Influence of Cathode Modification by Chitosan and Fe^(3+)on the Electrochemical Performance of Marine Sediment Microbial Fuel Cell

The electrochemical performances of cathode play a key role in the marine sediment microbial fuel cells(MSMFCs)as a long lasting power source to drive instruments,especially when the dissolved oxygen concentration is very low in seawater.A CTS-Fe^(3+)modified cathode is prepared here by grafting chitosan(CTS)on a carbon fiber surface and then chelating Fe^(3+)through the coordination process.The electrochemical performance in seawater and the output power of the assembled MSMFCs are both studied.The results show that the exchange current densities of CTS and the CTS-Fe^(3+)group are 5.5 and 6.2 times higher than that of the blank group,respectively.The potential of the CTS-Fe^(3+)modified cathode increases by 138 mV.The output power of the fuel cell(613.0 mW m^(-2))assembled with CTS-Fe^(3+)is 54 times larger than that of the blank group(11.4 mW m^(-2))and the current output corresponding with the maximum power output also increases by 56 times.Due to the valence conversion between Fe^(3+)and Fe^(2+)on the modified cathode,the kinetic activity of the dissolved oxygen reduction is accelerated and the depolarization capability of the cathode is enhanced,resulting higher cell power.On the basis of this study,the new cathode materials will be encouraged to design with the complex of iron ion in natural seawater as the catalysis for oxygen reduction to improve the cell power in deep sea.

Heavy metal pollution assessment in marine sediments in the Northwest coast of Sabah,Malaysia

Heavy metal contents along the Northwest coast of Sabah were determined to interpret the pollution level in the marine sediment. The metal abundance is regulated by the physico-chemical properties such as the average sediment pH(7.82, 9.00 and 8.99), organic matter(0.62%, 1.60%, and 2.27%), moisture content(25.00%, 29.70%, and 15.00%) and sandy texture in Kota Belud, Kudat and Mantanani Island,respectively. The major elements show Ca>Fe>Mg>Al>Mn for all study sites, while the heavy metals show Ni>Cr>Zn>Cu>Co>Pb, Cr>Ni>Zn>Cu>Pb>Co and Zn>Pb>Cr>Ni, for Kota Belud, Kudat and Mantanani Island, respectively. The pollution degree of heavy metals was evaluated by using the Sediment Quality Assessment(SQA). The SQA parameters indicated none to moderate pollution in Kota Belud that shows Class 0, Class 1 and Class 2 pollution. The parameters also indicated none to low pollution in Kudat and Mantanani Island that show only Class 0 pollution. The enrichment factor(EF) suggested minor to moderately severe metal enrichment by anthropogenic sources in Kota Belud, whereas only minor enrichment in Kudat and Mantanani Island. The modified pollution degree(MCD<1.5) and pollution load index(0 PLI<1) indicating only low pollution level in the marine sediments for all study sites. The objectives of this study are:(1) to determine the physico-chemical parameters of sediments,(2) interpret the heavy metal contents and(3) evaluate the sediment quality.

