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.     

The occurrence of cyanide formation in six full-scale publicly owned treatment works.

This paper presents results from an intensive monitoring program implemented at six full-scale publicly owned treatment works (POTWs) to investigate the fate and formation of cyanide in wastewater treatment processes, with a focus on chlorination and dechlorination processes. A review of historical monitoring data for cyanide species in these POTWs was also conducted. This POTW monitoring program provided a database for the investigation of cyanide formation in wastewater secondary treatment. Data from participating POTWs showed evidence of cyanide formation in this 1-year monitoring effort, although the cyanide formation pattern varied significantly from one plant to another and among seasons. Generally, the chlorination of thiocyanate (SCN-) seems to be the most important mechanism for the formation of cyanide in wastewater treatment processes, especially in chlorination and dechlorination. This hypothesis is supported by the findings of a related laboratory study of mechanisms of cyanide formation in POTWs. It is recommended that POTWs monitor SCN in influent and secondary effluent to identify its presence and adjust chlorine dose appropriately.     

Current Near‐to‐Nature Forest Management Effects on Functional Trait Composition of Saproxylic Beetles in Beech Forests

With the aim of wood production with negligible negative effects on biodiversity and ecosystem processes, a silvicultural practice of selective logging with natural regeneration has been implemented in European beech forests (Fagus sylvatica) during the last decades. Despite this near‐to‐nature strategy, species richness of various taxa is lower in these forests than in unmanaged forests. To develop guidelines to minimize the fundamental weaknesses in the current practice, we linked functional traits of saproxylic beetle species to ecosystem characteristics. We used continental‐scale data from 8 European countries and regional‐scale data from a large forest in southern Germany and forest‐stand variables that represented a gradient of intensity of forest use to evaluate the effect of current near‐to‐nature management strategies on the functional diversity of saproxylic beetles. Forest‐stand variables did not have a statistically significant effect on overall functional diversity, but they did significantly affect community mean and diversity of single functional traits. As the amount of dead wood increased the composition of assemblages shifted toward dominance of larger species and species preferring dead wood of large diameter and in advanced stages of decay. The mean amount of dead wood across plots in which most species occurred was from 20 to 60 m³/ha. Species occurring in plots with mean dead wood >60 m³/ha were consistently those inhabiting dead wood of large diameter and in advanced stages of decay. On the basis of our results, to make current wood‐production practices in beech forests throughout Europe more conservation oriented (i.e., promoting biodiversity and ecosystem functioning), we recommend increasing the amount of dead wood to >20 m³/ha; not removing dead wood of large diameter (50 cm) and allowing more dead wood in advanced stages of decomposition to develop; and designating strict forest reserves, with their exceptionally high amounts of dead wood, that would serve as refuges for and sources of saproxylic habitat specialists. Efectos Actuales del Manejo Casi Natural de Bosques sobre la Composición de Atributos Funcionales de Escarabajos Saproxílicos en Bosques de Haya     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

Nitromusk compounds in San Francisco Bay sediments

Synthetic nitromusk fragrances are used in a wide variety of consumer products and can enter aquatic environments through wastewater effluent. Although nitromusks are known to be hydrophobic, little attention has been paid to their behavior in sediments. A sediment extraction method using sonication was developed and used to analyze samples from San Francisco Bay. Both musk xylene (MX) and musk ketone (MK) were found at low levels, with mean concentrations of 0.034 and 0.038ngg(-1), respectively. The highest concentrations were found in the southernmost region of the Bay. Samples were also analyzed from a nearby tidal channel fed by a wastewater treatment plant outfall. At this location both musk xylene and musk ketone were found at higher concentrations of 0.13-0.24ngg(-1) MX and 1.08-2.74ngg(-1) MK. A metabolite of musk xylene was also found at levels up to 4.08ngg(-1), suggesting that these metabolites may play an important role in the fate of nitromusk compounds. Concentrations of all three compounds were highest at the earliest of four sampling dates, and a geographic survey of sediments along the tidal channel showed that concentrations decreased rapidly with distance from the outfall and were close to background before the channel reached the Bay.     

