长江口及邻近海域低氧现象的探讨
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摘要
本研究在实验室建立了海洋中浮游植物光合色素的高效液相色谱测定方法。并以此为基础，测定了长江下游徐六泾、长江口和毗邻东海北部海区悬浮颗粒物以及现场有机物降解培养实验中的颗粒物色素浓度，同时还测定了长江口E4柱状沉积物中的色素含量；分析了1999至2003年共计5个航次的长江口、东海颗粒有机碳样品并进行了相关的动力学探讨。在此基础上，以2005至2007年共计5次长江口现场观测为依托，同时充分考虑颗粒有机碳、营养盐等其他生物地化参数，结合历史资料和文献报道，针对长江口和毗邻海区夏季出现的底层水低氧现象，对其历史趋势、严重程度、发生机制进行了探讨和分析。
对长江口和毗邻东海的生物地球化学背景研究显示，长江口、陆架区域和黑潮为主的外海POC平均含量分别为26.5，7.7和3.3μM。断面分布上，底层较高的TSM值(117mg／L)有时甚至达到表层的13倍之高。在E4站位，连续站观测说明POC含量分布呈现周期变化：正弦函数拟合显示，长江口POC日变化周期约为13h，和长江口半日潮周期相吻合；结合文献资料估算E4站位POC在真光层的停留时间在10天左右，且向外海呈现增加的趋势。在从长江口到冲绳海槽的整个东海陆架上，我们观测到底层存在一个高悬浮颗粒物浓度的雾状层。配合文献中的流场数据，估算出通过该雾状层向冲绳海槽输运的POC通量为0.22×10~(12)g／yr，占长江输入东海POC通量的约2％。
2004年8月至2007年2月在长江下游徐六泾的月际观测表明，长江口徐六泾色素以叶绿素a(Chla)含量最高(平均值0.9μg／L)，2006年Chla含量比2005年增加了0.2μg／L，其余色素含量平均值从0.02μg／L到0.32μg／L不等。其中岩藻黄素(Fuco)是次于Chla的最高浓度色素(平均值0.3μg／L)，再次是多甲藻素(Perid，平均值0.1μg／L)。Chla含量季节变化不明显，Fuco和Perid等其他色素则存在一定季节变化，但差异小于100％。
2006年6月至10月长江口和毗邻海区悬浮颗粒物中Chla，Fuco，Perid和叶绿素b(Chlb)等色素含量(平均值)分别为1.3μg／L，900ng／L，290ng／L和64ng／L。6～8月Chla平均值差异很小。但具体每次调查期间的特征色素含量却有差别。6月Perid含量较高，在8月和10月则主要以Fuco为主。空间分布显示，Chla主要分布在长江口东经123°的区域，向西或向东含量均下降；Perid／Fuco比值则在东经122.5°左右较大，随着进入外海比值下降。垂向上，色素主要分布在表层和次表层，40m以下浓度很低。2005年8月调查区域更靠近长江口，类似的，主要以Chla(1.3μg／L)、Fuco(1.3μg／L)和Perid(0.2μg／L)等色素为主。2007年2月调查区域涵盖整个东海南部陆架，与夏季相比，该季节色素含量较低。Chla、Fuco、Perid和Chlb平均值分别降为0.6μg／L，240ng／L，40ng／L和76ng／L。2006年在调查海域南部观测到DV Chla，暗示南部海域原绿球藻的存在。
根据现场溶氧(DO)数据并结合文献资料，发现长江口外低氧发生在夏季。发生低氧的区域主要在东经122°～123.5°，北纬30°～33°之间。从可查的1959年8月以来，底层溶氧平均值从1959年的5.9mg／L降低到2006年8月的2.7mg／L，同时低氧面积从1959年8月的～1800km~2增加到2006年8月的15400km~2，同时伴随大量DO＜3mg／L的溶氧低值区。2006年8月氧亏损量达到1.7×10~6t，比文献中报道的1999年8月情况更为恶化。低氧面积、氧亏损量增加的同时，与历史情况相比长江口低氧区呈现北移的趋势，中心区域从北纬31°北移至2006年的北纬32.5°。
在调查中发现，较高的溶氧一般在较低的POC／Chla值下出现，随着POC／Chla值的增大，DO值逐渐降低。说明当有机物降解较彻底时，水体中溶解氧含量较低，有机物尚比较新鲜则溶解氧含量较高。
对溶氧与其他参数的进一步分析显示，AOU同时与有机物降解明显相关：底层样品的AOU与POC／PO4和POC／NO3呈负相关，说明有机物降解、营养盐再生与低氧伴随在一起。同时低氧与层化度Δρ／ΔZ有较好的相关性。综合温度、层化度和有机物降解等参数的多元回归分析也显示，AOU与层化度、有机物降解两者间存在较强的相关性，与温度的关系不大。说明长江口底层水的低氧是水体层化和有机物降解综合作用的结果，可以用式摘-1定量表达：
AOU=2.5+0.0015×T~2+0.2570×Δρ-0.3730×ln(POC／NO_3)摘-1
