Speciation of organic phosphorus in a sediment profile of Lake Taihu I: Chemical forms and their transformation

Organic phosphorus(nonreactive P,NRP)is a major component of P in sediments,but information about its chemical forms and dynamic transformation is limited.The chemical forms and dynamic behaviors of NRP in a sediment profile from Lake Taihu,a freshwater and eutrophic lake in China,were investigated.Five forms of NRP in the sediments were extracted based on a chemical fractionation technique,including easily labile NRP(NaHCO3-NRP),reactive metal oxide-bound NRP(HCl-NRP),humic acid-associated NRP(NaOH-NRPHA),fulvic acid-associated NRP(NaOH-NRPFA)and residual NRP(Res-TP).There were notable transformations with increasing sediment depth from the labile NaHCO3-NRP and NaOH-NRP pools to the recalcitrant HCl-NRP and Res-TP pools,which caused the NRP to become increasingly recalcitrant as the early diagenetic processes proceeded.Further analyses showed that the relative changes in contents of organic matter and reactive Fe oxides in the sediment profile triggered a competition for binding NRP fractions and led to the transformation of NRP.The results highlighted the importance of abiotic processes in regulating the diagenesis of organic P and its stability in sediments.     

Variations in concentrations and bioavailability of heavy metals in rivers caused by water conservancy projects: Insights from water regulation of the Xiaolangdi Reservoir in the Yellow River

Water regulation of the Xiaolangdi Reservoir of the Yellow River was chosen as a case to investigate variations in concentrations and bioavailability of heavy metals caused by water conservancy projects in rivers. Water and suspended sediment (SPS) samples were collected at downstream sampling sites along the river during this period. Concentrations and speciation of Zn, Cr, Cu, Ni, and Pb in water and SPS samples were analyzed, and their bioaccumulation was studied with Daphnia magna. This study indicated that the exchangeable and carbonate-bound fractions of heavy metals in SPS decreased along the studied stretch, and the dissolved heavy metal concentrations increased along the river with 1.6–15 folds. This is because sediment resuspension increased along the river during water regulation, giving rise to the increase of heavy metal release from SPS. The dissolved Zn, Cu, Ni, and Pb concentrations were significantly positively correlated with SPS concentrations, and their increase along the river was greater than Cr. The body burdens of heavy metals in D. magna exposed into samples collected from the reservoir outlet were 1.3–3.0 times lower than those from downstream stations, suggesting that the heavy metal bioavailability increased during water regulation. This should be considered in the reservoir operation.     

Effect of sediment size on bioleaching of heavy metals from contaminated sediments of Izmir Inner Bay

The effect of sediment size on metals bioleaching from bay sediments was investigated by using fine (< 45 μm), medium (45-300 μm), and coarse (300-2000 μm) size fractions of a sediment sample contaminated with Cr, Cu, Pb, and Zn. Chemical speciation of the metals in bulk and size fractions of sediment were studied before and after bioleaching. Microbial activity was provided with mixed cultures of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans. The bioleaching process was carried out in flask experiments for 48 days, by using 5% (W/V) of solid concentration in suspension. Bioleaching was found to be efficient for the removal of selected heavy metals from every size fraction of sediments, where the experiments with the smaller particles resulted in the highest solubilization ratios. At the end of the experimental period, Cr, Cu, Pb and Zn were solubilized to the ratios of 68%, 88%, 72%, and 91% from the fine sediment, respectively. Higher removal efficiencies can be explained by the larger surface area provided by the smaller particles. The changes in the chemical forms of metals were determined and most of the metal releases were observed from the reducible and organic fractions independent from grain size. Higher concentrations were monitored in the residual fraction after bioleaching period, suggesting they are trapped in this fraction, and cannot be solubilized under natural conditions.     

