Total and methyl mercury in the water,sediment, and fishes of Vembanad,a tropical backwater system in India

Mercury contamination in the water bodies of developing countries is a serious concern due to its toxicity, persistence, and bioaccumulation. Vembanad, a tropical backwater lake situated at the southwest coast of India, is the largest Ramsar site in southern India. The lake supports thousands of people directly and indirectly through its resources and ecosystem services. It is highly polluted with toxic pollutants such as heavy metals, as it receives effluent discharges from Kerala’s major industrial zone. In the present study, water, pore water, sediment, and fish samples collected from Vembanad Lake were analysed for total mercury (THg) and methyl mercury (MHg) contents. The maximum concentrations of THg and MHg in surface water samples were31.8 and 0.21 ng/L, respectively, and those in bottom water samples were 206 and 1.22 ng/L, respectively. Maximum concentration of THg in surface sediment was observed during monsoon season (2850 ng/g) followed by that in the pre-monsoon season (2730 ng/g) and the post-monsoon season (2140 ng/g). The highest sediment concentration of MHg (202.02 ng/g) was obtained during monsoon season. The spatial variation in the mercury contamination clearly indicates that the industrial discharge into the Periyar River is a major reason for pollution in the lake. The mercury pollution was found to be much higher in Vembanad Lake than in other wetlands in India. The bioaccumulation was high in carnivorous fishes, followed by benthic carnivores. The THg limit in fish for human consumption (0.5 mg/kg dry wt.) was exceeded for all fish species, except for Glossogobius guiris and Synaptura orientalis. The concentration of THg was five times higher in Megalops cyprinoides and four times higher in Gazza minuta. Significant variation was observed among species with different habits and habitats. Overall, risk assessment factors showed that the mercury levels in the edible fishes of Vembanad Lake can pose serious health impacts to the human population.     

Heavy metal assessment using geochemical and statistical tools in the surface sediments of Vembanad Lake, Southwest Coast of India

The geochemical distribution and enrichment of ten heavy metals in the surface sediments of Vembanad Lake, southwest coast of India was evaluated. Sediment samples from 47 stations in the Lake were collected during dry and wet seasons in 2008 and examined for heavy metal content (Al, Fe, Mn, Cr, Zn, Ni, Pb, Cu, Co, Cd), organic carbon, and sediment texture. Statistically significant spatial variation was observed among all sediment variables, but negligible significant seasonal variation was observed. Correlation analysis showed that the metal content of sediments was mainly regulated by organic carbon, Fe oxy-hydroxides, and grain size. Principal component analysis was used to reduce the 14 sediment variables into three factors that reveal distinct origins or accumulation mechanisms controlling the chemical composition in the study area. Pollution intensity of the Vembanad Lake was measured using the enrichment factor and the pollution load index. Severe and moderately severe enrichment of Cd and Zn in the north estuary with minor enrichment of Pb and Cr were observed, which reflects the intensity of the anthropogenic inputs related to industrial discharge into this system. The results of pollution load index reveal that the sediment was heavily polluted in northern arm and moderately polluted in the extreme end and port region of the southern arm of the lake. A comparison with sediment quality guideline quotient was also made, indicating that there may be some ecotoxicological risk to benthic organisms in these sediments.     

Biogeochemistry of mercury and methylmercury in sediment cores from Sundarban mangrove wetland, India—a UNESCO World Heritage Site

This study was performed to elucidate the distribution, concentration trend and possible sources of total mercury (Hg(T)) and methylmercury (MeHg) in sediment cores (<63 μm particle size; n?=?75) of Sundarban mangrove wetland, northeastern part of the Bay of Bengal, India. Total mercury was determined by atomic absorption spectrometry (AAS) in a Leco AMA 254 instrument and MeHg by gas chromatography-atomic fluorescence spectrometry (GC-AFS). A wide range of variation in Hg(T) (0.032-0.196 μg g(-1) dry wt.) as well as MeHg (0.04-0.13 ng g(-1) dry wt.) concentrations revealed a slight local contamination. The prevalent low Hg(T) levels in sediments could be explained by sediment transport by the tidal Hugli (Ganges) River that would dilute the Hg(T) values via sediment mixing processes. A broader variation of MeHg proportions (%) were also observed in samples suggesting that other environmental variables such as organic carbon and microbial activity may play a major role in the methylation process. An overall elevated concentration of Hg(T) in surface layers (0-4 cm) of the core is due to remobilization of mercury from deeper sediments. Based on the index of geoaccumulation (I (geo)) and low effects-range (ER-L) values, it is considered that the sediment is less polluted by Hg(T) and there is less ecotoxicological risk. The paper provides the first information of MeHg in sediments from this wetland environment and the authors strongly recommend further examination of Hg(T) fluxes for the development of a detailed coastal MeHg model. This could provide more refine estimates of a total flux into the water column.     

