Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

The arrival and discharge of conjugated estrogens from a range of different sewage treatment plants in the UK

The occurrence of free and conjugated estrogens was examined in a survey of eleven sewage treatment plants (STPs) and their discharge water in the United Kingdom using grab sampling. The STPs included trickling filter with and without tertiary treatment, and activated sludge with tertiary treatment. For three activated sludge plants both influent and effluent samples were compared. For a further 8 STPs only the effluent was examined. The estrone-3-sulphate, estradiol-3-sulphate and estriol-3-sulphate concentrations (up to 20 ng L⁻¹) were typically 5-fold that of the respective free estrogen concentration in the effluents. This represents a substantial additional ‘potential’ estrogen load arriving in the receiving waters. Estrone-3-glucuronide was found at 9 ng L⁻¹, estradiol-3-glucuronide at 7 ng L⁻¹, and estriol-3-glucuronide at 32 ng L⁻¹ in sewage influent. Except on one occasion, no glucuronide conjugates could be found in the effluent. The results suggest in most cases glucuronide conjugates will be completely transformed in sewage treatment whilst sulphate conjugates will only be partially removed.     

Toxicity test using medaka (Oryzias latipes) early fry and concentrated sample water as an index of aquatic habitat condition

The aim of the present study was to show a relationship between toxicity of 100-fold concentrated water and aquatic habitat conditions. Environmental waters are 100-fold concentrated with solid-phase extraction. Medaka early fry was exposed in these waters for 48 h. The number of death and disorder was counted at 1, 2, 3, 6, 12, 24, and 48 h; toxicity was expressed using inverse median effect time and median lethal time (ET (50)(-1), LT (50)(-1)). Average score per taxon (ASPT) for benthic animals and Index of Biotic Integrity (IBI) for fish were applied as indices of aquatic habitat conditions. The results of toxicity test were compared using ASPT and IBI. The different levels of toxicity were detected in the seawater of Japan. At the Husino River area, toxicity cannot be detected. In rivers, high toxicity appeared at urban districts without sewerage. By Spearman coefficient, the relationship between toxicity and high biochemical oxygen demand (BOD) were obtained. BOD household wastewater contains hydrophobic toxic matters; otherwise, seawater in industrial area does not show clear relationship between toxicity and chemical oxygen demand. Gas chromatography to mass spectrometry simultaneous analysis database may give an answer for the source of toxicity, but further test is required. Ratio of clear stream benthic animal sharply decreased over 0.25 of LT (50)(-1) or 0.5 of ET (50)(-1). Tolerant fish becomes dominant over 0.3 of LT (50)(-1) or 0.5-1.0 of ET (50)(-1). By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and ASPT was obtained at -0.773 (ET (50)(-1)) and -0.742 (LT (50)(-1)) at 1 % level of significance with a high negative correlation. Toxicity (LT (50)(-1) ) has strong correlation with the ratio of tolerant species. By Pearson product-moment correlation coefficient, correlation coefficient between toxicity and IBI obtained were -0.155 (ET (50)(-1)) and -0.190 (LT (50)(-1)) at 1 % level of significance and has a low or no correlation between toxicity and IBI. Even with low toxic environmental waters, toxicity test using 100-fold concentrated and medaka early fly could detect acute toxicity. The detected toxicity seemed to limit the inhabiting aquatic species in the water body.     

Accumulation of perfluorinated compounds in captive Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) in China

The accumulation of perfluorinated compounds (PFCs) in the sera of captive wildlife species Bengal tigers (Panthera tigris tigris) and African lions (Panthera leo Linnaeus) from Harbin Wildlife Park, Heilongjiang Province, in China were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). Perfluorooctanesulfonate (PFOS) was the predominant contaminant with a mean serum concentration of 1.18 ng mL(-1) in tigers and 2.69 ng mL(-1) in lions. Perfluorononanoic acid (PFNA) was the second most prevalent contaminant in both species. The composition profiles of the tested PFCs differed between tigers and lions, and the percentages of perfluorooctanoic acid (PFOA) were greater in lions than in tigers, indicating different exposures and/or metabolic capabilities between the two species. Assessments of the risk of PFC contamination to the two species were obtained by comparing measured concentrations to points of departure or toxicity reference values (TRVs). Results suggest no risk of PFOS exposure or toxicity for the two species.     

Total fluorine, extractable organic fluorine, perfluorooctane sulfonate and other related fluorochemicals in liver of Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from South China

The concentrations of 10 PFCs (perfluorinated compounds: PFOS, PFHxS, PFOSA, N-EtFOSA, PFDoDA, PFUnDA, PFDA, PFNA, PFOA, and PFHpA) were measured in liver samples of Indo-Pacific humpback dolphins (Sousa chinensis) (n = 10) and finless porpoises (Neophocaena phocaenoides) (n = 10) stranded in Hong Kong between 2003 and 2007. PFOS was the dominant PFC in the tissues at concentrations ranging at 26-693 ng/g ww in dolphins and 51.3-262 ng/g ww in porpoises. A newly developed combustion ion chromatography for fluorine was applied to measure total fluorine (TF) and extractable organic fluorine (EOF) in these liver samples to understand PFC contamination using the concept of mass balance analysis. Comparisons between the amounts of known PFCs and EOF in the livers showed that a large proportion (∼70%) of the organic fluorine in both species is of unknown origin. These investigations are critical for a comprehensive assessment of the risks of these compounds to humans and other receptors.     

