Umweltrelevanz von Diphenylamin — Ein Stoff der 3. EU-Altstoffprioritätenliste

Diphenylamine (DPA), the simplest secondary aromatic amine, is a compound from the third European Union (EU) list of priority pollutants. It was assigned to Germany to assess and control its environmental risks. DPA is most commonly used as a stabilizer agent in nitrocellulose-containing explosives and propellants, in the perfumery, and as an antioxidant in the rubber and elastomer industry. DPA is also widely used to prevent the post-harvest deterioration of apple and pear crops. It is a parent compound of many derivatives which are used for the production of dyes, pharmaceuticals, photography chemicals and further small-scale applications. At the beginning of the eighties, the estimated world production of DPA was ?40,000 tons per year (in Germany ?4,000 tons per year). The compound is still produced world-wide by the chemical industries. Recently published reports showed that DPA was found in soil and groundwater (within the ppb to ppm range). Some ecotoxicological reports demonstrated the potential hazard of various diphenylamines to the aquatic environment and to bacteria and animals as well. Studies on the biodegradability of DPA and its derivatives are very sparse. Therefore, further investigations are required to determine the complete dimensions of the potential environmental hazard and to introduce possible (bio)remediation techniques for sites that are contaminated with this compound or its derivatives. This review summarizes the environmental relevance of DPA as has been published in the literature thus far. It may possibly support the German authorities in their assessment of the risks of this priority pollutant.     

Acute toxicity of 30 pharmaceutically active compounds to freshwater planarians,Dugesia japonica

Pharmaceutically active compounds are produced worldwide and consumed in large quantities, so these chemicals are frequently detected in limnic environments posing potential ecological risks. Thirty pharmaceutically active compounds were selected for examination of their acute toxicity for freshwater planarians (Dugesia japonica). Among the 30 compounds tested, diclofenac, mefenamic acid, naproxen, propranolol HCl, and diphenhydramine HCl had a 48-h nominal LC₅₀ below10 mg L^?1, and for 18 chemicals, it exceeded 100 mg L^?1. The 96-h nominal LC₅₀ was below 10 mg L^?1 for diclofenac, mefenamic acid, naproxen, propranolol HCl, diltiazem HCl, diphenhydramine HCl, hydroxyzine HCl, and triprolidine HCl, and for 15 chemicals, it exceeded 100 mg L^?1. Among different therapeutic groups, analgesics were most toxic to planarians, and antibiotics were least toxic. Antihistamines and beta blockers varied in their acute toxicity to planarians. At the current environmental levels, none of the tested pharmaceutically active compounds may have acutely harmful impacts on aquatic invertebrates. To answer the question whether chronic, long-term exposure to pharmaceutically active compounds may entail ecological risks for aquatic ecosystems, further investigations with different end points in multiple species tests are needed.     

与环境污染物转化相关的细菌厌氧呼吸研究动态

基于细菌呼吸理论为基础的环境有毒物质降解为环境污染治理提供了新的策略和方法,是近年来研究的热点问题.细菌呼吸是自然界中一个最基本、最重要的生物代谢过程,具有很大的灵活性和多样性,且与生态环境密切相关.在厌氧条件下,细菌利用环境中多种有毒物质作为呼吸链末端电子受体进行厌氧呼吸,在有毒物质被还原甚至降解的同时实现电子在呼吸链上的传递,形成跨膜的质子浓度电势梯度,进而转化为其生长代谢所需的能量.细菌以环境有毒物质为电子受体的厌氧呼吸不断被发现,这对于深入理解细菌呼吸的本质具有重要的理论意义,同时对于有毒物质的降解及元素的生物地球化学循环具重要的环境学意义,对于提高对地球表面有毒物质污染生物修复策略的认识具有重要的现实意义.图1表1参45     

