Inorganic arsenic speciation at river basin scales: The Tinto and Odiel Rivers in the Iberian Pyrite Belt, SW Spain

The Tinto and Odiel rivers are heavily affected by acid mine drainage from mining areas in the Iberian Pyrite Belt. In this work we have conducted a study along these rivers where surface water samples have been collected. Field measurements, total dissolved metals and Fe and inorganic As speciation analysis were performed. The average total concentration of As in the Tinto river (1975 μg L⁻¹) is larger than in the Odiel river (441 μg L⁻¹); however, the mean concentration of As(III) is almost four times higher in the Odiel. In wet seasons the mean pH levels of both rivers (2.4 and 3.2 for the Tinto and Odiel, respectively) increase slightly and the amount of dissolved total arsenic tend to decrease, while the As(III)/(V) ratio strongly increase. Besides, the concentration of the reduced As species increase along the water course. As a result, As(III)/(V) ratio can be up to 100 times higher in the lower part of the basins. An estimation of the As(III) load transported by both rivers into the Atlantic Ocean has been performed, resulting in about 60 kg yr⁻¹ and 2.7 t yr⁻¹ by the Tinto and Odiel rivers, respectively.     

Acid mine drainage in the Iberian Pyrite Belt: 1. Hydrochemical characteristics and pollutant load of the Tinto and Odiel rivers

Acid mine drainage in the Iberian Pyrite Belt is probably the worst case in the world of surface water pollution associated with mining of sulphide mineral deposits. The Iberian Pyrite Belt is located in SW Iberian Peninsula, and it has been mined during the last 4,500 years. The central and eastern part of the Iberian Pyrite Belt is drained by the Tinto and Odiel rivers, which receive most of the acidic leachates from the mining areas. As a result, the main channels of the Tinto and Odiel rivers are very rich in metals and highly acidic until reaching the Atlantic Ocean. A significant amount of the pollutant load transported by these two rivers is delivered during the rainy season, as is usual in rivers of Mediterranean climate regions. Therefore, in order to have an accurate estimation of the pollutant loads transported by the Tinto and Odiel rivers, a systematic sampling on a weekly basis and a high temporal resolution sampling of floods events were both performed. Results obtained show that metal fluxes are strongly dependent on the study period, highlighting the importance of inter-annual studies involving dry and wet years.     

Heavy metal concentrations in molluscs from the Atlantic coast of southern Spain

Trace metals were determined in the two most abundant species of bivalve molluscs along the Atlantic coast of southern Spain (Donax trunculus and Chamelea gallina) and in the sediments where they live. The results show that the area near the mouth of the Huelva estuary is where the highest metal concentrations are found in sediments and in the two bivalve species. This is not surprising, considering that the Huelva estuary is the mouth of the Tinto and Odiel rivers, which have one of the highest levels of metal pollution of all the rivers of Europe. The two species of bivalves have different amounts of metals in their tissues. The concentrations of Cr, Cu, Pb, Zn, As and Hg in D. trunculus were significantly higher (p < 0.05) than in C. gallina; however, C. gallina contained more Ni and Cd. In both species the most abundant elements were Cu and Zn, while Hg showed the lowest values. There is a significant correlation (p < 0.05) for concentrations of Cu, Pb, Zn and Hg in D. trunculus and C. gallina relative to their concentrations in surface sediments.     

Use of sedimentary metals to predict metal concentrations in black mussel (Mytilus galloprovincialis) tissue and risk to human health (Sydney estuary, Australia)

Filter-feeding bivalves have been used extensively as an indicator of ecosystem condition and in management of estuarine environments. The current study aimed to determine whether sedimentary metals could predict metal concentrations in tissue of filter-feeding mussels (Mytilus galloprovincialis) and to identify areas of the estuary where mussel consumption posed a human health risk. Mussel tissue Cu and Zn concentrations (wet weight) were below guideline values for human consumption in all parts of the waterway, whereas Pb tissue concentrations exceed these guidelines (2.0 μg?g^?1 wet weight) in the upper reaches of some embayments of the estuary. Concentrations of Cu and Pb in the fine fraction (<62.5 μm) of bottom sediment reasonably predicted concentrations (dry weight) of these metals in mussel tissue (r ²?=?0.460 and p?=?0.001 and r ²?=?0.669 and p?<?0.0001, respectively) as these materials are resuspendable and available to filter-feeding estuarine animals, whereas total sediment and mussel tissue were poorly related. Lead concentrations (>350 μg?g^?1) in fine sediments indicated areas of this estuary where human health was at risk due to high tissue concentrations of this metal. These results give encouragement for the use of the metal concentration in fine sediments as an indicator of estuarine condition and risk to human health in this waterway. Mussels were distributed in all parts of the estuary, even in areas where metal concentrations exceeded sediment quality guidelines.     

