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.     

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 trace metal concentration in feathers of seabird (Larus dominicanus) sampled in the Florianópolis, SC, Brazilian coast

Cd, Co, Cr, Cu, Mn, Ni, Zn, and Pb were measured in feather samples of adult, subadult, and juvenile of Larus dominicanus, sampled in the Florianólis, SC, in the south of Brazil in December 2005, by flame atomic absorption spectrophotometry. The average of the distribution of Cd concentration in adult feathers (0.072 μg g^???1) was significantly different than that found in juvenile feathers (0.021 μg g^???1). Cu concentration averages were not significantly different between adults (13.30 μg g^???1), subadults (9.67 μg g^???1), and juveniles (13.76 μg g^???1). For adults and juveniles there was significant difference in feather concentrations for Cd, Co, Cr, Ni, and Pb. The distribution of Mn concentration averages in feathers differs between adults (11.36 μg g^???1) and juveniles (1.184 μg g^???1). Ni concentration averages of adults (5.92 μg g^???1) were significantly higher than those of juveniles (2.23 μg g^???1). For Pb, concentration averages were significantly higher in adults (7.53 μg g^???1) than in juveniles (1.47 μg g^???1). The concentration of Co and Cr in juvenile and subadults are statistically different when compared with the adults. In the present study, levels of Cd, Co, Cr, Mn, Ni, Zn, and Pb increased with age. The concentrations of essential trace elements in L. dominicanus were generally comparable to values reported in other studies. With non-essential metals (Cd, Pb, and Ni), in our study, L. dominicanus had lower values than those reported for their northern Atlantic counterparts.     

Organotin compounds in surface sediments from seaports on the Gulf of Gda??sk (southern Baltic coast)

Sediment samples were collected in two Polish ports of international significance--the Port of Gdańsk and the Port of Gdynia (Gulf of Gdańsk, Baltic Sea)--in order to assess their butyltin and phenyltin contamination; this was done in 2008, just after the total ban on using harmful organotins in antifouling paints on ships came into force. Altogether, 21 sampling stations were chosen to present a diversity of port sites: from port canals and shipyards to anchorages and dumping sites. The organic carbon content and grain size of all the sediment samples were determined, and some environmental parameters (oxygen content, salinity) were measured as well. Total concentrations of butyltin compounds in sediment samples were very different and ranged between 1 and 18,520 ng Sn g(-1) d.w. Phenyltin contents were distinctly lower and ranged from below the limit of detection (most samples) to 660 ng Sn g(-1) d.w. The highest concentrations of organotins were found in the shipyards, the maximum total organotin content (19,180 ng Sn g(-1) d.w.) being found in the Gdańsk Ship Repair Yard 'Remontowa'. Butyltin degradation indices indicate a recent tributyltin input into the port sediments. The results obtained from this work prove that the international ban on using organotins may not be enough to protect the marine environment. It is necessary to monitor organotin contamination in ports and establish concentration limits of these compounds for the disposal of dredged material at sea.     

Influence of a collapsed coastal landfill on metal levels in sediments and biota--a portent for the future?

In May 2008 a coastal landslide deposited landfill debris onto the shore near Lyme Regis, UK. Six months later, intertidal sediments and biota from the area were sampled to determine whether the landslip had affected distribution and bioavailability of metals in the area and if there were any biological effects. Highest sediment concentrations for the majority of metals occurred near the landslip zone and in several cases exceeded Threshold Effects or Probable Effects Levels (As, Cu, Hg, Ni, Pb, Zn). The 1 M HCl-extractable fraction of Cd, Pb and Zn in sediments also increased near the landslip. Metal bioaccumulation by intertidal biota showed variability between different species and metals, but there were several instances of increased accumulation near the landslip through increased availability from seawater, sediment and dietary sources. In most cases, metal concentrations in molluscs exceeded Oslo and Paris Commission (OSPAR) background concentrations (BCs) together with background assessment concentrations (BACs) at some sites. Kidney tissues in winkles (Littorina littorea) were measured for evidence of oxidative stress using the Total Oxyradical Scavenging Capacity (TOSC) assay. Responses to peroxynitrite, peroxyl and hydroxyl radicals suggested raised levels of TOSC in animals from the sites close to or east of the landfill waste. There have been very few studies of direct impact of landfills on the marine environment and this study could serve as a practical model for similar events driven by sea level rise.     

