Competitive adsorption/desorption of tetracycline, oxytetracycline and chlortetracycline on two acid soils: Stirred flow chamber experiments.

The objective of this work was to study the competitive adsorption/desorption of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) on two acid soils. We used the stirred flow chamber technique to obtain experimental data on rapid kinetic processes affecting the retention/release of the antibiotics. Both adsorption and desorption were higher on soil 1 (which showed the highest carbon, clay and Al and Fe oxides content) than on soil 2. Moreover, hysteresis affected the adsorption/desorption processes. Experimental data were fitted to a pseudo-first order equation, resulting qamax (adsorption maximum) values that were higher for soil 1 than for soil 2, and indicating that CTC competed with TC more intensely than OTC in soil 1. Regarding soil 2, the values corresponding to the adsorption kinetics constants (ka) and desorption kinetics constants for fast sites (kd1), followed a trend inverse to qamax and qdmax respectively. In conclusion, competition affected adsorption/desorption kinetics for the three antibiotics assayed, and thus retention/release and subsequent transport processes in soil and water environments.

Kinetics of tetracycline, oxytetracycline, and chlortetracycline adsorption and desorption on two acid soils.

The purpose of this work was to quantify retention/release of tetracycline, oxytetracycline, and chlortetracycline on two soils, paying attention to sorption kinetics and to implications of the adsorption/desorption processes on transfer of these pollutants to the various environmental compartments. We used the stirred flow chamber (SFC) procedure to achieve this goal. All three antibiotics showed high affinity for both soils, with greater adsorption intensity for soil 1, the one with the highest organic matter and Al and Fe oxides contents. Desorption was always <15%, exhibiting strong hysteresis in the adsorption/desorption processes. Adsorption was adequately modeled using a pseudo first-order equation with just one type of adsorption sites, whereas desorption was better adjusted considering both fast and slow sorption sites. The adsorption maximum (qmax) followed the sequence tetracycline > oxytetracycline > chlortetracycline in soil 1, with similar values for the three antibiotics and the sequence tetracycline > chlortetracycline > oxytetracycline in soil 2. The desorption sequences were oxytetracycline > tetracycline > chlortetracycline in soil 1 and oxytetracycline > chlortetracycline > tetracycline in soil 2. In conclusion, the SFC technique has yielded new kinetic data regarding tetracycline, oxytetracycline, and chlortetracycline adsorption/desorption on soils, indicating that it can be used to shed further light on the retention and transport processes affecting antibiotics on soils and other media, thus increasing knowledge on the behavior and evolution of these pharmaceutical residues in the environment.

Pollution of surface waters by metalaxyl and nitrate from non-point sources.

The mobility of contaminants in soil is highly dependent upon the characteristics of the contaminant chemical and the properties of the soil. In order to explore these relationships, the district of A Limia (Galicia, NW Spain) was selected as the study area--a cropland devoted to growing potatoes, where the soil had been managed intensively over the last 50 years. The soil was characterised by low slopes with the water table located very close to the soil surface. Our aim was to study the influence of high and intensive crop production on the water bodies and non-point source contamination, with a particular focus on metalaxyl and nitrate. The highest concentrations of metalaxyl occurred when rainfalls were low and in zones of the study area where natural hydrology was significantly altered by numerous drainage canals. The spatial and temporal distributions of the nitrate also showed a high variability, with the interaction between seasons and sampling area being the most significant factor in explaining the levels found.

As(V) retention on soils and forest by-products and other waste materials.

As(V) retention capacity is determined by means of adsorption/desorption trials performed for coarse and fine ground mussel shell, forest and vineyard soils with or without fine shell, pine wood ash, oak wood ash, pine sawdust and slate-processing fines. Pine ash shows the highest arsenic retention potential (with >97 % adsorption and ≤1 % desorption), followed by shell-amended forest soil (adsorption between 96 and 92 %), by un-amended forest soil (adsorption between 98 and 86 %) and by the amended vineyard soil (adsorption between 92 and 75 %). Sawdust is the material with the lowest arsenic retention capacity in most cases, with un-amended vineyard soil also showing poor results. In the case of oak ash, As(V) percentage adsorption becomes higher with increasing added arsenic concentrations, while this increase in added arsenic causes lower percentage adsorption in the case of slate fines. Regarding adsorption ability, As(V) adsorption data were fitted to Freundlich and Langmuir models, showing good fitting, with pine ash and shell-amended forest soil having the highest K F values. In view of that, mussel shell amendment would be useful to increase arsenic retention on forest and vineyard soils, while pine ash could be used to retain arsenic even from wastewaters.

Mercury removal using ground and calcined mussel shell.

We determined mercury retention on calcined and ground mussel shell, in presence and absence of phosphate, using batch and stirred flow chamber experiments. In batch experiments the calcined shell exhibited higher Hg adsorption, with good fitting to Freundlich equation (R2: 0.925-0.978); the presence of phosphate increased Hg adsorption; mercury desorption was 13% or lower, diminishing up to 2% under the presence of phosphates. In stirred flow chamber experiments calcined shell retained more Hg than ground shells (6300 vs. 4000-5200 micromol/kg); Hg retention increased an additional 40% on calcined shell and up to an additional 70% on ground shells when phosphates were present; mercury desorption was quite similar in all shell types (20%-34%), increasing up to 49%-60% in ground shells when phosphates were present. The higher Hg adsorption on calcined shell would be related to its calcite and dolomite concentrations; mercury-phosphate interactions would cause the increase in Hg retention when phosphates are present. Data on Hg desorption suggest that Hg retention was not easily reversible after batch experiments, increasing in the stirred flow chamber due to convective flow. Calcined and ground mussel shells could be recycled removing Hg from water, with the presence of phosphates in solution improving efficacy.

