长江河口水体有机胶体含量、来源及其对重金属行为影响的研究
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摘要
水体中的有机胶体是指粒径在1nm到0.45gm之间的有机粒子,是胶体的主要组成部分,其比表面积巨大,具有较强的吸附能力,吸附络合水体中的大部分重金属,在其运移和去除过程起着“胶体泵”(真正溶解态和颗粒态之间的传输带)作用,它们的絮凝沉淀、降解、迁移扩散等过程决定了重金属的去向和归宿,对其迁移以及生物有效性发挥了重要的作用。长江河口是长江流域陆源物质向东海运输的主要通道,长江河口地区亦是中国重要的运输和商业枢纽,是一个高度城市化和工业化的区域,河口水体不但接受了上游来水输入的有机胶体,同时还接受了河口地区城市生活污水和工业废水等排放的有机胶体,因而有机胶体较为丰富,成为长江河口区重金属的重要载体。因而,对长江河口水体有机胶体含量、来源及其对重金属行为影响的研究能进一步了解长江河口水环境中重金属的生物地球化学循环,对预防重金属污染,保障人类的健康具有重要的理论意义,同时也是水质监控与治理、保障供水安全的理论依据,具有重大的理论与现实意义。
本论文选择长江河口南支作为研究对象,采集一年四季大潮和小潮涨落潮过程水体(共111个样品),通过切向流超滤技术分离水体中的胶体,并分析、测试其胶体有机碳含量、三维荧光光谱特征、胶体态重金属含量,理清该区域有机胶体的含量、时空分布及其影响因素,并探讨了胶体有机质的类型和来源,最后分析有机胶体对重金属行为的影响,得到以下几点结论：
(1)胶体有机碳(1kDa-0.45μm, COC)作为有机胶体的一个重要的指标,长江河口水体COC含量较高(20.29-154.16μmol·L-1),年均值50.78μmol·L-1,占溶解有机碳(DOC)的平均比例为31.93%,在COC中,以中分子量胶体有机碳(5-500kDa, COC5k)为主,其次是大分子量胶体有机碳(500kDa-0.45μm, COC500k),小分子量胶体有机碳(1-5kDa, COC1k)含量最低。从时间分布上看,COC的浓度表现为冬季>夏季>秋季>春季,大潮>小潮,涨潮>落潮。COC浓度空间分布,近岸点高于河段中间点,且近上海点略高于近崇明点,由于受到人为活动的影响,近岸点季节变化明显大于河段中间点。
(2)2009年长江河口COC年通量大(0.7×106t),受到长江径流量夏丰冬枯的影响,季节通量,夏季最高,秋季次之,春季第三,冬季最小,夏季大量的有机胶体输入长江河口。
(3)长江河口水体胶体有机质(COM)三维荧光光谱除了检测出与溶解有机质(DOM)三维荧光光谱图中的紫外区类富里酸荧光峰A、海洋来源可见光区类富里酸荧光峰C、低激发态类酪氨酸荧光峰B1、高激发态类酪氨酸荧光峰B2以及低激发态类色氨酸荧光峰D1等5种荧光峰,还发现了高激发态类色氨酸荧光峰D2和陆源可见光区类富里酸荧光峰E,前五种荧光物质主要存在于分子量<1kDa的有机组分中,其次是小、中分子量胶体有机质(COM1k和COM5k),大分子量胶体有机质含量(COM500k)最低,最后两种荧光物质主要集中在胶体态中。
(4)各类荧光峰强度指示长江河口水体COM主要来源为人类生活和工农业生产排放(人为源),其次为陆地土壤和植物等有机质残体(陆源),接着是河口浮游生物和微生物分解(内源),河口潮汐过程带来的海洋来源有机质(海源)贡献最小。人为源、内源和海源胶体有机质小分子量胶体态所占比例高于陆源有机质。COM来源具有明显的季节性,陆源贡献表现为秋冬季节明显的大于春夏季节,且秋冬季节COMsk所占比例要高于春夏季节；夏季长江径流量大,河口受到潮汐作用相对弱于其它季节,因此海源贡献较弱；人为源贡献春秋季节高于夏冬季节,春季主要以酪氨酸为主,夏季酪氨酸和色氨酸相差不大,而秋冬季节主要以色氨酸为主,人为排放有机质为水体浮游生物提供食物使得浮游生物生命活动变强,因而内源COM浓度同样也是春秋两季强于夏冬两季。长江河口水体上海沿岸水体受到人为活动影响较强,因此人为排放的有机质要多于河段中间点和近崇明点水体。
(5)长江河口水体胶体态Cu、 Fe、 Mn、 Ni、Cr、Pb、 Zn、 Hg, As等占总溶解态的比例较高,其中胶体态Fe、 Mn、 Cu、 Ni、 Zn和As等6种重金属占总溶解态的比例超过50%。重金属元素的不同分子量胶体态浓度占胶体态比例存在明显的差别,大分子量胶体态Fe、 Mn占胶体态比例均超过65%,小分子量胶体态Pb和As占胶体态比例超过50%,Cu、Cr、 Ni、 Zn和Hg不同分子量胶体态所占比例差别较小,均未超过50%。
(6)长江河口水体胶体态重金属时空分布差异大。
