Temporal variability of iron concentrations and fractions in wetland waters in Sanjiang Plain, Northeast China

Chemical forms, reactivities and transformation of iron fractions in marshy waters were investigated with cross-flow filtration technique to study the iron environmental behavior. Iron fractions were divided into four parts: acid-labile iron (pre-acidification of unfiltered marshy water samples, 0.7 μm), high-molecular-weight iron (0.7-0.05 μm), medium-molecular-weight iron (0.05-0.01 μm), and low-molecular-weight iron ( 0.01 μm). The cross-flow filtration suggested that iron primarily exist in both the 0.7 μm and 0.01 μm size fractions in marshy waters. Rainfall is the key for rain-fed wetland to determine fate of iron by changing the aquatic biochemical conditions. By monitoring the variation of iron concentrations and fractions over three years, it was found that dissolved iron and acid-labile iron concentrations exhibit a large variation extent under different annual rainfalls from 2006 to 2008. The seasonal variation for iron species proved that the surface temperature could control some conversion reactions of iron in marshy waters. Low- molecular-weight iron would convert to acid-labile iron gradually with temperature decreasing. The photochemical reactions of iron fractions, especially low-molecular-weight iron had occurred under solar irradiation. The relative proportion of low-molecular-weight in total dissolved iron ranging from 28.3% to 43.2% were found during the day time, which proved that the observed decreasing concentration of acid lability iron was caused by its degradation to low molecular weight iron.     

Effects of inorganic chlorine source on dioxin formation using fly ash from a fluidized bed incinerator

Chlorine source is indispensable for polychlorinated dibenzo-p-dioxin and furan (PCDD/F) formation during municipal solid waste (MSW) incineration. Inorganic chlorine compounds were employed in this study to investigate their effects on PCDD/F formation through heterogeneous synthesis on fly ash surfaces. A fly ash sample obtained from a fluidized bed incinerator was sieved to different size fractions which served as the PCDD/F formation sources. The capability of different metal chlorides which facilitate the formation of PCDDs/Fs was found to follow the trends: Na ＜ Mg ＜ K ＜ Al ＜ Ca, when two particle fractions of ＞177 μm and 104-125 μm were used in the experiments. However, the capability of NaCl, MgCl2 and KCl did not seem much different from each other, whereas CaCl2 and AlCl3 were much more active in PCDD/F formation. NaCl and MgCl2 were relatively effective to produce more PCDDs, while KCl, AlCl3 and CaCl2 generated more PCDFs during heterogeneous reactions occurring on fly ash. 2,3,7,8-TCDF was the most significant contributor to the toxicity of the PCDDs/Fs formed from inorganic chlorine sources. Decreasing the sizes of fly ash particles led to more active formation of PCDDs/Fs when NaCl was used as inorganic chlorine in the experiment. The highest PCDDs/Fs produced from particles with size ＜37 μm, while the lowest PCDDs/Fs produced from particles with size ＞177 μm. The toxicity generally increased with decreasing size of the fly ash particles. The formation of PCDDs was mainly facilitated by the two size fractions, 104-125 μm and ＜37 μm, while formation of PCDFs was favored by the two other size fractions, ＞177 μm and 53-104 μm.     

Phosphorus speciation in the sediment profile of Lake Erhai, southwestern China: Fractionation and 31P NMR

The distribution characteristics of phosphorus(P) forms in the sediment profile of Lake Erhai,in southwestern China has been investigated by sequential extraction and 31P nuclear magnetic resonance spectroscopy(NMR) of NaOH extracts to understand P dynamics and its potential contribution to lake eutrophication.Contents of P fractions varied in the order of NH4Cl extracted P(NH4ClP) < bicarbonate-dithionite extracted P(BD-P) < HCl-P,Residual-P < NaOH extracted P(NaOH-P).The highly available NH4Cl-P represented less than 1% of total P(TP).BD-P and NaOH extracted reactive P(NaOH-rP) averaged 39%,while the ratio of Fe/P was higher than 15,indicating low P release from the sediments under permanent oxic condition.The less bio-available HCl-P,NaOH extracted nonreactive P(NaOH-nrP) and residual-P contributed 61% of TP.Regression analysis revealed that BD-P,NaOH-rP and HCl-P were positively correlated with the contents of Fe and Mn,Al and Fe,and Ca,respectively.The investigation of P compound groups in NaOH extracts by 31 P NMR showed that ortho-P and monoester-P were the largest two constituents of the P pool,followed by diester-P,phosphonate and pyro-P.A comparison of vertical variations of P groups in the sediment profile suggested that these compounds were involved in the P recycling to different extents in Lake Erhai.In particular,the lake exhibits high potential for labile P release from the surface sediments,which should be taken into consideration even after the outsourced P runoff ceased.     

