Occurrence and spatial distribution of metals in intertidal sediments of a temperate estuarine system (Bahía Blanca,Argentina)

Intertidal sediments of the inner and middle zone from the Bahía Blanca estuary were sampled for geochemical and environmental assessment of metals (Cd, Cu, Pb, Zn, Mn, Ni, Cr and Fe). Results indicate that both the organic matter content and the sediment grain size plays an important role in controlling the differential concentrations of the metals found in sediments from both zones. For most of the elements (except Mn), sediment metal concentrations were greater in the middle zone, although the concentrations did not exceed the maximums for quality of marine sediments. In this sense, anthropogenic impact (i.e., sewage drain) appears to be a key factor in the distribution of metals within the estuarine system. Comparing the levels obtained with quality levels (LEL and SEL), except Cu that showed levels slightly above the LEL, the rest of the concentrations of metals were lower to those levels. The low metal concentrations obtained within this highly impacted estuarine system suggest that the great volume of water that flooding the extensive flats in each tidal cycle has much importance. Although the potential risks of metals to the estuarine environment were low, taking into account the toxicity of some of these metals, continuity of monitoring is highly recommended.     

Heavy metal concentrations in sediments and in mussels from Argentinean coastal environments,South America

Among environmental contaminants, heavy metals are currently considered to be some of the most toxic ones present worldwide due to their harmful effects on organisms and ability to bioaccumulate in aquatic systems. In this work, the concentration of heavy metals (Cd, Cu, Pb, Zn, Ni and Cr) in Brachidontes rodriguezii and in the fine sediments of several coastal sites at the southwest of Buenos Aires Province, Argentina is analyzed. The Bahía Blanca Estuary and Pehuen-Có beach are located in a highly complex oceanographic and ecological regional system, which creates the basis of one of the most valuable Argentinean habitats for fishing commercial species. An assessment, which involved analyzing distribution pattern of trace metals, comparative studies with sediment and ecological quality guidelines; and a sequential and integrated index analyses approach (containing Metal Pollution Index, Biosediment Accumulation Factor, Geo-accumulation Index (Igeo), Pollution Load Index and the mean Probable Effect Level quotients), was followed to estimate enrichment and risks of heavy metals in the sediments and in the mussels from these study areas. The results showed higher concentrations of some heavy metals (e.g., Cd, Cr and Ni) in mussels collected at Pehuen-Có, while no spatial differences in sediments were observed. According to the international environmental regulations, mean values of trace metals in mussels allowed to place both sites between “unpolluted and moderately polluted” and between the “low and medium category” of pollution. Furthermore, the mean concentrations found were within the detected ranges in other coastal sites worldwide.     

Metals in tidal flats colonized by microbial mats within a South-American estuary (Argentina)

In this study, we measured the concentrations of metals (Cd, Cu, Pb, Ni, Cr, Zn, Hg, Mn, and Fe) and assessed the characteristics of tidal flats (grain size and organic matter content) in sediments and their overlying microbial mats fractions to evaluate the anthropogenic impact within the Bahía Blanca Estuary (BBE). Puerto Rosales (PR) and Almirante Brown (AB), located in the middle and inner zone of the estuary, respectively, were used as sampling sites. Sediments were composed mainly of silt–clay in AB, whereas first fine-grained particles were coarser in depth in PR. Regarding the concentration of metals in both fractions, we found differences between sites: There were higher concentrations of overall metals in AB relative to PR. In addition, higher concentrations of Cu were recorded in the first centimeters of AB tidal flats, whereas higher concentration of Cd were recorded in microbial mats of PR. Considering that the grain size was similar between sites, these results are consistent with the high concentration of organic matter found in AB, probably because this site is close to a former municipal dump and sewage discharges. Also, the higher Cd content found in PR site would highlight both the influence of untreated urban discharges and port anthropogenic activities. In conclusion, this study allowed identifying high values of some metals in the presence of microbial mats in the BBE, thus suggesting a possible interaction between both, at least for metals like Cu or Cd.     

