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.

The Determination of Heavy Metal Elements in Sipunculs nudus by MWD-ICP-AES

In order to develop a method for measuring of elements in Sipunculus nudus, the contents of Cu, Pb, Cd, Cr, Mn, As, Hg and Ba were determined by actively coupled plasma atomic emission spectrometry （MWD） and microwave digestion （ICP-AES）. The results showed that correlation coefficients al kept higher than 0.999 and the recovery rates of sample added standard solutions were in 98%-114%. The results indicated that the contents of Cu, Pb, Cd, Cr, Mn, As, Hg and Ba were 17.119, 3.781, 0.695, 7.351, 1997.982, 0.620, 0.144, 4.249 mg/kg respectively. The contents of Mn exceeded national limit by hundredfold, Cd sevenfold, Pd fourfold, Cd three-and-a-half-fold, and As onefold. Sipunculs nudus became seriously pol uted. Therefore, it is necessary to formulate robust policies to fol ow closely and pay close attention to coastal areas pol ution around Dongfang City.

Some New Results from the Electron Theory on the Elastical of Alkahoe Earth Metals and Rare Earth Elements

With the introduction of Poisson's ratio in the expression of Young's modulus,nearly all the theoretical values of the various elastic moduli for the alkaline earth metals and rare earth elements can be greatly refined, with the single exception of the theoreticalvalue of Young's modulus for Pr which is slightly increased This points to the validityof the new theory, that the bulk modulus is independent of the Poisson's ratio, and further that the valency electron structures of solids as determined by Yu's theory are correct.

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.

Determination of wholesome elements and heavy metals in safflower(Carthamus tinctorius L.)from Xinjiang and Henan by ICP-MS/ICP-AES

An inductively coupled plasma mass spectrometry （ICP-MS） or inductively coupled plasma atomic emission spectrometry （ICP-AES） was developed to determine 19 elements in safflower, a traditional Chinese medicinal herb from Xinjiang Autonomous Region and Henan Province of China. Totally 19 elements in safflower included heavy metals, i.e. As, Cd, Cu, Hg and Pb, and wholesome elements, i.e. Al, Ca, Co, Cr, Fe, Mg, Mn, Mo, Ni, P, Se, Sr, V and Zn. The results showed that the concentrations of heavy metals in safflower samples were both low, all of which met the national hygiene standards except for Pb in Xinjiang sample. Meanwhile, the distribution tendency of elements in the two samples was similar, which indicated that the plant might absorb given elements in a proportional way. The method can be used for the quality control of elements in safflower, and it provides a way for the determination of the contents of safflower from Xinjiang and Henan.

Heavy Metal Control in Domestic Rubbish by Source Screening and Suitability of Nutrient Elements as Turfgrass Medium

This paper, probing into heavy metal control in domestic rubbish by source screening and nutrient element analysis, revealed the feasibility of source control of heavy metals and the suitability of rubbish as turfgrass medium. Heavy metals in domestic rubbish were controlled by source screening before composting. The study consisted of a control with garden soil. The contents of main mineral elements and heavy metals in rubbish compost and control were determined by the method of ICP-AES. The results showed that heavy metal concentrations in rubbish were lower than those in garden soil, and little difference occurred between rubbish and garden soil in main mineral element concentrations. Based on this, it was concluded that rubbish compost was favorable for using as turfgrass medium and heavy metal control in rubbish by source screening was effective.

SPATIAL-TEMPORAL VARIATION OF HEAVY METAL ELEMENTS CONTENT IN COVERING SOIL OF RECLAMATION AREA IN FUSHUN COAL MINE

Grid method is employed for sampling covering soil at the test field,whic h is reclamation area filled by coal mining wastes for cropland in th e Fushun coal mine,Liaoning Province,the Northeast China.The soil samp les are taken at different locations,inclu ding three kinds of covering soil,th ree different depths of soil layers a nd four different covering ages of covering soil.The s patial-temporal variation of heavy metal element content in reclamatio n soil is stud-ied.The results indicate that the co ntent of heavy metal elements is decreasing year after year;the determin ant reason why the content of heavy metal elemen ts at 60cm depth layer is higher than t hat at 30cm depth layer and surface is fertiliz-er and manure application;the metal elements mainly come from external environment;there is no metal pollut ion coming from mother material(coal mining wastes)in plough layer of covering soil.

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.