Characterization of heavy metal desorption from road-deposited sediment under acid rain scenarios

Road-deposited sediments(RDS) on urban impervious surfaces are important carriers of heavy metals.Dissolved heavy metals that come from RDS influenced by acid rain,are more harmful to urban receiving water than particulate parts.RDS and its associated heavy metals were investigated at typical functional areas,including industrial,commercial and residential sites,in Guangdong,Southern China,which was an acid rain sensitive area.Total and dissolved heavy metals in five particle size fractions were analyzed using a shaking method under acid rain scenarios.Investigated heavy metals showed no difference in the proportion of dissolved fraction in the solution under different acid rain pHs above3.0,regardless of land use.Dissolved loading of heavy metals related to organic carbon content were different in runoff from main traffic roads of three land use types.Coarse particles(150 μm) that could be efficiently removed by conventional street sweepers,accounted for 55.1%-47.1%of the total dissolved metal loading in runoff with pH 3.0-5.6.The obtained findings provided a significant scientific basis to understand heavy metal release and influence of RDS grain-size distribution and land use in dissolved heavy metal pollution affected by acid rain.     

Impact of anions on the heavy metals release from marine sediments

Marine sediments from Lianshan Bay in Huludao, China, were studied in laboratory. A series of simulated experiments were carried out to investigate the influences of three kinds of anions CL^-, SO4^2- and HCO3^- on the release ofCd, Pb, Cu and Zn from the sediments. The results showed that the sequences about the impact of the three anions were Cl^-〉HCO3^-〉SO4^2＋. The release potential of heavy metals in the presence of each anions was in the following order： Cd≥Cu 〉Zn≈Pb. The correlations were positive between CI content and the quantity of Cd released from the marine sediment, whereas there was no significant relationship between CI content and amount of Cu and Zn released. For SO4^2- and HCO3^-, the release of the heavy metals from marine sediments was not obvious.     

Assessing the capacity of biochar to stabilize copper and lead in contaminated sediments using chemical and extraction methods

Because of its high adsorption capacity, biochar has been used to stabilize metals when remediating contaminated soils; to date, however, it has seldom been used to remediate contaminated sediment. A biochar was used as a stabilization agent to remediate Cu- and Pb-contaminated sediments, collected from three locations in or close to Beijing. The sediments were mixed with a palm sawdust gasified biochar at a range of weight ratios (2.5%, 5%, and 10%) and incubated for 10, 30, or 60?days. The performance of the different treatments and the heavy metal fractions in the sediments were assessed using four extraction methods, including diffusive gradients in thin films, the porewater concentration, a sequential extraction, and the toxicity characteristic leaching procedure. The results showed that biochar could enhance the stability of heavy metals in contaminated sediments. The degree of stability increased as both the dose of biochar and the incubation time increased. The sediment pH and the morphology of the metal crystals adsorbed onto the biochar changed as the contact time increased. Our results showed that adsorption, metal crystallization, and the pH were the main controls on the stabilization of metals in contaminated sediment by biochar.     

Partitioning of heavy metals in the surface sediments of Quanzhou Bay wetland and its availability to Suaeda australis

In order to investigate distributions of heavy metal pollution in Quanzhou Bay wetland, the total concentration and chemical partitioning of a number of heavy metals （Cu, Zn, Cd, Pb, Cr, Hg） in sediments of three sampling sites of Quanzhou Bay wetland and their availability to Suaeda australis were analyzed. The Geoaccumulation Index （Igeo） values reveal that the sediments of three sampling sites may all be considered as moderately contaminated for Pb and Zn, and all sediments might be strongly contaminated with cadmium. The partitioning analyses revealed the measured heavy metals in three sites are bound to the exchangeable fraction at lower concentrations. The measured metals in a considerable amount are bound to the reducible and oxidizable fractions, and a high proportion of the measured heavy metals were distributed in the residual fraction in the sediment samples. The concentrations of Cd in each chemical phase extracted from the sediments are above natural global background levels and should be further investigated because of its toxicity. Suaeda australis has different accumulation abilities for the measured heavy metals. For the root and stem, the bioaccumulation ability assessed by bioaccumulation factor （BAF） for the measured heavy metals follows the decreasing order as： Cu〉Cr〉 Zn〉Cd, Pb, Hg. In the leaf, stronger bioaccumulation ability for Hg is exhibited. The heavy metal concentrations in Suaeda australis roots have positive correlations with their available fractions, while the exchangeable fraction of Cu and Cd might have be more important to both mature plant roots and seedling roots uptake than other fractions; as for Cr, the oxidizable fraction might make a greater contribution to the plant root uptake; as for Zn, the reducible fraction might make so contribution ; and for Pb, the oxidizable fraction might make a significant contribution to the mature plant root uptake, however, the exchangeable fraction might have a significant contribution to the seedling root uptake.     

