Reduction Rates of Sedimentary Mn and Fe Oxides: An Incubation Experiment with Arctic Ocean Sediments

To test the hypothesis that manganese- and iron-reducing bacteria in marine sediments respond rapidly to seasonal pulses of fresh organic carbon settling to the sea floor, we amended wet metal oxide?Crich and metal oxide?Cpoor sediments from the Beaufort Sea, Canadian Arctic, with organic carbon in the form of shrimp powder and incubated them at room temperature. Neither Mn nor Fe was released to the aqueous phase from unamended metal oxide?Crich sediment during a 41-day incubation, but both elements were released from sediment aliquots amended with organic carbon. Dissolved Mn appeared in the aqueous phase after a lag period of 2 days or less and reached levels as high as 600 ??mol l^?1 before levelling out. The release of dissolved Mn was accompanied by a decrease in the concentration of solid-phase reducible Mn. Dissolved Fe did not appear until 2 weeks into the incubation and only after the concentration of dissolved Mn had levelled out. For low concentrations of amended organic carbon (0.3%), the kinetics of Mn reduction fit a second-order rate law with a rate constant k = 2 × 10^?3 g ??mol^?1 day^?1, but at intermediate and high organic carbon concentrations (0.7 and 1.3%), the reduction kinetics was better described by a pseudo-first-order rate law with a rate constant k?? = 1.6 × 10^?1 day^?1. A pulse of organic carbon settling to the sea floor can trigger reduction of Mn and Fe oxides within a few days in strongly seasonal sedimentary environments, such as in the Arctic.     

Anaerobic Carbon Mineralisation Through Sulphate Reduction in the Inner Shelf Sediments of Eastern Arabian Sea

Monsoon-induced coastal upwelling, land run-off, benthic and atmospheric inputs make the western Indian shelf waters biologically productive that is expected to lead to high rates of mineralisation of organic matter (OM) in the sediments. Dissimilatory sulphate reduction (SR) is a major pathway of OM mineralisation in near-shore marine sediments owing to depletion of other energetically more profitable electron acceptors (O₂, NO₃ ^?, Mn and Fe oxides) within few millimetres of the sediment-water interface. We carried out first ever study to quantify SR rates in the inner shelf sediments off Goa (central west coast of India) using the ³⁵S radiotracer technique. The highest rates were recorded in the upper 10 cm of the sediment cores and decreased gradually thereafter below detection. Despite significant SR activity in the upper ～12 to 21 cm at most of the sites, pore water sulphate concentrations generally did not show much variation with depth. The depth integrated SR rate (0.066–0.46 mol m^?2 year^?1) decreased with increasing water depth. Free sulphide was present in low concentrations (0–3 μM) in pore waters at shallow stations (depth <30 m). However, high build-up of sulphide (100–600 μM) in pore waters was observed at two deeper stations (depths 39 and 48 m), 7–11 cm below the sediment-water interface. The total iron content of the sediment decreased from ～7 to 5 % from the shallowest to the deepest station. The high pyrite content indicates that the shelf sediments act as a sink for sulphide accounting for the low free sulphide levels in pore water. In the moderately organic rich (2–3.5 %) sediments off Goa, the measured SR rates are much lower than those reported from other upwelling areas, especially off Namibia and Peru. The amount of organic carbon remineralised via sulphate reduction was ～0.52 mol m^?2 year^?1. With an estimated average organic carbon accumulation rate of ～5.6 (±0.5) mol m^?2 year^?1, it appears that the bulk of organic matter gets preserved in sediments in the study region.     

Trace metal and radionuclide pollution in marine sediments of the Aegean Sea (Izmir Bay and Didim)

To determine radioactivity and trace metal levels, surface sediments were collected from two important areas (?zmir Bay and Didim) in the Aegean Sea region of Turkey, and were analyzed for concentrations of ²¹⁰Po, ²¹⁰Pb and trace metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn). The average ²¹⁰Po and ²¹⁰Pb massic activities in sediments varied in the range of 24 ± 5 to 126 ± 6 Bq kg^?1 dry wt. and 18 ± 3 to 59 ± 4 Bq kg^?1 dry wt., respectively. Izmir Bay exhibited the highest polonium activities in sediments, likely due to specific sedimentation processes and other sediment characteristics. The trace metal results showed that the Izmir Bay is facing trace metal pollution. The metal concentrations in sediment samples are low compared to those from the other neighboring marine environments.     

