An evaluation of trace metal distribution, enrichment factors and risk in sediments of a coastal lagoon (Ria de Aveiro, Portugal)

This paper describes a sediment survey undertaken to unravel patterns of distribution and dispersion of trace metals in an Iberian Peninsula northwestern coastal lagoon (Ria de Aveiro). Cadmium, lead, chromium, copper and zinc were analyzed in bottom sediments. Geochemical normalization is performed and two different regression models for each metal versus aluminum are tested and compared using the respective enrichment factors (EF), an estimation of the relative importance of anthropogenic contributions to the studied sediments. Mean sediment quality guideline quotients (mSQGQ) are used to evaluate sediment quality and associated potential risk to biota with effects range low as empirical sediment quality guideline (SQG) in the basis for mSQGQ calculation. Additionally, the geoaccumulation index is calculated to compare studied sediment levels to global baseline levels. The application of SQGs revealed insufficient characterization capability, especially when contrasted to EF calculated from the regression methods. These pointed a mildly enriched system with localized “hot spot” areas. Therefore, it can be considered that bottom sediments in the Ria de Aveiro system are in their majority unpolluted, zinc being the only metal of concern, presenting enrichment in all four main channels. The major rivers outlets (Caster, Antuã, and Vouga) constitute point sources, thus presenting potential risk for biota. Yet, the strong tidal influence creates a damping effect by efficiently redistributing sediment bound metals.

Influence of medium range transport of particles from nucleation burst on particle number concentration within the urban airshed

An elevated particle number concentration (PNC) observed during nucleation events could play a significant contribution to the total particle load and therefore to the air pollution in the urban environments. Therefore, a field measurement study of PNC was commenced to investigate the temporal and spatial variations of PNC within the urban airshed of Brisbane, Australia. PNC was monitored at urban (QUT), roadside (WOO) and semi-urban (ROC) areas around the Brisbane region during 2009. During the morning traffic peak period, the highest relative fraction of PNC reached about 5% at QUT and WOO on weekdays. PNC peaks were observed around noon, which correlated with the highest solar radiation levels at all three stations, thus suggesting that high PNC levels were likely to be associated with new particle formation caused by photochemical reactions. Wind rose plots showed relatively higher PNC for the NE direction, which was associated with industrial pollution, accounting for 12%, 9% and 14% of overall PNC at QUT, WOO and ROC, respectively. Although there was no significant correlation between PNC at each station, the variation of PNC was well correlated among three stations during regional nucleation events. In addition, PNC at ROC was significantly influenced by upwind urban pollution during the nucleation burst events, with the average enrichment factor of 15.4. This study provides an insight into the influence of regional nucleation events on PNC in the Brisbane region and it the first study to quantify the effect of urban pollution on semi-urban PNC through the nucleation events. © 2012 Author(s).

Monitoring phase behavior of sub- and supercritical CO2 confined in porous fractal silica with 85% porosity

Phase behavior of CO2 confined in porous fractal silica with volume fraction of SiO2 φs = 0.15 was investigated using small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) techniques. The range of fluid densities (0<(FCO2)bulk<0.977 g/cm3) and temperatures (T=22 °C, 35 and 60 °C) corresponded to gaseous, liquid, near critical and supercritical conditions of the bulk fluid. The results revealed formation of a dense adsorbed phase in small pores with sizes D<40 A° at all temperatures. At low pressure (P <55 bar, (FCO2)bulk <0.2 g/cm3) the average fluid density in pores may exceed the density of bulk fluid by a factor up to 6.5 at T=22 °C. This “enrichment factor” gradually decreases with temperature, however significant fluid densification in small pores still exists at temperature T=60°C, i.e., far above the liquid-gas critical temperature of bulk CO2 (TC=31.1 °C). Larger pores are only partially filled with liquid-like adsorbed layer which coexists with unadsorbed fluid in the pore core. With increasing pressure, all pores become uniformly filled with the fluid, showing no measurable enrichment or depletion of the porous matrix with CO2.

Heavy metals in the sediments of Northern Moreton Bay, Queensland, Australia

This project was the first comprehensive assessment of heavy metals to be conducted in the sediments of Northern Moreton Bay since the 1970s and found that shipping and shipping related activities contributed significantly to the level of sediment contamination in the area. The study was also used to develop and test new methods of assessing heavy metal sediment quality.