Analysis of metallic elements dissolution in the Astragalus at different decocting time by using LIBS technique

Astragalus is an important traditional Chinese herb that has therapeutic potential in the treatment of diseases. In this study, the dissolution of metallic elements during the material decoction process was investigated using laser-induced breakdown spectroscopy(LIBS). The Ca, Mg, Al, and Fe in the drug residues, liquid, and vapor were selected for the study of the transfer of elements after different decocting times. It was found that the intensities of the spectral lines for these elements in the drug liquid increased with increasing decocting times.The contrast trend was observed in the residues and only calcium was detected in the vapor.Furthermore, the relative mass concentrations of Ca, Mg, Al, and Fe in the liquid were quantitatively determined by a combination of the standard addition method and calibrationfree-LIBS method by adding the standard concentration solution of Cu and Cd elements into the drug liquids, it can be found that the maximum error between Cd concentration calculated by internal CF-LIBS and the standard is within 10%. This provides a new method of achieving the on-line monitoring and analysis of metallic elements in the production of traditional Chinese medicines.

Mechanism of interaction relation between the rare-earth element Ce and impurity elements Pb and Bi in Ag-based filler metal

The mechanism of interaction relation between the rare-earth element Ce and elements Pb and Bi in Ag-based filler metal has been studied. The results show that the compounds CePb and CeBi with high melting point can be easily produced between these three elements in the filler metal, which greatly limited the formation of the isolated phase Pb or Bi and also eliminated the bad effect of impurity elements Pb and Bi on the spreading property of Ag-based filler metal. The metallurgical and quantum-mechanical bond formation analysis show that a strong chemical affinity was existed between the rare-earth element Ce and impurity elements Pb and Bi, which was proved by the XRD analysis results.

Effects of rare-earth elements on the glass-forming ability and mechanical properties of Cu_(46)Zr_(47-x)Al_7M_x(M = Ce,Pr,Tb,and Gd) bulk metallic glasses

Cu46Zr47-xA17Mx （M = Ce, Pr, Tb, and Gd） bulk metallic glassy （BMG） alloys were prepared by copper-mold vacuum suction casting. The effects of rare-earth elements on the glass-forming ability （GFA）, thermal stability, and mechanical properties of Cu46Zr47-xA17Mx were investigated. The GFA of Cu46Zr47-xA17Mx （M = Ce, Pr） alloys is dependent on the content of Ce and Pr, and the optimal content is 4 at.%. Cu46Zr47-xA17Thx（X = 2, 4, and 5） amorphous alloys with a diameter of 5 mm can be prepared. The GFA of Cu46Zr47-xA17Gdx（x = 2, 4, and 5） increases with increasing Gd. Tx and Tp of all decrease. Tg is dependent on the rare-earth element and its content. ATx for most of these alloys decreases except the Cu46Zra2Al7Gd5 alloy. The activation energies △Eg, △Ex, and △Ep for the Cu46Zr42A17Gd5 BMG alloy with Kissinger equations are 340.7, 211.3, and 211.3 kJ/mol, respectively. These values with Ozawa equations are 334.8, 210.3, and 210.3 kJ/mol, respec- tively. The Cu46Zr45Al7Tb2 alloy presents the highest microhardness, Hv 590, while the Cu46Zr43A17Pr4 alloy presents the least, Hv 479. The compressive strength （at.f.） of the Cu46Zra3A17Gd4 BMG alloy is higher than that of the Cu46Zr43Al7Tb4 BMG alloy.

Effect of occurrence mode of heavy metal elements in a low rank coal on volatility during pyrolysis

The harmful trace elements will be released during coal utilization, which can cause environment pollution and further endangering human health, especially for heavy metal elements. Compared to combustion, the release of heavy metal elements during coal pyrolysis process, as a critical initial reaction stage of combustion, has not received sufficient attention. In the present paper, a low rank coal, from Xinjiang province in China, was pyrolyzed in a fixed bed reactor from room temperature, at atmospheric pressure, with the heating rate of 10 °C/min, and the final pyrolysis temperature was from 400 to 800℃ with the interval of 100℃. The volatility of heavy metal elements (including As, Hg, Cd and Pb) during pyrolysis process was investigated. The results showed the volatility of all heavy metal elements increased obviously with increasing temperature, and followed the sequence as Hg > Cd > As > Pb, which was mainly caused by their thermodynamic property and occurrence modes in coal. The occurrence modes of heavy metals were studied by sink-andfloat test and sequential chemical extraction procedure, and it can be found that the heavy metal elements were mainly in the organic and residual states (clay minerals) in the raw coal. And most of the organic heavy metals escaped during the pyrolysis process, the remaining elements were mainly in the residual state, and the elements in Fe-Mn state also tended to remain in the char.

