A comparison of non-hydrolytic methods for extracting amino acids and proteins from coastal marine sediments

Advances in analytical techniques now allow for the potential analysis of intact peptides and proteins isolated from marine sediments. However, there is no established technique for the extraction of macromolecular materials from marine sediments. Six different methods for extracting the amino acid component from coastal marine sediments were compared to the standard hot acid hydrolysis technique for their percent recovery and amino acid composition. The standard hot acid hydrolysis on dried, whole sediments released the greatest concentration of total amino acids (PS-THAA; 3.52 mg gdwt^− 1 ± 10% (SMD)), yet this only accounted for 22% of the total nitrogen in Puget Sound sediments (Washington, USA). Repeated hydrolysis of the same samples did not improve the recovery of nitrogen by more than an additional 10%. Base extraction (0.5 N NaOH) was the second best method for recovering amino acid nitrogen, releasing 60% of the Puget Sound total hydrolyzable amino acids (PS-THAA) (corresponding to 13% of the total sedimentary nitrogen), and has the advantage that it does not rely on peptide hydrolysis to free the nitrogenous component from the sediment matrix. The amino acid distribution of the 0.5 N NaOH extract was not significantly different than the initial THAA. Other non-hydrolyzing methods released lower yields of amino acids (Triton X-100 ≥ hot water > 50 mM NH₄HCO₃ > HF), but might prove to be of use to investigators interested in specific fractions of sedimentary organic nitrogen because these four methods had distinctly different amino acid compositions (enrichments in basic amino acids and depletions in acidic amino acids). Treatments with HF both before and after traditional hydrolysis and/or extractions with base did not release any more of the sedimentary nitrogen. Our results are consistent with the hypothesis that a large fraction of the sedimentary nitrogen (TN) is protected within an organic matrix.     

Non-linear analysis of undrained cyclic strength of soft marine clay

Iwan models are used to simulate the non-linear and hysteretic behaviour of soils under cyclic loading conditions. However, the model in its original form cannot take into account the stiffness degradation which is observed during cyclic loading of soft clays. Studies show that the stiffness reduction (expressed as degradation index) can be represented as a function of the number of cycles and of a degradation parameter depending on the strain amplitude in the case of strain controlled cyclic loading tests. This degradation index has been incorporated into Iwan's series–parallel model as a single fatigue parameter to account for the degradation during cyclic loading. The comparisons made with the existing results of two marine clays tested under undrained cyclic triaxial and simple shear conditions provided an opportunity to understand the capability of the one dimensional model.     

Adsorption–desorption reactions and bioturbation transport of Ra in marine sediments: a one-dimensional model with applications

The distribution of trace metals in sediments and their exchange between sediments and overlying water is governed by multiple processes including molecular diffusion, bioturbation (porewater advection, porewater mixing, and particle mixing), chemical reactions and adsorption–desorption. To understand these processes and their relative contributions, a one-dimensional model was built, which includes bioturbation and adsorption–desorption processes, to describe the transport of ²²⁴Ra. Because ²²⁴Ra is adsorbed on MnO₂, ²²⁴Ra may serve as a proxy for trace metal transport. Three sites were sampled and both dissolved and adsorbed ²²⁴Ra were analyzed and modeled to understand the transport and exchange processes. It was found that particle transport of adsorbed ²²⁴Ra followed by desorption at the sediment/water interface typically represents the dominant flux. We have further been able to define conditions where the porewater transport for adsorption reactive metals like ²²⁴Ra (and other metals) may be out of the sediments whereas the active scavenging of ²²⁴Ra from the water column at the sediment water interface via adsorption reactions can result in a flux of ²²⁴Ra into the sediment. These processes are both predicted by the model and observed in sediment samples.     

