Spatial distribution and export of nutrients and metal elements in the subterranean estuary of Daya Bay

Subterranean estuaries(STE)are important seawater-groundwater mixing zones with complex biogeochemical processes,which play a vital role in the migration and transformation of dissolved materials.In this study,we first investigated the spatial distributions of dissolved inorganic nitrogen(DIN),dissolved inorganic phosphorous(DIP),dissolved inorganic silicon(DSi)and metal elements(As,Ba,Cr,Cu,Fe,Mn,Ni,Pb,and Zn)in STE including upper intertidal,seepage face and subtidal zones.We then estimated submarine groundwater discharge(SGD)and associated nutrient and metal element fluxes.From the generalized Darcy’s law method,SGD was estimated to be 30.13 cm/d,which was about 7 times larger than the inflow(4.16 cm/d).The nutrient and metal fluxes from SGD were estimated to be(5.33±4.99)mmol/(m^(2)·d)for DIN,(0.22±0.03)mmol/(m^(2)·d)for DIP,(16.20±2.05)mmol/(m^(2)·d)for DSi,(1325.06±99.10)μmol/(m^(2)·d)for Fe,(143.41±25.13)μmol/(m^(2)·d)for Mn,(304.06±81.07)μmol/(m^(2)·d)for Zn,(140.21±13.33)μmol/(m^(2)·d)for Cu,(84.49±2.94)μmol/(m^(2)·d)for Pb,(37.38±5.51)μmol/(m^(2)·d)for Ba,(27.88±3.89)μmol/(m^(2)·d)for Cr,(10.10±6.33)μmol/(m^(2)·d)for Ni,and(6.25±3.45)μmol/(m^(2)·d)for As.The nutrient and metal fluxes from SGD were relatively higher than those from the inflow,suggesting that nearshore groundwater acted as the sources of nutrients and metal elements discharging into the sea.The environmental potential pollution of coastal seawater was evaluated by pollution factor index(Pi),comprehensive water quality index(CWQI),and ecological risk index(ERI).Pb mainly caused potential danger of nearshore environment with considerable contamination(Pi=5.78±0.19),heavy pollution(CWQI=4.09)and high ecological risk(ERI=18.00).This study contributed to better understanding the behavior of nutrients and metal elements and improving the sustainable management of STE under the pressure of anthropogenic activities and climate change.

Ultrasonic Nebulizer Assisted LIBS: a Promising Metal Elements Detection Method for Aqueous Sample Analysis

A newly developed approach for trace metal elements detection for aqueous samples analysis is presented in this paper. The idea of this approach is to improve ablation efficiency by transforming the liquid sample into a dense cloud of droplets using an ultrasonic nebulizer. The resulting droplets are then subjected to analysis by laser induced breakdown spectroscopy （LIBS）. A purpose-built ultrasonic nebulizer assisted LIBS （UN-LIBS） system has been applied to the analysis of aqueous samples at trace levels of concentration. Experimental investigations of solution samples were carried out with various dissolved trace metal elements （Mn, Zn, Cu, Pb, Fe, Mg and Na） using this approach. The characteristics of UN-LIBS signal of the elements were investigated regarding the lifetime and S/B ratio and the calibration curves for trace metal elements analyses. The obtained LODs are comparable or much better than the LODS of the reported signal enhancement approaches when the laser pulse energy was as low as 30 mJ. The good linearity of calibration curves and the low LODs shows the potential ability of this method for metal elements analysis application. The density of the electrons was calculated by measuring the Stark width of the line of Ha. The possible mechanism of the LIBS signal enhancement of this approach was briefly discussed.

Main group metal elements for ambient-condition electrochemical nitrogen reduction

