Photolysis of 14C-sulfadiazine in water and manure

Photolysis of 14C-sulfadiazine in aqueous solution under simulated sunlight followed first-order kinetics. The impact of H2O2, humic acid, fulvic acid and acetone to enhance the photodegradation of sulfadiazine (SDZ) was studied. Six photoproducts, 4-OH-SDZ, 5-OH-SDZ, N-formyl-SDZ, 4-[2-iminopyrimidine-1(2H)-yl] aniline, 2-aminopyrimidine, and aniline were identified. Extrusion of SO2 was found to be the main degradation process during irradiation. These photoproducts can occur in water and soil upon sunlight exposure, when soil is treated with SDZ contained in manure. Due to photodegradation the experimental half-life of the SDZ in water was 32h and in the presence of photosensitizers the half-life values were 19.3-31.4h, 17.2-31.4h, 12.6-29.8h, and 3.8-30.7h for H2O2, humic acid, fulvic acid, and acetone, respectively depending on the concentration of the photosensitizers. The presence of photosensitizers markedly reduced SDZ persistence, indicating that indirect photolytic processes are important factors governing the photodegradation of SDZ in aqueous environments. Investigation revealed further persistence behavior of SDZ in manure. The half-life value of SDZ in manure was 158h.     

The degradation of dissolved organic nitrogen associated with melanoidin using a UV/H2O2 AOP

The aim of this study was to examine the simultaneous degradation of dissolved organic nitrogen (DON) and associated colour from wastewater containing melanoidins by an advanced oxidation process (AOP). UV irradiation of H2O2 was used as the mechanism to create the hydroxyl radical for oxidation. Melanoidins are large nitrogenous organic compounds that are refractory during biological wastewater treatment processes. The simultaneous degradation of DON and colour, present as a result of these compounds, was investigated using an AOP. The oxidation process was much more capable of removing colour (99% degradation), dissolved organic carbon (DOC) (50% degradation) and DON (25% degradation) at the optimal applied dose of hydrogen peroxide for the system (3300 mg l(-1)). This indicated that colour and DON removal were decoupled problems for the purpose of treating melanoidin by an AOP and thus colour removal can not be used as an indication of DON removal Colour was caused by organic molecules with molecular weight greater than 10 kDa. Oxidation caused a partial reduction of the DON (41-15% of the total dissolved nitrogen) and DOC (29-14% of the DOC) associated with the large molecular weight fraction (>10 kDa) and almost complete colour removal (87-3% of the total colour). The degraded DON was mostly accounted for by the formation of ammonia (31% of the nitrogen removed from the large fraction) and small molecular weight compounds (66% of the nitrogen removed from the large fraction). The degraded DOC appeared to be mostly mineralised (to CO2) with only 20% of the degraded compounds appearing as small molecular weight DOC.     

ECOSAR model performance with a large test set of industrial chemicals

The widely used ECOSAR computer programme for QSAR prediction of chemical toxicity towards aquatic organisms was evaluated by using large data sets of industrial chemicals with varying molecular structures. Experimentally derived toxicity data covering acute effects on fish, Daphnia and green algae growth inhibition of in total more than 1,000 randomly selected substances were compared to the prediction results of the ECOSAR programme in order (1) to assess the capability of ECOSAR to correctly classify the chemicals into defined classes of aquatic toxicity according to rules of EU regulation and (2) to determine the number of correct predictions within tolerance factors from 2 to 1,000. Regarding ecotoxicity classification, 65% (fish), 52% (Daphnia) and 49% (algae) of the substances were correctly predicted into the classes "not harmful", "harmful", "toxic" and "very toxic". At all trophic levels about 20% of the chemicals were underestimated in their toxicity. The class of "not harmful" substances (experimental LC/EC(50)>100 mg l(-1)) represents nearly half of the whole data set. The percentages for correct predictions of toxic effects on fish, Daphnia and algae growth inhibition were 69%, 64% and 60%, respectively, when a tolerance factor of 10 was allowed. Focussing on those experimental results which were verified by analytically measured concentrations, the predictability for Daphnia and algae toxicity was improved by approximately three percentage points, whereas for fish no improvement was determined. The calculated correlation coefficients demonstrated poor correlation when the complete data set was taken, but showed good results for some of the ECOSAR chemical classes. The results are discussed in the context of literature data on the performance of ECOSAR and other QSAR models.     

