Air-water PCB fluxes from southwestern Lake Michigan revisited

From simultaneous air and water polychlorinated biphenyl (PCB) measurements collected in September 2010, we re-evaluated the direction and magnitude of net air-water exchange of PCBs in southwest Lake Michigan and compared them with estimations made using similar approaches 15 years prior. Air and water samples were collected during a research expedition on Lake Michigan at 5 km off the coast of Chicago, with prevailing winds from the southwest of our location. Gas-phase ΣPCB concentrations ranged from 190 to 1100 pg m^?3 with a median of 770 pg m^?3, which is similar to the concentrations measured in the City of Chicago at the same time and similar to concentrations measured in this part of the lake over the last 20 years. Water dissolved-phase ΣPCB concentrations ranged from 150 to 170 pg L^?1 with a median of 160 pg L^?1, which is one-tenth of that measured in the 1990s. ?PCB net fluxes showed a slightly absorptive behavior, with a median of (?) 21 ng m^?2 day^?1 and an interquartile range of (?) 47 to (+) 5 ng m^?2 day^?1, where (?) and (+) fluxes indicate absorption and volatilization, respectively. Airborne PCB concentrations were higher when the winds were coming from Chicago and drive the deposition. Our fluxes are not significantly different from estimations from 1994 and 1995 and suggest that absorption of PCBs into the waters is slightly more prevalent than 15 years ago. It was confirmed that Chicago remains an important atmospheric source of PCBs to Lake Michigan.

     

Record of PCB congeners, sorbents and potential toxicity in core samples in Indiana Harbor and Ship Canal

Indiana Harbor and Ship Canal (IHSC) is an active navigational system that serves a heavily industrial area of southern Lake Michigan. We have determined the amount of polychlorinated biphenyls (PCBs), congener distributions, sorbent types and potential for dioxin-like PCB toxicity from two IHSC sediment cores. Vertical distributions of ΣPCBs (sum of 161 individual or coeluting congeners) ranged from 410 to 91000 and 1800 to 41000 ng g(-1) dry weight (d.w.) for cores 1 and 2, respectively. Core 1 showed its highest accumulation rate for the year ～1979 and exhibits a strong Aroclor 1248 signal in sediments accumulating over the last 60 years. It appears that from the late 1930s until the beginning of the 1980s there was a large and constant input of PCBs into this system. This pattern differs from lake cores from the Great Lakes region which commonly exhibit a rapid increase, a peak, followed by a sharp decrease in the PCB accumulation rates. Core 2 also has a strong Aroclor 1248 signal in the top layers, but deeper layers show evidence of mixtures of Aroclors and/or weathering processes. High levels of black carbon as a fraction of total organic carbon were found in both cores (median ～30%), which reflect the long history of local combustion sources. No strong relationship was found between ΣPCB concentration and sorbents. Both cores contain dioxin-like PCBs that are highest in concentration below the surface. The high levels of PCBs in the deep sediments are of concern because of plans to dredge this system.     

A semi-target analytical method for quantification of OH-PCBs in environmental samples

Environmental Science and Pollution Research - Hydroxylated polychlorinated biphenyls (OH-PCBs) are oxidative metabolites of PCBs and residuals found in original Aroclors. OH-PCBs are known to play...     

Uptake of Polycyclic Aromatic Hydrocarbons (PAHS) by Broad Leaves: Analysis of Kinetic Limitations

A kinetic model for the uptake ofpolycyclic aromatic hydrocarbons (PAHs) wasdeveloped from the anatomical structure of broadleaves. The model, which is supported by fielddata, includes the uptake from two pathways: outercuticle pathway and stomatal pathway, and withgrowth rate incorporated as a dilution term. Allthe parameters for the calculation of total masstransfer coefficient, k_OL, were estimated fromthe conductance of water vapor diffusion throughleaves. The results indicate that the stomatalpathway is a dominant pathway for dry gaseousdeposition of POPs on leaves and the uptake fromouter cuticle pathway can be neglected for the PAHsof molar volumes larger than phenanthrene becauseof the rate limitation in outer layer cuticle. Model sensitivity analyses demonstrates that withinthe range of environmental conditions and normalleaf structure, the surface area in stomata has themost significant effect on the uptake rate. If thestomatal pathway is closed, the kinetics of uptakeare so slow that accumulation appears independentof compound lipophilicity or molecular size. Ineither case, the leaf growth rate has little effecton the predicted accumulation     

城市工业区对沉积到密歇根湖的持久性有机污染物的数量和变化的影响

为密歇根湖建立了气相多氯联苯和反式-九氯杀虫剂的预测模型,考查所得数据可得出发展趋势.在本文中,我们叙述模型的结果以显示来自芝加哥地区的一股污染物的数量和它的变化如何对整个湖泊净污染物沉降的高度变动范围起作用.对整个湖泊来说,虽然年净气体交换与零没有多大区别,多氯联苯的年总沉降量约为3200kg.数据驱动模型显示,从每一天来说,持久性有机污染物(POPs)的净交换是否能从净沉降变成净挥发,这要看每股污染物影响的面积.这些研究发现说明①城市地区的控制能加速湖泊(污染物)的挥发;②从市区释放的POPs大半是挥发过程的结果.     

