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1.
由于海水盐度大、有机质含量低,从海水中提取和纯化克级溶解性有机质(dissolved organic matter,DOM)一直十分困难。基于Bond Elut PPL固相萃取小柱法进行海水DOM固体样品提取的放大试验,建立DOM自动化调酸、PPL树脂吸附技术,最后形成提纯、冷冻干燥PPL-DOM(通过PPL树脂提取的DOM)完整工艺。采用元素分析、三维荧光光谱、红外光谱和固态13C核磁共振(NMR)波谱法进行样品表征。结果表明:(1)该方法对近海表层海水DOM回收率稳定在50%以上,搭建的提取装置DOM日吸附量可达230mg;(2)鳌山湾四个季节批次PPL-DOM整体分析结果表明,样品的元素组成和光谱特征相似,表明方法适用性和稳定性较好;(3)三种水生态环境的PPL-DOM13C NMR谱图显示样品的基本特征相似,以烷基碳、碳水化合物碳、芳香碳和羧基碳/酰胺碳为主,其中偶极去相(dipolar dephasing)谱显示了DOM前体化合物来源的差异。多种结果表明放大后的PPL固相萃取法可稳定提取克级DOM样品。  相似文献   

2.
《Marine Chemistry》2007,103(1-2):122-130
Phosphomolybdenum blue (PMB) paired with cetyltrimethylammonium bromide (CTAB) can be extracted using a solid phase extraction technique on C18 sorbent. Based on this, a novel on-line solid phase extraction method coupled with flow injection (FI) analysis and colorimetric detection has been established to determine nanomolar level orthophosphate in seawater. A stopped flow technique was employed to assure the complete formation of the PMB–CTAB compound, which was sequentially extracted on an in-line Sep-Pak C18 cartridge. The adsorbed PMB–CTAB can be rapidly eluted by 0.56 mol/L H2SO4 in ethanol, and determined with a spectrophotometer at 700 nm. Experimental parameters, including reaction temperature, sample loading flow rate, stopped time and eluting flow rate, were optimized throughout the experiments based on univariate experimental design. The results show that reaction temperature and stopped time were the major factors affecting the formation of PMB–CTAB. Silicate concentration up to 5000 times higher than that of orthophosphate would not interfere with the determination of orthophosphate. Using artificial seawater with salinity of 35 as a matrix under the optimized conditions, the standard curve shows a linear range between 3.2 and 48.5 nmol/L, and the recovery and the detection limit of the proposed method are 96.4% and 1.57 nmol/L, respectively. The relative standard deviation (RSD) (n = 8), which was determined daily for 8 days, was 4.52% for the artificial seawater at a concentration of 32.4 nmol/L orthophosphate. Two typical seawater samples were analyzed using both the proposed method and the MAGnesium hydroxide-Induced Coprecipitation (MAGIC) method. The results of the two methods show no significant difference using the t test. Compared to the MAGIC method, the proposed method has the advantage of being more sensitive, faster, sample saving and easy for on-line analysis.  相似文献   

3.
Association constants of orthophosphate ion with Na+, Ca2+, and Mg2+ were measured at μ = 0.68 and 20°C. The results were used to calculate phosphate speciation in seawater. Free HPO42? ion and MgHPO4o are found to be the predominant species.  相似文献   

4.
The phosphate oxygen isotopic composition in naturally occurring particulate phosphatic compounds (δ18Op) 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 δ18Op 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 δ18Op of samples containing a mixture of phosphatic compounds. We analyzed a variety of environmental samples for δ18Op to demonstrate the utility of this approach for understanding sources and cycling of P.  相似文献   

