Effects of pine bark amendment on the transport of sulfonamide antibiotics in soils.

In the present work, laboratory column experiments were carried out to study the effect of pine bark amendment (at doses of 0, 12, 48 and 96 Mg ha-1) on the transport of three sulfonamide antibiotics (sulfadiazine -SDZ-, sulfamethazine -SMT-, and sulfachloropyridazine -SCP-) through two crop soils. All three sulfonamides showed high mobility in the unamend soils, with absence of retention in most cases. However, some differences were detected regarding the degree of interactions between sulfonamides and soils, being higher for soil 1, which was attributed to its higher organic carbon content. For both soils, interactions with the antibiotics studied followed the sequence SDZ < SMT < SCP, indicating an increase as a function of the hydrophobicity of sulfonamides. Pine bark amendment significantly increased the retention of the three sulfonamides in both soils. Specifically, in the case of soil 1, the incorporation of the highest dose of pine bark (96 Mg ha-1) caused that retention increased from 0% to 70.3% for SDZ, from 2.7% to 71.3% for SMT, and from 0% to 85.4% for SCP. This effect of pine bark is mainly attributed to its high organic carbon content (48.6%), including substances with potential to interact and retain antibiotics, as well as to its acidic pH (4.5). Therefore, pine bark amendment would be an effective alternative to reduce the transport of sulfonamides in soils and, thus, decrease risks of passing to other environmental compartments, as well as harmful effects on the environment and public health.

Adsorption/desorption and transport of sulfadiazine, sulfachloropyridazine, and sulfamethazine, in acid agricultural soils.

Batch-type experiments were used to study adsorption-desorption of three sulfonamides: sulfadiazine (SDZ) sulfachloropyridazine (SCP), and sulfamethazine (SMT), in five crop soils, whereas laboratory soil column experiments were employed to obtain data on transport processes. Adsorption results were satisfactorily adjusted to Linear and Feundlich equations, with R2 values above 0.95. Adsorption followed the sequence SDZ < SMT < SCP, showing higher values for soils with higher levels of organic carbon (OC) content. Conversely, desorption was higher in soils with less OC, and lower in soils with higher OC contents. The temporal moment analysis method gave values for the transport parameters τ and R which were significantly correlated with soil parameters related to organic matter, specifically OC and N concentrations. The higher retention of the three sulfonamides in soils with high organic matter content is a relevant fact, with value when programming management practices in agricultural soils, and specifically in relation to the spreading of animal manures, slurries, or waste containing these emerging pollutants.

Molecular Basis for the Mechanical Response of Sulfa Drug Crystals.

Comprehension of the nanomechanical response of crystalline materials requires the understanding of the elastic and plastic deformation mechanisms in terms of the underlying crystal structures. Nanoindentation data were combined with structural and computational inputs to derive a molecular-level understanding of the nanomechanical response in eight prototypical sulfa drug molecular crystals. The magnitude of the modulus, E, was strongly connected to the non-covalent bond features, that is, the bond strength, the relative orientation with the measured crystal facet and their disposition in the crystal lattice. Additional features derived from the current study are the following. Firstly, robust synthons well isolated by weak and dispersive interactions reduce the material stiffness; in contrast, the interweaving of interactions with diverse energetics fortifies the crystal packing. Secondly, mere observation of layered structures with orthogonal distribution of strong and weak interactions is a prerequisite, but inadequate, to attain higher plasticity. Thirdly, interlocked molecular arrangements prevent long-range sliding of molecular planes and, hence, lead to enhanced E values. In a broader perspective, the observations are remarkable in deriving a molecular basis of the mechanical properties of crystalline solids, which can be exploited through crystal engineering for the purposeful design of materials with specific properties.

Degradation of sulfadiazine, sulfachloropyridazine and sulfamethazine in aqueous media.

