Lighter Congeners Research Articles

Synthesis of Heavy Cyclodipnictadiphosphanes [ClE(μ-P-Ter)]2 [E = P, As, Sb, or Bi; Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl

A complete series of terphenyl-substituted 1,3-dichloro-1,3-dipnicta-2,4-diphosphanes {[ClE(μ-P-Ter)]2, where E = P, As, Sb, or Bi and Ter = 2,6-bis(2,4,6-trimethylphenyl)phenyl} was prepared and fully characterized. While the heavy derivatives with E = Sb or Bi can be accessed via conversion of silylated phosphanes with amino-dichloropnictanes and subsequent elimination of TerNH2, the lighter congeners could be prepared only by a metathesis reaction of [ClBi(μ-P-Ter)]2 with PCl3 and AsCl3. Spectroscopic and structural data indicate the existence of cis and trans isomers of [ClP(μ-P-Ter)]2 in contrast to all heavier derivatives, for which only the trans isomer was obtained.

Factors influencing atmospheric concentrations of polybrominated diphenyl ethers in Japan.

We used polybrominated diphenyl ether (PBDE) data in air at 38 sites across Japan (2009-2012), which were measured by the Japan Ministry of Environment (JMOE), to elucidate the time trend and seasonality of atmospheric PBDEs. In order to address few (7% for BDE-47) to many (63% for BDE-153 and 183) non-detect data, Tobit model, also called a censored regression model was used. The model revealed that the concentrations of PBDE congeners were influenced by a combination of year, temperature, rainfall rate, and population density. Greater declines were observed for BDE-47, -99, -153 and -183 (-21, -25, -17, -23%/year, p < 0.05) than for BDE-209 (-6%/year, p = 0.065). These trends were consistent with the estimated trends of penta-, octa- and deca-BDE contained in in-use products based on domestic demand for PBDEs in Japan and product lifespan. Seasonal patterns were opposite for light congeners (BDE-47 and -99), which increased with temperature, and heavy congeners (BDE-183, and -209), which decreased with temperature. Temperature-dependent emission (evaporation) for light congeners and temperature-independent emission (abrasion) for heavy congeners, coupled with seasonality of atmospheric boundary layer height, might explain these seasonal patterns. Human population density showed a positive correlation with all PBDE congener concentrations, whereas PBDEs showed negative correlation with rainfall rate.

Formation of [Bi11]3−, A Homoatomic, Polycyclic Bismuth Polyanion, by Pyridine‐Assisted Decomposition of [GaBi3]2−

Until now, polycyclic bismuth polyanions have not been known-thus discriminating bismuth from its lighter congeners. However, the synthesis of [K([2.2.2]crypt)]3 (Bi11 )⋅2 py⋅tol, allows us to present the first structurally characterized homoatomic, polycyclic bismuth polyanion, which exhibits the [P11 ](3-) "ufosan" structure. It was obtained upon treatment of [K([2.2.2]crypt)]2 (GaBi3 )⋅en with the solvent pyridine. The binary Zintl anion [GaBi3 ](2-) decomposes under oxidative coupling of pyridine molecules and release of H2 to form the title compound. The unprecedented reaction, its products and by-products were investigated by means of spectroscopy, spectrometry, and DFT studies. All findings reveal the specific reaction conditions to be crucial for the formation of the [Bi11 ](3-) ion-and indicate the possibility of the generation and isolation of further, large bismuth polyanions.

The Magnitude and Spatial Range of Current-Use Urban PCB and PBDE Emissions Estimated Using a Coupled Multimedia and Air Transport Model

