Heavy metals contribution of non-aqueous fluids used in offshore oil drilling

A monitoring program was performed to investigate heavy metal content alteration due to exploratory drilling for oil using non-aqueous fluids (NAFs) in Brazilian offshore, 900 m deep. Fourteen elements were monitored in 54 sites and it was verified that after drilling activities the average Ba concentration was remarkably increased with respect to background level, even 1 year after the activity. A minor increase in Mn and a moderate increase in Al concentrations were verified. The Cd, Cr, Ni, As, Co, Cu, Pb, V, and Zn concentrations were at the background levels, ca. 1 year after the NAFs drilling materials deposition on the seafloor. The Al, Ba, Cd, Cr, Cu, Ni and Zn mean concentrations were significantly different (P<0.05) between the three sampling operations (cruises) performed, while As, Cd, Fe and Pb presented different mean values according to the distance of the oil well, independent of the sampling operation. Interaction between sampling operation and distance was observed for Mn. In all sediment samples the Hg concentration was below the detection limit (0.07 μg g⁻¹).     

Partitioning of elements in a entrained flow IGCC plant: Influence of selected operational conditions

The partitioning of trace elements and the influence of the feed conditions (50:50 coal/pet-coke feed blend and limestone addition) was investigated in this study. To this end feed fuel, fly ash and slag samples were collected under different operational conditions at the 335 MW Puertollano IGCC power plant (Spain) and subsequently analysed. The partitioning of elements in this IGCC plant may be summarised as follows: (a) high volatile elements (70->99% in gas phase): Hg, Br, I, Cl and S; (b) moderately volatile elements (up to 40% in gas phase and ?60% in fly ash): As, Sb, Se, B, F, Cd, Tl, Zn and Sn; (c) elements with high condensation potential: (>90% in fly ash): Pb, Ge, Ga and Bi; (d) elements enriched similarly in fly ash and slag 30-60% in fly ash: Cu, W, (P), Mo, Ni and Na; and (e) low volatile elements (>70% in slag): Cs, Rb, Co, K, Cr, V, Nb, Be, Hf, Ta, Fe, U, Ti, Al, Si, Y, Sr, Th, Zr, Mg, Ba, Mn, REEs, Ca and Li. The volatility of As, Sb, and Tl and the slagging of S, B, Cl, Cd and low volatile elements are highly influenced by the fuel geochemistry and limestone dosages, respectively.     

Content, mobility and transfer behavior of heavy metals in MSWI bottom ash in Zhejiang province, China

Municipal solid waste incinerator (MSWI) bottom ash samples were taken from six cities of Zhejiang province, where 1/4 incinerators of China were located. The samples were instrumentally analyzed to detect the content of heavy metals. Sequential extraction procedure (SEP) was adopted to characterize the mobility and environmental impact of heavy metals. And the transfer coefficients of heavy metals from the input MSW to the bottom ash during the incineration were also calculated. It showed that the average content of Zn, Mn, Cu, Pb and Cr in the bottom ash exceeded 300 mg/kg, which was much higher than that in the soils. SEP results showed that although the residue fraction was the primary fraction of the heavy metals in the bottom ash, there were still 1.84 mg of Cd, 86.21 mg of Cu, 83.46 mg of Pb and 939.46 mg of Zn in 1 kg bottom ash having the potential of leaching, which indicated a great threat to the surrounding environment. The result of coefficients calculation revealed that almost all the Cu, Cr, Mn and Ni in the input MSW were transferred to the bottom ash during the incineration. Bottom ash was also the main destination of Cd, Co, As, Mo, Pb and Zn though considerable amounts of those metals were transferred to the raw gas.     

Trace metal distribution in fractions of solvent-refined coal by ICP-OES and implications regarding metal speciation

Separations of Amax solvent-refined coal according to its acid/base/neutral components and by selective elution from a silica column (SESC) to yield nine fractions have been carried-out. After ashing with H₂O₂-H₂SO₄, twenty metals (Mg, Al, P, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr, Mo, Cd, Sr, Zr, W, Hg and Ba) were analysed by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). A majority of elements (Zn, Cd, Hg, Cr, Mo, W, and Fe) were found concentrated in the acid fraction while Co, Ni and Cu preferred the neutral and base fraction. In the step gradient SESC fractions, the greatest concentration of metal was found in fractions that had been characterized as enriched with phenols.     

