Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Copper, zinc and lead speciation in salt marsh sediments colonised by Halimione portulacoides and Spartina maritima

Total concentrations and fractionation of Cu, Zn and Pb in seven operationally defined phases (exchangeable, carbonates, manganese oxides, organic complexes, amorphous iron oxides, crystalline iron oxides and residual) were determined in sediments colonised by the halophyte species Halimione portulacoides and Spartina maritima in a Tagus estuary salt marsh (Portugal). We aimed to determine whether the speciation of these metals was different in areas colonised by each halophyte. Higher concentrations of Cu, Zn and, in particular Pb, were found in the rhizosphere of S. maritima than in the root sediments of H. portulacoides. Geochemical fractionation of Cu, Zn and Pb in sediments of the salt marsh depended upon the metal, and for Zn and Pb clearly varied with depth and with the colonising species. The higher redox potential observed in sediments colonised by H. portulacoides may in part explain the observed differences in the speciation of Cu, Zn and Pb.     

Metal uptake capability of <Emphasis Type="Italic">Cyperus articulatus</Emphasis> L. and its role in mitigating heavy metals from contaminated wetlands

Wetland plants are biological filters that play an important role in maintaining aquatic ecosystem and can take up toxic metals from sediments and water. The present study investigated the seasonal variation in the accumulation potential of heavy metals by Cyperus articulatus in contaminated watercourses. Forty quadrats, distributed equally in 8 sites (six contaminated sites along Ismailia canal and two uncontaminated sites along the River Nile), were selected seasonally for sediment, water, and plant investigations. Autumn was the flourishing season of C. articulatus with the highest shoot density, length, and diameter as well as aboveground biomass, while summer showed the least growth performance. The photosynthetic pigments were markedly reduced under contamination stress. C. articulatus plants accumulated concentrations of most heavy metals, except Pb, in their roots higher than the shoots. The plant tissues accumulated the highest concentrations of Fe, Cd, Ni, and Zn during autumn, while Cu and Mn during spring, and Cr and Co during winter. It was found that Cd, Cu, Ni, Zn, Pb, and Co had seasonal bioaccumulation factor (BF) > 1 with the highest BF for Cd, Ni, and Zn during autumn, Co, Cu, and Pb in winter, spring, and summer, respectively. The translocation factor of most heavy metals, except Pb in spring, was <1 indicating potential phytostabilization of these metals. In conclusion, autumn is an ideal season for harvesting C. articulatus in order to monitor pollution in contaminated wetlands.     

Oxidation of acid-volatile sulfide in surface sediments increases the release and toxicity of copper to the benthic amphipod Melita plumulosa

Acid-volatile sulfides (AVS) are an important metal-binding phase in sediments. For sediments that contain an excess of AVS over simultaneously extracted metal (SEM) concentrations, acute or chronic effects should not result from the metals Cd, Cu, Ni, Pb and Zn. While AVS phases may exist in surface sediments, the exposure to dissolved oxygen may oxidize the AVS and release metals to more bioavailable forms. We investigated the role of oxidation of AVS, and specifically copper sulfide phases, in surface sediments, in the toxicity to juveniles of the epibenthic amphipod, Melita plumulosa. Sediments containing known amounts of copper sulfide were prepared either in situ by reacting dissolved copper with AVS that had formed in field sediments or created in sediments within the laboratory, or by addition of synthesised CuS to sediments. Regardless of the form of the copper sulfide, considerable oxidation of AVS occurred during the 10-d tests. Sediments that had a molar excess of AVS compared to SEM at the start of the tests, did not always have an excess at the end of the tests. Consistent with the AVS-SEM model, no toxicity was observed for sediments with an excess of AVS throughout the tests. However, the study highlights the need to carefully consider the changes in AVS concentrations during tests, and that measurements of AVS and SEM concentrations should carefully target the materials to which the organisms are being exposed throughout tests, which in the case of juvenile M. plumulosa is the top few mm of the sediments.     

