Immunoassay monitoring of polychlorinated biphenyls (PCBs) in the Great Lakes

Although polychlorinated biphenyls (PCBs) are no longer manufactured, they are still entering the environment. In some compartments of the environment, PCB concentrations are a serious concern. This is especially true in compartments which accumulate PCBs, and in food items consumed by humans and wildlife. Also, there are situations in which management decisions require rapid, sensitive, accurate measurements, which can be made in real time under field conditions. Methods to use an enzyme-linked immunosorbent assay (ELISA) for PCBs were developed and applied to sediments and fish muscle homogenates collected from the Great Lakes. The extraction methods developed can be applied in the field with non-hazardous solvents, in the absence of sophisticated laboratory equipment. The method detection limit for PCBs in dimethyl sulfoxide (DMSO) extracts of sediment was 0.9 mg/kg. For PCBs in isopropanol extracts of fish tissue, the method detection limit was 0.6 mg/kg. The resolution of the ELISA was 0.83 mg/kg at 1.1 mg/kg and 1.6 mg/kg at 1.7 mg/kg, for sediment and fish tissue, respectively.     

Environmental risk assessment of existing chemicals

Most of the existing chemicals of high priority have been released into the environment for many years. Risk assessments for existing chemicals are now conducted within the framework of the German Existing Chemicals Program and by the EC Regulation on Existing Substances. The environmental assessment of a chemical involves:

1. exposure assessment leading to the derivation of a predicted environmental concentration (PEC) of a chemical from releases due to its production, processing, use, and disposal. The calculation of a PEC takes into account the dispersion of a chemical into different environmental compartments, elimination and dilution processes, as well as degradation. Monitoring data are also considered.
2. effects assessment. Data obtained from acute or long-term toxicity tests are used for extrapolation on environmental conditions. In order to calculate the concentration with expectedly no adverse effect on organisms (Predicted No Effect Concentration, PNEC) the effect values are divided by an assessment factor. This assessment factor depends on the quantity and quality of toxicity data available.

In the last step of the initial risk assessment, the measured or estimated PEC is compared with the PNEC. This “risk characterization” is conducted for each compartment separately (water, sediment, soil, and atmosphere). In case PEC > PNEC an attempt should be made to revise data of exposure and/or effects to conduct a refined risk characterization. In case PEC is again larger than PNEC risk reduction measures have to be considered.     

Environmental Hazard- Assessment of chemicals and products

Part II: Persistence and Degradability of Organic Chemicals The criteria “Persistence” and “Degradability” are defined and explained, starting from the “functional” definition of the environment. In this definition, theenvironment is the counterpart of thetechnosphere, which consists of all processes controlled by man. A substance is persistent if there are no sinks (degradation processes). It is shown that persistence is the central and most important critérium of environmental hazard assessment of organic chemicals. It follows that all substances released into the environment should be degradable, preferentially into small inorganic molecules (mineralization). As examples for persistent substances, the polychlorinated biphenyls (PCB), the chlorofluorohydrocarbons (CFC), bis (2-ethylhexyl) phthalate (DEHP), and 2,3,7,8-tetrachloro-dibenzo-dioxin (TCDD) are discussed. Finally, an attempt to quantify persistence is made.     

Dietary and environmental estrogens and antiestrogens and their possible role in human disease

Recent reports have suggested that dietary and environmental estrogens such as organochlorine pollutants may play a role in the increased incidence of breast cancer in women and disorders of the male reproductive tract. For example, elevated levels of DDE and polychlorinated biphenyls (PCB) have been measured in women with breast cancer. However, it should also be noted that numerous environmental and dietary compounds have also been characterized as antiestrogenic and as inhibitors of mammary cancer cell growthin vitro and/orin vivo. Some of these compounds include 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related compounds, polynuclear aromatic hydrocarbons (PAH), other naturally-occurring TCDD receptor agonists, retinoids, phorbol esters, terpenes, fatty acids, and polysaccharides. Thus, it is possible that dietary and environmental estrogens and antiestrogens may be contra-active, and these interactions must be considered in the overall risk assessment of the potential adverse human and environmental health impacts of these chemicals.     

