Simultaneous removal of Cd(II) and As(V) by ferrihydrite-biochar composite: Enhanced effects of As(V) on Cd(II) adsorption.

The coexistence of cadmium (Cd(II)) and arsenate (As(V)) pollution has long been an environmental problem. Biochar, a porous carbonaceous material with tunable functionality, has been used for the remediation of contaminated soils. However, it is still challenging for the dynamic quantification and mechanistic understanding of the simultaneous sequestration of multi-metals in biochar-engineered environment, especially in the presence of anions. In this study, ferrihydrite was coprecipitated with biochar to investigate how ferrihydrite-biochar composite affects the fate of heavy metals, especially in the coexistence of Cd(II) and As(V). In the solution system containing both Cd(II) and As(V), the maximum adsorption capacities of ferrihydrite-biochar composite for Cd(II) and As(V) reached 82.03 µmol/g and 531.53 µmol/g, respectively, much higher than those of the pure biochar (26.90 µmol/g for Cd(II), and 40.24 µmol/g for As(V)) and ferrihydrite (42.26 µmol/g for Cd(II), and 248.25 µmol/g for As(V)). Cd(II) adsorption increased in the presence of As(V), possibly due to the changes in composite surface charge in the presence of As(V), and the increased dispersion of ferrihydrite by biochar. Further microscopic and mechanistic results showed that Cd(II) complexed with both biochar and ferrihydrite, while As(V) was mainly complexed by ferrihydrite in the Cd(II) and As(V) coexistence system. Ferrihydrite posed vital importance for the co-adsorption of Cd(II) and As(V). The different distribution patterns revealed by this study help to a deeper understanding of the behaviors of cations and anions in the natural environment.

Recent Advances in Electrochemiluminescence Biosensors for Mycotoxin Assay.

Rapid and efficient detection of mycotoxins is of great significance in the field of food safety. In this review, several traditional and commercial detection methods are introduced, such as high-performance liquid chromatography (HPLC), liquid chromatography/mass spectrometry (LC/MS), enzyme-linked immunosorbent assay (ELISA), test strips, etc. Electrochemiluminescence (ECL) biosensors have the advantages of high sensitivity and specificity. The use of ECL biosensors for mycotoxins detection has attracted great attention. According to the recognition mechanisms, ECL biosensors are mainly divided into antibody-based, aptamer-based, and molecular imprinting techniques. In this review, we focus on the recent effects towards the designation of diverse ECL biosensors in mycotoxins assay, mainly including their amplification strategies and working mechanism.

Remediation of a metal-contaminated soil by chemical washing and repeated phytoextraction: a field experiment.

Agricultural soil contaminated with potentially toxic metals poses great health risk to humans and it requires long-term remediation. Here, we investigate the remediation of metal-polluted agricultural soil by combining chemical washing with repeated phytoextraction. The polluted field was initially washed with 40 mmol L-1 FeCl3 (F) or 20 mmol L-1 FeCl3 + 40 mmol L-1 citric acid (F + C). After the application of organic fertilizer (O), lime (L), and sepiolite (S), Sedum plumbizincicola was cultivated for three successive crops from 2017 to 2019. Results showed that the soil washed with FeCl3 had high removal efficiencies of Cd (35.2%), Pb (24.3%), and Zn (26.6%). Although the shoot biomass and metal concentrations of S. plumbizincicola decreased significantly in the first crop, there were no significant differences in the subsequent two crops. Throughout the remediation process, the higher total removal efficiencies of Cd, Pb, and Zn were conducted in F + OLS treatment which observed in 71.0, 34.0, and 47.7%, respectively. The results, therefore, conclusively indicated that combining chemical washing with repeated phytoextraction showed considerable potential for the remediation of agricultural soils polluted with multiple metals. However, further studies are required to focus on the amelioration of the degraded soil quality and safe agricultural production.

Alkaline amendments improve the health of soils degraded by metal contamination and acidification: Crop performance and soil bacterial community responses.

