Influence of copper status on the accumulation of toxic and essential metals in cattle

The aim of the present study was to assess whether the use of pig slurry and associated copper accumulation in calves grazing pastures fertilized with pig slurry from the Deza region in NW Spain has a significant influence on toxic metal and essential metal levels, and to investigate whether copper accumulation is correlated with the levels of these other metals. Correlations between copper, toxic metals (cadmium, lead) and essential metals (molybdenum, iron, zinc, selenium, manganese and cobalt) concentrations were evaluated in liver and kidney of 195 calves from the region of Deza. Metal concentrations were determined by ICP-OES and correlations between pairs of elements by Pearson correlation analysis. There was a strongly significant positive association between copper and lead in the liver. Considering the trace metals, copper in the liver showed significant positive correlations with cobalt in both liver and kidney, and with molybdenum in the liver. In addition, significant correlations were observed between copper and most essential metals in kidney. These associations are similar to those found in different animal species experimentally dosed with copper and other metals, as well as in cattle exposed to normal copper concentrations.     

Stress-70 proteins in marine mussel Mytilus galloprovincialis as biomarkers of environmental pollution: a field study

In the present work we have investigated levels of stress-70 proteins in the gills of mussel Mytilus galloprovincialis collected seasonally from subtidal rocky shores at 6 different sites of the Rovinj coastal area (Northern Adriatic, Croatia). 1-D analysis (SDS-PAGE) using monoclonal mouse antibodies anti-HSP70 detected two bands of stress-70 proteins, 70 and 72 kDa constitutively present during the year. 2-D analysis (IEF+SDS-PAGE) proved that the antibodies used detected HSP70 (pI 5.7-5.9) and HSP72 (pI 5.5-5.6). The quantification of stress-70 proteins was possible using 200 ng of external HSP70 protein standard included on every blot. Maximal levels of HSP72 and HSP70 were observed in mussels in summer (September), and minimal levels in winter (December), and only HSP70 showed significant correlation with the sea temperature (r=+0.822, p<0.05). Acclimatization of mussels to a different lower salinity under experimental conditions proved that small changes in sea salinity (Delta=2 psu) could not cause significant stress-70 proteins induction. Results indicated that there are significant differences in HSP70 and HSP72 content in mussels from the control site (S-1) and mussels from other sampling sites with urban and industrial pollution. The usefulness of stress-70 proteins as biomarkers of environmental pollution is discussed.     

Activity of glutathione S-transferase in Spodoptera exigua larvae exposed to cadmium and zinc in two subsequent generations

The aim of our study was to establish changes in activity of important in detoxification enzyme-glutathione S-transferase (GST): in alimentary tract, fat body and Malpighian tubules of Spodoptera exigua larvae being under cadmium and zinc exposure through the first as well as the second generation. There was registered enhancement of the enzyme activity in the fat body and the Malpighian tubules caused by zinc as well as its decrease in the Malpighian tubules under cadmium action. Amounts of metals in the alimentary tract were either several times higher than in the diet ingested by larvae or than in the fat body. Metal concentration in the fat body correlated with the level of the enzyme activity (positive correlation for zinc and negative for cadmium). The effect of metal action differentiated dependently on time exposition.     

Toxicities and tolerances of Cd, Cu, Pb and Zn in a primary producer (Isochrysis galbana) and in a primary consumer (Perna viridis)

Studies on toxicities and tolerances of cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) in the brown alga Isochrysis galbana and in the green-lipped mussel Perna viridis were conducted by short-term bioassays using endpoints growth production and mortality, respectively. The 5-day EC(50) and 24-h LC(50) of these heavy metals were determined in the brown alga and mussel, respectively. The EC(50) values calculated for the alga were 0.74 mg/l for Cd, 0.91 mg/l for Cu, 1.40 mg/l for Pb and 0.60 mg/l for Zn. The LC(50) values for the mussels were 1.53 mg/l for Cd, 0.25 mg/l for Cu, 4.12 mg/l for Pb and 3.20 mg/l for Zn. These LC(50) values were within the concentration ranges as reported by other authors who used P. viridis as the test organism. Based on these EC(50) and LC(50) values, the alga was most sensitive to Zn, followed by Cd, Cu and Pb while the mussel was most sensitive to Cu, followed by Cd, Zn and Pb. Differences in the trophic levels, metal handling strategies, biology and ecology of the primary producer (brown alga) and the primary consumer (mussel) are believed to be the plausible causes for the different toxicities and tolerances of the metals studied.     