SO-MUM, a coupled atmospheric transport and multimedia urban model, was used to estimate spatially resolved (5 × 5 km(2)) air emissions and chemical fate based on measured air concentrations and chemical mass inventories within Toronto, Canada. Approximately 95% and 70% of Σ5PCBs (CB-28, -52, -101, -153, and -180) and Σ5PBDEs (BDE-28, -47, -100, -154, and -183) emissions of 17 (2-36) and 18 (3-42) kg y(-1), respectively, undergo atmospheric transport from the city, which is partly over Lake Ontario. The urban air plume was found to reach about 50 km for PCBs and PBDEs, in the direction of prevailing winds which is almost twice the distance of the wind-independent plume. The distance traveled by the plume is a function of prevailing wind velocity, the geographic distribution of the chemical inventory, and gas-particle partitioning. Soil wash-off of historically accumulated Σ5PCBs to surface water contributed ∼ 0.4 kg y(-1) (of mainly higher congeners) to near-shore Lake Ontario compared with volatilization of ∼ 6 kg y(-1) of mainly lighter congeners. Atmospheric emissions from primary sources followed by deposition to surface films and subsequent wash-off to surface water contributed ∼ 1 kg y(-1) and was the main route of Σ5PBDE loadings to near-shore Lake Ontario which acts as a net PBDE sink. Secondary emissions of PCBs and PBDEs from at least a ∼ 900,000 km(2) rural land area would be needed to produce the equivalent primary emissions as Toronto (∼ 640 km(2)). These results provide clear support for reducing inventories of these POPs.

ACCUMULATION OF POLYCHLORINATED BIPHENYLS (PCBS) IN NAVIGATION CHANNELS, HARBORS AND INDUSTRIAL AREAS OF THE BAHIA BLANCA ESTUARY, ARGENTINA

The usage and production of polychlorinated biphenyls (PCBs) was banned in Argentina in2002, approximately twenty to thirty years later than in other countries. A total of 29 sediment samples (upto 14 m deep) were analyzed for a mix of seven individual PCBs in a time series for over more than one year in twelve selected locations, including harbors, recreational docks and several industrialized coastal locations in Bahia Blanca Estuary, Argentina, South America. The GC/ECD results showed the dominance of three chlorinated compounds: CB180, CB52 and CB101, which showed a strong reduction with distance from the urban area. The principal components analysis differentiates light and heavy congeners variation, settling several hypotheses and the classification of sampling sites to determine the PCB burden. Considering literature reports, the present results were evaluated in the international PCB context, diminishing the scarcity of PCB data from the Southern Hemisphere and prompting the need of future monitoring approaches.

The Ground State of (CS)4 Is Different from That of (CO)4: An Experimental Test of a Computational Prediction by Negative Ion Photoelectron Spectroscopy

Cyclobutane-1,2,3,4-tetrathione, (CS)4, has recently been calculated to have a singlet ground state, (1)A1g, in which the highest b2g σ MO is doubly occupied and the lowest a2u π MO is empty. Thus, (CS)4 is predicted to have a different ground state than its lighter congener, (CO)4, which has a triplet ground state, (3)B1u, in which these two MOs are each singly occupied. Here, we report the results of a negative ion photoelectron spectroscopy (NIPES) study of the radical anion (CS)4(•-), designed to test the prediction that (CS)4 has a singlet ground state. The NIPE spectrum reveals that (CS)4 does, indeed, have a singlet ground state with electron affinity (EA) = 3.75 eV. The lowest triplet state is found to lie 0.31 eV higher in energy than the ground state, and the open-shell singlet is 0.14 eV higher in energy than the triplet state. Calculations at the (U)CCSD(T)/aug-cc-pVTZ//(U)B3LYP/6-311+G(2df) level support the spectral assignments, giving EA = 3.71 eV and ΔEST = 0.44 eV. These calculated values are, respectively, 0.04 eV (0.9 kcal/mol) smaller and 0.13 eV (3.0 kcal/mol) larger than the corresponding experimental values. In addition, RASPT2 calculations with various active spaces and basis sets converge on a (1)B1u-(3)B1u energy gap of 0.137 eV, in excellent agreement with the 0.14 eV energy difference obtained from the NIPE spectrum. Finally, calculations of the Franck-Condon factors for transitions from the ground state of (CS)4(•-) to the ground ((1)A1g) and two excited states ((3)B1u, (1)B1u) of (CS)4 account for all of the major spectral peaks and nicely reproduce the vibrational structure observed in each electronic transition. The close correspondence between the calculated and the observed features in the NIPE spectrum of (CS)4(•-) provides unequivocal proof that (CS)4, unlike (CO)4, has a singlet ground state.