2006年10月在现场进行的有机物降解实验中，色素在培养前后含量发生了明显的下降。实验条件分别控制为低氧(DO％＜50％)和富氧(DO％＞95％)两类。低氧条件下Chla和Fuco含量分别从0.8μg／L、1.0μg／L下降为0.3μg／L、0.5μg／L；富氧条件下Chla和Fuco含量分别从1μg／L、1.4μg／L下降为0.3μg／L、0.3μg／L。POC在实验前后含量也存在下降，含量分别从20.7μM(低氧)、28.6μM(富氧)下降为18.0μM(低氧)、16.3μM(富氧)。由于体系本身较高的营养盐含量，因此培养实验前后营养盐变化与有机物降解的耦合关系不明显，但低氧条件下氨氮实验前后存在明显增大，同时FCM技术检测显示细菌在实验过程中含量从910×10~3个／mL增加为最后的1300×10~3个／mL。聚球藻等FCM可检测的浮游植物在培养过程中含量下降明显，分别从低氧和富氧的270×10~2个／mL，200×10~2个／mL下降为最后的20×10~2个／mL、40×10~2个／mL。整个培养降解过程均伴随着体系的pH值下降。指数函数拟合显示，在本实验人工控制的条件下(特定的营养盐背景、较低的加富色素量及约20μM的POC浓度背景等)，Chla的降解常数k(d~(-1))在低氧和富氧下分别为0.22和0.18，Fuco分别为0.21和0.18(0.67＜r~2＜0.96)。Chla在富氧下半衰期比低氧短，说明低氧更有利于Chla的保存；Fuco则两种条件下降解速度差异不大。根据有机碳降解的估算显示，长江口夏季有机碳降解造成对溶氧的需求速率为1.7～1.9mmol m~(-3)d~(-1)。
进一步对长江口沉积物的色素分析显示，长江口和毗邻海区的表层沉积物中Chla平均含量65mg／g OC，最大值为170mg／g OC。然后是Fuco含量较高，平均值38mg／g OC；再其次是Perid，平均值17mg／g OC。Fuco和Perid与Chla的分布比较相似，在长江口门附近区域含量较低，在该低值区域南北含量较高。但Fuco的含量是Perid的约2倍。Chlb最大值出现在调查区域的东北角H1-6站位，含量为44mg／g OC，Chlb在沉积物中含量平均值14mg／g OC。沉积物中Perid／Fuco(0.46)和Fuco／Chla(0.56)等比值与水体中Perid／Fuco(0.56)和Fuco／Chla(0.56)比值相近，而Allo／Chla(0.23)则与水体中(0.01)差异较大，可能与色素不同的稳定性有关。在高沉积速率的长江口区域，表层沉积物中色素与水体中高Chla和低氧分布趋势相似，说明高生产力、低氧环境有利于色素在沉积物中的埋藏与保存。E4柱中的色素在表层出现最大值，并在40cm左右以上随着深度的增加而迅速降低，Chla含量变化范围0.4～147mg／g OC，另外Fuco、Zea、Allo等平均值分别为6.3、11和7.3mg／g OC。在沉积物中Chla分布与1998年洪水等历史事件的响应说明沉积物中色素作为生物标志物的有效性，同时色素与沉积物中的生物硅分布趋势、历史上现场水体Chla含量、长江径流量等变化趋势相吻合。色素随深度变浅含量迅速上升，与长江流域近几十年来营养盐通量增加、长江口赤潮增加相对应。Chla与δ15N的显著相关性(r~2=0.86，p=0.001)说明人文因素排放的化肥与长江口高Chla含量有密切关系。模式分析显示，Chla在长江口沉积物中含量呈明显的指数式下降(r~2=0.94)，降解常数k=1.39yr~(-1)。扣去该指数降解因素后，Chla在1980年后仍呈增大趋势，说明长江口水环境在上世纪80年代改革开放以来比之前更有利于色素的埋藏。
We established the HPLC method of phytoplankton pigments analysis in our lab and measured the samples from Xuliujing, the Changjiang estuary, East China Sea (ECS) and a sediment core. The distribution and dynamics of POC in the Changjiang estuary and ECS were discussed based on the data from 1999 to 2003, in order to shed light on the background of the study area. Further, based on the field observation data and a culture experiment, hypoxia in the Changjiang estuary and its adjacent area were studied.
