Historical record of polychlorinated biphenyls (PCBs) in the continental shelf of the Korea Strait.

The vertical distribution of PCBs was measured in a dated core from the continental shelf of the Korea Strait. The historical trend of deposition and fluxes of individual and total PCB agreed well with the dynamics of historical tendencies of PCBs consumption in South Korea up to mid-1980 and a peak of total PCBs of 810 ng kg-1 was recorded at the turn of the 1960s. A second period of deposition, when concentrations of total PCB up to 1007 ng kg-1 were reached, was evidenced between 1989 and 2010 after the ban of PCBs. Sediments deposited in 1990s-2010, and sediments deposited in the period of maximum PCBs use (1956-1983) are both enriched in the less chlorinated homologue groups (tri- and tetrachlorobyphenyls) and congener PCB 118. However, the ratio of dioxin-like PCBs, and dichloro- and hexachloro homologue groups disclosed compositional variations between the two time periods. Source analysis suggested that PCBs in the sediment record mainly originated from Kanechlor 300, Kanechlor 400 and Aroclor 1242 technical mixtures overlapped by secondary/unintentional combustion sources from regional steel making processes in the last decades (1990s-2010).

Monsanto, PCBs, and the creation of a "world-wide ecological problem".

For the past three decades, we have written on the history of occupational and environmental health, authoring books and articles on lead poisoning, silicosis, asbestosis, and angiosarcoma of the liver, among other diseases. One book, Deceit and Denial, focused specifically on the chemical and lead industries. Because of the rarity of historians who study this history, we have been asked to testify on behalf of workers who allege harm from these industrial materials and by state, county, and local governments who seek redress for environmental damages and funds to prevent future harm to children. In about 2010, we began testifying in law suits brought by individuals who claimed that they had suffered from cancers, specifically non-Hodgkin's lymphoma, because of polychlorinated biphenyls (PCBs) in their bodies. At that time, we wrote a Report to the Court about industry knowledge of the dangers of PCBs to workers and the environment. More recently, we have been approached by attorneys representing government agencies on the West Coast of the United States which are seeking funds to abate PCB pollution in their ports, bays, and waterways. The focus of these lawsuits is the Monsanto Corporation, the sole producer of PCBs in the United States from the 1930s through 1977. Through these law suits, an enormous trove of previously private Monsanto reports, papers, memos, letters, and studies have been made available to us and this paper is the result of our examination of these hundreds of thousands of pages. The documents from this collection (with the exception of privileged materials that Monsanto has not made public, and upon which we have not relied) are available on www.ToxicDocs.org , the website we have developed with Professor Merlin Chowkwanyun of Columbia's Mailman School of Public Health. (Almost all of the references that are from this collection can be accessed by readers by clicking on the reference hyperlink.) This monograph is adapted from a report to the court that was originally produced for litigation on behalf of plaintiffs in PCB lawsuits. We are grateful to the Journal of Public Health Policy for publishing this detailed examination of these documents and we hope it will stimulate further research into this important, and now public, archive of industry records.

Historical sediment record and levels of PCBs in sediments and mangroves of Jobos Bay, Puerto Rico.

Polychlorinated biphenyls (PCBs) were quantified in 18 surface sediment samples, 1 sediment core, and several mangrove tissue samples collected in Jobos Bay, Puerto Rico in September 2013. Total PCBs in surface sediments ranged from 0.42 to 1232ngg-1 dw. Generally, higher levels were observed near-shore close to urban and industrial areas. The levels suggest significant pollution in Jobos Bay with respect to PCBs. Two-thirds of the sites were dominated by lighter PCB congeners (tri- to penta-chlorinated PCBs) while one-third had heavy PCB congeners (hexa- to octa-chlorinated PCBs) dominant. Total PCBs in a sediment core indicated levels fluctuating according to historical usage patterns. Total PCBs were measured in mangal leaves (14-747ngg-1 dw), roots (0.26-120ngg-1 dw), and seeds (16-93ngg-1 dw), suggesting bioaccumulation from sediments. This is the first report of a historical profile of PCBs in the study area and of PCB bioaccumulation in mangroves. This article provides new and useful information on PCBs in the Caribbean area of the GRULAC region.

