Delivering on sustainable development goals in wastewater reuse for agriculture: Initial prioritization of emerging pollutants in the Tula Valley, Mexico.

Wastewater reuse for agricultural irrigation is a widespread beneficial practice, in line with the sustainable development goals. However, contaminants of emerging concern (CECs) present in wastewater, such as pharmaceuticals, pose an environmental risk. The Tula Valley in Mexico is one of the world's largest agricultural areas reusing wastewater for agriculture. However, no untargeted CEC monitoring has been undertaken there, limiting the information available to prioritise local environmental risk assessment. Furthermore, CEC environmental presence in the Global South remains understudied, compared to the Global North. There is a risk that current research efforts focus on CECs predominantly found in the Global North, leading to strategies that may not be appropriate for the Global South where the pollution profile may be different. To address these knowledge gaps, a sampling campaign at five key sites in the Tula Valley was undertaken and samples analysed using multi-residue targeted and untargeted liquid chromatography mass spectrometry methods. Using the targeted data, ten CECs were found to be of environmental risk for at least one sampling site: 4­tert-octylphenol, acetaminophen, bezafibrate, diclofenac, erythromycin, levonorgestrel, simvastatin, sulfamethoxazole, trimethoprim and tramadol as well as total estrogenicity (combination of three steroid hormones). Six of these have not been previously quantified in the Tula Valley. Over one hundred pollutants never previously measured in the area were identified through untargeted analysis supported by library spectrum match. Examples include diclofenac and carbamazepine metabolites and area-specific pollutants such as the herbicide fomesafen. This research contributes to characterising the presence of CECs in the Global South, as well as providing site-specific data for the Tula Valley.

Translating wastewater reuse for irrigation from OECD Guidelines: Tramadol sorption and desorption in soil-water matrices.

Treated and untreated wastewater is often used for agricultural irrigation and, despite the many benefits of this practice, it poses the risk of biologically active chemical pollutants (such as pharmaceuticals, like tramadol) entering the environment. The partitioning of tramadol between soil/water at environmentally relevant concentrations is important to understand its environmental toxicity. Kinetics and isotherm sorption studies based on the Organisation for Economic Cooperation and Development (OECD) 106 Guideline were undertaken, ensuring comparability to previous studies. Studies were undertaken in three soils of different characteristics using aqueous concentrations of tramadol from 500 ng L-1 (environmentally relevant) to 100 µg L-1 (comparable to previous studies). Two of the soils presented a significantly (p < 0.05) higher sorption at a lower initial tramadol concentration (5000 ng L-1), compared to 20,000 ng L-1. Hysteresis was observed in all studied soils, indicating the accumulation of tramadol. Higher sorption to soils correlated with higher clay content, with soil/water partitioning coefficients (Kd) of 5.5 ± 13.3, 2.5 ± 3.8 and 0.9 ± 3.0 L kg1 for soils with clay contents of 41.9%, 24.5% and 7.4%, respectively. Cation exchange was proposed as the main sorption mechanism for tramadol to soils when the pH was below tramadol's pKa values (9.41 and 13.08). A comparative kinetics study between tramadol in soil/calcium chloride buffer and soil/wastewater effluent demonstrated significantly higher (p < 0.05) tramadol sorption to soil from wastewater effluent. This has the environmental implication that clay soils will be able to retain tramadol from irrigation water, despite the organic content of the irrigation water. Therefore, our studies show that tramadol soil sorption is likely to be higher in agricultural environments reusing wastewater than that predicted from experiments using the OECD 106 Guideline calcium chloride buffer.

Meta-analysis and machine learning to explore soil-water partitioning of common pharmaceuticals.

The first meta-analysis and modelling from batch-sorption literature studies of the soil/water partitioning of pharmaceuticals is presented. Analysis of the experimental conditions reported in the literature demonstrated that though batch-sorption studies have value, they are limited in evaluating partitioning under environmentally-relevant conditions. Recommendations are made to utilise environmental relevant pharmaceutical concentrations, perform batch-sorption studies at temperatures other than 4, 20 and 25 °C to better reflect climate diversity, and utilise the Guideline 106 methodology as a benchmark to enable comparison between future studies (and support modelling and prediction). The meta-dataset comprised 82 data points, which were modelled using multivariate analysis; where Kd (soil/water partitioning coefficient) was the independent variable. The dependent variables fit into three categories: 1) pharmaceutical studied (including physical-chemical properties), 2) soil characteristics and 3) experimental conditions. The pharmaceutical solubility, the soil/liquid equilibration time (prior to adding the pharmaceutical), the soil organic carbon, the soil sterilisation method and the liquid phase were found to be significantly important variables for predicting Kd.