胶州湾表层海水中的正构烷烃及其来源解析

Distribution and Sources of n-alkanes in Surface Seawater of Jiaozhou Bay

正构烷烃是自然界中普遍存在的有机物质,其组成和分布与人类活动密切相关,是表征有机污染物来源的良好标志物.用气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)对2016年4月胶州湾表层海水中的正构烷烃进行检测,首次报道了胶州湾表层海水中正构烷烃的分布特征及来源解析.结果表明,其含量在1.756~39.09μg·L^(-1)之间,主要由连续分布的C11~C_(37)正构烷烃同系物组成,没有明显的奇偶优势,但碳数为C_(21)~C_(33)的正构烷烃约占总正构烷烃的95.0%.胶州湾表层海水中正构烷烃的高值区以湾口为主,在湾内东北部和西部也有出现,这一分布特征与胶州湾东北部和西部河流带来的工业废水、生活污水和湾口码头附近的船舶航运带来的正构烷烃输入有关.水交换较为充分的湾中部和湾外海域正构烷烃总量在1.756~2.842μg·L^(-1)之间,平均值为2.196μg·L^(-1),可视为胶州湾正构烷烃的环境背景值.其碳数分布有明显的C_(24)主碳峰,前峰群有微弱的奇碳优势,后峰群有微弱的偶碳优势,表明这部分正构烷烃以藻类和海洋细菌等生物自生输入为主.人类活动对胶州湾的影响很大,输入的正构烷烃主要集中在湾口及湾内近岸海域,由C_(21)~C_(33)正构烷烃同系物组成,呈现出有微弱偶碳优势的后峰群单峰形分布特征,代表高度风化的石油类污染物.其含量在9.606~39.09μg·L^(-1)之间,约占胶州湾总正构烷烃量的83.7%.整体来看,胶州湾表层海水对正构烷烃的去除机制以蒸发、稀释等物理风化过程为主,从湾内向湾外风化强度增大.

Hydrocarbons emitted by human activities probably constitute the largest class of contaminants that are present in coastal areas, because of widespread use of fossil fuels for power generation and logistics, and accidental spillages. The chemical composition of hydrocarbon mixtures found in the marine environment allowed the identification of relative contributions of different natural and anthropogenic sources. Identification of these hydrocarbons, especially n-alkanes, could act as tracers for the possible sources. To evaluate n-alkanes concentrations with emphasis on source analysis, surface water without visible oil was collected from the cruise in April 2016. Determination and quantification were performed by solvent extraction and gas chromatography-mass spectrometry. Various molecular diagnostic parameters were used to assess the contribution of different sources and origin of n-alkanes in surface seawater of Jiaozhou Bay. Concentrations of total dissolved n-alkanes（C11-C37） were between 1.756-39.09 μg·L-1 with a high carbon number predominance profile without odd-even carbon number preference. The n-alkane concentrations varied spatially depending on the distance away from main input sources and the ability of water exchange. It was at a higher concentration in the northeast and west coastal areas, as well as the mouth of Jiaozhou Bay. And concentrations were relatively lower in the inner area and outside of Jiaozhou Bay. In the sea area with strong water exchange, concentrations of total n-alkanes were around 2.196 μg·L-1, which could be considered as the environmental background level of n-alkanes in Jiaozhou Bay. Those n-alkanes were dominated with C24, with a slightly odd carbon number preference in low carbon n-alkanes and an even carbon number preference in high carbon n-alkanes. The values of CPI for the whole range of n-alkanes series, low carbon n-alkanes, and high carbon n-alkanes were 0.949, 1.026, and 0.980, respectively. Diagnostic indices and curves indicated that the dominant inputs of those n-alkanes were from marine biogenic input such as algae and marine bacteria. The concentration profiles of n-alkanes in other areas were characterized by no odd-even predominance in the range of C21-C33 with peaks center at C24 which were indicative of anthropic contributions as emission sources. N-alkanes dominating with anthropic sources comprised a high proportion（83.7%） of total n-alkanes. Activities of harbors and ships were the main contributors of Jiaozhou Bay n-alkanes. Physical processes, such as evaporation and dilution, were the principal weathering mechanisms. Because of its sufficient environmental capacity, Jiaozhou Bay was still moderately contaminated with petroleum.