An Assessment of HOx Chemistry in the Tropical Pacific Boundary Layer: Comparison of Model Simulations with Observations Recorded during PEM Tropics A

Reported are the results from a comparison of OH,H₂O₂CH₃OOH, and O₃ observationswithmodel predictions based on current HO_x–CH₄reaction mechanisms. The field observations are thoserecorded during the NASA GTE field program, PEM-Tropics A. The major focus ofthis paper is on thosedata generated on the NASA P-3B aircraft during a mission flown in the marineboundary layer (MBL) nearChristmas Island, a site located in the central equatorial Pacific (i.e.,2° N, 157° W). Taking advantage of thestability of the southeastern trade-winds, an air parcel was sampled in aLagrangian mode over a significantfraction of a solar day. Analyses of these data revealed excellent agreementbetween model simulated andobserved OH. In addition, the model simulations reproduced the major featuresin the observed diurnalprofiles of H₂O₂ and CH₃OOH. In the case ofO₃, the model captured the key observational feature whichinvolved an early morning maximum. An examination of the MBL HO_xbudget indicated that the O(¹D) + H₂Oreaction is the major source of HO_x while the major sinks involveboth physical and chemical processes involving the peroxide species,H₂O₂ and CH₃OOH. Overall, the generally goodagreement between modeland observations suggests that our current understanding ofHO_x–CH₄ chemistry in the tropical MBL isquite good; however, there remains a need to critically examine this chemistrywhen both CH₂O and HO₂are added to the species measured.     

Latitude versus Depth Simulations of Ecodynamics and Dissolved Gas Chemistry Relationships in the Central Pacific

Nutrient ecology and trace gas processing are intimately coupled in the surface ocean and participate in key linkages through the Earth biogeochemical system. We have added water column photochemistry for volatile sulfur and organic compounds to large scale nutrient cycle modules, in order to create a one dimensional, open ocean ecochemistry simulator. Phyto- and zooplankton, recyclers and biological waste products are represented through N and Fe densities. Dimethyl sulfide, carbonyl sulfide and the methyl halides are tracked individually along with certain precursors and nonmethane hydrocarbons. The model is applied along the 180 degree meridian in the Northern Hemisphere. Ecodynamics are validated against satellite ocean color maps. Biological/photochemical production terms are then iterated upon to match measured distributions for the trace gases. Data are most complete for dimethyl sulfide. Major patterns in its climatology are captured within individual ecological provinces. However, at the basin scale reduced sulfur release must be varied over almost an order of magnitude because the mechanism developed contains only one plant taxon. Based on sparser data, first order rate constants are estimated for phytoplanktonic exudation of the methyl halides. Parameters are also established for photolytic injection of carbonyl sulfide and propylene from the dissolved organics. Ocean general circulation models and interactive ocean-atmosphere transport simulations are discussed as frameworks for future application.     

海底资源与环境立体探测技术发展方向与对策

21世纪是人类全面开发利用海洋的新世纪。目前国际海底资源与环境探测，正在由海面、水中发展到空中、海底，形成立体的综合勘测。在21世纪前期，作为海洋大国，中国在维护海洋权益方面所面临的形势严峻复杂。如何发展、开发利用高新技术，以适应日新月异的世界海底资源与环境探测竞争需要，是广大海洋工作者都关心的课题。本文对立体探测技术发展方向和对策进行了简单探讨。     

辽宁区域海洋经济布局机理与可持续发展研究

通过对辽宁海洋资源的评价,海洋经济发展、海洋产业部门结构和海洋产业布局特点等的分析,并根据海域资源差异、区域海洋经济结构差异、海洋产业分布状况等,划分出辽宁渤海海洋经济区和黄海海洋经济区。探讨了区域海洋经济区的形成与区域海洋经济布局机理。采用定性与定量相结合、从定性到定量的研究方法,应用层次分析法确定辽宁海洋经济区的发展方向与重点海洋产业部门,提出了辽宁区域海洋经济可持续发展的对策和措施     

Primary alteration—oxidation of marine algal organic matter from oil source rocks of the North Sea and Norwegian Arctic: new findings

