Short-term variability of dissolved trace element concentrations in the Marne and Seine rivers near Paris

The concentrations of dissolved trace elements (Li, B, Mn, Cu, As, Rb, Sr, Mo, Cd, Ba, Pb) in the Marne and Seine rivers in the Paris urban area were monitored over a 2-year period. The resulting data indicated moderate contamination of waters by the most toxic elements (Cu, As, Cd and Pb). The River Marne upstream and the River Seine downstream of the city of Paris displayed similar concentrations. However higher fluxes of trace elements were observed in the Seine than in the Marne due to their different discharges. Li, B, Rb, Sr and Ba concentrations were correlated with river discharge and concentrations were higher during high river flow. This was interpreted as a dilution by discharge from a major natural or anthropogenic source. Mn, Cu, Mo, Cd and Pb concentrations were not correlated with discharge. Dissolved Mn, Cu and Cd increased rapidly in summer, whereas the concentration of Mo decreased. These variations were attributed to redox processes. During summer when the dissolved oxygen concentrations decrease, Mn, Cu, Cd and Pb are released into solution whereas Mo is immobilised. Like metals, variations in arsenic contents were not linked with discharge. Its similarity with phosphate distribution suggests similar controls involving phytoplankton uptake and release from sediments through organic matter mineralization.     

The geochemistry of Seine River Basin particulate matter: distribution of an integrated metal pollution index

Spatial analysis (1994-2001) and temporal trends (1980-2000) for particulate-associated metals at key stations in the Seine River Basin have been determined using a new metal pollution index (MPI). The MPI is based on the concentrations of Cd, Cu, Hg, Pb and Zn, normalized to calculated background levels estimated for each particulate matter samples for four fractions (clays and other aluminosilicates, carbonates, organic matter, and quartz). Background levels ascribed to each fraction were determined from a specific set of samples collected from relatively pristine areas in the upper Seine basin and validated on prehistoric samples. The unitless MPI is designed to vary between 0 for pristine samples to 100 for the ones extremely impacted by human activities and to assess the trends of general metal contamination and its mapping. Throughout the Seine basin, MPI currently range from 1 to 40, but values exceeding 100 have been found in periurban streams and the Eure tributary. Based on the MPI spatial distribution, the Seine River Basin displays a wide range of anthropogenic impacts linked to variations in population density, stream order, wastewater discharges and industrial activities. Correlations between the MPI and other trace elements indicate that anthropogenic impacts also strongly affect the concentrations of Ag, Sb, and P, marginally affect the concentrations of Ba, Ni, and Cr, and appear to have little effect on the concentrations of Li, Be, V, Co, and the major elements. Temporal MPI trends can also be reconstituted from past regulatory surveys. In the early 1980s, MPI were 2-5 times higher than nowadays at most locations, particularly downstream of Greater Paris where it reached levels as high as 250 (now 40), a value characteristic of present Paris urban sewage. The exceptional contamination of the Seine basin is gradually improving over the last 20 years but remains very high.     

Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005)

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y.     

Pollution status of the Indus River,Pakistan, through heavy metal and macronutrient contents of fish,sediment and water

Concentrations of Ag, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn and Hg, together with Na, K, Ca and Mg in 19 species of fish captured from the Indus River, Pakistan, are estimated by the atomic absorption method. Corresponding data for sediment and water from 11 sites along the down-stream route of the river are also reported. Mercury and arsenic concentrations were high (3.920 and 3.072 μg/g, respectively) in the muscle of fish from Guddu barrage as compared with those from other sites. Hetroptirus fossilus showed maximum concentrations of Ag, Cu and Pb in its muscle as compared with other fish. Labeo calbasu from Guddu barrage showed highest As concentration at 3.072 μg/g. Mystus vitatus from Chashma barrage contained maximum cadmium concentration at 0.990 μg/g. Several other fish exhibited elevated levels of metals along the downstream route of the river, a trend exhibited also by the elevated metal contents of sediment and water at Guddu and Lloyd barrages. The study indicated a gross pollution of the sediment and water at various locations of the river, e.g. As (7.452 μg/g) in sediment from Lloyd barrage, Hg (5.710 μg/g) in sediment from Jinnah barrage, Pb (2.709 μg/g) in sediment from Guddu barrage and Mn (0.038 μg/g) in water from Lloyd barrage. The macronutrients showed an inverse relationship with trace metals. Hetroptirus fossilus could be used as indicator species for Ag, Cu and Pb.     