巢湖表层沉积物中重金属的分布特征及其污染评价

以巢湖表层沉积物为研究对象,利用BCR连续提取法研究了沉积物中Cr、Co、Ni、Cu、Cd、Zn、V和Pb等8种重金属元素的分布特征,同时运用潜在风险指数法和地累积指数法综合评价了巢湖沉积物中重金属的生态风险。结果表明,巢湖沉积物中的重金属含量在空间上表现出东西高、中间低的分布特征。巢湖表层沉积物中Cr、Co、Ni、V和Cu 5种重金属都主要以残渣态为主,Zn和Cd主要以弱酸提取态为主,Pb以可还原态为主,同时,Co和Cu 2种元素的可交换态及可还原态含量占有较高比例,具有潜在危害性。相关性分析显示,Cr、Cu、Pb、Ni、Zn和Cd 6种重金属元素的来源和分布可能具有相似性,Co和V 2种重金属元素具有相似的地球化学行为且其主要来源可能与其他几种重金属不同。潜在生态风险指数评价结果表明,巢湖表层沉积物中8种重金属元素构成的生态危害顺序为:Cd>Pb>Co>Cu>Ni>Zn>V>Cr,Cd具有高的生态危害等级,其他7种重金属元素均为低生态危害等级。地累积指数法评价结果表明:巢湖沉积物重金属元素的富集程度为Cd>Zn>Pb>Co>Cu>V>Ni>Cr,Cr属于清洁级别,Co、Cu、V和Ni处于轻度污染水平,Zn和Pb处于偏中度污染,Cd达到了重污染水平。     

Temporal variations and bioaccumulation of heavy metals in different Suaeda salsa marshes of the Yellow River estuary,China

To understand the temporal variations and bioaccumulation of heavy metals in the coastal marshes, the concentrations of heavy metals (Cr, Ni, Pb, and Cu) in the two Suaeda salsa marshes [middle S. salsa marsh (MM) and low S. salsa marsh (LM)] of the Yellow River estuary were determined from May to November in 2008 by in situ sampling and inductively coupled plasma mass spectrometry (ICP-MS) analysis. Results showed that heavy metal concentrations in S. salsa of MM and LM were generally in the order of Cu?>?Cr?>?Pb?>?Ni, while those in sediments fell in the order of Cr?>?Ni?>?Cu?>?Pb. Heavy metal concentrations of S. salsa in MM and LM were different, and significant differences were observed in stems (F?=?4.797, p?=?0.046) and litters (F?=?6.799, p?=?0.026) for Ni. Litter was the main stock of heavy metals, and the allocations of Cr, Ni, and Pb reached 31.25–51.31, 28.49–42.58, and 29.55–66.79 % (in MM) and 36.73–48.60, 41.70–57.87, and 33.30–60.64 % (in LM), respectively. The ratios of roots/leaves (R/L) and roots/stems (R/S) for Cr and Ni in MM were mostly greater than 1, while those ratios in LM were mostly less than 1, indicating that Cr and Ni in S. salsa at LM had greater mobility compared with those at MM. Moreover, the [accumulation factor, AF]_plant of Cr, Ni, Cu, and Pb in LM, especially [AF]_root and [AF]_stem of Cr and [AF]_litter of Ni, was also higher than that in MM. These indicated that S. salsa grown in LM was more suitable for potential biomonitor or phytoremediation of Cr, Ni, Cu, and Pb if intertidal sediments were seriously contaminated with an increase of pollutant loading (especially heavy metals) in the Yellow River estuary. The use of biomonitor (S. salsa) living and growing in LM could yield valuable information not only on the presence of anthropogenic stressors, but, more importantly, on the adverse influence the stressors are having on the environment.     

Concentrations,spatial distribution,and pollution assessment of heavy metals in surficial sediments from upstream of Yellow River,China

Surface sediments were collected from 122 sites in the upstream of the Yellow River, China. The concentration of Fe, Mn, Cu, Ni, Zn, Cr, Pb, and Cd in sediments was investigated to explore the spatial distribution based on statistics and interpolation method. The results suggested that the concentrations of heavy metals were lower than potential effect levels (PEL). The samples above threshold effect level (TEL) for Pb and Zn were less than 10%, while almost 50% of samples for Ni exceeded PEL. Pb and Zn in sediments performed little or no adverse effects on the aquatic ecosystems. Higher concentrations of all heavy metals occurred in Qinghai and Gansu sections; the concentrations of Cu, Ni, and Zn were significantly higher than the Inner Mongolia section. Lower concentration of Fe, Mn, Cu, Ni, and Zn appeared in Qinghai section; the concentrations of Fe, Mn, Cr, and Pb manifested relatively steady and similar distributions and approximately decreasing tendency along the upstream of Yellow River.

