Distribution,fate and formation of non-extractable residues of a nonylphenol isomer in soil with special emphasis on soil derived organo-clay complexes

Anthropogenic contaminants like nonylphenols (NP) are added to soil, for instance if sewage-sludge is used as fertilizer in agriculture. A commercial mixture of NP consists of more than 20 isomers. For our study, we used one of the predominate isomers of NP mixtures, 4-(3,5-dimethylhept-3-yl)phenol, as a representative compound. The aim was to investigate the fate and distribution of the isomer within soil and soil derived organo-clay complexes. Therefore, ¹⁴C- and ¹³C-labeled NP was added to soil samples and incubated up to 180 days. Mineralization was measured and soil samples were fractionated into sand, silt and clay; the clay fraction was further separated in humic acids, fulvic acids and humin. The organo-clay complexes pre-incubated for 90 or 180 days were re-incubated with fresh soil for 180 days, to study the potential of re-mobilization of incorporated residues. The predominate incorporation sites of the nonylphenol isomer in soil were the organo-clay complexes. After 180 days of incubation, 22 % of the applied ¹⁴C was mineralized. The bioavailable, water extractable portion was low (9 % of applied ¹⁴C) and remained constant during the entire incubation period, which could be explained by an incorporation/release equilibrium. Separation of organo-clay complexes, after extraction with solvents to release weakly incorporated, bioaccessible portions, showed that non-extractable residues (NER) were preferentially located in the humic acid fraction, which was regarded as an effect of the chemical composition of this fraction. Generally, 27 % of applied ¹⁴C was incorporated into organo-clay complexes as NER, whereas 9 % of applied ¹⁴C was bioaccessible after 180 days of incubation. The re-mobilization experiments showed on the one hand, a decrease of the bioavailability of the nonylphenol residues due to stronger incorporation, when the pre-incubation period was increased from 90 to 180 days. On the other hand, a shift of these residues from the clay fraction to other soil fractions was observed, implying a dynamic behavior of incorporated residues, which may result in bioaccessibility of the NER of nonylphenol.     

Rain‐washing of foliar deposits of Dimilin®WP‐25 formulated in four different carrier liquids

Abstract

Dimilin^® WP‐25, a wettable powder formulation of diflubenzuron (DFB) [1‐(4‐chlorophenyl)‐3‐(2,6‐difluorobenzoyl) urea], was formulated in four different carrier liquids, viz., water; a light petroleum paraffinic oil, ID 585; a heavy paraffinic oil, Sunspray^® 7N; and a 1:2 mixture of a light petroleum aromatic solvent (Cyclosol^® 63) and canola oil; to provide four end‐use mixtures, Dim‐W, Dim‐585, Dim‐7N and Dim‐Cy‐C respectively, each containing 28 g of DFB per litre. Balsam fir branch tips clipped from greenhouse‐grown seedlings, and sugar maple branch tips clipped from field‐grown young trees, were exposed to uniform‐sized droplets (ranging in diameters from 135 to 190 μm) of the four end‐use mixtures which were atomized using a monodispersed droplet generator. Droplets were collected on the fir and maple branch tips and the initial residue per g fresh weight of foliage was determined by high‐performance liquid chromatography (HPLC). The branch tips were exposed to cumulative rainfall of 3, 6 and 10 mm at an intensity of 5 mm/h and at time intervals of 1, 12, 36 and 72 h after DFB treatment, to test the influence of ‘ageing’ of foliar residues on rainfastness. Foliar samples were collected for residue determination just before the onset of rainfall, and at 0.5 h post‐rain. DFB was quantified by the HPLC method. In the case of fir foliage, the Dim‐W formulation was the most susceptible to rain‐washing and the rainfastness did not increase with the ageing period of foliar deposits. In contrast, the three oil‐based mixtures showed greater rainfastness depending upon the carrier liquid and the ageing period. Rainfastness decreased in the order of Dim‐Cy‐C > Dim‐7N > Dim‐585 > Dim‐W. In contrast, the data on maple foliage indicated that the ageing of deposits increased the rainfastness of all the 4 end‐use mixtures. Dim‐585 was the most susceptible to rain washing, and rainfastness decreased in the order of Dim‐W > Dim‐Cy‐C > Dim‐7N > Dim‐585.     

