Characterisation of mineralogical forms of barium and trace heavy metal impurities in commercial barytes by EPMA, XRD and ICP-MS

This study was carried out to characterise the mineralogical forms of barium and the trace heavy metal impurities in commercial barytes of different origins using electron probe microanalysis (EPMA), X-ray diffraction (XRD) and inductively coupled plasma mass spectrometry (ICP-MS). Qualitative EPMA results show the presence of typically eight different minerals in commercial barytes including barite (BaSO4), barium feldspar, galena (PbS), pyrite (FeS2), sphalerite (ZnS), quartz (SiO2), and silicates, etc. Quantitative EPMA confirms that the barite crystals in the barytes contain some strontium and a little calcium, whereas trace heavy metals occur in the associated minerals. Analysis of aqua regia extracts of barytes samples by ICP-MS has shown the presence of a large number of elements in the associated minerals. Arsenic, copper and zinc concentrations correlate closely in all 10 samples. The findings suggest that barytes is not, as traditionally thought, an inert mineral, but is a potentially toxic substance due to its associated heavy metal impurities, which can be determined by an aqua regia digest without the need for complete dissolution of the barite itself. X-ray powder diffraction was not informative as the complex barite pattern masks the very weak lines from the small amounts of associated minerals.     

Characterisation of individual aerosol particles on moss surfaces: implications for source apportionment

The size, morphology and chemical composition of 8405 particles on moss surfaces (Hylocomium splendens) was investigated by scanning electron microscopy and energy-dispersive X-ray microanalysis. Two moss samples from three locations in Southern Norway (Alg?rd, Birkeland, Neslandsvatn) and two sampling years (1977 and 2005) each were selected leading to a total of 12 samples investigated. At all three locations, particle deposition decreased substantially with time. The major particle groups encountered include silicates, iron-rich silicates, metal oxides/hydroxides, iron oxides/hydroxides, carbonates, carbon-rich particles, silicate fly ashes, iron-rich silicate fly ashes, and iron oxide fly ashes. Between 1977 and 2005, the relative number abundance of the three fly ash groups decreased substantially from approximately 30-60% to 10-18% for the small particles (equivalent projected area diameter <1 microm), and from 10-35% to 2-9% for large particles with diameters ≥1 microm. This decrease of fly ash particles with time was overlooked in previous papers on atmospheric input of pollutants into ecosystems in Southern Norway. In general, the presence of fly ash particles is ignored in most source apportionment studies based on bulk chemical analysis. Consequently, the geogenic component (crustal component) derived from principal component analysis is overestimated systematically, as it has a similar chemical composition as the fly ash particles. The high abundance of fly ashes demonstrates the need to complement source apportionment based on bulk chemistry by scanning electron microscopy in order to avoid misclassification of this important anthropogenic aerosol component.     

Fractionation of elements by particle size of ashes ejected from Copahue Volcano,Argentina

The volcano Copahue, Neuquén province, Argentina has shown infrequent explosive eruptions since the 18th century. Recently, eruptive activity and seismicity were registered in the period July-October, 2000. As a consequence, ash clouds were dispersed by winds and affected Caviahue village located at about 9 km east of the volcano. Samples of deposited particles from this area were collected during this episode for their chemical analysis to determine elements of concern with respect to the health of the local population and its environment. Different techniques were used to evaluate the distribution of elements in four particle size ranges from 36 to 300 microm. X-ray powder diffraction (XRD) was selected to detect major components namely, minerals, silicate glass, fragments of rocks and sulfurs. Major and minor elements (Al, Ca, Cl, Fe, K, Mg, Mn, Na, S, Si and Ti), were detected by energy dispersive X ray analysis (EDAX). Trace element (As, Cd, Cr, Cu, Hg, Ni, Pb, Sb, U, V and Zn) content was quantified by inductively coupled plasma-mass spectrometry (ICP-MS). Nuclear activation analysis (NAA) was employed for the determination of Ce, Co, Cs, Eu, Hf, La, Lu, Rb, Sc, Sm, Ta and Yb. An enrichment was observed in the smallest size fraction of volcanic ashes for four elements (As, Cd, Cu and Sb) of particular interest from the environmental and human health point of view.     

