Andres Martinez

Inhalation and Dietary Exposure to PCBs in Urban and Rural Cohorts via Congener-Specific Measurements

Polychlorinated biphenyls (PCBs) are a group of 209 persistent organic pollutants, whose documented carcinogenic, neurological, and respiratory toxicities are expansive and growing. However, PCB inhalation exposure assessments have been lacking for North American ambient conditions and lower-chlorinated congeners. We assessed congener-specific inhalation and dietary exposure for 78 adolescent children and their mothers (n = 68) in the Airborne Exposure to Semi-volatile Organic Pollutants (AESOP) Study. Congener-specific PCB inhalation exposure was modeled using 293 measurements of indoor and outdoor airborne PCB concentrations at homes and schools, analyzed via tandem quadrupole GS-MS/MS, combined with questionnaire data from the AESOP Study. Dietary exposure was modeled using Canadian Total Diet Survey PCB concentrations and National Health and Nutrition Examination Survey (NHANES) food ingestion rates. For ∑PCB, dietary exposure dominates. For individual lower-chlorinated congeners (e.g., PCBs 40+41+71, 52), inhalation exposure was as high as one-third of the total (dietary+inhalation) exposure. ∑PCB inhalation (geometric mean (SE)) was greater for urban mothers (7.1 (1.2) μg yr–1) and children (12.0 (1.2) μg yr–1) than for rural mothers (2.4 (0.4) μg yr–1) and children (8.9 (0.3) μg yr–1). Schools attended by AESOP Study children had higher indoor PCB concentrations than did homes, and account for the majority of children’s inhalation exposure.

Polychlorinated biphenyls in the surficial sediment of Indiana Harbor and Ship Canal, Lake Michigan.

We report the results of the first intensive survey of polychlorinated biphenyls (PCBs) in the surficial sediment of the Indiana Harbor and Ship Canal (IHSC) in East Chicago, Indiana, a part of the Calumet River tributary of Lake Michigan that will be dredged to maintain depth for ship traffic. The tributary has previously been reported to be a large source of PCBs to Lake Michigan. PCB congeners were measured using tandem mass spectrometry in multiple reaction monitoring mode, a method that provides a high level selectivity and sensitivity for PCBs in complex environmental samples. The PCB concentrations (sum of 163 congeners or coeluting peaks) range from 53 to 35,000 ng g(-1) dry weight (d.w.) and are comparable to other PCB concentrations at contaminated tributaries in the United States, most of them (although not IHSC) established by law as Superfund sites. The PCB congener signal strongly resembles the original technical mixture Aroclor 1248 that has experienced a small amount of weathering--less than 2.5% by mass for the statistically different congeners--consistent with desorption, volatilization, and microbial dechlorination. The origin of the PCBs in IHSC is not known but Aroclor 1248 was used in hydraulic fluids, vacuum pumps, plasticizers and adhesives. Possible uses of this mixture in East Chicago included the equipment and auxiliary services for the adjacent steel mill and gas refinery and/or lubrication for the drawbridges spanning the canal.

Fate of PCB Congeners in an Industrial Harbor of Lake Michigan

We have quantified the release of polychlorinated biphenyls (PCBs) from Indiana Harbor and Ship Canal (IHSC) to Lake Michigan and the atmosphere. Navigational dredging is planned for this system, and there is concern that dredging will result in releases of PCBs. We have analyzed greater than 158 PCBs in surficial sediment, water, suspended particles, and air. We predicted the release of PCBs from sediments to water and from water to air. To quantify the level of confidence in our calculations, we used a Monte Carlo simulation for each congener flux. We determined that 4 +/- 0.05 kg of summation operatorPCBs were released from the sediment to the water and 7 +/- 0.1 kg of summation operatorPCBs were volatilized from the water to the air annually. We measured input from the upstream regions of the canal system of 45.0 kg yr(-1) and export to Lake Michigan of 43.9 kg yr(-1). The summation operatorPCBs mass balance accounts for nearly all the PCB inputs and losses to the navigational regions. The congener profiles in sediment, water, and air support our determination that the contaminated sediment is a major source of PCBs into the water and air above it. We have shown that the system is currently a significant source of PCBs to the air and to Lake Michigan, even under quiescent conditions.

