Impurities in industrial grade 4,4'-isopropylidene diphenol (bisphenol A): possible implications for estrogenic activity

Fifteen trace impurities, including a novel cyclohexene derivative, have been identified and quantified in samples of an industrial grade of the oestrogen-active compound 4,4'-isopropylidene diphenol (bisphenol A). All of these compounds, like bisphenol A itself, possess phenolic hydroxyl groups para to other substituents and all thus might also have oestrogenic properties. Published studies on the endocrine disrupting properties of bisphenol A have not considered potentially active impurities but full assessment of the oestrogenicity of bisphenol A, as it is used commercially, will become possible when adequate supplies of these compounds are available through synthesis.     

Comparative acute toxicity of leachates from plastic products made of polypropylene, polyethylene, PVC, acrylonitrile–butadiene–styrene, and epoxy to Daphnia magna

Purpose

The large global production of plastics and their presence everywhere in the society and the environment create a need for assessing chemical hazards and risks associated with plastic products. The aims of this study were to determine and compare the toxicity of leachates from plastic products made of five plastics types and to identify the class of compounds that is causing the toxicity.

Methods

Selected plastic types were those with the largest global annual production, that is, polypropylene, polyethylene, and polyvinyl chloride (PVC), or those composed of hazardous monomers (e.g., PVC, acrylonitrile?Cbutadiene?Cstyrene [ABS], and epoxy). Altogether 26 plastic products were leached in deionized water (3?days at 50°C), and the water phases were tested for acute toxicity to Daphnia magna. Initial Toxicity Identification Evaluations (C18 filtration and EDTA addition) were performed on six leachates.

Results

For eleven leachates (42%) 48-h EC50s (i.e the concentration that causes effect in 50 percent of the test organisms) were below the highest test concentration, 250 g plastic/L. All leachates from plasticized PVC (5/5) and epoxy (5/5) products were toxic (48-h EC50s ranging from 2 to 235?g plastic/L). None of the leachates from polypropylene (5/5), ABS (5/5), and rigid PVC (1/1) products showed toxicity, but one of the five tested HDPE leachates was toxic (48-h EC50 17?C24?g plastic/L). Toxicity Identification Evaluations indicated that mainly hydrophobic organics were causing the toxicity and that metals were the main cause for one leachate (metal release was also confirmed by chemical analysis).

Conclusions

Toxic chemicals leached even during the short-term leaching in water, mainly from plasticized PVC and epoxy products.     

饮用水的有机锡问题及对策

有机锡类化合物对环境生态和人类有很强内分泌毒性.其主要来源包括有机锡产品的生产和消耗、生物和化学甲基化效应.当前饮用水日益受到有机锡污染的严重威胁,主要原因有水源水的有机锡污染、PVC管材稳定剂的渗出和管网生物甲基化作用.通过分析提出解决饮用水有机锡问题应从3方面考虑,一是采用紫外光解或化学氧化处理受污染水源水,破坏水中有机锡化合物并消除其毒性;二是加强PVC管材质量要求,尽量采用低毒管材;三是定期更换给水管段以减少管网中生物甲基化导致的二次污染.     

Transformation of a non-oestrogenic steroid metabolite to an oestrogenically active substance by minimal bacterial activity

The majority of oestrogenic material excreted from humans and wildlife, and therefore released into sewers, is in a conjugated form. However, the finding of “free” oestrogens in sewage effluent suggests that these metabolites are somehow converted back into an active form, before or during passage through a sewage treatment process. When male fathead minnows (Pimephales promelas) were continuously exposed to oestradiol-3-glucuronide, in a continuous-flow system, it demonstrated no inherent oestrogenic activity. However, when fish were exposed to effluent generated from laboratory simulations of sewage treatment processes, to which had been added oestradiol-3-glucuronide, oestrogenic activity was observed, suggesting microbial activity was capable of degrading the steroid metabolite into a more potent oestrogen. Oestrogenic potency was determined by measuring changes in plasma vitellogenin (egg yolk precursor) concentrations and gonadosomatic index. The results suggest that inactive metabolites of steroids are very readily biotransformed into biologically active oestrogens.     

