Advanced oxidation processes in the treatment of trifluraline effluent

The treatment of an effluent from the production of trifluraline was studied using a 1-L, semi-batch, tank-stirred glass reactor for performing three different advanced oxidation processes (photoperoxidation, Fenton, photo-Fenton). A commercial, medium-pressure mercury lamp was used for sample irradiation. The degradation was monitored by measurements of absorptiometric color reduction, UV-visible absorption spectra, and chemical oxygen demand (COD). The obtained results showed that the photo-Fenton process was the most effective treatment for the trifluraline effluent.     

Using nematodes in soil ecotoxicology

Nematodes represent a very abundant group of soil organisms and non-parasitic species are important for soil quality and in the soil food web. In recent years, it has been shown that nematodes are appropriate bioindicators of soil condition and they are also suitable organisms for laboratory toxicity testing. The aims of this paper are to overview and critically assess methods and approaches for researching soil nematode ecotoxicology. In natural ecosystems, nematode abundance and community structure analyses were proved to be sensitive indicators of stress caused by soil pollutants and ecological disturbance. Community structure analyses may be approached from a functional or ecological point of view; species are divided into groups according to their feeding habits or alternatively the maturity index is calculated according to their ecological strategy. Many environmental factors have the potential to affect nematode community, which consequently results in high space and time variability. This variance is major handicap in field ecotoxicological studies because pollutant-nematode relationships are obscured. For prospective risk assessment of chemicals, several toxicity tests with nematodes were developed and are increasingly used. Sensitivity of these tests is comparable to tests with other soil species (e.g. enchytraeids, earthworms and springtails) while tests are less demanding to space and time. Most studies have focused on metal toxicity but organic compounds are almost overlooked. Endpoints used in tests were often mortality, reproduction or movement, but more sublethal endpoints such as feeding or biomarkers have been used recently too. Although there is an increasing amount of knowledge in soil nematode ecotoxicology, there is still a lot of various issues in this topic to research.     

PCDDs, PCDFs, dioxin-like PCBs and indicator PCBs in soil from five selected areas in Slovakia

There is a lack of information regarding persistent organic pollutants (POPs) in soil from Slovakia. This paper reports the concentrations of 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), 12 dioxin-like polychlorinated biphenyls (dl-PCBs) and 6 indicator PCBs associated with 32 soil samples collected in 2007 from areas in the vicinity up to several kilometres from four selected industrial PCDD/F sources in Slovakia and one background area.The results show that the total WHO₁₉₉₈-PCDD/F/dl-PCB-TEQ concentrations varied from 0.34 to 18.05 pg g⁻¹ dry weight (dw) and the average total TEQ concentrations in samples collected at the Šala, Košice, Krompachy and Dubová areas were 3.18, 2.64, 7.80, and 3.19 pg g⁻¹ dw respectively. The average of the total WHO₁₉₉₈-TEQ values in three soil samples representing the background Starina area was 0.66 pg g⁻¹ dw. The predominant contaminants among 2,3,7,8-substituted PCDD/Fs, dl-PCB, and indicator PCBs was OCDD, PCB 118, and PCB 153 respectively. The major contributors to the TEQ were 2,3,4,7,8-PeCDF, PCB 126, 1,2,3,7,8-PeCDD, PCB 156 and 1,2,3,4,7,8-HxCDF + 1,2,3,4,7,9-HxCDF in descending order.     

Methylsulfonyl PCB and DDE metabolites and their enantioselective gas chromatographic separation in human adipose tissues, seal blubber and pelican muscle

In the present investigation, eleven human adipose tissue samples, two seal blubber samples and two pelican muscles samples were analyzed with regard to their concentrations of PCB parent compounds as well as to the respective chiral methylsulfonyl metabolites 3-MeSO2-CB 91, 4-MeSO2-CB 91, 3-MeSO2-CB 95, 4-MeSO2-CB 95, 3-MeSO2-CB 149, 4-MeSO2-CB 149, 3-MeSO2-CB 132, 4-MeSO2-CB 132, 3-MeSO2-CB 174, and 4-MeSO2-CB 174 and the achiral metabolites 3-MeSO2-CB 49, 4-MeSO2-CB 49, 3-MeSO2-CB 101, 4-MeSO2-CB 101, 3-MeSO2-CB 110, 4-MeSO2-CB 110 and 3-MeSO2-DDE. In order to verify enantioselective transformation processes and to compare the different enzymatic transformation pathways in birds and mammals, the enantioselective excesses of the chiral PCB-metabolites were determined by enantioselective gas chromatography with electron capture and mass spectrometric detection using modified cyclodextrin phases, including heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/OV1701 (1:1) for the parent PCBs and heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl-)-beta-cyclodextrin/SE52 (1:4) for the metabolites, respectively.     