5.
For a better understanding of the phosphorus dynamics and bioavailability in temperate climates, sequential chemical extraction techniques were used to study sediment P-pools distribution and relative importance in a eutrophicated estuary.Results indicate a shift in importance from the iron-bound P fraction to the CaCO3-bound P fraction with increasing salinity, which suggests a decrease in bioavailable P from the most inner part of the estuary seaward, as the CaCO3 associated P is believed to be less available for organisms. Salt marsh plants also influence sediment P speciation, through higher organic P fractions (mainly humic acid associated P) when compared to non-vegetated sediments. The ratio of iron-bound P to iron-oxyhydroxides may be used as an indicator of P availability, since it reflects the number of available P sorption sites in the metal oxides. This ratio was lowest in the intermediate zone of the estuary (13.7) when compared to the outer site (29.6) and the upper site (26.1), suggesting saturation of sorption sites. Co-incident with this, the intermediate site is characterized by the occurrence of macroalgal blooms during summer. In the present case, superficial sediments in the Mondego estuary do not show a clear seasonal trend, either in total amounts of exchangeable P or P speciation. Pools of exchangeable P in the surface sediment were 30 times higher than the annual net-export of P (14 ton year−1) from the estuary. The annual P release from the sediment appears diminutive in comparison with the pool-size. Management measures to reduce nutrient input into coastal water systems should therefore consider that phosphorus availability may persist as a result of sediment supply, even after reducing the external point sources.  相似文献   

6.
A method for the determination of nanomolar concentrations of orthophosphate in oligotrophic seawater developed by Liang et al. (2007) has been modified to make it fully feasible for shipboard application and for faster sample throughput with minimized sample volume. The technique is based on the flow injection method with solid phase extraction on a Sep-Pak C18 cartridge and colorimetric detector. The Schlieren effect was minimized by rinsing the cartridge sequentially with 5 mL water and 2 mL 95% ethanol solution. With three micro pumps in parallel, savings of up to 80% in amount of reagents and 25% volume of seawater samples could be achieved in comparison to the previous method. Variation of stopped flow time and sample loading time gave 3 different standard curves, which corresponded to 3 linear ranges within 3.4 and 515 nM. The modified method permits the analysis of samples over a wide range of concentrations, and has been successfully applied to shipboard determination of trace orthophosphate in more than 200 seawater samples during a one-month cruise in the South China Sea. For seawater at concentrations of 20.6, 82.5, 206.2 nM orthophosphate, the relative standard deviations (RSD) (n = 6), determined daily for 6 days on board ship were 4.45%, 4.73% and 6.75%, respectively. Five seawater samples collected in the Station SEATS (South East Asia Time Series Station at 18°N, 116°E) were analyzed using the present method both on board and in a land-based laboratory, as well as with the magnesium hydroxide-induced coprecipitation (MAGIC) method, and showed no significant difference according to the statistical t-test.  相似文献   

7.
Systematic analyses have been carried out on two gas hydrate-bearing sediment core samples, HYPV4, which was preserved by CH4 gas pressurization, and HYLN7, which was preserved in liquid-nitrogen, recovered from the BPXA-DOE-USGS Mount Elbert Stratigraphic Test Well. Gas hydrate in the studied core samples was found by observation to have developed in sediment pores, and the distribution of hydrate saturation in the cores imply that gas hydrate had experienced stepwise dissociation before it was stabilized by either liquid nitrogen or pressurizing gas. The gas hydrates were determined to be structure Type I hydrate with hydration numbers of approximately 6.1 by instrumentation methods such as powder X-ray diffraction, Raman spectroscopy and solid state 13C NMR. The hydrate gas composition was predominantly methane, and isotopic analysis showed that the methane was of thermogenic origin (mean δ13C = −48.6‰ and δD = −248‰ for sample HYLN7). Isotopic analysis of methane from sample HYPV4 revealed secondary hydrate formation from the pressurizing methane gas during storage.  相似文献   

