Monitoring of labile metals in turbid coastal seawater using diffusive gradients in thin-films

Diffusive gradients in thin-films (DGT) have been investigated for in situ monitoring of labile metals in north Australian coastal seawater. Field and experimental data showed that DGT devices provided adequate detection limits, accuracy and precision for monitoring of near-pristine levels of labile Mn, Co, Cu, Cd and Pb when deployed for periods of 3 days. However, Zn could not be adequately determined due to high blank levels. The ratio of DGT-labile to 0.45 microm-filtered metal levels in natural seawater ranged from 0.44-0.63 for Cu but was close to unity for Co and Cd. Elevated levels of suspended particulate matter up to 57.3 mg l(-1) did not have an adverse effect on the performance of DGT.     

Trace metal speciation during dry and wet weather flows in the Tama River, Japan, by using diffusive gradients in thin films (DGT)

The labile species of Ni, Cu, Zn, Cd, and Pb in the Tama River, an urban river in Tokyo, Japan, were measured using diffusive gradients in thin films (DGT) method under dry and wet weather conditions, and the results were compared with total dissolved concentrations in hourly samples collected in parallel. A total of 10 DGT deployments were made and 251 hourly samples were collected during 2 rounds of sampling, conducted between August and October, 2006. Two types of diffusive gradients in thin films (DGT) devices-DGT-RG for labile inorganic and DGT-APA for total (inorganic and organic) labile species-were applied throughout the samplings. The proportions of metals measured by DGT, compared with the dissolved metal concentrations (filtered using a membrane of 0.5 microm pore size), were 38 +/- 5% (RG) and 45 +/- 8% (APA) for Ni and 45 +/- 22% (RG) and 53 +/- 23% (APA) for Zn. No labile Cu was detected throughout the sampling; Cu was assumed to be in stable complexed forms. Labile Pb was detected in 3 out of 10 deployments only; the rest were lower than the detection limit. Dissolved and labile Cd concentrations were below the detection limits. Three rain events encountered during the sampling periods were evaluated. Rains brought considerably higher loads of metals in dissolved form, and DGT measurements indicated that labile metal loads also increased. Selected DGT measurements were compared with the WHAM 6 speciation model and found to be similar to the model-computed results.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

Macroalgae and DGT as indicators of available trace metals in marine coastal waters near a lead–zinc smelter

The levels of Cd, Cu, Pb, and Zn were determined in the commonest species of green, red, and brown algae collected from five coastal sites in south-western Sardinia (Italy), an area with a long history of mining and smelting. The usefulness of employing Enteromorpha sp. and Padina pavonica (L.) Thivy to monitor metal pollution was evaluated, while diffusive gradients in thin films (DGT) devices were used to measure dissolved metals in seawater. Levels of Cd and Pb were high enough to be of environmental concern in the whole study area. A significant relationship was found between the content of Pb in P. pavonica and DGT-labile Pb in seawater, suggesting that gross elemental concentrations of nonessential metals such as Pb in algal tissues are apparently controlled by the abundance of dissolved metal species in the ambient seawater. The results pointed out the usefulness of using both DGT and algal methods for a better understanding of trace metal availability in coastal waters.     

Reactivity, interactions and transport of trace elements, organic carbon and particulate material in a mountain range river system (Adour River, France)

The background levels, variability, partitioning and transport of eleven trace elements-Ag, Al, As, Cd, Co, Cr, Cu, Mn, Pb, Zn and U-were investigated in a mountain range river system (Adour River, France). This particular river system displayed a turbulent hydrodynamic regime, characterized by flash-transient discharge conditions leading to fast shifts in suspended particulate matter (SPM) concentrations as high as two orders of magnitude (12 to 600 mg l(-1)). The distribution of SPM was accurately predicted with a "hysteresis" transport model, indicating that about 75% of the annual solids load was exported within 20 to 40 days. Dissolved and particulate concentrations of most trace elements were low compared to their concentrations in other reference river systems expect for Pb and Cr, associated with historical anthropogenic activities. Although dissolved and particulate metal concentrations were steady for most elements during low and average discharge conditions, significant changes were observed with increasing river discharge. The changes in trace element concentrations in the two compartments was found to induce a partitioning anomaly referred to as the particulate concentration effect. This anomaly was significant for Cr, Mn, Pb, Zn, Cu and organic carbon (p < 0.03). The processes driving this anomaly were possibly linked to the modification and/or increase of colloidal organic and inorganic vectors, suggested by the significant increase of DOC (p < 0.001) and dissolved Al concentrations (p < 0.05) during flood conditions. A complementary process linked to the influence of coarse particles of low complexation capacity and transported mainly during high discharge may also effect trace element concentrations. Annual metal fluxes transported by this river system were estimated using the hysteresis SPM model with consideration of these fate processes. Metals in the Adour River system are primarily exported into the Bay of Biscay (Atlantic Ocean).     