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.     

Effect of organic fractions on sorption properties of organic pollutants in sediments

Humic substrates are a major fraction of sediment organic matters, and the sorption of hydrophobic organic chemicals by humic substrates influences their behavior and fate in sediment. In this paper, organic matters were divided into non-humic substrates and humic substrates. Non-humic substrates include acid leaching fraction, acid extracted fraction, and lipid; humic substrates were fractionated into Ca-binding-FA(fulvic acid), Ca-binding-HA (humic acid), oxide-FA, oxide-HA, and humin. To study the effect of organic fractions on sorption properties, sorption kinetic and equilibrium sorption experiments of phenanthrene and pentachlorophenol(PCP) in five sediments were carried out. The results showed that the contents of acid leaching fraction and oxide-binding-HA were the main fractions to affect the sorption rate constant, and for the sorption capacity of phenanthrene, humin was the major fraction, followed by oxide-binding-HA, oxidebinding-FA, and so on. While for PCP, the factors of influence on sorption capacity were mainly CEC, Ca-binding-FA, and Ca-binding-HA.     

Distribution of Cu and Pb in particle size fractions of urban soils from different city zones of Nanjing, China

Soil samples from 4 defined city zones of Nanjing were randomly collected at 0-5 cm and 5-20 cm intervals and size fractions of soil particles were separated from undisturbed bulk soils by low energy dispersion procedure. The total contents of Cu and Pb in the different particle size fractions of the urban soils were analyzed by HNO3-HF-HClO4 digestion and flame atomic absorption spectrophotometer determination. The total content of Cu and Pb in soil particle size fractions varied with their size and with city zones as well. Both the content and variation with the size fractions of Pb was bigger than of Cu supporting our previous finding that there was Pb pollution to different degrees in the urban soils although the two elements were generally enriched in clay-sized fraction. Contaminated Pb tended to be preferentially enriched in the size fraction of 2000-250 μm and clay-sized fraction. While the size fractions of the soils from newly developed and preserved area contained smaller amount of Cu and Pb, the partitioning of them in coarse and fine particle size fractions were insignificant compared to that from inner residence and commercial area. The very high Pb level over 150 mg/kg of the fine particle fractions from the soils of the inner city could be a cause of high blood Pb level reported of children from the city as acute exposure to Pb of fine particles of the urban soil might occur by soil ingestion and inhalation by young children. Thus, much attention should be paid to the partitioning of toxic metals in fine soil particles of the urban soils and countermeasures against high health risk of Pb exposure by soil ingestion and dust inhalation should be practiced against the health problem of blood Pb for young children from the cities.     

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．     

Quantification, morphology and source of humic acid, kerogen and black carbon in offshore marine sediments from Xiamen Gulf, China

Three types of macromolecular organic matters (MOMs), i.e. humic acid (HA), kerogen+black carbon (KB), and black carbon (BC) were extracted from marine sediments of Xiamen Gulf, southeast of China. The chemical composition, morphological property and source of the three extractions were characterized by elemental analyzer/isotope ratio mass spectrometry (EA/IRMS) and scanning electron microscope (SEM). The results showed that KB was the predominant fraction in MOMs, which accounted for 61.79%-89.15% of the total organic content (TOC), while HA consisted less than 5%. The relative high contents of kerogen and BC, and low contents of HA in the samples indicated that anthropogenic input might be the major source of organic matter in marine sediments near the industrial regions. The characterization of SEM, not only revealed morphological properties of the three fractions, but also allowed a better understanding of the source of MOMs. The δ 13 C values of the three fractions suggested that materials from terrestrial C 3 plants were predominant. Furthermore, the anthropogenic activities, such as the discharge of sewage, coal and biomass combustion from industry nearby and agricultural practices within drainage basin of the Jiulong River, were remarkably contributed to the variations in δ 13 C values of MOMs in the offshore marine sediments.     

