化学连续提取法对太湖沉积物中磷的各种形态测定

为确定太湖沉积物中磷的各种形态含量,本文应用SMT 连续提取法对太湖梅梁湾表层沉积物样品和淡水沉积物标准物质BCＲ --684 中磷的各种形态进行测定。结果表明SMT 法具有一定的适用性和准确性。太湖沉积物中磷形态测定结果表明无机磷是太湖沉积物中磷的主要赋存形态,占总有效磷的 59. 22%,无机磷含量中非磷灰石态磷含量为139 μg /g,大于磷灰石态磷含量113 μg /g。     

库布齐沙漠颗粒物中磷的化学形态分析

采用7步连续浸提法对库布齐沙漠响沙湾沙粒中磷的各种存在形态进行了分析测定，并对沙粒样进行了分级形态研究。结果表明：在库布齐沙漠响沙湾沙粒中总磷（TP）的含量为137．21～362．09μg／g，其主要成分为无机磷（IP），平均占TP的比例为94．60％；而有机磷（Or—P）的含量为7．88～19．12μg／g，平均占TP的5．40％。在所有不同粒度的沙样中，自生钙结合磷（Ca—P）含量最高，占TP的58．95％～80．05％，其次是原生碎屑磷（De—P）。占TP的8．13％～30．22％，二者占IP的绝大部分；其他各形态磷含量的高低顺序为：有机磷（Or—P）〉吸附态磷（Ads—P）〉铁结合态磷（Fe—P）〉闭蓄态磷（Obs—P）〉铝结合态磷（AI—P）。在所取沙漠颗粒物样中TP、Ca—P、De—P、Or—P、AI—P各自的含量都是随颗粒物粒度的减小而增大，而Ads—P含量则相反；Fe—P、Obs—P的含量受颗粒物粒度变化的影响不大。     

贵州织金含稀土磷矿床稀土元素赋存状态研究

利用等离子质谱仪ICP-MS、扫描电镜配合能谱分析、电子探针分析方法,研究了贵州织金含磷岩系剖面稀土含量变化。结果表明,剖面上稀土含量与磷灰石含量变化呈正相关关系,说明稀土主要赋存于磷灰石矿物中;利用扫描电镜、电子探针分析方法对生物碎屑、白云石和胶磷矿进行单矿物微量元素分析研究表明,胶磷矿中稀土含量最高,生物碎屑和白云石稀土含量较低,说明织金含稀土磷矿床稀土元素赋存状态是以类质同象的形式存在于胶磷矿中;利用稀土元素化学物相分析研究同样表明只有少量的稀土元素被磷块岩中粘土矿物所吸附,大量的稀土元素以类质同相形式存在于胶磷矿中。     

桂林市七星区土壤汞赋存形式及其污染性研究

文章对桂林市七星区五个采样片区的土壤热释汞含量、部分样品汞的赋存形式以及其污染性状进行了分析,并对主要相态汞的来源进行了简单的分析。结果发现:桂林市七星区部分区段土壤汞存在轻度的污染,污染主要源于原始岩石背景含量较高;区内土壤中汞的赋存方式多种多样,组成差异也较大,其中以硫酸汞为主的高温热态汞含量最高,其次为硫化物形态汞,再次为以氧化物形态为主的中温热态汞,而吸附态汞和低温热态亚汞及低温热态汞含量较低,所占总汞含量小于10%。     

