On the quantitative importance of heterotrophic microplankton in the northern German Wadden Sea

To assess the importance of heterotrophic microplankton in the Wadden Sea, seasonal distribution and biomass of the main subgroups, that is, heterotrophic dinoflagellates, (separated into thecate and athecate forms), tintinnids, and aloricate ciliates, were studied in 1989 and 1990 in a total of six surveys covering the whole area of the northern German Wadden Sea. Heterotrophic microplankton biomass exhibited high spatial and temporal variation, ranging from 0 μg Cl^?1 to 66 μg Cl^?1, with maximum concentrations in spring., Mean stocks were lowest in winter (1.6 μg Cl^?1) and highest in spring (11.7 μg Cl^?1); intermediate concentrations were found in summer (8.5 μg Cl^?1). In winter, the heterotrophic microplankton was dominated by tintinnids. In spring and summer, aloricate ciliates and dinoflagellates made up the largest part of the biomass. A pronounced feature was a shift within the dinoprotist group from athecate to thecate forms in summer. In spring, maxima of athecate dinoflagellate carbon were associated with blooms ofPhaeocystis globosa, indicating a close trophic relationship. From rough estimates of the daily grazing potential, based on microheterotrophic biomass and conversion factors from the literature, it may be concluded that heterotrophic microplankton temporarily share a main role in the transfer of food and energy to higher trophic levels within the pelagic system of the Wadden Sea.     

Origin and composition of organic matter in tidal flat sediments from the German Wadden Sea

Two sediment cores of up to 550 cm length from an intertidal flat of the German Wadden Sea near the island of Spiekeroog were investigated for the quantity and composition of fossil organic matter (OM). The lowermost parts of the cores are dominated by grey mud of a salt marsh facies containing mainly terrestrial OM estimated to account for 60–75% of the total OM, based on δ¹³C values and the ratio of short to long chain n-alkanols. The terrigenous origin of the dominant fraction is indicated, among others, by high proportions of C₂₉ sterols and long chain n-alkanes typical of plant waxes. Coarse shell beds overlying the grey mud at 2–2.5 m depth represent a flooding and erosion event possibly related to heavy storm floods in the Middle Ages. Within the intertidal sand-dominated sediments in the upper parts of the cores total organic carbon (TOC) contents are generally low, ranging from 0.1% to 0.5%, and correlate well with the amount of mud fraction (r² 0.90). At the surface, marine OM has not undergone intense diagenetic alteration and so is the dominant fraction. Eroded peat particles are common throughout most of the sequence and values of the Phragmites peat indicator (PPI) > 5 indicate an origin from reed peat due to a high relative abundance of the n-C₂₄ alkane. Changes in the composition of microbial communities over the depth interval investigated are documented by varying compositions of unsaturated fatty acids with 16 and 18 carbons. Eicosapentaenoic acid (EPA) was detected along the entire cores and indicates the presence of EPA-producing bacterial strains.     

Distribution of uranium in German bottled and tap water

The results presented in this paper on uranium in bottled and tap water were determined within the scope of the project “European Groundwater Geochemistry: Bottled Water” of the Geochemistry Expert Group of EuroGeoSurveys. The analyses of bottled water provide an inexpensive approach to obtain information about European groundwater geochemistry. For this study, the uranium concentrations in 1785 European mineral water samples were analyzed by ICP–QMS in the BGR laboratories. The dataset is used to obtain a first impression about natural concentration levels and variation of uranium in groundwater (and bottled water) at the German and European scale.     

