Meixun Zhao

An interlaboratory study of TEX86 and BIT analysis of sediments, extracts, and standard mixtures

Two commonly used proxies based on the distribution of glycerol dialkyl glycerol tetraethers (GDGTs) are the TEX86 (TetraEther indeX of 86 carbon atoms) paleothermometer for sea surface temperature reconstructions and the BIT (Branched Isoprenoid Tetraether) index for reconstructing soil organic matter input to the ocean. An initial round-robin study of two sediment extracts, in which 15 laboratories participated, showed relatively consistent TEX86 values (reproducibility +/- 3-4 degrees C when translated to temperature) but a large spread in BIT measurements (reproducibility +/- 0.41 on a scale of 0-1). Here we report results of a second round-robin study with 35 laboratories in which three sediments, one sediment extract, and two mixtures of pure, isolated GDGTs were analyzed. The results for TEX86 and BIT index showed improvement compared to the previous round-robin study. The reproducibility, indicating interlaboratory variation, of TEX86 values ranged from 1.3 to 3.0 degrees C when translated to temperature. These results are similar to those of other temperature proxies used in paleoceanography. Comparison of the results obtained from one of the three sediments showed that TEX86 and BIT indices are not significantly affected by interlaboratory differences in sediment extraction techniques. BIT values of the sediments and extracts were at the extremes of the index with values close to 0 or 1, and showed good reproducibility (ranging from 0.013 to 0.042). However, the measured BIT values for the two GDGT mixtures, with known molar ratios of crenarchaeol and branched GDGTs, had intermediate BIT values and showed poor reproducibility and a large overestimation of the true (i.e., molar-based) BIT index. The latter is likely due to, among other factors, the higher mass spectrometric response of branched GDGTs compared to crenarchaeol, which also varies among mass spectrometers. Correction for this different mass spectrometric response showed a considerable improvement in the reproducibility of BIT index measurements among laboratories, as well as a substantially improved estimation of molar-based BIT values. This suggests that standard mixtures should be used in order to obtain consistent, and molar-based, BIT values.

Widespread dispersal and aging of organic carbon in shallow marginal seas

The occurrence of pre-aged organic carbon (OC) in continental margin surface sediments is a commonly observed phenomenon, yet the nature, sources, and causes of this aged OC remain largely undetermined for many continental shelf settings. Here we present the results of an extensive survey of the abundance and radiocarbon content of OC in surface sediments from the northern Chinese marginal seas. Pre-aged OC is associated with both coarser (>63 µm) and finer (<63 µm) sedimentary components; measurements on specific grain-size fractions reveal that it is especially prevalent within the 20–63 µm fraction of inner shelf sediments. We suggest that organic matter associated with this sortable silt fraction is subject to protracted entrainment in resuspension-deposition loops during which it ages, is modified, and is laterally dispersed, most likely via entrainment within benthic nepheloid layers. This finding highlights the complex dynamics and predepositional history of organic matter accumulating in continental shelf sediments, with implications for our understanding of carbon cycling on continental shelves, development of regional carbon budgets, and interpretation of sedimentary records.

Biomarker evidence for paleoenvironmental changes in the southern Yellow Sea over the last 8200 years

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 dominant community structure during the mid-late Holocene.

Holocene shifts in riverine fine-grained sediment supply to the East China Sea Distal Mud in response to climate change

