Heavy metal bioavailability and effects: II. Histopathology-bioaccumulation relationships caused by mining activities in the Gulf of Cádiz (SW, Spain)

The relationship between bioaccumulation of heavy metals (Zn, Cd, Pb and Cu) and histological lesions in different tissues of organisms is assessed in three different areas located in the southwest of Spain in the Gulf of Cádiz (Ría of Huelva, Guadalquivir estuary and Bay of Cádiz) affected and non-affected by mining activities. Data included in these relationships were obtained along the years 2000 and 2001 to address the impact of the Aznalcóllar mining spill on the Guadalquivir estuary. The bioaccumulation and the histological lesions measured in this seasonal study in the Gudalquivir estuary were linked to derive tissue quality guidelines (TQGs) by means of a multivariate analysis approach (MAA). Sediments collected in the same areas of study were used to expose organisms during the survey carried out in autumn 2001 and to address the relationship between bioaccumulation and histological lesions under laboratory conditions and related to chemicals bound to sediments. Lesions show that the organisms collected in the ría of Huelva and exposed to their sediments were severe, intermediate in the Guadalquivir estuary and absent in the Bay of Cádiz. Results show that the Guadalquivir estuary trends to recover its initial status quo previous to the mining spill. The link between chemical concentration and the lesions measured in the same tissues using MAA permits to derive tissue quality guidelines for two organisms, oysters (Crassostrea angulata) and clams (Scrobicularia plana) collected in the Guadalquivir estuary and associated with the heavy metals from the mining spill (Zn and Cd). The TQG values expressed as concentrations (mgkg-1--dry weight) not associated with biological effects are for oysters, Zn, 8603, Cd, 3.42; and for clams Zn, 800, Cd, 2.6.     

Seasonality of contamination, toxicity, and quality values in sediments from littoral ecosystems in the Gulf of Cádiz (SW Spain)

To seasonally evaluate littoral contamination, toxicity and quality values of sediments from the Gulf of Cádiz, we measured chemical concentrations and conducted toxicity tests in winter and summer and linked these results by means of multivariate analysis. Sediment samples were subjected to two separate, replicated sediment toxicity tests (Microdeutopus gryllotalpa amphipod survival, and Ruditapes philippinarum clam reburial), and to comprehensive sediment chemistry analyses (grain size, organic carbon, 14 heavy metals, and the surfactant linear alkylbenzenesulfonate (LAS)). Only sediments associated with an untreated urban discharge were toxic and related to high levels of surfactant LAS, Ag, and Pb. Multivariate analysis indicated that variables and chemicals associated with geochemical matrix and background levels (specific surface, Fe, Zn, Cu, V, Ni, and Co), chemicals associated with untreated urban discharge sources, and toxicity effects showed no seasonal variability. Only copper concentrations showed seasonal differences, being toxic during the winter and not toxic during summer. Multivariate analysis permits us to derive sediment quality values (SQVs); in terms of concentrations at or below which biological effects were not measured (mg kg(-1) dry sediment), are: LAS, 2.6; lead, 66.8; silver, 0.78; copper, 69.6.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

Dating of marine sediments and time evolution of heavy metal concentrations in the Bay of Cádiz, Spain

In this paper the time evolution of heavy metal concentration of Pb, Zn, Cd and Hg, in the sediments of the Bay of Cádiz (southwest of Spain) is studied during the past century, as a result of the industrial influence in the zone. The study has been performed using sedimentary profiles that have been extracted from the seabed. The measurement of 210Pb and 137Cs radionuclides has provided the dating of the sediment layers, up to a depth corresponding to the age of 115 years. The relative sedimentation rates obtained are around 0.2 cm/year. The 137Cs activity profile reflects the concentration of this radionuclide in the atmosphere and into aquatic systems during the second half of the twentieth century. This profile has been used to ratify the results provided by the 210Pb dating method.     

