Buenos Aires Province (República Argentina) has undergone, in the last years, a great increase in agricultural activities based on the incorporation of new technologies and reduction of diversity to meet the increasing food demand. The increase of intensive agricultural systems in Argentina involves the use of fertilizers and pesticides such as herbicides, insecticides, and fungicides. Chlorpyrifos is one of the insecticides most widely used in these crops and constitutes a risk for human health, birds, and aquatic biota such as macroinvertebrates and fishes. In order to assess the possible contamination that the use of this product may represent for the environment, it is necessary to study its interaction with the different types of soils because fate and transport of environmental pollutants may be influenced by their interactions with soil particles. The behavior of chlorpyrifos was analyzed through the study of the recoveries from spiked solid environmental matrices. A strong dependence with organic matter content was observed along with an important dependence with the initial concentrations employed. Here, we show that chlorpyrifos behavior on solid matrices not only depends on soil chemical composition. A significant dependence of recovery percentages with initial concentrations of the pesticide was evident in all cases. Recovery percentages decreased with an increase of the initial concentration employed, no matter the variations in matrices of chemical compositions.

Graphene oxide (GO) prepared by modified hummers method was used as adsorbent for removal of heavy metal ions. The oxygenous functional groups on the surface of GO were primarily responsible for the sorption of metal ions. The effects of the parameters of pH value, contact time, Cu(II) concentration, and adsorbent dosage on adsorption were examined. The sorption process conformed to the Freundlich isotherm, and the maximum sorption capacity of 117.5 mg g⁻¹ was observed at an initial pH value of 5.3 after agitating for 150 min. It was also found that Cu-pretreated GO could be desorbed by HCl and the reusability of GO could still maintain above 90 % of its initial capability after ten cycles. The results suggest that GO is an effective adsorbent for copper ions removal in water treatment.

Aquatic birds are often used as a health indicator of the marine ecosystem. African penguins living in the zoo make good research material as they form a link between the marine and the terrestrial ecosystem in terms of xenobiotic circulation. Tests were performed on whole herring—the food of the penguins—as well as on bird muscle, liver, brain, eggs, feathers and guano in order to determine total mercury, aldrin, dieldrin, endrin, isodrin, endosulfan isomers, endosulfan sulfate, methoxychlor, dichlorodiphenyltrichloroethane (DDT) and its metabolites. In herring and penguin, the tests did not show the presence of β-endosulfan, endosulfan sulfate, aldrin and isodrin. It was shown that penguins absorb about 36.8 μg of organochlorine pesticides and 4.6 μg of mercury with their food on a daily basis. Xenobiotics accumulate mostly in the liver, from where they are transported to the muscles and the brain, where the highest bioaccumulation factor is reached by endrin and pp’-DDT. Conceivably, the older the penguin, the higher is the concentration level of pesticides in its liver and brain. Molting was found to be the most effective way of eliminating mercury, dieldrin and methoxychlor from the system. Insecticides, such as DDT and its metabolites, were removed most effectively by females through laying of eggs. The standard four eggs laid within a year may have contained up to 20 % of the total amount of pesticides which had been absorbed with food, but no more than 5 % of mercury.

Anaerobic digestion is one of the most effective means for the stabilisation of sludge. However, it has a very slow rate-limiting hydrolysis phase which is attributed to the low biodegradability of cell walls and the presence of extracellular biopolymers. This study aims at investigating the effect of ultrasonic, microwave and combined microwave–ultrasonic treatment on biogas production, solids removal and dewaterability of anaerobically digested sludge. A comparison was made between the three pretreatment techniques conducting the digestion tests under similar conditions on the same synthetic sludge sample inoculated by digested sewage sludge. The experimental results depict that the combined microwave–ultrasonic treatment (2,450-MHz, 800-W and 3-min microwave treatment followed by 0.4-W/ml and 10-min ultrasonication) resulted in better digester performance than ultrasonic or microwave treatment. Mesophilic digestion of combined microwave–ultrasonic-pretreated sludge produced a significantly higher amount of methane (147 ml) after a sludge retention time of 17 days, whereas the ultrasonic- and microwave-treated sludge samples produced 30 and 16 ml of methane, respectively. The combined microwave–ultrasonic treatment resulted in total solids reduction of 56.8 % and volatile solid removal of 66.8 %. Furthermore, this combined treatment improved dewaterability of the digested sludge by reducing the capillary suction time (CST) down to 92 s, as compared to CST of 331 s for microwave-treated and 285 s for ultrasonically treated digested sludge samples. Optimisation tests were also carried out to determine the best combination.

Twenty-one plant leaf materials were screened for benzene adsorption efficiency in the static system, and the leaf material from Dieffenbachia picta, Acrostichum aureum, Ficus religiosa, Lagerstroemia macrocarpa, Alstonia scholaris, and Dracaena sanderiana were found to have high potential for benzene removal. The relation between quantity and composition of wax to benzene removal efficiency was studied. Although high quantities of wax occurred in some leaf materials, low benzene removal was clearly found if compared with other plant materials with the same wax quantity. Alpha-linoleic acid and dodecyl cyclohexane were found to be the main composition in plant leaf materials with high benzene adsorption, and it might be a key factor for benzene removal.

