Application of instrumental neutron activation analysis and inductively coupled plasma-mass spectrometry to studying the river pollution in the State of Minas Gerais

Instrumental neutron activation analysis (INAA) and inductively coupled plasma-mass spectrometry (ICP-MS) have been used for the determination of toxic heavy metals and other pollutants in the water of the Das Velhas river in the State of Minas Gerais, in south-east Brazil. Elemental concentrations of about 60 elements were measured in water samples collected to different parts of this river and from two affluents. There was a good agreement between the two analytical methods and the results were complementary. The results indicated an increase in the concentration of several polluting elements in the water from mining industry area.     

Analysis of heavy metals and sulphur-rich compounds in the water moss Fontinalis antipyretica L. ex Hedw.

The water moss Fontinalis antipyretica has been investigated to estimate heavy metal pollution in the river Elbe (middle Germany). Procedures of plant separation, digestion as well as an analytical method for ICP-MS analyses have been evaluated. Reproducibility and accuracy have been demonstrated on BCR 61 (NIST) reference material and results have been compared with AAS and AES data. The distribution of heavy metals in different plant segments of indigenous material has been analyzed. Exposition of plant material in the river Elbe have shown no correlation between the heavy metal content in plants and that of water samples. Cd and Zn concentrations found in the plant material are significantly enriched relatively to control samples. To understand the sophisticated ‘real system’ experiments have been carried out under laboratory conditions to investigate induced sulphur-rich compounds in the presence of heavy metals using HPLC including on-line derivatization.     

Determination of Heavy Metals in Soils, Sediments and Geological Materials by ICP-AES and ICP-MS

 Sixteen soil and sedimentary geological reference materials were analysed for As and the heavy metals Cd, Co, Cr, Cu, Ni, Pb and Zn by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS) in combination with total and partial dissolution of the samples. It can be demonstrated that none of the modern ICP methods is completely free from analytical problems. This applies in particular when the concentrations are close to the detection limits (e.g. in ICP-AES) and is mainly due to the wide variation in the bulk composition of soils resulting in complex matrix effects (e.g. in ICP-MS). In order to determine the extent of soil pollution by heavy metals, both partial and total dissolution have to be performed prior to analysis.     

Comparison of heavy metal analyses in hydrofluoric acid used in microelectronic industry by ICP-MS and thermal ionization isotope dilution mass spectrometry

An isotope dilution mass spectrometric (IDMS) method with the thermal ionization (TI) technique has been developed for the determination of trace impurities of Cr, Fe, Ni, Cu, Zn, Ag, Cd, Tl, Pb, Th, and U in high-purity HF (50% by weight) used in the semiconductor industry. The evaporation step of the HF solution was carried out in an apparatus which did not significantly contribute to contaminations of the heavy metals to be analysed. This apparatus allowed fast evaporation of the HF solution of up to 200 ml/h and therefore also a fast trace heavy metal/matrix separation was carried out. The evaporation step was also used in connection with inductively coupled plasma mass spectrometry (ICP-MS) when applying the isotope dilution technique and an external calibration for quantification, respectively. The detection limits for TI-IDMS were (in pg/g): Cr=30, Fe=400, Ni=70, Cu=20, Zn=1100, Ag=70, Cd=10, Tl=1, Pb=16, Th=3, and U=1. With ICP-MS in combination with the evaporation step, detection limits of less than 50 pg/g have been achieved for Cr, Ni, and Zn and of <5 pg/g for the other elements except Fe, which could not be determined in concentrations less than 100 ng/g. On the other hand, the detection limits were much higher when the HF matrix was not removed before measuring by ICP-MS. A comparison of the different ICP-MS methods (isotope dilution technique and external calibration for both HF evaporated samples and those with HF matrix) with the results of TI-IDMS has been carried out. An excellent agreement was achieved between the results of TI-IDMS and the two ICP-MS methods using the HF evaporation step, whereas the ICP-MS techniques without HF evaporation essentially deviated from these results. Fe was the only trace element of all investigated heavy metals which could only be analysed by TI-IDMS in high purity HF in a concentration of about 3 ng/g. Although ICP-MS with isotope dilution and external calibration resulted in comparable analytical data, the ICP-IDMS method has some practical advantages such as time-saving and more reliable results.     