Soil degradation due to heavy metal contamination and acidification has negative effects on soil health and crop growth. Many previous studies have tried to improve the growth of crops and decrease their metal uptake. The recovery of soil health, however, has rarely been focused in soil remediation. In this study, a pot trial was conducted with lettuce (Lactuca sativa L.) growing in heavy metal contaminated and acidic soils, to examine the effects of alkaline amendments (limestone, LS; calcium magnesium phosphate fertilizer, Pcm) and organic amendments (cow manure compost, CMC; biochar, BC) on the growth of lettuce and on the availability of heavy metals, enzyme activities, and bacterial community structures in the soils. The results showed that, in comparison with the CMC and BC treatments, LS and Pcm were more effective at improving lettuce growth and reducing metal concentrations in shoots. Urease and catalase activities in LS and Pcm amended soils were consistently higher than in those with CMC and BC. Additionally, the alkaline amendments dramatically improved the bacterial diversity and shaped more favorable bacterial community structures. Proteobacteria and Gemmatimonadetes were predominant in soils amended with alkaline treatments. The beneficial bacterial genera Gemmatimonas and f_Gemmatimonadaceae, which are vital for phosphate dissolution, microbial nitrogen metabolism, and soil respiration, were also enriched. The results suggest that alkaline amendments were superior to organic amendments, and thus may be useful for the future recovery of soil functions and health under heavy metal contamination and low pH.

Zero-valent iron (ZVI) Activation of Persulfate (PS) for Degradation of Para-Chloronitrobenzene in Soil.

Para-chloronitrobenzene (p-CNB) in soil has posed significant health risks because of its persistence and high toxicity. The efficacy of catalyzed Zero-Valent Iron (ZVI), activated persulfate, and ZVI-persulfate processes for the degradation of p-CNB in soil was investigated. The p-CNB removal rate significantly increased from 10.8 to 90.1% with increased ZVI dosage from 0.1 mmol g-1 to 1.0 mmol g-1. The p-CNB removal increased with the decrease of initial pH and a removal efficiency of 85.3% was obtained at an initial pH value of 6.8 in combined system. The p-CNB removal rate in the single persulfate system and ZVI system was 36.5% and 60.2%, while the ZVI-persulfate system showed more sufficient p-CNB removal capacity and the removal rate of p-CNB was 88.7%. Scanning electron microscopy (SEM) and Electron paramagnetic resonance (EPR) was adopted in order to explore the degradation mechanism by ZVI-Persulfate system in soil.

Adsorption and desorption of Cu2+ on paddy soil aggregates pretreated with different levels of phosphate.

Interactions between anions and cations are important for understanding the behaviors of chemical pollutants and their potential risks in the environment. Here we prepared soil aggregates of a yellow paddy soil from the Taihu Lake region, and investigated the effects of phosphate (P) pretreatment on adsorption-desorption of Cu2+ of soil aggregates, free iron oxyhydrates-removed soil aggregates, goethite, and kaolinite with batch adsorption method. The results showed that Cu2+ adsorption was reduced on the aggregates pretreated with low concentrations of P, and promoted with high concentrations of P, showing a V-shaped change. Compared with the untreated aggregates, the adsorption capacity of Cu2+ was reduced when P application rates were lower than 260, 220, 130 and 110mg/kg for coarse, clay, silt and fine sand fractions, respectively. On the contrary, the adsorption capacity of Cu2+ was higher on P-pretreated soil aggregates than on the control ones when P application rates were greater than those values. However, the desorption of Cu2+ was enhanced at low levels of P, but suppressed at high levels of P, displaying an inverted V-shaped change over P adsorption. The Cu2+ adsorption by the aggregate particles with and without P pretreatments was well described by the Freundlich equation. Similar results were obtained on P-pretreated goethite. However, such P effects on Cu2+ adsorption-desorption were not observed on kaolinite and free iron oxyhydrates-removed soil aggregates. The present results indicate that goethite is one of the main soil substances responsible for the P-induced promotion and inhibition of Cu2+ adsorption.

Ecological effects of soil properties and metal concentrations on the composition and diversity of microbial communities associated with land use patterns in an electronic waste recycling region.

Soil microbes play vital roles in ecosystem functions, and soil microbial communities may be strongly structured by land use patterns associated with electronic waste (e-waste) recycling activities, which can increase the heavy metal concentration in soils. In this study, a suite of soils from five land use types (paddy field, vegetable field, dry field, forest field, and e-waste recycling site) were collected in Longtang Town, Guangdong Province, South China. Soil physicochemical properties and heavy metal concentrations were measured, and the indigenous microbial assemblages were profiled using 16S rRNA high-throughput sequencing and clone library analyses. The results showed that mercury concentration was positively correlated with both Faith's PD and Chao1 estimates, suggesting that the soil microbial alpha diversity was predominantly regulated by mercury. In addition, redundancy analysis indicated that available phosphorus, soil moisture, and mercury were the three major drivers affecting the microbial assemblages. Overall, the microbial composition was determined primarily by land use patterns, and this study provides a novel insight on the composition and diversity of microbial communities in soils associated with e-waste recycling activities.

