Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide （CuO） oxidation method, the modification consisting in a solid phase extraction （SPE） and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations （RSDs） ranging from 0.57% to 8.04% （n=3）, while those with traditional liquid-liquid extraction （LLE） are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% （n=3）. Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 （produced from 10g dry sediment） in the research area is between 0.231 and 0.587mg. S/V and C/V ratios （1.028 ± 0.433 and 0.192±0.066, respectively） indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or （Ad/Al）v suggest that the TOMs has been highly degraded.
ZHANG TingLI XianguoSUN ShuwenLAN HaiqingDU PeiruiWANG Min
The area of East China Sea(ECS)inner shelf is an important sink of suspended particulates from Yangtze River(YR)and materials originated from YR basin.In this study,the parameters of lignin and alkane biomarkers in surface sediment samples from ECS inner shelf were determined to distinguish the sources and to trace the transport of terrigenous organic matters in the region.Our dataset showed that total alkanes with carbon numbers from 10 to 38(T-alkanes)were significantly correlated to both TAR(terrigenous/aquatic ratio)and HMW/LMW(the ratio of high molecular weight to low molecular weight alkanes)(r=0.88,P<0.05 for both),indicating that the majority of T-alkanes was predominantly originated from terrestrial sources,and T-alkanes are important constituents of terrestrial organic matters in the study area.The area was probably affected by petroleum pollution to a certain degree,as indicated by the values of carbon preference index(CPI),odd-over-even carbon number predominance(OEP)and the ratio of pristane to phytane(Pr/Ph).The values of Pr/n-C_(17) and Ph/n-C_(18) suggested a strong reductive sedimentary condition in the region with no obvious biodegradation.The content of eight lignin phenols(Σ8)decreased from the coast to the open sea,indicative of riverine input and hydrodynamic transport of terrigenous organic matters.Lignin degradation parameters presented an increasing trend from the coastline toward the open sea.The lignin vegetation parameters and alkane index(AI)suggested the predominance of non-woody angiosperms in the YR basin.The obvious correlation betweenΛ8(Σ8 normalized to 100 mg organic carbon),TAR and HMW/LMW reveals the significantly concurrent input of lignin and alkanes from terrestrial sources.
于2011年3月17日～4月6日对东、黄海海域进行了大面调查,采集了45个站位不同深度的海水样品,对溶解甲烷(CH4)浓度进行了测定,并估算了其海-气交换通量.结果表明,东、黄海表层海水中溶解甲烷的浓度变化范围是2.39～29.67nmol.L-1,底层海水中甲烷浓度范围是2.63～30.63 nmol.L-1,底层浓度略高于表层,表明底层水体或沉积物中存在甲烷的源.春季东、黄海海域表、底层溶解甲烷的分布特征基本一致,即从近岸向远海逐渐降低,主要受长江冲淡水输入和黑潮水入侵的影响.春季东、黄海海域表层海水中CH4饱和度为93%～1 038%.利用Liss and Merlivat公式(LM86)、Wanninkhof公式(W92)和现场测定的风速估算出春季东、黄海海域CH4的海-气交换通量分别为(2.85±5.11)μmol.(m2.d)-1和(5.18±9.99)μmol.(m2.d)-1,根据本研究结果和文献数据初步估算出东海和黄海年释放甲烷量分别为7.05×10-2～12.0×10-2Tg.a-1和1.17×10-2～2.20×10-2Tg.a-1.春季东、黄海海域表层海水中CH4均呈过饱和状态,是大气中CH4的净源.
The Yellow Sea （YS） environmental and ecological changes during the Holocene are driven by the interactions between the Yellow Sea Warm Current （YSWC）, the East Asian Winter Monsoon （EAWM） and the Kuroshio Current （KC）. We report marine biomarker records of brassicasterol, dinosterol and C37 alkenones in core ZY1 and core ZY2 from the South Yellow Sea （SYS） to reconstruct the spatial/temporal variations and possible mechanisms of phytoplankton primary productivity and community structure changes during the Mid-late Holocene. The contents of the corresponding biomarkers in the two cores are similar, and they also reveal broadly similar temporal trends. From 6kyr to 3kyr, the biomarker contents in the two cores were relatively low with small oscillations, followed by a distinct increase at about 3 kyr indicating productivity increases caused by a stronger EAWM. The alkenone/brassicasterol ratio （A/B） is used as a community structure proxy, which also showed higher values in both cores since 3 kyr, indicating increased haptophyte contribution to total productivity. It is proposed that the YS community structure has been mainly influenced by the YSWC, with stronger YSWC influences causing an increase in haptophyte contribution since 3 kyr. Some differences of the biomarker records between ZY2 and ZYI suggest spatial variations in response to YSWC and KC forcing. When the KC was intensified during the periods of 6-4.2kyr and 1.7-0kyr, the YSWC extended eastward, exerting more influence on core ZY1. On the other hand, when the KC weakened during 4.2-1.7 kyr, the YSWC extended westward, exerting more influence on the ZY2.
