Metal levels in sediments from the Minho estuary salt marsh: a metal clean area?

Total-recoverable metals (Al, Cr, Cu, Fe, Mn, Ni, Pb and Zn) in sediments from Minho estuary salt marsh were determined to evaluate possible increase in anthropogenic contamination by metals and to evaluate the possibility of this area to be considered a pristine area in terms of metals, which can be used as a reference site for other metal-contaminated national and international estuaries/salt marshes. This study revealed that the spatial distribution of metals in the salt marsh sediments was not homogeneous and that two sampling sites (sites 5 and 7) had indications of anthropogenic contamination. However, metal levels in these salt marsh sediments were lower than those observed in the wetlands of the main Portuguese estuaries. Comparison with Portuguese and international reference values used in the evaluation of the ecological quality of sediments, indicated that the sediments can be classified as “clean sediment” and that metal levels were lower or similar (only for Cu and Ni) to the values of ERL, which are the values that define the concentrations ranges that are rarely associated to adverse biologic effects in organisms. In addition, metal levels in the sediments were in chemical forms that were not easily available to organisms, indicating that these sediments probably will not have negative influences in the organisms living in the salt marsh, although no life-form ecological safety tests have been carried out. Therefore, the Minho estuary salt marsh area can probably be considered a pristine area in terms of metals and can be used as a reference for other metal-contaminated estuaries/salt marshes.     

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.     

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.     

Foliar nutrient and metal levels of crops in the Mount Cameroon area—reference values for plant nutrition and environmental monitoring

The growing population number and traffic loads, increasing environmental pressures, agricultural intensification, and the establishment of Mount Cameroon National Park demand farsighted environmental management in the region and the definition of a favorable ecological status. Since plants grow in the interface between soils and the atmosphere they can be used as passive biomonitors for the environmental quality. At the same time, the accumulation of nutrients and pollutants in crops is linked to human health, so that foliar elemental levels can be used as an integrative measure for environmental pollution and impact assessment. In the present study, we collected leaf samples of plantain, cassava, cocoyam, and maize on 28 sites at the southern flanks of Mt. Cameroon and determined 20 chemical elements. Air pollution in the study area comes from biomass and waste burning mainly, but emissions from traffic and a large refinery were believed to also play a significant role. However, spatial patterns in foliar elemental concentrations reflected the geochemistry rather than specific sources of pollution. Significant differences in foliar metal and nutrient levels were observed between the four species, indicating a different demand and uptake of specific elements. The results were compared to published data on nutrient concentrations in the tested species and the so-called reference plant. The data can be used as a baseline for future studies in plant nutrition and the environmental monitoring in inner tropical regions where these crops are grown.     

Analysis of heavy metal concentrations in sediments of selected estuaries of Malaysia—a statistical assessment

Statistical analysis of heavy metal concentrations in sediment was studied to understand the interrelationship between different parameters and also to identify probable source component in order to explain the pollution status of selected estuaries. Concentrations of heavy metals (Cu, Zn, Cd, Fe, Pb, Cr, Hg and Mn) were analyzed in sediments from Juru and Jejawi Estuaries in Malaysia with ten sampling points of each estuary. The results of multivariate statistical techniques showed that the two regions have different characteristics in terms of heavy metals selected and indicates that each region receives pollution from different sources. The results also showed that Fe, Mn, Cd, Hg, and Cu are responsible for large spatial variations explaining 51.15% of the total variance, whilst Zn and Pb explain only 18.93 of the total variance. This study illustrates the usefulness of multivariate statistical techniques for evaluation and interpretation of large complex data sets to get better information about the heavy metal concentrations and design of monitoring network.     

Trace metal fractionation in the Pichavaram mangrove–estuarine sediments in southeast India after the tsunami of 2004

The geochemistry of coastal sediments of southern India was altered after the tsunami in 2004. A five-step sequential extraction procedure was applied to assess the effects of tsunami on mobility and redistribution of selected elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn). Ten surface sediments and three cores were analyzed for different metal fractions (exchangeable, carbonate, reduced, oxidized, and residual). Total metal concentrations increased in mangrove sediments after the tsunami, but their spatial distribution did not show significant variation (except Mn). The sediments were mixed by the tsunami, and there was lack of variation in metal concentrations in different fractions with depth (except Pb and Mn). High concentrations of Pb and Zn occurred in the oxide fractions, whereas Cu, Cr, Cd, and Ni were high in the organic and sulfide-rich fractions. Metals in the residual fraction (lattice bound) had the highest concentration suggesting their non-availability and limited biological uptake in the system. Most of the metals (except Mn) do not constitute a risk based on the different geochemical indices.     