Evidence of elevated levels of polychlorinated biphenyl congeners in commonly consumed fish from Eleyele Reservoir, Southwestern Nigeria

Environmental pollution of water, which is a source of cheap and affordable protein in the form of fish on which the population depends on, is of great concern globally. The present study assesses the levels of polychlorinated biphenyls (PCBs) congeners in sediments and six commonly consumed cichlid species from Eleyele Reservoir, Southwestern Nigeria. The results indicate that the concentrations of heavier PCB congeners are higher than the lighter congeners in both sediment and fish tissue. The predominant PCB congeners in the sediment samples from this site were PCBs 8, 44, 114, 101, 189, 196, 206 and 209. The concentration of PCB congeners increased with increasing molecular weight from hepta-PCB to deca-PCB in all fish species. The trend in accumulation of total PCBs in fish was as follows: Tilapia guineensis (2,531.1 ± 74.6 ng/g) > Sarotherodon galilaeus (1178.7 ± 68.5 ng/g) > Oreochromis niloticus > (891.8 ± 49.6 ng/g) > Tilapia zillii (832.8 ± 38.2 ng/g) > Hemichromis fasciatus (475.7 ± 28.5 ng/g) > Sarotherodon melanotheron (333.2 ± 26.1 ng/g). In summary, data from this study shows that the levels of PCBs in cichlid species from Eleyele Reservoir are higher than the threshold level of 0.023-0.047 ng g(-1) recommended by United States Environmental Protection Agency. Such elevated PCB levels present significant health implications for human consumers and a threat to the resident fish communities.

Assessment and optimization of an ultrasound-assisted washing process using organic solvents for polychlorinated biphenyl-contaminated soil

The goal of this work was to evaluate a washing process that uses organic solutions for polychlorinated biphenyl (PCB)-contaminated soil, and includes an ultrasound pre-treatment step to reduce operational times and organic solvent losses. In a preliminary trial, the suitability of 10 washing solutions of different polarities were tested, from which three n-hexane-based solutions were selected for further evaluation. A second set of experiments was designed using a three-level Taguchi L27 orthogonal array to model the desorption processes of seven different PCB congeners in terms of the variability of their PCB concentration levels, polarity of the washing solution, sonication time, the ratio washing solution/soil, number of extraction steps and total washing time. Linear models were developed for the desorption processes of all congeners. These models provide a good fit with the results obtained. Moreover, statistically significant outcomes were achieved from the analysis of variance tests carried out. It was determined that sonication time and ratio of washing solution/soil were the most influential process parameters. For this reason they were studied in a third set of experiments, constructed as a full factorial design. The process was eventually optimized, achieving desorption rates of more than 90% for all congeners, thus obtaining concentrations lower than 5 ppb in all cases. The use of an ultrasound-assisted soil washing process for PCB-contaminated soils that uses organic solvents seems therefore to be a viable option, especially with the incorporation of an extra step in the sonication process relating to temperature control, which is intended to prevent the loss of the lighter congeners.

Dichlorosilylene: A High Temperature Transient Species to an Indispensable Building Block