Distribution and speciation of metals in sediments along Le An River

Distribution of metal concentration and metal speciation in sediments along Le An River were studied．A high concentration of copper in sediments was found at Gukou，receiving Dexing Copper Mine effluents．It was decreased from Gukou to Daicun rapidly，but tended to increase from Daicun to Caijiawan Speciation of Cu，Cd，Zn and Pb were studied by sequential selective chemical extraction．The speciation fractions were classified into three bioavailable categories：easily bioavailable，moderately bioavailable and inert bioavailable The geoaccumulation index，^Igeo，was used to illustrated the pollution level of heavy metals in sediments     

Phosphorus fractions and its release in the sediments of Haihe River, China

The amounts and forms of phosphorus (P) in surface sediments of Haihe River, Tianjin, North China, were examined using a sequential chemical extraction procedure. Five fractions of sedimentary P, including loosely sorbed P (NH4Cl-P), redox-sensitive P (BD-P), metal oxide bound P (NaOH-P), calcium bound P (HCl-P), and residual P (Res-P) (organic and refractory P), were separately quantified. The results indicated that the contents of di erent P fractions in the sediments varied greatly. The total P (TP) contents ranged from 968 to 2017 mg/kg. Phosphorus contents in NH4Cl-P, BD-P, NaOH-P, and HCl-P ranged from 6.7 to 26.6 mg/kg, 54.5 to 90.2 mg/kg, 185.2 to 382.5 mg/kg, and 252.3 to 425.5 mg/kg, respectively, which represented 1.2%–3.2%, 7.7%–13%, 33.3%–48.9%, and 36.2%–54.2% of the sedimentary inorganic P, respectively. For all the sediment samples, the rank order of P-fractions was Res-P > HCl-P > NaOH-P > BD-P > NH4Cl-P. The highly positive relationship between the amounts of P released from the sediments and those in the NH4Cl-P and BD-P fractions, indicated that NH4Cl-P and BD-P were the main fractions that can release P easily.     

Distribution and speciation of heavy metals in sediments at Caijiawan region

Metals in different fractions in samples from surface sediments，cores，riverbank soil，islet soil and agricultural soil at Caijiawan were determined．The effect of particle size，density gradient on metal accumulation in sediments were studied．The chronology of core samples indicated that the pollution history corresponded to the development history of Dexing Copper Mine．     

连环湖阿木塔泡沉积物中重金属形态及其对环境影响分析

采用了BCR三步提取法,对连环湖阿木塔泡AMT岩芯沉积物中的Mn、Cr、Cu、Fe、Ni、Pb和Zn等7种重金属元素的化学形态进行了分析。结果表明：Cr、Cu、Fe、Ni、Pb、zn元素以残渣态为主,Mn元素以可交换态及碳酸盐结合态为主。Cr、Cu、Ni、Pb的有机物及硫化物结合态、Fe—Mn氧化物结合态含量较高,Zn的有机物及硫化物含量较高。其中,Mn、Cr、Ni和Pb对环境产生危害的可能性最大,对这几元素应该予以足够的关注。     