Heavy metal distribution in surface sediments of the Tirumalairajan river estuary and the surrounding coastal area, east coast of India

Surface sediments collected at the Tirumalairajan river estuary and their surrounding coastal areas were analyzed for the bulk metal concentration. The sediments were collected from post- and premonsoon seasons. Dominances of heavy metals are in the following order: Fe > Mn > Zn > Pb > Cu in both seasons from estuary and coastal area. The results reveal that Fe, Mn, Cu, Pb, and Zn demonstrated an increased pattern from the estuary when compared to the coastal area. The heavy metal pattern of the sediments of the Tirumalairajan river estuary and its surrounding coastal area offered strong evidence that the coastal area was a major source of heavy metals to the estuarine region. For various metals, the contamination factor and geoaccumulation index (I _geo) have been calculated to assess the degree of pollution in sediments. The contamination factor and geoaccumulation index show that Zn, Pb, and Cu unpolluted to moderately pollute the sediments in estuarine part. This study shows the major sources of metal contamination in catchment and anthropogenic ones, such as agriculture runoff, discharge of industrial wastewater, and municipal sewage through the estuary and adjoining coastal area.     

Accumulation discrepancy of heavy metal and organic pollutants in three near-shore depositional environments, southeastern China

Heavy metal and organic pollutants in sediments along the coastal zone of southeastern China have been investigated. Sediment samples are retrieved from three depositional environments: coast, estuary, and tide-affected river mouth. The relative abundance of heavy metal and organic pollutants is related to their geochemical properties as well as depositional environments and anthropogenic discharge. Based on a sequential extraction method, it is revealed that anthropogenic Pb, Cr, Cu, and Cd are mainly bound to Fe–Mn oxides, suggesting that adsorption and co-precipitation of Fe–Mn oxides are in the control of their transfer processes from water column to sediment. Heavy metal bound to carbonates is also an important pool especially for Cd, Mn, and Pb. The main organic pollutants found in the study area include petroleum-related alkanes, phthalic acid ester, organic silicon, chlorophenol, phenyl ether, and amine. The accumulation of heavy metals and organics in surficial sediments has a decrease tendency from estuarine environment to coastal environment and to tide-affected river mouth.     

Temporal and spatial variability of trace metals in suspended matter of the Mandovi estuary,central west coast of India

Studies on the suspended particulate matter (SPM) in the Mandovi estuary, western India indicate that during the monsoon and pre-monsoon, the SPM increases, and the major and trace metals decrease from stations in the upstream to downstream of the estuary. SPM is consistently low at all stations during the post-monsoon. Trace metals (Cu, Ni, Zn, Cr, and Pb) show strong inter-relationships. They correlate well with Fe and Mn only during the monsoon. The concentrations of Cr, Cu, and Pb are high during the post-monsoon. Enrichment factors and I _geo values of metals indicate that Mn shows significant to strong pollution in all seasons, while Cr, Ni, and Zn during monsoon, and Cr during the post-monsoon show moderate pollution. SPM is controlled by the turbidity maximum, while major and trace metals are governed seasonally by a combination of river discharge, resuspension, spillage of Fe–Mn particulates, and anthropogenic contamination. Incursion of saline waters deep into the river channel during the dry season facilitates aggregation and settling of particulate-borne pollutants close to the discharge area, thereby keeping the estuarine waters free from major contamination.     