Mechanism and kinetics of aluminum dissolution during copper sorption by acidity paddy soil in South China.

Soil aggregates were prepared from a bulk soil collected from paddy soil in the Taihu Lake region and aluminum (Al) dissolution, solution pH changes during copper (Cu(2+)) sorption were investigated with static sorption and magnetic stirring. Kinetics of Cu(2+) sorption and Al dissolution were also studied by magnetic stirring method. No Al dissolution was observed until Cu(2+) sorption was greater than a certain value, which was 632, 450, 601 and 674 mg/kg for sand, clay, silt, and coarse silt fractions, respectively. Aluminum dissolution increased with increasing Cu(2+) sorption and decreasing solution pH. An amount of dissolved Al showed a significant positive correlation with non-specific sorption of Cu(2+) (R(2)>0.97), and it was still good under different pH values (R(2)>0.95). Copper sorption significantly decreased solution pH. The magnitude of solution pH decline increased as Cu(2+) sorption and Al dissolution increased. The sand and clay fraction had a less Al dissolution and pH drop due to the higher ferric oxide, Al oxide and organic matter contents. After sorption reaction for half an hour, the Cu(2+) sorption progress reached more than 90% while the Al dissolution progress was only 40%, and lagged behind the Cu(2+) sorption. It indicated that aluminum dissolution is associated with non-specific sorption.

An ultrasensitive electrochemical DNA biosensor based on graphene/Au nanorod/polythionine for human papillomavirus DNA detection.

An ultrasensitive electrochemical DNA biosensor for human papillomavirus (HPV) detection was developed by electrochemical impedance spectroscopy and differential pulse voltammetry. A capture probe was immobilized on a glassy carbon electrode modified with graphene/Au nanorod/polythionine (G/Au NR/PT). Two auxiliary probes were designed and used to long-range self-assemble DNA nanostructure. The target DNA can connect DNA structure to the capture probe on the electrode surface. [Ru(phen)3](2+) was selected as a redox indicator for amplifying electrochemical signal significantly. Enhanced sensitivity was obtained through combining the excellent electric conductivity of G/Au NR/PT architecture and the long-range self-assembly DNA nanostructure with the multi-signal amplification. The DNA biosensor displayed excellent performance for HPV DNA detection over the range from 1.0×10(-13) to 1.0×10(-10) mol/L with a detection limit of 4.03×10(-14) mol/L. Furthermore, the proposed method can also be used for the detection of HPV DNA in human serum samples and provides a potential application of DNA detection in clinic research.

Remediation of cadmium- and lead-contaminated agricultural soil by composite washing with chlorides and citric acid.

Composite washing of cadmium (Cd)- and lead (Pb)-contaminated agricultural soil from Hunan province in China using mixtures of chlorides (FeCl3, CaCl2) and citric acid (CA) was investigated. The concentrations of composite washing agents for metal removal were optimized. Sequential extraction was conducted to study the changes in metal fractions after soil washing. The removal of two metals at optimum concentration was reached. Using FeCl3 mixed with CA, 44% of Cd and 23% of Pb were removed, and 49 and 32% by CaCl2 mixed with CA, respectively. The mechanism of composite washing was postulated. A mixture of chlorides and CA enhanced metal extraction from soil through the formation of metal-chloride and metal-citrate complexes. CA in extract solutions promoted the formation of metal-chloride complexes and reduced the solution pH. Composite washing reduced Cd and Pb in Fe-Mn oxide forms significantly. Chlorides and CA exerted a synergistic effect on metal extraction during composite washing.

New insights into atrazine degradation by cobalt catalyzed peroxymonosulfate oxidation: kinetics, reaction products and transformation mechanisms.

The widespread occurrence of atrazine in waters poses potential risk to ecosystem and human health. In this study, we investigated the underlying mechanisms and transformation pathways of atrazine degradation by cobalt catalyzed peroxymonosulfate (Co(II)/PMS). Co(II)/PMS was found to be more efficient for ATZ elimination in aqueous solution than Fe(II)/PMS process. ATZ oxidation by Co(II)/PMS followed pseudo-first-order kinetics, and the reaction rate constant (k(obs)) increased appreciably with increasing Co(II) concentration. Increasing initial PMS concentration favored the decomposition of ATZ, however, no linear relationship between k(obs) and PMS concentration was observed. Higher efficiency of ATZ oxidation was observed around neutral pH, implying the possibility of applying Co(II)/PMS process under environmental realistic conditions. Natural organic matter (NOM), chloride (Cl(-)) and bicarbonate (HCO3(-)) showed detrimental effects on ATZ degradation, particularly at higher concentrations. Eleven products were identified by applying solid phase extraction-liquid chromatography-mass spectrometry (SPE-LC/MS) techniques. Major transformation pathways of ATZ included dealkylation, dechlorination-hydroxylation, and alkyl chain oxidation. Detailed mechanisms responsible for these transformation pathways were discussed. Our results reveal that Co(II)/PMS process might be an efficient technique for remediation of groundwater contaminated by ATZ and structurally related s-triazine herbicides.

