Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

A time-series study of particulate matter export in the North Pacific Subtropical Gyre based on Th : U disequilibrium

Depth profiles of total ²³⁴Th (dissolved+particulate) were collected at Station ALOHA (22°45N, 158°00W) in the North Pacific Subtropical Gyre during 9 cruises from April 1999 to March 2000. Samples were collected and processed by a new 2 L technique that enables more detailed depth resolution then previous ²³⁴Th studies. Significant zones of particle export (²³⁴Th deficiency) and particle remineralization (²³⁴Th excess) were measured both temporally and with depth. ²³⁴Th derived particulate carbon (PC) and nitrogen (PN) fluxes were determined with steady-state and non-steady-state models and PC/²³⁴Th and PN/²³⁴Th ratios measured with both in situ pumps and free-drifting particle interceptor traps deployed at 150 m. ²³⁴Th based export estimates of 4.0±2.3 mmol C m⁻² d⁻¹ and 0.53±0.19 mmol N m⁻² d⁻¹, were approximately 60% higher than those measured in PIT style sediment traps from the same time period, 2.4±0.2 mmol C m⁻² d⁻¹ and 0.32±0.08 mmol N m⁻² d⁻¹. Most of this difference is attributable to two large export events that occurred during October and December 1999, when traps undercollected for ²³⁴Th by a factor of 2 to 4. ²³⁴Th export (ThE) ratios based on ²³⁴Th derived PC flux/¹⁴C based primary production ranged from 4% to 22% (average=8.8%). Our results confirm the recent estimates of C export by Emerson et al. (Nature 389 (1997) 951) and Sonnerup et al. (Deep-Sea Research I 46 (1999) 777) and indicate that C export from the oligotrophic ocean must be considered when discussing C sequestration in global climate change.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

Recognition of environmental trace metal contamination using pine needles as bioindicators. The urban area of Palermo (Italy)

Pinus pinea L., collected in and around the city of Palermo were analysed for major and trace elements by INAA and ICP-MS. The chemical composition of pine needles suggests that the presence of Pb, Sb and Br in excess with respect to soil composition is due to anthropogenic emissions. The anomalously high values of these elements observed in the urban area decrease outside town. Lead isotope data confirm the anthropogenic origin of lead. The origin of Zn and Cu excess remains uncertain at the moment, although wholly-crustal origin appears doubtful. Morphological alterations attributable to phenol accumulation, such as modifications in the length of mesophyll cells and the appearance of lacunae in the distal portions, were observed in needles. The accumulation of phenols, linked to the presence of lead, gives rise to a specific pattern of metabolites providing mechanisms of detoxification and protection, so that the accumulation degree may be proposed as a marker of environmental pollution. Received: 4 June 1999 · Accepted: 24 June 1999     

Characteristics of selenium migration in soil–plant system of East Meshchera and Transbaikalia

Herein some results of comparative researches to determine the parameters of selenium migration in meadow biogeocenoses of East Meshchera and East Transbaikalia are presented. The parameters of selenium mobility in soils (i.e., the element total content, plant-accumulation coefficient (Kb) and/or mobile form ratio) in Urov biogeochemical provinces of the East Transbaikalia are quite comparable to the element migration parameters found in selenium-deficient landscapes of the same area. Selenium mobility indices and ecological status are significantly higher for meadow biogeocenoses of the East Meshchera (Moscow Region) and also for limestone soils.     

沉积物－水界面的生物地球化学作用

沉积物－水界面是天然水体在物理、化学和生物特征等方面差异性最显著和负责水体和沉积物之间物质输送和交换的重要边界环境。对沉积物－水界面生物地球化学的定义、研究方法和它在水体微量物质循环中所起的作用、物质迁移方式、典型氧化还原敏感性元素转化反应（Ｃ、Ｏ、Ｎ）、界面扩散通量和表面扩散亚层的意义和估算等进行了讨论。     

An Overview of the Applications of Lipid Carbon Isotope Compositions in the Paleoenvironmental and Paleoecological Reconstructions in Lacustrine and Peat Deposits

Lipids preserved in geological materials mainly originate from cell membrane and leaf waxes, and have the potential to infer biological sources, metabolic pathways, and environmental information. Thus,lipid-based proxies have been widely applied to reconstruct paleoenvironment and paleoecology in the Quaternary. Except the concentration and molecular composition, the carbon isotope compositions of lipids are also a type of important signal sources. For photoautotrophs, the carbon isotope compositions of lipids are mainly mediated by the carbon isotope discrimination during the photosynthesis and lipid biosynthesis processes. In contrast, the carbon isotope compositions of heterotroph derived lipids are controlled by substrates and the carbon isotope fractionation during biosynthesis. In this review, we overview the advances of applications of lipid carbon isotope ratios in lacustrine and peat deposits. In the near future, more attention is suggested to pay to instrumental techniques, such as reduce the sample amount, direct analysis the carbon isotope compositions of molecules with relatively large molecular weight (e.g. BHPs, GDGTs), and widely application of compound-specific radiocarbon isotope analysis. In addition, combination of carbon isotope ratios from multi lipids, or the application of dual carbon and hydrogen isotope ratios of lipids, will shed more information on the response of ecological processes to climate changes. Furthermore, more works are worthy to investigate the relation between biogeochemical processes and paleoclimate changes in the Quaternary.     

