双辽火山活动与松辽盆地南部无机CO_2气藏的成因联系——来自火山岩中流体-熔融包裹体的证据

针对松辽盆地南部的双辽火山群中碱性玄武岩及包含其中的地幔捕掳体的普通薄片鉴定、岩石地球化学分析、流体包裹体显微岩相学和激光拉曼光谱分析,研究表明:双辽火山岩以碱性橄榄玄武岩为主,玄武岩中的地幔捕掳体比较发育;对玄武岩斑晶以及地幔捕掳体中的流体-熔融包裹体测试显示玄武岩中的橄榄石斑晶和地幔捕掳体中的流体-熔融包裹体十分发育,其成分主要是CO2,此外还含有少量的CO,CH4,N2和H2O,与上地幔中的自由流体相组分一致。松辽盆地南部的CO2气藏主要是幔源-岩浆成因,成藏时间较晚,主要在新生代,与双辽火山活动的时间接近。尽管双辽火山活动规模较小,但是具有很强的释出CO2的能力,这些富含CO2和H2O的碱性玄武质岩浆很可能并未喷出地表,而是沿着深大断裂进入盆地内部,从而成为松南无机CO2气藏气源体之一。     

Characteristics of Aerosol Pollution Under Different Visibility Conditions in Winter in a Coastal Mega-City in China

To investigate chemical profiles and formation mechanisms of aerosol particles in winter haze events,comprehensive measurements including hourly concentrations of PM2.5 and water-soluble inorganic ions and related gasphase precursors were conducted via an online monitoring system from January to March of 2016 in Shenzhen, a coastal mega-city in south China. In this study, high concentrations of PM2.5, NO2 and lower levels of O3 were observed during haze periods in comparison with clear days(Visibility15 km). The major secondary ionic species were NH+4、NO-3 and SO2-4, which varied significantly on haze and clear days. The ratio of NO-3/SO2-4 in haze days was greater than that on clear days and tended to be larger when air pollution became more serious. At the same time, compared with previous studies, it has been found that the ratio has been increasing gradually in Shenzhen, indicating that the motor vehicle exhaust emissions have a more and more important impact on air quality in Shenzhen. Sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) was higher during the haze period than that in clean days, indicating efficient gas to particle conversion. Further analysis shows that high concentrations of sulfate might be explained by aqueous oxidation,but gas-phase reactions might dominate nitrate formation. This study also highlights that wintertime nitrate formation can be an important contributor to aerosol particles, especially during haze periods.     

崇明岛河网浮游植物和无机、有机氮的时空分布特征

为研究崇明岛河网浮游植物和无机、有机氮的时空分布特征及其相互关系,于2014年1、4、7和10月在崇明岛河网内选取界河、堡镇港、八滧港3条河道9个采样点采集浮游植物和表层水样,并选取崇西水闸作为对照点进行研究.结果表明:河网内浮游植物以绿藻和硅藻为主,其中水闸和堡镇港夏季裸藻生物量所占比例超过50%.八滧港总溶解性氮(TDN)的主要组分是溶解性无机氮,而水闸、界河和堡镇港溶解性有机氮(DON)在TDN中的比例在夏、秋季低于冬、春季,农田土壤释放可能是DON的重要来源.水温、溶解氧和化学需氧量是影响铵态氮浓度变化的重要环境因素.此外,通过冗余分析发现,铵态氮影响绿藻和裸藻分布,尿素影响甲藻分布.     