How Probability Survey Data Can Help Integrate 305(b) and 303(d)Monitoring and Assessment of State Waters

Section 305(b) of the United States’ Clean Water Act (CWA) requires states to assess the overall quality of waters in the states, while Section 303(d) requires states to develop a list of the specific waters in their state not attaining water quality standards (a.k.at impaired waters). An integrated, efficient and cost-effective process is needed to acquire and assess the data needed to meet both these mandates. A subset of presentations at the 2002 Environmental Monitoring and Assessment Program (EMAP) Symposium provided information on how probability data, tools and methods could be used by states and other entities to aid in development of their overall assessment of condition and list of impaired waters. Discussion identified some of the technical and institutional problems that hinder the use of EMAP methods and data in the analysis to identify impaired waters as well as development needs to overcome these problems.     

Comparative study of the microstructural and magnetic properties of fly ashes obtained from different thermal power plants in West Bengal, India

This paper deals with the physical nature of the fly ashes obtained from two thermal power plants, situated in West Bengal, India. The fly ash samples are characterized by using comprehensive techniques with an emphasis on their ultrafine nature. The particle sizes of the samples are estimated using scanning electron microcopy (SEM) and found to lie within 0.18–5.90 μm. For morphology and compositional analysis, we also use SEM coupled with energy dispersive X-ray spectrometry. From X-ray study of the fly ashes the nature of conglomeration is seen to be crystalline, and the major components are mullite (Al₆Si₂O₁₃) and quartz (SiO₂). The magnetic measurement of the fly ash samples was carried out by SQUID magnetometer. ⁵⁷Fe Mössbauer spectra are obtained using a conventional constant-acceleration spectrometer with a ⁵⁷Co/Rh Mössbauer source. The hyperfine parameters obtained, in general, support the findings as made from XRD analysis and provide a quantitative measure of different iron ions present in the samples. The paper presents experimental data on the physical aspects of the fly ash samples of the thermal power plants which comprise coarse, fine, and ultrafine magnetic particulate materials and attempts to provide an exhaustive analysis.     

Current status and perspectives of accelerated carbonation processes on municipal waste combustion residues

The increasing volumes of municipal solid waste produced worldwide are encouraging the development of processes to reduce the environmental impact of this waste stream. Combustion technology can facilitate volume reduction of up to 90%, with the inorganic contaminants being captured in furnace bottom ash, and fly ash/APC residues. The disposal or reuse of these residues is however governed by the potential release of constituent contaminants into the environment. Accelerated carbonation has been shown to have a potential for improving the chemical stability and leaching behaviour of both bottom ash and fly ash/APC residues. However, the efficacy of carbonation depends on whether the method of gas application is direct or indirect. Also important are the mineralogy, chemistry and physical properties of the fresh ash, the carbonation reaction conditions such as temperature, contact time, CO₂ partial pressure and relative humidity. This paper reviews the main issues pertaining to the application of accelerated carbonation to municipal waste combustion residues to elucidate the potential benefits on the stabilization of such residues and for reducing CO₂ emissions. In particular, the modification of ash properties that occur upon carbonation and the CO₂ sequestration potential possible under different conditions are discussed. Although accelerated carbonation is a developing technology, it could be introduced in new incinerator facilities as a “finishing step” for both ash treatment and reduction of CO₂ emissions.     

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.     