Averaged POC value in the Changjiang estuary, continental shelf and outer area where Kuroshio prevailed are 26.5, 7.7 and 3.3μM, respectively. Elevated TSM (117mg/L) were observed at the bottom, probably due to resuspension. At E4 station, continuous survey for 24h suggested that POC value varied periodically, following the pattern of a sinusoidal curve. Observed curve fit well with the assumed theoretical sinusoidal curve, with periodic of 13h, consistent with the tide. Residence time of POC at E4 station is on the order of weeks, increasing eastwards. POC flux through the nepheloid layer to the Okinawa Trough was estimated to be 0.22 × 10~(12)g/yr. ～2% of the Changjiang POC flux.
As indicated by the survey at Xuliujing, chlorophyll a concentration in 2006 increased 0.2μg/L than that in 2005, averaged 0.9μg/L Other pigments ranged from 0.02μg/L to 0.32μg/L, with fucoxanthin 0.3μg/L, peridinin 0.1μg/L. Seasonal variation of chlorophyll a is not clear, while as for the other pigments, difference among seasons is within 100%.
Chlorophyll a, fucoxanthin, peridinin and chlorophyll b averaged 1.3μg/L, 900ng/L, 290ng/L and 64ng/L from June to October, 2006. In respect of the diagnostic pigment, peridinin was higher in June and elevated fucoxanthin was found in August and October. Elevated chlorophyll a is found at 123°E, decreased both eastwards and westwards. Perid/Fuco ratio elevated at 122.5 °E, decreased with distance from the Changjiang estuary. Pigment mainly distributed at surface and subsurface layer, and depleted beneath 40m. In the cruise of August, 2005, which covered an area closer to the Changjiang, chlorophyll a, fucoxanthin and peridinin mean value were 1.3μg/L, 1.3μg/L and 0.2μg/L, respectively. As to the Feberary, 2007, which covered the whole ECS shelf, pigment values were generally lower than that in summer time, with mean value of chlorophyll a, fucoxanthin, peridinin and chlorophyll b being 0.6μg/L, 240ng/L, 40ng/L and 76ng/L DV chlorophyll a was observed at the southeast part, indicating the existence of Prochlorococcus.
Based on the field observation data, hypoxia occurred in summer time, between 122～123.5°E and 30～33°N. Average bottom DO value decreased from 5.9mg/L (1959) to 2.7mg/L (2006), with area increased from ～1800km~2 (1959) to 15400km~2 (2006). In August, 2006, vast area of DO less than 3 mg/L also was observed. The condition in 2006 was worse than that as reported in 1999. A comparison with former study reveals that the hypoxia area is moving northwards.