Oxygen isotopes of phosphatic compounds—Application for marine particulate matter, sediments and soils

The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (δ¹⁸O_p) can be used as a tracer for phosphate sources and to evaluate the cycling of phosphorus (P) in the environment. However, phosphatic compounds must be converted to silver phosphate prior to isotopic analysis, a process that involves digestion of particulate matter in acid. This digestion will hydrolyze some of the phosphatic compounds such that oxygen from the acid solution will be incorporated into the sample as these phosphatic compounds are converted to orthophosphate (PO₄³⁻). To determine the extent of incorporation of reagent oxygen into the sample, we digested various phosphatic compounds in both acid amended with H₂¹⁸O (spiked) and unspiked acid and then converted the samples to silver phosphate for δ¹⁸O_p analysis. Our results indicate that there is no isotopic fractionation associated with acid digestion at 50 °C. Furthermore, we found that reagent oxygen incorporation is a function of the oxygen to phosphorus ratio (O:P) of the digested compound whereby the percentage of reagent oxygen incorporated into the sample is the same as that which is required to convert all of the P-compounds into orthophosphate. Based on these results, we developed a correction for reagent oxygen incorporation using simple mass balance, a procedure that allows for the determination of the δ¹⁸O_p of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for δ¹⁸O_p to demonstrate the utility of this approach for understanding sources and cycling of P.     

Distribution and dispersal pattern of clay minerals in surface sediments, eastern Beibu Gulf, South China Sea

Clay minerology of sediments are useful in determining distribution,sources and dispersal routes of fine-grained sediments.In the present paper,clay minerals of surface sediments throughout the eastern part of Beibu Gulf has been investigated to reveal sources and transport of detrital finegrained sediments.Four distinct clay mineral suites were observed from cluster analysis of clay mineral compositions of the samples.From the distribution pattern of clay minerals,we conclude that kaolinte in the eastern gulf is mainly derived from South China Landmass;Smectite could not be transported mainly by surface current from north-western Hainan Island,and maybe minor portion of it from Red River;Illite is mainly transported by the currents from South China Sea.Chlorite has two sources,namely South China Sea and South China Landmass.The Zhujiang River derived sediments could not be one of the sources for the clay mineral here,because of very different composition and ratios.The distribution pattern of clay minerals in the eastern Beibu Gulf is mainly controlled by fine-grained sediment source and local currents.The Silt/Clay,Smectite/Kaolinte,and Smetite/(Chlorite+Illite) ratios could be used as indicators of fine-grained sediment dispersal in the gulf.     

The physical model with temperature and pressure controlled for measuring acoustic velocity of marine sediments

Abstract

The superficial marine sediment is an important boundary of ocean acoustic propagation. So, the acoustic property of seafloor surface is always research hotspot. The acoustic property of sediment is affected by temperature and pressure which is not considered by conventional lab acoustic measurement. A new type of system, called “Small-scale Geo-acoustic Physical Model Pilot System” (SGPMP) has been developed. The system measures geo-acoustic property of sediment under specific temperature, pressure and frequency conditions which can be controlled conveniently and accurately. The components, structure, measurement principle, error analysis and application example of this system are introduced in this article. As a laboratory platform, the system makes it convenient for us to study the relationship between the temperature, pressure, frequency and acoustic properties of marine sediment.     

南海西北部表层沉积物黏土矿物分布特征及其来源

黏土矿物研究在示踪物源、源区风化历史乃至洋流变迁能力等方面具有重要的作用,尽管目前对南海表层沉积物黏土矿物宏观分布特征已获得了较系统的认识,但在受珠江和海南岛物源共同影响的南海西北部其高分辨率的黏土矿物学工作还未开展。本文对南海西北部表层沉积物中的黏土矿物组成、结晶学特征进行了分析,讨论了研究区黏土矿物的物质来源。结果表明,南海西北部表层沉积物的黏土矿物组成以伊利石为主（平均45%）,蒙脱石（平均27%）与高岭石（平均21%）次之,绿泥石含量最少（平均6%）。在区域空间分布上,蒙脱石含量呈现西南高东北低的特征,伊利石含量则与之相反;高岭石含量表现为近岸高离岸低,而绿泥石含量呈现离岸高近岸低的特征。总体上,研究区表层沉积物黏土矿物组成与现代珠江沉积物组成差异较大,而与珠江口2.5 ka前的沉积物黏土矿物组成比较接近,并且结合研究区岩心揭露的全新世以来极低的沉积速率（4 cm/ka）以及上部很薄（小于0.6 m）的泥质沉积,推测该区表层沉积物可能并非是现代沉积的结果,更可能主要来自全新世末期古珠江输送的沉积物。除古珠江作为研究区表层沉积物中蒙脱石的一个主要来源外,海南岛北部河流也贡献了少量蒙脱石到其邻近的东南海域。运用高岭石/伊利石比值和伊利石化学指数等进一步对比分析表明,珠江是研究区沉积物中伊利石、高岭石和绿泥石的主要物源,其次台湾和海南岛也可能分别提供了少量富含伊利石/绿泥石和高岭石的沉积物。本工作对于南海西北部沉积物源-汇过程和相应的古环境研究有重要的参考意义。     

