Correlation relationships between physico-chemical properties and gas chromatographic retention index of polychlorinated-dibenzofurans

Correlation relationships between physico-chemical properties including vapor pressures (P), water solubilities (S), Henry's law constants (H(c)), n-octanol-water partition coefficients (K(ow)), sediment-water partition coefficient (K(pw)) and biotic lipid-water partition coefficient (K(bw), bioconcentration factor) of polychlorinated-dibenzofurans (PCDFs) and their gas chromatographic retention indices (GC-RIs) were established. A model equation between GC-RIs (= RI) and these physico-chemical properties (K) of PCDFs was in a form of log K = aRI2 + bRI + c with correlation coefficients (R2) greater than 0.94, except H(c). These equations were derived from six experimental data (five experimental data for log K(bw)) in each physico-chemical properties of PCDFs reported previously. The values of log P, log S, log H(c), log K(ow), log K(pw) and log K(bw) of PCDFs predicted by these equations based on their GC-RIs in the present study derviated from those calculated by the solubility parameters for fate analysis method in a previous study by 0.49, 0.32, 0.11, 0.34, 0.14 and 0.22 log units, respectively.     

Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).     

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.     

Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica

Where fuel oil spills have occurred on Antarctic soils polycyclic aromatic hydrocarbons (PAH) may accumulate. Surface and subsurface soil samples were collected from fuel spill sites up to 30 years old, and from nearby control sites, and analysed for the 16 PAHs on the USEPA priority pollutants list, as well as for two methyl substituted naphthalenes, 1-methylnaphthalene and 2-methylnaphthalene. PAH levels ranged from 41-8105 ng g-1 of dried soil in the samples from contaminated sites and were below detection limits in control site samples. PAH were detected in surface soils and had migrated to lower depths in the contaminated soil. The predominant PAH detected were naphthalene and its methyl derivatives.     

Acute toxicity of substituted phenols to Rana japonica tadpoles and mechanism-based quantitative structure-activity relationship (QSAR) study.

Acute 12 h and 24 h lethal toxicity (12 h-LC50 and 24 h-LC50) of 31 substituted phenols to Rana japonica tadpoles was determined. Results indicate that toxicity of phenols to tadpoles varied only slightly with length of exposure and the 12-h test could serve as surrogate of the 24-h test. A mechanism-based quantitative structure-activity relationship (QSAR) method was employed and 1-octanol/water partition coefficient (log K(ow))-dependent models were developed to study different modes of toxic action. Most phenols elicited their response via a polar narcotic mechanism and an excellent logK(ow)-dependent model was obtained. Soft electrophilicity and pro-electrophilicity were observed for some phenols and a good log K(ow)-dependent model was also achieved. Additionally, the significant dissociation of carboxyl on benzoic acid derivatives sharply reduced their toxicity. A statistically robust QSAR model was developed for all studied compounds with the combined application of log K(ow), energy of lowest unoccupied orbital (E(lumo)), heat of formation (HOF) and the first-order path molecular connectivity dices (1chi(p)).     

Nickel tissue residue as a biomarker of sub-toxic exposure and susceptibility in amphibian embryos

Although low level exposure to physicochemical agents is the most common environmental scenario, their effects on living organisms are very controversial. However, there is an increasing need to integrate low level exposures from risk assessment to remediation purposes. This study focus on the possibility to employ Ni tissue residue values as biomarkers of sub-toxic exposure and susceptibility to this metal in a range of almost pristine to sub-toxic concentrations for Rhinella arenarum embryos. For that purpose, three batches of amphibian embryos were pretreated during 10 days with three increasing concentrations of Ni starting in 2, 8 and 20 microg Ni(2+) L(-1) and ending in 16, 64 and 160 microg Ni(2+) L(-1) (in natural fresh waters this value ranges from 2 to 10 microgL(-1); the LC(50)-24h for R. arenarum is 26.2mg Ni(2+) L(-1)). For the experimental conditions, the Ni tissue residue values at 360 h post exposure were 0.5, 2.1 and 3.6 microg Ni g(-1) embryo w/w, respectively, corresponding to BCFs of 31, 33 and 23. The susceptibility to Ni in those experimental embryos was evaluated by means of challenge exposures to three lethal concentrations of this metal (10, 20 and 30 mg Ni(2+) L(-1)), registering survival during the following 10 days of treatment. As a general pattern, the lower, intermediate and higher pretreatments with Ni resulted in enhanced, neutral and adverse effects on embryonic survival, respectively. Thus, sub-toxic exposure to Ni could modify the resistance of the amphibian embryo to this metal and Ni tissue residue values could be considered as biomarkers of both, exposure and susceptibility.     