Effects of an estuarine plume-associated bloom on the carbonate system in the lower reaches of the Pearl River estuary and the coastal zone of the northern South China Sea

We observed a phytoplankton bloom downstream of a large estuarine plume induced by heavy precipitation during a cruise conducted in the Pearl River estuary and the northern South China Sea in May–June 2001. The plume delivered a significant amount of nutrients into the estuary and the adjacent coastal region, and enhanced stratification stimulating a phytoplankton bloom in the region near and offshore of Hong Kong. A several fold increase (0.2–1.8 μg Chl L⁻¹) in biomass (Chl a) was observed during the bloom. During the bloom event, the surface water phytoplankton community structure significantly shifted from a pico-phytoplankton dominated community to one dominated by micro-phytoplankton (>20 μm). In addition to increased Chl a, we observed a significant drawdown of pCO₂, biological uptake of dissolved inorganic carbon (DIC) and an associated enhancement of dissolved oxygen and pH, demonstrating enhanced photosynthesis during the bloom. During the bloom, we estimated a net DIC drawdown of 100–150 μmol kg⁻¹ and a TAlk increase of 0–50 μmol kg⁻¹. The mean sea–air CO₂ flux at the peak of the bloom was estimated to be as high as ∼−18 mmol m⁻² d⁻¹. For an average surface water depth of 5 m, a very high apparent biological CO₂ consumption rate of 70–110 mmol m⁻² d⁻¹ was estimated. This value is 2–6 times higher than the estimated air–sea exchange rate.     

A comparison of selective extraction soil geochemistry and biogeochemistry in the Cobar area, New South Wales

In parts of the deeply weathered and semi-arid environments of the Cobar area (NSW, Australia), detection of mineralisation using conventional soil sampling and total metal analysis is impeded. This is due to the intense leaching of trace elements within the weathered profile, discontinuous coverage of transported materials and the existence of diffuse regional geochemical anomalies of ill-defined source. Selective chemical extractions, applied to various regolith components, and biogeochemistry offer a means of isolating localised geochemical patterns related to recent dispersion of trace elements through the overburden. Lag geochemical patterns across the McKinnons deposit (Au) and Mrangelli prospect (Pb–Zn–As) reflect mechanical dispersion processes and minor hydromorphic effects. Concentrations of more mobile elements tend to be higher in the non-magnetic fraction, due to higher proportions of goethite and poorly crystalline hematite than in the magnetic fraction. The subdued soil geochemical responses for metals extractable by cold 40% hydrochloric acid (CHX) and for total element concentration reflect the leached nature of the residual profile, low grade of mineralisation, dilution by aeolian components and disequilibrium of fine fractions with coarser, relict Fe-oxides. The stronger contrast for CHX for most metals, compared with total extraction, indicates surface accumulation of trace elements derived from underlying mineralisation. Enzyme leach element anomalies are intense but generally located directly over bedrock sources or major structural breaks, irrespective of the nature of the overburden. Though mechanisms for the dispersion of trace elements extracted by enzyme leaching are not well established, the lack of lateral transport suggests vertical migration of volatile metal species (atmimorphic dispersion). The strong, multi-element response to mineralisation in cypress pine needles indicates significant metal recycling during the present erosional cycle. However, a comparison of the trace element concentrations in vegetation (cypress pine needles) and selective extractions of soils indicates that recycling by the plants is not the dominant mechanism for transportation of metals through the overburden. The vegetation may be responding to hydromorphic dispersion patterns at depth. The use of selective extractions may be useful in detecting mineralisation through deeply leached profiles, but offers even greater potential when integrated with biogeochemistry to detect targets buried by significant thickness of transported cover.     

Downscaling biogeochemistry in the Benguela eastern boundary current

Dynamical downscaling is developed to better predict the regional impact of global changes in the framework of scenarios. As an intermediary step towards this objective we used the Regional Ocean Modeling System (ROMS) to downscale a low resolution coupled atmosphere–ocean global circulation model (AOGCM; IPSL-CM4) for simulating the recent-past dynamics and biogeochemistry of the Benguela eastern boundary current. Both physical and biogeochemical improvements are discussed over the present climate scenario (1980–1999) under the light of downscaling.Despite biases introduced through boundary conditions (atmospheric and oceanic), the physical and biogeochemical processes in the Benguela Upwelling System (BUS) have been improved by the ROMS model, relative to the IPSL-CM4 simulation. Nevertheless, using coarse-resolution AOGCM daily atmospheric forcing interpolated on ROMS grids resulted in a shifted SST seasonality in the southern BUS, a deterioration of the northern Benguela region and a very shallow mixed layer depth over the whole regional domain. We then investigated the effect of wind downscaling on ROMS solution. Together with a finer resolution of dynamical processes and of bathymetric features (continental shelf and Walvis Ridge), wind downscaling allowed correction of the seasonality, the mixed layer depth, and provided a better circulation over the domain and substantial modifications of subsurface biogeochemical properties. It has also changed the structure of the lower trophic levels by shifting large offshore areas from autotrophic to heterotrophic regimes with potential important consequences on ecosystem functioning. The regional downscaling also improved the phytoplankton distribution and the southward extension of low oxygen waters in the Northern Benguela. It allowed simulating low oxygen events in the northern BUS and highlighted a potential upscaling effect related to the nitrogen irrigation from the productive BUS towards the tropical/subtropical South Atlantic basin. This study shows that forcing a downscaled ocean model with higher resolution winds than those issued from an AOGCM, results in improved representation of physical and biogeochemical processes.