Assessing the ecological condition of streams in a southeastern Brazilian basin using a probabilistic monitoring design

Prompt assessment and management actions are required if we are to reduce the current rapid loss of habitat and biodiversity worldwide. Statistically valid quantification of the biota and habitat condition in water bodies are prerequisites for rigorous assessment of aquatic biodiversity and habitat. We assessed the ecological condition of streams in a southeastern Brazilian basin. We quantified the percentage of stream length in good, fair, and poor ecological condition according to benthic macroinvertebrate assemblage. We assessed the risk of finding degraded ecological condition associated with degraded aquatic riparian physical habitat condition, watershed condition, and water quality. We describe field sampling and implementation issues encountered in our survey and discuss design options to remedy them. Survey sample sites were selected using a spatially balanced, stratified random design, which enabled us to put confidence bounds on the ecological condition estimates derived from the stream survey. The benthic condition index indicated that 62 % of stream length in the basin was in poor ecological condition, and 13 % of stream length was in fair condition. The risk of finding degraded biological condition when the riparian vegetation and forests in upstream catchments were degraded was 2.5 and 4 times higher, compared to streams rated as good for the same stressors. We demonstrated that the GRTS statistical sampling method can be used routinely in Brazilian rain forests and other South American regions with similar conditions. This survey establishes an initial baseline for monitoring the condition and trends of streams in the region.     

Analysis of trace elements (Cu, Cd, and Zn) in the muscle, gill, and liver tissues of some fish species using anodic stripping voltammetry

Heavy metal (Cu, Cd, Zn) concentration of the muscle, gill, and liver of Otolithes rubber, Pampus argenteus, Parastromateus niger, Scomberomorus commerson, and Onchorynchus mykiss are determined by anodic stripping voltammetry method. The results show that the concentration of Cu, Cd, and Zn varied between 0.44 and not detected, 0.585 and 0.001, and 0.450 and 0.005?μg/g, respectively. It is interesting that in O. mykiss, the mean value of copper concentration was more than other marine organisms of this study, while in P. niger, the mean value of copper was minimum. The results of this study indicate that in the different tissues of fish species (O. rubber, P. argenteus, P. niger, S. commerson, and O. mykiss), the concentrations of Cu, Cd, and Zn were significantly lower than the permissible FAO/WHO levels.     

Solid phase extraction of Cd,Pb, Ni,Cu, and Zn in environmental samples on multiwalled carbon nanotubes

A simple and sensitive solid phase extraction (SPE) method on multiwalled carbon nanotubes (MWCNTs) is presented for the determination of cadmium, lead, nickel, copper, and zinc at trace levels combined with flame atomic absorption spectrometry. The effects of parameters like pH, sample volume, sample and eluent flow rates, eluent concentration, and volume and type of eluent on the recovery of trace elements was examined. The metals retained on the nanotube at pH 6.5 as α-benzoin oxime complexes were eluted by 10 mL 2 M HNO₃ in acetone. The influence of matrix ions on the developed method was also evaluated. The preconcentration factor of the method was found to be 50. The detection limits for Cd(II), Pb(II), Ni(II), Cu(II), and Zn(II) were found as 1.7, 5.5, 6.0, 2.3, and 2.4 μg L^?1, respectively. To test the accuracy of the method, the method was applied to TMDA-70 fortified lake water and Spinach 1570A standard reference materials. Addition recovery studies were applied to tap water and cracked wheat samples, and determination of the analyte elements was carried out in some food samples with good results.     

