Dissolved trace metal distributions in Port Jackson estuary (Sydney Harbour), Australia

Concentrations of dissolved metals (Cd, Cu, Ni, Mn and Zn) were determined for summer and winter, under low-flow conditions in Port Jackson, a microtidal, well-mixed estuary in south-east Australia. Mean concentrations of Cd (0.04+/-0.02 microg/l), Ni (0.86+/-0.40 microg/l), Mn (20.0+/-25 microg/l) and Zn (6.47+/-2.0 microg/l) were below water quality guidelines. Concentrations of Cu (1.68+/-0.37 microg/l), however, slightly exceeded recommended values. Dissolved Ni and Mn behaved mostly conservatively, whereas Cd, Cu and Zn showed mid-estuarine maxima. Peaks in Cd, Cu and Zn concentrations were located in the upper estuary, independent of the salinity and suspended particulate matter loading, and were consistent with anthropogenic inputs of metals in the estuary. Concentrations of dissolved Cu were highest in summer, whereas concentrations of Cd, Ni and Mn were significantly lower in summer than winter (P< or =0.05). The increase in temperature and biological activity during summer explained the seasonal variation. The sequence of log K(d) values (20-30 salinity) was Mn>Zn>Cu>Ni. These results give unique information concerning the contemporaneous distribution of dissolved trace metals in the Port Jackson estuary and they provide a data set against which the long-term contamination may be assessed.     

Copper toxicity in the marine copepod Tigropus japonicus: low variability and high reproducibility of repeated acute and life-cycle tests

The intertidal copeopod Tigriopus japonicus, which is abundant and widely distributed along the coasts of Western Pacific, has been suggested to be a good marine ecotoxicity testing organism. In this study, a series of experiments were conducted to investigate the reproducibility and variability of copper (Cu) sensitivity of T. japonicus so as to evaluate its potential to serve as an appropriate test species. To understand the seasonal variation of Cu sensitivity, individuals of T. japonicus were collected from the field in summer and winter, and subjected to standard 96 h acute (static renewal) toxicity tests. 96 h-LC50 values of T. japonicus collected from the two seasons were marginally different (p = 0.05), with an overall coefficient of variation (CV) of 33%. Most importantly, our results indicated that chronic Cu sensitivity of T. japonicus was highly reproducible. The CVs of intrinsic rates of increase in the population of the control and Cu treatment (10 microg Cu l(-1)) groups were only 10-11% between 10 runs of a standardised complete life-cycle test. Moreover, different Cu(II) salts generally resulted in a similar 96 h-LC50 value while Cu(I) chloride was consistently slightly less toxic than Cu(II) salts. Given such a high reproducibility of toxic responses, it is advocated to use T. japonicus as a routine testing organism.     

Toxicities of antifouling biocide Irgarol 1051 and its major degraded product to marine primary producers

Irgarol 1051 (2-methythiol-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an algaecide commonly used in antifouling paints. It undergoes photodegradation which yields M1 (2-methylthio-4-tert-butylamino-6-amino-s-triazine) as its major and most stable degradant. Elevated levels of both Irgarol and M1 have been detected in coastal waters worldwide; however, ecotoxicity effects of M1 to various marine autotrophs such as cyanobacteria are still largely unknown. This study firstly examined and compared the 96 h toxicities of Irgarol and M1 to the cyanobacterium Chroococcus minor and two marine diatom species, Skeletonema costatum and Thalassiosira pseudonana. Our results suggested that Irgarol was consistently more toxic to all of the three species than M1 (96 h EC50 values: C. minor, 7.71 microug L(-1) Irgarol vs. > 200 microg L(-1) M1; S. costatum, 0.29 microg L(-1) Irgarol vs. 11.32 microg L(-1)M1; and T. pseudonana, 0.41 microg L(-1) Irgarol vs. 16.50 microg L(-1)M1). Secondly, we conducted a meta-analysis of currently available data on toxicities of Irgarol and M1 to both freshwater and marine primary producers based on species sensitivity distributions (SSDs). Interestingly, freshwater autotrophs are more sensitive to Irgarol than their marine counterparts. For marine autotrophs, microalgae are generally more sensitive to Irgarol than macroalgae and cyanobacteria. With very limited available data on M1 (i.e. five species), M1 might be less toxic than Irgarol; nonetheless this finding warrants further confirmation with additional data on other autotrophic species.     

