黄海麻坑群沉积物磷的保存与转化及环境效应

基于对北黄海典型麻坑群海域某单位麻坑内部和外缘沉积物中不同赋存形态的磷、甲烷（CH₄）和硫化物等参数的分析,探讨了麻坑独特的环境中磷的转化与埋藏机制、沉积物-水体系磷的释放及对区域磷循环的影响.研究表明,沉积物中碎屑态磷（Det-P）是磷主要的赋存形态（>50%）,其次是有机磷（Org-P）、铁结合态磷（Fe-P）和自生态磷（Auth-P）,交换态磷（Exch-P）对总磷的贡献较小;麻坑内部与麻坑外缘处沉积物中溶解态活性磷（DRP）向水体的释放通量分别为2.84μmol/（cm²·a）和1.03μmol/（cm²·a）,对上层水体的贡献依次为19.6%和3.03%,是上层水体磷的重要来源.麻坑内外磷的埋藏速率与转化过程存在不同;研究区地下水的渗漏是磷的沉积速率和释放通量都普遍高的原因.北黄海麻坑区沉积物中磷的保存与转化还与浅层CH₄的逸出相关,潜在提高黄铁矿的生成速率.较高的沉积物-水界面磷通量必然对区域富营养化等生态环境问题产生深远影响,值得关注.     

南四湖微山湖区沉积物磷形态分布特征

为了解南四湖污染底泥磷形态分布规律,对南四湖微山湖区0～25 cm沉积物分层进行了磷形态连续提取.结果表明,湖区沉积物中Ex-P、Al-P、Fe-P、Oc-P、Ca-P、De-P和Org-P平均含量分别为5.62、 4.08、 12.25、 13.34、 116.67、 232.36和396.79 mg/kg,不同形态磷含量次序为：Al-P＜Ex-P＜Fe-P＜Oc-P＜Ca-P＜De-P＜Org-P.沉积物中各形态磷含量在垂直方向上呈现明显的规律性,易交换态磷（Ex-P）、铁结合态磷（Fe-P）、闭蓄态磷（Oc-P）、有机磷（Org-P）含量随深度增加而逐渐降低,而铝结合态磷（Al-P）、钙结合态磷（Ca-P）、碎屑磷（De-P）含量则呈逐渐增加趋势.Sum1（Ex-P、Al-P、Fe-P之和）与上覆水PO^3-₄浓度呈显著正相关,其中Fe-P与水体磷酸盐含量关系相对比较密切,其相关系数高达0.72.沉积物磷形态在空间分布上,Oc-P、Ca-P、De-P 等惰性磷的差异性小于Ex-P、Al-P、Fe-P等潜在活性磷,Org-P介于二者之间.     

海岸带表层沉积物中磷的地球化学特征

通过连续提取法对莱州湾主要入海河流及近岸海域表层沉积物中5种形态磷进行了定量分析.结果表明,近海沉积物自生钙结合磷含量(45.6%)高于河流(37.3%),而铁结合磷(Fe-P)含量(18.2%)却低于河流(31.3%).在近海,可交换或弱结合磷含量和粉砂比例呈正相关,表明该形态磷主要吸附于细粒粉砂．河流沉积物Fe-P与Fe浓度呈显著正相关(P<0.01),表明河流沉积物Fe-P分布受沉积物活性铁含量的控制．河口处Fe-P普遍低于相应河流,这可能与海相泥沙输入及河口厌氧区硫酸盐还原或硫化物累积有关.近海沉积物总可提取态磷平均浓度总体呈现出由海洋向河口方向递减的趋势.     

海岸带表层沉积物中磷的地球化学特征

通过连续提取法对莱州湾主要入海河流及近岸海域表层沉积物中5种形态磷进行了定量分析.结果表明,近海沉积物自生钙结合磷含量(45.6%)高于河流(37.3%),而铁结合磷(Fe-P)含量(18.2%)却低于河流(31.3%).在近海,可交换或弱结合磷含量和粉砂比例呈正相关,表明该形态磷主要吸附于细粒粉砂.河流沉积物Fe-P与Fe浓度呈显著正相关(P0.01),表明河流沉积物Fe-P分布受沉积物活性铁含量的控制.河口处Fe-P普遍低于相应河流,这可能与海相泥沙输入及河口厌氧区硫酸盐还原或硫化物累积有关.近海沉积物总可提取态磷平均浓度总体呈现出由海洋向河口方向递减的趋势.     

