Chemodynamic properties of phthalate esters: Partitioning and soil migration

Phthalate esters (PEs) form a class of organic pollutants whose chemical and physical properties relevant to their environmental transport and distribution are not completely known. Three PEs encompassing a wide range of molecular weights were studied as model compounds. Soil-water partition coefficients and rates of migration through river sand in laboratory column experiments were determined. Diethyl phthalate (DEP) has a low K_p and is fairly mobile, while di-(2-ethylhexyl) phthalate (DEHP) is strongly adsorbed and relatively immobile. Di-n-butyl phthalate (DBP), with an intermediate K_p, has a moderate mobility and exhibits a distinct flow rate dependence related to the mechanism of the adsorption and/or desorption process.     

Toxicological properties of thio- and alkylphenols causing flavor tainting in fish from the upper Wisconsin River

EC50 Microtox (5 min, 25 degrees C) assay values for 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2,4-diisopropylphenol, 2,5-diisopropylphenol 2,6-diisopropylphenol, 3,5-diisopropylphenol, carvacrol, thymol, thiophenol, and thiocresol ranged from 2 x 10(-2) mM for thymol (least toxic) to 2 x 10(-4) mM for 2,4-diisopropylphenol and 4-isopropylphenol (most toxic).     

Electrochemical detoxification of four phosphorothioate obsolete pesticides stocks

The phosphorothioate pesticides are widely used for crop production and fruit tree treatment, but their disposal causes serious environmental problems. Four commercial phosphorothioate pesticides (Demeton-S-methyl, Metamidophos, Fenthion and Diazinon) were treated by an electrolysis system using Ti/Pt as anode and stainless steel 304 as cathode. A number of experiments were run in a laboratory scale pilot plant and the results are presented. For Fenthion the achieved reduction was over 60%, while for Demeton-S-methyl, Metamidophos and Diazinon was more than 50%. Diazinon had the lowest energy demand. The COD/BOD5 ratio was improved considerably after electrolysis for all four pesticides examined. As a conclusion, electrochemical oxidation could be used as a pretreatment method of the pesticides detoxification.     

Toxicological Appraisal of Carbon Monoxide

The draft Technical Report on Air Quality Criteria for Carbon Monoxide shows thorough familiarity with the relevant toxicological studies. The authors selected materials for discussion very judiciously. They present the pertinent information in sufficient detail to permit an independent judgment of its significance, in most instances. The conclusions are firmly based on the information which is presented.     

Correlating the physical-chemical properties of phthalate esters using the 'three solubility' approach

A quantitative structure-property relationship (QSPR) method for the correlation of physical-chemical properties and partition coefficients, namely the 'three solubility' approach, is described and applied to a group of 22 phthalate esters. The solubilities or 'apparent-solubilities' of these substances in the liquid state are compiled and correlated against Le Bas molar volume in the three primary media of air, water and octanol. From these solubilities the air-water (K(AW)), octanol-water (K(OW)) and octanol-air (K(OA)) partition coefficients are deduced. Estimated solubilities in water and octanol-water partition coefficients are shown to compare favourably with more recent accurate measurements. A set of selected values is presented, with error limits, which is recommended for use in modelling and assessment studies. Some environmental implications are discussed of the large range in property values for this series.     

Degradation of short-chain alkyl- and alkanolamines by TiO2- and Pt/TiO2-assisted photocatalysis