Materials selection for a dry atmospheric mercury deposits sampler.

In order to develop a sampler for measuring dry deposition rates for atmospheric mercury, suitable materials are needed that neither adsorb nor release mercury. In this paper, four materials (polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS), Teflon and glass) were tested. Each of the materials was placed in a beaker containing mercuric solution under varied conditions for pH, preservative concentration, initial mercuric concentration, temperature, acid type and contact time of the material. The concentrations of the mercuric solutions were determined using the cold-vapor atomic absorption (CVAA) technique. The experimental results show that glass has the lowest absolute net adsorption rates (NARs) of 0.026-1.13 pg/m2 among the materials tested. Teflon, PVC and ABS have NARs ranging from 0.54 to 10.4 microg/M2 over an adsorption duration of one or two weeks. ABS has significantly higher adsorption rates for mercury than PVC and Teflon, indicating its inappropriateness as the material for building the sampler. Teflon and PVC will be the materials of choice for the sampler. The experimental results can also be used in establishing appropriate sampling conditions in the field.     

Effects of mono-(2-ethylhexyl) phthalate (MEHP) on chicken germ cells cultured in vitro

In recent decades, many toxicological tests based on in vivo or in vitro models, mainly from mammalian (rat–mouse) and fish species, were used to assess the risks raised by contact or ingestion of molecules of pharmaceutical, agricultural, or natural origin. But no, or few, in vitro tests using other non-mammalian models such as bird have been explored despite their advantages: the embryonic gonads of birds have a high plasticity of development sensitive to estrogen, and sperm production is nearly two times faster than in rodents. Hence, we have established an in vitro culture of germ cells and somatic cells from chicken post-natal testis, and we have evaluated the sensitivity against the endocrine disruptor compound mono-(2-ethylhexyl) phthalate (MEHP) in comparison to previous studies using rodent and human models. After 96 h of exposure in presence of 10 μM MEHP, chicken seminiferous tubules cultures present a structural alteration, a reduction in cell proliferation and in germ cells population. Apoptosis of germ and somatic cells increases in presence of 1 μM MEHP. Furthermore, MEHP does not affect inhibin B and lactate production by Sertoli cells. These results are in accordance with previous studies using rat, mice, or human culture of testicular cells and in similar range of exposures or even better sensitivity for some “end-points” (biological parameters). In conclusion, the establishment of this postnatal testicular cells culture could be considered as an alternative method to in vivo experiments frequently used for evaluating the impact on the terrestrial wildlife species. This method could be also complementary to mammal model due to the limiting number of animals used and its elevated sensitivity.     

Dissipation and leaching of (14)C-monocrotophos in Soil Columns under subtropical climate

Dissipation and leaching behavior of 14C-monocrotophos was studied for 365 days under field conditions using PVC cylinders. The first set (24 cylinders) was spiked with 1.0 microCi 14C-labeled monocrotophos along with 1.06 mg unlabeled monocrotophos to give a concentration of 2 mg kg -1 in the soil up to 15 cm depth. The second set (24 cylinders) received 14C-labeled monocrotophos along with other non-labeled insecticides viz., dimethoate @ 300 g a.i ha-1, deltamethrin @ 12.5 g a.i ha-1, endosulfan @ 750 g a.i ha-1, cypermethrin @ 60 g a.i ha-1, and triazophos @ 600 g a.i ha-1 at an interval of 15 days each as recommended for the cotton crop. 14C-monocrotophos dissipated faster, up to 45% in first 90 days in columns treated with only monocrotophos compared to 25% in columns that received monocrotophos along with other insecticides. However, both the columns showed similar residues 180 days onward. After 180 days of treatment, 46% radiolabeled residues were observed, which reduced up to 39.6% after 365 days. Leaching of 14C-monocrotophos to 15-30 cm soil layer was observed in both the experimental setups. In the 15-30 cm soil layer of both soil columns, up to 0.19 mg 14C-monocrotophos kg-1d. wt. soil was detected after 270 days.     