Elevated DO value was accompanied with lower POC/chlorophyll a ratio. DO decreased with increasing POC/chlorophyll a value, indicating that low DO occurred when the organic matter contained less fresh content.
Analysis with other parameters reveals that AOU is correlated with
organic matter decay: the AOU is reversely correlated with POC/NO3.
Meanwhile, hypoxia showed good relationship with Δρ/ΔZ. Multiple analysis
suggested that AOU is closely correlated with stratification and organic matter decay. No clearly relationship was found between AOU and temperature in summer. Thus hypoxia in the Changjiang estuary is mainly the result of stratification and organic matter decay. The AOU could then be quantitatively expressed as follows:
AOU=2.5+0.0015 × T~2+0.2570 × Δρ-0.3730 × In(POC/NO_3)
An organic matter decay experiment was carried out on board in October, 2006, with condition controlled as low DO (DO%<50%) and high DO (DO%>95%). Pigments decreased apparently before and after the experiment. In the low DO condition, chlorophyll a and fucoxanthin decreased from 0.8μg/L and 1.0μg/L to 0.3μg/L and 0.5μg/L In the high DO condition, chlorophyll a and fucoxanthin decreased from 1 μg/L and 1.μg/L to 0.3μg/L and 0.3μg/L. POC value also decreased from 20.7μM(low DO), 28.6μM(high DO) to 18.0μM(low DO), 16.3μM(high DO), respectively. No clearly coupling between nutrients and POC were found probably due to the high nutrients background concentration. However, ammonia did increase through the experiment, probably due to the activity of bacteria, since bacteria increased from 910×10~3/mL to 1300×10~3/mL FCM-detectable phytoplankton decreased clearly through out the experiment, from 270×10~2/mL(low DO), 200×10~2/mL(high DO) to finally 20×10~2/mL(low DO), 40×10~2/ml_(high DO). Under such a specific experiment condition (i.e. high nutrient, POC value ～20μM, low pigments initial concentration), Chlorophyll a and fucoxanthin showed clearly exponentional decay, with decay constant k (d~(-1)) of 0.22(low DO), 0.18(high DO) and 0.21 (low DO), 0.18(high DO), respectively. Chlorophyll a concentration half life is longer under low DO condition, indicating that pigments decay slower under low DO condition. Estimate based on the POC decay suggest that the oxygen demand rate is 1.7-1.9mmol m~(-3) d~(-1) in the Changjiang estuary in summer.
Further analysis of sediment pigments reveals that chlorophyll a concentration of the surface sediment averaged 65mg/g OC in the Changjiang estuary and adjacent area, followed by fucoxanthin (38mg/g OC) and peridinin (17mg/g OC). Content of chlorophyll a, fucoxanthin and peridinin is depleted close to the Changjiang river mouth, surrounded by elevated area north and south. With regards to chlorophyll b, mean value is 14mg/g OC, with maximum 44mg/g OC. Pigment ratio of peridinin/fucoxanthin (0.46) and fucoxanthin/chlorophyll a (0.56) in the surface sediment is close to that (0.56 and 0.56, respectively) in the water column. Alloxanthin/chlorophyll a ratio in the sediment (0.23) differed much from that in the water column (0.01), probably due to the different stabilities. Distribution of chlorophyll a in the sediment is similar to the chlorophyll a and hypoxia in the water column, suggesting that elevated primary production and low DO concentration is propitious to pigments conservation. In respect to the E4 core, pigment showed elevated value at the surface and decreased dramatically with depth. Chlorophyll a ranged from 0.4～147mg/g OC. Averaged value of fucoxanthin, zeaxanthin, alloxanthin were 6.3, 11 and 7.3 mg/g OC, respectively. Chlorophyll a distribution in sediment core showed good agreement with that of Bio-silicate, in situ chlorophyll a content and the Changjiang water discharge. Dramatical increase of pigments at the upper part of the core, coincide with the history of eutrophication of the Changjiang and increasing blooms in the area. Modeling analysis suggests that chlorophyll a decayed in the core following an exponential pattern (r~2=0.94), with decay constant k=1.39yr~(-1). Considering the exponential decay process, chlorophyll a still showed increase trend after 1980s, indicating the water column was more suitable for pigments conservation after 1980s.
