Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils.

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers' breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils' hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.

Anthropogenic eutrophication of Lake Titicaca (Bolivia) revealed by carbon and nitrogen stable isotopes fingerprinting.

Cultural eutrophication is the leading cause of water quality degradation worldwide. The traditional monitoring of eutrophication is time-consuming and not integrative in space and time. Here, we examined the use of carbon (δ13C) and nitrogen (δ15N) isotopic composition to track the degree of eutrophication in a bay of Lake Titicaca impacted by anthropogenic (urban, industrial and agricultural wastewater) discharges. Our results show increasing δ13C and decreasing δ15N signatures in macrophytes and suspended particulate matter with distance to the wastewater source. In contrast to δ15N and δ13C signatures, in-between aquatic plants distributed along the slope were not only affected by anthropogenic discharges but also by the pathway of carbon uptake, i.e., atmospheric (emerged) vs aquatic (submerged). A binary mixing model elaborated from pristine and anthropogenic isotope end-members allowed the assessment of anthropogenically derived C and N incorporation in macrophytes with distance to the source. Higher anthropogenic contribution was observed during the wet season, attributed to enhanced wastewater discharges and leaching of agricultural areas. For both seasons, eutrophication was however found naturally attenuated within 6 to 8 km from the wastewater source. Here, we confirm that carbon and nitrogen stable isotopes are simple, integrative and time-saving tools to evaluate the degree of eutrophication (seasonally or annually) in anthropogenically impacted aquatic ecosystems.

Sulfamethoxazole biodegradation and impacts on soil microbial communities in a Bolivian arid high altitude catchment.

The processes controlling antibiotics fate in ecosystems are poorly understood, yet their presence can inhibit bacterial growth and induce the development of bacterial resistance. Sulfamethoxazole (SMX) is one of the most frequently detected sulfonamides in natural environments due to its low metabolism and molecular properties. This work presents pioneering results on SMX biodegradation and impact in high altitude soils (Bolivian Altiplano), allowing a better understanding of the persistence, spread and impact of this antibiotic at the global watershed scale. Our results showed significant dissipation of SMX in relation to its adsorption, hydrolysis and biotransformation. However, biodegradation appears to be lower in these mountain soils than in lowland soils as widely described in the literature. The half-life of SMX ranges from 12 to 346 days in non-sterile soils. In one soil, no biotic degradation was observed, indicating a likely high persistence. Biodegradation was related to OC content and to proximity to urban activities. Regarding the study of the impacts of SMX, the DGGE results were less sensitive than the sequencing. In general, SMX strongly changes the structure and composition of the studied soils at high altitudes, which is comparable to the observations of other authors in lowland soils. The phylum Actinobacter showed high sensitivity to SMX. In contrast, the abundance of ɣ-proteobacteria remained almost unchanged. Soil contamination with SMX did not lead to the development of the studied resistance genes (sul1 and sul2) in soils where they were absent at the beginning of the experiment. Thus, the presence of SMX resistance genes seems to be related to irrigation with wastewater carrying the studied resistance genes.

Assessment of the Sulfamethoxazole mobility in natural soils and of the risk of contamination of water resources at the catchment scale.

Sulfamethoxazole (SMX) is one of the antibiotics most commonly detected in aquatic and terrestrial environments and is still widely used, especially in low income countries. SMX is assumed to be highly mobile in soils due to its intrinsic molecular properties. Ten soils with contrasting properties and representative of the catchment soil types and land uses were collected throughout the watershed, which undergoes very rapid urban development. SMX displacement experiments were carried out in repacked columns of the 10 soils to explore SMX reactive transfer (mobility and reactivity) in order to assess the contamination risk of water resources in the context of the Bolivian Altiplano. Relevant sorption processes were identified by modelling (HYDRUS-1D) considering different sorption concepts. SMX mobility was best simulated when considering irreversible sorption as well as instantaneous and rate-limited reversible sorption, depending on the soil type. SMX mobility appeared lower in soils located upstream of the watershed (organic and acidic soils - Regosol) in relation with a higher adsorption capacity compared to the soils located downstream (lower organic carbon content - Cambisol). By combining soil column experiments and soil profiles description, this study suggests that SMX can be classified as a moderately to highly mobile compound in the studied watershed, depending principally on soil properties such as pH and OC. Potential risks of surface and groundwater pollution by SMX were thus identified in the lower part of the studied catchment, threatening Lake Titicaca water quality.

Antibiotic pollution in the Katari subcatchment of the Titicaca Lake: Major transformation products and occurrence of resistance genes.

An increasing number of studies pointed out the ubiquitous presence of medical residues in surface and ground water as well as in soil compartments. Not only antibiotics can be found in the environment but also their transformation products about which little information is generally available. The development of bacterial resistance to antibiotics is particularly worrying as it can lead to sanitary and health problems. Studies about the dissemination of antibiotics and associated resistances in the Bolivian Altiplano are scarce. We provide baseline information on the occurrence of Sulfamethoxazole (SMX) and Trimethoprim (TMP) antibiotics as well as on the most common human SMX transformation products (TP) and on the occurrence of sulfonamide resistance genes. The studied water and soil compartments presented high levels of antibiotic pollution. This situation was shown to be mainly linked with uncontrolled discharges of treated and untreated wastewaters, resulting on the presence of antibiotics in the Titicaca Lake. SMX TPs were detected in surface waters and on soil sampled next to the wastewater treatment plant (WWTP). SMX resistance genes sulI and sulII were widely detected in the basin hydrological network, even in areas unpolluted with antibiotics. Mechanisms of co-selection of antibiotic- and metal- resistance may be involved in the prevalence of ARG's in pristine areas with no anthropogenic activity and free of antibiotic pollution.

Mercury contamination level and speciation inventory in Lakes Titicaca & Uru-Uru (Bolivia): Current status and future trends.

Aquatic ecosystems of the Bolivian Altiplano (∼3800 m a.s.l.) are characterized by extreme hydro-climatic constrains (e.g., high UV-radiations and low oxygen) and are under the pressure of increasing anthropogenic activities, unregulated mining, agricultural and urban development. We report here a complete inventory of mercury (Hg) levels and speciation in the water column, atmosphere, sediment and key sentinel organisms (i.e., plankton, fish and birds) of two endorheic Lakes of the same watershed differing with respect to their size, eutrophication and contamination levels. Total Hg (THg) and monomethylmercury (MMHg) concentrations in filtered water and sediment of Lake Titicaca are in the lowest range of reported levels in other large lakes worldwide. Downstream, Hg levels are 3-10 times higher in the shallow eutrophic Lake Uru-Uru than in Lake Titicaca due to high Hg inputs from the surrounding mining region. High percentages of MMHg were found in the filtered and unfiltered water rising up from <1 to ∼50% THg from the oligo/hetero-trophic Lake Titicaca to the eutrophic Lake Uru-Uru. Such high %MMHg is explained by a high in situ MMHg production in relation to the sulfate rich substrate, the low oxygen levels of the water column, and the stabilization of MMHg due to abundant ligands present in these alkaline waters. Differences in MMHg concentrations in water and sediments compartments between Lake Titicaca and Uru-Uru were found to mirror the offset in MMHg levels that also exist in their respective food webs. This suggests that in situ MMHg baseline production is likely the main factor controlling MMHg levels in fish species consumed by the local population. Finally, the increase of anthropogenic pressure in Lake Titicaca may probably enhance eutrophication processes which favor MMHg production and thus accumulation in water and biota.