Assessment of the effects of Cr, Cu, Ni and Pb soil contamination by ecotoxicological tests

This study aimed to assess soil quality by chemical and ecotoxicological investigations and to check the correspondence between soil metal concentrations and ecotoxicity. For these purposes, surface soils collected at four adjacent roadside urban parks and at a former industrial area were characterized for C/N, organic matter content, texture, and pH. Cr, Cu, Ni and Pb, chosen among the most representative soil metal contaminants, were measured as total content and as available and water soluble fractions. In addition, the total concentrations of the investigated metals were used to calculate two chemical indices: the contamination and the potential ecological risk factors. The toxicity of the investigated soils was evaluated by an ecotoxicity test battery carried out on both soil samples (Vibrio fischeri, Heterocypris incongruens and Sinapis alba) and elutriates (Vibrio fischeri, Daphnia magna and Selenastrum capricornutum). The findings, both by the chemical and ecotoxicological approaches, would suggest that the soils with high metal contamination pose ecological risks. On the other hand, moderately metal contaminated soils did not exclude soil ecotoxicity. In fact, toxic effects were also highlighted in soils with low metal content, toxicity being affected by metal availability and soil characteristics. Moreover, the results suggest the importance of using a battery of tests to assess soil ecotoxicity.     

Concentrations of Cr, Cd, Cu, Zn and Fe in crab Charybdis longicollis and shrimp Penaeus semisulcatus from the Iskenderun Bay, Turkey

Copper, chromium cadmium, iron and zinc concentrations were determined in marine crab Charybdis longicollis and marine shrimp Penaeus semisulcatus in order to assess the impact of industrial activities and the sinking of M/V Ulla ship. Liver, gill and muscle sample solutions prepared analyzed using the atomic absorption spectrophotometry technique. The order of the metal concentrations found in muscle of crab was: Cu>Cr>Fe>Zn>Cd, while in muscle of shrimp the order was different: Cr>Cu>Zn>Fe>Cd. The highest Cu, Cr, Cd, Fe and Zn concentrations were found in the liver, and this was followed by the gill and muscle in both species. The levels of all metals in a given tissue were always higher in C. longicollis than in P. semisulcatus. Metals in both species show seasonal variations. In both species the highest concentrations were detected for all metals in summer.     

Assessing the ecological effects of human impacts on coral reefs in Bocas del Toro,Panama

Environmental and biological reef monitoring was conducted in Almirante Bay (Bahía Almirante) in Bocas del Toro, Panama, to assess impacts from anthropogenic developments. An integrated monitoring investigated how seasonal temperature stress, turbidity, eutrophication and physical impacts threatened reef health and biodiversity throughout the region. Environmental parameters such as total suspended solids [TSS], carbon isotopes (δ¹³C), C/N ratios, chlorophyll a, irradiance, secchi depth, size fractions of the sediments and isotope composition of dissolved inorganic carbon [DIC] of the water were measured throughout the years 2010 and 2011 and were analysed in order to identify different impact sources. Compared to data from Collin et al. (Smithsonian Contributions to the Marine Sciences 38:324–334, 2009) chlorophyll a has doubled at sites close to the city and the port Almirante (from 0.46–0.49 to 0.78–0.97 μg l^?1) and suspension load increased, visible by a decrease in secchi depth values. Visibility decreased from 9-13 m down to 4 m at the bay inlet Boca del Drago, which is strongly exposed to river run off and dredging for the shipping traffic. Eutrophication and turbidity levels seemed to be the determining factor for the loss of hard coral diversity, most significant at chlorophyll a levels higher than 0.5 μg l^?1 and TSS levels higher than 4.7 mg l^?1. Hard coral cover within the bay has also declined, at some sites down to <10 % with extremely low diversities (7 hard coral species). The hard coral species Porites furcata dominated the reefs in highly impacted areas and showed a strong recovery after bleaching and a higher tolerance to turbidity and eutrophication compared to other hard coral species in the bay. Serious overfishing was detected in the region by a lack of adult and carnivorous fish species, such as grunts, snappers and groupers. Study sites less impacted by anthropogenic activities and/or those with local protection showed a higher hard coral cover and fish abundance; however, an overall loss of hard coral diversity was observed.     

