Reactive sulfides relationship with metals in sediments from an eutrophicated estuary in Southeast Brazil

The potential association of acid-volatile sulfides (AVS) and reactive (HCl soluble) Fe with the distribution of reactive trace metals (Cu, Cd, Ni, Pb and Zn) was investigated in sediment cores collected in the Igua?u river estuarine system (Guanabara bay, Brazil), within the river (core R) and the bay (core B) areas. Moderate to extremely high AVS concentrations (33-314 micromol g(-1)) were found in the rapidly-accumulated sediments of this eutrophicated estuary. AVS showed significant correlations with Fe, Ni and Pb in core B, whereas no correlation between AVS and metals was observed in core R. Results suggest that the AVS:Fe molar ratio may often reflect the diagenetic conditions controlling the distribution of Cd and Cu in core B better than AVS and Fe levels themselves. A shift in the biogeochemical controls of metal distribution from the river to the open bay sediments is suggested, with a greater association of most metals with AVS and Fe in bay sediments.     

Bioelectricity generation and remediation of sulfide contaminated tidal flat sediment

A dramatic decrease in the catch of shellfish has been observed due to the high amount of Acid Volatile Sulfide(AVS) in the tidal flats in Japan.In the current study,an evaluation of simultaneous bioelectricity generation and remediation of sulfide contaminated tidal flat sediment has been done.The sediment samples collected from Tokyo Bay and Yamaguchi Bay,Japan,have been used in the laboratory test.A 2 L cylindrical shaped Sediment Microbial Fuel Cell(SMFC) has been used to evaluate the remediation of both sediment samples in the laboratory.Three different electrode materials carbon felt,carbon fiber and bamboo charcoal were used in the experiments to compare their efficiency to reduce the AVS from the sediment and generate bioelectricity.It was observed that the AVS reduction was higher at 5 cm depths for the Tokyo Bay sediment(100%) compared to the Yamaguchi Bay sediment(60%).The larger grain size for the Tokyo Bay sediment was the probable reason for this.The maximum voltage was around 100 and80 mV for Tokyo Bay and Yamaguchi Bay,respectively.     

Sequestration of metals through association with pyrite in subtidal sediments of the Nanpaishui Estuary on the Western Bank of the Bohai Sea, China

Measurements were made of the degree of trace metal pyritization (DTMP) and ancillary characteristics of four undisturbed sediment cores collected from the subtidal zone of the Nanpaishui Estuary on the Western Bank of the Bohai Sea, a seriously polluted inland sea in northeastern China. The remarkably low concentrations of organic carbon (<0.72%) in these sediments likely constrained sulfate reduction rates, and the low concentrations of acid volatile sulfide (AVS) (<12.5 μmol g⁻¹) limited the sequestration of metals through association with pyrite. The most consistent cause of inter-station differences and depth variations in the degree of pyritization was differences in pyrite metal concentrations rather than reactive metal concentrations. Reactive metal concentrations were in several cases negatively correlated with pore water concentrations, consistent with a dissolution/precipitation mechanism. The relationship between pore water metal concentrations and DTMPs was evidenced by a qualitative similarity of the inter-station variability of these same parameters.     

Blast furnace slag can effectively remediate coastal marine sediments affected by organic enrichment

There is an urgent need to control nutrient release fluxes from organically-enriched sediments into overlying waters to alleviate the effects of eutrophication. This study aims to characterize blast furnace slag (BFS) and evaluate its remediation performance on organically-enriched sediments in terms of suppressing nutrient fluxes and reducing acid volatile sulfide. BFS was mainly composed of inorganic substances such as CaO, SiO₂, Al₂O₃ and MgO in amorphous crystal phase. Container experiments showed that the phosphate concentration in the overlying water, its releasing flux from sediment and AVS of the sediment decreased by 17-23%, 39% and 16% compared to the control without BFS, respectively. The loss on ignition was significantly decreased by 3.6-11% compared to the control. Thus, the application of BFS to organically-enriched sediment has a suppressive role on organic matter, AVS concentration and phosphate releasing flux from sediments and therefore, is a good candidate as an effective environmental remediation agent.     