贵州铜仁坝黄磷矿中铀赋存状态的逐级化学提取研究

贵州铜仁坝黄磷块岩矿床富集放射性元素铀,利用逐级化学提取分析方法对该地区黄磷矿中铀的赋存状态进行探究,有助于进一步探讨磷块岩型铀矿的分布规律、成矿机理及铀资源的综合开发。本文采用经修改的Tessier法流程,提取了水溶态、可交换离子态、碳酸盐结合态、铁锰氧化物结合态、有机质黄铁矿态、强酸提取态和残渣态等七种不同形态的铀。研究发现:黄磷矿中的铀主要以独立铀矿物和类质同象置换的形式存在,分别占37.83%、37.21%,少量铀(占24.96%)以分散吸附形式存在。分析表明:独立铀矿物在富磷、黄铁矿脉和镜面擦痕发育的岩层中含量较高,说明热液活动有利于独立矿物形式铀的富集;类质同象铀与黄磷矿中的磷含量呈正相关关系,铀元素可能是以离子置换的方式赋存于胶磷矿的晶格缺陷中;吸附形态铀的含量受到岩石中黏土矿物含量和黄铁矿脉的影响,有机质黄铁矿态是吸附形态铀存在的主要方式,少量铀通过扩散作用吸附于黏土矿物表面。除类质同象铀因其存在形式不易被提取利用外,独立铀矿物及吸附形态铀对于未来优化资源配置具有现实意义。     

滇池现代沉积物中磷的地球化学及其对环境影响

湖泊沉积物中,磷是产生富营养化的重要元素.湖泊中磷元素含量、地球化学行为以及它的复杂矿物学特征,使人们对磷的研究极为重视.滇池湖中总磷超标10.3倍,底泥沉积物中P2O5平均含量0.52%,最高可达1.92%.滇池地处磷矿区,是磷质来源最丰富的湖泊,统计表明,磷含量每年在不断增长.滇池沉积物中磷主要以吸附态、有机态、铁结合态、钙结合态、铝结合态等几种形式存在.这些形态磷在底泥中是不稳定的,它们在环境改变条件下,又将磷释放到水体中.微生物在磷的循环过程中起了重要作用,乳酸菌对不溶性磷酸盐的分解,使湖泊中可溶磷含量增高.聚磷菌对磷元素的富集以及聚磷菌死亡后发生有机磷的矿化作用,是湖泊中水合磷酸盐矿物沉积的重要途径.当湖泊中这种不稳定的水合磷酸盐矿物在条件具备的情况下,经沉积物覆盖成岩作用后,最终形成磷灰石。     

海南高隆湾海滩生物碎屑分布及其对沉积物粒度特征的影响

在热带砂质海岸,生物碎屑是海滩沉积物的重要组成部分,其分布和变化影响海滩沉积物的粒度特征。采用添加过量盐酸和双氧水的方法对海南高隆湾海滩表层沉积物进行了去生物碎屑前后粒径分布的对比,并结合海滩高程测量分析,结果表明:（1）海滩剖面上沉积物中生物碎屑的含量主要受到海水动力的影响,且生物碎屑颗粒较粗、重量较大,在高潮时由波浪流推上海滩并滞留。（2）海滩沉积物中生物碎屑的分布主要受三方面影响:一是地形及常涌浪向;二是区域中养殖业产生的生物碎屑;三是岸外发育的珊瑚礁坪。（3）海滩沉积物中生物碎屑的含量随季节变化,冬季至春季由海水供给的生物碎屑减少、进一步分解,使得北部海滩生物碎屑含量减少;而珊瑚碎屑的稳定供给和春季较强的波浪动力条件又使研究区南部断面的生物碎屑含量增加。（4）海滩沉积物中粗颗粒所含生物碎屑多于细颗粒中的生物碎屑,生物碎屑粒径主要为-1~2,即粗砂至细砾。沉积物中生物碎屑含量愈大,对粒径参数的影响也愈大。     

黄河三角洲新生湿地磷分布特征及吸附解吸规律

采用改进的 Hedley 磷分级方法研究了黄河三角洲新生湿地由河向海过渡带表层土壤磷形态变化和分布特征,并通过等温吸附解吸实验阐明了沿程土壤对外源磷的持留能力和释放风险。结果表明,各样点无机磷占总磷93%以上,是磷的主要存在形态。土壤中有机磷含量较低,可能与较低的有机质含量有关。无机磷中稀盐酸磷是最主要存在形态,与各样点Ca/Al含量密切相关。有效磷含量在18.6~33.4 mg/kg之间,仅占总磷的3.2%~5.9%,可能会限制湿地植物的生长。覆有植被的土壤中有效磷含量显著高于河滩和海滩土壤,说明植被存在对有效磷的积累有一定促进作用。由吸附解吸实验可知,加入较低浓度（0.05~5 mg/L）的外源磷时,随着初始磷浓度的升高,土壤对磷的吸附量增加,吸附率为70%~99%,解吸率小于7%,这说明各样点土壤的除磷能力较强,且流失风险较低。     

