Effects of oxic and anoxic filtration on determined methyl mercury concentrations in sediment pore waters

Accurate determination of methyl mercury (MeHg) concentrations in sediment pore waters is crucial for an improved understanding of mercury (Hg) biogeochemistry, and for improved risk assessment of Hg contaminated sites. In the present study, effects of oxic (air) and anoxic (N₂) filtration (after centrifugation) on determined pore water MeHg concentrations were investigated in severely Hg contaminated pulp fibre sediments from two estuaries of the Bothnian Sea, Sweden. MeHg was determined in the filtrate using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID–GC–ICPMS), after ethylation with sodium tetraethylborate. Determined concentrations of MeHg were greater after anoxic filtration than after oxic filtration for all samples investigated, with MeHg(N₂)/MeHg(air) ratios ranging between 3.4 and 343. Adsorption to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces is proposed as the main mechanism responsible for MeHg removal during oxic filtration. This is supported by decreases in dissolved Fe and Mn concentrations during oxic filtration, and by decreases in dissolved sulphur concentrations during oxic filtration in the samples with largest effect on MeHg concentrations. The latter is explained by adsorption of SO₄²⁻ to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces. The effect of oxidation during filtration on pore water MeHg concentrations was largest in samples in which FeS(s) was not present, but with calculated pe-values below − 3. Thus, our results indicate that the largest errors with respect to pore water MeHg concentrations when filtering in air can be expected in samples with an intermediate redox potential, possibly buffered by a mixture of oxidation sensitive Fe(II/III) minerals.     

The distributions of uranium, radium and thorium isotopes in two anoxic fjords: Framvaren Fjord (Norway) and Saanich Inlet (British Columbia)

Depth profiles of the naturally-occurring radionuclides ²³⁸U, ²³⁴U, ²²⁶Ra, ²²⁸Ra and ²²⁸Th were obtained in two diverse anoxic marine environments; the permanently anoxic Framvaren Fjord in southern Norway and the intermittently anoxic Saanich Inlet in British Columbia. Concentrations of total H₂S were over three orders of magnitude greater in the anoxic bottom waters of Framvaren Fjord compared to those in Saanich Inlet.In Framvaren Fjord, the O₂/H₂S interface was located at 17 m. While dissolved ²³⁸U behaved conservatively throughout the oxic and anoxic water columns, concentrations based on the ²³⁸U/salinity ratio in oxic oceanic waters were almost 30% lower. Dissolved ²²⁶Ra displayed a sharp maximum just below the O₂/H₂S interface, coinciding with dissolved Mn (II) and Fe (II) maxima in this zone. It is suggested that reductive dissolution of Fe-Mn oxyhydroxides remobilizes ²²⁶Ra in this region.In Saanich Inlet, the O₂/H₂S interface was located at 175 m. Dissolved ²³⁸U displayed a strongly nonconservative distribution. The depth profiles of dissolved ²²⁶Ra and ²²⁸Th correlated well with the distribution of dissolved Mn (II) in the suboxic waters above the O₂/H₂S interface, suggesting that reduction of particulate Mn regulates the behavior of ²²⁶Ra and ²²⁸Th in this region.Removal residence times for dissolved ²²⁸Th in the surface oxic waters of both systems are longer than those generally reported for particle-reactive radionuclides in coastal marine environments. In the anoxic waters of Framvaren Fjord and Saanich Inlet, however, the dissolved ²²⁸Th removal residence times are quite similar to values reported for dissolved ²¹⁰Pb in the anoxic waters of the Cariaco Trench and the Orca Basin. This implies that the geochemistries of Th and Pb may be similar in anoxic marine waters.     