The photooxidation of C2H5NH2, (C2H5)2NH, HOC2H4NH2, (HOC2H4)2NH and (HOC2H4)3N using TiO2 and Pt/TiO2 as photocatalysts has been investigated. A laboratory set up was designed and a study on the influence of the concentration of the photocatalyst, the pH-value and the structure of the amine performed. The photocatalytic process was optimized with respect to the concentrations of the model substances during degradation. The decrease of the amine concentrations was found to be maximum at a pH of 10. The time-dependence of the formation of cationic breakdown products, such as NH3/NH4 and short-chain alkyl- and alkanolamines was studied by analyses with single column ion chromatography. The experimental data show that the photodegradation follows a Langmuir-Hinshelwood kinetic. The mineralization of the model substances also was monitored by measurements of the decrease of the TOC and of the formation of NO2 and NO3. The different mineralization efficiencies for the model substances studied are discussed with regard to their structure and adsorption behaviour on the photocatalyst. A possible breakdown mechanism involving the electrophilic attack of the hydroxyl radical is given. The applicability of the TiO2-assisted photocatalytic degradation of C2H5NH2 and (C2H5)2NH was tested at the pilot plant-scale with real solar radiation. The degradation rates and products obtained were similar to those found in the laboratory experiments.     

Toxicological effect of MPA-CdSe QDs exposure on zebrafish embryo and larvae

Cadmium selenium (CdSe) quantum dots (QDs) are semiconductor nanocrystals that hold wide range of applications and substantial production volumes. Due to unique composition and nanoscale properties, their potential toxicity to aquatic organisms has increasingly gained a great amount of interest. However, the impact of CdSe QDs exposure on zebrafish embryo and larvae remains almost unknown. Therefore, the lab study was performed to determine the developmental and behavioral toxicities to zebrafish under continuous exposure to low level CdSe QDs (0.05-31.25 mg L⁻¹) coated with mercaptopropionic acid (MPA). The results showed MPA-CdSe exposure from embryo to larvae stage affected overall fitness. Our findings for the first time revealed that: (1) The 120 h LC₅₀ of MPA-CdSe for zebrafish was 1.98 mg L⁻¹; (2) embryos exposed to MPA-CdSe resulted in malformations incidence and lower hatch rate; (3) abnormal vascular of FLI-1 transgenic zebrafish larvae appeared after exposure to MPA-CdSe including vascular junction, bifurcation, crossing and particle appearance; (4) larvae behavior assessment showed during MPA-CdSe exposure a rapid transition from light-to-dark elicited a similar, brief burst and a higher basal swimming rate; (5) MPA-CdSe induced embryos cell apoptosis in the head and tail region. Results of the observations provide a basic understanding of MPA-CdSe toxicity to aquatic organisms and suggest the need for additional research to identify the toxicological mechanism.     

Toxicological effects of marine palytoxin evaluated by FETAX assay

The FETAX (frog embryo teratogenesis assay Xenopus) is considered a useful bioassay to detect health hazard substances. In the study of the marine toxin palytoxin (PTX), FETAX has revealed evident impacts on embryo mortality, teratogenesis and growth at the two highest (370 and 37nM) concentrations used. Significant mortality rates, peaks in the number of malformed embryos and delays in growth were found, while the total sample number fell by about 80% at the end of the assay with the concentrated dose. The histological analysis to evaluate the morpho-functional induced modifications demonstrated damage to the nervous and muscle tissue, a general reduction in the size of the main inner visceral organs and severe injury to the heart structure in some specimens. No inflammatory response was observed.     

Toxicological assessment of chlorinated diphenyl ethers in the rat

Chlorinated diphenyl ethers are environmental contaminants that have been found in Great Lakes fish and birds. Because of their presence in the food chain, and potential for human exposure, the present short-term study was conducted to assess their toxicity. Groups of 10 male and 10 female rats were each given by gavage 2,2',4,4'6-pentachlorodiphenyl ether (CDE1), 2,2',4,4',5,6-hexachlorodiphenyl ether (CDE2) or 2,2',3,3',4,6'-hexachlorodiphenyl ether (CDE3) at dose levels of 0.04, 0.4, 4.0 or 40 mg/kg b.w./day for a period of 28 days. The control group received an equivalent volume of corn oil only (0.5 ml/100 g b.w.). Treatment with the three CDE congeners did not result in suppression of growth rate or food consumption. Increased liver weights were seen in the animals of both sexes fed 40 mg/kg CDE2, in males treated with 40 mg/kg CDE1, and in females with 40 mg/kg CDE3. Hepatic microsomal aminopyrine demethylase activity was significantly higher in the male rats administered 40 mg/kg CDE2, and aniline hydroxylase activity was elevated in the females following the same treatment. Serum glucose, calcium, protein and urea nitrogen of CDE1-treated males were higher than the control. Levels of uric acid, potassium and LDH of CDE3-treated females were also elevated. No hematological changes were observed. Histological examination revealed that the liver and thyroid were the target organs affected by CDE treatment but the morphological changes were mild even at the highest dose level. Changes in the liver consisted of nuclear vesiculation and increased cytoplasmic volume. Alterations in the thyroid were characterized by increased epithelial height and follicular collapse. Based on the data presented above, the 3 CDE congeners can only be considered moderately toxic in the rat.     