不同干燥方式对湖泊沉积物磷提取的影响

以滇池5个典型区域表层沉积物为例,研究了自然风干、低温烘干和真空冻干等3种干燥方式对沉积物中磷的形态含量及其生物有效性测定的影响。结果表明：烘干、风干过程促进了沉积物有机磷的降解转化和微生物磷的释放,导致有机磷的含量偏低,总磷含量却比冻干高。各形态磷受不同干燥方式的影响程度不同,风干样品中BD-P较高,冻干样品中NaOH-rP含量最高,NH4Cl-P、HCl-P、残渣磷（Residual-P）由于含量较低或其化学性质比较稳定而差异不大。冻干样品中生物可利用磷分别比风干、烘干高26.7%、20.2%,表明冻干处理能较为真实地反映沉积物中磷的组成特征,是比较理想的样品干燥方式。各形态含量顺序为：藻类可利用磷（AAP）〉NaHCO3可提取磷（Olsen-P）〉水溶性磷（WSP）〉易解吸磷（RDP）。沉积物中Olsen-P与NH4Cl-P、BD-P、NaOH-rP、活性磷及上覆水体总磷水平呈显著正相关,因此可作为评价滇池沉积物磷的生物有效性的重要指标。     

风浪扰动引起湖泊磷形态变化的模拟试验研究

为了解一次完整的大风浪过程(包括风浪扰动及扰动后的静风期)水体中各形态磷的变化情况及其影响因素,进行了室内模拟风浪扰动的试验研究。结果显示大风浪扰动初期水体中悬浮物(SS)、总磷(TP)、颗粒态磷(PP)和溶解性总磷(DTP)的浓度大幅增加,扰动持续半天后水体SS、TP、PP的浓度均达到最大值,扰动停止后,至少需要10d时间水体中SS、TP、PP的浓度才能回复到扰动前水平;扰动期间水体DTP浓度居于高值,但风浪停止后立即降低;整个风浪过程水体中溶解性反应磷(SRP)浓度变化不大。试验表明,扰动初期沉积物中Fe、Mn结合态磷能快速释放到水体中,但随着扰动的持续,水体复氧,释放到水体中的溶解性活性磷又能与Fe、Mn结合随悬浮物沉降到水底。扰动期间及随后静置1d时间内,水体中悬浮颗粒物的中值粒径连续下降,意味着悬浮颗粒物对磷的吸附能力在不断增强。但水体静置较长时间后,扰动引起的悬浮物几乎全部沉降,絮凝等作用导致水体颗粒物粒度增大。本研究说明虽然大风浪扰动初期能引起浅水湖泊中颗粒态和溶解态营养盐浓度的迅速提高,能够为水华蓝藻的快速生长提供大量可直接利用或酶解的营养盐,但随着风浪扰动的持续,由于水体复氧、水中颗粒物粒度不断细化、颗粒物中的有机成分比例不断增高等,悬浮颗粒物对活性磷的吸附能力也相应提高,两种作用相互削减使得风浪扰动后期水体活性磷浓度的增幅并不明显。     

Importance of terrestrially-derived,particulate phosphorus to phosphorus dynamics in a west coast estuary