Metals Associated with Suspended Sediments in Lakes Erie and Ontario, 2000–2002

Sediment traps were deployed in the three major basins of Lake Erie, and the central (Mississauga) basin of Lake Ontario, and refurbished seasonally over the period 2000–2002. In Lake Ontario, sediment down-flux rates and corresponding contaminant down-flux rates were highest in winter during periods of unstratified thermal conditions, and generally increased with depth due to the influence of resuspended bottom sediments during all sampling periods. Lake Ontario suspended sediments exhibited the highest concentrations of metals; concentrations of mercury and lead frequently exceeded guideline values for bottom sediments. Contaminant levels in Lake Ontario suspended sediments were similar to concentrations in bottom sediments in the same area. There was a spatial trend toward higher suspended sediment metals concentrations from the eastern basin to the western basin of Lake Erie, which is similar to the trend in bottom sediment contamination. In the eastern basin of Lake Erie, which is the deepest area of the lake, there was no trend in down-flux rate with depth in 2001; however, down-flux rates increased with depth in 2002. Suspended sediments in the western basin of Lake Erie were determined to be largely resuspended bottom sediments; all western basin samples collected in the study exceeded the guideline value for mercury (0.486 μg/g).     

Historical changes in the concentrations of polycyclic aromatic hydrocarbons (PAHs) in Lake Peipsi sediments

The distribution of 11 individual polycyclic aromatic hydrocarbons (PAHs) was analysed in a (210)Pb dated sediment core from the deepest area of Lake Peipsi and in four surface sediment samples taken from littoral areas. According to the concentrations in the core three groups of PAHs may be distinguished: (1) relatively stable concentrations of PAHs within the whole studied time interval; (2) very low concentrations in sediments accumulated before intensive anthropogenic impact (from 19th century up to the 1920s) following a slight increase and (3) an overall increase in PAH concentrations since the 1920s up to the present. Comprehensive analysis of PAHs in the core and monitoring data obtained in the 1980s together with the lithology of sediments show that an increase of anthropogenically induced PAHs correlates well with the history of fuel consumption in Estonia and speaks about atmospheric long-distance transport of PAHs. The continuous increase of PAH concentrations since the 1920s do not support the earlier hypothesis about the dominating impact of the oil shale fired power plants near the lake, because their emissions decreased significantly in the 1990s. The concentration of PAHs in the deep lake core sample correlates well with the content of organic matter, indicating absorption and co-precipitation with plankton in the sediment.     

Spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments of the Nansi Lake, China

Polycyclic aromatic hydrocarbons (PAHs) were measured in surface sediments and dated core sediments from the Nansi Lake of China to investigate the spatial and temporal distribution characteristics. The concentrations of 16 kinds priority PAH compounds were determined by GC-MS method. And ²¹⁰Pb isotope dating method was used to determine the chronological age of the sediment as well as the deposition rate. The results indicated that the total PAHs concentration ranges in surface and core sediment samples were 160 ~32,600 and 137 ~ 693 ng/g (dry wt.), respectively. The sediment rate and the average mass sedimentation were calculated to be 0.330 cm·year^???1 and 0.237 g·cm^???2·yr^???1 and the sediment time of the collected core sample ranged from 1899 to 2000. The peak of PAH concentrations came at recent years. The source analysis showed PAHs mainly came from the contamination of low temperature pyrogenic processes, such as coal combustion. The PAHs concentrations were lower than ERL and LEL values for most collected samples. However, in several surface sediment samples especially in estuary sites, the PAHs concentrations were not only higher than ERL and LEL values, but also higher than ERM values.     

