Trace metals in the hair of habitants of the Ok Tedi region, Papua New Guinea

It has long been known that mining activity can markedly change the level and distribution of certain heavy metals in the adjacent environment. This pollution can be quite widespread and long lasting and often has deleterious effects on the health of local populations. In the present study scalp hair was used as the biopsy material because of its ease of collection and long history of use in this connection. Hair was collected from all the local villages in the vicinity of the mine site, as well as from Papua New Guinean nationals from other provinces, and European expatriates who were employed by the mining company and who were resident in the area. Hair from local people showed a remarkably high iron content by comparison with previously studied populations. The extreme variations in hair iron levels were reflected in the differential distribution of levels according to location, age and sex. Hair cadmium was also high in the population studied. Hair copper, lead, zinc and mercury all appeared to be within 'normal' limits by comparison with other general populations. These results are discussed in the context of the environmental and social impact of the mining operations on the local people.     

The relationships between mercury and selenium in plankton and fish from a tropical food web

Background, aim, and scope  Selenium (Se) has been shown to reduce mercury (Hg) bioavailability and trophic transfer in aquatic ecosystems. The study of methylmercury (MeHg) and Se bioaccumulation by plankton is therefore of great significance in order to obtain a better understanding of the estuarine processes concerning Hg and Se accumulation and biomagnification throughout the food web. In the western South Atlantic, few studies have documented trace element and MeHg in fish tissues. No previous study about trace elements and MeHg in plankton has been conducted concerning tropical marine food webs. Se, Hg, and MeHg were determined in two size classes of plankton, microplankton (70–290 μm) and mesoplankton (≥290 μm), and also in muscle tissues and livers of four fish species of different trophic levels (Mugil liza, a planktivorous fish; Bagre spp., an omnivorous fish; Micropogonias furnieri, a benthic carnivorous fish; and Centropomus undecimalis, a pelagic carnivorous fish) from a polluted estuary in the Brazilian Southeast coast, Guanabara Bay. Biological and ecological factors such as body length, feeding habits, and trophic transfer were considered in order to outline the relationships between these two elements. The differences in trace element levels among the different trophic levels were investigated. Materials and methods  Fish were collected from July 2004 to August 2005 at Guanabara Bay. Plankton was collected from six locations within the bay in August 2005. Total mercury (THg) was determined by cold vapor atomic absorption spectrometry (CV-AAS) with sodium borohydride as a reducing agent. MeHg analysis was conducted by digesting samples with an alcoholic potassium hydroxide solution followed by dithizone-toluene extraction. MeHg was then identified and quantified in the toluene layer by gas chromatography with an electron capture detector (GC-ECD). Se was determined by AAS using graphite tube with Pin platform and Zeeman background correction. Results and discussion  Total mercury, MeHg, and Se increased with plankton size class. THg and Se values were below 2.0 and 4.8 μg g⁻¹ dry wt in microplankton and mesoplankton, respectively. A large excess of molar concentrations of Se in relation to THg was observed in both plankton size class and both fish tissues. Plankton presented the lowest concentrations of this element. In fish, the liver showed the highest THg and Se concentrations. THg and Se in muscle were higher in Centropomus undecimalis (3.4 and 25.5 nmol g⁻¹) than in Micropogonias furnieri (2.9 and 15.3 nmol g⁻¹), Bagre spp (1.3 and 3.4 nmol g⁻¹) and Mugil liza (0.3 and 5.1 nmol g⁻¹), respectively. The trophic transfer of THg and Se was observed between trophic levels from prey (considering microplankton and mesoplankton) to top predator (fish). The top predators in this ecosystem, Centropomus undecimalis and Micropogonias furnieri, presented similar MeHg concentrations in muscles and liver. Microplankton presented lower ratios of methylmercury to total mercury concentration (MeHg/THg) (34%) than those found in mesoplankton (69%) and in the muscle of planktivorous fish, Mugil liza (56%). The other fish species presented similar MeHg/THg in muscle tissue (of around 100%). M. liza showed lower MeHg/THg in the liver than C. undecimalis (35%), M. furnieri (31%) and Bagre spp. (22%). Significant positive linear relationships were observed between the molar concentrations of THg and Se in the muscle tissue of M. furnieri and M. liza. These fish species also showed significant inverse linear relationships between hepatic MeHg and Se, suggesting a strong antagonistic effect of Se on MeHg assimilation and accumulation. Conclusions  Differences found among the concentrations THg, MeHg, and Se in microplankton, mesozooplankton, and fishes were probably related to the preferred prey and bioavailability of these elements in the marine environment. The increasing concentration of MeHg and Se at successively higher trophic levels of the food web of Guanabara Bay corresponds to a transfer between trophic levels from the lower trophic level to the top-level predator, suggesting that MeHg and Se were biomagnified throughout the food web. Hg and Se were positively correlated with the fish standard length, suggesting that larger and older fish bioaccumulated more of these trace elements. THg, MeHg, and Se were a function of the plankton size. Recommendations and perspectives  There is a need to assess the role of selenium in mercury accumulation in tropical ecosystems. Without further studies of the speciation of selenium in livers of fishes from this region, the precise role of this element, if any, cannot be verified in positively affecting mercury accumulation. Further studies of this element in the study of marine species should include liver samples containing relatively high concentrations of mercury. A basin-wide survey of selenium in fishes is also recommended.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.     