Concentration and fate of trace metals in Mekong River delta

In the Mekong River delta and its associated coastal zone trace elements concentrations (Cd, Cu, Ni and Pb) were measured in the dissolved phase (DP) during dry (March 1997) and wet (October 1997) seasons. As, Co, Cr, Ni, Pb, and Al were also measured in suspended matter (SM) and total and organic carbon, trace elements (Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and macro elements in superficial sediments (S). Trace metal concentrations in DP and SM during the contrasting hydrological conditions were generally found within the range observed for uncontaminated environment. The average DP concentrations (nM) in the river for March and October are: Cd 0.03 and 0.09, Cu 15 and 14, Ni 7.8 and 8.4, Pb 0.51 and 0.50, respectively. In general there is no significant difference between the concentrations observed during dry and wet season. The evolution of the DP trace metal concentration in the surface water within the salinity gradient suggests no noticeable exchange between the particulate and dissolved phase. This result is in good agreement with those observed in most plume structures studied so far. The average concentrations in the SM (microg/g) (March, October) at the river end-member are: As (24; 11), Co (17; 9), Cr (49; 29), Ni (32; 18), Pb (42; 19) and Al (113,000; 67,000), respectively. All trace elements show higher concentrations in March than in October, with an average increase of two times. This is essentially related to grain size effect since smaller particles were supplied during dry season. These differences are not reflected in the mixing zone, which integrates the seasonal variations. The concentration of major elements (C total, C organic, Si, Al, Ca, K, Fe, Mg, Ti), trace elements (Pb, Zn, Cu, Ni, Mn, Cr, Cd, Hg) in superficial sediments, show similar values during the two seasons and does not show any important variation with depth, indicating either a very fast sedimentation rate and/or the absence of any significant contamination.     

Geochemical signals and source contributions to heavy metal (Cd, Zn, Pb, Cu) fluxes into the Gironde Estuary via its major tributaries

Daily measurements of water discharges and suspended particulate matter (SPM) concentrations and monthly sampling for trace element analyses (Cd, Zn, Pb and Cu) were conducted from 1999 to 2002 on the Garonne, Dordogne and Isle Rivers, the three main tributaries of the Gironde Estuary, France. Dissolved and particulate Cd, Zn, Pb and Cu concentrations in the Isle River were generally higher than those in the Garonne River, despite the known historical polymetallic pollution affecting the Lot-Garonne River system. Even if the relatively high dissolved metal concentrations in the Isle River may be of importance for the local ecosystem, metal inputs into the estuarine and coastal zones are mainly controlled by fluvial transport via the Garonne River. Characteristic element concentration ratios (e.g., Zn/Pb) in SPM and stream sediments from the Dordogne and Isle Rivers suggest two different metal source areas with distinct geochemical signals. Low Zn/Pb ratios (<8) and low Cu/Pb ratios (<0.8) have been attributed to upstream source zones in the Massif Central, featuring various ore deposits and mining areas. High Zn/Pb ratios were assigned to downstream sources (e.g., vineyards), partly explaining high Zn and Cu concentrations and high Cu/Pb ratios (>0.8) in SPM. Although SPM derived from the upstream parts of the studied watersheds may greatly contribute to the observed fluvial metal transport (up to approximately 80% for Pb), the results suggest that intensive agriculture also considerably influences gross metal (e.g., Zn, Cu) fluxes into the Gironde Estuary. Relative contributions of upstream and downstream source zones may vary from one year to another reflecting hydrological variations and/or reservoir management. Monitoring fluxes and identifying distinct geochemical signals from source areas in heterogeneous watersheds may greatly improve understanding of contaminant transport to the coast.     