Characterisation of the Sarcheshmeh copper mine tailings,Kerman province,southeast of Iran

Mineral processing operation at the Sarcheshmeh porphyry copper mine has produced huge quantities of tailings materials containing sulphide minerals in particular pyrite. These tailings materials were geochemically and mineralogically characterised to assess pyrite and chalcopyrite oxidation, acid mine drainage generation, and trace element mobility to lead development of a proper remediation plan. Five vertical trenches up to 4.2 m deep were excavated from the tailings surface, and 70 solid samples were taken in 0.3 m intervals. The samples were first mineralogically analysed. Pyrite was the main sulphide mineral found in the tailings. The gangue minerals include quartz ± muscovite–illite ± chlorite ± albite ± orthoclase ± halite. The samples were geochemically analysed for total concentrations of 62 elements, paste pH, SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. The maximum concentrations of SO₄ ^2? (1,300, 1,170, 1,852, 1,960 and 837 mg/L) were observed at a depth of 0.9 m in profiles A, B, C, D and E, respectively. The tailings have a high acid-producing potential and low acid-neutralising potential (pyrite 4–6 wt %, calcite 1 wt %). Fe₂(SO₄)₃, CuSO₄, MgSO₄ and MnSO₄ were the dominant secondary sulphate minerals in the tailings. The lowest pH values (2.9, 3 and 3) were measured at a depth of 0.3 m in the profiles A, B and C, 3.9 at a depth of 0.6 m in the profile D and 3 at a depth of 0.9 m in the profile E. The upper portions of the profiles C (1.8 m) and D (2.1 m) were moderately oxidised, while oxidation in the profiles A, B and E did not extend more than 1.2, 1.2 and 1.5 m beneath the tailings surface. Zn, Pb, Rb, U, Hf, Nd, Zr and Ga show almost a constant trend with depth. Cd, Sr, Th, La and Ce increased with increasing depth of the tailings materials while, Co, V, Ti, Cr, Cu, As, Mn, Ag, Mo and Ni exhibit initially a decreasing trend from tailings surface to the depths that vary between 0.9 and 1.2. They then remained constant with the depth. The results show pyrite and chalcopyrite oxidation at surface layers of the tailings and subsequent leaching of the oxidation products and trace elements by infiltrated atmospheric precipitation.     

Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

Quantifying Sediment Nitrogen Releases Associated with Estuarine Dredging

Experimental studies of sediment pore water NH₄ ⁺ chemistry, adsorbed NH₄ ⁺ concentrations, sediment?Cwater NH₄ ⁺ exchange and N₂?CN flux were carried out to quantify the mass of labile N that can be released during large-scale dredging activities. Pore water NH₄ ⁺ concentrations below 0.5-m sediment depth averaged 5 ± 2 mmol L^?1 with average adsorbed NH₄ ⁺ concentrations of 11 ??mol g^?1. Elevated NH₄ ⁺ concentrations found in rapidly accreting dredge channels are partly a result of the rapid advective burial of both reactive organic matter and pore water. Elutriate tests, a dilution of sediment with site water, yielded adsorbed NH₄ ⁺ concentrations very similar to those using the more typical KCl extraction. Intact deep sediment sections exposed to overlying water, used to simulate postdredging conditions, showed high initial fluxes of ammonium and no development of coupled nitrification?Cdenitrification under the cold incubation conditions. Despite high concentrations and effluxes of NH₄ ⁺ during dredging, the amount of NH₄ ⁺ release during dredging was <0.5% of northern Chesapeake Bay sediment fluxes. The likelihood of large environmental effects of nitrogen release during the dredging of navigational channels in the Chesapeake Bay is low.     