Antibiotics discharged to the environment constitute a main concern for which different treatment alternatives are being studied, some of them based on antibiotics removal or inactivation using by-products with adsorbent capacity, or which can act as catalyst for photo-degradation. But a preliminary step is to determine the general characteristics and magnitude of the degradation process effectively acting on antibiotics. A specific case is that of sulfonamides (SAs), one of the antibiotic groups most widely used in veterinary medicine, and which are considered the most mobile antibiotics, causing that they are frequently detected in both surface- and ground-waters, facilitating their entry in the food chain and causing public health hazards. In this work we investigated abiotic and biotic degradation of three sulfonamides (sulfadiazine -SDZ-, sulfachloropyridazine -SCP-, and sulfamethazine -SMT-) in aqueous media. The results indicated that, in filtered milliQ water and under simulated sunlight, the degradation sequence was: SCP > SDZ ≈ SMT. Furthermore, the rate of degradation clearly increased with the raise of pH: at pH 4.0, half-lives were 1.2, 70.5 and 84.4 h for SCP, SDZ and SMT, respectively, while at pH 7.2 they were 2.3, 9.4 and 13.2 h for SCP, SMT and SDZ. The addition of a culture medium hardly caused any change in degradation rates as compared to experiments performed in milliQ water at the same pH value (7.2), suggesting that in this case sulfonamides degradation rate was not affected by the presence of some chemical elements and compounds, such as sodium, chloride and phosphate. However, the addition of bacterial suspensions extracted from a soil and from poultry manure increased the rate of degradation of these antibiotics. This increase in degradation cannot be attributed to biodegradation, since there was no degradation in the dark during the time of the experiment (72 h). This indicates that photo-degradation constitutes the main removal mechanism for SAs in aqueous media, a mechanism that in this case was favored by humic acids supplied with the extracts from soil and manure. The overall results could contribute to the understanding of the environmental fate of the three sulfonamides studied, aiding to program actions that could favor their inactivation, which is especially relevant since its dissemination can involve serious environmental and public health risks.

Determination of sulfachloropyridazine residue levels in feathers from broiler chickens after oral administration using liquid chromatography coupled to tandem mass spectrometry.

Several antimicrobials are routinely used by the poultry farming industry on their daily operations, however, researchers have found for some antimicrobials that their residues persist for longer periods in feathers than they do in edible tissues, and at higher concentrations, as well. But this information is not known for other classes of antimicrobials, such as the sulfonamides. Therefore, this work presents an accurate and reliable analytical method for the detection of sulfachloropyridazine (SCP) in feathers and edible tissues from broiler chickens. This method was also validated in-house and then used to study the depletion of sulfachloropyridazine in those matrices. The experimental group comprised 54 broiler chickens, who were raised under controlled conditions and then treated with a commercial formulation of 10% sulfachloropyridazine for 5 days. Samples were analyzed via LC-MS/MS, using 13C6-sulfamethazine (SMZ-13C6) as an internal standard. Aromatic sulfonic acid solid phase extraction (SPE) cartridges were used to clean up the samples. The Limit of Detection (LOD) for this method was set at 10 µg kg-1 on feathers and liver; and at 5 µg kg-1 on muscle. Within the range of 10-100 µg kg-1, the calibration curves for all matrices presented a determination coefficient greater than 0.96. Our results show, with a 95% confidence level, that sulfachloropyridazine persisted in feathers for up to 55 days after ceasing treatment, and its concentrations were higher than in edible tissues. In consequence, to avoid re-entry of antimicrobial residues into the food-chain, we recommend monitoring and inspecting animal diets that contain feather derivatives, such as feathers meals, because they could be sourced from birds that might have been medicated with sulfachloropyridazine.

Submicron sized water-stable metal organic framework (bio-MOF-11) for catalytic degradation of pharmaceuticals and personal care products.

Water-stable and active metal organic frameworks (MOFs) are important materials for mitigation of water contaminants via adsorption and catalytic reactions. In this study, a highly water-stable Co-based MOF, namely bio-MOF-11-Co, was synthesized by a simplified benign method. Moreover, it was used as a catalyst in successful activation of peroxymonsulfate for catalytic degradation of sulfachloropyradazine (SCP) and para-hydroxybenzoic acid (p-HBA) as representatives of pharmaceuticals and personal care products, respectively. The bio-MOF-11-Co showed rapid degradation of both p-HBA and SCP and could be reused multiple times without losing the activity by simply water washing. The effects of catalyst and PMS loadings as well as temperature were further studied, showing that high catalyst and PMS loadings as well as temperature produced faster kinetic degradation of p-HBA and SCP. The generation of highly reactive and HO radicals during the degradation was investigated by quenching tests and electron paramagnetic resonance. A plausible degradation mechanism was proposed based on the functionalities in the bio-MOF-11-Co. The availability of electron rich nucleobase adenine reinforced the reaction kinetics by electron donation along with cobalt atoms in the bio-MOF-11-Co structure.

