镧改性沸石活性覆盖控制重污染河道底泥溶解性磷酸盐和铵释放研究

通过实验考察了镧改性沸石对水中磷酸盐和铵的吸附性能,并探讨了低溶解氧情况下镧改性沸石覆盖控制底泥溶解性磷酸盐和铵态氮释放的效率.镧改性沸石对水中磷酸盐和铵的吸附动力学过程满足准二级动力学模型.镧改性沸石对水中磷酸盐的吸附平衡数据可以采用Langmuir等温吸附方程加以描述,对水中铵的吸附平衡数据可以采用Langmuir、Freundlich和Dubinin-Radushkevich(D-R)等温吸附方程加以描述.当pH 7时,镧改性沸石吸附水中磷酸盐的机制包括配位体交换、路易斯酸碱反应和静电吸引,吸附水中铵的机制是阳离子交换.镧改性沸石覆盖不仅可以有效地控制溶解性磷酸盐从底泥向上覆水的释放,而且可以明显降低铵态氮从底泥向上覆水迁移的速率.镧改性沸石覆盖量越多,控制底泥铵态氮释放的效果越好.镧改性沸石覆盖层吸附从底泥中释放出来的溶解性磷酸盐后主要以较为稳定的形态存在,低溶解氧情况下不容易重新释放出来.上述结果表明,镧改性沸石适合作为一种覆盖材料用于控制低溶解氧情况下溶解性磷酸盐和铵态氮从底泥向上覆水的释放.     

基于液相31P核磁共振(NMR)技术的巢湖沉积物中有机磷形态研究

利用改进的沉积物有机磷提取方法和液相31P核磁共振(NMR)分析方法,研究了巢湖表层沉积物有机磷形态.结果表明:西部湖区表层沉积物总磷含量高于东部湖区,其平均含量分别为(1089.82±108.14) mg·kg-1和(497.80±51.59) mg·kg-1;东部湖区沉积物中有机磷百分含量(31.88％±2.41％)高于西部湖区(20.86％±1.65％);表层沉积物主要磷份组成包括膦酸盐(Phon-P)、正磷酸盐(Ortho-P)、磷酸单酯(Mono-P)、磷脂(Lipid-P)、DNA(DNA-P)、焦磷酸盐(Pyro-P);磷酸单酯为有机磷的主要组分,平均含量占总磷的22.12％±5.32％;磷酸单酯和DNA百分含量东部湖区大于西部湖区,磷酸单酯百分含量分别为25.99％±2.29％和16.30％±1.06％,DNA百分含量分别为5.61％±0.24％和3.85％±1.01％.31P核磁共振技术可以有效的应用于巢湖等富营养化湖泊沉积物磷形态分析;巢湖表层沉积物以无机磷为主,有机磷种类丰富,以磷酸单酯为主.     

太湖梅梁湾和月亮湾春夏两季沉积物扰动下BAPP的转化规律

采用室内模拟试验研究了沉积物扰动下上覆水中可被生物利用颗粒态磷(BAPP)的变化规律,并分析了BAPP与悬浮物中内源磷间的内在联系.试验用沉积物分别于春季和夏季采自太湖梅梁湾和月亮湾.结果表明,沉积物扰动降低了上覆水中生物有效磷(BAP)含量,降至初始状态的40%左右.BAPP也明显降低,其占BAP的百分比稳定在50%左右,梅梁湾春季除外.扰动状态下颗粒态磷(PP)生物有效性显著降低,第12h时,BAPP占PP的百分比仅为10%左右;这与悬浮物中NH₄Cl-P和Fe/Al-P的降低明显相关,但其与 (AAP+NH₄Cl-P)占Tot-P的百分比相关性更好[r=0.565(n=48)].这暗示,沉积物扰动可能延缓了水体富营养化发展进程.     