Impact of Oyster Farming on Diagenetic Processes and the Phosphorus Cycle in Two Estuaries (Brittany,France)

This study aims to compare the impact of oyster cultures on diagenetic processes and the phosphorus cycle in the sediments of the Aber Benoît and the Rivière d’Auray, estuary of Brittany, France. Our results showed clear evidence of the seasonal impact of oyster cultures on sediment characteristics (grain size and organic matter parameters) and the phosphorus cycle, especially in the Aber Benoît. At this site, seasonal variations in sulfide and Fe concentrations in pore waters, as well as Fe–P concentrations in the solid phase, highlighted a shift from a system governed by iron reduction (Reference) to a system governed by sulfate reduction (beneath oyster). This could be partly explained by the increase in labile organic matter (i.e., biodeposits) beneath oysters, whose mineralization by sulfate led to high sulfide concentrations in pore waters (up to 4,475 µmol l^?1). In turn, sulfide caused an enhanced release of phosphate in the summer, as adsorption sites for phosphate decreased through the formation of iron–sulfide compounds (FeS and FeS₂). In the Aber Benoît, dissolved Fe/PO₄ ratios could be used as an indicator of phosphate release into oxic water. Low Fe/PO₄ ratios in the summer indicated higher effluxes of phosphate toward the water column (up to 47 µmol m^?2 h^?1). At other periods, Fe/PO₄ ratios higher than 2 mol/mol indicated very low phosphate fluxes. In contrast, in the Rivière d’Auray, the occurrence of macroalgae, stranding regularly all over the site, clearly masked the impact of oyster cultures on sediment properties and the phosphorus cycle and made the use of Fe/PO₄ ratios more difficult in terms of indicators of phosphate release.     

Phase equilibria in the KFeS<Subscript>2</Subscript>–Fe–S system at 300–600 °C and bartonite stability

The article deals with phase relations in the KFeS₂–Fe–S system studied by the dry synthesis method in the range of 300–600 °C and at a pressure of 1 bar. At the temperature below 513?±?3 °C, pyrite coexists with rasvumite and there are pyrite–rasvumite–KFeS₂ and pyrite–rasvumite–pyrrhotite equilibria established. Above 513?±?3 °C pyrite and rasvumite react to form KFeS₂ and pyrrhotite, limiting the pyrite–rasvumite association to temperatures below this in nature. The experiments also outline the compositional stability range of the copper-free analog of murunskite (K _x Fe_2?yS₂) and suggest that mineral called bartonite is not stable in the Cl-free system, at least at atmospheric pressure and the temperature in the experiments. Chlorbartonite could be easily produced after adding KCl in the experiment. Possible parageneses in the quaternary K–Fe–S–Cl system were described based on the data obtained in this research and found in the previous studies. The factors affecting the formation of potassium–iron sulfides in nature were discussed.     

The Role of CaCO<Subscript>3</Subscript> Reactions in the Contemporary Oceanic CO<Subscript>2</Subscript> Cycle

The present analysis adjusts previous estimates of global ocean CaCO₃ production rates substantially upward, to 133 × 10¹² mol yr^?1 plankton production and 42 × 10¹² mol yr^?1 shelf benthos production. The plankton adjustment is consistent with recent satellite-based estimates; the benthos adjustment includes primarily an upward adjustment of CaCO₃ production on so-called carbonate-poor sedimentary shelves and secondarily pays greater attention to high CaCO₃ mass (calcimass) and turnover of shelf communities on temperate and polar shelves. Estimated CaCO₃ sediment accumulation rates remain about the same as they have been for some years: ~20 × 10¹² mol yr^?1 on shelves and 11 × 10¹² mol yr^?1 in the deep ocean. The differences between production and accumulation of calcareous materials call for dissolution of ~22 × 10¹² mol yr^?1 (~50 %) of shelf benthonic carbonate production and 122 × 10¹² mol yr^?1 (>90 %) of planktonic production. Most CaCO₃ production, whether planktonic or benthonic, is assumed to take place in water depths of <100 m, while most dissolution is assumed to occur below this depth. The molar ratio of CO₂ release to CaCO₃ precipitation (CO₂↑/CaCO₃↓) is <1.0 and varies with depth. This ratio, Ψ, is presently about 0.66 in surface seawater and 0.85 in ocean waters deeper than about 1000 m. The net flux of CO₂ associated with CaCO₃ reactions in the global ocean in late preindustrial time is estimated to be an apparent influx from the atmosphere to the ocean, of +7 × 10¹² mol C yr^?1, at a time scale of 10²–10³ years. The CaCO₃-mediated influx of CO₂ is approximately offset by CO₂ release from organic C oxidation in the water column. Continuing ocean acidification will have effects on CaCO₃ and organic C metabolic responses to the oceanic inorganic C cycle, although those responses remain poorly quantified.     

