Harmful Microalgae Detection: Biosensors versus Some Conventional Methods.

In the last decade, there has been a steady stream of information on the methods and techniques available for detecting harmful algae species. The conventional approaches to identify harmful algal bloom (HAB), such as microscopy and molecular biological methods are mainly laboratory-based and require long assay times, skilled manpower, and pre-enrichment of samples involving various pre-experimental preparations. As an alternative, biosensors with a simple and rapid detection strategy could be an improvement over conventional methods for the detection of toxic algae species. Moreover, recent biosensors that involve the use of nanomaterials to detect HAB are showing further enhanced detection limits with a broader linear range. The improvement is attributed to nanomaterials' high surface area to volume ratio, excellent biological compatibility with biomolecules, and being capable of amplifying the electrochemical signal. Hence, this review presents the potential usage of biosensors over conventional methods to detect HABs. The methods reported for the detection of harmful algae species, ranging from conventional detection methods to current biosensor approaches will be discussed, along with their respective advantages and drawbacks to indicate the future prospects of biosensor technology for HAB event management.

The Role of 8-Amidoquinoline Derivatives as Fluorescent Probes for Zinc Ion Determination.

Mass-spectrometry-based and X-ray fluorescence-based techniques have allowed the study of the distribution of Zn2+ ions at extracellular and intracellular levels over the past few years. However, there are some issues during purification steps, sample preparation, suitability for quantification, and the instruments' availability. Therefore, work on fluorescent sensors based on 8-aminoquinoline as tools to detect Zn2+ ions in environmental and biological applications has been popular. Introducing various carboxamide groups into an 8-aminoquinoline molecule to create 8-amidoquinoline derivatives to improve water solubility and cell membrane permeability is also a recent trend. This review aims to present a general overview of the fluorophore 8-aminoquinoline and its derivatives as Zn2+ receptors for zinc sensor probes. Various fluorescent chemosensor designs based on 8-amidoquinoline and their effectiveness and potential as a recognition probe for zinc analysis were discussed. Based on this review, it can be concluded that derivatives of 8-amidoquinoline have vast potential as functional receptors for zinc ions primarily because of their fast reactivity, good selectivity, and bio-compatibility, especially for biological applications. To better understand the Zn2+ ion fluorophores' function, diversity of the coordination complex and geometries need further studies. This review provides information in elucidating, designing, and exploring new 8-amidoquinoline derivatives for future studies for the improvement of chemosensors that are selective and sensitive to Zn2+.

An electrochemical DNA biosensor fabricated from graphene decorated with graphitic nanospheres.

Graphene decorated with graphitic nanospheres functionalized with pyrene butyric acid (PBA) is used for the first time to fabricate a DNA biosensor. The electrode was formed by attaching a DNA probe onto PBA, which had been stacked onto a graphene material decorated with graphene nanospheres (GNSs). The nanomaterial was drop-coated onto a carbon screen-printed electrode (SPE) to create the GNS-PBA modified electrode (GNS-PBA/SPE). A simple method was used to produce GNS by annealing graphene oxide (GO) solution at high temperature. Field emission scanning electron micrographs confirmed the presence of a spherical shape of GNS with a diameter range of 40-80 nm. A stable and uniform PBA-modified GNS (GNS-PBA) was obtained with a facile ultrasonication step. Thus allowing aminated DNA probes of genetically modified (GM) soybean to be attached to the nanomaterials to form the DNA biosensor. The GNS-PBA/SPE exhibited excellent electrical conductivity via cyclic voltammetry (CV) and differential pulse voltammetry (DPV) tests using potassium ferricyanide (K3[Fe(CN)6]) as the electroactive probe. By employing an anthraquinone monosulfonic acid (AQMS) redox intercalator as the DNA hybridization indicator, the biosensor response was evaluated using the DPV electrochemical method. A good linear relationship between AQMS oxidation peak current and target DNA concentrations from 1.0 × 10-16 to 1.0 × 10-8 M with a limit of detection (LOD) of less than 1.0 × 10-16 M was obtained. Selectivity experiments revealed that the voltammetric GM DNA biosensor could discriminate complementary sequences of GM soybean from non-complementary sequences and hence good recoveries were obtained for real GM soybean sample analysis. The main advantage of using GNS is an improvement of the DNA biosensor analytical performance.

