Properties,performance and associated hazards of state-of-the-art durable water repellent (DWR) chemistry for textile finishing

Following the phase-out of long-chain per- and polyfluoroalkyl substances (PFASs), the textile industry had to find alternatives for side-chain fluorinated polymer based durable water repellent (DWR) chemistries that incorporated long perfluoroalkyl side chains. This phase-out and subsequent substitution with alternatives has resulted in a market where both fluorinated and non-fluorinated DWRs are available. These DWR alternatives can be divided into four broad groups that reflect their basic chemistry: side-chain fluorinated polymers, silicones, hydrocarbons and other chemistries (includes dendrimer and inorganic nanoparticle chemistries). In this critical review, the alternative DWRs are assessed with regards to their structural properties and connected performance, loss and degradation processes resulting in diffuse environmental emissions, and hazard profiles for selected emitted substances. Our review shows that there are large differences in performance between the alternative DWRs, most importantly the lack of oil repellence of non-fluorinated alternatives. It also shows that for all alternatives, impurities and/or degradation products of the DWR chemistries are diffusively emitted to the environment. Our hazard ranking suggests that hydrocarbon based DWR is the most environmentally benign, followed by silicone and side-chain fluorinated polymer-based DWR chemistries. Industrial commitments to reduce the levels of impurities in silicone based and side-chain fluorinated polymer based DWR formulations will lower the actual risks. There is a lack of information on the hazards associated with DWRs, in particular for the dendrimer and inorganic nanoparticle chemistries, and these data gaps must be filled. Until environmentally safe alternatives, which provide the required performance, are available our recommendation is to choose DWR chemistry on a case-by-case basis, always weighing the benefits connected to increased performance against the risks to the environment and human health.     

Biodegradation potential of the genus Rhodococcus

A large number of aromatic compounds and organic nitriles, the two groups of compounds covered in this review, are intermediates, products, by-products or waste products of the chemical and pharmaceutical industries, agriculture and the processing of fossil fuels. The majority of these synthetic substances (xenobiotics) are toxic and their release and accumulation in the environment pose a serious threat to living organisms. Bioremediation using various bacterial strains of the genus Rhodococcus has proved to be a promising option for the clean-up of polluted sites. The large genomes of rhodococci, their redundant and versatile catabolic pathways, their ability to uptake and metabolize hydrophobic compounds, to form biofilms, to persist in adverse conditions and the availability of recently developed tools for genetic engineering in rhodococci make them suitable industrial microorganisms for biotransformations and the biodegradation of many organic compounds. The peripheral and central catabolic pathways in rhodococci are characterized for each type of aromatics (hydrocarbons, phenols, halogenated, nitroaromatic, and heterocyclic compounds) in this review. Pathways involved in the hydrolysis of nitrile pollutants (aliphatic nitriles, benzonitrile analogues) and the corresponding enzymes (nitrilase, nitrile hydratase) are described in detail. Examples of regulatory mechanisms for the expression of the catabolic genes are given. The strains that efficiently degrade the compounds in question are highlighted and examples of their use in biodegradation processes are presented.     

Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their potential precursors

Since 2000 there has been an on-going industrial transition to replace long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs) and their precursors. To date, information on these replacements including their chemical identities, however, has not been published or made easily accessible to the public, hampering risk assessment and management of these chemicals. Here we review information on fluorinated alternatives in the public domain. We identify over 20 fluorinated substances that are applied in [i] fluoropolymer manufacture, [ii] surface treatment of textile, leather and carpets, [iii] surface treatment of food contact materials, [iv] metal plating, [v] fire-fighting foams, and [vi] other commercial and consumer products. We summarize current knowledge on their environmental releases, persistence, and exposure of biota and humans. Based on the limited information available, it is unclear whether fluorinated alternatives are safe for humans and the environment. We identify three major data gaps that must be filled to perform meaningful risk assessments and recommend generation of the missing data through cooperation among all stakeholders (industry, regulators, academic scientists and the public).     