Residual effects of lead and zinc mining on freshwater mussels in the Spring River Basin (Kansas, Missouri, and Oklahoma, USA)

Concentrations of selected trace elements in surface water and fluvial sediment were investigated as possible factors limiting the distribution and abundance of freshwater mussels in the Spring River Basin, a 6600 km(2) watershed overlapping a former Pb and Zn mining and ore processing district in the central USA. Mussel taxa richness surveys and supporting physical habitat assessments were performed in 23 stream reaches dispersed throughout the basin and above and below former mining sites. Quantitative mussel density surveys were performed in the Spring River at one upstream reference location and one downstream location. Concentrations of 16 trace elements in the soft tissues of mussels and Asian clams (Corbicula fluminea) were determined at most survey sites. Comparable analyses were performed on surface water samples collected during base flow and peak flow synoptic surveys and sediment samples collected during base flow periods. Sites on the Spring River immediately upstream of heavily mined areas supported at least 21-25 species of mussels, whereas sites near the lower terminus of the river yielded evidence of 6-8 extant species. Between the upper and lower quantitative survey sites, mean mussel and clam densities declined by 89% and 97%, respectively. Tributary reaches below heavily mined areas lacked evident bivalve communities and contained concentrations of Cd, Pb, and Zn that continually or sporadically exceeded hardness-dependent water quality criteria and consensus-based sediment quality guidelines (probable effect concentrations). In less contaminated stream reaches supporting bivalves, concentrations of Cd, Pb, and Zn in mussels and clams were correlated spatially with the levels occurring in surficial sediment (0.50 < or = tau < or = 0.64, p < or = 0.03). In non-headwater perennial stream reaches, sediment Cd, Pb, and Zn levels were related inversely to mussel taxa richness (-0.80 < or = tau < or = -0.64, p < or = 0.004). Metal contaminant burdens in mussels and clams fluctuated measurably in association with variable stream flow conditions and accompanying changes in surface water and sediment chemistry. Concentrations of Cd, Pb, and Zn in mussels approximately paralleled the levels measured in composite clam samples (0.74 < or = tau < or = 0.79, p<0.001), implying C. fluminea could serve as a possible surrogate for native mussels in future metal bioaccumulation studies. Overall, streams draining heavily mined areas exhibited depauperate (or fully extirpated) mussel assemblages and correspondingly elevated concentrations of Cd, Pb, and Zn in water, sediment, and bivalve tissue. Other evaluated environmental chemistry parameters, and physical habitat conditions assessed at the stream reach scale, demonstrated little general relationship to the degraded status of these assemblages. We conclude that pollution attributable to former mining operations continues to adversely influence environmental quality and impede the recovery of mussel communities in a large portion of the Spring River Basin.     

Heavy metals in Lake Balaton: water column, suspended matter, sediment and biota

During the period 1999-2002, five sampling cruises have been carried out on Lake Balaton to assess trace metal distribution in the lake and to identify major sources. Eighteen elements, including Cr, Co, Ni, Cu, Zn, Cd, Pb (trace metals) and Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, S, Sr (major metals), were determined in one or more of the lake's compartments. Lower trace metal concentrations in rainwater were observed in June and February 2000, while much higher levels were present in September 2001 (during a storm event) and in snow (February 2000). In the Northern and Western parts of the lake, especially at the inflow of river Zala and the locations of the yacht harbours, metal concentrations were higher in almost all compartments. Because the lake is very shallow, storm conditions also change significantly the metal distributions in the dissolved and particulate phases. The Kis-Balaton protection system located on Zala river functions very efficiently for retaining suspended particulate matter (SPM; 72% retention) and associated metals. Metal concentrations in surface sediments of the lake showed a high variability. After normalisation for the fine sediment fraction, only a few stations including Zala mouth appeared to be enriched in trace metals. In zooplankton, Zn seemed to be much more elevated compared to the other trace metals. Based on the molar ratios of the trace metals in the various compartments and input flows of the lake, several trends could be deduced. For example, molar ratios of the trace metals in the dissolved and solid (suspended particulate matter and sediments) phases in the lake are fairly similar to those in Zala River.     