Allochthonous inputs of suspended particulate matter from freshwater environments to estuaries influence nutrient cycling and ecosystem metabolism. Contributions of different biogeochemical reactions to phosphorus dynamics in Tomales Bay, California, were determined by measuring dissolved inorganic phosphorus exchange between water and suspended particulate matter in response to changes in salinity, pH, and sediment redox. In serum bottle incubations of suspended particulate matter collected from the major tributary to the bay, dissolved inorganic phosphorus release increased with salinity during the initial 8 h; between 1–3 d, however, rates of release were similar among treatments of 0 psu, 16 psu, 24 psu, and 32 psu. Release was variable over the pH range 4–8.5, but dissolved inorganic phosphorus releases from sediments incubated for 24 h at the pH of fresh water (7.3) and seawater (8.1) were similarly small. Under oxidizing conditions, dissolved inorganic phosphorus release was small or dissolved inorganic phosphorus was taken up by particulate matter with total P content <50 μmoles P g^?1; release was greater from suspended particulate matter with total phosphorus content >50 μmoles P g^?1. In contrast, under reducing conditions maintained by addition of free sulfide (HS^?), dissolved inorganic phosphorus was released from particles at all concentrations of total phosphorus in suspended particulate matter, presumably from the reduction of iron oxides. Since extrapolated dissolved inorganic phosphorus release from this abiotic source can account for only 12.5% of the total dissolved inorganic phosphorus flux from Tomales Bay sediments, we conclude most release from particles is due to organic matter oxidation that occurs after estuarine deposition. The abiotic, sedimentary flux of dissolved inorganic phosphorus, however, could contribute up to 30% of the observed net export of dissolved inorganic phosphorus from the entire estuary.     

乌裕尔河流域颗粒有机碳的来源：碳同位素证据

以2008、2009年所采集的乌裕尔河9个点位水体中的悬浮物为研究对象,对丰、枯水期颗粒有机碳（POC）含量、碳同位素组成（^13C、^14C）及表观年龄进行了系统测试与分析,以期探讨河流中颗粒有机碳来源与流域土壤侵蚀的关系。研究结果表明,该河流中颗粒有机碳（POC）主要来源于未受玉米残体及根系输入影响的深层土壤,且土...     

Flux of particulate matter in the tidal marshes and subtidal shallows of the Rhode River estuary

There was a net influx of suspended particulate matter to the uppermost part of the Rhode River estuary during the several years of this study. Most of the influx was due to episodic discharges of suspended sediment from the watershed during heavy rains. In contrast, tidal exchange of particulate matter was not related to rainstorms. Sediment composition data and historical records indicate that marsh accretion accounts for only 13% of the sediment trapping although marshes occupy 60% of the study area. Influx of particulate matter to the marshes is directly related to the amount of time they are submerged during tidal cycles.     

珠江水体悬浮物碳稳定同位素组成与流域土壤侵蚀研究

以珠江流域水体悬浮物为研究对象,对其碳稳定同位素组成(δ13C)及颗粒有机碳(POC)的含量进行了测定和研究。结果表明:河流悬浮物同位素组成与珠江流域植被分布格局、土壤有机质密切相关;珠江悬浮物碳同位素组成主要受C3植被影响,其中,西江悬浮物碳同位素组成表现出较强的C4植被特征。东江水体悬浮物碳同位素组成在洪水季节表现出较强的C4植被特征,其它季节则表现出C3植被特征;北江水体悬浮物碳同位素组成无明显的C4植被特征。东江悬浮物样品POCδ13C值呈逐年上升趋势,与近年来流域内植被破坏和土壤侵蚀加剧相对应,并显示其侵蚀程度超过西江流域。     

Geochemistry of rare earth elements in the mainstream of the Yangtze River,China

Water, suspended matter, and sediment samples were taken from 8 locations along the Yangtze River in 1992. The concentration and speciation (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter, and residual forms) of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb, and Lu) were determined by instrumental neutron activation analysis (INAA).The contents of the soluble fraction of REEs in the river are low, and REEs mainly reside in particulate form. In the particles, the chondrite-normalized distribution patterns show significant LREE enrichment and Eu-depletion. While normalized to shales, both sediments and suspended matter samples show relative LREE enrichment and HREE depletion. REEs are relatively enriched in fine-grained fractions of the sediments.The speciation characteristics of REEs in the sediments and suspended matter are very similar. The amount of the five forms follows the order: residual>>bound to organic matter∼bound to Fe–Mn oxides>bound to carbonates>>exchangeable. About 65 to 85% of REEs in the particles exist in the residual form, and the exchangeable form is very low. High proportions of residual REEs reveal that REEs in sediments and suspended matter are controlled by their abundances in the earth's crust. Carbonate, Fe–Mn oxide and organic fractions of REEs in sediments account for 2.4–6.9%, 5.2–11.1%, and 7.3–14.0% of the total contents respectively. They are similar to those in the suspended matter. This shows that carbonates, Fe–Mn oxides and organic matter play important roles during the particle-water interaction processes. By normalization to shales, the 3 forms of REEs follow convex shapes according to atomic number with middle REE (Sm, Eu, and Tb) enrichment, while light REE and heavy REE are depleted.     