Environmentally safe sewage sludge disposal: the impact of liming on the behaviour of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn

Dewatered sewage sludge containing relatively high total concentrations of Cr (945 micrograms ml-1), Cu (523 micrograms ml-1), Ni (1186 micrograms ml-1) and Zn (2950 micrograms ml-1) was treated with quicklime and sawdust for sludge disinfection and post-stabilisation. The mobility of the heavy metals in the sludge samples was assessed by applying a modified five-step Tessier sequential extraction procedure. Water was added as a first step for estimation of the proportion of the easily soluble metal fractions. To check the precision of the analytical work the concentrations of heavy metals in steps 1-6 of the extraction procedure were summed and compared to the total metal concentrations. The mass balance agreed within +/- 3% for Cd, Cu, Cr, and Zn and within +/- 5% for Ni, Pb, Fe and Mn. Data from the partitioning study indicate that in the lime-treated sludge at a pH of 12 the mobility of Cu and Ni notably increased with the solubilisation of these metals from their organic and/or carbonate and Fe and Mn oxide and hydroxide fractions, respectively. Liming slightly decreased the proportion of other heavy metals in the easily soluble fractions while its impact on the partitioning between other sludge phases was almost insignificant. Due to the increased solubility of Ni and Cu as well as potential Cr oxidation at high pH, liming cannot be recommended for sludge disinfection. Addition of sawdust did not change the heavy metal partitioning.     

Glacial-interglacial changes in the occurrence of Pb, Cd, Cu and Zn in Vostok Antarctic ice from 240 000 to 410 000 years BP

Lead (Pb), cadmium (Cd), copper (Cu) and zinc (Zn) have been measured by electrothermal atomic absorption spectrometry in various sections of the 3623 m deep ice core drilled at Vostok, in central East Antarctica. The sections were dated from 240 to 410 kyear BP (Marine Isotopic Stages (MIS) 7.5 to 11.3), which corresponds to the 3rd and 4th glacial-interglacial cycles before present. Concentrations are found to have varied greatly during this 170 kyear time period, with high concentration values during the coldest climatic stages such as MIS 8.4 and 10.2 and much lower concentration values during warmer periods, such as the interglacials MIS 7.5, 9.3 and 11.3. Rock and soil dust were the dominant sources for Pb, whatever the period, and for Zn and Cu and possibly Cd during cold climatic stages. The contribution from volcanic emissions was important for Cd during all periods and might have been significant for Cu and Zn during warm periods.     

Fractionation and elemental association of Zn, Cd and Pb in soils contaminated by Zn minings using a continuous-flow sequential extraction

Fractionation and elemental association of Zn, Cd, and Pb in soils near Zn mining areas were studied using a continuous-flow sequential extraction approach. The recently developed sequential extraction procedure not only gave fractional distribution data for evaluation of the mobility or potential environmental impact of the metals, but also the extraction profiles (extractograms) which were used for study of elemental association. In addition, the elemental atomic ratio plot extractogram can be used to demonstrate the degree of anthropogenic contamination. Seventy-nine soil samples were collected in the vicinity of a Zn mine and were fractionated into 4 phases i.e. exchangeable (F1), acid soluble (F2), reducible (F3) and oxidizable (F4) phases. Most samples were contaminated with Zn, Cd and Pb. The reducible phase is the most abundant fraction for Zn and Pb (>50%) while Cd is concentrated in the first 3 extraction steps. The distribution patterns of Cd were obviously affected by soil pH. 55% of Cd appears predominantly in the F1 fraction for acidic soils while in neutral and alkaline soils, it was mostly (70%) found in the F2 + F3 fractions. The extractograms obtained from the continuous-flow extraction system revealed close association between Zn, Cd, Pb and Fe in the acid soluble phase, Cd-Pb and Zn-Fe in the reducible phase for contaminated soils. A correlation study of the 3 metals using a correlation coefficient was also performed to compare the results with the elemental association revealed by the extractograms. Atomic ratio plot extractograms of Zn/Fe, Cd/Fe and Pb/Fe in the reducible phase, where contaminated metals are predominant, can be used to evaluate the degree of anthropogenic contamination. From the elemental atomic ratio plot, it is obvious that the contaminants Cd and Pb are mostly adsorbed on the surface of Fe oxides. Zn, which is present in an approximately 1 ratio 1 ratio with Fe in contaminated soils, does not show a similar trend to that found for Cd and Pb.     

