氧化与还原条件下伊通河长春区段沉积物重金属形态特征的对比研究

利用改进的Tessier连续萃取法研究了伊通河长春市自由大桥处不同深度沉积物样品在氧化及还原条件下Cu,Pb,Zn和Ni的形态变化规律,同时分析了沉积物样品中酸可挥发性硫(Acidvolatilesulfide,AVS)和同时提取重金属(Simultaneousextractmetals,SEM)的含量.实验结果表明,样品经干燥、研磨处理后,Cu有机/硫化物结合态比例减少40%,锰氧化物结合态的比例显著增加;Pb,Zn和Ni3种元素有机/硫化物结合态比例均略有下降,变化幅度小于Cu,并重新分配到不同的化学相中.通过SEM中各金属含量与有机/硫化物结合态中金属含量的对比可知,还原性沉积物中Cu除了与硫化物结合外,很大一部分是以有机物形态存在的,Pb,Zn,Ni,Fe和Mn则主要以硫化物形态存在,各元素形态分析均不同程度地受到萃取剂的影响.

城市内河强还原性沉积物耗氧及相关因素研究

2009年7—8月间选择浙江省宁波市4条污染程度不同的内河,采集沉积物和水质样品.采用自制的多管、多电极沉积物耗氧研究装置测得沉积物耗氧(SOD)值高达13.8～9.4×104 mg/(m2.h),其中张桂河路林市场段(ST2站)SOD为87.0mg/(kg.h);同时测定了各站水质、沉积物理化指标.结果表明:水体水温和沉积物w(氨氮)与SOD有较高的相关性,而有机质、底层ρ(DO)和ρ(CODCr)与SOD的相关性较差.表观污染严重的站位其沉积物表现出强烈的"瞬时耗氧"现象,这很可能是造成水体缺氧的主要原因之一.

Phosphorus in Interstitial Water Induced by Redox Potential in Sediment of Dianchi Lake,China

The sediment redox potential was raised in the laboratory to estimate reduction of internal available phosphorus loads,such as soluble reactive phosphorus(SRP)and total phosphorus(TP),as well as the main elements of sediment extracts in Dianchi Lake.Several strongly reducing substances in sediments,which mainly originated from anaerobic decomposition of primary producer residues,were responsible for the lower redox potential.In a range of -400 to 200 mV raising the redox potential of sediments decreased TP and SRP in interstitial water.Redox potentials exceeding 320 mV caused increases in TP,whereas SRP maintained a relatively constant minimum level.The concentrations of Al,Fe, Ca^(2+),Mg^(2+),K^+,Na^+ and S in interstitial water were also related to the redox potential of sediments,suggesting that the mechanism for redox potential to regulate the concentration of phosphorus in interstitial water was complex.

Molecular Characterization of Sulfate-Reducing Bacteria Community in Surface Sediments from the Adjacent Area of Changjiang Estuary

Sulfate-reducing bacteria(SRB),which obtain energy from dissimilatory sulfate reduction,play a vital role in the carbon and sulfur cycles.The dissimilatory sulfite reductase(Dsr),catalyzing the last step in the sulfate reduction pathway,has been found in all known SRB that have been tested so far.In this study,the diversity of SRB was investigated in the surface sediments from the adjacent area of Changjiang Estuary by PCR amplification,cloning and sequencing of the dissimilatory sulfite reductase beta subunit gene(dsr B).Based on dsr B clone libraries constructed in this study,diversified SRB were found,represented by 173 unique OTUs.Certain cloned sequences were associated with Desulfobacteraceae,Desulfobulbaceae,and a large fraction(60%) of novel sequences that have deeply branched groups in the dsr B tree,indicating that novel SRB inhabit the surface sediments.In addition,correlations of the SRB assemblages with environmental factors were analyzed by the linear model-based redundancy analysis(RDA).The result revealed that temperature,salinity and the content of TOC were most closely correlated with the SRB communities.More information on SRB community was obtained by applying the utility of Uni Frac to published dsr B gene sequences from this study and other 9 different kinds of marine environments.The results demonstrated that there were highly similar SRB genotypes in the marine and estuarine sediments,and that geographic positions and environmental factors influenced the SRB community distribution.

