PCDD/F and dioxin-like PCB profiles in soils amended with sewage sludge, compost, farmyard manure, and mineral fertilizer since 1962.

BACKGROUND, AIM, AND SCOPE: Biowaste contains compounds of agricultural value such as organic carbon, nutrients, and trace elements and can partially replace mineral fertilizer (MIN) and improve the physical properties of the soil. However, the obvious benefits of land spreading need to be carefully evaluated against potential adverse effects on the environment and human health. Environmental contamination resulting from biowaste application is one of the key variables when assessing cost/benefits. This study provides data on the resulting concentration of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in the soil column as a result of the different types of fertilizers. MATERIALS AND METHODS: In a long-term field experiment established in 1962, we investigated the influence of the application of biowaste-derived fertilizers such as sewage sludge (SSL), compost (COM), and farmyard manure (FYM) to a luvisol derived from loess on the contents of PCDD/Fs and DL-PCBs. Control plots amended only with MIN served as a basis to compare the biowaste-amended soils with soils affected only by atmospheric deposition, thus experimentally separating the two pathways of soil contamination. Samples of the soil column down to a depth of 90 cm were taken in 2001 and analyzed for PCDD/Fs and dioxin-like PCBs according to US-EPA methods 1613 and 1668, respectively. RESULTS: Thirty-nine years of experimental SSL and COM applications exceeding four times the maximal amount as laid down in German legislation resulted in a doubling of the international toxicity equivalent (I-TEQ) budget for PCDD/Fs and a threefold increase for DL-PCBs as compared to test plots amended with MIN only. As compared to MIN, the application of FYM had no effect on the PCDD/F and PCB content in soil. The average contribution of the DL-PCBs to the WHO-TEQ was 19% in the MIN and FYM plots and somewhat higher in the COM (23%) and in the SSL (27%) plots. DISCUSSION: Although the test plots received four times the maximum application of SSL as laid down in the German SSL ordinance and the investigated region represents the upper end of the topsoil concentrations typically found in Germany, the soils treated with SSL and COM were still a factor of 4 below the German guideline value of PCDD/Fs for arable land. No enhancement of translocation of PCDD/Fs and PCBs into the corresponding subsoils due to the presence of dissolved humic matter or other surfactants potentially present in the biowaste was observed. The similarity of congener patterns in all soils, irrespective of the type of fertilizer applied, points towards atmospheric deposition of PCDD/Fs and DL-PCBs as the main intake route in the soils. The higher levels in the SSL- and COM-amended soils can be explained by the fact that both biowastes are subject to atmospheric deposition occurring at their origin. In the case of COM, it is accumulation in the foliage, while in the case of SSL, atmospheric particulate from wet and dry deposition is collected in the wastewater treatment system via urban runoff. CONCLUSIONS: It appears that the common practice of SSL applications in Germany does not pose a current threat to the agro-environment with regard to PCDD/Fs and DL-PCBs. However, time trend data on PCDD/Fs in SSL-amended soils will be needed to obtain a prognosis about the long-term effect of biowaste applications on soil quality.

Sorption-desorption behavior of atrazine on soils subjected to different organic long-term amendments.

Sorption of atrazine on soils subjected to three different organic amendments was measured using a batch equilibrium technique. A higher K(F) value (2.20 kg(-1)(mg L(-1))(-N)) was obtained for soil fertilized with compost, which had a higher organic matter (OM) content. A correlation between the K(FOC) values and the percentage of aromatic carbon in OM was observed. The highest K(FOC) value was obtained for the soil with the highest aromatic content. Higher aromatic content results in higher hydrophobicity of OM, and hydrophobic interactions play a key role in binding of atrazine. On the other hand, the soil amended with farmyard manure had a higher content of carboxylic units, which could be responsible for hydrogen bonding between atrazine and OM. Dominance of hydrogen bonds compared to hydrophobic interactions can be responsible for the lower desorption capacity observed with the farmyard manure soil. The stronger hydrogen bonding can reduce the leaching of atrazine into drinking water resources and runoff to rivers and other surface waters.

Influence of different organic amendments on the potential availability of metals from soil: a study on metal fractionation and extraction kinetics by EDTA.

The effects of long-term application of different organic amendments, as compared to mineral fertilizer, on Zn, Cu and Pb content and leachability in a luvisol derived from loess were assessed. The organic fertilizers, applied since 1962, were compost (COM) - from green organic household waste, sewage sludge (SLU) - from municipal water treatment facilities, farmyard manure (FYM) and the doses applied since 1997 were 90tha(-1), 10tha(-1) and 9tha(-1), once in 3years, respectively. The kinetics of metals extraction with 0.05moldm(-3) EDTA at pH 6.0 has been studied. The two first-order reactions model was fitted to the kinetic data and allowed to distinguish two pools for each metal: a "labile" fraction (Q(1)), quickly extracted with a rate constant k(1), and a "moderately labile" fraction (Q(2)), more slowly extracted, with a rate constant k(2). Simultaneously, the pseudo-total metal contents in the soil samples were determined after digestion with aqua regia (3:1 HCl+HNO(3)). The obtained parameters Q(1), k(1), Q(2), k(2), for the kinetics of extraction of each metal in the three replicates of each fertilization mode, as well as the pseudo-total metal contents, were statistically analysed. COM and SLU application resulted in an increase of the total contents of Pb, Zn and Cu in soil. Further, the percentage of labile Zn and Pb also increased in consequence of the application of those amendments, particularly COM. The increase was more noticeable for Zn. FYM, despite not increasing the total content of Pb, Zn or Cu, did also have an effect on the leachability of Zn and Pb, increasing their labile fraction in soil. These results point to a potential risk of increasing metals mobility in soil, mainly Zn, associated to the use of organic amendments, particularly COM or SLU.

Zea mays: benzoxazolinone detoxification under sulfur deficiency conditions--a complex allelopathic alliance including endophytic Fusarium verticillioides.

Benzoxazolinone detoxification is similar in plants grown under sulfur deficiency conditions and in control plants grown with an optimal S supply. However, when S-deficient plants were treated with metolachlor before benzoxazolin-2(3H)-one (BOA) incubation, detoxification was reduced, as indicated by a lower accumulation of the detoxification products BOA-6-O-glucoside and glucoside carbamate and by a loss of BOA-6-OH glucosyltransfease activity. Root colonizing microorganisms and the endophytic fungus Fusarium verticillioides participated in benzoxazolinone detoxification by converting the compound to 2-acetamidophenol (AAP) or O-hydroxyphenyl malonamic acid (OHPMA), a process accompanied by the appearance of phenoxazinone. Maize roots, however, absorbed AAP and OHPMA only in traces. Absorbed traces of OHPMA stimulated maize radicle growth, and traces of AAP stimulated cress. Phenoxazinone inhibited the growth of cress radicles at concentrations higher than 500 microM, whereas maize radicles were hardly affected. F. verticillioides did not convert benzoxazolinone to any known microbial degradation product when the medium of maize seedlings was inoculated with the fungus under sterile condition. Plant-fungus interactions seem to be important in plant survival of allelopathic attacks. This study points to a complicated network of allelopathic interactions that are influenced by biotic and abiotic factors, including herbicides.