Controls on trace metals in urban stream sediments : implications for pollution monitoring using sediment chemistry data

Contamination of urban streams is a rising topic worldwide, but the assessment and investigation of stormwater induced contamination is limited by the high amount of water quality data needed to obtain reliable results. In this study, stream bed sediments were studied to determine their contamination degree and their applicability in monitoring aquatic metal contamination in urban areas. The interpretation of sedimentary metal concentrations is, however, not straightforward, since the concentrations commonly show spatial and temporal variations as a response to natural processes. The variations of and controls on metal concentrations were examined at different scales to increase the understanding of the usefulness of sediment metal concentrations in detecting anthropogenic metal contamination patterns. The acid extractable concentrations of Zn, Cu, Pb and Cd were determined from the surface sediments and water of small streams in the Helsinki Metropolitan region, southern Finland. The data consists of two datasets: sediment samples from 53 sites located in the catchment of the Stream Gräsanoja and sediment and water samples from 67 independent catchments scattered around the metropolitan region. Moreover, the sediment samples were analyzed for their physical and chemical composition (e.g. total organic carbon, clay-%, Al, Li, Fe, Mn) and the speciation of metals (in the dataset of the Stream Gräsanoja). The metal concentrations revealed that the stream sediments were moderately contaminated and caused no immediate threat to the biota. However, at some sites the sediments appeared to be polluted with Cu or Zn. The metal concentrations increased with increasing intensity of urbanization, but site specific factors, such as point sources, were responsible for the occurrence of the highest metal concentrations. The sediment analyses revealed, thus a need for more detailed studies on the processes and factors that cause the hot spot metal concentrations. The sediment composition and metal speciation analyses indicated that organic matter is a very strong indirect control on metal concentrations, and it should be accounted for when studying anthropogenic metal contamination patterns. The fine-scale spatial and temporal variations of metal concentrations were low enough to allow meaningful interpretation of substantial metal concentration differences between sites. Furthermore, the metal concentrations in the stream bed sediments were correlated with the urbanization of the catchment better than the total metal concentrations in the water phase. These results suggest that stream sediments show true potential for wider use in detecting the spatial differences in metal contamination of urban streams. Consequently, using the sediment approach regional estimates of the stormwater related metal contamination could be obtained fairly cost-effectively, and the stability and reliability of results would be higher compared to analyses of single water samples. Nevertheless, water samples are essential in analysing the dissolved concentrations of metals, momentary discharges from point sources in particular.

Trace metals -- a potential threat to our fishing industry

Trace metals constitute a major form of water pollutant that can adversely affect fish production. The potentially toxic metals have been identified as lead, zinc, copper, arsenic, antimony, mercury beryllium, barium, cadmium, chromium, nickel, selenium among others. Preliminary laboratory studies have been directed to the determination of traces of lead in the aquatic biota and its toxicity. There are indications that the levels reported in effluents from some of the industries may be above the tolerant limits of local fish species and organisms that make up their food. Metal pollution could become a serious problem to freshwater fisheries in the future as a result of increasing urbanization and industrialization, unless efforts are made to prevent it

Trace metals in fresh water plankton

The uptake of Cu, Zn, and Cd by fresh water plankton was studied by analyzing samples of water and plankton from six lakes in southern California. Co, Pb, Mn, Fe, Na, K, Mg, Ca, Sr, Ba, and Al were also determined in the plankton samples. Special precautions were taken during sampling and analysis to avoid metal contamination.

The relation between aqueous metal concentrations and the concentrations of metals in plankton was studied by plotting aqueous and plankton metal concentrations vs time and comparing the plots. No plankton metal plot showed the same changes as its corresponding aqueous metal plot, though long-term trends were similar. Thus, passive sorption did not completely explain plankton metal uptake.

The fractions of Cu, Zn, and Cd in lake water which were associated with plankton were calculated and these fractions were less than 1% in every case.

