Measurement of environmental trace-metal levels in Mediterranean coastal areas with transplanted mussels and DGT techniques

Mussels (Mytilus galloprovincialis) and diffusive gradients in thin films (DGT) devices were deployed together for three one-month periods in coastal waters of Sardinia (Italy), in order to assess the levels of Cd, Cu, Ni, and Pb in areas differently affected by anthropogenic activities. DGT devices were more sensitive than mussels in detecting differences in metal concentrations between sites, while interpretation of the biomonitoring data revealed difficulties related to the biotic and abiotic factors that can influence the measurements. Regression analysis showed a significant correlation between Cd and Pb concentrations measured in the mussel tissues and bioavailable metal levels in seawater. Moreover transplanted mussels did not accumulate Cu and Ni following pre-exposure, although DGT showed significant concentrations of bioavailable forms of these metals in seawater. The results provided an estimate of the water quality with respect to dissolved metals and pointed out the usefulness of a combination of biomonitoring and DGT techniques for a better understanding of trace metal availability in coastal waters.     

Measurement of environmental trace-metal levels in Mediterranean coastal areas with transplanted mussels and DGT techniques

Mussels (Mytilus galloprovincialis) and diffusive gradients in thin films (DGT) devices were deployed together for three one-month periods in coastal waters of Sardinia (Italy), in order to assess the levels of Cd, Cu, Ni, and Pb in areas differently affected by anthropogenic activities. DGT devices were more sensitive than mussels in detecting differences in metal concentrations between sites, while interpretation of the biomonitoring data revealed difficulties related to the biotic and abiotic factors that can influence the measurements. Regression analysis showed a significant correlation between Cd and Pb concentrations measured in the mussel tissues and bioavailable metal levels in seawater. Moreover transplanted mussels did not accumulate Cu and Ni following pre-exposure, although DGT showed significant concentrations of bioavailable forms of these metals in seawater. The results provided an estimate of the water quality with respect to dissolved metals and pointed out the usefulness of a combination of biomonitoring and DGT techniques for a better understanding of trace metal availability in coastal waters.     

Trace metal distributions in Saint John Harbour sediments

The concentration and areal distribution of selected trace metals (Cu, Zn, Pb, Cd, Mo, Ni, Mn and Hg) in surficial sediments of Saint John Harbour, New Brunswick, Canada, were studied to determine the extent of anthropogenic input and to estimate the effects of dumping dredged material in the outer harbour. Hg and Cd are of especial concern, since the disposal of dredge material containing these two elements is regulated under the Ocean Dumping Control Act.The concentrations of all metals are low: Cu 16, Zn 53, Pb 24, Cd 0.16, Mo 3, Ni 16, Mn 296 and Hg 0.04 μg g^?1. Hg and Cd levels in sediments are well below the permissible limits of 0.75 and 0.6 μg g^?1, respectively, set by the Ocean Dumping Control Act.The mean concentrations of trace elements are similar to the low mean values in the unpolluted Bay of Fundy. There is an overall decline in concentrations of metals in the sediments from the inner to the outer harbour. Comparison of the metal levels in the sediments from different areas within the harbour indicate that there is a detectable anthropogenic input in the Courtenay Bay area. Trace metal levels at the dumpsite are significantly lower than in the Courtenay Bay area, where the bulk of the dredged material originates.     

SWASV speciation of Cd, Pb and Cu for the determination of seawater contamination in the area of the Nicole shipwreck (Ancona coast, Central Adriatic Sea)

The study reports for the first time on the heavy metal contamination of the waters surrounding a shipwreck lying on the sea floor. Square wave anodic stripping voltammetry has been used for a survey of the total and dissolved Cd, Pb and Cu contents of the seawater at the site of the sinking of the Nicole M/V (Coastal Adriatic Sea, Italy). Results show that the hulk has a considerable impact as regards all three metals in the bottom water, especially for the particulate fraction concentrations, which increased by factors of ∼9 (Cd), ∼3 (Pb) and ∼5 (Cu). The contaminated plume extended downstream for about 2 miles. Much lower contamination was observed for dissolved bottom concentrations; nevertheless Pb (0.56 ± 0.03 nmol/L) is higher than the Italian legal limits established for 2015 and Cd (0.23 ± 0.03 nmol/L) is very close the limit of Cd will be exceeded if the hulk is not removed.     