Quantum chemical study of the photolysis mechanisms of sulfachloropyridazine and the influence of selected divalent metal ions.

Sulfonamides have been found in aquatic environments. Degradation of sulfachloropyridazine (SCP) mainly proceeds through direct and indirect photolysis in the aquatic environment. However, the mechanisms underlying the triplet photolysis of SCP and the influence of metal ions on the photolysis mechanism have not yet been fully explained. In this study, we elucidated the triplet photolysis mechanisms of SCP and the effects of three selected metal ions (Zn(2+), Ca(2+), and Cu(2+)) on the SCP photolysis mechanisms using quantum chemical calculation. Optimization of molecular structures and reaction pathways analysis of SCP were carried out at the B3LYP/6-31+G(d,p) level of theory. Two minimum energy pathways were investigated in the triplet photolysis of SCP. In Step 2 of Path-I, the photolysis product of SCP is a sulfur dioxide extrusion product, (4-(3-chloro-6-iminopyridazine-1(6H)-yl)aniline). The estimated activation energies of Step 2 and Step 3 of Path-I were much higher than in Path-II. Therefore, Path-II was found as the lowest energy pathway to obtain the SCP photoproducts, and Step 2 of Path-II was confirmed as the rate-determining step (RDS) in the photolysis mechanism of SCP. For the RDS of Path-II, computations with the three metal ions complexes (IM1-Cu(2+), IM1-Ca(2+), and IM1-Zn(2+)) show that the metal ions Cu(2+) and Ca(2+) promote triplet-sensitized photolysis of SCP by reducing the activation energy of RDS of Path-II, whereas Zn(2+) showed an inhibitory effect in photolysis of SCP by increasing the activation energy.

Antibacterial, antifungal, phytotoxic, and genotoxic properties of two complexes of Ag(I) with sulfachloropyridazine (SCP): X-ray diffraction of [Ag(SCP)]n.

We report the synthesis, characterization, antibacterial and antifungal activities, phytotoxicity, and genotoxicity of two new complexes of silver(I) with sulfachloropyridazine (SCP), one of which is heteroleptic with SCP and SCN(-) ligands (Ag-SCP-SCN), the other of which is homoleptic (Ag-SCP); furthermore, the crystal structure of the homoleptic complex is disclosed. The heterocyclic N atom nearest to the Cl atom and the N(sulfonamide) atom could be coordination sites for the silver ion in the Ag-SCP-SCN complex. The Ag-SCP complex is a polymeric compound with metal-metal bonds, and the heterocyclic and sulfonamide N atoms are points of coordination for Ag(I) . Both complexes showed activity against all the tested bacteria, and in the cases of Escherichia coli and Pseudomonas aeruginosa, the action was better than that of SCP. In all cases, both silver-SCP complexes showed better antifungal activity than SCP, which was inactive against the tested fungi. Notably, the activity against P. aeruginosa, a nosocomial multidrug-resistant pathogen, was better than that of the reference antibiotic cefotaxim. Both silver-sulfa complexes displayed moderate activity against the tested yeast, especially for C. neoformans, which is an important fact considering the incidence of cryptococcosis, mainly in immune-deficient patients. No chromosomal aberrations were observed with the Allium cepa test, which is auspicious for further study of these complexes as potential drugs.

Sorption/desorption behavior of oxytetracycline and sulfachloropyridazine in the soil water surfactant system.

