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Reevaluating Lithium Chloride as a Safer Catalyst for Polylactide Synthesis: A Toxicological and Process Perspective 再评价氯化锂作为聚丙交酯合成的更安全催化剂:毒理学和工艺的观点
IF 3.4 Pub Date : 2025-06-30 DOI: 10.1021/acs.chas.5c00082
Sébastien Moins,  and , Olivier Coulembier*, 

We report a reinvestigation of lithium chloride (LiCl) as a catalyst for the ring-opening polymerization (ROP) of l-lactide, using octa(ethylene glycol) dimethyl ether (EG8) as a coordinating agent. Although conducted under inert atmosphere, the presence of trace water does not impair polymerization efficiency, eliminating the need for high-vacuum techniques or aggressive drying protocols. Water initiates the reaction via in situ formation of HO-Li+ species, which generate lithium lactate, the actual active species in the system. The Li+ coordination environment, modulated by EG8, governs both reactivity and stereocontrol, with prolonged reaction leading to partial epimerization of l-lactide into meso-lactide. The process proceeds with excellent control, as evidenced by narrow dispersities and linear Mn evolution, until interchain condensation occurs. Beyond this, the system enables polymerization from nonrecrystallized l-lactide and activates alcohol-based co-initiators such as 1-pyrenemethanol with quantitative end-group incorporation. This work provides mechanistic insight into LiCl-catalyzed ROP and highlights a safer, function-oriented approach to PLA synthesis under sustainable conditions.

本文报道了以八乙酸乙二醇二甲醚(EG8)为配位剂,氯化锂(LiCl)作为l-丙交酯开环聚合(ROP)催化剂的再研究。虽然在惰性气氛下进行,但微量水的存在不会影响聚合效率,从而消除了对高真空技术或侵略性干燥方案的需求。水通过原位生成HO-Li+引发反应,生成乳酸锂,这是系统中的实际活性物质。由EG8调节的Li+配位环境控制着反应性和立体控制,反应时间延长导致l-丙交酯部分外映成中位丙交酯。该过程在良好的控制下进行,如窄分散度和线性Mn演化所证明的那样,直到链间缩合发生。除此之外,该系统还可以从非再结晶的l-丙交酯中进行聚合,并通过定量端基掺入激活醇基共引发剂,如1-芘甲醇。这项工作为licl催化的ROP提供了机制见解,并强调了在可持续条件下更安全,功能导向的PLA合成方法。
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引用次数: 0
Domino Effect Risk Modeling and Analysis of Tank Area Accidents Based on Accident Chain and Multifactor Coupling 基于事故链和多因素耦合的油罐区事故多米诺效应风险建模与分析
IF 3.4 Pub Date : 2025-06-26 DOI: 10.1021/acs.chas.5c00024
Xue Li, Wei’ao Liu, Bing Chen, Ning Zhou*, Weibo Huang, Yiting Liang, Xiongjun Yuan and Zhaoyu Li, 

To explore the propagation laws of the domino effect in tank areas, this paper constructs a domino effect analysis model based on the unit accident chain and multifactor synergistic effect. The model not only evaluates the contribution of the unit accident chain to domino effect development but also analyzes the enhanced destructive effect when multiple factors interact. From the perspective of energy accumulation, the heat dose criterion is used to dynamically update the conditional probability tables in the dynamic Bayesian network (DBN), thus more realistically simulating the evolution of the domino effect. It overcomes the limitation of the traditional DBN that can only analyze the domino effect at specific time points and can identify critical vulnerabilities more accurately, providing timely decision support for reducing the impact of accidents. The effectiveness of this method is verified through case studies, confirming its reliability and practicality in analyzing the propagation patterns of the domino effect.