Assessment of EDTA heap leaching of an agricultural soil highly contaminated with heavy metals.

The efficiency of heavy metal removal from soil by EDTA leaching was assessed in a column leaching experiment at the laboratory scale and field heap leaching at the pilot scale using a sandy loam sierozem agricultural soil contaminated with Cd, Cu, Pb, and Zn. Soil amendment and aging were conducted to recover leaching soils. The percentages of Cd, Cu, Pb, and Zn removed by column leaching were 90%, 88%, 90%, and 67%, respectively, when 3.9 bed volumes of 50mM EDTA were used. At the pilot scale, on-site metal removal efficiencies using the selected leaching procedure were 80%, 69%, 73% and 62% for Cd, Cu, Pb and Zn, respectively. EDTA leaching decreased soil CEC, total P, total K and available K concentrations but increased organic matter and total Kjeldahl N concentrations. The subsequent amendment and soil aging further reduced the DTPA-extractable heavy metals in the leached soils. Growth of the first crop of pak choi in the leached soil was inhibited but the second crop grew well after the soil was aged for one year and the concentrations of Cd and Pb in the edible parts were below the Chinese statutory limits. The results demonstrate the potential feasibility of the field leaching technique using EDTA combined with subsequent amendment and soil aging for the remediation of heavy metal-contaminated agricultural soils.

[Aluminum dissolution and changes of pH in soil solution during sorption of copper by aggregates of paddy soil].

Size fractions of soil aggregates in Lake Tai region were collected by the low-energy ultrasonic dispersion and the freeze-desiccation methods. The dissolution of aluminum and changes of pH in soil solution during sorption of Cu2+ and changes of the dissolution of aluminum at different pH in the solution of Cu2+ by aggregates were studied by the equilibrium sorption method. The results showed that in the process of Cu2+ sorption by aggregates, the aluminum was dissoluted and the pH decreased. The elution amount of aluminum and the decrease of pH changed with the sorption of Cu2+, both increasing with the increase of Cu2+ sorption. Under the same conditions, the dissolution of aluminum and the decrease of pH were in the order of coarse silt fraction > silt fraction > sand fraction > clay fraction, which was negatively correlated with the amount of iron oxide, aluminum and organic matter. It suggested that iron oxide, aluminum and organic matters had inhibitory and buffering effect on the aluminum dissolution and the decrease of pH during the sorption of Cu2+.

Enhanced degradation of ortho-nitrochlorobenzene by the combined system of zero-valent iron reduction and persulfate oxidation in soils.

ortho-Nitrochlorobenzene (o-NCB) in soil poses significant health risks to human because of its persistence and high toxicity. The removal of o-NCB by both zero-valent iron (ZVI) and chemical oxidation (persulfate) was investigated by batch experiments. The o-NCB removal rate increases significantly from 15.1 to 97.3 % with an increase of iron dosage from 0.1 to 1.0 mmol g(-1). The o-NCB removal rate increases with the decrease of the initial solution pH, and a removal efficiency of 90.3 % is obtained at an initial pH value of 6.8 in this combined system. It is found that temperature and soil moisture could also increase the o-NCB removal rate. The o-NCB degradation rate increases from 83.9 to 96.2 % and from 41.5 to 82.4 % with an increase of temperature (15 to 35 °C) and soil moisture (0.25 to 1.50 mL g(-1)), respectively. Compared to the persulfate oxidation system and ZVI system, the persulfate-iron system shows high o-NCB removal capacity. o-NCB removal rates of 41.5 and 62.4 % are obtained in both the persulfate oxidation system and the ZVI system, while the removal rate of o-NCB is 90.3 % in the persulfate-iron system.

A novel three-dimensional AgI coordination polymer based on mixed naphthalene-1,5-disulfonate and aminoacetate ligands.