Characterization of minerals and organic phosphorus species in marine sediments using soft X-ray fluorescence spectromicroscopy

Phosphorus Near Edge X-ray Fluorescence Spectroscopy (P-NEXFS) data were collected on phosphorus containing phases including organic and inorganic compounds and minerals. Although phases containing P in the plus five oxidation state P(V) in a tetrahedral PO₄ structure have similar primary fluorescence peak positions, the size, shape, and positions of secondary spectral features are diagnostic for different compounds and minerals. In particular, calcium phosphates exhibited a notable post-peak shoulder at 2154.5 eV, while oxidized iron phosphates had a distinctive pre-peak feature at 2148 eV. Polyphosphates have a broad secondary peak located approximately 2 eV higher in energy than a similar feature in phosphate esters and diesters. Compounds containing P(V) in structures other than PO₄ tetrahedra such as phosphonates have a primary peak shifted about 1 eV lower than corresponding organo-phosphates. Organo-phosphates with P in the plus three oxidation state P(III) such as phosphines had primary fluorescence peaks shifted still further down in energy (2–3 eV). The substitution of aromatic carbon groups in close proximity to P structures in organic compounds generated both pre- and post-peak features as well as a number of secondary peaks. In addition, X-ray fluorescence mapping of P, Si, Al, Mg, and Na was conducted on a marine sediment sample with sub-micron spatial resolution. Phosphorus was heterogeneously distributed in the sample and not correlated on a broad scale with any other element examined. Much of the P present in the sample was located in small, 0.6–8 μm size, P-rich domains. Several P-rich regions were examined with P-NEXFS using a focused beam with 60 nm resolution and were found to consist of either calcium phosphate or polyphosphate phases. The presence of significant polyphosphate-dominated regions in a marine sediment sample supports the recent observations that such phases can play an important role in marine P cycling. The combination of fluorescence mapping and P-NEXFS data collection on fine particles provides a powerful new tool for environmental phosphorus studies.     

海洋沉积物黏土矿物相对含量不同计算方法对比研究

海洋沉积物黏土矿物相对含量计算存在多种计算方法,并不统一,限制了异源黏土矿物的整合和使用。文章选取了两种较为常见的计算方法,即Biscaye和国标中规定的计算方法,分别对东印度洋109个表层样品黏土矿物的相对百分含量进行计算,分析对比了两种方法计算结果之间的差异。结果显示,两种计算方法结果存在显著正相关,都能显示黏土矿物分布的变化趋势,4种黏土矿物相关系数由高到底分别为:蒙皂石0.986、伊利石0.974、绿泥石0.924、高岭石0.923。相对于Biscaye计算方法,国标计算方法会增加伊利石和高岭石的相对百分含量而降低蒙皂石和绿泥石的相对百分含量。两种计算方法黏土矿物的含量相关性较好,可以建立起相互数学转换关系式。但在不同的海区,由于矿物成因、结晶程度以及混层矿物的出现可能会使衍射峰形态发生改变,从而相关性系数和转换关系也会相应发生改变。     

Compressibility behaviour of lime-treated marine clay

The necessity to tap natural marine resources from the ocean beds represents a considerable challenge for the construction of offshore structures on weak marine deposits. The use of lime to improve the behaviour of soft clays is not new. The present investigation examines lime-induced changes in the compressibility of marine clay. The test results indicate a reduction of 1/2 to 1/3 in the compressibility of the soil system within 30 to 45 days of treatment. The formation of various cementation compounds due to soil–lime reactions improves the soil characteristics with time. The results encourage the application of lime column and lime injection techniques to improve the engineering behaviour of soft marine clayey deposits. However, one has to be cautious in applying the lime technique to marine clays that contain sodium sulfate.     