Suspended sediments and organic matter in mountain headwaters of the Amazon River: Results from a 1-year time series study in the central Peruvian Andes

Few studies have examined the dynamics of sediments and suspended organic matter and their export from headwater basins in the Andes Mountains to the Amazon River, despite the fact that the Andes are the primary source of sediments to the lower Amazon basin. We measured river discharge as well as the concentration, δ¹⁵N, δ¹³C, %N, and %OC of coarse and fine suspended sediments (CSS and FSS) in the Chorobamba River, located in the central Andean Amazon of Peru. Samples were taken at least weekly over an entire year (July 2004-July 2005), with additional sampling during storms. Concentrations of particulate organic matter (POM) were generally low in the study river, with concentrations increasing by up to several orders of magnitude during episodic rain events. Because both overall flow volumes and POM concentrations increased under stormflow conditions, the export of POM was enhanced multiplicatively during these events. We estimated that a minimum of 80% of annual suspended sediment transfer occurred during only about 10 days of the year, also accounting for 74% of particulate organic carbon and 64% of particulate organic nitrogen transport. Significant differences occurred between seasons (wet and dry) for δ¹³C of coarse and fine POM in the Chorobamba River, reflecting seasonal changes in organic matter sources. The time series data indicate that this Andean river exports approximately equal amounts of fine and coarse POM to the lower Amazon. The observation that the vast majority of sediments and associated OM exported from Andean rivers is mobilized during short, infrequent storm events and landslides has important implications for our understanding of Amazon geochemistry, especially in the face of incipient global change.     

Silicon isotope compositions of dissolved silicon and suspended matter in the Yangtze River, China

Silicon isotope compositions of main channel samples of the Yangtze River were systematically investigated along with their chemical compositions. The concentration of suspended matter in the Yangtze River tends to decrease from the upper reaches to the lower reaches, corresponding to settling of the sediments in the lakes and reservoirs due to reduction of the velocity of water flow. The silica contents of suspended matter vary from 52.1% to 56.9% and their δ³⁰Si values vary from 0 to −0.7‰, both similar to those of shales. From the upper to lower reaches, the silica contents of suspended matter tend to increase, whilst their δ³⁰Si values tend to decrease. Both trends reflect the increase of clay minerals and decrease of carbonates in suspended matter.The concentrations of dissolved silicon vary from 97 to 121 μmol/L and their δ³⁰Si values vary over a wide range from 0.7 to 3.4‰. From the upper to lower reaches, dissolved silica concentrations tend to decrease and their δ³⁰Si values tend to increase. These trends mainly reflect the change of chemical and isotopic characteristics of the tributaries from the upper to lower reaches. The major factors responsible for these changes may be the high meteoric precipitation and significant silicon absorption by grass (in wetlands) and rice (in paddy fields) in drainage areas of the middle and lower reaches.There is no correlation between δ³⁰Si of dissolved silicon and that of suspended matter. The Δ³⁰Si_Diss-SPM values vary over a wide range of 1.0-3.7‰, indicating that (1) they are out of isotopic equilibrium, (2) dissolved silicon and the associated suspended matter do not belong to one physico-chemical system, and (3) isotopic exchange rate between them is very slow.The δ³⁰Si value of dissolved silicon output from the Yangtze River to the East Sea is estimated to be 3.0‰, much higher than the values reported for the Amazon and Congo rivers. This increases the δ³⁰Si range of dissolved silicon in the world’s rivers from 0.4-1.2%; to 0.4-3.4%.     

