The main contaminant removal processes occurring in subsurface-flow constructed wetlands treating wastewater are reviewed. Redox conditions prevailing in the wetlands are analyzed and linked to contaminant removal mechanisms. The removal of organic matter and its accumulation in the granular medium of the wetlands are evaluated with regard to particulate and dissolved components and clogging processes. The main biological processes linked to organic matter transformation—aerobic respiration, denitrification, acid fermentation, sulfate reduction, and methanogenesis—are reviewed separately. The processes of removal of surfactants, pesticides and herbicides, emergent contaminants, nutrients, heavy metals and faecal organisms are analyzed. Advances in wetland modeling are presented as a powerful tool for understanding multiple interactions occurring in subsurface-flow constructed wetlands during the removal of contaminants.

The effect of hydraulic retention time (HRT) and seasonality on the removal efficiency of 26 organic microcontaminants from urban wastewater was studied in two pilot high-rate algal ponds (HRAPs). The targeted compounds included pharmaceuticals and personal care products, fire retardants, surfactants, anticorrosive agents, pesticides and plasticizers, among others. The pilot plant, which was fed at a surface loading rate of 7-29 g of COD m(-2)d(-1), consisted of a homogenisation tank and two parallel lines, each one with a primary settler and an HRAP with a surface area of 1.5 m(2) and a volume of 0.5 m(3). The two HRAPs were operated with different HRTs (4 and 8 d). The removal efficiency ranged from negligible removal to more than 90% depending on the compound. Microcontaminant removal efficiencies were enhanced during the warm season, while the HRT effect on microcontaminant removal was only noticeable in the cold season. Our results suggest that biodegradation and photodegradation are the most important removal pathways, whereas volatilization and sorption were solely achieved for hydrophobic compounds (log Kow>4) with a moderately high Henry's law constant values (11-12 Pa m(-3)mol(-1)) such as musk fragrances. Whereas acetaminophen, ibuprofen and oxybenzone presented ecotoxicological hazard quotients (HQs) higher than 1 in the influent wastewater samples, the HQs for the effluent water samples were always below 1.

Aerated batch reactors (2.5L) fed either with urban or synthetic wastewater were inoculated with microalgae (dominated by Chlorella sp. and Scenedesmus sp.) to remove caffeine, ibuprofen, galaxolide, tributyl phosphate, 4-octylphenol, tris(2-chloroethyl) phosphate and carbamazepine for 10 incubation days. Non-aerated and darkness reactors were used as controls. Microalgae grew at a rate of 0.25 d(-1) with the complete removal of N-NH4 during the course of the experiment. After 10 incubation days, up to 99% of the microcontaminants with a Henry's law constant higher than 3 10(-1) Pa m(3) mol(-1) (i.e., 4-octylphenol, galaxolide, and tributyl phosphate) were removed by volatilization due to the effect of air stripping. Whereas biodegradation was effective for removing ibuprofen and caffeine, carbamazepine and tris(2-chloroethyl) phosphate behaved as recalcitrant compounds. The use of microalgae was proved to be relevant for increasing the biodegradation removal efficiency of ibuprofen by 40% and reducing the lag phase of caffeine by 3 days. Moreover, the enantioselective biodegradation of S-ibuprofen suggested a biotic prevalent removal process, which was supported by the identification of carboxy-ibuprofen and hydroxy-ibuprofen. The results from microalgae reactors fed with synthetic wastewater showed no clear evidences of microalgae uptake of any of the studied microcontaminants.