Factors affecting the degradation of amoxicillin in composting toilet

The biological and non-biological factors that affect the degradation of amoxicillin in the composting process of feces have been investigated. The effect of living bacteria and the enzyme (beta-lactamase) on amoxicillin decay was examined, and our results indicated that the biological effects are likely to be negligible. Consequently, the effect of phosphate, ammonia and pH level as non-biological factors was investigated by monitoring the reduction rate of amoxicillin in phosphate and ammonia buffer solutions with several pH levels. Each reduction rate constant was integrated by a simulation model, and the each calculated amoxicillin reduction profile was compared to the reduction profiles of amoxicillin in the composting process of feces. The calculated results corresponded almost exactly to the experimental profiles. We therefore concluded that the degradation of amoxicillin in a toilet matrix was dependent on the concentration of ammonia, phosphate and hydroxyl ion.     

Development of extraction method of pharmaceuticals and their occurrences found in Japanese wastewater treatment plants

In this study, occurrence of 66 PPCPs (pharmaceuticals and personal care products) in liquid and solid phases of sewage sludge was elucidated. The extraction methods for the PPCPs from sludge were newly developed employing Pressurized Liquid Extraction (PLE) and Ultrasonic Solvent Extraction (USE). As an appropriate method, PLE using water (pH2), PLE using methanol (pH4), and USE using mixture of methanol and water (1/9,v/v, pH11) was found most effective because total recovery of most of the PPCPs indicated 40 to 130%. The developed extraction method with previously developed method for liquid phase analysis was applied to field survey at wastewater treatment plants (WWTPs) in Japan. 56 compounds were detected from the primary sludge and 61 compounds were detected from the excess sludge. The concentration was ranged between several ng/g and several μg/g. Solid-water distribution coefficient (Log K_d) ranged between 0.9 L/kg (Caffeine) and 3.7 L/kg (Levofloxacin) for primary sludge and between 1.4 L/kg (Sulpirid) and 4.3 L/kg (Mefenamic acid) for excess sludge.     

Fluorinated alkyl compounds including long chain carboxylic acids in wild bird livers from Japan

A wide range of fluorinated alkyl compounds (FACs) has been reported in wildlife in various locations in the world. However, such information regarding Japanese wildlife is rarely found. In the present study, we investigated the occurrence of 21 FACs, including perfluorinated alkyl sulfonates (PFASs), perfluorinated carboxylates (PFCAs), and fluorotelomer acids, in the livers of 10 wild bird species from two regions in northern Japan. To avoid interferences, FACs were quantified by a recently developed method using acetonitrile and solid-phase extraction followed by an ion exchange HPLC column separation. Apart from perfluorooctane sulfonate (PFOS), which was found at the highest levels of all the compounds detected, several long chain perfluorinated carboxylates (PFCAs) from C8 to C16, particularly perfluorotetradecanoic acid (PFTeDA) and perfluorohexadecanoic acid (PFHxDA), were detected for the first time. Additionally, 7:3 FTCA, a fluorotelomer acid, was also detected in most swan livers from Miyagi prefecture and all the birds from Tochigi prefecture. However, none of the sulfonamides and unsaturated telomer acids were detected in any species. Swans seem to be the least exposed wild birds to FACs among the investigated birds, signifying that feeding habits may reflect FAC accumulation in wild birds. The highest total concentration of detected FACs was 405 ng g⁻¹ wet wt., which was found in a Japanese sparrowhawk, indicating that the top predatory wild birds can accumulate several long chain carboxylic acids. However, the current FAC concentrations found in livers may suggest that these compounds alone would not cause a severe toxic effect in these species.     

石灰投加与搅拌对生态厕所的灭菌效果

以发展中国家农村地区的卫生条件改善为目的,开展了简易生态厕所的粪便堆肥处理实验。在投加石灰作为抑菌剂的条件下,研究了搅拌混合对杀灭致病微生物的影响,以及使堆肥终产物达到可接受风险值所需的最佳搅拌条件。实验确定了石灰的投加量,并应用Beta-Possion模型对堆肥处置过程中致病微生物对暴露人群的健康风险进行评价,从而从健康风险控制的角度确定了最佳的搅拌次数。研究结果表明,石灰投加量约占堆肥干重1.5%,手动搅拌50次,经搅拌后放置12 h能达到可接受的风险值(3.2×10-5)。