Although the mid-late Holocene cold and dry event about 4000years ago （the 4ka event） has been observed almost globally, it was most prominent in terrestrial climate proxies from the lower latitudes. Here we evaluate the oceanic response to this event in terms of a Holocene sea surface temperature （SST） record reconstructed using the U^7 index for Core B3 on the continen- tal shelf of the East China Sea. The record reveals a large temperature drop of about 5~C from the mid-Holocene （24.7~C at 5.6ka） to the 4ka event （19.2~C at 3.8ka）. This mid-late Holocene cooling period in Core B3 correlated with （i） decreases in the East Asia summer monsoon intensity and （ii） the transition period with increased E1 Nifio/Southern Oscillation activities in the Equatorial Pa- cific. Our SST record provides oceanic evidence for a more global nature of the mid-late Holocene climate change, which was most likely caused by a southward migration of the Intertropical Converge Zone in response to the decreasing summer solar insolation in the Northern Hemisphere. However, the large SST drop around Core B3 indicates that the mid-late Holocene cooling was regionally amplified by the initiation/strengthening of eddy circulation/cold front which caused upwelling and resulted in additional SST de- crease. Upwelling during the mid-late Holocene also enhanced with surface productivity in the East China Sea as reflected by higher alkenone content around Core B3.
Anammox （anaerobic ammonium oxidation） is an important process in many suboxic to anoxic marine environments for converting fixed nitrogen to N2, and has a major impact on the marine nitrogen cycle. Ladderane core lipids have been utilized as an indicator of the contribution of anammox to the marine nitrogen cycles. However, such studies have not been reported for the China seas and little is known about the importance of anammox within the nitrogen cycle of these marginal seas. In the research reported here, the ladderane core lipid contents of 17 surface sediment samples from the East China Sea are reported, and their spatial distribution is investigated. C^8-[5]-ladderane FAME, C20-[5]-ladderane FAME and C20-[3]- ladderane FAME have all been detected, suggesting that the anammox bacteria are widely present within the study area. The total contents of the three ladderane lipids （ZFAMEs） range from 24-355 ng/g （weight of dry sediments）, with higher contents occurring in the Minzhe Mud Zone and broadly coincident with the spatial distribution of hypoxia. It is suggested that the sedimentary ladderane core lipids are mainly produced in the water column and their sedimentary contents can be used as indicators of water column hypoxia.
Previous studies have indicated that the Yellow Sea underwent significant environmental changes during the Holocene, but many questions remain concerning the timing of the establishment of the modern circulation system, which would have major implications for the Yellow Sea ecosystem and carbon cycle. In this study, marine and terrestrial biomarkers were analyzed in Core YE-2 from a muddy area in the southern Yellow Sea to reconstruct Holocene environmental and phytoplankton community change. The content of three individual marine phytoplankton biomarkers (alkenones, brassicasterol and dinosterol) all display a similar trend, and their total contents during the early Holocene (362 ng/g) were lower than those during the mid-late Holocene (991 ng/g). On the other hand, the contents of terrestrial biomarkers (C27+C29+C31n-alkanes) during the early Holocene (1 661 ng/g) were about three times higher than those during the mid-late Holocene (499 ng/g). Our biomarker results suggest that the modern circulation system of the Yellow Sea was established by 5-6 ka, and resulted in higher marine productivity and lower terrestrial organic matter inputs. Biomarker ratios were used to estimate shifts in phytoplankton community structure in response to mid-Holocene (5-6 ka) environmental changes in the Yellow Sea, revealing a transition from a dinoflagellate-diatom dominant community structure during the early Holocene to a coccolithophore-dominant community structure during the mid-late Holocene.
Sea surface temperature (SST) records in the South Yellow Sea during the last 6200 years are reconstructed by the unsaturation index of long-chain alkenones (K 37 U ') in sediment core ZY2 from the central mud area.The SST records varied between 14.1 and 16.5°C (15.6°C on average),with 3 phases:(1) A high SST phase at 6.2-5.9 cal ka BP;(2) A low and intensely fluctuating SST phase at 5.9-2.3 cal ka BP;and (3) A high and stable SST phase since 2.3 cal ka BP.Variation of the SST records is similar to intensity of the Kuroshio Current (KC),and corresponds well in time to global cold climate events.However,the amplitude of the SST response to cooling events was significantly different in different phases.The SST response to global cooling event was weak while the KC was strong;and the SST response was strong while the KC was weak.The difference in amplitude of the SST response is possibly caused by the modulation effect of the Yellow Sea Warm Current which acts as a shelf branch of the KC and a compensating current induced by the East Asia winter monsoon.The warm waters brought by the Yellow Sea Warm Current cushion the SST decrease induced by climate cooling,and both the Kuroshio and East Asian winter monsoon play important roles in the modulation mechanism.The SST records display a periodicity of 1482 years.The same period was found in the KC records,indicating that variation of the SST records in the central South Yellow Sea is strongly affected by KC intensity.The same period was also found in Greenland ice cores and North Atlantic and Arabian Sea sediment cores,showing a regional response of marine environmental variability in the East China Seas to that in the global oceans.
WANG LiBoYANG ZuoShengZHANG RongPingFAN DeJiangZHAO MeiXunHU BangQi