水环境中邻苯二甲酸酯的迁移转化研究

邻苯二甲酸酯(PAEs)是一类普遍使用的化学工业品,并广泛存在于环境中.已有研究表明,PAEs环境内分泌干扰物,对人类和自然环境有非常大的危害.总结了PAEs在地表水中的分布和在水体中迁移转化的主要途径,如水解、光降解、与颗粒物(沉积物或悬浮颗粒物)的作用以及生物转化作用,并指出对它们进一步研究的重要性和今后主要的研究方向.     

Toxicological responses of earthworm (Eisenia fetida) exposed to metal-contaminated soils

The aim of this study was to evaluate the toxicological responses of earthworm (Eisenia fetida) induced by field-contaminated, metal-polluted soils. Biochemical responses and DNA damage of earthworm exposed to two multi-metal-contaminated soils in a steel industry park and a natural reference soil in Zijin Mountain for 2, 7, 14, and 28 days were studied. Results showed that three enzyme activities, including superoxide dismutase (SOD), acetylcholinesterase (AChE), and cellulase, in earthworm in metal-contaminated soils were significantly different from those of the reference soil. Cellulase and AChE were more sensitive than SOD to soil contamination. The Olive tail moment of the comet assay after 2-day exposure increased 56.5 and 552.0 % in two contaminated soils, respectively, compared to the reference soil. Our findings show that cellulase and DNA damage levels can be used as potential biomarkers for exposure of earthworm to metal-polluted soils.     

Toxicological assessment of chlorinated diphenyl ethers in the rat, Part II

Chlorinated diphenyl ethers (CDE's) are environmental contaminants that have been found in Great Lakes fish. Because of the paucity of toxicity data and potential for human exposure, the present short-term study was conducted to assess their potential toxic effects. Groups of 10 male and 10 female rats were administered the three CDE congeners (2,2',4,4',5-pentachlorodiphenyl ether (PCDE), 2,2',4,4',5,5'-hexachlorodiphenyl ether (HCDE), 2,2',3,4,4',6,6'-heptachlorodiphenyl ether (HPCDE] in diets at levels of 0.5, 5.0, 50 or 500 ppm for a period of 4 weeks. Decreased food consumption was observed with male and female rats fed the diet containing 500 ppm HPCDE. Treatment with the three isomers at the highest dose level produced an increase in liver weight in both sexes. While administration of PCDE produced an increase in hepatic aminopyrine demethylase activity, HCDE caused a significant increase in aminopyrine demethylase, aniline hydroxylase and ethoxyresorufin de-ethylase activities. HPCDE caused a significant increase in ethoxyresorufin de-ethylase activity. HPCDE at the highest dose level also caused a significant reduction in circulating lymphocytes in male rats. The 3 CDE's produced mild and adaptative histological changes in the liver and thyroid, but only HPCDE elicited mild changes in the thymus, bone marrow, and spleen. The above data indicate that HPCDE is immunosuppressive and that all three CDE isomers are considered to be moderately toxic in rats. The no-observable effects levels appear to be between 5-50 ppm in diet (0.36-3.0 mg/kg b.w.) for the three CDE's.     