A simple guideline to apply excitation-emission matrix spectroscopy(EEMs)for the characterization of dissolved organic matter(DOM)in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth.Dissolved organic matter(DOM)in pore waters accumulates products and intermediates of carbon cycling in sediments.The application of excitation-emission matrix spectroscopy(EEMs)in the analysis of subseafloor DOM samples is largely unexplored due to the redox-sensitive matrix of anoxic pore water.Therefore,this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water samples from anoxic marine sediments.The parameters determined by fluorescence spectra include 3D-index derived from EEMs after parallel factor analysis(PARAFAC),fluorescence index(FI)(contribution of terrigenous DOM),biological index(BIX)and humification index(HIX)derived from 2D emission spectra.First,we investigated the impacts of extensively-presented ions as typical electron acceptors,which are utilized by anaerobic microbes and stratified in marine sediments:Fe(II),Fe(III),Mn(II)and sulfide in anoxic pore water resulted in biases of fluorescent signals.We proposed threshold concentrations of these ions when the interference on EEMs occurred.Effective removal of sulfide from sulfide-rich samples could be achieved by flushing with N_(2)for 2 min.Second,the tests based on DOM standard were further verified using pristine samples from marine sediments.There was a significant change in the fluorescence spectra of DOM in anoxic sediments from the Rhône Delta.This study demonstrated that the change was caused by oxidation of the matrix rather than the intrinsic alteration of DOM.It was confirmed by extracted DOM via both EEMs analysis and Fourier transform ion cyclotron resonance mass spectrometry(FT-ICR-MS).Slight oxidation of sulfur-containing compounds(e.g.,sulfhydryl)and polyphenol-like compounds occurred.Finally,a sample preparation sequence is proposed for pore water from anoxic sediments.This method enables measurement with small volumes of the sample(e.g.,50µL in this study)and ensures reliable data without the interference of the redox-sensitive matrix.This study provides access to the rapid analysis of DOM composition in marine sediments and can potentially open a window into examining the carbon cycling of the marine deep biosphere.

Determination of Lignin in Marine Sediment Using Alkaline Cupric Oxide Oxidation-Solid Phase Extraction-on-Column Derivatization-Gas Chromatography

Lignin serves as one of the most important molecular fossils for tracing Terrestrial Organic Matters （TOMs） in marine environment. Extraction and derivatization of lignin oxidation products （LOPs） are crucial for accurate quantification of lignin in marine sediment. Here we report a modification of the conventional alkaline cupric oxide （CuO） oxidation method, the modification consisting in a solid phase extraction （SPE） and a novel on-column derivatization being employed for better efficiency and reproducibility. In spiking blanks, recoveries with SPE for the LOPs are between 77.84% and 99.57% with relative standard deviations （RSDs） ranging from 0.57% to 8.04% （n=3）, while those with traditional liquid-liquid extraction （LLE） are from 44.52% to 86.16% With RSDs being from 0.53% to 13.14% （n=3）. Moreover, the reproducibility is greatly improved with SPE, with less solvent consumption and shorter processing time. The average efficiency of on-column derivatization for LOPs is 100.8%±0.68%, which is significantly higher than those of in-vial or in-syringe derivatization, thus resulting in still less consumption of derivatizing reagents.Lignin in the surface sediments sampled from the south of Yangtze River estuary, China, was determined with the established method. Recoveries of 72.66% to 85.99% with standard deviation less than 0.01mg/10g dry weight are obtained except for p-hydroxybenzaldehyde. The lignin content ∑8 （produced from 10g dry sediment） in the research area is between 0.231 and 0.587mg. S/V and C/V ratios （1.028 ± 0.433 and 0.192±0.066, respectively） indicate that the TOMs in this region are originated from a mixture of woody and nonwoody angiosperm plants; the high values or （Ad/Al）v suggest that the TOMs has been highly degraded.

Rare earth elements distribution in marine sediments of Malaysia coasts

In the east coast Peninsular Malaysia region,sediments are transported by several rivers from the east Malaysia into the South China Sea estuary.In the vicinity of the five river estuaries core sediments were collected in order to investigate rare earth elements(REEs) profile.Core sediments were divided into strata of between 2 to 4 cm intervals and prepared for analyzing by ICP-AES.REE concentrations of 54.3 μg/gr at 24–26 cm in EC4 increased to 114.1 μg/gr at 20–22 cm in EC5.The measured concentration of ...

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.