Scavenging of heavy metals from particulates by brown seaweed

Concentrations of Cu, As, Pb, Zn and Ag (but not Cd, Co, Fe, Mn and Hg) in the tissues of benthic algae (Fucus vesiculosus) correlate significantly with concentrations in sediment. Metals which complex most strongly with algal tissues show the strongest correlations of algal tissue and sediment. Scavenging these metals from particulates may be an important source of uptake by the algae. If so, concentrations of Cu, As, Pb, Zn and Ag in algal tissues may not be good indicators of concentrations of these metals in solution.     

Contamination characteristics of heavy metals in wetland soils along a tidal ditch of the Yellow River Estuary, China

Surface soils (0–20 cm) were collected from along a tidal ditch of the Yellow River Estuary in August of 2007. Samples were subjected to a total digestion technique before they were analyzed for total concentrations of As, Cr, Cd, Cu, Ni, Pb, Zn, P and S in order to investigate heavy metal contamination levels in wetland soils nearby the tidal ditches and their main sources. Results showed that the mean concentrations of these heavy metals except for As and Cd were lower than the Class I criteria. Nearly all sampling sites showed lower contamination levels for As and Cd, while no contamination levels for other heavy metals. Cr, Cu, and Ni mainly originated from parent rocks, and Pb and As might originate from tidal seawater and oil field pollution, respectively; while Cd and Zn mainly originated from parent rocks and tidal seawater. Most of heavy metals showed significant correlations with total concentrations of P and S, however, no significant correlations were observed between them and soil pH, slat and soil organic matter.     

MELIMEX,an experimental heavy metal pollution study: Regulation of trace metal concentrations in limno-corrals

In three limno-corrals of the MELIMEX project the transport paths of the trace metals Cu, Zn, Cd, Hg and Pb and the reaction of the systems on increased metal loads were investigated. The metal balances lead to the conclusion that the biomass is the main factor responsible for the regulation of trace metal concentration. The observed sequence of relative residence times of the trace metals can be described with a steady-state model. Additional metal load decreases the ability of the limnic system to lower the metal concentration. The production of phytoplankton and its assimilation capacity for metals are reduced leading to relatively higher metal concentrations in the lake.     

Sponges as sentinels: patterns of spatial and intra-individual variation in trace metal concentration

If sponges are to be effective biomonitors we require a better understanding of the spatial scales over which metals vary in these organisms. We determined how concentration of Cd, Zn, Cu, Pb, Hg and Se varied over four spatial scales for two common estuarine sponge species in the Sydney region. We examined variability with a fully nested sampling design; between coastal lakes, within coastal lakes, between sponges and within sponges. Calculation of variance components confirmed that 'within-sponge' variation in Cd, Zn, Cu, Pb and Se concentrations were low (1-14%) relative to the two largest spatial scales (49-98%) examined. In contrast, Hg concentrations exhibited marked variability 'between-sponges' and were below detection at one location. There was little evidence that sponge size was a good predictor of metal concentration. Taken together, these outcomes confirm that fragments of these sponges could be successfully transplanted and therefore show promise as biomonitors of metal contamination.     

Heavy metal concentrations during storm events in a rehabilitated industrialized catchment

Water quality data collected on a fortnightly or monthly basis are inadequate for assessment and modelling of many water quality problems as storm event samples are underrepresented or missed. This paper examines the stormflow dynamics of heavy metals (Pb, Cu, Cd and Zn) in the Nant‐y‐Fendrod stream, South Wales, which has been affected by 250 years of metal smelting, followed by 35 years of landscape rehabilitation measures. For storm events of contrasting (very dry and very wet) antecedent conditions in May 2000 and February 2001, respectively, temporal changes in streamwater heavy metal concentrations above and below an in‐line flood detention lake are analysed. At the upstream site, peaks in total metal concentration were recorded on the rising limb for Pb (0·150 mg l^?1) and Cu (0·038 mg l^?1) but on the falling limb for Zn (1·660 mg l^?1) and Cd (0·006 mg l^?1) in the summer 2000 storm event, yielding clockwise and anticlockwise hysteretic loops respectively. In contrast, metal concentrations, although high throughout the winter storm event, were diluted somewhat during the storm peak itself. The Pb and Cu appear to be supplied by quickflow processes and transported in close association with fine sediment, whereas Zn and Cd are delivered to the channel and lake by slower subsurface seepage in dissolved form. In the winter 2001 event, antecedent soil moisture and shallow groundwater levels were anomalously high and seepage sources of dissolved metals dominated. Downstream of the lake, Pb and Cu levels and suspended sediment were high in the summer storm, but low in the winter storm, suggesting retention with deposition of fine sediment in the lake during the latter. In the winter storm, Zn and Cd levels were higher downstream than upstream of the lake, perhaps because of additional seepage inputs from the surrounding slopes, which failed to have an impact during summer. An understanding of the complex interplay of antecedent soil moisture and the dynamics of subsurface seepage pathways in relation to the three‐dimensional distribution of sources is important in modelling heavy metal fluxes and levels in contaminated urban catchments. Copyright © 2003 John Wiley & Sons, Ltd.     

