Determination of ammonium regeneration rates in the oligotrophic ocean by gas chromatography/mass spectrometry

A method has been developed for the determination of ammonium concentration and isotopic enrichment in seawater samples at the low nanomolar range (10–100 nmol/kg). It is based on the reaction of phenol/hypochlorite with ammonium to form indophenol, with subsequent solid phase extraction, derivatisation and analysis by Gas Chromatography Mass Spectrometry. The precision of the method was maximised by incorporating a deuterated indophenol internal standard. A system was developed which generated seawater with extremely low ammonium concentrations thus matching sample and standard matrices for quantitative analysis. Data are presented from a study of ammonium regeneration rates at three stations in the oligotrophic North–East Atlantic where ambient ammonium concentrations were < 21 nmol/kg. Results suggested that ammonium availability for phytoplankton was limited by the rate of ammonium regeneration. Efficient ammonium assimilation contributed to the very low ambient ammonium concentrations measured at these stations. The study highlights the need for the accurate determination of ammonium regeneration rates in studies of new production, particularly in extreme oligotrophic conditions. If not corrected for isotope dilution, f-ratio estimates may be overestimated by 10.7–13.7%.     

Gas chromatography and gas chromatography/mass spectrometry applied to the determination of a new pathway of pristane degradation by a marine mixed bacterial population

Degradation of pristane is rapidly achieved with high efficiency by a mixed bacterial population isolated from a marine biotope highly polluted with hydrocarbons.Analysis of the degradation products by gas chromatography and gas chromatography/mass spectrometry reveals that pristane is not only attacked according to classical mechanisms of β- and ω-oxidation, but also according to a new mechanism beginning with attack at the third carbon atom.Thanks to that mechanism, the population must be particularly suited to degradation of substrates resistant to α- and β-oxidations; this has been confirmed with an α-disubstituted structure.     

黑海参脂肪酸的气相色谱/质谱法分析

黑海参(Holothuria atra)体壁经Folch 法提取总脂, 用HCl-甲醇进行甲酯化处理, 以气相色谱/质谱法分析总脂中的脂肪酸组成。从黑海参中共分析出28 种化合物, 包括25 种脂肪酸甲酯和3 种脂肪醛二甲基缩醛。黑海参体壁中的饱和脂肪酸含量为22.93%, 以C_16:0(5.49%)和C_18:0(4.38%)为主; 不饱和脂肪酸含量为65.19%, 其中单不饱和脂肪酸33.86%, 主要为C_20:1(n-9)(15.90%); 多不饱和脂肪酸为31.33%, 主要为C_20:4(n-6)(19.57%)和C_20:5(n-3)(5.86%)。脂肪醛二甲基缩醛含量为7.28%, 表明黑海参体壁总脂中含有较丰富的缩醛型甘油酯。     

黑海参脂肪酸的气相色谱／质谱法分析

黑海参（Holothuria atra）体壁经Folch法提取总脂,用HCl-甲醇进行甲酯化处理,以气相色谱／质谱法分析总脂中的脂肪酸组成。从黑海参中共分析出28种化合物,包括25种脂肪酸甲酯和3种脂肪醛二甲基缩醛。黑海参体壁中的饱和脂肪酸含量为22．93％,以C16：0（5．49％）和C18：0（4．38％）为主;不...     

A catalytic oxidation method for the determination of total nitrogen dissolved in seawater

A detailed examination of a high-temperature catalytic oxidation method for liquid samples in the analysis of total nitrogen dissolved in seawater is reported. The nitrogenous compounds in liquid samples are oxidized on a platinum catalyzer at 680°C under oxygen atmosphere and the generated NO₂ is absorbed into a chromogenic reagent, followed by a spectrophotometric determination. The results of this method are much higher than those of wet oxidation methods. Molecular size dependency of the results clearly indicates that the above discrepancy is caused by the low oxidation capacity of the wet oxidation method against high-polymer organic matter dissolved in seawater. The results revealed that the concentration of total nitrogen in seawater is nearly constant from surface to bottom, ranging from 30 to 40 μM 1^?1, which organic nitrogen concentration higher in the surface layer, and a rapid decrease with depth. An examination of molecular size distribution indicates that the concentration of high-polymer organic nitrogen decreases rapidly from surface to deeper layers, with molecular sizes ranging from 5 × 10³ to 3 × 10⁴. Because of the well-defined principle of the oxidation process, its reliability, ease of sample handling and of analytical procedure on board or in the land laboratory, the present method is much more suitable for the marine analytical chemistry of total and organic nitrogen than the other previous methods.     

