Pesticide sorption and diffusion in natural clay loam aggregates

Pesticide sorption in soils is controlled by time-dependent processes such as diffusion into soil aggregates and microscopic sorbent particles. This study examines the rate-controlling step for time-dependent sorption in clay loam aggregates. Aggregates (5 mm) were stabilized with alginate, and adsorption of azoxystrobin, chlorotoluron, and cyanazine was measured in batch systems equilibrated for periods between 1 h and 7 days. Stepwise desorption was measured at 1- or 3-day intervals following 1 or 7 days of adsorption. Time-dependent adsorption was also measured on dispersed soil. Results were interpreted using process-based modeling. Adsorption on dispersed soil was described by intraparticle sorption and diffusion. Adsorption in the aggregates was much less than in suspension, suggesting that part of the sorption capacity of the dispersed soil was not available within the aggregates (approximately 50%). Adsorption and desorption were reversible and could be described by pore diffusion into the aggregate with effective diffusion coefficients between 0.5 x 10(-10) and 1 x 10(-10) m2 s(-1), a factor 3-6 slower than estimated theoretically. Intraparticle diffusion did not seem to contribute to sorption in the aggregates at this time scale. Apparent hysteresis was explained by nonattainment of equilibrium during the adsorption and desorption steps.     

Sorption of Selected Aromatic Substances��Application of Kinetic Concepts and Quantum Mechanical Modeling

Prediction of the sorption behavior of environmental pollutants is of utmost importance within the framework of risk assessments. In this work two approaches are presented with the aim to describe sorption of aromatic substances to geosorbents. First, analytical solutions of kinetic models were fitted to experimental data of batch sorption experiments with aniline and 1-naphthylamine onto animal manure-treated soil and the soil mineral montmorillonite. The models, accounting for equilibrium and nonequilibrium sorption coupled to transformation and/or irreversible sorption processes, could well reproduce the concentration course of the sorbates. Results suggest that the amounts transformed/degraded and irreversibly bound were higher for the soil than for the clay mineral. In the second part, quantum chemical calculations were performed on aniline and 1-naphthylamine interacting with acetic acid, acetamide, imidazole, and phenol as models of functional groups present in humic substances. Molecular modeling showed that formation of hydrogen bonds is the dominating binding mechanism in all modeled complexes, which are energetically very similar between aniline and 1-naphthylamine.     

Aroma extraction dilution analysis of Sauternes wines. Key role of polyfunctional thiols

The aim of the present work was to investigate Sauternes wine aromas. In all wine extracts, polyfunctional thiols were revealed to have a huge impact. A very strong bacon-petroleum odor emerged at RI = 845 from a CP-Sil5-CB column. Two thiols proved to participate in this perception: 3-methyl-3-sulfanylbutanal and 2-methylfuran-3-thiol. A strong synergetic effect was evidenced between the two compounds. The former, never mentioned before in wines, and not found in the musts of this study, is most probably synthesized during fermentation. 3-Methylbut-2-ene-1-thiol, 3-sulfanylpropyl acetate, 3-sulfanylhexan-1-ol, and 3-sulfanylheptanal also contribute to the global aromas of Sauternes wines. Among other key odorants, the presence of a varietal aroma (alpha-terpineol), sotolon, fermentation alcohols (3-methylbutan-1-ol and 2-phenylethanol) and esters (ethyl butyrate, ethyl hexanoate, and ethyl isovalerate), carbonyls (trans-non-2-enal and beta-damascenone), and wood flavors (guaiacol, vanillin, eugenol, beta-methyl-gamma-octalactone, and Furaneol) is worth stressing.     

Microbial aspects of atrazine biodegradation in relation to history of soil treatment

Among 15 soils with different cropping practices, seven which had an history of repeated atrazine applications showed accelerated degradation of this herbicide. By contrast, grassland or agricultural soils with no recorded atrazine application, at least for the last three years, had a low degradation potential. No direct relation was found between the rate of atrazine mineralisation and the size of the microbial biomass. In adapted soils, the amounts of extractable residues were lowered and the very high percentages of radioactivity from [ring-¹⁴C]atrazine recovered as [¹⁴C]carbon dioxide demonstrated that N-dealkylation and deamidation were the only processes for micro-organisms to derive carbon and energy for heterotrophic growth. Kinetics of microbial ¹⁴C accumulation revealed that atrazine ring carbon could be incorporated by direct oxidative condensation with structural components of the bacterial or fungal cell whereas side-chain carbon was preferentially used for biosynthesis of new protoplasmic cell material, as confirmed by the high turnover rate of radiolabelled microbial components. From the determination of the Michaelis–Menten parameters, V_m and K_m in the presence of different selective biocides, it was possible to conclude that fungi were probably less active in atrazine degradation than bacteria and that over years the microbial atrazine-degrading community showed an increased efficiency. © 1999 Society of Chemical Industry     

