Origin, separation and identification of environmental nanoparticles: a review

The biogeochemical and ecological impacts of environmental nanoparticles (ENPs) are some of the fastest growing areas of research today. However, efficient separation and collection of ENPs in natural systems remains difficult. This review article is focused on experimental investigation of separation and identification of ENPs, including nanoparticles with size fractions in the range of <2000, 450 to 2000, 100 to 450 and 1 to 100 nm. An automated ultrafiltration device (AUD) was used successfully to overcome the problem of efficiently collecting ENPs in large quantities in red soils. A significant amount of hematite nanoparticles was present on the surface coating of kaolinite nanoparticles and aggregated hematite nanoparticles overlapping the edge of a kaolinite flake in a size range of 5 to 8 nm. Synchrotron XRD technique is more straightforward and powerful than conventional XRD with oriented specimens and random powder methods for identifying nanoparticles, crystallinity, and particle size in red soils, particularly for the illite, kaolinite, goethite and hematite nanoparticles. The AUD apparatus can be employed to efficiently collect large quantities of soil and related ENPs for investigation of their structural characteristics and surface properties, which have significant impact on weathering reaction pathways, catalysis, the fate of vital elements and environmental pollutants, and ecosystem restoration.     

Fractionation of traffic-emitted Ce, La and Zr in road dusts

The introduction of catalytic converters has led to a new environmental problem since catalysts emit platinum group elements (PGEs) which are among the least distributed elements in nature. Along with PGEs the vehicle exhaust catalysts contain also a number of stabilizers, commonly oxides of rare earth elements and alkaline earth elements such as Ce, La and Zr. Since vehicular emission of these elements has received little attention so far this work attempts to offer insight into their distribution and fate in the environment by measuring their speciation in road dust samples collected along several highways in Germany and a city centre (Saarbrücken). Speciation of the elements (fractionation into associated mineralogical phases) was carried out via a conventional sequential extraction protocol and the complexing abilities of humic substances in the organic matter were investigated by selective extraction methods in combination with size segregation. For evaluation purposes soil samples spiked with catalytic converter material were analyzed, showing a much lower fraction of Ce, La and Zr mobilized in comparison to the road dust samples. It was found that the elements were effectively bound to humic substances in road dust with a preference for complexation with low molecular weight compounds (<1600 Da).     

Silver speciation in liver of marine mammals by synchrotron X-ray absorption fine structure and X-ray fluorescence spectroscopies

The chemical form of Ag in the livers of five species of marine mammals was examined using X-ray absorption fine structure (XAFS) and X-ray fluorescence (XRF) spectroscopies. The XAFS analysis suggested that Ag(2)Se was present in the livers of the Franciscana dolphin (Pontoporia blainvillei), Dall's porpoise (Phocoenoides dalli), and Baird's beaked whale (Berardius bairdii), whereas Ag(2)S was present in the livers of the striped dolphin (Stenella coeruleoalba) and pygmy killer whale (Feresa attenuata). XRF spectroscopy results revealed that the distribution patterns of Ag and Se in a thin section of the liver of the Franciscana dolphin were the same; this also implied that Ag was associated with Se in the liver. Thus, the interaction of Ag with Se or S may offer significant protection against the toxicity of Ag in marine mammals. The formation of either Ag(2)Se or Ag(2)S might depend on the Hg levels in the liver. Ag(2)Se was observed in liver samples with relatively high Ag/Hg ratio, whereas liver samples with low Ag/Hg ratio contained Ag(2)S.     

Long-term changes of heavy metal and sulphur concentrations in ecosystems of the Taymyr Peninsula (Russian Federation) North of the Norilsk Industrial Complex