Variability in Concentrations and Fluxes of Methane in the Indian Estuaries

In order to examine the fluxes of methane (CH₄) from the Indian estuaries, measurements were carried out by collecting samples from 26 estuaries along the Indian coast during high discharge (wet) and low water discharge (dry) periods. The CH₄ concentrations in the estuaries located along the west coast of India were significantly higher (113?±?40 nM) compared to the east coast of India (27?±?6 nM) during wet and dry periods (88?±?15 and 63?±?12 nM, respectively). Supersaturation of CH₄ was observed in the Indian estuaries during both periods ((0.18 to 22.3?×?10³ %). The concentrations of CH₄ showed inverse relation with salinity indicating that freshwater is a significant source. Spatial variations in CH₄ saturation were associated with the organic matter load suggesting that its decomposition may be another source in the Indian estuaries. Fluxes of CH₄ ranged from 0.01 to 298 μmol m^?2 day^?1 (mean 13.4?±?5 μmol m^?2 day^?1) which is ~30 times lower compared to European estuaries (414 μmol m^?2 day^?1). The annual emission from Indian estuaries, including Pulicat and Adyar, amounted to 0.39?×?10¹⁰ g CH₄?year^?1 with the surface area of 0.027?×?10⁶ km² which is significantly lower than that in European estuaries (2.7?±?6.8?×?10¹⁰ g CH₄?year^?1 with the surface area of 0.03?×?10⁶ km²). This study suggests that Indian estuaries are a weak source for atmospheric CH₄ than European estuaries and such low fluxes were attributed to low residence time of water and low decomposition of organic matter within the estuary. The CH₄ fluxes from the Indian estuaries are higher than those from Indian mangroves (0.01?×?10¹⁰ g CH₄?year^?1) but lower than those from Indian inland waters (210?×?10¹⁰ g CH₄?year^?1).     

Iron and Pyritization in Wetland Soils of the Florida Coastal Everglades

We explored environmental factors influencing soil pyrite formation within different wetland regions of Everglades National Park. Within the Shark River Slough (SRS) region, soils had higher organic matter (62.65 ± 1.88 %) and lower bulk density (0.19 ± 0.01 g cm^?3) than soils within Taylor Slough (TS; 14.35 ± 0.82 % and 0.45 ± 0.01 g cm^?3, respectively), Panhandle (Ph; 15.82 ± 1.37 % and 0.34 ± 0.009 g cm^?3, respectively), and Florida Bay (FB; 5.63 ± 0.19 % and 0.73 ± 0.02 g cm^?3, respectively) regions. Total reactive sulfide and extractable iron (Fe) generally were greatest in soils from the SRS region, and the degree of pyritization (DOP) was higher in soils from both SRS (0.62 ± 0.02) and FB (0.52 ± 0.03) regions relative to TS and Ph regions (0.30 ± 0.02 and 0.31 ± 0.02, respectively). Each region, however, had different potential limits to pyrite formation, with SRS being Fe and sulfide limited and FB being Fe and organic matter limited. Due to the calcium-rich soils of TS and Ph regions, DOP was relatively suppressed. Annual water flow volume was positively correlated with soil DOP. Soil DOP also varied in relation to distance from water management features and soil percent organic matter. We demonstrate the potential use of soil DOP as a proxy for soil oxidation state, thereby facilitating comparisons of wetland soils under different flooding regimes, e.g., spatially or between wet years versus dry years. Despite its low total abundance, Fe plays an important role in sulfur dynamics and other biogeochemical cycles that characterize wetland soils of the Florida coastal Everglades.     