Quantification of circulating tumour cells over time in dogs with appendicular osteosarcoma

Enumeration of circulating tumour cells (CTC) has shown promise for prognostication and guidance of therapeutic decisions in human cancers. The objective of this study was to enumerate CTC over time in dogs with naturally occurring osteosarcoma (OSA), and to determine correlation with patient outcome. Twenty-six dogs with OSA and no evidence of metastatic disease at the time of amputation were enrolled. Dogs were assessed for lung metastases and CTC prior to and following amputation, and at each chemotherapy visit. Twenty-one dogs completed the study. Nineteen dogs were euthanized and two were alive and free of metastases. Overall survival time ranged from 88 to 1058 days (median survival time (MST) 374 days). Increased serum alkaline phosphatase activity, advanced age, and higher body weight were significantly associated with lower MST. Dogs with OSA had a mean of 356 (0 to 4443) CTC/10⁶ leukocytes. In 12 of 15 dogs that developed radiographic evidence of metastasis, a pre-metastatic CTC spike was retrospectively detectable on average 36.5 (1–100 days) days prior to metastasis and was associated with significantly shorter MST (301 ± 64 vs. 626 ± 55 days; p = .0107). In a multivariable analysis, dogs with a CTC spike were 10× more likely to die compared with those without. These results suggest that a spike in CTC frequency precedes detection of metastasis in dogs with OSA and is associated with shorter survival. More frequent enumeration of CTC in a larger cohort of dogs with OSA may be warranted.     

Immunoglobulins in nasal secretions of dog puppies from birth to six weeks of age

In order to investigate local immune defence mechanisms in the dog, the concentration of immunoglobulins (Ig) G, A and M in nasal secretions (NS) and serum of 42 healthy, neonatal Rottweiler puppies was determined. Ig were measured with a commercially available, dog-specific ELISA during the first six weeks of life. On average, IgG was the predominant Ig isotype during the first three days of life. The IgA:IgG ratio changed between weeks 1 and 3 due to markedly decreasing IgG concentrations. Between the fourth and sixth week, IgG predominated again. During the first week, only 21-39% of puppies had measurable amounts of IgM in NS, in week 2, this percentage increased to 69%. Marked differences between litters and between individual puppies within litters were found. No puppy diseased during the observation period and all developed normally.     

Pedotransfer functions for the pool size of slowly mineralizable organic N in sandy arable soils

The major aim of this study was to evaluate how the pool size of slowly mineralizable, ‘old’ soil organic N can be derived from more easily accessible soil and site information via pedotransfer functions (PTF). Besides modeling, this pool size might be of great importance for the identification of soils with high mineralization potential in drinking‐water catchments. From long‐term laboratory incubations (ca. 200 days) at 35 °C, the pool sizes of easily mineralizable organic N (N_fast), mainly in fresh residues, and slowly mineralizable, ‘old’ soil organic N (N_slow) as well as their first‐order rate coefficients were obtained. 90 sandy arable soils from NW Germany served to derive PTFs for N_slow that were evaluated using another 20 soils from the same region. Information on former land‐use and soil type was obtained from topographical, historical, and soil maps (partly from 1780). Pool size N_slow very strongly depends on soil type and former land‐use. Mean pool sizes of N_slow were much lower in old arable lowland (105 mg N kg^–1) than upland soils (175 mg N kg^–1) possibly due to lower clay contents. Within lowlands, mean pool sizes in former grassland soils (245 mg N kg^–1) were 2 to 3 times larger than in old arable soils due to accumulation of mineralizable N. In contrast, mean pool sizes of N_slow were lowest in recently cleared, former heath‐ and woodland (31 mg N kg^–1) as a result of the input of hardly decomposable organic matter. Neither N nor C in the light fraction (density < 1.8 g cm^–3) was adequate to derive pool size N_slow in the studied soils (r² < 0.03). Instead, N_slow can be accurately (r² = 0.55 – 0.83) derived from one or two basic soil characteristics (e.g. organic C, total N, C : N, mineral fraction < 20 μm), provided that sites were grouped by former land‐use. Field mineralization from N_slow during winter (independent data set) can be predicted as well on the basis of N_slow‐values calculated from PTFs that were derived after grouping the soils by former land‐use (r² = 0.51***). In contrast, using the PTF without soil grouping strongly reduced the reliability (r² = 0.16).     