密云水库底泥和库滨区土壤中氨氧化细菌的多样性和丰度

采用分子生物学方法（T-RFLP、定量PCR）研究了密云水库底泥沉积物和库滨带土壤中氨氧化细菌（AOB）的多样性和丰度特征,并使用Canoco for Windows 4.5软件和皮尔森相关系数法,探究了环境因子对AOB群落的影响.结果表明,沉积物和库滨区土壤中AOB的多样性和数量都存在较大的差异.其中,AOB群落被聚成两大类：沉积物与土壤.沉积物样品中AOB群落结构与其它样品差异较大.沉积物中AOB的多样指数最低,而在农田土壤中AOB多样性指数最高.农田土壤中的amoA基因拷贝数最大,是底泥沉积物中的48倍.此外,RDA（Redundancy Analysis）分析表明,在沉积物和水陆交错带土壤中,AOB的优势种与NH₄⁺-N、NO₃^--N、TOC、pH成正相关关系,而在陆相土壤和农田土壤中,AOB的优势种与这些环境因子成负相关关系.其中,TOC是影响AOB的群落结构的关键理化因子.     

海河流域重污染河流表层沉积物氨基酸组成特征

为探明子牙河水系沉积物氮的主要形态,采用柱前衍生反相高效液相色谱-同位素内标法研究了表层沉积物中20种氨基酸的形态及组成特征.结果表明:子牙河水系沉积物中有机氮是氮的主要存在形态,沉积物有机氮(SON)平均浓度为3114 mg·kg^-1,总水解氨基酸氮(THAAs-N)占SON的45.53%;蛋白类氨基酸氮是THAAs-N的主体,占THAAs-N的90.24%,为沉积物潜在释放氮及矿化氮的主体;子牙河水系表层沉积物氨基酸以甘氨酸(Gly)、脯氨酸(Pro)摩尔含量最高,分别占THAAs的14.70%、10.00 %;根据官能团类型分类,蛋白类氨基酸为主要类别,占THAAs的89.50%;蛋白类氨基酸以中性氨基酸为主,平均含量为THAAs的40.69%;亚氨基酸及非蛋白类氨基酸的含量差异性从侧面反映出水系河流污染物来源;采用Glu/γ-Aba及DI指数判断有机质的降解程度,结果显示子牙河水系大部分区域沉积物有机质降解程度较低.     

沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.     

组合型生态浮床对上覆水和沉积物之间氮磷的影响

在天鹅湖水体中构建以水生植物和陆生喜水植物为实验植物,浮法控制器、水循环增氧系统和造浪-输送系统为辅助设备的组合型生态浮床.组合型生态浮床运行期间改变了水体的理化环境,影响了上覆水-沉积物中氮磷形态的迁移转化,跟踪监测在组合型生态浮床影响下上覆水和沉积物TN、NH4+-N和TP含量的浓度变化规律,探讨了在组合型生态浮床作用下,DO、Eh、pH对上覆水和沉积物中营养盐的影响,以及上覆水和沉积物中氮磷之间以及和各环境因子之间的相互关系.结果表明,实验期间上覆水中TN、NH4+-N和TP的去除率分别达到61.92%、63.09%和80.0%.沉积物中TN和NH4+-N的去除率分别达到23.79%和37.04%,沉积物中TP含量上升了43.71%.组合型生态浮床对上覆水环境因子如DO、Eh、pH等产生不同程度的影响,处理区上覆水中DO和Eh均高于对照区,DO由原来的8.7～8.9 mg·L-1上升到9.3～10.4 mg·L-1,Eh由原来的163～178 mV上升到191～198 mV,通过提高上覆水中DO和Eh有效抑制沉积物磷的释放并促进沉积物对上覆水中磷的吸附.pH的波动性较小,维持在7.51～8.32之间,并未促进沉积物磷释放.上覆水中TN、TP和NH4+-N以及与沉积物中的TN、NH4+-N之间呈极显著正相关,与沉积物中的TP极显著负相关;pH与上覆水和沉积物中的TN、TP和NH4+-N都无相关性;上覆水中的DO与Eh显著正相关,与沉积物中的TP显著负相关.     

