Volatile organotin compounds (butylmethyltin) in three European estuaries (Gironde, Rhine, Scheldt)

The occurrence of volatile organometallicspecies of tin was evidenced and investigatedin three major European estuaries, such as theGironde (F), the Rhine (NL) and the Scheldt(B/NL), along with the salinity gradient andfor all seasons. The most ubiquitous species,observed in surface water, were found to bemethylated forms of butyl-tin derivatives(Bu_nSnMe_4-n, n = 0–3), withconcentrations significantly higher in theScheldt (ca. 75–2000 fmol l^–1) than in theRhine (ca. 5–125 fmol l^–1) and the Gironde(ca. 5–90 fmol l^–1). Additionally,estuarine anoxic sediments were found tocontain large amount of such volatile tinspecies.The presence of volatile organic tin compoundsis then supposed to result from naturalmethylation processes of both inorganic metaland anthropogenic derivatives accumulated inthe sediments (i.e. tributyltin released fromship antifouling paintings and waste waterdischarges). These results suggest thatmicrobial mediated and/or chemical methylationmechanisms are likely to produce volatileorganotin species in anoxic estuarineenvironments. The production of volatileorganotin species is also mainly dependent onthe direct anthropogenic load of butyltincompounds within the estuary and on theresidence time of such compounds in the system.Estuarine profiles along with the salinitygradient demonstrate that all investigatedestuaries are continuous sources of volatiletin species, although these estuaries presentdifferent anthropogenic organotin discharges.In consequence, significant export of volatiletin species to the adjacent coastal waters werefound. Finally, the evaluation of the seasonalfluxes of volatile tin species to theatmosphere establishes that volatilisation is amajor sink for such compound in estuaries withlong water residence time (i.e. Scheldt, Gironde).     

Effects of a plume front on the distribution of inorganic and organic matter off the Rhône River

Hydrological and chemical structures off the Rhône River estuary resulting from the introduction of the river flow into the Mediterranean Sea are described. The effect of the fresh-water/sea-water interface on the distribution of inorganic and organic matter off the Rhône river is investigated. Strong vertical gradients of inorganic and dissolved organic matter such as lipids characterized the first few meters in this area (from 83.7 to 0.6 N-NO₃ µgat l^–1, from 6.39 to 0.92 N-NH₄ µgat l^–1 and from 299 to 73 µg l^–1 of total dissolved lipids). At the interface, substantial increases of particulate organic (PON: from 45 µg l^–1 at surface to 118 µg l^–1 at the interface, POC: from 462 to 876 µg l^–1, total particulate lipids: from 33 to 648 µg l^–1) and suspended matter in general (from 18 to 22.2 mg l^–1) were observed. High phytoplanktonic production may account for some of this enrichment, although passive accumulation might also be involved.     

Turbidity enhances feeding abilities of larval Pacific herring,Clupea harengus pallasi

Fishes inhabiting estuaries, rivers, and embayments are subject to turbid conditions. Larvae of many fishes utilize estuaries as nursery areas. For visual plankton feeders such as larval fishes, turbidity may reduce search and reaction distances, resulting in lowered feeding abilities. In this study feeding Pacific herring larvae, Clupea harengus pallasi, were exposed to suspensions of estuarine sediment and Mount Saint Helens volcanic ash at concentrations ranging from 0 mg · l^–1 to 8 000 mg · l^–1. In all experiments, maximum feeding incidence and intensity occurred at levels of suspension of either 500 mg · l^–1 or 1000 mg · l^–1 with values significantly greater than controls (0 mg · l^–1). Feeding decreased at greater concentrations. The suspensions may enhance feeding by providing visual contrast of prey items on the small perceptive scale used by the larvae. Larval residence in turbid environments such as estuaries may serve to reduce predation from larger, visual planktivores, while searching ability in the small larval perceptive field is not decreased.     