8.
《Marine Geology》2005,216(3):127-143
This study was carried out in order to understand the early diagenetic redistribution of phosphorus and relevant mass balance in the sediments of the East Sea. In two cruises during May 1993 and October 1995, 11 box cores were collected in the southwestern part of the East Sea. Dissolved phosphorus and iron were analyzed in the porewater from the cores. Sediment samples were analyzed for solid-phase P species and solid-phase Fe oxyhydroxide by sequential extraction.Phosphorus speciation results show that organic P is the major chemical form of phosphorus in young sediments within the upper 50 cm of sediment. However, the authigenic fraction of total P increases with depth, indicating the precipitation of carbonate fluorapatite (CFA) in the sediments. The authigenic CFA (Ca5(PO4)2.6(CO3)0.4F) was formed and buried at rates of 11–110 μmol cm−2 kyr−1. The main source of dissolved phosphorus for the precipitation of CFA is organic P. Dissolved phosphorus, released from the decomposition of organic P, diffuses upward to return to bottom water, or is sorbed to iron oxides in the oxidized sediments. As sedimentation proceeds, the iron oxide-bound P is released in the reduced layer and enters the dissolved phase, which contributes P to the formation of CFA in addition to that contributed by the organic P.The burial flux of reactive P (iron oxide-bound P+authigenic P+organic P) is 0.09–0.53 g P m−2 yr−1 that accounts for 18–58% of the reactive P arriving at the sediment/water interface. The burial flux of reactive P is high in the upper and lower continental margin sediment. The burial flux of reactive P in the Ulleung Basin sediment is less than those in the continental margin sites by a factor of 6, indicating that the reactive P burial flux is mainly dependent on sedimentation rate.  相似文献   

9.
We report a simplified synthesis, and some performance characteristics, for 8-hydroxyquinoline (8-HOQ) covalently bonded to a chemically resistant TosoHaas TSK vinyl polymer resin. The resin was used to concentrate trace metals from stored, acidified seawater samples collected from Jellyfish Lake, an anoxic marine lake in the Palau Islands. The Mn, Fe, and Zn profiles determined from the 8-HOQ resin extraction were similar to those determined using Chelex-100 resin. The Zn and Cd profiles did not exhibit removal by sulfide “stripping” in contrast to other anoxic marine basins. The profiles of Co and Ni also exhibited elevated concentrations in the anoxic hypolimnion. The solution speciation and saturation states for the metals were calculated using revised metal-bisulfide stability constants. The calculations suggest that the MS(HS)− species dominates the solution speciation for Mn, Co, Ni, Zn, Cd, and Pb. Cu(I) is modeled as the CuS− or Cu(HS)2− species, while Fe(II) behaves as the free Fe2+ cation. The Mn, Co, Ni, Cu and Cd concentrations appeared to be at least 10-fold undersaturated, while the Fe(II), Zn, and Pb concentrations were close to saturation with respect to their metal sulfides.  相似文献   

10.
Understanding phosphorus dynamics in marine environment is of great importance, and appropriate tracers for phosphorus cycling in oceans are invaluable. In this study, two methods were developed for extraction, purification, and determination of naturally occurring 32P and 33P in rainwater, marine plankton and sediments using both a low-level beta counter (LBC) and an ultra-low-level liquid scintillation spectrometer (LSS). Blanks, chemical yields and counting efficiencies were quantified for both methods. The chemical purification of 32P and 33P separated by both procedures was validated by their decay curves. The absorber thickness of aluminum for LBC was assessed as 39.2 mg/cm 2 . 32P and 33P specific activities in some rain samples were determined by both methods and showed good consistent results. The advantage of the LSS over the LBC is apparent in its high counting efficiency and in determining samples with high concentration of stable phosphorus. However, when measuring environmental samples with low concentration of stable phosphorus, such as rainwater, both methods can be used and each has its distinct advantage.  相似文献   

11.
末水条斑紫菜以组织捣碎机粉碎,在10 mmol/L磷酸盐缓冲液(p H 6.8)中反复冻融3次,收集上清液,通过膨化床疏水层析技术分离R-藻红蛋白(R-PE),剩余残渣用于硫酸多糖提取。使用膨化柱分离,粗提液中约17%的藻红蛋白可以被回收,DEAE-Sepharose离子交换树脂纯化后,约12%的R-藻红蛋白得到回收,光谱纯度大于3.2,纯化得率为0.66 mg/g鲜紫菜。吸收光谱、荧光发射光谱以及凝胶电泳均显示该藻红蛋白属于典型三峰型R-藻红蛋白。利用藻红蛋白提取后的残渣,每克条斑紫菜可回收到30.5 mg的粗多糖,其中硫酸基含量为21.8%。实验证明,微波辅助抽提与热水浸提对硫酸多糖得率无显著影响。纯化的R-藻红蛋白与紫菜硫酸多糖可用于食品、化妆品添加,或药品、保健品的开发。本文对探索次等紫菜生物质的综合、高值化利用,进一步促进我国相关产品的开发与应用具有重要意义。  相似文献   