伊通河沉积物重金属赋存特征的统计分析

分析了长春市伊通河卫星桥(1#),自由大桥(2#)和东大桥(3#)三个采样点不同深度的沉积物样品中Cu,Pb,Zn,Ni,Co,As的含量及赋存形态,并利用多元统计分析方法研究金属间以及不同形态与沉积物性质之间的相互联系,从而深入揭示城市河流沉积物中金属的空间累积规律。结果表明:伊通河1#和2#采样点不同深度的重金属浓度随深度变化幅度不明显,而3#采样点中Pb、Cu和Zn含量随深度变化显著,它们的相对标准偏差分别达到70.3%,48.1%和52.2%。三个采样点中Cu,Pb,Zn显著相关(r=0.914,0.798和0.949),而Ni,Co,As之间呈显著相关关系(r=0.924,0.843和0.812)。说明这2组金属可能分别具有相同的来源和迁移特性。形态分析结果指出,在沉积物中Cu主要与有机质或硫化物相结合,Pb,Zn和Ni主要存在于由铁氧化物结合态和有机/硫化物结合态中,以碳酸盐和锰氧化物形式存在的比例相对较少。统计分析进一步说明,Cu,Pb,Zn与锰氧化物结合方式类似,Pb在有机/硫化物结合态中可能主要与硫化物相结合,而不是有机质。Cu和Zn有机硫化物结合态的含量与有机质的含量密切相关。     

渤海东部和黄海北部沉积物中重金属分布特征

通过对渤海东部及黄海北部海域138个站位沉积物样品的重金属等含量分析,研究了该海域沉积物重金属元素分布特征及其控制因素.渤海东部及黄海北部海域沉积物中As、Cu、Cd、Cr、Co、Hg、Ni、Pb、V、Zn的平均含量分别为:9.87,20.1,0.15,58.9,11.6,0.02,26.7,23.0,74.0,65.5μg/g;重金属元素Cu、V、Cr、Co、Ni、Zn含量与有机碳含量、小于63μm细粒沉积物呈显著正相关,其在表层沉积物中的分布明显受到有机质含量和沉积物粒径的控制,而As、Hg分布没有明显受到有机质含量和沉积物粒径的影响.富集系数显示, Cr、Co、Ni、Pb、V和Zn为无富集;Cu为轻度富集;As、Cd和Hg为中度富集;依据Q-型聚类分析特征,将研究区域沉积物划分为3个不同的重金属分区,Ⅰ类区沉积物Hg富集程度较高;Ⅱ类区沉积物As富集程度较高;Ⅲ类区重金属元素含量普遍较高,尤其Cu、Zn和Cd含量明显增高.     

重金属元素BCR提取法及在太湖沉积物研究中的应用

采用BCR提取法,HCl-HNO3-HF消化法和ICP-AES仪器测定了西太湖沉积岩芯中Cu,Fe,Mn,Ni,Pb和Zn 6种重金属元素不同形态的质量分数.结果表明:采用BCR方法对太湖沉积物重金属元素形态进行提取,提取结果具有较高的精度和稳定性;受元素地球化学性质及沉积物理化性质的影响,Cu,Fe,Ni和Zn以残渣态为主;Mn以可交换态及碳酸盐结合态为主;Pb的有机物及硫化物结合态,Fe/Mn氧化物结合态以及残渣态的质量分数基本一致;重金属元素Fe/Mn氧化物结合态的质量分数与可还原态Mn质量分数有较好的正相关性,有机物及硫化物结合态的质量分数与有机质质量分数相关性较好.      

铜陵矿区河流沉积物重金属的迁移及环境效应

测定铜陵矿区的新桥至顺安河沉积物中5种重金属的全量和形态,并结合环境条件分析它们的迁移变化特征,以阐明不同重金属对河流沉积物环境影响的程度.结果表明,该区域沉积物重金属除Cr外,Cu、Zn、Pb、Cd的均值皆远超长江下游沉积物背景值,其中以Cu和Cd最显著.重金属横向迁移结果显示,矿山重金属会随着沉积物的距离增加而显著降低,新桥河沉积物的迁移变化显著高于顺安河沉积物.重金属Cu、Zn、Pb、Cr皆以残渣态为优势,Cd则以酸提取态为主;迁移过程中Cu、Zn、Cr残渣态逐步增加,毒性减弱;Pb、Cd的活性态比例增大,仍有较高的释放风险.重金属的纵向迁移结果表明,离矿山的位置远近对沉积柱金属的总量和形态起决定作用;新桥河沉积物金属总量高、活性组分多且垂向变化幅度相对较小,说明尾矿堆积速度较快且释放风险较高;顺安河金属总量较低但垂向变化幅度较大,且多种元素的变化趋势不同,说明矿区下游河流沉积物既受尾矿的影响,也受河流流域物质本身的影响.     