A review of acid sulfate soil impacts, actions and policies that impact on water quality in Great Barrier Reef catchments, including a case study on remediation at East Trinity

An estimated 666,000 ha of acid sulfate soils (ASS) occur within the Great Barrier Reef (GBR) catchments of Queensland, Australia. Extensive areas have been drained causing acidification, metal contamination, deoxygenation and iron precipitation in reef receiving waters. The close proximity of ASS to reef waters makes them a substantial threat to water quality. Another important issue linked with ASS is their release of soluble iron, which is known to stimulate nuisance marine algal blooms, in particular Lyngbya majuscula. Known blooms of the cyanobacteria in reef waters have been confirmed at Shoalwater Bay, Corio Bay, the Whitsunday area and Hinchinbrook Channel. Acid sulfate soils are intimately related to coastal wetland landscapes. Where landscapes containing ASS have been disturbed (such as for agriculture, aquaculture, marinas, etc.) the biodiversity of adjacent wetlands can be adversely affected. However, there is no clear knowledge of the real extent of the so-called "hotspot" ASS areas that occur within the GBR catchments. Management of ASS in reef catchments has benefited from the implementation of the Queensland Acid Sulfate Soils Management Strategy through policy development, mapping, training programs, an advisory service, research and community participation. However, major gaps remain in mapping the extent and nature of ASS. Areas of significant acidification (i.e. hotspots) need to be identified and policies developed for their remediation. Research has a critical role to play in understanding ASS risk and finding solutions, to prevent the adverse impacts that may be caused by ASS disturbance. A case study is presented of the East Trinity site near Cairns, a failed sugar cane development that episodically discharges large amounts of acid into Trinity Inlet, resulting in periodic fish kills. Details are presented of scientific investigations, and a lime-assisted tidal exchange strategy that are being undertaken to remediate a serious ASS problem.     

Reflectance spectral characterization and mineralogy of acid sulphate soil in subsurface using hypcrspectral data

Acid sulphate soil（ASS） is a kind of soil which is harmful to the environment.ASS is hard to efficiently assess efficiently in the subsurface,although it is detectable on the surface by remote sensing.This paper aims to explore a new way to rapidly assess ASS in the subsurface by introducing a proximal hyperspectral instrument,namely the HyloggerTM system which can rapidly scan soil cores and provide high resolution hyperspectral data.Some minerals in ASS,which usually act as indicators of the severity of ASS,such as iron oxides,hydroxides,and sulphates,as well as some clay minerals,such as kaolinite,have diagnostic spectral absorption features in the reflectance spectral range（400-2500 nm）.Soil cores were collected from a study area and hyperspectral data were acquired by HyloggerTM scanning.The main minerals related to ASS were characterized spectrally,and were subsequently identified and mapped in the soil cores based on their reflectance spectral characteristics.Traditional X-ray diffraction（XRD） and scanning electron microscope（SEM） were also applied to verify the results of the mineral identification.The main results of this study include the spectral characterisation of ASS and its main compositional minerals,as well as the distribution of these relevant minerals in different depth of cores.     

Monosulfidic black ooze accumulations in sediments of the Geographe Bay area, Western Australia

Mobilisation of sedimentary monosulfidic black ooze (MBO) may result in rapid deoxygenation and acidification of surface waters, and release of potentially toxic metals. This study examines the extent and nature of MBO accumulation in the Geographe Bay area, Western Australia. MBO accumulations were found to be widespread in benthic sediments of the Geographe Bay area with acid-volatile sulfide (AVS) contents as high as 320 μmol g⁻¹. The MBO materials often had unusually high dissolved sulfide (S^−II) concentrations in their pore-waters (up to 610 mg L⁻¹) and elevated elemental sulfur (S⁰) contents (up to 51 μmol g⁻¹). Dissolved S^−II is able to accumulate due to limited iron availability and S⁰ is largely its partial oxidation product. The availability of organic carbon and Fe limited MBO accumulation at many sites. A comparison of AVS and simultaneously extracted metal (SEM) concentrations has shown that metals are likely to be bound in sulfide complexes.     

The distribution of acid-volatile sulfide and simultaneously extracted metals in sediments from a mangrove forest and adjacent mudflat in Zhangjiang Estuary, China

The distribution of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) were studied in sediments collected from mangrove forest, forest fringe and adjacent mudflat in the Zhangjiang Estuary, China. The aim was to examine the spatial distribution of AVS and SEM in sediments of the Estuary and determine the influence of mangrove trees on AVS and SEM concentrations in the sediments. The results indicated that AVS concentrations in forest sediments were significantly lower than those in mudflat sediments. There was a significant positive correlation between AVS values and moisture contents in forest sediments, while LOI played an important role in AVS concentrations of mudflat sediments. In the forest sediment core, the peak value of AVS appeared deeper in the sediment profile compared to it appeared in the mudflat core. The distribution of SEM showed different trends from that of AVS, and potential toxicity existed in the upriver forest sediments.     