复合垂直流人工湿地中基质生物膜的特性

从基质生物膜量、生物膜厚度和脱氢酶活性等方面研究了以复合垂直流人工湿地中基质颗粒作为附着生长载体的生物膜的特性。结果表明,复合垂直流人工湿地中,基质生物膜的形成时间为40~60 d。进水水质不同,基质生物膜的形成时间有差异,进水中相对高的营养水平有利于基质生物膜的积累,60 d内形成的稳定生物膜量相差1.59倍;生物膜活性也较大,平均相差1.5倍。不同发育程度的生物膜表现出的活性不同,最佳活性厚度为150 um。人工湿地中不同层次基质生物膜厚度差异显著,最表层0~5 cm层次基质生物膜厚度2~3倍于10 cm以下层次,为最佳活性厚度的3~4倍,其生物膜的过量积累不仅不利于处理效率的提高,且易造成人工湿地的堵塞。     

Recent advances in photocatalytic treatment of pollutants in aqueous media

Photocatalysis can be an excellent solution for resolving the world's energy and environmental problems. It has a wide range of applications for the decontamination of diverse hazardous pollutants in aqueous media. Technological progress in this research field has been achieved toward the improvement of the solar sensitivity to enhance the efficiency of pollutant decontamination. As a result, various strategies have been introduced to upgrade photocatalytic performance with the modification of prototypical photocatalyst such as doping, dye sensitization, semiconductor coupling, mesoporous supports, single site, and nano-based catalysts. In this review, a brief survey is presented to describe those strategies based on the evaluation made against various pollutants (such as pharmaceuticals, pesticides, heavy metals, detergents, and dyes) in aqueous media.     

Determination of nonionic detergents in municipal wastewater

Hard (nonbiodegradable) nonionic surfactants are the most commonly used nonionics in Israel. This has no parallel in western industrial countries. Consequently, available methods for nonionic determination should be appropriately applied and validated under the particular local in vivo conditions. This study presents preliminary results of the application of modified available analycal hydrophilic and hydrophobic methods and procedures for nonionic detergents determination to the complex system of typical sewage effluents in Israel under in vitro (laboratory controlled), simulative, semi-in vivo, and in vivo (real, uncontrolled) local field conditions. Using the hydrophilic Cobalto thiocyanate method and applying several essential modifications and transformations have facilitated the obtaining of “summative,” averaged, factorized calibration curves which represent the local environmental reality. Based on the above in vitro-in vivo transformations, an unexpected low concentration of nonionic surfactants (3–4 mg/L) has been determined in typical local municipal sewage effluents.     

Environmental effects of new herbicides for vegetation control in forestry

Environmental fate of and toxicity data for ammonium ethyl carbamoylphosphonate [fosamine ammonium], N-(phosphonomethyl)glycine [glyphosate], and 3-cyclohexyl-6-(dimethylamino)-1-methyl-1,3,5-triazine-2,4(1H, 3H)-dione [hexazinone] which appear promising for vegetation control in forestry are reviewed. None of the three herbicides is very persistent in soil, with half-lives reported of about 7–10 days for fosamine ammonium, 8–19 weeks for glyphosate, and 1–6 months for hexazinone, depending on soil type and climatic conditions. Degradation in soil is primarily via microbial routes. Whereas hexazinone is a very mobile herbicide (with mobility dependent on soil type), fosamine ammonium and glyphosate are strongly adsorbed and not readily leached in many soil types. Based on bioassay results, the three herbicides exhibit “very low” to “low” toxicity. Fosamine ammonium is not mutagenic and was not teratogenic when fed to pregnant rats at 10,000 ppm. Data on hexazinone indicate no carcinogenic effect in rats, negative in bacterial and mammalian point mutation assays, and not embryotoxic or teratogenic at up to 5000 ppm in diet of rats. The three herbicides have minimum-to-nil effect on soil microorganisms and exhibit little or no potential for bioaccumulation. Limitations of the available data are discussed and suggestions are made for future studies.     