Distribution and accumulation of heavy metals in the sediments of Akkaya Dam,Nigde, Turkey

Twenty-one surface sediment samples were collected from Akkaya Dam. Heavy metal concentrations (Mo, Cu, Pb, Zn, Ni, Co, Mn, Fe, Cr, As, V and Cd), grain size, organic carbon and carbonate contents were studied in order to assess the extent of environmental pollution and to discuss the origin of these contaminants in sediments of dam. The sediments in the study area are mostly very fine sands. However, mud was observed in the northeast of the dam. Sediment pollution assessment was carried out using enrichment factor. The calculation of enrichment factors showed that Mo is depleted by 1.0 whereas Cu, Pb, Zn, Ni, Co, Mn, As, V, Cr and Cd are enriched by 3, 5.4, 7, 2.7, 2.2, 3.4, 42.3, 2.1, 1.8 and 7.2, respectively. Relatively high concentrations heavy metals occurred in north (textile industry area) and east (Karasu River) due to enrichment controlled by anthropogenic wastes. The results of correlation analysis show low–medium positive and negative correlations among metals, grain size, carbonate contents and organic carbon and indicate that heavy metals in sediments of the Akkaya Dam have different anthropogenic sources.     

Trace metals in sediments of Southeast Pacific Fjords, north region (42.5 degrees to 46.5 degrees S)

Analyses of trace metals in benthic sediments from selected fjords and channels between 41 degrees 30' and 46 degrees 50'S, 75 degrees -72.3 degrees W were made after the CIMAR 1 Fjords expedition co-ordinated by CONA-Chile in 1995; the metals analyzed include Ba, Cd, Co, Cr, Cu, Ni, Pb, Sr, V and Zn. The objective of this study was to establish baseline values for these metals and to compare them with similar studies made in comparable, but geographically distinct, environments. Box core samples were collected at 35 stations and metal analysis was by inductively coupled plasma-atomic emission spectroscopy (ICP-AES) using the MESS-2 reference standard. The ranked abundance by metal was Ba > Sr > V > Zn > Cr > Cu approximately Ni approximately Pb > Co > Cd; these metals were not homogenous across the region and coefficients of variation were >10%. There were distinct groupings by metal and geographical area including the fjords, basins and channels. Depth profiles of the metal concentrations also varied spatially, e.g. Guafo, Laguna San Rafael, Moraleda, Corcovado, Quitralco, and Jacaf were predominantly homogeneous with depth profiles indicative of pristine systems experiencing few human impacts. In contrast, Aysen, Cupquelan and Puyuguapi Fjords had higher concentrations towards the surface, indicating elevated inputs in recent years. No major differences in metal content of the sediments were observed when compared with values from comparable natural systems in the northern hemisphere. Principal component analysis (PCA) grouped several seemingly isolated locations as having the same metal signature and indicated the pattern of dispersion across the region.     

Heavy metal concentration in sediment, benthic, benthopelagic, and pelagic fish species from Musa Estuary (Persian Gulf)

The concentration of Cd, Co, Cu, Ni, and Pb was measured in sediment and three fish species collected from Musa Estuary, Persian Gulf. The concentration order of heavy metals in sediment were Ni > Co > Cu > Pb > Cd >. Concentrations of the heavy metals in the fish were apparently different among the three species. The concentrations of Cd and Ni in fish were Johnius belangerii > Euryglossa orientalis > Liza abu, while the Co and Cu levels were L. abu > E. orientalis > J. belangerii and E. orientalis > L. abu > J. belangerii, respectively. Result of regression analysis showed that there were no significant relationships between metal concentration in fish tissues and sediment, except for Ni concentration in the J. belangerii liver. The concentrations of studied metals in fish muscle were below the permissible limits proposed by FAO, WHO, and EC.     

Heavy metals in Patella caerulea (Mollusca, Gastropoda) in polluted and non-polluted areas from the Iskenderun Gulf (Mediterranean Turkey)

The concentrations of Cd, Cu, Zn, Fe, Pb, Ni, and Co were measured in gastropod mollusks Patella caerulea in the Mediterranean area. The organisms were collected at two coastal sites in Iskenderun Gulf during winter, spring, summer, and autumn 2008. Samples of the digestive gland, gill, and muscle were analyzed for heavy metals. The aim of study is to determine heavy metal levels in tissues of P. caerulea in different locations. Tissues of P. caerulea from the polluted site showed metal concentrations appreciably higher than unpolluted organisms. The highest metal levels were registered in the digestive gland of P. caerulea. Generally, digestive gland and gills showed higher metal concentrations than muscle. The average concentrations of heavy metals analyzed exhibited the following decreasing order: Fe > Zn > Cu > Ni > Cd > Pb > Co for both stations 1 and 2. Seasonal changes in metal concentrations were observed in the tissues of P. caerulea from a polluted and an unpolluted population.     

