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大型海藻基生物炭中多环芳烃分布特征及毒性评价

Distribution characteristics and toxicity evaluation of polycyclic aromatic hydrocarbons in macroalgal biochars

  • 摘要: 研究大型海藻基生物炭中多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)分布特征及毒性可为其资源化利用提供重要的依据。该研究利用索氏提取结合气相色谱质谱法分析了不同热解温度(200、300、400、500和600 ℃)的大型海藻(瓦氏马尾藻(Sagassum vachellianum)、羊栖菜(Sargassum fusiforme)、鼠尾藻(Sargassum thunbergii)、带形蜈蚣藻(Grateloupia turuturu)、粗枝软骨藻(Chondria crassicaulis)及孔石莼(Ulva pertusa))基生物炭中16种PAHs含量并对其毒性进行评价。结果表明,大型海藻基生物炭中均能检出PAHs(总量浓度为78.2~2 244.2 μg/kg),且其生成量整体随热解温度升高先增加后降低。大型海藻基生物炭中PAHs含量均低于欧洲生物炭标准(European Biochar Certificate,EBC,10.1版)规定的EBC-AgroOrganic等级限量值(4±2)mg/kg。大型海藻基生物炭中PAHs以2环和3环为主,4环PAHs在所有生物炭中均存在,而5环和6环PAHs仅在部分生物炭中被检出。此外,不同大型海藻基生物炭呈现各异的苯并a芘毒性当量浓度(BaP- Toxic Equivalence Quantity, TEQBaP)(0.196~46.151 μg/kg),其TEQBaP不仅依赖于生物炭中PAHs含量还与其环数和类型分布有关。在生物炭修复效果且潜在环境风险相近的基础上,结合产率及热解温度耗能,可选择热解温度较低的生物炭材料,为大型海藻基生物炭制备与应用的优化提供重要指导。

     

    Abstract: Biochar has been prevalently recognized as a readily available and environmentally friendly material in recent years. The excellent properties can be a developed pore structure, abundant functional groups, and outstanding cation exchange capacity. Therefore, biochar is often used for the fertilization and/or remediation of water and soil, as well as the long-term sequestration of carbon. Notably, the persistent organic pollutants (e.g. Polycyclic Aromatic Hydrocarbons (PAHs)) are inevitably generated to stagnate in the biochar during the pyrolysis stage. The concentrations and characteristics of these PAHs in the biochar vary significantly, according to the biomass feedstock, pyrolysis temperature, and pyrolysis conditions. Macroalgae plays crucial roles in carbon cycling to slow down eutrophication in the coastal sea ecosystems. Macroalgae can be expected to serve as the precursors for deriving biochars, due to the short growth cycle, abundance, and accessibility. Moreover, the conversion of macroalgae biomass to biochar is beneficial to the waste management and resource usage of macroalgae. However, it is still lacking on the content and toxicity of PAHs in the macroalgal biochars. In this study, the macroalgal biochars were produced from the Sagassum vachellianum, Sargassum fusiforme, Sargassum thunbergii, Grateloupia turuturu, Chondria crassicaulis, and Ulva pertusa at different pyrolysis temperatures (200, 300, 400, 500, and 600 ℃) under oxygen-limited conditions. Sixteen typical PAHs in the macroalgal biochars were extracted and determined using the Soxhlet extraction combined with gas chromatography-mass spectrometry (GC-MS). Their toxicities were evaluated in this case. The results showed that the PAHs were widely distributed in all tested macroalgal biochars. Specifically, the abundance of PAHs in the biochars first increased and then decreased, as the pyrolysis temperature increased. There was the lowest (78.2 μg/kg) total concentration of PAHs in the C. crassicaulis biochar that was prepared at 600 ℃ among the macroalgal biochars. By contrast, the highest (2 244.2 μg/kg) was achieved in the G. turuturu biochar prepared at 300 ℃, indicating the most abundant naphthalene and phenanthrene. The redundancy analysis revealed that there were different effects of pyrolysis temperature on the concentration and proportion of each PAH in the macroalgal biochar. The contents of PAHs in the macroalgal biochars were all lower than the limit value of EBC-AgroOrganic grade (4±2 mg/kg) stipulated in the European Biochar Certificate (EBC, Version 10.1). There were mainly composed of 2 and 3 rings for the PAHs in the macroalgal biochars that were prepared at the pyrolysis temperatures of 200℃-600℃. The 4-ring PAHs were presented in all the macroalgal biochars, whereas the 5- and 6-ring PAHs were detected only in some macroalgal biochars, in which the proportion was very low. In addition, the macroalgal biochars exhibited various toxic equivalence quantity of benzoapyrene (TEQBaP) at different pyrolysis temperatures. This change was attributed to the content, ring number, and type distribution of PAHs in the macroalgal biochars. There was the lowest (0.196 μg/kg) TEQBaP of the C. crassicaulis biochar that derived at 600 ℃ among the tested macroalgal biochars. By contrast, the highest (46.151 μg/kg) was also achieved in the S. thunbergii biochar that was derived at 400 ℃. The TEQBaP of the macroalgal biochars was lower than that of biochars reported previously. The energy consumption of pyrolysis temperature and yield were combined to determine the biochar remediation effect and similar potential environmental risks. Biochar materials with a lower pyrolysis temperature can be selected to provide important guidance for the production and application of macroalgal biochars, thereby improving the utilization of macroalgae.

     

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