时间分布上,胶体态Cu、 Fe浓度值从春季到冬季递增,且Fe浓度值高,季节变化大,受季节因素影响大；胶体态Mn, Cr浓度由低到高分别是夏季、秋季、春季和冬季,胶体态Ni、 Zn浓度由低到高分别是秋季、春季、夏季和冬季,季节变化较大,季节变化产生一定的影响；胶体态Pb浓度由低到高分别是夏季、秋季、冬季和春季,季节变化小,季节变化对胶体态Pb浓度产生的影响较小。从潮汐过程上看,胶体态重金属大潮高于小潮,涨落潮过程,春、冬季在大、小潮时总体上均表现涨潮浓度高于落潮,而夏、秋季总体上为涨潮浓度低于落潮。
长江沿岸、长江河口区域生产废水和生活污水排放、长江河口船舶航行对水体的扰动等均直接影响水体胶体态重金属浓度的时空分布特征。近上海点小分子量和大分子量胶体态Fe的浓度低于近崇明点,中分子量胶体态Fe高于近崇明点；近岸点小、中分子量胶体态Mn浓度为高于中间点,大分子量胶体态Mn和Cr浓度低于中间点,且近上海点浓度高于近崇明点；近上海点中分子量胶体态Cu和Ni,以及小分子量胶体态Ni和Zn浓度高于其它点,而大分子量胶体态Cu和中分子量胶体态Zn浓度低于近崇明点。
(7)长江河口较高浓度的胶体有机碳形成的“胶体泵”作用,使得重金属Fe、 Mn、 Cr表现为易于从真溶解态向胶体态、再向颗粒态转化进而沉降至沉积物中从水体中清除,重金属Cu、 Ni、 Zn、 Hg和As易于从颗粒态和真溶解态向胶体态转化,而留存于水体中,从而起到调节水体中的重金属行为的作用,影响其生物地球化学循环。
Organic colloids (1nm～0.45μm) is the main component of colloids in natural aquatic environment. It is particularly important due to its high specific surface area and strong potential adsorptive capacity. Most of heavy metals in natural water are combined in various organic colloids. Thus, organic colloids play a critical role in the biogeochemical cycles and bioavailability of heavy metals in aquatic environment, implying a reversibility of the "colloidal pumping" process (transformation between the particulate and dissolved phases through colloidal intermediates).
Yangtze River estuary is the main channel to transport terrigenous material from Yangtze River basin to the East China Sea. Yangtze River estuarine area is an important transportation and business hub, and it also is a highly urbanization and industrialization region. Organic colloid in this area is not only from upstream runoff, but also from municipal sewage and industrial wastewater. These organic colloids become the carrier of heavy metals due to huge specific surface. Thus, we would understand more about heavy metals'biogeochemical cycle by researched on character of organic colloids and its effects on heavy metals behavior in Yangtze River estuary. These researches have important theoretical sense to to prevent pollution, and to protect human health, meanwhile, they have important practical significance to monitor water quality, to make the theory of governance, and to ensure safety of water supply.
