Pyritization of trace metals in estuarine sediments and the controlling factors: a case in Jiaojiang Estuary of Zhejiang Province,China

Three undisturbed sediment samples were collected from the intertidal zone of the Jiaojiang Estuary of Zhejiang Province, China. The sediments were found to contain remarkably low concentrations of organic carbon (<0.6%) and acid volatile sulfide (AVS) (<30 μmol g⁻¹). The availability of these two substrates likely constrained sulfate reduction and pyritization of several trace metals, respectively. This was especially true at one station where AVS concentrations in the upper 20 cm averaged less than 0.05 μmol g⁻¹. Although the depth dependence of the degree of trace metal pyritization was generally consistent with expectations based on redox conditions, depth profiles of reactive-metal and pyrite-metal concentrations in several cases revealed more complex behavior and a positive correlation between reactive-metal concentrations and pore water metal concentrations.     

Accumulation and partitioning of heavy metals in mangrove rhizosphere sediments

A field study was conducted to clarify the effect of rhizosphere processes on the accumulation and partitioning of heavy metals (Pb, Zn, Cu, Cr, Cd and Ni) in mangrove sediments. Metals were fractionated by a sequential extraction procedure into three chemically distinct fractions: water soluble, exchangeable and carbonate bound (B1), Fe–Mn oxide bound (B2), and organic and sulfide bound (B3). Results indicate that rhizosphere processes tend to increase the metal concentrations in the rhizosphere sediments. However, plant uptake may result in the decrease of the metal concentrations in the rhizosphere sediments when the metal concentrations are relatively low in the bulk sediments. Compared with the bulk sediments, the rhizosphere sediments have low concentrations of heavy metals in the B1 and B2 fractions and high concentrations in the B3 fraction. Either an increase or decrease in the residual fraction of heavy metals in the rhizosphere sediments may appear, depending on whether the formation of the refractory metal-organic compounds or the activation of the residual fractions dominates. Results also indicate that mangrove plants absorb and store non-essential metals in the perennial tissues, thus reducing the export of non-essential metals via leaf litter transport. Mangrove plants are excellent candidates for phytostabilization of heavy metals in intertidal substrates.     

The geochemistry of redox sensitive trace metals in sediments

We analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the U.S. Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates ≤1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, we calculate the area of sediments below 1000 m water depth in which oxygen penetration is ≤1 cm to be 4% of the ocean floor. We conclude that sediments where oxygen penetrates ≤1 cm release Mn, V and Mo to seawater at rates of 140%–260%, 60%–150% and 5%–10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%–140%, 30%–80% and 20%–40%, respectively, of their dissolved riverine inputs. We modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates ≤1 cm. Our analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%–10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%–20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of Cd/Ca and V/Ca ratios observed in foraminifera shells over the last 40 kyr. This implies that the area of reducing sediments in the ocean deeper than 1000 m (4%) has not been greater than twice the present value in the recent past.     

Speciation of trace metals in sediments of a tropical estuary

Axial surveys were performed in the two river tributaries of the Cochin estuary, SW India during November 1988. Surficial sediments were subjected to sequential chemical extractions to delineate five metal fractions, namely, exchangeable, carbonate bound, easily reducible, organic/sulfide bound, and residual. The results indicated selective accumulation of Mn and Ni in carbonate bound and organic/sulfide forms, along with marginal amounts of Co in the exchangeable fraction. Large portions of Fe and Cr occurred in the residual fraction, whereas composite fractionation of Zn species was noticed. The exchangeable fractions of Fe and Cr as well as of easily reducible cobalt were below detection limits. The levels of Cr and Zn indicate anthropogenic inputs in this estuary, whereas Co and Ni show regional contamination exceeding natural levels. The analytical speciation procedure helps to deduce the sedimental diagenetic processes in the estuarine environment.     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Heavy metals in mangrove sediments of the central Arabian Gulf shoreline,Saudi Arabia

To assess heavy metals in mangrove swamps of Sehat and Tarut coastal areas along the Arabian Gulf, 18 sediment samples were collected for Al, V, Cr, Mn, Cu, Zn, Cd, Pb, Hg, Sr, As, Fe, Co, and Ni analysis. The results indicated that the distribution of some metals was largely controlled by anthropogenic inputs, while others were of terrigenous origin and most strongly associated with distribution of aluminum and total organic carbon in sediments. Mangrove sediments were extremely severe enriched with Sr (EF?=?67.59) and very severe enriched with V, Hg, Cd, Cu, As (EF?=?44.28, 37.45, 35.77, 25.97, and 11.53, respectively). Average values of Sr, V, Hg, Cd, Cu, Ni, As, and Cr were mostly higher than the ones recorded from the Mediterranean Sea, the Red Sea, the Gulf of Aqaba, the Caspian Sea, the Arabian and Oman gulfs, coast of Tanzania, sediment quality guidelines, and the background shale and the earth crust. Landfilling due to coastal infrastructure development around mangrove forests, oil spills and petrochemical and desalination effluents from Al-Jubail industrial city to the north were the anthropogenic activities that further enhanced heavy metals in the studied mangrove sediments.     