Heavy metal anomalies in the Tinto and Odiel River and estuary system,Spain

The Tinto and Odiel rivers drain 100 km from the Rio Tinto sulphide mining district, and join at a 20-km long estuary entering the Atlantic Ocean. A reconnaissance study of heavy metal anomalies in channel sand and overbank mud of the river and estuary by semi-quantitative emission dc-arc spectrographic analysis shows the following upstream to downstream ranges in ppm (μg g^?1): As 3,000 to <200, Cd 30 to <0.1, Cu 1,500 to 10, Pb 2,000 to <10, Sb 3000 to <150, and Zn 3,000 to <200. Organic-rich (1.3–2.6% total organic carbon, TOC), sandysilty overbank clay has been analyzed to represent suspended load materials. The high content of heavy metals in the overbank clay throughout the river and estuary systems indicates the importance of suspended sediment transport for dispersing heavy metals from natural erosion and anthropogenic mining activities of the sulfide deposit. The organic-poor (0.21–0.37% TOC) river bed sand has been analyzed to represent bedload transport of naturally-occurring sulfide minerals. The sand has high concentrations of metals upstream but these decrease an order of magnitude in the lower estuary. Although heavy metal contamination of estuary mouth beach sand has been diluted to background levels estuary mud exhibits increased contamination apparently related to finer grain size, higher organic carbon content, precipitation of river-borne dissolved solids, and input of anthropogenic heavy metals from industrial sources. The contaminated estuary mud disperses to the inner shelf mud belt and offshore suspended sediment, which exhibit metal anomalies from natural erosion and mining of upstream Rio Tinto sulphide lode sources (Pb, Cu, Zn) and industrial activities within the estuary (Fe, Cr, Ti). Because heavy metal contamination of Tinto-Odiel river sediment reaches or exceeds the highest levels encountered in other river sediments of Spain and Europe, a detailed analysis of metals in water and suspended sediment throughout the system, and epidemiological analysis of heavy metal effects in humans is appropriate.     

Distribution and speciation of heavy metals in surface sediments from the Yangtze estuary and coastal areas

The concentrations and speciation of heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the sediments of the nearshore area, river channel and coastal zones of the Yangtze estuary, China, were systematically investigated in this study. The concentrations of all heavy metals except Ni in the sediments of the nearshore area were higher than those of the river channel and coastal zones. In the nearshore area, the concentrations of most heavy metals except Hg in the sediments of the southern branch were higher than those of the northern branch because of the import of pollutants from the urban and industrial activities around. When compared with the threshold effect level (TEL) and geochemical background levels, Cr, Ni and As accumulated and posed potential adverse biological effects. The speciation analysis suggested that Cd, Pb and Zn in the sediments of the three zones showed higher bioavailability than the other heavy metals, and thus posed ecological risk. Significant correlations were observed among Cr, Cu, Ni and Zn (r > 0.77) in the nearshore area, Ni, Cu, Zn and Pb (r > 0.85) in the river channel and Ni, Cu, Cr, Pb and Zn (r > 0.75) in the coastal zone. Principal component analysis (PCA) indicated that the discharge of unban and industrial sewage, shipping pollution and the properties of the sediments (contents of Fe, Mn, Al, TOC, clay and silt) dominated the distribution of heavy metal in the nearshore area, river channel and coastal zones of the Yangtze estuary.     

(Pre-) historic changes in natural and anthropogenic heavy metals deposition inferred from two contrasting Swiss Alpine lakes

Continuous high-resolution sedimentary record of heavy metals (chromium (Cr), copper (Cu), lead (Pb), zinc (Zn), manganese (Mn), and mercury (Hg)), from lakes Lucerne and Meidsee (Switzerland), provides pollutant deposition history from two contrasting Alpine environments over the last millennia. The distribution of conservative elements (thorium (Th), scandium (Sc) and titanium (Ti)) shows that in absence of human disturbances, the trace element input is primarily controlled by weathering processes (i.e., runoff and erosion). Nonetheless, the enrichment factor (EF) of Pb and Hg (that are measured by independent methods), and the Pb isotopic composition of sediments from the remote lake Meidsee (which are proportionally more enriched in anthropogenic heavy metals), likely detect early mining activities during the Bronze Age. Meanwhile, the deposition of trace elements remains close to the range of natural variations until the strong impact of Roman activities on atmospheric metal emissions. Both sites display simultaneous increases in anthropogenic trace metal deposition during the Greek and Roman Empires (ca 300 BC to AD 400), the Late Middle Ages (ca AD 1400), and the Early Modern Europe (after ca AD 1600). However, the greatest increases in anthropogenic metal pollution are evidenced after the industrial revolution of ca AD 1850, at low and high altitudes. During the twentieth century, industrial releases multiplied by ca 10 times heavy metal fluxes to hydrological systems located on both sides of the Alps. During the last decades, the recent growing contribution of low radiogenic Pb further highlights the contribution of industrial sources with respect to wood and coal burning emissions.     