长江口盐沼滩面发育对有机碳深度分布的制约

通过对长江口崇明东滩高潮滩、中潮滩以及光滩柱状样的有机碳含量与碳稳定同位素组成（δ13C）、粒度组成等的测定，研究盐沼有机碳深度分布特征与形成机制。结果表明，盐沼土壤颗粒有机碳（POC）主要赋存于粒径小于0.016 mm的颗粒中，POC含量对粒径在0.002~0.004 mm区间的颗粒含量变化最敏感，说明盐沼POC主要来自长江径流悬移质，这与有机碳稳定同位素结果一致。土壤POC含量与不同粒径区间颗粒含量相关关系表明，高潮滩与中潮滩柱样的泥沙级配较为接近；光滩柱样POC含量与不同粒径区间颗粒含量相关关系特征与高、中潮滩柱样的基本类似，主要不同表现在粒径大于0.016 mm的粗颗粒，这很可能受控于盐沼不同高程部位动力沉积过程。盐沼植被对高、中潮滩柱样POC的贡献相当可观，个别层段高达55.6%；植被对土壤POC的贡献受到滩面过程的明显制约。滩面动力沉积过程形成盐沼垂向上独特的沙、泥纹层构造，其优良的封堵效能显著影响土壤有机碳的垂向分布。盐沼滩面动力沉积过程是塑造有机碳深度分布特征的关键因素。     

Transformation of phosphorus in the Elbe estuary

The distribution of dissolved and particle-bound phosphorus (P) was investigated in the Elbe estuary during March 1995. The forms of particulate P were studied with a sequential extraction technique. Organic P dominated particle-bound P in the outer reaches of the estuary (52%), decreased to a minimum of 21% in the turbidity zone, and increased to 33% further upstream. Fe-bound P was the second most important P species in the outer reaches (27%) and dominated in the turbidity zone (up to 57%) and upstream of the turbidity zone (up to 48%). The P:Fe ratio increased with decreasing salinity, from 0.11 in the outer reaches to about 0.22 at zero salinity. Dissolved inorganic P release from reverine suspended matter was about two to three times larger than release, from marine suspended matter and was dominated by release of Fe-bound P. Dissolved inorganic P release from marine and from riverine organic matter were of equal importance. Because marine suspended matter dominates in the estuary, this suggests riverine organic matter is remineralized much faster than marine organic matter. This is in line with the refractory nature of marine organic matter (no phytoplankton bloom) and the easily degradable character of the riverine suspended matter (phytoplankton bloom) in the Elbe estuary during March 1995.     

Phosphorus in suspended matter and sediments of a hypertrophic lake. A case study: Lake Dianchi,China

From June 2004 to December 2004, Lake Dianchi, which had large scale of cyanobacterial blooms was investigated in order to study P-fractionation in the suspended matter and the sediment. The investigation improves our understanding of phosphorus in Lake Dianchi and the relationship between phosphorus and cyanobacterial blooms. It contributes to the available literature on the behavior of P in hypertrophic lakes. The distribution of P-fractions in Lake Dianchi was not uniform from northwest to south, but was closely related to the trophic status of the whole lake. The concentrations of total phosphorus, labile P (NH₄Cl-P), Organic P (NaOH-NRP) and loss on ignition in suspended matter were positively correlated with the strength of cyanobacterial blooms. Total phosphorus in suspended matter was relatively stable for almost half an year and closely related to Chl. a concentration. The main content of organic phosphorus is in the cyanobacterial blooms. The concentrations of phosphorus bound to metal oxides and carbonates (NaOH-SRP and HCl-P) in sediment were similar to NaOH-SRP and HCl-P in the corresponding suspended matter. The latter two forms of P in suspended matter were not affected by cyanobacterial blooms, indicating that the inorganic phosphorus is derived from the sediment after resuspension from the sediment due to wind and wave action. The contribution of the different P-fractions to TP in sediment and in suspended matter indicates that NH₄Cl-P in the suspended matter is an important buffer for maintaining dissolved phosphorus in water.