Concentration of 7 Heavy Metals in Sediments and Mangrove Root Samples from Mai Po, Hong Kong

Concentration of 7 heavy metals, Zn, Fe, Cu, Cr, Cd, Pb and Ni in mudflat sediments, mangrove root sediments and root tissues of Acanthus ilicifolius, Aegicerus corniculatum and Kandelia candel from the Mai Po Nature Reserve, Northwest Hong Kong, were measured. Metal concentrations in the upper 0–10 cm of the sediment cores from the mudflat were 4–25% higher than those found in the bottom 21–30 cm. Relative Topsoil Enrichment Index approximated 1.0 for all the metals. Mudflat sediment concentrations of Fe, Ni, Cr, Cd and Cu were greater than those found in the mangrove sediments. Except for Fe, concentrations of the other 6 heavy metals were more elevated in the mangrove root sediments than in the corresponding root samples. Higher concentration factors for Zn, Fe and Cu may indicate bioaccumulation. Mean metal concentrations in both mudflat and mangrove sediments decreased in the order Fe > Zn > Pb > Ni > Cu > Cr > Cd. Mangrove root tissues also showed the same pattern except that Pb > Cu > Ni     

Distribution and ecological risk assessment of some heavy metals in coastal surface sediments along the Red Sea,Egypt

The ecological risk assessment for Al,Zn,Cu,Ni,V,Pb,Cd,and Hg in surface sediment collected from the Egyptian Red Sea coast was evaluated using the Geo-accumulation Index(I_(geo)).Sediment Enrichment Factor(SEF) and Potential Ecological Risk Index(PERI) methods.The predominant heavy metal,aluminum,showed high concentrations along both of Aqaba Gulf(4378.8 ± 2554.1 μg/g) and southern part of the Red Sea(2972.8 + 1527.5 μg/g).while it recorded the lowest concentration in Suez Gulf(829.7 ± 398.2 μg/g).The determined heavy metal concentrations had the order of Al Zn -Ni V Pb Cu Cd Hg.The statistical analyses showed some correlations among the heavy metals contents.Several international sediment quality guidelines were used to estimate the quality of the collected sediments.Interestingly,the recorded average heavy metals concentrations were lower than those of the permissible contents for sediment quality guidelines.The Geo-accumulation index calculations(I_(geo)) proved that the investigated region could be classified as an unpolluted area.Sediment Enrichment Factor(K_(SEF)) study showed high values in Suez Gulf region.The single pollution index analysis of heavy metals in the sediments(C~i_f) indicated that Al,Zn,V,and Pb were of natural origin,while Ni,Cd and Hg were seriously affected by human activities.Interestingly,amongst,all the determined heavy metals,Cd and Hg gave moderate ecological risk indicators.     

Field validation, in Scotland and Iceland, of the artificial mussel for monitoring trace metals in temperate seas

The artificial mussel (AM), a novel chemical sampling device, has been developed for monitoring dissolved trace metals in marine environments. The AM consists of Chelex-100 suspended in artificial seawater within Perspex tubing and enclosed with semi-permeable polyacrylamide gel at both ends. To validate the field performance of the AM in temperate waters, we deployed AMs alongside transplanted blue mussels Mytilus edulis in coastal environments in Scotland (Holy Loch, Loch Fyne, Loch Striven and Millport) and Iceland (Reykjavikurh?fn, Gufunes, South of thornerney, Hofsvik, Hvalfj?rethur and Sandgerethi) for monitoring trace metals. While uptake patterns of Cd between the AM and M. edulis were highly comparable, discrepancies were found in the accumulation profiles of the other metals (Cu, Cr, Pb and Zn), in particular Zn. Nonetheless, the AMs gave a better resolution to accurately reveal the spatial difference in dissolved metal contamination when compared with M. edulis. AMs complement the use of mussels since AMs indicate dissolved metals in seawater, whereas uptake by mussels indicates a mixture of dissolved and particulate metals. Our results also indicated that historical metal exposure of the transplanted M. edulis could significantly confound their metal concentrations especially when the deployment period was short (i.e. <34d). This study suggested that the AM can overcome problems associated with variable biological attributes and pre-exposure history in the mussel, and provides a standardized and representative time-integrated estimate of dissolved metal concentrations in different marine environments.     

Dissolved and particulate trace metals in a Scottish sea loch: an example of a pristine environment?

