Bioavailability of persistent organic pollutants in soils and sediments--a perspective on mechanisms, consequences and assessment

It has been observed that as soil-pollutant contact time increases, pollutant bioavailability and extractability decreases. This phenomenon has been termed 'ageing'. Decreased chemical extractability with increased soil-chemical contact time is evident where both 'harsh' techniques, e.g. dichloromethane Soxhlet extraction, and 'non-exhaustive' techniques, e.g. butanol shake extraction, have been used. It has also been observed that the amount of chemical extracted by these techniques varies considerably over time. Similarly, decreases in bioavailability with increased soil-pollutant contact time have been described in bacterial, earthworm and other organism studies. From these investigations, it has been shown that the fraction of pollutant determined to be bioavailable can vary between organisms. Thus, there is an immediate definition problem, what is bioavailability? Additionally, if bioavailability is to be assessed by a chemical means, which organisms should (or can) be mimicked by the extraction procedure? This review provides a background to the processes inherent to ageing, a discussion of its consequences on bioavailability and ends with some reflections on the appropriateness of chemical extraction techniques to mimic bioavailability     

An assessment of endocrine disrupting activity changes during wastewater treatment through the use of bioassays and chemical measurements.

The objective of this study was to assess the removal efficiencies of secondary wastewater treatment processes for compounds causing endocrine disrupting activity. The study used bioassays and chemical measurements, such as gas chromatography with mass spectrometry and enzyme immunosorbent assays. A total of seven full-scale water reclamation facilities using different unit operations and two pilot-scale membrane bioreactors were examined. Findings of this study imply that estrogenic disrupting activity in primary effluent is mainly caused by two steroidal hormones (17beta-estradiol and estriol) and, to a lesser extent, by synthetic chemicals, such as bisphenol A, 4-nonylphenol, and 4-tert-octylphenol. During secondary treatment, steroidal hormones were removed to a higher degree than nonylphenol and bisphenol A. The total estrogenic activity was removed by an average of 96%. The remaining concentrations of targeted steroids in secondary effluents, except for estriol, still had the potential to elicit a positive response in the human breast cell cancer assay. For the majority of facilities, the remaining activity was likely attributed to residual concentrations of two steroidal hormones (17beta-estradiol and estriol).     

The global re-cycling of persistent organic pollutants is strongly retarded by soils

'Persistent organic pollutants' (POPs) are semi-volatile, mobile in the environment and bioaccumulate. Their toxicity and propensity for long-range atmospheric transport (LRAT) has led to international bans/restrictions on their use/release. LRAT of POPs may occur by a 'single hop' or repeated temperature-driven air-surface exchange. It has been hypothesised that this will result in global fractionation and distillation-with condensation and accumulation in polar regions. Polychlorinated biphenyls (PCBs)--industrial chemicals banned/restricted in the 1970s--provide a classic illustration of POP behaviour. A latitudinally-segmented global PCB inventory has been produced, which shows that approximately 86% of the 1.3 x 10(6) tonnes produced was used in the temperate industrial zone of the northern hemisphere. A global survey of background surface soils gives evidence for 'fractionation' of PCBs. More significantly, however, very little of the total inventory has 'made the journey' via primary emission and/or air-surface exchange and LRAT out of the heavily populated source regions, in the 70 years since PCBs were first produced. Soils generally occlude PCBs, especially soils with dynamic turnover of C/bioturbation/burial mechanisms. This limits the fraction of PCBs available for repeated air-soil exchange. The forested soils of the northern hemisphere, and other C-rich soils, appear to be playing an important role in 'protecting' the Arctic from the advective supply of POPs. Whilst investigations on POPs in remote environments are important, it is imperative that researchers also seek to better understand their release from sources, persistence in source regions, and the significant loss mechanisms/global sinks of these compounds, if they wish to predict future trends.     

Residential indoor,outdoor, and workplace concentrations of carbonyl compounds: relationships with personal exposure concentrations and correlation with sources

Personal 48-hr exposures of 15 randomly selected participants as well as microenvironment concentrations in each participant's residence and workplace were measured for 16 carbonyl compounds during summer-fall 1997 as a part of the Air Pollution Exposure Distributions within Adult Urban Populations in Europe (EXPOLIS) study in Helsinki, Finland. When formaldehyde and acetaldehyde were excluded, geometric mean ambient air concentrations outside each participant's residence were less than 1 ppb for all target compounds. Geometric mean residential indoor concentrations of carbonyls were systematically higher than geometric mean personal exposures and indoor workplace concentrations. Additionally, residential indoor/outdoor ratios indicated substantial indoor sources for most target compounds. Carbonyls in residential indoor air correlated significantly, suggesting similar mechanisms of entry into indoor environments. Overall, this study demonstrated the important role of non-traffic-related emissions in the personal exposures of participants in Helsinki and that comprehensive apportionment of population risk to air toxics should include exposure concentrations derived from product emissions and chemical formation in indoor air.     

Nitrate storage by phytoplankton in a coastal upwelling environment

The storage of nitrate by phytoplankton cells during the early phases of upwelling was studied in coastal stations off northern Spain (southern Bay of Biscay) between 1990 and 1994. In this region, a persistent upwelling during summer is characterised by intermittent pulses of variable intensity, and increased nutrient concentrations in the surface layer. The main effect of an upwelling pulse on phytoplankton distribution is the shifting of the chlorophyll a and primary production maxima to near the surface. When the upwelling relaxes, thermal stratification of the water column occurs, and a distinct subsurface chlorophyll maximum develops below the production maximum. An accumulation of intracellular nitrate characterized the early phases of upwelling (mean = 2.73 μmol N m⁻³), maximum concentrations being attained at depths where biomass and production values were moderate. In contrast, phytoplankton cells from non-upwelling situations contained significantly lower concentrations of intracellular nitrate (mean = 0.17 μmol N m⁻³). The variations in the intracellular pool of nitrate may result from the differential allocation of resources within the cell as a result of variations in the energy available, since the uptake and assimilation of nitrate is a relatively expensive process involving several enzymatic systems. We hypothesize that nitrate storage by phytoplankton cells is characteristic of early phases of upwelling and is linked to patterns of carbon fixation. Average nitrogen budgets for upwelling and non-upwelling situations indicate that intracellular nitrate reserves are not responsible for maintaining high phytoplankton growth rates, since they only account for <2% of daily primary production during upwelling events. Received: 28 August 1996 / Accepted 3 December 1996     

Genetic structure of asexually reproducing Enteromorpha linza (Ulvales: Chlorophyta) in Long Island Sound

Heterotrophic bacterial uptake and turnover of glycolate were measured in the water column of the New York Bight apex during four seasonal cruises over almost a one-year period between May 1977 and March 1978. Glycolate turnover was most rapid in May and July, when primary productivity and estuarine runoff were high. Extremely rapid glycolate turnover times (<1 h) were detected at some stations during these months. Increased bacterial glycolate tunover did not accompany increased primary productivity in March, when water temperatures were lowest. Glycolate flux calculations indicate that the measured rates of glycolate consumption by bacteria always exceeded estimated glycolate production by phytoplankton, except in March. This excess may reflect an underestimation of phytoplankton production or the input of glycolate from other sources, such as estuarine runoff. Glycolate utilization appears to be seasonally important to bacteria in the New York Bight apex, coinciding with fluctuations in phytoplankton primary productivity.     

Redox-active ligands in artificial photosynthesis: a review

Environmental Chemistry Letters - Given the rising socioeconomic issues of fossil fuels, efficient artificial photosynthesis would be an important milestone toward a sustainable world. A key step...