Distribution of heavy metals in marine bivalves, fish and coastal sediments in the Gulf and Gulf of Oman

An assessment of marine contamination due to heavy metals was made in the Gulf and Gulf of Oman based on marine biota (fish and various bivalves) and coastal sediment collected in Bahrain, Oman, Qatar, and the United Arab Emirates (UAE) during 2000-2001. Sediment metal loadings were generally not remarkable, although hot spots were noted in Bahrain (Cu, Hg, Pb, Zn) and on the east coast of the UAE (As, Co, Cr, Ni). Concentrations of As and Hg were typically low in sediments and the total Hg levels in top predator fish commonly consumed in the region were < 0.5 microg g(-1) and posed no threat to public health. Very high Cd concentrations (up to 195 microg g(-1)) in the liver of some fish from southern Oman may result from food-chain bioaccumulation of elevated Cd levels brought into the productive surface waters by upwelling in the region. Very high As concentrations (up to 156 microg g(-1)) were measured in certain bivalve species from the region. Although not certain, the As is probably derived from natural origins rather than anthropogenic contamination.     

Marine risk assessment: linear alkylbenzenesulponates (LAS) in the North Sea

The fate of linear alkylbenzenesulponates (LAS) in estuaries and coastal areas of the North Sea has been characterized with simple environmental models. The predicted concentration range in the estuaries around the North Sea (0.9-9 microg LAS l(-1)) was validated by monitoring data (1-9 microg LAS l(-1)). In offshore sites of the North Sea, it is estimated--and experimentally verified for a few sites--that the LAS concentration is below analytical detection limit (i.e., 0.5 microg LAS l(-1)). The effects of LAS on marine organisms have been reviewed. For short-term acute tests, there was no significant difference (p = 0.83) between the mean LC50 values of freshwater and marine organisms (mainly pelagic species tested, 4.1 and 4.3 mg LAS l(-1), respectively). For longer-term chronic tests, it appeared that the sensitivity (mean no-observed effect concentration (NOEC) value) of marine and freshwater organisms (0.3 and 2.3 mg LAS l(-1), respectively) was significantly different pt-test = 0.007). The predicted no-effect-concentrations (PNEC) were 360 and 31 microg LAS l(-1), for freshwater and marine pelagic communities, respectively. Given that the maximum expected estuarine and marine concentrations are 3 to > 30 times lower than the PNEC, the risk of LAS to pelagic organisms in these environments is judged to be low.     

Copper accumulation by bacteria and transfer to scallop larvae

A bacterial copper-resistant strain was isolated from a hatchery-conditioned adult of the scallop Argopecten purpuratus and was identified as Vibrio sp. according to its physiological characteristics. The lowest concentration of Cu2+ required for its complete inhibition in VNSS medium was 50 microg ml(-1). The Vibrio strain was found to accumulate copper, exhibiting cellular and loosely bound copper levels of 201.14 and 493.21 microg g(-1) dry weight, respectively, after 24 h of incubation in VNSS medium supplemented with 15 microg ml(-1) of Cu2+, with cellular concentration factors of 10.17 and 14.35 after 12 and 24 h of exposure. When a scallop larvae culture was exposed to a concentration of 6.46 x 10(2) CFU ml(-1) of Cu-enriched Vibrio, they accumulated 20.42 +/- 1.12 and 30.96 +/- 1.85 microg Cu2+ g(-1) dry weight after 12 and 24 h, respectively. This study suggests that bacterial copper accumulation could be very active in marine environments increasing the occurrence of copper transfer to marine food chains.     