对长江口和毗邻东海的生物地球化学背景研究显示，长江口、陆架区域和黑潮为主的外海POC平均含量分别为26.5，7.7和3.3μM。断面分布上，底层较高的TSM值(117mg／L)有时甚至达到表层的13倍之高。在E4站位，连续站观测说明POC含量分布呈现周期变化：正弦函数拟合显示，长江口POC日变化周期约为13h，和长江口半日潮周期相吻合；结合文献资料估算E4站位POC在真光层的停留时间在10天左右，且向外海呈现增加的趋势。在从长江口到冲绳海槽的整个东海陆架上，我们观测到底层存在一个高悬浮颗粒物浓度的雾状层。配合文献中的流场数据，估算出通过该雾状层向冲绳海槽输运的POC通量为0.22×10~(12)g／yr，占长江输入东海POC通量的约2％。
2004年8月至2007年2月在长江下游徐六泾的月际观测表明，长江口徐六泾色素以叶绿素a(Chla)含量最高(平均值0.9μg／L)，2006年Chla含量比2005年增加了0.2μg／L，其余色素含量平均值从0.02μg／L到0.32μg／L不等。其中岩藻黄素(Fuco)是次于Chla的最高浓度色素(平均值0.3μg／L)，再次是多甲藻素(Perid，平均值0.1μg／L)。Chla含量季节变化不明显，Fuco和Perid等其他色素则存在一定季节变化，但差异小于100％。
2006年6月至10月长江口和毗邻海区悬浮颗粒物中Chla，Fuco，Perid和叶绿素b(Chlb)等色素含量(平均值)分别为1.3μg／L，900ng／L，290ng／L和64ng／L。6～8月Chla平均值差异很小。但具体每次调查期间的特征色素含量却有差别。6月Perid含量较高，在8月和10月则主要以Fuco为主。空间分布显示，Chla主要分布在长江口东经123°的区域，向西或向东含量均下降；Perid／Fuco比值则在东经122.5°左右较大，随着进入外海比值下降。垂向上，色素主要分布在表层和次表层，40m以下浓度很低。2005年8月调查区域更靠近长江口，类似的，主要以Chla(1.3μg／L)、Fuco(1.3μg／L)和Perid(0.2μg／L)等色素为主。2007年2月调查区域涵盖整个东海南部陆架，与夏季相比，该季节色素含量较低。Chla、Fuco、Perid和Chlb平均值分别降为0.6μg／L，240ng／L，40ng／L和76ng／L。2006年在调查海域南部观测到DV Chla，暗示南部海域原绿球藻的存在。
根据现场溶氧(DO)数据并结合文献资料，发现长江口外低氧发生在夏季。发生低氧的区域主要在东经122°～123.5°，北纬30°～33°之间。从可查的1959年8月以来，底层溶氧平均值从1959年的5.9mg／L降低到2006年8月的2.7mg／L，同时低氧面积从1959年8月的～1800km~2增加到2006年8月的15400km~2，同时伴随大量DO＜3mg／L的溶氧低值区。2006年8月氧亏损量达到1.7×10~6t，比文献中报道的1999年8月情况更为恶化。低氧面积、氧亏损量增加的同时，与历史情况相比长江口低氧区呈现北移的趋势，中心区域从北纬31°北移至2006年的北纬32.5°。
在调查中发现，较高的溶氧一般在较低的POC／Chla值下出现，随着POC／Chla值的增大，DO值逐渐降低。说明当有机物降解较彻底时，水体中溶解氧含量较低，有机物尚比较新鲜则溶解氧含量较高。
对溶氧与其他参数的进一步分析显示，AOU同时与有机物降解明显相关：底层样品的AOU与POC／PO4和POC／NO3呈负相关，说明有机物降解、营养盐再生与低氧伴随在一起。同时低氧与层化度Δρ／ΔZ有较好的相关性。综合温度、层化度和有机物降解等参数的多元回归分析也显示，AOU与层化度、有机物降解两者间存在较强的相关性，与温度的关系不大。说明长江口底层水的低氧是水体层化和有机物降解综合作用的结果，可以用式摘-1定量表达：
AOU=2.5+0.0015×T~2+0.2570×Δρ-0.3730×ln(POC／NO_3)摘-1
