Monitoring OH-PCBs in PCB transport worker’s urine as a non-invasive exposure assessment tool

In this study, we analyzed hydroxylated polychlorinated biphenyls (OH-PCBs) in urine of both PCB transport workers and PCB researchers. A method to monitor OH-PCB in urine was developed. Urine was solid-phase extracted with 0.1% ammonia/ methanol (v/v) and glucuronic acid/sulfate conjugates and then decomposed using β-glucuronidase/arylsulfatase. After alkaline digestion/derivatization, the concentration of OH-PCBs was determined by HRGC/HRMS-SIM. In the first sampling campaign, the worker’s OH-PCB levels increased several fold after the PCB waste transportation work, indicating exposure to PCBs. The concentration of OH-PCBs in PCB transport workers’ urine (0.55~11 μg/g creatinine (Cre)) was higher than in PCB researchers’ urine (< 0.20 μg/g Cre). However, also a slight increase of OH-PCBs was observed in the researchers doing the air sampling at PCB storage area. In the second sampling, after recommended PCB exposure reduction measures had been enacted, the worker’s PCB levels did not increase during handling of PCB equipment. This suggests that applied safety measures improved the situation. Hydroxylated trichlorobiphenyls (OH-TrCBs) were identified as a major homolog of OH-PCBs in urine. Also, hydroxylated tetrachlorobiphenyls (OH-TeCBs) to hydroxylated hexachlorobiphenyls (OH-HxCBs) were detected. For the sum of ten selected major indicators, a strong correlation to total OH-PCBs were found and these can possibly be used as non-invasive biomarkers of PCB exposure in workers managing PCB capacitors and transformer oils. We suggest that monitoring of OH-PCBs in PCB management projects could be considered a non-invasive way to detect exposure. It could also be used as a tool to assess and improve PCB management. This is highly relevant considering the fact that in the next 10 years, approx. 14 million tons of PCB waste need to be managed. Also, the selected populations could be screened to assess whether exposure at work, school, or home has taken place.     

Matrix effects on the de novo synthesis of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes

The formation of polychlorinated dibenzo-p-dioxins, dibenzofurans, biphenyls and benzenes in de novo synthesis experiments have been studied on model fly ashes with a wide range of matrices. The model fly ash consisted of 18 selected matrices with the addition of CuCl(2) x 2H(2)O, activated charcoal and NaCl. The studied matrices were not restricted to the commonly investigated matrices with defined chemical composition (silica gel, alumina, florisil) and industrially produced adsorbents with silicate structures (diatomaceous earths), but also included natural occurring matrices (clays, kaolin, bentonite and feldspars). In addition fly ashes from a hazardous waste incinerator were included in the study for comparison. Differences in the isomer composition (homologue profiles and isomer patterns) of the substances formed by de novo synthesis experiments are discussed in dependence on the chemical composition of the studied matrices. The de novo synthesis experiments on matrices with silicate structures resulted in high concentration of mainly perchlorinated aromatic compounds while for other matrices in particular alkaline matrices a homologue shift to lower chlorinated homologues and lower formation rates were found. The paper discusses the resulting PCDD/PCDF pattern and compares them to the PCDD/PCDF profile found in naturally occurring kaolin and ball clay (illite).     

Use of artificial sediments in a comparative toxicity study with larvae and postlarvae of the grass shrimp, Palaemonetes pugio

An artificial sediment was tested for use in evaluating the potential hazard of toxicants on benthic organisms. The seawater-sediment system was assessed by use of the pyrethroid insecticide, fenvalerate, as the model toxicant for testing with larvae of the grass shrimp, Palaemonetes pugio, an ecologically important estuarine species. The sediment was prepared from commercially available components, and mixed with the toxicant to provide concentrations of 1, 10 and 100 microg fenvalerate kg(-1) dry sediment in 20 ppt seawater. Sediment free of the insecticide served as the control. Throughout the study, fenvalerate was not detected in the water column, but was measured in sediment at the nominal concentration of 100 microg kg(-1). The P. pugio population was adversely affected by fenvalerate. The effect occurred at metamorphosis, when larvae changed from pelagic individuals to benthic organisms. At this period, larvae were in direct contact with sediment. A portion of the population was tolerant of the insecticide.     