Reduced iron associated with secondary nitrite maxima in the Arabian Sea

Dissolved iron and Fe(II) were measured in the oxygen minimum zone (OMZ) of the Arabian Sea in September 2004. The OMZ is a well-demarcated feature characterized by high rates of denitrification, and a deep nitrite maximum coinciding with oxygen levels below 1 μmol L⁻¹. This zone is significantly enriched in dissolved Fe relative to overlying and underlying waters and up to 50% of the dissolved Fe is present as Fe(II). The maxima in Fe(II) are at the same depth as the deep nitrite maxima, centered around 200–250 m. They coincide with a local maximum in total dissolved Fe, suggesting that Fe accumulates at this depth because of the greater solubility of Fe(II) over Fe(III). Fe(II) is thermodynamically unstable even at submicromolar oxygen levels, so active biological reduction is the most plausible source. To our knowledge, this is the first report of a potential link between Fe reduction, elevated dissolved Fe concentrations, and nitrite accumulation within an OMZ. Denitrification has a high Fe requirement associated with the metalloenzymes for nitrate and nitrite reduction, so in situ redox cycling of Fe has important implications for the nitrogen cycle.     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

Chemical forms of iron in the Connecticut River estuary

The ‘dissolved’ iron (that passed through a 0·4-μm filter) varied nonconservatively with salinity in the Connecticut River estuary. However, the total iron appeared to be conservative. Measurements of Fe(II) and Fe(III) showed that oxidation of Fe(II) was not a factor in the decrease of ‘dissolved’ iron in the low salinity region. A solubility model and analyses based on different pore-size filters indicated that a substantial amount of the ‘dissolved’ iron in the low salinity region was colloidal iron. The coagulation of fine colloidal particles led to the non-conservative behavior of ‘dissolved’ iron during estuarine mixing, but it did not necessarily lead to removal of total iron from the waters. Particulate iron was 80–90% of the total iron and it covaried with the total suspended matter during mixing and sediment resuspension. The residence time of water in the Connecticut River estuary was too short to allow removal of iron from the water column within the estuary.     

A sulfur budget for the Black Sea anoxic zone

A budget for the sulfur cycle in the Black Sea is proposed which incorporates specific biogeochemical process rates. The average sulfide production in the water column is estimated to be 30–50 Tg yr⁻¹, occurring essentially in the layer between 500 and 2000 m. About 3.2–5.2 Tg sulfide yr⁻¹ form during sulfate reduction in surface sediments of the anoxic zone. Total sulfur burial in anoxic sediments of 1 Tg yr⁻¹ consists of 10–70% (ca. 40–50% is the average) water column formed (syngenetic) component, the rest being diagenetic pyrite. As a maximum, between 3 and 5 Tg yr⁻¹ contribute sulfide to the bottom water or diffuse downward in the sediment. About 20–50 Tg yr⁻¹ sulfide is oxidized mostly at the chemocline and about 10–20% of this amount (4.4–9.2 Tg yr⁻¹) below the chemocline by the oxygen of the Lower Bosphorus Current. A model simulating the vertical distribution of sulfide in the Black Sea water column shows net consumption in the upper layers down to ca. 500 m, essentially due to oxidation at the chemocline, and net production down to the bottom. On the basis of the calculated budget anoxic conditions in the Black Sea are sustained by the balance between sulfide production in the anoxic water column and oxidation at the chemocline. On average the residence time of sulfide in the anoxic zone is about 90–150 yr, comparable to the water exchange time between oxic and anoxic zones. Hydrophysical control on the sulfur cycle appears to be the main factor regulating the extent of anoxic conditions in the Black Sea water column, rather than rates of biogeochemical processes.     