Trace metal and metalloid levels in surface water of Marcal River before and after the Ajka red mud spill, Hungary

The aim of this study was to compare and assess the dissolved concentrations of trace elements (As, Zn, Hg, Cd, Cr, Ni, Pb and Cu) in surface water of Marcal River before and after the red mud spill that occurred in Ajka, western Hungary, in October 2010. The caustic sludge flooded the surrounding settlements and polluted the nearby Torna Creek, which flows through the Marcal and Raba rivers into the Danube. A total of 92 surface water samples were collected from the Marcal River in the period of 2007–2012 and analysed for dissolved trace metal(loid)s by atomic absorption spectroscopy method. After the spill, the water management authority initially focused on acid dosing of surface waters to lower pH and was effective in lowering both pH and metal(loid) concentrations. Among the dissolved trace metal(loid)s, arsenic and nickel levels were moderately higher in the Marcal River 2 years since the spill compared to that observed in the pre-disaster period. The concentrations of dissolved trace metal(loid)s did not exceed the European water quality standards and the US Environmental Protection Agency aquatic life criteria values (excluding one sample for cadmium).     

Challenges with tracing the fate and speciation of mine-derived metals in turbid river systems: implications for bioavailability

The fast-flowing and highly turbid Lagaip River (0.5–10 g/L suspended solids) in the central highlands of Papua New Guinea receives mine-derived metal inputs in both dissolved and particulate forms. Nearest the mine, metal concentrations in suspended solids were 360, 9, 90, 740 and 1,300 mg/kg for As, Cd, Cu, Pb and Zn, while dissolved concentrations were 2.7, 0.6, 3.1, 0.1 and 25 μg/L, respectively. This creates a significant metal exposure source for organisms nearer the mine. However, because the Lagaip River is diluted by a large number of tributaries, the extent to which mine-derived metals may affect biota in the lower catchments is uncertain. To improve our understanding of the forms of potentially bioavailable metals entering the lower river system, we studied the partitioning and speciation of metals within the Lagaip River system. Dissolved and particulate metal concentrations decreased rapidly downstream of the mine due to dilution from tributaries. As a portion of the particulate metal concentrations, the more labile dilute acid-extractable forms typically comprised 10–30 % for As and Pb, 50–75 % for Cu and Zn, and 50–100 % for Cd. Only dissolved Cd, Cu and Zn remained elevated relative to the non-mine-impacted tributaries (<0.03, 0.5 and 0.3 μg/L), but the concentrations did not appreciably change with increasing dilution downriver. This indicated that release of Cd, Cu and Zn was likely occurring from the more labile metal phases of the mine-derived particulates. Chelex-labile metal analyses and speciation modelling indicated that dissolved copper and lead were largely non-labile and likely complexed by naturally occurring organic ligands, while dissolved cadmium and zinc were predominantly present in labile forms. The study confirmed that mine-derived particulates may represent a significant source of dissolved metals in the lower river system; however, comparison with water quality guidelines indicates the low concentrations would not adversely affect aquatic life.     

Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin,Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary–Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.     

Trace Metals in Upland Headwater Lakes in Ireland

Trace elements (n = 23) in Irish headwater lakes (n = 126) were investigated to determine their ambient concentrations, fractionation (total, dissolved, and non-labile), and geochemical controls. Lakes were generally located in remote upland, acid-sensitive regions along the coastal margins of the country. Total trace metal concentrations were low, within the range of natural pristine surface waters; however, some lakes (~20 %) had inorganic labile aluminum and manganese at levels potentially harmful to aquatic organisms. Redundancy analysis indicated that geochemical weathering was the dominant controlling factor for total metals, compared with acidity for dissolved metals. In addition, many metals were positively correlated with dissolved organic carbon indicating their affinity (or complexation) with humic substances (e.g., aluminum, iron, mercury, lead). However, a number of trace metals (e.g., aluminum, mercury, zinc) were correlated with anthropogenic acidic deposition (i.e., non-marine sulfate), suggesting atmospheric sources or elevated leaching owing to acidic deposition. As transboundary air pollution continues to decline, significant changes in the cycling of trace metals is anticipated.     