Isolating stable compounds with low-valent main group elements have long been an attractive research topic, because several of these compounds can mimic transition metals in activating small molecules. In addition, compounds with heavier low-valent main group elements have fundamentally different electronic properties when compared with their lighter congeners. Among group 14 elements, the heavier analogues of carbenes (R(2)C:) such as silylenes (R(2)Si:), germylenes (R(2)Ge:), stannylenes (R(2)Sn:), and plumbylenes (R(2)Pb:) are the most studied species with low-valent elements. The first stable carbene and silylene species were isolated as N-heterocycles. Among the dichlorides of group 14 elements, CCl(2) and SiCl(2) are highly reactive intermediates and play an important role in many chemical transformations. GeCl(2) can be stabilized as a dioxane adduct, whereas SnCl(2) and PbCl(2) are available as stable compounds. In the Siemens process, which produces electronic grade silicon by thermal decomposition of HSiCl(3) at 1150 °C, chemists proposed dichlorosilylene (SiCl(2)) as an intermediate, which further dissociates to Si and SiCl(4). Similarly, base induced disproportionation of HSiCl(3) or Si(2)Cl(6) to SiCl(2) is a known reaction. Trapping these products in situ with organic substrates suggested the mechanism for this reaction. In addition, West and co-workers reported a polymeric trans-chain like perchloropolysilane (SiCl(2))(n). However, the isolation of a stable free monomeric dichlorosilylene remained a challenge. The first successful attempt of taming SiCl(2) was the isolation of monochlorosilylene PhC(NtBu)(2)SiCl supported by an amidinate ligand in 2006. In 2009, we succeeded in isolating N-heterocyclic carbene (NHC) stabilized dichlorosilylene (NHC)SiCl(2) with a three coordinate silicon atom. (The NHC is 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) or 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes).) Notably, this method allows for the almost quantitative synthesis of (NHC)SiCl(2) without using any hazardous reducing agents. Dehydrochlorination of HSiCl(3) with NHC under mild reaction conditions produces (NHC)SiCl(2). We can separate the insoluble side product (NHC)HCl readily and recycle it to form NHC. The high yield and facile access to dichlorosilylene allow us to explore its chemistry to a greater extent. In this Account, we describe the results using (NHC)SiCl(2) primarily from our laboratory, including findings by other researchers. We emphasize the novel silicon compounds, which supposedly existed only as short-lived species. We also discuss silaoxirane, silaimine with tricoordinate silicon atom, silaisonitrile, and silaformyl chloride. In analogy with N-heterocyclic silylenes (NHSis), oxidative addition reactions of organic substrates with (NHC)SiCl(2) produce Si(IV) compounds. The presence of the chloro-substituents both on (NHC)SiCl(2) and its products allows metathesis reactions to produce novel silicon compounds with new functionality. These substituents also offer the possibility to synthesize interesting compounds with low-valent silicon by further reduction. Coordination of NHC to the silicon increases the acidity of the backbone protons on the imidazole ring, and therefore (NHC)SiCl(2) can functionalize NHC at the C-4 or C-5 position.

Removal of alkylphenols and polybromodiphenylethers by a biofiltration treatment plant during dry and wet-weather periods

This paper investigates the occurrence of alkylphenols (APs) and polybromodiphenylethers (PBDEs) in raw wastewater during dry and wet-weather periods, and their removal by physico-chemical lamellar settling and biofiltration techniques. Due to in-sewer deposit erosion and, to a lesser extent, to external inputs, raw effluents exhibit from 1.5 to 5 times higher AP and PBDE concentrations during wet periods compared with dry ones. The lamellar settler obtains high removal of APs and PBDEs under both dry and wet-weather flows (>53% for Σ(6)AP and >89% for Σ(4)PBDE), confirming the insensitivity of this technique to varying influent conditions. Indeed, despite the higher pollutant concentrations observed in raw effluents under wet-weather flows, adjusting the addition of coagulant-flocculent allows for efficient removal. By combining physical and biological processes, the biofiltration unit treats nutrient pollution, as well as Σ(6)AP and Σ(4)PBDE contamination (58 ± 5% and 75 ± 6% respectively). Although the operating conditions of the biofiltration unit are modified during wet periods, the performance in nutrient pollution, APs and light PBDE congeners remains high. Nevertheless, lower efficiency has been noted in nitrogen pollution, i.e. no denitrification occurs, and BDE-209 (not removed during wet-weather periods). In conclusion, this study demonstrates that the combination of both techniques treats AP and PBDE pollution efficiently during dry periods, but that they are also suitable for stormwater treatment.