深层地下水稀土元素无机形态及其对稀土特征的影响——以皖北任楼矿煤系含水层为例

在对皖北任楼矿煤系含水层地下水常规离子和稀土元素组成分析的基础上,运用Visual Minteq软件对溶解态稀土的无机形态进行了模拟。结果表明：煤系含水层地下水分为富SO₄^2-和富HCO₃^-(或富CO₃^2-)两类,二者pH值大致以8.20/8.36为界。富SO₄^2-水具有相对富HCO₃^-水偏低的稀土总量,但二者在PAAS(后太古代平均页岩)标准化图解上均表现为轻稀土亏损的型式。富SO₄^2-水中稀土无机形态包括Ln³⁺、LnCO₃⁺、LnSO₄⁺、Ln(CO₃)₂^-和Ln(SO₄)₂^-(Ln代表稀土元素),但富HCO₃^-水中以Ln(CO₃)₂^-和LnCO₃⁺为主,且各形态的相对含量与pH值和元素类型(如轻、重稀土)关系密切。HCO₃^-含量与地下水∑REE和/Nd_SN/Yb_SN存在明显的相关性,表明不同含量的稀土元素无机形态(尤其是Ln(CO₃)₂^-)对地下水中稀土元素总量和轻重稀土分异程度存在影响。     

The partitioning of nitrogen oxides in the lower Arctic troposphere during spring 1988

Surface observations of several nitrogen oxides in the Canadian high Arctic during the period March-April 1988 are reported. These include data on NO₂, the inorganic nitrates HNO₃ and particulate nitrate, and the organic nitrates PAN and C₃–C₇ alkyl-nitrates. It is found that the organic nitrates make up 70–80% of the sum of the measured nitrogen oxides. Based on concurrently measured sulphur oxides, the period of observation was divided into two halves with the first half representing less polluted, more aged air than the second. The preponderance of the organic nitrates was less in the first period than the second. In contrast, there was little difference in the inorganic nitrates and NO₂ concentrations. The dominant inorganic nitrate shifted from particulate nitrate in the first period towards gaseous HNO₃ in the second. No correlation between the nitrates (inorganic or organic) and O₃ was observed; although some indication of a positive correlation between NO₂ and O₃ has been reported earlier (Bottenheimet al., 1990). Possible explanations for these observations are proposed. A survey of other potential nitrogen oxides that may be present in the Arctic air but not measured in these experiments suggests that the nitrogen oxides not measured here constitute a minor fraction of the total reactive nitrogen (NO _y ).Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

辽东湾柱状沉积物中无机碳的形态

根据沉积物中无机碳的结合强度,运用连续浸取的方法将沉积物中的无机碳分成5种不同的形态:NaCl相、氨水相、NaOH相、盐酸羟胺相、HCl相。并以渤海辽东湾柱状沉积物为例,探讨了各形态无机碳的含量特征及其控制因素。研究表明,辽东湾不同层次沉积物中各形态无机碳的含量特征比较明显:氨水相>盐酸羟胺相≈盐酸相>NaOH相>NaCl相。氨水相、盐酸羟胺相和盐酸相无机碳占沉积物中总无机碳的绝大部分,大于80%;NaCl相和NaOH相无机碳只占总无机碳的一小部分。沉积物中各形态无机碳含量的变化受沉积环境如pH、Eh、Es、含水率、Fe3 /Fe2 、有机碳含量等因素的影响。其中NaCl相无机碳受pH、Eh影响较大;氨水相无机碳主要由含水率、Fe3 /Fe2 、pH、Eh控制;NaOH相无机碳主要由含水率、Eh和pH控制;盐酸羟胺相无机碳主要受含水率、Eh、有机碳的影响;HCl相无机碳的控制因素和盐酸羟胺相的相似,但它受pH和Eh的影响更显著。虽然有机碳和各个形态的无机碳都呈负相关关系,但它对每一形态的影响都不相同,其作用受其它环境因素的制约。环境的氧化能力越强,pH值越小,越不利于盐酸羟胺相和盐酸相无机碳的保存,而有利于NaCl相、氨水相和NaOH相无机碳的形成;环境的还原能力越强,pH值越大,越有利于盐酸羟胺相和盐酸相无机碳的保存,而不利于NaCl相、氨水相和NaOH相无机碳的形成。辽东湾沉积物的弱氧化-还原环境有利于盐酸羟胺相和盐酸相无机碳的保存。     