Trace metals in a tidal Mediterranean embayment

The Euvoikos gulf, and the strait of Euripos therein, is a restricted embayment on the eastern coast of Greece having a significant, unusual tidal phenomenon and receiving some domestic, trade and industrial wastes from the town of Chalkis and several coastal industries. The purpose of the present work was to study the influence of the tidal current and the anthropogenic inputs on the distributions of several trace elements (namely, Pb, Cu, Zn, Cr, Fe, Mn and Ni) in the seawaters (as dissolved and particulate species) and the sea-bottom sediments. Thorough mixing, resuspension and transport of fine particles and direct discharges are the major mechanisms affecting the distribution patterns.     

太湖五里湖区表层沉积物中酸挥发性硫化物和同步提取金属

湖泊底泥中的酸溶硫化物易与二价金属生成难溶金属硫化物,从而制约沉积物中二价有毒金属的化学活性以及生物有效性,进而影响沉积物的环境质量.对沉积物中的酸溶硫化物(AVS)和同步提取金属(SEM)进行测定,依据SEM/AVS的比值可以判定重金属生物有效性.通过对太湖五里湖、梅梁湾表层沉积物夏季和秋季AVS与SEM的采样分析,结果表明:研究区域内AVS的含量夏季高于秋季,SEM受季节影响很小,SEM/AVS大于1,且秋季高于夏季,初步判断该湖区沉积物中重金属具有潜在的生物毒性.     

Trace element content of seagrasses in the Leschenault Estuary,Western Australia

Estuarine environments are particularly vulnerable to human impacts. In this study, trace elements in Ruppia megacarpa, Halophila ovalis, sediment and porewater were analysed to assess the potential contamination of the Leschenault Estuary, Western Australia, from a primarily agricultural drain. Sediment concentrations of Cd, Cu, Mn, and Ni and were highest nearest the drain while Al, As, Cr, Fe and Zn and were highest further from the drain. H. ovalis showed greater accumulation of Fe, Al, and As than R. megacarpa. Concentrations of Fe, Al, As, and Ni were generally higher in below-ground plant parts than above, suggesting uptake of these trace elements via the sediment-route pathway. This study suggested that the drain was a source of Cu and Mn, with these elements entering the estuary through water inflows. As and Fe, were highest furthest from the drain suggesting input of trace elements from sources other than the drain under study.     

A metal particle from a Ca,Al-rich inclusion from the meteorite Allende,and the condensation of refractory siderophile elements

A small particle (ca. 10^?6 g) was magnetically separated from a Ca,Al-rich inclusion of the Allende meteorite. By using instrumental neutron activation analysis it was found that the elements Os, W, Re, Ir, Mo, Ru and Pt were enriched by a mean factor of about 7000 relative to Cl chondrites.A polished section of the grain showed that it consisted mainly of silicates, with a rounded particle of metal and sulfide (20 μm across) attached to it.Concentrations of up to 11% Pt were determined with the microprobe in the Ni-Fe center of the particle. Furthermore, Rh was for the first time measured in an Allende inclusion. It is enriched in about the same degree as Pt, Ir and W. The Ni-Fe center was surrounded by troilite. Mo was concentrated in the sulfide, while Os and Ru were inhomogeneously distributed over the metal + sulfide phases. The particle is interpreted as direct product of metal condensation of the solar nebula. The sulfide phase formed at lower temperatures and caused redistribution of the refractory siderophile elements. Condensation calculations for a metal alloy show that Fe and Ni are expected to be already present at higher temperatures than the condensation temperatures of pure Fe. Pt and Rh, having lower condensation temperatures than pure Fe should also be completely condensed above the condensation temperature of pure Fe. Kinetic considerations show that minimum times to grow this kind of particle should be of the order of 500 years at 10^?3 atm.     

Metal concentrations in water and sediments from tourist beaches of Acapulco, Mexico

A survey on the metal concentrations (As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V, Zn) in beach water and sediments is reported from the tourist destination of Acapulco city on the Pacific coast of Mexico. The concentration of dissolved trace metals (DTMs) in beach water and acid leachable trace metals (ALTMs) in sediments indicated that they are anthropogenic in nature due to the increased tourist activities in the crowded beach locations. The statistical analysis indicates Fe and Mn play a major role as metal scavengers in both the medium (water and sediment) and the higher value of other metals is site specific in the study area, indicating that they are transported from the local area. Comparison results suggest that the beach water quality has deteriorated more than the sediments and special care needs to be taken to restore the beach quality.     

