Assessment of metal mobility in sediment, commercial fish accumulation and impact on human health risk in a large shallow plateau lake in southwest of China.

Sediment heavy metal pollution in the Dianchi Lake has been a long-term environmental problem of concern. This study investigated the lake sediment heavy metal contamination level, mobility, commercial fish metal accumulation and its impact on human health. The results show high As, Hg and Cd concentration in the sediment, while Pb and Cr contamination are insignificant. Sediment sequential extraction analysis shows that Hg in sediment has the highest portion of mobile fraction, followed by As, while the portion of mobile fractions of Cd, Pb and Cr in sediment is very low. The high concentrations of Hg and As in surface water and porewater were consistent with the chemical fraction composition of the two elements in sediment. Three major commercial fish species, Culterichthys erythropterus, Carassius auratus and Hypophthalmichthys molitrix, were collected for analysis of metal concentrations in their muscles. Among the same size of fish, C. auratus has the highest As concentration due to its bottom habitat and omnivorous feeding habits. On the other hand, C. erythropterus has the highest Hg concentration due to its relatively high trophic level position. The average THQ value of metals in fish tissue decrease in the order of As > Hg > Pb > Cd > Cr and the total THQ of average metal concentration in fish species decreased in the order of C. auratus > C. erythropterus > H. molitrix. Both THQ and total THQ is below 1, suggested no non-carcinogenic human health risk of fish consumption. However, TR of As in C. auratus was above 1.00E-04 threshold value, indicated potential carcinogenic human health risk. The results from this study indicate that although moderately to heavily contamination of Hg, As, and Cd occurred in Dianchi Lake sediment, only Hg and As tend to transport to surface water and accumulate in commercial fish due to their higher mobility in sediment.

Synchrotron study of metal localization in Typha latifolia L. root sections.

Understanding mechanisms that control plant root metal assimilation in soil is critical to the sustainable management of metal-contaminated land. With the assistance of the synchrotron X-ray fluorescence technique, this study investigated possible mechanisms that control the localization of Fe, Cu, Mn, Pb and Zn in the root tissues of Typha latifolia L. collected from a contaminated wetland. Metal localizations especially in the case of Fe and Pb in the dermal tissue and the vascular bundles were different. Cluster analysis was performed to divide the dermal tissue into iron-plaque-enriched dermal tissue and regular dermal tissue based on the spatial distribution of Pb and Fe. Factor analysis showed that Cu and Zn were closely correlated to each other in the dermal tissues. The association of Cu, Zn and Mn with Fe was strong in both regular dermal tissue and iron-plaque-enriched dermal tissue, while significant (p < 0.05) correlation of Fe with Pb was only observed in tissues enriched with iron plaque. In the vascular bundles, Zn, Mn and Cu showed strong association, suggesting that the localization of these three elements was controlled by a similar mechanism. Iron plaque in the peripheral dermal tissues acted as a barrier for Pb and a buffer for Zn, Cu and Mn. The Casparian strip regulated the transportation of metals from dermal tissues to the vascular bundles. The results suggested that the mechanisms controlling metal localization in root tissues varied with both tissue types and metals.

Nitrogen transformations in constructed wetlands: A closer look at plant-soil interactions using chemical imaging.

