Copper (Cu) speciation in organic-waste (OW) amended soil: Instability of OW-borne Cu(I) sulfide and role of clay and iron oxide minerals.

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cutotal = 122 mg·kg-1) was amended over 11 years with Cu-rich pig slurry in which Cu was 100 % Cu(I) sulfide. Natural Cu associated with clay and iron oxide minerals persisted in the amended soil, but the exogenous Cu(I) sulfide was unstable. The increase in Cu concentration in the amended soil to 174 mg·kg-1 was accounted for the increase of Cu sorbed to kaolinite and Cu bound to organic matter. These results are important for better understanding the natural occurrence of Cu in soils and for assessing the environmental impacts of organic waste recycling in agricultural fields.

Influence of hydraulic loading rate and recirculation on oxygen transfer in a vertical flow constructed wetland.

The oxygen transfer rate (OTR) has a significant impact on the design and operation of vertical flow constructed wetlands (VFCWs) intended for organic matter removal and nitrification. Despite its key role, the information on real oxygen input in VFCWs is limited, being usually estimated by mass balance (stoichiometry), through which is calculated only the oxygen consumption rate (OCR). In this study, for the first time, the gas tracer method was applied to evaluate the oxygen transfer capacity of a real-scale VFCW (24.5 m2) applied to the treatment of domestic wastewater. Propane was used as tracer. The OCR and the OTR were evaluated in VFCW under hydraulic loading rates (HLR) of 60, 90, and 120 mm d-1 corresponding to recirculation rations of 0%, 50%, and 100%. The OTR in standard conditions (20 °C) ranged from 120 to 176 g O2 m-2 d-1. The highest OTR was found for the lowest HLR. For the operating conditions tested, the OTR obtained with gas tracer were higher than the OCR calculated by stoichiometry in VFCW, which ranged from 20.6 to 27.8 g O2 m-2 d-1. Besides, the OTR were sufficient to satisfy the VFCW oxygen demand for organic matter removal and nitrification. These results show that the gas tracer method for OTR determination may allow advances on the understanding of treatment processes and on the design of new VFCWs since its treatment performance requires aerobic conditions.