Geochemical analysis of marine sediments using fused glass disc by X-ray fluorescence spectrometry

A method was developed for content determination of Na, Mg, A1, Si, P,S, C1, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Nb, Zr, Y, Sr, Rb, Ba, La and Ce etc. covering 26 major, minor, and trace elements in marine sediment samples using fused glass disc by X-ray Fluorescence spectrometry. Calibration was made using marine sediment certified reference materials and the synthetic standard samples prepared by mixing several marine sediments with stream sediment and carbonate standard samples in different proportions. The matrix effect was corrected using theoretical alpha coefficients, experience coefficients and the scattered radiation as the internal standard （for the trace elements）. The accuracy of the method was evaluated by analysis of certified reference materials GBW07314, GBW07334 and GSMS6. The results are in good agreement with the certified values of the standards with RSD less than 2.60%, except for Y, Cr, Ga, Ce, La, Nb, Rb, and V with RSD less than 9.0% （n=12）.

Development of in-situ Marine Sediment Geo-Acoustic Measurement System with Real-Time and Multi Frequencies (the Second Generation)

Compared with the laboratory acoustic measurement of sediment samples, the in-situ acoustic measurement in marine sediment is considered more accurate and rehable, because it covers all of the surrounding environment factors and avoids the disturbance during the course of sampling and transporting of sediment samples. A new multi-frequency in-situ geoacoustic measurement system （MFIS^AMS） has been developed. The system can provide acoustic vdocity （compressional wave） and attenuation profiles of the uppermost 4 - 8 m sediment in the seafloor. It consists of 8 channels with 12 frequencies （multi-frequencies） and 0.5 - 2 MHz sampling rates. The data collected can be transmiuted in real-time. Associated with inclinometer and altimeter, it can provide the data for depth emendation. Acoustic velocity and attenuation data have been obtained from two in-situ experiments conducted in the Hangzhou Bay.

Application of confocal laser Raman spectroscopy on marine sediment microplastics

Marine sediment is the primary sink of microplastics and is an indicator of pollution levels.However,although there are well-developed detection methods,detection is rarely focused on lowmicrometer-sized particles,mainly due to technique limitations.In this study,a simplifi ed process omitting digestion procedures was developed to pretreat microplastics obtained from marine sediment and was coupled with micro-Raman spectroscopy to identify microplastics.Based on the overall analysis of the characteristic peak assignments,a Raman spectral reference library was constructed for 18 types of plastic.In addition,the eff ects of the measurement parameters were systematically described.Field research was then conducted to validate the developed process and investigate microplastic contamination in Huiquan Bay,Qingdao,China.This simplifi ed process could retain the original appearance of microparticles and accomplish the detection of<500μm-sized microplastics in environmental samples.Microplastics in the size range of 10-150μm accounted for 76%of all microplastics,and 56%of the total particles was particles smaller than 50μm.Polypropylene(42%)and polyethylene(20%)were predominant components of the particles.In particular,polypropylene particles smaller than 10μm were identifi ed in marine sediment.This work demonstrates that Raman spectroscopy is not only an eff ective tool for detecting environmental particles but also highly applicable for identifying particles extracted from marine sediment.

Pitfalls of acid leaching method for determining organic and inorganic carbon contents in marine sediments

Organic and inorganic carbon contents of marine sediments are important to reconstruct marine productivity,global carbon cycle, and climate change. A proper method to separate and determine organic and inorganic carbons is thus of great necessity. Although the best method is still disputable, the acid leaching method is widely used in many laboratories because of its ease-of-use and high accuracy. The results of the elemental analysis of sediment trap samples reveal that organic and inorganic carbon contents cannot be obtained using the acid leaching method, causing an infinitely amplified error when the carbon content of the decarbonated sample is 12%±1% according to a mathematical derivation. Acid fumigation and gasometric methods are used for comparison, which indicates that other methods can avoid this problem in organic carbon analysis. For the first time, this study uncovers the pitfalls of the acid leaching method, which limits the implication in practical laboratory measurement, and recommends alternative solutions of organic/inorganic carbon determination in marine sediments.