Assessment of enrichment factors and grain size influence on the metal distribution in riverbed sediments (Anll��ns River, NW Spain)

The metals distribution in the bed sediments of the Anllóns River was studied, with special emphasis on the evaluation of the metal distribution as a function of the granulometric fraction chosen for the analysis. Statistical significant differences between the distribution of K, Ca, Cr, Mn, As, Rb, Sr and Nb in the bulk (<2 mm) and fine fraction (<63 μm) were not found. Fe, Ni, Cu, Ga, Zr, Zn and Pb commonly appear in higher concentrations in the fine fraction, whereas Ti appears in higher concentrations in the bulk fraction. In general, it was observed that contamination phenomena tend to equalise the concentrations of both fractions, and this was mainly explained as the result of two processes. First, the formation of coatings over sands and, second, the formation of large aggregates (pseudo-sands) at sites located over basic rocks, whose chemical behaviour is closer to that of clays and could be responsible for significant adsorption processes. Normalisation techniques to evaluate contamination were applied by testing Nb, Sr, Rb or Ga as normaliser elements and by using crustal or shale average values for background concentrations. The most satisfactory result was obtained when using shale average values and Ga as the normaliser element. Arsenic was identified as the main contaminant of the basin, exceeding in all cases the low-effect reference values proposed by sediment quality guidelines and in two cases the medium-effect reference values. These sites were identified by multivariate techniques, which allow differentiating site 10 as affected by anthropogenic inputs related to past mining activities.     

Heavy metal distribution and enrichment in sediments of Mejillones Bay (23° S), Chile: a spatial and temporal approach

Concentrations of Ni, Cd, Pb, Cu, and Zn were measured in the surface sediments of Mejillones Bay at 32 sites ranging in depth from 10 to 95 m. A similarity dendrogram analysis separated the study area into two large sedimentary facies: a coastal zone with low metal concentrations and a deep zone with high metal concentrations. The abundances of Zn, Ni, and Pb increased between two sampling periods (5 years apart) in association with greater anthropogenic activity along the coastline of the bay at the present. The results were analyzed with the index of geoaccumulation and by applying the sediment quality guideline. Although similar to preindustrial levels, current Cu and Ni concentrations pose a likely threat to communities of benthic organisms. Concentrations of Zn and Pb are enriched, probably in connection with the industrial development of the zone, but do not reach dangerous levels for the benthic communities. Cd concentrations are toxic to benthic life, even though those measured herein are similar to preindustrial levels. Thus, these Cd levels are a result of the bay's natural characteristics (e.g., high biological productivity, the microxic water-sediment interface). The results of the Chilean aquatic sediment quality standards and the international standard (sediment quality guideline) were similar but differed from those found using the index of geoaccumulation, which suggests that the proposed reference values for Chilean aquatic sediment should be reviewed.     

Pool of mobile and immobile phosphorus in sediments of the large, shallow Lake Peipsi over the last 100?years

Temporal variations in sediment phosphorus (P) composition and mobility were estimated in surface sediments of accumulation (core PS509 44?cm) and erosion (core PS2009 30?cm) areas of the shallow, large Lake Peipsi sensu stricto (s.s.; 2611?km(2), unregulated water level). The P pool in sediments including buried and mobile P is evaluated for the first time, which will provide baseline data for the future modelling of internal loading in L. Peipsi. Five sedimentary P fractions (including inorganic and nonreactive P) were separately quantified: loosely adsorbed and pore-water P (NaCl-P); redox-sensitive fraction P (NaBD-P); P bound to oxides of non-reducible Fe and Al (NaOH-P); calcium-bound P, mainly from apatite minerals (HCl-P) and refractory, mainly organic P (Res-P). Concentrations of P fractions varied during the 100?years with the highest values around 2007-2008 and 1923-1935. The P in "active" layers that are available for bacteria and algae or those undergoing changes and diagenetic transformations in the sediment could follow sediments with the water content of ～88%. Potentially mobile P is not decreased in the sediments deposited 50-100?years ago and makes up ca 63?mg?m(-2)?y(-1) (with range 8.3-23.7% of the total P (TP)) in the accumulation area, and ca 0.047?mg?cm(-3) (with range 1.3-22.4% of TP) in the erosion area. The result shows that 13-60% of TP contained in the surface sediment (from 34 to 398?mg P m(-2) y(-1)) has been remobilised during accumulation and could be exported to the overlying water.     