Relationship between ore deposits in river catchments and geochemistry of suspended particulate matter from six rivers in southwest France

Here we present original data on the geochemical composition of fluvial particulate matter transported by the rivers of the Adour/Garonne basin, which drains one-fifth of the French land surface. Suspended particulate matter from the six main rivers in the basin, sampled at 'normal' flow and during a flood, is compared in terms of: grain size; particulate organic carbon; Fe; Mn; and trace element concentrations (e.g. Zn, Cd, Pb, Cu, Mo, Sn, Ni, Co, Cr, V, As, Hg, U, Th, W, Au, Ag, Ta). Three of the six studied rivers (Garonne, Dordogne and Isle Rivers) are the main tributaries of the Gironde estuary (southwest France), known for Cd pollution. The Adour and Gaves Rivers enter the Adour Estuary and the Charente River reaches the ocean by the Charente Estuary. Our data show, that Cd (and Zn) are not the only trace elements of eco-toxicological relevance transported into the Gulf of Biscay by these six rivers. Potentially toxic elements (e.g. As, Sn, U, Cu, Ag) show elevated concentrations in river particulates entering the estuaries, compared to world average concentrations [Martin and Whitfield, 1983, The significance of the river input of chemical elements to the oceans. In: C.S. Wong, E. Boyle, K.W. Bruland, J.D. Burton, E.D. Goldberg (editors), Trace Metals in Sea Water, Plenum, New York: pp. 265-296]. Comparing SPM sampled during 'normal' discharge and flood, the basin shows a distinct trace element composition of SPM mostly related to ore deposits in the upper basins (Massif Central and Pyreneans). This geochemical signal is partly masked during floods due to changes in grain size, but also due to increased erosion of the lower parts of the basins. This study proves pumping/centrifugation to be the most appropriate sampling/separation technique (recovery, representativity, contamination) by comparing different methods of SPM recovery.     

Metals and selenium in the liver and bone of three dolphin species from South Australia, 1988-2004

Metal and selenium concentrations (wet weight) were determined in the liver (Cd, Hg, Pb, Zn, Cu and Se) and bone (Pb and Cd) of common dolphins (Delphinus delphis, N=71) and bottlenose dolphins (Tursiops truncatus, N=12, and Tursiops aduncus, N=71) stranded or by-caught in South Australia from 1988 to 2004. Differences in metal burdens existed between species, stranding location, and relative age. T. aduncus had the greatest mean tissue burdens of liver Pb (0.45 mg/kg), Cd (6.45 mg/kg), Hg (475.78 mg/kg), Se (178.85 mg/kg) and Zn (93.88 mg/kg) and bone Pb (2.78 mg/kg), probably reflecting their coastal habitat and benthic prey. Mean Cu was highest in T. truncatus (21.18 mg/kg). Bone Cd was measured only in T. aduncus and averaged 0.05 mg/kg. Stranding location impacted metal burdens. Dolphins from Spencer Gulf had higher mean levels of liver Pb (0.39 mg/kg) while Gulf St Vincent dolphins had greater liver Hg (444.64 mg/kg), liver Se (163.12 mg/kg), and bone Pb (2.85 mg/kg). This may be due to high anthropogenic inputs of Pb and Hg into Spencer Gulf and Gulf St Vincent respectively. Liver Cd, Hg, Se and Pb increased with age in all species while Cu decreased with age, in keeping with previous studies. Se and Hg were positively correlated. The possibility that metallothioneins are driving observed correlations between Zn, Cd, Hg and Cu are discussed. Future research must investigate the toxicological consequences of the metal concentrations reported.     

