Manganese, iron and sulfur diagenesis and diffusive fluxes of porewater iron and manganese in sediments of Laizhou Bay, Bohai Sea
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摘要: 通过莱州湾4个站点沉积物柱样固相和孔隙水化学分析，揭示了Mn、Fe、S的成岩循环及其对陆源输入和人为扰动的响应。结果表明，水体富营养化未导致沉积物中有机碳富集，陆源低活性有机碳输入以及自然过程和人为扰动导致的沉积物强烈再悬浮致使沉积物有机碳含量和活性低，不利于硫酸盐还原，沉积物中总还原无机硫含量低（0.28～88 μmol/g）。孔隙水Mn2+主要来源于无定形或弱晶型锰氧化物的还原溶解，而MnCO3沉淀则是深部（>10 cm）孔隙水Mn2+消耗的主要机制。有机碳低活性以及沉积物强烈再悬浮有利于铁异化还原，该路径对有机碳厌氧矿化的平均贡献约为51%。在受黄河输入影响显著的站点（S6），动态的沉积环境促进了锰氧化还原，但抑制了铁和硫酸盐还原。莱州湾沉积物孔隙水Mn2+和Fe2+扩散通量位于其他受河流输入影响海域的低值端，这可归因于有机碳的低活性。Abstract: Based on analyses of solid-phase and porewater chemistry of sediment cores at four sites collected from Laizhou Bay of the Bohai Sea, we revealed diagenetic cycles of iron, manganese and sulfur and their responses to terrestrial inputs and anthropogenic perturbations. Results suggest that water eutrophication of the bay has not given rise to organic carbon (OC) enrichment in the sediments. Actually, contents and lability of sediment OC are generally low, largely due to the inputs of terrestrial refractory OC and intense sediment resuspension induced by natural processes and anthropogenic perturbations in the river-dominated area. This feature greatly dampens sulfate reduction, resulting in low accumulation of total reduced inorganic sulfide (0.28−88 μmol/g). Porewater Mn2+ is mainly from reductive dissolution of amorphous and poorly crystalline Mn oxides, while precipitation of MnCO3 is mainly responsible for Mn2+ consumption in sediment below 10 cm depth. Intense sediment resuspension and refractory nature of sediment OC encourage dissimilatory iron reduction, with relative contribution of this pathway to total anaerobic OC mineralization of about 51%, on average. At the site (S6) heavily influenced by the Huanghe River input, dynamic depositional regime facilitates reductive dissolution of manganese oxides, but dampens reduction of iron oxides and sulfate to some extent. Upward diffusive fluxes of porewater Mn2+ and Fe2+ in the sediments are at the lower end for sediments of other areas dominated by major river inputs, which is attributable to overall low lability of sediment OC.
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Key words:
- Diagenesis /
- porewater /
- sulfide /
- diffusive flux /
- marine sediment /
- iron /
- manganese /
- Laizhou Bay
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图 2 4个沉积物柱样中粒度的垂直分布
Fig. 2 Vertical profiles of grain-size distributions in four sediment cores
图 3 4个沉积物柱样中TOC、TN和δ13C的垂直分布
Fig. 3 Vertical profiles of TOC, TN, and δ13C in four sediment cores
图 4 4个沉积物柱样中固相锰形态垂直分布
Fig. 4 Vertical profiles of solid-phase mn forms in four sediment cores
图 6 4个沉积物柱样中固相还原硫形态垂直分布
Fig. 6 Vertical profiles of solid-phase reduced sulfur forms in four sediment cores
图 7 沉积物柱样中孔隙水Mn2+和Fe2+浓度剖面（圆圈）、拟合浓度剖面（实线）以及拟合生成速率（虚线）
Fig. 7 Vertical profiles of porewater Mn2+ and Fe2+ (circle), model-fitted concentration (solid line), and production rate (dashed line)
图 9 孔隙水Mn2+和Fe2+扩散通量与表层沉积物活性锰和活性铁含量的相关性
Fig. 9 Correlations of diffusive fluxes of porewater Mn2+ and Fe2+ with extractable Mn and Fe contents in surface sediments
图 10 沉积物中TRIS与TOC的含量关系（虚线为正常海洋沉积物TOC/TRIS质量比平均值2.8[63]）
Fig. 10 Relationship between TRIS and TOC in sediment cores (the dashed line shows the mean TOC/TRIS mass ratio of 2.8 for normal marine sediments)
表 1 PROFILE拟合得到的孔隙水Mn2+和Fe2+深度积分生成速率和扩散通量
Tab. 1 Depth-integrated rates of porewater Mn2+ and Fe2+ production, and diffusive fluxes fitted by PROFILE
站点 12 cm深度的深度积分速率/
（nmol·cm−2·d−1）扩散通量/
（μmol·m−2·d−1）Fe2+ Mn2+ Fe2+ Mn2+ S6 0.5 6.0 −1.0 −62.1 R4 1.3 2.6 −12.6 −14.2 N6 6.9 4.4 −38.9 −39.8 S5 1.9 5.7 −17.8 −53.7 
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