Abstract:
Manure often contains various veterinary drug residues and a large amount of dissolved organic matter (DOM). Veterinary drugs can enter the soil through manure application, and then enter water bodies through runoff and leaching processes, thereby posing a potential risk to the ecosystem safety and human health. Moreover, DOM may significantly affect the transport of veterinary drugs in the soil. However, the impact of manure DOM and its components on the transport of veterinary drugs in soil is still insufficiently explored by both experimental and modeling means.
Phyllostachys praecox plantations are widely distributed in southern China, and a large amount of manure is applied during the cultivation process. Therefore, this study focused on antibiotic transport in the soil of intensively managed
Phyllostachys praecox plantation. Through transport experiments in repacked columns (5 cm in diameter and 10 cm in height) of soil aggregates under saturated condition and numerical model simulations, we investigated the effects of pig manure DOM and its hydrophilic (HI) and hydrophobic (HO) fractions on the transport of four typical veterinary drugs (doxycycline, sulfamethazine, enrofloxacin, and florfenicol). In all inflow treatments, sulfamethazine and florfenicol exhibited high recovery rates (≥58.4% and ≥60.9%, respectively) in outflows from soil columns, while enrofloxacin and doxycycline were not detected in all outflow samples. This finding implies higher potential for sulfamethazine and florfenicol to be leached into shallow groundwater upon rainfall and irrigation. The additions of pig manure DOM and its HO fraction were found to significantly increase the recovery rate of florfenicol (by more than 20%) mainly through forming water-soluble complexes. Contrastingly, the addition of HI fraction of pig manure DOM slightly reduced the recovery rate of florfenicol, possibly through binding with florfenicol via hydrogen bonding and subsequent co-adsorption onto soil particles. Pig manure DOM could hardly affect the transport of sulfamethazine, and only the additions of its HI and HO fractions at high concentration (100 mg L
−1) led to a slight (by less than 10%) increase and decrease in the recovery rate of sulfamethazine, respectively. The performance of two-region model (TRM) (
R2: 0.966−0.993; root mean square error: 0.019−0.039) was better than that of convection dispersion equation (
R2: 0.951−0.992; root mean square error: 0.022−0.046) in simulating the breakthrough data of Br
−, which can be attributed to the good ability of TRM to describe the dominant role of macropores in conducting water in repacked columns of soil aggregates. TRM performed satisfactorily in simulating the non-equilibrium transport of veterinary antibiotics (
R2: 0.908−0.997; root mean square error: 0.014−0.092). Differences in calibrated model parameters between inflow treatments suggest that DOM and it polarity fractions could change the transport of veterinary antibiotics by altering adsorption site fraction in mobile water region and inter-regional mass transfer coefficient. Strongly sorbing veterinary drugs doxycycline and enrofloxacin could not pass through the soil column under all inflow treatments. This study found the differences in mechanisms by which manure-derived DOM and its polarity fractions affect veterinary drug transport, providing a scientific basis for optimizing the selection of manure products to be applied in
Phyllostachys praecox plantations, in order to minimize the risk of antibiotic pollution of local water bodies.