How polluted is the Yangtze river? Water quality downstream from the Three Gorges Dam

The concentrations of major anions and cations, nitrogen and phosphorus, dissolved and particulate trace elements, and organic pollutants were determined for the middle and lower reaches of the Yangtze River (Changjiang) from below the Three Gorges Dam (TGD) to the mouth at Shanghai in November 2006. The concentration of dissolved inorganic phosphate (DIP) was constant at a low level of 6-8 microgP/L, but the concentration of nitrate (NO(3)(-)) approximately doubled downstream and was closely correlated with K(+). This translated to a daily load of well over 1000 t of dissolved inorganic nitrogen (DIN) at Datong. The average concentrations of dissolved Pb (0.078+/-0.023 microg/L), Cd (0.024+/-0.009 microg/L), Cr (0.57+/-0.09 microg/L), Cu (1.9+/-0.7 microg/L), and Ni (0.50+/-0.49 microg/L) were comparable with those in other major world rivers, while As (3.3+/-1.3 microg/L) and Zn (1.5+/-0.6 microg/L) were higher by factors of 5.5 and 2.5, respectively. The trace element contents of suspended particles of As (31+/-28 microg/g), Pb (83+/-34 microg/g), and Ni (52+/-16 microg/g) were close to maximum concentrations recommended for rivers by the European Community (EC). The average concentrations of Cd (2.6+/-1.6 microg/g), Cr (185+/-102 microg/g), Cu (115+/-106 microg/g), and Zn (500+/-300 microg/g) exceeded the EC standards by a factor of two, and Hg (4.4+/-4.7 microg/g) by a factor of 4 to 5. Locally occurring peak concentrations exceed these values up to fourfold, among them the notorious elements As, Hg, and Tl. All dissolved and particulate trace element concentrations were higher than estimates made twenty years ago [Zhang, J., Geochemistry of trace metals from Chinese river/estuary systems: an overview. Estuar Coast Shelf Sci 1995; 41: 631-658.]. The enormous loads of anthropogenic pollutants disposed to the river were diluted by the large water discharge of the Yangtze even during the lowest flow resulting in the relatively low concentration levels of trace elements and organic pollutants observed. We estimated loads of e.g. As, Pb and Ni to the East China Sea to be about 4600 kg As d(-1), 3000 kg Pb d(-1), and 2000 kg Ni d(-1). About 6000 t d(-1) of dissolved organic carbon (DOC) was delivered into the sea at the time of our cruise. We tested for 236 organic pollutants, and only the most infamous were found to be barely above detection limits. We estimated that the load of chlorinated compounds, aromatic hydrocarbons, phenols, and PAHs were between 500 and 3500 kg d(-1). We also detected eight herbicides entering the estuary with loads of 5-350 kg d(-1). The pollutant load, even when at low concentrations, are considerable and pose an increasing threat to the health of the East China Sea ecosystem.     

Organochlorine pesticides, polychlorinated biphenyls and trace elements in wild European sea bass (Dicentrarchus labrax) off European estuaries

Polychlorinated biphenyls (PCBs) and organochlorine pesticides like dichloro-diphenyl-trichloroethane (DDTs), hexachlorocyclohexanes (HCHs), aldrin, dieldrin and trace elements (Cd, Cu, Se, Pb, Zn and Hg) were analysed in the muscle of European sea bass (Dicentrarchus labrax) sampled in Atlantic coastal regions near several important European river mouths (Gironde, Charente, Loire, Seine and Scheldt). High contamination levels were measured in the muscles of European sea bass sampled in the coastal regions near those river mouths (e.g. Σ ICES PCB = 133-10,478 μg kg^− 1 lw and Hg = 250-2000 μg kg^− 1 dw).The Scheldt and the Seine are still among the most contaminated estuaries in Europe. Each region presented their specific contamination patterns reflecting different sources due to the input of the respective rivers. As fish and fishery products are the main contributors of the total dietary intake of organochlorinated pollutants, regular consumption of European sea bass with the reported contamination levels may represent a significant exposure route for the general human population.     