Causation in risk assessment and management: models, inference, biases, and a microbial risk-benefit case study

Causal inference of exposure-response relations from data is a challenging aspect of risk assessment with important implications for public and private risk management. Such inference, which is fundamentally empirical and based on exposure (or dose)-response models, seldom arises from a single set of data; rather, it requires integrating heterogeneous information from diverse sources and disciplines including epidemiology, toxicology, and cell and molecular biology. The causal aspects we discuss focus on these three aspects: drawing sound inferences about causal relations from one or more observational studies; addressing and resolving biases that can affect a single multivariate empirical exposure-response study; and applying the results from these considerations to the microbiological risk management of human health risks and benefits of a ban on antibiotic use in animals, in the context of banning enrofloxacin or macrolides, antibiotics used against bacterial illnesses in poultry, and the effects of such bans on changing the risk of human food-borne campylobacteriosis infections. The purposes of this paper are to describe novel causal methods for assessing empirical causation and inference; exemplify how to deal with biases that routinely arise in multivariate exposure- or dose-response modeling; and provide a simplified discussion of a case study of causal inference using microbial risk analysis as an example. The case study supports the conclusion that the human health benefits from a ban are unlikely to be greater than the excess human health risks that it could create, even when accounting for uncertainty. We conclude that quantitative causal analysis of risks is a preferable to qualitative assessments because it does not involve unjustified loss of information and is sound under the inferential use of risk results by management.     

Metal bioremediation through growing cells

Heavy-metal pollution represents an important environmental problem due to the toxic effects of metals, and their accumulation throughout the food chain leads to serious ecological and health problems. Metal remediation through common physico-chemical techniques is expensive and unsuitable in case of voluminous effluents containing complexing organic matter and low metal contamination. Biotechnological approaches that are designed to cover such niches have, therefore, received great deal of attention in the recent years. Biosorption studies involving low-cost and often dead/pretreated biomass have dominated the literature and, subsequently, extensive reviews focusing on equilibrium and kinetics of metal biosorption have also come up. However, the low binding capacity of biomass for certain recalcitrant metals such as Ni and failure to effectively remove metals from real industrial effluents due to presence of organic or inorganic ligands limit this approach. At times, when pure biosorptive metal removal is not feasible, application of a judicious consortium of growing metal-resistant cells can ensure better removal through a combination of bioprecipitation, biosorption and continuous metabolic uptake of metals after physical adsorption. Such approach may lead to simultaneous removal of toxic metals, organic loads and other inorganic impurities, as well as allow optimization through development of resistant species. However, sensitivity of living cells to extremes of pH or high metal concentration and need to furnish metabolic energy are some of the major constraints of employing growing cells for bioremediation. The efforts to meet such challenges via isolation of metal-resistant bacterial/fungal strains and exploitation of organic wastes as carbon substrates have began. Recent studies show that the strains (bacteria, yeast and fungi) isolated from contaminated sites possess excellent capability of metal scavenging. Some bacterial strains possess high tolerance to various metals and may be potential candidates for their simultaneous removal from wastes. Evidently, the stage has already been set for the application of metal-resistant growing microbial cells for metal harvesting. This review focuses on the applicability of growing bacterial/fungal/algal cells for metal removal and the efforts directed towards cell/process development to make this option technically/economically viable for the comprehensive treatment of metal-rich effluents.     

重庆市“禁磷”绩效评估

国内外研究表明，水体中的磷16％左右来自使用含磷洗涤用品。为保护三峡水库水环境,防止库区水体富营养化，重庆市政府决定，从2003年１月１日起，在全市范围内禁止销售和使用含磷洗涤用品。含磷洗衣粉的磷含量平均为4%，无磷洗衣粉的磷含量平均为0.013%，“禁磷”后洗衣粉的磷削减率平均为99.7%。监测结果表明，“禁磷”前后主城区城市污水排放口总磷浓度平均降幅为15.12%、中等城市为18.36％、县城为33.66％；禁磷前，城市居民洗衣粉磷排放量占城市污水总磷的13.77％，禁磷后只占0.05％；禁磷前，农村居民洗衣粉磷排放量占农村生活污水总磷排放量的30.53％，禁磷后只占0.01％。按城市综合污水总磷浓度变化计算（考虑到城市公建商贸行业的洗涤剂用量），则禁磷后城镇削减磷排放量1 056.2 t/a；农村居民按洗衣粉实际使用量计算，入河生活污水削减磷1 203.8 t/a；城镇和农村共削减总磷排放量2 260 t/a，占重庆市磷污染负荷总量的6.0％。     