Heavy metal pollution and assessment of the tidal flat sediments near the coastal sewage outfalls of shanghai,China

Zn, Cu, Cr and Pb concentrations of the sediment collected from three tidal flat sites of Yangtze estuary were investigated in October 2003. Results showed that the average concentrations of heavy metals in the sediments were two to three times to the environment background values of Yangtze estuary tidal flat sediment. The heavy metal concentrations in the sediments near the Bailonggang (BLG) and Laogang (LG) sewage outfalls were obviously higher than those of Chaoyang (CY) tidal flat where there are no sewage outfalls near the coast. And the concentrations of heavy metals in the surface sediments of LG tidal flat decreased with the increasing of the distance to the sewage outfalls. The heavy metal concentration profile in the sediment core changed with the depth, and generally reached maximum values at the depth of plant roots. The assessment results showed that the sediments of LG, BLG and CY tidal flat had been polluted by heavy metals in different level. The pollution degree of heavy metals in the sediments was as follows: Zn > Cu > Pb > Cr. The potential ecological risks of the four heavy metals in three tidal flat sites sediment were all at a middle level, and Cu and Pb made the main contributions. The adverse ecological effects caused by the four heavy metals did not occur frequently.     

Correlations between heavy metals and organic carbon extracted by dry oxidation procedure in urban roadside soils

The organic fraction in soils has a significant influence on heavy metal transport. In this study, the organic carbon content was measured by dry oxidation procedure from 21 Xuzhou urban roadside soils to assess the relationships between the concentrations of heavy metals (Pb, Cu, Zn, and Cr) and the amount of organic carbon. The anthropogenic heavy metals (e.g. Pb, Cu, Zn) were strongly correlated with organic carbon (denoted by C_org−c) extracted by dry oxidation while natural heavy metal (e.g. Cr) showed no correlation to the C_org−c. The anthropogenic heavy metals were also strongly correlated with the amount of the total carbon. These results show that the anthropogenic heavy metals are mainly enriched in the organic matter in the Xuzhou urban roadside soils.     

长江口滨岸潮滩重金属源汇通量估算

根据2002～2003年长江口滨岸潮滩16个站位1年的沉积物重金属含量、粒度和密度等季节性测试数据,结合其他文献的沉积物累积速率资料,初步估算了长江口滨岸潮滩重金属的源汇通量。结果表明,2002年徐六泾以下的河口地区,沉积物中Cu、Pb、Fe、Mn、Zn、Cr的年滞留量分别为3425t/a、2751t/a、3451599t/a、69505t/a、14045t/a和3176t/a,石洞口排污口和黄浦江仍然是这几种重金属的主要污染输入来源之一。潮滩能有效滞留河口水体中的重金属,在长江口0m线以上的潮滩沉积物中,Cu、Pb、Fe、Mn、Zn、Cr的年沉降量分别占到整个河口区重金属沉降量的24.3%、27.6%、32.3%、32.4%、20.5%和23.2%。从潮滩重金属的沉降通量来看,南汇边滩的沉降通量最大,长江口南岸潮滩明显高于长江口北支潮滩,说明位于排污口下游的滩地能有效削减入海重金属污染负荷。     

Anthropogenic heavy metal signatures for the fast growing urban area of Natal (NE-Brazil)