Impact of bottom trawling on sediment characteristics—a study along inshore waters off Veraval coast, India

The present communication is a study on the impact of bottom trawling on the sediment characteristics along Veraval coast, which is the largest trawler port of India. Experimental bottom trawling was conducted from MFV Sagarkripa at five transects of water depths 15–20 m, 21–25 m, 26–30 m, 31–35 m and 36–40 m in commercial trawling grounds. Trawling was conducted for 12 months in a span of 15 months (September 2005–November 2006) excluding the trawl ban period (June to August). The sediment texture was analysed by pipette analysis and organic matter by wet oxidation method. The variations in organic matter and sediment texture were prominent between the stations selected at different depths. The sedimentary organic matter exhibited variations with different water depths and seasons. The organic matter content decreased with depth. Experimental trawling considerably reduced the organic matter content at all depths. Continued and incessant trawling operation can cause even more drastic reductions, where organic matter (OM) content is already very small. The sand proportion showed depth-wise variation; but seasonal and trawling effect was not significant showing highest values at 36–40 m depth. The silt proportion did not exhibit significant depth-wise variation. The seasonal variation of silt was significant whereas trawling effect imparted to silt was not evident. Trawling has no significant effect on clay concentration. But seasonal variation had great influence on the clay distribution and indicated significantly high depth–season interaction. The sediment of the study area was predominant in silt proportion. It was observed that the seasonal/natural variations were more prominent masking the trawling effect on silt.     

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.     

Short-term variability of water quality and its implications on phytoplankton production in a tropical estuary (Cochin backwaters—India)

Changes in the phytoplankton biomass (chlorophyll a), production rate, and species composition were studied over two seasons using the time series measurements in the northern limb of the Cochin estuary in relation to the prevailing hydrological conditions. The present study showed the significant seasonal variation in water temperature (F = 69.4, P < 0.01), salinity (F = 341.93, P < 0.01), dissolved inorganic phosphorous (F = 17.71, P < 0.01), and silica (F = 898.1, P < 0.01) compared to nitrogen (F = 1.646, P > 0.05). The uneven input of ammonia (3.4–224.8 μM) from upstream (Periyar River) leads to the inconsistency in the N/P ratio (range 6.8–262). A distinct seasonality was observed in Si/N (F = 382.9, P < 0.01) and Si/P (F = 290.3, P < 0.01) ratios compared to the N/P ratio (F = 1.646, P > 0.05). The substantial increase in chlorophyll a (average, 34.8 ± 10 mg m^???3) and primary production (average, 1,304 ± 694 mg C m^???3 day^???1) indicated the mesotrophic condition of the study area during the premonsoon (PRM) and it was attributed to the large increase in the population of nanoplankton (size < 20 μ ) such as Skeletonema costatum, Thalassiosira subtilis, Nitzschia closterium, and Navicula directa. In contrast, during the post monsoon (PM), low chlorophyll a concentration (average, 9.3 ± 9.2 mg m^???3) and primary production (average, 124 ± 219 mg C m^???3 day^???1) showed heterotrophic condition. It can be stated that favorable environmental conditions (optimum nutrients and light intensity) prevailing during the PRM have enhanced the abundance of the nanoplankton community in the estuary, whereas during the PM, the light limitation due to high turbidity can reduce the nanoplankton growth and abundance, even though high nutrient level exists.     

Assessment of the impact of on-site sanitation systems on groundwater pollution in two diverse geological settings—a case study from India

On-site sanitation has emerged as a preferred mode of sanitation in cities experiencing rapid urbanization due to the high cost involved in off-site sanitation which requires conventional sewerages. However, this practice has put severe stress on groundwater especially its quality. Under the above backdrop, a study has been undertaken to investigate the impact of on-site sanitation on quality of groundwater sources in two mega cities namely Indore and Kolkata which are situated in two different geological settings. The parameters for the studies are distance of groundwater source from place of sanitation, effect of summer and monsoon seasons, local hydro-geological conditions, and physico-chemical parameters. NO₃ and fecal coliform concentrations are considered as main indexes of pollution in water. Out of many conclusions which can be made from this studies, one major conclusion is about the influence of on-site sanitation on groundwater quality is minimal in Kolkata, whereas it is significant in Indore. This difference is due to the difference in hydrogeological parameters of these two cities, Kolkata being on alluvium quaternary and Indore being on Deccan trap of Cretaceous to Paleogene age.     

