邻苯二甲酸酯在长江重庆段水体的概率风险分析

以长江重庆段水体12个采样断面4种邻苯二甲酸酯（PAEs）的监测结果及水生生物的生态毒性参数无观察效应浓度（NOEC）为基础资料,采用安全阈值和概率曲线分布两种概率风险评价方法分析了邻苯二甲酸酯的相对生态风险。研究结果表明：邻苯二甲酸二甲酯（DMP）、邻苯二甲酸二乙酯（DEP）、邻苯二甲酸正丁酯（DBP）、邻苯二甲酸双（2 乙基己基）酯（DEHP）的安全阈值分别为4 31079、2171、147、199,对水生生物无风险。以5%水生生物物种受影响作为可接受的效应水平终点（HC5）,采用概率曲线分布进行分析,DBP、DEHP的浓度超过毒性值的风险概率分别为106×10-2、235×10-4,4种邻苯二甲酸酯风险大小依次为：DBP>DEHP>DEP>DMP,与安全阈值法结果一致。两种概率风险方法从不同的角度反映了污染物的生态风险。     

Occurrence of phthalate esters in water and sediment of urban lakes in a subtropical city, Guangzhou, South China

Extensive use of phthalate esters (PAEs) in both industrial processes and consumer products has resulted in the ubiquitous presence of these chemicals in the environment. This study reports the first data on the concentrations of 16 phthalate esters (PAEs) in water and sediments of the urban lakes in Guangzhou City. PAEs were detected in all samples analyzed, mainly originating from urban stormwater runoff, atmospheric deposition, as well as untreated discharge of industrial wastewater and municipal sewage. The Sigma(16)PAEs concentrations in water and sediments ranged from 1.69 to 4.72 microg L(-1) and 2.27 to 74.94 microg g(-1)-dry weight (dw), with the mean concentrations of 2.91 microg L(-1) and 20.85 microg g(-1)-dw, respectively, which indicates that sediment is a significant sink for PAEs. Variability of the Sigma 16PAEs concentrations in water and sediment in the urban lakes was almost consistent. The spatial distribution of PAEs was site-specific. Of the 16 PAEs, DMP, DEP, DnBP, DiBP, DMPP, and DEHP were present in all water and sediment samples. DnBP was abundant in water (53.0-81.2%), while no single dominant congener was found in sediments. The abundances of DiBP were similar to those of DEHP, and DiBP and DEHP collectively accounted for 77.2-97.6% of the Sigma 16PAEs concentrations. Congener specific analysis confirmed that DnBP was a predictive indicator for the dissolved summation operator16 PAEs concentration (correlation coefficient r=0.968, p<0.01), and that DiBP was a predictive indicator for the sediment summation operator16 PAEs concentration (r=0.975, p<0.01). As compared to the results for other studies, the urban lakes of Guangzhou were moderately polluted by PAEs.     

构建湿地去除酞酸酯的基质微生物和酶机制研究

随着塑料制品的广泛使用，酞酸酯的污染越来越引起人们的广泛关注。目前，DBP(邻苯二甲酸二丁酯)和DEHP(邻苯二甲酸二异辛酯)已成为全球最普遍的污染物之一。报告了复合垂直流构建湿地对含酞酸酯(DBP等)的污水污染的去除效果，以及湿地去除酞酸酯的基质微生物和酶方面的净化机理。具体结果如下：复合垂直流构建湿地对酞酸酯污染具有较好的净化效果，去除率高达99．9％以上；构建湿地对酞酸酯的净化主要发生在氧气含量相对较多的下行流池，上行流他的净化作用相对较差；同时分层实验还发现，构建湿地的净化作用主要集中在湿地上层基质中。通过研究，为进一步研究利用构建湿地处理酞酸酯污染提供了有益的参考。     

Determination of phthalate ester plasticizers in the aquatic environment of Southwestern Nigeria

Water from the Lagos, Oyo, Osun, Ondo, and Delta states of Nigeria and the cities' water treatment plants had been analized for the presence of ubiquitous phthalate esters using liquid chromatography. Extraction with CH₂Cl₂ and liquid chromatography was used for compound separation. Several phthalate esters, dimethyl- (DMP), diethyl- (DEP), and di-n-butyl- (DBP) were found present at levels of 10 mg L⁻¹ to 1472 mg L⁻¹ in river water and 91 mg L⁻¹ to 1219 mg L⁻¹ in tap water from the cities' water treatment plants. A study of uncontaminated water was done to establish blank levels.     

