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.     

Gonad differential proteins revealed with proteomics in oyster (Saccostrea cucullata) using alga as food contaminated with cadmium

As mercury and lead, cadmium (Cd) is one of the highly toxic metals in both the ocean and land environments, but its toxicological mechanism in organisms including human is still unclear because of the complex toxicological pathways in vivo. Here, the alga Chlorella vulgaris were cultivated at room temperature under the stress of cadmium (1 mg L⁻¹) to obtain a toxic food, and then the contaminated food were directly supplied to oyster (Saccostrea cucullata) in seawater. After feeding with C. vulgaris contaminated with Cd (C. vulgaris-Cd), the differential proteins in the oyster gonad (OG) were effectively separated and identified with proteomic approaches. Eleven protein spots were observed to be significantly changed in the OG feeding with C. vulgaris-Cd, which seven spots of these differential proteins were down-regulated while four spots were up-regulated. These altered spots were further excised in gels and identified by a combined technique of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/TOF MS) and database searching. A portion of these differential proteins were further proofed by real-time PCR and Western blotting. The results indicate that the major functions of these differential proteins were described as follows: binding, protein translocation, catalysis, regulation of energy metabolism, reproductive function and skeleton structure. These differential proteins in part may effectively provide a few novel biomarkers for the evaluation of Cd pollution level via a food pathway for harming halobios, mammal and human health, and for understanding the complex mechanisms of Cd toxicity in vivo.     

Trace metals and organochlorines in sediments near a major ocean outfall on a high energy continental margin (Sydney, Australia)

Sewage effluent from a large ocean outfall south of Sydney, southeastern Australia, is efficiently dispersed on this high energy continental margin. An enrichment of Ag, Cu, Pb and Zn is only detectable in the fine fraction (<62.5 microm) of sediment. Ag, Co, Cu, Ni, Pb and Zn in the bulk sample correlate strongly with the mud content of surficial sediment, making an identification of the anthropogenic trace metal source difficult using total sediment analyses. The concentrations of HCB and DDE in the total sediment are also slightly elevated near the outfall. In the vicinity of the outfall, the estimated sewage component in the fine fraction of sediment, using Ag, Cu and Zn in a conservative, two-endmember physical mixing model, is <5% and is <0.25% of the total sediment. A greater anthropogenic Pb component in the fine fraction (mean: 24.8%) of surficial sediment compared to Ag, Cu and Zn may suggest a source other than sewage to Sydney continental margin sediments.     

The use of sedimentary metal data in predictive modelling of estuarine contamination,assessment of environmental condition and pollutant source identification (Narrabeen Lagoon,Sydney, Australia)

Environmental Science and Pollution Research - Narrabeen Lagoon is recognized as an Intermittently Closed and Open Lake or Lagoon (ICOLL) and is the largest coastal lagoon (2.2&nbsp;km2) in the...     

Di- and tribromoindoles in the common oyster (Crassostrea virginica)

The sources/origins, fate and impacts of naturally occurring organobromine compounds in the marine environment are largely unknown. Soft tissue composites of the common oyster (Crassostrea virginica) collected from coastal Georgia (USA) were analyzed for organobromines by gas chromatography. Three simple bromoindoles (BIs)--two dibromo- and one tribromo congener--were detected and their molecular formulas elucidated by electron and negative chemical ionization GC-MS. Semi-quantitative estimates of BI concentrations in these samples using GC-ECD indicated that oysters sampled in November 1999 contained 5-10 times more BIs than those sampled in August 2000 and March 2001. Although their bromine substitution patterns are presently unknown, this first ever report of bromoindoles in C. virginica, a prolific and important commercial and ecological species, underscores its potential utility as a bioindicator of organobromines in the coastal marine environment.     