Impact of redox-stratification on the diversity and distribution of bacterial communities in sandy reef sediments in a microcosm

Relationships between microbial communities and geochemical environments are important in marine microbial ecology and biogeochemistry. Although biogeochemical redox stratification has been well documented in marine sediments, its impact on microbial communities remains largely unknown. In this study, we applied denaturing gradient gel electrophoresis （DGGE） and clone library construction to investigate the diversity and stratification of bacterial communities in redox-stratified sandy reef sediments in a microcosm. A total of 88 Operational Taxonomic Units （OTU） were identified from 16S rRNA clone libraries constructed from sandy reef sediments in a laboratory microcosm. They were members of nine phyla and three candidate divisions, including Proteobacteria （Alphas, Beta-, Gamma-, Delta-, and Epsilonproteobacteria）, Aetinobacteria, Acidobacteria, Bacteroidetes, Chloroflexi, Cyanobacteria, Firmicutes, Verrucomicrobia, Spirochaetes, and the candidate divisions WS3, SO31 and AO19. The vast majority of these phylotypes are related to clone sequences from other marine sediments, but OTUs of Epsilonproteobacteria and WS3 are reported for the first time from permeable marine sediments. Several other OTUs are potential new bacterial phylotypes because of their low similarity with reference sequences. Results from the 16S rRNA, gene clone sequence analyses suggested that bacterial communities exhibit clear stratification across large redox gradients in these sediments, with the highest diversity found in the anoxic layer （15-25 mm） and the least diversity in the suboxic layer （3-5 mm）. Analysis of the nosZ, and amoA gene libraries also indicated the stratification of denitrifiers and nitrifiers, with their highest diversity being in the anoxic and oxic sediment layers, respectively. These results indicated that redox-stratification can affect the distribution of bacterial communities in sandy reef sediments.

Redox conditions in sediments and during sedimentation in the Ontong Java Plateau,west equatorial Pacific

Redox-sensitive elements in sediments, such as manganese （Mn）, vanadium （V）, molybdenum （Mo）, and uranium （U）, are promising indicators of past redox conditions during sedimentation and early diagenesis. However, in the Ontong Java Plateau, west equatorial Pacific, there are sparse datasets of redox-sensitive elements in sediment cores. Here, we present a 250 ka record of redox sensitive elements from a 460 cm gravity core at site WP7 （3~56＇S, 156^.E, water depth 1 800 m）, which was recovered from the southwest Ontong Java Plateau during the 1993 cruise of R/V Science I of the Institute of Oceanology, Chinese Academy of Sciences （IOCAS）. Relative to the Post-Archean Australian Shale （PAAS）, authigenic Mn, cobalt （Co）, nickel （Ni）, Mo, V, U, and cadmium （Cd） were found at constantly low levels except when peaks occurred at several depth intervals. Manganese, Co, Ni, and Mo concentrations were elevated at 25-35 cm due to Mn redox cycling. The core was divided into three distinct sections, the top 0-25 cm being oxic, a suboxic section at 25-35 cm and from 35-460 cm which was anoxic. Differential authigenic enrichments of Co, Ni, Mo, V, U, and Cd at the same depth intervals were observed indicating that the enrichments happened during sedimentation or diagenesis and suffered no post settlement redox changes. Therefore, no significant changes in redox conditions during sedimentation must have happened. The water at depth on the Ontong Java Plateau during past 250 ka must have been well oxygenated, possibly resulted from the more or less continuous presence of oxygen-rich deep water like the modem Antarctic Intermediate Water （AAIW） and Antarctic Circumpolar Water （ACW）; while it＇s slightly less oxygenated in glacial intervals, possibly due to ventilation weakening and/or the surface productivity increase.

Diagenetic control of magnetic susceptibility variation in Core MD98-2172 from the Eastern Timor Sea