Serial batch leaching procedure for characterization of coal fly ash

Although many leaching methods have been used for various purposes by research groups, industries, and regulators, there is still a need for a simple but comprehensive approach to leaching coal utilization by-products and other granular materials in order to estimate potential release of heavy metals when these materials are exposed to natural fluids. A serial batch characterization method has been developed at the National Energy Technology Laboratory that can be completed in 2–3 days to serve as a screening tool. The procedure provides an estimate of cumulative metals release under varying pH conditions, and leaching the sample at increasing liquid/solid ratios can indicate the rate at which this process will occur. This method was applied to eight fly ashes, adapted to the acidic or alkaline nature of the ash. The leachates were analyzed for 30 elements. The test was run in quadruplicate, and the relative standard deviation (RSD) was used as a measure of method reproducibility. RSD values are between 0.02 and 0.70, with the majority of the RSD values less than 0.3. The serial batch leaching procedure was developed as a simple, relatively quick, yet comprehensive method of estimating the risk of heavy metal release from fly ash when it is exposed to natural fluids, such as acid rain or groundwater. Tests on a random selection of coal fly ashes have shown it to be a reasonably precise method for estimating the availability and long-term release of cations from fly ash.     

Sediment and Suspended Matter Lead Contamination in the Gulf of Kavala, Greece

Sediment and suspended particulate matter samples from 24 stations in the Gulf of Kavala have been examined for lead contamination. Grain size analysis and organic matter content were also performed. Total – anthropogenic sediment lead concentrations and enrichment factors at stations close to harbors and chemical industries were found higher (up to 209–135μg/g and 4.12 respectively), in relation to concentrations from the rest of the coastal zone. In the above areas, increased suspended particulate lead in the bottom of the water column was also recorded (up to 109μg/g). Total sediment lead concentrations composed of high natural Pb background increased with decreasing grain size, suggesting their association with the fine fractions of the sediments (31.1–66.0% mud presence) and the organic matter content (6–9% higher values). Overall, higher total lead concentrations in the sediments, determined by this work, appear to be significantly different from those reported for the Gulf of Kavala in previous studies and similar to those detected in other highly contaminated eastern Mediterranean coastal areas.     

Biomonitoring of tin and arsenic in different compartments of a limnic ecosystem with emphasis on Corbicula fluminea and Dikerogammarus villosus

Asian clam Corbicula fluminea, the amphipod Dikerogammarus villosus and the macrophyte Nuphar lutea were tested for investigating spatial and temporal variability in the bioavailability of tin and arsenic in the River Lippe, Germany. Samples were collected from September 2002 to May 2003 at a tin polluted site (source pollution) and a reference site. Additional screening sampling was carried out twice in April 2003 to test the extent of As and Sn concentration in periphyton (aufwuchs) samples. Accumulated Sn and As concentrations were measured with ICP-MS after sample processing (dissection, cryo-milling) and digestion. Quality control was performed by parallel analysis of three certified reference materials. Measurable As and Sn contents in plant tissues were only detectable in roots (below 30 microg kg(-1) and 20 microg kg(-1) for As and Sn, respectively). Homogenates from C. fluminea and D. villosus tissues showed site-dependent trace metal contents. Elevated bioavailability of Sn is present downstream of the sewage discharge of the world's biggest producer of tributyltin (TBT) at Luenen (northern Ruhr region). In comparison to C. fluminea, D. villosus shows higher concentrations of tin in samples from both sites. Arsenic concentrations in C. fluminea remain constant with increasing shell size, whereas tin shows a size-dependent accumulation. The results indicate that Corbicula fluminea and Dikerogammarus villosus are suitable passive biomonitoring organisms for Sn, but As levels might be actively regulated. The concentration of tin in the periphyton (aufwuchs) samples was found to be much higher in samples from a contaminated site (428 +/- 63 vs. 1949 +/- 226 microg kg(-1)).     

电感耦合等离子体质谱技术在环境监测中的应用进展

电感耦合等离子体质谱技术(ICP-MS)是目前发展最快的痕量元素分析测试技术之一。由于该技术提供了极低的检出限、极宽的动态线性范围,干扰少、分析精密度高,可进行多元素同时快速分析,可与多种分离技术及样品前处理方法和进样方法相结合等优点,得到了迅速的发展。介绍了ICP-MS的基本原理及仪器构造、与其他分析测试技术的比较及发展趋势,并着重介绍了其在环境监测和环境科学研究领域的应用。     

Assessment of water pollution in different bleaching based paper manufacturing and textile dyeing industries in India