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.

Investigating Catalase and Carbonic Anhydrase Enzyme Activities and Levels of Certain Trace Elements and Heavy Metals in Patients with Primary and Metastatic Hepatic Carcinoma

Hepatocellular carcinoma (HCC) is among most common terminal cancer types in the world. Primary etiological factors include cirrhosis, hepatitis, aflatoxin and alcohol. The current study was conducted to determine cytosolic erythrocyte carbonic anhydrase and catalase enzyme activities and levels of some trace elements. For this purpose, 40 patients with primary and metastatic hepatic cancer and 29 healthy volunteers enrolled to the study. Catalase and carbonic anhydrase enzyme activities and serum trace element levels were measured in patient and control groups. In the current study, serum copper, magnesium, manganese and zinc levels were lower in the primary and metastatic hepatic cancer group in comparison with the control group (P < 0.05). In contrast, serum iron, cobalt, cadmium and lead levels were higher in the patient relative to the control group (P < 0.05). In comparison with the control group, the catalase level was lower in primary and metastatic cancer group, while the carbonic anhydrase level was higher in the cancer group (P < 0.05). Changes in levels of trace elements and anti-oxidant enzymes may be the factors which influence the development and progression of liver cancer. The carbonic anhydrase enzyme can be a useful indicator in the diagnosis of cancer. However, this issue warrants further investigation.

Factors Controlling the Distribution of Transitional Metal Elements in Marine Hydrogenic Ferromanganese Crusts

A series of selective dissolution experunents were conducted on the hydrogeinc ferromanganese crusts collected near Line Island to study the geochemistry of Mn, Fe, Cu, Co, Ni and Ti. Despite of the fact that the very close intergrowth between amorphous ferric oxyhydroxides and 6-MnO2 exists in the hydrogenic ferromanganese crusts, there is no isomorphous substitution between iron and manganese. This is because the two elements in oxides have different crystal chemistry and geochemistry, such assertion bemg in agreement with the results of selective dissolution experiments. Transitional metal elements such as Cu, Co, Ni and Ti are enriched in different phases, i.e. Ni and Co are incorporated into 6-MnO2 while Cu and Ti are incorporated into ferric oxyhy- droxides. The distributions of the elements in amorphous ferric oxyhydroxides and δ-MnO2 are controlled by the existing states of the elements in the seawater and the crystal chemistry and geochemistry of these elements/inns in oxides.

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.

Analysis of Different Rare Metals, Rare Earth Elements, and other Common Metals in Groundwater of South West Bank/Palestine by ICP/MS-Data and Health Aspects

Ground water samples are collected from south West Bank/Palestine and analyzed for different rare elements (Rb, Zr, U, P, Ti, V), rare earth elements (La, Ce, and Nd), and other common trace metals (Li, Na, Mg, Ca, Sr, Ba, K, Bi) that most of them usually have no maximum acceptable limits as either they are considered not to be toxic to human health or there is no sufficient data about their toxicity to human health. This study was conducted to determine the water quality of ground water which is used for drinking in the study area. Water samples from ten groundwater wells were obtained in three different dates of the year (November 2012, March 2013, and April 2013). Three water samples were obtained from each well for each sampling date;so a total of 90 water samples were collected from the ten wells. The results obtained from this study suggest a possible risk to the population of the study area given the high concentration of some metals that have no maximum allowed concentration, and the fact that for many people in the study area, ground water is a main source of their water supply.

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.

Evaluation on environmental quality for heavy metal elements of Xihe soil

According to "Environmental quality standard for soil" and using As,Cd,Cr,Cu,Hg,Ni,Pb,Zn elements as evaluation index,the author evaluated soil environmental quality in Xihe area of Shenyang.The results show that the soil in Xihe area is polluted rifely by heavy metal elements.The polluted areas are mainly distributed near the upstreams of Xihe River,Shenxin River and Shenliao irrigation canal.There exist large distinctions among the heavy metal elements to the pollution degree.Cd pollution area is the biggest and the most serious in pollution degree.