Isotope dilution measurement of inorganic chromium(III) and total chromium in seawater

A reproducible, low-blank, isotope-dilution technique for the determination of inorganic Cr(III) and total dissolved chromium in seawater has been developed. Analysis of coastal water from Brittany, France, confirms that inorganic Cr(III) exists in excess of the thermodynamic equilibrium value calculated from the model of Elderfield (1970). A vertical profile of total chromium at 13°N on the East Pacific Rise confirms the general features of Cr behaviour: slight depletion at the surface (Cr = 2.0 nmol l⁻¹ compared to 2.6 nmol l⁻¹ below 1000 m) and bottom excess possibly due to Cr (III) release from sediments (up to 15.8 nmol l⁻¹). A maximum enrichment of six times the average seawater value is obtained in hydrothermal waters. The chromium content of metalliferous sediments is mainly due to scavenging from the water column; input of chromium into the ocean through hydrothermalism is negligible.     

Distribution of Trace Bioelements in the Subarctic North Pacific Ocean and the Bering Sea (the R/V Hakuho Maru Cruise KH-97-2)

A column concentration-high resolution inductively coupled plasma mass spectrometry (ICP-MS) determination was applied to measure the total dissolved concentrations of Fe, Co, Ni, Cu and Zn in seawater collected from the subarctic North Pacific (~45°N) and the Bering Sea in July–September 1997. Total adsorbable Mn was determined on board by column electrolysis preconcentration and chemiluminescence detection. The vertical profiles for Fe, Ni and Zn were nutrient-like. The deep water concentration of Fe was ~0.5 nM in the northeast Pacific (18°-140°W) and increased to ~1 nM in the northwest Pacific (161°E) and ~2 nM in the Bering Sea (57°N, 180°E). The deep water concentrations for Ni and Zn in the Bering Sea were also 1.3–2 times higher than in the North Pacific. The profiles for Co and Cu were examined in the subarctic North Pacific, and results obtained were consistent with previous reports. There was a significant correlation between the concentrations of Co and Mn except for surface mixed layer. The profiles for total adsorbable Mn were similar to the reported profiles for total dissolvable Mn. The deep water concentration of Mn in the Bering Sea was also 4 times higher than in the North Pacific. Iron and zinc were depleted in surface water of the subarctic North Pacific. The relationship between these trace elements and nutrients suggests that these elements could be a limiting factor of phytoplankton productivity. In the Bering Sea, surface water contained ~0.3 nM of Fe. The Zn concentration, which was less than the detection limit in surface water, increased at shallower depths (~30 m) compared with the subarctic North Pacific. These results imply a higher flux of Fe and Zn to surface water in the Bering Sea. This in turn may cause the ecosystem in the Bering Sea characterized by a dominance of diatoms and high regenerated production.     

Uptake and release of 51Cr(VI) and 51cr(III) by Barnacles (Balanus sp)

Barnacles (Balanus sp) were used to examine the uptake and release of chromium-51 added to sea water in two different valence states, ⁵¹Cr(VI) and ⁵¹Cr(III).Hexavalent chromium-51 (sodium chromate) forms a true ionic solution in filtered sea water and barnacles were able to accumulate chronium in soft tissues 543 times the levels found in sea water. The experiment showed that incorporated Cr(VI), is released to the water in such way that only 20%% of maximum uptake was lost by the organisms after 26 days. Addition of the hexavalent form to non filtered sea water showed that 2% of the total radioactivity was attached to the suspended particles. Here again chromium is mainly concentrated in soft tissues, showing a concentration factor of 380 related to total chromium available in aquarium (solution + suspended particles). From the total radioactivity incorporated by the organisms, 20 % was released after 56 days in the clearance experiment.Chromium, as trivalent chromic chloride, when added to sea water precipitates and is quickly removed from the water by the filter activity of the barnacles. Unlike the hexavalent form, trivalent chromium is not concentrated in soft tissues of the barnacles and is quickly released to the water through the organisms digestive system.     

