Optofluidic chip with directly printed polymer optical waveguide Mach-Zehnder interferometer sensors for label-free biodetection.

Optofluidic devices hold great promise in biomedical diagnostics and testing because of their advantages of miniaturization, high sensitivity, high throughput, and high scalability. However, conventional silicon-based photonic chips suffer from complicated fabrication processes and less flexibility in functionalization, thus hindering their development of cost-effective biomedical diagnostic devices for daily tests and massive applications in responding to public health crises. In this paper, we present an optofluidic chip based on directly printed polymer optical waveguide Mach-Zehnder interferometer (MZI) sensors for label-free biomarker detection. With digital ultraviolet lithography technology, high-sensitivity asymmetric MZI microsensors based on a width-tailored optical waveguide are directly printed and vertically integrated with a microfluidic layer to make an optofluidic chip. Experimental results show that the sensitivity of the directly printed polymer optical waveguide MZI sensor is about 1695.95 nm/RIU. After being modified with capture molecules, i.e., goat anti-human immunoglobulin G (IgG), the polymer optical waveguide MZI sensors can on-chip detect human IgG at the concentration level of 1.78 pM. Such a polymer optical waveguide-based optofluidic chip has the advantages of miniaturization, cost-effectiveness, high sensitivity, and ease in functionalization and thus has great potential in the development of daily available point-of-care diagnostic and testing devices.

Immobilization of zinc and cadmium by biochar-based sulfidated nanoscale zero-valent iron in a co-contaminated soil: Performance, mechanism, and microbial response.

Mining and smelting of mineral resources causes excessive accumulation of potentially toxic metals (PTMs) in surrounding soils. Here, biochar-based sulfidated nanoscale zero-valent iron (SNZVI/BC) was designed via a one-step liquid phase reduction method to immobilize cadmium (Cd) and zinc (Zn) in a copolluted arable soil. A 60 d soil incubation experiment revealed that Cd and Zn immobilization efficiency by 6 % SNZVI/BC (25.2-26.2 %) was higher than those by individual SNZVI (13.9-18.0 %) or biochar (14.0-19.3 %) based on the changes in diethylene triamine pentaacetic acid (DTPA)-extractable PTM concentrations in soils, exhibiting a synergistic effect. Cd2+ or Zn2+ replaced isomorphously Fe2+ in amorphous ferrous sulfide, as revealed by XRD, XPS, and high-resolution TEM-EDS, forming metal sulfide precipitates and thus immobilizing PTMs. PTM immobilization was further enhanced by adsorption by biochar and oxidation products (Fe2O3 and Fe3O4) of SNZVI via precipitation and surface complexation. SNZVI/BC also increased the concentration of dissolved organic carbon and soil pH, thus stimulating the abundances of beneficial bacteria, i.e., Bacilli, Clostridia, and Desulfuromonadia. These functional bacteria further facilitated microbial Fe(III) reduction, production of ammonium and available potassium, and immobilization of PTMs in soils. The predicted function of the soil microbial community was improved after supplementation with SNZVI/BC. Overall, SNZVI/BC could be a promising functional material that not only immobilized PTMs but also enhanced available nutrients in cocontaminated soils.

Biochar inhibited hydrogen radical-induced Cd bioavailability in a paddy soil.

Herein, hydrogen (H·) radical was observed as a new pathway to produce hydroxyl (OH·) radicals that promoted cadmium sulfide (CdS) dissolution and thus Cd solubility in paddy soils. In soil incubation experiments, the bioavailable Cd concentrations in flooded paddy soils were increased by 8.44 % as the soil was aerated for 3d. For the first time, the H· radical was observed in aerated soil sludge. The association of CdS dissolution with free radicals was thereafter confirmed in an electrolysis experiment. Both H· and OH· radicals in electrolyzed water were confirmed by the electron paramagnetic resonance analysis. In the system with CdS, water electrolysis increased soluble Cd2+ concentration by 60.92 times, which was compromised by 43.2 % when the radical scavenger was introduced. This confirmed the free radicals can lead to oxidative dissolution of CdS. The H· radical was generated in systems with fulvic acid or catechol irradiated by ultraviolet lights, indicating soil organic carbon could be an important precursor for H· and OH· radicals. Biochar application decreased soil DTPA-Cd by 22-56 % invoking mechanisms besides adsorption. First, biochar quenched radicals and reduced CdS dissolution by 23.6 % in electrolyzed water in which -C-OH of biochar was oxidized to CO. Second, biochar boosted Fe/S-reducing bacteria and thus compromised CdS dissolution, as affirmed by a reversal correlation between soil available Fe2+ and DTPA-Cd concentrations. A similar phenomenon occurred in Shewanella oneidensis MR-1-inoculated soils. This study provided new insights into the bioavailability of Cd and offered feasible measures to remediate Cd-contaminated paddy soils with biochars.

Mixture of controlled-release and conventional urea fertilizer application changed soil aggregate stability, humic acid molecular composition, and maize nitrogen uptake.

Controlled-release urea (CRU) fertilizer application has been shown to improve crop yield and nitrogen (N) use efficiency. However, its effects when mixed with conventional urea fertilizer on soil aggregate stability, humic acid (HA) molecular composition and crop N uptake remain unclear. Soil and plant samples were collected from a long-term (2008-2019) experiment on field maize (Zea mays L., 'Zhengdan 958') which included two types of fertilizers [conventional urea fertilizer (CUF), blended CUF with CRU fertilizer (CRF)], four N application rates (0, 150, 300 and 450 kg ha-1), each in three replicates. The results showed that at 300 kg N ha-1, compared to CUF treatment, the CRF treatment significantly improved soil aggregate characteristics [aggregate content with particle size larger than 0.25 mm (R0.25) by 9.6%, mean weight diameter by 19.8%, and geometric mean diameter by 21.7%]. CRF treatment also increased HA content by 5.5%, fulvic acid (FA) by 5.5%, lignin-like molecules by 0.94 times, and protein-like molecules by 3.69 times. At grain-filling stage, CRF treatments significantly increased the sum of soil NH4+-N and NO3--N content by 23.3-24.5%, sap bleeding rate by 12.8-18.2% and N delivery rate through bleeding sap by 60.6-87.7% compared to CUF treatments at the same N application rate. At the same rate of N application, the CRF treatments significantly improved the average yield during three growing seasons by 9.4-14.0% in contrast with CUF treatments. The regression equations showed that the maximum yield was 8294 kg ha-1 for CUF at the application rate of 312 kg N ha-1 while it was 9890 kg ha-1 for CRF at the application rate of 286 kg N ha-1. We conclude that the long-term application of CRF changed the HA molecular structure, enhanced the water stable aggregates, improved crop N uptake, and increased economically viable maize yield.