Biodegradation of phthalic acid esters by immobilized microbial cells

Microorganisms capable of degrading di-n-butyl phthalate (DBP) were immobilized by polyvinyl alcohol (PVA) and used for DBP degradation. The characteristics of DBP degradation by immobilized and free cells were investigated. The experimental results showed that the degradation rate of immobilized cells was higher than that of free cells. The optimal pH and temperature for DBP degradation were determined to be 7.0 and 25°C, respectively. The semi-continuous degradation test demonstrated that high-frequency feeding of low concentration (50 mg/L) was more favourable than low-frequency feeding of high concentration (150 mg/L) for DBP degradation. The main intermediates of DBP degradation by immobilized cells were identified using a gas chromatography/mass spectrometry method. The results revealed the presence of monobutyl phthalate, phthalic acid, and protocatechuate. A tentative pathway for DBP degradation was proposed, which demonstrated that the metabolic mechanism of immobilized cells remained the same as that of the free cells.     

Degradation and metabolite formation of 17beta-estradiol-3-sulphate in New Zealand pasture soils

Estrogens-sulphates such as 17beta-estradiol-3-sulphate and estrone-3-sulphate are excreted by livestock in the urine. These conjugates are precursors to the free counterparts 17beta-estradiol and estrone, which are endocrine disrupting chemicals. In this study microcosm laboratory experiments were conducted in three pasture soils from New Zealand to study the aerobic degradation and metabolite formation kinetics of 17beta-estradiol-3-sulphate at three different incubation temperatures. The degradation of 17beta-estradiol-3-sulphate followed a first-order kinetic and the temperature dependence of the rate constants was sufficiently described by the Arrhenius equation. Degradation was different between the three investigated soils and the rate constants across the soils were significantly correlated to the arylsulphatase activity at 7.5 and 15 degrees C. Estrone-3-sulphate and 17beta-estradiol were identified as primary metabolites and estrone as a secondary metabolite. Results suggest arylsulphatase activity originating from soil microbial biomass is the main driver for the degradation of 17beta-estradiol-3-sulphate.     

Kinetics of photocatalytic oxidation of trace organic compounds over titanium dioxide

The 350 nm UV-illuminated slurries of titanium dioxide were used to study the photocatalyzed degradation kinetics of dissolved organic carbon (DOC) as water contaminants. The initial rate data were well described by the Langmuir-Hinshelwood rate equation and the simplified Langmuir-Hinshelwood rate equation (i.e., ln(C₀/C)=K′t). The latter will be more easily used for predicting the degradation of DOC concentration at various elapsed times. In different DOC initial concentrations the apparent first-order rate constant (K′) decreased and half-life increased when the initial DOC concentration decreased. The Langmuir-Hinshelwood rate form will be the most convenient to describe the oxidation rate of DOC in the drinking water resources, if it is as brief as v=kKC.     