Heavy metal levels and esterase variations between metal-exposed and unexposed duckweed Lemna minor: field and laboratory studies

Environmental homogeneity is being continuously disturbed and affected by artificially introduced loads of chemical toxicants that also include heavy metals. The Tiljala wetlands of the eastern fringe of Calcutta, West Bengal (India) are a virtual sink for the deposition of urban and industrial wastes that get admixed with the aquatic environment. We have selected Lemna minor (duckweed), as a representative of the biota surviving therein for the present study. Concentrations of lead, cadmium, chromium, zinc, copper and mercury in the fronds of Lemna were measured to peep into the range of input of heavy metals in the duckweed subjects. Natural unexposed population of duckweed from a domestic pond in Batanagar area, 24 Parganas, West Bengal (India) was also found to accumulate similar concentrations of these metals when cultured in artificially contaminated water in the laboratory. The exposed individuals also exhibited polymorphism with respect to the loci of esterase, as compared to an unexposed control plants. Therefore, the present study suggests EST variations of L. minor to be a potential biomarker of heavy metal pollution.     

Accumulation of Cu,Zn, Cd,and Pb by Scenedesmus obliquus under nongrowth conditions

The aim of this work has been to assess the accumulation of copper, zinc, cadmium and lead by a test alga, Scenedesmus obliquus, under nongrowth conditions. The results provide an evidence that metals can be readily accumulated by algae and that accumulation is a function of the metal-to-algae exposure ratio. When the metals were added in combination in equimolar concentrations, the following order of affinity to algal surface was detected Zn > Cu ? Cd > Pb. However, when EDTA was added to the test water, metal accumulation was greatly retarded. Moreover, when algae loaded with one of the metals were washed with EDTA solution the major part of the accumulated metal was mobilized, indicating that EDTA had stronger metal binding affinity than any ligands liable to exist on algal surface. Metal accumulation by algal cells isolated from a culture in the logarithmic growth phase was of much higher magnitude than that displayed by cells isolated from a culture in the decline phase.     

Trace metal levels in tree barks as indicators of atmospheric pollution

Barks of six species of trees were sampled at thirty-nine different locations in Ibadan, Nigeria and were analysed for the trace metals lead, cadmium, cobalt, copper, zinc, manganese, and iron. Lead levels in barks from areas with relatively high traffic density were generally higher than lead levels in barks from areas with low traffic density. The lead level recorded in the high traffic density areas, 40–140 μg/g, is low compared to values reported for barks of trees along busy roads in developed countries. For the other metals, no correlation with traffic density was observed.     

Thallium: a review of public health and environmental concerns

Thallium (Tl) is a rare but widely dispersed element. All forms of thallium are soluble enough to be toxic to living organisms. Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc and has been responsible for many accidental, occupational, deliberate, and therapeutic poisonings since its discovery in 1861. Its chemical behavior resembles the heavy metals (lead, gold and silver) on the one hand and the alkali metals (K, Rb, Cs) on the other. It occurs almost exclusively in natural waters as monovalent thallous cation. The solubility of thallous compounds is relatively high so that monovalent thallium is readily transported through aqueous routes into the environment. Tl can be transferred from soils to crops readily and accrues in food crops. The fascinating chemistry and high toxicity potential make thallium and its compounds of particular scientific interest and environmental concern. Thallium was detected in base-metal mining effluents. The conventional removal of heavy metals from wastewater has little effect on thallium. In this review, various treatment options and removal technologies are enumerated in order to protect the environment from thallium toxicity.     