PCB contamination from sampling equipment and packaging

Work reported in this paper suggests that there are cases of contamination of soil and water samples by polychlorinated biphenyls (PCB) from paper and plastic packaging. Soil samples, which have been stored in paper bags for more than 20 years, share a similar congener distribution as the bags. Analyses showed a predominance of light congeners. PCB-analyses of water also indicate that water samples could be contaminated by plastic packaging. All analytical results of solid material packaging, as well as soil stored in the packaging, show a high relative amount of light weight PCB congeners. The paper bags that were analysed are made of strong paper and very popular among geochemists because of their watertight quality. These paper bags were manufactured more than 20 years ago. The plastic packaging that was analysed was produced in 1997 and 2008. The analyses of plastic and paper show that the raw material that has been used in the production at different times contains a wide concentration range of PCB. Re-sealable plastic bags, which contained the highest levels of PCB of the plastic material, are used by researchers world-wide as sampling bags for soils and sediments. This paper raises an important issue that packaging may potentially contaminate the samples that they hold.

Waste combustion as a source of ambient air polybrominated diphenylethers (PBDEs)

Abstract The first comprehensive set of U.S. data on polybrominated diphenylether (PBDE) concentrations from municipal waste combustion (MWC), with more than 40 PBDE congeners reported, was compared to ambient air levels of PBDEs in the U.S. The PBDE profiles in the raw MWC flue gas reflected the historical production and usage pattern of PBDE-based flame retardants in North America, which favored Penta- and Deca- BDE formulations. The pattern of selected, routinely measured in the environment, PBDEs (TeBDE-47, PeBDE-99, PeBDE-100, HxBDE-153 and DcBDE-209) was similar in the MWC emissions and profiles most commonly reported for the U.S. atmosphere. The mean Σ PBDE concentrations in the clean flue gases collected from the stack were 0.13 and 1.7 ng dscm −1 during the steady state and transients of MWC, respectively (which was 98.6% reduction compare to the levels in the raw flue gases). The major PBDE congeners in the MWC flue gases were those typically found in PBDE technical mixes (TeBDE-47, PeBDE-99, PeBDE-100, HxBDE-153, HpBDE-183, OcBDE-197, NoBDE-206, NoBDE-207, NoBDE-208, DcBDE-209). The profile of the PBDEs in the raw flue gas was dominated by heavier congeners, especially DcBDE-209, while the profile of the stack flue gases profile was dominated by the lighter congeners (TeBDE-47, PeBDE-99, PeBDE-100 accounted for around 80% of total stack emissions). Some of the MWC flue gas samples exhibited enrichment of lower brominated congeners that are minor or not present in the technical mixtures, suggesting that debromination occurs during combustion. Congeners substituted in non- and mono- ortho positions (TeBDE-77, PeBDE-126, HxBDE-156 and -169) were detected mostly during the transients of MWC.

Human Milk as a Vector and an Indicator of Exposure to PCBs and PBDEs: Temporal Trend of Samples Collected in Rome

Thirty-seven polychlorobiphenyl (PCB) congeners and seven polybromodiphenylether (PBDE) congeners were measured in human milk samples collected in Rome between 2005 and 2007. The comparison of results with two previous studies performed in Rome in 1984 and in 2000-2001 indicates a 64% decrease of PCB levels, still in progress; profile differences with time were also evident as lighter congeners are less relevant now; data are in good agreement with recent European studies. PBDE contamination profiles were different in individual samples and a similar variability was observed in data from different countries, suggesting different exposure pathways and profiles.

Porphyrin complexes of the period 6 main group and late transition metals

Metalloporphyrin complexes of the period six metals gold, mercury, thallium, lead and bismuth are often overlooked in favour of their lighter congeners. These complexes exhibit unusual coordination geometries, prominently featuring the metal centre residing out the porphyrin plane. Not only are these compounds chemically interesting, but several applications for these complexes are beginning to emerge. Gold and bismuth porphyrins have medicinal applications including novel chemotherapeutics and sensitizers for α-radiotherapy, while gold porphyrins have applications in materials chemistry and catalysis. This perspective serves to highlight trends in the synthesis and structure of these heavy metal complexes as well as illustrate the considerations necessary for rationally designing elaborate porphyrin architectures.