Nutrient loss and water quality under extensive grazing in the upper Burdekin river catchment, North Queensland

Increased sediment and nutrient losses resulting from unsustainable grazing management in the Burdekin River catchment are major threats to water quality in the Great Barrier Reef Lagoon. To test the effects of grazing management on soil and nutrient loss, five 1 ha mini-catchments were established in 1999 under different grazing strategies on a sedimentary landscape near Charters Towers. Reference samples were also collected from watercourses in the Burdekin catchment during major flow events. Soil and nutrient loss were relatively low across all grazing strategies due to a combination of good cover, low slope and low rainfall intensities. Total soil loss varied from 3 to 20 kg ha(-1) per event while losses of N and P ranged from 10 to 1900 g ha(-1) and from 1 to 71 g ha(-1) per event respectively. Water quality of runoff was considered moderate across all strategies with relatively low levels of total suspended sediment (range: 8-1409 mg l(-1)), total N (range: 101-4000 microg l(-1)) and total P (range: 14-609 microg l(-1)). However, treatment differences are likely to emerge with time as the impacts of the different grazing strategies on land condition become more apparent. Samples collected opportunistically from rivers and creeks during flow events displayed significantly higher levels of total suspended sediment (range: 10-6010 mg l(-1)), total N (range: 650-6350 microg l(-1)) and total P (range: 50-1500 microg l(-1)) than those collected at the grazing trial. These differences can largely be attributed to variation in slope, geology and cover between the grazing trial and different catchments. In particular, watercourses draining hillier, grano-diorite landscapes with low cover had markedly higher sediment and nutrient loads compared to those draining flatter, sedimentary landscapes. These preliminary data suggest that on relatively flat, sedimentary landscapes, extensive cattle grazing is compatible with achieving water quality targets, provided high levels of ground cover are maintained. In contrast, sediment and nutrient loss under grazing on more erodable land types is cause for serious concern. Long-term empirical research and monitoring will be essential to quantify the impacts of changed land management on water quality in the spatially and temporally variable Burdekin River catchment.     

Assessing the influence and distribution of shrimp pond effluent in a tidal mangrove creek in north-east Australia

Effluent from a land based shrimp farm was detected in a receiving creek as changes in physical, chemical and biological parameters. The extent and severity of these changes depended on farm operations. This assessment was conducted at three different stages of shrimp-pond maturity, including (1) when the ponds were empty, (2) full and (3) being harvested. Methods for assessing farm effluent in receiving waters included physical/chemical analyses of the water column, phytoplankton bioassays and nitrogen isotope signatures of marine flora. Comparisons were made with an adjacent creek that served as the farms intake creek and did not directly receive effluent. Physical/chemical parameters identified distinct changes in the receiving creek with respect to farm operations. Elevated water column NH(4)(+) (18.5+/-8.0 microM) and chlorophyll a concentrations (5.5+/-1.9 microg/l) were measured when the farm was in operation, in contrast to when the farm was inactive (1.3+/-0.3 microM and 1.2+/-0.6 microg/l, respectively). At all times, physical/chemical parameters at the mouth of the effluent creek, were equivalent to control values, indicating effluent was contained within the effluent-receiving creek. However, elevated delta(15)N signatures of mangroves (up to approximately 8 per thousand) and macroalgae (up to approximately 5 per thousand ) indicated a broader influence of shrimp farm effluent, extending to the lower regions of the farms intake creek. Bioassays at upstream sites close to the location of farm effluent discharge indicated that phytoplankton at these sites did not respond to further nutrient additions, however downstream sites showed large growth responses. This suggested that further nutrient loading from the shrimp farm, resulting in greater nutrient dispersal, will increase the extent of phytoplankton blooms downstream from the site of effluent discharge. When shrimp ponds were empty water quality in the effluent and intake creeks was comparable. This indicated that observed elevated nutrient and phytoplankton concentrations were directly attributable to farm operations.     

