Chlorine Substitution Pattern Research Articles

Unveiling chlorine's role: How it shapes the formation and light-activated oxygen dynamics of chlorophenol-derived environmental persistent free radicals

Environmental persistent free radicals (EPFRs) derived from chlorophenols, triggered by light or heat exposure, pose significant ecological concerns, yet the impact of chlorine substituents on EPFRs formation and reactivity remains inadequately understood. Through an intentional synthesis of chlorophenol-derived EPFRs with varying chlorine contents and positioning, we elucidated the role of chlorine in the photoactivation of molecular oxygen. Our combined experimental and theoretical analysis reveals that these EPFRs are primarily oxygen-centered phenoxy radicals, establishing a direct link between chlorine substitution patterns and their ability to activate molecular oxygen under visible light. Increased chlorine content enhances EPFRs formation by elevating the positive charge on the phenolic hydroxyl group’s hydrogen atom, facilitating its removal. Moreover, the capability of EPFRs to activate molecular oxygen was directly correlated with chlorine content, with 2,3,5,6-tetrachlorophenol-derived EPFRs showcasing the highest activity. This activity is attributed to their structural propensity for TCSQ·- species generation. Furthermore, our study established a significant correlation between the toxicity and activity of EPFRs, emphasizing the critical role of halogen substituents in determining the reactivity of EPFRs. These insights contribute to our understanding of their environmental and toxicological ramifications, underscoring the imperative for continued research aimed at mitigating their detrimental impacts.

Chlorine substitution-dependent toxicities of polychlorinated biphenyls to the earthworm Eisenia fetida in soil

Polychlorinated biphenyls (PCBs) with different chlorine substitution patterns often coexist in e-waste-processing sites. However, the single and combined toxicity of PCBs to soil organisms and the influence of chlorine substitution patterns remain largely unknown. Herein, we evaluated the distinct in vivo toxicity of PCB28 (a trichlorinated PCB), PCB52 (a tetrachlorinated PCB), PCB101 (a pentachlorinated PCB), and their mixture to earthworm Eisenia fetida in soil, and looked into the underlining mechanisms in an in vitro test using coelomocytes. After a 28-days exposure, all PCBs (up to 10 mg/kg) were not fatal to earthworms, but could induce intestinal histopathological changes and microbial community alterations in the drilosphere system, along with a significant weight loss. Notably, pentachlorinated PCBs with a low bioaccumulation ability showed greater inhibitory effects on the growth of earthworm than lowly chlorinated PCBs, suggesting that bioaccumulation was not the main determinant of chlorine substitution-dependent toxicity. Furthermore, in vitro assays showed that the highly chlorinated PCBs induced a high-percentage apoptosis of eleocytes in the coelomocytes and significantly activated antioxidant enzymes, indicating that the distinct cellular vulnerability to lowly/highly chlorinated PCBs was the main contributor to the PCBs toxicity. These findings emphasize the specific advantage of using earthworms in the control of lowly chlorinated PCBs in soil due to their high tolerance and accumulation ability.

Design, Synthesis and Biological Activity of New Hydroxamic Acids Containing 2-Imidazolylphenyl(oxy/thio)alkanoic Fragment

Background: Histone Deacetylase (HDAC) inhibitors are a new class of therapeutic compounds that show promising results in a series of preclinical and clinical anticancer studies. Hydroxamic acids belong to one of the most significant classes of HDAC inhibitors. The member vorinostat (SAHA) was approved by the U.S. Food and Drug Administration for the treatment of cutaneous T-cell lymphoma. Methods: A series of eight novel hydroxamic acids containing 2-imidazolylphenyl(oxy/thio) alkanoic fragment designed to target Histone Deacetylase (HDAC) were synthesized in five steps from easily accessible 2(3H)-benzoxazolones and 2(3H)-benzthiazolones. The newly synthesized compounds were characterized by 1H, 13C NMR, and elemental analysis. Results: The structure-activity relationship was examined via linker length alternation and variation of the heteroatom (oxygen or sulfur) and chlorine substitution pattern of the starting materials. The compounds were tested for their cytotoxic activity against two human cancer cell lines (HT-29 and MDA-MB-231). Our data indicate that the compound 6.1d is active in the micromolar range with IC50 of 9.7 μM for MDA-MB-231 cells. DNA fragmentation analysis of the most active compounds confirmed that apoptosis could be one of the mechanisms involved in cell death. Conclusion: Taken together, the results revealed that 6d may become a promising lead compound for new anticancer drugs discovery.