Use of physicochemical signatures to assess the sources of metals in urban road dust

Road deposited dust is a complex mixture of pollutants derived from a wide range of sources. Accurate identification of these sources is seminal for effective source-oriented control measures. A range of techniques such as enrichment factor analysis (EF), principal component analysis (PCA) and hierarchical cluster analysis (HCA) are available for identifying sources of complex mixtures. However, they have multiple deficiencies when applied individually. This study presents an approach for the effective utilisation of EF, PCA and HCA for source identification, so that their specific deficiencies on an individual basis are eliminated. EF analysis confirmed the non-soil origin of metals such as Na, Cu, Cd, Zn, Sn, K, Ca, Sb, Ba, Ti, Ni and Mo providing guidance in the identification of anthropogenic sources. PCA and HCA identified four sources, with soil and asphalt wear in combination being the most prominent sources. Other sources were tyre wear, brake wear and sea salt.

Isotopic and geochemical characterization of invader tilapia fishes from water bodies of West Bengal and Karnataka, India

The otoliths (N = 12) of freshwater invasive species tilapia (Tilapia mossambicus) collected from two water bodies located at Kolkata and Bangalore, India, were analyzed for stable isotopes (delta 18O, delta 14C) and major and trace elements in order to assess the suitability of using otoliths as a tracer of aquatic environmental changes. The stable isotope analysis was done using the dual inlet system of a Finnigan-MAT 253 isotope ratio mass spectrometer (Thermo-Fisher, Bremen, Germany). Concentrations of major and trace elements were determined using a Thermo X-Series II quadrupole mass spectrometer. The stable isotope composition in tilapia otolith samples from Bangalore and Kolkata water bodies are quite good agreeing with that of the respective lake/pond and rain water. Elemental composition revealed in a pattern of Ca > Fe > Na > Sr > K > Ba > Cr > Mg > As > Mn > Zn > Co > Cu > Cd > Pb. The otoliths from Kolkata pond water are more enriched in Ba, Zn, Pb, Mn, Se, Cu, Zn, Cd, and Ni whereas Cr and As were found to be higher in otolith samples from Bangalore lake. The enrichment factor (EF) values of Cr were higher for both the sampling location in comparison with other metals, although all the studied metals exhibited EF values >1. The PCA shows clustering of metals in the otolith which are related either with the metabolic and physiological attributes or waterborne source. The study demonstrated the potential of stable isotope techniques to distinguish otolith specimens from varied climatic zone, while elemental composition recorded the quality of water at both the locations. The role of climate driving the quality of water can be understood by detailed and continuous monitoring of otolith specimens in the future. Future method allows reconstruction of climate and water quality from old specimens from field exposures or museum collection.

Metals in surface sediments of large shallow eutrophic lake chaohu, china

Metal contents of surface sediments were analyzed temporally and spatially in Lake Chaohu, China. No obvious temporal variations were observed, which probably due to physio- and bio- mixing, e.g. wind and microbes, in this lake. Enrichment factor of some metals were generally greater than 1.0, suggesting significant anthropogenic impact on metal levels. Significantly positive correlations between concentrations of nutrient and metals indicated that the nutrients transported to this lake contributed, to some extent, to the enrichment of metals. The correlation between trace metals concentrations indicated the co-contamination of anthropogenically derived metal enrichment in surface sediment of Lake Chaohu.

Determination of arsenic species by capillary zone electrophoresis with large-volume field-amplified stacking injection

Determination of arsenic species by large-volume field amplified stacking injection-capillary zone electrophoresis (LV-FASI-CZE) is reported in this paper. Whole column injection was employed. The optimum buffer pH for the separation of weak acids was discussed. It was found that the optimum buffer to analyze the stacked arsenate (As(V)), monomethylarsonate (MMA), and dimethylarsinate (DMA) was 25 mm phosphate at pH 6.5. However, the optimum buffer to analyze the concentrated arsenite (As(III)) was 20 mm phosphate - 10 mm borate at pH 9.28. The limits of detection of the method developed were 0.026 mg/L for As(III), 0.023 mg/L for As(V), 0.043 mg/L for MMA, and 0.018 mg/L for DMA. An enrichment factor of 34-100 for several arsenic species was obtained. In the end, this method was applied to determine the arsenic concentration in the environmental reference materials to show the usefulness of the method developed.