Trace element concentrations in hair of healthy Chinese centenarians

Trace element concentrations, as indicators of micronutrient status of healthy centenarians, have not been widely analyzed. This study aimed to assess trace element concentrations in the hair of healthy centenarians. The effects of gender and age on element concentrations were also investigated. Eleven trace elements (Al, Ba, Cd, Cr, Cu, Fe, Mo, Pb, Se, Sr and Zn) in the scalp hair of 107 healthy Chinese centenarians were examined. The overall reference values (RVs) in mg/kg for the hair concentrations of trace elements in centenarians were as follows: Al, 14.95; Ba, 2.68; Cd, 0.06; Cr, 0.59; Cu, 6.21); Fe, 19.37; Mo, 0.50; Pb, 4.64; Se, 0.37; Sr, 4.84; and Zn, 154.37. Data analysis found that only Cu and Zn concentrations show a normal distribution, and there is no significant difference between males and females in any element except Zn. However, the levels of Al, Cd, Cr, Fe, Mo, Pb decrease and the levels of Ba, Cu, Se, Sr, Zn increase with age in the centenarian cohort. Results also revealed that sufficient Zn and Se concentrations as well as low exposure to heavy metals pollution contribute to the longevity of centenarians. The results imply the possibility of manipulating trace element concentrations, especially Zn and Se concentrations in tissues, as a means for therapeutic modality in geriatric disease.     

Health risk assessment of heavy metal exposure to street dust in the zinc smelting district, Northeast of China

Heavy metal contamination in the street dust due to metal smelting in the industrial district of Huludao city was investigated. Spatial distribution of Hg, Pb, Cd, Zn and Cu in the street dust was elucidated. Meanwhile, noncancer effect and cancer effect of children and adults due to exposure to the street dust were estimated. The maximum Hg, Pb, Cd, Zn and Cu contents in the street dust are 5.212, 3903, 726.2, 79,869, and 1532 mg kg^− 1, and respectively 141, 181, 6724, 1257 and 77.4 times as high as the background values in soil. The trends for Hg, Pb, Cd, Zn and Cu are similar with higher concentrations trending Huludao zinc plant (HZP). The exponential equation fits quite well for the variations of Pb, Cd, Zn and Cu contents with distance from the pollution sources, but not for Hg. The biggest contribution to street dust is atmospheric deposition due to metal smelting, but traffic density makes slight contribution to heavy metal contamination. According to the calculation on Hazard Index (HI), in the case of noncancer effect, the ingestion of dust particles of children and adults in Huludao city appears to be the route of exposure to street dust that results in a higher risk for heavy metals, followed by dermal contact. The inhalation of resuspended particles through the mouth and nose is almost negligible. The inhalation of Hg vapour as the fourth exposure pathway to street dust is accounting for the main exposure. Children are experiencing the potential health risk due to HI for Pb larger than safe level (1) and Cd close to 1. Besides, cancer risk of Cd due to inhalation exposure is low.     

Selenium in soils,spermatophytes and bryophytes around a Zn-Pb smelter,New South Wales,Australia