Effect of on-site sanitation on groundwater contamination in basaltic environment ’A case study from India

On-site sanitation is increasingly adopted in urban cities in India. The adoption of On-site sanitation system puts the groundwater resources in the vicinity of the system at a greater risk. Microbial contaminants as well as chemical contaminants like Chloride and Nitrate are generated from human waste. These contaminants travel through the medium and ultimately get in contact with the groundwater. Hence, the groundwater sources are vulnerable to nitrate contamination near the On-site sanitation systems. The present study indicates significant Nitrate and Chloride contamination in samples collected close to On-site sanitation systems. The recommended limit set by the Bureau of Indian standards (BIS) limit of 45 mg/l for Nitrate concentration is also exceeded in few samples. The study indicates that Bacterial as well as Nitrate contamination is more in Monsoon as compared to Summer.     

Impact of mining and refining on the distribution and accumulation of nickel and other heavy metals in sediments of subarctic Lake Kuetsjärvi,Murmansk Region,Russia

Research on the influence of the activities of Pechenganickel Mining and Metallurgical Company on sediment heavy-metal geochemistry of the subarctic Lake Kuetsj?rvi (north-western Russia) are described. It is estimated that during 60 years of mining/refining activity, 310 t of Ni, 120 t of Cu, 14 t of Co, 19 t of Zn, 0.087 t of Cd, 0.78 t of Pb and 0.053 t of Hg have accumulated in the lake sediments. The latter can be a source of secondary pollution and represent a danger for the lake ecosystem. The sedimentation rate in the lake is estimated to be within the range of 1.5-3 mm year(-1). The average concentrations of Ni, Cu, Hg and Co in superficial sediments have increased 25, 14, 11 and 5 times, respectively in the last century.     

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.     

Identification of the hydrogeochemical processes in groundwater using major ion chemistry: a case study of Penna–Chitravathi river basins in Southern India

Hydrogeochemical studies were carried out in the Penna–Chitravathi river basins to identify and delineate the important geochemical processes which were responsible for the evolution of chemical composition of groundwater. The area is underlain by peninsular gneissic complex of Archaean age, Proterozoic meta-sediments, and strip of river alluvium. Groundwater samples were collected covering all the major hydrogeological environs in pre- and post-monsoon seasons. The samples were analyzed for major constituents such as Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, CO₃ ^???, HCO₃ ^???, Cl^???, SO₂ ^???4, NO₃ ^???, and F^???. The groundwater in general is of Na^?+?–Cl^???, Na^?+?–HCO₃ ^???, Ca^2?+?–Mg^2?+?–HCO₃ ^???, and Ca^2?+?–Mg^2?+?–Cl^??? types. Na^?+? among cations and Cl^??? and/or HCO₃ ^??? among anions dominate the water; Na^?+? and Ca^2?+? are in the transitional state with Na^?+? replacing Ca^2?+? and HCO₃ ^??? Cl^??? due to physiochemical changes in the aquifer and water–rock interactions. The Ca^2?+?–Mg^2?+?–Cl^??? HCO₃ ^??? type water in one third samples suggest that ion exchange and dissolution processes are responsible for its origin. Change in storage of aquifer in a season does not influence the major geochemical makeup of groundwater. Gibbs plots indicate that the evolution of water chemistry is influenced by water–rock interaction followed by evapotranspiration process. The aquifer material mineralogy together with semiarid climate, poor drainage system, and low precipitation factors played major role in controlling groundwater quality of the area.     