Neutral poly- and perfluoroalkyl substances in air and seawater of the North Sea

Concentrations of neutral poly- and perfluoroalkyl substances (PFASs), such as fluorotelomer alcohols (FTOHs), perfluoroalkane sulfonamides (FASAs), perfluoroalkane sufonamidoethanols (FASEs), and fluorotelomer acrylates (FTACs), have been simultaneously determined in surface seawater and the atmosphere of the North Sea. Seawater and air samples were taken aboard the German research vessel Heincke on the cruise 303 from 15 to 24 May 2009. The concentrations of FTOHs, FASAs, FASEs, and FTACs in the dissolved phase were 2.6–74, <0.1–19, <0.1–63, and <1.0–9.0 pg L^?1, respectively. The highest concentrations were determined in the estuary of the Weser and Elbe rivers and a decreasing concentration profile appeared with increasing distance from the coast toward the central part of the North Sea. Gaseous FTOHs, FASAs, FASEs, and FTACs were in the range of 36–126, 3.1–26, 3.7–19, and 0.8–5.6 pg m^?3, which were consistent with the concentrations determined in 2007 in the North Sea, and approximately five times lower than those reported for an urban area of Northern Germany. These results suggested continuous continental emissions of neutral PFASs followed by transport toward the marine environment. Air–seawater gas exchanges of neutral PFASs were estimated using fugacity ratios and the two-film resistance model based upon paired air–seawater concentrations and estimated Henry's law constant values. Volatilization dominated for all neutral PFASs in the North Sea. The air–seawater gas exchange fluxes were in the range of 2.5?×?10³–3.6?×?10⁵ pg m^?2 for FTOHs, 1.8?×?10²–1.0?×?10⁵ pg m^?2 for FASAs, 1.1?×?10²–3.0?×?10⁵ pg m^?2 for FASEs and 6.3?×?10²–2.0?×?10⁴ pg m^?2 for FTACs, respectively. These results suggest that the air–seawater gas exchange is an important process that intervenes in the transport and fate for neutral PFASs in the marine environment.     

Changes in pH and organic acids in mucilage of Eriophorum angustifolium roots after exposure to elevated concentrations of toxic elements

The presence of Eriophorum angustifolium in mine tailings of pyrite maintains a neutral pH, despite weathering, thus lowering the release of toxic elements into acid mine drainage water. We investigated if the presence of slightly elevated levels of free toxic elements triggers the plant rhizosphere to change the pH towards neutral by increasing organic acid contents. Plants were treated with a combination of As, Pb, Cu, Cd, and Zn at different concentrations in nutrient medium and in soil in a rhizobox-like system for 48–120 h. The pH and organic acids were detected in the mucilage dissolved from root surface, reflecting the rhizospheric solution. Also the pH of root–cell apoplasm was investigated. Both apoplasmic and mucilage pH increased and the concentrations of organic acids enhanced in the mucilage with slightly elevated levels of toxic elements. When organic acids concentration was high, also the pH was high. Thus, efflux of organic acids from the roots of E. angustifolium may induce rhizosphere basification.     