Heavy metal contamination in sediments of an artificial reservoir impacted by long-term mining activity in the Almadén mercury district (Spain)

Sediments from the Castilseras reservoir, located downstream on the Valdeazogues River in the Almadén mercury district, were collected to assess the potential contamination status related to metals(oids) associated with river sediment inputs from several decommissioned mines. Metals(oids) concentrations in the reservoir sediments were investigated using different physical and chemical techniques. The results were analyzed by principal component analysis (PCA) to explain the correlations between the sets of variables. The degree of contamination was evaluated using the enrichment factor (EF) and the geoaccumulation index (Igeo). PCA revealed that the silty fraction is the main metals(oids) carrier in the sediments. Among the potentially harmful elements, there is a group (Al, Cr, Cu, Fe, Mn, Ni, and Zn) that cannot be strictly correlated to the mining activity since their concentrations depend on the lithological and edaphological characteristics of the materials. In contrast, As, Co, Hg, Pb, and S showed significant enrichment and contamination, thus suggesting relevant contributions from the decommissioned mines through fluvial sediment inputs. As far as Hg and S are concerned, the high enrichment levels pose a question concerning the potential environmental risk of transfer of the organic forms of Hg (mainly methylmercury) from the bottom sediments to the aquatic food chain.     

Assessing heavy metal pollution by biomonitoring honeybee nectar in Córdoba (Spain)

Environmental Science and Pollution Research - Nectar of honeybee colonies has been used in order to identify heavy metals and establish the benefit of this type of studies as a tool for...     

Analyses of ozone in urban and rural sites in Málaga (Spain)

Ozone concentrations were measured at two (urban and a rural) sites near the city of Málaga (Spain). The aim of this study was to determine the daily, monthly and seasonal variation patterns of ozone concentrations at both sites and to study the possible regional influences. The daily variations mostly have the usual features with the afternoon maximum and the night minimum being more pronounced in the urban area. The average monthly concentrations throughout the year start to increase in March reaching their maximum values in July for the urban site. However, in the rural area, the monthly variations are smaller reaching their maximum value in June. The hourly evolution of the ozone concentrations in both sampling sites is well defined in spring and summer and not so well defined in autumn and winter. Taking into account the four seasons, the rural concentrations are higher than the urban ones. Summer is the season when there are similar concentrations at both sampling sites. Average hourly summer afternoon ozone for the hours 12:00-20:00 LST exceeded the 110 microg m(-3) European Union guidelines for human health for 8 h ozone exposure at the urban and rural sites.     

Heavy metal levels in gonad and liver tissues—effects on the reproductive parameters of natural populations of Aphanius facsiatus

The impact of heavy metal levels (Cd, Cu, and Zn) on the reproductive parameters in natural populations of the Mediterranean killifish Aphanius fasciatus was monitored in four sites of the Tunisian coast. Our study covered a period of the reproductive cycle, from April to November 2009. The significantly higher levels of Cd, Cu, and Zn in the liver and gonads for both sexes (p?<?0.05) were observed in the most polluted site (Sfax coast). During the reproductive cycle of A. fasciatus, an unbalanced sex ratio in favor to females was observed for all the studied populations. The progression of the hepato- (HSI), gonadosomatic (GSI), and K-factor revealed a spatio-temporal variation between populations during the sampling period. Estradiol-17β amounts in the gonad tissues of females captured from the studied sites showed a significant difference, and the highest concentrations were noticed in the control site (Luza). Taking together, our data provide the first evidence of a physiologically stress and a disturbance of the reproductive status in natural populations of A. fasciatus.     

Environmental and socioeconomic assessment of impacts by mining activities—a case study in the Certej River catchment,Western Carpathians,Romania

Background, aim and scope

In the region of the Apuseni Mountains, part of the Western Carpathians in Romania, metal mining activities have a long-standing tradition. These mining industries created a clearly beneficial economic development in the region. But their activities also caused impairments to the environment, such as acid mine drainage (AMD) resulting in long-lasting heavy metal pollution of waters and sediments. The study, established in the context of the ESTROM programme, investigated the impact of metal mining activities both from environmental and socioeconomic perspectives and tried to incorporate the results of the two approaches into an integrated proposition for mitigation of mining-related issues.

Study site

The small Certej catchment, situated in the Southern Apuseni Mountains, covers an area of 78 km². About 4,500 inhabitants are living in the basin, in which metal mining was the main economic sector. An open pit and several abandoned underground mines are producing heavy metal-loaded acidic water that is discharged untreated into the main river. The solid wastes of mineral processing plants were deposited in several dumps and tailings impoundment embodying the acidic water-producing mineral pyrite.

Methods

The natural science team collected samples from surface waters, drinking water from dug wells and from groundwater. Filtered and total heavy metals, both after enrichment, and major cations were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major anions in waters, measured by ion chromatography, alkalinity and acidity were determined by titration. Solid samples were taken from river sediments and from the largest tailings dam. The latter were characterised by X-ray fluorescence and X-ray diffraction. Heavy metals in sediments were analysed after digestion. Simultaneously, the socioeconomic team performed a household survey to evaluate the perception of people related to the river and drinking water pollution by way of a logistic regression analysis.