Ozone-driven photocatalyzed degradation and mineralization of pesticide,Triclopyr by Au/TiO2

Triclopyr is a widely used pesticide which is non-biodegradable and enters aquatic systems. The ozone facilitated photocatalyzed degradation and mineralization of Triclopyr using Au-loaded titania as heterogeneous catalyst is reported. The oxidative degradation activity of the hazardous pesticide was investigated at pH 7.8 under varied reaction conditions, including in presence and absence of ozone, titania alone, in presence and absence of light and with different loadings of Au on support. Photocatalysis with 2% Au/TiO₂ in the presence of ozone yielded 100% degradation of Triclopyr in 2 h. The extent of degradation of pesticide and its mineralization were confirmed by GC-MS. For 10 mg/L of Triclopyr, 0.1 g/L of catalyst was found to be the optimum for mineralization. Results show that photocatalyzed ozonation with Au/TiO₂ as catalyst is a very effective for its removal. No leaching of Au was observed in triplicate runs. Catalyst was fully recoverable and reusable with no loss of activity.     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Interannual Changes in the C:N:P Ratios of Seston and Zooplankton of a High Mountain Lake in Sierra Nevada,Spain

We investigated the carbon, nitrogen and phosphorus content inthe seston and the zooplankton of a high-mountain lake duringthree years of contrasting physical and chemical conditions.Carbon in seston was ten times higher in 1995 than in 1996 and1997. Phosphorus content in seston was variable for the studyperiod, increasing gradually towards late summer in 1995, butpeaking abruptly in 1996 and 1997, reflecting atmosphericdepositions. Seston C:P were high and did not fit any definitepattern in 1995, and were particularly low after the thaw, increasing towards mid-summer in 1996 and 1997. As the seasonprogressed, major decreases in these ratios occurred coincidingwith important atmospheric inputs in the lake area. ZooplanktonN:P and C:P were negatively associated to the appearance ofrotifers and copepod nauplii in 1995, but positively correlatedto the ontogenetic development of the most abundant species,Mixodiaptomus laciniatus, in 1996. Seasonal variations inzooplankton N:P and C:P ratios showed limited interannual, butlarge intraannual variability. The comparison between the bulkcarbon in seston and zooplankton demands for this elementindicated that zooplankton were above food-quantity thresholdsfor maximum growth in 1995, 1996 and mid-season of 1997,therefore suffering only from food-quantity constraints afterthe thaw (nauplii dominance) and towards late season (adultdominance) in the latter year. The high C:P ratios in sestonrelative to zooplankton in 1995 imply that the zooplankton mayhave faced severe food-quality constraints (in terms ofphosphorus) during this year. Differences between bulkzooplankton and seston elemental nutrients are also discussed inrelation to the competitive abilities of species, andparticularly of Daphnia.     

Monitoring of eutrophication and nutrient limitation in the Izmir Bay (Turkey) before and after Wastewater Treatment Plant