Paper industries using different raw materials such as hard wood, bamboo, baggase, rice-straw and waste papers and bleaching chemicals like chlorine, hypochlorite, chlorine dioxide, hydrogen peroxide, sulphite and oxygen were studied to estimate organic pollution load and Adsorbable Organic Halides (AOX) per ton of production. The hard wood based paper industries generate higher Chemical Oxygen Demand (COD) loads (105–182 kg t⁻¹) and Biochemical Oxygen Demand (BOD) loads (32.0–72 kg t⁻¹) compared to the agro and waste paper based industrial effluents. The bleaching sequences such as C–EP–H–H, C–E–H–H, C–E–Do–D1 and O–Do–EOP–D1 are adopted in the paper industries and the molecular elemental chlorine free bleaching sequence discharges low AOX in the effluent. The range of AOX concentration in the final effluent from the paper industries was 0.08–0.99 kg t⁻¹ of production. Water consumption was in the range of 100–130 m³ t⁻¹ of paper production for wood based industries and 30–50 m³ for the waste paper based industries. Paper machine effluents are partially recycled after treatment and pulp mill black liquor are subject to chemical recovery after evaporation to reduce the water consumption and the total pollution loads. Hypochlorite bleaching units of textile bleaching processes generate more AOX (17.2–18.3 mg l⁻¹) and are consuming more water (45–80 l kg⁻¹) whereas alkali peroxide bleaching hardly generates the AOX in the effluents and water consumption was also comparatively less (40 l kg⁻¹ of yarn/cloth).     

Inventory methods for trees in nonforest areas in the great plains states

The US Forest Service’s Forest Inventory and Analysis (FIA) program collects information on trees in areas that meet its definition of forest. However, the inventory excludes trees in areas that do not meet this definition, such as those found in urban areas, in isolated patches, in areas with sparse or predominantly herbaceous vegetation, in narrow strips (e.g., shelterbelts), or in riparian areas. In the Great Plains States, little is known about the tree resource in these noninventoried, nonforest areas, and there is a great deal of concern about the potential impact of invasive pests, such as the emerald ash borer. To address this knowledge gap, FIA’s National Inventory and Monitoring Applications Center has partnered with state cooperators and others in a project called the Great Plains Initiative to design and implement an inventory of trees in nonforest areas. The goal of the inventory is to characterize the nonforest tree resource using methods compatible with those of FIA so a holistic understanding of the resource can be obtained by integrating the two surveys. The goal of this paper is to describe the process of designing and implementing the survey, including plot and sample design, and to present some example results from a reporting tool we developed.     

Monitoring the species of arsenic, chromium and nickel in milled coal, bottom ash and fly ash from a pulverized coal-fired power plant in western Canada

The concentration of As, Cr and Ni and their speciation (As3+;5+, Cr3+;6+ and Ni0;2+) in milled coal, bottom ash and ash collected by electrostatic precipitator (ESP) from a coal fired-power plant in western Canada were determined using HGAAS, ICP-AES and XANES. The chemical fractionation of these elements was also determined by a sequential leaching procedure, using deionized water, NH4OAC and HCI as extracting agents. The leachate was analyzed by ICP-AES. Arsenic in the milled coal is mostly associated with organic matter, and 67% of this arsenic is removed by ammonium acetate. This element is totally removed from milled coal after extraction with HCI. Arsenic occurs in both the As3+ and the As5+ oxidation states in the milled coal, while virtually all (>90%) of the arsenic in bottom ash and fly ash appears to be in the less toxic arsenate (As5+) form. Both Ni and Cr in the milled coal are extracted by HCI, indicating that water can mobilize Ni and Cr in an acidic environment. The chromium is leached by water from fly ash as a result of the high pH of the water, which is induced during the leaching. Ammonium acetate removes Ni from bottom ash through an ion exchange process. Chromium in milled coal is present entirely as Cr3+, which is an essential human trace nutrient. The Cr speciation in bottom ash is a more accentuated version of the milled coal and consists mostly of the Cr3+ species. Chromium in fly ash is mostly Cr3+, with significant contamination by stainless-steel from the installation itself.     