Detailed mineral magnetic measurements, integrated with grain-size distribution and X-ray diffraction （XRD） analyses, were made on the marine sediments of Core MD98-2172, retrieved from the Eastern Timor Sea. Values of magnetic susceptibility in this core drop sharply down-core from -3.85 m deep below sediment/water interface and are very low at -5.35 m. However, both XRD and grain-size distribution results show no sudden change in terrigenous input during sedimentation. Mineral magnetic results indicate that the depth of -3.85 m may be an oxic/anoxic boundary. Therefore, the sediments below -3.85 m have been subjected to intense reductive diagenesis, whereas the sediments above -3.85 m are seldom affected. The magnetic properties of the sediments shallower than 3.85 m are dominated by pseudo-single domain （PSD） magnetite, with little down-core variation in its content and grain size. Below -3.85 m, the magnetic mineral assemblages that have survived in the sediments may record different stages of the reductive diagenesis： （1） the sediments from the 3.85-5.35 m interval are at the stage of iron oxide reduction; t＇SD magnetite is the major magnetic contributor, but it becomes less abundant and coarser down-core; （2） the sediments below -5.35 m are at the stage of sulphate reduction; ferrimagnetie minerals almost vanish and paramagnetic minerals contribute to down-core susceptibility variations, including pyrite as evidenced by high-temperature magnetic susceptibility measurements. However, the susceptibility variations below -5.35 m of Core MD98-2172 show obvious periodicity, despite the intense effect of reduetive diagenesis. Furthermore, the down-core susceptibility variations are coincident with fluctuations in the quantity of fine detrital particles （〈8 μm）, which may come mainly from the advection of the Indonesia Throughflow （ITF） and/or river input from Timor. Therefore, for Core MD98-2172, susceptibility variation below -5.35 m, which potentially correspond to fluctuations in the quantity of fine particles, may record the histories of the development of the ITF and precipitation on Timor.

Superior Au-adsorption performance of aminothiourea-modified waste cellulosic biomass

Waste cellulosic biomass obtains various applications due to low-cost and eco-benign characteristics.A general strategy is proposed for waste cellulosic biomass to be modified with dialdehyde functional groups as intermediates through periodate partial oxidation.Finally,aminothiourea-modified waste cellulosic biomass can be prepared through Schiff reaction.Waste corn stalk,cotton and paper as typical precursors,were used to prepare cellulosic biomass,abbreviated as AT-S,AT-C and AT-P,respectively,and their adsorption behaviors of Au(III)from the hydrochloric acid medium were investigated.The pseudo-second kinetics equation as well as the Langmuir isotherm equation can be used to depict the adsorption process,and the maximum adsorption capacities of Au(III)are21.4,19.0and3.28mol/kg for AT-S,AT-C and AT-P at298K,respectively.The adsorption capacities of Au(III)on aminothiourea modified corn stalk(AT-S)is almost357times greater than that of raw corn stalk.To the best of our knowledge,AT-S has the highest adsorption capacity towards Au(III).AT-S also displays a superior separation selectivity towards Au(III)in the presence of Cu(II),Ni(II),Co(II),Pt(VI),Pd(II)and Rh(III).Furthermore,the characterization analysis of XRD,TG,SEM,TEM and FTIR confirms that AuCl4– has been reduced to elemental Au nanoparticles and deposit onto the surface of the biomass.It shows a prospect for waste corn stalk to be used to adsorb Au(III)from liquid phase and the possible fabrication of gold nanoparticles by a general adsorption process without any reductant.

Cathodic Hydrogen as Electron Donor in Enhanced Reductive Dechlorination

In situ capping is an attractive and cost-effective method for remediation of contaminated sediments,but few studies on enhancing contaminant degradation in sediment caps have been reported,especially for chlorinated benzenes.Electrically enhanced bioactive barrier is a new process for in situ remediation for reducible compounds in soil or sediments.The primary objective of this study is to determine if electrodes in sediment could create a redox gradient and provide electron acceptor/donor to stimulate degradation of chlorinated contaminant.The results demonstrate that graphite electrodes lead to sustainable evolution of hydrogen,displaying zero-order kinetics in the initial stages with different voltages.The constant rates of hydrogen evolution at 3,4,and 5 V are1.05,2.54,and 4.3 nmol·L 1·d 1,respectively.Even higher voltage can produce more hydrogen,but it could not keep long time because the over potentials on electrode surfaces prevent its function.The study shows that 4 V is more appropriate for hydrogen evolution.The measured and evaluated concentration of 1,2,3,5-tetrachlorobenzene in pore water of sediment and concentration of sulfate show that dechlorination is inhibited at higher concentration of sulfate.