Electrocatalytic N_(2) reduction under ambient-condition is considered to be the most appealing strategy to the conventional Haber-Bosch process for synthetic ammonia to alleviate greenhouse emissions and reduce environmental pollution, mainly powered by renewable energy. Recent years, rapid advances have been gained in this attractive research field, and numerous electrocatalysts have been exploited. However, its conversion efficiency is still far behind the requirement of industrial applications owing to the breakage of the N≡N triple bond, which is an energetically challenging kinetically complex multistep reaction and the strong competing reaction of hydrogen evolution reaction. Recently, main group metal-based catalysts have been demonstrated promising application prospect for ammonia production, significantly boosting their further application in this field. However, a comprehensive review of main group metal-based catalysts towards electrochemical ammonia production applications is still lacking. In this review, the fundamentals of N_(2) reduction, such as the reaction pathways, the reaction potential and the challenges of N_(2) reduction have been comprehensively discussed. And then, the role, mechanism, and effect of each main group element-based catalysts used for N_(2) reduction (Li, K, Al, Ga, Sn, Sb, Bi, and their compounds) are systematically summarized. Finally, several state-of-the-art strategies to promote their NRR catalytic performance, as well as the existing problems and prospects are put forward. This review is expected to guide the design and establishment of more efficient electrocatalytic N_(2) reduction systems based on main group metal elements in the future.

Investigation on the Quality of Irrigation Water in Southern Anhui and the Effects of Metal Elements in Irrigation Water on the Coke Sweet Aroma Style of Tobacco Leaves

[Objectives]The effects of metal elements in irrigation water in the tobacco areas of southern Anhui on the coke sweet aroma of tobacco leaves was determined.[Methods]53 representative areas for tobacco planting in southern Anhui were selected,and the quality of irrigation water,especially the content of metal elements,was investigated.[Results]The contents of micro(medium)elements in the irrigation water were too low to have a significant effect on the formation of the coke sweet aroma style of tobacco leaves.The contents of Mg,Ca and Zn were 0.7-8.0,<40 and 0.002-0.029 mg/L,respectively.The heavy metal contents of the irrigation water and other basic control items all met corresponding national standards.Furthermore,the tobacco planting experiment under controlled irrigation using paddy soil in the greenhouse proved that Zn was a negative correlation factor for forming the coke sweet aroma style of tobacco and the threshold value was≥10 mg/L in the irrigation water.Meanwhile,Mg was a positive correlation factor and the content of Mg to promote the coke sweet aroma style should be maintained at 40-90 mg/L.Ca and Mg had a synergistic effect,which was mainly appropriate for acid paddy soils.[Conclusions]This study improves the quality and yield of the coke sweet aroma of tobacco leaves,and has important theoretical and practical value for the formation of a popular agronomic control method.

Migration of Heavy Metal Elements in Reclaimed Irrigation Water-Soil-Plant System and Potential Risk to Human Health

[Objectives]To study the impact of heavy metal pollution of soil and plants during the process of reclaimed water for irrigation of green land in arid areas and the potential health risks to humans during use.[Methods]Taking Zhongwei City in Ningxia,a typical arid area,as the research area,the irrigation water,soil and green grass in the reclaimed water irrigation region and the original green water irrigation region were sampled,the heavy elements Hg,As,Zn,Pb,Cd,Cr were detected,and the Nemerow method,biological absorption coefficient,and health risk assessment were employed to evaluate the degree of soil pollution,plant absorption capacity,and human health risks.[Results]Compared with the original green water,the Hg,Cd,and Cr pollution of the reclaimed water irrigated green land was higher,the As,Zn,Pb pollution was lower,and the content of Hg and Cd was higher than the environmental background values of soil in Ningxia;the Cr content exceeded the risk intervention values of the first type of land in the Soil Environmental Quality—Risk Control Standard for Soil Contamination of Development Land(GB 36600-2018).Compared with the original green water irrigation region,it is found that the reclaimed water irrigation reduced the heavy metal pollution of the soil to a certain extent.The heavy metal content of tall fescue grass(Festuca arundinacea)in the reclaimed water irrigation region was Zn,Cr,Pb,As,Cd,and Hg from high to low;the order of the biological absorption coefficient was Cd>As>Zn>Pb>Hg>Cr;irrigation water exerted a certain effect on the content of heavy metals in plants and the biological absorption coefficient through the soil.Using the health risk assessment method recommended by Environmental Protection Agency of the United States of America(USEPA),it was found that the reclaimed water has the highest risk through the inhalation route,and the occupational population has a higher risk of skin contact with soil and plants.[Conclusions]This study is intended to provide data support and theoretical basis for the environmental safety risk research of the application of reclaimed water in arid areas to urban greening.