Acid mine drainage in the Iberian Pyrite Belt: 2. Lessons learned from recent passive remediation experiences

The Iberian Pyrite Belt (IPB), SW Spain and Portugal, contains about 100 abandoned mine wastes and galleries that release acid mine drainages (AMD) to the Tinto and Odiel rivers. In situ passive remediation technologies are especially suitable to remediate the drainages of these orphan sites. However, traditional remediation systems, designed for coal mines, have been demonstrated inefficient to treat the IPB mine waters. Due to their high acidity and metal loads, large amount of solids precipitate and fast clogging of porosity or passivation (coating) of the reactive grains occurs. To overcome these problems, the dispersed alkaline substrate (DAS) a mixture of fine-grained limestone sand and a coarse inert matrix (e.g., wood shavings) was developed. The small grains provide a large reactive surface and dissolve almost completely before the growing layer of precipitates passivates the substrate. The high porosity retards clogging. However, calcite dissolution only raises pH to values around 6.5, at which the hydroxides of trivalent metals (Al and Fe) precipitate, but it is not high enough to remove divalent metals. Caustic magnesia (MgO) buffers the solution pH between 8.5 and 10. A DAS system replacing limestone with caustic magnesia has been tested to be very efficient to remove divalent metals (Zn, Cd, Mn, Cu, Co, Ni, and Pb) from the water previously treated with calcite.     

Gross fluxes and estuarine behaviour of pesticides in the Scheldt estuary (1995-1997)

As part of the Fluxes of Agrochemicals into the Marine Environment (FAME) project, the gross fluxes of selected pesticides (i.e. the herbicides atrazine, simazine, alachlor and metolachlor, the atrazine degradation product desethylatrazine, the insecticide dichlorvos and the antifouling agent Irgarol 1051) transported by the river Scheldt and the Canal Ghent-Terneuzen were determined from March 1995 through February 1997. In general, the observed temporal trends were related to the application period of the pesticides, except for metolachlor for which elevated concentrations were observed in the winter of 1995-1996. Relatively large gross fluxes were found for desethylatrazine compared with its parent compound. A study on the estuarine behaviour of pesticides showed distinct differences between the compound classes. The mixing plots of the organophosphorus insecticides dichlorvos and diazinon revealed clear evidence of estuarine loss processes which agrees with their low DT50 values reported for water/sediment systems, their relatively high Henry's law constants and, for diazinon, its relatively high Koc value. The mixing plots of the acetanilides alachlor and metolachlor were strongly influenced by an additional direct emission into the estuary, which was evident from a maximum in dissolved concentration near a salinity of 10@1000. An apparent conservative behaviour was observed for the triazine compounds atrazine and Irgarol 1051. This was in contrast to simazine, which showed an apparent non-conservative behaviour. However, the time profiles of the riverine concentrations of simazine did not exclude that the observed curvature was solely caused by estuarine losses; therefore, additional modelling is required. In a follow-up study a suitable hydrological model of the Scheldt estuary was constructed; the results will be presented in a forthcoming paper (Steen, R.J.C.A., Evers, E.H.G., Van Hattum, B., Cofino, W.P. and Brinkman, U.A.Th. Net fluxes of pesticides from the Scheldt estuary into the North Sea: a model approach. Environmental Pollution, submitted.     

Temporal variability in dynamic and colloidal metal fractions determined by high resolution in situ measurements in a UK estuary

In recent environmental legislation, such as the Water Framework Directive in the European Union (WFD, 2000/60/EC), the importance of metal speciation and biological availability is acknowledged, although analytical challenges remain. In this study, the Voltammetric In situ Profiler (VIP) was used for high temporal resolution in situ metal speciation measurements in estuarine waters. This instrument simultaneously determines Cd, Cu and Pb species within a size range (ca. <4 nm) that is highly relevant for uptake by organisms. The colloidal metal fraction can be quantified through a combination of VIP measurements and analyses of total dissolved metal concentrations.VIP systems were deployed over tidal cycles in a seasonal study of metal speciation in the Fal Estuary, southwest England. Total dissolved concentrations were 4.97-315 nM Cu, 0.13-8.53 nM Cd and 0.35-5.75 nM Pb. High proportions of Pb (77 ± 17%) and Cu (60 ± 25%) were present as colloids, which constituted a less important fraction for Cd (37 ± 30%). The study elucidated variations in the potentially toxic metal fraction related to river flow, complexation by organic ligands and exchanges between dissolved and colloidal phases and the sediment. Based on published toxicity data, the bioavailable Cu concentrations (1.7-190 nM) in this estuary are likely to severely compromise the ecosystem structure and functioning with respect to species diversity and recruitment of juveniles. The study illustrates the importance of in situ speciation studies at high resolution in pursuit of a better understanding of metal (bio)geochemistry in dynamic coastal systems.     