Congener-based analysis of the weathering of PCB Aroclor 1242 in paper mill sludge

Aroclor 1242 contains a high percentage of lightly chlorinated congeners, which makes it susceptible to congener profile alterations as a result of physical–chemical environmental weathering by water washing, evaporation, and volatilization. The analysis of the variability of congener profiles in paper sludge samples using PCA, mixing models, and correlation ( R 2) analysis, provided an integrated description of the behavior of Aroclor 1242 after its release in the environment. The results showed that the total PCB concentration decreased as the sample experienced weathering, with the congener profile of Aroclor 1242 shifting towards resembling heavier Aroclors as lighter congeners were lost. Mixing model analysis confirmed that a sample containing weathered Aroclor 1242 could easily be misidentified by laboratories as containing a mix of heavier Aroclors. The R 2 analysis showed that the profile of the congeners within a homologue group remained the same after weathering. This analysis showed that congeners that belong to the same level of chlorination behave similarly in such a manner that retains their overall profile when exposed to physical weathering.

Alkali Metal Complexes of a tert-Butylphosphine-Bridged Biphenolate Ligand

The coordination chemistry of group 1 metals with a potentially tridentate, dianionic biphenolate phosphine ligand that carries a phosphorus-bound tert-butyl group is described. Deprotonation of bis(3,5-di-tert-butyl-2-hydroxyphenyl)-tert-butylphosphine (H2[tBu-OPO]) with two equivalents of n-BuLi, NaH, or KH in ethereal solutions produces the corresponding alkali metal complexes {[tBu-OPO]M2(solv)x}2 (M = Li, Na, K; solv = DME, THF). An X-ray diffraction study of the lithium derivative reveals a dimeric structure that contains two [tBu-OPO]Li2(DME) units linked by two dative O−Li bonds; the two lithium atoms in each monomeric [tBu-OPO]Li2(DME) are bridged by both phenolate oxygen donors with only one lithium being coordinated to the phosphorus donor. As a result, the Li4O4 moiety in {[tBu-OPO]Li2}2 constitutes three successive Li2O2 tetragons fused in an open cubane structure. The coordination of the phosphorus donor to lithium in {[tBu-OPO]Li2(DME)}2 is also confirmed by variable-temperature 31P{1H} and 7Li{1H} NMR studies. Interestingly, the sodium complex is composed of two [tBu-OPO]Na2(DME)2 units linked by a bridging DME; each [tBu-OPO]Na2(DME)2 subunit is structurally similar to its lithium analogue though adopting one more coordinated DME. The potassium complex also contains two [tBu-OPO]K2(THF)2 moieties linked with two dative O−K bridges; the structure of the monomeric [tBu-OPO]K2(THF)2 unit, however, is markedly distinct from those of its lighter congeners. In addition to the anticipated fac-coordination from the heteroatoms in the biphenolate phosphine ligand, one of the potassium atoms in monomeric [tBu-OPO]K2(THF)2 is π-bound to one of the aryl rings incorporated in the [tBu-OPO]2− backbone.

Spatial and temporal distribution of polychlorinated biphenyl (PCB) concentrations in soils of an industrialized city in Turkey

Surface soil (0–5 cm) samples from 43 sampling sites covering the entire urban territory of Bursa, an industrialized city in Turkey, were collected in each season and analyzed for 83 polychlorinated biphenyls (PCBs). The mean concentration of total PCBs (Σ83 PCBs) among all sites over the four seasons was 2121.51 pg/g dry weight (dw), with a range of 207.61–5461.95 pg/g dw. Total PCB concentrations in the soil samples collected near an industrial region were the highest in all seasons.In general, PCB patterns were dominated by low-chlorinated homologue groups (≤5 Cl groups at a 79% level). The predominant homologue group found in Bursa city soils was the penta-CBs (29.1%) followed by the tetra-CBs (25.5%) and tri-CBs (17.6%). A total of seven dioxin-like PCB congeners (CB-77, 81, 105, 114, 118, 123, and 126) were found in every sampling location and their mean total concentration for all locations and seasons was 259.27 pg/g dw, with a range of 7.02–1581.13 pg/g dw. A significant relationship (r = 0.77, p < 0.01) was found between the concentrations of dioxin-like PCBs and the seasonal average sum of PCB concentrations. A correlation between light congeners (<penta-CB) and total organic carbon (TOC) was not observed, whereas a significant correlation (r = 0.36, p < 0.05) for heavy congeners (≥penta-CB) and TOC was found.The pollution potential was assessed based on the values found in soils in different regions in relation to current guideline values. Overall, it was found that PCB levels in the urban soils of Bursa were much lower than both the target values and the values found in most European soils and other regions.