Asymmetric Synthesis of 4,4-(Difluoro)glutamic Acid via Chiral Ni(II)-Complexes of Dehydroalanine Schiff Bases. Effect of the Chiral Ligands Structure on the Stereochemical Outcome.

Four differently substituted chiral Ni(II)‐complexes of dehydroalanine Schiff base were prepared and reacted with BrCF2COOEt/Cu under the standard reaction conditions. The observed diastereoselectivity was found to depend on the degree and pattern of chlorine substitution for hydrogen in the structure of the dehydroalanine complexes. The unsubstituted complex gave the ratio of diastereomers (S)(2S)/(S)(2R) of 66/34. On the other hand, introduction of chlorine atoms in the strategic positions on the chiral ligands allowed to achieve a practically attractive diastereoselectivity of (∼98.5/1.5). Diastereomerically pure major product was disassembled to prepare 9‐fluorenylmethyloxycarbonyl (Fmoc) derivative of (S)‐4,4‐difluoroglutamic acid.

Integrating data gap filling techniques: A case study predicting TEFs for neurotoxicity TEQs to facilitate the hazard assessment of polychlorinated biphenyls

The application of toxic equivalency factors (TEFs) or toxic units to estimate toxic potencies for mixtures of chemicals which contribute to a biological effect through a common mechanism is one approach for filling data gaps. Toxic Equivalents (TEQ) have been used to express the toxicity of dioxin-like compounds (i.e., dioxins, furans, and dioxin-like polychlorinated biphenyls (PCBs)) in terms of the most toxic form of dioxin: 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD). This study sought to integrate two data gap filling techniques, quantitative structure–activity relationships (QSARs) and TEFs, to predict neurotoxicity TEQs for PCBs. Simon et al. (2007) previously derived neurotoxic equivalent (NEQ) values for a dataset of 87 PCB congeners, of which 83 congeners had experimental data. These data were taken from a set of four different studies measuring different effects related to neurotoxicity, each of which tested overlapping subsets of the 83 PCB congeners. The goals of the current study were to: (i) evaluate an alternative neurotoxic equivalent factor (NEF) derivations from an expanded dataset, relative to those derived by Simon et al. and (ii) develop QSAR models to provide NEF estimates for the large number of untested PCB congeners. The models used multiple linear regression, support vector regression, k-nearest neighbor and random forest algorithms within a 5-fold cross validation scheme and position-specific chlorine substitution patterns on the biphenyl scaffold as descriptors. Alternative NEF values were derived but the resulting QSAR models had relatively low predictivity (RMSE ∼0.24). This was mostly driven by the large uncertainties in the underlying data and NEF values. The derived NEFs and the QSAR predicted NEFs to fill data gaps should be applied with caution.

Dibenzo[b,f][1,4]oxazepines and dibenzo[b,e]oxepines: Influence of the chlorine substitution pattern on the pharmacology at the H1R, H4R, 5-HT2AR and other selected GPCRs

Inspired by VUF6884 (7-Chloro-11-(4-methylpiperazin-1-yl)dibenzo[b,f][1,4]oxazepine), reported as a dual H1/H4 receptor ligand (pKi: 8.11 (human H1R (hH1R)), 7.55 (human H4R (hH4R))), four known and 28 new oxazepine and related oxepine derivatives were synthesised and pharmacologically characterized at histamine receptors and selected aminergic GPCRs. In contrast to the oxazepine series, within the oxepine series, the new compounds showed high affinity to the hH1R (pKi: 6.8–8.7), but no or moderate affinity to the hH4R (pKi:≤5.3). For one oxepine derivative (1-(2-Chloro-6,11-dihydrodibenzo[b,e]oxepin-11-yl)-4-methylpiperazine), the enantiomers were separated and the R-enantiomer was identified as the eutomer at the hH1R (pKi: 8.83 (R), 7.63 (S)) and the guinea-pig H1R (gpH1R) (pKi: 8.82 (R), 7.41 (S)). Molecular dynamic studies suggest that the tricyclic core of the compounds is bound in a similar mode into the binding pocket, as described for doxepine in the hH1R crystal structure. Moreover, docking studies of all oxepine derivatives at the hH1R indicate that the oxygen and the position of the chlorine in the tricyclic core determines, if the R- or the S-enantiomer is the eutomer. For some of the oxazepines and oxepines the affinity to other aminergic GPCRs is in the same range as to hH1R or hH4R, thus, those compounds have to be classified as dirty drugs. However, one oxazepine derivative (3,7-Dichloro-11-(4-methylpiperazin-1-yl)dibenzo[b,f][1,4]oxazepine was identified as dual hH1/h5-HT2A receptor ligand (pKi: 9.23 (hH1R), 8.74 (h5-HT2AR), ≤7 at other analysed GPCRs), whereas one oxepine derivative (1-(3,8-Dichloro-6,11-dihydrodibenzo[b,e]oxepin-11-yl)-4-methylpiperazine) was identified as selective hH1R antagonist (pKi: 8.44 (hH1R), ≤6.7 at other analyzed GPCRs). Thus, the pharmacological results suggest that the oxazepine/oxepine moiety and additionally the chlorine substitution pattern toggles receptor selectivity and specificity.

