Dithizone-functionalized C18 online solid-phase extraction-HPLC-ICP-MS for speciation of ultra-trace organic and inorganic mercury in cereals and environmental samples

A simple and efficient dithizone-functionalized solid-phase extraction (SPE) procedure, online coupled with high-performance liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry, was developed for the first time for enrichment and determination of ultra-trace mercury (Hg) species (inorganic divalent Hg (Hg(II)), methylmercury (CH₃Hg(II)) and ethylmercury (C₂H₅Hg(II)) in cereals and environmental samples. In the proposed method, functionalization of the commercial C₁₈ column with dithizone, enrichment, and elution of the above Hg species can be completed online with the developed SPE device. A simple solution of 2-mercaptoethanol (1% (V/V)) could be used as an eluent for both the SPE and HPLC separation of Hg species, significantly simplifying the method and instrumentation. The online SPE method was optimized by varying dithizone dose, 2-mercaptoethanol concentration, and sample volume. In addition, the effect of pH, coexisting interfering ions, and salt effect on the enrichment was also discussed. Under the optimized conditions, the detection limits of Hg species for 5 mL water sample were 0.15 ng/L for Hg(II), 0.07 ng/L for CH₃Hg(II), and 0.04 ng/L for C₂H₅Hg(II) with recoveries in the range of 85%–100%. The developed dithizone-functionalized C₁₈ SPE column can be reused after a single functionalization, which significantly simplifies the enrichment step. Moreover, the stability of Hg species enriched on the SPE column demonstrated its suitability for field sampling of Hg species for later laboratory analysis. This environment-friendly method offers a robust tool to detect ultra-trace Hg species in cereals and environmental samples.     

Enzymatic activity and half-lives of capsaicin,dihydrocapsaicin, and pentadecanoic acid methyl ester in soil sprayed with hot pepper extract

Pest management is facing economic and ecological challenges in the United States and worldwide due to pest resistance, human and environmental hazards caused by use of synthetic pesticides. Natural product-based pesticides offer advantages that they are specific to the target species and typically have unique modes of action with little mammalian toxicity. Studies conducted at Kentucky State University revealed that the insecticidal and acaricidal performance of crude extracts from the fruits of Capsicum species justified the need for developing a natural pesticide formulation for agricultural use. Analysis of hot pepper extracts indicated the presence of three compounds having pesticidal efficacy: capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester. The main objectives of this investigation were to: i) determine the half-live (T_1/2 value) of capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester in soil sprayed with hot pepper formulation and ii) assess the impact of hot pepper formulation on total soil enzyme activity. Analysis of soil sprayed with pepper extracts indicated that T_1/2 values of capsaicin, dihydrocapsaicin, and pentadecanoic acid methyl ester were 7.3, 1.5, and 10.2 d, respectively. Hydrolysis of the fluorescein diacetate [3, 6-diacetylfluorescein (FDA)], used for measuring overall soil enzyme activities, indicated that total enzyme activities was slightly enhanced by 2% in soil sprayed with hot pepper extracts.     

Experimental study of chromium adsorption on minerals in the presence of phthalic and humic acids

The effect of phthalic acid (benzene 1,2 dicarboxylic acid), a surrogate compound for natural organic matter, and of humic acid, on the adsorption of chromium to the surface of minerals was observed. In ternary systems involving phthalic acid, chromium(III) adsorption decreases on clays, probably because of aqueous Cr(III)-phthalate complexation, preventing ionic-exchange. Phthalic acid was also found to reduce chromium(VI) adsorption onto alumina, because of a competitive effect. In ternary systems involving humic acid, Cr(III) adsorption is increased in the low pH range because of the formation of surface ternary complex S-L-Cr(III) and is decreased in the high pH range because of aqueous Cr(III)-humate complexation.     

Microbial Degradation of the Natural Rubber in Tire Tread Compound by a Strain of Nocardia

Tread compound of truck tires is based primarily on natural rubber or blends of natural rubber (NR) and synthetic polymers in combination with high grade carbon black. When the tread compound is attacked by a strain of Nocardia capable of degrading NR, part of the NR in the compound is mineralized, and part is disintegrated to very small black particles. The small black particles consist of the residual rubber and inorganic fillers. At higher NR content, large and deep cavities are formed on the surface of the pieces of the tread compound after microbial disintegration. At lower content of NR, large but very shallow cavities or very small pits can be seen on the tread surface. During microbial growth on the tread compound, isoprene oligomers with molecular weight of about two thousand are produced. Not only the isoprene oligomers, but also butadiene oligomers are produced during microbial disintegration of the tread compound of NR/synthetic rubber blend.     

