Lead immobilization in mechanochemical fly ash recycling

In previous studies, we focused on a mechanochemical process for recycling fly ash for use in cement; this process was expected to immobilize heavy metals in the fly ash, a desirable outcome in light of the fact that recycled fly ash is commonly used in the synthesis of inorganic materials. Here, we investigated the leaching of lead (Pb) from fly ash treated by a mechanochemical process and from cement prepared from the treated fly ash. We used lead oxide (PbO), a typical Pb compound in fly ash, as a model substance. Mechanochemical treatment of the fly ash inhibited Pb leaching by 93%, and further inhibition (more than 99.9%) was observed in cement produced from the treated fly ash. During the mechanochemical treatment, PbO was reduced to Pb by iron from the stainless-steel mill used for processing, and the lower solubility of Pb in water resulted in immobilization of the Pb.     

Determining storm sampling requirements for improving precision of annual load estimates of nutrients from a small forested watershed

This study sought to determine the lowest number of storm events required for adequate estimation of annual nutrient loads from a forested watershed using the regression equation between cumulative load (∑L) and cumulative stream discharge (∑Q). Hydrological surveys were conducted for 4 years, and stream water was sampled sequentially at 15-60-min intervals during 24 h in 20 events, as well as weekly in a small forested watershed. The bootstrap sampling technique was used to determine the regression (∑L-∑Q) equations of dissolved nitrogen (DN) and phosphorus (DP), particulate nitrogen (PN) and phosphorus (PP), dissolved inorganic nitrogen (DIN), and suspended solid (SS) for each dataset of ∑L and ∑Q. For dissolved nutrients (DN, DP, DIN), the coefficient of variance (CV) in 100 replicates of 4-year average annual load estimates was below 20% with datasets composed of five storm events. For particulate nutrients (PN, PP, SS), the CV exceeded 20%, even with datasets composed of more than ten storm events. The differences in the number of storm events required for precise load estimates between dissolved and particulate nutrients were attributed to the goodness of fit of the ∑L-∑Q equations. Bootstrap simulation based on flow-stratified sampling resulted in fewer storm events than the simulation based on random sampling and showed that only three storm events were required to give a CV below 20% for dissolved nutrients. These results indicate that a sampling design considering discharge levels reduces the frequency of laborious chemical analyses of water samples required throughout the year.     

Regulation of the dissolved phosphate concentration of a mountainous stream, Kitakyushu, southwestern Japan

The phosphate concentration in mountainous stream water can be a measure of the forest condition, because its concentration will be low when the biomass in the forest is increasing and vice versa when the forest is declining. To investigate the seasonal change in the dissolved phosphate concentration of the mountainous stream water of the Yamakami River, Kitakyushu, from June 2009 to August 2010, and the regulation mechanism of the phosphate concentration, solid-phase spectrophotometry, which can be applicable to natural water without any pretreatment procedures, was employed for the determination of phosphate at μg P L(-1) levels in natural water. The phosphate concentrations in the mountainous stream waters at 6 sites ranged from 2.2 to 13 μg P L(-1), and those from the catchment area of the steady state forest were 5.3 ± 1.6 (±1 SD) μg P L(-1). Changes in the concentration were fairly small even during a storm runoff. The average phosphate concentration of rain was 2.8 ± 0.7 μg P L(-1), about half of the concentration in the stream water. The rate of runoff in forest areas is generally considered to be about 50% of the total precipitation. For a forest under a climax condition, the phosphate concentration is estimated to be regulated by the fallout and evapotranspiration (α = 0.05). At one of the sites, an upstream tributary, where a fairly big landslide occurred before July in 2009, the phosphate concentration was the highest, suggesting that the biomass may still be decreasing. For all of the six sites examined, a characteristic seasonal change in phosphate concentration was observed, reflecting the local budget between the biological decomposition of plant matter and the consumption by the biomass. The increase in the phosphate concentration during late spring and early summer may result from the extensive decomposition of plant litter mainly supplied in autumn and of plant matter relating to spring blooming such as fallen flowers, pollen and immature fruits. The proposed method using the phosphate concentration in surface stream waters without the period of the seasonal change mentioned above is expected to be very helpful in diagnosing the condition of forests.     

Pyrolysis of tetrabromobisphenol-A containing paper laminated printed circuit boards

Tetrabromobisphenol-A (TBBA) is the most common brominated fire retardant. In this study, a TBBA containing paper laminated printed circuit board (PCB) prepared from novolac was pyrolysed by both TGA and in a quartz glass reactor between 40 and 1,000 degrees C. The products were online detected by MS. It was found that the PCB degraded in three steps. Step one (<270 degrees C) consisted of the evolution of water and CO(2) from the paper laminate. In the second step, between 270 and 370 degrees C, the fire retardant decomposed, releasing HBr and brominated aromatics. In the third step, at temperatures above 370 degrees C, the phenol resin decomposed and char was formed. Compared to pure TBBA, which mainly produces brominated phenols, the brominated products enclosed in the char released HBr during the last degradation step as well as during the second step. Most of the bromine left the resin in the form of HBr, with about 14% of the bromine being fixed in brominated aromatics and less than 2% remaining in the residue.     

Prediction of Fenton oxidation positions in polycyclic aromatic hydrocarbons by Frontier electron density

Five recalcitrant polycyclic aromatic hydrocarbons (PAHs) in ethanol were subjected to Fenton oxidation, and following GC-MS identification of respective oxidation products, their oxidation positions were compared to those predicted by Frontier electron density. Quinone forms of oxidation products were identified in each PAH. With the exception of fluorene, oxidation positions of quinone forms of products of acenaphthylene, anthracene, benz(a)anthracene, and benzo(a)pyrene corresponded with predicted positions in which Frontier electron density was high. From these results, it appears that determining the Frontier electron density of a PAH is a promising method for predicting the Fenton oxidation position.