Predicting gas chromatography relative retention times for polychlorinated biphenyls using chlorine substitution pattern contribution method

Various quantitative structure retention relationships have been published in an effort to understand and predict chromatographic retention times. This work presents a chlorine substitution pattern contribution (Cl-SPC) model for relative retention times (RRT) of polychlorinated biphenyls (PCBs), using 27 sets of previously published gas chromatography RRT data. The Cl-SPC model calculates the contribution factors (βk) for each of 19 chlorine substitution “patterns” (such as 2-, 2,4-, 2,3,6-, 2,3,4,5,6-, etc.) using multiple linear regression (MLR). The 27 separate MLRs had R2 values ranging from 0.961 to 1.000; the average absolute errors were 0.55% for the training sets and 0.95% for the test sets. Cross-validation of the model was carried out by splitting each data set into training and test sets for groupings based on nine PCB congener mixes commercialized by AccuStandard. No weakening of the model performance was observed when the size of data set used to develop the model was decreased from 209 to 39 congeners. In addition to the separate models, a single mixed model was fit combining all 27 data sets. The estimated random effects, which reflect the impact of GC configuration and operational conditions on RRTs, are minor compared with the fixed effects estimated for the βk values. The major advantages of the Cl-SPC model are its unmatched simplicity and equally excellent robustness when compared with other quantitative structure retention relationship models.

Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor.

Polychlorinated naphthalenes (PCNs) are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and are often called dioxin-like compounds. Chlorophenols (CPs) are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT) method and canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600−1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies.

Chlorination of poly(vinyl chloride) model compounds in radical‐complexing solvents

A potential route to the preparation of poly(1,2‐dichloroethylene) by the selective chlorination of poly(vinyl chloride) (PVC) was explored. During free‐radical chlorinations with Cl2, certain solvents play the very important role of forming complexes with the free chlorine atom that lead to changes in the pattern of chlorine substitution. In our work, the photochlorination of three model compounds for PVC, namely, 2,4‐dichloropentane, 3‐chloropentane, and 4‐chloroheptane, was carried out with molecular chlorine in the absence or presence of complexing solvents. The effects of these solvents on the chlorination selectivity were determined. During the conventional chlorination of sec‐alkyl chlorides with molecular chlorine, bridged‐radical intermediates are believed to be involved. They lead to vicinal dichlorides as the major products. However, we found that complexing solvents significantly increased the yields of geminal dichlorides instead. Such solvents also are well known to decrease reactivity in free‐radical chlorinations with Cl2. Thus, for both of these reasons, the chlorination of PVC with Cl2 in complexing solvents is unlikely to be useful for the preparation of poly(1,2‐dichloroethylene). J. VINYL ADDIT. TECHNOL., 22:405–409, 2016. © 2015 Society of Plastics Engineers

Serum concentrations of polychlorinated biphenyls (PCBs) in participants of the Anniston Community Health Survey