Constructed wetlands have long been used for domestic wastewater treatment. Despite the widespread application of constructed wetlands for wastewater remediation, they are still regarded as a black box in terms of the complex biogeochemical processes occurring internally, particularly with respect to plant-soil (and nitrogen) interactions. Additionally, many critical processes pertaining to nitrogen transformations in constructed wetlands are thought to occur in microzones within the rhizosphere, highlighting the need for studies with sub-cm spatial resolution. In this study we coupled nitrogen porewater measurements with chemical imaging to determine spatio-temporal patterns in porewater O2 and pH to assess the extent of plant-induced changes in soil redox dynamics that influence nitrogen biogeochemical cycling during dosed application of nitrogen-rich artificial wastewater. Planar optode imaging revealed extensive O2 fluxes to otherwise anoxic sediment via radial oxygen loss (ROL) from Typha latifolia roots. The contribution of photosynthetic O2 from this plant species was minimal as a strong oxic signal persisted in darkness (diel cycles). NH4+ and NOx- removal were strongly correlated with the extent of oxic and anoxic areas, a function largely attributed to the presence of plants and the associated enhanced microbial communities supported. The distribution of nitrogen species within the Typha rhizosphere exhibited reproducible trends as a function of distance from roots, with concentrations highest close to roots (1-5 mm from root surface) and subsequently decreasing at greater distances. Microscale spatio-temporal redox heterogeneity within the rhizosphere due to ROL imposed by plants promoted nitrogen removal likely by stimulating the coupling between nitrification and denitrification in these systems. Collectively, this study highlights the profound importance of plants in exerting controls on soil conditions and nitrogen cycling in constructed wetland systems. With careful considerations, constructed wetlands designed to promote wetland plants' functions may enhance nitrogen removal and mitigate nitrogen pollution.

The dynamics of cable bacteria colonization in surface sediments: a 2D view.

Cable bacteria that are capable of transporting electrons on centimeter scales have been found in a variety of sediment types, where their activity can strongly influence diagenetic reactions and elemental cycling. In this study, the patterns of spatial and temporal colonization of surficial sediment by cable bacteria were revealed in two-dimensions by planar pH and H2S optical sensors for the first time. The characteristic sediment surface pH maximum zones begin to develop from isolated micro-regions and spread horizontally within 5 days, with lateral spreading rates from 0.3 to ~ 1.2 cm day-1. Electrogenic anodic zones in the anoxic sediments are characterized by low pH, and the coupled pH minima also expand with time. H2S heterogeneities in accordance with electrogenic colonization are also observed. Cable bacteria cell abundance in oxic surface sediment (0-0.25 cm) kept almost constant during the colonization period; however, subsurface cell abundance apparently increased as electrogenic activity expanded across the entire surface. Changes in cell abundance are consistent with filament coiling and growth in the anodic zone (i.e., cathodic snorkels). The spreading mechanism for the sediment pH-H2S fingerprints and the cable bacteria abundance dynamics suggest that once favorable microenvironments are established, filamentous cable bacteria aggregate or locally activate electrogenic metabolism. Different development dynamics in otherwise similar sediment suggests that the accessibility of reductant (e.g., dissolved phase sulfide) is critical in controlling the growth of cable bacteria.

Bacterial community responses to the redox profile changes of mariculture sediment.

Suspended mariculture has significantly influences on the benthic sediment. However, our understanding on how bacterial communities respond to mariculture induced changes in redox profiles is limited. In present study, sediments from two maricultures and reference areas were collected and incubated for 28 day. The results indicated that the dominant pathway of organic matter mineralization in the sediment varied from groups, in the reference, it was the iron reduction, but in the two mariculture groups it was the SO42- reduction. Remarkable changes of bacteria community were recorded in the aerobic zone, where the abundances of 14 OTUs belonging to Gammaproteobacteria and Alphaproteobacteria were significantly higher than that in oxidation and anaerobic zones. However, 4 keystone OTUs were strictly anaerobic and belonging to Desulfobacteraceae (n = 3) and Marinilabiaceae (n = 1). The main environmental drivers determining sediment bacterial distribution were the particle organic carbon, dissolve oxygen, NO3-, and moisture content.

Correction to: Bioaccumulation and growth characteristics of Vallisneria natans (Lour.) Hara after chronic exposure to metal-contaminated sediments.

The correct name of the 9th Author is shown in this paper.

Worm tubes as conduits for the electrogenic microbial grid in marine sediments.