In the near pristine environment of a silled fjord on the west coast of Scotland samples were taken for the determination of dissolved and particulate trace metals (Fe, Mn, Cu, Ni, Cd, Zn and Pb), together with nutrient and hydrographic data, during 19 surveys carried out over a year. An indication of the pristine nature of the environment are the low concentrations of dissolved silicon, phosphate and nitrate which are considerably lower than those of coastal waters which are subject to larger anthropogenic burdens. Distributions of dissolved Cu, Ni and Cd were found to broadly reflect conservative mixing of freshwater and seawater with both end members having similar concentrations. The concentration of dissolved Cu and Ni in seawater entering upper Loch Linnhe (Cu 0.28 μg l⁻¹; Ni 0.26 μg l⁻¹) was consistent with the 1:1 conservative mix of Irish Sea water and North Atlantic surface water predicted from radio-caesium tracer experiments (Mackay & Baxter, 1985). Atmospheric input of trace metals to upper Loch Linnhe appeared to be a relatively minor term in the mass balance relative to fluvial inputs. Values of distribution coefficients Kd were similar to those previously reported for the coastal environment. Iron showed the strongest affinity for the suspended sediments; with particulate percentages of the total load usually greater than 80%. Lead and Mn showed a similar strong affinity to the particle phase. For Cu, Ni and Zn the mass of the element in the dissolved phase was generally greater than that in the particulate fraction. Cadmium, was least associated with the particles, with typically greater than 90% existing in the dissolved phase.     

乌梁素海大气重金属沉降入湖通量初步估算

重金属元素以大气颗粒物为载体,最终以沉降的方式进入湖泊水体,会引起湖泊的重金属污染.为调查大气沉降对乌梁素海重金属污染的贡献,于2013年7月1日至30日围绕乌梁素海进行大气沉降样品采集,分别测定Cu、Zn、Pb、Cd、Cr、Hg、As 7种重金属元素的含量,并在此基础上估算7月大气重金属沉降通量及入湖量.结果表明,乌梁素海重金属元素大气沉降通量大小依次为:ZnPbCuCrAsHgCd.结合社会调查情况及数据分析显示,大气微粒携带重金属借助风力迁移,较大的沉降通量出现在主风向的下风向区域,说明风向是影响乌梁素海大气重金属沉降通量的主要因素之一.排干输入与大气沉降方式下的乌梁素海重金属入湖量比较发现,大气沉降是除排干输入外湖泊的另一重要重金属污染源.Zn、Pb、Cu、Cr、As、Hg、Cd等重金属元素月入湖量分别为10.6、1.04、1.02、0.833、0.342、0.00514、0.00281t/月.通过估算底泥重金属增量来评价大气沉降对湖泊重金属的贡献表明,大气Hg、Zn、Pb、Cu、As、Cd、Cr等重金属沉降对湖泊贡献率分别为46.4%、44.7%、14.1%、12.0%、8.48%、4.75%、4.03%.     

Trace metals associated with deep-sea tailings placement at the Batu Hijau copper–gold mine,Sumbawa, Indonesia

The Batu Hijau copper–gold mine on the island of Sumbawa, Indonesia operates a deep-sea tailings placement (DSTP) facility to dispose of the tailings within the offshore Senunu Canyon. The concentrations of trace metals in tailings, waters, and sediments from locations in the vicinity of the DSTP were determined during surveys in 2004 and 2009. In coastal and deep seawater samples from Alas Strait and the South Coast of Sumbawa, the dissolved concentrations of Ag, As, Cd, Cr, Hg, Pb and Zn were in the sub μg/L range. Dissolved copper concentrations ranged from 0.05 to 0.65 μg/L for all depths at these sites. Dissolved copper concentrations were the highest in the bottom-water from within the tailings plume inside Senunu Canyon, with up to 6.5 μg Cu/L measured in close proximity to the tailings discharge. In general, the concentrations of dissolved and particulate metals were similar in 2004 and 2009.     