Evaluating coal tar-water partitioning coefficient estimation methods and solute-solvent molecular interactions in tar phase

Equilibrium partitioning coefficients between an industrial coal tar sample and water (K(CT/w)) were determined for 41 polar and nonpolar solutes in batch systems. Together with literature values, 69 K(CT/w) data were analyzed using the following model approaches: Raoult's law, the single parameter linear free energy relationship (SPLFER) with octanol-water partitioning coefficients (K(ow)), the linear solvation energy relationships (LSERs), SPARC and COSMOtherm. Estimations by Raoult's law and the SPLFER agreed well with the experimental log K(CT/w) values for the investigated coal tar, with root mean square errors (RMSE) of 0.31 and 0.33, respectively. LSER resulted in as good estimations (RMSE=0.29) as the previous two. The LSER analysis revealed significant hydrogen (H)-bond acceptor properties of the studied coal tar phase. Using naphthalene as a surrogate solvent for the coal tar phase, SPARC and COSMOtherm provided fairly good predictions (RMSE of 0.63 and 0.65, respectively) of log K(CT/w), without any additional empirical parameter. Further calculations using SPARC and COSMOtherm for partitioning between water and other tar-components (e.g., benzofuran, phenol and quinoline) suggested that minor components in coal tar do not significantly influence K(CT/w) of nonpolar solutes, and that Raoult's law and the SPLFER thus may be generally applied to these types of solutes, e.g., polycyclic aromatic hydrocarbons and alkylbenzenes, regardless of coal tar compositions. In contrast, partitioning of H-bonding solutes (e.g., phenols) can significantly vary depending on the amount of polar tar-components such as N-heterocyclic aromatic compounds. Therefore, the presented successful applications of Raoult's law and SPLFER to the studied coal tar could be a special case, and these simple approaches may not provide reasonable estimations for partitioning of H-bonding solutes from compositionally different coal tars.     

Biofilter treatment of volatile organic compound emissions from reformulated paint: complex mixtures, intermittent operation, and startup

Two biofilters were operated to treat a waste gas stream intended to simulate off-gases generated during the manufacture of reformulated paint. The model waste gas stream consisted of a five-component solvent mixture containing acetone (450 ppm(v)), methyl ethyl ketone (12 ppm(v)), toluene (29 ppm(v)), ethylbenzene (10 ppm(v)), and p-xylene (10 ppm(v)). The two biofilters, identical in construction and packed with a polyurethane foam support medium, were inoculated with an enrichment culture derived from compost and then subjected to different loading conditions during the startup phase of operation. One biofilter was subjected to intermittent loading conditions with contaminants supplied only 8 hr/day to simulate loading conditions expected at facilities where manufacturing operations are discontinuous. The other biofilter was subjected to continuous contaminant loading during the initial start period, and then was switched to intermittent loading conditions. Experimental results demonstrate that both startup strategies can ultimately achieve high contaminant removal efficiency (>99%) at a target contaminant mass loading rate of 80.3 g m(-3) hr(-1) and an empty bed residence time of 59 sec. The biofilter subjected to intermittent loading conditions at startup, however, took considerably longer to reach high performance. In both biofilters, ketone components (acetone and methyl ethyl ketone) were, more rapidly degraded than aromatic hydrocarbons (toluene, ethylbenzene, and p-xylene). Scanning electron microscopy and plate count data revealed that fungi, as well as bacteria, populated the biofilters.     

Molecular hologram derived quantitative structure-property relationships to predict physico-chemical properties of polychlorinated biphenyls

Polychlorinated biphenyls (PCBs) congeners with various degrees of chlorination and substitution patterns are among the most widespread and persistent man-made organic pollutants. They are toxic, lipophilic and tend to be bioaccumulated. The knowledge of the physico-chemical properties is very useful to explain the environmental behavior of PCBs and to perform an exposure assessment. In this paper, we have used a new molecular representation, the molecular hologram, to generate quantitative structure-property relationship models to predict the physico-chemical properties of biphenyl and all of its chlorinated congeners. The investigated properties include 1-octanol/water partition coefficient (logK(ow)), aqueous solubility (-logS(w)), aqueous activity coefficient (-logY(w)), Total molecular surface area, Henry's law constant (logH). The results show that this new quantitative structure-activity relationship approach presents highly predictive models for important physico-chemical properties of PCBs.     