Lead in the North Sea and the north east Atlantic Ocean

Lead has been determined in 105 water samples from the north east Atlantic and from the North Sea. Rigorous precautions were applied to avoid contamination during sampling and analysis.Two different analytical methods were used: ASV and AAS. Determinations with ASV were carried out on board, directly after sampling. After two months storage, acidified samples were analysed by AAS after freon dithiocarbamate extraction and nitric acid back extraction. Particulate lead was determined by AAS after an acid digestion.The profiles of lead concentration versus depth show around 160 pM at the surface and around 20 pM at the bottom, both in the Atlantic and in the Norwegian Sea. The shapes of the profiles are different, however, depending on the hydrography of the area sampled. The profiles from the north east Atlantic coincide with a recently published profile from the north west Atlantic. Moreover, these profiles have lead concentrations about a factor of three higher than those in the Pacific.Considering the high lead input to the North Sea, the lead concentrations found there are remarkably low, probably because of scavenging effects in estuaries leading to a short residence time in the water column. The dominant lead input in offshore regions is from the atmosphere. The highest lead levels are found in the northern North Sea, around 300 pM in surface water.In the Atlantic, particulate lead is a minor part of the total lead whereas in the North Sea the particulate fraction is larger, up to 40%.     

南极洲赖特谷万达盐湖中铬的垂直迁移

南极洲万达湖湖水上部为氧化环境,铬浓度较低,Cr~(6+)占主导地位,主要以CrO_4~(2-)形式存在;下部为还原环境,铬浓度高,Cr~(3+)为主,以Cr(OH)_2~+和Cr(OH)~(2+)形式存在。湖水中锰、铁的氧化物及氢氧化物颗粒对铬离子的吸附和释放过程,控制了湖水铬浓度的变化。     

Distribution of dissolved organic carbon in and near the Prydz Bay, Antarctica

INTRODUCTIONDissolvedorganiccarbon (DOC)makesupthesecondlargestofthebioactivepoolsofcar bonintheocean ,secondtothelargestpoolofdissolvedinorganiccarbon .Theglobaldissolvedorganiccarbonpoolisestimatedtobe 6 85Gt,avaluecomparabletothemassofCO2 intheat mosphere (Hedges,1 992 ) .Thesizeofthereservoir,aswellasitsdynamics ,indicatesthatDOCplaysacentralroleintheoceancarboncycle .AsitrelatestogreenhousegasessuchasCO2 andassociatesclimatecycle ,oceanicDOCbiogeochemicalcycleshavebeenoneoftheh…     

Lead in the southern East China Sea

At present, in most oceans the lead (Pb) biogeochemical cycling has been disturbed by anthropogenic Pb through atmospheric input. The Pb concentrations in the upper water positively correlate with atmospheric input fluxes of Pb. The North Pacific is affected greatly by atmospheric substances via long-range transport from eastern Asia, especially from Mainland China. Mainland China may export considerable amounts of pollutants into the seas via rivers and the atmosphere owing to its recent fast growth in industry and economy. The East China Sea lies in an important geographical position--a transit between Mainland China and the western North Pacific. However, no data are available for seawater concentrations of Pb, a representative element with anthropogenic origin. In this work seawater samples from both 5 and 30-50 m water layers of 15 stations occupied over a cyclonic eddy in the southern East China Sea were analyzed for particulate Pb (PPb) and dissolved Pb (DPb). The Mean concentration of DPb (approximately 128 ng/l) in the southern East China Sea upper waters (< or = 50 m) is approximately several times higher than those in the Pacific; the high DPb concentrations in the southern East China Sea waters correspond to much higher atmospheric supplies of Pb to the East China Sea. Thus, this study partly fills the 'data gap' of the marginal seas. Also, it indicates that the East China Sea may be considerably contaminated by deposited polluted aerosols. Spatial distributions of DPb in the surface water show a tendency of increasing concentrations with distance offshore, that depends on the magnitudes of atmospheric Pb inputs and on particle scavenging processes. In contrast to DPb, spatial distributions of PPb basically display an 'omega'-like picture and a tendency of decreasing concentrations with distance offshore. These are related to riverine and scavenging sources and to the drive by the eddy. Additionally, the residence times of DPb in the surface water were estimated to be about 2 years, agreeing well with the reported data.     

赤道太平洋上层水体颗粒态生物硅分布及与营养盐的关系

依托中国“大洋一号”第20和第21调查航次,分析测定了东、西赤道太平洋4个站位的颗粒态生物硅浓度及其粒级结构。结果显示赤道太平洋采样站各层位颗粒态生物硅(PBSi)总浓度分布范围为5~65 nmol/dm³,东赤道太平洋的调查站位颗粒态生物硅的总浓度平均值达46 nmol/dm³,是西赤道太平洋的近3倍。PBSi的粒径结果显示在东赤道太平洋调查站位0.8~20 μm粒径颗粒是PBSi的主要来源,其平均贡献率高达64%;而在西赤道太平洋2种粒径的生物硅贡献率相当。营养盐分布对PBSi的浓度及粒径分布有显著的影响,并在一定程度上控制了“硅质泵”的组成结构,是控制大洋生物泵运转的重要因素。     