Influence of different abiotic and biotic factors on the metalaxyl and carbofuran dissipation.

Metalaxyl and carbofuran dissipation was studied in response to different factors (soil bacterial communities, light irradiation, presence of an inorganic culture medium and presence of soil) and combinations of these factors in short-term experiments (48 h). The soil microbial communities have no effect on metalaxyl or carbofuran dissipation in the time scale employed. Light irradiation and soil promote metalaxyl and carbofuran dissipation by photodegradation and adsorption, respectively. However, photodegradation has a stronger effect on metalaxyl and carbofuran dissipation than the adsorption of the pesticides in the soil. The addition of the culture medium have no direct effect on pesticide dissipation, degradation by microbial communities or adsorption but its presence greatly increased photodegradation.

Comparison of batch, stirred flow chamber, and column experiments to study adsorption, desorption and transport of carbofuran within two acidic soils.

Different methods (batch, column and stirred flow chamber experiments) used for adsorption and desorption of carbofuran studies were compared. All tested methods showed that the carbofuran adsorption was higher in the soil with the higher organic matter content, whereas the opposite behaviour was observed for the percentage of carbofuran desorbed. However, different methods have revealed some discrepancies in carbofuran adsorption/desorption kinetics. Although batch method showed interesting data on equilibrium experiments, such as a low heterogeneity for the carbofuran adsorption sites independent of soil organic matter content, it had some disadvantages for carbofuran adsorption/desorption kinetic studies. The disadvantages were related with the excessive limitations of this method on kinetics, i.e., no difference could be detected between different soils. However, with column and stirred flow chamber methods the carbofuran adsorption/desorption kinetics of different soils could be compared. Moreover, the absolute values of carbofuran adsorption/desorption and its rate were higher in the stirred flow chamber than in the batch and column experiments. Using stirred flow chamber experiments the carbofuran desorption was significantly faster than its adsorption, whereas carbofuran using column experiments they were similar. These discrepancies should be considered when the results obtained only with one method is discussed.

Copper release kinetics from a long-term contaminated acid soil using a stirred flow chamber: effect of ionic strength and pH.

The effect of pH and ionic strength on copper release in a long-term Cu-polluted soil was studied using a stirred flow chamber. The presence of Ca(2+) and Na(+) was also evaluated. More copper was released as the ionic strength increased, and it was significantly higher in the presence of Ca(2+) than in the presence of Na(+). The maximum amount of Cu that could be released under experimental conditions increased logarithmically as the ionic strength increased, and the release rate parameters were not significantly correlated with ionic strength values. The maximum amount of Cu that could be released was similar for solutions with pH values between 5.5 and 8.5. For solutions with a pH value below 4.5, the amount of Cu released increased exponentially as the pH decreased. The release rate parameters and Cu release pattern were affected by pH, especially for more acidic solutions (pH values of 2.5 and 3.5).

Adsorption and desorption behavior of metalaxyl in intensively cultivated acid soils.

Metalaxyl adsorption and desorption behavior in acid soils were evaluated via batch and stirred-flow chamber experiments. On the basis of batch experiments (adsorption curves of the Giles C-type), metalaxyl has a low affinity for acid soils. Also, as derived from batch and stirred-flow chamber tests, its adsorption in acid soils is dictated mainly by their organic matter and clay contents. The high correlation between these two variables makes it rather complicated to resolve their effects. Metalaxyl adsorption occurs largely (80-99%) via fast adsorption reactions. On the other hand, the pesticide is desorbed in variable proportions (30-100%). The desorption parameters obtained by fitting the results to a pseudo-first-order reaction were correlated with no edaphic variable; however, the q(0)/q(max) ratio, which is a measure of reversibility in the adsorption-desorption process, exhibited significant negative correlation with the organic matter and clay contents.

Adsorption and desorption kinetics of carbofuran in acid soils.

Carbofuran adsorption and desorption were investigated in batch and stirred flow chamber (SFC) tests. The carbofuran adsorption capacity of the soils was found to be low and strongly dependent on their clay and organic carbon contents. Carbofuran sorption was due mainly (>80%) to fast adsorption processes governed by intraparticle diffusion. The adsorption kinetic constant for the pesticide ranged from 0.047 to 0.195 min(-1) and was highly correlated with constant n in the Freundlich equation (r=0.965, P<0.05). Batch tests showed carbofuran desorption to be highly variable and negatively correlated with eCEC and the clay content. The SFC tests showed that soil organic carbon (C) plays a key role in the irreversibility of carbofuran adsorption. Carbofuran desorption increased rapidly at C contents below 4%. The desorption kinetic constant for the compound (0.086-0.195 min(-1)) was generally higher than its adsorption kinetic constant; therefore, carbofuran is more rapidly desorbed than it is adsorbed in soil.

Phosphorus effect on Zn adsorption-desorption kinetics in acid soils.

The adsorption-desorption kinetics of Zn in the absence and presence of P was studied by using the stirred flow chamber technique. The results thus obtained were compared with those previously obtained for Cu. As with copper, the simultaneous addition of P and Zn in a 1:1 mole ratio to soil was found to significantly increased Zn adsorption relative to the absence of P. Unlike Cu, however, Zn was only adsorbed at fast adsorption sites in the absence of P. In any case, the increased adsorption of Zn in the presence of P was largely due to slow adsorption sites, where Zn(2+) ion acted as a bridging element between P and organic matter. Following adsorption in both the presence and absence of P, Zn was desorbed to a much higher extent than was Cu. However, the proportion of Zn desorbed after adsorption in the presence of P was significantly lower than in the absence of P. This indicates that Zn binds more strongly to adsorbing surfaces in the presence of P than in its absence.