In this study the effect of anthropogenic discharges on the heavy metal content in the Potengi–Jundiai river system near the fast growing city of Natal, NE-Brazil, is investigated. Due to the multiple anthropogenic source character without any predominating anthropogenic heavy metal discharge the area of Natal may serve as a characteristic place for the study of the impact of the fast growing Brazilian cities on the environment. In general the sediments of the Rio Potengi–Jundiai river system in the studied area are not severely polluted. However, close to waste water drain pipes a characteristic anthropogenic heavy metal signature is visible in enhanced Zn, Pb, Cu and Cd values relative to reference elements such as Al and Fe. Sources are domestic and animal waste, combustion products and hydrocarbons. These heavy metals are probably mainly bound to organic matter. The elements Sn, Hg and Ag in part also belong to the anthropogenic heavy metal signature. The elements Cr, Ni and V are characteristic of weathering heavy minerals in crystalline rocks exposed in the catchment area of the river system and are not significantly added from anthropogenic sources. These heavy metals are most likely predominantly bound to oxides and represent the pristine geogenic background of the system. They can thus be used as reference elements to monitor incipient accumulation of Zn, Pb, Cu and Cd due to anthropogenic input. The element characteristics found here match with those found in other fast growing urban areas such as the Sao Paulo metropolitan area.     

湘江入湖河段沉积物重金属污染及其Pb同位素地球化学示踪

湘江是我国重金属污染最严重的河流之一.本次工作利用等离子质谱(ICP-MS)和多接收同位素质谱(MC-ICP-MS)等技术,对湘江入湖河段沉积物进行了系统的重金属微量元素和Pb同位素分析.结果表明,湘江河床沉积物明显富集Bi、Sc、V、Mn、Ni、Cu、Zn、Pb、Cd、Sn、Sb等多种重金属微量元素,而湖盆沉积物重金...     

Heavy metals in Oka river sediments (Urdaibai National Biosphere Reserve, northern Spain): lithogenic and anthropogenic effects

 The Oka River basin is located in the Urdaibai National Biosphere Reserve, North Spain. In order to obtain a preliminary view of its environmental conditions, nitric acid extractable Fe, Mn, Zn, Pb, Cu, Cr, Ni and Co, organic matter content (L.O.I.), geochemical fractionation of heavy metals and mineralogical composition were analysed in surficial sediments (fraction <63 μm) collected in October 1991. Relatively high concentrations of metals occurred in a sampling site upstream, due to a local natural enrichment controlled by weathering of volcanic rocks. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated to the detrital phase. The significant increase of heavy metals found in some samples collected in the municipal area of Gernika suggested a pollution effect, related to anthropogenic wastes. Large amounts of metallic slags have been found mixed with the sediments upstream from this locality. Nevertheless, in view of their composition, it is unlikely that these slags constitute a significant source of heavy metals in the studied area. In a second sampling in October 1997 an apparent decreasing trend in some heavy metal levels was noted, particularly for Pb and Cu. Nowadays, enrichment factors relative to background values confirm moderate anthropogenic influence on Zn, Pb, Cu, Cr and Ni concentrations. However, heavy metal levels in the Oka river sediments are much lower than those detected in other major rivers of the Basque Country (Nervión, Urumea, Deba). Received: 7 July 1997 · Accepted: 4 July 1998     

Heavy metal pollution of coastal river sediments, north-eastern New South Wales, Australia: lead isotope and chemical evidence

 Heavy metal and metalloid concentrations within stream-estuary sediments (<180-μm size fraction) in north-eastern New South Wales largely represent natural background values. However, element concentrations (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn) of Hunter River sediments within the heavily industrialized and urbanized Newcastle region exceed upstream background values by up to one order of magnitude. High element concentrations have been found within sediments of the Newcastle Harbour and Throsby Creek which drains into urbanized and light industry areas. Observed Pb enrichments and low ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁶Pb/²⁰⁴Pb ratios are likely caused by atmospheric deposition of Pb additives from petrol and subsequent Pb transport by road run-off waters into the local drainage system. Sediments of the Richmond River and lower Manning, Macleay, Clarence, Brunswick and Tweed River generally display no evidence for anthropogenic heavy metal and metalloid contamination (Ag, As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, Zn). However, the rivers and their tributaries possess localized sedimentary traps with elevated heavy metal concentrations (Cu, Pb, Zn). Lead isotope data indicate that anthropogenic Pb provides a detectable contribution to investigated sediments. Such contributions are evident at sample sites close to sewage outlets and in the vicinity of the Pacific Highway. In addition, As concentrations of Richmond River sediments gradually increase downstream. This geochemical trend may be the result of As mobilization from numerous cattle-dip sites within the region into the drainage system and subsequent accumulation of As in downstream river and estuary sediments. Received: 5 September 1997 · Accepted: 4 November 1997     