2006年10月在现场进行的有机物降解实验中，色素在培养前后含量发生了明显的下降。实验条件分别控制为低氧(DO％＜50％)和富氧(DO％＞95％)两类。低氧条件下Chla和Fuco含量分别从0.8μg／L、1.0μg／L下降为0.3μg／L、0.5μg／L；富氧条件下Chla和Fuco含量分别从1μg／L、1.4μg／L下降为0.3μg／L、0.3μg／L。POC在实验前后含量也存在下降，含量分别从20.7μM(低氧)、28.6μM(富氧)下降为18.0μM(低氧)、16.3μM(富氧)。由于体系本身较高的营养盐含量，因此培养实验前后营养盐变化与有机物降解的耦合关系不明显，但低氧条件下氨氮实验前后存在明显增大，同时FCM技术检测显示细菌在实验过程中含量从910×10~3个／mL增加为最后的1300×10~3个／mL。聚球藻等FCM可检测的浮游植物在培养过程中含量下降明显，分别从低氧和富氧的270×10~2个／mL，200×10~2个／mL下降为最后的20×10~2个／mL、40×10~2个／mL。整个培养降解过程均伴随着体系的pH值下降。指数函数拟合显示，在本实验人工控制的条件下(特定的营养盐背景、较低的加富色素量及约20μM的POC浓度背景等)，Chla的降解常数k(d~(-1))在低氧和富氧下分别为0.22和0.18，Fuco分别为0.21和0.18(0.67＜r~2＜0.96)。Chla在富氧下半衰期比低氧短，说明低氧更有利于Chla的保存；Fuco则两种条件下降解速度差异不大。根据有机碳降解的估算显示，长江口夏季有机碳降解造成对溶氧的需求速率为1.7～1.9mmol m~(-3)d~(-1)。
进一步对长江口沉积物的色素分析显示，长江口和毗邻海区的表层沉积物中Chla平均含量65mg／g OC，最大值为170mg／g OC。然后是Fuco含量较高，平均值38mg／g OC；再其次是Perid，平均值17mg／g OC。Fuco和Perid与Chla的分布比较相似，在长江口门附近区域含量较低，在该低值区域南北含量较高。但Fuco的含量是Perid的约2倍。Chlb最大值出现在调查区域的东北角H1-6站位，含量为44mg／g OC，Chlb在沉积物中含量平均值14mg／g OC。沉积物中Perid／Fuco(0.46)和Fuco／Chla(0.56)等比值与水体中Perid／Fuco(0.56)和Fuco／Chla(0.56)比值相近，而Allo／Chla(0.23)则与水体中(0.01)差异较大，可能与色素不同的稳定性有关。在高沉积速率的长江口区域，表层沉积物中色素与水体中高Chla和低氧分布趋势相似，说明高生产力、低氧环境有利于色素在沉积物中的埋藏与保存。E4柱中的色素在表层出现最大值，并在40cm左右以上随着深度的增加而迅速降低，Chla含量变化范围0.4～147mg／g OC，另外Fuco、Zea、Allo等平均值分别为6.3、11和7.3mg／g OC。在沉积物中Chla分布与1998年洪水等历史事件的响应说明沉积物中色素作为生物标志物的有效性，同时色素与沉积物中的生物硅分布趋势、历史上现场水体Chla含量、长江径流量等变化趋势相吻合。色素随深度变浅含量迅速上升，与长江流域近几十年来营养盐通量增加、长江口赤潮增加相对应。Chla与δ15N的显著相关性(r~2=0.86，p=0.001)说明人文因素排放的化肥与长江口高Chla含量有密切关系。模式分析显示，Chla在长江口沉积物中含量呈明显的指数式下降(r~2=0.94)，降解常数k=1.39yr~(-1)。扣去该指数降解因素后，Chla在1980年后仍呈增大趋势，说明长江口水环境在上世纪80年代改革开放以来比之前更有利于色素的埋藏。
We established the HPLC method of phytoplankton pigments analysis in our lab and measured the samples from Xuliujing, the Changjiang estuary, East China Sea (ECS) and a sediment core. The distribution and dynamics of POC in the Changjiang estuary and ECS were discussed based on the data from 1999 to 2003, in order to shed light on the background of the study area. Further, based on the field observation data and a culture experiment, hypoxia in the Changjiang estuary and its adjacent area were studied.