Atmospheric dispersion of pollutants in Sado estuary (Portugal) using biomonitors

Epiphytic lichen transplants and aerosol samplers were put together in the Setubal area, Portugal. They were analysed by Instrumental Neutron Activation Analysis (INAA) and Proton Induced X-ray Emission (PIXE). The lichen dataset pointed out nine factors. No relevant differentiation was found towards different positioning of the lichens. T-transplants were delayed towards F-transplants, and for both after 3 and 6 months the accumulation was as much as at 9th month. Direct rainfall protection favoured accumulation for a few elements only. The elemental accumulation in lichens depended more on temperature and humidity conditions. Aerosol data towards lichen database showed an excellent correlation.     

On-road ultrafine particle concentration in the M5 East road tunnel,Sydney, Australia

The human health effects following exposure to ultrafine (<100 nm) particles (UFPs) produced by fuel combustion, while not completely understood, are generally regarded as detrimental. Road tunnels have emerged as locations where maximum exposure to these particles may occur for the vehicle occupants using them. This study aimed to quantify and investigate the determinants of UFP concentrations in the 4 km twin-bore (eastbound and westbound) M5 East tunnel in Sydney, Australia. Sampling was undertaken using a condensation particle counter (CPC) mounted in a vehicle traversing both tunnel bores at various times of day from May through July, 2006. Supplementary measurements were conducted in February, 2008. Over three hundred transects of the tunnel were performed, and these were distributed evenly between the bores. Additional comparative measurements were conducted on a mixed route comprising major roads and shorter tunnels, all within Sydney. Individual trip average UFP concentrations in the M5 East tunnel bores ranged from 5.53 × 10⁴ p cm^?3 to 5.95 × 10⁶ p cm^?3. Data were sorted by hour of capture, and hourly median trip average (HMA) UFP concentrations ranged from 7.81 × 10⁴ p cm^?3 to 1.73 × 10⁶ p cm^?3. Hourly median UFP concentrations measured on the mixed route were between 3.71 × 10⁴ p cm^?3 and 1.55 × 10⁵ p cm^?3. Hourly heavy diesel vehicle (HDV) traffic volume was a very good determinant of UFP concentration in the eastbound tunnel bore (R² = 0.87), but much less so in the westbound bore (R² = 0.26). In both bores, the volume of passenger vehicles (i.e. unleaded gasoline-powered vehicles) was a significantly poorer determinant of particle concentration. When compared with similar studies reported previously, the measurements described here were among the highest recorded concentrations, which further highlights the contribution road tunnels may make to the overall UFP exposure of vehicle occupants.     

Metal accumulation in the smooth toadfish, Tetractenos glaber, in estuaries around Sydney, Australia

This study determined the metal levels in sediments and tissues of a common estuarine fish, Tetractenos glaber (smooth toadfish), from two metal contaminated and two reference estuaries near Sydney, Australia. Metal levels were highest in sediments and fish from contaminated estuaries. Gonads contained the highest metal levels followed by muscle, gill and liver. Metal accumulation was gender-dependant (e.g. male gonads were >20 times higher in As than females; female gills were >30 times higher than males for Pb). Cadmium, Pb and Ni levels in fish tissues reflected sediment levels, indicating sediment and/or dietary metal uptake. Levels of As, Co, Cd & Pb in gills showed similar patterns to other tissues, suggesting that metals may have been taken up by gills through contaminated water. Similar metal patterns in tissues and sediments suggest more than one uptake pathway. This study indicates that multiple factors influence metal accumulation in fish.     

