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.     

Characterizing effects of uncertainties in MSW composting process through a coupled fuzzy vertex and factorial-analysis approach

A coupled fuzzy vertex and factorial-analysis approach was developed in this study for systematically characterizing effects of uncertainties in a municipal solid waste composting process. A comprehensive composting process model was also embedded into the system framework and used to address substrate decomposition and biomass growth, as well as the interactions between moisture contents, temperatures, and oxygen concentrations. The applicability of the proposed method was verified through a custom-made pilot-scale composting system. Results from fuzzy simulation indicated that the fuzzy vertex method could effectively communicate implicit knowledge into dynamic simulations and thus provide valuable information for enhancing composting process control under uncertainty. The factorial analysis was effective in quantifying the proportion to which the uncertainty of each single or interactive effect of model parameters contributes to the overall uncertainty of the system outcomes. Thus, sensitive parameters that may lead to errors or unreasonable predictions can be determined. The proposed study system could not only be used in characterizing combined effects of uncertainties for composting processes, but was also applicable to many other environmental modelling systems.     

Assessing the Geographic Representativeness of Genebank Collections: the Case of Bolivian Wild Potatoes

Abstract: Genebank collection databases can be used for ecogeographical studies under the assumption that the accessions are a geographically unbiased sample. We evaluated the representativeness of a collection of wild potatoes from Bolivia and defined and assessed four types of bias: species, species-area, hotspot, and infrastructure. Species bias is the sampling of some species more often than others. Species-area bias is a sampling that is disproportionate to the total area in which a species is found. Hotspot bias is the disproportionate sampling of areas with high levels of diversity. Infrastructure bias is the disproportionate sampling of areas near roads and towns. Each of these biases is present in the Bolivian wild potato collection. The infrastructure bias was strong: 60% of all wild potato accessions were collected within 2 km of a road, as opposed to 22%, if collections had been made randomly. This analysis can serve as a guide for future collecting trips. It can also provide baseline information for the application of genebank data in studies based on geographic information systems.     

Genetic protein variation in red mullet (Mullus barbatus) and striped red mullet (M. surmuletus) populations from the Mediterranean Sea

Starch-gel electrophoresis of allozymes was used to differentiate the two red mullet species (Mullus barbatus L. and M. surmuletus L.) in the Mediterranean Sea and, further, to investigate the genetic stock structure of M. barbatus in the eastern Mediterranean area. Twenty putative enzyme-coding loci were examined in eight M. barbatus samples caught in the Aegean and Ionian Seas (Greece) and in the Gulf of Lion (France), and two M. surmuletus samples caught in the Aegean and Gulf of Lion. A high degree of genetic polymorphism was found in both species. Species-specific electrophoretic patterns were found in PGI* and PGM*. Estimates of variance of allele frequencies among samples (F _ST) and ² analyses both revealed significant differences (P < 0.05) among the M. barbatus samples. Most of the genetic variation was among samples regardless of region. The mean value of Nei's genetic distance between the two species was 0.329. Genetic distance among M. barbatus samples was low (maximum Nei's D = 0.012), with the sample from Platania differing most from other M. barbatus samples. This is probably be due to founder effects existing at this area. These results suggest that allozyme analysis may provide important information on the genetic structure of the red mullet to ensure sustainable management of this species. Received: 7 May 1997 / Accepted: 13 October 1997     

Context dependency and generality of fever in insects

Fever can reduce mortality in infected animals. Yet, despite its fitness-enhancing qualities, fever often varies among animals. We used several approaches to examine this variation in insects. Texas field crickets (Gryllus texensis) exhibited a modest fever (1 °C increase in preferred body temperature, T _pref) after injection of prostaglandin, which putatively mediates fever in both vertebrates and invertebrates, but they did not exhibit fever during chronic exposure to heat-killed bacteria. Further, chronic food limitation and mating status did not affect T _pref or the expression of behavioural fever, suggesting limited context dependency of fever in G. texensis. Our meta-analysis of behavioural fever studies indicated that behavioural fever occurs in many insects, but it is not ubiquitous. Thus, both empirical and meta-analytical results suggest that the fever response in insects ‘is widespread, although certainly not inevitable’ (Moore 2002). We highlight the need for future work focusing on standardizing an experimental protocol to measure behavioural fever, understanding the specific mechanism(s) underlying fever in insects, and examining whether ecological or physiological costs often outweigh the benefits of fever and can explain the sporadic nature of fever in insects.     

Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Effects of pH, organic acids, and competitive cations on mercury desorption in soils

The effects of pH, organic acids, and competitive cations on Hg(2+) desorption were studied. Three representative soils for rice production in China, locally referred to as a yellowish red soil (YRS), purplish clayey soil (PCS), and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were, respectively, collected from Jiaxin County, Deqing County, and Xiasha District of Hangzhou City, Zhejiang Province. Most of the added Hg(2+) was adsorbed at low initial concentrations (<2 mg l(-1)). Desorption of the adsorbed Hg(2+) in 0.01M KCl (simulating soil solution) was minimal, but was significantly enhanced by the change of pH, and the presence of organic acids or competitive cations. The desorption of Hg(2+) in the soils decreased with pH from 3.0 to 5.0, leveled off at pH 5.0-8.0, but increased with pH from 7.0 to 9.0. The presence of organic ligands enhanced Hg(2+) desorption in the soils except for YRS, in which the addition of tartaric, malic, or oxalic acid reduced Hg(2+) desorption at low concentrations (<10(-4)M), but Hg(2+) desorption generally increased with organic acid concentration. Citric acid was most effective in increasing Hg(2+) desorption, followed by tartaric acid and malic acid; and oxalic acid was the least effective. Desorption of adsorbed Hg(2+) increased with increasing concentrations of added Cu(2+) or Zn(2+). Applied Cu(2+) increased Hg(2+) desorption more than Zn(2+) at the same loading rate. CAPSULE: The effects of organic acids and competitive cations on Hg desorption in soil-water system are related to their concentrations, basic chemical properties, and soil properties.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

Zinc and cadmium accumulation and tolerance in populations of Sedum alfredii

To investigate the variation of Zn and Cd accumulation and tolerance of Sedum alfredii (a newly reported Zn/Cd hyperaccumulator), field surveys and hydroponic experiments were conducted among three populations of this species: two originating from old Pb/Zn mines in Zhejiang (ZJ) and Hunan (HN) Provinces and one from a "clean" site in Guangdong (GD) Province, China. Under field conditions, up to 12,524 and 12,253 mg kg(-1) Zn, and 1400 and 97 mg kg(-1) Cd in shoots of ZJ and HN plants were recorded respectively. Under hydroponic conditions, ZJ and HN plants accumulated significantly higher Zn and Cd in their leaves and stems, and possessed significantly higher Zn and Cd tolerance than GD plants. Among the two contaminated populations, ZJ plants showed higher Cd tolerance and accumulation (in leaves) than HN plants. The present results indicate that significant differences in Zn and Cd accumulation and tolerance exist in populations of S. alfredii.