Using the Q10 model to simulate E. coli survival in cowpats on grazing lands

Microbiological quality of surface waters can be affected by microbial load in runoff from grazing lands. This effect, with other factors, depends on the survival of microorganisms in animal waste deposited on pastures. Since temperature is a leading environmental parameter affecting survival, it indirectly impacts water microbial quality. The Q₁₀ model is widely used to predict the effect of temperature on rates of biological processes, including survival. Objectives of this work were to (i) evaluate the applicability of the Q₁₀ model to Escherichia coli inactivation in bovine manure deposited on grazing land (i.e., cowpats) and (ii) identify explanatory variables for the previously reported E. coli survival dynamics in cowpats. Data utilized in this study include published results on E. coli concentrations in natural and repacked cowpats from research conducted the U.S. (Virginia and Maryland), New Zealand, and the United Kingdom. Inspection of the datasets led to conceptualizing E. coli survival (in cowpats) as a two-stage process, in which the initial stage was due to growth, inactivation or stationary state of the population and the second stage was the approximately first-order inactivation. Applying the Q₁₀ model to these datasets showed a remarkable similarity in inactivation rates, using the thermal time. The reference inactivation rate constant of 0.042 (thermal days)^− 1 at 20 °C gave a good approximation (R² = 0.88) of all inactivation stage data with Q₁₀ = 1.48. The reference inactivation rate constants in individual studies were no different from the one obtained by pooling all data (P < 0.05). The rate of logarithm of the E. coli concentration change during the first stage depended on temperature. Duration of the first stage, prior to the first-order inactivation stage and the initial concentration of E. coli in cowpats, could not be predicted from available data. Diet and age are probable factors affecting these two parameters however, until their environmental and management predictors are known, microbial water quality modeling must treat them as a stochastic source of uncertainty in simulation results.     

Thyroid hormone disrupting activities associated with phthalate esters in water sources from Yangtze River Delta

Thyroid hormone disrupting compounds in water sources is a concern. Thyroid hormone (TH) agonist and antagonist activities of water sources from the Yangtze River, Huaihe River, Taihu Lake and ground water in the Yangtze River Delta region were evaluated by use of a TH reporter gene assay based on the green monkey kidney fibroblast (CV-1). While weak TH receptor (TR) agonist potency was observed in only one of 15 water sources, antagonist potency was present in most of the water sources. TR antagonist equivalents could be explained by the presence of dibutyl phthalate (DBP), with concentrations ranging from 2.8 × 10¹ to 1.6 × 10³ μg DBP /L (ATR-EQ₅₀s). None of the ground waters exhibited TH agonist potencies while all of the samples from Taihu Lake displayed notable TR antagonist potencies. To identify the responsible thyroid active compounds, instrumental analysis was conducted to measure a list of potential thyroid-disrupting chemicals, including organochlorine (OC) pesticides and phthalate esters. Combining the results of the instrumental analysis with those of the bioassay, DBP was determined to account for 17% to 144% of ATR-EQ₅₀s in water sources. Furthermore, ATR-EQ_20–80 ranges for TR antagonist activities indicated that samples from locations WX-1 and WX-2 posed the greatest health concern and the associated uncertainty may warrant further investigation.     

Characterization of natural organic matter from eight Norwegian surface waters: Proton and copper binding

As a part of the International NOM-Typing Project, proton and copper binding studies were conducted on ultrafiltered (>1000 dal.) and dialysed (>100 dal.) natural organic matter (NOM) samples from eight Norwegian Lakes. The NOM samples were similar with respect to proton and copper binding, although minor differences were observed among the samples of different origin. Slight variations occurred for seasonal changes and lime additions. The proton binding pK_a values grouped in three distinct classes: pK_a1 = 4.20–4.28; pK_a2 = 6.61–6.87; and pK_a3 = 9.27–9.8. The average total proton binding site concentration of the NOM samples was: 12.7 meq/g total organic carbon (TOC). Two binding sites were established for copper with average log K1 = 4.84 and log K2 = 7.17. The average site concentration for samples isolated by reverse osmosis (RO) was 0.56 μmol/mg C. Copper binding characteristics appear to be influenced by the method of sample isolation. For NOM isolated by low pressure evaporation (evap), binding site concentrations are smaller, conditional stability constants are higher, variability of the copper complexation capacity is smaller, and correlation with elemental composition (C, N, H) is better than in the case of NOM isolated by RO.     