Serum concentrations of 35 ortho-substituted polychlorinated biphenyl congeners (PCBs) were measured in 765 adults from Anniston, Alabama, where PCBs were manufactured between 1929 and 1971. As part of the Anniston Community Health Survey (ACHS), demographic data, questionnaire information, and blood samples were collected from participants in 2005–2007. Forty-six percent of study participants were African-American, 70% were female, and the median age was 56years. The median concentration of the sum of 35 PCB congeners (ΣPCBs) was 528ng/g lipid, with a 90th percentile of 2600ng/g lipid, minimum of 17.0ng/g lipid, and maximum of 27,337ng/g lipid. The least square geometric mean ΣPCBs was more than 2.5 times higher for African-American participants than for White participants (866ng/g lipid vs. 331ng/g lipid); this difference did not change materially after adjustment for age, sex, body mass index (BMI) and current smoking. In spite of large differences in absolute PCB levels, relative contributions of individual congeners to ΣPCBs were quite similar between race groups. Nevertheless, while percent contributions to ΣPCBs for most of the most abundant penta- to heptachlorobiphenyls were higher among African-Americans, the percentages were higher in Whites for the lower-chlorinated PCBs 28 and 74 and for octa- to decachlorinated PCBs. No major differences were observed in geometric mean ΣPCBs between women and men when adjusted for age, race, BMI and current smoking (516ng/g lipid vs. 526ng/g lipid). Principal component analysis revealed groups of co-varying congeners that appear to be determined by chlorine substitution patterns. These congener groupings were similar between ACHS participants and the National Health and Nutrition Examination Survey (NHANES) 2003–04 sample of the general United States population, despite ACHS participants having serum concentrations of ΣPCBs two to three times higher than those in comparable age and race groups from NHANES.

The Effect of the Structure of Polychlorinated Biphenyls on their Hydroxylation, Oxidation, and Glutathionyl Conjugation Reactions

ObjectiveTo compare the nature of the metabolites formed from the phase I metabolism (hydroxylation and oxidation) and phase II metabolism (glutathionyl conjugation) of PCBs that have different chlorine substitution patterns. To discuss the structure-activity relationships and metabolic mechanisms of PCBs. Methods4-Cl-biphenyl (PCB3), 4,4'-Cl-biphenyl (PCB15), 3,4,3',4'-Cl-biphenyl (PCB77) were used for in vitro metabolic study. LC/MS and UV-Vis studies were performed for metabolites identification. ResultsThe cytochrome P-450 catalyzed hydroxylation rate decreased as the number of chlorine substitutions increased. In this reaction, PCB3 was fully metabolized, approximately half of the PCB15 was metabolized and PCB77 was not metabolized at all. The oxidation rate of PCB15-HQ was higher than that of PCB3-HQ under various oxidation conditions. The LC/MS and UV-Vis data suggest that in the conjugation reaction of PCB15-Q and GSH, the Michael addition reaction occurs preferentially over the displacement reaction. ConclusionThe metabolic profiles of polychlorinated biphenyls (PCBs) are dramatically affected by chlorine substitution patterns. It is suggested that the metabolic profiles of PCBs are related to their chlorine substitution patterns, which may have implications for the toxicity of PCB exposure.

Effects of Chain Length, Chlorination Degree, and Structure on the Octanol−Water Partition Coefficients of Polychlorinated n-Alkanes

Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.

Gas Phase Thermodynamic Properties of Polychlorinated Xanthones Predicted with DFT Method and Cl Substituted Position

The gas phase thermodynamic properties of 135 polychlorinated xanthones (PCXTs) are calculated using a combination of quantum mechanical computations performed with the Gaussian 03 program at the B3LYP/6-311G** level. It is found that the chlorine substitution pattern strongly influences the thermodynamic properties of the compounds. The thermodynamic properties of congeners with the same number of chlorines also depend on the chlorine substitution pattern, especially for ortho-substituted congeners. PCXT congeners with one phenyl ring fully chlorinated are found to be the least stable among the analogues. The effect of the chlorine substitution pattern is quantitatively studied by considering the number and position of Cl atom substitution ( N PCS). The results show that the N PCS model may be used to predict the thermodynamic properties for all 135 PCXT congeners. In addition, the values of molar heat capacities at constant pressure ( c p,m ) from 200 to 1000 K for PCXT congeners are calculated, and the temperature dependence relation of this parameter is obtained using the least-squares method.

Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCDD/Fs from 2,4,5-Trichlorophenol

An understanding of the reaction mechanism of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation is crucial for any attempt to prevent PCDD/Fs formation. Among the polychlorophenols, 2,4,5-trichlorophenol (2,4,5-TCP) has the minimum number of CI atoms needed to form 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (2,3,7,8-TeCDD), which is the most toxic among all 210 PCDD/F isomers. Experiments on the formation of PCDD/Fs from the 2,4,5-TCP precursor have been hindered by the strong toxicity of 2,3,7,8-TeCDD. In this work, we carried out molecular orbital theory calculations for the homogeneous gas-phase formation of PCDD/Fs from the 2,4,5-TCP precursor. Several energetically favorable formation pathways were revealed for the first time. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600-1200 K, using canonical variational transition state theory with small curvature tunneling contribution. The rate temperature formulas were fitted. This study shows that the formation of polychlorinated dibenzo-p-dioxins (PCDDs) from the 2,4,5-TCP precursor is preferred over the formation of polychlorinated dibenzofurans (PCDFs). The chlorine substitution pattern has a significant effect on the dimerization of chlorophenoxy radicals.

Electron ionization mass spectral fragmentation study of sulfation derivatives of polychlorinated biphenyls

BackgroundPolychlorinated biphenyls are persistent organic pollutants that can be metabolized via hydroxylated PCBs to PCB sulfate metabolites. The sensitive and selective analysis of PCB sulfate monoesters by gas chromatography-mass spectrometry (GC-MS) requires their derivatization, for example, as PCB 2,2,2-trichloroethyl (TCE) sulfate monoesters. To aid in the identification of unknown PCB sulfate metabolites isolated from biological samples, the electron impact MS fragmentation pathways of selected PCB TCE sulfate diesters were analyzed and compared to the fragmentation pathways of the corresponding methoxylated PCBs.ResultsThe most abundant and characteristic fragment ions of PCB TCE sulfate diesters were formed by releasing CHCCl3, SO3, HCl2 and/or CCl3 from the TCE sulfate moiety and Cl2, HCl, ethyne and chloroethyne from an intermediate phenylcyclopentadienyl cation. The fragmentation pattern depended on the degree of chlorination and the position of the TCE sulfate moiety (i.e., ortho vs. meta/para to the second phenyl ring), but were independent of the chlorine substitution pattern. These fragmentation pathways are similar to the fragmentation pathways of structurally related methoxylated PCBs.ConclusionKnowledge of the fragmentation patterns of PCB TCE sulfate diesters will greatly aid in determining the position of sulfate moiety (ortho vs. meta/para) of unknown PCB sulfate metabolites isolated from environmental or laboratory samples.

Bioaccumulation and biotransformation of 61 polychlorinated biphenyl and four polybrominated diphenyl ether congeners in juvenile American kestrels (Falco sparverius)

This study examined the bioaccumulation and dietary retention of 61 polychlorinated biphenyl (PCB) and four polybrominated diphenyl ether (PBDE) congeners in juvenile American kestrels (Falco sparverius). American kestrels were exposed to contaminants via egg injection and daily gavage dosing over the posthatch-to-fledgling period. Retention factors for PCBs were dependent on chemical hydrophobicity and chlorine substitution patterns and ranged from less than 1 to 16.4% for PCBs having vicinal hydrogen substitutions at meta-, para- carbons on at least one of the phenyl rings and between 13.2 and 81.5% for congeners containing chlorine substitutions at 4,4'-, 3',4,5'-, 3,4',5-, or 3,3',5,5'-positions. These results indicate that juveniles are capable of biotransforming PCBs according to the same structure-activity rules as adults. A toxicokinetic model, initially parameterized using adult toxicokinetic parameters, was used to describe concentration trends in juveniles over time. The adult model overestimated PCB concentrations but provided an adequate fit when elimination rate constants were increased by a factor of 12.7. Retention factors for the PBDE congeners 2,2',4,4'-tetrabromodiphenyl ether (BDE 47), 2,2',4,4',6-pentabromodiphenyl ether (BDE 100), 2,2',4,4',5-pentabromodiphenyl ether (BDE 99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE 153) were from 7.8 to 45.3% of the total dose. The retention of BDE 47 was similar that observed for readily cleared PCBs, whereas the remaining PBDEs exhibited retention factors consistent with those of persistent PCBs. Half-lives for PBDEs in juveniles were estimated to range from 5.6 to 44.7 d. Assuming differences in PBDE toxicokinetics between juveniles and adults similar to those measured for PCBs, adult American kestrel PBDE half-lives are expected to range from 72 to 572 d.