Chicago's Sanitary and Ship Canal sediment: Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, brominated flame retardants, and organophosphate esters.

The Chicago Sanitary and Ship Canal (CSSC) links the Great Lakes to the Mississippi River starting in downtown Chicago. In addition to storm water, the CSSC receives water from Chicagos wastewater treatment plants (WWTP). Such effluents are known to be sources of organic pollutants to water and sediment. Therefore in 2013, we collected 10 sediment samples from the CSSC and measured the concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), brominated flame retardants, and organophosphate esters (OPEs). Geometric mean concentrations of the summed concentrations of 16 PAHs ranged from 11,000 to 420,000 ng/g dw, with the highest concentrations located at each end of the canal. Total PCB concentrations had a geometric mean of 1,400 ± 500 ng/g dw. Brominated flame retardants were separated into two groups: polybrominated diphenyl ethers (PBDEs) and non-PBDEs. Concentrations of PBDEs and those of the non-PBDE flame retardants had a geometric average of 83 ± 19 and 7.0 ± 5.8 ng/g dw, respectively. The summed concentrations of 8 OPEs ranged from 470 to 2,800 ng/g dw, with the highest concentration detected at a site located downstream of the Stickney water reclamation plant. Using ANOVA results, some hypotheses on sources to the CSSC could be formulated: downtown Chicago is probably a source of PAHs, the Cal-Sag Channel may be a source of PCBs, and neither the WWTP nor the Cal-Sag Channel seem to be significant sources of brominated flame retardants or OPEs.

Spatial distribution of chlordanes and PCB congeners in soil in Cedar Rapids, Iowa, USA

Residential soils from Cedar Rapids, Iowa, USA were collected and analyzed for chlordanes and polychlorinated biphenyls (PCBs). This study is one of the very few urban soil investigations in the USA. The chlordanes concentrations ranged from 0 to 7500 ng g(-1) dry weight (d.w.), with a mean and standard deviation of 130 ± 920 ng g(-1) d.w., which is about 1000 times larger than background levels. ΣPCB concentrations ranged from 3 to 1200 ng g(-1) d.w., with a mean and standard deviation of 56 ± 160 ng g(-1) d.w. and are about 10 times higher than world-wide background levels. Both groups exhibit considerable variability in chemical patterns and site-to-site concentrations. Although no measurements of dioxins were carried out, the potential toxicity due to the 12 dioxin-like PCBs found in the soil is in the same order of magnitude of the provisional threshold recommended by USEPA to perform soil remediation.

Simulating and Explaining Passive Air Sampling Rates for Semivolatile Compounds on Polyurethane Foam Passive Samplers

Passive air samplers (PAS) including polyurethane foam (PUF) are widely deployed as an inexpensive and practical way to sample semivolatile pollutants. However, concentration estimates from PAS rely on constant empirical mass transfer rates, which add unquantified uncertainties to concentrations. Here we present a method for modeling hourly sampling rates for semivolatile compounds from hourly meteorology using first-principle chemistry, physics, and fluid dynamics, calibrated from depuration experiments. This approach quantifies and explains observed effects of meteorology on variability in compound-specific sampling rates and analyte concentrations, simulates nonlinear PUF uptake, and recovers synthetic hourly concentrations at a reference temperature. Sampling rates are evaluated for polychlorinated biphenyl congeners at a network of Harner model samplers in Chicago, IL, during 2008, finding simulated average sampling rates within analytical uncertainty of those determined from loss of depuration compounds and confirming quasilinear uptake. Results indicate hourly, daily, and interannual variability in sampling rates, sensitivity to temporal resolution in meteorology, and predictable volatility-based relationships between congeners. We quantify the importance of each simulated process to sampling rates and mass transfer and assess uncertainty contributed by advection, molecular diffusion, volatilization, and flow regime within the PAS, finding that PAS chamber temperature contributes the greatest variability to total process uncertainty (7.3%).