Trace metal contents of acidic,basic and neutral components of a cyclohexanol extract of Kosova Basin lignite

A sample of Kosova Basin lignite was extracted with cyclohexanol. The yield of extract was 19.98 wt%. The extract was fractionated into acidic, basic and neutral components and benzene- and petroleum ether-insoluble fractions. After ashing with HClO₄ and HNO₃, eleven elements (K, Ca, Mg, Fe, Pb, Zn, Cu, Mn, Cr, Cd and Ni) were analysed by atomic absorption spectroscopy and seven elements (Al, Ba, Sr, Be, B, Ga and V) by inductively coupled plasma optical emission spectroscopy. A majority of the elements (Fe, B, Al, Zn, Pb, Cu, Ca, Mg, Sr, Ga and V) were found concentrated in the acidic and phenol fractions, while K, Ni, Ga and Cu predominated in the amine fraction. The metals thus analysed were associated with heteroatoms.     

应用ICP-MS同时测定矿泉水中22种微量金属

研究结果表明应用ICP-MS可以同时测定饮用天然矿泉水中的Li、Be、B、Al、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Ge、As、Se、Sr、Mo、Ag、Cd、Sb、Ba、Pb、等微量金属元素.ICP-MS法具有快速、准确、处理简单、干扰少等优点.     

Chemometric analysis of trace elements distribution in raw and thermally treated high sulphur coals

In the present study, chemometric analysis is applied as a tool to evaluate the release behaviour of trace elements (TEs) during coal utilization processes. Principal component analysis (PCA) and linear discriminant Analysis (LDA) were applied on the TE concentrations of raw and thermally treated coals. PCA and LDA successfully predicted the association of 21 trace elements (Na, Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sb, Te, Pb) contained in coal and their thermal behavior at various temperatures. Application of chemometric on thermally treated coals shows that at temperature 450 °C, elements like Na, P, K, Fe, Ca, Mg, Al and Si have affinity with mineral matter and therefore have low volatility. Elements like Te, Sb and Ti may form their chlorides, which enhance the volatilities of these elements, while Co and Pb may form sulfides like Co₂S₄ and PbS. In the temperature range of 600-850 °C, either coal undergones an intense degradation of its structure during pyrolysis and the elements released may be adsorbed on coal surface or be volatile. The elements Cr, Co, V, Ni may react with sulphurous gases evolved during pyrolysis. At temperature 1000 °C, wide dispersion in data elements interact with carbon and sulphur compounds of coals. The formation of compounds like Si carbide, bassanite, gehlenite, anarthite may also be responsible for low volatilities of the elements Si, Al and Ca at higher temperatures. Predictive capabilities of PCA and LDA were evaluated in terms of TEs volatilities at different temperatures. The results of chemometric analysis are not only in good agreement with volatilities of TEs present in coals at various temperatures but also with FTIR analysis.     

微波消解-ICP-OES法测定黑芝麻中的18种矿质元素

采用HNO3/H2O2湿法微波消解制样,利用全谱直读电感耦合等离子原子发射光谱法(ICP-OES),全面详细地分析测定了黑芝麻中的矿质元素,共检出Ca、P、S、Mg、K、Al、Si、Fe、Na、Zn、Se、Sr、Cu、Mn、Ba、B、Ti、Cr等18种矿质元素,RSD值在1.21%～10.1%,其中13种元素在5%以内。黑芝麻中所含人体常量元素Ca、P、S、Mg、K、Na等的质量分数分别为1.79%,1.08%,0.59%,0.43%,0.41%和0.009 1%;微量元素Fe、Zn、Se、Cu、Mn、B、Cr、Sr、Si、Al等的含量分别为18.6,4.55,3.87,1.74,1.62,0.91,3.21,78.8,125.8 mg/100 g,未检出Pb、Hg、Cd、As以及Ni、Co、Mo等元素。     

Multi-element determinations of N,N-dimethylformamide (DMF) coal slurries using ICP-OES