Metabolism of aceclofenac in cattle to vulture‐killing diclofenac

The nonsteroidal anti‐inflammatory drug (NSAID) diclofenac is highly toxic to Gyps vultures, and its recent widespread use in South Asia caused catastrophic declines in at least 3 scavenging raptors. The manufacture of veterinary formulations of diclofenac has since been banned across the region with mixed success. However, at least 12 other NSAIDs are available for veterinary use in South Asia. Aceclofenac is one of these compounds, and it is known to metabolize into diclofenac in some mammal species. The metabolic pathway of aceclofenac in cattle, the primary food of vultures in South Asia, is unknown. We gave 6 cattle the recommended dose of aceclofenac (2 mg/kg), collected blood thereafter at intervals for up to 12 h, and used liquid chromatography with mass spectrometry in a pharmacokinetic analysis of aceclofenac and diclofenac in the plasma. Nearly all the aceclofenac administered to the cattle was very rapidly metabolized into diclofenac. At 2 h, half the aceclofenac had been converted into diclofenac, and at 12 h four‐fifths of the aceclofenac had been converted into diclofenac. Therefore, administering aceclofenac to livestock poses the same risk to vultures as administering diclofenac to livestock. This, coupled with the risk that aceclofenac may replace diclofenac in the veterinary market, points to the need for an immediate ban on all aceclofenac formulations that can be used to treat livestock. Without such a ban, the recovery of vultures across South Asia will not be successful.     

环境中植酸的分布、形态及界面反应行为

肌-肌醇六磷酸(myo-inositol-1,2,3,4,5,6-hexakisphosphate,IHP,myo-IP6)简称植酸(Phytic acid或phytate),是大多数土壤中最为丰富的有机磷,它在环境中的界面反应影响着磷素的迁移、循环、转化、生物有效性以及环境效应.本文简要总结了环境中植酸的分布与形态,并综述了其界面反应,包括铁铝氧化物、粘土矿物、碳酸钙等对植酸的吸附解吸,多价阳离子与植酸的络合反应以及沉淀作用.土壤矿物对植酸的吸附影响其转化和生物有效性,矿物对植酸磷的吸附量一般远高于正磷酸盐.其中,弱晶质铁铝(氢)氧化物对植酸的吸附能力一般较晶形铁铝(氢)氧化物大很多.同时,分析了矿物类型、介质pH、温度、共存离子等环境条件对植酸界面反应的影响,植酸吸附对矿物表面电荷性质、颗粒大小和分散稳定性等的作用,以及植酸在金属污染土壤修复中的应用前景.最后讨论了环境中植酸的主要研究热点和方向.     

Pharmaceutical compounds in aquatic environment in China: locally screening and environmental risk assessment

An environmental risk assessment was performed for pharmaceutical compounds present in the aquatic environment of China. Predicted environmental concentration (PEC) of the compounds were calculated according to European Medicines Evaluation Agency (EMEA) guidelines. Available ecotoxicological data compromised by applying a very conservative assessment factor (AF) were employed to calculate the predicted no-effect concentration (PNEC). The screening principle and the risk assessment were based on risk quotient (RQ), which derived from the PEC and related PNEC values. PEC results indicated that all the compounds except sulfadimethoxine and levocarnitine, should carry out phase II risk assessment in EMEA guideline. RQ values suggested that more than 36 pharmaceuticals may be imposed health threats to the aquatic environment; especially the antibiotic therapeutic class including amoxicillin, sulfasalazine, trimethoprim, oxytetracycline and erythromycin showed high RQ values. These substances with high RQ value (RQ≥1) were regarded as top-priority pharmaceuticals for control in the aquatic environment of China. However, the antibiotic substances which had low risk quotient (RQ <1), should be reassessed by its potentially induced resistance under low concentration in future.     

Preliminary survey of pharmaceutical residues in some important Romanian rivers

A number of important rivers of Romania were investigated for pharmaceutical and antifungal residues. In a post target approach analysis, a single-stage, high-resolution mass spectrometry was successfully applied for the screening of 43 pharmaceuticals and fungicides in water, using U-HPLC-Exactive Orbitrap MS at 50,000 full width at half maximum resolution. Detection was based on accurate masses and retention times. The study confirmed the presence of pharmaceuticals and antifungals such as diclofenac, sulfamethoxazole, carbamazepine, trimethoprim, thiabendazole, and clotrimazole, in water. Diclofenac and carbamazepine were the most frequently detected (eight samples); concentrations ranged from 5 to 50 ng L^?1. Low concentrations of griseofulvin were detected in the Prut River. Further monitoring studies should be carried out in order to fill the gaps of knowledge concerning the presence of pharmaceutical residues in Romanian water environment and to improve public understanding regarding the environmental risk of pharmaceutical contamination.     