In this paper,111water samples were collected from south branch of the Yangtze River estuary during flood and ebb periods of spring and neap tides in different seasons throughout a year. To investigate the content, types, distribution and source of colloidal organic carbon and its effected on heavy metals behavior in the water from Yangtze River estuary (China). Water samples were fractionated into total dissolved (<0.45μm), high molecular weight colloidal (500kDa-0.45μm), medium molecular weight colloidal (5-500kDa), low molecular weight colloidal (1-5kDa) and truely dissolved (<1kDa) fractions with the filters and cross-flow ultrafiltration (CFF) systems, and then all fractions were subsequently characterized for organic carbon content, three dimensional fluorescence spectral characterization and heavy metals content. The main conclusions were showed as follow:
(1) Concentration of colloidal organic carbon (COC) can be used as an indicator of organic colloids concent. A significant proportion of dissolved organic carbon (DOC) was found in colloidal fractions in estuarine water. In Yangtze River estuary, colloidal organic carbon (COC) concentrations was high (20.29μmol·L-1-154.16μmol·L"1, the average was50.78μmol·L-1), and ratios of COC in DOC varied from14.11%to50.50%(the average was31.93%). In COC, the ratio of medium molecular weight colloidal organic carbon (COC5k) was higher than high molecular weight (COCsook) and low molecular weight colloidal organic carbon (COCik). There was a significant temporal variation of COC in the Yangtze River estuary, such as: winter>summer>autumn>spring, spring tide> neap tide, and flood period> ebb period. In Spatial, COC concentrations in coast were higher than in middle of south branch, and water from coast of Shanghai urban slightly higher than from coast of Chongming. In addition, COC seasonal variation in coast was significantly larger than the other sampling sites, due to human activities.
(2) In2009, COC annual flux was0.7*106t. Yangtze River runoff in summer is huge, but few in winter, so COC seasonal flux in Yangtze River estuary was summer>autumn>spring>winter. A large number of COC were transported to estuary through Yangtze River.
(3) In Yangtze River estuary, seven types of fluorescence peaks were observed in three dimensional fluorescence spectrums of dissolved organic matter (DOM) and colloidal organic matter (COM). They were:UV fulvic-like fluorescence peak A, marine sources visible fulvic-like fluorescence peak C, low and high excitation tyrosine peak B1and B2, low and high excitation tryptophan fluorescence peak D1and D2, terrigenous visible fulvic-like fluorescence peak E. Peak A, B1, B2, D1, D2fluorescent substances were mainly existed in the truly dissolved organic matter (UOM,<1kDa), then in low and medium molecular weight colloidal organic matter (COM1k and COMsk,1-500kDa), last in the high molecular weight colloidal organic matter (COM500k). However peak D2and E fluorescent substances were mainly in the colloidal phase.
(4) COM in Yangtze River estuary were mainly originated from anthropogenic sources, secondly from terrigenous sources, thirdly from autochthonous sources (biological decomposition), and the last from marine sources. The concents of anthropogenic, autochthonous, and marine sources COM1k were higher than COM5k, and higher than COMsook, but the contents of terrigenous sources COMsk were higher than COM1k and COMsook.There was obvious seasonal variation of sources of COM in the Yangtze River estuary. Terrigenous inputs in autumn and winter were significantly larger than spring and summer, and COM5k proportion in autumn and winter was higher than spring and summer. Anthropogenic emissions in spring and autumn were higher than summer and winter; in spring colloidal proteins were mainly tyrosine, in summer tyrosine almost same to tryptophan, but in autumn and winter were mainly tryptophan. The COM from anthropogenic sources were the food of plankton, so autochthonous sources from biological activity significantly in spring and autumn were stronger than summer and winter too. Compare to other seasons, marine origins was weakest in summer, because of the huge runoff in this season. In spatial, anthropogenic sources in coast of Shanghai urban was higher than those in middle of south beanch and coast of Chongming as result of human activities.