QSARs for the toxicity of polychlorinated dibenzofurans through DFT-calculated descriptors of polarizabilities, hyperpolarizabilities and hyper-order electric moments

DFT-B3LYP method with 6-31G(**) basis set was employed to fully optimize the electronic structures of 135 polychlorinated dibenzofurans and parent compound, namely dibenzofuran. It was demonstrated that polarizability anisotropy and mean polarizability could change sensitively and systematically with chlorine number and substitution pattern. And new quantitative structure-activity relationships (QSARs) focused on the binding affinities of aryl hydrocarbon receptor (AhR), aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) induction potencies of PCDFs were developed. It was concluded that polarizability anisotropy in conjunction with hyperpolarizabilties and hyper-order electric moments, e.g. octupole moments could well interpret the variation of toxicity of different congeners and dispersion interaction should be the leading form among various interactions. Although the terms of hyperpolarizabilities and hyper-order electric moments were not the same significant ones as polarizability anisotropy, the long-range interactions characterized by them should not be ignored in explaining the toxicity.

A Concentration-Dependent Multi-Term Linear Free Energy Relationship for Sorption of Organic Compounds to Soils Based on the Hexadecane Dilute-Solution Reference State

A LFER of the type in the title is applied to sorption of numerous compounds to polyethylene and three soils for which sorption to natural organic matter (NOM) is presumed dominant. It provides fractional contributions to the Gibbs free energy of sorption corresponding to hydrophobic effects, dipolar/polarizability (D/P) effects in excess of the reference state, and the sum of possible specific forces such as H-bonding and pi-pi electron donor-acceptor (pi-pi EDA) interactions in excess of the reference state. Minimal inputs are the isotherm, the n-hexadecane-water partition coefficient and the Abraham pi parameter representing D/P effects. Sorption of all compounds to polyethylene can be described by considering only hydrophobic effects. Sorption of a calibration set of apolar compounds (aromatic and aliphatic hydrocarbons and chlorinated hydrocarbons) to the natural sorbents is well-described by a combination of hydrophobic and D/P effects. For the apolar set, D/P contributes approximately 15-40% (2-8% for cyclohexane) of sorption free energy. D/P effects increase with the degree of chlorination for aliphatic compounds. For aromatic compounds D/P effects increase with fused ring size but do not vary with degree of chlorination and chlorine substitution pattern. H-bonding contributes substantially to sorption of alcohols, and similarly for 2-nonanol and 2,4-dichlorophenol (33-44%). pi-pi EDA forces contribute to phenanthrene sorption in one case. The effects of concentration, sorbent aromaticity (literature NMR), and sorbent polarity [(O + N)/C] on hydrophobic and D/P contributions for all compounds indicate that (a) molecules fill sites of progressively greater hydrophilic character; (b) the energy penalty for cavity formation in the solid decreases with concentration due to plasticization and greater intermolecular contact; (c) sorbent aromatic content more than sorbent polarity controls D/P interactions. Basing free energy on an inert electrostatic chemical environment afforded by n-hexadecane permits evaluation of direct electrostatic forces in NOM that contribute to sorption.

Comparison of dissociation mechanism between collisionally activated dissociation and charge inversion using alkali metal targets for chlorophenol isomers

Chlorinated aromatic compounds are well-known environmental pollutants whose toxicities depend dramatically on the chlorine substitution pattern, making differentiation of chlorophenol isomers important for environmental analysis. Collisionally activated dissociation (CAD) spectra and charge inversion spectra of ortho-, meta-, and para-chlorophenols (ClC 6H 4OH) and their partially deuterated forms (ClC 6H 4OD) were measured using alkali metal targets. The peaks associated with C 6H 4O + and C 5H 5Cl + ions observed in the CAD spectra result from the loss of HCl and CO fragments, respectively, after the re-arrangement of the hydroxyl hydrogen atom. The peaks associated with C 6H 4OH − and ClC 6H 4O − ions observed in the charge inversion spectra result from Cl loss and from hydroxyl bond dissociation, respectively. Isomeric differentiation is possible based on the clear differences observed in the relative intensities of these pairs of peaks. Although the intensities of the peaks associated with C 6H 4O + relative to those of C 5H 5Cl + in the CAD spectra are independent of the target species, the intensities of the peaks associated with C 6H 4OH − relative to those of ClC 6H 4O − in the charge inversion spectra are target dependent. The isomeric dependence of the positive ion distribution patterns in the CAD spectra is proposed to be due to the differences in the rate of the hydrogen atom re-arrangement process. In contrast, the isomeric dependence of the negative ion distribution patterns in the charge inversion spectra is attributed to differences in the bond strength involved in the direct dissociation process in the neutral intermediate species.

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.