Different reaction mechanisms of diphenylether and 4-bromodiphenylether with nitrous acid in the 355 nm laser flash photolysis of mixed aqueous solution

The microscopic reaction mechanisms of diphenylether (DPE) and 4-bromodiphenylether (4-BrDPE) with nitrous acid (HNO(2)) in the absence of O(2) have been explored by the 355nm laser flash photolysis. It was proposed that OH radical, from the photolysis of HNO(2), added to DPE forms the C(12)H(10)O-OH adduct while added to 4-BrDPE forms the 4-BrDPE-OH and 4-BrOH-DPE adducts. The first-order decay rate constants of the C(12)H(10)O-OH adduct, 4-BrDPE-OH adduct and 4-BrOH-DPE adduct were measured to be (1.86+/-0.14)x10(5)s(-1), (2.19+/-0.04)x10(5)s(-1) and (1.56+/-0.03)x10(5)s(-1), respectively. The final photolysis products of DPE and HNO(2) identified by GC/MS analysis were phenol, o-hydroxydiphenylether, p-hydroxydiphenylether and p-nitrodiphenylether, while the final photolysis product of 4-BrDPE and HNO(2) identified by LC/MS analysis was mainly the dimer.     

Levels and trends of HBCD and BDEs in the European and Asian environments, with some information for other BFRs

In this paper, we review recent data for brominated flame retardants (particularly BDEs, HBCD and TBBP-A) in samples from the European and Asian environments, including recent temporal trend studies. Research is active and we cite over 100 studies published during 2005-2007. Environmental compartments studied comprise the atmosphere, indoor and outdoor air, sewage sludges, soils and sediments and a variety of biological samples and food chains. Findings include that the lack of reference materials for use in analytical quality control and method validation identified earlier has been addressed, and certified concentrations are now available for a number of BDE congeners in six pre-existing and one new reference materials. BDE209 was certified in three samples of indoor dust. The analysis of BDE209 remains problematic, but suitable methods for its determination are available and need to be applied. The contamination of indoor environments with BFRs has been recognised as representing a significant uptake pathway, particularly via dust. Additional data for TBBP-A are needed from areas, where it is produced and used, primarily Asia, as the worst-case scenario. As a reactive flame retardant it is less likely to leach from finished products. Also, issues regarding the importance of e-waste recycling as a source of BFRs to the local populations and the local environment require urgent study, certainly in China and possibly elsewhere. Generally, trends show a levelling in concentrations of BDEs and increases in concentrations of HBCD wherever determined and BDE209 in Asia.     

Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Spatial trends of polyfluorinated compounds in guillemot (Uria aalge) eggs from North-Western Europe

Polyfluorinated alkyl compounds (PFCs) are a group of chemicals of growing concern that have been detected in biological and abiotic samples worldwide. This study reports the concentrations of a suite of PFCs: perfluorooctyl sulfonate (PFOS), perfluorooctyl sulfonamide (PFOSA) and perfluorinated carboxylic acids (PFCAs) in guillemot (Uria aalge) eggs, collected in North-Western Europe, from Iceland, the Faroe Islands, Sweden and two locations in Norway. The highest concentrations of PFOS were found in samples from Sweden (mean 400 ng g(-1) wet weight (w.w.)), which were almost five times higher than concentrations found in Norwegian samples (mean 85 ng g(-1)w.w. from both sample sites). The concentrations found in Icelandic and Faroe samples were lowest (mean 16 and 15 ng g(-1)w.w., respectively). Only Swedish samples differed significantly from the other locations. In general, PFCAs show a different spatial trend than PFOS. Perfluorooctanoic acid (PFOA) was not detected in any sample and perfluorononanoic acid (PFNA) was only detected in samples from Sweden. The most abundant PFCA was perfluoroundecanoic acid (PFUA) with highest concentrations in samples from Sweden (mean 82 ng g(-1)w.w.), samples from the Faroe Islands had the second highest concentration (mean 57 ng g(-1)w.w.) and samples from Iceland and Norway had concentrations ranging between 18 and 30 ng g(-1)w.w. The original hypothesis was based on the idea that PFC concentrations are the highest close to more densely populated and industrialized areas and lower levels in remote areas. However, the geographic pattern is more complicated than predicted and varies among different PFCs.     