Distribution of heavy metals in the water column, suspended particulate matters and the sediment under hydrodynamic conditions using an annular flume

Sediment resuspension plays an important role in the transport and fate of heavy metals in the aquatic environment. In the present study, the release and binding forms of Cr, Cu, Zn, Pb under hydrodynamic conditions were investigated using an annular flume. Two sediments located at YLZ and GBD from Liangshui River, Beijing were resuspended for 10 hr at 0.159 and 0.267 m/sec, respectively. The concentrations of suspended particulate matters of YLZ were higher than those of GBD during resuspension, indicating that the former sediment is more sensitive to the velocity. Cr in the dissolved phase stayed nearly constant at about 2.25 and 1.84 μg/L for YLZ and GBD, respectively, due to the high percentage of its stable binding fractions in both sediments, while Cu, Zn, and Pb showed a fast release in the initial period of time. However, their concentrations in SPM generally decreased with time and were higher at the lower velocity of 0.159 m/sec, which resulted from the entrainment and depressing effect of larger size particles with lower heavy metal content, commonly referred to as the "particle concentration effect". In addition, the binding form and heavy metal fractions were also found to vary during the resuspension event. A decrease in the sulphide/organic matters bounded form in GBD sediment was observed, whereas no visible changes were perceived in YLZ site samples. This phenomenon is due to the oxidation of heavy metal-sulphide binding forms, which originated from its high acid volatile sulphide content in GBD sediment.     

Distribution and accumulation of biogenic silica in the intertidal sediments of the Yangtze Estuary

Sedimentary biogenic silica is known to be all important parameter to understand biogeochemical processes and paleoenviromental records in estuarine and coastal ecosystems. Consequently, it is of great significance to investigate accumulation and distribution of biogenic silica in sediments. The two-step mild acid-mild alkaline extraction procedure was used to leach biogenic silica and its early diagenetic products in intertidal sediments of the Yangtze Estuary. The results showed that total biogenic silica(t-BSi)in the intertidal sediments varied from 237. 7-419. 4 μmol Si/g. while the mild acid leachable silica(Si-HCl)and the mild alkaline leachable silica(Si-Alk)were in the range of 25. 1-72. 9μmol Si/g and 208. 1-350. 4 μmol Si/g. respectively. Significant correlations were observed for the grain size distributions of sediments and different biogenic silica pools in intertidal sediments. This confirms that grain size distribution Can significantly affect biogenic silica contents in sediments. Close relationships of biogenic silica with organic carbon and nitrogen Were also found, reflecting that there is a strong coupling between biogenic silica and organic matter biogeochemical cycles in the intertidal system of the Yangtze Estuary. Additionally, the early diagenetic changes of biogenic silica in sediments are discussed in the present study.     

不同粒径黄河沉积物中可提取腐殖质的含量分布及光谱特性

测定了黄河表层沉积物3种粒径组分（Ⅰ：100～300 μm;Ⅱ: 63～100 μm;Ⅲ: <63 μm）中总有机碳和可提取腐殖质的含量,分析了可提取腐殖质的紫外-可见吸收光谱、红外光谱和三维荧光光谱特征,探讨了不同粒径组分沉积物中可提取腐殖质含量分布及其化学组成特性.结果表明,沉积物有机质主要为粘土矿物吸附的天然腐殖质成分,总有机碳中可提取腐殖质的比例随沉积物有机质与矿物质相互作用的增强而降低,顺序为Ⅰ>Ⅱ>Ⅲ.3种粒径组分沉积物中可提取腐殖质的紫外-可见吸收光谱相似但相对峰强不同;红外光谱主要有5个吸收峰,各吸收峰面积百分含量的计算结果表明酚、醇及羧酸类官能团为主要的活性官能团,占可提取腐殖质组成的75%以上;三维荧光光谱主要有3个荧光峰,除了典型的类腐殖质荧光峰（峰A和峰C）外,还有源于小分子类蛋白或酚类物质的荧光峰（峰T′）.比较3种粒径组分沉积物中可提取腐殖质的紫外-可见、红外及三维荧光光谱的特征参数,发现Ⅰ、Ⅱ组分沉积物中可提取腐殖质的芳香度高,脂肪族和芳香族含量高于Ⅲ组分,而Ⅲ组分沉积物可提取腐殖质中酚、醇及羧酸类活性基团含量相对较高.     

崇明东滩表层沉积物中7Be活度的粒度效应

本文于2010年7月至2011年2月期间,每月于长江口区域崇明东滩的高、中、低不同潮滩采集表层沉积物样品,利用水淘选原理和沉积物分级装置进行粒度分级,获得从粗到细的A、B、C、D四种不同粒径大小（>63 μm、32~63 μm、16~32 μm以及8~16 μm）的样品组分及其相应的7Be活度。研究结果表明:粗粒级部分的含量随着离岸距离的增加而增高;细粒部分则反之。粒度由细到粗,7Be活度呈降低趋势。对分级后样品的粒径（φ单位）与7Be活度值做相关性研究发现,高、中潮滩沉积物7Be核素活度受降水影响大于低潮滩沉积物。相较于中低潮滩,位于高潮滩的14#站位,7Be活度与平均粒径的相关性最差。7Be活度和平均粒径相关性的季节性差异不甚明显。本研究结果表明,在利用7Be研究河口海岸区域中季节时间尺度颗粒悬浮物的输运和沉积过程当中,应充分考虑粒度效应的影响。     