(5) Heavy metals (Cu, Fe, Mn, Ni, Cr, Pb, Zn, Hg, and As) colloidal fractions were significant in dissolved pool. More than50%of dissolved Fe, Mn, Cu, Ni, Zn, and As were associated with colloidal materials. The distribution of each kind of colloidal heavy metals in different molecular weight was obvious difference. The percentages of Fec500k, Mnc500k were more than65%, the percentages of Pbc1k, Asc1k more than50%, each molecular weight percentages of Cu, Cr, Ni, Hg, and Zn were similarly, all exceed50%.
(6) There was a significant temporal and spatial distribution of colloidal heavy metals in Yangtze River estuary.
The concentration of Cuc, and Fec was increased from spring to winter, and Fec concentration affected by seasonal factors stronger than other heavy metals. Seasonal variation of Mnc and Crc was summer The spatial and temporal distribution of colloidal heavy metal concentrations were directly affected by the wastewater and sewage discharged from the industrial enterprises and residents along the Yangtze River and Yangtze River estuary, and navigation of ships in the Yangtze River estuary. Fec1k concentrations in the water from coast of chongming were higher than from coast of Shanghai urban, Fec5k instead; the highest concentrations of Fec500k appeared in the middle of south branch, the rest of the sites increasing from coast of chongming to coast of shanghai urban. k, Mnc5k concentrations in coast were higher than middle, but the highest concentrations of Mncsook, Crc500k were found in middle; Cuc5k, Nic1k, Nic5k, Znc1k concentrations in the water from coast of Shanghai urban were higher than from other sites, but Cuc500k and Znc5k concentrations in the water from coast of Chongming were higher than from other sites.
(7) The adsorption abilities among COC1k, COC5k, and COCsook on heavy metal were obvious different; it was easily transferred heavy metals Cu, Mn, Ni, Cr, Pb,and Zn from5-500kDa colloidal phase to1-5kDa and500kDa-0.45μm colloidal phase, becease the adsorption ablility of COCsk on these heavy metals was weakest; it was easily transferred heavy metals Fe from1-5kDa colloidal phase to5-500kDa colloidal phase, becease the adsorption ablility of COC1k on Fe was weakest; it was easily transferred heavy metals Hg, and As easily from500kDa-0.45μm colloidal phase to5-500kDa colloidal phase.
The affect of "colloid pump" was strong in Yangtze River estuary, because it has high concentrations of COC. Due to "colloid pump" effect, In Yangtze River estuary, heavy metal Fe, Mn, and Cr easily transferred from true dissolved phase to colloidal phase, then transferred to particle phase. However, heavy metal Cu, Ni, Pb, Zn, Hg, and As easily transferred from particle and turely dissolved phases into colloidal phase. Therefore, organic colloidal would adjust the distribution of these heavy metals, and affect the biogeochemical cycle of these heavy metals in Yangtze River estuary.