Holocene changes in fine-grained sediment supplies to the East China Sea outer shelf were uncovered, through the mineralogical and geochemical analysis of Core B3 in the East China Sea Distal Mud (ECSDM). Based on the lithology, accelerator mass spectrometry (AMS) 14C dating, and sea-level change, Core B3 can be divided into two major units: transgressive stage (Unit 1: 12.5–6.8 kyr) and highstand stage (Unit 2: 6.8–0 kyr). Significant discrepancy of dolomite/calcite ratio in the fine fractions (<16 µm) of Changjiang (dolomite/calcite = 3:1) and Huanghe (dolomite/calcite = 1:22) sediments was used as a new uniqueness provenance tracer to distinguish these two riverine sources. Both of the dolomite/calcite ratio and rare earth elements fractionation parameters in the fine-grained sediment indicated distinct provenance shifts of Core B3 during the Holocene. Unit 1 of Core 3 (12.5–6.8 kyr) mainly consists of the reworked and resuspension sediments of the East China Sea shelf during the Holocene transgression, while Unit 2 sediments (6.8–0 kyr) are most likely sourced from the Changjiang and Huanghe. Moreover, mixing curves of dolomite/calcite ratio reveal that the ECSDM continuously received the Changjiang sediment since 6.1 kyr with notable fluctuations, whereas the Huanghe sediment supply began in 6.8 kyr but abruptly stopped during 4.2–0.8 kyr and then appeared again since 0.8 kyr. Temporal changes of the Changjiang and Huanghe fine-grained sediment contribution to the ECSDM are closely related to the formation of modern oceanic circulation system since 6.8 kyr (shelf sea-level change), the ‘4.2 kyr’ climate event, and the followed transition to cold and dry climate condition in the northeastern China (global climate change), as well as the artificial shift of lower Huanghe course in ad 1128 in the war against invasion of the northern nomadic nation (human activities).

Holocene temperature records from the East China sea mud area southwest of the Cheju Island reconstructed by the U37K′ and TEX86 paleothermometers

As an important marginal sea under the influences of both the Changjiang River and the Kuroshio, the East China Sea (ECS) environment is sensitive to both continental and oceanic forcing. Paleoenvironmental records are essential for understanding the long-term environmental evolution of the ECS and adjacent areas. However, paleo-temperature records from the ECS shelf are currently very limited. In this study, the U37K′ and TEX86 paleothermometers were used to reconstruct surface and subsurface temperature changes of the mud area southwest of the Cheju Island (Site F10B) in the ECS during the Holocene. The results indicate that temperature changes of F10B during the early Holocene (11.6–6.2 kyr) are associated with global climate change. During the period of 6.2–2.5 kyr, the similar variability trends of smoothing average of ΔT (the difference between surface and subsurface temperature) of Site F10B and the strength of the Kuroshio suggest that the Kuroshio influence on the site started around 6.2 kyr when the Kuroshio entered the Yellow Sea and continued to 2.5 kyr. During the late Holocene (2.5–1.45 kyr), apparent decreases of U37K′ sea surface temperature (SST) and ΔT imply that the direct influence of the Kuroshio was reduced while cold eddy induced by the Kuroshio gradually controlled hydrological conditions of this region around 2.5 kyr.

Biomarker records of phytoplankton productivity and community structure changes during the last 14000 years in the mud area southwest off Cheju Island, East China Sea

The ecological environment in the East China Sea (ECS) and the Yellow Sea (YS) has changed significantly due to sea-level rising and the Kuroshio incursion since the last deglaciation. In this study, biomarker records of core F10B from the mud area southwest off Cheju Island (MSWCI) were generated to evaluate phytoplankton productivity and community structure changes in response to environmental evolution during the last 14 kyr. The contents of diatom, dinoflagellate and haptophyte biomarkers (brassicasterol, dinosterol and C37 alkenones) display similar trends, with increasing phytoplankton productivity during the last 14 kyr due to the increased influences of the Kuroshio, and especially due to the eddy-induced upwelling during the late Holocene. On the other hand, the contents of terrestrial biomarkers (C28 +C30 +C32n-alkanols) and terrestrial organic matter (TOM) proxies (TMBR’ and BIT) all reveal decreasing TOM input into the area around the sampling site for the 14 kyr, mostly due to sea-level rising. Phytoplankton biomarker ratios reveal a shift from a haptophyte-dominated community at 6.2–2.5 kyr BP to a diatom-dominated community at 2.5–1.45 kyr BP, likely caused by a stronger cold eddy circulation system at 2.5–1.45 kyr BP in the MSWCI.