The relative contribution of wood and poly(vinyl chloride) to emissions of PCDD and PCDF from house fires

Emissions of PCDD/F from poly(vinyl chloride) (PVC) burned in house fires has been estimated at <1 g I-TEQ/yr in the US. In the current literature-based study, amounts of wood (21,000 kg) and PVC (180 kg) in a new house of standard construction are calculated and previously published emission factors for wood (0.01–173 μg/t) and PVC (3–6554 μg/t) are reported. Test conditions under which emission factors are generated differ and may not be directly comparable. Typically, PVC is tested at small-scale under relatively poor combustion conditions and wood is tested at large-scale under good combustion conditions. Thus, overall emission from combustion of these two materials of construction in house fires on an as-used basis is estimated to be similar (on the order of 1 g/yr) and a small contributor to the PCDD/F sources inventory. No speculation is made with respect to contents, roofing or other materials of construction.     

Assessing demineralization treatments for PVC effluent reuse in the resin polymerization step

To reduce fresh water consumption in a polyvinyl chloride (PVC) plant, the effluent from a biological treatment must be demineralized to be re-used in the resin polymerization process. Demineralization is a critical process, since the quality and the stability of the PVC resins are highly influenced by the water quality used in the process. The main target values for water parameters are the following: conductivity <10 μScm^?1, TOC < 10 mg L^?1, and Al < 0.1 mg L^?1. To achieve this quality, several reverse osmosis membranes from different materials and suppliers were tested and compared in the demineralization treatment. Polyamide membranes showed higher salt rejection compared to cellulose acetate membranes yielding both types similar flux and permeability. Two-pass reverse osmosis treatment was necessary to reach conductivities lower than 10 μS cm^?1. On the other hand, a good quality effluent for reuse was obtained by combining RO and ionic exchange resins. Results showed that good quality PVC resins in terms of color, granulometry, porosity, and bulk density were obtained when demineralized water from two-pass reverse osmosis was used as fresh water, proving the feasibility of the effluent reuse in the PVC industry.     

PVC废物及其处理技术

PVC广泛应用于工业和日常生活中 ,PVC废物的产生量将会在将来一段时间内持续增长 ,对PVC废物处理处置问题研究成为固体废物处理处置的一个方向。目前 ,PVC废物还缺乏系统、完善的管理手段和处理技术。本文在分析PVC废物特点其环境潜在危害特性的基础上 ,比较分析各种PVC废物处理技术的优势和存在的问题 ,及国内外在PVC废物处理处置方面的具体实践 ,以期探讨PVC废物的处理对策并提出今后PVC废物处理的发展趋势和研究方向     

Carbon Monoxide and Sulfur Dioxide Adsorption on— and Desorption from Glass,Plastic, and Metal Tubings

It was planned to install 305 m (1000 ft) of tubing on a television tower to transport ambient air samples from different height levels to pollutant monitoring instruments at ground level. A feasibility study was undertaken to determine the sorption characteristics of sulfur dioxide and carbon monoxide on various conduit materials. Sorption studies were completed on 30.5 m (100 ft) lengths of 1.3 cm (Y2 in) diam tubings of glass, Teflon, tygon, polypropylene, PVC piping, aluminum, and stainless steel. Final tests were completed on 305 m of 1.9 cm (3/4 in) diam stainless steel tubing. The following variables were investigated: tubing diameter, gas concentration, flowrate through the tubing, temperature, humidity, and the effect of sorption with sulfur dioxide and carbon monoxide alone or together. The parameter ranges studied approximated either atmospheric or air sampling conditions. For carbon monoxide, there was no significant difference between the mean inlet and outlet tubing concentrations under the conditions of the study. With sulfur dioxide, there was neither tubing adsorption nor desorption under the experimental parameters studied, except for tygon, PVC, and aluminum. After a conditioning period with sulfur dioxide, tygon, PVC, and aluminum could also be used as air inlet conduits; tygon is not recommended.     