Electrogenic cable bacteria can couple spatially separated redox reaction zones in marine sediments using multicellular filaments as electron conductors. Reported as generally absent from disturbed sediments, we have found subsurface cable aggregations associated with tubes of the parchment worm Chaetopterus variopedatus in otherwise intensely bioturbated deposits. Cable bacteria tap into tubes, which act as oxygenated conduits, creating a three-dimensional conducting network extending decimeters into sulfidic deposits. By elevating pH, promoting Mn, Fe-oxide precipitation in tube linings, and depleting S around tubes, they enhance tube preservation and favorable biogeochemical conditions within the tube. The presence of disseminated filaments a few cells in length away from oxygenated interfaces and the reported ability of cable bacteria to use a range of redox reaction couples suggest that these microbes are ubiquitous facultative opportunists and that long filaments are an end-member morphological adaptation to relatively stable redox domains.

Influence of suspended mariculture on vertical distribution profiles of bacteria in sediment from Daya Bay, Southern China.

Mariculture is known to contribute to oxygen depletion, pH decline and accumulation of nutrients and organic matter in sediments. However, studies on the bacterial vertical distribution of mariculture area are very limited. The bacterial abundance in the non-culture site (3.8 ±â€¯0.8 × 109 copies g-1) was significantly higher than that in the three mariculture sites (1.2 ±â€¯0.2 × 109 copies g-1), and bacterial diversity in the non-culture site was significantly higher than that in fish cage-TF (p < 0.05). The vertical distribution profiles of bacteria in non-culture and oyster culture sites were similar but very different from that of fish cage-TF. In addition, significant downward trends in bacterial abundance and diversity were observed as sediment depth increased (p < 0.05), and the most relevant environmental factors were moisture content, total nitrogen, total organic carbon and carbon/nitrogen. The dominant bacterial phyla in sediment were Proteobacteria, Chloroflexi and Bacteroidetes.

Bioaccumulation and growth characteristics of Vallisneria natans (Lour.) Hara after chronic exposure to metal-contaminated sediments.

Metal-contaminated sediments in lakes is a global concern that poses toxicological risk to aquatic organisms. This study performed bioassays using the submerged macrophyte, Vallisneria natans (Lour.) Hara, exposed to contaminated sediments collected from five locations in Dianchi Lake, Yunnan, China. Among the sediments collected, Igeo showed enrichment of As and Cd in Dianchi Lake sediments. In spite of enriched toxic metals at some locations, laboratory bioassays found no significant difference in leaf biomass or leaf photosynthesis rate between the sites. Root biomass and root activity showed significant differences between locations and were negatively correlated with the concentration of As, Cd, Hg, and Pb in sediment but not related to Cr. The above correlations were strongest for Hg and As, respectively. Accumulation of Cd and Pb to leaves of bioassay plants was observed, but this was not evident for As and Cr. Overall, the results indicate that V. natans can be used as a bioassay organism and measures of root toxicity are sensitive to metal concentrations present in Dianchi Lake sediments. Furthermore, the study species holds promise for use as a biomonitor of Cd and Pb sediment metal content.

Seasonal differences in trace element concentrations and distribution in Spartina alterniflora root tissue.

The present study uses nanometer-scale synchrotron X-ray nanofluorescence to investigate season differences in concentrations and distributions of major (Ca, K, S and P) and trace elements (As, Cr, Cu, Fe and Zn) in the root system of Spartina alterniflora collected from Jamaica Bay, New York, in April and September 2015. The root samples were cross-sectioned at a thickness of 10 µm. Selected areas in the root epidermis and endodermis were mapped with a sampling resolution of 100 and 200 nm, varying with the mapping areas. The results indicate that trace element concentrations in the epidermis and endodermis vary among the elements measured, possibly because of their different chemical properties or their ability to act as micronutrients for the plants. Elemental concentrations (As, Ca, Cr, Cu, Fe, K, P, S and Zn) within each individual root sample and between the root samples collected during two different seasons are both significantly different (p < 0.01). Furthermore, this study indicates that the nonessential elements (As and Cr) are significantly correlated (p < 0.01) with Fe, with high concentrations in the root epidermis, while others are not, implying that Fe may be a barrier to nonessential element transport in the root system. Hierarchy cluster analysis shows two distinct groups, one including As, Cr and Fe and the other the rest of the elements measured. Factor analysis also indicates that the processes and mechanisms controlling element transport in the root system can be different between the nutrient and nonessential elements.