Environmental factors in the development of autism spectrum disorders

Autism spectrum disorders (ASD) are highly heterogeneous developmental conditions characterized by deficits in social interaction, verbal and nonverbal communication, and obsessive/stereotyped patterns of behavior and repetitive movements. Social interaction impairments are the most characteristic deficits in ASD. There is also evidence of impoverished language and empathy, a profound inability to use standard nonverbal behaviors (eye contact, affective expression) to regulate social interactions with others, difficulties in showing empathy, failure to share enjoyment, interests and achievements with others, and a lack of social and emotional reciprocity. In developed countries, it is now reported that 1%–1.5% of children have ASD, and in the US 2015 CDC reports that approximately one in 45 children suffer from ASD. Despite the intense research focus on ASD in the last decade, the underlying etiology remains unknown. Genetic research involving twins and family studies strongly supports a significant contribution of environmental factors in addition to genetic factors in ASD etiology. A comprehensive literature search has implicated several environmental factors associated with the development of ASD. These include pesticides, phthalates, polychlorinated biphenyls, solvents, air pollutants, fragrances, glyphosate and heavy metals, especially aluminum used in vaccines as adjuvant. Importantly, the majority of these toxicants are some of the most common ingredients in cosmetics and herbicides to which almost all of us are regularly exposed to in the form of fragrances, face makeup, cologne, air fresheners, food flavors, detergents, insecticides and herbicides. In this review we describe various scientific data to show the role of environmental factors in ASD.     

Biota-sediment accumulation factors for Dechlorane Plus in bottom fish from an electronic waste recycling site, South China

Biota-sediment accumulation factors (BSAFs) for Dechlorane Plus (DP), a highly chlorinated flame retardant, were determined in three bottom fish species, i.e., crucian carp, mud carp, and northern snakehead from an electronic waste recycling site in South China. The average BSAFs are 0.007, 0.01, and 0.06 for syn-DP, and 0.003, 0.025, and 0.001 for anti-DP in crucian carp, mud carp, and northern snakehead, respectively, suggesting low bioaccumulation potential of DP isomers in these fish. However, the bioaccumulation factors (BAFs) determined previously in the same sample set indicated that both DP isomers were highly bioaccumulative (BAFs>5000) in most of the samples. This implies that BSAF values may be inherently inconsistent affecting their reliability as a bioaccumulation indicator. The BSAFs for DP isomers are two orders of magnitude lower than those (average of 0.43-2.28) for extremely hydrophobic polychlorinated biphenyls (CBs 199, 203, 207 and 208), but are comparable to those (average of 0.0001-0.009) for decabromodiphenyl ether (BDE 209) determined in the same sample set. Despite of the different chemical structures of the three compound classes, significantly negative correlations between logarithm of octanol-water partition coefficients (log K(OW)s) and BSAFs of these chemicals were found, indicating that hydrophobicity is one of the key factors influencing the bioaccumulation of these compounds.     

Influence of alumina coating on characteristics and effects of SiO2 nanoparticles in algal growth inhibition assays at various pH and organic matter contents

Silica nanoparticles (NPs) belong to the industrially most important NP types. In a previous study it was shown that amorphous SiO(2) NPs of 12.5 and 27.0 nm are stable in algal growth inhibition assays and that their ecotoxic effects are related to NP surface area. Here, it was hypothesized and demonstrated that an alumina coating completely alters the particle-particle, particle-test medium and particle-algae interactions of SiO(2) NPs. Therefore, stability and surface characteristics, dissolution, nutrient adsorption and effects on algal growth rate of both alumina coated SiO(2) NPs and bare SiO(2) NPs in OECD algal test medium as a function of pH (6.0-8.6) and natural organic matter (NOM) contents (0-12 mg C/l) were investigated. Alumina coated SiO(2) NPs aggregated in all media and adsorbed phosphate depending on pH and NOM concentration. On the other hand, no aggregation or nutrient adsorption was observed for the bare SiO(2) NPs. Due to their positive surface charge, alumina coated SiO(2) NPs agglomerated with Pseudokirchneriella subcapitata. Consequently, algal cell density measurements based on cell counts were unreliable and hence fluorescent detection of extracted chlorophyll was the preferred method. Alumina coated SiO(2) NPs showed lower toxicity than bare SiO(2) NPs at concentrations ≥46 mg/l, except at pH 6.0. At low concentrations, no clear pH effect was observed for alumina coated SiO(2) NPs, while at higher concentrations phosphate deficiency could have contributed to the higher toxicity of those particles at pH 6.0-6.8 compared to higher pH values. Bare SiO(2) NPs were not toxic at pH 6.0 up to 220 mg/l. Addition of NOM decreased toxicity of both particles. For SiO(2) NPs the 48 h 20% effect concentration of 21.8 mg/l increased 2.6-21 fold and a linear relationship was observed between NOM concentration and effective concentrations. No effect was observed for alumina coated SiO(2) NPs in presence of NOM up to 1000 mg/l. All experiments point out that the alumina coating completely altered NP interactions. Due to the difference in surface composition the SiO(2) NPs, which had the smallest surface area, were more toxic to the alga than the alumina coated SiO(2) NPs. Hence, surface modification can dominate the effect of surface area on toxicity.     