Determination of trichloroacetic acid in environmental studies using carbon 14 and chlorine 36

Radioisotopes carbon 14 and chlorine 36 were used to elucidate the environmental role of trichloroacetic acid (TCA) formerly taken to be a herbicide and a secondary air pollutant with phytotoxic effects. However, use of ¹⁴C-labeling posed again known analytical problems, especially in TCA extraction from the sample matrix. Therefore—after evaluation of available methods—a new procedure using decarboxylation of [1,2-¹⁴C]TCA combined with extraction of the resultant ¹⁴C-chloroform with a non-polar solvent and its subsequent radiometric measurement was developed. The method solves previous difficulties and permits an easy determination of amounts between 0.4 and 20 kBq (10–500 ng g⁻¹) of carrier-less [1,2-¹⁴C]TCA in samples from environmental investigations. The procedure is, however, not suitable for direct [³⁶Cl]TCA determination in chlorination studies with ³⁶Cl. Because TCA might be microbially degraded in soil during extraction and sample storage and its extraction from soil or needles is never complete, the decarboxylation method—i.e. 2 h TCA decomposition to chloroform and CO₂ in aqueous solution or suspension in closed vial at 90 °C and pH 4.6 with subsequent CHCl₃ extraction—is recommended here, estimated V < 7%. Moreover, the influence of pH and temperature on the decarboxylation of TCA in aqueous solution was studied in a broad range and its environmental relevance is shown in the case of TCA decarboxylation in spruce needles which takes place also at ambient temperatures and might amount more than 10–20% after a growing season. A study of TCA distribution in spruce needles after below-ground uptake shows the highest uptake rate into current needles which have, however, a lower TCA content than older needle-year classes, TCA biodegradation in forest soil leads predominatingly to CO₂.     

Leaching of lead metallurgical slag in citric solutions--implications for disposal and weathering in soil environments

Metallurgical slags from primary lead smelting were submitted to a 30-day batch leaching procedure in 20 and 8 mM citric solutions in order to determine the kinetics of release of Pb, Cu, Zn and As. The experiment was coupled with the PHREEQC-2 speciation-solubility modelling and mineralogical study of newly formed products (SEM/EDS, XRD, TEM/EDS and Raman spectrometry). A strong scavenging of metals and metalloids from the 8 mM citric leachate was observed due to the formation of newly formed products. The secondary precipitate consisted of well-developed calcite (CaCO3) crystals and amorphous organo-mineral matrix composed of hydrous ferric oxides and amorphous SiO2. Metals (Pb, Zn, Cu) and arsenic released into the solution were subsequently bound onto the newly formed product (adsorption on oxides) or trapped within the calcite structure (Zn, Mn). Similar scavenging mechanism can be taken into account in real soil systems with lower concentration of citric acid. Then, the covering of slag dumps with a thick soil layer and subsequent re-vegetation might be a possible scenario for slag management on some metallurgical sites.     

Potential contribution of arbuscular mycorrhiza to cadmium immobilisation in soil

The contribution of arbuscular mycorrhiza (AM) to immobilisation of Cd in substrate was studied in two experiments. In the first experiment, substrates prepared by cultivating tobacco, either non-mycorrhizal or inoculated with the AM fungus Glomus intraradices were enriched with a range of Cd concentrations, and Cd toxicity in the substrates was assessed using root growth tests with lettuce as a test plant. The tests revealed lower Cd toxicity in the mycorrhizal than in the non-mycorrhizal substrate, and the difference increased with increasing total Cd concentration in the substrates. In the second experiment, extraradical mycelium (ERM) of G. intraradices exposed in vivo to Cd was collected and analysed on Cd concentration. The ERM accumulated 10–20 times more Cd per unit of biomass than tobacco roots. While Cd concentrations were lower in the biomass of mycorrhizal plants than of non-mycorrhizal plants, Cd immobilisation by ERM did not affect the total Cd content in mycorrhizal tobacco.

It is concluded that mycorrhiza may decrease Cd toxicity to plants by enhancing Cd immobilisation in soil. The results therefore suggest a potential role of AM symbiosis in the phytostabilisation of contaminated soils, where high Cd availability inhibits plant growth.     