Highly Sensitive Fluorescence Sensor for Carrageenan from a Composite Methylcellulose/Polyacrylate Membrane.

Carrageenans are linear sulphated polysaccharides that are commonly added into confectionery products but may exert a detrimental effect to human health. A new and simpler way of carrageenan determination based on an optical sensor utilizing a methylcellulose/poly(n-butyl acrylate) (Mc/PnBA) composite membrane with immobilized methylene blue (MB) was developed. The hydrophilic Mc polymer membrane was successfully modified with a more hydrophobic acrylic polymer. This was to produce an insoluble membrane at room temperature where MB reagent could be immobilized to build an optical sensor for carrageenan analysis. The fluorescence intensity of MB in the composite membrane was found to be proportional to the carrageenan concentrations in a linear manner (1.0-20.0 mg L-1, R2 = 0.992) and with a detection limit at 0.4 mg L-1. Recovery of spiked carrageenan into commercial fruit juice products showed percentage recoveries between 90% and 102%. The optical sensor has the advantages of improved sensitivity and better selectivity to carrageenan when compared to other types of hydrocolloids. Its sensitivity was comparable to most sophisticated techniques for carageenan analysis but better than other types of optical sensors. Thus, this sensor provides a simple, rapid, and sensitive means for carageenan analysis.

A New and All-Solid-State Potentiometric Aluminium Ion Sensor for Water Analysis.

An all-solid-state potentiometric electrode system for aluminium ion determination was developed with a new aluminium ion sensor as the working electrode based on a new ionophore for aluminium ion, 1,1'-[(methylazanediyl)bis(ethane-2,1-diyl)]bis[3-(naphthalen-1-yl)thiourea] (ACH). The reference electrode was a potassium ion sensor, which acts as a pseudo-reference. Both electrodes were made from Ag/AgCl screen-print electrodes fabricated from a non-plasticized and photocurable poly(n-butyl acrylate) membrane that contained various other membrane components. The pseudo-reference potential based on the potassium ion sensor was fixed in 0.050 M KNO3, and such concentration of K+ ion did not interfere with the measurement of the Al3+ ion using the aluminium sensor. With such a pseudo-reference and in the presence of 0.050 M KNO3 as a background medium, the aluminium sensor measured changes of aluminium ion concentrations linearly from 10-6 to 10-2 M Al3+ ion with a Nernstian response of 17.70 ± 0.13 mV/decade. A low detection limit of 2.45 × 10-7 M was achieved with this all-solid-state potentiometric system. The aluminium sensor was insensitive to pH effects from 2.0 to 8.0 with a response time of less than 50 s. Under optimum conditions, a lifetime of 49 days was achieved with good sensor selectivity, reversibility, repeatability, and reproducibility. The all-solid-state electrode system was applied to analyze the Al3+ ion content of water samples from a water treatment plant. Compared with the conventional potentiometric detection system for aluminium ions, the new all-solid-state aluminium ion sensor incorporating a pseudo-reference from the potassium sensor demonstrated similar analytical performance. It thus provided a convenient means of aluminium content analysis in water treatment plants.

A Highly Sensitive Impedimetric DNA Biosensor Based on Hollow Silica Microspheres for Label-Free Determination of E. coli.

A novel label-free electrochemical DNA biosensor was constructed for the determination of Escherichia coli bacteria in environmental water samples. The aminated DNA probe was immobilized onto hollow silica microspheres (HSMs) functionalized with 3-aminopropyltriethoxysilane and deposited onto a screen-printed electrode (SPE) carbon paste with supported gold nanoparticles (AuNPs). The biosensor was optimized for higher specificity and sensitivity. The label-free E. coli DNA biosensor exhibited a dynamic linear response range of 1 × 10-10 µM to 1 × 10-5 µM (R2 = 0.982), with a limit of detection at 1.95 × 10-15 µM, without a redox mediator. The sensitivity of the developed DNA biosensor was comparable to the non-complementary and single-base mismatched DNA. The DNA biosensor demonstrated a stable response up to 21 days of storage at 4 ℃ and pH 7. The DNA biosensor response was regenerable over three successive regeneration and rehybridization cycles.

