Riverine transfer of heavy metals from Patagonia to the southwestern Atlantic Ocean

The occurrence and geochemical behaviour of Fe, Mn, Pb, Cu, Ni, Cr, Zn and Co are studied in riverine detrital materials transported by Patagonian rivers. Their riverine inputs have been estimated and the nature of these inputs to the Atlantic Ocean is discussed. Most of the metals are transported to the ocean via the suspended load; there is evidence that Fe oxides and organic matter are important phases controlling their distribution in the detrital non-residual fraction. Most heavy metal concentrations found in bed sediments, in suspended matter, and in the dissolved load of Patagonian rivers were comparable to those reported for non-polluted rivers. There is indication that human activity is altering riverine metal inputs to the ocean. In the northern basins – and indicating anthropogenic effects – heavy metals distribution in the suspended load is very different from that found in bed sediments. The use of pesticides in the Negro River valley seems correlated with increased riverine input of Cu, mostly bound to the suspended load. The Deseado and Chico Rivers exhibit increased specific yield of metals as a consequence of extended erosion within their respective basins. The Santa Cruz is the drainage basin least affected by human activity and its metal-exporting capacity should be taken as an example of a relatively unaffected large hydrological system. In contrast, coal mining modifies the transport pattern of heavy metals in the Gallegos River, inasmuch as they are exported to the coastal zone mainly as dissolved load. Electronic Publication     

The loading history of trace metals and nutrients in Altata-Ensenada del Pabellón,lagoon complex,northwestern Mexico

This paper summarizes the geochemical investigations about the origin and loading history of some trace metals (Ag, Cu and Zn) and nutrients (N and P) in the coastal lagoon complex of Altata-Ensenada del Pabellón, Mexico, by using the radioactive chronometers 210Pb and 228Th and the stable isotopes of C and N. The examination of sediment cores collected at different locations in the lagoon system identified a slight enrichment in metals and nutrients in some points, which was mainly associated to organic matter accumulation. Stable C and N isotope ratios revealed wastewater inputs to the lagoon system and the 210Pb geochronology showed that anthropogenic impact started 50 years ago, with the beginning of the agriculture development and the associated urban growth of the surrounding area. Several atypical 210Pb and 228Th/232Th profiles demonstrated that biological and physical disturbances are common phenomena in these environments, that frequently mask the pollution records; and therefore, considering that the contaminated sediments at some locations in the lagoon system are frequently resuspended and re-oxygenated, the pollutants will continue to be easily remobilized in the food chain.     

Factors controlling metal distributions in the surface sediments of the Erdek Bay, Sea of Marmara, Turkey

A geochemical study of the Erdek Bay sediments in the Sea of Marmara, Turkey, was carried out to investigate the heavy metal distributions and sources. The bay has an average depth of 34 m and a two-layer water column stratification, with a pycnocline at 20 m. The distribution of "total" metal (Fe, Mn, Pb, Cu, Ni, Cr, Zn and Hg) concentrations, together with sequential selective extraction analyses, shows that the relatively high metal concentrations are mainly due to land-based natural inputs from the erosion products of mineralized zones and mafic-ultramafic rocks delivered to the bay by two rivers from the south. However, some Pb, Zn and Cu occur in the Fe-Mn-oxyhydroxide and organic fractions, suggesting, in part, some anthropogenic inputs in addition to the predominantly natural inputs. The vertical distribution of metal/A1 ratios in a gravity core in the bay shows no significant change with depth, except for an early diagenetic enrichment at 0.7-1.6 m below sea floor (mbsf) above a 4750-3500-year-old sapropelic layer. This distribution is a further indication of the insignificant antropogenic metal pollution in the bay.     

