Leaching characteristics of stabilized/solidified fly ash generated from ash-melting plant

This study was designed to elucidate the leaching characteristics of stabilized/solidified (S/S) fly ash generated by ash-melting. For this study, pH-dependent leaching tests, sequential extraction procedures, and column leaching tests were carried out. The pH-dependent leaching test results for Pb, Cu, and Zn showed that the heavy metal concentrations in the high-pH range were lower than the predicted values for hydroxide and carbonate. During sequential extraction, Cu and Pb were principally distributed in the S/S ashes' organic matter fraction in the chelating agent, suggesting that metals bind to the chelating agent. The percentage of the water-soluble fraction for Pb and Cu was low (<0.2 %). The fly ashes treated with a chelating agent and cement had low leachability potential for metals in the high-pH range. Column tests for S/S fly ashes showed that two leaching stages were distinguishable: one for short time, corresponding to faster metal leaching, and another for the leaching rate. Kinetic speciation was then applied to data obtained from column leaching tests. The first-order reaction/diffusion model showed a better fit for Ca, Pb, and Cu, suggesting that the initial dissolution of soluble compounds, such as metal chloride, was controlled by the first-order reaction (surface wash off). Subsequently, insoluble compounds such as hydroxide or carbonate might penetrate into the porous matrix by diffusion.     

Seaweed sex pheromones and their degradation products frequently suppress amphipod feeding but rarely suppress sea urchin feeding

Summary. A diverse group of brown seaweeds produce bouquets of C₁₁ metabolites, some of which act as pheromones that cue gamete release or attract sperm to eggs following release. We demonstrate that these C₁₁ metabolites and their degradation products also frequently and strongly deter feeding by the herbivorous amphipod Ampithoe longimana, but rarely by the herbivorous sea urchin Arbacia punctulata. Across the range of concentrations tested, seven of twelve C₁₁ metabolites or mixtures that we tested deterred feeding by the amphipod, but only two of eleven deterred the sea urchin. For those compounds where we could rigorously contrast the magnitude of deterrence against the amphipod with the magnitude of deterrence against the urchin, the amphipod was deterred significantly more than the urchin by five of six metabolites. Thus, C₁₁ compounds were more frequently and more strongly deterrent to the amphipod than to the sea urchin. These findings for C₁₁ metabolites conflict with previous investigations, where other classes of seaweed chemical defenses have been shown to deter feeding by large mobile herbivores like urchins and fishes but to be relatively ineffective against mesograzers, especially the species of amphipod that we used here. Our results suggest that C₁₁ metabolites are unusual among the known seaweed chemical defenses in that they are especially effective against mesograzers, which often consume seaweed spores, zygotes, and juveniles. The high concentrations of C₁₁ metabolites in brown algal eggs could allow these defenses to be especially important in defending gametes, zygotes, or young sporelings from herbivorous mesograzers. Received 26 February 1998; accepted 9 April 1998.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Assessment of the labile fractions of copper and zinc in marinas and port areas in Southern Brazil

The dissolved labile and labile particulate fractions (LPF) of Cu and Zn were analyzed during different seasons and salinity conditions in estuarine waters of marina, port, and shipyard areas in the southern region of the Patos Lagoon (RS, Brazil). The dissolved labile concentration was determined using the diffusive gradients in thin films technique (DGT). DGT devices were deployed in seven locations of the estuary for 72 h and the physicochemical parameters were also measured. The LPF of Cu and Zn was determined by daily filtering of water samples. Seasonal variation of DGT–Cu concentrations was only significant (p?<?0.05) at one shipyard area, while DGT–Zn was significant (p?<?0.05) in every locations. The LPF of Cu and Zn concentrations demonstrated seasonal and spatial variability in all locations, mainly at shipyard areas during high salinity conditions. In general, except the control location, the sampling locations showed mean variations of 0.11–0.45 μg?L^?1 for DGT–Cu, 0.89–9.96 μg?L^?1 for DGT–Zn, 0.65–3.69 μg?g^?1 for LPF–Cu, and 1.35–10.87 μg?g^?1 for LPF–Zn. Shipyard areas demonstrated the most expressive values of labile Cu and Zn in both fractions. Strong relationship between DGT–Zn and LPF–Zn was found suggesting that the DGT–Zn fraction originates from the suspended particulate matter. Water salinity and suspended particulate matter content indicated their importance for the control of the labile concentrations of Cu and Zn in the water column. These parameters must be taken into consideration for comparison among labile metals in estuaries.     

Roadside Rhododendron pulchrum leaves as bioindicators of heavy metal pollution in traffic areas of Okayama, Japan

The leaves of roadside Rhododendron pulchrum Sweet were examined as a bioindicator of traffic-related heavy metal pollution in Okayama. Total contents of heavy metals in roadside soil and the R. pulchrum leaves were determined. Results of correlation analyses showed significant correlations among Pb, Ni, and Zn contents of roadside soil and leaf samples. These results suggest that R. pulchrum is a useful bioindicator of heavy metal pollution in traffic areas. To identify traffic-related heavy metal pollution sources, traffic-related materials such as tires, asphalt pavement, and road paint were collected and analyzed. The results of analyses of our data show that Zn is emitted mainly from the abrasion of tires; Cr is emitted mainly from wear of the asphalt pavement. Furthermore, the respective lead isotope ratios in R. pulchrum leaves, soil, roadside dust, and traffic-related materials were measured using inductively coupled plasma mass spectrometry. The isotopic compositions of lead in R. pulchrum leaves were 207Pb/206Pb = 0.861-0.871 and 208Pb/206Pb = 2.093-2.127, which agrees well with ratios in automobile wheel balance weights, suggesting that lead-containing products associated with automobiles, such as wheel balance weights, contribute to traffic-related lead pollution.     