Lipid composition of water and surface sediments in Takapoto atoll lagoon (French Polynesia)

Dissolved, particulate and sedimentary lipid compounds were analyzed in samples collected in May 1988 at three sites in the lagoon of the closed atoll of Takapoto (Tuamotu archipelago, French Polynesia). The study provides background information dealing with water quality and the nature and concentration of lipids. Non-aromatic hydrocarbons and fatty acids were isolated from lipids and analyzed by gas chromatography/mass spectrometry. Non-aromatic hydrocarbon concentrations did not exceed 1000 ng l^-1 in water, and 2300 ng g^-1 in surface sediments and are among the lowest encountered in pristine marine environments. No noticeable petroleum pollution was evidenced in the lagoon. Nevertheless, traces of petroleum-derived compounds were detected at the central site for both surface and deep water. Total fatty acid concentrations varied in the range 6.3–14.4 g l^-1 for the particulate phase and in the range 0.5–3.2 g l^-1 for the dissolved phase. The molecular fingerprints of fatty acids and hydrocarbons evidenced a predominant algal, and to a lesser extent microbial, origin of the organic matter present in water and sediments. Mono- and polyunsaturated fatty acids, which are essential components for animal metabolism, were identified in noticeable amounts in suspended matter (1.8–4.6 g l^-1), and at highly variable levels in the dissolved phase (0.08–1.21 g l^-1).     

Production rates of Eurytemora affinis in the Elbe estuary,comparison of field and enclosure production estimates

Production rates of the calanoid copepod Eurytemora affinis were estimated from field studies in the Elbe estuary and from an enclosure experiment. As one basic parameter of production rates, the body length, was compared between both investigations. Most of the copepodid stages in the enclosure experiment reached a significant greater length than the copepodids in the estuary. The differences in length between copepods from the field and the experiment could mainly be explained by a four times higher chlorophyll-a level in the enclosure experiment. The better food supply also results in a higher individual growth rate for all instars in the enclosure experiment. Therefore the population of Eurytemora affinis in the Elbe estuary was regarded as food limited during certain times of the year, especially in late spring and summer.Maximum daily production rate in the enclosure experiment (40 µg dw l^–1 d^–1) was four times higher than in the estuary (12 µg dw l^–1 d^–1). The mean daily P:B ratio in the enclosure was 0.301 d^–1 compared to 0.11 d^–1 in the estuary.     

Storage,redistribution and net export of dissolved and sediment-bound nutrients,Vejle Fjord,Denmark

Sixty three percent of the nitrogen (total transported 2041 × 10³ kg y^–1) and 17% of the phosphorus (total 159 × 10³ kg y^–1) supplied from terrestrial sources to Vejle Fjord during the period September 1988 to October 1989 is exported to the Kattegat. The sediment nutrient concentrations in the estuary are mainly governed by hydrography and resuspension. The general wind-induced circulation consists of outgoing currents along the southern side and ingoing currents along the northern side of the estuary. The sediments in shallow water on the southern side had higher concentrations of nutrients.Resuspension resulted in large differences between gross sedimentation and net sedimentation, especially in shallow water. Gross sedimentation of total-N in shallow water was 819 × 10³ kg y^–1 compared to a net sedimentation of 19 × 103 kg y^–1. The shallow water areas in the estuary (10% of the area), had a net sedimentation of total-N which was less than 1% of the supply.Wave-induced resuspension only occurs in exposed parts of the deep water area, when wind velocities exceed 10 m s^–1. The concentration of nutrients in the sediments was found to increase with distance from the river (the source) and with increasing depth, as a result of resuspension near the river mouth in the inner part of the estuary. In sheltered parts of the estuary there was no wave-induced resuspension and the net sedimentation equals gross sedimentation. The rate of sedimentation in deep water areas was 12.2 g m^–2y^–1 for total-N and 2.1 gm^–2y^–1 for total-P.     

Rotifer distributions in the coastal waters of the northeast Pacific Ocean

Absolute abundance of rotifers was assessed from 5 to 80 km across the continental shelf off of the southern Oregon coast (U.S.A.) in the northeast Pacific Ocean. A total of 97 vertically stratified water samples were collected at 49 stations from two depths, 3 and 30 m. Coastal upwelling conditions were indicated, with decreased temperature, increased salinity and higher chlorophyll-a concentrations closer to shore. Two rotifer genera, Synchaeta and Trichocercaoccurred within 16 km of shore with densities increasing closer to shore. Synchaeta reached densities of 64 inds l^–1 while Trichocerca was sparse (<1 inds. l^–1). Rotifers were most abundant at 3 m and the densest aggregations appear to be associated with estuary outlets, suggesting that estuaries may be important in exporting rotifers to nearshore coastal waters.     

Organic matter transport in an Appalachian Mountain river in Virginia,U.S.A.