The 57Fe Mössbauer parameters of pyrite and marcasite with different provenances

Eighteen pyrite and twelve marcasite samples which have different provenances have been investigated to determine the systematics of the influence of mineralogical and geological factors on the ⁵⁷Fe Mössbauer spectra at 298 K. The following results have been obtained: there is no ambiguity in distinguishing single phase pyrite from single phase marcasite by means of ⁵⁷Fe Mössbauer spectroscopy at 298 K. At 298 K the average electric quadrupole splitting, 〈ΔE_Q〉, and average isomer shift, 〈δ〉, with respect to Fe metal, are 0.6110 ± 0.0030 mm s^?1 and 0.313 ± 0.008 mm s^?1, respectively, for the 18 pyrites; 〈ΔE_Q〉 = 0.5030 ± 0.0070 mm s^?1 and 〈δ〉 = 0.2770 ± 0.0020 mm s^?1 for the 12 marcasites. At 77 K, ΔE_Q is 0.624 mm s^?1 for pyrite and 0.508 mm s^?1 for marcasite. In distinguishing pyrites from marcasites, spectra obtained at 77 K are not warranted.The Mössbauer parameters of pyrite and marcasite exhibit appreciable variations, which bear no simple relationship to the geological environment in which they occur but appear to be selectively influenced by impurities, especially arsenic, in the pyrite lattice. Quantitative and qualitative determinations of pyrite/marcasite mechanical mixtures are straightforward at 298 K and 77 K but do require least-squares computer fittings and are limited to accuracies ranging from ±5 to ±15 per cent by uncertainties in the parameter values of the pure phases. The methodology and results of this investigation are directly applicable to coals for which the presence and relative amounts of pyrite and marcasite could be of considerable genetic significance.     

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

The Dynamics of Benthic Respiration at a Mid-Shelf Station Off Oregon

Mid-shelf sediments off the Oregon coast are characterized as fine sands that trap and remineralize phytodetritus leading to the consumption of significant quantities of dissolved oxygen. Sediment oxygen consumption (SOC) can be delayed from seasonal organic matter inputs because of a transient buildup of reduced constituents during periods of quiescent physical processes. Between 2009 and 2013, benthic oxygen exchange rates were measured using the noninvasive eddy covariance (EC) method five separate times at a single 80-m station. Ancillary measurements included in situ microprofiles of oxygen at the sediment–water interface, and concentration profiles of pore water nutrients and trace metals, and solid-phase organic C and sulfide minerals from cores. Sediment cores were also incubated to derive anaerobic respiration rates. The EC measurements were made during spring, summer, and fall conditions, and they produced average benthic oxygen flux estimates that varied between ?2 and ?15 mmol m^?2 d^?1. The EC oxygen fluxes were most highly correlated with bottom-sensed, significant wave heights (H _s). The relationship with H _s was used with an annual record of deepwater swell heights to predict an integrated oxygen consumption rate for the mid-shelf of 1.5 mol m^?2 for the upwelling season (May–September) and 6.8 mol m^?2 y^?1. The annual prediction requires that SOC rates are enhanced in the winter because of sand filtering and pore water advection under large waves, and it counters budgets that assume a dominance of organic matter export from the shelf. Refined budgets will require winter flux measurements and observations from cross-shelf transects over multiple years.     

Spatial and Temporal Variability of Benthic Respiration in a Scottish Sea Loch Impacted by Fish Farming: A Combination of In Situ Techniques