Review Study on the Accumulation and Release of Trace Metal Elements on Aluminum Containing Sediments in Drinking Water Distribution System

Accumulation and releasing of trace metal elements on aluminum containing sediments of inner drinking water pipe is discussed,as studied from five variations effecting:raw water quality,chemical reagents,solution pH and drinking water flow condition.In order to decrease the release of trace metal elements,and to ensure the pipe operation and human safety,water quality adjustment is suggested to avoid aluminum containing sediments formation in drinking distribution system.The maximum amounts of accumulation of common trace metal elements are given.Future trends of development in this field are also proposed.

Retention Factors for Trace Metal Elements in Solid Phase and Applicable Adsorption Models: Case of <i>Moringa oleifera</i>

Moringa oleifera is an edible plant cultivated throughout the tropical belt. It belongs to the family Moringaceae and is one of its 14 known species. This paper presents a synthesis of the main factors responsible for the retention of trace metal elements (TMEs) by Moringa oleifera seed powder, a natural adsorbent. The five main factors studied are metal concentration, solution pH, adsorbent particle size, adsorbent dose and adsorbent/adsorbate contact time. Through these factors, we present the optimal conditions for removal of these TMEs, as well as adsorption isotherm models appropriate for the conditions of retention of these metal cations by the adsorbent. The times of 20 min (GD) and 50 min (GND) are the equilibrium times obtained in our study. An optimal adsorbent mass (GD and GND powders) of 4.5 g was found. 20% to 97% abatement is observed for average pH values between 6 and 8. The coefficients of determination (R2) obtained (0.972, 0.963, 0.991 and 0.799) during the isotherm experiments carried out at 20°C, 30°C, 40°C and 50°C are close to 1. Also, the separation factor (RL), an essential characteristic of the Langmuir isotherm whose values are between 0 and 1, attest to the applicability of the Langmuir isotherm model to fit the experimental data of copper adsorption by Moringa powders. In this paper, we are particularly interested in the following TMEs (Mn, Ni, Cr, Cu, Cd, Co, Pb, Fe, Zn, Ag).

Anomalous Concentrations of Rare Metal Elements, Rare-scattered(Dispersed) Elements and Rare Earth Elements in the Coal from Iqe Coalfield, Qinghai Province, China

Total of 23 bench samples were taken from the No. 7 Coal of Iqe Coalfield, Qinghai Province, China, following Chinese Standard Method GB/T 482-2008 （2008）. These samples were analyzed by powder X-ray diffraction （XRD）, inductively coupled plasma mass spectrometry （ICP- MS） and X-ray fluorescence （XRF）. The results indicate that the No. 7 Coal belongs to a low rank （Ro.ran =0.659%） and high-ash coal （40.54%）. Compared to common Chinese and world low-rank coals, the lqe coal contains anomalous concentrations of rare metal elements, rare-scattered （dispersed） elements and rare earth elements. The highest contents of Rb, Cs, Ga and REY reach to 180, 26, 37, and 397 ppm, respectively. Their average contents of these elements are 10.9, 15, 4.8 and 3.5 times higher than those of world coals, respectively. Minerals in the coal include kaolinite, quartz, muscovite, siderite, and traces of rutile, and brookite. Kaolinite could be main host minerals of Rb, Cs, Ga and REY. The anomalous rare element Rb and Cs accumulation in the Iqe coal is related to both organic and inorganic matter. The REY concentrations may be related to circulation of thermal solutions, contained or sorbed by clayey particles, and organic matter as well.

Contents of Trace Metal Elements in Cow Milk Impacted by Different Feedstuffs

Feedstuff intake plays key role in impacting the yield and quality of milk. In this study, we discussed the contents of trace metal elements in cow milk impacted by different feedstuffs. We detected the contents of Pb, Cd, As, Cu, Mg, Ca, Fe and Zn in different feedstuffs and milk by atomic absorption spectrophotometry. The determinations of Pb, Cd and As contents were by graphite furnace A_AS and Cu, Mg, Ca, Fe and Zn was by flame atomic absorption spectrometry. The results showed that Pb, Cd, As and Cu presented in feedstuffs, but Pb, Cd and As were lowly detected in milk samples, and Cu was not detected in milk samples. The content of Mg in concentrates was lower than that in forages. However, the content of Mg in milk from concentrate feed was higher than that in forage feed. This suggested that the utilization of Mg in concentrate feed was higher than that in forage feed. The contents of Ca and Zn were opposite to Mg, and the utilization of Ca and Zn in forage feed was higher than that in concentrate feed. There was no obviously change law of Fe in different feedstuffs and milk samples. The relationship between the contents of trace metal elements in milk to feedstuffs would provide a theoretical basis for dairy farming. It would be useful for improving the milk yield and milk quality of dairy production.