Biodegradation of four phthalate esters in sludge

This study investigated the effects of ultrasonic pretreatment and various treatments on the aerobic degradation of four phthalic acid esters (PAEs) such as diethyl phthalate (DEP), benzyl butyl phthalate (BBP), di-n-butyl phthalate (DBP) and di-(2-ethyl hexyl)phthalate (DEHP) in sludge. The effect on PAE degradation of treating sludge with a 20 min sonication period at a power level of 0.1 W ml(-1) was evaluated. The degradation rates of the four PAEs were DBP>BBP>DEP>DEHP. Degradation rate constants (k(1)) and half-lives (t(1/2)) for the four PAEs (50 mg kg(-1)) ranged from 0.182 to 0.379 day(-1) and 1.8 to 3.8 days, respectively. The optimal pH for PAE degradation in sludge was 7.0 at 30 degrees C. PAE degradation was enhanced by the addition of yeast extract, brij 30 or brij 35 and inhibited by the addition of hydrogen peroxide. Our results show that a combination of ultrasonic pretreatment and biodegradation can effectively remove PAE from sludge.     

Trace phthalate and adipate esters contaminated in packaged food

A method for trace analysis of two plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA), contaminated in packaged curry paste were investigated by gas chromatography with flame ionization detector (GC-FID). Curry paste samples were extracted by ultrasonic and solid phase extraction using Florisil® cartridge. Analysis by the GC-FID system provided limits of detection for DEHA and DEHP at 12 and 25 μ g L^{? 1} and a linear dynamic range between 25 μ g L^{? 1} to 60 mg L^{? 1} with a coefficient of determination (R²) greater than 0.99. High recoveries were obtained, ranged from 91 to 99% and 88 to 98% for DEHP and DEHA with RSD lower than 7 and 10% respectively. The method detection limit and limits of quantitation were ranged from 27 to 30 and 90 to 100 μ g L^{? 1}. The analysis of curry paste samples showed concentrations of DEHP and DEHA in the range of 4.0 ng g^{? 1} to 0.61 μg g^{? 1}.     

Toxicological evaluation of constructed wetland habitat sediments utilizing 10-day sediment toxicity test and bacterial bioluminescence

A toxicological evaluation was conducted on wetland habitats created as a result of run-off from agricultural areas. These temporary wetlands were created by using drop pipes as a means of reducing erosional cutting in agricultural fields. Toxicity bioassays utilizing bacterial bioluminescence and Hyalella azteca were used to assess sediment pore water and whole sediment, respectively. Inhibition of bacterial bioluminescence was initially used to determine relative toxicities of pore water from ten wetland sites. Constructed wetland sites were compared to the University of Mississippi Biological Field Station, a relatively pristine reference site. The H. azteca ten day sediment toxicity test was utilized to assess sediment from four selected sites using survival and growth as toxicological endpoints. Results from the toxicological evaluation, along with extensive ecological evaluations, were used to assess the best approach for implementation of temporary wetland habitats with existing agricultural practices.     

Trace phthalate and adipate esters contaminated in packaged food

A method for trace analysis of two plasticizers, di-2-ethylhexyl phthalate (DEHP) and di-2-ethylhexyl adipate (DEHA), contaminated in packaged curry paste were investigated by gas chromatography with flame ionization detector (GC-FID). Curry paste samples were extracted by ultrasonic and solid phase extraction using Florisil(R) cartridge. Analysis by the GC-FID system provided limits of detection for DEHA and DEHP at 12 and 25 microg L(- 1) and a linear dynamic range between 25 microg L(- 1) to 60 mg L(- 1) with a coefficient of determination (R(2)) greater than 0.99. High recoveries were obtained, ranged from 91 to 99% and 88 to 98% for DEHP and DEHA with RSD lower than 7 and 10% respectively. The method detection limit and limits of quantitation were ranged from 27 to 30 and 90 to 100 microg L(- 1). The analysis of curry paste samples showed concentrations of DEHP and DEHA in the range of 4.0 ng g(- 1) to 0.61 microg g(- 1).