Sandwich-Type DNA Micro-Optode Based on Gold-Latex Spheres Label for Reflectance Dengue Virus Detection.

A DNA micro-optode for dengue virus detection was developed based on the sandwich hybridization strategy of DNAs on succinimide-functionalized poly(n-butyl acrylate) (poly(nBA-NAS)) microspheres. Gold nanoparticles (AuNPs) with an average diameter of ~20 nm were synthesized using a centrifugation-based method and adsorbed on the submicrometer-sized polyelectrolyte-coated poly(styrene-co-acrylic acid) (PSA) latex particles via an electrostatic method. The AuNP-latex spheres were attached to the thiolated reporter probe (rDNA) by Au-thiol binding to functionalize as an optical gold-latex-rDNA label. The one-step sandwich hybridization recognition involved a pair of a DNA probe, i.e., capture probe (pDNA), and AuNP-PSA reporter label that flanked the target DNA (complementary DNA (cDNA)). The concentration of dengue virus cDNA was optically transduced by immobilized AuNP-PSA-rDNA conjugates as the DNA micro-optode exhibited a violet hue upon the DNA sandwich hybridization reaction, which could be monitored by a fiber-optic reflectance spectrophotometer at 637 nm. The optical genosensor showed a linear reflectance response over a wide cDNA concentration range from 1.0 × 10-21 M to 1.0 × 10-12 M cDNA (R2 = 0.9807) with a limit of detection (LOD) of 1 × 10-29 M. The DNA biosensor was reusable for three consecutive applications after regeneration with mild sodium hydroxide. The sandwich-type optical biosensor was well validated with a molecular reverse transcription polymerase chain reaction (RT-PCR) technique for screening of dengue virus in clinical samples, e.g., serum, urine, and saliva from dengue virus-infected patients under informed consent.

A Colorimetric pH Sensor Based on Clitoria sp and Brassica sp for Monitoring of Food Spoilage Using Chromametry.

A developed colorimetric pH sensor film based on edible materials for real-time monitoring of food freshness is described. The mixed natural dyes from edible plants Clitoria sp and Brassica sp were extracted and incorporated into ι-carrageenan film as a colorimetric pH sensor film for monitoring food spoilage and its freshness. The color changes of the developed colorimetric sensor film were measured with chromametry and UV-vis spectroscopy, respectively. Experimental results show that colorimetric pH sensor film demonstrated statistically significant differences (p < 0.05) between CIE-L*a*b* coordinates color system indicated that the developed colorimetric sensor film was able to give a gradual change in color over a wide pH range. The color of the colorimetric sensor film also changes discretely and linearly with factors that contribute to food spoilage using shrimp and durian samples. Moreover, the developed colorimetric pH sensor film has the potential to be used as a safe, non-destructive testing and also a flexibly visual method for direct assessment of food freshness indicator during storage.

An Electrochemical DNA Biosensor for Carcinogenicity of Anticancer Compounds Based on Competition between Methylene Blue and Oligonucleotides.

A toxicity electrochemical DNA biosensor has been constructed for the detection of carcinogens using 24 base guanine DNA rich single stranded DNA, and methylene blue (MB) as the electroactive indicator. This amine terminated ssDNA was immobilized onto silica nanospheres and deposited on gold nanoparticle modified carbon-paste screen printed electrodes (SPEs). The modified SPE was initially exposed to a carcinogen, followed by immersion in methylene blue for an optimized duration. The biosensor response was measured using differential pulse voltammetry. The performance of the biosensor was identified on several anti-cancer compounds. The toxicity DNA biosensor demonstrated a linear response range to the cadmium chloride from 0.0005 ppm to 0.01 ppm (R2 = 0.928) with a limit of detection at 0.0004 ppm. The biosensor also exhibited its versatility to screen the carcinogenicity of potential anti-cancer compounds.

