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.     

Heavy metal concentration in deepwater rose shrimp species (Parapenaeus longirostris,Lucas, 1846) collected from the Marmara Sea Coast in Tekirdağ

Zn, Cd, Cr, Hg, As (total), Cu, Pb, and Ni levels of the deepwater rose shrimp (Parapenaeus longirostris, Lucas 1846), which were collected from the Tekirda? coast of the Marmara Sea, were evaluated. The Marmara Sea is the recipient of discharges from both land-based sources and the Black Sea Bosphorus stream. There are large numbers of anthropogenic activities in the coastal region of the northern Marmara Sea that include urban effluent, discharges from touristic resorts, agricultural runoff, fishing, and transportation. Heavy metal contamination of water resources may cause critical health problems for the people living around these water bodies. In deepwater rose shrimp (P. longirostris), the highest concentration level detected for Zn was 22.4?±?24.4 mg/kg in winter 2012, Cd 0.106?±?0.01 mg/kg in summer 2012, Cr 0.77?±?0.05 mg/kg in winter 2012, Hg 0.18?±?0.04 mg/kg in summer 2011, As 9.93?±?1.4 mg/kg in spring 2012, Cu 25.48?±?0.3 mg/kg in winter 2012, Pb 2.12?±?0.8 mg/kg in spring, and Ni 19.25?±?7.1 mg/kg in spring. The values of heavy metal analysis were compared to both the Turkish Food Codex (TFC) limits and international standards for human consumption. The Pb, As, and Cu levels were found to be higher than the maximum allowable limits.     

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.     

Assessment of water pollution in the Antuã River basin (Northwestern Portugal)

The Antuã River, located in northwestern Portugal, drains a region with a high population density and a strong economic dynamism. These factors, together with a lack of facilities for appropriate treatment of domestic and industrial sewage, are putting increasing pressure on water resources. In this context, the aim of the present study was to identify point sources of pollution and to assess the surface water quality in the Antuã basin by monitoring physicochemical variables. A total of 40 point sources of wastewater, including some with a high pollution load, were detected in the most populated and industrialized areas of the São João da Madeira and Oliveira de Azeméis municipalities. These sources explained the strong degradation of water quality observed in the upper and medium Antuã River and in one of its tributaries, where maxima of 49 mg l^?1 for biochemical oxygen demand, 29 mg l^?1 for Kjeldahl nitrogen and 3.7 mg l^?1 for total phosphorus, were found after five surface water monitoring campaigns. Despite the relevance of pollution problems, a considerable water quality improvement, promoted by favourable reaeration conditions, was observed in the final stretch of the river, giving evidence of a great self-depuration capacity. However, the Antuã is a significant contributor of nutrients to the Ria de Aveiro, the coastal lagoon where the river meets the Atlantic Ocean.     

Spatial distribution of major and trace elements in the water of Swarzędzkie Lake (Poland)

In order to characterize the contamination of the Swarzedzkie Lake and generate elemental distribution patterns 18 elements have been determined in samples of water, taken just above the bottom sediments. Analyses were carried out using two instrumental techniques - ICP-OES and ICP-MS. Two main sources of contamination were identified - diffuse pollution from agriculture and stormwater from the town. Three separate groups of elements were distinguished using cluster analysis and two groups using principal component analysis. These three groups are characterized as geogenic elements (Ag, As, Mg and Sb), elements supplied by the agricultural catchment (Ca, Mn, Sr, Na, K and Al) and elements originated from the urban contamination (Ni, Cr, Cu, Fe, V, Ba, Zn and Pb). PCA differentiated the above group of urban elements from the rest, originated from diffuse sources, with exception of alluminium, which was situated between two distinguished groups.     

Modelling the Transport of Oil–Mineral-Aggregates (OMAs) in the Marine Environment and Assessment of Their Potential Risks

Spilled oil can interact with suspended particles in marine environments and form oil–mineral aggregates (OMAs). Some OMAs with densities higher than seawater density can settle to the seedbed to pose potential risks to benthic organisms. To understand the transport and fate of oil associated with OMAs and evaluate their potential risks, an integrated hydrodynamic and fate/transport model has been used in a hypothetical case study of 1,000 tonnes of South Louisiana oil spilled in the Bristol Channel. Several scenarios have been simulated under different wave and current conditions. By using OMA properties derived from laboratory measurements reported in literature, it has been found that the risk to the benthos is unlikely for the two hypothetical cases with strong currents, but it is likely for the wave only (weak current) case. The effects of other factors such as OMA properties and sediment concentration were also examined in terms of their effects on the transport process and risks.     