Polycyclic aromatic hydrocarbons (PAHs) in surface sediments from the Bizerte Lagoon,Tunisia: levels,sources, and toxicological significance

To assess the status of polycyclic aromatic hydrocarbon (PAH) contamination in sediments from the Bizerte Lagoon (northern Tunisia), 18 surface sediment samples were collected in March 2011 and analyzed for 14 US Environmental Protection Agency priority PAHs by high-performance liquid chromatography. The total concentrations of the 14 PAHs (ΣPAHs) ranged from 16.9 to 394.1 ng g^?1 dry weight (dw) with a mean concentration of 85.5 ng g^?1 dw. Compared with other lagoons, coasts, and bays in the world, the concentrations of PAHs in surface sediments of the Bizerte Lagoon are low to moderate. The PAHs’ composition pattern was dominated by the presence of four-ring PAHs (45.8 %) followed by five-ring (26.8 %) and three-ring PAHs (12.7 %). The PAH source analysis suggested that the main origin of PAHs in the sediments of the lagoon was mainly from pyrolytic sources. According to the numerical effect-based sediment quality guidelines of the USA, the levels of PAHs in the Bizerte Lagoon should not exert adverse biological effects. The total benzo[a]pyrene toxicity equivalent values calculated for the samples varied from 3.1 to 53.7 ng g^?1 dw with an average of 10.6 ng g^?1 dw.     

Soil response to a 3-year increase in temperature and nitrogen deposition measured in a mature boreal forest using ion-exchange membranes

The projected increase in atmospheric N deposition and air/soil temperature will likely affect soil nutrient dynamics in boreal ecosystems. The potential effects of these changes on soil ion fluxes were studied in a mature balsam fir stand (Abies balsamea [L.] Mill) in Quebec, Canada that was subjected to 3 years of experimentally increased soil temperature (+4 °C) and increased inorganic N concentration in artificial precipitation (three times the current N concentrations using NH₄NO₃). Soil element fluxes (NO₃, NH₄, PO₄, K, Ca, Mg, SO₄, Al, and Fe) in the organic and upper mineral horizons were monitored using buried ion-exchange membranes (PRS? probes). While N additions did not affect soil element fluxes, 3 years of soil warming increased the cumulative fluxes of K, Mg, and SO₄ in the forest floor by 43, 44, and 79 %, respectively, and Mg, SO₄, and Al in the mineral horizon by 29, 66, and 23 %, respectively. We attribute these changes to increased rates of soil organic matter decomposition. Significant interactions of the heating treatment with time were observed for most elements although no clear seasonal patterns emerged. The increase in soil K and Mg in heated plots resulted in a significant but small K increase in balsam fir foliage while no change was observed for Mg. A 6–15 % decrease in foliar Ca content with soil warming could be related to the increase in soil-available Al in heated plots, as Al can interfere with the root uptake of Ca.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Determination of selenium by GFAAS in slurries of fish feces to estimate the bioavailability of this micronutrient in feed used in pisciculture

This paper presents a simple, fast and sensitive method to determine selenium in samples of feces and of fish feed by graphite furnace atomic absorption spectrometry (GFAAS) through the direct introduction of slurries of the samples into the spectrometer's graphite tube. The limits of detection (LOD) and quantification (LOQ) calculated for 20 readings of the blank of the standard slurries (0.50% m/v of feces or feed devoid of selenium) were 0.31 microg l(-1) and 1.03 microg l(-1), respectively, for the standard feces slurries and 0.35 microg l(-1) and 1.16 microg l(-1), respectively, for the standard feed slurries. The proposed method was applied in studies of bioavailability of selenium in different fish feeds and the results proved consistent with that obtained from samples mineralized by acid digestion using the microwave oven.     

Historical and geographical aspects of the increasing perfluorooctanoate and perfluorooctane sulfonate contamination in human serum in Japan

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have recently received attention due to their widespread contamination in the environment, as well as in wildlife and humans. We measured the PFOS and PFOA concentrations in historically recorded human serum samples at an age range between 20 and 59 years collected in Kyoto, 20 persons per each time point (n=100), and also the PFOS and PFOA concentrations in human serum samples at an age range between 20 and 59 years from 10 locations throughout Japan (n=200). The historical samples collected from 1983 to 1999 demonstrated that the PFOA concentrations in males and females from Kyoto have increased 4.4-fold and 4.3-fold at a rate of increase of 0.49 ng/ml/year and 0.42 ng/ml/year, respectively. In contrast, serum concentrations of PFOS reached a plateau in the late 1980s. There are also regional differences in both the PFOS and PFOA serum concentrations. The concentrations in serum [geometric mean (geometric standard deviation)] (ng/ml) in 2003-2004 ranged from 7.6(1.6) in the town of Matsuoka in Fukui prefecture to 27.8(1.6) in Kyoto city, and ranged from 2.3(1.5) in Matsuoka to 14.5(1.3) in Osaka city for PFOS and PFOA, respectively.