A slurry nebulisation technique was applied for elemental analysis of bituminous coals SARM 18, SARM 19 and four coals from three different seams in Witbank, South Africa, by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major elements (Al, Ca, Fe, Mg, S, Si and Ti) and trace elements (Ba, Cr, Mn, Ni, Sr, V, Zn and Zr) in coal were determined. Various slurry preparations were evaluated using two dispersants (glycerol and Triton X-100) and by varying the concentration of dispersants, between 0.1% and 1.0% (v/v). The effect of initially solubilising the ground coal in N,N-dimethylformamide (DMF) was investigated by varying the volume of DMF added. The effect of wet grinding with DMF was investigated. Wet grinding with DMF was shown to drastically reduce particle sizes (50.0% < 0.28 μm and 90.0% < 6.17 μm) as compared to dry grinding (50.0% < 5.25 μm and 90.0% < 11.1 μm). The reduced particle sizes and increased transport efficiency of the coal slurries led to improved analytical recoveries of elements in the reference coal, SARM 18. The best analytical recoveries for all elements were achieved using 0.1% Triton X-100 with 10.0% DMF. Results obtained by ICP-OES after wet grinding of the coal with DMF, using 0.1% Triton X-100, also gave excellent recoveries (Al, 100%; Ca, 103%; Cr, 106%; Fe, 102%; Mg, 100%; Mn, 104%; Ni, 109%; Si, 102%; Ti, 95.0%; and V, 108%). The results obtained with 10.0% DMF and 0.1% Triton X-100 were in agreement with certified values for all selected elements according to paired t-test at the 95.0% confidence level. Selected elements (Al, Ca, Fe, Mg, Mn, Si, Ti and V) were also analysed with X-ray fluorescence for comparison with results obtained from ICP-OES. Analysis by ICP-OES of microwave digested coal was also carried out. It is suggested that the DMF slurry technique could be used for routine analysis of bituminous coals.     

石墨炉原子吸收法测定硝酸银中的痕量元素

感光级硝酸银样品经一系列的化学处理后,上清液采用石墨炉原子吸收分光光度法测定其中Bi,Cd,Cr,Cu,Fe,Mn,Ni,Pb,Sb,Sn,Te,Se,Zn元素的含量,本方法测定Bi,Cd,Cr,Cu,Fe,Mn,Ni,Pb,Sb,Sn,Te,Se,Zn各元素均能得到良好的标准曲线,即r=0.99~1;Cu、Cr、Ni、Sb、Sn、Mn、Te、Se的回收率较好,一般可达到95%~110%,Zn、Bi、Cd、Pb的回收率较低,经常只有50%~60%。     

Geochemical implications of trace elements and sulfur in the saturate, aromatic and resin fractions of crude oil from the Mara and Mara Oeste fields, Venezuela

Ten trace elements (Cr, Zn, Fe, Mn, Cu, Co, Ni, Mo, V and Sr) and sulfur were determined in the saturate, aromatic and resin fractions of 15 crude oils from Mara (DM) and Mara Oeste (DMO) fields of the Maracaibo Basin, Venezuela. The oils studied are classified as unaltered or altered by biodegradation. In the altered oil, the depletion of n-alkanes, the absence of isoprenoids and the presence of steranes and hopanes unaltered by biodegradation are indicative of moderate biodegradation. The elements Zn, Fe, Mn, Cu, Ni, and Sr were detected in the saturated hydrocarbon fraction; Cr and V were detected in the aromatic fraction in addition to the above elements; whereas the elements detected for the resin fraction were Cr, Zn, Fe, Cu, Ni, Mo, V, and Sr. Co was not detected in any fractions of the oils analyzed. Sulfur was found in all fractions of the oils studied. It was proposed that Fe, Zn, Sr, and Mn could have entered the oil during migration or Fe, Zn and Mn as pollutants during oil extraction. Cr and Cu may be of biological origin and Mo could be incorporated into the reservoir through bacteria. Only S, V, and Ni in the resin fractions can be used as indicators of the origin and correlation of Mara and Mara Oeste oils. Based on the results obtained in this work, it can be established that the V/(V+Ni) ratio in the resin fraction can be used as a correlation parameter, for these oils.     

中低温煤焦油蒸馏过程中金属元素的迁移规律

以中低温煤焦油轻油和重油为实验原料,采用常压蒸馏获得170~200℃、200~240℃、240~270℃、270~300℃、300~320℃、320~340℃、340~360℃和360~390℃煤焦油馏分油;利用配有油品加氧制冷进样系统的ICP-OES测定了21种微量元素在馏分油中的含量,考察了不同馏分油中元素的分布情况。研究表明：在原煤焦油中,未发现Ag、Mg、Mo、Na、Ni、Fe、Mn、Cr及Ti元素,含量较高的元素有Sn、P、Al、Pb、Si,其中Sn元素在轻油和重油中的含量分别为11.78μg/g和14.04μg/g;在所有馏分油中,未发现Al、Mo、Fe、Mn、Cr及Ti元素,含量比较高的元素有Si、Sn、Na、Zn、Pb,特别是Si、Na、Sn、Zn、Ni、Pb及B元素可以有效富集于馏分油中。可能的原因是Ca、Fe、Mg、Al等金属以不同的盐类形态存在,在煤焦油脱水及<170℃蒸馏过程中,这些金属盐类会被部分带出,导致其在馏分油中的含量未富集或未检出;通过关联金属元素在馏分油中的分布与其组成的关系,馏分油中元素的分布可能与酚类化合物、杂环化合物和蒸馏温度等相关。酚类化合物及杂环化合物可能与Ag、B、Cu、Mo、Sn、Na、Zn、Ca、Pb等金属形成络合物或卟啉配合物,蒸馏温度一方面可以破坏Sn、Cd、Pb、Zn、Cu、Ca、Pb等元素在馏分油中的结合力,另一方面也可以促进这些元素与馏分油中的含氧、含氮等化合物更好地发生化合反应,进而影响金属元素在馏分油中的含量分布。     