Analysis of lignin-derived phenols in standard reference materials and ocean dissolved organic matter by gas chromatography/tandem mass spectrometry

A series of reference materials are proposed for intercomparison and quality control purposes during the quantification of lignin oxidation products (LOP) from diverse environmental matrices. These materials are all easily accessible and certified for diverse organic constituents (NIST and IHSS). They represent a suite of natural environmental matrices (from solids to aqueous) and are characterized by a wide range of organic carbon and lignin concentrations with abundant proportions of all major LOP. The variability of LOP concentrations and signatures for all these materials averages 3–5% and does not exceed 10%. Using these standards, a new quantification method was developed and validated for the determination of low-level CuO oxidation products using capillary gas chromatography–tandem mass spectrometry (GC/MS–MS). Tandem mass spectrometry provides both the high sensitivity and selectivity required for the identification and quantification of trace levels of dissolved lignin. The method is particularly useful for removing interference from co-eluting isotopes generated from the DOM matrix and during glucose amendment procedures of low-carbon samples. Such glucose amendment is not necessary, however, when the CuO to organic carbon weight-to-weight ratio can be kept at a value < 200–300.     

An improved method for the determination of ammonia in seawater

The Liddicoat, Tibbitts and Butler method for the determination of ammonia in seawater has been noticeably improved by replacing the UV lamp with a 300 VA tungsten lamp. The characteristics so achieved, a low blank value (0.012 ± 0.002a.u.), a good molar absorptivity (23.90 × 10⁻³) and a reasonably short reaction time (1 h), are such that this modified procedure is more convenient for routine work in chemical oceanography.     

红树植物白骨壤树叶挥发油化学组成特点及气相色谱/质谱分析

水蒸汽蒸馏法提取红树植物白骨壤Avicennia marina叶的挥发油,经气相色谱/质谱联机分析,检出13个色谱峰,鉴定出13个化合物,主要是2,6-二叔丁基-4-甲基苯酚,2-苯基-1,3-丁二烯和4-羟基-2-甲基苯乙酮等.并讨论了上述挥发油化学组成的特点及主要组分的用途.     

A simplified resorcinol method for direct spectrophotometric determination of nitrate in seawater

A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 10⁴ L mol^− 1 cm^− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.     

A simple indirect method for the determination of organic-carbon in marine particles

A simple indirect method for the determination of organic carbon in marine particulate matter is proposed. The recommended procedure is as follows: The dried sample is ashed at 450°C for about 24 hr. The ashed sample is put into a Teflon vessel followed by a mixed solution of nitric acid, perchloric acid and hydrofluoric acid. The vessel is sealed and allowed to stand at 150°C for 5 hr. The concentrations of Si and Al in the digested solution are determined. The organic carbon content (Cal-C, %) is calculated by the following equation: Cal-C=0.52 ([CF]–0.10 [Opal]–0.03 [A-Si]), where [CF] is the combustible fraction (%), [Opal] is the biogenic-SiO₂(%), and [A-Si] is the content of aluminosilicate mineral (%).     

A modified analytical method for the shipboard determination of nanomolar concentrations of orthophosphate in seawater

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.     

A simplified automated chelometric method for the determination of sulfate in interstitial water and seawater

A method is described for the determination of sulfate in interstitial water and seawater. After BaSO₄ precipitation, the Ba²⁺ excess is titrated with EDTA using an amalgated silver electrode for end-point detection. An accuracy better than 0.5% is obtained using this method.     

