Through failures of subsequent lines of defence they are developing into serious incidents. Overall, task failures are principally failures to provide adequate technical safety barriers and failures to operate provided barriers appropriately. Underlying management delivery failures were mainly found in equipment specifications and provisions, procedures and competence. The competence delivery system is especially important for identifying equipment condition, equipment isolation for maintenance, pre-start-up status and process deviations. Human errors associated with operating barriers were identified in fifty per cent of cases, were mostly mistakes and feature primarily in failure to prevent deviations and subsequently recover them. Loss of control associated with loss of containment was primarily due to the containment being bypassed (72% of incidents) and less to material strength failures (28%). Transfer pipework, connections in process plant and relief valves are the most frequent release points and the dominant release material is extremely flammable. It is concluded that the analysis of a large number of incidents in Storybuilder can support the quantification of underlying causes and provide evidence of where the weak points exist in major hazard control in the prevention of major accidents.