Process-response analysis for Hörnum tidal inlet in the German sector of the Wadden Sea

The Hörnum tidal inlet is located in the German sector of the Wadden Sea between the barrier islands Sylt and Amrum. On the basis of seven bathymetric surveys of the tidal inlet covering a 55-yr period from 1939 to 1994 and long-term records from two tide gauges, a process-response analysis for the inlet was carried out. Following the method described by Dean and Walton (1975), the volume of sediment stored in the ebb–tidal delta (V_ebd) was calculated for each survey. Furthermore, the cross-sectional area of the tidal inlet throat (A_c), and the area-height distribution (hypsographic curve) of the study area were established. Between 1939 and 1994, A_c increased by about 32%, whereas V_ebd diminished by about 18%. Earlier investigations by, e.g., O'Brien (1931), Walton and Adams (1976), Dean (1988), and Eysink and Biegel (1992) documented a strong positive correlation between these two morphological parameters and tidal currents in the inlet. In conformity with the literature, regression of the values of A_c with the corresponding fall velocities of the water level in the inlet (a direct indication of ebb–tidal currents) produced a correlation coefficient (r) of 0.87. However, V_ebd shows a weak negative correlation (r=−0.74) with fall velocities of the water level. Apparently, other factors than changes in ebb–tidal currents must have been responsible for the decrease in V_ebd. It is suggested that one factor might be the observed considerable increase in storminess, i.e. wave action, in the region since approximately 1960. Consequently, storm wave action on the ebb–tidal delta intensified and erosion was here initiated. As a result, the swash bars of the ebb–tidal delta, in particular, suffered from severe erosion between 1959 and 1994. As the ebb–tidal currents increased simultaneously, sand supply to the terminal lobe of the ebb–tidal delta increased as well, thereby balancing the loss of sediment from the terminal lobe caused by the increasing storminess. The results of this case study indicate that the ratio of ebb–tidal currents to (storm) wave action determines, in large part, the value of V_ebd.     

The chemical composition of sea water and pore water in the manganese nodule area of the Central Pacific

Analyses for the following elements were made on 118 samples of pore water and 23 samples of sea water from the radiolarian ooze area of the Central Pacific: Na, Ca, Br, Sr (major elements) and Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Rb, Ag, Sb, Cs, Eu, Ta, Hg, U.The average concentration of most of the elements analyzed is higher in the pore water than in the sea water. The enrichment of elements in both the pore water and the bottom near sea water relative to the average composition of the sea water depends on the residence times of the elements in the sea water — the shorter the residence time the greater the enrichment.The enrichment of an element in these sea and pore waters is also dependant on the chemical species in which it occurs in the sea water. The enrichment seems to be greater for hydroxides, less for complex chloride ions and there is no enrichment for simple ions. The enrichment of the elements occuring as hydroxides (Fe, Cu, Cr, Sc, Eu) or complex chlorides (Mn, Ni, Co, Zn, Ag, Hg, Se) results in precipitation from the sea water, which contributes to the growth of the manganese nodules as well as to the genesis of metalliferous sediments in this area. The greater enrichment in the pore water relative to the sea water accounts for the remobilization of these elements from the sediment as the main source of the material for the growth of the manganese nodules.

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Zusammenfassung 118 Porenwasser- und 23 Meerwasser-Proben aus dem Radiolarienschlammgebiet des Mittleren Pazifik wurden auf folgende Elemente analysiert: Na, Ca, Br, Sr (Hauptbestandteile) und Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Rb, Ag, Sb, Cs, Eu, Ta, Hg, U.Die durchschnittliche Konzentration der meisten bestimmten Elemente ist im Porenwasser höher als im Meerwasser. Die Elementaranreicherung sowohl im Porenwie im bodennahen Meereswasser ist im Vergleich zur weltweiten Durchschnittszusammensetzung des Meerwassers abhÄngig von den Verweilzeiten der Elemente im Meer — je kürzer die Verweilzeit, desto grö\er die Anreicherung.Die Anreicherung eines Elements in diesen Meeres- und PorenwÄssern hÄngt auch von der chemischen Spezies ab, in der es im Meerwasser vorkommt. Die Anreicherung scheint grö\er zu sein für Hydroxide, geringer für komplexe Chlorid-Ionen, und es gibt keine Anreicherung für einfache Ionen. Die Anreicherung der Elemente, die als Hydroxide (Fe, Cu, Cr, Se, Eu) oder komplexe Chloride (Mn, Ni, Co, Zn, Ag, Hg, Se) vorkommen, führt zur AusfÄllung aus dem Meereswasser. Diese AusfÄllung trÄgt bei zum Wachstum der Manganknollen und zur Entstehung von metalliferous sediments in diesem Gebiet. Die grö\ere Anreicherung im Porenwasser im Vergleich zum Meereswasser spricht für die Mobilisierung dieser Elemente aus dem Sediment als der wichtigsten Materialquelle für das Wachstum der Manganknollen.