长江口邻近海域表层沉积物中的细菌藿多醇及对低氧区的响应判别

作为新型细菌生物标志物的细菌藿多醇（bacteriohopanepolyols,BHPs）在有机质来源追踪和环境变化响应等方面有明确的指示作用.本文应用高效液相色谱串联大气压化学电离源质谱法（HPLC-APCI-MS）分析,在解析长江口邻近海域表层沉积物中BHPs的组成、分布和来源特征基础上,探讨了BHPs对长江口邻近海域季节性低氧的指示作用.结果表明,长江口邻近海域表层沉积物中共检测出12种BHPs,其含量范围（以TOC计）为3.79~269 μg·g^-1.BHPs以细菌藿四醇（bacteriohopanetetrol,BHT）、2-甲基BHT、氨基BHPs和腺苷藿烷及同系物为主要组分,分别占总量的40%、22%、12%和4%.各组分含量及相应指标呈现出明显的空间变化趋势,其中,主要来源于海洋自生来源的BHT呈现明显的"离岸增加"趋势;主要为陆源贡献的腺苷藿烷等土壤标志物BHPs呈现明显的"离岸降低"特征.Rsoil指数呈现出与腺苷藿烷等土壤标志物BHPs相似的空间分布格局,其陆源有机质贡献从近岸的61.5%下降至外海的1.66%,表明长江口邻近海域近岸有机质主要为陆源输入,而外海主要为海源贡献.细菌藿四醇同分异构体BHT-Ⅱ来源于厌氧氨氧化细菌,其相对含量的高值区与长江口低氧区分布相一致,且与底层水溶解氧（DO）含量呈显著负相关,表明低氧环境有利于BHT-Ⅱ的生成,BHT-Ⅱ可用于指示海洋低氧区环境特征.     

岷江干流表层沉积物中磷形态空间分布特征

近些年,岷江水体TP污染情况严重,而水体沉积物这一潜在污染源,对水质安全带来的威胁也不容忽视.为揭示岷江干流表层沉积物中磷形态的空间分布特征,于2016年12月,采集了岷江干流(阿坝~宜宾)表层沉积物样品,应用改进的SEDEX法对表层沉积物中的弱吸附态磷Ex-P、可提取态有机磷Org-P、铁结合态磷Fe-P、自生磷灰石磷Ca-P、碎屑磷De-P和非活性磷Res-P等6种磷形态质量浓度进行了测定.结果表明,岷江干流表层沉积物中总磷TP的质量浓度为522.17~979.22μg·g~(-1),已远超全国土壤磷素背景值700μg·g~(-1),表明岷江沉积物中TP浓度较高.从空间分布来看,岷江中游眉山河段中的表层沉积物是颗粒最细、有机质和TP质量浓度最高的区域.岷江干流表层沉积物磷的主要赋存形态为Ca-P和DeP,两者共占TP的质量分数为75%以上.同时,岷江干流表层沉积物中的生物可利用磷(Ex-P、Org-P和Fe-P总和)占TP的质量分数为10.31%~29.62%,其中以中游河段(尤其是眉山段、乐山段)质量浓度最高,这表明岷江中游河段表层沉积物中磷的生物可利用性较强,潜在环境风险较高.     