The distribution of inorganic nutrients and phytoplankton chlorophyll-a was investigated and N/P ratios were determined in Izmir Bay during 1996-2001. The average concentrations showed ranges of 0.01-0.19 and 0.01-10 microM for phosphate-phosphorus; 0.11-1.8 and 0.13-27 microM for (nitrate+nitrite)-nitrogen, 0.30-4.1 and 0.50-39 microM for silicate and 0.02-4.3 and 0.10-26 microg l(-1) for chlorophyll-a in the outer and middle-inner bays, respectively. The results are compared with the values obtained from the relatively unpolluted waters of the Aegean Sea. The N/P ratio is significantly lower than the assimilatory optimal (N/P=15:1) in conformity with Redfield's ratio N/P=16:1. Nitrogen is the limiting element in the Izmir Bay. Phosphate, which originates from detergents, is an important source for eutrophication in the bay, especially in the inner bay. In early 2000, a Wastewater Treatment Plant (WTP) began to treat domestic and industrial wastes. This plant treats the wastes about 60% capacity between 2000 and 2001. The sampling periods cover before and after treatment plant. Although the capacity of wastewater plant is sufficient for removal of nitrogen from the wastes, it is inadequate for removal of phosphate. This is also in accordance with the decreasing N/P ratios observed during 2000-2001 (after WTP) in the middle-inner bays.     

Nitrogen Budget of a Spruce Forest Ecosystem After Six-year Addition of Ammonium Sulphate in Southwest Sweden

A nitrogen (N) budget was constructed for a period of 6 years (1988–1993) in a Norway spruce stand with current deposition of 19 kg N and 22 kg S ha⁻¹ year⁻¹. The stand was fertilized annually by addition of 100 kg N and 114 kg S ha⁻¹ (NS). Above and below ground biomass, litterfall, fine- root litter production, soil solution and net mineralization were measured to estimate pools, fluxes and accumulation of nitrogen. The average needle litterfall in control (C) and NS plots in 1993 was 2.2 and 2.5 ton ha⁻¹ year⁻¹, respectively. The fine root litter production prior to treatment (1987) was 4.4 ton ha⁻¹ year⁻¹ and after treatment (1993) it was 4.5 and 3.9 ton ha⁻¹ year⁻¹ in C and NS plots, respectively. Net N mineralization in the soil profile down to 50 cm was estimated to be 86 and 115 kg ha⁻¹ year⁻¹ in C and NS plots, respectively in 1992. During the treatment period the uptake of N in the needle biomass in C and NS plots was 29 and 77 kg ha⁻¹ year⁻¹, respectively. No N was accumulated in needles of C plot where the NS plots accumulated 34 kg ha⁻¹ year⁻¹. Of the annually added inorganic N to NS plots 47% was accumulated in the above and below ground biomass and 37% in the soil. N fluxes via fine-root litter production in the C plots were much higher (54 kg ha⁻¹ year⁻¹) than that via litterfall (29 kg ha⁻¹ year⁻¹). The corresponding values in the NS plots were 65 and 43 kg ha⁻¹ year⁻¹, respectively. Most of the net N mineralization occurred in the FH layer and upper mineral soil. It is concluded that fine root litter and litterfall play an important role in the cycling of N. Despite a high N uptake the losses of N in litterfall and fine root litter resulted in an incorporation of N in soil organic matter.     

Dynamic of functional microbial groups during mesophilic composting of agro-industrial wastes and free-living (N2)-fixing bacteria application

Although several reports are available concerning the composition and dynamics of the microflora during the composting of municipal solid wastes, little is known about the microbial diversity during the composting of agro-industrial refuse. For this reason, the first parts of this study included the quantification of microbial generic groups and of the main functional groups of C and N cycle during composting of agro-industrial refuse. After a generalized decrease observed during the initial phases, a new bacterial growth was observed in the final phase of the process. Ammonifiers and (N₂)-fixing aerobic groups predominated outside of the piles whereas, nitrate-reducing group increased inside the piles during the first 23 days of composting. Ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), showed an opposite trend of growth since ammonia oxidation decreased with the increase of the nitrite oxidation activity. Pectinolytics, amylolytics and aerobic cellulolytic were present in greater quantities and showed an upward trend in both the internal and external part of the heaps.Several free-living (N₂)-fixing bacteria were molecularly identify as belonging especially to uncommon genera of nitrogen-fixing bacteria as Stenotrophomonas, Xanthomonas, Pseudomonas, Klebsiella, Alcaligenes, Achromobacter and Caulobacter. They were investigated for their ability to fix atmospheric nitrogen to employ as improvers of quality of compost. Some strains of Azotobacter chrococcum and Azotobacter salinestris were also tested. When different diazotrophic bacterial species were added in compost, the increase of total N ranged from 16% to 27% depending on the selected microbial strain being used. Such microorganisms may be used alone or in mixtures to provide an allocation of plant growth promoting rhizobacteria in soil.     