Corrosion behavior of B10 copper-nickel alloy beneath a deposit caused by sulfate-reducing bacteria with carbon source starvation in marine environments

Copper-nickel alloys can suffer severe localized corrosion in marine environments containing sulfate-reducing bacteria(SRB),but the effect of SRB on the under-deposit corrosion of copper-nickel alloys is unknown.In this work,the corrosion behavior of B10 copper-nickel alloy beneath a deposit caused by SRB with carbon source starvation in artificial seawater was studied based on electrochemical measurements and surface analysis.Results demonstrate that SRB with an organic carbon starvation can survive in artificial water but most SRB cells have died.The survived SRB cells can attach to the bare and deposit-covered B10 copper-nickel alloy,leading to the corrosion acceleration.Due to the limitation of organic carbon source,the pitting corrosion of B10 copper-nickel alloy caused by SRB is not serious.However,serious pitting corrosion of the deposit-covered B10 copper-nickel alloy can be found both in abiotic and biotic conditions,and the pitting corrosion and uniform corrosion are further accelerated by SRB.There is a galvanic effect between the bare and deposit-covered specimens in the presence of SRB in the early stage but the galvanic effect after 5 d of testing can be neglected due to the low OCP difference values.

Quantifying the sources of dissolved inorganic carbon within the sulfate-methane transition zone in nearshore sediments of Qi'ao Island, Pearl River Estuary, Southern China

The significance of the various biogeochemical pathways that drive carbon cycling and the relative fractions of dissolved inorganic carbon(DIC) produced by these reactions within the sulfate-methane transition zone(SMTZ) are still being debated. Unraveling these processes is important to our understanding of the benthic DIC sources and their contributions to the global carbon cycle. Here, we measure pore water geochemistry(chlorine, sulfate, methane, Ca^(2+), Mg^(2+), DIC and δ^(13)C-DIC) as well as solid geochemistry(sedimentary organic carbon(SOC) and δ^(13)C of SOC) in nearshore sediments from Qi'ao Island in the Pearl River Estuary of the Southern China Sea. Our analysis indicates that SOC originates from the mixing of carbon from terrestrial and marine sources, and that terrestrial materials dominate the net loss of SOC during the degradation of organic matter, especially at sites located near the river outlets. Sulfate reduction via SOC degradation is not appreciable in the upper sediment layer due to conservative mixing-dilution by freshwater. However, below this layer, the anaerobic oxidation of methane(AOM) and methanogenesis occur. Within the SMTZ, the δ^(13)C mass balance shows that the proportions of DIC derived from organoclastic SO_4^(2-) reduction(OSR) and AOM are 50.3% to 66.7% and 0.1% to 17.9%, respectively, whereas methanogenesis contributes 17.0% to 43.9%. This study reveals that the upward diffusion of DIC from ongoing methanogenesis significantly influences carbon cycling within the SMTZ in these estuarine sediments. As a result, we suggest that the plots of the ratio of change in sulfate to change in DIC in pore water should be used with caution when discriminating between sulfate reduction pathways in methane-rich sediments.

Mo marine geochemistry and reconstruction of ancient ocean redox states

Molybdenum(Mo) proxies, including bulk concentration and isotopic composition, have been increasingly used to reconstruct ancient ocean redox states. This study systematically reviews Mo cycles and their accompanying isotopic fractionations in modern ocean as well as their application in paleo-ocean redox reconstruction. Our review indicates that Mo enrichment in sediments mainly records the adsorption of Fe-Mn oxides/hydroxides and chemical bonding of H2 S. Thus, Mo enrichment in anoxic sediments generally reflects the presence of H2 S in the water column or pore waters. In addition to the effect of euxinia, sedimentary Mo enrichment is related to the size of the oceanic Mo reservoir. Given these primary mechanisms for oceanic Mo cycling, Mo abundance data and Mo/TOC ratios acquired from euxinic sediments in geological times show that fluctuations of the oceanic Mo reservoir are well correlated with oxygenation of the atmosphere and oceans and suggest that oxygenation occurred in phases. Mo proxies suggest that Mo isotopes in strongly euxinic sediments reflect the contemporaneous Mo isotopic composition of seawater, but other processes such as iron-manganese(Fe-Mn) adsorption and weak euxinia can result in different fractionations. Diagenesis may complicate Mo enrichment and its isotopic fractionation in sediments. With appropriate constraints on the Mo isotopic composition of seawater and various outputs, a Mo isotope mass-balance model can quantitatively reconstruct global redox conditions over geological history. In summary, Mo proxies can be effectively used to reconstruct oceanic redox conditions on various timescales due to their sensitivity to both local and global marine redox conditions. However, given the complexity of geochemical processes, particularly the effects of diagenesis, further work is required to apply Mo proxies to ancient oceans.