Abundances, distribution, and sources of trace metals in Nakaumi–Honjo coastal lagoon sediments, Japan

Bottom sediments from Nakaumi Lagoon and the Honjo Area in southwest Japan were analyzed to determine their geochemical compositions and to assess potential impacts by comparison with sediment quality guidelines. Present-day water quality was also assessed. Results showed that the water quality of Nakaumi Lagoon and the Honjo area contrasts between their upper and lower parts. Average abundances of As, Pb, Zn, Cu, Ni, and Cr in the Nakaumi sediments were 12, 25, 135, 32, 21, and 46 ppm, respectively, compared to 10, 24, 110, 26, 20, and 38 ppm in the Honjo area. All averages are greater than those of the upper continental crust. The elevated metal concentrations are probably related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter and possibly minor non-point anthropogenic sources. Trace metal contents are strongly correlated with Fe₂O₃, suggesting that Fe oxides play a role in controlling abundances. Metal concentrations exceed the NYSDEC lowest effect level and CCME interim sediment quality guidelines that indicate moderate impact on aquatic organisms. Average abundances of As and Zn are comparable to the Coastal Ocean Sediment Database threshold, whereas maximum concentrations exceed that value, indicating that the concentrations of these metals are potentially toxic. These enrichments suggest that regular monitoring may be desirable even where no point sources of metal pollution exist.     

Levels and distribution of persistent organochlorine pesticide residues in water and sediments of Gomti River (India)—a tributary of the Ganges River

This study reports the concentration levels and distribution pattern of the persistent organochlorine pesticide (OCPs) residues in the water and bed-sediments of the Gomti River collected seasonally over a period of 2 years. The water and bed-sediment samples were collected from eight different sites and analyzed for aldrin, dieldrin, endrin, HCB, HCH isomers, DDT isomers/metabolites, endosulfan isomers (alpha and beta), endosulfan sulfate, heptachlor and its metabolites, alpha-chlordane, gamma-chlordane and methoxychlor. In the river water and sediments SigmaOCPs residues ranged between 2.16 and 567.49 ng l(-1) and 0.92 and 813.59 ng g(-1), respectively. The results, further, suggested that source of DDT contamination is from the aged and weathered agricultural soils with signature of recently used DDT in the river catchments. To assess any adverse effect of OCPs contamination on river's biological component, the threshold effect level (TEL) was used. The results revealed that bed-sediments of the Gomti River are contaminated with lindane, endrin, heptachlor epoxides and DDT, particularly at site-4 and may contribute to sediment toxicity in the freshwater ecosystem of the river.     

Spatial and temporal distribution of tributyltin (TBT) in seawater, sediments and bivalves from coastal areas of Korea during 2001–2005

Tributyltin (TBT) concentrations were determined in seawater, sediments and bivalve samples collected from Korean coastal areas during 2001-2005, to investigate the levels and temporal variation in TBT contamination in relation to the timing of the imposition of regulations on TBT use in Korea. TBT concentrations ranged from <5.0 to 164 ng/L in seawater, from <7.0 to 9,576 ng/g dry weight in sediments, and from <7.0 to 6,296 ng/g dry weight in bivalves. The highest concentrations of TBT were found at locations close to intensive shipping traffic and industrial complexes, and the contamination at some hot spot areas was high enough to cause harmful effects on marine organisms. TBT concentrations and their occurrence in Korean coastal waters have been decreasing annually. In particular, TBT concentrations in seawater have dramatically decreased. This result is consistent with regulations and bans on the use of TBT in Korea.     

Influence of different nitrate–N monitoring strategies on load estimation as a base for model calibration and evaluation

Model-based predictions of the impact of land management practices on nutrient loading require measured nutrient flux data for model calibration and evaluation. Consequently, uncertainties in the monitoring data resulting from sample collection and load estimation methods influence the calibration, and thus, the parameter settings that affect the modeling results. To investigate this influence, we compared three different time-based sampling strategies and four different load estimation methods for model calibration and compared the results. For our study, we used the river basin model Soil and Water Assessment Tool on the intensively managed loess-dominated Parthe watershed (315 km²) in Central Germany. The results show that nitrate–N load estimations differ considerably depending on sampling strategy, load estimation method, and period of interest. Within our study period, the annual nitrate–N load estimation values for the daily composite data set have the lowest ranges (between 9.8% and 15.7% maximum deviations related to the mean value of all applied methods). By contrast, annual estimation results for the submonthly and the monthly data set vary in greater ranges (between 24.9% and 67.7%). To show differences between the sampling strategies, we calculated the percentage deviation of mean load estimations of submonthly and monthly data sets as related to the mean estimation value of the composite data set. For nitrate–N, the maximum deviation is 64.5% for the submonthly data set in the year 2000. We used average monthly nitrate–N loads of the daily composite data set to calibrate the model to achieve satisfactory simulation results [Nash–Sutcliffe efficiency (NSE) 0.52]. Using the same parameter settings with submonthly and monthly data set, the NSE dropped to 0.42 and 0.31, respectively. Considering the different results from the monitoring strategy and the load estimation method, we recommend both the implementation of optimized monitoring programs and the use of multiple load estimation methods to improve water quality characterization and provide appropriate model calibration and evaluation data.     

