Degradation-fragmentation of marine plastic waste and their environmental implications: A critical review

This review critically evaluates the plastic accumulation challenges and their environmental (primarily) and human (secondarily) impacts. It also emphasizes on their degradation and fragmentation phenomena under marine conditions. In addition, it takes into account the leachability of the various chemical substances (additives) embedded in plastic products to improve their polymeric properties and extend their life. Regardless of their effectiveness in enhancing the polymeric function of plastic products, these additives can potentially contaminate air, soil, food, and water. Several findings have shown that, regardless of their types and sizes, plastics can be degraded and/or fragmented under marine conditions. Therefore, the estimation of fragmentation and degradation rates via a reliable developed model is required to better understand the marine environmental status. The main parameter, which is responsible for initiating the fragmentation of plastics, is sunlight/UV radiation. Yet, UV- radiation alone is not enough to fragment some plastic polymer types under marine conditions, additional factors are needed such as mechanical abrasion. It should be also mentioned that most current studies on plastic degradation and fragmentation centered on the primary stages of degradation. Thus, further studies are needed to better understand these phenomena and to identify their fate and environmental effects.     

Thermal behaviour of hexanuclear titanium(IV) oxo isopropoxide carboxylates,and their usability as a single-source TiO2 CVD precursors

Hexanuclear oxo titanium(IV) isopropoxide carboxylates, of the general formula [Ti₆O₆(OPrⁱ)₆(O₂CR)₆] (R = Bu^t (1), CH₂Bu^t (2)) and [Ti₆O₆(OPrⁱ)₆(O₂CC(CH₃)₂Et)₆] · 0.5(C₇H₈) (3), have been synthesized as polycrystalline powders in order to study their thermal properties and usability as TiO₂ CVD precursors. Analysis of thermogravimetric and variable temperature (VT-IR) data shows that the thermal stability of the synthesized complexes decreases as follows 3 > 2 > 1. The composition of the vapors formed during the thermolysis of 1–3 were qualitatively analysed with VT-IR methods and mass spectrometry (MS-EI). According to obtained results, the decomposition of 1 and 2 proceeds with a partial decomposition and the formation of a volatile and stable titanium species, sufficient for their transport in vapors. The formation of volatile titanium-containing derivatives is an important factor that decides the application of 1 and 2 as precursors in CVD experiments. The high stability of 3 causes the thermal decomposition of this complex to be observed just above 573 K, and volatile titanium-containing derivatives were not detected in vapors. These results indicate that 3 could not be used as a precursor in CVD processes.     

Characterization of the volatile fraction emitted by Pinus spp. by one- and two-dimensional chromatographic techniques with mass spectrometric detection

The chemical composition of the needles of P. pinea, P. pinaster, P. halepensis, P. nigra, P. brutia, P. patula, P. radiata, P. taeda, P. elliotti, P. kesiya, P. sylvestris and P. eldarica was investigated. Headspace solid-phase microextraction and steam distillation extraction were used to collect the volatile fractions. Samples were analyzed using one-dimensional gas chromatography (1D-GC) and comprehensive two-dimensional gas chromatography (GC × GC) associated with a quadrupole and a time-of-flight mass detectors. Results showed that the analytical capabilities of 1D-GC are partially limited by the separation power of the columns. The higher sensibility and the absence of peak skewing of the time-of-flight mass analyzer, with the use of automated peak finding and deconvolution algorithms, allowed for the detection of trace components with qualitative full spectra and the extraction of true mass spectra from coeluting compounds, promoting their reliable identification and thus significantly improving results obtained by 1D-GC/MS, when using a quadrupole mass analyzer. The use of GC × GC resulted in enhanced separation efficiency and increased signal to noise ratio (sensitivity) of the analytes, maximizing mass spectra quality and improving compound detection and identification. This work shows the use of 1D-GC/ToFMS for the analysis of pine needles volatiles, achieving the detection of 177 compounds, that is more than twice the number previously identified by standard 1D-GC/MS. The analysis by GC × GC for the same sample allowed the detection of 212 compounds. The enantioselective GC × GC analysis performed for all the Pinus spp. under study achieved the detection of 422 different compounds. Cross-over phenomena according to operational conditions are highlighted and discussed.     