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Résumé Dans la région des boues á radiolaires de l'Océan Pacifique central 118 échantillons d'eau interstitielle et 23 échantillons d'eau de mer ont été prélevés et analysés. Les éléments suivants ont été déterminés: Na, Ca, Br, Sr (éléments principaux) et Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Rb, Ag, Sb, Cs, Eu, Ta, Hg, U.La concentration moyenne de la majorité des éléments analysés est plus grande dans l'eau interstitielle que dans l'eau de mer. L'enrichissement des éléments dans l'eau interstitielle ainsi que dans l'eau de mer près du fond, comparé aux valeurs moyennes dans l'eau de mer, dépend du temps de séjour de l'élément dans l'eau de mer — le plus court est le temps du séjour, plus fort est l'enrichissement.L'enrichissement d'un élément dans ces échantillons d'eau interstitielle et d'eau de mer dépend également de la forme chimique sous laquelle il se trouve dans l'eau de mer. Il semble que l'enrichissement est plus fort pour les hydroxides, et moindre pour les ions chlorurés complexes. Il n'ya pas d'enrichissement en ions simples. L'enrichissement des éléments sous forme d'hydroxides (Fe, Cu, Cr, Sc, Eu) ou de chlorures complexes (Mn, Ni, Co, Zn, Ag, Hg, Se) entraine la précipitation de ces éléments hors de l'eau de mer, ce qui contribut à la croissance des nodules de manganèse ainsi qu'à la genèse des sédiments métallifères dans cette région. L'enrichissement plus fort dans l'eau interstitielle par rapport à l'eau de mer rend compte de la remobilisation de ces éléments à partir du sédiment comme source principale de matière pour la croissance des nodules de manganèse.

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118 23 : Na, , Br, Sr ( ) Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, Se, Rb, Ag, Sb, Cs, u, , Hg, U. , . , , — , . - , : , . — Fe, Cu, Cr, Sc, u -, — Mn, Ni, , Zn, Ag, Hg, Se - . , . 3 , , .

     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

High-resolution profiles of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment

The remobilization of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment cores at Yingkou was assessed using diffusive equilibrium in thin films and diffusive gradients in thin films techniques. A relatively anoxic system (+33.7 to ?224.1 mV) in the sediment cores might cause the reductive release of iron, manganese and cobalt into pore water from the estuarine sediment. High-average concentrations of iron (47.85 μg ml^?1) and manganese (3.81 μg ml^?1) were observed using diffusive equilibrium in thin films on the sediment core, but the concentration of cobalt (18.02 ng ml^?1) was relatively low. A strong correlation between iron and cobalt was observed based on the vertical profiles of the metals. Manganese and iron were more readily released from the solid phase to the solution. The peak cobalt, copper and zinc concentrations were observed in the upper layer (2–4 cm) measured using diffusive gradients in thin films. However, the peak iron, manganese and cobalt concentrations were located in the deeper layer (≥7 cm). In addition, the concentration profiles measured using diffusive gradients in thin films of cobalt, copper and zinc were independent of the iron, manganese and cobalt distribution with respect to depth.     