Historical intake and elimination of polychlorinated biphenyls and organochlorine pesticides by the Australian population reconstructed from biomonitoring data.

Quantifying the competing rates of intake and elimination of persistent organic pollutants (POPs) in the human body is necessary to understand the levels and trends of POPs at a population level. In this paper we reconstruct the historical intake and elimination of ten polychlorinated biphenyls (PCBs) and five organochlorine pesticides (OCPs) from Australian biomonitoring data by fitting a population-level pharmacokinetic (PK) model. Our analysis exploits two sets of cross-sectional biomonitoring data for PCBs and OCPs in pooled blood serum samples from the Australian population that were collected in 2003 and 2009. The modeled adult reference intakes in 1975 for PCB congeners ranged from 0.89 to 24.5ng/kgbw/day, lower than the daily intakes of OCPs ranging from 73 to 970ng/kgbw/day. Modeled intake rates are declining with half-times from 1.1 to 1.3years for PCB congeners and 0.83 to 0.97years for OCPs. The shortest modeled intrinsic human elimination half-life among the compounds studied here is 6.4years for hexachlorobenzene, and the longest is 30years for PCB-74. Our results indicate that it is feasible to reconstruct intakes and to estimate intrinsic human elimination half-lives using the population-level PK model and biomonitoring data only. Our modeled intrinsic human elimination half-lives are in good agreement with values from a similar study carried out for the population of the United Kingdom, and are generally longer than reported values from other industrialized countries in the Northern Hemisphere.

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.

Applications of polychlorinated biphenyls.

BACKGROUND, AIM, AND SCOPE: In the 50 years or so that polychlorinated biphenyls (PCBs) were manufactured in the USA and elsewhere, they were widely used in numerous applications because of their desirable properties. The purpose of this paper is to review and summarize in one place the factual information about the uses of PCBs, as well as to correct some misconceptions that have arisen over the years. The focus is on applications in the USA for which there is ample documentation. However, use patterns were probably similar worldwide. MATERIALS AND METHODS: Review. RESULTS: PCBs were used primarily as electrical insulating fluids in capacitors and transformers and also as hydraulic, heat transfer, and lubricating fluids. PCBs were blended with other chemicals as plasticizers and fire retardants and used in a range of products including caulks, adhesives, plastics, and carbonless copy paper. In the USA, PCBs were manufactured from 1929 through mid-1977, although many products remained in service for decades after the manufacture of PCBs was terminated. This article reviews the historic uses of PCBs in the USA and discusses, where possible, the relative sales volumes. Especially with smaller volume, military, and third-party uses, documenting a use and/or differentiating between a commercial use and an experimental test batch is not possible. DISCUSSION: A major contribution of this paper is to differentiate reported commercial applications of PCBs that can be documented from those which cannot. Undocumented uses may include actual minor uses as well as reported applications that are unlikely ever to have been commercialized.

Historical PCB fluxes in the Mexico City Metropolitan Zone as evidenced by a sedimentary record from the Espejo de los Lirios lake.

The accumulation of PCBs over time was studied in a sediment core collected from Espejo de los Lirios, an ecological reserve located within the heart of Cuatitlan Izcalli, in the Northern part of Mexico City Metropolitan Zone. A (210)Pb-derived chronology, was used to reconstruct the historical PCB fluxes to the site during approximately 84 yr (1911-95). The highest input fluxes occurred in the 1977, after a significant increase after the late 1940s. This trend is clearly the consequence of the increasing emissions that are related to the onset of industrial activities starting from early 1970s. A phase of decrease, after the ban of the use in open systems, ended in 1989 and in 1995, at the time of sampling, the trend was toward a new increase to the highest levels. A reconstruction of PCB atmospheric concentration from sedimentary fluxes is attempted; and the estimate suggests that PCBs concentrations in the air of the Cuautitlán Izcalli seem not of concern. Nonetheless, the contamination levels found in the sediments are relatively high, reaching values above the threshold effect level (TEL) guidelines and, in two cases, close to the probable effect level (PEL) which mean that some adverse effects on the fauna may have occurred all over the time interval represented by the core.

