Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

The emissions of selected flame retardants were measured in 1- and 0.02-m³ emission test chambers and 0.001-m³ emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER_a) of TCPP varied between 20 ng m⁻² h⁻¹ and 140 μg m⁻² h⁻¹.The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER_u) of organophosphates were determined to be 10–85 ng unit⁻¹ h⁻¹. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER_a of between 0.2 and 6.6 ng m⁻² h⁻¹ and an SER_u of between 0.6 and 14.2 ng unit⁻¹ h⁻¹. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER_a of between 0.1 and 29 ng m⁻² h⁻¹ and decabromodiphenylether was not detectable at all.     

Time course of isocyanate emission from curing polyurethane adhesives

The time course of isocyanate emission from curing polyurethane (PUR) resins and adhesives was studied in two different emission test chambers. The measured emissions were strongly dependent on the type of experiment. The adhesives under investigation contained different types of diisocyanates and are used for different applications, e.g. for fixing of textile floor coverings. The influence of the curing mechanism on emission was studied by comparing the emission curves of one-component adhesives (OCA) and two-component adhesives (TCA). For TCA, the decrease in isocyanate emission was found to follow a two-step process during curing. In the first step, the emission is dominated by surface evaporation, and the decay of emission is mainly caused by the decrease in monomer content due to reaction. In the second step, the release is limited by internal diffusion. The influence of monomer reactivity on the emission profile could be demonstrated for 2,4′- and 4,4′-MDI. The less-reactive 2,4′-MDI caused prolonged emission. A strong dependence of emission rates on temperature and adhesive viscosity was also obvious. The evaluation of emission rates of different commercially available PUR adhesives showed the highest emission from systems that are applied at high temperatures. The high reactivity of diisocyanates requires special techniques for sampling and analysis. Therefore, an analytical method using HPLC–MS/MS was developed that enables limits of quantitation of <5 ng/m³ with a sampling volume of 100 l.     

A dynamic model of mating behavior in digger wasps: the energetics of male-male competition mimic size-dependent thermal constraints

I develop a state-based dynamic model of behavior to demonstrate that size-dependent differences in temperature tolerances are not necessary to account for the activity of small male digger wasps late in the day. In the model, males defend or patrol the nesting area, wait near nests, or feed away from the nesting area depending on time of day, energy reserves and size rank. I assume a large male competitive advantage, so mating opportunities decrease with size rank for territorial or patrolling males and are rare for all waiting males; the costs of patrolling or defense are higher than the costs of waiting. If energy reserves of all males are initially small, all males alternate feeding and territorial or patrolling behavior. If energy reserves are initially large, large males patrol or maintain territories until they risk starvation and leave the area to feed. At this time, smaller males that have conserved their resources by waiting and feeding may defend territories or patrol. I simulate the behavior of three populations representing two species of Microbembex by assuming large initial energy reserves for populations in which males were territorial and small initial reserves for populations in which males patrolled, and then convert the predicted time of activity to temperature using local regressions from field studies. Temporal patterns in the activity of large and small males were similar to those actually observed, and relationships between size and temperature predicted by the model corresponded to most observations and were sometimes positive. Thus, the delayed activity of smaller males does not correspond to activity at higher temperatures and is probably not attributable to size-dependent thermal tolerances, but may represent a temporal displacement of mating activity due to intra-sexual competition and mediated by energetics. The model makes testable predictions on the timing of feeding and depletion of energy reserves in relation to size and initial energy state, and suggests how differences among species may influence the temporal and spatial organization of male mating behavior. Received: 27 February 1997 / Accepted after revision: 26 July 1997     

Male coloration and chick condition in blue-footed booby: a cross-fostering experiment

Sexual selection models suggest that female choice is based on male traits that indicate their genetic or environmental condition, consequently enhancing her reproductive success by direct or indirect benefits. We investigated the relationship between male foot colour and offspring condition in the blue-footed booby, a socially monogamous seabird, with conspicuous and variably condition-dependent coloured feet that are selected by females. In a cross-fostering experiment, we found that chick condition was related to the foot colour of the foster father and, to some extent, to the foot colour of the genetic father; thus overall, the fathers sexual ornamentation (genetic and foster) explained 32% of variance of chick condition. These data suggest that foot colour, a dynamic sexually selected trait, is mostly a signal of parental contribution. In species in which males provide parental care, females may choose mates with higher parental ability. Overall, our data suggest that colourful integuments are honest signals of parental ability.Communicated by J. Graves     