ICP-OES标准加入法准确测定海水中的硼

硼作为海水中的重要组分,其准确测定对海洋环境生物地球化学过程研究具有重要意义。海水中硼的常用测定方法具有前处理步骤繁琐、耗时长、样品易被污染、灵敏度低等缺点,不适于大批量海水样品的准确测定。为剔除海水高盐基体效应及干扰,本文运用电感耦合等离子体发射光谱法(ICP-OES),将海水样品进行稀释,采用标准加入法建立工作曲线,对海水中硼含量进行准确测定。正交实验显示,ICP-OES最佳工作条件为射频功率1400 W,雾化气流量0.7 L/min,观测高度14 mm,进样泵速1.5 m L/min。标准加入法标准曲线相关系数大于0.999,相对标准偏差为0.76%~1.27%,加标回收率为94.6%~101.8%,方法检出限为1.073μg/L。实际的海水样品分析表明,该方法可消除海水基体干扰,减少测定误差,并且前处理操作简单快速,化学试剂用量少,回收率高,精密度好,灵敏度高,可用于海水及其它高盐样品中硼含量的准确测定。     

离子色谱-电感耦合等离子体质谱联用测定海水中的IO3^-和I^-

研究了离子色谱-电感耦合等离子体质谱（IC-ICPMS）联用技术直接进样测定海水中IO3^-和I^-的方法．采用IonPacAG23离子色谱保护柱分离IO3^-和I^-,以浓度4．0mmol／dm3的KOH为流动相,流量为1．0cm3／min,每个样品的分析时间为2．5min．采用2．5×10^-3cm^3的进样量,IO3^-和I^-的检出限分别达到0．6和0．4nmol／dm2,可满足海水中碘形态的定量分析．该方法的IO3^-和I^-浓度范围在2．0nmol／dm3～2．0μmol／dm3．     

共沉淀富集法测定海水中稀土元素含量方法研究

稀土元素已越来越多地应用于示踪各类地球化学体系的物质来源与岩石矿物形成等演化过程。但在进行海水样品的稀土元素检测时,由于样品的高盐特征和稀土元素的痕量特征又使得分析具有相当的挑战性。本研究旨在从高盐的海水基质中有效分离并富集痕量的稀土元素,同时结合电感耦合等离子体质谱（Inductively Coupled Plasma Mass Spectrometry, ICP-MS）技术对海水中的稀土进行定量分析。通过对海水样品稀土元素的定量限分析、加标回收实验和梯度加标回收实验,验证了方法的准确性,评估方法的分离富集效率。通过共沉淀过程中的pH比较、氢氧化钠与氨水作为共沉淀剂的比较,确定了富集过程中共沉淀剂用量、种类等影响因素。通过稀土元素配分曲线的绘制与类似样品结果进行比对,以及标准海水的检测结果,验证了方法在实际样品中的可行性。本研究探索了共沉淀富集法在分离富集海水中稀土元素的实验条件,实现高盐背景下痕量稀土的准确定量,并将其用于近岸海水与孔隙水的实际检测。     

Degradation of lubricating oils by marine bacteria observed by quantitative mass spectrometry

Bacterial degradation of the hydrocarbons of lubricating oils was investigated by mass spectrometric analysis which gives both total amount and the composition of hydrocarbon types of residual oil. An unused lubricating oil, which mainly consisted of hydrocarbon types with only a small percentage ofn-alkanes, was degraded by marineBacillus sp. andPseudomonas sp. with 55 % and 25 % decreases in 10 days, respectively. Susceptibility of respective hydrocarbon types to biodegradation was in the following order: alkanes > non-condensed cycloalkanes, mono-aromatics > condensed cycloalkanes. A used lubricating oil of different brand showed a larger decrease than the unused oil. Both species of bacteria degraded large portions of alkane fraction of Arabian light crude oil.     