Assessment of metal contamination in surface sediments of Jiaozhou Bay, Qingdao, China

An assessment of metal contamination in surface sediments of the Jiaozhou Bay, Qingdao, one of the rapidly developing coastal economic zones in China, is provided. Sediments were collected from 10 stations and a total of 15 heavy metals were analyzed. Concentrations of metals show significant variability and range from 210 to 620 ppm for Ti, 2.7 to 23 ppm for Ni, 4.2 to 28 ppm for Cu, 5.2 to 18 ppm for Pb, 12 to 58 ppm for Zn, 0.03 to 0.11 ppm for Cd, 5 to 51 ppm for Cr, 1.5 to 9.9 ppm for Co, 5.3 to 19 ppm for As, 12 to 32 ppm for Se, and 19 to 97 ppm for Sr. Based on concentration relationships and enrichment factor (EF) analyses, the results indicate that sediment grain size and organic matter played important roles in controlling the distribution of the heavy metals in surface sediments of the Jiaozhou Bay. The study shows that the sediment of the Jiaozhou Bay has been contaminated by heavy metals to various degrees, with prominent arsenic contributing the most to the contamination. The analysis suggests that the major sources of metal contamination in the Jiaozhou Bay are land-based anthropogenic ones, such as discharge of industrial waste water and municipal sewage and run-off. Notably, the elevated heavy metal concentrations of the Jiaozhou Bay sediments could have a significant impact on the bay's ecosystem. With the rapid economic development and urbanization around the Jiaozhou Bay, coastal management and pollution control should focus on these contaminant sources, as well as provide ongoing monitoring studies of heavy metal contamination within the bay.

Determination of heavy metal ions by capillary electrophoresis with contactless conductivity detection after field-amplified sample injection

A method has been developed for determining of heavy metal ions by field-amplified sample injection capillary electrophoresis with contactless conductivity detection. The effects of the 2-N-morpholinoethanesulfonic acid/histidine (MES/His) concentration in the sample matrix, the injection time and organic additives on the enrichment factor were studied. The results showed that MES/His with a low concentration in the sample matrix, an increase of the injection time and the addition of acetonitrile improved the enrichment factor. Four heavy metal ions (Zn2+, Co2+, Cu2+ and Ni2+) were dissolved in deionized water, separated in a 10 mM MES/His running buffer at pH 4.9 and detected by contactless conductivity detection. The detection sensitivity was enhanced by about three orders of magnitude with respect to the non-stacking injection mode. The limits of detection were in the range from 5 nM (Zn2+) to 30 nM (Cu2+). The method has been used to determine heavy metal ions in tap water.

Heavy metal accumulation reflecting natural sedimentary processes and anthropogenic activities in two contrasting coastal wetland ecosystems, eastern China

Due to the impacts of natural processes and anthropogenic activities, different coastal wetlands are faced with variable patterns of heavy metal contamination. It is important to quantify the contributions of pollutant sources, in order to adopt appropriate protection measures for local ecosystems. The aim of this research was to compare the heavy metal contamination patterns of two contrasting coastal wetlands in eastern China. In addition, the contributions from various metal sources were identified and quantified, and influencing factors, such as the role of the plant Spartina alterniflora, were evaluated. Materials and methods Sediment samples were taken from two coastal wetlands (plain-type tidal flat at the Rudong (RD) wetland vs embayment-type tidal flat at Luoyuan Bay (LY)) to measure the content of Al, Fe, Co, Cr, Cu, Mn, Mo, Ni, Sr, Zn, Pb, Cd, and As. Inductively coupled plasma atomic emission spectrometry, flame atomic absorption spectrometry, and atomic fluorescence spectrometry methods were used for metal detection. Meanwhile, the enrichment factor and geoaccumulation index were applied to assess the pollution level. Principle component analysis and receptor modeling were used to quantify the sources of heavy metals. Results and discussion Marked differences in metal distribution patterns between the two systems were present. Metal contents in LY were higher than those in RD, except for Sr and Mo. The growth status of S. alterniflora influenced metal accumulations in RD, i.e., heavy metals were more easily adsorbed in the sediment in the following sequence: Cu > Cd > Zn > Cr > Al > Pb ≥ Ni ≥ Co > Fe > Sr ≥ Mn > As > Mo as a result of the presence and size of the vegetation. However, this phenomenon was not observed in LY. A higher potential ecological risk was associated with LY, compared with RD, except for Mo. Based on a receptor model output, sedimentary heavy metal contents at RD were jointly influenced by natural sedimentary processes and anthropogenic activities, whereas they were dominated by anthropogenic activities at LY. Conclusions A combination of geochemical analysis and modeling approaches was used to quantify the different types of natural and anthropogenic contributions to heavy metal contamination, which is useful for pollution assessments. The application of this approach reveals that natural and anthropogenic processes have different influences on the delivery and retention of metals at the two contrasting coastal wetlands. In addition, the presence and size of S. alterniflora can influence the level of metal contamination in sedimentary environments.