Mercury biomethylation assessment in the estuary of Bilbao (North of Spain)

The relationship between the microbial methylation of mercury and the microbial activities in sediments and water collected from the estuary of Bilbao (North of Spain) was studied in three different sampling points and in two different seasons. Three different cultures were prepared with a sediment slurry to distinguish between biotic and abiotic methylation pathways and the variations of the methylmercury concentration and the variations of the population of total number of bacteria (TDC), anaerobic heterotrophic bacteria (AHB), sulphate-reducing bacteria (SRB) and Desulfovibrio were measured. From this work, it can be concluded that the variation of MeHg concentrations is a result of the methylation/demethylation processes in the sediments, and that the abiotic processes have a negligible contribution to those processes. According to the statistical analysis of the results (partial least squares analysis) a significant statistical correlation was established between methylmercury and the SRB counts.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

Effects of metals on condition and reproductive output of the smooth toadfish in Sydney estuaries, south-eastern Australia

This study determined the condition and reproductive output of a common estuarine toadfish, Tetractenos glaber, in two metal contaminated and two reference estuaries near Sydney, Australia. Female toadfish from metal contaminated estuaries were smaller and younger than in reference estuaries; however, it could not be resolved whether these differences were due to direct effects of metal contamination or differences in nutritional value of prey. Lipid content in liver and gonad tissues was inversely related with levels of As, Pb, Cd and Co in sediment. In contrast, protein content in liver, gonad and muscle tissues was positively related to sediment levels of Ni and Co. Increased levels of Pb in gonads were associated with decreased oocyte diameter and density. This suggests a reduction in egg size and fecundity, which ultimately may lead to a decline in female reproductive output. Changes in fish health and reproduction caused by chemical pollutants may alter fish population and community structure.     

Flame retardants, surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary (The Netherlands)

Sediment and mysids from the Scheldt estuary, one of the largest and most polluted estuaries in Western Europe, were analyzed for a number of contaminants that have been shown to possess endocrine-disrupting activity, i.e. organotins, polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), nonylphenol ethoxylates (NPE) and transformation products, nonylphenol (NP) and nonylphenol ether carboxylates (NPEC). In addition, in vitro estrogenic and androgenic potencies of water and sediment extracts were determined. Total organotin concentrations ranged from 84 to 348 ng/g dw in sediment and 1110 to 1370 ng/g dw in mysid. Total PBDE (excluding BDE-209) concentrations ranged from 14 to 22 ng/g dw in sediment and from 1765 to 2962 ng/g lipid in mysid. High concentrations of BDE-209 (240-1650 ng/g dw) were detected in sediment and mysid (269-600 ng/g lipid). Total HBCD concentrations in sediment and mysid were 14-71 ng/g dw and 562-727 ng/g lipid, respectively. Total NPE concentrations in sediment were 1422 ng/g dw, 1222 ng/g dw for NP and 80 ng/g dw for NPEC and ranged from 430 to 1119 ng/g dw for total NPE and from 206 to 435 ng/g dw for NP in mysid. Significant estrogenic potency, as analyzed using the yeast estrogen assay, was detected in sediment and water samples from the Scheldt estuary, but no androgenic activity was found. This study is the first to report high levels of endocrine disruptors in estuarine mysids.     

Metal accumulation in the greentail prawn, Metapenaeus bennettae, in Sydney and Port Hacking estuaries, Australia

Metal concentrations of the inshore greentail prawn, Metapenaeus bennettae, and surface sediments from locations within Sydney estuary and Port Hacking (Australia) were assessed for bioaccumulation and contamination. The current study aimed to assess metal concentrations in prawn tissue (tail muscle, exoskeleton, hepatopancreas and gills), relate whole body prawn tissue metal concentrations to sediment metal concentrations and animal size, as well as assess prawn consumption as a risk to human health. Metal concentrations were highest in sediment and prawns from contaminated locations (Iron Cove, Hen and Chicken Bay and Lane Cove) in Sydney estuary compared with the reference estuary (Port Hacking). Concentrations in sediments varied considerably between sites and between metals (As, Cd, Cr, Cu, Ni, Pb and Zn), and although concentrations exceeded Interim Sediment Quality Guideline-Low values, metals (As, Cd, Cr, Cu, Ni, Pb and Zn) were below Australian National Health and Medical Research Council human consumption guidelines in prawn tail muscle tissue. Metal concentrations in prawn tail muscle tissue were significantly different (p?≤?0.05) amongst locations for Pb, Zn and Cd, and metal concentrations were generally highest in gills tissue, followed by the hepatopancreas, exoskeleton and tail muscle. The exoskeleton contained the highest Sr concentration; the hepatopancreas contained the highest As, Cu and Mo concentrations; and the gills contained the highest Al, Cr, Fe and Pb concentrations. Concentrations of Pb, As and Sr were significantly different (p?≤?0.05) between size groups amongst locations.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in Great Barrier Reef (Australia) dugongs (Dugong dugon)