Sorption/desorption of antibiotics, oxytetracycline (OTC), and sulfachloropyridazine (SCP) was investigated in the presence of a nonionic surfactant Brij35. Batch sorption experiments indicated that Freundlich equation fits sorption isotherms well for OTC. The sorption coefficients, KF, values were computed as 23.55 mL g(−1) in the absence of Brij35 and 25.46 mL g(−1) in the presence of Brij35 in the monomer form (below critical micelle concentration CMC, of 74 mg L(−1)). However, the KF values reduced to 12.76 mL g(−1) in the presence of Brij35 at 2.5 g L(−1). Therefore, irrigation with surfactant-rich water may increase the leaching potential of OTC. In the case of SCP, the KF value, in the absence of Brij35, was 19.95 mL g(−1). As a result of increasing the concentration of Brij35 to 0.25 g L(−1) (about 2.5 CMC), KF values first increased and reached a maximum value of 95.49 mL g(−1) and then reduced to 66.06 mL g(−1), at surfactant concentration of 5 g L(−1). Unlike OTC, the presence of surfactant in irrigation water is likely to decrease SCP leaching. In the case of OTC, hysteresis was found at Brij35 concentrations below CMC. However, OTC desorbed readily from soil (no hysteresis) at Brij35 concentrations above CMC. In the case of SCP, no hysteresis was found in the presence of the surfactant, both below and above CMC. Further, the obtained values of the efficiency coefficient (E), reveals that Brij35 had the potential to release more OTC from the soil (E > 1) as compared to SCP (E < 1). From these results, it can be concluded that regular use of manure on agricultural soils, especially in regions where poor quality irrigation water is used, can increase OTC contamination of water resources.

Sorption of selected veterinary antibiotics onto dairy farming soils of contrasting nature.

The sorption potential for three sulfonamides (SAs), sulfamethoxazole (SMO), sulfachloropyridazine (SCP) and sulfamethazine (SM) and a macrolide, tylosin tartrate (TT) was assessed on six New Zealand dairy farming soils of contrasting physico-chemical properties. Kinetics studies showed that the sorption was rapid in the first few hours of the contact time (0-2h for SA and 0-4h for TT) and thereafter apparent equilibrium was achieved. Batch sorption isotherm data revealed that the degree of isotherm linearity (N) for SCP and SM varied between 0.50 and 1.08 in the six soils. Isotherms of both TT and SMO were mostly non-linear with the degree of non-linearity for TT (N=0.38-0.71) being greater than for SMO (0.42-0.75) in all soils except Manawatu (TT) and Te Kowhai (SMO) where a linear pattern was observed. Concentration-dependent effective distribution coefficient (Kd(eff)) values for the SMO, SCP and SM antibiotics in the soils ranged from 0.85 to 16.35 L kg(-1), while that for TT was 1.6 to 1,042 L kg(-1). The sorption affinity for all soils followed an order: TT>SCP>SM>SMO. Remarkable high sorption for tylosin in Matawhero soil as compared to other soils was attributed to the presence of oxygen containing acidic polar functional groups as evident in the FT-IR spectra of the soil. Furthermore, it was hypothesised that sorption of TT onto soils was mostly driven by metal oxide-surface mediated transformations whereas for sulfonamides it was primarily due to hydrophobic interactions.

Co-contaminants and factors affecting the sorption behaviour of two sulfonamides in pasture soils.

We investigated the effect of soil pH, organic carbon, ionic strength and steroid hormones on the sorption of sulfamethoxazole (SMO) and sulfachloropyridazine (SCP) in three pastoral soils of New Zealand. A model linking sorbate speciation with species-specific sorption coefficients describing the pH dependence of the apparent sorption coefficients was used to derive the fraction of each species of SMO. All soils displayed a decrease in sorption when pH was increased, with SMO exhibiting the highest sorption at pH 2. The cationic form of SMO appeared to sorb more close to pH ≥ pKa1 and, when pH ≥ pKa2 (6.5, 7.5 and 8.5) the anionic species seems to dominate, however, its sorption affinity to all soils was low. SMO sorption was affected by ionic strengths and organic carbon content, while the presence of hormones showed only a subtle decrease in SCP sorption in a selected model pasture soil.