Concentration and subcellular distribution of trace elements in liver of small cetaceans incidentally caught along the Brazilian coast

Concentrations of trace elements (V, Cr, Mn, Fe, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Mo, Ag, Cd, Sb, Cs, Ba, T-Hg, Org-Hg, Tl and Pb) were determined in liver samples of estuarine dolphin (Sotalia guianensis; n = 20), Franciscana dolphin (Pontoporia blainvillei; n = 23), Atlantic spotted dolphin (Stenella frontalis; n = 2), common dolphin (Delphinus capensis; n = 1) and striped dolphin (Stenella coeruleoalba; n = 1) incidentally caught along the coast of Sao Paulo State and Parana State, Brazil, from 1997 to 1999. The hepatic concentrations of trace elements in the Brazilian cetaceans were comparable to the data available in literature on marine mammals from Northern Hemisphere. Concentrations of V, Se, Mo, Cd, T-Hg and Org-Hg increased with increasing age in liver of both estuarine and Franciscana dolphins. Very high concentrations of Cu (range, 262-1970 microg/g dry wt.) and Zn (range, 242-369 microg/g dry wt.) were observed in liver of sucklings of estuarine dolphin. Hepatic concentrations of V, Se, T-Hg, Org-Hg and Pb were significantly higher in estuarine dolphin, whereas Franciscana dolphin showed higher concentrations of Mn, Co, As and Rb. Ratio of Org-Hg to T-Hg in liver was significantly higher in Franciscana dolphin than estuarine dolphin, suggesting that demethylation ability of methyl Hg might be lower in liver of Franciscana than estuarine dolphins. High hepatic concentrations of Ag were found in some specimens of Franciscana dolphin (maximum, 20 microg/g dry wt.), and 17% of Franciscana showed higher concentrations of Ag than Hg. These samples with high Ag concentration also exhibited elevated hepatic Se concentration, implying that Ag might be detoxified by Se in the liver. Higher correlation coefficient between (Hg+0.5 Ag) and Se than between Hg and Se and the large distribution of Ag in non-soluble fraction in nuclear and mitochondrial fraction of the liver also suggests that Ag might be detoxified by Se via formation of Ag2Se in the liver of Franciscana dolphin.     

Metallothionein in intestine of red mullet, Mullus barbatus as a biomarker of copper exposure in the coastal marine areas

Dietary metal exposure in fish is studied in native red mullet, Mullus barbatus, involving metallothionein (MT) response in the intestine, a primary site for metal uptake. Intestinal MTs (microg mg(-1) proteins), total proteins (mgml(-1) S50), Cu, Zn, Fe, Mn and Cd (microg ml(-1) S50) are considered as indicators of metal exposure in specimens from near-shore and off-shore locations of the Eastern Adriatic Sea. Metallothionein and Cu are statistically significantly higher in 68 specimens from the Kastela Bay, a near-shore area (30.0+/-6.71microg MT mg(-1) proteins; 0.30+/-0.08microg Cu ml(-1) S50), in comparison to 51 specimens from off-shore area, Solta Island (25.9+/-4.21microg MT mg(-1) proteins; 0.26+/-0.09microg Cu ml(-1) S50). Cytosolic Cu, a MT inducer, is significantly correlated (p<0.05, r=0.44) with MT in specimens from the Kastela Bay, independent on fish biometry. Our study indicates that cytosolic intestinal Cu and MT represent a measurable biochemical response in red mullet specimens, dwelling above sediments contaminated with Cu.     

Zinc concentrations in marine macroalgae and a lichen from western Ireland in relation to phylogenetic grouping, habitat and morphology