Tracing faecal pollution by coprostanol and intestinal bacteria in an ice-covered finnish lake loaded with both industrial and domestic sewage

The relationships existing between coprostanol (5β-cholestan-3β-ol), faecal indicator bacteria and various physico-chemical tracer and bacterial stress factors in an ice-covered Finnish lake were investigated. Field observations show that coprostanol lies below the theoretical mixing line, indicating a net removal, primarily by settling together with suspended sediments. Faecal indicator bacteria, however, are differently transported and are removed by various environmental factors e.g. industrial wastes. Thus, only faecal streptococci show a regional covariance to coprostanol. Principal component analyses reveal a strong correlation between coprostanol and faecal streptococci in water but not with coliforms and sulfite reducing sporing anaerobs. However, in sediments also coliforms are correlated significantly with coprostanol and faecal streptococci. Therefore it might be necessary to estimate the quality of those waters polluted by both industrial and faecal wastes by means of coprostanol, a principal sterol in sewage of man and higher animals, which is thus well suited as a chemical marker of faecal pollution.     

Limitations when quantifying microbial carbon and nitrogen by fumigation‐extraction in rooted soils

Soil microbial C and N (C_mic, N_mic) estimation by the chloroform fumigation‐extraction method is erroneous in densely rooted soils due to CHCl₃‐labile C and N compounds. The effect of a pre‐extraction with 50 mM K₂SO₄ and a pre‐incubation (conditioning at 25 °C for 7 days) on the flush in extractable, CHCl₃‐labile C (C‐flush) and N (N‐flush) was tested with reference to rooting density (0.3—75 mg root dry matter g^—1) in one arable and 3 grassland soils. In the arable soil and in the second horizon (10—20 cm) of a grassland soil, C‐flush values were not affected by the pre‐extraction. However, the pre‐extraction considerably reduced C‐flush values in the top soils of the grassland (above 10 cm). Only about 42 % was found in the pre‐extracted roots and the rest was lost during the pre‐extraction. The estimated concentrations of N_mic decreased due to pre‐extraction of soil samples with low root biomass. Clearly, the concentrations of N_mic were underestimated by introducing the pre‐extraction. Soil pre‐incubation reduced C‐flush values only slightly, whereas N‐flush values were not affected. It can be concluded that (1) CHCl₃‐labile root C and N is partly extracted with K₂SO₄ after pre‐incubation and (2) CHCl₃‐labile C and N removed with the roots during pre‐extraction is partly derived from microbial biomass. Soils with low rooting density (arable soils, grassland soils below approximately 10 cm depth) should therefore be fumigated and extracted without pre‐extraction. In densely rooted soils, fumigation extraction with and without pre‐extraction probably gives estimates for the minimum and maximum of C_mic and N_mic.     

Comparison of soil phosphorus extraction methods regarding their suitability for organic farming systems

Background

Organic farmers frequently report sufficient yield levels despite low or even very low soil phosphorous (P) contents questioning the applicability of widely used laboratory methods for soil P testing for organic farming.

Aims

The aim of this study was to compare the validity of a broad range of different soil extraction methods on soils under organic management from South West Germany and to test the correlation of the measured soil P concentration with plant offtake.

Methods

Twenty-two soil samples of eight different organic farms were extracted with different solutions: (1) water, (2) CAL, (3) Olsen, (4) Mehlich 3, (5) Bray P1, (6) Bray P2, (7) NaOH+Na₂EDTA, and (8) total P. The results were then correlated with above ground plant P.

Results

Spearman's rank correlation coefficient (r_s) of correlations between above ground plant P and extractable soil P (Water-P, CAL-P, and Olsen-P [+active charcoal {+AC}]) determined with ICP-OES were strong (0.94, 0.90, and 0.93, respectively). Among the tested methods, above ground plant P showed a strong correlation with CAL-P as detected by ICP-OES (r_s = 0.90) and colorimetry (r_s = 0.91). The comparison of CAL-P data provided by farmers and CAL-P analyzed during this research showed discrepancies between the results.

Conclusions

The results of this study indicate that the CAL method can be used in organic farming despite a low extraction of organic P (P_org). Furthermore, it is recommended for farmers to take soil samples for analyses regularly and interpret changes in P in the long-term instead of interpreting individual samples.