Forms and functions of inorganic carbon in the Jiaozhou Bay sediments

Inorganic carbon forms and their influencing factors, mutual transformation and contribution to carbon cycling in the Jiaozhou Bay sediments were discussed. The results show that inorganic carbon in sediments could be divided into five forms:NaCl form, NH₃·H₂O form, NaOH form, NH₂OH·HCl form and HCl form. Thereinto, NH₂OH·HCl form and HCl form account for more than 70% of total inorganic carbon. There was close relationship among every form of inorganic carbon and their correlativity was clearly different with different sedimentary environment except the similar strong positive correlation among NH₂OH·HCl form, HCl form and total inorganic carbon in all regions of the Jiaozhou Bay. All forms of inorganic carbon were influenced by organic carbon, pH, Eh, Es, nitrogen and phosphorus in sediments, but their influence had different characteristics in different regions. Every form of inorganic carbon transformed into each other continuously during early diagenesis of sediments and the common phenomenon was that NaCl form, NH₃·H₂O form, NaOH form and NH₂OH·HCl form might transform into steady HCl form. NaCl form, NH₃·H₂O form, NaOH form and NH₂OH·HCl form could participate in carbon recycle and they are potential carbon source; HCl form may be buried for a long time in sediments, and it may be one of the final resting places of atmospheric CO₂. Inorganic carbon which entered into sediments was about 4.98×10¹⁰ g in the Jiaozhou Bay every year, in which about 1.47×10¹⁰ g of inorganic carbon might be buried for a long time and about 3.51×10¹⁰ g of inorganic carbon might return into seawater and take part in carbon recycling.     

Episodic riverine influence on surface DIC in the coastal Gulf of Maine

Anomalously high precipitation and river discharge during the spring of 2005 caused considerable freshening and depletion of dissolved inorganic carbon (DIC) in surface waters along the coastal Gulf of Maine. Surface pCO₂ and total alkalinity (TA) were monitored by repeated underway sampling of a cross-shelf transect in the western Gulf of Maine (GOM) during 2004–05 to examine how riverine fluxes, mixing, and subsequent biological activity exert control on surface DIC in this region. Most of the variability in surface DIC concentration was attributable to mixing of low DIC river water with higher DIC, saline GOM waters, but net biological uptake of DIC was significant especially during the spring and summer seasons. The extent and persistence of the coastal freshwater intrusion exerted considerable influence on net carbon dynamics. Integrated over the 10-m surface layer of our study region (∼5 × 10⁴ km²), net biological DIC uptake was 0.48 × 10⁸ mol C during April–July of 2004 compared to 1.33 × 10⁸ mol C during April–July of 2005. We found the temporal signature and magnitude of DIC cycling to be different in adjacent plume-influenced and non-plume regions. Extreme events such as the freshwater anomaly observed in 2005 will affect mean estimates of coastal carbon fluxes, thus budgets based on short time series of observations may be skewed and should be viewed with caution.     

Dissolved inorganic carbon dynamics in the waters surrounding forested mangroves of the Ca Mau Province (Vietnam)