Dissolved and particulate metals in water from Sonora Coast: a pristine zone of Gulf of California

The purpose of this study was to investigate the distribution of metals (Cd, Pb, Hg, Cu, Fe, Mn, and Zn) in dissolved and particulate fractions in seawater from Bacochibampo Bay, Northern part of Mexico. Water samples were collected from November 2004 to October 2005. Metal analysis was done by graphite furnace atomic absorption spectroscopy. Results indicated highest concentrations of dissolved Cd and Zn in the sites localized at the mouth and center of the bay. During summer and spring, the highest levels of Cd, Mn, and Fe were detected, Zn in fall, and Pb and Cu in winter and spring. Mercury was the only metal that was not found in this fraction. In particulate fraction, Fe, Hg, and Mn were the most abundant elements in all the sampling sites, followed by Zn, Cu, Pb, and Cd. The highest levels of the majority of the metals were observed in the coastline, suggesting a continental and/or urban source for these chemicals. The highest level of Cd was detected during the summer and the rest of the metals in the fall. Statistically significant correlations were observed between dissolved and particulate forms of Pb:Mn, Cu:Fe, and Cu:Mn. The mean partition coefficient values were as follows: Fe>Mn>Cu>Pb>Cd>Zn. All dissolved metal concentrations found, except Pb, were lower than EPA-recommended water quality values. The levels of dissolved metals in this study reveal low bioavailability and toxic potential. However, further toxicological and sediment chemistry studies in this area are needed for a full risk assessment.     

Characterization and source identification of airborne trace metals in Singapore

Airborne particulate trace metals have important health implications. As a consequence, their concentrations are increasingly monitored in many urban locations worldwide. In this study, fine atmospheric particles (PM(2.5)) were collected in Singapore over a period of 83 consecutive days during 2000, and analysed to determine the concentration of trace elements using ICP-MS. Altogether, eighteen airborne trace metals were quantified: Al, Ag, Ba, Cd, Cr, Co, Cu, Fe, Ga, Li, Mn, Ni, Pb, Sr, Zn, V, Si, and Ti. While Li was the least abundant trace metal with a mean concentration of 0.2 ng m(-3), Zn showed the maximum mean concentration of 279.1 ng m(-3). Calculation of enrichment factors indicated that the elements Pb, Zn, Cd, V, Ni, Cr, and Cu were enriched by factors of 30 to 5000 relative to their natural abundance in crustal soil. The extent of metal pollution in the study area was assessed by comparing the measured concentrations to those reported in the literature for a selected number of urban sites in other parts of the world. Factor analysis was used to identify the major sources affecting particulate air pollution in Singapore. The sources that contribute to the loading of trace metal-bearing aerosols in the Singapore urban atmosphere include fuel oil-fired power plants, metal processing industry, land reclamation and construction activities, municipal solid waste incinerators, and traffic emissions.     

Trace metals: Inputs, sedimentation and accumulation in San Vicente Bay, Chile

The present study deals with sediment dynamics affecting sediment-associated metal distributions in an embayment system experiencing pollution from coastal industries. Sedimentary metal content may originate from diagenetic processes of foundation rock on the bottom, allochthonous minerals from natural sources, and metals from industrial effluents along the coast. The study presents experimental estimations of quantities of metals entering the bay in industrial wastewater, measurements of metal content in particulate material captured in sediment traps, and metals distribution in surface sediments. Quantitative estimations of metals entering the system in industrial effluent showed the relation Pb Zn > Cu > Cr Ni > Cd. That of metals associated with particulate material from traps was Zn > Cr Cu > Pb > Ni > Cd and the abundance of metals in sediments was Zn > Cr > Cu > Pb > Ni > Cd. Finally, rates of bottom sediment accumulation are estimated in relation to the time of residence of water in the bay. The experimental data on sedimentation and sediment abundance were consistent with field observations on distribution and accumulation at sites of major sedimentation in this bay.     