为探讨罐区多米诺效应的传播规律,本文构建了基于单位事故链和多因素协同效应的多米诺效应分析模型。该模型不仅评价了单位事故链对多米诺骨牌效应发展的贡献,而且分析了多因素相互作用时的增强破坏效应。从能量积累的角度出发,利用热剂量准则对动态贝叶斯网络(DBN)中的条件概率表进行动态更新,更真实地模拟了多米诺骨牌效应的演化过程。它克服了传统DBN只能在特定时间点分析多米诺骨牌效应的局限性,能够更准确地识别关键漏洞,为减少事故影响提供及时的决策支持。通过实例验证了该方法的有效性,验证了该方法在分析多米诺效应传播模式中的可靠性和实用性。
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引用次数: 0
Direct Prediction of Chemical Hazards in GHS Classification Using SMILES Representation for Health and Safety Applications 在健康和安全应用中使用SMILES表示直接预测GHS分类中的化学品危害
IF 3.4 Pub Date : 2025-06-19 DOI: 10.1021/acs.chas.5c00035
Takaaki Harada*, Rumiko Hayashi and Kengo Tomita, 

Physical, health, and environmental hazards of chemical substances are classified into hazard classes in the Globally Harmonized System of Classification and Labeling of Chemicals (GHS). Within each hazard class in the GHS classification, the degree of chemical hazard is mostly expressed as a category. The chemical hazard information is in high demand for risk assessment and accident prevention; however, the hazards of most chemical substances are undetermined yet. Investigations on chemical hazards involve a time-consuming step such as in vitro and in vivo studies, whereas more and more novel chemical substances are synthesized on a daily basis. It is essential to accelerate investigations into the identification of chemical hazards. Herein, we use deep learning models to predict the hazard classes and categories of chemical substances in the GHS classification. The chemical structure is expressed as the Simplified Molecular Input Line Entry System (SMILES) notation. A hazard class prediction model is trained on a data set of chemical structures in SMILES that are labeled as to whether they are classified into the hazard class or not. Similarly, a hazard category prediction model is trained on a data set of SMILES labeled with a hazard category within the hazard class. The average accuracy values of hazard class and category prediction models are 89.2 and 70.4%, respectively. Test-time augmentation is employed to gain the ability of robust prediction regardless of the input chemical structure in SMILES. The atoms of a molecule that contribute to the correct prediction are determined by calculating their attribution scores, which provide insight into our prediction models. Our chemical hazard prediction models can be used as a tool for risk assessment and prioritization of physicochemical studies on novel chemical substances.

化学物质的物理、健康和环境危害在全球化学品统一分类和标签制度(GHS)中被划分为危害等级。在GHS分类的每个危害类别中,化学品的危害程度大多用一个类别来表示。风险评估和事故预防对化学品危害信息的需求很大;然而,大多数化学物质的危害尚未确定。对化学物质危害的调查涉及到体外和体内研究等耗时的步骤,而越来越多的新型化学物质每天都在被合成。必须加快对查明化学品危害的调查。在此,我们使用深度学习模型来预测GHS分类中化学物质的危害等级和类别。化学结构表示为简化分子输入线输入系统(SMILES)符号。对smile中化学结构的数据集进行危险等级预测模型的训练,这些化学结构被标记为是否属于危险等级。类似地,危险类别预测模型在标有危险类别中的危险类别的SMILES数据集上进行训练。灾害等级和类别预测模型的平均准确率分别为89.2和70.4%。在smile中,测试时间的增加可以获得与输入化学结构无关的鲁棒预测能力。对正确预测有贡献的分子原子是通过计算它们的归因分数来确定的,这为我们的预测模型提供了洞察力。我们的化学危害预测模型可作为新化学物质理化研究风险评估和优先排序的工具。
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引用次数: 0
Assessment of Effective Dose in the Oil and Gas Industry of Saudi Arabia 沙特阿拉伯石油和天然气工业有效剂量评估
IF 3.4 Pub Date : 2025-06-12 DOI: 10.1021/acs.chas.5c00084
Abdulrahman Aliyu*, Luai M. Alhems and Abbas Mohammed, 