Bewertung der Umweltrelevanz von Arzneistoffen

Aim The aim of this work was to investigate, which human and veterinary pharmaceuticals are of high ecological relevance due to the input into the environment as well as with regard to the effects and behaviour in the environment. Furthermore, the state of knowledge concerning the ecologically relevant substances and the need of research was evaluated. Methods A two-step approach considering the criteria quantity of sold pharmaceuticals, concentrations, effects and fate in the environment was developed to identify the pharmaceuticals of potential ecological relevance. In a second step the identified individual substances and groups of substances were considered in more detail concerning metabolism, environmental behaviour and ecological effects. Results In a first step 29 out of approximate 2,700 licensed human pharmaceuticals and seven substances as well as three substance groups used in veterinary medicine were identified as potentially ecologically relevant. The detailed assessment in a second step lead to the conclusion, that of the human pharmaceuticals 9 substances as well as two substance groups concerning the environmental behaviour and seven substances concerning the effects are of high environmental relevance. Concerning the environmental behaviour six out of seven veterinary pharmaceuticals as well as three substance groups and only three substances concerning the ecological effects were classified as relevant for the environment. Discussion By means of the presented method it was possible to limit the scope of a wide spectrum of pharmaceuticals, so that a detailed assessment of only relevant active agents was possible. Nevertheless, it is a precondition that investigations concerning the occurrence, fate and effects of the individual compounds in the environment have been already carried out and published in the literature. Conclusions The method is suitable for a comprehensive assessment of the ecological relevance of pharmaceuticals, but for a lot of human and veterinary pharmaceuticals the data available in the literature are insufficient. Recommendations For a final extensive assessment of the environmental relevance for some of the human and veterinary pharmaceuticals more studies are necessary. Especially data concerning the environmental behaviour in water and soils, data from long-term-studies for the assessment of ecological effects and data concerning metabolites and mixtures of pharmaceutical compounds are lacking.     

Pharmazeutische Wirkstoffe und Umweltschutz

On 26 April this year the German Environmental Advisory Council (SRU) published a statement on ‘Pharmaceuticals in the environment’ and pointed considerable need for action to understand and to reduce the risks from diffuse pharmaceutical inputs in the environment. On the one hand, it is urgently necessary to improve the database for environmental risk assessments; on the other hand measures should already be taken to minimize harmful inputs. Fortunately, the new regulations for an application for an authorization to market new pharmaceuticals require an environmental risk assessment. However, there is a lack of information on possible impacts from long time admitted medicines which may be responsible for harmful active substances detectable in the environment. To remove this data deficit, a European programme for risk evaluation of old pharmaceuticals should be established. It is necessary for an adequate risk assessment to look at all impacts of one active substance or all substances same-directed in their active potential summativ and to generate regularly consumption data in particular for the use of veterinary products. The hot spots of contamination are the introduction of large scale volumes of active pharmaceutical ingredients for human use like diclofenac and carbamazepin as well as hormones into surface waters, as well as the application of antibiotics-loaded economic fertilizers on soils. Not to be neglected is the application of antiparasitics in animals kept on pasture. With the assessment of the use of pharmaceuticals for all purposes special attention is needed on antibiotic resistance. For the mitigation of environmental exposures there are exposures measures necessary to reduce use of antibiotics in farming, for the application of new effective technologies in treatment sewage — as for example ozonation, filtration with activated carbon or membrane filtration — as well as for the labelling of environmentally harmful medicinal products.     

