超临界CO2和液态CO2及气态N2注入采空区防灭火性能实验

为对比研究超临界态CO_2、液态CO_2和气态N_2注入采空区的防灭火性能,自主研制了模拟采空区残煤自燃过程实验系统,开展了超临界态CO_2、液态CO_2和气态N_2注入采空区防灭火实验。实验结果表明:12 MPa、39℃超临界态CO_2对采空区自燃残煤的降氧降温能力优于6 MPa、30℃液态CO_2优于6 MPa、39℃气态N_2;12 MPa、39℃超临界态CO_2对残煤的降温能力是6 MPa、30℃液态CO_2的1.7倍,是6 MPa、39℃气态N_2的10倍,对采空区的降温能力是液态CO_2的2倍,为气态N_2的8倍;12 MPa、39℃超临界CO_2对采空区的降氧速率比6 MPa、30℃液态CO_2和6 MPa、39℃气态N_2高12.5%;12 MPa、39℃超临界CO_2的降温能力是8 MPa、39℃超临界CO_2的1.7倍,因此适当提高超临界态CO_2的注入压力,防灭火性能更佳。     

封管法制备有机碳稳定同位素样品存在的问题和改进

有机碳稳定同位素的高精度测定是利用地质样品有机碳同位素研究气候和植被变化等的基础。通过实验发现低有机碳含量样品同位素测定误差相对较大,其中样品收集过程是主要的影响因素之一。本文针对这个问题,主要从杂质气体干扰入手,在一步冷冻分离CO_2和H_2O,或分步冷冻分离CO2和H2O的收集方法,以及改变收样管体积三方面进行条件实验研究,讨论了封管法制备有机碳稳定同位素样品气体收集过程对有机碳稳定同位素组成的影响。结果表明:(1)CO_2气体的纯化收集是封管法制备有机碳稳定同位素样品的一个重要步骤,收集时杂质气体含量越高,对样品有机碳稳定同位素组成的影响越大;(2)在相同的杂质气体背景条件下,与一步冷冻分离CO_2和H_2O的方法相比,分步冷冻CO2和H2O的方法能够显著减小杂质气体对有机碳稳定同位素测定的影响;(3)小体积收样管能够显著提高有机碳稳定同位素样品的离子流强度,进而提高低有机碳含量样品的稳定碳同位素测定精度。     

Experimental study of the evaporation of spreading liquid nitrogen

The investigation of cryogenic liquid pool spreading is an essential procedure to assess the hazard of cryogenic liquid usage. There is a wide range of models used to describe the spreading of a cryogenic liquid pool. Many of these models require the evaporation velocity, which has to be determined experimentally because the heat transfer process between the liquid pool and the surroundings is too complicated to be modeled. In this experimental study, to measure the evaporation velocity when the pool is spreading, liquid nitrogen was continuously released onto unconfined concrete ground. Almost all of the reported results are based on a non-spreading pool in which cryogenic liquid is instantaneously poured onto bounded ground for a very short period of time. For the precise measurement of pool spreading and evaporation weight with time, a cone-type funnel was designed to achieve a nearly constant liquid nitrogen release rate during discharge. Specifically, three nozzles with nominal flow rates of 3.4 × 10⁻² kg/s, 5.6 × 10⁻² kg/s and 9.0 × 10⁻² kg/s were used to investigate the effect of the release rate on the evaporation velocity. It is noted that information about the release rate is not necessary to measure the evaporation velocity in case of the non-spreading pool. A simultaneous measurement of the pool location using thermocouples and of the pool mass using a digital balance was carried out to measure the evaporation velocity and the pool radius. A greater release flow rate was found to result in a greater average evaporation velocity, and the evaporation velocity decreased with the spreading time and the pool radius.     

Effect of initial temperature on the explosion pressure of various liquid fuels and their blends

In this work, the effect of initial temperature on the explosion pressure, P_ex, of various liquid fuels (isooctane, toluene and methanol) and their blends (isooctane-toluene and methanol-toluene, with three different fuel-fuel ratios) was investigated by performing experiments in a 20-l sphere at different concentrations of vaporized fuel in air. The initial temperature was varied from 333 K to 413 K.Results show that, as the fuel-air equivalence ratio, Φ, is increased, a transition occurs from a “thermodynamics-driven” explosion regime to a “radiant heat losses-driven” explosion regime. The maximum pressure, P_max, is found in the former regime (Φ < 3), which is characterized by a trend of decreasing P_ex with increasing initial temperature. This trend has been explained by thermodynamics. In the latter regime (Φ > 3), P_ex increases with increasing initial temperature. This trend has been addressed to the decrease in emissivity (and, thus, radiant heat losses) with the increase in temperature.     

