PCDD/Fs and PCBs in butter samples from new European Union member states and a candidate country: analytical quality control, results and certain PCB-specific aspects

Milk and milk products have shown to be good indicator samples for the contamination of persistent organic pollutants (POPs) along the food chain. To gather information on whether exposure to dioxins and PCBs might cause a problem in countries about to join the European Union in 2004 or later, a study for evaluation of dioxin and levels of PCBs in 16 butter samples from eight countries (Cyprus, Czech Republic, Estonia, Lithuania, Poland, Romania, Slovenia and Slovakia) was performed. Comprehensive quality assurance/quality control (QA/QC) was requested. For this, eight quality control samples were included (in comparison to long-term mean, mean recovery for WHO-PCDD/F-TEQ of 97.9% with a CV of 3.0%, mean recovery for WHO-PCB-TEQ of 100.4% with a CV of 3.3%). Additionally, all butter samples were run as duplicates resulting in a confidence region of 95% statistical certainty of 4.6% for WHO-PCDD/F-TEQ and of 3.5% for WHO-PCB-TEQ. All samples except one from Romania were in the range of 0.21-0.59 pg WHO-PCDD/F-TEQ/g fat (upper bound), all samples except one from Romania and one from Estonia in the range of 0.32-0.82 pg WHO-PCB-TEQ/g fat (upper bound) and all samples except one from Romania and one from Estonia in the range of 0.57-1.23 pg sum WHO-TEQ/g fat (upper bound). The maximum values were found in samples from Romania (0.98 pg WHO-PCDD/F-TEQ/g fat; 1.75 pg WHO-PCB-TEQ/g fat) and Estonia (0.26 pg WHO-PCDD/F-TEQ/g fat; 1.62 pg WHO-PCB-TEQ/g fat). As a conclusion, all samples except one from Romania and one from Estonia were in the range of the actual low background contamination for PCDD/F and dioxin-like PCBs. The samples with elevated concentrations were below the EU action and maximum levels which have been valid since 2002, or will be applied from November 2006. In all samples except in one from Estonia, the contribution of dioxin-like PCBs to sum WHO-TEQ was 47-68% which reflects the usual range in Europe. In one sample from Estonia this contribution was 86% which points to a particular yet unknown PCB source. Thirty eight PCB congeners were determined allowing a detailed discussion of the relative contribution of individual congeners to the total PCB concentration. Correlation between PCB 153 and WHO-PCB-TEQ varied considerably between samples from different countries. Major tetra- or pentachlorinated mono-ortho PCBs without assigned TEFs were PCBs 60, 66, 74, and 110.     

Temporal change in the distribution patterns of hexachlorobenzene and dichlorodiphenyltrichloroethane among various soil organic matter fractions

Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2>0.97). The transfer rates of HCB and DDT followed the order FA>HA>BHA.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Growth performance and biochemical responses of three rice (Oryza sativa L.) cultivars grown in fly-ash amended soil

The disposal of fly-ash (FA) from coal-fired power stations causes significant economic and environmental problems. Use of such contaminated sites for crop production and use of contaminated water for irrigation not only decreases crop productivity but also poses health hazards to humans due to accumulation of toxic metals in edible grains. In the present investigation, three rice cultivars viz., Saryu-52, Sabha-5204, and Pant-4 were grown in garden soil (GS, control) and various amendments (10%, 25%, 50%, 75% and 100%) of FA for a period of 90 days and effect on growth and productivity of plant was evaluated vis-a-vis metal accumulation in the plants. The toxicity of FA at higher concentration (50%) was reflected by the reduction in photosynthetic pigments, protein and growth parameters viz., plant height, root biomass, number of tillers, grain and straw weight. However, at lower concentrations (10-25%), FA enhanced growth of the plants as evident by the increase of studied growth parameters. The cysteine and non-protein thiol (NP-SH) content showed increase in their levels up to 100% FA as compared to control, however, maximum content was found at 25% FA in Saryu-52 and Pant-4 and at 50% FA in Sabha-5204. Accumulation of Fe, Si, Cu, Zn, Mn, Ni, Cd and As was investigated in roots, leaves and seeds of the plants. Fe accumulation was maximum in all the parts of plant followed by Si and both showed more translocation to leaves while Mn, Zn, Cu, Ni and Cd showed lower accumulation and most of the metal was confined to roots in all the three cultivars. As was accumulated only in leaves and was not found to be in detectable levels in roots and seeds. The metal accumulation order in three rice cultivars was Fe > Si > Mn > Zn > Ni > Cu > Cd > As in all the plant parts. The results showed that rice varieties Saryu-52 and Sabha-5204 were more tolerant and could show improved growth and yield in lower FA application doses as compared to Pant-4. Thus, Sabha-5204 and Saryu-52 are found suitable for cultivation in FA amended agricultural soils for better crop yields.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