A simple guideline to apply excitation-emission matrix spectroscopy (EEMs) for the characterization of dissolved organic matter (DOM) in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth. Dissolved organic matter(DOM) in pore waters accumulates products and intermediates of carbon cycling in sediments. The application of excitation-emission matrix spectroscopy(EEMs) in the analysis of subseafloor DOM samples is largely unexplored due to the redoxsensitive matrix of anoxic pore water. Therefore, this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water sam...     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

Dissolved iodine in waters overlying and in the Orca Basin,Gulf of Mexico

The distribution and speciation of iodine, a biophilic redox-sensitive trace element, in waters overlying and in the Orca Basin, Gulf of Mexico, which contains hypersaline, anoxic and yet non-sulfide-bearing brine have been determined. The distribution of iodate and iodide in the oxic waters overlying the anoxic brine are similar to those reported in other oceans. However, in the oxic-anoxic mixing zone, iodate disappears while the concentration of iodide reaches a maximum of 8.1 μM, the highest concentration ever reported in open oceans. There is also a maximum in specific iodine of 30.7 nM‰^?1 at this depth. Specific iodine in oxic seawater is only about 10–14 nM ‰^?1. These features may be explained by the preferential dissolution of biogenic particles that have accumulated in a strong pycnocline. In the anoxic brine proper, the concentration of iodide is 3.8 μM and can be explained almost entirely by the simultaneous mobilization of chloride and iodide during the dissolution of evaporite beds as the specific iodine of 14.5 nM‰^?1 is only slightly higher than those observed in the oxic waters.     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O₂/H₂S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O₂/H₂S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.     

The geochemistry of iron and manganese in the waters and sediments of Bolstadfjord,S.W. Norway

The distributions of dissolved and solid phase Fe and Mn have been variously determined in vertical profiles through the water column and sediments at three stations in Bolstadfjord, S.W. Norway. Elevated concentrations of dissolved and suspended particulate Fe and Mn are associated with restricted deep waters as a result of redox reactions and with river discharge. The basin sediments are anoxic throughout but because of the greatly restricted circulation, remobilized Fe and Mn appear to remain predominantly trapped within the fjord. Differentiation of Fe and Mn occurs to the extent that Fe sulphide precipitation is ubiquitous in the sediments whereas the entrapment of Mn, probably through Mn carbonate precipitation, is found only in the sediments of the more seaward basin (maximum Mn content of 1·5% by weight).     

The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O₂H₂S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH₂S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe²⁺) and manganese (Mn²⁺) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO₃). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin.     

Benthic geochemistry of manganese in the Bay of Biscay,and sediment mass accumulation rate

Manganese is a major redox reactive element of benthic metabolism. We have built a database of existing knowledge on the benthic geochemistry of Mn in the Bay of Biscay, in order to comprehensively assess the behaviour of Mn in a variety of environments during early diagenesis. The database contains vertical profiles of particulate and dissolved Mn species of 59 cores collected during 17 cruises between 1997 and 2006 at nine stations positioned between 140 and 4,800 m water depths. At all studied stations, Mn species follow the conventional distribution, where Mn(III,IV) species are enriched in the oxic layer, and dissolved Mn is present in the anoxic sediments. A minor part of Mn-oxides originates from sedimenting particles. The major part is of diagenetic origin, and derives from the oxidation of upward-diffusing dissolved Mn(II). Mn-oxide inventories are higher at the deeper stations than at the shallower ones. This difference cannot be attributed to different sources of sedimenting particles, but it must depend on sedimentation rate and diagenetic processes. At depth, dissolved Mn(II) concentrations are constant. This probably reflects equilibrium with an authigenic Mn(II) phase, which is the ultimate phase into which Mn is fossilized. The Mn content of deeper anoxic sediments is similarly low in all the cores studied, associated with corresponding trends of Mn content in sedimenting particles of the Bay of Biscay. Bioturbation, rather than redox oscillations, can convey Mn(III,IV) species downwards into the anoxic sediments where they are reduced, associated with a peak of dissolved Mn. Because dissolved Mn(II) is re-oxidized when it diffuses towards the oxic layer, the inventory of the diagenetic Mn(III,IV) phase remains at steady state, especially at stations where the oxic layer is thick. It then becomes possible to calculate the residence time of diagenetic Mn(III,IV) particles within the oxic layer, using the upward-directed flux of pore water Mn(II). By applying this residence time to the accumulation of sediments within the oxic layer, we obtain the sediment mass accumulation rate. The values calculated for the sediments of the Bay of Biscay fit well with accumulation rates obtained from radionuclides or sediment traps. The method has also been validated with data collected in other marine sedimentary environments. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