Chromium(VI) distributions in the Arctic and the Atlantic Oceans and a reassessment of the oceanic Cr cycle

Chromium(VI) concentrations ranging between 3.0 and 6.1 nmol l⁻¹ and 3.1 and 7.3 nmol l⁻¹ were found in the Arctic and Atlantic Oceans, respectively. The vertical profiles show modest depletion of chromium(VI) in surface waters, but poor overall correlations between Cr(VI) and nutrient profiles. Given that Cr(VI) is the dominant oxidation state of chromium in open-ocean waters, these data are combined with literature data to reassess the distribution of Cr in oceanic waters. It is concluded that while Cr shows some characteristics of both “recycled” and “accumulated” vertical profiles, it does not fall clearly within either group.     

Vertical distribution of bacterial abundance in the northwest pacific ocean

Mixed populations of free-living marine bacteria were collected at depths from the surface to the bottom (1,960m in Suruga Bay and 1,585 m in the Japan Sea) in the northwest Pacific during deep-sea diving by the submersible,Shinkai 2000. Their abundance in total cell counts and in lipopolysaccharide (LPS) concentration was found to decrease with increasing depth, and the decreasing profiles were shown to be linear on logarithmic scales. The total cell counts and the LPS concentration showed a linear relationship on arithmetic scales, and the LPS content per cell was found to be 1.02×10^–14 g.     

Chromium(III) — chromium(VI) interconversions in seawater

The stable form of dissolved chromium in oxygenated seawater is Cr(VI). But Cr(III)-species are also present at an analytically significant level. It is shown that Cr(III) is oxidized only slowly by dissolved oxygen, and that manganese oxide is a strong catalyst for such oxidation. However, the low oceanic concentration of suspended MnO₂ impedes the conclusion that the former process is quantitatively less important than the latter one. The distribution of dissolved chromium among Cr(VI)- and Cr(III)-species is probably kinetically controlled.     

Marine geochemistry of cadmium

A detailed study of particulate and dissolved cadmium distributions on 83 seawater samples from six profiles in the open North Atlantic Ocean showed a relatively homogenous distribution. The mean concentration of cadmium was 60 ± 27 ng/kg and the median concentration of particulate cadmium was 0.2 ng/kg. Although there are regional differences in dissolved cadmium concentrations among stations, it is suggested that cadmium behaves essentially as an inert element in sea water.Particulate cadmium is enriched by about a factor of four in samples from less than 400 m compared to samples from deeper than 1000 m. The high concentrations in surface waters are suggested to be due to aeolian transport of anthropogenically derived cadmium.Additional analyses of cadmium in the Gulf of Maine show a mean value of 230 ng/kg. The higher values in the Gulf of Maine are ascribed to the influence of continental runoff. Twelve sediment samples from the open North Atlantic show a relatively homogenous distribution, ranging from 0.13 to 0.21 ppm on a dry-weight basis.     

Planktonic foraminiferal flux to the deep ocean: Sediment trap results from the tropical Atlantic and the central Pacific

The flux of planktonic foraminifera between 100 μm and 1 mm to the seafloor has been estimated for the central Pacific (abyssal plain east of Hawaii) and the tropical Atlantic (Demerara Abyssal Plain) based on sediment trap samples collected from various water depths. The faunas in each region are quite similar, with 4 to 5 species generally accounting for 70–80% of the total assemblage.

At both study sites, the total foraminiferal flux and the carbonate flux tend to decrease with depth. In addition, the flux of individual species of planktonic foraminifera varies significantly with depth, with the number of small, solution-susceptible species decreasing with increasing water depth. These results suggest that there is significant dissolution of small (< 150 μm) foraminifera as they settle through the water column. Material collected from the sediment-water interface directly below the Pacific sediment trap array contains no planktonic foraminifera, suggesting that the residence time of an individual on the seafloor before it dissolves, is extremely short.     