Effects of 12 years' operation of a sewage treatment plant on trace metal occurrence within a Mediterranean commercial sponge (Spongia officinalis, Demospongiae)

The present field study uses Spongia officinalis for assessing trace metals occurrence in time and space within Mediterranean rocky communities. Nine sites were selected in the Marseille area for studying spatial trends in 12 metal concentrations. Long term changes in 8 metal concentrations were assessed at sites that had been sampled before and 12 years after the opening of a treatment plant. Spongia officinalis highly concentrated all the trace metal surveyed excepted Hg and Cd. The overall contamination level registered provided a classification of the study sites which is congruent with that given by other studies on pollutant accumulation in neighbouring sandy-bottoms or benthic assemblages. Among the metals studied, Fe, Pb, Cr are those that best highlighted a pollution gradient. In the present study, only Cd concentration did not vary in space. Except for Ni, all pollutant concentrations clearly decreased between 1984 and 1999. This very impressive decrease in heavy metal concentrations within the Marseille area represents an indisputable evidence of the improvement of the seawater quality resulting from 12 years' operation of the Marseille sewage plant. Moreover, the significant decrease also recorded in the reference population at Port-Cros might reflect an overall improvement in the seawater quality of the NW Mediterranean.     

Untersuchungen über die Beeinflussung der planktischen Photosynthese durch anorganische Metallsalze im eutrophen Alpnachersee und der mesotrophen Horwer Bucht

The effects on phytoplankton photosynthesis of inorganic metal salts HgCl₂, CuSO₄, Cd(NO₃)₂, ZnCl₂ and Pb(NO₃)₂ were studied over monthly intervals. In experiments with individual metals, phytoplankton photosynthesis was not adversely affected if the concentration increase above background levels did not exceed 10^?9 mole Hg/l, 5·10^?9 mole Cu/l, 2·10^?8 mole Cd/l, 5·10^?8 mole Zn/l and 2·10^?7 mole Pb/l, respectively. However when the concentration was increased by 5·10^?10 mole Hg/l+5·10^?9 mole Cu/l+5·10^?9 mole Cd/l+5·10^?8 mole Zn/l+5·10^?8 mole Pb/l photosynthesis was significantly reduced, due to a synergetic effect of the combined metals. The influence of phytoplankton density, pH-value concentration of calcium, dissolved organic nitrogen and allochthonous debris on heavy metal toxicity was investigated. Changes in phytoplankton composition are believed to the main reason for the seasonal variation in the toxic effects of heavy metals.     

Space-time variations of river water chemistry in RF southern Far East

Concentrations and seasonal variations of water chemistry, including dissolved and particulate forms of Fe, Mn, Zn, Cu, Pb, Cd, and Ni in rivers of Primorskii Krai are determined. It is shown that, unlike the macrocomposition, the effect of hydrological regime on the concentration of dissolved metal forms is controversial and depends on anthropogenic load, watershed landscapes, and pH variations. Elevated concentrations of dissolved metal forms are recorded in the beginning of spring flood and during low-water period. Beyond the limits of local impact of wastewater, the concentrations of dissolved forms of Cu, Zn, Ni, Pb, and Cd in river waters of the region insignificantly differ from the clearest rivers of the World.     

The distributions of particulate heavy metals and its indication to the transfer of sediments in the Changjiang Estuary and Hangzhou Bay,China

Particulate heavy metals (Cu, Pb, Cd) were measured following intensive sampling in June and October 1994 at 70 stations in the Changjiang Estuary and Hangzhou Bay, China. In the study area, particulate Cu and Pb have a similar level that is higher than the concentration of particulate Cd. Cu, Pb and Cd concentrations in suspended sediments are higher than those in bed load. In the middle of Hangzhou Bay, heavy metal concentrations in suspended sediments and bed load are similar. This may be the result of the frequent exchange between them, which is due to the strong dynamic condition. A negative relationship was observed between concentrations of heavy metals in bed load and bulk density. Fine-grained sediments were the main carriers of heavy metals. Sedimentary dynamics dominate the fate of heavy metals in these sites. The distributions of metals (especially Cu) in suspended sediments can indicate the transfer of sediments in this area.     

Metals contamination along the watershed and estuarine areas of southern Bohai Sea,China

Distributions and magnitude of metals in water, sediment and soil collected from the watershed and estuarine areas of southern Bohai Sea, were investigated. The largest dissolved concentrations of As, Cu and Zn in water were 347.70, 2755.00, 2076.00 μg/L, respectively, much higher than corresponding drinking water guidelines. The greatest concentrations of Cu, Zn, Cr, Ni, Pb, As and Cd in sediments were 1462.2, 1602.17, 196.43, 67.15, 63.54, 73.86 and 1.41 mg/kg, dw, respectively. The mean concentrations of Cu, Ni, Cd, Zn, Cr, Pb and As in soils were 24.67, 24.73, 0.14, 64.75, 56.52, 25.12 and 9.34 mg/kg, dw, respectively. Land use was confirmed to be an important factor of influence on soil metal concentrations. Metal contents along the watershed of Jie River were significantly greater than in other locations. The detection of metals in relatively high concentrations from different environmental matrices in this region indicates the necessity of further studies.