PCDD/Fs, dioxin-like PCBs and marker PCBs in eggs of peregrine falcons from Germany

Thirty one egg samples of peregrine falcons were collected in different regions of Germany (South-West, North and East) and analysed for PCDD/Fs, PCBs and marker PCBs. Altogether, 37 PCB congeners were determined, allowing a more detailed discussion of different aspects of the relative importance of these individual congeners. For comparison with dioxin data from other studies, differences between toxic equivalency factors (TEF) have to be taken into consideration. The results of this study are discussed on the basis of WHO-TEFs for birds published in 1998. All samples showed high levels of PCDD/Fs (median of all samples: 368 pg WHO-PCDD/F-TEQ/g fat; range 137-1453) and even higher levels of PCBs (median 967 pg WHO-PCB-TEQ/g fat; range 243-7482). The upper range of these levels reach concentrations found at the beginning of the Belgian dioxin crisis when a significant reduction in hens' egg hatchability was observed. The relative contribution of PCBs to the total TEQ is on average 71% (range 55-92%) with a tendency to higher values in South-West Germany compared to different sites in East Germany or one site in northern Germany. Within a region, a wide range of contamination can be found. Even in the same cities (Stuttgart and Ludwigshafen), results derived from eggs collected in the same year (2003) varied by factors 5-10. These findings show the high degree of variation occurring even within the same kind of biological matrix. Therefore, to allow for comparison of regions or time trends, a considerable number of samples has to be analysed.     

Exemplifying whole-plant ozone uptake in adult forest trees of contrasting species and site conditions

Whole-tree O3 uptake was exemplified for Picea abies, Fagus sylvatica and Larix decidua in stands at high and low altitude and contrasting water availability through sap flow measurement in tree trunks, intrinsically accounting for drought and boundary layer effects on O3 flux. O3 uptake of evergreen spruce per unit foliage area was enhanced by 100% at high relative to low elevation, whereas deciduous beech and larch showed similar uptake regardless of altitude. The responsiveness of the canopy conductance to water vapor and, as a consequence, O3 uptake to soil moisture and air humidity did not differ between species. Unifying findings at the whole-tree level will promote cause-effect based O3 risk assessment and modeling.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

Cadmium accumulation in the female shore crab Carcinus maenas during the moult cycle and ovarian maturation

 The influence of moulting and ovarian maturation on cadmium accumulation in the tissues of female shore crabs Carcinus maenas exposed to 1 mg Cd l⁻¹ in the water was investigated. Cadmium accumulation in all tissues examined was markedly increased in crabs in the postmoult stages (A and B) compared to crabs in all other moult stages. During the moult cycle, average cadmium accumulation in the midgut gland ranged from 29 μg Cd g⁻¹ dw at premoult stage (D₂) to 589 μg Cd g⁻¹ dw at postmoult stage (A). Average cadmium concentrations in the haemolymph ranged from 0.56 μg Cd ml⁻¹ at intermoult stage (C₄) to 4.6 μg Cd ml⁻¹ at postmoult stage (A), while the gills accumulated from 103 μg Cd g⁻¹ dw in intermoult stage (C₃) to 352 μg Cd g⁻¹ dw in postmoult stage (A). Cadmium concentration in gills and haemolymph was also significantly higher in crabs in late premoult stage (D₃) compared to C₄-crabs, while midgut gland cadmium concentration remained elevated in C₁- and C₃- intermoult stages relative to C₄. During ovarian maturation the cadmium accumulation in midgut gland, gills, ovaries and haemolymph decreased. Average cadmium concentration in the midgut gland decreased from 63 μg g⁻¹ dw in ovarian Stage I to 19 μg g⁻¹ dw in ovarian Stage VI. The same pattern was observed for gills, haemolymph and ovaries. The present study demonstrates that cadmium accumulation in the female shore crab strongly depends on the physiological status of the animal. A possible association between physiological calcium requirements and cadmium accumulation during moulting is discussed. Received: 20 January 2000 / Accepted: 20 July 2000