     

Geochemical evidences of the anthropogenic alteration of trace metal composition of the sediments of Chiricahueto marsh (SE Gulf of California)

Seven sediment cores (60-80 cm) were collected at Chiricahueto marsh, a salt marsh influenced by agrochemical, domestic and industrial effluents. The concentrations of Ag, Al, Cd, Co, Cu, Fe, Li, Mn, Pb, V and Zn were studied in the solid phase at each 1-cm section. The profiles of Ag, Cd, Cu, Mn, Ni, Pb and Zn showed a slight recent pollution in the site with enrichment and anthropogenic factors higher than unity; and correlation analysis indicated a direct association with organic carbon. Al, Co, Cr, Fe, Li, and V concentration profiles displayed a negative correlation with organic C and positive with mud content and no consistent enrichment at surface. Based on the principal component analysis and correlation analysis, two principal groups of metals were identified. The first group includes Al, Co, Cr, Fe and Li, that are derived predominantly from the weathering of parent materials in the local bedrock; and the second group include most of the metals, which were relatively enriched at surficial sediments, that are produced mainly by anthropogenic activities such as agriculture (Cd, Cu and Zn), sewage effluents (Ag, Cd, Cu, Ni, Pb and Zn) and in lesser extent atmospheric deposition (Cd and Pb).     

北运河表层沉积物对重金属Cu、Pb、Zn的吸附

首先分析了北运河6个采样点表层沉积物中重金属含量及相关基本特征。通过实验室模拟实验,利用分配系数Kd评价沉积物对重金属Cu、Pb、Zn的吸附特性,进一步考察了水体pH变化和有机质对重金属在北运河沉积物上吸附的影响。结果表明,沉积物中重金属的含量顺序为Zn>Cu>Pb,去除有机质后,沉积物对重金属的吸附能力显著降低,但各采样点中的重金属含量,沉积物对重金属吸附能力,以及沉积物中的有机质含量并没有明显相关性,这可能是因为不同采样点中有机质种类与结构不同导致的。总之,北运河沉积物对Pb有很强的吸附能力,其次是Cu和Zn,而且,Cu、Zn、Pb的吸附量随着pH的升高逐渐增大,水体pH值对于Zn的吸附影响更大。     

Assessment of heavy metal contamination in Hindon River sediments: a chemometric and geochemical approach

The aim of this study was to assess the level of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface sediments of the Hindon River, India that receives both treated and untreated municipal and industrial discharges generated in and around Ghaziabad, India. Mean metals concentrations (mg kg⁻¹) were in the range of; Cu: 21.70-280.33, Cd: 0.29-6.29, Fe: 4151.75-17318.75, Zn: 22.22.50-288.29, Ni: 13.90-57.66, Mn: 49.55-516.97, Cr: 17.48-33.70 and Pb: 27.56-313.57 respectively. Chemometric analysis was applied to identify contribution sources by heavy metals while geochemical approaches (enrichment factor and geo-accumulation index) were exploited for the assessment of the enrichment and contamination level of heavy metals in the river sediments. Chemometric analysis suggested anthropic origin of Cu, Cd, Pb, Zn, and Ni while Fe showed lithogenic origin. Mn and Cr was associated and controlled by mixed origin. Geochemical approach confirms the anthropogenic influence of heavy metal pollution in the river sediments. The study suggests that a complementary approach that integrates chemometric analysis, sediment quality criteria, and geochemical investigation should be considered in order to provide a more accurate appraisal of the heavy metal pollution in river sediments. Consequently, it may serve to undertake and design effective strategies and remedial measures to prevent further deterioration of the river ecosystem in future.     

Relationship between heavy metals concentrations in egret species,their environment and food chain differences from two Headworks of Pakistan

Concentration of ten metals (Cd, Cr, Co, Cu, Fe, Li, Mn, Ni, Pb and Zn) were analyzed in the egg contents, prey and soil samples of little egret (Egretta garzetta) and cattle egret (Bubulcus ibis) from two Headworks to determine habitat and species-specific differences; to assess the importance of prey and habitat contamination as an exposure source for heavy metals. Concentration of Cu, Mn, Cr and Pb in egg contents, Fe, Co, Cu, Mn, Zn in prey and Fe, Co, Cu, Ni, Li in surface soils were significantly different (P < 0.05). Mean metal concentrations of Cr, Pb and Cd were relatively higher in little egret whereas Cu and Mn were higher in the egg contents of cattle egret. The mean concentrations of Cu, Mn and Zn were higher in prey samples of cattle egrets and Cr, Cd and Pb in prey samples of little egrets. In soil samples collected from little egret heronries metal concentrations were higher except Cu and Ni. Correlation Analysis and Hierarchical Agglomerative Cluster Analysis (HACA) identified relatively similar associations of metals and their source identification. Metals such as Fe, Cu, Mn, and Li were related with geochemical origin from parent rock material as well as anthropogenic input whereas Cr, Cd, Pb, Ni, Co and Zn were associated mostly with anthropogenic activities. The study suggested that eggs are useful bio-monitor of local heavy metal contamination.     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Effects of sediment burial disturbance on macro and microelement dynamics in decomposing litter of <Emphasis Type="Italic">Phragmites australis</Emphasis> in the coastal marsh of the Yellow River estuary,China