Natural, technologically enhanced, and industrial radionuclides contribute to occupational ionizing radiation exposure in the oil and gas industry, posing potential risks to workers and the environment. This study evaluates occupational dose levels in Saudi Arabia’s oil and gas sector from 2016 to 2022 using thermoluminescent dosimeters (TLDs). The results show that the annual effective dose (ED) remained below the 20 mSv/year occupational limit set by UNSCEAR, ICRP, and the IAEA, indicating minimal health risk. For the oil industry, the mean ED was 0.57 ± 0.35 mSv (range: 0.05–4.61 mSv), and for the gas industry, it was 0.57 ± 0.26 mSv (range: 0.11–1.62 mSv). The 95% confidence intervals, 0.57 ± 0.011 mSv for oil and 0.57 ± 0.018 mSv for gas, confirm the robustness of these estimates. Notably, this study highlights that TLD-based measurements yield more reliable, job-specific exposure estimates than commonly used computational models. The findings support ongoing regulatory compliance, promote adherence to ALARA principles, and provide a regional benchmark for radiation safety in the oil and gas sector.

天然的、技术增强的和工业放射性核素造成了石油和天然气工业中的职业性电离辐射暴露,对工人和环境构成潜在风险。本研究使用热释光剂量计(tld)评估了2016年至2022年沙特阿拉伯石油和天然气行业的职业剂量水平。结果表明,年有效剂量仍低于科委会、ICRP和国际原子能机构规定的20毫西弗/年职业限值,表明健康风险极小。对于石油行业,平均ED为0.57±0.35 mSv(范围:0.05-4.61 mSv),对于天然气行业,平均ED为0.57±0.26 mSv(范围:0.11-1.62 mSv)。95%置信区间(石油为0.57±0.011 mSv,天然气为0.57±0.018 mSv)证实了这些估计的稳健性。值得注意的是,该研究强调,与常用的计算模型相比,基于tld的测量结果产生了更可靠的、特定于工作的暴露估计。研究结果支持持续的监管合规,促进对ALARA原则的遵守,并为石油和天然气行业的辐射安全提供区域基准。
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引用次数: 0
Ceramic High Efficiency Particulate Air (HEPA) Filter Research and Development at Lawrence Livermore National Laboratory 劳伦斯利弗莫尔国家实验室的陶瓷高效微粒空气(HEPA)过滤器研究与开发
IF 3.4 Pub Date : 2025-06-11 DOI: 10.1021/acs.chas.4c00131
Michael Ross, Andrew T. Hoff, William M. Hochstedler, Sarah Case, Lauren R. Finkenauer, James P. Kelly, Mark Mitchell and Jeffery J. Haslam*, 

Ceramic high efficiency particulate air (HEPA) filter development program began at Lawrence Livermore National Laboratory (LLNL) over 20 years ago. Historical incidents motivated current safety systems at nuclear facilities. A ceramic filter that can survive a fire can provide robust, passive safety protection. Research has been conducted to improve the safety of nuclear facilities and to reduce operational and lifecycle costs, through ceramic filter technology that can survive fire conditions. The research focused on applications in both new facilities as well as meeting operational requirements necessary to retrofit filters into existing DOE facilities. The research has developed multiple filter technologies spanning traditional HEPA filter materials to advanced manufacturing technologies (e.g., electrospinning, additive manufacturing, etc.). This communication will present highlights of selected development efforts for ceramic HEPA filter research, current state-of-the-art for ceramic filters, and future needs including technical, regulatory, and commercial efforts.

陶瓷高效微粒空气(HEPA)过滤器的开发计划始于20多年前的劳伦斯利弗莫尔国家实验室(LLNL)。历史事件推动了当前核设施的安全系统。陶瓷过滤器可以在火灾中幸存,可以提供强大的被动安全保护。为了提高核设施的安全性,降低运行和生命周期成本,已经进行了研究,通过陶瓷过滤技术,可以在火灾条件下生存。研究的重点是在新设施中的应用,以及满足将过滤器改造到现有DOE设施中所必需的操作要求。该研究开发了从传统HEPA过滤材料到先进制造技术(如静电纺丝、增材制造等)的多种过滤技术。本次交流将重点介绍陶瓷HEPA过滤器研究的选定开发工作,陶瓷过滤器的最新技术,以及未来的需求,包括技术,监管和商业努力。
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引用次数: 0
Chemical Hazard Assessment of Vanadium–Vanadium Flow Battery Electrolytes in Failure Mode 失效模式下钒-钒液流电池电解液的化学危害评价
IF 3.4 Pub Date : 2025-06-11 DOI: 10.1021/acs.chas.5c00047
Kourosh Khaje, Behzad Fuladpanjeh-Hojaghan, Jürgen Gailer, Viola Birss and Edward P.L. Roberts*, 