Metabolic fate of the 14C-labeled herbicide clodinafop-propargyl in soil

The metabolic fate of ¹⁴C-phenyl-labeled herbicide clodinafop-propargyl (CfP) was studied for 28 days in lab assays using a soil from Germany (A_p horizon, silt loam, and cambisol). Mineralization amounted to 12.40% of applied ¹⁴C after 28 days showing a distinct lag phase until day 7 of incubation. Portions of radioactivity extractable by means of 0.01 M CaCl₂ solution (bioavailable fraction) decreased rapidly and were 4.41% after 28 days. Even immediately after application, only 57.31% were extracted with the aqueous solvent. Subsequent extraction using accelerated solvent extraction (ASE; acetonitrile/water 4:1, v/v) released 39.91% of applied ¹⁴C with day 0 and 26.16% with day 28 of incubation from the samples. Non-extractable portions of radioactivity thus, increased with time amounting to 11.99% (day 0) and 65.00% (day 28). A remarkable increase was observed between 14 and 28 days correlating with the distinct increase of mineralization. No correlation was found throughout incubation with general microbial activity as determined by DMSO reduction. Analysis of the CaCl₂ and ASE extracts by radio-TLC, radio-HPLC and GC/MS revealed that CfP was rapidly cleaved to free acid clodinafop (Cf), which was further (bio-) transformed; DT₅₀ values (based on radio-TLC detection of the parent compound) were far below 1 day (CfP) and about 7 days (Cf). TLC analysis pointed to 2-(4-hydroxyphenoxy)-propionic acid as further metabolite. Due to fractionation of non-extractable residues, most of the ¹⁴C was associated with fulvic and humic acids, portions in humin fractions and non-humics were moderate and low, respectively. Using a special strategy, which included pre-incubation of the soil with CfP and then mineralization of ¹⁴C-CfP as criterion, a microorganism was isolated from the soil examined. The microorganism grew using CfP as sole carbon source with concomitant evolution of ¹⁴CO₂. The bacterium was characterized by growth on commonly used carbon sources and by 16S rDNA sequence analysis. The sequence exhibited high similarity with that of Rhodococcus wratislaviensis (99.56%; DSM 44107, NCIMB 13082).     

Elevated CO2 facilitates C and N accumulation in a rice paddy ecosystem

Elevated CO2 can stimulate wetland carbon(C) and nitrogen(N) exports through gaseous and dissolved pathways, however, the consequent influences on the C and N pools are still not fully known. Therefore, we set up a free-air CO2 enrichment experiment in a paddy field in Eastern China. After five year fumigation, we studied C and N in the plant–water–soil system. The results showed:(1) elevated CO2 stimulated rice aboveground biomass and N accumulations by 19.1% and 12.5%, respectively.(2) Elevated CO2 significantly increased paddy soil TOC and TN contents by 12.5% and 15.5%, respectively in the 0–15 cm layer, and22.7% and 26.0% in the 15–30 cm soil layer.(3) Averaged across the rice growing period,elevated CO2 greatly increased TOC and TN contents in the surface water by 7.6% and 11.4%,respectively.(4) The TOC/TN ratio and natural δ15N value in the surface soil showed a decreasing trend under elevated CO2. The above results indicate that elevated CO2 can benefit C and N accumulation in paddy fields. Given the similarity between the paddies and natural wetlands, our results also suggest a great potential for long-term C and N accumulation in natural wetlands under future climate patterns.