12.
沉积物中磷的存在形态及其生物可利用性研究   总被引：12，自引：0，他引：12  
用MgCl2,NaOH和HCl对大亚湾的大鹏澳、南海的珠江口、厦门湾的胡里山沉积物进行了逐级提取和总磷分析,并以这3种沉积物为惟一磷源培养小球藻和球等鞭金藻,估算了藻类对沉积物中磷的可利用量.结果表明,3种沉积物总磷含量分别为449.3,650.1和643.9mg/kg;MgCl2和NaOH提取的生物可利用的非磷灰石无机磷分别为168.8,146.6和118.1mg/kg.非磷灰石无机磷占总磷的18.3%～32.6%.3种提取剂对3种沉积物提取的磷是HCl提取相最大,NaOH提取相次之,MgCl2提取相最小.小球藻和球等鞭金藻在3种沉积物中的最大相对生长率为4.3%～26.9%,两种藻在3种沉积物中的生长与非磷灰石无机磷和藻类可利用的颗粒磷量相对应.颗粒磷占非磷灰石无机磷的42.4%～78.2%,占沉积物中总无机磷的21.1%～27.1%,占总磷的11.8%～20.3%.  相似文献   

13.
Jian Ma  Dongxing Yuan  Ying Liang   《Marine Chemistry》2008,111(3-4):151-159
A cartridge of solid phase extraction (SPE), hydrophilic–lipophilic balance (HLB), has been used to enrich phosphomolybdenum blue (PMB) from water samples without any other additives. Based on this, the previous on-line SPE method established for the determination of nanomolar soluble reactive phosphorus (SRP) in seawater has been greatly improved. Cetyltrimethylammonium bromide (CTAB), the cationic surfactant needed for the formation of the PMB-CTAB paired compound that could be extracted on a Sep-Pak C18 cartridge using the previous method [Liang, Y., Yuan, D.X., Li, Q.L., Lin, Q.M., 2007. Flow injection analysis of nanomolar level orthophosphate in seawater with solid phase enrichment and colorimetric detection. Marine Chemistry 103, 122–130.], was not necessary. Thus the longer time and higher temperature required for the complete formation of the PMB-CTAB compound were no longer needed. In addition, with application of the sequential injection analysis technique the proposed method showed the advantages of being much faster, simpler, sample and reagent saving, as well as more convenient in operation. The PMB compound formed under room temperature was efficiently extracted on an in-line HLB cartridge, rapidly eluted by 0.15 mol/L NaOH solution, and finally determined with a laboratory-made spectrophotometer at 740 nm. Experimental parameters, including the volume of reagents added, sample loading flow rate, and eluting flow rate, were optimized. Time and temperature for the PMB reaction, and salinity effect were also studied, and these were found to have no severe effect on the detection. With variation of sample loading time at a fixed flow rate, a broadened determination range of 3.4 to 1134 nmol/L phosphate could be obtained. The recovery and the method detection limit of the proposed method were found to be 94.4% and 1.4 nmol/L, respectively. The relative standard deviation (n = 7) was 2.50% for the sample at a concentration of 31 nmol/L phosphate. Two typical seawater samples were analyzed with both the proposed method and the magnesium hydroxide-induced coprecipitation method and, using the t-test, the results of the two methods showed no significant difference.  相似文献   