Input-export fluxes of heavy metals in the Cochin estuary,southwest coast of India

Cochin estuary (CE) is one of the largest tropical estuaries along the southwest coast of India, sustaining rich bio-resources. Several studies enlighten the environmental changes in the CE caused by anthropogenic activities. In the present study, an attempt has been made to quantify the heavy metal (dissolved and particulate) fluxes brought by the six rivers into the CE with their exchange into the coastal ocean through the major inlet at Cochin during a steady flow period (October–November 2015). The water flux across the inlet was quantified using an acoustic doppler current profiler. The measured daily input of dissolved metals from the rivers was 2.43?×?10³ kg Fe, 334 kg Zn, 259 kg Ni, and 83 kg Cr, while that of particulate metals were 85.30?×?10³ kg Fe, 8. 6?×?10³ kg Mn, 236.9 kg Cr, and 111.9 kg Zn. The net export of metals through the Cochin inlet (per tidal cycle) was 3.3?×?10³ kg Fe, 515 kg Cr, 150 kg Zn, and 5 kg Ni in dissolved form and 3.32?×?10⁵ kg Fe, 1747 kg Mn, 1636 kg Cr, 1397 kg Zn, and 586 kg Ni in particulate form. The high concentrations of metals during ebb tides are clear indications of their contribution from the industrial conglomerates (industrial units of metallurgy, catalyst, fertilizer, and pesticides) located in the Periyar River. The significance of this study is that the export fluxes may increase further during the summer monsoon (June to September), which may impact the abundant fishery emanating in the coastal environment during the period due to intense upwelling.

     

Dolomite phosphate rock (DPR) application in acidic sandy soil in reducing leaching of phosphorus and heavy metals—a column leaching study

A column leaching study was designed to investigate the leaching potential of phosphorus (P) and heavy metals from acidic sandy soils applied with dolomite phosphate rock (DPR) fertilizers containing varying amounts of DPR material and N-Viro soils. DPR fertilizers were made from DPR materials mixing with N-Viro soils at the ratios of 30, 40, 50, 60, and 70 %, and applied in acidic sandy soils at the level of 100 mg available P per kilogram soil. A control and a soluble P chemical fertilizer were also included. The amended soils were incubated at room temperature with 70 % field water holding capacity for 21 days before packed into a soil column and subjected to leaching. Seven leaching events were conducted at days 1, 3, 7, 14, 28, 56, and 70, respectively, and 258.9 mL of deionized water was applied at each leaching events. The leachate was collected for the analyses of pH, electrical conductivity (EC), dissolved organic carbon (DOC), major elements, and heavy metals. DPR fertilizer application resulted in elevations up to 1 unit in pH, 7–10 times in EC, and 20–40 times in K and Ca concentrations, but 3–10 times reduction in P concentration in the leachate as compared with the chemical fertilizer or the control. After seven leaching events, DPR fertilizers with adequate DPR materials significantly reduced cumulative leaching losses of Fe, P, Mn, Cu, and Zn by 20, 55, 3.7, 2.7, and 2.5 times than chemical fertilizer or control. Even though higher cumulative losses of Pb, Co, and Ni were observed after DPR fertilizer application, the loss of Pb, Co, and Ni in leachate was <0.10 mg (in total 1,812 mL leachate). Significant correlations of pH (negative) and DOC (positive) with Cu, Pb, and Zn (P?<?0.01) in leachate were observed. The results indicated that DPR fertilizers had a great advantage over the soluble chemical fertilizer in reducing P loss from the acidic sandy soil with minimal likelihood of heavy metal risk to the water environment. pH elevation and high dissolved organic carbon concentration in soils after DPR fertilizer application are two influential factors.     

Heavy metal distribution in marine sediments from the southwest coast of Spain

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments.     