The effects of fish farm activities on sediment biogeochemistry were investigated in Loch Creran (Western Scotland) from March to October 2006. Sediment oxygen uptake rates (SOU) were estimated along an organic matter gradient generated from an Atlantic salmon farm using a combination of in situ techniques: microelectrodes, planar optode and benthic chamber incubations. Sulphide (H₂S) and pH distributions in sediment porewater were also measured using in situ microelectrodes, and dissolved inorganic carbon (DIC) fluxes were measured in situ using benthic chambers. Relationships between benthic fluxes, vertical distribution of oxidants and reduced compounds in the sediment were examined as well as bacterial abundance and biomass. Seasonal variations in SOU were relatively low and mainly driven by seasonal temperature variations. The effect of the fish farm on sediment oxygen uptake rate was clearly identified by higher total and diffusive oxygen uptake rates (TOU and DOU, respectively) on impacted stations (TOU: 70 ± 25 mmol O₂ m^?2 day^?1; DOU: 70 ± 32 mmol O₂ m^?2 day^?1 recalculated at the summer temperature), compared with the reference station (TOU: 28.3 ± 5.5 mmol O₂ m^?2 day^?1; DOU: 21.5 ± 4.5 mmol O₂ m^?2 day^?1). At the impacted stations, planar optode images displayed high centimetre scale heterogeneity in oxygen distribution underlining the control of oxygen dynamics by small-scale processes. The organic carbon enrichment led to enhanced sulphate reduction as demonstrated by large vertical H₂S concentration gradients in the porewater (from 0 to 1,000 μM in the top 3 cm) at the most impacted site. The impact on ecosystem functions such as bioirrigation was evidenced by a decreasing TOU/DOU ratio, from 1.7 in the non-impacted sediments to 1 in the impacted zone. This trend was related to a shift in the macrofaunal assemblage and an increase in sediment bacterial population. The turnover time of the organic load of the sediment was estimated to be over 6 years.     

The diagenetic geochemistry and contamination assessment of iron,cadmium, and lead in the sediments from the Shuangtaizi estuary,China

Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m^?2 a^?1), followed by Cd (0.54 mg m^?2 a^?1) and Pb (0.42 mg m^?2 a^?1). Low Fe²⁺ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe²⁺ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS₂). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb²⁺ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd²⁺ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.     

Sediment Denitrification in Two Contrasting Tropical Shallow Lagoons

Sediment denitrification was monthly evaluated in two tropical coastal lagoons with different trophic states using the ¹⁵N isotope pairing technique. Denitrification rates were very low in both environments, always <5.0 μmol N₂ m^?2 h^?1 and were not significantly different between them. Oxygen consumption varied from 426 to 4248 μmol O₂ m^?2 h^?1 and was generally three times higher in the meso-eutrophic than the oligotrophic lagoon. The low denitrification activity was ascribed to both low water NO₃ ^? concentrations (<2.0 μM) and little nitrate supply from nitrification. There was no correlation of denitrification with nitrate or ammonium fluxes. Sediments in temperate environments with similar oxygen consumption rates usually presented a higher proportion of nitrification–denitrification rates. Sediment oxygen consumption was a good predictor of sediment denitrification in both studied lagoons.     

Evaluation of Naturally Occurring Radioactivity Materials (NORM) of Soil and Sediments in Oil and Gas Wells in Western Niger Delta Region of Nigeria

Oil mineral leases (30, 58 and 61) in Delta and River States are the major oil blocks in the oil and gas rich Niger Delta region of Nigeria that is characterized by environmental degradation from oil and gas activities. This research work presents an analytical approach on natural radioactivity assessment in soil and sediment in 15 oil fields of these OMLs. Concentrations of natural radionuclides (²²⁶Ra, ²³²Th and ⁴⁰K) were determined using gamma spectroscopy. The mean activity concentration of ²²⁶Ra, ²³²Th and ⁴⁰K for OML30 is 40.2 ± 5.1, 29.9 ± 4.2 and 361.5 ± 20.0 Bq kg^?1, respectively; the corresponding values obtained for OML58 is 20.9 ± 2.8, 19.4 ± 2.5 and 260.0 ± 14.1 Bq kg^?1, respectively. While the mean activity concentration of ²²⁶Ra, ²³²Th and ⁴⁰K for OML61 is 29.3 ± 3.5, 21.6 ± 2.6 and 262.1 ± 14.6 Bq kg^?1, respectively. These values obtained show enhanced NORMs, but are well within the world range and values reported in some regions and countries of the world, and are slightly above control values, values obtained in Southwestern region of Nigeria and some countries reported average values. The study also examined some radiation hazard indices, the mean values obtained are 86.6 ± 9.3 Bq kg^?1, 0.6 Bq kg^?1, 40.8 ηGy h^?1, 0.05 μSv y^?1, 0.2 and 0.3 for radium equivalent activity (Ra_eq), representative level index (Iγ), absorbed dose rates (D), annual effective dose rates (E _ff dose), external hazard index (H _ex) and internal hazard index (H _in), respectively. These calculated hazard indices to estimate the potential radiological health risk in soil and sediment are well below their permissible limits. The soil and sediments from the study area provide no excessive exposures for the inhabitants and can be used as construction materials without posing any radiological threat or harm to the public users. However, oil-field workers and host community residents are cautioned against excess exposure to avoid future accumulative dose of these radiations from sludge and sediment of this area.     