Historical trends of PCDDs, PCDFs, dioxin-like PCBs and nonylphenols in dated sediment cores from a semi-enclosed bay in Korea: tracking the sources.

Two sediment cores, one at middle of the bay (core 1) and another at an outfall of a wastewater treatment plant (WWTP; core 2) were collected in Masan Bay, Korea, to investigate the historical records of contamination by polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (dl-PCBs), and nonylphenols (NPs). Vertical profiles of PCDD/Fs, dl-PCBs, and NPs in the two cores, dated using (210)Pb technique, were different but they had similar vertical profiles within the same core. The overall concentrations of these contaminants were greater in core 2 (0.05-110ng TEQkg(-1) dry wt for PCDD/Fs; 0.02-4.4ng TEQkg(-1) dry wt for dl-PCBs; 1.0-470microgkg(-1) dry wt for NPs) than in core 1 (0.72-8.0ng TEQkg(-1) dry wt for PCDD/Fs; 0.03-1.4ng TEQkg(-1) dry wt for dl-PCBs; 1.3-110microgkg(-1) dry wt for NPs). In particular, PCDD/F concentrations in core 2 were an order of magnitude greater than the concentrations in core 1. The highest concentrations of all target contaminants in cores1 and 2 were found at the surface layer (dated as 2005) and at 8-10cm ( approximately 2000), respectively. For sediment core 2, rapid changes in the concentrations and sources of target contaminants coincide with the establishment and operation of a WWTP; this suggested that discharges from WWTP contributed to contamination by PCDD/Fs, dl-PCBs and NPs in the bay. Analysis of data by non-parametric multidimensional scaling ordination showed that both the cores were influenced by different PCDD/F sources over time. Inventories and fluxes of PCDD/Fs, dl-PCBs, and NPs have rapidly increased since establishment of the WWTP, indicating that the discharge of WWTP is an important source of sediment contamination in aquatic environment.

Historical distribution of PCDDs, PCDFs, and coplanar PCBs in sediment core of Ariake Bay, Japan.

Persistent organic pollutants, particularly polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (co-PCBs) and toxic equivalent quantity (pg TEQ g(-1)) were determined in sediment samples collected from Ariake Bay, Japan. The total concentration of PCDDs/DFs in surface sediment of the Yabe River (17,000 pg g(-1) dry wt) was approximately 2.5-fold higher than that of the Chikugo River (7,000 pg g(-1) dry wt) which has the highest flow amount of about 40% inputting to the northern Bay. The congener profile suggested that dioxin sources could be close to the study area. The PCDDs concentration (12,000 pg g(-1) dry wt) in the sediment layer, which was corresponding to the 1960s, was reflected on the pentachlorophenol (PCP) contamination occurring at that time in Ariake Bay. The reflecting of PCP in the sediment core was significantly considered by hierarchical cluster analysis. Based on isomer-specific analysis, the tetrachlorodibenzo-p-dioxin composition showed a gradual increase from 1978-1982 toward the surface, indicating that the pollution source at that period might be more influenced by chloronitrofen than PCP. This fact was supported, based on the ratio of Sigma PCDD to Sigma PCDF concentration. The PCDDs/DFs-derived TEQ contributed more than 90% of the SigmaTEQ (PCDDs/DFs and co-PCBs) in all the detected sediment layers. The contribution of PCBs to the total TEQ was low; however, an increasing historical trend of concentration was clearly observed.

Temporal and spatial trends of atmospheric polychlorinated biphenyl concentrations near the Great Lakes.