A crossover–crossback prospective study of dibutyl-phthalate exposure from mesalamine medications and semen quality in men with inflammatory bowel disease

BackgroundPhthalates are widely used chemicals with ubiquitous exposure. Dibutyl-phthalate (DBP), a male reproductive toxicant in animals, is understudied in humans. Some mesalamine medications used to treat inflammatory bowel disease (IBD) have DBP in their coating, whereas other mesalamine formulations do not.ObjectivesTaking advantage of differences in mesalamine formulations, we investigated whether high-DBP exposure from mesalamine medications was associated with decreased semen parameters.Methods73 men with IBD taking mesalamine participated in a crossover-crossback prospective study. Men taking non-DBP containing mesalamine at baseline i.e., background exposure, crossed-over for four months to high-DBP mesalamine and then crossed-back for four months to their non-DBP mesalamine (B₁HB₂-arm;Background₁-High-Background₂) and vice versa for men taking high-DBP mesalamine at baseline (H₁BH₂-arm;High₁-Background-High₂). Men provided up to six semen samples (2: baseline, 2: crossover and 2: crossback).ResultsWe estimated crossover, crossback and carryover effects using linear mixed models adjusted for abstinence time, age, season and duration on high-DBP mesalamine at baseline. Semen parameters in B₁HB₂-arm (26 men, 133 samples) decreased after high-DBP mesalamine exposure (crossover versus baseline), especially motility parameters, and continued to decrease further even after crossback to non-DBP mesalamine (crossback versus crossover). The cumulative carryover effect of high-DBP (crossback versus baseline) was a decrease of % total sperm motility by 7.61(CI:− 13.1, − 2.15), % progressive sperm motility by 4.23(CI:− 8.05, − 0.4) and motile sperm count by 26.0% (CI:− 46.2%, 1.7%). However, H₁BH₂-arm (47 men, 199 samples) had no significant change during crossover or crossback.ConclusionsMen newly exposed to high-DBP mesalamine for four months had a cumulative reduction in several semen parameters, primarily sperm motility, that was more pronounced and statistically significant even after exposure ended for four months.     

Sidestream tobacco smoke constituents in indoor air modelled in an experimental chamber— Polycyclic aromatic hydrocarbons

Exposure to sidestream tobacco smoke is concerned with constituents in suspension in the indoor atmosphere. The natural dissipation of sidestream tobacco smoke has been investigated in a static atmosphere in a 10 m³ experimental chamber, and the rate of dissipation is expressed as T_0.5, the half-life of residence in the air. Respective T_0.5 of smoke components are calculated from the various sample data points, assuming a kinetic equation of the first-order process. Sidestream smoke has been generated by a smoking machine according to the Coresta standard protocol and then left to age over an 8-hour period, with subsequent sampling at defined time intervals. The experiments have been repeated over five days, and eight data point samples are obtained for each experiment. Besides nicotine, CO, and smoke particulate matter, interest has been focused on polycyclic aromatic hydrocarbons (PAH). The initial concentrations, C₀ for smoke particulate matter and nicotine (gas and particulate phases) are found to be 13.8 mg and 92 μg per cigarette per cubic meter, with T_0.5 being 2.6 and 2.1 hours, respectively. Low molecular-weight PAH have T_0.5 up to 20 hours, explainable only by their high concentrations in the gas phase, while the 3- to 7-ring PAH have T_0.5 of about 2 hours. The contribution of CO to ambient concentration is 91 mg per cigarette per cubic meter. The data can be useful in mathematical modellization studies regarding ventilation or exposure to sidestream smoke.     

Modeling of Cs migration in soils using an 80-year soil archive: role of fertilizers and agricultural amendments

An 80-year soil archive, the 42-plot experimental design at the INRA in Versailles (France), is used here to study long-term contamination by ¹³⁷Cs atmospheric deposition and the fate of this radioisotope when associated with various agricultural practices: fallow land, KCl, NH₄(NO₃), superphosphate fertilizers, horse manure and lime amendments. The pertinence of a simple box model, where radiocaesium is supposed to move downward by convectional mechanisms, is checked using samples from control plots which had been neither amended, nor cultivated since 1928. This simple model presents the advantage of depending on only two parameters: α, a proportional factor allowing the historical atmospheric ¹³⁷Cs fluxes to be reconstructed locally, and k, an annual loss coefficient from the plow horizon. Another pseudo-unknown is however necessary to run the model: the shape of historical ¹³⁷Cs deposition, but this function can be easily computed by merging several curves previously established by other surveys. A loss of ∼1.5% per year from the plow horizon, combined with appropriate fluxes, provides good concordance between simulated and measured values. In the 0–25 cm horizon, the residence half time is found to be ∼18 yr (including both migration and radioactive decay). Migration rate constants are also calculated for some plots receiving continuous long-term agricultural treatments. Comparison with the control plots reveals significant influence of amendments on ¹³⁷Cs mobility in these soils developed from a unique genoform.     