The Norilsk industrial ore smelting complex (Taymyr Peninsula, Russian Federation) has significantly impacted many components of local terrestrial and aquatic environments. Whether it has had a major impact on the wider Russian Arctic remains controversial as studies are scarce. From 1986 to 2004, data on heavy metal (Cu, Ni, Zn, Hg, Cd and Hg) concentrations in fish (burbot), moss, lichens, periphyton, hydric soils and snow in and around Norilsk and the most northern parts of the Taymyr Peninsula were analysed. Very high concentrations of Cu (203 μg L?1 ± 51 μg L?1) and Ni (113 μg L?1 ± 15 μg L?1) were found in the water of the Schuchya River close to Norilsk. Heavy metal concentrations in burbot liver were highest in Lake Pyasino near Norilsk compared to other study regions that were >100 km distant. From 1989-1996, Cu (121 μg L?1 ± 39 μg L?1 SD), Zn (150 μg L?1) ± 70 μg L?1) and Ni (149 μg L?1 ± 72 μg L?1) snow concentrations were greatest in Norilsk, but were low elsewhere. By 2004, these concentrations had dropped significantly, especially for Cu-74 μg L?1 (±18.7 μg L?1 SD), Zn-81.7 μg L?1 (± 31.3 μg L?1 SD) and Ni-80 μg L?1(±18.0 μg L?1 SD). Norilsk and its surroundings are subject to heavy pollution from the Norilsk metallurgical industry but these are absent from the greater Arctic region due to the prevailing winds and the Byrranga Mountains. Pollution abatement measures have been made so further investigations are necessary in order to assess their efficiency.     

Spatial distributions and eco-partitioning of soil biogeochemical properties in the Everglades National Park

Large-scale ecosystem restoration efforts, such as those in the Florida Everglades, can be long-term and resource intensive. To gauge success, restoration efforts must have a means to evaluate positive or negative results of instituted activities. Edaphic properties across the Everglades landscape have been determined to be a valuable metric for such evaluation, and as such, a baseline condition from which to make future comparisons and track ecosystem response is necessary. The objectives of this work were to document this baseline condition in the southern most hydrologic unit of the Everglades, Everglades National Park (ENP), and to determine if significant eco-partitioning of soil attributes exists that would suggest the need to focus monitoring efforts in particular eco-types within the ENP landscape. A total of 342 sites were sampled via soil coring and parameters such as total phosphorus (TP), total nitrogen (TN), total carbon (TC), total calcium, total magnesium, and bulk density were measured at three depth increments in the soil profile (floc, 0-10 cm, and 10-20 cm). Geostatistical analysis and GIS applications were employed to interpolate site-specific biogeochemical properties of soils across the entire extent of the ENP. Spatial patterns and eco-type comparisons suggest TC and TN to be highest in Shark River Slough (SRS) and the mangrove interface (MI), following trends of greatest organic soil accumulation. However, TP patterns suggest greatest storages in MI, SRS, and western marl and wet prairies. Eco-partitioning of soil constituents suggest local drivers of geology and hydrology are significant in determining potential areas to focus monitoring for future change detection.     

The seasonal distribution of heavy metals in Mussel sample from Yalova in the Marmara Sea, 2008�C2009

Concentration of the some heavy metals (Co, Cu, Fe, Ni, Pb and Zn) Mediterranean mussel Mytilus galloprovincialis from Yalova (Marmara Sea) were investigated seasonally. The mean concentrations of Co, Cu, Fe, Ni, Pb and Zn in the soft tissues were 4.08 ± 0.67, 5.54 ± 0.59, 156.72 ± 20.18, 3.71 ± 1.14, 2.92 ± 0.51 and 106.23 ± 5.66 mg kg(?-1) dry weights, respectively. There were no significant differences between the metal concentrations among the seasons (P > 0.05). The mean Pb and Zn concentrations were higher than the acceptable limit proposed by International Turkish standards.     

Exchangeable lead from prediction models relates to vetiver lead uptake in different soil types

Prediction models for exchangeable soil lead, published earlier in this journal (Andra et al. 2010a), were developed using a suite of native lead (Pb) paint-contaminated residential soils from two US cities heavily populated with homes constructed prior to Pb ban in paints. In this study, we tested the feasibility and practical applications of these prediction models for developing a phytoremediation design using vetiver grass (Vetiveria zizanioides), a Pb-tolerant plant. The models were used to estimate the exchangeable fraction of Pb available for vetiver uptake in four lead-spiked soil types, both acidic and alkaline, with varying physico-chemical properties and that are different from those used to build the prediction models. Results indicate a strong correlation for predictable exchangeable Pb with the observed fraction and as well with total Pb accumulated by vetiver grass grown in these soils. The correlation coefficient for the predicted vs. observed exchangeable Pb with p < 0.001 was 0.999, 0.996, 0.949, and 0.998 in the Immokalee, Millhopper, Pahokee Muck, and Tobosa soil type, respectively. Similarly, the correlation coefficient for the predicted exchangeable Pb vs. accumulated Pb in vetiver grass with p?< 0.001 was 0.948, 0.983, 0.929, and 0.969 for each soil type, respectively. This study suggests that the success of a phytoremediation design could be assessed upfront by predicting the exchangeable Pb fraction in a given soil type based on its properties. This helps in modifying the soil conditions to enhance phytoextraction of Pb from contaminated soils.     