Fat tissue samples from dugong (Dugong dugon) carcasses stranded at three sites along the Great Barrier Reef were analysed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Relatively high levels of PCDDs were determined in all three dugongs. In particular OCDD, the PCDD/F congener that is usually considered the least bioavailable of all 2,3,7,8 substituted congeners, was found at levels higher than reported for other marine mammals. Tissue accumulation of PCDDs by dugongs may be a consequence of sediment and/or seagrass ingestion during feeding, microbial biotransformation of PCDD precursors in the animal's hindgut or, alternatively, the possession of a selective degradation capability for PCDFs.     

Polybrominated diphenyl ethers (PBDEs) in human milk from Australia

Polybrominated diphenyl ethers (PBDEs) are flame retardants added to a multitude of products to reduce flammability. PBDEs have been widely detected and quantified in biota and humans in many industrialised countries from the Northern Hemisphere. However data concerning the levels of these compounds in the Australian population and environment remain limited. The objectives of this study were to determine PBDE concentrations and congener profiles in Australian human milk and compare this to concentrations found in other countries. Pooled human milk samples obtained from mothers residing in 12 regions of Australia were analysed by HRGC/HRMS for 18 PBDE congeners. In total, 157 human milk samples collected in 2002 and 2003 were divided into 17 regional pools. PBDEs were detected in all pools of human milk from Australia. The mean+/-standard deviation and median summation operatorPBDE concentrations were 11.1+/-3.2 and 11.0 ng g(-1) lipid, respectively with a range of 6.1-18.7 ng g(-1) lipid. The congener profile was dominated by BDE-47 followed by BDE-99, -100, -153, -154 and -183. Regional differences were evaluated, but no trends were observed. The data suggest regional differences are likely to be small if they exist at all. The concentrations of PBDEs found in Australian human milk were lower than those reported from North America but higher than those reported from Europe and Asia. Our results suggest that the exposure pathways which contribute to the PBDE body burden in the Australian population require a better understanding in order to determine future policy regarding their use and disposal.     

The recovery of populations of dogwhelks suffering from imposex in the Firth of Forth 1987-1997/98

The impact of tributyltin (TBT) contamination on dogwhelk (Nucella lapillus) populations was assessed at 33 sites in the Firth of Forth, UK, during spring 1997 and summer 1998. The sex ratio of the animals; the ratio of juveniles to adults; the degree of imposex, as determined by the relative penis size index (RPSI); and the total tin concentration in a sample of dogwhelk tissue were used as measurements of TBT impact on dogwhelk populations. These data were compared with data from a similar survey carried out at the same sites in the Firth of Forth in 1987 (Bailey, S.K., Davies, I.M., 1988. Tributyltin contamination in the Firth of Forth (1975-1987). Science of the Total Environment 76, 185-192.) before restrictions were introduced on the use of TBT. The results demonstrate a general recovery in dogwhelk populations from the impact of TBT at the majority of the sites studied, although at six of the sites, the RPSI value remains high enough to suggest breeding problems in the population. It is suggested that large vessels are responsible for localised cases of imposex within the Firth of Forth.     

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.     

Geochemical behavior of metals and metalloids in an estuary affected by acid mine drainage (AMD)

The Tinto and Odiel rivers in southwest Spain drain the world’s largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH?<?3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average?=?48 μg L^?1) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.