Influence of metal oxides in the colorimetric determination of acid volatile sulfide in sediments

The sediment of Lagoa dos Patos‐MS, Brazil, was investigated to verify the influence of metal sulfides and oxyhydroxides of Mn and Fe on the heavy metal availability. The spectrophotometric method of methylene blue was used, with 8 interlinked tubes containing the samples with SnCl₂, where N₂ was introduced to release the H₂S extracted with 6.0 mol L^–1 HCl, and trapped in 0.05 M NaOH solution. The influence of SO₄^2–, Mn(IV) and Fe(III) oxyhydroxides was investigated with samples constituted by a mixture of MnO₂; Na₂SO₄; FeCl₃, and sediments. The presence of SnCl₂ was very important to avoid the interferences of iron and manganese oxyhydroxides. The method of standard addition was applied and the efficiency was (100.8 ± 9.4)%. The ratio among the quantities of metals potentially available and the acid volatile sulfide (AVS) indicate that the system presents small metals availability to the benthic community, by the existence of sulfide capable to immobilize the metal as insoluble sulfide.     

武汉东湖沉积物中酸挥发性硫化物(AVS)的深度分布及其影响因素

提要沉积物中酸挥发性硫化物(AVS)是硫化物的生成、氧化和扩散等综合作用的反映,有机物的供给、硫酸盐的还原等因素都能影响其分布特征。本文对武汉东湖三个污染程度不同站点的AVS深度分布特征进行了研究,结果表明,AVS含量在一定深度沉积物中具有最大值,东湖沉积物中AVS的深度分布具有两种不同的模式,Ⅰ站和Ⅱ站AVS浓度峰在5cm左右的表层沉积物中,且AVS还原层深度较狭窄,而Ⅲ站AVS浓度峰处于10-20cm深度范围,沉积物中有机质负荷的差异是导致这种分布特征的重要原因。沉积物中有机质含量对AVS的深度分布具有重要影响,高有机质负荷导致AVS浓度峰向表层迁移,且AVS还原层分布于较狭窄的深度范围,对方涛等对流-扩散模型的应用表明,该模型在高有机质负荷沉积物中(Ⅰ、Ⅱ站)AVS深度分布的应用较为理想,然而低有机质负荷沉积物中(Ⅲ站)不能准确反映AVS的深度分布特征,说明其应用范围具有一定的局限性。     

Redox status and heavy metal risk in intertidal sediments in NW Spain as inferred from the degrees of pyritization of iron and trace elements

Mariculture is an important economic activity in shallow marine areas of the Rías Baixas (Galicia, NW Spain). The maintenance of high product quality requires surveillance of environmental quality, including the risk of metal toxicity. In this study the redox status of intertidal sediments in the Bay of San Simón, and the risk of toxicity posed by their As, Cd, Cr, Cu, Mn, Ni, Pb and Zn contents, were evaluated by determination of operationally defined reactive, silicate-bound, organic and pyrite-related fractions of these elements and of Fe. The large silicate-bound fractions of most of these metals indicate their lithogenic origin; the main exception is Pb, which in all respects exhibits singular behaviour associated with its predominantly anthropogenic origin in a ceramics factory. In sediments with larger fine-grained particle contents, which are oxic only in the top few centimetres, greater proportions of the trace elements are present as sulphides or associated with sulphide minerals: the degree of pyritization of Fe (DOP) is 46% overall, and the pyrite fraction of some elements doubtless increases at the expense of the reactive fraction, most overall degrees of trace metal pyritization (DTMPs) lying in the range 10-50%. A decline in pyrite genesis at depths below about 18 cm in these sediments is attributed to the exhaustion of organic matter susceptible to metabolization by sulphide-generating bacteria. In coarse-grained, oxic sediments the oxidation of sulphides makes pyrite-related fractions very small, and reactive and silicate-bound fractions are negatively correlated; reactive fractions associated with Fe-Mn oxyhydroxides are large, and DOP and DTMPs are low (generally much lower than in mud-rich sediments), except for Pb. Most of the elements studied are mainly present in forms that are neither bioavailable nor potentially bioavailable, and so do not constitute a significant environmental threat. However, the high DTMPs of Cu and Pb indicate significant potential bioavailability, which should be taken into account in evaluations of environmental quality and the risk to bivalve cultures.     