Exposure to metal mixtures and human health impacts in a contaminated area in Nanning, China

Cadmium and lead have been identified as very toxic metals, which are widely present in the environment due to natural and anthropogenic emissions. Many studies have shown that the food chain is the main pathway of cadmium and lead transfer from the environment to humans. It is well documented that many factors will affect their transfer through food chains. Previous investigations on heavy metals were mostly concentrated on one contaminant in isolation. However, in real environments, exposure to mixtures of metals is ubiquitous such that cadmium pollution is invariably being associated with lead and zinc, etc. This study focuses on the contamination and health effects of the metal mixtures. For this purpose, a dietary survey was taken for 3 groups in Nanning in October 2002. Samples of soils, plants (vegetables), urine and blood of humans were measured for Cd, Fe, Cu, Zn, Ca and Pb, in addition, the urinary indicators of renal dysfunction Albumin (ALB), N-acetyl-beta-D-glucosaminidase (NAG), Beta-2-microglobulin (beta2-MG) and Retinol-binding protein (RBP) in urine were also measured. Results showed that soil contamination with metal mixtures had caused significant renal dysfunction of the local residents living in the contaminated area, and the dose-response curve was somewhat altered by the mixed contamination of Cd and Pb as well as the intake of other minerals. The importance of mixtures of metal contamination and human health are also discussed in this paper.     

Partitioning of trace metals between soft tissues and shells of Patella aspera

This paper describes the partitioning of iron, manganese, zinc, copper, cadmium, cobalt, nickel and lead between the soft tissues and the shells of the gastropod mollusc Patella aspera. Specimens of the limpet P. aspera were collected from a clean coastal marine site (CMS) and from an estuarine contaminated site (ECS) on the south coast of Portugal. Fe and Zn concentrations were significantly lower on both populations and less variable in the shells than in the soft tissues. In contrast Mn concentrations were higher in the shells than in the soft tissues at ECS. The partitioning factor (PF), defined as the ratio between the mean metal concentrations in soft tissues and in the shells, was maximum for iron and minimum for manganese. Between the soft tissues and the shells, only manganese at ECS recorded a significant relationship between metal concentrations, suggesting that the mechanism that controls the accumulation of this essential metal in both tissues was different from the others. From the obtained data, in biomonitoring sewage contamination studies, shells of P. aspera can be considered as a good indicator for Mn while the soft tissues for Zn. As copper, cadmium, nickel and cobalt concentrations were much higher in the soft tissues than in the shells (< 0.1 microg g(-1)), this indicates that the shells were not a good indicator for these metals because they do not reflect the environmental bioavailability as do the soft tissues.     

Flux of heavy metal accumulation in various organs of the intertidal marine blue crab, Portunus pelagicus (L.) from the Kuwait coast after the Gulf War.

The metal levels of arsenic, chromium, copper, lead, magnesium, manganese, selenium, vanadium, and zinc concentrations were determined in various body organs, viz., hepatopancreas, gills, gonad, gastric stomach, and muscle of the blue crab, Portunus pelagicus (Crustacea: Decapoda) to assess the bioaccumulation of metals associated with petroleum input a decade after the 1991 Gulf War oil spillage. Sample solutions prepared were analyzed using an atomic absorption spectrophotometry. High concentrations of Zn and Cu in the muscle and hepatopancreas tissues were a strong indicative of high exposure of P. pelagicus to these metals. However, muscle tissue had been found to accumulate the highest values for all metal speciations analyzed. Copper, zinc, and chromium in samples collected from Station II covering the Kuwait City area were often in excess of those present in Station I and III. Arsenic, lead, magnesium, manganese, selenium, and vanadium were greater in individuals obtained from Station I. A significant correlation was found to exist between Se and V in crab muscle with a surge in Se metal concentration, which was found to be inversely proportional to that of V metal concentration irrespective of the sex of the crab. The difference in patterns of metal occurrence and the significant increase in the Cu and Zn concentrations in various organs of the crab were largely associated with the 1991 Gulf War oil spill. Such results could be used as a baseline for the monitoring of the level of metals in marine organisms of future studies.     

Prenatal exposure to environmental contaminants and behavioural problems at age 7–8 years

Animal studies showed that the developing brain is particularly sensitive to chemical exposure. Human studies carried out in areas with high exposures have proven neurodevelopmental disorders in relation to e.g. lead and PCBs. Whether these chemicals are associated with behavioural problems in childhood at current environmental levels is not well known. Therefore, we assessed the association between prenatal exposure to lead, cadmium, PCBs, dioxin-like compounds, HCB and p,p′-DDE and behavioural problems in 7–8 year old children. Prenatal exposure data were obtained from the Flemish mother–new-born cohort. Lead, cadmium, PCBs, dioxin-like compounds, HCB and p,p′-DDE were analysed in cord blood. When the child reached 7–8 years, 270 mothers completed the Strengths and Difficulties Questionnaire assessing their children's behavioural health. We found that doubling the prenatal lead exposure (cord blood lead levels) was associated with a 3.43 times higher risk for hyperactivity in both boys and girls. In addition, total difficulties were 5.08 times more likely in the highest tertile for prenatal lead exposure compared to the lowest tertile. In girls, total difficulties were 4.92 more likely when doubling cord blood p,p′-DDE, whereas no significant association was found in boys. Further, we noted in boys a 1.53 times higher risk for emotional problems when doubling cord blood cadmium, whereas no significant association was found in girls. These results indicate that the presence of environmental contaminants influences the mental health of the next generation.     