Sorption, desorption, and degradation of (4-chloro-2-methylphenoxy)acetic acid in representative soils of the Danubian Lowland, Slovakia

Herbicide leaching through soil into groundwater greatly depends upon sorption-desorption and degradation phenomena. Batch adsorption, desorption and degradation experiments were performed with acidic herbicide MCPA and three soil types collected from their respective soil horizons. MCPA was found to be weakly sorbed by the soils with Freundlich coefficient values ranging from 0.37 to 1.03 mg^1−1/n kg⁻¹ L^1/n. It was shown that MCPA sorption positively correlated with soil organic carbon content, humic and fulvic acid carbon contents, and negatively with soil pH. The importance of soil organic matter in MCPA sorption by soils was also confirmed by performing sorption experiments after soil organic matter removal. MCPA sorption in these treated soils decreased by 37-100% compared to the original soils. A relatively large part of the sorbed MCPA was released from soils into aqueous solution after four successive desorption steps, although some hysteresis occurred during desorption of MCPA from all soils. Both sorption and desorption were depth-dependent, the A soil horizons exhibited higher retention capacity of the herbicide than B or C soil horizons. Generally, MCPA sorption decreased in the presence of phosphate and low molecular weight organic acids. Degradation of MCPA was faster in the A soil horizons than the corresponding B or C soil horizons with half-life values ranging from 4.9 to 9.6 d in topsoils and from 11.6 to 23.4 d in subsoils.     

Potential of olive mill wastes for soil C sequestration

The present work deals with the potential of olive mill wastes as a C source for soil C sequestration strategy, which is based on the high lignocellulosic content that makes these wastes to degrade slowly during composting and after land application. A C balance was performed during the whole life cycle of two different two-phase olive mill wastes (TPOMW): C losses were calculated during the composting process and after soil application of the composting mixtures under laboratory conditions. The effect of the degree of stabilization of TPOMW on the overall C waste conservation efficiency was also evaluated. C losses after 34 weeks of TPOMW composting ranged from 40.58% to 45.19% of the initial C, whereas the amount of C evolved as CO2 after 8 months of incubation of soil amended with mature composts only represented between 20.6% and 21.9% of the added C. The total C losses considering the whole life cycle of the TPOMW showed lower losses compared to composts prepared with organic residues of different origin. Conversely to the typical behaviour of other organic wastes, the stabilisation degree of the TPOMW composting mixtures did not show any significant effect on the total C losses measured during composting and later land application. The low rate of degradation of TPOMW both during composting and after soil application makes the use of TPOMW as a C source an attractive strategy for soil C sequestration.     

Thyroid ultrasound volume, structure and function after long-term high exposure of large population to polychlorinated biphenyls, pesticides and dioxin

We examined 2,046 adults (834 males and 1,212 females aged 20-75 years) from polluted district in East Slovakia (POLL) and two neighboring upstream and upwind located districts of background pollution (BCGR). By ultrasound we estimated the thyroid volume (ThV), hypoechogenicity (HYE), nodules and cysts. Serum levels of thyrotropin (TSH), thyroperoxidase antibodies (TPOab) and thyroglobulin were estimated by electrochemiluminiscent assay and these of 15 PCB congeners, p,p'-DDE, p,p'-DDT, hexachlorobenzene (HCB) and hexachlorocyclohexane by high-resolution gas chromatography. In 320 subjects also selected hydroxylated and methylsulfonated PCB metabolites, polychlorinated dibenzo-dioxins (PCDDs), -furans (PCDFs), five dioxin-like coplanar and eight mono-ortho PCB congeners were estimated. Urinary iodine was measured by automatic microplate method. Reciprocal positive association was found between three major POPs (PCBs, DDE and HCB), the levels of these and also PCDDs plus PCDFs in polluted area being considerably higher than in background pollution area. ThV in groups of males and females from POLL with high PCBs level was significantly higher (p<0.001 by t-test) then in age and sex matched groups from BCGR with low PCBs level. In 1,048 males and females aged <60 years with serum PCBs level >1,000 ng g(-1) lipid (median=1,756 ng g(-1)) a significant effect of age on ThV was found (p<0.01 by ANOVA), while in 921 respective subjects with PCBs level <1,000 ng g(-1) (median=661 ng g(-1)) it was not. These findings supported the view on the additional effect of PCBs on ThV other than that of age. Since the urinary iodine in both districts showed optimal range, any interfering effect of unsatisfactory iodine intake on ThV may be excluded. The frequency of autoimmune thyroiditis signs such as HYE, increased serum level of TPOab and TSH resulting in subclinical or overt thyroid hypofunction was positively associated with sex, age and organochlorine levels. The increase of such frequency in males with POPs levels was much more abrupt than that in females. No considerable differences in the frequency of thyroid nodules as related to PCBs level were found.