Results and discussion

The inputs of acid mine waters drastically increased filtered heavy metal concentrations in the Certej River, e.g. Zn up to 130 mg L⁻¹, Fe 100 mg L⁻¹, Cu 2.9 mg L⁻¹, Cd 1.4 mgL⁻¹ as well as those of SO₄ up to 2.2 g L⁻¹. In addition, river water became acidic with pH values of pH 3. Concentrations of pollutant decreased slightly downstream due to dilution by waters from tributaries. Metal concentrations measured at headwater stations reflect background values. They fell in the range of the environmental quality standards proposed in the EU Water Framework Directive for dissolved heavy metals. The outflow of the large tailing impoundment and the groundwater downstream from two tailings dams exhibited the first sign of AMD, but they still had alkalinity.

Most dug wells analysed delivered a drinking water that exhibited no sign of AMD pollution, although these wells were a distance of 7 to 25 m from the contaminated river. It seems that the Certej River does not infiltrate significantly into the groundwater.

Pyrite was identified as the main sulphide mineral in the tailings dam that produces acidity and with calcite representing the AMD-neutralising mineral. The acid–base accounting proved that the potential acid-neutralising capacity in the solid phases would not be sufficient to prevent the production of acidic water in the future. Therefore, the open pits and mine waste deposits have to be seen as the sources for AMD at the present time, with a high long-term potential to produce even more AMD in the future.

The socioeconomic study showed that mining provided the major source of income. Over 45% of the households were partly or completely reliant on financial compensations as a result of mine closure. Unemployment was considered by the majority of the interviewed persons as the main cause of social problems in the area. The estimation of the explanatory factors by the logistic regression analysis revealed that education, household income, pollution conditions during the last years and familiarity with environmental problems were the main predictors influencing peoples’ opinion concerning whether the main river is strongly polluted. This model enabled one to predict correctly 77% of the observations reported. For the drinking water quality model, three predictors were relevant and they explained 66% of the observations.

Conclusions

Coupling the findings from the natural science and socioeconomic approaches, we may conclude that the impact of mining on the Certej River water is high, while drinking water in wells is not significantly affected. The perceptions of the respondents to pollution were to a large extent consistent with the measured results.

Recommendations and perspectives

The results of the study can be used by various stakeholders, mainly the mining company and local municipalities, in order to integrate them in their post-mining measures, thereby making them aware of the potential long-term impact of mining on the environment and on human health as well as on the local economy.

     

Impact of Zn–Pb mining in the Olkusz ore district on the Permian aquifer (SW Poland)

Long-term extensive mining of Zn–Pb ores in the Olkusz area resulted in significant changes of water table levels and chemical composition of water in all aquifers in this area. Within the Permian aquifer, hydrochemical type of water evolved in two general stages. Short-term effect was freshening in the zones of contact with overlying the Triassic limestones and dolomites. Long-term effect was a change in flow pattern and, as a consequence, an inflow of naturally altered and antropogenically contaminated water from the Triassic aquifer into the Permian complex. This was especially intensive in densely fissured and fault zones. As a result of all these processes, hydrochemical type of water shifted from multi-ion types with various combinations of ions towards higher shares of sulphates, calcium and magnesium.     

Selected trace metals in oysters (Crassostrea iridescens) and sediments from the discharge zone of the submarine sewage outfall in Mazatlán Bay (southeast Gulf of California): chemical fractions and bioaccumulation factors

Concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn in the soft tissue of Crassostrea iridescens and the associated surface sediments (bulk and bioavailable metal concentrations) from an area influenced by a sewage outfall in Mazatlán Bay (southeast Gulf of California), were determined by atomic absorption spectrophotometry. Significant spatial differences in metal concentrations in both the bulk and bioavailable forms in the sediments were identified. An enrichment of Cu, Ni, Pb and Zn in sites located on a south-north transect was detected indicating a dominant influence of the sewage outfall toward the north. C. iridescens accumulated more Zn, Cu, Ni, Fe, Cd; and less Mn, Cr and Pb than were bioavailable in the sediments, as measured using conventional extraction analysis. The degree of enrichment and the bioavailable metal concentrations in the sediments of the south portion of Mazatlán Bay is discussed. The potential ability of C. iridescens as a biomonitor of metallic pollutants is postulated.     