Bacterial extracellular polymeric substance (EPS): a carrier of heavy metals in the marine food-chain

The ecological implications of metal binding properties of bacterial EPS and its possible role in the bioaccumulation of pollutants in the marine food-chain was investigated using a partially purified and chemically characterized microbial EPS isolated from a species of Marinobacter. Various factors influencing metal sorption by the EPS including the influence of initial metal concentrations, incubation time, pH and sodium chloride concentrations on binding of lead (Pb2+) and copper (Cu2+) were evaluated. The bacterial EPS selectively bound more amount of Cu2+ per mg of EPS than Pb2+. Both copper and lead were sorbed more at near neutral pH than acidic pH. The sorption of Cu2+ increased with increasing copper concentration. The estimated maximum binding ability (MBA) of the EPS was 182 nmol copper and 13 nmol lead mg(-1) EPS. However, the sorption of these metals decreased with the increase in sodium chloride concentration. Furthermore, up to 35% of 14C-labeled Marinobacter was ingested by a benthic polychaete Hediste diversicolor. On an average, 29% of the ingested EPS was absorbed into tissues and 49% of the EPS was respired. It was apparent that the animals used the EPS as a source of energy and nutrition. The labile nature of the bacterial EPS and its ability to bind heavy metals might route the bound metals through the marine food chain, thereby transferring and aiding bioaccumulation of metal pollutants in the higher trophic animals.     

Assessment of arsenic and heavy metal concentrations in water and sediments of the Rio Grande at El Paso-Juarez metroplex region

The Rio Grande located along the US-Mexico border is affected by anthropogenic activities along its geographical course. Runoff and wind deposition of smelting residues may contribute to the pollution of the Rio Grande in the El Paso-Ciudad Juarez area. Few studies have addressed the presence or impacts of heavy metals or arsenic in this ecosystem. This study reports a survey of heavy metals (Cr, Cu, Cd, Ni, Pb, and Zn) and arsenic (As) in water and sediments of the Rio Grande collected from seven sites in the El Paso-Juarez region. Since water quality influences metal content in water, physical (temperature, flow and conductivity), and chemical (pH, dissolved oxygen, nitrates, alkalinity, and water hardness) parameters were measured at each site. Arsenic and heavy metal levels were determined using Inductively Couple Plasma (ICP) emission spectroscopy following EPA procedures. Zinc and lead were found as both total and dissolved metals in most of the samples, with concentrations of total recoverable metals reaching up to 105 and 70 microg/l, respectively. Most metals were found in sediment samples collected from four of seven sites. The highest Cu concentration (35 mg/l) was found at the American Dam site. Concentrations of metals found through this survey will be used as a reference for future studies in monitoring arsenic, heavy metals, and their impacts in the Rio Grande.     

Circulating levels of environmental contaminants are associated with dietary patterns in older adults

BackgroundFood intake contributes substantially to our exposure to environmental contaminants. Still, little is known about our dietary habits' contribution to exposure variability.ObjectiveThe aim of this study was to assess circulating levels of environmental contaminants in relation to predefined dietary patterns in an elderly Swedish population.MethodsDietary data and serum concentrations of environmental contaminants were obtained from 844 70-year-old Swedish subjects (50% women) in the Prospective Investigation of the Vasculature in Uppsala Seniors (PIVUS) study. Dietary data from 7-day food records was used to assess adherence to a Mediterranean-like diet, a low carbohydrate–high protein diet and the WHO dietary recommendations. Circulating levels of 6 polychlorinated biphenyl markers, 3 organochlorine pesticides, 1 dioxin and 1 polybrominated diphenyl ether, the metals cadmium, lead, mercury and aluminum and serum levels of bisphenol A and 4 phthalate metabolites were investigated in relation to dietary patterns in multivariate linear regression models.ResultsA Mediterranean-like diet was positively associated with levels of several polychlorinated biphenyls (118, 126, 153, and 209), trans-nonachlor and mercury. A low carbohydrate–high protein diet was positively associated with polychlorinated biphenyls 118 and 153, trans-nonachlor, hexachlorobenzene and p, p′-dichlorodiphenyldichloroethylene, mercury and lead. The WHO recommended diet was negatively related to levels of dioxin and lead, and borderline positively to polychlorinated biphenyl 118 and trans-nonachlor.ConclusionDietary patterns were associated in diverse manners with circulating levels of environmental contaminants in this elderly Swedish population. Following the WHO dietary recommendations seems to be associated with a lower burden of environmental contaminants.     