Organic material transport in the New River, Virginia, was investigated over a 12 month period. Collections were made using drift nets and grab water samples from bridges at two sites about 210 km apart. About midway between the two sampling sites is a 1920 ha impoundment used for flood control and power generation. Dissolved organic matter (DOM) ranged 1–50 mg l^–1 at Site 1, upstream from the impoundment, and 11–19 mg l^–1 at Site 2 and was the most abundant form of organic matter at both sites during most periods of the year. Fine particulate organic matter (FPOM) ranged 1–45 mg l^–1 at Site 1 and 1–9 mg l^–1 at Site 2. Concentration of coarse particulate organic matter (CPOM) ranged 0.1–0.7 mg l^–1 at Site 1 and 0.1–0.2 mg l^–1 at Site 2. On an annual basis, the organic matter loads at Site 1 and Site 2 were computed to be 67 000 and 76 800 T y^–1, respectively, suggesting that the impoundment trapped and processed POM, and that municipal and industrial treatment facilities between the study sites supplemented DOM in the river.     

Transport of coarse particulate organic matter in an Idaho river,USA

I investigated organic matter transport in the Henry's Fork of the Snake River, Idaho, USA, from August 1987 to November 1988. Mean discharge during the study was 15 m³ s^–1. Screens were used to sample very coarse (> 6 mm) transported aquatic macrophyte material (VCTMM). Drift nets were used to sample coarse (1–6 mm) and fine (0.25–1 mm) transported particulate organic matter (CTOM and FTOM). Mean monthly concentration of VCTMM was 0.064 mg AFDWl^–1 and was significantly higher than CTOM (0.024 mg AFDW l^–1) and FTOM (0.036 mg AFDW l^–1). VCTMM concentration was highest in December (0.163 mg AFDW l^–1) and lowest in May (0.018 mg AFDW l^–1). The sample position along a transect across the channel had a significant effect on the amount of transported organic matter collected in many months. The concentration of debris from individual species tracked the standing stock of that species during the growing season. In Fall, a dramatic increase in VCTMM corresponded to a decrease in macrophyte standing stock. FTOM and CTOM concentrations were highest in January (CTOM: 0.048; FTOM: 0.111 mg AFDW l^–1), lowest in November 1988 (<0.006 mg AFDW l^–1), were not correlated with discharge, and were inversely correlated with the standing stocks of macrophytes upstream, probably because macrophyte beds influenced the retentiveness of the channel. Standing stock of aquatic macrophytes was highest in September–October (5.2 kg wet weight m ^–2) and lowest in February (1.7 kg wet weight m^–2). Annual movement of particulate organic matter past the sampling point was about 45 000 kg AFDW, of which 21 000 kg was VCTMM, 8 000 kg was CPOM, and 16 000 kg was FPOM.     

Fluxes of bacterioplankton between a tidal estuary and the sea: returning to the “Outwelling Hypothesis”

The tidal dynamics of bacterioplankton communities at the outer part ofa shallow estuary (Ria de Aveiro, Portugal) were studied during 6 tidal cyclesat a fixed sampling site. Bacterial numbers (0.2–8.1 ×10⁹ cells l^–1), aminopeptidase activity(189–1662 nmol l^–1 h^–1),-glucosidase activity (1.7–67.0 nmoll^–1 h^–1) and potential glucoseincorporation (0.48–3.99 nmoll^–1 h^–1) followed a consistent patternof increase during ebb and decrease during flood.Fluxes of bacterioplankton populations and associated heterotrophic activitiesbetween the estuary and the coastal area during a tidal cycle were estimatedfrom the water flux as derived from a two-dimensional vertically-integratednumerical model. The net fluxes estimated for a tidal cycle ranged from–26.0 to –2.5 to × 10¹⁶ bacterial cells. The nettidal fluxes of potential heterotrophic activities ranged from –10 to–80 mol h^–1 for aminopeptidase, –0.33to –1.10 mol h^–1 for -glucosidase and–0.18 to +0.03 mol h^–1 for glucoseincorporation. Net fluxes were generally negative in sign indicating thetransfer of phyto- and bacterioplankton, as well as potential capacities for thedegradation and recycling of organic matter, from the outer estuarinecompartment to the sea.     