Annual Fluxes of Heavy Metal Elements in Atmospheric Dry and Wet Depositions in the Pearl River Delta Economic Region, Guangdong Province

There are 158 sampling points to be set up in the Pearl River delta economic region. The collecting period is mostly one year, namely, from July 2007 to July 2008. The eight heavy metal elements of Cr, Ni, Cu, Pb, Zn, As, Hg, and Cd in 474 dry and wet deposition samples were tested in terms of the standard procedures. Their average annual fluxes have no obvious difference between dry deposition and wet deposition. So these elements might be at an equilibrium or quasi-equilibrium state between dry deposition and wet deposition.

Trace metal elements: a bridge between host and intestinal microorganisms

Trace metal elements, such as iron, copper, manganese, and zinc, are essential nutrients for biological processes. Although their intake demand is low, they play a crucial role in cell homeostasis as the cofactors of various enzymes. Symbiotic intestinal microorganisms compete with their host for the use of trace metal elements. Moreover, the metabolic processes of trace metal elements in the host and microorganisms affect the organism's health. Supplementation or the lack of trace metal elements in the host can change the intestinal microbial community structure and function. Functional changes in symbiotic microorganisms can affect the host's metabolism of trace metal elements. In this review, we discuss the absorption and transport processes of trace metal elements in the host and symbiotic microorganisms and the effects of dynamic changes in the levels of trace metal elements on the intestinal microbial community structure. We also highlight the participation of trace metal elements as enzyme cofactors in the host immune process. Our findings indicate that the host uses metal nutrition immunity or metal poisoning to resist pathogens and improve immunity.

Health risk assessment of heavy metal pollution in groundwater of a karst basin,SW China

To investigate the presence of metal elements and assess their health risk for the populace in the Nandong Underground River Basin(NURB),we conducted an analysis of eleven common heavy metals in the water body.A Health risk assessment(HRA)model was employed to analyze 84 water samples from the NURB.The detection results revealed the following order of heavy metals concentrations:Fe>Al>Mn>Zn>As>Cd>Pb>Cr>Ni>Cu>Hg.Correlation analysis indicated a certain similarity in material source and migration transformation among these eleven metal elements.Our study identified that the health risks for local residents exposed to metal elements in the water of NURB primarily stem from carcinogenic risk(10^(−6)–10^(−4)a^(−1))through the drinking water pathway.Moreover,the health risk of heavy metal exposure for children through drinking water was notably higher than for adults.The maximum health risks of Cr in both underground and surface water exceeded the recommendation standard(5.0×10^(−5)a^(−1))from ICRP,surpassing the values recommended by the Swedish Environmental Protection Agency,the Dutch Ministry of Construction and Environment and the British Royal Society(5.0×10^(−6)a^(−1)).The results of the health risk assessment indicate that Cr in the water of NURB is the primary source of carcinogenic risk for local residents,followed by Cd and As.Consequently,it is imperative to control these three carcinogenic metals when the water was used as drinking water resource.

Organic/ Inorganic Occurrence of Metallic Elements of the Black Shale-Hosted Baiguoyuan Silver-Vanadium Deposit in Xingshan, Hubei

By means of kerogen purification, the proton induced X-ray emission (PIXE) and instrumental neutron activation analysis (INAA), the authors have studied the organic/inorganic occurrence modes of the metallic elements of the Baiguoyuan silver-vanadium deposit hosted in black shale in Hubei Province, China. The result shows that Au, Hg and Ta have a strong tendency to occur organically, with more than 70% of these elements being associated organically. Se, Ga, Ag and Hf are partly associated with organic matter, with more than 20% of them occurring organically. Compared with the above elements, Zn, Cu, As and Sb are weakly associated organically, and tend to be enriched in kerogen. However, Mn, Th, U, V, Co, Cr, AI, Fe and Sc usually occur inorganically. Of the rare earth elements (REE), La, Ce, Tb, Dy, Yb and Lu have stronger ability to be associated with organic matter than Sm and Eu.