Mercury concentration in fish from Piracicaba River (Minas Gerais, Brazil)

Mercury emissions from some upstream gold mining areas and recent findings of high natural Hg levels in sediments motivated studies on the Hg cycle in the Minas Gerais state. The study presents the total mercury amount found in Geophagus brasiliensis' muscular tissue (wet weight) and sediments from Piracicaba River. Mercury was analyzed using acid digestion followed by determination of total mercury by cold vapour atomic absorption spectrophotometry. This study was also complemented with the analysis of the limnological parameters (water temperature, conductivity, total dissolved solids, suspended particles, pH, dissolved oxygen, maximum depth, photic index and total carbon). The mercury concentration in sediments samples was higher than the mercury concentration in muscular tissue of fish. The lowest Hg level measured in fish was 0.0147 microg g( - 1), while the highest was 0.101 microg g( - 1). In the sediment samples, the lowest and highest levels were 0.02 microg g( - 1) and 0.16 microg g( - 1), respectively. The Hg concentrations in fish and sediment were both under the maximum limit permitted by the World Health Organization.     

Speciation of mercury in the strongly polluted sediments of the Deûle River (France)

The De?le River in Northern France experienced serious contamination from the metallurgical industry, especially from the smelter Metaleurop prior to 2003. In 2002 the surface sediments were collected from the bed of the river around 10 km above and 10 km below the smelter. Total mercury (HgT) and methylmercury (MeHg) concentrations exceeded the background value of 0.1 mg kg(-1). The average concentrations were 19.67 ± 1.02 mg kg(-1) and 10.88 ± 1.08 μg kg(-1), respectively. In 2003 the sediment core samples were collected at two different sites near the factory for survey depth profiles of Hg contamination. The concentrations of HgT and MeHg in sediment cores varied from 10.47 to 259.44 mg kg(-1) and from 3.24 to 82.61 μg kg(-1), respectively. The concentration of total mercury was significantly correlated with the methylmercury concentration in the sediment below a depth of 23.5 cm (R(2) = 0.81, p < 0.01). This may suggest that the production of MeHg is directly related to the HgT concentration. Nevertheless the MeHg/HgT ratio in the upper part of the sediment core was higher than that in the lower part. This suggests that HgT and MeHg may have been co-deposited together. However, the methylmercury production takes place in the surface sediment by microorganisms. The strong correlation observed between MeHg and acid volatile sulfides (AVS) suggests that MeHg variability is associated with the bacterial activity (presence of AVS).     

Monitoring the quality of the marine environment

As part of the monitoring program from Instituto Hidrográfico, since 1981 sediment and water samples have been collected from four different estuarine areas located along the continental coast of Portugal. The concentrations of different parameters were measured in the water and sediment samples. After normalization, the concentrations of chromium, mercury, lead and zinc in the sediments from the different areas were compared.     

Toxicity assessment of sediments associated with the wreck of s/s Stuttgart in the Gulf of Gdańsk (Poland)

The paper presents the results of toxicity determinations carried out on sediment samples collected in the vicinity of the wreck of the German s/s Stuttgart (the southern part of the Gulf of Gdańsk, off the Polish coast) in relation to the determination of polycyclic aromatic hydrocarbons (PAHs). The toxicity of surface and core sediment samples was assessed using two biotest organisms-the bioluminescent bacteria Vibrio fischeri and the ostracod Heterocypris incongruens. PAH levels in these samples were determined by GC-MS. The surface sediments collected at W2 (ca. 34 m north of the shipwreck) and W4 (ca. 415 m north-east of the wreck) as well as the core sediments collected at WR3 (ca. 400 m north-east of the wreck) were the most heavily polluted with substances toxic to the biotest organisms. The chronic and acute toxicities in the case of most of the surface sediment samples studied are correlated. This may suggest that not only hydrophobic chemicals (like PAHs from fuel residues) but also more polar chemicals (resulting from the conversion of aromatic hydrocarbons) are responsible for the toxicity levels found. There is a clear dependence between the levels of chronic toxicity and PAH concentrations in the core sediment samples. In addition, a simultaneous decrease in the PAH content and chronic toxicity was noted in all the core sediment samples at depths below 80 cm.     