Averaged POC value in the Changjiang estuary, continental shelf and outer area where Kuroshio prevailed are 26.5, 7.7 and 3.3μM, respectively. Elevated TSM (117mg/L) were observed at the bottom, probably due to resuspension. At E4 station, continuous survey for 24h suggested that POC value varied periodically, following the pattern of a sinusoidal curve. Observed curve fit well with the assumed theoretical sinusoidal curve, with periodic of 13h, consistent with the tide. Residence time of POC at E4 station is on the order of weeks, increasing eastwards. POC flux through the nepheloid layer to the Okinawa Trough was estimated to be 0.22 × 10~(12)g/yr. ～2% of the Changjiang POC flux.
As indicated by the survey at Xuliujing, chlorophyll a concentration in 2006 increased 0.2μg/L than that in 2005, averaged 0.9μg/L Other pigments ranged from 0.02μg/L to 0.32μg/L, with fucoxanthin 0.3μg/L, peridinin 0.1μg/L. Seasonal variation of chlorophyll a is not clear, while as for the other pigments, difference among seasons is within 100%.
Chlorophyll a, fucoxanthin, peridinin and chlorophyll b averaged 1.3μg/L, 900ng/L, 290ng/L and 64ng/L from June to October, 2006. In respect of the diagnostic pigment, peridinin was higher in June and elevated fucoxanthin was found in August and October. Elevated chlorophyll a is found at 123°E, decreased both eastwards and westwards. Perid/Fuco ratio elevated at 122.5 °E, decreased with distance from the Changjiang estuary. Pigment mainly distributed at surface and subsurface layer, and depleted beneath 40m. In the cruise of August, 2005, which covered an area closer to the Changjiang, chlorophyll a, fucoxanthin and peridinin mean value were 1.3μg/L, 1.3μg/L and 0.2μg/L, respectively. As to the Feberary, 2007, which covered the whole ECS shelf, pigment values were generally lower than that in summer time, with mean value of chlorophyll a, fucoxanthin, peridinin and chlorophyll b being 0.6μg/L, 240ng/L, 40ng/L and 76ng/L DV chlorophyll a was observed at the southeast part, indicating the existence of Prochlorococcus.
Based on the field observation data, hypoxia occurred in summer time, between 122～123.5°E and 30～33°N. Average bottom DO value decreased from 5.9mg/L (1959) to 2.7mg/L (2006), with area increased from ～1800km~2 (1959) to 15400km~2 (2006). In August, 2006, vast area of DO less than 3 mg/L also was observed. The condition in 2006 was worse than that as reported in 1999. A comparison with former study reveals that the hypoxia area is moving northwards.
Elevated DO value was accompanied with lower POC/chlorophyll a ratio. DO decreased with increasing POC/chlorophyll a value, indicating that low DO occurred when the organic matter contained less fresh content.
Analysis with other parameters reveals that AOU is correlated with
organic matter decay: the AOU is reversely correlated with POC/NO3.
