Study on the characteristics and diffusion fluxes of nutrients and metal elements in shallow sediment porewater of Shenzhen Bay and Maozhou River
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摘要: 为了解湿地微环境中营养盐和金属元素的分布特征及其内在联系，并进一步估算两者在沉积物−水界面的扩散通量，本文借助薄膜扩散梯度技术获取深圳湾和茅洲河红树林湿地浅层沉积物孔隙水中营养盐和金属元素浓度以及二维高分辨有效态硫浓度分布。研究结果表明：除了
${\rm{NO}}_3^- $ 和Mo外，茅洲河沉积物孔隙水中${\rm{NH}}_4^+ $ 、P与S2−和重金属Cd、Co、Cu、Fe、Ni、Pb与Zn的平均浓度均高于上覆水和深圳湾水体中平均浓度，这说明茅洲河沉积物孔隙水的污染程度更高，但深圳湾水体中营养盐和金属元素等污染物来源多于茅洲河。茅洲河有效态硫浓度空间分布不均匀，存在明显的生物扰动通道，浓度值也随着沉积物深度逐渐增高。深圳湾在沉积物−水界面处营养盐和金属元素的扩散通量为−0.27～0.006 5 μg/(cm2·d)，茅洲河的扩散通量为−0.061～0.069 μg/(cm2·d)。Abstract: In order to understand the distribution characteristics, relationships and diffusion fluxes of nutrients and metal elements across the sediment-water interface, we investigated the vertical profiles of nutrients and metal elements through the diffusive gradient in thin-films (DGT) technology in Shenzhen Bay (SZB) and Maozhou River (MZR). The two-dimensional high-resolution available sulfur (DGT-labile S) distributions were also synchronously measured. The results showed that the mean concentrations of${\rm{NH}}_4^+ $ , P and S2− and heavy metals of Cd, Co, Cu, Fe, Ni, Pb and Zn in porewater of MZR were significantly higher than those in the overlying water and the SZB, except for${\rm{NO}}_3^- $ and Mo. The pollution degree of nutrients and metal elements in porewater of MZR was generally higher than that in SZB, but the pollutants of nutrients and metal elements in SZB were more than those in MZR. The spatial distribution of DGT-labile S in MZR indicated the distinguish bioturbation-induced tubes, which enhanced the spatial heterogeneity and led the increasing of solute concentrations with sediment depths. The diffusion fluxes of nutrients and metal elements ranged from −0.27 μg/(cm2·d) to 0.0065 μg/(cm2·d) in SZB, and from −0.061μg/(cm2·d) to 0.069 μg/(cm2·d) in MZR.-
Key words:
- Shenzhen /
- diffusive gradient in thin-films /
- sediment /
- nutrients /
- heavy metals
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图 2 薄膜扩散梯度（DGT）技术装置示意图
Fig. 2 The diagram of diffusive gradients in thin-films devices
图 3 沉积物−水界面上DGT有效态氮、磷和硫浓度垂向分布
SZB和MZR分别代表深圳湾和茅洲河；蓝色和黄色背景颜色分别表示上覆水和沉积物中孔隙水
Fig. 3 Vertical distribution of DGT-labile N, DGT-labile P and DGT-labile S concentrations at sediment-water interface
SZB and MZR represent Shenzhen Bay and Maozhou River, respectively; blue and yellow backgrounds indicate the overlying water and pore water in sediment, respectively
图 4 沉积物−水界面上DGT有效态金属元素浓度垂向分布
SZB和MZR分别代表深圳湾和茅洲河；蓝色和黄色背景颜色分别表示上覆水和沉积物中孔隙水
Fig. 4 Vertical distribution of DGT-labile metal elements concentration across the sediment-water interface
SZB and MZR represent Shenzhen Bay and Maozhou River, respectively; blue and yellow backgrounds indicate the overlying water and pore water in sediment, respectively
图 5 深圳湾和茅洲河DGT有效态铁、硫、磷和钼的线性相关性
**代表在0.01层上显著，*代表在0.05层上显著
Fig. 5 Linear correlations among DGT-labile Fe, DGT-labile S, DGT-labile P and DGT-labile Mo in Shenzhen Bay and Maozhou River
** Representing significance at 0.01 level, * representing significance at 0.05 level
图 6 深圳湾和茅洲河DGT有效态硫的二维空间分布