Elemental composition of sediments in Lake Jinzai, Japan: Assessment of sources and pollution

Bottom sediments from Lake Jinzai in southwest Japan were analyzed to determine their chemical compositions and to assess the potential for ecological harm by comparison with sediment quality guidelines. The pollution status of lake sediments was evaluated by employing contamination factor (CF), pollution load index (PLI), and geoaccumulation index (I(geo)), focusing on a suite of elements in lakebed and core sediments. Elevated concentrations of As, Pb, Zn, Cu, TOC, N, and P were present in several layers of the upper core and other surface sediments. The elevated metal concentrations are likely related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter, and possibly minor non-point anthropogenic sources. Moreover, correlations between the concentrations of trace metals and organic carbon, nitrogen, phosphorus, and iron, suggest that these elements play a role in controlling abundances. Calculated CF, PLI, and I(geo) indicate that the sediments are strongly polluted with respect to As, moderately to strongly polluted with Zn, and moderately polluted with Pb and Cu. Metal concentrations exceed the New York State Department of Environmental Conservation (NYSDEC) lowest effect level and the Canadian Council of Ministers of the Environment (CCME) interim sediment quality guidelines that indicate moderate impact on aquatic organisms in the study area.     

Risk assessment of trace metals in an extreme environment sediment: shallow,hypersaline, alkaline,and industrial Lake Acıgöl,Denizli, Turkey

The major and trace element component of 48 recent sediment samples in three distinct intervals (0–10, 10–20, and 20–30 cm) from Lake Ac?göl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the <?60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Ac?göl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.     

Nature of distribution of mercury in the sediments of the river Yamuna (tributary of the Ganges), India

Suspended Particulate Matter (SPM), surface (bed sediments) and short length cores of sediments collected from the largest tributary of the river Ganges, namely the river Yamuna, were analysed for total mercury as well as its fractionation in various size and chemical sites in the sediments following standard procedures. Also, attempts were made to determine the vertical distribution in sediments in relation to the recent timescale of a few decades. Our observations indicate that the SPM in general showed higher levels of total mercury compared to the surface sediments while at places the enhancement could be by a factor of 10, say around 25 microg g(-1) in the downstream region that integrates the industrial midstream and agricultural downstream terrain near its confluence with the Ganges. Surface sediments in the upstream direction near the Himalayan foothills and SPM in the lower reaches showed significant high Index of Geoaccumulation (Igeo) as defined by Müller. Size fractionation studies indicate that the finer fraction preferentially showed higher levels of mercury while in the lower reaches of the river, the total mercury is equitably distributed among all size fractions. The proportion of the residual fraction of mercury in relation to mobile fractions, in general decreases downstream towards its confluence with the Ganges river. In sediment cores, the vertical distribution show systematic peaks of mercury indicating that addition of this toxic metal to the aquatic system is in direct proportion to the increase in various types of human activities such as thermal power plants, land use changes (urbanisation) in the midstream region and intensive fertiliser application in lower reaches of this vast river basin.     

Pool of mobile and immobile phosphorus in sediments of the large, shallow Lake Peipsi over the last 100?years

Temporal variations in sediment phosphorus (P) composition and mobility were estimated in surface sediments of accumulation (core PS509 44?cm) and erosion (core PS2009 30?cm) areas of the shallow, large Lake Peipsi sensu stricto (s.s.; 2611?km(2), unregulated water level). The P pool in sediments including buried and mobile P is evaluated for the first time, which will provide baseline data for the future modelling of internal loading in L. Peipsi. Five sedimentary P fractions (including inorganic and nonreactive P) were separately quantified: loosely adsorbed and pore-water P (NaCl-P); redox-sensitive fraction P (NaBD-P); P bound to oxides of non-reducible Fe and Al (NaOH-P); calcium-bound P, mainly from apatite minerals (HCl-P) and refractory, mainly organic P (Res-P). Concentrations of P fractions varied during the 100?years with the highest values around 2007-2008 and 1923-1935. The P in "active" layers that are available for bacteria and algae or those undergoing changes and diagenetic transformations in the sediment could follow sediments with the water content of ～88%. Potentially mobile P is not decreased in the sediments deposited 50-100?years ago and makes up ca 63?mg?m(-2)?y(-1) (with range 8.3-23.7% of the total P (TP)) in the accumulation area, and ca 0.047?mg?cm(-3) (with range 1.3-22.4% of TP) in the erosion area. The result shows that 13-60% of TP contained in the surface sediment (from 34 to 398?mg P m(-2) y(-1)) has been remobilised during accumulation and could be exported to the overlying water.     