Surfactant solubilization of hydrophobic compounds in soil and water

Reductions in the apparent soil-water partition coefficients (K_d ^*) for 28 polychlorinated biphenyls (PCBs) caused by the surfactant sodium dodecylsulphate (SDS) in the aqueous phase were studied. Above the critical micelle concentration (CMC) of the surfactant, K_d ^* was reduced by 2–3 orders of magnitude, but even far below CMC at environmentally relevant surfactant concentrations significant reductions in K_d ^* were observed. The plot of the soil-water partition coefficient (K_d) divided by K_d ^* versus the concentration of SDS allowed for the calculation of monomer (K_mn ^oc) and micellar (K_mc ^oc) surfactant-water partition coefficients normalized to organic carbon for each PCB congener. K_mn ^oc values were comparable with published values for the partition of PCBs between natural dissolved organic matter and lake water. K_mc ^oc values were up to 30 times higher than K_mn ^oc values and comparable with published octanol-water distribution coefficients. The findings of the present study underline the potential of surfactants at concentrations below their CMC to mobilize otherwise strongly bound hydrophobic compounds in soil-water systems.     

Deposition of semivolatile organic compounds to spruce needles

The deposition of atmospheric tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, α-HCH, γ-HCH, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 to spruce needles (Picea abies) was estimated for a period of 9 months. Accumulation in spruce as a result of dry gaseous deposition, particle bound deposition and wet deposition was calculated on the basis of the corresponding deposition rates and the compounds’ concentrations in the different atmospheric compartments. The comparison of the calculated values with the concentrations of the compounds measured in 9-month-old spruce needles showed that for many compounds each deposition pathway could explain a large part of the concentrations found in the needles.     

Toxicity testing of highly volatile chemicals with green algae

A gas-tight system for toxicity testing of highly volatile chemicals with the green algaChlamydomonas reinhardtii was developed. The procedure permits maintenance of constant and defined concentrations of the tested compounds in the vessels. To ensure sufficient CO₂-supply, new bipartite test vessels were used. These vessels allowed spatial separation of a HCO₃-/CO ₃ ^2? buffer used for CO₂ supply and the alga culture to avoid growth inhibition due to ionic strength. Several volatile chlorinated hydrocarbons have been tested. Their EC10 values were several orders of magnitude lower than those obtained with open test systems.     

Uptake and metabolism of 2,4,6-trinitrotoluene in higher plants

The fate of the explosive 2,4,6-TNT in plants is of major interest. Therefore, a method was developed to analyse TNT and derivatives in plant tissue. The method was utilized to investigate the uptake and metabolism of TNT inMedicago sativa andAllium schoenoprasum grown in hydroponic cultures containing TNT levels of 0.1 to 10 mg/1. Detectable concentrations of nitrotoluenes were significantly higher inAllium schoenoprasum than inMedicago sativa. The uptake of TNT in plants was directly related to the initial TNT level. The principal nitroaromatic components in roots and shoots of both plant species were identified as 4-ADNT and 2-ADNT in equal amounts, with substantially less TNT.     

Bioconcentration of superlipophilic persistent chemicals

According to present understanding, persistent superlipophilic chemicals — such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, Mirex etc — with log K_ow > 6 and cross sections > 9.5 Å, bioconcentrate in aquatic organisms only little from ambient water. The most convincing argument against it is that in bioconcentration experiments with superlipophilic chemicals amounts applied exceeded water solubility by several orders of magnitude. This paper describes various methods for determining bioconcentration factors (BCF) of superlipophilic compounds. As exemplified with octachlorodibenzo-p-dioxin, BCF values evaluated by these methods match well with those calculated by QSARs for fish and mussels based on log K_ow and water solubility. As expected, these BCF values exceed previous values by several orders of magnitude. For BCF evaluation of superlipophilic chemicals in aquatic organisms we recommend:

1. flow-through systems, kinetic method (OECD guideline No. 305 E)
2. ambient concentrations < water solubility
3. during the uptake and especially during the elimination phase no toxic effects of the test organisms should occur.

     

Determination of microbial activity in activated sewage sludge by dimethyl sulphoxide reduction

A method was developed to determine the dimethyl sulphoxide (DMSO) reduction rate in activated sewage sludge at nearly natural conditions. Linearity of microbially produced dimethyl sulphide with incubation time and sample size was shown. Apart from a fast, sensitive and highly reproducible automatic analysis of dimethyl sulphide, simultaneous determination of mineralisation, respiration and phenol degradation rates was possible. The DMSO reduction rate of samples taken from a municipal sewage plant ranged between 2 and 3 μmol/(g dry matter · h), respiration and mineralisation rates between 30 and 80 μmol/(g · h). Added¹³C₆-phenol was completely degradated after 96 h of incubation. A half-life of 14 h was calculated assuming first order decay. Dose response curves were obtained by incubating samples for 2, 6, 25, and 96 hours after addition of pentachlorophenol. At an incubation time of 6 h, the EC₅₀ values ranged from 20 mg/L (DMSO reduction) to 30 mg/L (phenol degradation) up to 180 mg/L (respiration and mineralisation). Increasing the incubation time to 96 h resulted in a lower EC₅₀ of 9 mg/L for DMSO reduction, whereas it increased to 500 mg/L for respiration and mineralisation.     