Pb, Zn, and Cu levels in tree barks as indicator of atmospheric pollution

Barks of seven species of trees were sampled at 32 locations having different pollution levels in Abeokuta, Nigeria. The concentrations of Pb, Zn, and Cu were determined by atomic absorption spectrometry. The Pb and Zn contents, 1.9-159.8 and 16.5-659.1 micrograms g-1, dry weight respectively, correlate with traffic volume, indicating pollution from anthropogenic sources. The results obtained for Cu, 4.2-20.7 micrograms g-1, dry weight, though lower, were still significant but did not show any correlation with traffic density. The study also confirms the suitability of Azadirachta indica (Dogoyaro--a very popular local tree) as a suitable bio-indicator of aerial fallout of heavy metals.     

Sedimentation rates and trace metal input history in intertidal sediments from San Simón Bay (Ría de Vigo, NW Spain) derived from 210Pb and 137Cs chronology

(210)Pb and (137)Cs dating methods, accompanied by a high-resolution geochemical study, were applied to intertidal sediments containing both fine and coarse-grained particles and also, anthropogenic Pb in order to establish sedimentation rates and historical trends in heavy metal input. Sedimentation rates were established according to the "Constant Flux:Constant Sedimentation" (CF:CS) (210)Pb dating model, which was preferred rather than the "Constant Rate of Supply-Minimum Variance" (CRS-MV) model. Variations in sediment grain-size were accounted for by application of several normalization procedures. Al was selected for grain-size correction. Corrected sedimentation rates obtained from (210)Pb dating were corroborated through a second independent radionuclide tracer and by comparison of peak trace metal inputs into the environment with peaks in the sediment. The Chernobyl maximum was identified in the normalized (137)Cs activity profile. Sedimentation rates of 6.2+/-1.2 mm y(-1) and 3.1+/-0.5 mm y(-1) for the upper (two muddy layers) and 6.0+/-2.0 mm y(-1) for the lower (sandy) intertidal mud flat deposits of San Simón Bay were determined. According to the established chronology, human-induced environmental changes were detected in total metal concentrations (Cu, Pb, Zn) and in sediment grain-size and composition.     

Physical resuspension and vertical mixing of sediments on a high energy continental margin (Sydney, Australia)

Four sediment cores from the continental margin adjacent to Sydney were analyzed for 210Pb, 137Cs, trace metals (Ag, Cd, Co, Cu, Mn, Ni, Pb, Zn), iron, dry bulk density, mud and moisture content. The concentrations of trace metals in the total sediment are low at all sites, although slightly elevated concentrations of Ag, Cu, Pb and Zn are present in the fine fraction of sediment (< 62.5 microns) near a major ocean outfall. Concentrations of trace metals in the fine fraction of sediment are similar in the upper 10-15 cm, indicating strong vertical mixing of the sediments, whereas an upward coarsening grain size in the upper 1-3 cm of sediment supports physical resuspension during storms. Sediment accumulation rates on the middle shelf adjacent to Sydney were estimated from downcore profiles of 210Pb and 137Cs and range between 0.2 and 0.4 cm yr-1. Although the mass fluxes of Cu, Pb and Zn within a distance of 2 km from the outfall (up to 36.1, 30.8 and 86.2 micrograms cm-2 yr-1, respectively) are greater than 20 km north of the outfall (< 23.5 micrograms cm-2 yr-1), the low concentrations of trace metals in sediments near the outfall support an efficient dispersal of anthropogenic contaminants on this continental margin.     

Pollution load of Pb,Zn, and Cd and mineralogy of the recent sediments of Jordan River/Jordan

The present geochemical analyses of Zn, Pb and Cd in eighteen subsurface sediment samples collected from two locations along the Jordan River show that Cd is anthropogenically enriched in these sediments. In the sediment column, the concentration of Zn, Pb and Cd decreases clearly with depth in the first location of the upper reach, due to the high rate of sedimentation in this location; whereas the enrichment of elements of the lower reach increases gradually towards the old sediments. The Anthropogenic factor of the studied metals lies in the sequence of Pb>Cd>Zn.     