长江口沉积物-铅的吸附动力学及环境影响

模拟研究不同水环境条件下长江口悬浮沉积时对Ｐｂ的吸附动力学,提供动力不模式,测定速率常数和分配系数。研究表明盐度和ＰＨ对吸附产生明显影响、ｋ１和ｋｄ分别与盐度存在着负指数关系;与ｐＨ存在线性关系。沉积物－Ｐｂ的吸附以化学作用为主。     

Sorption behaviour of benzyl butyl phthalate on marine sediments: Equilibrium assessments, effects of organic carbon content, temperature and salinity

Benzyl butyl phthalate (BBP) is an endocrine-disrupting chemical, and its sorption behaviour on marine sediments was investigated. BBP sorption on the sediments was a rapid process, which could reach equilibrium in 6 h. The sorption equilibrium results could be well described by a linear isotherm. The BBP partition coefficient, K_d, varied from 7.16 to 12.54 L/g in approximately proportion to the organic content of the sediments. After H₂O₂ oxidation for removing the organic material from the sediments, the K_d values were reduced by more than 70%, but the organic normalised partition coefficient averaged 2165 L/g for the H₂O₂-treated sediments, which was more than three times of 598 L/g for the raw sediments. The sorption of BBP on the sediments increased with a decrease in temperature and an increase in salinity. A salting constant of 1.14 L/mol was obtained for BBP in artificial seawater. These research findings are of importance to an assessment of the fate and transport of BBP and other similar endocrine-disrupting chemicals (EDCs) in seawater–sediment systems.     

厦门港表层沉积物对海水中铅的吸附动力学

模拟研究厦门港表层沉积物对海水中Ｐｂ的吸附动力学及水环境条件的影响,当海水温度由２０－３０℃、ＰＨ５－８和盐度３０－４变化时,吸附速率分别提高约５０％、、个数量和５倍。吸附速率与盐度之间呈负指数相关关系。吸附过程可用交换吸附动力学模式描述。测定吸附速率常数、表观活化能和平衡吸附量等参数研究表明,沉积物对Ｐｂ的吸附性质以华东作用为主。     

Permeability characteristics of lime treated marine clay

An attempt has been made to investigate the lime induced permeability changes in the permeability and engineering behavior of different lime column treated soil systems. Lime columns treated marine clay shows an increase in permeability up to a maximum value of 15–18 times that of untreated soil with time. The shear strength of the treated soil systems show an increment up to 8–10 that of untreated soil within a period of 30–45 days curing. In the case of lime injection systems, the permeability has been increased up to 10–15 times that of untreated soil, whereas the strength of the soil has been higher by 8–10 times that of untreated soil. Further, consolidation tests show a reduction in the compressibility up to 1/2–1/3 of original values. The test results revealed that both lime column and injection techniques could be used to improve the behaviour of underwater marine clay deposits.     

Scoping the effective marine environmental assessment of dredging and ocean disposal of coastal sediments in Korea

The application of scoping is reviewed to improve the efficiency and rationality of the marine environmental impact assessment system applied to the dredging of coastal sediments and the oceanic disposal of dredged material in Korea. Both the impact levels and those items requiring assessment vary in response to differing goals of the coastal activities involved and also to changes in the characteristics of different marine environments. As a consequence, different assessment fields need to be emphasized for evaluation of the impact that both dredging and dumping might have on the sites involved. The status of current assessment procedures is examined and its problems are diagnosed. Following a survey of interested parties and a review of case studies of the oceanic disposal of dredged sediment in other countries, checklists of core assessment items are proposed as part of a revamped review process, along with improvements to the assessment system.     