Chemical speciation and partitioning of trace metals (Cd, Co, Cu, Ni, Pb) in the lower Athabasca river and its tributaries (Alberta, Canada)

Concentrations of Cd, Co, Cu, Ni and Pb were measured in particulate and dissolved phases at 11 sites located upstream and near Athabasca oil sands development. The in situ discrimination between non-labile and labile dissolved metals was done using diffusive gradients in thin-films (DGT) devices. The DGT-labile fraction of Co and Ni was 30% lower near development sites whereas Cu, Cd and Pb showed minor changes spatially. It was found that an 8-fold increase in dissolved organic matter (DOM) near development induced a rapid decrease in DGT-labile metals. Dissolved metal concentrations were used along with DOM, major ions, nutrients, pH and conductivity to calculate the distribution of dissolved metal species using the speciation model WHAM. Labile-DGT metal concentrations agreed well with WHAM-predicted concentrations. It was also found that a significant amount of metals were associated with the non-DGT labile fraction (i.e. colloidal DOM) and colloid abundance was more important than suspended particulate matter abundance in influencing metal mobility near Athabasca oil soils development. Since changes in colloidal DOM levels are likely to be the result of surface mining activities, this confirms the serious effects of oil sands activities on metal biogeochemical cycles in the lower Athabasca River.     

Assessing the effects of domestic and international energy scenarios and emission reduction strategies on acidification in Finland

An integrated model system was developed and used to assess the effects of alternative energy production scenarios and reduction policies on acidification of lakes and forest soils in Finland. The analysis covered different energy scenarios and resulting emissions of sulfur oxides and nitrogen oxides in Finland, as well as ammonia emissions with various control requirements. In addition, emission reduction scenarios of varied ambition levels in the bordering areas of Finland and in other parts of Europe were included in the analysis. The impacts of the different scenarios were quantified with exceedances of critical loads for acidification and with the total areas where the critical loads are exceeded. The possibilities for reducing the areas with critical load exceedances with national or bilateral measures were investigated. The differences in areas at risk, if depositions from domestic and nearby sources are estimated with a regional model and point-source databases or with a continental scale model and coarser-scale emission data, were analyzed. The reasons for the differences and the implications for national-level assessment are discussed.     

Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure

Sequential extraction procedures have been used during the last decades to study and determine trace element mobility in aquatic sediments. However, the results obtained are operationally defined and, therefore, the significance of the analytical results is related to the extraction scheme used. So, there is a need for suitable reference materials for this type of study to enable the validation of the methodologies and to control the quality of the measurements. This paper describes the preparation of a sediment reference material, BCR-701, the homogeneity and stability studies and the analytical work performed for the certification of the extractable contents of some trace elements, following a collaboratively tested and optimised sequential (three-step) extraction procedure. The paper contains all the results and gives the methods used to certify the extractable contents (mass fractions expressed as mg kg-1 on a dry matter basis) of Cd, Cr, Cu, Ni, Pb and Zn in all steps. Moreover, indicative values are given for the aqua regia extractable contents of the six elements in the sediment and the residue obtained after sequential extraction.     