Analysis of heavy metals and sulphur-rich compounds in the water moss Fontinalis antipyretica L. ex Hedw.

The water moss Fontinalis antipyretica has been investigated to estimate heavy metal pollution in the river Elbe (middle Germany). Procedures of plant separation, digestion as well as an analytical method for ICP-MS analyses have been evaluated. Reproducibility and accuracy have been demonstrated on BCR 61 (NIST) reference material and results have been compared with AAS and AES data. The distribution of heavy metals in different plant segments of indigenous material has been analyzed. Exposition of plant material in the river Elbe have shown no correlation between the heavy metal content in plants and that of water samples. Cd and Zn concentrations found in the plant material are significantly enriched relatively to control samples. To understand the sophisticated real system experiments have been carried out under laboratory conditions to investigate induced sulphur-rich compounds in the presence of heavy metals using HPLC including on-line derivatization.     

A high-throughput solid-phase extraction microchip combined with inductively coupled plasma-mass spectrometry for rapid determination of trace heavy metals in natural water

Herein, a hyphenated system combining a high-throughput solid-phase extraction (htSPE) microchip with inductively coupled plasma-mass spectrometry (ICP-MS) for rapid determination of trace heavy metals was developed. Rather than performing multiple analyses in parallel for the enhancement of analytical throughput, we improved the processing speed for individual samples by increasing the operation flow rate during SPE procedures. To this end, an innovative device combining a micromixer and a multi-channeled extraction unit was designed. Furthermore, a programmable valve manifold was used to interface the developed microchip and ICP-MS instrumentation in order to fully automate the system, leading to a dramatic reduction in operation time and human error. Under the optimized operation conditions for the established system, detection limits of 1.64–42.54 ng L⁻¹ for the analyte ions were achieved. Validation procedures demonstrated that the developed method could be satisfactorily applied to the determination of trace heavy metals in natural water. Each analysis could be readily accomplished within just 186 s using the established system. This represents, to the best of our knowledge, an unprecedented speed for the analysis of trace heavy metal ions.     

Analytical approaches on some selected toxic heavy metals in the environment and their socio-environmental impacts: A meticulous review

Heavy metals are a group of metals and metalloids that have relatively high density and are toxic even at ppb levels. The excess intake of heavy metals in human bodies though the environment may cause various humans health problems. Analytical approaches of some selected toxic heavy metals in the environment and their socio-environmental impacts are discussed in this review. In this present investigation, we have also discussed the design and development of nanomaterials for the detection of metal ions along with kinetic approaches. The isolation or pre-concentration and determination of heavy metals from complex matrices become challenging for analytical chemists and researchers. The fundamentals on sample preparation and analysis of some selected heavy metals employing different analytical tools for qualitative and quantitative determination of these pollutants in real samples are also discussed. In addition, this compiled work enhanced our knowledge in learning about pathway mechanisms and the degree of their risk assessment.     

The Application of ICP-MS for Non-ferrous Metals Analysis

This paper reviews the current application of ICP-MS in non-ferrous metals analysis. Many analytical techniques that deal with the samples preparation,samples introduction, spectroscopic matrix interference, calibration and data treatment for non-ferrous metals analysis of ICP-MS are discussed. More and more fields such as geological,environment, biology and industry adopt ICP-MS as main analytical means for non-ferrous metals.     

Comparison of standard and reaction cell inductively coupled plasma mass spectrometry in the determination of chromium and selenium species by HPLC-ICP-MS

Elemental speciation is becoming a common analytical procedure for geochemical investigations. The various redox species of environmentally relevant metals can have vastly different biogeochemical properties, including sorption, solubility, bioavailability, and toxicity. The use of high performance liquid chromatography (HPLC) coupled to elemental specific detectors, such as inductively coupled plasma mass spectrometry (ICP-MS), has become one of the most important speciation methods employed. This is due to the separation versatility of HPLC and the sensitive and selective detection capabilities of ICP-MS. The current study compares standard mode ICP-MS to recently developed reaction cell (RC) ICP-MS, which has the ability to remove or reduce many common polyatomic interferences that can limit the ability of ICP-MS to quantitate certain analytes in complex matrices. Determination of chromium and selenium redox species is achieved using ion-exchange chromatography with elemental detection by standard and RC-ICP-MS, using various chromium and selenium isotopes. In this study, method performance and detection limits for the various permutations of the method (isotope monitored or ICP-MS detection mode) were found to be comparable and generally less than 1 μg L⁻¹. The method was tested on synthetic laboratory samples, surface water, groundwater, and municipal tap water matrices.     