Endemic pollinator response to organic vs. conventional farming and landscape context in the Cape Floristic Region biodiversity hotspot

The effects of organic management and landscape context on two highly endemic and important pollinator taxa (bees and monkey beetles) were studied in the Cape Floristic Region (CFR) biodiversity hotspot, where a quarter of the land is intensively managed mostly for grape production. This functional group was chosen as there is concern worldwide over pollinator decline, particularly in regions of high levels of endemism of both flora and fauna such as the CFR. Species richness and abundance of bees and monkey beetles were sampled and compared between organic and conventional vineyards, with natural vegetation as reference habitat. Species richness of monkey beetles, but not the species richness of bees, benefited from organic compared to conventional vineyard management. Our findings support the hypothesis that the effects of landscape context and management may be taxon dependent. Monkey beetles have been suggested as strong indicators of disturbance. These beetles are among the most important pollinator guilds in the CFR, as they help to sustain the endemic vegetation of this region. Protection of the remaining natural habitat in close proximity to farmland is an imperative conservation strategy in this region.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Sunlight-driven reduction of silver ion to silver nanoparticle by organic matter mitigates the acute toxicity of silver to Daphnia magna

Due to the unique antibacterial activities, silver nanoparticles (AgNPs) have been extensively used in commercial products. Anthropogenic activities have released considerable AgNPs as well as highly toxic silver ion (Ag⁺) into the aquatic environment. Our recent study revealed that ubiquitous natural organic matter (NOM) could reduce Ag⁺ to AgNP under natural sunlight. However, the toxic effect of this process is not well understood. In this work, we prepared mixture solution of Ag⁺ and AgNPs with varied Ag⁺% through the sunlight-driven reduction of Ag⁺ by NOM and investigated the acute toxicity of the solutions on Daphnia magna. Formation of AgNPs was demonstrated and characterized by comprehensive techniques and the fraction of unconverted Ag⁺ was determined by ultrafiltration-inductively coupled plasma mass spectrometry determination. The formation of AgNPs enhanced significantly with the increasing of solution pH and cumulative photosynthetically active radiation of sunlight. The toxicity of the resulting solution was further investigated by using freshwater crustacean D. magna as a model and an 8 hr-median lethal concentration (LC₅₀) demonstrated that the reduction of Ag⁺ by NOM to AgNPs significantly mitigated the acute toxicity of silver. These results highlight the importance of sunlight and NOM in the fate, transformation and toxicity of Ag⁺ and AgNPs, and further indicate that the acute toxicity of AgNPs should be mainly ascribed to the dissolved Ag⁺ from AgNPs.     

A case study of aggregation behaviors of titanium dioxide nanoparticles in the presence of dodecylbenzene sulfonate in natural water

The present work aims to ascertain the mechanisms of surfactant (dodecylbenzene sulfonate; DBS) effects on the aggregation behaviors of TiO₂ nanoparticles (TiO₂-NPs) in natural water samples. Aggregation experiments were conducted at a TiO₂-NPs concentration of 10 mg/L in deionized water and in natural water samples via dynamic light scattering and Zeta potential determination. Average attachment efficiency was calculated to compare the aggregation behaviors of nanoparticles in the two aqueous media. Results showed that the effects of DBS on aggregation could be interpreted by both Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO mechanisms. In natural water samples, aggregation did not occur rapidly and was able to develop slowly under all conditions, and the roles of DBS were obvious at high DBS concentration owing to the impacts of inherent components of natural water samples, such as colloids and natural organic compounds. Future aggregation studies should concentrate on multi-factor, multi-colloidal and dynamic aspects under similar environmental conditions.     

Towards more detailed determination of third party impact on risk on natural gas pipelines: Influence of population density

The paper presents a refined way to quantify the effects of third party interference on risk that is posed on people by transmission pipelines for natural gas. The main focus is set on the influence of population density on risk. Using the interdisciplinary approach, the presented study combines the knowledge from relevant risk assessment recommendations, physical consequences of hazardous events, existing history databases of hazardous event frequencies and urban planning. A quantitative boundary between two most populated types of area was established. A flexible risk coefficient was determined for a suburban type of populated area that is dependent on average population density. Consequently, a new approach for determination of a hazard distance from the pipeline and area boundaries for calculation of average population density was presented. This differs from the established methods described in some guidelines, but is based on results of applied quantitative risk assessment. The final result is more accurate determination of risk levels in suburban areas. Described methods may serve as a supplement to the existing models for quantitative risk assessment on pipelines used in natural gas transportation and may be used by pipeline operators as well as policy- and decision makers.     

Comparison of three-dimensional fluorescence analysis methods for predicting formation of trihalomethanes and haloacetic acids

This work investigated the application of several fluorescence excitation-emission matrix analysis methods as natural organic matter (NOM) indicators for use in predicting the formation of trihalomethanes (THMs) and haloacetic acids (HAAs). Waters from four different sources (two rivers and two lakes) were subjected to jar testing followed by 24 hr disinfection by-product formation tests using chlorine. NOM was quantified using three common measures: dissolved organic carbon, ultraviolet absorbance at 254 nm, and specific ultraviolet absorbance as well as by principal component analysis, peak picking, and parallel factor analysis of fluorescence spectra. Based on multi-linear modeling of THMs and HAAs, principle component (PC) scores resulted in the lowest mean squared prediction error of cross-folded test sets (THMs: 43.7 (μg/L)², HAAs: 233.3 (μg/L)²). Inclusion of principle components representative of protein-like material significantly decreased prediction error for both THMs and HAAs. Parallel factor analysis did not identify a protein-like component and resulted in prediction errors similar to traditional NOM surrogates as well as fluorescence peak picking. These results support the value of fluorescence excitation-emission matrix-principal component analysis as a suitable NOM indicator in predicting the formation of THMs and HAAs for the water sources studied.