Fenton''s type reaction and chemical pretreatment of PCBs

This study evaluates the effects of Fenton's reagent (FR) on the rate and extent of the oxidative degradation of individual mono, di-, tri- and tetrachlorobiphenyls in the commercial mixture DELOR 103, equivalent to AROCLOR 1248. The oxidation effect of FR strongly increased with increasing the molar ratio of Fe²⁺/H₂O₂. The most effective oxidation of DELOR 103 (10 μg.ml⁻¹) was achieved in a solution containing 1M H₂O₂ and 1 mM Fe²⁺. The FR elimination rate constants of PCB congeners decrease with increasing number of chlorine substituents in the biphenyl molecule and show a good correlation with the values of molecular weights of the PCB congeners and their 1-octanol/water partition coefficients.     

PCB congener selective biodegradation by the white rot fungus Pleurotus ostreatus in contaminated soil

Six strains of white rot fungi were tested for their biodegradation ability of low chlorinated polychlorinated biphenyl (PCB) commercial mixture (Delor 103) in real soil system. Phanerochaete chrysosporium and Trametes versicolor did not show any ability to degrade PCBs in soil. On the contrary, four strains of Pleurotus ostreatus were able to remove about 40% of Delor 103 in two months. All P. ostreatus strains decomposed PCBs selectively with the preference for congeners with chlorine atoms in ortho > meta > para position. Degradation efficiency decreased with increasing number of chlorination.     

Degradation pathways of PCBs upon UV irradiation in hexane.

The photodegradations of eight individual PCB congeners (5, 31, 52, 77, 87, 126, 138, 169) in hexane have been investigated employing a mercury lamp. All degradation reactions of the above mentioned PCB congeners are of the pseudo first order. The principal products of PCB decomposition are the less chlorinated biphenyls, and no PCB-solvent adducts are found. Symmetrical and coplanar PCB congeners show lower photoreactivities. The reactivities of the chlorine atoms at various positions of PCB rings are generally in the order: ortho > meta > para. Photodechlorinations occur mainly on the more substituted rings, when the numbers of chlorine atoms on the two phenyl rings are unequal. During photodegradation, some coplanar PCB congeners are formed, which make the TEQ of solutions to decrease slowly or even to increase.     

Dechlorination pathways of ortho-substituted PCBs by UV irradiation in n-hexane and their correlation to the charge distribution on carbon atom

The photodegradations of 22 individual polychlorinated biphenyl (PCB) congeners (including 21 non-coplanar ortho substituted and one non-ortho substituted) by irradiation with ultraviolet lamp in n-hexane solution were studied. Photoproducts were identified by matching their retention times and mass spectra with those of authentic standards. PCB congener with less than two chlorides was photodegraded within half an hour, if more than three chlorine on ring, the photodechlorination time for PCB needs one and half hours or more, sometimes even longer than 15 h. The half-life of PCB degradation by photodechlorination was much shorter than that by anaerobic biological dechlorination. Charge distribution on carbon atom combined with the monitoring products of individual PCB congeners were used to deduce the photodegradation pathways. The higher the charge distribution for carbon to which chlorine is attached, the easier for photodechlorination to occur. A lot of chlorine atoms attached PCB, the dechlorination was found to occur prior to the carbon with higher charge distribution at the benzene ring with more chlorine atoms attached.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Photochemical degradation of six polybrominated diphenyl ether congeners under ultraviolet irradiation in hexane

The photodegradation of six individual PBDE congeners (BDE-28, 47, 99, 100, 153, 183) in hexane was investigated under UV light in the sunlight region, employing a mercury lamp filtered with Pyrex glass. All photodegradation reactions followed the pseudo-first-order kinetics, with the half-lives ranging from 0.26h for BDE-183 to 6.46h for BDE-100. The photochemical reaction rates of PBDEs decreased with decreasing number of bromine substituents in the molecule, also in some cases were influenced by the PBDE substitution pattern. Principal photoproducts detected were less brominated PBDEs, and no PBDE-solvent adducts were found. Consecutive reductive debromination was confirmed as the main mechanism for the photodegradation of PBDEs in hexane. In general, debromination firstly occurred on the more substituted rings, when the numbers of bromine atoms on the two phenyl rings were unequal. For less brominated PBDEs, the photoreactivity of bromines at various positions of phenyl rings decreased in the order: ortho>para; while for higher brominated PBDEs, the difference became not significant.     