To see whether or not plankton metal uptake could deplete aqueous metal concentrations by measurable amounts (e.g. 20%) in short periods (e.g. less than six days), three integrated rate equations were used as models of plankton metal sorption. Parameters for the equations were taken from actual field measurements. Measurable reductions in concentration within short times were predicted by all three equations when the concentration factor was greater than 10^5. All Cu concentration factors were less than 10^5.

The role of plankton was regulating metal concentrations considered in the context of a model of trace metal chemistry in lakes. The model assumes that all particles can be represented by a single solid phase and that the solid phase controls aqueous metal concentrations. A term for the rate of in situ production of particulate matter is included and primary productivity was used for this parameter. In San Vicente Reservoir, the test case, the rate of in situ production of particulate matter was of the same order of magnitude as the rate of introduction of particulate matter by the influent stream.

Trace metals in common marine foods of the Pacific Coast

Trace metal analysis of 23 species of common Pacific Coast marine foods revealed high cadmium values for Bent-nosed clams (Macoma nasuta), Bay mussels (Mytilus edulis), Bay oysters (Osrtrea lurida), Pacific oysters (Crassostrea gigas), and Littleneck clams (Protothaca staminea). Metals were found to concentrate in the gills, heart, and visceral mass of all 10 species of bivalve mollusks examined. Swordfish (Xiphias gladius) and Salmon (Oncorhynchus tshawytscha) demonstrated the highest cadmium values for fish flesh.

Speciation of some trace metals (Fe, Cu, and Cd) in El-Mex Bay waters, Alexandria, Egypt

Surface- and bottom-water samples were collected from October 1996 to August 1997 to study levels of iron, copper, and cadmium species in their dissolved labile as well as non-labile and particulate forms in the waters of El-Mex Bay. The results showed that the non-labile concentration of the metals was generally more abundant than that of the labile form: its content reached more than 90% of the total dissolved metal for Cu and more than 80% for Fe. The particulate form was almost at the level of the labile form. The annual concentration of the trace metals of the labile form was 13 µglˉ¹ for Fe; 3µglˉ¹ for Cu, and 1.2 µglˉ¹ for Cd in the surface- and bottom-waters.

The distribution and concentration levels of trace metals in water and sediments of Lake Victoria, Kenya

The water and bottom sediments of Lake Victoria (Kenya) were analysed for A1, Fe, Mn, Zn, Pb, Cu, Cr and Cd. The total metal concentrations were determined and their mean variations and distributions discussed. The bottom lake waters showed higher concentration levels than the surface waters. The range of values (in mg/l) in the bottom and surface lake waters were as follows: Surface Waters: A1(0.08 - 3.98), Fe(0.09 - 4.01), Mn(0.02 - 0.10). Zn(0.01 -0.07), Pb(0.001- 0.007), Cu(not detected - 0.006), Cr(not detected - 0.004). Bottom Waters: A1(0.1 0 - 6.59), Fe(0.23 - 9.64), Mn(0.04 - 0.39), Zn(0.01- 0.08), Pb(0.002 - 0.009), Cu(not detected - 0.03). Cr(not detected -0.002). River mouths and shallow areas in the lake showed higher total metal concentrations than offshore deeper areas. Apart from natural metal levels, varied urban activities and wastes greatly contribute to the lake metal pollution as shown by high Pb and Zn levels in sediments, around Kisumu and Homa Bay areas. Other comparatively high values and variations could be attributed to the varied geological characteristics of the lake and its sediments. Compared to the established W.H.O (1984) drinking water standards manganese, aluminium and iron levels were above these limits whereas zinc, lead, chromium, copper and cadmium were below.