Ecosystem responses to anthropogenic and natural forcing over the last 100 years in the coastal areas of the East China Sea

Ecosystem changes of the coastal areas of the East China Sea (ECS) during the past 30 years have been characterized by increased productivity and increased occurrences of dinoflagellate red tides; both were commonly attributed to be caused by anthropogenic input of nutrients. However, climate-driven regime shifts were found in the Pacific, but they have not been observed in the ECS owing to the lack of continuous high resolution data. Hence, it is still a challenge to distinguish the influences of anthropogenic activities and climate changes on ECS shelf ecosystem. We compare phytoplankton biomarker (brassicasterol, dinosterol, and alkenones) data of five box cores from the coastal area of the ECS, which afford phytoplankton productivity and community structure records at decadal-scale resolution for the last 100 years. Phytoplankton productivity in all cores increased during the past 50 years, but community structure changes showed different trends. Relative diatom contribution revealed a decreasing trend during the past ca. 50 years in cores DH5-1 and CJ43 collected near the Changjiang Estuary, which were likely caused by increased N/Si and N/P ratios, providing conditions more favorable for dinoflagellates growth. In contrast, the relative diatom contribution increased in cores 32, 34, and DH6-3 further away and south of the Changjiang Estuary, suggesting limited influence of the Changjiang water. Instead, diatom increasing trend is likely caused by increased supply of phosphorus and silicate, as a result of larger Kuroshio intrusion flux and the corresponding strengthened coastal upwelling. Therefore, both anthropogenic activities and climate-driven coastal upwelling have contributed to increased productivities, but these two forcing mechanisms have resulted in contrasting community structure changes at different sites in the coastal area of the ECS.

Biomarker records of phytoplankton productivity and community structure changes in the Central Yellow Sea mud area during the Mid-late Holocene

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 6 kyr to 3 kyr, 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 ZY1 suggest spatial variations in response to YSWC and KC forcing. When the KC was intensified during the periods of 6–4.2 kyr and 1.7–0 kyr, 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.

Major mid-late Holocene cooling in the East China Sea revealed by an alkenone sea surface temperature record

Although the mid-late Holocene cold and dry event about 4000 years ago (the 4 ka 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 U37K′ index for Core B3 on the continental 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 5.6 ka) to the 4 ka event (19.2°C at 3.8 ka). 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 El Niño/Southern Oscillation activities in the Equatorial Pacific. 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 decrease. 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.

Upwelling and anthropogenic forcing on phytoplankton productivity and community structure changes in the Zhejiang coastal area over the last 100 years

Phytoplankton productivity and community structure in marginal seas have been altered significantly during the past three decades, but it is still a challenge to distinguish the forcing mechanisms between climate change and anthropogenic activities. High time-resolution biomarker records of two 210Pb-dated sediment cores (#34: 28.5°N, 122.272°E; CJ12-1269: 28.861 9°N, 122.515 3°E) from the Min-Zhe coastal mud area were compared to reveal changes of phytoplankton productivity and community structure over the past 100 years. Phytoplankton productivity started to increase gradually from the 1970s and increased rapidly after the late 1990s at Site #34; and it started to increase gradually from the middle 1960s and increased rapidly after the late 1980s at Site CJ12-1269. Productivity of Core CJ12-1269 was higher than that of Core #34. Phytoplankton community structure variations displayed opposite patterns in the two cores. The decreasing D/B (dinosterol/brassicasterol) ratio of Core #34 since the 1960s revealed increased diatom contribution to total productivity. In contrast, the increasing D/B ratio of Core CJ12-1269 since the 1950s indicated increased dinoflagellate contribution to total productivity. Both the productivity increase and the increased dinoflagellate contribution in Core CJ12-1269 since the 1950–1960s were mainly caused by anthropogenic activities, as the location was closer to the Changjiang River Estuary with higher nutrient concentration and decreasing Si/N ratios. However, increased diatom contribution in Core #34 is proposed to be caused by increased coastal upwelling, with higher nutrient concentration and higher Si/N ratios.