Formation of free cyanide and cyanogen chloride from chloramination of publicly owned treatment works secondary effluent: laboratory study with model compounds.

The potential generation of cyanide species in wastewater upon chlorination in the presence of residual ammonia (resulting in chloramine formation) was investigated in experiments with synthetic solutions and publicly owned treatment works (POTW) secondary effluent. This study demonstrated that low concentrations (approximately 5 to 25 microg/L as cyanide) of cyanogen chloride (CNCI), a highly toxic cyanide species not measured in total or free cyanide analyses, could be detected as a result of chloramination reactions in POTW secondary effluent. The potential for chloramination of nitrogen-bearing organic compounds to yield CNCl and/or free cyanide was demonstrated in experiments with synthetic solutions spiked with selected precursor organics: L-serine, benzene, catechin, and humic acid. The amino acid L-serine yielded the largest concentrations of CNCI upon chloramination. Additionally, detectable cyanide (approximately 10 microg/L) was observed in solutions of L-serine and in POTW secondary effluent that was chloraminated followed by dechlorination to prevent destruction of any free cyanide produced. Thus, chlorination of POTW secondary effluent containing residual ammonia can lead to chloramination of organic compounds and the resulting production of CNCl and free cyanide.     

Risk-based prenatal screening for trisomy 18 using alpha-fetoprotein,unconjugated oestriol and human chorionic gonadotropin

Nine centres collaborated to examine the feasibility of a screening method for trisomy 18 that was based on assigning individual risk, using a combination of maternal age and measurements of alpha-fetoprotein (AFP), unconjugated oestriol (uE3), and human chorionic gonadotropin (hCG). Second-trimester measurements of these analytes were obtained from 94 trisomy 18 pregnancies. In the 89 pregnancies without an associated open defect, the median levels for AFP, uE3, and hCG were 0.65, 0.43 and 0.36 multiples of the unaffected population median, respectively. The strongest individual predictor of risk for trisomy 18 was uE3, followed by hCG, AFP, and maternal age, in that order. Using a method of individual risk estimation that is based on the three markers and maternal age, 60 per cent of pregnancies associated with trisomy 18 would be detected at a risk cut-off level of 1:100, with a false-positive rate of about 0.2 per cent. One in nine pregnancies identified as being at increased risk for trisomy 18 would be expected to have an affected pregnancy. This risk-based screening method is more efficient than an existing method that is based on fixed analyte cut-off levels. Even though the birth prevalence of trisomy 18 is low, prenatal screening can be justified when performed in conjunction with Down syndrome screening and when a high proportion of women offered amniocentesis have an affected fetus.     

Effects of nitrosation on the formation of cyanide in publicly owned treatment works secondary effluent.

Cyanide has been detected in the effluents of some publicly owned treatment works (POTWs) at levels exceeding the influent concentration. The presence of nitrite ion (NO2-) as a common constituent in domestic wastewater effluents may play an important role in the formation of cyanide through reaction with certain kinds of organic compounds, especially aromatic compounds. Laboratory studies with seven organic compounds (aniline. p-toluidine, phenol, 1,2,4-trihydroxybenzene, L-serine, glycine, and benzoic acid) revealed that cyanide can be formed by reaction of nitrite with some of these compounds. The most substantial free cyanide (HCN. CN-) production observed at 25 degrees C was 0.15 mg/L from reaction of 0.01 mM 1.2.4-trihydroxybenze with 5 mg/L nitrite for 72 hours. Substantial free cyanide formation was also observed at pH 2-4 in experiments with POTW effluents when reactive organics and nitrite were both added to wastewater. Formation of cyanide through nitrosation was strongly pH dependent, being most significant at low pH (2 to 4) and negligible at neutral-to-high pH. This result points to nitrous acid (HNO2) as being more reactive than the dissociated NO2- ion. The reaction of these nitrite species with organics also occurs in conventional analyses for total cyanide which involve distillation under strongly acidic conditions. Sufficient sample pretreatment with sulfamic acid at the time of sampling, not at the time of analysis. is highly recommended to prevent biasing analytical measurement of total cyanide in POTW effluents.