Determination of Trace Germanium in Marine Sediments by Hydride Generation-Atomic Fluorescence Spectrometry (HG-AFS)

A method for the analysis of trace germanium in marine sediments by HG-AFS has been investigated. The experimental conditions such as the acidity of reduction reaction, the amount of sodium boro-hydride, the carrier gas flow rate, etc., were tested and optimized by using a kind of orthogonal design. The detection limit of the presented method is 0.95 μg L -1 for germanium. The calibration curve shows a satisfactory line in the concentration range 0-320 μg L -1 Ge with a variation coefficient of ±2.1%.

Engineering and microstructure properties of contaminated marine sediments solidified by high content of incinerated sewage sludge ash

Management of incinerated sewage sludge ash(ISSA)and dredged contaminated marine sediments(CMSs)is a great challenge for Hong Kong and other coastal cities due to limited landfilling capacity.The present study investigates the use of high content(20%of sediment by mass)of ISSA in combination with cement/lime for solidification/stabilization(S/S)treatment of CMSs to provide a way to reuse the wastes as construction materials.The results showed that ISSA being a porous material was able to absorb a large amount of water rendering a more efficient solidification process of the marine sediment which normally had a very high water content(w80%).The S/S treatment improved the engineering properties of the sediment,but reduced the workability,especially for the lime-treated samples.Lime can be used to replace ordinary Portland cement(OPC)for better heavy metal immobilization and carbon emission reduction.The hardened sediment samples prepared with 10%of lime and 20%of ISSA could attain a strength of 1.6 MPa after 28 d of curing.In addition,leaching tests confirmed that there was no environmental risk induced by these stabilized materials.The formation of hydrated cementitious compounds including calcium silicate hydrate(CeSeH)/calcium aluminate silicate hydrate(C-A-S-H)/hydrocalumite/calcite was mainly responsible for the strength development in the ISSA/lime-treated sediments.

Source and Enrichment Mechanism of Lithium in the Triassic Argillaceous Marine Sediments from Huangjinkou, Sichuan, China

In the Triassic marine sediments, an obvious enrichment of lithium has been found. The source and enrichment mechanism of lithium is unknown. Here, we report trace and rare earth element and isotope analyses for Triassic sedimentary samples from core ZK601, recovered from the Huangjinkou anticline in the Xuanhan basin. Lithium concentrations from the Leikoupo and Jialingjiang formations are much higher than the average concentrations in the crust of eastern China and in other marine sediments. Lithium concentrations are highest at depths of 3300–3360 m(in argillaceous marine sediments), and Li is positively correlated with Rb, Ga, Zr, Nb and other trace elements. The range of δ^(7)Li values in our samples is consistent with that in other Triassic marine carbonate rocks. Lithium concentrations and isotope ratios are negatively correlated in the argillaceous dolomite samples at depths of 3300–3360 m. We compared the results in this study with trace and rare earth elements in the clay from Sichuan and Chongqing, and propose that the clay in the argillaceous marine evaporites from Huangjinkou formed via the hydrolysis of volcanic ash during Early–Middle Triassic volcanic eruptions into brine basins, during which clay adsorbed Li from the brine and formed Li-rich argillaceous dolomites. The addition and hydrolysis of volcanic ash in the evaporative brine is also related to the formation of a new type of polyhalite.

An improved method for quantitatively measuring the sequences of total organic carbon and black carbon in marine sediment cores