Polychlorinated biphenyl (PCB) concentrations were measured in the atmosphere at six regionally representative sites near the five Great Lakes from 1990 to 2003 as part of the Integrated Atmospheric Deposition Network (IADN). Concentration data for several individual PCB congeners and for total PCBs were analyzed for temporal and spatial trends after correcting for the temperature dependency of the partial pressures. Atmospheric PCB concentrations are decreasing relatively slowly for tetra- and pentachlorinated congeners, an observation that is in agreement with primary emissions modeling. Relatively rapid decreases in PCB concentrations at the sites near Lakes Michigan and Ontario may reflect successful reduction efforts in Chicago and Toronto, respectively. Atmospheric PCB concentrations near Lakes Superior and Huron are now so low that the air and water concentrations may be close to equilibrium. Atmospheric PCB concentrations at sites near Lakes Michigan, Erie, and Ontario are relatively higher than those measured at sites near Lakes Superior and Huron. The highest PCB level was observed at the site near Lake Erie, most likely due to nearby urban activity. However, this relatively higher concentration is still 6-10 times lower than that previously reported at the Chicago site. A correlation between average gas-phase PCB concentration with local population indicates a strong urban source of PCBs. The temperature dependence of gas-phase PCB concentrations is similar at most sites except at Burnt Island on Lake Huron, where very low concentrations, approaching virtual elimination, prevent reliable temperature correlation calculations.

Towards a global historical emission inventory for selected PCB congeners--a mass balance approach 3. An update.

Previously published estimates of the global production, consumption and atmospheric emissions of 22 individual PCB congeners [Breivik K, Sweetman A, Pacyna JM, Jones KC. Towards a global historical emission inventory for selected PCB congeners - a mass balance approach. 1. Global production and consumption. Sci Total Environ 2002a; 290: 181-198.; Breivik K, Sweetman A, Pacyna JM, Jones KC. Towards a global historical emission inventory for selected PCB congeners--a mass balance approach. 2. Emissions. Sci Total Environ 2002b; 290: 181-198.] have provided useful information for later studies attempting to interpret contaminant levels in remote areas as well as in the global environment. As a result of the need for more contemporary emission data (following the year 2000), an update of this emission database is presented. This exercise takes into account new information on PCB production in Poland, as well as new data on the chemical composition of various technical mixtures for which less information had been available. The methodology to estimate temporal trends of PCB emissions associated with various types of PCB usage is improved. Projected emissions up to year 2100 are presented to facilitate predictions of future environmental exposure. The national emission data for each of the 114 countries considered is spatially resolved on a 1 degrees x1 degrees grid for each congener and year, using population density as a surrogate.

In situ reproduction, abundance, and growth of young-of-year and adult largemouth bass in a population exposed to polychlorinated biphenyls.

We conducted a two-year field study (2000-2001) in the Housatonic River, Massachusetts (USA) to determine if we could detect in situ population-level effects on largemouth bass (Micropterus salmoides) exposed to elevated levels of polychlorinated biphenyls (PCBs). Calculated whole-body PCB concentrations in adult bass in 2002 averaged 121 mg/kg (range = 34-556 mg/kg). Polychlorinated biphenyl concentrations in young-of-year (YOY) composites in 2000 and 2002 averaged 28 mg/kg (range = 21-41 mg/kg) and 19 mg/kg (range = 16-24 mg/kg), respectively. Laboratory studies of fish have reported PCB toxicity at exposure levels below and within the range of those found in the Housatonic River. We evaluated five field-derived metrics: reproductive activity, relative abundance of YOY, YOY growth rates, adult growth, and adult condition to determine whether we could detect effects of PCBs in the largemouth bass population. These computed metrics, when compared with data sets assembled for numerous largemouth bass populations in North America, provided no evidence of population-level impairment. Results of this study suggest that PCB tissue concentrations associated with effects in laboratory studies do not necessarily translate to detectable effects on largemouth bass populations in their natural environment.

Retrospective time-trend study of polybrominated diphenyl ether and polybrominated and polychlorinated biphenyl levels in human serum from the United States.

Six polybrominated diphenyl ethers (PBDEs), one hexabromobiphenyl [polybrominated biphenyl (PBB)], and one hexachlorobiphenyl [polychlorinated biphenyl (PCB)] were measured in 40 human serum pools collected in the southeastern United States during 1985 through 2002 and in Seattle, Washington, for 1999 through 2002. The concentrations of most of the PBDEs, which are commercially used as flame retardants in common household and commercial applications, had significant positive correlations with time of sample collection, showing that the concentrations of these compounds are increasing in serum collected in the United States. In contrast, PCB and PBB levels were negatively correlated with sample collection year, indicating that the levels of these compounds have been decreasing since their phaseout in the 1970s.