Guided ion beam and theoretical study of the reactions of Hf+ with H2, D2, and HD

The kinetic energy dependences of reactions of the third-row transition metal cation Hf(+) with H(2), D(2), and HD were determined using a guided ion beam tandem mass spectrometer. A flow tube ion source produces Hf(+) in its (2)D (6s(2)5d(1)) electronic ground state level. Corresponding state-specific reaction cross sections are obtained. The kinetic energy dependences of the cross sections for the endothermic formation of HfH(+) and HfD(+) are analyzed to give a 0 K bond dissociation energy of D(0)(Hf(+)-H)=2.11±0.08 eV. Quantum chemical calculations at several levels of theory performed here generally overestimate the experimental bond energy but results obtained using the Becke-half-and-half-LYP functional show good agreement. Theory also provides the electronic structures of these species and the reactive potential energy surfaces. Results from the reactions with HD provide insight into the reaction mechanisms and indicates that Hf(+) reacts via a statistical mechanism. We also compare this third-row transition metal system with the first-row and second-row congeners, Ti(+) and Zr(+), and find that Hf(+) has a weaker M(+)-H bond. As most third-row transition metal hydride cation bonds exceed their lighter congeners, this trend is unusual but can be understood using promotion energy arguments.

Estimating the half-lives of PCB congeners in former capacitor workers measured over a 28-year interval

To date, most estimates of the half-life of polychlorinated biphenyls (PCBs) in humans have been based on relatively short follow-up periods. To address this issue, we determined the half-lives of PCB congeners of occupational origin in the serum of former capacitor workers as part of a study conducted in 2003-2006--approximately 28 years after their last occupational exposure. A total of 241 persons from a source population of 6798 former capacitor workers were interviewed and asked to donate a blood sample for serum PCB congener analysis. A subgroup of 45 participants also had serum archived from 1976 and reanalyzed for the same 27 PCB congeners by the same laboratory. Our estimates of the half-lives of the congeners among these 45 persons were longer than those reported by Wolff et al. (1992), due primarily to the much longer interval between exposure and determination of serum PCB concentrations. Half-lives were significantly greater for the heavy versus light occupational congeners, for women versus men and for those with low versus high initial exposure. Current serum total PCB concentrations, expressed as the geometric mean of wet weight data, averaged 6.7 ng/g for the entire 241-person cohort, which represents a 10-fold decrease from values reported in the late 1970s, but is still nearly twice the average for persons of similar age residing in the same area, but without occupational exposure. In addition, current serum PCB concentrations remained significantly and positively associated with earlier occupational exposure, but were not associated with fresh water fish consumption. In general, the results support a consistent and long-duration trend of increased PCB body burden in this cohort of former capacitor workers compared with non-occupationally exposed individuals. The results may aid in further understanding the toxicological/epidemiological consequences of exposure to PCBs in humans.

Cover Picture: AgIISO4: A Genuine Sulfate of Divalent Silver with Anomalously Strong One-Dimensional Antiferromagnetic Interactions (Angew. Chem. Int. Ed. 9/2010)

Deep-black AgSO4 (Mr. Hyde) is a narrow-bandgap semiconductor and an extremely strong oxidant. W. Grochala and co-workers show in their Communication on page 1683 ff. that it differs in all important physicochemical properties from its lighter congener, unreactive colorless CuSO4 (Dr. Jekyll). Unusually strong antiferromagnetic coupling persists up to the temperature at which AgSO4 thermally decomposes (ca. 120 °C), which sets it apart from all other transition-metal sulfates.