Genotoxic effects of the herbicide Roundup® in the fish Corydoras paleatus (Jenyns 1842) after short-term, environmentally low concentration exposure

The glyphosate-based herbicide, Roundup^®, is one of the most used pesticides worldwide. In concert with the advent of transgenic crops resistant to glyphosate, the use of this pesticide has led to an increase in agricultural yields. The objective of this study was to evaluate the genotoxic effect that the herbicide Roundup^® (at a concentration of 6.67 μg/L, corresponding to 3.20 μg/L glyphosate) can have on the fish Corydoras paleatus. Treatment groups were exposed for 3, 6, and 9 days, and effects were analyzed using the piscine micronucleus test (PMT) and comet assay. A group subjected to filtered water only was used as a negative control. The PMT did not show differences between the control and exposed groups for any of the treatment times. In contrast, the comet assay showed a high rate of DNA damage in group exposed to Roundup^® for all treatment times, both for blood and hepatic cells. We conclude that for the low concentration used in this research, the herbicide shows potential genotoxic effects. Future research will be important in evaluating the effects of this substance, whose presence in the environment is ever-increasing.     

Heavy metal concentration in fish tissues inhabiting waters of “Buško Blato” reservoar (Bosnia and Herzegovina)

Heavy metals concentration (mercury, lead, cadmium, arsenic, copper, zinc and chromium) in tissues (muscles, liver, kidney and gonads) of Dalmatian barbelgudgeon, the nase, the souffie and brown trout, inhabiting waters of Busko Blato reservoir in Bosnia and Herzegovina, has been determined by atomic absorption spectrophotometry. The meat of the tested fish sorts does not contain elevated concentration of most analyzed heavy metals with exception of lead (higher than MAC in Italy, Germany and Denmark) and mercury (in muscles of brown trout higher than MAC in most countries). The lowest level of all heavy metals is always detected in gonads, with higher values in fry compared to milt for copper, zinc, chromium and arsenic. The highest copper concentration is observed in the liver from the souffie which is suggested as a suitable biomonitor for copper intoxication. In muscles of all fish sorts, lead was always present in much higher concentration than cadmium, while in kidneys of most fish sorts, lead and cadmium concentrations were similar. We showed that bioaccumulation of some heavy metals in the fish sorts analyzed is tissue and sex dependent. Also, we concluded that the small water exchange in reversible shallow reservoir does not induce elevated concentration of heavy metals in fish tissues inhabiting Busko Blato.     

An Analogy on Assessment of Urban Air Pollution in Turkey Over the Turn of the Millennium (1992–2001)

Rapid industrialization and urbanization in Turkey, especially over the last twenty five years, has provided better living standards to its residents, but it also caused a decrease in environmental quality. In late 1970's, air quality monitoring activities were started in some major cities by individual researchers in Turkey. It was just around the 1990's that a countrywide program on continuous air pollution monitoring in major province centers and selected large towns was launched. The impact of air pollution on people depend on various factors, such as existence and magnitude of coal powered energy generation plants, type of urban heating and their efficiency, and the numbers and specifications of vehicles. In this study, current Turkish urban air quality over the turn of the Millennium (1992–2001) is studied in the light of the country's worst cities in terms of outdoor air quality, the number of upper respiratory diseases, sinusitis, bronchitis, and pneumonia cases in these provinces reported by the state medical treatment facilities in 2001. The population that is under outdoor urban air pollution hazard was computed. A comparative analysis between the provinces that use natural gas and others that use fossil fuels was also completed in order to project monetary gains if the studied provinces will transform their indoor heating and industrial operations to be run by natural gas or other cleaner energy sources. If natural gas use in air polluted urban centers could be realized in the near future, approximately 212 to 350 million US dollars per annum could to be saved just by reducing health related problems caused by outdoor air pollution.     