Significance of urinary arsenic speciation in assessment of seafood ingestion as the main source of organic and inorganic arsenic in a population resident near a coastal area

In order to characterize the different sources of exposure to arsenic (As), urinary excretion of total As, the sum of inorganic As+MMA+DMA determined by the hydride generation-atomic absorption spectrophotometry technique, and the species As(3), As(5), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and arsenobetaine were determined in 49 workers at a steel foundry, with presumed occupational exposure to As, and 50 subjects from the general population, all males. No evidence of occupational exposure to As resulted from environmental monitoring performed in the foundry, although the analysis of minerals used as raw materials showed the presence of As, particularly in fossils and fine ores. The urinary concentrations of As(3), MMA, DMA, the sum of inorganic As+MMA+DMA and total As were not different in the two groups, while arsenobetaine appeared significantly higher in the controls than in the workers. The different species of urinary As were all significantly correlated. Urinary excretion of As(3) was associated with the consumption of mineral water and with residence in an industrial zone, while MMA, DMA, arsenobetaine, the sum of inorganic As+MMA+DMA and total As urinary excretion were associated with the consumption of crustaceans and/or shellfish 3 days or less before urine collection. Multiple regression analysis confirmed these results. In conclusion, in populations with a high consumption of seafood, living in areas characterized by coastal/marine As pollution, only speciation of As can identify a prevalent role of environmental sources, like the consumption of seafood contaminated by As, in determining urinary As excretion, and exclude an occupational origin of the exposure.     

Effects of arbuscular mycorrhizal inoculation on plants growing on arsenic contaminated soil

Arbuscular mycorrhizal fungi (AMF) may play an important role in phytoremediation of As-contaminated soil. In this study the effects of AMF (Glomus mosseae, Glomus intraradices and Glomus etunicatum) on biomass production and arsenic accumulation in Pityrogramma calomelanos, Tagetes erecta and Melastoma malabathricum were investigated. Soil (243 +/- 13 microg As g(-1)) collected from Ron Phibun District, an As-contaminated area in Thailand, was used in a greenhouse experiment. The results showed different effects of AMF on phytoremediation of As-contaminated soil by different plant species. For P. calomelanos and T. erecta, AMF reduced only arsenic accumulation in plants but had no significant effect on plant growth. In contrast, AMF improved growth and arsenic accumulation in M. malabathricum. These findings show the importance of understanding different interactions between AMF and their host plants for enhancing phytoremediation of As-contaminated soils.     

Maternal transfer of brominated flame retardants in zebrafish (Danio rerio)

In many species reproduction and embryonic development have been shown to be sensitive to environmental contaminants. Understanding embryonic exposure to environmental contaminants is thus highly important. In this study concentrations of brominated flame retardants (BFRs) were measured in zebrafish eggs after parental exposure for 42 days via the diet. Zebrafish were exposed to two doses of eleven structurally-diverse BFRs. Eight BFRs were detected in the female zebrafish and maternal transfer to eggs was evident for all eight compounds. The highest concentrations in eggs were observed for hexabromocyclododecane (HBCD) and 2,4,4'-tribromodiphenyl ether (BDE 28), followed by 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE 183) and tetrabromobisphenol A 2,3-dibromopropyl ether (TBBPA DBPE). Five potential BFR metabolites were tentatively identified in female fish and maternal transfer was observed also for these compounds. The lipid adjusted concentrations in eggs were significantly higher than the concentrations in female fish for several of the BFRs. Further, the results showed a generally higher transfer in the lower exposure level and also indicated a dependency on the physico-chemical properties of the compounds.