Source characterization and risk of exposure to atmospheric polychlorinated biphenyls (PCBs) in Ghana

With recent evidence that persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) are emerging in environmental media in some developing countries that otherwise have sparing production and usage history, it has become important to identify such contemporary source factors of PCBs and the risks this may pose, in line with the global consensus on POP management and elimination. The present study investigated contaminations from atmospheric PCBs in Ghana, deciphered source factors, and accessed risk of exposure to dioxin-like PCBs (DL-PCBs). Atmospheric PCBs were monitored by deployment of PUF-disk passive air samplers (PAS) at several sites across Ghana for 56 days. Atmospheric ∑₁₉₀PCB concentration in Ghana ranged from 0.28 ng/m³ in Kumasi to 4.64 ng/m³ at Agbogbloshie, a suburb in Accra noted for informal electronic waste (e-waste) recycling activities. As high as 11.10 ng/m³ of PCB concentration was measured in plumes from uncontrolled open burning of e-wastes at Agbogbloshie. Applying statistical source characterization tools, it emerged that e-wastes were a major contributor to the environmental burden of atmospheric PCBs in Ghana. The risk of DL-PCB toxicity via inhalation in the Agbogbloshie area was 4.2 pg TEQ/day, within similar order of magnitude of an estimated risk of 3.85 pg TEQ/day faced by e-waste workers working averagely for 8 h per day. It is suggested that elimination of e-waste sites would help to significantly reduce PCB-related toxicity issues in Ghana.

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Control of Contaminant Emissions From Fossil Fuel-Fired Boilers

The importance of fuels combustion was brought into sharp focus recently in a report on air pollution to the United States Senate in which it was stated, “These processes replace usable air with potentially harmful pollutants, and the capability of the atmosphere to disperse and dilute these pollutants—especially in urban areas where people, vehicles, and industries congregate in even greater numbers—is strictly limited.”¹ The overwhelming burden of emissions of sulfur compounds, as well as nitrogen compounds and particulate matter in the U. S. today, originates from the burning of coal and fuel oil in stationary combustion sources. Thus, combustion has a large influence on the quality of the atmosphere in most urban areas. The air pollution effects of these contaminants are many and varied and all are objectionable and undesirable. Without a doubt, the most serious air pollution problem in the nation today is that created by the combustion of fossil fuels.     

Environmental hazard — Assessment of chemicals and products

Part III: The Limits to Single Compound Assessment The principles and basic assumptions of single compound assessment are briefly reviewed. Limitations to this approach are shown, especially with regard to complex mixtures of similar substances, substitution products, and complicated (final) products containing chemicals and materials produced by the chemical industry. A new thinking in product lines and life cycles is emerging, leading to new assessment methods. In some cases, substitution has not improved the environmental performance of products, since very similar chemicals were used as substitutes.     

Polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in urban air and deposition in the United Kingdom

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) have been monitored in air and deposition at four UK urban sites (London, Cardiff, Manchester and Stevenage) since the beginning of 1991; data from the first 2 years are presented here. Median Σ2,3,7,8-substituted PCDD/F concentrations in air were 3.2, 4.0, 3.5 and 2.6 pg/m³ respectively for London, Cardiff, Manchester and Stevenage. Median Σ2,3,7,8-substituted PCDD/F deposition fluxes were 1.5 ng/m²/day in London, 1.4 ng/m²/day in Cardiff and Manchester and 0.79 ng/m²/day in Stevenage. Seasonal variations in the PCDD/F concentrations were observed at all sites for both air and deposition, with concentrations/fluxes generally elevated during the winter.     

Models for gas/particle partitioning,transformation and air/water surface exchange of PCBs and PCDD/Fs in CMAQ

We have added the capability to simulate polychlorinated biphenyls (PCBs) and polychlorinated dibenzo [p] dioxins and polychlorinated dibenzo-furans (PCDD/Fs) to the Community Multiscale Air Quality (CMAQ) modeling system, thus taking advantage of the latter's capability to simulate atmospheric advection, diffusion, gas-phase chemistry, cloud/precipitation, and aerosol processes. The modifications reported here include the addition to the CMAQ system of two gas/particle partitioning models options: the Junge–Pankow adsorption model and the K_OA absorption model, as well as chemical transformations and atmosphere/water surface exchange processes for these semi-volatile organics. Simulations for the purpose of model testing and validation were conducted for the years 2000 and 2002 on a domain covering most of North America. Both partitioning models give reasonable results when compared with available measurements. The model predictions of deposition and air concentrations also agree well with measurements. The modeling results also indicate that the long-range transport is important and anthropogenic emissions of PCBs and PCDD/Fs are dominant although surface exchange of PCBs may be important for some clean locations.     