本论文选择长江河口南支作为研究对象,采集一年四季大潮和小潮涨落潮过程水体(共111个样品),通过切向流超滤技术分离水体中的胶体,并分析、测试其胶体有机碳含量、三维荧光光谱特征、胶体态重金属含量,理清该区域有机胶体的含量、时空分布及其影响因素,并探讨了胶体有机质的类型和来源,最后分析有机胶体对重金属行为的影响,得到以下几点结论：
(1)胶体有机碳(1kDa-0.45μm, COC)作为有机胶体的一个重要的指标,长江河口水体COC含量较高(20.29-154.16μmol·L-1),年均值50.78μmol·L-1,占溶解有机碳(DOC)的平均比例为31.93%,在COC中,以中分子量胶体有机碳(5-500kDa, COC5k)为主,其次是大分子量胶体有机碳(500kDa-0.45μm, COC500k),小分子量胶体有机碳(1-5kDa, COC1k)含量最低。从时间分布上看,COC的浓度表现为冬季>夏季>秋季>春季,大潮>小潮,涨潮>落潮。COC浓度空间分布,近岸点高于河段中间点,且近上海点略高于近崇明点,由于受到人为活动的影响,近岸点季节变化明显大于河段中间点。
(2)2009年长江河口COC年通量大(0.7×106t),受到长江径流量夏丰冬枯的影响,季节通量,夏季最高,秋季次之,春季第三,冬季最小,夏季大量的有机胶体输入长江河口。
(3)长江河口水体胶体有机质(COM)三维荧光光谱除了检测出与溶解有机质(DOM)三维荧光光谱图中的紫外区类富里酸荧光峰A、海洋来源可见光区类富里酸荧光峰C、低激发态类酪氨酸荧光峰B1、高激发态类酪氨酸荧光峰B2以及低激发态类色氨酸荧光峰D1等5种荧光峰,还发现了高激发态类色氨酸荧光峰D2和陆源可见光区类富里酸荧光峰E,前五种荧光物质主要存在于分子量<1kDa的有机组分中,其次是小、中分子量胶体有机质(COM1k和COM5k),大分子量胶体有机质含量(COM500k)最低,最后两种荧光物质主要集中在胶体态中。
(4)各类荧光峰强度指示长江河口水体COM主要来源为人类生活和工农业生产排放(人为源),其次为陆地土壤和植物等有机质残体(陆源),接着是河口浮游生物和微生物分解(内源),河口潮汐过程带来的海洋来源有机质(海源)贡献最小。人为源、内源和海源胶体有机质小分子量胶体态所占比例高于陆源有机质。COM来源具有明显的季节性,陆源贡献表现为秋冬季节明显的大于春夏季节,且秋冬季节COMsk所占比例要高于春夏季节；夏季长江径流量大,河口受到潮汐作用相对弱于其它季节,因此海源贡献较弱；人为源贡献春秋季节高于夏冬季节,春季主要以酪氨酸为主,夏季酪氨酸和色氨酸相差不大,而秋冬季节主要以色氨酸为主,人为排放有机质为水体浮游生物提供食物使得浮游生物生命活动变强,因而内源COM浓度同样也是春秋两季强于夏冬两季。长江河口水体上海沿岸水体受到人为活动影响较强,因此人为排放的有机质要多于河段中间点和近崇明点水体。
(5)长江河口水体胶体态Cu、 Fe、 Mn、 Ni、Cr、Pb、 Zn、 Hg, As等占总溶解态的比例较高,其中胶体态Fe、 Mn、 Cu、 Ni、 Zn和As等6种重金属占总溶解态的比例超过50%。重金属元素的不同分子量胶体态浓度占胶体态比例存在明显的差别,大分子量胶体态Fe、 Mn占胶体态比例均超过65%,小分子量胶体态Pb和As占胶体态比例超过50%,Cu、Cr、 Ni、 Zn和Hg不同分子量胶体态所占比例差别较小,均未超过50%。
(6)长江河口水体胶体态重金属时空分布差异大。
时间分布上,胶体态Cu、 Fe浓度值从春季到冬季递增,且Fe浓度值高,季节变化大,受季节因素影响大；胶体态Mn, Cr浓度由低到高分别是夏季、秋季、春季和冬季,胶体态Ni、 Zn浓度由低到高分别是秋季、春季、夏季和冬季,季节变化较大,季节变化产生一定的影响；胶体态Pb浓度由低到高分别是夏季、秋季、冬季和春季,季节变化小,季节变化对胶体态Pb浓度产生的影响较小。从潮汐过程上看,胶体态重金属大潮高于小潮,涨落潮过程,春、冬季在大、小潮时总体上均表现涨潮浓度高于落潮,而夏、秋季总体上为涨潮浓度低于落潮。
长江沿岸、长江河口区域生产废水和生活污水排放、长江河口船舶航行对水体的扰动等均直接影响水体胶体态重金属浓度的时空分布特征。近上海点小分子量和大分子量胶体态Fe的浓度低于近崇明点,中分子量胶体态Fe高于近崇明点；近岸点小、中分子量胶体态Mn浓度为高于中间点,大分子量胶体态Mn和Cr浓度低于中间点,且近上海点浓度高于近崇明点；近上海点中分子量胶体态Cu和Ni,以及小分子量胶体态Ni和Zn浓度高于其它点,而大分子量胶体态Cu和中分子量胶体态Zn浓度低于近崇明点。
(7)长江河口较高浓度的胶体有机碳形成的“胶体泵”作用,使得重金属Fe、 Mn、 Cr表现为易于从真溶解态向胶体态、再向颗粒态转化进而沉降至沉积物中从水体中清除,重金属Cu、 Ni、 Zn、 Hg和As易于从颗粒态和真溶解态向胶体态转化,而留存于水体中,从而起到调节水体中的重金属行为的作用,影响其生物地球化学循环。
Organic colloids (1nm～0.45μm) is the main component of colloids in natural aquatic environment. It is particularly important due to its high specific surface area and strong potential adsorptive capacity. Most of heavy metals in natural water are combined in various organic colloids. Thus, organic colloids play a critical role in the biogeochemical cycles and bioavailability of heavy metals in aquatic environment, implying a reversibility of the "colloidal pumping" process (transformation between the particulate and dissolved phases through colloidal intermediates).