Comparison of extraction methods for volatile compounds of Muscat grape juice

Typical flavour of Muscat d’Alexandrie wines is mainly due to volatile compounds coming from grapes of this variety. Therefore, the choice of grapes is crucial to obtain musts with a great aromatic potential, which will contribute to the final aroma of wines derived from those musts. In this study, three sampling techniques, liquid-liquid extraction (LLE), solid phase extraction (SPE) and simultaneous distillation-extraction (SDE), were compared for the analysis of volatile compounds in Muscat grape juice. Results showed that although the three techniques can be recommended for the quantitative analysis of volatile compounds from musts, LLE and SPE are better sample preparation techniques than SDE, mainly for determination of polar compounds such as acids or alcohols.     

顶空液液萃取-气相色谱-质谱法用于白术挥发性成分的分析

采用高温顶空液相萃取再转移的方法,对中药白术中挥发性成分进行萃取分离富集,采用顶空液液萃取/气相色谱-质谱(HS-LP-LPE/GC-MS)联用法进行测定,并与传统水蒸汽蒸馏法(SD)提取的挥发性成分进行对比。对各种测定条件和影响因素进行了考察,最佳萃取条件为:1.0 mL PEG 400为高温萃取剂,样品用量1.2 g,萃取温度120℃,萃取时间60 min,再将萃取剂用1.0 mL正己烷进行反萃取后进行GC-MS分析;采用HS-LP-LPE/GC-MS鉴定了33个组分,占总组分含量93.18%;SD鉴定了31个组分,占总组分含量97.12%。两种方法共同检测到的组分有29个,均以苍术酮(Atractylone)含量最高。结果表明,两种方法所提取的组分基本相同,可用于白术挥发性成分的测定。     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

Sampling volatile organic compounds using a modified solid phase microextraction device

Headspace solid phase microextraction (headspace SPME) has been demonstrated to be an excellent solvent-free sampling method. One of the major factors contributing to the success of headspace SPME is the concentrating effect of the fiber coating toward organic compounds. The affinity of the fiber coating toward very volatile analytes, such as chloromethane, may, however, not be large enough for detection at the parts per trillion concentration level. Static headspace analysis, on the other hand, is very effective for these very volatile compounds. As analyte volatility decreases, the sensitivity of static headspace analysis drops. The complementary nature of these two sampling methods can be exploited by combining the SPME device with a gastight syringe. The sensitivity of the new sampling device is better than that of SPME for very volatile compounds or that of static headspace analysis for less volatile compounds. This new method can sample a wide range of compounds from chloromethane (b.p. −24°C) to bromoform (b.p. 149°C) with estimated limits of detection at the low parts per trillion level.     

气相色谱-质谱法测定水中25种挥发性有机物及其在污水厂应急溯源中的应用

采用吹扫捕集-气相色谱-质谱法测定水中25种挥发性有机物的含量,并研究了其在污水厂应急溯源中的应用。25种挥发性有机物在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3.143s)在0.6~5.0μg·L-1之间。以空白样品为基体进行加标回收试验,所得回收率在91.6%~102%之间,测定值的相对标准偏差(n=6)在2.7%~4.6%之间。在一起污水厂冲击案例中,通过污水管网采样及污水样品分析,确定污染因子二氯甲烷,并根据二氯甲烷浓度变化快速锁定污染源头,确保污水厂出口水质达标。     

冠心苏合丸中挥发性组分的分析及主成分冰片的测定

采用同时蒸馏-萃取法提取冠心苏合丸中的挥发性组分,测得两种冠心苏合丸中的挥发性组分含量分别为14％和9．8％。利用GC-MS方法对两种冠心苏合丸所得的挥发性组分进行分析,通过检索NIST98谱图库,并结合标准谱图库和有关文献,从冠心苏合丸的挥发性组分中分别确定出14、19种化学成分,分别占挥发性组分总检出量的97．24％和98．76％。用峰面积归一化法,得出各化学成分在挥发性组分中的相对百分含量。主要挥发性组分是冰片。并采用气相色谱法对冠心苏合丸中冰片的含量进行了测定冰片质量浓度在1．0～5、0mg／mL范围内成良好的线性关系,冰片的平均回收率为98％～106％。