Electrochemical Sunset Yellow Biosensor Based on Photocured Polyacrylamide Membrane for Food Dye Monitoring.

An enzyme-based electrochemical biosensor was investigated for the analysis of Sunset Yellow synthetic food dye. A glassy carbon electrode was coated with a poly(acrylamide-co-ethyl methacrylate) membrane to immobilize laccase using a single-step photopolymerization procedure. Poly(acrylamide-co-ethyl methacrylate) membrane was demonstrated to have acceptable water absorption and suitable for biosensor application. Sunset Yellow biosensor exhibited a linear response range from 0.08 to 10.00 µM with a detection limit of 0.02 µM. This biosensor was successfully used to determine Sunset Yellow in soft drinks with recoveries of 99.0-101.6%. The method was validated using high-performance liquid chromatography, indicating the biosensor can be as a promising alternative method for Sunset Yellow detection.

Optical DNA Biosensor Based on Square-Planar Ethyl Piperidine Substituted Nickel(II) Salphen Complex for Dengue Virus Detection.

A sensitive and selective optical DNA biosensor was developed for dengue virus detection based on novel square-planar piperidine side chain-functionalized N,N'-bis-4-(hydroxysalicylidene)-phenylenediamine-nickel(II), which was able to intercalate via nucleobase stacking within DNA and be functionalized as an optical DNA hybridization marker. 3-Aminopropyltriethoxysilane (APTS)-modified porous silica nanospheres (PSiNs), was synthesized with a facile mini-emulsion method to act as a high capacity DNA carrier matrix. The Schiff base salphen complexes-labelled probe to target nucleic acid on the PSiNs renders a colour change of the DNA biosensor to a yellow background colour, which could be quantified via a reflectance transduction method. The reflectometric DNA biosensor demonstrated a wide linear response range to target DNA over the concentration range of 1.0 × 10-16-1.0 × 10-10 M (R² = 0.9879) with an ultralow limit of detection (LOD) at 0.2 aM. The optical DNA biosensor response was stable and maintainable at 92.8% of its initial response for up to seven days of storage duration with a response time of 90 min. The reflectance DNA biosensor obtained promising recovery values of close to 100% for the detection of spiked synthetic dengue virus serotypes 2 (DENV-2) DNA concentration in non-invasive human samples, indicating the high accuracy of the proposed DNA analytical method for early diagnosis of all potential infectious diseases or pathological genotypes.

Electrochemical Biosensor for Nitrite Based on Polyacrylic-Graphene Composite Film with Covalently Immobilized Hemoglobin.

A new biosensor for the analysis of nitrite in food was developed based on hemoglobin (Hb) covalently immobilized on the succinimide functionalized poly(n-butyl acrylate)-graphene [poly(nBA)-rGO] composite film deposited on a carbon-paste screen-printed electrode (SPE). The immobilized Hb on the poly(nBA)-rGO conducting matrix exhibited electrocatalytic ability for the reduction of nitrite with significant enhancement in the reduction peak at −0.6 V versus Ag/AgCl reference electrode. Thus, direct determination of nitrite can be achieved by monitoring the cathodic peak current signal of the proposed polyacrylic-graphene hybrid film-based voltammetric nitrite biosensor. The nitrite biosensor exhibited a reproducible dynamic linear response range from 0.05⁻5 mg L−1 nitrite and a detection limit of 0.03 mg L−1. No significant interference was observed by potential interfering ions such as Ca2+, Na⁺, K⁺, NH4⁺, Mg2+, and NO3− ions. Analysis of nitrite in both raw and processed edible bird’s nest (EBN) samples demonstrated recovery of close to 100%. The covalent immobilization of Hb on poly(nBA)-rGO composite film has improved the performance of the electrochemical nitrite biosensor in terms of broader detection range, lower detection limit, and prolonged biosensor stability.

An Amperometric Biosensor for the Determination of Bacterial Sepsis Biomarker, Secretory Phospholipase Group 2-IIA Using a Tri-Enzyme System.