Iron and manganese diagenesis in deep sea volcanogenic sediments and the origins of pore water colloids

Volcanogenic sediments are typically rich in Fe and Mn-bearing minerals that undergo substantial alteration during early marine diagenesis, however their impact on the global biogeochemical cycling of Fe and Mn has not been widely addressed. This study compares the near surface (0-20 cm below sea floor [cmbsf]) aqueous (<0.02 μm) and aqueous + colloidal here in after ‘dissolved’ (<0.2 μm) pore water Fe and Mn distributions, and ancillary O_2(aq), and solid-phase reactive Fe distributions, between two volcanogenic sediment settings: [1] a deep sea tephra-rich deposit neighbouring the volcanically active island of Montserrat and [2] mixed biosiliceous-volcanogenic sediments from abyssal depths near the volcanically inactive Crozet Islands archipelago. Shallow penetration of O_2(aq) into Montserrat sediments was observed (<1 cmbsf), and inferred to partially reflect oxidation of fine grained Fe(II) minerals, whereas penetration of O_2(aq) into abyssal Crozet sediments was >5 cmbsf and largely controlled by the oxidation of organic matter. Dissolved Fe and Mn distributions in Montserrat pore waters were lowest in the surface oxic-layer (0.3 μM Fe; 32 μM Mn), with maxima (20 μM Fe; 200 μM Mn) in the upper 1-15 cmbsf. Unlike Montserrat, Fe and Mn in Crozet pore waters were ubiquitously partitioned between 0.2 μm and 0.02 μm filtrations, indicating that the pore water distributions of Fe and Mn in the (traditionally termed) ‘dissolved’ size fraction are dominated by colloids, with respective mean abundances of 80% and 61%. Plausible mechanisms for the origin and composition of pore water colloids are discussed, and include prolonged exposure of Crozet surface sediments to early diagenesis compared to Montserrat, favouring nano-particulate goethite formation, and the elevated dissolved Si concentrations, which are shown to encourage fine-grained smectite formation. In addition, organic matter may stabilise authigenic Fe and Mn in the Crozet pore waters. We conclude that volcanogenic sediment diagenesis leads to a flux of colloidal material to the overlying bottom water, which may impact significantly on deep ocean biogeochemistry. Diffusive flux estimates from Montserrat suggest that diagenesis within tephra deposits of active island volcanism may also be an important source of dissolved Mn to the bottom waters, and therefore a source for the widespread hydrogenous MnO_x deposits found in the Caribbean region.     

A Comprehensive Study of Silica Pools and Fluxes in Wadden Sea Salt Marshes

As an essential nutrient for diatoms, silica plays a key role in the estuarine and coastal food web. High concentrations of dissolved silica (DSi) were found in the seepage water of tidal freshwater marshes, which were therefore assumed to contribute to the silica supply to estuarine waters in times of silica limitation. A comprehensive budget calculation for European salt marshes is presented in this study. Earlier, salt marshes were considered to have even higher silica recycling rates than tidal freshwater marshes. Between 2009 and 2011, concentrations, pools and fluxes of silica in two salt marshes at the German Wadden Sea coast were determined (in soil, pore water, aboveground vegetation, freshly deposited sediments and seepage water). Subsequently, a budget was calculated. Special emphasis was placed on the influence of grazing management on silica cycling. Our results show that the two salt marshes were sinks for silica. The average import of biogenic silica (BSi) with freshly deposited sediments (1,334 kmol km^?2 year^?1) largely exceeded the DSi and BSi exports with seepage water (80 kmol km^?2 year^?1). Grazing management can affect silica cycling of salt marshes by influencing hydrology and vegetation structure. Abandoned sites had larger DSi export rates than grazed sites. One third of all BSi imports occurred in only one major flooding, underlining the relevance of rare events in the silica budget of tidal marshes. This aspect has been widely neglected in earlier studies, what might have led to an underestimation of silica import rates to tidal marshes hitherto.     

Ionic composition of pore water in shallow shelf deposits of the Laptev Sea

The cationic and anionic compositions of pore water in shallow deposits of Buor-Khaya Bay is studied. Significant concentration heterogeneity of the vertical ionic profile in the studied drill columns is shown. It is established that the vertical ionic profile of shelf deposits of the Laptev Sea is basically formed under the influence of thawing of underwater permafrost, hydrodynamic conditions, the water mass, and heat flows and depends on the lithological and granulometric types of the deposits. The highest concentrations of ions are registered in plant detritus represented by ground grass vegetation. A relationship between the ionic composition of pore water and cryogenic state of the sequence and its variability is demonstrated using the method of major components.     