广西珍珠湾红树林湿地沉积物重金属分布及评价

沉积物中的重金属属于持久性污染物,具有富集性、难降解性和毒性,长时间累积会对生态环境和人体健康造成威胁。为研究珍珠湾红树林湿地表层沉积物中的重金属含量分布特征及质量现状,2021年9月在珍珠湾红树林分布区采集13件表层沉积物样品,分析测试重金属含量。结果表明: 与国内其他红树林湿地相比,珍珠湾红树林湿地表层沉积物中的重金属含量处于相对较低水平; 地累积指数法显示大部分表层沉积物样品无重金属污染,仅有2个站位受到Cd和Hg的轻微污染,潜在生态风险指数法表明湾内各站位均为低生态风险; 相关性分析和主成分分析表明,Cd主要受江平江输入和珍珠湾东南部海水养殖的影响,其他元素主要为自然背景的岩石风化沉积,利用主成分-多元线性回归模型对重金属的来源进行解析认为,表明江平江输入的重金属贡献率为57%,海水养殖影响的重金属贡献率为43%。综上所述,珍珠湾红树林湿地整体生态状况良好,但仍需重点关注Cd的输入。     

Preliminary assessment of trace metals and polycyclic aromatic hydrocarbons in the sediments

Total concentrations of Cd, Cr, Co, Fe, Pb, Ni, Mn and Zn were determined by atomic absorption spectrophotometry in the surface sediments of Taylor Creek, Southern Nigeria. The most concentrated trace metals, ranging from 113.2 to 5160.7 mg/g-dry weights were Fe, Pb, Mn, Ni and Zn. There was no significant variation in sediment-associated metal levels (P>0.05). The metal pollution index was highest at Agbia/Nedugo and is attributed to local contamination of the Creek. The concentrations of low molecular weight polycyclic aromatic hydrocarbons (PAHs) were also detected and quantified in the sediments by capillary gas chromatography equipped with a flame ionization detector. The concentration levels of 178.1-1266.3 mg/g-wet weights were high for the PAHs. The results indicate that the pollutants, which are bio-accumulatable, could contribute to inferior biodiversity, and shifts in community composition from sensitive to tolerant taxa.     

Authigenic associations between selected rare earth elements and trace metals in lacustrine sediments

Surficial sediment samples were collected at 47 stations in Little Traverse Bay, Lake Michigan, to determine the geochemical associations between certain rare earth elements (REE's) and trace metals. Each sample was analyzed for carbonate carbon, organic carbon, grain size, and the elements Al, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, and Mn. Two distinct Ce subpopulatins were identified by graphical analysis, and an R-mode factor analysis was applied to data from the “enriched” Ce subpopulation (18 samples). Results show that the REE's and trace metals are primarily enriched in the authigenic phase of these sediments. Partial correlation analyses indicate that the REE's are primarily associated with hydrous Fe oxides relative to organic matter in this phase. The ratio of Ce/La concentrations increased markedly from the bay margins to the central trough of the bay, indicating that Ce, similar to Fe, exhibits a variable oxidation state in the authigenic phase of nearshore fine-grained sediments. The results of the present study suggest that the REE's and trace metals behave coherently in the authigenic phase of recent lacustrine sediments, and the REE's may be useful as geochemical tracers to differentiate between trace metal enrichments in surface sediments as a result of diagenesis and pollution loadings.     