Reduction of nitrate by NaY zeolite supported Fe, Cu/Fe and Mn/Fe nanoparticles.

Nano particles Fe, Cu/Fe and Mn/Fe supported on NaY zeolite (F@Y, CF@Y, and MF@Y) were prepared by two-step processes consisting of ion exchange and liquid-phase reduction. The characterization by XRD, SEM-EDX and BET-N2 adsorption demonstrated that Fe, Cu/Fe and Mn/Fe nano particles were successfully loaded onto NaY zeolite and exhibited larger BET surface area compared to nano-Fe0 (nZVI). Laboratory experiments showed that nitrate removal by metals@Y in unbuffered conditions reached nearly 100% at a dosage of 4g/L after 6h of reaction. Moreover, the nitrate removal was not sensitive to the initial solution pH. Even at a high pH of 9.0, metals@Y exhibited nitrate reduction above 94%. CF@Y demonstrated high N2 selectivity, due to the high content of Cu (20wt%) and Fe (41wt%) in CF@Y and the highly active metallic sites on its surface with positive charge. Kinetic data showed a good fit to a first-order kinetic model during early reaction times. A close fit to both a second-order and an nth-order kinetic model was shown for the whole of the reaction period. The data suggest that both liquid phase mass transfer and the intrinsic reaction rate control the process of nitrate reduction by metals@Y.

Nanoscale measurement of trace element distributions in Spartina alterniflora root tissue during dormancy.

This paper reports a nanometer-scale investigation of trace element (As, Ca, Cr, Cu, Fe, Mn, Ni, S and Zn) distributions in the root system Spartina alterniflora during dormancy. The sample was collected on a salt marsh island in Jamaica Bay, New York, in April 2015 and the root was cross-sectioned with 10 µm resolution. Synchrotron X-ray nanofluorescence was applied to map the trace element distributions in selected areas of the root epidermis and endodermis. The sampling resolution was 60 nm to increase the measurement accuracy and reduce the uncertainty. The results indicate that the elemental concentrations in the epidermis, outer endodermis and inner endodermis are significantly (p < 0.01) different. The root endodermis has relatively higher concentrations of these elements than the root epidermis. Furthermore, this high resolution measurement indicates that the elemental concentrations in the outer endodermis are significantly (p < 0.01) higher than those in the inner endodermis. These results suggest that the Casparian strip may play a role in governing the aplastic transport of these elements. Pearson correlation analysis on the average concentrations of each element in the selected areas shows that most of the elements are significantly (p < 0.05) correlated, which suggests that these elements may share the same transport pathways.

Vanadium uptake and translocation in dominant plant species on an urban coastal brownfield site.

This study, conducted at a brownfield site in New Jersey, USA, investigated factors controlling V uptake and translocation in naturally assembled plant species. Six dominant species were collected from 22 stations in the study area. We found that V concentration in the plants decreased in a sequence of root>leaf>stem. No significant differences were found among the six dominant plant species in terms of root V uptake efficiency (V BCF) and V root to shoot translocation (V TF). Although soil pH and TOC did not show significant impact on V accumulation in the roots, soil labile V content showed significant positive linear correlation (p<0.05) with plant root V. Non-linear regression analysis indicates that V translocation efficiency decreases with increasing concentration in the soil, implying that excessive V in the soil might inhibit its absorption by the plant roots. Leaf V concentration was constant in all the plant species regardless of the variation in soil V concentration. The study shows that the six dominant plant species on site had limited amount of V translocated to the aerial part of the plant.