Uncertainty analysis in 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) cancer dose–response for three occupational cohorts

While the U.S. EPA has issued a draft report with a 1% TCDD effective dose (ED₀₁) of 87.9 pg/kg/day based on continuous integration of key scientific evidence, a detailed and comprehensive uncertainty analysis has not been well documented. In this study, a new estimate for ED₀₁ was derived based on uncertainty analysis by quantitatively assessing the potential bias arising from the selection of kinetic models, dose–response models and cohorts. The cumulative serum lipid concentration (CSLC) and cumulative body burden (CBB) were reconstructed as dose metrics using a concentration- and age-dependent pharmacokinetic model (CADM), physiologically based pharmacokinetic model (PBPK), and age-dependent half-life model (FV), and the reconstructed dose metrics based on CADM and PBPK were generally higher than those based on the FV model. Three dose–response curves (linear, multiplicative and power) were used to link dose metrics and cancer risk to estimate ED₀₁, and the linear model resulted in the lowest ED₀₁, followed by the power model and multiplicative model, for the same cohort. Meanwhile, ED₀₁ based on the CADM model was the highest, followed by those based on the PBPK model and first-order model. Finally, the ED₀₁ was estimated to be 17.03 ± 7.83 pg/kg/day by statistically analyzing the distribution of ED₀₁ values based on various kinetic models, cohorts and dose–response models. The study presented here strengthens the scientific basis for understanding the potential health implications of TCDD exposure.     

The Kinetics of Caesium absorption by roots of winter wheat and the possible consequences for the derivation of soil-to-plant transfer factors for radiocaesium

Caesium (Cs) uptake in roots of winter wheat was found to follow a dual pattern similar to that established for potassium uptake in barley roots. This suggests the operation of two discrete uptake systems for Cs, as for potassium. The ‘System 1’ (low concentration) uptake mechanism for caesium, however, can be resolved into two hyperbolic components which both obey Michaelis-Menten kinetics. The Michaelis-Menten equation was used to derive a function which describes the variation in solution-to-root transfer factor for any element for which the appropriate root uptake constants (K_m andV_max) can be determined. This function successfully described available data for root uptake of caesium and potassium, predicting that the solution-to-root transfer factor decreases in relation to an increase in the substrate concentration of each respective element. At substrate concentrations equivalent to carrier-free radiocaesium concentrations, however, the solution-to-root transfer factor predicted by the function and by empirical data suggests that the relationship between root uptake and solution concentration of caesium is linear. These findings are discussed in relation to the comparative physiology of caesium and potassium uptake by plant roots and with respect to the application of the soil-to-plant transfer factor concept to radioecological studies.     

Phthalate exposure,flavonoid consumption and breast cancer risk among Mexican women

ObjectiveTo evaluate if selected phthalate exposure and flavonoid intake interact on breast cancer (BC) risk.Material and methodsInterviews and urine samples were obtained from 233 women with histologically confirmed BC and 221 healthy controls matched by age and place of residence, from various states of northern Mexico. Urinary metabolites concentrations of diethyl phthalate (DEP), butyl benzyl phthalate (BBzP) and dioctyl phthalate (DOP) were determined by solid-phase extraction coupled with high-performance liquid chromatography/isotope dilution/tandem mass spectrometry. Using a semiquantitative food frequency questionnaire, consumption of five types of flavonoids (anthocyanidins, flavan-3-ols, flavanones, flavones and flavonols) was estimated according to three food groups: vegetables, fruits and legumes-oil seeds.ResultsA higher intake of anthocyanidins and flavan-3-ols (from vegetables), synergistically increased the negative association between BBzP and BC. No other significant flavonoid-phthalate multiplicative interactions on the risk for BC were found.ConclusionThe consumption of some flavonoids may interact with exposure to phthalates on the risk of BC. Epidemiological and underlying mechanisms information is still insufficient and requires further investigations.     