南四湖及主要入湖河流表层沉积物重金属形态组成及污染研究

采用BCR（SM&T）方法对南四湖及主要入湖河流丰水季节表层沉积物中Cr、Cu、Mn、Ni、Pb、Zn 6种重金属元素的酸提取态、可还原态、可氧化态及残渣态进行了连续提取,分析了各水体单元表层沉积物重金属元素的形态组合特征、人为污染状况及潜在生态风险.研究结果表明,泗河、京杭运河、洙赵新河、府河上游、上级湖南部湖区及下级湖区表层沉积物中Cr、Cu、Ni、Zn以残渣态为主,其含量可占到该元素总量的80%～90％,人为污染程度较弱;老运河、府河入湖口、白马河表层沉积物中Cr、Cu、Ni、Zn的残渣态含量明显降低,而可提取态（酸提取态、可还原态、可氧化态）含量可增至80％以上,其中以可氧化态、酸提取态为主,人为污染程度较重;各水体单元表层沉积物中Pb、Mn以残渣态和可氧化态为主,其含量占Pb、Mn含量的95％、70％左右,基本未受人为污染.随着表层沉积物中有机物的矿化分解及环境条件的改变,老运河、府河入湖口、白马河等重金属人为污染较重的沉积物中Cr、Cu、Ni、Zn的可氧化态、酸提取态及可还原态可发生活化,具有较高的潜在生态风险.     

太湖梅梁湾岸边带底泥中重金属的形态与分布

选择太湖梅梁湾一处没有外源污染并具有藻类富集特征的岸边带进行了底泥中重金属形态与分布的研究.结果表明,Cu, Ni和Zn在水位变幅区及水向辐射区均有一定程度的富集;Cr和Pb则在水向辐射区有所富集(富集系数>1).岸边带底泥中这5种重金属的惰性形态百分率均显著低于开阔水体底泥,其中惰性态Ni在岸边带和开阔水体底泥中的含量分别为30.68%±0.56%和34.67%±2.72%,惰性态Pb则分别为25.45%±3.82%和34.17%±0.85%.重金属在岸边带底泥中的惰性形态含量低,说明其活性形态含量高,易于向上层水体迁移.藻类捕获型岸边带底泥中除了少量重金属会向上层水体释放外,总体可以作为湖泊重金属的汇.     

基于总量和形态的表层沉积物重金属污染及来源——以马鞍列岛海域为例

为了解马鞍列岛海域沉积物特征及重金属污染状况,于2017年6月采集了该海域表层沉积物样品,并对表层沉积物pH值、氧化还原电位（Eh）、粒度（D_[3,2]）等地球化学指标进行了同步原位调查,采用改进后的沉积物重金属形态分析的连续提取法（European Community Bureau of Reference （BCR））分析了7种重金属（Cr、As、Ni、Zn、Pb、Cu、Cd）各形态含量,并结合富集因子系数（EF）、地累积指数法（I_geo）等方法初步探索了马鞍列岛海域沉积物中重金属的污染特征及其来源.结果显示,马鞍列岛海域沉积物呈中性-弱碱性,属还原环境;近岛礁区以粉砾和粘粒为主,而远岛礁区以砂砾和粉砾为主;7种重金属总量均满足我国海洋沉积物质量I类标准;Cr、As、Ni以原生相为主,而Zn、Pb、Cu、Cd均以次生相为主;Cd以可交换态及碳酸盐结合态（F1）以及有机物及硫化物结合态（F3）为主要赋存形态,Zn、Pb、Cu以铁锰氧化物结合态（F2）为主要赋存形态,而Cr、As、Ni以残渣态为主要赋存形态;以Fe作为参比,7种重金属的富集程度顺序为Cd > Cu > Ni > Zn > Pb > Cr > As;通过空间污染状况分析发现,Cu、Cd在受人为活动影响较大的近岛礁区存在富集污染现象,其他重金属则主要表现为天然来源,除Ni外,Cu、Pb、Cd、As、Cr、Zn含量均呈近岛礁区>远岛礁区的空间分布特征.总体上,马鞍列岛国家级特别海洋保护区沉积物重金属污染程度较低,生态环境保护与底质修复效果较好.     