A tri-enzyme system consisting of choline kinase/choline oxidase/horseradish peroxidase was used in the rapid and specific determination of the biomarker for bacterial sepsis infection, secretory phospholipase Group 2-IIA (sPLA2-IIA). These enzymes were individually immobilized onto the acrylic microspheres via succinimide groups for the preparation of an electrochemical biosensor. The reaction of sPLA2-IIA with its substrate initiated a cascading enzymatic reaction in the tri-enzyme system that led to the final production of hydrogen peroxide, which presence was indicated by the redox characteristics of potassium ferricyanide, K3Fe(CN)6. An amperometric biosensor based on enzyme conjugated acrylic microspheres and gold nanoparticles composite coated onto a carbon-paste screen printed electrode (SPE) was fabricated and the current measurement was performed at a low potential of 0.20 V. This enzymatic biosensor gave a linear range 0.01-100 ng/mL (R² = 0.98304) with a detection limit recorded at 5 × 10-3 ng/mL towards sPLA2-IIA. Moreover, the biosensor showed good reproducibility (relative standard deviation (RSD) of 3.04% (n = 5). The biosensor response was reliable up to 25 days of storage at 4 °C. Analysis of human serum samples for sPLA2-IIA indicated that the biosensor has potential for rapid bacterial sepsis diagnosis in hospital emergency department.

Synthesis, Characterization and DNA-Binding Studies of Hydroxyl Functionalized Platinum(II) Salphen Complexes.

The platinum(II) salphen complex N,N'-Bis-4-(hydroxysalicylidene)-phenylenediamine-platinum(II); (1) and its two derivatives containing hydroxyl functionalized side chains N,N'-bis-[4-[[1-(2-hydroxyethoxy)] salicylidene] phenylenediamine-platinum(II); (2) and N,N'-bis-[4-[[1-(3-hydroxypropoxy)] salicylidene] phenylenediamine-platinum(II); (3) were synthesized and characterized. The structures of the complexes were confirmed by 1H and 13C NMR spectroscopy, FTIR, ESI-MS and CHN elemental analyses. The effects of the hydroxyl substituent on the spectral properties and the DNA binding behaviors of the Pt(II) complexes were explored. The binding mode and interactions of these complexes with duplex DNA (calf thymus DNA and porcine DNA) and also single-stranded DNA were studied by UV-Vis and emission DNA titration. The complexes interact with DNA by intercalation binding mode with the binding constants in the order of magnitude (Kb = 104 M-1, CT-DNA) and (Kb = 105 M-1, porcine DNA). The intercalation of the complex in the DNA structure was proposed to happen by π-π stacking due to its square-planar geometry and aromatic rings structure. The phosphorescence emission spectral characteristics of Pt(II) complexes when interacted with DNA have been studied. Also, the application of the chosen hydroxypropoxy side chains complex (3) as an optical DNA biosensor, specifically for porcine DNA was investigated. These findings will be valuable for the potential use of the platinum(II) salphen complex as an optical DNA biosensor for the detection of porcine DNA in food products.

Multimodel ensembles of wheat growth: many models are better than one.

Crop models of crop growth are increasingly used to quantify the impact of global changes due to climate or crop management. Therefore, accuracy of simulation results is a major concern. Studies with ensembles of crop models can give valuable information about model accuracy and uncertainty, but such studies are difficult to organize and have only recently begun. We report on the largest ensemble study to date, of 27 wheat models tested in four contrasting locations for their accuracy in simulating multiple crop growth and yield variables. The relative error averaged over models was 24-38% for the different end-of-season variables including grain yield (GY) and grain protein concentration (GPC). There was little relation between error of a model for GY or GPC and error for in-season variables. Thus, most models did not arrive at accurate simulations of GY and GPC by accurately simulating preceding growth dynamics. Ensemble simulations, taking either the mean (e-mean) or median (e-median) of simulated values, gave better estimates than any individual model when all variables were considered. Compared to individual models, e-median ranked first in simulating measured GY and third in GPC. The error of e-mean and e-median declined with an increasing number of ensemble members, with little decrease beyond 10 models. We conclude that multimodel ensembles can be used to create new estimators with improved accuracy and consistency in simulating growth dynamics. We argue that these results are applicable to other crop species, and hypothesize that they apply more generally to ecological system models.