Integrated survey of water pollution in the Suquía River basin (Córdoba, Argentina)

We report a combined two-year seasonal monitoring of Suquía River basin using both chemical parameters and biomarkers measured in Jenynsia multidentata, aiming to correlate external levels of contaminants with the response of oxidative stress biomarkers in this fish. Identified pollution sources correspond to city sewage as well as agricultural and small industry activities downstream from Córdoba city. Physicochemical parameters integrated into a water quality index (WQI) were measured in Suquía River during dry and wet seasons. Ag, Mn, Cu, Cr, Ni, Fe, Pb and Zn were also monitored in water and sediment samples. Biomarkers include detoxication and antioxidant enzymes: catalase (CAT), glutathione peroxidase (GPX), glutathione S-transferase (GST) and glutathione reductase (GR). Enzymes showed a pollution dependent response, with increased activities in fish collected close to the sewage exit and progressive drop further downstream, matching changes in the Water Quality index. The combined use of biomarkers with water quality parameters allowed both the identification of pollution sources and the evaluation of effects of contaminants on the aquatic biota.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.     

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.     

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.     

Evaluating the heavy metal contamination in sediments from the guadalquivir estuary after the Aznalcóllar mining spill (SW Spain): a multivariate analysis approach

The Doñana National Park is one of the most importantNatural Reserves in west Europe. The park and theGuadalquivir estuary were impacted by the release of 5million cubic meters of acid waste from the processing ofpyrite ore. Here are presented a multivariate analysisapproach to evaluate the extension and the magnitude of theaccidental spill on the estuarine sediments. Sediments wereused to analyze 6 different metals (Fe, Mn, Zn, Cd, Pb, Cu).Also the concentration of the metals in the differentgeochemical sediment fractions were determined as a means ofassessing the potential impact of the acid water from themine. The analysis of the results obtained permits toestablish that the impact of the accident was acute on theecosystem due to the set up of a treatment plan in June 1998and to the high hydrodynamic of the estuary that absorb theearly impact. Chronic contamination by Cu was also detectedduring the monitoring of the impact of the accident in theestuary but this did not appear to be related to theaccidental spill. Because the likelihood of long term adverseeffects from the heavy metal contamination of estuarinesediments, further ecotoxicological evaluations should becarried out for the estuary and the park using an integrated approach.     

Association of spinal deformities with heavy metal bioaccumulation in natural populations of grass goby, Zosterisessor ophiocephalus Pallas, 1811 from the Gulf of Gabès (Tunisia)

The present study illustrates an analysis of spinal deformities associated with metal accumulation in natural populations of Zosterisessor ophiocephalus derived from polluted (S1) and unpolluted (S2) areas in the Gulf of Gabès in Tunisia. Three basic types of spinal deformities were detected: kyphosis, scoliosis and lordosis. These basic deformities frequently co-occur. Spinal deformities were observed in 10.72% of the total examined fish (n = 494). Deformed fish were 3.85 times more frequent in S1 than in S2. In both sexes, the highest occurrence of deformities was observed in the 111-120 mm class decreasing thereafter with fish length. Hepatic concentrations of cadmium (Cd), copper (Cu) and zinc (Zn) were significantly higher in Z. ophiocephalus from S1 than those from S2. Comparisons between fish in each site showed that liver concentrations of Cd and Zn were significantly higher in deformed fish than in normal fish. The relationship between metals accumulation and observed spinal deformities as well as the suitability of this kind of studies for environmental monitoring are discussed.     

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.     

Monitoring of the Endangered Pinna nobilis Linné, 1758 in the Mar Grande of Taranto (Ionian Sea, Italy)

Two methods were used to calculate the meteorologically adjusted ground level ozone trends in southern Taiwan. The first method utilized is a robust linear regression method. The second approach uses a multilayer perceptron (MLP) artificial neural network (ANN) method. The observations obtained from 16 monitoring stations were analyzed and divided into six groups by hierarchical divisive clustering procedure. The daily maximum 1 and 8 h ozone concentrations for each group are then calculated. The meteorologically adjusted trends obtained by linear regression and MLP methods are smaller than the unadjusted trends for all groups and average time. It indicts that the meteorological conditions in Taiwan tend to increase ambient ozone concentrations in recent years.