Inter-Laboratory Comparison of No2 and SO2 Generated by Dynamic Dilution System Under Laboratory Conditions: A Technical Discussion

A workshop on analytical quality control (AQC) of ambient air quality measurement methods for nitrogen dioxide (NO₂) and sulphur dioxide (SO₂) was conducted by Central Pollution Control Board (CPCB) for officials involved in National Ambient Air Quality Monitoring (NAAQM) in India. Concentrations of NO₂ and SO₂ were generated by dynamic dilution system under laboratory conditions at low and high levels and measured using static dilution system and wet chemical methods laid down by CPCB under section 16(2)(h) of the air act 1981. CPCB provided the measured values as reference values for comparing the means obtained by the officials participated from thirteen organizations. A tolerance limit of ±15% of the reference values was specified to accept the results. Generated concentrations, which were unknown to the participants, were measured using gaseous sampling assembly (Envirotech APM 411, New Delhi, India), and wet chemical methods laid down by CPCB i.e. the same methodology which is used by the organizations to generate the data of NO₂ and SO₂ in ambient air. Simultaneously, concentrations were checked by CPCB using automatic analyzers as a check on reference concentration. It is observed that results of automatic analyzers for NO₂ and SO₂ were within a tolerance of ±5% with %RSD below 3. On the other hand, results of most of the participants showed variability in the measurements with %RSD ranging between ±0.8 and ±88.6 and exceedences of means from the tolerance limit with bias ranging between 1.4 and −59%. To check the cause of high variability in the measurements obtained under identical conditions, duplicate sampling was performed by one of the participants for SO₂ at low concentration level. In this study, results of wet chemical methods, automatic analyzers and results of duplicate sampling are analysed statistically to assess the cause of high variability in the measurements. Analysis of t-test and analysis of variance (ANOVA) showed highly significant results for NO₂ and SO₂ at high concentration levels (α 0.05) and for SO₂ at both the levels (α 0.01) respectively indicating some bias is existing either in the sampling or in analytical technique. Duplicate sampling performed to check precision in parallel measurements showed high %RSD indicating the presence of systematic error in sampling technique as the same calibration factor (CF) was used to measure the concentration of duplicate samples. Statistical analysis of flow rates of duplicate sampling showed that the sampling assembly could not maintain the constant flow rate within the ±10% with that measured at the start of the sampling. This resulted in high %RSD and deviation from the reference values for the results of most of the participants, even after accepting ±15% tolerance limit. There is a need to improve and evaluate this gaseous sample collection device under laboratory conditions to generate reliable database of NO₂ and SO₂ in ambient air.     

土壤重金属分析方法间检测结果一致性判断方法——数据对t值检验法的改进与完善

不同分析方法测定结果间的比较,或者说如何判断两种分析方法测定结果的一致性,是检测实验室经常遇到的实际问题。其应用场景包括方法标准验证实验、新方法与经典方法间的比对,特别是在缺少标准样品、测试数据不满足t值检验的条件下,选用合适的判据尤其重要。以采用单波长激发型能量色散X射线荧光光谱法、电感耦合等离子体质谱法、波长色散X射线荧光光谱法测定土壤和水系沉积物样品中Cd、As、Pb、Cu、Zn、Ni、Cr、Co、V、Mn、Mo、Sb等重金属含量所得数据为例,探讨了《环境监测分析方法标准制订技术导则》(HJ 168—2020)附录B中规定的"数据对t值检验法"的不足及改进办法,即用数据对相对偏差和再现性限合格率作为判据,判断分析方法测定结果的一致性。对一组验证样品分别用两种分析方法进行了测定,在数据对t值检验的基础上,取各元素测定结果的相对偏差与相关限值进行比较,或者取两者的差值与基准分析方法标准规定的再现性限进行比较,利用合格率大小协助判断了两分析方法测定结果的一致性。研究结果表明,此方法符合日常质控技术规范中关于精密度的规定,实用性强,是一条将数理统计原理与专业知识相结合的合理技术路线。     

A comprehensive physico-chemical, mineralogical and morphological characterization of Indian mineral wastes