分散固相萃取/高效液相色谱法测定土霉素菌渣中土霉素的残留量

文章拟建立一种从土霉素菌渣中提取并检测土霉素残留量的高效液相色谱法。用甲醇和冰乙酸作为提取剂提取样品,用分散固相萃取的方法净化样品,净化药剂为石墨化碳黑(GCB)和C18。通过加标回收实验,用高效液相色谱仪检测样品中土霉素含量。选用的色谱柱为PLRP-S,流动相为甲醇和0.05 mol/L草酸,两者比例为35:65(V:V)。检测波长为355 nm,柱温30℃。经检测,土霉素在0.1~2 000 mg/L范围内线性相关系数大于0.999,线性良好。1.0,4.0及8.0mg/g 3个加标水平的土霉素平均回收率范围是80.85%~109.59%,相对标准偏差(RSD)为2.45%~6.38%。土霉素菌渣中土霉素残留量平均为4.741 mg/g。实验表明,该方法具有简单、方便、快速、准确性强、灵敏度高的特点,可以应用于土霉素的分析检测。     

Estimation of Efficiency of Processing Soil Samples for Pesticide Residues Analysis

The efficiency of four sample processing methods was tested with eight different types of soils representing the major proportion of cultivated soils. The principle of sampling constant was applied for characterizing the efficiency of the procedures and testing the well-mixed status of the prepared soil. The test material was 14C-labeled atrazine that enabled keeping the random error of analyses ≤ about 1%. Adding water to the soil proved to be the most efficient and generally applicable procedure resulting in about 6% relative sample processing uncertainty for 20 g test portions. The expected error is inversely proportional to the mass of test portion. Smashing and manual mixing of soil resulted in about four times higher uncertainty than mixing with water. Grinding of soil is applicable for dry soils only, but the test procedure applied was not suitable for estimating a typical uncertainty of processing dry soil samples. Adding dry ice did not improve the efficiency of sample processing.     

Printed in great Britain Cr(VI) and other metallic mutagens in fly ash and welding fumes†

Particulate samples taken from both the indoor (working) and outdoor (community) environments contain a wide range of metallic trace elements most of which are mutagenic in at least one of the short term tests for genotoxicity currently in use. Because of the demonstrated presence of a short lived biologically active species (Cr(VI)), and the uncertainty with which the results of the screening of metallic compounds in short term tests can be interpreted in terms of human risk, great care must be taken to assure the appropriate collection, storage, and chemical and biological assay of such material. The sensitivity of the results for fly ash and welding fumes to variations in these protocols is demonstrated and discussed.     

Much Ado: How Big Is the Problem of Hydrolysis of Methyl Tertiary Butyl Ether (MtBE) to Form Tertiary Butyl Alcohol (tBA)?

Groundwater contaminated by the gasoline additive methyl tertiary butyl ether (MtBE) is also frequently impacted by tertiary butyl alcohol (tBA). The USEPA recently sponsored a study that discusses the possibility of hydrolysis of MtBE to form tBA during analytical procedures. This finding is important because it suggests that existing tBA data may not accurately depict tBA or MtBE concentrations in groundwater. This article discusses the mechanism and kinetics of MtBE hydrolysis, then presents three case studies of analytical results from sites in California, USA. Although these case studies are limited in scope, the data do not support the occurrence of the hydrolysis of MtBE to form tBA due to acid preservation of groundwater samples. At a minimum, this suggests that MtBE hydrolysis may not be as pervasive a problem as suggested in USEPA's study; therefore, concerns about the validity of historical tBA data may not be warranted. The reason for this result may be simple: there are two necessary factors that promote hydrolysis: low pH and high temperature (above 40°C). Although the static headspace analysis method used to obtain the data in the White et al. study may require heating to achieve adequate sensitivity, many laboratories perform purge-and-trap analyses without heating. Under those conditions, hydrolysis may not occur. However, it may be prudent to preserve samples with alkaline preservatives, to eschew high temperatures during the analysis of groundwater samples, or to neutralize the sample pH before heating.     

Polymer and invert emulsifying oil effects upon droplet size spectra of sprays

Abstract

A series of wind tunnel atomization studies were carried out to investigate the effects of polymer and invert suspension oil “drift control adjuvants” upon the droplet size distribution spectra produced by nozzles typically used in aerial and ground based spraying of pesticides. A D8–46 disc and core was used as a typical aerial application nozzle, and an 8003 fan nozzle was used for the ground based sprayers simulation. The droplet size spectra were evaluated in a wind tunnel using a Malvern 2600 laser particle size analyzer immediately upon mixing and at 15 minutes after re‐circulation through a pumping system. The addition of the polymer‐based adjuvants significantly increased the droplet size spectra parameters of the spray cloud, but all the polymer products showed signs of breakdown of their molecular arrangements in the liquid medium, as a result of agitation. The invert suspension oil adjuvant did not change the droplet size spectra markedly, nor did it show signs of breakdown of the internal liquid structure after re‐circulation.     

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op′-DDD, pp′-DDD, pp′-DDE, op′-DDT, pp′-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.