Correlations between speciation of Cd,Cu, Pb And Zn in sediment and their concentrations in total soft tissue of green-lipped mussel Perna viridis from the west coast of Peninsular Malaysia

Total concentrations and speciation of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) in surface sediment samples were correlated with the respective metal measured in the total soft tissue of the green-lipped mussel Perna viridis, collected from water off the west coast of Peninsular Malaysia. The aim of this study is to relate the possible differences in the accumulation patterns of the heavy metals in P. viridis to those in the surface sediment. The sequential extraction technique was employed to fractionate the sediment into 'freely leachable and exchangeable' (EFLE), 'acid-reducible,' 'oxidisable-organic' and 'resistant' fractions. The results showed that significant (P<.05) correlations were observed between Cd in P. viridis and Cd in the sediment (EFLE fraction and total Cd), Cu in P viridis and Cu in the sediment (EFLE and 'acid-reducible' fractions and total Cu) and Pb in P viridis and Pb in the sediment ('oxidisable-organic' fraction and total Pb). No significant correlation (P > .05) was found between Zn in P viridis and all the sediment geochemical fractions of Zn and total Zn in the sediment. This indicated that Zn was possibly regulated from the soft tissue of P. viridis. The present results supported the use of P viridis as a suitable biomonitoring agent for Cd, Cu and Pb.     

Heavy metal distribution and controlling factors within coastal plain sediments, Bells Creek catchment, southeast Queensland, Australia

Bells Creek catchment in southeast Queensland (Australia) is a non-industrialised coastal plain limited to small settlements and agricultural land. A study was initiated to examine elevated metal concentrations and to assess horizontal and vertical distribution of those elements. Ninety-nine samples were analysed for Cr, V, Ni, Cu, Zn, Pb, As, Fe, Mn and Al. Total organic carbon, sulfur content and mineralogy of samples along with land-use practices across the catchment were used to identify processes which influence metal distribution. A comparison between metal concentration within the study area and mean heavy metal content of standard sandstone showed that except for Mn, all other metals showed elevated levels throughout the catchment. When metal concentrations were compared to parent bedrock, however, it was concluded that elevated levels are likely to be natural. A normalisation procedure was applied to the data set and this analysis validated that elevated trace metal concentrations in most samples are not due to artificial contamination. While surficial estuarine sediments were only enriched in V, soils were dominantly enriched in Cr, Zn and V. Overall, geochemistry and mineralogy of the samples show the effect of both natural and anthropogenic inputs to the catchment, however, natural processes are more dominant than anthropogenic inputs in concentrating metals.     

Hyperaccumulation of Pb, Zn and Cd in herbaceous grown on lead-zinc mining area in Yunnan, China

A field survey of herbaceous growing on lead-zinc mining area in Yunnan, China were conducted to identify species accumulating exceptionally large concentrations of Pb, Zn and Cd in shoots. In total, 220 plant samples of 129 species of 50 families and 220 soil samples in which the plants were growing were collected. According to accumulation concentration in plant shoots and the concentration time levels compared to plants from non-polluted environments, 21 plant samples of 16 species were chosen as best-performing specimens, 11 plant samples of 10 species for Pb, 5 plant samples of 4 species for Zn and 5 plant samples of 5 species for Cd. Sonchus asper (L.) Hill in Qilinkeng had hyperaccumulation capacity to Pb and Zn. Corydalis pterygopetala Franch in Paomaping had hyperaccumulation capacity to Zn and Cd. All 5 Cd hyperaccumulators came from Lanping lead-zinc mining area. Out of 11 Pb hyperaccumulators, 7 came from Minbingying of Huice lead-zinc mining area. The average of the concentration time levels compared to plants from non-polluted environments were higher than 10 times in all plant samples, the concentration time levels changed from 203 times to 620 times for Pb, from 50 times to 70 times for Zn and from 145 times to 330 times for Cd. Out of 21 plant samples, translocation factor changed from 0.35 to 1.90, only translocation factor of 7 plant samples were higher than 1. Enrichment coefficients of all samples were lower than 1. These plant species were primarily heavy metal hyperaccumulator, and will be used in phytoremediation of the metallic pollutants in soils after further research in accumulation mechanism.     

