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1. Pb Mineral Precipitation in Solutions of Sulfate, Carbonate and Phosphate: Measured and Modeled Pb Solubility and Pb2+ Activity

   https://doi.org/10.3390/min11060620  

   Li, Xinxin; Azimzadeh, Behrooz; Martinez, Carmen Enid; McBride, Murray B. (June 2021, Minerals)

   Lead (Pb) solubility is commonly limited by dissolution–precipitation reactions of secondary mineral phases in contaminated soils and water. In the research described here, Pb solubility and free Pb2+ ion activities were measured following the precipitation of Pb minerals from aqueous solutions containing sulfate or carbonate in a 1:5 mole ratio in the absence and presence of phosphate over the pH range 4.0–9.0. Using X-ray diffraction and Fourier-transform infrared spectroscopic analysis, we identified anglesite formed in sulfate-containing solutions at low pH. At higher pH, Pb carbonate and carbonate-sulfate minerals, hydrocerussite and leadhillite, were formed in preference to anglesite. Precipitates formed in the Pb-carbonate systems over the pH range of 6 to 9 were composed of cerussite and hydrocerussite, with the latter favored only at the highest pH investigated. The addition of phosphate into the Pb-sulfate and Pb-carbonate systems resulted in the precipitation of Pb3(PO4)2 and structurally related pyromorphite minerals and prevented Pb sulfate and carbonate mineral formation. Phosphate increased the efficiency of Pb removal from solution and decreased free Pb2+ ion activity, causing over 99.9% of Pb to be precipitated. Free Pb2+ ion activities measured using the ion-selective electrode revealed lower values than predicted from thermodynamic constants, indicating that the precipitated minerals may have lower KSP values than generally reported in thermodynamic databases. Conversely, dissolved Pb was frequently greater than predicted based on a speciation model using accepted thermodynamic constants for Pb ion-pair formation in solution. The tendency of the thermodynamic models to underestimate Pb solubility while overestimating free Pb2+ activity in these systems, at least in the higher pH range, indicates that soluble Pb ion-pair formation constants and KSP values need correction in the models. 

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2. Sensing Antibiotics in Wastewater Using Surface-Enhanced Raman Scattering

   Yen-Hsiang Huang, Hong Wei (March 2023, Environmental Science & Technology)

   Rapid and cost-effective detection of antibiotics in wastewater and through wastewater treatment processes is an important first step in developing effective strategies for their removal. Surface-enhanced Raman scattering (SERS) has the potential for label-free, real-time sensing of antibiotic contamination in the environment. This study reports the testing of two gold nanostructures as SERS substrates for the label-free detection of quinoline, a small-molecular-weight antibiotic that is commonly found in wastewater. The results showed that the self-assembled SERS substrate was able to quantify quinoline spiked in wastewater with a lower limit of detection (LoD) of 5.01 ppb. The SERStrate (commercially available SERS substrate with gold nanopillars) had a similar sensitivity for quinoline quantification in pure water (LoD of 1.15 ppb) but did not perform well for quinoline quantification in wastewater (LoD of 97.5 ppm) due to interferences from non-target molecules in the wastewater. Models constructed based on machine learning algorithms could improve the separation and identification of quinoline Raman spectra from those of interference molecules to some degree, but the selectivity of SERS intensification was more critical to achieve the identification and quantification of the target analyte. The results of this study are a proof-of-concept for SERS applications in label-free sensing of environmental contaminants. Further research is warranted to transform the concept into a practical technology for environmental monitoring. 

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3. Ultrafast Detection of Arsenic Using Carbon-Fiber Microelectrodes and Fast-Scan Cyclic Voltammetry

   https://doi.org/10.3390/mi15060733  

   Manring, Noel; Strini, Miriam; Koifman, Gene; Xavier, Jonathan; Smeltz, Jessica L; Pathirathna, Pavithra (May 2024, Micromachines)

