Photochemical decomposition of environmentally persistent short-chain perfluorocarboxylic acids in water mediated by iron(II)/(III) redox reactions

The photochemical decomposition of short-chain (C(3)-C(5)) perfluorocarboxylic acids (PFCAs) was investigated. Direct photolysis in water proceeded slowly with the 220- to 460-nm light emission from a xenon-mercury lamp to form F(-), CO(2), and shorter-chain PFCAs. Addition of a small amount of Fe(3+) to the aqueous solutions of the PFCAs dramatically enhanced their photochemical decomposition under an oxygen atmosphere: when the (initial PFCA)/(initial Fe(3+)) molar ratio was 13.5 (initial PFCA concentration=67.3mM), the pseudo-first-order rate constants for the PFCA decomposition were 3.6-5.3 times those with photolysis alone, and the turnover number for the catalytic PFCA decomposition [i.e., (moles of decomposed PFCA)/(moles of initial Fe(3+))] reached 6.71-8.68 after 24h of irradiation. The catalysis can be explained by photoredox reactions between PFCA, Fe(3+)/Fe(2+) and oxygen via photo-induced complexation of Fe(3+) with the PFCAs.     

Handling the phosphorus paradox in agriculture and natural ecosystems: Scarcity,necessity, and burden of P

This special issue of Ambio compiles a series of contributions made at the 8th International Phosphorus Workshop (IPW8), held in September 2016 in Rostock, Germany. The introducing overview article summarizes major published scientific findings in the time period from IPW7 (2015) until recently, including presentations from IPW8. The P issue was subdivided into four themes along the logical sequence of P utilization in production, environmental, and societal systems: (1) Sufficiency and efficiency of P utilization, especially in animal husbandry and crop production; (2) P recycling: technologies and product applications; (3) P fluxes and cycling in the environment; and (4) P governance. The latter two themes had separate sessions for the first time in the International Phosphorus Workshops series; thus, this overview presents a scene-setting rather than an overview of the latest research for these themes. In summary, this paper details new findings in agricultural and environmental P research, which indicate reduced P inputs, improved management options, and provide translations into governance options for a more sustainable P use.     

Detection of dicofol and related pesticides in human breast milk from China, Korea and Japan

Previously, we demonstrated that the concentrations of DDTs were greater in breast milk collected from Chinese mothers than from Japanese and Korean mothers. To investigate dicofol as a possible source of the DDTs in human breast milk, we collected breast milk samples from 2007 to 2009 in China (Beijing), Korea (Seoul, Busan) and Japan (Sendai, Takarazuka and Takayama). Using these breast milk samples, we quantified the concentrations of dichlorobenzophenone, a pyrolysis product of dicofol (simply referred to as dicofol hereafter), dichlorodiphenyltrichloroethane and its metabolites (DDTs) using GC-MS. Overall, 12 of 14 pooled breast milk samples from 210 mothers contained detectable levels of dicofol (>0.1 ng g⁻¹ lipid). The geometric mean concentration of dicofol in the Japanese breast milk samples was 0.3 ng g⁻¹ lipid and significantly lower than that in Chinese (9.6 ng g⁻¹ lipid) or Korean breast milk samples (1.9 ng g⁻¹ lipid) (p < 0.05 for each). Furthermore, the ΣDDT levels in breast milk from China were 10-fold higher than those from Korea and Japan. The present results strongly suggest the presence of extensive emission sources of both dicofol and DDTs in China. However, exposure to dicofol cannot explain the large exposure of Chinese mothers to DDTs because of the trace levels of dicofol in the ΣDDTs. In the present study, dicofol was confirmed to be detectable in human breast milk. This is the first report to identify dicofol in human samples.     

Mass balance of arsenic and antimony in municipal waste incinerators

The arsenic and antimony balance in two municipal waste incinerators was investigated. Initially, the production rates of ash and wet scrubber effluent were estimated. Then the arsenic and antimony in the ash and wet scrubber effluent were determined, which gave an estimate of the elemental balance. The total amounts of arsenic and antimony in the municipal waste were 0.9 g/t and 30–44 g/t, respectively. The distributions to fly ash were 45–47% and 33–74% for arsenic and antimony, respectively. The distribution mechanisms of arsenic and antimony are discussed from the viewpoints of their thermodynamics as well as their initial valencies, which greatly affect their behaviour. Received: July 2, 1998 / Accepted: February 27, 1999     

Removal of organic polyelectrolytes and their metal complexes by adsorption onto xonotlite

Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed by adsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were approximately 80% and 30%, respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially, indicating that adsorption efficiency depends on the number of functional groups of humic substances. Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanning electron microscopy. The calculated heat of adsorption was of 330 kJ mol(-1) which was evaluated from the Clapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can be easily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to their precipitation.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

An estimate of the conversion rates of SO2 to SO2-4 and NO2 to HNO3+ NO3- for the evaluation air pollution in Beijing

The conversion rates of SO₂ to SO^2-₄ and NO₂ to HNO₃₊NO₃- are estimated from the field-data obtained in Beijing in summer, 1988. The results show that the conversion rate of NO₂ is about four times as much as that of SO₂; The conversion rates have a diurnal variation in a day. On the average, the rate of SO₂ is estimated to be 4.7% h^-1 during the daytime and 3.4% h^-1 during the nighttime. Similarly, the rate of NO₂ is estimated to be 17.2% h^-1 and 12% h^-1 respectively.     

Characterization of microbial consortia that reductively dechlorinate 4-chlorophenol and transform phenol to benzoate enriched from estuarine sediment of Lake Shinji

Monochlorophenols were degraded to benzoate via phenol by the initial dechlorination and the subsequent conversion of phenol to benzoate in anaerobic sediment samples of estuarine Lake Shinji under methanogenic conditions. To characterize bacteria that dechlorinate 4-chlorophenol and transform phenol to benzoate, we analyzed the microbial community structure of the enrichment culture with each 4-chlorophenol and phenol by the limiting dilution method with polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) of 16S rRNA gene. After serial dilution of the culture, the 4-chlorophenol-dechlorinating culture consisted of two dominant bacteria, one of which was most homologous with Dehalobacter sp. In the enriched culture with phenol, minor band homologous with Cryptanaerobacter phenolicass corresponded to the transformation activity.