Zinc concentrations in 19 species of marine macroalgae and a lichen from western Ireland (Spiddal, Co. Galway) were analysed by atomic absorption spectrophotometry. Algae were collected from a single site but occupied different shore levels and belonged to distinct phylogenetic groupings and to different (previously recognised) morphological groups. Concentrations ranged from 15-115 microg g(-1) dry weight. The greatest variation in concentration occurred amongst the red algal species, containing both maximum and minimum concentrations. Zn concentrations in brown and green algae were generally lower than those in red algae. When grouped according to thallus morphology, thin, branched sheets (which consisted mainly of red algae) contained the highest Zn concentrations. In filamentous algae, Zn levels were higher than in thick-leathery or coarsely branched algae. However, all green algal species examined had similar Zn concentrations, despite their different morphologies. In brown algae, the highest Zn levels were detected in mid-shore fucoids (Fucus vesiculosus and Fucus serratus), while thicker, subtidal and low-shore brown algae (Laminaria digitata, Halydris siliquosa) exhibited lower Zn concentrations. The lowest Zn concentrations were detected in high-intertidal species (Fucus spiralis, Pelvetia canaliculata), the only marine lichen examined (Ramalina siliquosa) and a red crustose alga (Corallina officinalis). In all morphological groups, red algal representatives contained relatively higher levels of Zn, the exception being Corallina officinalis. Zn levels in 4 species from a second, estuarine site in Galway Bay exhibited the same relative differences amongst species, but were all consistently higher than in algae from Spiddal. It is concluded that Zn accumulation in macroalgae is closely related to ecological growth strategies, following a functional-form model. However, the phylogenetic origin of species which determines carbohydrate and phenol composition, and responses to ambient environmental conditions ultimately determine, the availability of binding sites for polyvalent cations.     

Influence of the Danube River inputs on C and N stable isotope ratios of the Romanian coastal waters and sediment (Black Sea)

The main aim of this study was to estimate the influence of the seasonal variations of the Danube River particulate organic matter (POM) inputs on the Black Sea surface seawater POM and upper layer of sediments along the Romanian coast. Ratios of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotopes allowed differentiating river and marine organic matter sources. Danube River POM presented significantly lower average values of delta(13)C (-27.52+/-0.88 per thousand) and delta(15)N (4.88+/-1.45 per thousand) than seawater POM (delta(13)C=-24.70+/-2.37 per thousand and delta(15)N=6.75+/-1.96 per thousand), whereas surface sediment presented average values similar to seawater POM (delta(13)C=-24.02+/-2.39 per thousand and delta(15)N=7.29+/-2.16 per thousand). Stable isotope values showed that the Danube River influence on marine ecosystems decreased from the North to the South of the Romanian coast. Strong seasonal variations of C and N isotopic signatures were observed in all compartments studied with generally higher values in spring when the river was flooding.     

Effects of deposit feeder Stichopus japonicus on algal bloom and organic matter contents of bottom sediments of the enclosed sea

Algae growing in an enclosed sea may inhibit eutrophication because they absorb nutrients in the water. However, dead algae often cause anaerobic conditions in the water just above and on sediment after they are deposited on the bottom. We found that Stichopus japonicus inhibited the anaerobic processes coupling water sulfite production in sediment. The present study investigates whether S. japonicus inhibits algal flourish and influences sediment properties such as organic matter contents. Aquarium experiments were carried out at Komatsushima port in Tokushima Prefecture, western Japan. The aquaria used in the experiments were supplied with water directly from the adjacent sea (6 L/min), laid with sand of 10 cm depths, and lighted at 12 h intervals. Six aquaria each containing a sea cucumber from Komatsushima port and six aquaria without any were used in the experiments. Water temperature ranged between 9 and 15 degrees C during December 2000 and April 2001. Salinity ranged between 32 per thousand and 34 per thousand. Algae began to cover the bottom of the aquaria without S. japonicus after 2 weeks, whereas no growth was evident in the aquaria containing sea cucumbers. Chlorophyll a concentration in the surface sediment of the aquaria with S. japonicus (6.1+/-3.6 microg/g, mean S.D.+/-standard deviation) was significantly lower than that without it (60+/-17 microg/g, U-test, p<0.05). Phaeophytin concentration in the surface sediment of the aquaria with S. japonicus (0.9+/-0.09 microg/g) was also significantly lower than that without it (4.5+/-1.0 microg/g, U-test, p<0.05). TOC concentration in the surface sediment of the aquaria with S. japonicus (2.6+/-1.3 microg/g) was slightly lower than that without it (4.0+/-1.2 microg/g). These results showed that algal biomass and organic matter concentration of the bottom were decreased in the presence of S. japonicus. Therefore, S. japonicus inhibits algal bloom and decrease the contents of organic matter deposited on the bottom of enclosed sea areas.     