The growing demand for energy storage and the rising frequency of lithium ion battery failure events worldwide underscore the urgency of addressing the battery safety challenges. Ensuring the safe and reliable deployment of advanced battery technologies is paramount. Flow batteries present a promising solution for long-duration energy storage, yet their electrolytes pose potential hazards to human health and the environment. The largest scale vanadium–vanadium flow batteries have been reported in China, with a 100 MW/400 MWh system reportedly commissioned in 2022 and a 175 MW/700 MWh battery completed in December 2024. This is equivalent to 150–200 million liters of vanadium electrolyte. This study aims to assess the chemical hazards of the electrolytes in vanadium–vanadium flow battery during failure mode. There is little or no chemical hazard data for the electrolyte mixtures, and the hazard assessment was thus based on chemical reactivity and toxicity data for the individual electrolyte components. Potential failure modes are identified with overcharging (or high cell voltages) in particular presenting potential hazards due to the possible production of toxic gases. Depending on the electrolyte composition, these conditions could result in the evolution of Cl2, SO2, H2S, or PH3 gases, with immediate associated risks for human health. The two main all-vanadium flow battery chemistries use either sulfuric acid or sulfuric acid/HCl mixtures as the supporting electrolyte, with low concentrations of phosphoric acid often included in the sulfuric acid systems. The sulfuric acid–based cells generate oxygen and hydrogen at the positive and negative half-cell electrodes, respectively, during overcharge. On the other hand, the mixed H2SO4/HCl-based chemistries produce chlorine at the positive electrode during overcharge and potentially under normal charging conditions at high states-of-charge if the flow-rate is insufficient. Vanadium electrolytes containing chloride ions therefore present the most significant toxicity hazards in failure mode. The inherently safe design of battery management and control systems, along with electrolyte containment, is an essential measure to ensure safe flow battery operation. The next step involves designing controlled experiments to study overcharging effects on the electrolyte stability and degradation.

储能需求的增长和全球锂离子电池故障事件的增加凸显了解决电池安全挑战的紧迫性。确保先进电池技术的安全可靠部署至关重要。液流电池为长时间储能提供了一种很有前途的解决方案,但其电解质对人体健康和环境构成潜在危害。据报道,中国规模最大的钒钒液流电池,据报道,一个100兆瓦/400兆瓦时的系统于2022年投入使用,一个175兆瓦/700兆瓦时的电池于2024年12月完工。这相当于1.5亿到2亿升的钒电解质。本研究旨在评估钒钒液流电池失效模式下电解液的化学危害。电解质混合物的化学危害数据很少或根本没有,因此危害评估是基于单个电解质成分的化学反应性和毒性数据。潜在的失效模式被确定为过度充电(或高电池电压),特别是由于可能产生有毒气体而呈现潜在的危险。根据电解质成分的不同,这些条件可能导致Cl2、SO2、H2S或PH3气体的演变,对人体健康产生直接的相关风险。两种主要的全钒液流电池化学方法都使用硫酸或硫酸/盐酸混合物作为支撑电解质,硫酸体系中通常含有低浓度的磷酸。硫酸基电池在过充电时,在正半电池电极和负半电池电极分别产生氧和氢。另一方面,混合的H2SO4/ hcl基化学物质在过充电时在正极产生氯,如果流量不足,在正常充电条件下在高电荷状态下可能会产生氯。因此,含氯离子的钒电解质在失效模式下呈现出最显著的毒性危害。电池管理和控制系统的固有安全设计以及电解液密封是确保液流电池安全运行的重要措施。下一步包括设计控制实验来研究过充电对电解质稳定性和降解的影响。
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引用次数: 0
Occupational Exposure to Manganese from Welding Fumes during Arc Welding Operations: Data from the Field 电弧焊接作业中职业性暴露于焊接烟雾中的锰:来自现场的数据
IF 3.4 Pub Date : 2025-06-10 DOI: 10.1021/acs.chas.5c00048
Juliana H. Halbach*, Chandler M. Cottam and Ravyn Tyler, 