Electrochemical degradation of the antibiotic sulfachloropyridazine by hydroxyl radicals generated at a BDD anode.

The treatment of aqueous solutions of the antibiotic sulfachloropyridazine (SCP) was carried out at the natural pH of the solution (pH 4.5) with hydroxyl radicals (OH) generated at a BDD anode surface by electro-oxidation using an undivided electrochemical cell equipped with a three-dimensional carbon-felt cathode. Hydroxyl radicals are powerful oxidants and react with the antibiotic leading to its overall mineralization. The kinetic study showed that oxidative degradation of SCP follows pseudo first-order reaction kinetics, with a relatively short degradation time. The degree of mineralization of SCP solutions increased with the applied current, being higher than 95% after 8 h of electrolysis at 350 mA or higher current. To determine the degradation pathway upon the action of hydroxyl radicals, the cyclic and aliphatic by-products, as well as the released inorganic ions, were identified and quantified over electrolysis time. The values of the rate constants of reactions between OH and the SCP and its intermediates were determined by the competition kinetics method using p-hydroxybenzoic acid. The absolute rate constant for the OH-mediated degradation of SCP was found to be 1.92 × 10(9)M(-1)s(-1). Toxicity assessment by the Microtox method during the electro-oxidation of SCP solutions revealed the formation of compounds that can be more toxic than the parent molecule, but the overall results confirm the effectiveness of this electrochemical process for the removal of the antibiotic SCP and its by-products from aqueous media.

Electrochemical treatment of the antibiotic sulfachloropyridazine: kinetics, reaction pathways, and toxicity evolution.

The electro-Fenton treatment of sulfachloropyridazine (SCP), a model for sulfonamide antibiotics that are widespread in waters, was performed using cells with a carbon-felt cathode and Pt or boron-doped diamond (BDD) anode, aiming to present an integral assessment of the kinetics, electrodegradation byproducts, and toxicity evolution. H(2)O(2) electrogeneration in the presence of Fe(2+) yielded (•)OH in the solution bulk, which acted concomitantly with (•)OH adsorbed at the anode (BDD((•)OH)) to promote the oxidative degradation of SCP (k(abs,SCP) = (1.58 ± 0.02) × 10(9) M(-1) s(-1)) and its byproducts. A detailed scheme for the complete mineralization was elucidated. On the basis of the action of (•)OH onto four different SCP sites, the pathways leading to total decontamination includes fifteen cyclic byproducts identified by HPLC and GC-MS, five aliphatic carboxylic acids, and a mixture of Cl(-), SO(4)(2-), NH(4)(+), and NO(3)(-) that accounted for 90-100% of initial Cl, S, and N. The time course of byproducts was satisfactorily correlated with the toxicity profiles determined from inhibition of Vibrio fischeri luminescence. 3-Amino-6-chloropyridazine and p-benzoquinone were responsible for the increased toxicity during the first stages. Independent electrolyses revealed that their toxicity trends were close to those of SCP. The formation of the carboxylic acids involved a sharp toxicity decrease, thus ensuring overall detoxification.

Effects of agricultural conditions on the leaching behaviour of veterinary antibiotics in soils.

Antibiotics may be released to soils during the application of manure as fertiliser to land. The compounds may subsequently be transported to and contaminate groundwater and surface waters. This paper describes a series of lysimeter-based studies to explore the leaching behaviour of three veterinary antibiotics (sulfachloropyridazine, oxytetracycline and tylosin) under different conditions that could occur in the agricultural environment. The specific objectives were to: (1) explore the influence of slurry amendment and incorporation on leaching; (2) assess the effects of climate on leaching behaviour; and (3) evaluate the predictive capability of a leaching model used in the regulatory assessment of veterinary medicines. Sulfachloropyridazine was detected sporadically in leachate at concentrations up to 0.66 microg L(-1) under typical irrigation conditions and more frequently at concentrations up to 8.5 microg L(-1) under extreme irrigation conditions. Incorporation and timing of rainfall had no effect on leaching behaviour. Oxytetracycline and tylosin were not detected in any leachate samples. These differences in behaviour were explained by the sorption and persistence characteristics of the compounds. Comparison of the experimental measurements with simulations from the leaching model indicated that the model greatly underestimates the transport of antibiotics to groundwater which raises questions over the application of these models in the regulatory risk assessment process.