Evidence for destruction of PCBs by the OH radical in urban atmospheres

Evidence for reaction of polychlorinated biphenyl (PCB) congeners with the hydroxyl (OH) radical in the troposphere was observed in diurnal variations in ambient gas-phase PCB concentrations at three urban sampling sites located in the Chicago, IL; Baltimore, MD; and Jersey City, NJ urban/industrial areas. The magnitude of the depletion of individual PCB congeners decreased by about 10-20% for each additional chlorine substituent, reflecting slower reaction rates for higher MW congeners with the OH radical. Octa- and nonachlorobiphenyls, which are largely unreactive with the OH radical, were used as tracers to investigate the effects of dilution on diurnal variation. The environmental rate constants for disappearance of the PCBs range from about 1.0 day(-1) for trichlorobiphenyls to about 0.3 day(-1) for hexachlorobiphenyls. Assuming a OH radical concentration of 3 x 10(6) molecules cm (-3), the second-order rate constants for reaction of specific congeners with the OH radical are consistent with laboratory measurements. More importantly, the relative reactivity of PCB homologues agrees well with the relationship predicted by other researchers from laboratory measurements, suggesting that losses of PCBs during daytime tropospheric transport are due at least in part to reactions with the OH radical.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in human adipose tissues of Japan

Thirteen samples of human adipose tissue from cancer patients in Japan were analyzed for tetra- to octa- chlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). These compounds were identified in all the samples analyzed. All isomers identified have a pattern of chlorine substitution in 2, 3, 7 and 8 positions with the only exception of 1,2,3,4,6,7,9-hepta-CDD. In the case of PCDFs, the relatively higher persistency was found in the isomers with chlorine atoms at 4- (or 6-) position as compared with 1- (or 9-) position. Total PCDD concentrations were in the range of 160 to 1400 pg/g on wet weight basis, in which increasing levels were found from tetra- to octa-CDD. Total PCDF concentrations were in the range of 7 to 120 pg/g and the levels of individual congeners are rather uniform.     

Labile and non-labile desorption rate constants for 33 PCB congeners from lake sediment suspensions

Lake sediments contaminated with polychlorinated biphenyls (PCBs) were purged using a gas stripping technique to estimate desorption rate constants. Desorption profiles and modeling of the data clearly show a two-step release of PCBs from sediment suspensions that can be described as a labile (fast) release followed by a non-labile (slow) release. Data are summarized by labile and non-labile rate constants and by mass in each phase as a function of suspended solids concentration for twelve pure congeners and nine co-eluting data sets (twenty-one chromatograph peaks total). Labile desorption rate constants range from 113 days(-1) to 1.43 days(-1) for the 100 mg/l sediment suspension, from 67.7 days(-1) to 2.45 days(-1) for the 1000 mg/l sediment suspension, and from 8.41 days(-1) to 0.946 days(-1) for the 5000 mg/l sediment suspension. Labile rate constants consistently decreased with increasing suspended solids, and, in general, decreased with increasing degree of chlorination (reflected in increasing retention time in the chromatogram). No consistent trend was observed for the non-labile rate constants with suspended solids concentration or degree of chlorination. The average non-labile rate constant for the PCB congeners studied here was 0.154 days(-1) (s.d.=0.158; n=63). The distribution between the labile and non-labile phases also failed to indicate dependence on suspended solids concentration, chlorine substitution pattern, or molecular weight of the congener, although the data from the 5000 mg/l suspension consistently contained less labile components. The average distributions (n=63) were 60.1% in the labile phase and 39.9% in the non-labile phase.     

Dependence of GC-RRTs on the solvent-accessible surface area of dioxins and related compounds

The correlation between gas chromatograph relative retention times (GC-RRTs) of dioxins and related compounds, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated naphthalenes (PCNs), and their solvent-accessible surface area (SAS) was analyzed for congeners and isomers. GC-RRTs were linearly dependent on SAS for congeners while there was little dependence for isomers. However, by using classification parameters, Nad-Cl, Nad-H, N1,9Cl, and NalphaCl, based on the substitution positions and patterns of chlorine and/or hydrogen atoms bound to the molecular skeleton, a linear relationship was found among isomers. Furthermore, the GC-RRTs of CDD, CDF, and CN isomers, which are planar, decreased despite increasing SAS, and this tendency was enhanced with the above classification. The retention behavior was explained in terms of the effective enhancement of molecular hydrophobicity caused by an increase in the number of adjacent chlorine pairs.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.     

Influence of membrane permeation on biodegradation kinetics of hydrophobic compounds

The relationship between membrane permeation rate and biodegradation rate has been investigated for alkyl esters of p-aminobenzoic acid. The pseudo-first order biodegradation rate constants of these compounds increase with increasing alkyl chain length, and increasing hydrophobicity, until alkyl chain lengths of greater than five carbon atoms, for which the biodegradation rate constants remain constant. This relationship between biodegradation rate constant and hydrophobicity parallels that of the permeabilities of lipid membranes and aqueous diffusion layers towards these compounds. This indicates that the rate-determining step in the biodegradation of these esters is their diffusion into bacterial cells, and that they then undergo rapid transformation.     