Applications of inductively coupled plasma mass spectrometry and laser ablation inductively coupled plasma mass spectrometry in materials science

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have been applied as the most important inorganic mass spectrometric techniques having multielemental capability for the characterization of solid samples in materials science. ICP-MS is used for the sensitive determination of trace and ultratrace elements in digested solutions of solid samples or of process chemicals (ultrapure water, acids and organic solutions) for the semiconductor industry with detection limits down to sub-picogram per liter levels. Whereas ICP-MS on solid samples (e.g. high-purity ceramics) sometimes requires time-consuming sample preparation for its application in materials science, and the risk of contamination is a serious drawback, a fast, direct determination of trace elements in solid materials without any sample preparation by LA-ICP-MS is possible. The detection limits for the direct analysis of solid samples by LA-ICP-MS have been determined for many elements down to the nanogram per gram range. A deterioration of detection limits was observed for elements where interferences with polyatomic ions occur. The inherent interference problem can often be solved by applying a double-focusing sector field mass spectrometer at higher mass resolution or by collision-induced reactions of polyatomic ions with a collision gas using an ICP-MS fitted with collision cell. The main problem of LA-ICP-MS is quantification if no suitable standard reference materials with a similar matrix composition are available. The calibration problem in LA-ICP-MS can be solved using on-line solution-based calibration, and different procedures, such as external calibration and standard addition, have been discussed with respect to their application in materials science. The application of isotope dilution in solution-based calibration for trace metal determination in small amounts of noble metals has been developed as a new calibration strategy. This review discusses new analytical developments and possible applications of ICP-MS and LA-ICP-MS for the quantitative determination of trace elements and in surface analysis for materials science.     

The Utilization of Algae and Seaweed Biomass for Bioremediation of Heavy Metal-Contaminated Wastewater

The presence of heavy metals in water bodies is linked to the increasing number of industries and populations. This has serious consequences for the quality of human health and the environment. In accordance with this issue, water and wastewater treatment technologies including ion exchange, chemical extraction, and hydrolysis should be conducted as a first water purification stage. However, the sequestration of these toxic substances tends to be expensive, especially for large scale treatment methods that require tedious control and have limited efficiency. Therefore, adsorption methods using adsorbents derived from biomass represent a promising alternative due to their great efficiency and abundance. Algal and seaweed biomass has appeared as a sustainable solution for environmentally friendly adsorbent production. This review further discusses recent developments in the use of algal and seaweed biomass as potential sorbent for heavy metal bioremediation. In addition, relevant aspects like metal toxicity, adsorption mechanism, and parameters affecting the completion of adsorption process are also highlighted. Overall, the critical conclusion drawn is that algae and seaweed biomass can be used to sustainably eliminate heavy metals from wastewater.     

Determination of heavy metal complexes with humic substances by HPLC/ICP-MS coupling using on-line isotope dilution technique

An isotope dilution mass spectrometric (IDMS) method has been developed for the simultaneous determination of the complexes of 11 heavy metals (Ag, Cd, Cu, Mo, Ni, Pb, Tl, U, W, Zn and Zr) with humic substances (HS) by coupling HPLC with ICP-MS and applying the on-line isotope dilution technique. The HPLC separation was carried out with size exclusion chromatography. This HPLC/ICP-IDMS method was applied to samples from a brown water, ground water, sewage and seepage water as well as for a sample containing isolated fulvic acids. The total contents of heavy metals and of their complexes were analyzed in these samples with detection limits in the range of 5–110 ng/L. The analysis of heavy metal/HS complexes from the different waters resulted in characteristic fingerprints of the distribution pattern of heavy metals in the separated HS fractions. A comparison between the total heavy metal concentrations and their portions bound to humic substances showed distinct differences for the various metals. Simultaneous ¹²C detection was used for the characterization of HS complexes not identified by UV detection and for the determination of relative DOC concentrations of chromatographic peaks. Received: 21 February 1997 / Revised: 27 May 1997 / Accepted: 28 May 1997     