Yangtze River estuary is the main channel to transport terrigenous material from Yangtze River basin to the East China Sea. Yangtze River estuarine area is an important transportation and business hub, and it also is a highly urbanization and industrialization region. Organic colloid in this area is not only from upstream runoff, but also from municipal sewage and industrial wastewater. These organic colloids become the carrier of heavy metals due to huge specific surface. Thus, we would understand more about heavy metals'biogeochemical cycle by researched on character of organic colloids and its effects on heavy metals behavior in Yangtze River estuary. These researches have important theoretical sense to to prevent pollution, and to protect human health, meanwhile, they have important practical significance to monitor water quality, to make the theory of governance, and to ensure safety of water supply.
In this paper,111water samples were collected from south branch of the Yangtze River estuary during flood and ebb periods of spring and neap tides in different seasons throughout a year. To investigate the content, types, distribution and source of colloidal organic carbon and its effected on heavy metals behavior in the water from Yangtze River estuary (China). Water samples were fractionated into total dissolved (<0.45μm), high molecular weight colloidal (500kDa-0.45μm), medium molecular weight colloidal (5-500kDa), low molecular weight colloidal (1-5kDa) and truely dissolved (<1kDa) fractions with the filters and cross-flow ultrafiltration (CFF) systems, and then all fractions were subsequently characterized for organic carbon content, three dimensional fluorescence spectral characterization and heavy metals content. The main conclusions were showed as follow:
(1) Concentration of colloidal organic carbon (COC) can be used as an indicator of organic colloids concent. A significant proportion of dissolved organic carbon (DOC) was found in colloidal fractions in estuarine water. In Yangtze River estuary, colloidal organic carbon (COC) concentrations was high (20.29μmol·L-1-154.16μmol·L"1, the average was50.78μmol·L-1), and ratios of COC in DOC varied from14.11%to50.50%(the average was31.93%). In COC, the ratio of medium molecular weight colloidal organic carbon (COC5k) was higher than high molecular weight (COCsook) and low molecular weight colloidal organic carbon (COCik). There was a significant temporal variation of COC in the Yangtze River estuary, such as: winter>summer>autumn>spring, spring tide> neap tide, and flood period> ebb period. In Spatial, COC concentrations in coast were higher than in middle of south branch, and water from coast of Shanghai urban slightly higher than from coast of Chongming. In addition, COC seasonal variation in coast was significantly larger than the other sampling sites, due to human activities.
(2) In2009, COC annual flux was0.7*106t. Yangtze River runoff in summer is huge, but few in winter, so COC seasonal flux in Yangtze River estuary was summer>autumn>spring>winter. A large number of COC were transported to estuary through Yangtze River.