Controls on temporal variability of the geochemistry of the deep Cariaco Basin

Studies of the Cariaco Basin on the continental shelf of Venezuela, as a part of the Carbon Retention In A Colored Ocean (CARIACO) program, have revealed that the chemistry of the deeper waters of the system is more variable than previously believed. Small oxygen maxima have been observed on a number of occasions at depths where oxygen was previously absent, suggesting the occurrence of intrusions of oxygenated water into the region of the oxic/anoxic interface (250–300 m). Apparently because of these events, the oxic/anoxic interface deepened by about 100 m during the period of our observations. We also observed a dramatic decrease in H₂S concentrations at all depths below the oxic/anoxic interface during this same period. Bottom waters, for example, had an H₂S concentration of about 75 μM in November 1995, but since November 1997, concentrations in bottom water have not exceeded 55 μM. Water of sufficient density to sink to the bottom of the Basin has been observed on one occasion at sill depth just north of the eastern sill. However, based on a simple box model, the decrease in deep-water sulfide does not appear to be due to intrusion of oxygenated water alone, as concentrations of other measured species, and of hydrographic parameters, have remained constant with time. Instead, we postulate that an earthquake that took place in July 1997 resulted in a turbidity current that transported large quantities of coastal sediment containing oxidized iron into the deep waters of the basin. If the final products of reaction were elemental sulfur and iron sulfide, the sediment associated with the oxidized iron would have produced a turbidite layer about 10 cm thick. Previous earthquakes have produced turbidites of similar thickness.     

A comparison of iron limitation of phytoplankton in natural oceanic waters and laboratory media conditioned with EDTA

The solubility of iron in oxic waters is so low that iron can be a limiting nutrient for phytoplankton growth in the open ocean. In order to mimic low iron concentrations in algal cultures, Ethylenediaminetetraacetate (EDTA) is commonly used. The presence of EDTA enables culture experiments to be performed at a low free metal concentration, while the total metal concentrations are high. Using EDTA provides for a more reproducible medium. In this study Fe speciation, as defined by EDTA in culture media, is compared with complexation by natural organic complexes in ocean water where Fe is thought to be limited. To grow oceanic species into iron limitation, a concentration of at least 10⁻⁴ M EDTA is necessary. Only then does the calculated [Fe³⁺] concentrations resemble those found in natural sea water, where the speciation is governed by natural dissolved organic ligands at nanomolar concentrations. Moreover, EDTA influences the redox speciation of iron, and thus frustrates research on the preferred source of Fe-uptake, Fe(III) or Fe(II), by algae. Nowadays, one can measure the extent of natural organic complexation in sea water, as well as the dissolved Fe(II) state, and can use ultra clean techniques in order to prevent contamination. Therefore, it is advisable to work with more natural conditions and not use EDTA to create iron limitation. This is especially important when the biological availability of the different chemical fractions of iron are the subject of research. Typically, many oceanic algae in the smallest size classes can still grow at very low ambient Fe and are not easily cultivated into limitation under ambient sea water conditions. However, the important class of large oceanic algae responsible for the major blooms and the large scale cycling of carbon, silicon and other elements, commonly has a high Fe requirement and can be grown into Fe limitation in ambient seawater.     

Dissolved iron(II) in the Pacific Ocean: Measurements from the PO2 and P16N CLIVAR/CO2 repeat hydrography expeditions