Workers who perform arc welding are exposed to fumes generated by the joining of metals. One generated fume is manganese, a metal with heightened toxicological properties. This paper explores welders’ manganese exposures during the four most performed arc welding types: Shielded Metal Arc Welding (SMAW), Gas Tungsten Arc Welding (GTAW), Gas Metal Arc Welding (GMAW), and Flux Cored Arc Welding (FCAW). Exposure data were collected in varying field environmental conditions at Lawrence Livermore National Laboratory (LLNL) in Livermore, California. Conditions ranged from indoor shop areas controlled with local exhaust ventilation (LEV) to outdoor construction areas with variable wind directions and speeds. Exposure samples were taken for both inhalable and respirable fractions of manganese. This sampling effort was conducted in response to the updated 2016 Manganese Threshold Limit Values (TLVs) that were adopted into LLNL’s contract in 2019 to ensure compliance with the new, lower exposure standard. The resulting data collected from the field informed risk level determinations that were calculated using Bayesian Decision Analysis (BDA) to determine potential exceedances to the manganese TLVs. The resulting BDA outcomes indicate potential for manganese overexposure during SMAW, GMAW, and FCAW arc welding processes. LLNL leverages these BDA outcomes to make health and safety risk-based assessment decisions for a wide range of construction, research and development, engineering, and maintenance activities conducted by many of its 9,000+ employee workforce.

进行电弧焊的工人暴露在金属连接产生的烟雾中。一种产生的烟雾是锰,一种具有高度毒性的金属。本文探讨了焊工在四种最常用的电弧焊类型中的锰暴露情况:保护金属电弧焊(SMAW),气体钨极电弧焊(GTAW),气体金属电弧焊(GMAW)和药芯电弧焊(FCAW)。暴露数据是在加利福尼亚州利弗莫尔的劳伦斯利弗莫尔国家实验室(LLNL)在不同的野外环境条件下收集的。条件范围从采用局部排气通风(LEV)控制的室内商店区域到风向和风速可变的室外施工区域。采集了锰的可吸入和可呼吸部分的暴露样本。此次采样工作是为了响应更新的2016年锰阈值(tlv),该tlv于2019年被LLNL的合同采用,以确保符合新的低暴露标准。从现场收集的结果数据为风险水平确定提供了依据,使用贝叶斯决策分析(BDA)计算风险水平,以确定锰tlv的潜在超标情况。由此得出的BDA结果表明,在SMAW、GMAW和FCAW电弧焊过程中,锰可能过度暴露。LLNL利用这些BDA结果,为其9,000多名员工中的许多人进行的广泛的建筑、研发、工程和维护活动做出基于健康和安全风险的评估决策。
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引用次数: 0
Risk Assessment in a Chemical Laboratory Following an Explosive Incident Involving a Novel Diazonium Compound: Retrospective Analysis and Lessons Learned 涉及新型重氮化合物爆炸事件后化学实验室的风险评估:回顾性分析和经验教训
IF 3.4 Pub Date : 2025-06-06 DOI: 10.1021/acs.chas.4c00117
Samantha M. Kruse, Brynal A. Benally, Nathan R. Bays, Jessica Román-Kustas* and Ryan D. Davis*, 