CVM研究中支付意愿问卷“内容依赖性”的实证研究——以上海城市内河生态恢复CVM评估为例

为检验意愿价值评估法(Contingent Valuation Method,CVM)中争论的焦点问题——支付意愿的问卷"内容依赖性",本文以上海城市内河生态修复为评估对象,构建CVM的假想市场,设计评估顺序、评估对象尺度、嵌套物品等四重方案,通过720份问卷平行调查对同一评估对象在不同问卷中获得的支付意愿,并进行估计值比较和t检验。研究结果显示:支付意愿的数值随评估尺度的增加并不显著增加;单独评估比作为嵌套物品评估具有更高的支付意愿值;在问卷中先被评估的物品居民给出的支付意愿较高;整体物品的支付意愿小于各部分的加总。研究结果验证了国外实证研究文献报道的"范围不敏感"、"嵌入效应"、"顺序效应"、"部分—整体效应"等现象的存在。对此现象的解释主要是收入效应和替代效应。因此,在将CVM研究结果应用于公共政策中应充分考虑上述因素引起的偏差。     

Decolorization of Remazol Black-B using a thermotolerant yeast, Kluyveromyces marxianus IMB3

The ability of Kluyveromyces marxianus IMB3 to decolorize Remazol Black-B dye was investigated. The effect of environmental conditions, such as pH and temperature were examined. No noticeable effects on decolorization were observed when pH varied from 3.0-5.5. Maximum colour removal, 98%, was achieved at 37 degrees C. Little or no colour removal was detected when K. marxianus IMB3 was incubated under anaerobic conditions. Further investigation, in which decolorization was monitored under extreme temperatures and low pH (to inhibit growth) and using ten fold dense inoculum, revealed that decolorization was due to biosorption to the yeast cells and not due to a metabolic reaction.     

Possible involvement of plant ABC transporters in cadmium detoxification: a cDNA sub-microarray approach

As a nontolerant plant to a large number of toxic compounds, Arabidopsis thaliana is a suitable model to study regulation of genes involved in response to heavy metals. Using a cDNA-microarray approach, we identified some ABC transporters that are differentially regulated after cadmium treatments, making them putative candidates for being involved in Cd sequestration and redistribution in plants. Regarding yeast and fission yeast, in which Cd is able to form complexes either with glutathione (GSH) or phytochelatins (PC) subsequently transported into vacuoles via ABC transporters, it is also very likely that some plant ABC transporters are able to transport GS(2)-Cd or PC-Cd complexes into subcellular compartments or outside of the cell. The characterization of such transporters is of great interest for developing molecular biology approaches in phytoremediation.     