Simulation of pesticide runoff at Rosemaund Farm (UK) using the SoilFug model

A validation exercise of the SoilFug model using field runoff data from Rosemaund Farm (UK) is described. A comparison has been made of modelled and measured concentrations of several pesticides in surface water and soil during and after specific rain events following application. The field experiments were designed to obtain data on rainfall, outflows of water, pesticide application rates and concentrations in soil and water. The results were satisfactory for the undissociated pesticides (atrazine, carbofuran, dimethoate, isoproturon, lindane, simazine and trifluralin), whose concentrations in water were mostly predicted within an order of magnitude of measured data. The results for the dissociated pesticides (dichlorprop, MCPA, mecoprop) were less satisfactory, giving generally much higher predicted concentrations in water. The use of the SoilFug model is suggested for the calculation of predicted environmental concentrations (PECs) in water, since it generally produces acceptable results from a relatively small set of input data, most of which is generally available.     

Release of Ethanol to the Atmosphere During Use of Consumer Cleaning Products

Liquid laundry and hand dish washing detergents contain volatile organic compounds, Including ethanol, that may be liberated during use and contribute to photochemical air pollution. In this study, the release of ethanol to the atmosphere during simulated household use of liquid detergents was measured. Three replicate experiments, plus a blank, were conducted In a 20-m³ environmental chamber for each of four conditions: “typical” dish washing (DT), “high-release” dish washing (DH), “typical” laundry (LT), and “high-release” laundry (LH). Average amounts of ethanol transferred to the atmosphere per use (and the fraction of ethanol used so liberated) were 32 mg (0.038) for DT, 100 mg (0.049) for DH, 18 mg (0.002) for LT, and 110 mg (0.011) for LH. Thus, a large fraction of the ethanol added to wash solutions with liquid detergents is discharged to the sewer rather than transferred to the atmosphere during use.     

Thermal remediation of PCDD/Fs contaminated soil by zone combustion process

A new thermal process has been proposed for remediating soils contaminated by chlorinated organic compounds, e.g., PCDD/Fs and PCBs. This is to apply the "zone combustion process" which utilizes stable combustion of coke particles in the packed bed to soils with air flow across the bed. The usefulness and validity were obtained the results showing that more than 98.9% of PCDD/Fs in the soil was successfully removed in a laboratory-scale experiment. Some pretreatment of the soil sample, such as drying, pre-granulation and addition of limestone was found to make the removal efficiency better. Although, some fundamentals on the behavior of PCDD/Fs, e.g., decomposition/vaporization ratios and formation of other compounds cannot be certainly identified yet, the present results clearly show a way to remediate the contaminated soils and solid wastes.     

The air quality forecast rote: Recent changes and future challenges

Air quality forecasting is a recent development, with most programs initiated only in the last 20 years. During the last decade, forecast preparation procedure—the forecast rote—has changed dramatically. This paper summarizes the unique challenges posed by air quality forecasting, details the current forecast rote, and analyzes prospects for future improvements. Because air quality forecasts must diagnose and predict several pollutants and their precursors in addition to standard meteorological variables, it is, compared with weather forecasts, a higher-uncertainty forecast. Forecasters seek to contain the uncertainty by “anchoring” the forecast, using an a priori field, and then “adjusting” the forecast using additional information. The air quality a priori, or first guess, field is a blend of past, current, and near-term future observations of the pollutants of interest, on both local and regional scales, and is typically coupled with predicted air parcel trajectories. Until recently, statistical methods, based on long-term training data sets, were used to adjust the first guess. However, reductions in precursor emissions in the United States, beginning in the late 1990s and continuing to the present, eroded the stationarity assumption for the training data sets and degraded forecast skill. Beginning in the mid-2000s, output from modified numerical air quality prediction (NAQP) models, originally developed to test pollution control strategies, became available in near real time for forecast support. The current adjustment process begins with the analyses and postprocessing of individual NAQP models and their ad hoc ensembles, often in concert with new statistical techniques. The final adjustment step uses forecaster expertise to assess the impact of mesoscale features not resolved by the NAQP models. It is expected that advances in model resolution, chemical data assimilation, and the formulation of emissions fields will improve mesoscale predictions by NAQP models and drive future changes in the forecast rote.

Implications: Routine air quality forecasts are now issued for nearly all the major U.S. metropolitan areas. Methods of forecast preparation—the forecast rote—have changed significantly in the last decade. Numerical air quality models have matured and are now an indispensable part of the forecasting process. All forecasting methods, particularly statistically based models, must be continually calibrated to account for ongoing local- and regional-scale emission reductions.     

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.