Lead accumulation and association with Fe on Typha latifolia root from an urban brownfield site.

Synchrotron X-ray microfluorescence and X-ray absorption near-edge microstructure spectroscopy techniques were applied to Typha latifolia (cattail) root sections and rhizosphere soils collected from a brownfield site in New Jersey to investigate lead (Pb) accumulation in T. latifolia roots and the role of iron (Fe) plaque in controlling Pb uptake. We found that Pb and Fe spatial distribution patterns in the root tissues are similar with both metals present at high concentrations mainly in the epidermis and at low concentrations in the vascular tissue (xylem and phloem), and the major Pb and Fe species in T. latifolia root are Pb(II) and Fe(III) regardless of concentration levels. The sequestration of Pb by T. latifolia roots suggests a potential low-cost remediation method (phytostabilization) to manage Pb-contaminated sediments for brownfield remediation while performing wetland rehabilitation.

High-performance planar pH fluorosensor for two-dimensional pH measurements in marine sediment and water.

A new plate fluorosensor foil was developed for two-dimensional pH measurement in marine sediments and overlying waters. The fluorescent dye 8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) was covalently linked onto a transparent poly(vinyl alcohol) membrane backed by polyester sheet. Both excitation and emission bands of the immobilized HPTS showed large red shifts in comparison to HPTS in free solution. The ratio of fluorescence emission intensities at 540 nm following successive excitation at 506 and 428 nm was pH-sensitive and correlated with pH changes from 5.5 to 8.6. These properties are robust and insensitive to factors such as intensity of light source, temperature, and oxygen concentration. The plate sensor responded rapidly (< 2 min), reversibly, and with high precision to pH changes in solution and in sediment. The stability of the sensor was also tested by continually changing the pH between 6 and 8. Performance of the sensor did not vary after > 200 pH cycles. Furthermore, the sensor foil retained its original properties after continuous exposure to natural marine sedimentfor 2 months. The plate optode has been successfully used to measure two-dimensional pH distributions in intertidal flat and subtidal sediment. Images are readily obtained with inexpensive light-emitting diode (LED) excitation and commercial-grade digital cameras with typical pixel resolution of approximately 50 x 50 microm over areas > 150 cm2.

Selective trace analysis of sulfonylurea herbicides in water and soil samples based on solid-phase extraction using a molecularly imprinted polymer.

A molecularly imprinted polymer (MIP) was synthesized using the herbicide metsulfuron-methyl (MSM) as a template, 2-(trifluoromethyl)acrylic acid as a functional monomer, divinylbenzene as a cross-linker, and dichloromethane as a porogen. This polymer was used as a solid-phase extraction material for the quantitative enrichment of five sulfonylureas (nicosulfuron, thifensulfuron-methyl, metsulfuron-methyl, sulfometuron-methyl, and chlorsulfuron) in natural water and soil samples and off-line coupled to a reversed-phase HPLC/diode array detection (HPLC/DAD). Washing solvent was optimized in terms of kind and volume for removing the matrix constituents nonspecifically adsorbed on the MIP. It has been shown that the nonspecific binding ability of the sulfonylureas to the polymer largely increased along with increasing the concentration of Ca2+ ions in the water sample, whereas complexation of divalent ions with EDTA eliminated this interference completely. The stability of MIP was tested by consecutive percolation of water sample, and it was shown that the performance of the MIP did not vary even after 200 enrichment and desorption cycles. Recoveries of the five sulfonylureas extracted from 1 L of tap water and surface water samples such as river water and rainwater at a 50 ng/L spike level were not lower than 96%. The recoveries of sulfonylureas extracted from 10-g soil sample at the 50 microg/kg level were in the range of 71-139%. Depending on the particular compound, the limit of detection varied from 2 to 14 ng/L in water and from 5 to 12 microg/kg in soil samples. The MIP was also compared with a commercially available C-18 column and an immunoaffinity support with encapsulated polyclonal anti-MSM antibodies in sol-gel glass.