Understanding global carbon cycle is critical to uncover the mechanisms of global warming and remediate its adverse ef fects on human activities.Organic carbon in marine sediments is an indispensable part of the global carbon reservoir in global carbon cycling.Evaluating such a reservoir calls for quantitative studies of marine carbon burial,which closely depend on quantifying total organic carbon and black carbon in marine sediment cores and subsequently on obtaining their high-resolution temporal sequences.However,the conventional methods for detecting the contents of total organic carbon or black carbon cannot resolve the following specific difficulties,i.e.,(1)a very limited amount of each subsample versus the diverse analytical items,(2) a low and fluctuating recovery rate of total organic carbon or black carbon versus the reproducibility of carbon data,and(3)a large number of subsamples versus the rapid batch measurements.In this work,(i)adopting the customized disposable ceramic crucibles with the microporecontrolled ability,(ii)developing self-made or customized facilities for the procedures of acidification and chemothermal oxidization,and(iii)optimizing procedures and carbon-sulfur analyzer,we have built a novel Wang-Xu-Yuan method(the WXY method)for measuring the contents of total organic carbon or black carbon in marine sediment cores,which includes the procedures of pretreatment,weighing,acidification,chemothermal oxidation and quantification;and can fully meet the requirements of establishing their highresolution temporal sequences,whatever in the recovery,experimental efficiency,accuracy and reliability of the measurements,and homogeneity of samples.In particular,the usage of disposable ceramic crucibles leads to evidently simplify the experimental scenario,which further results in the very high recovery rates for total organic carbon and black carbon.This new technique may provide a significant support for revealing the mechanism of carbon burial and evaluating the capacity of marine carbon accumulation and sequestration.

Isolation and Genetic Analysis of Halophilous Bacteria from Marine Sediment Collected at Tianjin Port, China

[Objective] Marine sediment from Tianjin Port has a extremely high salinity.The bacteria which live in such habitats have evolved distinct physiological,metabolic,and morphological characteristics to survive.The objective of this study is to identify all the specific salt-tolerant characteristics and the genetic evolution of the bacteria in the sediment.[Methods] In this study,the total DNA of sediment from Tianjin Port was extracted,and 16S rDNA was used to conduct an analysis of the fauna of sediment bacteria. We also isolated sediment bacteria using beef extract-peptone media with seven different NaCl concentrations (0,0.5%,2%,5%,10%,15%,and 20%),aiming to analyze the dominant species of halophilous bacteria under different salinities.[Results] 1) With each stepwise increase of salinity from 0.5% to 20%,the total number of isolated bacterial colonies decreased.14 strains of bacteria were identified and classified by the16S rDNA sequencing analysis.Of these,four could tolerate 0~2% salinity,four could tolerate 0~5% salinity,one could tolerate 0~15% salinity,and one tolerated within the full 0~20% salinity range.Further four strains were only able to tolerate within a few narrow salinity ranges.such as 5%~10%,10%~15%,10%~20% and 15%~20%;2) The quantity of bacteria strains that can be isolated from the marine sediment decreased with the increase of salinity. Also, the Shannon wiener index and species richness index of marine sediment bacteria decreased significantly from 5% salinity.However,there were no significant differences in the species evenness index;3) When the salinity was 0~10%,the dominant species was Bacillus.When the salinity was 15%, Halomonas was the dominant species.When the salinity was 20%,there were no significant differences in the proportions of these species.[Conclusion] Our results showed that some bacteria could tolerate living conditions with high salinity,and we even found a species which can tolerate a wide range of salinities (0~20%).In further study,it would be valuable to analyze these bacteria's unique physiological and biochemical functions that allow them to adapt to environments with high salinity.It can provide theories to promote the development of microbial population resources in marine sediment and the reclaimation of salinized soil by salt tolerant microorganisms.

Optimization of Ultrasonic Extraction and Clean-up Protocol for the Determination of Polycyclic Aromatic Hydrocarbons in Marine Sediments by High-performance Liquid Chroma-tography Coupled with Fluorescence Detection

The procedures of ultrasonic extraction and clean-up were optimized for the determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. Samples were ultrasonically extracted, and the extracts were purified with a miniaturized silica gel chromatographic column and analyzed with high performance liquid chromatography (HPLC) with a fluorescence detector. Ultrasonication with methanol-dichloromethane (2:1, v/v) mixture gave higher extraction efficiency than that with dichloromethane. Among the three elution solvents used in clean-up step, dichloromethane-hexane (2:3, v/v) mixture was the most satisfactory. Under the optimized conditions, the recoveries in the range of 54.82% to 94.70% with RSDs of 3.02% to 23.22% for a spiked blank, and in the range of 61.20% to 127.08% with RSDs of 7.61% to 26.93% for a spiked matrix, were obtained for the 15 PAHs studied, while the recoveries for a NIST standard reference SRM 1941b were in the range of 50.79% to 83.78% with RSDs of 5.24% to 21.38%. The detection limits were between 0.75 ng L-1 and 10.99 ng L-1for different PAHs. A sample from the Jiaozhou Bay area was examined to test the established methods.