The Impact of Sediment and Carbon Fluxes on the Biogeochemistry of Methane and Sulfur in Littoral Baltic Sea Sediments (Himmerfjärden, Sweden)

Three sediment stations in Himmerfjärden estuary (Baltic Sea, Sweden) were sampled in May 2009 and June 2010 to test how low salinity (5–7 ‰), high primary productivity partially induced by nutrient input from an upstream waste water treatment plant, and high overall sedimentation rates impact the sedimentary cycling of methane and sulfur. Rates of sediment accumulation determined using ²¹⁰Pb_excess and ¹³⁷Cs were very high (0.65–0.95 cm?year^?1), as were the corresponding rates of organic matter accumulation (8.9–9.5 mol C?m^?2?year^?1) at all three sites. Dissolved sulfate penetrated <20 cm below the sediment surface. Although measured rates of bicarbonate methanogenesis integrated over 1 m depth were low (0.96–1.09 mol?m^?2?year^?1), methane concentrations increased to >2 mmol?L^?1 below the sulfate–methane transition. A steep gradient of methane through the entire sulfate zone led to upward (diffusive and bio-irrigative) fluxes of 0.32 to 0.78 mol?m^?2?year^?1 methane to the sediment–water interface. Areal rates of sulfate reduction (1.46–1.92 mol?m^?2?year^?1) integrated over the upper 0–14 cm of sediment appeared to be limited by the restricted diffusive supply of sulfate, low bio-irrigation (α?=?2.8–3.1 year^?1), and limited residence time of the sedimentary organic carbon in the sulfate zone. A large fraction of reduced sulfur as pyrite and organic-bound sulfur was buried and thus escaped reoxidation in the surface sediment. The presence of ferrous iron in the pore water (with concentrations up to 110 μM) suggests that iron reduction plays an important role in surface sediments, as well as in sediment layers deep below the sulfate–methane transition. We conclude that high rates of sediment accumulation and shallow sulfate penetration are the master variables for biogeochemistry of methane and sulfur cycling; in particular, they may significantly allow for release of methane into the water column in the Himmerfjärden estuary.     

Chemical characterization and sources of PM2.5 at 12-h resolution in Guiyang,China

The increasing emission of primary and gaseous precursors of secondarily formed atmospheric particulate matter due to continuing industrial development and urbanization are leading to an increased public awareness of environmental issues and human health risks in China. As part of a pilot study, 12-h integrated fine fraction particulate matter (PM_2.5) filter samples were collected to chemically characterize and investigate the sources of ambient particulate matter in Guiyang City, Guizhou Province, southwestern China. Results showed that the 12-h integrated PM_2.5 concentrations exhibited a daytime average of 51 ± 22 µg m^?3 (mean ± standard deviation) with a range of 17–128 µg m^?3 and a nighttime average of 55 ± 32 µg m^?3 with a range of 4–186 µg m^?3. The 24-h integrated PM_2.5 concentrations varied from 15 to 157 µg m^?3, with a mean value of 53 ± 25 µg m^?3, which exceeded the 24-h PM_2.5 standard of 35 µg m^?3 set by USEPA, but was below the standard of 75 µg m^?3, set by China Ministry of Environmental Protection. Energy-dispersive X-ray fluorescence spectrometry (XRF) was applied to determine PM_2.5 chemical element concentrations. The order of concentrations of heavy metals in PM_2.5 were iron (Fe) > zinc (Zn) > manganese (Mn) > lead (Pb) > arsenic (As) > chromium (Cr). The total concentration of 18 chemical elements was 13 ± 2 µg m^?3, accounting for 25% in PM_2.5, which is comparable to other major cities in China, but much higher than cities outside of China.