The presence of PCDDs and PCDFs in human breast milk from the Netherlands

Sixteen individual and two pooled human milk samples were analyzed for PCDDs and PCDFs. All detected PCDD and PCDF congeners had a 2,3,7,8-chlorine substitution pattern.The PCDDs and PCDFs were associated with the lipid fraction of the milk. Major components were 2,3,4,7,8-PnCDF (0.2 – 2.6 ppt), 1,2,3,6,7,8-HxCDD (0.2 – 5.7 ppt), 1,2,3,4,6,7,8-HpCDD (1.3 – 19.1) and OCDD (1.7 – 37.8 ppt), with concentrations on total milk basis.Minor components were 1,2,3,7,8-PnCDD, 1,2,3,7,8,9- and 1,2,3,4,7,8- HxCDD (⩽ 1 ppt). Qualitatively and quantitatively the milk samples from the Netherlands strongly resemble those from Sweden and West-Germany. A linear relationship was found between some congeners. This correlation was highest for congeners having an equal number of chlorine atoms or those with a difference of one chlorine atom.By using a one compartment open model for multiple doses, a maximum liver concentration of approximately 200 ppt 2,3,4,7,8-PnCDF in the neonate was calculated after six months.     

Desorption kinetics for selected PCB congeners from river sediments

Desorption of PCBs from sediment can significantly affect the ultimate fate and effects of PCBs in aquatic systems. Using a gas purging technique to strip soluble and sorbed polychlorinated biphenyls (PCBs) from solutions and sediment suspensions, Henry's law constants, approach to equilibrium, and desorption rate constants for four PCB congeners were measured. Henry's law constants were on the order of 10⁻⁴ m³ atm mole⁻¹. Desorption rate constants measured for a predominantly kaolinitic, low-organic carbon sediment were on the order of 0.03–0.1 days⁻¹. In contrast, desorption rate constants measured for a sediment composed of montmorillonite with a 3% organic carbon content were on the order of 0.009–0.04 days⁻¹. Desorption data suggest that equilibration times for PCBs with low chlorine content are on the order of six weeks, and months to years for PCBs with a significantly higher chlorine content.     

Prediction of the bioconcentration factor of PCBs in fish using the molecular connectivity index and fragment constant models.

Models based on molecular connectivity index (MCI) and fragment constant (FC) method were developed for prediction of the bioconcentration factor (BCF) for polychlorobiphenyls (PCBs) in fish. The mean residuals for the MCI and FC models were 0.195 and 0.223 log units, respectively. The two models were then compared in terms of their mean residuals. In addition to the chlorine atom substitution number, other important structural features exhibiting a significant influence on the BCFs of PCB congeners were discussed and incorporated to the models. These features include the degree of the ortho-substitution, the presence of chlorine pairs in the three- and five- positions, and the crowding of chlorine atoms on the phenyl ring.     

Factors affecting the biodegradability of biodegradable polyester in soil

The biodegradabilities of two polyester, P(3HB-co-3HV) and PCL, in soil were studied to examine the factors affecting the biodegradability of biodegradable plastics in soil. The polymers were mixed with soil and the time course of the biodegradation of the polymer was measured by analyzing the residual polymer. The polymer biodegraded little in early period of the test, but did in the first-order kinetics after a certain time which was dependent on the test substance and soil used. The rate constant and the induction period of the biodegradation were determined from the residual curve. The rate constant and the induction period for P(3HB-co-3HV) increased and reached to the constant values with increasing the particle size of the test substance. Both values depended on the kind of test soil and on the sampling date for the same kind of soil. The variation in the biodegradability among the same kind of soil was primarily attributed to the variation in water content of the soil. The rate constant and the induction period of PCL were smaller and longer than P(3HB-co-3HV), respectively.     

The effect of terpenes on the biodegradation of polychlorinated biphenyls by Pseudomonas stutzeri.

The effect of two terpenes, carvone and limonene, on the biodegradation of DELOR 103, a commercial mixture of polychlorinated biphenyls (PCBs), by Pseudomonas stutzeri, an isolate from long-term PCB-contaminated soil, was studied in detail. The addition of both carvone and limonene as potential inducers of the dioxygenase metabolic pathway exerted an enhancing effect on PCB biodegradation when glycerol and xylose were used as carbon sources, whereas no such effect could be determined with biphenyl and glucose as substrates. Promising biodegradation values were determined with xylose as carbon source and carvone as terpene inducer. In this system, 30-70% of the congeners were degraded in the presence of 10 mg l(-1) and 20 mg l(-1) carvone, respectively, irrespective of the used concentration, whereas only 7-37% of individual PCB congeners were eliminated from the system without terpene addition.     

Polychlorinated biphenyls and dibenzofurans retained in the tissues of a deceased patient with Yucheng in Taiwan

Various tissues from a deceased Yucheng (oil disease) patient were analyzed for individual polychlorinated biphenyl (PCB) and dibenzofuran (PCDF) congeners. With a few exceptions, PCBs with 5 or less chlorine atoms were almost completely excreted from the patient's tissues about two years after the ingestion of the toxic oil. In contrast, most PCB congeners with 6 or more chlorine atoms were retained in the tissues. The intestinal fat contains the highest level of PCBs while the liver contains the highest concentration of PCDFs. The major PCDF congeners retained in the tissues were 1,2,3,4,7,8-hexaCDF, 2,3,4,7,8-pentaCDF, and 1,2,4,7,8-pentaCDF. The former two congeners, especially 2,3,4,7,8-pentaCDF, are very toxic PCDFs; they may play important roles in the etiology of Yucheng.