Development and validation of a method for analysis of "dioxin-like" PCBs in environmental samples from the steel industry

A method, previously used for determination of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), has been modified for quantitative analysis of "dioxin-like" polychlorobiphenyls (PCBs) in environmental samples from the steel industry. The existing sample clean-up procedure, involving liquid chromatography on multi-layered silica and Florisil columns, has been extended to include a third chromatography stage on a basic alumina stationary phase. The additional clean-up stage is required for PCB analysis in order to eliminate interferences from relatively large concentrations of saturated cyclic and aliphatic hydrocarbons. Samples were analysed for WHO-12 congeners using high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) and standard solutions of the method US EPA 1668A. Replicate analysis of method blanks revealed background contamination for PCBs 118, 105 and 77, which are generally abundant in ambient air. These contaminants were taken into account using a subtraction method. The entire procedure was validated by replicate analysis (N = 3) of a certified reference sediment. The RSD for each WHO-12 congener was below 15%, 13C12-labelled PCB internal standard recoveries were in the range 70-95%. A waste dust sample collected in the electrostatic precipitator of a UK sinter plant was analysed for determination of PCDD/Fs and WHO-12 PCBs and exhibited a PCDD/F I-TEQ of 148.5 +/- 21.2 ngkg(-1) and a WHO-TEQ of 7.2 +/- 1.5 ngkg(-1). WHO-12 congeners contributed only 4.6% to the overall TEQ and PCB 126 was the major congener contributing to the WHO-TEQ (96%). The contribution to the overall TEQ of the waste dust sample was mainly attributed to PCDF followed by PCDD, which accounted for 86.6% and 8.7% to the overall TEQ, respectively.     

A new method for testing the sensitivity of active biomonitoring: an example of its application to a terrestrial moss

For the first time, the concepts of limit of detection and limit of quantification, commonly used in analytical chemistry, are applied to the field of active biomonitoring with terrestrial mosses, using the controls as blanks so that the limits indicate the error associated with the transplant technique. The application of these concepts to data corresponding to Hg concentrations in the surroundings of a chlor-alkali plant and a power plant, makes interpretation of the results easier by providing better spatial and temporal coherence. This procedure may allow improvement in the standardization of active biomonitoring techniques as it is applicable to all kinds of biomonitors. One disadvantage of the application of the limit of detection and limit of quantification is that they only take into account the alpha error, or risk of false positives, and do not take into account the beta error, or risk of false negatives.     

Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Using Multimedia Modeling to Expedite Site Characterization

GOAL, SCOPE AND BACKGROUND: This paper uses two case studies of U.S. Department of Energy nuclear weapons complex installations to illustrate the integration of expedited site characterization (ESC) and multimedia modeling in the remedial action decision making process. CONCEPTUAL SITE MODELS, MULTIMEDIA MODELS, AND EXPEDITED SITE CHARACTERIZATION: Conceptual site models outline assumptions about contaminates and the spatial/temporal distribution of potential receptors. Multimedia models simulate contaminant transport and fate through multiple environmental media, estimate potential human exposure via specific exposure pathways, and estimate the risk of cancer and non-cancer health outcomes. ESC relies on using monitoring data to quantify the key components of an initial conceptual site model that is modified iteratively using the multimedia model. CASE STUDIES: Two case studies are presented that used the ESC approach: Los Alamos National Laboratory (LANL) and Pantex. LANL released radionuclides, metals, and organic compounds, into canyons surrounding the facility. The Pantex Plant has past waste management operations which included burning chemical wastes in unlined pits, burying wastes in unlined landfills, and discharging plant wastewaters into on-site surface waters. CONCLUSIONS: The case studies indicate that using multimedia models with the ESC approach can inform assessors about what, where, and how much site characterization data needs to be collected to reduce the uncertainty associated with risk assessment. Lowering the degree of uncertainty reduces the time and cost associated with assessing potential risk and increases the confidence that decision makers have in the assessments performed.     

Environmental impact of unleaded gasolines in the bay of Cádiz (Spain)

Given the strategic situation of the José León de Carranza bridge, which spans the Bay of Cádiz (in the SW of Spain) and carries very heavy motor traffic, together with knowledge of the currents and tidal flows in the zone, we have used a technique of radioactive dating of sediments to study the temporal evolution presented by contamination from lead in the sediment column. This has allowed us to observe the environmental impact, in terms of the concentration of Pb in the sea bed sediments, that has been produced in the zone by the introduction of unleaded gasolines as substitutes for traditional automobile fuels that employ organic forms of tetra methyl lead as an antidetonant agent in the fuel.     