Radiation-induced adaptive response in fish cell lines

There is considerable interest at present in low-dose radiation effects in non-human species. In this study gamma radiation-induced adaptive response, a low-dose radiation effect, was examined in three fish cell lines, (CHSE-214 (Chinook salmon), RTG-2 (rainbow trout) and ZEB-2J (zebrafish)). Cell survival after exposure to direct radiation with or without a 0.1 Gy priming dose, was determined using the colony forming assay for each cell line. Additionally, the occurrence of a bystander effect was examined by measuring the effect of irradiated cell culture medium from the fish cell lines on unexposed reporter cells. A non-linear dose response was observed for all cell lines. ZEB-2J cells were very sensitive to low doses and a hyper-radiosensitive (HRS) response was observed for doses <0.5 Gy. A typical protective adaptive response was not detected in any of the three fish cell lines tested. Rather, it was found that pre-exposure of these cells to 0.1 Gy radiation sensitized the cells to subsequent high doses. In CHSE-214 cells, increased sensitivity to subsequent high doses of radiation was observed when the priming and challenge doses were separated by 4 h; however, this sensitizing effect was no longer present when the interval between doses was greater than 8 h. Additionally, a "protective" bystander response was observed in these cell lines; exposure to irradiated medium from fish cells caused increased cloning efficiency in unirradiated reporter cells. The data confirm previous conclusions for mammalian cells that the adaptive response and bystander effect are inversely correlated and contrary to expectations probably have different underlying mechanisms.     

The effect of complex formation on the adsorption characteristics of heavy metals

In most aqueous environmental systems, inorganic and organic metal complexes represent a significant contribution to the total soluble metal. Metal adsorption is often a highly pH-dependent phenomena. Such behavior can generally be attributed to changes in metal speciation with solution acidity as well as variation in the extent of surface protonation. Thus, because adsorbability may vary drastically between different metal species, (e.g. Cu²⁺ (aq) compared to CuOH⁺) a knowledge of metal species distribution is essential to understanding and interpreting metal adsorption behavior.Organic complexation has been reported to enhance, suppress and have no perceptible effect on trace metal adsorption. Such differences arise because adsorption depends on factors such as the ligand/metal ratio, adsorbability of the free ligand, and various solution parameters (e.g. pH). Most important in determining the effect of complexation on adsorption is the adsorbability of the resulting complexes. Thus, it is difficult to make generalizations about the influence of organic complexation on metal adsorption.Adsorption of metal complexes is frequently reported to be predominantly coulombic in nature; that is, binding of an anionic or cationic complex to an oppositely charged colloidal particle. However, electrostatic forces can often represent an insignificant contribution to the total free energy of adsorption and can be overshadowed by chemical reactions with the surface, hydrogen bonding, and hydrophobic effects.     

基于HJＧ１B数据的武汉市LST反演及热环境分析

以HJ 1B CCD/IRS4为主要数据源,采用单窗算法,反演了武汉市夏季高温代表日的地表温度,并用MODIS地表温度产品对反演结果进行了验证。在此基础上,提取热场变异复合指数来分析城市热岛空间分布特征,给出了城市热岛效应的定量化描述,并就不同下垫面对热岛效应的影响进行了研究。结果如下：（1）武汉城市热岛呈现整体上交错分布而局部小聚集的不规则特点,大热岛之中存在一些温度更高的小热岛;（2）武汉市2009~2012年夏季高温日平均LST为30611 K,多数城区温度达到309～317 K;（3）主城区热场变异复合指数均超过了0015,表现为较强－极强的热岛效应;6个等级的热岛效应强度的面积比例依次下降,而对应的LST平均值则逐渐升高;(4)不同地表覆盖类型LST相差较大,其在地表类型面积构成中的比例不同。研究成果可为城市热环境监测与生态评价提供科学依据     

Heterogeneous impact of agricultural support policies: evidence from Turkey

Agricultural support policies, which increase production to excessive levels, have been heavily criticized for their distortional effects on farmers’ decisions. High input consumption, which harms the environment, and the distribution of supports, which causes income inequality among farmers, are also the other factors that economists criticize these support policies. However, in recent years, the use and dependence on production and land have been increasing globally due to fears of food insecurity in several countries. In this article, the impact of a support policy on cotton farmers’ land in Turkey is evaluated using a detailed farm-level micro dataset. We use the dynamic panel model to consider the production dynamics, unobservable individual heterogeneity, and the endogeneity of the support variable. Our results show that considering the support variable as endogenous significantly increased its impact on farmers’ land. A farmer’s past land allocation decisions also affected their current lands holdings. However, the results varied considerably between regions and between different land sizes. Therefore, the findings show the importance of heterogeneity in the impact of support policies. We conclude that due to the heterogeneous impact of support policies, it might not be possible to discuss the effect of support policies using an average estimate applicable for all farmers. Therefore, a different support policy considering regional characteristics or farm size is necessary to obtain the desired policy outcomes.