Geological factors affecting the distribution of trace metals in glacial sediments of central Newfoundland

 In central Newfoundland (NTS 12A/10, 15, 16, 2H/1), As, Pb, and Zn concentrations in the clay-sized (<0.002 mm) and silt and clay-sized (<0.063 mm) fractions of till reflect compositional differences among and within rock terranes at scales of kilometers to tens of kilometers. In those fractions, till derived from volcanic bedrock of Victoria Lake Group (Tulks Hill) is notably enriched in As (50–>1000 ppm), exceeding levels commonly set for purposes of environmental protection. Near Pb-Zn mines at Buchans, geochemical variation with depth reflects the dispersal of detritus from mineralized bedrock, and differences in sediment type and provenance. There, surface sediments are rich in granitic debris derived from the Topsails igneous terrane 5 km north of Buchans and contain low concentrations of trace metals. These sediments are compositionally unrelated to either Buchans Group volcanic rock or an underlying, older till enriched in sulphide minerals and trace metals. Metal-rich till extending up to 10 km southwest of Buchans results from combined glacial and debris flow transport related to two distinct geological events. Trace metals are enriched (two- to fourfold) in the clay-sized fraction of till compared to the silt and clay-sized, and are associated with Al- and Mg-bearing minerals that preferentially concentrate in the clay fraction. The geochemistry of the silt and clay-sized fraction can approximate that of the <2-mm fraction. Background variations in till illustrate the important role of a geological framework to the interpretation of geochemical surveys and the origins of trace metals in the environment. Received: 31 October 1996 · Accepted: 27 May 1997     

Occurrence forms of trace metals in recent bottom sediments from the White and Barents Seas

For the first time based on determination of the geochemical occurrence forms of trace metals the main processes that control the accumulation of elements (Al, Mn, Fe, Mo, Cr, Ni, Co, Cu, Pb, Cd, and As) in the recent sediment cores from the White Sea and Barents Sea were quantified. A high-resolution study of the bottom sediment cores allowed us to estimate the short-term variations (periodicity of 10–15 years) in the accumulation of metals to reveal the periods of maximum Fe and Mn contents in the amorphous hydroxides fraction, which serve as effective adsorbents of the trace elements majority, including heavy metals. The Mn/Fe ratio in the amorphous hydroxides phase can be considered as geochemical indicators of early diagenesis.     

Assessment of trace metals contamination in stream sediments and soils in Abuja leather mining,southwestern Nigeria

This study is aimed at determining the level of environmental degradation as well as the concentration of trace elements in soil and stream sediments in order to evaluate the environmental impact of the mining operation. Twenty-five (25) soils and ten (10) stream sediment samples were collected from the study area. The physicochemical parameters were determined using appropriate instrumentation with the aid of a digital pH meter (Milwaukee meter) to measure the pH and electrical conductivity, total dissolved solids, moisture content and loss on ignition of the soil and stream sediment samples. The pH of the soil sample ranged from (6.10 to 7.19); Electrical conductivity ranged from (21.3 to 279.4 µS/cm), moisture content varied from (0.60% to 7.20%), and the LOI ranged from (2.03% to 18.62%). The results of the analysis showed that the concentrations of the trace elements in the soils and stream sediment samples were slightly higher than the background values. Plots of the trace elements in stream sediment samples show moderate, consistent decrease downstream except at points where there was mine water discharge into the main river. The pollution levels of heavy metals were examined in stream sediment and soil samples using different assessable indices, such as the enrichment factor, which showed significant-moderate enrichment for Cr, Th, Nb, Zn, Pb, Y and Zr and the geo-accumulation index, which showed practically moderate contamination with Cr, Ni and Sr based on regional background reference values. Geo-accumulation index and contamination index for soils and stream sediment revealed uncontaminated to moderate contamination. Likewise, elements with moderate contamination were Cr, Ni and Sr. The Pearson correlation showed that there were significant positive associations among selected metals in soil and stream sediment samples.     

Nitrate depuration of secondary sewage effluents in mangrove sediments

The sewage treatment plant (STP) at La Parguera, on the southwest coast of Puerto Rico, discharges an average of 228,000 dm³ of secondary sewage effluents per day into percolation ponds located at the landward margin of the coastal mangrove fringe. Effluents flowing from the STP percolation ponds to the adjacent mangrove fringe typically exhibited nitrate levels between 0.2 mM and 1.0 mM. Experimental determination of actual and potential denitrification using acetylene block and substrate disappearance techniques indicate that mangrove sediment microbial communities are capable of depurating 10 to 15 times the nitrate added in the STP effluent. Plots of porewater salinities vs nitrate concentrations show exponential decay of nitrate concentration. Our observations confirm the potential of mangrove sediment-microbial communities for nitrate depuration of secondary sewage effluents.     