Application of neural-based modeling in an assessment of pollution with mercury in the middle part of the Warta River

The level of pollution with various mercury species (organomercury, water- and acid-soluble mercury, mercury bound to humic matter and to sulphides) of the floodplain soils and sediments from middle part of the Warta River has been assessed using self-organizing maps (SOM). Chemometric evaluation allowed identification of moderately (median 173-187 ng g(-1), range 54-375 ng g(-1) in soil and 130 ng g(-1), range 47-310 ng g(-1) in sediment) and heavily polluted samples (662 ng g(-1), range 426-884 ng g(-1)). Heavily polluted were located mainly below and in the area of the Poznań city. Statistical comparison of mercury species distribution in floodplain soils of the Warta River shows different patterns for moderately and heavily polluted samples. In heavily polluted soils the contribution of mobile mercury (sum of organomercury species, water- and acid soluble species) is lower (4.2%) than in moderately polluted soils (6.1%). Higher contribution of mobile mercury was observed in sediments of the Warta River (12%). In case of moderately polluted samples, statistical differences in the contribution of mercury species are relatively low and thus the environmental risk from mercury deposited in aquatic system of the Warta River is relatively low. However, higher water levels and heavy floods may incite remobilisation of some organomercuries (2.2-2.9 ng g(-1) in soil and 10 ng g(-1) in sediment) and acid-soluble species of mercury (2.6-2.9 ng g(-1) in soil and 0.5 ng g(-1) in sediment).     

Geochemical characterisation of major and trace elements in the coastal sediments of India

Thirty-five surface sediment samples from the Indian continental shelf were recovered offshore from the mouths of the major rivers (Brahmaputra, Ganges, Narmada, Tapti, Godavari, Krishna and Cauvery) discharging into the coastal region of both east and west coasts were analysed using inductively coupled plasma atomic emission spectroscopy for selected major (i.e. Al, Ca, Fe, K, Ti, Mg and Na) and trace elements (e.g. Ba, Co, Cr, Cu, Ga, Ni, P and V), after total dissolution. The main objectives are to understand the processes controlling major and trace elements in the surface sediments and to identify natural and anthropogenic sources in the coastal environment using statistically regressed elemental concentrations to establish regional baseline levels. Metal enrichments observed close to the major urban areas in the east and west coasts are associated with the industrialised activities areas rich in Cu and Co in both the east and west coast sediments. Normalisation of metals to Al indicated that high enrichment factors are in the order of Ca>Ti≥Fe>Na>Mg>Co>Cu>Ga>V>Ba except K and P depletion. This indicated that the characteristic of estuarine sediment showed higher level along the west coast of India, which was reflected in the coastal sediments as similar to the source of its origin from the riverine composition and its abundances.     

Assessment of metal enrichments in tsunamigenic sediments of Pichavaram mangroves, southeast coast of India

The 26 December 2004-Tsunami has deposited sediments in the Pichavaram mangrove ecosystem, east coast of India. Ten surface and three core sediment samples were collected within thirty days of the event. High concentrations of Cd, Cu, Cr, Pb, and Ni were observed in the tsunamigenic sediments. With respect to Fe, Zn, and Mn, there was little variation as compared to pre-tsunami values. The geo-accumulation index was calculated in order to assess the contamination of heavy metals in the sediments. The sediments were extremely contaminated with respect to Cd and they showed moderate to strong contamination with respect to Cr, Pb and Ni. The study highlighted the future risk of enhanced metal pollution in near future in this mangrove ecosystem.     