滇池典型湖区沉积物粒径与重金属分布特征

对滇池3个代表性湖区(草海、湖心区、外海南部)表层(0~10cm)沉积物的粒径组成进行了分析,测试了不同粒径沉积物的主要理化性质和Cu、Cr、Ni、Zn、Pb、Fe、Mn、Cd等8种重金属的质量分数,并对滇池沉积物中重金属质量分数的粒径效应作了校正. 结果表明:滇池表层沉积物粒径主要分布在<250μm的范围内;粉砂(4~<63μm)所占比例最大,平均达到60%;黏土(<4μm)次之,平均占19%. 随着粒径的减小,大部分重金属质量分数在不同粒径的沉积物中呈增加趋势. 重金属在细粒径(<63μm) 沉积物中所占比例平均达79%,显著高于其他粒径(63~<125、125~<250μm). Cr、Cd、Cu、Pb、Zn和Ni具有相似的富集特性,其质量分数高值均出现在粒径为4~<63μm的沉积物中,该粒径沉积物中6种重金属的质量分数分别为土壤背景值的2.04、9.77、4.35、5.11、3.47和4.60倍;而w(Fe)和w(Mn)在各粒径沉积物中无明显差异. 黏土校正结果与不同粒径沉积物黏土校正的理论计算值相差不大. 黏土校正与参比元素校正都适合校正滇池不同粒径沉积物的重金属质量分数.      

水生腐殖酸分子量分布研究——Ⅰ.串联凝胶色谱法测定水生腐殖酸分子量分布

考察了测定水生腐殖酸分子量分布及其平均分子量的串联凝胶色谱法。结果表明,使用Sepbadex G-25和G-100两种凝胶的色谱柱系统的分离范围可从分子量1000左右到数万,几乎包括了水生腐殖酸分子量分布的整个区段。这样的串联凝胶色谱柱的标定曲线为一折线,可用分段函数近似地加以描述。     

DOM结构特征及其对17β-雌二醇光降解的影响

参照国际腐殖酸协会(IHSS)推荐的方法从滇池底泥提取出胡敏酸(HA)和富里酸(FA),以Sigma Aldrich胡敏酸(SAHA)为参照,利用元素分析、13C核磁共振和紫外-可见光谱对HA和FA的来源和结构进行了表征,并探讨了3种溶解性有机质(DOM)对17β-雌二醇(E2)光降解的影响.结果表明:HA、FA和SAHA具有相似的元素组成,3种腐殖酸的(N+O)/C值分别为0.50、0.82和0.55,与核磁共振13C谱分析的极性指数(0.32、0.42和0.33)一致.HA和FA来自于内源,具有较高的N含量和较多的缔合芳香结构,而SAHA是外源性有机质,具有更高的芳香度.低浓度的3种腐殖酸均能促进E2发生服从准一级动力学规律的光化学降解过程.E2在纯水中光降解速率为0.0071h-1,而在5mgC/L的HA、FA和SAHA作用下,E2光降解速率分别为0.0597、0.1178和0.2048h-1.3种腐殖酸促进E2光降解能力的差异主要是由含氧能团和芳香结构含量差异所致.活性氧分子探针鉴定显示HO?是腐殖酸体系受光照后产生的一种重要活性氧,其氧化降解E2的量占到了E2降解总量的70%左右.与低浓度腐殖酸相比,高浓度的3种腐殖酸均会对E2光降解产生抑制作用.     

水生腐殖酸分子量分布研究——Ⅰ.串联凝胶色谱法测定水生腐殖酸分子量分布

考察了测定水生腐殖酸分子量分布及其平均分子量的串联凝胶色谱法。结果表明,使用Sepbadex G-25和G-100两种凝胶的色谱柱系统的分离范围可从分子量1000左右到数万,几乎包括了水生腐殖酸分子量分布的整个区段。这样的串联凝胶色谱柱的标定曲线为一折线,可用分段函数近似地加以描述。     