Pyritization of tubes and burrows from Late Pleistocene continental shelf sediments off North Norway

Four different types of pyritized tubes and three types of pyritized burrow fillings are described from Pleistocene glaciomarine sediments in Andfjorden, northern Norway. The tubes and burrows probably originated from tubicolous and burrowing polychaetes respectively. The decomposition of the organic matter in the tubes and burrows created a reducing micro-environment favouring precipitation of pyrite. By comparison with Holocene tubes from marine sediments in Andfjorden and FugloSyfjorden, it is seen that pyritization commenced with isolated spherules. These spherules with incipient pyrite crystals and framboids were formed mainly on the inner wall of the tube. Presence of a monosulphide in the Holocene Fugløyfjorden material suggests that the pyritization process has reached a later phase; the final result would be a completely pyritized trace fossil. It is shown that single pyrite crystals (octahedra) generally attain greater size in the burrow fillings than in the tubes. The microstructure found in some of the pyritized tubes is interpreted as a reflection of the microstructure in the original wall. Finally, the implications for the depositional environment in Pleistocene in Andfjorden is investigated with reference to the benthic skeletal macrofaunal assemblage in the sequence. The pyritized trace fossils occur frequently in an opportunistic assemblage from a period (c. 14,000–13,000 yr BP) characterized by some oxygen deficiency. Later (13,000–10,000 yr BP) they play a minor role in an established assemblage under improved oxygen conditions.     

Enrichment of trace metals in surface sediments from the northern part of Point Calimere, SE coast of India

This study deals with the geochemical nature of distribution, enrichment of total trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) in bulk sediments and its association with sediment texture, carbonates and organic carbon. Sixty surface sediment samples were collected during two different seasons in 2002 and 2003 along the coastal regions in three transects from Nagapattinam town, north of Point Calimere in southeast coast of India. The sediments are mostly sandy silt and are dominated by the carbonate content. Organic carbon distribution indicates that they are brought in by the minor river input. Enrichment of trace metals is clearly identified by the domination of Pb, Zn, Cd with high values than the average crustal values and comparison of trace metals from other coastal regions in the southeast coast of India. Statistical analysis clearly indicates that Fe and Mn control the distribution of trace metals and are concentrated in the finer particles and organic carbon fraction. The increase in concentration signifies the need for regular monitoring of the offshore coastal region in southeast coast of India which was recently destroyed by the 2004 December tsunami event, and which is also located near the Sethu Samuthram Ship Canal Project.     

High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

Geochemistry of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan Province (P. R. China): implications on sources of trace metals

This paper reports a geochemical study of trace metals and Pb isotopes of sediments from the lowermost Xiangjiang River, Hunan province (P. R. China). Trace metals Ba, Bi, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, Mo, Cd, Sn, Sb, Pb, Tl, Th, U, Zr, Hf, Nb and Ta were analyzed using ICP-MS, and Pb isotopes of the bulk sediments were measured by MC-ICP-MS. The results show that trace metals Cd, Bi, Sn, Sc, Cr, Mn, Co, Ni, Cu, Zn, Sb, Pb and Tl are enriched in the sediments. Among these metals, Cd, Bi and Sn are extremely highly enriched (EF values >40), metals Zn, Sn, Sb and Pb significantly highly (5 < EF < 20), and metals Sc, Cr, Mn, Co, Ni, Cu and Tl moderately highly (2 < EF < 5) enriched in the river sediments. All these metals, however, are moderately enriched in the lake sediments. Geochemical results of trace metals Th, Sc, Co, Cr, Zr, Hf and La, and Pb isotopes suggest that metals in the river sediments are of multi-sources, including both natural and anthropogenic sources. Metals of the natural sources might be contributed mostly from weathering of the Indosinian granites (GR) and Palaeozoic sandstones (PL), and metals of anthropogenic sources were contributed from Pb–Zn ore deposits distributed in upper river areas. Metals in the lake sediments consist of the anthropogenic proportions, which were contributed from automobile exhausts and coal dusts. Thus, heavy-metal contamination for the river sediments is attributed to the exploitation and utilization (e.g., mining, smelting, and refining) of Pb–Zn ore mineral resources in the upper river areas, and this for the lake sediments was caused by automobile exhausts and coal combustion. Metals Bi, Cd, Pb, Sn and Sb have anthropogenic proportion of higher than 90%, with natural contribution less than 10%. Metals Mn and Zn consist of anthropogenic proportion of 60–85%, with natural proportion higher than 15%. Metals Sc, Cr, Co, Cu, Tl, Th, U and Ta have anthropogenic proportion of 30–70%, with natural contribution higher than 30%. Metals Ba, V and Mo might be contributed mostly from natural process.