   Arsenic contamination poses a significant public health risk worldwide, with chronic exposure leading to various health issues. Detecting and monitoring arsenic exposure accurately remains challenging, necessitating the development of sensitive detection methods. In this study, we introduce a novel approach using fast-scan cyclic voltammetry (FSCV) coupled with carbon-fiber microelectrodes (CFMs) for the electrochemical detection of As3+. Through an in-depth pH study using tris buffer, we optimized the electrochemical parameters for both acidic and basic media. Our sensor demonstrated high selectivity, distinguishing the As3+ signal from those of As5+ and other potential interferents under ambient conditions. We achieved a limit of detection (LOD) of 0.5 μM (37.46 ppb) and a sensitivity of 2.292 nA/μM for bare CFMs. Microscopic data confirmed the sensor’s stability at lower, physiologically relevant concentrations. Additionally, using our previously reported double-bore CFMs, we simultaneously detected As3+-Cu2+ and As3+-Cd2+ in tris buffer, enhancing the LOD of As3+ to 0.2 μM (14.98 ppb). To our knowledge, this is the first study to use CFMs for the rapid and selective detection of As3+ via FSCV. Our sensor’s ability to distinguish As3+ from As5+ in a physiologically relevant pH environment showcases its potential for future in vivo studies. 

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4. Atomically dispersed Pb ionic sites in PbCdSe quantum dot gels enhance room-temperature NO2 sensing

   https://doi.org/10.1038/s41467-021-25192-4  

   Geng, Xin; Li, Shuwei; Mawella-Vithanage, Lalani; Ma, Tao; Kilani, Mohamed; Wang, Bingwen; Ma, Lu; Hewa-Rahinduwage, Chathuranga C.; Shafikova, Alina; Nikolla, Eranda; et al (August 2021, Nature Communications)

   Abstract Atmospheric NO₂is of great concern due to its adverse effects on human health and the environment, motivating research on NO₂detection and remediation. Existing low-cost room-temperature NO₂sensors often suffer from low sensitivity at the ppb level or long recovery times, reflecting the trade-off between sensor response and recovery time. Here, we report an atomically dispersed metal ion strategy to address it. We discover that bimetallic PbCdSe quantum dot (QD) gels containing atomically dispersed Pb ionic sites achieve the optimal combination of strong sensor response and fast recovery, leading to a high-performance room-temperature p-type semiconductor NO₂sensor as characterized by a combination of ultra–low limit of detection, high sensitivity and stability, fast response and recovery. With the help of theoretical calculations, we reveal the high performance of the PbCdSe QD gel arises from the unique tuning effects of Pb ionic sites on NO₂binding at their neighboring Cd sites. 

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5. Probing the Ni ²⁺ ‐selective Response of Fluorescent Probe NiSensor‐1 with the NiCast Photocaged Complex ^{† ‡}

   https://doi.org/10.1111/php.13567  

   Hickey, Erin E.; Kennedy, Daniel P.; Gwizdala, Celina; Basa, Prem N.; Müller, Peter; MacDonald, John; Burdette, Shawn C. (December 2021, Photochemistry and Photobiology)

   Abstract CTEA (N,N‐bis[2‐(carboxylmethyl)thioethyl]amine) is a mixed donor ligand that has been incorporated into multiple fluorescent sensors such as NiSensor‐1 that was reported to be selective for Ni²⁺. Other metal ions such as Zn²⁺do not produce an emission response in aqueous solution. To investigate the coordination chemistry and selectivity of this receptor, we prepared NiCast, a photocage containing the CTEA receptor. Cast photocages undergo a photoreaction that decreases electron density on a metal‐bound aniline nitrogen atom, which shifts the binding equilibrium toward unbound metal ion. The unique selectivity of CTEA was examined by measuring the binding affinity of NiCast and the CTEA receptor for Ni²⁺, Zn²⁺, Cd²⁺and Cu²⁺under different conditions. In aqueous solution, Ni²⁺binds more strongly to the aniline nitrogen atom than Cd²⁺; however, in CH₃CN, the change in affinity virtually disappears. The crystal structure of [Cu(CTEA)], which exhibits a Jahn–Teller–distorted square pyramidal structure, was also analyzed to gain more insight into the underlying coordination chemistry. These studies suggest that the fluorescence selectivity of NiSensor‐1 in aqueous solution is due to a stronger interaction between the aniline nitrogen atom and Ni²⁺compared to other divalent metal ions except Cu²⁺. 

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