Arsenic and antimony species in surface transects and depth profiles across a frontal zone: The Chatham Rise,New Zealand

Measurements of total dissolved arsenic (As(III+V)) and antimony (Sb(III+V) and their simple methylated species are presented for samples collected from three vertical profiles and along three surface transects in the Chatham Rise region, east of New Zealand. As(III+V) concentrations showed a slight increase with depth (16–17 nM at 25 m to 20 nM at 100 m) whereas Sb(III+V) concentrations were conservative with depth (1.02–1.12 nM). Along the three surface water transects, As(III+V) and Sb(III+V) concentrations showed little variation, with average concentrations of 18±2 and 0.99±0.05 nM, respectively. Inorganic arsenic was not correlated with orthophosphate (r²=0.01). Monomethyl- and dimethyl-arsenic (MMAs, DMAs) concentrations (0.04–0.01 and 0.65–0.07 nM, respectively) decreased with depth, suggesting surface water production by biota and degradation at depth. Along the Chatham Rise transect, DMAs concentrations increased on the Rise (0.65 nM maximum) compared to waters north and south of the Rise (∼0.22 nM). Fluctuation in MMAs concentrations were also seen for water samples collected on the Chatham Rise. Monomethyl-, dimethyl- and trimethyl-antimony (MMSb, DMSb, TMSb) species were detected in water samples collected along all the three surface water transects suggesting surface water production by biota. Concentrations of MMSb, DMSb and TMSb in water samples were fairly constant along all the three surface transects (0.06–0.07, 0.015–0.025 and 0.005–0.015 nM, respectively), showing no significant enrichment on the Chatham Rise. These arsenic and antimony results support the current global view that inorganic As and Sb are conservative and the methyl species are of biological origin.     

南极普里兹湾及其邻近海域溶解有机碳的分布

中国南极科学考察第16航次期间(1999年11月～2000年4月),在南极普里兹湾及邻近海域的不同站位与水深采集海水样品用于溶解有机碳测定,通过高温催化氧化法完成样品的分析.结果表明,在调查期间,南极普里兹湾及其邻近海域各测站上层水体(0～100m)溶解有机碳浓度的变化范围为14.3～181.1μmol/dm3,平均为52.5μmol/dm3,该变化幅度比Ross海、太平洋等海域的相应值略大.溶解有机碳垂直分布的特征是0大于25大于50大于100m,即随深度的增加溶解有机碳浓度逐渐减小,与生物活动在垂直方向上的强弱变化相关.根据200m以深水柱溶解有机碳的垂直分布,可确定研究海域难降解溶解有机碳的浓度为40.4μmol/dm3,与其他研究所报道的数值(～42μmol/dm3)相近.上层水体(0～100m)过剩溶解有机碳的空间分布显示,64°S以北海域溶解有机碳过剩较多,而64°S以南海域则过剩溶解有机碳较少.溶解有机碳浓度与分布特征显示,普里兹湾及其邻近海域溶解有机碳浓度与南大洋其他海域相当,具有低溶解有机碳的一般特征.溶解有机碳浓度的空间分布呈现由西南向东北方向逐渐增加的趋势,这可能与南极陆架夏季上层水的北向扩展有关.生物活动及水体运动是研究海域溶解有机碳分布的主要影响因素.     

Effects of hexavalent and trivalent chromium on the reproduction of Neanthes arenaceodentata (polychaeta)

This study compared the very different responses of the polychaete Neanthes arenaceodentata to chronic exposure of hexavalent (Cr VI) and trivalent (Cr III) chromium. The polychaetes were exposed to sublethal concentrations of Cr VI and Cr III for periods of 440 days (three generations) and 293 days (two generations), respectively. In the Cr VI test, polychaete reproduction ceased at 100 μg litre^?1, and the number of young produced was reduced at the 12·5 to 50 μg litre^?1 levels and above. However, polychaetes that lived in Cr III during the test showed no adverse effects in 50400 μg litre^?1.     

早第四纪西太平洋底栖有孔虫群与大洋深层水环流演化的关系

选取赤道西太平洋ODP 807站位(3°36.42′N,156°37.49′E,水深2 803.8m,岩心长822.9m)26.27～43.02mbsf层段中的底栖有孔虫进行研究,以便了解早更新世2.5～1.6Ma BP时期古生产力和深水环流的变化。结果显示,这一时期底栖有孔虫堆积速率(BFAR)、表生种和内生种比值(E/I)、Uvigerina spp.百分含量和有机碳百分含量(TOC%)等替代指标反映了西太平洋古生产力总体上呈现冰期高、间冰期低的特点,而其中Bulimina alazanensis的丰度变化则相反,反映了该种有可能更适合温暖、低营养的底层水环境。2.5～1.6 MaBP时期底栖有孔虫在丰度上以Uvigerina spp.为主,指示了早更新世西太平洋深层水受北部水团的控制更强。     