Selective sensing of mercury(II) using PVC-based membranes incorporating recently synthesized 1,3-alternate thiacalix[4]crown ionophore

The construction and electrodes characteristics of poly(vinylchloride) (PVC)-based polymeric membrane electrode (PME) and coated graphite electrode (CGE), incorporating 1,3-alternate thiacalix[4]crown as ionophore for estimation of Hg(II) ions, are reported here. The best potential response was observed for PME-1 having membrane composition of: ionophore (6.2 mg), PVC (100.0 mg), 2-nitrophenyl octyl ether (2-NPOE; 200.0 mg), and sodium tetraphenyl borate (NaTPB; 2.0 mg); for CGE-1 with the membrane composition: ionophore (3.5 mg), PVC (40.0 mg), 2-NPOE (80.0 mg), and NaTPB (2.0 mg). The electrodes exhibits Nernstian slope of 29.16 mV/decade with PME-1 and 30.39 mV/decade with CGE-1 for Hg(II) ions over wide concentration range, i.e., 1.0?×?10^?1 to 5.0?×?10^?6?M with PME-1 and 1.0?×?10^?1 to 5.0?×?10^?7?M with CGE-1. Lower detection limits were found to be 9.77?×?10^?6?M for PME-1 and 7.76?×?10^?7?M for CGE-1 with response time varying from 10 to 20 s. Also, these electrodes work within pH range of 2.0–6.0 for PME-1 and 1.5–6.5 for CGE-1. Overall, CGE-1 has been found to be better than PME-1. CGE-1 has been used as indicator electrode for the potentiometric titration of Hg(II) ions with EDTA as well as successfully applied for determination of Hg(II) content in wastewater, insecticide, dental amalgam, and ayurvedic medicines samples with very good performance (0.9974 correlation coefficient in the comparison against volumetric method).     

超临界水无害化共处理PVC和医疗垃圾焚烧飞灰的可行性探讨

采用超临界水氧化降解PVC同时无害化处理医疗垃圾焚烧飞灰,利用PVC脱氯形成的中间产物盐酸提取医疗垃圾焚烧飞灰中的重金属,达到飞灰无害化的目的。结果显示,超临界水可以将飞灰颗粒打碎,从而提高盐酸提取重金属的速率和效果,但是在超临界水中还存在重金属的固定过程,过长的反应时间和过高的反应温度都会降低重金属的提取效率。在提取过程中,Cu和Zn优先于Pb被盐酸浸出,而Pb被浸出后很容易被超临界水进一步固定。综合考虑重金属在超临界水中的变化特性,总结出超临界水处理飞灰和PVC的最佳条件为:PVC与飞灰质量比0.5:1,温度400℃,提取时间90 min。处理后的飞灰再次经过水洗后,其重金属浸出浓度低于USEPA规定的限制值。本研究为飞灰的无害化处理提供一条新的思路。     

Two dechlorinated chlordecone derivatives formed by in situ chemical reduction are devoid of genotoxicity and mutagenicity and have lower proangiogenic properties compared to the parent compound

Chlordecone (CLD) is a chlorinated hydrocarbon insecticide, now classified as a persistent organic pollutant. Several studies have previously reported that chronic exposure to CLD leads to hepatotoxicity, neurotoxicity, raises early child development and pregnancy complications, and increases the risk of liver and prostate cancer. In situ chemical reduction (ISCR) has been identified as a possible way for the remediation of soils contaminated by CLD. In the present study, the objectives were (i) to evaluate the genotoxicity and the mutagenicity of two CLD metabolites formed by ISCR, CLD-5a-hydro, or CLD-5-hydro (5a- or 5- according to CAS nomenclature; CLD-1Cl) and tri-hydroCLD (CLD-3Cl), and (ii) to explore the angiogenic properties of these molecules. Mutagenicity and genotoxicity were investigated using the Ames’s technique on Salmonella typhimurium and the in vitro micronucleus micromethod with TK6 human lymphoblastoid cells. The proangiogenic properties were evaluated on the in vitro capillary network formation of human primary endothelial cells. Like CLD, the dechlorinated derivatives of CLD studied were devoid of genotoxic and mutagenic activity. In the assay targeting angiogenic properties, significantly lower microvessel lengths formed by endothelial cells were observed for the CLD-3Cl-treated cells compared to the CLD-treated cells for two of the three tested concentrations. These results suggest that dechlorinated CLD derivatives are devoid of mutagenicity and genotoxicity and have lower proangiogenic properties than CLD.     