We investigated the effects of four commercial formulations of herbicides (glyphosate [GLY], metsulfuron-methyl [MET], bispyribac-sodium [BIS], and picloram [PIC]) individually, and in three 50:50 mixtures (GLY–MET, GLY–BIS, GLY–PIC) on the common toad Rhinella arenarum (Anura: Bufonidae) tadpoles. Enzymatic parameters such as, glutathione S-transferase (GST), butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) activities, as well as erythrocyte nuclear abnormalities (ENA) were studied. Interactions between herbicides in mixtures were evaluated and classified as additive, synergistic, or antagonistic. Toxicity results (48-h LC₅₀) showed that PIC was the most toxic herbicide, followed by BIS, GLY, and MET, while GLY–PIC was the most toxic mixture, followed by GLY–BIS, and GLY–MET. All commercial herbicide formulations and their mixtures significantly inhibited BChE activity in exposed tadpoles. The AChE activity was also inhibited by all herbicides and their mixtures, except by GLY–BIS. The inhibition of GST activity was only significant for GLY, MET, PIC, and GLY–MET. A significant increase in the frequency of ENA was found for tadpoles exposed either to commercial herbicide formulations or to mixtures, except for GLY. All the mixtures showed synergism for BChE activity while for AChE only the GLY–MET and GLY–PIC mixtures acted synergistically. GLY–MET showed synergism for GST, whereas for ENA, the mixture GLY–BIS was antagonistic. This study with R. arenarum tadpoles demonstrates that the interactions between three of the most intensively used herbicides in soybean crops results in synergistic effects on mortality and neurotoxicity and synergistic or additive effects in genotoxicity.

The congener-specific degradation pattern of polychlorinated biphenyls (PCBs) in Aroclor 1254 was investigated using a novel bacterial strain, Stenotrophomonas sp. JSG1, and it was accelerated by the surfactant, β-cyclodextrin. In addition, 4-chorobenzoic acid (CBA) degradation was also confirmed by the estimation of CBA depletion rate, microbial growth, and release of free chloride ion in mineral medium. Metal ions such as Ni²⁺, Hg²⁺ Ba²⁺, Cu²⁺, and NaCl (>4 %) were found greatly influencing the PCB degradation. However, Ca²⁺, Mg²⁺, Fe²⁺, and Mn²⁺ have not shown any impact on biodegradation. The bphC gene, which encodes an extradiol aromatic ring cleavage dioxygenase was successfully amplified and cloned. Phylogeny-based pairwise alignment of nucleotide sequences suggested that the cloned gene belongs to the extradiol dioxygenase family, but it showed high diversity to the traditional bphC gene. Results of the present investigation revealed that the Stenotrophomonas sp. JSG1 is an effective novel bacterium, which can be used in the PCB remediation studies.

This study examined the potential for regrowth of Escherichia coli in laboratory-incubated microcosms spiked with ultraviolet (UV)-disinfected sewage effluent and extracts derived from turfgrass or leaf litter. A second part of the study examined the potential of nutrients for predicting E. coli in two urban streams with point source effluent. Microcosms containing effluent and vegetation extracts were incubated for 72 h, samples were withdrawn over six time periods for measurement of E. coli. Streams were sampled every 2 weeks and E. coli and nutrients measured. E. coli counts in the microcosms exceeded the Texas state secondary contact recreation standard for surface water quality within 12 h for the turfgrass and within 18 h for leaf litter extracts. Univariate analysis of variance found that the interaction between vegetation extract source and concentration was more important than source of vegetation or concentration of extract alone. In the two streams sampled downstream of a point source effluent discharge, between 82 and 92 % of the variance in annual E. coli during high stream flow and between 55 and 57 % of the variance in annual E. coli during low stream flow was described by stream water-dissolved organic carbon (DOC) and dissolved organic nitrogen (DON), NH₄-N, NO₃-N, or PO₄-P. Once effluent is discharged to surface water, particularly during high flow conditions, DOC and DON derived from the landscape and nitrogen and PO₄-P derived from the effluent will provide ideal conditions for E. coli regrowth in surface waters downstream of the point source discharge.

A simple flow-based method was developed for the selective separation of arsenic species (+3 and +5) using a macrocycle-immobilized solid phase extraction (SPE) system, commonly known as molecular recognition technology (MRT) gel. Arsenic species in solution or in the eluent were subsequently quantified with graphite furnace atomic absorption spectrometry. The separation behaviors of As(III) and As(V) on MRT–SPE were investigated. It was found that As(V) can be selectively collected on the SPE system within the range of pH 4 to 9, while As(III) was passed through the MRT–SPE. The retention capacity of the MRT–SPE material for As(V) was found to be 0.25 ± 0.04 mmol g⁻¹. The detection limit of the method for As(V) was 0.06 μg L⁻¹, and the relative standard deviation was 2.9 % (n = 10, C = 1 μmol L⁻¹). Interference from the matrix ions was studied. In order to validate the developed method, certified reference materials of effluent wastewater and groundwater samples were analyzed, and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of tri- and pentavalent arsenic in natural water samples showing satisfactory recoveries (≥ 98.7 %).

The speciation of mercury (Hg) is a major determinant of its methylation rate by sulfate-reducing bacteria (SRB), considered the primary methylators. Under anoxic conditions, sulfur (S) cycling may have a significant influence on Hg complexation and methylation, by influencing both SRB activity and the pool of available reduced S ligands, as the presence of zero-valent sulfur (S(0)) in sulfidic water results in the formation of polysulfides. While SRB frequently coexist with S-oxidizing bacteria in natural environments, the effect that these organisms may have on methylation by SRB is not understood. In this study, we investigate the role of S(0) in methylation by SRB monocultures and cocultures with phototrophic green or purple S-oxidizing bacteria. In the coculture experiments, the presence of S-oxidizers was found to increase Hg methylation rates, apparently by maintaining favorable chemical speciation in the environment. The measured Hg methylation rates were in accord with predictions based on geochemical modeling of speciation. In SRB monoculture experiments conducted in the presence and absence of S(0), the data showed that at limited total Hg, the presence of polysulfides resulted in decreased Hg methylation, presumably by causing a decrease in the most bioavailable Hg–sulfide complexes. These results indicate that models of Hg speciation and methylation in the environment should include a detailed investigation of S redox speciation.