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Studies concerning the lability and bioavailability of trace metals have played a prominent role in the search for contamination of water resources. This work describes the first application yet of the diffusive gradients in thin films technique (DGT) to the determination of the fraction of free plus labile metals in waters from the Amazon Basin. Due to the complexity of the use of DGT for samples with low ionic strength and high organic matter content (characteristic of Amazonian rivers), a new analytical procedure was developed. The method is based on the determinations of apparent diffusion coefficients (D_ap) in the laboratory, by performing deployments in samples collected in the corresponding sites of study. The D_ap thereby determined is then used for in situ measurements. The suitability of the proposed approach for determination of labile Al, Cd, Co, Cu, Mn, Ni, and Zn in the Amazon River and Rio Negro (English: Black River) was evaluated. Except for Co, Mn (in a deployment at Rio Negro), Ni and Zn (in a deployment at Amazon River), labile in situ measurements were lower or similar to dissolved concentrations, indicating suitability of the proposed approach.     

Distribution of heavy metals in the dissolved and suspended phase of the sea-surface microlayer, seawater column and in sediments of Singapore’s coastal environment

Concentrations of heavy metals were determined in the water column (including the sea-surface microlayer, subsurface, mid-depth and bottom water) and sediments from Singapore’s coastal environment. The concentration ranges for As, Cd, Cr, Cu, Ni, Pb and Zn in the seawater dissolved phase (DP) were 0.34–2.04, 0.013–0.109, 0.07–0.35, 0.23–1.16, 0.28–0.78, 0.009–0.062 and 0.97–3.66 μg L⁻¹ respectively. The ranges for Cd, Cr, Cu, Ni, Pb and Zn in the suspended particulate matter (SPM) were 0.16–0.73, 6.72–53.93, 12.87–118.29, 4.34–60.71, 1.10–6.08 and 43.09–370.49 μg g⁻¹, respectively. Heavy metal concentrations in sediments ranged between 0.054–0.217, 37.48–50.52, 6.30–21.01, 13.27–26.59, 24.14–37.28 and 48.20–62.36 μg g⁻¹ for Cd, Cr, Cu, Ni, Pb and Zn, respectively. The lowest concentrations of metals in the DP and SPM were most frequently found in the subsurface water while the highest concentrations were mostly observed in the SML and bottom water. Overall, heavy metals in both the dissolved and particulate fractions have depth profiles that show a decreasing trend of concentrations from the subsurface to the bottom water, indicating that the prevalence of metals is linked to the marine biological cycle. In comparison to data from Greece, Malaysia and USA, the levels of metals in the DP are considered to be low in Singapore. Higher concentrations of particulate metals were reported for the Northern Adriatic Sea and the Rhine/Meuse estuary in the Netherlands compared to values reported in this study. The marine sediments in Singapore are not heavily contaminated when compared to metal levels in marine sediments from other countries such as Thailand, Japan, Korea, Spain and China.     

Total and Leachable Heavy Metals in Muddy and Sandy Sediments of Egyptian Coast Along Mediterranean Sea

The assessment of marine pollution due to metals was made for surficial sediments sampled from 20 sites along Mediterranean coast of Egypt. The samples were dried, acid digested and analyzed for leachable and total heavy metal contents (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) by flame atomic absorption spectrophotometer (air–acetylene) with deuterium background correction. Evaluation of the heavy metals pollution status was carried out using enrichment factors (EFs), the effect range-low (ERL) and the effect range-median (ERM). The study showed high concentrations of Cd, Co, Pb, Ni and moderate concentrations of Cr, Cu and Mn were contaminated in the sediments of studied sites. The results of Spearman correlation, factor and cluster analysis of the heavy metals analyzed in the collected sediment were discussed. The main source of contamination is the offshore oil field and industrial wastes, which arise due to the ineffective and inefficient operation equipments, illegal discharge and lack of supervision and prosecution of offenders.     

Heavy Metals Monitoring using Bivalves from Mediterranean Sea and Red Sea

The concentrations of heavy metals (Cd, Co, Cu, Fe, Mn, Ni, Pd and Zn) were measured in the Bivalves (Modiolus auriculatus and Donax trunculus) collected from the Egyptian coasts of Mediterranean Sea and Brachiodonates sp. from the Egyptian coasts of Red Sea. The average concentrations of the heavy metals analyzed exhibited the following decreasing order: Fe > Zn > Cu > Mn > Ni > Co > Pb > Cd for both Mediterranean Sea and Red Sea. The analyses of Cd, Co, Ni, Pb, and Zn showed higher average concentrations for samples collected from Red Sea than that collected from Mediterranean Sea, while Fe, Cu and Mn showed the reverse results. Fe was used as a normalizing agent for all studied metals and exhibited presence of two locations from each of Mediterranean Sea and Red Sea have anthropogenic inputs of heavy metals. These results suggest that the coastal area in both Mediterranean Sea and Red Sea of Egypt might be considered relatively unpolluted with heavy metal.     