Distinction between sortable silts and aggregated particles in muddy intertidal sediments of the East Frisian Wadden Sea, southern North Sea

In muddy sediments, the distinction between sortable silt and aggregated silty clay is important for the understanding of fine particle dynamics because both have different hydraulic properties. The Wadden Sea of the southern North Sea is severely depleted in fine-grained sediments mainly due to high energy levels along the diked coastline. As a result, muddy sediments are restricted to a narrow belt along the diked mainland shore. In the present study, the mechanism by which this mud is deposited and how floc deposition and break-up are reflected in the size distribution, has been investigated. For this purpose, surficial sediments from four intertidal nearshore transects were monitored and repeatedly sampled in the course of two years. High-resolution grain-size analyses were performed by an automated settling tube and a Sedigraph particle analyser for the sand and mud fractions, respectively.The grain size frequency distributions of the fine fractions demonstrate that the Wadden Sea muds are composed of two subpopulations, a well-sorted coarse silt and an unsorted silty clay population. A depletion of grain size around 8 μm (7 phi) demarcates the grain-size boundary between the two populations, suggesting that the finer mud population (< 8 μm) is deposited in the form of flocs and aggregates which are hydraulically equivalent to the local sands and coarser silts. Floc break-up and reconstitution in response to seasonally changing energy regimes lead to apparent seasonal sedimentation patterns in the back-barrier tidal basins. Furthermore, in the course of sample preparation, the flocs and aggregates are broken down into their constituent particles. This mechanical artefact in the size distributions produces an artificial seasonal fining/coarsening pattern. It was found that the comparison of clay/silt and < 8 μm/63 − 8 μm particle ratios are good indicators of floc behaviour. Higher ratios are found in mixed flats which are relatively protected from wave action, thereby promoting deposition of flocs. In addition, progressive size sorting and mixing processes along the transects are recognized in the frequency distributions of sands. The skewness pattern shows a landward decrease in positive values, which is exactly opposite to previously reported patterns, suggesting progressive winnowing of fine particles caused by increased wave action over the last decade. This effect of climate change further promotes depletion of fine-grained sediments in the basin.     

Application of formaldoxime colorimetric method for the determination of manganese in the pore water of anoxic estuarine sediments

The formaldoxime colorimetric method for manganese, previously utilized for freshwater and seawater samples of large volume, has been modified for the analysis of small volume, iron-rich sediment pore water samples. Using as little as 3 ml of sample and the addition of EDTA to destroy the Fe-formaldoxime interference (at concentrations of 9 μM Mnl^?1), a precision of 3% is obtained.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

东沙群岛海域沉积物游离烃和孔隙水特征及其地球化学意义

对东沙群岛海域HD170和HD196A两个站位，通过系统的顶空气和孔隙水离子取样测试，对柱状样沉积物和底层水中游离甲烷的含量和沉积物孔隙水的离子组成特征以及孔隙水的来源进行了分析。游离气的分析表明，多数沉积物样品中游离甲烷的含量小于20μL／kg，但在HD196A站位，随着沉积物在海底以下埋深的增加，其中的游离甲烷含量迅速增加，在754～774cm，沉积物中游离甲烷的含量达到了7468．66μL／kg，推测其下存在巨大的烃类供应源。孔隙水的^86St／^87Sr同位素测试显示，本文所研究的两个站位沉积物孔隙水来源于正常的海洋沉积过程，而δ^11B的特征表明，沉积物中存在着与海水交换的吸附水，并且HD170站位的交换更多。柱状样沉积物孔隙水中，Ca^2＋、Mg^2＋与SO4^2-浓度表现出随着深度增加而明显降低的趋势，其中HD196A站位的硫酸盐甲烷界面小于10mbsf，暗示了该站位深部很可能赋存天然气水合物。     

Geochemical behaviour of iron and manganese ions in the Ningyo-Toge uranium deposit district, southwest Japan

The Ningyo-Toge uranium deposit is one of the typical sedimentary uranium deposits in Japan. In general, during weathering, U is removed from the basal granite through underground water. The underground water in this area is rich in U, and has a comparatively high concentration of Fe and Mn.

