大辽河水系沉积物剖面磷的形态和分布特征

用柱状采样器在大辽河水系采集4个沉积物柱,利用选择性连续提取法研究了沉积物中磷的形态,探讨了磷与铁、铝、钙和有机质含量之间的关系及磷的生物有效性.结果表明,大辽河水系沉积物总磷(TP)含量在323～2 619 mg·kg~(-1)之间.除浑河剖面25～47 cm深度外,钙结合态磷(Ca-P)含量最高,约占TP的40%以上.其次为铁结合态磷(Fe-P)和残渣态磷(RES-P),各占TP的15%～25%.第三为闭蓄态磷(RS-P)和铝结合态(Al-P),各占TP的5%～10%. 溶解与弱结合态磷(S/L-P)的含量仅占TP的0.5%以下.浑河剖面25～47 cm深度,P的大量积累导致Fe-P、Al-P含量升高,分别占TP的19.6%～34.1%和6.2%～23.4%;而Ca-P占TP的含量下降,为TP的14.6%～35.6%.河流下游(大辽河)沉积物较上游(浑河和太子河)沉积物含有较高的S/L-P、Al-P和Fe-P,因此有较高的释放风险和生物可用性.相关分析表明,除浑河剖面25～47 cm深度外,沉积物Fe结合P(Fe-P+RS-P)、Ca-P 和RES-P分别与沉积物Fe、Ca和有机质含量正相关,但Al-P与Al的含量不相关;而且,TP含量与Fe、有机质含量正相关,与Al、Ca含量不相关.大部分沉积物中Fe与TP的摩尔比为20.9～33.9,表明有进一步固定磷的能力. 磷的生物有效性分析结果表明,大辽河水系沉积物中潜在生物有效磷含量在67.99～1 450.86 mg·kg~(-1),对水体富营养化构成潜在威胁.

Chemical Forms and Distribution of Phosphorus in the Sediment Profiles of the Daliaohe River Systems

The Daliaohe river system in China has been seriously affected by long-term intensive industrial, urban and agricultural activities. The objective of this study was to determine the total phosphorus (TP) content and forms of phosphate in the sediments and investigate geochemical relationships between P forms and mineral matrix elements and P bioavailability. Four sediment profiles were taken in the Daliaohe river systems. TP content in the sediment was measured by ICP-OES and chemical forms of phosphate were measured by sequential selective extraction method. Results indicated that TP ranged from 323 to 2619 mg·kg~(-1). In the sediments except 25-47 cm depth of sediment profile in the Hun river, the content of Ca bound P (Ca-P) was the highest, with more than 40% of TP. The contents of Fe bound P (Fe-P) and residual P (RES-P) were 15% to 25% of TP, while the contents of reductant soluble P (RS-P) and Al bound P (Al-P) were generally 5% to 10% of TP. However, the content of soluble and loosely bound P (S/L-P) was only less than 0.5% of TP. Huge accumulation of P in the 25-47 cm depth of the sediment profile in the Hun river led to a bigger increase in the contents of Fe-P and Al-P than Ca-P, where Al-P, Fe-P and Ca-P contents were 6.2%-23.4%, 19.6%-34.1% and 14.6%-35.6% of TP, respectively. Correlation analysis showed that sum of Fe-P and RS-P, Ca-P, and RES-P were positively correlated to Fe, Ca, and sediment organic matter (SOM) contents, respectively in the sediments except the 25-47 cm depth of sediment profile in the Hun river. In addition, TP content was positively correlated to Fe and SOM contents. The molar ratios of Fe to TP generally ranged from 20.9 to 33.9, indicating that most of sediments have capability to further retain P. Potential bioavailable P (BAP) including S/L-P, Al-P and Fe-P in the sediments was 85.43 to 1830.5 mg·kg~(-1), and this part of phosphorus might pose a potential risk to the eutrophication of the Daliaohe river system and its estuary.