Determination and occurrence of endocrine disrupting compounds,pharmaceuticals and personal care products in fish (Morone saxatilis)

Endocrine disrupting compounds (EDCs), pharmaceuticals and personal care products (PPCPs) have attracted much attention due to widespread contamination in aquatic environment. In this study, we determined 13 EDCs and PPCPs in fish blood, bile and muscle by using gas chromatography-mass spectrometry (GC-MS). The limits of quantitation (LOQ) were in the ranges of 0.23–2.54, 0.22–2.36 ng·mL⁻¹, and 0.24–2.57 ng·g⁻¹ dry weight (dw) for fish blood, bile and muscle, respectively. Recoveries of target compounds spiked into sample matrices and passed through the entire analytical procedure ranged from 65% to 95%, from 60% to 92% and from 62% to 91% for blood, bile and muscle, respectively. The methods were applied to the analysis of fish from a lake in California. Target compounds were relatively low in bile, and only bisphenol A (BPA) and diclofenac were measurable near the LOQ. Seven of 13 compounds were detected in blood, with total concentrations up to 39 ng·mL⁻¹. Only BPA was frequently found in muscle, with mean concentration of 7.26 ng·g⁻¹ dw. The estimated daily intake of BPA through fish consumption for U.S. resident was significantly lower than the tolerable daily intake recommended by the European Food Safety Authority. This study showed that the exposure to the bisphenol A from fish diet is unlikely to pose a health risk.     

应用超敏感酵母HUG1-yEGFP生物传感器筛选基因毒性化合物

为了扩展本实验室构建的响应于DNA损伤信号的超敏感酵母HUG1-yEGFP生物传感器的检测范围并积累参考数据,为实际应用打下实验基础,本研究对26种与环境及人类生活息息相关的化合物的基因毒性进行了检测,筛选出8种具有基因毒性的化合物,并将其结果与现有微生物检测系统的检测结果进行了对比。结果显示,超敏感酵母HUG1-yEGFP生物传感器的检测结果与以细菌为宿主细胞的Ames试验或SOS显色法的检测结果的吻合度高于50%,与以酵母为宿主细胞的GSA检测系统的检测结果的吻合度高于85%。以真核生物酵母为宿主的检测系统与以原核生物细胞为宿主的检测系统的结果的差异反映了它们抗胁迫机制的不同。本研究应用超敏感酵母HUG1-yEGFP生物传感器特异性检测出3种化合物为基因毒性阳性,这3种化合物是代森锰锌、孔雀石绿及丙烯酰胺,均被报道具有潜在致癌性。本研究结果表明,超敏感酵母HUG1-yEGFP生物传感器可以有效地对环境污染有关的基因毒性化合物进行检测,可以作为其他现有检测系统的补充,应用于环境化学污染的健康风险评价。     

Determination of 1‐octanol/water partition coefficients of isocyanate compounds by an HPLC method

The octanol/water partition coefficients (P _ow) of six monoisocyanate and five diisocyanate compounds were determined by high performance liquid chromatograph (HPLC) methods. Two HPLC peaks, a broad tailed peak followed by a sharp one, were observed with all compounds. The later peak was identified as the isocyanate compound. The P _ow value for each isocyanate compound was determined by fitting the capacity factor of the peak to the regression equation drawn from those of reference compounds. The hydrophobic substituent constants for the isocyanate group were calculated with each of the compounds. The value of this constant was strongly dependent on the type of carbon bound to the isocyanate group and the average values for the aromatic and aliphatic isocyanate groups were 0.35 and — 0.52, respectively. Because of the reactivity of those compounds in the aquatic environment, the P _ow has little relevance to calculation of their environmental fate and ecotoxicity.     

固-液异相催化剂在环境科学领域中的应用

异相催化是催化反应的重要组成部分，其应用十分广泛。固一液异相催化作为环境科学领域中的一项比较新颖的技术，在研究污染物在多介质环境中的迁移转化行为、开发受污染环境修复及污废水处理新技术等诸多方面都具有很大的发展潜力。因此，对不同类型固一液异相催化剂在环境科学领域的应用研究逐渐成为国内外环境科学领域的研究热点之一。其中，金属和金属氧化物因对某些氧化一还原反应具有较好的催化作用，在饮用水脱氮、污废水脱卤及深度氧化处理等水处理领域的应用较为广泛；固态酸催化剂能催化聚合、裂化、水解反应，因此与某些有机污染物的降解密切相关；将同相催化剂固定化为异相催化剂，同样成为新技术开发的方向之一；天然催化剂对污染物在多介质环境中行为影响的研究近年来也屡有发表。此外，载体因对催化剂的活性及应用具有重要影响，也日益受到关注。文章对环境科学领域中固一液异相催化剂的应用研究进行了综述。     