Input of heavy metals to the forest floor as a result of Cracow urban pollution

The influence of Cracow's urban pollution on small forest ecosystems was studied during 1998-2000. Seven sites located at different distances from the Cracow conurbation and from busy road were selected. Two sites were situated 26 and 31 km from Cracow town along an eastern transect, the other five-3, 8, 14, 26 and 35 km respectively, from Cracow-along a southern transect. At the beginning of September, five litter traps were set at each site. The quantity of litter fall, along with percentage composition of each species, were estimated for an area of 1 m(2). The concentration of Cd, Pb, Cu, Zn and Fe in the litter fall and the input of these metals to the forest floor were determined. The input of cadmium ranged from 84 microg m(-2) at Kornatka in 1998 to 382 microg m(-2) at Bonarka in 2000. The input of lead was about 10 times higher than cadmium and varied from 406 microg m(-2) at Weglówka in 1998 to 3717 microg m(-2) at Bonarka in 2000. Input of Cu, Zn and Fe to the forest floor showed the similar tendency. During 1998-2000, the highest heavy metal concentrations in the litter fall and their impact on the forest floor were always found at sites close to the Cracow conurbation and, in the eastern transect, close to a steel works. Input of metals to the forest floor tended to decrease with increasing distance from the centre of Cracow.     

有色金属国际价格波动的影响因素研究

有色金属作为国际上流通量较大的大宗产品,近年来其价格的频繁剧烈波动受到学界和业界的高度关注。从有色金属国际贸易的交易量数据看,中国、美国、巴西等20个国家是有色金属国际贸易的主体,贸易量较大的是铜、铝、铅、锌四种有色金属。本文选取了国际贸易中铜、铝、铅、锌四种有色金属的主要进口国和出口国,在已有研究的基础上,从供需、实体经济和货币金融三个维度选取变量,运用国家之间构成的面板数据,建立PVAR模型,分析四种有色金属价格的波动及其影响因素;通过铜、铝、铅、锌四种有色金属价格的脉冲响应函数,比较分析铜、铝、铅、锌四种有色金属价格波动影响因素的不同。研究发现:(1)铜、铝、铅、锌四种有色金属价格波动均受国内生产总值和货币供应量的影响,供需因素对有色金属价格产生长期的影响,货币供给量对有色金属价格的影响短暂而剧烈;(2)国内生产总值和贸易量与铜价的波动密切相关,货币供应量和消费者价格指数与铝、铅、锌价格的波动密切相关;(3)有色金属主要贸易国的各个变量对铜、铝、铅、锌价格波动的贡献程度不同。铜贸易国的贸易量对铜价波动的贡献度要高于其他有色金属贸易国家;铝、铅、锌贸易国家的金融因素对铝、铅、锌价格的影响要强于铜贸易国家。最后,本文从进口国角度对中国有色金属进口提出了建议:中国是铜、铝、铅、锌四种有色金属的最大进口国,应密切关注有色金属价格走势,建立健全有色金属价格的实时监测和预警机制,加快对有色金属价格波动的反应速度,利用金融手段避险趋利。     

Cadmium, copper, mercury, and zinc concentrations in tissues of the king crab (Pseudocarcinus gigas) from southeast Australian waters.