From April 2008 to November 2009, a field decomposition experiment was conducted to investigate the effects of sediment burial on macro (C, N) and microelement (Pb, Cr, Cu, Zn, Ni, and Mn) variations in decomposing litter of Phragmites australis in the coastal marsh of the Yellow River estuary. Three one-off sediment burial treatments [no sediment burial (0 mm year^?1, S₀), current sediment burial (100 mm year^?1, S₁₀), and strong sediment burial (200 mm year^?1, S₂₀)] were laid in different decomposition sites. Results showed that sediment burials showed significant influence on the decomposition rate of P. australis, in the order of S₁₀ (0.001990 day^?1)?≈?S₂₀ (0.001710 day^?1)?>?S₀ (0.000768 day^?1) (p?<?0.05). The macro and microelement in decomposing litters of the three burial depths exhibited different temporal variations except for Cu, Zn, and Ni. No significant differences in C, N, Pb, Cr, Zn, and Mn concentrations were observed among the three burial treatments except for Cu and Ni (p?>?0.05). With increasing burial depth, N, Cr, Cu, Ni, and Mn concentrations generally increased, while C, Pb, and Zn concentrations varied insignificantly. Sediment burial was favorable for C and N release from P. australis, and, with increasing burial depth, the C release from litter significantly increased, and the N in litter shifted from accumulation to release. With a few exceptions, Pb, Cr, Zn, and Mn stocks in P. australis in the three treatments evidenced the export of metals from litter to environment, and, with increasing burial depth, the export amounts increased greatly. Stocks of Cu and Ni in P. australis in the S₁₀ and S₂₀ treatments were generally positive, evidencing incorporation of the two metals in most sampling times. Except for Ni, the variations of C, N, Pb, Cr, Cu, Zn, and Mn stocks in P. australis in the S₁₀ and S₂₀ treatments were approximated, indicating that the strong burial episodes (S₂₀) occurred in P. australis marsh in the future would have little influence on the stocks of these elements. With increasing burial depths, the P. australis was particularly efficient in binding Cu and Ni and releasing C, N, Pb, Cr, Zn, and Mn, implying that the potential eco-toxic risk of Pb, Cr, Zn, and Mn exposure might be very serious. This study emphasized the effects of different burials on nutrient and metal cycling and mass balance in the P. australis marsh of the Yellow River estuary.     

Inconsistency and comprehensiveness of risk assessments for heavy metals in urban surface sediments

Numerous indices have been developed to assess environmental risk of heavy metals in surface sediments, including the total content based geoaccumulation index (I_geo), exchangeable fraction based risk assessment code (RAC), and biological toxicity test based sediment quality guidelines (SQGs). In this study, the three indices were applied to freshwater surface sediments from 10 sections along an urbanization gradient of the Grand Canal, China to assess the environmental risks of heavy metals (Cu, Pb, Zn, Cd, and Cr) and to understand discrepancies of risk assessment indices and urbanization effects regarding heavy metal contamination. Results showed that Cd, Zn, and Pb were the most enriched metals in urban sections assessed by I_geo and over 95% of the samples exceeded the Zn and Pb thresholds of the effect range low (ERL) of SQGs. According to RAC, Cu, Zn, Cd, and Cr had high risks of adversely affecting the water quality of the Grand Canal due to their remarkable portions of exchangeable fraction in surface sediment. However, Pb showed a relative low risk, and was largely bounded to Fe/Mn oxides in the urban surface sediments. Obviously, the three assessment indices were not consistent with each other in terms of predicting environmental risks attributed to heavy metals in the freshwater surface sediments of this study. It is recommended that risk assessment by SQGs should be revised according to availability and site specificity. However, the combination of the three indices gave us a comprehensive understanding of heavy metal risks in the urban surface sediments of the Grand Canal.     