Development of a synthetic PCB mixture resembling the average polychlorinated biphenyl profile in Chicago air

Studies of environmental and toxic effects of polychlorinated biphenyls (PCBs) are ideally performed with PCB mixtures reflecting the composition of environmental PCB profiles to mimic actual effects and to account for complex interactions among individual PCB congeners. Unfortunately, only a few laboratory studies employing synthetic PCB mixtures have been reported, in part because of the challenges associated with the preparation of complex PCB mixtures containing many individual PCB congeners. The objective of this study was to develop a PCB mixture that resembles the average PCB profile recorded from 1996 to 2002 at a satellite station of the Integrated Atmospheric Deposition Network located at the Illinois Institute of Technology (IIT) in Chicago, Illinois, using commercial PCB mixtures. Initial simulations, using published Aroclor profiles, showed that a mixture containing 65% Aroclor 1242 and 35% Aroclor 1254 was a good approximation of the target profile. A synthetic Chicago air mixture (CAM) was prepared by mixing the respective Aroclors in this ratio, followed by GC/MS/MS analysis. Comparison of the PCB profile of the synthetic mixture with the target profile suggests that the synthetic PCB mixture is a good approximation of the average IIT Chicago air profiles (similarity coefficient cos θ = 0.82; average relative percent difference = 84%). The synthetic CAM was also a reasonable approximation of the average of 184 PCB profiles analyzed in 2007 at 37 sites throughout Chicago as part of the University of Iowa Superfund Basic Research Program (isbrp), with a cos θ of 0.70 and an average relative percent difference of 118%. While the CAM and the two Chicago air profiles contained primarily di- to pentachlorobiphenyls, higher chlorinated congeners, including congeners with seven or eight chlorine atoms, were underrepresented in the synthetic CAM. The calculated TCDD toxic equivalency quotients of the synthetic CAM (2.7 ng/mg PCB) and the IIT Chicago air profile (1.6 ng/mg PCB) were comparable, but lower by two orders of magnitude than the isbrp Chicago air profile (865 ng/mg PCB) due to surprisingly high PCB 126 levels in Chicago air. In contrast, the calculated neurotoxic equivalency quotients of the CAM (0.33 mg/mg PCB) and the two Chicago air profiles (0.44 and 0.30 mg/mg PCB, respectively) were similar. This study demonstrates the challenges and methods of creating and characterizing synthetic, environmental mixtures of PCBs.     

PCB dechlorination hotspots and reductive dehalogenase genes in sediments from a contaminated wastewater lagoon

Polychlorinated biphenyls (PCBs) are a class of persistent organic pollutants that are distributed worldwide. Although industrial PCB production has stopped, legacy contamination can be traced to several different commercial mixtures (e.g., Aroclors in the USA). Despite their persistence, PCBs are subject to naturally occurring biodegradation processes, although the microbes and enzymes involved are poorly understood. The biodegradation potential of PCB-contaminated sediments in a wastewater lagoon located in Virginia (USA) was studied. Total PCB concentrations in sediments ranged from 6.34 to 12,700 mg/kg. PCB congener profiles in sediment sample were similar to Aroclor 1248; however, PCB congener profiles at several locations showed evidence of dechlorination. The sediment microbial community structure varied among samples but was dominated by Proteobacteria and Firmicutes. The relative abundance of putative dechlorinating Chloroflexi (including Dehalococcoides sp.) was 0.01–0.19% among the sediment samples, with Dehalococcoides sp. representing 0.6–14.8% of this group. Other possible PCB dechlorinators present included the Clostridia and the Geobacteraceae. A PCR survey for potential PCB reductive dehalogenase genes (RDases) yielded 11 sequences related to RDase genes in PCB-respiring Dehalococcoides mccartyi strain CG5 and PCB-dechlorinating D. mccartyi strain CBDB1. This is the first study to retrieve potential PCB RDase genes from unenriched PCB-contaminated sediments.