Diazonium compounds are synthetically useful in the production of dyes and textiles, however they are highly explosive under dry conditions. Explosion prevention becomes more difficult when new diazonium compounds are synthesized, because while some syntheses include a counterion to increase their stability, this is not always a reliable method to prevent an explosive incident. Due to the uncertainty surrounding the explosiveness of different diazonium compounds, it is important to understand how to safely clean up after an incident and how to determine when it is safe to return a laboratory to typical operational use, particularly when the incident involves a novel compound where a standard does not exist for instrument calibration. Here, an explosive event is discussed involving the synthesis of 4-bromo-benzenediazonium-2-carboxylate. Following the explosive incident and 3-step cleanup, which involved a precautionary neutralization step, samples were collected from the fume hood where the incident occurred. Because the incident involved an unstable, novel compound that is not commercially available and was deemed unsafe to resynthesize for instrument calibration, we assessed the risk of further explosion by analyzing for the stable decomposition products. Mass spectrometry analysis confirmed that the residue in the fume hood contained 5-bromosalicylic acid, a decomposition product of 4-bromo-benzenediazonium-2-carboxylate. Samples were taken from multiple points in the fume hood and analyzed to estimate the spatial distribution of the decomposition product. Based on this analysis, we inferred that the primary decomposition product was far more abundant than residual energetic, indicating the energetic had been consumed or neutralized to a trace quantity where the risk of further explosion was low. The steps presented here─specifically, initial neutralization and then analyzing the spatial distribution of expected decomposition products to assess risk when a novel explosive material is detonated in a confined space─were our approach to assess further risk following an explosion due to a novel diazonium compound without the need for any further handling or resynthesis of the energetic. Here, we present our approach and critically analyze these steps by discussing retrospective lessons learned and alternative analytical approaches.

重氮化合物在染料和纺织品的生产中是有用的,但是它们在干燥条件下是高度易爆的。当合成新的重氮化合物时,防爆变得更加困难,因为虽然一些合成物包括反离子以增加其稳定性,但这并不总是防止爆炸事件的可靠方法。由于不同重氮化合物的爆炸性存在不确定性,了解事故后如何安全清理以及如何确定何时可以安全地将实验室恢复到典型的操作使用是很重要的,特别是当事故涉及到没有仪器校准标准的新化合物时。本文讨论了一个涉及4-溴苯二氮-2-羧酸盐合成的爆炸事件。在爆炸事件和包括预防性中和步骤的三步清理之后,从事件发生的通风柜中收集了样本。由于该事件涉及一种不稳定的新型化合物,这种化合物没有商业上的可用性,并且被认为不安全,无法重新合成用于仪器校准,因此我们通过分析稳定分解产物来评估进一步爆炸的风险。质谱分析证实,通风柜中的残留物含有5-溴水杨酸,这是4-溴苯二氮-2-羧酸盐的分解产物。从通风柜的多个点采集样本并进行分析,以估计分解产物的空间分布。根据这一分析,我们推断初级分解产物远比残余能源丰富,表明能源已被消耗或中和到微量,进一步爆炸的风险较低。本文介绍的步骤──具体地说,是初步中和,然后分析预期分解产物的空间分布,以评估在密闭空间内引爆一种新型爆炸物时的风险──是我们评估新型重氮化合物爆炸后进一步风险的方法,无需进一步处理或重新合成能量。在这里,我们提出我们的方法,并通过讨论回顾经验教训和替代分析方法批判性地分析这些步骤。
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引用次数: 0
Systematic Approach to Laboratory Safety Assessment: A Case Study from a University Setting 实验室安全评估的系统方法:以大学为例
IF 3.4 Pub Date : 2025-06-05 DOI: 10.1021/acs.chas.5c00054
Amirhossein Naserbakht, Faezeh Tavassoli, Farzaneh Mostaed Mohsenabadi and Mehran Ghalenoei*, 

This study systematically assessed chemical and physical hazards in 28 educational laboratories at the Qazvin University of Medical Sciences using the assessment and classification of hazards in laboratories (ACHiL) framework. The assessment involved walkthrough inspections, interviews, and checklist-based evaluations aligned with the guidelines of the Occupational Safety and Health Administration (OSHA), Globally Harmonized System (GHS) for Classification and Labeling of Chemicals, and National Fire Protection Association (NFPA). Among the 540 chemicals analyzed, 57% were classified as high risk, including substances such as methanol, phenol, nitric acid, and sulfuric acid. The Toxicology, Environmental Health, and Microbiology laboratories showed the highest concentrations of hazardous chemicals. Physical hazards, including electrical risks, ultraviolet radiation, and hot surfaces, were also identified and classified based on WHO and NFPA protocols. The results underscore the urgent need for enhanced chemical safety training, consistent use of personal protective equipment (PPE), improved ventilation systems, and regular inventory updates. This methodology offers a replicable model for laboratory risk assessment and contributes to the advancement of occupational health and safety in academic environments.