Suspected flunixin poisoning of a wild Eurasian Griffon Vulture from Spain

Exposure to residues of the nonsteroidal anti‐inflammatory drug (NSAID) diclofenac present in livestock carcasses has caused extensive declines in 3 Gyps vulture species across Asia. The carcass of a wild Eurasian Griffon Vulture (Gyps fulvus) was found in 2012 on an Andalucian (Spain) game hunting reserve and examined forensically. The bird had severe visceral gout, a finding consistent with Gyps vultures from Asia that have been poisoned by diclofenac. Liver and kidney samples from this Eurasian Griffon Vulture contained elevated flunixin (an NSAID) levels (median = 2.70 and 6.50 mg/kg, respectively). This is the first reported case of a wild vulture being exposed to and apparently killed by an NSAID outside Asia. It is also the first reported instance of mortality in the wild resulting from environmental exposure to an NSAID other than diclofenac. Caso de Sospecha de Envenenamiento por Flunixin de un Buitre Leonado en España     

水环境中的微塑料：环境危害的本证和反证及主要研究空白

科学界与公众对微塑料(microplastics, MPs)的污染越来越重视。我们对文献进行了系统综述,以评价MPs对环境危害的证据权重。我们发现MPs在地表水和沉积物中均有存在。主要以珠状组成为主的碎片和纤维只是检测到的MP形态中的一小部分。检测出的MPs环境浓度很低,与能够影响生物分子水平上的毒性终点、以及摄食、繁殖、生长、组织炎症和死亡率的浓度有数量级的差别。MPs作为疏水性有机化合物的携带者使其在生物体中富集的作用很弱。现有数据表明MPs对环境造成的危害并不明显。实验室毒性实验中使用的MPs与环境中检测到的MPs在颗粒形态、尺寸范围和浓度等方面都有差距。研究中环境介质的选择少受关注。我们亟需开展更高质量的整体监测和更多实际环境效应的研究。只有这样,我们才能够全面表征MPs的环境风险,以便制定实施真正改善环境质量的管控措施。 精选自Emily E. Burns, Alistair B.A. Boxall. Microplastics in the aquatic environment: Evidence for or against adverse impacts and major knowledge gaps. Environmental Toxicology and Chemistry,2018,37:2776–2796.
详情请见 https://doi.org/10.1002/etc.4268
     

孤对电子杂环化合物的代谢化学和生物学研究进展

地球环境特别是化石燃料中存在着大量含硫,氮和氧孤对电子杂环化合物.对孤对电子杂环化合物代谢机制的研究具有重要的科学意义和实践价值.生物法降解这些杂环化合物具有较化学法无可比拟的优势,主要表现在生物法具有反应专一性好,反应条件温和,可实现许多化学上难以实现的反应.本文结合课题组的近期研究,尝试论述国内外的部分研究进展.     

Comparative in vitro metabolism of chloroxylenol,chlorophene, and triclosan with rat,mouse, and human hepatic microsomes

A number of studies have reported the presence of chlorinated phenols, commonly used as antiseptics, in the environment. Chloroxylenol, chlorophene, and triclosan are three such chemicals believed to have leached into water supplies through the wastewater treatment facilities. Understanding how these compounds are metabolized is important in determining the risks of chemical exposure. In this study, we compared the in vitro metabolism of these three chlorinated phenols with rat, mouse, and human liver microsomes. The structures of the metabolites formed during the microsomal reactions were identical when rat, mouse, and human liver extracts were used, but variations existed in the kinetics of the reactions.     