Atmospheric emission and cycling of carbonmonoxide in the Scheldt Estuary

Axial profiles of dissolved carbon monoxide(CO) from four surveys of the Scheldt estuaryconfirmed that the estuary is a source ofatmospheric CO, with an emission range of 4–404nmol m^–2 h^–2. Surface water COconcentration and atmospheric emission werespatially variable, with an order of magnitudedifference between the upper and lower estuaryin spring, and seasonally variable with highestlevels in spring and lowest in winter. AnnualCO emission was estimated to be 700 (396–1032)× 10³ mol, equivalent to 0.02–0.05% ofdissolved organic carbon (DOC) input to theestuary. CO photoproduction rates were an orderof magnitude greater in the upper estuary inspring and correlated with DOC concentration.Total CO production from DOC photodegradationwas estimated to be 8.5–18 × 10³ mol COd^–1, equivalent to 0.21–0.44% of riverineDOC input in spring. The deficit betweenproduction and emission suggests that microbialCO oxidation accounts for 68% of photoproducedCO, with highest oxidation rates at lowsalinities. The results indicate that suspendedparticulate material indirectly influencesestuarine CO distribution and emission.Assuming that the Scheldt is representative, estuaries do notcontribute significantly to the oceanic or global CO budgets.     

Is bacterioplankton production in the Ria de Aveiro influenced by salt marshes and bed sediment?

The contribution of potential export of materials from bottom sedimentsand salt marshes into the water column of a shallow estuarine system of Ria deAveiro to the observed high bacterial productivity in the mid section of thisestuary was evaluated. Vertical profiles of physical, chemical and bacterialvariables were studied in the marine and brackish water zones, and oftransversal profiles in the brackish zone only. Although the concentrations ofseston (17–241 mg l^–1), particulate organiccarbon (3–15.5 mg l^–1) and chlorophyll(1.2–7.0 g l^–1) varied widely, thevertical and transversal profiles were without much variation. Total bacterialnumber (0.2–8.5 × 10⁹ cellsl^–1) and the number of particle-attached bacteria(0.02–2.50 × 10⁹ cellsl^–1)along vertical and transversal profiles did not differ much, but the rate ofbacterial production (0.05–14.2 g C l^–1h^–1) and dissolved organic carbon concentration(6.0–69.2 mg l^–1) were frequently highernear the salt marsh margin at the brackish water transect. The increase inproductivity could not be associated with runoff of particulate matter butcoincided with the inputs of dissolved organic carbon. The results of verticaland transversal profiles point to a minor role of particulate matter additionsfrom the salt marsh area or from bed sediments.     

Spatial variability of stable carbon and nitrogen isotope ratios in a Mediterranean coastal lagoon

Exploring the trophic pathway of organic matter within the Mauguio lagoon (southern France, western Mediterranean), we found spatial differences in the isotopic composition (both δ¹³C and δ¹⁵N values) of organic matter sources (primary producers, particulate and sedimentary organic matter), which were mirrored in the upper trophic levels (invertebrates and fish). On average, δ¹³C was heavier by about 1.5–2‰ in the location under marine influence than in the sites influenced by freshwater discharge. The opposite trend was found for δ¹⁵N, which attained maximum values in the north-central zone influenced by freshwater delivery. For both C and N stable isotope ratios, the highest spatial variability was found in organic matter sources (2–3‰), while invertebrates and fish exhibited less variability (\~1–2‰). The differences observed may be related to both anthropogenic (wastewater input) and natural (marine vs. terrestrial inputs) factors. Discharge of wastewater, which affects the innermost location, generally determines an increase in the relative abundance of ¹⁵N. In addition, terrestrially derived nutrients and organic matter, which also affect the innermost location, are known to determine a shift towards ¹³C-depleted values. Our results substantiate the finding that the analysis of carbon and nitrogen stable isotopes can help in elucidating origin and fate of organic matter in coastal lagoons, which are characterised by a great spatial variability and complexity.     

The application of a laboratory apparatus for the study of nutrient fluxes between sediment and water

Sediments of the river Elbe estuary have been studied to assess their impact on the total nitrogen budget of the estuary. A new laboratory incubation apparatus was used to provide a means of regulating important parameters such as temperature and oxygen concentrations. With this apparatus sediment cores from a typical shallow water area with high organic carbon content were incubated under varying oxygen concentrations in the overlying water. Measurements of ammonium, nitrite, nitrate and nitrous oxide in the water phase were carried out and the fluxes between sediment and water phase calculated. During aerobic conditions in the water phase overall nitrate fluxes between + 4 and –3.5 mmol Nm^–2d^–1 across the sediment/water interface were observed. Under anaerobic conditions the fluxes increased up to –10 mmol Nm^–2 d^–1. Nitrous oxide was formed within the sediment under both aerobic and anaerobic conditions. Fluxes into the water phase were highest when the oxygen concentrations in the water phase were low (between 0.1 and 0.6 mg l^–1).     