This paper provides a comprehensive characterization of mineral waste such as fly ash, bottom ash, slag and construction demolition (C&D) collected from four different thermal power plants, three steel plants and three C&D waste generation sites in India. To determine utilisation potential and environmental concerns, as received fly ash, bottom ash, slag and C&D waste were analysed for physico-chemical, mineralogical and morphological properties. The physico-chemical properties analysed include pH, moisture content, acid insoluble residue, loss on ignition(LOI), carbon content, fineness, chloride content, sulphate content, reactive silica content, XRF and heavy metal analysis. Morphological and mineralogical characteristics were investigated using scanning electron microscopy–energy dispersive X-ray. Particle size distribution was obtained using particle size analyser. The material analysed has different compositions and were selected with a view to determine their suitability for different applications in cement and concrete industry and for further research studies.     

Distribution and contamination assessment of heavy metals in sediment of the Second Songhua River, China

The Second Songhua River was subjected to a large amount of raw or primary effluent from chemical industries in Jilin city in 1960s to 1970s, resulting in serious mercury pollution. However, an understanding of other trace metal pollution has remained unclear. The objective of this study was to investigate trace metal contamination in the sediment of the river. Bottom sediment samples were taken in the river between Jilin city and Haerbin city in 2005. An uncontaminated sediment profile was taken in the Nen River at the same time. Total concentrations of Al, Fe, Mg, Ca, K, Na, Ti, Mn, V, Sc, Co, Cu, Cr, Ni, Pb and Zn in the sediment samples were measured by ICP-MS or ICP-OES, following digestion with various acids. Concentrations of Co, Cu, Cr, Ni, Pb and Zn in the surface sediments were 5.1–14.7, 18.5–78.9, 2.4–75.4, 7.2–29.0, 13.5–124.4, and 21.8–403.1 mg/kg, respectively, generally decreasing along the course of the river from Jilin city to Haerbin city. Background concentrations of trace metals were reconstructed by geochemical normalization to a conservative element scandium. Results showed that concentrations of Co, Cr, and Ni in the sediment were generally only slightly higher than or equal to their background values, while concentrations of Cu, Pb, and Zn in the some sediment samples were significantly higher than their background values. In detail, the sediment at Jilin city was moderately contaminated by Cu, and the sediment of the Second Songhua River was moderately contaminated by Pb and Zn. The top layer (0–10 cm depth) and bottom layers (30–46 cm depth) of one sediment profile at Wukeshu town were generally moderately polluted by Pb and Zn. Synthetically, the surface sediment in the studied river section was classified as natural sediment without ecological risk by the sediment pollution index (SPI) of Cu, Cr, Ni, Pb and Zn. Only the 30–45 cm depth of the sediment profile at Wukeshu town was classified as low polluted sediment by the SPI of these metals, recording a historical contamination of the river in the 1960s to 1970s. This buried contamination of trace metals might pose a potential risk to water column under disturbance of sediment. Foundation item: The National Basic Research Priorities Program of China (2004CB418502)     

原子荧光法和电感耦合等离子体质谱法测定水中锑的比较

分别用原子荧光法(AFS)和电感耦合等离子体质谱法(ICP-MS)测定水中锑。AFS法和ICP-MS法均线性良好,相关系数分别为0.999 8和0.999 9,检出限分别为0.17和0.03μg/L,相对标准偏差均1.15%,加标回收率分别为96.6%~111.9%和95.4%~111.5%,2种方法均能很好地用于水中锑的测定。其中,ICP-MS法适合较清洁地表水和地下水样品中锑的分析,AFS法则对地表水、地下水和废水样品均适用。     

石墨炉原子化机理研究方法评述

评述了近年来石墨炉原子化机理研究中用得较多的研究方法,包括热力学方法、动力学方法、原子吸收光谱法、X射线衍射法、X射线光电子能谱法、俄歇电子能谱法、扫描电镜法、分子吸收光谱法和质谱法.每种方法均有其优缺点,综合运用多种研究方法,特别是理论研究与实验研究相结合,更好地阐明原子化机理.