Analytical intercomparison results from the 1990 Intergovernmental Oceanographic Commission open-ocean baseline survey for trace metals: Atlantic Ocean

“Dissolved” (< 0.4 μm filtered) and “total dissolvable” (unfiltered) trace element samples were collected using “clean” sampling techniques from four vertical profiles in the eastern Atlantic Ocean on the first IOC Trace Metals Baseline expedition. The analytical results obtained by 9 participating laboratories for Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, and Se on samples from station 4 in the northeast Atlantic have been evaluated with respect to accuracy and precision (intercomparability). The data variability among the reporting laboratories was expressed as 2 × SD for a given element and depth, and was comparable to the 95% confidence interval reported for the NASS seawater reference standards (representing analytical variability only). The discrepancies between reporting laboratories appear to be due to inaccuracies in standardization (analytical calibration), blank correction, and/or extraction efficiency corrections.Several of the sampling bottles used at this station were not adequately pre-cleaned (anomalous Pb results). The sample filtration process did not appear to have been a source of contamination for either dissolved or particulate trace elements. The trace metal profiles agree in general with previously reported profiles from the Atlantic Ocean. We conclude that the sampling and analytical methods we have employed for this effort, while still in need of improvement, are sufficient for obtaining accurate concentration data on most trace metals in the major water masses of the oceans, and to enable some evaluation of the biogeochemical cycling of the metals.

Interference effects in the extraction of trace metals from estuarine waters

We have found that a commonly used complexation and solvent extraction technique (using mixed dithiocarbamates/Freon/HNO3) does not always extract Cd, Co, Cu and Ni from estuarine samples with the same efficiency as from Milli-Q water. For samples collected from the Derwent Estuary (Australia), the reduced extraction efficiency only occurred for unfiltered samples, but low extraction efficiencies were also observed for a (filtered) riverine certified reference material (SLRS-3) suggesting that the effect may be widespread. We have not been able to identify the reason for the low extraction efficiency and, although it is strongly correlated with the presence of high concentrations of suspended solids, dissolved organic matter and particulate iron, we have no experimental evidence to directly link any of these parameters to the effect. It is possible that similar effects may occur in other techniques which rely on a preconcentration step prior to analysis and that some literature values of heavy metals in estuarine waters may be low. We propose a modification of the standard complexation/solvent extraction method which overcomes these difficulties without adding significantly to the time taken for analyses.

Anodic Stripping Voltammetry at Bismuth-Coated and Uncoated Carbon Microdisk Electrodes:Application to Trace Metals Analysis in Flood Samples

This article reports on the performance of a bismuth-coated carbon microdisk electrode (BiFμE) for the determination of trace heavy metals by anodic stripping voltammetry (ASV). The BiFμE was prepared by electrodeposition of a metallic bismuth film onto the microdisk, by applying an in-situ electroplating procedure. To test the performance of the BiFμE, ASV measurements were performed on synthetic solutions containing Cd2+, Pb2+, and Cu2+ as target ions. The results indicated that cadmium and lead gave well-defined ASV peaks with no interference, and their quantitative determination could be carried out straightforwardly. In particular, linear calibration curves over the range 5.0 x 10-8-1.0 x 10-6M for both ions, and detection limits of 7.8 and 2.9 nM, for cadmium and lead, respectively, after applying a 60 sec preconcentration step, were obtained. The reproducibility was also satisfactory, the relative standard deviation (RSD) being within 2.5% for both ions. Copper, instead, gave an ASV response that. in most experimental conditions, overlapped with that of bismuth. This circumstance made the determination of copper at the BiFμE difficult. Since the latter element could be detected reliably at the uncoated carbon microdisk electrode (CμE), both BiFμE and CμE were employed, respectively, for the determination of lead and copper ions in drinking water, wine, and tomato sauce.

Properties of poly(sodium 4-styrenesulfonate)-ionic liquid composite film and its application in the determination of trace metals combined with bismuth film electrode

A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) can be effectively improved at the PSS-BMIMPF6 modified GC.

Narion/Poly(sodium 4-styrenesulfonate) mixed coating modified bismuth film electrode for the determination of trace metals by anodic stripping voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation-exchange polymers, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA-PSS/BiFE). The characteristics of GC/NA-PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltarnmetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L-1 for Cd(II) and 93 ng L-1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA-PSS/BiFE can be a reproducible and robust toot for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface-active compounds.