Geochemical aspects of Amynteon lignites, Northern Greece

Several lignite samples were collected from Amynteon lignite mine, Northern Greece. Chemical analysis for major and trace elements was conducted with the help of X-ray fluorescence and inductively coupled plasma-atomic emission spectroscopy methods. Trace element concentrations of Amynteon lignites have equal or slightly higher values when compared to other worldwide coals. Boron content implies that the lowest lignite beds raised in a middle brackish environment, while the upper lignite beds had a fresh water environment of deposition. Correlation and cluster analysis revealed an inorganic affinity for the elements Al, Si, Ti, Fe, Mg, K, Na, Ni, Cu, Ba, Mo and Sr, while Ca, Cr, Mn, Zn, P, Cd, Sb, Pb, S, B, Co and W, and only F showed an organic affinity. The calculated slagging and fouling indices indicate medium to high slagging and high to severe fouling propensity.     

Prediction of the distribution of trace elements between the product streams of the Prenflo gasifier and comparison with reported data

The equilibrium distribution of the major, minor and trace elements in Pittsburgh No. 8 coal has been predicted for gasification under the conditions of the Prenflo gasifier using the FACT and MTDATA suites of predictive programs. The databases normally available with these programs have been supplemented with the MIRO-NPL oxide melt representation, a model of oxide melts from the field of geochemical modelling and representation of trace element solution in oxide melts based on the IMCC model. The results have been compared with observations at the Fürstenhausen Prenflo plant available in the literature. The gasifier is modelled as two regions: in the first the temperature is high (1400-2300 K) and the reacting mixture consists of the coal, carrier gas, added steam and oxygen. In the second region the equilibrium mixture from the first is quenched by addition of an equal amount of the cooled, dried product gas, then cooled in 10 K steps from 1073 to 473 K. The observed and predicted distributions of the elements are in general agreement. The elements may be grouped into those which are virtually immobile (Cr, Ni, Ba, Mn, V), somewhat mobile (Mo, Cu, Be), mobile (Sb, B) and almost totally mobilised (As, Cd, Pb, Tl, Sn, Zn) according to predictions, and this grouping is consistent with the experimental mobility as deduced from the relative abundances in slag, fly ash and filter cake. On cooling, arsenic is found to persist in the gas at 473 K at the highest fraction of the input level of any of the trace elements, which is consistent with observations.     

电感耦合等离子体质谱法( ICP-MS)测定地下水中痕量元素

用电感耦合等离子体质谱法(ICP-MS)测定了地下水中痕量元素(Cd、Co、Cr、Cu、Mn、Mo、Ni、Pb、As、Se、Zn、Ba、Fe),应用在线加入内标校正干扰效应,元素检出限为0.002-0.179 μg,/L,加标回收率为96.50 ％～103.10％,相对标准偏差(RSD)＜2.31％.试验结果表明该法测...     

Trace elements in Turkish biomass fuels: Ashes of wheat straw, olive bagasse and hazelnut shell

Ash contents of wheat straw, olive bagasse and hazelnut shells were 7.9%, 3.9%, 1.2%, respectively, which seemed to be within the average values of ash of biomass. The microstructure of ashes included smooth, polygonal, granular and molten drop structures. A large percentage of particles present in ashes are commonly ∼1-20 μm in size. SEM/EDS analyses performed on the major ash forming elements in different ashes indicated that Si, Ca, K and Mg and P were generally the most abundant species. Trace element levels in ash samples of various biomass types such as hazelnut shell, wheat straw, olive bagasse were analysed using ICP spectroscopy. The elements determined were some of those considered being of great environmental concern such as, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb. In all of the ashes studied Fe had the highest concentration among other trace elements, Mn was the second element that exhibited higher concentrations. The order of concentration of elements in the ashes from the highest to the lowest values was as follows: Fe > Mn > Zn > Cu > Ni > Cr > Pb > Co.     