The tactics of mutual mate choice and competitive search

A model of mutual mate choice is described, formulated as a dynamic game, which yields predictions about mating behaviour under the influence of time constraints, choice costs and competition for mates. These variables were examined because they may result in a change in the distribution of qualities among unmated individuals of both sexes over the course of the breeding season. The model predicts that mutual choice gives rise to assortative mating, although high costs of choice and/or inaccurate assessment both lead to lower overall correlations between the qualities (or the attractiveness) of mates. When all individuals are present from the start of the breeding season, the correlation between the qualities of individuals pairing at a given time declines throughout the season, so that mates are more closely matched among individuals who pair early than among those who pair late (and extra-pair copulation may thus be more common among the latter). Delayed arrival of lower-quality individuals may, however, lead to an increase in this correlation with time during the early part of the season. The mean quality of unmated males and females declines over time, because more attractive individuals tend to mate sooner. As a result of this decline, and because of time constraints, superior individuals become less choosy as the season progresses. If choice is costly, however, then inferior individuals become more selective with time during the early part of the season, and the level of choosiness peaks later for such individuals. Received: 28 March 1996 / Accepted after revision: 21 September 1996     

Influence of ozone on the sampling and storage of volatile organic compounds in canisters

A dynamic dilution system was used for the study of the influence of ozone on the sampling and storage of volatile organic compounds (VOCs) at 0, 4, 7 and 14 days in “TO-Can” canisters at two ozone concentrations, 60 and 150 ppbv. Among the 31 ozone precursors VOCs, a representative mixture containing five alkenes, five aromatics, acetylene and 1,3 butadiene was selected using the Clausius–Clapeyron equation. Here, we demonstrate that the presence of ozone have no influence on the concentrations of VOCs after 14 days storage period and consequently no problem of representativity of the sampling appears after 14 days of storage. The main explanation is the degradation of ozone in contact with deactivated walls of canisters.     

测井剖面定量地层对比新技术

根据岩性地层对比原理,本文提出一个测井剖面定量地层对比模式。该模式由三部份组成:1.利用“多变量最优分段方法”将两对比测井剖面的地层进行分段处理;2.利用“爬山法”计算分属不同测井剖面的任意两段地层之间的相似性指标;3.根据相似性指标,利用“动态规划”方法确定地层对比结果。本文还利用上述模式进行了定量地层对比的实例研究,其结果比较令人满意。     

水泥厂粉尘防治的环境经济效益分析

以雎水煤矿水泥厂技改为例，分别对新、老生产线粉尘污染进行了预测和调查监测。用无组织和有组织源强，计算了技改后的粉尘削减量，求得直接效益及环保投资回收期，并试用人力资本法、市场价值法，概算了间接效益。最后对无组织源强确定法作了讨论。     

Characterization of a new smog chamber for evaluating SAPRC gas-phase chemical mechanism

A new state-of-the-art indoor smog chamber facility (CAPS-ZJU) has been constructed and characterized at Zhejiang University, which is designed for chemical mechanism evaluation under well-controlled conditions. A series of characterization experiments were performed to validate the well-established experimental protocols, including temperature variation pattern, light spectrum and equivalent intensity (J_NO2), injection and mixing performance, as well as gases and particle wall loss. In addition, based on some characterization experiments, the auxiliary wall mechanism has been setup and examined. Fifty chamber experiments were performed across a broad range of experimental scenarios, and we demonstrated the ability to utilize these chamber data for evaluating SAPRC chemical mechanism. It was found that the SAPRC-11 can well predict the O₃ formation and NO oxidation for almost all propene runs, with 6 hr Δ(O₃ – NO) model error of –3% ± 7%, while the final O₃ was underestimated by ~20% for isoprene experiments. As for toluene and p-xylene experiments, it was confirmed that SAPRC-11 has significant improvement on aromatic chemistry than earlier version of SAPRC-07, although the aromatic decay rate was still underestimated to some extent. The model sensitivity test has been carried out, and the most sensitive parameters identified are the initial concentrations of reactants and the light intensity as well as HONO offgasing rate and O₃ wall loss rate. All of which demonstrated that CAPS-ZJU smog chamber could derive high quality experimental data, and could provide insights on chamber studies and chemical mechanism development.     

水下振动台关键技术的研究

本文从理论和实践两方面分析研究了水下振动台的若干关键技术问题,主要包括运动部件的设计、冷却系统的设计、密封系统的设计、压力平衡系统的设计等。解决了水下振动台设计所存在的难题。