鸭绿江河口西岸潮间带柱状沉积物中重金属的分布特征及其对流域变化的响应

2010年和2011年在鸭绿江西水道和西岸潮间带共采集4根柱状样,通过对2mPb测年、粒度、总有机碳、重金属元素等多指标综合分析,探讨了：（1）鸭绿江河口西水道和西岸潮间带柱状沉积物中重金属的垂向分布及其来源：（2）重金属分布的粒度控制作用：（3）不同时期的粒度和重金属分布变化及其对流域变化的响应。结果表明：f1）Cu和zn可能来源于有机质降解的内源释放：Cr和Ni表征了岩石风化剥蚀形成陆源碎屑的自然来源：Cd和Pb反映了人类活动的影响。（2）除西岸潮间带的Cd和Pb含量可能部分受来源影响外,研究区的粒度效应是控制鸭绿江地区重金属含量分布的最主要因素。（3）粒度变化与流域演变密切相关,重金属含量对流域变化和人类活动响应明显,大致以1940年、1970年、1995年为界分为四个沉积阶段：1940年以前,自然演变对鸭绿江河口西岸潮间带的重金属分布控制明显,而1940年来至今,人类活动的控制作用日益凸显。     

Assessment of heavy metals in sediments near Hazira industrial zone at Tapti River estuary, Surat, India

Heavy metal accumulation due to industrial activities has become a very sensitive issue for the survival of the aquatic life. Therefore, distributions of several heavy metals have been studied in the surface sediments of Tapti–Hazira estuary, Surat, to assess the impact of anthropogenic and industrial activities near estuary. Totally 60 sediment samples were collected from four different sites at Tapti–Hazira estuary, Surat from January 2011 to May 2011 and examined for metal contents. The average heavy metal load in the study area are found to be 43.28–77.74 mg/kg for Pb, 48.26–72.40 mg/kg for Cr, 117.47–178.80 mg/kg for Zn, 71.13–107.82 mg/kg for Ni, 123.17–170.52 mg/kg for Cu, 0.74–1.25 mg/kg for Cd, 14.73–21.69 mg/kg for Co. Calculated enrichment factors (EF) reveal that enrichment of Pb and Cd is moderate at all sites, whereas other metals Cr, Ni, Zn, Co, and Cu show significant to very high enrichment. Geo-accumulation index (I _geo) results revealed that the study area is nil to moderately contaminated with respect to Cd, moderately to highly polluted with respect to Pb, Zn, and Cu and high to very highly polluted with respect to Co and Cr.     

Metal contamination of surface sediments of the Sfax–Chebba coastal line,Tunisia

Concentrations of several heavy metals (Pb, Cr, Cd, Cu, Zn and Fe) in surface sediment were determined to investigate the distributions and the metallic pollution status in Sfax–Chebba coastal area (southeast of Tunisia). Sediment samples were collected from 20 locations, representing three different site groups (i.e., site I: urban zone, site II: pre-urban zone and site III: rural zone). Heavy metal contents were analyzed by Atomic Absorption Spectrometry. The obtained results showed that generally, heavy metal concentrations in the coastal sediments near Sfax city (urban zone) were higher than those at other stations because of the anthropogenic activities. These concentrations exceeded the threshold effect levels. This was confirmed by the chemometric approaches (enrichment factors, geoaccumulation index and principal component analysis) which showed a significant impact of multiple anthropogenic sources. Moderate to extremely severe enrichment of sediments in terms of Pb, Cr, Cd, Cu and Zn were shown to exist in site I. Severe enrichment by Cd was also observed in other sites. Based on the geoaccumulation index, Pb, Cr, Cd, Cu and Zn can be considered as unpollutants to extreme pollutants.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.