Occurrence and distribution of hexabromocyclododecane in sediments from seven major river drainage basins in China

The concentrations and geographical distribution of hexabromocyclododecane (HBCD) were investigated in 37 composite surface sediments from seven major river drainage basins in China, including Yangtze River, Yellow River, Pearl River, Liaohe River, Haihe River, Tarim River and Ertix River. The detection frequency of HBCD was 54%, with the concentrations ranged from below limit of detection (LOD) to 206 ng/g dry weight. In general, the geographical distribution showed increasing trends from the upper reaches to the lower reaches of the rivers and from North China to Southeast China. Compared to other regions in the world, the average concentration of HBCD in sediments from Yangtze River drainage basin was at relatively high level, whereas those from other six river drainage basins were at lower or similar level. The highest HBCD concentration in sediment from Yangtze River Delta and the highest detection frequency of HBCD in Pearl River drainage basins suggested that the industrial and urban activities could evidently affect the HBCD distribution. HBCD diastereoisomer profiles showed that γ-HBCD dominated in most of the sediment samples, followed by α- and β-HBCD, which was consistent with those in the commercial HBCD mixtures. Further risk assessment reflected that the average inventories of HBCD were 18.3, 5.87, 3.92, 2.50, 1.77 ng/cm 2 in sediments from Pearl River, Haihe River, Tarim River, Yellow River and Yangtze River, respectively.     

Effects of physical and chemical characteristics of surface sediments in the formation of shallow lake algae-induced black bloom

Surface sediments are closely related to lake black blooms. The dissolved oxygen （DO） distribution and its penetration depth in surface sediments as well as the migration and transformation of redox sensitive elements such as Fe and S at the sediment-water interface are important factors that could influence the formation of the black bloom. In this study, dredged and undredged sediment cores with different surface properties were used to simulate black blooms in the laboratory. The Micro Profiling System was employed to explore features of the DO and ∑H2S distribution at the sediment-water interface. Physical and chemical characteristics in sediments and pore waters were also analyzed. The results showed that sediment dredging effectively suppressed the black blooms. In the undredged treatment, DO penetration depth was only 50 μm. Fe^2＋ concentrations, ∑H2S concentrations, and ∑H2S production rates were remarkably higher in surface sediments and pore waters compared to control and dredged treatments. Furthermore, depletion of DO and accumulation of Fe^2＋ and ∑H2S in surface sediments and pore waters provided favorable redox environments and necessary material sources for the blooms. The study results proved that physical and chemical characteristics in surface sediments are important factors in the formation of the black bloom, and could provide scientific guidance for emergency treatment and long-term pre-control of black blooms.     

Speciation of organic phosphorus in a sediment profile of Lake Taihu II. Molecular species and their depth attenuation

The understanding of organic phosphorus(P) dynamics in sediments requires information on their species at the molecular level,but such information in sediment profiles is scarce.A sediment profile was selected from a large eutrophic lake,Lake Taihu(China),and organic P species in the sediments were detected using solution phosphorus-31 nuclear magnetic resonance spectroscopy(31 P NMR) following extraction of the sediments with a mixture of 0.25 mol/L NaOH and 50 mmol/L EDTA(NaOH-EDTA) solution.The results showed that P in the NaOH-EDTA extracts was mainly composed of orthophosphate,orthophosphate monoesters,phospholipids,DNA,and pyrophosphate.Concentrations of the major organic P compound groups and pyrophosphate showed a decreasing trend with the increase of depth.Their half-life times varied from 3 to 27 years,following the order of orthophosphate monoesters > phospholipids DNA > pyrophosphate.Principal component analysis revealed that the detected organic P species had binding phases similar to those of humic acid-associated organic P(NaOH-NRP HA),a labile organic P pool that tends to transform to recalcitrant organic P pools as the early diagenetic processes proceed.This demonstrated that the depth attenuation of the organic P species could be partly attributed to their increasing immobilization by the sediment solids,while their degradation rates should be significantly lower than what were suggested in previous studies.