Method to assess component contribution to toxicity of complex mixtures: Assessment of puberty acquisition in rats exposed to disinfection byproducts

A method based on regression modeling was developed to discern the contribution of component chemicals to the toxicity of highly complex, environmentally realistic mixtures of disinfection byproducts(DBPs). Chemical disinfection of drinking water forms DBP mixtures.Because of concerns about possible reproductive and developmental toxicity, a whole mixture(WM) of DBPs produced by chlorination of a water concentrate was administered as drinking water to Sprague–Dawley(S–D) rats in a multigenerational study. Age of puberty acquisition,i.e., preputial separation(PPS) and vaginal opening(VO), was examined in male and female offspring, respectively. When compared to controls, a slight, but statistically significant delay in puberty acquisition was observed in females but not in males. WM-induced differences in the age at puberty acquisition were compared to those reported in S–D rats administered either a defined mixture(DM) of nine regulated DBPs or individual DBPs. Regression models were developed using individual animal data on age at PPS or VO from the DM study. Puberty acquisition data reported in the WM and individual DBP studies were then compared with the DM models. The delay in puberty acquisition observed in the WM-treated female rats could not be distinguished from delays predicted by the DM regression model, suggesting that the nine regulated DBPs in the DM might account for much of the delay observed in the WM. This method is applicable to mixtures of other types of chemicals and other endpoints.     

Evaluating the effectiveness of marine actinobacterial extract and its mediated titanium dioxide nanoparticles in the degradation of azo dyes

Aim of the present study was to synthesize titanium dioxide nanoparticles （YiO2 NPs） from marine actinobacteria and to develop an eco-friendly azo-dye degradation method. A total of five actinobacterial isolates were isolated from Chennai marine sediments, Tamilnadu, India and analyzed for the synthesis of TiO2 NPs using titanium hydroxide. Among these, the isolate PSV 3 showed positive results for the synthesis of TiO2 NPs, which was confirmed by UV analysis. Further characterization of the synthesized TiO2 NPs was done using XRD, AFM and FI＇-IR analysis. Actinobacterial crude extract and synthesized TiO2 NPs was found efficient in degrading azo dye such as Acid Red 79 （AR-79） and Acid Red 80 （AR-80）. Degradation percentage was found to be 81% for AR-79, 83% for AR-80 using actinobacterial crude extract and 84% for AR-79, 85% for AR-80 using TiO2 NPs. Immobilized actinobacterial ceils showed 88% for AR-79 and 81% for AR- 80, dye degrading capacity. Degraded components were characterized by FT-IR and GC-MS analysis. The phytotoxicity test with 500 μg/mL of untreated dye showed remarkable phenotypic as well as cellular damage to Tagetes erecta plant. Comparatively no such damage was observed on plants by degraded dye components. In biotoxicity assay, treated dyes showed less toxic effect as compared to the untreated dyes.     