Fig. 6 2D distributions of the DGT-labile S in Shenzhen Bay and Maozhou River
图 7 深圳湾和茅洲河营养盐（a）和金属元素（b）在沉积物−水界面扩散通量
Fig. 7 Diffusion fluxes of nutrients (a) and metal elements (b) at sediment-water interface in Shenzhen Bay and Maozhou River
图 8 深圳湾（a）和茅洲河（b）沉积物−水界面上各种参数 PCA 图
Fig. 8 PCA of chemical parameters across the sediment-water interface in Shenzhen Bay (a) and Maozhou River (b)
表 1 各种参数在水体中的提取率和上覆水中的扩散系数
Tab. 1 Extraction rate in water and diffusion coefficient in overlying water of various parameters
参数 $ {{\rm{NH}}_4^+} $ ${ {\rm{NO}}_3^-} $ P S2− Cd Co Cu Fe Mo Ni Pb Zn 提取效率 0.84 1.03 0.96 0.95 0.94 0.98 1.03 0.89 0.98 1.05 0.96 0.88 扩散系数 23.96 7.53 8.22 21.59 7.64 7.82 7.89 7.67 8.27 7.83 10.07 8.25 注：扩散系数单位为10−6 cm2/s，参数获取网址为http://www.easysensor.net/。 
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表 2 深圳湾和茅洲河在上覆水和孔隙水中DGT有效态氮、磷和硫浓度（单位：mg/L）
Tab. 2 The concentrations of DGT-labile N, DGT-labile P and DGT-labile S in overlying water and pore water of Shenzhen Bay and Maozhou River (unit: mg/L)
站点 ${{\rm{NH}}_{4 {\rm{DGT}}}^+ }$ ${{\rm{NO}}_{3 {\rm{DGT}}}^- }$ ${\rm{P}}_{\rm{DGT}} $ ${{\rm{S}}_{ {\rm{DGT} } }^{2-}}$ 深圳湾 上覆水 范围 0.05～0.20 0.07～0.09 0.04～0.10 0.003～0.12 均值 0.12 0.08 0.06 0.05 孔隙水 范围 0.04～0.24 0.06～0.13 0.06～0.29 0.01～0.15 均值 0.07 0.09 0.16 0.07 茅洲河 上覆水 范围 0.07～0.13 0.39～0.54 0.07～0.45 0.01～0.13 均值 0.10 0.45 0.21 0.06 孔隙水 范围 0.05～0.30 0.09～0.40 0.53～2.52 0.15～0.68 均值 0.11 0.17 0.89 0.45
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表 3 深圳湾和茅洲河在上覆水和孔隙水中DGT有效态金属元素浓度
Tab. 3 The concentrations of DGT-labile metal elements in overlying water and pore water of Shenzhen Bay and Maozhou River
站点 CdDGT浓度/
(μg·L−1)CoDGT浓度/
(μg·L−1)CuDGT浓度/
(μg·L−1)FeDGT浓度/
(mg·L−1)MoDGT 浓度/
(μg·L−1)NiDGT浓度/
(μg·L−1)PbDGT浓度/
(μg·L−1)ZnDGT浓度/
(μg·L−1)深圳湾 上覆水 范围 0.17～0.25 0.12～1.14 1.33～3.16 0.16～0.32 120.77～174.03 4.82～6.59 1.44～1.54 65.03～77.74 均值 0.21 0.49 2.27 0.22 132.77 5.32 1.49 69.55 孔隙水 范围 0.12～0.19 0.31～1.16 0.72～2.05 0.49～2.97 88.90～364.31 3.16～7.88 1.35～2.04 48.31～119.09 均值 0.14 0.57 1.05 1.68 145.54 4.71 1.61 75.91 茅洲河 上覆水 范围 0.17～0.26 0.35～1.44 7.51～15.09 0.15～5.60 63.19～100.08 13.43～22.35 1.20～1.38 40.53～52.90 均值 0.21 0.70 9.43 1.40 74.18 17.27 1.33 45.71 孔隙水 范围 0.19～1.00 0.55～8.02 10.03～190.22 3.03～9.07 52.99～74.25 17.62～127.62 1.34～2.76 49.52～300.03 均值 0.36 2.05 54.98 4.70 61.17 39.02 1.62 104.70
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表 4 不同地点沉积物−水界面处磷和金属元素的扩散通量（单位：10−3 μg/(cm2·d)）
Tab. 4 Diffusion fluxes of phosphorus and metal elements at sediment-water interface in different sites (unit: 10−3 μg/(cm2·d))
地点 P Cd Co Cu Fe Mo Ni Pb Zn 文献 太湖 −21～65 nd nd nd nd nd nd nd nd 文献[35] 洞庭湖 −3～20 nd nd nd nd nd nd nd nd 文献[12] 泰国宋卡湖 nd −0.015～0.004 7 0～0.58 −0.34～0.19 −94.95～2580.27 nd 0～0.53 −0.25～0.33 −7.85～2.09 文献[36] 珠江口 nd nd nd −44～24 nd nd −56～18 nd −3.5～11 文献[37] 白洋淀 nd 0.17 nd −43～30 nd nd −160～79 0.86～720 −41～1 420 文献[38] 三峡水库 nd nd nd nd nd −120～300 nd nd nd 文献[39] 营口湾 nd 0.75 −0.21 −126.90 −1 623.00 nd −1.22 18.46 −0.11 文献[40] 深圳湾 0.26 0.13 5.55 −5.36 6.55 −267.06 −7.7 1.4 −48.29 本文 茅洲河 −1.22 0.57 −7.88 46.12 −29.78 68.73 −61.44 1.76 15.49 本文 注：表中“nd”代表没有数据。
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