Histopathological lesions and DNA adducts in the liver of European flounder (Platichthys flesus) collected in the Seine estuary versus two reference estuarine systems on the French Atlantic coast

An epidemiological survey was conducted in the Seine estuary and in two smaller and relatively preserved estuaries on the French Atlantic coast in order to estimate the occurrence of liver lesions in European flounder, Platichthys flesus, and also to seek putative risk factors for the recorded pathologies. Four hundred and seventy-eight fish of both sexes and of different size ranges were sampled in the three studied areas, 338 of which in the Seine estuary. All fish were examined for histopathological liver lesions, while DNA adducts and otoliths were analyzed on a subsample. Five categories of hepatic lesions were recorded with the following prevalence for the Seine estuary: 36.7 % inflammations, 8 % parasites (mainly encysted nematodes), 6.5 % foci of cellular alteration (FCA), 5.3 % foci of necrosis or regeneration (FNR), and 1.5 % tumors. Inflammation occurrence increased according to age, contrary to parasitic infestations and FCA which were more prevalent in young fish, notably those of <1 year old (group 0). Tumors were only observed in females of more than two winters. Females exhibited a higher prevalence of tumors (3.0 %) and FCA (6.5 %) than males (0 and 2.6 %, respectively). Parasitic and infectious lesions and FNR were equally distributed in males and females. The prevalence of FNR was also shown to vary according to sampling season, with significantly more occurrences of liver necrosis in the fish collected in summer than in spring. Spatial differences were observed with a higher occurrence of encysted parasites in flounders from the upper Seine estuary, while inflammations predominated in flounders living downstream. Temporal trends were also noted, with an increased prevalence of parasitic infestations, inflammations, and FCA in the 2002–2003 period in comparison to the 1996–1997 one. The three flounder populations from the Seine estuary (Normandy), Ster estuary (Brittany), and Bay of Veys (Normandy) showed different spectra of hepatic lesions. Flounders from the Bay of Veys had relatively few liver lesions as compared to flounders from the two other estuaries. Flounders from the Ster estuary exhibited the highest prevalence of parasites (37.2 %) and inflammations (51.1 %). Finally, FCA and liver tumors occurred at very similar levels in both flounder populations from the Seine and the Ster estuaries. Group 0 flounders inhabiting the upper Seine estuary were more prone to parasitic and pre-neoplastic hepatic lesions and had higher levels of liver DNA adducts than the older ones living downstream. It was postulated that group 0 European flounders may serve as valuable bioindicators for assessing the quality of estuarine waters and the health status of euryhaline fish populations.     

Photooxidation of arsenite by natural goethite in suspended solution

Iron and arsenic have been found to coexist in a water environment and the fate of arsenite in the aquatic system is influenced by iron. Goethite is a form of iron hydroxide, which is commonly found in sediments. In previous studies, we have used iron complexes to degrade organic pollutants. Results have shown that some organic pollutants could be totally degraded by iron complexes and our work indicated that iron might cause conversion of arsenic when irradiated. This work attempts to investigate the conversion of arsenite [As(III)] using natural goethite, as the iron source, to quantify the effect of various factors on photooxidation. We also consider the possible mechanism for photooxidation of As(III) using a suspension of natural goethite. The As(III) concentration variation under illumination was compared with the one in the dark to quantify the contribution of light to As(III) oxidation to As(V) in goethite suspended solution. The experiments under N₂ and air atmosphere confirmed the participation of dissolved oxygen. The photooxidation efficiency of As(III) under different conditions was compared to determine the effect of different environmental factors such as pH value, goethite concentration, and humic acid concentration on the photooxidation reaction. In the solution containing 100 μg L^?1 arsenite and 0.1 g?L^?1 suspended goethite at pH 3.0, nearly 80 % of As(III) was photooxidized after irradiation by a 250-W metal halogen lamp (λ?≥?313 nm) after 6 h. The effects of initial pH and goethite concentration and humic acid concentration were all examined. The results show that the greatest efficiency of photooxidation of As(III) was at pH 3.0. The extent of photooxidation decreased with increasing goethite concentration and fell sharply in the presence of humic acid under the conditions in this work. Although about 80 % of As(III) was photooxidized after irradiation by a 250-W halogen lamp at pH 3.0 in the presence of goethite suspension, photooxidation was also affected by factors such as pH, concentration of goethite, and presence of humic acid. The scavenger experiments showed that the HO? radical and photogenerated hole are the predominant oxidants in this system responsible for 87.1 % oxidation of As(III), while HO ₂ ^? /O ₂ ^?? is responsible for 12.9 % oxidation of As(III).