Lead isotopes in environmental sciences: a review

Lead (Pb) isotopic analyses proved to be a very efficient tool for tracing the sources of local and global Pb pollution. This review presents an overview of literature published on the use of Pb isotopic analyses of different environmental matrices (atmospheric aerosols, lichens, tree rings, peat deposits, lake, stream, marine sediments, soils, etc.). In order to gain more insight, the isotopic compositions of major sources of Pb in the environment as determined by several authors are described in detail. These include, above all, the former use of leaded gasoline, coal combustion, industrial activities (e.g., metallurgy) and waste incineration. Furthermore, this review summarises analytical techniques (especially ICP-MS) used for the determination of Pb isotopes in environmental samples.     

Lead contamination and isotope signatures in the urban environment of Hong Kong

The source and the extent of Pb pollution in the urban environment of Hong Kong were investigated at five different urban settings selected on the basis of their annual average daily traffic (AADT) varying from less than 100 to 61,700. In addition, a small distant island without any traffic was selected to establish the possible baseline values. The surface environmental samples studied consisted of street and tunnel dusts, gully sediments, and a limited number of roadside topsoils. The analytical results clearly indicated variable degrees of Pb contamination in these urban settings. However, the level of contamination varied significantly among different types of samples collected at the same location. Pb concentrations of roadside topsoils (79+/-22 micrograms/g) and gully sediments (278+/-88 micrograms/g) were lower than those of the corresponding road dusts (327+/-54 micrograms/g). The Pb isotope compositions in different urban settings varied considerably. The bedrock in the small island had the lowest Pb concentration (12 micrograms/g) but with the highest 206Pb/207Pb ratio (1.2206), whereas the tunnel ceiling dusts with the highest level of Pb (1410 micrograms/g) had the lowest 206Pb/207Pb ratio (1.1062). Despite the significant differences in vehicle types and traffic volumes, and the presence of several different petroleum retailers in Hong Kong, the Pb isotope ratios of road dusts (206Pb/207Pb: 1.1553+/-0.0043, 208Pb/207Pb: 2.4408+/-0.0084) varied within a relatively narrow range among all the five urban sampling sites. On the other hand, the Pb isotopic compositions of gully sediments (206Pb/207Pb: 1.1515+/-0.0145, 208Pb/207Pb: 2.4322+/-0.0198) varied noticeably within the same setting, but were reasonably comparable across the different study sites. In general, the 206Pb/207Pb ratios of road dusts can be used to estimate the direct contribution from automobile emissions, whereas those of gully sediments might reflect the effects of the mixing of different anthropogenic sources. The Pb isotope signatures in the urban environment of Hong Kong clearly suggested that anthropogenic Pb in the environment originated from Pb ore with a low 206Pb/207Pb ratio (such as the Australian Pb ore and similar sources in Southeast Asia) were significantly different from those of the anthropogenic Pb present in the neighboring Pearl River Delta (PRD) region.     

137Cs and excess 210Pb deposition patterns in estuarine and marine sediment in the central region of the Great Barrier Reef Lagoon, north-eastern Australia

This paper focuses on the distribution of 137Cs and 210Pb(xs) in 51 estuarine and marine sediment cores collected between the Upstart Bay and Rockingham Bay in the Great Barrier Reef Lagoon, north-eastern Australia. Historical records of 210Pb(xs) and 137Cs atmospheric deposition and present day terrestrial inventories in north-eastern Australia are presented. 210Pb(xs) and 137Cs fluxes measured on suspended sediments in the Burdekin River are considered to be a source of recent inputs of these nuclides to the nearshore region of this part of the Great Barrier Reef. Direct correlations between sediment nuclide inventories, maximum detectable depths, and sediment mass accumulation rates (MARs), calculated using both 137Cs and 210Pb(xs), are explored. In relation to inventories of 210Pb(xs), 60% of atmospheric fallout 137Cs appears to be missing from the sediments. The reasons for these differences in two tracers, primarily of atmospheric origin, are discussed in terms of the geochemical properties of these two nuclides. Evidence is presented to support the hypothesis that the 137Cs distribution in these cores can be a useful independent tracer which provides confirmation of MARs calculated from the decay of 210Pb(xs).     