Exploitation of reversed micelles as a medium in mimetic peroxidase-catalyzed fluorogenic reaction between hydrogen peroxide and l-tyrosine.

The peroxidase activity of mimetic enzyme, iron tetrasulfonatophthalocyanine (FeTSPc), was characterized in reversed micelles of hexadecyltrimethylammonium bromide (CTAB) formed in n-heptane-n-pentanol solution (2:1, V:V). The assay is based on its catalytic effect on the oxidation reaction of l-tyrosine (l-tyr) by hydrogen peroxide. The influences of environmental factors, such as the water content, CTAB concentration and pH, on the peroxidase activity of FeTSPc were investigated. It was observed that the reaction rate was distinctly enhanced in CTAB reversed micelles as compared with the rate in aqueous solution. Under optimum conditions, application of the FeTSPc-catalyzed fluorescence system in reversed micelles to the determination of H(2)O(2) and FeTSPc led to a highly sensitive system compared with that in aqueous solution, permitting detection limits of 5x10(-9) mol l(-1) H(2)O(2) and 2.3x10(-9) mol l(-1) FeTSPc. The advantages and limitations of employing the reversed micellar media in such mimetic peroxidase-catalyzed fluorescent detection schemes were discussed.

Residue analysis of the pharmaceutical diclofenac in different water types using ELISA and GC-MS.

A highly sensitive and specific indirect competitive enzyme-linked immunosorbent assay (ELISA) for the determination of diclofenac in water samples was developed. With pure water, the limit of detection (LOD, S/N = 3) and IC50 were found to be 6 ng/L and 60 ng/L, respectively. The analytical working range was about 20-400 ng/L. Highest cross-reactivity (CR) of 26 tested pharmaceuticals, metabolites, and pesticides was found for 5-hydroxydiclofenac (100%). Other estimated values were well below 4% and, therefore, are negligible. The assay was applied for the determination of diclofenac in tap and surface water samples as well as wastewater collected at 20 sewage treatment plants (STPs) in Austria and Germany. Humic substances were identified as main interference in surface water. Wastewater samples which were only submitted to filtration and dilution yielded about 25% higher diclofenac concentrations using the ELISA compared to GC-MS. However, the ELISA turned out to be a simple, inexpensive, and accurate method for the determination of diclofenac both in influent and effluent wastewater after rather simple sample preparation, i.e., filtration, acidification, and readjustment to neutral pH-value, and at least 10-fold dilution with pure water.

Flow injection fluorescence immunoassay for gentamicin using sol-gel-derived mesoporous biomaterial.

Sol-gel-derived mesoporous biomaterials were used for the first time in the flow-injection fluorescence immunoassay system. Anti-gentamicin antibody was immobilized in a mesoporous sol-gel material using tetramethoxysilane as a precursor and poly(ethylene glycol) as a template. The sol-gel glass was used to develop an immunoaffinity column for the flow-injection immunoassay of gentamicin. Little unspecific adsorption of gentamicin on the sol-gel and no antibody leaching under harsh elution conditions were found. The immunoassay is based on the competition between gentamicin and fluorescein isothiocyanate-labeled gentamicin for a limited number of encapsulated antibody binding sites. NaOH solution of 5 x 10(-3)mol/L is used for the regeneration of encapsulated antibody binding sites after each measurement, which allows the immunoreactor to be used for up to 20 times without any loss of reactivity. Sample preconcentration is not needed and a single assay can be performed within 10 min. The calibration for gentamicin has a working range of 250-5000 ng/mL with a detection limit of 200 ng/mL, which is close to that of the fluorescence immunoassay and fluorescence polarization immunoassay using the same reactants. Comparison of the results from this method with that obtained from HPLC showed an excellent correlation.