Level of Contamination of Fishponds Water in Pesticide Residues and Metallic Trace Elements (Pb, Cd, As, Hg): Case of Fishponds of ZEPREGUHE (Daloa, Côte d’Ivoire)

Fishponds waters intended to satisfy the nutritional needs of the populations in terms of supply of fish resources are strongly and unfortunately exposed to the mobility and dispersion of metallic trace elements (TMEs) or to the persistence in the environment and in the form of pesticide residues from human activities. The objective of this work is to evaluate, on the one hand, the levels of identified pesticide residues and, on the other hand, those of researched TMEs (lead, cadmium, mercury and arsenic) in the waters of ponds used for fish farming in Zépréguhé, a locality located 9 km from the town of Daloa in the centre-west of C&ocirc;te d’Ivoire. The dosage of the samples carried out by means of a gas chromatograph coupled to a mass spectrometer (GC/MS) made it possible to detect nine (9) pesticide molecules, including eight (8) organochlorines and a single molecule from the pyrethroid family, obtained from the detection limit of 0.006 μg/L and the quantification limit of 0.018 μg/L. The maximum average concentration was obtained with α-endosulfan for a content reaching 0.8038 μg/L and well above the maximum admissible concentration of 0.1 μg/L. The TMEs were quantified using an atomic absorption spectrophotometer (AAS). Arsenic is the most abundant metal with an average concentration of 9.497 μg/L. With the exception of lead, these measured levels are above the acceptable limit values for freshwater. This study showed that human activities such as the use of fertilisers and plant protection products in plantations, sand extraction and road traffic have a negative impact on the quality of the water in ponds used for fish breeding.

Heavy metal accumulation by panicled goldenrain tree(Koelreuteria paniculata) and common elaeocarpus(Elaeocarpus decipens) in abandoned mine soils in southern China

Phytoremediation can be used as a sustainable technology for mine spoil remediation to remove heavy metals. This study investigated the concentration of 7 heavy metal contamination in soil and plant samples at an abandoned mine site. We found that, after vegetation remediation at the abandoned mine site, the reduction rates for 7 heavy metals were in the range of 4.2%-86%, where reduction rates over 50% were achieved for four heavy metals （Zn, Mn, Cd, Ni）. Transfer coefficients of the panicled goldenrain tree （Koelreuteria paniculata Laxm） and the common elaeocarpus （Elaeocarpus decipens） for Zn, Mn, Ni, and Co were more than 1. Enrichment coefficients of both trees for Mn were higher than 1. Our results suggest that the panicled goldenrain tree and the common elaeocarpus tree may act as accumulators in remediation. Moreover, the woody vegetation remediation in abandoned mining areas play an important role in improving scenery besides removing heavy metal from contaminated soil.

A Fundamental DFT Study of Anatase(TiO2) Doped with 3d Transition Metals for High Photocatalytic Activities

Anatase（TiO_2） has been widely used in photocatalysis. However, it can only absorb near-ultraviolet light with a wavelength below approximately 388 nm due to a wide band gap. Therefore a modification should be made for anatase to increase its capability in utilizing more abundant visible light. We investigated the doped anatase with the most promising 3d transition metal elements, and the results showed that the visible light absorption intensity was increased significantly due to the reduced band gap and the cavitation effects. As compared to other 3d transition metals, Cu was found to be the most effective one in improving anatase photocatalytic effects. In addition, greater Cu concentration doped in the anatase increased the photocatalysis effects but reduced the anatase stability, therefore, an optimized Cu concentration should be considered to optimize the anatase photocatalysis activity.

Geochemical anomaly and the causes of transition metal accumulations in late Permian coal from the eastern Yunnan-western Guizhou region