Influence of water treatment residuals on phosphorus solubility and leaching

Laboratory and greenhouse studies compared the ability of water treatment residuals (WTRs) to alter P solubility and leaching in Immokalee sandy soil (sandy, siliceous, hyperthermic Arenic Alaquod) amended with biosolids and triple superphosphate (TSP). Aluminum sulfate (Al-WTR) and ferric sulfate (Fe-WTR) coagulation residuals, a lime softening residual (Ca-WTR) produced during hardness removal, and pure hematite were examined. In equilibration studies, the ability to reduce soluble P followed the order Al-WTR > Ca-WTR = Fe-WTR > hematite. Differences in the P-fixing capacity of the sesquioxide-dominated materials (Al-WTR, Fe-WTR, hematite) were attributed to their varying reactive Fe- and Al-hydrous oxide contents as measured by oxalate extraction. Leachate P was monitored from greenhouse columns where bahiagrass (Paspalum notatum Flugge) was grown on Immokalee soil amended with biosolids or TSP at an equivalent rate of 224 kg P ha(-1) and WTRs at 2.5% (56 Mg ha(-1)). In the absence of WTRs, 21% of TSP and 11% of Largo cake biosolids total phosphorus (PT) leached over 4 mo. With co-applied WTRs, losses from TSP columns were reduced to 3.5% (Fe-WTR), 2.5% (Ca-WTR), and <1% (Al-WTR) of applied P. For the Largo biosolids treatments all WTRs retarded downward P flux such that leachate P was not statistically different than for control (soil only) columns. The phosphorus saturation index (PSI = [Pox]/ [Al(ox) + Fe(ox)], where Pox, Al, and Fe(ox) are oxalate-extractable P, Al, and Fe, respectively) based on a simple oxalate extraction of the WTR and biosolids is potentially useful for determining WTR application rates for controlled reduction of P in drainage when biosolids are applied to low P-sorbing soils.     

Boosted Regression Tree Models to Explain Watershed Nutrient Concentrations and Biological Condition

Boosted regression tree (BRT) models were developed to quantify the nonlinear relationships between landscape variables and nutrient concentrations in a mesoscale mixed land cover watershed during base‐flow conditions. Factors that affect instream biological components, based on the Index of Biotic Integrity (IBI), were also analyzed. Seasonal BRT models at two spatial scales (watershed and riparian buffered area [RBA]) for nitrite‐nitrate (NO₂‐NO₃), total Kjeldahl nitrogen, and total phosphorus (TP) and annual models for the IBI score were developed. Two primary factors — location within the watershed (i.e., geographic position, stream order, and distance to a downstream confluence) and percentage of urban land cover (both scales) — emerged as important predictor variables. Latitude and longitude interacted with other factors to explain the variability in summer NO₂‐NO₃ concentrations and IBI scores. BRT results also suggested that location might be associated with indicators of sources (e.g., land cover), runoff potential (e.g., soil and topographic factors), and processes not easily represented by spatial data indicators. Runoff indicators (e.g., Hydrological Soil Group D and Topographic Wetness Indices) explained a substantial portion of the variability in nutrient concentrations as did point sources for TP in the summer months. The results from our BRT approach can help prioritize areas for nutrient management in mixed‐use and heavily impacted watersheds.     

Evaluating Infiltration Requirements for New Development Using Extreme Storm Transposition: A Case Study from Dane County,WI

Changes in land use and extreme rainfall trends can lead to increased flood vulnerability in many parts of the world, especially for urbanized watersheds. This study investigates the performance of existing stormwater management strategies for the Upper Yahara watershed in Dane County, WI to determine whether they are adequate to protect urban and suburban development from an extreme rainfall. Using extreme storm transposition, we model the performance of the stormwater infiltration practices required for new development under current county ordinances. We find during extreme rainfall the volume of post‐development runoff from impervious surfaces from a typical site would increase by over 55% over pre‐development conditions. We recommend the ordinance be strengthened to reduce vulnerability to flooding from future urban expansion and the likely increase in the magnitude and frequency of extreme storms.     

Elimination of Methanol and Ethanol by Biofiltration: An Experimental Study

This study presents the experimental results obtained during long-term operation of two biofilters treating two alcohols: methanol and ethanol. The biofilters used for this purpose were previously packed with a compost material made from tobacco processing residues. The alcohols concentrations tested lay between 0.40 and 3.20 g/m³ for methanol, and 0.55 and 5.05 g/m³ for ethanol. The empty bed residence time in each biofilter was 60 s. Biofilter inlet loads of less than 190 and 300 g/m³/h for the methanol and ethanol additions respectively, were thereafter evaluated. In addition, the concentrations of nutrient nitrogen were also varied, from 0.1 to 2.0 g-N/l and from 0.3 to 11.3 g-N/l for the ethanol and the methanol, respectively. The results thus obtained have made it possible to select the optimal nitrogen concentrations which, for the cases examined, turn out to be 0.3 g-N/l and between 2 and 3.8 g-N/l for the ethanol and methanol substrates, respectively. The maximum elimination capacities obtained in this study were 82 and 150 g/m³/h, respectively for the methanol and ethanol cases. It was therefore concluded that, for a readily biodegradable compound such as ethanol, the nitrogen requirement is substantially lower than that needed for the methanol degradation, the latter appearing to be more difficult to degrade biologically under similar operating conditions. The production rate of the co-product carbon dioxide during methanol and ethanol biofiltration was also investigated. Also, a good correlation was found to exist between the temperature and the conversion achieved in the biofilter.