Effects of metals on sea urchin development: A rapid bioassay

Embryos of sea urchins show a differential response to Cd, Cu, Cr, Ni and Zn. The responses are also stage-specific. The different morphological effects of various metals reflect the differentiation of the early embryonic cells. Since fertilization can be inhibited in the presence of metals, especially Cu, the ability of the gametes to undergo fertilization can then be used as a biological indicator for a rapid assay, 10–20 min., of marine pollutants. Since embryo-genesis up to plutei stage requires only 20 h, this duration is also short compared to other systems utilizing embryonic or larval forms.     

Differences in the acute toxicities of tributyltin between the Caprellidea and the Gammaridea (Crustacea: Amphipoda)

Tests for the acute toxicity of tributyltin (TBT) were conducted on amphipod crustaceans collected from Otsuchi Bay, Japan. Five species of caprellids and three species of gammarids, which belong to a closely related ecological niche, were used for the exposure experiments at seven test concentrations (0, 0.001, 0.01, 0.1, 1, 10 and 100 microg TBTCl/l) for 48 h at 20 degrees C. The 48-h LC50 values of the caprellids were 1.2-6.6 microg TBTCl/l, and these were significantly lower than those of the gammarids (17.8-23.1 microg TBTCl/l). This suggests that caprellids are more sensitive to TBT than gammarids. Furthermore, the proportions of TBT and its derivatives, dibutyltin (DBT) and monobutyltin (MBT), were measured in the amphipods collected from Otsuchi Bay. In the caprellids, TBT was the predominant compound, accounting for 72% of the total butyltin which reflected the butyltin ratio in seawater, while in the gammarids, TBT's breakdown products (DBT and MBT) predominated, accounting for 75% of the total butyltin. This difference suggests that caprellids may have lower metabolic capacity to degrade TBT than gammarids. Therefore, the difference in sensitivity to TBT among the amphipods is thought to be related to the species-specific capacity to metabolize TBT.     

Coral skeletal delta(15)N reveals isotopic traces of an agricultural revolution

This study introduces a new method of tracing the history of nutrient loading in coastal oceans via delta(15)N analysis of organic nitrogen preserved in the skeleton of the massive Porites coral. Four coral cores were collected in Bali, Indonesia, from reefs exposed to high levels of fertilizers in agricultural run-off, from lagoonal corals impacted by sewage, and from a reef located 30 km offshore. Skeletal delta(15)N in the agriculturally exposed coral declined from 10.7+/-0.4 per thousand in 1970-1971, when synthetic fertilizers (-0.8 per thousand+/-0.2 per thousand) were introduced to Bali, to a depleted "anthropogenic" baseline of 3.5 per thousand+/-0.4% in the mid-1990s. delta(15)N values were negatively correlated with rainfall, suggesting that marine delta(15)N lowers during flood-bourn influxes of waste fertilizers. Reef cores exposed to untreated sewage in terrestrial discharge were enriched (7.8 and 7.3+/-0.4 per thousand), while the offshore core reflected background oceanic signals (6.2+/-0.4 per thousand). delta(15)N, N concentration, and C:N systematics indicate that the N isotopic composition of skeletal organic matter was generally well preserved over 30 years. We suggest that skeletal organic delta(15)N can serve as a recorder of past nitrogen sources. In Bali, this tracer suggests that the intensification of Western style agricultural practices since 1970 are contributing to the degradation of coastal coral reefs.     