Affinage electrolytique des ferronickels

Electrorefining of ferronickels is possible in a cell without diaphragm with the electrolyte CaCl₂ 5 M at 98°C.Behavior of the following impurities have been studied: Ag(I), Au(III), Bi(III), Cd(II), Co((II), Cu(I), Fe(II), Hg(II), Ni(II), Pb(II), Pd(II), Sb(III) and Sn(II).The electrochemical system Ni(II)/Ni(O)is much more reversible in this electrolyte and the only other electrochemical system which appears at the same potential is Cu(I)/Cu(O).Ferronickels of 23.2;72.2 and 94.4% in nickel have been refined in this medium without purification of the electrolyte. Nickel of a purity between 98.7 and 99.7% is obtained.In order to increase the nickel purity and for continuous operation of the method a purification of the electrolyte is necessary. Two methods are proposed: anion exchange resin and liquid—liquid extraction with tri-n-butyl phosphate (TBP).Partition coefficients and ion-exchanger capacities are given for following impurities: Fe(III), Fe(II), Co(II), Cu(II), Mn(II), Zn(II), Cr(III) and Pb(II).Percent extracted by TBP for following impurities are given: Fe(III), Fe(II), Co(II), Cu(II), Zn(II), Mn(II), Cr(III), Pb(II), Al(III), Bi(III), Sb(III) and Sn(IV).A continuous purification of the electrolyte by ion-exchange has been done in the refining of a ferronickel 94.4% in nickel. Nickel obtained is 99.74%.CaCl₂ 5 M appears to be a good electrolyte for electro-refining of nickel.     

ICP-MS法测定注射用双黄连(冻干)无机阳离子的含量

注射用双黄连(冻干)样品经微波消解后,利用电感耦合等离子体质谱(ICP-MS)测定其中B、Al、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、As、Cd、Ba、Hg等15种微量元素的含量。结果表明,方法回收率为81.6%～96.3%,检出限为0.001～1.53 ng/g,方法快捷、准确、灵敏度高,可以用于注射用双黄连(冻干)的微量元素的测定,同时也进一步完善了注射用双黄连(冻干)无机元素分析,为其质量控制提供了参考依据。     

Properties of water-soluble and insoluble particulate matter emitted from dewatered sewage sludge incineration in a pilot-scale ash melting furnace

Emission of inorganic particulate matter (PM) from the incineration of dewatered sewage sludge has been investigated in a novel ash melting furnace. The sludge containing 79 wt% water was incinerated in an oxygen-enriched atmosphere at the primary temperature of 1400 °C, and its unburned volatile was combusted at 1100 °C in a secondary combustion chamber. A 13-stage low-pressure-impactor and the conventional impinger methods were employed for PM sampling at the outlet of the secondary combustion chamber. The results indicate that, PM is dominated by volatile and semi-volatile elements including Br, Cl, P, S, Na, K, Zn, As, Cu, Mn and Ni. Less refractory elements were found. PM has two major fractions: <0.22 and ?0.22 μm. Their chemical forms as well as water solubility are different between two fractions. The majority of Br, nearly half of Cl, and 40% of S and P are present in the small fraction. They are mostly water-soluble due to the association with alkali elements and heavy metals. The water-insoluble calcium sulfate and calcium/iron phosphate were, however, found in the large fraction of PM. Regarding the cations, the water solubilities of Na, K, Mn and Ni are close to their proportions partitioned into the small fraction of PM, since their water-soluble species were preferentially formed in this fraction. A relatively weak correlation for Al, Ca and As, while no such a correlation were found for Cu, Zn and Fe, due to the complex compounds formed for them.     

A Rock-Iron-Solubilizing Compound from Root Exudates of Tephrosia purpurea

Root exudates from Tephrosia plants contained a rock-iron [Fe(OH)₃] -solubilizing compound. This was purified to apparent homogeneity and appears to possess an iron-binding phenolic moiety linked to a proteinaceous component that may act as a receptor. The lyophilized purified fraction showed maximum Fe(OH)₃-solubilizing activity at 50°C under acidic pH. Its activity was influenced by trace ions (Co, Cu, Zn, B, Mo, Mn) and toxic metal ions (Ni, Al, Pb, Cr, Hg), but ions such as Na, K, Mg, and Ca had no significant effects on its Fe(OH)₃-solubilizing activity.