Fractionation and extractability of sulfur, iron and trace elements in sulfidic sediments

This study describes iron and sulfur fractionation, and the related extractability of selected trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in estuarine sediments. The sediments were sulfidic, with moderately high concentrations of pore-water sulfide (200-600 micromol l(-1)) and acid-volatile sulfide (AVS; 9.9-129 micromol g(-1)). Pyrite-S concentrations increased with depth, with 63-251 micromol g(-1) at site W1 and 312-669 micromol g(-1) at site W2. The degree of sulfidisation was generally high (>80%), indicating that Fe may be limiting pyrite accumulation. The ratios of AVS to pyrite-S increased with sediment depth, as expected for the pyritisation of solid-phase AVS. Cadmium, Pb and Zn extractability in 1M HCl indicated that these elements are not significantly sequestered during pyritisation, whereas sequestration may be important for As, Cu and possibly Ni. Extractability trends for Cr suggest that diagenesis in sulfidic sediments may enhance Cr reactivity. Overall, replacement of AVS by pyrite during diagenesis may enhance the reactivity of Cd, Cr, Pb and Zn, whereas As, Cu and possibly Ni may be rendered less reactive.     

Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

Heavy metals in sediments,soils, and aquatic plants from a secondary anabranch of the three gorges reservoir region,China

We investigated the occurrence of cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), Znic (Zn), iron (Fe), manganese (Mn), and magnesium (Mg) in sediments, as well as in related soils and aquatic plants in the Liangtan River, a typical secondary anabranch of the Yangtze River in the Three Gorges Reservoir Region (TGRR) of China. We found that sediments accumulated more metals than soils and aquatic plants. Concentrations of the nine metals in sediments and soils followed the same sequence, while their concentrations in aquatic plants followed a different sequence. Potential adverse effects of contaminated sediments on benthic fauna were evaluated, and the results showed that the toxic effect on benthic organisms followed the sequence Zn?>?Ni?>?Cr?>?Cu?>?Cd?>?Pb. The potential ecological risk index analysis indicated that Cd in sediments had considerable ecological risk, whereas Cr, Cu, Zn, Ni, and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in sediments of the Liangtan River was 174.9, indicating moderate ecological risk. The transfer factor trend of metals for aquatic plants showed that Cd and Ni had the most and least accumulation, respectively. For Cu, Cd, Mg, Pb, and Cr, a significant positive correlation of the metal concentrations was observed between sediments and soils, but no correlations (excluding Cr) were detected between sediments and aquatic plants. Our study indicated that anthropogenic input may be the primary source of metal contamination in the Liangtan River, and that Zn and Cd pollution in the Liangtan River should be further explored.     

Accumulation and biological cycling of heavy metal in four salt marsh species, from Tagus estuary (Portugal)

Pools of Zn, Cu, Cd and Co in leaf, stem and root tissues of Sarcocornia fruticosa, Sarcocornia perennis, Halimione portulacoides and Spartina maritima were analyzed on a bimonthly basis, in a Tagus estuary salt marsh. All the major concentrations were found in the root tissues, being the concentrations in the aboveground organs neglectable for sediment budget proposes, as seen by the low root-aboveground translocation. Metal annual accumulation, root turnovers and cycling coefficients were also assessed. S. maritima showed the higher root turnovers and cycling coefficients for most of the analyzed metals, making this a phytostabilizer specie. By contrast the low root turnover, cycling coefficient and low root necromass generation makes S. perennis the most suitable specie for phytoremediation processes. Although the high amounts of metal return to the sediments, due to root senescence, salt marshes can still be considered sinks of heavy metals, cycling heavy metals mostly between sediment and root.     

The origin of speciation: trace metal kinetics over natural water/sediment interfaces and the consequences for bioaccumulation

The speciation of heavy metals was measured over a variety of natural and undisturbed water/sediment interfaces. Simultaneously, two benthic species (oligochaete Limnodrilus spp. and the midge Chironomus riparius) were exposed to these sediments. Under occurring redox conditions, free ion activities of trace metals Cd, Cu, Ni, Pb, and Zn were measured with a chelating exchange technique, while geochemical conditions (i.e., redox) remained in tact. Free ion activities were compared with total dissolved concentrations in pore waters and surface waters in order to relate speciation to bioaccumulation. Limnodrilus spp. and C. riparius have accumulation patterns that could be linked to time-dependent exposure concentrations, expressed as chemical speciation, in the surface water and the sediment's pore water. Concentrations of free metal ions in the overlying surface water, rather than in sediment pore water, proved to be the best predictor for uptake. For the first time, measurements are obtained from sediments without disturbing physical-chemical conditions and thus bioavailability, a major restriction of other studies so far.