The polycyclic aromatic hydrocarbon and geochemical biomarker composition of sediments from sea lochs on the west coast of Scotland

Sediments from twelve sea lochs on the west coast of Scotland were analysed for parent and branched 2- to 6-ring polycyclic aromatic hydrocarbons (PAHs), n-alkanes and geochemical biomarkers (triterpanes). Where possible at least fourteen sediment samples were collected at random from each sea loch. All sea lochs were remote, most had limited industrial and urban inputs, although all had fish farms. Four lochs had moderate total PAH concentrations and eight lochs had high total PAH concentrations. Total PAH concentration was related to organic carbon content and particle size distribution, with sandier sediments having lower PAH concentrations. The highest total PAH concentrations, normalised for organic carbon, were in Loch Linnhe and Ballachulish Bay (Loch Leven), close to an aluminium smelter. PAH concentration ratios showed that pyrolysis was the main source of PAHs in most lochs. Only sediments from Loch Clash showed evidence of petrogenic input based on their geochemical biomarker (triterpane and sterane) and n-alkane profiles. PAH profiles were similar across lochs apart from Loch Linnhe and Ballachulish Bay, which had a greater proportion of heavy parent PAHs. West coast sediments had a smaller proportion of heavy PAHs than sediments collected from voes in Shetland and a smaller proportion of alkylated PAHs relative to sediments collected from coastal waters around Orkney.     

Fluorine in the rocks and sediments of volcanic areas in central Italy: total content, enrichment and leaching processes and a hypothesis on the vulnerability of the related aquifers

Rock, sediment and water samples from areas characterised by hydrothermal alterations in the Sabatini and Vico Volcanic Districts, near Rome and the large city of Viterbo, respectively, were collected and analysed to determine the total fluorine (F) content and to understand the F geochemical background level in the volcanic districts of central Italy. Leaching and alteration processes controlling the high concentration of F in water were also investigated. Fluorine concentrations were directly determined (potentiometrically) by an F selective electrode in water samples, while the procedure for rock samples included preliminary F dissolution through alkaline fusion. F concentrations higher than 800 mg kg(-1) were commonly found in the analysed rocks and sediments; the concentration depended on the lithology and on the distance from the alteration areas. A specific successive sampling campaign was conducted in three areas where the F content in sediments was particularly high; in the same areas, measurements of CO(2) flux were also performed to investigate the possible deep origin of F. To verify the relationships among the high F contents in rocks and sediments, the leaching processes involved and the presence of F in the aquifer, we also collected water samples in the western sector of the Sabatini Volcanic District, where hydrothermal manifestations and mineral springs are common. The data were processed using a GIS system in which the F distribution was combined with morphological and geological observations. The main results of our study are that (1) F concentrations are higher in volcanic and recently formed travertine (especially in hydrothermally altered sediments) than in sedimentary rocks and decrease with distance from hydrothermal alteration areas, (2) F is more easily leached from hydrothermally altered rocks and from travertine and (3) sediments enriched with F may indicate the presence of deep regional fractures that represent direct pathways of hydrothermal fluids from the crust to the surface.     

Chemical availability of mercury in stream sediments from the Almadén area, Spain

The chemical speciation, fractionation and availability of mercury in sediments from a cinnabar mining area (Almadén, Spain) was studied with different extraction and analytical procedures, in order to determine the degree to which the ecosystem is harmed by this pollutant. Three total extraction procedures, a sequential extraction and the speciation of organo-mercury compounds were performed in nine sediment samples. In the study area, although concentrations of mercury can be extremely high (up to 1,000 mg kg(-1)), no organomercury compounds were detected (< 2 microg kg(-1) and the availability of this element seems restricted. One of the methods for total extraction presented considerably lower recovery in Almadén's sediments, yet the results were controlled with certified reference materials. This disagreement was attributed to the fact that the mercury is in a refractory form. Sequential extraction was able to show that most of the mercury is associated with sulfides (probably as metacinnabar) or in the residual refractory phase (probably as red cinnabar).