Concentrations of phthalate esters and identification of other additives in PVC children’s toys

This study was intended to provide data on the composition of soft PVC toys, addressing the widest practicable range of chemical additives and including non-phthalate additives. The study also included toys from as many countries as possible, since for many, no data were available. A total of 72 toys were purchased in 17 countries. The majority (64) were PVC or had PVC sections. In almost all the soft PVC toys analysed, phthalates comprised a sizeable proportion (most frequently 10–40%) of the total weight of the toy. The predominant phthalates detected were diisononyl phthalate (DINP) and di(2-ethylhexyl) phthalate (DEHP). Other phthalates identified in high concentrations in some toys include isomeric mixes of diisooctyl phthalate (DIOP) and diisodecyl phthalate (DIDP). The estrogenic chemical nonylphenol was isolated from 13 toys, while 2 toys were found to contain the fungicide Fungitrol 11 (Folpet). 78% of PVC toys contained one or more extractable organic compounds in addition to those reported above. Some of these data have been released previously by Greenpeace and made available on the internet.This report, however, which is intended for a technically expert audience, has been peer reviewed and contains further analytical data that have not been published before.     

Bisphenol A content in fish caught in two different sites of the Tyrrhenian Sea (Italy)

Bisphenol A (BPA) is an endocrine disruptor (ED) that is abundant in the environment because of its extensive use in human-manufactured products. In this study, the BPA concentration was measured in the muscle and liver of five edible fish, characterized by different habitat and habits, caught in two different sites of the Tyrrhenian Sea (Italy). Our results show that: (i) fish livers are about 2.5 times more polluted than muscle; (ii) fish caught in the Gulf of Naples are more polluted than those from the Latium coasts, ranging from 1.2-fold more for White Bream to 6.6-fold for Grey Mullet; and (iii) the percentages of fish found to be BPA-polluted in the Gulf of Naples ranged from 73% (for Bass) to 90% (for Mullet), while the Latium fish range from 60% (for Bass) to 90% (for Mullet). These data indicate that consumers of fish caught in the Gulf of Naples are at a greater risk for BPA-induced endocrine pathologies compared to those who consume fish caught along the Latium coasts.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

不同助剂增韧改性W-EP/PVC复合材料性能

采用不同的助剂(MBS、CPE、NBR)对W-EP/PVC(废环氧树脂/PVC)复合材料进行增韧改性,并对改性后的复合材料进行表征。结果表明,单一助剂的添加可显著提高冲击强度,但拉伸强度有所降低;助剂的加入均会使共混体系流变性能有一定程度降低;粉末丁腈橡胶中丙烯腈含量影响复合材料力学性能。MBS和粉末丁腈橡胶P83的改性效果较好,两者组成的双改性剂具有协同作用,且MBS/P83添加比例为7/3时,复合材料性能达到最佳。     

Dilemmas facing regulatory and advisory bodies dealing with conflicting results.

Regulatory and advisory bodies have to take into account the possibility that conventional toxicological screening and testing methods may be failing to pick up relevant effects, with the implication that testing may need to go down to much lower exposure levels and use specifically designed studies. In the paper, attention is focused on the problems of understanding endocrine disrupting activity. The shape of the dose-response curve for endocrine disrupters may differ from that normally associated with toxic chemicals (the monotonic sigmoid curve). Thus, prediction of both the nature of the effects of potential endocrine disrupters and the intensity of those effects at different doses may be equally difficult. Endocrine effects are not currently amenable to analysis by a single apical assay. While existing toxicological tests can pick up many end-organ and functional effects that are relevant to endocrine disturbances, they are generally poor at exploring apparently subtle effects such as disturbances of brain endocrine homeostatic mechanisms which may be critical for normal development.