广州地区不同粒径段大气颗粒物中水溶性有机碳的吸光贡献

对广州地区春季（2015年3~4月）、夏季（2015年6~7月）、秋季（2015年9~10月）、冬季（2015年12月~2016年1月）四个季节6个粒径段（<0.49、0.49~0.95、0.95~1.5、1.5~3.0、3.0~7.2以及7.2~10.0μm）的大气颗粒物样品中水溶性有机碳（WSOC）的浓度和光学性质等变化特征进行了研究.结果表明,WSOC的浓度水平呈现冬季[（5.07±2.80）μg/m³]>秋季[（3.87±1.51）μg/m³]>春季[（3.60±1.16）μg/m³]>夏季[（2.42±0.51）μg/m³]的季节变化特征;WSOC的质量平均直径（MMD）为0.57μm （春）、0.42μm （夏）、0.49μm （秋）和0.56μm （冬）.WSOC的质量吸收效率MAE₃₆₅差异较大,分布在0.18~1.42m²/g之间,冬季最高;吸收波长指数AAE值分布在3.6~9.8之间.细颗粒物（<3μm）中WSOC对PM₁₀WSOC总吸光的贡献达到了90%以上,其中<0.49μm颗粒物的贡献超过50%.在300~500nm之间,春季、夏季、秋季和冬季WSOC对颗粒物总吸光比例平均值分别为5.23%、2.95%、3.04%和6.92%;其中<0.49μm粒径段的贡献最高,分别为3.11%、1.79%、1.65%和3.45%.进一步通过特征紫外吸光度SUVA值的分析表明芳香性和分子量可能是影响WSOC吸光能力的重要因素.粒径越小颗粒物含有越多的不饱和键,使得MAE₃₆₅值较高.     

滇池典型陆生和水生植物溶解性有机质组分的光谱分析

应用紫外-可见光谱、傅里叶红外光谱与三维荧光光谱,对采自滇池外海及湖滨农田的2种典型陆生植物(玉米、紫茎泽兰)和5种水生植物(芦苇、水红花、水葫芦、眼子菜、茭草)所提取的DOM(溶解性有机质)组分进行了光谱分析. 结果表明,陆生与水生植物DOM的紫外-可见光谱曲线基本类似,吸光度均随波长的增加而降低. 陆生植物DOM的SUVA₂₅₄(单位溶解性有机碳浓度下波长254 nm处吸收系数)值大于水生植物,表明滇池外源输入的DOM腐殖化程度大于内源. 植物叶中DOM的A₂₅₀/A₃₆₅(A₂₅₀、A₃₆₅分别为波长250和365 nm处的紫外吸光度比值)小于茎,表明叶中DOM的芳香性和分子量都大于茎. 陆生与水生植物DOM均有相似的红外特征峰带,其中—COO-、—CH₂、—CO、—OH、—NH₂的特征峰明显,表明它们是构成陆生和水生植物DOM的主要官能团. 三维荧光光谱分析表明,陆生植物茎的DOM中含有类富里酸物质,而叶的DOM中含有类腐殖酸物质. 水生植物除了水葫芦叶的DOM中含有类腐殖酸物质外,其他样品无论茎、叶都含有类富里酸物质. 除水葫芦叶外,同种植物茎的DOM中存在类色氨酸物质,而叶中不存在.      

水环境中秸秆源溶解有机质的组成及光化学活性特征

利用紫外-可见吸收光谱、三维荧光光谱和稳态光化学反应技术,对水环境中水稻和小麦秸秆短期（91d）分解释放的溶解有机质（DOM）的组成、结构和光化学活性进行了研究.结果表明：在水环境中,秸秆分解释放DOM过程可分为物理淋溶、易分解组分分解和难分解组分分解三个阶段,其中易分解组分是该分解过程中秸秆DOM的主要来源;随分解周期增长,秸秆源DOM的芳香性、腐殖化程度及分子量不断增大,而生物可利用性逐渐减小;秸秆源DOM中的类酪氨酸、类腐殖酸和类富里酸在秸秆分解过程中逐渐累积,至分解末期,3种组分在水稻和小麦秸秆DOM中的含量分别增加了4.2%~14.3%和5.9%~12.8%,而类色氨酸和溶解性微生物分泌物相对不稳定,会被逐渐分解;秸秆源DOM的紫外和荧光光谱特征指数SUVA₂₅₄、E2/E3、S_275~295、S_R、BIX和FI均与其光生HO×、¹O₂和三线态DOM间具有良好的相关关系（r > 0.61,P < 0.05）,因此秸秆源DOM的光化学活性由其芳香结构、分子量及生物可利用性共同决定.鉴于此,研究认为,探讨生物可利用组分的光化学活性,及构建光谱特征指数预测DOM光化学活性的数学模型,是今后秸秆源DOM生态环境作用研究的两项重要内容.