The three-dimensional coordination polymer poly[[bis(µ3-2-aminoacetato)di-µ-aqua-µ3-(naphthalene-1,5-disulfonato)-hexasilver(I)] dihydrate], {[Ag6(C10H6O6S2)(C2H4NO2)4(H2O)2]·2H2O}n, based on mixed naphthalene-1,5-disulfonate (L1) and 2-aminoacetate (L2) ligands, contains two Ag(I) centres (Ag1 and Ag4) in general positions, and another two (Ag2 and Ag3) on inversion centres. Ag1 is five-coordinated by three O atoms from one L1 anion, one L2 anion and one water molecule, one N atom from one L2 anion and one AgI cation in a distorted trigonal-bipyramidal coordination geometry. Ag2 is surrounded by four O atoms from two L2 anions and two water molecules, and two AgI cations in a slightly octahedral coordination geometry. Ag3 is four-coordinated by two O atoms from two L2 anions and two AgI cations in a slightly distorted square geometry, while Ag4 is also four-coordinated by two O atoms from one L1 and one L2 ligand, one N atom from another L2 anion, and one AgI cation, exhibiting a distorted tetrahedral coordination geometry. In the crystal structure, there are two one-dimensional chains nearly perpendicular to one another (interchain angle = 87.0°). The chains are connected by water molecules to give a two-dimensional layer, and the layers are further bridged by L1 anions to generate a novel three-dimensional framework. Moreover, hydrogen-bonding interactions consolidate the network.

[Estrogens determination of livestock dung based on UE-SPE-HPLC/FLD].

A method for detecting the estrogens estriol, 17beta-estradiol, ethinyl estradiol, and bisphenol A in livestock dung was established by the combination of ultrasonic extraction (UE), solid phase extraction (SPE) purification, and high performance liquid chromatography (HPLC) with fluorescence detector (FLD). The dung samples were extracted with ethyl acetate ultrasonication for 30 min, and purified with C18 solid phase extraction column and related solvents. The test four estrogens in the dung samples were isolated with Inertsil ODS-SP-C18 reversed-phase columns (150 mm x 4.6 mm, 5 microm), and the isolated estrogens were detected with HPLC/FLD. The mobile phase of HPLC for the detection was methanol/acetonitrile/water (volume ratio of 20:30:50), with a flow rate of 0.8 mL x min(-1). The excitation and emission wavelengths of FLD were 280 and 310 nm, respectively, the HPLC column temperature was 40 degrees C, and the injection volume was 20 microL. Good linearity (correlation coefficient greater than 0.9995) was observed by the HPLC/FLD detection when the test four estrogens concentrations were in the range of 1.00-1000.00 microg x L(-1). The detection limit of estriol, bisphenol A, 17beta-estradiol, and ethinyl estradiol was 3.35, 5.01, 2.13, and 1.12 microg x kg(-1), respectively. When the added estrogens concentrations of pig, cow, and chicken dung samples were 0.05, 0.40, and, 1.00 microg x kg(-1), the average recovery of the four estrogens was 75.1%-91.1%, 78.4%-117.0%, and 78.6%-97.8%, respectively, with the relatively standard deviations (RSD, n = 6) all less than 6%. By adopting the established SPE-HPLC/FLD method to detect the estrogens in real pig, cow, and chicken dung samples from parts of the large-scale livestock raising farms in Nanjing of East China, the detection reproducibility was high, and the detection limit was low, being available and effective for the detection of the estrogens in livestock dung.

[Kinetic characteristics of Cr(III) oxidation by delta-MnO2].

The kinetics of Cr(III) oxidation by synthesized vernadite(delta-MnO2) was investigated through magnetic stirring and fractional centrifugation. The oxidation procedure of Cr(III) by delta-MnO2 could be divided into two first-order reactions, a fast reaction followed by a slow one. In high Cr(III) concentration solution, the reaction was also well sub-simulated with diffusion equation and Elovich equation according to the reaction phases. The rate constants markedly increased with temperature rising. The ratio of Cr(VI)/Mn(II) gradually decreased and eventually reached the theoretical value (0.667) with the reaction. Cr(VI), Cr(III) and Mn(II) adsorbed on delta-MnO2 only accounted 0.1 to 3% of the total amounts. The Cr(VI)/Mn(II) ratio on the surface of MnO2 was much smaller than the theoretical value due to the release of Mn(II) to the solution lagged behind Cr(VI). When Cr(III) was in low concentration, Cr(III) oxidation was controlled by the diffusion and adsorption of Cr(III). While in high Cr(III) concentration, the key step was the diffusion of Mn(II) to solution.