Long-term study of palladium in road tunnel dust and sewage sludge ash

The present work summarizes data about palladium contents of road tunnel dust from 1994 to 2007 and sewage sludge ash from 1972 to 2006. Since palladium is emitted from automotive catalytic converters as elemental particles, road dust is quiet useful to study traffic-related Pd emissions. Very high Pd values of up to 516 μg Pd kg⁻¹ were found in the road dust samples collected in 2007. Heavy metals of all urban emissions, also dental practice effluent, are enriched in sewage sludge ash and thus this matrix is useful for the documentation of palladium emission caused by the use of Pd alloys in dental medicine. In sewage sludge ash highest Pd contents of maximum 460 μg Pd kg⁻¹ were found in the years 1986-1997. In both matrices correlations of Pd content to Pd demand of industry are discussed.     

Lagrangian sampling of 3-D air quality model results for regional transport contributions to sulfate aerosol concentrations at Baltimore,MD, in summer 2004

We use ensemble-mean Lagrangian sampling of a 3-D Eulerian air quality model, CMAQ, together with ground-based ambient monitors data from several air monitoring networks and satellite (MODIS) observations to provide source apportionment and regional transport vs. local contributions to sulfate aerosol and PM_2.5 concentrations at Baltimore, MD, for summer 2004. The Lagrangian method provides estimates of the chemical and physical evolution of air arriving in the daytime boundary layer at Baltimore. Study results indicate a dominant role for regional transport contributions on those days when sulfate air pollution is highest in Baltimore, with a principal transport pathway from the Ohio River Valley (ORV) through southern Pennsylvania and Maryland, consistent with earlier studies. Thus, reductions in sulfur emissions from the ORV under the EPA's Clean Air Interstate Rule may be expected to improve particulate air quality in Baltimore during summer. The Lagrangian sampling of CMAQ offers an inexpensive and complimentary approach to traditional methods of source apportionment based on multivariate observational data analysis, and air quality model emissions separation. This study serves as a prototype for the method applied to Baltimore. EPA is establishing a system to allow air quality planners to readily produce and access equivalent results for locations of their choice.     

Recommendations on chemicals management policy and legislation in the framework of the Egyptian–German twinning project on hazardous substances and waste management

The sustainable management of chemicals and their associated wastes—especially legacy stockpiles—is always challenging. Developing countries face particular difficulties as they often have insufficient treatment and disposal capacity, have limited resources and many lack an appropriate and effective regulatory framework. This paper describes the objectives and the approach of the Egyptian–German Twinning Project under the European Neighbourhood Policy to improve the strategy of managing hazardous substances in the Egyptian Environmental Affairs Agency (EEAA) between November 2008 and May 2011. It also provides an introduction to the Republic of Egypt’s legal and administrative system regarding chemical controls. Subsequently, options for a new chemical management strategy consistent with the recommendations of the United Nations Chemicals Conventions are proposed. The Egyptian legal and administrative system is discussed in relation to the United Nations’ recommendations and current European Union legislation for the sound management of chemicals. We also discuss a strategy for the EEAA to use the existing Egyptian legal system to implement the United Nations’ Globally Harmonized System of Classification and Labelling of Chemicals, the Stockholm Convention and other proposed regulatory frameworks. The analysis, the results, and the recommendations presented may be useful for other developing countries in a comparable position to Egypt aspiring to update their legislation and administration to the international standards of sound management of chemicals.     