Environmental stress and recovery: the geochemical record of human disturbance in New Bedford Harbor and Apponagansett Bay, Massachusetts (USA).

Sediments record the history of contamination to estuaries. Analysis of the concentrations of toxic organic compounds, contaminant and crustal metals, organic carbon content and isotopic composition in sediment cores from two estuarine systems in Buzzards Bay allowed reconstruction of human impacts over 350 years. Vertical distributions of the contaminants correlate with changes in the nature of watershed/estuarine activities. All contaminants were highly enriched (tens to hundreds times background) in modern New Bedford Harbor sediments. Enrichment began around the turn of the 20th century for all but PCBs, which were first synthesized in the 1930s. An increase in organic carbon content and a shift of carbon isotopes toward a more terrestrial signature illustrates increasing anthropogenic impact in New Bedford as population grew along with the industrial base. Institution of environmental protection measures in the late 20th century was reflected in decreased, although still substantially elevated, concentrations of contaminants. A lack of industrial development in Apponagansett Bay resulted in much lower concentrations of the same indicators, although specific contaminants related to the early whaling industry increased significantly above background as early as the late 18th century. The similarity of indicators in older portions of cores from NBH and unimpacted Apponagansett Bay demonstrates that cores can be used to establish reference conditions as successfully as using separate sites judged a priori to represent the reference state. The historical reconstruction approach provides the basis for establishing relationships between environmental stressors and factors that drive the stressors, as well as a framework for the assessment of ecological response(s) to environmental stressors over a range of time and/or exposure scales.

Effects of historic PCB exposures on the reproductive success of the Hudson River striped bass population.

Scientists and regulatory agencies have expressed concern that exposures to polychlorinated biphenyls (PCBs) might be contributing to reductions in the abundance of fish populations exposed to these chemicals. The specific effects of concern involve impairment of fish reproduction, including both reduced egg production and decreased viability of eggs and larvae. We tested hypotheses concerning the effects of PCBs on fish populations using long-term data sets available for the striped bass population of the Hudson River, NY, a population that has long been a subject of regulatory concern because of potential effects of PCB exposures. The data sets examined include both measurements of PCB concentrations in adult female striped bass over the period from 1976 through 1997 and estimates of the numbers of striped bass eggs, larvae, and juveniles produced annually during this same period. We found strong correlations between estimates of the abundance of spawners and the number of eggs and larvae produced by those spawners and also between independent estimates of year-class strength derived from different sampling programs. However, we found no relationships between PCB exposure and any measure of striped bass abundance or reproduction. Although inconsistent with the expected effects of PCB exposures, trends in all measures of striped bass abundance and reproductive success were consistent with the expected effects of striped bass harvest restrictions that were imposed during the 1980s. Our results demonstrate a need for caution in inferring risks to populations in nature from effects observed in laboratory studies.

Gas-phase polychlorinated biphenyl and hexachlorocyclohexane concentrations near the Great Lakes: a historical perspective.

The Integrated Atmospheric Deposition Network (IADN) has been measuring gas-phase, polychlorinated biphenyl (PCB) concentrations at sites near Lakes Michigan and Superior for over a decade. Data through 2000 were used in this study to investigate PCB temporal trends in the Great Lakes atmosphere. Decreasing trends were found at both sites, and half-lives of approximately 20 yr were calculated using IADN data. However, when these data were supplemented by historical data for Lakes Michigan and Superior dating back to 1977, half-lives dropped to 10 and 6 yr, respectively. These latter half-lives agreed well with half-lives in other environmental compartments. Exponential curves fitted to the historical and IADN data indicated little decline in PCB concentrations in the basin since the mid-1990s. A similar historical analysis of alpha-and gamma-hexachlorocyclohexane (HCH) data indicated that IADN data were the best predictor of trends, resulting in half-lives of around 4 yr for both compounds. Gamma-HCH concentrations, however, have shown little decline in recent years, most likely because of its continuing use. PCB and alpha-HCH temporal trends indicated that bans on these substances have helped to remove them from the atmosphere. This work also showed that decades of data may be necessary to properly interpret long-term temporal trends in gas-phase organochlorine concentrations.