本研究使用实验室危害评估和分类(ACHiL)框架系统地评估了加兹温医科大学28个教育实验室的化学和物理危害。评估包括根据职业安全与健康管理局(OSHA)、全球化学品分类和标签协调系统(GHS)和国家消防协会(NFPA)的指导方针进行巡视检查、访谈和基于检查清单的评估。在分析的540种化学物质中,57%被列为高风险物质,包括甲醇、苯酚、硝酸和硫酸等物质。毒理学、环境卫生和微生物学实验室显示,有害化学物质的浓度最高。物理危害,包括电气风险、紫外线辐射和热表面,也根据世卫组织和NFPA协议进行了识别和分类。研究结果强调,迫切需要加强化学品安全培训、持续使用个人防护装备(PPE)、改进通风系统和定期更新库存。这种方法为实验室风险评估提供了一个可复制的模型,并有助于促进学术环境中的职业健康和安全。
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引用次数: 0
Temperature and Pressure Characteristics, and the Hazards of Thermal Decomposition of Organic Peroxides 温度和压力特性,以及有机过氧化物热分解的危害
IF 3.4 Pub Date : 2025-06-02 DOI: 10.1021/acs.chas.4c00146
Pin Liu,  and , Xiongmin Liu*, 

Organic peroxides are widely used substances and are hazardous materials. Pressure vessel testing (PVT) is an important method for evaluating rapid thermal decomposition and the hazards of organic peroxides. However, it is difficult to evaluate volatile organic peroxides using PVT. In this paper, the hazardous material characteristic is that temperature and pressure undergo rapid changes during thermal decomposition. The pressure and temperature behaviors of the peroxide thermal decomposition process are investigated using a mini closed pressure vessel test (MCPVT), and the relationship between MCPVT and PVT is explored. The results showed a good linear relationship between the parameter (dP/dt)Max × (dT/dt)Max ((dP/dt)max is the maximum pressure rise rate and (dT/dt)max is the maximum temperature rise rate) of MCPVT and orifice diameter (D) of PVT. The linear equation is y = 6.576 × 104 × −3.994 × 104 (where y = (dP/dt)Max × (dT/dt)Max, x = D). According to the linear equation, the grade classification of rapid thermal decomposition and hazards of organic peroxides is divided into four levels: “none”, “low”, “medium”, and “violent”. In addition, the volatility and thermal decomposition exothermic properties of organic peroxides were studied by thermogravimetric differential thermal analysis (TG-DTA), and it has been found that the peroxides di-t-butyl peroxide (DTBP), cumene hydroperoxide (CHP), dicumyl peroxide (DCP), and t-butyl peroxy acetate (TBPA) are volatile. It is important for fuel additives to have appropriate volatility.

有机过氧化物是一种用途广泛的有害物质。压力容器试验(PVT)是评价有机过氧化物快速热分解和危害的重要方法。然而,使用pvt对挥发性有机过氧化物进行评价是困难的。在本文中,危险物质的特点是在热分解过程中温度和压力发生快速变化。采用微型密闭压力容器试验(MCPVT)研究了过氧化物热分解过程的压力和温度行为,并探讨了MCPVT与PVT的关系。结果表明,MCPVT参数(dP/dt)Max × (dt /dt)Max ((dP/dt) Max为最大升压速率,(dt /dt)Max为最大温升速率)与pvt孔径(D)之间存在良好的线性关系,线性方程为y = 6.576 × 104 ×−3.994 × 104(其中y = (dP/dt)Max × (dt /dt)Max, x = D)。根据线性方程,将有机过氧化物的快速热分解及危害等级划分为“无”、“低”、“中”、“剧烈”四个等级。此外,用热重差热分析(TG-DTA)研究了有机过氧化物的挥发性和热分解放热性能,发现过氧化物有挥发性,包括过氧化物二叔丁基(DTBP)、过氧化氢异丙烯(CHP)、过氧化二氨基(DCP)和过氧乙酸叔丁酯(TBPA)。燃油添加剂具有适当的挥发性是很重要的。
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Journal of chemical health & safety
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