A high-throughput oxidative stress biosensor based on Escherichia coli roGFP2 cells immobilized in a k-carrageenan matrix.

Biosensors fabricated with whole-cell bacteria appear to be suitable for detecting bioavailability and toxicity effects of the chemical(s) of concern, but they are usually reported to have drawbacks like long response times (ranging from hours to days), narrow dynamic range and instability during long term storage. Our aim is to fabricate a sensitive whole-cell oxidative stress biosensor which has improved properties that address the mentioned weaknesses. In this paper, we report a novel high-throughput whole-cell biosensor fabricated by immobilizing roGFP2 expressing Escherichia coli cells in a k-carrageenan matrix, for the detection of oxidative stress challenged by metalloid compounds. The E. coli roGFP2 oxidative stress biosensor shows high sensitivity towards arsenite and selenite, with wide linear range and low detection limit (arsenite: 1.0 × 10(-3)-1.0 × 10(1) mg·L(-1), LOD: 2.0 × 10(-4) mg·L(-1); selenite: 1.0 × 10(-5)-1.0 × 10(2) mg·L(-1), LOD: 5.8 × 10(-6) mg·L(-1)), short response times (0-9 min), high stability and reproducibility. This research is expected to provide a new direction in performing high-throughput environmental toxicity screening with living bacterial cells which is capable of measuring the bioavailability and toxicity of environmental stressors in a friction of a second.

An optical biosensor from green fluorescent Escherichia coli for the evaluation of single and combined heavy metal toxicities.

A fluorescence-based fiber optic toxicity biosensor based on genetically modified Escherichia coli (E. coli) with green fluorescent protein (GFP) was developed for the evaluation of the toxicity of several hazardous heavy metal ions. The toxic metals include Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III). The optimum fluorescence excitation and emission wavelengths of the optical biosensor were 400 ± 2 nm and 485 ± 2 nm, respectively. Based on the toxicity observed under optimal conditions, the detection limits of Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(III) that can be detected using the toxicity biosensor were at 0.04, 0.32, 0.46, 2.80, 100, 250, 400, 720 and 2600 µg/L, respectively. The repeatability and reproducibility of the proposed biosensor were 3.5%-4.8% RSD (relative standard deviation) and 3.6%-5.1% RSD (n = 8), respectively. The biosensor response was stable for at least five weeks, and demonstrated higher sensitivity towards metal toxicity evaluation when compared to a conventional Microtox assay.

Microencapsulated Aliivibrio fischeri in alginate microspheres for monitoring heavy metal toxicity in environmental waters.

In this article a luminescence fiber optic biosensor for the microdetection of heavy metal toxicity in waters based on the marine bacterium Aliivibrio fischeri (A. fischeri) encapsulated in alginate microspheres is described. Cu(II), Cd(II), Pb(II), Zn(II), Cr(VI), Co(II), Ni(II), Ag(I) and Fe(II) were selected as sample toxic heavy metal ions for evaluation of the performance of this toxicity microbiosensor. The loss of bioluminescence response from immobilized A. fischeri bacterial cells corresponds to changes in the toxicity levels. The inhibition of the luminescent biosensor response collected at excitation and emission wavelengths of 287 ± 2 nm and 487 ± 2 nm, respectively, was found to be reproducible and repeatable within the relative standard deviation (RSD) range of 2.4-5.7% (n = 8). The toxicity biosensor based on alginate micropsheres exhibited a lower limit of detection (LOD) for Cu(II) (6.40 µg/L), Cd(II) (1.56 µg/L), Pb(II) (47 µg/L), Ag(I) (18 µg/L) than Zn(II) (320 µg/L), Cr(VI) (1,000 µg/L), Co(II) (1700 µg/L), Ni(II) (2800 µg/L), and Fe(III) (3100 µg/L). Such LOD values are lower when compared with other previous reported whole cell toxicity biosensors using agar gel, agarose gel and cellulose membrane biomatrices used for the immobilization of bacterial cells. The A. fischeri bacteria microencapsulated in alginate biopolymer could maintain their metabolic activity for a prolonged period of up to six weeks without any noticeable changes in the bioluminescence response. The bioluminescent biosensor could also be used for the determination of antagonistic toxicity levels for toxicant mixtures. A comparison of the results obtained by atomic absorption spectroscopy (AAS) and using the proposed luminescent A. fischeri-based biosensor suggests that the optical toxicity biosensor can be used for quantitative microdetermination of heavy metal toxicity in environmental water samples.