Indicator of paleosalinity: Sedimentary sulfur and organic carbon in the Jurassic–Cretaceous Tetori Group,central Japan

A simple geochemical technique using the ratio of total sulfur (TS) to total organic carbon (TOC) was successfully used to reconstruct paleoenvironments in the Jurassic–Cretaceous Tetori Group, central Japan. The TS to TOC ratio is often employed as an effective parameter to separate modern marine or brackish sediments from freshwater deposits. To test the TS/TOC method for paleoenvironmental interpretation of the Tetori Group, we first analyzed TS/TOC for samples for which depositional conditions (i.e. marine, brackish or freshwater) had been recognized paleontologically. The results indicate that the method can effectively separate sedimentary rocks deposited under freshwater from marine and brackish settings. Once we had established the effectiveness of this method, we applied it to three sections of the Tetori Group, central Japan. Stratigraphic fluctuations in TS/TOC values revealed episodic incursions of marine or brackish conditions in the dominantly freshwater depositional sequence in the middle of the Jobu Formation of the Itoshiro Subgroup at the Izumi section, Fukui Prefecture. The same paleoenvironment is also suggested to occur at the top of the Tetori Group in the Tateyama section, Toyama Prefecture. This research provides important information to paleogeographers who currently lack evidence from facies fossils to indicate if the uppermost part of the Tetori Group represents marine or brackish settings. A chemostratigraphy of TS/TOC parameters potentially could provide a correlation among Jurassic–Cretaceous sequences along continental margins over East Asia.     

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Pe?a Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Pe?a Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.     

Effects of antifouling paint components (TBTO,copper and triazine) on the early development of embryos in cod (Gadus morhua L.)

To assess the risk of antifoulant use to the commercially important cod (Gadus morhua L.), fertilised cod eggs were exposed to triazine, copper and TBTO singly or combined in laboratory tests with running seawater. At the highest tested concentrations (11.5 microg Cu l(-1); 5 microg TBTO l(-1)) larval mortality was increased. The highest concentration of triazine (40 microg l(-1)) did not cause any significant mortality. Fertilised eggs that had been exposed to all the three chemicals singly for five days showed a higher buoyancy than the controls. No synergistic or antagonistic effects were indicated. Embryos/larvae exposed to 0.004-0.8 microg TBTO l(-1) did not show any changed respiration compared to the controls after hatching. It is concluded that existing known field concentrations of the three antifoulants are hardly expected to cause detectable effects on fish embryonic/larval development.     

In situ trace metal speciation in a eutrophic lake using the technique of diffusion gradients in thin films (DGT)

We evaluated the application of DGT (diffusion gradients in thin films) as a tool to determine Cu, Zn, Ni, Cd, Pb and Mn concentrations and speciation in a hardwater eutrophic lake. This technique was used in situ during six sampling periods over one year in Lake Greifen. The DGT-labile species of Cu and Ni amounted to 15-25% of the total dissolved concentrations. Speciation by ligand-exchange/DPCSV indicated that Cu and Ni were predominantly organically complexed (>99%). Thus, the DGT-labile species for Cu and Ni were much more abundant than the free ionic and inorganic species determined by ligand-exchange/DPCSV. The results can be explained by incomplete metal exchange of very strong complexes with the chelating resin in the DGT devices, metal exchange of less abundant weaker complexes, and by slow diffusion of exchangeable organic complexes. For Zn (36 to >90% DGT-labile) and Mn (50 to 100% DGT-labile), the results indicated that these metals are less strongly organically complexed. A larger fraction of Zn occurred in DGT-labile species in the hypolimnion than it did in the surface water, probably due to a larger concentration of strong ligands in the productive surface water. DGT-labile Cd- (0.01-0.02 nM) and Pb-species (0.03-0.06 nM) were detected at very low levels. The combination of measurements of dissolved and DGT-labile species showed a decrease of Cu, Zn, Cd and Mn concentration at 2.5 m from June to August, which was probably linked to intensive sedimentation of organic matter during summer stagnation. Mixing and oxygenation of the lake in winter-spring led to an increase in dissolved and DGT-labile Ni, Zn and Cd, whereas Mn decreased in the hypolimnion.