Occurrence,spatial and seasonal variation,and environmental risk of pharmaceutically active compounds in the Pearl River basin,South China

● 38 PhACs and 2 pesticides were detected in the three rivers of the Pearl River basin. ● Anti-inflammatory/analgesics drugs were the predominant PhACs. ● The concentrations of PhACs showed seasonal and spatial variation. ● Diazepam and ibuprofen were the two PhACs with a moderate environmental risk. The occurrence, fate, and environmental risk of 40 pharmaceutically active compounds (PhACs) from surface waters and sediments were comprehensively investigated in the Beijiang River, Xijiang River, and Maozhou River of the Pearl River basin, South China. Salicylic acid and diclofenac (anti-inflammatory drugs), gemfibrozil (a lipid regulator), carbamazepine (an antiepileptic drug), diazepam (a psychoactive drug), and 2-methyl-4-chloro-phenoxyacetic acid (MCPA, a pesticide) were the most ubiquitous compounds in the studied region. The average concentrations of detected PhACs in surface waters and sediments ranged from 0.17 to 19.1 ng/L and 0.10 to 10.4 ng/g, respectively. Meanwhile, PhACs concentration in surface waters and sediments varied greatly among and within the Beijiang River, Xijiang River, and Maozhou River. The largest annual flux of PhACs of the Xijiang River and Beijiang River was more than 11 000 kg per annum, whereas only 25.7 kg/a in the Maozhou River. In addition, the estimated emissions of PhACs in the Beijiang River, Xijiang River, and Maozhou River ranged respectively from 0.28 to 4.22 kg/a, 0.12 to 6.72 kg/a, and 6.66 to 91.0 kg/a, and the back-estimated usage varied with a range from 12.0 to 293 kg/a, 6.79 to 944 kg/a, 368 to 17 459 kg/a. Moreover, the emissions of PhACs showed a close relationship with the gross domestic product (GDP) of each city along the Pearl River. The environmental risk assessment suggested that diazepam and ibuprofen had a moderate risk in this region.     

Distribution,fate and persistence of organochlorine compounds formed during production of bleached pulp

The processes governing distribution of a xenobiotic compound discharged initially into the environment are discussed, and attention is drawn to (a) binding to organic matter in the sediment phase which affects both persistence and toxicity to biota and (b) the role of atmospheric transport for compounds of low water solubility and high vapour pressure. Important limitations in the use of sum parameters such as EOCI are pointed out. The important distinction between biodegradation and biotransformation is pointed out, and significant experimental determinants noted. Pathways for the aerobic metabolism of chlorophenolic compounds are discussed, and attention is drawn to the role of O‐methylation as an environmentally significant alternative to biodegradation. Evidence for the biodegradation of chlorinated aliphatic acids and hydrocarbons under both aerobic and anaerobic conditions is presented. Anaerobic metabolism of chlorophenolic compounds is discussed with respect to (a) de‐O‐methylation of chloroguaiacols, (b) dechlorination of chlorocatechols and (c) reduction of chlorovanillins. It is emphasized that current evidence provides a complex metabolic picture, and that only partial dechlorination may occur. Brief attention is given to the important issue of the persistence of chlorolignin, and attention drawn to technical issues which render this problem difficult of access by traditional procedures. Biohalogenation—particularly by fungi—is noted, though its quantitative contribution cannot be estimated at the moment. A number of important unresolved issues are underscored: (a) the problem of determining rates of microbial reactions which may be translated to environmental situations, (b) the cardinal role not only of the number of chlorine atoms in an aromatic compound but also the substitution pattern and (c) limitations in current understanding of the role of anaerobic bacteria in bringing about biodegradation and biotransformation.     

稳定同位素技术在污染环境生物修复研究中的应用

稳定同位素技术主要应用于地球化学,它是将人工合成的同位素标记特定的化合物,追踪标记物在生命活动中的变化规律,目前该项技术也广泛应用于环境微生物学、生态学、生物医学等领域.生物修复是利用存在于土壤、地下水和海洋等环境中的生物特别是微生物将有毒、有害的污染物降解为二氧化碳和水,或转化为无害物质,从而使污染的生态环境修复为正常生态环境的过程.这些降解微生物都来自于小部份可培养微生物,对于大部份未可培养降解微生物,通常在实验室条件下很难得到.而利用稳定同位素技术,如13C标记底物,收集利用该底物的微生物核酸,就可以得到具有降解作用的功能微生物,为环境污染生物修复提供重要的菌源和功能基因.环境中的许多物质都可以用SIP来标记,这些标记物主要有PLFA-SIP、DNA-SIP、RNA-SIP等,它们都可以用来在复杂样本中进行有特殊代谢功能微生物的鉴定和分析,在利用微生物进行生物修复中具有重要的意义.图2表1参42