Meanwhile, hypoxia showed good relationship with Δρ/ΔZ. Multiple analysis
suggested that AOU is closely correlated with stratification and organic matter decay. No clearly relationship was found between AOU and temperature in summer. Thus hypoxia in the Changjiang estuary is mainly the result of stratification and organic matter decay. The AOU could then be quantitatively expressed as follows:
AOU=2.5+0.0015 × T~2+0.2570 × Δρ-0.3730 × In(POC/NO_3)
An organic matter decay experiment was carried out on board in October, 2006, with condition controlled as low DO (DO%<50%) and high DO (DO%>95%). Pigments decreased apparently before and after the experiment. In the low DO condition, chlorophyll a and fucoxanthin decreased from 0.8μg/L and 1.0μg/L to 0.3μg/L and 0.5μg/L In the high DO condition, chlorophyll a and fucoxanthin decreased from 1 μg/L and 1.μg/L to 0.3μg/L and 0.3μg/L. POC value also decreased from 20.7μM(low DO), 28.6μM(high DO) to 18.0μM(low DO), 16.3μM(high DO), respectively. No clearly coupling between nutrients and POC were found probably due to the high nutrients background concentration. However, ammonia did increase through the experiment, probably due to the activity of bacteria, since bacteria increased from 910×10~3/mL to 1300×10~3/mL FCM-detectable phytoplankton decreased clearly through out the experiment, from 270×10~2/mL(low DO), 200×10~2/mL(high DO) to finally 20×10~2/mL(low DO), 40×10~2/ml_(high DO). Under such a specific experiment condition (i.e. high nutrient, POC value ～20μM, low pigments initial concentration), Chlorophyll a and fucoxanthin showed clearly exponentional decay, with decay constant k (d~(-1)) of 0.22(low DO), 0.18(high DO) and 0.21 (low DO), 0.18(high DO), respectively. Chlorophyll a concentration half life is longer under low DO condition, indicating that pigments decay slower under low DO condition. Estimate based on the POC decay suggest that the oxygen demand rate is 1.7-1.9mmol m~(-3) d~(-1) in the Changjiang estuary in summer.
Further analysis of sediment pigments reveals that chlorophyll a concentration of the surface sediment averaged 65mg/g OC in the Changjiang estuary and adjacent area, followed by fucoxanthin (38mg/g OC) and peridinin (17mg/g OC). Content of chlorophyll a, fucoxanthin and peridinin is depleted close to the Changjiang river mouth, surrounded by elevated area north and south. With regards to chlorophyll b, mean value is 14mg/g OC, with maximum 44mg/g OC. Pigment ratio of peridinin/fucoxanthin (0.46) and fucoxanthin/chlorophyll a (0.56) in the surface sediment is close to that (0.56 and 0.56, respectively) in the water column. Alloxanthin/chlorophyll a ratio in the sediment (0.23) differed much from that in the water column (0.01), probably due to the different stabilities. Distribution of chlorophyll a in the sediment is similar to the chlorophyll a and hypoxia in the water column, suggesting that elevated primary production and low DO concentration is propitious to pigments conservation. In respect to the E4 core, pigment showed elevated value at the surface and decreased dramatically with depth. Chlorophyll a ranged from 0.4～147mg/g OC. Averaged value of fucoxanthin, zeaxanthin, alloxanthin were 6.3, 11 and 7.3 mg/g OC, respectively. Chlorophyll a distribution in sediment core showed good agreement with that of Bio-silicate, in situ chlorophyll a content and the Changjiang water discharge. Dramatical increase of pigments at the upper part of the core, coincide with the history of eutrophication of the Changjiang and increasing blooms in the area. Modeling analysis suggests that chlorophyll a decayed in the core following an exponential pattern (r~2=0.94), with decay constant k=1.39yr~(-1). Considering the exponential decay process, chlorophyll a still showed increase trend after 1980s, indicating the water column was more suitable for pigments conservation after 1980s.
引文
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