Correlations in the chemical composition of rural background atmospheric aerosol in the UK determined in real time using time-of-flight mass spectrometry

An aerosol time-of-flight mass spectrometer (ATOFMS) was used to determine, in real time, the size and chemical composition of individual particles in the atmosphere at the remote inland site of Eskdalemuir, Scotland. A total of 51,980 particles, in the size range 0.3-7.4 microm, were detected between the 25th and 30th June 2001. Rapid changes in the number density, size and chemical composition of the atmospheric aerosol were observed. These changes are attributed to two distinct types of air mass; a polluted air mass that had passed over the British mainland before reaching Eskdalemuir, interposed between two cleaner air masses that had arrived directly from the sea. Such changes in the background aerosol could clearly be very important to studies of urban aerosols and attempts at source apportionment. The results of an objective method of data analysis are presented. Correlations were sought between the occurrence of: lithium, potassium, rubidium, caesium, beryllium, strontium, barium, ammonium, amines, nitrate, nitrite, boron, mercury, sulfate, phosphate, fluorine, chlorine, bromine, iodine and carbon (both elemental and organic hydrocarbon) in both fine (d < 2.5 microm) and coarse (d > 2.5 microm) particle fractions. Several previously unreported correlations were observed, for instance between the elements lithium, beryllium and boron. The results suggest that about 2 in 3 of all fine particles (by number rather than by mass), and 1 in 2 of all coarse particles containing carbon, consisted of elemental carbon rather than organic hydrocarbon (although a bias in the sensitivity of the ATOFMS could have affected these numbers). The ratio of the number of coarse particles containing nitrate anions to the number of particles containing chloride anions exceeded unity when the air mass had travelled over the British mainland. The analysis also illustrates that an air mass of marine origin that had travelled slowly over agricultural land can accumulate amines and ammonium.     

238Pu, 239,240Pu, 241Am, 90Sr and 137Cs in soils around nuclear research centre Rez, near Prague

Forty-four soil samples were taken around the nuclear research centre Rez, near Prague. The mean activity concentrations of 238Pu, 239,240Pu, 241Am, 90Sr and 137Cs in uncultivated soil were 0.010, 0.26, 0.12, 2.7 and 23 Bq.kg(-1), respectively. Contents of radionuclides in cultivated soil were lower and in forest soil higher than in uncultivated soil. The mean activity ratios of 238Pu/239,240Pu, 241Am/239,240Pu, 90Sr/239,240Pu and 239,240Pu/137Cs in uncultivated soil were 0.041, 0.47, 10.9 and 0.013, respectively. The mean activity ratios in cultivated and forest soils were close to the values given above. It follows from the results that the source of 239,240Pu, 90Sr and 137Cs in the studied area is deposition from atmospheric nuclear tests, in the case of 137Cs also deposition from Chernobyl accident. The contribution of the research centre effluents was not proved for these radionuclides. Increased activity ratio of 241Am/239,240Pu indicates the presence of 241Am in the soils studied emanating from sources other than nuclear tests. Uniform distribution of the 241Am/239,240Pu activity ratio around the nuclear research centre and the absence of an area with evidently higher activity ratio, including at sites lying in the main wind direction, suggest that the additional activity of 241Am does not originate from the nuclear research centre. The additional source might be the deposition following the Chernobyl accident.     

A study about remedial measures to reduce 222Rn concentration in an experimental building

Radon gas emanating from underground can spread to adjoining closed areas. It can concentrate and reach levels which represent a risk to people's health. It is well known that radon presence in most areas depends mainly on the area's geological features. Indoor radon concentrations further depend on the type of structure, construction materials and the technology used for the building. Therefore, indoor radon monitoring is of primary importance for deciding whether remedial measures are to be adopted for reducing harmful concentrations. This approach has been tried by measuring radon concentration in an experimental building situated in Milan (Italy). This building situated in a geological area that is considered at low radon risk. The results were obtained after analysing radon concentration in indoor rooms, crawl spaces, soil gas and in the atmosphere outside and by measuring before and after adoption of remedial measures. The study shows that improper building design can give rise to higher indoor radon accumulation even in an area of poor radon exhalation. Furthermore, the results enable quantification of the effectiveness of the remedial measures.     

Ethics, genetics and dynamics: an emerging systematic approach to radiation protection of the environment

There is now a general consensus of opinion that an explicit approach is necessary to demonstrate radiation protection of the environment, and that this approach needs to be developed in a systematic way. The framework that is emerging links ethical and moral issues (anthropocentric, biocentric, and ecocentric) to broad-based principles and objectives of environmental protection (sustainable development, maintaining biological diversity, and habitat protection) and then links these, in turn, to the needs of current environmental management practices, such as environmental exploitation, pollution control, and nature conservation. The relevance of this to radiation is that its effects (such as causing early mortality, morbidity, reduced reproductive success, as well as resulting in observable (scorable) cytogenetic damage) are those that may have a bearing on these same environmental management practices. The devise that would appear to be most useful to bridge the gap between our disparate data on radiation effects and the needs of environmental management, is that of adding to the concept of Reference Man in the shape of a small set of Reference Animals and Plants. This approach has now been adopted by the ICRP, adding new dynamics-the motive forces, both moral and physical-to the subject. The way is now clear for rapid progress to be made on a number of fronts.