Assessing possible visitor-use impacts on water quality in Yosemite National Park, California

There is concern that visitor-use associated activities, such as bathing, dish washing, wastewater production, and stock animal use near lakes and streams, could cause degradation of water quality in Yosemite National Park. A study was conducted during 2004-2007 to assess patterns in nutrient and Escherichia coli (E. coli) concentrations in the Merced and Tuolumne Rivers and characterize natural background concentrations of nutrients in the park. Results indicated that nutrient and E. coli concentrations were low, even compared to other undeveloped sites in the United States. A multiple linear regression approach was used to model natural background concentrations of nutrients, with basin characteristics as explanatory variables. Modeled nitrogen concentrations increased with elevation, and modeled phosphorus concentrations increased with basin size. Observed concentrations (±uncertainty) were compared to modeled concentrations (±uncertainty) to identify sites that might be impacted by point sources of nutrients, as indicated by large model residuals. Statistically significant differences in observed and modeled concentrations were observed at only a few locations, indicating that most sites were representative of natural background conditions. The empirical modeling approach used in this study can be used to estimate natural background conditions at any point along a study reach in areas minimally impacted by development, and may be useful for setting water-quality standards in many national parks.     

Variations in some environmental characteristics including C and N stable isotopic composition of suspended organic matter in the Mandovi estuary

Chemical and isotopic (??¹³C and ??¹⁵N) investigation of the Mandovi estuary along the Indian west coast affected strongly by the seasonal monsoon cycle was carried out. The Mandovi estuary is a major waterway for Goa and extensively used for transportation of iron and manganese ore. In addition, with large population centers as well as agricultural fields located on its shores, the estuary is assumed to have been influenced by human activities. Measurements of chemical and isotopic parameters made in the lower part of the estuary during the southwest (SW) monsoon and post-monsoon seasons reveal distinct changes, and it is observed that despite considerable enrichment of macronutrients during the SW monsoon, productivity of the estuary (phytoplankton biomass), as inferred from the chlorophyll-a content, is not as high as expected. This is due to occurrences of high turbidity and cloud cover that limits photosynthetic productivity. The isotopic characterization (C and N isotopes) of suspended organic matter produced/transported during the monsoon and post-monsoon seasons of year 2007 provides a baseline dataset for future isotopic studies in such type of tropical estuaries.     

A study on the phytoaccumulation of waste elements in wetland plants of a Ramsar site in India

Some wetland plant species are adapted to growing in the areas of higher metal concentrations. Use of such vegetation in remediation of soil and water contaminated with heavy metals is a promising cost-effective alternative to the more established treatment methods. Throughout the year, composite industrial effluents bringing various kinds of heavy metals contaminate our study site, the East Calcutta Wetlands, a Ramsar site at the eastern fringe of Kolkata city (formerly Calcutta), India. In the present study, possible measures for remediation of contaminated soil and water (with elements namely, Ca, Cr, Cu, Pb, Zn, Mn, and Fe) of the ecosystem had been investigated. Ten common regional wetland plant species were selected to study their efficiency and diversity in metal uptake and accumulation. Results showed that Bermuda grass (Cynodon dactylon) had the highest total Cr concentration (6,601 ± 33 mg kg^???1 dw). The extent of accumulation of various elements in ten common wetland plants of the study sites was: Pb (4.4?C57 mg kg^???1 dw), Cu (6.2?C39 mg kg^???1 dw), Zn (59?C364 mg kg^???1 dw), Mn (87?C376 mg kg^???1 dw), Fe (188?C8,625 mg kg^???1 dw), Ca (969?C3,756 mg kg^???1 dw), and Cr (27?C660 mg kg^???1 dw) indicating an uptake gradient of elements by plants as Ca>Fe>Mn>Cr>Zn>Cu>Pb. The present study indicates the importance of identification and efficiency of metal uptake and accumulation capabilities by plants in relation to their applications in remediation of a contaminated East Calcutta Wetland ecosystem.