(3) In Yangtze River estuary, seven types of fluorescence peaks were observed in three dimensional fluorescence spectrums of dissolved organic matter (DOM) and colloidal organic matter (COM). They were:UV fulvic-like fluorescence peak A, marine sources visible fulvic-like fluorescence peak C, low and high excitation tyrosine peak B1and B2, low and high excitation tryptophan fluorescence peak D1and D2, terrigenous visible fulvic-like fluorescence peak E. Peak A, B1, B2, D1, D2fluorescent substances were mainly existed in the truly dissolved organic matter (UOM,<1kDa), then in low and medium molecular weight colloidal organic matter (COM1k and COMsk,1-500kDa), last in the high molecular weight colloidal organic matter (COM500k). However peak D2and E fluorescent substances were mainly in the colloidal phase.
(4) COM in Yangtze River estuary were mainly originated from anthropogenic sources, secondly from terrigenous sources, thirdly from autochthonous sources (biological decomposition), and the last from marine sources. The concents of anthropogenic, autochthonous, and marine sources COM1k were higher than COM5k, and higher than COMsook, but the contents of terrigenous sources COMsk were higher than COM1k and COMsook.There was obvious seasonal variation of sources of COM in the Yangtze River estuary. Terrigenous inputs in autumn and winter were significantly larger than spring and summer, and COM5k proportion in autumn and winter was higher than spring and summer. Anthropogenic emissions in spring and autumn were higher than summer and winter; in spring colloidal proteins were mainly tyrosine, in summer tyrosine almost same to tryptophan, but in autumn and winter were mainly tryptophan. The COM from anthropogenic sources were the food of plankton, so autochthonous sources from biological activity significantly in spring and autumn were stronger than summer and winter too. Compare to other seasons, marine origins was weakest in summer, because of the huge runoff in this season. In spatial, anthropogenic sources in coast of Shanghai urban was higher than those in middle of south beanch and coast of Chongming as result of human activities.
(5) Heavy metals (Cu, Fe, Mn, Ni, Cr, Pb, Zn, Hg, and As) colloidal fractions were significant in dissolved pool. More than50%of dissolved Fe, Mn, Cu, Ni, Zn, and As were associated with colloidal materials. The distribution of each kind of colloidal heavy metals in different molecular weight was obvious difference. The percentages of Fec500k, Mnc500k were more than65%, the percentages of Pbc1k, Asc1k more than50%, each molecular weight percentages of Cu, Cr, Ni, Hg, and Zn were similarly, all exceed50%.
(6) There was a significant temporal and spatial distribution of colloidal heavy metals in Yangtze River estuary.
The concentration of Cuc, and Fec was increased from spring to winter, and Fec concentration affected by seasonal factors stronger than other heavy metals. Seasonal variation of Mnc and Crc was summer
(7) The adsorption abilities among COC1k, COC5k, and COCsook on heavy metal were obvious different; it was easily transferred heavy metals Cu, Mn, Ni, Cr, Pb,and Zn from5-500kDa colloidal phase to1-5kDa and500kDa-0.45μm colloidal phase, becease the adsorption ablility of COCsk on these heavy metals was weakest; it was easily transferred heavy metals Fe from1-5kDa colloidal phase to5-500kDa colloidal phase, becease the adsorption ablility of COC1k on Fe was weakest; it was easily transferred heavy metals Hg, and As easily from500kDa-0.45μm colloidal phase to5-500kDa colloidal phase.
The affect of "colloid pump" was strong in Yangtze River estuary, because it has high concentrations of COC. Due to "colloid pump" effect, In Yangtze River estuary, heavy metal Fe, Mn, and Cr easily transferred from true dissolved phase to colloidal phase, then transferred to particle phase. However, heavy metal Cu, Ni, Pb, Zn, Hg, and As easily transferred from particle and turely dissolved phases into colloidal phase. Therefore, organic colloidal would adjust the distribution of these heavy metals, and affect the biogeochemical cycle of these heavy metals in Yangtze River estuary.
引文
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