This study evaluates the dynamics of nitrogen compounds generated by infiltration of wastewater from an inactive cesspit in the unconfined and sedimentary Adamantina Aquifer in Urânia, Brazil. A monitoring station, consisting of an 11.2 m well (1.8 m in diameter) with an array of 12 tensiometers and 12 suction lysimeters, was installed to monitor the shallow unsaturated zone from 0.5 to 9 m depth. A monitoring well was also installed below the water level to monitor the shallow aquifer. High amounts of ammonium (up to 96 mg/L NH4+-N) and nitrate (up to 458 mg/L NO3−-N) were observed in the unsaturated zone porewater which is comparable to active septic systems effluents. The distribution of NO3−, Cl− and Na+, typical constituents of sewage effluents, varied seasonally and spatially, which is correlated with changes in infiltration rates between the wet and dry seasons and with hydraulic conductivity variations in interlayered sandy and clayey sediments. A detailed monitoring of porewater geochemistry demonstrated the occurrence of several important reactions affecting nitrogen dynamics in the unsaturated zone: i) oxidation of organic matter, ii) ammonification, iii) nitrification, iv) methanogenesis, v) denitrification and likely, vi) sulfate reduction. The changes in nitrogen compound distribution and δ15NNO3 and δ18ONO3 values in porewater, in association with the N2O concentration and δ15NN2O and δ18ON2O signatures in gas samples, indicate the occurrence of nitrification and denitrification, suggesting the coexistence of reducing and oxidizing microsites in the unsaturated zone. This study indicated that cesspits can generate a significant amount of nitrate even a few years after being inactivated which can represent a potential long-term source of nitrate to groundwater in highly populated areas.

Balancing the nitrogen derived from sewage effluent and fertilizers is essential for efficiently utilizing the nitrogen and minimizing the environmental degradations when applying sewage effluent. Pot experiments of maize (Zea mays L.) under drip irrigation were performed using 15N labeled urea to quantify the nitrogen balances of sewage effluent and fertilizers. Field experiments were conducted to confirm the findings of pot experiments. Four nitrogen rates ranging from 0 to 2.64 g/pot (0–210 kg/ha equivalently) for pot experiments and from 0 to 180 kg/ha for field experiments were established applying either secondary sewage effluent (SW) or groundwater (GW). Both pot and field experiments revealed that SW irrigation boosted nitrogen uptake and yield of maize compared to GW irrigation. However, the sewage-derived effects decreased with increasing nitrogen rates. SW irrigation could facilitate the uptake of 15N labeled urea relative to GW irrigation. Nonetheless, the nitrogen containing in effluent possibly had lower uptake effectiveness than the fertilizer urea for maize, suggesting greater potential for nitrogen losses resulting from effluent nitrogen compared to urea nitrogen. The percentage utilization of effluent nitrogen declined from 43 to 34% in 2014 and 48 to 32% in 2015 as nitrogen rates increased from 0 to 2.64 g/pot. Besides, the percentages utilization of total nitrogen (including effluent and fertilizers) under SW irrigation increased from 43 to 55% in 2014 and from 48 to 55% in 2015 when the rates increased from 0 to 1.76 g/pot, and subsequently decreased to 48% in 2014 and 44% in 2015 at the rate of 2.64 g/pot. This result was strengthened by the pattern of nitrogen recovery efficiency observed in the field experiments. Overall results of pot and field experiments recommended an optimal rate of 120 kg/ha for maize under drip irrigation applying SW to maximize nitrogen use efficiency and achieve an acceptably high yield.

Compound-specific isotope analysis (CSIA) receives increasing interest for its ability to detect natural degradation of pesticides and pharmaceuticals. Despite recent laboratory studies, CSIA investigations of such micropollutants in the environment are still rare. To explore the certainty of information obtainable by CSIA in a near-environmental setting, a pulse of the pesticide bentazone, the pesticide metabolite 2,6-dichlorobenzamide (BAM), and the pharmaceuticals diclofenac and ibuprofen was released into a mesoscale aquifer with quasi-two-dimensional flow. Concentration breakthrough curves (BTC) of BAM and ibuprofen demonstrated neither degradation nor sorption. Bentazone was transformed but did not sorb significantly, whereas diclofenac showed both degradation and sorption. Carbon and nitrogen CSIA could be accomplished in similar concentrations as for “traditional” priority pollutants (low μg/L range), however, at the cost of uncertainties (0.4−0.5‰ (carbon), 1‰ (nitrogen)). Nonetheless, invariant carbon and nitrogen isotope values confirmed that BAM was neither degraded nor sorbed, while significant enrichment of 13C and in particular 15N corroborated transformation of diclofenac and bentazone. Retardation of diclofenac was reflected in additional 15N sorption isotope effects, whereas isotope fractionation of transverse dispersion could not be identified. These results provide a benchmark on the performance of CSIA to monitor the reactivity of micropollutants in aquifers and may guide future efforts to accomplish CSIA at even lower concentrations (ng/L range).

Although diclofenac is frequently found in aquatic systems, its degradability in the environment remains imperfectly understood. On the one hand, evidence from concentration analysis alone is inconclusive if an unknown hydrology impedes a distinction between degradation and dilution. On the other hand, not all transformation products may be detectable. As a new approach, we therefore developed GC-IRMS (gas chromatography-isotope-ratio mass-spectrometry) analysis for carbon and nitrogen isotope measurements of diclofenac. The method uses a derivatization step that can be conducted either online or offline, for optimized throughput or sensitivity, respectively. In combination with on-column injection, the latter method enables determination of diclofenac isotope ratios down to the sub-μgL–1 range in environmental samples. Degradation in an aerobic sediment-water system showed strong nitrogen isotope fractionation (εN = −7.1‰), whereas reductive diclofenac dechlorination was associated with significant carbon isotope fractionation (εC = −2.0‰). Hence dual element isotope analysis bears potential not only to detect diclofenac degradation, but even to distinguish both transformation pathways in the environment. In an explorative survey, analysis of commercial diclofenac products showed significant differences in carbon and nitrogen isotope ratios, demonstrating a further potential to track, and potentially even to authenticate, commercial production batches.