Dissolved inorganic carbon (DIC) and ancillary data were obtained during the dry and rainy seasons in the waters surrounding two 10-year-old forested mangrove sites (Tam Giang and Kiên Vàng) located in the Ca Mau Province (South-West Vietnam). During both seasons, the spatial variations of partial pressure of CO₂ (pCO₂) were marked, with values ranging from 704 ppm to 11481 ppm during the dry season, and from 1209 ppm to 8136 ppm during the rainy season. During both seasons, DIC, pCO₂, total alkalinity (TAlk) and oxygen saturation levels (%O₂) were correlated with salinity in the mangrove creeks suggesting that a combination of lower water volume and longer residence time (leading to an increase in salinity due to evaporation) enhanced the enrichment in DIC, pCO₂ and TAlk, and an impoverishment in O₂. The low O₂ and high DIC and pCO₂ values suggest that heterotrophic processes in the water column and sediments controlled these variables. The latter processes were meaningful since the high DIC and TAlk values in the creek waters were related to some extent to the influx of pore waters, consistent with previous observations. This was confirmed by the stochiometric relationship between TAlk and DIC that shows that anaerobic processes control these variables, although this approach did not allow identifying unambiguously the dominant diagenetic carbon degradation pathway. During the rainy season, dilution led to significant decreases of salinity, TAlk and DIC in both mangrove creeks and adjacent main channels. In the Kiên Vàng mangrove creeks a distinct increase of pCO₂ and decrease of %O₂ were observed. The increase of TSM suggested enhanced inputs of organic matter probably from land surrounding the mangrove creeks, that could have led to higher benthic and water column heterotrophy. However, the flushing of water enriched in dissolved CO₂ originating from soil respiration and impoverished in O₂ could also have explained to some extent the patterns observed during the rainy season. Seasonal variations of pCO₂ were more pronounced in the Kiên Vàng mangrove creeks than in the Tam Giang mangrove creeks. The air–water CO₂ fluxes were 5 times higher during the rainy season than during the dry season in the Kiên Vàng mangrove creeks. In the Tam Giang mangrove creeks, the air–water CO₂ fluxes were similar during both seasons. The air–water CO₂ fluxes ranged from 27.1 mmol C m⁻² d⁻¹ to 141.5 mmol C m⁻² d⁻¹ during the dry season, and from 81.3 mmol m⁻² d⁻¹ to 154.7 mmol m⁻² d⁻¹ during the rainy season. These values are within the range of values previously reported in other mangrove creeks and confirm that the emission of CO₂ from waters surrounding mangrove forests are meaningful for the carbon budgets of mangrove forests.     

Time series of carbonate system variables off Otaru coast in Hokkaido, Japan

We report several biogeochemical parameters (dissolved inorganic carbon (DIC), total alkalinity (TA), dissolved oxygen (DO), phosphate (PO₄), nitrate + nitrite (NO₃ + NO₂), silicate (Si(OH)₄)) in a region off Otaru coast in Hokkaido, Japan on a “weekly” basis during the period of April 2002–May 2003. To better understand the long-term temporal variations of the main factors affecting CO₂ flux in this coastal region and its role as a sink/source of atmospheric CO₂, we constructed an algorithm of DIC and TA using other hydrographic properties. We estimated the CO₂ flux across the air–sea interface by using the classical bulk method. During 1998–2003 in our study region, the estimated fCO_2sea ranged about 185–335 μatm. The maximum of fCO_2sea in the summer was primarily due to the change of water temperature. The minimum of fCO_2sea in the early spring can be explained not only by the change of water temperature but also the change of nutrients and chlorophyll-a. To clarify the factors affecting fCO_2sea (water temperature, salinity, and biological activity), we carried out a sensitivity analysis of these effects on the variation of fCO_2sea. In spring, the biological effect had the largest effect for the minimum of fCO_2sea (40%). In summer, the water temperature effect had the largest effect for the maximum of fCO_2sea (25%). In fall, the water temperature effect had the largest effect for the minimum of fCO_2sea (53%). In winter, the biological effect had the largest effect for the minimum of fCO_2sea (35%).We found that our study region was a sink region of CO₂ throughout a year (−0.78 mol/m²/yr). Furthermore, we estimated that the increase of fCO_2sea was about 0.56 μatm/yr under equilibrium with the atmospheric CO₂ content for the period 1998–2003, with the temporal changes in the variables (T, S, PO₄) on fCO_2sea, thus as the maximum trend of each variable on fCO_2sea was 0.22 μatm/yr, and the trend of residual fCO₂ including gas exchange was 0.34 μatm/yr. This result suggests that interaction among variables would affect gas exchange between air and sea effects on fCO_2sea. We conclude that this study region as a representative coastal region of marginal seas of the North Pacific is special because it was measured, but there is no particular significance in comparison to any other area.