Maternal transfer of organochlorine compounds to oocytes in wild and farmed gilthead sea bream (Sparus aurata)

To investigate the transfer of lipophilic organochlorine compounds to the gonads in gilthead sea bream females, liver and oocytes from wild and farmed females, just before spawning, were analysed by gas chromatography coupled to tandem mass spectrometry after clean-up of the fatty extracts by normal phase HPLC. This analytical methodology allowed us to achieve limits of detection of around 0.1 ng/g. Data obtained show that the chemicals studied are transferred from the liver to oocytes in ratios up to 0.51. In general this means that less than a half of pollutant load is transferred from liver to oocytes. A significant correlation (p<0.05) between log K(ow) and ratios (oocytes/liver) was found. Compounds with larger Log K(ow) present lower lipid-based concentration ratios (oocytes/liver). We have inferred that the reason the fugacity model is not accomplished is specifically dependent on the vitellogenesis process, which involves the transfer of lipids from the liver to oocytes in teleostei. No significant differences (t-Student) have been found between wild and farmed females transfer ratios (oocytes/liver).     

Biotic and abiotic degradation of illicit drugs, their precursor, and by-products in soil

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories.     

Groundwater contamination by chlorinated naphthalenes and related substances caused by activities of a former military base

Water samples derived from two different aquifer layers of six sampling sites were analysed by GC/MS in order to characterize a groundwater contamination caused by chemicals used for wood impregnation. Mono- and dichlorinated naphthalenes, chlorobenzo(b)thiophene, 1-chloro-4-naphthol, 1-chloronaphthoic acid, acenaphthene and methyled naphthalenes were identified as the main pollutants and quantified. 1-Chloro-4-naphthol and 1-chloronaphthoic acid are discussed as possible indicators for anaerobic degradation processes. Results of inorganic and compound specific stable carbon isotope analyses revealed only a minor degree of microbiological transformation. Thus, sorption was characterized as the main attenuation process within the aquifer affecting the contamination described.     

Deposition and leaching of tebuthiuron on sugar cane straw applied with and without alkyl polyglycoside adjuvant

A laboratory experiment was carried out aiming to study the effects of an alkyl polyglycoside adjuvant (APG) on deposition and leaching of the herbicide tebuthiuron applied on sugar cane straw. Tebuthiuron, at concentration of 1200 mg L(-1), was applied separately and in tank mix with the APG adjuvant, at concentrations of 0.07 and 0.09% (wt v(-1)), using a spraying volume of 204 L ha(-1). A precipitation equivalent to 20 mm of rain was simulated, 24 h after the applications, to evaluate the herbicide leaching. The quantification of tebuthiuron was carried out by the high performance liquid chromatography (HPLC). It was observed that the addition of APG adjuvant at 0.07% (wt v(-1)) provided an increase of 11.5% in the deposition of tebuthiuron on straw, reduction of 50.4% in the drift of the herbicide and it did not affect significantly the leached amount (68.5%), when compared with the treatment where tebuthiuron was applied alone (70.8%). At the concentration of 0.09% (wt v(-1)), the APG adjuvant caused an increase of 22.7% in the deposition; it reduced the drift of the herbicide by 99.9% and reduced the leached amount by 7.6% thereby increasing the retention of the herbicide by straw.     

铁炭微电解-Fe~（2＋）/K_2S_2O_8降解甲基橙

针对偶氮类有机物废水具有色度大,难降解的特点,以对二甲基氨基偶氮苯磺酸钠（甲基橙）为模拟研究对象,对水体系中铁炭微电解-Fe2＋/K2S2O8降解甲基橙的方法进行了研究。通过正交实验确定出该方法各因素的影响程度,进一步通过单因素影响实验确定该方法的最佳条件是：铁炭微电解填料、FeSO4和K2S2O8投加量分别为300 g/L、1.3mmol/L和0.7 mmol/L,初始pH值为7.0。在最佳条件下,甲基橙COD和色度去除率分别能达到64.7%和68.2%。     

An exploration of the relationship between adsorption and bioavailability of pesticides in soil to earthworm

A study was conducted to determine the adsorption/desorption of butachlor, myclobutanil and chlorpyrifos on five soils using a batch equilibration technique and to study the relationship between bioavailability to Allolobophora caliginosa and the adsorption/desorption of these three pesticides. The results showed that the adsorption/desorption processes of the tested compounds were mainly controlled by soil organic matter content (OM) and octanol/water-partitioning coefficient (K(ow)), and that the bioavailability of the pesticides was dependent on characteristics of pesticides, properties of soils, and uptake routes of earthworms. Bioconcentration of butachlor and myclobutanil was negatively correlated with Freundlich adsorption constant K(af) and K(df). However, only a slightly positive correlation between bioconcentration and K(af) and K(df) was observed for chlorpyrifos due to its high affinity onto soil.