Use of stable isotope ratios of fish larvae as indicators to assess diets and patterns of anthropogenic nitrogen pollution in estuarine ecosystems

A stable isotope study was carried out to investigate the feeding ecology of the common goby Pomatoschistus microps larvae (Krøyer, 1838), and to assess differences in the response of planktonic food web to nutrient enrichment, in two ecosystems from the Southern European coast with different levels of historical pollution (estuaries of the Minho and Lima Rivers). At each estuary and time (July 2012, November 2012, February 2013, and June 2013), the fish larvae of two size classes (class 0: 0–10 mm; class 1: 10–15 mm), particulate organic matter (POM), and pelagic zooplankton were collected. The stable isotope mixing model SIAR revealed that, despite temporal differences in the relative proportion of prey items ingested, in both estuaries P. microps larvae feed on both planktonic-hyperbenthic food sources, predating mainly on copepods (from 34% to 60%), Mysidacea (from 16% to 28%), and brachyuran zoea (from 14% to 29%). Fish larvae size classes did not differ significantly for δ¹⁵N, and exhibited a very narrow range of the δ¹³C signature. Enriched δ¹⁵N values of all biota in the Lima estuary throughout the study period, with a marked nitrogen enrichment in colder months, are indicative of higher anthropogenic inputs of nitrogen (e.g. sewage and industrial discharges, agriculture) into this system. The δ¹⁵N values of fish larvae and other planktonic groups can be a sensitive bioindicator, because they are highly correlated with the nitrogen content of water (ammonium), indicating that this element has transferred through the planktonic food web. Enriched carbon isotope ratios were observed in warmer months, in both estuaries, and the heavier δ¹³C values in Lima are best explained by differences in the degree of marine influence. This research emphasises the utility of stable isotopes in trophic interactions studies, highlighting the relevance of the stable nitrogen isotope of zooplanktonic communities as a reliable bioindicator to detect patterns of anthropogenic nitrogen contamination in estuarine ecosystems.     

Concentration and annual accumulation values of heavy metals in lake sediments: Their significance in studies of the history of heavy metal pollution

The first part of the paper discusses the significance of using either concentration or accumulation values for expressing the results of investigations of lake sediment cores aimed at studying the history of heavy metal pollution. Neither the values for heavy metal concentration in the lake sediment, whether expressed per gram dry sediment or per gram soluble (organic) sediment, nor the values for their total annual accumulation per unit area of the lake bottom, can, on their own, provide an accurate picture of past pollution conditions, but when considered in combination they render a fairly reliable and detailed interpretation. The second part of the paper deals with Pb, Cd and Hg analyses of cores of varved sediments from several lakes in N. Sweden. Pb and Cd pollution increased during the second half of the 19th century. In most lakes, Hg pollution seems first to have started during the 20th century. Marked increases in both concentration and accumulation of heavy metals took place during the 20th century. For recent decades, the estimated accumulation rates of heavy metals from anthropogenic sources are: Pb 0.5–1.5 µg cm^–2 yr^–1, Cd 15–30 ng cm^–2 yr^–1 and Hg 1–2 ng cm^–2 yr^–1, Higher values were recorded in lakes affected by local emissions.     

Clonal propagation of Enset (Ensete superbum (Roxb.) Cheesman) through shoot tip cultures

Summary The morphogenetic potential of the shoot tip explants ofEnsete superbum (Roxb.) Cheesman, a wild relative of the cultivated bananas, was investigated and an effective clonal propagation method devised. Shoot tip explants grown in modified MS medium containing 1.5 mg l^–1 BAP and 1 mg l^–1 KIN developed corms which on transfer to medium containing 3 mg l^–1 IBA and 1.5 mg l^–1 BAP, regenerated a large number of shoots from the surface of the corm, the origin of which was traced to single hypodermal cells. Shoots were rooted on a half-strength MS medium salts containing 3 mg l^–1 IBA and 0.1 mg l^–1 BAP. The rooted plantlets were hardened and planted in the field where the plants looked normal.     