The dissipation and transport of veterinary antibiotics in a sandy loam soil.

The environmental fate of the antibiotics sulfachloropyridazine and oxytetracycline was investigated in a sandy loam soil. Liquid pig manure was fortified with the compounds and then applied to soil plots to investigate leaching, dissipation and surface run-off under field conditions. Additionally, as the macrolide antibiotic tylosin had been administered to the pigs from which the slurry had been sourced, this was also analysed for in the samples collected. Sulfachloropyridazine dissipated rapidly with DT(50) and DT(90) values of 3.5 and 18.9 days but oxytetracycline was more persistent with DT(50) and DT(90) values of 21.7 and 98.3 days. Both sulfachloropyridazine and oxytetracyline were detected in surface run-off samples at maximum concentrations of 25.9 and 0.9microg/l respectively but only sulfachloropyridazine was detected in soil water samples at a maximum concentration of 0.78microg/l at 40cm depth 20 days after treatment. Tylosin was not detected in any soil or water samples. The results indicated that tylosin, when applied in slurry, posed very little risk of accumulating in soil or contaminating ground or surface water. However, tylosin may pose a risk if used to treat animals on pasture and risks arising from transformation products of tylosin, formed during slurry storage, cannot be ruled out. Oxytetracycline posed a very low risk of ground or surface water contamination but had the potential to persist in soils and sulfachloropyridazine posed a moderate risk of contaminating ground or surface water but had low potential to accumulate in soils. These findings were consistent with the sorption and persistence characteristics of the compounds and support a number of broad-scale monitoring studies that have measured these antibiotic classes in the environment.

Changes in antibacterial activity of triclosan and sulfa drugs due to photochemical transformations.

Sulfa drugs and triclosan represent two classes of antibacterials that have been found in natural waters and for which photodegradation is anticipated to be a significant loss process. Parent antibacterial compounds and the products of photolysis reactions were compared for three sulfa drugs and triclosan to determine the extent to which photolysis affects their antibacterial potency on Escherichia coli DH5alpha. Sulfathiazole (median effective concentration [EC50] = 20.0 microM), sulfamethoxazole (EC50 = 12.3 microM), and sulfachloropyridazine (EC50 = 6.9 microM) inhibited bacterial growth but did not affect respiratory activity. Photolysis products of these sulfa drugs did not retain any measurable ability to inhibit growth. Triclosan inhibited both the growth (EC50 = 0.24 microM) and respiratory activity of E. coli DH5alpha. Triclosan photolysis products also exhibited no measurable effect on growth or respiratory activity. These experiments indicate that the products of triclosan and sulfa drug photolysis are unlikely to possess antibacterial activity in natural waters. The rapid screening method used for these two classes of compounds will be useful for helping to identify photolabile antibacterial compounds, for which photoproducts could require further investigation.

The effect of pH and ionic strength on the sorption of sulfachloropyridazine, tylosin, and oxytetracycline to soil.

Antimicrobial agents are the most heavily used pharmaceuticals in intensive husbandry. Their usual discharge pathway is application to agricultural land as constituents of animal manure, which is used as fertilizer. Many of these compounds undergo pH-dependent speciation and, therefore, might occur as charged species in the soil environment. Hence, pH and ionic strength of the soil suspension can affect the sorption behavior of these compounds to soil. Consequently, the soil sorption of three antimicrobial agents--sulfachloropyridazine (SCP), tylosin (TYL), and oxytetracycline (OTC)--was investigated. Their respective sorption coefficients in two agricultural soils ranged from 1.5 to 1,800 L/kg. Sorption coefficients were greater under acidic conditions. Addition of an electrolyte to the solution led to decreased sorption of TYL and OTC by a factor of 3 to 20, but it did not influence the sorption of SCP. This behavior was analyzed by accounting for the pH-dependent speciation of TYL and OTC and considering the presence of OTC-calcium complexes. It appears that the decreased sorption of TYL and OTC with increasing ionic strength results from competition of the electrolyte cations with the positively charged TYL species and the positively charged OTC complexes. A model linking sorbate speciation with species-specific sorption coefficients can describe the pH dependence of the apparent sorption coefficients. This modeling approach is proposed for implementation in the assessment of sorption of ionizable compounds.