Environmental quality assessment combining sediment metal levels, biomarkers and macrobenthic communities: application to the óbidos coastal lagoon (Portugal)

Macroinvertebrate benthic communities are one of the key biological components considered for the assessment of benthic integrity in the context of the Water Framework Directive (WFD). However, under moderate contamination scenarios, the assessment of macrobenthic alterations at community level alone could be insufficient to discriminate the environmental quality of coastal and transitional waters. Keeping this in view, sediment quality of moderately contaminated sites in a coastal lagoon (óbidos lagoon, Portugal) was assessed by the combination of sediment metal levels, Carcinus maenas biomarkers (accumulated metals and oxidative stress responses) and macrobenthic communities. Two sites were selected in confined inner branches (BS and BB) and a third one in the middle lagoon (ML). The site BB presented slightly higher levels of metals in sediment but biological variables calculated for macrobenthic data were not significantly different between sites. The biotic index M-AMBI that is being applied to assess environmental quality of transitional waters in the scope of the WFD pointed either to high (site ML) or good quality status (BS and BB) in the selected sites. However, crabs from BB site presented significantly higher levels of Ni in hepatopancreas than those from ML and macrobenthic community structure was significantly different between BB and ML. Additionally, spatial differences were obtained for oxidative stress parameters suggesting that BB site presented stressors for crabs (higher GST and lower GSH_t at BB site). Factor analysis (PCA) integrating sediment contamination, biomarkers in crabs and macrobenthic data also distinguished BB site as the most environmentally disturbed. On the other hand, at ML site, some macrobenthic variables (equitability and polychaetes’ diversity) were found to be enhanced by current environmental conditions, suggesting the existence of a better sediment quality. Current results pointed to the usefulness of integrating macrobenthic community alterations with responses at organism level (bioaccumulation and biochemical endpoints) in order to increase the accuracy of environmental quality assessment in lagoon systems. Moreover, the application of different statistical methods was also found to be recommendable.     

The trace metal levels in milk and dairy products consumed in middle Anatolia—Turkey

In this study, aluminium (Al), lead (Pb), cadmium (Cd), selenium (Se) and arsenic (As) contents in milk and different dairy product samples were measured. Pb, Cd, As, Al and Se contents in the milk and different dairy products ranged from 0.054 mg/kg (milk powder)?1.100 mg/kg (Ka?ar cheese), 0.009 mg/kg (whey powder and yogurt)?1.051 mg/kg (Tulum cheese), 0.010 mg/kg (whey powder)?0.146 mg/kg (butter), 2.848 mg/kg (ice cream)?8.778 (drained yogurt) and n.d. (ice cream, milk and whey powder, yogurt, ayran and Lor cheese)?0.434 mg/kg (Tulum cheese), respectively. The 75% of White and Ka?ar cheeses, 50% of Lor and 12.5% of Tulum cheese samples contained higher Pb according to the legal limits established by the Turkish Food Codex and European Communities regulation and 12.5% of Tulum cheese sample contained Cd. It was concluded that Pb contents of milk and dairy products from this region might be highly hazardous to human     

On the effects of the dispersant Corexit 9500© during the degradation process of n-alkanes and PAHs in marine sediments

In many coastal countries, oil spill contingency plans include several alternatives for removal of the spilled oil from the ocean. Frequently, these plans include dispersants. Because this process applies chemical substances that may add toxicity to oil that already contains toxic compounds, it is, at times, a controversial method to fight oil pollution. Additionally, local conditions may result in particular complications. We investigated the possible effects of the dispersant Corexit 9500© under conditions similar to those of subtropical oceans. We used fuel oil #6+ diesel as the test mixture. Under certain conditions, at least part of the dispersed oil may reach the sediment, particularly if the dispersant is applied in coastal waters. Nine experimental units were used in this experiment. Similar conditions of water temperature, salinity, air fluxes into the experimental units, and hydrocarbon concentrations in sediments were used. Two treatments and one control, each one with three replicates, were carried out. We concentrated our investigation on sediment, although measurements of water were also taken. Our results suggest that once the oil has penetrated the sediment, no significant differences exist between oil that contains dispersant and oil without dispersant. Noticeable degradation of aliphatic hydrocarbons occurred mainly in the low molecular weight aliphatic hydrocarbons and not in the others. Apparently, degradation of aromatics was easier than that of alkanes. However, some differences were noticed for the degradation of PAHs in the sediment, suggesting a faster degradation under particular conditions in aerobic environments such as under this experiment.