14.
Concentrations of microbial ATP in 15 New Zealand lakes were determined using 2 extraction techniques. ATP was found in both the paniculate (>0.45 μm) and dissolved (<0.45 μm) fractions of the water samples. Higher concentrations of paniculate ATP were obtained when ATP was extracted directly from freshwater samples rather than following pre‐concentration on to membrane filters. Recovery of particulate ATP declined with increasing volumes of sample filtered. The magnitude of the filtration effect varied unpredictably between lakes and within lakes with time. Corrections for the presence of dissolved ATP were necessary before estimates of particulate ATP could be made by the direct extraction technique. Concentrations of dissolved ATP up to 1.2 μg L‐1 were observed. The direct extraction technique is recommended for more accurate determination of particulate ATP in New Zealand freshwaters.  相似文献   

15.
This study characterizes humic substances (HS) from two soils colonized by Spartina maritima at different physiographical positions in estuarine environments on the north-western coast of the Iberian Peninsula: the Villaviciosa site, a stand close to the main tidal channel, and the Ortigueira site, located in the low salt marsh. Humic and fulvic acids were extracted from the soils and characterized qualitatively by the following spectroscopic techniques: Fourier transform infrared spectroscopy, fluorescence spectroscopy and solid-state 13C nuclear magnetic resonance.The characterized HS showed a predominance of low humified compounds with a high proportion of aliphatic components and a low degree of aromaticity. The HS composition differed substantially between sites. In the Villaviciosa soil, the large amount of nonpolar aliphatic components and the very low degree of aromaticity may indicate a significant contribution of marine organic matter and/or microbial material to the HS. However, in the HS from the Ortigueira soil, the higher proportion of polysaccharides together with the presence of lignin-derived compounds may indicate greater inputs of vascular plant material. The δ13C isotopic composition of the bulk soils highlights the large input of Spartina maritima debris to the Ortigueira site, whereas in the Villaviciosa site, organic contributions from this C4 vascular plant were not so evident.The results indicate that in these soils colonized by Spartina maritima, physiographical position has an important effect on the composition of soil HS and, therefore, must be considered in the study of organic matter characteristics in such estuarine environments.  相似文献   

16.
《Oceanologica Acta》1998,21(4):543-550
Humic acids from sediments of different depositional environments have been studied by solid-state 13C NMR and the results compared with the traditional wet chemical analysis. Results obtained are well in agreement with the previous literature reports that the carboxyl content measured by NMR correlated better with the total acidity, as well as with the carboxyl content obtained by wet chemical analysis after correction for amino acid carboxyl is made (following hydrolysis of peptide bonds). There is a large discrepancy between the NMR and wet chemical measurements of phenolics. NMR spectra was also indicative of branched paraffinic structures in the humic acids from the Arabian Sea; the humic acids of sediments from estuarine and coastal areas of the Bay of Bengal being dominated by carbohydrates and aromatic structures and to a lesser extent by paraffinic structures. These differences are attributed to their different biogeochemical origin.  相似文献   

17.
Cd, Cu, Fe, Ni, Pb and Zn were determined in 123 samples from the Baltic Sea proper. The trace metals were extracted directly on board the vessel, using a dithiocarbamate-Freon procedure. Final analyses of the extracts are performed onshore by atomic absorption spectrometry.Similar trace-metal concentrations are found in different areas of the Baltic proper. Most values fall in the following ranges: Cd, 30–60 ng 1?1; Cu, 0.6–1.0 μg 1?1; Fe, 0.3–0.9 μg 1?1; Ni, 0.6–0.9 μg 1?1; Pb, 0.05–0.2 μg 1?1; and Zn, 1.5–3.5 μg 1?1. The metal-concentrations are generally independent of depth. However, copper exhibits a small but significent decrease in concentration below 80 m.Filtration did not affect trace-metal concentrations, with the exception of iron in waters from lower layers. Similarly, storage under acid conditions was shown to affect only the concentration of iron. An electro-chemical technique was also used to determine Cu in some samples.  相似文献   