The presence of partially oxidized algal organic matter in oil-prone marine source rocks, is the rule rather than the exception. Partially oxidized, algal kerogen can still act as a significant source of liquid hydrocarbons. However, the corresponding peak of C₁₂ + hydrocarbon generation is shifted to a considerably lower maturity level compared with that of the classical Type II kerogen. The extent of primary alteration-oxidation of marine algal kerogen is monitored by means of solid state microfluorescence spectroscopy. A new parameter, the Primary Alteration Factor (PAF) is established, and the relationships between PAF and H/C, O/C, HI, TOC and between PAF and %₀δ¹³C are determined. The present data show large variations in the bulk chemistry of immature marine algal kerogens, and reveal evidence for gradational dehydrogenation/oxidation of the source organic matter. This contrasts with the recently proposed mechanism for kerogen formation. SEM analysis reveals a relationship between the physical breakdown of algal organic matter and the formation of liptodetrinite. FTIR analysis shows that the incorporation of primary oxygen in the kerogen macromolecules is not in the form of carbonyl or carboxyl functionalities. The presence of highly unreactive, stable oxygen, associated with aromatic structures in partially oxidized algal kerogen, is suggested by resistance of the kerogen to graphitization. The FTIR data also suggest the presence of aryl ether oxygen. The present findings raise fundamental questions regarding the mechanisms of kerogen cracking and kerogen formation, and have important implications for petroleum exploration.     

Mid-chain ketocarboxylic acids in the remote marine atmosphere: Distribution patterns and possible formation mechanisms

In remote marine aerosol samples collected from the North Pacific ocean, Enewetak Atoll, American Samoa, and New Zealand, series of mid-chain ketocarboxylic acids in the range of C₆-C₁₈ were detected. All the positional isomers, except for the 2-oxo and 3-oxo species, were detected for major ketoacid families (e.g. C₉, C₁₁ and C₁₃). Higher ketoacid concentrations (up to 19 ng/m³) were obtained in the northern North Pacific aerosol samples, which generally showed an odd carbon-numbered predominance with 5-oxoundecanoic acid being the major species. By contrast, lower concentrations were obtained in the lower-latitude or subtropical aerosol samples, where even carbon-numbered ketoacids were relatively abundant.The distribution patterns of the odd carbon-numbered ketoacids could not be explained by the primary emissions from source materials including terrestrial higher plants, soil particles, and ocean surfaces. We consider that the isomeric ketocarboxylic acids are produced in the atmosphere by the photochemical oxidation of semi-volatile monocarboxylic acids, which are counterparts of the oxidative degradation of unsaturated fatty acids emitted from seawater surfaces. Atmospheric production of the ketoacids is seemingly enhanced in the northern North Pacific, probably due to an enhanced primary productivity.     

A method for estimating microporosity of fine‐grained sediments and sedimentary rocks via scanning electron microscope image analysis

This study presents a method of two‐dimensional scanning electron microscope image analysis that directly quantifies microporosity abundance in clay‐rich, fine‐grained sediments. The method is novel in that it is specifically designed to circumvent the challenge to porosity quantification posed by mineral surface charging and topographical artifacts created during Ar‐ion cross‐section polishing. It utilizes the finding that differences in circularity values can be used to distinguish micropores from blemishes in a thresholded image. This method is powerful because it is fast and provides a direct microporosity estimation technique to augment or replace experimental data. The pore size range to which the method is applicable is clear and can be selected depending on the application of the analysis. When used appropriately, the method can be implemented on microporous sediments and sedimentary rock in general. The method is developed using marine muds of Pliocene and Miocene ages from the Nankai margin (burial depths from approximately 200 to 1100 m). The close match between imaging‐derived microporosity and bulk N₂ microporosity measurements shows that porosity in these young and relatively shallowly buried sediments is dominated by pores of sizes that can be imaged by scanning electron microscopy. In Kumano, forearc basin sediments of the Nankai Trough, results of this method show a significant increase in microporosity with burial depth, probably due to microporosity preservation during compaction and possibly early volcanic ash diagenesis.     

江苏省海洋经济与区域经济耦合协调性研究

伴随着海洋资源开发和海洋科技进步,海洋产业在国民经济中扮演着日益重要的角色,海洋经济与区域经济的协调发展成为研究热点。江苏省是沿海地区经济发展强省,但其海洋经济发展优势并不突出,为了对其海洋经济与区域经济的耦合协调发展状态及耦合发展的制约因素进行研究,文章在探析海洋经济系统与区域经济系统耦合发展机理的基础上,借鉴物理学耦合度函数构建了海洋经济与区域经济的耦合协调度模型,并对2006~2012年江苏及其他沿海省市海洋经济与区域经济的耦合协调度进行了评价。结果表明2006~2012年间,江苏省海洋经济与区域经济的耦合协调度不断提高,逐步迈入了磨合发展的关键期,但海洋产业发展模式落后和海陆互动性弱等因素导致其与沿海其他省市相比仍有较大差距。本研究能够为江苏海洋经济发展提供科学建议。