Rates of microbial degradation of petroleum components as determined by computerized capillary gas chromatography and computerized mass spectrometry

The biodegradation rates of Arabian light crude oil components under the action of a marine mixed microbial culture were monitored in a quasicontinuous culture during a 60 day experiment. The saturated hydrocarbons were degraded more rapidly and extensively (74%) than the aromatics (50%), whereas the biodegradation of asphaltenes (30%) and of resins (< 5%) was very low. The joint use of computerized high-resolution chromatography and of computerized mass spectrometry permitted classification of the petroleum constituents according to their biodegradability: (i) highly susceptible, − and iso-alkanes; (ii) susceptible, 6, 1, 5 and 2 ring alkanes, 1 ring and sulphur aromatics; (iii) moderately susceptible, 3 and 4 ring alkanes, 2 and 3 ring aromatics; (iv) resistant, tetra-aromatics, steranes, triterpanes, naphtheno-aromatics; and (v) highly resistent, penta-aromatics, asphaltenes and resins. Unlike saturates, aromatics were degraded at a rate that was in relation to the number of rings of the molecules. The microbial activity leads to the formation of a residue which can be considered as a form of stable organic matter. The biodegradation potential of a mixed microflora is much more elevated in continuous culture systems than in batch cultures.     

Isotope dilution sector-field inductively coupled plasma mass spectrometry combined with extraction chromatography for rapid determination of 241Am in marine sediment samples: A case study in Sagami Bay, Japan

²⁴¹Am is a useful tracer for understanding biogeochemical processes in the marine environment. ²⁴¹Am also poses a potential radiation threat to human health due to the continuous increase of its concentration in the global environment. We report a rapid analytical method for determining ²⁴¹Am in marine sediments using isotope dilution sector-field inductively coupled plasma mass spectrometry (SF-ICP-MS) combined with a high-efficiency sample introduction system (APEX-Q). A selective CaF₂ co-precipitation procedure followed by TRU extraction chromatography was employed to effectively remove the major sediment matrix and to pre-concentrate ²⁴¹Am. We achieved an extremely low detection limit of 0.32 fg/g or 0.041 mBq/g (for 1 gram sediment), which is better than that of alpha spectrometry, and it allowed the accurate determination of ²⁴¹Am in low-level marine sediment samples. The accuracy and precision of the developed analytical method was evaluated using a laboratory prepared Am isotope standard solution and Ocean Sediment reference material (IAEA-368). The results were satisfactory. For sediment samples, overall chemical recoveries varied from 60–90%. The developed method was applied to the study of ²⁴¹Am depth distribution in Sagami Bay, Japan, where we observed different depth profiles between ²⁴¹Am activity and ^239+240Pu activity.     

A solvent extraction method for the colorimetric determination of nanomolar concentrations of silicic acid in seawater

A solvent extraction method for measuring nanomolar concentrations of silicic acid in seawater is described. The procedure is based on the formation of beta silicomolybdic acid by reaction of silicic and molybdic acids at low pH, extraction of the combined acid into n-butanol and reduction with a mixture of p-methylaminophenol sulfate and sulfite. The concentration of the resulting blue silicomolybdous acid in the extract is determined colorimetrically. The method has 30 times the sensitivity and 14 times the precision of standard aqueous analyses. Molar absorbance is 2.29 × 10⁵ in seawater with a precision of ± 2.5 nM Si for concentrations <- 50 nanomolar. Sensitivity in seawater is 70% of that in deionized distilled water owing to a significant salt effect. Natural concentrations of arsenate, arsenite and germanic acid cause negligible interference; however, phosphate interference is equivalent to 11 ± 1 nM Si over a broad range of phosphate concentrations, resulting in an error of ± 1 nM in the corrected silicic acid concentration measurement.     

高压密闭消解-电感耦合等离子体光谱和质谱联合测定海洋地质样品中52种元素

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method(HPCD), is studied by an inductively coupled plasma optical emission spectrometry(ICP-OES) and an inductively coupled plasma mass spectrometry(ICP-MS). The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error(RE) for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials(GBW07309, GBW07311, GBW07313), rock reference materials(GBW07103, GBW07104,GBW07105), and cobalt-rich crust reference materials(GBW07337, GBW07338, GBW07339), the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation(RSD) and the relative error(RE) are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.