太湖草藻型湖区磷赋存特征及其环境意义

研究草藻型湖区上覆水和沉积物磷赋存特征及环境意义有助于明晰磷在沉积物-水界面的迁移转化过程,对于深入理解不同类型湖区的富营养化过程及富营养化湖泊的治理具有重要现实意义.在太湖典型草藻型湖区进行四季多点采样,分析草藻型湖区水体及沉积物中不同磷形态的时空差异,并揭示其环境意义.结果表明:①藻型湖区上覆水中总磷(TP)、溶解性总磷(DTP)、溶解性无机磷(DIP)和颗粒态磷(PP)显著高于草型湖区,时间分布上大都表现出夏秋高于冬春的特点,PP是TP的主要组成部分,占比71. 8%～89. 6%.叶绿素(Chl-a)浓度与上覆水中磷赋存形态呈相似的时空分布特征.②藻型湖区表层沉积物TP含量为372. 38～529. 64 mg·kg~(-1),草型湖区为304. 29～454. 27 mg·kg~(-1),藻型湖区表层沉积物TP含量明显高于草型湖区,冬季沉积物TP含量最高,夏季最低,这与外源污染的输入以及不同环境条件下内源磷在沉积物和上覆水间的迁移转化有关.③沉积物中不同磷赋存形态数量分布由小到大依次均为:NH_4Cl-P、Fe-P、Org-P、Res-P、Al-P和Ca-P.表层沉积物Mobile-P(NH_4Cl-P+Fe-P+Org-P)在TP中的占比藻型湖区为9. 10%～16. 93%,略高于草型湖区8. 11%～13. 50%,Res-P在TP中占比藻型湖区为10. 06%～14. 97%,草型湖区为11. 02%～20. 28%.藻型湖区内源磷释放风险大,不利于磷的固定与埋藏.不同类型的湖区富营养化程度明显不同,在磷的释放与埋藏中也表现出不同变化特点.藻型湖区因其较高的内源磷负荷和释放潜力,值得特别关注.     

胶州湾沉积物中的磷及其环境指示意义

研究了胶州湾沉积物中磷形态的地球化学分布特征、控制因素及环境意义,将胶州湾沉积物中的磷分为可交换态磷、铝结合态磷、铁结合态磷、闭蓄态磷、自生钙磷、碎屑态磷和有机磷7种不同的形态,并结合210Pb测年法计算了不同年代各形态磷的埋藏通量,在此基础上,分析了胶州湾沉积物中磷所给出的环境信息.结果表明,无机磷是胶州湾沉积物中磷的主要形态,有机磷只占较小的比例,无机磷中钙磷占的比例相对较大,其中碎屑态磷是含量最高.磷的含量及埋藏通量的垂向分布受到pH、盐度、温度、生物扰动、沉积速率等环境因子的影响.相关分析及元素的OC/OP比值分析证明,近20a,陆源输入是胶州湾沉积物主要来源,并且沉积速率不断增大.由于近年来采取的较为得力的治污与排放措施,胶州湾的环境状况已有明显改观.研究还表明,Fe-P,Al-P和Oc-P的含量与海域污染程度有较密切的关系,可作为表征海洋沉积环境污染状况的指示因子之一.     

长江口柱状沉积物中磷的存在形态及其分布特征研究

对长江口的柱状沉积物进行了总磷测定,并运用SEDEX方法分析了长江口柱状沉积物中5种形态磷的含量和分布。研究结果表明,柱状样沉积物不同站位各种形态磷的垂直分布各不相同,由表至底呈现多种分布状态,与沉积环境、沉积后的成岩作用有关。长江口柱状样沉积物有机磷的降解速率常数变化结果表明,长江口海域有机磷的降解主要发生在沉积物表层和次表层。2个柱状样沉积物中氮磷比远低于16:1,说明长江口近岸海域沉积物中的磷主要来自陆源。对柱状样的年代分析表明,总磷含量随年代的变化有明显的区域特征性,长江口总磷含量的髙值与长江较大输沙量的年份具有一致性。     

长江口邻近海域沉积物中生物硅溶解行为研究

对长江口邻近海域进行调查,分析沉积物中生物硅的空间分布特征,探讨影响生物硅溶解以及保存的因素.结果表明,生物硅含量的平面分布具有近岸高于远海的分布趋势,陆源输入、沉积速率以及水动力条件是影响生物硅在沉积物中埋藏的主要因素.生物硅溶解速率常数随空间以及深度无明显变化规律,间隙水中硅酸盐相对于生物硅溶解度的不饱和程度、有机外壳对生物硅的包裹以及间隙水中Al离子浓度等因素会影响生物硅的溶解进而会影响其在沉积物中的保存和间隙水中硅酸盐浓度的变化.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.