乌鲁木齐市冬季重污染天气下PM_(2.5)中重金属污染特征及来源解析

通过乌鲁木齐市2013年2月5日至26日一次重污染天气过程中,在6个采样点位进行细颗粒物PM_(2.5)的采集,并对其中的13种重金属(Cu、Sr、Mo、Cd、Pb、V、Cr、Mn、Fe、Co、Ni、As、Hg)含量、Mull污染指数、空间分布以及溯源进行了分析。结果显示:采样期间乌鲁木齐市重金属浓度在0.23~178 ng/m~3之间,浓度水平排序PbMnCrFeAsVCuNiSrCdMoCoHg,其中Cd、Hg、Pb、Cr、As浓度均高于乌鲁木齐市背景值和国内外其他城市水平,且Mull污染指数处于较严重的污染水平;在重金属元素浓度的空间分布上,铁招和南公园点位重金属浓度较高,31中学和市监测站相对较低。     

Interseasonal distribution and partitioning of heavy metals in subtidal sediment of Qua Iboe Estuary and associated Creeks, Niger Delta (Nigeria)

An analysis of the distribution and chemical forms of selected metals: cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb) in subtidal sediments of Qua Iboe Estuary and adjourning creeks, collected between June 2000 and January 2001, were studied using a sequential chemical extraction method. The concentration of metals in each extracted fraction was determined using inductively coupled plasma spectrometer (ICP-AES). Pb, Cd and Cu appear to be the most abundant metal in the sediments of the systems, and are predominantly associated with the residual, organic and oxidisable phases. Results indicate that there are also insignificant components that are bound to both the exchangeable and carbonates fractions. Ni is largely associated with bioavailable phases with insignificant bound to organic matter and residual fractions. In general, an insignificant component of Cd and Pb are bound to organic matter phase. Moreover, speciation results indicate that metal contamination in the ecosystems investigated primarily comes from human-mediated sources. Thus, based on index of geoaccumulation calculated, sediments of these ecosystems have been classified as uncontaminated by Cr, Cu and Ni, strongly contaminated by Pb and extremely contaminated by Cd.     

Risk assessment of trace metals in an extreme environment sediment: shallow,hypersaline, alkaline,and industrial Lake Acıgöl,Denizli, Turkey

The major and trace element component of 48 recent sediment samples in three distinct intervals (0–10, 10–20, and 20–30 cm) from Lake Ac?göl is described to present the current contamination levels and grift structure of detrital and evaporate mineral patterns of these sediments in this extreme saline environment. The spatial and vertical concentrations of major oxides were not uniform in the each subsurface interval. However, similar spatial distribution patterns were observed for some major element couples, due mainly to the detrital and evaporate origin of these elements. A sequential extraction procedure including five distinct steps was also performed to determine the different bonds of trace elements in the <?60-μ particulate size of recent sediments. Eleven trace elements (Ni, Fe, Cd, Pb, Cu, Zn, As, Co, Cr, Al and Mn) in nine surface and subsurface sediment samples were analyzed with chemical partitioning procedures to determine the trace element percentage loads in these different sequential extraction phases. The obtained accuracy values via comparison of the bulk trace metal loads with the total loads of five extraction steps were satisfying for the Ni, Fe, Cd, Zn, and Co. While, bulk analysis results of the Cu, Ni, and V elements have good correlation with total organic matter, organic fraction of sequential extraction characterized by Cu, As, Cd, and Pb. Shallow Lake Ac?göl sediment is characteristic with two different redox layer a) oxic upper level sediments, where trace metals are mobilized, b) reduced subsurface level, where the trace metals are precipitated.     

Spatial distribution of heavy metals content in soils of Amik Plain (Hatay, Turkey)

The purpose of the study was to investigate the total and bio-available contents of heavy metals (Cd, Co, Ni, and Pb) and to determine their spatial variability in the Amik Plain, Turkey. Samples of surface and subsurface soil were collected at 132 sites in the research area. All of the total metal concentrations except Ni were considerably lower than their maximum allowable concentrations. Mean available Pb concentrations at both depths were above the permissible limits, while the other metal concentrations were within the proposed limits. Semivariograms of all the total metal contents, pH, and available Ni and Pb content were best fitted to spherical models, while available Cd and Co contents were best fitted to exponential models. Block kriging was used to interpolate values at unmeasured locations, generating maps of spatial variation for each heavy metal and pH.