Estimation of soil sorption coefficients of veterinary pharmaceuticals from soil properties.

Environmental exposure assessment of veterinary pharmaceuticals requires estimating the sorption to soil. Soil sorption coefficients of three common, ionizable, antimicrobial agents (oxytetracycline [OTC], tylosin [TYL], and sulfachloropyridazine [SCP]) were studied in relation to the soil properties of 11 different soils. The soil sorption coefficient at natural pH varied from 950 to 7,200, 10 to 370, and 0.4 to 35 L/kg for OTC, TYL, and SCP, respectively. The variation increased by almost two orders of magnitude for OTC and TYL when pH was artificially adjusted. Separate soil properties (pH, organic carbon content, clay content, cation-exchange capacity, aluminum oxyhydroxide content, and iron oxyhydroxide content) were not able to explain more than half the variation observed in soil sorption coefficients. This reflects the complexity of the sorbent-sorbate interactions. Partial-least-squares (PLS) models, integrating all the soil properties listed above, were able to explain as much as 78% of the variation in sorption coefficients. The PLS model was able to predict the sorption coefficient with an accuracy of a factor of six. Considering the pH-dependent speciation, species-specific PLS models were developed. These models were able to predict species-specific sorption coefficients with an accuracy of a factor of three to four. However, the species-specific sorption models did not improve the estimation of sorption coefficients of species mixtures, because these models were developed with a reduced data set at standardized aqueous concentrations. In conclusion, pragmatic approaches like PLS modeling might be suitable to estimate soil sorption for risk assessment purposes.

Molecular modeling of hapten structure and relevance to broad specificity immunoassay of sulfonamide antibiotics.

Molecular modeling of hapten structure was used to predict and influence, through appropriate synthetic work, the outcome of an immunization program. Examination of the structures of sulfonamide antibiotics led to the development of a hypothesis and the consequent synthesis of a sulfacetamide-protein immunogen aimed at the generation of broad specificity anti-sulfonamide antibodies. The antisera generated, alongside anti-sulfachlorpyradizine antisera generated at the same time, were characterized for cross-reactions against a range of sulfonamide drugs, and were found to exhibit good but not the desired broad specificity. Discussion is presented as to the reasons for the failure of the hypothesis. Further hypotheses are developed and speculation is made as to the future of molecular modeling in immunochemical research.

Stability of sulfonamide antibiotics in spiked pig liver tissue during frozen storage.

A bulk portion of homogenized pig liver tissue was spiked at room temperature with 0.2 mg/kg (twice the Australian maximum residue limit) of each of sulfathiazole, sulfachlorpyridazine, sulfadimidine (sulfamethazine), sulfaquinoxaline, and sulfadimethoxine. After subsampling and packaging, selected individual packaged units were tested to confirm homogeneity of the prepared material. The material was stored frozen at -20 degrees C and analyzed in replicate by liquid chromatography on 11 sampling dates over a period of about 6 months. Analytical data were plotted on a log-linear scale and subjected to linear regression on the basis of first-order kinetics for the decay. Storage stabilities (decay half-lives at -20 degrees C) calculated from the mean slope of regression lines were sulfadimethoxine, 567 days; sulfadimidine, 457 days; sulfachlorpyridazine, 312 days; sulfathiazole, 291 days; and sulfaquinoxaline, 271 days. Significant depletion (65% loss) of residue was observed for sulfaquinoxaline during preparation of spiked bulk liver tissue. An extension of the study to measure the storage stability of sulfaquinoxaline under accelerated decay conditions (refrigerator temperature, 4 degrees C) showed it to be relatively unstable, with a decay half-life of 11 days. Results demonstrate the need for both regulatory agencies and testing laboratories to be aware of potential errors associated with improper transport, storage, and handling of tissue samples submitted for antibiotic testing.