Effects of readily dispersible colloid on adsorption and transport of Zn, Cu, and Pb in soils

Soil colloids (<0.002 mm) were extracted from three types of soils to make the colloid-bound forms of Zn, Cu, and Pb solution. The clay mineral types and composition of the colloids, the adsorption characteristics of the colloids, and the effect of readily dispersible colloid on the transport of metals and the quality of the soils and groundwater were studied. The results showed that the adsorption capacity of Cu, Zn, and Pb was greater for the Aquic Vertisols (Shajiang Black soil) as compared to the Udic Luvisols (Brown soil) and Usdic Luvisols (Cinnamon soil), due to the difference of clay content and clay mineral composition in the different soils. The adsorption capacity of Pb was much higher than that of Zn and Cu for the same soils, which would contribute to the chemical properties of metals and specific adsorption characters of the colloids. The mobility of Zn in soils was greater than that of Cu and Pb, while similar trend was found in the transportation processes for Zn and Cu. The concentration of Zn and Cu in leachates increased as the leaching solution volume increased, but the migration of Pb was negligible, and the concentration of Pb could not been detected in leachates even after 7.5 pore volume leaching solution. The influence of mobility on Zn and Cu transport was different for different type of colloids. The mobility caused by readily dispersible colloids from Aquic Vertisols was greater as compared to that of Udic Luvisols and Usdic Luvisols. Analysis of soils after column leaching indicated that Zn was distributed much deeper than Cu, but Pb was almost not migrated, and mainly accumulated in the soil surface. Therefore, Zn had greater tendency for the groundwater pollution than Cu and Pb, and Pb tends to contaminate the surface soils.     

“城郊乡”梯度下土壤Cu、Zn、Pb含量的空间变异特征

为揭示城市化、工业化等人为活动对土壤环境质量的影响,选择能反映上海城郊乡梯度差异的中心城区、城郊结合部和远郊,采用地统计学方法对表层土壤样品Cu、Zn、Pb的空间变异结构和分布特征进行了对比分析。结果表明:城市土壤Pb、Cu、Zn的变异系数范围为0.24~0.62,均属中等变异强度。徐汇区土壤Cu、Pb、Zn符合正态分布,闵行区土壤Cu、Pb和Zn符合对数正态分布,奉贤区土壤Zn呈正态分布,土壤Cu、Pb符合对数正态分布。由中心城区到远郊,城市土壤Cu、Pb、Zn的各项统计特征值和变异系数均有较大差异,存在明显的空间分布差异。半方差函数分析结果表明,徐汇区作为中心城区,土壤Cu、Pb、Zn符合球状模型,土壤Cu、Zn具有强烈的空间相关性,土壤Pb具有明显的空间自相关。奉贤区以农业用地为主,土壤Pb符合线性模型,土壤Cu符合高斯模型,土壤Zn符合指数模型,具有强烈的空间相关性。闵行区地处城郊结合部,土壤Cu、Pb、Zn的半方差拟合模型均为线性模型,表现为纯块金形式,以随机变异为主,空间相关性弱。采用Kriging最优内插法进行无偏估值,绘制了表层土壤重金属含量的空间分布图,中心城区、城郊结合部、郊区土壤重金属的空间分布受城市化、工业化、城市交通等因素的影响,均表现出不同的空间分布规律。     

Effects of Se and Zn supplementation on the antagonism against Pb and Cd in vegetables