北江干流沉积物重金属污染生态风险评价

通过北江干流水体沉积物重金属含量,研究其典型污染物的潜在生态风险。采集了北江干流韶关至清远段7份沉积物样品,经混酸消解后,以电感耦合等离子体质谱仪测定沉积物中重金属含量,并对沉积物重金属分布特征进行了分析。同时利用Hakanson的潜在生态危害指数（RI）评价模式,对北江干流沉积物重金属生态风险进行了评价。评价结果表明,北江干流沉积物中重金属综合生态危害程度均表现为很高级别,其生态危害因子Pb、Cd已成为北江干流突发性水污染事故潜在预警因子。     

Comparison of sediment pollution in the rivers of the Hungarian Upper Tisza Region using non-destructive analytical techniques

The rivers in the Hungarian Upper Tisza Region are frequently polluted mainly due to mining activities in the catchment area. At the beginning of 2000, two major mining accidents occurred in the Romanian part of the catchment area due to the failure of a tailings dam releasing huge amounts of cyanide and heavy metals to the rivers. Surface sediment as well as water samples were collected at six sites in the years 2000–2003, from the northeast-Hungarian section of the Tisza, Szamos and Túr rivers. The sediment pollution of the rivers was compared based on measurements of bulk material and selected single particles, in order to relate the observed compositions and chemical states of metals to the possible sources and weathering of pollution. Non-destructive X-ray analytical methods were applied in order to obtain different kinds of information from the same samples or particles. In order to identify the pollution sources, their magnitude and fate, complementary analyses were carried out. Heterogeneous particulate samples were analyzed from a large geographical territory and a 4-year time period. Individual particles were analyzed only from the “hot” samples that showed elevated concentrations of heavy metals. Particles that were classified as anthropogenic were finally analyzed to identify trace concentrations and chemical states of heavy metals.     

Electrochemical removal and simultaneous sensing of mercury with inductively coupled plasma-mass spectrometry from drinking water

Mercury is a naturally occurring metallic chemical element in environment. Environmental levels of mercury vary between water resources. The concentration level of mercury in drinking water is 30 ng/L, which is accepted by US Environmental Protection Agency. Therefore, the simultaneous sensing and treatment of water by recently improved technologies are very important. In this work, inductively coupled plasma-mass spectrometry (ICP-MS) and electrochemical techniques were applied together to determine and remove mercury for the first time. ICP-MS was chosen as a sensitive, multielement capable, powerful, and reliable spectrometry type between other heavy metals determination methods, and it is also applied to research drinking water resources. New nanodimensional surfaces were constructed to respond to specific mercury behavior, and simple, cost-efficient, and practical electrochemical techniques were used to remove mercury existing in drinking water samples. After electrodeposition of mercury over the proposed electrode, treated, clean, and mercury-free water samples were obtained.     

Recent advances on hydrogels based on chitosan and alginate for the adsorption of dyes and metal ions from water

In contemporary times, water resources have become increasingly scarce and suffer from anthropogenic pollution sources with an organic and inorganic origin that are products of industrial, agricultural, and everyday waste. Contamination with heavy metals and dyes in wastewater is considered a risk for water sources that can leak into underground and surface sources, leading to increased biological and chemical contamination. The pollutant removal process is performed by adsorption treatment methods, which is the most common method, and it is considered an effective method with a high and economical removal rate.In this review, we discuss the use of biobased hydrogel adsorbents in the removal of organic dyes and metal ions from water. The literature indicates that hydrogels exhibit rapid absorption kinetics and a dye removal absorption capacity that can reach more than 100 mg/g and sometimes more than 2000 mg/g, with a metal adsorption capacity ranging from 38 mg/g to more than 440 mg/g. These results are discussed and compared by taking into account hydrogel materials that contain biopolymers such as alginate, chitosan or both. In general, absorption depends mainly on biobased materials, which have a natural origin and can be utilized to synthesize hydrogels to remove pollutants, dyes and heavy metals. Chitosan and alginate are prominent materials for this use and they can be incorporated with other components to obtain hydrogels or nanocomposite materials with different efficacies to remove dyes and metal ions.     