The concentration of 39 trace elements in coal from the late Permian taken from the eastern Yunnan-western Guizhou region was determined using inductively coupled plasma mass spectrometry. It was found that the mean content of Ti, V, Cr, Mo, Co, Ni, Y, and Zr is higher than the national average. The occurrence of Mn, Ni, and Co in the different coalfields is distinctly different. Most of the enriched transition metal elements exist mainly as inorganic minerals. In the Zhina coalfield, Co, Ni, and Nb are primarily associated with sulfur. Mn, Cs, and Mo are mostly sulfides. Almost all Co was organic and a significant part of the Ni is also organic in the Liupanshui coalfield. Cs, Co, and Ni are related to sulfur in the coal taken from eastern Yunnan. Carbonate is the main form of Mn in the coal from eastern Yunnan and the Liupanshui coalfield. Ti is the oxide in the coal samples where Ti is enriched. Zr is in the form of zircon in the samples where Zr is enriched. The situation for most of the transition metal elements is consistent with terrestrial genesis. Coal seams are universally influenced by the sea. The strongly seawater effected peat bog with a reductive and alkaline environment favors the relative enrichment of Mn. A reducing environment is conducive to transition metal element enrichment.

Heavy metal: a misused term?

The use of the term"heavy metal"is regularly questioned by the scientific community.Here,we followed the evolution(1970–2020)in the number of published papers including this term in their title.Thus,we can evidence a continuous,albeit sometimes stabilizing,increase especially in environmental journals.After several other warning opinions,we propose that it should be replaced in the scientific literature by terms like"metal","metalloid","trace metal elements"or"potentially toxic element".

DEFORMATION ANALYSIS OF SHEET METAL SINGLE-POINT INCREMENTAL FORMING BY FINITE ELEMENT METHOD SIMULATION

Single-point incremental forming （SPIF） is an innovational sheet metal forming method without dedicated dies, which belongs to rapid prototyping technology. In generalizing the SPIF of sheet metal, the deformation analysis on forming process becomes an important and useful method for the planning of shell products, the choice of material, the design of the forming process and the planning of the forming tool. Using solid brick elements, the finite element method（FEM） model of truncated pyramid was established. Based on the theory of anisotropy and assumed strain formulation, the SPIF processes with different parameters were simulated. The resulted comparison between the simulations and the experiments shows that the FEM model is feasible and effective. Then, according to the simulated forming process, the deformation pattern of SPIF can be summarized as the combination of plane-stretching deformation and bending deformation. And the study about the process parameters＇ impact on deformation shows that the process parameter of interlayer spacing is a dominant factor on the deformation. Decreasing interlayer spacing, the strain of one step decreases and the formability of blank will be improved. With bigger interlayer spacing, the plastic deformation zone increases and the forming force will be bigger.

Growth, Metabolism and Yield of Rice Cultivated in Soils Amended with Fly Ash and Cyanobacteria and Metal Loads in Plant Parts

Soil amendment with fly ash（FA） and combined supplementation with N_2-fixing cyanobacteria masses as biofertilizer were done in field experiments with rice. Amendments with FA levels, 0, 0.5, 1.0, 2.0, 4.0, 8.0 and 10.0 kg/m2, caused increase in growth and yield of rice up to 8.0 kg/m2, monitored with several parameters. Pigment contents and enzyme activities of leaves were enhanced by FA, with the maximum level of FA at 10.0 kg/m2. Protein content of rice seeds was the highest in plants grown at FA level 4.0 kg/m2. Basic soil properties, p H value, percentage of silt, percentage of clay, water-holding capacity, electrical conductivity, cation exchange capacity, and organic carbon content increased due to the FA amendment. Parallel supplementation of FA amended plots with 1.0 kg/m2 N_2-fixing cyanobacteria mass caused further significant increments of the most soil properties, and rice growth and yield parameters. 1000-grain weight of rice plants grown at FA level 4.0 kg/m2 along with cyanobacteria supplementation was the maximum. Cyanobacteria supplementation caused increase of important basic properties of soil including the total N-content. Estimations of elemental content in soils and plant parts（root and seed） were done by the atomic absorption spectrophotometry. Accumulations of K, P, Fe and several plant micronutrients（Mn, Ni, Co, Zn and Cu） and toxic elements（Pb, Cr and Cd） increased in soils and plant parts as a function of the FA gradation, but Na content remained almost unchanged in soils and seeds. Supplementation of cyanobacteria had ameliorating effect on toxic metal contents of soils and plant parts. The FA level 4.0 kg/m2, with 1.0 kg/m2 cyanobacteria mass supplementation, could be taken ideal, since there would be recharging of the soil with essential micronutrients as well as toxic chemicals in comparative lesser proportions, and cyanobacteria mass would cause lessening toxic metal loads with usual N_2-fixation.