The antagonistic effects of supplementation of Zn and Se to the soil on vegetables were studied in this work. In the pot experiment, Se (Se4+) and Zn (Zn2+) were applied, respectively, to the soil, in which the Chinese cabbage (Brassica rapa) and the lettuce (Lactuca sativa L.) were planted. As a result, Se and Zn were enriched evidently in the two vegetables. The contents of Pb and Cd in the two vegetables were decreased markedly while contents of some healthy mineral elements, like Mn and Mg, were increased to some extent when Se and Zn were applied. The antagonism of Se and Zn against Pb and Cd in plants was suggested. The farmland experiment on the lettuce was conducted to explore further the effect of supplementation of Zn and Se under the actual field conditions. Result came out to be that the enrichment of Zn and Se restrained the accumulation of Pb and Cd in the lettuce remarkably, as well as enhanced the absorption of some other nutritional elements, like Fe, Mn, Cu, Ca and Mg. Therefore, application of Se and Zn was proved to be an effective and feasible method to improve trace elements nutrition in the vegetables.     

The relationship of dissolved Pb to some dissolved trace metals (Al, Cr, Mn, and Zn) and to dissolved nitrate and phosphate in a freshwater aquatic system in Mauritius

The relationship of some dissolved trace metals (Al, Cr, Mn, Zn, and Pb) with one another and to dissolved phosphate and nitrate in a freshwater aquatic system at Flic en Flac and Grand River North West (GRNW) in Mauritius (1850 km2, 20 degrees S and 57 degrees E, Western Indian ocean) is reported following trace metal determination using inductively coupled plasma mass spectrometry (ICP-MS). Dissolved Al (<200 ng ml(-1)), Cr (<50 ng ml(-1)), Mn (<50 ng ml(-1)), Zn (< 100 ng ml(-1)), and Pb (<50 ng ml(-1)) upstream, downstream GRNW and in the marshes and rivulet at Flic en Flac were found to be below the recommended EEC maximum admissible concentrations and within the ambient drinking water quality standards in Mauritius. Dissolved Pb was significantly positively correlated to both dissolved Cr and Zn suggesting that the cycling for dissolved Pb is linked to the cycling of both dissolved Cr and Zn along GRNW. The common influential cycling of Pb and Zn was further reinforced as both dissolved Pb and Zn were significantly positively correlated to dissolved phosphate, which suggested a biological role in the cycling of Zn and Pb. The role of biological activity or adsorption to biological systems in Pb cycling along GRNW is further suggested as dissolved Pb was significantly correlated to dissolved nitrate. The apparent absence of the dissolved Al, Cr, and Mn with dissolved nitrate and phosphate could be attributed to factors such as the lower sensitivity of the GRNW to metal uptake during biological activity during the time frame considered. The cycling of dissolved Al and Mn was also not linked to the cycling of Cr, Zn, and Pb as no significant correlation was found along GRNW.     

Polynuclear aromatic hydrocarbons,phenols, and trace metals in selected soil profiles and plant bioindicators in the Holy Cross Mountains,south-central Poland

This report presents the results of PAH, phenol, and selected trace element (Cd, Cu, Hg, Pb, S, and Zn) determinations on detailed soil profiles and associated plant bioindicators (including lichen Hypogymnia physodes, moss Hylocomium splendens, pine Pinus sylvetris) from the three most representative habitats in the Holy Cross Mts, south-central Poland. This study is only part of a larger ongoing environmental study that includes complex sulfur isotope and element determinations in three national parks in N, central and S parts of Poland. The highest concentrations of PAHs (1887 ppb) and numerous trace elements are found in the organic horizon-O and humic horizon-A of each soil type. Different plant species and their individual tissues reveal considerable variability in the concentration of PAHs, phenols and elements examined. Most of the H. physodes thalli also reveal higher concentrations of individual hydrocarbons and some elements (including S and Zn) than their host bark. The highest concentration levels of phenols (1217 ppb) are noted in the 1-year pine needles. Most of the PAHs and elements examined seem to be of anthropogenic origin. The only exception is the distribution pattern of elements in southwestern part of the study area, which is linked to the local bedrock geochemical anomaly. The results of this study indicate that the content of PAHs, Cd, Cu, Hg, Pb, S and Zn in the soils and plant bioindicators examined has not changed considerably since 1998.     