Heavy metal (As,Cd, Hg,Pb, Cu,Zn, Se) concentrations in muscle and bone of four commercial fish caught in the central Adriatic Sea,Italy

Heavy metal (As, Cd, Cu, Pb, Zn, Hg and Se) concentrations in the muscle and bone of four fish species (Mullus barbatus, Merluccius merluccius, Micromesistius poutassou, and Scomber scombrus) from the central Adriatic Sea were measured and the relationships between fish size (length and weight) and metal concentrations in the tissues were investigated. Samples were analyzed by inductively coupled plasma-atomic emission spectrophotometry with automatic dual viewing. In the muscle, results of linear regression analysis showed that, except for mercury, significant relationships between metal concentrations and fish size were negative. Only mercury levels were positively correlated with Atlantic mackerel size (p?<?0.05). No significant variations of heavy metal concentrations were observed in muscles of the examined species, but a significant difference (p?<?0.01) was found for As, Cd, Pb, and Se concentrations in bone. All the investigated metals showed higher values in the muscle than in bone, except for lead and zinc. Regarding cadmium, lead, and mercury maximum levels, set for the edible portion by European legislation, several samples exceeded these values, confirming the heavy metal presence in species caught near the Jabuka Pit.     

Determination of heavy metals (Cd, Cr, Cu, Fe, Ni, Pb, Zn) by ICP-OES and their speciation in Algerian Mediterranean Sea sediments after a five-stage sequential extraction procedure

Surface sediment samples (n = 18) were collected from the Algerian Mediterranean coasts and analyzed for seven metals using inductively coupled plasma-optical emission spectrometry in order to asses the distribution and bioavailability of metals and to study the anthropogenic factors affecting their concentrations. Sediment samples were size-fractionated into three sizes: 1,080–500 (coarse), 500–250 (medium), and <250 mm (fine). Bulk sediments were subjected to both sequential extraction and total digestion to evaluate the reliability of the sequential extraction procedure (SEP), while the fractions have been only sequentially extracted for metals speciation. The metals were sequentially extracted into five phases namely exchangeable (P1), carbonates (P2), Fe–Mn oxides (P3), organic (P4) and residual (P5). Metal recoveries in sequential extractions were ±20% of the independently measured total metal concentrations; the high recovery rates indicate the good reliability of the SEP used in this study. Correlation coefficients indicated that the grain size has an effect on the distribution of metals in the investigated samples. The order of metal levels in the fractions was medium > fine > coarse for all the metals. The average total extractable metal concentrations for Cd, Cr, Cu, Fe, Ni, Pb, and Zn were 1.1, 8.8, 4.7, 1,291.3, 13.9, 5.7 and 20.4 μg/g, respectively. The northeastern shelf had the lowest metal levels while the highest were in northwestern part mainly due to the significant tourism activities in the northwestern part. Comparison of our results to Earth’s crust values and to previous studies points out that our samples were relatively unpolluted with respect to the heavy metals investigated; most of the metals are not from anthropogenic sources. Enrichment factors as the criteria for examining the impact of the anthropogenic sources of heavy metals were calculated, and it was observed that the investigated samples were not contaminated with Cr, Cu, and Fe, moderately contaminated with Ni, Pb, and Cd, and contaminated with Cd in some sites. The P5 phase had the highest percents of Cr, Cu, Fe, Ni, and Zn. Cadmium and lead were predominant in the P4 phase, while Cu, Fe and Zn were distributed in the order P5 > P3 > P4 > P2 > P1. The following order of bioavailability was found with the heavy metals Pb > Cr > Cd > Ni > Zn > Cu > Fe.     

Assessment of Cu, Pb, and Zn contamination in sediment of north western Peninsular Malaysia by using sediment quality values and different geochemical indices