Recovery and characterisation of carbon fibres from waste CFRP using supercritical n-butanol

ABSTRACT

The high-performance carbon fibres can be recycled from waste carbon fibre/epoxy resin composites by supercritical n-butanol. Recycling experiment designed by response surface method was used to investigate quantitative relation between degradation rate of epoxy resin and process parameters. Thus, the optimum process parameters could be obtained, and effects of process parameters and layers on degradation rate and mechanical performance of the recycled carbon fibres were analysed. The tensile strength of the recycled carbon fibre under the optimum process parameters was 94.53% of that of the original carbon fibre, tensile modulus was 93.57% of that of the original carbon fibre and interfacial shear strength was 90% of that of the original carbon fibre.     

Life cycle inventory of the commercial production of compost from oil palm biomass: a case study

This paper compared the life cycle inventory (LCI) obtained from three commercial oil palm biomass composting projects in Malaysia which use the open windrow composting system. The LCI was obtained and calculated based on the functional unit of 1 t of compost produced. The input of the inventory are the feed materials such as empty fruit bunches (EFB) and palm oil mill effluent (POME); and utilities which include electricity generated at palm oil mill and diesel used. Composting 2.0–2.5 t of EFB and 5.0–7.5 t of POME required diesel from 218.7 to 270.2 MJ and electricity from 0 to 6.8 MJ. It is estimated that the composting emitted from 0.01 to 0.02 t CO_2eq/t_compost mainly from diesel used to operate machineries. Composting saved 65 % of time required for a complete degradation of POME when compared to ponding system, and 89 % of time required for a complete degradation of EFB compared to mulching. In terms of land required, it required 36 % less land as compared to ponding for POME and 99 % less land as compared to mulching for EFB. Based on the case study, diesel was found to be the main contributor to the environmental impact. There is a potential of upgrading the process to be more economical and environmental friendly. Using electricity as the source of energy has a lower footprint for the composting process. Instead of using raw POME, studies had reported that using treated POME either from anaerobic ponding or digested tank can accelerate the composting process.     

Transfer of eight phthalates through the milk chain — A case study

This survey determined the levels of eight phthalates – i.e. dimethyl phthalate (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DiBP), di-n-butyl phthalate (DnBP), benzylbutyl phthalate (BzBP), di(2-ethylhexyl) phthalate (DEHP), dicyclohexyl phthalate (DCHP) and di-n-octyl phthalate (DnOP) – in several Belgian milk and dairy products. Samples were obtained from various farms, a dairy factory and from different shops in order to investigate phthalate contamination “from farm to fork”. At several stages in the milk chain, product contamination with phthalates – mostly DiBP, DnBP, BzBP and DEHP – was observed. At farm level, the mechanical milking process and the intake of phthalate containing feed by the cattle were found to be possible contamination sources. At industry and retail level, contact materials including packaging materials were additional contamination sources for phthalates in milk and dairy products.     

Dietary intake of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) from fish and meat by residents of Nanjing,China

Concentrations of 14 polybrominated diphenyl ether (PBDEs) and 28 polychlorinated biphenyl (PCBs) congers were measured in 137 samples of fish and meat from Nanjing, a city in the Yangtze River Delta, China. Total concentrations of PBDEs were less in fish (mean of 180 pg/g ww; range 8.0–1100 pg/g ww), but more in non fish foods (mean of 180 pg/g ww; range 15–950 pg/g ww) than those reported from other countries. The total dietary intake of PBDEs and PCBs by humans were 9.9 ng PBDE/d and 870 ng PCB/d, respectively. The daily intake by a 60 kg adult of 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ_WHO) from PCBs was estimated to be 49 pg ^PCBTEQ_WHO/d (0.82 pg ^PCBTEQ_WHO/kg bw), which is less than the tolerable daily intake suggested by the World Health Organization (WHO). The daily intake of meat and fish accounted for 57.2% and 42.8% of the total intake of ^PCBTEQ_WHO.