Discovery of Hydroxylated Polychlorinated Biphenyls (OH-PCBs) in Sediment from a Lake Michigan Waterway and Original Commercial Aroclors

Hydroxylated polychlorinated biphenyls (OH-PCBs) were measured in surficial sediment from Indiana Harbor and Ship Canal (IHSC), East Chicago, IN and five original Monsanto Aroclors. These compounds were measured using gas chromatography with tandem mass spectrometry (GC-MS/MS) and certified standards that allowed us to identify 65 individual or coeluting congeners. Concentrations in the sediment ranged from 0.20 to 26 ng/g dry weight. Profiles of most samples were similar and were dominated by mono- to penta-chlorinated OH-PCBs. Interestingly, most of the samples strongly resembled the OH-PCB profiles of Aroclors 1221, 1242, 1248, and 1254, yet 25% of OH-PCBs measured in the sediment were not detected in Aroclors. A strong positive correlation was found between ΣOH-PCB and ΣPCB (p < 0.0001) and also between many individual OH-PCB:PCB pairs (p < 0.05). Analysis of OH-PCB:PCB pairs suggest PCB degradation is unlikely as a source of OH-PCBs in IHSC sediment. We are the first to report levels of OH-PCBs in sediment and Aroclors, and our discovery is significant because it is likely that OH-PCB contamination exists in sediment anywhere that PCB contamination from Aroclors is present.

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.

Inventory of PCBs in Chicago and Opportunities for Reduction in Airborne Emissions and Human Exposure

Urban areas are important regional sources of airborne polychlorinated biphenyls (PCBs) and population-scale airborne exposure, yet a comprehensive bottom-up source inventory of PCB emissions has never been quantified at urban scales in the United States. Here we report a comprehensive parcel level inventory of PCB stocks and emissions for Chicago, Illinois, developed with a transferable method from publicly available data. Chicagos legacy stocks hold 276 ± 147 tonnes ∑PCBs, with 0.2 tonnes added annually. Transformers and building sealants represent the largest legacy categories at 250 and 20 tonnes, respectively. From these stocks, annual emissions rates of 203 kg for ∑PCBs and 3 kg for PCB 11 explain observed concentrations in Chicago air. Sewage sludge drying contributes 25% to emissions, soils 31%, and transformers 21%. Known contaminated sites account for <1% of stocks and 17% of emissions to air. Paint is responsible for 0.00001% of stocks but up to 7% of ∑PCBs emissions. Stocks and emissions are highly concentrated and not correlated with population density or demographics at the neighborhood scale. Results suggest that strategies to further reduce exposure and ecosystem deposition must focus on the largest emissions sources rather than the most contaminated sites or the largest closed source legacy stocks.

Sediment pore water distribution coefficients of PCB congeners in enriched black carbon sediment

More than 2300 sediment pore water distribution coefficients (KPCBi ds) of 93 polychlorinated biphenyls (PCBs) were measured and modeled from sediments from Indiana Harbor and Ship Canal. KPCBi ds were calculated from previously reported bulk sediment values and newly analyzed pore water. PCBs in pore waters were measured using SPME PDMS-fiber and ∑PCB ranged from 41 to 1500 ng L(-1). The resulting KPCBi ds were ~1 log unit lower in comparison to other reported values. A simple model for the KPCBi d consisted of the product of the organic carbon fraction and the octanol-water partition coefficient and provided an excellent prediction for the measured values, with a mean square error of 0.09 ± 0.06. Although black carbon content is very high in these sediments and was expected to play an important role in the distribution of PCBs, no improvement was obtained when a two-carbon model was used.