Degradation of carbon disulphide (CS2) in soils and groundwater from a CS2 -contaminated site

This study is the first investigation of biodegradation of carbon disulphide (CS₂) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS₂-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10-2 h-1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H₂S) were found to be intermediates of degradation, but did not accumulate in vials. A 13C/12C enrichment factor of -7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a 13C/12C enrichment factor of -23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS2-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H₂S indicates that biodegradation of CS₂ is occurring and stable carbon isotopes are a promising tool to quantify CS₂ degradation.

Geochemistry of transition, non-transition and rare-earth elements in the surficial sediments of continental shelf of Kerala and an annex to the Cochin estuarine system

The metals present in the surface sediments have high demand on a global perspective, and the main reservoir of these elements is believed to be the ocean floor. A lot of studies on metals are going on throughout the world for its quantification and exploitation. Even though, some preliminary attempts have been made in selected areas for the quantitative study of metals in the western continental shelf of India, no comprehensive work has been reported so far. The importance of this study also lies on the fact that there has not been a proper evaluation of the impact of the Great Tsunami of 2004 on the coastal areas of the south India. In View of this, an attempt has been made to address the seasonal distribution, behavior and mechanisms which control the deposition of metals in the sediments of the western continental shelf and Cochin Estuary, an annex to this coastal marine region.Surface sediment samples were collected seasonally from two subenvironemnts of southwest coast of India, (continental shelf of Kerala and Cochin estuarine system), to estimate the seasonal distribution and geochemical behavior of non-transition, transition, rare-earth elements, Th and U. Bottom water samples were also taken from each station, and analysed for temperature, salinity and dissolved oxygen, hence the response of redox sensitive elements to oxygen minimum zone can be addressed. In addition, other sedimentary parameters such as sand, silt, clay fractions, CaCO3 and organic carbon content were also estimated to evaluate the control factors on level of metals present in the sediment. The study used different environmental data analysis techniques to evaluate the distribution and behavior of elements during different seasons. This includes environmental parameters such as elemental normalisation, enrichment factor, element excess, cerium and europium anomalies and authigenic uranium.

Spatial Variability and Contamination of Heavy Metals in the Inter-tidal Systems of a Tropical Environment

Heavy metals in the surface sediments of the two coastal ecosystems of Cochin, southwest India were assessed. The study intends to evaluate the degree of anthropogenic influence on heavy metal concentration in the sediments of the mangrove and adjacent estuarine stations using enrichment factor and geoaccumulation index. The inverse relationship of Cd and Zn with texture in the mangrove sediments suggested the anthropogenic enrichment of these metals in the mangrove systems. In the estuarine sediments, the absence of any significant correlation of the heavy metals with other sedimentary parameters and their strong interdependence revealed the possibility that the input is not through the natural weathering processes. The analysis of enrichment factor indicated a minor enrichment for Pb and Zn in mangrove sediments. While, extremely severe enrichment for Cd, moderate enrichment for Zn and minor enrichment of Pb were observed in estuarine system. The geo accumulation index exhibited very low values for all metals except Zn, indicating the sediments of the mangrove ecosystem are unpolluted to moderately polluted by anthropogenic activities. However, very strongly polluted condition for Cd and a moderately polluted condition for Zn were evident in estuarine sediments

Chemometric study on the trace metal accumulation in the sediments of the Cochin Estuary―Southwest coast of India

The distribution and accumulation of trace metals in the sediments of the Cochin estuary during the pre-monsoon, monsoon and post-monsoon periods were investigated. Sediment samples from 14 locations were collected and analysed for the metal contents (Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb), organic carbon, total nitrogen, total sulphur and grain size. The data were processed using statistical tools like correlation, factor and cluster analysis. The study revealed an enrichment of Cd and Zn in the study area particularly at station 2, which is confirmed by enrichment factor, contamination factor and geoaccumulation index. The factor analysis revealed that the source of Cd and Zn may be same. The study indicated that the spatial variation for the metals like Mg, Cr, Fe, Co, Ni, Cu, Zn, Cd and Pb were predominant unlike Mn which shows a temporal variation. The strong association of trace metals with Fe and Mn hydroxides and oxides are prominent along the Cochin estuary. The anthropogenic inputs of industrial effluents mainly control the trace metals enrichment in the Cochin estuary