Heavy metal geochemistry of saltmarsh soils from the Ría of Ortigueira (mafic and ultramafic areas, NW Iberian Peninsula)

Concentrations of Fe, Mn, Ni, Cu, Cr and Zn in their total, silicate, organic, reactive and pyrite fractions were determined in soils collected from the Ortigueira saltmarshes (Esteiro, Ladrido and Mera, NW Iberian Peninsula), from sediments of the Landoi and Esteiro Rivers, and from sludge generated by a nearby dunite mine. The Esteiro saltmarsh presented clear enrichments of the four metals studied (first 10 cm), especially of Ni and Cr, whose concentrations were among the highest. It is proposed that the elevated Cr and Ni levels found in the Esteiro saltmarsh were derived from recent contributions of the mine, which are partially discharged into the Landoi River. Total Cu and Zn concentrations were lower than the corresponding ones for Cr and Ni. Under suboxic conditions, Ni, Cr, Cu and Zn were mainly associated with the reactive fraction. Under anoxic conditions, Cu and Ni were associated mainly with the pyrite phase. Pyritic Zn and Cr concentrations were relatively low and similar in all three saltmarshes; however, where anoxic-sulfidic conditions prevailed these two metals were mainly associated with the reactive and organic fractions.     

Uptake of heavy metals and As by Brassica juncea grown in a contaminated soil in Aznalcóllar (Spain): the effect of soil amendments

Two crops of Brassica juncea (L.) Czern. were grown in a field experiment, at the site affected by the toxic spillage of acidic, metal-rich waste in Aznalcóllar (Seville, Spain), to study its metal accumulation and the feasibility of its use for metal phytoextraction. The effects of organic soil amendments (cow manure and mature compost) and lime on biomass production and plant survival were also assessed; plots without organic amendment and without lime were used as controls. Plots, with or without organic amendment, having pH < 5 were limed for the second crop. Soil acidification conditioned plant growth and metal accumulation. The addition of lime and the organic amendments achieved higher plant biomass production, although effects concerning metal bioavailability and accumulation were masked somewhat by pH variability with time and between and within plots. Tissue metal concentrations of B. juncea were elevated for Zn, Cu and Pb, especially in leaves of plants from plots with low pH values (maxima of 2029, 71 and 55 microg g(-1), respectively). The total uptake of heavy metals in the plants was relatively low, emphasising the problems faced when attempting to employ phytoextraction for clean-up of pluri-contaminated sites.     

Mercury, methylmercury, and selenium in blood of bird species from Doñana National Park (Southwestern Spain) after a mining accident

Total mercury (Hg), monomethylmercury (MeHg), and selenium (Se) were determined in blood of 11 bird species living in Doñana National Park (DNP, Southwestern Spain) and the surrounding area in 1999 and 2000 after a mine spill accident. The total Hg contents found varied from 1.00 to 587 ng/mL, with an MeHg percentage higher than 80 %, except in mallard species. In all the cases, the concentrations found were below the threshold of high risk for the bird populations. The parameters which most affected the accumulation of Hg and MeHg in the birds studied were, first, species, or trophic position, and second sampling area. Age does not seem to have a great influence on the content of Hg in the blood of these birds. The levels of Se found ranged from 108 to 873 ng/mL, and they were not affected by species, trophic level, age, or sampling area. The blood Hg concentrations of birds living in the area directly affected by the toxic mud, outside the park, were higher than those found in the other birds, and this could be explained by the mine spill accident happened in 1998.     

Mercury species accumulation and trophic transfer in biological systems using the Almadén mining district (Ciudad Real,Spain) as a case of study

The impact of mercury (Hg) pollution in the terrestrial environments and the terrestrial food chains including the impact on human food consumption is still greatly under-investigated. In particular, studies including Hg speciation and detoxification strategies in terrestrial animals are almost non-existing, but these are key information with important implications for human beings. Therefore, in this work, we report on Hg species (inorganic mercury, iHg, and monomethylmercury, MeHg) distribution among terrestrial animal tissues obtained from a real-world Hg exposure scenario (Almadén mining district, Spain). Thus, we studied Hg species (iHg and MeHg) and total selenium (Se) content in liver and kidney of red deer (Cervus elaphus; n?=?41) and wild boar (Sus scrofa; n?=?16). Similar mercury species distribution was found for both red deer and wild boar. Major differences were found between tissues; thus, in kidney, iHg was clearly the predominant species (more than 81 %), while in liver, the species distribution was less homogeneous with a percentage of MeHg up to 46 % in some cases. Therefore, Hg accumulation and MeHg transfer were evident in terrestrial ecosystems. The interaction between total Se and Hg species has been evaluated by tissue and by animal species. Similar relationships were found in kidney for both Hg species in red deer and wild boar. However, in liver, there were differences between animals. The possible underlying mechanisms are discussed.     