长江口外表层沉积物黏土矿物分布特征（英文）

依据对长江口外表层沉积物187个站位沉积物样品的黏土矿物含量分析,研究了长江口外表层沉积物黏土矿物的组合特征和分布规律。长江口外表层沉积物伊利石为优势矿物,平均含量为60.3%;次之为蒙脱石,平均为14.9%;高龄石平均含量13.5%,绿泥石平均含量为12.3%。黏土矿物的组合类型以伊利石-蒙脱石-高岭石-绿泥石型为主,伊利石-高岭石-绿泥石-蒙脱石型次之;长江口外表层沉积物黏土矿物主要为陆源成因,物质主要来源于黄河和长江的供给。Q型聚类分析显示,现代黄河物质及老黄河物质主要沉积于研究区东北部北纬29°30′以北地区,长江物质主要在研究区西部及中部区域沉积。     

Pollutants behaviour and temperature effect on chemical piles treated marine clay

Weak marine clay deposits are present in several regions of the world and they are imposing severe problems for structures founded in these deposits. The use of chemicals lime to improve the properties of these soft deposits is not new. In the present investigation, a test programme was carried out to study the influence of temperature on the engineering behaviour of chemical piles treated clays in the presence of sulphate and chloride contaminated marine environment. The formation of various cementation compounds due to soil-lime reactions were identified by X-ray diffraction studies, and the attributed changes occurred in the engineering properties of the soil systems were also brought out. The test results indicated that the increase in temperature has improved the engineering properties of soil significantly.     

大凌河与辽河入海口沉积物黏土矿物组成研究

采用X射线物相分析,对大凌河和辽河13个表层沉积物样品和4个柱状样中168个现代沉积物样品的主要黏土矿物含量组成进行分析。研究结果表明:大凌河沉积物黏土矿物组合为蒙脱石-伊利石-高岭石-绿泥石,辽河沉积物黏土矿物组合为伊利石-蒙脱石-绿泥石-高岭石。大凌河沉积物中蒙脱石与伊利石百分含量比值多大于1,而辽河沉积物该比值都小于1,且通过ISKc端元图能较清晰地区分两类沉积物,黏土矿物可以作为两条河流沉积物的判别标志。大凌河流域和辽河流域均以物理风化为主,辽河流域物理风化略强。流域内地质背景和气候条件等因素的差异造成了两条河流沉积物黏土矿物组成的不同。     

Analysis and distribution of iron sulfide minerals in recent anoxic marine sediments

Acid-volatile sulfide (AVS), pyrite-sulfur, iron and organic carbon distributions were examined in sediments from a variety of oxic and anoxic marine environments. Multiple determinations of AVS using different acid conditions showed that most extractants give similar AVS concentrations, with the exception of stannous chloride in hot HCl which digested between 10 and 81% of pyrite-sulfur.An extensive examination of iron sulfide minerals in sediments, using scanning electron microscopy combined with simultaneous elemental analysis, showed that identifiable iron sulfides were almost always pyrite. Occurrence of greigite observable by SEM was limited to one site and mackinawite was not found in any samples. Thus, if these minerals are precursors to pyrite formation, as has been frequently hypothesized, they must be primarily present as coatings on other mineral grains or submicron particles.     

沉积物中重金属的归一化问题——以Al为例

沉积物的来源、粒度和矿物组成是影响重金属在动力沉积过程中的行为的最显著的因素,用某些参考元素（如Ａｌ、Ｌｉ等）归一化的目的是为了减小沉积物中重金属含量的波动,以揭示人文活动（例如污染）的影响。通过对国内一些河流沉积物中重金属的Ａｌ归一化结果的分析,认为在岩石的风化和变质过程中元素与Ａｌ的相对迁移能力的差异和各种生物过程均可使重金属的Ａｌ归一化值产生显著的变化,在某些情况下Ｍ／Ａｌ值并不一定能准确地描述人类活动对沉积物中重金属的影响。Ａｌ归一化仅能部分地校正粒度分布引起的重金属含量的变化,但不能消除矿物组成的影响。