The concentrations of cadmium, copper, mercury, and zinc were determined in muscle (body, claw, and leg), hepatopancreas, and gill tissues of Pseudocarcinus gigas, an exceptionally large, long-lived, and deep-dwelling crab species. The accumulation patterns observed are discussed in terms of both intra- and interspecies variations, with particular attention to the possible consequences of the extreme size and depth range of P. gigas. Metal concentrations did not depend significantly on sex of the crab. Significant differences between tissues were detected for all metals, and the distribution of metal between the tissues was different for each metal. Significant correlations were found between metal concentrations in the various tissues and crab size, and these are discussed and rationalised. The concentrations of mercury and zinc in muscle tissue increased with crab size and were high compared to other crab species. The concentrations of cadmium and copper present in edible tissues were not especially high compared to other crab species, but the concentration of cadmium in the hepatopancreas is of dietary concern.     

Allozyme polymorphisms and heavy metal levels in the green-lipped mussel Perna viridis (Linnaeus) collected from contaminated and uncontaminated sites in Malaysia

It has been widely reported that heavy metal contamination in coastal waters can modify the allozyme profiles of marine organisms. Previous studies have recorded elevated metal concentrations in sediments and mussel tissues off Peninsular Malaysia. In the present study, horizontal starch gel electrophoresis was carried out to estimate the levels of allelic variation of the green-lipped mussel, Perna viridis, collected from one contaminated and three relatively uncontaminated sites off Peninsular Malaysia. Fourteen polymorphic loci were observed. In addition, the concentrations of cadmium, copper, lead, mercury and zinc were determined in the sediments and in the soft tissues of the mussels. Mussels from contaminated site, evidenced by high metal pollution indices (MPI) of the sediment and the mussel tissues, showed the highest percentage of polymorphic loci (78.6%), while those collected from the uncontaminated sites had lower MPI of the sediment and mussel tissue, and exhibited lower percentages of polymorphic loci (35.7-57.1%). The population from the contaminated site showed the highest excess of heterozygosity (0.289) when compared to that of the populations from the three uncontaminated sites (0.108-0.149). Allozyme frequencies at the phosphoglucomutase (PGM; E.C. 2.7.5.1) locus also differed between the contaminated and uncontaminated populations. Previous studies have shown that exposure to heavy metals can select or counter-select for particular alleles at this locus. The present results suggest that allozyme polymorphism in P. viridis is a potential biomonitoring tool for heavy metal contamination but further validation is required.     

Trace metal occurrence and distribution in sediments and mangroves,Pumicestone region,southeast Queensland,Australia

The Pumicestone region is a unique catchment in northern Moreton Bay, southeast Queensland. The region supports a wide range of land-use activities as well as attractions such as nature conservation areas. One environmental aspect that has not previously been addressed in this area is the occurrence of minor and trace metals in estuarine sediments associated with the main estuaries of the region. The trace metals included in this investigation are: vanadium, chromium, molybdenum, cobalt, nickel, copper, zinc, cadmium, lead and arsenic. To determine and evaluate the occurrence and distribution of metals in the area, several components have been analysed: bedrock material, pre-industrial settings, recent estuarine sediments, soils of estuarine origin and mangrove pneumatophores. The 40 sites chosen for sediment and soil samples cover a variety of estuarine settings and represent a range of natural conditions in terms of channel and bank morphology, tidal energy, vegetation cover, relationship to bedrock, water salinity and land disturbance. The chemical, mineralogical and statistical analyses employed in this study enabled (a) establishment of background values for the area, (b) determination of relationships between metals and (c) identification of sites with anomalous metal concentrations. All the metals found in the sediments of the area are sourced from the geological bedrock. The dominant trace elements identified in sediments are Zn, V and Cr. The remaining metals are highly variable spatially. All trace metals are controlled by the presence of Fe and Mn oxides, and by the grainsize of the sediment. Typically, fine-grained Fe-rich materials tend to adsorb more trace metals than sandy sediments. In soils that have developed from estuarine muds, some metals such as Cr, Mo, Pb and As tend to be in larger quantities than in the estuarine counterparts. Some of the elements, which occur in significant amounts in the sediment, have been detected in mangrove tissue (Avicenniamarina) such as V, Cr, Zn, Fe and Mn. Of particular note is Cu, which is present in mangrove tissue in quantities many times exceeding the sediment concentration. The comparative analysis of pre-industrial settings and recent sediments and soils highlighted some areas of metal enrichment such as acid-affected sites where oxidation of pyrite has mobilised metals from sediments; these metals are then redistributed in Fe-rich surficial layers. Disturbed banks within the estuaries are also likely to have low levels of metal enrichment due to boating activities.