Remediation of metalliferous soils through the heavy metal resistant plant growth promoting bacteria: Paradigms and prospects

Various industrial, agricultural and military operations have released huge amounts of toxic heavy metals into the environment with deleterious effects on soils, water and air. Under metal stress, soil microorganisms including plant growth promoting bacteria (PGPB) have developed many strategies to evade the toxicity generated by the various heavy metals. Such metal resistant PGPB, when used as bioinoculant or biofertilizers, significantly improved the growth of plants in heavy metal contaminated/stressed soils. Application of bacteria possessing metal detoxifying traits along with plant-beneficial properties is a cost effective and environmental friendly metal bioremediation approach. This review highlights the different mechanisms of metal resistance and plant growth promotion of metal resistant PGPB as well as the recent development in exploitation of these bacteria in bioremediation of heavy metals in different agroecosystems.     

The determination of trace elements in crude oil and its heavy fractions by atomic spectrometry

A literature review on the determination of trace elements in crude oil and heavy molecular mass fractions (saturates, aromatics, resins and asphaltenes) by ICP-MS, ICP OES and AAS is presented. Metal occurrences, forms and distributions are examined as well as their implications in terms of reservoir geochemistry, oil refining and environment. The particular analytical challenges for the determination of metals in these complex matrices by spectrochemical techniques are discussed. Sample preparation based on ashing, microwave-assisted digestion and combustion decomposition procedures is noted as robust and long used. However, the introduction of non-aqueous solvents and micro-emulsions into inductively coupled plasmas is cited as a new trend for achieving rapid and accurate analysis. Separation procedures for operationally defined fractions in crude oil are more systematically applied for the observation of metal distributions and their implications. Chemical speciation is of growing interest, achieved by the coupling of high efficiency separation techniques (e.g., HPLC and GC) to ICP-MS instrumentation, which allows the simultaneous determination of multiple organometallic species of geochemical and environmental importance.     

Analysis of inorganic nitrogen and related anions in high salinity water using ion chromatography with tandem UV and conductivity detectors

Over 97% of the Earth's water is high salinity water in the form of gulfs, oceans, and salt lakes. There is an increasing concern for the quality of water in bays, gulfs, oceans, and other natural waters. These waters are affected by many different sources of contamination. The sources are, but not limited to, groundwater run-off of nitrogen containing fertilizer, pesticides, cleaning agents, solid wastes, industrial waters, and many more. The final destinations of these contaminants are rivers, lakes, and bayous that eventually will lead to bays, gulfs, and oceans. Many industries depend on the quality of these waters, such as the fishing industry. In addition to wild marine life, there are large aquariums and fish and shrimp farms that are required to know the quality of the water. However, the ability of these industries to monitor their processes is limited. Most analytical methods do not apply to the analysis of high salinity waters. They are dependent on wet chemistry techniques, spectrophotometers, and flow analyzers. These methods do not have the accuracy, precision, and sensitivity when compared to ion chromatography (IC). Since the inception of IC, it has become a standard practice for determining the content of many different water samples. Many IC methods are limited in the range of analytes that can be detected, as well as the numerous sample sources of which the methods are applicable. The main focus of current IC methods does not include high salinity waters. This research demonstrates an ion chromatographic method that has the ability to determine low level concentrations of inorganic nitrogen and related anions (nitrite-N, nitrate-N, phosphorous-P, sulfate, bromide, chloride, sulfide, fluoride, ammonia, calcium, and magnesium) in a single run using a combination of UV and conductivity detectors. This method is applicable to various waters, and uses both freshwater and high salinity water samples.     

Green Carbon Materials for the Analysis of Environmental Pollutants

Green carbon materials (GCMs) have attracted great attention as they have unique mechanical, optical, and electrical properties that make them suitable for the development of the next generation of miniature, low-power, and mobile sensors. In this review paper, an attempt has been made to explore green carbon materials where their synthesis methods, conjugation with other types of nanomaterials to form nanocomposites, thus combining different properties into one single novel material, and environmental analysis applications are detailed. Green carbon materials have great significance in the analysis of environmental pollutants because they increase the effective area of an electrode, improve the rate of electron transfer between the analytes and the electrode, and help in catalysis, which in turn increases the efficacy of an electrochemical reaction, absorption, detection, and elimination. Moreover, functionalized green carbon materials when used in sensors for fast, economic environmental pollutant analysis are found to be highly sensitive to monitoring heavy metals and other polluting impurities in air, water sources, soils, etc. This review covers research and advancements in a broad span from 2013 to 2021, and some of the leading and fascinating research articles from the early years of the century have also been incorporated.