Determination and evaluation of cadmium, lead and nickel in greenhouse soils of Almería (Spain)

This study determines total levels of three (Cd, Pb and Ni) potentially toxic trace elements in western Almería (Spain) greenhouse surface soil horizons using microwave digestion; it establishes the geochemical baseline concentration, and it investigates possible relationships between soil properties and elemental concentrations. The results show that the soil concentration of these heavy metals is lower than mentioned in the European and Spanish normative, but they are higher than those reported by other authors working on agricultural soils. The obtained geochemical baseline concentrations (mg kg(-1)) were: Cd 0.4-0.8, Pb 2.5-89.9 and Ni 16.1-30.7. Using the upper baseline criterion, 88% of greenhouse soils have relatively higher content of heavy metals because of their Cd, Pb and Ni concentration. Moreover, soil properties are related to heavy metals contents suggesting that among Cd, Pb and Ni have a similar origin and those total metal concentrations are controlled primarily by soil compositions.     

Bioaccumulation of the pharmaceutical 17α-ethinylestradiol in shorthead redhorse suckers (Moxostoma macrolepidotum) from the St. Clair River, Canada

17α-ethynylestradiol (EE2), a synthetic estrogen prescribed as a contraceptive, was measured in Shorthead Redhorse Suckers (ShRHSs) (Moxostoma macrolepidotum) collected near a wastewater treatment plant (WWTP) in the St. Clair River (Ontario, Canada). We detected EE2 in 50% of the fish samples caught near the WWTP (Stag Island), which averaged 1.6 ± 0.6 ng/g (wet weight) in males and 1.43 ± 0.96 ng/g in females. No EE2 was detected in the samples from the reference site (Port Lambton) which was 26 km further downstream of the Stag Island site. Only males from Stag Island had VTG induction, suggesting the Corunna WWTP effluent as a likely source of environmental estrogen. EE2 concentrations were correlated with total body lipid content (R² = 0.512, p < 0.01, n = 10). Lipid normalized EE2 concentrations were correlated with δ¹⁵N (R² = 0.436, p < 0.05, n = 10), suggesting higher EE2 exposures in carnivores. Our data support the hypothesis of EE2 bioaccumulation in wild fish.     

Wet deposition of mercury in the U.S. and Canada, 1996–2005: Results and analysis of the NADP mercury deposition network (MDN)

One of the most critical measurements needed to understand the biogeochemical cycle of mercury, and to verify atmospheric models, is the rate of mercury wet-deposition. The Mercury Deposition Network (MDN) operates sites across North America to monitor total mercury in wet-deposition. MDN's primary goal is to provide both spatial and temporal continental-scale observations of mercury wet-deposition fluxes to support researchers, modelers, policy-makers and the public interest. MDN represents the only continental-scale mercury deposition database with a >10-year record of continuous values. This study provides analysis and interpretation of MDN observations at 10 years (1996–2005) with an emphasis on investigating whether rigorous, statistically-significant temporal trends and spatial patterns were present and where they occurred. Wet deposition of mercury ranges from more than 25 μg m^?2 yr in south Florida to less than 3 μg m^?2 yr in northern California. Volume-weighted total mercury concentrations are statistically different between defined regions overall (Southeast ≈ Midwest > Ohio River > Northeast), with the highest in Florida, Minnesota, and several Southwest locations (10–16 ng L^?1). Total mercury wet-deposition is significantly different between defined regions (Southeast > Ohio River > Midwest > Northeast). Mercury deposition is strongly seasonal in eastern North America. The average mercury concentration is about two times higher in summer than in winter, and the average deposition is approximately more than three times greater in summer than in winter. Forty-eight sites with validated datasets of five years or more were tested for trends using the non-parametric seasonal Kendall trend test. Significant decreasing mercury wet-deposition concentration trends were found at about half of the sites, particularly across Pennsylvania and extending up through the Northeast.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.