Tracing estuarine organic matter sources into the southern North Sea using C and N isotopic signatures

Sources and distribution of particulate organic matter in surface waters of the Humber and Thames estuaries and in the East Anglian plume in the southern North Sea were investigated in winter 2006/2007. Carbon (C) and nitrogen (N) stable isotopes provided evidence for the presence of three particulate organic matter sources; riverine plankton (δ¹³C ?30 ‰ and δ¹⁵N 7.9 ‰) identified in the Thames estuary only, marine plankton (average δ¹³C ?21.4 ‰ and δ¹⁵N 4.5 ‰) and a third source with an enriched ¹³C signature (>?16.7 ‰) and elevated C:N ratio (>12.7). Particulate organic matter with enriched ¹³C values were observed throughout the Humber estuary and at the marine end-member of the Thames estuary. While bacterial cycling of organic carbon undoubtedly takes place within these estuaries, these processes on their own are unlikely to account for the isotopic signatures seen. The ¹³C enriched organic matter source is suggested to be due to particulate organic matter input from marsh plants and seagrasses such as Spartina spp. and Zostera on the adjacent salt marshes and mudflats and/or macroalgae along the banks of the estuaries. This ¹³C enriched signal was also identified approximately 50 km offshore within the southern North Sea, in the East Anglian plume, which transports UK riverine water off-shore in a discrete plume. This plume therefore provides a mechanism to transport this estuarine derived organic matter pool offshore out of the estuaries. These results indicate that estuarine derived organic matter from marsh plants, seagrasses and/or macroalgae contributes to the southern North Sea organic matter pool and is therefore likely to contribute to winter-time shelf sea carbon and nitrogen cycles.     

Seasonal change in the proportion of bacterial and phytoplankton production along a salinity gradient in a shallow estuary

We intended to evaluate the relative contribution of primary production versus allochthonous carbon in the production of bacterial biomass in a mesotrophic estuary. Different spatial and temporal ranges were observed in the values of bacterioplankton biomass (31–273 g C l^–1) and production (0.1–16.0 g C l^–1 h^–1, 1.5–36.8 mg C m^–2 h^–1) as well as in phytoplankton abundance (50–1700 g C l^–1) and primary production (0.1–512.9 g C l^–1 h^–1, 1.5–512.9 mg C m^–2 h^–1). Bacterial specific growth rate (0.10–1.68 d^–1) during the year did not fluctuate as much as phytoplankton specific growth rate (0.02–0.74 d^–1). Along the salinity gradient and towards the inner estuary, bacterio- and phytoplankton biomass and production increased steadily both in the warm and cold seasons. The maximum geographical increase observed in these variables was 12 times more for the bacterial community and 8 times more for the phytoplankton community. The warm to cold season ratios of the biological variables varied geographically and according to these variables. The increase at the warm season achieved its maximum in the biomass production, particularly in the marine zone and at high tide (20 and 112 times higher in bacterial and phytoplankton production, respectively). The seasonal variation in specific growth rate was most noticeable in phytoplankton, with seasonal ratios of 3–26. The bacterial community of the marine zone responded positively – generating seasonal ratios of 1–13 in bacterial specific growth rate – to the strong warm season increment in phytoplankton growth rate in this zone. In the brackish water zone where even during the warm season allochthonous carbon accounted for 41% (on average) of the bacterial carbon demand, the seasonal ratio of bacterial specific growth rate varied from about 1 to 2. During the warm season, an average of 21% of the primary production was potentially sufficient to support the whole bacterial production. During the cold months, however, the total primary production would be either required or even insufficient to support bacterial production. The estuary turned then into a mostly heterotrophic system. However, the calculated annual production of biomass by bacterio- and phytoplankton in the whole ecosystem showed that auto- and heterotrophic production was balanced in this estuary.     

Arsenic and antimony release from sediments in a Mediterranean estuary

An ancient realgar mine is responsible for the contamination of a riverine system in central Corsica. Nearby the mine, high As and Sb concentrations are found (up to 2–3 mg l^-1 and 2–3 g l^-1 respectively). A significant increase of the As and Sb concentrations in water is found in the water of the mixing zone of river and sea (Bravona estuary; chlorinity 7000–7800). In the same area, a decrease of As and Sb concentrations in sediments is observed. Fe and Mn exhibit the same behaviour. The possible involvement of redox processes is discussed. However, owing to insufficient reducing capacity and insignificant variation of redox potential values along the various estuarine sites (from 320 down to 280 mV), this scenario is rather doubtful. Desorption from FeOOH particles is the most likely process in the Bravona estuary. The impact of these contaminated waters on the marine environment is discussed. Owing to decrease by dilution, as well as the reduced water flow of the estuary, the net supply of As and Sb to the Tyrrhenian Sea is approximately 5 and 1.5 t y^-1 for As and Sb respectively. The possible harmful influence of the Bravona river should be of local concern only, and the emphasis of this study is, therefore, on a better knowledge of in situ processes.