18.
Nutrients, chlorophyll a, primary production (14C), and standard oceanographic parameters were measured seasonally from 1983 to 1988 along the axis of a karstic estuary of the central Adriatic Sea (the Krka River estuary). Because of anthropogenic phosphorus discharges, the surface-layer orthophosphate concentrations (up to 1.7 mmol m−3), phytoplankton biomass (chlorophyll a up to 23 mg m−3) and primary production (up to 108 mg C m−3 h−1) were significantly higher in ibenik Bay (lower estuary) than in the other estuarine subregions, and the coastal sea in particular. In contrast, nitrate and orthosilicate (up to 59 and 65 mmol m−3, respectively) distributions during autumn and winter were ascribed to dilution of Krka River nutrients along the estuary. As a consequence, the surface-layer inorganic N/P ratio was extremely high in the upper estuary (averages up to 180), but this ratio was reduced up to three times in ibenik Bay and the coastal sea. In spring and summer, nitrate and orthosilicate, but not orthophosphate, were almost exhausted from the water because of biological utilization. In the saline layer below the halocline (depth 2–5 m) oxygen saturation varied over a large range, particularly in the upper estuary (16–176%), and nutrient concentration ratios differed from those in the surface layer. A nutrient regeneration stoichiometric model was derived, based on a linear regression analysis: AOU:Si:N:P = 276:16:6:0.4. Anthropogenic nutrient inputs should be urgently reduced to re-establish a natural nutrient environment.  相似文献   

19.
To estimate the influence of mercury emitted from submarine fumaroles, the horizontal and vertical distribution of mercury in sediment of Kagoshima Bay was studied. The fumaroles are located in the northern bay head area, and the sediment samples had been taken from 52 points throughout the bay with a gravity core sampler. The core samples obtained were cut at a thickness of 1–2 cm and used for measurements. The total concentration of mercury in surface sediment in the northern and central areas of the bay was 51–679 μg kg− 1 (average 199 μg kg− 1, n = 22) and 23–100 μg kg− 1 (average 55 μg kg− 1, n = 30), respectively. The highest value was obtained in the vicinity of the fumaroles. The mercury concentration in sediment near the fumaroles varied with depth, which may reflect the variation in fumarolic activity. A successive extraction method was applied to the speciation of mercury in the sediment. The results showed that sediment taken in the vicinity of submarine fumaroles contained a higher percentage of mercury bound with organic matter.  相似文献   

20.
Coastal environments with reducing waters and/or sediments represent potential sinks for 99Tc discharged to sea. Here, we have examined estuarine sediments from four geochemically distinct locations that have been exposed to 99Tc discharged from Sellafield. Both the relative uptake and the operationally defined sediment “component” that holds the Tc were investigated in order to establish whether particular biogeochemical processes are predominately responsible for reducing and binding Tc in sediments. Despite the artefacts that can pose problems for sequential extractions, this scheme [Int. J. Environ. Anal. Chem. 51 (1993) 187] appears to be robust with regard to Tc. The results show that relative uptake of Tc varied greatly between the sites, with the highest occurring at an almost permanently anoxic fjord (Mariager Fjord, Denmark), followed by a brackish, seasonally eutrophic fjord (Roskilde Fjord, Denmark), then a sub-oxic salt marsh (which receives particle bound radionuclides from a more reducing mud patch; Esk Estuary, UK) and finally sulfidic and iron-reducing muddy sandy sediments (Needle's Eye, Solway Firth, Scotland). High relative uptake at the fjords was explained by the greater mixing of Tc-labelled oxic seawater into the part of the system where reduction of TcO4− was possible. Uptake at Mariager Fjord was higher than at Roskilde Fjord, reflecting the highly reducing geochemical conditions in the water body. Low uptake at Needle's Eye may be related to the speciation of technetium at this site as the sequential extraction data suggest that Tc is associated with the carbonate phase here. Tc carbonates are largely soluble, and this is the first observation of Tc association with carbonate fractions in the natural environment. The other three sites showed that organic matter, in conjunction with reducing conditions, was very important for binding and retaining Tc in sediments. The specific role of sulfides in controlling Tc retention in sediments was unclear because sulfides and organic matter are leached simultaneously in the sequential extraction scheme we applied, but there was evidence that Tc was not associated with acid-volatile iron monosulfides.  相似文献   

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