小清河表层沉积物重污染区重金属赋存形态及风险评价

测定了小清河表层沉积物重污染区间隙水中重金属(Cu、As、Pb、Zn、Cr、Cd和Ni)的质量浓度,采用改进的BCR顺序提取法分析了沉积物中重金属的赋存形态,并分别基于美国水质基准(CCC、CMC)和风险评价编码法(RAC)、潜在生态风险指数法对间隙水和表层沉积物中重金属的毒性及生态风险进行评价.结果表明,小清河沉积物间隙水中的重金属基本不会对水生态系统产生毒性.除As外,表层沉积物中6种重金属的含量显著高于土壤背景值,呈现明显的累积效应.沉积物中Cu、As和Ni主要赋存于残渣态,Pb、Cr主要赋存于可氧化态和残渣态,Zn、Cd以酸可溶解态和可还原态为主.Cd、Zn、Cr和Pb的有效态含量高于残渣态,有较高的二次释放潜力.RAC的评价结果表明,沉积物中Cu、Pb、Cr和As处于无风险到低风险级,Ni处于低风险到中等风险级,Cd处于中等到高风险级,Zn处于中等到极高风险级,不同重金属RAC的平均值依次为CdZnNiAsCuCrPb.潜在生态风险指数法的评价结果表明,沉积物中除Cd有强~很强生态风险外,其他6种重金属均表现为低生态风险,RI值介于136.83~264.83,研究区采样点处于中等~强生态风险.     

渤海湾表层沉积物各形态重金属的分布特征与生态风险评价

根据2008年春对渤海湾的调查,通过分级萃取的实验方法以及总量和分形态风险评价的手段,重点研究了渤海湾表层沉积物各形态重金属的分布特征、影响因素和潜在生态风险.结果表明,重金属在渤海湾中央的泥质区富集,自然来源是控制V、Ni、Cu、Pb、Co和Cd分布的主要因素,而Zn和Cr较易受环境变化或人为输入等影响,其中Pb作为大气沉降和陆源输入都存在的重金属,其受控因素与其他重金属有一定差异.形态分析表明,V、Zn和Cr以残渣态为主,Co、Ni和Cu则是可浸取态占优势.其中Co的可浸取态质量分数在A断面先增加后降低,Ni的可浸取态质量分数在海河口附近A3站达最大值(98.86%),Cu和Pb的可浸取态高值区出现在A断面的中央区域,优势形态是铁锰氧化物结合态,Cu在湾口的A10站降到最小值(43.83%),在黄河口的D1站达最大值(73.89%).风险评价表明,重金属总量富集因子由大到小:Pb>Cd>Zn>Cr>V>Co>Cu>Ni,其中Pb、Cd和Zn的富集因子均大于1,但渤海湾沉积物总体质量良好,潜在生态风险较低.从形态角度评价,V和Cr基本无污染,Zn局部轻微污染,Co大部分轻度污染,Cu由无污染到中度污染,Ni由轻度污染到重度污染,Pb则属重度污染,其中Pb在渤海湾口A11站的P%(次生相与原生相分布比值)达1 329%.综合评价得出,Pb是渤海湾沉积物污染最严重的重金属,Cu和Zn有潜在污染,V、Cr和Co基本清洁.