Correlation of the partitioning of dissolved organic matter fractions with the desorption of Cd,Cu, Ni,Pb and Zn from 18 Dutch soils

Eighteen Dutch soils were extracted in aqueous solutions at varying pH. Extracts were analyzed for Cd, Cu, Ni, Pb and Zn by ICP-AES. Extract dissolved organic carbon (DOC) was also concentrated onto a macroreticular resin and fractionation into three operationally defined fractions: hydrophilic acids (Hyd), humic acids (HA) and fulvic acids (FA). In this manner, change in absolute solution concentration and relative percentage for each fraction could be calculated as a function of extraction equilibrium pH. The soils were also analyzed for solid phase total organic carbon and total recoverable metals (EPA Method 3051). Partitioning coefficients were calculated for the metals and organic carbon (OC) based on solid phase concentrations (less the metal or OC removed by the extraction) divided by solution concentrations. Cu and Pb concentrations in solution as a function of extract equilibrium pH are greatest at low and high pH resulting in parabolic desorption/dissolution curves. While processes such as proton competition and proton promoted dissolution can account for high solution metal concentrations at low pH, these processes cannot account for higher Cu and Pb concentrations at high pH. DOC increases with increasing pH, concurrently with the increase in Cu and Pb solution concentrations. While the absolute concentrations of FA and HA generally increase with increasing pH, the relative proportional increase is greatest for HA . Variation in HA concentrations spans three orders of magnitude while FA concentrations vary an order of magnitude over the pH range examined. Correlation analysis strongly suggests that HA plays a major role in increasing the concentration of solution Cu and Pb with increasing pH in the 18 soils studied. The percentage of the OC that was due to FA was nearly constant over a wide pH range although the FA concentration increased with increasing pH and its concentration was greater than that of the HA fraction at lower pH values (pH = 3-5). Thus, in more acidic environments, FA may play a larger role than HA in governing organo-metallic interactions. For Cd, Ni, and Zn, the desorption/dissolution pattern shows high metal solution concentrations at low pH with slight increases in solution concentrations at extremely high pH values (pH>10). The results presented here suggest that the effects of dissolved organic carbon on the mobilization of Cd, Ni, and Zn may only occur in systems governed by very high pH. At high pH, it is difficult to distinguish in this study whether the slightly increased solution-phase concentrations of these cations is due to DOC or hydrolysis reactions. These high pH environments would rarely occur in natural settings.     

Physico-chemical and toxicological characterization of the historic estuarine sediments: a multidisciplinary approach

The accumulation rates, the geochronology of metals and PAH contamination, and the Microtox toxicity are studied in five sediment cores (50 cm length) covering different areas of the Santander Bay, Northern Spain. Chronology given by (210)Pb and (137)Cs reveals significant differences in accumulation rates between sites (0.2-1.1 cm/year), as well as a variable degree of anthropogenic enrichment factors for Fe, Mn, Cu, Pb, Zn, Ni (from 1 to 15) and concentrations of summation Sigma 16PAHs (from 0.01 to 23.84 mg/kg dw) in sediments over the last 90 years. The results indicate the increasing contamination pressure from industrial and urban activities along the Bay. No toxic results from the Microtox test are obtained either with pore water or with normalised sediment aqueous extracts (European Norm EN 12457), suggesting low water solubility and low availability of contaminants in the studied sediments. However, the EC50 values from the Microtox Basic Solid Phase Test (BSPT) ranged from 0.03% to 2.35%, showing vertical toxicity profiles in accordance with metal and PAHs behaviour. The correlation degrees of Microtox BSPT toxicity to chemical concentration in sediment profiles are widely variable showing a high site-dependent toxicity. The oligochaete Limnodrilus hoffmeisteri has been used as a chronic bioassay over surface sediments of two of the studied sites, showing results coherent with the Microtox BSPT acute test results. Global results of the present work provide regional geochemical baselines for metals and PAHs and toxicological data now make it possible to obtain a preliminary quality assessment of the Santander Bay sediment profiles.