Characterization of iron diagenesis in marine sediments using refined iron speciation and quantized iron(Ⅲ)-oxide reactivity:a case study in the Jiaozhou Bay,China

As a case study, refined iron（Fe） speciation and quantitative characterization of the reductive reactivity of Fe（Ⅲ）oxides are combined to investigate Fe diagenetic processes in a core sediment from the eutrophic Jiaozhou Bay.The results show that a combination of the two methods can trace Fe transformation in more detail and offer nuanced information on Fe diagenesis from multiple perspectives. This methodology may be used to enhance our understanding of the complex biogeochemical cycling of Fe and sulfur in other studies. Microbial iron reduction（MIR） plays an important role in Fe（Ⅲ） reduction over the upper sediments, while a chemical reduction by reaction with dissolved sulfide is the main process at a deeper（〉 12 cm） layer. The most bioavailable amorphous Fe（Ⅲ） oxides [Fe（Ⅲ）am] are the main source of the MIR, followed by poorly crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）pc）]and magnetite. Well crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）wc] have barely participated in Fe diagenesis. The importance of the MIR over the upper layer may be a combined result of the high availability of highly reactive Fe oxides and low availability of labile organic matter, and the latter is also the ultimate factor limiting sulfate reduction and sulfide accumulation in the sediments. Microbially reducible Fe（Ⅲ） [MR-Fe（Ⅲ）], which is quantified by kinetics of Fe（II）-oxide reduction, mainly consists of the most reactive Fe（Ⅲ）am and less reactive Fe（Ⅲ）pc. The bulk reactivity of the MR-Fe（Ⅲ） pool is equivalent to aged ferrihydrite, and shows down-core decrease due to preferential reduction of highly reactive phases of Fe oxides.

Application of Strontium Isotopic Stratigraphy to Dating Marine Sedimentary Units:A Case Study from the Permian Stratotype Section in Southern China

The calibration of sedimentary rock absolute dates is one of the difficulties in sedimentological and stratigraphic research.Since strontium(Sr)resides in seawater much longer(≈10^(6) a)than the seawater intermixing time(≈10^(3) a),the Sr isotopic composition of global seawater is uniform at any time and results in a stable system throughout geological history,based on which a global Sr isotope composition dating database has been established for age-calibration of marine strata.The Permian stratigraphic sections in the northern part of the Upper Yangtze block,southern China,record continuous marine sediments with clear stratigraphic boundaries and is suitable for stratigraphic dating of Sr isotopes.Based on sampling and Sr isotopic compositions of Permian carbonate strata in the northern part of the Upper Yangtze,a Permian Sr isotope evolution curve was established.According to the basic principles of Sr isotope stratigraphy,the global Strontium isotope age database can be used to calibrate the Permian stratigraphic dates in the northern Upper Yangtze.The results show that the Sr isotope evolution curves for the marine carbonate rocks in the Permian stratigraphic section of the Upper Yangtze present a decreasing trend from the mid-Qixia stage(P_(2))to the mid-Wujiaping stage(P_(3)),and then rise from the middle Wujiaping stage to the end of Changxing stage(P_(3)).When the Permian Sr-isotope evolution curve is compared with the global Sr isotope evolution curve in the northern Upper Yangtze,the two are consistent in their long-term evolutionary trend,indicating that Permian global geological events are important controlling factors for the composition and evolution of Sr isotopes.The 87 Sr/86 Sr value decreased gradually in the background of large-scale regressions at the turn of middle to late Permian period,revealing that the Emeishan basalt eruption occurred near the Maokou/Wujiaping boundary(GLB).Srisotope stratigraphy dating was performed on the boundaries of the Qixia Formation/Maokou Formation,Maokou Formation/Wujiaping Formation(GLB),Wujiaping Formation/Changxing Formation(WCB)and the Permian/Triassic(PTB)using the Global Strontium Isotope Age Database.The results are 270.4 Ma,261.2 Ma,254.5 Ma and 249.7 Ma,respectively.Based on this,the eruption age of the Emeishan basalts is defined at about 261.2 Ma.,which is more coincident with that acquired from other previous dating methods on the eruption age of the Emeishan basalts,and therefore proves that the application of Sr isotopic stratigraphy to dating marine sedimentary units is an effective method.