The redox speciation of dissolved iron in seawater was evaluated at 121 locations in the Pacific Ocean at depths of 15-1000 m, using the method of luminol chemiluminescence. The results indicate that reduced iron, Fe(II), is ubiquitous in surface seawater with a relatively consistent pattern of occurrence. Surface maxima were present in most profiles, with median concentrations of 25-30 pM representing 12-14% of the total dissolved iron. Concentrations decreased monotonically with depth to<12 pM within the upper euphotic zone. This pattern was observed during both day and nighttime sampling events, which suggests that non-photochemical production mechanisms can produce photochemical-like signatures. Further, if theoretical rates of Fe(II) oxidation are applicable to the open ocean, then the employed sampling methods precluded assessment of photochemically-produced Fe(II), regardless of ambient light conditions. For this and other reasons, the concentrations reported here for the upper water column likely represent lower limits of labile iron concentration, and suggest that dissolved iron may be more available for uptake than previously believed. Deeper in the water column, Fe(II) was also frequently detected, though it constituted a small fraction of the total dissolved iron. Possible source mechanisms at these depths include thermal (dark) reduction of Fe(III) organic complexes or remineralization of sinking biogenic particles containing Fe(II). In the northern Philippine Sea between the Japanese coast and the Izu-Bonin volcanic arc system, Fe(II) concentrations were found to be atypically high, possibly because of high atmospheric dust deposition near the surface and transport of sediment-derived iron at depth.     

Spatial and Temporal Distribution of Oxidation Events Occurring Below the Sediment-Water Interface

Abstract. Irrigation and bioturbation lead to transport of dissolved oxygen into anoxic sediments. The depthdistribution of local oxygen input and the total time of oxygen presence was measured at randomly sampled locations within anoxic sediments, originating from the North Sea.
In the laboratory, continuous redox potential records, displaying a transient increase and decrease when in contact with oxygen for a limited time, were used to record oxidation events'. Oxygen microelectrodes were used to confm the presence of oxygen. Measurements were performed for 180 d at 230 locations in the top 6 cm of sediment cores containing the natural macrofauna community.
4783 oxidation events m^-2· d^-1 were recorded within the upper 6 cm of the sediment. The number and duration of oxidation events declined with sediment depth below the oxic zone. Oxygen was present in the anoxic sediment, as determined from redox potential measurements, ≥ 6 h per day at 10% of the randomly chosen locations within the upper 3 cm. The overall distribution of oxidation events and their duration suggest that local, pulsed additions of oxygen by irrigation may be sufficient to maintain an oxidised sediment layer ( sensu J orgensen amp; R evsbech , 1989). Oxic environments along burrow walls rapidly fluctuate between oxic and anoxic conditions. Using oxygen microelectrodes the presence of oxygen (oxic conditions) in these halos was found to range from 2 to 12 h per day. Continuous redox measurements show that oxidised conditions fluctuate with the oxygen pulses and display the same durations, although these may range up to 21 h per day. Oxic and oxidised sediment volumes are estimated to represent < 1% and 3.7%. respectively, of the anoxic sediment to 6 cm depth. Recognition of temporal variability and spatial heterogeneity of sedimentary conditions may prove valuable for future conclusions drawn in other research fields.     

东山湾海水中Fe(II)和Fe(III)相互转化围隔实验研究

根据2008 年8 月与11 月在东山湾海域获得的调查资料对表层水中溶解态Fe(II)和Fe(III)含量、浮游植物叶绿素a、营养元素及其浓度等环境参数进行分析。结果表明, 夏、秋季海水中Fe(II)浓度及其在总溶解铁中所占比例均与浮游植物叶绿素a 呈正相关, 其相关系数分别为0.7959、0.9219。现场围隔实验表明, 海水中总溶解态Fe 含量在24 h 内有较大的变化, 最大减少量达到17.4%。DS2 站点海水中Fe(II)浓度及其在总溶解铁中所占比例随光照强度增加而增加。最高值与初始值相比较, 叶绿素a 较高的DS2 站点海水中Fe(II)浓度增加较叶绿素a 较低的DS5 号站点高0.053μg/L。Fe(II)和Fe(III)加富实验研究了溶解态的Fe(II)和Fe(III)在海水中相互转化。高浓度的Fe(II)在海水中被氧化成Fe(III),海水中浮游植物也会引发光还原作用使Fe(III)还原成Fe(II)。