Chromium in Cascadia Basin,northeast Pacific Ocean

Water samples from a Pacific Ocean basin have been analysed for a number of forms of chromium. Total Cr, almost entirely as dissolved Cr(VI), steadily increases with depth and correlates most closely with silica data. Mid-depth regeneration of Cr is suggested by a multiple regression equation which includes Cr(total), silica and phosphate data.The release of Cr and silica from bottom sediments is apparent as the continental margin is approached. Box model transport calculations suggest that a Cr flux from the sediments on the order of 100 nmol Cr m^?2 day^?1 could be balanced by horizontal and vertical eddy diffusion coefficients of 10⁶ and 10 cm² s^?1, respectively, and by horizontal and vertical advection rates of 10^?2 and 10^?4 cm s^?1, respectively.     

Biogeochemical impact of a model western iron source in the Pacific Equatorial Undercurrent

Trace element distributions in the source waters of the Pacific Equatorial Undercurrent (EUC) show the existence of elevated total acid-soluble iron concentrations. This region has been suggested to contribute enough bioavailable iron to regulate interannual and interglacial variability in biological productivity downstream in the high-nitrate low-chlorophyll upwelling zone of the eastern equatorial Pacific. We investigated the advection and first-order biogeochemical impact of an imposed, data-based iron maximum in the western Pacific EUC using an ecosystem model forced by a global dynamical model. We imposed two source profiles of iron constrained by total acid-soluble iron measurements. Though the data for total acid-soluble iron included both dissolved and acid-soluble particulate iron species, we treated all of the total acid-soluble iron as if it was dissolved and bioavailable. A deeper (270 m) source was centered in the density horizon of the observed iron maximum and a shallower (180 m) source was located in the core of our model's EUC, where a dissolved iron maximum has been frequently postulated. These source runs were compared with a control run that contained no specific source of iron associated with the EUC. In the source runs elevated iron concentrations were simulated in the EUC across its entire zonal span, evident as a subsurface plume of dissolved iron slightly below the core of the EUC. In the control run there was no iron maximum associated with the EUC. Upwelling of iron-replete water in the central and eastern equatorial Pacific increased integrated primary productivity in the Wyrtki box (180°W:90°W, 5°S:5°N, 0:200 m) by 41% and 66% for the deeper and shallower iron perturbation, respectively. The source runs increased the realism of the zonal extent of HNLC conditions and the meridional distributions of biological productivity, relative to the control run. However, in the source simulations surface chlorophyll concentrations were too high by a factor of two and maximum surface nitrate concentrations were too low, relative to climatologies. The relative abundance of diatoms roughly doubled upon the input of additional iron, exceeding field observations. Though biogeochemical data are limited and we did not adjust parameters to optimize the model fits to observations, these results suggest that acid-soluble particulate iron supplied to the EUC in the western equatorial Pacific is unlikely to be entirely bioavailable.     

Geochemical and hydrodynamic constraints on the distribution of trace metal concentrations in the lagoon of Nouméa, New Caledonia

Seawater samples were collected in the lagoon of Nouméa (southwest New Caledonia) along two transects from eutrophic coastal bays to the oligotrophic barrier reef. Land-based emissions to the lagoon were measured with dissolved and particulate concentrations of chromium (Cr) and nickel (Ni), used as tracers of both terrigenous and industrial (Ni ore treatment) activities, as well as dissolved and particulate concentrations of zinc (Zn), used as a tracer of urban effluents. The spatial variability of metal concentrations was related to geochemical and hydrodynamic conditions, i.e., respectively: (1) natural and anthropogenic emission sources, and chemical processes occurring in the water column; and (2) water residence times. The parameter used to describe the residence time of water masses was the local e-flushing time, i.e. the time required for a tracer mass contained within a given station to be reduced by a factor 1/e. High metal concentrations were found in coastal areas (up to 9000 ng dissolved Ni L⁻¹), and steeply decreased with distance from the coast (down to 101 ng dissolved Ni L⁻¹ near the barrier reef) to reach levels similar to those found in remote Pacific waters, suggesting a rapid renewal of waters close to the barrier. Distributions of metals in the lagoon are controlled upstream by land-based emission sources and later chemical processes. Then hydrodynamics constrain metal distributions, as shown by the observed relationship between local e-flushing times and the spatial variability of metal concentrations. In addition, a change in the direction of prevailing winds yielded a decrease of dissolved metal concentrations at the same site by a factor of 2.5 (Cr and Ni) and 2.9 (Zn). It is suggested that the residence time is a key parameter in the control of elemental concentrations in the lagoon waters, as much as land-based emission sources.