Decomposition of algal lipids in clay-enriched marine sediment under oxic and anoxic conditions

A series of laboratory incubation experiments were conducted to examine the decomposition of algal organic matter in clay-enriched marine sediment under oxic and anoxic conditions. During the 245-day incubation period, changes in the concentrations of TOC, major algal fatty acid components （14：0, 16：0, 16：1, 18：1 and 20：5）, and n-alkanes （C16-C23） were quantified in the samples. Our results indicate that the organic matters were degraded more rapidly in oxic than anoxic conditions. Adsorption of fatty acids onto clay minerals was a rapid and reversible process. Using a simple G model, we calculated the decomposition rate constants for TOC, n-alkanes and fatty acids which ranged from 0.017-0.024 d^-1, 0.049-0.103 d^-1 and 0.011 to 0.069 d-l, respectively. Algal organic matter degraded in two stages characterized by a fast and a slow degradation processes. The addition of clay minerals montmorillonite and kaolinite to the sediments showed significant influence affecting the decomposition processes of algal TOC and fatty acids by adsorption and incorporation of the compounds with clay particles. Adsorption/association of fatty acids by clay minerals was rapid but appeared to be a slow reversible process. In addition to the sediment redox and clay influence, the structure of the compounds also played important roles in affecting their degradation dynamic in sediments.

Impact of Phenanthrene on Denitrification Activity and Transcription of Related Functional Genes in Estuarine and Marine Sediments

The effects of phenanthrene(Phe)on the denitrification activity and denitrifying genes(narG,nirS and nosZ)were evaluated by dose-response experiments in sediments of Dagu River Estuary(DRE)and Jiaozhou Bay(JZB).The results showed that potential denitrification activity(PDA),N2O,NO3−and NO2−reduction rates of both areas were inhibited with an increase of Phe concentrations.The PDA,N2O,NO3−and NO2−reduction rates of both areas was highest and lowest in the control(DRE:0.453,0.427,7.439 and 3.222mgNkg−1 h−1,JZB:0.592,0.555,8.470 and 3.793mgNkg−1 h−1)and highest Phe amended treatments(DRE:0.069,0.001,4.486,and 1.563 mgNkg−1 h−1;JZB:0.114,0.024,5.527 and 2.200 mgNkg−1 h−1).The inhibition rate of PDA was highest,follow by NO2−reduction and then NO3−reduction.Moreover,with the increasing of Phe concentrations,total bacteria count and the abundance of denitrifying genes were decreased.And N2O accumulation was promoted with the addition of Phe for both areas.Based on the comparison of EC50 values,denitrifiers harboring three genes were more sensitive to Phe than PDA,and denitrifiers harboring nirS gene were more sensitive,followed by nosZ gene,and then narG gene.Furthermore,according to correlation analysis,the relative abundance of denitrifying genes was much more positively correlated with PDA,NO3−and NO2−reduction than total bacteria count.In addition,the denitrification activity and total bacteria count in JZB were more inhibited than that of DRE.This study is useful for understanding the impact of Phe pollution on denitrification in estuary and marine sediments,with profound implications for the management of aquatic ecosystems regarding eutrophication(N-removal)and greenhouse effect.