Benthic foraminiferal response to trace element pollution—the case study of the Gulf of Milazzo, NE Sicily (Central Mediterranean Sea)

The response of benthic foraminiferal assemblages to trace element pollution in the marine sediments of the Gulf of Milazzo (north-eastern Sicily) was investigated. Since the 1960s, this coastal area has been a preferred site for the development of two small marinas and a commercial harbour as well as for heavy industry. Forty samples collected in the uppermost 3–4 cm of an undisturbed layer of sediment in the littoral environment were used for this benthic foraminiferal analysis. The enrichment factors (EFs) of selected trace elements (As, Co, Cr, Cu, Mn, Ni, Pb and Zn) were also calculated. Changes both in benthic foraminiferal assemblages and in some trace elements concentrations have provided evidence that the gulf’s littoral zone can be subdivided into three sectors characterised by environmental changes in the marine ecosystem. In the sector unpolluted, close to the Milazzo Cape, foraminiferal assemblages exhibit high values of species richness and foraminiferal density while trace element concentrations and their EFs are very low. Here, the highest densities of Miliolids and epiphytic species are present. On the contrary, in the sector polluted, from the marinas to the crude oil refinery, foraminiferal density and species diversity are low, and assemblages are dominated, albeit with very low densities, by species that tolerate stressed environmental conditions, such as LOFAs, agglutinants and Ammonia spp. Here, the highest trace elements concentrations of Pb, Zn and Cu and related EFs were detected. Eastwards, in the sector moderately polluted, foraminiferal populations are quite poor. They are characterised by low values of species richness and foraminiferal densities, nevertheless trace element concentrations become lower than in the other sectors and their EFs are often below 1. Deformed foraminifera, with percentages up to 7.14 %, were found in all three of the sectors. Differences in benthic foraminiferal assemblages, coupled with results from statistical analysis, indicate that anthropogenic trace element pollution could be considered as one of the most important causes of the modifications of foraminiferal assemblages in the study area.     

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.     

Biomonitoring ²¹°Po and ²¹°Pb in marine brachyuran crabs collected along the coast of Kudankulam, Gulf of Mannar (GOM), India

Activities of 21?Po and 21?Pb in whole-body and in various tissues of brachyuran crabs collected along the Kudankulam coast were studied. A non-uniform distribution of these radionuclides was observed between the various tissues. Of all the tissues, 21?Po and 21?Pb were found to accumulate more in the hepatopancreas and intestine. Among the crabs studied, Charybdis lucifera registered higher 21?Po and 21?Pb activity. Muscle tissue in all the species registered lower activity. The 21?Po/21?Pb activity ratio was found to be greater than unity. The biological concentration factor for organs varied between ~ 10? and 10? for 21?Po and ~102 and 10? for 21?Pb. A significant variation in the accumulation of 21?Po and 21?Pb was noted between species and between seasons (p < 0.05). The mean whole-body internal dose ranged from 1.42 to 6.86 μGy h?1 for 21?Po and from 3.0 × 10?3 to 8.0 × 10?3 μGy h?1 for 21?Pb. The external dose for 21?Po and 21?Pb was 2.41 × 10?? to 5.76 × 10?? μGy h?1 and 4.14 × 10?? to 8.26 × 10?? μGy h?1, respectively. The activity levels recorded are in agreement with values recorded in related organisms in other parts of the world. The total committed effective dose due to the intake of both radionuclides ranged from 80.3 to 871.7 μSv y?1. The median dose calculated due to 21?Po and 21?Pb in certain crabs in Kudankulam is less and would not pose any significant radiological impact on health or a cancer risk to the public, and the seafood is considered safe for human consumption.     

The study of heavy metal pollution and accumulation in water, sediment, and fish tissue in Kızılırmak River Basin in Turkey

The accumulation of heavy metals such as Pb, Hg, Co, Cr, Cu, Zn, and Br were determined in water, sediment, muscle, and gill of three fish species (Leuciscus cephalus, Capoeta tinca, Capoeta capoeta) which were collected in K?z?l?rmak River Basin (Delice River). The metal concentration showed a general trend of Br>Zn> Pb>Cr>Cu>Hg>Co in water and Cr>Zn>Pb> Cu>Co>Hg>Br in sediment samples while Zn> Cu>Pb>Br>Cr>Hg>Co were in muscle and Zn>Pb>Cu>Cr>Br>Hg>Co were in the gill tissue.