In this area, three types of Fe minerals can be recognized in different modes of occurrence: (1) in the oxide zone brownish Fe-hydroxide mineral with ferric ion, i.e. goethite (-FeOOH); (2) in the reduced zone of the mine gallery pale-blue Fe-hydroxide mineral with some ferrous ion, i.e. lepidocrocite (γ-FeOOH); and (3) Fe-sulphate minerals such as melanterite (FeSO₄·7H₂O), etc. Some uranyl sulphate minerals, uranopilite and zippeite, are closely associated with these Fe-sulphate minerals. Under weakly alkaline conditions of the oxidizing environment, Mn-hydroxide (MnOOH) coexists with goethite as alternative thin laminae with shale, or coprecipitates resembling a marine Mn nodule, in the size of 0.5 cm in diameter. Radioactive anomalies have been recognized frequently for these Mn sediments due to absorption of Ra by the sediments.     

The influence of mussel beds on nutrients in the Western Wadden Sea and Eastern Scheldt estuaries

The uptake and release of materials by intertidal mussel beds were directly measured in two cultivated Dutch estuaries. Generally, chlorophylla, seston, and particulate organic carbon were taken up, while ammonium, orthophosphate, and silicate were released. The observed rates were higher than values computed from organismic observations and similar to those observed for intertidal oyster reefs in South Carolina. Specific estuarine material turnover rates varied from 1 week to 38 weeks when calculated with mussel bed fluxes. The fastest turnover rates were for chlorophylla and ammonium. These results support the idea that dense assemblages of bivalves are major components in the recycling of nutrients in estuaries.     

Temperature distribution in karst systems: the role of air and water fluxes

A better understanding of heat fluxes and temperature distribution in continental rocks is of great importance for many engineering aspects (tunnelling, mining, geothermal research, etc.). This paper aims at providing a conceptual model of temperature distribution in karst environments which display thermal ‘anomalies’ as compared with other rocks. In temperate regions, water circulation is usually high enough to ‘drain‐out’ completely the geothermal heat flux at the bottom of karst systems (phreatic zone). A theoretical approach based on temperature measurements carried out in deep caves and boreholes demonstrates, however, that air circulation can largely dominate water infiltration in the karst vadose zone, which can be as thick as 2000 m. Consequently, temperature gradients within this zone are similar to the lapse rate of humid air (～0.5 °C 100 m^?1). Yet, this value depends on the regional climatic context and might present some significant variations.     

A geochemical comparison of manganese oxide deposits of the Hawaiian Archipelago and the Deep Sea

Data are presented on the composition of manganese crusts collected within the Hawaiian Exclusive Economic Zone (HEEZ). These crusts were obtained in 80% of the dredge hauls between 800 and 3000 m. Although the chemistries of crusts on the Cenozoic Hawaiian Ridge and an older Cretaceous seamounts south and north of the ridge are quite similar, there are marked differences, both in composition and in mineralogical organization, between shallow and deep crusts. Shallow crusts (<1500 m) are composed of five distinct phases (i.e. silicate, apatite, iron oxide, manganese oxide, and non-associated copper), whereas the deep crusts display no obvious inter-elemental organization based on dendrograms. The mean composition of HEEZ crusts differs from that of Eastern Tropical Pacific nodules in that crusts are comparatively rich in As, Pb, Co, Ce, Fe, and Ti, whereas nodules have comparatively more Cu, Ni, and Sr. Compositional differences between shallow crusts and nodules are discussed in terms of (1) element source; (2) Mn-oxide mineralogy; and (3) redox conditions in the adjacent seawater. It is concluded that the major differences between crust and nodules is due to metal sources; water column for crusts, sediments for nodules. Advective processes within the O₂ minimum also affect the HEEZ crusts.