A large response range reflectometric urea biosensor made from silica-gel nanoparticles.

A new silica-gel nanospheres (SiO2NPs) composition was formulated, followed by biochemical surface functionalization to examine its potential in urea biosensor development. The SiO2NPs were basically synthesized based on sol-gel chemistry using a modified Stober method. The SiO2NPs surfaces were modified with amine (-NH2) functional groups for urease immobilization in the presence of glutaric acid (GA) cross-linker. The chromoionophore pH-sensitive dye ETH 5294 was physically adsorbed on the functionalized SiO2NPs as pH transducer. The immobilized urease determined urea concentration reflectometrically based on the colour change of the immobilized chromoionophore as a result of the enzymatic hydrolysis of urea. The pH changes on the biosensor due to the catalytic enzyme reaction of immobilized urease were found to correlate with the urea concentrations over a linear response range of 50-500 mM (R2 = 0.96) with a detection limit of 10 mM urea. The biosensor response time was 9 min with reproducibility of less than 10% relative standard deviation (RSD). This optical urea biosensor did not show interferences by Na+, K+, Mg2+ and NH4+ ions. The biosensor performance has been validated using urine samples in comparison with a non-enzymatic method based on the use of p-dimethylaminobenzaldehyde (DMAB) reagent and demonstrated a good correlation between the two different methods (R2 = 0.996 and regression slope of 1.0307). The SiO2NPs-based reflectometric urea biosensor showed improved dynamic linear response range when compared to other nanoparticle-based optical urea biosensors.

Land management policy shift influenced seasonal variation of erosion-induced nitrogen and phosphorus outputs from intensive agricultural catchment.

A shift in policy to intensive agricultural production and land management often leads to excessive fertilizer application and accelerated erosion with consequent detrimental effects to water bodies. We investigated the impact of that shift by quantifying the spatial and temporal change in sediment sources and associated total nitrogen (TN) and total phosphorus (TP) pollutants output loads in an intensive agricultural catchment in North China across one year (November 2021-November 2022). We describe the implications of this work for intensive agriculture elsewhere in China and other countries. Seasonal sediment source apportionment was estimated at the catchment outlet using Berillium-7 (7Be) combined with compound-specific stable isotope (CSSI) signatures from sources and sediments. Diagnostic 'fingerprints' in MixSIAR were used to discriminate sediment sources between forest and crop farmland converted from forest (F + C(F)), crop farmland (C), and vegetable farmland (V). Our study identified F + C(F) as the dominant sediment source (mean 55.24 ± 2.91 %), intermediate on V (mean 30.06 ± 2.20 %), and least on C (mean 14.70 ± 2.13 %). Sedimentation ranged from 37.98 ± 3.02 to 89.60 ± 12.68 t·ha-1·event-1 and coincided with shifted land use policy and rainfall distribution. The TN and TP in sediment were both mainly derived from F + C(F) (averaged 22.27 ± 4.26 t·event-1 and 11.62 ± 2.28 t·event-1) and least from V (averaged 1.63 ± 0.29 and 2.09 ± 0.33 t·event-1). Despite being a significant sediment source, V contributed little sediment TN and TP input for eutrophication. Our findings imply that F + C(F) are diffuse sources of catchment pollution over the short term. These results describe the successful use of CSSI and 7Be to cost-effectively quantify the seasonal variation of sediment TN and TP loads from land-use-specific sources in the catchment under shifting land management policy in China with potential for use elsewhere. These findings enable soil conservation strategies and land management practices optimized for implementing targeted pollutant abatement initiatives in intensive agriculture in China and elsewhere.