Blood and serum samples from 372 15-year-old adolescents were collected in two cities in Sweden and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The objective was to (1) determine the levels of 13 elements in blood and serum from the teenagers; and (2) for each element, investigate the correlation between the concentrations in blood and serum. The concentrations in blood and serum were generally in line with that usually reported for the essential elements Co, Cu, Zn and Se, and generally low for the 'non-essential' elements Cd, Hg, Pb. The median concentrations were in blood and serum, respectively: of Co 0.31 and 0.48 microg/l, Cu 0.92 and 1.0 mg/l, Zn 6.1 and 0.99 mg/l, Se 110 and 100 microg/l, Rb 2.8 and 0.24 mg/l, Hg 1.1 and 0.44 microg/l, Pb 16 and 0.33 microg/l. The median concentration of W in blood was <0.2 microg/l (below the detection limit) and in serum 0.087 microg/l. The median concentrations of Cd, Rh, Pd, Pt and Tl were below the detection limits. Statistically significant correlations were found between the concentrations in blood and serum for Co, Cu, Zn, Se, Rb, W, Hg and Pb. The levels presented in this study constitute baseline levels or levels generally not exceeded in adolescents for 13 elements, including essential, ubiquitous toxic, and rare elements.     

Estuarine capacity in removal of trace metals from contaminated river water, Southern Caspian Sea

In the present investigation, the flocculation of dissolved Cd, Cu, Ni, Pb, Mn and Zn with initial concentrations of 1, 2.5 and 5 mg/L in Tadjan River water during mixing with the Caspian Sea water has been studied in order to determine estuarine capacity to remove dissolved metals in the accidental contamination of the river. The flocculation process was investigated on a series of mixtures with salinities ranging from 0.1 to 11 p.p.t. The flocculation rates were indicative of the nonconservative behaviour of Cd, Cu, Ni, Pb, Mn and Zn during estuarine mixing. The order of the final flocculation rate of dissolved metals at 1, 2.5 and 5 mg/L of initial metal concentrations in the river water is as follows:Cu (99%)>Cd (95%)>Zn (88%)>Mn (85%)>Pb (83%)>Ni (73%), Cu(95.6%)>Pb(92.4%)>Cd (90%)>Zn(88.4%)>Mn (81.6%)>Ni(78.8%) and Cd (100%)>Cu(88%)>Ni (85.2%)>Pb (84%)>Zn (83.2%)>Mn (81.2%), respectively. The results also revealed that removal of dissolved metals is not influenced by pH changes and precipitation processes. The flocculation rates revealed that the overall dissolved metal pollution loads may be reduced to about 70% up to about more than 90% during estuarine mixing of Tadjan River with the Caspian Sea water.     

Distribution and behavior of trace metals in the sediment and porewater of a tropical coastal wetland

Vertical profiles (0-30 cm below surface) of four trace metals-Cadmium (Cd), Chromium (Cr), Lead (Pb) and Zinc (Zn)-in the sediment and sediment porewater of an ecologically important intertidal mudflat in the Mai Po and Inner Deep Bay Ramsar Site were thoroughly studied over a period of 10 months (from March 1999 to January 2000). Two surveys, one in summer and another in winter, involving a total of eight sampling stations were conducted to study the seasonal variation of the remobilization characteristics of these trace metals in the mudflat sediment. The range of depth averaged concentration of these trace metals in the mudflat sediment was: 0.3-0.8 microg/g (Cd); 9.8-91.0 microg/g (Cr); 7.3-69.1 microg/g (Pb); and 39.5-192.0 microg/g (Zn), while that in the sediment porewater was: 0.3-121.1 microg/l (Cd); 3.0-2704.1 microg/l (Cr); 2.6-105.6 microg/l (Pb); and 32.6-4238.3 microg/l (Zn). In general, levels of dissolved trace metals in the sediment porewater were much higher in the summer than in the winter while their concentrations in the sediment were more or less the same throughout the year. Enrichment of Cd, Pb and Zn in the sediment porewater of the upper oxic layer and that of Cr in the oxic-sub-oxic boundary was generally observed. Regions in the vicinity of the Mai Po mangroves and the river mouths of Shenzhen River and Shan Pui River were found to be hotspots of trace metal pollution. Benthic diffusive fluxes of trace metals from the mudflat sediment were also estimated. Of the four trace metals, cadmium showed the greatest tendency toward remobilization from the sediment phase to the more bio-available porewater phase.     