Biogeochemistry of dissolved carbon,major, and trace elements during spring flood periods on the Ob River

Detailed knowledge of the flood period of Arctic rivers remains one of the few factors impeding rigorous prediction of the effect of climate change on carbon and related element fluxes from the land to the Arctic Ocean. In order to test the temporal and spatial variability of element concentration in the Ob River (western Siberia) water during flood period and to quantify the contribution of spring flood period to the annual element export, we sampled the main channel year round in 2014–2017 for dissolved C, major, and trace element concentrations. We revealed high stability (approximately ≤10% relative variation) of dissolved C, major, and trace element concentrations in the Ob River during spring flood period over a 1‐km section of the river channel and over 3 days continuous monitoring (3‐hr frequency). We identified two groups of elements with contrasting relationship to discharge: (a) DIC and soluble elements (Cl, SO₄, Li, B, Na, Mg, Ca, P, V, Cr, Mn, As, Rb, Sr, Mo, Ba, W, and U) negatively correlated (p < 0.05) with discharge and exhibited minimal concentrations during spring flood and autumn high flow and (b) DOC and particle‐reactive elements (Al, Fe, Ti, Y, Zr, Nb, Cs, REEs, Hf, Tl, Pb, and Th), some nutrients (K), and metalloids (Ge, Sb, and Te), positively correlated (p < 0.05) with discharge and showed the highest concentrations during spring flood. We attribute the decreased concentration of soluble elements with discharge to dilution by groundwater feeding and increased concentration of DOC and particle‐reactive metals with discharge to leaching from surface soil, plant litter, and suspended particles. Overall, the present study provides first‐order assessment of fluxes of major and trace elements in the middle course of the Ob River, reveals their high temporal and spatial stability, and characterizes the mechanism of river water chemical composition acquisition.     

The degree of trace metal pyritization in subtidal sediments of a mariculture area: application to the assessment of toxic risk

Four 2–3 m sediment cores were taken at the sites on the periphery of mussel raft concentrations in the subtidal zone of the inner Ría de Vigo (Galicia, NW Spain) with a view to evaluate the potential risk to mariculture from sediment-borne trace elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn). The distribution of each of these elements in reactive, organic, pyrite and silicate-bound fractions was determined at 64 samples, and these data were used to calculate the degree of trace metal pyritization (DTMP) of each metal/metalloid. In the top 10–20 cm, relatively oxic conditions led to As, Cd, Cu, Pb and Zn having large reactive fractions due to their association with Fe and Mn oxyhydroxides. At lower levels, anoxic conditions favoured by intense diagenesis led to the precipitation of trace metals and metalloids as sulphides, with or without association with pyrite. Particularly large pyrite fractions in the 20–100 cm layer are attributed to the organic matter of this layer being more marine in origin than that of deeper sediments. DTMP was greatest for Cu and As, and least for Pb, Zn and Cr. The risk of trace element toxicity in the event of disturbances instituting oxic conditions in these sediments is discussed.     

Evaluation of metal contamination in coastal sediments of the Bay of Bengal, India: geochemical and statistical approaches

Surface sediment samples collected from the inner shelf region of the Bay of Bengal, were analysed for the major elements and total and acetic acid available trace elements (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Si, Zn) to evaluate geochemical processes influencing their distribution. Major elemental analysis showed that the sediments had high concentrations of Si and relatively low concentrations of Al and Fe. Both major elemental and trace metal concentrations indicated that the sediments represent weathered products of granite and charnockite. Normalization of metals to Al indicated relatively high enrichment factors for Pb, Cd, Zn and Cr. The higher proportions of nondetrital Pb (66%), Cd (41%) and Co (28%) reveal metal contamination due to anthropogenic inputs. Factor analysis (FA) identified six possible types of sedimentological and geochemical associations. The dominant factor accounting for 26.9% of the total variance identifies an anthropogenic input and accumulation of nondetrital Cd, Co, Cr, Ni and Pb. Association of these metals with CaCO3 reveals that shell fragments in the surface sediments are likely act as a carrier phase for nondetrital metals. The results are discussed in the context of the sources and pathways of elements in the Bay of Bengal.     

Dissolved trace elements in a nitrogen-polluted river near to the Liaodong Bay in Northeast China

Dissolved trace element concentrations (Ba, Fe, Mn, Si, Sr, and Zn) were investigated in the Haicheng River near to the Liaodong Bay in Northeast China during 2010. Dissolved Ba, Fe, Mn, and Sr showed significant spatial variation, whereas dissolved Fe, Mn, and Zn displayed seasonal variations. Conditions such as water temperature, pH, and dissolved oxygen were found to have an important impact on redox reactions involving dissolved Ba, Fe, and Zn. Dissolved Fe and Mn concentrations were regulated by adsorption or desorption of Fe/Mn oxyhydroxides and the effects of organic carbon complexation on dissolved Ba and Sr were found to be significant. The sources of dissolved trace elements were found to be mainly from domestic sewage, industrial waste, agricultural surface runoff, and natural origin, with estimated seasonal and annual river fluxes established as important inputs of dissolved trace elements from the Haicheng River into the Liaodong Bay or Bohai Sea.