Surface sediments were collected from the north western aquatic area (13 intertidal sites and 5 river drainages) of Peninsular Malaysia, which were suspected to have received different anthropogenic sources. These sites included town areas, ports, fishing village, industrial areas, highway sides, jetties and some relatively unpolluted sites. The present study revealed that 4.79-32.91 μg/g dry weight for Cu, 15.85-61.56 μg/g dry weight for Pb, and 33.6-317.4 μg/g dry weight for Zn based on 13 intertidal surface sediments while those based on 5 river drainage surface sediments were 10.24-119.6 μg/g dry weight for Cu, 26.7-125.7 μg/g dry weight for Pb and 88.7-484.1 μg/g dry weight for Zn. In general, the metal levels in the drainage sediments are higher than in the intertidal sediments, suggesting dilution factor in the intertidal sediment and direct effluent from point sources in the drainage sediment. In particular, the total concentrations of Cu, Pb, and Zn for the sampling site at Kuala Kurau Town exceeded the Effect Range Median values for Cu, Pb, and Zn for assessments of sediment quality values for freshwater sediment as proposed by MacDonald et al. (Arch Environ Contam Toxicol 39:20-31, 2000), thus adverse biological effects would be observed above this level. Assessment using enrichment factor (using Fe as a normalizer) and geoaccumulation index showed that the three metals at Kuala Kurau Town and Juru Industry drainage were evidenced as having more enrichment and mostly due to non-natural sources. However, caution should be exercised that the interpretation can only become valid when the ratios, indices, and sediment quality values are combined. This is due to the fact that not all the established indices are applicable and, to a certain extent, some of them should be further revised and improved to suit a different metal for Malaysian sediment. Undoubtedly, sites near drainages at Kuala Kurau Town and Juru River Basin need greater attention to mitigate the heavy metal pollution in the future.     

Bioaccumulation of metals (Cd, Cu, Zn) by the marine bivalves M. galloprovincialis, P. radiata, V. verrucosa and C. chione in Mediterranean coastal microenvironments: association with metal bioavailability

The concentrations of Cd, Cu and Zn in both the whole soft tissue and separate organs (gills, mantle, muscle and digestive gland) of wild bivalves (Mytilus galloprovincialis, Pinctada radiata, Venus verrucosa and Callista chione) from three different coastal microenvironments of Greece were monitored from 2003 to 2004. In parallel, by employing appropriate analytical protocols for metal partitioning, the labile fraction of the metals was determined in the dissolved phase, suspended particulate matter and sediments. Differences in the metal levels were detected both among the study areas as well as among the bivalves examined. Significant bioaccumulation was demonstrated regarding Zn in M. galloprovincialis specimens from the highly industrialized Gulf of Elefsis and Cd in P. radiata and V. verrucosa from the Maliakos Gulf, which is influenced by extended agricultural activity occurring at the neighbouring area and a river outflow. Data of the metal levels in the various environmental phases were correlated with their concentrations in bivalves’ tissues. The clear relationships obtained in many cases among the labile metal concentrations and the bioaccumulated concentrations in bivalves point out that the labile fraction of a metal is the most bioavailable. The lack of positive correlation for C. chione confirms the occurrence of effective mechanisms of internal regulation of metal concentrations.     

Assessing the effects of dam building on land degradation in central Iran with Landsat LST and LULC time series

This study aimed to analyze the impact of Zayandehrood Dam on desertification using the spatio-temporal dynamics of land use/land cover (LULC) and land surface temperature (LST) in an arid environment in central Iran from 1987 to 2014. The LULC and LST images were calculated from Landsat TM, ETM+, and OLI data, and their accuracies were assessed against reference data using error matrix and linear regression analysis. Results showed that salty and bare lands increased up to 57,302 ha, while agricultural lands declined substantially (28,275.58 ha) in the region. The changes in LULC classes resulted in dramatic variations in LST values. The average temperature showed a 5.03 °C increase, and the minimum temperature increased by 5.66 °C. LST had an increasing trend in bare lands (8.74 °C), poor rangelands (6.8 °C), agricultural lands (9.46 °C), salty lands (9.6 °C), and residential areas (3.18 °C) in this 27-year period. Rainfall and temperature trend analysis revealed that the main cause of these extreme changes in LULC and LST was largely attributed to the drying up of Zayandehrood River due to dam construction and allocating water mainly for industrial sectors. Results indicate that in addition to LULC changes, the spatio-temporal variations of LST can be used as an effective index in desertification assessment and monitoring in arid environments.