Assessment of heavy metal levels in Almendares River sediments--Havana City, Cuba

The Almendares River watershed covers a large portion of Havana, Cuba and is centrally important to both recreational and other activities in the region. In order to assess current water quality conditions prior to planned remediation efforts, the spatial distribution of six heavy metals and other compounds were determined in river sediments at fifteen sampling stations in the watershed. Metal concentrations in sediments ranged from 86.1 to 708.8 for Zn, 39.3 to 189.0 for Pb, 71.6 to 420.8 for Cu, 84.4 to 209.7 Cr, 1.5 to 23.4 for Co, and 1.0 to 4.3 for Cd microg/g dry weight sediment. Calculated enrichment factors (EF; measured metal versus background mineral conditions) were almost always greater than 1.0, suggesting significant anthropogenic impact on metal levels in the river. The highest EF values were seen immediately below Cotorro (EF>10 for Pb, Cu, and Cd), a suburban town that has an active secondary smelter, and below the largest municipal landfill in Havana (EF>10 for Pb, Cu, Cd, and Zn). Further, three sampling stations had multiple metals at concentrations higher than probable effects concentrations (PEC), implying possible local ecotoxicological impacts. Finally, sequential extractions of the sediments indicated that heavy metals were largely associated with the organic fraction, and it was estimated that up to 62% of metals in the sediments would be susceptible to release back into the water column if hydraulic or other changes occurred in the river. These data are being used to prioritize decisions related to the remediation of the river system.     

Accumulation of heavy metals and As in wetland birds in the area around Doñana National Park affected by the Aznalcollar toxic spill

The impact of the spill from the mine in Aznalcollar (Seville, Spain) on waterfowl in the Do?ana National Park is assessed. The concentrations of Cu, Pb, Cd, Zn nd As in the liver and eggs of 16 species of waterfowl found dead in the Park between April and November 1998 were determined. The highest levels were found for Zn, followed by Cu, Pb, Cd and As. The main parameters related to the accumulation of these elements in the waterfowl studied were species and trophic level. The other variables studied--distance from the spill, days of exposure, sex, size, and age--are important, although this depends on the element studied. Zn and Cu from the spill have entered the food chain of the aquatic birds studied, but Cd, Pb and As have not. There is currently no evidence to suggest that the trace element concentrations measured have reached toxic levels.     

Heavy-metal pollution of sediments from Szczecin Lagoon and the Gdansk Basin, Poland

Concentrations of Al, V, Mn, Fe, Co, Cu, Ni, Zn, Sr, Mo, Cd, Sb, Pb, Th, U, REE, Na, K, Mg, Ca, Si, P, S, Ti, Cr and Ba were determined in the <63 microm fraction of bottom sediments of the Szczecin Lagoon and the Gdansk Basin, Baltic Sea, by ICP-MS, ICP-AES and XRF methods. Sediment samples from the Szczecin Lagoon displayed somewhat higher concentrations of P, Mn, Cr, Cu and possibly Cd, Pb and Zn in those collected in October 1997 after the exceptional flooding of the Oder River than in those collected in December 2000. The data suggest that the flood resulted in the enhanced transport of redox-sensitive and anthropogenic elements in the Oder River and their subsequent redeposition mainly in the western part of Szczecin Lagoon. The sediments of the Szczecin Lagoon also appear to be the most polluted with heavy metals within the Polish Exclusive Economic Zone (EEZ) of the Baltic Sea. Cd, Pb, Zn and Cu are anthropogenically enriched in top layers of sediment cores from the Gdansk Basin, but the decrease of these elements with depth in the core is not systematic. The rare earth element (REE) patterns in sediments from both these areas do not appear to have been greatly modified during transport from their source into the southern Baltic. Factor analysis (FA) of the compositional data shows that sediments from Szczecin Lagoon can be divided into three main groups depending on their composition. It is concluded that clay minerals and organic matter build aggregates and flocs, which effectively concentrate trace metals and sink down to form a 'fluffy layer'.