The elaboration of the 'Stockholm convention' on persistent organic pollutants (POPs): a negotiation process fraught with obstacles and opportunities

The conclusion in December 2000 of the negotiations for the 'Stockholm Convention' can clearly be labeled as a success. The Convention text was negotiated in merely five sessions of the Intergovernmental Negotiating Committee (INC) and accomplished after its fifth session despite the fact that numerous controversial issues, such as the inclusion of new substances under the ambit of the Convention, the acknowledgement of the precautionary principle or--clearly most controversial--the financing mechanisms, remained to be resolved. This paper attempts to provide a somewhat impressionistic account of the negotiations leading to the conclusion of the 'Stockholm Convention' as experienced by the members of the Swiss delegation participating in the negotiations of the INC. Besides a brief overview on the 'history' of the negotiations, it will focus on some issues of special interest--and controversy--to the negotiators, and finally attempt to provide an outlook on the future of the work performed by the INC and the implementation of the Convention. Issues of special interest are environmental policy issues, capacity building and financing, trade-related issues, precautionary principles, and technical and scientific issues.     

Characterization of dioxin-like contamination in soil and sediments from the ��hot spot�� area of petrochemical plant in Pancevo (Serbia)

Purpose

Combinatorial bio/chemical approach was applied to investigate dioxin-like contamination of soil and sediment at the petrochemical and organochlorine plant in Pancevo, Serbia, after the destruction of manufacturing facilities that occurred in the spring of 1999 and subsequent remediation actions.

Materials and methods

Soil samples were analyzed for indicator polychlorinated biphenyls (PCBs) by gas chromatography/electron capture detection (GC/ECD). Prioritized soil sample and sediment samples from the waste water channel were analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). Microethoxyresorufin o-deethylase (Micro-EROD) and H4IIE?Cluciferase bioassays were used for monitoring of dioxin-like compounds (DLC) and for better characterization of dioxin-like activity of soil samples.

Results

Bioanalytical results indicated high dioxin-like activity in one localized soil sample, while the chemical analysis confirmed the presence of large quantities of DLC: 3.0?×?10⁵ ng/g d.w. of seven-key PCBs, 8.2 ng/g d.w. of PCDD/Fs, and 3.0?×?10⁵ ng/g d.w. of planar and mono-ortho PCBs. In the sediment, contaminant concentrations were in the range 2?C8 ng/g d.w. of PCDD/Fs and 9?C20 ng/g d.w. of PCBs.

Conclusions

This study demonstrates the utility of combined application of bioassays and instrumental analysis, especially for developing and transition country which do not have capacity of the expensive instrumental analysis. The results indicate the high contamination of soil in the area of petrochemical plant, and PCDD/Fs contamination of the sediment from the waste water channel originating from the ethylene dichloride production.     

Biomonitoring of polychlorinated biphenyls in Bavaria/Germany—long-term observations and standardization

In the 1980s, it was demonstrated that semi-volatile organic compounds (SVOCs) like polychlorinated biphenyls (PCBs) accumulate in plant leaves. Plants are at the base of the food chain, and therefore a starting point for transfer of PCBs to animals and related human exposure. For two decades, the Environment Agency of the German federal state of Bavaria (LfU) has been operating long-term monitoring stations to measure the impact of organic air pollutants. Standardized ryegrass, curly kale, and spruce needles are used as bioindicators for the atmospheric entries of PCBs into vegetation. From the end of 1990s to 2009, there was a marked decline in the concentrations of indicator PCBs (i-PCBs) and a minor decline in PCB-TEQ levels. After 2009, the concentrations leveled off. In rural areas, the median concentrations of Σ6 i-PCB in ryegrass and curly kale were about 3 and 4 μg/kg dm in 2000, and have been about 0.5 and 1 μg/kg dm since 2009, respectively. Concentrations in spruce needles fell from 0.9 to 0.4 μg/kg dm. Median PCB-TEQ concentrations in the bioindicator plants ranged from 0.05 to 0.23 ng/kg dm between 2002 and 2009 and from 0.15 to 0.05 ng/kg dm after 2009. Indicator PCB and PCB-TEQ concentrations were several times higher at the urban station in Munich than at the rural areas, reflecting the emissions from in-use PCB stocks in the building sector. The likely reason of the slower decrease of PCB-TEQ compared to i-PCBs is the formation of PCB-126 by dechlorination of industrial PCBs in open applications.